EPA 600/2-76-270
October 1976
Environmental Protection Technology Series
CONVERTING CHLOROHYDROCARBON
WASTES BY CHLOROLYSIS
industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
ervironmental technology. Elimination of traditional grouping was consciously
pi anned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
viows and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
Thi 3 document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/2-76-270
October 1976
CONVERTING
CHLOROHYDROCARBON WASTES
BY CHLOROLYSIS
by
James K. Shiver
Repro Chemical Corporation
1629 K Street. NW
Washington, DC 20006
Contract No. 68-03-0456
Program Element No. 1AB604
EPA Project Officers:
Max Samfield Robert R. Swank
Industrial Environmental Research Lab. Southeast Environmental Research Lab.
Research Triangle Park, NC 27711 Athens, GA 30601
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
Contents
Page
List of Tables iv
Conclusions . 1
Recommendations 3
Introduction 4
Magnitude of the U.S. Chlorohydrocarbon 6
Waste Problem
Magnitude of the U.S. Pesticide Waste 9
Problem
Criteria for Acceptability as Chlorolysis 11
Feedstock
Pretreatment of Chlorolysis Feedstock 14
Chlorine Availability 16
Alternate Methods of Treating Chloro- 18
hydrocarbon Wastes
Impact of Chlorolysis on the Carbon 22
Tetrachloride Market
Impact of Chlorolysis on the Carbonyl 24
Chloride Market
Impact of Chlorolysis on the Hydrogen 26
Chloride Market
Recommendations for Chlorolysis 27
A. Plant capacity and process variations 27
B. Pretreatment/Purification Needs 29
C. Site Locations 29
D. Mode of Implementation 30
E. Relative Cost Advantage 31
Bibliography 32
-------
List of Tables
Table Page
I Chlorohydrocarbon Wastes 35
IA Composition of VCM and Solvent Wastes 37
II Sulfur Containing Pesticides 38
III Phosphorus and Sulfur Containing Pesticides 42
IV Phosphorus Containing Pesticides 45
V Nitrogen Containing Pesticides 46
VI Oxygen and Chlorine Containing Pesticides 53
VII U.S. Army Pesticide Suitable for
Chlorolysis with Pretreatment 58
VIII Qualitative Pesticide Solubilities In
Selected Solvents 59
IX Chlorine Producers and Announced
Expansions 60
X Carbon Tetrachloride Producers 62
XI Carbonyl Chloride Producers 63
IV
-------
Conclus ions
1. There are about 190MM Ib/year (86,400 metric tons) of
chlorohydrocarbon wastes generated in the U.S. by vinyl chloride
monomer and chlorinated solvents producers that would be
suitable chlorolysis feedstocks.
2. The distribution of these wastes is about 80 per cent from
vinyl chloride monomer production and 20 per cent from
solvents production.
3. The wastes are produced primarily in Gulf Coast locations
where the critical raw material hydrocarbons and chlorine are
readily available.
4. The pesticide manufacturers do not produce wastes that are
suitable chlorolysis feedstocks.
5. The supply of chlorine over the next five years will be
adequate to meet the needs of a chlorolysis plant to process
25,000 U.S. tons/year (22,700 metric tons) of waste.
6. The 91,000 U.S. tons (82,700 metric tons) of carbon tetrachloride
produced by a chlorolysis plant can be assimilated by the
market provided the fluorocarbon market continues to grow.
-------
7. A regional waste disposal unit which embodies a chlorolysis
unit and is capable of processing other wastes should be
constructed in a Gulf Coast location.
8. A regional waste disposal facility is estimated to cost
about $40MM and would have a 5-14 per cent return on the
invest.ment at capacity.
-------
Recommendatioiis
1. Preparation of a design and capital estimate is recommended to
establish a more quantitative basis for proceeding with the
implementation of a regional waste disposal unit.
2. The base case feedstock recommended for design of the chlorolysis
plant is 60 per cent VCM wastes mixed with 40 per cent solvent
wastes.
3. Examination of the sensitivity of the plant capacity to
feedstock variations is recommended. The range to be examined
is from 100 per cent VCM waste to about 20 per cent VCM mixed
with 80 per cent solvents waste.
4. Consideration of the Bay St. Louis, Mississippi NASA facility
as a location for the regional waste disposal unit is recommended,
5. Evaluation of the viability of other potential feedstocks is
recommended,
-------
Introduction
The disposal of wastes generated in the manufacture of
chlorohydrocarbons such as vinyl chloride, perchloroethylene ,
trichloroetaylene and various pesticides has become a significant
problem in the United States. In 1972, an estimated 350,000
tons per year of hard-to-treat residue were generated during
the production of almost 10 million tons per year of chlorinated
hydrocarbons. Methods of disposing of these wastes range from
ocean discharge, burial, and deep well injection to open-pit
burning and enclosred- incineration. Use of the non-destructive
methods results in undesirable environmental exposures. Similarly.
use of the destructive methods, although more acceptable environmentally,
JS wasteful of critical raw material resources.
Conservation of these resources by conversion to industrially
useful materials in an environmentally acceptable manner is very
desirable. A proprietary process ' offers the potential of
fulfilling both of these, requirements. This process is capable of
converting chlorohydrocarbon wastes to carbon tetrachloride by
exhaustive chlorination.
-------
The assessment 01" the magnitude of the waste chlorohydro-
carbon problem in the US and the applicability of this new
technology as a means of resolving the problem was undertaken on
behalf of the USEPA. Inherent in this assessment was a detailed
definition of the waste problem, potential economics, impact of
this new technology in the carbon tetrachloride market, and the
availability of chlorine.
This report summarizes the results of the assessment program
sponsored by the USEPA under contract number 68-03-0456.
-------
Magnitude of the U.S. chlorohydrocarbon Waste Problem
A survey of current chlorohydrocarbon and pesticide producers
was conducted to ascertain the present magnitude of the waste
problem. The results of this survey, summarized in Table I,
show that the waste chlorohydrocarbons come from two major
industries, vinyl chloride monomer, and chlorinated solvents.
The reports received from these industries indicate that the
volume of waste generated annually averages about 190MM pounds
(86,360 metric tons) and is made up of 150MM pounds (68,200 metric
tons) of VCM wasteland 40MM pounds (18,200 metric tons) of solvent
waste.
The wastes arre produced in EPA regions IV, VI, and VII.
The majority of ttre- waste, 106 out of the total 190MM Ibs. is
produced in EPA Region VI which is the Gulf Coast area. This
high concentration of waste producers which ranges from Corpus
Christi, Texas to New Orleans, Louisiana indicates that a central
disposal facility located in this highly industrialized region
could prove viable.
-------
The wastes are characterized to a degree by their producing
processes. The vinyl chloride wastes have the unique characteristic
of containing hydrogen in the molecule whereas the solvent wastes
do not contain hydrogen. This comes about through the higher
degree of chlorination and higher temperatures required to
make chlorinated solvents. Typical analyses of the waste fractions
from both vinyl chloride and chlorinated solvents operations
are presented in Table IA, The components in these wastes range
from GI through Cg chlorohydrocarbons and chlorocarbons. They
are all suitable feeds for a chlorolysis process. By the
same token, the fractions containing Cj., C2 / and €3 chlorohydro-
carbons are suitable feeds for a conventional chlorinalysis
process as is discussed later in this report. However, the
prime concern is how much of these materials are or could be
made available for chlorolysis.
The majority of the waste producers are still dependent upon
contract services for the disposal of their wastes. Fees for
a typical incineration service range from $120-150 per U.S. ton
of waste processed. This fee is expected to continue to rise in
-------
concert with labor and raw material rates. Hence, it is believed
that a loweir cost service, such as is possible with chlorolysis,
could attract a substantial portion of the waste chlorohydrocarbons
now being incinerated. An estimated 65MM Ibs/year of vinyl
chloride wastes and 40MM Ibs/year of chlorinated solvent wastes
are projected to be convertible to the use of chlorolysis if
the contract service is provided at a cost of $100 per U.S. Ton.
However, the total 105MM Ib/yr. of waste would produce about
180-190MM Ib/yr. of carbon tetrachloride. This volume of product
represents about 34--per cent of the total market for carbon
tetrachlorLde and as such could not be readily accommodated.
A more realistic volume to consider is not to exceed 20 per cent
of the market. This would limit the initial chlorolysis plant
capacity tD the processing of 50MM Ibs/yr. (25,000 U.S. tons/yr.)
of wastes.
The normal feed for this unit should be a mixture of 60 per
cent by weight vinyl chloride waste and 40 per cent by weight solvent
wastes.
-------
Magnitude of the U.S. Pesticide Waste Problem
. The results of the survey also revealed that the pesticide
industry does not produce significant quantities of waste suitable
for chlorolysis. This finding is particularly significant
because more than 200 pesticides are produced in the United States,
However, an analysis of these pesticides was made to ascertain why
this should be the case. This analysis showed that of the 209
pesticides identified in Tables II through IV, forty (40)
contain sulfur, thirty two (32) contained a combination of sulfur
and phosphorus, eLeven (11) contain only phosphorus, seventy
three (73) contain nitrogen, forty (40) contain oxygen and only
thirteen (13) contain the most desirable elements carbon hydrogen
and chlorine. These thirteen compounds are:
Aldrin o-Dichlorobenzene
Chlordane p-Dichlorobenzene
DD Pentac
DDT Perthane •
Ethylene dichloride TCBC
Benzene hexachloride
Heptachlor
Lindane
-------
Of these compounds, Aldrin, ehlordane, and DDT are the largest
volume pesticides but each has been banned by the USEPA for
environmental reasons. Ethylene dichloride, although used as a
pesticide, is manufactured primarily as an intermediate enroute to
polyvinyl chloride polymer and could be processed to useful
product by this route.
The ether compounds, DD, benzene hexachloride, heptachlor,
lindane , c.ichlorobenzene , Pentac, Perthane, and TCBC are products
manufactured in too low a volume, mostly less than 1MM Ib/year'^)
(~450 metric tons)., to be of great significance as a source of
waste chlorohydrocarbons.
The elements- contained in the balance of the pesticides (196)
make them questionable candidates for chlorolysis but will be
considered in the section of this report dealing with the
criteria ::or acceptability as chlorolysis feedstocks.
The survey also revealed that no private firm had retained
any stock,5 of banned pesticides but that government agencies had
significant stocks. The list of materials and amounts of each type
of formulation are summarized in Table vil
10
-------
Criteria for Acceptability as Chlorolysis Feedstock
Theoretical consideration of the criteria indicates that
almost any chlorinated hydrocarbon would make a suitable feed.
However, the presence of elements other than carbon, hydrogen
and chlorine in a compound give rise to significant questions
regarding product handling and corrosion. Furthermore, the
presence of particulate materials such as inorganic catalyst
particles and/or free carbon could pose a significant mechanical
problem in the operation and maintenance of critical control
equipment.
(4)
The chlorolysis process has been used successfully to
process chlorohydrocarbons. It has also been shown to have potential
for processing oxygenated chlorohydrocarbons. Carbonyl chloride is
coproduced with the carbon tetrachloride when oxygenated chloro-
hydrocarbons are processed.
However, the presence of small amounts of sulfur have been
shown to be extremely corrosive to the nickel tube used for
constructing the reactor. The sulfur content of the feed must
be kept below 25 ppm to be acceptable.
11
-------
This criterion can probably be met by diluting the sulfur
containing feed with other feeds. This method of dealing with
the sulfur problem is projected to limit the rate at which sulfur
•
containing feeds could be processed and the volume of storage
required for inventory.
The effect of nitrogen and/or phosphorus when combined in
the feed materials is unknown. The most critical aspects of
these elements are that nitrogen trichloride is explosive and
phosphorus trichloride is pyrophoric. Neither of these compounds
is desirable for the aforementioned reasons. Their presence would
seriously complicate the operation of a chlorolysis plant.
The presence of particulate materials in the feed, particularly
inorganics and free carbon present problems in that they could be
expected to accumulate in the system and also interfere with the
operation of the critical pressure control valves required to
maintain the operating pressure at 120 atmospheres. For these
reasons, the feed to the reactor must be cleaned. Filtration or
distillation are considered as preferred pretreatment methods.
These provisions will be dealt with in another section of this report
12
-------
In summary, acceptable feeds for chlorolysis must be free
of particulates, must not contain sulfur in excess of 25 ppm and
must not contain nitrogen or phosphorus. They may, however,
contain some oxygen.
13
-------
Pretreatmer.t of Chlorolysis Feedstock
Pretreatment of the wastes and banned pesticides appears to
be essential for effective operation of a chlorolysis plant.
The presence of particulate material .in the waste chlorohydrocarbons
offers the potential of plugging or jamming the critical pressure
control devices of a chlorolysis plant. These particulates are
fine carbon particles generated in typical ethylene dichloride
pyrolysis operations and catalyst fragments carried through in
fluidized bed type chlorinators. The carbon particles appear to
be too fin'e to remove by conventional filtration. Consequently,
an evaporation or distillation method appears most suitable.
A sophisticated fractional distillation does not appear to be an
essential Ingredient of this process.
Pretrsatment of banned formulated pesticides is quite complex
because of the large number of formulations possible. The wettable
powder type of formulation can be processed by first extracting
the active ingredients from the support using a suitable solvent.
Several useful solvents and the qualitative solubilities of various
pesticides in these solvents has been included as Table VIII.
14
-------
Xylene , benzene, meth\lene chloride, and carbon tetrachloride
would be the most compatible solvents for use with the chlorolysis
process. Carbon tetrachloride would be most desirable because it would
be routinely available. The use of other solvents may prove to
be necessary on a selected basis.
Filtration is the- preferred method for separating the inert
carriers from the ex-tract. This technique represents the least
energy intensive mode of operation with the best reliability.
Concentration of the extract may or may not be necessary.
In summary, the installation of a pretreatment system which
embodies the capability of both filtration and evaporation or
distillation is considered an essential adjunct to a chlorolysis
plant.
15
-------
(Chlorine Availability
. A list of chlorine producers is presented in Table IX.
The total installed capacity in 1973 was 31,480 tons per day
(28,620 metric tons). Several major expansions have been
announced with some of these plants now on-stream. The total
announced capacity is 10,765 tons per day (*-9800 metric tons) to be
in place by 1980. The majority of these expansions are to be located
in the Gulf Coast region of the united States where the prime users
are located.
'The timing of these expansions appears to be satisfactory
for coping with projected growth rates in the consuming industries.
However, major dislocation of supply could occur if the energy
situation again becomes critical. Optimistically, this is not
expected to occur. Conversion of power generating facilities
on the Gulf Coast from critical natural gas users to oil and/or
coal users could be expected to alleviate a possible chlorine
shortage resulting from a short supply of natural gas.
16
-------
The volume of chlorine required to operate a chlorolysis
unit converting 25,000 tons per year (22,700 metric tons) of
typical vinyl chloride monomer waste is 300 tons per day
(273 metric tons). This volume represents about 3 per cent
of the announced plant expansions. Thus, it would appear that
the chlorine requirements of a chlorolysis plant could be
readily accommodated by the chlorine industry within the
next five years.
17
-------
Alternate Methods of Treating Chlorohydrocarbon Wastes
Incineration is relied upon as the most effective method
now practiced in the United States for the disposal of chloro-
hydrocarbon wastes. Two approaches, conventional thermal
incineration and catalytic incineration have been developed.
Catalytic incineration as represented by the B. F. Goodrich
"Catoxid" process is the most recent addition.(8) This
technology is based upon the operation of a fluid bed reactor
with hydrogen chloride, water and carbon dioxide as products.
It appears to be suitable for operation in conjunction with large
vinyl chlcride plants which can readily accept the hydrogen
chloride vithout purification.
An apparently attractive alternate to incineration is
chlorination to perchloroethylene, trichloroethylene and carbon
tetrachloride. The patent literature indicates that Dow, Diamond
Alkali and Pittsburgh Plate Glass have developed processes
suitable ::or the conversion of C^ through C$ hydrocarbons to
chlorinated solvents.
18
-------
The Dow Chemical process as revealed in U. S. patent number
2,422,324 claims the ability to convert Cj, ^2 , and €3 hydro-
carbons and their partially chlorinated derivatives to a mixed
product of perchloroethylene and carbon tetrachloride. The
patent further claims a yield of 94-95% of desirable products
with the balance being hexachlorobenzene. The operating
temperature of the process is about 600°C. Unfortunately, the
hexachlorobenzene is one of the hard to treat wastes typical
of solvent processes.
The Diamond Alkali process as described in British Patent No.
673,565 claims the ability to convert ethylene dichloride to
perchloroethylene and trichloroethylene. This process operates
at a temperature of about 400°C using Fuller's earth as catalyst
in a fluid bed. The combined yield of perchloroethylene and
trichloroethylene is about 90 per cent. The balance of the product
is undefined but is estimated to contain such materials as
hexachloroethane, hexachlorobutadiene, hexachlorobenzene,
tetrachloroethane and pentachloroethane. These latter two
compounds may be recycled and pyrolyzed to trichloroethylene and
19
-------
perchloroethylene. The operating temperature when compared
against that of the Dow process does not appear to be adequate to
convert €3 chlorohydrocarbons to useful products. Thus, the
hexachlorobutadiene and hexachlorobenzene would be residues from
this process.
However, the process does have merit as a means of process-
ing vinyl chloride wastes to useful products because the chlorina-
tion of ethylene dichloride to both trichloroethylene and perchloro-
ethylene must proceed through the intermediate €2 chlorohydrocarbons,
The Pittsburgh Plate Glass process is described in several
patents issued in Britain, France, and the United States. U.S.
Patent Ncs. 3,267,162 and 3,288,868 disclose the use of a
fluid bed catalytic oxychlorination process for the conversion of
ethylene cichloride and other €2 chlorohydrocarbons to trichloro-
ethylene end. perchloroethylene. This process is operated at a
temperature of about 400°C. The trade literature indicates that
the yield of products is about 85%. The balance probably goes to
•carbon oxides and waste chlorocarbons such as hexachlorobutadiene
and hexacMorobenzene .
20
-------
The process also appears to offer the possibility of
processing vinyl chloride wastes to useful products.
The results of the industry survey show that at least two
and probably three companies are processing their vinyl chloride
monomer wastes by chlorination to solvents. This appears
logical in that three of the major vinyl chloride producers are
also solvent producers.
However, there is a total of 50-50MM Ibs/yr. (23,000-27,000
metric tons) of vinyl' chloride waste that could be made available
for chlorolysis that are currently projected for incineration at sea.
In summary, it is possible to process a portion of the vinyl
chloride monomer wastes by presently known technologies. However,
each of these technologies produces residues more difficult to
process. These residues must be processed either by chlorolysis
or incineration.
21
-------
Impact of Chlorolysis on the Carbon Tetrachloride Market
The total industry capacity for carbon tetrachloride is
estimated to be about 540,000 U.S. tons per year (*»491,000 metric
tons) . However, this capacity is flexible because perchloroethylene
and carbor tetrachloride are coproducts. The ratio of these
products can be varied to satisfy swings in the marketplace. The
known producers and their estimated capacities are shown in-
Table X.
About 80 per cent of the carbon tetrachloride produced is
used in the manufacture of Freon-11 and 12 for refrigeration and
propellan't usage. The balance of 20 per cent is used for
miscellansous applications and export.
Growth of the carbon tetrachloride market has been closely
related tD the growth of the fluorocarbon market. The growth of
this market through 1975 has been about 6 per cent per year. The
fastest growth has been experienced by the propellant application.
This represents some 40 per cent of the fluorocarbon market.
However, the recent concern about the depletion of the ozone
layer attributed to the C^ fluorocarbons is projected to slow the
22
-------
growth of the propellent market.. This slow down is expected to
continue until the ozone depletion question is resolved.
Introduction of additional carbon tetrachloride capacity
during this period looks at first glance to be undesirable.
However, it could be accomplished with the proper pricing
strategy.
A chlorolysis unit rated at 25,000 U.S. tons/year of residues
would produce about 92,000 U.S. tons (83,640 metric tons) of carbon
tetrachloride. This represents 17 per cent of the current
industry capacity. This influx of new capacity could have
significant effect upon the producers which still use the carbon
bisulfide route for:manufacture.
However the future of the carbon tetrachloride market is
undefinable until the ozone depletion situation is resolved.
23
-------
Impact of Chlorolysis on the Carbonyl Chloride Market
The total industry capacity for carbonyl chloride is
estimated to be about 620,000 U.S. tons per year (^565,000 metric
tons). ThB known producers and their estimated capacities are
shown in Table XI. Most of this capacity is used captively
for the manufacture of isocyanates, carbamates and polycarbonates.
The major consumer is the isocyanate industry which is projected to
grow at the rate of 10-21 per cent per year. Expansions in
carbonyl chloride capacity will be made consistent with the
growth in isocyanate capacity.
Hence, by 1980 the additional carbonyl chloride capacity
required is estimated to be 500MM Ibs/yr. (^230,000 metric tons).
It is estimated that a chlorolysis unit to process 25,000
tons/yr. cf residue could produce a maximum of about 15,000 U.S.
tons (""13,600 metric tons) of carbonyl chloride. This volume of
material could be readily absorbed into the isocyanate market.
However, the chlorohydrocarbon wastes identified in this
study do not contain oxygen and would not yield carbonyl chloride.
24
-------
Injection of oxygen into the reactor would be necessary to induce
the formation of carbonyl chloride. This technique must be
explored experimentally to verify that it can be used.
25
-------
Impact of Chlorolysis on the Hydrogen Chloride Market
The total industry capacity for 100 per cent hydrochloric
acid is about 2 . OMM U.S. tons per year (-"1.8MM metric tons) .
About 85 per cent of this capacity is by-product from other
processes. Less than half of the capacity is used in definable
markets. The balance is either used in oxyhydrochlorination
processes or it is neutralized.
Thus, the introduction of new hydrochloric acid capacity could
not be effected economically. A chlorolysis unit processing
25,000 tor.s per year (^22,700 metric tons) of vinyl chloride
residues would produce a maximum of about 30,500 U;S. tons of
hydrochloric acid (^27,700 metric tons) . Effective utilization
of this hydrochloric- acid within the confines of a chlorolysis
plant is very desirable. The options available for this need
include oxyhydrochlorination of ethylene to make saleable ethylene
dichlorida or conversion back to chlorine by either the Kel Chlor
process or the Uhde electrolysis process.
Facilities to accomplish this objective should be estimated
as part of the chlorolysis plant.
26
-------
Recommendations for Chlorolysis
A. Plant capacity and process variations
The waste chlorohydrocarbon supply indicates that a plant
with a capacity to process 25,000 U.S. tons/year of waste
would be viable. This capacity should be adequate to serve
the needs of the industry when allowance is made for
incineration facilities that are projected to come
on stream in the time period required to construct a
chlorolysis plant.
The reactor in this plant should be of a segmented
design with two to three spare sections provided for
flexibility in use and to permit change out of corroded
sections.
A base case design for the plant should be made with
a feed that is a mixture containing 60 per cent by weight
VCM wastes and 40 per cent by weight chlorinated solvents
wastes. The effect of variations in feedstock composition
upon reactor capacity should also be examined.
27
-------
Suggested cases for examination are:
1. 100 per cent vinyl chloride wastes.
2. Solvent wastes with minimum vinyl
chloride wastes.
The second case is proposed to evaluate the limiting
composition that can be fed to the reactor and still
hav
-------
B. Pretreatment/Purification Needs
Pretreatment of all wastes will be necessary. A
combination system providing filtration and distillation
capability is recommended. This system must contain an
autoclave for use in extracting pesticides from their
inert carriers.
Purification of the carbon tetrachloride to meet
the specifications for fluorocarbon use is recommended
because this is the market in which the product will
most likely move. Purification of carbonyl chloride
will be necessary to make it acceptable for use in
isocyanate processes. Removal of chlorine, hydrogen
chloride, and carbon tetrachloride to less than 1.0 weight
per cent is recommended.
C. Site Locations
The majority of the chlorohydrocarbon wastes and
chlorine producers are located in the Gulf Coast area
ranging from Corpus Christi, Texas to New Orleans, Louisiana.
29
-------
The major concentration is from Houston, Texas to
New Orleans.
Location of a chlorolysis plant anywhere in the
area between Houston and New Orleans would be suitable.
The location must be accessible by both water and rail
transport. The Bay St. Louis, Mississippi area which
offers these characteristics is recommended for
consideration. However, an economic study is recommended
to isstablish the best compromise on freight rates.
D. Modi; of Implementation
A chlorolysis unit should best be implemented with
a dual parallel reactor system such that at least one
reactor can 'be in operation at all times. This mode of
implementation is recommended because future wastes as
yet undefined could result in serious corrosion problems
and/or require frequent shutdowns.
Installation of the carbonyl chloride recovery and
packaging system should be deferred until it can be
30
-------
appropriately scheduled to coincide with a significant
growth in the isocyanate area. The capacity of this
system should not exceed 15,000 U.S. tons/year (13,600
metri c tons) .
A thermal incinerator capable of processing wastes
that are not acceptable for chlorolysis is recommended
for inclusion in the system. This should be capable of
v
incinerating the carbonaceous material recovered from
the pretreatment step of the chlorolysis unit.
E. Relative Cost Advantages
A chlorolysis plant designed for a capacity of
25,000 U.S. tons/year (22,700 metric tons) would produce
92,000 U.S. tons/year (83,600 metric tons) of carbon
tetrachloride and 30,500 U.S. tons/year (27,700 metric
tons) of hydrogen chloride. The sale of carbon tetrachloride
at $320-400 per U.S. ton would produce a gross sales income
of $29.5-36.8MM per year. The administrative, sales, and
general expenses for large volume contractual sales is
estimated to be about 10 per cent.
31
-------
The manufacturing cost was estimated as follows:
Raw Materials
We.stes @ $100 per ton $(2,500,000)
Chlorine @ $150 per ton 97,500 tons 14,640,000
Miscellaneous 1,OOP,OOP
Total $13,140,000'
Cost of Conversion 8,750,000
Total production cost $21,890,000
On this basis, the gross profit before tax would be in
the range of $4.5-llMM for capacity operation.
The investment projected for the chlorolysis plant
is estimated to be about $20MM for the primary facilities.
The auxiliary facilities for use of the hydrogen chloride,
pretreatment and incineration facilities are estimated
to add an additional $20MM for a total of $40MM. The
return on this investment at capacity operation is estimated
to be in the range of 5-14 per cent.
The magnitude of the return on investment projected
for the established solvents processes is about 10 per cent.
Thus, the chlorolysis process appears to be competitive with
established technology.
32
-------
Incineration on the other hand is a losing proposi-
tion when no effort is made to recover chlorine. Typically,
shipboard incineration of 13,000 tons/year (11,800 metric
tons) of vinyl chloride wastes would cost about $1.6MM at
a processing cost of $120 per U.S. ton.
In summary, a large scale regional chlorolysis plant
provides the potential for economics competitive with
existing solvents processes.
33
-------
Bibliography
1. Hot Option for Disposal of Hydrocarbon Wastes
Chemical Week, April 19, 1972, page 37.
2. Process for the Manufacture of Carbon Tetrachloride
Krekeler et.al., U.S. Patent NO. 3,651,157 March 21, 1972
3. Process for the Manufacture of Carbon Tetrachloride
Krekeler et.al., U.S. Patent NO. 3,676,508 July 11, 1972.
4. The Rich Pressure Chlorolysis of Hydrocarbons to Carbon
Tetrad".loride--A New Process for the Utilization of
Chlorinated Hydrocarbon Wastes.
Krekel«'.r, Schmitz, and Rebhan, Hoechst, A.G.
Presented at the National Conference on the Management and
Disposal of Residues, February 3-5, 1975, Washington, D.C.
5. Synthetic Organic Chemicals, Pesticides, and Related Products,
United States Tariff Commission Report 1974.
6. World Wide Pesticide Inventory, Solid Waste Management
Division, U.S. Army Environmental Hygiene Agency,
Aberdeen Proving Ground, Maryland.
7. Chemical Marketing Reporter, August 5, 1976
8. Energy Conservation in The Chemical Industry Through New
Process Development—The B. F. Goodrich Catoxid Process.
Fabstein and Elder, Presented at the Federal Energy
Administration, Project Independence Hearing, San Francisco,
California, October 7, 1974,
34
-------
Table 1
Chlorohvdrocarbon Wastes
VCM Producers
EPA
Region
Waste Volume
MM Ib/yr
Compos ition
Current
Treatment
VI
VI
VI
VI
-VI
9.0
7.0
11.0
27.0
6.0
10.0
5.0
10.0
25.0
18.0
10.6
19.3
CH1.9C11.1 (lights)
CH1.4C11.2 (heavies)
Incineration/
Chlorinolysis
CH1 5c:l-0.8 (heavies) Incineration
CH1.9C11.1 (lights)
CH2.1C10.9 (lights)
CH1.5cll.5 (heavies)
Chlorinolysis
Incineration/
Chlorinolysis
4clQ.8 (heavies) Incineration
(heavies)
(lights)
(heavies)
Incineration
Used in another
process
Partial recovery/
incineration
VII
yn
IV
TOTAL
29.9
12.0
9.0
25.0
151.5
MM Ib/yr
CH1.6C10.7 (heavies) Chlorinolysis
CH1".5C10.8 (heavies) Chlorinolysis
(heavies)
Incineration
7 (heavies) Incineration
35
-------
EPA
Region
Table I (Cont'd)
Chlorohydrocarbon Wastes
Solvent Producers
Waste Volume
MM Ib/yr
Composition
Current
Treatment
IV
0.48
C6H6C16
Landfill
VI
10.0
C4C16
Incine ration
VI
20.0
Deep Well
VI
3 .0
C4C16
Incineration
VI
10.0
43.0
C4C16
Burial
36
-------
Table IA
COMPOSITION OF VCM & SOLVENT WASTES
Component
VCM
Lights
% by wt.
Heavies
% by wt .
SOLVENTS
% by wt.
CHC13
CC14
9.92
16.85
0.7
C2H5C1
<"2^4<-'^2
C2H3C13
C2H3C1
C2H2C12
C2HC13
C2H2C14
3 .76
30.2
10.85
4.45
2 .86
2 .2
48 .5
0.5
2 .3
25.
C3H3C13
C3H4C12
C3H6C12
0.7
2 .7
1.7
C4H5C1
C4H6C12
C4C16
14.5
2.7
26.0
65.0
G6H6-xC1x
Unknowns
6.21
0.4
3 .9
8.1
10.0
Total
100 .0
100.0
100 .0
37
-------
NAME
Table II
SULFUR CONTAINING PESTICIDES
TRADE NAME
Antu
MFC .
Penick
PRODUCT FORM.
B , CO
FORMULA
(solid)
Asulam
Asulox
May and Baker L,CO
C8H10N2°4S
(solid)
Diallate
Avadex
Monsanto
EC,G
CgH17OSCl2N
(liquid)
U)
00
Triallate
Captan
Avadex BW
Far Go
Orthocide
Monsanto
Stauffer
Chevron
EC,G
D, WP
CgH16OSCl3N
(ii qui d)
C9H602SC13N
(solid)
Dexon
Chemagro
G,WP
C8H10N3S03Na
(solid)
Capta f ol
Di folatan
Chevron
D, T, F
C1QH702C14NS
(solid)
Endosulfan
Thiodan
FMC
D,EC,T,WP,G,CO
CgH4Cl&03S
(solid)
Ep tarn
Stauffer
EC , G
CgH19NOS
(1iquid)
Ethion
FMC
D,EC,G,T,WP
C9H22°4?2S4
(1iqu id)
Ametryne
Evik
Ge sapex
Geigy
WP
C8H13N5S
(solid)
Ferbam
FMC
Pennwalt
WP
C9H18N3S6Fe
(powder)
Folpe t
Phaltan
Chevron
Stauffer
D , WP
C9H4°2KSC13
(solid)
-------
Table II (Cont'd)
SULFUR CONTAINING PESTICIDES
NAME
Maneb
Thiabendazole
Methomyl
MCA600
Nabam
DO-14
Mo 1 inate
Phenothiozine
Nitralin
Oxycarboxin
TRADE NAME
Lethan 384
Manzate
Tersan LSR
Dithane M-22
Mertect
Lannate
Mobam
Morestan
Dithane D-14
Dithane A-40
Niacide
Omite
Ordram
*
Planavin
Plan tvax
MFG. PRODUCT FORM.
Rohm and Haas CO, PC
DuPont WP
Rohm and Haas
Pennwalt
Merck WP,F
DuPont SP
Mobil G,WP
Chemagro WP
Rohm and Haas D,CO,WP
FMC
FMC D,WP
Uniroyal D,EC,WP
Stauffer EC,FM,G
West T,WP
Shell L,WP
Uniroyal L,WP
TECHNICAL
FORMULA
C9H1?02NS
(oil)
[C4H6N2S4]X
(solid)
C HNS
10*7 3
(solid)
C5H10°2N2S
(solid)
C10H702NS
(solid)
CloH6ON2S2
(solid)
C4H6N2S4Na2
(solid)
(solid)
C19H2604S
( 1 iquid )
CgH^ 7ONS
(liquid)
C12HgNS
(solid)
C13K19°6N3S
(solid)
Ci2H1304;.JS
(solid)
-------
MRME
Prome tryne
Cycloate
Butylate
Te trachlorothiophene
Aldicarb
Terbutryn
Tetradi fon
Thiram
Pebulate
Metham-Sodium
Table II (Conf d)
SULFUR CONTAINING PESTICIDES
TRADE NAME MFG.
Geigy
Caparol
Gesagayd
Ro-Neet
Sutan
Phenphene
Temik
Igran SOW
GS14260
Terrazole
Tedion
Thanite
Arasam
Thylate
Tersan
Ti Ham
Vapam
Vegadex
Stauffe r
S tauffer
Pennwalt
Carbide
Geigy
Olin
PRODUCT FORM.
WP
EC,G
EC,G
EC
WP
EC,G.L,S,T,WP
FMC D,EC,WP
Thomas Hayward
Hercules T
DuPont
Stauffer
Stauffer
Monsanto
D,WP
EC , G
EC , G
TECHNICAL
FORMULA
(solid)
C11H21ONS
(1iqui d)
C11H23ONS
(liquid)
c4ci4s
(solid)
C7H1402N2S
(solid)
C10H19N5S
(solid)
C5H5N2C13S
(1iquid)
C12H602C14S
(solid)
C12H15°2NS
(liquid)
C6H12N2S4
(solid)
C1QH21ONS
(1iquid)
C2H8NS202Na
. (solid)
C8U14NC1S2
(1iquid)
-------
Table II (Cont'd)
SULFUR CONTAINING PESTICIDE!^
TECHNICAL
NAME TRADE NAME MFG. PRODUCT FORM. FORMULA
Vernolate Vernam Stauffer EC,G C1QH21ONS
(1iqui d)
Zinck FMC D,WP [C4H6N2S4]xZny
Rohm and Haas (solid)
S tauffer
-------
Table III
PHOSPHOROUS AND SULFUR CONTAINING PESTICIDES
NAME
TRADE NAME
Abate
Ak ton
MFG.
Cyanami d
Shell
PRODUCT FORM.
EC , G
EC
TECHNICAL
FORMULA
C16H20P2°6S3
(liquid)
C12Hi403PSCl3
(1iqu id)
Fensulfathion
Diazinon
Aspon
Be tason
Pref ar
Dasanit
Def
Sarolex
Alf atox
Bas udin
Stauffer
Stauffer
Chemagro
Chemagro
Geigy
EC,G,FM
EC,FM,G
EC,L,T
EC
D , EC , G , PC , S , WP
( liquid )
C14H2404NFS3
( liquid )
C11H17°4PS2
(li qua d)
C H P O S*
(li qua d)
C12H21N2°3PS
(li qua d)
Dimethoate
Cygon
Rogor
Cyanamid
Mon tedi son
Sumitomo
EC , WP
(solid)
Dioxathion
Disu1fo ton
Chlopyrifos
Dowco 179
DeInav
Di sys ton
Dursban
Dyfonate
Hercules
Chemay ro
Dow
Stauffer
EC
FM,G.L,T
EC,G,T,WP
G,EC
C12H26°6P2S4
(liquid)
C8H18°2PS2
(1iqu id)
C9H11O3C13NPS
(solid)
CLOH15OPS2
( liquid)
EPN
DuPont
E C,WP,G,T
C14H14N04PS
(solid)
-------
Table III (Cont'd)
NAME
Fenthion
Azenphosmethyl
Malathion
Demeton-0-Methyl
Sulfoxide
Methyl Parathion
Prophos
Ortho 9006
Methamidophos
Acephate
Parathion
PHOSPHOROUS AND SULFUR CONTAINING PESTICIDES
TRADE NAME
Baytex
Entex
Folex
Mexphas
Gophacide
Guthion
Imidan
Cythion
Meta-SystoxR
Metron
Methyl Niran
Folidol M
Me tacide
Nitrox
Mocap
Mon itor
Tamaron
Orthene
MFG. PRODUCT FORM.
Chemagro EC , G , T
Mobil EC
Chemagro T , B
Chemagro EC,WP,L
Stauf fer EC,WP
Cyanamid T,CO,EC,WP,D
Chemagro EC,L,T
Monsanto EC,WP,S
Stauf fer
Kerr McGee
Mobil EC,G
Chevron L,T
Chemagro
Chevron G,PC
Monsanto D,EC,G,L,WP
Stauf fer
Kerr McGee
TECHNICAL
FORMULA
C10H1503PS
( 1 iqui d )
Cl2H27ps3
( 1 iquid )
C14H13°2C12N
(solid)
C12H16°3N3PS
(solid)
CllH1204NPS2
(solid)
C10H1906PS2
( liquid)
C6H1504PS2
(liquid)
C8H1005NPS
C8H1902PS2
( 1 iquid)
C2H302NPS
(solid)
C4H1003NPS
(solid)
C10H1405NPS
(liquid )
-------
Table III (Cont'd)
PHOSPHOROUS AND SULFUR CONTAINING PESTICIDES
Phorate
Ronnel
Methidiathon
Demeton
Carbophenothion
Dichlorofenthion
Thionazin
TRADE NAME
Thiame t
Korlan
Trolene
Nankor
Supra cide
Systox
Trithion
VC-13
Zinophos
MFC- .
Cyanaraid
vow
Ge igy
Chemagro
Stauffer
Mobil
Cyanamid
PRODUCT FORM.
EC , G , L , PC , S
EC
EC , L
EC,WP,G
EC
EC,G
TECHNICAL
FORMULA
C7H1702PS3
(liquid)
C8H803C13PS
(solid)
(solid)
C8H19°3PS2
(1iquid)
C11H16°2C1FS3
(1iquid)
(liqu id)
C8H1303N2PS
(1 i a u i d )
-------
Table IV
PHOSPHOROUS CONTAINING PESTICIDES
Ui
NAME
Monocrotophos
Dicrotophos
Dichlorvas
Trichlorfon
TRADE NAME
Azodrin
Bidrin
Ciodrin
Vapona
Dylox
Dipterex
Gardona
Rabon
MFC .
Shell
Shell
Shell
Shell
Chemagro
Shell
PRODUCT FORM .
L
L
D,EC
EC, G , L , S , T
G , L, S , SP
D,S . WP
TECHNICAL
FO RK'JLA
CyH 05PN
(I iqui d )
C8HI505rN
(liquid)
C14H1906P
(1 iqui d)
C4H704PC12
(liquid)
C4H804PC13
(solid)
C10H902PC14
(solid)
Me vinphos
Phosdrin
Shell
EC,L,S,T
(liquid)
Naled
Dibron
Chevron
EC,L,T
C4H704Cl2Br2P
(solid)
Phos fon
Mobil
D , L
C19H32C13P
(solid)
Phosphamidon
Dimecron
Chevron
D,L,S,T
C10H19°5NPC1
(liquid)
Ruclene
Dow
EC ,CO
C12H22O3NC1P
(solid)
-------
Table V
NITROGEN CONTAINING PESTICIDES
NAME
TRADE NAME
MFC .
PRODUCT FORM.
TECHNICAL
FORMULA
Atrazine
Aatrex
Geigy
WP, L
Chi oramben
Amiben
Amchem
G, L, S
C7H5°2C12
(solid)
Te rbutol
Azak
He rcules
G, WP
C17H27N°2
(solid)
Barban
Carbyne
Gulf
EC
C11H9N02C12
(1iqui d)
Propoxur
Baygon
Chemagro
D,EC,G,L,PC,
T , WP
C11H15°3N
(solid)
Chlonitrolid
Bayluscide
Chemagro
WP ,G
C15H15°5N3C12
(solid)
Benomyl
Benlate
Tersan 1991
DuPont
WP
C13H18N4°3
(solid)
Phenmedipham
Be tanal
Nor.Am.
EC
C16H16N2°4
(solid)
Binapacry1
Morocide
FMC
Hoechst
D,WP
C15H17°6N2
(solid)
Bladex
Shell
G,WP
C9H13N6C1
(solid)
Bromacil
Hyvar X
Hyvar X-L
Hyvar X-P
Krovar I
Krovar II
DuPont
WP , S,P
(solid)
-------
Table V (Cont1d)
NAME
NITROGEN CONTAINING PESTICIDES
TRADE NAME MFG. PRODUCT FORM.
TECHNICAL
FORMULA
Bromoxynil
Bromoxynil
Octanoate
Hetalkamate
Carbaryl
Carbofuran
Formetanate
Propham
Chlorbromuron
Chlordimeform
Chloropicrin
Chloroxucon
Chlorpropham
Brominal
Buctril
Bux Ten
Sevin
Furadan
Carzol
Chem Hoe
Maloran
Fundal
Galecron
Chlor-O-Pic
Picfume
Tenoran
Chloro IPC
CIPC
Amchem
Chipman
Chevron
Carbide
FMC
Nor.Am.
PPG
Geigy
Nor.Am.
Geigy
Great Lakes
Niklor
Dow
Geigy
PPG
EC
EC
EC,G,T
D, FM,G,L,P,T,
WP
G,F
SP
EC,G,F
G, WP
D,EC ,SP
L , PC
WP
EC,G
(solid)
C15H17NBr2°2
(1iqui d)
C13H19°2N
(solid)
C12H11°2N
(solid)
C12H14°3N
(solid)
:11H15°2N3
(solid)
C10H13°2N
(solid)
C9H10°2N2ClBr
(solid)
C10H13N2C1
(solid)
( 1 iquid)
(solid)
(solid)
-------
NAME
Table V (Cont'd)
NITROGEN CONTAINING PESTICIDES
TRADE NAME
MFG.
PRODUCT FORM.
TECHNICAL
FORMULA
Dinitramine
Cobex
U.S. Borax
EC
C11H13°4:"V3
(solid)
Cycloheximide
Acti Dione
TUCO
WP
C15H15°4N
(solid)
Cycocel
Cyanami d
C5H13NC12
(solid)
oo
Dodine
Chlorothalonil
DCHA
Cyprex
MeIprex
Daconil 2787
Bravo
Bo tran
Cyanamid
Diamond
Shamrock
TUCO
WP
C,WP,F
D,WP
C15H3°2N3
(solid)
(solid)
C6H3N2°2C12
(solid)
Deet
Det
Diethyl toluamide
Metadelphene
MGK
Chem Form
Her cules
PC ,S , L
(1 iquid)
Dichlobenil
Casoron
Thompson
Hayward
G , WP
(solid)
Dinoseb
S inox
Sinox General
Basani te
Caldox
Gebutor
Subitex
Dow
BASF
Hoechst
EC,S
C10H12°5N2
(liquid)
Diphenamid
Dyraid
Enide
Blanco
TUCO
L,WP,G
C16H17°N
(solid)
Diphenylamine
Cyanamide
WP
C12H11N
(solid)
-------
NAME
Table V (Cont'd)
NITROGEN CONTAINING PESTICIDES
TRADE NAME
MFC .
PRODUCT FORM.
TECHNICAL
FORMULA
Diuron
Kamex
Karmex DL
Krovar I
Krovar II
DuPont
WP,F
C9H10°-'2C12
(solid)
Dyrene
Chemagro
G, WP
C9H5N4C13
(solid)
Fluometuron
Cotoran
Geigy
WP
C10H11°N2F3
( sol id)
Fluorodifen
Ge igy
EC,G,WP
C13H7N2°5F3
(solid)
Norea
Herban
He rculos
WP
C13H20°N2
(solid)
I sopropalin
PaarIan
Elanco
EC
:15H23°4N3
(1iqu i d)
Karathane
Dinocap
Arathane
Mildex
Rohm & Haas
WP,G,C
C18H24°6N2
(liquid)
Alachlor
Lasso
Monsanto
EC ,G
C14H20°2NC1
(1iquid)
Linuron
Lorox
Afalon
DuPon t
Hoe chs t
G, WP
C9H10°2N2C12
(solid)
Maleic Hydrazido
MH-30
Sucker Stuff
Chem.Form
Ansul
Uniroya 1
L,S
C4H4°2N2
(solid)
Metrobromuron
Geigy
G, WP
(solid)
-------
NAME
Table V (Cont ' d )
NITROGEN CONTAINING PESTICIDES
TRADE NAME
MFG.
PRODUCT FORM.
TECHNICAL
FORMULA
. P r . s
C . _ H _ _ 0 _ N
1 / £. _> ^
(so lid)
MGK 326
MGK
T, s, PC
(1iqu id)
Monuron
Tel var
DuPon t
WP, F
C9H11°N2C1
(solid)
Monuron TCA
Urox
Allied
EC,G,L
C11H12°3N2C14
(solid)
tn
O
Neburon
Kloben
DuPont
WP
(solid)
Tetramethrin
Neo Pynamin
FMC
EC,PC,S,T,D
C19H22°4N
(solid)
Nico tine
Chcm. Form. L
C10H14N2
(1iqui d)
Nitrofen
TOK
Rohm & Haas EC,WP
C12H7°3NC12
(solid)
Cypraz ine
Paraquat
Outfox
Gramoxone
Gulf
Chevron
EC
C9H14N5C1
( 1 iqui d)
+ 2
(solid)
C H M
U12M14 "2
Parinol
Parnon
El anco
(solid)
PCNB
Terra clor
Brassico L
Olin
Hoechst
:,D,EC,FM, G,L, WP
(solid)
-------
Table V (Cont'd)
NITROGEN CONTAINING PESTICIDES
NAME
TRADE NAME
MFG.
PRODUCT FORM.
TECHNICAL
FORMULA
Picloram
Tordon
Dow
CO
C6H3°2N2C13
(solid)
Piperalin
Pipron
Elanco
EC
C16H21°2NC12
(liquid)
Princep
Geigy
SP
(solid)
Propanil
Rogue
Stam F-34
Monsanto EC
Rohm & Haas
(solid)
Propazine
Milogard
Gesamil
Ge igy
WP
(solid)
Pyrazon
Pyramin
BASF
WP
C10H8°N3C1
(solid)
Propachlor
Ramrod
Mons an to
G, WP
C11H14°NC1
(solid)
Randox
Monsan to
EC, G
(liquid)
SADH
Alar .85
Uni royal
C,L,SP
C6H12°3N2
(so lid)
Siduron
Tupersan
DuPont
WP
C14H20°N2
(solid)
Ethoxyquin
Stop Scald
Monsanto
EC
'C14H18°N
(liquid)
Karbutilate
Tandex
FMC
G, WP
C14H21°3N3
(solid)
-------
Table V (Cont'd]
*r>r\/-ITM rr*\Tva TM T tan
NAME
2,3,6-TBA
Terbacil
cn
to
Carboxin
Dowco 139
TRADE NAME
Trysben
Sinbar
Urab
Vi tavax
Ze ctran
TECHNICAL
MFG. PRODUCT FORM. FORMULA
DuPont L,S CgHlo02NCl3
(solid)
DuPont V^JP C9H13°2N2C1
(solid)
Allied EC,L,P Cl 1H13°3N2C13
(solid)
Uniroyal G , WP C12K13°3N
(solid)
Dow EC,S,WP C H QON
J. Z J. O 4. £.
(solid)
-------
Table VI
OXYGEN AND CHLORINE CONTAINING PESTICIDES
NAME
TRADE NAME
MFG.
PRODUCT FORM.
TECHNICAL
FORMULA
Chloropropylate
Acaralate
Geigy
EC
C17"lG°3C12
(solid)
Aldrin
Shell
G , S , L
C12"6C14
(solid)
Allethrin
Pynamin
Sumitomo
C19H26°3
(1iquid)
Ui
u>
Banvel
Dicamba
VeIsicol
G, S
C8H6°3C12
(solid)
Chlordane
Chlordane
Velsicol
D,EC,G,WP
C11H4C18
(liquid)
Chlorobenzilate
Acaraben
Geigy
EC
C16H14°3C12
(liquid)
Chloroneb
2,4-D
Demosan 65W
Tersan SP
2,4,D
DuPont
Thompson Hayward
Dow
Chipman
Diamond
WP
EC,G,L,T
C8H8°2C12
(solid)
C8H6°3C12
(solid)
DACTHAL
DACTHAL
Diamond
G, WP
T nC/ A
10 6 4 4
(solid)
DALAPON
2,4-DB
Basfapon
Dowpon
Butoxone
BASF
Dow
Chipman
SP, C
CO,EC,L,S
C3H4°2C12
(solid)
C10H10°3C12
(solid)
-------
Table VI (Cont'd)
ui
NAME
DD
DDT
Dichlone
Dichlorprop
Dico fol
Dieldrin
Dimethrin
Diphacin
D-trans Allethrin
Endothall
Endr in
Entocon ER-512
OXV5SI? A"S CHLORIDE COMTAINTMr: PKSTTCIDES
TRADE NAME MFG. PRODUCT FO RM.
Vidden D
Telone &
Te lone C
DDT
Phygon
Kelthane
Diphacinone
Bioallethrin
Aquathol
Shell
Dow
Montrose
FMC
Diamond
Rohm & Haas
Shell
MGK
Velsi co1
MGK
PennwaIt
Shell
Velsicol
Zoecon
EC,L,T,WP
D, WP
EC
EC, WP
D,EC,G,WP
EC, T
D, CO
T,S,PC
CO, G
D,EC,G,WP
EC, G
TECHNICAL
FORMULA
C3H6C12
(liquid)
C14H9C15
(solid)
C10H3°2C12
(solid)
C9H8°3C12
(solid)
C14H9°C15
(solid)
(solid)
C19H26°2
( liquid)
C23H15°3
(solid)
C19H27°3
(1iquid)
C8H4°5
(solid)
(solid)
C17H30°2
V1iquid)
-------
Table VI (Cont'd)
(J\
Ui
NAME
Entocon ZR-515
Erbon
Ethylene Dichloride
Ethylhexanediol
Fortified Hexachloride
Glytac
Heptachlor
Indalone
Kepone
Lindane
MCPA
MCPB
OXYGEN AND CHLORINE CONTAINING PESTICIDES
TRADE NAME MFG. PRODUCT FORM.
Zoecon EC , G
Baron Dow EC
Diamond L
Rutgers 612 Carbide L
BHC Hooker T
EGT Oxychem L,S
Velsicol D,EC,G
Butopyronoxyl FMC L
TECHNICAL
FORMULA
°1
(
Cl
C2
(
C3
(
C6
°4
8H32°3
liquid )
1H9°3C15
(solid)
H4C12
liquid)
Hia°2
1 iquid )
H6C16
(solid)
H 0 Cl
44 6
(solid)
C10H4C17
(solid)
Cl
1H17°4
Y-BHC (90%)
Rhomene
Chiptox
Rhonox
Thistrol
Cen-Trol
Allied
Hooker
Chipman
Diamond
Amchem
Chipman
D,W,B
C,T
EC
EC,L,S,CO
(liquid)
(solid)
C6H6C16
(solid)
(solid)
Cll"l3°3C1
(solid)
-------
Table VI (Cont'd)
NAME
OXYGEN AND CHLORINE CONTAINING PESTICIDES
"TRADE NAME'
fKUUUUT fUKM.
TECHNICAL
c u KMLi Jj /\
MCPP
VtPar
Vineland
S,EC,T
C10H11°3C1
(solid)
Methcxychlor
Marl ate
Moxie
DuPont
Ansul
Chem. Form.
D,EC ,G
WP ,T
C16H15°2C13
(solid)
01
Mirex
Orthodichlorobenzene
Orthopheny1phenol
1,2 DCS.
Dowicide 1
Hooker
Monsan to
Hooker
Dow
L, PC
Flakes
(solid)
C2H4C12
(liquid)
C12H5°
(solid)
Paradichlorobenzene
Santochlor
PDB
Monsanto
PPG
Allied
C6H4C12
(solid)
PCP
Santobri te
Monsanto
Dow
Vulcan
P,S,EC,WP
CCHOC1C
b D
(solid]
Pentac
Hooker
WP
cioclio
(solid)
Perthane
Rohm S Haas
EC,WP,D
C18H20C12
(solid)
Piperonyl butoxide
Butacide
FMC
MGK
D,WP,T,S
PC
C18H30°5
(liauid)
Protect
Gulf
C12H5°3
(solid)
-------
NAME
Table VI (Cont'd)
OXYGEN AND CHLORINE CONTAINING PESTICIDES
TRADE NAME
MFG.
PRODUCT FORM.
TECHNICAL
FORMULA
Pyrethrins
Pyrethrum
FMC
MGK
Prentiss
Penick
D,EC,L,CO
PC
(varied)
(liquid)
Resmethrin
Nia 17370
Chryson
SBP 1382
FMC
Sumitomo
Penick
PC
C22H25°3
(solid)
Rotenone
Silvex
Prentiss D,L,WP
Penick
FMC
Thompson Hayward EC
Dow
C23H19°6
(solid)
C9H7°3C13
(solid)
2,4,5-T
Ded-Weed
Thompson Hayward
Diamond
Dow
EC
C8H5°3C13
(solid)
TCBC
Monsanto
C _ H . C 1 .
74 4
(liquid)
Toxaphene
Hercules
D,EC,G,WP
C9H10C18
(solid)
Warfarin
Coumafene
Dethmor
Penick
Prentiss
D,CO
C19H16°4
(solid)
-------
Table VII
U.S. ARMY PESTICIDES SUITABLE FOR CHLOROLYSIS WITH PRETREATMENT
Quantity
Concentration
Pesticide
DDT
Lindane
DDr.:-Lindane
Ch.Lordane
&
100%
75%
10%
5%
25%
20%
5%
75%
12%
15%
5%
72%
Form
powder
powder
dust
dust
liquid
liquid
liquid
powder
liquid
liquid
dust
liquid
U.S.
2
95
1
6
32
37
2817
2
36
21
25
50
Tons
.47
.8
.32
.3
.4
.5
.0
.0
.0
.0
.0
.0
Metric
2 .
87 .
1 .
5 .
29.
34.
2561 .
1.
32.
19 .
22 .
45.
Tons
25
1
2
7
5
1
0
8
7
1
7
5
2, 4-D
50% liquid
78.0
70.9
2,4,5-T
65.3% liquid
36.0
32 .7
.2 ,4-D/2,4,5-T 33.5% liquid
132.5
120.5
TOTAL
3373.29
3066. 75
58
-------
Table VIII
en
QUALITATIVE PESTICIDE SOLUBILITIES IN SELECTI
Chloropropylate
Aldrin
Banvel
Chlordane
Chloroneb
2,4-D
Dacthal
2,4-DB
DDT
Dichlone
Dichlorprop
Dleldrin
Dimothrin
Diphacin
Endathall
Endrin
Erbon
Heptachlor
Lindane
MCPP
Methoxychlor
Mirex
PCP
Butacide
Rotenone
Silvex
2,4,5-T
TCBC
Toxaphene
Warfarin
DMF Acetone
S
S
S S
S
10%
vs
s . . s
ss ss
282 gpl
MS MS
S S
S
7*
S
S S
s s .
s
s s
s s
s
s
s
s
Alcohol Xylenc
S S
VS MS
S S
S
S
VS
s s
ss s
51 gpl
: MS MS
S S
20%
(MeOH)
SS
S S
S
S S
S
S S
14.3%
VS
S S
S
S (Me OK)
S
S S
S S
MS
B c n 7. c n o
S
S
25%
SS
S
ss
85 gpl
MS
S
0.01%
S
S
S
S
S
S
S
S
ss
Mcthylcne
Chloride
S
SS
MS
S
Carbon
Tet Ether
7%
S
SS
MS
S
s
7.2%
VS
S
MS
S
0.1%
S
s
s
V>0%
s
• s
-------
Table IX
CHLORINE PRODUCERS
Chlor:.ne Producers
Name
Alcoa
Allied Chemical
Diamond Shamrock
Dow Chemical
Du Pont
Ethyl
FMC
Goodrich
Hooker
Kaiser
Linden Chlorine
Mob ay
Monsanto
Olin
Pennwalt
PPG
Shell
Sobin
Stauf f er
Vulcan
Wyandotte
Paper Companies
Other
Total
AND ANNOUNCED EXPANSIONS
C
470
1650
2000
10100
940
640
790
300
1780
535
460
200
250
1625
950
3330
375
310
980
375
1550
690
1180
31480
US Tons/
day
apacity
425
1500
1820
9180
850
580
720
270
1620
485
420
180
225
1475
865
3030
340
280
890
340
1410
625
1070
28600
M Tons/
day
60
-------
Table IX (Cont'd)
CHLORINE PRODUCERS AND ANNOUNCED EXPANSIONS
Announced Chlorine Expansions^
Company
Diamond Shamrock
Hooker
N. L. Industries
Georgia Pacific
PPG
DuPont
Pennwalt
Hooke r
Mobay
Weye rhauser
Dow Chemical
Vulcan
Olin
Total
Capacity
1200
1000
400
220
800
750
1000
200
275
200
120
500
1000
500
1000
600
1000
10765
U.S. Tons/day
On Stream
1974
1974
1978
1974
1975
1977
1977
1977
1977
1975
1975
1976
1977
1978
1979
1977
1978
By permission Chemical Marketing Reporter
61
-------
Allied Che:nical
Dow Chemical
FMC - Allied
Stauffer Cnemical
Vulcan Materials
Table X
CARBON TETRACHLORIDE PRODUCERS
Capacity
US Tons/year Metric Tons/year
4,000
138,000
150 ,000
210,000
38,000
540 ,000
3 ,640
125,500
136,400
191 ,000
34 , 500
491 ,000
By permission Chemical Marketing Reporter
62
-------
Table XI
CARBONYL CHLORIDE PRODUCERS
Capacity
US Tons Metric Tons
Allied Chemical
BASF Wyandotte
Cheme tron
DuPont
General Electric
Mobay
Olin
Rubicon
Union Carbide
Upjohn
49 ,000
28,000
5,000
68,000
30,000
137,500 '
85,000
63,000
55,000
100,000
620,500
45,000
25,500
4,500
61,800
27,300
125,000
77,300
57,300
50,000
91,000
564,700
By permission Chemical Marketing Reporter
63
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
3PA-600/2-76-270
2.
3. RECIPIENT'S ACCESSION NO.
:.. TITLE AND SUBTITLE
CONVERTING CHLOR^;ff¥I>RO£A;RBQN WASTES BY
CHLOROLYSIS
5. REPORT DATE
October 1976
6. PERFORMING ORGANIZATION CODE
i'. AUTHOR(S)
James K. Shiver
8. PERFORMING ORGANIZATION REPORT NO.
). PERFORMING ORGANIZATION NAME AND ADDRESS
Repro Chemical Corporation
.629 K Street, NW
Washington, B.C. 20006
10. PROGRAM ELEMENT NO.
1AB604
11. CONTRACT/GRANT NO.,
68-03-0456
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORTANO PERIOD COVERED
Final; 1/75-6/76
14. SPONSORING AGENCY CODE
EPA-ORD
^.SUPPLEMENTARY NOTES project officers for this report are: M.Samfield, IERL-RTP; and
H.R.Swank, SERL-Athens.
. ABSTRACT
rep0r^ gjves results of an assessment of the magnitude of the waste
chlorohydrocarbon problem in the U.S. , and a study of the applicability of the conver-
sion of this wzjste by chlorolysis as a means of resolving the problem. An estimated
86,400 metric tons per year of chlorohydrocarbon waste is generated in the U.S. A
)ortion of this waste is treated by chlorolysis to solvents, and by incineration. The
mlance is disposed of by deep well injection or burial. The identified waste is a
suitable feeds :ock for a chlorolysis operation if it is pretreated to remove particulate
materials and moisture. Geographically, the waste is generated primarily along the
rulf Coast, from Corpus Christ! to New Orleans. The Gulf Coast concentration
indicates that a regional waste disposal facility (including a chlorolysis unit, a waste
)retreatment unit, and a conventional incineration unit) would be viable. Preparation
of a design and firm capital estimate is recommended as the next step in an overall
irogram leading to such a regional facility.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Vaste Disposal
Chlorohydroc arbons
Chlorine
Incinerators
Waste Treatment
Pesticides
Carbon Tetra-
chloride
Phosgene
Hydrogen Chlo-
ride
Pollution Control
Stationary Sources
Chlorolysis
13B
07C
07B
06F
13. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
68
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-J 3)
64
------- |