Industrial Manufacturing Process Quality Corbel
Evaluation Series * G1/79-G*
Tbxsc
AMINATION PROCESSES
U.S. ENVIRONMENTAL PROTECTION AGENC
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01/79-05
January 1979
EPA - IMPQCE Series
TOXIC POLLUTANT IDENTIFICATION:
AMINATION PROCESSES
by
ELBERT C. HERRICK
JOHN A. KING
The MITRE Corporation
METREK Division
McLean, Virginia 22101
Grant No. 805620
Technical Advisor: Paul E. desRosiers
Project Officer: David R. Watkins, IERL-CI
U.S. ENVIRONMENTAL PROTECTION AGENCY
INDUSTRIAL AND EXTRACTIVE PROCESSES DIVISION
OFFICE OF ENERGY, MINERALS AND INDUSTRY
OFFICE OF RESEARCH AND DEVELOPMENT
WASHINGTON, D.C. 20460
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ABSTRACT
This study provides an environmental evaluation of amination by
ammonolysis, a very widely used unit process in the chemical industry.
As representative examples of this unit process we have considered
in depth the formation of methylamines from methanol, of ethylamines
from ethanol, of aniline from phenol, of ethanolamines from ethylene
oxide, and ethylenediamine from ethylene dichloride and from ethan-
olamine. Process descriptions with flow diagrams are presented and
compared for the six processes. The constituents of the waste dis-
charges have been identified and tabulated as to type, with the point
sources located on the flow diagram of each process. The treatment
and disposal of the waste discharges from the six amination processes
are presented in terms of the segregated point source discharges.
These aminations are shown to have several common chemical pollutants
in emissions and other waste discharges. Amination by ammonolysis
processes, in general, are considered to fall into three groups,
which have characteristic types of chemical discharges.
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TABLE OF CONTENTS
LIST OF FIGURES
LIST OF TABLES
EXECUTIVE SUMMARY
1.0 GENERAL DESCRIPTION OF THE PROCESS OF AMINATION
BY AMMONOLYSIS 1-1
1.1 Types of Ammonolytic Reaction 1-1
1.2 Grouping Based on Behavior of Ammonia 1-2
1.2.1 Double decomposition 1-2
1.2.2 Dehydration 1-2
1.2.3 Simple addition 1-2
1.2.4 Multiple activity 1-3
1.3 Mechanism of the Ammonolysis of Alcohols 1-3
1.4 Typical Examples of Amination by Ammonolysis 1-6
1.4.1 Methylamines from Methanol 1-7
1.4.2 Manufacture of Ethylamines 1-10
1.4.3 Manufacture of Aniline by Ammonolysis
of Phenol 1-15
1.4.4 Manufacture of Ethanolamines by
Ammonolysis of Ethylene Oxide 1-22
1.5 Differences Between Amination of Hydroxy- and
Chloro-aliphatics 1-26
1.5.1 Ethylenediamine from Ethylene Dichloride 1-27
1.5.2 Ethylenediamine from Ethanolamine 1-33
1.6 Amine Synthesis by Hydrogenation of Nitro
Compounds 1-38
2.0 PROCESS DESCRIPTIONS 2-1
2.1 Methylamines from Methanol 2-1
2.1.1 Rohm and Haas Methylamines Process 2-1
2.1.2 Leonard Process Company Methylamines
Process 2-4
2.1.3 Methylamines Process at the Belle Plant
of DuPont 2-6
2.1.3.1 Analytical Data on Wastewater
Discharges at the Belle Plant 2-10
2.1.4 Methylamines Process at the DuPont
Houston Plant 2-19
2.1.4.1 Analytic Data on Wastewater
Discharged at the Houston
Plant 2-24
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TABLE OF CONTENTS (Continued)
2.2 Ethylamines from Ethanol 2-35
2.3 Aniline Manufacture by Ammonolysis of Phenol 2-38
2.4 Manufacture of Ethanolamines by Ammonolysis
of Ethylene Oxide 2-42
2.5 Manufacture of Ethtlenediamine by the
Ammonolysis of Ethylene Bichloride 2-45
2.6 Manufacture of Ethylenediamine by Ammonolysis
of Ethanolamine 2-50
3.0 EVALUATION OF SIX PROCESSES USING AMINATION BY
AMMONOLYSIS FOR DISCHARGE SIMILARITIES 3-1
3.1 Comparison of Flowsheets 3-1
3.2 Comparison of Constituents of Air, Water, and
Solid Discharges from Related Discharge Points
in the Six Amination by Ammonolysis Processes 3-5
3.2.1 Discharges from the Methylamines
Process 3-5
3.2.2 Discharges from the Ethylamines Process 3-10
3.2.3 Discharges from the Manufacture of
Aniline by Ammonolysis of Phenol 3-14
3.2.4 Discharges from the Manufacture of
Ethanolamines by the Ammonolysis of
Ethylene Oxide 3-18
3.2.5 Discharges from the Manufacture of
Ethylenediamine by the Ammonolysis of
Ethylene Dichloride 3-18
3.2.6 Discharges from the Manufacture of
Ethylenediamine by the Ammonolysis of
Ethanolamine 3-22
3.3 Evaluation of Similarities and Dissimilarities
of Discharges from Six Selected Aminations by
Ammonolysis 3-30
4.0 STATE-OF-THE-ART DISCHARGE TREATMENT AND DISPOSAL
FOR SIX SELECTED AMINATIONS BY AMMONOLYSIS 4-1
4.1 Air Pollution Controls for Air Point Sources 4-1
4.2 Water Pollution Controls for Water Point Sources 4-8
4.3 Solid Waste Treatment and Disposal 4-12
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TABLE OF CONTENTS (Concluded)
Page
5.0 CONCLUSIONS 5-1
5.1 Commonality of Waste Discharges 5-1
5.2 Extent of the Process of Amination by
Ammonolysis in the U.S. Organic Chemical
Industry 5-2
5.3 Use of Dissimilarities in Waste Discharges
as a Basis for Division of Amination
Processes into Related Groups 5-4
BIBLIOGRAPHY 6-1
REFERENCES 7_1
APPENDIX - CORRESPONDENCE A-l
VI
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LIST OF FIGURES
Figure Number
2.1 Rohm & Haas Process for Methylamines
2.2 Leonard Process for Methylamines
2.3 Methylamines Manufacture, Belle Plant
2.4 Methylamines Manufacture, DuPont
Houston Plant 2-21
2.5 Leonard Process for the Manufacture
of Ethylamines 2-36
2.6 Scientific Design Process for Manufacture
of Aniline from Phenol 2-39
2.7 Scientific Design Process for Manufacture
of Ethanolamines from Ethylene Oxide 2-44
2.8 Process for Manufacture of Ethylenediamine
from Ethylene Dichloride and Ammonia 2-46
2.9 Apparatus for the Separation of
Ethylene Dichloride and Ammonia 2-48
2.10 Leonard Process for Manufacture of
Ethylenediamine from Monoethanolamine 2-51
3.1 Methylamines Manufacture, Belle Plant 3-7
3.2 Leonard Process for the Manufacture
of Ethylamines 3-12
3.3 Scientific Design Process for Manufacture
of Aniline from Phenol 3-16
3.4 Scientific Design Process for Manufacture
of Ethanolamines from Ethylene Oxide 3-20
3.5 Process for Manufacture of Ethylenediamine
from Ethylene Dichloride and Ammonia 3-24
3.6 Apparatus for the Separation of
Ethylenediamine from Crude Product 3-25
3.7 Leonard Process for Manufacture of
Ethylenediamine from Monoethanolamine 3-28
3.8 Comparison of Discharges from Six
Selected Aminations by Ammonolysis 3-32
4.1 Methylamines Manufacture, Belle Plant 4-2
4.2 Leonard Process for the Manufacture
of Ethylamines 4-3
4.3 Scientific Design Process for Manufacture
of Aniline from Phenol 4-4
4.4 Scientific Design Process for Manufacture
of Ethanolamines from Ethylene Oxide 4-5
4.5 Process for Manufacture of Ethylenediamine
from Ethylene Dichloride and Ammonia 4-6
4.6 Apparatus for the Separation of
Ethylenediamine from Crude Product 4-7
4.7 Leonard Process for Manufacture of
Ethylenediamine from Monoethanolamine 4-9
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LIST OF TABLES
Table Number Page
1.1 Physical Properties of Methylamines 1-8
1.2 Physical Properties of Ethylamines 1-12
1.3 Physical Properties of Aniline 1-19
1.4 Physical Properties of Ethanolamines 1-24
1.5 Physical Properties of Ethylenediamine
and Higher Ethyleneamines • 1-28
2.1 Methylamines Process, Wastewater, Belle
Plant No. 1 Dehydrator Bottoms, 4/29/75-
6/2/75 2-12
2.2 Methylamines Process, Wastewater, Belle
Plant No. 2 Dehydrator Bottoms, 4/29/75-
6/2/75 2-13
2.3 Methylamines Process, Wastewater, Belle
Plant No. 1 Methanol Recovery Column
Bottoms, 4/29/75-6/2/75 2-14
2.4 Methylamines Process, Wastewater, Belle
Plant No. 2 Methanol Recovery Column
Bottoms, 5/14/75-6/2/75 2-15
2.5 Methylamines Process, Wastewater, Belle
Plant Vent Dehydrator Bottoms, 4/29/75-
6/2/75 2-17
2.6 Methylamines Process, Wastewater, Belle
Plant Discharge from Five Bottom Streams
Compared to Discharge from Other Sources
5/14/75-6/2/75 2-18
2.7 Methylamines Process, Wastewater, Belle
Plant Wastewater Treatment Sewer, 4/29/75-
6/2/75 2-20
2.8 Methylamines Process, Wastewater, Houston
Plant Dehydrator Bottoms, 2/3/75-2/17/75
& 3/20/75-4/18/75 2-25
2.9 Methylamines Process, Wastewater, Houston
Plant Vent Dehydrator Bottoms, 2/3/75-
2/17/75 & 3/20/75-4/18/75 2-26
2-10 Methylamines Process, Wastewater, Houston
Plant Methanol Recovery Column, 2/3/75-
2/17/75 & 3/20/75-4/18/75 2-27
2-11 Methylamines Process, Wastewater, Houston
Plant Fume Scrubber Tank, 2/3/75-2/17/75
& 3/20/75-4/18/75 2-28
2-12 Methylamines Process, Wastewater, Houston
Plant Cooling Water Slowdown, 8 Samples
Between 2/5/75-4/16/75 2-29
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LIST OF TABLES (Concluded)
Table Number
2.13 Methylamines Process, Wastewater, Houston
Plant, Steam Pump Condensate, 8 Samples
Between 2/5/75-4/16/75 2-30
2.14 Comparison of Results, Houston Plant
vs. Belle Plant, Waste Loads Tabulated
as Pounds per M Pounds of Amines Produced 2-33
2.15 Houston Plant, Historical TOD Data 2-34
3.1 Comparison of Ammonolysis Processes 3-2-
3.2 Pollutant Discharges from the Methylamines
Process 3-6
3.3 Pollutant Discharges from the Ethylamines
Process 3-11
3.4 Pollutant Discharges from the Manufacture
of Aniline by Ammonolysis of Phenol 3-15
3.5 Pollutant Discharges from the Manufacture
of Ethanolamines by Ammonolysis of
Ethylene Oxide 3-19
3.6 Pollutant Discharges from the Manufacture
of Ethylenediamine by Ammonolysis of
Ethylene Dichloride 3-23
3.7 Pollutant Discharges from the Manufacture
of Ethylenediamine by Ammonolysis of
Ethanolamine 3-27
5.1 U.S. Production of Synthetic Organic
Chemicals Using Amination by Ammonolysis 5-3
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EXECUTIVE SUMMARY
The U.S. Environmental Protection Agency has been authorized
under recently enacted laws to regulate toxic or hazardous chemicals
in both products and waste discharges from manufacturing operations.
These laws include the Toxic Substances Control Act of 1976, PL 94-
469; Clean Air Act as amended in 1977, PL 95-95; Clean Water Act of
1977, PL 95-217; and the Resource Conservation and Recovery Act of
1976, PL 94-580.
Regulation of the organic chemical industry is extremely complex
because of the large number of products and their many different end
uses. In 1976, the U.S. Tariff Commission reported over 7,000 dif-
ferent organic compounds in commercial production which were estimated
to total 289 billion pounds.
Therefore, the U.S. Environmental Protection Agency and the
chemical process industry face many issues associated with regulating
toxic chemicals, and the need to identify those toxic chemicals which
may occur in feedstocks, products and waste discharges.
Organic chemicals are manufactured by the use of one or more
unit processes. If the unit process .used to manufacture a number of
chemicals is identified and if typical toxic discharges and product
contaminants for the unit process are indicated, the regulatory
process would be simplified.
In the "Catalog of Organic Chemical Industry Unit Processes"
(MTR-7823), we have identified 22 major unit processes and 19 minor
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unit processes used in the commercial manufacture of 263 organic
chemicals. From this catalog, we have chosen the unit process of
"Amination by Ammonolysis" for evaluation.
Amination by Ammonolysis. As representative examples of
amination by ammonolysis, we have evaluated the formation of methyl-
amines from methanol, of ethylamines from ethanol, of aniline from
phenol, of ethanolamines from ethylene oxide, and ethylenediamine
from ethylene dichloride and from ethanolamine. Process descriptions
with flow diagrams are given for each of the six processes. In all
cases data were obtained from the open literature except for the
extensive operating data supplied by DuPont to the U.S. Environmental
Protection Agency for their methylamines plants in Belle, West
Virginia, and Houston, Texas.
The flow diagrams and conditions of ammonolysis for the six
processes are compared. The methylamines, ethylamines, aniline and
ethylenediamine from ethanolamine are produced by vapor phase
catalytic processes. These are carried out under moderately high
temperatures of 260-460°C and medium pressures of 75-250 psi, except
for the ethylenediamine process which requires 375° psi. The ethanol-
amines and ethylenediamine from ethylene dichloride processes use
aqueous liquid phase systems at relatively low temperatures of 50-
160°C and pressures from 150-1000 psi.
Pollutant Identification. The constituents of the discharges
from each process, as determined by a literature search, have been
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tabulated as to source and type of discharge—air, water, or solid.
The point sources of the discharges are located on the flow diagram
of each process. We have actual operating data for the methylamines
process as carried out at the DuPont plant at Belle, West Virginia.
Five wastewater streams were analyzed for dimethylamine, monoethyl-
amine, trimethylamine, methanol, dimethylformamide, dimethylacetamide,
methyl acetate and methyl formate. Results of the analyses are listed
in Tables 2.1 through 2.5 with the concentration in ppm and total
pounds discharged per day given for each of these constituents.
The discharges for each process are listed for comparison in
Table 3.8 using generic groupings wherever possible. Study of the
table shows that there are a number of common discharges, both of
specific compounds and of generic groups. Obviously, ammonia and
amines are found in the discharges from each process. Catalyst fines
are discharged from the four processes requiring catalysts: methyl-
amines, ethylamines, aniline, and ethylenediamine from ethanolamine.
Nondistillable high molecular weight polymers are formed in four
processes: for aniline, and for the three difunctional products -
ethanolamines, ethylenediamine from ethylene dichloride, and ethylene-
diamine from ethanolamine.
Processes for the two monofunctional products - methylamines and
ethylamines - have common discharges of amides, ethers, an aldehyde
and carbon monoxide. Processes for the three difunctional products -
ethanolamine, ethylenediamine and ethylenediamine from ethylene
XII
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dichloride - have common discharges of piperazine and substituted
piperazines. Mbrpholine and substituted morpholines are discharged
from the two processes where ethanolamine is a product or feedstock.
Dissimilarities in waste discharges among the six processes are
surprisingly few. The major ones occur in the ethylenediamine from
ethylene dichloride process due to the presence of the halogen atoms.
Ethylene dichloride dehydrohalogenates to give vinyl chloride in
amounts up to 3% of the ethylene dichloride introduced. Also two
moles of HC1 are formed for every mole of ethylenediamine produced.
The HC1 must be neutralized with sodium hydroxide forming sodium
chloride. These large amounts of salt contaminated with nondistillable
high molecular weight polymers present a difficult disposal problem,
probably requiring a secured landfill.
Control Technologies. Section 4 presents the expected treatment
and disposal of the discharges from the six amination processes in
terms of segregated point source discharges. Air pollution controls
include scrubbers for vents and flares, if required, for nonconden-
sible gases.
Water pollution controls are generally based on biological
treatment with an acclimated seed in an aerated lagoon. In treatment of
the wastewater from the methylamines process at the Belle plant DuPont
has shown that a dilution of 10-15 times is necessary to obtain satis-
factory biological treatment. DuPont also showed that filtration gave
an insignificant reduction in BOD, and would not support expenditures
for filtration equipment.
Xlll
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DuPont studies of carbon treatment showed erratic performance
with only minor reduction in BOD. for biotreated methylamines waste.
Therefore, pending further carbon treatability studies, the BATEA
(Best Available Technology Economically Available) should be set the
same as BPCTCA (Best Practical Control Technology Currently Available)
which is biological treatment with an acclimated seed in an aerated
lagoon.
Incinerators are used to dispose of the high molecular weight
condensation products from the amination processes. In the methyl-
amines and ethylamines processes an oil layer is separated by a
decanter for incinerator. Bottoms from the aniline still and the
triethanolamine still are sent to an incinerator. In the ethylene-
diamine processes the bottoms remaining after distillation of the
desired polyamines are disposed of by incineration.
The only one of the six amination processes which has a continu-
ing solid waste disposal problem is the manufacture of ethylenediamine
by the ammonolysis of ethylene dichloride. Two moles of sodium
chloride are produced for every mole of ethylenediamine manufactured.
Since this sodium chloride is contaminated with high molecular weight
nondistillable polyamines it would require disposal in a secured
landfill.
The four catalytic processes - methylamines, ethylamines, aniline
from phenol, and ethylenediamine from ethanolamine - would all require
periodic catalyst charges. If economics warranted, these spent
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catalysts would be returned to the supplier to recover their metal
values. Otherwise, the spent catalysts would have to be disposed of
in a secured landfill.
Generic Amination Pollutant Discharges. In our conclusions in
Section 5, we have shown that there are several common chemical
pollutants in emissions and other waste discharges in most aminations.
The amination processes appear to fall into three groups having
characteristic types of chemical discharges. All three groups have
waste discharges containing ammonia and amines. Further, if a
catalyst is used in the process, catalyst fines occur in the discharge.
The first group of amination processes consist of processes in
which the feedstock contains one or more halogen atoms. A halogen
acid is formed, generally hydrochloric acid, which must be neutral-
ized. The resulting sodium chloride, which is contaminated with
nondistillable high molecular weight polyamines, must be disposed of
in a secured landfill. This group would also have the chlorocompound
used as a feedstock, and any of its decomposition products, in the
waste discharges.
The second group consists of the processes leading to tnonofunc-
tional products, such as methylamines and the other alkylamines.
This group would be characterized by common discharges of amides,
ethers, aldehydes and carbon monoxide.
The third group consists of the processes leading to difunctional
products. Common discharges include nondistillable high molecular
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weight polymers and heterocyclic nitrogen and oxygen compounds, such
as piperazine, substituted piperazines, morpholine and substituted
morpholines. The group could be subdivided into aliphatic and
aromatic subgroups. The aromatic subgroup forms nondistillable high
molecular polymers, even if monofunctional, such as aniline.
Recommended Actions. Amination by ammonolysis is an important
process in the synthetic organic chemical industry of the United
States, as shown by Table 5.1. Eighteen chemicals, or related groups
of chemicals are manufactured in 53 plants. These plants have an
annual capacity, or annual production rate, of over 1.2 billion
pounds. Predicted common waste discharges for these chemicals, or
others, manufactured by the process of amination by ammonolysis
should be considered in their monitoring and regulation. Process
changes aimed at decreasing or preventing these waste discharges should
be encouraged.
Emission of amines, particularly dialkylamines, to the environ-
ment may be potentially hazardous since reaction with nitrous acid,
or oxides of nitrogen, forms nitrosamines. Diethylnitrosamine and
dimethylnitrosamine are known potent carcinogens. Special precau-
tions must be taken to prevent waste streams containing dialkylamines
coining in contact with streams containing nitrous acid to prevent
the formation of the carcinogenic•dialkyl nitrosamines.
Additionally, inasmuch as potentially toxic chemicals occurring
in and carried forward into process and waste streams could
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contaminate process products, the identified amination process
pollutants should be regarded as potential amination product contami-
nants. Such products may be subject to regulation under TOSCA or
other product regulations.
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1.0 GENERAL DESCRIPTION OF THE PROCESS OF AMINATION BY AMMONOLYSIS
1.1 Types of Ammonolytic Reactions
Amination by ammonolysis is the process of forming amines by the
action of ammonia. The use of primary and secondary amines as aminat-
ing agents (aminolysis) is also included. This is justified in view
of the similarity of underlying principles and manufacturing practices
as well as the industrial utility of the secondary and tertiary amines
thus formed. Also included is hydroammonolysis in which ammonia-
hydrogen mixtures are used with a hydrogenation catalyst. By this
technique amines may be prepared directly from carbonyl compounds
which with ammonia alone would result in the preponderant formation
of nitriles or aldimines.
We have also included in our table of ammonolytic reactions the
formation of four amides. Benzene-sulfonamide and p-chlorobenzene-
sulfonamide are made by the action of ammonia on the corresponding
sulfonyl chloride. Urea, which is the diamide of carbonic acid, is
made from carbon dioxide and ammonia. The initial condensation
yields ammonium carbamate, which on heating, first forms carbaric and,
then cyanic acid, which reacts with ammonia to give urea. Groggins
(1952) has also included the synthesis of urea in his chapter on
amination by ammonolys is. The formation of dii-ethylformamide is an
example of aminolysis in that the aminating agent is dimethylamine
which reacts with methyl formate.
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Another example of aminolysis is the reaction of trimethylamine
with ethylene oxide to form the choline base, beta-hydroxyethyl-
trimethylammonium hydroxide. This reacts with hydrochloric acid to
form the commercial animal feed additive choline chloride.
1.2 Grouping Based on Behaviour of Ammonia
Ammonolytic reactions may be divided into four groups based on
the behaviour of ammonia in the reaction.
1.2.1 Double decomposition, in which the NH_ molecule is split
into - NH_ and -H fragments, the former becoming part of the newly
formed amine, while the latter unites with the radical, like -Cl,
which is being substituted. An example in the amination table is
the formation of ethylenediamine from ethylene dichloride.
1.2.2 Dehydration, in which NH~ serves as a dehydrant and water
and amines result from the ammonolysis of alcohols and from the
hydroammonolysis of carbonyl compounds. The commercial synthesis
of methylamines is exclusively from the reaction of ammonia and
methanol over a dehydration catalyst. Ethylamines are reported to
be made commercially by three processes: (a) ethanol and ammonia
passed over a dehydration catalyst, (b) ethanol, ammonia, and hydrogen
passed over a dehydrogenation catalyst such as supported nickel, (c)
acetaldehyde, ammonia, and hydrogen passed over a hydrogenation
catalyst such as nickel sulfide - tungsten sulfide (Kiirk-Othmer, 1978).
1-2.3 Simple addition, in which both fragments of the NH.
molecule enter the new compound, as in the formation of ethanolamine
from ethylene oxide and ammonia.
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1.2.4 Multiple activity, in which nascent or recycled amines
compete with ammonia as a coreactant resulting in the formation of
secondary and tertiary amines by aminolysis. This occurs during
the manufacture of both the methylamines and ethylamines.
1. 3 Mechanism of the Ammonolysis of Alcoho_lg_
The vapor place ammonolysis of alcohols is more complicated
than that of esters or halides because of side reactions. While
there is much information available on operating conditions, effect
of flow rates and the effects of catalysts there is little to be
found in the literature on actual mechanism.
Egly and Smith (1948) studied the effect of operating variables
on methylamine production from methanol and ammonia over activated
alumina. The following nine reactions are postulated as occurring
under commercial operating conditions:
1. CH3OH + NH3 * CH3NH2 + 1^0
2. CH3OH + CH3NH2 *
3. CH3OH + (CH3)2NH
4. 2CH3OH % CH3OCH3 + H2 CH3NH2
8. (CH3)3N % CH3N=CH2 + CH4
9. (CH3)3N + NH3 * (CH3)2NH +
1-3
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The catalyst used consisted of 5/32-inch activated alumina
pellets. Conversions and product distribution were studied for
operation at 0 - 10 psig and at 200 psig for a range of reactor
temperatures from 350° to 500°C and space velocities from 200 to
20,000/hr. There appeared to be an optimum space velocity for any
given temperature and pressure at which maximum conversions were
obtained. Equilibria are essentially independent of pressure but
pressure operation permits increased throughput from a given reactor.
The proportion of trimethylamine produced can be reduced by proper
choice of space velocities and temperatures, or by adding water to
the feed. Trimethylamine can be completely eliminated by recycling.
The only mention of mechanism in Egly's paper is a statement that
these are evidently bimolecular reactions on the catalyst, which do not
go through unsaturated compounds.
The ammonolysis of alcohols is probably an example of aliphatic
nucleophilic substitution in which the attacking reagent (the nucleo-
phile) brings an electron pair to the substrate, using this pair to
form the new bond, and the leaving group (the nucleofuge) comes
away with an electron pair:
R X + Y —» R Y + X
Y may be neutral or negatively charged: RX may be neutral or
positively charged. Y must have an unshared pair of electrons, so
that all nucleophiles are Lewis bases.
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The reaction of ammonia and methanol is bimolecular (Ely and
Smith, 1948). We would expect an SN2 mechanism, or substitution
nucleophilic bimolecular. In this mechanism there is backside attack,
o
that is, the nucleophile approaches the substrate from a position 180
away from the leaving group. The reaction assumes a one-step process
with no intermediate. The C-Y bond is formed as the C-X bond is
broken:
Y + —^C —> Y • • -XC • • • X » Y C <^- + X
' I "^
The effect of the attacking nucleophile is shown by the following
principles (March, 1977):
1. A nucleophile with a negative charge is always a more power-
ful nucleophile than its conjugate acid (assuming the latter is also
a nucleophile). Thus OH~ is more powerful than H^O, and NH ~ is
more powerful than NH,.
2. In comparing nucleophiles whose attacking atom is in the
same row of the periodic table, nucleophilicity is roughly in the
order of basicity, though basicity is thermodynamically controlled
and nucleophilicity is kinetically controlled. An approximate order
of nucleophilicity is:
NH- > RO- > OH" > R2NH > ArCT > NH3 > Pyridine > F~ > H20 > C104~
In the gas phase nucleophilic ions are totally free.
The leaving group comes off more easily the more stable it is
as a free entity. This is usually inverse to its basicity, and the
best leaving groups are the weakest bases. Since XH is always a
1-5
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weaker base than X~, nucleophilic substitution is always easier at
a substrate RXH+ than at RX. As an example OH and OR are not leaving
groups from ordinary alcohols and ethers but can come off when the
groups are protonated or converted to ROH" + or RORH . Reactions in
which the leaving group does not come off until it has been protonated
are called SNlcA or SN2cA, depending on whether the reaction, after
protonation is an SN1 or SN2 process. The cA stands for conjugate
acid, since its substitution takes place on the conjugate acid of the
substrate. The ions ROH/1" and RORH+ can be observed as stable enti-
ties at low temperatures in super-acid solutions (March, 1977).
Thus we expect the ammonolysis of methanol to be a SN2cA process.
The catalytic process could be considered somewhat similar to proto-
nation except that the transfer of ions would take place on the
catalyst surface from the formation of reactive species.
Roberts and Caserio (1964) bear out these conclusions with a
statement that since acid catalysts such as ZnCl2 and NH,C1 are
beneficial an SN~ attack on the oxonium salt of the alcohol is
indicated. Roberts and Caserio (1977) conclude that the commercial
use of aluminum oxide as an acidic catalyst performs the function of
making OH a better leaving group.
1.4 Typical Examples of Amination by Ammonolysis
We will consider the formation of methylamines from methanol, of
ethylamines from ethanol, of aniline from phenol, of ethanolamines from
ethylene oxide and ethylenediamine from both ethylene dichloride and
ethanolamine.
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1.4.1 Methvlamines from Methanol
Commercial production of mono-, di, and trimethylamine is essen-
tially restricted to the high-temperature ammonolysis of methanol
with ammonia in the presence of solid acidic dehydration catalysts
such as alumina. Domestic commercial manufacture of the methylamines
was begun by Commercial Solvents in the middle 1920's, followed
within a few years by Rohm and Haas and du Pont. Physical properties
of the methylamines are listed in Table 1.1
A U.S. patent to Martin and Swallen of Commercial Solvents in
1932 describes a process for production of monomethylamine by
passing methanol and a molecular excess of ammonia at temperatures of
300 to 500°C and space velocities of 50 to 3500 over clay or aluminum
silicate catalysts. The following year the same authors patented a
process for production of dimethylamine by passing a mixture of
gaseous methylamines rich in monomethylamine, at 425 - 475°C over
aluminum silicate catalyst. Arnold in a patent to du Pont in 1935
described an amine process with similar operating conditions using
a prepared silica gel catalyst impregnated with a dehydrating oxide,
such as alumina. Recycling of trimethylamine is described in a U.S.
patent to I.G. Farben by Herold and Smeykal in 1937. Millington in
a 1938 patent to duPont describes a process for converting trimethy-
lamine to mono- and dimethylamine over a dehydration catalyst.
Other patents pertaining to synthesis of methylamines under
quite similar conditions with some variation in catalysts include:
1-7
-------
TAIU.K I. L
PHYSICAL I'KOI'KKTlliS OK MCTIIYLAMINMS
Molecular Welglil
Specific Gravity 20°t:/20°C
I'inmdci per U.S. Call on, 68°f
lliiiiiiiK I'oint, °C at 1 aim.
freezing Point, "C al 1 aim.
Vapor I'resaure, nun llg at 20"))
VlsriKil ty , Cuiitlpolse al 25°C
flauli I'oint, Tag. Open Cup, "V
Critical Temperature, °C
Crllical Pressure, atm.
Itet'mcL ive Index, n at 20"(;
Appear. nice and Odor
MONDMKTIIYIAMINIi DU
CII3NII2 1
ANIIYDKOUS 40% f)(l% ANIIYDUODS
31.06 - - 45.08
(1. 66 0. 90 0. 88 0. 66
•>.YI 7.5 7.3 5.45
-!>..! 44 11 6.9
-91.5 -38 - -92.2
0 280 475 1277
1. 5U - 0.18
8 to 18
156.9 - - 164.6
;i.b - - 51.7
1.351 - - 1.347
('oloi 1 e:,a Jlijuid or gas ul ill ainmoii 1 acal, 1 laliy
limiYLAHINE
40% 60%
_
0.90 0.83
7.5 6.9
52 36
-37 -60
212 395
1.7°
4
-
-
-
odor and substantially
TKimgTHYI.AHINIi
ANHYDROUS 25%
59.11
0.63
5.27
2.9
-117.1
1432
0.177
-
160.1
40.2
1.345
free of suspended
-
0.93
7.8
38
6
346
1.64''
41
-
-
-
matter.
40%
-
0.88
7.4
32
4
470
1.85U
<80
-
-
-
Al 40°C
Air 1'roducl.s, Alky li
BEST AVAILABLE COPY
-------
Punnett to National Aniline and Chemical (1938) and Goshorn to Sharpies
Chemicals in 1944 and 1946.
A number of patents have issued on the separation and/or purifi-
cation of the methylamine mixtures. Olin (1945 to Sharpies Chemicals)
describes addition of an inorganic base to the amine as an aid to
separation by distillation. He assumed that the base converted the
carbon dioxide to a carbonic acid salt and formaldehyde to a formic
acid salt which were retained in the aqueous phase on distillation.
In a latter patent in 1945 Olin described the use of an aromatic
solvent, such as xylene, to selectively extract trimethylamine.
Two patents to 1CI (Tyerman, 1951) claim the extractive distillation
of monomethylamine with a compound such as tetrahydronaphthalene and
the extractive distillation of dimethylamine with aniline.
Kramis (1958 to duPont) in a forerunner of present processes
described the separation of monomethylamine from a mixture of mono-,
di-, and trimethylamines by a continuous extractive distillation
with water. He stated that water especially suited for recycle
could be recovered from the bottom of the extractive column, or in
a second column for continuous dehydration of aqueous monomethylamine.
Three more recent patents use hydrogen and carbon monoxide, the
precursors of methanol. Kurtz (Union Carbide, 1969) claims methyl-
amines produced from hydrogen, carbon monoxide and ammonia which are
reacted over a copper-chromia catalyst at 350 - 400°C and 4000 to
5000 psig.
1-9
-------
Two patents to Bayer AG (Enders and Hullstrung, 1972 and Enders,
1972) describe the synthesis of methylamines from carbon monoxide,
hydrogen and nitrogen over catalysts containing zirconium or hafnium,
or uranium,or thorium, at temperatures of 300 to 600°C and pressures
of 50 to 600 atmospheres.
These patents illustrate the emphasis on hydrogen and carbon
monoxide as feedstocks which can be obtained by the gasification
of coal.
The Leonard process is the only one available for licensing for
production of methylamines. A Netherlands Application of 1966 to
Jackson Leonard describes the preparation of the catalyst. A silica-
alumina catalyst, containing 10 - 15 weight % of alumina, is treated
with 1 to 50 atmospheres of steam and impregnated with 0.05 to 0.95%
by weight of an activator such as Ag PO , Re«S7, MoS_ or CoS. The
2
catalyst was placed in a reactor at 300 - 450°C and 20 Kg/cm filled
with a mixture of preheated ammonia (64%) and methanol (36%) to yield
a mixture containing ammonia (53.4%) monomethylamine (7.0%), dimethyl-
amine (3.7%), trimethylamine (5.4%), water (20.2%), and carbon monoxide
and hydrogen (0.3%).
1.4.2 Manufacture of Ethylamines
One method of preparing the ethylamines uses essentially the
same process as utilized for the methylamines - vapor-phase ammono-
lysis of ethanol in the presence of a dehydration catalyst. A mix-
ture of products is formed. However, monoethylamine, diethylamine
1-10
-------
and triethylamine differ sufficiently in vapor pressure to make
unnecessary the complex isolation schemes required to isolate the
methylamines. Physical properties of the ethylamines are listed in
Table 1.2.
Ethylamines are also prepared by passing ammonia, hydrogen, and
ethanol continuously over a dehydrogenation catalyst in a gas-solid
heterogeneous reaction. Catalysts include supported metallic silver,
nickel or copper. There is no net consumption of hydrogen, which
acts to maintain catalyst activity by retarding coke formation. A
mixture of amines is produced and recycle is used to obtain the spec-
ific amines which are needed.
An alternative method used only in special circumstances to
produce ethylamines employs the vapor-phase hydroammonolysis of
acetaldehyde at a pressure of 200 atm and about 320°C using a nickel
sulfide - tungsten sulfide catalyst (Groggins, 1952). The reaction
is shown below:
NH H
QIC = 0 —3 CH.C OH —» CH.CH = NH
3 j I ->
NH2 H
2
NiS -
Large excesses of both ammonia and hydrogen are required.
There are considerably fewer patents pertaining to manufacture
of ethylamines compared to those claiming methylamines. Most of
these patents claim ethyl and higher amines by the ammonolysis of
alcohols containing between 2 and 8 carbon atoms.
1-11
-------
TABLE 1.2
PHYSICAL PROPERTIES OF ETHYLAMINES
Molecular Weight
Specific Gravity at 20°C/4°C
Freezing Point (°C)
Vapor Pressure - Temperature °C
40 Tirm
100 mm
300 mm
760 mm
Refractive Index (IL at 20 °C)
pKa at 25 "C in Water
Viscosity (centipoises) at 25°C
Critical Temperature (°C)
Critical Pressure (atm.)
Flash Point (closed cap)
°F
°C
Surface Tension at 20 °C (dynes /cm)
Latent Heat of Vaporization
at Boiling Point (Kcal./Kg.)
Aze trope
BP (°C) at 760 mm. Hg.
% Water
MONOETHYLAMINE
ANHYDROUS 70%
45.08
0.6820 0.8046
-81.0 <-90.0
-39.2
-25.0
-3.5 16.0
16.6 38.0
1.37633
10.67b
0.575° 1.240d
183.2
55.50
<0.0 <0.0
<-17.8 <-17.8
19.87
144.8
Nonazetrope
Nonazetrope
DIETHYLAMINE
(C2H.)2 NH
ANHYDROUS
73.14
0.7085
-50.0
-10.5
7.0
31.0
55.9
1.3864
10.98b
0.330
223.5
36.60
<0.0
<-17.8
20.05
94.2
Nonazetrope
Nonazetrope
TRIETHYL AMINE
(C2H5) N
ANHYDROUS
101.09
0.7280
-114.6
12.0
32.5
62.0
88.8
1.4010
10.74b
0.335
262.0
30.00
10.0
-12.2
20.65
82.6
75.0
10.0
At 8.4°C
For the reaction: amine + HO = [Amine • H+] + [OH~] . K, = [Amine • H+1 [OH~1 = ioniza-
, Amine
tion constant of amine base. log — = -log K, = pK,; pK- + pK = 14 at 25°C. pKQ = 1
pK, = - log K , where K is the ionization constant of the conjugate acid of the base.
D Si 3.
At - 33.5°C
dAt 20°C
SOURCE: Virginia Chemicals, Amines, 1976.
1-12
-------
A U.S. patent issued in 1944 to Olin and McKenna of Sharpies
Chemicals describes the manufacture of ethylamines by passing ethanol,
ammonia and hydrogen over a reduced pelleted nickel hydrogenation
catalyst at 159°C and a space velocity of 2070. Whitehead of ICI in
1951 describes the production of ethylamines by passing ammonia and
ethanol over a basic aluminum phosphate catalyst at 400°C, at a pres-
sure of 270 psi.
Another hydroammolytic process is described in a U.S. patent
to Davies, et al, of ICI in 1952 in which one mole of ethanol, 4.5
moles of hydrogen and 0.9 mole of ammonia was passed over a foraminate
copper/aluminum catalyst (which had been treated with a 5% solution
of barium hydroxide octahydrate) at 260°C and 17 atm. pressure. A
mixture of ethylamines was obtained at a pass conversion of 94% and
yield of 92%, based on ethanol. By "foraminate catalyst" is meant
the formation of an active skeletal structure by extraction of 20 to
70% of aluminum with aqueous alkali. The catalyst in the example
above was prepared by extracting with aqueous alkali at least 20% of
the original aluminum content of an alloy containing 55% Cu and 45%
Al by weight.
A British patent to Taylor of ICI in 1952 describes essentially
the same process. Another U.S. patent to Taylor, et al, of ICI in
1953 extends the hydroammonolytic process to the use of foraminate
catalysts of aluminum with nickel, cobalt or iron.
1-13
-------
A U.S. patent to Lemon, et al, of Union Carbide in 1962 claims
the reduction of by-products, particularly acetonitrile, in a
hydroammonolytic process using two reaction zones. Ethanol, ammonia
and hydrogen in a mole ratio of 1 to 3. 8 to 3.9 were fed in the vapor
phase to a catalyst bed consisting essentially of reduced copper on
an alumina support. The catalyst bed was maintained at 260°C and
the residence time limited to ten seconds. The product effluent was
passed directly to a second catalyst bed consisting of reduced
nickel on a rigid, porous, mineral support composed essentially of
silica. The catalyst bed was maintained at 200°C and the contact
time over the catalyst was held to 11.1 seconds. The product efflu-
ent from the second reaction zone showed a decrease in acetonitrile
from 19.7 wt. % to 0.0% and a decrease in ethanol from 3.7 wt.% to
0.0%.
a Hungarian patent (Kisgergely, et. al. 1970) similar to Davies,
et al., 1952, describes a hydroammonolytic process using a nickel
foraminate catalyst. The catalyst was prepared from a 55:45 nickel/
aluminum alloy by treating with 2% sodium hydroxide until the aluminum
content decreased to 27%, washing with water, and soaking 10 hours in
a 2% calcium hydroxide suspension.
Two foreign patents describe the formation of ethylamines by
ammonolysis of acetaldehyde. A Netherlands application to Lonza in
1965 claims the preferential synthesis of monethylamine by adding
2 moles of acetaldehyde to 16 moles of liquid ammonia at 9 atm. while
1-14
-------
maintaining the temperature at 20°C. The reaction mixture is hydro-
genated continuously over a nickel catalyst at 120°C and 150 atm.
pressure with a two minute contact time. A 100% conversion was claimed,
to give a mixture of 97.5% monoethylamine and 2.5% diethylamine.
A German patent to Ruhrchemie AG (Feightinger, et al. , 1973)
claims the production of diethylamine and triethylamine by ammonolysis
of acetaldehyde with gaseous ammonia followed by hydrogenation over
Cr203 promoted 52-55% Ni catalyst at 60 - 120°C and 120 - 130 atm.
pressure.
A U.S. patent to National Distillers (McLain, 1968) claims mono-
ethylamine synthesis by passing ethylene and ammonia over a catalyst
of 2% palladium metal supported on alumina held at 120°C.
1.4.3 Manufacture of Aniline by Ammonolysis of Phenol
Aniline (benzeneamine) [62-53-3] is the simplest of the primary,
aromatic amines. Aniline was first produced by Unnerdorben in 1826
by dry distillation of indigo. In 1840, Fritsche obtained the same
oily liquid by heating indigo with potash, and gave it the name
aniline. Hofmann proved the structure in 1843, by showing that it
was obtained by the reduction of nitrobenzene.
Bechamp discovered in 1854 that nitro compounds could be reduced
in the presence of iron and acetic acid. Perkin applied this reaction
in 1857 for the manufacture of aniline which was of great significance
for development of the dye industry. Hydrochloric acid was later
substituted for the acetic acid. It was then found that ferrous aalt
1-15
-------
of the acid functioned catalytically, so that in industrial practice
only 2 percent of the theoretical amount of hydrochloric acid was used.
Several reactions are involved but the final overall result may be
written as:
5m^
+ 9 Fe + 4H-0 > 4 ||S + 3 Fe,0
^ v~n ^~~~^ J H
Fed-
This process is now obsolete, but Mobay Chemical Company is construct-
ing a plant using this process for pigment-grade iron oxide with the
concomitant production of aniline.
The Bechamp reduction process was followed by the ammonolysis of
chlorobenzene. This process could compete where large scale produc-
tion of chlorine and chlorinated products gave cheap chlorobenzene.
The reaction follows:
CL Nfl.
^JL ^t£
|l J + NH (aq.) » \\ ^\ + HC1
" J Cu2Cl2 ^
This was used commercially until 1966 when Dow shut down the process.
The bulk of the aniline in the United States is now made by the
continuous, vapor phase, catalytic reduction of nitrobenzene using
either a fluidized or fixed bed reactor. Catalysts used include
copper oxide, sulfides of nickel, molybdenum, or tungsten and palla-
dium - vanadium/lithium - aluminum spinels. The catalyst is main-
tained at temperatures below 350°C to obtain a better than 98% yield
of aniline.
1-16
-------
The reaction follows:
NO- Vapor phase NH,
^z + 3H0 /k^ + 2H^O
catalyst
A relatively small amount, less than 10%, of aniline produced
in the United States is manufactured by Rubicon Chemicals, Inc. , using
a liquid phase catalytic reduction process, as developed by ICI.
The process with which we will be concerned in the rest of this
report is the relatively new route to ariline by ammonolysis of phenol.
This process was developed by Halcon International, Inc. The first
commercial-scale plant was started up by Mitsui Petrochemical Indus-
tries, Ltd., Japan, in August, 1970. The capacity is 20,000 metric
tons/yr.
The reaction of phenol with ammonia follows:
OH NH
' + NH ' ^ + HO
3 7 fj 2
The reaction is reversible. Aniline production is favored by higher
ammonia to phenol ratios and lower reaction temperatures. The for-
ward reaction is mildly exothermic so is favored by lower temperature.
Previous attempts to commercialize the ammonolysis of phenol to
aniline were thwarted by problems of low yield, slow reaction rate
and poor product recovery. These problems were overcome by two key
innovations of Halcon: a series of Halcon-developed alumina-based
catalysts, and improvements in purification technology that allow
separation of aniline and phenol in a single distillation column.
1-17
-------
Capital costs for the phenol route are one-quarter those of
equivalent capacity via nitrobenzene reduction technology, which
makes the process attractive despite higher feedstock cost. No
catalyst regeneration facilities are needed. Waste disposal problems
are minimal compared to the conventional route (Becker and Russell,
1973).
The physical properties of aniline are given in Table 1.3.
Four German patents were issued to Halcon International in 1970
on the aniline from phenol process for which there are apparently no
U.S. patent equivalents. Chou describes the distillation procedure
by which the troublesome problem of separation of aniline from the
phenol-aniline mixture was overcome. A mixture of the two containing
64% aniline was fractionated in a column of 35 theoretical plates at
300 mm and a reflux ratio of 6.5 to 1 to give aniline of 99.9% purity.
The distillation residue contained 60% aniline. Mixtures containing
water were fractionated with or without addition of benzene, to re-
move water as the azetrope with aniline or benzene. The anhydrous
residue was fractionated in another column of 60 - 75 theoretical
plates at 140 - 150 mm. at a reflux ratio of 3.5 to 1 to give aniline
of 99.9 to 99.93% purity. For this procedure to be effective the
starting mixture must contain more aniline than phenol on a molar
basis.
Russell describes the manufacture of aniline by separate
evaporation of phenol and ammonia, mixing the streams and passing
1-18
-------
TABLE 1.3
PHYSICAL PROPERTIES OF ANILINE
PROPERTY
Boiling Point, °C
101.3 k Paa (760 mm Hg)
4.4 k Pa (33 mm Hg)
1.2 k Pa (9 mm Hg)
Melting Point, °C
Density, d
at 20/4 °C
at 15/15 °C
at 20/20 °C
Refractive Index, K.
20
Viscosity at 20°C, m Pa-s (=cP)
Dissociation Constant, pK
at 20°C
at 40°C
at 60°C
Enthalpy of Dissociation, kJ/mol (kcal/mol)
Heat of Combustion, kJ/mol (kcal/mol)
lonization Potential, eV
Dielectric Constant, e at 25°C
Dipole Moment at 25°C (calcd), Cm x 10
Specific Heat, 20-25°C
Latent Heat of Vaporization, J/g (cal/g)
Flash Point, (closed cap), °C
a
Vapor Pressure, kPa
at 151°C
at 102°C
,-30
(Debye)
VALUE
184.4
92
71
-6.15
1.02173
1.0268
1.022
1.58545
4.423-4.435
4.60
7.6
8.88
21.7 (5.19)
3389.72 (810.55)
7.70
6.987
5.20 (1.56)
0.518
476.3 (113.9)
76
39.99
6.67
TO convert kPa to mm Hg multiply by 7.50.
SOURCE: Kirk - Othmer, Vol. 2 (1978).
1-19
-------
over a catalyst. In an example, 0.5 mole/hr of liquid phenol was
evaporated at 330 - 340°C, and 10 moles/hr. of liquid ammonia were
evaporated at 110 - 120°C. The vapors were mixed and passed over
850 ml. of a silica catalyst containing 9.9% alumina at 16.8 atm. and
385°C to give 93% of clear, pale yellow aniline.
Becker and Fernandez describe the vapor-phase amination of phenol
2
with excess ammonia at 400 - 460°C, 16.9 kg/cm pressure, and 0.058
hr~ weight rate of flow over silica-alumina catalysts containing 35 -
55% alumina. The catalysts were regenerated when the reaction tem-
perature increased to 570°C.
Becker and Khoobiar describe an improvement in catalysts by
incorporating <1% Na20 in an alumina catalyst. A freshly precipitated
gel containing 90% Al^, 2.2% Si02, 1.6% Na20, 0.13% Fe^ and the
rest water was heated 2 hours with 0.6% HC1 at 80 - 90'C to give a
catalyst of 0.2% Na^O content. Using this catalyst, ammonia and
phenol in a 20 to 1 molar ratio were passed over the catalyst at 16.9
atm. and 363°C to give aniline at 98.9% conversion.
Interest of another company in this process is shown by a 1972
German patent to Wollensak of Ethyl Corporation. Wollensak claims
the formation of alkyl substituted anilines by reaction of the corres-
ponding phenol with ammonia (3 - 25 hr. , 250 - 325°C) in the presence
of the appropriately substituted cyclohexanone, which can be forned
in situ, and a palladium or platinum catalyst.
1-20
-------
Four Japanese patents have issued to Mitsui Petrochemicals
Industries who operate the only commercial plant producing aniline
from phenol. These patents are principally concerned with catalyst
compositions and variations. Shirohara, et al. , in two Japanese
patents issued in 1971 claim improved catalysts composed of alumina
or silica, also containing MgO, B-0 or ThO-. The second patent
includes pelletizing with powdered copper. Shirohara, et al., in two
Japanese patents issued in 1974 use gamma alumina catalysts previously
treated with alkali and then carboxylic acids. The second patent
uses a gamma alumina catalyst previously treated with H-BO , boric
acid.
A Japanese patent issued in 1976 to the University of Brussels
describes a non-catalytic process to prepare aniline by ammonolysis
of phenol with an aqueous solution of ammonia under pressure. A 25%
solution of ammonium hydroxide containing 31% phenol was heated at
2
440°C and 1000 kg/cm to give 74.4% aniline with 32% conversion.
Ammonolysis of phenol in the liquid phase over catalysts was
reported by Hamada, et al., of the National Chemistry Laboratory of
Industry of Japan, in 1977. Catalysts used at 300 - 350°C included
SnCl2, A1C1 , FeCl3, CoCl2, LiCl, H3P04 and NH4C1. The most effective
catalyst was SnCl2 which give 56% of aniline with 95% selectivity at
340°C.
Some success has been achieved in preparing aniline from cyclo-
hexanol. Carrubba and Golden of Halcon International in a 1967 U.S.
1-21
-------
patent describe a process in which improved yields are obtained by
recycling an overhead portion of the high boiling by-products. Ammo-
nia (1360 parts), hydrogen (80 parts), cyclohexanol (1000 parts), and
recycle (194 parts) were treated at 315°C and 50 psi over a platinum-
silica catalyst to yield 788 parts of aniline, 104 parts of cyclo-
hexylamine, high-boiling material 207 parts, ammonia 1190 parts,
cyclohexanol 30 parts, hydrogen 190 parts, and water 175 parts.
Distillation of the 207 parts of high-boiling material at 400°C and
25 mm yielded 194 parts of overhead which was recycled. The 13 parts
of residue was discarded as waste. The amine yield was 95% as com-
pared to 88% in a control reaction in which the recycle stream was
eliminated.
1.4.4 Manufacture of Ethanolamines by Ammonolysis of Ethylene
Oxide
Ethanolamines were first prepared in 1860 by Wurtz, who heated
ethylene chlorohydrin with aqueous ammonia in a closed tube. Ethanol-
amines were first separated in 1897 by Knorr using fractional dis-
tillation. The first commerical production of triethanolamine was in
1928, followed by large scale production of mono- and diethanolamines
in 1931.
The ethanolamines are colorless liquids at room temperature with
a density slightly higher than that of water. Ethanolamines are
miscible in all proportions with water and alcohol, but are almost
completely insoluble in nonpolar solvents, such as ether. The
1-22
-------
ethanolamines have a mild ammonical odor, show marked hygroscopic
tendencies, and react readily with acid gases, such as carbon dioxide
and hydrogen sulfide. Table 1.4 lists some of the physical properties
of the ethanolamines.
Ethanolamines are prepared commercially by the reaction of
ethylene oxide with ammonia (Wickert, 1934, and Ruark, 1942). The
reactions follow:
NH. + CH0 - CH0 > NH0 CH. CH0 OH
3 2x / 2 222
NH2 CH2 CH2 OH + CH2 - CH2 »• NH (CH2 CH2 OH) 2
NH (CH0 CH0 OH)0 + CH0 - CH0 > N (CH0 CH0 OH) ,
2. 2. 2. 2. s 2. 223
The reaction is exothermic and is usually carried out at temper-
atures of 50 - 100°C under pressures of 150 - 300 psi. It may be run,
at controlled temperature and pressure, either in a coil-type reactor
by continuously pumping aqueous ammonia and ethylene oxide into the
coil, or in a kettle-type reactor by slowly pumping ethylene oxide
into the ammonia solution in the agitated kettle. Because water aids
temperature control by removing heat of reaction, most commercial
processes use 28 - 50% aqueous ammonia.
Lowe, et al., in patents to Oxirane in 1956 and 1958 claim to
have developed a technique requiring low concentrations of water.
In an example seven moles of 60% aqueous ammonia were reacted with
one mole of ethylene oxide at 100 - 160°C and 60 - 100 atm. for 30
seconds to give 23% ethanolamines containing 60% monoethanolamine.
1-23
-------
TABLE 1.4
PHYSICAL PROPERTIES OF ETHANOLAMINES
PROPERTIED
Chemical Abstracts Name
CAS Registry Number
Formula
Freezing Point, °C
Boiling Point, °C, 760 mm Hg
Specific Gravity, 20/20°C
Viscosity, mPa-a = cP, at 25°C
ja-Heptane Solubility, at 25°C, g/lOOg
aAt 99.7 kPa (748 mm Hg) .
bAt 30/20°C.
SOURCE: Kirk - Othmer, 1963 and 1978.
COMMON NAMES
MONOETHANOLAMINE
2 - ami noe th ano 1
[141-43-5]
NH2 C2H4OH
10
170
1.0179
19
0.06
DIETHANOLAMINE
2,2'-iminodiethanol
[111-42-2]
NH (C2H4OH)2
27.5
270a
1.0919b
580
0.01
TRIETHANOLAMINE
2,2',2"-nitrilotrie
[102-71-6]
N (C2H4OH)3
17.9
360
1.1258
601
0.02
-------
Modifications of the process are described by Schwoegler (1943,
1945) and Reid and Lewis (1930, 1933). Schwoegler (1945) gives an
example in which ammonia and ethylene oxide in a 15:1 ratio are
pumped to a reactor at 130°C and 1600 psi pressure. The product con-
tains 78.3% monoethanolamine, 16% diethanolamine, and 4.4% triethanol-
amine.
Reid and Lewis in a U.S. patent to Carbide and Carbon Chemicals
Corporation in 1930 describe a process in which ethylene oxide is
gradually added to aqueous ammonia at such a rate that the concentra-
tion of uncombined ethylene oxide in the reaction mixture is always
low with respect to the concentration of uncombined ammonia so that
formation of by-products is minimized. The reaction temperature is
kept below 100°C.
Ropuszynski, et. al. (1967) produced ethanolamines from 96.5%
ethylene oxide and 24% aqueous ammonia solution using a double reactor
which made it possible to carry out the process under normal pressure
at about 40°C.
Weibull, et. al. (1970) used ion exchange resins as catalysts to
obtain predominantly monoethanolamine. Liquid ammonia, containing
0.2% water and ethylene oxide in a molar ratio of 80 to 1 were mixed
at 35 - 75°C in a preheater and pumped through a reactor filled with
Dowex 50 x 8 (50 - 100 mesh). The reaction was carried out at 100°C
and 100 atm. pressure to give 93.3% monoethanolamine, 6.4% diethano-
lamine and 0.3% triethanolamine.
1-25
-------
Badische AG in a French patent of 1970 claims high yields by
rapid, turbulent flow through a coil reactor. In an example, 18.7 kg.
of 80% ammonia and 2 kg. of ethylene oxide were injected at room
temperature at 12.5 cm/second into a 9 mm spiral tube, 60 meters
long. The coil reactor was kept at 122°C by oil cooling and the
pressure maintained at 90 atm. The liquid product contained 78% mono-,
19% di-, and 3% triethanolamine.
Lutz (1975) describes a tubular reactor having a diameter to
length ratio of 1 to 200 - 6000.
Kusaka (1977) describes the liquid phase reaction of ammonia with
ethylene oxide during which the excess ammonia was recovered. This
reduced the consumption of ammonia by about 50%.
A couple of recent patents pertain to separation of the crude
ethanolamine mixtures containing ethylene glycol. A U.S.patent of
1974 to Cocuzza describes feeding the crude mixture into the middle
portion of a distilling column, withdrawing monoethanolamine from
the top and a mixture of monoethanolamine and ethylene glycol from
a point between the top and the middle of the column. The latter
mixture was reacted with ethylene oxide and the product distilled to
separate the monoethanolamine from di- and triethanolamine. An equi-
valent British patent to Societa Italiana Resine S.p.A. issued in 1975.
1.5 Differences Between Amination of Hydroxy- and Chloro-aliphatics
The synthesis of ethylenediamine by the ammonolysis of ethylene
dichloride and by ammonolysis of ethanolamine will be used to illus-
trate the differences between amination of hydroxy- and chloro-aliphatics.
1-26
-------
Ethylenediamine was first prepared in 1871 by A.W. Hofmann, who
heated ethylene dichloride and alcoholic ammonia in a closed tube.
Ethylenediamine and the higher members of the ethyleneamine series
were obtained from the reaction product by treatment with lime.
Essentially the same process, altered in detail, was adapted for
commercial production. Pilot plant production of the ethyl eneamines
was started in 1933 at the Mellon Institute, followed by commercial
production by Carbide and Carbon Chemicals Corporation (now Union
Carbide Corporation) and Dow Chemical Company.
Because of the bifunctional nature of both the dichloride and
the diamine the higher ethyleneamines are by-products which are avail-
able commercially. These include diethylenetriamine, triethylenete-
tramine, and tetraethylenepentamine. Physical properties for ethy-
lenediamine and these higher ethyleneamines are given in Table 1.5.
1.5.1 Ethylenediamine from Ethylene Dichloride
Ethylenediamine is produced by the direct reaction of ethylene
dichloride and ammonia, as follows:
Cl CH2 CH2 Cl + 2NH3 - H2N CH2 CH2 NH? + 2HC1
A secondary dehydrochlorination reaction also occurs yielding vinyl
chloride in amounts up to 3% of the ethylene dichloride introduced.
The reaction is as follows:
Cl CH2 CH2 Cl + NH3 - NH4C1 + CH2 = CH Cl
Commercial production of ethylenediamine generally employs liquid
phase ammonolysis with aqueous ammonia. Reaction conditions vary but
1-27
-------
I'd ruin I ,i
Krucz lilts I'oliit. °C
llolllnu I'ulut, "C 760 imu IIC
-Specific Gravity, 25/25°C
Vl:icoaily, cl', 20°C.
Kliiali I'oiiit, °tf
IMIYSICAI. I'KDl'
IC'I'IIYI.KNI'lllAMINIi
2 ' 2 ' 2 2
11.0
117.0
i.h
100
TAIIUi 1.5
Oh' KTIIYMiNKDt AMINii AMI) III CHICK KTllYl.lDNIiAMlNCS
Dlli'l'IIYI.IiMK'rUIAHTNK
-15
206. 7
0. 'J50
1. 1
•fKIETUYUiNETCTRAHIHE
277.4
0.977
26.7
265
TETRAEIIIYl.tMliPliNVAHIME
NH2(CII2Cll Nil) CM Cll Mil.
0. 992
96.2
310
E: Kirk-ULIiuiur, 196'I.
BEST AVAILABLE COPY
-------
in all cases a mixture is formed. At comparatively low temperatures
and pressures, predominantly ethylenediamine is formed in low yield.
At higher temperatures and pressures the yields are greater but the
proportion of the polyethylene polyamines is higher. Ethylenediamine
formation is also favored by the use of concentrated ammonia solu-
tions in ratios up to 15:1 over ethylene dichloride.
Curine, et al., in a 1931 U.S. patent to Carbide and Carbon
Corporation describes the treatment of ethylene dichloride with
excess aqueous ammonia at 110°C and 10 atm. pressure in a horizontal
pressure reactor equipped with a stirrer. The mixture of reaction
products containing ethylendiamine hydrochloride, ammonium chloride
and an aqueous solution of ammonia are passed into a stripper column
to recover most of the ammonia for recycle. Sodium hydroxide may be
fed continuously to liberate ammonia from the ammonium chloride and
ethylenediamine from the hydrochloride. The process is made continuous
by feeding additional ethylene dichloride and ammonia to the reactor.
No catalyst is necessary for the reaction but the rate is accelerated
by the presence of cuprous chloride.
Use of cuprous chloride is described in a U.S. patent to Lauter
of Wingfoot Corporation in 1935. Ethylene dichloride, aqueous ammonia
and cuprous chloride are heated under pressure to form a complex salt.
The diamine is separated from the complex salt by distilling the
reaction product with caustic soda.
1-29
-------
Goodyear Tire and Rubber Company obtained two foreign patents in
1932 and 1936 describing the use of zinc chloride and zinc oxides as
catalysts. The complex salts of zinc are dissolved in liquid ammonia
and carbon dioxide added. The carbonate of ethylenediamine is pre-
cipitated and decomposed by heating with water (Herold and Sennervald,
1936) .
A British patent to Farbenfabriken Bayer in 1955 claims improved
yields of diamine by using a 50 - 65 % solution of ammonia. Using
65% aqueous ammonia at 120°C and 60 - 70 atm. pressure all the ethy-
lene dichloride was reacted and the product contained 67% of ethy-
lenediamine and 33% polyethylenepolyamines.
Dylewski, et al., in a U.S. patent to Dow in 1956 describe a
process whereby 1 mole ethylene dichloride and 6.4 moles of ammonia
in 35% aqueous solution plus 0.115 mole of diethylenetriamine were
kept at 150 - 225°C for 11 seconds at 2000 psig pressure. The
reaction product was cooled, made alkaline with 50% sodium hydroxide
and steam distilled to separate the ethyleneamines from the residue
which was principally tetraethylenepentamine. The ethyleneamines
were separated by fractional distillation to give ethylenediamine
47.5%, diethylenetriamine 10%, tetraethylenepentamine, 19.5%, and
vinyl chloride, 3.6% (all in wt%).
Montecatini in an Italian patent in 1961 describes how to
remove the by-product vinyl chloride. The recycle ammonia contains
the vinyl chloride which reacts to give insoluble and troublesome
1-30
-------
anionic exchange resins. Vinyl chloride is separated from ammonia by
absorption of ammonia solution in a tower at 6 atm. pressure and
40°C with 24% ammonia solution, and in a second tower at atmospheric
pressure with water. Vinyl chloride is discharged at the head of
the second tower.
A Polish article (Leszczynski, et al., 1967) deals with studies
of three pilot-scale pressure reactors. They found that an empty
vertical tube gave the highest yields of ethylenediamine. A Japanese
patent of 1968 to Japan Soda Company describes a method to prepare
ethylenediamine of a desired concentration (above 80%) by adding a
certain amount of sodium hydroxide to an aqueous solution.
Muhlbauer in a U.S. patent to Jefferson Chemical Company in 1968
describes a process to produce anhydrous ethylenediamine. A 50%
aqueous solution of ammonia is placed in a reaction zone with ethylene
dichloride at 80 - 140°C and 500 - 1000 psig. for 10 - 20 minutes to
give the ethylenediamine dihydrochloride and the amine hydrochloride
by-products. The crude reaction product is sent to a separation zone
where the ammonia and water are evaporated. The liquid component is
discharged to a combination neutralization-separation zone where it
is contacted with 30 - 60 wt% of sodium hydroxide at 120 - 180°C.
The water and free amines are volatilized leaving a liquid slurry of
sodium chloride and sodium hydroxide. The slurry is filtered, washed
with water and recycled. The aqueous amine fraction is distilled.
1-31
-------
A British patent to Blears and Simpson in 1969 describes a
process producing high yields of ethylenediamine. A 60 wt% aqueous
ammonia solution at 165°C is mixed with ethylene dichloride at room
temperature in at 92:1 molar ratio. The mixture is introduced into
a reactor at 1400 psig. pressure with an inlet temperature of 145°C
and an outlet temperature of 180°C. The product consisted of 87.2%
ethylenediamine and 11% of diethylenetriamine.
Several references pertain to the separation and recovery of
ethylenediamine from the reaction mixture. A Polish article (Kubica,
et al., 1968) describes a method which allows the use of ammonolysis
mixtures without removing ammonia from them. Also claimed are low
losses of ethylenediamine and sodium hydroxide with the sodium
chloride of sufficient purity for electrolysis. The method is based
on the fact that the solubility of the ethyleneamines decreases with
their increasing molecular weight. The distribution coefficient of
ethylenediamine between the layer of higher polyethylene polyamines
and the sodium hydroxide layer was determined as a function of the
sodium hydroxide concentration. The required apparatus consisted of
three evaporators, a separator-column, extractor plus crystallizer,
centrifuge (for sodium chloride removal), rectification column and
partial condenser.
A U.S. patent (Milligan and Cour, 1969) describes a process for
amine recovery by using an organic solvent, such as xylene, for
azetropic distillation of water from the treated reaction mixture.
1-32
-------
A German patent (Adam and Merkel, 1971) to BASF describes the use of
pyridine in an azetropic distillation to dehydrate ethylenediamine.
1.5.2 Ethylenediamine from Ethanolamine
In this process for the production of ethylenediamine, mono-
ethanolamine, water, ammonia and recycled products are fed to a
catalytic reactor. The reaction takes place in a hydrogen atmosphere
at moderate temperatures and high pressure. The reaction is as
f o Hows :
H2
catalyst
This process as licensed by Leonard Process Company has none of the
organic-laden-salt pollution or vinyl-chloride-hazards of the con-
ventional ethylene dichloride feedstock routes (Kohn, 1978). Offer-
ing a capital-cost saving of aoout 17% over a e thy lene-di chloride-
feed plant, this route is claimed to give a 25 to 50% reduction in
utilities expenditures. The disparity in raw-materials price of
about 30c/lb. for ethanolamine versus about llc/lb for ethylene
6
dichloride should be more than made up by the route's lack of pollu-
tant effluents- and auxiliary equipment needed to treat them.
The process has been made feasible by the development of a pro-
prietary amination catalyst by Societe Chimique de la Grande Paroisse
SA (Paris), who are joint developers with Leonard Process Company.
Continuous testing has demonstrated a 2000 hour catalyst life with
no dropoff in activity. Ultimate catalyst life-expectancy is being
determined.
1-33
-------
In the ethylene dichloride process sodium hydroxide is the
catalyst in a liquid-phase reaction that also produces vinyl chloride
and hydrochloric acid as byproducts. In addition, a 10,000 metric-
ton/year plant generates about 30,000 Ib/hr of a salt solution con-
taining roughly 10 - 12% sodium chloride. Organics must be removed
from this stream and the salt must be disposed of.
BASF AG, Ludwigshafen, West Germnay, has had an ethylenediamine
from ethanolamine process in its facilities at Ludwigshafen and at
Antwerp, Belgium for several years. The process uses a BASF-developed
catalyst. BASF's route is reported to produce substantial amounts of
piperazine which is no problem for them since they have outlets for it.
A new proprietary process based on ethylene oxide has just been
announced by Union Carbide Corporation (Anonymus a & b, 1978). The
70 million-lb/yr addition costing over $50 million will double the
current capacity of the Taft, Louisiana plant. (Another 60 million
Ib/yr of capacity exists at Carbide's Texas City, Texas installation.)
This new process uses ethylene oxide, as chief reactant, along
with ammonia. It depends on a new propietary catalyst. Carbide
claims that the process requires less energy, and allows more flexi-
bility in determining product mixes.
The new facility will be brought on in two stages. The first,
set for completion by early 1980, will produce higher amines - includ-
ing diethylenetriamine, triethylenetetramine and tetraethylenepenta-
mine. The second stage, expected to be finished by early 1981, will
enlarge capacity for all ethyleneamines, including ethylenediamine.
1-34
-------
In what may be a related process a German patent issued to Best
from Union Carbide in 1977 describes the sequential ammonolysis of
ethylene glycol to ethanolamine and then to ethylenediamine. The
catalyst was a prepared supported composition of Ni - Re. The
catalysts are claimed to be selective with only small amounts of
piperazine formed.
The patent literature shows that interest in the use of ethanol-
amine as a route to ethylenediamine has existed for some time. A U.S.
patent to MacKenzie of Dow Chemical in 1958 uses catalysts of Raney
nickel, cobalt, copper chromite, platinum or palladium. In an example,
ethanolamine and 350 mole% of ammonia were passed continuously over
a Raney nickel catalyst at 195°C and 1950 psi pressure. A residence
time of 26 minutes gave a conversion of 75% to 24.1% ethylenediamine,
29.8% piperazine and 14.5% of diethylenetriamine.
Lichtenberger and Weiss in a German patent (1958) claim improved
yields using a Ni-MgO catalyst obtained by decomposition of Ni-Mg
formates. Only traces of piperazine were found. An equivalent French
patent was issued to the same company in 1959. (Societe d'Electrochi-
mie - 1959).
A French patent to BASF AG, Ludwigshafen, West Germany, describes
the preparation of a catalyst from cobalt carbonate and nickel for-
mate (Winderl, et al., 1963). A mixture of 9.2 kg cobalt carbonate
and 0.9 kg of nickel formate is calcined, and the oxide mixture
sintered at 1050°C in the presence of air. The prepared catalyst
1-35
-------
(500 ml) was treated 24 hours at 325°C and 24 hours at 375°C with
30 L. of hydrogen/hour. The reactor is pressured at 200 atm. with
hydrogen and the catalyst treated with 50 L. H2/hr., 850 ml. liquid
NH3/hr., 31 g. ethanolamina/hr, and 5 g. diethanolamine/hr. for 10
hours. The product contained 93 g. water, 211 g. ethylenediamine,
71 g. piperazine, 22 g. ethanolamine, and 24 g. diethanolamine.
This represents a 93% conversion of ethanolamine and a 74.5% yield
of ethylenediamine (based on ethanolamine).
BASF has used this process in their facilities at Ludwigshafen
and at Antwerp, Belgium, for several years. BASF has outlets for the
substantial amounts of piperazine produced by this process.
A recent U.S. patent to BASF (Boettger, et al., 1977) claims
an improved catalyst which reduces the amount of piperazine and other
by-products. The catalyst composition, calculated on the metal con-
tent of the catalyst, consists of 70 to 95% by weight of a mixture of
cobalt and nickel and 5 to 30% by weight of copper. The preferred
weight ratio of cobalt to nickel is 1:1 with a preferred content of
15% by weight of copper. In an example a catalyst containing 10%
by weight of cobalt oxide, 10% by weight of nickel oxide and 4% by
weight of copper oxide on aluminum oxide was reduced with hydrogen at
250°C. To the catalytic reactor there was added 100 parts/hour of
ethanolamine and 350 parts by volume of liquid ammonia at 160°C and
a hydrogen pressure of 300 atmospheres gauge. Ammonia was distilled
from the reaction discharge which then amounted to 115 parts/hour,
1-36
-------
consisting of 49% ethylenediamine, 36% ethanolamine, 6% piperazine
and 8% polyamines. The yield of ethylenediamine after a single pass
is 77% based on reacted ethanolamine.
A Franch patent (Mo Och Domsjo Aktiebolag, 1969) claims a stable
new catalyst prepared by melting a mixture of nitrates of Ni, Co, Fe ,
and Al (1:1:1:8 metal equivalents) to remove water, followed by .heating
at 800°C in air, and 4 hours under hydrogen at 400°C. Ethanolamine
and anhydrous ammonia were reacted over the catalyst at 225°C for 5
2
hours at a hydrogen pressure of 50 kg/cm . Conversion of ethanolamine
of 84% was attained to give 43% ethylenediamine, 25% piperazine, 2%
diethylenetriamine, 5% aminoethylpiperazine and 7% 2-hydroxy-1.4-
diaminobutane.
In a recent Russian patent (Tereshchenko, et al., 1977) an
improved catalyst was claimed by using 0.2 - 2.0 wt% Ni on chromium
oxide.. Ethylenediamine was prepared by amination of ethanolamine
with ammonia in a 1:25 molar ratio in the presence of the above
catalyst and hydrogen at 150 - 210°C and 80 - 170 atm.
A U.S. patent to Jefferson Chemical Company (Moss and Godfrey,
1964) , describes a catalyst and reaction conditions which favor the
formation of piperazine over ethylenediamine. Of interest are the
other reaction products which are identified including N-methylethyl-
enediamine, N-ethylethylenediamine, 1-methylpiperazine, 1-ethylpiper-
azine, N-aminoethylpiperazine, N-hydroxyethylpiperazine, and 2-(2-
aminoethylamino) ethanol.
1-37
-------
Two patents refer to the use of ethylene glycol as feedstock
which undergoes sequential aminolysis to ethanolamine and then to
ethylenediamine. A U.S. patent to Allied Chemical Corporation (Fitz-
William, 1964) using a Ni-Cu catalyst in about 1:1 ratio gave 46%
yield of ethylenediamine. A recent German patent to Union Carbide
(Best, 1977) uses, as catalyst, supported compositions of Ni - Re.
The catalysts are claimed to be selective for ethanolamine and ethy-
lenediamine with only small amounts of piperazine being formed.
1.6 Amine Synthesis by Hydrogenation of Nitro Compounds
The synthesis of amines by hydrogenation of nitro compounds is
one of the methods by which amination by reduction may be carried out.
In amination by reduction, in contrast to ammonolysis, a bond between
carbon and nitrogen already exists in the molecule. Nitro compounds
can be converted to amines by hydrogenation in the presence of a
catalyst in either the liquid or the vapor phase.
In section 1.4.3 we discussed the synthesis of aniline by the
ammonolysis of phenol. Aniline manufacture in the United States is
based predominantly on the continuous, vapor phase, catalytic reduc-
tion of nitrobenzene. About 8%, based on name plate capacity, is
manufactured by Rubicon Chemicals, Inc. using a liquid catalytic
reduction process. They are currently adding a 220 million pounds
per year plant which will increase the capacity of the existing
Geismar, Louisiana, facility to 280 million pounds per year.
1-38
-------
The gas phase heterogeneous catalytic hydrogenation of nitrobenzene
to aniline using a copper catalyst is shown below:
N°2 270 - 475'C ^2
+ 3H2 » jp^j + 2H20
1 atm. x?^
copper on
silica
The liquid phase heterogeneous catalytic reduction of nitrobenzene
to aniline using a nickel catalyst is shown below:
atm.
+3H2
nickel on
kieselguhr
1-39
-------
2.0 PROCESS DESCRIPTIONS
In this section we will present flow diagrams for each of the
six processes to be considered along with a narrative description
of the process. As far as is possible we will indicate the main
streams, side streams and air, water and solid discharges. In all
cases the data was obtained from the open literature except for the
DuPont data on their methylamines plants in Belle, West Virginia and
Houston, Texas. This data was submitted to the U.S. Environmental
Protection Agency, Effluent Guidelines Division during 1974 and 1975.
Extensive operating data was presented to show that the original
guidelines raw waste loads were too low.
2.1 Methylamines from Methanol
We will present flowsheets and discussions of four processes for
production of methylamines. The two DuPont plants differ in several
respects. The Houston plant does not have parallel operations, it
recycles 70% more amines at the same production levels, all trimethy-
lamine is recycled, and additional fume scrubbing facilities have
been added. The Leonard Process Company has the only process avail-
able for license. The Rohm and Haas process, as described by Chopey
in 1961 gives more details of operating conditions than the other
processes.
2.1.1 Rohm and Haas Methylamines Process
The flow diagram of the Rohm and Haas methylamines process is
given in Figure 2.1. The feed methanol was vaporized by steam and
2-1
-------
combined with an ammonia stream plus recycled amines. The mixture
passed through two preheaters, or heat exchangers in series, in which
steam and a diphenyl-diphenyl oxide mixture heated the stream to
about 660°F.
The process stream, at 75 psig, entered a vertical reactor and
passed upward through tubes containing an undisclosed dehydrating
catalyst (Alumina or silica alumina catalysts are commonly used.).
Heat control was obtained by means of a diphenyl-diphenyl oxide mix-
ture. The reaction took place at 660 - 750°F.
The product mixture was cooled and condensed, and then entered
a low-pressure stripper operating at about 60 psig. The water, which
was virtually amine free, left as bottoms and was sent to the city
sewer. The overhead dry mixture of amines and unreacted ammonia was
passed through a one-stage reciprocating compressor to raise the
pressure to 250 psig. The dry compressed gaseous amines-ammonia
mixture was fed to a still for ammonia removal. The ammonia stream,
which left overhead at about 115°F, contained about 7% trimethy1amine.
It passed through a reducing valve that lowered the pressure to 75
psig and was recycled to the beginning of the process.
The mixed-amines bottoms stream emerged from the ammonia strip-
per at 240°F and went to a 100 ft. distillation column, where extrac-
tive distillation with water yielded trimethylamine as overhead pro-
duct, which was ready for storage and stripping. This column operated
at about 175 psig, and water was introduced at the top.
2-2
-------
Amiiionid-rich recycle, 7!i psnj.
I XI'/UMON
AmmnnUi
Ammonia -
rich
recycle
— * 1
COOI1K COMDtNSEK
CATALYTIC
CONVERTERS
( 1 on stream
1
Dipheuyl mixture — *•
(hudlincj agent) ^
span:
n
PHEIIEATERS |
.-
Stedm— >.
Amiiunia
amine-
methanol
mixture - -
' 1
Kec.vUe umines I
-L
^
\
— »
»- —
r
-H
-
r
Ammonia
ami tie-
^~A r~R s~*
2H2h
*\
Dipheuyl
in Ix hire
i.imlrul
^
v+JD*
r
»-
We I iimine-
diiiuonia
meUuiiol mixture.
mixture
. 60 psicj ,-».
\c
L:
LOW-
PRESSUK
STRIPPE
CuO F., 1 I. ,/
75 ,,slg. fv) 1
• * — i
Condensate I |
\
Water Lo
Q©
Steam-*
disposal
Dry
dlillllu-
diiuiunid
mixture,
2b() psig
Auuiionia-
rich
recycle,
115 F.
pX
Ualer — »
FIUST
STILL
»-
Aiuine
mixture
$
Tl
Ami ne
mixture,
240 F.
Triiiiethylamine, to
storage or recycle
TRIMET1IYL-
AMINE
SEPARATOR
Aqueous
mono-
dime thylamine
solution
HIGH
PRESSURE
STRIPPER
Dry mono- and
dimethylamine
mixture
125 psig.
Water to
disposal
Mnnomethylamine, t
storage or recycl
SECOND
SI ILL
Dimethylamlne, to
storage or recycle
Wet bottoms
(removed iiilerini UenLly)
bOIIHCE: Chopey, 1961.
FIGURE 2.1
1(011(1 & HAAS PROCESS I OR METIIYLAMINES
-------
The column bottoms was a 25 - 35% aqueous solution of mono- and
dimethylamine. This went to the high pressure stripper which removed
the water added in the previous step. A water-free product then
entered the second still for final separation of the amines.
This vessel operated at 125 psig yielding monomethylamine over-
head. The dimethylamine was removed a few plates up from the bottom
of the column, to assure that there was no residual water in the
stream. The water bottoms were allowed to accumulate and were removed
as required.
The three methylamines plants that Rohm and Haas operated at
that time incorporated bubble- cap trays, sieve trays and packing in
the five separation columns downstream from the converter at each
plantsite. The packing was generally Raschig rings. The columns
were about 70 ft. high except for the 100 ft. trimethylamine separator.
2.1.2 Leonard Process Company Methylamines Process
The flow diagram of the Leonard Process Company for the produc-
tion of methylamines is given in Figure 2.2. Ammonia, methanol and
recycle liquid are fed continuously through a vaporizer and preheater
into an amination catalyst packed converter. (A Netherlands patent
application to Jackson Leonard in 1966 describes methylamine catalysts.
Silica alumina is impregnated with 0.05 - 0.95 wt.% of an activator
like Ag3?04, Re2S7, MoS2> or CoS.). Part of the exothermic heat of
reaction is used in the feed preheater.
2-4
-------
10
I
Ul
Preheater
II, + CO
A
Crude
product
storage
Methanol Anunorila
Vaporizer
Recycle
10 C
c
o
o
o
Water
3
o
o
s §
"o
o
Y
Waste-
water
SOURCE: Leonard Process Co., 1973.
FIGURE 2.2
LEONARD PROCESS FOR METHYLAMINES MANUFACTURE
-------
The crude reaction product is fed to a series of four distillation
columns. The first column separates excess ammonia and part of the
trimethylamine-ammonia azetrope which is recycled. Bottoms go to
the trimethylamine column where water is added for extractive distil-
lation and pure trimethylamine goes overhead to product storage or
recycle. Bottoms are fed to the monomethylamine column where pure
monomethylamine goes overhead to storage or recycle. The monomethyl-
amine column bottoms go to the dimethylamine column where pure di-
methylamine goes overhead to product storage or recycle. Water is
drained from the bottom to waste. All the products are 99% pure.
The overall yield from both ammonia and methanol is above 95%.
Sixteen companies in eleven different countries used this pro-
cess as of 1973. Three additional European plants were scheduled
for completion by 1975.
2.1.3 Methylamines Process at the Belle Plant of DuPont
The flow diagram for the methylamines process at the Belle,
West Virginia, plant of DuPont is given in Figure 2.3, as revised
on December 17, 1974 (Quarles, 1975). The distillation train of the
Belle methylamines plant is also used to recover amine and methanol
values from the wastes of three other processes.
A test spanning five weeks was conducted at the Belle plant
from April 29 to June 2, 1975. During much of this time production
of the products which shared -common equipment was discontinued so
that the waste loads from methylamines could be isolated and analyzed
2-6
-------
Noncoridenslules
vented to
atmosphere
Steam Water
I
Oil Layer to
I nc inerator
c
ra
o
&
Covered
sewer
to waste
* — Liquid Purge
from Product C
Vents from
Metliylamim.'s
Product b
Product f.
Steam-*-
=i e
o
O
o
V^ y
Steam
bteam
Y
Waste
Metlianol Waste-
Irom water
Product A
&
Steam
Steam
- — .
Waste
Waste- Methanol
wa ter from
Product B
S 0
>•! Product)*-
r
^->
i-
0
01
Q
Oil layer to
Incinerator
Covered
sewer
to waste
FIGURE 2.3
METHYLAM1NES MANUFACTURE, BELLE PLANT
SOimCfc:
-S, I97i>.
-------
separately. Tables 2.1 to 2.5 include data on the wastes discharged
in the bottom streams from five pieces of equipment. Table 2.6 com-
pares the combined discharges from these five sources to the dis-
charge from other sources. Table 2.7 gives data on the combined
discharges to the wastewater treatment sewer. The data from these
tables will be discussed following a description of the process.
The flowsheet of the Belle methylamines plant as given in
Figure 2.3 shows parallel distillation trains for part of the distil-
lation system, and the points of introduction of recovery streams
from products A, B, and C. Three potential products are shown,
trimethylamine (TMA), dimethylamine (DMA), and monoethylamine (MMA).
All three amines are present in the product stream from the converter
based on chemical equilibrium. Relatively little cantrol of the
equilibrium ratios is possible. The converter output is set to
meet the sales demand for the limiting product. All excess of the
other amines must be recycled. Thus the flow through any given dis-
tillation column is independent of whether a product is sold or re-
cycled. The distillation train requires full separation of each
amine and recycle of excess over sales. Thus the potential pollution
load is a function of the total throughput of the columns, not the
amount sold.
Similar to the two processes described previously the Belle
plant, as shown in Figure 2.3, passes methanol, ammonia and recycle
through a vaporizer and preheater into the catalytic converter.
2-e
-------
The product stream is combined with an overhead stream from a vent
dehydrator and sent to the ammonia column. The vent dehydrator is
fed from the vents from methylamines and products A and B, and a
liquid purge from product C. From the ammonia column the ammonia
taken off overhead goes to recycle and the mixed-amines bottoms goes
to the TMA column. Steam is added and extractive distillation with
water gives TMA as overhead product. At this point the bottoms from
the TMA column are split and sent to parallel distillation trains,
initially to the No. 1 dehydrator and No. 2 dehydrator. However,
the load on these two trains is not equal and they do not vary in
exactly the same manner, so sampling of all five discharge streams
and flow proportioning is necessary to arrive at a true pollution
load.
The water-free overhead product from the dehydrators is sent to
the No. 1 and No. 2 mono-columns for final separation of the two
amines. Product MMA is obtained from the overhead and product DMA
from the bottom of the mono-columns.
A side stream from each dehydrator is combined with a waste
methanol stream from product A for one train and a waste methanol
stream from product B for the other train and sent to the No. 1 and
No. 2 methanol recovery columns. A waste water stream is taken from
each dehydrator.
The methanol overhead from the methanol recovery columns is
returned to recycle. The bottoms are sent to decanters where an oil
2-9
-------
layer is separated for incineration. The bottoms from the dehydrators
go to a covered sewer to wastewater treatment.
2.1.3.1 Analytical Data on Wastewater Discharges at the Belle
Plant. As mentioned previously, wastewater discharges were sampled
and analyzed in a five week test conducted at the Belle plant from
April 29 to June 2, 1975. Production rate averaged 79% of capacity
during the test without capacity operation being attained during
any part of the test. Operation was exemplary during the test
period with no start-ups or shutdowns, and no steam upsets. The
dumping of large quantities of waste load from the columns can be
caused by steam upsets. When the distillation train is pushed to
capacity, the columns become very sensitive to upset. If the plant
had been operated at capacity, a much higher variability and higher
BOD would have been observed.
Six continuous composite samples were taken daily from the
five columns and the combined waste stream from the amines plant.
The No. 2 methanol recovery column was not sampled properly until
May 14 when an improper sampling arrangement was corrected and a
plugged line cleared. Each of the six samples was analyzed daily
for pH, COD, BOD5 (acclimated seed) and TKN. TOG analyses were be-
gun on all samples on May 9. Analysis were begun on May 7 for di-
methylamine (DMA), monomethylamine (MMA), trimethylamine (TMA),
methanol, dimethylformamide (DMF) , dimethylacetamide (DMAC), methyl
acetate and methyl formate. Analyses were continued through June 2
2-10
-------
for all chemicals except for methyl acetate and methyl formate which
were analyzed for 17 days through May 23.
Tables 2.1 through 2.5 present analytical data in ppm for the
above listed items for the five columns. The data include values
for the average, standard deviation (SD) and average plus 3 SD. Also
listed are pounds per day discharged for the same three categories.
We will discuss the data on the specific chemicals rather than BOD,
COD, etc.
Tables 2.1 and 2.2 for the No. 1 and No. 2 dehydrators show
general similarity except that No. 2 discharged about twice as much
methanol, methyl acetate and methyl formate. Methanol accounts for
more than all the other discharges, 61 - 126 Ibs/day, with methyl
acetate next at 32 - 51 Ibs/day, followed by methyl formate at 18 -
29 Ibs/day (all discharge values given in this report will be the
average value unless otherwise stated). No TMA was detected, with
only very small amounts of DMA and MMA at 1.4 - 1.8 Ibs/day discharge.
Only traces of DMF and DMAC were detected.
Tables 2.3 and 2.4 refer to the No. 1 and No. 2 methanol recovery
columns. The big difference between the discharges from the two
columns is the DMA value of 160 Ibs/day for No. 2 column compared to
1.4 Ibs/day for No. 1 column. This resulted from very high values
for the period from May 24 to May 28, 1978 with the discharge of
DMA reacting 1100 Ibs/day on May 28, 1978. This would certainly
2-11
-------
TAIJLE 2.1
MliTHYLAMINES PROCESS, WASTEWATER, BELLE PLANT
NO. 1 DEHYDRATOR BOTTOMS, 4/29/75 - 6/2/75
BOD - A
COD
TKN
TOC
PH
Dime thy lamine (DMA)
Monomethylamine (MMA)
Trimethylamine (TMA)
Methanol
DimeLhylformamide (DMF)
Dimethylacetamide (DMAC)
Acetate
Formate
AVERAGE
128
188
11
169
12.7
3
3
0
127
2
0.4
69
38
PPM (EXCEPT pi
STANDARD
DEVIATION
219
236
4
166
0.1
5
4
0
218
7
1
44
23
0
AVERAGE
+3 SD
784
896
23
666
13
17
15
0
781
22
3
201
108
POUNDS
AVERAGE
62
92
5
79
-
1.5
1.4
0
61
0.9
0.2
32
18
PER DAY DISCHARGED
STANDARD
DEVIATION
103
111
2
78
-
2.4
1.7
0
105
3.3
0.5
21
11
AVERAGE
+3 SD
372
427
11
314
-
8.6
6.6
0
377
10.8
1.6
95
52
I
M
ro
-------
TABLE 2.2
METHYLAMINES PROCESS, WASTEWATER, BELLE PLANT
NO. 2 DEHYDRATOR BOTTOMS, 4/29/75 - 6/2/75
BOD - A
COD
TKN
TOG
PH
Dimethylamine (DMA)
Monomethylamine (MMA)
Trlmethylamine (TMA)
Methanol
Dlmethylformamide (DMF)
Dimethylacetamide (DMAC)
Acetate
Formate
AVERAGE
167
299
13
188
12.7
2.5
2.0
0
174
0.1
0.3
67
40
PPM (EXCEPT pH)
STANDARD
DEVIATION
152
338
4
64
0.2
3.6
2.3
0
149
0.3
1.4
57
28
AVERAGE
+3 SD
623
1312
25
380
13.1
13.3
8.9
0
622
0.9
4.4
239
124
POUNDS
AVERAGE
121
216
9
136
-
1.8
1.5
0
126
0.1
0.2
51
29
PER DAY DISCHARGED
STANDARD"
DEVIATION
117
255
3
48
-
2.6
1.6
0
112
0.2
1.0
43
21
AVERAGE
+3 SD
471
981
18
279
-
9.5
6.4
0
463
0.7
3.2
181
90
N5
I
M
CO
-------
TABLE 2.3
METHYLAMINES PROCESS, WASTEWATER, BELLE PLANT
NO. 1 METHANOL RECOVERY COLUMN BOTTOMS, 4/29/75 - 6/2/75
BOD - A
COD
TKN
TOC
PH
Dimethylamine (DMA)
Monomethylamine (MMA)
Trimethylamine (TMA)
Methanol
Dimethylformamide (DMF)
Dimethylacetamide (DMAC)
Acetate
Formate
AVERAGE
772
2773
111
1892
12.9
6
42
0
52
1.4
7.7
72
363
PPM (EXCEPT pH)
STANDARD
DEVIATION
192
976
55
696
0.2
10
78
0.2
58
3.2
25
75
368
AVERAGE
+3 SD
1349
5702
111
3979
13.6
36
275
0.6
225
11
84
297
1467
POUNDS
AVERAGE
192
685
28
455
-
1.4
10
0
13
0.3
1.9
17
90
PER DAY DISCHARGED
STANDARD
DEVIATION
52
238
13
164
-
2.4
19
0
14
0.8
6.1
18
92
AVERAGE
+3 SD
348
1399
67
946
-
8.5
66
0.1
56
2.7
20
71
364
I
M
-P-
-------
TABLE 2.4
MET11YLAMINES PROCESS, WASTEWATER, BELLE PLANT
NO. 2 METHANOL RECOVERY COLUMN BOTTOMS, 5/14/75 - 6/2/75
BOD - A
COD
TKN
TOC
pH
Dimethylamine (DMA)
Monomethylamine (MMA)
Trimethylamine (TMA)
Methanol
Dimethylformamide (DMF)
Dimethylacetamide (DMAC)
Acetate
Formate
AVERAGE
3134
5029
435
6631
12.9
1406
23
0
257
78
11
81
787
PPM (EXCEPT pH)
STANDARD
DEVIATION
4972
3926
758
5493
0.3
2350
42
0
627
223
32
52
640
AVERAGE
+3 SD
18052
16807
2708
23110
13.7
8458
147
0
2137
747
107
235
2706
POUNDS
AVERAGE
367
598
50
779
-
160
3
0
36
7
2
10
103
PER DAY DISCHARGED
STANDARD
DEVIATION
556
437
83
621
-
260
6
0
92
25
5
7
90
AVERAGE
+3 SD
2036
1909
298
2642
-
940
21
0
313
82
16
31
378
tSJ
I
Ln
-------
seem to be the result of an upset in the column. The other values are
comparable to the discharges from the dehydrator columns except for
methyl formate which is considerably higher at 90 - 103 Ibs/day dis-
charge.
Table 2.5 refers to the vent dehydrator. This is a very impor-
tant piece of equipment at both the Belle and Houston plant sites.
Noncondensables formed in the converter are continuously vented from
the process. These and other volatile components are collected and
stripped in the vent dehydrator. The aqueous wastes are discharged
to the sewer and volatile components recycled to the process. Analy-
sis of these aqueous wastes shows high values for DMA (231 Ibs./day
average), DMF (129 Ibs/day) and methyl acetate (184 Ibs/day). There
are moderate amounts of methanol (80 Ibs/day), methyl formate (54 Ibs/
day) and DMAC (46 Ibs/day).
Table 2.6 compares the discharges from the bottom streams of
the five columns to the discharges from "other sources", with no
information as to what the other sources are. They are certainly
significant since in most cases they are equal to, or greater than,
the combined discharges from the five columns. DMA and DMF are almost
twice as great from other sources (736 vs 449 and 330 vs 184 Ibs/day).
However, the methyl acetate discharge is much greater from the five
bottom streams, 158 vs 12 Ibs/day and methyl formate is almost three
times as great, 320 vs 127 Ibs/day.
2-16
-------
TABLE 2.5
METHY1 AMINES PROCESS, WASTEWATER, BELLE PLANT
VENT DEHYDRATOR BOTTOMS, 4/29/75 - 6/2/75
BOD - A
COD
TKN
TOG
PH
Dime thy lamine (DMA)
Monomethylamine (MMA)
T rime thy lamine (TMA)
Methanol
Dimethylf ormamide (DMF)
Dime thy lacetamide (DMAC)
Acetate
Fo rma t e
AVERAGE
2672
3600
263
2567
12.7
1193
13
0
416
662
222
903
271
PPM (EXCEPT pH)
STANDARD
DEVIATION
4416
5568
453
4258
0.2
2638
43
0
1022
2064
546
1299
790
AVERAGE
+3 SD
15921
20303
1621
15340
13.4
9108
141
0
3482
6852
1861
4799
2641
POUNDS
AVERAGE
547
746
52
504
-
231
3
0
80
129
46
184
54
PER DAY DISCHARGED
STANDARD
DEVIATION
889
1160
82
854
-
508
9
0
192
410
115
271
158
AVERAGE
+3 SD
3213
4227
298
3065
-
1754
28
0
656
1359
391
997
529
N>
I
-------
TABLE 2.6
METHYLAMINES PROCESS, WASTEWATER, BELLE PLANT
DISCHARGE FROM FIVE BOTTOM STREAMS COMPARED TO DISCHARGE
FROM OTHER SOURCES 5/14/75 - 6/2/75
DISCHARGE, POUNDS PER
FIVE BOTTOM SOURCES
AVERAGE STANDARD
DEVIATION
BOD - A
COD
TKN
TOG
Dimethylamine (DMA)
Monomethylamine (MMA)
Trimethylamine (TMA)
Methanol
Dimethylformamide (DMF)
Dimethylacetamide (DMAC)
Acetate
Formate
1241
2170
149
2017
449
20
0
375
184
7
158
320
1373
1199
139
1355
697
25
0.1
334
471
9
72
237
DAY,
AVERAGE
+3 SD
5362
5767
566
6084
2540
95
0.2
1378
1598
34
370
1030
DISCHARGE, POUNDS PER
OTHER SOURCES
AVERAGE STANDARD
DEVIATION
1262
1772
558
1858
736
11
4
355
330
5
12
127
2132
4806
1062
3463
1369
12
5
471
700
3
20
206
DAY,
AVERAGE
+3 SD
7657
16190
3744
12246
4843
47
18
1768
2429
14
71
744
K)
M
CO
-------
Table 2.7 gives the analyses of the materials in the stream to
the waste water treatment sewer in ppm and the pounds/day discharged.
The amounts are about equal to the sum of the discharges from the
five columns and other sources, as given in Table 2.6. The main
discharge is DMA, 1389 Ibs/day, with about half as much methanol,
690 Ibs/day. There are surprising amounts of the three by-products,
DMF, 719 Ibs/day, methyl formate, 346 Ibs/day and methyl acetate,
172 Ibs/day.
2.1.4 Methylamines Process at the DuPont Houston Plant
The flowsheet of the DuPont Houston methylamines plant is shown
in Figure 2.4 (Quarles, 1975). The basic process is the same as the
Belle plant with the following major differences:
• Houston does not have any parallel operations, the process
is single line.
• Houston recycles approximately 70% more amines at the same
production levels as Belle because of different process con-
ditions. This high recycle reduces unit waste loads on a
throughput basis because the recycle does not generate addi-
tional water of reaction.
• Trimethylamine (TMA) was not being produced at Houston so all
TMA was recycled. This reduced the water of reaction being
discharged and the by-products formed.
• To reduce air pollution Houston has additional fume scrubbing
facilities, compared to Belle, to capture leakage from pump
2-19
-------
TABLE 2.7
METHYLAMINES PROCESS, WASTEWATER, BELLE PLANT
WASTEWATER TREATMENT SEWER, 4/29/75 - 6/2/75
BOD - A
COD
TKN
TOC
pH
Dimethylamine (DMA)
Monomethylamine (MMA)
Trimethylamine (TMA)
Methanol
Dimethylformamide (DMF)
Dimethylacetamide (DMAC)
Acetate
Formate
AVERAGE
2150
2942
489
1962
12.5
783
8.5
1.7
353
311
43
88
177
PPM (EXCEPT pH)
STANDARD
DEVIATION
2041
2461
529
1970
0.2
1097
8.6
2.4
390
730
92
45
76
AVERAGE
+3 SD
8273
9876
2076
7872
13.2
4074
34
9
1524
2501
320
223
406
POUNDS PER DAY DISCHARGED
(5/14/75 - 6/2/75)
AVERAGE STANDARD AVERAGE
DEVIATION +3 SD
2336
3726
689
3798
-
1389
18
4
690
719
11
172
346
3031
5079
1060
4121
-
2259
18
5
813
1541
6
86
143
11434
18963
3869
16161
-
8166
71
18
3128
5342
28
430
776
I
K>
O
-------
Water
Fume
Pickup
Header
(U
OJ -0
3 "§
U- S-
cj
on
Waste-
water
Atmosphere
Waste-
water
t
Water
SOURCE: Quarles, 1975.
FIGURE 2.4
METHYLAMINES MANUFACTURE, DU PONT HOUSTON PLANT
2-21
-------
glands, relief valves, maintenance work, and similar sources.
This converts some air discharges to water-born wastes for
treatment.
• Houston uses cooling tower water for the bulk of the cooling
requirements, whereas Belle uses once-through non-contact
cooling water. Houston does use about 400 gpm of once-through
cooling water in the summer and about 60 gpm at other times.
• Houston operates at below design capacity to minimize air
pollution.
• Houston distillation columns have more reserve capacity than
the Belle system.
In July, 1972, the Houston methylamines unit was shutdown. In
1974 the unit was renovated and extensively upgraded to allow opera-
tion with minimal odor emissions. In this renovation, the ability
to produce TMA. was lost, and the unit capacity was lowered on mono-
methylamine (MMA.) and dimethylamine (DMA) to about 35% below design
capacity. The reduction of total amine capacity was over 40%.
Two major new odor emission control systems were added. One
was the Relief Valve Containment System, which collects any discharge
from the many relief valves in the process. The gases are scrubbed
and recovered, but the new recovery loading to the vent dehydrator
was one of the factors making it necessary to reduce capacity. The
second odor control system is the Fume Scrubber. This provides air-
sweep removal at certain locations such as pump shafts where small
2-22
-------
leaks are likely, at locations where other leaks are likely, and gives
the ability to prevent leaks from escaping during repairs. The system
discharges to the waste collection facilities. The small quantity of
amines contained are sufficient to constitute a serious odor problem
if they were allowed to escape.
The capacity at which a methylamines plant operates has a
marked effect on liquid waste loading. The maximum steam to distilla-
tion columns is generally used, as limited by column flooding. As
product rate increases, the volume of the water of reaction increases
proportionately. Since the steam rate to the columns is fixed, the
liquid to vapor ratio in the column increases and results in a lower
enrichment per plate. This decrease in efficiency is exponential
for the number of plates involved. The unit waste load would be
expected to double if the operating rate of Houston were returned to
design rates. In addition the sensitivity of the process to distur-
bance and upsets would increase. When disturbances are absent the
plant will operate smoothly for days at a time with relatively low
waste loadings.
Deletion of TMA manufacture at Houston reduces the waste load
in at least two significant ways:
o More water of reaction is formed per pound of TMA. than for
the other amines, thus the wastewater flow is reduced di-
rectly. The organic content is also reduced as a result of
lower liquid/vapor ratio in the column, as discussed above.
2-23
-------
o When TMA is removed as product versus recycling, exothermic
heat in the reactor increases, thus raising reactor tempera-
ture and forming more by-products. Not only do these by-
products ("oils") directly increase the waste load, but they
interfere with operation of the distillation columns and
hinder the efficiency of waste stream clean-up.
The methylamines unit is a continuous operation, essentially at
steady-state conditions. Most variations are small, with larger scale
upsets due to water and steam pressure changes, sudden rainstorms,
and vent system loading variations due to tank car loading and unload-
ing. Rainstorms affect the process through thermal impact on the
distillation system.
2.1.4.1 Analytical Data on Wastewater Discharged at the Houston
Plant. Analytical data in ppm are presented in Tables 2.8 through
2.11 for the bottom waste streams from the dehydrator, vent dehydrator,
methanol recovery column and the fume scrubber tank. Data was obtained
from samples collected February 3 through February 17, 1975, and a
second period from March 20 through April 18, 1975. Tables 2.12 and
2.13 contain data on the cooling water blowdown and the steam pump
condensate from grab samples taken daily, composited and analyzed
weekly during the above two time periods.
The dehydrator bottoms, vent dehydrator bottoms and methanol
recovery bottoms were sampled with a continuous sampling system pro-
portioned manually to the waste flow. The composite samples were
2-24
-------
TABLE 2.8
METHYLAM1NES PROCESS, WASTEWATER, HOUSTON PLANT
DEHYURATOR BOTTOMS, 2/3/75 - 2/17/75 & 3/20/75 - 4/18/75
PH
COD
TOD
TSS
NH3 - N
TKN
TOG
BOD - A
Methylamlne (MMA)
Dimethylamlne (DMA)
Trimethylamlne (TMA)
Methanol
AVERAGE
11.3
750
704
9
1.9
9
260
422
1.3
0
0
460
PPM (EXCEPT pH)
STANDARD
DEVIATION
1.5
1432
1261
10
2.6
6
416
796
1.2
0.2
0.2
1079
AVERAGE
+3 SD
14
5047
4485
38
10
28
1509
2810
4.8
0.7
0.5
3695
POUNDS
AVERAGE
-
290
271
3.4
0.7
3.4
100
163
0.5
0
0
178
PER DAY DISCHARGED
STANDARD
DEVIATION
-
555
488
3.7
1.0
2.4
162
311
0.5
0.1
0.1
417
AVERAGE
+3 SD
-
1955
1735
15
4
11
585
1094
1.9
0.3
0.2
1430
NJ
I
N>
Oi
-------
TABLE 2.9
METHYLAMINES PROCESS, WASTEWATER, HOUSTON PLANT
VENT DEHYDRATOR BOTTOMS, 2/3/75 - 2/17/75 & 3/20/75 - 4/18/75
pH
COD
TOD
TSS
NH3 - N
TKN
TOG
BOD - A
Methylamlne (MMA)
Dimethylaraine (DMA)
Trlmethylamlne (TMA)
Methanol
AVERAGE
10.2
33
246
8
41
59
37
68
31
11
0.4
9
PPM (EXCEPT pH)
STANDARD
DEVIATION
0.5
53
503
8
89
113
64
148
90
58
1.9
20
AVERAGE
+3 SD
11.8
193
1754
32
309
398
228
511
300
184
6
69
POUNDS
AVERAGE
-
2.6
19
0.6
3.2
4.6
2.9
5.2
2.4
0.9
0
0.7
PER DAY DISCHARGED
STANDARD
DEVIATION
-
4.1
39
0.6
6.9
8.8
4.9
11.4
6.9
4.4
0.2
1.5
AVERAGE
+3 SD
-
15
136
2.5
24
31
18
39
23
14
0.5
5
(xO
I
-------
TABLE 2.10
METHYLAMINES PROCESS, WASTEWATER, HOUSTON PLANT
METHANOL RECOVERY COLUMN, 2/3/75 - 2/17/75 & 3/20/75 - 4/18/75
pH
COD
TOD
TSS
NH - N
TKN
TOG
BOD - A
Methylamine (MMA)
Uirnethylamine (DMA)
TrLmethylamine (TMA)
Methanol
AVERAGE
12.0
2536
3399
15
25
203
2149
892
66
4.3
0.5
9
PPM (EXCEPT pH)
STANDARD
DEVIATION
0.9
1326
1670
24
43
170
4174
418
94
14
2
41
AVERAGE
+3 SD
14
6516
8410
87
155
711
14670
2146
348
45
7
132
POUNDS
AVERAGE
-
120
160
0.7
1.2
10
104
42
3.1
0.2
0
0.4
PER DAY DISCHARGED
STANDARD
DEVIATION
-
63
79
1.1
2.0
8
208
20
4.4
0.6
0.1
1.9
AVERAGE
+3 SD
-
308
396
4
7
34
727
101
16
2
0.3
6
NJ
I
IxJ
-------
TABLE 2.11
METHYLAMINES PROCESS, WASTEWATER, HOUSTON PLANT
FUME SCRUBBER TANK, 2/3/75 - 2/17/75 & 3/20/75 - 4/18/75
pll
COD
TOD
TSS
NH3 - N
TKN
TOG
BOD - A
Methylamine (MMA)
Dlmethylamine (DMA)
Trimethylamine (TMA)
Methanol
AVERAGE
7.2
88
1249
42
269
308
168
442
66
18
291
15
PPM (EXCEPT pH)
STANDARD
DEVIATION
1.8
187
1018
36
204
220
160
458
178
8
221
12
AVERAGE
+3 SD
12.4
649
4304
150
881
968
648
1561
60
5
954
51
POUNDS
AVERAGE
-
0.1
2.2
0.1
0.5
0.5
0.3
0.7
0.1
0
0
0
PER DAY DISCHARGED
STANDARD
DEVIATION
-
0.3
2.4
0.6
0.4
0.4
0.3
0.7
0.3
0.1
0.1
0
AVERAGE
+3 SD
-
1.0
9.2
0.3
1.5
1.8
1.3
2.9
1.1
0.2
0.2
0.1
KJ
I
l-o
oo
-------
TABLE 2.12
METHYLAMINES PROCESS, WASTEWATER, HOUSTON PLANT
COOLING WATER SLOWDOWN, 8 SAMPLES BETWEEN 2/5/75 - 4/16/75
pH
COD
TOD
TSS
NH3 - N
TKN
TOG
BOD - A
Methylamine (MMA)
Dimethylamine (DMA)
T rime thy lamlne (TMA)
Methanol
AVERAGE
7.2
15
5
6
1.4
7
16
14
0
0
0
0
PPM (EXCEPT pH)
STANDARD
DEVIATION
0.5
16
8
4
2
14
6
20
0
0
0
0
AVERAGE
+3 SD
8.6
62
29
18
7
48
34
75
0
0
0
0
POUNDS
AVERAGE
-
0.4
0.1
0.1
0
0.2
0.4
0.3
0
0
0
0
PER DAY
DISCHARGED
STANDARD AVERAGE
DEVIATION +3 SD
-
0.4
0.2
0.1
0.1
0.3
0.2
0.5
0
0
0
0
-
1.5
0.7
0.4
0.2
1.2
0.8
1.8
0
0
0
0
N)
-------
TABLE 2.13
METHYLAMTNES PROCESS, WASTEWATER, HOUSTON PLANT
STEAM PUMP CONDENSATE, 8 SAMPLES BETWEEN 2/5/75 - 4/16/75
PPM (EXCEPT pH)
PH
COD
TOD
TSS
NH - N
TKN
TOG
BOD - A
Methylamlne (MMA)
Dimethylamine (DMA)
Trimethylamine (TMA)
Methanol
AVERAGE
8.2
36
12
4
0.4
0.6
25
15
0
0
0
0
STANDARD
DEVIATION
0.4
65
13
5
0.9
0.9
18
21
0
0
0
0
AVERAGE
+3 SD
9
231
51
17
3
3
79
77
0
0
0
0
POUNDS PER DAY DISCHARGED
AVERAGE
-
3.2
1.1
0.3
0
0.1
2.2
1.3
0
0
0
0
STANDARD
DEVIATION
-
6
1.2
0.4
0.1
0.1
1.6
1.8
0
0
0
0
AVERAGE
+3 SD
-
21
4.6
1.5
0.3
0.3
7
7
0
0
0
0
I
CO
o
-------
analyzed daily. The fume scrubber tank (a batch operation not
present at the Belle plant) was sampled with a daily grab sample.
The Houston methyamines plant was running at about 60-65% of
design capacity during the test period to maintain adequate control
over emissions of amines to the atmosphere and because of other fac-
tors pending further facility improvements. Because of these restric-
tions the plant was not operated at design rated capacity during the
test period. For most chemical processes unit waste loads will not
be constant with regard to production rate, since many losses are
fixed and independent of production rate. Lower unit waste loads
would then normally be expected for higher capacity operation.
However, in the cases of an amines plant, the waste loads depend
heavily on distillation train efficiency. As a distillation system
is pushed to capacity not only does the average loss in the drawoff
streams increase, but the variability also increases as the columns
are more sensitive to upset. Therefore, the unit loads during the
test period are lower than would be expected if the plant were opera-
ted at design capacity. Any decrease in unit loads because of distri-
bution of the fixed load over a slightly larger base would probably
be much more than offset by increased variability as facilities are
operated closer to maximum capacity. The unit waste loads of this
test should be doubled based on reduced distillation efficiency at
capacity.
2-31
-------
The Houston results are compared with the Belle plant results in
Table 2.14 with waste loads tabulated as pounds per M (1000) pounds
of amines produced. The Houston average values are in general lower
because of operation at lower capacity and the recycle of all TMA.
Houston results show a higher degree of variability because the
Houston test covered a significantly longer period of time.
The long term variances associated with the operation are shown
in Table 2.15. The data is in terms of Total Oxygen Demand (TOD),
since these analyses were primarily used for operational control.
The data of Table 2.15 show that the period of the present test,
February and March 1975, are two of the three lowest waste load months
of the 17 months reported. Controls were somewhat improved over
early periods but process upsets from plant steam supply fluctuations,
cooling tower water temperature changes with a rainstorm, loss of
treatment chemicals, utility failures, and mechanical malfunctions
cannot be totally eliminated.
The TOD data, as summarized in Table 2.15 show the highest monthly
value (March, 1972) to be about 4.5 times the average plus 3 stan-
dard deviations of the test period. Any monthly waste load limit
should have an appropriate value above the average plus 3 standard
deviations to account for the degree of variability shown in long
term operation.
Data was only presented for the three methylamines and methanol
in the waste stream from the Houston plant. No by-product information
2-32
-------
TABLE 2.14
COMPARISON OF RESULTS - HOUSTON PLANT VS. BELLE PLANT
WASTE LOADS TABUJATED AS POUNDS PER M POUNDS OF AMINES PRODUCED
Mean
Std. Dev.
Mean +
3 Std.
Dev.
BOD^
"" j
H IJ
2.9 4.1
4.9 1.1
18 7.4
COD
H B^
4.2 11
5.9 4.0
22 23
TOC
H 1
1.8 6.0
2.0 1.8
8 11
NH.N
H IS
0.06 0.16
0.04 0.08
0.18 0.4
TKN
H _B
0.21 1.1
0.13 0.54
0.60 2.7
TSS
1L I
0.06 0.15
0.05 0.08
0.20 0.39
ro
I
CO
H - Houston results
B - Belle results
-------
TABLE 2.15
HOUSTON PLANT
Revised 4/18/75
HISTORICAL TOD DATA
July-August 1971
October-November 1971
December 1971
March 1972
April-May 1972
June 1972
July 1972
June 1974
July 1974
August 1974
September 1974
October 1974
November 1974
December 1974
January 1975
February 1975
March 1975
Pounds Per
Mean
495
6,
2,
1,
1,
592
277
275
600
871
479
920
701
964
404
985
553
043
938
362
299
Day
Standard
Deviation
637
853
170
20,214
566
817
578
759
4,931
536
259
6,050
542
3,763
1,249
629
577
Number of
Values
8
29
17
23
32
24
11
10
24
20
30
31
29
23
30
27
29
Average
1975 Sampling Test
Average - 362 (30 days)
Highest Day - 1,488
1,162
2-34
-------
was given. The actual discharges in pounds per day are much smaller
for the Houston plant because it is a smaller plant. The annual
capacity of the Houston plant is 165 million pounds compared to 26
million pounds for the Belle plant (SRI International, 1978).
2.2 Ethylamines from Ethanol
Ethylamines can be prepared by essentially the same process as
is employed in the preparation of the methylamines—the vapor phase
ammonolysis of ethanol in the presence of a dehydration catalyst. We
will describe the process in which ethylamines are prepared by passing
ammonia, ethanol and hydrogen over a dehydrogenation catalyst in a
gas-solid heterogeneous reaction. Catalysts include metallic silver,
nickel or copper- There is little consumption of hydrogen, which
acts to maintain catalyst activity by retarding coke formation. A
mixture of amines is produced, but there are sufficient differences
in vapor pressure to obviate the complex separation schemes required
in the isolation of the methylamines. Recycle is used to obtain the
specific amines which are required for sale.
The flow diagram for the Leonard process for the manufacture of
ethylamines is given in Figure 2.5. Anhydrous ethanol, ammonia,
recycle ammonia and recycle amines are fed continuously to a vaporizer.
This stream is combined with recycle hydrogen, and make-up hydrogen
as required, and passed through a heat exchanger and superheater into
the catalytic reactor. The vapor stream is at reaction temperature
as it enters the top of the reactor.
2-35
-------
RECYCLE AMINES
10
CjJ
ETHANOL j — |
AMMONIAC
L
1]
1
_J *i
H R
HEAT
VAPORIZER EXCHANGER
I
,ry( ,fr\
*yj xy
prvri F NII 1
.5
I |
COMPRESSOf
A
V
^/
GAS
1 II
tf*\ RECYCLE 1
t ^=^ H0
2
1 r-^ H^
MAKE-UP 1 -*Y A ^
ii f \ 1 / i 1
\\2
1 >
1
^J (?\+- vv
I T * I
1 1 1
— I
7^-
T
— *
NH^ MONO
SEPARATOR COLUMN COLUMN
CATALYTIC
REACTOR
^
pj
V
(^
^^>
1
— 1
7
t
1 1
DI
w
^->-
COLUMN
SOURCE: McKetla, 1977
r
A
T
PRODUCT
COOLER
(
V
/
£
J
^
L
J
^
Pn
x^
k
>»
/ r^'
1 S t
'(
rr.
r~*
TO WASTE
TRI
DECANTER COLUMN
MONOETHYLAMINE
PRODUCT
*• DIETHYLAMINE
PRODUCT
TRIETHYLAMINE
PRODUCT
FIGURE 2.5
LEONARD PROCESS FOR THE
MANUFACTURE OF ETHYLAMINES
-------
Reaction temperature, pressure and catalyst composition must be
obtained from the patent literature. A reduced pelleted nickel hydro-
genation catalyst is used at 159°C and a space velocity of 2070 (Olin
and McKenna, 1944). Another patent uses a foraminate copper/aluminum
catalyst (which had been treated with a 5% solution of barium hydrox-
ide octahydrate) at 260°C and 17 atm pressure (Davies, et al., 1952).
A patent assigned to Union Carbide claims the reduction of by-products,
particularly acetonitrile, by using two reaction zones (Lemon, et al,
1962). A catalyst bed consisting of reduced nickel on an alumina sup-
port was maintained at 260°C and the residence time limited to ten
seconds. The product effluent was passed directly to a second cata-
lyst bed consisting of reduced nickel on silica. The bed was main-
tained at 200°C and the contact time held to 11.1 seconds. The pro-
duct effluent from the second reaction zone showed a decrease in
acetonitrile from 19.7 wt% to 0.0%, and a decrease in ethanol from
3.7 wt% to 0.0%.
The amine reaction mixture is first sent to a product cooler and
then to a gas separator for removal of hydrogen for recycle. Other
noncondensable gases, such as carbon monoxide, would probably be
bled off at this point. The first column removes ammonia which is
returned to recycle. The second column separates monoethylamine over-
head for product storage, or recycle. The third column separates
diethylamine overhead for product storage, or recycle.
2-37
-------
The bottoms from the di-column are sent to a decanter where a
waste stream is separated. The overflow from the decanter is sent
to the tri-column where triethylamine is separated as the bottoms for
transfer to storage, or recycle. The overhead is returned to the
decanter. Triethylamine forms an azetrope with water which boils at
75°C and contains 10% water.
2. 3 Aniline Manufacture by Ammono lys is of Phenol
The flow diagram of 'the Scientific Design Co. process for the
manufacture of aniline from phenol is given in Figure 2.6 (Becker and
Russell, 1973). The reaction of phenol with ammonia producess aniline
and water:
OH NH
2
0 +M ' - > +H°
The reaction is reversible. Aniline production is favored by higher
ammonia to phenol ratios and lower reaction temperatures. The for-
ward reaction is mildly exothermic and is favored by lower temperature.
A second equilibrium exists between ammonia, aniline and dipheny-
lamine:
NH9
I 2
•! i i + NH.
-------
PIPE REACTOR
SEPARATOR AMMONIA
RECOVERY STILL
DRYER
PURIFICATION
STILL
AMMONIA
PHENOL
"2'N2
X
RECYCLE AZEOTROPE
ANILINE
HEAVIES
SOURCE: BECKER AND RUSSELL, 1973.
FIGURE 2.6
SCIENTIFIC DESIGN PROCESS FOR MANUFACTURE
OF ANILINE FROM PHENOL
-------
An excess of ammonia insures a high conversion. The heat of
reaction is calculated at 2.4 K cal./g. mole at reactor conditions.
This small amount of exotherm permits the use of an adiabatic packed
bed reactor, without internal cooling at higher NH^/ phenol ratios,
resulting in a low adiabatic temperature rise. What is required is
a highly reactive catalyst to give complete conversion in a short
residence time.
The dissociation of ammonia to nitrogen and hydrogen limits the
maximum economic temperature that is practical in the reactor. This
reinforces the need for a low temperature and short residence time.
As shown in Figure 2.6, phenol, ammonia and recycle ammonia are
vaporized in a preheater and fed into an adiabatic pipe reactor con-
taining a suitable catalyst. Several unique, high conversion, Lewis
acid type catalysts have been made up of aluminas derived from pre-
cipitated gel containing less than 1.0% alkali metal and having sur-
face areas of more than 150 sq. m./g. Another class of catalyst can
be described as containing 35-55% by weight of alumina (out of a
total silica-alumina blend) and having a surface area in excess of
100 sq.m./g. Another class of suitable catalysts could be selected
from the group consisting of silica-alumina, zirconia alumina,
titania-alumina, phosphoric acid and tungsten oxide.
The most important aspects of these catalysts are their acidity,
their limitation on alkali metal content and their surface area.
2-40
-------
The effluent gases from the reactor are cooled and fed to the
first column in the purification train to recover ammonia for re-
cycle. This column employs straightforward distillation to remove
aniline, water and the small quantity of diphenylamine from the
bottom. The overhead gases pass through a separator to remove any
quantities of nitrogen or hydrogen that eventually build up. From
the separator the stripped overhead ammonia is sent through a com-
pressor into the makeup stream.
The product stream from the bottom of the ammonia recovery still
is sent to the drying column where water is removed overhead.
The third purification step recovery of specification aniline
is considerably more difficult because aniline and phenol have
almost identical vapor pressure curves. However, aniline phenol
mixtures are non-ideal as evidenced by the formation of a maximum
boiling azetrope which boils at 186°C at atmospheric pressure and
contains 42% phenol. Despite the negative deviation from ideality
at atmospheric pressure, separation would almost seem impractical.
Scientific Design investigated several exotic approaches to
the purification problem and found that the volatility is unexpectedly
a strong function of temperature. As a result if the distillation
is carried out below 600 mm. pressure, economic separation can be
achieved as long as the feed composition is richer in aniline than
phenol. This composition is readily attained when the new Scientific
Design catalysts are used.
2-41
-------
A single column produces pure aniline as overhead product. The
small quantity of azetrope is withdrawn several trays from the bottom
of the column and is recycled to the reactor. The bottoms from the
column contain the diphenylamine.
Aniline derived from phenol exhibits considerably higher product
purity than nitrobenzene-derived anilines generally available. Using
ASTM standards, phenol-derived aniline stored in a nitrogen atmos-
phere for 500 hours will generally retain an APHA color of better than
40 platinum-cobalt units, compared to 60-80 for nitrobenzene derived
anilines. When heated at 150°C for 30 minutes, most anilines will
develop colors in the range of 100-300 units, while aniline from the
phenol process generally stays below 100 units, and often below
50 units.
2.4 Manufacture of Ethanolamines by Ammonolysis of Ethylene Oxide
The flow diagram for the Scientific Design process for the manu-
facture of ethanolamines by ammonolysis of ethylene oxide is given
in Figure 2.7 (Scientific Design, ]975). Since specific operating
conditions are not given for this process we will use general condi-
tions from the literature, in particular as described for the Dow
process (Weaver and Smart, 1959).
Liquid ethylene oxide, aqueous ammonia and recycle amines are
combined and pumped together under enough pressure to maintain the
liquid phase into a coil-type reactor. The reaction is highly exo-
thermic and is usually carried out at temperatures of 50-100°C under
2-42
-------
pressures of 150-300 psi. If a kettle type reactor is used, ethylene
oxide is slowly pumped into the ammonia solution with agitation.
Because water aids temperature control, by removing heat of reaction,
most commercial processes use 28-50% aqueous ammonia.
Ethylene oxide/ammonia/recycle amine feed ratios are used to
control the distribution of the amines produced in the reactor so
as to accomodate varying market demands for each of the products.
A Union Carbide patent describes a process in which ethylene
oxide is gradually added to aqueous ammonia at such, a rate that the
concentration of uncombined ethylene oxide in the reaction mixture
is always low with respect to the concentration of uncombined ammonia
so that formation of by-products is minimized (Reid and Lewis, 1930).
The reaction temperature is kept below 100°C.
From the reactor the effluent is pumped, to an ammonia stripper
operating at about 50 psi and 135°C to remove unreacted excess ammonia.
The overhead from the stripper, together with fresh ammonia makeup,
enters an ammonia absorber where the aqueous ammonia solution is
prepared for reaction. The bottoms from the ammonia stripper are
fed to an evaporator running at atmospheric pressure and 115°C. The
water removed here is recycled to the absorber as makeup water
to control concentration of the aqueous ammonia input stream. Pro-
duct from the evaporator goes to a dehydrator operating at 150 mm Hg
pressure and 140°C, which removes the water to conform with speci-
fication limits.
2-43
-------
AMMONIA
ABSORBER
AMMOJUA
RIAC10K STRTPPEil
tMP.QRAnON DRYING MEA PEA TEA
SYSTEM COLUMN COLUMN COLUMN COLUMN
ti
RECYCLE
AMINES
AMMONIA
ETIIYI.ENE
OXIDE
*
RECYCLE UA1LT.
MEA PROmiCT
DEA PRODUCT
TEA PRODUCT
TARS TO
WASTE
SOURCE: HYDROCARBON PROCESSING. 19/1
FIGURE 2.7
SCIENTIFIC DESIGN PROCESS FOR MANUFACTURE
OF ETHANOLAMINtS FROM ETHYLtNE OXIDE
-------
The bottoms from the dehydrator are pumped to a crude-amine
surge tank and drawn from there through the three amine finishing
columns in series. These all run at a low vacuum of less than
10 mm Hg provided by three stage steam jets. Each of the three
amines is produced at a purity of 99%.
The bottoms from the triethanolamine (TEA) column consisting
of tars, other condensation products and some residual TEA are sent
to waste.
2.5 Manufacture of Ethylenediamine by the Ammonolysis of Ethylene
Dichloride
Flow diagrams for the manufacture of ethylenediamine by the
ammonolysis of ethylene dichloride are given in Figures 2.8 and 2.9.
The reaction is carried out in the aqueous liquid phase without a
catalyst. Ethylene dichloride, water and ammonia are introduced
into a fractionating tower which may be of the bubble cap or packed
type (Nicolaisen, 1957). Recycle ammonia may be introduced at one
or several points. Operating temperatures range from 30-40°C in
the upper part of a reactor-fractionator to 100-200°C in the lower
part. Operating pressures range from 300-1000 psi or higher. The
heat of reaction generated in the tower serves to evaporate ammonia
and ethylene dichloride which are fractionated. Ammonia passes
overhead and ethylene dichloride remains in the mid-portion of the
tower.
The ammonia passing overhead is liquefied in the cooler and
either totally or partly returned to the tower as reflux. The
2-45
-------
RECYCLE
NH3
COOLER
V
SURGE
TANK
H20
NaOH
(AQUEOUS)
•CONTROL VALVE
FRACTIONATING TOUER
REBOILER
C2H4(NH2)2«2HC1
+WATER
QR
C2H4(NH2)2
+WATER+NaCl
SOURCE: U.S. PATENT 2,805,254
FIGURE 2.8
PROCESS FOR MANUFACTURE OF ETHYLENEDIAMINE
FROM ETHYLENE DICHLORIDE AND AMMONIA
2-46
-------
remaining ammonia flows through a control valve to a surge tank and
then is recycled to the tower. The control valve is used to regulate
the ratio of ammonia used for reflux and recycle.
Water and ethylenediamine dihydrochloride pass downwardly in
the tower. The bottoms, free of ammonia and ethylene dichloride are
removed from the bottom of the tower, a portion passes to a -reboiler
from which vapors are returned to the bottom of the tower. The pro-
ducts, ethylenediamine dihydrochloride in aqueous solution together
with higher polyamines dihydrochlorides are sent to a neutralizer.
In an alternative procedure the free amine is liberated by the
addition of sodium hydroxide to the tower. The sodium hydroxide is
charged in aqueous solution to the tower at a point below the inlet
line for make-up ammonia. In this case the bottoms product consists
of an aqueous solution of sodium chloride, ethylenediamine and
higher amines.
Figure 2.9 illustrates a process for the separation of amines
from the crude product which minimizes the difficulties previously
encountered (Marullo, 1965). The rectification of the amines is
carried out in the presence of salt, and scale formation in the con-
centrator, ordinarily caused by sodium chloride, is avoided. The
crude neutralized solution is fed into a concentrator which is kept
at atmospheric pressure and 130°C. This temperature is high enough
to completely evaporate ethylenediamine, polyamines and water from
the crude product. Sodium chloride separates in the concentrator
2-47
-------
CRUDE
NEUTRALIZED
PRODUCT
RECYCLE LIQUID
COLUMN
NO. 1
PRODUCT
EDA
+
POLYAMINES
COLUMN
NO. 2
• POLYAMINES
-------
and the salt suspension is periodically or continuously sent to the
centrifuge.
The salt, as separated by the centrifuge, is contaminated by
tars and nondistillable polyamines and is sent to waste. The liquid
from the centrifuge is recycled to the concentrator.
The liquid in the concentrator is kept under forced circulation
by a pump which passes it through a heater. The vapors leaving the
concentrator are continuously fed into a column from which water is
separated overhead and ethylenediamine and polyamines as bottoms.
The bottoms from the first column are fed to a second column
where the ethylenediamine, boiling at 117°C, is removed overhead.
The bottoms consisting of higher polyamines can be marketed, as is,
or separated by further distillation. Crude diethylenetriamine may
be obtained by heating up to 120°C at 6-8 mm pressure. Crude tri-
ethylenetetramine is obtained by heating up to 135°C at 6-8 mm
pressure.
Vinyl chloride, which is produced in amounts up to 3% of the
ethylene dichloride charged, forms anion exchange-type resins
through a series of polymerization and polycondensation reactions.
These resins accumulate in the recycle ammonia and are completely
insoluble in the reaction solutions. They will eventually seriously
interefere with the operation of the process if permitted to
accumulate.
2-49
-------
The method described below separates the recycled ammonia from
vinyl chloride thereby reducing the formation of resins to an amount
so small that continuous operation is not hindered (Costabello, 1965).
Vinyl chloride separates from aqueous ammonia due to its low
solubility in the ammoniacal solutions. Gaseous ammonia, obtained
by expansion to 10 atmospheres, is absorbed by a 24% aqueous solu-
tion of ammonia in a washing tower under 6 atmospheres pressure at
40°C. The unabsorbed ammonia and vinyl chloride leaving the first
tower are washed with water in a second tower under atmospheric pres-
sure at about 40°C. The ammonia is completely absorbed and vinyl
chloride is vented for waste disposal.
2.6 Manufacture of Ethylenediamine by Ammonolysis of Ethanolamine
A flow diagram for the manufacture of ethylenediamine by the
ammonolysis of ethanolamine is given in Figure 2.10 (Kohn, 1978).
Monoethanolamine, ammonia, hydrogen and recycled products are fed
to a vaporizer. The gaseous mixture then flows to a fixed-bed
reactor in which the amination catalyst is present in pellet form.
The Leonard process uses a proprietary amination catalyst devel-
oped by Societe Chimique de la Grande Paroisse SA (Paris). This
catalyst has been demonstrated to have a 2000 hour catalyst life
with no dropoff in activity. Ultimate catalyst life is being deter-
mined .
Several catalysts have been described in the patent literature.
Catalysts of Raney nickel, cobalt, copper chromite, platinum or
2-50
-------
MEA
VAPORIZER
Ul
REACTOR
RECYCLE-GAS
COMPRESSOR
CONDENSER
COLUMN
1
COLUMN
-\ 2
t
T
EDA
PURIFICATION
UNIT
PIP
COLUMN
3
MEA
POLYAMINE
SEPARATION
SECTION
DETA1
AEP
HEP
SOURCE: KOHN, 1978
FIGURE 2.10
LEONARD PROCESS FOR MANUFACTURE OF
ETHYLENEDIAMINE FROM MONOETHANOLAMINE
-------
palladium were reported by Mac Kenzie of Dow Chemical in 1958. A
French patent to BASF AG describes the preparation of an amination
catalyst from cobalt carbonate and nickel formate (Winder1, et al,
1963). A recent U.S. patent to BASF AG uses a catalyst composition
of 70 to 95% by weight of a mixture of cobalt and nickel and 5 to
30% by weight of copper, as calculated on the metal content (Boettger,
et al., 1977). The preferred weight ratio of cobalt to nickel is
1:1 with a preferred content of 15% by weight of copper.
The reaction takes place in a hydrogen atmosphere, at a temper-
ature not exceeding 300°C and a pressure not over 250 atmospheres.
The time of reaction is "on the order of seconds." The amination
is mildly exothermic so that external cooling on the reactor is
required to control reaction temperature.
Upon leaving the reactor, the aminated stream flows to a sepa-
rator, actually a partial condenser, where the vapor and liquid
phases are dissociated.
The vapor phase, consisting almost completely of ammonia and
hydrogen, recycles through a compressor to the reactor. The liquid
phase enters column 1, where any remaining ammonia is removed. The
ammonia then passes through a condenser, where it is liquefied, and
then returns to the vaporizer for recycle. The water distilled off
in column 2, contains only trace amounts of organics - according to
Leonard and can go to a biotreatment facility.
2-52
-------
The bottoms, from column 2 contain ethylenediamine (EDA),
diethylenetriamine (DETA), piperazine (PIP), and substituted pipera-*
zines including aminoethylpiperazine (AEP) and hydroxyethylpipera-
zine (HEP). These bottoms flow into column 3 of the unit's distilla-
tion section.
Ethylenediamine and piperazine are stripped off as overheads in
column 3 and are sent to a purification unit. Bottoms from column
3 go to the polyamine separation section, which in essence is a.batch
distillation unit in plants having a capacity of less than 10,000
metric tons/year. Larger facilities can have continuous stripping
operations for separation of the various coproducts and unreacted
monoethanolamine (MEA) which is recycled to the reactor.
The basic process yields a product mix (by weight) of about
69% EDA, 7% DETA, 14% PIP and 2% HEP. The output of EDA and DETA
can be further maximized - and output of PIP minimized - by recycling
the piperazine product stream (shown as a dashed line on the flow
diagram). In tests where this has been done the product mix consisted
of 74% EDA, 8% DETA, 4% PIP, 10% AEP, and 4% HEP-
Leonard claims a capital investment saving of about 17% by using
the monoethanolamine (MEA) process as compared to the conventional
ethylene dichloride process. The bulk of the capital investment
savings accrue from not needing expensive equipment for separating
and processing the organic-laden salt streams and vinyl chloride gas
streams that typically issue from the ethylene dichloride process.
2-53
-------
In addition the ethylene dichloride process requires a larger and
more complex reaction system than does the MEA process, and because
of its corrosive nature also requires more expensive materials of
construction.
2-54
-------
3.0 EVALUATION OF SIX PROCESSES USING AMINATION BY AMMONLYSIS
FOR DISCHARGE SIMILARITIES
3.1 Comparison of Flowsheets
The flowsheets for the manufacture of five chemicals, or closely
related chemical groups, using six processes involving amination by
ammonolysis have been presented in Figures 2.1 through 2.10. Four
flowsheets were presented for the manufacture of the methylamines -
monomethylamine, dimethylamine and trimethylamine (Figures 2.1
through 2.4). Single flowsheets are given for the manufacture of the
ethylamines - monoethylamine, diethylamine and triethylamine (Figure
2.5); for the manufacture of aniline from phenol (Figure 2.6), and
for the manufacture of the ethanolamines - monoethanolamine, diethanol-
amine, and triethanolamine - from ethylene oxide (Figure 2.7).
Two processes are described for the manufacture of ethylene-
diamine, the ammonolysis of ethylene dichloride (Figures 2.8 and 2.9)
and the ammonolysis of monoethanolamine (Figure 2.10). Coproducts
with ethylenediamine are diethylenetriamine, triethylenetetramine
and tetraethylenepentamine.
The conditions of ammonolysis for the six processes are tabulated
in Table 3.1. The methylamines, ethylamines, aniline and ethylene-
diamine from ethanolamine are produced by vapor phase-catalytic
processes. They are all carried out under moderately high temperatures
of 260-460°C and medium pressures of 75-250 psi except the ethylene-
diamine process requires 3750 psi.
3-1
-------
TABLE 3.1
COMPARISON OF AMMONOLYSIS PROCESSES
Product Type Temperature Pressure
.!C_ psi
Methylamines Vapor phase, catalytic 350-500 75
Ethylamines Vapor phase, catalytic 260-400 250
Aniline Vapor phase, catalytic 400-460 240
Ethanolamines Liquid phase, aqueous 50-160 300-1000
Ethylenediamine
i (from ethylene
r° dichloride) Liquid phase, aqueous 100-140 150-1000
Ethylenediamine
(from ethanolamine) Vapor phase, catalytic 300 <3750
-------
The ethanolamines and ethylenediamine from ethylene dichloride
processes are carried out in aqueous-liquid phase systems. These
processes use relatively low temperatures of 50-160°C. Pressures
cover a wider range from 150-1000 psi for the aqueous-liquid phase
systems.
In the four catalytic processes the reactor is followed by a
separator to remove non-condensible gases. For methylamines this may
be merely a surge tank where hydrogen and carbon monoxide are bled
off for waste disposal, probably incineration. In the aniline pro-
cess hydrogen and nitrogen are removed, also for incineration. The
ethylamines and ethylenediamine from ethanolamine processes use
hydrogen in the processes so it is recycled from the separator
In five of the six processes the product stream subsequent to
passage through the separator (if required) enters an ammonia recovery
column, or ammonia stripper. The ammonia overhead from this column
is returned as recycle for charging to the reactor.
The ethylenediamine from ethylene dichloride process also re-
cycles ammonia but in a somewhat different manner. Ammonia is eva-
porated in the reactor-fractionator and passes overhead to a cooler
from which all, or a portion, of the ammonia may be returned to the
reactor- fractionator. The remaining ammonia passes through a cont-
rol valve into a surge tank from which it is returned to the reactor-
fractionating tower as recycle.
3-3
-------
All of the processes utilize a dehydrator except ethylamines.
In three processes, aniline, ethanolamines and ethylenediamine from
ethanolamine, the dehydrator follows the ammonia recovery column.
In the methylamines process the trimethylamine column follows the
ammonia recovery column and removes trimethylamine as overhead with
the bottoms passing to the dehydrator. In the ethylenediamine from
ethylene dichloride process the crude neutralized product from the
reactor-fractionating tower is sent to a concentrator from which the
overhead passes to a dehydrating column.
The final phase of each process consists of one or more distill-
ing columns with the capability of producing products meeting desired
specifications. In cases where multiple products are obtained
methylamines, ethylamines and ethanolamines recycle to the reactor
is provided for each product stream. This allows manufacture of
products required to meet current sales demand. The Houston plant
of DuPont has been modified to recycle all trimethylamine in order
to meet environmental standards for pollution control.
In the aniline process an aniline-phenol azetrope is recycled
to the reactor from the purification still. In the ethylenediamine
from ethylene dichloride process two recycle streams may be used.
Piperazine may be recycled from the ethylenediamine still and ethan-
olamine is recycled from the polyamine separation section. No
recycle is used in the distillation of ethylenediamine in the
ethylene dichloride process.
3-4
-------
3. 2 Comparison of Constituents of Air, Water, and Solid Discharges
from Related Discharge Points in the Six Amination by Ammono-
lysis Processes
In this section we will compare the constituents of the dis-
charges from each process, as determined by a literature search.
These will be tabulated as to source and type of discharge air,
water, or solid. The table will be followed by a flowchart on which
the point sources of the discharges will be located. Other consti-
tuents may be present in the discharges but we believe the major
components have been identified.
3.2.1 Discharges from the Methylamines Process
We will use the methylamines process as described in Section
2.1.3 for the DuPont plant at Belle, West Virginia, since we have
the most information on discharges for this plant. The constituents
of the discharges are listed in Table 3.2 with the source and type
of discharge. Points of discharge have been shown on the flowchart
of the process in Figure 3.1 with the constituents listed for each
point of discharge on the page following the chart.
In Tables 2.1 through 2.5 the analysis in ppm for several
constituents and the pounds discharged per day for each constituent
are given for the No. 1 and No. 2 Dehydrator bottoms, the No. 1 and
No. 2 Methanol Recovery bottoms and the Vent Dehydrator bottoms.
The constituents so analyzed include dimethylamine, monoethylamine,
trimethylamine, methanol, dimethylformamide, dimethylacetamide,
methyl acetate and methyl formate.
3-5
-------
TABLE 3.2
POLLUTANT DISCHARGES FROM THE METHYLAMINES PROCESS
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
POLLUTANT
Methanol
Ammonia
Mono me thy 1 amine
Dimethylamine
Trimethylamine
Alumina, Silica,
Silver phosphate
Molybdenum sulfide,
Cobalt sulfide, etc.
Dimethylformamide
Dimethylacetamide
Methyl acetate
Methyl formate
Methyl ether
Methane
Formaldehyde
Carbon monoxide
Nitrogen
Hydrogen
"Oils"
SOURCE
Feedstock
Feedstock
Product
Product
Product
Catalyst fines
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
TYPE OF DISCHARGE
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Solid
Water
Water
Air, Water
Air, Water
Air, Water
Air
Air, Water
Air
Air
Air
Water
3-6
-------
Point 1
Mcnconciensibles
vented to
atmosphere
He t ha no 1 Ammonia
UJ
I
L
tf V 7
Steam Water Preheater . Recycle
i
i •*!
f
Vent
Oehydrator
•s — Liquid Purge
from Product C
* 1
Waste-
water
Point 2
o
Oil Layer to Q
Incinerator \
Point 7 I
Covered
sewer
to waste
Point 5
1
- Vents from
Methylamir.es
Product B
Product C
— c >, < — Steam
s'So1" f
vT-S0 i
^ J Waste
Mathanol
from
Product A
A
f— \
• s- -, S v f .. • £ Steam — >• ° ^ I— o
.oyv V-P"^ >5t.'c
v |r Waste V^ y/
Waste- Waste- Methanol
water wa ter from
Point 3 Point 4 Product B
^ i II /"MA \ 1 ^ i
-^ '-MProductla-1 ^-^ <^-
• *o \ y • <-)
0 C) X^^^X 0
1 - 1 1 \ J
) *•
/DMA\
^
i-
o
ta
o
OJ
Q
i
Oil layer to
Incinerator
Point 8
Covered
sewer
to waste
Point 6
FIGURE 3-1
METHYLAMINES MANUFACTURE, BELLE PLANT]
SOURCE: Quarles, 1975.
-------
POINT SOURCE POLLUTANTS
FOR METHYLAMINES MANUFACTURE
FOR FIGURE 3.1
Point I
Carbon Monoxide
Hydro gen
Methane
Nitrogen
Point 2
Ammonia
Methanol
Monome thylamine
Dimethylamine
Dimethylformamide
Dimethylacetamide
Methyl acetate
Methyl formate
Methyl ether
Formaldehyde
Points 3 & 4
Points 5 & 6
Ammonia
Methanol
Catalyst fines
Monomethylamine
D ime thy 1amine
Dimethylformamide
Dimethylacetamide
Methyl acetate
Methyl formate
Methyl ether
Formaldehyde
Ammonia
Methanol
Monomethylamine
Dimethylamine
Trimethylamine
Dimethylformamide
Dimethylacetamide
Methyl acetate
Methyl formate
Methyl ether
Formaldehyde
Points 7 F-
"Oils"
-------
The largest load is carried by the Vent Dehydrator at Point 2
which in average pounds per day discharged shows 231 for dimethyl-
amine, 80 for methanol, 129 for dimethyIformamide, 46 for dimethyl-
acetamide, 184 for methyl acetate, and 54 for methyl formate.
The No. 1 and No. 2 Dehydrators at Points 3 and 4 carry a much
lighter load. Five of the analyzed constituents are below 10 pounds
per day average discharge. For the others the No. 1 Dehydrator
shows 61 for methanol, 32 for methyl acetate and 18 for methyl for-
mate. Wastewater from the No. 2 Dehydrator contains in average
pounds per day discharged 126 pounds of methanol, 51 pounds of methyl
acetate and 29 pounds of methyl formate. Although these are parallel
operations there are noticeable differences, particularly in the
methanol discharge.
The No. 1 and No. 2 Methanol Recovery Columns bottoms which are
sent to a decantor for separation from an oil layer carry the lightest
load of pollutants. It is interesting that this is the principal
discharge point for methyl formate with the average pounds discharged
per day being 90 for the No. 1 Column and 103 for the No. 2 Column.
A striking difference between the parallel operations is the average
discharge per day of 160 pounds of dimethylamine from the No. 2
Column and only 1.4 pounds from the No. 1 Column. All the other
discharges are below 15 pounds per day except for methyl acetate
at 17 pounds from No. 1 Column and methanol at 36 pounds from No. 2
Column.
3-9
-------
Data for the total wastewater as found in the wastewater
treatment sewer is given in Table 2.7. The amounts of monomethyl-
amine and trimethylamine are quite low at 18 and 4 average pounds
per day respectively. The largest discharge is for dimethylamine
which amounts to 1389 pounds per day average discharge with a
standard deviation of 2259 pounds. This is of considerable signi-
ficance since dimethylamine reacts with nitrous acid to form the
potent carcinogen dimethylnitrosamine (N-nitrosodimethylamine), as
shown below:
(CH3)2 NH + HONO —*- (CH3)2 NNO + H20
Obviously, air or water emissions containing dimethylamine should not
be allowed to contact nitrous acid.
3.2.2 Discharges from the Ethvlamines Process
In Table 3-3 we have listed the pollutant discharges, their
source and type of discharge. The expected points of discharge are
given in Figure 3-2 which is followed by a listing of the pollutants
expected at each point.
The details available from the DuPont plants on the methylamines
process are lacking for the ethylamines process. The pollutants
listed were found in the literature, or based on close analogies to
those in the methylamines process.
Point 1 represents a bleed for noncondensible gases which would
be used as a build-up of carbon monoxide and ethylene occurred.
Points 2, 3 and 5 represent vents on the respective columns. Point 4
3-10
-------
TABLE 3-3
POLLUTANT DISCHARGES FROM THE ETHYLAMINES PROCESS
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
POLLUTANTS
Ethanol
Ammonia
Hydrogen
Monoethylamine
Diethylamine
Triethylamine
Alumina, Silica,
Aluminum phosphate,
Copper, Nickel, etc.
Acetonitrile
Ethyl ether
Ethylene
Acetaldehyde
Diethylacetamide
Carbon Monoxide
SOURCE
Feedstock
Feedstock
Feedstock
Product
Product
Product
Catalyst fines
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
TYPE OF DISCHARGE
Air, Water
Air, Water
Air
Air, Water
Air, Water
Air, Water
Solid
Air, Water
Air
Air
Air, Water
Water
Air
3-11
-------
RECYCLE AMINES
I
M
to
ETHANOL
HEAT
VAPORIZER EXCHANGER
CATALYTIC
REACTOR
PRODUCT
COOLER
GAS NH3
SEPARATOR COLUMN
SOURCE: McKetta/ 1977
TO WASTE
Point 4
TRI
DECANTER COLUMN
MONOETHYLAMINE
PRODUCT
DIETHYLAMINE
PRODUCT
TRIETHYLAMINE
PRODUCT
FIGURE 3-2
LEONARD PROCESS FOR THE
MANUFACTURE OF ETHYLAMINES
-------
POINT SOURCE POLLUTANTS
FOR ETHYLAMINES MANUFACTURE
FOR FIGURE 3-2
Point 1 Point 2
Hydrogen Monoethylamine
Carbon Monoxide Acetaldehyde
Ethylene Ethyl ether
Ammonia
Point 3 Point 4
Diethylamine Monoethylamine
Acetonitrile Diethylamine
Ethanol Triethylamine
Catalyst fines
Acetonitrile
Diethylacetamide
Point 5
Triethylamine
Acetonitrile
3-13
-------
is the only place where removal of liquid waste is indicated on the
flowchart. Catalyst fines would also be removed at this point.
3.2.3 Discharges from the Manufacture of Aniline by Ammonolysis
of Phenol
In Table 3-4 are listed the pollutant discharges from the manu-
facture of aniline by ammonolysis of phenol together with their
source and type of discharge. The expected points of discharge are
given in Figure 3-3 which is followed by a listing of the pollutants
expected at each point.
The product stream from the reactor is fed to an ammonia recov-
ery column from which the overheads pass through a separator. At
this Point 1 the noncondensible gases hydrogen and nitrogen are
removed along with traces of ammonia. The bottoms from the ammonia
recovery column are sent to a drying column where at Point 2 water
is removed along with traces of ammonia and aniline.
The bottom stream from the drying column enters the purification
still from which aniline is obtained as overhead product with traces
vented at Point 3.
The major discharge of pollutants occurs at Point 4 which
represents the bottoms, or "heavies," from the pruification still.
The major impurity, diphenylamine, is discharged at this point
together with catalyst fines and any nitrogen-containing high mole-
cular weight polymers formed in the process. Small amounts of phenol
and aniline would also be expected to be present.
3-14
-------
TABLE 3-4
POLLUTANT DISCHARGES FROM THE MANUFACTURE
OF ANILINE BY AMMONOLYSIS OF PHENOL
Pollutants
Source
Type of Discharge
1. Phenol
2. Ammonia
3. Silica, Alumina.
Magnesium Oxide,
Thorium oxide,
Boron oxide,
Stannous chloride,
Aluminum chloride,
etc.
4. Aniline
5. Diphenylamine
6. Nitrogen
7- Hydrogen
8. Nitrogen-containing
high molecular
weight polymers
Feedstock
Feedstock
Water
Air, Water
Catalyst fines
Product
Side reaction
Side reaction
Side reaction
Side reaction
Solid
Air, Water
Solid
Air
Air
Solid
3-15
-------
PIPE REACTOR
SEPARATOR AMMONIA
RECOVERY STILL
DRYER
PURIFICATION
STILL
AMMONIA
•*!*
PHENOL
I
l->
CT>
Point 1
H2'N2
SOURCE: BECKER AND RUSSELL, 1973.
Point 2
RECYCLE AZEOTROPE
Point 3
ANILINE
HEAVIES
Point 4
FIGURE 3-3
SCIENTIFIC DESIGN PROCESS FOR MANUFACTURE
OF ANILINE FROM PHENOL
-------
POINT SOURCE POLLUTANTS FOR MANUFACTURE OF
ANILINE BY AMMONOLYSIS OF PHENOL
FOR FIGURE 3.3
Point 1
Hydrogen
Nitrogen
Ammonia
Point 2
Ammonia
Aniline
Point 3
Aniline
Point 4
Phenol
Catalyst fines
Aniline
Diphenylamine
Nitrogen - containing high molecular weight polymers
3-17
-------
3.2.4 Discharges from the Manufacture of Ethanolamines by the
Ammonlysis of Ethylene Oxide
In Table 3-5 we have listed the pollutant discharges, their
source, and type of discharge for the manufacture of ethanolamines
by the ammonolysis of ethylene oxide. The expected points of dis-
charge are given in Figure 3-4 and the following page lists the
pollutants expected at each point.
The pollutants were obtained from literature references and by
assuming that analogous compounds were obtained to those formed in
the manufacture of ethylenediamine by ammonolysis of ethanolamine.
The first three columns, as represented by Points 1, 2 and 3, would
be expected to vent traces of ethylene oxide and ammonia.
The next three columns run at a low vacuum of less than 10 mm.
Hg. The vents from these three columns are represented by Points 4,
5 and 6. The listed pollutants were assigned on the basis of their
respective boiling points.
The bottoms from the last column, denoted Point 7, contain the
high molecular weight condensation products formed in the process.
These products would contain nitrogen, or oxygen, or both, in a
mixture of linear and cross-linked condensation type polymers. These
would be formed at the high temperatures in the stills from the com-
pounds containing two or more reactive groups.
3.2.5 Discharges from the Manufacture of Ethvlenediamine by the
Ammonolysis of Ethylene Bichloride
In Table 3-6 we have listed the pollutant discharges, their
source, and type of discharge which are expected from the manufacture
3-18
-------
Table 3.5
POLLUTANT DISCHARGES FROM THE MANUFACTURE
OF ETHANOLAMINES BY THE AMMONOLYSIS
OF ETHYLENE OXIDE
Pollutants
1. Ethylene oxide
2. Ammonia
3. Monoethanolamine
4. D i ethanolamine
5. Triethanolamine
6. Morpholine
7. Piperazine
8. Ethylene glycol
9. Diethylene glycol
10. N-Hydroxyethyl-
piperazine
11. N-Hydroxyethyl-
morpholine
12. N-Ethylpiperazine
13. N-Ethylmorpholine
14. N-Ethylethanolamine
15. High molecular weight
condensation products
Source
Feedstock
Feedstock
Product
Product
Product
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Type of Discharge
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Solid
3-19
-------
AMMONIA
ABSORBER
AMMO_NIA_
REACTOR STRTPPER
EVAPORATION DRYING MEA DEA
S'YSTEM COLUMN COLUMN COLUMN
TEA
COLUMN
RECYCLE WATER
MEA PRODUCT
co
O
TARS TO
WASTE
SOURCE: HYDROCARBON PROCESSING, 1975
FIGURE 3-4
SCIENTIFIC DESIGN PROCESS FOR MANUFACTURE
OF ETKANOLAMINES FROM ETHYLENE OXIDE
-------
POINT SOURCE POLLUTANTS FOR MANUFACTURE
OF ETHMOLAMINES BY THE AMMONOLYSIS OF ETHYLENE OXIDE
FOR FIGURE 3.4
Points 1. 2 and 3
Ethylene Oxide
Ammonia
Point 4
Monoethanolamine
Morpholine
Piperazine
N-Ethylpiperazine
N-Ethylmorpholine
N-Ethylethanolamine
Point 5
Diethanolamine
Diethylene Glycol
N-Hydroxyethylpiperazine
Ethylene Glycol
Point 6
Triethanolamine
Point 7
Triethanolamine
High molecular weight
condensation products
3-21
-------
TABLE 3-6
POLLUTANT DISCHARGES FROM THE MANUFACTURE OF
ETHYLENEDIAMINES BY THE AMMONOLYSIS OF ETHYLENE DICHLORIDE
Pollutants
1. Ethylene dichloride
2. Ammonia
3. Ethylenediamine
4. Diethylenetriamine
5. Triethylenetetramine
6. Tetraethylenepentamine
7. Higher polyamines
8. Sodium hydroxide
9. Sodium chloride
10. Vinyl chloride
11. 1, 2-di-(N-piperazyl)
ethane
12. 1, 4-di-(2-aminoethyl)
piperazine
13. Ethyl-di-(2-amino-
ethyl) amine
14. Piperazine
15. Insoluble anionic
exchange-type resins
Source
Feedstock
Feedstock
Product
Product
Product
Product
Side reaction
Additive
Additive reaction
product
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Type of Discharge
Air, Water
Air, Water
Air, Water
Air, Water
Water
Water
Solid
Solid
Solid
Air
Air. Water
Air, Water
Air, Water
Water
Solid
3-22
-------
of ethylenediamine by the ammonolysis of ethylene dichloride. The
anticipated points of discharge are given in Figures 3-5 and 3-6
which are followed by a listing of the pollutants expected at each
point.
Vinyl chloride, which is produced in amounts up to 3% of the
ethylene dichloride formed, would be present in the recycle ammonia
stream at Point 1, with perhaps traces of ethylene dichloride. Vinyl
chloride forms insoluble anion exchange-type resins through a series
of polymerization and polycondensation reactions which would accumu-
late at Point 2.
Sodium chloride is separated by the centrifuge at Point 3,
together with any excess sodium hydroxide. The salt is contaminated
by tars and nondistillable higher polyamines.
Vents from the No. 1 and No, 2 columns in Figure 3-6 labelled
Points 4 and 5 respectively are expected to contain ethylenediamine.
The remaining pollutants are found in the bottoms from Column No. 2
as listed under Point 6. Further batch distillation could separate
the higher amines from the impurities such as piperazine and
alkylated piperazines.
3.2.6 Discharges from the Manufacture of Ethylenediamine by
the Ammonolysis of Ethanolamine
In Table 3-7 we have listed the pollutant discharges, their
source, and type of discharge which are expected from the manufacture
of ethylenediamine by the ammonolysis of ethanolamine. The antici-
pated points of discharge are given in Figure 3-7, which is followed
by a listing of the pollutants expected at each point.
3-23
-------
RECYCLE
C H C1
^2 4 Z
HO...
ruinu t
NH i ,. ,
o
£-
"*w~
~j7
NH
'_"!.'
Point I
1*. COOLER — /vW SURGE
*- OUULLU -^ i> TANK
CONTROL VALVE
< NH ,
^ _. nii^
-< FRACTIONATING TOWER
(AQUEOUS) | _J
REBOILER
+WATER
OR
C2H4(NH2)2
+WATER+NaCl
SOURCE: U.S. PATENT 2,805,254
FIGURE 3-5
PROCESS FOR MANUFACTURE OF ETHYLENEDIAP.1INE
FROM ETHYLEME DICHLORIDE AND AMMONIA
3-24
-------
Point 4
CRUDE
NEUTRALIZED
PRODUCT
RECYCLE LIQUID
>_ NAC1
TO WASTE
CENTRIFUGE
SOURCE: U.S. PATENT 3,202,713
FIGURE 3-6
APPARATUS FOR THE SEPARATION OF ETHYLENED1AMINE
FROM CRUD'E PRODUCT
3-25
-------
POINT SOURCE POLLUTANTS FROM THE MANUFACTURE OF
ETHYLENEDIAMINES BY THE AMMONOLYSIS OF ETHYLENE DICHLORIDE
FOR FIGURES 3-5 AND 3-6
Point 1
Ethylene dichloride
Ammonia
Vinyl chloride
Point 2
Insoluble anionic exchange-type resins
Point 3
Sodium chloride
Sodium hydroxide
Higher polyamines
Point 4
Ethylenediamine
Point 5
Ethylenediamine
Point 6
Diethylenetriamine
Triethylenetetramine
Tetraethylenepentamine
1,2-di-(N-piperazyl) ethane
l,4-di-(2-aminoethyl) piperazine
Ethyl-di-(2-ami'.ioethyl) amine
Piperazine
3-26
-------
TABLE 3-7
POLLUTANT DISCHARGES FOR THE MANUFACTURE OF
ETHYLENEDIAMINE BY AMMONOLYSIS OF ETHANOLAMINE
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
Pollutants
Ethanolamine
Ammmonia
Hydrogen
Ethylenediamine
Diethylenetriamine
Triethylenetetramine
Tetraethylenepentamine
Higher polyamines
Nickel, copper
chromite, cobalt,
platinum,
Magnesium oxide,
copper oxide,
ferric oxide,
chromium oxide, etc.
Piperazine
N-Ethylpiperazine
N- Amino e thy Ipiperazine
N-Hydroxy ethyl-
Source
Feedstock
Feedstock
Feedstock
Product
Product
Product
Product
Product
Catalyst :
Side reac
Side reac-
Side reac
piperazine
14. N-MethyIpiperazine
15. 2- (2-Aminoethylamino)
ethanol
16. N-Methylethylenediamine
17. N-Ethylethylenediamine
18. Morpholine
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Side reaction
Type of Discharge
Air, Water
Air, Water
Air
Air,. Water
Air, Water
Water
Water
Solid
Solid
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
Air, Water
3-27
-------
VAPORIZER
RECYCLE-GAS
COMPRESSOR
I
K>
oo
REACTOR
Point,. I
SEPARATOR
7
CONDENSER
NH-
PolntJ.
COLUMN
*\ 1
T
H90
PoinJLl
COLUMN
EDA
I
PURIFICATION
UNIT
COLUMN
3
PIP ~
Point 5
|
MEA
POLYAMINE
SEPARATION
SECTION
T
Point 6
DETA
SOURCE:
Point 7
TO WASTE
KOHN, 1978
AEP
HEP
FIGURE 3-7
LEONARD PROCESS FOR MANUFACTURE OF
ETHYLENEDIAMINE FROM MONOETHANOLAMWE
-------
POINT SOURCE POLLUTANTS FOR MANUFACTURE OF
ETHYLENEPIAMINE BY AMMONOLYSIS OF ETHANQLAMINE
FOR FIGURE 3-7
Point 1
Ammonia
Ethanolamine
Hydro gen
Point 5
Piperazine
Ethy1enediamine
Point 2
Ammonia
Ethylenediamine
Point 3
Ethylenediamine
Morpholine
Point 6
Ethanolamine
Diethylenetriamine
Triethylenetetramine
Tetraethylenepentamine
N-Ethylpiperazine
N-Aminoethylpiperazine
N-Hydroxyethylpiperazine
N-Methylpiperazine
2-(2-Aminoethylamino) ethanol
Point 4
Ethylenediamine
Piperazine
N-Methylethylenediamine
N-Ethylethylenediaraine
Point 7
Catalyst fines
Higher polyamines
3-29
-------
The aminated stream from the reactor flows to a separator,
actually a partial condenser, where at Point 1 ammonia and hydrogen
with traces of ethylenediamine are separated and recycled through a
compressor to the reactor. The liquid phase enters column 1 where
at Point 2 any remaining ammonia is removed along with traces of
ethylenediamine. Water is distilled off in column 2, at Point 3,
containing traces of ethylenediamine and morpholine. According to
Leo.nard, the process licensor* this water can go directly to a bio-
treatment facility.
Ethylenediamine and piperazine are stripped off as overheads in
column 3 and are sent to a purification unit where they would be
present at Points 4 and 5.
The bottoms from column 3 are sent to a polyamine separation
section which in essence is a batch distillation unit. The several
compounds listed under Point 6 would be discharged here. The solid
wastes consisting of catalyst fines and nondistillable higher poly-
amines would be discharged at Point 7.
3.3. Evaluation of Similarities and Dissimilarities of Discharges
from Six Selected Aminations by Ammonolysis
In Section 3 we have been evaluating the six processes using
amination by ammonolysis for discharge similarities. In Section 3.1
the flowsheets for the processes were compared. In Section 3.2 we
made a detailed study of the expected air, water and solid discharges
and their discharge points on the flowsheets for each of the six
processes.
3-30
-------
In this Section 3.3 we will evaluate the discharges for
similarities and dissimilarities to determine if a general pattern
of pollutant discharges may be deciphered for the process of
amination by ammonolysis.
In Table 3-8 we have listed the discharges for each process
using generic groupings where possible. Study of the table shows
that there are a number of common discharges both of specific com-
pounds and of generic groups. Obviously, ammonia and amines are
found in the discharges from each process. Catalyst fines are
discharged from the four processes requiring catalysts: methylamines,
ethylamines, aniline, and ethylenediamine from ethanolamine. Non-
distillable high molecular weight polymers are found in four processes:
for aniline, and for the three difunctional products—ethanolamines,
ethylenediamine from ethylene dichloride, and ethylenediamine from
ethanolamine.
The two monofunctional products—methylamines and ethylamines—
have common discharges of amides, ethers, an aldehyde and carbon
monoxide. The three difunctional products—ethanolamine, ethylene-
diamine from ethanolamine and ethylenediamine from ethylene dichloride
have common discharges of piperazine and substituted piperazines.
Morpholine and substituted morpholines are discharged from the two
processes where ethanolamine is a product or feedstock.
Dissimilarities among'the six processes are surprisingly few.
The major ones occur in the ethylenediamine from ethylene dichloride
3-31
-------
TABLE 3-8
COMPARISON OF DISCHARGES FROM SIX SELECTED AMINATIONS BY AMMONOLYSIS
AMINATION PRODUCTS
DISCHARGES
Methylamines
Ammonia, methanol, methyl amines, catalyst fines (alumina, silica,
cobalt sulfide), amides, ethers, esters, formaldehyde, CO.
Ethylamines
Ammonia, ethanol, ethylamines, catalyst fines (alumina, silica, Ni,
Cu) amides, ethers, acetaldehyde,. CO, acetonitrile
Aniline
Ammonia, phenol, aniline, catalyst fines (alumina, silica, MgO,
A1C1,.), diphenylamine, nitrogen-containing high molecular weight
polymers
Ethanolamines
Ammonia, ethylene oxide, alkanolamines, glycols, morpholine,
substituted morpholines, piperazine, substituted piperazines,
nitrogen and/or oxygen-containing high molecular weight polymers
Ethylenediamine
(from ethylene dichloride)
Ammonia, ethylene dichloride, ethylenediamine, higher polyamines,
piperazine, substituted piperazines, nondistillable high molecular
weight polyamines, vinyl chloride, sodium chloride, insoluble
anionic exchange-type resins
Ethylenediamine
(from ethanolamine)
Ammonia, ethanolamine, ethylenediamine, higher polyamines,
piperazine, substituted piperazines, nondistillable high molecular
weight polyamines, morpholine, catalyst fines (MgO, Ni, Co,
ferric oxide)
-------
process due to the presence of the halogen atoms. Ethylene dichloride
dehydrohalogenates to give vinyl chloride in amounts up to 3% of the
ethylene dichloride introduced. Two moles of HC1 are formed for
every mole of ethylenediamine produced. The HC1 must be neutralized
with sodium hydroxide forming sodium chloride. These large amounts
of salt contaminated with nondistillable high molecular weight
polyamines present a. difficult disposal problem.
3-33
-------
4.0 STATE-OF-THE-ART DISCHARGE TREATMENT AND DISPOSAL FOR SIX
SELECTED AMINATIONS BY AMMONOLYSIS
In this Section 4 we will present the expected treatment and
disposal of the discharges from the six amination processes in terms
of segregated point source discharges. There is little direct infor-
mation on these processes in the literature so our determinations
will be based principally on current pollution engineering practices.
4.1 Air Pollution Controls for Air Point Sources
Information, on .the.methy.lamines process at the .Belle plant of
DuPont was available (Quarles, 1975), as given in Figure 4-1.
Although their flow sheet shows the noncondensibles at Point 1 to be
vented to the atmosphere we assume there would be enough CO, hydrogen
and methane to support direct combustion (flare).
We assume that the ethylamines process would be analogous to
methylamines, as shown in Figure 4-2. Noncondensibles consisting of
CO, hydrogen and ethylene would be flared from a vent at Point 1.
The aniline process, as shown in Figure 4-3, would have a flare
at Point 1 to burn hydrogen and traces of ammonia.
We do not expect air point pollution sources from the ethanol-
amines process,. as shown in Figure 4-4-. The column vents at Points 1
through 6 would be. connected to scrubbers with the discharges treated
as wastewater.
The ethylenediamine from ethylene dichloride process is shown
in Figures 4-5 and 4-6. A vent at Point 1 would be connected to a
scrubber followed by a flare for the vinyl chloride. Vents on
4-1
-------
Point 1
Noncondensible
vented to
atmosphere
Steam I
1
Vent
Dehydrat
Waste- 1
water
Point 2
0
- < ^
1 3 *
T ,£ 1 Methanol Ammonia
jater Preheater Recycle
-------
RECYCLE AMINES
•P-
I
OJ
ETHANOL
AMMONIA
i-iEAT
VAPORIZER EXCHANGER
RECYCLE
II
Point 1
COMPRESSOR
JJ
MAKE-
>r£f
Point 2
I
—I
GAS NH3
SEPARATOR COLUMN
SOURCE: McKettax 1977
MONO
COLUMN
CATALYTIC
REACTOR
PRODUCT
COOLER
Point 3
^
^
DI
COLUMN
TO WASTE
Point 4
TRI
DECANTER COLUMN
k MONOETHYLAMINE
~^ PRODUCT
> DIETHYLAMINE
PRODUCT
TRIETHYLAMINE
PRODUCT
Point 1
Direct combustion (flare)
Points 2.3,5
Scrubbers
Point 4
Incinerator
FIGURE 4.2
LEONARD PROCESS FOR THE
MANUFACTURE OF ETHYLAMINES
-------
PIPE REACTOR
SEPARATOR AMMONIA
RECOVERY STILL
PRYER
PURIFICATION
STILL
ARMONIA
PHENOL
Point 1
H2'N2
SOURCE: BECKER AND RUSSELL/ 1973.
H2° Point 2
RECYCLE AZEOTROPE
FIGURE 4-3
SCIENTIFIC DESIGN PROCESS FOR MANUFACTURE
OF ANILINE FROM PHENOL
Point 3
ANILINE
HEAVIES
Point 4
Point 1
Direct combustion (flflire)
Points 2,3
Scrubber
Point 4
Incineration
-------
AMMONIA
ABSORBER
A_MMONIA_
REACTOR STRIPPER
EVAPORATION DRYING
SYSTEM • COLUMN
MEA PEA TEA
COLUMN COLUMN COLUMN
RECYCLE WATER
MEA PRODUCT
I
Ul
SOURCE: HYDROCARBON PROCESSING. 1975
TARS TO
.WASTE
Points 1.2,3.4.5.6
Scrubber
Point 7
Incinerator
FIGURE 4-4
SCIENTIFIC'DESIGN PROCESS FOR MANUFACTURE
OF ETHANOLAMINES FROM ETHYLENE OXIDE
-------
Point 2
NaOH
(AQUEOUS)
RECYCLE NH.
NH.
COOLER
Point 1
SURGE
TANK
CONTROL VALVE
FRACTIONATING TOWER
REBOILER
C2H4(NH2)2-2HC1
+WATER
OR
C2H4(NH2)2
+WATER+NaCl
Point 1
Scrubber
Direct combustion (flare)
Point 2
Filtration for removal
to secured landfill
SOURCE: U.S. PATENT 2,805,254
FIGURE 4-5
PROCESS FOR MANUFACTURE OF ETHYLENEDIAM1NE
FROM ETHYLENE DICHLORIDE AND AMMONIA
4-6
-------
Point 3
Secured landfill
Points 4,5
Scrubber
Point 6
Batch distillation followed
by incineration
CRUDE
NEUTRALIZED
PRODUCT
Point *
RECYCLE LIQUID
NAC1
TO WASTE
CENTRIFUGE
SOURCE: U.S. PATENT 3,202,713
FIGURE 4-6
APPARATUS FOR THE SEPARATION OF ETHYLENEDIAMINE
FROM CRUDE PRODUCT
4-7
-------
columns 1 and 2 at Points 4 and 5 would be connected to scrubbers
with the discharges treated as wastewater.
The process for manufacture of ethylenediamine from monoethanol-
amine is shown in Figure 4-7. Vents from the separator and all
columns are connected to scrubbers with the discharges treated as
wastewater.
4.2 Water Pollution Controls for Water Point Sources
In the methylamines process from the DuPont Belle plant, as
shown in Figure 4-1, wastewater is treated from Points 2 through 6.
DuPont has shown that biological treatment of undiluted wastes when
operating at plant capacity is almost certainly unfeasible (Quarles,
1975) . A dilution of 10-15 times is indicated. Filtration studies
have shown that the BOD- reduction is insignificant and does not
support expenditures for filtration equipment. Treatability studies
with carbon show erratic performance with minor reduction in BOD,.
for biotreated amines waste. Therefore, the BATEA (Best Available
Technology Economically Available) should be set the same as BPCTCA
(Best Practical Control Technology Currently Available) which is
biological treatment with an acclimated seed in an aerated lagoon.
This is pending further treatablility studies.
A letter of August 23, 1977, reproduced in the Appendix, des-
cribes the process used by IMC. They state that "the wastewaters
generated from the dimethylamine process are mixed together with
the majority of other process wastewaters and sent to a holding
4-8
-------
MEA
NH-
1
VAPORIZER
REACTOR
Points 1.2,3,4,5,6
Scrubber
Point 7
Incinerator
RECYCLE-GAS
COMPRESSOR
:i ^>—
NH3, H
Point 1
SEPARATOR
4-
CONDENSER
NH0
Point 2
COLUMN
Point 3
COLUMN
*\ 2
Point 4
tEDA
^_
PURIFICATION
UNIT
COLUMN
3
*"™f^
T
PIP
Point 5
'
MEA
POLYAMINE
SEPARATION
SECTION
Point 6
DETA
*-
AEP
HEP
T
Point 7
SOURCE:
TO WASTE
KOHN, 1978
FIGURE 4-7
LEONARD PROCESS FOR MANUFACTURE OF
ETHYLENEDIAMINE FROM MONOETHANOLAMINE
-------
lagoon prior to spray irrigation. Therefore, IMG's 'state-of-the-
art1 is sprayed irrigation of these wastewater.
The ethylamines process "is shown in Figure 4-2. This is
expected to be very closely related to the methylamines process.
As carbon monoxide and ethylene build up in the recycle hydrogen
stream a portion will be bled off at Point 1 and flared. Vents from
the mono-, di-, and triethylamine columns at Points 2, 3 and 5 are
connected to-wet scrubbers. The wastewater from the scrubbers is
diluted and sent for biological treatment, with an acclimated seed in
an aerated lagoon: The condensation products, or "oils", collected
from the decanter at Point 4 are sent to an incinerator.
The Scientific Design process for manufacture of aniline from
phenol is given in Figure 4-3. There are no U.S. plants, but a
Japanese plant of Mitsui has been operating since 1970. Waste dis-
posal problems are claimed to be minimal. Hydrogen, with traces of
ammonia, would be flared at Point 1. Vents from Points 2 and 3 would
be connected to wet scrubbers. The wastewater from the scrubbers is
sent for biological treatment with an acclimated seed in an aerated
lagoon (Baird, et al., 1977; Joel, et al., 1977). In a study of
conjugate dialysis, aniline and phenol were removed from wastewater
by acid-base conjugation- (Smith, et al., 1976). A U.S. patent to
Dow describes a method for removing and recovering aniline from an
aqueous solution by molecular sorption on anion exchange resins and
elution with aqueous strong mineral acid. The "heavies" at Point 4,
4-10
-------
including nitrogen containing high molecular weight polymers, would
be sent to an incinerator.
The Scientific Design Process for manufacture of ethanolamines
by the ammonolysis of ethylene oxide is given in Figure 4-4. Vents
from the six columns, as represented by Points 1 through Point 6,
would be connected to wet scrubbers. The wastewater from the scrub-
bers would be sent for biological treatment with acclimated seed in
an aerated lagoon (Chabrabarty, et al., 1969). A Japanese patent
claims purification of alkanolamine-containing wastewater by passing
it through strongly acidic cationic exchange resin layers. The "tars",
or high molecular weight condensation products from Point 7 are sent
to an incinerator.
The conventional process for manufacture of ethylenediamine by
ammonolysis of ethylene dichloride is shown in Figures 4-5 and 4-6.
The vent from the surge tank at Point 1 is connected to a wet scrub-
ber. The vents from columns No. 1 and No. 2 are also connected to
wet scrubbers. The wastewaters from the scrubbers are sent for bio-
logical treatment with an acclimated seed in an aerated lagoon. The
bottoms from column No. 2 at Point 6 are sent to a batch distillation
column for recovery of desired higher amines, such as diethylenetri-
amine and triethylenetetramine. Bottoms from the batch still are
sent to an incinerator.
The new Leonard process for manufacture of ethylenediamine by
ammonolysis of monoethanolamine is not yet in use in operating plants
4-11
-------
in the U.S. This catalytic process eliminates many of the waste-
treatment problems associated with the conventional ethylene dichloride-
feedstock route. Vents from the separator and the columns, as repre-
sented by Points 1 through 6 are connected to wet scrubbers. The
wastewater from the scrubbers would be sent for biological treatment
with acclimated seed in an aerated lagoon. The bottoms from the
polyamine separation section at Point 7 would be sent to an incinerator.
4.3 Solid Waste Treatment and Disposal
The only one of the six processes which has a continuing solid
waste disposal problem is the manufacture of ethylenediamine by the
ammonolysis of ethylene dichloride as shown on Figure 4.6 at
Point 3. Two moles of sodium chloride are produced for every mole
of ethylenediamine manufactured, by neutralization of the HC1,
formed in the reaction, with sodium hydroxide. This sodium chloride
would be contaminated with high molecular weight nondistillable
polyamines so would probably require disposal in a secure landfill.
The four catalytic processes, tnethylamines, ethylamines, aniline
from phenol, and ethylenediamine from ethanolamine would all require
periodic catalyst changes. If economics warranted, these spent
catalysts would be returned to the supplier to recover their metal
values. Otherwise the spent catalysts would have to be disposed of
in a secured landfill.
4-12
-------
5.0 CONCLUSIONS
5.1 Commonality of Waste Discharges
The waste discharges from each of the six processes have been
listed for comparison in Table 3.8 using generic groupings wherever
possible. A careful study of the table shows that there are a
number of common discharges, both of specific compounds, and of
generic groups. Ammonia and amines are found in the discharges from
each of the six processes, as would be expected. Nondistillable high
molecular weight polymers are formed in four processesr for aniline,
and for the three difunctional products - ethanolamines, ethylene-
diamine from ethylene dichloride, and ethylenediamine from ethanol-
amine.
Processes for the two monofunctional products - methylamines and
ethylamines - have common discharges of amides, ethers, an aldehyde
and carbon monoxide. Processes for the three difunctional products -
ethanolamine, ethylenediamine from ethanolamine, and ethylenediamine from
ethylene dichloride have common discharges of piperazine and substituted
piperazines. Morpholine and substituted morpholines are common discharges
from the two processes where ethanolamine is a product or feedstock.
Catalyst fines are common discharges for the four processes
requiring catalysts: methylamines, ethylamines, aniline, and
ethylenediamine from ethanolamine. The fines consist of silica,
alumina, and metals, or metallic compounds, including nickel, cobalt,
and copper.
5-1
-------
Emission of amines, particularly diaIkylaminas, to the environment
may be potentially hazardous since reaction with nitrous acid, or
oxides of nitrogen, forms nitrosamines. Diethylnitrosamine and
dimethylnitrosamine are known potent carcinogens. The formation of
dimethylnitrosamine (N-nitrosodimethylamine) from dimethylamine and
nitrous acid is shown below:
(CH3)2NH + HONO > (CH3)2NNO + H20
Special precautions must be taken to prevent mixing waste streams
containing dialkylamines with those containing nitrous acid.
5.2 Extent of the Process of Amination by Ammonolysis in the U.S.
Organic Chemical Industry
We have shown in Section 5.1 that there are a number of common
wastes discharges from the six processes studied as typical of the
process of amination by ammonolysis. The extent to which this
process is used in the U.S. production of synthetic organic chemicals
is shown in Table 5.1. Eighteen chemicals, including some which are
closely related groups of chemicals, are manufactured in 53 plants
(some plants may produce several of the alkylamines). These plants
have an annual capacity, or annual production rate, of over 1.2
billion pounds. Urea is listed separately since it alone is manu-
factured in 47 plants- with an annual effective capacity of 6.8
million metric tons.
This multiplicity of 'products and plants and the large volume
of production shows the importance of the process of amination by
5-2
-------
TABLE 5.1
U.S. PRODUCTION OF SYNTHETIC ORGANIC CHEMICALS
USING AMINATION BY AMMONOLYSIS
Annual Capacity
(Millions of Pounds)
50J
Producing
Chemical Plants
Aminoanthraguinones 2
Butylamines 3
Chloroanilines 2
Chlorobenzenesulfonamide 2
Choline chloride 6
Dimethylformamide 3
Ethanolamines 5
Ethylamines 4
Ethylenediamine 3
Glycine 4
Hexamethylenediamine 1
Isopropylamine, mono 4
Methylamines 5
Monomethylamine (5)
Dimethylamine (.5)
Trimethylamine (5)
Morpholine 1
o-Phenylenediamine 4
Stearamide- 4
Total 53
Urea 47
1976 Production.
2
Thousands of Metric Tons.
Sources: 1978 Directory of Chemical Producers, SRI International, 1978.
Synthetic Organic Chemicals, Production and Sales, 1977, U.S.
International Trade Commission, 1977.
435
50]
93
200
33]
326
431
-0.31
1,230.3
6,8022
-------
ammonolysis. Prediction of common waste discharges from these
chemicals, or others, manufactured by the process of amination by
ammonolysis will be of great help in their monitoring and regulation.
Process changes aimed at decreasing or preventing these discharges
could be encouraged.
5.3 Use of Dissimilarities in Waste Discharges as a Basis for
Division of Amination Processes into Related Groups
In our detailed consideration of the six amination by ammonolysis
processes, we have noted many common discharges with surprisingly few
dissimilarities. On further consideration, we have observed that
these dissimilarities may be used to divide the amination processes
into three related groups.
One group would consist of processes in which the feedstock
contains one or more halogen atoms, as illustrated by our study of
the manufacture of ethylenediamine from ethylene dichloride. Two
moles of HC1 are formed for every mole of ethylenediamine produced.
The HC1 must be neutralized with sodium hydroxide, forming sodium
chloride. These large amounts of salt are contaminated with non-
distillable high molecular weight polymers, so must be disposed of in
a secured landfill. This group would also have the chlorocompound
used as a feedstock, and any of its decomposition products, in the
waste discharges.
Besides the ethylenediamines several examples from Table 5.1
include:
5-4
-------
aminoanthraquinones from chloroanthraquinones, chloroanilines from
dichlorobenzenes, chlorobenzenesulfonamide from benzene sulfonyl
chloride, glycine from chloroacetic acid, morpholine from dichloro-
ethyl ether, and o-phenylenediamine from o-dichlorobenzene.
A second group would consist of the monofunctional products
which were represented in our study by the methylamines and ethylamines,
These had common discharges of amides, ethers, an aldehyde and carbon
monoxide. Other examples from Table 5.1 would include butylamines
and isopropylamines.
The third group consists of the difunctional products which are
represented in our study by the ethanolamines and ethylenediamine.
Common discharges include nondistillable high molecular weight poly-
mers, piperazine, and substituted piperazines. If a hydroxy group is
present in either feedstock or product, as in the ethanolamines,
morpholine and substituted morpholines are present in the waste
discharges. Aromatic compounds could be considered in this classifi-
cation as a subgroup because they form nondistillable high molecular
weight polymers, even if monofunctional, as shown by aniline in our
s tudy.
In any of the processes using catalysts there would also be a
waste discharge of catalyst fines. This would be expected in the
second group for monofunctional groups, but could also occur in the
other two groups.
5-5
-------
BIBLIOGRAPHY
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Hawley, G.. G., coeditbry The- Condensed Chemical' Dictionary. 9th ed.
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March, J., Advanced Organic Chemistry—Reactions, Mechanisms and
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6-1
-------
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7-1
-------
REFERENCES (Continued)
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20. G. 0. Cunne, Jr. and F. W. Lommen to Carbide and Carbon Chemicals
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1952.
22. T. L. Davis and R. C. Elderfield, "The Catalytic Preparation of
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1956.
24. R. S-. Egly'and E. T.'" Smith, "Effect'of Operating Variables on
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7-2
-------
REFERENCES (Continued)
25. E. Enders and D. Hullstrung to Bayer AG, "Process for the
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26. E. Enders to Bayer AG, "Process for the Production of Methylamine
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28..,. H. Feichtinger, W. .£luy, J. Falbe to Ruhrchemie AG,. "Di-and
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29. C. Fitz-William to Allied Chemical Corp., "Production of Ethylene-
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31. Goodyear Tire and Rubber Co., "Ethylenediamine," German Patent
624,379, June 18, 1936, as cited in Chemical Abstracts 30:
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32. R. H. Goshorn to Sharpies Chemicals, "Manufacture of Amines,"
U.S. Patents 2,394,515 and 2,394,516, February 5, 1946.
33. R. H. Goshorn to Sharpies Chemicals, "Manufacture of Amines,"
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34. H. Hamada, T. Matsuzaki and K. Wakabayashi to National Chemical
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35. P. Herold and K. Sennewald to I. G. Farbenindustrie, "Ethylene-
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36. P. Herold and K. Smeykal to I. G. Farben, "Production of Mono-
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7-3
-------
REFERENCES (Continued)
37. S. Hichitaro and S. Tsukada to Japan Soda Co., Ltd., "Preparation
of Ethylenediamine of Desired Concentration," Japan 68 19,526,
August 23, 1968, as cited in Chemical Abstracts 70; 57110k, 1969.
38. A. R. Joel and C. P- L. Grady, Jr., "Inhibition of Nitrification-
Effects of Aniline after Biodegradation," J. Water Pollution
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39. C. T. Kautter to Shell Development Co., "Alkylolamines," U.S.
Patent 2, .051, 486, August 18, 1936.
40. C. T. Kautter to Shell Development Co., "Alkylolamines,"
.Canadian Patent 356,624, March 1.7, 1936, as cited in Chemical
Abstracts 30:29869. 1936.
41. L. Kisgergely, G. Kineses, B. Szeiler, E. Csaszar, G. Csizmazia,
G. Hodossy and J. Schmall, "Selective Production of Ethylamines ,"
Hungarian Teljes 213, April 8, 1970, as cited in Chemical
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42. K. Kobayashi and T. Funaki, "Purification of Alkanolamine —
containing Wastewater," Japan Kokai 74 66,590, as cited in
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43. P. M. Kohn, "Ethylenediamine Route Eases Pollution Worries,"
Chemical Engineering 85 (7); 90-91. March 27, 1978.
44. C. J. Kramis to DuPont, "Process for Separation of Methylamines ,"
U.S. Patent 2,848,386, August 19, 1958.
45. J. Kubica, Z. Leszcsynski and J. Strezelecki, "Continuous
Extraction-distillation Method for the Isolation of Ethyl eneamines ,
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v 1968,
46. A. N. Kurtz to Union Carbide, "Production of Methylamines," U.S.
Patent 3,444,203, May 13, 1969.
47- H. Kusaka to Yokkaichi Chemical Co., "Ethanolamines , " Japan 77
02,887, January 25, 1977 as cited in Chemical Abstracts 87:
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48. W. M. Lauter to Wingfoot Corp., "Alkylene Diamines," U.S.
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7-4
-------
REFERENCES (Continued)
49. R. C. Lemon, S. Depot and R. C. Myerly to Union Carbide,
"Production of Amines," U.S. Patent 3,022,349, February 20, 1962.
50. Jackson D. Leonard, "Catalysts for the Preparation of Methyl-
amine," Netherlands Appl., 6,607,964, December 9, 1966, as cited
in Chemical Abstracts 67;2752d. 1967.
51. Leonard Process Co. Inc., "Methylamines," Hydrocarbon Processing
52(11)150, 1973.
52. Z. Leszczynski, J. Kubica, A. Pile and W. Bacia, "Reactor Studies
of the Production Process of Ethylenediamine and Its Derivatives
from Dichlorpethane. and Aqueous Ammonia. Solutions." .Przem. Chem.
46/4):210-213, 1967 (Polish), as cited in Chemical Abstracts 67:
32273r, 1967.
53. R. Lichtenberger and F. Weiss to Societe d'EIectrochimie d'Electro-
metallurgie et des Acieries Electriques d'Ugine, "Ethylenediamine,"
German Patent 1,100,645, Appl. July 7, 1958 as cited in Chemical
Abstracts 56;4617f. 1962.
54. Lonza Ltd., "Preparation of Mono- and Dialkylamines," Netherlands
Appl. 6,408,377, January 25, 1965, as cited in Chemical Abstracts
.63:493h, 1965.
55. A. J. Lowe, D. Butler and E. M. Meade to Qxirane, "Alkanolamines,"
U.S. Patent 2,823,236, February 11, 1958.
56. A. J. Lowe, D. Butler and E. M. Meade to Oxirane Ltd., "Alkanol-
amines," British Patent 760,215, October 31, 1956, as cited in
Chemical Abstracts 51:10564s. 1957.
57. M. Lutz, "Reactor for Continuous Production of Ethanolamines,"
East German Patent 112,751, May 5, 1975 as cited in Chemical
Abstracts 84:104977z. 19.76.
58. G. F. MacKenzie to Dow Chemical Co., "Conversion of Ethanolamine,"
U.S. Patent 2,86-1,995, November 25, 1958.
59. J. Martin and L. C. Swallen to Commercial Solvents, "Process for
the Production of Dimethylamine," U.S. Patent 1,926,691,
September 12', 19-33-.
60. J. Martin and L. C. Swallen to Commercial Solvents, "Production
of Methylamine," U.S. Patent 1,875,747, September 6, 1932.
7-5
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REFERENCES (Continued)
61. G. Marullo to Montecatini, "Separation of Amines," U.S. Patent
3,202,713, August 24, 1965.
62. D. M. McClain to National Distillers, "Alkylamines from Olefins
and Ammonia," U.S. Patent 3,412,158, November 19, 1968.
63. J. G. Milligan and T. Cour to Jefferson Chemical Co., "Amine
Recovery," U.S. Patent 3,448,152, June 3, 1969.
64. P. E. Millington to DuPont, "Synthesis of Amines," U.S. Patent
2,112,970, April 5, 1938.
65. Montecatini, ."Ethylenediamine,." Italian-Patent. 617,348, February
17, 1961, as cited in Chemical Abstracts 55;11019d. 1961.
66. Mo Och Domsjo Aktiebolag, "Catalytic Conversion of Aliphatic
Alcohols and Aminoalcohols into Amines," French Patent 1,575,557,
July 25, 1969, as cited in Chemical Abstracts 72;100002g. 1970.
67. P. Moss and N. Godfrey to Jefferson Chemical Co., "Method for
the Simultaneous Production of Acyclic and Polycyclic Amines,"
U.S. Patent 3,151,115, September 29, 1964.
68. H. G. Muhlbauer to Jefferson Chemical Co., "Anhydrous Ethylene-
diamine," U.S. Patent 3,394,186, July 23, 1968.
69. B. H. Nicolaisen to Olin Mathieson Chemical Corp., "Manufacture
of Ethylenediamine," U.S. Patent 2,805,254, September 3, 1957.
70. J. F- Olin and J. F. McKenna to Sharpies Chemicals, "Manufacture
of Aliphatic Amines," U.S. Patent 2,365,721, December 26, 1944.
71. J. F. Olin to Sharpies Chemicals, "Separation of Trimethylamine
Mixtures," U.S. Patent 2,377,511, June 5, 1945.
72. J. F. Olin to Sharpies Chemicals, "Purification of Amine Reaction
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2,394,515, October 30, 1945.
73. E. B. Punnett to National Aniline and Chemical, "Catalytic
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74. C. C. Quarles, "Methylamine Manufacturing Effluents, Part I," A
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7-6
-------
REFERENCES (Continued)
75. C. C. Quarles, "Methylamine Manufacturing Effluents, Part II,"
A Special Report for the U.S. Environmental Protection Agency,
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76. C. C. Quarles, "Methylamine Manufacturing Effluents, Part III,"
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77- C. C. Quarles, "Methylamine Manufacturing Effluents, Part IV,"
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78. C. C. Quarles, "Comments by DuPont Relative to Organic Chemicals
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Glycol, Methylamines and Oxo Chemical Processes," (40 FR 34409-
34417), September 15, 1975.
79. E, W. Reid and D. C. Lewis to Carbide and Carbon Chemicals Corp.,
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cited in Chemical Abstracts 24:2756. 1930.
80. E. W. Reid and D. C. Lewis to Carbide and Carbon Chemicals Corp.,
"Ethanolamines," U.S. Patent 1,904,013, April 18, 1933.
81. S. Ropuszynski, 0. Staroojciec and E. Mularezyk, "Synthesis of
Ethanolamines from Liquid Ethylene Oxide and Aqueous Ammonia
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(Polish) as cited in Chemical Abstracts 68:68389t, 1968.
82. R. G. Ruark to Carbide and Carbon Chemicals Co., "Mixed Aryl
Hydroxyaryl Amines," U.S. Patent 2,275,470, March 10, 1942.
83. J. L. Russell to Halcon International, "Aniline from Phenol,"
German Offen. 1,954,274, May 27, 1970, as cited in Chemical
Abstracts 73;35024v, 1970.
84. R. N. Sargent to Dow Chemical Co., "Repetitive Process for the
Removal and/or Recovery of Amines from Aqueous Solutions,"
Til'S.'Patent 3,159,632, December 1, 1964.
7-7
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REFERENCES (Continued)
85. E. J. Schwoegler to Sharpies Chemicals, "Condensation of Amines
with Alkylene Oxides, as in the Production of Diethylamino-
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86. E. J. Schwoegler and J. F. Olin to Sharpies Chemicals,
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88. Y. Shinohara, T.... Yamaski, A,. Miyama and T. Ono to Mitsui
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89. Y. Shinohara and A. Arayama to Mitsui Petrochemical Industries
"Aromatic Amines," Japan 74 14,737, April 10, 1974, and
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90. J. K. Smith, S. V. Desai, R. E. C. Weaver and E. Klein,
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91. Societe d'Electrochimie d'Electrometallurgie et des Acieries
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7-8
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REFERENCE (Concluded)
96. A. W. C. Taylor, P. Davies, P. W. Reynolds to ICI, "Production
of Amines," U.S. Patent 2,636,902, April 28, 1953.
97. G. Tereshchenko, V. Krotova, T. Mikhailova, N. Yushina and
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98. W. Tyerman to ICI, "Extractive Distillation of Methylamines,"
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100. University of Brussels, "Aromatic Amines," Japan Kokai 76 16,624,
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101. D. G. Weaver and J. L. Smart, "Glycols and Ethanolamines,
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102. B. J..G. Weibull, L. U. F. Thorsell and S. 0. Lindstrom to Mo
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103. W. Whitehead and ICI, "Aliphatic Amines," British Patent 649,980,
February 7, 1951.
104. J. N. Wickert to Carbide and Carbon Chemicals Co., "Hydroxy-
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105. S. Winderl, E. Haarer, H. Corr and P. Hornberger to BASF AG,
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7-9
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APPENDIX
CORRESPONDENCE
A-l
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IMC PLAZA . LIBERTYVILLE. ILLINOIS 60048 . TELEPHONE 312 • 362-8100
INTERNATIONAL MINERALS & CHEMICAL CORPORATION
August 23, 1977
Dr. Ronald Barbaro
7036 Lee Park Court
Falls Church, Virginia, 22042
Dear Dr. Barbaro:
Mr. Paul desRosiers of the U.S. EPA requested various waste
treatment data regarding IMC's dimethylamine manufacturing
facilities from Mr. Edward Lantz of IMC.
The waste waters generated from the dimethylamine process
are mixed together with the majority of other process waste
waters and sent to a holding lagoon prior to spray irrigation,
There-fore, IMC's "state-of-the-art" is spray irrigation of
these waste waters.
Should you have any further questions, please contact the
undersigned at your convenience.
Very truly yours,
INTERNATIONAL MINERALS & CHEMICAL CORPORATION
Douglas/H. Larsen
Environmental Consultant
DKL/nw
cc: E. L. Lantz
L. W-ebb
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