-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Ethylene glycol Monoethyl Ether (187)
IUC Name 2-methoxyethanor1'
Common Names
Structural Formula
CH3OCH2CH2OH
Molecular Wt. 76.11
(1)
Melting Pt. -85.1
(1)
Density (Condensed) Q.9647^ @ 204 4 C Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
Boiling Pt. 125
(i:
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water Infinite
Hot Water
EthanolVery soluble
Others: Ether, benzene
Acid, Base Properties Neutral
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification
Coast Guard Classification
Comments '^ni|r'"°5 • ^astman Chemical Products. Celanese C.hemiral Co; llninn Carbide
Corporation.
References (1) 1570
(2) 1571
37
-------
H. M. Name Ethyleneqlycol m
IUC Name
HAZARDOUS WASTES PROPERTIES
WORKSHEET •
onoethyl ether acetate (188)
Structural Formula
Common Names Ethyl ene Glvcol Monoethvl- CH3COOCH?CH?OC,
Ether Acetate
Molecular Wt. 132.17^
Density (Condensed) 0.9748
Vapor Pressure (recommended
1.2 mm @ 20 C^1^
Flash Point 120,FU)
Flammability Limits in Air
Explosive Limits in Air (wt
Solubility^
Cold Water
Others: Ether, acetone
Acid, Base Properties
("Cellusolve" Acetate)
?H5 ;
Melting Pt. -61.7 C(1> Boiling Pt. 156.4 C(1) t
& 20/20 C(1' Density (gas) 4.72(1) @
air = T.OO
55 C and 20 0
@
Autolgnition Temp. 715 F(1)
(wt %) Lower Upper
. %) Lower 1.71 percent L.E.LUpper
G> i
•
Hot Water Ethanol Soluble
!
>
Highly Reactive with ;
/
Compatible with ' :
;
Shipped in !
ICC Classification
(2)
Comment-; Sources' ': A.I.D
Coast Guard Classification i
. Chemical Co: Amsco Division: Ashland Chemical C.n: CPS Chpmiral f.o
Celanese Chemical CQ^ E.AStman Chemical ProdlirtQ? Stnnpu-Muollpr Tnr; Thnmncnn-HauuiarH .;
Chemical Co; Union Carbide
Co.
References (1 ) 0766 '••
(2) 1571 ;
(3) 1570
38
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tsnprnpyl Fthpr (232)
IUC Name
Common Names Isopropyl ether
Structural Formula
2-Isopropoxypropane
Molecular Wt. 102.17(1)
(CH3)2CHOCH(CH3),
Density (Condensed) 0.719
@ 25 C
Melting Pt. -60 C
(1)
(1)
Vapor Pressure (recommended 55 C and 20 Q
Density (gas) 3.52^
air = 1.00
Boiling Pt. 68.5
150 mm
(3 25 C
(1)
400 mm
48.2 C
(2)
Flash Point -18 FUJ
Autoignition Temp. 830 Fv';
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %)
SolubilW2)
Cold Water Slightly soluble
Lower 1.4 percent
Hot Water
Upper 21.0 percent
Soluble in all
Ethanol proportions
Others: Ether
Acid, Base Properties_
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments Sourcesv
Coast Guard Classification
A.I.D. Chemical Co; Allied Chemical Corp: Amsco
Industries: F. H. Ross & Co; Rngpr r.hpmiral r.n; <;hpii
stonoy Muollcr In
Suburban Chemical Co; Thompson-Hayward Chemical Co; Union Carbide Corp
References (1)
(2)
(3)
0766
1570
1571
39
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Prooylene oxide (362)
Structural Formula
IUC Name
Common Names_ Propvlene Oxide
1,2-Epoxypropane, Propene oxide
OCH2CHCH3
Molecular Wt. 58.08^ Melting Pt. -104.4 c^ Boiling Pt. 33.9
Density (Condensed) 0.8304 @ 2Q/gO C^ Density (gas) 2.0^ 9
air = 1.00
Vapor Pressure (recommended 55 C and 20 C)
400 mm @ 17.8 C^ 760 mm @ 33.9 C^ @
Flash Point -35 F Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (voi %} Lower 2.1% Upper 21.5%
Solubility
(2)
Cold Water Soluble in 100 parts Hot Water Ethanol ^oluble
Others: Ether •
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification
Comments Sources^ ': jASF Wyandotte Cor; Dow-Chemical Co; Jefferson Chemical Co; 01 in
Chemicals: Qxirane Corp: Union Carbide C.nrp.
References (1) 0766
(2) 1492
(3) 1571
40
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tetrahydrofuran (426)
Structural Formula
IUC Name
Common Names Tetrahydrofuran
Cyclotetramethylene
Molecular Wt. 72.10(1) Melting Pt. -108.5 C(1) Boiling Pt. 65-4 C(1)
Density (Condensed) Q.RRR @ 2Q/4 C^' Density (gas) 2.5^ @
air = 1.00
Vapor Pressure (recommended 55 C and 20 C)
Flash Point i pO) Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility (3)
Cold Water soluble Hot Water Ethanol Soluble
Others: Kpt.nnps, pt.hpr<;, hydrorarbon*;
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification Coast Guard Classification
Comments Sources^ ': Ashland Chemical Co; Conray Products Co; E. I. duPont de Nemours & Co;
International Chemical Corp; McKesson Chemical Co; Pyramid Chemical Sales Co; Quaker Oats Co;
Western Eaton Solvents & Chemicals Co.
References (1) 0766
(2) 1492
(3) 1571
41
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dioxane (153)
Structural Formula
IUC Name
Common Names Diethylene dioxide
Dioxane
Molecular Wt. 88.10(1) Melting Pt. 10 C(1) Boiling Ft.101-1
Density (Condensed) 1.0353 @ 20/4 C Density (gas) G>
Vapor Pressure (recommended 55 C and 20 C)
40 mm @ 25.2 C^ 100 m @ 45.1 C
^
Flash Point 54 F Autoignition Temp. 356
Flammability Limits .in Air (wt %) Lower _ Upper_
Explosive Limits in Air (wt. %) Lower 1.97 percent upper 22.2 percent
^
Soluble in all
Cold Water Soluble in all proportions ^ Ethanol proportions
Others: Fther, acetone, organic solvents, acetic acid
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in
ICC Classification Coast Guard Classification
Comments Mfq.^3 . Amsco Division; Ashland Chemical Co; J. T. Baker Chemical Co; Corco
rhPitriral r.n; Rrant Chemicals, Inc; MC&B Manufacturing Chemists: Southland Solvents and
Chemical Co; Stoney-Mueller, Inc; Union Carbide Corp.
References (1) °766
(2) 1570
(3) 1571
-------
PROFILE REPORT
Pi nitrobenzene (163)
1. GENERAL
Dinitrobenzenes range from white to yellowish crystals and are
described as being highly toxic. They comprise three possible \.
isomers: l,2-(mp, 118 C), l,3-(mp, 89 C) and l,4-(mp, 173 C).1492
The 1,3-isomer is prepared by the direct nitration of benzene using
nitric acid and sulfuric acid. The material produced on a commercial
basis generally consists of a mixture of isomers containing 91 to 94 percent
1433
of the meta compound. Oxidation of primary aromatic amines is the
method used to prepare 1,2- and 1,4-dinitrobenzene since these compounds
cannot be obtained in good yield by direct nitration. Meta-dinitrobenzene
has been used as a substitute for TNT and other high explosives but because
of its toxicity and the availability of more powerful explosives, it no
1433
longer is utilized in this way.
Meta-dinitrobenzene is produced commercially by E. I. duPont de Nemours
and Company.1571 It is considered unsuitable for handling on a mass-production
1 /I O O
basis because of its hazardous nature.
Physical/chemical properties of the three isomers are summarized in the
attached worksheets.
2. TOXICOLOGY
Dinitrobenzene is described as being extremely toxic. It has an
irritating effect on the respiratory system and causes the skin to become
bluish in color.
43
-------
3. OTHER HAZARDS
The dinitrobenzenes are considered to be severe explosion hazards. '
When these materials are heated to decomposition, they emit highly toxic fumes
of oxides of nitrogen and explode. All of the dinitrobenzenes should be
treated as highly toxic materials and the skin, eyes and lungs should be
protected accordingly.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
In handling dinitrobenzene, direct skin contact must be prevented by use
of suitable protective clothing. These materials are to be protected from
shock and heat to prevent fire and/or explosion.
Pertinent shipping regulations may be found in the Code of Federal
Regulations, Title 49, Transportation, Sections 73.364, 73.371, 73.345 and
73.346 under the headings of dinitrobenzol, solid and dinitrobenzol, liquid.
Under these regulations, dinitrobenzenes are classed as Poison B.
Disposal/Reuse
Disposal or reuse of waste dinitrobenzene streams must take into account
the explosive and toxic nature of these materials. It is assumed that dilute
aqueous waste streams containing dinitrobenzene are treated in the same manner
as the dinitrophenol waste streams, i.e., secondary treatment using acclimated
activated sludges and aeration (see Profile Report on dinitrophenol [164]).
Recommended provisional limits for dinitrobenze in the environment are
as follows:
44
-------
Contaminant Basis of
and Environment Provisional Limit Recommendation
Dinitrobenzene in air 0.01 mg/M 0.01 TLV
Dinitrobenzene in water 0.05 ppm (mg/1) Stokinger and
and soil Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dinitrobenzenes are expected to appear primarily as aqueous waste streams
in low concentrations and only rarely as concentrated waste. The processing
options are briefly described in the following paragraphs together with recom-
mendations as to their adequacy.
Concentrated Dinitrobenzenes
In the event it becomes necessary to dispose of a significant quantity
of concentrated dinitrobenzene, incineration appears to be the only accept-
able technique currently available. Qualified personnel familiar with
handling toxic and explosive materials must be available to operate the
facility. The dinitrobenzene must be diluted with other combustible materials
which are not explosive and incinerated under controlled conditions where
oxides of nitrogen are removed from the effluent gas by scrubbers, and/or
1435
catalytic or thermal devices. Combustion should be carried out at a
minimum temperature of 1,800 F over a minimum residence time of 2.0 seconds.
Dilute Aqueous Waste
Dinitrobenzene appears as aqueous waste in the manufacturing process.
Other sources of waste are from water used in the cleaning of equipment used
in dinitrobenzene service. It is assumed that methods used to dispose of
aqueous dinitrobenzene waste are similar to methods for dinitrophenol, i.e.,
secondary treatment utilizing activated sludges. The adequacy of this prac-
tice is in doubt due to the apparent difficulty of microorganisms to degrade
aromatic nitro compounds. Until data are available to show that dini-
trobenzenes can be degraded satisfactorily in secondary treatment facilities,
45
-------
it is recommended that aqueous waste streams be concentrated and treated as
discussed in the section on concentrated dinitrobenzenes.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The dinitrobenzenes do not appear to be candidate waste stream consti-
tuents for National Disposal Sites since they may be treated by common
industrial techniques. It is anticipated that the great majority of the
aqueous dinitrobenzene waste generated in the chemical industries will con-
tinue to be treated at the source of the waste generation, and/or industrial
disposal facilities but that emphasis should be changed from biological
treatment processes to concentration and subsequent controlled incineration
until the efficiency of the biological processes is proven. In the event
concentrated material becomes contaminated, it can be incinerated as dis-
cussed in the section on Concentrated Dinitrobenzenes.
46
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. New York,
Reinhold Publishing Corporation, 1957. 1,467.p.
1044. Marion, C. V., and G. W. Malaney. Ability of activated sludge miro-
organisms to oxidize aromatic organic compounds. ln^ proceedings;
Eighteenth Industrial Waste Conference, Engineering Bulletin of
Purdue University, 1963. p. 297-308
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1963. p. 297-308.
1435. John Zink Company. NO 1071m. Bulletin number NO 1071m. John Zink
Company, Tulsa, Oklahoma. 4 p.
1492. Merck and Company. The Merck index of chemicals and drugs. Rahway
New Jersey, 1960. 1,043 p.
1571. 1971-72 OPD Chemical buyers guide. 59th ed. Schnell Publishing
Company, Inc. 1971. 1,584 p.
1655. Fieser, L. F., and M. Fieser. Organic chemistry. Boston, D. C.
Heath and Company, 1957. 1,112 p.
1656. Condon, F. E., and H. Meislich. Introduction to organic chemistry.
New York, Holt, Reinhart, and Winston, Inc. 1956. 841 p.
47
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Qinitrobenzene (163)
Structural Formula
IUC Name 1.2-dinitrobenzene
Common Names 0-dinitrobenzol, ortho-dinitrobenzene
302.8 C G>
Molecular Wt. 168.11 Melting Pt. 118 C Boiling Pt.@_/_70 mm.
Density (Condensed) 1.571 @ OC/4C Density (gas) 5.79 (air=1g °
Vapor Pressure (recommended 55 C and 20 C)
Flash Point 302 F Autoignition Temp.
Flammability Limits in Air (wt %) Lower__ Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Slightly Soluble^ Hot Water Ethanol Soluble^
Others: Very soluble in chloroform^ hot alcohor2'
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in
ICC Classification Coast Guard Classification
Comments Volatile with steanr '
References (V) (0766)
(2) (1570)
(3)
48
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Pi nitrobenzene
Structural Formula
IUC Name 1.4-di nitrobenzene
Common Names 1,4-dinitrobenzene. para-dinitrobenzol
CfiH4(N02),
Molecular Wtl^ 168.11 Melting Ptl1) 172 C Boiling Pt. 299C 0 777 mm
Density (Condensed) @ Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
Flash Point _ Autoignition Temp.
Flammability Limits in Air (wt %) Lower _ Upper_
Explosive Limits in Air (wt. %} Lower _ Upper_
Solubility* .
Cold Water insnluhlp^1) Hot Water Ethanol Slightly Soluble
Others: Soluble in chloroform'1' acetic
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification
Comments Vnlatilo unth cteam *-D orally in cats: 29.4mg/kg^ '
References (1) (1570)
(2) (1492)
49
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Pi nitrobenzene (163)
IDC Name 1,3-dinitrobenzene
Common Names m-dinitrobenzol. meta-dinitrobenzene
Structural Formula
Molecular WtP^ 168.11
Melting Pt.O) qn r
Boiling Pt.0)@ 756 mm.
Density (Condensed)
@
Density (gas)
@
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water insnluhlcill.
Hot Water
Ethanolyer Sol
Others: So1Mb1e in ether(1). rhlnroform(1) very soluble in benzene(1)
Acid, Base Properties _
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification
Coast Guard Classificatio
Comments Volatile with
References (1) (1570)
(2) (1492)
50
-------
PROFILE REPORT
Dinitrophenol (164)
1. GENERAL
The dinitrophenols are yellowish crystals described as being highly
toxic and readily adsorbed through the intact skin. They comprise
six possible position isomers:1492'0766'1570 2,3-(mp, 144 C); 2,4-(mp,
112 C); 2,5-(mp, 108 C); 2,6-(mp, 63 C); 3,4-(mp, 134 C); 3,5-(mp, 126 C).
Partially or fully nitrated phenols are obtained in industry by hydro-
lyzing the corresponding chloro compounds with dilute alkali. The dinitro-
phenols are then reduced to yield amino phenols which are employed as in-
1433
termediates -for dyes, Pharmaceuticals, and photographic chemicals.
Large scale commercial facilities for the manufacture of dinitrophenol
are operated by American Aniline Products, American Hoechst Corporation and
1571
Southern Dyestuff Company. Physical/chemical properties are summarized
in the attached worksheets.
2. TOXICOLOGY
Dinitrophenol is a moderate to severe health hazard for both acute and
chronic exposures. Liver and kidney damage have been reported in chronic
poisoning. Fatal cases have been reported in the literature from the
inhalation of the dust in a concentration estimated to be 40 mg/M .
Dinitrophenol is readily absorbed through intact skin and its vapors are
1492
absorbed through the respiratory tract.
Based upon comparable data and experience for dinitro-o-cresol, it is
believed that a level of 0.2 mg/M for an exposure time of eight hours is
safe. Care should be exercised in handling to prevent contact of the
material with the skin, eyes, or clothing.
51
-------
3. OTHER HAZARDS
The 2,3-dinitrophenol is considered to be a severe explosion hazard.
The 2,4- and 2,6-isomers are only moderately hazardous in this respect.
Information on 2,5-, 3,4- and 3,5- is not available but should be assumed
to represent a potential hazard. All the dinitrophenols should be treated
as moderate to highly toxic materials and the skin, eyes and lungs should
be protected accordingly.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
1564
The recommended control procedure for dinitrophenols requires that
direct skin contact be prevented by use of suitable protective clothing.
Where exhaust ventilation cannot effectively control dust and mist exposures,
respirators should be provided. Strict personal cleanliness and frequent
change of clothing is advised. Safety showers and eye wash fountains should
be provided in areas where these materials are handled.
Pertinent shipping regulations may be found in the Code of Federal
Regulations, Title 49, Transportation, Sections 73.345 and.73.362a. Under
these regulations, dinitrophenol solutions are classed as Poison B.
Disposal/Re use
Southern Dyestuff Company is currently under partial sponsorship
by the EPA to conduct studies pertaining to experimental treatment processes
for aqueous dinitrophenol waste streams. The main effort of the research
is directed toward the development of secondary disposal techniques to
handle dilute waste water streams containing 2,4-dinitrophenol. The
1621
Hyperion Plant in El Segundo, California will accept dinitrophenol only
under controlled conditions and at very low volumes.
52
-------
Recommended provisional limits of dinitrophenol in the environment
are as follows:
Contaminant and Maximum Concentration and Basis for
Environment Point Source Release Rate Recommendation
Dinitrophenol in 0.002 mg/M3 0.01 TLV
Air
Dinitrophenol in 0.010 ppm(mg/l) Stokinger and
Water and Soi1 Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dinitrophenol is expected to appear primarily in aqueous waste streams
at low concentrations and only rarely as concentrated waste. The processing
options are briefly described in the following paragraphs together with re-
commendations as to their adequacy.
Concentrated Dinitrophenol
In the event it becomes necessary to dispose of a significant quantity
of concentrated dinitrophenol, three disposal options are available. These
options are:
Option No. 1 - Recycle. The first option is to contact the manufacturer
and determine if it is possible to return the material. Southern Dyestuff
Company has indicated a willingness to accept concentrated dinitrophenol
for reprocessing. The option of recycling the material is adequate and
should be used whenever possible.
Option No. 2 - Incineration. Incineration is the second choice option
provided controlled combustion processes where the oxides of nitrogen are
1435
scrubbed from the effluent gas are used or where a thermal device is
used to reduce the oxides of nitrogen to their elemental form. The material
should be combusted at a minimum temperature of 1,800 F for at least 2.0
seconds.
53
-------
Option No. 3 - Sanitary Landfill. Sanitary landfills are generally
not recommended because of the potential of ground and surface water pol-
lution as well as possible occupational hazards resulting from on-site
handling. However, California Class I-type landfills are adequate
when the material is contained and has low vapor pressure.
Dilute Aqueous Haste
Dinitrophenol appears in the aqueous waste streams manufacturing pro-
cess. Other sources of vfaste are water used in the cleaning of equipment
used in dinitrophenol service. Methods for adequately handling the disposal
of dilute aqueous solutions of dinitrophenol are currently under study by
the Southern Dyestuff Company under the partial sponsorship of EPA
since effectiveness of the present secondary treatment techniques utilizing
activated sludges to dispose of dilute aqueous waste are in question.
Dinitrophenol can, under controlled conditions, be discharged into a
1 CO!
municipal sewage system at very small volumes, but the adequacy of this
practice is in doubt due to the apparent difficulty of microorganisms to
1044
degrade aromatic nitro compounds. Until data are available to show
that dinitrophenol can be degraded satisfactorily in secondary treatment
facilities, it is recommended that aqueous waste streams be concentrated
and treated as discussed in the section on concentrated dinitrophenol.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The dinitrophenols do not appear to be candidate waste stream con-
stituents for National Disposal Sites. It is anticipated that systems
to handle the great majority of the aqueous dinitrophenol waste generated
in the chemical process industries will continue to be located at the
source of the waste generation,, but that empahsis should be changed from
biological treatment processes to concentration and subsequent controlled
54
-------
incineration until the adequacy of the biological processes is proven.
In the event concentrated material becomes contaminated, manufacturers
of dinitrophenol can be contacted and arrangements made to return the
material for recycling, or, if need be, it can be incinerated as dis-
cussed in the section on Concentrated Dinitrophenol.
55
-------
7. REFERENCES
0620. Information available on empty containers and emergency situations.
(PB 197 146), Washington, Working Group on Pesticides, Sept. 1970.
58 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1433. Kirk-Othmer. Encyclopedia of chemical technology. 2d ed. 22 v.
and suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1435. John Zirk Company. NOX destructor. Bulletin No. NOX 1071m. Tulsa,
Oklahoma.
1450. Personal communication. Dr. Huber, Southern Dyestuff Company, to
W. P. Kendrick, TRW Systems, Mar. 28, 1972.
1492. Merck and Company, Inc. The Merck index of chemicals and drugs.
Rahway, New Jersey, 1960. 1,643 p.
1564. 2,4-Dinitrophenol. (Hygienic Guide Series). Detroit, American
Industrial Hygiene Assn. 2 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, 1966. 1,500 p.
1571. OPD Chemical buyers directory. New York, Schnell Publishing Company,
1971. 1,584 p.
1621. Personal communication. S. Sheridan, City of Los Angeles, Bureau of
Sanitation, to W. P. Kendrick, TRW Systems, Apr. 24, 1972.
56
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dinitrophenol (164)
IUC Name 2,3-dinitrophenol
Conmon Names 2,3-dinitrophenol
Structural Formula
1-hydroxy-2,3-di ni trobenzene
(N02)2C6H3OH
Molecular Wt. 184/
144 c
o:
_ Melting Pt.
Density. (Solid) 1.68P1' @ 20_C Density (gas) 6.35^ @
Boiling Pt._
Vapor Pressure (recommended 55 C and 20 0
Air = 1
Flash Point
Autoignitlon Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Solubility ^
Cold Water Slightly soluble Hot Water_
Others: ether (very soluble)
Acid, Base Properties
Upper_
Upper_
Very soluble in
Ethanol hot ethanol
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification
Coast Guard Classification
Comment. Sources1^ Not listed
References (1) 0766
(2) 1570
(3) 1571
57
-------
Vapor Pressure (recommended 55 C and 20 C)
•
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dinitrophenol (164)
IUC Name 2,4-dinitrophenol
Common Names 2,4-dinitrophenol
Structural Formula
orally rats 30 mg/kg* '
(N02)2C6H3OH
Molecular Wt.
Density (Solid) 1.683
Melting Pt.
112 C
.(1)
@ 24
Density (gas) 6. 35
"(D
Boiling Pt._
&
Air = 1
Flash Point
Autoignition
Flammability Limits in Air (wt %) Lower_
Explosive. Limits in Air (wt. %) Lower
Upper_
Upper_
SolubilIty
(2)
Cold Mater Slightly soluble Hot Water_
Others: ether, benzene, chloroform
Acid, Base Properties
Ethanol
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification
Coast Guard Classification
Comments Sources
(3).
AmpHran Aniline Prndnrt*:. Tnr.; Southern Dvestuff Company
References (1) 0766
(2) 1570
(3) 1571
(4) 1492
58
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dim'trophenol (164)
IUC Name 2.5-dinitrophenol
Common Names 2,5-dinitrophenol
Structural Formula
(N02)2C6H3OH
Molecular Wt.
Density (Condensed)_
184.11
(1)
Melting Pt. 108 C
(1)
Density (gas)_
Boiling Pt._
0
Vapor Pressure (recommended 55 C and 20 C)
G>
Flash Point
Autoignition Temp.
Lower
Flammability Limits in Air (wt %) Lower_
Explosive,Limits in Air (wt. %}
Solubility(1)
Cold Water Slightly soluble
Upper_
Upper_
Hot Water
Slightly
Ethanol soluble
Others: Soluble in hot alcohol, ether, fixed alkali hydroxide
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification
Commen ts
Coast Guard Classification
References (1) 1492
53
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dinitrophenol (164)
Structural Formula
IUC Name 2,6-dinitrophenol
Common Names 2.6-dinitrophenol
(N02)2C6H3OH
Molecular Wt. ] 84 • ] 1 _ Melting Pt. 63 c _ Boiling Pt.
Density (Condensed)_ _ @ __ Density (gas) 6.35^ @ _
Air = 1
Vapor Pressure (recommended 55 C and 20 C)
& &
Flash Point Autoignition Temp._
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
(4) (2) Very soluble in
Cold Water Slightly soluble^ ' Hot Water Solub1ev ; Ethanol hot ethanoU^
Others: ether (very); benzene, chloroform
Acid, Base Properties .
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification_
Comments Sources: ' American Hoechst Corp., Organic Intermediate Dept.
References (1) 0766
(2) 1570
(3) 1571
(4) 1492 .
60
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dinitrophenol (164)
IUC Name 3.4-dinitrophenor '
Common Names 3,4-dinitrophenol
Structural Formula
Molecular Wt. 184.11
:D
Melting Pt. 134 C
(1)
Density (Condensed) 1.672U' @
Density (gas)
Boiling Pt._
(3
Vapor Pressure (recommended 55 C and 20 C)
&
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Solubility (1)
Cold Water Slightly soluble
Upper_
Upper_
Hot Water
Others: Soluble in ether
Acid, Base Properties
Ethanol Soluble
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification_
Comments
Coast Guard Classification
References (1) 1570
61
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dinitrophenol (164)
IUC Name 3,5-dinitrophenol
(1)
Structural Formula
Common Names 3.5-dim'trophenol
(N02)2C6H3OH
Molecular Wt.
184.11
(1)
Density (Condensed) 1.702
UT
Melting Pt. 126.1 C(1) Boiling Pt._
Density (gas) @
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water
Hot Water
Ethanol Soluble
0)
Others: Soluble in benzene, chloroform, slightly soluble in ligroin
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification_
Comments
Coast Guard Classification
References (1) 1570
-------
PROFILE REPORT
Diphenylamine (167)
1. GENERAL
Diphenylamine is a white crystalline substance described as being
highly toxic. The commercial product is sold as very pale tan flakes,
light tan fused solid, and amber to brown liquid.
Diphenylamine is produced by heating aniline with aniline hydrochloride
at 210 to 240 C at a pressure of 90 psi. If a catalyst is used, aniline will
form diphenylamine in the absence of the hydrochloride. Diphenylamine is
widely used as a rubber antioxidant, as an intermediate for Pharmaceuticals,
and when fused with sulfur as an insecticide. It has also been used as a
stabilizer for explosives and in the preparation of azo dyes.
Commercial facilities for the manufacture of diphenylamine are operated
by American Cyanamid Co. and E. I. duPont de Nemours and Company, Inc.1571
The physical/chemical properties of diphenylamine are summarized in the
attached worksheet.
2. TOXICOLOGY
Diphenylamine is highly toxic when ingested, inhaled, or absorbed through
the skin.0766 The Threshold Limit Value (TLV) Of 10mg/M3 is based on industrial
experience and is known to be sufficiently low to prevent systemic poisoning.
Although the vapor pressure is low J, diphenylamine may be irritating to
mucous membranes , if inhaled as thf the dust or vapor. Animal experi-
ments indicate that it is poorly absorbed through the skin. Symptoms
of diphenylamine poisoning include bladder trouble, tachycardia, hyperten-
sion and skin trouble.
Protective clothing, safety glasses, and respirators (if dust exposure
is possible) should be used when handling diphenylamine. The decomposition
products evolved upon heating dephenylamine are highly toxic.0766
63
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3. OTHER HAZARDS
Diphenylamine" should be kept away from open flames, sparks and heat.
Although it emits .highly toxic fumes when heated to decomposition, it
is only considered a slight fire hazard. Diphenylamine is not considered
hazardous to health under normal conditions of industrial use.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
Although experiments indicate that diphenylamine is not readily
absorbed through the skin, direct skin contact should be prevented by use
of suitable protective clothing. Where exhaust ventilation cannot
effectively control dust and mist exposures, respirators should be provided.
Bul'k diphenylamine may be stored in steel equipment for extended
periods of time provided that the temperature is maintained below 65 C.
Prolonged storage at temperatures above 65 C will accelerate discoloration
of the product.1669
Diphenylamine is shipped in polyethylene lined paper bags, and 8,000
and 10,000 gallon tank cars. Shipping classification for diphenylamine is
chemical-NOI-no labels required.
Disposal/Reuse
Diphenyl is found as dilute waste in the tars which appear as bottom
products in the manufacturing processes. Aqueous waste streams are not
associated with the manufacture of diphenylamine. Criteria for disposing
of organic diphenylamine waste streams must take into account the toxicity
of the material, and byproducts of disposal. Recommended provisional
limits for diphenylamine in the environment are as follows:
64
-------
Contaminant in Provisional Limit Basis for Recommendation
Air
Diphenylamine 0.1 mg/M3 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Diphenylamine 0.5 ppm(mg/l) Stokinger & Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Diphenylamine is expected to appear primarily in organic waste
streams at low concentrations and only rarely as concentrated waste.
The processing options are briefly described in the following paragraphs
together with recommendations as to their adequacy.
Concentrated Diphenylamine
In the event it becomes necessary to dispose of a significant
quantity of concentrated diphenylamine wastes, and purification/recycling
is impractical, then incineration of the diphenylamine is the recommended
method of disposal. The material must be incinerated under controlled
conditions where oxides of nitrogen are removed from the effluent gas by
scrubbers and/or thermal or catalytic devices. Land burial of con-
centrated diphenylamine wastes is a satisfactory means of disposal pro-
vided the site is acceptable from a geologic and ground water hydrology
standpoint and meets California Class 1-type landfill standards.
Dilute Organic Waste Streams
Diphenylamine appears as dilute waste in the tars which appear as
bottoms products in the manufacturing processes. Currently, these tars
are disposed of in a plant landfill. Disposal of dilute waste in
plant landfills is a satisfactory means of disposal provided the site
is acceptable from a geologic and ground water hydrology standpoint and
meets California Class 1 landfill requirements. Incineration is also
an adequate method of disposal.
65
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Diphenylamine is not judged to be a candidate waste stream constituent
requiring National Disposal Site treatment since the various waste forms
containing this material can be treated at the site of generation with the
common industrial and municipal techniques discussed in Section 5.
66
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7. REFERENCES
0766. Sax, N.I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Book Corp. 1968. 1251 p.
14330 Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22v. and
suppl. New York, Interscience Publishers, 1963.
1435. John Zink Company. NOV destructor. Bulletin number NO 1071m.
Tulsa. 4 p. x x
1520. Personal communication. Mr. Hunt, American Cyanamid Company to
W. P. Kendrick, TRW Systems, Apr. 12, 1972.
1569. National Fire Protection Association. Manual of hazardous chemical
reactions, 1971. 4th ed. Boston, 1971. 308 p.
1571. Schnell Publishing Co. 1971-72 OPD chemical buyers guide. 59th ed.
New York, 1971, 1584 p.
1656. Condon, F. E., and H. Meislich. Introduction to organic chemistry.
New York, Holt, Rinehart and Winston Inc. 1960. 841 p.
1669. American Cyanamid Company. Diphenylamine. Bound Brook, New Jersey
1969. 1 p.
67
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H. M. Name Diphenylamine (167)
IUC Name
Common Names Diphenylamine
Phenylaniline
Molecular Wt. 169.24^'
Density (Condensed )1 .16 ^ @
HAZARDOUS WASTES PROPERTIES
WORKSHEET #167
Structural Formula
(C,Hr)o NH
Melting Pt. 52.9 C^ Boiling Pt. 302 C^
Density (gas) 5. 82^ @
(Air=l)
Vapor Pressure (recommended 55 C and 20 C)
1 mm @ 108.3 C^ @ @
Flash Point 307 F^
(cc)
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Solubility
Cold Water Insoluble(5)
Autoignition Temp. 846 F'1^
Lower Upper
Lower Upper
Hot Water Ethanol Soluble^
Others: Freely soluble in oroDvl alcohol, benzene, ether, glacial acetic acid, carbon,...
/-,\ disulfi(iev '
Acid, Base Properties Appx neutral v '
Highly Reactive with Hexachloromelamine, trichloromelamine^ '
Forms salts with strong acids ^ '
Compatible with mild steeP '
Shipped in polyethylene lin^d paper baas, tank cars^6'
ICC Classification
Commpnt? Mfq^ ' American Cvanamid
Coast Guard Classification
Co.. E. I. duPont de Nemour<: and r.n Tnr
References (1) (0766)
(2) (1656)
(3) (1433)
(4) (1569) (7) (1571)
(5) (1492)
(6) (1669)
68
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PROFILE REPORT ON
HALOGENATED ALIPHATIC HYDROCARBON FUMIGANTS
Ethylene Bromide (182). Methyl Bromide (267). Methyl Chloride (268)
1. GENERAL
Introduction
Fumigants are chemicals which are distributed through space as gases,
and therefore, at a given temperature and pressure must exist in the gaseous
state in sufficient concentration to be lethal to the insect pest. This
physical requirement greatly limits the number of insecticides which may
be used as fumigants, and most of the fumigants marketed today are
halogenated hydrocarbons with high vapor pressures. Methyl bromide is one
of the most widely used general fumigants, and ethylene bromide (ethylene
dibromide) is an effective soil fumigant because of its slower release rate
of vapors. Methyl chloride, though not used primarily as a fumigant, is often
employed in aerosol bombs to control flying insects in enclosed premises.
The 1970 production figures for the three fumigants are: ethylene
bromide, 296,826,000 Ib; methyl bromide, 21,047,000 Ib; and methyl chloride,
422,678,000 Ib. All three commodities are expected to sustain a moderate-
co-good growth rate in the near future despite the fact that ethylene
bromide is also used as a component of antiknock fluid in conjunction with lead
alkyls and the possible phasing out of leaded gasoline.
Manufacture
Ethylene Bromide. Ethylene bromide is manufactured by reacting ethylene
and bromine in either batch or continuous processes, with the final product
obtained by fractional distillation after washing the reactor effluent with
•I QQQ
dilute aqueous alkali to remove small quantities of hydrogen bromide.
The U.S. producers of ethylene bromide include the following ' :
69
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Dow Chemical Company, Midland, Michigan.
Ethyl Corporation, Bromet, Arkansas.
Ethyl Corporation, Houston, Texas.
Great Lakes Chemical Corporation, El Dorado, Arkansas.
Houston Chemical Company, Beaumont, Texas.
Michigan Chemical Corporation, El Dorado, Arkansas.
Methyl Bromide. Methyl bromide is usually manufactured by using elemen-
tary bromine together with a reducing agent as the source of hydrogen bromide
for reaction with methanol. The reducing agents that have been employed
include sulfur dioxide, hydrogen sulfide, and sulfur raw oil, and both
1808
batch and continuous processes have been carried out industrially.
The current U.S. producers of methyl bromide are '506»'818:
Dow Chemicar Company, Midland, Michigan
Great Lakes Chemical Corporation, El Dorado, Arkansas.
Kerr-McGee Chemical Corporation, Los Angeles, California.
•Michigan Chemical Corporation, St. Louis, Michigan.
Methyl Chloride. The two principal processes for industrial production
of methyl chloride are chlorination of methane and reaction of hydrogen
chloride with methanol. The methanol-hydrogen chloride reaction yields methyl
chloride as the sole product, whereas chlorination of methane yields other
chlorinated hydrocarbon coproducts of equal commercial importance in
substantial amounts, such as methylene chloride and carbon tetrachloride.
The U.S. producers of methyl chloride include the following ' :
Allied Chemical Corporation, Moundsville, West Virginia.
Ancon Chemical Corporations West Lake, Louisiana
Dow Chemical Company, Freeport, Texas.
Dow Chemical Company, Pittsburgh, California.
Dow Corning Corporation, Carroll ton, Kentucky.
Dow Corning Corporation, Midland, Michigan.
E. I. Du Pont de Nemours & Company, Niagara Falls, flew York.
Ethyl Corporation, Baton Rouge, Louisiana
Vulcan Materials Company, Chemical Division, Newark, New Jersey.
Union Carbide Corporation, Institute, West Virginia.
70
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Uses
Ethylene bromide is used mostly as an ingredient of automobile and
aircraft fuels to aid in removing lead from the engine cylinders. The
next most important use is an active ingredient of grain fumigant formulations
for insect control and of soil fumigants for the control of wireworms and
nematodes. Other much smaller uses are as a nonflammable solvent for
resins, gums, and waxes, and as an intermediate in synthesis.
The major use of methyl bromide is in the extermination of insect and
rodent pests, as the compound is very suitable for the fumigation of food
commodities and areas in which they are processed and stored, as well as
for tobacco and nursery stock. Methyl bromide has also been used as a fire
extinguisher, although its application is limited due to its high toxicity.
In moderately small amounts, methyl bromide is used in organic synthesis,
1433
particularly as a methylating agent.
The principal uses of methyl chloride are in the manufacture of silicon.
butyl rubber, tetramethyl lead, and methyl cellulose. Methyl chloride is
also used as a fumigant in controlling flies and other flying insects, but
the application in this area amounts to a small proportion of its total usage.
Other industrial applications include its use as a methylating agent in
the production of quaternary ammonium compounds and of triptane, and as
starting material in the manufacture of methylene chloride, chloroform,
carbon tetrachloride, and of various broraochloro- and chlrofluoro-methanes.1433
Sources and Types of Wastes
The sources of ethylene bromide, methyl bromide, and methyl chloride
wastes may include the following: (1) manufacturers of the chemicals; (2)
pesticide formulators; (3) wholesalers of the chemicals; (4) professional
applicators; (5) agricultural users; (6) government facilities that store,
transport, and use the chemicals; (7) commercial and industrial processes
utilizing these chemicals—gasoline formulation in the case of ethylene
bromide and silicone, butyl rubber, tetramethyl lead and methyl cellulose
manufacturers in the case of methyl chloride.
71
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In general, ethylene bromide, methyl bromide, and methyl chloride
wastes can be classified as either diluted or concentrated wastes. Diluted
aqueous wastes include those generated in the waste waters of the manu-
facturers and formulators. Diluted gaseous wastes include gas streams in
the manufacture of other products that require purification and removal
of these toxic halohydrocarbons, and also any gas streams released to the
atmosphere containing these compounds. Concentrated wastes normally
include any unused or contaminated chemicals, and materials left in
containers after emptying.
As fumigants, methyl bromide and ethylene dibromide have both been used
alone or in combination with each other in various proportions. The most
common methyl bromide formulation is as a liquified gas containing 2 percent
1808
chloropicrin stored in returnable pressurized containers. Ethylene
bromide is frequently used mixed with carbon tetrachloride, carbon disulfide
1808
or ethylene dichloride, although it is sometimes formulated as emusifiable
concentrates. Any surplus methyl bromide and ethylene bromide fumigants will
probably be found in these common commercial formulations.
Physical and Chemical Properties
The physical and chemical properties of ethylene bromide, methyl
bromide and methyl chloride are summarized in the attached worksheets.
2. TOXICOLOGY
Ethylene bromide is highly toxic to man and animals, and is readily
absorbed through lungs, intact skins, and the gastrointestinal tract.
Continued exposure to low doses causes irritation of the eyes, nose,
respiratory tract, and finally paralysis of the hind legs from which the
animal may recover eventually. Through errors in labeling, it has been
used occasionally in place of ethyl bromide in anesthesias leading to
cases of fatal poisoning as a result of cardiac failure. Contact with
I DQQ
the skin may cause injury with blister formation.
-------
Methyl bromide is a highly toxic substance of insidious action.
Single exposures to 1,000 ppm for 30 to 60 minutes are dangerous to
life. The effects are on both respiratory and central nervous system,
although death is usually caused by lung irritation resulting in congestion
and edema. The early symptoms of fatal poisoning are headache, visual
disturbances, nausea and vomiting, smarting of the eyes, irritation of
the skin, listlessness, vertigo, and tremor. Exposure to concentrations
as low as 100 to 500 ppm over a period of time may lead to chronic
poisoning, resulting in a variety of symptoms and signs, most of which are
due to injury of the central nervous system and include blurred or double
vision, slurred speech, numbness of the extremities, mental confusion,
hallucinations, tremor, coma, or frequent fainting attacks. Recovery
is often prolonged and there may be permanent injury, such as sensory
disturbances, weakness, disturbances of guilt,irritability, and blurred
vision. In addition, liquid methyl bromide is an extreme irritant to
the skin and may produce severe burns.
Methyl chloride is a dangerous anesthetic and narcotic, about one-fourth
as active as chloroform, and presents serious problems to life and health
when inhaled in high concentrations. Poisoning by methyl chloride produces
the following characteristic symptoms: drowsiness, mental confusion, coma,
nausea, vomiting, and in severe cases, convulsions and death. It is
dangerous in that after apparent recovery from seemingly mild exposures,
serious and sometimes fatal return of symptoms may occur even after
an interval of several days. It is absorbed quickly but eliminated rather
slowly, and for this reason repeated exposures are hazardous. Recovery
after what may appear to be a relatively slight exposure may be delayed
2 to 3 weeks, and after severe exposure some effects on the nervous system
may be present for months or even years. Severe exposure may also effect
the liver, kidneys, and blood forming tissues, lead to an increase in
pulse rate, temperature, and breathing rate. Acute poisoning of methyl
chloride is relatively rare, but might occur with exposures to well over
500 ppm. The type of poisoning occuring most frequently is due to repeated
-------
exposure to concentrations less than 500 ppm. Although methyl chloride
is in its vapor state at ordinary temperatures and will produce little or
no local effect, a stream of concentrated vapor striking the skin may
result in a condition resembling frost bite followed by reddening, and
occasionally, blister formation. '
The American Conference of Governmental Industrial Hygienists
recommended Threshold Limit Values (TLV) for these compounds in air are:
q q
ethylene bromide, 20 ppm or 145 mg/M ; methyl bromide, 15 ppm or 60 mg/M ;
3
and methyl chloride, 100 ppm or 210 mg/M .
Because of their volatility, the water pollution hazards arising from
the human toxicity of methyl bromide and methyl chloride are relatively
slight. For ethylene bromide, the approximate lethal dose to man has been
1312
estimated to be 65 mg/kg body weight.
No actual published data of aquatic toxicity for the three compounds
were found. However, the National Research Council's Committee on Hazardous
Materials, based on the physical properties of these compounds and their
chemical similarity to other chemicals of known toxicity, has given a Grade 3
aquatic toxicity rating to ethylene bromide and a Grade 1 aquatic toxicity
rating to methyl bromide and methyl chloride. Although a Grade 3 rating
normally indicates a threshold range of 1 to 100 ppm to aquatic life and a
Grade 1 rating a threshold range of 1,000 to 10,000 ppm to aquatic life,
these ratings were also modified in some cases for chemicals having low
water solubility or high volatility to account for the lower probability
of water pollution, and this explains the low aquatic toxicity ratings
given to methyl bromide and methyl chloride.
3. OTHER HAZARDS
Ethylene bromide is a nonflammable liquid, but reacts vigorously with
metals such as aluminum, magnesium, sodium and potassium, strong alkalies,
and oxidizing agents. An explosion may result if a mixture of liquid
ammonia and ethylene bromide is allowed to warm up to room temperature.
74
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At atmospheric pressure methyl bromide is practically nonflammable.
Methyl bromide is also not particularly corrosive to most metals, although
it attacks aluminum and magnesium and their alloys. With aluminum, methyl
bromide forms the spontaneously ignitable aluminum trimethyl.181°
Methyl chloride is thermally stable, but may break down to produce
hydrogen chloride and other toxic gases at high temperatures. It hydrolyzes
slowly in water or upon contact with moisture, with the formation of
hydrochloric acid, and is therefore corrosive. In addition, the hydrochloric
acid formed attacks most metals with the evolution of hydrogen, which may
form explosive mixtures with air. When dry, methyl chloride is inert
towards most engineering materials except zinc, aluminum, magnesium, and
their alloys. However, once reaction of methyl chloride with these metals
or alloys initiates, it is greatly accelerated by the reaction products,
resulting in rapidly increasing pressure if confined, and the release of
1811
gases which may ignite spontaneously.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, Transportation
Ethylene bromide, methyl bromide, and methyl chloride are all toxic
by inhalation or skin contact. Full protective clothing and the use of a
respirator are recommended in their handling and application. In cases
of accidental contact, all contaminated clothing should be removed
immediately and the skin washed thoroughly with soap and water. * '
Storage of these chemicals should be in cool, dry, well-ventilated
areas, away from acute fire hazards. Because of their low boiling points,
containers or storage vessels of methyl bromide and methyl chloride should
also be protected from excessive heat and against sudden rise in
temperatures.1810'1811
Methyl bromide is classified by the U.S. Department of Transportation
(DOT) as a Poisonous Liquid, Class B, and methyl chloride is classified
by DOT as a Flammable Compressed Gas. As such, both chemicals must be
packed in DOT specification containers when shipped by rail* water, or
75
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highway and all DOT regulations governing loading, handling, shipping,
and labeling must be complied with. Ethylene bromide is not classified by
DOT, but due to its toxic nature, the same regulations governing the
handling, loading, and shipping of Class B Poisonous Liquids should also
be followed here.
Additional information on the safe handling and use of methyl bromide
and methyl chloride are described in greater detail in the Chemical Safety
Data Sheets SD-35 and SD-40 published by the Manufacturing Chemists
Association.
Disposal/Reuse
Contaminated or degraded ethylene bromide, methyl bromide and methyl
chloride are usually not considered for reprocessing, although manufac-
turers would normally accept these for disposal. For safe disposal of
ethylene bromide, methyl bromide, or methyl chloride, the following pro-
visional limits are recommended:
Contaminant Basis for
in Air Provisional Limits Recommendation
Ethylene bromide 1.45 mg/M3 0.01 TLV
Methyl bromide 0.6 mg/M3 "
Methyl chloride 2.1 mg/M3
Contaminant in Basis for
Water and Soi1 Provisional Limits Recommendation
Ethylene bromide 7.25 ppm (mg/1) Stokinger and
Woodward Method
Methyl bromide 390 ppm (mg/1) Stokinger and
Woodward Method
Methyl chloride 10.5 ppm (mg/1) Stokinger and
Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Ethylene bromide, methyl bromide and methyl chloride generally do
not present pollution problems to the chemical industry and very few
76
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specific efforts have been made to study their control or disposal. For
these reasons, most of the removal, disposal, or recovery techniques dis-
cussed here are near future processes where no quantitative data are
available.
Removal from Air
Option No. 1 - Refrigerated Condensation. When present in suffi-
ciently high concentrations, refrigerated condensation has been used and
is the recommended method for removing ethylene bromide, methyl bromide,
or methyl chloride from air or a gas stream.1965'1966'1972'1986 The
halohydrocarbons are almost completely recovered, and the remaining
traces can be removed by the other processes described here.
Option No. 2 - Monoethanolamine Scrubbing. Monoethanolamine (MEA) is
commonly used for the removal of acid gases (hydrogen sulfide and carbon
dioxide) in scrubbing towers. The absorption of ethylene bromide and methyl
bromide by MEA has been used in the analytical determination of these
pnpq ?rni
compounds in air. ' This indicates that MEA scrubbing could also
be conceivably employed in removing these compounds from air on the
commercial scale, although it remains to be demonstrated that the fouled
MEA could be readily regenerated by methods such as steam stripping.
Option No. 3 - Alkaline Alkoxide Scrubbing. Ethylene bromide, methyl
bromide, and methyl chloride could all be readily absorbed from the air by
scrubbing with a solution of potassium or sodium hydroxide in anhydrous
i ^m ?n^?
methanol and ethanol. Ul'tuo In the case of ethylene bromide, vinyl
bromide is immediately formed, although further dehalogenation occurs very
slowly in the alcoholic solution.2030 For methyl bromide and methyl chlo-
ride, either the dimethyl ether or the methyl ethyl ether is formed, depend-
ing on whether methanol or ethanol is used in the absorbent. In fact, the
reaction between alkyl halides and alkali alkoxides is the well-known
Williamson ether synthesis and provides a method of preparing symmetrical
1808
and unsymmetrical ethers. The time required to reach TOO percent
77
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conversion of a known amount of methyl bromide in a potassium hydroxide -
methanol solution at different temperatures has been measured and reported
203? •
by Dumas and Latimer, and their results showed that complete conversion
was obtained in 7 hr at 75 F or only 45 min at 157 F with IN potassium
hydroxide in methanol. However, similar experiments have not been conducted
with either methyl chloride or ethylene bromide, and the effectiveness of
alkali alkoxides as an absorbent for the alkyl halides on the commercial
scale has yet to be proven.
Option No. 4 - Alcohol Scrubbing. Dow has experimented with the use of
methanol scrubbing for the removal of methyl bromide from air, but to date
only marginal results are obtained for the low methyl bromide concentration
ranges (0.1%) investigated. When higher concentrations of methyl
bromide in the air are encountered, however, Dow believes methanol scrubbing
would be an effective means to achieve a high rate of removal. Ethylene
bromide has also been reported to be readily absorbed from air by shaking
2030
with ethyl alcohol, but again,data are not available to determine the
applicability of the process on commercial scale.
Option No. 5 - Adsorption with Activated Carbon. Activated carbon is
extensively employed for the removal of traces of gas impurities from air
and it has been suggested that small quantities of ethylene bromide, methyl
bromide, or methyl chloride could be effectively removed from air by passage
through activated-carbon traps or beds.1986'1987
Rejnoval from Water
Ethylene bromide is only slightly soluble in water and most if it can
be removed from water in a gravity separator or a settling pond due to
its density which is more than twice that of the water. ' Methyl
bromide is practically insoluble in water and is also extremely volatile,
and hence does not contribute to water pollution. Methyl chloride is
-------
slightly soluble in water but again is also very volatile and can be
readily removed from water by simple physical methods. Some of the
techniques used for treating water contaminated with these compounds are
described below briefly.
Option No. 1 - Steam Stripping. Steam stripping is a widely used disposal
method in the chemical and petrochemical industry and can be used to remove
1970 1972 1987
ethylene bromide, methyl bromide, or methyl chloride from water. »••"«-,u
The waste gases from stripping must be burned in incinerators equipped
with adequate scrubbing to totally prevent air pollution.
Option No. 2 - Blowing with Air. The Manufacturing Chemists Association
recommends removing methyl chloride from water by blowing the contaminated
water with air, and burning the outlet air stream in cases of gross
loll
contamination, with a flash arrestor on the vent line. Air blowing
can also be used in removing the equally volatile methyl bromide
from water.
Option No. 3 - Adsorption with Activated Carbon. The engineering firm
of Camp, Dresser, and McGee has completed a pilot scale investigation on the
use of both powdered and granular activated carbon for the removal of
chlorinated hydrocarbons from the combined waste waters of several chemical
plants in the Niagara Falls, New York area, including the Du Pont facility
1971 19Q?
there that manufactures methyl chloride. ' Although the removal of
any of the individual compounds was not separately studied, the pilot work
was considered a success and Camp, Dresser, and McGee is currently designing
a full scale physical-chemical waste treatment facility to serve the
industrial concerns in the area. It has also been claimed that activated
carbon can be used to remove traces of ethylene bromide from water.
However, activated carbon treatment is of value mainly for the adsorption
of organic compounds of relatively high molecular weight and its effectiveness
in removing ethylene bromide or methyl chloride from water requires
further investigation.
79
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In addition, because of the volatility of methyl bromide and methyl
chloride, adequate treatment of waste waters contaminated with small
quantities of these compounds could probably be achieved in conventional
municipal facilities with aeration.
Disposal/Recovery of Concentrated Wastes
Option No. 1 - Incineration. The complete and controlled high tempera-
ture oxidation of halohydrocar'bons in air or oxygen with adequate scrubbing
and ash disposal facilities offers the greatest immediate potential for
the safe disposal of these compounds with the possibility of recovering
the greater part of all of the halogens in some usuable form. In particular,
Dow Chemical is currently in the process of designing incinerators to
*
dispose of the concentrated ethylene bromide and methyl bromide wastes
at its Midland Plant. The off gas from the incinerator will
contain both hydrogen bromide and bromine, both of which are harmful
pollutants if released to the atmosphere. The hydrogen bromide can be
readily removed by scrubbing with caustic soda, but Dow claims to encounter
some problems with bromine removal. However, it is not clear whether
Dow has fully investigated the several methods available for the separation
of bromine vapors from air: (1) contacting the air-bromine mixture with
moist scrap iron leading to the formation of ferrous bromide; (2) absorption
in ammonia solution with the formation of ammonium bromide; (3) absorption
in ferrous bromide solution with the formation of ferric bromide; (4)
alkaline absorption in which bromine reacts with sodium hydroxide or
carbonate to form sodium bromate, sodium bromide, and either water or
carbon dioxide; (5) lime absorption in which bromine reacts with calcium
hydroxide to form calcium bromide and bromate; (6) reduction of bromine
by means of sulfur dioxide giving rise to the formation of a spray of
fine droplets of hydrobromic and sulfuric acids that could later be
trapped by a solution of the same mixed acid circulating in an absorption
tower; and (7) absorption with a concentrated solution of sodium bromide
Auxiliary fuel will be required in the combustion of ethylene bromide.
-------
1 ono
cooled below OC in packed towers. The absorbed bromine that is bound
chemically in the form of bromide, bromate or hydrogen bromide can all be
recovered by either acidification with sulfuric acid or reoxidizing with
chlorine. For small quantities of methyl bromide and ethylene bromide, both
compounds could be safely disposed of by dissolution in a flammable solvent
and spraying the mixture into the fire box of any incinerator equipped with
an afterburner and alkali scrubber. In the case of methyl chloride,
combustion units designed for the disposal of chlorinated organic wastes
and capable of recovering chlorine in the form of usable hydrogen chloride
have been developed, and a7,0001b/hr plant is now under construction for
E. I. DuPont de Nemours and Company in Victoria, Texas by Union Carbide
1743
Corporation. .Properly designed and operated incineration is therefore
considered as the best current and near future method for the disposal of
concentrated ethylene bromide, methyl bromide, and methyl chloride wastes.
Option No. 2 - Chemical Degradation. The use of chemical reagents to
decompose concentrated ethylena bromide, methyl bromide or methyl chloride
wastes to less toxic forms has not been specifically reported in the
literature. Based on the known reactions of these compounds, however, it
appears that: (1) metal alkoxides could be used to react with methyl
bromide or methyl chloride leading to the formation of ethers and metallic
1808
bromides or chlorides according to the Williamson ether synthesis;
(2) sodium in liquid ammonia could be used to react with methyl bromide
or methyl chloride leading to the formation of methane, methyl amine, and
sodium bromide or chloride; and (3) zinc could be added to ethylene bromide
with the formation of ethylene and zinc bromide. Since these methods generally
do not lead to the recovery of valuable halogens and little is known of the
optimum conditions under which the chemical reagents could be applied,
chemical degradation could not be recommended as a technique for the
disposal of the halohydrocarbons at the present time.
Option No. 3 - Release to Atmosphere. Methyl bromide is degraded
rapidly in the presence of sunlight and air and small amounts of the material
could be safely disposed of by slowly releasing the liquified gas to the
2173
atmosphere in a^ well-ventilated outdoor location.
81
-------
The disposal of large volumes of ethylene bromide, methyl bromide or
methyl chloride wastes in landfill sites, open pits, lagoons and by on-site
burning, deep-well disposal, or deep sea burial are not recommended
practices because of volatility of these compounds and the obvious contri-
butions to air and water pollution.
To summarize, the only demonstrated method*for the removal of the
halohydrocarbons from air is refriegerated condensation when these
compounds are present in sufficiently high concentrations. The use of
MEA, alkaline alkoxide and alcohol scrubbing or activated carbon to remove
traces of these halohydrocarbons from air seems feasible, but due to the
lack of sufficient supporting data could only be considered as near future
waste treatment processes. Adequate methods for the removal of the
halohydrocarbons from water include steam stripping, and blowing with air
in the case of the more volatile methyl bromide and chloride. Again,
activated carbon adsorption to remove traces of these compounds from water
could not be considered as a proven method. To dispose of concentrated
ethylene bromide, methyl chloride, or large volumes of methyl bromide wastes,
the only adequate method is by incineration. Small quantities of concen-
trated methyl bromide could be safely disposed of by venting to the
atmosphere.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Methyl bromide is usually packaged in returnable pressurized cylinders
and the empty containers are shipped back to the manufacturers. In addition,
residual methyl bromide could be adequately disposed of by careful venting
to the atmosphere. Ethylene bromide is mainly used in gasoline formulations,
and methyl chloride is generally used as a starting material or.as a
methylating agent in chemical manufacture. As such, both ethylene bromide
and methyl chloride wastes could be adequately handled along with other
halohydrocarbon wastes (e.g., chlorinated solvents) from manufacturing
plants. The degree of toxicity of all three compounds is moderate when
compared with that of the more toxic halohydrocarbons such as carbon tetra-
chloride. For the above reasons, ethylene bromide, methyl bromide, and
-------
methyl chloride are not considered as candidate waste stream constituents
for National Dispoal Sites.
-------
7. REFERENCES
0096. Fire protection guide on hazardous materials. 4th ed. Boston,
National Fire Protection Association International, 1972. 950 p.
0225. American Conference of Governmental Industrial Hygienists.
Threshold limit values for 1971. Occupational Hazards, p.35-40,
Aug. 1971.
0278. Code of Federal Regulations. Title 49--transportaion, parts 71 to
90. (Revised as of January 1, 1967). Washington, U.S.
Government Printing Office, 1967. 794 p.
0311. National Academy of Sciences. Evaluation of the hazard of bulk
water transportation of industrial chemicals--a tentative guide.
Report to the United States Coast Guard by the Committee on
Hazardous Materials, Advisory to the U.S. Coast Guard, Division
of Chemistry and Chemical Technology, National Research Council.
Washington, U.S. Government Printing Office, 1970. 25 p.'
1301. Matheson gas data book. 4th ed. New York, Herst Litho Inc., 1966.
500 p.
1312. Christensen, H. E. Toxic substances annual list 1971. Washington,
U.S. Government Printing Office, 1971. 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed.
New York, Interscience Publishers, 1964. V.~3, 927 p. V.5, 884 p.
1506. Methyl bromide and methyl chloride. Jji Chemical profiles.
New York, Schnell Publishing Company, Inc. 1970.
1718. United States Tariff Commission. Synthetic organic chemicals:
United States production and sales, 1970. Washington, U.S.
Government Printing Office, 1972. 262 p.
"O
1743. Halswitt, C., and J. A. Mraz. HC1 removed from chlorinated organic
waste.. Chemical Engineering. 79 (IT): 80-81, May 15, 1972.
1808. Jolles, Z. E. Bromine and its compounds. New York, Academic Press,
1966. 940 p.
1810. Chemical safety data she^t SP-18--properties and essential
information for safe handling and use of methyl bromide.
Washington, Manufacturing Chemists Association, 1968. 15 p.
1811. Cheml c?.1 safety fteta sh?-et StK40--properties and esspntial
information for safe handling and use of methyl chloride.
Washington, Manufacturing Chemists Association, TSFO. 18 p.
-------
REFERENCES (CONTINUED)
1965. Personal communication. H. Rentz, Great Lakes Chemical Corp.
to C. C. Shih, TRW Systems, June 9, 1972. Methyl bromide and
ethylene bromide waste treatment.
1966. Personal communication. D. L. Touzeau, Michigan Chemical Corp.
to C. C. Shih, TRW Systems, June 9, 1972. Methyl bromide waste
treatment.
1967. Personal communication. C. Carter, Michigan Chemical Corp. to
C. C. Shih, TRW Systems, June 9, 1972. Ethylene bromide waste
treatment.
1968. Personal communication. R. Namedz, Michigan Chemical Corp. to
C. C. Shih, TRW Systems, June 9, 1972. Ethylene bromide waste
treatment.
1969. Personal communication. W. Bricker, Dow Chemical Company to
C. C. Shih, TRW Systems, June 12, 1972. Methyl bromide waste
treatment.
1970. Personal communication. M. Kelly, Dow Chemical Company to
C. C. Shih, TRW Systems, June 12, 1972. Methyl bromide and
ethylene bromide waste treatment.
1971. Personal communication. G. Amery, E. I. DuPont de Nemours &
Company to C. C. Shih, TRW Systems, June 13, 1972. Methyl
chloride waste treatment.
1972. Personal communication. H. L. Mayo, Dow Chemical Company to
C. C. Shih, TRW Systems, June 13, 1972. Methyl chloride
waste treatment.
1986. Personal communication. S. Clift, Kerr-McGee Chemical Corp. to
C. C. Shih, TRW Systems, June 14, 1972. Methyl bromide waste
treatment.
1987. Personal communication. J. McKeever, Dow Chemical Company to
C. C. Shih, TRW Systems, June 14, 1972. Methyl chloride
j waste treatment.
1992. Personal communication. R. Woodward, Camp, Dresser and McGee to
C. C. Shih, TRW Systems, June 19, 1972. Methyl chloride waste
treatment.
2029. Sinclair, W. B. and P. R. Crandall.
dibromide in liquid and gas phases
Journal of Economi c Entomology, 45
Determination of ethylene
by the use of monoethanolamine.
(1): 80-82, Feb. 1952.
-------
REFERENCES (CONTINUED)
2030. Kennett, B. H. Determination of ethylene dibronride and ethylene
chlorobromide in air. Journal of Agricultural and Food
Chemistry, 2 (13): 691-692, June 23, 1954.
2031. Winteringham, F. P. W. Method for the micro-determination of the
sorption of fumigants. Journal of the Society of Chemical
Industry Transactions, 65 (2): 48-51, !Feb. 1946.
2032. Dumas T., and R. A. Latimer. The coulometric determination of
methyl bromide. Journal of Agricultural and Food Chemistry,
10 (4): 276-279, July - Aug. 1962.
2173. Lawless, E. W., T. F. Ferguson, A. F. Meiners and A. C. Aspoas.
Method for disposal of spilled and unused pesticides. Kansas
City, Missouri, Midwest Research Institute, preliminary draft,
Apr. 1972. 272 p.
86
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
ri. M. Name Ethylene bromide (182)
IUC Name 1.2 -Dibromoethane
Common NamesEthylene dibromlde
Structural Formula
CH?Br . CH,Br
<">
Molecular Wt. 187.!
Melting Pt. 9.3 c
Density (Condensed) 2.172
9 25 C
(1)
Boiling Pt.131.5
Density (gas)_
Vapor Pressure (recommended 55 C and 20 Q
8.5 mm @ 20 C '2' 11 mm_
Flash Point
25 C
(1)
119.9 mm
75 C
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 0-43% @ 30 C (1) Hot Water
Ethanol Soluble
Others: Completely mlscible with carbon tetrachloride, benzene, gasoline, ether,
and anhydrous alcohols. \ '
Acid, Base Properties
Highly Reactive with aluminum, magnesium, sodium and potassium, strong alkalies, and
oxidizing agents. *• '
Compatible with_
Shipped in
bottles, 55-gal drums, tank cars
ICC Classification
Coast Guard Classification
Coitments Etny1ene bromide is a clear,'colorless liquid with a characteristic sweet odor.
References (1)
(2) 1433
87
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name "ethyl Bromide (267)
IUC Name Bromomethane
Common Names
Structural Formula
CH3Br
Molecular Wt. 94.95
Density (Condensed) 1.732
00
Melting Pt. -93 C u; Boiling Pt. 3.6 C
_ C^ Density (gas) 3.27 @ 0 C ^
^1'
Vapor Pressure (recommended 55 C and 20 C)
1250 mm @ 20 C ^
(Air = 1)
0
Flash Point Practically u;
nonflammable
Flammability Limits in Air (Vol%)
Explosive-Limits in Air (wt. %)
Solubility
Cold Water less than 0.1 wt %
Autoignition Temp.537
L owe r 10.0
Lower
Upper 15.4
Upper
Hot Water
Ethanol Soluble
Others: Soluble in ethyl ether, carbon tetrachloride, chloroform, carbon disulfide,
benzene^''
Acid, Base Properties
TTT
Highly Reactive with aluminium, magnesium, and their alloys
Compatible with
Shipped in metal containers or tank cars (rare) ' '
ICC Classification Poisonous Liquid, class B Coast Guard Classification Poisonous liquid,B
Comments Extreme1y hazardous liquid and vapor under pressure.
References (1) 1810
(2) 1618
88
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Methyl Chloride (268)
IUC Name Chloromethane
Common Names
Structural Formula
CH3C1
Molecular Wt. 50.491
Melting Pt. -97.6 C
Density (Condensed)0.920
_, @ 20 C Density (gas) 3.58
(Air = 1)
Vapor Pressure (recommended 55 C and 20 C)
101 mrn^Hq^ _@_ -80 F . 355.6 mm Hgg -40 F
Autoignition Temp.632 C
Boiling Pt. -23.8 C
8 -15 C
1093.6mm Ho @ 5 F
Flash Point Below 0 C
Flammability Limits in Air (\/0-\%) Lower 10-7
Explosive Limits in Air (wt. %) Lower_
Upper 17.4
Upper
Solubility
Cold Water 0.46 wt % at 20 C
Hot Water 0.26wt $ at 40 C Ethanol soluble
Others: readily soluble in alcohols, chloroform, and mineral oils.
Acid, Base Properties Hydroloyres in the presence of moisture to hydrochloric acid.
Highly Reactive with aluminum, and to lesser extent with zinc magnesium, the alloys thereof
whpn HruK anrl alkali mofalc
Compatible with most otner engineering materials.
Shipped in as a liquid under pressure in cylinders and tank cars.
ICC Classification Flammable compressed gas coast Guard Classification
Inflammable
Comment Methy1 chloride is thermally stable, but also flammable and subject to
decomposition upon contact with moisture. At high temperatures, it may break down to
produce hydrogen chloride and other toxic gases. _
References (1) 1811
89
-------
PROFILE REPORT
Ethylenimine _(19Q]_
1. GENERAL
Ethylenimine is a colorless flammable liquid having very high toxicity.
It is an extremely reactive compound, the reactivity stemming from the ease
with which ring opening occurs due to the strained nature of the three-
1514
member ring.
In June 1963, the Dow Chemical Company announced a new process which
used ammonia and ethylene dichloride as raw materials. With its pro-
cess, Dow was the first large scale U.S. producer of ethylenimine.
Other commercial facilities for the manufacture of ethylenimine are operated
by Borden Inc., Chemirad Corporation, Dow Chemical Company, and Polysciences,
Inc. Physical/chemical properties are summarized in the attached work-
sheet.
2. TOXICOLOGY
Ethylenimine is a highly toxic material. It is corrosive to the skin
1514
and is readily absorbed in toxic amounts. It is a skin sensitizer and
1492
necrotizing agent. Liquid ethylenimine is capable of causing a severe
burn to the eyes, which may result in partial or total loss of vision. High
concentrations of ethylenimine vapor (~100 ppm) may cause eye irritation.
This material has a high oral toxicity. Serious illness may result from
the ingestion of a relatively small amount.15 The inhalation of ethylemi-
nine monomer at a concentration slightly above 25 ppm for 8 hours will kill
1492
rats and guinea pigs. In 30 to 60 minutes 250 ppm is dangerous to man.
1514
Available experimental evidence would indicate that no exposure should
exceed 100 ppm regardless of the length of exposure time.
91
-------
1514
3. OTHER HAZARDS '^
Ethylenimine is a highly toxic material and special precautions must
be taken when handling or using it. It is extremely flammable in either
the liquid or vapor form. Ethylenimine vapors may explode when exposed
to electric sparks, static electricity, excess heat, or an open flame.;
Undiluted ethylenimine can polymerize violently in the presence of
acids or acid-forming materials. Extreme care must therefore be taken to
avoid contact with these materials except under controlled conditions
such as in the production of polyethylenimine.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage and Transportation
Glass, 304 and 316 stainless steels and mild steel are satisfactory
materials for handling ethylenimine. Most copper and copper-bearing alloys
are not recommended. Silver solder should never be used to fabricate
ethylenimine handling equipment, since silver forms an explosive compound
with ethylenimine. Almost all rubbers and most plastics are unsatisfactory
because of excessive swelling.
Detailed descriptions for ethylenimine handling and transportation
1514
are provided by Dow Chemical Company. It is important that storage
tanks be provided with protective and warning devices such as temperature
indicators, high-temperature alarms, safety valves, rupture disks and <
check valves to guard against the dangers of accidentally contaminating
the contents of the tank.
Disposal/Reuse
Criteria for disposing of organic ethylenimine waste streams should
be in keeping with handling requirements of the highly toxic and flammable
material. Incineration of organic waste streams containing ethylenimine
should be done under controlled conditions.
92
-------
The aqueous waste solution should be sent to a holding pond or tank
and maintained at or below pH 4 until analysis indicates polymerization is
1514
complete. In this manner the ethylenimine is rendered non-toxic.
Recommended provisional limits for ethylenimine in the environment
are as follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Ethylenimine 0.005 ppm (0.01 mg/M3) 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Ethylenimine 0.05 ppm (mg/1) Stokinger & Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Ethylenirnine is expected to appear primarily as organic waste streams
or as aqueous waste streams in .low concentrations and only rarely as con-
centrated waste. The processing options are briefly described in the fol-
lowing paragraphs, together with recommendations as to their adequacy.
Concentrated Ethyl em'mine
It is important that storage tanks be provided with protective
warning devices such as temperature indicators, high temperature alarms,
safety valves, rupture disks and check valves to guard against the dangers
of accidentally contaminating the contents of the tank. Should acidic or
reactive contaminants enter the ethylenimine storage tank from a process
line or some other source, rapid polymerization or reaction could occur
and make it necessary to hurriedly dump the contents of the tank.
In such a situation, the ethylenimine can be disposed of in two ways.
First, it can be mixed with acidic water in an acid scrubber similar to
1514
that described by Dow. The ratio of acidic water to ethylenimine
should be about 20:1. The exit scrubber solution should be sent to a
covered holding pond or tank. It should be maintained at or below pH 4
until analysis indicates polymerization is complete.
93
-------
Second, the contents of the ethylenimine storage tank can be pumped
directly into a covered pond or holding tank containing an acid solution
maintained at pH 4 or less. The polymerization rate can be somewhat
increased if mechanical mixing is provided. Regardless of which disposal
procedure is utilized the solution should be held in the tank or covered
pond until analysis shows polymerization of the ethylenimine to be
complete.
The above procedures are presented as precautionary measures designed
to cope with unexpected accidental occurrences. It should be emphasized
that if proper protective devices and handling procedures are utilized,
emergencies which require rapid disposal of the contents of storage tanks
should never occur. Dow has stored and consumed large volumes of ethyle-
nimine for a considerable period of time without experiencing a single
1514
emergency incident.
Dow suggests that the polymer solution can then be pumped directly
into the waste stream. This practice is not recommended because (1)
the pH of the solution must first be adjusted to neutral, and (2) it is
not certain that the polymer is biodegradable, although other works0534
describing materials with similar backbones and functional groups support
the supposition that it is. It is suggested that further investigation of
the biodegradability of the ethylenimine polymer be conducted, and until
experimental confirmation is made, this method of disposal should be con-
sidered less desirable than incineration discussed below.
Dilute Ethylenimine Waste Streams
Ethylenimine wastes are expected to appear as organic waste streams or
as aqueous waste streams. Methods for adequately handling the disposal of
dilute ethylenimine waste streams are discussed below.
94
-------
Dilute Organic Waste Streams. Organic waste streams containing
ethylenimine can be adequately disposed of by controlled incineration
where oxides of nitrogen are removed from the effluent gas by scrubbers
1435
and/or thermal or catalytic devices.
Dilute Aqueous Waste Stream. Aqueous waste streams containing
ethylenimine should be held in a tank or covered pond and maintained at
or below pH 4 until analysis indicates polymerization is complete.
The pH is adjusted to 7 and the solution subjected to secondary treatment
consisting of aeration and acclimated activated sludge.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Ethylenimine is not considered a candidate waste stream constituent
for National Disposal Site treatment. Since this material is so highly
reactive a responsive disposal system at the site of occurrence must be
available should contaminants enter the concentrated ethylenimine storage
tank or tank car and cause rapid polymerization. If the recommended pro-
cedure is followed (see the Concentrated Ethylenimine Section), the
resulting material may be handled as aqueous waste at the plant site
along with any dilute aqueous waste being generated there. Any dilute
organic waste streams containing ethylenime should be incinerated at the
plant site under controlled conditions discussed in the paragraph or
Dilute Organic Waste Streams.
95
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7. REFERENCES
0534. Jones, H. R. Environmental control in the organic and petrochemical
industries. New York, Noyes Data Corporation, 1971. p. 181-195.
1433. Kirk-Othmer encyclopedia of chemical technology. 2nd ed., 22 v. and
suppl. New York, Intersciences Publishers, 1963-1971.
1435. John Zink Co. NO destructor. Bulletin number NO 1071 m. Tulsa,
4 p. x x
1492. Merck and Company. The Merck index of chemicals and drugs.
Rahway, New Jersey, 1960. 1,043 p.
1514. The Dow Chemical Company. Ethylenimine. Midland, Michigan, 1965.
63 p.
1570. The Chemical Rubber Company. Handbook of chemistry and physics.
47th ed., Cleveland, 1962. 2,100 p.
1571. Schnell Publishing Company. 1971-72 OPD chemical buyers guide.
1971. 1,584 p.
1670. Chemical Week buyers' guide issue. Chemical Week. 109 (17):1-618,
Oct. 1971.
96
-------
H. M. Name Ethylenimine (190)
IUC Name * ...
HAZARDOUS WASTES PROPERTIES
WORKSHEET
Structural Formula
/ n\
Aziraneu', Dihydroazirine, Aziridinev''
Common Names Azacyclopropaneif ' . Dimethvlemineu; . C.H.N
Ethyl eneiminev<"'
Molecular Wt. 43.07^
Density (Condensed) 0.832
Vapor Pressure (recommended 55 C
160 mm @ 20 C^ '
Flash Point 12 F(4^
Flammability Limits in Air (wt %
Explosive Limits in Air (wt. %)
Solubility -Oiubi0 in ail
Cold Water proportions^ '
C. 0
Melting Pt. -78 C(5) Boiling Pt. 56 C^)
? 20 C .4 CU) Density (gas) 1.48(4) @
Air=l
and 20 0
756 mm & 56 C @
Autolgm'tion Temp. 612 P4^
(• Lower Upper
Lower Upper
Hot Water Ethanol Soluble^1
Others: Soluble in all proportions in most organic solvents' '
Acid, Base Properties Strongly
alkaline^2^
Highly Reactive with Acids, acyl
chlorides, amines, ammonia, hydroxy cpds., thiols, hydrogen
and many other cpds/ ' Polymerizes easily' ' silver, forms an explosive cpd™'
Compatible with Glass, Teflon, mild pj^stainless steel, the following are NOT recommended for
use: copper and copper-bearing al
loys' ''
Shipped in Glass, mild or stainless steer '
ICC Classification III-AGO-WI(4)
Comments Toxicity is very high
4B 240^4^ Coast Guard Classification
and handling must be done with great care^ ' 9>
Borden Inc.. Chemirad Corp.. Dow Chemical r.n , and Pniycrienros j^r
References (1) (1570) (4)
(2) (1492) (5)
(3) 0571)
(1514)
(1670)
-------
PROFILE REPORT
Glycerol Monolactate Trinitrate (GLTN) (524)
1. GENERAL
GLTN is a powerful, high brisance, liquid explosive with many of the
properties of nitroglycerin. The first step in preparation is to esterify
glycerol with lactic acid by prolonged heating of a glycerol lactic acid
mixture containing 4 percent excess lactic acid. The resulting mixture is
then nitrated with a 40:60 mixture of nitric and sulfuric acids maintained
at 20 C. Crude GLTN is extracted from this reaction product with ether,
neutralized with sodium bicarbonate, washed, and dried with calcium
chloride. The product contains about 5 percent nitroglycerin because it
is not considered practical to prepare pure GLTN. GLTN is used as a
0474
gelatinizer for nitrocellulose.
The physical/chemical properties for GLTN are summarized in the
attached worksheet.
2. TOXICOLOGY
GLTN like nitroglycerin, which is present in GLTN, can cause dilation
of blood vessels, headaches, nausea, vomiting, methemoglobinemia, cyanosis,
reduced blood pressure, central nervous system depression, coma and
respiratory paralysis through inhalation, ingestion or skin absorption.
Alcoholic beverages aggravate the health hazard. A Threshold Limit Value
(TLV) for GLTN has not been established, but the TLV of 0.2 ppm for
1142
nitroglycerin would appear to apply to GLTN.
99
-------
3. OTHER HAZARDS
GLTN is a high explosive that is so sensitive to heat and impact that
it undergoes detonation, if confined, when subjected to very mild thermal or
mechanical shock by a flame or percussion. It will explode when heated to
223 C.0474 The material should be handled only by experienced explosive
ordnance personnel.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
As in the manufacture of nitroglycerin, wash waters and acid nitrating
solutions used in GLTN manufacture must be stored until all GLTN has been
decomposed by acid hydrolysis. Recovery and recycling of the spent acid
is possible, after the GLTN has decomposed. Because GLTN is a high explosive
it is recommended that no GLTN be released to the environment.
GLTN is stored as a liquid under the DOD regulations for a Class 9
Explosive.0474 It is not normally shipped as such outside the boundaries
of the plant in which it is manufactured. ;io Department of Transportation (DOT)
classification has been assigned to GLTN, and it cannot be shipped via common
carrier.
The safe disposal of GLTN is defined in terms of the recommended
provisional limits in the atmosphere, and in water and soil.
These recommended provisional limits are as follows:
Contaminant in.Air Provisional Limit Basis for Recommendation
GLTN 0.02 mg/M3* 0.01 TLV*
Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
GLTN 0.1* mg/L* Stokinger and Woodward
Method*
*Estimated from data for similar compounds
100
-------
The waste forms containing GLTN are for the most part surplus and
obsolete military munitions scheduled for disposal, and manufacturing wastes
composed of scrap explosive and explosive-contaminated "inert" materials.
(The "inert" materials are almost always combustible wastes—straw, cardboard,
paperboard, fiberboard, and the like). The quantities by location of the
GLTN, and of the waste forms in which it is contained, are included in the
quantities listed under the heading "High Explosives" in the table covering
"Explosive Manufacturing Wastes," and under the heading "Propellent, nitro-
cellulose Base" in the table for "Obsolete Conventional Munitions" in
Volume 14 of this report.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
GLTN which is collected from spills and catch tanks, and that which is
considered unsuitable for use (contaminated or unstable to KI test), is
currently disposed of by absorption in sawdust, wood pulp or fullers earth,
after which it is carefully burned in an open burning area used for
explosives disposal. If GLTN is spilled on the ground, the contaminated
ground is removed with low-impact tools and burned. Ignition of GLTN is
usually accomplished by placing a black powder squib on the surface of the
absorbed GLTN. As expected, the products of combustion contain considerable
NOV. This method of disposal is not satisfactory unless, due to the
A
specific character of the waste undergoing treatment, the safety hazards of
disposal via the techniques being developed exceed the environmental impact
of the NO generated by open burning.
X
Methods currently under investigation for minimum environmental impact,
low hazard disposal of nitroglycerin are potentially applicable to the
disposal of GLTN. Bacterial degradation and controlled incineration, with
afterburners and scrubbing for abatement of NO , are two techniques being
/\
investigated. Neither of these methods is available for use on GLTN at
this time. Additional research is required.
GLTN wastes should be handled only by experienced ordnance disposal
personnel with a background in GLTN or nitroglycerin disposal.
101
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
GLTN is not a candidate waste stream constituent for National Disposal
Sites, in wastes other than gelatinized nitrocellulose. GLTN, as such, is
not normally transported or used outside the complexes where it is manu-
factured, and facilities for its disposal are available at the sites of
manufacture. It is anticipated that GLTN wastes other than gelatinized
nitrocellulose will continue to be treated at these facilities. Gelatinized
nitrocellulose, as noted in Profile Report (523), is a candidate waste stream
constituent for controlled incineration at National Disposal Sites.
102
-------
7. REFERENCES
0474. Tomlinson, W. R., Jr. revised by 0. E. Sheffield. Properties of
explosives of military interest. Technical Report No. 1740,
Rev. 1, Pictinny Arsenal, 1958. 348 p.
1142. JANAF Hazards Working Group. Chemical rocket propel!ant hazards,
v.2. CPIA Publication No. 194, Silver Springs, Maryland.
May 1970.
103
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Glycerol Monolactate Tn'nitrate (524)
Structural Formula
IUC Name
Common Names GLTN
-- n-unu,
H2-ON6
0 QN02
i n r ru ru
I2-0-C-CH-CH3
/i. explodes
Molecular Wt. 299u; Melting Pt. Boiling Pt. 223 C
Density (Condensed)1.47g/cc @ 23 _C Density (gas) &
Vapor Pressure (recommended 55 C and 20 Q
& 9 0
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
_
0)
Cold Water O.Olg/lOOg at 25 Cu; Hot Water at 60 C Ethanol.
Others: miscible with ether, ether-alcohol, acetone"'
Acid, Base Properties
Highly Reactive with Hydrolysis takes place in add solution^
Compatible w1th_
Shipped in
ICC Class
Comments
ICC Classification not shipped^ coast Guard Classification not shipped^1 ^
References (1) 0474
-------
PROFILE REPORT
Hydrazine Azide/Hydrazine (527)
1. GENERAL
Hydrazine is widely used as a mono-propellant in rocket engines where
the hydrazine is decomposed to expanded volume gaseous products by passage
over a catalyst bed. One of the disadvantages of hydrazine as a propellent
is that it has a relatively high freezing point (1.5 C). Blends of hydra-
zine azide and hydrazine have lower freezing points than hydrazine and
these blends improve rocket performance (Specific Impulse) which has led
to much experimental activity with these blends. The lowest freezing
point (-17.5 C) is obtained for the blend containing 77 percent hydrazine
by weight. It is this blend that will be discussed in this Profile
Report.
Hydrazine azide/hydrazine blends have been prepared by at least three
methods. The first method involves the reaction of sulfuric acid with
sodium azide to form hydrazoic acid which is discharged into hydrazine to
form hydrazine azide. The second method involves the metathesis of sodium
azide and hydrazine sulfate to form hydrazine azide and sodium sulfate.
The third method involves the reaction of butyl alcohol and sodium azide
to give hydrazine azide and C^OHNa.2169'2238 The first method is
preferred, since the hydrazine azide is prepared in an excess of hydrazine
2338
which makes the process very simple and eliminates waste streams.
The third method was abandoned because of low yields and the second method
gave a product contaminated with sodium sulfate that reduced the activity
of decomposition catalyst beds.
Though small quantities of hydrazine azide/hydrazine blends have been
prepared and shipped, it is doubtful that these blends will become an item
of commerce because these blends have been found to be very corrosive to
stainless steel.
105
-------
The physical/chemical properties for a hydrazine azide/hydrazine blend
containing 77 percent hydrazine are summarized on the attached worksheet.
2. TOXICOLOGY
The toxicology of hydrazine azide/hydrazine blends has not been
evaluated. Since hydrazine is the major component of the blends, it can be
assumed that the toxicity will be at least equal to that for hydrazine (see
Profile Report on Hydrazine [212]). A worker at TRW Systems who inhaled
the vapors from a 1-gram sample of a blend for a few minutes in the
laboratory reported a detached feeling that left in about two hours. It
is therefore recommended that exposure to inhalation and skin contact with
vapors of the blends be avoided until the toxicity is defined.
3. OTHER HAZARDS
Hydrazine azide/hydrazine blends will present the same fire hazards as
hydrazine. These are discussed in the hydrazine Profile Report (212). Im-
pact tests indicate the binary system hydrazine azide/hydrazine is not sen-
sitive to 120Kg-cm of shock with one exception. A detonation did occur on
the second bounce when testing one sample saturated with hydrazine azide.
2338
Also, no detonation propagation could be demonstrated for the blends.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Adequate procedures for the safe handlings transportation and storage
of the blends have not been defined because the blends are regarded as an
experimental material. On one occasion 10-lb quantities in a polyethylene
container packed in a wooden box were shipped as a Corrosive Liquid under
a White label. Because hydrazine azide/hydrazine blends attack stainless
steel, it is doubtful that additional quantities will be shipped for
evaluation as a monopropellant.
Personnel who are required to handle wastes containing or contaminated
with hydrazoic acid/hydrazine blends should wear rubber protective clothing,
106
-------
and use forced air supply respiratory equipment. Hydrazine azide/hydrazine
blends will probably be encountered only as excess or contaminated material.
The safe disposal of hydrazine azide/hydrazine is defined in terms
of the recommended provisional limits in the atmosphere, in potable water,
and in marine habitats. These recommended provisional limits are as
follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Hydrazine 0.013 mg/M3 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Hydrazine 0.065 mg/1 Stokinger and Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Because blends of hydrazine azide/hydrazine are an experimental
material, disposal processes have not been established. It is recommended
that material be disposed of by incineration. The blends should be diluted
with water and sprayed into an incinerator with a scrubber similar to that
used for hydrazine (see Profile Report on Hydrazine [212]).
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Because only experimental quantities of hydrazine azide/hydrazine blends
have been prepared, it is not likely that any of the blends will be sent
to National Disposal Sites for disposal. If at some future date the blends
are manufactured, then wastes containing the blends will be candidates for
National Disposal Sites. The techniques for disposal, as discussed in
Section 5, will be similar to those used for disposal of hydrazine wastes.
107
-------
7. REFERENCES
2169. Fedoroff, B. T. Encyclopedia of explosives and related items, v.l
Picatinny Arsenal, 1960. 692 p.
2338. Rockenfeller, J. D. Development of improved monopropellants,
AFRPL-TR-70-108. East Hartford, Connecticut, United Aircraft
Corporation, 1970. p.29. •
108
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydrazine Azide/Hydrazlne (527)
IUC Name Hydrazim'um Azlde/Hydrazine
Common Names
Structural Formula
Weight ratio: 77 parts N2H4> 23 parts N
compound"^ m
Molecular Wt. a blend not a Meltlna Pt. -17.5Cu; Boiling Pt._
Density (Condensed)1-083 g/cc g 25
Vapor Pressure (recommended 55 C and 20 0
7.7 torr
20
-(1)
23.5 torr @ 40 C
Density (gas)_
(1)
520 torrg 55 Cv
Flash Point
Autoignition Temp._
Flamiability Limits in Air (wt %) Lower
Explosive Limits in Air (wt.
Lower
Solubility
Cold Water_
Others:
soluble^1)
Hot Water soluble1
Upper.
Upper_
(1)
Ethanolslightly soluble
Acid, Base Properties
Highly Reactive with oxidizing agents('X
Compatible with
. polyethylene
*1 ^
Shipped in polyethylene enclosed in a wood boxu)
ICC Classification corrosive liquid(1) coast Guard Classification,
Comments Experimental monopropellant. not produced
References (1) 2338
109
-------
PROFILE REPORT
Hydroqulnone (220)
Hydroquinone is a white crystalline solid of moderate to high toxieity.
It is widely distributed in nature as a component of the glucoside arbutin,
1433
found in the leaves of many plants. Its performance as a reducing agent
provides the basis for its widespread use as a photographic developer and
antioxidant.
There are a number of patented processes for the manufacture of hydro-
quinone but the method employed by the Eastman Chemical Products Division of
Eastman Kodak, in Kingsport, Tennessee, is believed to be representative of
those which are of commercial importance. The process used at Kingsport
is essentially a three-step operation. In the first step aniline is
oxidized to quinone in the presence of an excess of manganese dioxide and
sulfuric acid. In the second step, quinone is steam distilled from the re-
action liquor and immediately brought into contact with a water suspension
of iron dust that reduces the quinone to hydroquinone. The third step is
the purification of hydroquinone to the quality desired.
Hydroquinone is available in technical and photographic (higher purity)
1433
grades and is shipped in TOO-and 325-lb (net) fiber drums. In addition
to Eastman, the other domestic producers of technical grade hydroquinone are
Carus Chemical Company, Diamond Shamrock Corporation, and the DuPont
Company.
million Ib.
1718
Company. Their combined production during 1970 was approximately 13.6
The principal large-scale use of hydroquinone is as a reducing agent
1433
in photographic developers. For this application it is used in dilute
1686
aqueous solution; a common concentration is 10 g in a liter of developer.
It is also employed as an antioxidant in a variety of products including
111
-------
rubber and edible fats and ®ils. The antioxidant activity of hydro-
quinone is also the basis f@t? Us use as a polymerizatiom inhibitor
(stabilizer) for reactive vinyl monomers. When used as an antioxidant-
stabilizer hydroquinone or its derivatives generally comprise less than
1433
2 percent of the materials involved.
The physical/chemical properties of hydroquinone are summarized in the
attached worksheet.
2. TOXICOLOGY0756' 1492
Under normal conditions of use, (low concentrations, moderate tempera-
tures, closed systems, etc.) hydroquinone does not present a serious hazard.
However, ingestion of relatively large quantities of material is potentially
dangerous. For example, the ingestion of 1 g by an adult has been reported
to cause nausea, vomiting, a feeling of suffocation, shortness of breath,
cyanosis, convulsions, delirium and collapse. Death has followed the in-
gestion of 5 g of the material. Many of these symptoms may be attributable
to the strong excitation effect of hydroquinone on the central nervous sys-
tan.1433
Skin contact may result in dermatitis, although the actual causitive
agent may be quinone0 formed by the oxidation of hydroquinone in the pre-
sence of moisture. Quinone may also be responsible for the corneal
staining and opacification which has occurred in workers exposed for pro-
longed periods to concentrations of vapor not high enough for the production
of systemic effects.
A Threshold Limit Value (TLV) of 2 mg/M of air has been recommended
for this material.
3. OTHER HAZARDS
Hydroquinone is considered to be only a slight fire and explosion
rd when expose
lease toxic fumes.
hazard when exposed to fire or heat. However, such exposure may re-
112
-------
Caution should be exercised when contacting hydroquinone with strong
oxidizing agents„ since it is a potent reducing agent. A highly exothermic
1569
reaction with sodium hydroxide has also been reported.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
The safe handling and use of hydroquinone requires that care be taken
to avoid prolonged exposure to its dust and vapor through use of dust masks
and gloves. Careful design of equipment to prevent leaks during manufacture
and use, and adequate ventilation are very important. To further mini-
mize exposure during the manufacturing process, Eastman requires that
employees be rotated through various operations in the department and that
uniforms be changed and showers taken at the end of each workday.
Hydroquinone is shipped in 100-and 325-lb fiber drums which do not re-
quire special hazardous material labels.
In general, the precautions necessary to prevent the contamination of
hydroquinone and thus guard its economic value are adequate to assure its
safe handling.
Disposal/Reuse
Purification of hydroquinone by recrystallization is a normal phase of
the manufacturing process and hydroquinone users with the required
equipment may employ this technique to recover slightly contaminated material.
An adequate process for
visions for limiting
for oxidation to the msr© velatil©
and vapor 1s probably not a §©
1s In the fora oi
disposal of hydroquinone must include pro-
of dust and vapors and the opportunity
toxic qulnone. The problem of dust
sine© almost all hydroquinone waste
solutions of hydroquinone or, in the case
113
-------
of spent photographic developer, hydroquinone monosulfinate. Oxida-
tion to quinone is not rapid in acidic or neutral solutions and can be pre-
vented in the presence of another reducing agent such as sodium sulfite
1686
which is present in photographic developers.
Aqueous waste solutions are amenable to common municipal secondary
1686
waste treatment processes. The hydroquinone molecule, containing only
carbon, hydrogen and oxygen atoms, can also be burned in a properly designed
and operated incincerator.
Recommended provisional limits for hydroquinone 1n the environment
are as follows:
Contaminant and Basis for
Environment Provisional Limits Recommendation
Hydroquinone in 0.02 mg/M 0.01 TLV
air
Hydroquinone in 0.10 ppm (mg/1) Stokinger and
water and soil Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The preferred processing options for the disposal of hydroquinone
wastes are briefly described in the following paragraphs together with
judgments as to their adequacy.
Option No. 1 - Waste Water Treatment
The major portion of hydroquinone wastes are expected to be in the
form of dilute aqueous solutions. Hydroquinone can be effectively removed
from such waste streams by conventional secondary sewage treatment (bio-
chemical oxidation) methods. Of those processes, activated sludge is the
most efficient, with aerated lagoons or trickling filters equally effective
1686
if sufficient residence time for complete decomposition 1s available.
114
-------
Anaerobic processes (faculative ponds) are not recommended for hydroquinone
waste streams which contain components incorporating sulfur atoms (e.g.,
photographic process effluents) because of the danger of HgS production.
Concentrated hydroquinone wastes may also be treated by common munici-
pal secondary waste water treatment methods after adequate dilution. The
required dilution will depend upon the capacity of the treatment plant in
l fiftfi
question; hydroquinone exerts a BOD of 1.12 Ib/lb of waste.
The direct introduction of untreated hydroquinone wastes into surface
or underground waters is not recommended because of the known high toxicity
of the material to fish and other fauna.
Option No. 2 - Incineration
Incineration of hydroquinone in a well designed and operated incinerator
is an acceptable waste disposal method. Hydroquinone should be combusted at
a minimum temperature of 1,800 F for a minimum of 2.0 seconds. Care must be
taken to avoid leakage of unburned hydroquinone vapors, and to remove harm-
ful combustion products (e.g., S02, NOX) produced by other components in the
waste mixture.
The incineration option is most applicable to concentrated hydroqui-
none wastes and in areas removed from ready access to appropriate municipal
or private secondary treatment facilities.
Option No. 3 - Land Burial
Landfill or deep well disposal of hydroquinone waste streams is not
generally recommended because of the danger of release of this water-soluble,
toxic substance to the environment. In addition to possible leaching of
hydroquinone by rain or subterranean water, its possible oxidation to the
more toxic, volatile, and less biodegradable quinone must be considered as
contraindicative for burial disposal methods. However, a landfill meeting
California Class I requirements is adequate. (See Volume 3, Landfill Disposal
Process Description.)
115
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Hydroquinone is not a candidate waste stream constituent for disposal
at National Disposal Sites. Waste streams containing this material can be
effectively and safely disposed of, at or near the sites of waste generation,
by conventional waste water treatment of controlled incineration.
116
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1569. National Fire Protection Association. Manual of hazardous chemical
reactions 1971. 4th ed. NFPA No. 491M. Boston. 308 p.
1571. OPD Chemical buyers directory. New York, Schnell Publishing Company,
1971. 1,584 p.
1679. Shearon, W. H. Jr., Davy, L. G. and H. Von Bramer. Hydroauinone
manufacture. Industrial and Engineering Chemistry. 44(9):1730-
1735, Aug. 1952.
1686. Personal communication. L. E. West, Eastman Kodak Company, to
H. E. Green, TRW Systems, May 9, 1972.
1718. United States Tariff Commission. Synthetic organic chemicals, United
States production and sales, 1970. TC publication 479. Washington,
U.S. Government Printing Office, 1972. 262 p.
117
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Hydroquinone (220)
Structural Formula
IUC Name 1,4-dihydroxybenzene
Common Names ^ M,4-benzenediol. quinol, hydroquinol
HOC6H4OH
Molecular Wt. 110.1 Melting Pt/1) 170.5 C Boiling Pt/^286.2 C
Density (Condensed) ^ n .353 @ 20/4 C Density (gas^^.fli {
Vapor Pressure^ \Vecommended 55 C and 20 C)
1 mm @ 132.4 C 9 ^^
Flash Point (1)329 F (cc) Autoignition Temp. ^Oft) F
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility (2)
Cold Water 5.8g/100g solution @ 15 C 9.4g/100q solution Ethanol Very soluble
Others: Ether @ 28'5 C
Acid, Base Properties Neutral
Highly Reactive with Oxidizing agents^ , sodium hydroxide^ '
Compatible with_
Shipped in Fiber drums^ '
ICC Classification • Coast Guard Classification
Comments Source^ ': Allied Chem.. Diamond Shamrock, Eastman r.hemiral Prndut
Mallinckrodt Chemical Works. J. T. Baker Chemiral rn. „ r.amg r.hpmirai rn
References (1) 0766 (4) 1679
(2) 1433 (5) 1571
(3) 1569
118
-------
PROFILE REPORT
Maleic Anhydride (249)
1. GENERAL
Maleic anhydride is a toxic solid at room temperature, appearing as
white rombic needles in the crystalline form. The products of commerce
are shipped as flakes, briquettes and as a liquid at temperatures between
1497
55 and 60 C. Most of the maleic anhydride produced commercially is
1433
made by the catalytic oxidation of benzene in the vapor phase. It is
primarily used in polyester resins, lesser quantities being used to make
fumaric acid, agricultural chemicals, alkyd surface coatings, lubricants,
copolymers, and plasticizers.
As of 1970, large scale commercial facilities for the manufacture of
maleic anhydride (production greater than 20 million Ib annually) were
operated by six companies, Monsanto producing 75 million Ib of the 237 mil-
lion Ib produced annually. Physical/chemical properties are summarized
in the attached worksheet.
2. TOXICOLOGY
Maleic anhydride is a strong irritant to the skin, eyes and the mucous
membrane. It is very irritating to the eyes and can cause painful conjunc-
tivitis and possible corneal dullness. If it is left in contact with the
skin, painful irritation can result, particularly if the skin is moist.
Oral ingestion may cause death or permanent injury after very short exposure
:ti ve
1497
to small quantities. A detailed description of personnel protective
equipment is provided by the Manufacturing Chemists Association Inc.
for handling both the solid and molten material. Toxicological effects in
o
man are characterized by a Threshold Limit Value (TLV) of 0.25 ppm (1 mg/M ).
119
-------
3. OTHER HAZARDS
Maleic anhydride is an irritant to the skin and mucous membrane
T A r\i
cially in the presence of moistun
hazard when exposed to heat or flame.
1497
especially in the presence of moisture. It is also a moderate fire
This material emits toxic fumes when heated and can react on contact
with oxidizing materials such as the alkali metals or amines at temper-
atures above 150 C. The flammable limits (by volume) are 1.4 percent to
7.1 percent. It is recommended that the material not be heated above
70 C1570 since the closed cup flash point is 102 C.1497
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Precautions must be taken to guard against health and fire hazards
whenever maleic anhydride is handled. Although maleic anhydride does not
1433
present a severe fire hazard, it is recommended that spark-resistant
tools be used in handling the material and explosion venting be provided
in general construction of equipment and buildings in which flammable
1497
vapors or dusts are liable to concentrate.
Maleic anhydride is shipped as flakes, briquettes and in the molten
form. Briquettes and flaked maleic anhydride are packaged and shipped in
multiwall paper bags, fibre drums and metal drums. Molten maleic anhydride
is shipped in tank cars and tank trucks constructed of mild or stainless
steels.1497
A description of personnel protective equipment to be used when handling
maleic anhydride is available from the Manufacturing Chemists Association,
1497
Inc. This includes a discussion of eye, respiratory, head and body
protection.
120
-------
Disposal/Reuse
Most of the maleic anhydride produced commercially is made by the
1433
catalytic oxidation of benzene in the vapor phase. It is also obtained
as a byproduct in the oxidation of naphthalene and from butylenes by catalytic
vapor-phase oxidation similar to the benzene process. The catalytic
1499
vapor-phase oxidation is a continuous process having no contact with water
since water is not used or generated in the process. Hence, any contami-
nation of water would probably stem from the washdown of equipment, such
as storage tanks or tank cars, and clean up of spills. This in itself does
not present a major problem since maleic anhydride is easily hydrolized by
water to maleic acid which is readily soluble in water and may be easily
neutralized with sodium hydroxide. The resultant dilute aqueous solution
will generally exhibit no evidence of toxicity, taste or odor problems in
the context of disposal to municipal or industrial treatment plants, this
1497
neutralized solution is readily oxidized biologically.
Maleic anhydride and maleic acid are found as dilute wastes in the
tars which appear as bottoms products from the vacuum columns in the manu-
facturing processes. One manufacturer currently disposes of this waste
in a privately owned sanitary landfill. Test wells surround the landfill
to check migration of any material. The tars are also used as boiler feed
1499
in some plants thus disposing of the material by incineration.
Any method of maleic anhydride disposal must be evaluated with respect
to its environmental impact. Recommended provisional limits of maleic an-
hydride in the environment are as follows:
Contaminant and Basis for
Environment Provisional Limits Recommendation
Maleic Anhydride 0.0025 ppm (0.01 mg/M3) 0.01 TLV
in Air
Maleic Anhydride 0.05 ppm (mg/1) Stokinger and
in Water and Soil Woodward Method
121
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Maleic anhydride is expected to appear in low concentrations in tars
produced during manufacture. It is anticipated that it will also be present
as maleic acid in water used to clean up spills or equipment. Concentrated
maleic anhydride waste will appear as contaminated or off grade product.
1499
Generally, the contamination will be caused by hydrolysis or the material
will be discolored making it unfit for use in some manufacturing processes.
The processing options are briefly described in the following paragraphs
together with recommendations as to their adequacy.
Concentrated Maleic Anhydride
Essentially, four options are available for the disposal of concentrated
maleic anhydride wastes. These are recycle, incineration, landfill and deep
sea burial.
By far, the most appropriate method of disposal of concentrated maleic
anhydride wastes is to recycle the material. This is accomplished either
by locating a consumer willing to use low grade material or by reprocessing
1499
the material at the plant for captive use. If recycling is impossible,
controlled incineration is the disposal method of choice. Incineration
must be controlled to ensure that the waste maleic anhydride, as well as
any other material in the waste stream, is completely oxidized to nontoxic
combustion products.
The use of landfills for the disposal of concentrated maleic anhydride
wastes should be considered only when the options of recycle and incineration
are impractical and the landfill is of the California Class I type. The
use of deep sea burial is not recommended since injury to aquatic life is
possible and once dumped, control of the material is lost.
122
-------
Dilute Waste Streams
The following sections will discuss the methods used to dispose of
waste streams containing maleic anhydride in dilute form.
Option No. 1 - Secondary Treatment. Waste water containing maleic
acid from maleic anhydride equipment wash downs can be adequately handled
in municipal sewers after neutralization of the dilute solution. Once
neutralized by NaOH addition and in dilute aqueous solution there is no
evidence of toxicity, taste or odor problems in the context of disposal
to municipal or industrial treatment plants since the sodium maleate (in
dilute form) is readily oxidized biologically.
Option No. 2 - Incineration. Incineration of the tar byproducts
containing maleic anhydride is an adequate means of disposing of this
1944
material particularly since the tars can be used as fuel in boilers.
Care must be taken to ensure that complete oxidation of the maleic anhydride,
as well as any other materials in the waste stream, is attained.
Option No. 3 - Sanitary Landfill. Sanitary landfills are currently
used to dispose of tars containing maleic anhydride and maleic acid.
This method is recommended only when the landfill utilized meets
California Class I landfill standards since this will minimize the pos-
sibility of water contamination.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Maleic anhydride is not judged to be a candidate waste stream constit-
uent requiring National Disposal Site treatment since the various waste forms
containing this material can be treated at the site of generation with common
industrial and municipal techniques. Also, some concentrated maleic an-
hydride wastes, depending on other waste stream constituents, are particu-
1499
larly well suited for recycling and this is currently being done.
123
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed. '
New York, Reinhold Publishing Company, 1968. 1,251 p.
1316. Noller, C. R. Chemistry of organic compounds. 2d ed. Philadelphia,
W. B. Saunders, 1957. 978 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers. 1963-1971.
1497. Manufacturing Chemists Association, Inc. Properties and essential
information for safe handling and use of maleic and anhydride.
Chemical Safety Data Sheet SD-88. Oct. 1962. 13 p.
1499. Personal communication. T. Morgan, Tenneco Chemicals Inc., to
W. P. Kendrick, TRW Systems, Apr. 3, 1972.
1501. Faith. W. L. , D. B. Keyes, and R. L. Clark. Industrial chemicals.
3d ed. New York, John Wiley and Sons Inc., 1950. 852 p.
1502. Personal communication. D. Hosmer, Monsanto Chemical Company, to
W. P. Kendrick, TRW Systems, Apr. 3, 1972.
1506. Chemical profiles. jjr^Oil, Paint, and Drug Reporter. Chemical
Marketing Newspaper, New York, Schnell Publishing Company, Inc.
200 p.
1507. Maleic anhydride. Technical Bulletin, Tenneco Chemicals Inc.,
Heyden Division, New York. 16 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, 1966. 1,500 p.
1571. OPD Chemical buyers directory. New York, Schnell Publishing Company,
1971. 1,584 p.
124
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Maleic Anhydride (249)
IUC Name
Common Names Tcxilic Anhydride rcis-butenedioic
Anhydride
Structural Formula
C4 H2 °3
Molecular Wt.
98.06
Melting Pt. 56 C
Density (Condensed) 1.314 @ 60
Density (gas) 3.4
(3)
Boiling Pt. 197-9 c
(1)
Vapor Pressure (recommended 55 C and 20 C)
1 mm Hr
44 c
Flash Point 218 F (c/c)
"(3) •
Autoignition Temp.890 F
(3)
Flammability Limits in Air'(Vol. %) Lower 1.4
Explosive Limits in Air (wt. %) Lower
Upper 7.1
Upper
Solubility
Cold Water Soluble
Hot Water Decomposes to
Ethanol
Others: Soluble in Ether, Acetone, Chloroform
the acid
Acid, Base Properties
Highly Reactive with Alkali Metals, amines, any oxidizing agent
Compatible with Mild Steel. Stainless Steel, Aluminum
Shipped in Drums and tank cars when liquid; paperbags. drums when solid
ICC Classification 20, 28 Coast Guard Classification
Comment;; Mfg.: Allied Chem. Corp.; Ciba Products Co.; Eastern Color. & Chem. Co.
(2\
Mnnsantn Co,; Tar Residuals Inc.; USS Chemicalc;
References (1) 1570
(2) 1571
(3) 0766
125
-------
PROFILE REPORT
Manganese Methyl cyclopentadienyltricarbonyl (502)
1. GENERAL
Production
There is one producer of manganese methyl cyclopentadienyltricarbonyl
,) in the United States, the Ethyl Corporation, which produces
(2128 2177)
an undisclosed amount at its Orangeburg, South Carolina plant. ' ;
Ethyl owns at least six, patented processes for the production of ChLC(.H.Mn(CO)o
1433 2177
of which only one is currently in use. Methyl cyclopentadiene is
reacted with metallic sodium to form methyl cyclopentadienyl sodium. This in
turn is reacted with manganese chloride to yield biscyclopentadienylmanganese
plus sodium chloride. The mixture is scrubbed with oil and water and the
resultant pure biscyclopentadienylmanganese is reacted with carbon monoxide
to yield the manganese methylcyclopentadienyltricarbonyl . The final product
contains traces of manganese cyclopentadienyltricarbonyl, which are
2174
considered acceptable.
Use
At present, CH3C5H4Mn(CO)3 is used as an additive to distillate type
fuel oils to improve combustion under the trade name CI-2. The utilities
industries have found it particularly useful for reducing the opacity of
21 7i
their stack gases.
the manganese oxides.
pi "1C
their stack gases. As a fuel component it is combusted completely to
The Ethyl Corporation hopes to expand its use considerably as an anti-
2128
knock additive to gasoline (trade name AK-33X) to replace lead tetraethyl.
It is anticipated that, beginning with the 1975 model year, cars will have
to be equipped with catalytic afterburners to satisfy the projected
pollution requirements. At present, all proposed catalysts are poisoned by
lead, but not by manganese; hence the interest in CH-^CgH^lMCO).,. Projected
additions range from 0.025 to 0.05 g Mn/gal. gasoline as Mn metal, compared
to the present addition of 2.3 to 2.4 g Pb/gal. gasoline as Pb metal. At
127
-------
$2.10/lb m tank car quantities, however, it is not economically competitive
2175
with lead tetraethyl at present.
pi -ic
It has been experimentally determined that all Mn that would be
emitted from automobile exhausts would be in the form of the oxides. The
CI-LC5H.Mn(CO)3 is unstable with respect to sunlight, and decomposes slowly
to a brown flocculent material. No chemical analysis has ever been
PI 7fi 91 77
performed on these decomposition products. I/DS<:I//
2. TOXICOLOGY
Health and Safety Standards
The HEW 1971 Annual List of Toxic Substances reports that 0.12 mg/nr
of manganese cyclopentadienyltricarbonyl produced symptoms of pulmonary
disorder and disorders of the central nervous system in man. The mode of
entry was by inhalation. Since the methyl cyclopentadienyltricarbonyl is
chemically similar to the cyclopentadienyltricarbonyl, it is reasonable to
assume that manganese methyl cyclopentadienyltricarbonyl would produce the
same effects.
Epidemiology
Since the reported symptoms of manganese cyclopentadienyltricarbonyl
poisoning are the same as those reported for manganese metal poisoning,
i.e., pulmonary disorders and impairment of the central nervous system, it
is reasonable to assume that the mechanisms are similar. It is generally
believed that manganism is caused by enzyme inhibition in the central
nervous system. CaNa2 EDTA administered intravenously provides relief in
the early stages of disease; prolonged chronic illness is essentially
incurable. The epidemiology of manganese poisoning is discussed more
fully in the Profile Report on Manganese (499).
2197 2198
On the basis of experimental evidence, />tl*° Russian workers suggest
an LD50 of 150 mg/kg for white mice and an LD50 of 80 mg/kg for white rats
for manganese cyclopentadienyltricarbonyl. Administration was by direct
-------
insertion into the gastrointestinal tract. In addition to the symptoms of
manganism, extensive hemolysis was found in the subject animals. It is
postulated that this was due to cyclopentadiene which split off the original
molecule.
3. OTHER HAZARDS
Manganese methyclopentadienyltricarbonyl is flammable with a flash
pi TiT
point in excess of 200 F. It decomposes slowly in sunlight to
unidentified products whose potential hazards cannot be evaluated until such
time as they are characterized.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage, and Transportation
Manganese methylcyclopentadienyltricarbonyl is a flammable liquid of
relatively low vapor pressure (0.08 torr at 20 C) and high flash point
pi yc
(greater than 200 F). As a component of gasoline, the maximum
anticipated concentration is 0.20 g/gal. or 0.05 g Mn/gal gasoline as Mn
2128
metal. CH-CrH.MnCCOU must be stored in opaque containers, for it is
decomposed by sunlight to a brown flocculent material of unknown composition.
2174 2177
' Otherwise, it remains quite stable below its flash point, which
21 75
is in excess of 200 F. It should be shipped in steel drums or tank cars,
suitably labeled as a Class B poison, flammable liquid.
Disposal/Reuse
When distillate fuels or gasoline containing CH~C5H.Mn(CO)o are
combusted, the only manganese compounds released are mixtures of the oxides.
2128
Field studies of stack emissions from stationary sources indicated
concentrations of 0.1 to 0.2 yg/m 1,000 ft downwind (compared to 0.01 to
3 3
0.2 yg/m background) and 0.03 to 0.05 yg/m 1,500 ft downwind (compared to
o
0.02 yg/m background). On-site soil samples contained 12 to 109 ppm Mn,
while off-site soil samples contained 28 to 61 ppm Mn. The samples may
have been contaminated with indigenous coal dust which runs 1,000 ppm Mn.
129
-------
Since the toxic effects of manganese methyl cyclopentadienyltricarbonyl
are believed to be due to its manganese component, the acceptable criteria
for its release to the environment are defined in terms of the following
provisional limits.
Basis for
Contaminant and Environment Provisional Limits Recommendation
Manganese Methyl cyclopenta- 0.05 mg/M3 as Mn 0.01 TLV for Mn
dienyltricarbonyl in Air
Manganese Methyl cyclopenta- 0.05 ppm as Mn Drinking Water
dienyltricarbonyl in Water Standard for Mn
and Soil
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
As an additive to gasoline or other fuels, CHgCj-HJMCOK compares very
favorably to lead tetraethyl. It has a lower vapor pressure (0.08 torr vs.
0.47 torr at 20 C), a lower anticipated concentration in gasoline (0.20 g/gal.
vs. 3.75 g/gal. for Pb(C2H5).4), and is probably somewhat less toxic (symp-
toms induced in man at 0.12 mg/M vs. a Threshold Limit Value (TLV) for
o
Pb(C9H(-K of 0.075 mg/M ). Its handling, storage, and transportation under
c. ID T-
its classification as a Class B poison, flammable liquid, are adequate at
present and for the foreseeable future.
Its susceptibility to decomposition under the action of sunlight is
widely known, and the producer and users exercise care that it not be exposed.
The decomposition products have not been characterized, however, so any
possible hazards associated with decomposition cannot be evaluated at this
time 2193S219592174,2176,2177
Currently, the addition of 2.3 to 2.4 g Pb/gal gasoline as
•5
provides a maximum urban air concentration of 2.3 yg/m , or 1/100 of the
TLV for Pb. If it is assumed that lead tetraethyl is replaced completely
by manganese methyl cyclopentadienyltricarbonyl in the concentration of 0.025
21 28
to 0.05 g Mn/gal . gasoline, then the Mn air level from automobile
exhausts will be approximately fifty times less than the present Pb level,
-------
or 1/1250 of the TLV for Mn. It is unlikely that this would present a
health hazard, notwithstanding the apparent lack of safety margin in the
3
present TLV of 5 mg/m for Mn.
The Chemistry and Physics Branch of the U.S. Environmental Protection
Agency is sponsoring an experimental study of CH3C5HJ1n(CO)o additions
to gasoline, which will be conducted by the Dow Chemical Company. Initial
results are expected in November 1972. Similarly the Chemistry and Physics
Branch will soon begin a joint study with the U.S. Navy on the consequences
of CH3C5H.Mn(CO)3 additions to jet fuel used in engine overhauling and
testing.
Production of Manganese Methylcyclopentadienyltricarbonyl
There are two waste streams associated with the production of manganese
methylcyclopentadienytricarbonyl by the Ethyl Corporation in its Orangeburg,
South Carolina facility: an oil soluble stream, and a water soluble
2177
stream. These streams are
options available for each one.
Oil Soluble Stream
2177
stream. These streams are treated individually and there are several
Option No. 1 - Incineration of the Oil Stream and Venting to the
Atmosphere. This is the present procedure. Any organic manganese compounds
'?
present are converted to the oxides. There is no monitoring of manganese
emissions, although state requirements with regard to opacity, S02, and
oxides of nitrogen are being met consistently. It is necessary to
determine the emission level of manganese before an evaluation can be made
with regard to the adequacy of this option.
Option No. 2 - Incineration of the Oil Stream and Wet Scrubbing of
the Exhaust Gases. If it is determined that manganese emissions from the
— " " 3
incinerator cause the Threshold Limit Value of 5 mg/M to be exceeded
within the plant or the provisional limit of 0.05 mg/M to be exceeded
131
-------
outside of the plant, a wet scrubber could be installed to bring the air
emissions to an acceptable level. The effluent from the scrubber could
be combined with the water soluble waste stream.
Hater Soluble Stream
Option No. 1 - Discharging_the Water Stream Into the Local River.
This is the present procedure. It is probably unsatisfactory since the
effluent runs 4.2 mg Mn/1 and the U. S. Public Health Service recommends
a maximum Mn concentration of 0.05 ppm in drinking water. However, the
plant influent which is derived from ground water, runs 2.6 mg/1. If the
river water contains significant manganese (close to the limit) this
technique is not adequate.
Option No. 2 - Precipitating the Manganese in a Settling Pond Prior
to Discharging into the Local River. If the manganese contained in the
effluent is indeed objectionable, it can be precipitated quite easily by
temporary storage of the effluent in a settling pond in which the pH is
adjusted within the range 8.5 to 9 by the addition of lime. Water of this
pH would meet USPHS specifications with regard to pH and would be
essentially manganese-free.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
At present, manganese methylcyclopentadienyltricarbonyl does not
constitute a hazard or threat to the general public. The manganese oxides
resulting from its combustion as a gasoline additive would not constitute
an air pollution problem, and would represent a considerable improvement
over the combustion products of the lead tetraethyl currently in. use.
The handling, storage, and transportation of CH3CgH^Mn(CO)3 are
adequate at present and for the foreseeable future, providing the
manufacturer's admonitions to avoid exposure to sunlight are obeyed. The
photochemical decomposition of CH^CgHaMnCCOK has been observed, but not
characterized. There is a small, but finite chance that poisonous manganese
2181 2195
carbonyls are evolved. ' It is recommended that the decomposition
products be characterized in a laboratory setting.
132
-------
It is recommended that a determination be made of manganese air
emissions resulting from the incineration of the oil soluble waste stream
at the Ethyl Corporation's production facility at Orangeburg, South Carolina.
If it is found that the emissions exceed recommended levels, a wet scrubbing
unit should be installed to remove them. The effluent from the scrubbing
unit could then be mixed with the water soluble waste stream.
The plant influent at 2.6 mg Mn/1 is already considerably higher than
the U. S. Public Health Service recommended Drinking Water Standard of 0.05
mg/1. It is raised to 4.2 mg/1 within the plant. These values have been
reported to the U. S. Army Corps of Engineers and the Environmental
2177
Protection Agency. If it is desired to reduce the Mn content, the
addition of lime in a settling pond would prove a simple expedient. The
precipitation of the manganese would not involve the creation of any
volatiles.
Manganese methylcyclopentadienyltricarbonyl can be handled quite
adequately at the industrial level and is therefore not a candidate waste
stream constituent for national disposal.
133
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corp., 1968. 1,251 p.
1312. Christensen, H.E. Toxic substances: Annual list. U.S. Department
of Health, Education, and Welfare. Health Services and Mental
Health Administration. National Institute for Occupational Safety
and Health. Rockville, Maryland, 1971, 512 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 22 v. and suppl.
New York, Interscience Publishers, 1966. 899 p.
2128. Personal communication. L. B. Andrew, Ethyl Corp. to M. Appel, TRW
Systems, July 10, 1972.
2174. Personal communication. G. Robinson, Ethyl Corp. to M. Appel, TRW
Systems, July 20, 1972.
2175. Personal communication. Mr. Rowe, Ethyl Corp. to M. Appel, TRW
Systems, July 20, 1972.
2176. Personal communication. E. Desmond, Ethyl Corp. to M. Appel, TRW
Systems, July 20, 1972.
2177. Personal communication. T. Taylor, Ethyl Corp. to M. Appel, TRW
Systems, July 21, 1972.
2181. Basolo, F. and R. H. Pearson. Mechanisms of inorganic reactions,
2d ed. New York, Wiley, 1967. 701 p.
2193 Personal communication. D. Hanson, U.S. Environmental Protection
Agency to M. AppelI, TRW Systems, July 26, 1972. Manganese
methylcyclopentadienyltricarbonyl.
2194. Personal communication. G. Roush, Ethyl Corp. to M. Appel, TRW
Systems, July 27, 1972.
2195. Personal communication. J. Maran, U. S. Environmental Protection
Agency to M. Appel, TRW Systems, July 27, 1972.
2197. Arkhipova, 0. G., el al. Toxic properties of manganese
methylcyclopentadienyl antiknock substances. U.S.S.R. Literature
on Air Pollution and Related Occupational Disease, 12:85, 1963.
2198. Arkhipova, 0. G., et al. Toxicity within a factory of the vapor of
' a new antiknock compound. Hygienic Sanitation, 30(4):40, 1965.
134
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name Manganese methylcyclopentadienyltricarbonyl
(502)
Common Names CI-2, AK-33X
Structural Formula
218
(1)
Molecular Wt.
Density (Condensed) 1.3884 T
1.5 C
Melting Pt.
20 C Density (gas)
(2)
Boiling Pt. 228-6 c
@ (extrapolated
Vapor Pressure (recommended 55 C and 20 0
0.08 mm Hg (3 20 C 9.3 mm Hgg 100 C
Flash Point
200F
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
Lower
Solubility
Cold Water_
Others:
insoluble
most organic solvents
Hot Water insoluble
Upper.
Upper_
Ethanol soluble
Acid, Base Properties_
Highly Reactive with
Compatible with_
Shipped in steel drums (1 gal. 5 gal. 55 gal) tank cars (4000, 6000, 8000 gal)
ICC Classification C1ass B poison, flam, liquid.Coast Guard Classification
Comments decomposes in sunlight to unidentified prnHnrtc
References (1) 2176
(2) 2176
135
-------
PROFILE REPORT
Nitroaniline (300)
1. GENERAL
The nitroanilines are yellowish crystaline substances described as being
highly toxic. They comprise three possible position isomers; 2-(mp:71 C),
3-(mp:112 C), and 4-nitroaniline (mp:146 C). All three isomers have
been used as dyestuff intermediates, although pigments using 4-nitroaniline
have now been virtually supplanted by inorganic pigments and other more
lightfast materials.
2-Nitroaniline is prepared by ammonalysis of ortho-nitrochlorobenzene
or by nitration and desulfonation of sulfanilic acid. It is used to prepare
1433
a few azo and anthraquinone dyes. 3-Nitroaniline is prepared by partial
reduction of 1,3-dinitrobenzene. It is used in organic synthesis and as a
1433
dye intermediate. 4-Nitroaniline is prepared by ammonolysis of
4-nitrochlorobenzene or by nitration of acetanilide followed by hydrolysis.
Its principal uses and their approximate share of production are: rubber
antioxidant, 40 percent; gasoline additives, 20 percent; dyes and pigments,
20 percent; Pharmaceuticals and veterinary, 7 percent; agricultural chemicals,
three percent; miscellaneous, 10 percent.
Commercial facilities for the manufacture of 4-nitroaniline are
(\ 7
operated by American Aniline (2 X 10 Ib/yr), Monsanto (10 Ib/yr), and
Universal Oil (3 X 106 Ib/yr). Southern Dyestuff Company makes limited
quantities for captive use. Sources for the 2- and 3-isomers may be
1571
found in OPD Chemical Buyers Guide.
137
-------
2. TOXICOL0.6Y 1498
Nitroaniline is a hazardous material because of its ability to
produce cyanosis upon absorption into the bo.dy. Significant adsorption
may occur either by inhalation of the dust or from contact with the skin.
While skin exposure may be hazardous, the rate of absorption through the
intact skin is relatively low. Nitroaniline is mildly irritating to the
eyes and may cause some cornea damage, A value of 1 ppm by volume or
3
6 mg/M in air has been suggested as
considered safe for an 8-hr exposure.
3. OTHER HAZARDS
3
6 mg/M in air has been suggested as the maximum allowable concentration
Nitroaniline is a moderate fire hazard when exposed to heat or flame or
when chemically reacted with oxidizers. Contact with the skin and eyes,
1498
as well as the inhalation of vapors and dust should be avoided.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Nitroaniline is not a serious industrial hazard if workers are adequately
instructed and supervised in proper methods of handling the chemical. When-
ever possible, nitroaniline should be handled within a wholly closed system.
Equipment should be designed to avoid spills and to prevent dust from
1498
escaping into the air.
A description of personnel protective equipment and instructions on
its use are recommended by the Manufacturing Chemists Assn0 The
Department of Transportation (DOT) regulations are very detailed and
specific concerning packages which may be used to transport nitroaniline
(see Section 73.365 and 73.373 of the DOT regulations). Under the DOT
regulations, nitroaniline is classified as a Class B poison.
138
-------
Disposal /Reuse
Disposal or reuse of waste nitroaniline streams must take into account
the toxic nature of these materials. It is assumed that dilute aqueous waste
streams containing nitroaniline are treated in the same manner as dini-
trophenol waste streams, i.e., secondary treatment using acclimated activated
sludges and aeration (see Profile Report on Dinitrophenol [164]).
Recommended provisional limits for nitroaniline in the environment are
as follows:
Basis of
Contaminant and Environment Provisional Limits Recommendation
Nitroaniline in air 0.01 ppm ., 0.01 TLV
(0.06
Nitroaniline in water and 0.30 ppm (mg/1 ) Stokinger and
soil Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Nitroanilines are expected to appear primarily as aqueous waste streams
in low concentrations and only rarely as concentrated waste. The processing
options are briefly described in the following paragraphs together with
recommendations as to their adequacy.
Concentrated Nitroanilines
In the event it becomes necessary to dispose of a significant quantity
of concentrated nitroaniline, and purification/recycling is impractical, then
incineration of nitroaniline is the recommended method of disposal. Quali-
fied personnel familiar with handling toxic materials must be available. The
material must be incinerated under controlled conditions where oxides of
nitrogen are removed from the effluent gas by scrubbers and/or thermal or
1435
catalytic devices. Combustion should be carried out at a minimum
temperature of 1,800 F for at least 2.0 seconds.
139
-------
Dilute Aqueous Waste Streams
Nitroanilines appear as aqueous waste in the manufacturing process.
It is assumed that methods used to dispose of aqueous nitroaniline waste
are similar to methods used for dinitrophenol, i.e., secondary treatment
utilizing activated sludges. The adequacy of this practice is in doubt due
to the apparent difficulty of microorganisms to degrade aromatic nitro com-
1044
pounds. Until data are available to show that nitroanilines can be
degraded satisfactorily in secondary treatment facilities, it is recommended
that aqueous waste streams be concentrated and treated as discussed in the
section on concentrated nitroaniTines.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The nitroanilines do not appear to be candidate waste stream consti-
tuents for National Disposal Sites. It is anticipated that the great
majority of the aqueous nitroaniline waste generated in the chemical in-
dustries will continue to be treated at the source of the waste generation *
but it is recommended that emphasis should be changed from biological treat-
ment processes to concentration and subsequent controlled incineration until
the adequacy of the biological processes is proven. In the event concen-
trated material becomes contaminated, it can be incinerated as discussed in
the section on concentrated nitroanilines.
140
-------
7. REFERENCES
0766. Sac, N. I., Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Book Corporation, 1968. 1,251 p.
1044. Marion, C. V., and G. W. Malaney. Ability of activated sludge
microorganisms to oxidize aromatic organic compounds. lr^
Proceedings; Eighteenth Industrial Waste Conference, Engineering
Bulletin of Purdue University, 1963. p. 297-308.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed., New York,
Interscience Publishers, 1963.
1435. John Zink Co., NOX destructor, bulletin number NOX 1071m. John Zink
Co., Tulsa. 4 p.
1492. Merck and Company. The Merck indes of chemicals and drugs. Rahway,
New Jersey, 1960. 1,643 p.
1498. Manufacturing Chemists Association. Properties and essential infor-
mation for safe handling and use of paranitroaniline. Safety data
sheet SD-94. Washington, 1966. 14 p.
1506. Schnell Publishing Company, Inc. Chemical profile, p-nitroaniline.
1969. 1 p.
1570. The Chemical Rubber Company. Handbook of chemistry and physics.
47th ed. Cleveland, 1962. 2,100 p.
1571 Schnell Publishing Company, Inc. 1971-72 OPD chemical buyers guide.
59th ed. New York, 1971. 1,584 p.
141
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitroaniline (0) (300)
IUC Name 2-nitroaniline
Structural Formula
Common Names
ortho-nitroaniline
Molecular Wt.
Density (Condensed)
138.13
(1)
_ Melting Pt. 71.5 C
@ 15 C Density (gas)_
(1)
Boiling Pt. 284 C
(1)
Vapor Pressure (recommended 55 C and 20 C)
1mm'2' @ 142.4 C
(3 165 C
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
(1)
Lower
Upper_
Upper_
Solubility
Cold Water very slight
Hot Water slight
Ethanolsli9ht» very (hot
Others: very, benzene, CHC1, acetone
Acid, Base Properties basic, forms water sol, salts with acids
(2)
Highly Reactive with acids
Compatible with_
Shipped in
ICC Classification
Coast Guard Classification
Comments dye-stuff ^ntermed
(2)
References (1) 1570
(2) 1492
(3) 1571
142
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitroaniline (n)
Structural Formula
IDC Name 3-nitroaniline
Common Names meta-nitroaniline
Molecular Wt. 138.13^ Melting Pt. 114 r/1) Boiling Pt. 305-7 C^1)
Density (Condensed) 1.430 @ 4_ _C Density (gas) @ (aecomp)
Vapor Pressure (recommended 55 C and 20 C)
0.16 mm'^(a 10QC & @ .
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive'Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water 1g/800 ml^ Hot Water Ethanol lg/20 ml^
Others: lq/11.5 ml (MeOH)(2) CHC13(1)
Acid, Base Properties Forms water soluble salts with minprai ariHc W very slightly
Highly Reactive with acids
Compatible with_
Shipped in
ICC Classification Coast Guard Classification
Comments Toxic-absorbed through skinJ2^ dye intPrmprfiatP^2)
Suppliers: American Cyanamid. Cnnray PrnHnrt^, Jrctn rhamicai Co
References (1) 1570
(2) 1492
(3) 1571
(4) 1655
143
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitroaniline (p)
IDC Name 4-nitroaniline
Common Names para-nitroaniline
Structural Formula
Molecular Wt. 138.13
(1)
Density (Condensed) 1.424
_ Melting Pt. 148.5-9.5 C
@ 20 _C Density (gas)
(1)
Boiling Pt. 331.7 C
.(1)
Vapor Pressure (recommended 55 C and 20 C)
0.03 mm @ 106 C
Flash Point
390
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Solubility
Cold Water 1g/1250 ml
Others: Ether (lg/30 ml)
Hot Water lg/45 ml
Upper_
Upper_
Acid, Base Properties_
Ethanol 1g/25 ml
Basic - forms water sol. salts mineral acids ^ '
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Poison B
Very tnxic.^ dvPStaff intPnnpHi.tP
Coast Guard Classification
(3) nj (4) Sherwin
Poison B
Chemical. Fallek Chemical, American Hoechst Corp. (organic inter)
References (1) 1570
(2) 0766
(3) 1492
(4) 1571
144
-------
PROFILE REPORT
Nitrobenzene (301)
1. GENERAL
Nitrobenzene is a pale yellow liquid with a distinct almond-like odor.
It is highly toxic when ingested, inhaled, or absorbed through the skin.
The most important application of nitrobenzene is in the manufacture of
aniline for the synthesis of dyestuffs. At least 85 percent of the nitro-
benzene manufactured in the United States is used by the dye industry.
Other uses of nitrobenzene are for the manufacture of rubber chemicals,
photographic chemicals and drugs. '
The present industrial use of nitrobenzene as a starting material for
dyestuffs and other organic intermediates stems largely from the impetus
provided by its ease of manufacture. The current method for the commercial
manufacture of nitrobenzene is the direct nitration of benzene using mixed
1433
sulfuric and nitric acids.
Large scale commercial facilities for the manufacture of nitrobenzene
are operated by Allied, Cyanamid, First Chemical, Mobay, Monsanto, and
15
Rubicon.
worksheet.
2. TOXICOLOGY
Nitrobenzene exhibits the high toxicity typical of nitroaromatic com-
pounds. It is readily absorbed by contact with the skin, inhalation of the
1433
vapor, or by ingestion. The maximum allowable concentration in air is
1 ppm (5 mg/M ). The ready absorption of nitrobenzene through the skin
is the major potential hazard in handling this material. Significant ab-
sorption continues as long as the oily liquid remains on the skin surface
145
Rubicon. Physical/chemical properties are summarized in the attached
-------
1494
or as long as contaminated articles of clothing are worn. The Hygienic
Guide Series states that- nitrobenzene may be almost immediately fatal if
large areas of the body are in contact with the liquid or if massive con-
centrations are inhaled.
The odor of nitrobenzene can usually be detected without difficulty in
n
1513
1513
concentrations of 0.05 ppm in the atmosphere. Nitrobenzene, soluble in
water to the extent of 0.19 parts nitrobenzene in 100 parts water at 20 C,
is odorous in water at low concentrations; 0.03 mg/1 has been reported as the
1494
the Threshold Limit Value. Acute aquatic toxicity occurs at about
IdQA IdQ?
30 mg/1. H The lethal dose orally in rabbits is 700 mg/kg.' ^
3. OTHER HAZARDS
Nitrobenzene is a hazard to health due to its high toxicity and is
considered to be a moderate fire and explosion hazard when exposed to heat
1433
or flame. This material is classified by the Department of Transpor-
tation (DOT) as a "Poisonous Liquid" Class B and each shipping container must
bear the DOT poison label. The handling of nitrobenzene should be carefully
controlled with precaution and procedures such as the use of protective
clothing, face protection and adequate ventilation. The lower explosive
limit in air is 1.8 percent by volume at 200 F, the upper limit has not'been
1494
reported. 4
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Nitrobenzene is highly toxic when absorbed through the skin, inhaled
as vapor, or swallowed. Although the vapor given off at elevated tempera-
tures is flammable, nitrobenzene can be handled with little danger of fire
since the flash point of the liquid (88 C) is much higher than the tempera-
tures at which it is normally handled. Containers specified for nitro-
benzene are listed in the Code of Federal Regulations, Title 49, paragraphs
173.345 and 173.346. Usual containers are as follows:
146
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Spec. 5, 5A, 5B, or 5C metal, barrels or drums,
Spec. 17C or 17E single-trip metal drum containers,
Spec. 15A, 15B, 15C, 16A or 19A - wooden boxes with glass or
earthenware inside containers,
Spec. 103, 103W, 103A or 103A-W - tank cars,
Spec. MC300, MC301, MC302, MC303 or MC305 - tank motor vehicles.
Detailed handling instructions for small containers, drums, tank trucks
1494
and tank cars are supplied by the Manufacturing Chemists Assn., along
with personnel protective equipment.
Disposal/Reuse
Nitrobenzene is prepared by the direct nitration of benzene, using a
nitric acid-sulfuric acid mixture. The batch process utilizes reaction
vessels specially built of cast iron or steel and fitted with agitators.
Newer plants use a continuous process, as typified by the Biazzi process,
for the production of nitrobenzene. The sequence of operations is essen-
tially the same as in the batch process, the main differences being the
use of smaller reaction vessels, lower nitric acid concentrations, and
1433
higher reaction rates.
The reduction of nitrobenzene to aniline outranks all other uses of
nitrobenzene as an industrial chemical, only 15 percent of the nitrobenzene
produced is for other uses.1501 Both Mobay1521 and Rubicon1519 utilize all
their nitrobenzene production at the manufacturing site. Waste streams
associated with the manufacturing process are aqueous in nature and are
given primary and secondary treatment consisting of treatment with lime and
digestion with activated sludge before being discharged into waterways.
Treatment facilities are in operation for handling aqueous nitrobenzene
waste streams that reduce the BOD loading 90 percant to 95 percent.
Recommended provisional limits for nitrobenzene in the environment
are as follows:
147
-------
Contaminant and Basis for
Environment Provisional Limits Recommendation
Nitrobenzene in 0.01 ppm (0.05 mg/M3) 0.01 TLV
air
Nitrobenzene in 0.25 ppm (mg/1) Stokinger and
water and soil Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Nitrobenzene is expected to appear primarily as aqueous waste streams
in low concentrations and only rarely as concentrated waste. The processing
option,; are briefly described in the following paragraphs together with
recommendations as to their adequacy.
Concentrated ^Nitrobenzene
In the event it becomes necessary to dispose of significant quantities
(55- gel. drum or 10,000-gal. tank car) of concentrated nitrobenzene, two
disposal options are available. The first option is to contact the manu-
facturer and determine if it is possible to return the material. E. I.
duPont de Nemours has indicated a willingness to accept concentrated
nitrobenzene for reprocessing provided the contaminant or contaminants in
the nitrobenzene are compatible with their reprocessing system and the
economic aspects of the situation are favorable. The second option is
incineration since nitrobenzene is flammable and amenable to the treatment.
Combustion should be carried out at a minimum temperature of 1,800 F for
at least 2.0 seconds.
Small amounts of nitrobenzene can be adequately disposed of by dilution
provided proper secondary treatment facilities have organisms acclimated to
this material (see section on Dilute Aqueous Waste).
The open burning of nitrobenzene is not an adequate means of disposing
of this material since oxides of nitrogen as well as incomplete combustion
products may be generated during its combustion. Controlled combustion
148
-------
processes where the oxides of nitrogen are scrubbed from the effluent gas
or where a thermal or catalytic device is used to reduce the oxides of
nitrogen to their elemental form is acceptable.
Although landfill techniques are used extensively throughout the chem-
ical industry, it is recommended that this practice be continued only when
landfills meet California Class I requirement:..
Dilute Aqueous Waste
Nitrobenzene appears as wasfe in water at concentrations in the order
of parts per million. ' Haste treatment facilities are in operation
that handle nitrobenzene aqueous waste and some waste water treatment
facilities combine both plant aqueous wastes and domestic sewage. ~ In
the latter case, effluent from the plant is given primary treatment, fol-
lowed by treatment with lime to adjust the pH from 2.5 to 7. The effluent
is mixed with municipal sewage end allowed to equilibrate one day after
which it is lagooned for 20 hours with mechanical aeration. BOD reduction
runs from 90 percent to 95 percent. Secondary treatment utilizing accli-
mated activated sludge systems for nitrobenzene aqueous waste should
be adequate.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that systems to handle the great majority of the
aqueous nitrobenzene waste generated in the chemical process industries
will continue to be located at the source of the waste generation. For
concentrated nitrobenzene waste, it will not be necessary to have a
specific facility at a National Disposal Site provided: (1) it can be
recycled, or (2) incinerated in a safe manner (see section on Concentrated
Nitrobenzene) at the manufacturers' site.*
*However, incinerators designed for handling other organic wastes (at
National Disposal Site) will be capable of handling Nitrobenzene.
149
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7. REFERENCES
0314. Jones, H. R. Environmental control in the organic and petrochemical
industries. Review No. 3. Park Ridge, New Jersey, Noyes Data
Corporation, 197.1. 264 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d. ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1316. Noller, C. R. Chemistry of organic compounds. 2d ed. Philadelphia, -
W. B. Saunders Company, 1957. 978 p.
1432. Personal communication. R. Wilson, Du Pont de Nemours and Company,
Inc., to W. P. Kendrick, TRW Systems, Mar. 24, 1972.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1492. Merck and Company, Inc. The Merck index of chemicals and drugs,.,
Rahway, New Jersey, 1960. 1,643 p,.
1494. Manufacturing Chemists Association. Properties and essential
information for safe handling and use of nitrobenzene. Chemical
Safety Data Sheet SD-21. Washington, 1967. 15 p.
1501. Faith, W. L., Keyes, P. B., and R. L. Clark. Industrial chemicals.
Library of Congress Card No. 65-21450. New York, John Wiley and
Sons, Inc., 1965. 852 p.
1506. 1968 Chemical profiles. Schnell Publishing Company, Inc., New, Yprk.
200 p.
1513. Du Pont de Nemours and Company. Du Pont nitrobenzene. Product
information, Wilmington, Delaware. 5 p.
1519. Personal communication. C. Rappe, Rubicon Company, to W. P. Kendrick,
TRW Systems, Apr. 3, 1972.
1520. Personal communication. Mr. Hunt, American Cyanamid Company, to
W. P. Kendrick, TRW Systems, Apr. 12, 1972.
1521. Personal communication. E. E. Bailey, Mobay Chemicals, to W. P.
Kendrick, TRW Systems, Apr. 13, 1972.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, Chemical Rubber Company, 1966. 1,500 p.
1571. OPD Chemical buyers directory. New York, Schnell Publishing Company,
1971. 1,584 p.
1572. American Cyanamid Company. Oil of myrbane. Technical Bulletin C-43.
Bound Brook, New Jersey, 1971. 2 p.
150
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Nitrobenzene (301)
Structural Formula
IUC Name Nitrobenzene
Common Names Nitrobenzene, Nitrobenzol, Oil of Myrbane
Molecular Wt. 123.11 Melting Pt. 5.7 C^ Boiling Pt. 210.9 C
Density (Condensed) 1.19867 @ 25/4 Cv Density (gas) 4.75
g Pt. a./ t' '
.Density (qas) 4.75(1)
Vapor Pressure (recommended 55 C and 20 Q Air " 1'°
(4) ,.* ...
1 mm @ 44.4 C 22 mm g 100 CVH' 50 mm @ 120 C '
Flash Point 87.8 C (C.C.)(4) Autoignition Temp.(900
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower 1.8% at 200 F( ^ Upper_
Solubility Slightly^ 0.19/100 1.0/100 parts water
Cold Water parts water^ Hot Water at 200 C Ethanol Very soluble
Others: ether, benzene (very)
Acid, Base Properties
Highly Reactive with Highly flammable
Compatible with anY metal container is usually satisfactory, paraffin or plastic drum
liners should not be
Shipped in tank cars, tank truck, steel drums.
ICC Classification . Coast Guard Classification DOT Reg. 73.346^
Comments Sources:^ ' A.I.D. Chemical Co., Inc; Allied C.hpmiral rnrp; AmoHran Cy^namiH Co:
E. I. duPont de Nemours & Co., Inc; First Chemical Corp; McKesson Chemical Co; Metchler
Chemical Co. Inc.
References (1) 0766 (4) 1513
(2) 1570 (5) 1572
(3) 1571
151
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PROFILE REPORT
meta-and para-Nitrochlorobenzene(302)
1. GENERAL
Nitrochlorobenzene (meta and para) are yellow crystals having melting
points of 46 C and 82 C, respectively. 9 Both materials are highly
toxic and have similar effects on the body. Their effects are analogous
to those of nitrobenzene?
Mononitrochlorobenzenes can be obtained from benzene by a combination
of nitration and halogenation. The order of the operations determines the
positional isomer content of the product. meta-Nitrochlorobenzene is ob-
tained by nitration of benzene followed by chlorination. By reversing the
order, a mixture results containing about two parts of the para isomer to
one of the ortho. On a technical scale, fairly sharp separation of the
isomers resulting from nitration is made by freezing out the bulk of the
higher-melting para compound, fractionating the liquid portion, and further
freezing.1655
Domestic production of £-nitrochlorobenzene was reported as over 88.9
1718
million Ib for the year of 1970. Production figures are not avail-
able for the meta compound. Manufacturers of the meta compound are E. I.
1718
du Pont de Nemours and Company Incorporated and Universal Oil
1718
Products. The para compound is manufactured by American Aniline
1718 1718
Products, E. I. du Pont de Nemours Company Incorporated,
1718 1718
Monsanto Company, and Universal Oil Products.
2. TOXICOLOGY0766
Intoxication from these materials can be serious. When absorbed, they
form methenoglobin and give rise to cyanosis and blood changes. Their effects
are analogous to those of nitrobenzene (See Profile Report on nitrobenzene [301]),
They can cause poisoning by the pulmonary route and their effects are cumu-
lative. The toxic hazard rating for ingestion and inhalation is high for both
materials.
153
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3. OTHER HAZARDS
In industry it is the dust of these materials that is most often the
source of intoxication. Protective goggles, gloves and breathing masks
capable of removing airborne dust should be worn when working with these
materials in the open. There is only a moderate fire hazard associated
with the nitrochlorobenzenes.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage, and Transportation
Gloves and chemical goggles should be worn to protect the hands and
eyes when handling nitrochlorobenzene flakes or crystals. A breathing
mask capable of eliminating nitrochlorobenzene dust is recommended when
handling these materials in other than fume hoods or closed systems.
The nitrochlorobenzenes (meta and para) are shipped as crystals and
flakes according to Department of Transportation (DOT) regulations.°278They
are classed as"Poison B"and require a poison label on all packages.
These materials should be stored in tightly closed containers away
from heat or flame. When heated to decomposition, they emit highly toxic
fumes of oxides of nitrogen and phosgene. They can also react with
oxidizing materials.
Disposal/Reuse
A definition of acceptable criteria for the disposal of meta and para-
nitrochlorobenzenes must also take into account acceptable criteria for the
release of hydrogen chloride, hydrochloric acid, and nitrogen oxides to the
environment, since current practice in nitrochlorobenzene disposal involves
1432
some processes that reduce nitrochlorobenzene to these materials.
Current disposal techniques utilize incineration and land burial.
These methods are acceptable provided the recommended provisional limits
154
-------
in nitrochlorobenzene, hydrogen chloride, hydrochloric acid and nitrogen
oxides in the environment are not exceeded. The recommended provisional
limits are as follows:
Contaminant and
Environment
p_-Nitrochlorobenzene
in air
rn-Ni trochl orobenzene
in air
Hydrogen chloride in
air
Hydrochloric acid in
air
Nitrogen oxides
in air
£-Ni troch1orobenzene
in water and soil
m-Ni trochlorobenzene
in water and soil
Provisional Limits
0.01 mg/M3
0.01 mg/M3
0.05 ppm (0.07 mg/M3)
0.05 ppm (0.07 mg/M3)
0.05 ppm (0.07 mg/M3)
0.05 ppm (mg/1)
0.05 ppm (mg/1)
Basis for
Recommendation
0.01 TLV
Based on p-Nitro-
chlorobenzene
0.01 TLV
0.01 TLV
0.01 TLV
Stokinger and
Woodward method
Based on p-Nitro-
chl orobenzene
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The nitrochlorobenzenes are expected to appear primarily as dilute
organic waste streams and to a much lesser degree as dilute aqueous waste
and concentrated waste. The processing options are briefly described in
the following paragraph together with recommendations as to their adequacy.
In the event it becomes necessary to dispose of a significant quantity
of concentrated nitrochlorobenzene, two adequate disposal options are avail-
able. The first option is to incinerate the material. It is expected that
either a rotary kiln or liquid combustor, depending upon the form of the
waste, followed by secondary combustion and aqueous or caustic scrubbing
would be an acceptable disposal method. Primary combustion should be
carried out at a minimum of 1,500 F for at least 0.5 seconds with secondary
combustion at a minimum temperature of 2,200F for at least 1.0 second.
155
-------
The chloride abatement problem may be simplified by insuring against
elemental chlorine formation through injection of steam or methane into
the combustion process. The nitric oxides may be abated through the use
of thermal or catalytic devices. The second option is to bury the material
in a California Class I type landfill. It is recommended that dilute organic
waste be disposed of by incineration. Concentration followed by
incineration is the recommended method of disposing of dilute aqueous waste.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The nitrochlorobenzenes are expected to appear primarily as dilute
organic waste and to a much lesser degree as dilute aqueous waste and
concentrated waste. Processes for handling the disposal of these wastes
will be located at manufacturing sites and/or industrial disposal facilities
and represent common industrial technology. Therefore, these compounds
are not judged to be candidate waste stream constituents for National
Disposal Sites.
156
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7. REFERENCES
0278. Code of Federal Regulations, Department of Transportation. Title 49,
Parts 71-90. Washington, Superintendent of Documents, U. S.
Government Printing Office, 1967. 794 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1432. Personal communication. H. W. Larson, E. I. du Pont de Nemours and
Company, to W. P. Kendrick, May 17, 1972.
1492. Merck and Company, Inc. The Merck index of chemicals and drugs.
Rahway, New Jersey, 1960. 1,643 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, Chemical Rubber Company, 1966. 1,500 p.
1655. Fieser, L. F., and M. Fieser. Organic chemistry. 3d ed. Boston,
D. C. Heath and Company, 1956. p. 574-575.
1718. United States Tariff Commission. Synthetic organic chemicals.
U. S. production and sales, 1970. TC Publication 479. Washington,
U. S. Government Printing Office, 1972. 262 p.
157
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name m-nitrochlorobenzene (302)
M) Structural Formula
IUC Name 1 -chloro-3-nitrobenzene
Common Names m-chloronitrobenzene
(1)
C6H4C1N02
Molecular Wt.1' ]57.56 Melting PtP 44 C Boiling Pt. 235-6
Density (Condensed) 1.534 @ 20/4 (r Density (gas) & ,__
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Inso1ubl£ ' Hot Water Ethanol Slightly solubll1
Others:^'Soluble in ether benzene CSp chloroform acetic acid
Acid, Base Properties .
Highly Reactive with Can react with oxidizing materials
Compatible with Glass, metals, earthenware '
Shipped in_
ICC Classification Poison B3 Coast Guard Classification •
/4\
Comments Mfg. by. E. j. du Pont. HP Npmnnr<: and rxnpany incorporatfld' UnivarEal Oil Product^
References (1) 1570 (4) 1718
(2) 0766
. (3) 0278
158
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name p-nitrochlorobenzene (302)
, . Structural Formula
IUC Name l-chloro-4-nitrobenzene '
Common Names p-chloronitrobenzene '
C6H4C1N02
Molecular WtP ) 157.56 Melting Ptft 83 C Boiling
Density (Condensed) 1.520 Density (gas)
Vapor Pressure (recommended 55 C and 20 0
Flash Point 127 C Autoignition Temp._
Flammabilicy Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubil ity
Cold Water Insoluble^1 ' Hot Water Ethanol Slightly soluble '
Others: Soluble in ether , CS?
Acid, Base Properties
Highly Reactive with
Compatible with Glass, metals, earthenware3
Shipped in
(3)
ICC Classification Poison B Coast Guard Classification
(41
Comments Mfg. by- American Aniline Products Incorporated; Monsanto Company.
References (1) 1570 (4) 1718
(2) 0766
(3) Q278
159
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PROFILE REPORT
ON NITROPARAFFINS
Nitroethane (303). Nitromethane (308). 1-Nitropropane (311)
1 . GENERAL
Introduction
The nitroparaffins treated in this report have all been selected as
probable candidate waste stream constituents for industrial disposal. These
materials are similar in that they are commodity chemicals made by the same
process with relatively low toxicity, well-defined and safe methods of
industrial handling and common methods of disposal. The nitroparaffins
are, therefore, discussed as a class in this report.
Manufacture and Use1 433 ' ] 501
The major method of manufacture of nitroparaffins is by the reaction
of propane with nitric acid in the molar ratio of 1 to 5 at 390 to 400 C and
100 to 125 psi. All four lower nitroparaffins are produced by varying the
conditions and the relative amounts can be adjusted somewhat to meet
market demands.
HN03 - * CH3N02( 10-30%) + C2H5N0
+ [CH3-CH(N02)-CH3 + CH3-CH2-CH2-N02] (55-65%)
The nitroparaffins are used as intermediates in the production of
nitro alcohols, alkanol amines, polynitro compounds, and hydroxylamine
and its salts. Other major uses are as cosol vents for polymers, extraction
or partition sol vents, react ion media, recrystallization sol vents and other
minor solvent uses. Smaller amounts of nitroparaffins are used in high
explosives, as special purpose additives in gasoline and diesel fuels.and
as a stabilizer for halogenated alkanes.
161
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Physical and Chemical Properties
The physical and chemical properties discussed in this report are in-
cluded in the attached worksheets.
2. TOXICOLOGY0766'1433
The nitroparaffins are classified by most toxicologists as slightly
toxic in marked contrast to the aromatic nitrocompounds. The chief indus-
trial hazard is by inhalation. High concentrations of nitroparaffin vapors
produce a mild irritation of the respiratory tract and early symptoms of
intoxication such as headache or nausea, which disappear promptly when ex-
posure is reduced. Large doses may cause methemoglobinemia, cyanosis and
injury to the liver and kidneys. Repeated skin contact does not cause
allergies or other adverse physiological effects.
The Threshold Limit Values (TLV) and Maximum Allowable Concentrations
are listed below. The values for the nitropropanes are thought to be very
1433
conservative.
TVL MAC
nitroparaffins ppm mg/M3 ppm
Nitromethane 100 250 100
Nitroethane 100 310 100
1-Nitropropane 25 90
2-Nitropropane 25 90
3. OTHER HAZARDS0766'1433'1569
The mononitroparaffins are relatively stable, but impact under confined
conditions can cause explosion of nitromethane. A combination of high
temperature and pressure can cause nitromethane to act as a monopropellant.
Alkaline solutions of the nitroparaffins should not be reduced to dryness
since the metal salts are explosive.
162
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4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling. Storage and Transportation
The nitroparaffins are toxic to a certain extent by inhalation and,
for this reason, should be handled in a well-ventilated area. Respirators
are recomended when necessary. Although accidental contact is not dangerous
to the skin, good technique requires that it be kept .to a minimum. '
Commercial-grade nitroparaffins are shipped and stored in ordinary
carbon steel. However, wet nitroparaffins containing more than 0.1 to 0.2
percent water may become discolored when stored in steel for long periods,
even though corrosion of the steel is not excessive. Aluminum and stain-
less steel are completely resistant to corrosion by wet nitroparaffins.
Storage of nitroparaffins in contact with lead or copper or alloys con-
taining these metals should be avoided. Polymeric materials for gaskets,
hoses, etc.,' should be tested for their suitability before exposure to
nitroparaffins.
The commercial nitroparaffins have flash points greater than 100 F and
hence do not require a U.S. Department of Transportation (DOT) red label. The
ignition temperatures of the lower homologs are relatively high for organic
solvents. When ignited, nitromethane burns with a lazy flame, which often
dies out spontaneously, and in any case is readily extinguished with water
which floats on the heavier nitromethane. The nitropropanes burn more
vigorously, but less so than gasoline.
Since nitromethane can explode under conditions of heat, shock and
pressure, it preferably should be stored in the 55-gal. drums in which it
is shipped. These containers are of lightweight construction so that
there is little possibility that they might develop sufficiently high
internal pressure either to ignite the nitromethane or to allow it to
burn as a monopropellant. Bulk-storage tanks should be isolated, buried,
or barricaded to protect them from projectile impacts should an
163
-------
explosion occur in nearby equipment or facilities. With the exception
of nitomethane, there are no restrictions on shipment or storage of
the lower mononitroparaffins. Nitroethane or the nitropropanes in
unconfined quantities have not been exploded by heat and/or shock applied
under extreme test conditions.
Disposal/Reuse
Commercial manufacturers who use nitroparaffins as chemical ../'
intermediates, generally reuse all unreacted materials. Manufacturers who
use nitroparaffins in various solvents recycle them indefinitely. When
used in explosives or as a fuel, they are completely combusted.
Recommended provisional limits for the nitroparaffins discussed in this
report are listed below.
Contaminant
in Air
Nitromethane
Nitroethane
1-Nitropropane
2-Nitropropane
Provisional Limit
ppm mg/M3
1.0
1.0
0.25
0.25
2.5
3.1
0.90
0.90
Basis for
Recommendation
0.01 TLV
0.01 TLV
0.01 TLV
0.01 TLV
Contaminant in
Mater and Soil
Nitromethane
Nitroethane
1-Nitropropane
2-Nitropropane
Provisional Limit
ppm or mg/1
12.5
15.5
4.5
4.5
Basis for
Recommendation
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
Stokinger and
Woodward Method
164
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Recycling
Presently, manufacturers who use nitroparaffins as solvents or chemical
intermediates recycle all possible material. This is the method of choice.
Option No. 2 - Incineration
Unusable nitroparaffins that are unfit for recyling can be incinerated.
incineration of large quantities
by catalytic or scrubbing processes.
The incineration of large quantities of material may require NO removal
A
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The wastes generated by the industries that use nitroparaffins can be
handled on site by recyling and common incineration methods. They should
not be considered as candidate waste constituents requiring National Dis-
posal Site treatment.
165
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7. REFERENCES
0766. Sax. I.R., Dangerous properties of industrial materials, Sd.ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical tecthnology. 3d ed. 22 V.
New York, Interscience Publishers, 1966.
1492- The Merck index of chemicals and drugs. 7th ed. Rahway,
New Jersey, Merck Company, Inc,, I960. 1,634 p.
1501. Faith, W.L., D.B. Keyes, and R.L,. Clark. Industrial Chemicals.
3d ed. New York, John Wiley and Sons, Inc., 1965. 824 p.
1569. Manual of hazardous chemical reactions. Boston National Fire
Protection Association, 1971. 308 p.
1570. Weast, R.C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
166
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitroethane
Structural Formula
IUC Name nitroethane
Common Names
CH3-CH2-N02
Molecular Wt. 75.07 Freezing Pt. -90 C Boiling Pt. 114.0
Density (Condensed) 1.052 & 20/20 C^1? Density (gas) 2.58^ @
Vapor Pressure (recommended 55 C and 20 C)
15.6 mm @ 20 C(1)
Flash Point 82 P Autoignition Temp. 778 F
Flammability Limits Fin Air (wt %) Lower 4.0%^2j _ Upper_
Explosive Limits in Air (wt. it) Lower 3.4%0) _ ' Upper_
SolubiT-ity
Cold Water 4.5 g/ml(200)^2^ Hot Water Ethanol miscible^2^
Others: miscible. methanol, ether;^ ' soluble, chloroform, alkaline aq. solution.'2'
Acid, Base Properties
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification ; Coast Guard Classification_
Comments :
References (1) 0766
(2) 1492
167
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitroparaffins (309)
IUC Name
Common Names class of compounds including
C-|-C3 compounds.
Structural Formula
See 309a, 309b, 303, 311.
Molecular Wt.
Density (Condensed)
Melting Pt.
Density (gas)_
Boiling Pt..
0
Vapor Pressure (recommended 55 C and 20 0
0
Flash Point 103-120 F
(IT
Autoignition Temp._
Flammability Limits in Air (wt X) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water_
Others:
Hot Water
Ethanol
Acid, Base Properties slightly acidic; salts of inorganic bases may be explosive.
:D
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification
Coast Guard Classification
Comments the nitroparaffins are dangerous when heated in confined containers.
References (1) 0766
168
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitroparaffins (309)
IUC Name 2-nitropropane
Common Names
Structural Formula
N02
CH3-CH-CH3
Molecular Wt. 89.09
Freezing Pt. -93 C
(I!
Density (Condensed) 0.992 @ 20/20
Density (gas) 3.06
Boiling Pt. 120 C
(1)
Vapor Pressure (recommended 55 C and 20 0
10 mm
& 15.8 C
1)
Flash Point 103 F
(1)
Autoignition Temp. 802 F
Flammability Limits in Air (wt %)' Lower
Lower
Explosive Limits in Air (wt. %)
f
Solubility
Cold Water 1.7 Ml/100 ml^2)
2.6%
Hot Water
Upper_
Upper_
Others: miscible with many organic solvents. '
Acid, Base Properties
Ethanol misciblp
(3)
Highly Reactive with
Compatible with
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 0766
(2) 1492
(3) 1570
169
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nltroparaffins (309)
Structural Formula
IUC Name nitromethane
Common Names nitrpcarbol
CH3-N02
Molecular Wt. 61.04 Freezing Pt. -29 C^' Boiling Pt. 101
Density (Condensed) 1.130 @ 20/4 C^' Density (gas) 2.11 @
Vapor Pressure (recommended 55 C and 20 C)
1)
27.8 mm @ 20 Cv
Flash Point 95 r]' Autoignition Temp.785 F^
Flammability Limits in Air (wt %) Lovyer Upper
Explosive Limits in Air (wt. %) Lower 7.3% Upper_
*
Solubility
Cold Water 9.10%^ Hot Water Ethanol soluble^
Others: soluble - ether, dimethylformamaide.(^)
Acid, Base Properties
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification Coast Guard Classification
Comments Forms an explosive sodium salt which bursts into flame on contact with
References (1) 0766
(2) 1492
170
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name 1-Nitropropane (311)
Structural Formula
IUC Name 1-nltropropane
Common Names
CH3-CH2-CH,-N02
Molecular Wt. 89.09 Freezing Pt. -1Q8 C Boiling Pt. 132
Density (Condensed) 1.003 @20/20 d1) Density (gas) 3.06 @
Vapor Pressure (recommended 55°C and 20°Q
7.5 mm @ 20 C^1 ^ @ @
Flash Point 120 F^) Autoignition Temp. 789 F^
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower 2.6% Upper_
Solubility
Cold Water 1.4 ml/100 ml Hot Water Ethanol
Others: miscible with many organic solvents^ '
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in_
ICC Classification Coast Guard Classification
Comments
References (1) 0766
(2) 1492
(3) 1570
171
-------
PROFILE REPORT
AROMATIC NITRO COMPOUNDS
4-Nitrophenol (310), 4-Nitrotoluene (312)
1. GENERAL
Introduction
The aromatic nitro compounds treated in this report have been selected
as probable candidate waste stream constituents for industrial disposal.
The materials are similar in that they are commodity chemicals with similar
toxicity, well-defined methods of industrial handling and common methods
of disposal. These compounds are, therefore, discussed as a class in this
report.
1433
Manufacture and Use
The aromatic nitrophenols can be made by both direct and indirect
routes. However, phenol because of its hydroxyl group is both readily
nitrated and oxidized making a nitration by the conventional nitric acid
route uneconomical. Consequently, commercial routes utilize indirect two-
step procedures. The preferred technique is the hydrolysis of the cor-
responding nitrochlorobenzene with 15 percent sodium hydroxide at 160 C.
The nitrophenols are used as intermediates in the preparation of
dyestuffs, plant sprays (parathion), aminophenols and photochemicals.
The nitrotoluenes are manufactured by the direct nitration of toluene
in either batch (liquid phase) or continuous (gas phase) processes. Care
must be used to prevent an accumulation of excess nitric acid as this will
oxidize toluene reducing the yield and at the same time producing explosive
tetranitromethane. A typical product mixture contains 62 to 63 percent
173
-------
o-nitrotoluene, 3 to 4 percent m-nitrotoluene and 33 to 34 percent p-nitro-
toluene. The reaction product is washed free of acid and distilled into
ortho-, meta-, and para-rich fractions.
The nitrotoluenes are used principally in the synthesis of dyes such
as new magenta and turquois blue.
Physical and Chemical Properties
The physical and chemical properties of the compounds discussed in
this report are included in the attached worksheets.
2. TOXICOLOGY0766'1433'1492
As a class, the nitrophenols are very toxic compounds not only when
ingested but also when inhaled or absorbed through the skin. The charac-
teristic effects of poisoning are an enhancement of metabolism with a rise
in body temperature, headache, heavy sweating, thirst, fatigue and just
before death a sudden rise in body temperature. Chronic exposure is often
characterized by hyperthermia, methemoglobinemia, depression, liver and
kidney damage, cataracts, eczema, inflammation of the lymphatic glands and
degeneration of the nails. The para-isomer is the most toxic of the three
mononitrophenols.
The toxic properties of the nitrotoluene are similar to those of
nitrobenzene but less pronounced. Poisoning can occur by ingestion, in-
halation and skin absorption and is characterized by headaches, drowsiness,
nausea, vomiting and in severe repeated cases, methemoglobinemia with
cyanosis, liver injury and jaundice.
The Threshold Limit Value (TLV) and Maximum Allowable Concentration
that have been established are:
Substance TLV - MAC-
ppm mg/M mg/M
p-nitrophenol — — 4
p-nitrotoluene 5 30
174
-------
3. OTHER HAZARDS
No special hazards other than those mentioned elsewhere in this report
are connected with the manufacture and use of these compounds.0766'1433'1492'
1569
4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling. Storage and Transportation '
The nitroaromatic hydrocarbons treated in this report are all very
toxic by inhalation, ingestion or skin contact. These materials should
only be handled in well-ventilated areas and protective clothing and res-
pirators are recommended where necessary. The toxic nature of these com-
pounds is such that all unnecessary contact with these compounds should be
avoided. In case of accidental contact, all contaminated clothing should
be removed instantly and the skin washed thoroughly with soap and water.
Bicarbonate solutions will help in the removal of the nitrophenols. A
change of clothing may be necessary after handling large amounts of these
compounds.0766'1433
Storage should be in a cool, dry, well-ventilated area, away from
acute fire hazards.
These materials are shipped under a variety of U. S. Department of
Transportation (DOT), U. S. Coast Guard and International Air Transport
Association (IATA) regulations. Since all the compounds treated in this
report have flash points above 100 C (212 F), none require DOT warning
labels for hazardous chemicals. The primary danger in shipping is due to
toxicity and information on safe handling and use of these compounds can
be found in the Chemical Data Sheets published by the Manufacturing Chemists
Association, standard reference sources, or manufacturers Technical Data
Sheets.
175
-------
Disposal/Reuse
Recommended provisional limits for the nitro compounds discussed in
this report are listed below.
$»
Contaminant and Basis for
Environment Provisional Limits Recommendation
3
Nitrophenol in 0.002 mg/M Based on similar
ai r compounds
Nitrotpluene in 0.05 ppm (0.30 mg/M3) 0.01 TLV
air
Nitrophenol in 0.010 ppm (mg/1) Based on similar
water and soil compounds
Nitrotoluene in 1.50 ppm (mg/1) Stokinger and
water and soil Woodward Method
The manufacture of nitrophenols and nitrotoluenes produces a dilute
stream of waste water from a washing or precipitation step. The streams
can be either acid or alkaline. A small amount of distillation bottoms
is also produced.
The Manufacturing Chemists Association Chemical Data Sheet SD-21 for
2479
a nitrobenzene suggests that small quantities can be disposed of by
open burning or as slurry by flushing down the sewer. Disposal of larger
quantities by landfill in areas reserved for toxic wastes is suggested.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Treatment of Waste Water to Reduce Biological
and Chemical Oxygen Demand
The nitrophenols and nitrotoluenes are biodegradable to acclimated
activated sludges. In addition, microorganisms are very sensitive to shock
by these compounds and release of abnormal amounts can cause failure of an
176
-------
1543 2479
activated sludge treatment plant. ' For these reasons, it is rec-
ommended that waste streams be treated on site. Discharge of partially
treated waste water should be done only with approval of the local municipal
treatment plant and in a continuous, low level manner.
Option No. 2 - Incineration
Contaminated material that cannot be reclaimed is best disposed of
by controlled incineration. The toxic nature of these compounds requires
extreme care to maintain complete combustion at all times. Incineration
of large quantities may require the use of scrubbers and/or thermal or
1435
catalytic devices to control the level of effluent oxides of nitrogen.
Option No. 3 - Flushing Small Quantities Down the Sewer as a Slurry
This alternative is suggested by the Manufacturing Chemists Association
for nitrobenzene and would presumably also be applicable to the nitrotol-
2479
uenes. It should not be considered as a valid method of disposal since
accumulation of nitrotoluene or nitrotoluene vapors in drains and/or sewers
could pose a serious hazard to unsuspecting personnel. In addition, in-
sufficient dilution could cause damage to activated sludge sewage treatment
plants.
Option No. 4 - Landfill of Large Quantities of Nitrotoluene at
Special Toxic Wastes Landfill Sites
This method is suggested by the Manufacturing Chemists Association
for nitrobenzene and should also be applicable to the nitrotoluenes.
This method of disposal is not considered adequate unless the landfills
are of the California Class 1 type since these nitro compounds are toxic,
mobile and slightly volatile. In addition, their solubility of 100 to 150
ppm in water presents a long-term potential hazard to underground water
supplies.
177
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Dilute aqueous wastes are best treated on site or in conjunction with
municipal sewage treatment systems by conventional biological treatments.
Unusable concentrated nitrotoluene and nitrophenol materials are best dis-
posed of by common industrial incineration techniques. Therefore, the
nitro compounds discussed in this report are not judged to be candidate
waste stream constituents requiring National Disposal Site treatment.
178
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1435. John Zink Company. NO destructor. Bulletin No. NO 1071m, Tulsa,
John Zink Company. T p.
1492. Merck and Company, Inc. The Merck index of chemicals and drugs.
Rahway, New Jersey, 1960. 1,643 p.
1543. Ludzack, F. J., and M. B. Ettinger. Journal Water Pollution Control
Federation. 32:1,173-1,200, 1960.
1569. Manual of hazardous chemical reactions. Boston National Fire
Protection Association, 1971. 308 p.
2479. Nitrobenzene chemical safety data sheet SD-21, Washington, 1956.
16 p.
179
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name p-Nitrophenol (310)
- Structural Formula
IUC Name 4-nitrophenol
Common Names
Molecular Wt. 139.1 Melting Pt. 113-114 C Boiling Pt. 279 C
Density (Condensed) 1.270 @ 120/4 C^1' Density (gas) _@
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
So1ub111t-y 1.6 g/100 ml 25 C(4) 29 g/100 ml 90 C <4> (
Cold Water Moderate!2) _ Hot Water Very(3) _ Ethanol Very
Others: very, chloroform, ether; addition of base of carbonate to aqueous solutions
increases solubility (2)
Acid, Base Properties _ acidic. K = 7x1Q-8 _
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification Coast Guard Classification_
Conmen ts
References (1) 0766 (4) 1433
(2) 1492
(3) 1570
180
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name p-Nitrotoluene (312)
IUC Name 4-ni'trotoluene
Common Names methyl ni trobenzene
Structural Formula
137.1
Molecular Wt.
Density (Condensed) 1.286
Melting Pt. 51.9 C
r(D
Density (gas)_
Boiling Pt. 238.3
@
Vapor Pressure (recommended 55 C and 20 C)
1)
1 mm @ 53.7
Flash Point 223
' ;_ Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper
Solubility
Cold Water very slightly
(2)
Hot Water
Ethanol soluble
(2)
Others: soluble, benzene, ether, chloroform, acetone,
carbon disulfide.(3)
Acid, Base Properties
(2)
carbon tetrachloride,
Highly Reactive with
Compatible with
Shipped in
IATA: Poison B, poison label
ICC Classification
Comments
Coast Guard Classification
References (1) 0766
(2) 1492
(3) 1570
181
-------
PROFILE REPORT
Oxalic Acid (317)
1. GENERAL
Oxalic acid is the first member of the homologous series of organic,
dicarboxylic acids. It is widely distributed in plants, particularly in
those of the "Oxalis" and "Rumex" families, where it occurs in the cell
1492
sap as the potassium or calcium salt. The acid is commercially avail-
able as the dihydrate, an odorless, crystalline material which is supplied
1433
in particle sizes ranging from fine powder to coarse granular. The
principal hazards associated with the dihydrate and the less frequently en-
countered anhydrous acid and their solution? are a consequence of the
acidity of oxalic acid, its volatility and its ability to form insoluble
salts.1492
There are several synthetic routes for the preparation of oxalic
acid, but only two are in current use by the major, domestic
manufacturers. The acid is manufactured by Allied Chemical, by the
heating of sodium formate, in Buffalo, New York (capacity: 10 million
Ib/year), and Marcus Hook, Pennsylvania (capacity: 10 million Ib/year).
Pfizer, Inc. produces the material (capacity 12 million Ib/year) in Groton,
Connecticut as a by-product of the fermentation process used for the pro-
duction of citric acid. ' Both manufacturing processes require
extensive reuse of reaction by-products and recrystallization liquors for
economi c
quality.
economic viability, thus providing an impetus for control of effluent
Oxalic acid is employed in a variety of applications by organizations
ranging in size from small to very large.1006,1492,1433,1567 Its prin_
cipal uses and their approximate share of the market are: textile
finishing, stripping and cleaning, 27 percent; metal and equipment cleaning,
183
-------
27 percent; chemicals, 25 percent; leather tanning, 2 percent; other
(laundry, photography, etc.), 19 percent. There is a gradual trend to
replace oxalic acid, in some of its applications., with more innocuous,
materials.1567
The physical/chemical properties of oxalic acid are summarized In the
attached worksheet.
2. TOXICOLOGY0766
Acute oxalic poisoning results from ingestion of a solution of the
acid. There is marked corrosion of the mouth, esophagus and stomach, with
symptoms of vomiting, burning abdominal pain, collapse and sometimes con-
vulsions. Death may follow quickly. The systemic effects are attributed
to the removal by oxalic acid of the calcium in the blood. The renal tu-
bules become obstructed by insoluble calcium oxalate, leading to massive
kidney failure. Inhalation of the dust or vapor may cause symptoms of
irritation of the upper respiratory tract and gastrointestinal disturbances.
ToxicologicalDevaluation indicates that the Threshold Limit Value for
3
man is 1 mg/M . Toxicity data for species other than man are sparse, but
1492
an oral LD in dogs of 1.0 g/kg has been reported.
3. OTHER HAZARDS
Oxalic acid causes severe contact dermititus typical of strong organic
.°766 This acidity is also likely ti
tions with concentrated basic substances.
acids. This acidity is also likely to be manifest by exothermic reac-
Explosive reactions have been reported for mixtures of oxalic acid
with sodium chlorite and sodium hypochlorite. Since oxalic acid is
a reducing agent, care should be taken to preclude its contact with strong,
concentrated oxidizing agents.
184
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Care should be taken to avoid inhalation of oxalic acid dust or pro-
longed skin contact with the acid. Normal, safe industrial practice for
the handling of strong acids should provide adequate protection.
Oxalic acid is usually supplied as the dihydrate and packed in fiber
1433
drums. It is classed by the International Air Transport Association
as Poison B, requiring a poison label and limited to a maximum of 25 kg on
passenger flights and 95 kg on cargo flights.
Disposal/Reuse
Purification of oxalic acid by recrystallization is a normal part of
1433
the manufacturing process and oxalic acid users with the required equip-
ment may employ this technique to recover slightly contaminated material.
An adequate process for the disposal of oxalic acid must include two
important steps. First, the waste must be diluted with water to lower the
concentration of oxalic acid to <10 percent (will not cause death if
swallowed ) to reduce danger of poisoning, eliminate dust and provide a
heat-sink for the second required step; neutralization with base. Salt
formation by neutralization eliminates the danger of acid bums and reduces
the volatility of the material. The particular base to be used in the
neutralization depends on the nature of the final disposal process (Section
5).
Recommended provisional limits for oxalic acid in the environment are
as follows:
185
-------
Contaminant and Basis for
Environment Provisional Limits Recommendation
Oxalic acid in 0.01 mg/M3 0.01 TLV
ai r
Oxalic acid in 0.05 ppm (mg/1) Stokinger and
water and soil Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The preferred processing options for the disposal of oxalic acid wastes
are briefly described in the following .paragraphs together with judgments as
to their adequacy.
Option No. 1 - Incineration
One common method for the disposal of industrial oxalic acid waste is
to neutralize it with limestone to form insoluble calcium oxalate which is
then incinerated. This is probably the best method for disposal of
oxalic acid since the products of combustion are harmless carbon dioxide
and calcium oxide which can be recycled to neutralize more acid waste.
The efficient collection of calcium oxide requires either electrostatic
or wet collection equipment downstream of the incinerator.
Combustion of oxalic acid without neutralization is not recommended
since toxic carbon monoxide and formic acid are among the materials pro-
duced. In addition, there is the strong possibility of the release to the
atmosphere of some of the volatile oxalic acid.
Option No. 2 - Waste Water Treatment
Effective disposal of oxalic acid by the activated sludge process has
1 C A O
been reported. This process is adequate for waste disposal but is
generally more expensive and difficult to operate than incineration (see
Waste Disposal Process Descriptions, Volumes III and IV).
186
-------
Other biological treatments such as aerated lagooning are less accept-
able. The soluble salts (potassium or sodium oxalate) that are required
for their efficient operation introduce the possibility of drainage into
ground water.
In view of the wide range of size and sophistication of the industrial
organizations using oxalic acid, ' it would not be surprising if
some small volume users discard their waste directly into sewer systems and
streams. Although not recommended, this practice will not be harmful pro-
vided the quantity is small and well diluted since oxalic acid in aqueous
solution is decomposed by ultraviolet radiation with the liberation of
1433
carbon dioxide.
Option No. 3 - Land Burial
Many users of oxalic acid neutralize their waste streams with lime-
stone and bury the recovered calcium oxalate in Class 2 landfill or deep
wells. These methods are not generally recommended because of the
danger of release of oxalic acid by the leaching action of acidic wastes.
Another potential danger lies in inadvertent contact with strong oxidizing
agents in the burial area. Disposal in California Class I-type landfills
is adequate if strong oxidizing agents are not present.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Oxalic acid does not appear to be a candidate waste stream constituent
for disposal at National Disposal Sites. The hazards associated with
oxalic acid can be alleviated by the simple process of dilution and
neutralization and it can then be effectively and safely eliminated in
incinerators equipped with particulate removal devices, or buried in a
Clas 1 type landfill.
187
-------
7. REFERENCES
0766.. Sax, N. I. Dangerous properties of industrial materials. 3d ed,.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemvcal technology. 2d ed. 22 v.. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1492. Merck and Company, Inc. The Merck rndex of chemicals and drugs..
Rahway, New Jersey, 1960. 1,643 p.
1506. 1968 Chemical profiles. Schnell Publishing Company, Inc., New York.
200 p.
1543. Ludzack, F. J., and M. B.. Ettinger. Chemical structures resistant
to aerobic chemical stabilization. Water Pollution Control
Federation, 32(11) :1,173-1,200.. Nov. 1960.
1567. Personal communication. A. Thomas, Phizer Inc., to H. E. Green., TRW
Systems, Apr. 20, 1972.
1569. National Fire Protection Association. Manual of hazardous chemical
reactions 1971. 4th ed. NFPA No. 491M. Boston. 308 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, 1966. 1,500 p.
188
-------
H. M. Name Oxalic Acid (317)
IUC Name Ethanedioic Acid
Common Names
Molecular Wt. 90.04^
Density (Condensed) 1.90 @
Vapor Pressure (recommended 55 C
0.92 mm @ 60 C^
Flash Point
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Solubility, (4)
Cold Water 8.7 g/100 g @ 20
HAZARDOUS WASTES PROPERTIES
WORKSHEET
C2H2°4
Structural Formula
H02C-C02H
n> n^Sub"
Melting Pt. 189.5 Cu/ Boiling Pt. 157 Cu; limes
17 /4 Cl density (gas) &
and 20 C)
-------
PROFILE REPORT
Phosgene (Carbonyl Chloride) (329,101)
1. GENERAL
At ordinary temperatures and pressures, phosgene is a colorless, non-
flammable, highly-toxic gas with an odor like that of musty hay. It is
readily liquified to a colorless to light yellow liquid and is shipped in
steel cylinders as a liquified gas under its own vapor pressure (10.7 psig
at 70 F). Phosgene is made by the addition of chlorine to carbon monoxide
in the presence of a catalyst, usually carbon granules.
CO + C12 •* COC12
Because much heat is evolved, the reaction is usually started in a water-
cooled reactor and then as the reaction nears completion, the temperature is
allowed to rise slightly. Phosgene is easily separated from the starting
materials because it has a much lower vapor pressure than either carbon mon-
oxide or chlorine. The unreacted chlorine and carbon monoxide are recycled.
Phosgene is used in organic synthesis in the manufacture of dyes, phar-
maceutical s, herbicides, insecticides, synthetic foams, polymers and as a
chlorinating agent (acetyl chloride). Any unreacted phosgene discharged
from a reactor must be treated as discussed in Section 5.
The physical/chemical properties for phosgene are summarized in the
attached worksheet.
191
-------
2. TOXICOLOGY
Human Toxicity
Phosgene is a highly toxic gas, being over 10 times as toxic as chlorine.
Serious symptoms may not develop until several hours after exposure. The
immediate symptoms produced by a fatal dose may be relatively mild since
phosgene elicits no marked respiratory reflexes. Phosgene is a lung irritant
and causes severe damage to the alveoli of the lungs. This is followed by
pulmonary edema, resulting in asphyxiation. Its effects are probably due
to hydrolysis and the formation of hydrochloric acid inside the body. The
most pronounced symptoms of phosgene poisoning are coughing with bloody
sputum and weakness which may last for months.
The least detectable odor of phosgene is 5.6 ppm, the least concentration
that affects the throat is 3.1 ppm, the least concentration causing irritation
of the eyes is 4.0 ppm and the least concentration causing coughing is 4.8 ppm.
A concentration of 200 to 500 ppm is lethal to most animals in a few minutes.
The median lethal dosage for phosgene (U. S. Army symbol - CG), expressed
as a function of exposure time and CG concentration in air, is 3,200 mg -
3 2442
min/M . The effects of phosgene are cumulative. The maximum concen-
tration to which animals can be exposed for several hours without serious
symptoms is 0.1 ppm. This is accepted as both the Maximum Allowable Con-
centration (MAC) for 8-hr exposure, and the Threshold Limit Value (TLV).
3. OTHER HAZARDS
Phosgene does not create a fire or explosion hazard. It is slightly
soluble in water and slowly hydrolyzes to liberate hydrochloric acid. When
used in dry equipment with anhydrous reagents, it is not corrosive to ordi-
nary metals. In the presence of moisture, corrosion develops in most metals
except monel and tantalum. Glass equipment may also be used with moist
phosgene.
192
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Transportation, and Storage
Personnel handling and using phosgene must have available gas masks of
a design approved by the U. S. Bureau of Mines for phosgene service with
cannisters approved for use with phosgene.
All equipment intended for use in phosgene service must be adequately
designed to withstand the-pressures to be encountered and be without any
leaks.
Phosgene is classified by the Department of Transportation (DOT) and
the U. S. Coast Guard as a Class A poison and is shipped under the "Poison
Gas" label in steel cylinders up to one ton in size without safety devices.
These containers are usually used only for the storage of phosgene and
must be stored away from sources of heat to prevent dangerous hydrostatic
pressures from developing in the cylinder.
Disposal/Reuse
Phosgene waste is almost always in the form of a dilute gaseous vent
stream contaminant, when discharged from the containers or from the reactors
in which it is used as a reagent. Recovery and reuse of this vented phos-
gene is generally economically impractical. The discharged phosgene must
be treated by the methods described below. Safe disposal of phosgene is
defined in terms of the recommended provisional limits for the atmosphere,
and for water and soil environments. These recommended provisional limits
are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
Phosgene 0.004 mg/M3 0.01 TLV
Contaminant in Basis
Water and Soil Provisional Limit Recommendation
Phosgene 0.02 mg/1 Stokinger and
Woodward Method
193
-------
Contaminated tank car lots of phosgene should, if safe for transportation,
be returned to the manufacturer for reprocess and recovery.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of phosgene in the gaseous
state are briefly described in the following paragraphs, together with;
recommendations as to adequacy. The Manufacturing Chemist Association
does not publish a recommended method for phosgene disposal, but instead
recommends that any unused material be returned to the vendor.
0
Option No. 1 - Scrubbing With Caustic
Phosgene has been treated by discharging the gas into a scrubbing
tower containing 5 percent sodium hydroxide solutions. However, a
discussion with a manufacturer of phosgene indicated that a packed
column containing a solution of sodium hydroxide, potassium hydroxide or
ammonia is required. The contact time in the column must be rather lon-g.
With adequate attention to dilution (high stacks, forced air, etc.),
packed bed scrubbers and towers have been used. Because of the extremely
toxic character of phosgene, the existing engineering data is not sufficient
to enable design of scrubbing systems with the required safety. It is
recommended that additional data be generated to enable design of safe
disposal systems for phosgene.
Option No. 2 - Reaction With Alcohols
Phosgene roacts with alcohols to yield first chloroformates and then
carbonates. The carbonates have a market for the manufacture of polymers.
This method, if properly performed, allows nearly complete removal of
phosgene from a gas stream. However, again adequate details are lacking
to enable design of safe systems. Additional work is required to obtain
the engineering data necessary to assure complete removal of phosgene.
194
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Option No. 3 - Elevated Temperature Hydrolysis
With Steam and Na0COo Scrubbing
' * • £ «3
A suggested approach, is reaction with steam at moderately elevated
temperatures to yield C02 and HC19 followed by sodium carbonate solution
scrubbing to remove the HC1. The reactions are as follows:
COC12 + H20 4 C02 + 2 HC1
2 HC1 + Na2C03 + 2 NaCl(aq)+ HgO + C02*
The engineering parameters necessary for design of the hydrolysis system
are not available in the literature. The engineering parameters required
for design of the HC1 scrubbing system are available.
No data is currently available on the COC12 content of waste streams
discharged from the currently used versions of the above three disposal
options. Based on engineering principles, the elevated temperature reaction
with steam followed by sodium carbonate solution is the preferred option,
the reaction with alkali solution in a packed tower is second in preference,
and the reaction with alcohol third in order of preference.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that phosgene wastes generated in chemical processes
and either excess phosgene or small quantities left in returned cylinders
can be handled best at the source of the wastes rather than at a National
Disposal Site. However, the necessary design parameters for the disposal
method described in Section 5 are lacking. We recommend that a "proof of
concept" experiment be performed, and that the necessary engineering data
be obtained experimentally.
The "proof of concept" experiments would consist of the reaction of
dilute phosgene-airstreams with steam in a carbon-packed, jacketed glass
195
-------
column at various flow rates, initial phosgene concentrations and temperatures,
The data obtained by analysis of the effluents would be used in conjunction
with thermodynamic data from the literature to derive the equilibrium
constants, reaction rate constants, and other engineering parameters needed
for safe system design.
196
-------
7. REFERENCES
1141. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Manufacturing Chemists Association, Sept. 1969. 14 p.
1301. Matheson Company, Inc. Matheson gas data book. 4th ed. East
Rutherford, New Jersey, 1966. 500 p.
1487. Personal communication. Mr. Huff, Chemetron Corporation, to J. R.
Denson, TRW Systems, Mar. 27, 1972.
2442. Department of the Army and Air Force. Military chemistry and chemical
agents. TM-3-215, AFM-355-7. Washington, Dec. 1963. 101 p.
197
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
i
H. H..Name Phosgene (101)
Structural Formula
IUC Name Phosgene
Common Names Carbonyl Chloride
COC1
2
Molecular Wt. 98.93 Melting Pt. -127.85 C Boiling Pt7.56 C
Density (Condensed) 1.417g/cc @ 0 ' C Density (aas) 3.4 @ 20 _C
Vapor Pressure (recommended 55 C and 20 C)
1.08 atm @ 10 C 1.55 atm? 20 C 3.99 atm @ 50
Flash Point Autoignition Temp. -
Flammability Limits in Air (wt %) Lower - Upper -
Explosive Limits in Air (wt. %) Lower - Upper -
Solubility
Cold Water Slightly (hydrolyzes) Hot Water hydrolyzes Ethanol reacts
Others: Soluble in benzene
1 Acid, Base Properties Hydrolyzes in H,0 to give HC1
Highly Reactive with Alcohols, amines
Compatible with In anhydrous form, compatible with most metals
Shipped in steel cylinders, special, one ton cylinders
ICC Classification C1ass fl poison Coast Guard Classification Class A poison
Commen ts
References (1)
198
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PROFILE REPORT
Polychlorinated Biphenyls (507)
1. GENERAL
Polychlorinated biphenyl and polychlorinated polyphenyls range in form
and appearance from mobile oily liquids to fine white crystals and hard
transparent resins. They are non-oxidizing, permanently thermoplastic, of
1727
low volatility, and non-corrosive to metals.
Aroclor is the registered trademark of Monsanto Company, the sole sup-
1726
plier and manufacturer of polychlorinated biphenyls i.n the United States.
These materials are obtained when benzene is heated to between 700 and
800 C and the vapor passed through molten lead or hot tubes to form bi- and
terphenyls. The bi- and terphenyls are then halogenated to form the
Aroclors.1316
Polychlorinated biphenyls were produced by Swan Chemical Company in
1929 in response to the electrical industry's need for an explosion proof
insulating fluid for transformers. Monsanto acquired Swan in the early
thirties and in the same period new applications opened up for polychlori-
nated biphenyls as industrial heat-transfer media. Monsanto promoted the
use of these materials in the 1960's for sealants, chlorinated rubber,
1726
adhesive, printing inks and insecticides. These materials have also
been used as a component or extender in elastomers, paints, lacquers,
1727
varnishes, pigments and waxes.
The polychlorinated biphenyls have come under heavy attack from environ-
mental groups and in Congress from Representative William Ryan (Dem., New
York) because of their similarity to DDT in their effect on eggs and animal
life. As a consequence of this adverse environmental impact, Monsanto is
now limiting the sale of polychlorinated biphenyls to applications involving
199
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completely closed systems. In effect, insulation of electrical equipment
is the only domestic market now permitted for these materials. Monsanto is
refunding full payment for unopened drums of material and paying freight
costs for the return of opened drums of material to be destroyed in the
incinerator at the company's Sauget, Illinois plant.
General physical properties of the Aroclor chlorinated compounds are
found in the attached worksheets.
2. TOXICOLOGY
At ordinary temperatures the polychlorinated polyphenyls have not pre-
sented industrial toxicological problems. The hazard of potential toxic
exposure increases with increased volatility. Thus, the Aroclors with a
lower level of chlorine substitution present more of a potential problem
from the standpoint of inhalation even though they may be less inherently
toxic than their more highly substituted homologues.
The chlorinated diphenyls have two distinct actions on the body, namely,
a skin effect and a toxic action on the liver. The lesion produced in the
liver is an acute yellow atrophy. This hepato-toxic action of the chlorinated
diphenyls appears to be increased if there is exposure to carbon tetrachloride
at the same time. The higher the chlorine content of the diphenyl compound,
the more toxic is it liable to be. Oxides of chlorinated diphenyls are more
toxic than the unoxidized materials.
The skin lesion is known as chloracne, and initially consists of small
pimples and dark pigmentation of the exposed areas. Later, comedones and
pustules develop. In persons who have suffered systemic intoxication the
usual signs and symtoms are nausea, vomiting, loss of weight, jaundice,
edema and abdominal pain. Where the liver damage has been severe, the
patient may pass into coma and die.
Inhalation tests on animals indicate that the maximum safe concentra-
tion of vapor is in the range of 0.5 to 1.0 milligrams per cubic meter of
200
-------
air for the lower chlorinated Aroclor compounds. The Threshold Limit Value
(TLV) (maximum allowable concentration for an 8-hr working day) set by the
American Conference of Government Hygienists are 1.0 milligram of the lower-
chlorinated Aroclor compounds per cubic meter of air and 0.5 milligrams per
cubic meter of air for the more highly chlorinated compounds such as
Aroclor 1254.
3. OTHER HAZARDS
There is only a slight fire hazard when chlorinated diphenyls are ex-
posed to heat or flame. The viscous polyphenyl liquids and resins will
not support combustion when heated alone, and they impart fire-reistance to
other materials. Continuous repeated skin contact with polychlorinated
polyphenyls must be avoided because of the possible occurrence of
chlorance. Although reports of this condition caused by these
I 7O7
materials are rare, it can be produced by excessive skin contact.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
The polychlorinated polyphenyls are compatible with most metals from
room temperature to 125 C. Organic resins show less resistance and detailed
1727
information on this subject has been supplied by Monsanto. Liquid poly-
chlorinated polyphenyls are shipped in steel drums, cans and tank cars.
Solid materials are generally shipped in steel drums, fiber drums and
I 797
bags. Freight and rail classification for these materials is NOIBN
(not otherwise indexed by name). Truck classification is NOI (not otherwise
indexed).
Safety in the handling and use of polychlorinated biphenyls required
that exposure to the liquids and their vapors be minimized. Workmen must
be supplied with proper protective clothing and ventilating systems must be
designed and maintained to provide work areas with vapor concentrations be-
low the limits mentioned in Section 2.
201
-------
1727
Disposal/Reuse
Monsanto1s polychlorinated biphenyl manufacturing operations have ex-
perienced a tightening of standards on handling these materials. To prevent
water contamination, there is none of the hosing down found in most chemical
plants. Other measures include complete monitoring of all vents and traps
for leaks at all sample points. All tanks are closed and all of the air
and gas that escapes the plant is passed through a Brink mist eliminator.
In addition, process temperatures have been lowered to prevent vaporization.
Clothing is provided for all workers, and after the clothes are cleaned
all the cleaning fluid is collected for destruction by incineration. The
incinerator operates at a temperature of 3,000 F. Hydrochloric acid evo-
lution is prevented by use of a water scrubber and by neutralization of the
resulting fluid. Recommended provisional limits for polychlorinated poly-
phenyl to the environment are as follows:
>
1
Contaminant and Basis for
Environment Provisional Limit Recommendation
Lower Chlorinated 0.01 mg/M3 .01 TLV
Aroclors in Air
Higher Chlorinated 0.005 mg/M3, .01 TLV
Aroclors in Air
Lower Chlorinated 0.05 ppm (mg/1) Stokinger and
Aroclors in Water Woodward Method
and Soil
Higher Chlorinated 0.025 ppm (mg/1) Stokinger and
Aroclors in Water Woodward Method
and Soil
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Polychlorinated polyphenyls are expected to appear as concentrated
17?fi
and dilute organic wastes as solids, liquids and vapors. The processing
options are briefly described in the following paragraphs together with re-
commendations as to their adequacy.
202
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Concentrated Polychlorinated Biphenyls
Contaminated polychlorinated biphenyls are reprocessed by Monsanto by
1 "
passing the material through a series of clay filters. Concentrated
materials that cannot be reprocessed in this manner are incinerated at
3,000 F and the effluent gas scrubbed to remove any chlorine containing
products. These are adequate means of disposal/reuse.
Dilute Solid Polychlorinated Biphenyl Hastes
Materials containing polychlorinated biphenyls such as plastics are
placed in incinerators at relatively low temperatures for disposal. The
polychlorinated biphenyls are not destroyed in this process and may be
emitted to the atmosphere. High temperature (3,000 F) incinerators with
effluent gas scrubbers (see section on concentrated polychlorinated bi-
phenyls) are also used. The high temperature incinerators are adequate
for the disposal of these materials. The low temperature incinerators
are not recommended because of incomplete destruction of the polychlorinated
biphenyls.
Dilute Liquid Organic Polychlorinated Biphenyl Wastes
Cleaning fluids used to clean work clothes are incinerated as described
in the section on concentrated polychlorinated biphenyls. Tars and/or bot-
toms containing these materials should be disposed of in a similar manner.
Dilute Aqueous Polychlorinated Biphenyl Wastes.
Although dilute aqueous wastes have not been identified with poly-
chlorinated biphenyl manufacture, it is recommended that any such waste be
concentrated and incinerated as described in the section on concentrated
polychlorinated biphenyls.
203
-------
Dilute Vapor Polychlorinated Biphenyl Wastes
All of the air and gas that escapes the Monsanto plant is passed
I ~]OC
through a Brink mist eliminator. This is an adequate means of control
provided federal, state and local emission standards are not exceeded.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Polychlorinated biphenyl wastes are expected to appear in both concen-
trated and dilute forms. Adequate means of handling the disposal of these
wastes are located at industrial disposal facilities and represent common
industrial technology. Users are encouraged by the manufacturer to return
concentrated waste for disposal (see Section 1). Dilute wastes should be
treated as discussed in Section 5. These materials are not judged to be
candidate waste stream constituents for National Disposal Sites.
204
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1316. Noller, C. R. Chemistry of organic compounds. 2d ed. Philadelphia,
W. B. Saunders Company, 1957. 978 p.
1660. Hot option for disposal of hydrocarbon wastes. Chemical Week.
110(16):37-38, Apr. 1972.
1726. Pollution cops lot not 'appy. Chemical Week, 108(16) :19-20, Apr. 1971
1727. Monsanto. The Aroclor polychlorinated polyphenyls. Technical
Bulletin No. .O-FF/1. St. Louis, Missouri. 24 p.
205
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polychlorinated biphenyls (507)
Structural Formula
IUC. Name
Common Names Polychloginated polyphenyls
Aroclor T221
Molecular Wt. Pour Pt. Crystals 1 C Distillation Range 275-320 C
Density (Condensed) 1.182-1.192 @ 25/15.5 C , @
Vapor Pressure (recommended 55 C and 20 C)
Flash Point 141-150 C Fire Point. 176 C Cleveland Open Cup
Cleveland Open Cup
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Insoluble Hot Water Ethanol
Others: Soluble in most common solvents
Acid, Base Properties Acidity-maximum (mgm. KOH/ gm.) 0.014
Highly Reactive with_
Compatible with A variety of solvents, oils and resins, most metals
Shipped in Tank car, steel drum, 50-1b can.
ICC Classification NOIBN Coast Guard Classification_
Corranents Mfg: Monsanto. Material is a colorless mobile oil
References (1) 1727
206
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polychlorinated biphenyls (507)
IUC Name
Common Names Polychlflrinated Polyphenyls
Aroclor '
Structural Formula
Molecular Wt.
Pour Pt.
_-35.5 C
.Distillation Range 290-325 C
Density (Condensed) 1.270-1.280 @ 25/15.5 C Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
37.8 C @
5 x 10"3 mm
Flash Point 152-154 C
Open Cleveland Cup
FlammabilHy Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Fire Pt. 238 C Cleveland Open Cup
Lower Upper
Lower
Upper
Hot Water
Solubility
Cold Water Insoluble
Others: Soluble in most common solvents
Acid, Base Properties Acidity-maximum (Mqm. KOH/qm.) 0.014
Ethanol
Highly Reactive with_
Compatible with A variety of solvents, oils and resins, most metals
Shipped in Tank car, 550-lb steel drum, 50-lb can.
ICC Classification
Coast Guard Classification
Comments Mfg: Monsanto. Material is practically colorless mobile oil
References (1) 1727
207
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Polychlorinated Biphenyls (507)
Structural Formula
IUC Name
Common Names Polychlorinated Polyphenyls
Aroclor 1248
Molecular Wt. Pour Pt. -7C Distillation Range: 340-375 C
Density (Condensed) 1.405-1.415 & 65/15.5 C Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
3.3 mm @ 150 C ^3.7 x IP"4 & 37.8 C @
Flash Point 193-196 C Fire Pt. None
Cleveland Open Cup
Flammabiljty Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Insoluble Hot Water Ethanol_
Others: Soluble in most common sol vents
Acid, Base Properties Acidity-maximum (Mgm. KOH/Gm.) 0.010
Highly Reactive with_
Compatible with A variety of solvents, oils and resins, most metals
Shipped in Tank car, 600-lb steel drum, 50-lb. can
ICC Classification NOIBN Coast Guard Classification
Mfg: Monsanto. Material i<; mlnrlp<:<: tr> light yellow-grean, clear mobile oil
References (1) 1727
208
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polvchlorinated Biphenyls (507)
Structural Formula
IUC Name
Common Names Polvchlorinated Polyphenyls
Aroclor* 1242
Molecular Wt. p0ur Pt. -19_C QisiUlatinn Ranns 3?5-3fifi r
Density (Condensed) \ .381-1.392 @ 25/15.5 C Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
4.3 @ 150 C 1 x 1Q"3 mm 9 37.8 r. _@
Flash Point 176-180 C - Fire Pt. None
Cleveland Open Cup
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Insoluble Hot Water Ethanol_
Others: Soluble in most common solvents
Acid, Base Properties Acidity- maximum (Mgm. KOH/am.) 0.010
Highly Reactive with_
Compatible with A variety of solvents, oils and resins, most metals
Shipped in Tank car, 600-lb steel drums. 50-lb can.
ICC Classification NOIBN Coast Guard Classification
Mf9- Monsanto. Material is practically colorless mobile oil
References (1) 1727
209
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polvchlorinated Riphenyls (507^
Structural Formula
IUC Name
Common Names Polvchlprinated Polvphenvls .
Aroclor" 1254
Molecular Wt. Pour Pt. 10 C Distillation Range: 365-.390 C
Density (Condensed) i .495-1.505 @ 65/15.5 C Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
LJ @ 150 C %6 x IP'5 mm 9 37.8 C @
Flash Point None Fire .Point: None _
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Insoluble Hot Water Ethanol_
Others: Soluble in most common sol vents
Acid, Base Properties Acidity-maximum (Mqm. KOH/qm.) 0.010
Highly Reactive with_
Compatible with A variety of solvents, oils and resins, most metals
Shipped in Tank car, 600-1b steel drum, 50-1b can
ICC Classification NOIBN . . Coast Guard Classification_
Comments Mfg: Monsanto- Material is light yellow viscous oil
References (1) 1727
210
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polychlorinated Biphenyls (507)
Structural Formula
IUC Name
Common Names Polychlflrinated Polyphenyls
Aroclor 1260
Molecular Wt. Pour Pt: 31 C Distillation Range: 385-420 C
Density (Condensed) 1.555-1.566 @ 90/15.5 C Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
2 mm @ 175 C 9 &
Flash Point None Fire Pt: None
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Insoluble Hot Water Ethanol.
Others: Soluble in most common sol vents
Acid, Base Properties Acidity-maximum (Mgm. KOH/Gm.) 0.014
Highly Reactive with_
Compatible with A variety of solvents, oils and resins, most metals
Shipped in Tank car, 600-1b steel drum, 50-lb can
ICC Classification NOIBN Coast Guard Classification_
Comments Mfg: Monsanto. Material is light yellow soft sticky resin
References (1) 1727
211
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polvchlorinated Biphenyls(507)
Structural Formula
IUC Name
Common Names Polychlorinated Polyphenyls
AroclorR 1262
Molecular Wt. Pour Pt: 35-38 C Distillation Ranije: 395-425 C
Density (Condensed) 1.572-1.583 @ 90/13.5 C Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
Flash Point None Fire Pt: None
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Insoluble Hot Water . Ethanol
Others: Soluble in most common sol vents
Acid, Base Properties Acidity-maximum (Mgm. KOH/Gm.) 0.014
Highly Reactive with
Compatible with A variety of solvents, oils and resins, most metals.
Snipped in Tank car> 600-lb steel drum, 50-lb can
ICC Classification NOIBN Coast Guard Classification
Mfg: Monsanto. Material is light yllnw stirky
References (1) 1727
-------
HAZARDOUS WASTES PROPERTIES
' WORKSHEET
H. M. Name Polychlorinated Biphenyls(507)
Structural Formula
IUC Name
Common Names Polychlorinated Polyphenyls
AroclorR 1268
Molecular Wt. Softening Pt: 150-170 C Distillation Range: 435-450 C
Density (Condensed)l .804-1.811 @ 25/25 C Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point None Fire Pt: None
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower [ Upper_
Solubility
Cold Water Insoluble Hot Water Ethanol
Others: Soluble in most common sol vents
Acid, Base Properties Acidity-maximum (Mgm. KOH/Gm.) 0.05
Highly Reactive with_
Compatible with A variety of solvent;, oils and resins, most metals
Shipped in 200-1 b fiber drum, 50-lb ce.
ICC Classification NOIBN Coast Guard Classification^
Comments Mfg: Monsanto- Material is .-.ite to off-white powder
References (1) 1727
213
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polychlorinated Biphenyls (507)
Structural Formula
IUC Name
Common Names Polychlorinated Polyphenyls
AroclorK 4465
Molecular Wt. Softenina Pt: fin-66 p nistination Ranae: 230-320 C
Density (Condensed) 1.670 @ 25/25 C Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point None Fire Pt: None
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Insoluble Hot Water Ethanol.
Others: Soluble in most common solvents
Acid, Base Properties Acidity-maximum (Mqin. KOH/Gin.) 0.05
Highly Reactive with
Compatible with A variety of solvents, oils and resins, most metals
Shipped in 500-1 b steel drum, 50-lb can
ICC Classification NOIBN Coast Guard Classification_
Comments Mfg: Monsanto. Material is light-yellow, clear, brittle resin
References (1) 1727
214
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name _Po1ych1orinated Biphenyls (507)
Structural Formula
IUC Name
Common Names Polychlorinated Polyphenvls
AroclorR 5442
Softening Pt: 46-52 C Pour Pt: 46 C Distillation Ranae: 215-300_C_
Density (Condensed) 1.470 @ 25/2S C Density (gas) @
Vapor Pressure (recommended 55 C and 20 0
& & @
Flash Point 247 C Fire Pt: >350 C
Cleveland Open cup
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Insoluble Hot Water Ethanol
Others: Soluble in most common solvents
Acid, Base Properties Acidity-maximum (Mgm. KOH/Gm.) 0.05
Highly Reactive with_
Compatible with A vareity of solvents, oils and resins, most metals
Shipped- in 450-1b steel drum, 50-lb can
ICC Classification NOIBN Coast Guard Classification,
Comments Mf9: Monsanto. Material is yellow transparent sticky resin
References (1) 1727
215
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polychlorinated Biphenyls (507)
Structural Formula
IUC Name
Common Names Polychlorinated Polyphenyls
Aroclor 5460
Molecular Wt. Softeninq Pt: 98-105.5 C Distillation Ranee: 280-335 C
Density (Condensed) 1.670 @ 25/25 C Density (gas) ja at 5 "m- Hg"
Vapor Pressure (recommended 55 C and 20 Q
@ 9 0
FlashPoint None Fire Pt: None
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Insoluble Hot Water Ethanol.
Others: Soluble in most common solvents
Acid, Base Properties Acidity-maximum (Mqm. KOH/Gm.) 0.05
Highly Reactive with_
Compatible with A variety of solvents, oils and resins, most metals
Shipped in (Flaked) 100-lb bag
ICC Classification NOIBN Coast Guard Classification
Comments Mfg: Monsanto. Material is clear, yellow-to-amber, brittle resin
References (1) 1727
216
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Polychlorinated Biphenyls (507)
Structural Formula
IUC Name
Common NamesPolychlprinated Folyphenyls
AroclorK 2565
Molecular Wt. Softening Pt: 66-72 C Distillation Range: -
Density (Condensed) 1.734 @ 25/25 C Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point None . Fire Pt: None
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Insoluble Hot Water Ethanol_
Others: Soluble in most common solvents
Acid, Base Properties Acidity-maximum (Mgm. KOH/Gm.) 1.4
Highly Reactive with_
Compatible with A vareity of solvents, oils and resins, most metals
Shipped in 500-lb steel drum. 50-lb can
ICC Classification NOIBN Coast Guard Classification_
Comments Mf9: Monsanto. Material is black, opaque, brittle resin
References (1) 1727
217
-------
PROFILE REPORT
Polyvinyl Nitrate (PVN) (535)
1. GENERAL
PVN is an insoluble explosive which is not used because of its poor
stability and because it cannot be placed into solution with a solvent. *
If used, it would have some of the applications of nitrocellulose. PVN can
be prepared by the nitration of polyvinyl alcohol with a mixture of nitric
acid and acetic anhydride, or with a mixture of nitric acid and carbon
tetrachloride. It is a readily flammable substance which burns without
melting.
Since PVN is not manufactured or used, it has not received DOD storage
and handling classifications, and shipping regulations covering, the material
have not been published. If it should be manufactured in the future,
shipping, handling and disposal procedures should be similar to those for
nitrocellulose (see Profile Report on Nitrocellulose, [534]).
The physical/chemical properties for PVN are summarized on the
attached worksheet.
219
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2. REFERENCES
0474. Tomlinson, W. R., Jr., revised by 0. E. Sheffied. Properties of
explosives of military interest, Technical Report No. 1740, Rev. 1,
Apr. 1958, Picatinny Arsenal. 348 p.
2169. Fedoroff, B. T., Encyclopedia of explosives and related items, v 1,
Picatinny Arsenal, 1960. 692 p.
220
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
II. H. Name Polyvinyl nitrate (535)
IUC Name
Common Names PVN
Structural Formula
(Cc
(89)n
Molecular Wt.
Density (Condensed)_
o:
Melting Pt. 50 C
(1)
Density (gas)_
Boiling Pt..
&
Vapor Pressure (recommended 55 C and 20 C)
Flash Point
Autoignition Temp._
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Solubility
Cold Water Insoluble"^
Hot Water
Ethanol
Others:
Acid, Base Properties.
Highly Reactive with_
Compatible with
Shipped in
ICC Classification None
Coast Guard Classification None
Comments Explosion temperature 265; has KPPH pmrinrpH only in the laboratory, fnr
experimental use, because of its instability.
References (1
C474
221
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PROFILE REPORT
Quinone (365)
1. GENERAL
Quinone is a common name for 1,4-benzoquinone, a yellow, crystalline
solid having a characteristic, irritating odor. It is the simplest member
of a large family of dioxo derivatives of dihydroaromatic compounds found
widely distributed in nature. Both synthetic and naturally occurring
quinones are of considerable commercial value as dyes, chemical intermedi-
ates, fungicides and drugs.
The principal domestic manufacturer of quinone is the Eastman Chemical
Product Division of Eastman Kodak. The material is manufactured at the
Kingsport, Tennessee plant by the oxidation of aniline in the presence of an
excess of manganese dioxide and sulfuric acid. Quinone is steam dis-
tilled from the reaction liquor and then purified, by recrystallization, for
sale in 50-lb (net) fiber drums. The remaining portion of the oxidation
solution is neutralized and filtered. The material obtained from the fil-
trate, after evaporation, is a technical grade of manganese sulfate called
Tecmangam, which is sold for use as a source of available manganese in
fertilizers and in animal feed.
Benzoquinone is an important chemical intermediate in the manufacture
I £07
of dyes, vitamins, bactericides, insecticides, fungicides, and, of
course, hydroquinone (see Profile Report on hydroquinone [220]). It is also
useful as a polymerization inhibitor for unsaturated polyesters and as a
1687
tanning agent in the leather industry. There are a number of other,
specialized applications which make use of its oxidizing properties.
2. TOXICOLOGY0766'1687
Quinone can cause severe local damage to the skin and mucous membranes
by contact with it in the solid state, in solution, or in the form of con-
densed vapor. Contact may result in discoloration, irritation, erythema,
223
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swelling, the formation of papules and vesicles, and after prolonged expos-
ure, necrosis. Repeated exposure to high vapor concentrations may cause a
greenish-brown stain or a grayish-white opacity of the cornea. In a few
cases there has been an appreciable loss of visual accuity. No evidence
has been found for a systemic effect.
The distinctive, irritating odor of quinone provides some measure of
warning of its presence in harmful concentrations. . Its odor becomes per-
ceptible at or just above 0.1 ppm and is quite definite in the region of
0.15 ppm and irritating at 0.5 ppm.
3. OTHER HAZARDS
Quinone itself does not constitute a fire or explosion hazard? however,
if present at the site of a fire or explosion, it may emit toxic fumes when
heated.0766 Care shouli
strong reducing agents.
heated. Care should also be taken to avoid uncontrolled contact with
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Personnel handling quinone should be familiar with its toxicological
properties. Gloves and goggles should be provided for their protection and
provisions should be made to keep the atmospheric concentration well below
0.1 ppm of air by volume. A careful medical examination of the eyes is ad-
visable before and during continued exposure to this chemical.1687
Disposal/Reuse
Quinone may be purified by recrystallization or by sublimation. Users
of this material may employ either technique to recover contaminated quinone
224
-------
if the required equipment is available and if the precautions outlined in
the section on handling, storage, and transportation are observed.
An adequate process for the disposal of quinorie must take into account
that it: (1) is toxic as a vapor, or a solid, or in solution; (2) has a high
sublimation pressure; (3) is soluble in water; (4) is resistant to biochemi-
cal attack because of its toxicity to lower organisms and its high oxidation
state. These properties favor disposal processes which provide for control
of vapor emission and rapid, complete conversion to innocuous products. Al-
ternatively, quinone may be converted (e.g., by-reduction) to less volatile
and/or more easily degraded forms before final disposal.
Recommended provisional limits for quinone in the environment are as
follows:
Contaminant and Basis for
Environment Provisional Limits Recommendation
Quinone in air 0.001 ppm (0.004 mg/M3) 0.01 TLV
Quinone in water 0.02 ppm (mg/1) Stokinger and
and soil Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The preferred processing options for the disposal of quinone wastes
are briefly described in the following subsections together with judgments
as to their adequacy.
Option No. 1 - Incineration
Incineration in a properly designed and operated incinerator is recom-
mended as the most satisfactory method for the disposal of waste quinone.
It is necessary that the incinerator be designed to burn the quinone com-
pletely (minimum of 1,800 F for at least 2.0 seconds) and that leackage of
unburned quinone vapors be eliminated. This option is applicable to both
concentrated and dilute quinone.wastes provided that an appropriate
incineration method is used.
225
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Option No. 2 - Waste Water Treatment
Biochemical waste water treatment processes are less satisfactory than
incineration for the disposal of quinone waste streams. Quinone is toxic
to most microbiota,,.is relatively resistant to oxidation since it is itself
an oxidizing agent, and is sufficiently volatile to be a potential odor and
toxicity problem in open lagoons. Treatment by the activated sludge process
using well acclimated seed is the most satisfactory biochemical treatment
method for chemically unmodified quinone wastes.
Quinone wastes can be rendered significantly more biodegradable by
prior reduction to hydroquinone or a hydroquinone derivative. Sodium sul-
1433
fite and sulfur dioxide are suitable reducing agents. Reduction to
hydroquinone, in addition to providing a more easily destroyed compound,
also eliminates the problems posed by the volatility of quinone.
Option No. 3 - Land Burial
Land burial disposal processes are generally less satisfactory than
Options Nos. 1 and 2 for disposal of quinone wastes. The high sublimation
pressure of this material poses the threat of release of toxic quinone fumes
to the atmosphere. Another possible route to environmental contamination is
the leaching of this water soluble material by rain or liquid wastes. A pro-
perly located and operated burial facility, meeting California Class I require-
ments may limit the impact of leaching but is unlikely to completely eliminate
the danger of sublimation.
Reduction of the quinone to hydroquinone prior to burial reduces its
potential for environmental damage (Option, No. 2). However, since hydro-
quinone is readily oxidized to quinone, the improvement must be regarded as
temporary.
, 6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Quinone does not appear to be a candidate waste stream constituent requiring
disposal at National Disposal Sites. This material is currently effectively
and safely disposed of at or near the sites of waste generation using the
methods cited in Section 5.
226
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7. REFERENCES
0766. Sax, N. I. Dangerous properties of Industrial materials. 3d ed.
New York, Reinhold Publishing Company, 1968. 1,251 p.
1433. Kirk-Othrner encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1492. Merck and Company, Inc. The Merck index of chemicals and drugs.
Rahway, New Jersey, 1960. 1,643 p.
1571. OPD Chemical buyers directory. New York, Schnell Publishing Company,
1971. 1,584 p.
1679. Shearon, W. J. Jr., L. G. Davy, and H. Von Bramer. Hydroquinone
manufacture. Industrial and Engineering Chemistry, 44(9):1,730-
1,735, Aug. 1952.
1687. Eastman Chemical Products, Inc. £-Benzoquinone. Technical Data
Sheet No. D-112. New York.
o
227
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Quinone (365)
Structural Formula
IUC Name 1.4-Benzoquinone
Common Names ara-Quinne, -benzoquinone
f\ A
1,4-cyclohexadieneone, chinone D H
OCH0
Molecular Wt. 108.10 Melting PtP^ 115.7 C Boiling Pt.^2^ Sublimes
Density (Condensedy '}.318 . @ 20 C/4 C . Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
98 mm @ 25 C @ @
Flash Point Autoignition Temp._
Flammabijity Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower . Upper_
Solubil ity '
Cold Water 1 g/lOOg solv. @ 25 C Hot Water Ethanol 6g/100g solv. @
Others: Acetone (36g). Ethyl acetate (18g), Benzene (18g) 25 C
Acid, Base Properties Neutral
Highly Reactive with Reducing agents
Compatible with_
Shipped in 50-lb fiber
Comment-: Volatile with steanr , sources:^ ' Eastman Chemical Products. Orlex Dyes and
ICC Classification Coast Guard Classification
ents VoTatile with st
Chemicals Corporation
References (1) 1492 (4) 1687
(2) 1433
(3) 1571
228
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PROFILE REPORT
Tetraethyl- and Tetramethyllead (425.427)
1. GENERAL
Tetraethyllead (TEL) and tetramethyllead (TML) are colorless, oily
liquids of very high toxicity. Individually and in mixtures they consti-
tute the major gasoline antiknock agents now in use. More stringent ex-
haust emission standards are expected to reduce their predominance as
gasoline additives. They are commonly believed to be the major source
of environmental lead pollution and they are likely to interfere with the
operation of the automobile antipollution equipment that will be necessary
to meet future exhaust emission requirements.
Although many synthetic schemes for the.preparation of TEL and TML
have been disclosed in the technical and patent literature, there are only
1433
two basic processes in domestic, commercial use. By far the more im-
portant of the two involves the reaction of sodium-lead alloy with ethyl
or methyl chloride as shown in Equation 1. Upon completion of the reaction,
the TEL or TML is steam distilled to remove it from the other products.
The organolead compounds are then purified by washing with dilute solutions
of oxidizing agents (e.g., hydrogen peroxide, sodium dichromate) and then
with water. After purification, the TEL and TML are usually mixed with the
other ingredients that make up the antiknock fluid and with an identifying
dye. The compounded fluid is then pumped into tank cars or bulk-storage
tanks. This process, in several modifications, is used by Du Pont (Antioch,
California, and Deepwater, New Jersey), Ethyl Corporation (Baton Rouge,
Louisiana and Houston, Texas) and Houston Chemical (Beaumont, Texas) with
a combined capacity (1971) of 790 million Ib per year.
1 NaPb + 4 C2H5C1 -»• (C2H&)4Pb + 3 Pb + 4 NaCl (1)
229
-------
Nalco Chemical (Freeport, Texas) uses an electrolytic process for TML,
based on the electrolysis of a solution of methyl magnesium chloride and ex-
cess methyl chloride in an ether solvent, with lead metal acting as the
1433
anode. The overall electrolytic reaction is shown in Equation 2. The
capacity of the Nalco plant is 40 million Ib per year.
2 CHgMgCl + CH3C1 + Pb + (CH3)4Pb + 2 MgCl2 (2)
TEL and TML are also available for use in antiknock fluids as mixtures
of organolead compounds produced by a redistribution reaction of mixtures
of TEL and TML in the presence of Lewis-acid catalysts (Equation 3).
The production capacity for the redistributed mixtures is included in the
total 830 million Ib per year capacity cited above.
Me4Pb + Et4Pb + Me4Pb + Me3EtPb + Me^Pb + MeEt3Pb + Et4Pb (3)
The only nonanti knock use for TEL and TML of commercial importance is
in the preparation of organomercury fungicides, another group of mater
ials under investigation as a possible environmental danger.
The physical/chemical properties of TEL and TML are summarized in the
attached worksheets.
2. TOXICOLOGY0766' 1433
Tetraethyl- and tetramethyHead are extremely toxic materials. Acute
or chronic poisoning may result from ingestion, inhalation or absorption
through skin. Overexposure to TEL or TML severely affects the central ner-
vous system. The initial symptoms are weakness, nervousness, severe con-
stipation and colic-like pains. Heavy or prolonged exposure may result in
death.
The American Conference of Government and Industrial Hygienists has
recommended Threshold Limit Values (TLV's) for TEL and TML of 0.10 mg/M3 and
0.15 mg/M3 (as Pb) respectively.
230
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3. OTHER HAZARDS
Tetraethyl- and tetramethyllead are considered to be fire hazards when
exposed to heat and flame. The hazardous nature of a fire involving
these materials is substantially increased by the danger of exposure to the
toxic fumes of TEL, TML, and their decomposition products.'
These organolead compounds are also known to react exothermically with
1433
halogens, mineral acids and oxidizing agents.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage, and Transportation
The most significant potential for exposure to TEL and TML occurs in
the manufacture of the compounds and their blending into gasoline at the
1433
refinery. Subsequent to the blending operation at the refinery, ex-
posure to these materials is limited by the low concentration in gasoline
(less than 4 ml/gal.) and the normal methods of handling the fuel at ser-
vice stations.
In the manufacturing and blending operations emphasis has been placed
on eliminating vapor, dust and liquid leaks. Adequate exhaust ventila-
tion must be provided in all work areas to maintain the concentration of
TEL and TML vapors well below the recommended Threshold Limit Values (TLV)
of 0.10 mg/M3 and 0.15 mg/M3 (as Pb) respectively. Personnel likely to
contact these materials in concentrated form should be provided with proper
protective gloves and be made thoroughly cognizant of the danger they pose.
Regular medical examinations should be an integral part of a program
to guard against the danger of lead intoxication. The medical examina-
tion should include a urine or, preferably, a blood test to monitor the
level of lead in the worker's body. The mean normal lead concentration in
whole blood is said to be 0.03 mg/100 cc and in urine a concentration of
0.03 mg of lead per liter is considered normal.
231
-------
TEL and TML are generally stored and shipped in steel vessels. Acci-
dental spills which occur in handling or transport can be decontaminated by
reaction of the lead compound with dilute potassium permanganate or bromine
solution.1433
Both of these fetraalkyllead compounds are classified by the Depart-
ment of Transportation (DOT), Coast Guard and IATA as Poison B, requiring
a poison label. The IATA does not permit their shipment on passenger flights
and limits cargo flights to a maximum of 220 liters.0766
Disposal/Reuse
The recovery and reuse of lead and lead compounds is an integral part
of the manufacture of TEL and TML. Only 25 percent of the lead in the
NaPb alloy (see Equation 1) is utilized on each pass through the process.
It is a matter of economic necessity that the excess lead be recovered,
purified and returned to the process.
Tetraethyl- and tetramethyllead wastes are most likely to appear as
dilute aqueous solutions generated in their manufacture, and as com-
ponents of the sludge and scale which collect in plant and refinery storage
and mixing facilities.
The adequate treatment of the waste requires that the hazards involved
in handling these toxic materials be reduced, that their concentration in
I 7O7
effluent aqueous streams be at acceptable levels (<1 ppm ), and that
the lead-containing compounds removed from the wastes be converted to forms
suitable for reuse. All of those requirements can be met by the conversion
of the organic lead compounds to inorganic lead compounds. The inorganic
materials can be more easily removed from solution and reduced to metallic
lead in a smelting operation. Other advantages of the organic to inorganic
conversion accrue by virtue of lessened volatility and reduction of the
high lipoid solubility of the organic materials (responsible for their ease
of absorption through the skin). .
232
-------
The recommended provisional limits for tetraethyl- and tetramethyl-
lead in the environment are as follows:
Concentration and Basis of
Environment Provisional Limits Recommendation
TEL in air .0010 mg/M3 as Pb 0.01 TL.V
TML in air .0015 mg/M3 as Pb 0.01 TLV
TEL in water and soil 0.05 ppm (mg/1) as Pb Drinking water
standards
TML in water and soil 0.05 ppm (mg/1) as Pb Drinking water
standards
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processes currently employed for the disposal of tetraalkyllead
wastes are all basically the same, differing only in detail as dictated by
the location and nature of the waste generation source.
Current Disposal Processes
Dilute, aqueous solutions of organic lead compounds generated in the
manufacturing process are the major type of TEL and TML wastes. The con-
taminated water is produced during steam distillation, washing, purifica-
tion and maintenance operations. The aqueous wastes are collected in
settling pits to recover lead and insoluble lead salts. The water from
the settling pits is then treated to adjust its pH to 8 to 9.5 in the pre-
sence of precipitating agents such as ferrous sulfate or sodium carbon-
ate. ' Precipitated lead salts are recovered for recycling to
17ftfi 17ft7
lead metal, ' and the water is allowed to return to the environment.
Despite the ubiquity of the disposal method described above, it is
now generally agreed that it does not reduce the lead concentration in ef-
fluent streams to acceptable levels. In view of the inadequacy of the
current disposal process, the DuPont plant in Antioch, California has been
forced to store its lead-containing wastes pending the completion of an
incineration facility to convert them to a form more amenable to recycle by
233
-------
1787
lead smelters. The problem of lead recycling is especially complicated
at the Antioch plant, which uses a continuous rather than batch TEL synthe-
sis.1787
The Baton Rouge plant of the Ethyl Corporation has also experienced
17ftfi
difficulty in maintaining acceptably low lead effluent concentrations.
They are pursuing conventional (unspecified) methods of reducing those
concentrations.
The scale and sludge which form in TEL and TML storage, mixing and
transport vessels are another source of tetraalkyllead waste. The former
practice of dumping the old tanks containing lead residues at sea is no
I787 17R8
longer used. ' The lead sludges are buried or sold to secondary
1788
smelters for recycle. Petroleum refineries follow the practice of ex-
posing the sludges to the air (weathering) until they are "inactive," after
1788
which they are landfilled. Presumably, the weathering process results
in the slow oxidation of the lead compounds to insoluble PbO. However, it
seems likely that the evaporation of toxic organic lead compounds cannot
be avoided in this essentially uncontrolled exposure and that this method
may result in local atmospheric organic lead pollution. This method of
disposal is not adequate.
Near Future Disposal Processes
The disposal processes outlined in the following subsections do not
appear to be in actual use at this time. They are currently under develop-
ment or have been reported in the literature.
Option No. 1 - Incineration. An incineration process to convert organic
and inorganic lead wastes to PbO for recycle to lead metal is now under
1787
development. The use of this or a similar process for treatment of
TEL and TML waste streams is recommended as the most desirable method of
reducing their deleterious effects on the environment. An acceptable lead
waste burning installation must be fitted with efficient scrubbing devices
234
-------
to prevent the contamination of stack effluents with toxic lead or lead-
containing particulates and/or vapors.
Option No. 2 - Ion Exchange. Strongly acidic cation exchange resins
have been shown to effect almost complete removal of organic lead compounds
from typical TEL aqueous waste streams. The inorganic lead compounds were
removed by conventional means before the stream was introduced to the ion
exchange column and the final concentration of lead in the effluent water
was less than 1 ppm. After elution from the column with caustic soda the
eluate was subjected to oxidative chlorination, affording almost complete
conversion to recoverable inorganic lead compounds. Although a judgment
with respect to economic practicality of this process is not possible with
the data in hand, the removal of organic lead compounds from TEL wastes
with ion exchange resins appears to be technically attractive. A complete
disposal system incorporating this process must also provide for rendering
the inorganic lead obtained suitable for conversion to metallic lead.
Option No. 3 - Improved Precipitation Methods. A number of methods
designed to improve the removal of lead-containing compounds from TEL and TML
I 7Q7
aqueous wastes are now under study. One such method involves the treat-
ment of aqueous effluents from tetraa Iky Head manufacture by: (1) adjusting
the pH of the effluent to between 8.0 to 9.5; (2) intimately contacting the
aqueous effluent with an ozone-containing gas in the presence of a soluble
carbonate; (3) precipitating the converted inorganic lead compounds; and (4)
separating the precipitated compounds. Reduction of the dissolved
organic lead content to below 5 ppm is claimed. Any improved precipi-
tation should be coupled to a process for conversion of the precipitated
lead compounds to metallic lead for reuse.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Aqueous tetraethyl- and tetramethyllead waste streams are not
candidates for disposal at National Disposal Sites. The aqueous, organo-
lead wastes are generated at six manufacturing facilities belonging
to relatively large, sophisticated chemical firms. Although these
wastes are not currently treated in a completely acceptable manner, the
235
-------
problems are under intensive study and appear to be amenable to solution
by the application of existing technology.
The lead-containing sludges and scales formed in TEL and TML storage,
transportation and mixing vessels present a more complicated problem.
Their sources are both more numerous and more diverse than those of the
aqueous wastes, ranging in size and sophistication from major oil refin-
eries to local, owner-operated service stations. Many of these purveyors
of tetraalkyllead-containing gasolines will be unable to dispose of sludge
and scale wastes in an acceptable manner. Therefore, the lead-containing
sludges and scales may represent a class of materials that could be pro-
fitably sent to National Disposal Sites for treatment by incineration and
subsequent recycle to metallic lead.
Another, perhaps controlling factor that must be considered with re-
gard to the applicability of tetraalkyllead wastes to National Disposal
Sites is the probable diminishing use of these compounds as gasoline addi-
tives. A governmental decision to ban the use of the lead antiknock
compounds in gasoline may render the question of the disposal of their
wastes academic.
236
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7. REFERENCES
0534. Jones, H. R. Environmental control in the organic and petrochemical
industries. Pollution control review No. 3. Park Ridge, New
Jersey, Noyes Data Corporation, 1971. 257 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Book Corporation, 1968. 1,251 p.
1046. Nozaki, M. and H. Hatotani. Treatment of tetraethyl lead
manufacturing wastes. Water Research. 1:167-177, 1967.
1433. Kirk-Othmer encyclopedia of chemical technology, 2d ed. 22 v. anH
supol., New York, Interscience Publishers, 1963-1971.
1506. Schnell Publishing Company, Inc. Chemical profile, lead alkyls.
New York, 1971. 1 p.
1570. The Chemical Rubber Company. Handbook of chemistry and physics.
47th ed. Cleveland, 1962. 2,100 p.
1718. United States Tariff Commission. Synthetic organic chemicals,
United States production and sales, 1970. TC publication 479.
Washington, U.S. Government Printing Office, 1972. 262 p.
1786. Personal communication. N. Garland, Ethyl Corporation to H. E. Green,
TRW Systems, June 30, 1972.
1787. Personal communication. R. Herbert, E. I. du Pont de Nemours, Inc.,
to H. E. Green, TRW Systems, June 30, 1972.
1788. Personal communication. W. Philipson, E. I. du Pont de Nemours, Inc.,
to H. E. Green, TRW Systems, June 30, 1972.
237
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tetraethvllead (425)-
Structural Formula
IUC Name Tetraethyllead
Common Names Lead tetraethvl. TEL
(CH3CH2)4Pb
Molecular Wt. 323.44 Melting Pt. -136.8 C Boiling Pt.' 700 C (d)
Density (Condensed)*^i .6528 @ 20 C/4 C Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
9 0\ (1)
0.47 mm @ 20 C 2.5 mm 9 55 C ; 19 mm @ 91 C
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility ^
Cold Water Insoluble Hot Water Ethanol si. ?0i.
Others: Benzene, ether, gasoline
Acid, Base Properties
Highly Reactive with Oxidizing agents;^3' acids and halogens^
Compatible with
Shipped in Steel
(3)
ICC Classification Poison B Coast Guard Classification Poison B
(2\
Coranents Begins to decompose at or above 1QQ cvc/
Sources+ *> DuPont. Houston r.hemiral f.nrp . Malm r^mjr?i Et^yl Corp
References (1) 1570 (4) 1718
(2) 1433
(3) 076fi
238
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tetramethyllead (427)
Structural Formula
IUC Name Tetramethyllead
Common Names Lead tetramethyl, TML
(CH3)4Pb
Molecular Wt. _J67.__33 Melting Pt. -27.5 C Boiling Pt. 110 C
Density (Condensed)^ 1.9952 @ 20 C/4 C Density (gas)^j.2 @
Vapor Pressure (recommended 55 C and 20 C)
22.5 mm @ 20 C 116.6 mm & 55 C @
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility^
Cold Water Insoluble Hot Water Ethanol si. sol.
Others: benzene, ether, gasoline
Acid, Base Properties ; ._
Highly Reactive with Oxidizing agents; acids and halogens
Compatible with
Shipped in Steel
ICC Classification Poison B . '_ Coast Guard Classification Poison B
(4)
Comments Sources :' Du,Pontt Nalco Chemical, Fthyl Corp.
References (1) 1570 (4) 1718
(2) H33
(3) 0766
239
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PROFILE REPORT
Tetranitromethane (428)
1. GENERAL
Tetranitromethane is a very toxic colorless liquid that melts at 13 C.
It has been used as a rocket propellant, as either oxidizer or monopropellant.
At present, its chief use is as an additive to racing car fuels. A minor
use is a reagent in a qualitative test for unsaturated compounds.
Tetranitromethane is prepared by reacting acetic anhydride with anhydrous
Mam
1411
nitric acid. Manufacture and sales are limited to one company, Hummel
Chemical Company.
Procedures for adequate handling, storage and transportation are not well
documented in the published literature. In general, tetranitromethane can be
handled in equipment fabricated from most .common metals except copper or
copper alloys. Fluorocarbon and silicon-based lubricants can be used, but
not petroleum-based lubricants. Teflon, polyethylene,.butyl Bibber and
silicone rubber are all compatible with tetranitromethane. . It is shipped
as an oxidizing material requiring a yellow label.
2. TOXICOLOGY
Tetranitromethane irritates the eyes and respiratory passages and does
damage to the liver. It appears as an impurity in crude TNT and is thought
to be the cause for the irritating properties of that material. It can cause
pulmonary edema, mild methaemoglobinemea and fatty degeneration of the liver
and kidneys. Animal experiments indicate that concentrations as low as 0.1
ppm have proved rapidly fatal. Concentrations of 3.3 to 25 ppm produce
rapid and marked irritation of mucous membranes of the eyes, mouth and upper
respiratory tract. The Threshold Limit Value (TLV) recommended by American
Conference of Governmental Industrial Hygienists (ACGIH) is 1 ppm.
241
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3. OTHER HAZARDS
When shocked or exposed to heat, tetranitromethane can explode. It can
form a powerful explosive when mixed with other nitrocompounds that are
oxygen deficient or with low molecular weight hydrocarbons, benzene, or
highly unsaturated hydrocarbons. When tetranitromethane is burned,
visible plumes of oxides of nitrogen are liberated, and a small concentration
(part per million range) of hydrogen cyanide is present in the combustion
products. There are no reports on measurements of concentrations or
quantities of these toxic combustion products.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Adequate procedures for the safe handling and storage of tetranitrome-
thane are described in the JANAF Propulsion Committee's Chemical Rocket Propel-
1142
lant Hazards publication. Tetranitromethane is classified by the Department
of Transportation (DOT) as an oxidizing material and is shipped under a yellow
label0°766
The safe disposal of C(N02)4 is* defined in terms of the recommended
provisional limits in the atmosphere and in water and soil environments.
These recommended provisional limits are as follows:
Contaminant in Ai> Provisional Limit Basis for Recommendation
Tetranitromethane 0.08 mg/M3 0.01 TLV
Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
Tetranitromethane 0.4 mg/1 Stokinger and Woodward
Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Tetranitromethane does not present a waste management problem, because
only small quantities are produced with a more than adequate market in
242
-------
blending fuels for race cars. The manufacturer, Hummel Chemical Company,
will buy back for recycle any excess tetranitromethane in storage. If
it becomes necessary to dispose of excess or contaminated tetranitromethane,
the procedure recommended by JANAF Hazards Working Group for liquid
nitro compounds is presumably followed. The procedure calls for open burning,
and may be summarized as follows: Tetranitromethane, collected or stored in
drums, cans or carboys, is destroyed by open burning at remote burning sites.
Container tops or drum bungs are removed, combustible material carefully
placed around the containers (avoiding any spillage) and the tetranitromethane
is ignited with a black powder squib. This procedure is not entirely satis-
factory, since it makes no provision for the control of the toxic effluents,
NO and HCN. Suggested procedures are to employ modified enclosed pit
J\
burning, using blowers for air supply, and passing the effluent combustion
gases through loosely packed earth (as an adsorbent), or through wet
scrubbers. (Described in detail as a combustion process system for disposal
of hazardous wastes). No engineering data on tetranitromethane combustion
product characteristics is available for use in design of modified enclosed
pit burning systems.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Because there is little probability that tetranitromethane in other
than laboratory reagent quantities will require disposal, it is our conclusion
that this material is not a candidate waste stream constituent for National
Disposal Sites.
243
-------
7. REFERENCES
0766. Sax, N. I'. Dangerous properties of industrial materials. New York,
Reinhold Publishing Company, 1957. 1,467 p.
1142. JANAF Hazards Working Group. Chemical rocket/propellant hazards.
V.2. Silver Springs, Maryland, Chemical Propulsion Information
Agency (CPIA), No. 194, May 1970.
1411. Chemical Week. 1972 Buyers' guide issue. New York, McGraw-Hill
Inc., Oct. 27, 1971. 618 p.
1485. Horning, E. C. Organic synthesis. V.3. iJew York, John Wiley and
Sons. 1955. p 803 - 805.
1486. Personal communication. G. B. Schonen, Hummel Chemical Company to
J. R. Denson, TRW Systems, Mar. 28, 1972.
244
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tetranitromethane (428)
IUC Name
Common Names
Structural Formula
C(NO
2'4
Molecular Wt. 196.04 0)
Density (Condensed) T.650
Vapor Pressure (recommended 55 C and 20 C)
10 torr. a 22.7
Melting Pt. _ L2.^_(: __ LlL Boiling Pt. 125-? C (1)
c Density (gas)
@
Flash Point
C
C
torr g 30 C 25.8 torr p 40 C
Autoignition Temp.
Flammability Limits in Air (wt %) Lov.'er
.
Explosive Limits in Air (wt. %) L«,wer
Upper_
Upper
Solubility
Cold Uater ^soluble
Others' soluble in ether
Acid, Base Properties
hot Water insoTuple
Ethanol miscible
Highly Reactive with reducing substances (explosive), KCit in alcohol.
Compatible with most common ™etals, e>.. «pt coppe-- anj copper-base alloys
Shipped in
Yellow label
ICC Classification Oxidizing Material
Comments
Yellow label
Coast Guard Classification Oxidizing
References (1) (0766)
245
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PROFILE REPORT
Tricresyl Phosphate (440)
1. GENERAL
Introduction
The common grades of tricresyl phosphate (TCP) are a mixture of ortho-,
meta-, and para- or meta- and para-isomers. It was designated as a pro-
bable candidate waste stream constituent for industrial disposal because it
is a relatively high volume commodity chemical which has well-defined and
safe methods of industrial handling and disposal.
Manufacture/Use1501'1506
Tricresyl phosphate is manufactured from equivalent amounts of technical
cresol with a minimum amount of o-cresol, and phosphorus oxychloride by a
continuous or batch process. Reaction temperatures range from 150 to
300 C and reaction times from 6 to 9 hours. Hydrogen chloride is
removed continuously during the reaction by purging with an inert gas or
maintaining the reactor under vacuum.
3 CH3CgH4OH + POC13 * (CH3CgH40)3PO + 3 HC1
The crude material is washed with hot sodium hydroxide (2%) to remove residue
hydrochloric and phosphoric acids, cresol and other impurities, and it is
given a final water wash. The material is suitable for use in functional
fluids and lubricant additives (45%). A refined grade for use as a plasticizer
and flame retardant (45%) is produced by vacuum distillation. For certain
applications, trace amounts of cresol are removed by treating the refined
material with alkaline permanganate, activated charcoal or zinc and acid.
247
-------
Air filtration media (4%) and miscellaneous applications account for the
remainder of the uses. TCP has been replaced as a gasoline additive.
Major manufacturers and plant sites are: '
FMC Corporation; Nitro, West Virgina
Frontier Chemical Corporation; Newark, NewJersey
Monsanto Company; St. Louis, Missouri
Stauffer Chemical Company; Point Pleasant, West Virgina
Physical and Chemical Properties
The physical and chemical properties of TCP are discussed in the
attached worksheets.
2. TOXICOLOGY0766
Most cases of tricresyl phosphate poisoning have followed ingestion,
but poisoning by inhalation or skin absorption is also possible. There
have been several mass outbreaks of poisoning due to adulteration of food
or drink with TCP or the addition of lubricating oils containing TCP to
edible cooking oils.
Early symptoms of actual poisoning are transient gastrointestinal
upset, nausea, vomiting, diarrhea and abdominal pain. These are followed
in one to three weeks by degeneration of the peripheral motor nerves which
is manifested by soreness of the lower leg muscles and "numbness" of the
toes and fingers. This is followed in a f'.w days by weakness of the toes
and bilateral wrist-drop. More serious poisoning causes further paralysis
and even death by damage to the central nervous system. Sensory changes
are completely absent. Recovery is slow and the degree of residual para-
lysis depends on the degree of poisoning. The order of toxicity for the
three isomers is ortho, meta, para. The Threshold Limit Value (TLV) is
0.1 mg/M3.
248
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3. OTHER HAZARDS
The fire hazard of TCP when exposed to heat or flame is slight, but
incomplete combustion or heating to decomposition results in the emission
of highly toxic oxides of phosphrous.
4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling, Storage and Transportation
Tricresyl phosphate is a non-volatile, non-corrosive and only slightly
flammable liquid that is shipped under no special Department of Transpor-
tation (DOT) or IATA regulations.0766'2351 It is a bulk chemical and is
most commonly sold in 1- and 5-gal. metal cans, 55-gal. drums, tank trucks,
c cars
0766
and tank cars. Standard safety practices should be observed for
storage.
TCP can be absorbed by the body by inhalation or through the skin,
and good ventilation should be provided in areas where mists or aerosols
may be present. Protective clothing is recommended where necessary. In
cases of accidental contact, all contaminated clothing should be removed
immediately and the skin washed thoroughly with soap and water.
Disposal
The manufacture of TCP results in waste material in the form of semi-
solid distillation bottoms which are presently disposed of by landfill.
Another byproduct of manufacture is a very dilute aqueous stream (20 ppm)
1492
of TCP. This stream also contains high (100 ppm or more) concentrations
of cresol and other phenolics and is best considered in the Profile Reports
on cresol (124) or phenol (327).1501
249
-------
Tricresyl phosphate with a low content of the ortho-isomer is used as
plasticizer for polyvinyl chloride and acetate polymers and cellulose plas-
tics. It is also used as a flame retardant in polyester, polyurethane and
polyvinyl chloride plastics. Items made from these plastics are used in
1433 2400
thousands of applications. ' Practically none are reused, but dis-
posed of with municipal wastes, either by landfill or incineration. '
TCP is also used as an anti-wear additive in conventional hydrocarbon
lubricants as well as an important constituent in special lubricants and
hydraulic fluids. Used, out-of-date, or contaminated fluids are not
reprocessed and are usually disposed of by landfill. '
The recommended provisional limits for TCP in the environment are as
follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
TCP 0.001 mg/M3 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
TCP 0.005 ppm (mg/1) Stokinger and Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Municipal Disposal of
Plastic Material Containing Tricresyl Phosphate
Tricresyl phosphate is used as a plasticizer and flame retardant in the
thousands of products that are presently disposed of by municipal landfill
and incineration activities. TCP can be destroyed with proper incineration.
This is adequate as long as phosphorus oxide emissions are not significant.
14Q? ?4flfl
Its low solubility in water (20 ppm) ' and great affinity for plastics
makes the danger due to underground water leaching very small. It is recom-
mended, however, that the bulk concentration in soil of TCP in any form be
maintained below 0.005 ppm.
250
-------
Option No. 2 - Landfill of Heavy Distillation
Bottoms from Manufacture
Refined TCP is produced by distilling technical material under vacuum.
The chemical composition of the distillation bottoms is similar to TCP but
of higher molecular weight. Landfill of concentrated TCP wastes is recom-
mended only in sites meeting California Class 1 standards.
• Option No. 3 - Landfill of Contaminated or Used
Hydraulic and Lubricating Fluids :
TCP is used as a lubricant and hydraulic fluid additive as well as
being a major constituent in many synthetic lubricants and special purpose
liquids. In these applications, small amounts are used at many scattered
sites. These fluids are periodically changed due to breakdown, contamination,
equipment failure or routinely in critical applications. Their exact fate is
not known but it is generally thought that most material is landfilled at
local municipal sites. The small amounts landfilled from this source along
with the low solubility of TCP (20 ppm) ' probably presents no exces-
sive long-term hazard to underground water supplies. As mentioned previously,
however, TCP bulk soil concentration should be maintained below 0.005 ppm.
Option No. 4 - Recycling of Spent Fluids
Containing Tricresyl Phosphate
Although it is only partially feasible at present, the best method of
disposal of fluids containing TCP is by recycling or downgrading the ap-
plication. In applications that require very high standards, such as,
aircraft fluids, the fluids are changed regularly for safety reasons. Also,
unused fluids are often discarded because of prolonged storage. Although
these materials are unsuitable for aircraft applications, they may still be
premium fluids for applications requiring lesser standards. Other fluids
which have been slightly degraded might be reprocessed to upgrade them for
reuse.
251
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
All of the wastes generated in relation to the production and use of
TCP can be treated either by industrial and municipal methods such as land-
fill and incineration. TCP is not judged to be a candidate waste stream
constituent requiring National Disposal Site treatment.
252
-------
7. REFERENCES
0590. Personal communication. R. Mahaffey, Wapco Company, to W. P. Kendrick,
TRW Systems, Feb. 11, 1972.
0604. Personal communication. R. Mahaffey, Wapco Company, to W. P. Kendrick,
TRW Systems, Feb. 15, 1972.
0766. Sax, I. R. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of polymer science and technology. 12 v.
New York, Interscience Publishers, 1964-1970.
1492. The Merck index of chemicals and drugs. 8th ed. Rahway, New Jersey,
Merck Company, Inc., 1968. 1,715 p.
1501. Faith, W. L., D. B. Keyes, and R. L. Clark. Industrial chemicals.
3d ed. New York, John Wiley and Sons, Inc., 1965. 824 p.
1506. Oil, paint and drug reporter profiles. New York, Schnell Publishing
Company, Inc., 1970.
1570. Weust, R. C., ed. Handbook of chemistry and physics. 48th ed.
Cleveland, Ohio, Chemical Rubber Company, 1969. 2,100 p.
1718. U.S. Tariff Commission. Synthetic organic chemicals; U.S. production
and sales, 1970. TC Publication 479. Washington, U.S. Government
Printing Office. 262 p.
2351. Baskin, A. D. Handling guide for potentially hazardous commodities,
Chicago Railway Systems and Management Association, 1972.
2400. Product data sheet for tricresyl phosphate. New York, Stauffer
Chemical Company. 2 p.
253
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Trycresyl phosphate (440)
IUC Name tri-3-tolyl phosphate
Common Names
Structural Formula
Molecular Wt. 368.37
Density (Condensed) 1.150
(<> 25 C
Melting Pt. 25-26
Density (gas)
Boiling Pt. 258-263 C (4
&
Vapor" Pressure (recommended 55 C and 20 C)
y 4 mm & 260 C^
Flash Point 410 C
(2T
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %} Lower_
Upper_
Upper_
Solubility
Cold Water insolublelH
Hot Water <2Q ppm at_85 C
Ethanol
Others: soluble ether' ' most organic solvents. '
Acid, Base Properties^
neutral
Highly Reactive with_
Compatible with
Shipped in_
ICC Classification
Commen ts
Coast Guard Classification
References (1) 0766
(2) 1492
254
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Tricresyl phosphate (440)
IUC Name tri-2-tolyl phosphate
Common Names o-tolylphosphate
Structural Formula
Molecular Wt. 386.34
Density (Condensed) 1.17
Melting Pt. -25 to -30 r
20 C Density (gas) 12.7
Boiling Pt.410
0) e
Vapor Pressure (recommended 55 C and 20 C)
•(2)
17 mm @~ 270-275 C
Flash Point 437 F
(1)
Autoignition Temp. 725 p •
Flammability Limits in Air (wt %} Lower Upper
Explosive Limits in Air (wt. %) Lower_
Upper
Solubility
Cold Water
insoluble
Hot Water
Others: soluble-ether, chloroform, benzene; ' slightly-hexane, 1 igroin.
Acid, Base Properties neutral
Ethanol slightly
Highly Reactive with
Compatible with_
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 0766
(2) 1501
(3) 1570
255
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Trirrp<:y1 phncphatP (440)
IUC Name tri-4-tolyl phosphate
Common Names
Structural Formula
PO,
Molecular Wt. 368.37
Melting Pt. 77-78 C
(1)
Density (Condensed)1.247
25 C
(i;
Density (gas)_
Boiling Pt. 244 C (3.5 mm)'
G>
Vapor Pressure (recommended 55 C and 20 C)
3.5 mm @ 244 C^
'Flash Point 410 C
(2)
Autoignition Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %)
Lower
Upper_
Upper_
Solubil ity
Cold Water <20 ppm
(2)
Hot Water <20 ppm at 85
Others: soluble ether, chloroform, benzene, ' most organic solvents
Ethanol
(2)"
Acid, Base Properties_
neutral
Highly Reactive with_
Compatible with_
Shipped in
ICC Classification
Comments
Coast Guard Classification
References (1) 0766
(2) 1492
256
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tricresyl Phosphate* (440)
IDC Name tritolyl phosphate
Common Names TCP, Lindol, Celluflex, Kronitex. Phosplex
Structural Formula
PO,
Molecular Wt. 368.36
Pour Pt. -28 C
(1)
Density (Condensed) @
Vapor Pressure (recommended 55 C and 20 C)
IP
Density (gas)_
Boiling Pt.^265 C(1Qmm)
&
(I!
Flash Point 455 C
13}
r(3)
Autoignition Temp. 655 C'
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower
Upper
Solubil ity
Cold Water «0.002%
Hot Water <.Q02% at 85 C
(1)
Ethanol
Others: misclble with all common organic solvents^ '
Acid, Base Properties neutral, commercial material may have traces or cresol.
Highly Reactive with_
Compatible with
Shipped in
ICC Classification
Coast Guard Classification
Comments *Commercial material is a mixture of the three isomeric tritovl phosphates, usual 1 y^
excluding as much as possible of very toxjc or^o-isomer. Decomposes to highly toxic
fumes of phosphorus oxides.
References (1) 1492
(2) 0766
(3) 2400
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-k
3. Recipient's Accession No.
4. Title and subtitle-Recommended Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste. Volume XI, Industrial
and Municipal Disposal Candidate Waste Stream Constituent Pro-
file Reports - Organic Compounds (continued)
5. Report Date
Issuing date - Aug. 1973
6.
7. Author(s) R. S. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
G. I. Gruber, M. J.. Santy, and C. C. Shin
8- Performing Organization Rept.
No' 21485-6013-RU-OO
9. Performing Organization Name and Address
TRW Systems Group, One Space Park
Redondo Beach, California 90278
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-03-0089
12. Sponsoring Organization Name and Address
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
Volume XI of 16 volumes
16. Abstracts
This volume contains summary information and evaluation of waste management methods
in the form of Profile Reports for organic compounds. These Profile Reports were pre-
pared for either a particular hazardous waste stream constituent or a group of related
constituents. Each Profile Report contains a discussion of the waste stream con-
stituents, their toxicology and other associated hazards, the definition of adequate
management for the waste material, an evaluation of the current waste management
practices with regard to their adequacy, and recommendation as to the most appropriate
processing methods available and whether the waste material should be considered as a
candidate for National Disposal, Industrial Disposal, or Municipal Disposal.
17. Key Words and Document Analysis. 17o. Descriptors
Organic Compounds
Industrial Disposal Candidate
Municipal Disposal Candidate
Hazardous Wastes
Ethers
Derivatives of Benzene
Glycols
Nitro-Organo Compounds
Polychlorinated Biphenyls
Organo-Halides
17b. Identifiers/Open-Ended Terms
Tetraethyl- and Tetramethyllead
Phosgene
Alkyl Hal ides
Halogenated Aliphatic Hydrocarbons
Quinone
Chloropicrin
Benzoyl Peroxide
Cyanuric Triazide
Hydrazine
Maleic Anhydride
Nitroaniline
Oxalic Acid
Tricresyl Phosphate
17c. COSATI Field/Group
Q7E; ] 35 . -,
18. Availability Statement
Release to public.
- 258 -
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
264
22. Price
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