Document BRgDdOyL4YVZq6NKj76Kr1bew

DRAFT TR 76-399 CHEMICAL MARKET INPUT/OUTPUT ANALYSIS OF BIPHENYL AND DIPHENYL OXIDE TO ASSESS SOURCES OF ENVIRONMENTAL CONTAMINATION William M. Maylan Philip H. Howard Cancar for Chamlcal Hazard Assessment Syracuse Research Corporation Merrill Lane, University Heights Syracuse, New York 13213 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 MGNS 053263 a0TICE This document is a preliminary draft. It has not been formally released by EPA end should not at this stage be construed to represent Agency policy. It la being circulated for comment on its technical accuracy and policy impli cations. ii HOMS 053264 Table of Concents 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 ManufacturingandProduction Technology A. Biphenyl ' 1. Thermal Dehydrogenation of Benzene a. Manufacture b. Production Volumes c. Economics d. Environmental Management a. 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 Page 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 Hi HONS 053265 Table of Contents (Coat'd) X. By-Product From Chlorobenzene-Phenol Process e. Manufacture b. Production Volumes c. Shipping d. Economics a. Environmental Management 2. Catalysis of Phenol a. Production Volumes b. Environmental Management c. Economics Use and Use Process Technology A. Biphenyl 1. Dye Carrier a. Manufacture b. Dye Carrier Use c. Environmental Management d. Areas of Use e. Economics f. Alternative Products g. 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. Isopropylblphenyl (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 iv MONS 053266 Table of Contents (Cont'd) (II) Production Volumesand Uses (III) Economics b. Methylbiphenyl c. Ethyl- and Butylbiphtnyl 5. Eutectic Heat Transfer Fluid 6. Folybromlnated Biphenyl (PBB) a. ' Manufacture b. Production Volumes c. Economics d. Alternatives B. Diphenyl Oxide 1. Eutectic Heat Transfer Fluid a. Users b. Production Volumes c. Economics d. Environmental Management a. Use Alternatives (Jh 2. Dowfax*y a. Manufacture b. Production Volumes c. Economies d. Environmental Management ' a. Alternative Products ' 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 v plge 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 37 58 58 59 59 HONS 053267 Table of Contents (Cont'd) 5. Butylated Monochlorodiphanyl Oxide e. Manufacture b. Production Volumes c. Environmental Management d. Economics ' e. Alternatives 6. Decarbromodlphenyl Oxide a. Manufacture b. Production Volumes c. Economics d. Environmental Management e. Alternatives 7. Minor Commercial Uses of DiphenylOxide a. Chloromethyldlphenyl Oxide ' b. Methoxymethyldlphanyl 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. Coel 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 7ft vl HONS 053268 Table of Concents (Cont'd) VIII. Material Btlanc* - Exposure to the Environment A. Biphenyl 1. Dye Carrier 2. Fungicide*. 3. Dovtherm '**' 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. Perfumea*and Soaps 3. Dowthenr A IX. Environmental Perspectives A. Occupational Exposure to Man 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. Bioconcentration X. Environmental Assessment A. Biphenyl B. Diphenyl Oxide Appendix A - Physical Properties Appendix B - Material Safety Data Sheets REFERENCES Pane 73 75 75 75 77 7.7 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 HONS 0532*9 List of Tables III-l. V-l. VIII-1. VIII-2. IX-1. United Stetes Biphenyl Producers Textile Chemical Specialty Firms Who Hake Biphenyl Dye Carriers Estimated Environmental Releases of Biphenyl Estimated Environmental Releases of Diphenyl Oxide Chlorination of Biphenyl Utilizing Water Renovetlon Conditions Page 10 37 76. 79 86 viii HONS 053270 Llat of Figures IXI-1. Annual Biphenyl Production (SRC Estimation) III- 2. Currdnt Annual Biphenyl Use In the United States IXI-3. Domestic Diphenyl Oxide Use in 1975 IV- 1. Biphenyl From Thermal Dehydrogenation of Benzene IV-2. Ceneral Process for Hydrodealkylating Toluene toBenzene IV- 3. Diphenyl Oxide From Chlorobenzene - Phenol Process V- l. Polyester Fiber to Garment Flow Diagram V-2. Dyeing and Finishing of Polyester Fabrics V-3. Process Manufacture of Dowfax<*>'Solutions 1X-1. Reduction of Concentration Owing to Biodegradation Analysis of Culture Cells and Water 11 14 15 18 23 28 36 39 54 85 HONS 053271 lx 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 affects. The standards sstablishad by OSHA ars directed at protecting workers who might be exposed occupationally to air vapors or partlculatss 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 FCB (poly chlorinated biphenyl) isomers are formed whan sewage, which contains biphenyl. Is discharged to waste treatment plants utilizing chlorine for disinfection and deodorizatlon (Carlson at al., 1973; Gaffney, 1974, 1976; Johnsen, 197S). Biphenyl and diphenyl oxide have also been shown to bioconcentrate In fish (Neely e al., 1974). This report considers environmental sources of biphenyl and diphenyl oxide and estimations of the amounts which may be exposed to the environment. 1 MONS 053272 II. Historical Development and Future Outlook A. Historical Development 1. Biphenyl Biphenyl (diphenyl; phenylbenzene), (CgHj)^, was first reported In 1862 by Fittlg, who prepared it by the action of metallic sodium on bromobenzena. Berthelot prepared biphenyl in 1867 by passing benzene vapors through a red hot tube. In 1875, Btlchner 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 comnercial quantities for use as a heat transfer fluid In the refining of lubricating oils. Be set up a pilot plant for this purpose. Soon .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 time, Dow Chemical Co. entered the commercial biphenyl field with Dowtherm^A, a eutectic mixture of biphenyl end diphenyl oxide for use In heat transfer. Historically, the two principal manufacturers of biphenyl have been the Monsanto Co. and the Dow Chemical Co. (Verser, 1976; Poffenberger, 1965). The earliest commercial reactors were vessels holding a bath 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 benzane 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> HONS 053273 Patent* have also bean 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 conmercial potential of racoverlng a bi phenyl by-product formed when toluene Is hydrodealkylated to benzene was realized. Today, tha 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 70X of the current annual biphenyl production of 86 million pounds Is obtained by refining the dealkylated toluene by-product (SRC estimation). The remaining BOX 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 tha lata 1940's, biphenyl began to be used as a mild fungicide when coated on Individual fruit wrappers, although the patent describing this us* was dated somewhat earliar (Mispley and Barber, 1940). More recently, biphenyl has been impregnated onto paper pads used In closed fruit packages. These fungicidal uses still exist today, but at a level which has slowly decreased due to better transportation and refrigeration systems. In the 1960's, biphenyl found use as a dye carrier for disperse dye applications to polyester fibers. The use of biphenyl dye carriers has accelerated so greatly In the past six years that this use represents the largest 3 HONS 053274 single application of biphenyl at present, consuming nearly 60Z 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 lsopropylbiphenyl. Approximately 10 million pounds of lsopropylbiphenyl are annually produced, at present, for applications In carbonless paper. Commercial production of flame retardant PBB's (polybTominated biphenyls), which began In 1970, was terminated In November, 1974, a year after PBB'a 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 mlx-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, phenoxyben2ene, DPO) In 1925-1926, using It as a heat transfer fluid In a steam power process. These experiments eventually lad to the development of Dowthen^ A, a eutectic heat transfer mixture of 73.5X diphenyl oxide and 26.5Z biphenyl. In the early 1930's. Dowtherm A has been e wldely-used heat transfer fluid since that time. 4 M0NS 053275 The original American patenta describing diphenyl oxide pro duction were easlgned 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 NajCO^ or NaOH, under pressure with copper catalysts. The second patent (Hale and Britton, 1933) refers to the Dow process of phenol production from chlorobenzene and aqueous base. In this process, diphenyl oxide is formed as a by-product. Historically, nearly all of the diphenyl oxide produced in the U.S. hes 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 rsactlng phenol in the presence of a catalyst. The only commercially important early use of diphenyl oxide, other than for Dowthen<rS*> A heat transfer fluid, was for applications with per fumes and soaps. Diphenyl oxide has a characteristic geranium odor. Use In perfumes and soaps is still important, with roughly 100,000 pounds annually consumed. Historically, most of diphenyl oxide produced has been used to formulate Dowthen(r) A. Houghly two-thirds of the estimated 6 million pounds of diphenyl oxide produced in 1975 was used in Dowtherm(") A (SRC estimation). Other commercially important current uses of diphenyl oxide include Dowfai (alkylated sulfonatsd derivatives) surface-active agents, deca- bromodlphenyl oxide flame retardants, diphenyl oxide dye carriers, and butylchlorodlphanyl oxide capacitor fluid. Dowfaj^ production started in the early 1960's and decabromodlphenyl oxide and diphenyl oxide dye carriers started in the 1970's. Butylchlorodiphenyl oxide la discussed in Future Outlook - Diphenyl Oxide. 5 HONS 053276 Several diphenyl oxide derivatives, chloromethyl diphenyl oxides, end methoxymethyl diphenyl oxide, hove minor commercial uses In polymer and realn 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 851 Increase in the polyester market by 1980 and a 1701 Increase by 1985. Biphenyl, however. Is only one of perhaps eight to ten commercially Important dye carriers used In polyester dyeing. After consulting with Industry spokesmen, It Is estimated (SRC estimation) that biphenyl dye carriers make up approximately 25-301 of the total dye carrier market at present. The total dye carrier markat Is sxpscted to increase by 471 by 1980. This 472 figure is smaller than the 851 polyester growth figure because technological Improvements in dyeing techniques should decrease the amount of dye carrier which is required. If biphenyl maintains 25-301 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. annuslly (SRC estimation). Increased biphenyl consumption is also projected for heat transfer fluids and alkylated biphenyls. Dow has announced an expansion of their Dovtherm A units, to be completed by 1978 (Anon., 1976 a). In early 1976, Monsanto began commercial production of Therminol VP-1 heat transfer fluid, which will compete 6 HONS 053277 with Dow's Dowthenii A. Therminol VP-1 and Dowtharm A hava Identical chemical compoeitione. Isopropylblpheny1, used In carbonlaaa paper, and nethylblphanyl, uaad aa a dye darrler, are also expected to increase output by 1980. A guess would project that nearly 10 million additional pounds of biphenyl will be uaad for heat transfer and alkylation by 1980 (SRC estimation). The projected phase-out of PCD'a by Monsanto would decrease the needed biphenyl production by nearly 21 alllion pounds annually. However, alternatives to PCB's may Include another biphenyl derivative. Effects to the biphenyl market by the PCB phase-out cannot be ascertained at this time. 2. Diphenyl Oxide There will be large Increases in the production of diphenyl oxide by 1980. Until the end of 1975, the only commercial quantities of diphenyl oxide were obtained from Dow's chlorobenzene-phenol process as a by-product. This amounted to approximately 6 million pounds annually (SRC estimation). However, at the end of 1975, Monsanto began commercial production of diphenyl oxide for use in Tharminol 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 butylchlorodiphenyl oxide, but also for Dowtherm A and decabromodiphenyl oxide (Anon., 1976 a). An estimated $10 million of this expansion had been completed by April, 1976. The primary reason for Dow's diphenyl oxide expansion appears to be synthesis of butylchlorodlphcnyl oxide. Dow Is hoping that butylchlorodlphenyl oxide will be accepted as a PCB replacement in capacitors. Test quantities utilized by McCraw-Edison appear promising. Dow says It hopes to hava production capacity In excess of 5 million lba/year of butylchlorodlphenyl oxide by the end 7 HONS 053278 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 bucylchlorodlphenyl oxide as a FCB substitute. It should be noted, however, that other companies are developing and evaluating FCB substitutes different from butylchlorodlphenyl oxide. Several PCB users have Indicated that butylchlorodiphanyl oxide may not be the best available alternative. 8 HONS 053279 III. Market Input/Output Data A. Production Tabl* III-l lists th* domestic producars of reflnad blphanyl with their raapaetiv* production aitas, year*, and capacities. Also llaead in Table III-l are th* petrochemical companies who commercially supply unrefined blphanyl faed atock (by-product from toluene dealkylation) to biphenyl refiners. Annual bi phenyl production Is shown In Figure III-l. Two companies have stopped refined biphenyl production. First Is Geneva Industries of Houston, Texas, who sold their biphenyl refinery to Pilot Industries In 1974. Second Is Bethlehem Steel Corp. of Sparrow* Point, Maryland, who termi nated blphanyl refining in 1974. Th* Dow Chemical Co. and Monsanto Industrial Chemicals Co. are the only domestic producars of diphenyl oxide. The Dow production site is located In Midland, Michigan, while Monsanto's site is located at their Chocolate Bayou facility In Alvin, Texas. Dow has been Involved In the production of diphenyl oxide since the early 1930's. Monsanto began commercial production at the end of 1975. Dow did not release their annual production volumes, as the Information Is considered confidential (Otis, 1976). However, before the current diphenyl oxide expansion, Dow obtained all of their diphenyl oxide as by-products from their chlorobenzene-phenol process. Capacity of this phenol process has been estimated at 48-70 million pounds annually (SRI, 1975 a, 1976). Since approxi mately 0.1 pound of diphenyl oxide Is formed for every 1.0 pound of phenol formed (Hahn, 1970), the annual diphenyl oxide output would be 4.8 to 7.0 million pounds; end, therefore, 6 million pounds may be a good estimate of the annual 9 MONS 053280 Table III-l. United States Biphenyl Producers 1. Cheaol, lac. 2. CFS Chaaleal Co. c Dlv. of Chealstry 4 Pollution Sciences 3. Dm Chealcal Co. 4. East Coast Chealcal Co. 5. Honsaato Industrial Cbealcals 6. Pilot Industries 7. Sun Oil of Pena. (Saudis) S. Sybron Corp., Tsnatex Cbealcals Olv. Beftoed Steheevl Producers - 197b Creeasboro, MC Old Irldse, KJ Tears 1972 - Preseat Bay City* Ml Cedar Grove, NJ Aaalstoa, AL Voustoa, TX Corpse Cbrlati, TX Lyndfuirst, Mi 1933 - Present 1974 - Present 1933 - Present 1974 - Present 1970 - Present 1971 - Present Eat lasted Capacity (a 10* lb/yr) s <l 10 - 20 1-4 43 13 - 20 10 - 20 10 Biobanrl Paad Stock Producers - Caaasrclally Available Product 1. Coastal States Gas Producing Co. 2. Cooden Oil sad Chealcal Co. 3. Bow Chealcal Co. 4. Coif Oil Corp. Corpus Christ!, TX Big Spring, TX Bay City, Ml Philadelphia, PA HONS 053281 Figure I1I-1- Annual Biphenyl Production (SRC Estlnatlons) KOB) capacity. Of couraa, that figure is somewhat higher currently, depending upon how auch of the chlorobenzene expansion has been completed. . The production capacity of Monsanto's facility for diphenyl oxide is considered proprietary and has, therefore, not bean obtained. Monsanto produces diphenyl oxide by reacting phenol with catalyse. ' B. Importation Prior to 1974, there la no record in the literature of any importation of biphenyl or diphenyl oxide. However, the 1974 edition of "Imports of Benaenold Chemicals and Products"(UnitedStetes International Trade Commission) lists the following Imports; Biphenyl Phenyl Ether(Diphenyl Oxide) 10,758 pounds 43,201 pounds It should be noted that this reference source includes only surveys conducted at the major ports of entry. The above quantities are relatively lnslgnlfleant when compared to che total biphenyl and diphenyl oxide consumption in the United States| they represent less than IX of the yearly consumption. "Imports of Benzenoid Chemicals and Products" (1967-1974 editions) alto Hat 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 SBC. It Is possible that soma 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 hsat transfer fluids with compositions identical to Dowthemr' A. These heat transfer fluids, made overseas, are listed in Section V-B-l; quantities which may be Imported were not obtainable. 12 HONS 053283 C. Exportation No figures revealing export quantities of biphenyl or diphenyl oxide were avellable. After consulting with Industry spokesmen. It Is believed that smell quantities of biphenyl dye carriers ere 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 uees of biphenyl and 1973 uses of diphenyl oxide, respectively. Quantities used in each appli cation are included where known or estimated. 13 HONS 0S32B* f Figure 1II-2. Current Annual Biphenyl Use In the United States HONS 0 5 3 2 0 5 I Siiffao-ittiw dpnti d m SRC EitMiioM. Figure III-3. Dosesclc Diphenyl Oxide Use In 1975 HONS 0 5 3 2 8 6 IV. General Manufacturing and Production Technology A. Biphenyl 1. Thermal Dehydrogenation of Benzene Monsanto Industrials Chemicals Co., located In Anniston, Alabama, Is tha only current biphenyl producer to use the thermal dehydrogenation of benzene process. Both Monsanto and Dow began using the process In the 1930'a; 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: 700-850*C ^ (100%) (80-85%) (4.9%) (2.3%) Higher Polyphenyla (2%) + + Carbon Ac temperatures 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 reacdon, 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, 1963). 16 M0NS 053287 Figure IV-1 illustrates the typical process method of biphenyl production from thermal dehydrogenation of benzene. The raw material benzene end 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 ths temperature to 700-850*C, the time of exposure to the higher temperatures being on the order of one second. Under these conditions, a well-designed thermal reactor yields a condensed product containing 12-152 by weight of biphenyl, tarphenyl, and polyphenyls corresponding to approximately 202 by weight of the biphenyl, and the remainder aa unreacted benzene. The yield of biphenyl, based on benzene consumed, should be 80-852 of theory. The yield of biphenyl plus tarphenyl and other polyphenyls should be 90-952 of theory. At a 152 conversion per pats, the yield of biphenyl la 0.80 lb end that of terphenyl, etc. Is 0.12 lb par pound of consumed benzene. The mechanical loss of benzene is 0.02-0.04 lb par pound of consumed benzene (Foffanberger, 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 blphenyl-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' esmperature (Sanders and Slocombe, 1955; Poffenbargsr, 1950, 1965). Beat is generated in the thermal reactor by maans 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 MOMS 053288 HONS 0 5 3 2 6 9 Figure IV-1. Biphenyl From Thermal Dehydrogenation of Benzene m* V Metal surfaces Bads of Iron, nickel, or copper catalyze this carbon formation; therefore, metal surfaces are coeted with carbide, nitride, or oxide to reduce the cetalytlc 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: 30 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 captively used to produce PCB's (SRC estimation). Approxi mately 21 million pounds of biphenyl are required for the annual PCB production of 40 million pounds. Additionally, slightly less than one million pounds of biphenyl may be supplied by Monsanto for fungicidal purposes (SRC estimation). Monsanto has also just begun production of a heat transfer fluid called Therminol VP-1, which Is an eutectic mixture of 26.5Z biphenyl and 73.52 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 la probably twice that of current utilization. In 1970, Monsanto produced 83 million lbs of PCB's (Versar, 1976), which would require approximately 44 million pounds of biphenyl. After 1970, Monsanto restricted PCB aales to closed system uses; hence, production was cut approximately In half. 19 MONS 053290 Economic* Th* currant selling price of Monsanto's biphenyl Is $0.36/lb; however, most Is captively used In synthesis of PCB's. To estimate th* raw material coat to produce biphenyl vie thermal dehydrogenation of benzene, th* yields previously described have been assumed: 1 lb of consumed benzene yields 0.80 lb biphenyl and 0.12 lb terphanyl, 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 Th* only wastes from th* 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, th* 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 th* 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. *. 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 dlaadvantag* Is price, $0.36/lb compared to $0.16-$0.25/lb for dealkylatcd 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. 20 HONS 053291 2. By-Product From Dealkylation of Toluene The companies liatad below are all currently refining biphenyl from a by-product obtained when toluene la hydrodealkylated to benzene: Chemol, Inc. Dow Chemical Co. East Coast Chemical Co. Pilot Industries Sun Oil of Penn. Sybron Corp., Tanatex Chemical Dlv. Greensboro, NC Bay City, Ml 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), Cosdan 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 es the end product. The reeetlons 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) + h2 -------------> + CH^ (Doelp, 1966) The types of reactions contributing most to the nonselective product formation are the following: 21 HONS 053292 (2) 2 O) (biphenyl) + H, ---- > H^ \ (methylblpheny1) (4) (fluorene) b. Process Description Figure XV-2 Illustrates the general process for hydrodealkylatlng 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*F temperature. The hydrogen-to-toluene mole ratio Is 4-12. This stoichiometric excess of hydrogen helps to suppress the non-selectlve resctlons. Contact time In the reactor averages 20-80 seconds (Doelp, 1966). Catalysts are used In several processes. 22 MONS 053293 M6n RmJuito Furts or Cflkinf Figure IV-2 General Process for Hydrodealkylating Toluene to Benzene MOHS 0 5 3 2 9 4 Ths product from the reactor is condensed through heat ex changer* and the fuel gas (hydrogen and methane) la vented off for fuel uses. Bentena la separated from the non-selectlve products by fractional distillation. The yield of benzene from toluene la greater than 951 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; Derrlg, 1976; Doelp, 1966): Biphenyl Toluene Fluorenes Methyl biphenyls Anthracene - Pyrene Other Aromatic Hydrocarbons 501 15-201 10-151 51 31 31 91 The weight of the bottoms residue is approximately 21 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 95-971 purity is commonly obtained, which Is quite suitable for use In dye carriers. The residues from the biphenyl distillation are either added to fuels or used In coking operations. Bulk shipments of biphenyl to customers Is done via railway or truck tankers In a molten state (biphenyl melts at 69*C). 24 HONS 053295 c. Production Volumes Estimated capacities of the biphenyl refiners are listed in Table I1I-1, p.10. Roughly 60 million pounds, of refined biphenyl are currently being obtained from dealkylaced 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 dealkylatlng toluene can be appreciated. Some of the dealkylation units idled or cut-back in 1970 are now running nearer to capacity and new units are being installed. This Increase in dealkylation of toluene has resulted in a biphenyl by-product from which profits can be realized. Therefore, the biphenyl by-product has found use as fuel additlvas or as a refined product. The biphenyl by-product can be sold to biphenyl refiners for $0.35 per gallon of which approximately 50Z by weight is biphenyl (Derrlg, 1976). The biphenyl content of the by-product would, therefore, have a selling value of about $0.085/lb. The refined biphenyl can be sold to dye carrier manufacturers 25 MONS 053296 for $0.16-$0.23/lb., depending upon the purity. This would indlcete that re fined biphenyl obtained from dealkylation of toluene accounta for annual aalaa of $10-13 Billion. The quoted prices for this biphenyl in 1973 was $0.03-$0.07 lass 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 VIX-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 0.3 - 2.0 atm. pressure and 600-800*7. Of the benzene which reacts, 43Z yields phenol, 25* yields biphenyl, and the rest yields gaseous products (Porter, 1946). .The biphenyl is obtained by distillation. This process for the production of phenol is so minor a commercial method that it receives virtually no mention in the available literature. B. Diphenyl Oxide 1. By-Product From Chlorobenzene-Phenol Process a. Manufacture 26 HONS 053297 The Dow Chemical Co., plane site located In Midland, MI, produces diphenyl oxide aa a by-product from their phenol production via chloro benzene. Thle 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 10-15X 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 reectlon. 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 Che 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 (hydroxydlphenyl), and a catalyst (copper salts) (Faith at al., 1965). The reactants are then pumped through a nickel-lined, counter-current heat exchanger which raises the reactants' temperature to 275-300'C. The flow Is Injected Into a continuous-flow tubular reactor of 4000-5000 pel pressure and heated to 400*C. Contact time is usually 15-20 minutes at the 400*C temperature. The selective and non-selectlve reactions which occur In the reactor are the following: 27 MONS 053298 HONS 053299 Figure IV-3. Diphenyl Oxide from Chlorobenzene - Phenol Process Whan leaving che reactor, che reaction produces are passed through the heat exchanger onca again, to warm the Incoming reactants and to cool the reaction produces. The reaction produces 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 of diphenyl oxide and un- rcacted monochlorobenzene. The oil Is distilled to produce diphenyl oxide and the monochlorobenzene Is recycled to the reactor. The aqueous sodium phenoxlde layer Is passad to a neutralizer and treated with hydrochloric acid prepared from the HC1 gas by-product from the chlorinator. The neutralization reaction which produces phenol Is: . The product from the neutralizer is density separated to produce an aqueous NaCl layer and a phenol-rich layer. The phenol layer is distilled to obtain USP grade phenol. The NaCl layer Is extracted with benzene Co remove phenol content, and the NaCl solution Is returned to the electrolytic call. The phenol-benzene mixture Is distilled to obtain hlgh-purity phenol (Poffenberger, 1968; Faith at_al., 196S). The overall yield of phenol based on monochlorobenzene is 90-9SX by weight. Conversion per pasa through the reactor is 35-451 (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 la not Introduced into the high pressure pump to limit the non-salectlve reaction. Small amounts of ortho and para-phenvlohenol are formed as by-produecs during the neutralization and are separated from the phenol-rich layer during 29 MQNS 053300 distillation. Ortho-phenylphenol Is used as a dye carrier and as an active Ingredient In Lyaoi cleaner. The diphenyl oxide obtained from the Initial distillation of the oil-layer from the reactor is a "technical" grade diphenyl oxide. This technical grade can be purified to 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 Ho. 110-288-72). The additional 10Z 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 M0NS 053301 c. Shipping The technical end 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 colls 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 Is captlvely used to make Dowtherm A, DowfasP surfactants, butyl- chlorodlphenyl oxide, and decabromodlphenyl 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. 31 HONS 053302 This would indicate that diphenyl oxide will be prepared directly Iron chloro benzene and caustic soda. Dow holds tha original patent describing diphenyl oxide manufacture by this direct route (Hale, 1930). The chemistry of this reaction is: + 2NaOH + 2NaCl + HjO The current selling prices of chlorobanzsna and sodium hydroxide are $0.29/lb and $0.125/lb, respectively (Chemical Marketing Reporter). At a 90Z yield, one pound of formed diphenyl oxlda would consume $0.49 of raw materials. Since Dow makes tha chlorobenzene and NaOH, cost would ba considerably less than the sailing price. e, Environmental Management All diphenyl oxlde-phenollc product losses in the sewer are treated by tha 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 dlphanyl oxide at their Chocolate Bayou complex in Alvin, Texas in late 1975. Monsanto did not ravesl any datalls concerning their process except that the overall process involves reacting phenol vlth catalysts. The original description of producing dlphanyl oxide by catalyzing phenol is contained In a German patent (SchOllkopf, 1929). The patent describes phenol as being heated to 350*C in an autoclave with activated fullar's earth to 32 HONS 053303 give a 15X yield of diphenyl oxide. The procese preeently being ueed by Monaento nay be very' elnllar. Undoubtedly, superior catalysts and techniques have been developed to Increase reaction yields and rates vhich make the process economi cal. A Simple flow-diagram Illustrating this process would be: The selective chemical reaction should be: 2C6HS0H -> <c6h3)2o + h20 The diphenyl oxide grade produced by Monsanto Is 99.91 pure (Monsanto Technical Sheet IC/PP-49). a. Production Volumes Monsanto has been producing diphenyl oxide only since late 33 MOMS 053304 1975. Capacity or production volumes at the facility are not available aa the Information la conaldered proprietary. The large percentage of production vlll be uaed captlvely to make Thermlnol VP-1 (Pane, 1976), vhich la a heat tranafar fluid of Identical compoeltion to DovthertsA. The unit which producee Thermlnol VP-1 waa placed on-atream In early 1976 (Garxa, 1976). b. Environmental Management Waatea generated by Monaento'a diphenyl oxide proceaa are treated by the company'a own waate treatment facility (Pane, 1976). The water by-product produced during the proceaa will be Included In the waatea treated by Monaanto. The efficiency of the treatment facility upon the diphenyl oxide waatea la unknown. c. Economica The current celling prlcea of Monaanto'a diphenyl oxide la 60.80/lb In bulk ahlpmenta. Aaaume 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 conaumea $0,332 worth of phenol. 34 HONS 053305 V. Da* and Dee Procaaa Technology ' A. Biphenyl 1. 'Dye Carrier Ac the preaent time, nearly 60Z of the refined biphenyl produced In Cha U.S. la conaunad In dyeing aaalatanta called dye carrlera. Polyeacer flbera, such aa Dacronand Teryleni, are difficult to dye becauae the polymers themsslves are practically Inert to most forma of chemical attack. To enable dyes to peuetrete Into theee polyeeter fibers, the fibers must be treated with compound* which cause the fibers to swell. Theaa swelling compounds, or "carriers" as they are usually called, are aromatic chemicals that Improve the rate, color Intensity, and uniformity of dyeing when added to the dyebath. a. Manufacture The compenies who produce biphenyl are generally not the companies who formulate biphenyl into dye carrier products. Flgurs V-l lllustratss the overall schematic for tha virgin polyester flber-to-flnlshed garment process. The companies who produce the due carrier chemicals sell these chemi cals to textile chemical specialty firma. Twenty-four of the larger textile chemical specialty firma who sell biphenyl products are identified in Table V-l. The specialty firma receive the biphenyl chemical and add approximately 10X surfactants, or emulsifiers, which vlll render the waterinsoluble biphenyl emulslflable 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 ethylana oxide) ars tha most recommended types. However, a small amount of anionic emulsifier, such as sodium salts of naphthalene sulfonic add, formaldehyde condensation 35 MONS 053306 HONS 053307 Figure V-l. Polyester Fiber to Garment Flow Diagram (adapted from Otis, 1976, and various personal commlcatlons) Table V-l. Textile Chemical Specialty Firm* Who Make Biphenyl Dya Carrier* Firm 1. Arol Chemical Products Co. 2. Chemical Processing of Georgia 3. CNC Chemical Corp. 4. DePaul Chemical Co. 3. W.F. Fancourt 6. Finetax, Inc. 7. High Point Chemical Corp. 8. Independent Chemical Corp. 9. Jordan Chemical Co. 10. Lutex Chemical Corp. 11. Millaaster Oxyx, Refined Onyx Div. 12. Piedmont Chemical Ind. 13. Raytax Chemical Corp. 14. Richmond Oil, Soap & Chemical 15. SAB Chemicals Co. 16. Sandos Color & Chemical 17. A.E. Staley Mfg. Co. 18. Standard Chemical Products 19. Star Chemical Inc. 20. Sun Chemical Corp. 21. Tanatex Chemical Corp. 22. U.S. Oil Co. 23. Vlrkler Chemical Co. 24. WOoneocket Color & Chemical Site Basic 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 Arosolvs PC-7 Chemeryl COD Chemkar 209 Carrier A Depco Jat Carrier 296 Neoport BT Accelerit BP Carrier 100 Speco Carrier 23 Jocar L0C Super-Lok 845 Dacar BC High Point, NC Charlotte, NC Philadelphia, PA Jersey City, NJ Hanover, NJ Charlotte, NC Charlotte, NC Macon, GA New York, NY Lyndhurst, NJ East Providence, RI Charlotte, NC Woonsocket, RI Carrier L-300 Raycar IBP Rocar 4921-A Sabcar #235 Dllatln FBL Charlab LBPW Standye Car 180 Carrier P-40 Sunkem 660 Carolld AL Uscoslst 810 Vircocarrler B Woonco Dys Assist M 37 HONS 053308 product*, sodium lignin sulfonate., and sulfonated turkay oil and oehar alkylary1 aulfonataa, nay ba preaant to maintain proper dyeing lavala. The surfactants added by each individual apeclalty firm* are conaldered proprietary. The biphenyl dye carrier product nay alao contain other comon dye carrlera, especially methylblphenyl and chlorinated aolventa. Methylbiphenyl la a common by-product obtained at the aane time that biphenyl la re fined from dealkylated toluene bottoma and haa excellent dye carrier propertlea. The chlorinated aolventa may lnduda trlchlorobenzena and perchloroethylane. b. Dye Carrier Dae The textile chemical apeclalty flrma. In turn, aall the biphenyl dy* carrier product* to the fabric producer* and dyers, who are the one* who actually use the biphenyl product. As many as four to five hundred fabric dyer* exist In the U.S. who use biphenyl as a dya carrier (estimate by Industry spokesmen). Therefore, no effort was made to Identify all dyera. How ever, Industry spokesman indicated that three particular fabric producers repre sented a "slcable" portion of the polyester market. Those three are: (1) Burlington Industries (2) J.F. Stevens, Inc. (3) Decrlng-Mllllksn & 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 Rhodhlss, North Carolina and Roanoke, Virginia, In addition to 125 plants In tha U.S. Figure V-2 Illustrates the general unit operation* for dyeing and finishing polyester fabrics. The following stepwise procedure is recommended by Dow: 38 HONS 053309 BjfcMri Vapar RdM Biftmufi Vapar RiImh <o HONS 053310 Figure V-2. Dyeing and Finishing of Polyescer Fabrics Step #1 #2 #3 #4 #5 #6 #7 *8 #9 #10 111 #12 #13 #14 Water Heat to 120*F Polyester Fabric Sequeaterant Lubricant Anionic Dispersant Acetic Acid 70S Dye Carrier Disperse Dyestuffs . Heat to 260*F Run for 45 minutes Cool to 160*F Emulsified Perchloroethylene Wash 25,000 lbs 1,000 lbs 15 lbs 10 lbs 10 lbs 15 lbs 40 lbs 20 lba 25 lbs In general practice, the concentration of biphenyl verlee from 3-12Z of the weight 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 unpresaurized. 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 commonly use exhaust fans to vent biphenyl vapors to the outside atmosphere (the 0.2 ppm TLV Is being challenged, Section 1X-A). After the fabric has been washed. It will still contain small amounts of biphenyl. The vacuum drier effectively removes this biphenyl, and the vapors are sgsln vented to the outside. Small crystals of biphenyl mey 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 95X of tha biphenyl added as dye carrier Is re leased In the waste waters. Since the biphenyl Is In an emulsified state, It 40 MONS 053311 li too difficult to separate from the vatar; otharvlaa. It could bo rouaed. It appaara that moat of tha analler dyers ralaaaa thalr wastewaters dlractly to dty-county sawaga treatment facilltlaa whila savaral of tha largar milla hava on-aito traatmant (aaa Section XX-B-1). - d. Areaa of Uaa Nearly 22 aillllon pounda par yaar of blphanyl dye carriers are estlnatad to be used in dyeing of polyester carpets and draperies in Georgia (Varsar, 1976; Gaffney, 1976). This relatively small geographical area accommodates 250 to 300 allla representing 65Z of the world's carpat and rug narket. A similar quantity of biphenyl may wall be used in the fabric mills of North Carolina. The textile mills of Naw England also uaa sig nificant amounts of blphanyl. a. Economics ' Tha biphenyl producers are currently selling 50-55 million pounds of biphenyl to the textile chemical specialty firms at a $0.16-$0.22/lb price. This would indicate annual sales of $8-12 million. Tha textile chemical firms process the biphenyl into dya carrier products and sell tha products to tha fabric dyars at a price which is often 100% and mors, above tha price which they paid for the blphanyl. f. Alternative Products Tha following chemicals are all commercially used dya carriers which can ba used in place of biphenyl: 41 HONS 053312 (1) Butyl Benzoate - pOOCH2CH2CH2CH3 Sailing Price: Manufacturers: (2) o-Phenylphenol - $0.30/lb CPS Chemical Co., Cindet Cbanlcala, Finetax, Talaleol, Pflaar, Tanatax HO. Sailing Prlca: Manufacturer : (3) Trlchlorobensana - $1.50/lb Sow Chanleal Sailing.Prlca: Manufaeturara: (4) Dichlorobenzane - Cl $0.39/lb Dow Chanleal, Hookar, Standard Chlorlna FI Q1 Cl and Sailing Price: Manufaeturara: (3) Mathyl Salicylate - $0.31/lb Allied, Dow, ICC Induatrlas, Monsanto, PPG, Solvent Chanleal, Specialty Organics, Standard Chlorine POOCH, OH Selling Prlca: Manufaeturara: (6) Parehloroethylena - $1.00/lb Dow, Monsanto, Tenneco ci2c - cci2 Sailing Price: Manufaeturara: $0.165/lb Diamond Shamrock, Dow, DuPont, Ethyl Corp., Occidental, PPG, Stauffer, Vulcan 42 HONS 053313 (7) Methyl Naphthalenes - (CH3>x Manufacturer*: Crowley Hydrocarbon, Koppars, Marathon Oil g. Alternative Proceaae* A commercial waterlee* dyeing procesa for textiles ha* been t 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 D.S. (Anon., 1976 c). 2. Biphenyl Fungicide In Fruit Packaging Biphenyl has been used for nearly 30 years as a mild fungicide In citrus fruit wrappers and packaging. It would be impossible to ship citrus fruit across the U.S. or overseas in cartons, without a blue mold preventive like biphenyl. Years ago, "orange crates" of open lattice wood ware 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 43 HONS 053314 aathoda and to lnvaatlgata potantlal problems. Aa a reault of the work by IPC, biphenyl vea given a clean "bill--of-healthn by the FDA (Versarf 1976). . a. Manufacture The two American producera of biphenyl-impregnated papera are Hated below: (1) Crown Zellerbach Corp. San Franclaco, CA (2) Paper-Pale Corp. Orlando, FL Biphenyl tlaaue wrappers are still manufactured aa described In the original patent (Mispley and Barber, 1940). The biphenyl la bonded to the tlaaue 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 blphanyl par 1000 aq. ft. surface area (Cosner, 1976). Two pads are lnaerted into each container of fruit, one on top and one on bottom. The tlasues 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 mathod has ylalded inferior pro tection. The air permeability of corrugated boxes allows the biphenyl to dissipate (sublime). ' b. Production Volumes Approximately 600,000 to 800,000 pounds of biphenyl are consumed for fungicide papers per year at present (Cosner, 1976). Production Is seasonal, as would be expected from Its use In fruit protection. 44 MONS 053315 Tan years ago, at laaat aavaral million pound* of biphenyl wax* annually consumed for fungicidal puxpoaaa. However, Che advene of faster domeetlc transportation has lowered the need considerably. Today, a slseeble portion of the blphanyl papers produced ara used for ovaraaaa shipments. Domestic use la still Important, though, for long-haul shipment and doaed container storage. The amount of blphanyl used as a fungicide has bean de creasing In recant years. Future projections indicate, at bast, a stable market! however, slight decreases can be axpectad. c. Economics A high-grade purity biphenyl Is required for fungicidal uses. The currant 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 sals of blphanyl papers may amount to several million dollars par year. d. Environmental Management The nature of this biphenyl use Indicates that all of the biphenyl so used will eventually be exposed to the environment. A large per centage of biphenyl papers will eventually be disposed In solid trash disposals and/or Incinerated. e. Alternatives One coamercial alternative to biphenyl Is o-phenylphenol (g-hydroxyblphanyl). Ortho-phenvlphenol Is obtained as a by-product during Dow's phenol production from chlorobensena, the same process from which diphenyl oxide Is recovered. The o-phenylphenol is converted to the sodium salt which Is used to control molds end rota of citrus snd other fruits and for the 45 HONS 053316 disinfection of domestic and agricultural buildings, warahouaaa, and rafrigaratcd stores. Fries is slightly higher than biphenyl, but Its wider-range of protection Is a definite advantage. It is an active ingredient in certain Lyaof^cleaners. 3. Polychlorinated Biphenyl (PCB) PCB production and uaa has been thoroughly studied in a previous IPX 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 thalr 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 tha finished product. .Currently, Monsanto makes four different PCB products; Arodor 1221, 1242, 1016, and 1254. The dlfferenca is in chlorine content which ranges from 21Z in Arodor 1221 to 54X in Arodor 1254. b. Production Volumes Monsanto produced 40.4 million pounds of PCB's in 1974 and B.5 million pounds in tha 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 Currant sailing price of PCB products averages about $6 per gallon (11.36 lbs/gallon). Total annual sales would therefore be nearly $11.1 million. 46 MONS 053317 4. Alkylated Biphenyl e. Isopropylblphenyl . Commercially, leopropylblphenyl la the moat Important of the alkylated blphenyla. Tanatex Chemical Dlvlalon In Lyndhurat, HJ la the largest domestic producer of leopropylblphenyl (Cohen, 1976); Pilot Industries of Houston, TX also manufactures the chemical (Barrow, 1976). (1) Manufacture leopropylblphenyl is manufactured by a Freldel-Crafts reaction of biphenyl with propylene, the chemistry being: A1C1 Primarily, the monolaopropyl derivative la 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). HSarly all of the production la used In carbonless paper (Cohan, 1976). Manufacture started about 1971 and has accelerated to the present volume. In 1971, Monsanto terminated PCB's aalas for carbonless paper, and leopropylblphenyl has been used as a substitute for PCB In this application. Isopropylblphenyl may find future applications In hsat transfer and capacitor fluids. It nay be a component In Monsanto's proprietary dielectric fluid trade named "MCS-1238" (Versar, 1976). Monsanto has been testing "MCS-1238" as a possible PCB replacement. 47 HONS 053318 (ill) Economics . The currant selling price of lsopropylbiphenyl Is $0.56/lb, which would Indicate annual sales of $5.6 million to the carbonises paper Industry. b. Kathylblphenyl Mathylblphenyl la obtained as a by-product when toluene la hydrodealkylated to benzene. It commonly exists as an Impurity In the grade of biphenyl sold for dye carrier use; however, mathylblphenyl alone exhibits excellent dye carrier properties. Small quantities of mathylblphenyl ere Iso lated end sold by Pilot Industries of Houston, IX, but commercial-scale pro duction has yet to occur (Barrow, 1976). Since mathylblphenyl has such good dye carrier properties, It la conceivable that efforts to synthesize It may have commercial Importance In future years. c. Ethyl- and Butylblphanyl Ethyl- and butylblphanyl are produced by Freldel-Crafts reaction of blphanyl with ethylene and butylene, respectively. Pilot Industries produces small quantities for applications In heat transfer, but they are not coemerclally Important yet (Barrows, 1976).' 5. Eutectic Heat Transfer Fluid See Section V-B-l. 6. Polybromlnated Biphenyl (PBB) PBB production and use has been thoroughly studied In a previous EPA report (Mumma and Wallace, 1975), so only brief review will be given here. 48 MONS 053319 a. Manufacture Commercial production of PBB'e vea terminated In 1974, the coomerclal producer* being Michigan Chemical Corp. of St. Louis, MI, and White Chemical Corp. of Bayonne, NJ. The termination vaa precipitated when. In 1973, PBB'b ware Inadvertantly fad to dairy cowa with harmful affacta. The manufacturing proceaa of FBB'a la considered proprietary, but patent literature (Moore et al.. 1974; Mitchell, 1973) describee production via bromlnatlon of biphenyl by bromine chloride or liquid bromine. FBB'a ware used exclusively aa flame retardants for plastics. b. Production Volumes Michigan Chemical produced a total of about 11.2 million pounds of FBB's during the period of 1970 to 1975, and White Chemical produced about 100,000 pounds of FBB's from 1970 to 1973 (termination data for White Chemical). c. Economics The 1975 selling price of the major FBB product (Flremaster BP-6) was $0.75/lb. Combining this with the largest production year, 1974 (4.8 million pounds), raveals 1974 sales of nearly $3.6 million. d. Alternative* On* viable alternative la decabromodlphenyl oxide (see Section V-B-6 for this discussion). B. Diphenyl Oxide 1. Eutectic Beat Transfer Fluid The major current use of diphenyl oxide is for manufacture of a 49 MONS 053320 utaetie haat transfer mixture composed of 73.51 diphenyl oxide and 26.SZ biphanyl. Thia mixture has been markated by Dow Chemical Co. as Dowthani A since the eerly 1930's. Dow produces Dowthen^A In Midland, Michigan. Mon santo Industrial Chemicals, In Alvin, Texas, began producing an idantlcal mix ture called Thanalnol TP-1 In early 1976. Dow and Monsanto are tha only ' domestic producers; however, all of the known world producers of this particular mixture are listed below; Producer Country Product Dow Chemical Monsanto Imperial Chemical Mlppon Steal Chemical Bayar Progll USA USA Great Britain Japan Hast Germany Prance Dowthern* A Therminol VP-1 Thermex Therm S-300 Dlphyl Gliotherm The biphenyl-diphenyl oxide eutectic mixture is used as both a heating and cooling heat tranafar media. It Is used In liquid phase at tam- peratures from 60*F to 750*F, and In the vapor phase at temperatures from 495*? to 750*F. It is non-corrosive, so carbon steel Is usually selected for equipment In which It will be used. Physical propartles of tha mixture are listed on the Material Safety Data Sheets for DovtherJ 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 the liquid and do not affect operation as long as their concen tration doas not exceed 10Z. At 750*F, tha decomposition rate varies between 0.8Z and 3.0Z per 100 hours (Oanslger, 1966). Dow has an analysis and purification service and can reprocess deteriorated Dowtherm If polymerisation Is not too advanced. Charles E. Sech - Consulting Associates (In Michigan) sells a purification 50 HONS 053321 system to individual users of Dowtherm(B0) A, which la nothing nora than a singleplata dlatlllatlon column. The impurities from the distillation are usually added to fual'olls because their heating value, as well as that of Dowtherm, is qulta high (Sech, 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 Dowtherm0A, were made In the U.S. from 1955-1965 alone (Danzlger, 1966). It la 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 Dovtharii A. This would correspond to s 1975 production of slightly less than 5.5 million pounds of Dowtherm. Biphenyl use accounted for roughly 1.5 million pounds. Dow la currently expanding their facilities which produce diphenyl oxide and Dowtheri 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 overeeas, 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 MQNS 053322 Economics Ttis following sailing prices ara for DowtheriJ A: ' 5 gallon pall 55 gallon drum 4000 gallon tankars $0.84/lb $0.79/lb $0.66/lb Ths 1975 salas of Dowtherif A would roughly ba $4 million considering a 5.5 million pound production. d. Environmental Management Occupational axposuta to vapors of the eutectic mixture have bean regulated by OSHA atandards. Manufacture involves only mixing of liquid diphenyl oxide and biphenyl. It seems unlikely that any quantity would be released to the environment during manufacture except' by accidental sp'lll or leak. Dow's "Material Safety Data Sheet" for DowthenP A calls for Incineration of spilled materials (see Appendix B). Users of the mixture can have contaminated quantities re processed by Dow or use old quantities as a burning fuel. e. Use Alternatives One of the major alternatives to Dowtherm A Is petroleum- derived oils. Numerous oils are Included In thia category and collectively, these petroleum-derived oils are probably the most widely used heat transfer media at temperature levels above that of moderate-presaura steam (up to 550*F). Theaa oils are obtained as hlgh-bolllng fractions from petroleum. Several com mercial products are listed below: (1) Moblltherm 600 (2) Rumble-Therm 500 (3) Security 205 (4) Tellus 7Z Mobil Oil Co. Exxon Corp. Gulf Oil Corp. Shell Oil Co. 52 MONS 053323 la useable at tamparacuraa up Co 750*7, while Cha petroleum olla hava a lisle favor of the petroleum oils, and the extra cost of heat-trsclng pipes as Dovtherm freezes at 34*7. 2. DowfaP Dovfax*' 1* th ertdenaae for dodocyldlphonyl oxldo dlsulfonlc add, dlsodium salt manufactured by Dow Chemical In Midland, Michigan. DovfaJ surfactants are anionic wetting agents of the sulfonete type which are used In latex production, agricultural formulations, cleaning compounds, dye aeslsts, detergents, and In textile fiber production (Dow Products & Services Catalog). a. Manufacture A flow diagram Illustrating the manufacture of Dovf*j$ is shown in Plgure 7-3. Diphenyl oxide Is alkylated with either n-dodecyl chloride or 1-dodecane to dodecyldiphenyl oxide. The dodacyldlphenyl oxide Is dissolved In an organic solvent, such as hexane or oc.tane, at 8-18*C, and chlorosulfonic acid la then stirred Into the solution. The chemical reaction Is: -2HC1> 53 HONS 053324 in HONS 053325 1 >^<hVilWnd 1M41 i Figure V-3 Process Manufacture of Dovfax Solutions Tha solution la allowed to danslty aaparata and tha upper layar of organic solvant la dacantad. An aquaoua HaOH solution la now addad to tha bottom layar to nautrallas tha dodacyldlphenyl oxide diaulfonlc acid to the dlaodlum salt. Evap oration of tha solution to dryness gives a buff to white powder of dodacyldlphenyl oxide diaulfonlc add, dlaodlum aalt (Valenta and Stelnhauer, 19(4). Three Dowfai products are available from Dow: (1) DovfaxK 2A1 Surfactant Solution (2) DowfaxS? 3B2 Solution (3) Dowfaxr 2A0 (1) and (2) above are solutions containing 45Z active In gredient of dodacyldlphenyl oxide diaulfonlc add, dlaodlum salt, while (3) la tha acid form (not neutralised with NaOH). b. Production Volumes ' Production volumes vers not available from Dow; however, SRC estimates that Dow captively consumes about 0.75 million pounds annually of diphenyl oxide to synthesis Dovfai^surfactants. This vould mean an annual production of roughly 2.3 million pounds of DowfaaJ surfactants. Dow Introduced this product in the early 1960's. Projections for future growth were not obtained. c. Economics The current selling price of DovfaaJ 2A1 Surfactant Solution la $0.47/lb; therafors, the selling price of the dry powder dodecyldlphenyl oxide diaulfonlc add, dlaodlum aalt Is approximately $1.00/lb. This would indicate annual salaa of $2.3 million. d. Environmental Management It is doubtful If significant quantities of diphenyl oxide are released to the environment via manufacture of Dowfaa^. Sewer wastes 55 MOWS 053326 containing.diphenyl oxide ere treated by Dow' Michigan Divlelon Haete Treatment Plant (Otle, 1976). Treatment efficiency of the plant with reepaet to diphenyl oxide le unknown. . e. Alternative Produeta There are numerous eurfactanta commercially available on the American market. Many are organic derivatives of high molecular weight alkyl aulfatea or eulfonatea. Dowfai can be Included In the group of surface- active agents having astar or ether linkages. Other chemicals Included In this group are: (1) Sulfosucclnlc add esters (2) Coconut oil adds, 2-sulfoethyl eater, sodium salt (3)- Dodacyl aulfoacetate, sodium salt (4) Herring oil, aulfonated, sodium salt (5) Isooctylphenol, ethoxylated and sulfonated, sodium salt (6) n-Octylphanol, ethoxylated and aulfonated, sodium salt Selling prices on the above vary from $0.53 - $1.00/lb. 3. Diphenyl Oxide Dye Carriers Diphenyl oxide dya carriera 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 csrrlers (see Section V-A-l). XAS-1075L assays 90% diphenyl oxide and the remainder as methylnaphthalenes and naphthalenes (Dow Form Ho. 110-288 72). Diphenyl oxide is used the same as biphenyl as a dya carrlar. The textile chemical specialty firm which apparently hendles most of the diphenyl oxide dye carriers la Chemical Processing of Georgia In Dalton, Georgia. a. Volume of Uee Company spokesman for Chemical Processing of Georgia estimate 56 HONS 053327 diphenyl oxldn dye carrier use at much lata than one alllion par year currently. Mo great lncraaaa la expected in tha near future. SRC aatlaatas the current use of diphenyl oxide In dye carriers at roughly 0.25 million pounds par year. . b. Economics Current selling price for Dow "Industrial grads diphenyl oxide la $0.52/lb, up from $0.32/lb In 1973. After the chemical specialty flras add emulsifiers and proprietary Ingredients, tha cost to the textile dyers aay ha 100-2002 greater. This would sake the total sales of diphenyl oxide dye carriers In the neighborhood of $0.35 million par year. c. Environmental Management Same as for biphenyl. See Section V-A-l. . d. Alternative Products - Same as for blphanyl. See Section V-A-l. 4. Perfumes and Soaps Due to Its characteristic geranium odor, diphenyl oxide has been used In perfume formulations since the early 1930's. a. Manufacture The major manufacturers of diphenyl oxide perfumes are: (1) Glvaudan Corp. (2) Floraaynth, Inc. Clifton, NY Mew York, MY Actual compositions of perfume products are considered proprietary; howavar, the concentration of diphenyl oxide In the final producta la listed below (Opdyke, 1974): 57 MOMS 053328 Soap. Usual 0.05 Maximum 0.20 Concentration* in X Detergent Creams. Lotions Perfume 0.005 0.05 0.15 0.03 0.10 0.40. The largest user of diphenyl oxide in soaps and detergents has been suggested to .be Proctor & Gamble Company, corporate offices in Cln- cinnsti, Ohio. Before compounding the "perfume" grade diphenyl oxide into perfumes, it is 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 0.8. amounts to about 100,000 lbs/yr (Opdyke, 1974). This figure is down from 200,000 lbs/yr in 1965 (Cantrlll, 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 war* imported for thle use (United States International Trade Commission, "Imports of Bensenoid.Chemicals and Products 1974"). Before 1974, there is no record of any imports. c. Economies The current sailing price for "perfume" grade diphenyl oxide is $0.8S/lb, which le up from $0.51/lb in 1965. After formulation into fragrance products, the price will be many times greater. 58 HONS 053329 d. Environmental Management The nature of fragrance product! Indicates that all 100,000 lbs/yr uae will be exposed to man and the environment. It should be noted that biological data (Opdyke, 1974) suggest no adverse effects due to human use of di phenyl oxide In perfumes and soaps. e. Alternative Products Perfume formulators (Mahinlta, 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 compered to alternatives. 5. Butylated Monochlorodlphenyl Oxide Butylated monochlorodlphenyl oxide has recently been marketed by Dow Chemical in Midland, Michigan, under the tradensme "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-Edlson 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 la probably accomplished by monochlorination of diphenyl oxide followed by butylation. Monochlorination of diphenyl oxide Is described in a Dow patent (Bennia, 1974). According to the patent, diphenyl oxide, con taining 0.005 moles of 981 H^SO^ as catalyst, Is chlorinated to yield the following products: 6Z o-chlorodlphenyl oxide, 671 j>-chlorodiphenyl oxide, 101 dlchlorodlphenyl oxide, and 151 unreacted diphenyl oxide. 59 HONS 053330 The monochlorodiphenyl oxide can be butyleted by FreldelCrafts reaction (AlCl^ catalyst) with butene or butyl chloride. The general formula for XFS-4169L la (Branaon. 1975): > Ci ^Vn b. Production Tolunea " .M.3 ' Until 1976, only pllot-quantltlea of XFS-4169L wera being produced, but Dow aeaured the electrical Industry that It would have a capacity rata of one million pounde per year during the first quarter of 1976 (Branson, 1975). Dow now saya (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 butylated 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. Environmentel Management Sewar wastes containing diphenyl oxide are treated by Dow Michigan Division Wasta Treatment Plant (Otis, 1976); however, significant quantities of diphenyl oxide should not be released from the XPS-4169L process as unreacted diphenyl oxide can be recycled for chlorination. Specific environ' mental management techniques concerning the ehlorodlphenyl 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 expansive for 55 gallon drums, most 60 HONS 053331 expensive for 5 gallon pail*, Large aeala production flguraa to lover tha calling prlca to $12 par gallon ($1.40/lb). If S million pounds par year ara sold, this would raprasant salas of $7 million. a. Alternatives Butylated monochlorodlphanyl oxide was dsvaloped to ba an altarnatlva to the toxic and persistent PCB's, which sell for $6-$7 per gallon. However, because of environmental contamination resulting from thalr use, PCB'a will no longer ba produced In the future. Many corporations ara presently In volved In research and tasting of new compounds to replace PCB's. Some of the primary possibilities have been summarized In a previous EPA - Office of Toxic Subetances Report (Terser, 1976); they are listed belowt (1) Dioctyl Phthalate (2) Dllsononyl Phthalate (3) Isopropyl Dlchlorobiphenyl (4) Silicones (5) Diary1 Sulfone 6. Deeabromodlphenyl Oxide Decabromodiphenyl oxide (deeabromodlphenyl ether, decabromo- phanoxylbenzane) Is used as a fleam retardant In certain types of flame re sistant polystyrene, polypropylene, polybutylene, terephthalate, ABS resins, and other plastic materials (Lavek and Williams, 1975). a. Manufacture The four domestic producers of deeabromodlphenyl oxide are: Producer Site Tradename (1) Dow Chemical Co. (2) Graat Lakes Chemical Corp. (3) Hexeel Corp., Pina Organics, subsld. (4) White Chemical Corp. Midland, MI El Dorado, AR Sayrevllle, NJ Bayonne, NJ ! . FR-300-BA Great Lakes DE-83 -- -- 61 MONS 053332 Details concerning actual manufacturing method* are con- idared proprietary and are not available. A survey of patent literature re vealed no information concerning decabromodiphenyl oxide production. A Dow patent (Moore et. el., 1974) describe* bromination of biphenyl vlth bromine chloride. Dacabromobiphanyl is obtained by adding a stoichiometric excess of bromine chloride, under pressure In a closed vessel, to biphenyl In the presence of an Al&3 catalyst. Decabromodiphenyl oxide could concelveably 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 ars presently consumed per year to produce decabromodiphenyl oxide. This would correspond to an annual decabromodiphenyl oxide production of 2.8 million pound*. Commerclsl production of decabromodiphenyl oxide began in 1972. Company spokesmen are projecting increases in production during the next several years; an exact percentage was not availsbls. . c. Economics Decabromodiphenyl oxide (Dow's FR-300-BA) Is currently selling for $1.80/lb, which 1* up from $1.08/lb In 1973. Annual sales could smount to nearly $5 million. d. Environmental Managamant Hastes from decabromodiphenyl oxide production units should contain only small amounts of diphenyl oxide. The total diphenyl oxide which may be exposed by these units la probably insignificant when compared to other diphenyl oxide uses. Effectiveness of diphenyl oxide wests treatment Is dis cussed in Section IX-B-2. 62 HONS 053333 Alternative* Several years ago, polybrominated biphenyls (PBB's) ware an Important commercial flam* retardant. Dacabronodlphenyl oxide waa davalopad to conpata with PBB's.for various applications, but decabromodlphanyl 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 (Mumma and Wallace, 1975). One of the new flame retardants, with applications similar to decabromodlphanyl oxide. Is Cltrex BC-26, sold by Cities Service Company In Rockville, Conn. (Mumma and Wallace, 1973). Cltrex BC-26 Is a halogenated organic containing 29Z bromine and 40X chlorine with a price comparable to decabromodlphanyl oxide. Other comparable flame retardants Include (Tabor, 19'73): (1) Tetrabromoblsphenol-A (2) Pentabromochlorocyclohexane (3) Dibromoneopentyl Glycol (4) Trls (2,3-dlbromopropyl)phosphate $0.57/lb $1.10/lb $0.55/lb $0.65/lb 7. Minor Commercial Uses of Diphenyl Oxide a. Chloromethyldlphenyl Oxida Chloromethyldlphenyl oxide and dl(chloromethyl)dlphenyl oxide are produced In small quantities snd are used to make thermosetting foams and resins. The production technology was developsd by Dow Chemical (Doedens and Rosenbrock, 1961), but the only U.S. producer of chloromethyl dlphenyl oxide and dl(chloromathyl)dlphanyl oxide Is Stauffer Chemical In Edison, NJ (Insera, 1976). Stauffer has produced these chemicals since 1971. 63 MONS 053334 Diphenyl oxide reacts with formaldehyde and hydrochloric add to produce a variety of chloromethylated compounds. The degree of chlor ination determines the distribution of laomara. Chloromethylatlon to 25.21 chlorine, for example, would produce the following Isomer distribution (Dow Form Ho. 110-288-72)1 HCHO + UC1------------ ^ (0.251) + <0>^ci (2.352) Pure materials csn be recovered by use of solvent extraction and distillation (Doedens and Cordts, 1961). The total combined production of chloromethyl and dl(chloromethyl)dlphenyl 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. Hethoxymethyldiphenyl Oxide Methoxymathyldlphanyl oxide Is also produced by Stauffer Chemical In Edison, NJ. Production volumes are less than those for chloromethyldiphenyl oxide (Insera, 1976). 64 HONS 053335  Diphenyl oxide end formaldehyde ere ueed ee the ecertlng materlala to produce nethoxynethyldlphenyl oxide. Verloue leoaere ere formed, ee ahown for chloronethyldlphenyl oxide. The mono-para and mono-ortho leomers shown below make-up the bulk of production. CHjOCHj Methoxymethyldlphenyl oxide la ueed to manufacture Weetlnghouee'e Doryl reelne (Cogley, 1976). Doryl realna are ueed In high temperature vamiah appllcatlone for electrical lneulatore. c. Peatlddee Diphenyl oxide haa been Identified In a peatlcide plant'a raw effluent (Webb at al., 1973) via gaa chromatography - mate spectrometry. A eurvay of patent literature revealed that Clba-Ceigy Corporation holda patanta deacrlblng lnaectldde production from diphenyl oxide. However, the Clba-Galgy peatlcide production facilities (In McIntosh, Alabama) failed to reapond to lnqulrlea aaklng about diphenyl oxide uae, perhapa due to proprietary conalderatlona. The following aynthesla la an example of diphenyl oxide uae in Insecticides detailed in a Clba-Ceigy patent (Franks and Traber, 1972): n CH> "* (2) :h2ci + CHjCQCHjCOjCjHj --iL-caHtoa--^ HjCHjCOCHj 65 HONS 053336 (3) ch2ch2coch3 + (CH30)2P(0)CH2C02CH3 h-cchc ^ [jCHjCCHj - CHCOjCHj Ciba-Celgy ha* marketed tha following paatleldea with a dlphanyl oxlda moiety: (Chloroxuron) (Fluorodifan) It la doubtfull that tha abova pastlddas ara aynthaalzed with dlphanyl oxlda aa a raw natarlal, but diphenyl oxlda nay ba genaratad In by-product anounta large anough to detect via gaa chromatograph - aasa apectrometer. This may account for tha Identification of dlphanyl oxide In pesticide effluents, but this Is only speculation. Ha have not been able to determine If diphenyl oxlda la definitely used as a raw material for pesticide production, and this possibility still exists. HONS 053337 66 VI. Soured of Biphenyl and Diphenyl Oxide Occurring in Nature A. Biphenyl 1. 'Petroleum Aromatic compounda of almoat every known type have bean found In petroleum. Biphenyl and lta three mono-methyl derlvatlvea have been Identi fied and leolated from crude petroleum (Hunt and O'Neal, 1967). Biphenyl, which bolle at 255*C, wee Isolated In the dinuclear aromatic portion of petroleum boiling la the range 255* to 275*C. Heir end Mayer (1964) have estimated that biphenyl makes up 0.008X by volume of crude 9 petroleum. In 1973, 3.1 x 10 barrels of crude oil were produced In the United States (SRI, 1975 b). This translates to approximately 1.3 x 10*1 gallons of crude oil of which an estimated 0.008Z by volume was biphenyl. Converting eo weight measurement, an estimated 80 million pounds of biphenyl was present ae a naturally occurring constituent of the petroleum domestically produced In 1973. In addition, nearly 5 x 101<J 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 beesuse It la not reflnedi 0.008X is much too small to recover. It has been estimated that the total oil Influx Into the ocean from routina 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 end domestic 67 HONS 053338 wags 1* between 11 - 12,000 Billion pounds pr ysr (Bluasr t al., 1971). Assuming 0.008Z by volums blphsnyl eoncsnt, slapls calculation suggssts that approximately 1,000 pounds of blphsnyl la annually ralaasad into tha envlron- aant with splllad dll. Kathylblpbanyls aaount to an satlmatad volums Z, rslatlvs to cruda patrolaua, of approxlmataly 0.0404Z (Hair and Kayar, 1964; Yaw and Mair, 1966). This amounts to flva tlmas tha voluaa of plain blphanyl. 2. Foods Stavana st_ si. (1966) ldsntifisd blphanyl In tha volatlla con- tltuanta of gtapas by usa of a capillary gas chromatograph attached to a Baas pactronatar. Blphanyl had pravlously been ldsntifisd In orange volatiles by gchultt at al. (1964); however, Schultx at al. attributed tha biphenyl's presence to packaging materials which were Impregnated with funglatat biphenyl. The grapes uaad by Stavana in his Investigation wars handled In bulk, and funglatat blphanyl could not have coma from packaging. It would seen possible, therefore, that biphenyl say be a naturally occurring constituent of grape volatiles. Klnlln et_al. (1972) Identified biphenyl In the volatile consti tuents of roaatad filbert nuts while Walradt at al. (1971) found blphanyl in peanut volatiles. Stoll at al. (1967) Identified biphenyl aa one of 202 consti tuents praaant in coffee concentrate. The amounts of biphenyl which aay occur In foods Is very small and It Is very doubtful if any significant quantities of biphenyl are exposed to tha anvlronBent via this route. B. Diphenyl Oxide 1. Plants HONS OS3339 In addition to biphenyl, Stevens at al. (1966) Identified dlpbsnyl 68 oxide In the volatile constltuanta of grapes. Klmland et_ al. (1972) Identified diphenyl oxide es one of many compounde present In Greek tobacco. ' The amounts of diphenyl oxide which may be released to the environ ment from plants Is probably very small. HONS 0533*0 69 VII. Generation of Biphenyl and Diphenyl Oxide By-Producta . ' Section IV (General Manufacturing and Production Technology) dlacuaaed the procaaaaa by which biphenyl and diphenyl oxide by-producta ara obtained and refined comerclally. Thia aectlon examinee biphenyl and dlphanyl oxide gener ation in proceaaea In which they are not refined or Intended to be refined. A. Biphenyl 1. Dealkylation of Toluene The comercial producera of refined biphenyl, from the dealkylatad toluene by-product, are Identified In Section III (Production) and Section IV-A-1, along with the petrochemical company aourcea of the by-product. The companlea Hated below alao produce benzene by dealkylatlng toluene; however, they do not refine the biphenyl etream or aell It to refInert. Company* Site 1. Aahland Oil Co. 2. Crown Central Petroleum Corp 3. Enjay Chemical Co. (Exxon) A. Leonard, Inc. 5. Monsanto (. Shell Oil Co. 7. Signal Oil A Gaa Co. 8. South Hampton Co. 9. Sunray-DX Cutlattaburg, KY Houston, IX Baytown, TX Mount Pleasant, MI Alvin, TX Odessa, TX Houston, IX Stllabea, IX Tulsa, OK The biphenyl streema generated by the above companies are added to fuels, usually fuel oils. The amount of biphenyl added to fuels via toluene dealkylation totala nearly 20-25 million pounds annually (SRC estimation). 2. Naphthalene Feedstocks Most of the nephthalene produced by petroleum operetors Is petroleum-derived. Naphthalene and/or naphthalene pracuraora occur In * Hahn, 1970, p. 411-412 70 MONS 0533A1 significant quantities In the following petroleum-derived straama (Srakine, 1970), and tha streams ara usas aa naphthalan* feedstock to product a purified naphtha lene. (1) Petroleum straans ara catalytlcally rafornad with tha Intention of producing high-octane aotor and aviation gaaollne, and It is possible to operate tha reformer to yield heavy "bottoms" that contain a high portion of aethylnaphthalanes and naphthalenes. Biphenyl Is found as a by-product In tha "bottoms". (2) Catalytic cracking is used to convert heavy petroleun fractions into lighter gasoline components, and one of the products of cracking contains naphthslane precursors. Biphenyl Is also formed during cracking. The typical composition of naphthalene feedstocks obtained from catalytic re formates and cracking ara (Doelp, 1966): Catalytic Reformates (Wt 2) Catalytic Cracking (Wt 1) biphenyl & aeenaphthenee alkylnaphthalenes alkylbentenes other aromatics 62 55% 20X 19Z 62 352 252 342 Naphthalene la obtained by hydrodealkylatlng the alkylnaphthalenes by tha same method as previously described for hydrodealkylatlng toluene to bentane (Section IT-A-2). Once again, the biphenyl by-product which la produced will probably be added to fuels. HONS 053342 71 3. Coal Tar Biphenyl waa firat identified In the hlgh-bolling fraetlona from coal tar distillation In 1875 by BUchner (Poffenberger, 1950). Coal tar aaounta to about 3X by weight of the coal which la processed. Along with many other hydrocarbons, blphanyl la part of the hlgh-bolllng fraetlona, dlatllllng in the range'250*-300*C; however, no chemlcala are aepareted comarclally from thla range. A fraction dlatllllng aalnly In the range 240*-270*C la eoployed at coking lnatallatlona aa waah oil for ecrubblng banzola from coal gaa, but moat of the olla In thla range are ueed In creoaote blenda (McNeil, 1969). Theae craoaote olla are uaed for coating wood aa a preaervatlve, uaually on railroad tlea and talephone polea. Due to the nature of thla uae, any biphenyl content of the creoaote oil will be expoeed to the environment from weathering effacta, which may leach or vaporize the biphenyl from the treated wood. Approximately 160 million gallone of creosote oil la 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 waa biphenyl. Applying Dolansky'a figures to the U.S. consumption of 160 million gallons of creoaote oil annually reveals that approximately 10 million pounds of biphenyl Is contained in this consumption. It la 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 waa produced domesti cally (Vnitad Statas 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 apperently ended up in fuels or coking operations, but this la not known for certainty. . HONS 053343 72 4. Automobile Exhaust ' It Is likely that biphenyl la a component of the exhaust gee emitted by en automobile engine; however, there is no proof In the literature to support this supposition. Schofield (1974) lists the various hydrocarbon components Identified In auto emissions, which he obtained from the General Motors Research Laboratories. The hydrocarbon list contains 1.11% by volume of unidentified aromatics, and It may be possible that biphenyl Is Included in these unidentified aromatics. Schofield does identify- the presence of ben- sene at a volume concentration of 2.13%, and at the elevated temperatures of en 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 estlmatsd to be 29,400 million pounds In 1971 (Council on Environmental Quality, 1973). If even a fraction of a percent of these emissions la biphenyl, sizeable quantities could be released directly to the envlromnnt. B. Diphenyl Oxide . 1. Caprolactam - Nylon Production Over 90% of the caprolactam produced in the U.S. Is used to manu facture Nylon 6. The following deta suggest that diphenyl oxide Is formed as a by-product during the production of caprolactum or Its precursors: (1) Phenyl ether (diphenyl oxide) haa been Identified In a settling pond of a nylon plant in concentrations of 0.03 mg/1 (Webb at el., 1973), and (2) Diphenyl oxide has been leolated as an Impurity in technical caprolactam In concentrations of 10 ppm (Kolar and Klacel, 1962). 73 MONS 053344 . Caprolactam la commercially synthesized from processes based on cyclohexanone. It la difficult to predict any dlphanyl oxlda by-product for mation during theaa procaaaaa. Bowavar, cyclohexanone la praparad, in ona cooMrdal process, by catalytic hydroganatlon of phenol. Phenol can be catalyzed to produce dlphanyl oxide, aa ahown by Monaanto's corniercial method. It may, tharefore, be possible that diphenyl oxide Is formed in small amounts during the manufacture of cyclohexanone via phenol. 2. Bituminous Coal Tar Dlphanyl oxide has been identified aa one of 133 Individual compounds present In bituminous coal tar (Karr at al., 1967). The fate of diphenyl oxide which may be present In coal tar Is unknown. 74 MONS 053345 VIII. Material Balance - Exposure to tbs Environment This section sttempts to define qusntltetively 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 (FCB's, alkylated biphenyls, Dovfa^, butylatad monochlorodlphenyl oxide, decabromodlphenyl oxide, chloromethyldlphenyl oxide, or pesticides). A. Biphenyl Table VIII-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 SX of the biphenyl Is exhausted as vspor, so the large bulk Is released In the waste waters. A discussion Involving the environmental fate of this water-released biphenyl is presented In Section IXB-l. The high estimate given In Table VIII-1 waa obtained by aasuming that only SOX of the released biphenyl was effectively treated or treated at all; the low eatlmate vaa obtained by asaumlng all of the biphenyl was treated with a 95X' efficiency. 2. Fungicide As described In Section V-A-2, the biphenyl used as fungldds Is bound by solvents to either tissue paper or to paper pads. The biphenyl will 75 HONS 053346 Table VIII-1. Estlaated Eoyimne1ntal Releasee of Biphenyl Use* Current Annual Use, Production or Content (X106 1&*) Quantities of Biphenyl (SRC Estlnatlons) Current Annual Environmental Release Estimates (X106 lbs) High Low Estimated 1966-1975 Use, Production, or Content (X1Q* lbs) Estimated 1966-1975 ' Environmental Release <X10` lbs) High Low Dye Carrier Fungicide DovtherJ A Creosote Oils Petroleum Naphthalene Feedstocks and Toluene Dealkylation By-Product, Unrefined Coal Tar, excluding Creosote Oil Fractions Automobile Exhaust so 0.6*0.8 1.5 10 110 30-60 3-10 _ 25 0.6-0.8 mil* 10 null* mil* unknown unknown 3 0.3-0.* 10 _ 250-300 20-30 10-15 100 1000 200-300 _ unknown. 30-100 125-150 20-30 mil* 100 ' 0.01 saall* unknown unknown 15-18 10-15 '- 100 '- _ unknown * See discussions la this section NGNS 0 5 3 3 4 7 eventually dissipate from the papers ee air eDlaalone, due to biphenyl's volatility, If left open to the atmosphere. The high eetinate given In Table VIII-1 vas obtained by assuming all of the biphenyl vas allowed to dlealpete; the low estimate by assuming one-half of the papers were des- troyed by Incineration, thereby destroying the biphenyl. 3. Dowthenl A It would aecD unlikely that large amounts of Dowtheni A are released to the environment because decoapoaed or Impure Dowtherm can be used for fuel purposes or purified via distillation. There Is no sec "working-life" for Dowtheni A (Anderson, 1976). As long at 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 la simply "topped-off" with fresh Dowtherm. ' Because DowthenjA can last for years, the quantities in current use must be quite high. SRC estimates that 5.3 million pounds of DowtheniA were produced in 1975. It is possible that 30-40 million pounds or more ara currently being used. An attempt to produce an exact figure for currant 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 HONS 053348 5. Petroleum IC would (earn unlikely that any large quantitlee of tha vary . low parcantaga' of biphenyl preeent In petroleum will be ezpoaad to the environ ment. In Section VI-A-1, It waa eatimated that approximately 1000 pounda of blphanyl are axpoaad to the environment annually from oil apllla. For the tan- year period between 1966-1975, a figure of 10,000 pounda waa aaaumed for releaae determination. 6. Naphthalene Feedetock and Toluene Dealkylation By-Product, Unrefined Aa for petroleum, It would aeem unlikely that any large quan- tltlea of biphenyl preaent in theae aourcea will be expoaed to tha environ ment. The biphenyl from theae aourcea will probably be added to fuel olle which are burned. The biphenyl that la burned for fuel ehould be dettroyed and, therefore, not releaaed to the environment. 7. Coal-Tar, Excluding Creoaote 011a Aa explained In Section V1I-A-3, the eventual fate of thla product la not certain; therefore, no eatlmate la made. 8. Automobile Exhauat See dlacuaalon of Section VII-A-4. B. Diphenyl Oxide Table VIII-2 llata the eatlmatad environmental releaaea of diphenyl oxide. Explanation of aatlmatea are dlacuaaed below. 1. Dye Carrier 0S33*9 All of the diphenyl oxide uaed In dye carrlera la releaaed from the dyeing planta, either In air emlaalona or In vaate watara aa prevloualy 78 Table VII1-2. Estimated Environmental Releases of Diphenyl Oxide Dae* Dye Carrier Perfume and Soap Dosthen? A Current Annual Use (X106 lbs) Quantities of Diphenyl Oxide (SRC Estimation) Current Annual Environmental Release Estimates (X106lba) High Low Estimated 1966-1975 Use (HO6 lbs) Estimated 1966-1975 Environmental Release (X106 lbs) High 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 MONS 0 5 3 3 5 0 described for biphenyl dye carriers. The high estimate given la Table VIII-2 was obtained by assuming that only SOX of the released diphenyl oxide was affectively 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 asaumes that 50X of the released diphenyl oxide Is treated effectively. 3. Dowthen^A See discussion in Section VIII-A-3. 80 HONS 053351 IX. Environmental Perspective* A. Occupational Exposure to Man The following OSHA Threshold Limit Values have been estsbllshed for exposure to biphenyl and diphenyl oxide in air: Biphenyl Diphenyl Oxide 1.0 ppm (time weighted average) There ere no OSHA recommendations to control direct contact of biphenyl or di phenyl oxide in solid or liquid form; possible skin absorption of these sub stances is apparently not considered to have measureable health significance. The following toxicity data are available for the two chemicals (Christensen and Luginbyhl, 197S; Opdyke, 1974; Haas jet al., 1975): Biphenyl: inhalation - human oral - rat oral - rabbit skin - rabbit fish - fat-head minnow TDL : 4400 ug/m3 LD : 3280 mg/kg ID": 2400 mg/kg LD": 2500 mg/kg TL'W(96 hre): 1.5 mg/1 Diphenyl Oxide: oral - rat skin - rabbit LD..: 3370 mg/kg LD": > 3000 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 anvlronmental health). They have recommended a biphenyl vapor on the argument that (1) references listed in "Documentation of the Threshold Limit Values" are not velid for biphenyl, and (2) employees in some industries have been exposed to greater than SO mg of biphenyl vapor per cubic mater of air for years with no discernible long-term health effects (Todd, 1976). The present environmental (workplace) atandard is Intended to prevent irritation and 81 M0NS 053352 Injury to the respiratory passages. It la primarily bated upon tha tubJactive reapontea of human volunteers who complained of eye, note, and throat Irritation whan exposed to a mixture of biphenyl and diphenyl oxide at concentration! well below 7 ppm (American Conference of Governmental Induatrial Hygienittt, 1974). B. Release to the Environment 1. Biphenyl Moat of the biphenyl releated to the environment by man it re- leated by the textile dyeing industry, the larger dyers (Burlington, for ex ample) operate mills which have their own watte treatment facilities to process wastes while most other dyers apparently release wastes to city or county facilities. a. Effectiveness of Biphenyl Watte Treatment The exact effectiveness of treatment of biphenyl wastes by each treatment plant cannot be ascertained because the individual treatment planta 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, NC. Burlington operates their own waste treatment facility at this mill. Mr. Joe AmeSn, 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. HONS 053353 82 and all other factory wastes. Mr. Am*an alao raporta that In community waste traatnant planta operated by Burlington in othar cities, a 15X or more addition of commlty solid wastes to tha Burlington wastes reduces COD levels of the affluent to 50-100 ag/1. Dr. Patar 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 bean directed at potential PCB formation during chlorine pre-treatments. This PCB formation is discussed In more detail In Section IX-B-l-c. Biphenyl has been detected In river water by Webb at el (1973) and Hites (1973). Hites identified biphenyl, trlchlorobensene, and butyl bensoate in the waters of the Merrimack River at 0.1-0.5 ppb concentra tion. Hites attrlbutss the presence of these organics to upstream textile factories. Also, W.C. Tichner of the Environmental Resources Center of Georgia Institute of Technology has been studying the problem of biphenyl effluents from polyester carpet manufacturing in Ceorgia. Tinehar haa meaaured biphenyl concantrationa In atreama 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 ' MOMS 053354 83 ratal, typical treatment cultural ware obtained and pre-conditioned to tha dya carriera. All cultural received an initial dya concentration of SO ppm. Ex traction! of the culture and tha water eyetarn were made at varloua tinea and analytad. Figure IX-1 showa hov long the microorganism! took to reduce tha concentration of the dya carrier containing 95Z biphenyl and of the other dye carriers (Baas e al., 1975). Tha biphenyl was totally blodagraded in about 48 hours. What may be note-worthy from Figure IX-1 is the relative inability of trichlorobsnzene and perchloroethylane to biodegrade. These two chlorinated hydrocarbons are used in large quantities as dya 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 aa 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 dlonlzed water held at 20*C, and than 1 mg/1 of chlorine was added and the reactants kept in contact for one hour (Versar, 1976). Carlson at al. (1975) conducted a detailed laboratory analysis to determine chlorine incorporation into biphenyl and other aromatic compounds under conditions utilized for water renovation. Table IX-1 is a summary of PCB formation under the various aqueous conditions used (Carlson at, al., 1975). The results shown in Table IX-1 confirm the possibility of chlorine incorporation into the biphenyl nucleus under a variety of conditions. 84 HONS 053355 Flfura IX-X. Reduction of Concentration Owing to Biodegradation - Analyala of Culture Celia and Hater (Haaa at al., 1975) 85 MONS 053356 HONS 0 5 3 3 5 7 Tabic IX-1. Chlorination of Biphenyl Utilizing Hater Renoration Conditions (Carlson at al., 1975) Cfclocioa turn c-(0d)2 c*(a>2 c*(a>2 co<oa>2 e*(oa)2 c(oa)2 Ca(0Cl)2 C(0C1)2 Cb(oa), ct, MCI ClI MCI < MCI *0 3.3 $.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 U 2.0 u 10.4 2.2 7.0 CMarlw, Of* 100 100 100 100 10 20 33 30 100 10.0 293 24* 030 1330 2930 Booctiai Tim, kr 24 40 72 120` 120 120 120 120 120 0.23 0.23 0.23 0.73 0.23 0.23 0.4 1.0 1.7 2.3 0.004 0.02 0.04 0.13 0.27 .2.2 9.3 0.1 0.0 24 3.2 litantaJ wlMita (m4 ap*rlMatlly Co kt *.# at/1. `lllfetr dklorteotH town <1m prrnat. 2- 13 32 34 49 0.1 0.44 1.4 4.0 0.0 120 430 5-10 40 100 200 M of Cfcloriaotoi Tritet IT? i, 10 27 47 02 0.12 0.31 1.2 4.9 7.4 10 190 10 130 00 so 370 110 00 4.4'- 20 40 300 30 Dr. Gaffney has reeanely reported (Gaffney, 1976) that hit (tudlaa hava determined that PCB's ara formed during pra-chlorlnatlon of sawaga containing blphanyl at tha waste treatment facllltlaa ha haa baan atudylng. Tha raaulta ara balng praparad for publication at thla time. Dr. Gaffnay indicated that tha PCB laomara predominately formad ara the 2-chloro, 2,2'-dlchloro, 2,4'dlchloro laomara. A relatively small amount of trlchloro laomar has also baan datactad. Hydroxylatlon of tha blphanyl In the severs anrouta to tha waste treatment facllltlaa greatly aids tha chlorination of the biphenyl nucleus. Dr. Richard Johnsen has also conducted laboratory studies of blphanyl chlorination under conditions which may exist at waata treatment plants (Johnsen, 1975). Biphenyl In water (5 ppm) was addad to chlorinated water given chlorine concentrations of 8, 83, and 830 ppm. Under ambient conditions and after aging for 24 hours and 1 wash, the samples were analyzed, along with suitable controls, by gas chromatography. The results wera somewhat surprising; whan chromatographs of biphenyl reacted with Clg-vater (83 ppm and 830 ppm) for 1 day are superimposed over a chromatograph of Arochlor 1221 (a coumarclal PCB), striking overlaps are observable, although peak heights are not the same. This prsliminary work by Dr. Johnsen is being continued. Dr. E.L. Kothny has suggested an Interesting source of PCB and other chlorinated orgenlcs found In the environment (Kothny, 1976). He has proposed that the chlorine released from sea salt particles might chlorinate organics such as blphanyl found in the atmosphere. There is, howsvsr, no evi dence to support this contention at present. HOMS 053358 87 2. Dlphanyl Oxide . The information and data given below haa been acquired from the Dew Chemical Co. (Otla, 1976). a. Effectlveneaa of Waata Treatment "Generally, organic chemlcala with a BODj (5 day biochemical oxygen demend) value in exceaa of 60 percent of the atolchlometrlcally required mount of oxygen are readily degraded In conventional waete treatment facllitlee. Under favorable waate treatment condltlona, concentrationa of diphenyl oxide in waate atreama have been reduced up to 95X. Thla magnitude of reduction la typi cal of that encountered with municipal waatea. Analytical methoda are available for meaeurlng the concentrationa of diphenyl oxide In watera and waate atreama. In the event of a groaa dlacharge of diphenyl oxide into a river, technlquea are available that can predict the downatrean concentrationa of diphenyl oxide baaed on aone known ratea and routea of removal from the river. Theee route* include adcrobialdegradation (by a variety of aquatic microorganlama), abaorptlon on uepended aollda, and volatility from water" (Dow Technical Data Sheet - XAS1075L). b. Biodegradation "The moat deairable environmental property of diphenyl oxide la ita ability to blodagrada into carbon dioxide and water in the preaence of naturally occurring microorganlama. Thla obaervatlon la aupported by a variety of teata Including the atandard biochemical oxygen demand (BOD) taat, an oxygen probe teat, and teata which meaaure the chemical dieappearance from aoll and river aedlmenta. A poatulated mechaniem of diphenyl oxide converalon to carbon dioxide and watar under the Influence of aerobic microorganlama la believed to 88 MCNS 053359 Involve some catechol-Hkn intermediates. However, positive proof for this nechanlem has proven difficult because of the transient existence of the interedlate compounds" (Dow Technical Data Sheet - XAS-1075L). c. Bloeoncentratlon "Detection of chemical residues In fish has been the key environmental alert for DDT and PCB's. Consequently, the potential of diphenyl oxide to bioconcentrate was determined.* Bloeoncentratlon 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 e limited ex tent, quite unlike DDT or PCB's. When placed In fresh water, the fish were found to eliminate diphenyl oxide rapidly, 50X each day compared to SOX each 30 days for an Isomer of PCB's. These results show that hazardous ox persistent concentrations of diphenyl oxide In fish are unlikely to occur" (Dow Technical Data Sheet - XAS-1075L). * Results published by Neely at el. (1974). The log bloeoncentratlon factor was experimentally determined as 2.29 (therefore, bloeoncentratlon factor - 190). 89 MONS 053360 X. Environmental Assessment A. Biphenyl Biphenyl ia being releaaad to the environment in quantities which Bay total 60 million pounds annually and perhaps even higher (SRC estimate). The largest known source of biphenyl releaae 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 waatewaters from the dyeing factories to either muni cipal treatment facilities or to on-site treatment facilities. Comon forma 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 sero in only 48 hours (Baas et. el., 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 la the evidence which indicates that biphenyl-containing sewage may be chlorinated to FCB isomers during pre-chlorination processes for disin fection and deodorization (Gaffney, 1974, 1976; Carlsen, 1975; Johnsen, 1975). 90 HONS 053361 Laboratory experiments which hava mimicked treatment facility methods have found that tha biphanyl nuclaus can ba chlorinated with four, or uaually laaa, chlorine atone. Conmerclally prepared PCB'e hava a much greater degree of chlorination and hava certainly lesa biodegradability than the PCB lsomera which may be gen erated at vaete treatment planta. Although aufflcient reaearch has yet to be done for condueive reaulta, tha preaent indication* euggeet that chlorination of biphenyl-containing aawage deaarvea a great deal of consideration and par- hapa restriction. Another major aourca 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 tha 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 ralaaaed to the atmosphere by biphenyl's volatilisation or to water by leaching from creosote oils (SBC estimate). An uncertain but potentially significant source of biphenyl exposure to the atmosphere le automobile exhaust. It le possible that biphenyl is one of the many hydrocarbons present in auto amissions; however, there is no avlal- able monitoring data to confirm this supposition. Even if biphenyl is present in only a very small fraction of a percent, the annual quantity emlttad could be very large due to tha 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 (SBC estimation). The two major sources 91 MONS 053362 Laboratory experiments which have mimicked treatment facility methoda have found that the biphenyl nudeua can be chlorineted with four, or ueually laea, chlorine atoms. Commercially prepared PCB'a have a much greater degree of chlorination and have certainly leae biodegradability than the PCB laomera which may be gen erated at waate treatment planta. Although aufflclent reaearch haa yet to be done for conducive 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 la present in creosote oils because it is one of the constituents in the blgh-bolling 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 vary large due to the enormous amounts of hydrocarbons esiittad 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 HONS 053363 91 of diphony1 oxldt roloast art aoap and pacfuma uae and dya carrlar uaa. Han has baan exposed to diphenyl oxide aa an ingredient in some soapa and perfumes since the early 1930's. Laboratory and practical experience have suggested no advaraa affects from diphenyl oxide use via perfumes and soaps. Tha Council of Europe (1970) included diphenyl oxide in the list of temporarily admissible artificial flavouring aubstences (Opdylte, 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. 92 HONS 0S3364 Appendix A Physical Properties HONS 053365 93 Biphenyl (Monsanto Tsch. Bull. 1C/FF-29) Malting point,.*C 69 Bolling point at 760 am Hg, *C 10.5 an Hg, *C 255 118 Spaelflc gravity, 20*/4*C 77*/4*C 1.04 0.99 Lbs./gallon at 77*C Refractive lndsx, n77 8.23 1.588 Viscosity at 70'C, Saybolt Sac. 100*C, Saybolt Sac. 31.2 28.8 Surfaca tanslon at 129,2*C, dynes/cm 39.5 Flash point, closed cup, *C Open cup, *C 113 124 Latent hast of fusion, Btu/lb. 53.1 Specific hast, Btu/lb/*F 0.43 Odor Pleasant, peculiar Appearance Colorless to pale yellow crystallized solid or flakes Molecular Height 154.20 Empirical Formula Structural Formula Wi r\~r\ Solubilities - Crams biphenyl per 100 cc of solvent Hydrocarbons Hater* Solvents Mineral Spirits Casollne (Texaco) Kerosene Bensene Xylene Turpentine Toluene Solubility 16.9 24.1 17.5 81.5 56.9 24.2 62.0 0.00018 * 95% Biphenyl dye carrier (Haas at al., 1975) c 26 26 27 27 27 24 18 94 HONS 053366 Diphenyl Oxide (Dow Porn Ho. 110-288-72) Nolacular Haight Bolling Point *C 760 nmHg Spaclfic Gravity 25/25*0 Pound par gallon, 25*C Rafractlve Indax, 25*C Praata Point *C Plaah Point *F COC Fir* Point *P Auto Ignition Point *F Latant Boat of Taporlcatlon Cal/mola at B.P. Approxlnata Solubility g/lOOg Solvent at 25*C Acetone Ether Benzene Methanol Hater Carbon tatra chloride ii-Haptane DIPHENYL OXIDE GRADE Technical Perfuma Induetrial 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* 238* 1144* 11,800 - 255* 1.065*1.075 8.92 - 15* 235* 255* - m m m m . 20.8 ppn m m m m m m. 21 ppn _m m m 21 ppn m - Solubility of DPO la watar at 25*C........................................................................ 20.8 ppn Solubility of watar in DPO at 2S*C ......................................................... 0.071Z Solubility of watar In DPO at 30*C........................................................................ 0.077X BOILING POINTS OF DIPHENYL OXIDE Boiling Point MM Hg 257.9*C 181.3*C 147.1*C 121.0*C 77.0*C 760 100 30 10 1 MONS 0533*7 95 Appendix B Material Safety Data Sheata 96 HONS 053368 MATERIAL SAFETY DATA SHEET (APPROVED AY THE U.S. DEPARTMENT OP LAbOR AS eimilor" to I bra. 0$HA*30) .-tmu *_a Me*, J* AW WMIW` NAVi S.ct.un l NAME 4. PRODUCT D_O_W CHE_MI_CAL_ O.S.A MIDLAND. MICHIGAN 48640 i *n r i . v h---------ymtwKtixrn Vj****!---------- *^sc.......... -- .12.23------1-- ----- --------------^rflw'.vjr _517 636 4400 k Diphenyl Oxide, Technical --------Diphenyl Ether jictl 1 INGREDIENTS Diphenyl oxide 95 (Not a specification value) SOILING POINT <*F.I S<lli> 3 iOB PHYSICAL DATA SOLUBILITY IN WATER VAPOR PREMURE VAPOR 8INIITVI...R 11 ^PPJARANCJ^ JO'cl -- SPECIFIC GRAVITY (M,0= 1) % VOLATILE BY VOLUME FIRE AMD EXPLOSION HAZARD DATA ITT|F t.AMMABlK b MIT* tT Ml 4 205-f Cleveland Open Cup r.Li___ QJ5__________ sia=l_ .cagynao rrn ALCOHOL FOAM IX IFOAM >EVtHTtH WflofiCTION tou'utTTmcmT AND HASAHCl JjCTcQj____ jjflcHEMICAL Insoluble 1.070 (i n/LT -h-l-h 1.5 n___________________ None. STABILITY (NORMAL CONDITIONS) fcbtibiSiSHA + 4 a> Old S REACTIVITY DATA STABLE Vi ftKUIHTT incompat. water Paco base ""|coBRosivf r--iOXIO(JINO 1 [MATERIAL I6ILITY *TrrYninrEKfc"o<rTTBirwBorYf------- Non*. hazardous ' polvmcriz* ATION ieav.bif.4H* f4 *.4,6 * MAY OCCUR iJULLMOlt. S*ciMi A ,.. ttid m crif"MTTfn.xrn KfUiirirariri rwr SPILL OR LEAK PROCEDURES Small spills - absorb In sweeping compound. Large spills - call Dow emergency number for lnscruccions. Burn or bury in accordance with local ordinances. HONS 053369 Diphenyl Oxide, Technical MATERIAL SAFETY DATA SHEET <t. t X.T VV1 . .r.ffAg.1 . Viw >"healthhaiabd paVa DOW CHEMICAL U. S. A. i tingle dote oral; LD, 4000 mg/kg for both recs end guinea pigs. Estlmat- B; from theta data, the lethal dote for a 100 pound person may be In the ige 3/4 cupful. Mild to moderate irritation; unlikely to cause Injury. Krtiffrt------------------------------------------ ------------------------------------------------------- Occasional contact - no adverse effects expected. Mild to moderate Irritation upon repeated, prolonged contact. JKTWtrsrjT-- - No LD,, determined because of lack of indication of" Wot readily absorbed - problem from absorption._______________________________ [Ly^^^^pyj^^^ad-gn-adftt-gflnCral.--No problem at room tenBrtur. Disagreeable odor, possible liver Injury at high concentration. eri iuw iTH PlOfflNO NArm EYES & SKIN: Flush with plenty of water; get medical atten- Mivcteivi tlon if irritation develops. Remove contaminated clothing PLVtOtO* and free of chemical before reuse. 1NHA1ATI0N: If discomfort develops from breathing vapors, get iMmicr tOasiTMC patient to fresh air. ' INGESTION: No known antidote; treat symptomatically. ciout oa COMtUlVQHl S<t SPECIAL PROTECTION INFORMATION LSufficitnt to control to TLV. gi f* ii'a . -- 'When disagreeable odors occur, full-face mask and canister for organic vapors. --- Clean clothing. 0 .l.t . a * Lnjf.KTiNll^MAvT*u**Lr *1afrMm4*iOIi ..... ..... mV'V t>Mr S_rgCJAL_ PRECAUTIONS OR OTHER COMMENTS WAUmV'smA I Use reasonsble care. Store in cool, dry place. M0NS 053370 MATERIAL SAFETY DATA SHEET I 4.*.' I )v|0 M THE U. S. DEPART*** r OF LAlO# AS * ' t* UiH.V Zl| -a> r ranMnti.H.' 1* HAMS**! moouct"' < ..mtT.-jr-. - i J ^Nv POINT ,'F.) 'flluft! 10*I .ap?s DiNiirr *. * n S.c. a 3 PHYSICAL OAfA 441 _SOLyJ!LI1 *Ul WATlH Q25UC I S 7 J jJ / ^ -- spcci'-c *:'vy it il.lo a-'cn; fU* -- *. ov.i-it.e sv clum<___ _j_.Nct \pplirasi* {'* 4 TTTTZ".j.nt kMC *ti**ao UKCO 235 `r Tag Closed Cup FIXE AND EXPLOSION HtZARO OATa 0.6 3 232*F I.. I--I *TS ("73 r--lAlXOhOL re; rei-RY .-- ---- .fj-i-,I.--.,uI -xil.fog,t tiAIworur, .-,1I rIfi*oxa,<i.........-I--X---`-c-s----------- ------j-m--i-c--a--i.-----:>-- Non* 5.3 3 3U< *TA*IU*> s:LB.i{as:i'T5"irr5------- *. i i L r \ S'aELE * >* .NJTA4LI .. . rg* b IWC0**aT. f").r riAiio risAit ItlLlTY REACTiviTY oata ' [~~|:oaA?ti .i . 0s*v ............................................ 1% *: it t-- .......... Nsr.* NiiA*90US aTiJn MAY OCCUR #111 NOT e as* r>oni r * tf.-.*Ar * . .t . s>iLt"dRTZf Moctouilw !!AJ| Mi 'm.A* II ACLtfAWt. ' - C ------------------- Scoop up and salvag* if possible ^ * ~. HONS 053371 Obsorv* F*d*ral, State and Local laws. Cor.tac t The Dow Chenictl Co.r.sjnv f>r disposal instructions. aiphatiyl, High Purity ATERIAL SAFETY DATA SHEET <co,,r.. MgALTH HAwAftO Q*Ta DOW Ch-.MiCAL u.s.a. Mr0LA#O, ow single dose oral toxicity. LDjo rats is greater than 4000 mg/kg. ' i time ting from these data, the lethal dose for a 100 lb. person .may be Ik-ounces._________________________________________________________ _______ _______ p to slight irritation but no corneal injury. hare' single exposure not likely to causa significant irritation, Prolonged fcr repeated exposure may cause slight irritation. ,iot likely to be absorbed in toxic amounts. l_V: 0.2 ppn or 1 mg/m' (1974) fiWli jrsi------------------------------ Respiratory irritation. "I EVES t Flush with plenty of water for S minutes and get medical; help if ill effects occur. SKIM: Wash with soap and water. !. Remove groaaly contaminated clothing and wash betori reuse. i XNHAIATIONj If ill effects occur, get parson to fraah air :i::d ' . get medical help. INGESTION: Not likely a problem. If large 1 amounts are swallowed, see above, promptly induce vomiting ; and get medical help.* $.>.. | JMCUt. PROTECTION INFORMATION -------------------- ------ ---- ---------------------- -- Respiratory protection required in absence of propar environmental control. If required, use an approved dust respirator. vr-pr;. ------------------------------------------ -------- - Clean body covering clothing. -- -......................--............. . ....-- ............. H '" *vat-.nru**t* r i.** .* o-.* . i j ho tic..UJ'iiiili.' yC Js' f-jy * i': 4 iw>. : ^ ^ L> to -- er-. V : *V*; i:"* 1W n9A4 rrrrr 4449494 03 Eve fountain and washing facilitlss nar work area. 1 S.aiIah~9 iPECIAL PRECAUri'o.Ni ON Of'-j l COMNENTt' "SXOW.kiA . esiua `~ Practice reaeonable care and cleanliness to avoid gross skin and eye contact. 'Avoid breathing vapors and dusts if generated. a*N0TZ TO PHYSICIAN: No specific antidata known. Treatment depends or. tr.e sound judgment of the physician and the individual reactions of the patient. - MOUS 053372 100 IVIAlfcMIAL SAI-tlY UAIAOUCCI (APPROVED St THE U.t. DEPARTMENT OP LASOR AS "ettenNclly s.w.lmr" Utm Q$HA 101 ........................ --~..........* '< 4*4 .< . ( *> |l lt?9 k4 |kll M> i* ,t4 , ,Mn *1 It* f Mfi 4>. 17Z* JTV;"Tt.fc A' i"****i Secfien \ NAME l PRODUCT ----------------------------- ----'cTiT-synr-s.rgBbi1 DOW CHEMICAL U.S.A. MIDLAMD. MICHIGAN <8640 7Vr I ELU *w"W|fN """ '"'""TWJfifVTIftTrVr'Hi November 13x19 7A _[ __ niV'il-rfi'Ti----------- J------------ --------- --------------------------------------- TB<nrrar DOWTHERlP A heat transfer fluid Set Men 3 INGREDIENTS iiuriucr. St 7 636.4400 ---------- % srty^Mus* * Diphenyl oxide Diphenyl (Not specification values) 13.5 }ippt 16.5 SOILING POINT ff Settle* 3 494.8 PHYSICAL PATA tOCUm.ltY IN WATER specific gravity tHio=n *.*!. * UM V .and MCVhOO ued> 255-f Cleveland Open Cup I I - OL*TIUB Y VOLUME omat(q odqr Fme"*wo gxptosioH hazard data l^bAMMAkLK UWtTM .ST^ IN *iH i.r.u. 0.5X (500*F) 0.3 .flppm g feO'F lu., - 6.2% (500*F) iTjeMeMM TMm j-* r\i$srL gu caasmou. iwfrrnrr,?vi*rJ*vfmiatwtiTttoHviw**MtT anohIzaaoi Self-contained breathing apparatus may be needed in enclosed spaces. STABILITY NORM*c CON-D1ITIONS) Settle* S RfACTIVITY Data `EBNsmswi istebis----------------------------------------------- STABLE UNSTAtLKI U*Ttrt.*i.k Vo AV&-D |incompat. Q*A,eR ,,JD ACID_ IIILlTY r il^rct. r'.rfn AAdtiOcYf * P")eAtg {""[corrosive noxiotzmo 1 X|MATtIAL None NAJaROOUI POLYmIRIZ. AtlOH MAY OCCUR MILL NOT c dMt>i ndNi to avo.o \r a AC cKflfc., -- V"' ua. urut unn. Settle* * SPILL OR LEAK PROCEDURES HSUWft BT1M 'HI ' Soak up with absorbent material. L Incineration in approved equipment. MONS 053373 ii DOWTHER^8 A HATERlAL SAFETY DATA SHEET kmt., DOW CHEMICAL U. V A. J" ReALf'H1wVi`iiTtF=OATTa ow single dose oral toxicity. LDW rats is in the range of 2000 co 4000 mg/kg. Itimating from Chose data, the lethal dose for a 100 lb. person may be 2 o 4 fluid ounces. InR'rj'"------------------------------------------------------ ; p to mild irritation but no corneal injury. I f.............................. '* -- urt single exposure not likely to cause significant irritation. r repeated exposure may cause up to mild irritation. ' * Prolonged 'rrsnsfrv.. "KoflfEeXy "to'be absorbed-in toxic amounts. Very"'fow-in" ^lclty.y_this, rojjte..------------------------------------------------------------:.......................................7...... '.V: lpp (W73) . r. -------------------------------------------------------------------------------- ---------------- ---------------- ---------- -- Inhalation - vapors have a disagreeable odor. tEYES: Flush with plenty of water for 5 minutes and get medical eye help if ill effects occur. SKIM: Promptly flush skin with plenty of water. Remove badly contaminated clothing and wash H;",H before reuse. INHALATION: Not likely a problem due to dis owing agreeable odor. If ill effects occur, get person to fresh air wwur end get medical help. INGESTION: Not likely a problem. If lrge amounts are swallowed, see above, promptly induce i vomiting and get medical help.* .CWll.M . . Pa Iv 4 ( SwrtlMi I SPECIAL PROTECTION INFORMATION *y!*" Good room ventilation usually adequate for most operations, 'ntrol vapors to TLV.;____________________________________________________ ___ " ft a'">*^T'ifor`t"on TpefTTy'typei ---- -- |6ne likely to be needed. For emergencies of % hour or less, full face mask '.us an organic vapor canister. strrr; reri-^r.tc--------------------- lean body covering clothing. 0, f1 ]*? MOAMeLbvjy |AJTV I.ICTI J_ LJwEtCHEEt WV |ttl T-^OU M r^e rtgwr ^L.eie a St: '* HVfc.BC.Ht raiISP'1nCM1AffLi.-E' PRECAUTIONS OR OTHER COMMENTS Jactlce reasonable care and caution. Avoid breathing vapors if generated. ifOld direct contamination of water because of fish toxicity. ' i. nOTE TO PHYSICIAN: No specific antidote known. Treatment depends on the >und Judgment of the physician and the individual reactions of the patient. HONS 053374 107 REFERENCES Aaeen, J. (1976), Personal Communication, Sanitary Englnear, Burlington Induatrlaa, Greensboro, N.C., Hay 1976. American Confaranca of Covarnmantal Induatrlal Hyglanlata (1974), "Documentation of tha Thraahold Limit Valuaa". Andaraon, L. (1976), Faraonal Communication, Dow Chemical Co., Midland, Ml, May 1976. Anon. (1976 a), "Journal of Commerce,"'April 22, 1976, p. 5. Anon. 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