EPA 560/6-77-003
        CHEMICAL MARKET INPUT/OUTPUT ANALYSIS
            OF SELECTED CHEMICAL SUBSTANCES
    TO ASSESS SOURCES OF ENVIRONMENTAL CONTAMINATION
          TASK II. BIPHENYL AND DIPHENYL OXIDE
                         October 1977
                   Office of Toxic Substances
              U.S. Environmental Protection Agency
                   Washington, D.C. 20460

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EPA 560/6-77-003                                                 TR 76-599
                                FINAL REPORT
                        CHEMICAL MARKET INPUT/OUTPUT
             ANALYSIS OF SELECTED CHEMICAL' SUBSTANCES TO ASSESS
                   SOURCES OF ENVIRONMENTAL CONTAMINATION
                    TASK II:  BIPHENYL AND DIPHENYL OXIDE
                              William M. Meylan
                              Philip H. Howard
                      Contract No. 68-01-3224 - Task II
                              SRC No. L1273-07
                                October 1977
                      Project Officer - Thomas E. Kopp
                                Prepared for:

                         Office of Toxic Substances
                    U.S. Environmental Protection Agency
                          Washington, D.C.   20460
                Document is available to the public through the
             National Technical Information Service, Springfield,
                               Virginia   22151.

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                                   NOTICE
     This report has been reviewed by the Office of Toxic Substances,  EPA,




and approved for publication.  Approval does not signify that the contents




necessarily reflect the views and policies of the Environmental Protection




Agency, nor does mention of trade names or commercial products constitute




endorsement or recommendation for use.
                                      ii

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                              Table of Contents                          Page


I.    Introduction                                                          1

II.  Historical Development and Future Outlook                             2

     A.   Historical Development                                           2

          1.   Biphenyl                                                    2
          2.   Diphenyl Oxide                                              4

     B.   Future Outlook                                                   6

          1.   Biphenyl                                                    6
          2.   Diphenyl Oxide                                              7

III. Market Input/Output Data                                              9

     A,   Production                                                       9
     B,.   Importation                                                      12
     C,, .  Exportation                                                      13
     D,,   Use  Patterns                                                     13

IV.  General Manufacturing  and  Production  Technology                       16

     A,.   Biphenyl                                                         16

          1.   Thermal Dehydrogenation of  Benzene                         16

               a.   Manufacture                                           16
               b.   Production  Volumes                                    19
               c.   Economics         ,                                     20
               d.   Environmental Management                              20
               e.   Alternative Biphenyl                                  20

          2.   By-Product  From  Dealkylation of Toluene                    21

               a.   Chemistry                                              21
               b.   Process Description                                   22
               c.   Production  Volumes                                    25
               d.   Environmental Management                              25
               e.   Economics                                              25

          3.   By-Product  From  Partial Oxidation of Benzene               26

               a.   Process Description                                   26

     B,.   Diphenyl  Oxide                                                   26
                                       iii

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                         Table of Contents (Cont'd)                       Page


          1.    By-Product From Chlorobenzene-Phenol Process                26

               a.   Manufacture                                            26
               b.   Production Volumes                                     30
               c.   Shipping                                               31
               d.   Economics                                              31
               e.   Environmental Management                               32

          2.    Catalysis of Phenol                                         32

               a.   Production Volumes                                     33
               b.   Environmental Management                               34
               c.   Economics                                              34

V.   Use and Use Process Technology                                        35

     A.   Biphenyl                                                         35

          1.    Dye Carrier                                                 35

               a.   Manufacture                                            35
               b.   Dye Carrier Use                                        38
               c.   Environmental Management                               40
               d.   Areas of Use                                           41
               e.   Economics                                              41
               f.   Alternative Products                                   41
               g.   Alternative Processes                                  43

          2.    Biphenyl Fungicide in Fruit Packaging                       43

               a.   Manufacture                                            44
               b.   Production Volumes                                     44
               c.   Economics                                              45
               d.   Environmental Management                               45
               e.   Alternatives                                     .      45

          3.   Polychlorinated Biphenyl  (PCB)                              46

               a.   Manufacture                                            46
               b.   Production Volumes                                     46
               c.   Economics                                              46

          4.   Alkylated Biphenyl                                          47

               a.   Isopropylbiphenyl                                      47

                    (i)  Manufacture                                       47
                                        iv

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                    Table of  Contents  (Cont'd)                       Page
             (ii)    Production Volumes and Uses                      47
             (ill)   Economics                                        48

          b.    Methylbiphenyl                                        48
          c.    Ethyl- and Butylbiphenyl                              48

     5.    Eutectic  Heat Transfer Fluid                               48
     6.    Polybrominated Biphenyl (PBB)                              48

          a.    Manufacture                                           49
          b.    Production Volumes                             .       49
          c.    Economics                                             49
          d.    Alternatives                                          49

B,   Diphenyl Oxide                                                  49

     1.    Eutectic Heat Transfer Fluid                               49

          a.    Users                                                 51
          b.    Production Volumes                                    51
          c.    Economics                                             52
          d.    Environmental Management                              52
          e.    Use Alternatives                                      52
                fib
     2.    Dowfax^                                                    53

          a.    Manufacture                                           53
          b.    Production Volumes                                    55
          c.    Economics                                             55
          d.    Environmental Management                              55
          e.    Alternative Products                                  56

     3.   Diphenyl Oxide Dye Carriers                                56

          a.    Volume  of Use                                         56
          b.   Economics                                             57
          c.    Environmental Management                              57
          d.    Alternative Products                                  58

     4.   Perfumes and Soaps                                         57

          a.    Manufacture                                           57
          b.    Volume  of Use                                         58
          c.    Economics                                             58
          d.    Environmental Management                              59
          e.    Alternative Products                                  59

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                         Table of Contents (Cont'd)                       Page


          5.    Butylated Monochlorodiphenyl Oxide                         59

               a.    Manufacture                                           59
               b.    Production Volumes                                    60
               c.    Environmental Management                              60
               d.    Economics                                             60
               e.    Alternatives                                          61

          6.    Deeabromodiphenyl Oxide                                    61

               a.    Manufacture                                           61
               b.    Production Volumes                                    62
               c.    Economics                                             62
               d.    Environmental Management                              62
               e.    Alternatives                                          63

          7.    Minor Commercial Uses of Diphenyl Oxide                    63

               a.    Chloromethyldiphenyl Oxide                            63
               b.    Methoxymethyldiphenyl Oxide                           64
               c.    Pesticides                                            65

VI.  Sources of Biphenyl and Diphenyl Oxide Occurring in Nature           67

     A.   Biphenyl                                                        67

          1.   Petroleum                                                  67
          2.   Foods                                                      68

     B.   Diphenyl Oxide                                                  68

          1.   Plants                                                     68

VII. Generation of Biphenyl and  Diphenyl  Oxide By-Products                70

     A.   Biphenyl                                                        70

          1.   Dealkylation of Toluene                                    70
          2.   Naphthalene Feedstocks                                     70
          3.   Coal Tar                                                   72
          4.   Automobile Exhaust                                         73

     B.   Diphenyl Oxide                                                  73

          1.   Caprolactam -  Nylon Production                             73
          2.   Bituminous Coal Tar                                        74
                                       vi

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                          Table of Contents (Cont'd)                      Page


VIII. Material Balance - Exposure to the Environment                       75

      A.   Biphenyl                                                        75

           1.   Dye Carrier                                                75
           2.   Fungicide^.                                                75
           3.   Dowtherm^A                                               77
           4.   Creosote Oils                                              77
           5.   Petroleum                                                  78
           6.   Naphthalene Feedstock and Toluene Dealkylation             78
                By-Product, Unrefined
           7.   Coal-Tar,  Excluding Creosote  Oils                          78
           8.   Automobile Exhaust                                         78

      B.   Diphenyl Oxide                                                  78

           1.   Dye Carrier                                                78
           2.   Perfumes/gand  Soaps                                         80
           3.   DowthernTA                                                80

  IX.  Environmental Perspectives     '                                      81

      A.   Occupational  Exposure  to Man                                   81
      B.   Release to  the  Environment                                      82

           1.   Biphenyl                                                  82

                a.   Effectiveness of Biphenyl Waste Treatment             82
                b.   Environmental Chlorination of  Biphenyl               84

           2.   Diphenyl Oxide                                            88

                a.   Effectiveness of Waste Treatment                     88
                b.   Biodegradation                                         88
                c.   Bioconcentration                                      89

  X.   Environmental Assessment                                            90

      A..   Biphenyl                                                         90
      B.   Diphenyl Oxide                                                  91

  Appendix A  -  Physical Properties                                         93

  Appendix B  -  Material Safety Data Sheets                                  96

  REFERENCES                                                                103
                                        vii

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                               List of Tables                          Page


III-l.    United States Biphenyl Producers                              10

V-l.      Textile Chemical Specialty Firms Who Make Biphenyl Dye        37
          Carriers

VIII-1.   Estimated Environmental Releases of Biphenyl                  76

VII1-2.   Estimated Environmental Releases of Diphenyl Oxide            79

IX-1.     Chlorination of Biphenyl Utilizing Water Renovation           86
          Conditions
                                      viii

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                               List of Figures                          Page


III-l.     Annual Biphenyl Production (SRC Estimation)                    11

III-2.     1976 Annual Biphenyl Use in the United States                  ^

III-3.     Domestic Diphenyl Oxide Use in 1975                            15

IV-1.     Biphenyl From Thermal Dehydrogenation of Benzene               18

IV-2.     General Process for Hydrodealkylating Toluene to Benzene       23

IV-3.     Diphenyl Oxide From Chlorobenzene - Phenol Process             28

V-l.      Polyester Fiber to Garment Flow Diagram                        36

V-2.      Dyeing and Finishing of Polyester Fabrics                      39

V-3.      Process Manufacture of Dowfax^ Solutions                       54

IX-1.     Reduction of Concentration Owing to Biodegradation -           85
          Analysis of Culture Cells and Water
                                       ix

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I.   Introduction




     Occupational exposures to the compounds biphenyl and diphenyl oxide (phenyl




ether) have been regulated by the Occupational Safety and Health Administration.




The standards established by OSHA are directed at protecting workers who might




be exposed occupationally to air vapors or particulates of biphenyl or diphenyl




oxide.  Until recently, however, little thought has been given to the amounts




of biphenyl or diphenyl oxide that are released to the environment, and thus




indirectly result in human exposure or environmental damage.  Of additional




concern are reports which have suggested that various PCS (polychlorinated




biphenyl) isomers are formed when sewage, which contains biphenyl, is discharged




to waste treatment plants utilizing chlorine for disinfection and deodorization




(Carlson et al., 1975; Gaffney, 1974, 1976; Johnsen, 1975).  Biphenyl and




diphenyl oxide have also been shown to bioconcentrate several hundred times in




fish and, therefore, small concentrates in water may result in significant con-




centrations in fish.  This report considers environmental sources of biphenyl




and diphenyl oxide and estimations of the amounts which may be exposed to the




environment.

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II.  Historical Development and Future Outlook




     A.   Historical Development




          1.    Biphenyl




               Biphenyl (diphenyl; phenylbenzene),  (C,HC)0,  was first reported in
                                                     0 _> L



1862 by Fittig, who prepared it by the action of metallic sodium on bromobenzene.




Berthelot prepared biphenyl in 1867 by passing benzene vapors through a red hot




tube.  In 1875, Blichner found biphenyl in high-boiling fractions from coal-tar




distillation (Poffenberger, 1950).




               In 1927, Theodore Swann of the Federal Phosphorus Co. was asked




to supply biphenyl in commercial quantities for use as a heat transfer fluid in the




refining of lubricating oils.  He set up a pilot plant for this purpose.  Soon




after, the chlorination of biphenyl assumed commercial importance when the Swann




Corp. developed the "Aroclor" series of PCB's (polychlorinated biphenyls); how-




ever, Monsanto took over the PCB production in the early 1930's.  About that



                                                                          
time, Dow Chemical Co. entered the commercial biphenyl field with Dowtherm  A,




a eutectic mixture of biphenyl and diphenyl oxide for use in heat transfer.




Historically, the two principal manufacturers of biphenyl have been the Monsanto




Co. and the Dow Chemical Co. (Versar, 1976; Poffenberger, 1965).




               The earliest commercial reactors were vessels holding a bath of




molten lead at 750C, through which benzene vapors were bubbled (Scott, 1933;




Durgin and Jenkins, 1933).  Later reactors used electrical resistance heaters to




raise the temperatures above 650C.  The major technical problem was the tendency




of benzene to decompose at very high temperatures to give carbon and heavy tar




deposits which clogged the heat exchange surfaces.   Practically all of the patents




covering the manufacture of biphenyl have been proposed as solutions to this problem.

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               Patents have also been issued which identify biphenyl as a major




by-product of phenol produced by the partial oxidation of benzene (Porter, 1946;




Dundee, 1964).  Biphenyl appeared on the U.S. market in 1964 which was refined




from this process (Poffenberger, 1965).  However, biphenyl currently produced by




this method has little commercial importance due to the limited capacity of




phenol production via partial oxidation of benzene.




               In the late 1960's the commercial potential of recovering a bi-




phenyl by-product formed when toluene is hydrodealkylated to benzene was realized.




Today, the biphenyl obtained from the dealkylated toluene by-product is the most




important commercial source of biphenyl.  This apparently occurred due to large




available quantities of the low-cost by-product and a sharp demand for biphenyl




dye carriers.  Approximately 70% of the current annual biphenyl production of




85 million pounds is obtained by refining the dealkylated toluene by-product




(SRC estimation).  The remaining 30% of the biphenyl production is produced by




Monsanto1s process of thermally reacting benzene vapors.




               The earliest uses of biphenyl involved heat transfer agents and




synthesis to PCB's.  During the late 1940's, biphenyl began to be used as a mild




fungicide when coated on individual fruit wrappers, although the patent describing




this use was dated somewhat earlier (Mispley and Barber, 1940).  More recently,




biphenyl has been impregnated onto paper pads used in closed fruit packages.




These fungicidal uses still exist today, but at a level which has slowly decreased




due to better transportation and refrigeration systems.




               In the 1960's, biphenyl found use as a dye carrier for disperse




dye applications to polyester fibers.   The use of biphenyl dye carriers has




accelerated so greatly in the past six years that this use represents the largest

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single application of biphenyl at present, consuming nearly 60% of the annual


biphenyl production of 85 million pounds (SRC estimation).   Large quantities of


biphenyl, nearly 21 million pounds annually, are still being used for PCB manu-


facture; however, present legislation to eliminate PCB production will eli-


minate this use of biphenyl.  Several million pounds of biphenyl are annually


destined for heat transfer fluids.  Since 1970, alkylated biphenyls have become


commercially important, especially isopropylbiphenyl.  Approximately 10 million


pounds of isopropylbiphenyl are annually produced, at present, for applications


in carbonless paper.


               Commercial production of flame retardant PBB's (polybrominated


biphenyls), which began in 1970, was thought to have been terminated in November,


1974, a year after PBB's were mistakenly added to cattle feed in Michigan


(Mumma and Wallace, 1975).  However, decabromo- and octabromobiphenyl were


commercially produced in 1975 and 1976 for export purposes (Neufeld et^ al^., 1977).


In 1976, about 130 thousand pounds of biphenyl were consumed in the production of


these two PBB products.


          2.   Diphenyl Oxide


               Dr. Herbert H. Dow carried out experiments with diphenyl oxide


(phenyl ether, diphenyl ether, phenoxybenzene, DPO) in 1925-1926, using it as


a heat transfer fluid in a steam power process.  These experiments eventually


led to the development of Dowtherm"^ A, a eutectic heat transfer mixture of

                                                                       fS\
73.5% diphenyl oxide and 26.5% biphenyl, in the early 1930's.  DowthemT*'A


has been a widely-used heat transfer fluid since that time.

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               The original American patents describing diphenyl oxide pro-




duction were assigned to the Dow Chemical-Co.  The first patent (Hale, 1930)




described the production of diphenyl oxide as heating equimolar amounts of




chlorobenzene and aqueous base, such as Na~CO_ or NaOH, under pressure with




copper catalysts.  The second patent (Hale and Britton, 1933) refers to the Dow




process of phenol production from chlorobenzene and aqueous base.  In this




process, diphenyl oxide is formed as a by-product.  Historically, nearly all



of the diphenyl oxide produced in the U.S.  has been obtained from the by-product



from Dow's chlorobenzene-phenol process.  However, Monsanto has recently entered



the commercial diphenyl oxide market.  A new Monsanto unit, completed in late



1975, produces high-purity diphenyl oxide in a one step process which involves



reacting phenol in the presence of a catalyst.




               The only commercially important early use of diphenyl oxide,


                       
other than for Dowthemr A heat transfer fluid, was for applications with per-



fumes and soaps.  Diphenyl oxide has a characteristic geranium odor.  Use in



perfumes and soaps is still important, with roughly 100,000 pounds annually



consumed.  Historically, most of diphenyl oxide produced has been used to




formulate Dowtherm  A.  Roughly two-thirds of the estimated 6 million pounds



                                                       
of diphenyl oxide produced in 1975 was used in Dowthernr^ A (SRC estimation).



               Other commercially important current uses of diphenyl oxide


              
include Dowfax^ (alkylated sulfonated derivatives) surface-active agents, deca-



bromodiphenyl oxide flame retardants, diphenyl oxide dye carriers, and butyl-



chlorodiphenyl oxide capacitor fluid.  Dowfax^production started in the early




1960's and decabromodiphenyl oxide and diphenyl oxide dye carriers started in



the 1970's.  Butylchlorodiphenyl oxide is discussed in Future Outlook - Diphenyl



Oxide.

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               Several diphenyl oxide derivatives, chloromethyl diphenyl oxides,



and methoxymethyl diphenyl oxide, have minor commercial uses in polymer and



resin production.




     B.   Future Outlook'



          1.   Biphenyl




               The sizeable increase in biphenyl production from 1970 to the




present is primarily due to the dye carrier use of biphenyl in polyester dyeing.



Future increases in production may, therefore, be aligned with increases in the poly-



ester market.  Several industry spokesmen are projecting an 85% increase in the



polyester market by 1980 and a 170% increase by 1985.  Biphenyl, however, is



only one of perhaps eight to ten commercially important dye carriers used in



polyester dyeing.  After consulting with industry spokesmen, it is estimated



(SRC estimation) that biphenyl dye carriers make up approximately 25-30% of the



total dye carrier market at present.  The total dye carrier market is expected



to increase by 47% by 1980.  This 47% figure is smaller than the 85% polyester



growth figure because technological improvements in dyeing techniques should



decrease the amount of dye carrier which is required.



               _If_ biphenyl maintains 25-30% of the dye carrier market, an addi-



tional 20-25 million pounds of biphenyl will be used for dyeing by 1980.  Present



biphenyl consumption in dye carriers is estimated at 50 million Ibs. annually



(SRC estimation).



               Increased biphenyl consumption is also projected for heat transfer


                                                                                 (S)
fluids and alkylated biphenyls.  Dow has announced an expansion of their Dowthernr^ A



units, to be completed by 1978 (Anon., 1976 a).  In early 1976, Monsanto began



commercial production of Therminol VP-1 heat transfer fluid, which will compete

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with Dow's Dowtherm^A.  Therminol VP-1 and DowthemP A have identical chemical



compositions.  Isopropylbiphenyl, used in carbonless paper, and methylbiphenyl,



used as a dye carrier, are also expected to increase output by 1980.  A guess



would project that nearly 10 million additional pounds of biphenyl will b,e used



for heat transfer and alkylation by 1980 (SRC estimation).



               The projected phase-out of PCB's which is required by section 6e



of the Toxic Substances Control Act (PL 94-469) would decrease the needed



biphenyl production by nearly 21 million pounds annually.  However, alternatives



to PCB's may include another biphenyl derivative.  Effects to the biphenyl



market by the PCB phase-out cannot be ascertained at this time.



          2.   Diphenyl Oxide



               There will be large increases in the production of diphenyl oxide



by 1980.  Until the end of 1975, the only commercial quantities of diphenyl oxide



were obtained from Dow's chlorobenzene-phenol process as a by-product.  This



amounted to approximately 6 million pounds annually (SRC estimation).  However,



at the end of 1975, Monsanto began commercial production of diphenyl oxide for



use in Therminol VP-1 heat transfer fluid.  Also, Dow has announced a $37 million



expansion of their chlorobenzene complex to be completed in 1978.  This will in-



clude expansion of diphenyl oxide production, primarily for use in butylchloro-


                                     
diphenyl oxide, but also for Dowthernf^A and decabromodiphenyl oxide (Anon., 1976 a)




An estimated $10 million of this expansion had been completed by April, 1976.



               The primary reason for Dow's diphenyl oxide expansion appears to



be synthesis of butylchlorodiphenyl oxide.  Dow is hoping that butylchlorodiphenyl



oxide will be widely accepted as a PCB replacement in capacitors.  McGraw-Edison,



a capacitor manufacturer, has totally converted to the use of this Dow product in

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1976, making a reality of commercial production.   Dow says it hopes to have




production capacity in excess of 5 million Ibs/year of butylchlorodiphenyl




oxide by the end of 1976 (Anon., 1976b).   If this 5 million Ib figure proves




correct, then diphenyl oxide production in the U.S. will have doubled in a




year's time.  The degree of diphenyl oxide expansion in the future may be




determined by industry's acceptance of butylchlorodiphenyl oxide as a PCB




substitute.  It should be noted, however, that other companies are developing




and evaluating PCB substitutes different from butylchlorodiphenyl oxide.

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III. Market Input/Output Data




     A.   Production




          Table III-l lists the domestic producers of refined biphenyl with their




respective production sites, years, and capacities.  Also listed in Table III-l




are the petrochemical companies who commercially supply unrefined biphenyl feed




stock (by-product from toluene dealkylation) to biphenyl refiners.  Annual bi-




phenyl production is shown in Figure III-l.




          Two companies have stopped refined biphenyl production.  First is Geneva




Industries of Houston, Texas, who sold their biphenyl refinery to Pilot Industries




in 1974.  Second is Bethlehem Steel Corp. of Sparrows Point, Maryland, who termi-




nated biphenyl refining in 1974.




          The Dow Chemical Co. and Monsanto Industrial Chemicals Co. are the only




domestic producers of diphenyl oxide.  The Dow production site is located in




Midland, Michigan, while Monsanto's site is located at their Chocolate Bayou




facility in Alvin, Texas.  Dow has been involved in the production of diphenyl




oxide since the early 1930's.  Monsanto began commercial production at the end




of 1975.




          Dow did not release their annual production volumes, as the information




is considered confidential  (Otis, 1976).  However, before the current diphenyl




oxide expansion, Dow obtained all of their diphenyl oxide as by-products from




their chlorobenzene-phenol process.  Capacity of this phenol process has been




estimated at 48-70 million pounds annually  (SRI, 1975 a, 1976).  Since approxi-




mately 0.1 pound of diphenyl oxide is formed for every 1.0 pound of phenol




formed (Hahn, 1970), the annual diphenyl oxide output would be 4.8 to 7.0 million




pounds; and, therefore, 6 million pounds may be a good estimate of the annual

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                              Table III-l.   United States Biphenyl Producers
Refined Biphenyl Producers - 1976
Producer . .
1.
2.
3.
4.
5.
6.
7.
8.
Chemol , Inc .
CPS Chemical Co., Div. of
Chemistry & Pollution
Sciences
Dow Chemical Co.
East Coast Chemical Co.
Monsanto Industrial Chemicals
Pilot Industries
Sun Oil of Penn. (Suntide)
Sybron Corp., Tanatex
Chemicals Div.
Production Site
Greensboro, NC
Old Bridge, NJ
Bay City, MI
Cedar Grove, NJ
Anniston, AL
Houston, XX
Corpus Christi, TX
Lyndhurst, NJ
Years Estimated Capacity (x 10 Ib/yr)
1972

1971
1974
1933
1974
1970
1971
- Present
"""
- Present
- Present
- Present
- Present
- Present
- Present
5
< 1
10 -
1-4
45
15 -
10 -
10


20


20
20

                              Biphenyl  Feed Stock Producers - Commercially Available Product
1.  Coastal States Gas Producing
    Co.
2.  Cosden Oil and Chemical Co.
3.  Dow Chemical Co.
4.  Gulf Oil Corp.
Corpus Christi, TX

Big Spring,  TX
Bay City,  MI
Philadelphia,  PA

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r^

I
           120-r
        
        Q.
        m
           100 H
            90-
            80-|
            70-|
           60-|
           50H
           40H
           30
                                                         84.6
                                  PCB Production CutBack
                                                                                         Considers PCB Ban
O Data From United States International Trade
  Commission,"Synthetic Organic Chemicals"
                 I	1	1	1	1	1	1	1	1	1	1    I    I     I     I     I     I
                  1966 1967  1968  1969 1970 1971 1972 1973 1974 1975  1976  1977 1978 1979 1980 1981 1982
                                                         Year
                        Figure III-l.   Annual Biphenyl Production (SRC Estimations)

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capacity.  Of course, that figure is somewhat higher currently,  depending upon


how much of the chlorobenzene expansion has been completed.


          The production capacity of Monsanto's facility for diphenyl oxide is


considered proprietary and has, therefore, not been obtained.  Monsanto produces


diphenyl oxide by reacting phenol with catalyst.


     B.   Importation


          Prior to 1974, there is no record in the literature of any importation


of biphenyl or diphenyl oxide.  However, the 1974 edition of "Imports of Benzenoid


Chemicals and Products" (United States International Trade Commission) lists the


following imports:


               Biphenyl                              10,758 pounds
               Phenyl Ether (Diphenyl Oxide)         43,201 pounds


It should be noted that this reference source includes only surveys conducted


at the major ports of entry.  The above quantities are relatively insignificant


when compared to the total biphenyl and diphenyl oxide consumption in the United


States;  they represent less than 1% of the yearly consumption.


          "Imports of Benzenoid Chemicals and Products" (1967-1974 editions)


also list imports of unspecified "textile assistants" ranging from 1.4 to 4.7


million  pounds annually.  The chemical ingredients of these textile assistants have


not been determined by SRC.  It is possible that some of these textile assistants


are biphenyl dye carriers, although it would be surprising if more than one million


pounds of biphenyl are imported via this route.


          It is also possible that quantities of biphenyl and diphenyl oxide are

                                                                        @\
imported as heat transfer fluids with compositions identical to Dowthernr'A.


These heat transfer fluids, made overseas, are listed in Section V-B-1; quantities


which may be imported were not obtainable.
                                       12

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     C.   Exportation




          No figures revealing export quantities of biphenyl or diphenyl oxide




were available.  After consulting with industry spokesmen, it is believed that




small quantities of biphenyl dye carriers are exported to Canada and Mexico.




Also, biphenyl fungicide pads are used for overseas shipments of fruit, but




this quantity is less than a million pounds.  Overseas exportation, in bulk




quantities, appears to be virtually unknown.




     D.   Use Patterns




          Figure III-2 and Figure III-3 diagram the 1976 uses of biphenyl and




1975 uses of diphenyl oxide, respectively.  Quantities used in each application




are included where known or estimated.
                                      13

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i
         Biphenyl  	
-* Dye Carriers
                                       - Heat Transfer
                                  Derivatives
                              0.6-0.8
                          - Dowtherm  A
                                                                  - Therminol VP-I
                                                         21
                                                                *-PCB's
                                                     9    Alkylated
                                                          Biphenyls
                                        -* Fruit Paper Fungicide

                                                                                Methylbiphenyt
                                                                                Ethylbiphenyl
                                                                                 Isopropylbiphenyl
                                                                                 Butylbiphenyl
                                                              Dye Carrier


                                                              Heat Transfer


                                                              Carbonless Paper


                                                               Heat Transfer
                                                                             Note:
                                                                              All Figures Indicate Biphenyl Consumption x 10s Ibs.
                                                                              and are SRC Estimations.
                        Figure  III-2.    1976  Annual Biphenyl  Use  in  the United  States

-------
i
         Diphenyl
            Oxide
                                  0.25
                                             Dye Carrier
                                          -* Heat Transfer
                                    Derivatives
                                   0.1
Dowtherm  A
                                                                         Therminol VP I
                                                           * Chloromethyldiphenyl oxide
'^ Di(chloromethyl)diphenyl oxide


' Methoxymethyl diphenyl oxide

0.75
                                                              Oecabromodiphenyl oxide 
                                                           - Butylchlorodiphenyl oxide
                                                       0.75

                       -* Polymers, Foams
                                                                                                    Polymers, Foams
                       -* Dory' resins
                       * Fire retardant
                          Capacitor fluid
                                                              Dowfax   ( Dodecyldiphenyloxidisulfonic acid, Disodium salt)
                                          * Perfumes and Soaps
                                                     Surfaceactive agents
                                                                                 Note:
                                                                                   All Figures Indicate Diphenyl oxide Consumption x 106 Ibs.
                                                                                   and are SRC Estimations.
                                          Figure III-3.   Domestic Diphenyl Oxide Use in 1975

-------
IV.   General Manufacturing and Production Technology

     A.   Biphenyl

          1.   Thermal Dehydrogenation of Benzene  .

               Monsanto Industrials Chemicals Co., located in Anniston, Alabama,

is the only current biphenyl producer to use the thermal dehydrogenation of

benzene process.  Both Monsanto and Dow began using the process in the 1930's;

however, Dow termination their process in 1968 in favor of biphenyl production

from dealkylated toluene.

               a.   Manufacture

                    The chemistry involved in the thermal dehydrogenation of

benzene is shown in the following reaction:
                                       (0.08%)
                                               +    Higher
                                                  Polyphenyls
                                                     (2%)
+  H_  +  Carbon
    (4.9%)
At temperatures of 700-850C, benzene reacts by a homogeneous gas-phase reaction

(in which a benzene molecule joins with another benzene molecule or with a poly-

phenyl molecule, liberating hydrogen and forming biphenyl or higher polyphenyls)

or by a heterogenous gas-solid phase reaction, giving carbon and hydrogen.  Most

process development work has been directed to repressing the second reaction, which

is catalyzed by metals, particularly iron, copper, and nickel (Poffenberger, 1965).
                                      16

-------
                    Figure IV-1 illustrates the typical process method of

biphenyl production from thermal dehydrogenation of benzene.  The raw material

benzene and recycled benzene are vaporized and heated to about 600C and then

injected into a thermal reactor at 1-2 atm. pressure.  The reactor raises the

temperature to 700-850C, the time of exposure to the higher temperatures being

on the order of one second.  Under these conditions, a well-designed thermal

reactor yields a condensed product containing 12-15% by weight of biphenyl,

terphenyl, and polyphenyls corresponding to approximately 20% by weight of the

biphenyl, and the remainder as unreacted benzene.  The yield of biphenyl, based

on benzene consumed, should be 80-85% of theory.  The yield of biphenyl plus

terphenyl and other polyphenyls should be 90-95% of theory.  At a 15% conversion

per pass, the yield of biphenyl is 0.80 Ib and that of terphenyl, etc. is 0.12 Ib

per pound of consumed benzene.  The mechanical loss of benzene is 0.02-0.04 Ib

per pound of consumed benzene (Poffenberger, 1950, 1965).

                    The product from the reactor is condensed in a heat exchange

system and then distilled to drive off the benzene which is recycled.  The
                 i
biphenyl-rich still residues are then vacuum distilled to separate the biphenyl

from the terphenyls, etc.  Benzene in the noncondensable gas (mostly hydrogen)

vented from the heat exchange system is recovered either by compression or

activated charcoal adsorbers.  All of the benzene is passed through the heat

exchangers to raise the benzene temperature and to cool the reactor products'

temperature (Sanders and Slocombe, 1955; Poffenberger, 1950, 1965).

                    Heat is generated in the thermal reactor by means of electrical

resistance elements.  At temperatures above 650C, benzene has a tendency to

decompose to give carbon and heavy tar deposits which coat heat exchange surfaces.
                                      17

-------
                                                 Benzene
                     H2Gas
                   Compressor
                      or
                    Activated
                    Charcoal
00
Gas Vent   f .
                        Benzene
                           Feed'
                                                        Distill
                                                       Column
                                                                    Biphenyl.-Polyphenyl
                                                           12-15% Biphenyl
                                                           1 -5% Polyphenyls
                                                           80-85% Benzene
                                                      Thermal
                                                       Reactor
                                                                                                                   *> Biphenyl
                                                                                        8% oTerphenyl
                                                                                       49%m-Terphenyl
                                                                                       23%p-Terphenyt
                                                                                       20% Triphenylene, Quaterphenyls, etc.
                                                                                                                        To
                                                                                                                     Terphenyl
                                                                                                                     Processing
                                                                      (Adapted from Poffentaerger 1950.1965; Sanders and Slocomtae. 1955]
                                   Figure  IV-1.    Biphenyl  From Thermal  Dehydrogenation of  Benzene

-------
Metal surfaces made of iron, nickel, or copper catalyze this carbon formation;

therefore, metal surfaces are coated with carbide, nitride, or oxide to reduce

the catalytic effects (Prutton, 1940; Moose and Pritchard, 1934).

                    The following shipping information is available (Monsanto

Technical Bulletin 1C/FF-29):

          Shipping Classification (U.S.)!         Diphenyl (phenyl benzene)

          Labelling:                              Product label

          Standard Containers:                    50 Ib net multiwall bags
                                                  260 Ib net fibre drums
                                                  Tank trucks
                                                  Tank cars

               b.   Production Volumes

                    Monsanto is the only domestic biphenyl producer currently

utilizing thermal dehydrogenation of benzene.  Most of the biphenyl presently

made by Monsanto is captively used to produce PCB's (SRC estimation).  Approxi-

mately 21 million pounds of biphenyl are required for the annual PCB production

of 40 million pounds.  Additionally, slightly less than one million pounds of

biphenyl may be supplied by Monsanto for fungicidal purposes (SRC estimation).

Monsanto has also just begun production of a heat transfer fluid called Therminol

VP-1, which is an eutectic mixture of 26.5% biphenyl and 73.5% diphenyl oxide.

Several million pounds of biphenyl may be required for annual production of

Therminol VP-1.

                    The capacity of Monsanto's Anniston, Alabama biphenyl unit

is probably twice that of current utilization.  In 1970, Monsanto produced 85

million Ibs of PCB's  (Versar, 1976), which would require approximately 44 million

pounds of biphenyl.  After 1970, Monsanto restricted PCB sales to closed system

uses; hence, production was cut approximately in half.


                                     19

-------
               c.   Economics




                    The current (1976)  selling price of Monsanto's biphenyl is




$0.36/lb; however, most is captively used in synthesis of PCB's.




                    To estimate the raw material cost to produce  biphenyl via




thermal dehydrogenation of benzene, the yields previously described have been




assumed:  1 Ib of consumed benzene yields 0.80 Ib biphenyl and 0.12 Ib terphenyl,




etc.  Also, the current selling price of benzene is $0.80/gallon  or $0.11/lb.




                    Therefore, one pound of biphenyl consumes $0.136 worth of




benzene raw material.  Additional costs must be added for equipment, labor,




insurance, transportation, etc.




               d.   Environmental Management




                    The only wastes from the process are the crude still pot




residues, which will be high molecular weight hydrocarbons, tars, and carbon.




It is very likely that a small amount of biphenyl will be present in these




residues; however, a chemical composition breakdown of the still  pot residues




was not available.  Also, the environmental fate of these residues was not




determined, but it is suspected that the residues are burned for  fuel purposes




or used in coking operations.  Due to the nature of the process,  large amounts




of biphenyl cannot be released to the environment and any amounts which may be




released are very much smaller than amounts released by the dyeing industry.




               e.   Alternative Biphenyl




                    The advantage of Monsanto biphenyl is the purity, a very




high-grade product compared to biphenyl normally produced from dealkylation




of toluene.  The disadvantage is price, $0.36/lb compared to $0.16-$0.25/lb




for dealkylated toluene biphenyl.  Since the lower-grade biphenyl is suitable




for dye carrier application, Monsanto1s biphenyl is not very competitive for




this large quantity use.





                                       20

-------
          2.   By-Product From Dealkylatlon of Toluene
               The companies listed below are all currently refining biphenyl
from a by-product obtained when toluene is hydrodealkylated to benzene:
          Chemol, Inc.                              Greensboro, NC
          Dow Chemical Co.                          Bay City, MI
          East Coast Chemical Co.                   Cedar Grove, NJ
          Pilot Industries                          Houston, TX
          Sun Oil of Penn.                          Corpus Christi, TX
          Sybron Corp., Tanatex Chemical Div.       Lyndhurst, NJ
               Dow Chemical and Sun Oil generate their own by-product, while the
other companies listed above purchase the by-product feedstock from one of the
following petroleum companies:  Coastal States Gas Producing Co. (Corpus Christi,
TX), Cosden Oil and Chemical Co. (Big Spring, TX) , Dow Chemical (Bay City, MI),
or Gulf Oil Corp. (Philadelphia, PA).
               a.   Chemistry
                    Hydrodealkylation involves the removal of one or more alkyl
groups from alkylbenzenes to produce high-grade benzene as the end product.  The
reactions are carried out either thermally or catalytically in the presence of
excess hydrogen at elevated temperatures and pressures.  When toluene is used
as the starting material, the. principal hydrodealkylation reaction leading to
the selective product formation of benzene is:
(1) .   LL         "*"     H2  -              +    CH4     (Doelp, 1966)

The types of reactions contributing most to the nonselective product formation
are the following:
                                      21

-------
(2)
 (3)
                                             H.,
                                               (biphenyl)
                                                 (methylbiphenyl)
 (4)
D.
+   2H,
                                                     (fluorene)






                    Figure IV-2 illustrates the general  process  for hydrodealkylating




toluene to benzene.   The various companies employ slightly  different  techniques




to accomplish the basic operations;  however,  the overall processes are  quite




similar.




                    The toluene feed and hydrogen-rich gas  are heated to an elevated




temperature and pumped into a tubular reactor of 400 - 1000 psig pressure  and




811 - 1033F temperature.  The hydrogen-to-toluene mole  ratio  is 4-12.  This




stoichiometric excess of hydrogen helps to suppress the  non-selective reactions.




Contact time in the reactor averages 20-80 seconds (Doelp,  1966).  Catalysts




are used in several processes.
                                      22

-------
10
                      Toluene Feed
                 Hydrogenrich Gas 
                                                                            Fuel Gas
                                                   Reactor
                                                     Biphenyl
                                                      Products
                                                 94-97% Pure
                                                                      Distill
                                                                      Column
                                                                                                                        Benzene Product
Bottoms: Biphenyl 40-70%
       Fluorenes
       Methylbiphenyl
       Toluene
       Anthracene
       Pyrene
                                                                    Residues to
                                                                   Fuels or Coking
                          Figure  IV-2.   General Process  for Hydrodealkylating Toluene  to  Benzene

-------
                    The product from the reactor is condensed through heat ex-

changers and the fuel gas (hydrogen and methane) is vented off for fuel uses.

Benzene is separated from the non-selective products by fractional distillation.

The yield of benzene from toluene is greater than 95% of theoretical.

                    The bottoms residue from the benzene fractionator will vary

slightly from company to company.  However, an average composition for this

residue would be (Earhart, 1976; Derrig, 1976; Doelp, 1966):

                    Biphenyl                 50%
                    Toluene                  15-20%
                    Fluorenes                10-15%
                    Methyl biphenyls         5%
                    Anthracene               3%
                    Pyrene                   3%
                    Other Aromatic           9%
                      Hydrocarbons

The weight of the bottoms residue is approximately 2% of the weight of toluene

feed.  Therefore, approximately one pound of biphenyl is formed for every 100

pounds of toluene which is dealkylated.

                    These bottoms from the benzene fractionator have two uses.

Economically, the best use is to refine the biphenyl or sell the bottoms to

biphenyl refiners (if the refined biphenyl can be sold).  Otherwise, these

bottoms are usually added to fuel oils and burned as fuels.

                    The biphenyl is refined from the other hydrocarbons in the

benzene fractionator bottoms by distillation.  A biphenyl product of 95-97%

purity is commonly obtained, which is quite suitable for use in dye carriers.

The residues from the biphenyl distillation are either added to fuels or used

in coking operations.

                    Bulk shipments of biphenyl to customers is done via railway

or truck tankers in a molten state (biphenyl melts at 69C).


                                      24

-------
               c.   Production Volumes




                    Estimated capacities of the biphenyl refiners are listed




in Table III-l, p. 10.  Roughly 60 million pounds of refined biphenyl are currently




being obtained from dealkylated toluene (SRC estimation).  Ten years ago, the




figure was very nearly zero.  The sharp increase has come since 1970.




               d.   Environmental Management




                    The nature of this production method limits biphenyl release




to the environment to virtually nothing.  More biphenyl is probably spilled




during loading of tankers than released in plant effluents (Earhart, 1976).




Appendix B contains Material Safety and Handling Sheets.




               e.   Economics




                    The biphenyl by-products from toluene dealkylation have




become available recently due to economic considerations concerning benzene.




The price of benzene has risen from $0.22/gallon in 1970 to nearly $0.80/gallon




in 1976.  With the current price of toluene in the $0.55/gallon range, the




profit potential of obtaining benzene by simply dealkylating toluene can be




appreciated.  Some of the dealkylation units idled or cut-back in 1970 are now




running nearer to capacity and new units are being installed.  This increase in




dealkylation of toluene has resulted in a biphenyl by-product from which profits




can be realized.  Therefore, the.biphenyl by-product has found use as fuel




additives or as a refined product.




                    The biphenyl by-product can be sold to biphenyl refiners for




$0.35 per gallon of which approximately 50% by weight is biphenyl (Derrig, 1976).




The biphenyl content of the by-product would, therefore, have a selling value




of about $0.085/lb.  The refined biphenyl can be sold to dye carrier manufacturers
                                       25

-------
for $0.16-$0.25/lb., depending upon the purity.   This would indicate that re-




fined biphenyl obtained from dealkylation of toluene accounts for annual sales




of $10-15 million.  The quoted prices for this biphenyl in 1973 was $0.03-$0.07




less per pound than current prices.




                    A number of petrochemical companies produce a biphenyl by-




product from dealkylating toluene, but do not refine the biphenyl and do not sell




it to refiners.  They use it only as an additive to fuel oils.  These companies




and the quantities of biphenyl put in fuel oils will be discussed in Section




VII-A-1.




          3.   By-Product From Partial Oxidation of Benzene




               CPS Chemical Co. of Old Bridge, NJ is currently refining small




quantities of biphenyl from a by-product obtained when phenol is formed by




partial oxidation of benzene.  Production volumes of this refined biphenyl are




much less than one million pounds annually.




               a.   Process Description




                    A vapor phase mixture of benzene and oxygen are passed




through a tubular reactor of 0.5 - 2.0 atm. pressure and 600-800F.  Of the




benzene which reacts, 43% yields phenol, 25% yields biphenyl, and the rest




yields gaseous products (Porter, 1946).  The biphenyl is obtained by distillation.




                    This process for the production of phenol is so minor a




commercial method that it receives virtually no mention in the available




literature.




     B.   Diphenyl Oxide




          1.   By-Product From Chlorobenzene-Phenol Process




               a.   Manufacture
                                      26

-------
                      The  Dow Chemical  Co.,  plant  site  located  in Midland, MI,



  produced  diphenyl  oxide  as  a by-product  from  their  phenol  production via ehloro-



  benzene until  the  phenol operation was shut-down in 1975.   This entire  process



  is  illustrated in  Figure IV-3.



                      Brine undergoes electrolysis to produce hydrogen gas,



  chlorine  gas,  and  caustic soda  (NaOH).   The chlorine  is  used  to chlorinate



  benzene to  monochlorobenzene.   A one  mole  ratio  of  monochlorobenzene and a  2-2  1/2



  mole ratio  of  a 10-15% aqueous  caustic soda solution  are then introduced into a



  high pressure  pump along with a small percentage of diphenyl  oxide.  The di-



  phenyl  oxide is added to repress its  own formation  during  the hydrolysis reaction.



  It  should be noted that  the quantity  of  diphenyl oxide produced as by-product



  can be  partially controlled by  the quantity of diphenyl  oxide recycled  to the



  high pressure  pump.   It  provides a degree  of  flexibility to a process designed



  primarily for  the  production of phenol.  Other materials added to the reactants



  in  comparatively small quantities are anticorrosion agents (amines), emulsifiers



  (hydroxydiphenyl), and a catalyst (copper  salts) (Faith  et^ al., 1965).



                      The  reactants are then pumped through a nickel-lined,



  counter-current heat exchanger  which  raises the  reactants'  temperature  to



  275-300C.  The flow is  injected into a  continuous-flow  tubular reactor of



  4000-5000 psi  pressure and  heated to  400C.   Contact  time  is  usually 15-20



  minutes at  the 400C temperature. The selective and  non-selective reactions
 which occur  in  the  reactor  are  the  following:


                          Cl
                          i

(selective)
                       I s\  1

                                   2NaOH
                                                                Na
                                                                         H20
                          ONa
(non-selective)
                                                                               +   NaCl
                                       27

-------
NI
oo
               Brine
                           Technical Grade

                           Diphenyl Oxide
                                                                                                                               Benzene-Phenol

                                                                                                                               Mixture
                                                                                                                      NaCI Layer (aq I
                             Figure IV-3.   Diphenyl  Oxide from Chlorobenzene - Phenol  Process

-------
                    When leaving the reactor, the reaction products are passed
through the heat exchanger once again, to warm the incoming reactants and to
cool the reaction products.  The reaction products are then allowed to settle
in a density separator.  Two phases are obtained: (1) an aqueous sodium phenoxide
phase, and (2) an oil phase consisting principally of diphenyl oxide and un-
reacted monochlorobenzene.  The oil is distilled to produce diphenyl oxide and
the monochlorobenzene is recycled to the reactor.  The aqueous sodium phenoxide
layer is passed to a neutralizer and treated with hydrochloric acid prepared
from the HC1 gas by-product from the chlorinator.  The neutralization reaction
which produces phenol is:
    !)Na                                   OH
  Qj   +   HCl(aq)  	->    [Q
NaCl
                    The product from the neutralizer is density separated to
produce an aqueous NaCl layer and a phenol-rich layer.  The phenol layer is
distilled to obtain USP grade phenol.  The NaCl layer is extracted with benzene
to remove phenol content, and the NaCl solution is returned to the electrolytic
cell.  The phenol-benzene mixture is distilled to obtain high-purity phenol
(Poffenberger, 1968; Faith et^ al., 1965).
                    The overall yield of phenol based on monochlorobenzene is
90-95% by weight.  Conversion per pass through the reactor is 35-45% (Faith
et^ al^., 1965).  Approximately 0.1 pound of diphenyl oxide is formed per pound
of phenol formed (Hahn, 1970), but additional diphenyl oxide will be produced if
it is not introduced into the high pressure pump to limit the non-selective
reaction.  Small amounts of ortho and para-phenylphenol are formed as by-products
during the neutralization and are separated from the phenol-rich layer during
                                     29

-------
distillation.  Ortho-phenylphenol is used as a dye carrier and as an active



                   (R)
ingredient in Lysoi^ cleaner.




                    The diphenyl oxide obtained from the initial distillation




of the oil-layer from the reactor is a "technical" grade diphenyl oxide.   This




technical grade can be purified to Dow1s "perfume" grade diphenyl oxide.   Puri-




fication can be done by crystallization from solution in methyl alcohol (Britton




and Reed, 1933).  The technical and perfume grades differ only slightly in odor,




the distinction being apparent only to individuals trained in screening by ol-




factory response.  Dow also offers an "industrial" grade diphenyl oxide.   This




industrial grade is intended for use as a dye carrier, and assays about 90%




diphenyl oxide  (Dow Form No. 11028872).  The additional 10% makeup is primarily




naphthalenes and methyl naphthalenes (also effective dye carriers).




               b.   Production Volumes




                    Production quantities of diphenyl oxide from the Dow facility




are considered confidential information (Otis, 1976), and cannot be obtained.




However, the now defunct (terminated in 1975) phenol capacity of Dow's chloro-




benzene process had been estimated at 48-70 million pounds annually (SRI, 1975,




1976).  Since approximately 0.1 Ib of diphenyl oxide are formed per pound of




phenol formed, the annual diphenyl oxide capacity could have been 4.8-7.0 million




pounds.  Therefore, up to 1975, the annual diphenyl oxide production from this




process is estimated at 6 million pounds.




                    The Dow chlorobenzene and diphenyl oxide facilities at




Midland, MI are currently undergoing revision and expansion to be completed in




1978.  Ten million dollars of the total $37 million expenditure for this re-




vision and expansion have been completed to date (Anon., 1976 a).  Estimates of




future diphenyl oxide capacities are not available.
                                        30

-------
               c.   Shipping
                    The technical and industrial grades of diphenyl oxide are
shipped via tank cars and tank trucks in a molten state.  Freezing point of the
molten diphenyl oxide is approximately 80F, so only minimal heating from steam
coils is required to maintain a molten form.  Size of the tankers can range from
4,000-10,000 gallon railway tankers to 5,000 gallon trucks.  No extra-ordinary
precautions are required during shipping.
                    Technical grade diphenyl oxide can also be shipped in black
iron drums of 55 gallon capacity.  Perfume grade diphenyl oxide is shipped in
55 gallon galvanized steel drums.  These drums are equipped with dip pipes for
convenient removal of the diphenyl oxide in molten form.  Drum warmers may be
required to obtain the molten state.
               d.   Economics
                    The following selling prices (1976) are for bulk shipments
of diphenyl oxide:
                    industrial grade      $0.52/lb
                    technical grade       $0.60/lb
                    perfume grade         $0.85/lb
                    However, the large percentage of Dow's diphenyl oxide
production is captively used to make Dowthenn"'A, Dowfax*^ surfactants, butyl-
chlorodiphenyl oxide, and decabromodiphenyl oxide.  Since the diphenyl oxide is
obtained as by-product, cost estimations are difficult.
                    In the expansion and revision of the chlorobenzene pro-
cesses now underway at the Dow Midland facility, phenol production via
chlorobenzene will be eliminated in favor of phenol production from cumene.
                                      31

-------
This would indicate that diphenyl oxide will be prepared directly from chloro-


benzene and caustic soda.  Dow held the original patent describing diphenyl


oxide manufacture by this direct route (Hale, 1930).  The chemistry of this


reaction is:

        Cl
  o  ff\]   j.  oxT nu  Cu Catalyst^ /^\\   /^X
  2  K)l   +  2NaOH  	^-^((jAKCj)    +   2NaC1
The current selling prices of chlorobenzene and sodium hydroxide are $0.29/lb and

$0.125/lb, respectively (Chemical Marketing Reporter, 1976).  At a 90% yield,

one pound of formed diphenyl oxide would consume $0.49 of raw materials.  Since


Dow makes the chlorobenzene and NaOH, cost would be considerably less than the

selling price.

               e.   Environmental Management


                    All diphenyl oxide-phenolic product losses in the sewer are


treated by the Dow Chemical, Michigan Division, Waste Treatment Plant (Otis, 1976).

Treatment efficiency for the diphenyl oxide in the Dow treatment plant is unknown.


          2.   Catalysis of Phenol


               Monsanto Industrial Chemicals began producing diphenyl oxide at

their Chocolate Bayou complex in Alvin, Texas in late 1975.  Monsanto did not'


reveal any details concerning their process except that the overall process


involves reacting phenol with catalysts.

               The original description of producing diphenyl oxide by catalyzing


phenol is contained in a German patent (SchOllkopf, 1929).  The patent describes


phenol as being heated to 350C in an autoclave with activated fuller's earth to
                                      32

-------
give a 15% yield of diphenyl oxide.  The  process presently being used  by Monsanto

may be very  similar.  Undoubtedly, superior  catalysts and techniques have been

developed  to increase reaction yields  and rates which make the process economi-

cal.  A  simple flow-diagram illustrating  this process would be:
     Phenol
   Feedstock
                                    Recycled Phenol
                                           Water
                                   High-Grade 
                                 Diphenyl Oxide
                                                                       Low-Grade
                                                                       Diphenyl Oxide Bottoms
           2 C,HCOH-
              O D
                     The  selective chemical reaction should  be:

                      catalyst -s.  ,  N _
H20
                     The diphenyl oxide grade produced by Monsanto is 99.9% pure

 (Monsanto Technical Sheet  IC/FF-49).

                a.   Production Volumes

                     Monsanto has been producing diphenyl oxide only since late
                                       33

-------
1975.  Capacity or production volumes at the facility are not available as the




information is considered proprietary.  The large percentage of production will



be used captively to make Therminol VP-1 (Pane, 1976), which is a heat transfer


                                         (S)
fluid of identical composition to Dowtherm^ A.   The unit which produces Therminol



VP-1 was placed on-stream in early 1976 (Garza, 1976).



               b.   Environmental Management



                    Wastes generated by Monsanto's diphenyl oxide process are



treated by the company's own waste treatment facility (Pane, 1976).  The water



by-product produced during the process will be included in the wastes treated



by Monsanto.  The efficiency of the treatment facility upon the diphenyl oxide



wastes is unknown.



               c.   Economics



                    The current selling price  (1976) of Monsanto's diphenyl



oxide is $0.80/lb in bulk shipments.



                    Assume a 90% yield of diphenyl oxide from the phenol raw



material and a phenol price of $0.27/lb (Chemical Marketing Reporter, 1976).



Then 1 pound of  formed diphenyl oxide consumes $0.332 worth of phenol.

-------
V.   Use and Use Process Technology


     A.   Biphenyl


          1.   Dye Carrier


               At the present time, nearly 60% of the refined biphenyl produced


in the U.S. is consumed in dyeing assistants called dye carriers.  Polyester

                      /|^            fl^
fibers, such as Dacroir^ and Terylene  , are difficult to dye because the polymers


themselves are practically inert to most forms of chemical attack.  To enable


dyes to penetrate into these polyester fibers, the fibers must be treated with


compounds which cause the fibers to swell.  These swelling compounds, or "carriers"


as they are usually called, are aromatic chemicals that improve the rate, color


intensity, and uniformity of dyeing when added to the dyebath.


               a.   Manufacture


                    The companies who produce biphenyl are generally not the


companies who formulate biphenyl into dye carrier products.  Figure V-l illu-


strates the overall schematic for the virgin polyester fiber-to-finished garment


process.  The companies who produce the dye carrier chemicals sell these chemi-


cals to textile chemical specialty firms.  Twenty-four of the larger textile


chemical specialty firms who sell biphenyl products are identified in Table V-l.


                    The specialty firms receive the biphenyl chemical and add


approximately 10% surfactants, or emulsifiers, which will render the water-


insoluble biphenyl emulsifiable in the dyebath.  Both nonionic and anionic


emulsifiers are used with biphenyl to create the aqueous emulsions.  The non-


ionic emulsifiers (condensation products of alkylphenols with ethylene oxide)


are the most recommended types.  However, a small amount of anionic emulsifier,


such as sodium salts of naphthalene sulfonic acid, formaldehyde condensation
                                      35

-------
                                                                           Largest:
                                                                             Burlington
                                                                             Deer ingMill Been
                                                                             J. P. Stevens
                                                                                        Dye
                                                                                        and
                                                                                        Finish
                                                                                Colored
                                                                                Fabrics
Cut
and
Sew
Examples:
  Farah
  Levi
  Etc.
                                                    Majors:
                                                      Dow
                                                      Finetex
                                                      Hooker
                                                      Monsanto
                                                      Pfizer
                                                      Standard Chlorine
                                                      Vetsi col
                                                                                Chemical
                                                                                CPS Chemical
                                                                                Dow
                                                                                East Coast Chemical
                                                                                Monsanto
                                                                                Pilot Industries
                                                                                Sun Oil of Pennsylvania
                                                                                Tanatex
Figure V-l.
Polyester  Fiber  to  Garment  Flow Diagram   (adapted  from  Otis,  1976,  and various
                        personal  communications)

-------
  Table  V-l.   Textile  Chemical Specialty  Firms  Who  Make  Biphenyl  Dye  Carriers
                Firm
      Site
Basic Product Name
 1.    Arol Chemical Products Co.
 2.    Chemical Processing of Georgia

 3.    CNC Chemical Corp.
 4.    DePaul Chemical Co.

 5.    W.F. Fancourt
 6.    Finetex, Inc.
 7.    High Point Chemical Corp.
 8.    Independent Chemical Corp.
 9.    Jordan Chemical Co.
10.    Lutex Chemical Corp.
11.    Millmaster Oxyx, Refined Onyx
        Div.
12.    Piedmont Chemical Ind.
13.    Raytex Chemical Corp.
14.    Richmond Oil, Soap & Chemical
15.    SAB Chemicals Co.
16.    Sandoz Color & Chemical
17.    A.E. Staley Mfg. Co.
18.    Standard Chemical Products
19.    Star Chemical Inc.
20.    Sun Chemical Corp.
21.    Tanatex Chemical Corp.
22.    U.S. Oil Co.
23.    Virkler Chemical Co.
24.    Woonsocket Color & Chemical
Jersey City, NJ
Dalton, GA

Central Falls, RI
Long Island City, NY

Greensboro, NC
East Patterson, NJ
High Point, NC
Brooklyn, NY
Folcroft, PA
Chattanooga, TN
Lyndhurst, NJ

High Point, NC
Charlotte, NC
Philadelphia, PA
Jersey City, NJ
Hanover, NJ
Charlotte, NC
Charlotte, NC
Macon, GA
New York, NY
Lyndhurst, NJ
East Providence, RI
Charlotte, NC
Woonsocket, RI
       Arosolve PC-7
       Chemcryl COD
       Chemkar 209
       Carrier A
       Depco Jet Carrier
         296
       Neoport BT
       Accelerit BP
       Carrier 100
       Speco Carrier 23
       Jocar LOG
       Super-Lok 845
       Decar BC

       Carrier L-300
       Raycar LBP
       Rocar 4921-A
       Sabcar #235
       Dilatin FBL
       Charlab LBPW
       Standye Car 180
       Carrier P-40
       Sunkem 660
       Carolid AL
       Uscosist 810
       Vircocarrier B
       Woonco Dye Assist  M
                                        37

-------
products, sodium lignin sulfonate, and sulfonated turkey oil and other alkylaryl
sulfonates, may be present to maintain proper dyeing levels.  The surfactants
added by each individual specialty firms are considered proprietary.
                    The biphenyl dye carrier product may also contain other
common dye carriers, especially methylbiphenyl and chlorinated solvents.  Methyl-
biphenyl is a common by-product obtained at the same time that biphenyl is re-
fined from dealkylated toluene bottoms and has excellent dye carrier properties.
The chlorinated solvents may include trichlorobenzene and perchloroethylene.
               b.   Dye Carrier Use
                    The textile chemical specialty firms, in turn, sell the
biphenyl dye carrier products to the fabric producers and dyers, who are the
ones who actually use the biphenyl product.  As many as four to five hundred
fabric dyers exist in the U.S. who use biphenyl as a dye carrier  (estimate by
industry spokesmen).  Therefore, no effort was made to identify all dyers.  How-
ever, industry spokesmen indicated that three particular fabric producers repre-
sented a "sizable" portion of the polyester market.  Those three are:
           (1)  Burlington Industries
           (2)  J.P. Stevens, Inc.
           (3)  Deering-Milliken & Co.
The corporate offices of all three are located in New York City, and all have
various plants situated throughout the United States.  Burlington, for example,
has mills  located in Greensboro, Kernersville, and Rhodhiss, North Carolina and
Roanoke, Virginia, in addition to 125 plants in the U.S.
                    Figure V-2 illustrates the general unit operations for
dyeing and finishing polyester fabrics.  The following stepwise procedure is
recommended by Dow:

                                      38

-------
CO
VO
                              Dye Carrier
                            Dyestuffs. Etc. '
                     Fabric
                                                          Biphenyl
                                                        Vapor Release
Dye
Bath
                                                      Release to
                                                   Waste Treatment
                                                                                   Wash
                                                    Biphenyl
                                                 Vapor Release
Vacuum
 Drier
                                                                                                                              Finished Fabric
                            Figure V-2.   Dyeing  and  Finishing of Polyester  Fabrics

-------
          Step #1   Water                         25,000 Ibs
               #2   Heat to 120F
               #3   Polyester Fabric               1,000 Ibs
               #4   Sequesterant                      15 Ibs
               #5   Lubricant                         10 Ibs
               #6   Anionic Dispersant                10 Ibs
               #7   Acetic Acid 70%                   15 Ibs
               #8   Dye Carrier                       40 Ibs
               #9   Disperse Dyestuffs                20 Ibs
               #10  Heat to 260F
               #11  Run for 45 minutes
               #12  Cool to 160F
               #13  Emulsified Perchloroethylene      25 Ibs
               #14  Wash

                    In general practice, the concentration of biphenyl varies

from 3-12% of the weight of fabric (Carter, 1976; Monsanto Technical Bulletin

1C/FF-29).  After washing, the fabric is dried and "heat set" in a vacuum drier.

The dyebath liquor and wash water are released to waste treatment, which may be

in-plant or city-county facilities.

               c.   Environmental Management

                    The dyebath vessel can either be pressurized or unpressurized.

When dyeing at atmospheric pressure takes place, biphenyl vapors will be released

from the dyebath.  OSHA regulations permit a TWA (time weight average) of 0.2 ppm

for biphenyl so dyers commonly use exhaust fans to vent biphenyl vapors to the

outside atmosphere.  After the fabric has been washed, it will still contain

small amounts of biphenyl.  The vacuum drier effectively removes this biphenyl,

and the vapors are again vented to the outside.  Small crystals of biphenyl may

infrequently remain in the fabric after heat setting, but biphenyl1s tendency

to sublime under normal conditions leads to disappearance of these crystals.

                    At least 95% of the biphenyl added as dye carrier is re-

leased in the waste waters.  Since the biphenyl is in an emulsified state, it
                                     40

-------
is too difficult to separate from the water;  otherwise,  it could be reused.




It appears that most of the smaller dyers release their  wastewaters directly




to city-county sewage treatment facilities while several of the larger mills




have on-site treatment (see Section IX-B-1).




               d.   Areas of Use




                    Nearly 22 million pounds  per year of biphenyl dye carriers




are estimated to be used in dyeing of polyester carpets  and draperies in




Georgia (Versar, 1976; Gaffney, 1976).  This  relatively  small geographical




area accommodates 250 to 300 mills representing 65% of the world's carpet and




rug market.




                    A similar quantity of biphenyl may well be used in the




fabric mills of North Carolina.  The textile  mills of New England also use sig-




nificant amounts of biphenyl.




               e.   Economics




                    The biphenyl producers are currently selling 50-55 million




pounds of biphenyl to the textile chemical specialty firms at a $0.16-$0.22/lb




price.  This would indicate annual sales of $8-12 million.  The textile chemical




firms process the biphenyl into dye carrier products and sell the products to




the fabric dyers at a price which is often 100% and more, above the price which




they paid for the biphenyl.




               f.   Alternative Products




                    The following chemicals are all commercially used dye




carriers which can be used in place of biphenyl:
                                     41

-------
(1)   Butyl Benzoate -
          Selling Price:
          Manufacturers:
(2)   o-Phenylphenol -
$0.30/lb (1976)
CPS Chemical Co., Cindet Chemicals, Finetex,
Velsicol, Pfizer, Tanatex
     HO.
                         DMO
          Selling Price:
          Manufacturer :

(3)  Trichlorobenzene -
          Selling Price:
          Manufacturers:

(4)  Dichlorobenzene -
          Selling Price:
          Manufacturers:
(5)  Methyl Salicylate -
          Selling Price:
          Manufacturers:

(6)  Perchloroethylene -
$1.50/lb (1976)
Dow Chemical
$0.39/lb (1976)
Dow Chemical, Hooker, Standard Chlorine
            ci
$0.31/lb  (1976)
Allied, Dow, ICC Industries, Monsanto, PPG, Solvent
Chemical, Specialty Organics, Standard Chlorine
$1.00/lb  (1976)
Dow, Monsanto, Tenneco
                             ci2c - cci2
          Selling Price:
          Manufacturers:
$0.165/lb  (1976)
Diamond Shamrock, Dow, DuPont, Ethyl Corp., Occidental,
PPG, Stauffer, Vulcan
                                      42

-------
(7)  Methyl Naphthalenes -
          Manufacturers:   Crowley Hydrocarbon, Koppers, Marathon Oil






               g.   Alternative Processes




                    A commercial waterless dyeing process for textiles has been




developed by Martin Processing Inc., Martinsville, VA.  The company claims that,




compared to conventional processes, it will eliminate water pollution, cut




energy consumption in half, and reduce capital investment 60%.  The process




makes use of a combination of organic solvents maintained in a closed system




within the equipment.  Solvents are continuously purified and recycled, and no




dyes are lost, the company says.  According to Martin, which will market the




process early in 1977 through its Temple Machinery Co. Division, the process is




applicable to about half of the 14 billion yards of fabric piece dyed annually




in the U.S. (Anon., 1976 c).




          2.   Biphenyl Fungicide in Fruit Packaging




               Biphenyl has been used for nearly 30 years as a mild fungicide




in citrus fruit wrappers and packaging.  It would be impossible to ship citrus




fruit across the U.S. or overseas in cartons, without a blue mold preventive




like biphenyl.  Years ago, "orange crates" of open lattice wood were used to let




air circulate through and reduce mold formation.  However, this exposed the




fruit to the drying effects of air, external molds, water, dirt, etc.  The




new sealed cartons prevent all these problems, but absolutely require a mold




retardant.




               During the mid-19501s, the FDA investigated the toxicity of




biphenyl.  The Institute of Paper Chemistry (IPC) was chosen to determine analysis






                                      43

-------
methods and to investigate potential problems.  As a result of the work by IPC,




biphenyl was given a clean "bill-of-health" by the FDA (Versar, 1976).




               a.   Manufacture




                    The two American producers of biphenyl-impregnated papers




are listed below:




               (1)  Crown Zellerbach Corp.        San Francisco, CA




               (2)  Paper-Pak Corp.               Orlando, FL




                    Biphenyl tissue wrappers are still manufactured as described




in the original patent (Mispley and Barber, 1940).  The biphenyl is bonded to




the tissue paper by a solvent carrying the biphenyl; the solvent consisting of




liquid paraffin oil fortified with paraffin wax.  The tissue paper will contain




about 1.75-2.97% of its weight as biphenyl and 7% to 9% of its weight as solvent.




                    Paper pads are impregnated in a similar fashion with 4 Ibs




of biphenyl per 1000 sq. ft. surface area  (Cosner, 1976).  Two pads are inserted




into each container of fruit, one on top and one on bottom.  The tissues are




used to wrap each piece of fruit individually.




                    Efforts have been made to coat the insides of corrugated




paper boxes with a biphenyl paste, but this method has yielded inferior pro-




tection.  The air permeability of corrugated boxes allows the biphenyl to




dissipate (sublime).




               b.   Production Volumes




                    Approximately 600,000 to 800,000 pounds of biphenyl are




consumed for fungicide papers per year at present (Cosner, 1976).  Production




is seasonal, as would be expected from its use in fruit protection.
                                      44

-------
                    Ten years ago, at least several million pounds of biphenyl




were annually consumed for fungicidal purposes.  However, the advent of faster




domestic transportation has lowered the need considerably.  Today, a sizeable




portion of the biphenyl papers produced are used for overseas shipments.  Domestic




use is still important, though, for long-haul shipment and closed container




storage.




                    The amount of biphenyl used as a fungicide has been de-




creasing in recent years.  Future projections indicate, at best, a stable




market; however, slight decreases can be expected.




               c.   Economics




                    A high-grade purity biphenyl is required for fungicidal




uses.  The current selling price of Monsanto's high-grade biphenyl is $0.36/lb,




indicating biphenyl sales for fungicides of $0.21 to $0.28 million annually.




The sale of biphenyl papers may amount to several million dollars per year.




               d.   Environmental Management




                    The nature of this biphenyl use indicates that all of the




biphenyl so used will eventually be exposed to the environment.  A large per-




centage of biphenyl papers will eventually be disposed in solid trash disposals




and/or incinerated.




               e.   Alternatives




                    One commercial alternative to biphenyl is -phenylphenol




(o-hydroxybiphenyl).  Ortho-phenyIpheno1 can be obtained as a by-product during




Dow's phenol production from chlorobenzene, the same process from which diphenyl




oxide was recovered.  The o-phenylphenol is converted to the sodium salt which




is used to control molds and rots of citrus and other fruits and for the
                                      45

-------
disinfection of domestic and agricultural buildings, warehouses, and refrigerated




stores.  Price is slightly higher than biphenyl, but its wider-range of protection



                                                                     CD
is a definite advantage.  It is an active ingredient in certain Lysol^cleaners.




          3.   Polychlorinated Biphenyl (PCB)




               PCB production and use has been thoroughly studied in a previous




EPA report  (Versar, 1976), so only a brief review will be given here.  This use




of biphenyl has been stopped by Monsanto and no manufacturer is allowed to




produce PCB's two years after the effective date (January 1, 1977) of the Toxic




Substances Control Act  (Section 6e, PL94-469).




               a.   Manufacture




                    Monsanto, the sole domestic manufacturer of PCB's, manufactured




this chemical in their  Sauget, Illinois plant.  The PCB manufacturing operation




is conducted in two steps.  First, biphenyl is chlorinated with anhydrous chlorine




in the presence of ferric chloride to produce crude PCB's and then the crude PCB's




are distilled to obtain the finished product.




                    Until recently Monsanto made four different PCB products;




Aroclor 1221, 1242, 1016, and 1254.  The difference is in chlorine content which




ranges from 21% in Aroclor 1221 to 54% in Aroclor 1254.




               b.   Production Volumes




                    Monsanto produced 40.4 million .pounds of PCB's in  1974 and




8.5 million pounds in the first quarter of 1975  (Versar, 1976).  The average




chlorine content is roughly 48% when all PCB products are lumped together.




Therefore,  approximately 21 million pounds of biphenyl are consumed annually




to produce  PCB's.




               c.   Economics




                    Current selling price (1976) of PCB products averages about




$6 per gallon (11.36 Ibs/gallon).  Total annual sales would therefore be nearly




$11.1 million.




                                      46

-------
          4.   Alkylated Biphenyl




               a.   Isopropylbiphenyl




                    Commercially, isopropylbiphenyl is the most important of




the alkylated biphenyls.  Tanatex Chemical Division in Lyndhurst, NJ is the




largest domestic producer of isopropylbiphenyl (Cohen, 1976); Pilot Industries




of Houston, TX also manufactures the chemical (Barrow, 1976).




                    (i)  Manufacture




                         Isopropylbiphenyl is manufactured by a Freidel-Crafts




reaction of biphenyl with propylene, the chemistry being:
DHO
                        -2
                         Primarily, the monoisopropyl derivative is formed,




but small amounts of the diisopropyl derivative will also exist.




                    (ii) Production Volumes and Uses




                         Currently, about 10 million pounds of isopropyl-




biphenyl are annually produced (SRC estimation).  Nearly all of the production




is used in carbonless paper (Cohen, 1976).  Manufacture started about 1971 and




has accelerated to the present volume.  In 1971, Monsanto terminated PCB's




sales for carbonless paper, and isopropylbiphenyl has been used as a substitute




for PCB in this application.




                         Isopropylbiphenyl may find future applications in heat




transfer and capacitor fluids.  It may be a component in Monsanto's proprietary




dielectric fluid trade named "MCS-1238" (Versar, 1976).  Monsanto has been testing




"MCS-1238" as a possible PCB replacement.






                                      47

-------
                  (iii)  Economics




                         The 1976 selling price of isopropylbiphenyl is




$0.56/lb, which would indicate annual sales of $5.6 million to the carbonless




paper industry.




               b.   Methylbiphenyl




                    Methylbiphenyl is obtained as a by-product when toluene is




hydrodealkylated to benzene.  It commonly exists as an impurity in the grade




of biphenyl sold for dye carrier use; however, methylbiphenyl alone exhibits




excellent dye carrier properties.  Small quantities of methylbiphenyl are iso-




lated and sold by Pilot Industries of Houston, TX, but commercial-scale pro-




duction has yet to occur (Barrow, 1976).




                    Since methylbiphenyl has such good dye carrier properties,




it is conceivable that efforts to synthesize it may have commercial importance




in future years.




               c.   Ethyl- and Butylbiphenyl




                    Ethyl- and butylbiphenyl are produced by Freidel-Crafts




reaction of biphenyl with ethylene and butylene, respectively.  Pilot Industries




produces small quantities for applications in heat transfer, but they are not




commercially important yet (Barrow, 1976).




          5.   Eutectic Heat Transfer Fluid




               See Section V-B-1.




          6.   Polybrominated Biphenyl (PBB)




               PBB production and use has been studied in previous EPA reports




(Mumma and Wallace, 1975; Neufeld eit al., 1977), so only brief review will be




given here.

-------
               a.   Manufacture




                    Commercial production of PBB's was thought to have been ter-




minated in 1974  (Mumma and Wallace, 1975), the commercial producers being




Michigan Chemical Corp. of St. Louis, MI, and White Chemical Corp. of Bayonne,




NJ.  The suspected termination was precipitated when, in 1973, PBB's were




inadvertently fed to dairy cows with harmful effects.  However, decabromo- and




octabromobiphenyl were commercially produced in 1975 and 1976 for export purposes




by White Chemical (Bayonne, NJ) and by Fine Organics (Sayreville, NJ) (Neufeld




et al., 1977).




                    The manufacturing process of PBB's is considered proprietary,




but patent literature  (Moore et al., 1974; Mitchell, 1973) describes production




via bromination  of biphenyl by bromine chloride or liquid bromine.




                    PBB's were used exclusively as flame retardants for plastics,




and are currently exported for this purpose.




               b.   Production Volumes




                    Michigan Chemical produced a total of about 11.2 million




pounds of PBB's  during the period of 1970 to 1975, and White Chemical produced




about 100,000 pounds of PBB's from 1970 to 1973.  In 1976, 805 thousand pounds




of PBB's were produced (Neufeld et^ al., 1977).  The total production of PBB's




from 1970 to 1976 was  13.334 million pounds.




               c.   Economics




                    The 1975 selling price of the major PBB product  (Firemaster




BP-6) was $0.75/lb.  Combining this with the largest production year, 1974 (4.8




million pounds), reveals 1974 sales of nearly $3.6 million.




               d.   Alternatives




                    One viable alternative is decabromodiphenyl oxide (see




Section V-B-6 for this discussion).





                                     49

-------
     B.   Diphenyl Oxide

          1.   Eutectic Heat Transfer Fluid

               The major current use of diphenyl oxide is for manufacture of a

eutectic heat transfer mixture composed of 73.5% diphenyl oxide and 26.5%

biphenyl.  This mixture has been marketed by Dow Chemical Co. as Dowthemr^A

since the early 1930's.  Dow produces Dowtherm^ A in Midland, Michigan.  Mon-

santo Industrial Chemicals, in Alvin, Texas, began producing an identical mixture

called Therminol VP-1 in early 1976.  Dow and Monsanto are the only domestic

producers; however, all of the known world producers of this particular mixture

are listed below:

Producer                           Country                      Product
Dow Chemical                       USA                          DowthemP'A
Monsanto                           USA                          Therminol VP-1
Imperial Chemical                  Great Britain                Thermex
Nippon Steel Chemical              Japan                        Therm S-300
Bayer                              West Germany                 Diphyl
Progil                             France                       Gilotherm

               The biphenyl-diphenyl oxide eutectic mixture is used as both a

heating and cooling heat transfer media.  It is used in liquid phase at tem-

peratures from 60F to 750F, and in the vapor phase at temperatures from 495F

to 750F.  It is non-corrosive, so carbon steel is usually selected for equipment

in which it will be used.  Physical properties of the mixture are listed on the

Material Safety Data Sheets for Dowthernr' A in Appendix B.

               The eutectic mixture is stable except at the upper temperature

levels.  The first decomposition effect of elevated temperatures is a polymeri-

zation to materials of higher molecular weight, but these polymers remain in

solution in the liquid and do not affect operation as long as their concentray

tion does not exceed 10%.  At 750F, the decomposition rate varies between 0.8%

and 3.0% per 100 hours (Danziger, 1966).  Dow has an analysis and purification

service and can reprocess deteriorated Dowtherm if polymerization is not too

advanced.  Charles E. Sech - Consulting Associates (in Michigan) sells a purification


                                       50

-------
system to individual users of DowthernP^A,  which is nothing more than a single-




plate distillation column.  The impurities from the distillation are usually




added to fuel oils because their heating value, as well as that of Dowtherm,




is quite high (Sech, 1976).



               a.   Users




                    The eutectic mixture has numerous applications in synthetic



fiber production and finishing, petroleum refining, and plastics manufacturing.


                                                (g)

About 2500 new installations, utilizing Dowtherm  A, were made in the U.S. from



1955-1965 alone  (Danziger, 1966).  It is virtually impossible to identify all



users of the product as the use is so wide-spread.



               b.   Production Volumes



                    SRC estimates that approximately two-thirds of Dow's 1975



diphenyl oxide production  (SRC estimation - 6 million pounds) was used to form-


              (S)
ulate DowthernP^ A.  This would correspond to a 1975 production of slightly less



than 5.5 million pounds of Dowtherm.  Biphenyl use accounted for roughly



1.5 million pounds.



                    Dow is currently expanding their facilities which produce



diphenyl oxide and Dowtherm^ A.  Estimates of future capacities are not available.



                    The capacity of Monsanto's new Therminol VP-1 unit is also



not available.   Due to the large available sources of the eutectic mixture




overseas, the U.S. production  is consumed domestically.  It would seem unlikely



that Monsanto's  production in  the near future would be larger than Dow's current



production.




                    World-wide consumption of the eutectic mixture exceeded



1 million gallons (8.83 million Ibs) in 1962 (Davies, 1963).






                                      51

-------
               c.   Economics
                                                                       (6)
                    The following selling prices (1976)  are for Dowtherm^A:

               5 gallon pail                    $0.84/lb
               55 gallon drum                   $0.79/lb
               4000 gallon tankers              $0.66/lb
                    The 1975 sales of Dowtherm^A would roughly be $4 million

considering a 5.5 million pound production.

               d.   Environmental Management

                    Occupational exposure to vapors of the eutectic mixture

have been regulated by OSHA standards.

                    Manufacture involves only mixing of liquid diphenyl oxide

and biphenyl.  It seems unlikely that any quantity would be released to the

environment during manufacture except by accidental spill or leak.  Dow1s

"Material Safety Data Sheet" for Dowthernr^A calls for incineration of spilled

materials (see Appendix B).

                    Users of the mixture can have contaminated quantities re-

processed by Dow or use old quantities as a burning fuel.

               e.   Use Alternatives

                    One of the major alternatives to Dowtherm^A is petroleum-

derived oils.  Numerous oils are included in this category and collectively,

these petroleum-derived oils are probably the most widely used heat transfer

media at temperature levels above that of moderate-pressure steam (up to 550F).

These oils are obtained as high-boiling fractions from petroleum.  Several com-

mercial products are listed below:

          (1)  Mobiltherm 600                     Mobil Oil Co.
          (2)  Caloria 43                         Exxon Corp.
          (3)  Security 205                       Gulf Oil Corp.
          (4)  Tellus 7Z                          Shell Oil Co.
                                      52

-------
                    Dowthernr^A has advantage over petroleum oils due to a higher



                                                                            
film temperature which can be sustained before degradation occurs.  DowthernT^ A




is useable at temperatures up to 750F,'while the petroleum oils have a limit



of 600F.  In addition, Dowtherm^ A maintains a cleaner operating surface during



                                          (S)
normal use.  The disadvantages of Dowthenn^ A include a price differential in



favor of the petroleum oils, and the extra cost of heat-tracing pipes as Dowtherm



freezes at 54F.


                     /6N

          2.   Dowfax^


                     flb
               Dowfax^ is the tradename for dodecyldiphenyl oxide disulfonic


                                                                             /o\

acid, disodium salt manufactured by Dow Chemical in Midland, Michigan.  Dowfax^



surfactants are anionic wetting agents of the sulfonate type which are used in



latex production, agricultural formulations, cleaning compounds, dye assists,




detergents, and in textile fiber production (Dow Products & Services Catalog).



               a.   Manufacture



                    A flow diagram illustrating the manufacture of Dowfax^ is



shown in Figure V-3.



                    Diphenyl oxide is alkylated with either n-dodecyl chloride



or 1-dodecene to dodecyldiphenyl oxide.  The dodecyldiphenyl oxide is dissolved



in an organic solvent, and sulfonation is carried out with S0_.  The chemical



reaction is:
                                                                             SO H)

-------
      1  Dodecene
               or 
n  Dodecyl Chloride
                               Diphenyl
                                Oxide
Alkylation
 Reactor
                                                                     SO,
Organic
Solvent
Reactor
                                                           Recycled Organic Solvent
 Density
Separation
                          Dowfax Solutions
                                               Evaporator
                                                                                    Neutral izer
                                                                                      NaOH
                                                                                    [Adapted From Valenta and Stienhauer, 1964 ]
                     Figure  V-3.   Process Manufacture  of Dowfax^Solutions

-------
The solution is allowed to density separate and the upper layer of organic sol-




vent is decanted.  An aqueous NaOH solution is now added to the bottom layer to




neutralize the dodecyldiphenyl oxide disulfonic acid to the disodium salt.  Evap-




oration of the solution to dryness gives a buff to white powder of dodecyldiphenyl




oxide disulfonic acid, disodium salt (Valenta and Steinhauer, 1964; Branson, 1977).




                    Several Dowfax^ products are available from Dow:




               (1)  Dowfa^ 2A1  Surfactant Solution

               (2)  Dowf axv 3B2  Solution

               (3)  Dowfax^ 2AO




                    (1) and (2) above are sodium salt solutions containing 45%




active ingredient of mono and di alkyldiphenyl oxide disulfonate, where the alkyl




group is C1 and C-n, respectively.  (3) Is the acid form (not neutralized with




NaOH).




               b.   Production Volumes




                    Production volumes were not available from Dow; however,




SRC estimates that Dow captively consumes about 0.75 million pounds annually of




diphenyl oxide to synthesis Dowfax  surfactants.  This would mean an annual




production of roughly 2.3 million pounds of Dowfax*^ surfactants.  Dow introduced




this product in the early 1960's.  Projections for future growth were not obtained.




               c.   Economics


                                                      /e\

                    The selling price (1976) of Dowfax^ 2A1 Surfactant Solution




is $0.47/lb; therefore, the selling price of the dry powder dodecyldiphenyl oxide




disulfonic acid, disodium salt would be approximately $1.00/lb.  This would indicate




annual sales of $2.3 million.




               d.   Environmental Management




                    It is doubtful if significant quantities of diphenyl oxide



                                                         (E)
are released to the environment via manufacture of Dowfax^   Sewer wastes






                                      55

-------
containing diphenyl oxide are treated by Dow's Michigan Division Waste Treatment

Plant (Otis, 1976).  Treatment efficiency of the plant with respect to diphenyl

oxide is unknown.

               e.   Alternative Products

                    There are numerous surfactants commercially available on

the American market.  Many are organic derivatives of high molecular weight

                                     
alkyl sulfates or sulfonates.  Dowfax  can be included in the group of surface-

active agents having ester or ether linkages.  Other chemicals included in this

group are:

          (1)  Sulfosuccinic acid esters
          (2)  Coconut oil acids, 2-sulfoethyl ester, sodium salt
          (3)  Dodecyl sulfoacetate, sodium salt
          (A)  Herring oil, sulfonated, sodium salt
          (5)  Isooctylphenol, ethoxylated and sulfonated, sodium salt
          (6)  ri-Octylphenol, ethoxylated and sulfonated, sodium salt

Selling prices on the above vary from $0.55 - $1.00/lb.

          3.   Diphenyl Oxide Dye Carriers

               Diphenyl oxide dye carriers were made commercially available in

the U.S. in 1973.  Dow Chemical supplies the "industrial" grade diphenyl oxide

to the textile specialty chemical firms as described for biphenyl dye carriers

(see Section V-A-1).  This industrial grade assays 90% diphenyl oxide and the

remainder as methylnaphthalenes and naphthalenes (Dow Form No. 110-288-72).

Diphenyl oxide is used the same as biphenyl as a dye carrier.

               The textile chemical specialty firm which apparently handles

most of the diphenyl oxide dye carriers is Chemical Processing of Georgia in

Dalton, Georgia.

               a.   Volume of Use

                    Company  spokesmen for Chemical Processing of Georgia estimate
                                      56

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diphenyl oxide dye carrier use at much less than one million per year currently.

No great increase is expected in the near future.

                    SRC estimates the current use of diphenyl oxide in dye carriers

at roughly 0.25 million pounds per year.

               b.   Economics

                    Recent selling price (1976) for Dow "industrial grade

diphenyl oxide is $0.52/lb, up from $0.32/lb in 1973.  After the chemical

specialty firms add emulsifiers and proprietary ingredients, the cost to the

textile dyers may be 100-200% greater.  This would make the total sales of

diphenyl oxide dye carriers in the neighborhood of $0.35 million per year.

               c.   Environmental Management

                    Same as for bipheriyl.  See Section V-A-1.

               d.   Alternative Products

                    Same as for biphenyl.  See Section V-A-1.

          4.   Perfumes and Soaps

               Due to its characteristic geranium odor, diphenyl oxide has been

used in perfume formulations since the early 1930's.

               a.   Manufacture

                    The major manufacturers of diphenyl oxide perfumes are:

               (1)  Givaudan Corp.                Clifton, NJ
               (2)  Florasynth, Inc.              New York, NY

                    Actual compositions of perfume products are considered

proprietary; however, the concentration of diphenyl oxide in the final products

is listed below (Opdyke, 1974):
                                     57

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                            Concentrations in %


          Soap          Detergent          Creams, Lotions           Perfume


Usual     0.05           0.005                  0.05                  0.15


Maximum   0.20           0.03                   0.10                  0.40


                    The largest user of diphenyl oxide in soaps and detergents


has been suggested to be Proctor & Gamble Company, corporate offices in Cin-


cinnati, Ohio.


                    Before compounding the "perfume" grade diphenyl oxide into


perfumes, it is common to increase the purity by chemical means (Mahinka, 1976).


Crystallization is probably the most common method.


               b.   Volume of Use


                    Recent estimates of diphenyl oxide use in fragrances in the


U.S. amounts to about 100,000 Ibs/yr (Opdyke, 1974).  This figure is down from


200,000 Ibs/yr in 1965 (Cantrill, 1968).  The 100,000 Ibs/yr figure is expected


to remain stable in the near future.


                    Nearly one-half of the diphenyl oxide currently used in


fragrance products is imported.  In 1974, 43,201 pounds of diphenyl oxide were


imported for this use (United States International Trade Commission, "Imports
                   *

of Benzenoid Chemicals and Products 1974").  Before 1974, there is no record of


any imports.


               c.   Economics


                    The selling price (1976) for "perfume" grade diphenyl oxide


is $0.85/lb, which is up from $0.51/lb in 1965.  After formulation into fragrance


products, the price will be many times greater.
                                        58

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               d.   Environmental Management




                    The nature of fragrance products indicates that all 100,000




Ibs/yr use will be exposed to man and the environment.  It should be noted that




biological data (Opdyke, 1974) suggest no adverse effects due to human use of di-




phenyl oxide in perfumes and soaps.




               e.   Alternative Products




                    Perfume formulators (Mahinka, 1976; Graham, 1976) cite many




aromatic ethers which are useable in perfumes.  The only reason diphenyl oxide




is chosen in certain instances is its relatively low cost compared to alternatives.




          5.   Butylated Monochlorodiphenyl Oxide




               Butylated monochlorodiphenyl oxide has recently been marketed by




Dow Chemical in Midland, Michigan, under the tradename "XFS-4169L".  Dow hopes




that this product will be a viable alternative to PCB's used in capacitors.




In September 1975, Dow began manufacturing XFS-4169L in pilot-quantities for




use by McGraw-Edison and other U.S. capacitor producers (Anon., 1976 b) and




is in the process of expanding capacity.




               a.   Manufacture




                    Specific details of manufacture were not available from




Dow, but production is probably accomplished by monochlorination of diphenyl




oxide followed by butylation.  Monochlorination of diphenyl oxide is described




in a Dow patent (Hennis, 1974).  According to the patent, diphenyl oxide, con-




taining 0.005 moles of 98% H-SO, as catalyst, is chlorinated to yield the




following products:  8% ^-chlorodiphenyl oxide, 67% p_-chlorodiphenyl oxide, 10%




dichlorodiphenyl oxide, and 15% unreacted diphenyl oxide.
                                      59

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                    The monochlorodiphenyl oxide can be butylated by Freidel-




Crafts reaction (Aid- catalyst) with butene or butyl chloride.   The general




formula for XFS-4169L is (Branson, 1975):
               b.   Production Volumes




                    Until 1976, only pilot-quantities of XFS-4169L were being




produced, but Dow assured the electrical industry that it would have a capacity




rate of one million pounds per year during the first quarter of 1976 (Branson,




1975).   Dow now says (Anon., 1976 b) that it hopes to have production capacity




in excess of 5 million Ibs/yr by the end of 1976.  Five million pounds of




butylated monochlorodiphenyl oxide would consume roughly 3 million pounds of




diphenyl oxide.  The diphenyl oxide and chlorobenzene expansion presently under




construction at Dow is designed to produce the additional capacity of required




diphenyl oxide.




               c.   Environmental Management




                    Sewer wastes containing diphenyl oxide are treated by Dow




Michigan Division Waste Treatment Plant (Otis, 1976); however, significant




quantities of diphenyl oxide should not be released from the XFS-4169L process




as unreacted diphenyl oxide can be recycled for chlorination.  Specific environ-




mental management techniques concerning the chlorodiphenyl oxides were not




obtained from Dow.




               d.   Economics




                    1976 selling prices of XFS-4169L range from $21.50 to




$30 per gallon depending upon volume; least expensive for 55 gallon drums, most






                                      60

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expensive for 5 gallon pails.  Large scale production figures to lower the

selling price to $12 per gallon ($1.40/lb).  If 5 million pounds per year are

sold, this would represent sales of $7 million.

               e.   Alternatives

                    Butylated monochlorodiphenyl oxide was developed to be an

alternative to the toxic and persistent PCB's, which sell for $6-$7 per gallon.

However, because of environmental contamination resulting from their use, PCB's

will no longer be produced in the future.  Many corporations are presently in-

volved in research and testing of new compounds to replace PCB's.  Some of the

primary possibilities have been summarized in a previous EPA - Office of Toxic

Substances Report (Versar, 1976); they are listed below:

               (1)  Dioctyl Phthalate
               (2)  Diisononyl Phthalate
               (3)  Isopropyl Dichlorobiphenyl
               (4)  Silicones
               (5)  Diaryl Sulfone

          6.   Decabromodiphenyl Oxide

               Decabromodiphenyl oxide (decabromodiphenyl ether, decabromo-

phenoxylbenzene) is used as a flame retardant in certain types of flame re-

sistant polystyrene, polypropylene, polybutylene, terephthalate, ABS resins,

and other plastic materials  (Levek and Williams, 1975).

               a.   Manufacture

                    The four domestic producers of decabromodiphenyl oxide are:

Producer                            Site                       Tradename

(1)  Dow Chemical Co.               Midland, MI                FR-300-BA
(2)  Great Lakes Chemical Corp.     El Dorado, AR              Great Lakes DE-83
(3)  Hexcel Corp.,                  Sayreville, NJ
        Fine Organics, subsid.
(4)  White Chemical Corp.           Bayonne, NJ
                                      61

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                    Details concerning actual manufacturing methods are con-




sidered proprietary and are not available.  A survey of patent literature re-




vealed no information concerning decabromodiphenyl oxide production.  A Dow




patent (Moore et al., 1974) describes bromination of biphenyl with bromine




chloride.  Decabromobiphenyl is obtained by adding a stoichiometric excess of




bromine chloride, under pressure in a closed vessel, to biphenyl in the presence




of an Aid- catalyst.  Decabromodiphenyl oxide could conceiveably be prepared




by a similar method.  The bromine content in decabromodiphenyl oxide is nearly




83% by weight (Tabor, 1973).




               b.   Production Volumes




                    SRC estimates that roughly 0.5 million pounds of diphenyl




oxide are presently consumed per year to produce decabromodiphenyl oxide.  This




would correspond to an annual decabromodiphenyl oxide production of 2.8 million




pounds.  Commercial production of decabromodiphenyl oxide began in 1972.




                    Company spokesmen are projecting increases in production




during the next several years; an exact percentage was not available.




               c.   Economics




                    Decabromodiphenyl oxide (Dow's FR-300-BA) is currently




selling  (1976) for $1.80/lb, which is up from $1.08/lb in 1973.  Annual sales




could amount to nearly $5 million.




               d.   Environmental Management




                    Wastes from decabromodiphenyl oxide production units should




contain only small amounts of diphenyl oxide.  The total diphenyl oxide which




may be exposed by these units is probably insignificant when compared to other




diphenyl oxide uses.  Effectiveness of diphenyl oxide waste treatment is dis-




cussed in Section IX-B-2.






                                      62

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               e.   Alternatives

                    Several years ago, polybrominated biphenyls (PBB's) were

an important commercial flame retardant.  Decabromodiphenyl oxide was developed

to compete with PBB's for various applications, but decabromodiphenyl oxide cost

nearly twice as much as PBB's.  However, domestic PBB production was terminated

in November 1974, after dairy cattle were mistakenly fed a PBB product (Mumma

and Wallace, 1975).  PBB's are still produced for export (Neufeld et^ al.,  1977).

                    One of the new flame retardants, with applications similar

to decabromodiphenyl oxide, is Citrex BC-26, sold by Cities Service Company in

Rockville, Conn. (Mumma and Wallace, 1975).  Citrex BC-26 is a halogenated

organic containing 29% bromine and 40% chlorine with a price comparable to

decabromodiphenyl oxide.

                    Other comparable flame retardants include (Tabor, 1973):

                (1)  Tetrabromobisphenol-A                  $0.57/lb
                (2)  Pentabromochlorocyclohexane            $1.10/lb
                (3)  Dibromoneopentyl Glycol                $0.55/lb
                (4)  Tris (2,3-dibromopropyl)phosphate      $0.65/lb

          7.   Minor Commercial Uses of Diphenyl Oxide

               a.   Chloromethyldiphenyl Oxide

                    Chloromethyldiphenyl oxide and di(chloromethyl)diphenyl

oxide are produced in small quantities and are used to make thermosetting foams

and resins.

                    The production technology was developed by Dow Chemical

(Doedens and Rosenbrock, 1961), but the only U.S. producer of Chloromethyl-

diphenyl oxide and di(chloromethyl)diphenyl oxide is Stauffer Chemical in

Edison, NJ  (Insera, 1976).  Stauffer has produced these chemicals since 1971.
                                     63

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                    Diphenyl oxide reacts with formaldehyde and hydrochloric



acid to produce a variety of chloromethylated compounds.  The degree of chlor-



ination determines the distribution of isomers.  Chloromethylation to 25.2%



chlorine, for example, would produce the following isomer distribution (Dow Form



No. 110-288-72):
                 HCHO + HC1
                                             (0.25%)
  (2.35%)


CH2C1   CH2C1
                                                                    (10.5%)


                                                            CH0C1   CH.C1
                                                              2     i  L
Pure materials can be recovered by use of solvent extraction and distillation



(Doedens and Cordts, 1961).



                    The total combined production of chloromethyl and di(chloro-



methyl)diphenyl oxide amounts to much less than 100,000 pounds per year  (Insera,



1976).  Initial hopes for large-scale production have failed to materialize and



significant growth in the future is not forecast.



               b.   Methoxymethyldiphenyl Oxide



                    Methoxymethyldiphenyl oxide is also produced by Stauffer



Chemical in Edison, NJ.  Production volumes are less than those for chloro-



methyldiphenyl oxide (Insera, 1976).
                                      64

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                    Diphenyl oxide and formaldehyde are used as the starting


materials to produce methoxymethyldiphenyl oxide.  Various isomers are formed,


as shown for chloromethyldiphenyl oxide.  The mono-para and mono-ortho isomers


shown below make-up the bulk of production.
                              CH2OCH3
                    Methoxymethyldiphenyl oxide is used to manufacture Westing-


house's Doryl resins (Cogley, 1976).  Doryl resins are used in high temperature


varnish applications for electrical insulators.


               c.   Pesticides


                    Diphenyl oxide has been identified in a pesticide plant's


raw effluent  (Webb et al. , 1973) via gas chromatography - mass spectrometry.  A


survey of patent literature revealed that Ciba-Geigy Corporation holds patents
                              v

describing insecticide production from diphenyl oxide.  However, the Ciba-Geigy


pesticide production facilities  (in Mclntosh, Alabama) failed to respond to in-


quiries asking about diphenyl oxide use, perhaps due to proprietary considerations.


                    The  following synthesis is an example of diphenyl oxide use


in insecticides detailed in a Ciba-Geigy patent (Franke and Traber, 1972) :
(1)
+ HCl
                                   HCHO-HC1
                                      65

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(3)
                    Ciba-Geigy has marketed the following pesticides with a




diphenyl oxide moiety:
            (Chloroxuron)
(Fluorodifen)
                    It is doubtful that the above pesticides are synthesized




with diphenyl oxide as a raw material, but diphenyl oxide may be generated in




by-product amounts large enough to detect via gas chromatograph - mass spectro-




meter.  This may account for the identification of diphenyl oxide in pesticide




effluents, but this is only speculation.  We have not been able to determine if




diphenyl oxide is definitely used as a raw material for pesticide production,




and this possibility still exists.
                                      66

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VI.  Sources of Biphenyl and Diphenyl Oxide Occurring in Nature



     A.   Biphenyl



          1.   Petroleum



               Aromatic compounds of almost every known type have been found



in petroleum.  Biphenyl and its three mono-methyl derivatives have been identi-



fied and isolated from crude petroleum (Hunt and O'Neal, 1967).



               Biphenyl, which boils at 255C, was isolated in the dinuclear



aromatic portion of petroleum boiling in the range 255 to 275C.  Mair and



Mayer  (1964) have estimated that biphenyl makes up 0.008% by volume of crude


                             9
petroleum.  In 1973, 3.1 x 10  barrels of crude oil were produced in the United



States (SRI, 1975 b).  This translates to approximately 1.3 x 10   gallons of



crude oil of which an estimated 0.008% by volume was biphenyl.  Converting to



weight measurement, an estimated 80 million pounds of biphenyl were present as



a naturally occurring constituent of the petroleum domestically produced in



1973.  In addition, nearly 5 x 10   gallons of crude petroleum were imported in



1973 (SRI, 1975 b), which may have contained an estimated 30 million pounds of



biphenyl.  Note that the combined total of biphenyl content in domestically



produced and imported crude oil, 110 million pounds, is slightly higher than the



amount of biphenyl which is refined annually, 85 million pounds  (SRC estimation).



The biphenyl which is present in petroleum appears to be used in fuels because



it is not refined; 0.008% is much too small to recover.



               It has been estimated that the total oil influx into the ocean



from routine discharges from tankers, accidents in port and on the high seas



in exploration and production, in storage, in pipeline breaks, from spent lubri-



cants, from incompletely burned fuels, and from untreated industrial and domestic
                                      67

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sewage is between 11 - 12,000 million pounds per year (Blumer et^ al., 1971).




Assuming 0.008% by volume biphenyl content, simple calculation suggests that




approximately 1,000 pounds of biphenyl are annually released into the environ-




ment with spilled oil.




               Methylbiphenyls amount to an estimated volume %, relative to




crude petroleum, of approximately 0.0404%  (Mair and Mayer, 1964; Yew and Mair,




1966).  This amounts to five times the volume of plain biphenyl.




          2.   Foods




               Stevens e al. (1966) identified biphenyl in the volatile con-




stituents of grapes by use of a capillary  gas chromatograph attached to a mass




spectrometer.  Biphenyl had previously been identified in orange volatiles by




Schultz t ajL. (1964); however, Schultz et_ al^. attributed the biphenyl's presence




to packaging materials which were impregnated with fungistat biphenyl.  The grapes




used by Stevens in his investigation were  handled in bulk, and fungistat biphenyl




could not have come from packaging.  It would seem possible, therefore, that




biphenyl may be a naturally occurring constituent of grape volatiles.




               Kinlin et_ al. (1972) identified biphenyl in the volatile consti-




tuents of roasted filbert nuts while Walradt et_ al.  (1971) found biphenyl in




peanut volatiles.  Stoll t al. (1967) identified biphenyl as one of 202 consti-




tuents present in coffee concentrate.




               The amounts of biphenyl which may occur in foods are very small




and it is very doubtful if any significant quantities of biphenyl are exposed




to the environment via this route.




     B.   Diphenyl Oxide




          1.   Plants




               In addition to biphenyl, Stevens et^ al. (1966) identified diphenyl
                                      68

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oxide in the volatile constituents of grapes.   Kimland et al.  (1972)  identified




diphenyl oxide as one of many compounds present in Greek tobacco.




               The amounts of diphenyl oxide which may be released to the environ-




ment from plants are probably very small.
                                      69

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VII. Generation of Biphenyl and Diphenyl Oxide By-Products

     Section IV (General Manufacturing and Production Technology) discussed the

processes by which biphenyl and diphenyl oxide by-products are obtained and

refined commercially.  This section examines biphenyl and diphenyl oxide gener-

ation in processes in which they are not refined or intended to be refined.

     A.   Biphenyl

          1.   Dealkylation of Toluene

               The commercial producers of refined biphenyl, from the dealkylated

toluene by-product, are identified in Section III (Production) and Section IV-A-1,

along with the petrochemical company sources of the by-product.  The companies

listed below also produce benzene by dealkylating toluene; however, they do not

refine the biphenyl stream or sell it to refiners.

Company                                             Site

1.   Ashland Oil Co.       .                         Cutlettsburg, KY
2.   Crown Central Petroleum Corp.                  Houston, TX
3.   Enjay Chemical Co. (Exxon)                     Baytown, TX
4.   Leonard, Inc.                                  Mount Pleasant, MI
5.   Monsanto                                       Alvin, TX
6.   Shell Oil Co.                                  Odessa, TX
7.   Signal Oil & Gas Co.                           Houston, TX
8.   South Hampton Co.                              Stilsbee, TX
9.   Sunray-DX                                      Tulsa, OK

               The biphenyl streams generated by the above companies are added

to fuels, usually fuel oils.  The amount of biphenyl added to fuels via toluene

dealkylation totals nearly 20-25 million pounds annually  (SRC estimation).

          2.   Naphthalene Feedstocks

               Most of the naphthalene produced by petroleum operators is

petroleum-derived.  Naphthalene and/or naphthalene precursors occur in
*Hahn, 1970, p. 411-412

                                       70

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significant quantities in the following petroleum-derived streams (Erskine,  1970),

and the streams are used as naphthalene feedstock to produce a purified naphtha-

lene.

          (1)  Petroleum streams are catalytically reformed with the intention

               of producing high-octane motor and aviation gasoline, and it is

               possible to operate the reformer to yield heavy "bottoms" that

               contain a high portion of methylnaphthalenes and naphthalenes.

               Biphenyl is found as a by-product in the "bottoms".

          (2)  Catalytic cracking is used to convert heavy petroleum fractions

               into lighter gasoline components, and one of the products of

               cracking contains naphthalene precursors.  Biphenyl is also

               formed during cracking.

The typical composition of naphthalene feedstocks obtained from catalytic re-

formates and cracking are (Doelp, 1966):

                                   Catalytic                        Catalytic
                               Reformates (Wt %)                 Cracking (Wt %)

biphenyl & acenaphthenes              6%                                6%
alkylnaphthalenes                    55%                               35%
alkylbenzenes                        20%                               25%
other aromatics                      19%                               34%

               Naphthalene is obtained by hydrodealkylating the alkylnaphthalenes

by the same method as previously described for hydrodealkylating toluene to ben-

zene (Section IV-A-2).  Once again, the biphenyl by-product which is produced

will probably be added to fuels.
                                      71

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          3.   Coal Tar




               Biphenyl was first identified in the high-boiling fractions from




coal tar distillation in 1875 by Bvichner (Poffenberger, 1950).  Coal tar amounts




to about 3% by weight of the coal which is processed.  Along with many other




hydrocarbons, biphenyl is part of the high-boiling fractions, distilling in the




range 250-300C; however, no chemicals are separated commercially from this




range.  A fraction distilling mainly in the range 240-270C is employed at




coking installations as wash oil for scrubbing benzole from coal gas, but most




of the oils in this range are used in creosote blends (McNeil, 1969).  These




creosote oils are used for coating wood as a preservative, usually on railroad




ties and telephone poles.  Due to the nature of this use, any biphenyl content




of the creosote oil will be exposed to the environment from weathering effects,




which may leach or vaporize the biphenyl from the treated wood.




               Approximately 160 million gallons of creosote oil are consumed




annually (SRI, 1974).  Dolansky (1974), in an analysis of creosote oil, determined




that 60% of the oil was composed of a hydrocarbon fraction and that 1.35% of the




hydrocarbon fraction was biphenyl.  Applying Dolansky's figures to the U.S.




consumption of 160 million gallons of creosote oil annually reveals that




approximately 10 million pounds of biphenyl are contained in this consumption.




It is probably reasonable to assume that the bulk of this biphenyl will be ex-




posed to the environment.




               In 1974, 677 million gallons of coal tar were produced domesti-




cally (United States International Trade Commission).  Excluding that portion




of the coal tar distilled to creosote oils, the coal tar probably contained from




several to 10 million pounds of biphenyl which apparently ended up in fuels or




coking operations, but this is not known for certainty.
                                    72

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          4.   Automobile Exhaust




               It is likely that biphenyl is a component of the exhaust gas




emitted by an automobile engine; however, there is no proof in the literature




to support this supposition.  Schofield (1974) lists the various hydrocarbon




components identified in auto emissions, which he obtained from the General




Motors Research Laboratories.  The hydrocarbon list contains 1.11% by volume




of unidentified aromatics, and it may be possible that biphenyl is included




in these unidentified aromatics.  Schofield does identify the presence of ben-




zene at a volume concentration of 2.15%, and at the elevated temperatures of




an automobile engine it is possible that the benzene could react chemically




to form biphenyl.  Section IV-A-1 describes Monsanto's commercial production




of biphenyl by passing benzene vapors through a thermal reactor.




               The total emissions of hydrocarbons from transportation sources




was estimated to be 29,400 million pounds in 1971 (Council on Environmental




Quality, 1973).  If even a fraction of a percent of these emissions is biphenyl,




sizeable quantities could be released directly to the environment.




     B.   Diphenyl Oxide




          1.   Caprolactam - Nylon Production




               Over 90% of the caprolactam produced in the U.S. is used to manu-




facture Nylon 6.  The following data suggest that diphenyl oxide is formed as




a by-product during the production of caprolactum or its precursors: (1) Phenyl




ether  (diphenyl oxide) has been identified in a settling pond of a nylon plant




in concentrations of 0.05 mg/1 (Webb at al., 1973); and (2) diphenyl oxide has




been isolated as an impurity in technical caprolactam in concentrations of




10 ppm (Kolar and Klacel, 1962).
                                      73

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               Caprolactam is commercially synthesized from processes based on




cyclohexanone.  It is difficult to predict any diphenyl oxide by-product for-




mation during these processes.  However, cyclohexanone is prepared, in one




commercial process, by catalytic hydrogenation of phenol.  Phenol can be




catalyzed to produce diphenyl oxide, as shown by Monsanto's commercial method.




It may, therefore, be possible that diphenyl oxide is formed in small amounts




during the manufacture of cyclohexanone via phenol.




          2.   Bituminous Coal Tar




               Diphenyl oxide has been identified as one of 133 individual




compounds present in bituminous coal tar (Karr et^ al., 1967).  The fate of




diphenyl oxide which may be present in coal tar is unknown.
                                      74

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VIII.  Material Balance - Exposure to the Environment


     This section attempts to define quantitatively the amounts of biphenyl and


diphenyl oxide released to the environment by man.  Only uses which are releasing


or could potentially release substantial amounts of biphenyl and diphenyl oxide


to the environment are discussed.  The following areas are not discussed because


quantities which may be released are insignificant by comparison: production of


refined biphenyl and diphenyl oxide and chemical synthesis (PCB's, alkylated

                 j^
biphenyls, Dowfax , butylated mpnochlorodiphenyl oxide, decabromodiphenyl oxide,


chloromethyldiphenyl oxide, or pesticides).


     A.   Biphenyl


          Table VIII-1 lists the estimated environmental releases of biphenyl.


Explanations of the high-low estimates are given below.


          1.   Dye Carrier


               Virtually all of the biphenyl used in dye carriers is released


from the dyeing plants, either in air emissions or in waste waters.  Industry


spokesmen estimate that less than 5% of the biphenyl is exhausted as vapor,


so the large bulk is released in the waste waters.  A discussion involving the


environmental fate of this water-released biphenyl is presented in Section IX-


B-l.  The high estimate given in Table VIII-1 was obtained by arbitrarily assuming


that only 50% of the released biphenyl was effectively treated or treated at


all; the low estimate was obtained by assuming all of the biphenyl was treated


with a 95% efficiency.                                                ,.'


          2.   Fungicide


               As described in Section V-A-2, the biphenyl used as fungicide is


bound by solvents to either tissue paper or to paper pads.  The biphenyl will
                                      75

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                   Table VIII-1.   Estimated Environmental Releases of Biphenyl
Use* or
Dye Carrier
Fungicide
/B\
Dowthernf0'^ A
Creosote Oils
Petroleum
Naphthalene Feedstocks
and Toluene Dealkylation
By-Product, Unrefined
Coal Tar, excluding
Creosote Oil Fractions
Automobile Exhaust
Current Annual
Use, Production
Content (X106 Ibs)
50
0.6-0.8
1.5
10
110
30-40
3-10
-
Quantities of Biphenyl
Current Annual
Environmental Release
Estimates (X106 Ibs)
High Low
25 3
0.6-0.8 0.3-0.4
small* -
10 10
small* -
small* -
unknown -
unknown unknown
(SRC Estimations)
Estimated 1966-1975
Use, Production, or
Content (X106 Ibs)
250-300
20-30
10-15
100
1000
200-300
30-100
-
Estimated 1966-1975
Environmental Release
(X106 Ibs)
High Low
125-150 15-18
20-30 10-15
small* -
100 100
0.01
small* -
unknown
unknown unknown
* See discussions in this section

-------
eventually dissipate from the papers as air emissions, due to biphenyl's



volatility, if left open to the atmosphere.  The high estimate given in



Table VIII-1 was obtained by assuming all of the biphenyl was allowed to



dissipate; the low estimate by assumming one-half of the papers were des-



troyed by incineration, thereby destroying the biphenyl.


                       
          3.   Dowthernr A

                                                                    /m

               It would seem unlikely that large amounts of Dowtherra^ A are



released to the environment because decomposed or impure Dowtherm can be used



for fuel purposes or purified via distillation.


                                                          (5)
               There is no set "working-life" for Dowtherm^ A (Anderson, 1976).



As long as decomposition does not occur, the fluid can be used for many years



(decomposition is dependent upon working temperature).  In actual practice,



the impurities are periodically removed from the system and the system is



simply "topped-off" with fresh Dowtherm.



               Because Dowtherm^ A can last for years, the quantities in



current use must be quite high.  SRC estimates that 5.5 million pounds of



Dowtherm^ A were produced in 1975.  It is possible that 30-40 million pounds



or more are currently being used.  An attempt to produce an exact figure for



current use was unsuccessful.



          4.   Creosote Oils



               As explained in Section VII-A-3, due to the nature of the use



of creosote oils, any biphenyl content will be exposed to the environment



through use.  Due to biphenyl's volatility, this biphenyl will be exposed



to the air as vapor emissions or may be leached by water from the treated wood.
                                       77

-------
          5.   Petroleum

               It would seem unlikely that any large quantities of the very

low percentage of biphenyl present in petroleum will be exposed to the environ-

ment.  In Section VI-A-1, it was estimated that approximately 1000 pounds of

biphenyl are exposed to the environment annually from oil spills.  For the ten-

year period between 1966-1975, a figure of 10,000 pounds was assumed for release

determination.

          6.   Naphthalene Feedstock and Toluene Dealkylation By-Product,
               Unrefined

               As for petroleum, it would seem unlikely that any large quan-

tities of biphenyl present in these sources will be exposed to the environ-

ment.  The biphenyl from these sources will probably be added to fuel oils

which are burned.  The biphenyl that is burned for fuel should be destroyed

and, therefore, not released to the environment.

          7.   Coal-Tar, Excluding Creosote Oils

               As explained in Section VII-A-3, the eventual fate of this

product is not certain; therefore, no estimate is made.

          8.   Automobile Exhaust

               See discussion of Section VII-A-4.

     B.   Diphenyl Oxide

          Table VIII-2 lists the estimated environmental releases of diphenyl

oxide.  Explanations of estimates are given below.

          1.   Dye Carrier

               All of the diphenyl oxide used in dye carriers is released from

the dyeing plants, either in air emissions or in waste waters as previously
                                      78

-------
                          Table VIII-2.   Estimated  Environmental  Releases  of Diphenyl  Oxide
vo
Quantities of Diphenyl Oxide (SRC Estimation)
Current Annual
Use*
Dye Carrier
Perfume and Soap
(8)
Dowtherm^ A
Current Annual
Use (X106 Ibs)
0.25
0.10
4.0
Environment
Estimates
High
0.13
0.10
small*
:al Release
(X106lbs)
Low

.013
0.05
-
Estimated 1966-1975
Environmental Release
Estimated 1966-1975 (X16 lbs)
Use (X106 Ibs) High Low

1.0 0.5 0.05
1.0-2.0 1.0-2.0 0.5-1.0
30-40 small*
         * See discussion in this section

-------
described for biphenyl dye carriers.  The high estimate given in Table VIII-2


was obtained by assuming that only 50% of the released diphenyl oxide was


effectively treated or treated at all; the low estimate was obtained by


assuming all of the diphenyl oxide was treated with a 95% efficiency.


          2.   Perfumes and Soaps


               It can be assumed that all of the diphenyl oxide used in per-

fumes and soaps will be released to the environment.  The high estimate given

in Table VIII-2 assumes no treatment at waste water facilities to degrade

diphenyl oxide content; the low estimate assumes that 50% of the released


diphenyl oxide is treated effectively.
                       /g\
          3.   Dowthernr^ A

               See discussion in Section VIII-A-3.
                                      80

-------
IX.  Environmental Perspectives

     A.   Occupational Exposure to Man

          The following OSHA standards have been established for exposure to

biphenyl and diphenyl oxide in air:
                                                      3
       Biphenyl          0.2 ppm (approximately 1 mg/m ) (time weighted average)

       Diphenyl Oxide    1.0 ppm (time weighted average)

There are no OSHA recommendations to control direct contact of biphenyl or di-

phenyl oxide in solid or liquid form; possible skin absorption of these sub-

stances is apparently not considered to have measureable health significance.

          The following toxicity data are available for the two chemicals

(Christensen and Luginbyhl, 1975; Opdyke, 1974; Haas e al., 1975; Branson, 1977)
                                                                 3
          Biphenyl:  inhalation - human          *TD  : 4400 yg/m
                     oral - rat                   LD^: 3280 mg/kg
                     oral - rabbit                LDsn: 240 m8/k
                     skin - rabbit                U> ": 2500 mg/kg
                     fish - fathead minnow        TL  (96 hrs): 1.5 mg/1
                          - fathead minnow        LC  (96 hrs): 5.3 mg/1

          Diphenyl
            Oxide:   oral - rat                   LDSO: 337 m8/k
                     skin - rabbit                LD^JJ: > 5000 mg/kg
                     fish - fathead minnow        LC^ (96 hrs): 5.5 mg/1
*Key to Abbreviations

     TD   - lowest published toxic dose
     LD^ - lethal dose 50 percent kill
     TL   - tolerance median
     LC,.- - lethal concentration 50 percent kill
                                     81

-------
     B.   Release to the Environment




          1.    Biphenyl




               Most of the biphenyl released to the environment by man is re-




leased by the textile dyeing industry.  The larger dyers (Burlington, for ex-




ample) operate mills which have their own waste treatment facilities to process




wastes while most other dyers apparently release wastes to city or county




facilities.




               a.   Effectiveness of Biphenyl Waste Treatment




                    The exact effectiveness of treatment of biphenyl wastes by




each treatment plant cannot be ascertained because the individual treatment




plants do not monitor biphenyl levels.  Instead, they monitor BOD and/or COD




levels.




                    To provide an example of COD levels before and after treatment,




SRC contacted the largest Burlington Industries' mill, which is located in




Greensboro, NC.  Burlington operates their own waste treatment facility at this




mill.  Mr. Joe Ameen, Sanitary Engineer for the mill, reports that COD normally




measures 1200-1500 mg/1 on the influent stream to waste treatment while the




effluent normally measures 200-300 mg/1.  The effluent is discharged into a




river.  In addition to biphenyl, the influent stream contains other dye carriers,




such as trichlorobenzene, butyl benzoate, etc., dyestuffs, emulsifiers, and all




other  factory wastes.  Mr. Ameen also reports that in community waste treatment




plants operated by Burlington in other cities, a 15% or more addition of community




solid wastes to the Burlington wastes reduces COD levels of the effluent to 50-




100 mg/1.




                    Dr. Peter Gaffney of the Biology Department of Georgia




State University has been studying biphenyl problems in water at municipal
                                      82

-------
waste treatments for several years.  He states (Gaffney, 1976) that biphenyl is




effectively processed by the treatment plants; however, his concern has been




directed at potential PCB formation during chlorine pre-treatments.. This PCS




formation is discussed in more detail in Section IX-B-l-c.




                    Biphenyl has been detected in river water by Webb et al.




(1973) and Kites (1973).  Kites identified biphenyl, trichlorobenzene, and




butyl benzoate in the waters of the Merrimack River at 0.1-0.5 ppb concentra-




tion.  Kites attributes the presence of these organics to upstream textile




factories.




                    Also, W.C. Tichner of the Environmental Resources Center




of Georgia Institute of Technology has been studying the problem of biphenyl




effluents from polyester carpet manufacturing in Georgia.  Tincher has measured




biphenyl concentrations in streams at the point of effluent discharge to several




miles downstream.  He has found that the biphenyl concentration drops quite




rapidly after effluent discharge.  He attributes this phenomenon to the vola-




tility of biphenyl (Tincher, 1976).  It is worth noting that rather than complete




biphenyl degradation, at waste treatment plants, or complete volatilization occurr-




ing, various degradation intermediates may be present  (usually not determined)




such as, phenylphenol (Gaffney, 1977 a).  There has apparently been no work done




showing the kinetics of biphenyl degradation completely to carbon dioxide and




water; this would be desireable.




                    In 1974, the Sun Oil Co. commissioned Dr. J. Ferguson of




Johns Hopkins University to experimentally determine biodegradation rates for




biphenyl and other common dye carriers.  To determine aerobic biodegradation
                                      83

-------
rates, typical treatment cultures were obtained and pre-conditioned to the dye




carriers.  All cultures received an initial dye concentration of 50 ppm.  Ex-




tractions of the culture and the water system were made at various times and




analyzed.




                    Figure IX-1 shows how long the microorganisms took to reduce




the concentration of the dye carrier containing 95% biphenyl and of the other




dye carriers (Haas et al., 1975).  The biphenyl was totally biodegraded in about




48 hours.




               b.   Environmental Chlorination of Biphenyl




                    Dr. Peter Gaffney first reported finding PCB's in a sewage




treatment plant's trickling filter bed in 1974 (Gaffney, 1974).  He suggested




that the PCB's were generated as a result of a high biphenyl influx from a tex-




tile mill coupled with a waste water pre-chlorination for odor control and dis-




infection.  It was determined later, however, that commercial PCB's were entering




this waste treatment facility.  In laboratory tests, Gaffney found that PCB's




were formed when 10 mg/1 of biphenyl were added to dionized water held at 20C,




and then 1 mg/1 of chlorine was added and the reactants kept in contact for one




hour  (Versar, 1976).




                    Carlson &t^ al. (1975) conducted a detailed laboratory




analysis to determine chlorine incorporation into biphenyl and other aromatic




compounds under conditions utilized for water renovation.  Table IX-1 is a




summary of PCB and chlorobiphenyl formation under the various aqueous conditions




used  (Carlson et al., 1975).  the results shown in Table IX-1 confirm the




possibility of chlorine incorporation into the biphenyl nucleus under a variety




of conditions.
                                       84

-------
  100
                                                      1,2,4-Trichlorobenzene

                                                      and Perchloroethykene
o
I
o
u
                                                3-Methyl-Methyl Sal icy late
    40-
    20-
                                Elapsed Time ( Hours)
Figure  IX-1.
         Reduction of  Concentration Owing to Biodegradation - Analysis of

         Culture Cells and Water  (Haas  et al. , 1975)
                                85

-------
                  Table  IX-1.   Chlorination  of Biphenyl  Utilizing Water  Renovation Conditions
                                  (Carlson  et al.,  1975)
oo
Chlorine
Source
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
C12
NaOCl
C12
NaOCl
ci2a
NaOCl
pH
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
2.1
2.8
4.9
10.4
2.2
7.0
Chlorine,
ppm
100
100
100
100
10
20
35
50
100
10.9
295
266
830
1350
2950
Reaction
Time, hr
24
48
72
120
120
120
120
120
120
0.25
0.25
0.25
0.25
0.25
0.25
Reaction,
0.4
1.0
1.7
2.5
0.004
0.02
0.04
0.15
0.27
2.2
9.3
0.1
0.6
16
5.2

2-
15
32 
56
69
0.1
0.44
1.4
4.0
8.8
120
450
5-10
40
180
280
Ppb of Chlorinated Product
3-, 4- 2,2' 2,3'-2,4' 4,4'-
10
27
47
82
0.12
0.51
1.2
4.9
7.4
10 20
190 10 130 40


80 80 370 500
110 80 30
           Saturated biphenyl solution found experimentally to be 6.0 mg/1.
            Higher chlorinated isomers also present.

-------
                    Dr. Gaffney has conducted an investigation to determine if


chlorobiphenyls can be produced in wastewater treatment plants because of the


use of chlorine with municipal wastes containing biphenyl (Gaffney, 1977 b).


The results indicated that various chlorobiphenyl isomers are produced during


final chlorination.  The chlorobiphenyl isomers predominately formed are the


2-chloro, 2,2'-dichloro, and 2,4'-dichloro isomers.   A relatively small amount


of trichlorobiphenyl was also detected.  It should be noted that the term PCB


should be reserved for only those biphenyl molecules having three or more


chlorine atoms attached.  Laboratory chlorination of influent and effluent from


a municipal waste treatment facility also results in the formation of these and


other chloro-organic substances (Gaffney, 1977 b).


                    Dr. Richard Johnsen has also conducted laboratory studies


of biphenyl chlorination under conditions which may exist at waste treatment


plants (Johnsen, 1975).  Biphenyl in water (5 ppm) was added to chlorinated water


given chlorine concentrations of 8, 83, and 830 ppm.  Under ambient conditions


and after aging for 24 hours and 1 week, the samples were analyzed, along with


suitable controls, by gas chromatography.  The results were somewhat surprising;
     i

when chromatographs of biphenyl reacted with Cl^-water (83 ppm and 830 ppm) for


1 day are superimposed over a chromatograph of Arochlor 1221 (a commercial PCB),


striking overlaps are observable, although peak heights are not the same.  This


preliminary work by Dr. Johnsen is being continued.


                    Dr. E.L. Kothny has suggested an interesting source of PCB


and other chlorinated organics found in the environment (Kothny, 1976).  He has


proposed that the chlorine released from sea salt particles might chlorinate


organics such as biphenyl found in the atmosphere.  There is, however, no evi-


dence to support this contention at present.
                                       87

-------
          2.   Diphenyl Oxide




               The information and data given below have been acquired from the




Dow Chemical Co. (Otis, 1976).




               a.   Effectiveness of Waste Treatment




                    "Generally, organic chemicals with a BOD- (5 day biochemical




oxygen demand) value in excess of 60 percent of the stoichiometrically required




amount of oxygen are readily degraded in conventional waste treatment facilities.




Under favorable waste treatment conditions, concentrations of diphenyl oxide in




waste streams have been reduced up to 95%.  This magnitude of reduction is typi-




cal of that encountered with municipal wastes.  Analytical methods are available




for measuring the concentrations of diphenyl oxide in waters and waste streams.




In the event of a gross discharge of diphenyl oxide into a river, techniques are




available that can predict the downstream concentrations of diphenyl oxide based




on some known rates and routes of removal from the river.  These routes include




microbial degradation  (by a variety of aquatic microorganisms), absorption on




suspended solids, and volatility from water"  (Dow Technical Data Sheet - XAS-




1075L).




               b.   Biodegradation




                    "The most desirable environmental property of diphenyl oxide




is its ability to biodegrade into carbon dioxide and water in the presence of




naturally occurring microorganisms.  This observation is supported by a variety




of tests including the standard biochemical oxygen demand (BOD) test, an oxygen




probe test, and tests which measure the chemical disappearance from soil and




river sediments.  A postulated mechanism of diphenyl oxide conversion to carbon




dioxide and water under the influence of aerobic microorganisms is believed to






                                     88

-------
involve some catechol-like intermediates.  However, positive proof for this

mechanism has proven difficult because of the transient existence of the inter-

mediate compounds" (Dow Technical Data Sheet - XAS-1075L).

               c.   Bioconcentration

                    "Detection of chemical residues in fish has been the key

environmental alert for DDT and PCB's.  Consequently, the potential of diphenyl

oxide to bioconcentrate was determined.*  Bioconcentration is a measure of the

relative distribution of a test chemical between fish tissue and exposure water.

Diphenyl oxide has been found to bioconcentrate to only a limited extent, quite

unlike DDT or PCB's.  When placed in fresh water, the fish were found to eliminate

diphenyl oxide rapidly, 50% each day compared to 50% each 30 days for an isomer

of PCB's.  These results show that hazardous or persistent concentrations of

diphenyl oxide in fish are unlikely to occur" (Dow Technical Data Sheet - XAS-

1075L).

                    The potential for biphenyl to bioconcentrate was also deter-

mined by Dow Chemical.  Neely et^ a!L., (1974) determined the bioconcentration as

the ratio of the uptake rate of the exposure chemical to the clearance rate.

For biphenyl, the bioconcentration was found to be 438+48 while for diphenyl

oxide the bioconcentration was 196+39.
*Results published by Neely e^t al.,  (1974).  The log bioconcentration factor
 was experimentally determined as 2.29 (therefore, bioconcentration factor = 196)
                                      89

-------
X.   Environmental Assessment




     A.   Biphenyl




          Biphenyl is being released to the environment in quantities which may




total 60 million pounds annually and perhaps even higher (SRC estimate).  The




largest known source of biphenyl release is from biphenyl's use as a dye carrier




in the dyeing industry.  Approximately 50 million pounds of biphenyl are annually




used for dyeing applications (SRC estimate).  This biphenyl is usually released




in the wastewaters from the dyeing factories to either municipal treatment




facilities or to on-site treatment facilities.  Common forms of waste treatment




appear to be successful in the processing of biphenyl wastes (Gaffney, 1976).




Laboratory experiments have shown that typical cultures from water renovation




facilities are able- to reduce biphenyl concentrations to nearly zero in only 48




hours  (Haas et^ al., 1975).  However, since biphenyl is not monitored at treat-




ment facilities, the efficiency of general treatment cannot be determined with




certainty.  Also, the method of treatment may be a significant factor in the




amount of biphenyl converted by biodegradation.  Tihcher (1976) has found that




the concentration of biphenyl released to streams rapidly falls below 1 ppm




after  release, due to biphenyl's volatility.  This suggests that methods which




allow biphenyl wastes to be exposed to the atmosphere for periods of time during




treatment may allow quantities of biphenyl to be released into the air by volatil-




ization.




          A major concern of biphenyl release to waste treatment plants from the




dyeing industry is the evidence which indicates that biphenyl-containing sewage




may be chlorinated to PCB or chlorobiphenyl isomers during pre-chlorination




processes for disinfection and deodorization  (Gaffney, 1974, 1976, 1977b;
                                    90

-------
Carlsen, 1975; Johnsen, 1975).  Laboratory experiments which have mimicked




treatment facility methods have found that the biphenyl nucleus can be chlor-




inated with four, or usually less, chlorine atoms.   Commercially prepared PCB's




have a much greater degree of chlorination and have certainly less biodegrada-




bility than the PCB and chlorobiphenyl isomers which may be generated at waste




treatment plants.  Although sufficient research has yet to be done for conclusive




results, the present indications suggest that chlorination of biphenyl-containing




sewage deserves a great deal of consideration and perhaps restriction.




          Another major source of biphenyl release to the environment is from




creosote oils which are used to preserve wood, especially railroad ties and




telephone poles.  Biphenyl is present in creosote oils because it is one of the




constituents in the high-boiling fractions of coal tar from which these creosote




oils are derived.  It is likely that nearly 10 million pounds of biphenyl are




annually released to the atmosphere by biphenyl1s volatilization or to water by




leaching from creosote oils (SRC estimate).




          An uncertain but potentially significant source of biphenyl exposure




to the atmosphere is automobile exhaust.  It is possible that biphenyl is one of




the many hydrocarbons present in auto emissions; however, there is no available




monitoring data to confirm this supposition.  Even if biphenyl is present in




only a very small fraction of a percent, the annual quantity emitted could be




very large due to the enormous amounts of hydrocarbons emitted by autos.




     B.   Diphenyl Oxide




          Diphenyl oxide is being released to the environment in quantities which




may total 0.25 million pounds annually (SRC estimation).  The two major sources
                                       91

-------
of diphenyl oxide release are soap and perfume use and dye carrier use.   Man




has been exposed to diphenyl oxide as an ingredient in some soaps and perfumes




since the early 1930's.  Laboratory and practical experience have suggested




no adverse effects from diphenyl oxide use via perfumes and soaps.  The Council




of Europe (1970) included diphenyl oxide in the list of temporarily admissible




artificial flavouring substances (Opdyke, 1974); however, spokesmen for Dow




Chemical (Branson, 1977) indicate that flavouring should mean odor and not




food additive.  They question the use of diphenyl oxide as a food additive




without more data.




          Industrial effluents from plants using diphenyl oxide as a dye carrier




can apparently be effectively treated in conventional waste treatment facilities




(Dow Technical Literature - XAS-4169L) when such treatment is used.
                                      92

-------
    Appendix A





Physical Properties
         93

-------
Biphenyl (Monsanto Tech. Bull. 1C/FF-29)
Melting point, C
Boiling point at 760 mm Hg, C
                10.5 mm Hg, C
Specific gravity, 20/4C
                  77/4C
                    69
                  '255
                   118
      Vapor pressure 0.0097 mm Hg at 25C**
Lbs./gallon at 77C
Refractive index, n
77
D
Viscosity at 70C, Saybolt Sec.
            100C, Saybolt Sec.
 1.04
 0.99
 8.23
 1.588
31.2
28.8
Surface tension at 129,2C, dynes/cm    39.5
Flash point, closed cup,  C
              Open cup,  C
Latent heat of  fusion, Btu/lb.
Specific heat,  Btu/lB/F
Odor
Appearance
Molecular Weight
Empirical Formula
Structural  Formula
                   113
                   124
                    53.1
                     0.43
                    Pleasant, peculiar
           Colorless to pale yellow crystallized solid or  flakes
                   154.20
                C6H5C6H5
 Solubilities  - Grams biphenyl per  100  cc  of  solvent
               Solvents                            Solubility
Water
bons Mineral Spirits
Gasoline (Texaco)
Kerosene
Benzene
Xylene
Turpentine
Toluene

16.9
24.1
17.5
81.5
56.9
24.2
62.0
0.00018*
0.00075 at 25C**
26
26
27
27
27
24
18

     * 95% Biphenyl dye carrier  (Haas et al., 1975)
    ** Branson  (1977)
                                    94

-------
Diphenyl Oxide (Dow Form No. 110-288-72)
                                               DIPHENYL OXIDE GRADE
                                     Technical        Perfume        Industrial
Molecular Weight
Boiling Point C 760 mmHg
Specific Gravity 25/25C
Pound per gallon, 25 C
Refractive Index, 25 C
Freeze Point C
Flash Point F COC
Fire Point F
Auto Ignition Point F
Latent Heat of Vaporization
Cal/mole at B.P.
Approximate Solubility g/lOOg
Solvent at 25 C
Acetone
Ether
Benzene
Methanol
Water
Carbon tetra chloride
n-Heptane
170.2
257
1.070
8.92
1.578
26
239
258
1144
11,800



00
00
oo
oo
20.8 ppm
00
00
170.2
257
1.070
8.92
1.579
27
239
258
1144
11,800



OO
00
00
oo
21 ppm
00
00
_
255
1.065-1.075
8,92
-
15
235
255
-
-



00
00
00
oo
21 ppm
oo
00
 Solubility  of  DPO  in water  at  25C	20.8 ppm
 Solubility  of  water in  DPO  at  25C  	  ...........   0.071%
 Solubility  of  water in  DPO  at  30C	0.077%
                       BOILING POINTS OF DIPHENYL OXIDE
                Boiling Point                         MM Hg
257. 9C
181. 3C
147. 1C
121. 0C
77.0C
760
100
30
10
1
  Vapor pressure 0.019 mm Hg at 258C*
  *Branson (1977)
                                   95

-------
Diphenyl Oxide (Dow Form No. 110-288-72)
                                               DIPHENYL OXIDE GRADE
                                     Technical        Perfume        Industrial
Molecular Weight
Boiling Point C 760 mmHg
Specific Gravity 25/25C
Pound per gallon, 25 C
Refractive Index, 25C
Freeze Point C
Flash Point F COC
Fire Point F
Auto Ignition Point F
Latent Heat of Vaporization
Cal/mole at B.P.
Approximate Solubility g/lOOg
Solvent at 25C
Acetone
Ether
Benzene
Methanol
Water
Carbon tetra chloride
n-Heptane
170.2
257
1.070
8.92
1.578
26
239
258
1144
11,800



00
00
00
00
20.8 ppm
oo
00
170.2
257
1.070
8.92
1.579
27
239
258
1144
11,800



00
00
00
00
21 ppm
00
00
 .
255
1.065-1.075
8.92
-
15
235
255
-
-



00
00
00
00
21 ppm
00
00
 Solubility  of  DPO  in water  at  25C	20.8  ppm
 Solubility  of  water in DPO  at  25C	0.071%
 Solubility  of  water in DPO  at  30C	0.077%
                       BOILING POINTS  OF DIPHENYL OXIDE
                Boiling  Point                         MM Hg
257. 9C
181. 3C
147. 1C
121. 0C
77.0C
760
100
30
10
1
  Vapor pressure 0.019 mm Hg at 25C*
  *Branson (1977)
                                   95

-------
         Appendix B






Material Safety Data Sheets
            96

-------
MATERIAL SAFETY  DATA SHEET
(APPROVED BY THE U.S. DEPARTMENT OF LASOR AS  "essantiolly similar" to form OSHA-20)
                                                       Act af 1970 0-.1 iboll 131 b. jj lor :
                              Section I   NAME & PRODUCT
MA:; ji; iC V-iPER'S N AVL CITY. STATE. Z.P CODE
DOW CHEMICAL U.S.A. MIDLAND, MICHIGAN 48640
L^A't T  S P O r* M WRlTTCN
February 19. 1973
E V.  R C E f J C v '
517-
PREPARED S> iSignoture) 	 N ^^ 	 > , ^^S"
> HO *1 t
636-
j^1
NO.  Z4 HOURS
4400

          Diphenyl Oxide, Technical
Diphenyl Ether
Section 2 INGREDIENTS
Diphenyl oxide
(Not a specification value)
%
95
TLV
1 P!
                                Section 3  PHYSICAL DATA
BOILING POINT ?F.)
VAPOR PRESSURE (mmHgol 20c)
VAPOR DENSITY (oir = 1)
4QR
__-
___



SOLUBILITY IN WATER
SPECIFIC GRAVITY (H20= 1)
r, VOLATILE BY VOLUME
Insoluble
1.070 ft ?7Mr.
 - _
APPEARANCE _ . Colorless liciuid
                         Section 4  FIRE AND EXPLOSION HAZARD DATA
> . A 5 H = O 1 N T
205 'f
IANO METHOD OSEDI
EXTINGUISHING
MEDIA 	 -

fx
WATER
FOG
Cleveland
IXjFOAM
Open Cup
r -i ALCOHOL
|X | FOAM
r L, AMMA B LE
L.F.L. (j

fx
co?
L'MITS
.8
ra
(STP IN AIRp
DRY
CHEMICAL
|u. F. L.
OTHER
_Q _
1.5

 SKEf.AL FIRE FIGHTING PnOTECTION EQUIPMENT AND HAZARDS
 None.
                              Section 5  REACTIVITY DATA
STABILITY
(NORMAL CONDITIONS)
X STABLE
INCOMPAT.
IBILITY
UNSTABLE
MA TfiftlA L5 TO A
LjWATER
0
THEP

CONDITIONS TO AVOID
/OIO
n___ _ n v 1 nt 7 IMf* '
ACID BASE I (CORROSIVE MATERIAL

 None.
HAZARDOUS
POLYMERIZ-
ATION

X
MAY
OCCUR
WILL NOT
OCCUR
CONDITIONS TS AVOID
Section 6 SPILL OR LEAK PROCEDURES
 Small spills  -  absorb in sweeping compound.
 Large spills  -  call Dow emergency number  for  instructions
  ' ;S A . ME THOD
 Burn or bury  in accordance with local  ordinances.
                                      97

-------
Mfl
       Diphenyl Oxide, Technical

   ATERiAL SAFETY DATA SHEET  (CO,T.,
DOW CHEMICAL U.S.A.

MIDLAND, MICHIGAN 43640
                                 Section 7  HEALTH HAZARD DATA
  tow single dose oral; LDgo  4000 mg/kg for both  rats and guinea  pigs.   Estinat
  ng from these data,  the  lethal dose for a  100 pound person may be in the
 range  of 3/4 cupful.	
 E > L C 3 : T A C i'
 |Mild  to  moderate irritation; unlikely  to  cause injury.
  [Occasional contact  -  no  adverse effects  expected.
  Mild  to  moderate irritation upon repeated,  prolonged contact.
I
I
     :1SO" = TCN               No LD   determined  because of lack of  indication of
  Not readily absorbed  - problem from absorption.	'	
  LV:  1  ppm - based on  odor control.  No problem at room temperature.
  Disagreeable odor, possible liver injury  at  high concentration.
1

-'
f\
1
t
a

.

EYE
'

FLUSH
fliTH
FLOWING
WATER



EYES & SKIN: Flush with plenty of water; get medical atten-
tion if irritation develops. Remove contaminated clothing
and free of chemical before reuse.
INHALATION: If discomfort develops from breathing vapors, get
patient to fresh air.
INGESTION: No known antidote; treat symptomatically.


NEVER GIVE
FLUIDS OR
INOUCE
VOMITING
IS UNCONS-
CIOUS OR
HAVING
CONVULSIONS
                          Section 8  SPECIAL PROTECTION INFORMATION
  t: -i T ,. A i  ON

  Sufficient to control  to  TLV.
                                 	
    "' i~A"f 5 KT~3'!~"3 TcTcTio'f T' i. p"e cTTx"ty p <

  When disagreeable odors  occur, full-face mask and canister  for organic vapors,
      T .f: :_OTHING
  Clean  clothing.
I
           ,
        !     \:>3r NOR^A'-'-vlylsArErY cLssiri
 f RO'I ECTlO" 3
                                  (The iilcrnotion herein ij given in good foith, bjt no wo.-ront>, eipreited or implied, it mode)

-------
MATERIAL SAFETY  DATA SHEET
(APr^O'/iD 3f Th= U.S. DEPARTMENT Or I.A30R Ai - "sssMLL NOT
X L o-cus
C 5N > r :CNi T3 A ,' J, r

                             Sectijn 6   5P1LL OS LcAX PROCOUSi=3
 Scoop  up and  salvage if  possible.
 Observe  Federal,  Stats  and Local  laws
 for disposal instructions.
                 Contact The Dow Chemical Corr.oanv
                                        99

-------
 I
I
     3iphenyl, High Purity

1ATERIAL SAFETY DATA SHEET  {CONT,
                                                              DO'V CH-.vdC
                                                              M.3LASD, -I t;-ii
                                 Sect.on ''  HEALTH H^ZARO CUT
!Low single dose oral  toxicity.   LD5o  rats is .greater than 4000 mg/kg.
Estimating front thesa data,  the  lethal dose for a 100 Ib. person .-.ay b
4-5 ounces.
   ' - - "4C:
  Up  to  slight  irritation but no corneal injury.
  Shore  single  exposure not likely to cause significant irritation.  Prolonged
  or repeated exposure may cause slight irritation.
I
  Not  likely  to  be  absorbed in toxic amounts.
I
T!_V:  0.2__p_?m  or  1  mg/m3  (1974)

Respiratory irritation.
          SYZS:.  Flush with plenty of vater for 5 minutes and get T.edicaL .,.,,,,=
        help
               if  ill effects occur.   SKIM:  Wash with scii
          Remove  grossly contaminated cio:.hing a-.l wash befTr.i r-2Lij=
           NHALATION:   If ill effects occur, ^^
          gat medical  help.   INGESTION:  Not likely a problen
          amounts are  swallowed, see above, promptly ir.duca vomiting
          and get medical help.*

Co.ntrol  dusts  or mists to TLV.
   Respiratory protection required in absence of proper environ
   If  recuirod,  use an approved dust respirator.
   Clean  body covering clothing.
                            no -,-.<
          _,	:'^. Vo."k"N?LE*    p  Eye _f our. tain and v a shir.': facilibiss  n-ar  v;o:rk area.
                   .__._.   _^.--_   -.___._.__,.______.._..._.._.        	
   Practice reasonable care and cleanliness to avoid gross  :;;kin  and  aye  contact.
   Avoid  breathing vapors and dusts if generated.


   *NOT2  TO PHYSICIAN:  No specific antidote known.  Traatrr.eni: depends on  the
    sound judgment of the physician and the individual reactions  of  the  pacier.-.
                                          100

-------
MATERIAL  SAFETY  DATA SHEET
(APPROVED SY THE U.S. DEPARTMENT OF LABOR AS.. "cssentiolly similor" to form OSMA-20)
                                                               (,< 1970 end he
                                  Section 1   NAME & PRODUCT
 A ..,-- "  ..' t .- <: AMfc

      CHEMICAL  JS
                                     C i I 'i 'J 7 i T  Z ; P C O O E

                                  MIDLAND. MICHIGAN 48640
            . H f T M
                 1974
                                  'Signofure)
                                                        E'-C < "HO'IE MC. ;j

                                                        517 - 636 - 4400
 T K ., :_ t N - *.'. 
 DOWTHERM A heat transfer  fluid
                                      Section 2  INGREDIENTS
                         Diphenyl oxide
                         Diphenyl
                                                                             73.5
                                                                             26.5
                                                                     jlppm
                                    (Not specification values)
                                    Section 3   PHYSICAL DATA
 BOILING POINT (F.)
 VAPOR PPFSSURf: (inmHejot 20*c)
 VAPOR DENSITY (air = I)
                                6"
                           >i
                                               SOLUBILITY IN WATER
                                            SPECIFIC GRAVITY jH2o-D	1.050-1.075 & 25/25
                                               n VOLATILE BY VOLUME
                             iquM_a.r
                            Section 4  FIRE AND EXPLOSION HAZARD DATA
  LASH "^I'Jl trO METHOD USCD.
     255T Cleveland Open Cup
                                                     L LIMITS .3 T P IH AIR1
                                                0.5% (500F)     |u.,.L.  6.2% (500F)
EXTIMCUISHINO
MEDIA 	
I WATER
i|ALCOH<
|	[FOAM
                                                  :o2
  C r; ,.M. !'=. r r IC-1 r INC PHOT CC flON fcQ'JIPMENT AND MA; AMOS
                                                        __      OTHER
                                                       -.DRY       i	1
                                                       JCHEMICAL   I	| _
 Self-contained  breathing apparatus may  be needed in enclosed spaces
                                  Section 5   REACTIVITY DATA
    STABILITY
 :NO.VAL CONDITIONS)


P"77"1
               UNSTABLE
                      COKTMTIONC TO AVOID
 IHCOMPAT.
 I8ILITY
 None
         LJ''A1ER    LJACID     LJBASE     	CORROSIVE     [_X.
                                                            OXIDIZING
                                                            MATERIAL
         .. *:o.!'>: t: ( 13:1 vriornjc fs

HAZARDOUS
POLYMERIZ-
ATION



	

X
MAY

OCCUR
'WILL NOT
OCCUR
CuMUiriONS TO AVOID




      	Section 6   SPILL OR LEAK PROCEDURES
      '.. * ' ' f L 'J .'- C A', i M A ~! !" d i A -. ' -j~>i FT.' ^Af (TT7 OH &* ' i '7e (.    ' '
 Soak up with absorbant material.
 Incineration in  approved equipment.
                                            101

-------
i
    DOWTHERM A
 1ATERIAL SAFETY DATA SHEET ,CONT,
                                   DOW CHEMICAL U.S.A.
                                   MIDLAND. MICHIGAN 4864G
                               Section 7  HEALTH HAZARD DATA
 tow'single  dose  oral toxicity.   LD5P rats is in the range of 2000  to  4000 mg/kg.
Estimating  from  these data,  the lethal dose for a 100 Ib. person  may be 2
o 4 fluid  ounces.
I
 p to mild irritation but no corneal injury.
   f:
   lort single  exposure not likely to cause significant irritation.   Prolonged
 or repeated exposure may cause up to mild irritation.
 i
 i
                TIk~ely  to be absorbed in toxic~ amounts.   Very low in
                 route.
 LV:  JLpPjn (1973)	
 >'".:"; '"?'~* !:

 I
       I  r I-10T NOPMLl.Y|v Ifti^STV CL4SSKS      I  Is A F E 1 V O L 4SS E i     I JC-KVICM
  I.ECTIONJ  LJ.'if-CE1S   |A_|/
-------
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                                      103

-------
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                                      104

-------
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                                      105

-------
Kolar, B. and Klacel, Z. (1962), Chemicky Prumysl 12:326-332.

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                                      106

-------
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                                       107

-------
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                                      108

-------
                                   TECHNICAL REPORT DATA
                            (Please read Imiiructions on llic reverse before completing)
I. REPORT NO.
  EPA 560/6-77-003
                             2.
                                                           3. RECIPIENT'S ACCESSION-NO.
4. TITLE ANDSUBTITLE
  Chemical Market Input/Output Analysis  of  Selected
  Chemical Substances to Assess Sources  of  Environmental
  Contamination:   Task II. Biphenyl and  Diphenyl Oxide
             5. REPORT DATE
                 October 1976
             6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
  William M. Meylan
  Philip H. Howard
             8. PERFORMING ORGANIZATION REPORT NO

                 TR 76-599
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Center for  Chemical Hazard Assessment
  Syracuse  Research Corporation
  Merrill Lane
  Syracuse, New York   13210
                                                           10. PROGRAM ELEMENT NO.
             11. CONTRACT/GRANT NO.
                 EPA 68-01-3224 - Task II
 12. SPONSORING AGENCY NAME AND ADDRESS
  Office of Toxic  Substances
  U.S. Environmental Protection Agency
  Washington, D.C.    20460
             13. TYPE OF REPORT AND PERIOD COVERED
                 Final Report
             14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT

       This report  considers the sources of  environmental contamination  from
  biphenyl and diphenyl oxide.  Biphenyl is  manufactured in commercial quantities
  for use in dye  carriers,  heat transfer fluids,  derivatives such as PCB's  and
  alkylated biphenyls,  and  fruit fungicides.   Diphenyl oxide is manufactured in
  commercial quantities for use in dye carriers,  heat transfer fluids, derivatives
  such as butylchlorodiphenyl oxide, decabromodiphenyl oxide, surfactants,  and
  perfumes and soaps.   Thus, this report concentrates on the commercial  production
  and use of biphenyl  and diphenyl oxide.  Standards established by the  Occupational
  Safety and Health Administration have controlled the occupational exposure to
  biphenyl and diphenyl oxide; however, large  quantities of these chemicals are
  released to the external  environment, particularly to waste treatment  facilities
  which may utilize chlorine disinfection,   Laboratory studies indicate  that the
  biphenyl nucleus  can undergo chlorination  to various chlorobiphenyl isomers during
  treatment chlorine disinfection.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.IDENTIFIERS/OPEN tNDED TERMS  C. COSATI Field/Group
18. DISTRIBUTION STATEMENT
 Document is  available to the public  through
 the National Technical Information Service,
 Springfield,  Virginia   22151.
                                               19. SECURITY CLASS (This Report)
                           21. NO. OF PAf.bS
                              117
                                              20. SECURITY CLASS (This (ingf)
                           22. PRICI-
EPA Form 2220-1 (9-73)
                                         109

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