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

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                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.

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                                                  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

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                     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

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                      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

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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.

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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.

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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,

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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.

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     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.

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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.

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     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

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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.

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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

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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

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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

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     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

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     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

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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

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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

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(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

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     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

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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

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     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 600C.  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 400C 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

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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 400C.  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

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     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

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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

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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

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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

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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

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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

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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  DevelopmentThe  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
                                                          C8H10N24S
                                                             (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
                                                          C9H224?2S4
                                                            (1iqu id)
         Ametryne
Evik
Ge sapex
Geigy
                                                                             WP
C8H13N5S
  (solid)
         Ferbam
                                                              FMC
                                                              Pennwalt
                                                                             WP
                                                          C9H18N3S6Fe
                                                            (powder)
         Folpe t
Phaltan
Chevron
Stauffer
                                     D , WP
                                                          C9H42KSC13
                                                            (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)
C5H102N2S
(solid)
C10H702NS
(solid)
CloH6ON2S2
(solid)
C4H6N2S4Na2
(solid)

(solid)
C19H2604S
( 1 iquid )
CgH^ 7ONS
(liquid)
C12HgNS
(solid)
C13K196N3S
(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)
                                                         C12H152NS
                                                            (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


                                     C16H20P26S3
                                       (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 )
                                     C11H174PS2
                                       (li qua d)


                                     C H P O S*
                                       (li qua d)
                                     C12H21N23PS
                                        (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
                                     C12H266P2S4
                                       (liquid)


                                     C8H182PS2
                                       (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 )
C14H132C12N
(solid)
C12H163N3PS
(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)

                                                          C8H193PS2
                                                            (1iquid)
C11H162C1FS3
   (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
                     C10H195NPC1
                       (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
                                      C7H52C12
                                        (solid)
Te rbutol
                               Azak
                                                   He rcules
                                     G, WP
                                      C17H27N2
                                        (solid)
Barban
Carbyne
                                                   Gulf
                                                                    EC
                                      C11H9N02C12
                                       (1iqui d)
Propoxur
Baygon
Chemagro
D,EC,G,L,PC,
T , WP
C11H153N
  (solid)
Chlonitrolid
Bayluscide
Chemagro
WP ,G
C15H155N3C12
  (solid)
Benomyl
Benlate
Tersan 1991
                                                   DuPont
                                                                    WP
                                      C13H18N43
                                        (solid)
Phenmedipham
Be tanal
                                                   Nor.Am.
                                                                    EC
                                      C16H16N24
                                        (solid)
Binapacry1
Morocide
FMC
Hoechst
                                     D,WP
                     C15H176N2
                        (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)
                      C15H17NBr22
                       (1iqui d)
C13H192N
  (solid)
                                      C12H112N
                                         (solid)
                                      C12H143N
                                         (solid)
                                       :11H152N3
                                         (solid)
                      C10H132N
                        (solid)
C9H102N2ClBr
   (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
                                                          C11H134:"V3
                                                             (solid)
          Cycloheximide
Acti Dione
                                                             TUCO
                                                                              WP
                                                          C15H154N
                                                             (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
                                                          C15H32N3
                                                             (solid)
                                                              (solid)


                                                          C6H3N22C12
                                                              (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
                                                          C10H125N2
                                                           (liquid)
          Diphenamid
Dyraid
Enide
                    Blanco
                    TUCO
                                                                              L,WP,G
                                                          C16H17N
                                                            (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
                                      C10H11N2F3
                                         ( sol id)
Fluorodifen
                    Ge igy
                                                                    EC,G,WP
                                      C13H7N25F3
                                         (solid)
Norea
                               Herban
                                                   He rculos
                                                                    WP
                                                          C13H20N2
                                                             (solid)
I sopropalin
                               PaarIan
                                                   Elanco
                                                                    EC
                                                           :15H234N3
                                                             (1iqu i d)
                               Karathane
                               Dinocap
                               Arathane
                               Mildex
                                                   Rohm & Haas
                                    WP,G,C
                                       C18H246N2
                                         (liquid)
Alachlor
                               Lasso
                                                   Monsanto
                                                                    EC ,G
                                                          C14H202NC1
                                                             (1iquid)
Linuron
Lorox
Afalon
DuPon t
Hoe chs t
                                                                    G, WP
C9H102N2C12
   (solid)
Maleic Hydrazido
MH-30
Sucker Stuff
Chem.Form
Ansul
Uniroya 1
                                                                    L,S
C4H42N2
   (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
                                                          C9H11N2C1
                                                            (solid)
          Monuron TCA
                                          Urox
                                                              Allied
                                                                              EC,G,L
                                                          C11H123N2C14
                                                            (solid)
tn
O
          Neburon
                                          Kloben
                                                              DuPont
                                                                              WP
                                                                                                      (solid)
          Tetramethrin
Neo Pynamin
                                                              FMC
                                                                              EC,PC,S,T,D
                                      C19H224N
                                         (solid)
                                          Nico tine
                                                              Chcm. Form.     L
                                                          C10H14N2
                                                            (1iqui d)
          Nitrofen
                                          TOK
                                                              Rohm & Haas     EC,WP
                                                          C12H73NC12
                                                            (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
                                                          C6H32N2C13
                                                            (solid)
Piperalin
Pipron
                                                     Elanco
                                                                    EC
                                     C16H212NC12
                                       (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
                                     C10H8N3C1
                                       (solid)
Propachlor
                                Ramrod
                                                     Mons an to
                                    G, WP
                                     C11H14NC1
                                       (solid)
                                 Randox
                                                     Monsan to
                                    EC, G
                                                                                             (liquid)
SADH
                                Alar  .85
                     Uni royal
               C,L,SP
C6H123N2
  (so lid)
Siduron
Tupersan
                                                     DuPont
                                                                    WP
                                     C14H20N2
                                       (solid)
Ethoxyquin
Stop Scald
                                                     Monsanto
                                                                    EC
                                     'C14H18N
                                       (liquid)
Karbutilate
                                Tandex
                                                     FMC
                                    G, WP
                                     C14H213N3
                                       (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 C9H132N2C1
(solid)
Allied EC,L,P Cl 1H133N2C13
(solid)
Uniroyal G , WP C12K133N
(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"lG3C12
                                                           (solid)
                                       Aldrin
                  Shell
                                      G , S , L
                                                        C12"6C14
                                                           (solid)
        Allethrin
Pynamin
                                                         Sumitomo
                                                         C19H263
                                                          (1iquid)
Ui
u>
         Banvel
                                        Dicamba
                  VeIsicol
                                      G, S
C8H63C12
  (solid)
         Chlordane
                                        Chlordane
                  Velsicol
                                      D,EC,G,WP
C11H4C18
 (liquid)
         Chlorobenzilate
                                        Acaraben
                  Geigy
                                                                              EC
                                                         C16H143C12
                                                          (liquid)
         Chloroneb
         2,4-D
Demosan 65W
Tersan SP

2,4,D
                                                         DuPont
                  Thompson Hayward
                  Dow
                  Chipman
                  Diamond
                                                                              WP
                                                                              EC,G,L,T
C8H82C12
    (solid)

C8H63C12
    (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
C3H42C12
    (solid)

C10H103C12
    (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)
C10H32C12
   (solid)
C9H83C12
   (solid)
C14H9C15
   (solid)

   (solid)
                                                                                                   C19H262
                                                                                                    ( liquid)
C23H153
   (solid)
C19H273
  (1iquid)
C8H45
   (solid)

   (solid)
C17H302
  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
8H323
liquid )
1H93C15
(solid)
H4C12
liquid)
Hia2
1 iquid )
H6C16
(solid)
H 0 Cl
44 6
(solid)
C10H4C17
(solid)
Cl
1H174
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"l33C1
                     (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
                                       C10H113C1
                                          (solid)
        Methcxychlor
Marl ate
Moxie
DuPont
Ansul
Chem. Form.
D,EC ,G
WP ,T
C16H152C13
  (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
                   C18H305
                    (liauid)
         Protect
                                                          Gulf
                                                          C12H53
                                                            (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
                                                                                       C22H253
                                                                                          (solid)
Rotenone
Silvex
                  Prentiss             D,L,WP
                  Penick
                  FMC

                  Thompson  Hayward    EC
                  Dow
                                       C23H196
                                          (solid)
                                       C9H73C13
                                          (solid)
2,4,5-T
                               Ded-Weed
                  Thompson Hayward
                  Diamond
                  Dow
                                                                     EC
                                       C8H53C13
                                          (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
C19H164
  (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^;ffI>ROA;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

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