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I an enclosing a copy of our contractors draft report on the Market Input/Output of Biphenyl and Diphenyl Oxide for your review and Garment. Any suggestions ar corrections which you would care to mate would be most appreciated. If it is at all possible, I would like your response by April 15. Sincerely yours. Thomas E. Kopp Project Officer Special Actions Office of Toxic Substances (WH-557) 202/755-8043 DSW 012701 STLCOPCB4002625 ADDRESSEES 1. Mr. H.W. Earhart Manager, Special Aromatic Products Sun Oil Company P.O. Box 2608 Corpus Christi, Texas 78403 2. Mr. Chester E. Otis Manager, Envirorraental Affairs Dow Chemical USA Bennett Building 2030 Dow Center Midland, Michigan 48640 3. Dr. Peter Gaffney Biology Department Georgia State University Atlanta, Georgia 30303 4. Dr. Joseph Highland Environmental Defense Fund 1525 18th Street, N.W. Washington, D.C. 20036 5. Mr. K. warren Easley Monsanto Chemical Caqpany 1101 17th Street, N.W. Washington, D.C. 20036 6. Mr. J. Cole Weber Monsanto Chemical Co. - BZSK 800 N. Lindbergh Boulevard St. Louis, Missouri 63166 7. Mr. John Hesse Water Resources Ocmnissicn Department of Natural Resources State of Michigan Lansing, Michigan 48926 8. Dr. Dean Branscn Dow Chemical Catpany 2030 Dow Center Midland, Michigan 48640 DSW 012702 STLCOPCB4002626 -2- * 9. Mr. Carl Brainier EPA, Region V 230 South Dearborn street Chicago, Illinois 60604 .10 Dr. Charles F. Jelinek Acting Deputy Associate Director far Technology Food and Drug Adninistration Department of Health, Education and Welfare Washington, D.C. 20204 .11 Mr. Mike Jones Office of Strategies and Air Standards Environmental Protection Agency Peeaarrh. Triangle Park, N.C. 27711 .12 Mr. William Holirberg Director Operations Division Office of Pesticide Programs Environmental Protection Agency Washington, D.C. 20460 13. Mr. Carl Schaffer Director, Effluent Guidelines Division Office of water Planning and Standards Environmental Protection Agency Washington, D.C. 20460 DSW 012703 STLCOPCB4002627 DRAFT TR 76-599 CHEMICAL MARKET INPUT/OUTPUT ANALYSIS OF BIPHENYL AND DIPHENYL OXIDE TO ASSESS SOURCES OF ENVIRONMENTAL CONTAMINATION William M. Meylan Philip H. Howard Center for Chemical Hazard Assessment Syracuse Research Corporation Merrill Lane, University Heights Syracuse, New York 13210 Contract No. 68-01-3224 - Task II SRC No. L1273-07 October 1976 Project Officer - Thomas E. Kopp Prepared for: Office of Toxic Substances . U.S. Environmental Protection Agency Washington, D.C. 20460 DSW 012704 STLCOPCB4002628 H0TICE This document is a preliminary draft. It has not been formally released by EPA and should not at this stage be construed to represent Agency policy. It is being circulated for comment on its technical accuracy and policy impli cations. DSW 012705 ii STLCOPCB4002629 Table of Contents I. Introduction II. Historical' Development and FutureOutlook A. Historical Development - 1. Biphenyl 2. Diphenyl Oxide B. Future Outlook 1. Biphenyl 2. Diphenyl Oxide III. Market Input/Output Data A. Production B. Importation C. Exportation D. Use Patterns IV. General Manufacturing and Production Technology A. Biphenyl ' 1. Thermal Dehydrogenation of Benzene a. Manufacture b. Production Volumes e. Economics d. Environmental Management e. Alternative Biphenyl 2. By-Product FromDealkylation of Toluene a Chemistry b. Process Description c Production Volumes d. Environmental Management e. Economics 3. By-Product From Partial Oxidation ofBenzene a. Process Description B. Diphenyl Oxide 1 2 2 2 4 6 6 7 9 9 12 13 13 16 16 16 16 19 20 20 20 21 21 22 25 25 25 26 26 26 DSW 012706 ill STLCOPCB4002630 Table of Contents (Cont'd) 1. By-Product From Chlorobenzene-Phenol Process a. Manufacture b. Production Volumes C. Shipping d. Economics e. Environmental Management 2. Catalysis of Phenol a. Production Volumes b. Environmental Management c. Economics and Use Process Technology Biphenyl 1. Dye Carrier a. Manufacture b. Dye Carrier Uee c. Environmental Management d. Areas of Use e. Economics f. Alternative Products 8* Alternative Processes . 2. Biphenyl Fungicide in Fruit Packaging a. Manufacture b. Production Volumes c. Economics d. Environmental Management e. Alternatives 3. Polychlorinated Biphenyl (FCB) a. Manufacture b. Production Volumes c. Economics 4. Alkylated Biphenyl a. Isopropylbiphenyl (1) Manufacture ' . Page 26 26 30 31 31 32 32 33 34 34 35 35 : 35 35 38 40 41 41 41 43 43 44 44 45 45 45 46 46 46 46 47 47 47 lv OSW 012707 STLCOPCB4002631 Table of Contents (Cont'd) (11) Production Volumes and Uses (ill) Economics b. Methylbiphenyl c. Ethyl- and Butylbiphenyl 5. Eutectic Heat Transfer Fluid 6. Polybromineted Biphenyl (PBB) a. Manufacture b. Production Volumes c. Economics d. Alternatives Diphenyl Oxide 1. Eutectic Heat Transfer Fluid a. Users b. Production Volumes c. Economics d. Environmental Management e. Use Alternatives 2. Dowfax a. Manufacture b. Production Volumes c. Economics d. Environmental Management e. Alternative Products 1 3. Diphenyl Oxide Dye Carriers a. Volume of Use b. Economics c. Environmental Management d. Alternative Products 4. Perfumes and Soaps a. Manufacture b. Volume of Use c. Economics d. Environmental Management e. Alternative Products Page 47 48 48 48 48 48 49 49 49 49 49 49 51 51 52 52 52 53 53 55 ' 55 55 56 56 56 57 57 58 57 57 58 58 59 59 DSU 012708 STLCOPCB4002632 Table of Contents (Cont'd) 5. Butylated Monochlorodiphenyl Oxide a. Manufacture b. Production Volumes c. Environmental Management d. Economics ' e. Alternatives 6. Decarbromodiphenyl Oxide a. Manufacture b. Production Volumes c. Economics d. Environmental Management e. Alternatives 7. Minor Commercial Uses of DiphenylOxide a. Chloromethyldiphenyl Oxide ' b. Methoxymethyldlphenyl Oxide c. Pesticides VI. Sources of Biphenyl and Diphenyl Oxide Occurring in Nature A. Biphenyl 1. Petroleum 2. Foods B. Diphenyl Oxide 1. Plants VII. Generation of Biphenyl and Diphenyl Oxide By-Products A. Biphenyl 1. Dealkylation of Toluene ' 2. Naphthalene Feedstocks 3. Coal Tar 4. Automobile Exhaust B. Diphenyl Oxide 1. Caprolactam - Nylon Production 2. Bituminous Coal Tar page 59 59 60 60 60 61 61 61 62 62 62 63 63 63 64 65 67 67 67 68 68 68 70 70 70 70 72 73 73 73 74 DSW 012709 STLCOPCB4002633 Table of Concencs (Coat'd) VIII. Material Balance - Exposure to the Environment A. Biphenyl .1. Dye Carrier 2 Fungicide#. 3. Dowtherm A 4. Creosote Oils 5. Petroleum 6. Naphthalene Feedstock and Toluene Dealkylation By-Product, Unrefined 7. Coal-Tar, Excluding Creosote Oils 8. Automobile Exhaust B. Diphenyl Oxide 1. Dye Carrier 2. Perfume&gand Soaps 3. Dowtherm A IX. Environmental Perspectives A. Occupational Exposure toMan B. Release to the Environment 1. Biphenyl a. Effectiveness of Biphenyl Waste Treatment b. Environmental Chlorination of Biphenyl 2. Diphenyl Oxide a. Effectiveness of Waste Treatment b. Biodegradation c. Bloconcentratlon X. Environmental Assessment A. Biphenyl B. Diphenyl' Oxide Appendix A - Physical Properties Appendix B - Material Safety Data Sheets REFERENCES Page 75 75 75 75 77 77 78 78 78 78 78 78 80 80 81 81 82 82 82 84 88 88 88 89 90 90 91 93 96 103 vii DSW 012710 STLCOPCB4002634 Lise of Tables I1I-1. United States Biphenyl Producers V-l. Textile Chemical Specialty Firms Who Make BiphenylDye Carriers VIII-1. Estimated Environmental Releases of Biphenyl VIII-2. Estimated Environmental Releases of Diphenyl Oxide IX- 1. Chlorination of Biphenyl Utilizing Water Renovation Conditions Page 10 37 76. 79 86 viii DSW 012711 STLCOPCB4002635 List of Figures III-l. Annual Biphenyl Production (SRC Estimation) III-2. Current Annual Biphenyl Use in the United States III- 3. Domestic Diphenyl Oxide Use in 1975 IV-- 1. Biphenyl From Thermal Dehydrogenation of Benzene IV-2. General Process for Hydrodealkylating Toluene toBenzene IV- 3. Diphenyl Oxide From Chlorobenzene - Phenol Process V- l. Polyester Fiber to Garment Flow Diagram V-2. V-3. Dyeing and Finishing of Polyester Fabrics Process Manufacture of Dowfax(^>Solutions IX-1. Reduction of Concentration Owing to Biodegradation Analysis of Culture Cells and Water Page u 14 15 18 23 28 36 39 54 85 DSW 012712 ix STLCOPCB4002636 I. Introduction Occupational exposures to the compounds biphenyl and diphenyl oxide have been regulated by the Occupational Safety and Health Administration because of their potentially toxic effects. The standards established by OSHA are directed at protecting workers who might be exposed occupationally to air vapors or particu- t lates 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 PCB (poly chlorinated biphenyl) Isomers are formed when sewage, which contains biphenyl,jis discharged to waste treatment plants utilizing chlorine for disinfection and ; deodorlzation (Carlson at al., 1975; Gaffney, 1974, 1976; Johnsen, 1975). Biphenyl and diphenyl oxide have also been shown to bioconcentrate in fish (Neely et al., 1974). This report considers environmental sources of biphenyl and diphenyl oxide and estimations of the amounts which may be exposed to the environment. OSW 012713 1 STLCOPCB4002637 II. Historical Development and Future Outlook A. Historical Development 1. Biphenyl Biphenyl (diphenyl; phenylbenzene), (CgH^, was first reported in 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, Bttchner found biphenyl in high-boiling fractions from coal-tar distillation (Foffenberger, 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. Sooa- .after, the chlorination of biphenyl assumed commercial importance when the Swann Corp. developed the "Arodor" series of PCB's (polychlorinated biphenyls); how ever, Monsanto took over the PCB production in the early 1930's. About that (E) time, Dow Chemical Co. entered the commercial biphenyl field with Dowtharm^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 bach of molten lead at 750*C, through which benzene vapors were bubbled (Scott, 1933; Durgln and Jenkins, 1933). Later reactors used electrical resistance heaters to raise the temperatures above 650*C. 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. 2 OSW 012714 STLCOPCB4002638 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 (Poffenbarger, 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 70Z of the current annual biphenyl production of 85 million pounds is obtained by refining the dealkylated toluene by-product (SRC estimation). The remaining 30Z of the biphenyl production is produced by Monsanto's 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 (Mlspley 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 DSW 012715 3 STLCOPCB4002639 slagle application of biphenyl at present, consuming nearly 60S 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 (polybromlnated ` biphenyls), which began in 1970, was terminated in November, 1974, a year after PBB's were mistakenly added to cattle feed in Michigan (Mumma and Wallace, 1975). The PBB's added to the cattle feed were thought to be a magnesium oxide mineral supplement, but a mix-up in storage by Michigan Chemical Corp. (who manufactured both the PBB's and magnesium oxide) caused bags of PBB to be circulated to the farmers. The PBB's caused contamination of dairy cattle and resulting dairy products. Nearly 11,000 cattle were reportedly destroyed by 1975 (Mumma and Wallace, 1975). 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<r) A, a eutectic heat transfer mixture of 73.52 diphenyl oxide and 26.5X biphenyl, in the early 1930's. Dowtherm A has been a widely-used heat transfer fluid since that time. 4 DSW 012716 STLCOPCB4002640 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 N00* 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 Dowtherm^ 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 or cipnenyi ozu prouuceu ui was uses id uowtiierm a iokv# estimation). Other commercially important current uses of diphenyl oxide Include (alkylated sulfonated derivatives) surface-active agents, deca- bromodiphenyl oxide flame retardants, diphenyl oxide dye carriers, and butyl- chlorodlphenyl oxide capacitor fluid Dowfax** production started in the early 1960' s and decabromodlphenyl oxide and diphenyl oxide dye carriers started in the 1970's. Butylchlorodlphenyl oxide is discussed in Future Outlook - Diphenyl Oxide. DSW 012717 5 STLCOPCB4002641 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 85Z increase in the polyester market by 1980 and a 170Z increase by 1985. Biphenyl, however, is \ only one of perhaps eight to ten commercially Important dye carriers used in I polyester dyeing. After consulting with industry spokesmen, it is estimated (SRC estimation) that biphenyl dye carriers make up approximately 25-30Z of the total dye carrier market at present. The total dye carrier market is expected to increase by 47Z by 1980. This 47Z figure is smaller than the 85Z polyester growth figure because technological improvements in dyeing techniques should decrease the amount of dye carrier which is required. If biphenyl maintains 25-30Z 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 lbs. annually (SRC estimation). ` Increased biphenyl consumption is also projected for heat transfer fluids and alkylated biphenyls. Dow has announced an expansion of their Dovthern(rS^) A units, to be completed by 1978 (Anon., 1976 a). In early 1976, Monsanto began commercial production of Thermlnol VP-1 heat transfer fluid, which will compete 6 DSW 012718 STLCOPCB4002642 with Dow's Dowthani A. Therminol VP-1 and Dowthern^ A have identical chemical compositions. Isoptopylbiphenyl, used in carbonless paper, and methylbiphenyl, used as a dye barrier, are also expected to increase output by 1980. A guess would project chat nearly 10 million additional pounds o biphenyl will be used for heat transfer and alkylation by 1980 (SRC estimation). The projected phase-out of PCB'a by Monsanto 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 f There will be large Increases in the production of diphenyl oxfle 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, byjE also for Dowtherm A and decabromodiphenyl oxide (Anon., 1976 a). An estimated $18plllloa of this expansion had been completed by April, 1976. The primary reason for Dow's diphenyl oxide expansion appears to be synthesis of butylchlorodlphenyl oxide. Dow is hoping that butylchlorodlphenyl oxide will be accepted as a PCB replacement in capacitors. Test quantities utilized by McGraw-Edison appear promising. Dow says it hopes to have production capacity in excess of 5 million lbs/year of butylchlorodlphenyl oxide by the end , DSW 012719 STLCOPCB4002643 of 1976 (Anon., 1976 b). If this 5 million lb 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. Several PCB users have indicated that butylchloro diphenyl oxide may not be the best available alternative. * DSW 012720 8 STLCOPCB4002644 III. Market Input/Output Data A. ProductionTable 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 blphenyl 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 conmercial 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 q DSW 012721 STLCOPCB4002645 Table III-l. United States Biphenyl Producers Producer 1. Chebo1, Inc. 2. CPS Chemical Co., Dlv. of Chemistry t Pollution Science* 3. Dow Chemical Co. 4. Eaat Comat Chemical Co. S. Honaanto laduatrlal Chemical* 6. Pilot Induatrlea 7. Sun Oil of Peon, (Suntlda) 8. Sybron Corp., Tanatex Chemical* Olv. Refined llphenyl Producer* - 1976 Production Site Creeaaboro, MC Old Bridge, NJ Tears 1972 - Present ay City, HI Cedar Crove, NJ Annleton, AL Houaton, TX Corpua Chrlatl, TX Lyndhurst, NJ 1933 - Present 1974 - Present 1933 - Present 1974 - Present 1970 - Present 1971 - Present Estimated Capacity (x 106 lb/yr) 3 <1 10 - 20 1-4 43 15 - 20 10 - 20 10 Biphenyl Feed Stock Producers - Commerclally Available Product 1. Coastal States Gaa Producing Co. 2. Cosden Oil and Chemical Co. 3. Dow Chemical Co. 4. Gulf Oil Corp. Corpus Chrlstl, TX lg Spring, TX Bay City, HI Philadelphia, PA DSW tsj nj 120 110 100 SO 80 70 60 50 40 30 --I-----1------ 1----- 1----- 1------1 I I I I I 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) capacity. Of course, that figure is somewhat higher currently, depending upon how ouch 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 Phenyl Ether (DiphenylOxide) 10,758 pounds 43,201 pounds It should be noted that this referencesource 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 12 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 Dowtharm<**) A. These heat transfer fluids, made overseas, are listed in Section V-B-l; quantities which may be Imported were not obtainable. OSW 012724 12 STLCOPCB4002648 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 current uses of biphenyl and 1975 uses of diphenyl oxide, respectively. Quantities used in each appli cation are included where known or estimated. DSW 012725 13 STLCOPCB4002649 iT aK93I 50 ' Dye Carriers Dowtherm WA 2-4 HmI Transfer Therminel VP--I 85 Biphenyl Derivatives 21 PCB'i 9 Afcylatad * Biphanyta <1 MettiyMphenyl <1 Ettiytbiphanyl Dye Carrier Heat Tramler Itopropy(biphenyl-----Carbonleu Paper <1 - Butylbiphenyl -Heat Transfer 0 4-08 Fruit Paper Fungicide AM Figure* Indteaia Biphenyl Canaumplian a 10* Iba. and era SRC Estimthon*, mo l>0 Figure 111-2 Current Annual Biphenyl Use In the United States ^N1) D> STLCOPCB4002650 STLCOPCB4002651 3 1 a Diphanyl Qaida Ln O tzo; M N) 0.25 Dya Carriar Haat Tiamlir ' Dowtharm A Thorminol VP--I Darivadvoi <0.1 Chloromathyldiphanyl oxida <0.1 DHchloromatttyOdiphanyl oxida <0.1 Mattioxymathyl diphanyt oxida 0.75 -* Dacabromodiphanyl oxida - Polyman, Foams Polyman, Foams Dory! rosins Capacitor fluid > Butykhloradiptianyt oxida Capacitor fluid 0.75 1 Dowfax(Dodacyldiptionyloxidisulfonic acid, Disodium salt) ' Surlaca--activa apants 0.1 Parfumot and Soaps Nola: All Figwas Indicata Diphanyt oxida ComumsHlo* x 10* I and an SRC Euanations. 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: (4.91) At temperature* of 700-850*C, 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 D$W 012728 STLCOPCB4002652 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 600*C 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 veil-designed thermal reactor yields a condensed product containing 12-1.5% 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 lb and that of terphenyl, etc. is 0.12 lb per pound of consumed benzene. The mechanical loss of benzene is 0.02-0.04 lb 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 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). Beat is generated in the thermal reactor by means of electrical resistance elements. At temperatures above 650*C, benzene has a tendency to decompose to give carbon and heavy car deposits which coat heat exchange surfaces. 17 DSW 012729 STLCOPCB4002653 DSW 012730 18 STLCOPCB4002654 liphinyl Figure IV-1. Biphenyl From Thermal Dehydrogenation o f 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 lb net multiwall bags 260 lb 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 captlvely 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 26.5Z biphenyl and 73.5Z 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 lbs 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 DSW 012731 STLCOPCB4002655 c. Economics The current 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 lb of consumed benzene yields 0.80 lb biphenyl and 0.12 lb 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, Monsanto's biphenyl is not very competitive for this large quantity use. DSW 012732 STLCOPCB4002656 2. By-Product From Dealkylation of Toluene The companies listed below are all currently refining biphenyl from a by-product obtained when toluene is hydrodealkylated to benzene: Chemol, Inc. Dow Chemical Co. East Coast Chemical Co. Pilot Industries Sun Oil of Penn. Sybron Corp., Tanatex Chemical Div. Greensboro, NC Bay City, MI Cedar Grove, NJ Houston, TX Corpus Chrlstl, TX 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 Chrlstl, 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 catalytlcally 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) + H,, + CH4 (Doelp, 1966) The types of reactions contributing most to the nonselectlve product formation are the following: 21 DSW 012733 STLCOPCB4002657 (biphenyl) (3) CH (methylblpheny1) + H2 (A) > + 2H2 (fluorene) b. Process Description 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 pslg pressure and 811 - 1033*? temperature. The hydrogen-to-toluene mole ratio is 4-12. This stoichiometric excess of hydrogen helps to suppress the non-selectlve reactions. Contact time in the reactor averages 20-80 seconds (Doelp, 1966). Catalysts are used in several processes. DSW 012734 22 STLCOPCB4002658 TdMMlW HydruoM-ridi Gw tCoO GFmI w Baum Product Biptianyl 40-70% Fluoranai Midiyfbi|dianyl Tatuarw Andiracana Pyrana O (/> Ratiduatto Futit or Cefcmf OtPo UU)1 Figure IV-2. General Process for Hydrodealkylatlng Toluene Co Benzene STLCOPCB4002659 The product from the reactor la 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 95Z 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 50Z Toluene 15-20Z Fluorenes 10-15Z Methyl biphenyls 5Z Anthracene 3Z Pyrene 3Z Other Aromatic 9Z Hydrocarbons The weight of the bottoms residue Is approximately 2Z 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 95-97Z purity Is cosmonly 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 cankers In a molten state (biphenyl melts at 69*C). DSW 012736 STLCOPCB4002660 c. Produceion Volumes Estimated capacities o the biphenyl refiners are listed in Table 111-1, 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 hee resulted in a biphenyl by-product from which profits can be reellzed. 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 502 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 DSW 012737 25 STLCOPCB4002661 for $0.16-$0.25/lb., depending upon Che 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 VXX-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 600-800*F. Of the benzene which reacts, 43Z yields phenol, 25Z 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 DSW 012738 26 STLCOPCB4002662 The Dow Chemical Co., plant site located in Midland, MI, produces diphenyl oxide as a by-product from their phenol production via chloro benzene. 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 10-152 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 ajL, 1965). The reactants are then pumped through a nickel-lined, counter-current heat exchanger which raises the reactants' temperature to 275-300*0. The flow is injected into a continuous-flow tubular reactor of 4000-5000 psl pressure and heated to 400*C. Contact time is usually 15-20 minutes at the 400*C temperature. The selective and non-selective reactions which occur in the reactor are the following: (selective) Cl ONa Cl 27 DSW 012739 NaCl STLCOPCB4002663 j ! A OSW 012740 28 STLCOPCB4002664 H C I(G 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 phenoxlde phase, and (2) an oil phase consisting principally o 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 phenoxlde layer is passed to a neutralizer and treated with hydrochloric acid prepared from the HC1 gas by-product from the chlorlnator. The neutralization reaction which produces phenol is: . OH + HCl(aq) ----------------- > [Oj + NaC1 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 USF 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 90-952 by weight. Conversion per pass through the reactor is 35-452 (Faith at 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-selectlve 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 -Q DSW 012741 STLCOPCB4002665 distillation. Ortho-phenylphenol is used as a dye carrier and as an active ingredient 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 Dow's "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, product specification XAS-1075-L. This Industrial grade is intended for use as a dye carrier, and assays about 90Z diphenyl oxide (Dow Form No. 110-288-72). The additional 10X make-up 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 phenol capacity of Dow's chlorobenzene process has been estimated at 48-70 million pounds annually (SRI, 1975, 1976). Since approximately 0.1 lb of diphenyl oxide are formed per pound of phenol formed, the annual diphenyl oxide capacity would be 4.8-7.0 million pounds. Therefore, 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 DSW 012742 STLCOPCB4002666 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 80*F, 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 are for bulk shipments of diphenyl oxide: industrial grade technical grade perfume grade $0.52/lb $0.60/lb $0.85/lb However, the large percentage of Dow's diphenyl oxide production iscaptlvely used to make Dowthen^A, Dowfaj^ surfactants, butyl- chlorodiphcnyl 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 processes now underway at the Dow Midland facility, it is believed that phenol production via chlorobenzene will be eliminated in favor of phenol production from cumene. DSU 012743 31 STLCOPCB4002667 This would indicate that diphenyl oxide will be prepared directly from chloro benzene and caustic -soda. Dow holds the original patent describing diphenyl oxide manufacture by this direct route (Hale. 1930). The chemistry of this reaction is: . C~t~lyst^> + 2**C1 + h2o The current selling prices of chlorobenzene and sodium hydroxide are $0.29/lb and $0.125/lb, respectively (Chemical Marketing Reporter). At a 902 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 sever 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 (SchtSUkopf, 1929). The patent describes phenol as being heated to 350"C in an autoclave with activated fuller's earth to OSM 012744 32 STLCOPCB4002668 give a 15Z 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: Paadnock Raeydad Phanoi . The selective chemical reaction should be: i c6a5oa > (c6Hj)2o + h2o The diphenyl oxide grade produced by Monsanto is 99.9Z pure (Monsanto Technical Sheet 1C/FF-49). a. Production Volumes Monsanto has been producing diphenyl oxide only since late 33 OSW 012745 STLCOPCB4002669 1975. Capacity or production volumas at the facility are not available as the Information is considered proprietary. The large percentage of production will be used captlvely to make Therminol VP-1 (Pane, 1976), which is a heat transfer fluid of Identical composition to Dowtherm<D^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 prices of Monsanto's diphenyl oxide is $0.80/lb in bulk shipments. Assume a 90Z 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. 34 DSW 012746 STLCOPCB4002670 V. Use and Use Process Technology ' A. Biphenyl - 1. 'Dye Carrier Ac the presenc time, nearly 60% of Che refined biphenyl produced In che U.S. is consumed In dyeing assistance called dye carriers. Polyester fibers, such as Dacron^ and Teryleni, 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, Che 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 Chat 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 flber-to-flnlshed garment process. The companies who produce the due carrier chemicals sell these chemi cals to textile chemical specialty firms. Twency-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 waterinsoluble biphenyl emulslfiable 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 DSW 012747 STLCOPCB4002671 \iu DSW 012748 36 STLCOPCB4002672 Figure V - l. Polyeater Fiber to Garment Flow Diagram (adapted from O tis, 1976, and various personal communications) Table V-l. Textile Chemical Specialty Firms Who Make Biphenyl Dye Carriers Firm _ 1. Arol Chemical Products Co. 2. Chemical Processing of Georgia 3. CNC Chemical Corp. 4. DePaul Chemical Co. 5. W.F. Fancourt 6. Floatex, Znc. 7. High Point Chemical Corp. 8. Independent Chemical Corp. 9. Jordan Chemical Co. 10. Lutex Chemical Corp. 11. Mlllmaster 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. Tenetex Chemical Corp. 22. U.S. Oil Co. 23. Virkler Chemical Co. 24. Woonsocket Color & Chemical Site Basle Product Name 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 Arosolve PC-7 Chemcryl COD Chemkar 209 Carrier A Depco Jet Carrier 296 Neoport BT Accelerlt BP Carrier 100 Speco Carrier 23 Jocar LOC Super-Lok 845 Decar BC High Point, NC Charlotte, NC Philadelphia, FA Jersey City, NJ Hanover, NJ Charlotte, NC Charlotte, NC Macon, GA New York, NY Lyndhurst, NJ East Providence, RI Charlotte, NC Woonsocket, RI Carrier L-300 Raycar LBP Rocar 4921-A Sabcar #235 Dllatln FBL Charlab LBPW Standye Car 180 Carrier P-40 Sunkem 660 Carolid AL Uscosist 810 Vircocarrier B Woonco Dye Assist DSW 012749 37 STLCOPCB4002673 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 hlphenyl 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, Kerneravllle, 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 DSW 012750 STLCOPCB4002674 I i i DSW 012751 39 STLCOPCB4002675 Figure V-2. Dyeing and Finishing o f Polyester Fabrics Seep #1 Water #2 Heat to 120*F #3 Polyester Fabric #4 Sequesterant #5 Lubricant 16 Anionic Dispersant #7 Acetic Acid 70Z #8 Dye Carrier #9 Disperse Dyestuffs . #10 Heat to 260*F #11 Run for 45 minutes #12 Cool to 160*F #13 Emulsified Perchloroethylene #14 Wash 25,000 lbs 1,000 lbs 15 lbs 10 lbs 10 lbs 15 lbs 40 lbs 20 lbs 25 lbs In general practice, the concentration of biphenyl varies from 3-12Z of the might of fabric (Carter, 1976; Monsanto Technical Bulletin 1C/FF-29). After washing, the fabric la 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 TLV of only 0.2 ppm for biphenyl vapors, so dyers con&only use exhaust fans to vent biphenyl vapors to the outside atmosphere (the 0.2 ppm TLV is being challenged. Section IX-A). After the fabric has bees washed. It will still contain small amounts of biphenyl. The vacuum drier affectively 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 biphenyl's tendency to sublime under normal conditions leads to disappearance of these crystals. At least 95Z of the biphenyl added as dye carrier is re leased in the waste waters. Since the biphenyl is in an emulsified state, it DSW 012752 STLCOPCB4002676 la coo difficult to separate from the water; otherwise. It could be reused. Zt 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 65Z 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 era 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 100Z 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: DSW 012753 41 STLCOPCB4002677 (1) Butyl Benzoate - COOCH2CH2CH2CH3 Selling Price: Manufacturers: (2) o-Phenylphenol $0.30/lb CPS Chemical Co., Cindet Chemicals, Finetex, Velslcol, Pfizer, Tanatex Selling Price: $1.50/lb Manufacturer : Dow Chemical (3) Trlchlorobenzene - Selling.Price Manufacturers : (4) Dichlorobenzene - Dow Chemical, Booker, Standard Chlorine end Selling Price: Manufacturers: (5) Methyl Salicylate - $0.31/lb Allied, Dow, ICC Industries, Monsanto, PPG, Solvent Chemical, Specialty Organics, Standard Chlorine Selling Price: Manufacturers: (6) Perchloroethylene - $1.00/lb Dow, Monsanto, Tenneco C1C - cci2 Selling Price: Manufacturers: $0.165/lb Diamond Shamrock, Dow, DuPont, Ethyl Corp., Occidental, PPG, Stauffer, Vulcan DSW 012754 42 STLCOPCB4002678 (7) Methyl Naphthalenes - <CH3>, Manufacturers: Crowley Hydrocarbon, Hoppers, 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 60Z. 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. Tears 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-1950's, the FDA Investigated the toxicity of biphenyl. The Institute of Paper Chemistry (IPC) was chosen to determine analysis DSW 012755 STLCOPCB4002679 methods and to investigate potential problems. As a result of the work by I?C, 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-Pale 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 1.75-2.97Z of its weight as biphenyl and 7Z to 9Z of its weight as solvent. Paper pads are impregnated in a similar fashion with 4 lbs 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. DSk 012756 STLCOPCB4002680 Ten years ago, at leaat 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* . A1ternatives One consaercial alternative to biphenyl is o-phenylphenol (o-hydroxybiphenyl). Ortho-phenylphenol is obtained as a by-product during Dow's phenol production from chlorobenzene, the same process from which diphenyl oxide is recovered. The o-phenylphenol is converted to the sodium salt which is used to control molds and rota of citrus and other fruits and for the OSW 012757 STLCOPCB4002681 disinfection of domestic end agricultural buildings, warehouses, end refrigerated stores. Price Is slightly higher than biphenyl, but its vlder-range of protection is a definite advantage. It is an active ingredient in certain Lyso^ cleaners. 3. Polychlorinated Biphenyl (PCB) PCB production and use has been thoroughly studied in e previous EPA report (Versar, 1976), so only a brief review will be given here. a. . Manufacture Monsanto, the sole domestic manufacturer of PCB's, manufactures 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. .Currently, Monsanto makes four different PCB products; Arodor 1221, 1242, 1016, and 1254. The difference is in chlorine concent which ranges from 21Z in Arodor 1221 to 54% in Arodor 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 of PCB products averages about $6 per gallon- (11.36 lbs/gallon). Total annual sales would therefore be nearly $11.1 million. 46 QSW 012758 STLCOPCB4002682 4. Alkylated Biphenyl a. Isopropylblphenyl . Commercially, isopropylblphenyl is the most important of the alkylated biphenyls. Tanatax Chemical Division in Lyndhuret, NJ la the largest domestic producer of isopropylblphenyl (Cohen, 1976); Pilot Industries of Houston, TX also manufactures the chemical (Barrow, 1976). (i) Manufacture Isopropylblphenyl is manufactured by a Freidel-Crafts reaction of biphenyl with propylene, the chemistry being: Primarily, the monoisopropyl derivative is formed, but small amounts of the dilsopropyl derivative will also exist. (11) Production Volumes and Uses Currently, about 10 million pounds of isopropyl- biphenyl are annually produced (SBC estimation). Nearly all of the production is used in carbonless paper (Cohan, 1976). Manufacture started about 1971 and has accelerated to the present volume. In 1971, Monsanto terminated PCB's sales for carbonless paper, and isopropylblphenyl has been used as a substitute for PCB in this application. Isopropylblphenyl 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. qsw 012759 47 STLCOPCB4002683 (iii) Economics The current selling price of lsopropylblphenyl Is $0.56/lb, which would indicate annual sales of $5.6 million to the carbonless paper industry. b. Methylbipbenyl Methylblphenyl 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, methylblphenyl alone exhibits excellent dye carrier properties. Small quantities of methylblphenyl are iso lated and sold by Pilot Industries of Houston, TX, but commercial-scale pro duction has yet to occur (Barrow, 1976). Since methylblphenyl 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 Preidel-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 (Barrows, 1976).' 5. Eutectic Heat Transfer Fluid See Section V-B-l. 6. Polybrominated Biphenyl (PBB) PBB production and use has been thoroughly studied In a previous EPA report (ttumma and Wallace, 1975), so only brief review will be given here. DSW 012760 STLCOPCB4002684 a. Manufacture Commercial production of PBB's was terminated in 1974, the commercial producers being Michigan Chemical Corp. of St. Louis, Ml, and White Chemical Corp. of Bayonne, NJ. The termination was precipitated when, in 1973, PBB's were inadvertently fed to dairy cows with harmful effects. ' The manufacturing process of PBB's is considered proprietary, but patent literature (Moore et al., 1974; Mitchell, 1973) describes production via bromlnation of biphenyl by bromine chloride or liquid bromine. PBB's were used exclusively as flame retardants for plastics. 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 (termination date for White Chemical). c. Economics The 1975 selling price of the major PBB product (Flremaster 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 decabromodlphenyl oxide (see Section V-B-6 for this discussion). . B. Diphenyl Oxide 1. Eutectic Heat Transfer Fluid The major current use of diphenyl oxide is for manufacture of a 49 osw 012761 STLCOPCB4002685 eutectic heat transfer mixture composed of 73.5Z diphenyl oxide and 26.SZ biphenyl. This mixture has been marketed by Dow Chemical Co. as DowthertJ A since the early 1930's. Dow produces Dowther^ A in Midland, Michigan. Mon santo Industrial Chemicals, in Alvin, Texas, began producing an identical mix ture 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 Dow Chemical Monsanto Imperial Chemical Nippon Steel Chemical Bayer Progil Country USA USA Great Britain Japan West Germany France' Product Dowtherm A Therminol VP-1 Thermex Therm S-300 Diphyl Gllotherm 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 60aF to 750*7, and in the vapor phase at temperatures from 495*F to 750*7. It is non-corrosive, so carbon steel la usually selected for equipment in which it will be used. Physical properties of the mixture are listed on the Material Safety Data Sheets for A in Appendix B. The eutectic mixture is stable except at the upper temperature levels. Tha first decomposition effect of elevated temperatures is a polymeri sation to materials of higher molecular weight, but these polymers remain in solution in tha liquid and do not affect operation as long as their concen tration does not exceed 10Z. At 750*7, the decomposition rate varies between 0.8Z and 3.0Z per 100 hours (Danzlger, 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 DSW 012762 STLCOPCB4002686 system to individual users of Dowtherm<E") 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 (Sach, 1976). a. Users The eutectic mixture has numerous applications in synthetic fiber production and finishing, petroleum refining, and plastics manufacturing. About 2500 new installations, utilizing Dowtherm*'A, ware made in tha U.S. from 1955-1965 alone (Danzlger, 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 ulate Dowthert^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 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 lbs) in 1962 (Davies, 1963). 51 DSW O12763 STLCOPCB4002687 c. Economics The following selling prices are for Dovthe A: '5 gallon pall 55 gallon drum 4000 gallon Cankers $0.84/lb $0.79/lb $0.66/lb The 1975 sales of 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 except1 by accidental spill ot leak. Dow's "Material Safety Data Sheet" for Dowther^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 550*F). These oils are obtained as hlgh-bolling fractions from petroleum. Several com mercial products are listed below: (1) Mob11therm 600 (2) Humble-Therm 500 (3) Security 205 (4) Tellus 7Z Mobil Oil Co. Exxon Corp. Gulf Oil Corp. Shell Oil Co. 52 DSW 012764 STLCOPCB4002688 A has advantage over petroleum oils due to a higher - film temperature vhlch can be sustained before degradation occurs. Dovthernr* A is useable at temperatures up to 750F, while the petroleum oils have a limit of 600*F. In addition, A maintains a cleaner operating surface during normal use. The disadvantages of Dovtherm*^ A include a price differential in favor of the petroleum oils, and the extra cost of heat-tracing pipes as Dovtherm freezes at 54*F. 2. Dowfax' is the tradename for dodecyldiphenyl oxide disulfonlc acid, disodium salt manufactured by Dow Chemical in Midland, Michigan. Dowfa^ surfactants are anionic vetting 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 Dovfa^ 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, such as hexane or octane, at 8-18aC, and chlorosulfonic acid is then stirred into the solution. The chemical reaction is: 53 DSW 012765 STLCOPCB4002689 n-mca DSW 012766 54 STLCOPCB4002690 Figure V-3. Process Manufacture o f Dowfax'Solutions The solution Is slloved 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 dlsodlum salt. Evap oration of the solution to dryness gives a buff to white powder of dodecyldiphenyl oxide disulfonic acid, dlsodlum salt (Yalenta and Steinhauer, 1964). Three Dowfaa^ products are available from Dow: (1) Dowfaxgv 2A1 Surfactant Solution (2) Dowfaxjt? 3B2 Solution (3) Dovfax*^ 2A0 (1) and (2) above are solutions containing 45X active in gredient of dodecyldiphenyl oxide disulfonic acidr dlsodlum salt, while (3) is the scld form (not neutralized with NaOH). b. Production Volumes ' Production volumes were not available from Dow; however, SRC estimates that Dow captlvely consumes about 0.75 million pounds annually of diphenyl oxide to synthesis Dowfai surfactants. This would mean an annual production of roughly 2.3 million pounds of Dowfai surfactants. Dow introduced this product in the early 1960's. Projections for future growth were not obtained. c. Economics The current selling price of DowfaaJ 2A1 Surfactant Solution is $0.47/lb{therefore, the selling price of the dry powder dodecyldiphenyl oxide disulfonic add, dlsodlum salt is approximately $1.00/lb. This would Indicate annual sales of $2.3 million. d. Environmental Management It is doubtful if significant quantities of diphenpl oxide are released to the environment via manufacture of Dowfu^. Sewer wastes 55 DSW 012767 STLCOPCB4002691 containing.diphenyl oxide ere treated by Dow*a 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. Dowfaa^ can be included in the group of surface- active agents having ester or ether linkages. Other chemicals Included in this group are: (1) Sulfosucclnlc add esters (2) Coconut oil acids, 2-sulfoethyl ester, sodium salt (3)- Dodecyl sulfoaeetate, sodium salt (4) Herring oil, sulfonated, sodium salt (5) Iaooctylphenol, ethoxylated and sulfonated, sodium salt (6) n-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, Dow Product XAS-1075L, to the textile specialty chemical firms as described for biphenyl dye carriers (see Section V-A-l). XAS-1075L assays 90Z 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 taxtile 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 DSW 012768 STLCOPCB4002692 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 Current selling price 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 100-200Z 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 biphenyl. See Section V-A-l. . d. Alternative Products - Same as for biphenyl. See Section V-A-l. A. 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) Glvaudan Corp. (2) Ploraaynth, Inc. Clifton, NT . New York, NT Actual compositions of perfume products are considered proprietary; however, the concentration of diphenyl oxide In the final products is listed below (Opdyke, 1974): DSW 012769 57 STLCOPCB4002693 Concentrations in X 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 end detergents has been suggested to .be Proctor & Gamble Company, corporate offices In Cln- clnnatl, Ohio. Before compounding the "perfume" grade diphenyl oxide into perfumes, it la common to Increase the purity by chemical means (Mahlnka, 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 lbs/yr (Opdyke, 1974). This figure Is down from 200,000 lbs/yr In 1965 (Cantrill, 1968). The 100,000 lbs/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. Economies The current selling price 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. DSW 012770 58 STLCOPCB4002694 d. Environmental Management The nature of fragrance products indicates that all 100,000 lbs/yr use trill 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 Monochlorodlphenyl Oxide Butylated monochlorodlphenyl 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. Since September 1975, Dow has manufactured 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 patane (Hannla, 1974). According to the patent, diphenyl oxide, con taining 0.005 moles of 98Z H^SO^ as catalyst, is chlorinated to yield the following products: 8Z o^chlorodlphenyl oxide, 67Z -chlorodiphenyl oxide, 10Z dlchlorodlphenyl oxide, and 15Z unreacted diphenyl oxide. DSM 012771 59 STLCOPCB4002695 The monochlorodlphenyl oxide cen be butyleted by Freidel- Crefte reection (AlGl^ cetalyst) with butene or butyl chloride. The general formula for XF'S-4169L Is (Branson, 1975): . I n - 0,1,2,3 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 capedty in excess of 5 million lbs/yr by the end of 1976. Five million pounds of butyleted monochlorodlphenyl 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 Current selling prices of XFS-4169L range from $21.50 to $30 per gallon depending upon volume; least expensive for 55 gallon drums, most DSW 012772 60 STLCOPCB4002696 expensive for 5 gallon palls. 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 Dichloroblphenyl (4) Silicones (5) Diaryl Sulfone 6. Decabromodiphenyl Oxide Decabromodiphenyl oxide (decabromodiphenyl ether, decabromo- phenoxylbenzene) is used as a flams 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. (2) Great Lakes Chemical Corp. (3) Hexcel Corp., Fine Organics, subsld. (4) White Chemical Corp. Midland, MI El Dorado, AR Sayrevllle, NJ Bayontne, NJ 61 . FE-300-BA Great Lakes DE-83 -- DSW 012773 STLCOPCB4002697 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 bromlnation of biphenyl with bromine chloride. Decabromoblphenyl is obtained by adding a stoichiometric excess of bromine chloride, under pressure in a closed vessel-, to biphenyl in the presence of an AlCl^ catalyst. Decabromodiphenyl oxide could conceiveably be prepared by a similar method. The bromine content in decabromodiphenyl oxide Is nearly 83X 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 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 DSW 012_7_7,4 STLCOPCB4002698 e. Alternatives Several years ago, polybrominated biphenyls (PBB's) were an Important commercial flame retardant. Decabromodlphenyl oxide was developed to compete with PBB's.for various applications, but decabromodlphenyl oxide cost nearly twice as much as PBB's. However, PBB production was terminated in November 1974, after dairy cattle were mistakenly fed a PBB product (Munnna and Wallace, 1975). One of the new flame retardants, with applications similar to decabromodlphenyl oxide, is Cltrex BC-26, sold by Cities Service Company in Rockville, Conn. (Momma and Wallace, 1975). Cltrex BC-26 is a halogenated organic containing 29Z bromine and 40Z chlorine with a price comparable to decabromodlphenyl oxide. Other comparable flame retardants include (Tabor, 19'73): (1) Tetrabromobisphenol-A (2) Pentabromochlorocydohexane (3) Dibromoneopentyl Glycol (4) Trie (2,3-dlbromopropyl)phosphate $0.57/lb $1.10/lb $0.55/lb $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 (lasers, 1976). Stauffer has produced these chemicals since 1971. DSW 012775 63 STLCOPCB4002699 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. Chloromethylatlon to 25.2% chlorine, for example, would produce the following isomer distribution (Dow Form No. 110-288-72): .Cl Pure materials can be recovered by use of solvent extraction and distillation (Doedens and Cordts, 1961). The total combined production of chloromethyl and di(chloromethyl)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 Hethoxymethyldlphenyl oxide is also produced by Stauffer Chemical in Edison, NJ. Production volumes are less than those for chloro sis thyldiphenyl oxide (Insera, 1976). DSW 012776 64 STLCOPCB4002700 I Diphenyl oxide end 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. ,OCH. :h2och3 SMa Methoxymethyldiphenyl oxide is used to manufacture Westinghouse'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 ejt sJL., 1973) via gas chromatography - mass spectrometry. A survey of patent literature revealed that Clba-Geigy Corporation holds patents describing insecticide production from diphenyl oxide. However, the Clba-Geigy pesticide production facilities (in McIntosh, 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 Clba-Geigy patent (Franks and Traber, 1972): K >(1) 3 + hci --HCrHrT0-.HC1-- (2) 65 STLCOPCB4002701 ch2ch2coch3 + (CH30)2P(0)CH2C02CH3 --PaH"CQB0 ^ Wg)>-CH; i2ch2cch3 chco2ch3 Ciba-Geigy has marketed the following pesticides with a diphenyl oxide moiety: (Chloroxuron) (Fluorodifen) It is doubtfull 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 la definitely used as a raw material for pesticide production, and this possibility still exists. QSW 012778 66 STLCOPCB4002702 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 bolls at 255*C, was Isolated In the dlnuclear aromatic portion of petroleum boiling la the range 255* to 275*C. Hair and Mayer (1964) have estimated that biphenyl makes up 0.0082 by volume of crude petroleum. In 1973, 3.1 x 109 barrels of crude *oil were produced In the United States (SRI, 1975 b). This translates to approximately 1.3 x 101* gallons of crude oil of which an estimated 0.0082 by volume was biphenyl. Converting to weight measurement, an estimated 80 million pounds of biphenyl was present as a naturally occurring constituent of the petroleum domestically produced In 1973. In addition, nearly 5 x 10^ gallons of crude petroleum was 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 la not refined} 0.0082 ie 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 DSW 012779 STLCOPCB4002703 aevaga is between 11 - 12,000 million pounds per year (Blunter at al., 1971). Assuming 0.008Z by volume biphenyl content, simple calculation suggests that approximately 1,000 pounds of biphenyl is annually released into the environ ment with spilled oil. Methylbiphenyls amount to an estimated volume Z, relative to crude petroleum, of approximately 0.0404Z (Malr and Mayer, 1964; Yew and Malr, 1966). This amounts to five times the volume of plain biphenyl. 2. Foods Stevens et 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 Schulte et al. (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. Klnlin e al. (1972) identified biphenyl in the volatile consti tuents of roasted filbert nuts while Valradt jet al. (1971) found biphenyl in peanut volatiles. Stoll jet al. (1967) identified biphenyl as one of 202 consti tuents present in coffaa concentrate. The amounts of biphenyl which may occur in foods is 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 DSW 012780 STLCOPCB4002704 oxide in the volatile constituents of grapes.. Kialand 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 is probably very small. DSW 012781 69 STLCOPCB4002705 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 connerclal 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 dealkylatlng toluene; however, they do not refine the biphenyl stream or sell it to refiners. Company* Site 1. Ashland Oil Co. 2. Crown Central Petroleum Corp. 3. Enjay Chemical Co. (Exxon) 4. Leonard, Inc. 5. Monsanto . 6. Shell Oil Co. 7. Signal Oil ft Gas Co. 8. South Hampton Co. 9. Sunray-DX Cutlettsburg, XT Houston, TX Baytown, TX Mount Pleasant, 1 Alvin, TX Odessa, IX Houston, TX Stllsbee, TX Tulsa, OR 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 DSW 012782 STLCOPCB4002706 significant quantities in the following petroleum-derived streams (Srskine, 1970), and the streams are uses as naphthalene feedstock to produce a purified naphtha lene. (1) Petroleum atreama 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 Reformates (Wt X) Catalytic Cracking fWt 2) biphenyl & acenaphthenes alkylnaphthalenes alkylbenzenes other aromatics 6X 55X 20X 19X 6X 35 X 25 X 34X naphthalene is obtained by hydrodealkylating the alkylnaphthalenes by the same method as previously described for hydrodealkylating toluene to bencena (Section IV-A-2). Once again, the biphenyl by-product which is produced will probably be added to fuels. DSW 012783 71 STLCOPCB4002707 3. Coal Tar Biphenyl was first Identified In the high-boiling fractions from coal tar distillation in 1875 by BUchner (Poffenberger, 1950). Coal tar amounts to about 3Z 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*-300*C; however, no chemicals are separated conmerclally from this range. A fraction distilling mainly In the range 240#-270*C 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 Is consumed annually (SRI, 1974). Dolansky (1974), in an analysis of creosote oil, determined that 60Z of the oil was composed of a hydrocarbon fraction and that 1.35Z of the hydrocarbon fraction was biphenyl. Applying Dolansky's figures to the tJ.S. consumption of 160 million gallons of creosote oil annually reveals that approximately 10 million pounds of biphenyl is 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 was 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. 012784 72 STLCOPCB4002708 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 1.11Z 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 2.15Z, 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 90Z 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 (Rolar and Klacel, 1962). DSM 012785 STLCOPCB4002709 Caprolactam la commercially aynthesized from proceaaea baaed on cyclohexanone. It la difficult to predict any diphenyl oxide by-product for mation during theae proceaaea. However, cyclohexanone ia prepared, in one commercial proceaa, by catalytic hydrogenation of phenol. Phenol can be catalyzed to produce diphenyl oxide, aa ahown by Monsanto's commercial method. It may, therefore, be posaible that diphenyl oxide la formed in email 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 bituaiinous coal tar (Karr et al.. 1967). The fate of diphenyl oxide which may be present in coal tar ia unknown. DSW 012786 74 STLCOPCB4002710 VIII. Material Balance - Exposure to the Environment This section attempts to deine 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 biphenyls, Dowfax(S*>, butylated monochlorodlphenyl oxide, deeabromodlphenyl oxide, chloromethyldlphenyl oxide, or pesticides). A. Biphenyl Table VII1-1 lists the estimated environmental releases of biphenyl. Exploration of the high-low estimates are discussed 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 leas than SZ of the biphenyl is exhausted as vapor, so the large bulk is released in the waste waters. A discussion involving the environmental fats of this water-released biphenyl is presented in Section IX- B-l. The high estimate given in Table VIII-1 was obtained by assuming that only 50Z 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 95Z 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 DSW 012787 STLCOPCB4002711 T* Table VII1-1. Eat1mted Environmental Releases of Biphenyl Use* Current Annual Use, Production or Content (X106 its) Quantities of Biphenyl (SRC Estimations) Current Annual Environmental Release Estimates (X10* lbs) High Low uiiMteA 1966_1975 Um> Productlo0i or Content (X106 lbs) Estimated 1966-1975 ' Environmental Release (X106 lbs) High Low Dye Carrier 30 Fungicide Dowthera(r8^) A 0.6-0.8 1.5 v| Creosote Oils Petroleua 10 110 Naphthalene Peedetocks and Toluene Dealkylation By-Product, Unrefined 30-40 Coal Tar, excluding Creosote Oil Fractions 3-10 Automobile Exhaust - 25 0.6-0.8 small* 10 small* small* unknown unknown 3 0.3-0.4 10 - 250-300 20-30 10-15 100 1000 200-300 unknown. 30-100 - 125-150 20-30 small* 100 0.01 small* unknown unknown 15-18 10-15 100 - unknown o * See discussions in this section Co O to OoD CD STLCOPCB4002712 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 paperB were des- - troyed by incineration, thereby destroying the biphenyl. 3. A It would seem unlikely that large amounts of A are released to the environment because decomposed or Impure Dowtherm can be used for fuel purposes or purified via distillation. 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 A can last for years, the quantities in current use must be quite high. SRC estimates that 5.5 million pounds of 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 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 DSN 012789 STLCOPCB4002713 5. Petroleum Ic would seem unlikely thac any large quantities of the very low percentage' of biphenyl present in petroleum will be exposed to the environ ment. In Section VI-A-l, It was estimated that approximately 1000 pounds of biphenyl are exposed to the environment annually from oil spills. For the tenyear 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 Sea discussion of Section VII-A-4. B. Diphenyl Oxide Table VIII-2 lists the estimated environmental releases of diphenyl oxide. Explanation of estimates are discussed 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 "8 DSW 012790 STLCOPCB4002714 Table Vlll-2. Estimated Environmental Releases of Diphenyl Oxide Dae* Dye Carrier Perfume and Soap Dovtheraf^ A Current Annual Use (X106 lba) Quantities of Diphenyl Oxide (SRC Estimation) Current Annual Environmental Release Estimates (X106lba) High Low Estimated 1966-1975 Use (X106 lbs) Estimated 1966-1975 Environmental Release (X106 lbs) Sigh Low 0.25 0.10 4.0 0.13 0.10 small* .013 0.05 - 1.0 1.0-2.0 30-40 0.5 1.0-2.0 small* . 0.05 0.5-1.0 - * See discussion in this section o Co at IV) described for biphenyl dye carriers. The high estimate given in Table VIII-2 was obtained by assuming that only 50Z 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 95Z 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 50Z of the released diphenyl oxide Is treated effectively. See discussion In Section VIII-A-3. OSW 012792 80 STLCOPCB4002716 IX. Environmental Perspectives - A. Occupational Exposure to Man The following OSHA Threshold Limit Values have been established for exposure to biphenyl and diphenyl oxide in air: Biphenyl 3' 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 Luglnbyhl, 1975; Opdyke, 1974; Haas et al., 1975): Biphenyl: . inhalation - human oral - rat oral - rabbit skin - rabbit fish - fat-head minnow TDL : 4400 ug/m3 LD : 3280 mg/kg LD~: 2400 mg/kg LDf*: 2500 mg/kg TL~(96 hrs): 1.5 mg/1 Diphenyl Oxide: oral - rat skin - rabbit LD..: 3370 mg/kg LD^j: > 5000 mg/kg The 0.2 ppm OSHA standard for biphenyl air exposures is being chal lenged by Stewart-Todd Associates of Wayne, PA (consultants for occupational medicine and environmental health). They have recommended a biphenyl vapor 3 TLV of 10 ppm (approximately 50 mg/m ) to the Threshold Limits Committee based on the argument that (1) references listed in "Documentation of the Threshold Limit Values" are not valid for biphenyl, and (2) employees in some industries have been exposed to greater than 50 mg of biphenyl vapor per cubic meter of air for years with no discernible long-term health effects (Todd, 1976). The present environmental (workplace) standard is Intended to prevent irritation and 81 DSW 012793 STLCOPCB4002717 injury to the respiratory passages. It is primarily based upon the subjective responses of human volunteers who complained of eye, nose, and throat irritation when exposed to a mixture of biphenyl and diphenyl oxide at concentrations well below 7 ppm (American Conference of Governmental Industrial Hygienists, 1974). 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 treat ment, SRC contacted the largest Burlington Industries' mill, which is located in Greensboro, HC. 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. OSW 012794* 82 STLCOPCB4002718 I and all other factory wastes. Mr. Ameen also reports that In community waste treatment plants operated by Burlington in other cities, a 15X or more addition of community solid wastes to the Burlington wastes reduces COD levels of the affluent 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 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 PCB formation is discussed in more detail in Section ZX-B-l-c. Biphenyl has been detected in river water by Webb e al. (1973) and Hites (1973). Hites identified biphenyl, trichlorobenzene, and butyl benzoate in the waters of the Merrimack River at 0.1-0.5 ppb concentra tion. Hites attributes the presence of these organics to upstream textile factories. Also, W.C. Tlchner 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. Ha has found that the biphenyl concentration drops quite rapidly after effluent discharge. He attributes this phenomenon to the vola tility of biphenyl (Tincher, 1976). 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 ' DSW 012795 STLCOPCB4002719 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 95Z biphenyl and of the other dye carriers (Haas et, al., 1975). The biphenyl was totally biodegraded in about 48 hours. What may be note-worthy from Figure IX-1 is the relative inability of trichlorobenzene and perchloroethylene to biodegrade. These two chlorinated hydrocarbons are used in large quantities as dye carriers. 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. In laboratory tests, Gaffney found that PCB's were formed when 10 mg/1 of biphenyl were added to dionlzed water held at 20*C, and then 1 mg/1 of chlorine was added and the reactants kept in contact for one hour (Versar, 1976). Carlson et al. (1975) conducted a detailed laboratory analysis to determine chlorine incorporation into biphenyl and ocher aromatic compounds under conditions utilized for water renovation. Table IX-1 is a summary of PCB 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. DSW 012796 84 STLCOPCB4002720 A24S47-U I Figure IX-1. Reduction of Concentration Owing to Biodegradation - Analysis of ' Culture Cells and Vater (Haas et al., 1975) DSW 012797 85 STLCOPCB4002721 Table IX-1. Chlorination of Biphenyl Utilizing Water Renovation Conditions (Carlaon jet al., 1975) v Cblwtw bam Cn(0Cl)2 Ca(0Cl>2 Cn(0Cl)2 Cn(0CI)2 Cn<0Cl)2 Ca(0Cl)j Ca(OCl)2 c*<ou>2 Ca(OCl), HnOCl Cl* IU0C1 Cli* HftOCl r J.J J.J J.J J.J J.S J.J J.S J.J J.S I.I 2.4 4.4 10.4 2.2 7.0 QtUrlwif 9f too too too too 10 20 so too 10.0 29J 244 030 UJO 29JO Onactlon Tim, br 24 44 72 120 120 120 120 120 120 0.2J 0.25 0.2J 0.2S 0.2J 0.2S tMCtlMi X 0.4 1.0 1.7 2. J 0.004 0.02 0.04 0.1S 0.27 .2.2 9.3 0.1 0.4 14 3.2 2- IS 32 54 49 0.1 0.44 1.4 4.0 4.4 120 490 5-10 40 100 200 btantal biphenyl WinCim Iwl i<M>ln<Illlf to bn 4.0 /!. Slfhnr cblnrimtnO Imtn aim promt. bb nf Cblnrtwcad ProOnct J-,4- 2.2* t.J'-t.b1 10 27 47 42 0.12 0.51 1.2 4.9 7.4 10 190 10 130 00 40 370 110 0 1 20 40 soo 30 DSW 012798 "Dr. Gaffney has recently reported (Gaffney, 1976) that his studies have determined that PCB's are formed during pre-chlorination of sewage containing biphenyl at the waste treatment facilities he has been studying. The results are being prepared for publication at this time. Dr. Gaffney indicated that the PCB isomers predominately formed are the 2-chloro, 2,2'-dichloro, 2,4'dichloro isomers. A relatively small amount of trichloro Isomer has also been detected. Hydroxylation of the biphenyl in the sewers enroute to the waste treatment facilities greatly aids the chlorination of the biphenyl nucleus. 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; when chromatographs of biphenyl reacted with Clj-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. DSW 012799 87 STLCOPCB4002723 2. Diphenyl Oxide The information and data given below has 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 stolchlometrlcally 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 95Z. 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 - XAS1075L). 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 OSW 012800 88 STLCOPCB4002724 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. Bioconcentretlon "Detection of cheaicel residues in fish has been the key environmental alert for DDT end 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 ex tant, 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). * Results published by Neely et_ al. (1974). The log bioconcentration factor was experimentally determined as 2.29 (therefore, bioconcentration factor - 190). DSW 012801 89 STLCOPCB4002725 X. Environmental Assessment A. Biphenyl Biphenyl la 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 muni cipal 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 at al., 1975). However, since biphenyl is not monitored at treatment facilities, the efficiency of general treatment cannot be determined with certainty. Also, the method of treatment may be a signi ficant factor in the amount of biphenyl converted by biodegradation. Tlncher (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 volatilization. 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 FCB isomers during pre-chlorination processes for disin fection and deodorlzatlon (Gaffney, 1974, 1976; Carlsen, 1975; Johnsen, 1975). OSW 012802 90 STLCOPCB4002726 Laboratory experiments which have mimicked treatment facility methods have found that the biphenyl nucleus can be chlorinated with four, or usually less, chlorine atoms. Commercially prepared PCB's have a much greater degree of chlorination and have certainly less biodegradability than the PCB isomers which may be gen erated 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 per haps 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 bi phenyl are annually released to the atmosphere by biphenyl's 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 avial- able 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 DSW 012803 91 STLCOPCB4002727 Laboratory experiments which have mimicked treatment facility methods have found that the biphenyl nucleus can be chlorinated with four, or usually less, chlorine atoms. Commercially prepared PCB'a have a much greater degree of chlorination and have certainly leas biodegradability than the PC8 isomers which may be gen erated 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 per haps 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 bi phenyl are annually released to the atmosphere by biphenyl's volatilization or to water by leaching from creosote oils (SBC 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 avialable 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 DSW 012804 91 STLCOPCB4002728 of diphenyl oxide release are soap and perfune 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 soapa. The Council of Europe (1970) Included diphenyl oxide in the list of temporarily admissible artificial flavouring substances (Opdylce, 1974). 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. DSM 012805 92 STLCOPCB4002729 Appendix A Physical Properties DSW 012806 93 STLCOPCB4002730 Biphenyl (Monsanto Tech. Bull. 1C/FF-29) Melting point,.*C 69 Bolling point at 760 mm Hg, *C 10.5 mm Hg, *C 255 118 Specific gravity, 20*/4*C 77*/4*C 1.04 0.99 Lbs./gallon at 77*C Refractive index, n^ 8.23 1.588 Viscosity at 70*C, Saybolt Sec. 100*C, Saybolt Sec. 31.2 28.8 Surface tension at 129,2*C, dynes/cm 39.5 Flash point, closed cup, *C Open cup, *C 113 124 Latent heat of fusion, Btu/lb. 53.1 Specific heat, Btu/lb/*F 0.43 Odor Pleasant, peculiar Appearance Colorless to pale yellow crystallized solid or flakes Molecular Weight 154.20 Empirical Formula Structural Formula Wi Solubilities - Grams biphenyl per 100 cc of solvent Hydrocarbons Water* Solvents Mineral Spirits Gasoline (Texaco) Kerosene Benzene Xylene Turpentine Toluene Solubility 16.9 24.1 17.5 81.5 56.9 24.2 62.0 0.00018 c 26 26 27 27 27 24 18 * 95Z Biphenyl dye carrier (Haas et al., 1975) 94 DSW 012807 STLCOPCB4002731 Diphenyl Oxide (Dow Form No. 110-288-72) Molecular Weight Bolling Point *C 760 ounHg Specific Gravity 25/25*0 Found 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 DIPHENYL OXIDE GRADE Technical Perfume Industrial 170.2 257* 1.070 8.92 1.578 26* 239* 258* 1144* 11 ,800 170.2 257* 1.070 8.92 1.579 27* 239* 258* 1144* 11,800 255* 1.065-1.075 8.92 - 15* 235* 255" - m m m 20.8 ppm m m m m' 21 ppm ,,m m m m 21 ppm m m Solubility of DF0 in water at 25*C . Solubility of water in DP0 at 25*0 . Solubility of water in DP0 at 30*0 . BOILING POINTS OF DIPHENYL OXIDE Boiling Point MM Hg 257.9*0 181.3*0 147.1*0 121.0*0 77.0*0 760 100 30 10 1 95 DSW 012808 STLCOPCB4002732 Appendix B Materiel Safety Data Sheets DSW 012809 96 STLCOPCB4002733 MATERIAL SAFETY DATA SHEET (APPROVED BY THE U.S. DEPARTMENT OF LAbOR AS imilr" is i&rni OSHA-20) |ll *.. * *4 etl * * t ' -.1 * m '* *.#.* i *** U* *'* **' | . A* . ' i/(j jr- i A U. - l*n. f +* *4b ** wi,jFi;ig)t|N't N*V( DOW CHEMICAL.U.S. A.. l *" Y" 1 V WrfTVf t n Section \ NAME A PftOOUCT * ~T"rrTfi" k yt cw:> MIDLAND. MICHIGAN 48640 wwTFT.-t-rT .jTiVaCr.'i------ l-A <; i lie * ~'.?7-n. i.o 14 . : 517 - 636 4400 Diphenyl Oxide, Technical __ Diphenyl Ether sielii'n a " INISREOIENTS" Diphenyl oxide 95 (Not a specification value) BOILING POINT <*F.) VAPOR PRESSURE (mmHa>20<> Sacrlan 3 4.QR PHYSICAL DATA SOLUBILITY IN WATER SPECIFIC GRAVITY (H,0= 11 vaPOR OENSITY (a>r = 11 _appearance . Colorless liauid volatile by volume ___ Sactian 4 FIRE ANO EXPLOSION HAZARD DATA * . AlH IN T UNO MiTNOO USCOt M.AMMAILl b MITI (IT* IN AIM* 205 f Cleveland Open Cup u.r.L (j,8 . EXTINGUISHING pe C OI a p mvo?* sifoam mtssr01- EK OSS-oa. v f t<*L ri^t FiCHTiNO FffOTtCTiON CUHMCr AND MAZAHCI Insoluble 1.070 ft vifLr |w-p - n" 1.5 None. STABILITY (NORMAL CONDITIONS) Sacfian S REACTIVITY DATA esNoiTiONi re tioio STABLE UNSTABLE INCOMPAT. ISILITY uarcAiawt TO Avoid PlwATER [> orma BASE r | i1 'lOXIOlflNC I,.jCQRRmvC _____ | [MATERIAL_______ _______ rrn .ci-ij-j rs inrawr* snorvf------------------ -- None. HAZARDOUS POLTmERIZ* MAY OCCUR COXOtTIONt TO A *0(0 aTIOn _ __ T.. WILL NOT X OCCUR , B- - . Sactian 6 SPILL OR LEAK PROCEDURES .. b hi VAE|N N CAi( MATiAlAI.lt i( L k A lilV D* LpTO Small spills - absorb in sweeping compound. Large spills - call Dow emergency number for Instructions . S* ~ % fc MC IhDO Burn or bury in accordance with local ordinances. DSW 012810 STLCOPCB4002734 Diphenyl Oxide, Technical 1ATERIAL SAFETY DATA SHEET <cont., ___ _-- _ ....... ........................................ ........ ............... ...____ _MlChlCAN 4H4J0 --~~ ~r ---- --- - 'health hazard data chemical u.s.a. -- -- ow single dose oral; LDf 4000 mg/kg for both rats and guinea pigs. Estimat ng from these data, the lethal dose for a 100 pound person may be in the ange of _3/4_ cupful_.' 'TTT c rVc * "" Mild to moderate irritation; unlikely to cause injury. -r^j-yvr.trv----------------------------------Occasional contact- no adverse effects expected. Mild to moderate irritation upon repeated, prolonged contact. | No LD# determined because of lack of indication of Not readily absorbed - problem from absorption. j*1 v 1 1 -- ' 1 ^*"1" " " "' " - n i -- -- m `Ly:. 1 ,ppm_-.based on odor-control. No problem at room temperature. Disagreeable odor, possible liver injury at high concentration. I ~T~ " "ere ' EYES & SKIN: Flush with plenty of water; get medical atten tion if irritation develops. Remove contaminated clothing plush and free of chemical before reuse. .Th I INHALATION: If discomfort develops from breathing vapors, get - PLOWING : 1 WATER patient to fresh air. * INGESTION: No known antidote; treat symptomatically. N|*C Ci*f PLUiot on iN9ucr l OMIT INC I# FaTIInT It UNCOKV CIOUS o having C9N>ULtiQNt S*erlo" SPECIAL PROTECTION INFORMATION -Sufficient to control to TLV. a i a T 5** 'iTMB1p<5Vif5 aptcify ryp*i 1 '" _ 'When disagreeable odors occur, full-face mask and canister for organic vapors. "'"'TV' Tf *'. cTmiwg' "" Clean clothing. 11 "l.J-JT fiJMVA-.'.T !jY IliSlTAHfCOVfJCt.iLOAPtPAPM* ltUOV aiRtirt I |*i rn t>oc imicloi | iChkmical l iOAKciu aocoecs T*0*-T COC1LII Ji SvCaOw 4-.LN1 _ _ OTH(A Sactlan SPECIAL PRECAUTIONS OR OTHER COMMENTS *V k)k rare*; is As<ii.iNft AMO tTOfclMC Use reasonable care. Store in cool, dry place. DSW 012811 r STLCOPCB4002735 MATERIAL safety data sheet i r/80 ft f The U. S. Of PaR T T OF LaAOR AS " vn:iall iimiIo' 1 v> tj.m OiH A i'll I-- > I b*. *** r * I W< *H *> ** '* P4"r4** **' ** * *****J- * ' 0r w*p taS-f ,~4 V *f. *r ' ` ^ .#4 ** a * * * * ` -*`1 * ,'*M f ** < 1 J ' ' " r \ * 4*4< DO'.t CHEMICAL U.S.A. " # 3%V ft4 *t"t c * wi*A'S February 16, 1976 "r ot nL4 Sip'nenvl. High Purity Section NAMS 4 *a09UCT " *. T TTS.. 2* : w MIDLAND. MICHIGAN 43340 S.er.an i INGREDISN TS CTT'f"-;. : 517 - 633 - 4400 Biphenyl, minimum i i S.et n 3 PHYSICAL OaTa SO NO POINT ,-F.) | -----------5TI--------------------------- solwRili *t in w* riSR 82 5SC /**'. 9RSSSJR! i'n..H| J04l -* * -M OSNjjry **r s n 1 i -- -- 5PECIF C irtliA 1) ", vYL A":L! SY VP'.u** ap*arance White solid; odor - moth ball3 sfin 4 FiVs an'o'exploIioh HAZARD oata"' - ...... -1ST INC vi**U9UlCO A 233 jf Tag Closed Cup 0.6 3 232F j .CS 7j C/ 1 ! l.lo q'en' 5 2 5 ! r.'ot .\oolititle I. 5.3 1 31 t . . . __Q *ATER FOG J3FOAM o AFOLCaO'4HOL noric riON uj.vr.' * E:____ Uv.`-.?-'2i*A,,J-J None STAaiLl'Y Section S : .6.;r5m sat..-'5------------ j 5 yimC 1 r' tr ^ i'ASLi NiTASLE REACTIVITY ?aTA incO'a r. taiLlTY "Y f"~)ATeW f to CIO ' wmm ~:4.KBvraJTCatevt" |~~jaA4E [~~]'-.CaR?SI '; c X|ma * . Ntr.e HAiAOOUI aTiOn .. MAT . > t .an, ro A J-; OCCUR ILl NOT ???- S<tun A Viii* ****. ' li'AtLiiAU^ ' SPILL 0 R * L EA/TpS OC 6 DURIS* " '< . 1----------------------------------- Scoop up and salvage if possible OSW 012812 . v v Observe faderal, State and Local laws. tr disposal instructions. Contact The Dow Chenicn. Cc'yinv . STLCOPCB4002736 diphenyl, High Purity 'ATERIAL SAFETY DATA SHEET <co*r. - 7___HEALTH ~HZi aB0"j5*Ta DOW Ch3.iC.il. U.S.A. ow single dose oral toxicity. LDm rata is greater than 4000 mg/kg. i tins ting from these data, the lethal dose for a 100 l'o, person .-nay be n-o ounce*. * *C ; - ~ rr' " *'* p to slight irritation but no corneal injury. hort' single exposure not likely to cause significant irritation. Prolonged ir repeated exposure may cause slight irritation. - Vs * *i jn-*"* " ` iot likely to be absorbed in toxic amounts. Vi s - : S ~ " " I i-n i I i . -- ir -- - * -- LV: 0.2 ppm or 1 mg/m* (1974) K-*'1 ** 'j"T<fT'`iiijit Respiratory irritation. * ' it* EYES: Flush with plenty of water for 5 minute3 and get medical; I help if ill effects occur. SKIM: Wash with soap and water. ' ! Remove grossly contaminated clothing end wash before reuse. | 4ttM INHALATION: If ill effect* occur, get person to freuh air n::d ! l><*g get medical help. INGESTION: Not likely a problem. If large AATf* AT UtAiT amounts are swallowed, see above, promptly indues vomiting and get medical help.* j; _5___ i vNiJi ;x . 1I I 5*>: ....................... ...... < " ' $. 1 "SPECUI. PROTECT 1Ch"INFOS*aTion "==~ ITrrETT "-*-- .... ------- ------------- Control dusts o_r mists to TLV. 'Tf*':* '-.'i"r#y*.'oN rtf -- " ' ....... -- "' -------- Respiratory protection required in absence of proper environmental control. If required, use an approved dust respirator. Clear, body covering clothing l!3Ti5.5 ! ____ I'? ><,. r.t __ l_ I..IT., !_rri*_p * : <_'*- . 0*e<4 fountain and washing facilities nar work area. sctin * SPECIAL MECAUTIOni <34 Jf'-S't C0nTS llai' 'a 'i -NOw*tw *> i_jTlo4'V*c' Practice reasonable care and cleanliness to avoid gross skin and eye contact. 'Avoid breathing vapors and dusts if generated. " j *MOTE TO PHYSICIAN: No specific antidote known. Treatment depends or. me sound judgment of the physician and the individual reactions of the patient. . DSW 012813 " 100 STLCOPCB4002737 IV1AI LK1AL bAf-t 1 Y UA I A i>HCC I IAPPROVED BY THE U.S. DEPARTMENT OF LABOR AS `'*nn*llr to (on OJIIAlO) l . A * ** |ft4R * *! ** * >>. ** **' *. ** tI. tif M'ir m*-#0 >*' * * * *'* ** *** i 4A-J *! A| ft* 1 a4 M*t * I.. *A| / ** i" )**A t ) * ** h,**ft l* ((i < *. ; t ,.< I A t a*<1 *<! 1 NAME k PROOUCT ------------- cm--Hj.*rmi.r?-5bim DOW CHEMICAL U.S.A. ____ MIDLAND, MICHIGAN 48640 47i**rp ` *k^rkiiMMfiti'T*rWv*VcNn''""" "it**;cr>r>ttd w* Nloovemb. er 13 ,, 1974 __________ TiiV il'WivTk DOWTHERl'tf A heat transfer fluid Sactian 2 'WROimi* INCREOIENTS -rsruVc j4 hc S17 636 4400 ' K'. Diphenyl oxide Diphenyl (Not specification values) 73.5 }lpl *6.5 BOILING POINT |*P.) Saciian 3 PHYSICAL DATA ---------- zfgzrrB--------------------------- SOLUBILITY IN WATER vaPOR PRESSURE (aaHih 20'>) 0 SPECIFIC GRAVITY (HjO= 1) VAPOR OENS1TY Im = 1) >1 _____ -. VOLATILE by volume appearance Stray_rp_lQred liquid, aromatic,.odor.* Scctlan 4 PIPE ANO EXPLOSION HAZARD DATA L AIM **0Nf AND MCTHOC UCO` L4UMA ML fc UlMTf .T# ivJ Alftt 255 f Cleveland Open Cup a.p.l. 0.5% (500F) L3.8ppm 60 "F L.050-1.075 O 25, ^ |u.p.u. 6.27. (500oF E XTINCUIShiNO I (--3 WATER rro mcdu----------[ US) FG____ I XIpoam I--I ALCOHOL 1 Ifoam TOFTTaliSi'triflc inoT te TtOK kaUOMH* ANO HSA*Oi r--i LXlco? r~iORY r~1 LxIchemical I J Self-contained breathing apparatus may be needed in enclosed " spaces STABILITY Sactla* 5 c6ncuYion t6 avAio NORMAL CONDITIONS! 3: stable 1 UHiTAtUI ms u iuB Vo a vi o INCOMPAT. IBIUTY TTi A(.r,4'vJ ____ D*c,fL OT*w if ecTiri. rVrf*l' AArfftOcti ........ * None hazardous POLYMERIZ ATION MAY OCCUR ILL NOT cBnoition4 to avo.o REACTIVITY DATA CORROSIVE l--nOXIOlZIHC 1 XImaterial ........- --= iuTtir4* SPILL OR LEAk^PROCEDURES" , . ' ' v m t p l m m i*i7 M*irio*L >* f l . a%r r> on ir3 .cc Soak up with absorbant material. "v*;r **5*r ' Incineration in approved equipment. OSW 012814 STLCOPCB4002738 j DOWTHERM A . 1ATERIAL SAFETY DATA SHEET CONT.j DOW CHEMICAL u. S.A. . ........ .......... ........... ....... ;---- -------------------------------------------------------------------PIOLAHO, MICHIGAN 4*4.0 ....... '* ' 1 P , '} 1 ' . ' ` 1,1 ` ....................7 HEALTH HAZARD DATA *1 --- ... ' * ' -- -- ,ow single dose oral toxicity. LDy, racs is in the range of 2000 to 4000 mg/kg. itimacing from these data, the lethal dose for a 100 lb. person may be 2 o 4 fluid ounces. _ i:' C i ' * *7* *" ' " ~~ ---- 'j to mild irritation but no corneal injury. -r.` .v i - * 5 i--~ --------------------------------------- ------ ---------- iort single exposure not likely to cause significant irritation. Prolonged r repeated exposure may cause up to mild irritation. ' "iTi-THA-T-s,. 'Not'lflcely to'be absorbed~in toxic amounts. Very"'low~in" ' oxicity by_this route.:.................................................................................. W. Ippm (1973) > t "J"-TT.'c AT idiiijHL '' nhalation - vapors have a disagreeable odor. ansm EYES: Flush with plenty of water for 5 minutes and get medical EYE help if ill effects occur. SKIN: Promptly flush skin with plenty of water. Remove badly contaminated clothing and wash f U)SH ,lJri before reuse. INHALATION: Not likely a problem due to dis- J LOWING agreeable odor. If ill effects occur, get person to fresh air WATER and get medical help. INGESTION: Not likely a problem. If A large amounts are swallowed, see above, promptly induce vomiting and get medical help.* wINUTeS " ., * . .\ i . *; *Cuir.K < PAT 1 : )11 .-VS .*! * s . Sactlan I SPECIAL PROTECTION INFORMATION `Good room ventilation usually adequate for most operations. "ntrol vapors to TLV_.;___________________________________________________ ________ ______ *' &A'*OrtT>'iTSTfc t>6n >Mc7I/t^pai ~ ~ -- One likely to be needed. For emergencies of % hour or less, full face mask '.us an organic vapor canister. j"<7"c T-~e"Tc ~ lean body covering clothing. "' -- -- I f l**OT NOAMalwvK/ 1*TY tkillCI ).fCTiOJ_ _ V\. |cir<OUT tioc t->l a** ri|Hr sowawKi rnnT|H iaeitv1QCoLIXiUitLuM rv-* m*' ** 1 UjMAtUf , ____ .>M^^fctSCNcTU 9 SPLgJetAL PRECAUTIONS O* QTHg* COMMENTS 4^1 fiAlMN HANUCiNO ANQ irQRINa ' - LJactice reasonable care and caution. Avoid breathing vapors if generated, void direct contamination of water because of fish toxicity. ] r,0TE TO PHYSICIAN: No specific antidote known. Treatment depends on the 3und judgment of the physician and the individual reactions of the patient. DSW 012815 in? STLCOPCB4002739 REFERENCES Ameen, J. (1976), Personal Communication, Sanitary Engineer, Burlington Industries, Greensboro, N.C., May 1976. American Conference of Governmental Industrial Hygienists (1974), "Documentation of the Threshold Limit Values". Anderson, L. 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(1933), U.S. Patent No. 1,894,266, January 17, assigned to Monsanto Co. Earhart, H.W. (1976), Personal Communication, Manager-Special Aromatic Products, Sun Oil Co., Corpus Chrlatl, TX, April-May 1976. Environmental Protection Agency (1975), "National Conference on Polychlorinated Biphenyls," (Nov. 19-21, 1975, Chicago, IL) EPA-560/6-75-004, Contract No. 68-01-2928. Ersklne, M.G. (1970), "Naphthalene," in Chemical Economics Handbook. Stanford Research Institute, Menlo Park, CA. Faith, W.L., Keyes, D.B. and Clark, R.L. (1965), Industrial Chemicals. 3rd Edition, John Wiley & Sons Inc., New York, pp. 130-1, 585-88. DSW 012817 104 STLCOPCB4002741 Frank*, A. and Traber, W. (1972), German Offen. 2,223,380, aasigned to CibaGeigy, Nov. 30. Gaffney, P. (1974), "Letters - PCB's: Another Source?," Science 183:367-70. Gaffney, P. (1976), Personal Communication, Georgia State University, Atlanta, GA, June 1976. Garza, N. (1976), 'Mho's Building in HP1-USA," Hydrocarbon Processing, March, p. 43. Graham, W. (1976), Personal Communication, Florasynth, Inc., Nev York, NY, April 1976. Haas, J.M., Eerhart, H.W. end Todd, A.S. (1975), "Environmental Guide to Dye Carrier Selection," American Dyestuff Reporter, March 1975. Hahn, A.V.G. (1970), The Petrochemical Industry. McGrew-Hill, pp. 411-12, 475. Hale, W.J. (1930), U.S. Patent No. 1,744,961, Jan. 28, assigned to Dow Chemical Co. Hale, W.J. and Britton, J.W. (1933), U.S. Patent No. 1,882,824, Oct. 18, assigned to Dow Chemical Co.' Hennls, H.E. (1974), U.S. Patent No. 3,793,377, Feb. 19, assigned to Dow Chemical Co. Hites, R.A. (1973), "Analysis of Trace Organic Compounds In New England Rivers," J. Chromatogr. Scl. 11(11):570-4. Hunt, R.H. and O'Neal, M.J. (1967), "Petroleum (Composition)," Kirk-Othmer Encycl. Cham. Technol.. 2nd Edition, 14:849. Insera, W. (1976), Personal Communication, Stauffer Chemical Co., Edison, NJ, May 1976. Johnsen, R. (1975), "Chlorination of Waters for Disinfection - A Study of the Production of Undesirable Chlorinated Products," National Conf. on Poly chlorinated Biphenyls (Nov. 19-21, Chicago, IL), EPA Contract No. 68-01-2928. Earr, C., Jr., Estep, P.A., LoChang, T. and Camberlatl, J.R. (1967), U.S. Bureau of Mines Bulletin No. 637, p. 198. Klmland, B., Aasen, A.J. and Enzell, C.R. (1972), Acta Chem. Scand, 26(6): 2177-84. Kinlln, T., Muralldhara, R., Pictet, A., Sanderson, A. and Walradt, J. (1972), "Volatile Components of Roasted Filberts," J. Agr. Food Cham. 20:1021-8. 105 DSW 012818 STLCOPCB4002742 Kolar, B. and Klacelj Z. (1962), Chemicky Prumysl 12:326-332. Kothny, E. (1976), "Letters - Living with PCB's," Chem. Eng. Mews, Jan. 19, p. 5. . Levek, R.P. and Williams, D.O. (1975), "Flame Retardants," Modern Plastics Encyclopedia. 52(10A):203. Mahinkia, M. (1976), Personal Communication, Glvaudan Corp, Clifton, NJ, April 1976. Malr, B.J. and Mayer, T.J. (1964), "Composition of Dinudear Aromatics, C._ to C^, in the Light Gas Oil Fraction of Petroleum," Anal. Chem. 36:351-362. MeMe11, D. (1969), "Tar and Pitch," Kirk-Othmer Encycl. Chem. Technol.. 2nd Ed., 19:675. Mispley, R.G. and Barber, W.&. (1940), O.S. Patent No. 2,173,453, assigned to Crown-Zellerbach Corp., Sept. 19. Mitchell, L.C. (1973), "Process for Production of Polybromlnated Aromatics," U.S. Patent No. 3,763,248, Oct. 2, assigned to Ethyl Corp. Moore, D.E., Mills, J.F. and Schneider, J.A. (1974), "Bromlnatlon with Bromine Chloride Under Pressure," U.S. Patent No. 3,845,146, Oct. 29, aasigned to Dow Chemical Co. Moose, J.E. and Pritchard, W.N. (1934), U.&. Patent No. 1,968,154, July 31, assigned to Monsanto Co. Mumma, C.E. and Wallace, D.D. (1975), "Pollution Potential of Polybromlnated Biphenyls," Midwest Research Institute - EPA Contract No. 68-01-2105, Office of Toxic Substances, June 1975. Neeley, W., Branson, B. and Blau, G. 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