*• WLB:TDI1:01 iffy LISTING BACKGROUND DOCUMENT FOR DINITROTOLUENE, TOLUENEDIAMINE AND TOLUENE DIISOCYANATE PRODUCTION1 Kill: Product washwaters from the production of dinitrotoluene via nitration of toluene (C,T) K112: Reaction by-product water from the drying column in the production of toluenediamine via hydrogenation of dinitrotoluene (T) K113:. Light ends from the purification of toluenediamine in the production of toluenediamine via hydrogenation . .'. of dinitrotoluene (T) -. ..K114V Vicinals from the purification of toluenediamine l'__ , ; in the production of toluenediamine via hydrogenation \ ' of dinitrotoluene (T.) : K115: Heavy ends from the purification of toluenediamine in the production of toluenediamine via hydrogenation of dinitrotoluene (T) K116: Organic condensate from the solvent recovery column in the production of toluene diisocyanate via phosgenation of toluenediamine (T) *One waste from TDI production (EPA Hazardous Waste No. K027, Centrifuge and distillation residues from toluene diisocyanate "i production) was previously listed. A background document for Vl' this listing has been available in the public docket at EPA L^ Headquarters and at EPA regional libraries since May 19, 1980. H v- 4 \ t TABLE OF CONTENTS PAGE I. Summary of Basis for Listing 1 II. Sources of the Wastes 2 A. Profile of the Industry 2 B. Manufacturing Processes 4 1. Nitration of toluene to form dinitrotoluene (DNT) 5 2. Hydrogenation of DNT to form toluenediamine (TDA) 3 3. Formation of toluene diisocyanate (TDI) from TDA 12 III. Composition of the Wastes 16 IV. Waste Management 22 V. Basis for Listing 27 A. Hazards Posed by the Wastes 27 B. Degree of Hazards Posed by These Wastes 34 C. Mismanagement 37 D. Environmental Effects of the Hazardous Constituents 40 E. Health Effects of the Hazardous Constituents 43 VI. References 51 VII. Appendix I 52 VIII. Appendix II 53 I. Summary of Basis for Listing The above-listed solid wastes resulting from the nitration of toluene to produce dinitrotoluene (DNT), from the hydrogenation of DNT to toluenediamine (TDA), and from the reaction of TDA with phosgene to form toluene diisocyanate (TDI), are hazardous solid wastes. The Administrator has determined that wastes from the above processes pose a substantial present or_potential hazard to human health or the environment when improperly transported, stored, disposed of or otherwise managed, and therefore should be subject to appropriate management requirements under Subtitle C of RCRA. This conclusion is based on the following.considerations:. - 1) Wastes from the production of dinitrotoluene, toluene diamine,. and.toluene diisocyanate typically contain significant concentrations of one or more of the toxic compounds: 2,4-dinitrotoluene, 2,6-dinitrotoluene, 2,4- toluenediamine, 2,6-toluenediamine, 3,4-toluenediamine, 2-amino-l-methylbenzene (o-toluidine), 4-amino-l-methyl- benzene (p_-toluidine) , aniline, carbon tetrachloride, tetrachloroethylene, chloroform, and phosgene. 2) A number of these, compounds — namely, 2,4-dinitrotoluene, 2,4-toluenediamine, o-toluidine, chloroform, carbon tetra chloride, and tetrachloroethylene— have been identified by the Agency's Carcinogen Assessment Group (CAG) as known or potential, carcinogens. In addition, several of these compounds have been shown to be mutagens in bacterial or mammalian test systems, and cause reproductive, terato genic, or otherwise chronic systemic effects. 3) Dinitrotoluene product washwaters (waste Kill) are also corrosive (pH = 1 - 2), due to the high concentrations of sulfuric and nitric acids. 4) These wastes are produced in large amounts: an approximate total of 647,000 kkg of DNT, TDA, and TDI production wastes are generated annually. 5) These toxicants, moreover, are mobile and persistent in the environment. In fact, a number of these toxicants have been found in drinking water or surface water, as well as in air, and, thus, have been shown to leach and be sufficiently persistent to escape into the environment and present a substantial hazard to human health or the environment, if improperly managed, such as disposal in unlined surface impoundments, or inadequate incineration. II. Sources of the Wastes2 A. Profile of the Industry The manufacture of toluene diisocyanate (TDI) from toluene involves the production of dinitrotoluene (DNT) and toluenediamine (TDA) as intermediates. As of 1983, five domestic companies were producing TDI at seven locations (see Table 1). Two other major manufacturers produce DNT and/or TDA primarily for sale to TDI manufacturers. The Air Products plant at Pasadena, TX is a key supplier of DNT and TDA, while the duPont plant at Deepwater, NJ is also a major producer of DNT. There are several other producers of DNT and TDA; however, their production levels may be quite low, and some are producing TDA for captive use in the manufacture of "dyes or other chemical products. (Table 4, which later discusses quantity and management data for the waste streams of concern, includes not only data based upon the production volumes of the DNT and TDA produced for captive use in TDI production, but also includes the production volumes of the DNT and TDA produced for sale to other facilities as intermediates in TDI production.) TDI production capacity in the U.S. was 315,000 kkg in 1983. The U.S. International Trade Commission reported the total production of TDI (80:20 mixture of the 2,4- and 2,6- isomers) 2The information presented in this section is taken in large part from a 1983 report prepared by S-Cubed. TABLE 1 - PRODUCERS OF TOLUENE DIISOCYANATE (TDI)1 RAW CAPACITY3 PRODUCER MATERIAL PRODUCTS2 (106 kg/yr) Mobay Chemical Corp. toluene 1,2,3 59 Baytown, TX Mobay Chemical Corp. toluene 1,2,3 57 New Martinsville, WV Olin Corp. dinitro 2 45 Lake Charles, LA toluene Olin Corp. toluene 2 34 Moundsville, WV BASF Wyandotte Corp. -dinitro .2 57 Geismar, LA toluene Dow Chemical toluene 2 45 Freeport, TX diamine Rubicon Chemicals toluene 2 18 Geismar, LA TOTAL 315 ionly manufacturers of TDI are listed within this table. Other manufacturers produce DNT and/or TDA intermediates but do not produce TDI (see text). 2Rey to Products: 1 = pure 2,4-TDI 2 = 80:20 mixture of 2,4- and 2,6-TDI 3 = 65:35 mixture of 2,4- and 2,6-TDI 3Nameplate capacity for TDI production as of 1983 (SRI International, 1983 Directory of Chemical Producers - United States, Stanford Research Institute, Menlo Park, CA, 1983). domestically in 1980, 1981, and 1982. Reported production data for DNT and TDA were less specific. However, based upon reaction stoichiometry and estimates of process yields from process residuals reported by manufacturers, it was possible to estimate the amounts of DNT and TDA (as the 80:20 mixture of the 2,4- and 2,6- isomers) produced in association with these levels of TDI in 1980, 1981, and 1982. In particular, the production estimates are: PRODUCTION ESTIMATES (in kkg) 1980 1981 1982 DNT 344,000 346,000 337,000 TDA 215,000 216,000 210,000 TDI 267,000 268,000 261,000 Five of the seven TDI-manufacturing plants produce only an 80:20 mixture of 2,4-TDI and 2,6-TDI, while two plants produce an 80:20 mixture, a 65:35 mixture of 2,4-TDI and 2,6-TDI, as well as pure 2,4-TDI. Almost all TDI is used to make polyurethanes, including polyurethane foam products (85% of production), coatings, elastomers, and adhesives. B. Manufacturing Processes The manufacture of toluene diisocyanate typically involves three distinct continuous chemical processes: 1. nitration of toluene to form dinitrotoluene (DNT); 2. hydrogenation of DNT to form toluenediamine (TDA); and 3. reaction of TDA with phosgene to form TDI. As shown in Table 1, four TDI plants begin the production process with toluene and incorporate all three of these steps, two plants purchase DNT for use as a raw material, and one purchases TDA for use as a raw material. The Air Products plant at Pasadena, TX, with a reported annual capacity for TDA of 57,000 kkg, is a key supplier of TDA, as well as DNT. The duPont plant at Deepwater, NJ, is also a major producer of DNT. The following is a description of the major commercial processes utilized in the manufacture of DNT, TDA, and TDI. 1. Nitration of toluene to form dinitrotoluene (DNT) In general, toluene is nitrated with nitric acid in the presence of sulfuric acid, which acts as a solvent and a catalyst. Increasing the acidity and temperature increases the degree of nitration. The dinitration of toluene is represented by the overall reaction: CH3 CH3 (Q) +2HN03 H2S°4 * Gi— (N02)2 + 2H20 •oluene "llVS Dinitrotoluene C (DNT) As shown in Figure 1, sulfuric and nitric acids are added to a recycled acid stream to form the nitrating solution. This solution is combined with toluene in the nitration reactor. The reactor is jacketed, and continuously cooled to remove the heat of reaction. The reactor contents must be vigorously agitated because toluene is not very soluble in the mixed acids. Most TDI manufacturers use either nitration-grade toluene (99.8% purity) or highly refined toluene (99.5+% purity) as a feedstock. The two-phase product from the nitration reactor is Vent Gas Washwater n Kill _ DNT Product HNO3 *- H2S04 Acid Recovery Water Piqure 1. Typical Process Flow Diagram for the Nitration ot Toluene allowed to separate into organic and acid layers. Spent acid from the acid separation unit is sent to a recovery unit where water (a by-product of the nitration reaction) is separated and re-used in the washing process. The recovered acid solution is reconstituted into a nitrating solution containing the desired concentrations of sulfuric and nitric acids. After addition of make-up sulfuric and nitric acids, the nitrating acid solution consists of about 50% sulfuric acid, 20% nitric acid, 12% nitro- sylsulfuric acid, and 8% nitroorganics.