-------
ON
-P-
O
1
Cooling
water
Heat 1 1
1 II
HC1
•
(193 XJ
Substitution
Steam
Acetic acid
1 J*
194 XJ
Esterification
Cooling water
sTlt
H2S04
1
196
Condensation
4 T
Est
CO 0
1 p>
erification 1
Cooling water
"*°nit I5tri
H2S04
195
Condensation
oonng
water
n
so3
1 ^
197
Addition
XJ
199
Ammonolysis
Dimethyl amine
1 ISteam
Ami da t ion
200
Figure 10. Methane Section Process Flow Sheet (Cont.)
-------
Cooll
St
ng water
Ttl
Cooling water
tO - steay [ (
201
Carbonylatlon
Water fr>o
^^i 202 ^^
Oxidation
CS2 Heat
1 \ >c
206 XI
Condensation
o
LJ
Water
rr
IROH ^" Cooling water
itlon 203
Ion
XJ
Aniline 1
204
Condensation
^
Condens
NH3
205
Hexa-
[ methylene-J
itetramlne;
Heat
N02
\
207
Oxidation
•<
Figure 10. Methane Section Process Flow Sheet (Cont.)
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 157
Methyl Chloride
CH4 + C12 * CH3C1 + HC1
!• Function - As of 1970, chloromethane was made either b'y the chlori-
nation of methane (70%) or the hydrochlorination of methanol (22%).
The chlorination of methane process sequence requires four main
steps; reaction, HC1 recovery, chlorides recovery and chlorides re-
fining. High purity methane, chlorine and recycle methane are pre-
mixed and fed to the reactor. The reactor effluent, containing
organic chlorides, HC1, excess methane, and only traces of chlorine,
is cooled and fed to the HC1 recovery system.
The first column in this system is an absorber designed for
efficient HC1 removal. The bulk of the absorbing liquor is HC1 azeo-
trope (about 20 percent by weight HC1). The rich acid is thus above
the azeotrope and allows stripping of anhydrous HC1. The second
column distills off anhydrous HC1 and produces the required azeotrope
in the bottoms. For high yields of methyl chloride, the amount of
recirculating methane is increased.
The HCl-free gases from the absorber are washed with caustic
soda to remove final traces of HC1 and are then ready for chlorides
recovery by compression, cooling, and drying with sulfuric acid.
2. Input Materials - Basis - 1 metric ton methyl chloride
Methane - 179 kg/Mg (358 Ib/ton) product 1445 m3 (15,713 ft3/ton)
Chlorine - 1587 kg/Mg (3,174 Ib/ton) product 1405 kg (3,097 Ibs/ton)
Sulfuric Acid
Caustic Soda
6-404
-------
3. Operating Parameters
Temperature - 400 - 500°C (752-932°F)
Pressure - 200 kPa (2 atm)
Flow Rate - not given
Catalyst - None
4. Utilities
Electric Power - not given
Cooling Water - not given
5. Waste Streams
Dehydrator (air)
Purge on recycled methane to remove inerts
CH4 - 1 kg/Mg (2 Ib/ton) product
CH3C1 - 13 kg/Mg (26 Ib/ton) product
CH2C12 - 2 kg/Mg (4 Ib/ton) product
CHC13 - 1 kg/Mg (2 Ib/ton) product
- 1 kg/Mg (2 Ib/ton) product
Waste acid solution is discharged from the dehydrator.
Waste caustic solution is discharged from the washer. where traces
of HC1 are removed from the product gases .
6. EPA Source Classification - None
7. References
Sittig, M. , Pollution Control in the Organic Chemical Industry,
Noyes Data Corporation, Park Ridge, N.J., 1974, p. 105-
Austin, G. T., "Industrially Significant Organic Chemicals - Part 3,"
"Chemical Engineering," March 18, 1974, p. 89,90.
Lowenheim, F. A. and Moran, M. K. , Industrial Chemicals , 4th Edition,
John Wiley & Sons, New York, N.Y. , 1975, p. 531,532.
6-405
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 158
Methylene Chloride (chlorination of methane)
CH^ + 2C12 > CH2C12 + 2HC1 + co-products
1. Function - Processes for CHLC1- manufacture are based on chlorination
of methane, although the other chloromethanes are probable co-products
of this route, their relative proportions are determined by process
operating conditions.
A typical methane chlorination synthesis of methylene chloride
and co-products is as follows. A preheated mixture of methane and
chlorine passes into a vessel where reaction is promoted by a control
of feed-gas flow rate and the reactor temperature. In addition to
chloromethanes, the exit gas contains unreacted methane and hydrogen
chloride. Initial separation of the product group from CH, and HC1 is
generally affected by scrubbing the effluent gas with a refrigerated
mixture of higher chloromethanes, in which the methane and hydrogen
chloride are only slightly soluble. The methane, freed from acid by
water scrubbing, is recycled to the chlorinator and the chloromethanes,
containing the desired CH_C1~, after washing, alkali scrubbing, and
drying, pass to a sequence of fractionating columns.
2. Input Materials
Methane - 0.179 kg/kg product
Chlorine - 1.587 kg/kg product
3. Operating Parameters
Temperature: 360 - 500°C (680 - 932°F)
6-406
-------
Pressure: 205 kPa (2 atm)
Catalyst: UV light from mercury vapor lamps
4. Utilities
Not given
5. Waste Streams - Scrubbing water effluent with chloromethanes to
remove methane and hydrogen chloride from the desired products
results in the following emissions.
CH - 1 g/kg product
CH Ci - 13 g/kg product
CH
2C12 - 2 g/kg product
CHCl - 1 g/kg product
CC1, - 1 g/kg product
Water scrubbing to free HCl from methane stream should lead to
emissions of CLand a waste acid solution. Alkali used in neutra-
lizing the latter and in scrubbing the CH_C12 - containing stream
yield spent caustic as a further pollutant.
Note that methylene chloride forms toxic products, such as phosgene,
when exposed to hot surfaces or open flames.
6. EPA Source Classification Code - None
7. References
Hedley, W. H., et. al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 115.
6-407
-------
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 7," Chemical Engineering, June 29, 1974, p. 154.
"Air Pollution from Chlorination Processes," prepared for Office
of Air Program, Environmental Protection Agency, Contract No.
CPA 70-1, Task Order No. 23, March, 1972.
6-408
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 159
Chloroform (chlorination of methane)
CH, + C12 >• mixed products including CHC13
1. Function - Chloroform was formerly made by reaction of chlorinated
lime (bleaching powder) and acetone, acetaldehyde, or ethanol, but
this appears to be uneconomical in most cases. Currently, chlorination
of methane is the principal route to chloroform, with other chloro-
methanes usually co-produced. Control of the chlorine/methane feed
ratio and other operating conditions influence the yield of CHCl.,.
A two-stage chlorination provides the maximum yield. Purification
of chloroform is accomplished by extraction with concentrated sul-
furic acid followed by repeated distillation.
Chloroform may also be made by substituting methanol for methane.
2. Input Materials - Basis - 1 metric ton chloroform
Methane- 187 m3 (6,604 ft3)
Chlorine- 1780 kg (3924 Ibs)
3. Operating Parameters
Temperature: elevated (250 - 800°C ?) (482-1472°F)
Pressure: not given
Catalyst: ultraviolet light (optional)
4. Utilities
Not given
5. Waste Streams - Various chloromethanes might be emitted from the
methane chlorinator. Neutralization of sulfuric acid used in puri-
fication and by-product hydrochloric acid may lead to spent caustic
and traces of acid in the waste water flow.
6-409
-------
Note that chloroform slowly oxidizes to phosgene on exposure to
sunlight.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -"
Part 3," "Chemical Engineering," March 18, 1974, p. 89.
"1975 Petrochemical Handbook," "Hydrocarbon Processing," November
1975, p. 127.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 266.
6-410
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 160
Carbon Tetrachloride (chlorination of methane)
CH. + C10 >• CC1, + CHC1, + CH0C10 + CH,C1
42 4 3223
1. Function - Since the 1950's chlorination of hydrocarbons, particularly
methane, has been a more important production route to carbon tetra-
chloride in the United States than chlorination of carbon disulfide.
The chemical process is referred to as chlorinalysis, which involves
the simultaneous breakdown of hydrocarbons and chlorination of molecular
fragments. As methane and chlorine react in this manner, some carbon
tetrachloride is produced, along with varying amounts of other chloro-
methanes. The relative quantities depend on the composition of the
hydrocarbon starting material and the conditions of chlorination. With
a C12/CH, molar ratio of 0.6, and a reaction temperature of 340-370°C,
the following yields are obtained: CCl,-2%, CHC13~10%, CH-Cl2-29%,
CfLCl-58%. Recycling partially chlorinated materials and using light
as a catalyst permits essentially complete conversion to carbon tetra-
chloride. The gas flow must be rapid to keep the likelihood of an
explosion to a minimum. This process requires corrosion resistant
metals (Ni) and exacting controls since the reaction is quite exothermic.
In Hlils process, a 5:1 ratio of C19 to CH, by volume is reacted at
650°C, the temperature being controlled by regulating the gas flow rate.
A heat exchanger cools the exit gas to 450°C before it is passed to a
second reactor for the addition of more methane. Perchloroethylene is
the principal co-product in this case.
6-411
-------
Crude carbon tetrachloride is generally purified by neutralization
and drying, followed by distillation. Additional purification can be
obtained at the distillation stage by maintaining the carbon tetrachloride
for a prolonged period under total reflux before actually starting the
distillation itself. Decomposition of carbon tetrachloride upon contact
with water or on heating in air make it practical to add a small quantity
of stabilizer to the commercial product.
Carbon tetrachloride may also be prepared from carbon disulfide:
CS2 + 3C12 2pfc ) CC14 + S2C12
>. CC14 + 6S
4S + 2C12 »• 2S2C12
Carbon tetrachloride is also a by-product of the vigorous chlorination
and dehydrochlorination of ethylene dichloride and the Deacon process.
2. Input Materials - Basis - 1 metric ton product
Methane - 110 kg (242.5 Ibs)
Chlorine - 2.210 kg (4872 Ibs)
3. Operating Parameters
Temperature - 250-650°C (482-1202°F)
Pressure - atmospheric
Catalyst - light (optional)
Reaction time - very short
6-412
-------
4. Utilities - Basis - 1,000 kg CC14
Electricity, GJ - 0.486 (135 kWh)
Steam (1.2 MPa, 12 bar), kg-135 (298 Ibs)
Steam (0.95 MPa, 4.5 bar), kg-135 (298 Ibs)
Cooling water, m3 - 85 (22,457 gal)
Fuel, GJ-0.837 (2 x 105 kcal)
5. Waste Streams - Various chloromethanes emitted from the process during
the early repeated-chlorination stage (8 Ibs./lOO Ibs. product). An
alkali of some sort is used to neutralize hydrochloric acid (118 Ibs./
100 Ibs. product) which is formed by the chlorination reaction and
traces of the spent liquid might appear in wastewater flow.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 2," "Chemical Engineering," February 18, 1974, p. 127.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 132,133.
Faith, W. L., et. al., Industrial Chemicals. 3rd Ed., John Wiley & Sons,
Inc., New York, N.Y., 1965, p. 229-231.
Sittig, M., Organic Chemical Processes, Noyes Press, Inc., Pearl River,
N.Y., 1972, p. 39,40.
6-413
-------
7. References (continued)
"1973 Petrochemical Handbook," "Hydrocarbon Processing," November 1973,
p. 156-157.
"1975 Petrochemical Handbook," "Hydrocarbon Processing," November 1975,
p. 126.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 232.
6-414
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 161
Chlorodifluoromethane (chloroform and hydrogen fluoride)
(SKI,)
CHC1, + 2HF —*• CHC1F2 + 2HC1
1. Function - Chlorodifluoromethane is derived by reaction of chloro-
form with anhydrous hydrogen fluoride, catalyzed by antimony tri-
chloride.
2. Input Materials
Chloroform
Anhydrous hydrogen fluoride
3. Operating Parameters
Temperature: not given
Pressure: not given
Catalyst: SbCl,
4. Utilities - not given
5. Waste Streams - Various chlorofluoromethanes are potential gaseous
emittants. By-product hydrochloric acid and caustic solution used
in neutralization may appear in waste water streams.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 9 (1966), p. 743,
746.
6-415
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 162
Carbon Tetrabromide (from carbon tetrachloride)
AlBr
CC1. --> CBr.
4 4
1. Function - Carbon tetrachloride reacts with aluminum tribromide
at high temperature to yield carbon tetrabromide.
2. Input Materials
Carbon tetrachloride
Aluminum tribromide
3. Operating Parameters
Temperature - 100°C (212°F)
Pressure - Not given
4. Utilities - Not given
5. Waste Streams - The various bromethanes are possible emissions from
this process. Carbon tetrachloride, aluminum hydroxide, and possibly
some HBr or Br_ may be present in the waste streams.
>.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 131.
6-416
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 163
Dichlorodifluoromethaiie and Trichlorofluoromethane
(catalytic fluorination of carbon tetrachloride)
SbCl,- catalyst
3CC14 + 2SbF3
6HF + 2SbCl3 >- 2SbF + 6HC1
SbCl5
2CC14 + 3HF >• CClgF + CCl^ + 3HC1
1. Function - Preparation of these two chlorofluoromethanesis not by
direct fluorination but rather by the replacement of chlorine atom
of carbon tetrachloride with fluorine due to the action of SbF, con-
taining antimony pentahalide, either SbCl,- or SbF,., as catalyst.
The industrial process uses liquid hydrogen fluoride as an inex-
pensive source of fluorine arid involves continuous regeneration
of a small initial batch of SbF .
The process is usually conducted at about 100°C and from 0 to 3.45
MPa (0-34.0 atm) with gaseous HF. Dichlorodifluoromethane and
hydrochloric acid, which is insoluble in liquid HF, are taken off
to a column which readily separates the partially fluorinated sub-
\
stance CC1-F.
2. Input Materials - Basis - 1 metric ton dichlorodifluoromethane
Carbon tetrachloride CC14 - 1600 kg (3527 Ibs)
Antimony (III) fluoride SbF- - small
Hydrogen fluoride - 413 kg (911 Ibs)
6-417
-------
3. Operating Parameters
Temperature: 0-100°C (0-212°F)
Pressure: 0-3.45 MPa (0-34.0 atm)
Catalyst: SbCl5 (or SbF5)
4- Utilities - Not given
5. Waste Streams - Hydrogen chloride produced, which is insoluble in
liquid HF, must be removed and neutralized before ultimate disposal,
leading to possible pollution of waste liquid flow by HCl, spent
caustic, and perhaps traces of dissolved HF. Any gas-phase reaction
is a potential source of chlorofluorohydrocarbons to be emitted to
the air.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 4," "Chemical Engineering," April 15, 1974, p. 86, 87.
U.S. Patent 3,381,044 (April 30, 1968).
Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,
Noyes Development Corp., Park Ridge, N.J.,1969, p. 232.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 325, 326.
6-418
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO.164
Carbon Bisulfide (catalytic methane-sulfur reaction)
CH. + 4S > CS0 + 2H0S
4 22
1. Function - The basic production of CS? in the United States is
currently limited to the catalytic reaction of methane (or natural
gas) and sulfur vapor; this Thacker process having almost com-
pletely (70%) replaced the older charcoal-sulfur retort method.
This system provides yields of over 90 mole percent carbon disulfide
per pass with the use of active catalysts such as silica gel. The
process usually operates in the temperature range 500-700°C, and the
pressure may be about 170 kPa (25 psi). Space velocities, based on
hydrocarbon gas charge, in this case methane, are on the order of 100-
400 volumes of gas per hour per unit volume of catalyst. Sulfur is
usually charged in slightly higher than stoichiometric amounts.
The hydrogen sulfide formed may be used as an end product or it
may be reconverted to elemental sulfur, for recycle to the reaction
system, in a separate partial oxidation unit using the Glaus process.
This involves burning H2S with air to form sulfur dioxide, which then
reacts with the remaining H2S, at about 300°C in the presence of catalyst,
to form sulfur. The Glaus process permits about 95% conversion to
sulfur based on the hydrogen sulfide charge.
The process flow for the carbon disulfide formation reaction is
as follows. Molten sulfur, maintained at about 130°C, is transferred
to a sulfur boiler where it is vaporized and further heated to 575-650°C
to convert the sulfur vapor to the diatomic form. Methane, or natural
6-419
-------
gas from which higher molecular weight paraffins are substantially
removed, is preheated to 550-650°C and mixed with the sulfur vapor.
The mixed stream, with or without additional heating, is passed down-
ward through a fixed-bed catalytic reactor for the formation of CS_.
The reason for avoiding higher molecular weight hydrocarbons in the
feed is that under specified conditions, these are more reactive than
CH, and will combine with sulfur to produce polymerization and conden-
sation products, leading to catalyst contamination.
The reactor effluent is cooled to about 130°C and the unreacted sul-
fur is separated in a gas-sulfur separator and recycled to the process.
Simultaneously, small amounts of sulfur dust in the product stream are
removed by scrubbing with liquid sulfur. The carbon disulfide is
separated from H-S by preferential absorption in a suitable mineral oil
solvent from which it is subsequently stripped and sent to a distilla-
tion section.
The stripped carbon disulfide is separated from small amounts of
impurities in two successive distillations with low-boiling impurities
removed overhead in the first column. The bottoms material from this
section is distilled in a second column where the final high-purity CS0
is recovered as the distillate. The off-gas from the carbon disulfide
absorber contains 90-95% H_S and passes to the sulfur recovery unit.
Due to the corrosive nature of sulfur and hydrogen sulfide at
high temperatures, stainless-steel alloys are employed in the preheaters
and reactor units. High-chromium (25% Cr) and stabilized nickel-
chromium alloys are satisfactory.
6-420
-------
2. Input Materials - Basis - 1 metric ton CS_
Methane:(or natural gas stripped of higher molecular weight paraffins)
345 m3 (12,184 ft3)
Sulfur:(vapor) 925.kg (2,039 Ibs)
3. Operating Parameters
Temperature: 500-700°C (932-1292°F)
Pressure: 130-300 kPa (1.28-2.96 atm)
Catalyst: activated Al_0 + Cr-O-
(others - alumina, silica-alumina, bauxite, silica-zirconia)
Hourly space velocity: 600 per hr.
4. Utilities
Not given
5. Waste Streams - Carbon disulfide manufacture contains a large number
of potential emission sources and hence pollutants. The sulfur boiler
and the introduction of recycle sulfur at the start of the process flow
may lead to sulfur vapor escaping. Heating the methane or natural gas
feed stream could be a source of gaseous hydrocarbons. Light mercaptans
and heavy di-acid polysulfides are formed. The Glaus sulfur recovery
unit and the purification of carbon disulfide by staged distillation
should give off undetermined amounts of sulfur compounds, including
H2S and S0_.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 2," ''Chemical Engineering," February 18, 1974, p. 127.
6-421
-------
7. References (continued)
Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience
Publishers, New York, N.Y., Vol. 4 (1964), p. 376-378.
Hahn, A. V., The Petrochemical Industry; Markets and Economics, McGraw-
Hill Book Co., New York, N.Y., 1970, p. 168,169.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 224,225.
6-422
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 165
Perchloromethyl Mercaptan (chlorination of carbon disulfide)
CS2 + 6C12 > SC12 + Closer
1. Function - Perchloromethyl mercaptan is prepared by the chlorination
of carbon disulfide at 20°C in the presence of iodine as a catalyst.
The reaction is carried out in glass-lined jacketed vessels. Chlori-
nation is continued until 3-5% excess chlorine is present. (The
excess chlorine converts any S-Cl- to SCI-).
The reaction mixture is then fractionally distilled under a
20 in. vacuum to remove the SC1_, excess chlorine, unreacted CS» and
CCl^, . An 85% yield of 97-98% purity product is obtained. Perchloro-
methyl mercaptan is an intermediate for the fungicide Captan.
2. Input Materials
Carbon disulfide
Chlorine
3. Operating Parameters
Temperature - 20°C (68°F)
Pressure (for distillation) --2.66 kPa (0.026 atm)
Catalyst - Iodine
4- Utilities - Not given
5. Waste Streams - Emission probably contains traces of reactants, hydrolysis
products of chlorinated compounds, and sulfur from decomposition of
S2CV
6-423
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 19 (1969), p. 374.
Senning, A., Editor, Sulfur in Organic and Inorganic Chemistry,
Marcel Dekker, Inc., New York, N. Y., Vol. 1, 1971 , p. 244.
Kharasch, N. and Meyers, C.Y., The Chemistry of Organic Sulfur Compounds,
Vol. 1, 1961 , p. 362-364.
6-424
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 166
Hydrogen Cyanide (reaction of methane, ammonia, and air)
2CH4 + 2NH3 + 302 >• 2HCN + 6H20
1. Function - As of January 1971, 70% of the hydrogen cyanide produced
in the United States was manufactured via the Andrussow process. In
the process a mixture of air, CH,, and NH_ in a volume ratio of 6:1:0.9
is passed over the catalytic surface at a pressure of about 250 kPa
(22 psig) and gas velocity of .53 m/sec. A typical catalyst consists
of a number of layers of woven, 80-mesh 90% platinum - 10% rhodium
gauze made of 3-mil wire. The hot gases from the reactor are quenched
(to prevent polymerization of HCN), and unreacted ammonia is removed
(as (NH,)_SO,) or recycled. The off-gas, with ammonia removed goes
to a cold water acidic absorber to remove HCN which is then stripped
and fractionated by conventional means. Assuming recycle of unreacted
NH_, the ultimate yield of HCN can be 87% of the theoretical value.
The DEGUSSA and Fluohmic processes are variations of the Andrussow
process.
2. Input Material - Basis - 1 metric ton HCN (99.5%)
Methane - 115m3
Air - 7500 m3
Ammonia - 830 kg (assuming 75% yield)
Phosphoric acid, 85% (stabilizer)
Sulfuric acid, sp.gn.1.7 - 725 kg
6-425
-------
3. Operating Parameters
Temperature - 1000-1200°C (1832-2192°F)
Pressure - ~250 kPa (2.47 atm)
Gas feed velocity - .53 m/sec.
Catalyst: Pt/Rh mesh
4. Utilities - Not given
5. Waste Streams - Possible air emissions - NH3, CH^, HZ, HCN, CO. Waste
water - solutions of sulfuric acid, and ammonium sulfate.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology? 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 6 (1965), p. 576-580.
Lowenheim, F. A. and Moran, M. M., Industrial Chemicals. 4th Edition,
John Wiley & Sons, New York, N. Y., 1975, p. 482-486.
6-426
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 167
Ethyl Orthoformate(from HCN/HCl/EtOH)
NH
TTpi " T?t~OH
HCN + EtOH > H-C-OEt • HC1 r,» HC(OEt).,
cold J
•'•• Function - Ethyl orthoformate is prepared in a two-step process by
reacting hydrogen cyanide, ethanol, and hydrochloric acid at room
temperature followed by reaction with ethanol in the cold.
2. Input Material
Hydrogen cyanide
Ethanol
Hydrochloric acid
3. Operating Parameters
Temperature: 1st Step - room temperature
2nd Step - reduced temperature
4. Utilities - Not given
5. Waste Streams - Unreacted HCN, EtOH, and HC1 should be present along
with ammonia and/or ammonium salts.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 6 (1965), p. 574.
6-427
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 168
Cyanogen Chloride (chlorinatlbri of hydrogen cyanide)
NaCN (aq) + C±2 >• NCC1+ NaCl
HCN + C12 > NCC1H- HC1
1. Function - Cyanogen chloride is readily formed by the reaction of
hydrogen cyanide and chlorine in the liquid phase. A possible pre-
liminary stage in cyanogen chloride manufacture is the reaction of
hydrogen cyanide with sodium hydroxide in aqueous solution to form
NaCN. Sodium cyanide may then be chlorinated in aqueous solution
(pH <8.5) to give NCC1.
2. Input Materials
Hydrogen cyanide
Chlorine
3. Operating Parameters
Not given
4. Utilities
Not given
5. Waste Streams - chlorine gas, HCN, and NCC1 are all possible air-
borne emissions. Wastewater will probably contain trace of
hydrogen cyanide as well as spent caustic and sodium chloride
from scrubbing operations used to nuetralize the hydrochloric
acid by-product.
6. EPA Source Classification Code - None
6-428
-------
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 3.
Hahn, A. V., The Petrochemical Industry; Markets and Economics,
McGraw-Hill Book Co., New York, N.Y., 1970, p. 160.
6-429
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 169
Cyanuric Chloride (polymerization of cyanogen chloride)
Cl
3C1-C=N
C
i
Cl
1. Function - Cyanuric chloride is prepared by the vapor phase
polymerization of cyanogen chloride.
2. Input Materials
Cyanogen chloride
Charcoal carrier impregnated with 3.75% CaCl2, BaCl2, or S^l-
3. Operating Parameters
Temperature: 250-480°C (482-896°F) .
4. Utilities - Not given.
5. Waste Streams - Spent polymerization catalysts may be present in
process wastes. Possible atmospheric emissions include cyanogen
chloride and by-products.
6. EPA Source Classification Code - None.
7. References
British Patent 602,816 (June 3, 1948).
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 20 (1969), p. 667.
6-430
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 170
Acetone Cyanohydrin
(CH3)2CO + HCN ->• (CH3)2COHCN
1. Function - Acetone cyanohydrin is manufactured on an industrial
scale by the base-catalyzed condensation of acetone and hydrogen
cyanide. The reaction temperature is normally kept under 40°C.
The product must be acidified to prevent decomposition.
2. Input Materials
Acetone - 0.6 kg/kg product
Hydrogen cyanide
Unspecified acid •
3. Operating Parameters
Temperature: < 40°C (104°F)
Pressure: atmospheric pressure
Catalyst: caustic soda
4. Utilities
Not given
5. Waste Streams - Information available on this process was too limited
to identify specific pollutant sources. However, reactants are probably
present in air emissions from reactor vents and purification procedures.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 6 (1965), p. 672.
6-431
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7. References Ccontinued)
Waddams, A. L., Chemicals from Petroleum, 3rd Ed., John Murray Ltd.,
London, Eng., 1973, p. 127.
6-432
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 171
Methacrylic Acid (from acetone cyanohydrin)
(CH3)2COHCN
P
CH2=C(CH3)CONH2 • H2S04 + H20 ™ )CH2=C(CH3)COOH
-• Function - In the preparation of methacrylic acid, acetone cyano-
hydrin and concentrated sulfuric acid are pumped to a hydrolysis
kettle where they react to form methacrylamide sulfate. This
conversion is usually carried out at 130 - 150° C.
After cooling, the crude intermediate is taken to a second
reactor where is combines with water to form methacrylic acid
and ammonium bisulfate.
The product stream is then pumped to the acid-stripping
column where methacrylic acid and some water distill. The resi-
due, made up of sulfuric acid, ammonium bisulfate, and water, is
sent to the ammonium sulfate plant.
The overhead from the acid-stripping column enters a recti-
fier column where methacrylic acid comes over the top, is condensed,
and is sent to the wash column. Crude methacrylic acid comes off
on the top of the wash column, and is shipped to other plants for
further distillation. The water solution from the bottom of the
column is recycled to the rectified column to complete methacrylic
acid recovery.
Polymerization inhibitors are added at the acid-stripping
column and the rectified columns.
6-433
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2. Input Materials
Acetone cyanohydrin - 1.18 kg/kg product
Sulfuric acid
Water
Polymerization inhibitors
3. Operating Parameters
Temperature: first reactor - 130-160° C (266-320°F)
second reactor - 90° C (194°F)
Pressure: Not given
4. Utilities - Not given
5. Waste streams - The waste water stream from the rectifier column
probably contains small quantities of methacrylic acid and poly-
merization inhibitors. Traces of methacrylic acid and other
organics may be discharged to the air by various processing
equipment.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967), p. 333.
6-434
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 172
Methacrylic Esters (from acetone cyanohydrin)
(CH3)2COHCN
H2S04 + ROM CH2
1. Function - Methacrylic esters are prepared from acetone cyanohydrin
in the same manner as methacrylic acid (see Process No. 171). In
this process variation, the methacrylamide sulfate intermediate is
reacted with ethyl, n-butyl, isobutyl, n-hexyl, or n-lauryl alcohol
*
rather than water to yield the corresponding ester.
Ester recovery operations are essentially the same as those used
in methacrylic acid purification. An alcohol recovery section is
necessary, however, to strip excess alcohol from the rectifier bottoms
for recycle.
2. Input Materials
Acetone cyanohydrin
Sulfuric acid
Water
Alcohol
Polymerization inhibitors
3. Operating Parameters - see Process No. 171
4. Utilities
Cooling water - 166 kg/kg product
Steam -0.25 kg/kg product
Many other alcohols are also used.
6-435
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5. Waste Streams - Waste water from the alcohol-recovery column
probably contains some methacrylic acid, alcohol, and polymeri-
zation inhibitors. Traces of alcohol and methacrylic acid may also
be discharged through reactor and various distillation column vents.
Sulfuric acid is discharged in waste water streams.
COD - 1.78 x 105 mg/1
BOD5 - 2.07 x 104 mg/1
TOC - 6.99 x 104 mg/1
6. EPA Source Classification Code - None
7. References
Sittig, M., Pollution Control in the Organic Chemical Industry, Noyes
Data Corporation, Park Ridge, N.J., 1974, p. 164-166.
6-436
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 173
Acetylene (BASF process)
2CH, >• CHECH + 3H0
4 t-
1. Function - In the United States, the initial commercial pro-
duction of acetylene from hydrocarbon sources began in 1951. Today,
most of the manufacture of acetylene for chemical synthesis is based
on the process researched by Badische Anilin-und Soda-Fabrik (BASF)
in the 1920's.
In this so-called partial oxidation, or one-stage combustion
method, the necessary energy for cracking the feedstock is derived
by partial combustion of the hydrocarbon feed. Natural gas or other
methane-rich feedstock is mixed with a limited amount of oxygen
sufficient for complete combustion, and fed through a specially de-
signed distributor or burner to a single reaction zone in which
ignition occurs. Improved results are claimed for variations which
involve preheating of the separate gas streams (Societe Beige de
1'Azote, SBA) or preheating the premixed composite feed (Hydrocarbon
Research, Inc.). The Montecatini process, in addition employs pres-
sure operations of up to six atmospheres and effects partial cooling
of the burner gas by injecting higher hydrocarbons after the flame,
resulting in production of ethylene and additional acetylene.
Design of the burner is of considerable importance and is a
common point of process variation. Preignition, stability, and blow-
off of the flame, the possibility of backfiring through the burner
head ports,and deposition of carbon on the burner walls all depend
6-437
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on the burner design and the gas and flame velocities. The com-
bustion of the gas mixture must be as uniform as possible across the
reaction chamber so that the residence time of the reactant hydro-
carbon is as short as possible, usually on the order of 1 to 10
milliseconds.
Yields of acetylene based on carbon in the natural gas feed
vary from 30 - 36% by weight for the various processes. The com-
position of the cracked gas produced from a natural gas feedstock
by the BASF one-stage combustion process is given in the following
table:
Composition of BASF Process Gas
Component % by Volume
acetylene 8.5
hydrogen 57.0
carbon monoxide 25.3
carbon dioxide 3.0
methane 4.0
higher acetylenes 1.0
inert material 1.0
The actual operation of the BASF converter begins with separate
preheating of methane and oxygen (95 - 98% pure) to about 650°C.
The feed streams are then mixed in a venturi-type chamber in a molar
ratio of about 0.6:1.0, oxygen to methane. The mixed gas is passed
to the flame space through a number of tubular channels in a burner
block. About one third of the methane entering the burner is cracked
to acetylene, the remainder is burned with 0~. The pyrolysis products
6-438
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are immediately quenched to about 280°C by one or more water sprays
located in the lower part of the reactor, and the effluent gases pass
through scrubbers for the removal of water and soot. Higher acetylenes
present in the pyrolysis gas must be removed because of this tendency
to polymerize. Electrostatic units, combined with water scrubbers,
moving coke beds, and bag filters, are being used for soot removal.
The unstable, explosive nature of acetylene imposes certain
limitations on the use of customary separation techniques. Studies
indicate that operating conditions where acetylene partial pressure
exceeds 100 to 200 kPa or where temperatures exceed 95 - 105°C
should be avoided. All commercial processes for the recovery of
hydrocarbon-derived acetylene are based on absorption/desorption
techniques using one or more selective solvents (i.e., dimethy-
formamide).
2. Input Materials
Methane - 4.11 kg/kg acetylene produced
Oxygen - 4.75 kg/kg acetylene produced
3. Operating Parameters
Temperature: .1480 - 1540°C (2,696-2,804°F)
Pressure: reduced
4. Utilities - Not given
5. Waste Streams - Hydrocarbons from the feedstock may be emitted
to the air. Water spray used to quench the reaction mixture may
pick up traces of dissolved gases, such as carbon oxides, hydrogen,
6-439
-------
5. Waste Streams (continued)
or hydrocarbons, which would eventually find their way to waste
water streams. Carbon black may give rise to particulates suspended
in air or water.
Flow - 0.0047 m3/kg (561 gal/103 Ibs)
COD - 1,274 mg/1
5.95 g/kg
BOD5 - 410 mg/1
1.92 g/kg
TOC - 393 mg/1
1.80 g/kg
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 178-180.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 30-33.
6-440
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 174
Vinyl Acetate (from acetylene)
0
HC^CH + CH3COOH > CH2=CHOCCH
1. Function - Until 1967 vinyl acetate was produced in the United States
predominantly from acetylene. By 1973 about 75% of the vinyl acetate
was manufactured by the vapor-phase oxyacetylation of ethylene.
In the acetylene process, the acetylene is specially purified
to remove H~S and phosphorus compounds. It is then mixed with gaseous
acetic acid and fed into a fixed-bed reactor with zinc acetate on
carbon as catalyst. Reactor temperature is maintained at 175-200°C.
The reactor effluent is condensed, light ends removed, and vinyl acetate
distilled.
2. Input Materials
Acetylene - 325 kg/metric ton vinyl acetate
Acetic acid - 710 kg/metric ton vinyl acetate
3. Operating Parameters
Temperature - 175-200°C (347-392°F)
Pressure - not given
Catalyst - Zinc acetate on carbon
4. Utilities - not given
5. Waste Streams - Waste gases may contain traces of light ends (methyl
acetylene, allene, acetylene). Waste waters may contain traces of acetic
acid.
6. EPA Source Classification Code - None
6-441
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7. References
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals. 4th
Edition, John Wiley & Sons, New York, N.Y., 1975, p. 862-867.
Waddam, A. L., Chemicals from Petroleum, 3rd Edition, John Wiley
& Sons, New York, N. Y., 1973, p. 42.
6-442
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 175
1,1-Difluoroethane (hydrofluoric acid and acetylene)
H-C=C-H + 2HF > CH CHF2
1. Function - 1,1-Difluoroethane is derived by passing acetylene and a
selected catalyst into the bottom of a stainless steel column of
liquid hydrogen fluoride. The gaseous reaction products are
washed with soda lime, distilled and condensed.
2. Input Materials - Basis - 0.93 part.
Acetylene: 1 part
Hydrogen fluoride: 1.6 parts
BF3 (10%): 0.52 parts
3. Operating Parameters
Temperature: 0-20°C (0.68°F)
Pressure: 68.9-517 kPa (0.58-5.10 atm)
Catalyst: Anhydrous stannic-chloride
Contact Time: 20 sec.
4. Utilities - Not given.
5. Waste Streams - Acetylene, difluorethane, and HF "may be emitted
to the atmosphere. Soda lime sludge should be present.
6. EPA Source Classification Code - None.
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 9 (1966), p. 835.
U. S. Patent 2,830,099 (April 8, 1958).
6-443
-------
U. S. Patent 2,425,991 (1947).
Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd
Edition, Noyes Development Corp., Park Ridge, N. J., 1969, p. 246.
6-444
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 176
1,1,1-Chlorodifluoroethane (chlorination of dif luoroethane)
AIBN
HC1
1. Function - 1,1,1-Chlorodifluoroethane is prepared by chlorinating
1,1-dif luoroethane in the presence of azobis-isobutyronitrile (AIBN)
2. Input Materials
Dif luoroethane
Chlorine
3. Operating Parameters
Temperature: 70-100°C (158-212 °F)
Pressure: 2.59 - 3.79 MPa (25.5-37.9 atm)
Catalyst: AIBN
Reaction Time: 2-8 seconds.
4. Utilities - Not given.
5. Waste Streams - Spent caustic and salt are pollutants from the
scrubber used to remove hydrochloric acid by-product. Some
chlorine may be emitted to the air as well as chlorinated com-
pounds, acetylene and vinyl chloride.
6. EPA Source Classification Code - None.
7. References
Sittig, M., Organic Chemical Process Encyclopedia - 1969,
2nd Edition, Noyes Development Corp., Park Ridge, N. J., 1969,
p. 169.
6-445
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 177
Methyl Butynol (ethynylation of acetone)
Cflf \E,
J ,:
OH
HC=CH ^ HC=C-C-CH^
-'-• Function - 2-Methyl-3-butyn-2-ol is produced by ethynylation of
acetone with excess acetylene in liquid ammonia in the presence of
sodamide (NaNH9) or some other basic catalyst. The reaction is
carried out at a temperature of 10-40°C and high pressure (1.97 MPa).
The process is terminated by adding a material to decompose the
catalyst. The pressure is then dropped to atmospheric in a suitable
flash tank. Ammonia and excess acetylene are recycled to the reactor,
and unreacted acetone is removed from the product in a distillation
column. A second distillation step takes the methyl butynol overhead
as an azeotrope containing 28.4% water, leaving behind deactivated
catalyst salts and heavy by-products.
2. Input Materials
Acetylene
Acetone
Ammonia
3. Operating Parameters
Temperature: 10-40°C (50-104°F)
Pressure: 1.97 MPa (19.4 atm)
Catalyst: NaNH2 (alkali or alkaline earth oxides also acceptable)
6-446
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4. Utilities - Not given
5. Waste Streams - Recycling of ammonia and excess acetylene to the
reactor is a potential source of leaks to the atmosphere. Distil-
lation to remove remaining reactants may cause atmospheric emission
of solvents. The second distillation bottoms include deactivated
catalyst salts and heavy by-products, which will eventually appear
in waste water flow.
6- EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 208.
Ibid., Vol. 12 (1967), p. 120.
Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4
(1972), p. 291.
6-447
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 178
Methyl Pentynol (acetylatlon of 2-butanone)
« CH.OH ™2CH3
CH-^CHCH +HCECHCS7-* CV^0-"
LH3 2° 3 OH
1. Function - 3-Methyl-l-pentyn-3-ol is manufactured by the reaction
of acetylene and 2-butanone in dimethylacetal of formaldehyde as
the solvent. Sodamide, sodium or potassium hydroxide, potassium
t-butoxide, or other alkali or alkaline earth oxides are used as
condensing agents.
A typical yield for this process is 50% based on 2-butanone.
2. Input Materials
2-Butanone - 1.47 kg/kg product
Acetylene
Dimethylacetal of formaldehyde (solvent purposes only)
3. Operating Parameters
Temperature: not given
Pressure: not given
Catalyst: NaNH2, NaOH or KOH, KOC(CH3>3, or other alkali or alkaline
earth oxides.
4. Utilities - Not given
5. Waste Streams - See description under Process No. 177.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 208.
6-448
-------
7. References (continued)
Ibid., Vol. 12 (1967), p. 120.
6-449
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 179
1,1,2,2-Tetrachloroethane (chlorinatlon of acetylene)
HC^CH + 2C12 - > HCC12CHC12
1. Function - Chlorine and acetylene are mixed independently with portions
of a mixture of tetrachloroethane and antimony trichloride. These two
mixtures, one containing chlorine (60-80°C) and the other acetylene
(80-100°C) are then brought in contact under controlled conditions. The
product 1,1,2,2-tetrachloroethane is distilled from the reaction mixture
and mostly used for production of trichloroethylene. Less than 10% of
trichloroethylene is derived directly from acetylene.
2. Input Materials
Acetylene
Chlorine
3. Operating Parameters
Temperature - 70-80°C (158-176°F)
Pressure - Not given
4- Utilities - Not given
5. Waste Streams - The following air emissions arise from the reflux condenser
vent of the chlorination reactor.
Ethane - 1.25 g/kg product
Methane - 1.25 g/kg product
Tetrachloroethane - 0.50 g/kg product
Waste water flow may contain traces of tetrachloroethane and alkali metal
compounds from washing operations as well as suspended particles of iron
or other inorganic catalyst species used.
6-450
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6. EPA Source Classification Code - None
7. References
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th
Edition, John Wiley and Sons, New York, N.Y., 1975, p. 607, 608,
845-848.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 161-163,
Hedley, W. H., et al., "Potential Pollutants from Petrochemical
Processes," Technomic Publishing Co., Westport, Conn., 1975.
6-451
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 180
Trichloroethylene (from tetrachloroethane)
CHC12CHC12 -£-»• CHC1=CC12 + HC1
^•' Function - The cracking of tetrachloroethane in the presence of a
catalyst of BaCl~ on carbon is the currently preferred method of
production. The reaction takes place at 250-300°C and produces a
mixture of trichloroethylene and 10 percent perchloroethylene, which
may be separated by distillation. After distillation from heavy
ends, a small amount (20 ppm by weight) of trimethylamine or pyrrole-
based compounds may be added to stabilize the product.
A small amount of trichloroethylene can be made by pyrolyzing
1,1,2-trichloroethane in the presence of air or 0~:
2CH2C1CHC12 + 02 -£-*• 2 CC12=CHC1 + H20
2. Input Materials
Tetrachloroethane
3. Operating Parameters
Temperature,. ._. ,^^_. _250-30Q°C (482-572.°F)
Catalyst 30 percent BaCl2/C
4. Utilities
Not given
5* Waste Streams - No specific information was available, but one would
expect some HC1 and various chlorohydrocarbons to be present in the
gaseous and aqueous waste streams.
6. EPA Source Classification Code - None
6-452
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7. References
Austin, G. T., "The Industrially Significant Organic Chemicals
Part 8," "Chemical Engineering," July 22, 1974, p. 115.
Faith, W. L. et al., Industrial Chemicals, 3rd Ed., John Wiley
& Sons, Inc., New York, N. Y., 1965, p. 784.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed.,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 190.
6-453
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 181
Synthesis Gas (catalytic steam-hydrocarbon reforming)
CH + H0 - > CO + 3H
2H20
CO
1. Function - Synthesis gas is any mixture of carbon monoxide and
hydrogen, in variable proportions, usually intended for conversion
to ammonia, purified hydrogen, hydrocarbons, alcohols, or other
organic compounds. By 1965, catalytic steam-hydrocarbon reforming
used to recover hydrogen from hydrocarbon feedstocks up to and
including light gasoline fractions, and producing more hydrogen,
and synthesis gas mixture than any other method. In this process,
gaseous hydrocarbons, such as methane are reacted with steam at
650°C to 1050°C in the presence of a suitable nickel catalyst to
produce carbon oxides and hydrogen at about the same temperatures.
Important factors to be considered in the design of a steam-
hydrocarbon reforming plant are:
1) Process Hydrocarbon. Basic requirements for a satisfactory
hydrocarbon feed to a steam-reforming operation are:
a) Freedom from sulfur compounds. The total sulfur
content should be less than 1-5 parts per million,
since sulfur acts as a catalyst poison.
b) Absence of unsaturated hydrocarbons. These compounds
tend to deposit carbon on the reforming catalyst,
causing both loss of activity and physical deteriora-
tion.
6-454
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c) The hydrocarbon feed should be in the vapor phase
when it contacts the catalyst.
2) Operating Pressure. Ammonia and methanol synthesis, petroleum
hydrogenation, hydrogen liquefaction, and the pressure storage
of hydrogen gas all require hydrogen at elevated pressures
ranging up to 100 MPa (1000 atm). Since natural gas is often
available at pipeline pressures of 4 MPa (40 atm) or more,
and steam may be generated efficiently at this pressure,
carrying out the steam hydrocarbon reforming process at
higher pressures, 1.8-3.2 MPa (18-32 atm), may result in
substantial economics. Increased pressure operation also
permits heat recovery from the reaction product stream at
higher temperature levels, due to the higher partial pressure
of the excess steam in the gas mixture.
3) Catalyst selection. Several commercial catalyst are available.
These catalysts contain 20-35% nickel oxide mixed with refrac-
tory cement. Coimpregnation of a small amount of magnesium
oxide with the nickel oxide has been found to improve the
activity and stability of alumina-supported catalyst.
4) Tube surface temperature. The low strength of 25-20 chrome-
nickel steel tubes imposes an external surface temperature
limit of 930-980°C for operation at pressure greater than
1 MPa (10 atm).
5) Steam-hydrocarbon ratio. At atmospheric pressure, hydrocarbons
may be reacted to produce hydrogen with less than 0.1%
residual CH, by using two molecules of steam per atom of
6-455
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carbon in the hydrocarbon, and carrying out the
reaction at temperatures above 870°C. As the
operating pressure is increased, the ratio is generally
increased to between 3 and 4 molecules of steam per carbon
atom in the feed material.
6) Product gas temperature at furnace outlet. This parameter
is important in determining the amount of unreacted methane
remaining in the product stream and is influenced by the
maximum allowable tube surface temperature, the tube diameter,
and the type of furnace.
7) Flue gas temperature. The flue gas temperature will probably
be between 900°C and 1050°C, and the flue gas will be raised
to preheat the furnace feed streams and to generate steam.
8) Carbon monoxide removal. Substantially complete removal of
CO from the product stream is required when synthesis gas
is used as a source of hydrogen in the synthesis of ammonia.
This processing step is accomplished by causing the raw gas
mixture to react with steam via the water gas shift. The carbon
dioxide formed is scrubbed with appropriate solvents.
2. Input Materials
Natural gas (methane) or other hydrocarbon feed
Steam - 2 to 6 kg/kg synthesis gas produced
3. Operating Parameters
Temperature: 650-1050°C (1202-1922°F)
6-456
-------
3. Operating Parameters (continued)
Pressure: 1.8-3.2 MPa (17.8-31.6 atm)
Catalyst: 20-35% nickel oxide on alumina support
Residence time: 0.2-10 seconds
4. Utilities - Not given
5. Waste Streams - Condensates from catalytic reforming generally contain
spent catalyst particles, hydrogen sulfide formed from residual sulfur
in the feed, and ammonia formed by reaction of air with the hydrocarbons
at elevated temperatures.
Regeneration of the activated carbon used for sulfur removal may
lead to gaseous emissions of hydrogen sulfide and/or sulfur dioxide,
if this operation is performed on site.
It is unlikely that hydrocarbons from the feed stream or carbon
monoxide from the product stream would be emitted to the air.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 275,276.
Ibid., Vol. 10 (1966), p. 415-419.
U.S. Patent 3,367,882 (February 6, 1968).
Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition
Noyes Development Corp., Park Ridge, N.J., 1969, p. 623.
6-457
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 182
Synthesis Gas (continuous, non-catalytic partial oxidation)
C02 - *• 2CO
CO + 3H2
CO
Function - Synthesis gas is a mixture of carbon monoxide and hydrogen
with minor amounts of carbon dioxide and nitrogen. There are two
general processes used - the steam reforming process (using a nickel
catalyst) and the process described here, the non-catalytic partial
oxidation process.
The partial oxidation process involves the burning of hydrocarbons
in air or oxygen to produce a gas containing hydrogen and carbon monox-
ide with small quantities of methane, CO- and water vapor. The use
of oxygen yields a product gas of lower nitrogen content often
necessary for subsequent uses of synthesis gas.
The mixture of hydrocarbon and oxygen is pre-heated to 235-650°C
(455-1202°F) depending on the composition of the gas stream. It
then passes to a reactor which operates at 1100-1600°C (2012-2912°F)
and pressures up to 4 MPa (40 atm) . The hot effluent gases are cooled
in a heat exchanger, compressed and C02 removed by absorption in water
or ethanolamine solution.
The non-catalytic partial oxidation process can operate on any
hydrocarbon feedstock that can be compressed or pumped. No desulfuri-
zation process is necessary since there is no catalyst involved that
can be poisoned.
6-458
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2- Input Materials
o
Natural gas (methane) - 0.27 kg/Nm of crude dry gas produced
o
(Nm = normal cubic meters, 0°C, 760 mm Hg.
Steam - 13.40 kg/1000 Nm of crude dry gas or 0.05 kg/kg natural gas
feed (steam saturated at 246°C (470°)).
3 3
Oxygen - 0.26 Nm /Nm of crude dry gas
3. Operating Parameters
Temperature: 1100-1600°C (2012-2912°F)
Pressure: 1.48-4.24 MPa (14.6-41.8 atm)
Residence time: <10 seconds
4. Utilities
3
Boiler feed water - 0.83 kg/Nm crude dry gas
3
Cooling water - 0.32 kg/Nm crude dry gas
3
Fresh water - 67.0 kg/1000 Nm crude dry gas
3
Electricity - 16.2 kJ/Nm crude dry gas
5. Waste Streams - The partial oxidation process produces 0.12 kg of
3
condensate per Nm of crude dry product gas. Again as in catalytic
reforming, it is doubtful that reactants, natural gas or oxygen,
are emitted to the atmosphere during feed to the reactor. For
natural gas, no soot will appear in the waste water flow. Carbon
dioxide from stripping of the gas absorption system may be vented
to the air.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 419-422.
6-459
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 183
Urea (once-through process)
2NH- + CO, >- H?NCOONH,
,j £t * ~ &• "
1. Function - All commercial production of urea is based on the reaction
of ammonia and carbon dioxide to form ammonium carbamate which in
turn decomposes to urea and water.
The reaction is run at 175-190°C and a pressure of 16-25 MPa
(160-250 atm). Under these conditions, the equilibrium urea con-
versions of only 40-70% can be expected. The effluent contains
ammonium carbamate, urea and excess ammonia. The unreacted carbamate
is decomposed to ammonia and carbon dioxide gas by heating the effluent
at low pressure. The gaseous mixture is separated from the urea solu-
tion and used to produce ammonium salts by absorbing NH_, either in
sulfuric or nitric acid. C0~ is vented to the air.
Urea is recovered from the stripped effluent solution either by
evaporation or crystallization. Biuret, a condensation product of
urea forms under conditions of high temperature and reduced pressure,
and must be minimized for certain industrial uses of urea. Urea,
produced by crystallization, contains only 0.2-0.3% of biuret.
Product produced by evaporation contains a much higher biuret con-
tent.
Urea is marketed in the form of small spherical particles called
prills. These are formed by spraying molten urea, at the top of a
50M cylinderical column into a counter current stream of air.
6-460
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The molten urea freezes into spheres which are collected at the
column bottom. The biuret content in this material is 0.6-1.5%.
2. Input Material
Ammonia - 1.87-1.77 kg/kg urea produced
Carbon dioxide (from synthesis gas) - 0.91-1.47 kg/kg urea produced
3. Operating Parameters
Temperature: 175-190°C (347-374°F)
Pressure: 16-25 Mpa (160-250 atm)
4. Utilities - Not given
5. Waste Streams - The high vapor pressure of ammonium carbamate at
elevated temperatures, may result in atmospheric emissions of that
species from the urea synthesis reactor. Some ammonia may be emitted
during solidification of urea by evaporation as a by-product of
biuret formation. The prilling tower may be a source of particulates
as well.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 9," "Chemical Engineering," August 5, 1974, p. 97.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 21 (1970), p. 43-45.
U.S. Patent 3,072,721 (January 8, 1963).
Sittig, M., Organic Chemical Process Encyclopedia - 1969,
2nd Edition, Noyes Development Corp., Park Ridge, N.J., 1969, p. 690.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 857.
6-461
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 184
Urea (recycle processes)
1. Function - The urea synthetic processes can be divided into two general
classes, the "once through process," described as a separate process,
and the "recycle process." The recycle process is one in which
unreacted carbon dioxide and ammonia either in the free form or
combined as ammonium carbamate, are returned to the system for
further conversion to urea.
There are many versions of the recycle process which differ
basically in the manner in which the CCL and NH, are recovered and
returned to the reactor. There may be two or three stages of car-
bamate decomposition each succeeding stage operated at a lower pres-
sure and temperature.
Ammonia and carbon dioxide gases are liquified (compressed)
and charged to a steam-heated, silver lined autoclave which
is maintained at 175 - 200°C and 170 - 408 atm. The
ammonia and carbon dioxide are converted to ammonium carbamate
which decomposes to urea. The product mix consists of 35% urea, 15%
ammonia, 21% ammonium carbamate and 14% water. The product is fed
to a carbamate decomposer at a pressure reduced from that of the
6-462
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reactor. Here carbamate decomposes into NH~ and CO^, the gas
is recovered, cooled, and recycled to be again converted to ammonium
carbamate. The effluent solution is passed to a second carbamate
decomposer which is operated at a lower temperature and pressure.
Additional carbamate decomposition occurs here, the gases being
collected, cooled and recycled as before and the effluent passing
to a third carbamate decomposer which again operates at a lower
temperature and pressure. Effluent from the third stage passes to
a crystallizer where urea crystals are recovered.
2. Input Materials - Basis - 1 metric ton urea
Ammonia - 2000 kg
Carbon dioxide - 900 kg
3. Operating Parameters
Temperature: Reactor - 175-200°C (347-392°F)
1st Decomposition stage - 150°C (302°F)
2nd Decomposition stage - 130°C (266°F>
3rd Decomposition stage - 120°C (248°C)
Pressure: Reactor - 17.2-41.4 MPa (170-408 atm)
1st Decomposition stage - 1.8 MPa (18 atm)
2nd Decomposition stage - 0.4 MPa (4 atm)
3rd Decomposition stage - 100 kPa (1 atm)
4. Utilities - Data for Stamicarbon recycle urea plant producing
fertilizer grade plus, biuret content = 0.2-0.25%
Basis - 1000 kg urea
Steam - (2.6 MPa) - 1100 kg
3
Cooling water - 65 m
Power - 504 MJ (140 kw)
6-463
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5. Waste Streams - Loss of NH, to the atmosphere during staged decom-
position and absorption are possible emissions. CO™ may also be
emitted in the various stripping operations.
6. EPA Source Classification Code - None
7. References
Kirk-Othaier, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 21, (1970), p. 45-51.
"1975 Petrochemical Handbook," "Hydrocarbon Processing," November,
1975, p. 210-11.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., (1975), p. 854-857.
6-464
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 185
Guanidine (from urea)
SO
^•* Function - Guanidine may be manufactured by the reaction of urea
with ammonia and sulfur dioxide. Urea, liquid sulfur dioxide, and
ammonia (in molar ratio 1:3:7) are heated to 275°C under pressure
for approximately 30 minutes. Guanidine (as the sulfate) is obtained
in 80% yield. The reaction product is dissolved in water and filtered
to remove sulfur. The solution is concentrated and treated with nitric
acid to form guanidine nitrate. Guanidine is usually marketed as the
nitrate or the chloride.
2. Input Materials
Urea
S02
NH3
3. Operating Parameters
Temperature: 245-2 75 °C
Pressure: 20.2 MPa (200 atm)
Time: 30 minutes
4- Utilities - Not given
5. Waste Streams
Air - NH3 and S02
Water - Traces of reactants and products
Solid waste - Sulfur
6-465
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6. EPA Source Classification Code - None
7. References
Astle, M. J., Industrial Organic Nitrogen Compounds, Reinhold Publishing
Corp., New York, N.Y., 1961, p. 301.
Boivin, J. L., "Canadian J. Chem," _34, 827 (1966).
6-466
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 186
Cyanuric Acid (thermal decomposition of urea)
OH
0 i
" 4? ^
yCv IT N
3 H/ V2 ™3 + IJ
2 2 HO*»XSlI
1. Function - Heating urea for several hours at 200-300°C results
in deamination and the formation of cyanuric acid.
For temperatures much above 300°C, the yield of product de-
creases due to depolymerization.
Conversion to cyanuric acid occurs in stages. Initially, urea
melts at 133°C to form a free-flowing liquid. As heating continues,
the reaction mass thickens and finally solidifies, although at this
point significant amounts of urea, biuret, H~NCONHCONH_, and triuret,
H-NCONHCONHCONH-, are present. Additional heating converts these to
cyanuric acid. The product of pyrolysis strongly adheres to the walls
of the reactor and is removed with great difficulty. Several methods
have been patented to overcome such problems.
(1) conducting pyrolysis on a molten tin or lead bath
(2) conducting pyrolysis in a fluidized bed
(3) recycling 60-90% of crude cyanuric acid into a rotating kiln
to mix with urea prior to pyrolysis
(4) running the reaction in certain high-boiling organic solvents
(5) heating urea at 165°C for about two hours to get a liquid mix-
ture consisting of urea, biuret, triuret, and cyanuric acid,
followed by further pyrolysis for ten minutes at 240-270°C
on a rotating heated drum.
6-467
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Crude cyanuric acid produced by pyrolysis may be contaminated
with as much as 20-30% impurities consisting mostly of ammelide and
ammeline with minor amounts of melamine, biuret, urea, and triuret.
Two general purification techniques will be described.
Cyanuric acid may be dissolved in ammonium hydroxide solution or
hot dimethylformamide solution. Filtering the mixture will remove
most of the impurities. The product may be precipitated from the
ammonium solution by acidification with mineral acid or from the
DMF solution by cooling and adding carbon tetrachloride.
Crude cyanuric acid may also be purified by heating it in
10-20% sulfuric, nitric, or hydrochloric acid for several hours.
This process hydrolyzes most of the ammelide, ammeline, and melamine
to cyanuric acid. The slurry is then filtered or centrifuged and
the solids collected are washed with water to remove residual traces
of the acid used earlier. Cyanuric acid can be dried in any con-
ventional dryer, up to a maximum temperature of 200°C, to give a
product of at least 98% purity.
2. Input Materials - urea
3. Operating Parameters
Temperature: 200-300°C (392-572°F)
Pressure: 101 kPa (1 atm)
4. Utilities
Not given
5. Waste Streams - Ammonia produced during decomposition of urea is
probably emitted to the atmosphere. All other compounds (cyanuric
acid, biuret, triuret, ammeline, ammelide, melamine) are solids at
ordinary temperatures, and although they occur in the liquid phase
6-468
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during reaction, the vapor pressures are probably too low to lead
to any pollution problems.
Purification is a source of additional emissions. The precipi-
tation method will lead to the presence of the various solvents or
acid in wastewater. The acid-digestion process waste is probably
neutralized, leading to spent caustic in wastewater. Drying operations
should not pose any significant pollution problems.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 20 (1969), p. 667, 668.
6-469
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 187
Oxo Aldehydes (oxo process)
RCH=CH0 + CO + H- cobalt ; RCH CH CHO + R-CHCHO
2 2 carbonyl 2 2 j
1. Function - The oxo process consists of the hydroformylation of
olefins to give aldehydes (and ultimately alcohols) of the next
higher homologue. The olefin feed is usually mixed with a slurry
of the cobalt catalyst (usually in the form of cobalt naphthenate)
and introduced to the converter together with the synthesis gas.
The reaction takes place in the liquid phase at 130-175°C and 200-
300 atm.
The liquid reaction products go to a phase separator then to
a cobalt removal system (decobalter). The cobalt catalyst is re-
generated and recycled. The crude aldehydes are refined by distillation.
2. Input Materials
Olefin - (90%)
Synthesis gas - [CO (98-99%) + H2 (98-99%)]
Co catalyst
Steam
co2
3. Operating Parameters
Temperature - 130-175°C
Pressure - 200-300 atm. (20.2-30.4 MPa)
6-470
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4. Utilities - Not given
5. Waste Streams -
Air - Emissions stemming from the formation of by-products such as
paraffins from hydrogenation of starting olefin; olefin feed and syn-
thesis gas leaks.
Water or solid wastes - Wastes resulting from the high-boiling oxygenated
compounds formed from condensation of aldehydes and alcohols.
6. EPA Source Classification Code - None
7. References
Sittig, M. ,"0xo Products From Olefins," in Pollution Control in the
Organic Chemical Industry, Noyes Data Corporation, Park Ridge, New
Jersey, 1974, p. 175.
US Petrochemicals, Technologies, Markets, and Economics, Brownstein,
A. M., Ed., The Petroleum Publishing Company, Tulsa, Oklahoma, 1972,
pp. 92-93.
Hahn, A.V., The Petrochemical Industry; Markets and Economics.
McGraw-Hill Book Company, New York, 1970, pp. 104-105.
"Oxo Process" in Chemical and Process Technology Encyclopedia.
Considine, D. M., Ed-in-Chief, McGraw-Hill Book Company, New York,
1974, pp. 793-794.
Haberstroh, W. H» and Collins, E.M.,"Oxo Chemicals," in Riegels'
Handbook of Industrial Chemistry, 7th edition, Kent, J. A., Ed.,
Van Nostrand Reinhold Company, New York, 1974, pp. 774-775.
6-471
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 188
Oxo Alcohols
RCH2CHO
OlP H2
2RCH.CHO > R-C-CHO —^> R-CHCH OH
2 II I 2
HCCH2R CH2CH2R
1. Function - Alcohols are usually the ultimate product of the oxo-process
(Process No. 187). The alcohols are obtained by: (a) direct reduction
of the aldehyde; (b) dimerization of the aldehyde by aldol condensation
followed by reduction to the alcohol; or (c) single stage low pressure
oxo process. In (a), the aldehyde from the decobalter is hydrogenated at
elevated temperature and pressure to give the alcohol. In (b) the
aldehyde from the decobalter is fed into a condensation reactor where
the aldolization is carried out in the presence of caustic. Water is
continually removed from the consendation reaction to drive it to
completion. The resulting aldehyde is then hydrogenated to the alcohol.
An alternate route was recently introduced. Olefin feed and
recycled catalyst are charged to the first of a series of packed reactors
at controlled rates. Synthesis gas (H2:CO = 2.5:1) is fed separately to
each reactor. The overhead stream from the final reactor is sent
directly to the recovery column. The bottoms from the recovery column
contain catalyst complex in a mixture of alcohols and heavy ends. This
stream is recycled to the first reactor with periodical purging to
remove built-up heavy ends.
6-472
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This reaction is carried out in alkaline medium with a specially
promoted cobalt carbonyl catalyst. The dimer and monomer alcohols
are obtained directly from the reaction mixture.
2. Input Materials
Aldehyde
Hydrogen
Phosphine-promoted cobalt carbonyl
Nickel catalyst
Zinc compound
Olefin
Synthesis gas
Caustic
3. Operating Parameters
a. Temperature - 150-200°C (302-392°?)
Pressure - (1500-3000 psi) 10.3-20.6 MPa (102-204 atm)
b. Temperature - 90-230°C (194-446°F)
Pressure - < than (a)
c. Temperature - Not given
Pressure - < 30 atm. 3.04 KPa (30 atm)
4. Utilities - Not given
5. Waste Stream - Air - hydrocarbons from leaks. Water - High boiling
oxygenated intermediates, byproducts, and heavy ends. A typical plant
o q
survey showed: Flow - 1.59 m /454 kg, COD - 1.21 kg/m and 1.93 kg/
454 kg, BOD5 - 0.9 kg/m3, 1.43 kg/454 kg, and TOC - 0.549 kg/m3,
.87 kg/454 kg.
6. EPA Source Classification Code - None
6-473
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7. References
Sittig, M.,"0xo Products from Olefins," in "Pollution Control in the
Organic Chemical Industry," Noyes Data Corporation, Park Ridge,
New Jersey, 1974, pp. 175-177.
Long, F.W., "Technology and Markets of Petrochemicals Derived from
Synthesis Gas," in "US Petrochemicals: Technologies, Markets, and
Economics," Brownstein, A. M., Ed., The Petroleum Publishing Company,
Tulsa, Oklahoma, 1972, pp. 92-94.
Waddams, A.L., Chemicals From Petroleum, 3rd Edition, John Murray Ltd.,
London (1973), p. 204-206.
6-474
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 189
Phosgene (catalytic reaction of carbon monoxide
and chlorine)
Co + ci2catalyst> coci2
1. Function - Phosgene is manufactured by reacting chlorine gas and carbon
monoxide in the presence of activated carbon. Dry carbon monoxide of
the highest possible purity is metered and mixed in a reactor with dry
and pure chlorine at a temperature of 200°C and 2 to 4 psig over gas-
mask grade activated charcoal.
The hot effluent gases leaving the reactor are led to a condenser,
where liquid phosgene is removed. The non-condensable gases are scrubbed
with a hydrocarbon solvent to remove entrained phosgene. Nearly
all phosgene is used at the point of manufacture, mostly in the manu-
facture of isocyanates for polyurethane resins.
2. Input Materials
3
Carbon monoxide - 230 m /metric ton product
Chlorine - 720 kg/metric ton product
3. Operating Parameters
Temperature - 200°C (392°F)
Pressure- 13.8-27.6 kPa (0.14-0.27 atm)
Catalyst - activated charcoal 15 kg/metric ton product
4. Utilities - Not given
6-475
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5. Waste Streams - Any phosgene waste (not feasible to recycle) is
scrubbed with sodium hydroxide.
6. EPA Source Classification Code - None
7. References
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N. Y., 1975, p. 624-627.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Supplemental Volume (1971) p. 677-681.
Austin, G. T., "The Industrially Significant Organic Chemicals - Part
8," "Chemical Engineering," July 22, 1974, p. 108-109.
6-476
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 190
Sodium Formate (carbon monoxide and sodium hydroxide)
HO
NaOH + CO —=-> HCOONa
1. Function - Clean and compressed synthesis gas (source of carbon monoxide)
is introduced countercurrently into a 25-30% sodium hydroxide solution
at 160-200°C to give sodium formate. Sodium formate crystals are
obtained by drying the reaction product.
2. Input Materials
Synthesis gas (source of carbon monoxide)
Sodium hydroxide
3. Operating Parameters
Temperature - 160-200°C (320-392°F)
Pressure - 140-170 kPa (1.38-1.68 atm)
4. Utilities - Not given
5. Waste Streams - Waste water is likely to contain sodium hydroxide.
Atmospheric emissions of carbon monoxide and hydrogen are possible.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 10 (1966), p. 101.
Gmelins Handbuck der Anorganische Chemie, System-Nummer 21, 8 Auflage
Erganzungsband, Lieferung 4, Verlag Chemie, 1967, p. 1398.
6-477
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 191
Methanol (high-pressure catalytic synthesis)
CO + 2H2 + CH3OH AH°9g = -90.79 kJ
1. Function - Methanol synthesis from CO and H? is favored by high pres-
sures and low temperatures. The temperature and pressure applied in
commercial processes is dependent on: composition of synthesis gas
utilized, and rate of reaction at a given temperature and pressure in
the presence of a given catalyst.
The main source of synthesis gas at present is the steam reforming
of natural gas. Very exact process control is needed to maintain a
desired carbon monoxide - hydrogen ratio.
The reforming of natural gas by steam may be represented by the
following equation
3CH4 + C02 + 2H20 -»• AGO + 8H2
The synthesis gas is compressed to remove water and entrained
oil. The compressed mixture of gases is passed through a catalytic
converter. Commercial processes usually operate at temperatures
ranging from 350°C to 400°C and at pressures in the 19.6-29.4 MPa range.
Catalyst used in the high-pressure synthesis consists mainly of mixtures
of chromium oxide and zinc oxide. Close control of operating parameters
to suppress side reactions is of utmost importance. The mixture of
gases from the converter pass through a condenser and then through a
separator. The crude methanol condensate is subsequently purified
in a two-step distillation. By-products are mixed alcohols (19.3 g/kg
methanol) and dimethyl ether (20.4 g/kg methanol).
6-478
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Methanol plant equipment must be resistant to carbon monoxide
at high temperatures and pressures.
Copper-based catalyst have been known to increase the rate of
the reaction for the formation of methanol from synthesis gas, but
were readily inactivated by sulfur impurities present in synthesis
gas. Improved methods of removing sulfur from synthesis gas and
newly-perfected copper-zinc catalyst has led to a new low-pressure
process for the manufacture of methanol from synthesis gas. The new
low-pressure process developed by Imperial Chemical Industries Limited
of United Kingdom operates at pressures nearly half of those utilized
in usual processes. Some methanol was also produced in the liquid phase
oxidation of butane—rich hydrocarbon gas (Process No. 227) . However,
this process has not been in commercial use since 1973.
2. Input Materials
1) Synthesis gas - produced by steam reforming of 0.829 kg natural
gas per kg CH^OH.
a) 5.8-7.3 kg CO/kg CH^H (based on 12-15% conversion of CO)
b) .87-1.31 kg H2/kg CH3OH (based on H2:CO molar ratio of 2.1-2.5)
2) Carbon dioxide - recovered from reformer flue gases.
3. Operating Parameters
Temperature: 350-400°C (662-752°F)
Pressure: 20-30 MPa (200-300 atm.)
Catalyst: Cr_03 + ZnO
6-479
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4. Utilities - Basis - 10.5 kg/sec (1000 tons/day) capacity
o
Cooling water - 2.089 m /sec (33,110 gal/min)
o
Makeup water - 70.0 dm /sec (1,100 gal/min)
Power - 11.0 GJ (3.06 Mw)
Natural gas - 13.49 Nm3/sec (1.715 M scfh)
5. Waste Streams - Major waste water streams are from slab and vessel
washdowns together with bottoms from the methanol purification process.
o
This amounts to 0.4-2.1 m /kg of product (100-500 gal/ton) and contains
i
some oils, methanol, and higher-boiling organic compounds to the extent
of about 0.2-0.5 kg/1000 m3.
Plant 1 Plant 2
Flow 0.492 m3/kg 0.352 m3/kg
COD 320 mg/1 4,930 mg/1
0.16 g/kg 1.74 g/kg
BOD- 119 mg/1 2,620 mg/1
0.059 g/kg 0.92 g/kg
TOC 107 mg/1 583 mg/1
0.053 g/kg 0.21 g/kg
6. EPA Source Classification Code - None
7. References
Chemistry In The Economy - American Chemical Society Study,p. 31, 1973.
Hedley, William H., et al., Potential Pollutants From Petrochemical
Processes, Technomic Publishing Co., Westport, Conn., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 13 (1967), p. 375-378.
Sittig, M., Pollution Control in the Organic Chemical Industry, Noyes
Data Corp., Park Ridge, N.J., 1974, p. 158-159.
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INDUSTRIAL ORGANIC CHECMICALS PROCESS NO. 192
Methylamines
(vapor-phase aimnonolysis of methanol)
1. Function - The manufacture of methylamines is a classic example of
vapor phase ammonolysis of alcohols. Methylamine, with smaller
quanties of both dimethylamine and trimethylamine, is produced
by passing methanol and ammonia, in a 1:5 volume ratio and pre-
heated to 350°C, over a dehydrating catalyst at space velocities
of 0.75 - 1.5 and a catalyst temperature of 450°C. The process
is usually carried out under atmospheric pressure, but it can be
performed under pressures in excess of 690 kPa (6.8 atm) with
direct fractionation of the products at these conditions. Catalysts
commonly used are alumina (A^Os) , aluminum silicate, aluminum
phosphate, and diammonium phosphate. Conversion of the ammonia
is 13.5% to primary, 7.5% to secondary, and 10.5% to tertiary amine.
Part of the exothermic heat of reaction may be used in the feed
preheater.
Since exclusive production of one of the amines is difficult and
frequently uneconomical, much of the process development con-
cerning methanol ammonolysis has dealt with the problem of
satisfactory separation of the three co-products. Recycling of
the less desirable amines to increase the yield of the desired
product is generally effective even if the secondary or tertiary
6-481
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amine is preferred. If dimethylamine is desired, the other two
amines may be recycled without separation from each other.
Separation or fractionation of the product stream is rather
difficult because the boiling points of the methylamines all
lie in a temperature range of only about 10°C.
The crude product can be separated by a series of four column
distillations. The first column is maintained at a suitable
temperature and pressure so that the trimethylamine—ammonia
azeotrope to be recycled is recovered overhead, the recyclable
ammonia from the upper middle of the column, and a mixture of mono-,
di-, and some tri-methylamine as bottoms. The mixture goes to
the trimethylamine (TMA) column where water is added for ex-
tractive distillation and pure TMA is collected overhead and sent
to storage or recycle. The bottoms from this operation are sent
to the mono-methylamine (MMA) column where pure MMA is removed overhead.
Finally, the MMA column bottoms are sent to a fourth column where
pure dimethylamine goes overhead with water drained from the
bottom to waste.
Procedures have also been devised for separating the methylamines
from mixtures by extractive distillation. Mono-methylamine is
separated from the other two by absorbing the vapors in a liquid
in which it has the lowest «olubility of the three, such as di-
methylaniline, 1,2,3,4-tetrahydronaphthalene, or diraethylcyclohexyl-
amine. Fractional distillation of this solution yields MMA over-
head. Dimethylamine is separated from MMA and TMA by subjecting
the mixture to extractive distillation using aniline, morpholine,
6-482
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dimethylformamide, or diethanolamine, in which DMA is the most
soluble. The diemthylamine is recovered by flashing from the
solvent. By using solvents in which TMA is the least soluble,
the member of the series may be distilled from mixture.
2. Input Materials - kg/kg of desired methylamine produced
Methanol (industry average factor/highest value)
a) MMA; 1.05/1.2
b) DMA: 1.45/1.6
c) TMA: 1.65/1.8
Ammonia (assuming 97% yield)
a) MMA; 0.565
b) OMA: 0.389
c) TMA: 0.297
3. Operating Parameters
Temperature: 450°C (842°F)
Pressure: 690 kPa (6.8 atm)
Catalyst: A^OS
4. Utilities - basis: 45.4 kg (100 Ib) of anhydrous product
Steam - 590 kg (1300 Ibs)
Water - 13.2 m3 .(3500 gallons)
Electricity - 32.4 MJ (9 kWh)
5. Waste Streams - The staged distillation process is the source of
most of the pollutants in methylamine manufacture. The bottoms
from the DMA column, the last in the series of four, are drained
to wastewater and will contain some of all three methylamines in
solution.
6-483
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Two examples of the wastewater are:
Flow
COD
BOD5
TOG
#1
3.58 I/kg
22.56 g/kg
6.303 g/1
0.35 g/kg
99 rng/1
41.65 g/kg
11.634 g/1
#2
3.57/1/kg
4.21 g/kg
1.178 g/1
0.62 g/kg
1.74 mg/1
13.63 g/kg
3.808 g/1
Atmospheric emissions of hydrogen and cqrbon monoxide and of
methylamines will arrise from crude product storage and final
storage, respectively.
6. EPA Source Classification Code - None
7. References
"1973 Petrochemical Handbook," "Hydrocarbon Processing,"
November, 1973, p. 150.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 2 (1963), p. 122.
6-484
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 193
Methyl Chloride
1. Function
Methyl chloride is produced by the action of hydrogen chloride
on methanol, with the aid of a catalyst, in the vapor phase. Vapors
of methanol and hydrogen chloride are continuously mixed in approxi-
mately equimolecular ratios and passed through a preheater maintained
at about 180°C.
The gas mixture is then passed at substantially atmospheric
pressure through a converter at a temperature of 340°C to 350°C. The
converter is packed with previously ignited alumina gel of 8 to 12
mesh size or a similar catalyst, such as zinc chloride on pumice,
cuprous chloride, or activated carbon. Space velocities of about
3 3
7.79 m (275 cubic feet) per hour per 28 dm (cubic foot) of gross
catalyst volume are generally used (based on gas volumes at STP).
The effluent gases from the reactor are scrubbed with water
to remove excess HC1, followed by an alkali wash, and a sulfuric
acid wash (to dry the product). Crude methyl chloride is distilled
under pressure at -24°C to yield pure methyl chloride.
2. Input Materials - Basis - 1 metric ton methyl chloride
Methanol - 360 kg/Mg (720 Ib/ton) of product 700 kg (1,543 Ibs)
HC1 - 1587 kg/Mg (3,174 Ib/ton) of product 800 kg (1,769 Ibs)
Sulfuric Acid
Caustic Soda
6-485
-------
3. Operating Parameters
Preheater temperatures: 180 - 200°C (356 - 392°F)
Converter temperatures: 350PC (662°F)
Pressure: atmospheric
3
Space velocity: 275 m /hr
Catalyst: Alumina gel. Cuprous chloride on activated carbon or
pumice. Zinc chloride on activated carbon or pumice. Phosphoric
acid on activated carbon.
4. Utilities
Not given
5. Waste Streams - Waste water from scrubbers contains traces of HC1,
some alkali and sulfuric acid.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1967), p. 106,107.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 533.
6-486
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 194
Methyl Acetate (by esterification)
+ CELOH >• CHgCOOCHg +
1. Function - In a general procedure for manufacturing methyl esters
the aliphatic carboxylic acid (in this case acetic acid) is reacted
with an excess of methanol in ethylene dichloride as solvent. Sul-
furic acid is used as catalyst for the reaction. The mixture is
heated to reflux from 6 to 15 hours. After cooling the reaction
product is washed with water, sodium bicarbonate, water and dried
by conventional methods. The ethylene dichloride is removed by
distillation. The crude ester is then distilled.
2. Input Materials
Methanol
Acetic acid
H2S04
Ethylene dichloride
3. Operating Parameters
Temperature: Reflux
Pressure: 101 kPa (1 atm)
Catalyst: H-SO,
Time: 6-15 hrs
4. Utilities - Not given
5. Waste Streams - Waste water may contain dilute solutions of salts
of acids, traces of methanol, methyl acetate, and other organic by-
products.
6-487
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 8 (1965), p. 350,
U.S. Patent 2,787,636 (April 2, 1957).
6-488
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 195
Methyl Acetoacetate (action of metallic sodium on methyl acetate)
£> Na®
2CH C-OCH + 2Na > CH^C = CH-COOCH,
NaOCH3
[CH3COCHCOOCH3P'Nas' + E^SO^ * CH3
1. Function - Methyl acetoacetate is prepared by the reaction of high-purity
methyl acetate with metallic sodium in absolute methanol. The sodium
derivative is then neutralized with sulfuric acid to give the product.
The crude ester is separated and purified by vacuum distillation.
2. Input Materials
Methyl Acetate
Metallic sodium
Absolute Methanol
Sulfuric acid
3. Operating Parameters - Not given
4. Utilities - Not given
5. Waste Streams - Hydrogen, a by-product; may be released into the atmos-
phere. Wastewaters may contain sodium hydroxide and sodium bisulfate
as well as traces of methanol and sulfuric acid.
6. EPA Source Classification Code - None
6-489
-------
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 154-155.
6-490
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 196
Dimethyl Ether
1. Function - Dimethyl ether is produced from methanol using sulfuric
acid as the dehydration catalyst or by passage over catalyst such
as alumina.
A mixture of methyl alcohol and concentrated sulfuric acid is
slowly heated to 110-140°C. In this temperature range the reaction
is initiated. An azeotrope of ether-water-alcohol distills from
the reactor at 110 °C and passes to a scrubber. The vapors pass
count ercurrently to a slow moving stream of dilute sodium hydroxide.
The vapors from the top of the scrubber run to a continuous frac-
tionation column where separation takes place. Alcohol and sulfuric
acid are recycled.
2. Input Material
Methanol
Sulfuric Acid
3. Operating Parameters
Temperature: 140°C (284°F)
Pressure: 101 kPa (1 atm)
Catalyst: I^SO^
4. Utilities - Not given
5. Waste Streams - Waste water may contain traces of ether, aldehydes,
and peroxides as well as sodium sulfate from neutralization.
6-491
-------
Some reduction of sulfuric acid occurs with evolution of sul-
fur dioxide. Tarry materials are disposed as solid waste.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 8 (1965), p. 474-
476.
Houben-Weyl, Methoden der Organischen Chemie, Vierte Auflage,
George Thieme Verlag, Stuttgart, Bd. 6, T. 3, (1965), p. 13.
Faith, W. L., et^ al^., Industrial Chemicals, 3rd Edition, John Wiley
and Sons, New York, N. Y., 1965 , p. 335-336.
6-492
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 197
Dimethyl Sulfate
. „ , „„ 45-47°C,
1. Function - Dimethyl sulfate is obtained in a continuous process
utilizing dimethyl ether and liquid sulfur trioxide as the input
materials. Gaseous dimethyl ether is bubbled into the bottom of
an aluminum tower filled with dimethyl sulfate. Liquid sulfur tri-
oxide is introduced at the top of the tower. The mildly exothermic
reaction is controlled at 45-47°C. The reaction product (96-97%
dimethyl sulfate) is continuously withdrawn and purified by vacuum
distillation over sodium sulfate.
2. Input Materials
Dimethyl ether (74.3 kg/hr)
Sulfur trioxide (129.1 kg/hr)
3. Operating Parameters
Temperature 45-47°C (113-117°F)
4. Utilities
Not given
5. Waste Streams - Possible gaseous emissions of SO . The bottoms from
- •--'•" X
distillation contain sulfuric acid and methyl hydrogen sulfate.
6. EPA Source Classification Code - None
7. Reference
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 19 (1969), p. 492.
6-493
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 198
Methyl Formate
CH,OH + CO -> HCOOCH
J /*iTT f\Tfin
1. Function - Methyl formate may be prepared industrially by the reaction
of methanol with carbon monoxide (from synthesis gas) in the presence
of metal alkoxides. Hydrogen reacts with excess carbon monoxide to
form methanol which is re-cycled.
2. Input Materials
Methanol
Synthesis gas (CO + H~)
CH3ONa (CH OH + Na)
3. Operating Parameters
Temperature - 80°C (176°F)
Pressure - 2.96 kPa (300 atm)
Residence time - 350 sec.
4. Utilities - Not given
5. Waste Streams - By product of the reaction, e.g., dimethyl ether. Also
some high-boiling tars are formed.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 4 (1965), p. 434-435.
Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Wiley
and Sons, New York, N.Y., 1973 , p. 204.
6-494
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 199
Formamlde
HCOCH 4- NH * HCNH2 + CB^OH
1. Function - Formamlde can be manufactured by the reaction of ammonia
with methyl formate. Formamide was used as a source of HCN. This HCN
process is considered obsolete now.
2. Input Materials
Methyl formate
Ammonia
3. Operating Parameters
Temperature - 40°C (104°F)
Pressure - 140 kPa (200 psi) (1.38 atm)
4. Utilities - Not given
5. Waste Streams - Gaseous emission of methanol, ammonia and methyl formate
are possible.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 6 (1965), p. 576.
Ibid., Vol. 10 (1966) p. 105.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 484.
6-495
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 200
N , N-Dime thy 1 f o rmami de
CH3OH
1. Function - N , N-Dimethylf ormamide (DMF) is derived from the reaction of
methyl formate with dime thy lamine. The reaction product is separated
from methanol and unconverted reactants by distillation.
2. Input Materials
Methyl formate
D ime thy lamine
3. Operating Parameters
Not given
4. Utilities - Not given
5. Waste Streams - Possible atmospheric emissions are - methanol, methyl
formate and dime thy lamine.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 10 (1966), p. 109.
Astle, M.J., Industrial Organic Nitrogen Compounds - ACS Monograph No. 150,
Reinhold Publishing Corp., 1961 p. 74.
6-496
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 201
Acetic Acid (from methanol by carbonylation)
CH3OH + CO > CH3COOH
1. Function - Methanol is carbonylated with carbon monoxide to produce
acetic acid. Various types of catalysts have been proposed for the
carbonylation of methanol. The catalyst most widely employed consists
of two main components: 1) a carbonyl-forming metal from the iron
sub-group (iron, cobalt, or nickel), and 2) either BF or
H3P04.
2. Input Materials - Basis - 1 metric ton acetic acid
Methanol - 610 kg/Mg acetic acid 553 kg (1,175 Ibs/ton)
Carbon monoxide - 787 kg/Mg acetic acid 467 kg (1,030 Ibs/ton)
3. Operating Parameters
Temperature: 200 - 300°C (392-572°F)
Pressure: 20 to 70 MPa (197-691 atm)
Flow rates: not given - > reaction time 1-3 minutes; vapor or
liquid phase
Size of Equipment : not given - tubular reactor type
Types of catalysts: Fe, Co, or Ni acetate + BF_ or HJ?0, . Monsanto
has a new catalyst ( a soluble rhodium-metal -carbonyl complex acti-
vated with an iodide promoter) which permits this reaction to pro-
ceed at pressures as low as 210 kPa (~ 2 atm) and allows use of
synthesis gas as a CO source.
4. Utilities - Basis: 45.5 Gg/yr (100 M Ib/yr) capacity:
Water
o
Cooling - 287 dm /s (4,560 gpm)
6-497
-------
Makeup - 6.1 dm /s (97 gpm)
Power - 6.98 GJ (1940 kWh)
Steam - 15.8 Mg/hr (34,800 Ib/hr)
5. Waste Streams - Reaction section - off-gas scrubber vent (air)
Hydrogen - 5.5 kg/Mg acetic acid
Carbon monoxide - 204 kg/Mg acetic acid
Methane - 12.7 kg/Mg acetic acid
Methanol - 14.9 kg/Mg acetic acid
Light ends - 2.2 kg/Mg acetic acid
About 40 kg (-88 pounds) of organics (50% propionic acid and 50%
higher organics) are produced in the liquid waste stream per Mg
(tonne) of acetic acid produced. The waste stream amounts to about
200 dm /Mg (50 gallons per ton) of product including drains.
6. EPA Source Classification Code - None
7. References
Yakaoka, S., "Acetic Acid," Report No. 37, Stanford Research Institute,
Menlo Park, California, March, 1968.
Gloyna, E. F., and Ford, D. L., "The Characteristics and Pollutional
Problems Associated with Petrochemical Wastes," for FWPCA, Contract
No. 14-12-461, February, 1970.
Austin, G. T., "Industrially Significant Organic Chemicals - Part 1,"
"Chemical Engineering," January 21, 1974, p. 128,129-
Sittig, M., Acetic Acid and Anhydride, Noyes Development Corporation,
Pearl River, N. Y., 1965, p. 24-29-
6-498
-------
7. References (continued)
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 10,11.
6-499
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 202
Formaldehyde
(catalytic air oxidation of methanol)
CH3OH + air
1. Function - All formaldehyde in the United States is produced from
methanol by either vapor-phase catalytic oxidation or by a combination
oxidation-dehydrogenation process. The product is usually marketed
as formalin — a 37% solution stabilized with 9% methanol.
The catalytic conversion of methanol to formaldehyde involves the
reaction of a mixture of methanol vapors and air over a stationary
catalyst at appr&ximately atmospheric pressure. Because methanol and
air form explosive mixtures in the range 6-37% by volume of methanol
in air at 60°C, the commercial processes operate either at methanol
concentrations of nearly 50% or 5-10% by volume of methanol in air.
In the catalytic conversion of methanol to formaldehyde, using silver
catalyst, dehydrogenation and oxidation of methanol may occur
s imultaneously.
CH3OH >• HCHO + H2 -20 Kcal.
CH3OH + 1/2 02 * HCHO + H20 +38 Kcal.
Clean air is heated and mixed with methanol vapors in a controlled
ratio (1:1). Temperature may vary between 450°-700°C with the optimum
around 635°C. Gases from reactors are quenched and the excess methanol
in the resulting methanol-formaldehyde solution is removed by fractiona-
tion.
6-500
-------
In the direct oxidation of methanol to formaldehyde in the
presence of iron-molybdenum oxide catalyst, a low (5-10%) methanol
concentration stream in air is used. The product is essentially
free of methanol.
Formaldehyde may also be produced in a vapor-phase oxidation of
propane-rich LPG. However, this process has not been used since
February 1973 when Celanese Corporation closed its Bay City, Texas
plant.
2. Input Materials-- (data for silver-catalyzed, oxidation-dehydrogenation
process)
Methanol - 438 g/kg of 37% formaldehyde
Air - 888 g/kg of 37% formaldehyde
3. Operating Parameters
1) Oxidation - dehydrogenation
Temperature: 635°C (600-700°C) (1175°F)
Pressure: 146 kPa (1.44 atm)
Catalyst: crystalline silver
Reaction time: 0.5 second
2) Direct oxidation
Temperature: 300-400°C (572-752°F)
Pressure: ~100 kPa (atmospheric)
Catalyst: iron-molybdenum oxide
4. Utilities - Basis: 45.4Gg/yr (100 M Ib/yr) capacity for production
of 37% HCHo by silver-catalyzed dehydrogenation-
oxidation
3
Water, cooling - 88.3 dm /sec (1400 gpm)
o
Water, process - 2.4 dm /sec (38 gpm) (includes water for steam generation)
Steam - 0.794 kg/sec (6300 Ib/hr)
Power - 107 kW (143 hp)
6-501
-------
5. Waste Streams - Off-gases from the absorber of the absorption and
purification section will lead to the following atmospheric emissions:
CO - 63.5 g/kg 37% formaldehyde
H2 - 7.6 g/kg 37% formaldehyde
CH^ - 1.25 g/kg 37% formaldehyde
ECHO - trace
CH OH - trace
formic acid - in water
The major wastewater sources are the scrubber waters and the
dimethyl ether by-product. The total aqueous stream should not
o o
exceed 0.42 dm /kg (100 gal/ton) containing 1-5000 mg/dm COD unless
on-site truck washing is practiced.
6. EPA Source Classification Code - None
7. References
"1973 Petrochemical Handbook," "Hydrocarbon Processing," November 1973,
p. 135,136.
"1975 Petrochemical Handbook," "Hydrocarbon Processing," November
1975, p. 149,150.
Hedley, W. H. , et al., Potential Pollutants From Petrochemical Processes,
Technomic Publishing Co., Eastport, Conn., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 86-88.
6-502
-------
7. References (continued)
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 6," "Chemical Engineering," May 27, 1974, p. 101.
Chemistry in The Economy - American Chemical Society Publication,
1973, p. 32.
Walker, J. F., Formaldehyde, 3rd Edition, ACS Monograph 159, 1964,
p. 16-24.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 422.
6-503
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 203
Ethylene Glycol (from formaldehyde & CO via glycolic acid)
BF H
CH00 + CO + H00 — > HOCH0C00H — >• HOCH-CH-OH
2. 2 22 cat. 2 2
1. Function - Although more than 90% of ethylene glycol produced is made
by catalytic oxidation of ethylene to ethylene oxide, followed by
hydration, a reaction of formaldehyde, water, and carbon monoxide
is also being used. These three chemicals combine at 200°C and
about 70 MPa to form glycolic acid.
This is followed by hydrogen reduction of the product glycolic
acid in the presence of a copper oxide-magnesium oxide catalyst (at
200°C and 10 MPa).
2. Input Materials Per kg ethylene glycol
Formaldehyde 650 g
Carbon monoxide 625 g
Hydrogen 75 g
Sulfuric Acid 45 g
Water
3. Operating Parameters
Temperature: 200°C (392°F)
Pressure: 70 MPa; 10 MPa for hydrogenation
Catalyst: BF for acid formation CuO - MgO (for hydrogenation)
4 -1
Space Velocity: 2 x 10 hrs
4. Utilities
Not given
6-504
-------
5. Waste Streams - Carbon monoxide fed to the primary reaction vessel
is a possible, atmospheric emission. Process slops may carry formal-
dehyde, methanol, higher alcohols, and organic a"cids to waste water
flow.
6. EPA Source Classification Code - None
7. References
Faith, W. L. et al., Industrial Chemicals. 3rd Ed., John Wiley & Sons,
New York, N.Y., 1965 , p. 375, 376, 377.
Chemical Technology, Barnes and Noble Books, New York, N.Y.,
Vol. 4 (1972), p. 294.
6-505
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 204
Methylenedianiline (condensation of aniline and formaldehyde)
HC1
NH4OlT "2" ^y^y ""2 V^/ ""2 ' 3H2° + 2NH4C1
1. Function - The production of methylenedianiline is a two-stage
process. Aniline is neutralized with concentrated hydrochloric
acid in aqueous solution at 100°C to form aniline hydrochloride.
The solution is cooled to 15°C and 40% formaldehyde solution
added, followed by heating at 55 - 60°C for four hours. The
reaction mixture is then chilled again, and the product pre-
cipitated out with dilute ammonium hydroxide. The product may
be further purified by recrystallization from alcohol or water.
2- Input Materials
Basis - 1 kg (Ib) product
Aniline - 1.66 kg (3.66 Ibs)
Formaldehyde (40%) - 0.68 kg (1.50 Ibs)
Concentrated hydrochloric acid - 1.68 &
Ammonium hydroxide
Water - 3.57 £
3. Operating Parameters
Temperature: 55 - 60°C (131 - 140°F)
Pressure: not given
Catalyst: not given
4. Utilities - Not given
6-506
-------
5. Waste streams - Waste water streams may contain ammonium hydroxide,
ammonium chloride, and aniline compounds in solution. There will
be no gaseous emissions. Resinous materials formed on contact
of aniline and formaldehyde will be disposed of in process wastes.
6. EPA Source Classification Code - None
7. References
Scalon, J.T., J. Amer. Chem. Soc., _57, May, 1935, p. 890, 891.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 414.
6-507
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 205
Hexamethylenetetramine
(condensation of formaldehyde with ammonia)
N ^
I CH2, xCH2 '
6HCHO + 4NH, >• I N
' -CH2
1- Function - Hexamethylenetetramine is a heterocyclic fused ring
structure made by the condensation reaction of aqueous formaldehyde
with liquid or gaseous ammonia.
A slight excess of ammonia may be introduced to prevent side
reactions which occur at pH values below 8. The process is performed
at 62-66°C and about 280 kPa (2.76 atm) in an aqueous solution within
a steel, tower-type reactor.
After addition of activated charcoal for the removal of impurities,
the liquid is filtered and then evaporated at reduced pressure (2-4
kPa, 0.02-0.04 atm) to collect the crystalline product. The crystalline
solid mass is then centrifuged, washed, and dried to yield hexamethylene-
tetramine, usually of a purity better than 99%. According to industry
sources, the yield is 97% from formaldehyde or 93.5% from ammonia.
2. Input Materials
Formaldehyde - 3.58 kg of 37% solution per kg of product (based on
97% yield)
Ammonia - 0.519 kg/kg product (93.5% yield)
3. Operating Parameters
Temperature: 62-66°C (144-151°F)
Pressure: 280 kPa (2.76 atm)
6-508
-------
4. Utilities - Not given
5- Waste Streams - Reactor off-gases contain formaldehyde, ammonia, and
methanol (from formaldehyde production). If this stream is incinerated,
NO will be emitted to the atmosphere. The bleed line from the centri-
X
fuge wash, a waste water stream, will contain dissolved formaldehyde,
ammonia, methanol, and hexamethylenetetramine. The drier used in
final preparation of hexamethylenetetramine will emit formaldehyde,
methanol, and ammonia vapors to the air.
6. EPA Source Classification Code - None
7. References
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Company, Westport, Conn., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 98.
Austin, G. T., "The Industrially Significant Organic Chemicals - Part 6,"
"Chemical Engineering," May 27, 1974, p. 104.
U.S. Patent 3,288,790 (November 29, 1966).
Sittig M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,
Noyes Development Corp., Park Ridge, N.J., 1969, p. 364.
Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4
(1972), p. 563.
6-509
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 206
Dimethyl Sulfide (from methanol/carbon disulfide)
4CH3OH + CS2 > 2(CH3)2S + 2H20 + C02
1. Function - Dimethyl sulfide may be produced by the reaction of
methanol with carbon disulfide in the vapor phase in a fixed bed
catalyst of activated alumina. Methyl mercaptan is the chief
by-product.
2. Input Materials
Methanol
Carbon disulfide
Catalyst (activated alumina)
3. Operating Parameters
Temperature: 370-535°C (698-995°F)
Pressure: 414 kPa (4.08 atm)
4. Utilities - Not given
5. Waste Streams - Unreacted methanol and carbon disulfide should be
present along with some methyl mercaptan and possible H_S.
6. EPA Source Classification Code - None
7. References
Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edi-
tion, Noyes Development Corp., Park Ridge, N. J., 1969, p. 266.
U. S. Patent 2,930,816 (March 29, 1960).
6-510
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 207
Dimethyl Sulfoxide (NC>2 oxidation of (City ,.5)
0
(CH3)2S + N02 ^- II + NO
S
/\
CH3 CH3
(DMSO)
1. Function - Dimethyl sulfide is oxidized with a dimethyl sulfoxide
solution of nitrogen dioxide in a reactor at 40-50°C. The reactor
contents pass into a 100°C zone where dimethyl sulfide is sparged
from the crude product with nitrogen. The crude dimethyl sulfoxide
(DMSO) is then neutralized and distilled.
The flow of nitrogen dioxide into the reactor is kept insuffi-
cient to oxidize all of the dimethyl sulfide so that all the N0_
is converted to NO, which is insoluble in DMSO and escapes the exit-
gas stream. This stream passes through a heat exchanger to condense
some of the dimethyl sulfide for recycle back to the reactor. The
gases remaining are conducted to a second reactor where excess N0~
converts the residual sulfide to the sulfoxide. The gases from
this reactor contain substantially no organic matter and are oxidized
with oxygen in a third reactor to regenerate the N0». The gases
finally pass through a DMSO scrubber to remove nitrogen dioxide
prior to venting to the atmosphere.
2. Input Materials
Dimethyl sulfide
Nitrogen dioxide in dimethyl sulfoxide solution
6-511
-------
3. Operating Parameters
Temperature: 20-50°C (68-122°F)
Pressure: 101 kPa (1 atm)
4. Utilities - not given
5. Waste Streams - The gas stream which is vented from the DMSO scrubber
to the atmosphere will consist of C02, 02, N2, and -0.3% nitrogen
oxides (NO ) . The liquid stream from the scrubber contains N02,
but this is recycled back into the process. There could also be
emissions of NO, N02, N203, and N2 from the second and third reactors,
where additional conversion was accomplished. Some liquid waste
could originate from the neutralization of crude dimethyl sulfoxide.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 19 (1969), p. 332, 333.
U.S. Patent 2,935,533 (May 3, 1960).
Sittig, M., Organic Chemical Process Encyclopedia - 1969. 2nd Edition,
Noyes Development Corp., Park Ridge, N.J., 1969 , p. 268.
Chemical Technology, Barnes and Noble Books, New York, N.Y.,
Vol. 4 (1972), p. 585.
6-512
-------
SECTION VI
NAPHTHALENE
6-513
-------
COAL AND PETROLEUM RESIDUES
NAPHTHALENES
208
Ui
Acenaphthene
Naphthalene .
209
>Alkylnaphthalenes
Naphthalene
210
213
214
217
Chloronaphthalenes
Bromonaphtha 1 enes
1- Nitronaphthalene
211 212
>. 1-Naphthylamine . 1-Naphthol
1-Naphthalene sulfonic acid
218 219'
^ 2-Naphthalene sulfontc acid ^ 2-Naphthol
220
Phthalic anhydride
215
216
> Tetrahydronaphthalene
DecahydronaphthaleneJ
221
-} Tetrachlorophthalic anhydride
222
Phthalonitrile
223
-)Anthraquinone
224
Anthraquinone
225
Phthalimide
226
kAnthranilic acid
Figure 11. Naphthalene Section Chemical Tree
-------
I
Ui
t-1
Ul
HN00
Heat
I
Nitration
210
Steam
1
_ HCI
fn s
211
Hydrogenationi
Nj
jT
213
Chlorlnatlon
n2QU4
Water 1 Heat
212
Solvent
1
Heat
I
208
Separation
Catalytic 209
Desulfur1zat1on
Steam
214
Bromlnatlon
215
Hydrogenatlon
/TetrahydroA
(naphthalene)
HSO
at , H
i I
NaOH
\ ,
219]
Substitution and
acidification
-*N( 1-Naphtol
Figure 12. Naphthalene Section Process Flow Sheet
-------
I
Ul
Cooling
TetrachO
rophthallc
,anhydr1dey
Phthalo-^
nltrlle
h"
Heat Oleum Clz
i i 1 >x>
221
ChloHnatlon
XI
Heat «,
222
Ammonolysis and
dehydration
~<3
Benzene
Cooling water 1 H2S01,
^-^ ^nl\\i?>°^
A.nthra-
qulnone
224,223
-
-------
INDUSTRIAL ORGANIC CHECMICALS PROCESS NO. 208
Separation of the Naphthalenes (Alkylnaphthalenes)
1. Function - Alkylnaphthalenes are found in coal tar, lignite
tar, crude oil, drip-oil, heavy petroleum reformate, and gas oil
(4%). The alkylnaphthanes are separated from the naphthalene
fractions usually either by fractionation or solvent extraction,
or both, depending on the purity desired.
In the separation by fractionation, the coal tar or petroleum
fraction feed is sent to a fractionator which produces a naphthalene
concentrate, and a middle product of alkylnaphthalenes, and heavy
aromatics bottoms. The more common present commercial sources
of alkylnaphthalenes are aromatic petroleum fractions of appropriate
boiling range 227 - 268°C (440 - 515°F) cut.
The solvent extraction process consists of first distilling the
feed to get a middle cut in the 204 - 285°C (400 - 550°F) from
the light cycle oil cut. A solvent extraction process known
as the Unisorb process is then used to separate the naphthalene
homologs (alkylnapthalenes) from the lower aromatics. An extract
is produced containing over 85% of the naphthalene homologs (including
acenaphthene) from the charge stock while rejecting lower aromatics.
The process contains a fixed absorbent bed which is operated
isothermally and at constant pressure.
6-517
-------
2. Input Materials
coal tar
light cycle oils
catalytic gas oils
drip-oil
reformer bottoms
3. Operating Parameters - not given
4. Utilities - not given
5. Waste Streams - The air vent streams may contain paraffins or olefins as
well as low boiling aromatics and solvent vapors. The solvents
commonly used in solvent extraction of alkylnaphthalenes are
furfural and sulfur dioxide.
6. EPA Source Classification Code - None
7. References
Brownstein, A. M., "U.S. Petrochemicals, Technologies, Markets,
and Economics," The Petroleum Publishing Company, Tulsa, Oklahoma,
1972, pp. 213-215.
Kirk-Othmer, Encyclopedia of Chemical Technology," 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967), pp. 678-690.
Broughton, D. B. and Hardison, L. C., "Unisorb Extracts Naphthalene
Homologs," Hydrocarbon Proc. and Petrol. Refiner, 1962, 41(5),
125-128.
6-518
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 209
Desulfurization of Hydrocarbons
RCH2SH + CuCl2 —*- (RCH2S)2 + CuCl (1)
CuCl + 02 —>• CuCl2 + CuO (2)
RCH2SH + H2 molyMate* RCH3 + H2S
1. Function - Hydrocarbon feeds from petroleum sources may contain signi-
ficant amounts of sulfur containing compounds principally hydrogen
sulfide and mercaptans. If these stocks are to be used in reactions
involving catalysts, which are "poisoned" by sulfur compounds, these
compounds must then be removed.
There are three methods of treating hydrocarbon feeds to eliminate
the undesirable sulfur compounds. These may be classified as 1) oxida-
tion, 2) catalytic desulfurization and 3) extraction.
Oxidation - Mercaptans are converted to disulfides by exposing the
hydrocarbon stream to cupric chloride, CuCl-. The copper salt may be
deposited on an inert substrate and used as a slurry or as a fixed
catalytic bed. Sulfur compounds are converted to the inactive disul-
fides, but are still present in the feed. CuCLmay be regenerated
with air either during or after the reaction.
Catalytic desulfurization - Mercaptans are converted to the lower
boiling hydrocarbons by loss of hydrogen sulfide. Hydrogen and a
cobalt molybdate or alumina catalyst are used. Oxygen and nitrogen
compounds behave similarly to sulfur compounds and thus this catalytic
desulfurization process has become important in the upgrading of
reformer feed stocks. Commercial processes use temperatures of
o
350-450°C with pressures up to 1500 psig (100 Kg/cm ).
6-519
-------
Extraction - In some cases, the sulfur containing organics are ex-
tracted and recovered from the hydrocarbon stock by adding an organic
solvent to the caustic soda (or potash) which is being used as the
extraction liquid. The solution is subsequently regenerated by air
blowing to oxidize mercaptans to disulfides.
2. Input Materials
Naphthalene feed
Hydrogen
Catalyst - cobalt molybdate
3. Operating Parameters
Temperature 350-450°C (662-842°F)
Pressure up to 10.34 MPa (102 atm)
Catalyst cobalt molybdate
4. Utilities
Not given
5. Waste Streams - Hydrogen sulfide, ammonia, mercaptans
6. EPA Source Classification Code - None
7. References
Chemical Technology, Barnes and Noble, New York, N.Y., Vol. 4
(1972), p. 55-56.
6-520
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 210
1-Ni t ronaphthalene
1. Function - 1-Nitronaphthalene is prepared by nitrating naphthalene
with mixed acid at 50-60°C. The organic phase is separated and washed
with hot water until free of acids. The product contains about 0.5-1%
2,4-dinitronaphthalene and 3% 2-nitronaphthalene. These are easily
removed by crystallization or by sweating (partial melting). The
nitration of naphthalene gives a 94% yield of the 1-isomer. The
relatively small amount of 2-isomer is easily removed with the other
by-products by crystallization from alcohol.
2. Input Materials
Naphthalene
Mixed Acids (1 part 62% HN03 + 3 parts 80% H2S04>.
3. Operating Parameters
Temperature: 50-60°C (122-140°F)
Pressure: 100 KPa (1 atm)
4. Utilities - Not given
5. Waste Streams - Air vent streams may contain oxides of nitrogen. Waste
streams from the washing and purification processes contain nitric and
sulfuric acids, naphthalene, a-nitronaphthalene, 6-nitronaphthalene,
2,4-dinitronaphthalene, and alcohols.
6. EPA Source Classification Code - None
6-521
-------
7. References
Kirk and Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 83.
Ibid.. Vol. 13 (1967) p. 704.
Howe, A. P. and Hass, H.B., Ind. Eng. ChemQS. 251, (1946).
Astle, M. J., Industrial Organic Nitrogen Compounds, Reinhold Publishing
Corp., New York, N.Y., 1961 , p. 320-21.
6-522
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 211
1-Naphthylamine (reduction of 1-nitronaphthalene)
NO
+ HC1 + 4H00 + 9Fe
•'•• Function - 1-Naphthylamine is prepared by the catalytic reduction
of 1-nitronaphthalene with iron powder and hydrochloric acid. The
product mixture is made alkaline and 1-naphthylamine is distilled
out with superheated steam. The yield in this process approximates
96%. By-products of this reaction are 2-naphthylamine, 1,5-naphthalene
diamine and l,l'-binaphthylamine.
2. Input Materials
1-Nitronaphthalene
Iron powder
Hydrochloric acid (dilute)
3. Operating Parameters
Temperature: 80 ° C
Pressure: 100 kPa (1 atm)
4. Utilities - Not available
5. Waste Streams - Air vent streams would include HC1 vapor and hydrogen.
Waste water streams contain hydrochloric acid, iron salts (including
chlorides), some 1-naphthylamine and 1-nitronaphthalene.
6. EPA Source Classification Code - None
7. References
Kirk and Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 83.
Chemical Technology, Barnes and Noble, New York, N.Y., Vol. 4
(1972), p. 520.
6-523
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 212
1-Naphthol (from l-naphithylamine)
200° 14 atm
1. Function - The best and most economical process for the production of
1-naphthol is the hydrolysis of 1-naphthylamine in aqueous sulfuric
acid at 200°C and 14 atm. pressure. The yield is 95% and the product
is pure. The purity of the product gives this process a distinct
advantage over the alkali fusion of the sulfonic acid derivative,
the method of choice for 2-naphthol, since the product purity from
this process is often too low for many applications.
2. Input Materials
1-Naphthylamine 1.06 kg/kg product
Sulfuric acid (aqueous)
3. Operating Parameters
Temperature - 200°C (392°F)
Pressure - 1.42 MPa (14 atm)
4. Utilities - not given
5. Waste Streams - Effluents would contain ammonium sulfate, sulfuric acid,
1-naphthylamine and 1-naphthol.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition.
Interscience Publishers, New York, N.Y., Vol. 13 (1967) p. 717.
Chemical Technology, Barnes and Noble, New York, N.Y., Vol. 4 (1972) p. 326.
6-524
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 213
CHLORONAPHTHALENES
+ HC1 (1)
>80°C
Polychl°ronaphthalenes
3, 3
1. Function - Commercial quantities of 1-chloronaphthalene and mixtures
of polychloronaphthalenes are produced by passing chlorine gas into
molten naphthalene (80° C) . If 1-chloronaphthalene production is
favored, catalysts are not normally required.
If a polychloronaphthalene mixture is the desired product, ferric
or antimony chloride catalyst must be added to the reaction mixture
to promote chlorine addition. Chlorination is begun at 80°C, and the
temperature is slowly raised as the reaction proceeds. During the
process, the chlorination mixture is continually agitated.
When the desired point has been reached, the chlorination mixture
is neutralized by stirring in the molten state with aqueous alkali,
washed with water, and dried under vacuum.
2. Input Materials
Naphthalene
Chlorine
Sodium hydroxide
Water
6-525
-------
3. Operating Parameters
Temperature - >_ 80°C (176°F)
Pressure - not given
Catalyst - for polychloronaphthalenes FeClg or SbCl3 (0.5%)
4. Utilities - Not given
5. Waste Streams - Wastewater streams from washing operations probably
contain sodium chloride, sodium hydroxide, and traces of naphthalene
and chlorinated naphthalenes. Chlorine gas may be discharged from
various processing equipment.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964) p. 300.
6-526
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INDUSTRIAL ORGANIC CHECMICALS PROCESS NO. 214
Bromonaphthalenes
Br
f^Y^
+ HBr
!• Function - ^-Bromonaphthalene and lesser amounts of dibromonaphthalenes
are produced by the interaction of naphthalene and bromine in car-
bon tetrachloride or water. Iron catalysts are required if car-
bon tetrachloride serves as the reaction medium. Hydrogen bromide
by-product is allowed to escape, preferably being washed by in-
coming raw material. The crude product is then dried and frac-
tionated, giving oc-bromonaphthalene in 72 - 75% yield.
2. Input Materials
Naphthalene - 0.82 - 0.86 kg/kg product
Bromine
Water or carbon tetrachloride
3. Operating Parameters
Temperature: 100°C (212°F)
Pressure: not given
Catalyst: iron (in CCl^)
*• Utilities - Not .given
5. Waste Streams - Air vent streams contain hydrogen bromide, the
principal by-product of the reaction. Carbon tetrachloride will
be present in the air vent streams from solvent recovery systems,
when this solvent is used as the reaction medium. Waste streams
will contain HBr, naphthalene, and some bromonaphthalenes when
water is used as the solvent medium. Sodium bromide will be
present in waste water when caustic soda is used to neutralize
the HBr absorbed in the water.
6-527
-------
6. EPA Source Classification Code - None
7. Reference
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 3 (1964), p. 775.
6-528
-------
INDUSTRIAL ORGANIC CHECMICALS PROCESS NO. 215
Tetrahydronaphthalene
1. Function - 1,2,3,4-Tetrahydronaphthalene, more commonly known
as tetralin, is produced exclusively by the catalyic hydro-
genation of naphthalene. This reduction is carried out at 150°C*
in the presence of nickel or modified nickel catalysts.
Since active nickel catalysts are poisoned by sulfur compounds,
represented predominatly in naphthalene by thianaphthene,
commerical naphthalene must be desulfurized prior to hydro-
genation. This is accomplished by treatment with Sodium or by
a catalytic dehydrosulfurizing process.
2. Input Materials
Naphthalene (desulfurized)
Hydrogen
3. Operating Parameters
Temperature: 150°C (302°F)
Pressure: 100 - 200 KPa (1 - 2 atm)
Catalyst: nickel or modified nickel
4. Utilities - Not given
* Heat-exchanges are necessary to control the temperature of this
exothermic reaction, since destructive hydrogenation occurs
at high temperatures.
6-529
-------
5. Waste Streams - Air vent streams from the reactor contain hydrogen
and may have small quantities of tetrahydronaphthalene and naphthalene.
When the product is purified by extractive distillation the air
vent streams may contain tetrahydronaphthalene, naphthalene and some
solvent (diethylene glycol for example).
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967), p. 676-77.
6-530
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 216
Decahydronaphthalenes
CO
L. Function - Commercial decahydronaphthalene, a mixture of cis-
and trans-isomers more commonly known as Decalin, is prepared
by the catalytic hydrogenation of naphthalene.* The reaction may
be carried out in the fused-state (above 100°C) or in the liquid
phase at 2.5 - 4.0 MPa (25 - 40 atm) and 200 - 260°C. Both pro-
cess variations employ copper or nickel catalysts.
2. Input Materials
Naphthalene (desulfurized)
Hydrogen
3. Operating Parameters
Temperature: fused state - >100°C (212°F)
liquid phase - 200 - 260°C (232-500°F)
Pressure: fused state - not given
liquid phase - 2.5 - 4.0 MPa (25-40 atm)
Catalyst: copper or nickel
4. Utilities - Not given
5. Waste Streams - Air vent streams from the reactor will contain
hydrogen and some naphthalene and decahydronaphthalene. Air vent
streams from the purification system contain naphthalene decahydro-
naphthalene and solvent when extractive distillation is used to
purify the product.
* The naphthalene feed is desulfurized by the methods discussed in
Process No. 209.
6-531
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6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967), p. 677.
6-532
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 217
1-Naphthalenesulfonic Acid
1. Function - Commercially, 1-naphthalenesulfonic acid is prepared
by sulfonating naphthalene with 98% sulfuric acid below 60°C.
Isolation is accomplished by liming, conversion of the calcium salt
to the sodium salt by soda ash, and drying. The technical product
contains about 77.5% 1-naphthalenesulfonate, 10.2% 2-naphthalenesulfonate,
5.7% disulfonate, 2.7% sodium sulfate, and 3.7% water.
2. Input Materials
Naphthalene
Sulfuric acid (98%)
Lime
Soda ash
3. Operating Parameters
Temperature - <60°C (140°F)
Pressure - 101 kPa (1 atm)
4. Utilities - Not given
5. Waste Streams - Air vent streams from the reactor will contain some
sulfur dioxide and small quantities of naphthalene. The overhead
gases from the concentrator contain sulfur dioxide and naphthalene.
Calcium sulfate and calcium carbonate are recovered from neutralization
and washing steps. Waste wash water contains some sulfuric and
naphthalene sulfonic acids.
6-533
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967), p. 700.
Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4
(1972), p. 597.
6-534
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 218
2-Naphthalenesulfonic acid
1. Function - 2-Naphthalenesulfonic acid is commercially prepared by
treating naphthalene with about one part of 93-96% sulfuric acid
at 160°C.
1-Naphthalenesulfonic acid, which constitutes about 15% of the
crude product, is hydrolyzed back to naphthalene by steam, and the
latter is recovered by steam distillation. The sulfonation mixture
is then added to water, and 2-naphthalenesulfonic acid is precipi-
tated as the sodium salt by the addition of sodium chloride.
2. Input Materials
Naphthalene
Sulfuric acid (93-96%)
Sodium chloride
Water
3. Operating Parameters
Temperature - 160°C (320°F)
Pressure - Not given
4. Utilities - Not given
5. Waste Streams - Sodium chloride, sodium sulfate, and caustic acid may
be present in process wastes.
6-535
-------
6. EPA Source Classification Code - None
''• References
Klrk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13, (1967), p. 700.
6-536
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 219
2-Naphthol (from 2-naphthalenesulfonic acid).
SO Na ^^ ^^ ^ONa
NaOH, 325°C
ONa
•"-• Function - In commercial practice, 2-naphthol is prepared by fusing
the sodium salt of 2-naphthalenesulfonic acid with sodium hydroxide
in a cast-iron or nickel-steel kettle at 325°C. The melt is run into
cold water, acidified with sulfuric acid, and the free 2-naphthol is
separated. The product is washed well with water, distilled jg. vacuo,
and sublimed. The yield is almost 80% of the theoretical.
2. Input Materials
2-Naphthalenesulfonic acid (sodium salt) - 1.80 kg/kg product
Sodium hydroxide
Sulfuric acid
Water
3. Operating Parameters
Temperature: 325°C (617°F)
Pressure: not given
4* Utilities - Not given
5. Waste Streams - The waste water from washing operations probably contains
quantities of sodium sulfate, naphthalenesulfonic acids, and naphthols.
6-537
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967) p. 718.
6-538
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 220
Phthalic Anhydride (from naphthalene)
+ 902 (air) >- 2 K)l 0 + 4H20 4- 4C02
0
1. Function - As of January 1, 1975, 36% of the U.S. capacity for
phthalic anhydride production was based on naphthalene feedstock.
Both petroleum naphthalene (>80°C) and desulfurized coal-tar naphtha-
lene (78°) are converted to phthalic anhydride by vapor-phase air
oxidation in the presence of a vanadium pentoxide catalyst.
There are three processes in use for the air oxidation of
naphthalene. Two of these include a fixed catalyst bed process
and these are adaptable to both naphthalene and o-xylene feed stocks.
The third process involves a fluidized catalyst bed and has been
applied only to naphthalene. A significant by-product of all three
processes is maleic anhydride and maleic acid. Small amounts of
benzoic acid are recovered from the fixed bed processes.
The most widely used oxidation processes are the fixed bed pro-
cesses. These differ in the catalyst composition employed and the
temperature range of operation. The original process employed a
catalyst consisting of 65% ^2°5' 30% Mo03 and 5% CuO or Mn^. It
operated at 400-475°C and gave yields of phthalic anhydride of
approximately 65%.
The von Heyden process, a low-temperature, fixed-bed air oxidation,
also accounts for considerable naphthalene-based phthalic anhydride
production. Reaction temperatures are maintained in the 350-360°C
range with 4-5 sec contact time. The catalyst is usually vanadium
6-539
-------
pentoxide on silica with 20-30% potassium sulfate. Yields in the
neighborhood of 82% are obtained by this process with limited by-
production of maleic anhydride, maleic acid, etc.
The third process employs an air-fluidized bed of V^O,- into which
is injected naphthalene in vapor form. The bed is maintained at
340-380°C and 1 atmosphere. The air/feed ratio can be maintained at
2 to 3x a lower value than in the fixed bed system. It is not possi-
ble to use o-xylene as a feedstock in this system and as a result
the use of this system is decreasing as the difficulty in obtaining
naphthalene feedstock increases. Yields from this process approxi-
mate 85%. The vaporous effluent in all these processes is passed
through heat exchangers where phthalic anhydride crystallizes and
deposits on the walls. Heat is then applied and the crude product
is melted out and collected. Using this procedure 98-99% of the
phthalic anhydride in the effluent is recovered.
The crude product is purified by a chemical soak in sulfuric
acid and caustic followed by a heat soak at 150-250°C. This heat
treatment removes water and other impurities such as maleic acid
and anhydride as well as benzoic acid. The residual phthalic anhydride
is vacuum distilled in batch or continuous operation.
2. Input Materials - Basis - 1 metric ton phthalic anhydride
Naphthalene (>80° or desulfurized) 1,250 kg (2,756 Ibs)
Air (15°C, 59°F) 26,000 m3 (918, 181 ft3)
Sulfuric acid
Sodium hydroxide
Water
6-540
-------
3. Operating Parameters
Temperature: High temperature, fixed bed
Von Heyden
Fluidized bed
Pressure: Von Heyden
Fluidized bed
Catalyst: High Temperature, fixed bed
Von Heyden
400-475°C (752-887°F)
350-360°C (662-680°F)
340-380°C (644-716°F)
48-55 kPa (0.47-0.54 atm)
101 kPa (1 atm).
65° V205, 30% Mo03, 5%
(CuO or Mn_0.)
on Si02 + 20-30%
Reaction
Time:
Fluidized bed
Fluidized bed
Von Heyden
Fixed bed
Finely divided
19-20 sec
4-5 sec
0.1-0.6 sec
4. Utilities - Basis 0.72 kg/sec capacity (50M Ib/yr)
Water
Cooling, makeup (stream generation), makeup (cooling) - 61,000 gph
Electricity
Process - 2.0 MW
Utilities - 88 kW
o
Fuel - 3.3 dm /sec average (420 cfh)
*
5. Waste Streams
Spray scrubber effluent (water)
Phthalic anhydride - trace
Maleic anhydride - 16.7 Kg/Mg phthalic anhydride
Spray scrubber effluent (air)
These values are characteristic of the first fixed-bed process.
6-541
-------
5. Waste Streams (continued)
Naphthalene - trace
Phthalic anhydride - 9.5 Kg/Mg phthalic anhydride product
Maleic anhydride - 26 Kg/Mg phthalic anhydride
Other - 23.7 Kg/Mg phthalic anhydride (assumed to be organic in nature)
Phthalic anhydride recovery columns (solid)
Phthalic anhydride - 69.3 kg/Mg phthalic anhydride
Other - 51 kg/Mg phthalic anhydride (assumed to be organic in nature;
specific compound information not available)
6. EPA Source Classification Source - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 8," "Chemical Engineering," July 22, 1974, p. 109.
Sittig, M., Chemicals from Aromatics, Noyes Development Co.,
Park Ridge, N.J., 1966, p. 50.
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 15 (1968), p. 450.
"1971 Petrochemical Handbook," "Hydrocarbon Processing," November
1971, p. 189.
Sittig, M., Pollution Control in the Organic Chemical Industry.
Noyes Data Corp., Park Ridge, N.J., 1974, p. 186-188.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 658-660.
6-542
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 221
Tetrachlorophthalic Anhydride
0 + 4C1,
0 + 4HC1
Cl
1. Function - Tetrachlorophthalic anhydride is produced by the high-
temperature chlorination of phthalic anhydride in fuming sulfuric
acid. Antimony pentachloride may be used as a catalyst.
2. Input Materials
Phthalic anhydride
Chlorine
Sulfuric acid (fuming)
3. Operating Parameters - Not given
4- Utilities - Not given
5. Waste Streams - Wastewater from the acid scrubber may contain sodium
hydroxide, and traces of phthalic anhydride, and various chloro-
substituted phthalic anhydrides.
6. EPA Source Classification Code -None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 15 (1968), p. 446.
6-543
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 222
Phthalonitrile (from phthalic anhydride)
CN
+ 3H 0
CN Z
1. Function - One competitive route to phthalonitrile involves the
vapor-phase reaction of phthalic anhydride and ammonia. This conver-
sion takes place at high temperatures over an alumina catalyst.
Phthalimide and/or phthalamide intermediates are probably involved.
2. Input Materials
Phthalic anhydride
Ammonia
3. Operating Parameters
Temperature - Not given
Pressure - Not given
Catalyst - Alumina
4. Utilities - Not given
5. Waste Streams - Effluents from the ammonia stripper and/or separator
probably contain ammonia, phthalic anhydride, phthalonitrile, and
reaction intermediates such as phthalamide and phthalimide.
6. EPA Source Classification Code - None
6-544
-------
7. References
Kirk-Othmer, Ehcylcopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 15 (1968), p. 447.
Throdahl, M. C., Zerbe, R. 0., and Beaver, D. J., Ind. Eng. Chem.,
43, 926 (1951).
6-545
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 223
Anthraquinone (solvent method)
.0 +
CO
50-60°C
!
2A1C1.
COC,H
COO-Aid,
100-110°C
cone.
1. Function - The most frequently used route to anthraquinone involves
the condensation of phthalic anhydride and benzene to give o-benzoyl-
benzoic acid which undergoes ring closure by dehydration. Overall
this can be considered a modified Friedel-Crafts reaction. Two
general methods are utilized to produce the product, the solvent
method and the ball mill method.
In the solvent method, phthalic anhydride is added to a cast-iron
kettle containing aluminum trichloride and a large excess of benzene.
An aluminum chloride complex of o-benzoylbenzoic acid is formed with
an evolution of heat. The temperature is regulated so that it slowly
reaches 50-60°C. Hydrogen chloride evolved during the reaction is
discharged to a condenser-scrubbing system.
When the evolution of HC1 is complete the reaction mass is trans-
ferred to an acid proof reactor containing dilute H-SO, which decomposes
the complex to o-benzoylbenzoic acid and water soluble aluminum sulfate.
The water and benzene solutions are separated and the o-benzoylbenzoic
acid recovered by treating the benzene phase with aqueous sodium
6-546
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carbonate. The benzene is separated, distilled and recycled. The
sodium salt of o-benzoylbenzoic acid is neutralized and filtered out
of the aqueous phase.
The o-benzoylbenzoic acid is washed, dried and treated with
concentrated l^SO^ or oleum at 100-110°C. Practically quantitative
yields of high-purity anthraquinone are obtained. If further purifi-
cation is required it may be done by sublimation.
2. Input Materials
Phthalic anhydride - 0.75 kg/kg product
Benzene
Aluminum chloride (anhydrous)
Sulfuric acid
Sodium carbonate
Sodium hydroxide (HC1 scrubber)
Water
3. Operating Parameters
Temperature: condensation - 50-60°C (122-140°F)
dehydration - 100-110°C (212-230°F)
Pressure: not given
4. Utilities - Not given
5. Waste Streams - The principal pollutant sources in this process are
most likely wastewater effluents from the HC1 scrubber, phase separations,
and filtering and washing operations.
Hydrogen chloride scrubber
6-547
-------
Sodium chloride and caustic soda are probably present in this waste
stream
Aqueous phase separation
The discarded aqueous phase of the aluminum chloride complex decom-
position product is likely to contain sulfuric acid as well as various
aluminum salts.
Benzene extraction
The extract water probably contains quantities of benzene and other
organics, i.e., purification solvents.
Filtering/washing operations
Hydrochloric or sulfuric acid and various sodium salts are probably
the principal pollutants in the waste stream.
Indeterminate quantities of phthalic anhydride, benzene, and o-benzoyl-
benzoic acid may be present in all wastewater effluents.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience
Publishers, New York, N.Y., Vol. 2, (1963), p. 435.
6-548
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 224
Anthraquirione (ball mill method)
IUSO,
5~20% oleum
+ H20 + 2A1C13
1. Function - As mentioned in Process No. 223, the ball mill method is
one of two general routes to anthraquinone from phthalic anhydride and
benzene. In this process, the reactants are mixed in practically
stoichiometrical quantities with only a slight excess of benzene pre-
sent. Consequently, the product of the condensation reaction is
discharged as a dry aluminum chloride complex of o-benzoylbenzoic acid
which can be ring-closed directly to anthraquinone by treatment with
strong sulfuric acid or 5-20% oleum.
Alternately, the complex may be anhydrously decomposed to o-benzoyl-
benzoic acid and subsequently dehydrated by the method described in
Process No. 223 . The yield and quality of the product obtained by this
procedure are almost the same as in the solvent method.
However, the ball mill operation has two distinct advantages over
the solvent method. Practically no solvent recovery is necessary, and
the liberated hydrogen chloride is free of corrosive action since decom-
position of the aluminum chloride complex is carried out anhydrously.
2. Input Materials
Phthalic anhydride - 0.75 kg/kg product
Benzene
6-549
-------
2. Input Materials (continued)
Aluminum chloride (anhydrous)
Sulfuric acid or oleum (5-20%)
Aqueous sodium hydroxide (HC1 scrubber)
3. Operating Parameters - see Process No. 224.
4- Utilities - Not given
5. Waste Streams - Wastewater from the HC1 scrubber probably contains sodium
chloride, sodium hydroxide, and traces of phthalic anhydride and benzene.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience
Publishers, New York, N.Y., Vol. 2 (1963), p. 436.
6-550
-------
INDUSTRIAL ORGANIC CHEMICALS
Phthalimide
PROCESS NO. 225
1. Function - On an industrial scale, phthalimide is produced by
saturating molten phthalic anhydride with dry ammonia and heating
the mixture to 170-240°C under pressure.
Alternately, the cyclic imide can be prepared in 95-97% yield
by heating the anhydride with concentrated aqueous ammonia solution and
eventually raising the temperature to 300°C. Phthalimide is isolated
by evaporating the product solution to dryness.
2. Input Materials
Phthalic anhydride - 1.05 kg/kg product
Ammonia (anhydrous or aqueous)
3. Operating Parameters
Temperature - anhydrous process - 170-240°C (338-464°F)
aqueous process - 300°C (572°F)
Pressure - anhydrous process - elevated
aqueous process - atmospheric
4. Utilities - Not given
6-551
-------
5. Waste Streams - In the anhydrous process, the principal pollutant
source is probably the ammonia absorber off-gas, containing ammonia
and smaller quantities of phthalic anhydride. In the aqueous
process, waste gases from evaporation may also contain quantities
of ammonia and phthalic anhydride.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience
Publishers, New York, N.Y., Vol. 15 (1968), p. 447.
6-552
-------
INDUSTRIAL ORGANIC CHEMICALS
Anthranllic Acid
NaOH
PROCESS NO. 226
1.
2.
3.
COOH
+ NaOCl
NaOH
NaCl
4.
•CONH-
Function - Anthranilic acid is prepared in high yield by the action
of sodium hypochlorite or hypobromite on phthalimide in alkaline
solution at 80°C. The ring is opened by hydrolysis and the phthal-
amidic acid intermediate undergoes the Hofmann reaction.
Anthranilic acid is precipitated on neutralization of the
alkaline solution.
In commercial operations, sodium hypochlorite or hypobromite
is probably prepared in situ by passing chlorine or bromine into
the sodium hydroxide solution.
Input Materials
Phthalimide
Sodium hydroxide
Chlorine or bromine
Water
Mineral acid
Operating Parameters
Temperature: 80°C (176°F)
Pressure: not given
Utilities - Not given
6-553
-------
5. Waste Streams - Hypochlorous acid or the hypobromous acid may be
detected in any air vent streams from the reactor. Chlorine and/or
bromine will also be present. Waste water streams contain some
sodium chloride and small quantities of anthranilic acid.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 3 (1964), p. 434.
6-554
-------
SECTION VII
PARAFFINS
6-555
-------
ETHANE,PROPANE,BUTANE_
227
241
Butyraldehyde
233
Acetic acid
Acetone
- Butyric acid
' Ethyl acetate
-^Ethyl alcohol
-^ Formic acid
-} Methyl acetate
Methyl alcohol
^Methyl ethyl ketone
-^Propionic acid
-> n-Propyl alcohol
-^Butadiene
234
Carbon tetrachloride
PARAFFINS
-^Butyric acid
228
-$• n-Propyl amines
229!
-^Propionaldehyde
230
n-Propyl chloride
249
-^Benzophenone
235
237
Perch!oroethylene-
,Nitroethane
Nitromethane
236
-> Hexachloroetnane
238
^n-Butenes
Nitropropanes
239
Polybutenes
240
j> Butadiene
231
n-Propylamines
232
Butyronitrile
PENTANE , ISOPENTANE
242
248
Amyl chlorides .
Dichloropentanes
-^ Isoamylenes
247
243
> Amyl ami nes
244
04 C
Amy! mercaptans
^Isoprene
^Isoprene
alcohols.
Amyl ether
^ Pentylenes
Figure 13. Paraffins Section Chemical Tree
6-556
-------
I
Ul
Ul
Cooling water
"Tit 1
227
Oxidation
Acetic acid
Methyl ethyl ketone
Propionic acid
Butyric acid
Formic acid
Ethyl acetate
Methyl acetate
Ethyl alcohol
Methyl alcohol
Acetone
Propyl alcohol
Butyraldehyde
-WJJ
Heat
Amination
n-Propyl ale.
st!am I Na'CN
2321X1
Figure 14. Paraffins Section Process Flow Sheet
-------
Benzene Cooling
r 1T- iT
Steam
Heat HN03
| I >O
Nitromethane " 237 Xj
Ml ti*nni"nn*inpfl ^*— ^ MIIIMII imi ^*i^m
NHrobutane
1
Ui
Ul
oo
Heat
e241j^
NaOH Cooling
H1T12 It
234.235
""• "• Clilut iiidliuii
water
A
*B
Heat Quench water
238
N3**
O ^
{ Carbon \
•"1 tetra- 1 —
V chloride /
fc/Perchloro.- \ —
\ ethyl ene t
n-Butenes 1
»
249
Condensation
NaOH 'Heat C1,2
\ \ \ *
»»i
236
Chlorlnatlon
A1C13 Butane
239
Pnl vtnc^vi T/fUnn
CH3CN
TI n
Ox1dat1ve 24°
dehydrogenatlon
w Ben zophenon
< { ^
__BJHexachloro
^^ ethane
^_^
Jp x^ — ^>
^2S /
^^^j^ r
1 V_
<$ ^~"
•< /
V
Figure 14. Paraffins Section Process Flow Sheet (Cont.)
-------
Coolii
ig water
u
C12
242
Chlorlnatlon
I 1
Cooling water
Cooling water
Heat Water I I
* (S
248
Dehydrogenation
tiexane
1H2SO,,
HaOH^
246
Extraction
XI
Ui
Ui
HH3
243
Amonolysis
n Heat
XI
NaOH, aq. Alcohol
[ £ *
244
Hydrolysis
x|
NaSH
1 />
245 1X1
Substitution 1
Cooll
St
ng water
ea?J|
Heat Wat
\ \
247
Dehydrogenation
er
XJ
Figure 14. Paraffins Section Process Flow Sheet (Cont.)
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 227
Acetic Acid and by-products (oxidationof n-butane)
C4H10 + 02 (Air) * CH3COOH + by-products
1. Function - The most economical route to acetic acid, and one which
accounted for 46% of the total 1973 production in the United States,
is the liquid-phase oxidation of a natural gas or light petroleum
fraction containing 95% n-butane.
The oxidation of n-butane is carried out at 150-225°C and 5.5 MPa
(-800 psig) in the presence of a transition-metal acetate, usually cobalt
acetate. Compressed air and liquid butane are fed to a liquid phase
reactor. Reaction product is withdrawn, cooled and sent to a decanter
for phase separation. The hydrocarbon-rich phase is recycled to the
reactor. The aqueous phase is sent to the recovery and purification
system. Off-gases primarily nitrogen, oxides of carbon and n-butane,
are scrubbed for butane recovery and vented through an expander turbine
to recover energy. Low boiling organics are separated from the crude
acetic acid by conventional distillation. Recovered by-products include
methanol, acetone, n-propyl alcohol and methyl ethyl ketone. Depending
on reaction conditions, formic, propionic and butyric acids and their
esters (methyl, ethyl) may also be recovered. Azeotropic distillation is
used to purify the crude acetic acid to glacial acetic acid.
2. Input Materials - Basis - 1 metric ten products
*
n-Butane - 1.08 kg/kg acetic acid 965 kg (2127 Ibs/ton)
Alr 3750 m3 (1.32 x 105 ft3/ton)
*
The hydrocarbon feed also contains some propane, ethane, isobutane, and
other lights.
6-560
-------
3. Operating Parameters
Temperature - 150-225°C (302-437°F)
Pressure - 5.52 MPa (54.5 atm)
Catalyst - cobalt acetate
*• Utilities - Not given
5. Waste Streams - Various wastewater streams from the purification section
may contain acetic acid and a variety of alcohols, aldehydes, ketones,
esters, other organic acids, ethers, and high-boiling impurities.
Quantities of butane, propane, ethane, etc., are probably discharged to
the atmosphere from the reaction section. No specific information was
available.
6. EPA Source Classification Code - None
7. References
Austin, George T., "The Industrially Significant Organic Chemicals -
Part 1," "Chemical Engineering," January 21, 1974, p. 128,129.
Ibid., Part 4, April 15, 1974, p. 89,90.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Interscience
Publishers, New York, N.Y., Vol. 8 (1965) p. 396,397.
Lowry, R. P. and Aguilo, A., "Hydrocarbon Processing," November, 1974, p. 105.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition, John
Wiley and Sons, New York, N.Y., 1975, p. 11,12.
6-561
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 228
n-Propyl Amines (from n-prbpyl alcohol)
1. Function - Propyl alcohol reacts with ammonia at moderately high
temperature (300-500°C) and pressures of 1-20 MPa (10-200 atm) to yield
mono-, di- and tripropyl amines. The mixture of amines formed is thought
to be in equilibrium and the yield of each of them can be increased by
recycling the others. The product ratio may also be controlled by the
ratio of reactants and the operating temperature- A catalyst consisting
of activated alumina is commonly used in these reactions. Silica, and
magnesium oxide as well as alumina containing Fe_0_, TiO_ and cobalt,
Z. j £•
nickel and chromium oxides have been used to promote amine formation.
2. Input Materials
n-Propyl alcohol
Ammonia
3. Operating Parameters
Temperature: 300-500°C (572-932°F)
Pressure: 1-20 MPA (10-200 atm)
Catalyst: alumina
6-562
-------
4. Utilities - Not given
5. Waste Streams - Waste effluents from strippers, separators, etc.,
may contain ammonia, n-propyl alcohol, and all of the n-propylamines.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.-Y., Vol. 2 (1963), p. 117.
Astle, M.J., Industrial Organic Nitrogen Compounds, Reinhold Publishing
Corporation, New York, N.Y., 1961 , p. 8-9.
6-563
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 229
Propiorialdehyde .(from n-propyl alcohol)
!• Function - Small quantities of propionaldehyde are produced by the
dehydrogenation of n-propyl alcohol. This conversion is carried
out at 200- 300° C in the presence of copper compounds or iron oxide.
Reaction equipment is usually stainless steel, but aluminum
is also satisfactory.
2. Input Materials - n-propyl alcohol
3. Operating Parameters
Temperature - 200-300°C (392-572 °F)
Pressure - Not given
Catalyst - copper compounds (copper chromite) or iron oxide
4. Utilities - Not given
5. Waste Streams - Waste gases from this process may contain hydrogen,
n-propyl alcohol, and propionaldehyde.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed. , Interscience
Publishers, New York, N.Y. , Vol. 16 (1968), p. 550.
6-564
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 230
n-Propyl Chloride (from n-propyl alcohol)
ZnCl2
HC1
1. Function - n-Propyl chloride is produced by heating n-propyl alcohol
in concentrated hydrochloric acid. Zinc chloride catalyzes the re-
action.
2. Input Materials
n-Propyl alcohol
Hydrochloric acid (cone.)
3. Operating Parameters
Temperature: not given
Pressure: not given
Catalyst: ZnCl2
4. Utilities - Not given
5. Waste Streams - Water-spent catalyst, propyl chloride, and tars
may be present in the separator waste effluents.
6. EPA Source Classification Code - None
7. Reference
Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4
(1972), p. 192, 270.
6-565
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 231
n-Propyl Amine (from n-propyl chloride)
2NH2
NH
CH.CH0CH0NH_ + CH.CH.CH-Cl —^ (CH,CHOCH_) 9NH + NH, Cl
3 i L L 3 / 2. j £. & *. n
m
^-- Function - n-Propyl amine is commercially produced by the reaction of
n-propyl chloride and ammonia. The reaction is carried out under
pressure at moderately high temperatures (160-170°C). Normally the
primary, secondary and tertiary amine derivatives are formed. The
primary amine yield may be maximized by operating at excess ammonia
concentrations. Yields of secondary and tertiary amines are increased
by recycling the primary amine.
2. Input Materials
n-Propyl chloride
Ammonia
3. Operating Parameters
Temperature: 160-170°C (320-338°F)
Pressure: 2.7 MPa (27 atm)
4- Utilities - Not given
5. Waste Streams - Waste effluents from the ammonia stripper may contain
quantities of ammonia, propyl chloride, and primary, secondary, and
tertiary propyl amines.
6-566
-------
6. EPA Source Classification Code - None
7. References
Astle, M.J., Industrial Organic Nitrogen Compounds, Reinhold Publishing
Corp., New York, N.Y., 1961 , p. 5.
6-567
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 232
Butyronitrile (from n-propyl chloride)
aq. CELCH CH2OH
NaCN - ~ - > CHCHCHCN + NaCl
1. Function - Butyronitrile is prepared by the reaction of n-propyl
chloride and sodium cyanide in aqueous n-propanol.
2. Input Materials
n-Propyl chloride
Sodium cyanide
n-Propyl alcohol
Water
3. Operating Parameters - Not given
4. Utilities - Not given
5. Waste Streams - Waste streams from the purification section probably
contain sodium chloride, propyl alcohol, propyl chloride, butyronitrile,
and sodium cyanide. Some air emissions of propyl chloride, propanol,
and hydrogen cyanide may also occur.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience
Publishers, New York, N.Y., Vol. supplement (1971), p. 598.
6-568
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 233
n-Butyric Acid (oxidation of n-butyraldehyde)
1/2
1. Function - Some butyric acid is prepared commercially by the oxi-
dation of n-butyraldehyde. In this process, air or oxygen is
passed into n-butyraldehyde in the presence of a catalyst such as
manganese butyrate or a cobalt salt.
Yields of about 90% are possible over a wide range of tempera-
tures.
2. Input Materials
n-Butyraldehyde - 0.91 kg/kg butyric acid
Air or oxygen
3. Operating Parameters
Temperature: 30-50°C (86-122°F)
Pressure: not given
Catalyst: 0.5% manganese butyrate
Cobalt salts
4. Utilities
Not given
5. Waste Streams - Although no information was available, some n-
butyraldehyde and butyric acid are probably present in the reactor
off-gas. Process slops may also be a source of these pollutants,
as well as reaction by-products.
6. EPA Source Classification Code - None
6-569
-------
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 3 (1964). p. 880.
Chemical Technology. Barnes and Noble Books, New York, N.Y.,
Vol. 4 (1972), p. 426.
Goldstein, R. F., The Petroleum Chemicals Industry, 2nd Edition,
John Wiley and Sons, New York, N.Y., 1958 , p. 331.
6-570
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 234
Carbon Tetrachloride and Perchloroethylene
(hydrocarbon chlorinolysis)
C» - C, Hydrocarbons + Cl™ > mixed chlorocarbons and
chlorohydrocarbons + HC1
1. Function - Large quantities of perchloroethylene, carbon tetra-
chloride, and other chlorohydrocarbons are co-produced by the
simultaneous chlorination and pyrolysis of paraffinic hydrocar-
bons. In commercial practice, this conversion is carried out by
reacting ethane, propane, LPG, or natural gas with an excess of
chlorine at 500 - 700°C.
Gaseous reaction products are quenched and most organics con-
densed. Any HC1 remaining in the condensed crude is neutralized
with dilute caustic, and the product is decanted from the aqueous
phase, dried, and distilled.
Light end organics such as carbon tetrachloride and trichloro-
ethylene are condensed and purified by further distillation. Per-
chloroethylene, hexachloroethane, and higher-boiling bottoms are
separated, and the saleable compounds are neutralized, dried, and
inhibited (if an olefinic linkage is present). Depending on econo-
mic factors, any of the various products may be recycled to the
reactor.
Generally, trichloroethylene production is favored by lower reaction
temperatures, i.e., 300-500°C.
6-571
-------
2. Input Materials
Ethane, propane, LPG, or natural gas
Chlorine
Sodium hydroxide
Polymerization inhibiters
Water
3. Operating Parameters
Temperature: 500-700°C (932-1292°F)
Pressure: not given
4. Utilities
Not given
5. Waste Streams - Generally, the same types of pollution would be
expected as in Process Nos. 235 and 236.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 2,""Chemical Engineering," February 18, 1974, p. 127.
Ibid, Part 7, June 24, 1974, p. 156.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 132, 199.
"1973 Petrochemical Handbook," "Hydrocarbon Processing," November
1973, p. 114.
6-572
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 235
Perchloroethylene (chlorinatidn of mixed hydrocarbons)
Hydrocarbons + Cl» - >• mixed chlorohydrocarbons
mixed chlorohydrocarbons - > CC1, + CC12=CC12 + HC1
2CC1. :sj=^. CC10=CC1_ + 2C10
4 22 2.
1. Function - Perchloroethylene is now produced from a mixture of hydro-
carbons. The usual starting materials are methane, ethane, ethylene,
LPG, propane, ethylene dichloride, or process wastes from vinyl
chloride manufacture, which are chlorinated to yield saturated chloro-
hydrocarbons. These are then pyrolyzed to yield mixtures of predomi-
nantly trichloroethylene, carbon tetrachloride, and perchloroethylene .
The desired product may be separated and the rest returned to the
reactor.
The formation of the mixed chlorohydrocarbons is carried out at
100-125°C and 5-10 atm; the pyrolysis is carried out at 400-700°C.
Perchloroethylene is also produced in a modified Deacon process
which uses HC1 and air:
CH2=CH2 + 4HC1 + 202 Cl.C - CC1, + 4H.O
With an excess of oxygen, the mixed product is typically 5-10%
dichloroethylene, 25-35% trichloroethylene, and 50-60% perchloro-
ethylene, which can be separated by fractionation. Fluid catalysts
are commonly used; chlorination, oxychlorination and dehydrochlori-
nation may proceed simultaneously in the same vessel.
6-573
-------
In the past, the dominant process started with acetylene and
chlorine:
HC=CH + C12 - >• CHC12CHC12 + CC13CHC12 + HC1
CHC12CHC12 + CC13CHC12 + Ca(OH>2 -
This process is no longer economical.
2. Input Materials (typical)
Basis - 1 metric ton perchloroethylene and 1,350 kg HC1
Propane, kg 200 (441 Ibs)
Chlorine, kg 2,500 (5,512 Ibs)
3. Operating Parameters
Step one:
Temperature, °C 100-125 (212-257°F)
Pressure, MPa 0.507-1.01 (5-10 atm)
Step two:
Temperature, °C 400-700 (752-1292°F)
4. Utilities
Not given
5. Waste Streams - Although no information was available, mixed chloro-
hydrocarbons and hydrogen chloride may be present in the waste gases
of various production steps. Heavy ends from distillation columns
are usually incinerated.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 7," "Chemical Engineering," June 24, 1974, p. 156.
6-574
-------
Hahn, A. V., The Petrochemical Industry - Market and Economics,
McGraw-Hill Book Co., New York, N.Y., 1970, p. 312,313.
Faith, W. L., et al., Industrial Chemicals. 3rd Edition,
John Wiley & Sons, New York, N.Y., 1965, p. 577,578.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 606.
6-575
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 236
Hexachloroethane (from perchloroethylene)
Cl Cl Fed,
**C=C + C19 =+ CC1-CC1.
cr vci z J
1. Function - In commercial practice, hexachloroethane is produced by
the chlorination of perchloroethylene at 100-140°C. This reaction
is carried out in a lead-lined vessel in the presence of ferric
chloride.
When 50-60% conversion to hexachloroethane is attained, the
reaction is halted. After treatment with alkali to neutralize
dissolved hydrogen chloride, the product solution is allowed to
crystallize. The crystals are removed by centrifuging, and unre-
acted perchloroethylene is recovered and recycled to the chlorinator.
2. Input Materials
Perchloroethylene
Chlorine
Sodium hydroxide
Water
3- Operating Parameters
Temperature: 100-140°C (212-284°F)
Pressure: not given
Catalyst: FeCl3
4. Utilities
Not given
6-576
-------
5. Waste Streams - Waste water from the purification section probably
contains sodium chloride, caustic, various chlorinated by-products,
and traces of perchloroethylene and hexachloroethane.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 200.
6-577
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 237
(L ^C- Nitroparaffins (from propane)
CH,CH0CH, + HNO, * C, - C, nitroparaff ins + oxygenated by-products
J £ J J J. J
1. Function - Propane is oxidized in the vapor phase with 65% nitric
acid. The nitration is carried out in a silica-clad stainless steel
reactor at 390-450°C and 0.8-1.2 MPa (8-12 atm). Approximately 40%
of the nitric acid is converted to nitroparaffins, the remainder acts
as an oxidizing agent, resulting in the oxygenated by-products, and
is reduced to nitric oxide (NO). This is reoxidized to nitrogen
dioxide which is utilized to produce additional nitroparaffins. The
combined yield of HNO_ to organic nitrates is 90%.
The temperature affects the reaction rate of reaction, the pro-
duct composition (high temperature favors 1-nitro compounds), and the
yield of oxidation products. High pressure increases rate but not
product composition. The yield of nitromethane and 2-nitropropane
may be increased at the expense of the other nitroalkanes by the use
of 0.03-0.2 moles of an oxygenated sulfur compound.
The nitroalkanes, aldehydes and ketonesare condensed leaving
unreacted propane and nitric oxide in the gas phase. Propane is
separated and recycled, the NO is oxidized with air to N02 which
is absorbed in water to produce HNO-. This nitric acid solution
is brought up to strength by the addition of concentrated HNO, and
returned to the process. The aldehydes and ketones are separated
from the nitroalkanes by solvent extraction with chlorinated aromatics.
The nitroalkanes are separated and purified by fractional distillation.
6-578
-------
2. Input Materials
Propane - 0.68 - 0.91 kg/kg product
Nitric acid - 0.98 - 1.30 kg/kg product
Water
Air
3. Operating Parameters
Temperature: 370-450°C (698-842°F)
Pressure: 0.8-1.2 MPa (8-12 atm)
4. Utilities
Not given
5. Waste Streams - Waste water from washing operations probably contains
a number of by-product aldehydes, ketones, acids, alcohols, and ole-
fins. These same pollutants plus carbon monoxide, NO , and propane
'X.
may be present in waste gases from separators and other purification
equipment.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967), p. 873-874.
Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4
(1972), p. 546-550.
6-579
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 238
n-Butenes (dehydration of n-butane)
CH,CH.CH,,CH, > n-C.HQ + H0
J Z £. J l\ O i
1. Function - In the Phillips process, n-butenes are produced by the
dehydrogenation of n-butane to serve as intermediates en route to
*
butadiene. The feed, preferably 98% n-butane, is dried carefully
over bauxite and charged to externally heated tubular reactors filled
with alumina-chromia catalyst. The dehydrogenation is carried out at
566-593°C and 108-239 kPa (1-20 psig) with 30% n-butane conversion
per pass and 80% selectivity to n-butenes. The process operates
cyclically, alternate reactors being used one hour for dehydrogenation
and one hour for catalyst regeneration.
Hydrogen, C.. - C~ hydrocarbons, and other conversion by-products
are separated from the reactor effluent by fractionation. The remaining
C, hydrocarbon mixture is separated by extractive distillation with
aqueous furfural or acetonitrile in two fifty-plate columns. Unreacted
n-butane is collected overhead, washed with water, and recycled. The
n-butenes remain in the solvent bottoms, from which they are separated
by subsequent distillation and washed with water. Recovery of n-butenes
as a 90-95% concentrate usually runs on the order of 80-90%.
*
n-Butenes produced by this process may also be used in the preparation
of other derivatives.
**
This is carried out at 791 kPa (100 psig) with an air-flue gas mixture
containing 2-3% oxygen.
6-580
-------
2. Input Materials
n-Butane (98%) - 1.44-1.62 kg/kg product
Furfural or acetonitrile
Water
3. Operating Parameters
Temperature: 566-593°C (1050-1099°F)
Pressure: 108-239 kPa (1-2.3 atm)
Catalyst: alumina-chromia
Space Velocity: 700
4. Utilities - Not given
5. Waste Streams - Furfural or acetonitrile and various C, hydrocarbons
are probably present in air and wastewater emissions from extractive
distillation and washing operations. Quench waters from the dehy-
drogenation section may also contain C/ hydrocarbons as well as residue
gas, tars, and oils.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience
Publishers, New York, N.Y., Vol. 3 (1964), p. 834.
Friedman, L., Womeldorph, D.E. and Stevenson, D. H., Proc. Am. Petrol.
Inst., Sec. Ill, 38, 202-218, 1958.
6-581
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO 239
Polybutenes
1. Function - Commercial polybutenes are viscous, tacky liquids with
molecular weights ranging from 300-3,000. They are produced by the
aluminum chloride-catalyzed polymerization of dried, desulfurized butane/
butylenes refinery streams obtained from catalytic or thermal cracking
operations. The isobutylene in the feed is polymerized to the greatest
extent, so the product is composed predominantly of polyisobutylenes with
indeterminate but minor quantities of poly(n-butenes) and insignificant
amounts of n- and isobutane.
The yield of polybutenes from this process is about 83%, based on
butylene feedstock. Unreacted butanes and the butylenes may be recycled
or returned to the refinery.
2. Input Materials
Butane/butylenes refinery stream butylenes -1.2 kg/kg product
3. Operating Parameters
Temperature - Not given
Pressure - Not given
Catalyst - A1C1
4- Utilities - Not given
5. Waste Streams - Air emissions from this process may contain quantities
of C, hydrocarbons, dimers, trimers, etc., and polymerization solvents,
i.e., alcohols, ethers, alkyl halides. Spent A1C1 catalyst and
reaction by-products may be present in solid or liquid process wastes.
However, no specific information was available.
6-582
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed. , Interscience
Publishers, New York, N.Y., Vol. 3 (1964), p. 946-55.
Ibid.. Vol. 14 (1967).
6-583
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 240
Butadiene (oxidative dehydrogenation of n-butenes)
n-^,ng CH2=€HCH=CH2
1. Function - Since 1971, the Phillips process has employed an oxidative
dehydrogenation in the production of butadiene from n-butenes. In
this process, a compressed air/steam mixture is heated, mixed with
n-butene, and passed over the oxidative dehydrogenation catalyst.
The C, components are recovered and the butadiene is extracted
and purified by the methods described in Process No. 59.
The significant attribute of this process is the savings in fuel:
oxidative dehydrogenation is an exothermic rather than an endothermic
process, and so requires significantly less energy than other dehydro-
genation processes.
2. Input Materials
n-Butenes - (90-95%)
Air - 10% of butylene feed
Water - (18 vols/vol butadiene)
Hydrogen - (acetylenics removal)
Furfural or acetonitrile
3. Operating Parameters
Temperature - 620-675°C (1148-1247°F)
Pressure - low partial pressures
Space velocity - 400 vols/hr per volume catalyst
Catalyst - Ca, Ni, PO.
6-584
-------
4. Utilities - Not given
5. Waste Streams - Waste flows from butadiene production facilities were
417 m /Gg (100 gal/ton) of product.
The principal pollutant sources should be the quench waters con-
taining tars, oils and soluble hydrocarbons and the solvent extract
and wash waters (if acetonitrile or furfural is used) containing
acetonitrile, furfural and C, hydrocarbons. Some air emissions of
furfural or acetonitrile may also occur.
PH: 8-9
TOG: 100-200 g/m3
Filtered COD: 250-375 g/m3
3
Suspended solids: 200-500 g/m
3
Total solids: 3-4 kg/m
6. EPA Source Classification Code - None
7. References
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, pp. 164-167.
Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Murray
Ltd., London, 1973, pp. 156-157.
6-585
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 241
Butadiene (Houdry process)
CH2=CH-CH=CH2
1. Function - In the Houdry process, 95+% n-butane is dehydrogenated
in one step to a mixture of butenes and butadiene. Fresh feed and
recycle C, hydrocarbons are preheated to 593°C and passed over an
activated alumina catalyst bed impregnated with 18-20% chromic oxide.
The reactors are brick-lined horizontal drums operating at pressures
of 13.8-20.7 kPa (0.14-0.2 atm) and a space velocity of about 2 (liquid
volume of feed per hour per volume of catalyst space).
Butadiene is separated from the reactor effluent by the methods
described in Process No. 59, and unreacted butane and butenes are
recycled. Depending on economic considerations, Houdry units can be
run to maximize production of butadiene or butenes. Maximum production
of butadiene corresponds to a yield of 57-63%.
2. Input Materials
n-Butane (95+%) - 1.7-1.9 kg/kg butadiene
Hydrogen (acetylenics removal)
Furfural or acetonitrile
3. Operating Parameters
Temperature - 593°C (1099°F)
Pressure - 13.8 - 20.7 kPa (0.14-.20 atm)
Catalyst - alumina with 18-20% chromic oxide
Space Velocity - 2 (see above)
6-586
-------
4. Utilities - Not given
5. Waste Streams - A typical waste water flow from a butadiene production
3
facility was 417 m /Gg (100 gal/ton) of product.
The principal sources of pollutants should be the quench waters
containing tars, oils, and soluble hydrocarbons and the solvent extract
and wash waters (if acetonitrile or furfural are used as extractants)
containing acetonitrile or furfural and C, hydrocarbons. Some air
emissions of furfural or acetonitrile may also occur.
TOC: 100-200 g/m3
Filtered COD: 250-375 g/m3
3
Suspended solids: 200-500 g/m
Total solids: 3-4 kg/m3
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 3 (1964), p. 800-
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 167-168.
6-587
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 242.
Amyl Chlorides (from pentane/isopentane)
C5H12 + C12 * C5HUC1 + HC1
-*-• Function - Mixtures of isomeric amyl chloride are produced by the
continuous vapor-phase chlorination of a n-pentane-isopentane re-
finery cut. In this process, the pentane feed is dried with hydrogen chloride
to prevent corrosion of the steel equipment, combined in excess with
chlorine gas, and passed through a heated pipe still. Conversion takes
place in the absence of light and catalysts.
The mixed vapors from the reactor are cooled rapidly and passed
through a series of four continuous fractionation columns. Hydrogen
chloride and most of the pentane are stripped in the first two columns.
Amyl chloride is taken overhead and polychloropentanes from the bottom
of the third column. Any residual pentane is removed from the amyl
chloride in the fourth column. With additional equipment, dichloropentane
may be isolated from the polychloropentane mixture as a saleable by-product.
2. Input Materials
Pentane/isopentane
Chlorine
3. Operating Parameters - Not given
4- Utilities - Not given
5. Waste Streams - Process leaks may result in the discharge of hydrogen
chloride, chlorine, pentanes, and various C chlorohydrocarbons to the
atmosphere. No specific information was available.
6-588
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience
Publishers, New York, N.Y., Vol. 2 (1963), p. 375.
6-589
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 243
Amyl Amines (from amyl chloride)
(C5H1;L)2NH + C5HnCl + NH3 > (C5H11)3N + NH4C1
1. Function - One commercial route to amyl amines involves the reaction
of ammonia and amyl chloride.
As in all reactions between ammonia and alkyl halides, quantities
of di- and tri- substituted amines are also formed.
2. Input Materials
Amyl chloride
Ammonia
3. Operating Parameters
Not given
4. Utilties
Not given
5. Waste Streams - Effluents from the ammonia stripper may contain
amyl chloride, ammonia, and various amyl amines. Ammonium chloride
and heavier organics are probably present in some waste stream
from the purification section, but no specific information was
available.
6. EPA Source Classification Code - None
6-590
-------
7. References
Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing
Co., New York, N. Y., 1956 , p. 245.
6-591
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 244
Amyl Alcohols (from amyl chlorides)
Oleic
CJH....C1 + NaOH .7" C,.HniOH + NaCl
5 11 acid 5 11
1. Function - Isomeric amyl alcohols are produced by the high-temperature
hydrolysis of mixed amyl chlorides. This continuous hydrolysis is
carried out with aqueous sodium hydroxide in the presence of sodium
oleate catalyst. In most process variations, the reaction slurry is
passed through two digesters. Amyl alcohols, pentylenes, chlorides,
and minor amounts of amyl ether distill overhead from the second
digester and brine is drawn from the bottom. The remaining slurry
is recycled to the first digester so that the initial charge of oleic
acid, which is converted to sodium oleate, does not need constant
replenishment.
Pentylenes and unreacted amyl chlorides are stripped from the
alcohol by steam distillation, and the chlorides are recycled. The
alcohol is fractionated into commercial compositions and sold along
with the pentylene and amyl ether by-products.
2. Input Materials
Amyl chlorides, mixed
Sodium hydroxide
Water
Oleic acid
3. Operating Parameters
Temperature: not given
Pressure: not given
Catalyst: oleic acid
6-592
-------
4. Utilities
Not given
5. Waste Streams - The principal pollutant source in this process is
probably the waste water from the brine decanter, containing sodium
chloride, sodium hydroxide, and traces of amyl alcohols, amyl chlorides,
pentylenes, and amyl ether. All of these organics may also be present
in the waste water from the amyl alcohol recovery column.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963) p. 375.
6-593
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 245
Amyl Mercaptans (from amyl chloride)
NaSH alc°hol> CHSH + NaCl
1. Function - A mixture of isomeric amyl mercaptans is produced by
the interaction of amyl chloride and sodium or potassium hydrosul-
fide in alcohol.
2. Input Materials
Amyl chloride
Sodium or potassium hydrosulf ide
Solvent alcohol
3. Operating Parameters
Not given
4. Utilities
Not given
5. Waste Streams - Indeterminate quantities of sodium or potassium
chloride, amyl chloride, amyl mercaptans, sodium or potassium
hydrosulf ide, the solvent alcohol, and reaction by-products such
as diamyl sulfide may be present in process wastes.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 20 (1969), p. 212-13.
Ibid., Vol. 2 (1963), p. 375.
6-594
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 246
Isoamylenes Cfrom C,. hydrocarbons)
1. Function - Isoamylenes (2-methyl-l-butene and 2-methyl-2-butene) are
extracted from a catalytically cracked C^ gasoline stream with 65%
aqueous sulfuric acid. This extraction is carried out in multiple
absorption stages at temperatures of 0-10°C.
The isoamyl alcohols formed dissolve in the aqueous phase and are
washed with caustic and water to remove residual acid. This aqueous
phase is separated and contacted with hexane or a similar solvent at 50°C
to reconvert the isoamyl alcohols to isoamylenes. After caustic and
water washings, hexane is stripped from the solution to recover the
isoamylene concentrate. Recovery from the C,. hydrocarbon feed is about
22.5%. However, this figure may be as low as 7.5%, depending on the
amylene concentration of the feed.
**
2. Input Materials
C_ hydrocarbons - 3.72 kg/kg isoprene
Sulfuric acid - 8.50 kg/Mg isoprene
Sodium hydroxide - 10.0 kg/Mg isoprene
Hexane - 31.5 kg/Mg isoprene
The GC hydrocarbons feedstocks usually contain about 30% isoamylene
by weight, but concentrations may be as low as 10%. About 75% of the
isoamylene in the feed is recovered.
The data given is based on isoprene production for which the isoamylene
serves as an intermediate.
6-595
-------
3. Operating Parameters
Temperature - extraction - 0-10°C (32-50°F)
Hexane treatment - 50°C (122°F)
Pressure - not given
4. Utilities - see Process Nos. 235 and 236.
**
5. Waste Streams
Amylene recovery section - separation vessel (water)
Sodium hydroxide - 3.05 kg/Mg isoprene
Sodium sulfate - 14.0 kg/Mg isoprene
Amylene recovery section - amylene recovery column (water)
n-Hexane - 19.0 kg/Mg isoprene
6. EPA Source Classification Code - None
7. References
"1973 Petrochemical Handbook," "Hydrocarbon Processing," November, 1973,
p. 101.
6-596
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 247
Isoprene (from isoamylenes)
?3 -
CH CH -C=Ci
f 3
CH-0=CH-C=CH0 + H,
CH3-CH=C-CH3
600°C
1. Function - One of the most popular routes to isoprene involves the
dehydrogenation of isoamylenes extracted from C,- gasoline (see Process
No. 246). in this process, the amylene feed and a C_ recycle stream
from a downstream purification unit are mixed with steam passed to a
catalytic reactor operating at 600°C and atmospheric pressure. A
mixture of iron oxide, K~CO_, and Cr-O, catalyzes the conversion to
isoprene with by-production of hydrogen, carbon dioxide, and a variety
of C» - C,. hydrocarbons.
The C, and C,. hydrocarbons are recovered from the reactor
effluent in an absorber-stripper section. The dry gas from the
absorber usually serves as fuel gas, typically containing: hydrogen,
methane, ethylene, ethane, propylene, propane, butylene, butane,
butadiene, isoprene, t-amylenes, piperylenes, other C 's and absorber
oil. Approximately 322 kg of fuel gas are produced per Mg of isoprene.
Upon leaving the stripper, the overhead product is processed for
light ends removal. The light ends (mainly C^'s) are fed to a debutanizer
which recovers the C, fraction overhead for use as fuel gas and a bottom
product for recycle to the reactor. The bottom product of the light ends
column is the crude isoprene, which is fed to a Shell Acetonitrile
process unit for purification.
6-597
-------
2. Input Materials
Isoamylenes - see Process No. 246.
3. Operating Parameters
Temperature - 600°C (1112°F)
Pressure - 100 kPa (1 atm)
Catalyst - Iron oxide, K2CO~, Cr-O™ mixture
**' Utilities - basis: 1.15 kg/sec capacity (80 M Ib/yr)
o _
Cooling water - 1.05 m /sec (1.0 M gph)
3
Process water - 16.0 dm /sec (15,200 gph)
Steam - 6.36 kg/sec (50,500 Ib/hr)
Electrical power - 9.72 EJ (2.7 MW)
Fuel - 2.16 m3/sec (275,000 cfh)
5. Waste Streams
Dehydrogenation section - partial condensers (water)
Isoprene - 0.5 kg/Mg product
Amylenes - 1.5 kg/Mg product
Isoprene recovery section - extractive distillation column (air)
Acetonitrile - 5.0 kg/Mg product
6. EPA Source Classification Code - None
7. References
"1973 Petrochemical Handbook Issue," Hydrocarbon Processing, Nov. 1973, p. 140.
Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975.
*
Includes utilities for isoamylene extraction—Process No. 247.
6-598
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 248
Isoprene (direct dehydrogenation of isopentane)
CH3
CH,CH2CH-CH3 Catal7st > CH2=CHC=CH2
CH3
1* Function - A promising, new route to isoprene involves a single-
step, fixed-bed dehydrogenation of isopentane or a C,. fraction
obtained by catalytic cracking. In this process, fresh C- feed-
stock is combined with recycle from the isoprene recovery section
and heated to 540-620°C. The dehydrogenation takes place over a
chromia-alumina catalyst in a cyclic series of three reactors
operating at 74-81 kPa (0.7-0.8 atm) partial vacuum.
The product stream is quenched by direct contact with a quench
oil stream and compressed before passing into the recovery section.
In the recovery section, a conventional absorber, stripper, and
debutanizer system recovers the C,. compounds which are then charged
to the isoprene purification section. The purification section
(Shell acetonitrile process) gives isoprene product (99% + pure),
1,3-pentadiene, and recycled isopentane-pentylenes.
This process had been used for the manfacture of isoprene
only on a pilot plant scale. Yields of 51.5% based on
isopentane and 58.6% based on a C_ gasoline fraction have been re-
ported.
2. Input Materials
C,. hydrocarbons
Isopentane - 2.06 kg/kg isoprene
CL gasoline fraction -1.76 kg/kg isoprene
6-599
-------
3. Operating Parameters
Temperature: 540-620°C (1004-1148°F)
Pressure: 74-81 kPa (0.72-0.81 atm)
Catalyst: chromia-alumina
Space velocity: 1.5-3.5 hr
4. Utilities
Not given
5. Waste Streams - Generally, the same types of pollution would be
expected as in Process No. 247-
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 12 (1967), p. 75.
6-600
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 249
Aid,
+ CC1,
Benzophenone
H20
1- Function - Benzophenone is manufactured principally by the Friedel-
Crafts reaction of benzene and carbon tetrachloride. Carbon tetra-
chloride and anhydrous aluminum chloride are charged to a jacketed
agitated, iron vessel and thiophene-free benzene is fed in over a
period of three to five hours with cooling. The hydrogen chloride
evolved is removed by an absorption tower that is coupled with a
settling tank where carbon tetrachloride is recovered.
The temperature of the mixture is allowed to rise to 35°C
(95°F) for 0.5 hour after the benzene has been added. The viscous
mass is transferred to a still containing water, heated to boil
with a steam injector, and held at that temperature by the heat of
reaction. The vapors are fed to the absorption system mentioned
above.
The crude benzophenone is vacuum distilled and crystallized
from a solvent.
2. Input Materials - Basis: 113.4 kg (250 Ib) batch
Benzene - 115.7 kg (255 Ib)
Carbon tetrachloride - 476 kg (1,050 Ib)
Aluminum chloride - 104.3 kg (230 Ib)
Water (hydrolysis) - 378.5 dm3 (100 gal)
6-601
-------
3. Operating Parameters
Temperature: reaction - 20°C (68°F)
final reaction - 35°C (95°F)
Equipment: jacketed, iron reactor
4. Utilities - Not given
5. Waste Streams
Water: Waste streams may contain some acid, small amounts of car-
bon tetrachloride, some aromatic residues, aluminum chloride hydrol-
ysis products.
Solids: Aluminum hydroxide by hydrolysis of aluminum chloride-
aromatic complexes, tars from still bottoms, and still bottoms from
recovery of recrystallizing solvent.
Air: Possible hydrogen chloride vapors.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 3 (1964), p. 439-
444.
6-602
-------
SECTION VIII
PROPYLENE
6-603
-------
PROPYLENE
PROPVLENE
ON
ON
O
251A
252
alcohol
253
»Glycerol - )• Dlchlorohydrin
,254 255
^Glyceraldehyde
251B
-)Acetone-
256
_}B1sphenol A
)0iacetone alcohol
259
262
Isophorone
263A
Ketene
263 B
Diketene
Hexylene glycol
oxide — — — ) Methyl isobutyl ketone — 2Q - ^Methyl Isobutyl carbinol
264
Nonene
, Dodecene
Isodecyl alcohol
^Heptanes 266 )lsooctyl alcohol ^^ ^ Propylene Section Chemical Tree
-------
PROPYLENE
267
-^ Isopropyl alcohol-
ogg 272
) Isopropyl chloride ^Isopropyl phenol
269,370
' Acetone
271
_lii_\ Isopropyl amine*
273
>Aceton1trile
i Acrylonitrile.
274
Aery1 amide
275
. Succinonitrile
^Acrylic acid——^ Butyl acrylate
278
• Isobutyraldehyde
279
Isobutanol
280
• Isobutyl acetate
281
-^Isobutyic acid
^n-Butyraldehyde
282
n-Butanol
> n-Butyric acid ) n-Butyric anhydride
284
, Butyl amines
—-—^Propylerte chlorohydrin ———>Propylene oxide—, —
i ) Propylene glycol
. Dipropylene glycol
288
-=22—^Polypropylene glycol
Epichlorohydrin
289 290 291
—> Allyl alcohol i ) 01chlorohydrin
292|
tGlycerol
293
-^Glycerol tri(polyoxypropylene) ether
Figure 15. Propylene Section Chemical Tree (Cont.)
6-605
-------
PROPYLENE
ON
ON
O
OS
1 ^ Acetone
36 294 .. 295
\Cumcnc '— ^Cumpnp hydroperoxide • - -
296
—^rt-Mpfrhvl itwnno .— — n\ Phenol
• — 21£i — ^ Propylene chlorohydrin
>Allyl chloride ) Dichlorohydrin - • • » Epichlorohydrin
317 318 J- 319'
\A11vl alrnhnl , ? \riurnrr.l
320
321
\ i 9 T Tri rhlnronrnnflnp
322
,_,„, ^Propylene dirhlorldp
323
^nifhlorop»-npenes
297
... ^26 Xylcnol
pop ?99
"D s Chlorophenols ^Chloranll
— 30D ) Aniline
301i ^ Sodium phenate 3°2A'B )Ani-olc
30-yi 303B
. .."T!: ..) Salicylic acid 9.
304 305
v ri«-irthpyarml \ r vcl ohexanone
307 308
30? .^Nitroanisolc- — ~- ) Anisidines
311
1 ) Nonyl phenol
11?
rf . ^\ Octyl phenol
1131
_,„ ,.\ Unrlnrvlnhrnnl
3141
Anhpnnl *ifi1 "fnnic acids
Figure 15. Propylene Section Chemical Tree (Cont.)
-------
CT\
O
Cooling water
Cooling water1
Steam'
Refrig
Epoxidation 25Z
& Hydration
/
2-Butanol H2i°2
51A
V
Cooling water
•TO ,.^|[
254
Hydroxylatlon
0
Isopr
t
•pc ID]
Hydrogen *
transfer j
Acetic acid
Steam I HCI
253
Substitution
HCI
Cooli
JH20
pH [Phenol
Alkylation
256
Steam Cooling water
i n
Aldol
condensation
257
Heat
Condensation 262
& Dehydration
Heat
263 A.B
Pyrolysis '
Figure 16. Propylene Section Process Flow Sheet
-------
O
oo
Cooli
nq water
it
C12
I J*
321 "
322 ^
Chlorinatlon
x-K
Cooling water
Steam f 1
"tllli
Isobutane
320
Epoxidatlon
^
Coolant
C,, Refinery gas Steaj" tl
1 Heat 1 1 1
I ~ t 1 It
Solvent
1 A1 Heat
HPO,
62 ^ 276 "^ 264
•Addition Oxidation Ol.lgomerization
x^"^""^ '
JL JL JL
Propylene"
[dlchloridel
Steam
CO H2
266
Oxo Process
Steam
1
»'
260
Hydrogenation
Benzene
Figure 16. Propylene Section Process Flow Sheet (Cont.)
-------
I
(^
o
Isopropyl
alcohol
Water
Steam 1
Cooling wate
Steam
Heatl
H2SO,, Refrlgl 1
267 ^
Hydration
•
NH3
IT
273
Ammox1dat1on
Heat
Cooling water
271
Amnonolysis
^
Heat
270^269
Oxidation
^
HC1
268
Substitution
Phenol
272
Frledel -Crafts
reaction
Aceto- \ / Acrylo-
nltrlle I I nltrile
Solvent
L
Addition
275
Sucdnonitrile
Figure 16. Propylene Section Process Flow Sheet (Cont.)
-------
I
I-1
o
Heat
1
Toluene
C|2 .P t
Heat
CO 1
323 ^ Z7S
Chlorlnation Oxo Process
Acetic anhydride
n-Butyr- 1 I Isobutyr-
aldehyde I \ aldehyde
Cooll
SI
ng water
T tl
Alcohol
A1r 1 «¥*
J _n * *
233
Oxidation
?
f3 H2 P Stef
f * /A *
Reductive Z84j
ami nation |
Heat
1 *\ o
282
Hydrogenation
Water
11
279
Hydrogenation
Cooling water
Air
\
Oxidation
281
HS04
Acetic
280
Esterlflcatlon
Figure 16. Propylene Section Process Flow Sheet (Cont.)
-------
ON
Cooling
water
1 285T2
c s>
286 "0
\
)
288
AHHi+inn
Steam
289
Isomerizatlon
Glycerol
Heat 1 (COM
Polyether 293
formation
N3
/>
A
,|
!
Poly-
propylene
glycol
Glycerol
:ri(polyoxy
prqpylene
ether
1
1
Hydroperoxide
Water 1 Na.CO,
J 1 \3J> x^\
292
Epoxidation
8 Hydrolysis
C12
290
Chlorlnatlon
** I \
f Glycerul 1
v_y
.0 ^~^\
_!Y, ,./D1chlor
-------
H,PO,
1 "4
IHeat
*
Benzene
I
36
Alkylatlon
Water 1
,.He,at n Heat
Ar I R i
1 294
i Hydroperox 1 datl on
Steam „
296
Dehydrogenatlon
g wa ter ^™
team A 1
ill,
H2S04
295
Cleavage
ro-Methyl-
l styrene J
Heat
Cooling water)
Steam 41 jMethanolp
Figure 16. Propylene Section Process Flow Sheet (Cont.)
-------
(^
I-"
U>
NaOH
Steam I
Water _
[ Heat P
+ t /A
3171
Substitution
Tt2
290
Addition
Salicylic
Acid &
Methyl sal icy!ate
Dodecene
Nonene
Octene
311,312,313
Alkylation'
Na?H Dimethyl
Steam I sulate
So
Went
1 Heat
Alkali
Dehydro- 291
chlorination
Figure 16. Propylene Section Process Flow Sheet (Cont.)
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 250
Acrolein
n
2.
CH0=CH-CH + H00
1. Function - Acrolein is produced by a limited vapor-phase oxidation
of propylene in the presence of a catalyst. Oxygenated by-products
complicate the product recovery and purification.
2. Input Materials
Propylene (98%) - 1.161 Mg/Mg (2,322 Ib/ton) product
3. Operating Parameters
Temperature - 290-380°C (550-720°F)
Pressure - 410-580 kPa (4.05-5.72 atm)
Flow rates - not given
Size of equipment - not given - fixed bed reactor
Types of catalysts - copper-oxide and bismuth-molybdenum
4. Utilities - Basis - 9.1 Gg/yr (20 M Ib/yr) capacity
o
Cooling water - 378 dm /s (6,000 gpm)
Steam - 4.1 Mg/hr (9,100 Ib/hr)
Power - 12.3 GJ (3,430 kWh)
Fuel - 350 kW (1.2 M Btu/hr)
5. Waste Streams
Propylene recovery section - propylene absorber off-gas
Propylene - 71 kg/Mg (142 Ib/ton) product
Propane - 3.5 kg/Mg (7 Ib/ton) product
Carbon monoxide - 73.5 kg/Mg (147 Ib/ton) product
6-614
-------
6. EPA Source Classification Code - None
7. References
Muller, R. G., "Glycerine and Intermediates," Report No. 53,
Stanford Research Institute, Menlo Park, California, 1969.
U. S. Patent 2,451,485 and 2,846,842.
Hancock, E. G., Propylene and Its Industrial Derivatives, John Wiley
and Sons, New York, N.Y., 1973, p. 23.
Chemical Technology, Barnes and Noble Books, New York, N.Y.,
Vol. 4 (1972), p. 364-427.
6-615
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 251A.B
Allyl Alcohol; Acetone (from acrolein)
0 0
II II
CH2=CH-CH + R-CH2OH - >- CH2=CH2~CH2OH + R-CH
0 OH 0
II I II
-CH-R - >- CH=CH-CHOH + R--C-R
CH2=CH-CH
1. Function - Acrolein undergoes hydrogen transfer with either a primary
or secondary alcohol in the presence of a metal alkoxide catalyst to
form allyl alcohol and the aldehyde or ketone that corresponds to the
donor alcohol.
It is not possible for all manufacturers to use the optimum
alcohol donor. Alcohols used and the corresponding by-products
are: ethyl alcohol (acetaldehyde) , n-propyl alcohol
(propionaldehyde) , isopropyl alcohol (acetone) , and secondary (2-)
butanol (methyl ethyl ketone) . 2-Butanol is a typical example of
an alcohol which gives high allyl alcohol selectivity while producing
a valuable by-product.
2. Input Materials
Acrolein - 1.044 Mg/Mg (2,088 Ib/ton) product
2-butanol - 1.310 Mg/Mg (2,621 Ib/ton) product
3. Operating Parameters
Temperature - 20-80°C (68-176°F)
Pressure - 100 kPa (1 atm)
Flow rates - m. g.
Types of catalyst - aluminum alkoxides
6-616
-------
4. Utilities - Basis: 8.7 Gg/yr 0-9.2 M Ib/yr) capacity
3
Cooling water - 156 dm /s (2,473 gpm)
Steam - 14.06 Mg/hr C31,000 Ib/hr)
Power - 922 MJ (256 kWh)
Refrigeration - 29°C (-20°F) - 700 kW (2.4 M Btu/hr)
3
Nitrogen - 140 dm /hr (5 scfh)
5. Waste Streams -
Product recovery and purification - light ends column (water)
Acrolein - 1.25 kg/Mg (25 Ib/ton) product
Methyl ethyl ketone - 12.5 kg/Mg (25 Ib/ton) product - some 2-butanol
Product recovery and purification - heavy ends column (water)
Butanol - 7.5 kg/Mg (15 Ib/ton) product
Allyl alcohol - 5 kg/Mg (10 Ib/ton) product
Polymer - 53.5 kg/Mg (107 Ib/ton) product
Aluminum hydroxide - 82 kg/Mg (164 Ib/ton) product
Trace quantities of acrolein, hydroquinene, and methyl ethyl ketone,
and 2-butanol
6. EPA Source Classification Code - None
7. References
Muller, K. G., "Glycerine and Intermediates," Report No. 58, Stanford
Research Institute, Menlo Park, California, 1969-
Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Murray,
London, 1973, p. 131.
Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4,
(1972), pp. 287,388.
6-617
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 252
Glycerin (from allyl alcohol)
CH2=CHCH2OH
-CH-CH0OH + H00 > HOCH0CH-CH0OH
22 2j 2
OH
1. Function - Allyl alcohol is epoxidized with hydrogen peroxide to
form glycidal which is hydrated to glycerin. The overall process
may be considered a hydroxylation catalyzed by tungstic acid. The
epoxidation reaction occurs in a three-section reactor maintained
at 45°C for a period of 1.1 hours per section. The product glycidal
is purified, then hydrated in a tubular reactor, with a 10 minute
residence time, at 145°C.
2. Input Materials
Allyl alcohol - 746.5 kg/Mg (1,493 Ib/ton) product
Hydrogen peroxide - 447 kg/Mg (894 Ib/ton) product
Caustic soda - 9 kg/Mg (18 Ib/ton) product
3. Operating Parameters
Temperature: 45°C (3-section reactor), 145°C (tubular reactor)
Pressure: not given
Flow rates: not given
Size of Equipment: not given
Types of Catalysts: tungstic acid
6-618
-------
4. Utilities - Basis: 11.65 Gg/yr (25.7 M Ib/yr) capacity
q
Cooling water - 86.69 dm /s (1,374 gpm)
Steam - 1.1 MPa (10.8 atm) -20.487 Mg/hr (45,167 Ib/hr)
380 kPa (3.75 atm)-11.747 Mg/hr (25,898 Ib/hr)
Power - 510 MJ (141 kWh)
2
Makeup Water - 3.6 dm /s (57 gpm)
5. Waste Streams
Hydroxylation section - allyl alcohol recovery column - to flare
(air)
Allyl alcohol - 6 kg/Mg (12 Ib/ton) product
Butanol - 2 kg/Mg (4 Ib/ton) product
Acrolein - 20 kg/Mg (40 Ib/ton) product
Miscellaneous light impurities - 22 kg/Mg (44 Ib /ton) product
Glycerin recovery and purification - light ends column (water)
Allyl alcohol - 4 kg/Mg (8 Ib/ton) product
Glycerin - 3.5 kg/Mg (7 Ib/ton) product
Miscellaneous light impurities - 23.5 kg/Mg (47 Ib/ton) product
6. EPA Source Classification Code - None
7. References
Muller, K. G., "Glycerine and Intermediates," Report No. 58,
Stanford Research Institute, Menlo Park, California, 1969.
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, John
Wiley and Sons, New York, N.Y., 1975, p. 436.
Hancock, E. G., Propylene and Its Industrial Derivatives, John
Wiley and Sons, New York, N.Y., 1973, p. 24-25.
6-619
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 253
Dichlorohydrin (from glycerol)
HOCH2CHOHCH OH + 2HC1 * CIO^CHCICH^H
or
C1CH2CHOHCH2C1 + 2H20
1. Function - In the past, dichlorohydrin has been produced by the
interaction of crude glycerol and an excess of hydrogen chloride.
This reaction is normally carried out at 100-160°C in a 4% solution
of acetic acid.
The major by-products of this reaction are water, polyglyceride,
and a mixture of acetates. Polyglyceride formation may be inhibited
by lower reaction temperatures (~ 100°C), although this necessitates
HC1 recycling. Vacuum distillation is normally sufficient to reduce
acetate production.
2. Input Materials
Glycerol - 0.79 kg/kg dichlorohydrin
Hydrogen chloride - excess
Water
3. Operating Parameters
Temperature - 100-160°C (212-320°F)
Pressure - Not given
Catalyst - acetic acid - 16 g/kg dichlorohydrin
4. Utilities - Not given
6-620
-------
5. Waste Streams - Various waste streams may be present depending on
the purification procedures employed (different reaction temperatures
require different purification techniques). However, tars, acetic
acid, various acetates, dichlorohydrin, and other halides from the
surge-tank wastes are probably the principal pollutants.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 314.
6-621
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 254
Glyceraldehyde (from acrolein)
CH0=CHCHO + H,CL ug ' CH,-CHCHO + H_0
2 £ £ pno * / > 2.
Ncr
CH_-CH-CHO + H.O > HOCH0CHOHCHO
\2/ 2 2
V0^
1. Function - Synthetic glyceraldehyde is prepared by the hydroxylation
of acrolein via glycidaldehyde intermediate. If pH is maintained
at 8 during the reaction, acrolein and hydrogen peroxide combine to
form glycidaldehyde.
The intermediate is then hydrolyzed to give nearly quantitative
yields of glyceraldehyde.
In some cases, acrolein may be converted directly to glyceraldehyde
by treatment with hydrogen peroxide in the presence of OsO, catalyst.
2. Input Materials
Acrolein - 0.65 kg/kg glyceraldehyde
Hydrogen peroxide
Water
3. Operating Parameters
Temperature - Not given
Pressure - Not given
pH - 8
4- Utilities - Not given
5. Waste Streams - Wastewater from the separator may contain small quantities
of acrolein, hydrogen peroxide, glycidaldehyde, and glyceraldehyde.
6-622
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 261.
6-623
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 255
Glycerol (hydrbgenation of glyceraldehyde)
Ni °
HOCH CHOHCHO + H2 > HOCH2CHOHCH2OH
1. Function - One route to glycerol starts with propylene involving
intermediates of acrolein, glycidaldehyde, and glyceraldehyde. The
final intermediate, glyceraldehyde, is converted to glycerol by
hydrogenation in the presence of nickel catalyst.
2. Input Materials
Glyceraldehyde
Rydrogen
3. Operating Parameters
Temperature - 200°C (392°F)
Pressure - Not given
Catalyst - Nickel
4. Utilities - Not given
5. Waste Streams - Air vent streams would contain hydrogen gas. Purification
by vacuum distillation separates glyceraldehyde and glycerol. Vents
from purification system contain glycerol, waste water streams would
contain glycerol and some glyceraldehyde. Because of the low vapor
pressures of the reactants and products the process should be essentially
free of air pollution.
6. EEA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 261-262.
6-624
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 256
Bisphenol-A (from phenol & acetone)
2C,H,.OH + CH0COCH, >- C(C,H,OH)0 + H00
o _> j 3 ! o 4 Z £.
1. Function - 2,2-Bis(4-hydroxyphenyl)propane, also known as bis-
phenol-A, is produced by reacting phenol with acetone in the pre-
sence of acid catalyst.
A number of by-products are formed in conjunction with the
main reaction. The earlier processes eliminated these impurities
by batchwise crystallization, while the new process, the Hooker
process, employs a continuous distillation and extractive crystal-
lization under pressure to purify the product.
Phenol and acetone at a molar ratio of approximately 3 to 1
are mixed, saturated with hydrogen chloride gas, and sent to the
reaction vessel. Reaction conditions are about 40°C, close to
atmospheric pressure, with a mercaptan used as a catalyst. The
crude product is stripped of HC1 and water of reaction. The over-
head is decanted into an organic phase (consisting mainly of phenol
which is recycled) and an aqueous phase. The latter goes on to an
HC1 recovery unit, and water is sent to disposal.
Bottoms from the stripper are sent to a series of purification
distillation chambers, where excess phenol, isomers, and heavy ends
are removed from the system for either recycle or disposal. Distil-
late from the last chamber is sent to the extraction operation, which
produces a slurry of pure crystals. The filtrate from the centrifuge
6-625
-------
is partially recycled to the crystallizer, and the remainder is
concentrated in an evaporator to produce liquid bisphenol-A.
2. Input Materials
Phenol - 862.5 kg/Mg (1725 Ib/ton) product (excluding recycled excess)
Acetone - 265.9 kg/Mg (531.7 Ib/ton) product
3. Operating Parameters
Temperature: 40°C (104°F)
Pressure: Near atmospheric
Flow Rates: Not given
Catalysts: HC1, and mercaptan
4. Utilities
Water (process) - 250 kg/Mg (500 Ib/ton) product
(gross cooling) - 197 Mg/Mg (394,000 Ib/ton) product
5. Waste Streams - Aqueous waste streams are produced by the hydrogen
chloride recovery unit, the crystallizer, and the final evaporator.
Total water flow - 458.8 dm /Mg (133.6 gal/ton) product
COD - 17.1 kg/Mg (34.2 Ib/ton) product
TOC - 5.2 kg/Mg (10.3 Ib/ton) product
Phenol - 7.1 kg/Mg (14.2 Ib/ton) pressure
6. EPA Source Classification Code - None
7. References
Anon., "Development Document for Effluent Limitations Guidelines
and Standards of Performance: Organic Chemical Industry," Contract
No. 68-01-1509, prepared for Environmental Protection Agency, June
1973.
Sittig, M., "Pollution Control in the Organic Chemical Industry,"
Pollution Technology Review No. 9, Noyes Data Corporation, 1974,
p. 85-87.
6-626
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 257
Diacetone Alcohol (condensation of acetone)
2(CH3)2CO > (CH3)2COHCH2COCH3
1. Function - Diacetone alcohol is prepared by the aldol condensation
of acetone flowing over a solid alkali or alkaline earth catalyst in a
fixed-bed catalytic reactor. The reaction is normally carried out
near room temperature or below.
To secure good yields it is necessary to remove the diacetone
alcohol as fast as it is formed.
Once the product solution is out of contact with the catalyst,
the dimer has little tendency to revert to acetone and accumulates.
Acetone, being more volatile, is continually removed by distillation
and recycled. Acetone-free diacetone alcohol is obtained by fractional
distillation under vacuum.
2. Input Materials
Acetone
3. Operating Parameters
Temperature - 10-23°C (50-73°F)
Pressure - Not given
Catalyst - Ba(OH)_ or similar compounds
4. Utilities - Not given
5. Waste Streams - Some acetone and diacetone alcohol may be present in
air emissions from various processing equipment.
6-627
-------
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Chemicals - Part 7,"
"Chemical Engineering, June 24, 1974, p. 153.
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes. Technomic Publishing Co., 1975, p. 309.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 165-166,
Ibid., Vol. 12 (1967).
6-628
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 258
Hexylene Glycol
PAT
(CH3)2COHCH2COCH3 + H2 ^A1> > (CH3)2COHCH2CHOHCH3
1. Function - Hexylene glycol is commercially prepared by the hydrogenation
of diacetone alcohol.
In normal plant procedure, acetone is the raw material, undergoing
preliminary condensation to diacetone alcohol.
2. Input Materials^
Diacetone alcohol (from acetone - 1.2 kg/kg hexylene glycol)
Hydrogen
3. Operating Parameters - Not given
4. Utilities
Not given
5. Waste Streams - Air vent streams from the reactor contain hydrogen and
acetone. Off-gas streams from the purification process contain acetone
and some diacetone alcohol.
6. EPA Source Classification Code
None
7. References
Hancock, E. G., Propylene and Its Industrial Derivatives, John Wiley
and Sons, Inc., New York, 1973, p. 258.
6-629
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 259
Mesityl Oxide (dehydration of diacetone alcohol)
(CH3)2COHCH2COCH3 — * (CH3)2C=CHCOCH3 + H20
1. Function - Mesityl oxide is commercially produced by dehydrating
diacetone alcohol at 100°C in the presence of sulfuric acid.
2. Input Materials - Diacetone alcohol and H^SO,
3. Operating Parameters
Temperature - 100°C (212°F)
Pressure - Not given
4. Utilities - Not given
5. Waste Streams - Wastewater from the dehydration column may contain some
acetone and diacetone alcohol.
6. EPA Source Classification Code - None
7. References
Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 12 (1967) p. 136.
Waddams, A. L., Chemicals From Petroleum, 3rd Edition, John Murray
Publishers, Ltd., London, Eng., 1973, p. 126.
6-630
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 260
Methyl Isobutyl Ketone (hydrogenation of mesityl oxide)
(CH3)2C-CHCOCH3+ H2 »• (CH3> 2CHCH2COCH3
1. Function - Methyl isobutyl ketone is made commercially by the selective
catalytic hydrogenation of the olefinic linkage in mesityl oxide. The
reaction may be run in the vapor phase at 150-170°C and 100 kPa
(1 atm) or in the liquid phase at 60-130°C and 1-25 atm. Copper or
Raney nickel catalysts are used.
In normal plant procedure, acetone is the raw material undergoing
conversion to diacetone alcohol, mesityl oxide, and finally methyl
isobutyl ketone (see Process Nos. 257 and 259). Methyl isobutyl carbinol
is a by-product of this reaction.
2. Input Materials
Mesityl oxide
Hydrogen
3. Operating Parameters
Vapor Phase - Temperature: 150-170°C (302-338°F)
Pressure: 100 kPa (1 atm)
4. Utilities - Not given
5. Waste Streams - Air emissions from the purification section may contain
mesityl oxide, methyl isobutyl ketone, methyl isobutyl carbinol, and
other by-products.
6. EPA Source Classification Code - None
6-631
-------
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 7," "Chemical Engineering," June 24, 1974, p. 153.
Hedley, W- H., et al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975} p. 309.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 12 (1967), p. 134.
6-632
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 261
Methyl Isobutyl Carbinol (from methyl isobutyl ketone)
catalyst v
1. Function - Methyl isobutyl carbinol is produced on a commercial scale
by the hydrogenation of methyl isobutyl ketone.
It is also isolated and collected as a by-product of methyl
isobutyl ketone synthesis (see Process No. 260).
2. Input Materials
Methyl isobutyl ketone
Hydrogen
3. Operating Parameters
Temperature: 150-190°C (302-374°F)
Pressure: 345-689 kPa (3.4-6.8 atm)
4« Utilities - Not given
5. Waste Streams - Some air emissions may be present. The probable
pollutants are methyl isobutyl ketones, methyl isobutyl carbinol,
and reaction by-products.
6. EPA Source Classification Code - None
7. References
Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing
Co., New York, N.Y., 1956, p. 202, 228.
Hahn, A. V., The Petrochemical Industry, McGraw-Hill Book Co.,
New York, 1970, p. 367.
6-633
-------
7. References (continued)
Hancock, E. G., Propylene, John Wiley and Sons, New York, 1973,
p. 258-259.
6-634
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 262
Isophorone (vapor-phase condensation of acetone)
3(CH3)2CO
1. Function
Isophorone is prepared by the vapor phase condensation of three
molecules of acetone in the presence of an alkaline catalyst. A
*
liquid phase condensation may also be employed. In the vapor phase
process, acetone is passed over calcium oxide, hydroxide,or carbide
at 350°C and atmospheric pressure to give isophorone, water and by
products such as: diacetone alcohol and mesityl oxide. The iso-
phorone is purified by vacuum distillation.
2. Input Materials - Acetone
3. Operating Parameters
Vapor phase
Temperature: 350°C (662°F)
Pressure: 100 kPa (1 atm)
Catalyst: CaO, Ca(OH) or CaC_
Liquid phase
Temperature: 140-170°C (284-338°F)
Pressure: not given
4. Utilities - not given
6-635
-------
5. Waste Streams - Air emissions from purification operations may con-
tain unconverted acetone, mesityl oxide, diacetone alcohol, other
reaction by-products and isophorone.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963) p. 166.
Sherwood, P. W., "Petroleum Refiner," .33 (12), 144 (1954).
6-636
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 263A
Ketene (pyrolysis of acetone)
(CH3)2CO > CH2CO + CH4
1. Function - On a commercial scale, ketene is prepared by the straight
pyrolysis of acetone. In the noncatalytic process, acetone is heated
to 600°C where it cracks to ketene and methane. Ketene is a highly
reactive material, unstable in storage- It is manufactured only for
captive use in further synthetic operations. Ketene dimerizes spon-
taneously and is a commercial by-product of ketene synthesis.
2. Input Material - Acetone
3. Operating Parameters
Temperature - 650-670°C (1202-1238°F)
Pressure - not given
Contact time - 0.25-5 sec.
4. Utilities - Not given
5. Waste Streams - The off-gas from the reactor should contain large
quantities of methane, and smaller amounts of acetone and possibly
acetic acid (reaction of ketene and water) .
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 1," "Chemical Engineering," January 21, 1974, p. 129.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 12 (1967), p. 91.
6-637
-------
7. References (continued)
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 18.
6-638
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 263B
Diketene (dimerization of ketene)
2CH2CO CH2C CH2C(0) 0
1. Function - Diketene is a commercial by-product of ketene synthesis
from acetic acid (see Process No. 105) or acetone (see Process No.
263A). The dimerization occurs spontaneously.
For description of the other items see Process No. 263A.
6-639
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 264
Nonene and Dodecene (oligomerization of propylene)
HPO
3CH =CHCH« ' CqH,R
£^ ,j ,7 J-xJ
HPO
4CH0=CHCH, ——±-*- C, 9H,,
^ J J_.£. ^T-
1. Function - Nonene and dodecene are coproduced when a C^ refinery
stream (40-60% propylene/propane) is oligomerized in the presence
of a phosphoric acid catalyst at 200°C and 3.45-6.89 MPa.
In some cases, the oligomerization is done with the intention
of producing gasoline, from which cuts of nonene and dodecene
can be fractionated. In other cases, the tetramer and/or trimer are
the primary products desired and the oligomerization is carried out
in such a way as to maximize production of both or either of these.
For instance, if the demand for dodecene exceeds the quantity con-
tained in a once-through oligomerization product, some or all of
the dimer and trimer are recycled to increase or maximize production
of the tetramer.
The trimer and tetramer cuts that are fractionated from the
oligomerization product are not pure trimer and tetramer, but are
mixtures of olefins that consist principally of polypropylene having
average molecular weights corresponding to those of nonene and dode-
cene.
2. Input Materials
*
Propylene (component of C- Refinery Gas)
*
The figures presented represent maximized production of nonene and
dodecene.
6-640
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2. Input Materials (continued)
For nonene - 1.21 kg/kg
For dodecene - 1.27 kg/kg
3. Operating Parameters
Temperature: 200°C (392°F)
Pressure: 3.45-6.89 MPa (34-68 atm.)
Catalyst: H^PO,
*• Utilities - Not given
5. Waste Streams - Since all of the co-products of nonene and dodecene
manufacture are utilized, there are no process wastes to be dealt
with, except spent phosphoric acid catalyst. However, propylene,
nonene, dodecene, and other olefins may be leaked to the atmosphere
by various processing equipment.
6. EPA Source Classification Code - None
7. References
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975, p. 335.
6-641
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 265
Isodecyl Alcohol (oxo process)
CO
1. Function - Isodecyl alcohol, actually a mixture of trimethyl
heptanols, is prepared from nonene by the oxo process. In this pro-
cess, a mixed stream of nonylenes is combined with synthesis gas at
160°C and 1.38 MPa (137 atm) in the presence of cobalt naphthenate
catalyst to produce a mixture of C1f. aldehydes.
The intermediate aldehydes are then hydrogenated to isodecyl
alcohol at 150°C and 10.0 MPa (100 atm) over a nickel or copper
chromite catalyst:
Purification is carried out in the manner described in Process
Nos. 278 and 282. Yields in the neighborhood of 64% are obtained.
2. Input Materials
Nonene - 1.25 kg/kg product
Synthesis gas
Hydrogen
3. Operating Parameters
Aldehyde Production
Temperature: 160°C (320°F)
Pressure: 13.8 MPa (137 atm)
Catalyst: Cobalt naphthenate
6-642
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3. Operating Parameters (continued)
Hydrogenation
Temperature: 150°C (302°F)
Pressure: 10.0 MPa (100 atm)
Catalyst: Ni or Cu chromite
4. Utilities - Not given
5. Waste Streams - Generally, the same types of pollution would be
expected as in Process Nos. 187 and 188.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 3," "Chemical Engineering," March 18, 1974, p. 92.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 14 (1967), p. 373-89.
6-643
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 266
Isooctyl Alcohol (from heptane)
CO
1. Function - Isooctyl alcohol, actually a mixture of isomeric Cft
alcohols, is manufactured by the oxo process. Heptene and synthesis
gas are reacted at 150°C and 20.7 MPa (3000 psi) in the presence of
a cobalt carbonyl catalyst, to yield a mixture of intermediate
octaldehydes.
After separation, the octaldehydes are hydrogenated to isooctyl
alcohol at 150°C and 10.0 MPa (100 atm) over a nickel chromate catalyst.
The intermediate aldehyde and the crude alcohol product are puri-
fied by the methods described in Process Nos. 278 and 282. This pro-
cess gives a 57% yield based on heptene.
2. Input Materials
Heptene - 1.33 kg/kg product
Synthesis gas
Hydrogen
3. Operating Parameters
Temperature: 150°C (302°F)
Pressure: octaldehyde production - 20.7 MPa
hydrogenation - 10.0 MPa
Catalyst: octaldehyde production - cobalt carbonyl
hydrogenation - nickel chromate
6-644
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4. Utilities - Not given
5. Waste Streams - Generally, the same types of pollution would be
expected as in Process Nos. 187 and 188.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 14 (1967). p. 373-89.
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 6," "Chemical Engineering," May 27, 1974, p. 106.
6-645
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 267
2-Propanol (Isopropyl Alcohol; Indirect Hydration Process)
CH3CH=CH2 + (CH3)2CHOS03H
S02 + CH3CHOHCH3 - >
1. Function - The basic reactions of the indirect hydration process
for the production of isopropyl alcohol are described in the above
formulae.
Crude propylene is scrubbed to remove mercaptans and hydrogen
sulfide, distilled to remove higher hydrocarbons and hydrogenated
to remove the acetylenics.
The liquefied propylene feed stock is combined with recycled
propylene and passed into a sulfuric acid absorption column. Most
of the propylene is absorbed. The spent gas containing propylene
and propane is scrubbed with caustic and sent to liquefied petrol-
eum gas (LPG) .
The extract is sent to the hydrolyzer-stripper where it is
diluted with water to obtain the sulfate esters. The ester solu-
tion is then stripped with steam to remove the 2-propanol and di-
isopropyl ether. The alcohol and ether vapors are scrubbed with
caustic solution to remove acidic compounds and entrained acid.
The alcohol and ether are separated by distillation, the ether
being taken overhead as a water-ether azeotrope. The alcohol-water
mixture is distilled and the distillate sent to a dehydrating
column where the remaining water is removed azeotropically. The
6-646
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ternary azeotrope is condensed and sent to a decanter where two layers
are formed. The upper layer consists of alcohol and azeotropic components,
the lower layer is water.
2. Input Materials
Refinery propylene stream (>50% propylene)
Sulfuric acid (70-80 wt %)
Caustic soda
Azeotropic agent (benzene, isopropyl ether or ethyl ether)
3. Operating Parameters
Absorber (reactor) temperature: 60-90°C (140-190°F)
Absorber (reactor) pressure: 791 kPa-28.6 MPa (7.8-28.3 atm)
4. Utilities - Not given
5. Waste Streams
Air: possible compressor seal leaks, recycle gas line leaks,
spent gas vent on reactor would result in propylene emissions.
Water: Waste water from dehydration column and crude storage may
contain small amounts of isopropyl ether, hydrocarbons, and
propanoic acid. Spent caustic soda solution contains caustic soda,
sodium sulfate, and 2-propanol. Waste water from the decanter may
contain isopropanol and azeotropic components.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 16 (1967), p. 568-
570.
Kent, J. A., Riegel's Handbook of Industrial Chemistry, Ed., 7th
Edition, Van Nostrand Reinhold Company, New York, N. Y., 1974, p.
794.
6-647
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 268
Isopropyl Chloride (from isopropyl alcohol)
(CH3) 2CHOH 4- HC1 *• (CKj 2CHC1 + H20
1. Function - Isopropyl chloride is readily formed by the reaction
of isopropyl alcohol and hydrochloric acid.
2. Input Materials
Isopropyl alcohol
Hydrochloric acid
3. Operating Parameters - Not given
4. Utilities - Not given
5. Waste Streams - Air and water effluents from the separator may contain
isopropanol, isopropyl chloride, and hydrogen chloride.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 16 (1968), p. 567.
6-648
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 269
Acetone (oxidation of isopropanol)
(CH3)2CHOH + 1/2 02 - >• (CH3)2CO + H20
1. Function - A significant amount of acetone is produced by the
catalytic oxidation of isopropyl alcohol. In this process, iso-
propanol is mixed with air and fed to a reactor maintained at 500 °C
and 345 kPa (50 psi) . Copper or silver catalysts are used.
Reactor products are treated similarly to those from the straight
dehydrogenation process .
If run in the liquid phase, this process yields hydrogen peroxide
as a by-product.
(CH3)2CHOH + 02 - >
2. Input Materials
Isopropanol - 1.15 kg/kg product
Air
3. Operating Parameters
Temperature: 500°C (932°F)
Pressure: 345 kPa (3.4 atm)
Catalyst: copper or silver
4. Utilities - Not given
5. Waste Streams
Isopropanol stripping still and intermediate flush column (water)
6-649
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5. Waste Streams (continued)
Water flow - 1.46 m3/Mg product (350 gal/ton)
COD - 1.1 kg/Mg product (2.2 Ib/ton)
BOD - 3.25 kg/Mg product (6.5 Ib/ton)
TOC - 0.35 kg/Mg product (0.7 Ib/ton)
The waste water contains acetone, isopropanol and traces of
heavier organics.
Vent on absorber (air) - acetone and isopropanol vapors.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 1," "Chemical Engineering," January 21, 1974, p. 130.
Hedley, W. H. et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 161.
6-650
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 270
Acetone (catalytic dehydrogenation of isopropanol)
(CH3)2CHOH > (CH3)2CO + HZ
•*•• Function - As of November 1974, 42% of the U. S. capacity for
acetone production was based on the dehydrogenation or oxidation
(see Process No. 269) of isopropyl alcohol. In the dehydrogenation
process, isopropanol is fed to a packed tubular reactor. The
reaction takes place at 380°C in the presence of brass or zinc oxide
catalyst, with a yield of 95%.
The hot reactor effluent contains acetone, unreacted isopropanol,
hydrogen, and minor amounts of by-products, such as propylene and
diiospropyl ether. The mixture is cooled and the noncondensable gases
are scrubbed with water. Because the resultant gas stream is mainly
hydrogen, a part of it can be recycled to control catalyst fouling.
The liquids are fractionally distilled taking reconcentrated acetone
overhead and a mixture of isopropanol and water as bottoms. In a
second fractionating column, the aqueous isopropyl alcohol is concen-
trated for 'recycle to the reactor. The water removed may be rejected
or reused in the gas scrubber.
2. Input Material - Isopropanol - 1.25 kg/kg acetone
3. Operating Parameters
Temperature - 380°C (716°F)
Pressure - Not given
Catalyst - brass or ZnO
6-651
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4. Utilities - Basis: 2.16 kg/sec (150 M Ib/yr) capacity
3
Cooling water - 379 dm /sec (6000 gpm)
3
Makeup water - 6.3 dm /sec (100 gpm)
Power - 1080 MJ (300 kW)
Steam - 10.1 kg/sec (80,000 Ib/hr)
Natural gas - 8.8 MW (30 M Btu/hr)
5. Waste Streams
Isopropanol stripping still and intermediate flash column (water),
o
Water flow - 1.46 m /Mg product (350 gal/ton)
COD - 1.1 kg/Mg product (2.2 Ib/ton)
BOD - 3.25 kg/Mg product (6.5 Ib/ton)
TOG - 0.35 kg/Mg product (0.7 Ib/ton)
The wastewater contains acetone, isopropanol, and traces of heavier
organics.
Vent on absorber (air)
Acetone and isopropanol vapors
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals - Part 1,"
"Chemical Engineering," January 21, 1974, p. 129.
Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Interscience
Publishers, New York, N.Y., Vol. 1 (1963), p. 160.
6-652
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INDUSTRIAL ORGANIC CHEMI.CALS PROCESS NO. 271
Isopropyl Amine (.from isopropyl alcohol or acetone)
A1PO 1*2
CH3CHCH3 + NH3 -35Qof- CE
OH
NH0
Ni I 2
1. Fvinction - Isopropyl amine is made principally by two vapor phase
catalytic processes. The first involves the alkylation of ammonia by
isopropyl alcohol. This reaction is run at 350°C under a pressure
of 100-200 atmospheres using an aluminum phosphate catalyst. An
excess (3 to 5x) of ammonia is used in order to promote primary amine
formation. Secondary and tertiary amines are by-products and must be
separated. The amines appear to be in equilibrium and the secondary
and tertiary amines are therefore recycled.
Acetone, ammonia and hydrogen are combined at 140°C and 740 psi
over Raney nickel to give a 97% yield of isopropylamine. Secondary
and tertiary amines are also present as by-products of this reaction.
2. Input Materials
Isopropyl Alcohol
Ammonia
Acetone
Hydrogen
3. Operating Parameters
Ammonylsis
Temperature - 350°C (662°F)
Pressure - 10.1-20.3 MPa (100-200 atm)
6-653
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3. Operating Parameters (Continued)
Catalyst - Aluminum phosphate
Reductive Ammination
Temperature - 130-180°C (266-356°F)
Pressure - 0.507-10.1 MPa (5-100 atm)
Catalyst - Raney nickel
4. Utilities - not given
5. Waste Streams - Waste water streams from strippers may contain ammonia,
isopropyl alcohol, acetone, isopropyl amines and more highly substituted
amines. Air effluents may contain ammonia, acetone, isopropyl amine and
isopropyl alcohol.
6. EPA Source Classification Code - None
7. References
E. G. Hancock, Propylene and Its Industrial Derivatives, John Wiley
and Sons, New York, N.Y., 1973, p. 223-234.
A. L. Waddams, Chemicals from Petroleum, 3rd Edition, John Murray
Publishers, Ltd., London, 1973, p. 128.
6-654
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 272
Isopropyl Phenols (from isopropyl chloride and phenol)
(CH3)2CHC1
^ CH(CH3)2
*•• Function - Isopropyl phenols are produced by Friedel-Craf ts re-
action of phenol and isopropyl chloride in the presence of A1C1,,
BF3, or H2SO, catalyst.
Ortho- and para-isopropylphenol are the primary products,
although some polysubstitution does occur.
2. Input Materials
Phenol
Isopropyl chloride
3. Operating Parameters
Temperature: not given
Pressure: not given
Catalyst: A1CL,, BF™, or H-SO,
4. Utilities - Not given
5. Waste Streams - Waste water from the HC1 scrubber should contain
sodium chloride and caustic, phenol, isopropyl chloride, spent
catalyst, and isopropylphenol . The air effluent may contain HC1,
isopropyl chloride, and reaction by-products. Tars from the still
bottoms are probably incinerated.
6. EPA Source Classification Code - None
7. References
Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4
(1972), p. 129, 269.
6-655
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 273
Acrylonitrile/Acetonitrile (ammoxidation of propylene)
CH2=CHCH3 + NH3 + 02(air) »• CH2=CHCN + HCN + CH^N + H20 + C02
1. Function - The entire production of acrylonitrile in the United States
is obtained by the ammoxidation of propylene. In this vapor-phase process,
refinery propylene (90f%), fertilizer grade ammonia (99.5+%), and air are
combined in a fluidized bed reactor at 450°C and 200 kPa (2 atm). The
reaction is catalyzed by a Sohio developed product, Catalyst 41 (50-60%
bismuth phosphonohydrate on A1?0,J , which increases the yield of acryloni-
trile and decreases the production of acetonitrile and hydrogen cyanide.
Approximately 15 kg of acetonitrile and 75 kg of hydrogen cyanide are
produced per Mg of acrylonitrile.
The reactor effluent is scrubbed in a countercurrent absorber,
and excess ammonia is neutralized with sulfuric acid. The organic
materials are recovered from the absorber water by distillation.
Hydrogen cyanide, water, light ends, and high boiling impurities are
then removed from the crude acrylonitrile by fractionation at atmospheric
pressure. Acetonitrile and hydrogen cyanide are collected as saleable
by-products.
2. Input Materials - Basis - 1 metric ton acrylonitrile
Propylene - 1.0 kg/kg product 1175 kg (2,590 Ibs/ton)
Ammonia - 0.5 kg/kg product 475 kg (1,047 Ibs/ton)
Air - 10.0 kg/kg product 6090 m3 (2.15 x 105 ft/ton)
Sulfuric acid
Catalyst small
6-656
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3. Operating Parameters
Temperature: 450°C (842°F)
Pressure: 200 kPa (2 atm)
Reaction Time: 10-20 sec.
4. Utilities - Basis: 2.87 kg/sec capacity (200 M Ib/yr)
Cooling water - 1.89 m /sec (30,000 gpm)
Refrigeration - 907 Mg (1000 tons)
3
Process water - 315 cm /sec (5 gpm)
Electricity - 3.6 GJ (1000 kW)
Steam - 25.2 kg/sec (200,000 Ib/hr)
3
Inert gas, high pressure - 23.6 dm /sec (3000 scfh)
5. Waste Streams - Reaction section - absorber off-gases to flare (air)
Acrylonitrile - 5.0 kg/Mg product
Carbon monoxide - 200 kg/Mg product
Propane - 50.0 kg/Mg product
Propylene - 100 kg/Mg product
Acetonitrile - trace
Ammonia - trace
Purification section - off gas from drying column to flare (air)
Hydrogen cyanide - 1 kg/Mg product
Reaction section - neutralizer (water)
Wastewater contains ammonium sulfate
Purification section - stripper (water)
Wastewater may contain acetonitrile.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 1, "Chemical Engineering," January 21, 1974, p. 131.
"1973 Petrochemical Handbook," "Hydrocarbon Processing," November, 1975, p. 99.
Hedley, W. H., et. al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975.
6-657
-------
7. References (continued)
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals. 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 46,47.
6-658
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 274
Acrylamide (hydration of acrylonitrile)
CH2=CHCN
HO
1. Function - The hydratlon of acrylonitrile to acrylamide sulfate
followed by dilution accounts for most acrylamide production at
the present time. This reaction is carried out at 155-175° by
adding acrylonitrile to sulfuric acid at the concentration corre-
sponding to its mono hydrate. Dilution with water converts the
acrylamide sulfate intermediate to acrylamide and sulfuric acid.
To prevent hydrolysis to acrylic acid, free acid must be re-
moved from the crude product solution. This is most commonly
achieved by neutralization with ammonia or sodium hydroxide to
form water-insoluble sulfate salts. The salts are then removed
by filtration and the filtrate is concentrated and /or cooled to
recover crystals of acrylamide. The mother liquor is frequently
purged and recycled to serve as the medium for further neutrali-
zation.
The sulfuric acid may be directly separated from the crude
product mixture without neutralization. This is accomplished by
means of an ion exchange column which separates the product mixture
into successive fractions of sulfuric acid, acrylamide-acrylic
acid and acrylamide.
In July 1974, one U.S. company began producing acrylamide by
the direct hydrolysis of acrylonitrile over special catalysts.
A number of catalysts have been developed that allow the hydrolysis
6-659
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of acrylonitrile in aqueous solution to yield the acrylamide
directly, obviating the need for the separation procedure necessary
in the sulfuric acid hydrolysis. These catalysts consit for the
most part of activated metallic oxides and are regenerable. These
reactions are run at 100°C and it is necessary to include a water
soluble inhibitor to prevent polymerization of the acrylamide. In
one case where the catalyst was 40% Cu salt - 25.5% Cr the inhibitor
used was N-nitroso-N-phenyl hydroxyamine ammonium salt. For a 7%
aqueous solution of acrylonitrile 25 ppm was sufficient to inhibit
the polymerization.
2. Input Materials
Acrylonitrile - 0.95 kg/kg acrylamide
Concentrated sulfuric acid
Water
Ammonia or sodium hydroxide
3. Operating Parameters
Temperature - hydrolysis
reaction - 155-175°C (311-347°F)
neutralization 50°C (122°F)
catalytic - 90-105°C (194-221°F)
Pressure - not given
4. Utilities - not given
5. Waste Streams - The principal pollutants from this process should be
the impurities removed from the mother liquor following acrylamide
separation. Acrylic acid, acrylonitrile, ammonia or caustic soda,
inorganic sulfates, and traces of acrylamide may be present in this
waste stream.
6-660
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The principal pollutants from the catalytic process are the
impurities remaining in the mother liquor following the recrystal-
lization of acrylamide. Unreacted acrylonitrile, inhibitor and
some acrylamide are present. Catalyst is recovered by filtration
and except for fines does not present a problem.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 1., (1963), p. 278-280.
U.S. Patent 3,699,194 (1974).
U.S. Patent, 3,689,558 (Dow Chemical 1974).
6-661
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 275
Succinonitrile (from acrylonitrile)
CH =CHCN + HCN >- NCCH2CH2CN
1. Function - Succinonitrile, also known as ethylene cyanide, is
manufactured by reacting acrylonitrile with HCN in the presence
of a catalyst (~5 wgt % acrylonitrile) and an inert solvent (tert-
butyl alcohol). The acrylonitrile is added gradually to prevent
polymerization.
2. Input Materials
Acrylonitrile
Hydrogen Cyanide
Catalyst: (Triton B) (benzyltrimethylammonium hydroxide)
Solvent: tert-Butyl Alcohol
3. Operating Parameters
Temperature: 55-60° C (131-140°F)
Pressure: 101 kPa (1 atm)
Reaction time: 5 hrs.
4. Utilities - Not given
5. Waste Streams - Wastewater streams from the purification section
may contain alcohol and smaller quantities of acrylonitrile,
hydrogen cyanide, catalyst, and polymers of acrylonitrile.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 6 (1965), p. 641.
6-662
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 276
Acrylic Acid (oxidation of propylene)
CH =CHCH3 + 02 *• CH2=CHCHO + H20
CH2=CHCHO + 1/2 02 »• CH2=CHCOOH
1. Function - The fastest-growing route to acrylic acid involves a
one-or two-stage oxidation of propylene in the presence of a molybdenum
oxide catalyst.
In the two-step process, propylene, steam, and preheated air are
fed to the first reactor filled with oxidation catalyst. The tempera-
ture is maintained at 330 - 370°C by circulating heat transfer medium.
The crude acrolein product is fed directly to the second reactor where
it is converted to acrylic acid at 260 - 300°C. The reaction may be
run in a single reactor by raising the temperature to 350 - 400°C and
using a pressure of 98-196 kPa.
Regardless of the conversion technique, the reactor effluent is
introduced to an absorber where acrylic acid is scrubbed as an aqueous
solution. Acrylic acid in the solution is then extracted with a sol-
vent. After solvent separation and light ends removal, high purity
acrylic acid is obtained at the final rectifier. Some acetic acid
by-product may be recovered.
2. Input Materials
Propylene - 0.83 kg/kg acrylic acid
Air
Steam - see utilities
3. Operating Parameters
Temperature: one stage - 350 - 400°C (662-752°F)
two stage - first reactor - 330 - 370°C (626-698°F)
second reactor - 260 - 300°C (500-572°F)
6-663
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Pressure: 100 - 200 kPa (1-2 atm.)
Catalyst: MoCL
A ~
4. Utilities - Basis: 0.31 kg/sec capacity (21.6 M Ib/yr)
Steam - 3.11 kg/sec (24,700 Ib/hr)
Power - 0.97 GJ (270 kW)
Cooling water - 379.1 dm /sec (6,009 gpm)
3
Makeup water - 20.3 dm /sec (322 gpm)
Electricity - 3.9695 (1,100 kWh) metric ton
5. Waste Streams - Overhead of solvent recovery column (air)
Acetone - 0.35 kg/Mg product
Acrolein - 1.85 kg/Mg product
Ethyl acetate - 1.85 kg/Mg product
Off-gas from the C- recovery system (air)
Ethyl acetate - 36.8 kg/Mg product
Propylene - 6.25 kg/Mg product
Carbon monoxide - 502 kg/Mg product
Heavy ends from acrylic acid finishing system (water)
Acrylic acid - 4 kg/Mg product
Polymers - 20.6 kg/Mg product
Hydroquinone - 10.65 kg/Mg product
Bottom from ethyl acetate recovery system (water)
Acetic acid - 35.7 kg/Mg product
Acrylic acid - 5.9 kg/Mg product
Ethyl acetate - 27.25 kg/Mg product
*
Data is based on the one-step oxidation.
6-664
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6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals
ii
Part 1, Chemical Engineering, January 21, 1974, p. 130,313.
"1973 Petrochemical Handbook," Hydrocarbon Processing,
November, 1973, p. 96.
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
6-665
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 277
n-Butyl Acrylate (from acrylic acid)
CH2=CHCOOH + n-C4H9OH - KIH
*• Function - One competitive process for making n-butyl acrylate
involves the direct esterification of acrylic acid with n-butanol.
Sulfuric acid is normally used as the catalyst and benzene is
used as a water entrainer to assist in driving the reaction to
completion.
2. Input Materials
Acrylic acid
n-Butanol
Benzene
3. Operating Parameters
Temperature: not given
Pressure: not given
Catalyst: H^SO,
4. Utilities - not given
5. Waste Streams - Waste water streams, if present, may contain acrylic
acid, sulfuric acid, n-butanol, n-butyl acrylate, and benzene.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 2," "Chemical Engineering," February 18, 1974, p. 126, 127.
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y.,Vol. 1 (1963), p. 299.
6-666
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 278
n-Butyraldehyde (oxo process)
CH2=CHCH3 + CO 4- H2 - >• CH3CH2C
1. Function - In the oxo process, propylene is reacted with synthesis
gas in the liquid phase at 140-170°C and 20-30 MPa (200-300 atm) .
An aromatic liquid such as toluene is used as the solvent, and cobalt
carbonyl compounds catalyze the reaction. n-Butyraldehyde , isobutyral-
dehyde, and some butanol are produced. In modern plants the ratio of
n-butyraldehyde to isobutyraldehyde is 4:1. The cobalt catalyst is
separated from the crude oxo product and recycled to the reactor with-
out any loss.
The two aldehydes may be hydrogenated and the corresponding
alcohols separated by distillation, or the aldehydes may be separated
and hydrogenated individually.
The remainder of the product mixture, containing butanols, esters,
and heavy ends, is separated in a third column to yield small quantities
of butanol and a residue which is used as fuel.
2. Input Materials
Propylene - 0.75 kg/kg n-butyraldehyde
Synthesis gas (CO and H )
Toluene (or other solvents)
3. Operating Parameters
Temperature - 140-170°C (284-338°F)
Pressure - 20-30 MPa (197-296 atm)
Catalyst - Cobalt carbonyl compound
6-667
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4. Utilities
Not given
5. Waste Streams
Catalyst recovery section (air, water)
Air vents discharge carbon monoxide, propylene, and propane. Some
catalyst recovery systems have a wastewater stream.
Purification section (air)
Various light end by-products may be flared to the atmosphere.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 2", "Chemical Engineering," February 18, 1974, p. 126.
"1973 Petrochemical Handbook," "Hydrocarbon Processing," November
1973, p. 107.
Hedley, W. H., et. al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975.
6-668
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 279
Isobutanol (hydrogenation of isobutyraldehyde)
(CH3)2CHCHO + H2 *• (CH3)2CHCH2OH
1. Function - Isobutanol is produced by the catalytic hydrogenation of
isobutyraldehyde in a process similar to that used to make n-butanol
from n-butyraldehyde. The reaction is carried out at 10.0 MPa pres-
sure, and water is added to suppress ether formation.
Some n-butanol is also produced by this reaction due to aldehyde
isomerization. The isobutanol, n-butanol, and other by-products
are separated by the methods described in Process No. 282.
2. Input Materials
Isobutyraldehyde - 1.10 kg/kg product
Hydrogen
Water
3. Operating Parameters
Temperature: 130-250°C (266-482°F)
Pressure: 10.0 MPa (100 atm)
Catalyst: nickel, copper chromite, or molybdenum sulfide
*• Utilities - Not given
5. Waste Streams - The same general types of pollution would be ex-
pected as in Process No.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 6," "Chemical Engineering," May 27, 1974, p. 104.
6-669
-------
7. References (continued)
"1973 Petrochemical Handbook Issue," Hydrocarbon Processing,
November 1973, p. 107.
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes. Technomic Publishing Co., 1975.
Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Murray,
Ltd., London, England, 1973, p. 205.
6-670
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 280
Isobutyl Acetate (from isobutanol)
H SO,
CH3COOH
!• Function - Isobutyl acetate is formed by tlie esterification of acetic
acid with isobutyl alcohol in the presence of sulfuric acid. The
reaction is carried out at the reflux temperature of the ternary azeo-
trope of isobutyl alcohol, isobutyl acetate and water. The vapor
mixture distilling at this temperature is sent to a separator where
the water is separated into an aqueous and alcohol-ester fraction.
The alcohol-ester layer is distilled giving an alcohol-ester azeotrope
and pure ester.
2. Input Material - basis 1 kg is'obutyl acetate
Isobutyl alcohol .9 kg/kg
Acetic acid .94 kg/kg
Sulfuric Acid 0.1%
3. Operating Parameters
Temperature: 85-89°C (185 - 192°F)
Pressure: 100 kPa (1 atm.)
Catalyst: Sulfuric acid
4. Utilities
Not available
5. Waste Streams - Isobutyl alcohol and isobutyl acetate will be emitted
from the reflux condenser. Waste water streams from the separator
contain acetic acid, dilute sulfuric acid, isobutyl alcohol and
isobutyl acetate. Air vent streams from the purification system
6-671
-------
(distillation) will contain isobutyl alcohol and isobutyl acetate.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 2,""Chemical Engineering," February 18, 1974, p. 126.
Faith, W. L., et al., Industrial Chemicals, 3rd Ed., John Wiley and
Sons, Inc., New York, 1965, p. 176-78.
6-672
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 281
Isobutyric Acid (oxidation of isobutyraldehyde)
(CH3)2CHCHO + 1/2 02 1- (CH3)2CHCOOH
-1-- Function - Isobutyric acid is prepared in 95% yield by the air
oxidation of isobutyraldehyde at 30-50°C.
The crude product is best purified by azeotropic distillation
with water followed by fractional distillation.
In some cases, ispbutyl alcohol may be the raw material for
this oxidation.
2. Input Materials
Isobutyraldehyde - 0.86 kg/kg product
Air
Water
3. Operating Parameters
Temperature: 30-50°C
Pressure: not given
4. Utilities - Not given
5. Waste Streams - Waste water from distillation procedures may contain
isobutyraldehyde, traces of isobutyric acid, and isobutanol, if used
as the raw material in the synthesis. Waste gases from the purifi-
cation section probably contain isobutyraldehyde and/or isobutanol.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 3 (1964), p. 880.
6-673
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 282
n-Butanol
1. Function - About half of the commercial n-butanol is produced by the
hydrogenation of n-butyraldehyde. In nearly all plant processes, the
butyraldehyde feedstock is prepared by the oxo-reaction of propylene,
so it contains isobutyraldehyde as well (see Process No. 278). In
modern processes the hydrogenation reaction tends to isomerize the
mixture to n-butanol.
A number of operating parameters have been reported for this
reaction. In most cases, the butyraldehyde feed is converted with
hydrogen over a fixed-bed catalyst such as nickel, copper chrom^te,
or molybdenum sulfide at 130-250°C and 3-20 MPa (30-200 atm) .
The crude n-butanol is purified by rectification in two columns.
In the first column, the low boiling impurities, isobutanol and water,
are separated as overhead. The higher-boiling impurities are removed
in the second column by continuous discharge of the bottoms, product,
and pure n-butanol is taken overhead.
2. Input Materials
n-Butyraldehyde (+ some isobutyraldehyde) - 1.09 kg/kg n-butanol
Hydrogen
6-674
-------
3. Operating Parameters
Temperature - 130-250°C
Pressure - 3-20 MPa (30-200 atm)
Catalyst - nickel, copper chromite, or molybdenum sulfide
4. Utilities - Not given
5. Waste Streams
Hydrogenation reactor (air)
Tail gas vent discharges hydrogen and some organic vapors
Distillation column (organic liquid)
Heavy ends are usually burned.
This process involves no waste water and minimal air pollution.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals - Part 2,"
"Chemical Engineering," February 18, 1974, p. 126.
"1973 Petrochemical Handbook Issue," "Hydrocarbon Processing,"
November 1973, p. 153.
Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975.
\
Waddams, A. L., Chemicals from Petroleum, 3rd Ed., John Murray, Ltd.,
London, England, 1973, pp. 204-206.
6-675
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 283
n-Butyric Anhydride
2C3H?COOH + (CH3CO)20
2CH2CO - KC
1. Function - Butyric anhydride may be prepared by an exchange between
butyric acid and acetic anhydride, or by the spontaneous reaction
of butyric acid and ketene.
Since ketene may be synthesized from acetic acid (see Process
No. 105), these reactions may be run in conjunction with each other.
This system would require an initial input of either acetic acid
or acetic anhydride.
2. Input Materials
Butyric acid
Acetic acid or acetic anhydride
3. Operating Parameters - Not given
4. Utilities - Not given
5. Waste Streams - Effluents from separation and purification operations
may contain acetic acid, acetic anhydride, unreacted butyric acid,
and butyric anhydride.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 3, (1964), p. 880.
6-676
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 284
n- Butyl. Amines (from n-butyraldehyde)
•"•• Function - The most common route to n-butylamine involves the hydro-
genation of n-butyraldehyde and alcoholic ammonia. The reaction is
carried out at 90-125°C and elevated pressure in the' presence of a
nickel catalyst.
The yield of n-butylamine is about 80% with smaller amounts of
di- and tri-n-butylamine by-products.
2. Input Materials
n-Butyraldehyde - 1.23 kg/kg n-butylamine
Ammonia
Hydrogen
Alcohol (solvent)
3. Operating Parameters
Temperature: 90-125 °C
Pressure: -500-1000 kPa (5-10 atm)
Catalyst: nickel
4- Utilities - Not given
5. Waste Streams - The separator effluent may contain quantities of
ammonia, n-butyraldehyde, alcoholic solvent, spent catalyst, various
butylamines , and by-product n-butanol.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 117, 124.
6-677
-------
7. References (continued)
Ibid., Vol. 3 (1964), p. 868.
Koddo, N., Chem. Eng.. 50(9), 149-68 (1952)
6-678
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 285
Propylene Chlorohydrin (from propylene)
C10 + H00 spfc HOC1 + HC1
L 2
HOC1
CH,CH-CH9OH +
Jf f.
Cl
10%
OH
90%
1. Function - The bulk of propylene chlorohydrin produced in this
country is made by the hydrochlorination of propylene. The method
involves passing chlorine, propylene and water into a rubber-lined
steel or acid-proof brick reactor at 35-50°C. The chlorine and
water react to form hypochlorous acid and hydrochloric acid in a
reversible reaction. The olefin is added to the hypochlorous acid
at a rate which is maintained to produce a chlorohydrin of 3-5%.
More concentrated solutions promote side reactions which yield
bis(chloroisopropyl) ether and propylene dichloride.
The vent gases from the chlorohydrin tower are passed through
a partial condenser to remove propylene dichloride and bis(chloro-
isopropyl) ether. The residual gas is scrubbed to remove HC1 and
in some cases recycled to the tower to recover any residual propy-
lene. The propylene dichloride is purified and sold.
2. Input Materials
Propylene
Chlorine
Water
6-679
-------
3. Operating Parameters
Temperature: 35-50°C (95-122°F)
Pressure: 110-130 kPa (1.14-1.27 atm)
4. Utilities - not available
5. Waste Streams - Waste water from scrubbing operations may contain
sodium chloride and caustic soda. Reaction by-products, such as
bis(chloroisopropyl) ether, may be present in air and waste water
emissions from other purification sources. A portion of the re-
cycled propylene may be vented to control the concentration of
inert gases in the propylene feed. These emissions may contain
ethylene, propylene, butane, hydrogen chloride and chlorine.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 8,""Chemical Engineering," July 22, 1974, p. 111.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 16 (1968) > p. 600-602.
Waddams, A. L., Chemicals from Petroleum, 3rd Ed., John Murray, Ltd.,
London, England, 1973, p. 137, 138.
6-680
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 286
Propylene Oxide (chlorohydrin process)
2CH3CHOHCH2C1 + Ca(OH)2 - >• 2CH3CH-CH2 + CaCl2
1. Function - As of July 1973, 70% of the U.S. capacity for propylene
oxide production was based on the chlorohydrin process. In normal
plant procedure, the propylene chlorohydrin feedstock is synthesized
as described in Process No, 285. This dilute chlorohydrin solution
is mixed with a 10% slurry of lime and pumped to a steam-heated flash
hydrolyzer for conversion to propylene oxide. The reaction is carried
out under ambient conditions.
The oxide is flashed out of the reaction zone as quickly as pos-
sible to prevent its further hydrolysis to propylene glycol. The
lime slurry is used in excess and this excess may be recovered for
recycle in thickeners which provide for the removal of the spent cal-
cium chloride brine by decantation. This effluent consists of 5%
aqueous CaCl? containing traces of lime and propylene glycol.
The overhead from the hydrolyzer is largely propylene oxide
and water. It is contaminated with propylene dichloride, chloro-
prenes from dehydrochlorination of propylene dichloride, and propional-
dehyde from isomerization of propylene oxide. This crude product is
purified by fractionation in multiple distillation columns.
2. Input Materials
Propylene chlorohydrin
(from propylene - 0.94 kg/kg propylene oxide)
10% Calcium hydroxide - 1.17 kg/kg product
6-681
-------
3. Operating Parameters
Temperature: 25°C (77°F)
Pressure: -atmospheric (100 kPa)
4. Utilities* - Basis - 0.72 kg/sec capacity (30 M Ib/yr)
Cooling water - 259 dm /sec (4100 gpm)
Nitrogen - 23.6 dm3/sec (3000 cfh)
Power - 648 MJ (180 kW)
Refrigeration - 1.109 Gg (1222 tons)
Steam - 7.31 kg/sec (58,000 Ib/hr)
*
5. Waste Streams
Purge gas from caustic absorber (air)
Ethane - 8.5 kg/Mg product
Butane - 8.5 kg/Mg product
Propylene - 8.5 kg/Mg product
Hydrogen chloride - 0.5 kg/Mg product
Chlorine - 0.5 g/Mg product
Off gas from tail gas absorber (air)
Propylene oxide - 4.1 kg/Mg product
Hydrogen chloride - 0.5 g/Mg product
Chloride - 0.5 g/Mg product
Water effluent
The major waste stream would probably contain calcium chloride and
traces of lime and propylene glycol.
6. EPA Source Classification Code - None
Includes Process No. 285
6-682
-------
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 8," "Chemical Engineering," July 22, 1974, p. 111.
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975, p. 147-148.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 16 (1968), p. 600.
6-683
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 287
Mono- and Dipropylene Glycols
CH0OCHCH, + ELO >• CH CHOHCIUOH
L | j / J f-
CH3CHOHCH2OH
1* Function - Propylene glycol is produced by hydration of propylene
oxide under pressure at temperatures up to 200°C. No catalysts are
used.
Some dipropylene glycol, tripropylene glycol, and minor quantities
of higher glycols are co-produced by the continued reaction of propy-
lene oxide.
The proportion of higher glycols is controlled by the molar
ratio of propylene oxide to water in the initial reaction mixture:
the greater the dilution, the greater the production of propylene
glycol and the higher the cost of recovering the pure products from
solution. Usually about 15 moles of water are used per mole of
propylene oxide in order to maximize propylene glycol production.
This yields about 13% by weight dipropylene glycol and 1.5% tri-
propylene glycol.
Although most dipropylene glycol is recovered as a by-product
of this process, some is produced by reacting propylene glycol with
propylene oxide.
2- Input Materials
Propylene oxide
For propylene glycol - 0.77 kg/kg
6-684
-------
2. Input Materials (continued)
For dlpropylene glycol - 0.95 kg/kg
Water - 3.7 kg/kg product
3. Operating Parameters
Temperature: ~200°C
Pressure: not given
4. Utilities - Not given
5. Waste Streams - The principal pollutant source in this process is
waste water flow from the dehydrator, containing quantities of
propylene oxide and propylene glycol.
6. EPA Source Classification Code - None
7. References
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 8," "Chemical Engineering," July 22, 1974, p. 110-111.
6-685
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 288
Polypropylene Glycol
CH3CHOHCH2OH + nCHOCHCH - > HO(CH0) H
1. Function - Polypropylene glycol is produced by the base-catalyzed
addition of propylene oxide to propylene glycol. The reaction
takes place around 150°C.
Commercial polypropylene glycols have molecular weights ranging
from 400 to 4000.
2. Input Materials
Propylene oxide
Propylene glycol
3. Operating Parameters
Temperature: 150°C
Pressure: Not given
Catalyst: KOH or other bases
4. Utilities - Not given
5. Waste '.Streams - The same types of pollution would be expected as in
Process No. 287. Spent catalyst may also be present.
6. EPA Source Classification Code - None
7. References
Austin, G. T-, "The Industrially Significant Organic Chemicals -
Part 8," "Chemical Engineering," July 22, 1974, p. 110.
6-686
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 289
Ally! Alcohol (isomerization of propylene oxide)
CH3CH-CH2 - ~> CH2=CHCH2OH
1. Function - Allyl alcohol is produced in 80-85% yield by the
catalytic isomerization of propylene oxide. This rearrangement is
carried out in the liquid phase in jacketed, stirred tank-type
reactors at 200-300°C and 1-25 atm. Both lithium phosphate and
lithium arsenate catalysts are used.
2. Input Material - Propylene oxide - 1.21 kg/kg allyl alcohol
3. Operating Parameters
Temperature: 200-300°C (392-572°F)
Pressure: 0.1-2.5 MPa (1-25 atm)
Catalyst: lithium phosphate or arsenate
4. Utilities - Basis - 284 g/sec capacity (19.8 M Ib/yr)
Steam - 1.16 kg/sec (9200 Ib/hr)
Power - 302.4 MJ (84 kW)
Fuel - 1159 MJ (1.1 M Btu/hr)
o
Nitrogen - 157 scm /sec (20 scfh)
5. Waste Streams
Isomerization section - product column (water)
Allyl alcohol - 13 kg/Mg product
plus traces of n-propyl alcohol, tars, and xylene
Catalyst tar removal section - auxiliary liquid column (water)
Terphenyls - 12.5 kg/Mg product
Lithium phosphate - 5 kg/Mg product
Tars - 25.5 kg/Mg product
6-687
-------
6. EPA Source Classification Code - None
7. References
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975, p. 151.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 624.
6-688
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 290
Dichlorohydr in
CH2=CHCH2OH + C12 *- ClCH2-CHCl-CH2OH (1)
CH2=CHCH2C1 + HOC1 >- HOCH2CHC1CH2C1 (2)
1. Function - Dichlorohydrin is an intermediate in the production of
glycerine. There are two principal processes used in the synthesis
of dichlorohydrin. The starting materials in both processes are
derived from propylene.
Allyl alcohol is chlorinated with chlorine gas to the dichloro-
hydrin. The product mixture contains 1,2-dichlorohydrin and 1,3-
dichlorohydrin which need not be separated if this is the intermediate
step in the synthesis of epichlorohydrin.
Allyl chloride is used as the starting material in a continuous
chlorohydrination process. Chlorine, water and allyl chloride are
fed to a stirred-reactor operating at 30-80°C and atmospheric pressure.
The allyl chloride is kept low to inhibit side reactions which form
1,2,3-trichloropropane and chloroethane. The reaction yields a mix-
ture of 1,2- and 1,3-dichlorohydrin in a 70-30 ratio.
The reactor effluent is lead to a separator where the aqueous
and organic phases are separated. The aqueous phase is recycled to
the reactor after additional chlorine is added. The organic phase
is converted to epichlorohydrin.
2. Input Materials
Allyl alcohol
Chlorine
6-689
-------
2. Input Materials (continued
Allyl chloride - 0.98 kg/kg epichlorohydrin
Chlorine/water - 0.90 kg/kg epichlorohydrin
3. Operating Parameters
Temperature: 30-80°C (86-176°F)
Pressure: 100 kPa (1 atm)
4. Utilities - Not given
5. Waste Streams - Vent gases from the reactor may contain allyl alcohol,
allyl chloride, chlorine, dichlorohydrin and reaction by products
such as propylene dichloride.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 316-317.
Hancock, E. G., Propylene and Its Industrial Derivatives, 'John
Wiley and Sons, New York, N.Y., 1973, p. 24.
6-690
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 291
Epichlorohydrin (from dichlorohydrin)
C1CH0CHC1CH«OH + 1/2 Ca(OH)0 - CH0-CHCH0C1 + 1/2 CaCl, -I- H00
i. L Z \Z i 2. t. /
C1CH,CHC1CH9OH + NaOH - CH0-CHCH0C1 + NaCl + H,0
i, Z ^Z i / i.
1. Function - Epichlorohydrin is commercially produced by the dehydro-
chlorination of dichlorohydrin. In this process, crude dichloro-
hydrin (see Process No . 290) is treated with a lime slurry or
caustic soda in a column-type reactor at 70-100°C and atmospheric
pressure. The solvent is trichloropropane .
The crude epichlorohydrin is removed from the reaction mixture
as a water azeotrope by steam stripping. Final purification is
accomplished by a two-column distillation train.
If the product is to be used in glycerol production, it need
not be purified.
2. Input Materials
Dichlorohydrin (crude mixture)
Calcium hydroxide - 1.01 kg/kg epichlorohydrin or
Sodium hydroxide - 1.09 kg/kg epichlorohydrin
3. Operating Parameters
Temperature: <60°C (<140°F)
Pressure - 101 kPa (1 atm)
A. Utilities
Not given
5. Waste Streams
Tail gas absorber vent (air)
6-691
-------
Chlorine - 0.5 g/Mg product
Hydrogen chloride - 0.5 g/Mg product
Allyl chloride - 2 kg/Mg product
Reactor vent (air)
Allyl chloride - 2 kg/Mg product
Epichlorohydrin - 1.5 kg/Mg product
Trichloropropane - 0.5 kg/Mg product
Chlorine - 0.5 g/Mg product
Hydrogen chloride - 0.5 kg/Mg product
The major water pollution problem would probably be a slurry
containing lime or caustic soda, calcium chloride or sodium chloride,
and small amounts of epichlorohydrin.
6. EPA Source Classification Code - None
7. References
Hedley, W. H., et al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
Sittig, M., Pollution Control in the Organic Chemical Industry,
Noyes Data Corp., Park Ridge, N.J., 1974, p. 131, 132.
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, p. 335, 336.
6-692
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 292
Glycerol (from peroxidation of allyl alcohol)
CH7=CHCH0OH + (CH,),C-OOH - >• CH0-CH-CH0OH -f (CH.)
*• £• j j ^z, if. j
0
Na2CO
CH-CH-CHOH + H0 — - —
22
\
Q OH
1. Function - This process has become competitive with the hydrochlorination
of allyl alcohol in the synthesis of glycerin. The trend has been away
from chlorination to peroxidation because in the former process the
chlorinated products are discarded, for lack of markets, while the
products of hydroperoxidation are all saleable.
Allyl alcohol is epoxidized by reaction with a hydroperoxide. The
hydroperoxide that is used is chosen carefully so that its degradation
product is saleable or useable in an allied process. The hydroperoxides
commonly used are t-butyl hydroperoxide (degradation product, t-butyl-
alcohol) and ethyl benzene hydroperoxide (degradation product, phenyl
methyl carbinol) . The glycidol produced is hydrolyzed to produce
glycerin. Although the reactants in this process are more expensive
than those in the chlorohydrin-glycerin process, their cost is recoverable
since all products are utilized.
2. Input Materials
Allyl alcohol - 0.67 kg/kg glycerol
t-Butyl hydroperoxide - 1.1 kg/kg glycerol
3. Operating Parameters
Temperature: 25-30°C (77-86°F)
Pressure: 1.6-3.6 KPa (16-35 atm)
6-693
-------
4. Utilities - Not given
5. Waste Streams - Air streams may contain allyl alcohol and degradation
products of the hydroperoxide (t-butyl alcohol, for example). Waste
water streams may contain allyl alcohol, glycidol, sodium carbonate and
t-butyl alcohol or methyl phenyl carbinol depending on the hydroperoxide
used.
6. EPA Source Classification Code - None
7. References
R. G. Muller, "Glycerin and Intermediates," Report No. 58, Stanford
Research Institute, Menlo Park, California, 1969.
"Hydrocarbon Processing," Nov. 1961, p. 249.
Hedley, W. H. et al., Potential Pollutants From Petrochemical Processes,
Prepared for EPA, Final Report MRC-DA-406, Contract 68-02-0226, Dec. 1973,
p. 149-150.
6-694
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 293
Glycerol Tri(polyoxypropylene) Ether (GTPE)
HOCH2CHCH2 + 3
OHOH (T
1. Function - Glycerol tri(polyoxypropylene) ether is formed by the
base-catalyzed reaction of glycerol and propylene oxide. The con-
version is normally carried out at 125°C and 446 kPa (4.4 Atm) .
Near the end of the reaction, some ethylene oxide is usually
added to impart certain desired properties characteristic of poly-
oxyethylene linkages.
GTPE is prepared in a variety of molecular, weights.
2. Input Materials
Glycerol
Propylene oxide
Ethylene oxide
3. Operating Parameters
Temperature: 125°C (257°F)
Pressure: 446 kPa (4.4 atm)
Catalyst: KOH
4. Utilities - Not given.
5. Waste Streams - Waste streams from purification operations are likely
to contain quantities of propylene oxide, spent catalyst, glycerol,
GTPE, and by-products such as propylene glycol.
6-695
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6. EPA Source Classification Code - None.
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals
Part 6", "Chemical Engineering", May 27, 1974, p. 103.
6-696
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INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 294
Cumene Hydroperoxide
0-OH
1. Function - The hydroperoxide ts made from cumene by an air oxidation
process. A mixture of cumene, water, sodium carbonate, sodium stearate
and a small amount of cumene hydroperoxide, which functions as an
oxidation initiator, is fed to a liquid phase oxidation vessel. The
oxidizing agent is air, and the reaction is carried out at 130°C and
274-446 kPa (2.70-4.40 atm) until 35-50% of the cumene is converted to the
hydroperoxide. The oxidation product is distilled so that most of the
unreacted cumene goes overhead, and the cumene hydroperoxide to bottom.
As of January 1, 1975, almost 91% of synthetic phenol capacity was
based on the acid-catalyzed cleavage of cumene hydroperoxide.
2- Input Materials
Cumene
Air
Sodium carbonate
Sodium stearate
Water
3. Operating Parameters
Temperature - 130°C (266°F)
Pressure - 274-446 kPa (2.70-4.40 atm)
4. Utilities - Not given
6-697
-------
5. Waste Streams - Waste water contains sodium carbonate, sodium stearate,
phenol and acetone. The air vents may emit cumene, acetone and traces
of mesityl oxide.
Plant 1 Plant 2
Flow 2.33 x 10~3 m3/kg (279-6 1.37 x 10~3m /kg (164 gal/
gal/1000 Ibs) 1000 Ibs)
COD 4,700 mg/1 84,304 mg/1
11.1 g/kg 11.4 g/kg
BOD,. 2,410 mg/1 17,575 mg/1
5
5.6 g/kg 24 g/kg
TOG 194 mg/1 77,406 mg/1
0.45 g/kg 105.6 g/kg
Lower values for plant 1 due to installation of dephenolizer facilities
(steam strippers).
6. EPA Source Classification Code - 3-01-034-01
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals - Part 1,"
"Chemical Engineering," January 21, 1974, p. 130.
Ibid., Part 8, July 22, 1974, p. 107,108.
"1973 Petrochemical Handbook," "Hydrocarbon Processing," November 1973,
p. 158.
"1975 Petrochemical Handbook," "Hydrocarbon Processing," November 1975,
p. 170.
Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,
Technomic Publishing Co., 1975.
Sittig, M., Pollution Control in the Organic Chemical Industry. Noyes
Data Corp., Park Ridge, N.J., 1974, p. 182,183.
6-698
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 295
Phenol (decomposition of cumene hydroperoxide)
0
OH + CH3CCH3
1. Function - Cumene hydroperoxide decomposes under the influence of
sulfuric acid to acetone and phenol. Approximately 88% of the phenol
produced in the United States in 1974 was made by this process. The
hydroperoxide is usually made from crude cumene and may contain benzene
and a-methyl styrene.
2. Input Materials
Cumene hydroperoxide
Sulfuric acid
3. Operating Parameters
Temperature - 70-80°C (158-176°F)
Pressure - 50-152 kPa (0.5-1.5 atm)
Catalyst - Sulfuric acid
4- Utilities - Not given
5. Waste Streams
Crude Phenol surge (water)
Cumene trace
Acetone - 4.5 x 10~ kg/kg phenol
Phenol - 7.5 x 10~ kg/kg phenol
Evaporator Residue
Acetophenone - .00175 kg/kg phenol
Phenol - 7.5 x 10~ kg/kg phenol
Polymeric matter - 0.11 kg/kg phenol
-4
Cumyl phenol - 8.5 x 10 kg/kg phenol
6-699
-------
6. EPA Source Classification Code - None
7. Reference
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N.Y., 1975, pp. 612-613.
Hedley, W. H., et al., "Potential Pollutants from Petrochemical Processes,"
for Control Systems Laboratory, NERC, Environmental Protection Agency,
Contract No. 68-02-0226, Task No. 9, pp. 121-122.
6-700
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 296
g-Methylstyrene (dehydrogenation of cumene)
A
> C6H5C(CH3)=CH2 + ^
1. Function - Most conmercial a-methylstyrene is produced by the
dehydrogenation of cumene. In a typical operation, a mixture
of three parts steam to one part cumene is passed rapidly over
an iron oxide catalyst at temperatures of 500-600 °C.
The crude dehydrogenation mixture contains cumene and a-
methylstyrene, as well as small amounts of benzene, toluene,
ethylbenzene, styrene, and tars. All of the usable components
are separated and purified through a series of fractional
distillations and recycled.
2. Input Materials
Cumene
Steam
3. Operating Parameters
Temperature: 550-600°C (1022-1112°F)
Pressure: not given
Catalyst: iron oxide
4. Utilities - Not given.
5. Waste Streams - Wastewater streams from the separators and super-
heater probably contain a variety of heavy-end aromatic hydro-
carbons, tars, and spent catalyst. Organic solids from still
bottoms are usually incinerated.
6. EPA Source Classification Code - None.
6-701
-------
7. References
Klrk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y-, Vol. 19, (1969) p. 81.
6-702
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 297
2,6-Xylenol (methylation of phenol)
1. Function - 2,6-Xylenol is a by-product of the methylation of phenol
to produce o-cresol. The xylenol isomer is present in approximately
25% of the yield. Phenol is reacted with methanol at about 300°C and a
pressure of 4.13 MPA (41 atm) over an alumina catalyst. Small amounts
of meta and para alkylated products are formed as well as some phenyl
ethers formed by oxidative coupling. The crude product is separated and
purified by crystallization.
2. Input Materials
Phenol
Methanol
Alumina
3. Operating Parameters
Temperature: 300°C (572°F)
Pressure: 4.13 MPA (41 atm)
Catalyst: Al_03
4. Utilities - Not given
5. Waste Streams - Air vent streams would contain methanol and small
quantities of phenol. Wastewater effluents from purification operations
probably contain small quantities of ethers and m- or p- substituted
cresols and xylenols. Unreacted methanol and phenol may also be present
in trace amounts.
6-703
-------
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 6 (1965) p.
Hahn, A. V.,The Petrochemical Industry, McGraw-Hill Book Co., New York
1970, p. 576-78.
6-704
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 298
CHLOROPHENOLS
(Chlorination of phenols)
OH OH OH
Cl
+ Cl,
(1)
Cl
or
+ HC1
(2)
Cl Cl
1. Function - The most widely used method for the preparation of mono-
chlorophenols is the direct chlorination of phenol in the absence of a
solvent. The product is a mixture of o- and p-chlorophenols with
preponderance of the para isomer. The reaction will proceed step-
wise to the di-, tri- and tetrachloro- products although the rate slows
with each additional atom of chlorine added to the phenol substrate.
The dichlorophenols can be produced by direct regulated action of
chlorine in a solvent such as glacial acetic acid or chloroform.
Chlorination in aqueous solution gives 2,4,6-trichlorophenol rapidly
and quantitatively.
Pentachlorophenol is produced by chlorinating the more highly
substituted chlorophenols in the presence of FeCl_ or A1C1- since the
rate of chlorination has decreased to the point that the uncatalyzed
reaction becomes prohibitably slow.
6-705
-------
The chlorophenols can be separated from unreacted phenol by
adding potassium carbonate which reacts with the chlorinated phenols
to form the water-soluble salts. Phenol is not basic enough to react
and can therefore be extracted from the water solution.
The chlorophenol isomers can be separated by fractional distillation.
Pentachlorophenol, 2,4-dichlorophenol, 2,3,4,6-tetrachlorophenol, 2,4,6-
trichlorophenol and p-chlorophenol are all soluble products. o-Chloro
and 2,6-dichlorophenol have no commercial use and are recycled for
further chlorination.
2. Input Materials
Phenol
Chlorine
Potassium carbonate
AtimiiTHim trichloride or ferric chloride
3. Operating Parameters
Temperature - 50-155°C (122-311°F)
Pressure - not given
Catalyst - for pentachlorination - A1C1 or *eCl_ (0.05-1.0%)
4. Utilities - Not given
5. Waste Streams - Waste water streams from washing operations and still
bottoms probably contain quantities of potassium chloride, HC1, phenol
chlorine and chlorophenols. Chlorine, HC1 and extraction solvents are
present in air emissions.
6. EPA Source Classification Code - None
6-706
-------
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1968) p. 300.
6-707
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 299
Chloranil (from 2,4,6-trichlorophenol)
C3T Nf NCI
0
1. Function - Chloranil or 2,3,5,6-tetrachloro-l,4-benzoquinone is
prepared by the action of chlorine and fuming sulfuric acid on
2,4,6-trichlorophenol.
2. Input Materials
2,4,6-Trichlorophenol
Chlorine
Sulfuric acid (fuming)
3. Operating Parameters - Not given.
4. Utilities - Not given.
5. Waste Streams - Effluents from purification operations may contain
2,4,6-trichlorophenol and other chlorophenols, chlorine, sulfuric
acid, chloranil and a variety of reaction by-products.
6. EPA Source Classification Code - None.
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 334.
6-708
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 3QQ
Aniline (ammonolysis of phenol)
1. Function - Currently, the most economical route to aniline is the
ammonolysis of phenol. In this process, ammonia and phenol are
preheated and fed to a fixed-bed catalytic reactor where the con-
version takes place over alumina. The reactor effluent is partially
condensed and unconverted ammonia is compressed and recycled. The
water of reaction is removed from the crude aniline stream by distil-
lation, at the same time unreacted phenol distills as an azeotrope
with water and is recycled. High purity aniline product is recovered
by distillation from heavies. This process offers less by-products
than other commercially used processes.
2. Input Materials
Phenol - 1.05 kg/kg product
Ammonia - 0.20 kg/kg product
3. Operating Parameters
Temperature: not given
Pressure: not given
Catalyst: alumina
4. Utilities
Not given
5. Waste Systems - Off-gases from the separator ,may contain hydrogen,
nitrogen, and some ammonia. Traces of aniline and phenol may be
present in the waste gas from the dryer. The rejected heavies from
6-709
-------
the final distillation could be present in waste water streams, but
are probably incinerated. Overall, waste disposal problems are
considered minimal.
6. EPA Source Classification Code - 3-01-034-01
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 1, "Chemical Engineering," January 21, 1974, p. 132.
"1973 Petrochemical Handbook Issue," "Hydrocarbon Processing,"
November 1973, p. 105.
"1975 Petrochemical Handbook", Hydrocarbon Processing," November
1975, p. 114.
6-710
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 301
Sodium Phenate
+ HaOB
1. Function - In the commercial production of sodium phenate, phenol
and a slightly greater than equimolar quantity of hot aqueous sodium
hydroxide (concentration about 50%) are mixed in thermocoil autoclaves.
The solution is heated to approximately 130°C and is evaporated to
dryness, first at atmospheric pressure and in later stages by the
application of a vacuum. This operation is sometimes carried out in
heated ball milla in order to yield a dry, powdered product.
2. Input Materials
Phenol
50% aqueous sodium hydioxide
3. Operating Parameters
Temperature - 130°C
Pressure - Not given
4. Utilities - Not given
5. Waste Streams - The principal source of air pollutions in this process
is the evaporation step when a mixture of water vapor and phenol is
emitted.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 17 (1968) p. 148.
6-711
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 3Q2A,B
ANISOLE
1. Function - Anisole is made by the Williamson reaction which is the
alkylation of a phenate salt. The most economical route to anisole
is described by equation (1) and involves the reaction of sodium
phenate and methyl chloride. An alternate method, utilized more in
the past, was based on the use of dimethylsulfate as the alkylating
agent (2).
In both methods, the sodium phenate is prepared in situ by combining
molten phenol and sodium hydroxide at 45-60°C. The alkylating agent
is added and the temperature is then increased to 100°C. The yield in
both processes approximates 95%.
2. Input Materials
Phenol (2) 0.92 kg/kg anisole
Sodium hydroxide
(1) methyl chloride
(2) dimethyl sulfate
3. Operating Parameters
Temperature - 45-100°C (113-212°F)
Pressure - not given
4. Utilities - not given
6-712
-------
5. Waste Streams - Waste streams from purification processes may contain
sodium chloride or sodium sulfate, depending on the process used,
sodium hydroxide, phenol, sodium phenate, anisole and methyl chloride
or dimethyl sulfate, depending on the process utilized. Methyl
chloride may also be present in the off-gases of various processing
equipment.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 15 (1968) p. 167.
6-713
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 303A.B
Salicylic Acid and Methyl Salicylate
C,HcONa + CO- - »• C,H. (OH) (COONa)
o 5 i o 4
CfiH4 (OH) (COONa) + HC1 - »- CgH^OH) (COOH) + NaCl
1. Function - In the preparation of salicylic acid, an excess of
carbon dioxide at 5 - 6 atm. pressure is charged to a thermocoil
autoclave containing dry, powdered sodium phenate (see Process
No. 301) . The conversion to sodium salicylate requires several
hours at 140 - 170°C. Any regenerated phenol is recovered by
vacuum distillation.
The crude product is then cooled, dissolved in water,
and filtered to remove impurities. Acidification of this sodium
salicylate solution with hydrochloric acid or sulfuric acid
results in the precipitation of salicylic acid.
Further purification of the technical product to yield USP
salicylic acid is achieved by sublimation. In order to eliminate
the risk of dust explosions, caused by frictional electricity during
this operation, a stream of inert gas (nitrogen with some carbon
dioxide) is circulated through the sublimation chamber. The products
obtained are USP salicylic acid and a slightly colored technical
grade sublimed acid. The yields of technical-grade and USP salicylic
acid from this entire process are 88% and 84%, respectively.
6-714
-------
Methyl salicylate is an Important commercial product in the
perfume and flavoring industries. Production in 1972 was in ex-
cess of 5,000,000 pounds. It is produced from salicylic acid,
which has been purified by sublimation, by esterification with
methyl alcohol in the presence of catalytic amounts of sulfuric
acid. The ester product is purified by vacuum distillation with
the water and unreacted methanol recycled to the system.
2. Input Materials
Sodium phenate (from phenol - 0.74 kg/kg salicylic acid)
Carbon dioxide
Water
Hydrochloric acid or sulfuric acid
Nitrogen
3. Operating Parameters
Temperature: carboxylation - 140 - 170°C (252 - 338 °F)
acidification - not given
Pressure: carboxylation - 500 - 600 kPa (5-6 atm)
acidification - not given
4. Utilities
Based on production of 4,000 pounds of salicylic acid/day
Steam - 0.158 kg/sec (1,250 Ib/hr)
Power - 3,600 MJ (1,000 kWh)
5. Waste Streams - The principal pollutant source in this process
should be the waste water stream from centrifuging operations.
The mother liquor is likely to contain sodium chloride or sulfate,
hydrochloric or sulfuric acid, various reaction by-products, and
traces of phenol and salicylic acid.
6-715
-------
The wash water stream contains salicylic acid, sulfuric acid
and methanol. The vent streams from the esterification and distil-
lation steps will contain some methanol.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 17, (1968),
p. 723-25.
"Phenol," in Chemical Economics Handbook, Stanford Research Institute,
Menlo Park, California.
Shreve, R. N., Chemical Process Industries, 3rd Edition, McGraw
Hill Book Company, New York, N. Y., 1956, p. 864.
Groggins, Unit Processes in Organic Synthesis, 5th Edition,
McGraw Hill Book Company, New York, N.Y., 1958, p. 367.
6-716
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 304
Cyclohexanol (hydrogenation of phenol)
C-H-OH + 3H0 >C,HinOH
O J 2. D 11
-*-• Function - Some cyclohexanol is produced by the catalytic hydro-
genation of phenol. The reaction takes place over active nickel
at 70-80°C and elevated pressure.
Cyclohexanone is a by-product of this reaction, and may be
removed by condensation with benzaldehyde in the presence of
alkali.
2. Input Materials
Phenol
Hydrogen
Benzaldehyde
Alkali
3. Operating Parameters
Temperature: 70-80°C (126-176°F)
Pressure: not given
Catalyst: activated nickel
4. Utilities - Not given
5. Waste Streams
Some phenol, cyclohexanol, and cyclohexanone
may be present in air emissions from purification processes.
Wastewater streams, if present, may contain alkali, benzaldehyde,
cyclohexanone, and condensation products.
6. EPA Source Classification Code - None
6-717
-------
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 6 (1965), p. 684.
6-718
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 305
Cyclohexanbne (oxidation of cyclohexanol)
O"
1. Function - Small quantities of cyclohexanone may be produced by parsing
cyclohexanol over copper catalyst with air at 140"C.
2. Input Materials
Cyclohexanol
Air
3. Operating Parameters
Temperature - 140 °C
Pressure - Not given
Catalyst - Copper
4. Utilities - Not given
5. Waste Streams - Waste water streams contain sodium hydroxide and
dissolved organics. Light ends column vent emits cyclohexane,
cyclohexanol and cyclohexanone.
6. EPA Source Classification Code - None
7. References
Hedley, W. H. , et al. , Potential Pollutants from Petrochemical Processes,
Final Report, Contract 68-02-0226, Task 9, December 1973, p. 224.
Waddams, A. L., Chemicals from Petroleum, 3rd Ed., John Murray Ltd.,
London, England, 1973, p. 136.
6-719
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 306
Cyclohexanone (hydrogenation of phenol)
O"
2
1. Function - Some cyclohexanone is produced by a hydrogenation reaction
similar to that employed to make cyclohexanol from phenol. The dis-
tinguishing variation is the milder catalyst used in this process.
Phenol and hydrogen are fed to a hydrogenator, where they are
reacted in the liquid phase at 100-200°C and 1-4 atm pressure in the
presence of a palladium-on-carbon catalyst. After scrubbing and
cooling, the reaction mixture is removed to a distillation column,
where high boilers are removed and cyclohexanone is recovered. This
method accounts for approximately 20% of the total of cyclohexanone
produced commercially in the United States.
2. Input Materials - Basis kg cyclohexanone
Phenol - 1.005 kg
3
Hydrogen - 0.64 m
Palladium-on-charcoal - small
3. Operating Parameters
Temperature - 100-200°C (212-392°F)
Pressure - 101-404 kPa (1-4 atm)
Catalyst - Palladium-on-charcoal
4. Utilities - Not given
6-720
-------
5. Waste Streams - Air vent systems contain some hydrogen. Waste water
from the scrubber will contain phenol, small quantities of cyclo-
hexanol and cyclohexanone. Vents from the overhead take-off system
in the distillation process will emit cyclohexanol and cyclohexanone.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals - Part 3,"
"Chemical Engineering," March 18, 1974, p. 92.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 6 (1965), p. 686.
Waddams, A. L., Chemicals From Petroleum, 3rd Edition, John Murray,
London, England, 1973, p. 136.
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, Inc., 1975, p. 306-307.
6-721
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO.307
o- and p-Nitfophenols (from phenol)
OH OH OH
N02
1. Function - Some o- and p-nitrophenol is produced by the nitration of
phenol with dilute nitric acid at low temperatures. The presence of an
OH group on the ring activates it and permits a significant amount of
oxidation resulting in a relatively large proportion of by-products.
The nitration produces the ortho-isomer in about a 4x excess. The over-
all yield however, is 40% ortho, 13% meta, 14% para, and 33% oxidation
products. The more volatile ortho isomer is almost quantitatively
stripped from the crude product by steam distillation. The residue
is heated and recrystallized in dilute acid to obtain the para isomer.
2. Input Materials
Phenol - for o-nitrophenol - 1.69 kg/kg product
for p-nitrophenol - 5.20 kg/kg product
total product - 1.28 kg/kg product
Nitric acid (20% aqueous)
3. Operating Parameters
Temperature - ~20°C (~68°F)
Pressure - 101 kPa (1 atm)
4. Utilities
Not given
6-722
-------
5. Waste Streams - Process waste effluents probably contain a variety
of resinous by-products, dinitrophenols and trinitrophenols, oxalic
acid, nitric acid, phenol, and small amounts of p-nitrophenol.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 13 (1967) , p. 892, 893.
6-723
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 308
o- And p-Phenetidiiie (from o- and p-nitrophenol)
OH
NO.
OCH CH
NOJ
+ NaCl
1. Function - Ortho- and para-phenetidine are usually prepared from nitro-
phenol isomers by ethylation (Williamson Reaction) and reduction. The
initial step is the formation of the ethyl-phenyl ether by the displace-
ment of chloride from the ethyl chloride by the o- or para-nitrophenate
ion. Either ethyl chloride or diethyl sxilfate may be used as the
alkylating agent.
The nitrated phenol ether is then reduced to the corresponding
amine using iron turnings and hydrochloric acid as the reducing system.
2. Input Materials
o- and p-Nitrophenol
Ethyl sulfate or ethyl chloride
Sodium hydroxide
Hydrochloric acid
Iron filings
Water
3. Operating Parameters
Alkylation Reduction
Temperature - 20-30°C (68-86°F)
Pressure - 101 kPa (1 atm)
Temperature - 200°C (392°F)
Pressure - 101 kPa (1 atm)
6-724
-------
4. Utilities
Not given
5. Waste Streams - Aqueous wastes from separation probably contain sodium
chloride, ethyl chloride, ethyl alcohol, nitrophenol and phenetidene
isomers, and a variety of reduction by-products. Ethyl chloride, ethyl
alcohol, and HC1 may be discharged from reactor vents and various types
of purification equipment.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New york, N.Y., Vol. 2 (1963), p. 422, 423.
6-725
-------
INDUSTRIAL ORGANIC CHEMICALS
Nitroanisoles (from nitrophenol)
PROCESS NO. 309
3.
4.
5.
6.
7.
OCH
3
OCH0
2H20
Function - The o- and p-isomers of nitroanisole are produced by
methylating the corresponding isomers of nitrophenol with a
reagent such as dimethyl sulfate. The reaction is carried out in
hot aqueous sodium hydroxide.
Input Materials
o- and p-Nitrophenol
Dimethyl sulfate
Sodium hydroxide
Water
Operating Parameters - not given
Utilities - not given
Waste Streams - Air and water effluents from separation probably
contain quantities of sodium hydroxide and sodium sulfate (water
only), dimethyl sulfate, and reaction by-products such as methanol.
EPA Source Classification Code - None
References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 15 (1968), p. 148, 168.
6-726
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 310
ANISIDINE
(reduction of nitroanisole)
OCR
OCHfl
OCH
Fe or Sn
HC1
OCH,
1. Function - Ortho- and para-anisidines are produced from o- and p-
nitroanisole by reduction with tin or iron filings and hydrochloric
acid.
The ortho and para isomers are separated by steam distillation.
2. Input Materials
o- and p-Nitroanisole
Hydrochloric acid
Tin or iron filings
3. Operating Parameters
Not given
4. Utilities
Not given
5. Waste Streams - Liquid and/or solid wastes from purification may contain
iron or tin salts and other reaction by-products.
6. EPA Source Classification Code - 3-01-034-01
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 422.
6-727
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 311
Nonylphenol
1- Function - Nonylphenol Is commercially prepared by the alkyla-
tion of phenol with a mixture of isomeric nonylenes (propylene
trimers). The reaction is carried out at 50-100°C and 345 kPa
(3.4 atm) in the presence of boron trifluoride catalyst.
The conversion takes place in the liquid phase and yields a
mixture of isomers, mostly para- with some 2,4-dinonyl substi-
tution. Both continuous and batch processes are used.
Following alkylation, the crude product is washed several
times and heated under vacuum to remove traces of reactants and
water. The final purification step is a vacuum distillation at
10-20 mm Hg.
2. Input Materials
Phenol - 0.46 kg/kg product
Nonene - 0.76 kg/kg product
3. Operating Parameters
Temperature: 50-100°C (122-212°F)
Pressure: 345 kPa (3 atm)
Catalyst: BF_
4« Utilities - Not given.
5. Waste Streams - The main source of pollution is the wastewater from
the product washing step. The water contains spent catalyst,
phenol, and traces of product.
6-728
-------
6. EPA Source Classification Code - None
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals
Part 7", "Chemical Engineering", June 24, 1974, p. 155.
Hedley, W. H., ^t al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 908.
6-729
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 312
Octylphenol
C6H5OH + CgH16 - *
!• Function - Octylphenol is prepared by alkylating phenol with iso-
butylene dimer. The product is a mixture of isomers.
The reaction conditions and purification procedures are
similar to those used in nonylphenol production.
2. Input Materials
Phenol
Diisobutylene
H2S04
3. Operating Parameters
Temperature: 120°C (248°F)
Pressure: Not known
Catalyst: Hos°4
4. Utilities - Not given.
5. Waste Streams - The principal waste stream from this process is the
product wash water. This may contain phenol, sulfuric acid and
traces of Octylphenol.
6. EPA Source Classification Code - None.
7 . References
Goldstein, R. F. , The Petroleum Chemicals Industry. John Wiley and
Sons, Inc., New York, N.Y. , 1958, p. 191-2.
Chemical Technology, Barnes and Noble Books, New York, N.Y.,
Vol. 4 (1972), p. 149.
6-730
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 313
Dodecylphenol
1. Function - Dodecylphenol is produced from phenol and propylene
tetramer (dodecene) , and consists mainly of a mixture of p-
alkylphenols derived from various isomeric branched-chain dodecy-
lenes .
The alkylation process is quite similar to that used to
make nonylphenol.
2. Input Materials
Phenol - 0.38 kg/kg product
Dodecene - 0.86 kg/kg product
3. Operating Parameters
Temperature: 50-100°C (122-212°F)
Pressure: 345 kPa (3 atm)
Catalyst: BF
4. Utilities - Not given.
5. Waste Streams - The main source of pollution is the waste water
from the product washing step. The water contains spent catalyst,
phenol and traces of dodecylphenol.
6. EPA Source Classification Code - None.
7. References
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 7", "Chemical Engineering", June 24, 1974, p. 155.
6-731
-------
Hedley, W. H., jit al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 908.
6-732
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 314
Phenolsulfonic Acids (from phenol)
H
O] +
+ H20
1. Function - Phenolsulfonic acid is commercially prepared by the
direct sulfonation of phenol with concentrated sulfuric acid at
100°C.
The yield based on phenol is approximately 94%. Although
the p-isomer predominates (96%), some o-phenolsulfonic acid is
also produced.
2. Input Materials
Phenol - 0.57 kg/kg product
Sulfuric acid (cone.) - 0.60 kg/kg product
3. Operating Parameters
Temperature: 100°C (212°F)
Pressure: Not given
4. Utilities - Not given.
5. Waste Streams - The principal pollutant from this process should
be spent caustic, present in the waste water from caustic washing
operations.
6. EPA Source Classification Code - None.
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 15 (1968), 211 and
Vol. 19, (1969) p. 311-18.
6-733
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 315
Allyl Chloride
CH3CH=CH2 + C12 » C1CH2CH=CH2 + HC1
1. Function - Allyl chloride is made by chlorinating propylene at
400-500°C. At temperatures of 300°C and less, addition to the
double bond is the predominant reaction and 1,2-dichloropropane is
formed.
The reaction is carried out in an adiabatic reactor designed to
provide rapid and intimate mixing. The reaction temperature is con-
trolled by balancing the mole ratio of the feed (usually 4 moles of
propylene to one mole of chlorine) and the propylene preheat tempera-
ture. The commonly used temperature range is 500-510°C, at 200 kPa
(1.9 psig).
2. Input Materials
Propylene - 723 kg/Mg product 1^71%)
Chlorine - 1.323 Mg/Mg product (70%)
3. Operating Parameters
Temperature: 500-510°C (932-950°F)
Pressure: 200 kPa (1.97 atm)
4. Utilities
Not given
5. Waste Streams
Absorber vent (air)
Propylene - 13.5 kg/Mg product
Ethyl chloride - 13.5 kg/Mg product
6-734
-------
The water pollution source from the allyl chloride process would
probably be spent caustic from the absorber.
6. EPA Source Classification Code - None
7. References
Anon., "Air Pollution from Chlorination Processes," prepared for OPA,
Environmental Protection Agency, Contract No. CPA 70-1, March 1972.
Muller, R. G., "Glycerine and Intermediates," Report No. 58, Stanford
Research Institute, Menlo Park, California, 1969.
Sittig, M., Pollution Control in the Organic Chemical Industry,
Noyes Data Corp., Park Ridge, N.J., 1974, p. 75,76.
6-735
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 316
Prbpylerie Chlbrohydrirt (from allyl chloride)^
OS02OH
CH2=CH-CH2C1 + H2S04 > CH3-CH-CH2
r
,-CH-C
CH3-CH-CH2C1 + H20 »• CH3-CH-CH2C1
1. Function - Small quantities of propylene chlorohydrin are produced
by the acid catalyzed hydration of allyl chloride. This system
yields l-chloro-2-propanol free of 2-chloro-l-propanol.
2. Input Materials
Allyl chloride
Water
Sulfuric acid
3- Operating Parameters
Temperature - 3.55-4.56 MPa (35-46 atm)
Pressure - 170-240°C (338 - 464°F)
Catalyst - sulfuric acid
4. Utilities
Not given
5. Waste Streams - Although no specific information was available,
wastewater streams from the purification section may contain traces
of sulfuric acid, allyl chloride, and propylene chlorohydrin.
6. EPA Source Classification Code - None
6-736
-------
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 310.
G. Frosberg and L. Smith, Acta Chem. Scand., !_, 578 (1947).
Hancock, E. G., Propylene and Its Industrial Derivatives, John Wiley
and Sons, New York, N.Y., 1973, p. 225.
6-737
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 317
Allyl Alcohol (from allyl chloride)
H.O
H2C=CHCH2C1 + NaOH —2—>• H2C=CHCH2OH + KaCl
1. Function - Some allyl alcohol is prepared from propylene glycol.
One competitive route to allyl alcohol involves the
hydrolysis of allyl chloride with dilute (5%) caustic solution.
The reaction is run at 150-160° C and a pressure of 1.38 MPa (14 atm).
The alcohol is recovered by injecting steam to form the water-
allyl alcohol azeotrope. The water is removed by ternary allyl ether
azeotrope. A second distillation then yields pure allyl alco-
hol. The principal by-product is allyl ether which can be mini-
mized by the addition of dilute caustic solution at a rate such
that the pH is maintained in the range 8-11.
2. Input Materials
Allyl chloride
Sodium hydroxide (5% aqueous solution)
Allyl ether
3. Operating Parameters
Temperature: 150-160° C (302-320°F)
Pressure: 1.38 MPa (14 atm)
4. Utilities
Not given
5. Waste streams - The principal pollutant sources in this process
are probably distillation waste water and solvent handling.
Allyl chloride and allyl alcohol, as well as diallyl ether, may
6-738
-------
be involved. Spent caustic waste streams from the reactor may
also contain allyl chloride and allyl alcohol.
6. EPA source Classification Code
None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 1 (1963), p. 588.
Fanbaun, A. W., H. A. Cheney and A. J. Charniavsky, Chem. Eng.
Prog., 43_, 280, (1947).
U.S. Patent 2,318,033.
Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing
Corp., New York, N.Y., 1956, p. 196-197.
6-739
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 318
Glycerol (from allyl chloride via allyl alcohol)
C12 + H20 y, N HOC1 + HC1
CH =CHCH2OH + HOC1 *• CH2OHCHOHCH2C1
•*•• Function - Some glycerol is produced from allyl chloride via pre-
liminary hydrolysis to allyl alcohol (see Process No. 317). The
allyl alcohol is then chlorohydrinated with aqueous chlorine solu-
tion to yield a mixture of monochlorohydrins.
The chlorohydrin intermediates are converted to glycerol in
90% yield (based on allyl alcohol) by hydrolysis with sodium
hydroxide:
CH2OHCHOHCH2C1 + NaOH —* CH2OHCHOHCH2OH + NaCl
The crude product is a dilute aqueous solution containing 5%
or less of glycerol. To obtain a high purity product, the crude
mixture is first concentrated to about 80% glycerol in multiple-
effect evaporators. Salt produced by the reaction is removed by
centrifuging. Additional concentration of the product, followed by
final desalting, yields 98% glycerol. Finally, colored substances
are removed by solvent extraction and the product is refined by
steam-vacuum distillation.
2- Input Materials
Allyl alcohol - 0.70 kg/kg product
Chlorine
Water
Sodium bicarbonate 10% aqueous solution
6-740
-------
3. Operating Parameters
Temperature: hydrochlorination - 14°C (57.2°F)
hydrolysis - 150°C (302°F)
Pressure: hydrochlorination - 100 KPa (1 Atm)
hydrolysis - elevated
4. Utilities - Not given
5. Waste Streams - The vents from the acid scrubber may omit hydrogen
chloride and chorine. Waste water will contain some sodium salts,
allyl alcohol and acids.
6. EPA Source Classification Code - None.
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 10, (1966) p. 624.
6-741
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 319
Glycerol (from epichlorohydrin)
CH2OCHCH2C1
HOCH2CHOHCH2C1 + NaOH > CH0OCH CH0OH + H00 + NaCl
CH.OCHCH0OH + H.O > HOCH-CHOHCH-OH
2 | 2 2 i z
1. Function - The production of glycerol from epichlorohydrin involves
a series of three reactions carried out at 157-180°C and 1.14 MPa
(11.2 Atm). First, epichlorohydrin is hydrated to monochlorohydrin
in basic solution.
Glycerol chlorohydrin is then dehydrochlorinated to glycidol
by treatment with caustic.
In the final reaction, glycidol is hydrated to glycerol.
Pipe reactors are used in this process with residence times
of 7-9 minutes. The crude glycerol product is purified in the
manner described in Process No. 318
2. Input Materials
Epichlorohydrin - 1.05 kg/kg product
Sodium hydroxide - 0.49 kg/kg product
Sodium carbonate - 73.0 g/kg product
Toluene - 6.0 g/kg product
HC1 - 83.5 g/kg product
3. Operating Parameters
Temperature: 157-180°C (315-356°F)
Pressure: 1.14 MPa (11.2 Atm)
Residence time: 420-540 sec.
6-742
-------
4- Utilities - Basis: 0.361 kg/sec capacity (25.2 M Ib/yr)
Cooling water - 124 dm /sec (1960 gpm)
Power - 547.2 MJ (152 kWh)
Steam (300 psi) - 4.10 kg/sec (32,520 Ib/hr) (2.07 MPa)
3
Process water - 3.03 dm /sec (48 gpm)
5. Waste Streams -
Glycerol purification section - second effect evaporator (water)
Glycerol - 4.5 kg/Mg product
Glycerol purification section - centrifuge (solid)
Sodium chloride - 431 kg/Mg product
Glycerol purification section - centrifuge (solid)
Sodium chloride - 431 kg/Mg product
Glycerol purification section - film evaporator (water)
Glycerol - 9.5 kg/Mg product
Sodium chloride - 82.5 kg/Mg product
Miscellaneous impurities - 61 kg/Mg product
Glycerol purification section - toluene recovery column (water)
Toluene - 4.5 kg/Mg product
Glycerol purification section - light ends column (water)
Glycerol - 0.95 kg/Mg product
Toluene - 1.55 kg/Mg product
6. EPA Source Classification Code - None.
7. References
Hedley, W. H. , et^ &L., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 10 (1966), p. 624.
6-743
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 320
Propylene Oxide (peroxidation of propylene)
2(CH3)3CH 4- | 02 * (CH3)3COOH + (CH^COH.
(CH3)3COOH + CH2=CHCH3 —* CH -CHCH3 + (CH^COH
1- Function - Increasing quantities of propylene oxide are now being
produced by the peroxidation of propylene. The organic peroxygen
carrier is usually t-butyl hydroperoxide, formed by the liquid-phase
air oxidation of isobutane at 125-150°C and 3.55 MPa (35 Atm) in
the presence of soluble molybdenum catalysts.
t-Butyl alcohol is the principal by-product of this reaction
and also functions as a product.
After separation, the t-butyl hydroperoxide is used to oxidize
propylene to propylene oxide and is reduced in the process to t-
butyl alcohol. Tungsten, vanadium, or molybdenum catalyst systems
catalyze this liquid-phase epoxidation.
It has been reported that the yield of propylene oxide from
propylene is about 93% of the theoretical. However, this process
yields considerably more t-butyl alcohol than propylene oxide (2.2
kg/kg propylene oxide).
2. Input Materials
Propylene - 0.78 kg/kg propylene oxide
Isobutane 'v 3 kg/kg product
Air
6-744
-------
3. Operating Parameters
Temperature: isobutane oxidation - 125-150°C (257-302°F)
epoxidation - not given
Pressure: isobutane oxidation 3.55 MPa (35 Atm)
epoxidation - not given
Catalyst: tungsten, vanadium, or molybdenum ([Mo(CO) ]
systems
4. Utilities - 100 kg/sec capacity (70 M Ib/yr)
3
Cooling water - 1.89 m /sec (30,000 gpm)
Refrigeration - 454 Mg (500 tons)
Electricity - 3600 MJ (1000 kW)
Steam - 12.6 kg/sec (100,000 Ib/hr) at 4.14 MPa (40.8 Atm)
3
Inert gas - 23.6 sdm /sec (300 scfh)
5. Waste Streams
Hydroperoxide preparation section - absorber (air)
Isobutane - 3.5 kg/Mg product
n-Butane - 0.5 kg/Mg product
Propylene oxide recovery section - vent from vaporizing
column (air)
Propylene - 10 kg/Mg product
Solvent recovery section - evaporator waste (liquid and
(solid)
Toluene - 1.0 kg/Mg product
Heavy ends - 50.0 kg/Mg product
Propylene oxide purification section - off gas from column to
flare (air)
Ethylene oxide - 2.0 kg/Mg product
Acetalahyde, etc. - 3.5 kg/Mg product
6. EPA Source Classification Code - None.
6-745
-------
7. References
Medley, W. H., £t al., Potential Pollutants from Petrochemical
Processes, Technomic Publishing Co., 1975.
6-746
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 321
1,2,3-Trichloropropane (from propylene)
H3C-CH=CH2 + 2C12 1- C1CH2-CH-CH2C1 + HC1
Cl
1. Function - 1,2,3-Trichloropropane is made by chlorinating
propylene at low temperature (25-40° C). The principal product
of this reaction is propylene dichloride. In the absence of a
catalyst however 20 percent of the product is 1,2,3-trichloropro-
pane. The products are easily separated by distillation.
2. Input Materials
Propylene
Chlorine
Propylene dichloride
3. Operating Parameters
Temperature: 25-40° C (77-104°F)
Pressure: 100 KPa (1 atm)
4. Utilities - Not available
5. Waste streams - Overhead gas streams contain chlorine, propylene,
hydrogen chloride some propylene dichloride.
6. EPA Source Classification Code - None
7. References
Astle, M. J., The Chemistry of Petrochemicals, New York, N.Y.,
Reinhold Publishing, 1956, p. 60-62.
6-747
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 322
Propylene Bichloride
CH3CHC1CH2C1
1. Function - Propylene dichloride is produced as a by-product of the
propylene chlorohydrin process for the synthesis of glycerin.
Some may also be produced as a by-product of the chlorination
of propylene to produce allylchloride. Propylene dichloride
does not itself have industrial uses however it may be easily
cracked to produce carbon tetrachloride and perchloroethylene.
The chlorine necessary to react with the propylene is present
as a result of the equilibrium HOC1 + HC1 £ Cl- + H-0. The
formation of propylene dichloride is promoted when the olefin
concentration in the propylene chlorohydrin process falls too
low or when the chlorohydrin concentration exceeds 5-6% in the
system. Under the usual operating conditions 0.1 kg of propylene
dichloride is formed per kg of propylene oxide.
2. Input Materials
Propylene
Chlorine
Water
3. Operating Parameters
Temperature: 30-40° C (86-104°F)
Pressure: 100 KPa (1 atm)
6-748
-------
4. Utilities*
Cooling water 259dm3/sec (4100 gpm)
Nitrogen 23.6 dm3/sec (3000 cfh)
Power 648 MJ (180 KW)
Refrigeration 1.109 Gg (1222 tons)
Steam 7.31 Kg/sec (58,000 Ib/hr)
5. Waste Streams* - Propylene dichloride is a by-product of propylene
chlorohydrin production and as such the waste streams will be
identical to this process. Air vent streams contain propylene
and chlorine. Waste water contains HC1, HOC1, some chlorohydrin.
6. EPA Source Classification Code - None.
7. References
Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John
Murray, London, 1973, p. 137-138.
Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing
Corp., New York, 1956, p. 60-61.
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 2-3.
*See propylene chlorohydrin waste streams.
6-749
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS HO. 323
Dichloropropenes
CH2=CHCH, + 2C12 - »• CHC1=CHCH2C1 + CH2=CHCHC12 + 2HC1
90% 10%
1. Function - 1,3-Dichloropropene and 3,3-dichloropropene are the chief
secondary products of allyl chloride manufacture, which involves the
high-temperature reaction of propylene and chlorine.
The dichloropropene yield may be increased by using an excess
of chlorine or smaller amounts of propylene. Chlorination at tempera-
tures below 300°C yields the addition product, 1,2-dichloropropane.
The reaction is carried out in the vapor phase under conditions
similar to those used in the production of allyl chloride, temperature
500-510°C (932-950°F) and 142-284 kPa (1.4-2.8 atm) . The propylene
is preheated to 250-350°C (482-662°F) to prevent the addition of
chlorine to the double bond on mixing. The product ratio can be
controlled to some extent by the ratio of reactants charged. The
use of excess chlorine to increase the product ratio of 1,3-dichloro-
propene to allyl chloride is limited, however, by the possibility of
over chlorination of the propylene.
The product mixture is separated by passing the effluent gas
stream into an HC1 absorption column. Next the gas is passed
into an organic absorbing solvent to remove propylene. The chlori-
nated propylenes are separated by fractional distillation.
2. Input Materials - Basis - 1 kg product
Propylene - 0.723 kg/kg
Chlorine - 1.32 kg/kg
6-750
-------
3. Operating Parameters
Temperature: preheater - 340°C (650°F)
reactor - 500-510°C (932-950°F)
Pressure: 142-284 kPa (1.4-2.8 atm)
4. Utilities - Not given
5. Waste Streams - The principal sources of pollution are the air vent
stream on the absorber which may emit propylene and the wastfe water
from the absorber which contains spent caustic.
6. EPA Source Classification Code - None
7. References
Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing
Corp., New York, 1956, p. 60-61.
Hedley, W. H., et al., "Potential Pollutants from Petrochemical
Processes," prepared for Control Systems Laboratory, NERC,
Environmental Protection Agency, Contract No. 68-02-0226, Task
No. 9, 1973, p. 136.
6-751
-------
SECTION IX
TOLUENE
6-752
-------
TOLUENE
TOLUENE
W&
J •) Benzonitrile
333i
345!
349
^ Benzoic acid
326
> Phenol
327 328
>3,5-Dinitrobenzoic acid ^3,5-Oiaminobenzoic acid
329' 330
;—^m-Nitrobenzoic acid ^ m-. or p-Aminobenzoic acids
331
) Sodium benzoate
i
-4 Benzyl chloride
332
••) Benzyl benzoate
|
Benzyl alcohol
335
—_—> Benzyl ami ne
-} Benzyl dichloride
336i -337
> Benzotrichloride ^Benzoyl chloride — ^Benzamide
338
———^Nitrotoluene-
339 330
> Nitrobenzoic acids — ^ Aminobenzoic acids
^D1nitrotoluene*i » Dinitrobenzoic acids-328 ) Diaminobenzoic acids
343i
,4-Diaminotoluene
-> 2,6-Diaminotoluene
341 344
. ^Toluidines > m-Chlorotoluene
p-Chlorotoluenes —.—— ^ p-Chlorobenzaldehyde
. •) o- & p-Chlorobenzoic acids ) o- & p-Chlorobenzoyl chlorides
>Benzene
i Xylene
) Hethylcyclohexane ^ Methylcyclohexanol ^ Methylcyclohexanone
353 354 355 356
^Benzoin - — - ^Benzil - » Benzilic acid
\ Benzaldehyde
357
-)p-Toluenesu1fonyl chloride-
358
p-Toluenesulfonaraide
Figure 17. Toluene Section Chemical Tree
6-753
-------
Cooll
St
ng water
T II
Air
325
Oxidation
Heat
/> 1
*•«
NH3
1 P.
324 1
Anmonolysls 1
Heat
F,-HC11
V I
Benzyl C00lin9 **?
alcohol Heat f
; A i 11
332
Ester1f.1 cation
Cooling water
H2SO,, fl
I W* Hef 11
32?|
Nitration 1
Cooling water
Tr» Til
329!
Nitration
Heat
AiV i
326
Oxidation
'XJ
Na.CO,
1 P
* /A
33l|
Salt formation I
3,5-
Dinltrp-
benzoic
acid
leat
4
f
328
Reduction
3,5-
01amino-
benzole
acid
Figure 18. Toluene Section Process Flow Sheet
-------
Ul
Ui
Heat
Fe° Cooling water
|Cj2p Stef|l
345
Chlorlnatlon
Cooling water
"i» "til
350
Hydrogenation
^XJ
HS04
I Mater
ITfc
33ftl
Nitration 1
Heat
eam I
Steam
p-
(Chlorobenz-
ialdehyde
o- S p
Chloro-
benzoic
acids
Chlorlnatlon 346
& Hydrolysis
Cool
St
D
«3
ing water
rl
Chromic
acid Steam
I ftv t
339 1
Oxidation I
pe<> Cooling water
1HC1 Heat \ I
1 fc HI
341 1
Reduction 1
H2SOM
j HN03
340
Nitration
Chlorobenzojtr
«
ichloride
iteam 1
i I
Cooling water
nrtO 1
Chlorination and 1
hydrolysis |
Air
352
Oxidation
f
330
Reduction
"T\ 2
uri Cooling water
FTP, II
344 1
Replacement 1
H2
343
Reduction
O- i p-
Chloro-
benzoyl
ichloride
Methyl-
eye lo-
hexanone
(m- Chloro-1
f2,4 & 2,6-
Diamino-
Ltoluenes
Figure 18. Toluene Section Process Flow Sheet (Cont.)
-------
1
Cooll
Ste
ng water
T II
Fuel
1? „
349 ^
Transalkylatlon
1 1
Cooling water
s,T|J
Cooling water
02 Steam ||
1 J> 1 11-
Heat
1 Oleum
PC15
It ^>
Oxidation Sulfonation and
substitution
1 L
Steam
Cooling water
IICV A
3331
Chi or1 nation I
fp-Toluene-i
sulfonyl
chloride
~J
Ui
Cool
t
Ing water
Til
Ethanol
IT
354
Condensation
Mater
Heat 1
NH3
* 0
358
Ammonolysls
^
Cooling water
Steam 11
Acetic acid
HN03
Figure 18. Toluene Section Process Flow Sheet (Cont.)
-------
I
-J
Ln
V
i
\
)
Steam
Hj
Hater
1 NaOH
4 » A
fdrolysls
Cooling water
Steam || NH3
33<
Amlnatlon
Benzole
acid
Cooling water
Heat Q Steam |j
1 /A 1 11
C|°3HNO
1 HNO
i ^ 336 1 342
Exchange I Oxidation
(BenzylamineI
Steam
Cooling
water
Ammonolysls
337
^1
Heat
Reduction
32
Figure 18. Toluene Section Process Flow Sheet (Cont.)
-------
INDUSTRIAL ORGANIC CHECMICALS PROCESS NO, 324
Benzonitrile
rtrr
n
-3
1. Function - Benzonitrile is produced in the United States chiefly
by the ammonolysis of toluene in the vapor phase. The reaction
takes place in a reactor that consists of a shell containing a catalyst
chamber heated with a heat transfer medium from outside the shell.
Benzonitrile produced in each pass is stripped from the exit gases
which are recycled with makeup toluene and ammonia. The optimum
operating conditions are described as employing molybdenum oxide on
alumina as a catalyst, maintaining temperature between 524-552°C, and
operating at pressures of 1 atm. of less. Conversion per pass ranges
from 5-10%. Overall yields from 60-85% based toluene are reported.
2. Input Materials - Basis: 1 kg benzonitrile
Toluene - 0.89 kg
Ammonia - 0.16 kg
MoOs catalyst - quantities not given
3. Operating Parameters
Temperature: 524-552°C (975 - 1025°F)
Pressure: 101 KPa (1 atm) or less
Yield: 60-85% based on toluene
*• Utilities - Quantities not given
5. Waste Streams - Off gases contain ammonia, hydrogen cyanide and toluene.
Air vent streams from the purification system would contain toluene.
6. EPA Source Classification Code - None
6-758
-------
7. Reference
Astle, M.J., Industrial Organic Compounds, Reinhold Publishing Cor-
poration, New York, 1961, p. 227-228.
6-759
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 325
CH, Benzoic Acid COOH
1. Function - The preferred industrial process in the manufacture
of benzoic acid, in the United States, is the air oxidation of
toluene.
The reaction is carried out in the liquid phase at 110 - 150°C
at pressures of 273 - 490 kPa (2.7 - 5 atm) using a cobalt salt
usually the naphthenate as the catalyst. The heat of reaction
is controlled by refluxing toluene and water-jacketed cooling.
Water of reaction is removed from condensed off gas before the
toluene is returned to the reactor heel. Material in the autoclave
heel continously overflows to a stripper where toluene is re-
cycled. The bottoms, which contains the crude benzoic acid, are
sent to a crystallizer, or a distillation tower. Yields of
relatively pure material of 90% based on toluene are cited.
2. Input Materials - Basis 1 kg benzoic acid.
Toluene .83 kg/kg
Air 1.71 kg/kg
Cobalt naphthenate .008 - .024 kg/kg
3. Operating Parameters
Temperature: 110 - 150°C (230-302°F)
Pressure: 273 - 490 kPa (2.7 - 5 atm)
Catalyst: 0.1 - 0.3% of toluene
6-760
-------
4- Utilities - Based on 100 M Ib/yr capacity
Water - .545 m3/sec (518,000 gPh)
Steam - 5.93 kg/sec. (47,000 Ibs/hr)
Power 2,320
5. Waste Streams - Air vent stream from the purification contains
toluene, some benzaldehyde and some benzyl alcohol. The air
vent from the separator (centrifuge) contains toluene vapors.
The waste water contains benzoic acid, benzaldehyde and benzyl
alcohol.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 3 (1967), p. 420-439.
Sittig, M., Organic Chemical Process Encyclopedia, 2nd Edition,
Noyes Development Corporation, Park Ridge, New Jersey, 1969, p. 101.
Hedley, W.H. et. al., Potential Pollutants from Petrochemical
Processes, Final Report, Contract 68-02-0226, Task 9, MRC-DA, 406,
December 1973, p. 111-112.
6-761
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 326
Phenol (oxidation of Benzole acid)
OOH copper
+ 1/2 02 catalyst Ik-^J + C02
1. Function - Benzoic acid is melted in biphenyl, mixed with a small
amount of manganese-promoted cupric benzoate and fed to an oxidizer
(reactor). A mixture of air and steam is sparged into the reactor,
where the benzoic acid is oxidized to phenol.
Purification is accomplished by distillation. Phenol and water
are taken off overhead and benzoic acid is taken from the column
bottom and returned to the reactor. The bottoms may be extracted
firstjto recover organics for recycle. The phenol and water are
separated by azeotropic distillation.
2. Input Materials
Benzoic acid
Air
Catalyst
3. Operating Parameters
Temperature - 230°C (446°F)
Pressure - 138-172 kPa (1.36-1.7 atm)
Mn-cupric benzoate - not given
4. Utilities - Not given
5. Waste Streams
Centrifuged separator (solid)
Tar -0.10 kg/kg phenol (204 Ib/ton)
Phenyl benzoate -0.0015 kg/kg phenol (3.1 Ib/ton)
6-762
-------
5. Waste Streams (continued)
Acetone -0.0018 kg/kg phenol (3.6 Ib/ton)
Manganese benzoate -0.005 kg/kg phenol (10 Ib/ton)
Copper benzoate -0.002 kg/kg phenol (4.3 Ib/ton)
Separator effluent
Toluene -0.0011 kg/kg phenol (2.14 Ib/ton)
6. EPA Source Classification Code - None
7. References
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,
John Wiley & Sons, New York, N.Y., 1975, p. 618-619.
Hedley, W. H., et al., "Potential Pollutants from Petrochemical Processes,"
Prepared for Environmental Control Systems Laboratory, NERC, Environmental
Protection Agency, Contract No. 68-02-0226, Task No. 9, 1973, p. 111-112.
6-763
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. .327
3 t5-Dinitrobenzoic Acid
;QOH
H0SO, n 7/N
, 9. a.^ O_N -C I 1
3
1. Function - 3,5-Dinitrobenzoic acid is primarily manufactured by
nitrating benzoic acid with a mixture of fuming nitric and sulfuric
acids. The sulfuric acid forms a hydrated molecule and removes the
water of reaction. The nitration occurs at elevated temperatures
(70-90°C).
2. Input Materials - Basis: 1 kg 3,5-dinitrobenzoic acid
Benzoic acid - 0.6 kg
HN03 - 0.6 kg (99+% acid)
3. Operating Parameters
Temperature: 70-90°C (158 - 194°F)
Pressure: atmospheric
4. Utilities
Quantities not given
5. Waste Streams - Off -gas will contain oxides of nitrogen and some
sulfur dioxide. Waste water from the purification process contains
nitric and sulfuric acids, benzoic acid and some 3,5-dinitrobenzoic
and 3-nitrobenzoic acid.
6. EPA Source Classification Code - None
7. References
Astle, M.J., Industrial Organic Nitrogen Compounds, American Chemical
Society Mongraph Series, Reinhold Publishing Corporation, New York,
1961, p. 334.
6-764
-------
INDUSTRIAL ORGANIC CHECMICALS PROCESS NO. .328
3,5-Diaminobenzoic Acid
COOH COOH
+ 4H2°
1. Function - 3,5-Diaminobenzoic acid is commercially produced by the
catalytic reduction of dinitrobenzoic acid. The process is similar
to that used to manufacture m,p-aminobenzoic acids. The reaction
occurs in the liquid phase at about 1 atmosphere pressure. The hydro-
gen is fed in large excess to a slurry of catalyst, dinitrobenzoic acid
and water at temperatures greater than 85°C. The product acid is then
filtered to remove catalyst and cooled to precipitate the product.
2. Input Materials - Basis: 1 kg diaminobenzoic acid
Dinitrobenzoic acid - 1.5 kg
Hydrogen - >0.03 kg
Catalyst - quantities not given
3. Operating Parameters
Temperature: 85°C (185°F)
Pressure: lOOKPa (1 atm).
Catalyst: Pd, Cu, Pt, or Ni
4. Utilities
Not given
5. Waste Streams - Off-gas from the reactor contains hydrogen. Waste
water contain 2,5-dinitrobenzoic acid and 3,5-diaminobenzoic acid.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 3, (1964) pp. 435-436.
6-765
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 329
m-Nitrobenzoic Acid
+ HN03-H2S04
!• Function - The product of the nitration of benzoic acid is m-nitro-
benzoic acid with the principal byproduct being ortho-nitrobenzoic
acid. Almost no p-nitrobenzoic acid is formed and the ortho isomer
can be minimized by proper selection of the reaction temperature.
The rate of reaction increases with temperature, however the
amount of m-isomer decreases with temperature while the amount of
ortho isomer increases. The operating temperature must be a
compromise between optimum rate of production and purity of
product.
The reaction is carried out in sulfuric acid and a maximum
in rate of nitration is found at 89-90% sulfuric acid.
2. Input Materials
Benzoic acid
Nitric acid
Sulfuric acid
3. Operating Parameters
Temperature - 25-45°C
Pressure - Atmospheric
Sulfuric acid - 90%
6-766
-------
4. Utilities - Not given
5. Waste Streams - Air vent streams contain oxides of nitrogen.
Waste water streams will contain benzoic acid, some m-nitrobenzoic
acid.
6. EPA Source Classification Code - None
7. References
Hoggett, J. G., Moodie, R. B., Penton, J. R. , and Schofield, K.,
Nitration and Aromatic Reactivity, Cambridge University Press,
London, 1971, pp. 16, 18, 151, 160, 178.
6-767
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 330
m-or p-Aminobenzoic Acids
•C°°H + 3H2 -£*S— yP-jV + 2H20
1. Function - These acids are manufactured chiefly by the reduction of
m-or p-nitrobenzoic acids by catalytic hydrogenation or, less fre-
quently, by reduction with tin or iron and HC1. One patent for
p-aminobenzoic acid claims an 85% yield when hydrogenating p-nitro-
benzoic acid with a Pt or Pd catalyst in water.
A thin slurry of p-nitrobenzoic acid and catalyst in water is agitated
at about 800 RPM and held at 85°C. Hydrogen is then introduced until
no more absorption is noted and the p-nitrobenzoic acid dissolves as
the reaction proceeds. The partial pressure of H_ is from 200-700 mm Hg
in the atmospheric pressure process. The product acid is filtered and
cooled to precipitate a 99% product. The mother liquor from pre-
cipitation is reused in the next batch.
2. Input materials - Basis: 1 kg of aminobenzoic acid
Nitrobenzoic acid (m-, or p-) - 1.2 kg
H2 - >0.04 1.2 kg
Catalyst: Pt, Mi, Pd, or Cu - quantities not given
3. Operating parameters
Temperature: 85°C
Pressure: atmospheric
Agitation: 800 RPM
4. Utilities
Quantities not given
6-768
-------
5. Waste streams - The off gas from the hyd rogenation reactor contains
hydrogen, when iron powder and hydrochloric acid is used hydrogen
chloride is present in the off gas. Waste wash water from the
centrifuge contains aminobenzoic acid, ferric chloride and HC1. The
product contains some m-or p-nitrobenzoic acids.
6. EPA Source Classification Code
None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-
science Publisher, New York, N.Y., Vol. 3 (1967) p. 434-436.
6-769
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 331
Sodium Benzoate
COOH
+ NaOH ft, Ifl + HOH
1. Function - Sodium benzoate is generally produced by the addition of
benzole acid to a hot solution of sodium carbonate or sodium hydr-
oxide. The resulting solution is treated with charcoal or, in some
cases, potassium permanganate, and is filtered and dried.
2. Input Materials - Basis: 1 kg sodium benzoate
Benzoic acid - 0.85 kg
NaOH - >0.3 kg
NafiC03 (alternate) - >0.74 kg
Charcoal - quantity not given
KMnO^ - quantity not given
3. Operating Parameters
Quantities not given
4. Utilities
Quantities not given
5. Waste Stream - Waste water streams contain sodium hydroxide or
sodium carbonate and water use to wash the benzoate product contains
NaOH, Na2C03, NaHC03 and some sodium benzoate. There will be some
carbon dioxide in the off-gas.
6, EPA Source Classification Code
None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition, Inter-
science Publishers, New York, N.Y., Vol. 3 (1967), p. 433.
6-770
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 332
C=0
Benzyl Benzoate
COOH
COOH
Function - Benzyl benzoate is produced commercially by two routes.
The most commonly used commercial process is the Cannizaro reaction
in which benzaldehyde, catalyzed by sodium hydroxide, undergoes an
oxidation-reduction reaction giving benzyl alcohol and benzoic
acid. These compounds undergo an esterification catalyzed by the
NaOH to produce benzyl benzoate. The second process involves a
direct esterification of benzoic acid and benzyl alcohol catalyzed
by a boron trifluoride hydrochloric acid complex. The reactions
are carried out at 75-90°C at 1 atm pressure.
Input Materials - Basis: 1 kg benzyl benzoate (benzaldehyde
route)
Benzaldehyde - 2 kg
NaOH catalyst/reactant - quantities not given
Operating Parameters
Temperature: 75-90°C (167-194°F)
6-771
-------
Pressure: 100 kPa (1 atm)
Catalyst: NaOH or any strong base
4. Utilities
Quantities not given
5. Waste Streams - Waste water contains sodium hydroxide, sodium ben-
zoate and some benzaldehyde. No significant quantities of air pollu-
tants would result from this process.
6. EPA Source Classification Code - None
7. References
Shreve, R. N., Chemical Process Industries, McGraw-Hill Book Co.,
New York, 1967, p. 512.
6-772
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 333
Benzyl Chloride, Benzyldichloride, Benzotrichloride
CH3 CH2C1 CHC1
' C12 *" VJ + Cl2-****> lyi + C12 *• ILJJ + HC1
1. Function - The chlorination of toluene to the three products,
mono-, di-, and tri-chloromethyl benzene, can be considered as a
single process since the extent of chlorination cannot be exactly
controlled.
The use of excess toluene will result in a predominance of
benzyl chloride. Stopping the reaction when the product density
reaches 1.283 will result in a product that is predominantly
benzyl chloride and allowing the reaction to continue until the
product density reaches 1.38 will yield benzotrichloride.
The reaction must be carried out in glass or polymer lined
reactors since iron catalyses nuclear substitution. The tempera-
ture is controlled in this exothermic reaction by the reflux of
toluene.
2. Input Materials
Toluene
PCI- or PC15 (optional)
3. Operating Parameters
Temperature: 110° C
Catalyst: PCI or PCI. (optional)
Spec. Eqpt.: Cl? resistant container for benzyl - glass
for benzotrichloride
6-773
-------
4. Utilities - Not given
5. Waste streams - HC1 is neutralized with a weak base before disposal,
so chloride salts will be waste.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 5(1969), p. 281-287.
Austin, G. T., "The Industrially Significant Organic Chemicals-
Part 1," "Chemical Engineering," January 21, 1974, p. 132.
6-774
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 334
Benzyl Alcohol
CH2C1
+ NaOH - > + NaCl
1. Function - Benzyl alcohol Is manufactured in the United States
exclusively by hydrolysis of benzyl chloride. Sodium hydroxide or
sodium carbonate is usually employed but use of the carbonate
minimizes formation of by-products such as dibenzyl ether.
A charge consisting of 1349.4 kg (2,975 Ib) of water, 1428.8
kg (3,150 Ib) benzyl chloride, and 714.4 kg (1,575 Ib) sodium car-
3
bonate is put into a 3.785 m (1,000 gal) steel jacketed reactor,
agitated, and heated to reflux for 24 hours. The reaction is
cooled, sodium chloride added to saturation, and the layers allowed
to separate. The lower aqueous layer is drained to the sewer while
the upper layer of crude benzyl chloride is purified by vacuum dis-
tillation.
2. Input Materials
Benzyl chloride - 1.34 kg/kg alcohol
Sodium carbonate - 0.67 kg/kg alcohol
Water - 1.27 kg/kg alcohol
3- Operating Parameters
Temperatures: 210°C (410°F)
Reaction Time: 24 hours
3
Equipment: 3.75 m (1,000 gal) steel-jacketed reactor
6-775
-------
4. Utilities - Not given
5. Waste Streams - Aqueous layer saturated with sodium chloride and
containing sodium carbonate used to be discharged to the sewer but
may be disposed of differently now. Waste water may contain
traces of benzyl chloride.
6. EPA Source Classification Code - None
7. References
' Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 3 (1964), p. 443-
444.
6-776
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 335
Benzyl Amine
,CH2NH2
+ NH^Cl
1. Function - Benzylamine is produced commercially by the ammonolysis
of benzyl chloride. The reaction is carried out at elevated
temperatures (100-200° C) and pressure (100 KPa-2.76 MPa) and a
4 to 10 X excess of aqueous ammonia. The major product under these
conditions of excess ammonia is the primary amine, although some
secondary, tertiary and quaternary salts are formed. The water
and ammonia are separated and recycled and the amines separated
and purified by distillation.
2. Input Materials
Benzyl chloride
65% aqueous ammonia
3- Operating Parameters
Temperature: 150-200° C (302-392°F)
Pressure: 100 kPa-2.76 MPa (1-27 atm)
4. Utilities - Not given
5. Waste streams - by-product secondary and tertiary amines quaternary
salts are formed. Ammonium chloride sent to other processes.
6. EPA Source Classification Code - None
7. References
Astle, M. J., Industrial Organic Nitrogen Compounds, Reinhold
Publishing Corp., New York, N.Y., 1961, p. 6-8.
6-777
-------
7. References (continued)
Shreve, R. N., Chemical Process Industries^ McGraw Hill Book
Company, New York, N.Y., 1967, p. 815-816.
6-778
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 336
Benzoyl Chloride
CC13 COOH
1. Function - Benzotrichloride and catalyst (zinc chloride impregnated
on pumice) are run into a glass-lined steel reactor which has
previously been half filled with molten benzoic acid. A glass-
coated agitator is used to stirr the mixture and tank temperature
is maintained at 122-130°C for about eight hours. A Karbate (impreg-
nated carbon) condenser removes the hydrochloric acid formed in the
reaction. The benzoyl chloride is purified by distillation.
2. Input Materials
Benzotrichloride
Benzoic acid
3. Operating Parameters
Temperature: 122-130°C (252-266°F)
Pressure: 101 kPa (1 atm)
Catalyst: zinc chloride on pumice
4- Utilities - Not given
5. Waste Streams - Waste waters may contain traces of benzoic acid,
benzotrichloride, and zinc chloride.
6. EPA Source Classification Code - None
7. Kirk-Othemer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 3 (1964), p. 424.
6-779
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 337
Benzamide
^- Function - Benzamide is produced by the acylation of ammonia with
benzoyl chloride. The reaction may be carried out under anhydrous
conditions by passing anhydrous ammonia into a solution of benzoyl
chloride in an inert solvent such as diethyl ether. In a commercial
operation it is more usual to add the benzoyl chloride to a cold
(0°C), concentrated aqueous solution of ammonia from which the benza-
mide percipitates. The crude benzamide is washed with water and
purified by recrystallization.
2. Input Materials
Benzoyl chloride
Ammonia (anhydrous or concentrated aqueous solution)
3. Operating Parameters
Temperature - 0°C (32°F)
Pressure - 101 kPa (1 atm)
4. Utilities - Not given
5. Waste Streams - Air streams may contain ammonia and some hydrogen
chloride. Waste water from product recovery and purification contains
ammonia, HCl, NH.C1 and benzoic acid.
6. EPA Source Classification Code - None
6-780
-------
7. References
Kirk-Othmer, Encyclopedia ot Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 69-71.
6-781
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 338
Nitrotoluene
H2S04/HN03
1. Function - Nitrotoluenes are manufactured by nitration of toluene
by a nitrating agent usually consisting of a mixture of sulfuric
and nitric acid and recycled fortified acid. The ratio of H-SO,,
HNO_ and H»0 as well as the temperature and rate of agitation has
to be controlled to ensure high yield, favorable ratio of desired
isomer, and to minimize dangerous side reactions. Nitration is
done at relatively low temperatures (<40°C) . The crude product is
washed with water, alkali, and water. The isomeric nitrotoluenes
are then separated from toluene and other organics by steam dis-
tillation and subsequently dried. Separation of the o-, m-, and p-
isomers is done by a series of vacuum distillations.
2. Input Materials - basis: 1000 kg yield of nitrotoluene
Toluene - 690 kg
Nitric acid - 450 kg
Sulfuric acid - 810 kg
Water - 240 kg
10% NaOH solution - 22 kg
3. Operating Parameters
Temperature: 25°C [initially] (77°F)
35-40°C [final] (95-104°F)
6-782
-------
Equipment: Toluene nitration is normally carried out in cast-
iron or stainless-steel nitrators sized for 3,000 gal batches of
toluene.
4. Utilities - None given
5. Waste Streams - Heavy tar residues from final fractionation
stage are disposed of and would contain a complex mixture of
organic by-products in the amount of approximately 40 kg/1000 kg
nitrotoluene. Waste waters may contain also alkali used in wash-
ings, spent acid, and soluble organic by-products.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 13 (1967), p. 844-^
848.
Albright, L.F. and Hanson, C., "Industrial and Laboratory Nitrations,"
ACS Symposium Series 22, 1976, p. 190-218.
6-783
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 339
Nitrobenzoic Acids
:OOH
[0]
1- Function - m, and p-Nitrotoluene may be oxidized with chromic
acid to yield the corresponding m-, and p-nitrobenzoic acids, o-
Nitrotoluene is not affected by chromic acid. o-Nitrotoluene is oxidized
by potassium permanganate to give o-nitrobenzoic acid.
2. Input Materials
Nitrotoluene
Potassium permanganate (to oxidize o-nitrotoluene or p-nitrotoluene)
/
Chromic acid (to oxidize m- and p-nitrotoluene)
3. Operating Parameters
Temperature: 25-50°C (77-122°F)
Pressure: 101 kPa (1 atm)
4. Utilities - Not given
5. Waste Streams - Neutralization of reaction waste liquors would give
wastewater streams containing salts of the acid or alkali used.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N. Y., Vol. 13 (1967), p. 848-
850.
6-784
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 340
Dinitrotoluene (nitration of toluene)
CH~ + HNC- -H9SO. - *• mixed nitrotoluenes
CH« "» J.J.i*W« — LLfJ\J\J I ' UOi"1|~\V ]F~*>JH'\
J J ^ H- ,Z ^^^*^r -^
1. Function - The reaction of nitric acid and toluene to produce
dinitrotoluene can be thought of as a two stage reaction. The
first stage being the mononitration of toluene. The nitrating
agent is the acid mixture 48% sulfuric, 18% nitric, 14% nitro-
sylsulfuric, 12% water and 8% nitroorganics, which is typical
of the fortified spent acid from the dinitration stage. The
temperature is initially 25° C raised to 40° C to complete the
reaction. The reactor must be vigorously agitated since the
toluene is not very soluble in the mixed acids. A typical pro-
duct mix is 62% ortho, 33% para and 3% meta. The mixture may
be separated or used as is in the second nitration step.
The acid mixture used in the second stage contains, for a
typical mixture, 50% sulfuric, 20% nitric, 12% nitrosylsulfuric
6% water and 12% nitroorganics. The temperature must be
increased to 55 to 85° C at 1 atm pressure. Nitration of the
pure p-isomer yields 2,4-dinitrotoluene with no significant
amounts of by-product. Nitration of the unresolved product of
the mononitration yields an 80-20 mixture of 2,4 and 2,6-
dinitrotoluene, respectively. The product mixture may be separated
into the pure isomers by crystallization or used directly for
the manufacture of toluenediisocyanate.
6-785
-------
2. Input Materials
Toluene: 506.25 kg/Mg of product
Nitric Acid: 721.25 kg/Mg of product
Sulfuric Acid: 1311 kg/Mg of product
Nitrosyl sulfuric acid: 262 kg/Eg of product
?. Operating Parameters
Temperature: mononitration 25-40° C (77-104°F)
dinitration 50-85° C (122-185°F)
Pressure: 100 KPa
4. Utilities - Not available
5. Waste Streams
Decantors (water) - Wastewater from the decanters, containing
small amounts of nitrated toluene, is discarded and may end up
in sewer lines.
Absorber (air) - Reactor vents go to the absorber to oxidize
the NO to NO- which is absorbed in water to produce nitric acid.
Vent from absorber discharges air and unabsorbed oxides of nitrogen.
Washer vents (air) - Air saturated with water and some nitrated
toluenes will be discharged from the washer vent.
6. EPA Source Classification Code - None
7. References
Austin, G. T., "Industrially Significant Organic Chemicals,"
"Chemical Engineering," April 15, 1974.
Sittig, M., "Pollution Control in the Organic Chemical Industry,"
Noyes Data Corporation, Park Ridge, N.J., 1974, p. 126-27.
Brownstein, A. M., "U.S. Petrochemicals - Technologies, Markets
and Economics," The Petroleum Publishing Company, Tulsa, Oklahoma, 1972.
6-786 -
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 341
Toluidines
NO,
NH,
Fe
HC1_L
'2 ^2
Function - The toluidines are made from the nitrotoluenes by reduc-
tion. The process most commonly used is the metal-acid process,
the most widely utilized combination being iron and hydrochloric
acid. Nitrotoluene, powdered iron, and a small amount of
water are mixed in a reaction vessel. Hydrochloric acid is added
at a rate such that the heat of reaction will maintain a brisk
rate of reaction. The converted toluidine is steam distilled,
from the reactor, separated, and purified by distillation. Approx-
imately 3.1% of the toluidine remains in the aqueous layer most
of which may be recovered by solvent extraction.
Catalytic hydrogenation has been replacing the iron-acid
method in recent years yielding a purer product at lower cost. The
reduction is done in the vapor phase, passing hydrogen and the
nitrotoluene vapor through a fluidized bed of copper clad silica
gel.
Input Materials
Iron reduction: Nitrotoluene
Hydrochloric acid - iron powder
Catalytic reduction. Nitrotoluene
Hydrogen
6-787
-------
3. Operating Parameters
Iron reduction: Temperature: 100° C (212°F)
Pressure: 100 kPa (1 atm)
Catalytic reduction: Temperature: 250-300° C (482-572°F)
Pressure: 238 kPa (2.5 atm)
Catalyst: Copper on silica
4. Utilities - Not available
5. Waste streams - the major waste water stream is from the steam
stripper for the aqueous layer and contains approximately 0.2%
toluidine as well as some HC1. Some toluidine hydrochloride is
lost in the waste water from the reactor after steam distillation.
Air streams contain hydrogen chloride and some particulates.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 79, 421.
Ibid., Vol. 13 (1967} p. 852.
Kent, J. A., Riegel's Handbook of Industrial Chemistry, 7th
Edition, Van Nostrand-Reinhold Company, New York, N.Y., 1974.
6-788
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 342
Dinitrobenzoic Acids
COOH
(N02) --H IVjJ—
22
1. Function - 2,4-Dinitrotoluene and 2 , 6-dinitrotoluene are obtained
by the dinitration of toluene by conventional nitrating process.
The corresponding benzoic acids may be obtained by nitrating in the
presence of CrO_ or Na2Cr?07.
2. Input Materials
Toluene
3. Operating Parameters
Temperature: 0°C (32°F)
Pressure: 101 kPa (1 atm)
Time: 1 to 2 hr
4. Utilities - not given
5. Waste Streams - Typical nitration waste streams (NO , spent acid)
~"~ X
should be present as well as some chromium salts in the sludge.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer , Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y. , Vol. 13 (1967), p. 851.
6-789
-------
7. References (continued)
Tadeuz, Urbanski, et al., Biul. Wojskowej Akad. Tech. 9, No. 97,
73-83 (1960).
Adolph, E. et al., Tetrahedron, 19(6), 801-7 (1963).
6-790
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 343
2,4- and 2,6-Diaminotoluenes
1. Function - The usual industrial dinitration of toluene gives a
mixture of 2,4- and 2,6-dinitrotoluenes in a 80:20 ratio. A
conventional liquid phase hydrogenation yields the 2,4- and
2 , 6-diamino toluenes . The mixture of the diamines is used to
manufacture the corresponding diisocyanates used in urethane
manufacture.
2. Input Materials
Dinitrotoluenes - 1.57 kg/kg Diaminotoluenes
Hydrogen - 0.106 kg/kg Diaminotoluenes
3. Operating Parameters
Temperature: 90-190°C (194-374°F)
Pressure: 606 kPa (6 atm)
Catalyst: palladium on carbon
Phase: liquid
Reactor type: jacketed kettle
Solvent: water
4. Utilities - Basis: 9.41 Gg (20.75 M lb)/yr. capacity (based on
DuPont patents)
3
Cooling water - 568 m (150,000 gal.) /hour
3
Demineralized water - 681 m (180,000 gal.) /hour
Steam - 5.94 Mg (13,100 lb)/hour
Fuel - 5.9 GJ (5.6 M BTU)/hour
Electricity - 634 MJ (176 kWh)/hour
6-791
-------
5. Waste Streams
Recovery section (water), Toluidlne - 11 gm/kg Diaminotoluenes
Purification section (water), Toluenediamine - 9.8 gm/kg
Diaminotoluenes
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience
Publishers, New York, N.Y., 2nd Edition, Vol. 20 (1969), p. 562.
Yen, Y. C., Isocyanates - Part I, Report No. 1-A, Stanford Research
Institute, Menlo Park, California, June 1968.
Sittig, M., Organic Chemical Process Encyclopedia - 1969, Noyes
Development Corp., Park Ridge, N.J., 1969.
Albright, Lyle F., and Hanson, Carl, "Industrial and Laboratory
Nitrations", ACS Symposium Series 22, 1976, p. 314.
6-792
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 344
m-Chlorotoluene
NaNO,
CuCl
+ N,
1. Function - m-Chlorotoluene is made by the replacement of the amino
group of m-toluidine with a chlorine by formation of a diazonium
salt and the reaction of the diazonium salt with cuprous chloride.
The reaction is carried out by dissolving the m-toluidine in a 2.5X
excess of aqueous hydrochloric acid containing the cuprous chloride.
A solution of sodium nitrite is added giving nitrous acid in situ.
The product is insoluble in water and separates as a nonaqueous
layer. Purification is accomplished by distillation. Urea may be
added to remove excess nitrous acid.
2. Input Materials - Basis: 1 kg m-chlorotoluene
meta-Toluidine - 0.85 kg
Hydrochloric acid (2.5X excess)
Sodium nitrite
Cuprous chloride
3. Operating Parameters
Temperature: 0.5°C
Pressure: 100 kPa (1 atm)
4. Utilities - Not available
5. Waste Streams - Air vent streams contain hydrogen chloride, nitrogen,
nitric oxide and nitrogen dioxide. Waste water streams contain
hydrochloric acid, m-toluidine hydrochloride, some copper salts and
small quantities of m-chlorotoluene.
6-793
-------
6. EPA Source Classification Code - None
7. References
Astle, M. J., Industrial Organic Nitrogen Compounds, Reinhold
Publishing Corp., New York, 1961, p. 198-200.
6-794
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 345
o- and p-Chlorotoluenes
CH
Cl
1. Function - Ortho-and para-chlorotoluenes are prepared by direct
catalytic chlorination of toluene. The reaction is carried out in
a liquid phase reactor at a temperature of 110-130°C and 1 atmos-
phere pressure, in the presence of iron powder to facilitate ring
chlorination. By-products of the reaction are dichlorotoluenes
and higher chlorinated derivatives. These are separated from the
mono-chloro products by distillation. The o- and p- isomers are
separated by fractional crystallization.
2. Input Materials - Basis: 1 Kg chlorotoluene
Toluene - .91 Kg/Kg
Chlorine - .70 Kg/Kg
Iron Turnings
Sodium hydroxide (10% aqueous to neutralize chlorinated toluenes)
3. Operating Parameters
Temperature - 110-130°C
Pressure - 100 kPa (1 atm)
4. Utilities - Not available
5. Waste Streams - Air vent streams contain chlorine, hydrogen chloride
and some toluene. Vent on absorber emits chlorine, some toluene.
Water from decanter contains sodium hydroxide, sodium chloride some
dichlorotoluenes. Vent stream from stripping column contains
toluene.
6-795
-------
6. EPA Source Classification Code - None
7. References
Faith, W.L. et al., Industrial Chemicals, 3rd Edition, John Wiley
and Sons, New York, N.Y., 1965, p. 261-263.
Sittig, M., Pollution Control in the Organic Chemical Industry,
Noyes Data Corporation, Park Ridge,N.J., 1974, p. 103.
6-796
-------
INDUSTRIAL ORGANIC CHEMICALS
p-Chlorobenzaldehyde
HCC1
+ Cl
PROCESS NO. 346
HCO
Function - p-Chlorobenzaldehyde is produced by hydrolyzing p-
chlorobenzalchloride, a side chain chlorination product of p-
chlorotoluene. p-Chlorotoluene is chlorinated at 160°C and
1 atmosphere pressure in a glass lined reactor, to prevent metal
catalyzed ring chlorination. The extent of chlorination is
estimated by measuring the density of the reaction product.
This method of control results in by-product of chlorobenzylchloride
and chlorobenzotrichloride.
The crude chlorobenzal chloride is hydrolyzed by boiling water
yielding chlorobenzaldehyde and by-products of chlorobenzylalcohol, and
chlorobenzoic acid.
Input Materials - Based on 1 Kg chlorobenzaldehyde
Chlorotoluene - 0.9 Kg
Chlorine - 70.5 Kg
Water - 70.13 Kg
Operating Parameters
Temperature - 160°C
Pressure - 100 kPa (1 atm)
Utilities - Not given
6-797
-------
5. Waste Streams - Vent on gas absorber emits hydrogen chloride and
chlorine. Waste water streams may contain hydrochloric acid,
benzoic acid, chlorobenzylalcohol and some chlorobenzaldehyde.
Because the heat of reaction for the chlorination is controlled
by the reflux of chlorotoluene some chlorotoluene vapors may be
emitted.
6. EPA Source Classification Code - None
7. References
Faith, W.L. et al., Industrial Chemicals, 3rd Edition, John Wiley and
Sons, New York, N.Y., 1965, p. 120,121.
6-798
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 347
Chlorobenzoic Acids (o- and p-)
CC1,
+ 3C1,
Fe
CC1,
+ 3HC1
+ 3HC1
Function - Chlorobenzoic acids may be prepared by a variety of
methods based on well-known reactions. The ortho and para acids
can be made from o-chlorotoluene and p-chlorotoluene, respectively,
by chlorinating the substituted toluene in the side chain to the
chloro-benzotrichloride stage (indicated by the density of the
reaction product), and then hydrolyzing.
Mixed o, p-acids are manufactured by reacting mixtures of o,
p-chlorotoluenes. The meta acid can be made by direct chlbrination
of benzoic acid.
Input materials - Basis: 1 kg p-chlorobenzoic acid
p-chlorotoluene - 0.81 kg
Chlorine - >1.3 kg
6-799
-------
Water - >0.23 kg
Catalyst - quantity not given
3. Operating parameters
Temperatures: 160°C chlorination; 100°C hydrolysis
Pressure: 100 kPa (1 atm)
Catalyst: zinc chloride
4. Utilities - none available
5. Waste Streams - Hydrogen chloride is emitted from the vent in
the gas absorber, possibly some chlorine is also emitted. Waste
water streams may contain sodium hydroxide, sodium chloride,
sodium chlorobenzoate, zinc chloride and by-products of chloro-
benzaldehyde and chlorobenzylalcohol depending upon the purity of
the chlorobenzotrichloride hydrolyzed.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, Vol. 3 (1967), pp. 436-437.
Faith, W. L., D. B. Keyes and R. L. Clark, Industrial Chemicals,
3rd Edition, John Wiley and Sons Inc., New York, 1965, pp. 141-142.
6-800
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 348
Chlorobenzoyl Chlorides (o- and p-)
HC1
COOH
COC1 + HC1
1. Function - Chlorobenzoyl chloride Is made by the reaction of chloro-
benzoic acid and chlorobenzotrichloride. This may be operated as
part of the process for producing benzole acid. The product, benzole
acid, is mixed with unhydrolyzed benzole acid precursor, chloro-
benzotrichloride and heated.
2. Input Materials
Chlorobenzoic acid
Chlorobenzotrichloride
3. Operating Parameters
Temperature: 150-250°C (302-482°F)
Pressure: 100 kPa (1 atm)
4- Utilities - Not available
5. Waste Streams - Vent from gas absorber emits some hydrogen chloride
and chlorine. Bottoms from the distillation column contain unreacted
chlorobenzoic acid and chlorobenzochloride.
6. EPA Source Classification Code - None
7. References
Staff, Chemical Origins and Markets, Chemical Information Services,
Stanford Research Institute, Menlo Park, California (1967), p. 21.
6-801
-------
References (continued)
Hahn, A. V., The Petrochemical Industry, McGraw-Hill Book Co.,
New York, (1970), p. 518.
6-802
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 342
Benzene and Xylenes (disproportionation; hydrodealkylation)
92% H9^r 1 + — (CH3)2 (1)
+ CH, (2)
80% H2 ^ •* "
1. Function - Benzene and xylene are formed by the disproportionation
of toluene. Benzene can be produced by the hydrodealkylation (2)
of toluene. Both of these processes are becoming increasingly
important because of the rising demand for benzene in industry. Petrol-
eum stocks have been the principal sources of benzene in recent
timesj hut the ratio of benzene/toluene/xylenes produced by the
catalytic reformer processes is almost exactly opposite to the
demand for these products. It was necessary therefore to develop
process to produce benzene from toluene and xylene. Both catalytic
and thermal processes are employed.
There are four major processes used to convert alkyl benzenes
to benzene: Howdry (a fixed bed catalytic process), Hydeal
(catalytic dealkylation) , Hydrodealkylation, and the Thermal
Hydrodealkylation (a non-catalytic, elevated temperature and
pressure) .
2. Input Materials
Hydrogen
Toluene
C0 Aromatics
o
Alkylbenzenes
6-803
-------
3. Operating Parameters
Detol: temperature - 538-649° C (1000-1200° F)
pressure - 3.5-8.3 MPa (34-82 atm)
catalyst - poison resistant, non-noble metal
compound pellets
Hydeal: Not given
Hydrodealkylation: temperature - 593-760° C (110-1400° F)
pressure - 3.5-7.0 MPa (34-68 atm)
THD: Not given
4* Utilities - disproportionation of toluene
Electric power - 263 MJ (73 kWh)
Steam - 1.2 Mg (1.5 short tons)
Cooling water (AT 10° C) - 2.1 Mg (3.6 short tons)
Fuel - 2.0 GJ (0.7 x 106 kcal)
5. Waste streams - C- aromatic hydrocarbon plus diphenyl and higher
condensed aromatics as bottoms. Lighter paraffins and olefins
as overhead or raffinate. By-product formation 29 kg (64 lb)/
1000 kg (metric ton) product.
6. EPA Source Classification Code - None
7. References
Anon., "Detol," "Hydeal," "Hydrodealkylation," and "Thermal
Hydrodealkylation," Pet. Refiner, 40(11), 236, 251, 252, 298 (1961),
Mager, E. M., "Aromatics Production," U.S. Petrochemicals,
Technologies, Markets, and Economics, Brownstein, A. M., Ed.,
The Petroleum Publishing Company, Tulsa, Okla., 1972, pp. 123-125.
6-804
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 350
Methylcyclohexane
3
, „ catalyst .
1. Function - Methylcyclohexane is produced commercially by the
catalytic reduction of toluene. Since the reaction is catalyzed
by Raney nickel, a catalyst which is severly poisoned by sulfur
compounds, it is necessary to desulfurize the toluene or to use
sulfur-free toluene as the starting material. The reaction is
carried out in the liquid phase at 220° C and pressures of 25-
34 atm. It is usually carried out in a series of reactors to
reduce the amount of recycle, cooling methylcyclohexane in order
to avoid excessive catalyst bed temperatures which can lead to
isomerization.
2. Input Materials
Toluene
Hydrogen
3. Operating Parameters
Temperature: 220° C to 270° C (428-518° F); average
conditions 220° C (428° F)
Pressure: 2.5-3.6 MPa (25-34 atm)
Catalyst: Supported nickel or platinum catalyst
4. Utilities - Not given
5. Waste Streams - rearrangement by-products such as dimethylcyclo-
pentanes, ethylcyclopentanes, and paraffinic residues as still bottoms
or overheads.
6-805
-------
6. EPA Source Classification Code - None
7. Reference
Hydrocarbon Processing and Petroleum Refiner .40(11^. 234, 1961.
6-806
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 351
Methylcyclohexanol
1. Function - Large scale manufacture of methylcyclohexanol employs
the oxidation of methylcyclohexane. The process can start by
the direct oxidation of methylcyclohexane. The oxidation is most
preferably carried out in the presence of metaboric acid, although
other special boron compounds can be used. Oxygen reacts with
methylcyclohexane to form methylcyclohexyl hydroperoxide, which
on reaction with metaboric acid is believed to form a peroxyborate.
This peroxyborate is thought to react subsequently to make cyclohexyl
borate esters. Caustic may be used in neutralization of product.
The water of reaction must be maintained at very low levels or
product yield is decreased. The process for producing methyl-
cyclohexanol is similar, if not identical, in some cases to that
used to produce cyclohexanol. Methylcyclohexanol is also pro-
duced by the hydrogenation of o, p-cresols.
2. Input Materials - Basis: 1 kg methylcyclohexanol
Methylcyclohexane - 0.98 kg
Oxygen - 0.16 kg
Metaboric acid - quantity not given
Caustic - quantity not given
3. Operating Parameters
Temperature: 185 - 200°C (365-392°F)
Pressure: 2040 - 4800 (20 - 47 atm)
Catalyst: boric acid or none (5% of Hydrocarbon)
6-807
-------
4. Utilities - Quantities not given
5. Waste Streams - The principal source of air pollution occurs during
the removal of the water of reaction by azeotropic distillation
of cyclohexane-water. Boric acid is recovered and cyclohexane is
recycled. Some cyclohexane may be present in the air vent streams.
Spent caustic from hydrolysis of borate esters as well as small
quantities of cyclohexanol will be present in the waste process
water.
6. EPA Source Classification Code - None
7. References
Considine, D.M., Chemical and Process Technology, McGraw-Hill
Book Company, New York, 1974, pp. 337-338.
Sittig, M., Organic Chemical Process Encyclopedia 1969, 2nd Edition,
Noyes Development Corporation, Park Ridge, New Jersey, 1969, p. 203.
Waddams, A.L., Chemicals from Petroleum, 3rd Edition, John Murray,
London, 1973, p. 240-241.
6-808
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 352
Me thylcyclohexaaene
CH,
_/ \-OH + 1/2 o2 -£2i:—+- CH3-\ Vo + H2
1. Function - Conmercial processes employ air oxidation of methylcyclo-
hexanol to produce methylcyclohexanone.
The reaction occurs in a fixed bed multitubular reactor in the
vapor phase. A silver or copper catalyst is used.
2. Input Materials - Basis - 1 kg methylcyclohexanone
Methylcyclohexanol - 1 kg
Air - >0.14 kg
Catalyst - quantity not given
3. Operating Parameters
Temperature: ~630°C (1166°F)
Pressure: atmospheric
Catalyst: silver or copper
4. Utilities - Not given
5. Waste Streams - No specific information was found. Gaseous emissions
would include methylcyclohexanol, methylcyclohexanone, and a host
of by-products from side reactions depending on catalyst efficiency.
The condensed water which is separated and disposed of may contain
methylcyclohexanone as well as other organic impurities from the
high temperature oxidation.
6-809
-------
6. EPA Source Classification Code - None
7. References
Sittig, M., Organic Chemical Process Encyclopedia, 2nd Edition,
Noyes Development Corporation, Park Ridge, N.J., (1969), p. 433.
U.S. Patent 2,930,679 (March 29, 1960).
6-810
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 353
Benzaldehyde
+ 02(air)
CHO
Cat.
!• Function - Toluene can be directly oxidized in the vapor phase
to benzaldehyde by using a mixture of air and toluene vapors
(14:1 weight ratios) in the presence of a 93% uranium oxide,
7% molybdenum oxide catalyst. Small amounts of CuO are added
to minimize oxidation to maleic anhydride.
Direct oxidation of toluene is not the only process used.
Some quantities are manufactured by hydrolyzing benzal chloride.
2. Input Materials - Basis: 1 kg Benzaldehyde (direct oxidation
route)
Toluene - 2.2 kg
Air - 30.2 kg
Catalyst - quantity not given
3. Operating Parameters
Temperature: 500°C (932°F)
Pressure: 101 kPa (1 atm)
Catalyst: molybdenum oxide - 7%/uranium oxide - 93% with
cuprous oxide
4* Utilities - quantities not given
5. Waste Streams - By-products such as benzoic acid, maleic anhydride,
CO, C0», anthraquinone, and high boiling oils; scrubber wastes.
6. EPA Source Classification Code - None
6-811
-------
7. References
Faith, W- L., et al., Industrial Chemicals, John Wiley and Sons,
Inc., New York, N.Y., 3rd Edition, 1965, p. 120-124.
Hahn, A. V., The Petrochemical Industry; Market and Economics,
McGraw-Hill Book Co., New York, N.Y., 1970, p. 519-518.
6-812
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 354
Benzoin
JCHO
KCN
EtOH
1. Function - Benzoin is manufactured by the reductive condensation of
benzaldehyde in an alkaline cyanide solution. The reaction occurs in
the liquid phase in alcohol (commonly ethyl alcohol) which will
solubilize benzaldehyde, cyanide,and benzoin. The reaction is carried
out at reflux conditions.
2. Input Materials - Basis - 1 kg benzoin
Benzaldehyde - 1 kg
Potassium cyanide catalyst - quantity unknown
3. Operating Parameters
Temperature - 80°C (reflux temperature of ethyl alcohol) (176°F)
Pressure - 101 kPa (1 atm)
Time for reaction - 1-3 hours
Catalyst - potassium cyanide
4- Utilities - Not given
5. Waste Streams - The reflux of ethyl alcohol to control the heat of
reaction may cause the presence of ethanol and HCN in the vent streams.
Potassium cyanide, ethanol, and benzaldehyde will be found in the waste
water streams.
6. EPA Source Classification Code - None
6-813
-------
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 3 (1967), p. 365.
6-814
-------
INDUSTRIAL ORGANIC CHEMICALS
Benzil
CuSO,
aq. Py.
PROCESS NO. 355
1. Function - The a-diketone benzil is obtained in high yield by oxidation
of benzoin with nitric acid in acetic acid solution or with copper
sulfate in aqueous pyridine. Reaction occurs at reflux conditions.
2. Input Materials - Basis: 1 kg benzil
Benzoin - 1 kg
CuSO., pyridine - quantities not given
Water or HNO
Acetic acid
3. Operating Parameters
Temperature - 230°C (reflux condition) (446°F)
Pressure - 101 kPa (1 atm)
Catalyst - CuSO,
4. Utilities - Not given
5. Waste Streams - Pyridine, acetic acid, HNO™, as well as products and
reactants may be present in wastewater. The reaction occurs at reflux.
Thus, pyridine, acetic acid, and nitric acid may be present in vent gas\
6. EPA Source Classification Code - None
6-815
-------
7. References
Kirk~0thmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishing Co., New York, N.Y., Vol. 12 (1967), p. 146-147.
U. S. Pat. 2,377,749 (June 5, 1945).
6-816
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 356
Benzilic Acid
KOH HO-C-
140°C
P
1. Function - Benzilic acid is produced from benzil by a base catalyzed
»
rearrangement. The reaction is run in water at slightly elevated
pressure and a temperature of 140°C (melting point of benzil = 137°C).
Alternately a sodium hydroxide-sodium bromate catalyst mixture is
employed at a temperature of 85-90°C and ambient pressure.
At the conclusion of the reaction (4-5 hours) the sodium salt
of benzilic acid is neutralized with hydrochloric acid and crystallized
from the solution as it cools to room temperature. The product
separated after washing, is of sufficient purity for use in most
applications. Crystallization from benzene can be employed to produce
a benzilic acid of superior purity.
2. Input Materials
Potassium hydroxide - 0.2 kg
Benzil - 1 kg
Hydrochloric acid - 0.16 kg
3. Operating Parameters
Temperature - 140°C
Pressure - Not given
4. Utilities - Not given
6-817
-------
5. Waste Streams - Air vent streams may contain some hydrogen chloride.
Waste water contain potassium chloride, potassium hydroxide, sodium
benzilate, minor amounts of benzilic acid.
6. EPA Source Classification Code - None
7. References
Doering and Urgan, J. Am. Chem. Soc., 78, 5938 (1956).
Ballard, D. A., and Dehn, W. M., Org. Syn. Coll., Vol. 1, 89 (1941).
6-818
-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 357
p-Toluenesulfonyl Chloride
+ so.
J3
(oleum)
PC1
+ POC1- + HC1
1. Function - p-Toluenesulfonyl chloride is produced, industrially
from toluene, oleum and phosphorus pentachloride. The first stage
produces p-toluenesulfonic acid. Toluene and oleum are combined
to give o- and p-toluene sulfonic acid. The p-isomer is favored
at higher temperatures, however the o-isomer can be isomerized to
the p- by heating to 140°C. The solution is neutralized with
or BaCO,, percipitating BaSO. and leaving the sulfonic acids in
solution from which they are recovered by crystallization.
The sulfonic acids are converted to the sulfonyl chlorides
through the action of phosphorous pentachloride. The use of PCI-
instead of Cl« obviates the need for non-ferrous reaction vessels
and reaction in the absence of light.
An alternate route to p-toluenesulfonyl chloride is also a two
step process using chlorosulfonic acid as both the sulfonating and
the chlorinating reagent.
C1S03H
6-819
+ HC1
-------
so2ci
An excess of chlorosulfonic acid is used to drive the reaction
to completion.
2. Input Materials - Basis - 1 kg p-toluenesulfonyl chloride (SO^, PClj
route)
Toluene - 0.48 kg
Oleum - 2.1 kg
PC15 - .31 kg
3. Operating Parameters
Temperature: sulfonation - 30-40°C (86-104°F)
chlorination - 80°C (176°F)
Pressure: 100 kPa (1 atm)
4. Utilities - Not given
5. Waste Streams - The air vent stream from the gas absorber will con-
tain hydrogen chloride. Barium sulfate and. phosphate will precipi-
tate on neutralization of the sulfonating solution. Waste wash water
streams may contain small amounts of sulfuric and phosphoric acids
and their salts as well as p-toluenesulfonic acids.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 19 (1969), p. 298-99.
Chemical Technology, Barnes and Noble Books, New York, N.Y.,
Vol. 4 (1972), p. 595, 612.
6-820
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 358
p-Toluenesulfonamide
/^\
S02NH2 + NH4C1
1. Function - Toluenesulfonamide is prepared by reacting toluenesulfonyl
chloride with ammonia*
2. Input Materials - Basis: 1 kg toluenesulfonamide
Ammonia - 0.1 kg
Toluenesulfonyl chloride - 1.1 kg
Catalyst - quantity not given
3- Operating Parameters
Temperature: room temperature or lower
Pressure: atmospheric
4. Utilities
Quantities not given
5. Waste Streams - Hydrogen chloride may appear in the air vent streams as
well as ammonia although most of the HC1, reacts with the excess ammonia
gas used, to form ammonium chloride. The NH.C1 will be present in the
waste water streams as well as small amounts of toluenesulfonamide.
6. EPA Source ClassificationCode
None
7. Reference
Chemical Technology. Barnes and Noble Books, New York, N.Y., Vol. 4
(1972), p. 611-613.
6-821
-------
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,
Interscience Publishers, New York, N.Y.., Vol. 19 (1969), p. 255-260.
6-822
-------
SECTION X
XYLENES
6-823
-------
XYLENES
XYLENES
CX>
NJ
-e-
359
\
/
\
/
X
} Ethylbenzene
^ o-Xylene
^p-Xylene-
360
361
-> Phthalic anhydride
Isophthalic acid
362 A.B
*
Terephthallc acid * Dimethyl.Terephthalate
Xyienes — ) Nitroxylenes ^Xylidines
Figure 19. Xylenes Section Chemical Tree
-------
cr>
I
oo
K3
Ul
1
I Xylenes I
if
Nitration 363
XI
1 *
Reduction
364
I p-Xylene J
Water
Acetic acid
[Air .
Oxidation
362 A.B
Tere-
phthalic
. acid & .
Dimethyl Terephthaiate
Acetic acid
Cooling water
III
Air
* ./*
360
Oxidation
XI
Ethyl-
benzene
Figure 20. Xylenes Section Process Flow Sheet
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 359
o-t m-, and p-Xylenes and Ethyl Benzene
1. Function - Over 90% of the domestic production of xylenes is the
result of catalytic reforming or hydroforming of certain petrol-
eum fractions. Disproportionation and transalkylation of toluene
is a minor source of xylenes. A typical cut of C0 stock has the
o
following composition:
ethyl benzene
p-xylene
m-xylene
o-xylene
Wt. % in
distillate
9-13%
17-20%
45-53%
18-24%
M.P., °C
-95.0
13.2
-47,9
-25.2
B.P., °C
136.2
138.4
139.1
144.4
By a process termed super-fractionation, ethyl benzene (99.7%
purity) can be separated from the xylenes. In addition, o-xylene
can be separated from the other xylenes by fractional distillation.
The differences in melting points allow for practical separa-
tion of the m- and p-isomers.
The dried feedstock (^ 10 P.P.M. H20) is cooled to -40°C and
passed to a crystallizer at -62°C to -66°C. Crystals of p-xylene
formed are centrifuged, partially melted and recrystallized at
-31°C. The mother liquor (rich in m-xylene) can be recycled or
isomerized to yield more p-xylene.
Isomerization processes may employ a platinum on a silica-
alumina support as a catalyst. Isomerization occurs in the vapor
6-826
-------
phase in the presence of hydrogen at temperatures around 450°C
and pressures in the 10-25 atm range. The product of isomeriza-
tion is recycled to the crystallization unit.
Other processes of interest in the isolation of xylenes in-
clude:
1. Preferential adsorption of p-xylene on a solid absorbent
from a mixture of CQ aromatics (Parex process).
o
2. Separation of pure m-xylene via sulphonation, formation
of clathrates, or formation of an HF-BF3 complex.
3. Separation of m- and p-isomers by formation of Werner-
type complexes.
2. Input Materials
CQ aromatics
o
3. Operating Parameters
Separation of ethyl benzene
(Three 200 ft column in series containing 350 plates. Reflux ratio
25:1 to 50:1.)
Crystallization (p-xylenes)
1st - Temperature: -62°C-66°C (144-151°F)
Pressure: not given
2nd - Temperature: -31°C (88°F)
Pressure: not given
Isomerization
Temperature: -450°C (842°F)
Pressure: 1.01-2.53 MPa (10-25 atm)
Catalyst: Platinum on a silica-alumina support
6-827
-------
4. Utilities
Distillation of ethylbenzene and o-xylene: Not given
Crystallization of p-xylene (Chevron Process, Crude Feed)
Basis: 45.4 Og/yr (100 M lb/yr) capacity
o
water - 40 dm /s (600 gpm)
steam - 2.3 Gg/hr (5 M Ib/hr)
power - 10.8GJ (3,000 kWh)
Isomerization of m-xylene (alumina-silica catalyst, Crude Feed)
Basis: 45.4 Gg/yr (100 M lb/yr) capacity
3
water - 44 dm /s (700 gpm)
steam - 7.3 Mg/hr (16,000 Ib/hr)
power - 1.4 GJ (400 kWh)
fuel - 30 MW (100 M Btu/hr)
5. Waste Streams
Distillation - Not given.
o
Crystallization - Sludge 0.3-1.7 m /Mg (100-500 gallons/ton of
3
p-xylene) containining 3g-5kg/m (3-5,000 mg/1)
of organic material is produced.
Isomerization - Separator has an off-gas vent that would expel
organic vapors.
6. EPA Source Classification Code - None.
7. References
Brownstein, A. M., U. S. Petrochemicals, The Petroleum Publishing
Company, Tulsa, Oklahoma, 1972.
Gloyna, E. F., and Ford, D. L., "The Characteristics and Pollution
Problems Associated with Petrochemical Wastes", for TWPCA, Contract
No. 14-12-461, February, 1970.
6-828
-------
Ries, H. C., "Xylenes Separation", Report No. 25, Stanford Research
Institute, Menlo Park, California, 1967.
Anon., "Development Document for Effluent Limitations Guidelines
and Standards of Performance", prepared for Environmental Protection
Agency, Contract No. 68-01-1509, June, 1973.
Austin, G. T., "The Industrially Significant Organic Chemicals -
Part 9", "Chemical Engineering,"August 5, 1974, p. 99.
Waddams, A. L., Chemicals From Petroleum, 3rd Edition, John Wiley
and Sons, New York, N. Y., 1973, p. 209-221.
6-829
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 360
Phthalic Anhydride (from o-xylene)
!• Function - Phthalic anhydride (PAN) is manufactured by air oxida-
tion of o-xylene in a fixed catalyst bed reactor. Oxidation is
achieved by feeding the mixture of vaporized o-xylene and preheated
air (1:10) to a reactor containing a V?0,- based propietary catalyst.
The reaction takes place at a temperature of V550°C with a contact
time of the order of .10 to .15 seconds. Heat is removed by cir-
culating molten salts across the reactor. Many plants can operate
at will on o-xylene or naphthalene feedstock.
The vapors leaving the reactor are condensed, then melted and
fed into a pre-decomposer. In the pre-decomposer maleic and benzoic
acid are removed and any phthalic acid present is dehydrated.
Final purification is done by distillation in vacuum.
2. Input Materials
o-xylene 975 kg/metric ton product
air 25,000 m at 15°C/metric ton product
3. Operating Parameters
Temperature: 550°C (1022°F)
Pressure: not given
Catalyst: propietary catalyst based on 7,0,.
£ .J
Contact Time: 0.10 to 0.15 sec
Av. Plant Capacity: 18 to 45 million kg/yr
6-830
-------
4. Utilities - not given
5. Waste Streams - Waste gas - Most waste gas is scrubbed with water.
Removal rates have been shown to be in excess of 99% of all organic
acids, however total aldehydes removal is poor with concentrations
in the effluent varying between 8 and 26 ppm as formaldehyde.
The scrubbing water discharges at 115 - 130°F with 1.7 - 2.5% total
acidity as maleic acid.
A phthalic anhydride plant producing 100 million pounds of PAN
a year could have a scfubbet effluent with an ultimate oxygen
demand of from 400 to in excess of 1200 Ibs/hr.
6. EPA Source Classification Code - None
7. References
Sittig, M., Pollution Control in the Organic Chemical Industry,
Noyes Data Corp., Park Ridge, N. J., 1974, p. 186-188.
Fawcett, R. L., "Air Pollution Potential of Phthalic Anhydride
Manufacture," Journal of the Air Pollution Control Associationr JO
(7): 461-465, 1970.
M
Austin, G. T., "Industrially Significant Organic Chemicals - Part 8,
"Chemical Engineering", July 22, 1974, p. 109-110.
"1973 Petrochemicals Handbook", "Hydrocarbon Processing", November,
1973, p. 159-160.
Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Wiley
and Sons, New York, N. Y., 1973, p. 228-230.
Lowenheim, F. A. and Koran, M. K., Industrial Chemicals, 4th Edition,
John Wiley and Sons, New York, N. Y., 1975, p. 661-664.
6-831
-------
Hedley, W- H. et al., "Potential Pollutants from Petrochemical
Processes", Prepared for Control Systems Laboratory, NERC, Environ-
mental Protection Agency, Contract No. 68-02-0226, Task No. 9,
1973, p. 95-96.
6-832
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 361
OOH
CH3
1. Function - As of 1971 Amoco and Arco were the only two producers of
isophthalic acid in the U.S. In the Amoco process m-xylene is oxi-
dized in the liquid phase at 150-250°C and a pressure of 15-30 atm.
Air is used as the oxidizing agent and the reaction is carried out
in acetic acid as solvent, in the presence of a bromine-promoted
cobalt salt as catalyst. The isophthalic acid produced will con-
tain varying amounts of terephthalic acid depending on the purity
of the m-xylene feedstock.
2. Input Materials
m-xylene
Acetic acid
Catalyst
3. Operating Parameters
Temperature: 150-250°C (301-481°F)
Pressure: 1.52-3.04 MPa (15-30 atm)
Catalyst: cobalt salt activated by bromine
4. Utilities - not given
5. Waste Streams - Potential water wastes are IPA, terephthalic acid,
and acetic acid.
6. EPA Source Classification Code - None
6-833
-------
7. References
Hedley, W. H., et. ai,, Potential Pollutants from Petrochemical
Processes, Prepared for Control Systems Laboratory, NERC, Environ-
mental Protection Agency, Contract No. 68-02-0226, Task No. 9,
1973.
Waddams, A. L., Chemicals From Petroleum, 3rd Edition, John Wiley
and Sons, New York, N, Y,, 1973 , p. 232-235.
6-834
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 362.A.B
Terephthalic Acid and Dimethyl Terephthalate
COOH
^ "X
o.
COOH
1. Function - Terephthalic acid (TPA) is produced by the air oxidation
of p-xylene in the liquid phase.
p-Xylene dissolved in acetic acid reacts with air in the pre-
sence of a cobalt proprietary catalyst in a reactor at 200°C and
400 p.s.i. The hot slurry from the reactor effluents is fed into a
crystallizer. Acetic acid, unreacted p-xylene and water are removed
at this step and by further centrifugation. Acetic acid and p-
xylene are recycled. The crude TPA is leached with acetic acid at
high temperature. The resulting TPA of better than 99% purity is
washed with hot water to remove traces of catalyst and acetic acid.
Subsequent hydrogenation in fixed-bed reactors, crystallization and
drying yield fiber grade TPA. A new route to TPA involves the
ammoxidation of p-xylene and the subsequent hydrolysis of terephthalo-
nitrile to terephthalic acid. The Hercules-Witten process produces
dimethyl terephthalate from p-xylene without isolation of TPA.
2. Input Materials
p-xylene - 680 kg/metric ton polymer grade TPA
air - not given
acetic acid - not given
6-835
-------
3. Operating Parameters
Temperature: 200°C (392°F)
Pressure: 2.76 MPa (27.2 atm)
Catalyst: Bromine promoted cobalt catalyst
4. Utilities - not given
5. Waste Streams - Off-gas from scrubber contain some organic vapors;
wastewaters contain acetic acid, traces of catalyst, and terephth-
alic acid.
/ *3
Water flow rate - 3.62 x 10~ - 9.09 x 10~ m/kg
(86.8 - 2180 gal/ton)
COD 5,400 - 24,950 g/m3 (1.95 - 227 lb/1000 Ib)
BOD5 3,600 - 7,500 g/m3 (1.30 - 68.3 lb/1000 Ib)
TOG 4,200 - 3,730 g/m3 (1.52 - 34 lb/1000 Ib)
6. EPA Source Classification Code - None
7. References
Sittig, M., Pollution Control in the Organic Chemical Industry
Noyes Data, Park Ridge, N.J., 1974, p. 198-203.
"1973 Petrochemical Handbook", "Hydrocarbon Processing", November,
1973, p. 183-185.
Hedley, W. H., et. al., Potential Pollutants in the Petrochemical
Processes, Prepared for Control Systems Labotatory, NERC, Environ-
mental Protection Agency, Contract No. 68-02-0226, Task No. 9,
1973.
Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Wiley
and Sons, 1973, p. 232-237.
6-836
-------
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th
Edition, John Wiley and Sons, 1975, p. 807-813.
6-837
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 363
Nitroxylen.es
GIL
1. Function - Xylenes, o-, m- or p-isomers, can be nitrated to place nitro
groups on the benzene ring. Ortho-xylene gives the 4-nitro and the
4,6-dinitro isomers; meta-xylene gives the 4-nitro isomer, and para-
xylene the 2,3-dinitro-or 2,6-dinitro-p-xylene, or the 2-nitro-p-xylene.
The extent of nitration, the number of nitro groups placed in the
ring, is a function of acid strength and temperature. The extent of
side chain oxidation is dependent on the same two factors; therefore,
with polynitrated products a compromise must be reached.
Mononitration of xylenes is carried out near room temperature,
25°C (77°F) with a mixture of nitric 30% and sulfuric (55%) acids
and at atmospheric pressure.
2. Input Materials
Xylenes
Nitric-sulfuric acid mixture
3. Operating Parameters
Temperature - 25-40°C (77-104°F)
Pressure - 100 kPa (1 atm)
4. Utilities - Not given
6-838
-------
5. Waste Streams - Spent acid is recovered and recycled to the system.
Air emissions from the reactor may contain oxides of nitrogen. Waste
water from the product washing procedure contains sodium carbonate,
some nitroxylenes and nitrate salts.
6. EPA Source Classification Code - None
7. References
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, N.Y., Vol. 22 (1970), p. 484.
Chemical Technology, Barnes and Noble Books, New York, N.Y.,
Vol. 4 (1972), p. 172-174.
6-839
-------
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 364
Xylidines (reduction of nitroxylenes)
catalyst __
2 + H2
\
3
1. Function - The xylidines are made by the reduction of nitroxylenes.
The only technical process used at present is hydrogen reduction.
A molybdenum sulfide catalyst is used for this reaction.
2. Input Materials
Nitroxylenes
Hydrogen
MoS_ on an inert support
3. Operating Parameters
Temperature - 165-170°C (330-340°F)
Pressure - 20.7 MPa (205 atm)
Catalyst - MoS-
Nitroxylene feed - 0.44 vols/vol catalyst/hr.
Recycle feed - 1.2-1.6 vols/vol
Recycle gas - 80-85% H» and 0.6% H S
4. Utilities - Not given
5. Waste Streams - Waste water from product wash contains sodium carbonate.
Vents emit some hydrogen.
6. EPA Source Classification Code - None
7. Reference
Brown, C. L., and Smith, W. W., "Production of Xylidines by High Pressure
Hydrogenation," Ind. Eng. Chem.. Vol. 40, (1948), pp. 1538-42.
6-840
-------
APPENDIX A
INDUSTRIAL CHEMICALS AND SOLVENTS GLOSSARY
6-841
-------
Table A-l lists specific industrial compounds and their
uses. Also included are the major producers listed in
alphabetical order for each compound, the plant locations,
plant capacities, and total annual production where
available. Capacities given are for 1975 and total
chemical production is for the specific year noted.
Capacity and production estimates are given in millions
of kilograms per year (MM kg) and millions of pounds
per year (MM Ibs).
6-842
-------
References
1. Hawley, G. G. (ed.). The Condensed Chemical Dictionary. 8th Edition,
Van Nostrand Reinhold Company, 1971.
2. Staff. Directory of Chemical Producers - U.S.A. Chemical Information
Services, Stanford Research Institute, Menlo Park (California), 1975.
3. Staff. Chem. Sources. Directories Publishing Co., Flemington, New
Jersey, 13th Edition, 1972.
4. Staff. "Recession Stifles Output of Top 50 Chemicals." Chemical and
Engineering News, American Chemical Society, May 5, 1975, p. 31.
5. Staff. "Facts and Figures - The U.S. Chemical Industry." Chemical
and Engineering News, American Chemical Society, June 2, 1975, p. 33.
6-843
-------
Table A-l. INDUSTRIAL CHEMICALS AND SOLVENTS.
00
Acenaphthene
Acetal
Acetalde-
hyde
Acetaldol
Dye intermediate;
Pharmaceuticals;
insecticide; fungi-
cide; plastics
Solvent; cosmetics;
organic synthesis;
perfumes; flavors
Acetic acid; acetic
anhydride; n-butanol;
2-ethylhexanol; per-
acetic acid; pentaery-
thritol; pyridlnes;
chloral; 1,3-butylene
glycol; trimethyl-
propane manufacturing
intermediate
Rubber accelerators;
age resistors; synthesis;
perfumery; engraving; ore
flotation; solvent; sol-
vent mixture for cellu-
lose acetate; fungicides;
organic synthesis;
printer's rollers; cad-
mium plating; dyes;
drugs; dyeing assis-
tant; synthetic polymers
Manufacturer(s)z>^
Hoffmann - La Roche,
Inc., Burdick & Jackson
Labs., Inc., subs id.
Fritzche Dodge & Olcott
Inc.
Celanese Corp. -
Celanese Chem, Co., dlv.
Eastman Kodak Co. -
Eastman Chem. Products ,
Inc-, subsld, Texas
Eastman Co., div.
Monsanto Co. - Monsanto
Polymer & Petrochems. Co.
Publicker Indust. Inc.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Location(s)2*3
Muskegon, Mich.
1975
Capacity2
KM kg (MM Ib)
_
Total1*'5 '
production
MM kg (MM Ib)
for year of estimate
.
East Hanover, N.J.
Bay City, Tex.
Clear Lake, Tex.
Pampa, Tex.
Longview, Tex.
Texas City, Tex.
Philadelphia, Pa.
Norco, La.
Institute & South
Institute & South
Charleston, W. Va,
90.8 (200) 731.6 (1611.10-1970
227 (500)
2.3 (5)
2.3 (5)
2.3 (5)
90.3 (200)
Total •
67^.2 (1H85)
-------
Chemical
Table A-l. (Continued)
Manufacturer(s)2 »3 Location(s)2J3
1975
Capacity2
MM kg (MM Ib)
Total1**5
production
MM kg (MM Ib)
for year of estimate
00
4^
Ui
Acetamide Organic synthesis
(reactant, solvent,
peroxide stabilizer);
general solvent; lac-
quers ; explosives;
soldering flux;
hygroscopic agent;
wetting agent;
penetrating agent
Acetanilide Rubber accelerator;
inhibitor in hydro-
gen peroxide; stabilizer
for cellulose ester
coatings; manufacture of
intermediate (paranitro-
aniline, paranitroace-
tanilide, parahexylene-
diamine); synthetic cam-
phor; pharmaceutical
chemicals; dyestuffs;
precursor in penicillin
manufacture; medicine
(antiseptic)
Acetic Acetic anhydride, cellu-
acld lose acetate, and vinyl
acetate monomer; acetic
esters; chloroacetic
production of plastics;
Pharmaceuticals, dyes;
insecticides, photo-
graphic chemicals, etc.;
food additive (as vine-
gar) ; natural latex
coagulant; oil-well
acidizer; textile
printing
Heicos Inc.
Mallinckrodt, Inc. -
Indust. Chems. Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. Tennessee
Eastman Co., div.
Merck & Co. Inc. -
Merck Chem. Div.
Salsbury Labs
Syntex Corp. - Arapahoe
Chems. Div.
Borden Inc. - Borden
Chem. Div. Petrochems.
Celanese Corp. - Cela-
nese Chem. Co., div.
Eastman Kodak Co. -
Eastman Chem. Prod. Inc.,
subsid. - Tenn. Eastman
Co., div.
PMC Corp. - Chem. Group
Indust. Chem. Div.
Monsanto Co. - Monsanto
Polymers & Petrochems. Co.
Publicker Indust. Co.
Union Carbide Corp. -
Chems. & Plastics Div.
Delaware Water
Gap, Pa.
St. Louis, Mo.
Kingsport, Tenn.
Albany, Ga.
Charles City, Iowa
Newport, Tenn.
Gelsmar, La.
Bay .City, Texas
Bishop, Tex.
Clear Lake, Tex.
Pampa, Tex.
Kingsport, Tenn.
52.2 (115) 930.7 (2050)-1971
50
181.6
250
181.6
(110)
(tfOO)
(550)
(JJOO)
Bayport, Tex.
Texas City, Tex.
Philadelphia, Pa.
Brownsville, Tex.
Taft, La.
Texas City, Tex.
18.2 (40)
181.6 (400)
36.3 (80)
268 (590)
111 (90)
15.4 (100)
Total -
1305 (2875)
-------
Table A-I. (Continued)
Acetic
anhydride
00
Acetone
Cellulose acetate fi-
bers and plastics; vinyl
acetate; dehydrating
and acetylating agent in
production of Pharma-
ceuticals, dyes, per-
fumes, explosives, etc.;
aspirin
Chemicals (methyl iso-
butyl ketone, methyl
Isobutyl carbinol
methyl methacrylate
bisphenol-A); paint;
varnish; lacquer sol-
vent; to clean & dry
parts of precision
equipment; solvent for
potassium iodide &
permanganate; deluste-
rant for cellulose
acetate fibers; speci-
fication testing of
vulcanized rubber
products
Celanese Corp. - Cela-
nese Chem. Co., div.
Celanese Fibers Co., div.
Eastman Kodak Co. -
Eastman Chem. Products.
Inc.. siibsid. -Ten- .
nessee Eastman Co., div.
PMC Corp. - Chem. Group
Indust. Chem. Div.
Union Carbide Corp.-
Chem. & Plastics Div.
Allied Chem. Corp. .-
Specialty Chems. Div.
Clark Oil & Refining
Corp. - Clark Chem.
Corp., subsid.
Dixie Chem. Co.
Dow Chem. U-.S.A.
Eastman Kodak Co. -
Eastman Chem. Products.,
Inc., subsid. - Tennes-
see Eastman Co., div.
Exx6n Corp. - Exxon
Chem. Co., div. - Exxon
Chem. Co. U.S»A.
Georgia-Pacific Corp. -
Chem. Div.
The Goodyear Tire & Rub-
ber Co. - Chem. Div.
Location(s)2'3
Pampa, Tex. "1
Cumberland, Md. 1
Narrows , Va . 1
Rock Hill, S.O.
Rome , Ga . J
Klngsport, Tenn.
Meadville, Pa.
Brownsville, Tex.l
Texas City, Tex. J
Prankf ord , Pa .
Blue Island, 111.
Bayport , Tex .
Oyster Creek, Tex.
Kingsport, Tenn.
1975
Capacity2
MM kg (MM Ib)
386
272.4
27.2
102
Total
787.7
143
24
11
109
36
(850)
(600)
(60)
(225)
(1735)
(315)
(53)
(24)
(240)
(80)
Bayway, N.J.
Plaquemlne, La'.
Bayport, Tex.
Total1*'5-
Production
MM kg (MM Ib)
for year of estimate
708.5 (1560.6)-1972
902.2 (1987.2)-1973
63.6 (140)
78.1 (172)
-------
Table A-l. (Continued)
Chemical
Acetone
(continued)
00
Acetone
Cyanohydrin
Acetonitrile
Usage1
(see previous page)
Insecticides; inter-
mediate for organic
synthesis, especially
methyl methacrylate
Solvent in hydro-
carbon processes,
especially for buta-
diene; specialty sol-
vent; intermediate;
separation of fatty
acids from vegetable
oils; manufacture of
synthetic Pharma-
ceuticals
Manufac t urer (_s_ )..2_*_^
Monsanto Co. - Monsanto
Polymers & Petrochems. Co
Oxirane Chem. Co.
Publicfcer Indust. Inc.
Shell Chera. Co. -
Base Chems.
Skelly Oil Co.
Standard, Oil of Calif, -
Chevron Chem. Co., sub-?
sld.^Qronite Additives
& Indust. Chem&. Div. -
Indust, Chems.
Union Carbide Corp..-
Chems. & Plastics Div*
Union Carbide Carlbe,
Ine., s-ubsld.
United States Steel Corp.
USS Chems., div.
E. I. du Pont de Nemours
& Co. Inc. - Industrial
Chems. Dept,
Rohm & Haas Co. - Rohm &
Haas Texas Inc., subsid.
Eastman Kodak Co. - East-
man Chem, Products, Inc.,
subsid., Texas Eastman
Co., div.
The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid.4 Chems. Dept.
Locatlon(s)2'3
Chocolate Bayou,
Tex.
Bayport, Tex.
Philadelphia, Pa.
Deer Park, Tex.
Dominquez, Calif.
Norco, La.
El Dorado , Kans .
Richmond^ Calif.
Total1"5
1975 production
Capacity2 MM kg (MM lb)
MM kg (MM lb) for year of estimate
122.6
18.2
15.9
181.6
45.4
15.4
25-9
15
(270)
-------
Table A-l. (Continued)
oo
j>-
oo
Chemical
Ac e t o -
phenone
Acetylene
Perfumery; solvent;
intermediate for
Pharmaceuticals,
resins, etc.;
flavoring
Vinyl chloride &
vinylidene chloride;
vinyl acetate; welding
& cutting metals; neo-
prene; acrylonitrile;
acrylates; per- & tri-
chloro-ethylene; cyclo-
octatetraene; tetra-
hydrofuran; carbon black
Manufacture(s)2*3
Allied Chem. Corp.
Speciality Chems-
Skelly Oil Co.
Universal Oil Pro-
ducts Co. - Chems.
& Plastics Group -
Chem, Dlv.
Chemical Use
Aircoa Inc.
Air Products & Chems.,
Inc., Specialty Gas
Dept.
Lo ca t ion (sj 2^3
Frankfort, Pa.
El Dorado, Kans.
East Rutherford
N.J.
Calvert City, Ky.
Louisville, Ky.
Hometown, Pa.
Rohm & Haas Co. - Rohm &
Haas Texas Inc., subsid.
Solox, Inc.
Tenneco Inc. - Tenneco
Chems., Organics &
Polymers Div.
Total
Capacity2
MM kg (MM Ib)
Chemetron Corp. -
Indus t . Gases Div.
Dow Chem. U.S.A.
Gaspro Inc.
Liquid Air Corp. of
North America — South-
western Region
Monochem. , Inc .
Northern Gases, Inc.
Occidental Petroleum
Corp. - Hooker Chem. Corp.
subsid., Hooker Chems. &
Plastics Corp. , subsid.
Electrochemical & Speci-
alty Chems. Div.
Pryor, Okla
Preeport , Tex.
Honolulu, Hawaii
Houston, Tex.
Geismar, La.
Waukesha, Wise.
Tacoma, Wash.
0.5
6.8
<0.5
_
81.7
_
4.5
(1)
(15)
(<1)
(180)
(10)
Deer Park, Tex.
Chattanooga, Tenn.
Houston, Texas
15-9 (35)
45- H
(100)
Total4*5
production
MM kg (MM Ib)
for yearof estimate
36.3 (80) 230.2 (507) -197**
109 (240)
(chemical and non-
chemical use)
-------
Table A-l. (Continued)
Chemical Usage1
Acetylene (see previous page)
(continued)
00
-P-
VO
Acetylene
(continued)
Manufacturer(s)2*3
Union Carbide Corp, -
Chems. & Plastics
Div.
Union Carbide Caribe,
Inc., subsid.
Non-Chemical Us'age
Airco, Inc. - Arco
Indust, Gases Div,
Air Products & Chems.
Inc.
American Cyanaraid Co. -
Specialty Gas Dept. -
Indust. Chems. & Plastics
Dlv.
Burdett Oxygen Co.
Paul Carroll Oxygen Co.
Chemetron Corp, - Indust.
Gases Div.
Location(s)2'3
Ashtabula, Ohio
Institute & South
Charleston, W. Va.
Seadrlft, Tex.
Taft, La.
Texas City, Tex.
Penuelas, P.R.
Houston, Tex.
Albany, Ga.
Bladensburg, Md.
Creighton, Pa.
Dallas, Tex.
Granite City, 111.
Greensboro, N.C.
Hampton, Va.
Iselin, N.J.
Kingsport, Tenn.
Memphis, Tenn.
Omaha, Neb.
Parkersburg, W. Va.
Rapid City, S.D.
New Orleans, La.
Norristown. Pa.
Abilene, Tex.
Belton, Tex.
Cleveland, Ohio
Columbus, Ohio
Conshohocken, Pa.
Dallas, Tex.
Denver, Colo.
Detroit, Mich.
Total
Capacity2
MM kg (MM Ib)
3* (75)
15-9 (35)
3.6 (8)
9.1 (20)
6.8 (15)
8.2 (18)
36.3 (80)
n.a.
Total (Chem.
use) =
-------
Table A-l.(Continued)
Chemical
Acetylene
(continued)
Usage1
(see previous page)
Manufacturer(3)2 * 3
Cheiaetion Corp. (cont'd)
00
Welding & Indusfc.
Products, Ltd. - subsid.
East Texas Oxygen Co.
Kansas Oxygen, Inc.
Liquid Air Corp. of North
America - Northwestern
Region
•?• Southeastern Region
Location(s)2j3
1975
Capacity2
MM kg (MM Ib)
Evansville ,, Ind,
Hodgkins, 111.
Jackson, Miss.
Jacksonville, Pla.
Knoxville, Tenn.
McKees Rocks, Pa.
Memphis, Tenn.
Miami, Pla.
New Orleans, La.
North Grafton, Mass.
Peoria, 111.
Pryor, Okla.
Sty Paul, Minn.
Southaven, Miss.
Tampa, Pla.
Ewa,(0ahu), Hawaii
Tyler* Tex.
Hutchinson, Kans .
Anchorage , Alas .
Boise, Idaho
Fairbanks , Alas .
Medford, Ore.
Missoula, Mont.
Portland, Ore.
Spokane, Wash.
Augusta, Ga.
Decautur, Ala.
Lake Charles, La.
Orlando, Pla.
- Southwestern Region Abilene, Tex.
Lubbock, Tex.
Odessa, Tex.
Phoenix, Ariz.
Tucson, Ariz.
- Western Region
Manitowoc Gases, Inc.
Las Vegas, Nev,
Reno, Nev.
Sacramento, Calif.
San Bernardino,
Calif.
Santa Pe Springs ,
Calif.
Union City, Calif.
Hanitowoc, Wise .
Total"*5
production
MM kg (MM Ib)
for year of estimate
(see previous page)
-------
Table A-l.(Continued)
Chemical
Acetylene
(Continued)
00
Oi
Aerolein
Aery1amide
Usage1
(see previous page)
Intermediate for
synthetic glycerol,
polyurethane, poly-
ester resins,
methionine,
Pharmaceuticals;
herbicide; tear gas
Synthesis of dyes, etc.;
polymers or copolymers
as plastics, adhesives,
paper & textile sizes,
soil conditioning
agents; flocculants;
sewage & waste treat-
ment; ore processing;
permanent press fabrics
Manufacturer(s)2'3
Northern Gases, Inc.
Pacific Oxygen Co.
Selox, Inc.
Union Carbide Corp. -
Ferroalloys Div.
Linde Div.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp.--
Chems. & Plastics Div.
American Cyanamid Co.-
Indust. Chems. & plastics
Div.
Bio-Red Labs
Dow Chem. U.S.A.
The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid. - Chems. Dept.
Locatlon(s)2*3
Waukesha, Wise.
Oakland, Calif.
Greenville, S.C.
Ashtabula, Ohio
Albany, N.Y.
Albuquerque, N.M.
Altoona, Pa.
Amarillo, Tex.
Baltimore, Md.
Billings, Mont.
Birmingham, Ala.
Boise, Idaho
Butte, Mont.
Carter Lake, Iowa
Casper, Wyo.
Charlotte, N.C.
Columbus, Ohio
Dallas, Tex.
Denver, Colo.
Des Moines, Iowa
Duluth, Minn.
East Buffalo, N.Y,
East Chicago, Ind.
Norco, La.
Taft, La.
Linden, N.J.
New Orleans, La.
Richmond, Calif.
Midland, Mich.
Lima, Ohio
1975
Capacity2
MM kg (MM Ib)
Total1**5
production
MM kg (MM Ib)
for; _ye.ar of estimate
(see previous page)
27-7 (61) -1974
18.2 (40) -1973
-------
Table A-l. (Continued)
Chemical
Acrylic
acid
Ui
to
Acrylo-
nitrile
Adipic
acid
Monomer for polyacrylic
& polymethacrylic acids
& other acrylic polymers
Acrylic & modacrylic
fibers & high-strength
whiskers; ABS & acrylo-
nitrlle-styrene copply-
mers; nitrile rubber;
cyanoethylation of cot-
ton; synthetic soil
blocks (aerylonitrile
polymerized in wood
pulp); organic
synthesis; grain
fumigant
Manufacture of nylon &
of polyurethane foams;
preparation of esters
for use as plasticisers
& lubricants; ingredient
of foods, as acldulant;
insecticides; adhesives
Manufacturer(s)2j 3
American Aniline & Ex-
tract Co,, Inc.
Celanese Corp. - Cela-
nese Chem, Co., div.
Dow Badische Co.
Rohm & Haas Co., Rohm &
Haas Texas Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
American Cyanamid Co. -
Indust. Chems. & Plastics
Div.
E. I. du Pont de Nemours
& Co., Inc . -
Elastomer Chems. Dept.
Indust. Chems. Dept.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid. - Chems. Dept.
Allied Chem. Corp.
Celanese Corp. - Cela-
nese Chem. Co., div.
E. I. du Pont de Nemours
& Co., Inc. - Plastics
Dept.
El Paso Natural Gas Co, -
El Paso Products Co.,
subsid.
Location(s)2'3
Philadelphia, Pa.
Clear Lake, Tex.
Pampa, Tex.
Freeport, Tex.
Deer Parkj Tex.
Taft, La.
New Orleans, La.
Beaumont, Tex.
Memphis, Tenn.
1975
Capacity2
MM kg (MM Ib)
100 -(220)
36.3 (80)
18.2 (HO)
181.6 (1)00)
90.8 (200)
Total =
131-3 (950)
90.8 (200)
136.2 (300)
113-5 (250)
Chocolate Bayou, La. 208.8 (160)
Lima, Ohio
Hopewell, Va.
Bay City, Tex.
Orange, Tex.
Victoria, Tex,
Odessa, Tex.
177 (390)
Total =
726.il (1600)
11.3 (25)
56.7 (125)
136.2 (300)
136.2 (300)
36.3 (80)
Total14'5
production
MM kg (MM Ib)
For year of estimate
37.5 (82.5) -1968
611.2 (1352.9J-1973
626.5 (1380) -1972
-------
Table
A-l.
(Continued)
00
Ul
LO
Chemical
Adipic
acid
(continued)
Alkylnaph-
thalenes
(methyl)
Allyl
alcohol
Allyl
chloride
(see previous page)
Organic synthesis;
insecticides
Esters for use in
resins & plastici-
zers; intermediate
for Pharmaceuticals &
other organic chemi-
cals; manufacture of
glycerol & acrolein;
military poison gas;
herbicide
Preparation of allyl
alcohol & other de-
rivatives ; thermo-
setting resins for var-
nishes , plastics, ad-
hesives; synthesis of
Pharmaceuticals, glycerol
ft insecticides
Manufacturer(s)2 * 3
Monsanto Co. - Monsanto
Indust. Chems. Co. -
Monsanto Textiles Co.
Crowley Hydrocarbon
Chems., Inc.
Koppers Co., Inc. -
Organic Materials Div.
Marathon Oil Co.
PMC Corp. - Chem. Group -
Indust, Chem. Div.
Shell Chem. Co. -
Base Chems.
Dow Chem. U.S.A.
Shell Chem. Co. -
Base Chems.
Location(s)2'3
Luling, La.
Pensacola, Pl'a.
1975
Capacity2
MM kg (MM Ib)
27.2 (60)
255 (562)
Total «
659.2 (1152)
Total*'5
production
MM kg (MM Ib)
for year of estimate
(see previous page)
Houston, Tex.
Kent, Ohio
Oklahoma City,
Okla.
Paulsboro, N.J.
Follansbee, W. Va.
Kobinson, 111.
Bayport, Tex.
Deer Park, Tex.
Freeport, Tex.
Deer Park, Tex.
NorcOj La.
Amino-
benzoic
acid
(m,o,p)
Dyes; drugs; perfumes
& Pharmaceuticals; dye
intermediates
Bofors Indust., Inc.
Salsbury Labs.
Linden, N.J.
Charles City, Iowa
Wilmington, N.C.
Salsbury Labs.
The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.
Wilmington, N.C.
St. Bernard, Calif.
-------
Table A-l. (Continued)
Chemical
Manufacturer(s)2'3
Locatlon(s)2'3
1975
capacity2
MM kg (MM Ib)
Total1**5'
production
MM kg (MM Ib)
for year of estimate
<&>
Ui
Amino-
benzoic
apid
(m,o,p)
(continued)
Amino-
ethyl-
ethanol-
amine
Amyl
acetates
Amyl
alcohols
(8 isomers)
Arayl-
amine
Textile finishing
compounds (antifuming
agents, dyestuffs,
eationic surfactants);
resins, rubber products,
insecticides, & certain
medicinals
Solvent for lacquers &
paints; extraction of
penicillin; photographic
film; leather polishes;
nail polish; warning
odor; flavoring agent;
printing & finishing
fabrics; solvent for
phosphors in fluorescent
lamps.
Solvent; raw material for
pharmaceutical prepara-
tions ; organic synthesis;
lubricants; plasticizers;
additives for oils; &
paints; flotation agent;
medicine
Chemical Intermediate;
dyestuffsj rubber chemi-
cals; insecticides;
synthetic detergents;
flotation agents; corro-
sion inhibitors; solvent;
gasoline additive;
Pharmaceuticals
Bofors Indust., Inc.
Northern Pine Chems., Inc.
Salsbury Labs.
Warner-Lambert Co. -
Parke, Davis & Co.,
subsid.
Dow Chem. U.S.A.
Hodag Chem. Corp.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Commercial Solvents Corp.
Publicker Indust. Inc.
Institute & South
Charleston, W.Va.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Organic Chems.
Pennwalt Corp., Chem. Div.
The Ames Labs., Inc.
Pennwalt Corp. - Chem.
Div.
Virginia Chems. Inc. -
Indust. Chems. Dept,
Linden, N.J.
Franklin, N.J.
Wilmington, N.C.
Holland, Mich.
Freeport, Tex.
Skokie, 111.
Conroe, Tex.
Institute & South
Charleston, W. Va.
Texas City, Tex.
Terre Haute, Inc.
Philadelphia, Pa.
Institute & South
Charleston, W. Va.
Texas City, Tex.
Rochester, N.Y.
Wyandotte, Mich.
Milford, Conn.
Wyandotte, Mich.
Portsmouth, Va.
(12) -1973
-------
Table Arl. (Continued)
00
Ui
Ui
Amyl Synthesis of other amyl
chloride compounds; solvent;
rotogravure ink vehiclesj
soil fumigation
Amyl Synthesis of organic sul-
tnercaptans fur* compounds; chief
constituent of odorant
used in gas lines to
locate leaks
Amyl Dispersing & mixing
phenol agent for paint pastes;
antiskinning agent for
paint, varnish, & oleo-
resinous enamelsj organic
synthesis; Manufacture
of oil-soluble resins;
plasticizer; germicidej
fumigant
Aniline Rubber accelerators &
antioxidants ; dyes &
intermediates; photo-
graphic chemicals
(hydroquinone); iso-
cyanates for urethane
foams; Pharmaceuticals;
explosives; petroleum
refining; diphenylaminej
phenolics; herbicides,
fungicides
Aniline Dyes; intermediates;
hydro- dyeing & printing;
chloride aniline black
Manufacturer(s)2 * 3
Columbia Organic Chem.
Co.
Eastman Kodak - East-
man Organic Chems.
Pennwalt Corp.
Pennwalt Corp. -
Chem. Div,
Productol Chem. Co.
American Cyanamid Co. -
Organic Chems. Div.
E. I. du Pont de
Nemours & Co., Inc.
Elastomer Chems. Dept.
Indust. Chems. Dept.
First Mississippi Corp.
First Chem. Corp., subsid.
Mobay Chem. Corp. -
Indust. Chems. Div.
Rubicon Chems. Inc.
American Cyanamid Co. -
Organic Chems. Div.
Locat-.ion(s)2'3
Columbia, S. C.
Rochester, M. Y.
Greens Bayou, Tex.
Wyandotte, Mich
Santa Fe Springs,
Calif.
Bound Brook, N. J.
Willow Island, W. Va.
Beaumont, Tex.
GIbbstown, N. J.
Pascagoula, Miss.
New Martinsville,
W. Va.
Gelsmar, La.
Bound Brook, N. J.
1975
capacity2
MM kg (MM Ib)
Total*'5
production
MM kg (MM Ib)
foryear of estimate
27.2 (60)
22.7 (50)
90-8 (200)
59 (130)
45.4 (100)
*»5.ll (100)
25 (55)
Total =
315 (695)
207.3 (456.6) -1973
-------
Table A-l. (Continued)
Manufacturer (s)2 * *
Locatlon(s)2 *_3
1975
Capacity2
MM kg (MM Ib)
Total**5
production
MM kg (MM Ib)
for year of estimate
Anisidine
Intermediate for azo dyes
ft for quaiacol; azo
dyestuffs
00
Ln
Anisole
Anthranilie
acid
Anthraqui-
none
Solvent ; perfumery ;
vermicide; intermediate
Dyes; drugs; perfumes
& Pharmaceuticals
Intermediate for dyes;
& organics; organic
inhibitor; bird repel-
lent for seeds.
Aldrich Chem. Co., Inc.
Eastman Kodak Co. -
Eastman Organic Chems.
American Color & Chem.
Corp,
E. I, du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes ft Chems. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co,
Salsbury Labs.
Chem. Formulators, Inc.,
Chem. Div.
Continental Oil Co. -
Conoco Chems, - Pitt-
Consol Chems.
Eli Lilly & Co. -
Tippecanoe Labs.
Givaudan Corp. - Chems.
Div,
Salsbury Labs.
The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.
American Cyanamid Co. -
Organic Chems. Div.
E. I. du Pont de Ne-
mours & Co. - Organic
Chems. Dept.
GAP Corporation
Sterling Drug Inc. -
Milwaukee, Wise .
Rochester, N. Y.
Lock Haven, Pa.
Deepwater, N. J.
St. Louis3 Mo.
Wilmington, N. C.
Nitro, W. Va.
Newark, N. J.
Lafayette, Inc.
Clifton, N. J.
Wilmington, N. C.
St. Bernard, Ohio
Boundbrook, N. Y.
WiImington, Del.
Linden, N. J.
Rensselaer, N. Y.
-------
Table A-l. (Continued)
CO
Ln
Chemical
Benzalde- Organic synthesis (es-
hyde pecially of dyes & dye
intermediates); sol-
vent for oils, resins,
some cellulose ethers,
cellulose acetate &
nitrate flavoring com-
pounds; synthetic per-
fumes; manufacture of
cinnamic acid, ben-
zole acid; Pharmaceu-
ticals & soaps; photo-
graphic chemicals;
baking chemicals;
medicine
Benzamide Organic synthesis
Benzene Styrene; phenol; syn-
thetic detergents;
cyclohexane for nylon;
aniline; DDT; maleic
anhydride; dichloro-
benzene; benzene hexa-
chloride; nitrobenzene;
diphenyl; insecticides;
fumigants; solvent;
paint removers; rubber
cement; antiknock
gasoline
Manufacturer(s)2'3
Alco Standard Corp. -
Monroe Ghem. Co., div.
Kalama Chem. Inc.
Northwest Indust.,
Inc. - Velsicol Chem.
Corp., subsid.
St'auffer Chem. Co. -
Specialty Chem. Div.
Tenneco Inc. - Organics
& Polymers Div.
Universal Oil Products
Co. - Chems. & Plastics
Group, Chem. Div.
Aceto Chem. Co., Inc. -
Arsynco, Inc., subsid.
Guardian Chem. Corp. -
Eastern Chem. Div.
Allied Chein. Corp. -
Union Texas Petroleum
Div.
Amerada Hess Corp. -
Hess Oil Virgin Islands
Corp.t subsid.
American Petrofina, Inc.
American Petrofina Co.
of Texas, subsid.
Cosden Oil & Chems.
Co., subsid.
Armco Steel Corp.
Ashland Oil, Inc. -
Ashland Chem. Co., div.
Petrochems. Div.
Atlantic Richfield Co. -
ARCO Chem. Co., div.
Location(s)2'3
Eddystone, Pa.
Kalama, Wash.
Chattanooga, Tenn.
Edison, N. J.
Fords, N. J.
East Rutherford,
N. J.
Carlstadt, N. J.
Hauppauge, N. Y.
Winnie, Tex.
St. Croix,
Virgin Islands
Port Arthur, Tex.
Big Spring, Tex.
Houston, Tex.
Middletown, Ohio
Ashland, Ky.
North Tonawanda,
N. Y.
Houston, Tex.
Wilmington, Del.
Bethlehem, Pa.
Lackawanna, N. Y.
Sparrows Po1nt, Md.
1975
capacity2
MM kg (MM Ib)
Total*1'5
production
MM kg (MM Ib)
for jLearcj* estimate
10 (22) 3694 (8136)- 1971
50 -CllO.2)
50 (110,2)
100 (220.5)
3 (6.6)
6.7(1^.7)
166.8(367.5)
50 (110.2)
146.8(323-4)
53-4(117.6)
13-3(19.4)
25 (55-1)
50 (110.2)
-------
Table A-l. (Continued)
Chemical
Benzene
(cont'd)
OO
Ui
00
Man ufac t urer(s)2"
CF&I Steel Corp.
The Charter Co., Char-
ter Oil Co., subsid.
Cities Service Co.,
Inc. - North American
Petroleum Group
Coastal States Gas Corp.
Coastal States Market-
ing, Inc., subsid.
Commonwealth Oil Re-
fining Co., Inc. -
Commonwealth Petro-
chems., Inc., subsid,
Crown Central Petro-
leum Corp.
Dow Chem. U.S.A.
Exxon Corp. - Exxon
Chem. Co., div. -
Exxon Chem. Co. U.S.A.
Gulf Oil Corp. - Gulf
Oil Chems. Co., div. -
Petrochems. Div.
Interlake, Inc. -
Jones & Laughlin In-
dust., Inc. - Jones &
Laughlin Steel Corp.,
subsid.
Kerr-McGee Corp. - South-
western Refining Co.,
Inc., subsid.
Marathon Oil Co.
The Mead Corp. -
Metals & Minerals Div.
Looation(s)2'3
Pueblo, Colo.
Houston, Tex.
1975
capacity2
MM kg (MM Ib)
10 (22)
16.7(36.7)
Total1"5
production
MM kg (MM Ib)
for year of estimate
(see previous page)
Lake Charles, La.
Corpus Christi,
Tex.
Penuelas, P. H.
Pasadena, Tex.
Aliqulppa, Fa.
Corpus Chrlstl,
Tex.
Texas City, Tex.
Woodward, Ala.
83.1(183.7)
233-6(511.5)
617 (1359.7)
66.7(117)
Bay City, Mich.
Freeport, Tex.
Baton Rouge, La.
Baytown, Tex.
Alliance, La.
Philadelphia, Pa.
Port Arthur, Tex,
Toledo, Ohio
100.1(220.5)
133.5(291)
210.2(529.2)
206.9(155.7)
233.6(511.5)
110 (212.5)
126.8(279.3)
3.3(7.3)
33.1(73-5)
26.7(58.8)
20 (M.I)
1.7(10.3)
-------
Table A-l. (Continued)
Chemical
Benzene
(continued)
Usage1
(see 2nd prev. page)
CTs
00
Ul
Manufacturer(s)2 ' 3
Mobil Oil Corp. - Mobil
Chem. Co., div. -
Petrochems. Div.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Northwest Indust., Inc.
Lone Star Steel Co.,
subsid.
Penzoil Co. - Atlas
Processing Co., subsid.
Phillips Petroleum Co.
Phillips Puerto Rioo
Core Inc., subsid.
Republic Steel Corp. -
Iron & Chem. Div.
Shell Chem, Co. - Base
Chems.
Skelly Oil Co.
Standard Oil Co. of
California
Standard Oil Co. (Ind.)
Amoco Oil Co., subsid.
Sun Oil Co. - Sun Oil
Co. of Pa.,
Suhtide Refining Co.,
subsid.
Tenneco Inc. - Tenneco
Oil Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Oil Co. of Calif.
Union Pacific Corp. -
Champlin Petroleum Co.,
subsid.
United States Steel
Corp. - USS Chems., div.
Location(s}2» 3
Beaumont , Tex.
Chocolate Bayou,
Tex.
1975
capacity2
MM kg (MM Ib)
200 (
-------
Table A-l. (Continued)
00
Chemical
Benzene-
sulfonic
acid
Benzenedi-
sulfonic
acid
Benzil
Benzilic
acid
Benzole
acid
Benzoin
Benzo-
nitrile
Phenol; resorcinol;
organ!c synthesis;
catalyst
Organic synthesis;
insecticide
Chemical
Intermediate
Sodium & benzyl ben-
zoates; plasticizers;
alkyd resins; vulcaniza-
tion retarder; food
preservative; season-
Ing tobacco; flavors,
perfumes; dentifrices;
medicine (germicide)
Organic synthesis;
intermediate; photo-
polymerization catalyst
Manufacture of benzo-
guanamlne; intermediate
for rubber chemicals;
solvent for nitrile
rubber, specialty lac-
quers, and many resins &
polymers, & for many
anhydrous metallic salts
Manufacturer(s)2^3
Nease Chem. Co., Inc.
Stauffer Chem. Co,,
Agricultural Chem. div.
Jim Walter Corp. - U.S.
Pipe & Foundry Co.,
subsid., Chem. Div-
Koppers Co., Inc. -
Organic Materials Div.
Jim Walter Corp. - U.S.
Pipe & Foundry Co.,
subsid., Chem. Div.
Napp Chems. Inc.
Stauffer Chem. Co. -
Specialty Chem. Div.
Kalama Chem., Inc.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Northwest Indust.,
Inc. - Velsicol Chem.
Corp,, subsid.
Pfizer Inc. - Chems.
Div.
Tenneco Inc. - Tenneco
Chems., Inc., Organic s
& Polymers Div.
Napp Chems., Inc.
Stauffer Chem. Co. -
Specialty Chem. Div.
Northwest Indust. Inc. -
Velsicol Chem. Corp.,
Subsid.
Location(s)2'3
State College, Pa
Henderson, Nev.
Birmingham, Ala.
Petrolia, Pa.
Birmingham, Ala.
LodI, N. J.
Edison, N. J.
Kalama, Wash.
St. Louis, Mo.
Beaumont, Tex.
Chattanooga, Tenn.
Terre Haute, Ind.
Garfield, N. J.
LodI, N. J.
Edison, N. J.
Chattanooga, Tenn.
Total1*'8
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM l.b) for year of estimate
5*1.5 (120
^.5 (10)
22.7 (50)
2.7. (6)
5.4 (12)
Total =
117.1 (258)
36.8 (81) -197M
-------
Table *~1- (Continued)
Chemical
Manufacturer(s)2 *
Location(s)2'
1975
capacity2
MM kg (MM Ib)
Total1*'5
production
MM kg (MM Ib)
for yeaj? of estimate
Benzo-
phenone
oo
Benzo-
quinone
Benzo-
trichlo-
ride
Organic synthesis;
perfumery; odor fixa-
tive; derivatives
are used as ultravio-
let absorbers; flavor-
ing; polymerization
inhibitor for styrene
Manufacture of dyes
& hydroquinone
Synthetic dyes;
organic synthesis
Aceto Chem. Co., Inc.-
Arsynco, Inc ., subsid.
GAP Corp. - Chem. Div.
Norda Inc.
Orbis Products Corp.
Universal Oil Products
Co. - Chems. & plastics
Group - Chem. Div.
Warner-Lambert Co, -
Parke, Davia & Co.,
subsid.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Frank Enterprises
Northwest Indust., Inc.
Velsicol Chem. Corp.,
subsid.
Occidental Petroleum
Corp., Hooker Chem.
Corp., subsid - Hooker
Chems. & Plastics Corp.,
subsid, - Electrochemi-
cal & Specialty Chems.
Div.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
Carlstadt, N. J.
Rensselaer, N. Y.
Boonton, N. J.
East Hanover, N. J.
Newark, N. J.
East Rutherford, N. J.
Holland, Michigan
Kingsport, Tenn.
Columbus, Ohio
Chattanooga, Tenn,
Niagara Falls, N. Y.
Fords, N. J.
-------
Table A-l. (Continued)
Chemical
Manufacturer (_s_)2 *3
LocatlonCs)2*3
1975
capacity2
MM kg (MM Ib)
Total1**5
production
MM kg (MM Ib)
for year of estimate
Benzoyl
chloride
00
Benzyl
alcohol
Benzl-
amlne
Medicine; intermediate
for production of ben-
zoyl groups; inter-
mediate for other
organ!cs
Perfumes & flavors;
photographic developer
for color movie films;
dyeing nylon filament,
textiles and sheet
plastics; solvent for
dyestuffs, cellulose
esters, casein, waxes,
etc.; heat-sealing poly-
ethylene films; inter-
mediate for benzyl
esters & ethers; local
anesthetic; cosmetics,
ointments, emulsions;
ball point pen Inks;
stencil inks.
Chemical intermediate
for dyes, Pharmaceuti-
cals, & polymers
Northwest Indust., Inc. -
Velsicol Chem. Corp.,
subsld.
Occidental Petroleum
Corp., Hooker Chem.,
Hooker Chems. & Plastics
Corp., subsid. - Electro-
chemical & Specialty
Chems. Div.
Stauffer Chem. Co. -
Specialty Chem. Div.
Tenneco Chems., Inc. -
Tenneco Chems., Inc.,
Organics & Polymers Div.
Alco Standard Corp. -
Monroe Chem. Co., div.
Cloray NJ Corp.
Givaudan Corp. - Chems.
Div.
Northwest Indust.,
Inc. - Velsicol Chem.
Corp., subsid.
Orbis Products Corp.
Stauffer Chem. Co. -
Specialty Chem. Div.
Tenneco Inc. - Tenneco
Chems., Inc. — Organics
& Polymers Div.
Universal Oil Products
Co. - Chems. & Plastics
Group - Chem. Div.
Aceto Chem. Co., Inc. -
Arsynco, Inc., subsid.
Miles Labs., Inc. -
Sumner Div.
Uniroyal, Inc. - Uni-
royal Chem., div.
Chat tanooga, Tenn.
Niagara Falls,
Edison, N. J.
Fords, N. J.
Eddystone, Pa.
Newark, N. J.
Clifton, N. J.
Chattanooga, Tenn.
Newark, N. J.
Edison, N. J.
Fords, N. J.
East Rutherford,
N. J.
Carlstadt, N. J.
Zeeland, Mich.
Naugatuck, Conn.
-------
Table A-l. (Continued)
Chemical
Manufacturer(s)2'3
Locations )2'3
1975
capacity2
MM kg (MM Ib)
Total1"5-
production
MM kg (MM Ib)
for year of estimate
Benzyl
benzoate
0V
00
Benzyl
chloride
Benzyl
dichlorlde
Biphenyl
Fixative & solvent for
musk in perfumes &
flavors; medicine
(external); plasticizer;
miticide
Dyes; intermediates;
benayl compounds; syn-
thetic tannins; per-?
fumery; Pharmaceuticals j
manufacture of photo-p
graphic developer;
gasoline gui? Inhibi-
tors ; penicillin
precursors; quaternary
ammonium compounds
Dyes
Organic synthesis; heat
transfer agent; fungi-
cides; dyeing assistant
for polyester
Monsanto Co. - Monsanto
Flavor/Essence, Inc.
Monsanto Indust * Chems.
Co.
Northwest Indust,, Inc.-
Velsicol Chem. Corp.,
subsid.
Pfizer Inc. -
Chems. Div*
Universal Oil Products
Co. - Chems. & plastics
Group - Chem. Div-.
W, R. Grace & Co. -
Hatoo Group - Hatco
Chem. Div.
Monsanto Co. — Monsanto
Indust. Chems. Co.
Northwest Indust., Inc.
Velsicol Chem, Corp.,
sub S, id.
Sfcauffer Chem. Co. -
Specialty Chem. Div.,
Tenneoo Inc. - Tenneao
Chems,., Inc. - Organlcs
& Polymers Div.
GAP Corp. - Chem. Fiv.
Tenneco Inc. - Tenneco
Chems., Inc. - Organ!cs
& Polymers Div.
Bethlehem Steel Corp.
Chemol, Inc.
DQW Chem. U.S.A.
Monsa,nto Co. T Monsanto
Indust. Cheps. Co.
Pilot Chem. Co. -r Pilqt
Indust. of Texas, suhsid.
Sybron Corp. - The
Tanatex Chetiu Co., div.
Woonsocket Color & Chem.
Co.
St. Louis, Mo.
St. Louis, Mo.
Chattanooga, Tenn,
Greensboro, N. C.
East Rutherford,
N. J.
Fords, N. J.
Rensselear, N. Y.
Great Meadows,
N. J.
Sparrows Point, Md.
Greensboro, N. C.
Bay City, Mich.
Freeport, Tex.
Anniston, Ala.
Houston, Tex.
Lyndhurst, N. J.
Woonsocket, R.- I,
(15)
40.9 (90)
Bridgeport, N. J.
Chat1;anoqga, Tenn.
Edison, H. 1.
Fords, N. J[.
3* (75)
1.5 (10)
5 (11)
3^^ (7)
Total -
536 (118)
2.3 ( 5) -1971
-------
Table
A-l.
(Continued)
Chemical
Bisphenol
A
00
Bromo-
benzene
Bromo-
naphtha-
lene
Butadiene
Epoxy, polycarbonate,
phenoxy, & polysul-
fone resins
Solvent; motor fuels;
top-cylinder com-
pounds; crystallizing
solvent; organic
synthesis
Organic synthesis;
microscopy;
refractometry
Principally in sty-
rene-butadiene rubber,
& to a lesser degree in
polybutadiene and
nitrile elastomers;
as the starting material
for adiponitrile (nylon
66); in latex paints;
resins; organic
intermediate
Manufacturer(s)2' 3
Dow Chem. U.S.A.
Gen. Electric Co. -
Plastics Business Div,
Engineering Plastics
Product Dept.
Shell Chem. Co. -
Polymers & Detergent
Products
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc., subsid.
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Organic Chems.
Guardian Chem. Corp. -
Eastern Chem. Div,
R.S.A. Corp.
Atlantic Richfield Co.
ARCO Chem. Co., div.
Copolymer Rubber &
Chem. Corp.
Dow Chem. U.S.A.
El Paso Natural Gas Co. -
El Paso Products Co.,
subsid,
Exxon Corp. - Exxon Chem.
Co. U.S.A. - Exxon Chem.
Co., div.
The Firestone Tire & Rub-
ber Co., Firestone
Synthetic Rubber & Latex
Co., div.
Locations)2'3
Freeport, Tex.
Mount Vernon, Ind.
Deer Park, Tex.
Total4*5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM 1'b) for year of estimate
Midland, Mich.
Rochester, N. Y.
Hauppauge, N. Y.
Ardsley, N. Y.
Channelview, Tex.
Baton Rouge, La.
Bay City, Mich.
Freeport, Tex.
Odessa, Tex.
Baton Rouge, La.
Orange, Tex.
U5-4 (100)
32.7 (72)
68 (150)
(319-7)-1973
Marietta, Ohio
Penuelas, P. R.
18.2 (1)0)
31-8 (70)
Total -
196.1 (1132)
127 (280)
58.1 (128)
10.9 (21)
39 (86)
90.8 (200)
151.1 (310)
99.9 (220)
1663 (3662.8)-1973
-------
Table *-!• (Continued)
Chemical
Butadiene
(continued)
Usage'
(see previous page)
OS
oo
Manufacturer(s)2' 3
Qetty Oil Co.
Mobil Oil Corp. - Mobil
Chem. Co., div. -
Petrochems. Div.
Monsanto Co, - Monsanto
Polymers & Petrochems.
Co.
Neches Butane Products
Co.
Northern Natural Gas Co.
Northern Petrochem. Co.,
subsid., Polymers Div.
Petro-Tex Chem. Corp. -
Petro-Tex Chem. Co.,
subsid.
Phillips Petroleum Co, -
Petrochem. & Supply Div.
Puerto Rico Olefins Co.
Shell Chem. Co. - Base
Chems.
Standard Oil Co. (Ind.) -
Amoco Chems. Corp., sub-
sid.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Carbide, Inc
Subaid.
Location(s)2'3
Delaware City,
Del.
Beaumont, Tex.
Chocolate Bayou
Port Neches, Tex,
Morris, 111.
Houston, Tex.
Phillips, Tex.
Penuelas, P. R.
Deer Park, Tex,
Chocolate Bayou,
La.
Seadrift, Tex.
Taft, La.
Texas City, Tex.
Penuelas, P. R.
Total1"5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
9.1 (20)
36.3 (80)
511.5 (120)
290.6 (640)
29.5 (65)
14119.5 (990)
131.7 (290)
90.8 (200)
120.3 (265)
10.9 (90)
20.1 (15)
10.9 (90)
20.1 (15)
70.1 (155)
Total =
1,985.3 (1,373)
(see previous page)
-------
Table A-l. (Continued)
Chemical
n-3utyl
acetate
I
sec-Butyi
acetate
tert-
Butyl
acetate
n-Butyl-
acrylate
Solvent in production of
lacquers, lacquer enamels;
pyroxylin solutions;
leather dressings; per-
fumes, flavoring extracts;
solvent for natural gums &
synthesis resins; dehy-
drating agent
Solvent for nitro-
cellulose i Xacquers;
thinners; nail enamels;
celluloid products;
artificial leather;
leather finishes;
plastic wood;.washable
wallpaper
Possible antiknock
agent in gasoline
Intermediate in organic
synthesis; polymers &
copolymers for solvent
coatings, adheslves,
paints, binders;
emulsifier
Manufacturer(s)2*3
Celanese Corp. - Cela-
nesfe Chem. Cor.', div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid - ^enn.
Eastman Co., div.
Publicker Indust. Inc.
-Union Carbide Corp^ -
& Plastics Div.
EXxon Corp. - Exxon
£henu Co.
"Jtercules, inc.
Shell Chem, Co. -
Jndust. Cheras./Petro-
chems.
(See also - n-Butyl
acetate)
Exxon Corp. - Exxon
Chem\ po.
(See also - n-Butyl
acetate)
Celanese Corp. - Cela-
nese Chern. Co., div.
Dow Bad!sche Co,
Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Locatlon(s)2'3
Bishop, Tex.
Klngsport!( Tenn.
Philadelphia, Pa.
Institute & South
Charleston, tf. Va*
Texas City, Tex.
Baton Rouge, ia.
Hattlesburg, Miss.
Deer Park, Tex.
Baton Rouge, La.
Clear Lake, Tex.
Pampa, Tex.
Freeport, Tex.
Deer Park, Tex.
Institute & South
Charleston, W. Va.
Taft, La.
1975
capacity2
MM kg (MM lb)
6.8 (15)
6.8 (15)
6.8 (15)
22.7 (50)
Total te
^3-1 (95)
Total"*5-
preduction
MM kg (MM lb)
for jrear of estimate
43.M (95.7) -1972
-------
Table &-!-• (Continued)
Chemical.
n-Butyl
alcohol
00
ON
sec-
Butyl
alcohol
tert-
Butyl
alcohol
Preparation of esters,
especially Butyl ace-
tate; solvent for
resins & coatings;
plasticizers; dyeing
assistant; hydraulic
fluids; detergent
formulations; dehydrat-
ing agent (by azeo-
tropic distillation);
intermediate; "butyl-
ated" melamine
resins
Preparation of methyl
ethyl ketone; solvent;
organic synthesis
Alcohol denaturant
Manufacturer(s)2 >3
Celanese Corp. - Cela-
nese Chem. Co., div.
Continental Oil Co. -
Conoco Chems.
Dow Badische Co.
Eastman Kodak Co. -
Eastman Chem. Products
Inc., subsid. - Texas
Eastman Co., div.
W. R. Grace & Co. -
Hateo Group - Hatco
Chem. Div.
Oxochem Enterprise
Publicker Indust. Inc.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc., subsid.
Celanese Chem, Co.
Exxon Corp. - Exxon
Chem. Co.
Shell Chem. Co. -
Indust. Chems./Petro-
chems.
Shell Chem. Co. -
Indust. Chems./
Petrochems.
Oxirane Chem. Co.
Location(s)z*3
Bay City, Tex.
Bishop, Tex.
Clear Lake, Tex.
Westlake, La.
Freeport, Tex.
Longview, Tex.
Fords, N. J.
Penuelas, P. R.
Philadelphia, Pa
Deer Park, Tex.
Seadrift, Tex.
Penuelas, P. R.
Bay City, Tex.
Bishop, Tex.
Clear Lake, Tex.
Baton Rouge, La.
Deer Park, Tex.
Martinez, Calif.
Bayport, Tex.
1975
capacity2
MM kg (MM Ib)
68.1 (150)
20.I* (1(5)
2.3 (5)
43.1 (95)
31.8 (70)
36.3 (80)
15.9 (35)
36-3 (80)
27.2 (60)
18.2 (40)
Total =
299.6 (660)
Total**5
production
MM kg (MM Ib)
for year of estimate
235.4 (518.6) -1973
205.6 (453) -1973
508.5 (1120) -1973
-------
Table A-l- (Continued)
Chemical
Manufacturer(s)2 *
Location(s)2*3
1975
capacity2
MM kg (MM lb)
Total4*5
production
MM kg (MM lb)
for year ofestimate
tert-
Butyl-
phenol
00
ON
00
tert-
Butyl-
toluene
n-Butyr-
aldehyde
Chemical intermediate
for synthetic resins,
plasticizers, surface-
active agents, perfumes,
& other products; a
permissible antloxi-
dant for aviation
gasoline; plasticizer
for cellulose acetate
intermediate for anti-
oxidants, special
starches, oil soluble
phenolic resins; pour-
point depressors &
emulsion breakers for
petroleum oils & some
plastics; synthetic
lubricants; insec-
ticides ; industrial
odorants
Solvent; intermediate
Poly vinyl butyral;
butyrate plastics
Dow Chem. U.S.A.
Ethyl Corp.
Productol Chem. Co.
Schenectady Chem.,
Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Shell Chem. Co. -
Base Chems .
Celanese Corp. -
Celanese Chem. Co.,
div.
Eastman Kodak Co. -
Eastman Chem. Pro-
ducts, Inc., subsid. -
Texas Eastman Co., div.
Oxochem Enterprise
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Midland, Mich.
Orangeburg, S. C.
Santa Fe Springs,
Calif.
Rotterdam Junction,
N. Y.
Bound Brook, N. J.
Martinez, Calif.
Bay City, Tex.
Bishop, Tex.
Freeport, Tex.
Longview, Tex.
Penuelas, P. R.
Deer Park, Tex.
Institute & South
Charleston, W. Va.
Seadrift, Tex.
Penuelas, P. R.
136.2 (300)
227 (500)
158.9 (350)
111.2 (245)
68.1 (150)
136.3 (300)
Total »
837.6 (18«5>
-------
Table A-l. (Continued)
I
00
Chemical
n-Butyrlc
acid
n-Butyric
anhydride
n-Butyr-
onltrile
Carbon
disul-
fide
Synthesis of butyrate
ester perfume &
flavor ingredients;
Pharmaceuticals; de-
liming agent; dis-
infectants; emulsi-
fying agents;
sweetening gasolines
Manufacture of butyrates;
drugs; tanning agents
Basic material- in in-
dustrial, chemical &
pharmaceutical inter-
mediates & products;
poultry medicines
Viscose rayon; cel-
lophane ; manufacture of
carbon tetrachlorlde
& flotation agents;
veterinary medicine;
solvent
Man_uf_a c t u r e r (s)2 * _3
Celanese Corp. - Cela-
nese Chem. Co., div.
Eastman Kodak Co, -
Eastman Chem. Products,
Inc., subsld. - Tenn.
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div,
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Lonza Inc.
FMC Corp. - Chem.
Group - Indust.
Chem. Div.
Pennwalt Corp. -
Chem. Div.
PPG Indust,, Inc. -
Chem. Div. - Indust.
Chem. Div.
Stauffer Chem. Co. -
Indust. Chem. Div.
Location(s)2'3
Pampa, Tex.
Eastman, Terni.
Institute & South
Charleston, W. Va.
Klngsport, Tenn.
Institute & South
Charleston, W. Va.
Longview, Tex.
Mapleton, 111.
South Charleston,
W. Va.
Greens Bayou, Tex.
Natrium, W. Va.
Delaware City, Del.
Le Moyne, Ala.
1975
capacity2
MM kg (MM lb)
Total"*5-
production
MM kg (MM lb)
f o ryear o f e s t i ma t e
81.7 (180)
1.5 (10)
27.2 (60)
158.9 (350)
113-5 (250)
Total =
385.9 (850)
351-8 (775) -1972
Carbon
tetra-
bromide
Organic synthesis
Great Lakes Chem, Corp.
Olin Corp, - Designed
Products Div.
El Dorado, Ark.
Rochester, N. Y.
-------
Table A-l. (Continued)
00
Chemical
n-Butyl-
amlne
sec-Butyl-
amine
tert-Butyl-
amine
p-tert-
Butyl-
benzoic
acid
1,3
Butylene
glycol
Butylenes
Intermediate for
emulsifying agents;
Pharmaceuticals, in-
secticides; rubber
chemicals; dyes;
tanning agents
Intermediate for rubber
accelerators; insec-
ticides; fungicides;
dyestuffs; Pharmaceu-
ticals
Polyesters; polyure-
thanes; surface active
agents; plasticlzers;
humectant; coupling
agent; solvent; food
additive & flavoring
Polymer & alkylate gaso-
line ; polybutenes;
butadiene; Intermediate
for Ci, & C5 aldehydes,
alcohols, St other
derivatives;
Solvent; cross-link-
ing agent; butadiene
synthesis; synthesis
of Ci, & C5 derivatives
Manufacturer(s) 2 * 3
Air Products & Chems .
Pennwalt Corp. -
Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Div,
Va. Chems , Inc . -
1975
capacity2
Location(s)2'3 KM kg (MM Ib)
Pensacoia,
Wyandotte,
Institute
Charleston
Portsmouth
Fla.
Mich.
& South
, W. Va.
, Va.
Total1"5
production
MM kg (MM Ib)
for year of estimate
1.82 (i|) -1973
Indust. Chems. Dept.
Pennwalt Corp. -
Chem. Div.
Va. Chems. Inc. -
Indust. Chems. Dept.
Monsanto Co. - Monsanto
Indust. Chem. Co.
Rohm & Haas Co. - Rohm
& Haas Tex Inc., subsid.
Shell Chem. Co. -
Base Chems.
Celanese Corp. -
Celanese Chem. Co., dlv.
Dow Chem. U.S.A.
Gulf Oil Corp. - Gulf
Oil Chems, Co., div. -
Petrochems div.
Petro-Tex Chem. Corp.
Petro-Tex Chem. Co.,
subsid.
Wyandotte, Mich.
Portsmouth, Va.
Texas City, Tex.
Deer Park, Tex.
Martinez, Calif.
Bishop, Tex.
Bay City, Mich.
Freeport, Tex.
Cedar Bayou,
Tex.
Houston, Tex.
10,074 (22,190>-1967
-------
Table A-l. (Continued)
Chemical
Carbon
tetra-
chloride
00
Refrigerants & propel-
lants; metal degreasing;
agricultural fumigant;
chlorinating organic
compounds; production of
semiconductors
ManufacturerCsl2^.3
Allied Chem. Corp. -
Specialty Chem. Dlv.
Dow Chemical U.S.A.
E. I. du Pont de
Nemours & Co,, Inc. -
Organic Chems. - Dept.
Freon® - Products Dlv.
PMC Corp. - Chem.
Group - Indust. Chem.
Div.
Inland Chem. Corp.
Stauffer Chem. Co, -
Indust. Chem. Div.
Vulcan Materials, Co.
Chems. Div.
Loeationfs)2'3
Moundsville, W. Va .
Freeport, Tex.
Pittsburg, Oal.
Plaquemine , La .
Corpus Christi,
Tex.
South Charleston,
W. Va.
Hanati, P. R.
Le Moyne, Ala.
Louisville, Ky.
Niagara Palls,
N. Y.
Geismar, La.
Wichita, Kans.
Total lt>5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
3.6
59
20.4
15.1
136.2
90.8
31.8
68.1
(8) 158.3 (1009.D -1971
(130)
(15)
(100)
(300)
(200)
(TO)
(150)
15.9 (35)
18.2 (10)
Total =
716.1 (1578)
-------
Table A-l.(continued)
Chemical
Cellulose
acetate
(Jo
Chloranil
Chloro-
acetic
acid
m-chloio-
aniline
o-chloro-
aniline
Acetate fiber; lacquers;
protective coating
solutions; photographic
film, transparent sheet-
ing, thermoplastic mold-
ing composition, cigaret-
te filters, magnetic
tapes, osmotic cell
membrane
Agricultural fungicide;
dye intermediate; ele-
trodes for pH measure-
ments ; vulcanizing
agent
Herbicide; Intermediate
in production of car-
boxymethylcellulose,
ethyl chloroacetate,
glycine, synthetic
caffeine, sarcosine,
thioglycolic acid,
EDTA, 2,4-D, 2,4,5-T
Intermediate for azo
dyes & pigments; Phar-
maceuticals; Insecti-
cides ; agricultural
chemicals
Dye intermediate; stan-
dards for colorlmetrlc
apparatus; manufacture
of petroleum solvents
& fungicides
Manu f ac t ur e r ( s ) 2 * 3
Celanese Corp. -
Celanese Fibers Co.,
div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Textile Fibers Dept.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
FMC Corp. - Chem.
Group - Fiber Div.
Dow Chem. U.S.A.
Hercules Inc. -
Coating & Specialty
Products Dept.
The Procter & Gamble
Co. - The Buckeye
Cellulose Corp., subsid.
E. I. du Pont de Nemours
& Co., Inc., Organic
Chems. Dept. - Dyes &
Chems-. Div.
GAP Corp. - Chem. Div.
E. I. du Pont de Nemours
& Co., Inc. - Organic
Chems. Dept, - Dyes &
Chems. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Location (sj^2'^_
Narrows, Va.
Rock Hill, S. C.
Rome, Ga.
Waynesboro, Va.
Kingsport, Tenn.
Meadville, Pa.
Midland, Mich.
Hopewell, Va.
Memphis, Tenn.
Deepwater, N. J.
Linden, N. J.
Deepwater, N. J.
Luling, La.
1975
capacity.2
MM kg (MM Ib)
22? (500)
27-2(60)
156.6(315)
11-3(25)
Total -
422.2(930)
Total **'5
production
MM kg (MM Ib)
for year, of estimate
209.8 (462.2) -1973
29.1 (64.2) -1969
9.1(20)
1.1(3)
Total =
30.9 (68)
-------
Table A-l. (Continued)
Chemical
p—chloro-
aniline
Chloro-
benzalde-
hyde
00
*vj
u>
Chloro-
benzene
Dye intermediate;
Pharmaceuticals; agri-
cultural chemicals
Intermediate in the
preparation of tri-
phenyl methane &
related dyes; organic
intermediate
Phenol; chloronitro-
benzene; DDT; aniline;
solvent carrier for
methylene diisocyanate;
intermediate & solvent
Manufacturer(s)2'3
E. I. du Pont de Nemours
& Co., Inc., Organic
Chems. Dept. - Dyes &
Chems. Div.
Monsanto Co. - Monsanto
Indus t. Chems. Co.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.
subsid - Electrochemi-
cal & Specialty Chems.
Div.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
Allied Chem. Corp. -
Indust. Chems. Div.
Dow Chem. U.S.A.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Montrose Chem. Corp.
of California
Occidental Petroleum
Corp, - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.,
subsid. - Electrochemi-
cal & Specialty Chems.
Div.
PPG Indust., Inc. -
Chem. Div. - Indust.
Chem. Div.
Standard Chlorine
Chem, Co., Inc.
Location(s)2'3
1975
capacity2
MM kg (MM Ib)
1* 5
Total '
production
MM Kg (MM Ib)
for year of estimate
Deepwater, N. J,
Luling, La.
Niagara Falls,
N. Y.
Fords, N. J.
Syracuse (Solvay),
N. Y.
Midland, Mich.
Sauget, 111.
Henderson, Nev.
Niagara Falls,
N.Y.
Natrium, W. Va.
Delaware City,
11.3 (25)
136.2 (300)
52.2 (115)
31.8 (70)
6.8 (15)
11-3 (91)
31 (75)
Total -
313.7 (691)
183.2 (403.5) -1972
-------
Table A-l. (Continued)
00
Chloro-
benzoic
acid
Chloro-
benzoyl
chloride
Chloro-
dlfluoro-
ethane
Chloro-
form
Chloro-
naphtha-
lene
Intermediate for the
preparation of dyes,
fungicides, Pharma-
ceuticals & other
organic chemicals
Intermediate for
Pharmaceuticals, dyes
6 other organic
chemicals
Refrigerant; solvent;
aerosol propellant;
Intermediate
Pluorocarbon refrig-
ants & propellantsj
fluorocarbon plastics;
dyes & drugs; general
solvent; analytical
chemistry; fumlgant;
insecticides
Wax; condenser impreg-
nation; moisture-, flame-
acid- j Insect-proofing
of wood, fabric & other
fibrous bodies; mois-
ture-, & flame-proofing
covered wire & cable;
solvent (for rubber,
aniline & other dyes;
mineral & vegetable
oils, varnish gums
& resins, & other
waxes when mixed
in the molten state
Manufaeturer(s)2*3
Tenneco Inc. - Tenneco
Chems., Inc. - Organlcs
& Polymers Div.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
E. I. du Pont de Nemours
& Co., Inc., Organic
Chems. Dept. - Preon®
Products Div.
Pennwalt Corp. -
Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Div,
Allied Chem. Corp. -
Specialty Chems. Div.
Diamond Shamrock Corp, -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.
Dow Chem. U.S.A.
Stauffer Chem. Co. -
Indust. Chem. Div.
Vulcan Materials Co. -
Chems. Div.
American Color & Chem.
Corp.
GAP Corp. - Chem. Div.
JKoppers Co., Inc. -
Organic Materials
Div.
Location(s)2'
Fords, N. J.
Fords, H. J.
Antloch, Calif.
Deepw&ter, N. J.
East Chicago, Ind.
Louisville, Ky.
Montague, Mich.
Calvert City, Ky.
Institute & South
Charleston, W. Va.
Moundsvllle, ¥. Va.
Belle, W. Va.
Preeport, Tex.
Louisville, Ky.
Geismar, La.
Newark, N. J.
Wichita, Kans.
Lock Haven, Pa.
Linden, N. J.
Bridgeville, Pa.
1975
capacity2
MM kg (MM Ib)
Total ""S
production
MM kg (MM Ib)
fpr^rear of est Imate
13.6 (30)
8.2 (18)
45-4 (100)
34.1 (75)
4.5 (10)
13.6 (30)
Total =
133 (293)
106.8 (235.2) -1972
-------
Table A-l. (Continued)
Chemical
o-
cresol
00
p-cresol
Cresylic
acid
See m- eresol
See m-cresol
Phosphate esters;
phenolic resins; wire
enamel solvent; plastici-
zers; gasoline additives;
laminates coatings for
magnet wire for small
electric motors; dis-
infectants ; metal
cleaning cumpounds*
phenolic resins flota-
tion agents; surfactants >
chemical intermediates;
oil additives; solvent
refining of lubricating
oils; scouring com-
pounds; pesticides
Marmfacturer(s)2*3
Continental Oil Co. -
Conoco Chems. - Pitt
Consol Chems.
Koppers Co., Inc. -
Organic Materials Div.
The Merichem Co.
Productol Chem. Co.
Stimson Lumber Co. -
Northwest Petrochem.
Corp., div.
American Cyanamid Co, -
Organic Chems. Div.
The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.
Continental Oil Co. -
Conoco Chems. - Pitt-
Cons ol Chems.
Crowley Tar Products Co.
Ine.
Koppers Co., Inc. -
Organic Materials Div.
The Merichem Co.
Mobil Oil Corp. -
North American Div.
Productol Chem. Co.
Stimson Lumber Co. -
Northwest Petrochem.
Corp.> div.
U.S. Steel Corp. -
USS Chems., div.
Locatlon(s)2'3
Newark, N. J.
1975
capacity2
MM kg (MM Ib)
.
Total"'5
production
MM kg (MM Ib)
for year of estimate
See m-cresol
Follansbee, W. Va.
Houston, Tex.
Santa Fe Springs,
Calif.
Anacortes, Wash.
Bound Brook, N. J.
Chicago, 111.
Newark, N. J.
Houston, Tex.
Follansbee, W. Va.
Houston, Tex.
Beaumont, Tex.
Paulsboro, N. J.
Santa Fe Springs,
Calif.
Anacortes, Wash.
Clairton, Pa.
22.7 (50)
15-9 (35)
15.ft (100)
l._1 (3)
13.6 (30)
13.6 (30)
9-1 (20)
Total -
121.7 (268)
See m-cresol
31.7 (69.9) -1971
-------
Table A-l. (Continued)
oo
Chemical
Chloro-
nitro-
benzene
Chloro-
phenols
m-chloro-
toluene
ochloro-
toluene
p-chloro-
toluene
cresol
Intermediate, especially
for dyes; manufacture
of p-nitrophenol, from
which parathion is made
Intermediate in synthesis
of dyes & drugs; denatu-
rant for alcohol; selec-
tive solvent in refining
mineral oils
Solvent; Intermediate
Solvent & Intermediate
for organic chemicals
& dyes
Solvent & intermediates
for organic chemicals &
dyes
Disinfectant; phenolic
resins; tricresyl phos-
phate; ore flotation;
textile scouring agent;
organic Intermediate;
mfg. of salicylaldehyde;
coumarin, & herbicides;
in food antioxidants;
surfactant
Manufact ur e r (s)2 * 3
E, I. du Pont de Nemours
& Co., Inr. - Organic
Chems. Dept. - Dyes &
Chems. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Aldrich Chem. Co., Inc.
Dow Chem. U.S.A.
Eastman Kodak Co, -
Eastman Organic Chems.
Monsanto Co. - Monsanto
Indus t. Chems. Co.
Specialty Organics, Inc.
R.S.A. Corp.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsld., Hooker
Chems. & Plastics Corp.,
subsld, - Electrochemi-
cal & Specialty Chems.
Dlv.
Tenneco Inc. - Tenneco
Chems,, Inc. - Organics
& Polymers Div.
(See o-chlorotoluene)
Koppers Co., Inc. -
Organic Materials Dlv.
Location(s)2'3
Deepwater, N. J.
1975
capacity2
MM kg (MM Ib)
20.4 (45)
Total1" 5-
production
MM kg (MM Ib)
for year of estimate
_
Sauget, 111.
Milwaukee, Wise.
Midland, Mich.
Rochester, N. Y.
Sauget, 111.
Irwindale, Calif.
Ardsley, N. Y.
Niagara Falls,
Fords, N. J.
Oil City, Pa.
43.1 (95)
Total -
63.5 (140)
Total m,p,p cresol
10.5 (23-1) -1970
-------
Table A-l. (Continued)
Chemical
Usage1
Manufacturer (si.2..* 3
Location(s)2'3
1975
capacity2
MM kg (MM Ib)
Total*'5-
production
MM kg (MM Ib)
foryearof estimate
ON
00
Croton- Intermediate for n-
aldehyde butyl alcohol & 2-
ethyl-hexyl alcohol;
solvent; preparation of
rubber accelerators;
purification of lubrica-
ting oils; insecticides;
tear gas; fuel-gas warn-
ing agent; organic
synthesis; leather tan-
ning; alcohol denaturant
Crotonic Synthesis of resins,
acid polymers, plasticizers,
drugs
Cumene Production of phenol,
acetone, & alpha-
methylstyrene; solvent
Union Carbide Corp. -
Chems, & Plastics Div.
Institute &
Charleston, W. Va.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Ashland Oil, Inc. - Ash-
land Chem. Co., div, -
Petrochems, Div.
Clark Oil & Refining
Corp. - Clark Chem.
Corp., subsid.
Coastal States Gas Corp.
Coastal States Marketing,
Inc., subsid.
Dow Chem. U.S.A.
Gulf Oil Chems. Co.,
div. - Gulf Oil Corp. -
Petrochems, Div.
Marathon Oil Co.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Phillips Petroleum Co. -
Petrochem & Supply Div.
Skelly Oil Co.
Kingsport, Tenn.
Ashland, Ky.
Blue Island, 111.
Corpus Christi,
Midland, Mich.
Philadelphia, Pa.
Port Arthur, Tex.
Texas City, Tex.
Chocolate Bayou,
Phillips, Tex.
El Dorado, Kans,
136*2 (300) 1325.7 (2920) -197*1
50 (110)
63.6 (140)
4.5 (10)
204.3 (^50)
204.3 (450)
95.3 (210)
290.6 (640)
0.5 (1)
63.6 (140)
-------
Table A-l. (continued)
GO
^4
00
Chemical
Cumene
(con* t)
Cumene
hydro-
peroxide
Cyano-
acetlc
acid
Cyanogen
chloride
Cyanuric
acid
Cyanuric
chloride
(see previous page)
Production of acetone
& phenol; polymerization
catalyst, particularly
In redox systems, used
for rapid polymerization
Organic synthesis
Organic synthesis; tear
gas; warning agent in
fumigant gases
Organic synthesis
Chemical synthesis;
dyestuffs; Pharmaceuti-
cals; explosives;
surfactants
Manufact urer(s)2'3
Standard Oil of Calif. -
Chevron Chem. Co., sub-
sid., Oronlte Additives
& Indust. Chems. Div. -
Indust. Chems.
Standard Oil Co. (Ind.)
Amoco Chems. Corp.,
subsid.
Sun Oil Co. - Sun Oil
Co. of Penn., subsid. --
Suntide Refining Co.,
subsid.
Texaco Inc.
Union Carbide Corp. -
Union Carbide Carlbe,
Inc., subsid.
Allied Chem. Corp. -
Specialty Chems. Div.
Hercules Inc., Organics
Dept. - Synthetics Dept.
Reichhold Chems., Inc. -
Specialty Chems. Div.
Kay-Fries. Chems., Inc.
Nilok Chems., Inc.
PMC Corp. - Chem. Group-
Indus t . Chem, Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Cib;a-Geigy Corp. -
Agricultural Div.
Nilok Chems., Inc.
Locatlon(s)2'3
El Segundo, Calif.
Westville, N. J.
Penuelas, P. R.
Frankford, Pa.
Gibbstown, N. J.
Gibbstown, N. J.
Austin, Tex.
Stony Point, N. Y.
Memphis, Tenn.
South Charleston,
Everett , Mass .
Mclntosh, Ala.
St. Gabriel, La.
Memphis, Tenn.
1975
capacity2
MM kg (MM Ib)
45.4 (100)
Texas City, Tex. 22.7 (50)
Corpus Christ!, 113-5 (250)
63.6 (140)
290.6 (640)
Total =
1648 (363D
Total4'5
production
MM kg (MM Ib)
for year of estimate
(see previous page)
-------
Table A-l- (Continued)
Chemical
Cyclo-
hexane
oo
^j
vo
Cyclo-
hexanol
Manufacture of nylon;
solvent, for 'cellulose
ethers, fats, oils,
waxes, bitumens, resins,
crude rubber; extracting
essential oils; chemical
(organic synthesis, re-
crystallizing medium);
paint & varnish remover;
glass substitutes;
vapor has been u,sed as
lubricant for steel
(experimental)
Soap making; to in-
corporate solvents &
phenolic insecticides;
source of adipic acid
for nylon; textile
finishing solvent;
blending agent;lacquers;
paints & varnishes;
finish removers;, dry
cleaning; emulsified
products; leather
degreasing; polishes;
plasticizers; plas-
tics ; germicides
Manufacturer(s)2 *3
American Petrofina, Inc.
Cosden Oil & Chem. Co.,
subsid.
Commonwealth Oil Refin-
Co., Inc. - Corco
Cyclohexane, Inc. -
subsid.
Exxon Corp. - Exxon
Chem, Co., div. - EXxon
Chem. Co. U.S.A.
Gulf Oil Corp. - Gulf
Oil Chems. Co., div. -
Petrochems. Div.
Phillips Petroleum Co. -^
Phillips Puerto Rico
Core Inc., subsid.
Texaco Inc,
Union OiJ Co. of Calif-.
Union Pacific Corp, -
Champlin Petroleum Co.,
subsid.
Allied Chem. Corp. -
Fibers Div.
Celanese Corp. - Cela-
nese Chem, Co., div.
Dow Bad!sche Co.
El Paso Products Co.,
subsid, - El Paso
Natural Gas Co.
Monsanto Co. -- Monsanto
Indust. Chems. Co. -
Monsanto Textiles Co.
Nipro, Inc.
flohm & Haas Co. T Rohm
& Haas Ky. Inc.* subsid.
Location(s)2'3
Big Spring, Tex.
Penuelas, P. R.
Baytown, Tex.
Port Arthur, Tex.
Borger, Tex.
Sweeny, Tex.
Quayama, P. R.
Port Arthur, Tex.
Beaumont, Tex,
Corpus Christi,
Hopewell, Va.
Bay City, Tex.
Freeport, Tex.
Odessa, Tex.
Luling, La.
Pensacola, Pla.
Augusta, Ga,
Louisville, Ky.
Total*'5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
45.3 (99.8) 1062.lt (2340) -1974
117-7 (259.2)
117.7 (259.2)
97-1 (213.8)
117.7 (259.2)
252.8 (556.8)
214.7
m.7 (259.2)
3,00 (220.3)
67 (147.6)
Total =
1323.4 (2915.1)
325.5 (716.9) -1968
-------
Table A-l. (Continued)
Chemical
Cycln-
hex.,
00
00
o
Cyclo-
hexene
Cyelo-
hexyl-
amine
Organic synthesis;
particularly of adipic
acid & caprolactam (about
95%}', polyvlnyl chloride
& its copolymers, &
methacrylate ester poly-
mers; solvent for DDT in
aerosol bombs; general
wood stains; paint &
varnish removers; spot
& stain removers; de-
greasing of metals;
in polishes; leveling
agent in dyeing & de-
lustering silk; lube
oil additive; general
solvent
Organic synthesis;
catalyst solvent; oil
extraction
Boiler-water treatment;
corrosion inhibitor
in boilers; rubber
accelerator; inter-
mediate
Manufacturer's )_2 * 3
Allied Chem. Corp. -
Fibers Div.
Celanese Corp. - Cela-
nese Chem. Co., div.
Dow Badische Co.
El Paso Natural Gas Co. -
El Paso Products Co.,
subsid.
Monsanto Co. - Monsanto
Textiles Co.
Nipro, Inc.
Rohm & Haas Co. - Rohm
& Haas Ky. Inc. - subsid.
Union Carbide Corp. -
Cheras. & Plastics Div.
Phillips Petroleum Co. -
Petrochem, & Supply Div.
Uniroyal, Inc. - Uniroyal
Chem., div.
Abbott Labs. -
Chem. Div,
Monsanto Co. - Monsanto
Indust. Chems. Co.
Virginia Chems., Inc. -
Indust. Chems. Dept.
LocationCs)2 » 3
Hopewell, Va.
Bay City, Tex.
Freeport, Tex.
Odessa, Tex.
1975
capacity2
MM kg (MM lt>)
157.1 (316)
45.4 (100)
113-5 (250)
29 (64)
Total1" $•
production
MM kg (MM Ib)
for year of estimate
313-5 (756.5) -1971
Pensacolas Pla.
Augusta, Ga.
Louisville, Ky.
Taft, La.
Phillips, Tex.
Naugatuck, Conn.
Wichita, Kans.
Sauget, 111.
Portsmouth, Va.
227 (500)
68.1 (150)
18.2 (40)
31.8 (70)
Total -
701.4 (15115)
4.5 (10)
1 (2)
3.6 (8)
Total =
9-1 (20)
-------
Table A-l. (Continued)
oo
CO
Chemical
Decahydro-
naphtha-
lene
Decanol
Diacetone
alcohol
Solvent for oils, fats,
waxes, resins, rubber,
etc.; substitute for
turpentine; cleaning
machinery; stain-re-
mover ; shoe creams,
floor waxes, etc. ;
cleaning fluids;
lubricants
Plasticizers; deter-
gents i synthetic lubri-
cants; solvents; per-
fumes; flavorings
Solvent for nitro-
cellulose, cellulose
acetate, variovis oils,
resins, waxes, fats,
dyes, tars; lacquers;
dopes, coating composi-
tion; wood preservatives;
stains; rayon & artifical
leather; imitation gold
leaf; dyeing mixtures;
antifreeze mixtures;
extraction of resins &
waxes; preservative for
animal tissues; metal-
cleaning compounds;
hydraulic compression
fluids; stripping
agent (textiles); labora-
tory reagent; the techni-
cal grade, containing
acetone, has greater
solvent power
Manufacturer(s)2*3
E. I. du Pont de Ne-
mours S Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div,
Lonza Inc.
Continental Oil Co. -
Conoco Chems.
The Proctor S Gamble
Co.
Celanese Corp. - Cela-
nese Chem. Co., div.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics
Div.
LocationCs)2'3
Deepwater, N. J.
Mapleton, 111.
Westlake, La.
Ivorydale, Ohio
Bishop, Tex.
Deer Park, Tex.
Dominguez, Calif.
Institute & South
Charleston, W. Va.
1975
capacity2
MM kg (MM Ib)
Total1*'5
production
MM kg (MM Ib)
for r ear of estimate
Diamino-
benzoic
acid
Bofors Indust., Inc.
Salsbury Labs.
Linden, N. J.
Wilmington, N. C.
-------
Table A-l. (Continued)
Chemical
Dichloro-
aniline
oo
to
Dichloro-
ben?ene
(m,p,p)
Usage1
Dye intermediate;
intermediate for
biologically active
compounds
Mfg. of 3,1-dichloro-
anilinej solvent for a
wl
-------
Table A-l. (Continued)
Chemical
Manufacturer(s)2 *3
Location(s)2*3
1975
capacity2
MM kg (MM Ib)
Total1"5
production
MM kg (MM Ib)
for year of estimate
00
00
Dichloro- General solvent for
ethylene organic materials; dye
(vinyl- extraction; perfumes;
idene lacquers; thermoplastics;
chloride) organic synthesis;
medicine; copolymerised
with vinyl chloride or
acrylonitrile to form
various kinds of
saran; other copolymers
are also made; adhesives;
component of synthetic
fibers
Dichloro- General solvent; selee-
ethyl tive solvent for produc-
ether tion of high-grade lubri-
cating oils; textile
scouring & cleansing;
fulling compounds; wet-
ting & penetrating com-
pounds ; organic synthe-
sis; paints, varnishes,
lacquers; finish removers;
spotting & dry cleaning;
soil fumigant
Dichloro- General solvent; inter-
hydrin mediate in organic syn-
thesis ; paints, varnishes,
lacquers, celluloid
cements; water colors'
binder; photographic
lacquers
Dichloro- Solvent for oils, greases,
pentane rubber, resins & bi-
tuminous materials; removal
of tar; reclaiming rubber;
paint & varnish removers;
degreasing of metals;
insecticide; soil fumi-
gant; removal of wax
deposits on oil-well
equipment
Dow Chem. U.S.A.
PPG Indust., Inc. -
Chem. Div. - Indust,
Chem. Div.
Preeport, Tex.
Plaquemine, La.
Lake Charles, La.
Buckman Labs., Inc.
Dow Chem. U.S.A.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Organic Chems.
Cadet, Mo.
Memphis, Tenn.
Preeport, Tex.
Institute & South
Charleston, W. Va.
Rochester, N. Y.
-------
Table A-l. (Continued)
Chemical
Dichloro-
propene
Dicyclo-
hexyl-
amine
Usage1
Organic synthesis;
soil fumigants
Intermediate; insecti-
cides; plasticizer;
corrosion inhibitors;
antioxidants in rubber;
lubricating oils, fuels;
catalysts for paint,
varnishes & inks ;
detergents; extractant
Manufacturer^)2,1 3
Dow Chemical U.S.A.
Abbott Labs, - Chem.
Div,
Va. Chems. Inc. -
Indust . Chems . Dept .
LocationCs]2 *
Preeport , Tex
Wichita, Kans
1
.
Portsmouth, Va
00
00
Diethanol- Liquid detergents for
amlne emulsion paints, cutting
oils, shampoos, cleaners,
& polishes; textile
specialties; absorbent
for acid gases; chemical
intermediate for resins &
plasticizers, etc.;
solubilizing 2,4-D
Diethylene Polyurethane & unsatu-
glycpl rated polyester resins;
triethylene glycol; tex-
tile softener; petroleum
solvent extraction; de-
hydration of natural gas;
plasticizers & surfac-
tants; solvent for
nitrocellulose, & many
dyes & oils; humectant
for tobacco, casein,
synthetic sponges, paper
products; cork composi-
tions; book-binding
adhesives; dyeing as-
sistant ; cosmetics
Allied Chem. Corp. -
Specialty Chems. Div.
Dow Chem. U.S.A.
Olin Corp. - Designed
Products Div.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Allied Chem. Corp. -
Specialty Chems. Div.
BASF Wyandotbe Corp. -
Indust. Chems. Group
Celanese Corp. -
Celanese Chem. Co., dlv.
Dixie Chem. Co.
Dow Chem. U.S.A.
Eastman Kodak Co. - East-
man Chem. Products, Inc.,
subsld. - Texas East-
man Co., div.
Orange, Tex.
1975
capacity2
MM kg (MM Ib)
Total1* '-
production
MM kg (MM Ib)
for year of estimate.
9.1 (20)
50.^t (111)
-1971
Preeport, Tex.
Midland, Mich.
Brandenburg, Ky .
Port Heches, Tex.
Seadrift, Tex.
13.6
15.9
11.3
31
113.5
(30)
(35)
(25)
(75)
(250)
•Total =
197-5 (435)
Orange, Tex.
Gelsmar, La.
Clear Lake, Tex.
Bayport, Tex.
Freeport, Tex.
Plaquemine, La.
Longview, Tex.
1.5
9.5
10.9
_
10.9
21.3'
3.6
(10)
(21)
(21)
(21)
(17)
(8)
122 (268.7) -1973
Includes mono- and tri-ethanol amines
-------
Table A-l. (Continued)
00
00
Chemical
Diethylene
glycol
(Con't)
Diefchylene
glycol
mono-
butyl
ether
Diethylene
glycol
mono-
butyl
ether
acetate
Usage1
(see previous page)
Solvent for nitro-
cellulose, oils, dyes,
gums, soaps, polymers;
plasticizer intermediate
Solvent for oils, resins,
gums, also for cellulose
nitrate & polymeric
ings; plasticizers in
lacquers & coatings
Mamifacturer(s)^^3
Northern Natural Gas
Co - Northern Petro-
chem. Co., subsid. -
Polymers Div.
LocationCs)2*3
Morris, 111.
Inc., subsid.
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Olin Corp. - Designed
Products Div.
Shell Chem. Co. -
Base Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. - East-
man Chem. Products, Inc.,
subsid. - Tex. Eastman
Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
Midland, Mich.
Longview, Tex.
Brandenburg, Ky.
Geismar, La,
Port Neches, Tex.
Institute & South
Charleston, W. Va.
Longview, Tex.
Institute & South
Charleston, W. Va.
1975
capacity2
MM kg (MM Ib)
13.6 (30)
Total1"5
production
MM kg (MM Ib)
for year of production
(see previous page)
Olin Corp. - Designed
Products Div.
PPO Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div. -
PPG Indust. (Caribe)
Shell Chem. Co. -
Base Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. 8 Plastics Div.
Union Carbide Caribe,
Brandenburg, Ky.
Beaumont, Tex.
Guayanllla, ?. R.
Geismar, La.
Port Neches, Tex.
Seadrirt, Tex. T
Taft, La.
Penuelas, P. R. 1
2.3
1.5
18.2
1.5
16.3
97.6
(5)
(10)
(10)
(10)
(36)
(215)
Total -
218 (480)
6.8 (15)
-1972
-------
Table A-l. (Continued)
Chemical
Manufacturer(s)2 * 3
Location(s)2'3
1975
capacity2
MM kg (MM Ib)
Total1" s-
production
MM kg (MM Ib)
for year of estimate
oo
00
CTv
Diethylene
glycol
mono-
ethyl
ether
Diethylene
glycol
mono-
ethyl
ether
acetate
Diethylene
glycol
mono-
hexyl
ether
acetate
Diethylene
glycol
mono-
methyl
ether
Solvent Tor dyes, nitro-
cellulose, & resins, mu-
tual solvent for mineral
oil-soap & mineral oll-
sulfonated oil mixtures;
nonaqueous stains for
wood; for setting the
twist & conditioning
yarns & cloth; textile
printing; textile soaps;
lacquers; organic syn-
thesis; brake fluid
diluent
Solvent for cellulose
esters, gums, resins;
coatings & lacquers;
printing inks
Solvent; brake fluid
component; Intermediate
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. -- Texas
Eastman Co., div.
Olin Corp, - Designed
Products Div.
Shell Chem. Co. -
Base Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Dow Chem. U.S.A.
Eastman Kodak Co. - East-
man Chem, Products, Inc.,
subsid. - Texas Eastman
Co., div.
Olin Corp. - Designed
Products Div.
PPO Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div.
Shell Chem. Co. - Base
Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Midland, Mich.
Longview, Tex.
Brandenburg, Ky.
Geismar, La.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
20.il (il5) -1972
Midland, Mich.
Longview, Tex,
Brandenburg, Ky.
Beaumont, Tex.
Geismar, La.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
6.8 (15) -1972
-------
Chemical
Table A-l. (Continued)
Manufa,cturer(s)2> 3
Location(s)2*3
1975
capacity2
MM kg (MM Ib)
Total1"5
production
MM kg (MM Ib)
for year^jxf estimate
00
oo
Diethylene
glycol
mono-
methyl
ether
acetate
Diethylene
glycol
dibutyl
ether
Diethylene
glycol
diethyl
ether
Diethylene
glycol
dimethyl
ether
Diethyl-
amine
Diethyl
sulfate
High-boiling, inert
solvent with applica-
tion in extraction pro-
cesses & in coatings
& inks; diluent in
vinyl chloride disper-
sions; extractant for
uranium ores
Solvent for nitrocellu-
lose ; resins, lacquers;
high-boiling medium &
solvent for organic
synthesis
Solvent; anhydrous reac-
tion media for organo-
metallic syntheses
Rubber chemicals; tex-
tile specialties;
selective solvent; dyes;
flotation agents; resins;
pesticides; polymeriza-
tion inhibitors; Pharma-
ceuticals ; petroleum
chemicals; electroplat-
ing; corrosion
inhibitors
Ethylating agent in
organic synthesis
Union Carbide Corp. -
Chems, & Plastics Div.
Union Carbide Corp. -
Chems. & Plastics Div.
The Ansul Co. - Chem.
Div,
Olin Corp. - Designed
Products Div.
Air Products & Chems.,
Inc.
Pennwalt Corp. - Chem.
Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Va. Chems. Inc. -
Indust. Chems. Dept.
Union Carbide Corp. -
Chems. & Plastics Div.
Institute & South
Charleston, W. Va.
Institute & South
Charleston, W. Va.
Marinette, Wise.
Rochester, N. Y.
Pensacola, Pla.
Wyandotte, Mich.
Taft, La.
Portsmouth, Va.
Institute & South
Charleston, W. Va.
5 (11.1) -1972
-------
Table A-l. (Continued)
OO
00
00
Chemical
DIfluoro- Refrigerant; aerosol
ethane propellant; Intermediate
Diiso- Alkylation; intermediates;
butylene antioxldants; surfactants;
lube additives; plastici-
zers; rubber chemicals
DIketene Production of aceto-
arylamides; pigments &
toners; pesticides; food
preservatives; pharma-
ceutical intermediates
Dimethyl- Acid gas absorbent; sol-
amine vent; antioxidants; mfg.
of dimethylformamide &
dimethylacetamide; dyes;
flotation agent; gasoline
stabilizers; pharmaceuti-
cals; textile chemicals;
rubber accelerators;
electroplating; dehalring
agent; missile fuels;
pesticide propellant;
rocket propellants;
surfactants
N,N-dl- Dyes; intermediate's;
methyl- solvent; manufacture of
aniline vanillin; stabilizer
(acid accepter)
Manufacturer(s)2*3
Allied Chem. Corp. -
Specialty Chems. Div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Preon® products div.
The B. P. Goodrich Co. -
B. F. Goodrich Chem.
Co., div.
Petro-Tex Chem. Corp. -
Petro-Tex Chem. Co.,
subsld.
Texaco Inc.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsld. - Tenn.
Eastman Co., div.
PMC Corp. - Chem. Group -
Indust. Chem. Div.
Air Products & Chems.,
Inc.
Commercial Solvents Corp.
E. I. du Pont de Ne-
mours & Co., Inc.,
Biochems. Dept.
GAF Corp. - Chem. Div.
Allied Chem. Corp. -
Specialty Chems. Div.
American Cyanamid Co. -
Organic Chems. Div.
E, I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Dept.
Dye Specialities, Inc.
Location(s)2*3
Baton Rouge, La.
Louisville, Ky.
Port Neches, Tex.
Houston, Tex.
Port Arthur, Tex.
Kingsport, Tenn.
Meadvllle, Pa.
Pensacola, Fla.
Terre Haute, Ind.
Belle, W. Va.
Calvert City, Ky.
Buffalo, N. Y.
Bound Brook, N. J.
Deepwater, N. J.
Jersey City, N. J.
1975
capacity2
MM kg (MM Ib?
Total1**5
production
MM kg (MM Ib)
fgr_y_e_ar_._pf_ estimate
55-2 (121.5) -1973
-------
Chemical
Table A-l. (Continued)
Locations)2'3
1975
capacity2
MM kg (MM Ib)
Totall|>5
production
MM kg (MM Ib)
for year of estimate
oo
00
VO
Dimethyl Refrigerant; solvent;
ether extraction agent; propel-
lant for sprays; chemical
(reaction medium); cata-
lyst & stabilizer in
polymerization
N,N-dl- Solvent for vinyl resins
methyl- & acetylene, butadiene,
formamide acid gases; catalyst
in carboxylation reac-
tions ; organic synthesis
Dimethyl Methylating agent for
sulfate amines & phenols
Dimethyl Gas odorant; solvent
sulfide for many inorganic
substances; catalyst
impregnator
Dimethyl Solvent for polymeriza-
sulfoxide tion & cyanide reactions;
analytical reagent; spin-
ning polyacrylonitrile &
other synthetic fibers;
industrial cleaners pesti-
cides, paint stripping;
hydraulic fluids;
preservation of cells at
low temperatures; diffu-
sion of drugs, etc.,
into blood stream by
topical application;
medicine; plant patho-
logy & nutrition
E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
Union Carbide Corp. -
Chems. & Plastics Div.
Air Products & Chems.,
Inc.
E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
Lachat Chems. Inc.
E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems.Dept. -
Indust. Chems. Dept.
Crown Zellerbach Corp. -
Chem. Products Div.
Pennwalt Corp. - Chem.
Div.
Phillips Petroleum Co. -
Petrochem. & Supply Div.
Crown Zellerback Corp. -
Chem. Products Div.
Belle, W. Va.
Institute & South
Charleston, W. Va.
Pensacola, Fla.
Belle, W. Va.
Chicago Heights,
111.
Belle, W. Va.
Linden, N, J.
Bogalusa, La.
Beaumont, Tex.
Phillips, Tex.
Bogalusa, La.
Camas, Wash.
-------
Table A-l. (Continued)
Chemical
Manufacturer(s ) 2 J 3
Location(s)2'3'
1975
capacity2
MM kg (MM Ib)
Total1**5-
production
MM kg (m Ib)
for year of estimate
oo
^o
o
Dinitro-
benzene
Dinitro-
benzoic
acid
Dinltro-
toluene
Dioxane
Organic synthesis;
dyes; camphor substitute
in celluloid ,production
Dioxo-
lane
Organic synthesis;
toluidines; dyes;
explosives
Solvent for cellulosics
& wide range- of organic
products; lacquers;
paints i varnishes;
paint & varnish re-
movers j wetting & dis-
persing agent in tex-
tile processing, dye
baths, stain and print-
ing compositions;
cleaning & detergent
preparations; cements;
cosmetics; deodorants;
fuinigants; emulsions;
polishing compositions;
stabilizer for chlori-
nated solvents; scintil-
lation counter
Low-boiling solvent &
extractant for oils,
fats, waxes, dyes, &
cellulose derivatives
Ashland Oil, Inc. -
Ashland Chem. Co., dlv.
Chem. Products Div.
Bofors Indust., Inc.
Salsbury Labs.
Air Products & Chems,,
Inc.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.
Rubicon Chems. Inc.
Dow Chem. U.S.A.
Ferfo Corp. - Grant
Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Dlv.
Ferro Corp. - Grant
Chem. Div.
Great Meadows,
Linden, N. J,
Charles City,
Iowa
Pensacola, Fla.
Deepwater, N. J.
Geismar, La.
Freeport, Tex.
Baton Rouge, La.
Institute & South
Charleston, W. Va.
Baton Rouge, La.
-------
Table A-l. (Continued)
Chemical
Diphenyl-
amine
oo
vo
Dlphenyl
oxide
Rubber antioxidants &
acceleratprs; stabiliz-
ers for plastics; solid
rocket propellants;
pesticides; explosives;
dyes; Pharmaceuticals
Organic synthesis;
perfumery, particularly
soaps; heat-transfer
medium; resins for
laminated electrical
insulation
Manufacturer (_s)_2_*_3
American Cyanamid Co,
Organic Chems. Div.
E. I. du Pont de Ne-
mours & Co., Indust.
Chems. Dept.
First Mississippi
Corp. - First Chem.
Corp., subs id,
Rubicon Chems. Inc.
Dow Chem. U.S.A.
Locatlon(s)2*3
Bound Brook, N. J.
Gibbstown, N. J.
Pascagoula, Miss.
Geismar, La.
Midland, Mich.
1975
capacity2
MM kg (MM Ib)
Total1*'5
production
MM kg (MM lb)
for ygar of estimate
Diphenyl- Intermediates; dyes
thiourea (sulfur colors, indigo,
methyl indigo); vulcani-
zation accelerator;
synthetic organic
Pharmaceuticals; flota-
tion agent; acid
inhibitor
Dipropy- Solvent for nitrocellulose; Dow Chem. U.S.A.
lene shellac; partial solvent
glycol for cellulose acetate;
solvent mixtures; lacquers; p^ducts Div.
coatings; printing anks
Oxirane Chem. Co.,
Texaco Inc., Jefferson
Chem. Co., Inc., subsId,
Union Carbide Corp. -
Chems. & Plastics Div.
American Cyanamid Co. -
Organic Chems. Div.
Monsanto Co. - Monsanto
Indus t. Chems. Co.
Olin Corp. - Designed
Bound Brook, N. J.
Nitro, W. Va.
Preeport, Tex.
Plaquemine, La.
Brandenburg, Ky.
Bayport, Tex.
Port Neches, Tex.
Institute & South
15.9 (35)
5.1 (12)
2.3 (5)
5.9 (13)
3.2 (7)
5.4 (12)
Total =
38.1 (84)
24.2 (53-3) -1973
-------
Table A-l. (Continued)
Chemical
Dodecene
00
Dodecyl-
aniline
Dodecyl-
phenol
Epiehloro-
hydrln
Flavors; perfumes;
medicine; oils; dyes;
resins
Intermediate
Solvent; intermediate
for surface-active
agents; oil additives;
resins; fungicides;
bactericides; dyes;
Pharmaceuticals, ad-
hesives; rubber
chemicals
Major raw material for
epoxy & phenoxy resins;
mfg. of glycerol; cur-
ing propylene-based
rubbers; solvent for
cellulose esters &
ethers; high wet-
strength resins for
paper industry
Manufacturer (s)2 ^3
Atlantic Richfield Co. -
ARCO Chem. Co., div.
Continental Oil Co. -
Conoco Chems.
Exxon Corp. - Exxon
Chem. Co., dlv. -
Exxon Chem. Co. U.S.A.
Gulf Oil Corp. - Gulf
Oil Chems. Co., div.
Petrochems. Div.
The Humphrey Chem. Co.
Sun Oil Co. - Sun Oil
Co. of Penn., subsid.
Texaco Inc.
Union Oil Co. of Calif.
Monsanto Co. - Monsanto
Indust. Chems. Co.
GAP Corp. - Chem. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Productol Chem. Co.
Union Carbide Corp. -
Chems. & Plastics Div.
Dow Chem. U.S.A.
Shell Chem. Co. - Base
Chems.
Locatlon(s)2'3
Wilmington, Calif.
Westlake, La.
Baton Rouge, La.
Cedar Bayou, Tex.
North Haven, Conn.
Duncan, Okla.
Marcus Hook, Pa.
Toledo, Ohio
Port Arthur, Tex.
Beaumont, Tex.
Sauget, 111.
Calvert City, Ky.
Kearnv, N. J.
Santa Fe Springs,
calif.
Marietta, Ohio
Preeport, Tex.
Deer Park, Tex,
Norco, La.
1975
capacity2
MM kg (MM Ib)
Total1* >5
production
MM kg (MM Ib)
forvear of estimate
12M.8 (275)
72.6 (160)
27.2 (60)
Total -
224.7
81.7 (180) -1973
-------
Table A-l. (Continued)
Chemical
Ethanol
00
VO
co
Ethyl
acetate
Solvent for resins, fats,
oils, fatty, acids, hydro-
carbons, alkali hydroxi-
des; extractive medium;
manufacture of inter-
mediates, organic deri-
vatives (especially ace-
taldehyde), dyes, syn-
thetic drugs, elasto-
mers , detergents, clean-
ing solutions, surface
coatings, cosmetics,
-Pharmaceuticals» ex-
plosives., anti-freeze;
beverages5 antisepsis;
medicine
General solvent in
coatings & plastics;
organic synthesis;
smokeless powders;
Pharmaceuticals
Manufacturer^ )2 *_j_
Commercial Solvents
Corp.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Georgia-Pacific Corp. -
Chem. Div.
Grain Processing Corp.
Inland Chem. Corp.
National Distillers &
Chem. Corp. - Chems.
Div. - U.S. Indust.
Chems. Co., div.
Publicker Indust. Inc.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Celanese Corp. -
Celanese Chem. Co., div,
Eastman Kodak Co. -
Eastman Chem, Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Monsanto Co. - Monsanto
Indus t. Chems. Co. -
Monsanto Polymers &
Petrochems. Co.
Publicker Indust. Inc.
Union Carbide Corp.
Chems. and Plastics Div.
Location(s)2'3
Terre Haute,
Longview, Tex.
Bellingham, Wash.
Muscatine, Iowa
Juneau, Wise-.
Tuscola, 111.
Gretna, La.
Philadelphia, Pa.
Deer Park, Tex.
Texas City, Tex.
Bishop, Tex.
Pampa, Tex.
Kingsport,, Tex.
Longview, Tex.
Trenton, Mich.
Springfield, Mass.
PhiladeIphis, Pa.
1975
capacity2
MM kg (MM Ib)
71.1 (161)
11.9 (26.3)
196.7 (133.2)
178.9 (39D
119.2 (262.6)
357.6 (787.7)
Total •
938.8 (2067.8)
27.2 (60)
9 (20)
9 (20)
6.8 (15)
Total"'5
production
MM kg (MM Ib)
for year of estimate
862.6 (1900) -1971
(20)
(20)
Brownsville, Tx.
Institute and South
Charleston, W.Va. 15.1 (100)
Texas City, Tex.
Total =
115.8 (255)
Ethyl Organic synthesis;
aceto- antipyrine; lacquers;
acetate dopes; plastics;
manufacture of dyes,
Pharmaceuticals, anti-
malarials, vitamin B;
flavoring
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Lonza Inc.
Kingsport, Tenn.
Mapleton, 111.
-------
Chemical
Table Art- (Continued)
LocationCs)2'3
1975
capacity2
MM kg (MM Ib]
Total1**5
production
MM kg (MM Ib)
for f_e ar _c> f . es t i ma t e
Ethyl
aery late
Polymers; acrylic
paints; intermediates
oo
Ethyl-
ami ne
Ethyl
benzene
Dye intermediates;
solvent extraction;
petroleum refining;
stabilizer for rubber
latex; detergents;
organic synthesis
Intermediate in produc-
tion of styrene;
solvent
Celanese Corp. - Cela-
nese Chem. Co., div.
Dow Badisehe Co.
Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
s ub s i d.
Union Carbide Corp. -
Chems. S Plastics Div,
Air Products & Chems.,
Pennwalt Corp. -
Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Virginia Chems. Inc. -
Indust. Chems. Dept.
American Petrofina,
Inc. - Cosden Oil &
Chem. Co., subsld.
ARCO/Polymers, Ine.
The Charter Co. -
Charter Oil Co., subsid.
Charter International
Oil Co., subsid.
Commonwealth Oil Refin-
ing Co., Inc. - Styro-
chem Corp., subsid.
Clear Lake, Tex.
Pampa, Tex.
Freeport , Tex .
Deer Park, Tex.
Taft, La.
Pensacola, Pla.
Wyandotte, Mich.
Taft, La,
Portsmouth, Va.
Big Spring, Tex.
Houston, Tex.
Port Arthur, Tex.
Houston, Tex.
Penuelas, P. R.
75 (165.2)-1968
Gulf Oil Chems. Co.,
div. - Petrochems.
Div.
25.2 (55.5) -1972
61.3 (135) 2588 (5700) -1974
(100)
245.2
15.9 (35)
40.9 (90)
Cos-Mar, Inc.
Dow Chem. U.S.A.
El Paso Natural Gas
Co., El Paso Products
Co. , subsid.
Poster Grant Co., Inc.
Oulf Oil Corp. -
Carville, La.
Freeport, Tex.
Midland, Mich.
Odessa, Tex.
Baton, Rouge, La.
Welcome, La.
326.9 (720)
846.7 (1865)
158.9 (350)
124.8 (275)
440.4 (970)
256.5 (565)
-------
-Table A-l. (Continued)
Ethyl
benzene
(oon't)
oo
VO
Ui
Ethyl
bromide
Ethyl
cellulose
Usage1
(See previous page)
Organic synthesis;
medicine (anesthetic)i
refrigerant; solvent;
grain & fruit
fumigant
Hot-melt adhesives &
coatings for cables,
paper, textiles, eta.;
extrusion wire insula-
tion; protective coatt
Ings; pigments-grind*
ing.base; toughening
agent for plastics;
printing inks; molding
powders; proximity
fuses; vitamin prepara-
tion; casing for rocket
propellants; food &•
feed additive
Manufacturer (s)2' 3
Monsanto Co, - Monsanto
Polymers & Petrochems.
Co.
Phillips Petroleum Co. -
Petrocheffi. & Supply Div.
Standard Oil Coj (Ind.)
Amqco Ghents. Corp.,
subsid.
Sun Oil Co, , Sun Oil
Co. of Pa., subsid. -\
Suntide Refining Co.,
subsid.
Tenneco Ino, -r Tenneco
Oil Co.,- div.
Union Carbide Corp. -
Chems. It Plastics Div.
Dow Chem. U.S.A.
Great Lakes Chem. Corp.
Northwest Indust., Inc. i-
Michigan Chem. Corp.,
subsid.
American Polymers, Inc.
Hercules Inc. - Coatings
4 Specialty Products
Dept.
Location!s)2'3
Chocolate Bayou,
Tex.
Texas City, Tex,
Phillips, Tex.
Texas City, Tex.,
Corpus Christ!,
Tex.
Chalmette, La.
Seadrift, Tex.
Midland, Mich.
El Dorado, Ark.
St. Louis, Mich.
Patterson, N. J.
1975
capacity2
MM kg (MM ,l.b)
667.4 (1170)
Total ""*
production
MM kg (MM Ib)
for year of.estimate
previous page)
«7.7 (106>
11.8 (26)
151 ,», (3«0)
Total *
3873.1 (853D
2.9 (6.5) -1973
-------
Table A-l. (Continued)
Chemical
Ethyl
chloride
OO
Ethyl
chloro-
acetate
Ethyl
cyano-
acetate
Ethylene
Manufacture of tetra-
ethyl lead & ethyl-
cellulose ; anesthetic;
organic synthesis,
alkylating agent;
refrigeration;; analy-
tical reagent; solvent
for phosphorus, sulfur,
fats, oils, resins &
waxes; insecticides
Solventi organic
synthesis; military
poison gas; vat
dyestuffs
Organic synthesis;
Pharmaceuticals;
dyes
Manufacture of ethyl
alcohol, ethylene
glycols, ethylene
dichloride, aluminum
alkyIs, vinyl chloride,
ethyl chloride, ethy-
lene oxide, ethylene
chlorohydrin, acetalde-
hyde, linear alcohols,
polystyrene, styrene,
polyethylene, poly-
vinyl chloride, SBR,
polyester resins trl-
chloroethylene, etc.;
refrigerant; cryogenic
research; agricultural
chemistry; welding &
cutting of metals;
anesthetic
Manufacturer(5)2
LOGatIpn(sI2 ' 3
Total1**5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
Dow Chem. U.S.A.
Ethyl Corp.
PPO. Indust., Inc. -
Chem. Div. - Indust.
Chem, Div.
Shell Chem. Co. -
Base Chems .
Stauffer Chem. Co. -
Plastics Div. -
Polymers West
Freeport , Tex.
Baton Rouge, La.
Pasadena, Tex.
Lake Charles, La.
Deer Park, Tex.
Carson, Calif.
31
95.3
68.1
51.5
38.6
50
(75) 299.7 (660.1) -1973
(210)
(150)
(120)
(85)
(110)
Total =
310.5 (750)
Dow Chem. U.S.A.
Kay-Fries Chems. Inc.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Kay-Fries Chems. Inc.
Lonza Inc.
Allied Chem. Corp. -
Union Texas Petroleum
Div.
Midland, Mich.
Stony Point, H. Y.
St. Louis, Mo.
Stony Point, N. Y.
Mapleton, 111.
Geismar, La.
Houston, Tex.
_
-
-
-
-
3^0.5
227
-
-
(750) 10,710.0 (23,590)-1971
(500)
ARCO/Polymers, Inc. -
Atlantic Richfield Co. -
ARCO Chem. Co., div.
Chemplex Co.
Cities Service Co., Inc.
North American Petroleum
Group
Continental Oil Co. -
Conoco Chems.
Dow Chem. U.S.A.
E. I. du Pont de Ne-
mours & Co., Inc. -
Plastics Dept.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Wilmington, Calif.
Clinton, Iowa
Lake Charles, La.
Westlake, La.
Bay City, Mich.
Freeport, Tex.
Plaquemine, La.
Orange, Tex.
Longview, Tex.
15.1 (100)
227 (500)'
426.8 (910)
295-1 (650)
77.2 (170)
1135 resoo)
499.lt (1100)
371-5 (825)
363.2 (800)
-------
Table A-l. (Continued)
Sthylene
(cont'd)
Usage1
(See previous page)
00
El Paso Natural Gas Co. -
El Paso Products Co.,
subsid.
Exxon Corp. - Exxon
Chem. Co., dlv. -
Exxon Chem. Co. U.S.A.
The B. P. Goodrich Co. -
B. P. Goodrich Chem. Co.,
div.
Gulf Oil Corp. - Gulf
Oil Chems. Co., div. -
Petrochems. Div.
Mobil Oil Corp. - Mobil
Chem. Co., div. -
Petrochems. Div.
Monsanto Co. - Monsanto
Polymers 6 Petrochems.
Co.
National Distillers &
Chem. Corp. - Chems.
Div. - U.S. Indust.
Chems. Co., div.
Northern Natural Gas Go.
Northern Petrochem. Co.,
subsid., Polymers Div.
Olin Corp. - Designed
Products Div.
Petro Gas Producing Co.
Phillips Petroleum Co.
Puerto Rico Olefins Co.
Shell Chem. Co. - Base
Chems.
Standard Oil Co. (Ind.) -
Amoco Chems. Corp.,
subsid.
SunOlin Chem. Co.
Location(s)2'3
Odessa, Tex.
Baton Rouge, La.
Baytown, Tex.
1975
capacity2
MM kg (MM Ib)
231.7
771.8
31.8
(517)
(1700)
(70)
Total4'5
production
MM kg (MM Ib)
for year of estimate
(See previous page)
Calvert City, Ky.
Cedar Bayou, Tex.
Port Arthur, Tex.
Beaumont, Tex.
Chocolate Bayou,
Texas City, Tex.
Tuscola, 111.
- Morris, 111.
Brandenburg, Ky.
Groves, Tex.
Sweeny, Tex.
Penuelas, P. R.
Deer Park, Tex.
Norco, La.
Chocolate Bayou,
Claymont, Del.
158.9 (350)
190.7
522.1 (1150)
295.1 (650)
68.1 (150)
158.9 (350)
363.2 (800)
5^.5 (120)
9 (20)
517.6 (1140)
45* (1000)
681 (1500)
250 (550)
45* (1000)
102 (225)
-------
Ethylene
(cont'd)
«£,
vo
00
Ethylene
carbonate
Ethylenp
chloro-
hydrln
Ethylene
diamlne
Usage1
(See pi*evious pafee)
Table A.-1. (Continued)
Mamxfacturer(s)2> 3
Texaco Inc. - Jefferson
Chem, Co., Inc., subsid.
Union Carbide Corp. *.
Chems. S? Plastics Div.
Onion Carbide CaribeA,
.Inc.,
Location(s)2'3
Port Neches, Tex.
Seadrift, Tex.
Jaft, La.
Texas City, Tex.
Tbrrance, Calif.
Whiting, In
-------
Table A-l. (Continued)
Chemical
Ethylene
dibrcmide
I
00
Ethylene
dichloride
Scavenger for lead in
gasoline; grain & fruit
f umigant; general sol-
vent ; waterproofing
preparations; organic
synthesis; insecticide;
medicine
Vinyl chloride; chlori-
nated solvent intermedi-
ate; coupling agent in
antiknock gasoline;
paint, varnish & finish
removers; metal degreas-
ing; soaps ft scouring
compounds; wetting &
penetrating agents;
organic synthesis; ore
flotation
Manufacturer(s)2 * 3
Dow Chem, U.S.A.
Ethyl Corp. - Brine
Products Dlv.
Great Lakes Chem. Corp.
Northwest Indust.,
Inc. - Michigan Chem.
Corp., subsid.
PPG Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div.
Allied Chem. Corp. -
Indust. Chems. Div.
Continental Oil Co. -
Conoco Chems.
Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co., Electro Chems. Div,
Dow Chem. U.S.A.
Ethyl Corp.
The B. P. Goodrich Co.
B. F. Goodrich Chem.
Co., div.
PPG Indust.
Chem.
Chem.
Div.
Div.
Inc. -
- Indust.
- PPG
PPG Indust..(Caribe)
Shell Chem. Co. -
Base Chems.
Stauffer Chem. Co, -
Plastics Div. - Poly-
mers West
Locations)2'3
Magnolia, Ark.
Midland, Mich.
Magnolia, Ark.
El Dorado, Ark.
El Dorado, Ark.
Beaumont, Tex.
Lake Charles, La.
Guayanilla, P. R.
Deer Park, Tex.
Norco, La.
Carson-, Calif.
1975
capacity2
MM kg (MM Ib)
Baton Rouge, La.
West lake, La.
Deer Park, Tex.
Freeport , Tex.
Oyster Creek, Tex.
Plaquemine, La.
Baton Rouge, La.
Pasadena, Tex.
Calvert City, Ky .
295.1
151
118
590.2
199.4
526.6
249. T
118
408.6
(650)
(1000)
(260)
(1300)
(1100)
(1160)
(550)
(260)
(900)
454 (1000)
379.1 (835)
544.8 (1200)
528.9 (1165)
136.2 (300)
Total*'5
production
MM kg (MM Ib)
for year of estimate
152.1 (335) -1973
3505 (7,720)-197*
-------
A-l. (Continued)
Chemical
Ethylene
dichloride
(cont'd)
Ethylene
glyeol
I
VD
O
O
Usage*
(See previous page)
Coolant & antifreeze;
asphalt-emulsion paints;
heat-transfer agent in
refrigeration & electron
tubes; low-pressure lami-
nates ; brake fluids;
glyeol diacetate; poly-
ester fibers & films;
low-freezing dynamite;
solvent; extractant for
various purposes; sol-
vent mixtures for cel-
lulose esters & ethers,
especially cellophane;
cosmetics £up to 53O;
lacquers; alkyd resins;
printing inks; wood
stains; adhesives;
leather dyeing; tex-
tile processing; tobac-
co; ingredient of
deicing fluid for
airport runways
Manufacturer(s)2 * 3
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Vulcan Materials Co. -
Chems. Div.
Allied Chem. Corp. -
Specialty Chems. Div.
BASF Wyandotte Corp. -
Indust. Chems. Group
Calcasleu Chem. Corp.
Celanese Corp. - Cela-
nese Chem. Co., div.
Dixie Chem. Co.
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
ICI United States Inc. -
Specialty Chems. Div.
Northern Natural Gas Co.,
Northern Petrochem. Co.,
subsid, - Polymers Div.
Olin Corp. - Designed
Products Div.
PPG Indust., Inc. -
Chem. Dlv. - Hous ton
Chem. Co., div. -
PPG Indust. (Caribe)
Shell Chem. Co. - Base
Chems.
Location(s)2*3
Port Nechea, Tex.
Taft, La.
Texas City, Tex.
Geismar, La.
Orange, Tex.
Geismar, La.
Lake Charles, La.
Clear Lake, Tex.
Bayport, Tex.
Preeport, Tex.
Plaquemine, La.
Longview, Tex.
New Castle, Del.
Morris, 111.
Brandenburg, Ky.
Beaumont, Tex.
Guayanilla, P. R.
Geismar, La.
Total4'5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
31.8 (70)
68.1 (150)
68.1 (150)
109 (240)
Total -
5,579-7 (12,290)
18.2 (40)
68.1 (150)
81.7 (180)
136.2 (300)
65.8 (145)
199.8 (440)
22.7 (50)
4.5 (10)
136.2 (300)
22.7
45.4 (100)
181.6 (400)
45.4 (100)
(See previous page)
1,398 (3,080)-1974
-------
Table A-l. (Continued)
I
VO
O
Chemical
Ethylene
glycol
(cont'd)
Ethylene
glycol
diacetate
Ethylene
glycol
dlbutyl
ether
Ethylene
glycol
diethyl
ether
Ethylene
glycol
dimethyl
ether
Ethylene
glycol
monoace-
tate
Usage1
(See previous page)
Solvent for cellulose
esters & ethers;
resins; lacquers;
printing inks; per-
fume fixative; non-
discoloring plastlci-
zer for ethyl &
benzyl cellulose
High-boiling inert
solvent; specialized
solvent & extraction
applications
Organic synthesis (reac-
tion medium); solvent &
diluent for detergents
Solvent
Solvent for nitro-
cellulose, cellulose
acetate, camphor
Manufacturers)z *3
Texaco Inc. - Jefferson
Chem. Co., Inc^,,subsid.
Union Camp Corp. -•
Chem. Products Div,
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc., subsid.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Corp. -
Chems. & Plastics Div.
The Ansul Co. - Chem.
Div.
Glyco Chems., Inc.
Scher Brothers, Inc.
Location(s)
2*3
Port Neches, Tex.
Dover, Ohio
Seadrift, Tex.
Taft, La.
Penuelas, P. R.
Klngsport, Tenn.
Institute & South
Charleston, W. Va.
Institute & South
Charleston, W. Va.
Marinefcte, Wise.
Williamsport, Pa.
Clifton, N. J.
1975
capacity2
MM kg (MM Ib)
Total1*'5
production
MM kg (MM Ib)
for year of g_stlma_te_
163.4 (360) (See previous page)
395 (870)
136.2 (300)
286 (630)
Total -
2-009
-------
Table A-l. (Continued)
Manufacturer(s)2 *3
Location(s)2>
1975
capacity2
MM kg (MM Ib)
Total4'5
production
MM kg (MM Ib)
for year of estimate
I
VD
O
Ethylene Solvent for nitrocellu-
glycol lose resins; spray lac-
mono- quers; quick-drying
butyl lacquers; varnishes;
ether enamels; dry-cleaning
compounds; varnish
removers; textile
(preventing spotting in
printing or dyeing);
mutual solvent for
"soluble" mineral oils
to hold soap in solution
& to improve the emulsi-
fying properties
Ethylene High-boiling solvent for
glycol nitrocellulose lacquers,
mono- epoxy resins, multicolor
butyl lacquers; film coalescing
ether aid for polyvinyl acetate
acetate latex
Ethylene Solvent for nitrocellulose;
glycol natural & synthetic resins;
mono- mutual solvent for formula-
ethyl tion of soluble oils; lac-
ether quers & lacquer thlnners;
dyeing & printing tex-
tiles; varnish removersj
cleaning solutions;
leather; anti-icing addi-
tive for avaltion fuels.
Sthylene Solvent for nitrocellu-
glycol lose; oils & resins; re-
mono- tards "blushing" in lac-
ethyl quers; varnish removers;
ether wood stains; textiles;
acetate leather
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Olin Corp. - Designed
Products Div.
Shell Chem. Co. - Base
Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. - East-
man Chem. Products, Inc.,
subsid. - Tenn.
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Olin Corp. - Designed
Products Div.
Shell Chem. Co. - Base
Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Olin Corp. - Designed
Products Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Midland, Mioh.
Longview, Tex.
Brandenburg, Ky,
Geismar, La.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
Kingsport, Tenn.
Institute & South
Charleston, W. Va.
Midland, Mich.
Longview, Tex.
Brandenburg, Ky.
Oeismar, La.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
Seadrlft, Tex.
Longview, Tex.
Brandenburg, Ky.
Institute & South
Charleston, W. Va.
(120) -1972
77.2 (170) -1972
-------
Table A-l. (Continued)
I
\D
O
Chemical
Ethylene
glycol
mono-
he xyl
ether
Ethylene
glycol
mono-
ethyl
ether
Ethylene
glycol
mono-
methyl
ether
acetate
Ethylene
glycol
mono-
octyl
ether
Usage1
High-boiling solvent
Solvent for nitro-
cellulose, cellulose
acetate, alcohol-
soluble dyes, natural
& synthetic resins;
solvent mixtures;
lacquers; enamels;
varnishes; leather;
perfume fixative;
wood stains; sealing
moixture-proof cello-
phane; jet fuel deicing
additive
Solvent for nitrocellu-
lose, cellulose acetate,
various gums, resins,
waxes, oils; textile
printing; photographic
film; lacquers; dopes
Solvent for cellulose
esters;
plasticiser
Manufacturer(s)2 *3
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Olin Corp. - Designed
Products Div,
Pierce Chem. Co.
PPG Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div.
Shell Chem. Co.
Base Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div,
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn..
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
LocationCs)2'3
Midland, Mich.
Longview, Tex.
Brandenburg, Ky.
Roekford, 111.
Beaumont, Tex.
Geismar, La.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
Taft, La.
Kingsport, Tenn.
Institute & South
Charleston, W. Va.
1975
capacity2
MM kg (MM Ib)
Total1**5
production
MM kg (MM Ib)
for year of e_stJLmatji
(95) -1972
-------
Table A-l. (Continued)
VO
O
Chemical
Ethylene
glycol
mono-
phenyl
ether
Ethylene
glycol
mono-
propyl
ether
Ethylene
oxide
Solvent for cellulose
acetate, dyes inks, re-
sins; perfume & soap
fixative; bacterial
agent; organic synthesis
of plasticizers, germi-
cides, perfume materials
& Pharmaceuticals
Manufacture of ethy-
lene glycol & higher
glycols; polyester fi-
ber & film; surfactants;
aerylonitrile; ethanol-
amines; petroleum demulsi-
fier; fumigant; rocket
propellant
Manufacturer(s)2'3
Dow Chem. U.S.A.
Olin Corp. - Designed
Products Inc.
Allied Chem. Corp. -
Specialty Chems. Div.
BASF Wyandotte Corp. -
Indust. Chems. Group
Calcasieu Chem. Corp.
Celanese Corp. -
Celanese Chem. Co., div.
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Northern Natural Gas -
Co - Northern Petrochem.
Co., subsid. - Poly-
mers Div.
Olin Corp. - Designed
Products Div.
PPG Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div.
PPG Indust. (Caribe)
Shell Chem. Co. -
Base Chems.
SunOlin Chem. Co.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc.» subsid.
Locations)2'3
Midland, Mich.
Brandenburg, Ky.
Longvlew, Tex.
Morris, 111.
Brandenburg, Ky.
Beaumont, Tex.
Guayanilla, P. R
Geismar, La.
Claymont, Del.
Port Heches, Tex.
Seadrift, Tex.
Taft, La.
Penuelas, P. R.
1975
capacity2
MM kg (MM Ib)
Orange , Tex .
Geismar, La.
Lake Charles, La.
Clear Lake, Tex.
Preeport , Tex.
Plaquemine, La.
22.7 (50)
100 (220)
74.9 (165)
136.2 (300)
90.8 (200)
181.6 (400)
18.2 (40)
90.8 (200)
50 (110)
38.6 (85)
136.2 (300)
136.2 (300)
1)3.1 (95)
227 (500)
367.7 (810)
201.3 (150)
277 (610)
Total =
2,195-1 (1,835)
Total1"5
production
MM kg (MM Ib)
for year of estimate
1,798 (3,960) -1971
-------
Chemical
Table A-l. (Continued)
Mariufacturer(s) 2* 3
Location(s)2'3
1975
capacity2
MM kg (MM ID)
Total1*'5
production
MM kg (MM Ib)
for^yearof estimate
Ethyl
ether
O
Ui
2-
Ethyl
hexanol
Manufacture of ethylene
& other chemical syn-
thesis; industrial sol-
vent (smokeless powder);
analytical chemistry;
anesthetic; perfumery;
extractant; alcohol
denaturant
Ethyl
ortho-
formate
Ethyl
oxalate
Ethyl
sodium
oxalacetate
Plasticizer for PVC
resins; defearning agent;
wetting agent; organic
synthesis; solvent
mixtures for nitrocel-
lulose, paints, lac-
quers , baking finishes;
penetrant for merceriz-
ing cotton; textile
finishing compounds;
plasticizers; inks;
rubber; paper; lubri-
cants; photography;
dry cleaning
Intermediate
Solvent for cellulose
& ethers, many natural
& synthetic resins; radio
tube cathode fixing lac-
quers; dye intermediate;
Pharmaceuticals; perfume
preparations; organic
synthesis
dyes; synthesis
Hercules Inc. -
Coatings & Specialty
Products Dept.
Mallinckrodt, Inc. -
Medicinal Div.
National Distillers &
Chem. Corp. - Chenis.
Div.
Publicker Indust., Inc.
Squibb Corp. - E. R.
Squibb & Sons, Inc.,
subsid. - U.S. Pharma-
ceutical Co. -
Operations
Union Carbide Corp. -
Chems. & Plastics Div.
Dow Badische Co.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
W. R. Grace & Co. -
Hatco Group - Hatco
Chem. Div.
Oxochem Enterprise
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc., subsid.
Kay-Fries Cherns., Inc .
PMC Corp.
Chem. Group - Indust.
Chem. Div.
PMC Corp.
Chem. Group - indust.
Chem. Div.
Hopewell, Va.
1 (2)
27.2 (60) -197*1
St. Louis, Mo.
Tuscola, 111.
Philadelphia, Pa.
New Brunswick,
1
18.2
4.5
1
(2)
(10)
(10)
(2)
Institute It South
Charleston, W. Va.
Texas City, Texas
Freeport, Tex.
Longview, Tex.
Fords, N. J.
Penuelas, P. R.
Deer Park, Tex.
Seadrift, Tex.
Penuelas, P. R.
Stony Point, N. Y.
Baltimore, Md.
6.8 (15)
Total =
32.2 (71)
Baltimore, Md.
-------
Table A-1- (Continued)
Chemical
Formalde-
hyde
(oontld)
(See previous page)
I
vo
O
Porma-
mide
Solvent, softener,
intermediate in or-
ganic synthesis
Manufacturer(s)2 * 3
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.,
subsid, - Durez Dlv.
Heichhold Chems., Inc.
Rohm & Haas Co.
Skelly Oil Co. -
Chembond Corp.,
subsid.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Dlv.
Union Carbide Corp. -
Chems. & Plastics Div.
Univar Corp. - Pacific
Resins & Chems., Inc.,
subsid.
Wright Chera. Corp.
E. I., du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
Location(s)2 ' 3
North Tonawanda,
N. Y.
Hampton, S. C.
Houston, Tex,
Kansas City, Kans.
Malvern, Ark.
Moncure, N. C.
Tacoma, Wash.
Tuscaloosa, Ala.
White City, Ore.
Philadelphia, Pa.
Springfield, Ore.
Winnfield, La.
Fords, N. J.
Garfield, N. J.
Bound Brook, N. J.
Eugene , Ore .
Acme, N. C.
1975
capacity2
MM kg (MM Ib)
61.3
22.7
51.5
22.7
50
51.5
21.8
32.7
113.5
11.3
31.8
31.8
81
45. «
51.5
13.1
36.3
(135)
(50)
(120)
(50)
(110)
(120)
(18)
(72)
(250)
(25)
(70)
(70)
(185)
(100)
(120)
(95)
(80)
Total -
3,808.0 (8,389)
Belle, W. Va.
-------
Table A-l. (Continued)
Chemical
Formalde-
hyde
VO
o
Urea & Melamine resins;
phenolic resins; ethylene
glyeol; pentaerythritol;
hexamethylenetetramine;
fertilizer; acetals; other
chemicals; dyes; medicine
(disinfectant, germicide);
embalming fluids; preser-
vative; hardening agent;
reducing agent, as in
recovery of gold & sil-
ver; corrosion inhibi-
tor in oil wells; durable-
press treatment of tex-
tile fabrics; possible
condensation to sugars
& other carbohydrates
for food use (ex-
perimental)
Manufacturer (s)2 J 3
Allied Chem. Corp. -
Specialty Chems. Div.
Borden Inc. - Borden
Chem. Div. - Adhesives
& Chems., Div., East
Adhesives & Chems., Div.,
West
Celanese Corp. - Cela-
nese Chem. Co., div.
Commercial Solvents
Corp,
E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
Indust. Chems. Dept.
GAP Corp. - Chem. Div.
Georgia-Pacific Corp. -
Chem. Div.
Gulf Oil Corp, - Gulf
Oil Chems. Co., div. -
Indust. & Specialty
Chems. Div.
Hercules Inc. -
Synthetics Dept.
Monsanto Co. - Monsanto
Polymers & Petrochems,
Co.
1975
capacity2
location(s)2'3
South Point, Ohio
Demopolis , Ala.
Diboll, Tex.
Fayetteville, N. C.
Louisville, Ky.
Sheboygan, Wise.
Fremont, Calif.
Kent, Wash.
La Grande , Ore .
Missoula, Mont.
Springfield, Ore.
Bishop, Tex.
Newark, N. J.
Rock Hill, S. C.
Seiple, Pa.
Belle, W. Va.
La Porte, Tex.
Healing Springs,
N. C.
Linden, N. J.
Toledo, Ohio
Calvert City, Ky .
Albany, Ore.
Columbus, Ohio
Coos Bay, Ore.
Crossett, Ark.
Taylorsville, Miss.
Vienna, Ga.
Vicksburg, Miss.
Louisiana, Mo.
Wilmington, N. C.
Addyston, Ohio
Chocolate Bayou,
Tex.
Eugene , Ore .
Springfield, Mass.
MM kg (MM Ib)
140.7
45.4
36.3
106.7
36.3
59
102.1
36.3
29.5
40.9
109
681
53.1
53.1
29.5
222.5
136.2
90.8
68.1
118
45.1
54.5
54.5
45.4
72.6
54.5
45.4
20.4
77.2
45.4
45.4
88.5
45.4
133.9
(310)
(100)
(80)
(235)
(80)
(130)
(225)
(80)
(65)
(90)
(240)
(1500)
(117)
(117)
(65)
(490)
(300)
(200)
(150)
(260)
(100)
(120)
(120)
(100)
(160)
(130)
(100)
(45)
(170)
(100)
(100)
(195)
(100)
(295)
Total*'5
production
MM kg (MM Ib)
for year of estimate
976 (2,150) -1971
-------
Table A-l. (Continued)
Chemical
Formic
acid
o
00
Pumaric
acid
Dyeing & finishing of
textiles & paper; leather
treatment; chemi-
cals (formates, oxalic
acid, organic esters);
manufacture of fumigants,
insecticides, refriger-
ants ; solvents for
perfumes, lacquers;
electroplating; medi-
cine; brewing (anti-
septic) ; silvering
glass; cellulose for-
mate; natural latex
coagulant; ore flota-
tion; vinyl resin
plasticizers; animal
feed additive
Modifier for polyester,
alkyd, & phenolic res-
ins; paper-size resins;
plasticizers; rosin es-
ters & adducts; upgrading
natural drying oils (es-
pecially tall oil) to
improve drying character-
istics; in foods, to re-
place citric & tartaric
acids as acidulant &
flavoring agent (PDA
approved); mordant;
organic synthesis
Manufacturer(s)2 J 3
Celanese Corp. -
Celanese Chem. Co.,
div.
Middleboro Indust.,
Inc.
Sonoco Products Co.
Union Carbide Corp. -
Chems. & Plastics Dlv.
Allied Chem. Corp. -
Specialty Chems. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsld. - Hooker
Chem. Corp., subsld. -
Hooker Chems. & Plastics
Corp., subsid, - Puerto
Rico Chem. Co., subsid.
Petro-Tex Chem. Corp. -
Fetro-Tex Chem. Co.,
Subsid.
Pfiaer Inc. - Chems. Div,
Tenneeo Inc. - Tenneco
Chems., Inc. - Organics
5 Polymers Div.
U.S. Steel Corp. - USS
Chems., div.
Location(s)2*3
Pampa, Tex.
Middleboro,
Mass.
Hartsville, S. C.
Brownsville, Tex.
Moundsville, W. Va.
St. Louis, Mo.
Areclbo, P. R.
Houston, Tex.
Terre Haute, Ind.
Garfield, N. J.
Neville Island, Pa.
1975
capacity2
MM kg (MM Ib)
4.5 (10)
3-2 (7)
.5 CD
22.7 (50)
Total =
30.9 (68)
6.8 (15)
13.6 (30)
Total1*'5-'
production
MM kg (MM Ib)
fgjr_yejir of estimate.
19-1 (42) -1974
3.6 (8)
11.3 (25)
4,5 (10)
4.5 (10)
Total •
Ml*.5 (98)
-------
Chemical
Table A-l. (Continued)
Manufacturer^)2'3
Location(s)2*3
1975
capacity2
MM kg (MM Ib)
Total1"5
production
MM kg (MM Ib)
for year of estimate
I
vo
O
Glycer- Biochemical research;
aide- intermediate; nutrition;
hyde preparation of polyes-
ters, adhesives; cellu-
lose modifier; leather
tanning
Glycerol Alkyd resins; eello-
(natural phane; explosives;
& ester gums; p-harmaceu-
synthetic) ticals; perfumery;
plastieizer for
regenerated cellulose;
cosmetics; foodstuffs;
conditioning tobacco;
liqueurs; solvent;
printer's ink rolls;
polyurethane poly-
ols; emulsifying
agent; rubber stamp
& copying inks; binder
for cements & mixes;
paper coatings &
finishes; special
soaps; lubricant &
softener; bacteriostat;
penetrant; hydraulic
flui d; h ume c t ant
Natural:
Acme-Hardesty Co., Inc.
Alba Mfg. Co.
Ashland Oil, Inc. -
Ashland Chem. Co., div.,
Chem. Products Div.
Chicago Sanitary Pro-
ducts Co.
Colgate-Palmolive Co,
Darling &. Co.
Dow Chem. Co.
Emery Indust., Inc. -
Western Operations
The Greyhound Corp. -
Armour & Co., subsid. -
Armour-Dial, Inc., div.
The Andrew Jergens Co.
H, Kohnstamm & Co., Inc.
Kraftco Corp. -
Humko Sheffield Chem.
Lever Brothers Co.
Millmaster Onyx Corp. -
A. Gross & Co., div.
Murro Chem. Co.
Pacific Soap Co.
Pioneer Soap Co., Inc.
Jenkintown, Pa.
Aurora, 111.
Hammond, Ind.
Mapleton, 111.
Chicago, 111.
Berkeley, Calif.
Jeffersonville, Ind.
Jersey City, N. J.
Kansas City, Kans.
Chicago, 111.
Anchorage, Alas.
Cincinnati, Ohio
Santa Fe Springs,
Calif.
Montgomery, 111.
Cincinnati, Ohio
Clearing, 111.
Memphis, Tenn.
Baltimore, Md.
Edgewater, N. J.
Hammond, Ind.
Los Angeles, Calif.
St. Louis, Mo.
Newark, N. J.
Portsmouth, Va.
Vernon, Calif.
San Francisco,
Calif.
158.1 (3^8.2) -19&9
-------
Table A-l. (Continued)
Chemical
Glycerol
(contTd)
Usage1
(See previous page)
I
vO
H1
O
Glycerol
trlfpoly-
oxypropy-
lene)
ether
Manufacturer (s ) 2 » 3
The Procter & Gamble Co.
The Hewitt Soap Co.,
Inc. , subsid.
Purex Corp., Ltd.
PVO Internat'l. Inc.
Safeway Stores, Inc. -
Newport Products Co.,
dlv.
Stepan Chem. Co. -
Surfactant Dept,
Union Camp Corp, -
Chem. Products Div.
Woburn Chem. Corp.
Synthetic:
Dow Chem. U.S.A.
PMC Corp. - Chem,
Group - Indust. Chem.
Div.
Shell Chem. Co. -
Base Chems .
ICI U.S. Inc. -
Specialty Chems. Div.
Olin Corp. - Designed
Products Div.
Pelron Corp.
Union Carbide Corp. -
Chems. & Plastics Div.
Witco Chem. Corp. -
Organics Div.
Location(s)2'3
Baltimore, Md.
Chicago, 111.
Dallas, Tex.
Ivorydale, Ohio
Kansas City, Kans.
Long Beach, Calif.
Port Ivory, N. Y.
Quincy , Mass.
Sacramento, Calif.
St. Louis, Mo.
Dayton, Ohio
Bristol, Pa.
Omaha, Neb.
Philadelphia, Pa.
Boonton, N, J.
Oakland, Calif.
Anaheim, Calif.
Elwood, 111.
Pleldsboro, N. J.
Dover, Ohio
Kearny, N. J.
Preeport, Tex.
Bayport, Tex.
Deer Park, Tex,
Norco, La.
New Castle, Del,
Brandenburg, Ky .
Lyons, 111.
Institute & South
Charleston, W. Va.
Clearing , 111.
Total4'5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
(See previous page)
-
~
-
~
~
-
-
50 (110)
18.2 (4o)
51.5 (120)
22.7 (50)
Synthetic Total =
145-.3 (320)
-
-
-
-
-
-------
Table Ar-1. (Continued)
Chemical
Glycine
Glyoxal
Guanidine
Heptene
Organic synthesis;
medicine; biochemical
research; buffering
agent; chicken feed
additive; reduces
bitter taste of
saccharin
Mfg. of te-xtile resins
for permanent press
process; dimensional
stabilization of rayon
& other fibers; inaolu—
bilizing agent for com-
pounds containing poly-
hydroxyl groups (poly-
vinyl alcohol, starch,
& celluloslc materialsH
insolubilizing of pro-
teins (casein, gelatin
& animal glue); embalm-
ing fluids; leather
tanning; paper coatings
with hydroxyethylcellu-
lose; reducing agent in
dyeing textiles
Organic synthesis
Organic synthesis; plant
growth retardant; lubri-
cant additive; catalyst
surfactants
Manufacturer(s)2*3
Chattem Drug & Chem.
Co. - Chattem Chems.
Div.
American CyanatnidT Co. •
Organic Chems, Div. —
(Captive Use)
Union Carbide Corp. -
Chems. & Plastics Div,
Witco Chem. Corp. -
0-rganics Div_
Location(s)2*3
Chattanooga* Tenn.
Charlotte, N. C.
Taft, La.
Clearing, 111.
1975
capacity2
MM kg (MM lb)_
Total1**5
production
MM kg (MM Ib)
for year of ._es_tiroatg
American Petrofina Inc.
Cosden Oil & Chem. Co.,
subsid.
Getty Oil Co.
The Humphrey Chem. Co.
Phillips Petroleum Co. -
Petrochem^ It Supply Div.
Standard Oil Co. (Ind.) -
Amoco Chems» Corp.,
subsid.
Big Spring, Tex.
Delaware City, Del.
North Haven, Conn.
Phillips, Tex.
Yorktown, Va.
20*1 (450) -1967
-------
Table A-l. (Continued)
Chemical
Manufacturer(s)2'3
Location (jO2 *
1975
capacity2
MM kg (MM Ib)
Total1**5
production
MM kg (MM Ib)
for year_ of estimate
Hexa-
chloro-
ethane
Hexa-
decyl
alcohol
r
^o
^_i
to
Hexa-
methy-
lene
glyccl
Hexa-
methy-
lene
tetra-
mine
Organic synthesis; re-
tarding agent in fer-
mentation; camphor sub-
stitute in nitrocellu-
lose; rubber accelera-
tor; pyrotechnics &
smoke devices; solvent;
explosives; medicine
Perfumery; emulsifier;
emollient; foam stabili-
zer in detergent; face
creams; lotions, lip-
sticks; toilet prepara-
tions; chemical inter-
mediate; detergents;
Pharmaceuticals; cosme-
tics; base for making
sulfonated fatty alco-
hols ; to retard evapor-
ation of water, when
spread as a film on
reservoirs, or sprayed
on growing plants
Solvent; resin inter-
mediate ; coupling
agent
Catalyst in phenol-
formaldehyde & resorcinol-
formaldehyde resins; in-
gredient in rubber-to-
textile adhesives; pro-
tein modifier; organic
synthesis; pharmaceuti-
cals; ingredient of high
explosive cyclonite
(q.v.); fuel tablets
Hummel Chem. Co., Inc.
Ashland Oil, Inc. -
Ashland Chem. Co.,
dlv. - Chem. Products
Div.
Continental Oil Co. -
Conoco Chems.
Glvaudan Corp. -
Chems. Div,
The Procter & Gamble
Co.
Robinson-Wagner Co.,
Inc.
Guardian Chem. Corp.
Eastern Chem. Div.
Borden Inc. - Borden
Chem. Div. - Adhesives
& Chems. Div. - East
W. R. Grace & Co. -
Indust, Chems. Group -
Dewey & Almy Chem. Div.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.
subsid. - Durez Div.
Plastics Engineering Co,
Tenneco Inc- - Tenneco
Chems., Inc. - Organics
Polymers Div.
Union Carbide Corp. -
Chems. & Plastics Dlv,
Wright Chem. Corp,
South Plainfield,
N. J.
Mapleton, 111.
Westlake, La.
Clifton, N. J.
Ivorydale, Ohio
Sacramento, Calif.
Mamaroneck, N. Y.
Hauppauge, N. ¥.
Demopolis, Ala.
Fayettevllle, N. C.
Nashua, N. H.
North Tonawanda,
Sheboygan, Wise.
Fords, N. J.
Bound Brook, N, J.
Acme, N. C.
2.72 (6.0) «1971
5.4 (12) ^5.7 (100.7) -1973
10.9 (24)
12.7 (28)
3.6
10 (22)
14.1 (3D
Total •
61.3 (135)
-------
Chemical
Table A-l. (Continued)
Manufacturer(s)2' 3
Location(s)2
1975
capacity2
MM kg (MM Ib)
Total'*'5'
production
MM kg (MM Ib)
for year of estimate
Hydrogen
cyanide
ON
VO
M
U>
Hydro-
quinone
m-
hydroxy-
benzoic
acid
Manufacture of acrylo-
nitrile, acrylates,
adiponitrile, cyanide
salts, dyes; fumigant
for orchards & tree
crops; chelates
Photographic deve-
loper (except color
film); dye intermediate;
medicine; antioxidant;
inhibitor; stabilizer
in paints & varnishes,
motor fuels & oils;
antioxidant for fats
& oils; inhibitor of
polymerization
Intermediate for plas-
ticizers; resins; light
stabilizers; petroleum;
additives; pharmaceuti-
cals; intermediates;
synthetic drugs
American Cyanamid
Co. - Indust. Chems. &
Plastics Div.
Dow Chem. U.S.A.
E. I. du Pont de Ne-
mours & Co., Inc. -
Elastomer Chems, Dept.
Indust. Chems. Dept, >
Plastics Dept.
Hercules Inc . - Coat-
ings & Specialty Products
Dept.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co,
Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
subsid.
The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid, - Chems. Dept.
Carus Corp. - Carus
Chem. Co. ., div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
The Goodyear Tire &
Rubber Co, - Chem. Div.
Mallinckrodt, Inc. -
Washine Div.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
New Orleans, La.
12.2 (27)
138.1 (304.3) -1973
Freeport, Tex
Beaumont, Tex
Laplace, La.
Memphis, Tenn.
Victoria, Tex.
Glens Pall
N. 1.
Chocolate Bayou, Tex.
Texas City, Tex.
Deer Park, Tex.
Lima, Ohio
La Sails, 111.
Kingsport, Tenn.
Bayport, Tex.
Lodi, N. J.
Garfield, H. J.
2.3
13.6
9.1
(5)
(30)
(20)
57.6 (127)
18.2 (40)
1.1 (2.4)
25.4 (56)
34.1 (75)
81.7 (180)
13.6 (30)
Total =
269 (592.4)
3-5 (7.7)
7-3 (16.0)
2.7 (6.0)
Total -
13.5 (29.7)
-------
Table A-"!, (continued)
ON
VD
Chemical
Isoamyl
alcohol
Isoamyl
chloride
Isoamylene
Isobutanol
Isobutyl
acetate
Isobutyral-
dehyde
Photographic chemicals;
organic synthesis; phar-
maceutical products;
medicine; solvent; deter-
mination of fat in mi!4c;
microscopy; flavoring
(Mixtures, us-ually also
containing normal amyl
chloride); solvent
(nitrocellulose, var-
nishes, lacquers, neo-
prene); rotogravure
inks? soil fumigation;
organic compounds
Organic synthesis;
dental & surgical
anesthetic; high octane
fuel manufacture
Organic synthesis; la-
tent solvent in paints &
lacquers; intermediate
for amino coating re-
sins; substitute for n-
butyl alcohol, paint re-
movers ; fluororaetrlc
determinations.; liquid
c hromat ography
Solvent for nitrocellu-
lose in thlnners, seal-
ants, & topcoat lacquers;
perfumery; flavoring
agent
Intermediate for rubber
antioxidants & accelera-
tors, for neopentyl
glycol; organic
synthesis
Manufacturer(s)2*3
Publicker Indust. Inc..
Union Carbide Corp.. -
Chems. & Plastics Div.
Phillips Petroleum Co.
Petrochem & Supply Div.
Bow Badische Co.
W. R. £race & Co. -
Hatco Group - Hatco
Chem. Div.
Oxochem Enterprise
Eastman Kodak Co. -
Eastman Chem. Products
Inc., subsid. - Tenn.
Eastman Co., div.
Fritzche Dodge &
Olcott Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Celanese Corp. -
Celanese Chem, Co., div.
Dow Badische Co.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Oxochem Enterprise
Union Carbide Corp. -
Chems. & Plastics Div. -
Union Carlbde Caribe,
Inc., subsid.
Location(s)2*3
Gretna, La.
Philadelphia, Pa.
Institute & South
Charleston, W. Va.
1975
capacity2
MM kg (MM lb)
Total1**5
production
MM kg (MM lb)
for year of estimate
Phillips, Tex.
Preeport, Tex.
Fords, N. J.
Penuelas, P, R.
Kingsport, Tenn.
East Hanover, N. J.
Institute & South
Charleston, W. Va.
Texas City, Tex.
Bishop, Tex.
Preeport, Tex.
Longview, Tex.
Penuelas, P. R.
Texas City, Tex.
Penuelas, P. R.
5.3 (11.75) -1972
-------
Table A-l. (Continued)
Chemical
Iso-
butyric
acid
Iso-
decanoic
acid
I
vo
M
Ui
Iso-
ol
Iso-
decyl
chloride
Iso~
octyl
alcohol
Manufacture of esters
for solvents, flavors,
& perfume bases; dis-
infecting agent;
deliming hides;
varnish; tanning
agent
Intermediate for metal
salts, ester type
lubricants, plasticlzers
Antifoaming agent in
textile processing
Solvent for oils, fats,
greases, resins, gums,
extractants, cleaning
compounds; intermediate
for insecticides, Phar-
maceuticals , plasticizers,
polysulfide rubbers,
resins, & cationic sur-
factants
Ingredient of plastici-
zers ; intermediate for
non-ionic detergents &
surfactants; synthetic
drying oils, cutting &
Manufacturer(s)2 * 3
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics
Div.
Exxon Corp. -
Exxon Chem. Co., div. -
Exxon Chem. Co. U.S.A.
(Jetty Oil Co.
Union Carbide Corp. -
Chems. & Plastics Div.
U.S. Steel Corp. - USS
Chems., div.
Exxon Corp. - Exxon
Chem. Co., div. - Exxon
Chem. Co. U.S.A.
Getty Oil Co.
Location(s)2*3
Kingsport, Tenn,
Texas City, Tex.
Baton Rouge, La.
Delaware City, Del.
Institute & South
Charleston, W. Va.
Haverhill, Ohio
1975
capacity2
MM kg (MM Ib)
Total1*'5
production
MM kg (MM Ib)
for year of estimate
81.7 (180) -1974
Baton Rouge, La.
Delaware City, Del.
55.Jl (122) -196?
-------
Table A-l. (Continued)
Chemical
Manufacturer(s)2 * 3
Location(s)2'3
Total4*5
1975 production
capacity2 MM kg (MM Ib)
HM_kg (MM Ib) for year of estimat
Ice- (See previous page)
octyl lubricating oils, hydrau-
aleohol lie fluids; resin sol-
(cont'd) vent; emulsifier; anti-
fearning agent; Intermed-
iate for insecticides,
Pharmaceuticals, plas-
ticizersj polysulfide
rubbers, resins, &
cationic surfactants
U.S. Steel Corp. -
USS Chems., div.
Delaware City,
Del.
I
v£>
l-»
ON
Isophorone
Isqphthalic
acid
Isoprene
Isopropanol
In solvent mixtures
for finishes; for poly-
vinyl & nitrocellulose
resins; pesticides;
staving lacquers
Polyester, alkyd, poly-
urethane, & other high
polymers; plasticizers
Monomer for manufacture
of polyisoprene;
chemical intermediate
Manufacture of acetone
6 its derivatives; manu-
facture of glycerol &
isopropyl acetate; sol-
vent for essential &
other oils, alkaloids,
gums, resins, etc.;
latent solvent for cel-
lulose derivatives;
coatings solvent;
deicing agent for li-
quid fuels; Pharmaceu-
ticals; perfumes;
lacquers; extraction pro-
cesses ; dehydrating
agent; preservative
Union Carbide Corp. -
Chems. & Plastics
Div.
Standard Oil Co, (Ind.)
Amoco Chems. Corp.,
subsid.
Institute & South
Charleston, W. Va,
Joliet, 111.
Caribe Isoprene Corp.
Exxon Corp, - Exxon
Chem. Co., div. - Exxon
Chem. Co. U.S.A.
The Goodyear Tire &
Rubber Co. - Chem. Div.
Neches Butane Products
Co.
Shell Chem. Co. - Base
Chems.
Atlantic Richfield Co. -
ARCO Chem. Co., div.
Eastman Kodak Co. - East-
man Chem. Products, Inc.,
subsid. - Texas Eastman
Co., div.
Exxon Corp. - Exxon Chem.
Co., div. - Exxon Chem.
Co. U.S.A.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Ponce, P, R.
Baton Rouge, La.
Beaumont, Tex.
Port Neches, Tex.
Deer Park, Tex.
Wood River, 111.
Channelview, Tex.
Longview, Tex.
Baton Rouge, La.
Deer Park, Tex.
Dominguez, Callf.
Texas City, Tex.
Whiting, Ind.
(90)
Total *
I»0.9 (90)
30
(66)
(10)
53-6 (118)
151.8 (33*1.3) -1971
76.3 (168)
*»5.4 (100)
55.8 (123)
Total *
182
15.9 (35)
279-2 (615)
276.9 (610)
91* (207)
85
85
(187)
(187)
Total -
835.8 (18*1)
-------
Table A-l. (Continued)
Chemical
Iso-
propyl
acetate
VO
Iso-
propyl-
amine
Iso-
prcpyl
chloride
Isopropyl-
phenol
Ketene
Solvent for nitrocellu-
lose, resin gums, etc.;
paints, lacquers, &
printing inks, organic
synthesis
Solvent; intermediate in
synthesis of rubber ac-
celerator, Pharmaceuti-
cals, dyes, insecticides;
bactericides, textile
specialties, & surface-
active agents; dehairing
agent; solubilizer for
2,4-D acid
Solvent; intermediate;
isopropylamine
Intermediate for syn-
thetic resins, plasti-
cizers, surface active
agents, perfumes
Acetylating agent, gen-
erally reacting with com-
pounds having an active
hydrogen atom; reacts
with ammonia to give
acetamide; starting
point for making var-
ious commercially im-
portant products, espe-
cially acetic anhydride
& acetate esters
Manufacturer^)2* 3
Eastman Kodak Co. -
Eastman Chem, Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
Air Products & Chems.,
Inc.
Pennwalt Corp. - Chem.
Div,
Union Carbide Corp. -
Chems. & Plastics Div.
Va. Chems. Inc. -
Indust. Chems. Dept.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. -
Hooker Chems. &
Plastics Corp., sub-
sid. , Electrochemical
4 Specialty Chems. Div.
Ethyl Corp. - Productol
Chem. Co.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Location(s)2*3
Kingsport, Tenn.
Institute & South
Charleston, W. Va.
Texas City, Tex.
Pensaeola, Pla.
Wyandotte, Mich.
Tart, La.
Portsmouth, Va.
Niagara Palls, N. Y.
Orangeburg, S. C.
Santa Fe Springs,
Calif.
Muscatine, Iowa
1975
capacity2
MM kg (MM Ib)
Total1"5
production
MM kg (MM Ib)
for year of estimate
13-6 (30)
Total -
18.1 (40)
-------
Table Ar*l. (Continued)
Chemical
Maleic
acid
Maleic
anhydride
I
VO
M
00
Malic
acid
Mesityl
oxide
Organic synthesis (malic,
suecinic, aspartic,
tartaric, propionlc, lac-
tic, malonic , acrylic,
hydraerylic acids);
dyeing & finishing of
cotton, wool & silk;
preservative for oils
£ fats
Polyester resins; alkyd
coating resins; fumaric
acid manufacture; pesti-
cides ; preservative for
oils S fats; paper;
permanent-press resins
(textiles)
Medicine; manufacture
of various esters &
salts; wine manufacture;
chelating agent; food
acidulant; flavoring
Solvent for cellulose
esters & ethers, oils,
gums, resins, lacquers,
roll-coating inks,
stains, ore flotation;
paint & varnish-removers;
insect repellent
Manufacturer(s)2'3
Pfanstiehl Labs.,
Inc.
Allied Chem. Corp. -
Specialty Chems. Div,
Koppers Co., Inc. -
Organic Materials Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Petro-Tex Chem. Corp. -
Petro-Tex. Chem, Co.,
subsid.
Reichhold Chems., Inc.
Tenneeo Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
U.S. Steel Corp. - USS
Chems., div.
Allied Chem. Corp. -
Specialty Chems. Div.
Norse Labs. Inc.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Location(s)2'3
Waukegan, 111.
1975
capacity2
MM kg (MM IB)
Total1*'5
production
KM kg (MM lb)
year of estimate
Moundsvllle, W. Va.
Brldgevllle, Pa.
St. Louis, Mo.
Houston, Tex.
Elizabeth, N. J.
Morris, 111.
Fords, N. J.
9.1
15.1
^7.7
22. r
13.6
27.2
10
(20)
(34)
(105)
(50)
(30)
(60)
(22)
128.5 (283) -1971
Neville Island,
Moundsvllle, W. Va.
Santa Barbara, Calif.
Deer Park, Tex.
Dominguez, Calif.
Institute & South
Charleston, W. Va.
18.2 (»0)
Total =
163.9 (361)
-------
Table A-l. (Continued)
Chemical
Meth-
acrylic
acid
Meth-
acrylo-
nitrile
Meth-
allyl
alcohol
Meth-
allyl
chloride
Methanol
Monomer for large-vol-
ume resins & polymers;
organic synthesis; many
of the polymers are
based on esters of the
acid, as the methyl,
butyl, or losbutyl
esters (see acrylic
resin)
Vinyl nitrile monomer;
copolymer with styrene,
butadiene, etc.j elasto-
mers , coatings,
plastics
Intermediate
Manufacturer!s)2 * 3
E. I. du Pont de Ne-
mours & Co., Inc. -
Bioehems. Dept.
Hohm & Haas Co.
The Standard Oil
Co. (Ohio); Vistron
Corp., subsid. -
Chems. Dept.
Intermediate for pro-
duction of insecticides,
plastics, Pharmaceuticals,
other organic chemicals;
fumigant for grains,
tobacco, & soil
Manufacture of formalde-
hyde & dimethyl terephtha*
late; chemical synthesis
(methyl amines, methyl
chloride, methyl meth-
acrylate, etc.); avia-
tion fuel (for water
injection); automotive
antifreeze; solvent for
nitrocellulose, ethylcel-
lulose, polyvinyl butyral,
shellac, rosin, manila
resin, dyes; denaturant
for ethyl alcohol; de-
hydrator for natural
gas
FMC Corp. - Ghem. Group
Indust. Chem. Div.
Stauffer Chem. Co. -
Specialty Chem. Div.
Air Products & Chems.,
Inc.
Borden Inc. - Borden
Chem. Div. - Petrochems.
Celanese Corp. -
Celanese Chem, Co., div.
Commercial Solvents
Corp.
E. I. du Pont de Ne-
mours & Co., Inc. -
Elastomer Chems. Dept,
Plastics Dept.
Ga.-Pacific Corp. -
Chem. Div,
Location(s)2'3
Belle, W. Va.
Bristol, Pa.
Lima, Ohio
1975
capacity2
MM kg (MM lb)
Baltimore, Md.
Edison, N. J.
Fensacola, Pla..
Gelsmar, La.
Bishop, Tex.
Clear Lake, Tex.
Sterlington, La.
Beaumont, Tex
Orange, Tex.
Total14'5
production
MM kg (MM lb)
for year of estimate?
30.9 (68) -1968
149.8 (330)
479.4. (1,056)
179.8 (396)
689.2 (1,518)
149.8 (330)
599.3 (1,320)
344.6 (759)
3,082 (6,790) -1974
WJ. 0.11(3 C: ,-LGA. Jit . U \ ( jy )
Plaquemine, La. 299 -6 (660)
-------
Table A-l. (Continued)
Chemicj.1
Methanol
(cont'd)
I
VO
ro
o
Methyl
acetate
Methyl
aceto-
acetate
Methyl-
amine
Usage1
(See previous page)
Paint remover com-
pounds ; lacquer
solvent; Intermediate
Solvent for cellulose
ethers; ingredient of
solvent mixtures for
cellulose esters;
organic synthesis
Intermediate for acceler-
ators, dyes, Pharmaceuti-
cals; insecticides; fun-
gicides; surface active
agents; tanning; dyeing
of acetate textiles;
fuel additive; polymeri-
zation inhibitor; com-
ponent of paint remov-
ers ; solvent; photo-
graphic developer;
rocket propellant
Manuf a c t ure r (sj 2 * 3
Hercules Inc. -
Synthetics Dept,
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
subsid.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
Borden Inc. - Borden
Chem. Div. - Thermo-
plastic Products
Eastman Kodak Co. -
Eastman Organic Chems.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. -
Tenn. Eastman Co., div.
Lonza Inc.
Air Products & Chems.,
Inc.
Commercial Solvents
Corp.
E. I, du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
GAP Corp. - Chem. Div.
Rohm and Haas Co.
Locatignisl2*3
Hercules, Calif.
Plaquemine, La.
Texas City, Tex.
Deer Park, Tex.
Houston, Tex.
Bainbridge, N. Y.
Compton, Calif.
Demopolis, Ala.
Illiopolis, 111.
Leominster, Mass.
Rochester, N. Y.
Springfield, Mass.
Institute & South
Charleston, W. Va,
Kingsporfc, Tenn.
Mapleton, 111.
Pensacola, Pla.
Terre Haute, Ind.
Belle, W. Va.
La Porte, Tex.
Calvert City, Ky.
Philadelphia, Pa.
Total4'5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
299-6 (660)
299.6 (660)
65.9 (1,152)
239.7 (528)
Total =
3,796.3 (8,362)
(See previous page)
22,7 (50)
8.2 (18)
7^.9 (165)
11.8 (26)
it.5 (10)
6.3 (1*0
Total =
128.5 (283)
85.1 (187.M -1973
-------
Table A-l. (Continued)
I
VO
N>
Chemical
N-methyl-
anillne
Methyl
butynol
Methyl
chloride
Organic synthesis;
solvent; acid ac-
ceptor
Stabilizer in chlori-
nated solvents; vis-
cosity reducer & stab-
ilizer; electroplating
brightener; inter-
mediate
Catalyst carrier in low-
temperature polymeriza-
tion (butyl rubber);
tetramethyl lead; sill-
cones ; refrigerant; medi-
cine; fluid for thermo-
metric & thermostatic
equipment; methylating
agent in organic syn-
thesis, such as methyl-
cellulose ; extractant &
low-temperature solvent;
propellant in high-
pressure aerosols;
herbicide
Manufacturer's )2_J__3
Allied Chem. Corp. -
Specialty Chems. Div.
American Cyanamid Co. -
Organic Chems. Div.
Air Products & Chems.,
Acetylenic Chems.
Div.
Hoffmann-La Roche Inc.
Location(s)2'3
Buffalo, N. Y.
Bound Brook, "N. J.
Calvert City, Ky.
Nutley, N. J.
1975
capacity2
MM kg (MM Ib)
Total1**5
production
MM kg (MM Ib)
for year__of_ estimate^
Allied Chem. Corp. -
Specialty Chems. Div.
Continental Oil Co. -
Conoco Chems ,
Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.
Dow Chem. U.S.A.
Dow Corning Corp.
E. I, du Pont de Ne-
mours & Co., Inc. -
Indus t. Chems. Dept .
Ethyl Corp .
Oen. Electric Co. -
Chem, & Metallurgical
Div. - Silicone Pro-
ducts Dept .
Stauffer Chem. Co. -
Indust. Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Vulcan Materials Co. -
Chems. Div.
Moundsville, W. Va.
Westlake, La.
Belle, W. Va.
Flaquemine, La.
Carrollton, Ky.
Midland, Mich.
Niagara Palls, N. Y.
Baton Rouge, La.
Waterford, N. Y.
Louisville, Ky.
Institute & South
Charleston, W. Va.
Geismar, La.
Newark, N. J.
Wichita, Kans.
11.3
15.4
H.3
68.1
9.1
6.8
36.3
45.4
22.7
6.8
22.7
-
(25)
(100)
(25)
(150)
(20)
(15)
(80)
(100)
(50)
(15)
(50)
201.8 (114.5) -1973
Total
286 (630)
-------
Table A-l. (Continued)
Chemical
Methyl-
eye lo-
hexane
Methy1-
cyclo-
hexanol
Methyl-
cyclo-
hexanone
Methyl-
dioxo-
lane
Methyl
formate
Methylene
chloride
Solvent for cellulose
ethers; organic
synthesis
Solvent; lacquers;
solvent for cellulose
esters ft ethers for lac-
quers; antioxldant for
lubricants; blending
agent for special
textile soaps &
detergents
Extractant & solvent for
oils, fats, waxes, dye-
stuffs, & cellulose
derivatives
Organi c synthe sis;
cellulose acetate sol-
vent; military poison
gases; fumigant; lar-
vlcides
Paint remover/s; special
photographic film; fumi-
gant; solvent degreasing;
solvent mixtures for
cellulose esters & ethers;
textile & leather coat-
ings; refrigeration; local
anesthetic; pharmaceutical
ft food extraction; plas-
tics processing; spotting
agent; dewaxing; chemical
(organic synthesis); as a
propellant for aerosols;
blowing agent In foams
Manufacturer(s)2*3
Phillips Petroleum Co. -
Petrochem. & Supply
Div.
Lanza Inc..
Prank Enterprises
Location(s)2^3
Phillips, Tex.
Mapleton, 111.
Columbus, Ohio
1975
capacity2
MM kg (MM Ib)
Total1"5
production
MM kg (MM Ib)
for year of e^stlmat^e
Celanese Corp. -
Celanese Chem. Co.,
div.
E. I. du Pont de Ne-
mours & Co., Inc, -
Biochems. Dept.
Allied Chem. Corp. -
Specialty Chems. Div.
Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.
Dow Chem. U.S.A.
E. I. du Pont de Ne-
mours & Co., Inc. -
Indust. Chems. Dept.
Stauffer Chem. Co. -
Indust. Chem. Div.
Pampa, Tex.
Belle, W. Va.
Moundavllle, W. Va.
Belle, W. Va.
Freeport, Tex.
Plaquemine, La.
Niagara Palls,
Louisville, Ky.
22.7
27.2
68.1
10.9
18.2
27.2
(50)
(60)
(150)
(90)
(to)
(60)
214 (471.3) -1973
-------
Table A—1« (Continued)
I
VO
K>
OJ
Chemical
Methylene
chloride
(cont'd)
Methylene
d-lanlllne
Methyl
ethyl
ketone
Usage1
(See previous page)
Determination of tungs-
ten & sulfates; polymer
& dye intermediate;
corrosion inhibitor;
epoxy resin hardening
agent
Solvent in nitrocellu-
lose coatings & vinyl
films; "Glyptal" re-
sins; paint removers;
cements & adhesives;
organic synthesis;
manufacture of smoke-
less powder; cleaning
fluids; printing;
catalyst carrier;
Note: does not dis-
solve cellulose ace-
tate and most waxes
Manufacturer(3)2'3
Vulcan Materials Co, -
Chems, Div.
Allied Chem. Corp. -
Specialty Chems. Div.
Dow Chem. U.S.A.
Location(s)2*3
Geismar, La.
Newark, N. J.
Wichita, Kans.
Moundsville, W. Va.
Midland, Mich.
Total1**5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
Eastman Chem. Products,
Inc., subsid. - Tenn,
Eastman Co., div.
Exxon Corp. - Exxon
Chem, Co., div. -
Exxon Chem. Co. U.S.A.
Shell Chem. Co. - Base
Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Bayway, N. J.
'Deer Park, Tex.
Martinez, Calif.
Norco, La.
Brownsville, Tex.
18.2 (40)
13.6 (30)
Total =
236.1 (520)
(See previous page)
Mobay Chem. Corp, -
Indust . Chems . Div .
Rubicon Chems, Inc.
Atlantic Richfield
Co. - ARCO Chem. Co.,
div.
Celanese Corp. -
Celanese Chem. Co. ,
div.
Dart Indust . , Inc . -
Chem. Group - Chem.
Specialties Sector -
Aztec Chems .
Dixie Chem. Co.
Eastman Kodak Co. -
New Martinsville,
W. Va.
Geismar, La.
Channel view, Tex.
Pampa, Tex.
Elyria, Ohio
Bayport , Tex.
Kingsport, Tex.
_
-
29 (64)
52.2 (115)
1.4 (3)
-
229.6 (505.8) -1971
90.8 (200)
15.1 (100)
22.7 (50)
27.2 (60)
Total =
268.8 (592)
-------
Table A-l. (Continued)
Chemical
Manufacturer's)2 * 3
Location(s)2'3
19T5
capacity2
MM kg (MM Ib)
Totalkt5
production
MM kg (MM Ib)
for year of estimate
Methyl- Solvent for dyestuffs;
isobutyl oils, gums, resins,
carbinol waxes, nitrocellulose
& ethyleellulose; or-
ganic synthesis; froth
flotation; brake fluids
Methyl Solvent for paints, var-
isobutyl nishes, nitrocellulose
ketone lacquers; manufacture of
methyl amyl alcohol;
extraction processes,
Including extraction of
uranium from fission pro-
ducts; organic synthesis;
denaturant for alcohol
Methyl- Stabilizer in chlorinated
pentynol solvents; viscosity re-
ducer i electroplating
brightening; intermediate
in syntheses of hypnotics
& isoprenoid chemicals;
solvent for polyamide re-
sins; acid inhibitor;
prevention of hydrogen
embrlttlement; medicine
(soporific & anesthetic)
Methyl- Perfumery; flavoring;
phenyl- dyes; laboratory
carbinol reagent
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Exxon Corp. - Exxon
Chem. Co., div. -
Exxon Chem. Co. U.S.A.
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Air Products & Chems.
Inc. - Acetylenic
Chems. Div.
Hoffman-La Roche Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Deer Park, Tex.
Dominguez, Calif.
Institute & South
Charleston, W. Va.
Kingsport, Tenn.
Bayway, N. J.
Deer Park, Tex.
Domingue z, Cal1f,
Institute & South
Charleston, W. Va.
Calvert City, Ky.
Nutley, N. J.
Institute & South
Charleston, W. Va.
13.6 (30)
18.2 (40)
36.3 (80)
15.9 (35)
29.5 (65)
Total =
113.5 (250)
15-9 (35) -1973
70.3 (15^.83-1973
-------
Table A-l. (Continued)
Chemical
a-methyl-
styrene
Polymerization monomer,
especially for polyester
Manufacturer(s)2 * 3
Allied Chem. Corp. -
Specialty Chems. Div.
Clark Oil & Refining
Corp. - Clark Chem.
Corp., subsid.
Dow Chem. U.S.A.
Ga. -Pacific Corp. -
Chem. Div.
Skelly Oil Co.
Union Carbide Corp. -
Total1"5
1975 production
capacity2 MM kg (MM Ib)
Location(s)2'3 MM kg (MM Ib) for year of estimate
Frankford, Pa.
Blue Island, 111.
Midland, Mich.
Plaquemine, La.
El Dorado, Kans .
Bound Brook, N. J.
6.8
2.3
4.5
-------
Table A-l. (Continued)
Chemical
Manufacturer (s)2 *3
Locatlon(s)2'3
1975
capacity2
MM kg (MM Ib)
Total^'5-
production
MM kg (MM Ib)
for, year of estimate
6-naph-
thalene
sulfonic
acid
a-naphthol
B-naphthol
Neo-
pentanoic
acid
Nitroanisole
Nitro-
benzene
Starting point in the
manufacture of beta-
naphthol, beta-naph-
tholsulfonic acid,
beta-naphthylami ne-
sulfonic acid; etc.
Dyes; organic synthesis;
synthetic perfumes
Dyes; pigments; anti-
oxldants for rubber,
fats, oils; insecticide;
synthesis of fungicides;
Pharmaceuticals, per-
fumes
Intermediate, as a
replacement for some
natural materials
Organic synthesis;
manufacture of inter-
mediates for dyes
& Pharmaceuticals
Manufacture of aniline;
solvent for cellulose
ethers; modifying es-
teriflcation of cellu-
lose acetate; ingredient
of metal polishes & shoe
polishes; manufacture
of benzidine, quino-
line, azobenzene, etc.
American Cyanarnid Co. -
Pine Chems. Dept.
(See also a-naph-
thalene sulfonic acid)
Union Carbide Corp. -
Chems. & Plastics Div.
American Cyanamid Co.
Organic Chems. Div.
Exxon Corp. - Exxon
Chem. Co., div. -
Exxon Chem. Co. U.S.A1.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.
Monsanto Co, - Monsanto
Indust. Chems. Co.
Allied Chem. Corp. -
Specialty Chems. Div.
American Cyanamid Co. -
Organic Chems. Div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Elastomer Chems. Dept. -
Indust. Chems. Dept.
First Miss. Corp. -
First Chem. Corp.,
subsid.
Mobay Chem. Corp. -
Indust. Chems. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Rubicon Chems. Inc.
Bound Brook, N. J.
Institute & South
Charleston, W. Va.
Willow Island,
Baton Rouge, La.
Deepwater, N. J.
St. Louis, Mo.
Moundsville, W. Va.
Bound Brook, N. J.
Willow Island,
W. Va.
Beaumont, Tex.
Gibbstown, N. J.
Pascagoula, Miss.
New Martinsville,
W. Va.
Sauget, 111.
Geismar, La.
10.8 (23-8) -1955
25 (55)
38.6 (85)
27,2 (60)
90.8 (200)
61.3 (135)
61,3 (135)
4.5 (10)
34 (75)
Total »
483.5 (1,065)
250.2 (551.2) -1972
-------
Table A-l. (Continued)
Chemical
Manufacturer(s)2'3
LocatlQH(s)2'3
1975
dapaoity2
MM, Kg (MM lb)
Total"'5
production
MM kg (MB lb)
for ,year Of estimate
vo
Hltro- Organic synthesisj
benzole preparation of anes-
aoid theties & as tntermed-
(m,o,p) late in the manufacture
of dyes & s
agents
Nitro- Propellant! solvent for
ethane nitrocellulose, cellulose
acetate, cellu^Qse ae'e-
topropionate, e.€flltflose
acetobutyrate, vinyl,
alkyd, & many other
resins, waxes, fats &
dyestuffs; chemical
synthesis
Nitro- Organic synthesis! for
toluene production of toluld^ne,
tolidine, fueh,sin, &
various synthetic 'dyes
Nonene Organic synthesis; wet-r
ting agent; lube oil
additive; polymer
gasoline
Bofors Indust., Inc.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept.
Dyes i Chems. Div.
Salsbury Labs.
Sterling' Drug Inc. -
flhe Hilton-Davis
Chem. Co., div.
Commercial Solvents
Corp,
E. I. du Pont de Ne-
ffiouFs & Co., Inc. -
Orgariio Chems. Dept, T
Dyes & Chems. Div.
First Miss. Corp. r
^irst Chem. Corp.,
subsid.
Atlantic RJehfield Co. -
AI^CO Ch«m, Co., div.
Exxon Corp, - Exxon
Chem. Co., div. -
Exxon Chem. Co, U.S.A.
The, Humphrey Chen. Co.
Sun Oil Co. - Sun Oil
Co. of Fenn., subsid.
Onion Oil Co. of Calif,
Linden, N. J.
DeepWater, N. J.
Charles City, Iowa
Cincinnati, Ohio
Sterlington,, La.
Deepwater, N. J,
Pascagoula, Hiss.
East Chicago, Ind.
Baton Rouge, La.
North Haven, Conn.
Karcus Hoo^c, Pa.
Beaumont, Tex.
-------
Table A-l- (Continued)
Chemical
Nonyl-
phenol
VO
bo
oo
Oetyl-
phenol
Non-ionic surfactant
(nonbiodegradable); lube
oil additives; stabili-
zers, petroleum demulsi-
fiers, fungicides; bacte-
ricides; dyesj drugs; ad-
he sives; rubber chemicals;
phenolic resins &
plasticizers
Nonionic surfactants;
plasticizers; antioxi-
dants; fuel oil stabi-
lizer; intermediate for
resins, fungicides,
bactericides, dyestuffs
adhesives, rubber
chemicals
Paralde- Substitute for acetalde-
hyde hyde; rubber accelera-
tors; rubber antloxl-
dants; synthetic or-
ganic chemicals; dye-
stuff intermediates;
medicine; solvent for
fats, oiIs, waxes,
gums, resins; leather;
solvent mixtures for
cellulose derivatives
Manufacturer(s)2 * 3
Borg-Warner Corp . -
Borg-Warner Chems. -
Weston Div,
Exxon Corp . - Exxon
Chem. Co. , div. -
Exxon Chem. Co. U.S.A.
GAF Corp. - Chem. Div.
Monsanto Co . - Monsanto
Indust . Chems . Co .
Productol Chem. Co .
Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
subsid.
Texaco Inc. - Jefferson
Chem. Co. , Inc. , subsid.
Uniroyal, Inc. - Uni-
royal Chem., div.
GAP Corp. - Chem. Div.
Productol Chem, Co.
Schenectady Chems.,
Inc.
Rohm & Haas Co . - Rohm
& Haas Texas Inc.,
subsid.
Location(s)2'3
Morgantown, W. Va.
Bay way , N . J .
Calvert City, Ky .
Linden, N. J.
Kearny, N. J.
Sante Pe Springs,
Calif.
Philadelphia, Pa.
Deer Park, Tex.
Port Neches, Tex.
Naugat uc k , Conn .
Linden, N. J.
Santa Fe Springs,
Calif.
Rot t er dam June 1 1 on ,
N. Y.
Philadelphia, Pa.
Deer Park, Tex.
1975
capacity2
MM kg (MM Xb)
9-1 (20)
4.1 (9)
2.3 (5)
9.1-(20)
11.3 (25)
1 (2)
9.1 (20)
2.3 (5)
13.6 (30)
4.5 (10)
Total -
66.3 (1^6)
-
-
_
_
-
Total1* >s
production
MM kg (MK lb)
for year of estimate
_
Lonza Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Mapleton, 111.
Institute & South
Charleston, W. Va.
-------
Table A-l. (Continued)
Chemical
Penta-
erythritol
Perchloro-
ethylene
Alkyd resins; rosin &
tall oil esters; special
varnishes; pharmaceuti-
cals; plasticizers;
insecticides; synthetic
lubricants; explosives;
paint swelling agents
Dry cleaning solvent;
vapor-degreasing sol-
vent; drying agent for
metals & certain other
solids; vermifuge; heat-
transfer medium, mfg.
of fluorocarbons
1-pentene
Organic synthesis;
blending agent for
high octane motor fuel
Manufacturer(s)2'3
Celanese Corp, - Cela-
nese Chem. Co., div,
Commercial Solvents
Corp.
Hercules Inc. -
Synthetics Dept.
Pan American Chem.
Corp.
Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.
Dow Chem. U.S.A.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Freon® Products Div.
Ethyl Corp.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. -
Hooker Chems. & Plastics
Corp., subsid. -
Electrochemical &
Specialty Chems. Div.
PPG Indust., Inc. -
Chem. Div. - Indust.
Chem. Div.
Stauffer Chem. Co. -
Indust. Chem. Div.
Vulcan Materials Co. -
Chems. Div.
Phillips Petroleum Co. -
Petrochem. & Supply Div.
Location(s)2'3
Bishop, Tex.
Seiple, Pa.
Louisiana, Mo.
Toledo, Ohio
1975
capacity2
MM kg (MM Ib)
34 (75)
11.3 (25)
18.2 (110)
11.3 (25)
Total*'5
production
MM kg (MM Ib)
for year of estimate
46.8 (103.2) -
1973
Deer Park, Tex.
Preeport, Tex.
Pittsburg, Calif.
Plaquemine, La.
Corpus Christ!,
Baton Rouge, La.
Taft, La.
Lake Charles, La.
Louisville, Ky.
Geismar, La.
Wichita, Kans.
Phillips, Tex.
Total =
74.9 (165)
72.6 (160)
54.5 (120)
9.1 (20)
68.1 (150)
72.6 (160)
22.7 (50)
22.7 (50)
90.8 (200)
31.8 (70)
68.1 (150)
22.7 (50)
Total =
535-7 (1,180)
332.8 (733) -1974
-------
Tabl*
(Continued)
tfsage*
Polymerization inhibitor;
organic synthesis
P-£hene- Manufacture of tlyes;
laboratory reagent
O\
1
vb
i
Dyestuffs intermediates
tidene Pharmaceuticals; medi-
cine; laboratory
reagent
Phenol Phenolic resins; «poxy
resins (bisphenol^A);
nylon-6 Ccaprolactam);
2,i*i-D; selective solvent
Tor refining lubricating
oils; adtpic api^i sali'-
cyllc acid; phenolphtha*-
lein; pentachlpt'ophen^l;
acetophenetidine^ picric
acidj germlcidal paints;
Pharmaceuticals; labpra-
bory reagent ; dyes &
indicators ; slimicide
Monsanto Co. - Monsanto
Indust. Chems» Cb.
Monsanto 60. - Monsanto
Indust. Chems. "Co.
Salsbury
Chem, Corp. -
Specialty Chems. Div.
Clark til 6 Refining
Corp. *- Clark Chem.
Corp., subsid.
Dow Chem. U.S.A.
Georgian-Pacific vCorp. -
Chem. Div.
Kalama Chem. Inc.
Koppers Co,, Inc. -
The Herichem Co.
Monsanto.Co, - Monsanto
Polymers & Petrochems.
Co.
Productol Chem. Co.
Reichhold Chems., Inc.
Skelly Oil Co.
Standard Oil Co. of
Calif. - Chevron Chem.
Co., subsid. - Oronite
Additives ft Indust.
Chems. Div. *- Indust.
Chems.
Stimson Lumber Co. -
Northwest Petrochem.
Corp., div.
Union Carbide Corp. -
Chems. & Plastics Div. -
Onion Carbide Carlbe,
Inc., subsid.
U.S. Steel Corp. - USS
Chems., div.
tioeatlpnta)**,*
St. Louis, to.
1975
capacity2
MM kg (MM.Ib)
Total1|>6-
production
MM kg (MM Ib)
for. ye.ar .of estimate
St. Mills, Mo.
Saugefc, 111.
Wilnlngtont N. C.
Frankford, Pak
Blue Island, 111.
Midland, Mich.
Oyster Creek^ Tex.
?laquemine. La.
Kalama, Wash*
Follansbee, W. Va,
Houston^ Tex.
Chocolate Bayou,
Tex.
Sante Fe Springs,
Calif.
Tuscaloosa, Ala.
El Dorado, Kans.
Richmond, Calif.
Anacortes, Wash.
Bound Brook, N. J.
Penuelas, P. R.
Clairton, Pa.
Haverhlll, Ohio
238.3 (525)
ltd (88)
45.1 (100)
l8l.6 (100)
130.3 (28T)
25 (55)
201.3 (150)
61.3 (135)
13.1 (95)
25 (55)
1,103.2
68.1 (150)
90.8 (200)
127.1 (280)
Total =
1,280.3 (2,820)
-------
Table A-l. (Continued)
SO
CO
Chemical
Phenol-
sulfonic
acids
Phenyl
anthra-
nilic
acid
Phenylene-
diamine
Water analysis; labora-
tory reagent; electro-
plated tin coatings
baths; manufacture of
intermediates & dyes;
Pharmaceuticals
Azo dye intermediate;
photographic develop-
ing agent; fur dyes;
photochemical measure-
ments ; intermediate
in manufacture of
antioxidants & ac-
celerators for
rubber; detection of
nitrous acid; textile
developing agent;
organic synthesis;
laboratory reagent
Manufacturer(s)2 ' 3
Productol Chem. Co.
Jim Walter Corp. - U.S.
Pipe & Foundry Co.,
subsid. - Chem. Div.
Witco Chem, Corp. -
Ultra Div.
Sterling Drug Inc. -
Fairmount Chem. Co.,
The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.
Toms River Chem. Corp.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.
The B. F. Goodrich
Co. - B. F. Goodrich
Chem. Co., div.
Martin Marietta Corp. -
Martin Marietta Chems.
Sodyeco Div.
Ashland Oil, Inc. -
Ashland Chem, Co., div.
Chem. Products Div.
GAP Corp. - Chem. Div.
Location(s)2*3
Sante Fe Springs,
Calif.
Birmingham, Ala.
Paterson, N. J.
Rensselaer, N. Y.
Deepwater, N. J.
Newark, N. J.
St. Bernard, Ohio
Toms River, N. J,
Deepwater, N. J.
Henry, 111.
Sodyeco, N. C.
Great Meadows,
N. J.
Rensselaer, N. Y.
Totale*'5'
production
MM kg (MM Ib)
for year of _estinmate
29.1
-1971
-------
Table A-l. (Continued)
Total*' 5-
1975 production
capacity2 MM kg (MM Ib)
Organic synthesis, es-
pecially of isocyanates
polyurethane & poly-
carbonate resins, car-
fa antates, organic car-
bonates & chloroform™
ates; pesticides;
herbicides; dye manu-
facture
CO
K)
Manufacturer ( s ) 2 • 3
Allied Chem. Corp. -
Specialty Chems. Div.
BASF Wyandotte Corp. -
Indust. Chems. Group
Chemetron Corp. -
Chems. Group - Organic
Chems. Div.
E. I. du Pont de Ne-
mours & Co . , Inc . -
Elastomer Chenis. Dept.
FMC Corp. - Chem.
Group - Indust. Chem.
Div.
Gen. Electric Co. -
Plastics Business Div. -
Engineering Plastics
Product Dept.
Mobay Chem. Corp. -
Indust. Chems. Div.
Olln Corp. - Agri-
cultural Chems. Div.
Designed Products Div.
PPG Indust., Inc. - Chem.
Div. - Indust. Chem. Div.
Rubicon Chems. Inc.
Stauf f er Chero. Co . -
Agricultural Chem. Div.
Story Chem. Corp. -
Ott Div.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Onion Carbide Corp. -
Chems. 4 Plastics Div.
The Upjohn Co. - Polymer
mer Chems. Div.
Van De Mark Chem. Co.,
Inc.
Location(s)2 » 3
Moundsville, W. Va.
Geismar, La.
La Porte, Tex.
Deepwater Point,
N. J.
Baltimore, Md.
Mount Vernon, Ind.
Cedar Bayou, Tex.
New Martinsville,
W. Va.
Lake Charles, La.
Ashtabula, Ohio
Barberton, Ohio
Geismar, La.
Cold Creek, Ala.
Muskegon, Mich.
Port Neches, Tex.
Institute 4 South
Charleston, W. Va.
La Porte, Tex.
Lookport, N. Y.
MM kg (MM Ib) for year of estimate
44.5
25
9.1
61.3
2.7
27.2
59
111.2
51.5
22.7
2.3
56.7
11.3
1.5
13.6
50
90.8
(98) 330.6 (728.2) -1973
(55)
(20)
(135)
(6)
(60)
(130)
(2»5)
(120)
(50)
(5)
(125)
(25)
(10)
(30)
(110)
(200)
3.6 (8)
Total -
650.1 (1,432)
-------
Table
A-l.
(Continued)
Chemj^ca.1
Phthalie
anhydride
I
vo
LO
CO
Phthali-
mide
Alkyd resins; plastici-
zers; hardener for
resins; polyesters; syn-
thesis of phenolphthalein
& other phthaleins, many
other dyes; chlorinated
products; pharmaceutical
Intermediates; insecti-
cides; diethyl phthalate;
dimethyl phthalate;
laboratory reagent
Synthetic indigo, via
anthranilic acid;
fungicide; organic
synthesis; laboratory
reagent
Manufacturer(s)2'3
Allied Chem. Corp. -
Specialty Chems. Div.
BASF Wyandotte Corp. -
Colors & Chems. Group
Exxon Corp. - Exxon
Chem. Co., div. - Exxon
Chem. Co. U.S.A.
Koppers Co., Inc. -
Organic Materials Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.,
subsid. - Puerto Rico
Chem. Co., subsid.
Standard Oil Co. of
Calif. - Chevron Chem.
Co ., subsid. - Oronite
Additives & Indust.
Chems. Div. - Indust.
Chems.
1975
capacity2
Location(s)2'3 MM kg (MM lb)
El Segundo, Calif.
South Kearny, N. J.
Baton Rouge, La.
Bridgeville, Pa.
Cicero, 111.
Bridgeport, N. J.
Texas City, Tex.
Arecibo, P. R.
15.9
59
10.9
1(0.9
59
38.6
59
15.4
(35)
(130)
(90)
(90)
(130)
(85)
(130)
(100)
Richmond, Calif.
The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.
St. Bernard,
Ohio
Total'"5-
production
MM kg (MM lb)
for year of estimate
1111.5 (979) -1971
22.7 (50)
Stepan Chem. Co. -
Surfactant Dept .
Union Carbide Corp. -
Chems. & Plastics Div.
U.S. Steel Corp. - USS
Anaheim, Calif.
Elwood, 111.
Pieldsboro, N. J.
Institute & South
Charleston, W. Va.
Neville Island,
Pa.
22.7 (50)
22.7 (50)
45. 1 (100)
68.1 (150)
Total =
517.6 (1,140)
-------
Table A-l. (Continued)
Chemical
Phthalo-
nltrile
Piperazine
Poly-
butenes
Polyethy-
lene
glycol
Intermediate In organic
synthesis, especially
pigments & dyes; base
material for high
temperature lubricants
& coatings; Insecticide
Corrosion inhibitor;
anthelmintic; insecti-
cide; accelerator for
curing polychloroprene
Hot-melt adheslves;
sealing tapes; special
sealants; cable In-
sulation; polymer modi-
fier; viscosity index
improvers; lube oil
additive
Chemical intermediates
(lower molecular weight
varieties); plasticizers;
softeners.& humectants;
lubricants; bases for
cosmetics & Pharmaceu-
ticals; solvents; bin-
ders; metal & rubber
processing; permissible
additives to foods &
animal feed; laboratory
reagent
Manufacturer(s)2*3
Locatlon(s)2*3
Calif. - Chevron Chem.
Co., subsid. - Oronlte
Additives & Indust.
Cheras. Dlv. - Indust.
Chems.
Standard Oil Co. (Ind.)
Amoco Chems, Corp.,
subsid.
Ashland Oil, Inc. - Ash-
land Chem. Co., div. -
Chem. Products Div.
BASF Wyandotte Corp. -
Indust. Chems. Group
Dow Chem. U.S.A.
Hodag Chem. Corp.
Olin Corp, - Designed
Products Div.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Texas City, Tex.
Wood River, 111.
Janesville, Wise.
Wyandotte, Mich.
Freeport, Tex.
Skokie, 111.
Brandenburg, Ky.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
1975
capacity2
MM kg (MM Ib)
Total"'5
production
MM kg (MM Ib)
for year of estimate
Fleming Labs., Inc.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Dlv.
American Petroflna, Inc. -
Cosden Oil & Chem. Co.,
subsid.
Exxon Corp. - Exxon
Chem. Co., div. - Exxon
Chem. Co. U.S.A.
The Lubrizol Corp.
Standard Oil Co. of
Charlotte, W. C.
Conroe , Tex .
Taft, La.
Texas City, Tex.
Big Spring, Tex.
Bay way , N . J .
Deer Park, Tex.
Richmond, Calif.
-
-
:
9.1 (20)
20.4 (45)
40.9 (90)
20.4 (45)
104.H (230) -1967
77.2 (170)
10.9 (90)
Total =
208.8 (460)
-------
Table A-l. (Continued)
Chemical
Usage1
Manufacturer(s)2 ' 3
Locatlon(s)2*3
1975
capacity2
MM kg (MM Ib)
Total1**5-
production
MM kg (MM Ib)
for year of estimate
Poly-
ethylene
glycol
chloride
Poly-
propylene
glycol
I
vo
u>
Cn
Propane
Solvents for cleaning
extracting, '& dewaxing
Hydraulic fluids; rubber
lubricants; antlfcam
agents; intermediates
in urethane foams, ad-
hesives, coatings,
elastomers; plastici-
zers; paint formula-
tions; laboratory
reagent
Organic synthesis;
household & industrial
fuel; manufacture of
ethylene, extractant;
solvent; refrigerant;
gas enrichener; aerosol
propellant; mixture for
bubble chambers
BASF Wyandotte Corp, -
Indus t. Chems. Group
E, R. Carpenter Co.,
Inc. - Choate Chem.
Co., subsid.
Dow Chem. U.S.A.
Hodag Chem. Corp.
ICI United States Inc.
Specialty Chems. Dlv.
Nalco Chem. Co. -
Petroleum & Process
Chem. Div, - Visco
Chems.
Olin Corp. - Designed
Products Div.
Pelron Corp. - Texaco
Inc. - Jefferson Chem.
Co ., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
WItco Chem. Corp. -
Organics Div,
Air Products & Chems.
Inc. - Specialty Gas -
Dept. Chemicals -
Intermediates Mktg.
Matheson Gas Products
Phillips Petroleum Co.
Petrochemical & Supply
Div. - Customer Ser-
vice Center
Technical Petroleum Co.
Washington, N. J.
Wyandotte, Mich.
Bayport, Tex.
Freeport, Tex..
Midland, Mich.
Skokie, 111.
New Castle, Del.
Sugar Land, Tex.
Brandenburg, Ky,
Conroe, Tex.
Institute & South
Charleston, W. Va.
Clearing, 111.
Allentown, Pa.
Lyndhurst, N. J.
Borger, Tex.
Chicago, 111.
38.8 (85.5) -1973
21,802 (48,022)-1971
-------
Table A-l. (Continued)
Chemical
Propion-
adlehyde
Propion3c
acid
(propanoic
acid)
VO
CO
Propyl-
amine
Propyl
chloride
Propylene
Manufacture of poly-
vinyl acetals & other
plastics; synthesis
of rubber chemicals;
disinfectant;
preservative
Propionates, some of
which are used as mold
inhibitors in bread &
fungicides in general;
emulsifying agents;
solutions for electro-
plating nickel; per-
fume esters; artifical
fruit flavors; Pharma-
ceuticals; solvent mix-
tures for cellulose
derivatives; pretreat-
ment of zinc oxide
Intermediate; laboratory
reagent
Solvent; intermediate
propylamine
Isopropyl alcohol, poly-
propylene , synthetic
glycerol, acrylonitrile,
propylene oxide, heptene,
eumene, polymer gasoline,
anticipated use for
acrylic acid & in vinyl
resins
Manufacturer^) 2*^
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Celanese Corp. -
Celanese Chem. Co., div.
Commercial Solvents Corp.
Eastman Kodak Co. -
Eastman Chem. Products
Inc., subsid. - Tenn.
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics Div,
Pennwalt Corp. - Chem.
Div.
Va. Chems. Inc. - Indust.
Chems. Dept.
Publicker Indust. Inc.
Amerada Hess Corp.
American Petrofina,
Inc. - Cosden Oil &
Chem. Co., subsid.
ARCO/Polymers, Inc.
Ashland Oil, Inc. -
Ashland Chem. Co., div.,
Petrochems. Div.
Atlantic Richfield Co. -
ARCO Chem. Co., div.
BASF Wyandotte Corp. -
Indust. Chems. Group
capacity*;
Location(s)2*3 MM kg {MM Ib.)
Longview, Tex.
Seadrift, Tex.
Texas City, Tex.
Pampa, Tex.
Sterlington, La.
Kingsport , Tenn .
Institute & South
Charleston, W. Va.
-
-
5.1
1.4
9.1
11.3
(12)
(3)
(20)
(25)
Total =
27.2 (60)
Wyandotte, Mich.
Portsmouth, Va.
Philadelphia, Pa.
Port Reading, N. J.
Big Spring, Tex.
Eldorado, Tex.
Mount Pleasant, Tex.
Houston, Tex.
Ashland, Ky.
Louisville, Ky.
North Tonawanda
Channel view , Tex .
East Chicago , Ind .
Wilmington, Calif.
Geismar, La.
-
-
-
59
59
15
25
68.1
75
13.6
22.7
6.8
30
45.4
22.7
•(130)
(130)
C33)
(55)
(150)
(165)
(30)
(50)
(15)
(66)
(100)
(50)
Total"'5
1975 production
MM kg (MM Ib)
for year of estimate
27.1 (60.1) -1973
7.6 (16.7) -1972
4,5*111 (10,010) -1974
-------
Table A-l. (Continued)
Chemical
Prooylene
(cont'd)
Usage V
(See previous page)
ON
VO
co
Manufacturer(s) 2_*3
The Charter Co. -
Charter Oil Co.,
subsid. - Charter
Internat'l Oil Co.,
subsid.
Chemplex Co.
Cities Service Co.,
Inc. - North American
Petroleum Group
Clark Oil & Refining
Corp. - Clark Chem.
Corp., subsid.
Coastal States Gas
Corp. - Coastal
States Marketing,
Inc., subsid.
Continental Oil Co. -
Conoco Chenis.
Dow Chem. U.S.A.
E. I. du Pont de Ne-
mours & Co., Inc. -
Plastics Dept.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
El Paso Natural Gas
Co., El Paso Products
Co., subsid.
Exxon Corp. - Exxon
Chem. Co., div. -
Exxon Chem. Co. U.S.A.
Getty Oil Co.
The B. P. Goodrich
Co. - B. F. Goodrich
Chem. Co., div.
Gulf Oil Corp. -
Gulf Oil Chems. Co.,
div, - Petrochems. Div.
Marathon Oil Co.
Location(s) 2) 3
Houston, Tex.
1975
capacity2
MM kg (MM Ib)
34 (75)
Total1**5
production
MM kg (MM Ib)
for year of estimate
(See previous page)
Clinton, Iowa
Lake Charles, La.
Blue Island, 111.
Corpus Christ!, Tex.
Westlake, La.
Bay City, Mich.
Freeport, Tex.
Plaquemlne, La.
Orange, Tex.
Longview, Tex.
Odessa, Tex.
Baton Rouge, La.
Baytown, Tex.
Bayway, N. J.
Delaware City,
Calvert City, Ky.
Cedar Bayou, Tex.
Philadelphia, Pa.
Port Arthur, Tex.
Detroit, Mich.
Texas City, Tex.
Beaumont, Tex.
61.3 (135)
210.6 (530)
20.') (45)
25 (55)
18.2 (40)
t5.ll (100)
200 (440)
72.6 (160)
68.1 (150)
136.2 (300)
79.4 (175)
710.5 (1,565)
249.7 (550)
145.3 (320)
81.7 (180)
63.6 (140)
56.7 (125)
84 (185)
252 (555)
45.4 (100)
129.4 (285)
220.2 (485)
-------
Table A-l. (Continued)
Propy-
lene
(cont'd)
Usage1
(See previous page)
OS
00
Manufacturer(s)2'3
Mobil Oil Corp. -
Mobil Chem. Co., div. -
Petrochems. Div.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Northern Natural Gas
Co. - Northern Petro-
chem., subsid. -
Polymers Div.
Novamont Corp.
The Oil Shale Corp. -
Lion Oil Co., subsid.
Petro Gas Producing Co.
Phillips Petroleum Co.
Puerto Rico Olefins Co.
Shell Chem. Co. -
Base Chems.
Skelly Oil Co.
Standard Oil Co. of
Calif. - Chevron Chem.
Co., subsid. - Oronite
Additives & Indust.
Chems. Div. -
Indust. Chems.
Standard Oil Co. (Ind.)
Amoco Chems. Corp.,
subsid.
The Standard Oil Co.
(Ohio)
Sun Oil Co. - Sun Oil
Co. of Penn., subsid.
Suntide Refining Co.,
subsid.
Location(s)2'3
Beaumont, Tex.
Chocolate Bayou,
Morris, 111.
Kenova, ¥. Va.
El Dorado , Ark .
Groves, Tex.
Sweeny, Tex.
Penuelas, P. R.
Deer Park, Tex.
Dominguez, Calif.
Norco, La.
El Dorado , Kans .
El Segundo, Calif.
Richmond, Calif.
Total1"5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
220.2
250
90.8
81
-
25
68.1
295.1
199.1
79.5
100
11.8
18.2
93.1
(185) (See previous page)
(550)
(200)
(-185)
(55)
(150)
(650)
(1,100)
(175)
(220)
(26)
(10)
(205)
Chocolate Bayou,
Tex.
Texas City, Tex.
Wood River, 111.
Lima, Ohio
Toledo, Ohio
Duncan, Okla.
Marcus Hook, Pa.
Toledo, Ohio
Corpus Christ!,.
Tex.
179.3 (395)
172.5
59
81.7
88.5
36.3
151.1
25
91
(380)
(130)
(180)
(195)
(80)
(310)
(55)
(200)
-------
Table A-l. (Continued)
Chemical.
Propy-
lene
(cont'd)
VO
UJ
Propylene
ehloro-
hydrin
Propy-
lene
dichloride
Propy-
lene
oxide
(See previous page)
Organic synthesis
(introducing hydroxy-
propyl group)
Intermediate for per-
chloroethylene &
carbon tetrachloride;
lead scavenger for
antiknock fluids;
solvents for fats,
oils, waxes, gums, &
resins; solvent mix-
tures for cellulose
esters & ethers;
scouring compounds;
spotting agents; metal
degreasing agents;
soil fumigant for
nematodes
Propylene glycol &
other glycols; urethane
foams; surfactants &
detergents; isopropanol
amines; fumigant; syn-
thetic elastomer
(homopolymer)
Texaco Inc.
Jefferson Chem. Co.,
Inc., subsid.
Texas City Refining
Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Union Oil Co. of Calif.
Eastman Kodak Co. -
Eastman Organic Chems.
Dow Chem. U.S.A.
Olin Corp. - Designed
Products Div.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Caribde Corp. -
Chems. & Plastics Div.
BASF Wyandotte Corp. -
Indust. Chems. Group -
Dow Chem. U.S.A.
Olin Corp. - Designed
Products Co.
Oxirane Chem. Co.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Locations)2'3
Port Arthur, Tex.
Westville, N. J.
Port Neches, Tex.
Texas City, Tex.
Seadrift, Tex.
Taft, La.
Texas City, Tex.
Torrance, Calif.
Whiting, Ind.
Penuelas, P. R.
Beaumont, Tex.
Rochester, N. Y.
Freeport, Tex.
Plaquemine, La.
Brandenburg, Ky.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
Wyandotte, Mich.
Preeport, Tex.
Plaquemine, La.
Brandenburg, Ky.
Bayport, Tex.
Port Neches, Tex.
1975
capacity2
MM kg (MM Ib)
11.3 (25)
25 (55)
59 (130)
45.4 (100)
50 (110)
90.8 (200)
109 (240)
125 (275)
208.8 (1(60)
43.1 (95)
Total =
6,751 (It,870}
11.3 (25)
4-5 (10)
Total1* >5
production
MM kg (MM Ib)
for year of estimate
(See previous page)
11.3 (25)
Total =
315-5 (695)
79.^ (175)
340.5 (750)
100 (220)
59 (130)
404 (890)
68.1 (150)
Total =
1,051 (2,315)
808
(1,780) -1974
-------
Table A-l. (Continued)
I
\O
•>
O
Chemical
Fyridine
(natural
&
synthetic)
Quinone
Resorcinol
Resor-
cylic
acid
Sali-
cylic
acid
Synthesis of vitamins
& drugs; solvent; water-
proofing; rubber chemi-
cals; denaturant for
alcohol & antifreeze
mixtures; dyeing assist-
ant in textiles;
fumgicides
Mfg. of dyes & hydro-
quinone
Resorcinol-formaldehyde
resins; dyes; pharma-
ceuticals; cross-link-
ing agent for neoprene;
rubber tackifier; ad-
hesives for wood veneers
& rubber-to-textile com-
posites ; medicine;
mfg. of styphnic acid
Dyestuff & pharmaceuti-
cal intermediate; chemi-
cal intermediate in
synthesis of fine or-
ganic chemicals;
light stabilizers;
resins
Mfg. of aspirin & other
medlclnals; preserva-
tive; dyes; perfumes;
prevulcanization inhib-
itor; organic Inter-
mediate; fungicide
Manufacturer(s)2'3
Natural:
Crowley Tar Products,
Inc .
Koppers Co . , Inc . -
Organic Materials Div.
Synthetic :
Reilly Tar & Chem.
Corp.
Warner-Lambert Co . -
Nepera Chem. Co., Inc.,
subsid.
Location(s)2 * 3
Bait imore , Md .
Houston, Tex.
Follansbee, W. Va.
Indianapolis , Ind.
Harriman, N. Y.
1975
capacity2
MM kg (MM lb)
_
-
_
16 C35)
2.3 (5)
Synthetic Total
18.3 (40)
Total1**5
production
MM kg (MM lb)
for year of estimate
3.1} (7.42) -1968
=
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Prank Enterprises
Koppers Co., Inc. -
Organic Materials Div.
Kingsport, Tenn.
Columbus, Ohio
Petrolia, Pa.
11.3 (25)
Total =
11.3 (25)
11.8 (26)
-1970
Aldrich Chem. Co., Inc.
Koppers Co., Inc. -
Organic Materials Div.
Dow Chem. U.S.A.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Milwaukee, Wise.
Petrolia, Pa.
Midland, Mich.
St. Louis, Mo.
7-7 (17)
9-1 (20)
6.2 (13.6) -1969
-------
Table A-l. (Continued)
Chemical
Sali-
cylic
acid
(cont'd)
Sodium
acetate
VO
Sodium
carboxy-
methyl
cellulose
(See previous page)
Dye & color intermed-
iate ; Pharmaceuticals;
cinnamic acid; soaps;
photography; purifica-
tion of glucose; meat
preservation; medicine;
electroplating; tanning;
dehydrating agent; buf-
fer in foods; laboratory
reagent
Detergents, soaps, food
products (especially
dietetic foods & ice
cream), where it acts as
water binder, thickener,
suspending agent, & emul-
sion stabilizer; textile
manufacturing (sizing);
coating paper & paper
board to lower porosity;
drilling muds; emulsion
paints; protective
colloid; Pharmaceuticals;
cosmetics
Manufacturer(g)2 *^_
Sterling Drug Inc. -
The Hilton-Davis
Chemical Co., div,
Tenneco Inc. - Tenneco
Chems., Inc. -
Organics & Polymers
Div.
Allied Chem. Corp. -
Specialty Chems. Div.
Dan River, Inc.
Howerton Gowen Chems.,
Inc.
Mallinckrodt, Inc. -
Indust. Chems. Div.
Washine Div.
Hitter Chem, Co., Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
BASF Wyandotte Corp. -
Indust. Chems. Group
Location(s)2*3
Cincinnati, Ohio
Garfield, N. J.
Marcus Hook, Pa.
Danville, Va.
Roanoke Rapids,
N. C.
St. Louis, Mo.
Lodi, N. J.
Amsterdam, N. Y.
Niagara Palls,
N. Y.
Wyandotte, Mich.
1975
capacity2
MM kg (MM lb)_
3.2 (7)
(10)
Total =
24.5 (54)
Co. - The Buckeye Cel-
lulose Corp., subsid.
United Aircraft Corp. -
Essex Internat'l Inc.,
subsid.
Muncle, Ind.
1.8 (4.0)
Brown Co .
Hercules Inc. - Coatings
& Specialty Products
Dept.
H. Kohnstamm & Co.,
Inc.
The Procter & Gamble
Berlin, N. H.
Harbor Beach, Mich.
Hopewell, Va.
Camden, N. J.
Clearing, 111.
Memphis, Tenn,
-
1.5 (10.0)
18 (10.0)
0.9 (2.0)
0.5 (1.0)
3.2 (7.0)
1.1 (2.5)
Total =
30.2 (66.5)
Total"5
production
MM kg (MM Ib)
for year of estimate
(See previous page)
29.5 (61.9) -1970
-------
Table A-l. (Continued)
Chemical
Locations)2'3
1975
capacity2
MM kg (MM Ib)
Total4'5
production
MM kg (MM Ib)
for year of estimate
Sodium
formate
Sodium
phenate
Sorbic
acid
Reducing agent;
medicine; manufacture of
formic acid & oxalic
acid; organic chemicals;
mordant; tanning; wall-
paper printing; plating
Antiseptic; salicylic
acid; organic synthesis
Fungicide; food pre-
servative; eopolymeri-
zation; upgrading of
drying oils; cold rub-
ber additive; inter-
mediate for plastici-
zers & lubricants
Commercial Solvents
Corp.
Hercules Inc. -
Synthetics Dept.
Pan American Chem.
Corp.
Tenneco Inc. - Tenneco
Chems., Inc. -
Organics & Polymers Div.
American Petrofina, Inc,
American Petrofina Co.
of Texas, subsld.
Colt Indust., Inc. -
Crucible Stainless Steel
& Alloy Div.
National Steel Corp. -
Great Lakes Steel Div. -
B. F. Div.
Republic Steel Corp. -
Iron & Chem. Div.
Sharon Steel Corp. -
Fairmont Coke Works
Shenango Inc.
Wheeling-Pittsburgh
Steel Corp.
American Hoechst Corp. -
Dyes & Pigments Div.
Pfizer Inc. -
Chems. Div.
Seiple, Pa.
Louisiana, Mo.
Toledo, Ohio
Fords, N. J.
Port Arthur, Tex.
Midland, Pa.
Zug Island
(River Rouge),
Mich.
_Chicagoa 111.
Cleveland, Ohio
Fairmont, W. Va.
Neville Island, Pa.
Monessen, Pa.
Coventry, R, I.
Groton, Conn.
-------
Table A-l. (Continued)
T
Polystyrene plastics;
SBR, ABS, S'SAN res-
ina; protective coatings
(styrene-butadiene latex;
alkyds); styrenated poly-
esters ; rubber-modified
polystyrene; copolymer
resins» intermediate
Suc6inic ftefticinei organic
acid ^ithesls; mfg. of lac^
quers, dyes, esters for
perfumes, suceinates;
photography^ in fopds
as a sequestrant, buffer,
neutralizing agent
Total1"5
1975 production
capacity2 MM kg (MM Ib)
Manufacturers )2'3
American Petroflna,
Inc. T- Cosden Oil &
Chem. Co., subsid.
ARCO/Polymers, Inc.
Cos-Mar, Inc1.
Dow Chem. U.S.A.
El Paso Natural Gas
Co. - El Paso Co.,
subsid.
Foster Grant Co ,( , Inc .
Gulf OH Corp.. T Gulf
Oil Chems. Co., div. -
Petroehems . Div,
Monsanto Co. - Monsanto
Polymers & Petroehems .
Co.
Standard Oil Co, (Ind.) -
Amoco Chems . Corp . ,
subsid.
Sun Oil Co. - Sun Oil
Co. of Penn., subsid.
Location(s)2'3
Big Spring, Tex.
Beaver Valley, Pa.
Houston, Tex.
Carville, La.
Preeport , Tex .
Midland, Mich..
Odessa, Tex.
Baton Rouge, La.
Welcome, La.
Texas City, Tex.
Texas City, Tex.
Corpus Christ!,
Tex,
MM kg (MM Ib) for year of estimate
51.5
199.8
51.5
272.1
719.1
181.6
51.5
372.3
227
590.2
385.9
36.3
(120) 2,721 (6,000) -1971
(410)
(120)
(600)
(1,650)
(100)
U20)
(820)
(500)
(1,300)
(850)
(80)
Suntlde Refining Co.
subsid.
Union Carbide Corp. -
Chems. & PlastJ.es Dlv.
Allied Chem. Corp. -
Specialty Chems. Div.
Richardson-Merrell,
Inc. - J. T. Bak,er
Chem. Co,, subsid.
Seadrdft, Tex.
Marcus Hook, Pa.
Phillipsburg, N. J.
136,2 (300)
Total *
3..311.2 (7,300)
-------
Table A-l. (Continued)
Succino-
nltrlle
Sulfo-
lane
cr>
I
Synthesis
gas
Tere-
phthalic
acid
Tetra-
chloro-
ethane
Tetra-
chloro-
phthalic
anhydride
Organic synthesis
Extraction of aromatic
hydrocarbons from oil
refinery streams;
fractionation of wood
tars, tall oil, & other
fatty acids; polymeriza-
tion solvent; plastiei-
ser; component of hydrau-
lic fluid; textile
finishing
Organic synthesis; mfg.
of alcohols (Oxo process);
low-Btu fuel gas
Production of linear,
crystalline polyester
resins, fibers & films
by combination with
glycols, e.g., "Dacron,1
"Mylar," "Terylene;"
also used as a reagent
for alkali in wool; ad-
ditive to poultry feeds
Solvent; cleansing &
degreasing metals; paint
removers, varnishes, lac-
quers , photographic
film; resins & waxes;
extraction of oils &
fats; alcohol denatu-
rant; organic synthesis;
insecticides; weed kil-
ler; fumigant
Intermediate in dyes,
Pharmaceuticals, plasti-
cizers, & other organic
materials; flame-
retardant in epoxy
resins
Guardian Chem. Corp. -
Eastern Chem. Div.
R.S.A. Corp.
Phillips Petroleum Co.,
Petrochem. & Supply Div.
Shell Chem. Co. -
Base Chems.
Hauppauge, N. Y.
Ardsley, H. Y.
Phillips, Tex,
Norco, La,
Eastman Kodak Co, -
-Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div,
Hercules Inc. -
Synthetics Dept.
Standard Oil Co. (Ind.)
Amoco Chems. Corp.,
subsid.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics
Corp., subsid. -
Electrochemical &
Specialty Chems. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Kingspcrt, Tenn.
Wilmington, N. C.
Decatur, Ala.
Joliet, 111.
Taft, La.
1,557 (3,^30) -1974
113-5
363.2 (800)
45.if (100)
Total =
522.1 (1,150)
Bridgeport, N. J.
-------
Table A-l. (Continued)
VO
•C-
Ui
Chemical
Tetra-
ethyl
lead
(TEL)
Tetra-
hydro-
naphtha-
lene
Tetra-
hydro-
phthalic
anhydride
Tetra-
methylene-
diamine
Toluene
-2, II-
dlamine
Antiknock gasoline ad-
ditive; certain ethyl-
ation operations
Solvent; chemical
intermediate
Chemical intermediate
for light-colored al-
kyds* polyesters,
plasticizers & ad-
hesives; Intermediate
for pesticides;
hardener for resins
Chemical intermediate
Dye intermediate; direct
oxidation black for furs
& hair; source for
toluene-2,i}-diisocya~
nate
Manufacturer (s) 2 *_3
E. I. du Pont de Ne-
mours & Co., Inc. -
Oganic Chemicals
Dept. - Petroleum
Chems. Dlv.
Ethyl Corp.
Nalco Chem. Co. -
Petroleum & Process
Chem. Div.
PPG Indust., Inc. -
Chem, Div. - Houston
Chem. Co., div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Dyes & Chems. Div.
Lonza Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Petro-Tex Chem. Corp.
Petro-Tex Chem. Co.,
subsid.
BASF Wyandotte Corp. -
Indust. Chems. Group
Air Products & Chems.,
Inc.
American Cyanamid Co. -
Organic Chems. Div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.
GAP Corp. - Chem. Div.
Olin Corp. - Agricul-
tural Chems. Div. -
Designed Products Dlv.
Rubicon Chems. Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Location(s)2'3
Antoich, Calif.
Deepwater, N. J.
1975
capacity2
MM kg (MM Ib)
Kb.* (310)
Total*'5
production
MM kg (MM Ib)
for year of estimate
216.7 (513.1) -1968
Baton Rougei La.
Pasadena, Tex.
Freeport, Tex.
Beaumont, Tex.
Deepwater, N. J.
Mapleton, 111.
Institute & South
Charleston, W. Va.
Houston, Tex.
Wyandotte, Mich.
Pasadena, Tex.
Bound Brook, N. J.
Deepwater, N. J.
Rensselaer, N. Y.
Lake Charles, La.
Ashtabula, Ohio
Brande nb urg, Ky.
Rochester, N. Y.
Geismar, La.
Institute & South
Charleston, W. Va.
158.9 (350)
18.2 (40)
iJ5.4 (100)
Total*=
376.8 (830)
* Includes TEL,
TML and mixtures.
-------
*Pable A-l. (Gbntinued)
Toluene-
sulfonic
acids
ON
Toluene-
sulfon-
amide
Toluene-
sulfonyl
chloride
Trichloro-
benzene
Usage1
Dyes; Organic synthesis;
acid catalyst
Organic synthesis;
plasticiaers & resins;
fungicide & mildewcide
in paints & coatings
Organic synthesis; inter-
mediate in the synthesis
of saccharin & dyestuffs
Solvent in chemical
mfg.; dyes & inter-
mediates; dielectric
fluid; synthetic trans-
former oils; lubricants;
heat-transfer medium;
insecticides
Manufacturer^)2*3
American Cyanainid Co. -
Organic Chems . Div.
Cities Service Co.,
Inc. *- North American
Chems . & Metals Group -
Indust . Chems-. Div.
Monsanto Co . - Monsanto
Indust . Chems <. Co .
Wease Chem. Co., Inc.
Jim Walter Corp;. - U.S*
Pipe S Foundry 'Co , ,
subsid. - Chem. Div.
Monsanto Co. •*. Monsanto
Indust . Chems . Co .
Monsanto Co. - Monsanto
Indust-. Chems. Co.
Dow Chem. U.S.A.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. *• Hooker
Chems. & Plastics
Corp., subsid. -
Electrochemical &
Specialty Chems. Div.
Sobin Cheros., Inc. -
Montrose Chem. Div,
Solvent Chem. Co., Inc.
Standard Chlorine
Chem. Co., Inc.
Location (s)^.'?
•Bound Brook;, N, J.
Copperhill^ ^Tenn.
St. Louis, Mo.
State College, Pa.
Birmingham, Ala.
St. Louis, Mo.
St. Louis, Mow
Midland, Mich.
Niagara Falls,
N. Y-.
Newark, N. J.
Maiden, Mass.
Niagara Palls,
H. Y.
Delaware City,
Del.
Kearny, N. J.
1975
capacity2
MM kg (MM.lto)
Total1"5
production
MM kg {MM lb)
for^year. ,af \e_st i_ma_tg.
-------
Table A-l. (Continued)
Trichloro-
ethane
Trichloro-
ethylene
Solvent for cleaning
precision instruments;
aerosol propellant;
metal degreasing;
pesticide; solvent for
fats, oils, waxes,
resins, other products;
organic synthesis
Metal degreasing; ex-
traction solvent for
oils, fats, waxes; sol-
vent dyeing; dry clean-
Ing ; refrigerant &
heat exchange liquid;
organic syntheses;
fumigant; medicine
(anesthetic); clean-
ing & drying electronic
parts
1975
capacity2
Manufacturer(s) 2> 3
Dow Chem. U.S.A.
Ethyl Corp.
PPG Indust. , Inc. -
Chem. Div. - Indust.
Chem. Div.
Vulcan Materials Co. -
Chains, Div.
Location(s)2'3
Freeport, Tex.
Baton Rouge, La.
Lake Charles, La.
Geismar, La.
MM kg
15«.
22.
79.
29.
To
286
(MM Ib)
1 (310)
7 (50)
1 (175)
5 (65)
tal •
(630)
Total1"5
production
MM kg (MM Ib)
for year of estimate
170.1 (371.6) -1971
1,2,3-TTl-
chloro-
propane
Paint & varnish remover;
solvent; degreasing agent
Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co. f Electro Chems.
Div.
Dow Chem. U.S.A.
Ethyl Corp.
Occidental Petroleum
Corp. - Hooker Chem Corp.
subsid. - Hooker Chems.
& Plastics Corp.,
subsid. - Electrochemi-
cal & Specialty Chems.
Div.
PPO Indust., Inc. -
Chem. Div. - Indust.
Chem. Div.
Dow Chem. U.S.A.
Shell Chem. Co. -
Base Chems.
Deer Park, Tex.
Freeport, Tex.
Baton Rouge, La.
Taft, La.
Lake Charles, La.
Freeport, Tex.
Deer Park, Tex.
15.1 (100)
68.1 (150)
22.7 (50)
18.2 (10)
127.1 (280)
Total =
281.5 (620)
-------
Table A-l - C Cont inued)
I
VO
•P**
00
1,1,2-Tri-
chloro-
1,2,2-tri-
fluoro-
ethane
Tri-
ethanol-
amine
Triethyl-
amlne
Trl-
ethylene
glycol
Dry cleaning solvent;
fire extinguishers; re-
frigerant ; air-condi-
tioning units; to make
chlorotri fluoroethylene;
blowing agent; polymer
intermediate; solvent
drying; drying electro-
nic parts £ precision
equipment
Patty acid soaps used
in drycleaning, cosmet-
ics, household deter-
gents, & emulsions;
wool scouring; textile
antifume agent & water-
repellent ; dispersion
agent; corrosion inhi-
bitor; softening agent,
humectant, & plasticl-
zer; insecticide; che-
lating agent; rubber
accelerator
Catalytic solvent in
chemical synthesis; ac-
celerator activators
for rubber; wetting,
penetrating & water-
proofing agents of
quarternary ammonium
types; curing & harden-
ing of polymers (e.g.,
core-binding resins);
corrosion inhibitor
propellant
Solvent for nitrocellu-
lose; various gums &
resins; lacquers; or-
ganic synthesis; air-
conditioning units;
bactericlde (in vapor
form); humectant in
printing inks; textile
conditioner; fungicide
Manufacturer(s)2»3
Allied Chem. Corp. -
Specialty Chems. Div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Preon® Products Div.
Union Carbide Corp. -
Chems. & Plastics Div.
(See diethanolamlne)
Air Products fr Chems.,
inc.
Pennwalt Corp. -
Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Va. Chems. Inc. - Indust.
Chems. Dept.
Allied Chem. Corp. -
Specialty Chems. Div.
Celanese Corp. - Cela-
nese Chem. Co., div.
Dixie Chem. Co.
Dow Chem. U.S.A.
Location(s)2'3
Baton Rouge, La.
Antioch, Calif.
Deepwater, N. J.
East Chicago, Ind.
Louisville, Ky.
Montague, Mich.
Institute & South
Charleston, W. Va.
Pensacola, Pla,
Wyandotte, Mich.
Taft, La.
Portsmouth, Va.
Orange, Tex.
Clear Lake, Tex.
Bayport, Tex,
Freeport, Tex.
Plaquemine, La.
1975
capacity^
MM kg (MM lb-)
Total"'5
production
MM kg (MM lb)
fgr__yjBar__of^estimate
(108) -1974
1.1 (3)
1.1 (3)
0.9 (2)
15.9 (35)
51.3 (113.1) -1973
-------
Table A-l. (Continued)
VO
*>
VO
Chemical
Tri-
ethylene
glycol
(cent1d)
Tri-
ethylene
glycol
dimethyl
ether
Trl-
methyl-
amine
Usage1
(See previous page)
Solvent for gases;
coupling immiscible
liquids
Manufacturer(s)z'3
Eastman Kodak Co. -
Eastman Ohem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Olln Corp. - Designed
Products Div.
PPQ Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div. -
PPQ Indust. (Caribe)
Shell Chem. Co. -
Base Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc., subsid.
The Ansul Co. -
Chem. Div.
Organic synthesis, es- Air Products & Chems.,
pecially of chlorine salts; Inc.
warning agent for natu-
ral gas; manufacture of
disinfectants; flota-
tion agent; insect
attractant; quaternary
ammonium compounds;
plastics
Commercial Solvents Corp.
E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
GAF Corp. - Chem. Div.
Rohm & Haas Co.
Locations)2'3
Longview, Tex.
Brandenburg, Ky,
Beaumont, Tex.
Guayanilla, P. R.
Gelsmar, La.
Port Neches, Tex.
Institute & South
Charleston, W. Va.
Seadrlft, Tex.
Taft, La.
Penuelas, P. R.
Marlnette, Wise .
Pensacola, Pla.
Terre Haute, Ind.
Belle, W. Va.
La Porte, Tex.
Calvert City, Ky.
Philadelphia, Pa.
1975
capacity2
MM kg (MM Ib)
<0.5 (
-------
Table A-l. (Continued)
Chemical
Tri-
iscbuty-
lene
Urea
Synthesis of resins, &
intermediate organic
compounds; lubricating
oil additive, raw
material for alkyla-
tion in producing
high octane motor fuels
Fertilizer; animal feed;
plastics; chemical inter-
mediate; stabilizer in
explosives; medicine;
adhesives; separation of
hydrocarbons (as urea
adducts); sulfamlc
acid production; flame-
proofing agents; vis-
cosity modifier for
starch or casein-based
paper coatings; re-
ported helpful in treat-
ing sickle-cell anemia
Manufacturer(s)2*3
The B. P. Goodrich
Co. - B. P. Goodrich
Chem. Co,, div.
Agway Inc.
Air Products & Chems.,
Inc.
Allied Chem. Corp. -
Specialty Chems..Div. -
Union Texas Petroleum
Div. - Agricultural Div.
American Cyanamid Co. -
Agricultural Div.
Borden Inc. - Borden
Chem. Div. - Petrochems.
CP Indust., Inc. -
Chattanooga Nitrogen
Complex - Donaldsonvilie
Nitrogen Complex -
Fremont Nitrogen Complex
N. C. Nitrogen Complex
Coastal States Gas
Corp. - Colorado Inter-
state Corp., subsid, -
Wycon Chem. Co., subsid.
Columbia Nitrogen Corp.
Cooperative Farm Chems.
Association
Gardinier Big River, Inc.
Gen. Amer. Oil of Tex. -
Premier Petrochem. Co.,
subsid.
Goodpasture, Inc.
W. R. Grace & Co. -
Agricultural Chems, Group
Hercules Inc. - Synthe-
tics Dept.
Location(s)2'3
Port Neches, Tex.
Clean, N. Y.
Pensacola, Fla.
South Point, Ohio
Geismar, La.
Omaha, Neb.
New Orleans, La.
Geismar, La.
Tyner, Tenn.
Donaldsonvllle,
La.
Fremont, Neb.
Tunis, N. C.
Cheyenne, Wyo.
Augusta, Ga.
Lawrence, Kans.
Helena, Ark.
Pasadena, Tex.
Dimmitt, Tex.
Memphis, Tenn.
Hercules, Calif.
Louisiana, Mo.
1975
capacity2
MM kg (MM Ib)
Total4'5
production
MM kg (MM Ib)
for year of estimate
51.5 (120)
22.7 (50)
63.6 (140)
201.3 (450)
127.1 (280)
131.7 (290)
177.1 (390)
36.3 (80)
331.4 (730)
18.2 (40)
154.4 (340)
45.4 (100)
27.2 (60)
181.6 (400)
59 (130)
95.3 (210)
22.7 (50)
122.6 (270)
36.3 (80)
86.3 (190)
3,350 (7,38o)-1974
-------
Table A-l. (Continued)
Chemical
Urea
(cont1d)
Usage1
(See previous page)
Ui
Manuf acturer(s)2!>3
Kaiser Aluminum & Chem.
Corp. - Kaiser Agri-
cultural Chems. Div.
Lone Star Gas Co. -
Nipak, Inc., subsid.
Miss. Chem. Corp.
Mobil Oil Corp. -
Mobil Chem, Co., div. -
Petrochems. Div.
N-Ren Corp. - Cherokee
Nitrogen Div. - High
Plains Div.
Olin Corp. - Agricul-
tural Chems. Div.
Phillips Pacific Chem.
Co.
Phillips Petroleum Co. -
Fertilizer Div.
Reichhold Chems., Inc.
St. Paul Ammonia Pro-
ducts, Inc.
J. R. Simplot Co. -
Minerals & Chem. Div.
Skelly Oil Co. - Hawk-
eye Chem. Co., subsid.
The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid. - Chems.. Dept.
Tenn. Valley Authority
Terra Chems. Internat'l,
Inc.
Triad Chem.
Loeatlon(s)2'3
Savannah , Ga .
Kerens, Tex.
Pryor, Okla.
Yazoo City, Miss.
Beaumont, Tex.
Pryor, Okla.
Plainview, Tex.
Lake Charles, La.
Kennewick, Wash.
Beatrice, Net).
St. Helens, Ore.
East Dubuque, 111.
Pocatello, Idaho
Clinton, Iowa
Lima , Ohio
Muscle Shoals, Ala.
Port Neal, Iowa
Total1"5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
72.6
77.2
122.6
168
45.4
18.2
51.5
115-3
10.9
50
50
72.6
-
54.5
217.9
63.6
154.4
(160) (See previous page)
(170)
(270)
(370)
(100)
(40)
(120)
(320)
(90)
(110)
(110)
(160)
(120)
(180)
(140)
(340)
Donaldsonville, La.
(970)
-------
Table A-l. (Continued)
Chemical
Urea
(con'd)
Vinyl
acetate
Usage1
(See previous page)
Polyvinyl acetate,
polyvinyl alcohol, poly-
vinyl butyral, & poly-
vinyl chloride-acetate
resins (q.v.); these are
used particularly In
latex paints; paper
coating; adhesives;
textile finishing;
safety glass inter-
layers
Manufacturer(s) 2 ' 3
Tyler Corp. - Atlas
Powder Co., subsld.
Union Oil Co. of Calif.
Collier Carbon & Chem.
Corp., subsid.
U.S. Steel Corp. -
USS Agri-Chems. div.
Valley Nitrogen Pro-
ducers, Inc.
The Williams Companies
Agrlco Chem. Co.,
subsid.
Borden Inc. - Borden
Chem. Div. - Petrochems.
Celanese Corp. - Cela-
nese Chem. Co., div.
E. I. du Pont de Ne-
mours & Co,, Inc. -
Plastics Dept.
National Distillers &
Chem. Corp. - Chems.
Div. - U.S. Indust.
Chems. Co., div.
National Starch 4 Chem.
Corp.
Reichhold Chems., Inc. -
Reichhold Chem. Del
Caribe, Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Location(s)2'3
Joplin, Mo.
Brea, Calif.
Kenai, Alas.
1975
capacity2
MM kg (MM Ib)
59 (130)
50 (110)
308. T (680)
Total1*'5
production
MM kg (MM Ib)
for year of estimate
(See previous page)
Cherokee, Ala.
22.7' (50)
El Centre, Calif.
Helm, Calif.
Blythevllle, Ark.
Donaldsonville, La.
110.7
31.8
299.6
299.6
(310)
(70)
(660)
(660)
Total -
5,057.6 (11,1*0)
Geismar, La.
Bay City, Tex.
Clear Lake, Tex.
Pampa, Tex.
La Porte, Tex.
68.1
136.2
158.9
29.5
158.9
(150)
(300)
(350)
(65)
(350)
Deer Park, Tex.
Long Mott, Tex.
Rio Piedras, P. R.
Texas City, Tex.
170.2 (375)
31.8 (70)
6.8 (15)
120.3 (265)
Total -
880.8 (1,910)
635-6 (1,100) -1971
-------
Tab le A-l. (Cont Inued)
Chemical
Vinyl
chloride
Polyvinyl chloride (q,
ft copolymers; organic
synthesis j adhesives
for plastics
VO
Ln
CO
Manufacturer(s)2 *3
v.) Allied Chem. Corp. -
Indust. Chems. Dl v.
Borden Inc. - Borden
Chem. Div. - Petrochems.
Continental Oil Co. -
Conoo.o Chems.
Dow Chem. U.S.A.
Ethyl Corp.
The B. F. Goodrich Co. -
B. P. Goodrich Chem.,
Co., subsid.
Monochem, Inc.
PPG Indust., Inc. -
Chem. Div. - Indust.
Chem. Div. - PPG Indust.
(Caribe)
Shell Chem. Co. - Base
Chems.
Stauffer Chem, Co. -
Plastics Div. - Poly-
mers West
Tenneco Inc. - Tenneco
Chertis., Inc.. - Organic s
& Polymers Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Locatlon(s)2'3
Baton Rouge, La.
Geismar, La.
Westlake, La.
Freeport , Tex.
Oyster Creek, Tex.
Plaquemlne, La.
Baton Rouge, La.
Pasadena, Tex.
Calvert City, Ky.
Geismar, La.
Lake Charles, La.
Quayanilla, P. R.
Deer Park, Tex.
Norco, La.
Carson, Calif.
Total1"5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
136.2
-
295.1
90.8
317.8
177.1
136.2
68.1
151
136.2
181.6
227
381.1
317.8
79.5
(300) 2,512 (5,600) -1971
(650)
(200)
(700)
(390)
(300)
(150)
(1,000)
(300)
(loo)
(500)
(810)
(700)
(175)
Houston, Tex.
Texas City, Tex.
102.1 (225)
68.1 (150)
Total =
3,169 (6,980)
-------
Table A-l. (Continued)
CT»
V0
Ui
Ch_emlc_ajl
Vinyli-
dene
chloride
Vinyl
toluene
in-xylene
o-xylene
Copolymerized with vinyl
chloride or acryloni-
trile to form various
kinds of saran; other
copolymers are also made;
adhesives; component of
synthetic fibers
Solvent; Intermediate
Solvent; intermediate for
dyes & organic synthesis,
especially isophthalic
acid; insecticides;
aviation fuel
Mfg. of phthalic an-
hydride; vitamin &
pharmaceutical synthesis;
dyes; insecticides; motor
fuels
Manufacturer(s)2 *3
Dow Chem. U.S.A.
PPG Indust., Inc. -
Chem. Div. - Indust.
Chem. Divf.
Dow Chem.' U.S.A.
Foster Grant Co., Inc.
Atlantic Richfield
Co. - ARCO Chem. Co.,
div.
American Petrofina,
Inc. - Cosden Oil &
Chem. Co._, subsid.
Atlantic Richfield Co. -
ARCO Chem. Co., div.
Cities Service Co.,
Inc. - North American
Petroleum Group
Coastal States Gas
Corp. - Coastal States
Marketing, Inc., subsid.
Commonwealth Oil Refin-
ing Co., Inc. - Common-
wealth Petrochems.,
Inc., subsid.
Crown Central Petroleum
Corp.
Exxon Corp, - Exxon
Chem. Co., div. -
Exxon Chem. Co. U.S.A.
Kerr-MeGee Corp. - South-
western Refining Co.,
Inc., subsid.
Locatlon(s)2'3
Freeport, Tex.
Plaquemine, La.
1975
capacity2
MM JCK (MM Ib)
-
Total"'5'
production
MM kg (MM Ib)
for year of estimate
77.2 (170) -1971
Lake Charles, La.
Midland, Mich.
Baton Rouge, La.
Channelview, Tex.
Big Spring, Tex.
Houston, Tex.
Lake Charles, La.
Corpus Christ!,
Penuelas, P. R.
Pasadena, Tex.
Baytown, Tex.
Corpus Christ!, Tx.
15.9 (35)
8.2 (18)
95.3 (210)
51.5 (120)
18.2 do)
63.6 (110)
31 (75)
222,5 (190)
")5.1 (100)
(78)
-1970
(824.8) -1970
-------
Table A-l. (Continued)
Chemical
o-xylene
(cont'd)
Ln
Ln
p-xylene
Usage1
(See previous page)
Synthesis of tere-
phthalic acid for
polyester resins &
fibers ("Dacron,"
"Mylar," "Terylene");
vitamin & pharmaceu-
tical syntheses;
insecticides
Manufacturer(s)2 J 3
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Phillips Petroleum Co. -
Phillips Puerto Rico
Core, Inc., subsid.
Shell Chem. Co. - Base
Chems.
Standard Oil Co. of
Calif. - Chevron Chem.
Co., subsid. - Oronlte
Additives & Indust.
Chems. Div. - Indust.
Chems.
Sun Oil Co. - Sun Oil
Co. of Penn,, subsid. -
Suntide Refining Co.,
subsid.
Tenneco Inc. - Tenneco
Oil Co., div.
Atlantic Richfield Co. -
ARCO Chem. Co.s div.
The Charter Co. -
Charter Oil Co., subsid.,
Charter Internat'l Co.,
subsid.
Cities Service Co.,
Inc, - North American
Petroleum Group
Exxon Corp. - Exxon
Chem, Co., div. -
Exxon Chem. Co. U.S.A.
Hercor Chem. Corp.
Phillips Petroleum Co. -
Phillips Puerto Rico
Core Inc., subsid.
LooatiQn(s)2*
Chocolate Bayou,
Tex.
Guayama, P. R.
Deer Park, Tex.
Richmond, Calif.
Corpus Christ!,
Tex.
Chalmette, La.
Houston, Tex.
Houston, Tex.
Lake Charles, La.
Baytown, Tex.
Penuelas, P. R.
Guayama, P. R.
1975
capacity2
MM kg (MM Ib)
Total1*1*
production
MM kg (MM Ib)
for year_ _p_f^estimat_e_
13.6 (30) (See previous page)
59 (130)
90.8 (200)
67.2
72.6 (160)
70.4 (155)
Total =
915-3 (2,016)
181.6 (iioo) 1,216.7 (2,680) -1974
6.8 (15)
15.9 (35)
181.6 (Hoo)
238.3 (525)
34 (75)
-------
Table A-l. (Continued)
Total '•
I
vo
Ui
Chemical Usage1
p-xylene (See previous page)
( cont ' d)
Manufacturer(s)2' 3
Shell Chem. Co. -
Base Chems.
Standard Oil Co. of
Calif. - Chevron Chem.
Co., subsid. - Oronite
Additives 8 Indust.
Chems. Div. - Indust.
Chems .
Standard Oil Co. (Ind.) -
Amoco Chems . Corp . ,
Location(s)2'3
Deer Park, Tex.
El Segundo, Calif.
Pascagoula, Miss.
Richmond, Calif.
Decautur, Ala.
Texas City, Tex.
1975 production
capacity2' MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
45.1
HO. 7
50
121.8
121.8
(100) (See previous page)
(310)
(110)
(275)
(275)
Xylenol
(mixed 2,
4~; 2,5-;
3, it-;
3,5-)
Xylidlne
(mixed 2,3-;
2 , if- ; 2,5-;
2,6-)
Disinfectants; solvents,
Pharmaceuticals, insect-
icides ft fungicides;
plasticizers; rubber
chemicals; additives to
lubricants & gasoline;
manufacture of poly-
phenylene oxide
(2,6-isomer only);
wetting agents;
dye stuffs
Dye intermediates;
organic syntheses;
Pharmaceuticals
subsid.
Sun Oil Co. - Sun Oil
Co. of Penn., subsid.
Suntide Refining Co.,
subsid.
Tenneco Inc. - Tenneco
Oil Co., div.
Koppers Co., Inc. -
Organic Materials Div.
Productol Chem, Co.
Stimson Lumber Co. -
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.
Corpus Christi,
Chalmette, La.
Follansbee, W. Va.
Santa Pe Springs,
Calif.
Anacortes, Wash.
Deepwater, N. J.
136.2 (300)
15.l| (100)
Total =
1,325.7 (2,920)
-------
APPENDIX B
RAW MATERIALS
6-957
-------
Table B-l. RAW MATERIALS FOR THE
INDUSTRIAL ORGANIC CHEMICALS INDUSTRY
*Acetaldehyde
*Acetaldol
*Acetam"lide
*Acetic acid
*Acetic anhydride
*Acetone
*Acetone cyanohydrin
*AGetonitrile
Acetyl chloride
*Acetylene
*Acrolein
*Acrylic acid
*Acrylonitrile
Air
Alkyl amines -^
Alkyl benzenes -I group
... , ., ., I names
Alkyl chloridesj
*Allyl alcohols
*Allyl chlorides
Alumina gel
Aluminum chloride
Ammonia
Ammonium salts
(e.g., carbonate)
*Amyl alcohols
*Amyl chlorides
*Aniline
*Aniline hydrochloride
Aniline sulfate
Antimony (III) fluoride
Aromatics, C8-groups
*Benzaldehyde
*Benzene
*m-Benzene disulfonic acid
*p-Benzene disulfonic acid
*Benzene sulfonic acid
*Benzil
*Benzoic acid
*Benzoin
*p-Benzoquinone
*Benzotrichloride
*Benzoyl chloride
*Benzyl chloride
Bromine
*Bromobenzene
*1,3-Butadiene
*n-Butane
2-Butanone
*l-Butene
*2-Butene
*n-Butenes
*n-Butyraldehyde
*n-Butyl alcohol
*sec-Butyl alcohol
*tert-Butyl alcohol
*tert-Butyl toluene
*Butyric acid
Calcium carbonate
Calcium hydroxide
Calcium oxide
Carbon
Carbon dioxide •
Carbon monoxide ,1
*Carbon disulfide
*Carbon tetrachloride
Catalytic gas oils
a-Cellulose
Charcoal
Chlorine (dry)
*Chloracetic acid
*Chlorobenzene
*Chloroform
*Chlorotoluene
Coal tars
Cobalt toluate
*Crotonaldehyde
*Cumene
*Cumene hydroperoxide
*Cyanogen chloride
*Cyclohexane
*Cyclohexanol
*Cyclohexanone
*Diacetone alcohol
Diallyl ether - group name
*o-Di chlorobenzene
*m-Di chlorobenzene
*Dichlorohydrin
*Diethylene glycol dibutyl ether
Diethylene glycol monoethers - group
._.. ., , ., name
*Diethyl ether
6-958
-------
Table B-l (Continued). RAW MATERIALS FOR THE
INDUSTRIAL ORGANIC CHEMICALS INDUSTRY
Diethyl oxalate
*1,1-Di f1uoroethane
*Diisobutylene
Dimethyl acetal
*Dimethyl sulfate
*Dimethyl sulfide
*Dinitrobenzenes
*Dinitrobenzoic acid
*Dinitrotoluene
*Diphenyl oxide
*Dodecene
Drip oils
*Epichlorohydrin
*Ethane
*Ether
*Ethyl acetate
*Ethyl alcohol
*Ethyl benzene
*Ethyl chloroacetate
*Ethyl chloride
Ethyl formate
Ethyl sulfate
Ethyl toluene
Ethylene
*Ethylene chlorohydrin
*Ethylene diamine
*Ethylene dibromide
*Ethylene dichloride
*Ethylene glycol
*Ethylene oxide
Flue gas
*Formaldehyde
*Formic acid
*Fumaric acid
Furfural
*Glyceraldehyde
*Glycerol
*Heptene
Hexyl alcohol
Hydrochloric acid
Hydrofluoric acid
Hydrogen
Hydrogen bromide
Hydrogen chloride
*Hydrogen cyanide
Hydrogen fluoride
Hydrogen peroxide
*Hydroquinone
Hypochlofous acid
Iron sulfate
*Isoamylenes
Isobutane
Isobutene
*Isobutyl alcohol
Isobutylene
*Isobutyraldehyde
Isopentane
*Isopropyl alcohol
*Isopropyl chloride
*Ketene
Lead
Lead amalgam
Light cycle oils
*Maleic acid
*Maleic anhydride
Manganese dioxide
*Mesityl oxide
*Methallyl chloride
Methane
*Methyl acetate
*Methyl alcohol
*Methyl chloride
*Methyl cyclohexane
*Methyl ethyl ketone
*Methyl formate
Methyl iodide
*Methyl isobutyl ketone
Methyl propene
*Methylene chloride
Monoethylene glycol monoether
group name
*Naphthalene
*l-Naphthalene sulfonic acid
*2-Naphthalene sulfonic acid
Natural gas
Nitric acid
6-959
-------
Table B-l (Continued). RAW MATERIALS FOR THE
INDUSTRIAL ORGANIC CHEMICALS INDUSTRY
*Nitrobenzene
m-Ni trochlorobenzene
Nitrogen
Nitrogen dioxide
(dinitrogen tetraoxide)
*o-Nitroanisole
*p-Nitroanisole
*o-Nitrophenol
*p-Nitrophenol
Nitrosylsulfuric acid
*Nitrotoluene
*Nonene
Octyl alcohol
"Olefins"
Oxalic acid (dihydrate)
Oxygen
*Pentane
Peracetic acid
*Perchloroethylene
*Phenol
*Phosgene
Phosphorous tribromide
*Phthalic anhydride
*Phthalimide
Polychloroaromatics
Potassium t-butoxide
Potassium cyanide
Potassium hydrosulfide
Potassium hydroxide
Potassium permanganate
Potassium sulfide
*Propane, liquid
*n-Propyl alcohol
*n-Propyl chloride
Propylene
*Propylene chlorohydrin
Propylene glycol
*Propylene oxide
*Pyridine
Refinery gas caustic
extract
Reformer bottoms
Silica gel
Sodium
*Sodium acetate
Sodium bicarbonate
Sodium bisulfite
Sodium carbonate
Sodium carbonate
emulsifier
*Sodium chloroacetate
Sodium chloride
Sodium cyanide
Sodium dichromate
Sodium ethoxide
*Sodium formate
Sodium hydrosulfide
Sodium hydrosulfite
Sodium hydroxide
Sodium perborate
*Sodium phenate
Sodium "salt"
Sodium stearate
Sodium sulfide
Sodium sulfite
Sulfur, organic derivatives
Sulfur dioxide
Sulfur dioxide, liquid
Sulfur trioxide
Sulfuric acid
Oleum
Sulfuric acid, monohydrate
Synthesis gas
*1,1,2,2-Tetrachloroethane
Tetrahydrofuran
*Trichloroaniline
*1,1,2-Trichloroethane
*Tri chloroethylene
2,4,6-Trichlorophenol
Toluene
*Toluene sulfonyl chloride
*Toluidine
Tolunitrile
*Urea
Water
Water, demineralized
Water, distilled
Water, steam
6-960
-------
Table B-l (Continued). RAW MATERIALS FOR THE
INDUSTRIAL ORGANIC CHEMICALS INDUSTRY
*m-Xylene
*o-Xylene
*p-Xylene
Zeolite, synthetic
Zinc
* Indicates chemical is also a product of this industry.
6-961
-------
APPENQIX C
CATALYSTS
6-962
-------
Table C-l. CATALYSTS USED IN THE PRODUCTION
OF INDUSTRIAL ORGANIC CHEMICALS
Acetic acid
Alkali metals
Alumi na
Alumina, modified anhydrous Gamma
Alumina, gel
Alumina-chromia
Aluminum turnings
Aluminum alkoxides
Aluminum chloride
Amine bases
Ammonium chloride
Ammonium metavanadate
Ammonium persulfate-ammonium bromide
Aniline hydrochloride
Antimony, partially fluorinated
Antimony (III) chloride
Antimony (V) chloride
Antimony (V) fluoride
Barium chloride on carbon
Barium hydroxide
Bauxi te
Bismuth-molybdenum
Boric acid
Boron trifluoride
Brass
Bromine
Calcium carbide
Calcium chloride
Calcium nickel phosphate stabilized
with 2% Chromium oxide
Calcium oxide
Carbon
Carbon, activated
Carboxyl salts of divalent transition
metals, e.g., zinc isovalerate
Chromic acid
Cobalt acetate
Cobalt carbonyl compounds
Cobalt carbonyl compounds, phosphorus
promoted
Cobalt compounds
Cobalt-manganese activated by bromine
Cobalt-manganese activated by acetaldehyde
Cobalt-manganese activated by methyl
ethyl ketone
Cobalt naphthenate
Cobalt oxides
Cobalt "salts"
Cobalt "salts" activated by bromine
Cobalt stearate
Copper
Copper, solid, promoted by cobalt or
chromium on asbestos
Copper-silica
Copper acetate
Copper chromite
Cuprammonium nitrate
Cupric chloride
Cupric chloride impregnated on a fluid -
or fixed-bed support
Cupric oxide
Cupric sulfate
Cuprous oxide
Diatomaceous earth
Dichlorohydrin
Disul fides
Dowex 50 ion exchange resin
6-963
-------
Table C-l. (Continued). CATALYSTS USED IN THE
PRODUCTION OF INDUSTRIAL ORGANIC CHEMICALS
Ethyl acetate
Ferric acetate
Ferric bromide
Ferric chloride
Ferric oxide-chromium oxide-potassium oxide
Friedel-Crafts reagents
Fuller's earth
Gamma radiation from Cobalt-60
Nickel
Nickel, activated
Nickel, activated, on asbestos carrier
Nickel-chromium catalyst, reduced
Nickel acetate
Nickel oxide in refractory cement
Nickel chromite
Nickel chromate
Nickel, Raney
Nickel sulfide
Heavy metal salts
Hydrochloric acid
Ion exchange resins
Iron turnings
Iron-molybdenum oxide
Lewis acid catalyst
Light
Lithium arsenate
Lithium phosphate
Lithium "salt"
Magnesium
Magnesium oxide
Manganese acetate
Manganese butyrate
Manganese oxide
Mercaptans
Metaboric acid
Molybdenum chloride
Molybdenum oxides
Molybdenum sulfide
Oleic acid
Palladium
Palladium catalyst, supported
Palladium chloride promoted for metal
oxidation by cooper chloride
Phosphoric acid, solid
Phosphoric acid, on kieselguhr
Phosphorus, red
Phosphorous trichloride
Phosphorous pentachloride
Platinum
Platinum-rhodium mesh
Platinum oxide
Potassium carbonate
Potassium cyanide
Potassium hydroxide
Potassium sulfate
Rhodium-carbonyl complex
Silica-alumina
Silica gel catalyst
6-964
-------
Table C-l. (Continued). CATALYSTS USED IN THE
PRODUCTION OF INDUSTRIAL ORGANIC CHEMICALS
Silica-zerconia
Sodamine
Sodium
Sodium hydroxide
Silver
Silver, crystalline
Silver oxide
Sulfuric acid
Tin
p-Toluene sulfonic acid
Triethyl phosphate
Tungsten
Tungsten sulfide
Tungstic acid
UV light from mercury vapor lamps
Uranium oxide
Vanadium
Vanadium pentoxide
Water
Zinc chloride
Zinc compounds
Zmc oxide promoted with alumina and chromates
Zmc oxide on pumice
Zirconium chloride
6-965
-------
APPENDIX D
INDUSTRIAL ORGANIC CHEMICALS
6-966
-------
Table D-l. INDUSTRIAL ORGANIC CHEMICALS
NAME
ACETAL
ACETALOEHYDE
ACETAMIDE
ACETANILIDE
ACETIC ACID
ACETIC ANHYDRIDE
ACETONE
ACETONE CYANQHYORIN
ACETONITRILE
ACETOPHENONE
ACETYL CHLORIDE
ACETYLENE
ACROLEIN
ACRYLAMIDE
ACRYLIC ACID AND ACRYLATE ESTERS
ACRYLQNITRILE
AOXPIC ACID
ADIPQNITRILE
ALKYLNAPHTHALENES (METHYL
AUYL ALCOHOL
ALLYL CHLORIDE
AHINOBENZOIC ACID (M,P)
AM1NOETHYLETHANOLAMINE
P»AMINOPHENOL
AMYL ACETATES
ANYL ALCOHOLS (8 ISOMERS)
AMYL CHLORIDE
AMYL MERCAPTANS
AMYL PHENOL
ANILINE
AMILINE HYDROCHLORIOE
ANISIOINE
ANXSOLE
ANTHRANILIC ACID
AMTHRAQUINONE
BENZALDEHYDE
6-967
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
NAME
BENZAMIDE
BENZENE
BENZENEDISULFQNIC ACID
BENZENESULFONIC ACID
BENZ!l
BENZILIC ACID
BENZOIC ACID
BENZOIN
BENZONITRILE
BENZOPHENONE
BENZQTRICHLORIDE
BENZOYL CHLORIDE
BENZYL ALCOHOL
BENZYLAMINE
BENZYL BENZOATE
BENZYL CHLORIDE
BENZYL DICHLORIDE
BIPHENYL
BI8PHENOL A
BROMQBENZENE
BROMQNAPHTHALENE
BUTADIENE
U6UTENE
N-BUTYLACETATE
N*BUTYLACRYLATE
N»BUTYL ALCOHOL
SEC-BUTYL ALCOHOL
TERT*BUTYL ALCOHOL
N«BUTYLAMINE
8EC»BUTYLAMINE
TERT»BUTYLAMINE
P.TERT.BUTYLBENZOIC AGIO
1,3 BUTYLENE SLYCQL
TERT«8UTYLPHENOL
N.BUTYRALDEHYDE
N«BUTYRIC ACID
N.BUTYRIC ANHYDRIDE
N.BUTYRONITRILE
6-968
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
NAME
CAPRQLACTAM
CARBON DISULFIDE
CARBON TETRA8RQMIOE
CARBON TETRACHLQRIDE
CELLULOSE ACETATE
CHLOROACETIC ACID
M*CHLQRQANILINg
0-CHLORQANILINE
P«CHLORQANILINE
CHLORQBENZALDEHYDE
CHLOR08ENZENE
CHLOROBENZOIC ACID
CHLOROBENZOTRICHLORIDE (D,P)
CHLQRQBENZOYL CHLORIDE
CHLORODIFLUOROETHANE
CHLQRQQIFLUQRQMETHANE
CHLOROFORM
CHLORONAPHTHALENE
O.CHLORONJTR08EN2ENE
P«CHLORONITR08ENZENE
CHLOROPHENOLS
CHLOR03ULFONIC ACID
M*CHLOROTOLUENE
0«CHLOROTOLUENE
P-CHLORQTQLUENE
CMLOROTRIFLUOROMETHANE
CROTONALDEHYOE
CROTONIC ACID
CjMENE
CUMENE HYDROPEROXIDE
CfANOACETIC ACID
CYANOGEN CHLORIDE
CYANURIC ACID
CYANURIC CHLORIDE
CYCLOHEXANE
CYCLOHEXANOL
CYCLOHEXA^ONE
CYCLOHEXENE
6-969
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
NAME
CYCLQHEXYLAMINE
CYCLOQCTADIENE
OECANQL
DIACETQNE ALCOHOL
DIAMINQBENZQIC ACID
DICHLOROANILINE
M»DICHLORQ8ENZENE
0»OICHLORQBENZENE
P*DICHLQROBENZENE
OICHLQKODIFLUORQMETHANE
1,2-OXCHLQRQETHANE
DICHLQROETHYL ETHER
OZCHl,OROHYORIN
DICHIOROPROPENE
OICYCIOHEXYI.AM1NE
DIITHYLAMINE
OIITHYUENE GLYCOL
OIETHYIENE GUYCOL DIETHYt, ETHER
OXITHYLENE GlYCOL DIMETHYL ETHER
OIITHYLENE GUYCOL MONOBUTYU ETHER
OI6THYIENE GLYCOU MONOIUTYl. ETHER ACETATE
OIETHYLENE GUYCOL MQNOETHYU ETHER
OIETHYUENE GLYCOL MONOETHYL ETHER ACETATE
OIETHYLENE GLYCOL MQNQMgfHYL ETHER
OIETHYL SULFATE
OIPLUOROETHANE
OIISQ8UTYLENE
OIKETENE
DIMETHYLAMINE
N,N»OIMETHYLANILINE
DIMETHYL ETHER
N,N»-OIMETHYLFORMAMIOE
DIMETHYL HYORAZINE
DIMETHYL SULFATE
DIMETHYL SiJLFXDE
DIMETHYL SULFOXIDE
DIMETHYL TEREPHTHALATE
3,5*DINITRQBENZOIC ACID
6-970
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
MAME
2,4*DINITROPHENOL
OJNITRQTQLUENE
OJQXANE
OlOXQLANE
DIPHENYLAMINE
DIPHENYL OXIDE
OIPHENYITHIOUREA
OIPRQPYLENE SLYCOL
OODECENE
DQDECYLANIL1NE
QODECYLPHENQL
EPICHLQRQHYDRIN
ETHANOL
EHTANOI.AMINE
ETHYL ACETATE
ETHYL ACETOACETATE
ETHYL ACRYLATE
ETHYLAMINE
ETHYLBENZENE
ETHYL BROMIDE
ETHYL CELLULOSE
ETHYL CHLORIDE
ETHYL CHLOROACETATE
ETHVLCYANOACETATE
ETHYLENE CARBONATE
ITHYLENE CHLOROHYDRIN
ETHYLENE DIAMINE
ITHYLENE DIBROMJDE
fTHYLENE SLYCOL
ETHYLENE SLYCOL OIACETATE
ETHYLENE SLYCOL DIMETHYL ETHER
ETHYLENE SLYCOL MONQBUTYl ETHER
ITHYLENE SLYCOL MQNOBUTYL ETHER ACETATE
ITHYLENE SLYCOL MONOETHYL4 ETHER
ETHYLENE SLYCOL MONOETHYLS ETHER ACETATE
ETHYLENE SLYCOL MONQMETHYL ETHER
ITHYLENE SLYCOL MQNQMETHYL ETHER ACETATE
ETHYLENE SLYCOL MONOPHEMYL ETHER
6-971
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
ETHYLENE 6LYCQL MQNQPROPYL ETHER
ETHYLENE OXIDE
ETHYL ETHER
2»ETHYL HEXANQL
ETHYL ORTHOFORMATE
ETHYL OXALATE
ETHYL SODIUM OXALACETATE
FORMALDEHYDE
FQRMAMIDE
FORMIC ACID
FUMARIC ACID
6LflrCEROL(NATURAL&3YNTHETIC)
SLYCEROL DICHLOROHYDRIN
BLYCEROL TRHPOLYOXYPROPYLENE) ETHER
G^YCINE
5LYOXAL
HEPTENE
HEXACHLOROBENZENE
HEXACHLOROETHANE
HEXAOECYL ALCOHOL
HEXAMETHYLENEDIAMINE
HEXAMETHYLENE GLYCOL
HEXAMETHYLENE TETRAMINE
HYDROGEN CYANIDE
HYDROQUINONE
PwHYOROXYBENZOIC ACID
ISOAMYLENE
X808UTANOL
I80BUTYL ACETATE
I30BUTYLENE
I80BUTYLRALDEHYDE
I80BUTYRIC ACID
I80DECANDL
isoocTYL ALCOHOL
XSOPENTANE
X80PHORONE
J80PHTHALIC ACID
I30PRENE
6-972
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
MAME
IS0PRQPANQL
ISOPRQPYL ACETATC
I80PRQPYLAMINECMQNQ)
ISQPRQPYL CHLORIDE
ISOPROPYLPHENQL
KETENE
MALEIC AGIO
MALEIC ANHYDRIDE
MALIC ACID
ME3ITYI OXIDE
METANII.IC ACID
METHACWYUC ACID
NETHALLYU CHLORIDE
HEfHANOL
METHYL ACETATE
METHYL ACETOACETATE
METHYLAMINE
N.METNYLANILINE '
METHYL BUTYNOL
MITHYL CHLORIDE
METHYLCYCLOHEXANE
MITHYLCYCLOHEXANONE
METHYLENE CHLORIDE
METHYLENE OIANILINE
METHYL ETHYL KETONE
METHYL FORMATE
METHYLISOBUTYL CARBINOL
METHYLIS08UTYL KETONE
METHYL METHACRYLATE
METHYLPENTYNOL
A»METHYLSTYRENE
MORPHOLINE
A«NAPHTHALENE SULFONIC ACID
B-NAPHTHALENE SULFONIC ACID
A»NAPHTHQL
8»NAPHTHOL
NEOPENTANOIC ACID
Q»NITROANILINE
6-973
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
NAME
P*NITRQANILINE
0*NITRQANISQLE
P«NITRQANXSQLE
NITROBENZENE
NITRQBENZQIC ACID (M,0,P)
NITROETHANE
NJTRQMETHANE
NITRQPHENOL
NITROPROPANE
NITROTQLUENE
NONENE
NQNYLPHENOL
OCTYLPHENOL
PARAIDEHYDE
PINTAERYTHRITOL
NsPENTANE
J.PENTENE
PERCHUQROETHYLENE
PIRCHUOROMfTHYI. MERCAPTAN
OePHENETIOINE
P«PMENETIOINE
PHENOU
PHCNOtSULFONJC ACIDS
PHCNYU ANTHRANIUC ACID
PHSNYI.ENEOIAMINE
PHOSGENE
PHTHA^IC ANHYDRIDE
PMTHAUIMIDE
S*PICQUINE
PIPERAZXNE
POLY8UTENES
POLYETHYLENE GLYCQL
POLYPROPYLENE SLYCOL
P^OPIONALOEHYDE
PROPIONIC ACID
N-PROPYL ALCOHOL
PROPYLAMINE
PROPYL CHLORIDE
6-974
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
SAME
PRQPYLENE
PRQPYLENE CHLQRQHYDRIN
PRQPYLENE DICHLORIDE
PRQPYLENE GLYCQL
PRDPYLENE OXIDE
PYRIOINE (NATURAL ft SYNTHETIC)
OU7NONE
RESORCINOL
RESQRCYLIC ACID
SALICYLIC ACID
SODIUM ACETATE
SODIUM BENZOATE
SODIUM CARBOXYMETHYL CELLULOSE
SODIUM CHLOROACETATE
SODIUM FORMATE
SODIUM PHEMATE
3QRBIC ACID
STYRENE
9UCCINIC ACID
8UCCINONITRILE
SULFANILIC ACID
SULFOLANE
TANNIC ACID
TEREPHTHALIC ACID
TETRACHLOROETHANE
TETRACHLOROPHTHALIC ANHYDRIDE
TITRAETHYL LEAD
TEfRAHYDRONAPHTHALENE
TITRAHYOROPHTHALIC ANHYDRIDE
TlfRAMETHYLENEDIAMlNE
TITRAMETHYLETHYLENEDIAMINE
TOLUENE
TOLUENE»2,4«DIAMINE
2,4-TOLUENE DIISOCYANATE
TOLUENE DIISOCYANATES(MIXTURE)
TOLUENESULFONAMIDE
TOLUENESULFQNXC ACIDS
TOLUENESULFONYL CHLORIDE
6-975
-------
Table D-l. (Continued). INDUSTRIAL ORGANIC CHEMICALS
NAME
TOLUIOINES
mCHLOROBENZENE
l,i,l*TRICHLORQETHANE
TRICHLQRQETHYLENE
TRICHLORQFLUQRQMETHANE
t,2,3«TRICHLOROPRQPANE
i,t,2»TRIC*LORQ«l,2,2»TRIFLUROETHANE
TRJETHYUM1NE
TRJETHYLENE 6LYCOU
TRIETHYLENE GUYCOl DIMETHYL ETHER
TRIISOBUTYUENE
TRIMETHYLAMINE
UREA
VINYI ACETATE
VINYU CHLORIDE
VINYLIOENE CHLORIDE
VINYL TOLUENE
XYLENES, MIXED
O-XYLENE
XYLENOL
XYLIDINE
6-976
-------
APPENDIX E
INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
6-977
-------
Table E-l. INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
A380TT LABORATORIES
ACETO CHEMICAL CO, INC,
ACME«HAROESTY CO, INC,
ADO PROCESSING CORP,
ASWAY, INC
AIRCO CHEMICALS AND PLASTICS
AIR PRODUCTS AND CHEMICALS INC,
AIR PRODUCTS AND CHEHICALS INC,
AIR PRODUCTS AND CHEMICALS INC,
AIR PRODUCTS AND CHEMICALS INC,
AKZONA INC,
ALBA MANUFACTURING CO,
ALCO STANDARD CORP,
ALDRICH CHEMICAL co,
ALLIED CHEMICAL CORP.
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
-LLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP.
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP.
AMERICAN ANILINE AND EXTRACT CO,
AMERICAN COLOR AND CHEMICAL CORP.
AMERICAN CYANAMID CO.
AMERICAN CYANAMIO CO,
AMERICAN CYANAMID CO,
AMERICAN CYANAMID CO,
AMERICAN CYANAMID CO,
AMERICAN CYANAMID CO,
AMERICAN HOECHST CORP,
AMERICAN PETROFINA INC.
CITY
NORTH CHICAGO
CARLSTAOT
JENKINTOWN
ABBEVILLE
CLEAN
LOUISVILLE
CALVERT CITY
HOMETOWN
PASADENA
PENSACOLA
LOWLAND
AURORA
EODYSTONE
MILWAUKEE
BATON ROUGE
BUFFALO
DANVILLE
ELIZABETH
EL SEGUNDO
FRANKFORD
GEISMAR
KQPEWELL
MARCUS HOOK
MOUNOSVILLE
OMAHA
ORANGE
SOUTH POINT
SYRACUSE
PHILADELPHIA
LOCK HAVEN
BOUNDBROOK
CHARLOTTE
LINDEN
MARIETTA
NEW ORLEANS
WILLOW ISLAND
COVENTRY
BIG SPRING
STATE
IL
NJ
PA
LA
NY
KY
KY
PA
TX
FL
TN
IL
PA
WI
LA
NY
IL
NJ
CA
PA
LA
VA
PA
WV
NE
TX
OH
NY
PA
PA
NJ
NC
NJ
OH
LA
WV
RI
TX
6-978
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
AMERICAN POLYMERS INC,
AMES LABORATORIES IMC,
ANSUL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO/POLYMERS INC,
ARMOUR AND COMPANY
ASHLAND CHEMICAL CO,
ASHLAND CHEMICAL CO,
ASHLAND CHEMICAL CO,
A$HLANO CHEMICAL co,
ASHLAND CHEMICAL CO.
BASF XYANDQTTE CORP,
BASF WYANDOTTE CORP,
BASF WYANDOTTE CORP,
BASF WYANOOTTE CORP,
8ECKMAN INSTRUMENTS, INC,
BEKER INDUSTRIES CORP,
BETHLEHEM STEEL CORP,
BIQ^RAD LABORATORIES
BLUE SPRUCE CO,
BQFQRS INDUSTRIES INC,
BOROEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
BOROEN CHEMICAL
BORDEN CHEMICAL
BOROEN CHEMICAL
BORDEN CHEMICAL
BOROEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
CITY
PATTERSON
MILFORO
MARINETTE
BEAVER VALLEY
CHANNELVIEW
EAST CHICAGO
HOUSTON
PORT ARTHUR
WILMINGTON
HOUSTON
MONTGOMERY
ASHLAND
GREAT MEADOWS
HAMMOND
JANESVILLE
MAPLETON
GEISMAR
KEARNY
WASHINGTON
WYANOOTTE
PALO ALTO
CARLSbAO
SPARROWS POINT
RICHMOND
EDISON
LINDEN
BAINBRIDGE
COMPTON
DEMOPOLIS
OIBOLL
FAYETTEVILLE
FREMONT
GEISMAR
ILLIOPOL2S
KENT
LA GRANDE
LEOMINSTER
LOUISVILLE
STATE
i
NJ
CT
WI
PA
TX
IN
TX
TX
CA
TX
IL
KY
NJ
IN
WI
IL
LA
NJ
NJ
MI
CA
NM
MD
CA
NJ
NJ
NY
CA
AL
TX
NC
CA
LA
IL
WA
OR
MA
KY
6-979
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
BORDEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
80RG*WARNER CORP,
BROWN CO,
BUCKMAN'LABORATORIES INC.
BUCKMAN LABORATORIES INC,
CALCASIEU CHEMICAL CORP,
CARI8E ISOPRENE CORP,
CARUS CORP,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO.
CELANESE CHEMICAL CO,
C5LANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CF INDUSTRIES
CF INDUSTRIES
CF INDUSTRIES
CF INDUSTRIES
CHARTER CHEMICALS
CHATTEM DRUG AND CHEMICAL CO,
CHATTEM DRUG AND CHEMICAL CO,
CHEMETRON CHEMICALS
CHEMICAL FORMULATORS INE,
CHEMICAL & POLLUTION SCIENCES, INC,
CHEMICAL PRODUCTS CORP,
CHEMOL INC,
CHEMPLEX CO,
CHEVRON CHEMICAL CO,
RICHMOND CHEMICAL CO,
CHICAGO SANITARY PRODUCTS CO,
CI8A*G£IGY CORP
CI8A*GEIGY CORP
CITIES SERVICE CO INC
CITIES SERVICE CO INC
CITY
MISSOULA
SHEBOYGAN
SPRINGFIELD
MORGANTOWN
BERLIN
CADET
MEMPHIS
LAKE CHARLES
PONCE
LASALLE
BAY CITY
BISHOP
CLEAR LAKE
NARROWS
NEWARK
PAMPA
ROCK HILL
ROME
DONALDSONVILLE
FREEMONT
TUNIS
TYNER
HOUSTON
CHATTANOOGA
LONG BEACH
LAPQRTE
NITRO
OLD BRIDGE
CARTERSVILLE
GREENSBORO
CLINTON
EL SEGUNDO
RICHMOND
CHICAGO
MCINTOSH
ST. GABRIEL
COPPERHILL
LAKE CHARLES
STATE
MT
HI
OR
WV
NH
MO
TN
LA
PR
IL
TX
TX
TX
VA
NJ
TX
SC
GA
LA
NE
NC
TN
TX
TN
CA
TX
WV
NJ
GA
NC
IA
CA
CA
IL
AL
LA
TN
LA
6-980
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
CLARK CHEMICAL CO.
CLORAY NJ CORP,
COASTAL STATES GAS CO,
COASTAL STATES GAS CO,
COLGATE PALMOLIVE co,
COLGATE PALMOLIVE CO,
COLGATE PALMOLIVE CO,
COLGATE PALMOLIVE co,
COLT INDUSTRIES INC,
COLUMBIA NITROGEN CORP.
COMMERCIAL SOLVENTS CORP,
COMMERCIAL SOLVENTS CORP.
COMMERCIAL SOLVENTS CORP,
COMMONWEALTH OIL REFINING CO.
CONTINENTAL OIL COMPANY
CONTINENTAL OIL COMPANY
COOPERATIVE FARM CHEMICAL ASSOC.
COPOLYMER RUBBER AND CHEMICAL CORP,
C03*MAR INC
CRQMPTQN & KNOHLES CORP,
CRQMPTON 4 KNOWLES CORP,
CRQWLEY HYDROCARBON CHEMICALS INC,
CROWLEY HYDROCARBON CHEMICALS INC,
CRQWLEY HYDROCARBON CHEMICALS INC,
CSOWLEY TAR PRODUCTS
CRQWLEY TAR PRODUCTS
CRQKN ZELLERBACH CORP,
CROWN ZELLERBACH CORP,
DAN RIVgR INC,
DARLING AND CO.
DART INDUSTRIES INC,
DIAMOND SHAMROCK CORP,
DIAMOND SHAMROCK CORP,
DIAMOND SHAMROCK CORP,
DIXIE CHEMICAL CO
DON CHEMICAL CO,
DOM BADISCHE CO.
DOM CHEMICAL CO,
CITY
BLUE ISLAND
NEWARK
CHEYENNE
CORPUS CHRISTI
BERKELY
JEFFERSONVILLE
JERSEY CITY
KANSAS CITY
MIDLAND
AUGUSTA
SEIPLE
STERLINGTON
TERRE HAUTE
PENUELAS
NEWARK
WESTLAKE
LAWRENCE
BATON ROUGE
CARVILLE
GIBRALTAR
READING
HOUSTON
KENT
OKLAHOMA CITY
BALTIMORE
HOUSTON
BOGALUSA
CAMAS
DANVILLE
CHICAGO
ELYRIA
BELLE
CEDARTOWN
DEER PARK
BAYPQRT
ANCHORAGE
FREEPORT
BAY CITY
STATE
IL
NJ
WY
TX
CA
IN
NJ
KA
PA
GA
PA
LA
IN
PR
NJ
LA
KA
LA
LA
PA
PA
TX
OH
OK
MD
TX
LA
WA
VA
IL
OH
WV
GA
TX
TX
AK
TX
MI
6-981
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
DOW CHEMICAL CO,
DOW CHEMICAL CO,
DOW CHEMICAL CO,
OOW CHEMICAL CO,
DOW CHEMICAL CO.
DOW CHEMICAL CO,
DON CORNING
DOW CORNING
El DU PONT OE NEMOURS & CO
El DU PONT OE NEMOURS & CO
II DU PONT DE NEMOURS & CO
El DU PONT DE NEMOURS & CO
El DU PONT DE NEMOURS & CO
El DU PONT DE NEMOURS & CO
61 OU PONT DE NEMOURS & CO
El DU PONT DE NEMOURS & CO
El OU PONT DE NEMOURS ft CO
EZ DU PONT DE NEMOURS & CO
El OU PONT OE NEMOURS & CO
El DU PONT DE NEMOURS & CO
El OU PONT DE NEMOURS CO
El DU PONT DE NEMOURS CO
El DU PONT DE NEMOURS CO
El DU PONT DE NEMOURS CO
El DU PONT DE NEMOURS CO
El DU PONT DE NEMOURS CO
El DU PONT DE NEMOURS CO
El DU PONT DE NEMOURS & CO
DYE SPECIALTIES INC
EASTERN COLOR AND CHEMICAL co
EASTMAN KODAK co,
EASTMAN KODAK CO,
EASTMAN KODAK CO.
EL. PASO NATURAL GAS CO.
EMERY INDUSTRIES INC.
EMERY INDUSTRIES INC,
EMKAY CHEMICAL CO,
ENSERCH CORP,
CITY
FREEPORT
MAGNOLIA
MIDLAND
OYSTER CREEK
PITTS8URG
PLAQUEMINE
CARROLLTON
MIDLAND
ANTIOCH
BEAUMONT
BELLE
CAPE FEAR
CORPUS CHRISTI
DEEPWATER POINT
EAST CHICAGO
GIBBSTQUM
HEALING SPRINGS
LAPLACE
LAPORTE
LINDEN
LOUISVILLE
MEMPHIS
MONTAGUE
NIAGARA FALLS
ORANGE
TOLEDO
VICTORIA
WAYNESBORQ
JERSEY CITY
PROVIDENCE
KIN6SPORT
LQNGVIEM
ROCHESTER
ODESSA
CINCINNATI
CITY OF COMMERCE
ELIZABETH
KERENS
STATE
TX
AR
MI
TX
CA
LA
KY
MI
CA
TX
WV
NC
TX
NJ
IN
NJ
NC
LA
TX
NJ
KY
TN
MI
NY
TX
OH
TX
VA
NJ
RI
TN
TX
NY
TX
OH
CA
NJ
TX
6-982
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
ENSERCH CORP,
ESNARK, INC,
ESMARK, INC,
ETHYL. CORP.
ETHYL CORP,
ETHYL CORP,
ETHYL CORP,
EXXON CHEMICAL CO,
EXXON CHEMICAL CO,
EXXON CHEMICAL CO,
FAIRMONT CHEMICAL CO,
FERRQ CORP,
FERRO CORP,
FIRESTONE TIRE AND RUBBER CO,
FIRST MISSISSIPPI CORP,
FLEMING LABORATORIES INC,
FMC CORP,
FHC CORP,
FMC CORP,
FMC CORP,
FOSTER«GRANT CO, INC,
FRANK ENTERPRISES
FRITZCHE DOOSE 4 OLCOTT INC,
5AF CORP,
5AF CORP,
GAF CORP,
GAROINIER 9IG RIVER, INC.
GENERAL AMERICAN OIL OF TEXAS
GENERAL ELECTRIC CO,
GENERAL ELECTRIC CO,
GENERAL ELECTRIC co,
THE GENERAL TIRE & RUBBER CO,
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP.
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP.
CITY
PRYOR
BEAUMONT
WINCHESTER
BATON ROUGE
MAGNOLIA
ORANGEBURG
PASADENA
BATON ROUGE
BAYTOHN
BAYWAY
NEWARK
BATON ROUGE
SANTA FE SPRINGS
ORANGE
PASCAGOJLA
CHAROLTTE
BALTIMORE
BAYPORT
MEAOVILLE
SOUTH CHARLESTON
BATON ROUGE
COLUMBUS
EAST HANOVER
CALVERT CITY
LINDEN
RENNSELEAR
HELENA
PASADENA
MOUNT VERNON
SELKIRK
WATERFORD
ASHTABULA
ALBANY
BELLINGHAM
COLUMBUS
COOS BAY
CROSSETT
PLAQUEMINE
STATE
OK
TX
MA
LA
AR
SC
TX
LA
TX
NJ
NJ
LA
CA
TX
MS
NC
MD
TX
PA
MV
LA
OH
NJ
KY
NJ
NY
AR
TX
IN
NY
NY
OH
OR
MA
OH
OR
AR
LA
6-983
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP,
GEORGIA' PACIFIC CORP,
GETTY OIL CO,
GIVAUDAN CORP,
GOOOPASTUREi INC,
9F GOODRICH CHEMICAL, CO,
BF GOODRICH CHEMICAL CO,
BF GOODRICH CHEMICAL CO,
GOODYEAR TIRE AND RUBBER CO,
GOODYEAR TIRE AND RUBBER CO,
W, R, GRACE AND CO,
W, R, GRACE AND CO,
W, R, GRACE AND CO.
GRAIN PROCESSING CORP,
GREAT LAKES CHEMICAL CORP,
GUARDIAN CHEMICAL CORP,
GULF OIL CO,
GULP OIL CO,
GULF OIL CO,
GULF OIL CO,
GULF OIL CO,
GULF OIL CO,
HARDWICKE CHEMICAL CO,
HEICO, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HOOAG CHEMICAL CORP,
HOWERTQWN GQWEN CHEMICALS, INC.
HUMMEL CHEMICAL CO,
HUMPHREY CHEMICAL CO,
CITY
RUSSELLVILLE
TAYLORSVILLE
VIENNA
DELAWARE CITY
CLIFTON
OIMMITT
CALVERT CITY
HENRY
PORT NECHES
BAYPORT
BEAUMONT
FORDS
MEMPHIS
NASHUA
MUSCATINE
EL DORADO
HAUPPAUSE
ALLIANCE
CEDAR BAYOU
PHILADELPHIA
PORT ARTHUR
VICKS3URG
WELCOME
ELGIN
DELAWARE MATER GAP
BURLINGTON
GIB8STOHN
GLENN FALLS
HARBOR 8EACH
HERCULES
HOPEWELL
LOUISIANA
PLAQUEMINE
WILMINGTON
SKOKIE
ROANOKE RAPIDS
SOUTH PLAINFIELD
NORTH HAVEN
STATE
SC
MS
GA
DE
NJ
TX
KY
IL
TX
TX
TX
NJ
TN
NH
IA
AR
NY
LA
TX
PA
TX
MS
LA
SC
PA
NJ
NJ
NY
MI
CA
VA
MO
LA
NC
IL
NC
NJ
CT
6-984
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
ICC INDUSTRIES, INC,
ICC INDUSTRIES, INC,
ICI UNITED STATES
INLAND CHEMICAL CORP,
INLAND CHEMICAL CORP,
JEFFERSON CHEMICAL CO.,
JEFFERSON CHEMICAL CO,,
JOC OIL, INC,
ANDREW JERGENS CO,
KAISER CHEMICALS
KALAMA CHEMICALS, INC,
KAY-FRIES CHEMICALS, INC,
KEWANEE INDUSTRIES, INC,
H, KOHNSTAMM AND CO,, INC,
1.1 L4A*lklAV«L4k* A L • M «* A « L 1 M
INC,
INC,
unite, irnuua I rc*t
H, KOHNSTAMM AND CO,,
H, KOHNSTAMM AND CO,, INC,
KQPPERS CO., INC,
KOPPERS CO,, INC,
K3PPERS CO,, INC,
KOPPERS CO,, INC,
KKAFTCQ CORP,
LACAT CHEMICALS INC,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
ELI LILLY AND CO,
LONZA, INC,
LUBRIZOL CORP,
LUBRIZOL CORP,
MALLINCKROOT, INC,
MALLINCKROOT, INC,
MALLINCKROOT, INC,
MARATHON OIL CO,
MARATHON OIL CO,
MARTIN MARIETTA CORP,
MERCK AND COMPANY INC,
MERICHEM CO,
CITY
DOVER
NIAGARA FALLS
NEW CASTLE
JUNEAU
MANATI
CONROE
PORT NECHES
HOUSTON
CINCINNATI
SAVANNAH
KALAMA
STONY POINT
GLOUCESTER CITY
CAMDEN
CLEARING
BRIDGEVILLE
CICERO
FOLLANSBEE
PETROLIA
MEMPHIS
CHICAGO HEIGHTS
BALTIMORE
EOGEWATER
HAMMOND
LOS ANGELES
ST, LOUIS
LAFAYETTE
MAPLETON
DEER PARK
DEER PARK
LODI
RALEIGH
ST. LOUIS
ROBINSON
TEXAS CITY
SODYECO
ALBANY
HOUSTON
STATE
OH
NY
OE
NX
PR
TX
TX
TX
OH
GA
WA
NY
NJ
NJ
IL
PA
IL
WV
PA
TN
IL
MO
NJ
IN
CA
MO
IN
IL
TX
TX
NJ
NC
MO
IL
TX
NC
GA
TX
6-985
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
MIDDLEBORO INDUSTRIES, i^c,
MILES LABORATORIES, INC,
MILLMASTER ONYX CORP.
MISSISSIPPI CHEMICAL CORP.
MOBAY CHEMICAL co,
MQBAY CHEMICAL CO,
MQ8JL OIL CORP,
MONOCHEM, INC,
MONSANTO CO,
MONSANTO CO,
MONSANTO co,
MONSANTO CO,
MONSANTO CO,
MONSANTO co,
MONSANTO co,
MONSANTO co,
MONSANTO co,
MONSANTO co,
MONSANTO co,
MONSANTO co.
MONSANTO co,
MONSANTO co,
MONSANTO co,
MONSANTO co,
MONTROSE CHEMICAL CORP. OF CALIFORNIA
MURRO CHEMICAL co.
NALCO CHEMICAL CO.
NALCO CHEMICAL CO,
NAPP CHEMICALS, INC,
NATIONAL DISTILLERS AND CHEMICAL CORP,
NATIONAL DISTILLERS AND CHEMICAL CORP,
NATIONAL STARCH AND CHEMICAL CORP,
NATIONAL STEEL CORP,
NEASE CHEMICAL CO,, INC,
NEASE CHEMICAL CO,, INC,
NECHES BUTANE PRODUCTS CO,
NIPRO, INC,
NORDA, INC,
CITY
MIDDLE3QRO
ZEELAND
NEWARK
YAZOO
CEDAR BAYOU
NEW MARTlNSVlLLt
BEAUMONT
GEISMAR
ADOYSTON
ANNISTON
BRIDGEPORT
CHOCOLATE BAYOU
OECATUR
EUGENE
EVERETT
KEARNY
LULING
NITRO
PENSACOLA
ST. LOUIS
SAUGET
SPRINGFIELD
TEXAS CITY
TRENTON
HENDERSON
PORTSMOUTH
FREEPORT
SUGARLAND
LODI
DEER PARK
TUSCULA
LONG MQTT
ZUG ISLAND
FERNALD
STATE COLLEGE
PORT NECHES
AUGUSTA
BOONTON
STATE
MA
MI
NJ
MS
TX
HV
TX
LA
OH
AL
NJ
TX
AL
OR
MA
NJ
LA
WV
FL
MO
IL
MA
TX
MI
NV
VA
TX
TX
NJ
TX
IL
TX
MI
OH
PA
TX
GA
NJ
6-986
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
NORSE LABS, INC,
NORTHERN FINE CHEMICALS
NORTHERN NATURAL GAS CO,
NORTHWEST INDUSTRIES INC,
NORTHWEST INDUSTRIES INC,
NORTHWEST INDUSTRIES INC.
NORTHWEST INDUSTRIES INC,
N«REN CORP,
N«REN CORP,
OCCIDENTAL PETROLEUM
OCCIDENTAL PETROLEUM
OCCIDENTAL PETROLEUM
OCCIDENTAL PETROLEUM
OLIN CORP,
OLIN CORP,
OLIN CORP,
OL2N CORP,
QRBIS PRODUCTS CORP,
OXIRANE CHEMICAL CO,
QXQCHEM ENTERPRISE
PACIFIC SOAP CO,
PAN AMERICAN CHEMICAL CORP,
PARKE'DAVIS & CO,
PELRON CORP,
PENNWALT CORP,
PENNWALT CORP,
PENNWALT CORP^
PENNWALT CORP,
PENNWALT CORP,
PENNWALT CORP,
PETRO*TEX CHEMICAL CORP,
PFANSTIEHL LABROATQRIES, INC
CHAS, PFIZER & CO,i INC
CHAS, PFIZER & CO,, INC
CHAS, PFIZER 4 CO., INC
PHILLIPS PACIFIC CHEMICAL CO,
PHILLIPS PETROLEUM CO,
PHILLIPS PETROLEUM CO,
CITY
SANTA BARBARA
FRANKLIN
MORRIS
BEAUMONT
CHATTANOOGA
EL DORADO
ST, LOUIS
PLAINVIEW
PRYOR
ARECIBO
NIAGARA FALLS
NORTH TANAWANOA
TAFT
ASHTABULA
BRANDENBURG
LAKE CHARLES
ROCHESTER
NEWARK
8AYPORT
PENUELAS
VERNON
TOLEDO
HOLLAND
LYONS
BEAUMONT
CALVERT CITY
GENESEO
GREENS BAYOU
THOROFARE
WYANDOTTE
HOUSTON
WAUKEGAN
GREENSBORO
GROTON
TERRE HAUTE
KENNENECK
BEATRICE
BQRGCR
STATE
CA
NJ
IL
TX
TN
AR
MI
TX
OK
PR
NY
NY
LA
OH
KY
LA
NY
NJ
TX
PR
CA
OH
MI
IL
TX
KY
NY
TX
NJ
MI
TX
IL
NC
CT
IN
WA
NE
TX
6-987
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
PHILLIPS PETROLEUM CO,
PHILLIPS PETROLEUM CO,
PHILLIPS PETROLEUM co,
PIERCE CHEMICAL co,
PILOT CHEMICAL co,
PIONEER SOAP co,
PLASTICS ENGINEERING CORP,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PUBLICKER INDUSTRIES INC,
PUBLICKER INDUSTRIES INC,
PUERTO RICO OLEFINS co,
PUREX CORP,
PURE* CORP,
PYO INTERNATIONAL, INC,
REICHGLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICAL INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
CITY
GUAYAMA
PHILLIPS
SWEENEY
RQCKFQRO
HOUSTON
SAN FRANCISCO
SHEBOYGAN
BARBERTON
BEAUMONT
GUAYANILLA
LAKE CHARLES
NATRIUM
BALTIMORE
CHICAGO
DALLAS
DAYTON
IVORYOALE
KANSAS CITY
LONG BEACH
MEMPHIS
SACRAMENTO
GRETNA
PHILADELPHIA
PENUELAS
BRISTOL
OMAHA
BQONTON
AUSTIN
ELIZABETH
HAMPTON
HOUSTON
KANSAS CITY
MALVERN
MQNCURE
MORRIS
ST. HELENS
TACOMA
TUSCALOOSA
STATE
PR
TX
TX
IL
TX
CA
WI
OH
TX
PR
LA
WV
MO
IL
TX
OH
OH
KA
CA
TN
CA
LA
PA
PR
PA
NE
NJ
TX
NJ
SC
TX
KA
AR
NC
IL
OR
WA
AL
6-988
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
RE1CHOLO CHEMICALS, INC.
REILY TAR 8, CHEMICAL CORP,
REPUBLIC STEEL CORP,
REPUBLIC STEEL CORP,
RICHARDSON*MERRELL INC.
RITTER CHEMICAL CO,
RQBINSON-WAGNER INC,
ROHM & HAAS CO,
ROHM & HAAS CO,
ROHM & HAAS CO,
ROHM & HAAS CO.
ROHM & HAAS CO,
R.S.A, CORP,
RUBICON CHEMICALS INC,
SALISBURY LABS
SALISBURY LABS
SCHENECTAOY CHEM., INC,
G.O.SEARLE & CO,
SHARON STEEL CORP,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO.
SHENAN60 INC,
SNfRWIN WILLIAMS CO
J, R, SIMPLOT CO,
SKELLY OIL CO,
SKELLY OIL CO,
SKELLY OIL CO,
SKELLY OIL CO,
SOLVENT CHEMICAL CO,
SOLVENT CHEMICAL CO.
SQNOCO PRODUCTS CO,
SOUTH HAMPTON CO,
SPECIALTY ORGANICS, INC.
SQUIBB CORP,
CITY
WHITE CITY
INOIANOPOLIS
CHICAGO
CLEVELAND
PHILLIPSBURG
AMSTERDAM
MAMARONECK
BRISTOL
DEER PARK
KNOXVILLE
LOUISVILLE
PHILADELPHIA
AROSLEY
GEISMAR
CHARLES CITY
WILMINGTON
ROTTERDAM JUNCTION
NORWOOD
FAIRMONT
DEER PARK
DOMINGUEZ
GEISMAR
MARTINEZ
NORCO
HOOD RIVER
NEVILLE ISLAND
ST. BERNARD
POCATELLO
CLINTON
EL DORADO
SPRINGFIELD
WINNFIELD
MALDEN
NIAGRA FALLS
HARTSVILLE
SILSBEE
IRWINDALE
NEW BRUNSWICK
STATE
OR
IN
IL
OH
NJ
NY
NY
PA
TX
TN
KY
PA
NY
LA
IA
NC
NJ
OH
WV
TX
CA
LA
CA
LA
IL
PA
OH
ID
IA
KA
OR
LA
MA
NY
SC
TX
CA
NJ
6-989
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
STANDARD CHLORINE CHEMICAL CO,
STANDARD CHLORINE CHEMICAL CO,
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF OHIO
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFPER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STEFAN CHEMICAL CO,
STEFAN CHEMICAL CO,
STEPAN CHEMICAL CO,
STERLING DRUG, INC,
STERLING DRUG, INC.
STERLING DRUG, INC,
STIMSON LUMBER COMPANY
ST. PAUL AMMONIA PRODUCTS, INC,
STORY CHEMICAL CORP,
SUNOCO
SjNOCQ
SUNOCO
SJNOCO
SUNOLIN CHEM, CO.
SYBRON CORP,
SYNTEX CORP,
TENNECO CHEMICALS, INC.
TENNECO CHEMICALS, INC.
TENNECO CHEMICALS, INC.
TENNECO CHEMICALS, INC.
CITY
DELAWARE CITY
KEARNY
CHOCOLATE BAYOU
DECATURE
JOLIET
TEXAS CITY
WOOD RIVER
YORKTOWN
LIMA
CARSON
COLD CREEK
DELAWARE CITY
EDISON
HENDERSON
LE MOYNE
LOUISVILLE
NIAGARA FALLS
PERRY
ANAHEIM
ELWOQO
FIELDSBORO
CINCINATTI
MEMPHIS
RENSSELAER
ANACORTES
EAST DU3UQUE
MUSKEGON
CORPUS CHRISTI
DUNCAN
MARCUS HOOK
TOLEDO
CLAYMONT
LYNDHURST
NEWPORT
CHALMETTE
FORDS
GARFIELD
HOUSTON
STATE
DE
NJ
TX
AL
IL
TX
IL
VA
OH
CA
AL
DE
NJ
NV
AL
KY
NY
OH
CA
IL
NJ
OH
TN
NY
WA
IL
MI
TX
OK
PA
OH
DE
NJ
TN
LA
NJ
NJ
TX
6-990
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME
TENNESSEE VALLEY AUTHORITY
TERRA CMEM INTERNATIONAL, INC.
TIXACO, INC,
TEXACO, INC,
TEXAS-U.S, CHEMICAL CO,
TOMS RIVER CHEMICAL CORP.
TRIAD CHEMICAL
TYLER CORP.
UNION CAMP CORP,
UNION CAR8IOE CORP,
UNION CARBIDE CORP.
UNION CARBIDE CORP,
UNION CARBIDE CORP,
UNION CARBIDE CORP.
UNION CARBIDE CORP,
UNION CARBIDE CORP,
UNION CARBIDE CORP.
UNION CARBIDE CORP,
UNION CARBIDE CORP,
UNION OIL OF CALIFORNIA
UNION OIL OF CALIFORNIA
UNION OIL OF CALIFORNIA
UNION PACIFIC CORP, CHAPLIN
UNIRQYAL, INC,
UNITED AIRCRAFT
UNITED STATES STEEL CORP,
UNITED STATES STEEL CORP,
UNITED STATES STEEL CORP,
UNITED STATES STEEL CORP,
UNIVAR CORP,
UNIVERSAL OIL PRODUCTS CO,
UNIVERSAL OIL PRODUCTS CO,
UPJOHN CO,
VALLEY NITROGEN PRODUCERS, INC,
VALLEY NITROGEN PRODUCERS, INC,
VAN OE MARK CHEM, CO,
VIRGINIA CHEMICALS, INC,
VULCAN MATERIALS CO,
CITY
MUSCLE SHOALS
PORT NEAL
PORT ARTHUR
NESTVILLE
PORT NECHES
TOMS RIVER
OONALDSONVILLE
JOPLIN
DOVER
ASHTABULA
BOUND BROOK
BROWNSVILLE
INSTITUTE AND SOUTH
MARIETTA
NIAGRA FALLS
PENUELAS
SEADRIFT
TAFT
TEXAS CITY
BEAUMONT
BREA
KENAI
CORPUS CHRISTI
NAUGATUCK
MUNCIE
CHEROKEE
CLAIRETON
HAVERHILL
NEVILLE ISLAND
EUGENE
EAST RUTHERFORD
MCCOOK
LAPORTE
EL CENTRO
HELM
LOCKPORT
PORTSMOUTH
GEISMAR
STATE
AL
IA
TX
NJ
TX
NJ
LA
MO
OH
OH
NJ
TX
CHARLESTONWV
OH
NY
PR
TX
LA
TX
TX
CA
AL
TX
CT
IN
AL
PA
OH
PA
OR
NJ
IL
TX
CA
CA
NY
VA
LA
6-991
-------
Table E.I. (Continued). INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
NAME CITY STATE
VULCAN MATERIALS CO, WICHITA KA
JIM WALTER CORP, BIRMINGHAM AL
WARNER LAMBERT CO, HARRIMAN NY
WHEELING PITTS8URG STEEL; CORP, MQNESSEM PA
WHITE CHEMICAL CORP, BAYONNE NJ
WILLIAMS COMPANIES BLYTHEVILLE AR
WILLIAMS COMPANIES CATQOSA OK
WILLIAMS COMPANIES DONALDSONVILLE LA
WITCO CHEMICAL CORP, CLEARING IL
WITCO CHEMICAL CORP, PATERSQN NJ
WOBURN CHEMICAL co, KEARNY NJ
WOONSOCKET COLOR AND CHEMICAL CO. WOONSOCKET RI
WRIGHT CHEMICAL CO, ACME NC
6-992
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7.AUTHORIS) "
P.airjond Liepins and Forest Mixon (RTl), Charles Hudak
anaJTerry B. Parsons (Radian)
9. PEHFORMsNG ORGANIZATION'rMAME AND ADDRESS
Research Triangle Institute
P.O. Box 1219U
Ressa.rch Triangle Park, HC 27709
1. REPORT NO.
TECHNICAL REPORT DATA
(PicBfe rcaiJ Jiatrnctions on trie reverse before completing)
3. RECIPIENT'S ACCESSION-NO
I. T;TUE AND SUBTITLE
Industrial Process Profiles for Environmental User
Chapter 6. The Industrial Organic Chemicals Industry
12. SPONSORING AGENCY NAME-AMD ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. ENVIRONMENTAL PROTECTION AGEMCY
Cincinnati, Ohio
5 REPORT DATE
February 1977J
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1AB015: ROAP 21AFH-025L
11. CONTRACT/GRANT NO.
68-02-1325/T.ask 70
13. TYPE OF REPORT ANH PERIOD i
Initial:
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
10. ABSTRACT
The catalog of Industrial Process Profiles for Environmental Use was developed as an
aid in defining the environmental impacts of industrial activity in the United Stages,
Entries for each industry arc in consistent format and form separate chapters of the
study. Industrial organic chemicals are the product of at least one chemical reactior
in this industry and will undergo at least one additional treatment step in a down-
stream processing industry. These compounds are intermediate materials in the manu-
facture of such products as plastics, synthetic fibers, Pharmaceuticals and sxir-
factants among others. The industry is discussed in terms of ten feedstock groups:
"benzene, butylenes, sources of cresylic acids, ethylene, methane, naphthalene,
paraffins5 propyiene, toulene and xylenes. Ten chemical trees, ten process flow
sheets and 36.5 process descriptions have been prepared to characterise the Industry.
Within each process description available data have been presented on function, input
materials, operating parameters, utilities, waste streams, EPA Source Classification
Code arid references. Data related to the subject matter, including company, product
and raw material data, are included as appendices.
KEY WORDS *ND DOCUMENT ANALYSIS
Pollution
DESCRIPTORS
Industrial Processes
I Chemical Engineering,
Organic Compounds
Organic Chemistry
IP. DtST-l;3UTION S TA I'tMfcN T
Uulimit3d
b. IDENTIFIERS/OPEN ENDED Tt«Mf
Process Assessment
Environmental Impact
Industrial Organic
Chemicals
19. SECURITY CLASS (This Report)
Unclassified
Unclassified
:. COSATi Fiold/C.roup
13E
13H
OTA
11C
07C
2i. NO. C»; PAGHS
6-993
ft U.S. GOVERNMENT PRINTING OFFICfc 1978 -659-5IO/Z1
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