ee SEPA Materials Balance for Anilines SIPID AFINAL REPORT LEVEL I MATERIALS BALANCE ANILINES Prepared for: U.S, ENVIRONMENTAL PROTECTION AGENCY OFFICE OF PESTICIDES AND TOXIC SUBSTANCES Task No. 10 Contract No. 68-01-5793 Michael Callahan - Project Officer Elizabeth F. Bryan - Task Manager Prepared by: JRB ASSOCIATES, INC. 8400 Westpark Drive McLean, Virginia 22102 Project Manage: Task Leader: Karen Slimak Robert L. Hall Contributing Writer: Ronald Burger Submitted: May 9, 1980ABSTRACT This report presents a Phase I materials balance study of a group of anilines specified in a Task Order from the Office of Toxic Substances, U.S. Environmental Protection Agency. The compounds studied were aniline, aniline hydrochloride, aniline hydrobromide, o-, m, and p-nitroanilines, 16 other nitroanilines, and 15 other chloro- and bromoanilines. Areas of major interest were production quantities, producers, consumption quantities, and emissions to air, land, and water related to these processes. The estimated anounts of 1978 production (where available) were as follovs: aniline, 279,000 kkg; aniline hydrochloride, 4.6 - 100 kkg; o-nitroaniline, 3641 kkg; mnitroaniline, 0 ~ 2.3 kkg; p-nitroaniline, 13,000 kkg. Emissions were estimated when direct data were unavailable. The results (Am kkg/year) were: aniline, 20 kkg to air, 0.08 - 5.6 kkg to water; aniline hydro~ chloride, 0 kkg to air, 4.6 - 100 x 107? kkg to water; p-nitroaniline, 0.13 kkg to air, 117 kkg to water. Throughout the report, estinates and assumptions were nade where justified, in Meu of direct data. ‘Types of information required for future studies are noted.abstract List of Tables List of Figures TABLE OF CONTENTS Executive Summary 1.0 Introduction 2.0 Aniline 2a 2.2 2.3 2.4 2.5 2.6 Physical Properties Materials Balance for Aniline Direct 2.3.1 2.3.2 2.3.3 Production of Aniline Production Processes, Producers, and Locations Amounts Produced Enissions Due to Direct Production Indirect Production 2.4.1 2.4.2 2.4.3 2.4.4 Degradation of Products Derived From Anilines Petroleum Industry Automobile Exhaust Hydrolysis of Acetanilide Imports of Anilines 2.5.1 2.5.2 2.5.3 Amounts Emissions Due to Imports Summary Table Consumption and Use of Aniline 2.6.1 2.6.2 2.6.3 2.6.4 Total Consumption Categories of Use Use Within Each Category Enissions By Category of Use Page vi viii tx 2-11 2-11 Rell 2-16 2-16 2-163.0 Aniline Hydrochloride, m-Chloroaniline Hydrochloride a4 3.1 Physical Properties of Aniline Hydrochloride 341 3.2 Materials Balance for Aniline Hydrochloride 33 3.3. Direct Production 33 3.3.1 Production Processes, Producers, and Locations 343 3.3.2 Amounts Produced 3-4 3.3.3 Emissions Due to Direct Production 35 3.4 Indirect Production 3-6 3.5 Imports 3-6 3.5.1 Quantity Imported 36 3.5.2 Emissions Due to Imports 37 3.6 Consumption and Use 347 3.6.1 Emissions Due to Dye Manufacture 347 3.6.2 Emissions Due to Photographic Chemical Manufacture 3-8 3.6.3 Summary of Euissions Due to Consumption 39 3.7. Emissions Due to Exports 38 4.0 Aniline Hydrobromide aed 5.0 9 ~ Nitroaniline 5-1 5.1 Physical Properties 5-1 5.2. Materials Balance for o-Nitroaniline Sel 5.3. Direct Production 503 5.3.1 Production Process, Producers, and Locations 5-3 5.3.2 Amounts Produced 5-3 5.3.3. Emissions Due to Production 5-4 5.4 Indirect Production 5-5 5.5 Imports 5-5 5.5.1 Amounts 55 5.5.2 Emissions Due to Imports 5-66.0 7.0 5.6 Consumption and Use 5.6.1 Categories of Use 5.6.2 Amounts of Use 5.6.3 Buissions by Category of Use m - Nitroaniline 6.1. Physical Properties 6.2 Materials Balance for n-Nitroaniline 6.3 Direct Production 6.3.1 Production Processes, Producers, and Locations 6.3.2 Quantity Produced 6.3.3 Emissions Due to Direct Production 6.4 Indirect Product ion 6.5 Imports 6.5.1 Anounts Inported 6.5.2. Enissions Due to Inports 6.6 Consumption and Use 6.6.1 Total Consumption 6.6.2 Emissions Due to Dye Manufacture 6.6.3 Emissions Due to Manufacture of Other Products 6.7 Emissions Due to Exports p - Mitroaniline 7.1 Physical Properties 7.2, Materials Balance for p-itroantline 7.3. Direct Production 7.3.1 Production Processes, Producers, and Locations 7.3.2 Amounts Produced aa 56 5-6 7 63 63 64 64 65 65 66 66 6-9 698.0 9.0 4 1s 7.6 a7 7.3.3 Enissions Due to Direct Production Indirect Production Imports 7.5.1 Amounts Imported 7.5.2 Eaissions Due to Imports Consumption and Use 7.6.1 Total Consumption 7.6.2 Categories of Use 7.6.3. Emissions by Category of Use Emissions Due to Export Other Nitroanilines 8.1 8.2 8.3 8.4 8.5 Properties Materials Balance for Mitroanilines Product ion 8.3.1 Producers and Locations 8.3.2 Amounts Produced Imports 8.4.1 Anounts 8.4.2 Bpissions Due to Imports Consumption and Use Chloro- and Bronoanilines 9.1 9.2 9.3 94 Physical Properties Materials Balance for Chloro~ and Bronoantlines Direct Production 9.3.1 Production Processes, Producers, and Locations 9.3.2 Amounts Produced 9.3.3 Bnissions Due to Direct Production Indirect Production iv 7-4 7-7 7-8 7-8 1-8 7-9 7-9 7-16 3-4 84 8-49.4.1 Chlorination of Waste Anilines 9.5 Imports 9.5.1 Anounts 9.6 Consumption and Use 10.0 Locations of Enissions 11.0. Data Gaps List of References Appendices 9-2 9-5 9-5 10-1 u-1 BLTable # 2a 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.12 2.14 2.15 3a 5. 5.2 5.3 LIST OF TABLES Enission Factors for Aniline Release to the Air Imports of Aniline Enissions Due to Inports of Aniline Industrial Consumption of Aniline, 1974-78 (kkg/yr) Aniline: Consunption by Isocyanate Manufacture Aniline: Consumption During Production of Rubber Chenicals Aniline: Consumption by the Chemical Dye Category Aniline: Consumption During the Production of Druge Aniline: Consumption During the Miscellaneous Components Aniline: Emissions Generated During Production of Isocyanates (kkg) Aniline: Emissions Generated During Production of Rubber Chemicals (kkg) aniline: Emissions Generated During Production of Dyes and Intermediates (kkg) Aniline: Emissions Generated During Production of Hydroquinone (kkg) Aniline: Emissions Generated During Drug Manu- facture (kkg) Aniline: Generated Emissions During Manufacture of Those Compounds in the Miscellaneous Category Aniline Hydrochloride: Emissions Generated During Consumption Producers of © ~ Nitroaniline by Year Production of © - Nitroaniline, 1978 (kkg) Table of Imports © - Nitroaniline (kkg) vi 212 2-35 2-17 2-36 2-37 2-38 2-39 2-40 aan 2-42 2-43 2-44 2-45 2-465.4 6.1 7a 7.2 8.2 8.3 a1 9.2 9.3 10.1 ‘Industrial Consumption of ortho-Nitroaniline Industrial Consumption of meta~Nitroaniline (kkg) Producers of pata-Nitroaniline by Year, Including Production Where Available Enissions of p - Nitroaniline During Synthesis Industrial Consumption of Pata-nitroaniline (kkg) Categories and Anounts of par Consumption 1974-78 (kkg/yr) nitroaniline pata-Nitroaniline Emissions Generated During Its Use Physical Properties of Nitroanilines Producers of Nitroanilines, 1974-1978 Imports of Nitroaniline Compounds 1974 to 1978 (ekg /yr) Physical Properties of Chloro- and Bromoanilines Imports of Chloro- and Bromoaniline Compounds 1974-1978 (kkg/yr) Consumption and Uses of Chloroanilines Locations of Emissions vid 6-6 7-4 7-6 7-10 9-6 9-5 10-2Figure Es-1 ES-2 B8-3 Es~6 Es-5 2a 2.2 2.3 5.1 61 Ma 91 LIST OF FIGURES Materials Balance for Aniline, 1978 Materials Balance for Aniline Hydrochloride, 1978 Materials Balence for ortho-Nitroaniline, 197 Materials Balance for neta-Nitroaniline, 1978 Materials Balance for para-Nitroaniline, 1978 Materials Balance for Aniline, 1978 Process Flow for Catalytic Vapor-phase Hydro- genation of Nitrobenzene Locations of Aniline Production Sites and Plant Capacities Materials Balance for Aniline Hydrochloride, 1978 Materials Balance for o-Nitroaniline Materials Balance for meta-Nitroaniline Materials Balance for para-Nitroaniline Locations of Nitroaniline Producers, 1978 Chloro- and Bromoaniline Production viii 2-4 2-5 3-2 5-2 o2 73 9-3EXECUTIVE SUMMARY ‘This Phase I materials balance reports on emissions due to production and use of several representatives of the class of anilines. The compounds desig- nated by the Task Order for study were the three isomeric nitroanilines, aniline hydrochloride, aniline hydrobromide, and a list of 38 other nitro-, chloro-, and bromoanilines, plus the parent compound, aniline. Of these compounds, no infor- mation was available on three (2,4,6-tribromoaniline hydrobromide, 2-bromo~4,6- @ichloroaniline, and 4-brono-3, 5-dichloroaniline) . The anilines studied were characterized as being solids at room tenperature with very low water solubilities and relatively low vapor pressures. The excep- tions to this generalization were aniline itself (a water-soluble liquid), o- and g-chloroaniline (Liquids), and all aniline salts (very water-soluble). Aniline Aniline is synthesized industrially by vapor-phase hydrogenation of nitro~ benzene. An estimated 279,000 kkg were produced in 1978, Generated emissions due to direct production were estimated to be 20 kkg to air and 0.08 - 5.6 kkg to water. Aniline was consumed by the following six categories of uses in 1978: isocyanate synthesis (148,000 kkg; 50% of total consumption), rubber chemicals (80,000 kkg; 27%), dyes and intermediates (17,800 kkg; 6%), hydro- quinone (14,800 kkg; 5%), drugs (8,900 kkg; 32), and miscellaneous uses (herbi- cides, fibers totalling 27,000 kkg; 9%). In addition a small anount of aniline hydrochloride was synthesized from aniline, Between 47% and 60% of aniline production was used captively, mostly for isocyanate synthesis. Inports and exports each contributed less than 1% to aniline availability and use, respect ively. Generated emissions due to aniline consumption (by category of use) were estimated to be: isocyanate synthesis, 19 kkg to air, 3,700 kkg to water; rubber chemicals, 20 kkg to air, 3,900 kkg to water; dyes and intermediates, 4 kg to air, 900 kkg to water; hydroquinone, 4 kkg to air, 700 kkg to water; drugs, 0 kkg to air, 85 kkg to water; and miscellaneous, 3 kkg to air, 680 kkg to water, These data are shown on the aniline materials balance, included here as Figure FS-1.Aniline Hydrochloride Aniline hydrochloride 1s the salt formed by neutralizing aniline base with ECL. Direct production data were not available from USITC or from the producers thenselves, so production was estimated on the basis of deductions and impress- fons gained from industrial sources to be 4.6 - 100 kkg/yr. Generated emissions due to production were estimated to be ~0 kkg to air and 4.6 - 100 x 10” *kkg to water. Imports and exports nade very snall contributions to production and con- sunption totals. Aniline hydrochloride was stated by an industry source to be used alnost exclusively in the dye industry. Based on information from these personal communications, enissions to water during dye production were estinated to be in the range 2.3 - 77 x 10” kkg aniline hydrochloride per year, Figure ES-2 is the materials balance for aniline hydrochloride. Aniline Hydrobromide Although it was judged that aniline hydrobromide was synthesized from aniline in a manner analogous to aniline hydrochloride, no information was available on production or consumption of aniline hydrobromide. ‘o-Nitroaniline g-Nitroaniline is synthesized by the annonolysis of o-chloronitrobenzene. A reported 3,641 kkg/year were produced in 1978. Generated emissions due to this production were estimated to be 69 kkg to water. It was not possible to estinate air emissions. -Nitroaniline has two major industrial uses; syn~ thesis of o-phenylenediamine and synthesis of dyes. No quantitative data were available so estimates of generated emissions from those consumption processes were not possible. Figure £8-3 displays the available information about o-nitroaniline, m-Nitroaniline m-Nitroaniline is synthesized by the partial reduction of n-dinitrobenzene. No production data were available, indicating the snaller industrial role played by m-nitroaniline relative to the ortho and para isomers. A rough est inate placed production in the range 0 - 2.3 kkg/yr. in 1978. 47 kkg were reportedas imports in 1978. Major uses for m-nitroaniline were as an intermediate in the synthesis of dyes, as photographic anti-fogging agents, and in coceidio- statics, interior paint pigments, and synthetic sweeteners. Quantitative con- sumption and use data were also unavailable. Lack of data in these areas pre- cluded estimation of reasonable emissions due to production and consumption processes. Refer to Figure ES-4 for the materials balance of n-nitroaniline. peNitroantline prNitroaniline is synthesized by the annonolysis of p-chloronitrobenzene. Te ds quantitatively the most important of the three nitroaniline isomers, with an estimated production in 1978 of 13,000 kkg. Generated emissions due to pro- duction were estimated to be 0.13 kkg to air and 117 kkg to water. p-Nitro- aniline was used chiefly in the rubber chemicals industry (6,000 kkg; 40z of total consumption). Other uses were dyes and intermediates (20%), gasoline additives (20%), pharmaceuticals and veterinary (7%), agricultural chenicals (1), and miscellaneous (10%). The X contributions were 1969 values, Generated emissions due to these uses were estimated to total 68 kkg to air and 600 kkg to water in 1978. These data are summarized on the materials balance for p-nitro- aniline, Figure ES-5. Other Nitroanilines The other anilines containing a nitro group (with or without other ring substituents) were considered as a group. No quantitative data were available on either production or use. Therefore, emissions could not be estimated. In general, these compounds were used predominantly by the dye industry, Chloro- and Bromoanilines As with nitroanilines, the halogenated anilines were considered as a group. No quantitative data were available, so emissions could not be estimated, These compounds seem to be used primarily by the dye industry. xdAll anilines were produced in the eastern half of the U.S., with the greatest concentrations of aniline capacity along the east coast and Gulf coast. ‘This report contains many best~judgement estimates of important numbers. Production and consumption data for nitroantlines, haloantlines, and aniline hydrochloride will be required for meaningful emissions estinates for these classes. Another key quantity that was missing was a documented aqueous waste stream analysis for an aniline production plant. These data will be necessary for more detailed analysis of aniline emissions. xiiES-1 —TATERTALS BALANCE FOR ANI LINE (exe) somes Gort 7 comantnanrs oF aad a “= wemparce a we es 148,000 a tis. ee wes Iepecte 4 v 0 7 19003920) == [as.00n,f pacominene $e on £ 5 eo sma = {earn pe F o + es Tescntide fr Ores — fyiecitortde 2 porte ae? 06 aio eto” 2 ne ee e100 1+ 10,008 10,00ES-2 1978 MATERIALS CALANCE FOR ANILINE HYDROCHLORIDE (exe) vTaaiNeNTALneAseS (ag) > vet cea one Peo esateee [= “0 ~o ~» ° T > -!BS—3 MATERIALS BALANCE FOR Q - NITROANILINE Cxxe) ' , , ,ES-4 MATERIALS CALANCE FOR m-SITROANILINE (xxo) consumer ve —- 1_Sounces 1 i n i Es il es S tomy mo ' : ' er 2» foves ino fonrannaas JMETA-NITRO- INTERMEDIATES. bina ~ Lo ~o vo [Lx syntaeric 2 ___} contaninants _ : + enoDge ox Ss 4 7 7 5 5 Tf anoregearnge |} feournnans — ; Ht vwromts [Po] O-pucnyene~ 1+} contantnants 1 1 + 1 1 Lo coccrpiastaris] —?— comtaminants, |————_________>. ee PA oven —? { conranmanrs > ee ee Loy) exports |}-——2-——=>} contaminants |} >ES- 5 ATERIALS BALANCE FOR e-NITROANILINE (xx) VINORTAL RELEASES (hb) : ' ' a wren ate oa 5 ty oe tL eonaninne > en on a I + 0 ~o a0 oe 2 coneasinants ~o ~o ~o ~o scnitronsiioe LE 100 . to Trotting SSS : . 7 7 [enais, a8 eancannante| a aa co ee EY ngorts send tees inary * [ooneanioancs ® « ’ grteaierad a et 5 ‘ : pss niseerianeoe contaminate + : CW________________, , : : : bere 2 _fepcainete + 9 ° . : cs 0 . °1,0 INTRODUCTION This report was prepared in response to a task order from the U.S. Environ- mental Protection Agency (EPA) for a Phase I materials balance study on anilines. ‘The study includes the compounds aniline, aniline hydrochloride, aniline hydrobromide, o-, m-, and p-nitroaniline, plus several other chloro-, brono-, and nitro- derivatives. The EPA was primarily concerned with possible sources of release to the environment and the anounts involved, since the compounds are highly toxic. These substances can be absorbed through skin, ingested, or inhaled (Hawley, 19775 TRW, 1973a). In order to present efficiently the data on many different but related com pounds, each compound being studied was the topic of a separate chapter. Within each chapter were sections on emissions due to production, consumption, and other processes, Tables and figures showing 1978 data were interspersed in the text, but data for other years were presented at the end of each chapter. In the tables reporting "releases" (emissions) data, the term "releases to soil" was defined as "material applied to the soil," as opposed to material ap- plied to a landfill. A landfill was interpreted as a form of waste storage rather than as a sink. The rationale was that anilines in solid form in a landfill are lost to water through leaching or to air through slow evaporation. These generalizations were particularly true of aniline itself. Thus, the lack of entries in a "releases to soil" colum only means that if aniline-containing solids were placed in a landfill, the anount of aniline present would have been apportioned to air and water to reflect long-term reality. On the other hand, actual "release to soil" would include use of pesticides, fertilizers, or other chemicals that would yield aniline due to microbial or photochemical degradation. Such releases would be tabulated as sources of aniline. Le2.0. ANILINE 2,1 PHYSICAL PROPERTIES ‘The compound aniline (aminobenzene) is the parent compound for many of the 40 anilines to be studied in this report, It is a liquid at room temperature. Its physical properties can be summarized as follows: (Hawley, 1977; Weast, 1977-78; Strecher, 1968): Hy Aniline Mol. We. 93.13 Melting point 6.2°C Boiling point 184.4°C Solubility in Cold #20 35 g/1 (0.38 M) Solubility in Boiling #20 64 g/1 (0.68 M) Temperature at which vapor pressure = 1 Torr 34.8 pKa 4.63 Of particular interest are aniline's water solubility and vapor pressure. Aniline 4s soluble even in cold water. Its vapor pressure is low compared, for instance, to toluene (1 Torr at -92°C) and benzene (1 Torr at -58°C). 2.2 MATERIALS BALANCE FOR ANILINE Figure 2.1 shows the materials balance for aniline, It demonstrates the sources of aniline (production, imports), the consumptive and non-consumpt ive uses of aniline (e.g., isocyanate production), and the estimated emissions to air, land, and water due to each process, This materials balance diagran is for the most recent year for which reasonably complete data are available: 1978. ‘The purpose of this chapter is to explain the assumptions and calcula~ tions that yielded the values reported in the figure. 21Froune 2.2 TATERIALS BALANCE FOR ABI LINE (xx) pent 1 T » 30 >m20 : twos Dees) “eens ee om = a Swe ca ere 21880 Torte re Es 9,000 300,000 L_ | 7 19,00 ,0002,3. DIRECT PRODUCTION OF ANILINE The processes by which aniline is produced were divided into direct (or plan ned) production and indirect production. This section discusses direct product- ion of aniline. 2.3.1 Production Processes, Producers, and Locations Aniline can be synthesized industrially by the vapor-phase reduction of nitro~ benzene or by ammonolysis of chlorobenzene (TRW Systems Group, 1973b). However, the Stanford Research Institute Chemical Economics Handbook (McCaleb, 1979) cites only the nitrobenzene reduction process as the current method of aniline synthesis. Therefore, it was assumed that at least 95% of aniline production takes place by the process: cat. 250 Nitrobenzene Aniline ‘The process flow for catalytic vapor-phase hydrogenation of nitrobenzene is in Figure 2.2 (Syracuse Research Corp., 1976), A more complete description of the process is found in Appendix A. The hydrogenation is carried out in the vapor phase (i.e., the temperature is greater than 211°C, the boiling point of nitrobenzene). ‘The locations of aniline production sites and each plant's capacity are shown in Figure 2.3. The seven production plants are all in the eastern half of the country, with two in New Jersey, two in West Virginia, and three on the Gulf Coast. 2-3FIGURE 2.2 CATALYTIC VAPOR-PHASE HYDROGENATION OF NITROBENZENE 1. Mivobenenesaporiser 11 Aniioe—vster ster and deca, . 2. Reslr wih lind cata t ba. 8 Cre ane sl 3. Cooling ten, 19. Reboter for endearing el 4 Gaus ers 20. Condenser S. Pretec rondo 6. Hrdeegen sory compresor ng 6, 13. Counter-current extraction epluan for antline-vater. 2.3.2 Amounts Produced Data were available on the production of aniline for the past several years. The anount of aniline produced in 1978 was estimated to be 279,000 kkg. This value vas selected from the data presented in Figure 2.3 on the basis of the following: 1) Partial USITC production data for 1979 showed that for the eight months from January through August, 1979, 195,416 kkg of aniline were produced. 2) The monthly production values showed no discernable trend, so annual production vas estimated by linear extrapolation of the 8-month production: (195,416 kkg/8 mo.) x (1.5) = 293,000 kkg/12 mos. predicted for 1979. 3) In order to estimate the 1978 production, equal growth rates were assumed for 1977-1978 and 1978-1979. ‘The estimated 1978 production was: (1977 production) + 1919 prod.) = (4977 prod.), estimated 1978 production = 265,000 + 285,990-265,000 = 279,000 kkg produced in 1978. ven though this value was based on estimated productions, it was 2hstill a more valid production value than the sum of plant capacities because it was bracketed by two production values. We estimated that the 1979 estimated production was within 10% of what the true yearly total will be. The uncertainty associated with the estimated 1978 production was estimated to be +202, based on possible variation in the 1979 production value and a possible deviance from the growth rate extrapolation between 1977 and 1979. As noted in the Remarks column, three production plants used their aniline captively, that is, the aniline was used as a feedstock for another process in the same plant. At least 177,000 kkg of capacity was dedicated to captive use in 1978. This was 47% of total capacity. On the basis of this, it was estimated that 47% of actual production was also used captively. The amount estimated to have been used captively was (279,000 kkg) x (0.47) = 132,000 kkg. Lowenheim and Moran (1975) estimated that, in general, about 60% of aniline production was used captively. USITC requires reporting of all aniline production greater than 2.3 kkg/year, whether it was captively used or not. As the MeCaleb (1979) estimate of 1980 production shows (Figure 2.3), @ sig- nificant increase in aniline production ts expected. This is due largely toa projected increase in use of aniline for isocyanate synthesis, Increases in the capacities of duPont's Beaumont, Texas, and Biggstow, New Jersey, plants; First Chemical's increase; and Rubicon's expasnion have been responses to this increased demand. 2.3.3 Emissions Due to Direct Production 2.3.3.1 Generated Emissions to Air Overall emissions of aniline to air during production were considered to be the sum of emissions due to the production process itself + those due to product storage + those due to product transport, Data on emission amounts were not readily available for any of these steps. We therefore estimated the anounts of generated emissions to air by using the following operation for each step: (kkg produced, stored, or transported) x (emission factor in kkg/kkg) = kkg re~ leased due to production, storage, or transport, The estimated emissions to air calculated by this process wer: 19 kkg/yr generated during production; L.1 kkg/yr generated due to storage; and 7 x 107 kkg/yr released during transport, The total generated enission due to direct production was 20 kkg in 1978. The emission factors used to estimate these amounts are summarized in Table 2.1. 2-6TABLE 2.1 EMESSION FACTORS FOR ANILINE RELEASE TO THE AIR DUE TO PRODUCTION PROCESS EMISSION FACTOR Production 6.9 x 10° kkg/kkg (generated emissions) Cleaning 2 Storage 4 x 107 kkg/kkg (generated emissions) Transport 7 x 107 kkg/kkg (actual enissions) Disposal, 1 Aniline can be released to the air during the following steps in the production process (see Figure 2.2 leaks at connections and pumps; carry- over at finishing still vent. The emissions factor for production was obtained from direct data on air emissions at the Beaumont, Texas, aniline plant of duPont. (Hydroscience, Inc., 1977.) We estimated its uncertainty to be 420% (their complete report is due at the end of December, 1979). In applying this emission factor to yearly production, we assumed the following: 1) All of the aniline produced in 1978 was synthesized by hydrogenation of nitrobenzene, 2) All plants carrying out this process have components and emission sources similar to those at the Beaumont plant. Emissions to air during production were estimated to b (279,000 kkg/yr) x (6.9 x 107? kkg/kkg) = 19 kkg/yr Taking {nto account the combined uncertainties of the production value and the emission factors, we estimated the uncertainty of the amount of emissions gen- erated to be 230%, 2-7The emission factor for storage was obtained from plant data by Hydroscience, Ine. (1977), We estimated its uncertainty to be +20%, In applying this enission factor to the anount of aniline stored, we assumed the following: 1) All aniline plants store the sane fraction of their product as the Beaumont, Texas, duPont plant for which the emission factor was estimated, The amount of enissions gen- erated due to storage was: (279,000 kkg) x (4 x 1076 kkg/kkg) © 1.1 kkg of generated emissions to air due to storage in 1978. ‘The emission factor for losses due to transport was 7 x 10° kkg/kkg. It was estimated by using a nodel a study of spill/release risk in the petroleum “ Andustry (U.S. Coast Guard, 1973-1976; U.S. Army Corps of Engineers, 1973-1976; Science Applications, Inc., 19775 Sclence Applications, Inc., 19783 U.S. Depart= ment of Energy, 1978). The bases for this application were: 1) The modes of transportation for ofl and aniline were basically the sane (pipes, barrels, tank cars). 2) The petroleum industry studies cited above predicted that approximately 7 x 10° of the total product moved would be lost during transport and handling. 3) This loss was estimated to be divided 10% to air and 90% to water because of aniline’s low vapor pressure, moderate solubility in water, and the likelihood that most spills would be cleaned up by hosing down the area before significant evaporation occurred. 4) The anount of aniline transported was zero for plants that used the aniline captively. Therefore, this anount of production was sub- tracted from the total in order to get the amount of aniline transported: 279,000 kkg produced ~ 132,000 kkg used captively = 147,000 kkg transported. The anount of enissions released to air due to transport of domestic aniline was: (147,000 kkg transported) x (7 x 107° kkg/kkg) x (0.10 fraction to air) = 1 x 107? kkg/year. 2.3.2.2 Generated Emissions to Water Overall emissions of aniline to water during production were considered to be the sum of emissions due to the production process itself plus those due to product transport. Data on emission amounts during these processes were un- available. However, emission factors were available for each category, and these were used to estimate respective emissions. The estimated emissions to water were: 0,08 - 5.6 kkg/year generated by the production process; and 1x 107 kkg/yr released during transport. The sum of these contributions was 0.09 ~ 5.6 kkg generated during aniline direct production for release to water during 1978. 2-8In each case, the following operation was applied: (kkg produced or trans~ ported) x (emission factor in kkg/kkg) = kkg of emissions generated or released. Aniline may be released to water at the following points during its produc~ tion by hydrogenation of nitrobenzene (see Figure 2.2): Leaks at connections and pumps, purge valve of crude aniline still, condensate of final water boil~ off in finishing still, waste water from extraction column. In the absence of direct data on water emissions, an estimate was derived from an estimated emission factor of 3 x 107° kkg/kkg. This value vas based on the following: 1) MITRE Corp. (1978) edtes the following data reported by two aniline manu facturers: Aniline release into the raw waste stream averaged 0.067 kg/kkg product. The range was 0,005 ~ 0.49 kg/kkg product, but there was no indication of the nunber of samplings included or who the manufacturers were. 2) This generated release factor vould be lowered by effluent treatment. We estimated that 95% of aniline would be renoved. 3) The discharged water, therefore, contained (6.7 x 10> kkg/kkg product) x (0.05 fraction not removed = 3 x 10 kkg/ikg product. This was the average emission factor for actual releases to water. The range of emission factors was 3x 107? - 2 x 107 kkg/kkg produced. Application of these emission factors to the estination of eaissions ytelded: (279,000 kkg produced) x (3 x 10° kkg/kkg produced) = 0.84 kkg released to water due to aniline production in 1978. The range of values, calculated in the same way, was 0.08 ~ 5.6 kkg released. ‘The emission estimates spanned a range of 70-fold. ‘The uncertainties of the minimum and maximum values were unknown. Statistical information on the effluent analyses that were the bases for the emission factors might be found in EPA Organics and Plastics (1976), 308, Response BPR Master the primary soure File Listing. Because of the importance of this estinated emission to water, it should be checked for credibility by the following steps: 1) Probably the major source of aniline enissions to water is the wastevater effluent from the extraction column (process 13 in Figure 2.2), 2) The influent contains water saturated with aniline; therefore, the aniline concentration is approximately the physical Limit: 35 g/1 or 129 g/gal. 3) Assune the efficiency of the extraction columnis 98% (Appendix A). 4) Obtain the yearly production of one or more plants. 5) Obtain the flow rates of effluent water from the respective extraction columns. 6) Calculate the enission factor for generated emissions (1.0. before treatment) in this waste stream by the operation: (129 x 107° kkg/gal influent) x (0.02 fraction in waste stream) x (annual waste stream volumes, gal) + (annual production, kkg) = emission factor, kkg/kkg product. 7) Comparison of the value with the reported emission factor [avg. 6.7 x 107 kkg/kkg product tn overall raw Yoad (MITRE Corp., 1978} would perait roush evaluation of con sistency or inconsistency between the two emission factors. Anilines may also be released to vater during transport. No data were readily available on water enissions during transport. Therefore, the water emissions due to transport of aniline were estinated by the operation: (kkg aniline transported) x (emission factor, kkg released per kkg transported). The amount of emissions estimated by this procedure was 9 x 107? kkg/yr. The emission factor used to obtain this estinate was 6.3 x 10° kkg/kkg transported. It was estimated by using as a model a study of spill/release risk in the petroleum industry (U.S. Coast Guard, 1973-1976; U.S. Army Corps of Engineers, 1973-1976; Science Applications, Ine., 19775 Setence Applications, Inc., 19785 U.S. Department of Energy, 1978). The bases for this application were: 1) The modes of transportation for ofl and aniline vere basically the same (pipes, barrels, tank cars). 2) The petroleum industry studies cited above predicted that approximately 7 x 10°°% of the total product moved would be lost during transport and handling. 3) This loss was estimated to be divided 10% to air and 90% to water because of aniline's low vapor pressure, moderate solubility in water, and the likelihood that most spills would be cleaned up by hosing down the area before significant evaporation occurred. 4) The amount of aniline transported was zero for plants that used the aniline captively. Therefore, this anount of production was subtracted from the total in order to get the anount of aniline transported: 279,000 kkg produced ~ 132,000 kkg used captively = 147,000 kkg transported. The amount of emissions released to water during transport of domestic aniline was (147,000 kkg transported) x (7 x 10% kkg/kkg) x (0.9 fraction to water) = 9 x 107? kkg/yr. This value was a low-side estimate because aniline is less vicous than ofl and would therefore leak and spill more rapidly. We estimated the uncertainty for the release of aniline to water during transport to be +500%, -50%Z.2.3.3.3 Emissions Due to Disposal of Solid Residues Solid residue containing aniline could be produced at the following points in the flow schene (Figure 2.2): walls of reactor; condenser surfaces; traps at bottom of crude and finished aniline stills; sludge from wastevater treat- ment. We estimated that these residues would contain negligible aniline. This was based on the following: 1) The solids were Itkely to be polymers and con- densation products of aniline and/or nitrobenzene. Aniline would be a vapor or a liquid at operating temperatures. 2) Mechanically included aniline vould be washed out of the residues by the gas or liquid flows across the residue, In order to better evaluate the possibility of emissions in aniline containing solids, the following are needed: 1) More detailed information on the production process (the nature of the trapped materials and other residues; 2) chemical analysis of residues; 3) rate of removal of residues; 4) methods of treatment for water wastes and solid residues. 2.4 INDIRECT PRODUCTION 2.4.1 Degradation of Products Derived from Anilines Several of the compounds produced from anilines have the potential to yield anilines back by a simple reaction (usually either hydrolysis or oxidation). Examples would be hydrolysis of acetanilide or hydrolysis of phenyl isocyanates. Hydrolysis of even 0.01% of the 148,000 kkg of phenyl isocyanates produced in 1978 (see Table 2.4) would yield almost 15 kkg of aniline release. This possibility could be evaluated by studies on the rate of degradation of these compounds and their end-products. 2.4.2 Petroleum Industry, The following references in Chemical Abstracts might serve as a starting point for analysis in this area: (a) C.A. 89, abstract 149248g (1978), aniline 4n coal liquefaction products; (b) C.A. 89, abstract 113699r (1978), aniline in tar from underground coal gasification; (c) C.A. 89, abstract 484200 (1978), aniline in astewater from coal gasification.2.4.3 Automobile Exhaust Phone conversations with EPA mobile emissions chemists lead to the sugges- tion that anilines are present at trace levels in automobile exhaust. Upper bounds on releases could be obtained from the operation: (detectability limit tn ppb) x (kkg exhaust/yr.). This contribution (if any) may change as fuel con sumption patterns change to synthetic or modified fuels with different nitrogen contents. 2.4.4 Hydrolysis of Acetanilide Acetanilide is described as a "very widely used over-the-counter analgesic’ (Casarett and Doull, 1975), One of its minor reactions in vivo is deacetylation to produce aniline (Casarett and Doull, 1975). By using annual consumption Figures for acetanilide analgesics and biochemical data on proportion hydrolyzed or rate of hydrolysis, the anount of excreted anfline could be evaluated. 2.5. IMPORTS OF ANILINE 2.5.1 Amounts ‘The amounts of aniline imported were available in USITC publications for four of the last five years. Less than 1 kkg had been imported between January and August, 1978, Based on this, we estimated that 1 kkg of aniline was imported in 1978, The uncertainty of this value was estimated to be +50%, -25%. The other values available are presented in Table 2.2, TABLE 2.2 IMPORTS OF ANILINE (kkg/year) 1978 1977 1976 1975 1974 iu nr. are 6288 9214 1 For the months January through August, 1978 (M%cCaleb, 1979). SOURCE: USITC, n.r. = not reported‘The amount of aniline imported was variable, but was generally a small fraction of total production. The 1974 value, which was higher because of a domestic petroleum shortage due to the oil enbargo, was 3.6% of production that year. 2.5.2 Emissions Due to Imports 2.5.2.1 Emissions to Air Aniline can be released to the air during the storage and transport of imported aniline. These enissions are due to spills, leaks, and evaporation during transfer between containers. No data were avatlable on the anounts of aniline lost to the air in these ways, We estimated that the emissions of aniline to the air during importing procedures was 4 x 10° kkg in 1978. This value was obtained by summing the contribution of enissions during transportation and handling (7 x 10” x 10° keg/year). kkg/year) and the contribution of storage losses, The emission factor used to estimate the emissions due to transportation and handling was 7 x 10 a study of spill/release risk in the petroleum industry (U.S. Coast Guard, 1973-19765 U.S. Corps of Engineers, 1973-1976; Science Applications, Inc., 19775 Science Applications, Inc, 1978; U.S. Department of Energy, 1978). The bases for this application were: aniline were basically the sane (pipes, barrels, tank cars), 2) The petroleum kkg/kkg imported. It was estimated by using as a model 1) The modes of transportation for of1 and industry studies cited above predicted that approximately 7 x 10°z of the total product moved would be lost during transport and handling, 3) This loss was estimated to be divided 10% to air and 90% to water because of aniline’s low vapor pressure, moderate solubility in water, and the probability that most spills would be cleaned by hosing down the area before significant evaporation occurs. The emission factor estinated for release of aniline to air during transport and handling was (7 x 1078) x (0,10) = 7 x 107 kkg/kkg. Application of this emission factor to the amount of aniline imported in 1978 yielded: (1 kkg) x (7 x 1079 kekg/kkg) = 7x 107 kkg emitted to air during transport and handling of imports. This estinate represented 2 lov-side value because aniline is significantly less viscous than of1 and would therefore leak nore rapidly than oil. We estinated the uncertainty of aniline emission at +500%, -50%. 2-13The enission factor used to estimate emissions to air during storage was 4 x 107° kkg/kkg stored, This factor was estimated by Hydroscience, Inc. (1977). Pending an uncertainty estimate by the authors (their report is expected by the end of December, 1979), we estimated the uncertainty of the enission factor to be £202. In applying this emission factor to the estimation of aniline released to air during storage, we used the following basis: 1) The storage of imported aniline used the sane equipment and procedures as the storage of donestic aniline, The amount of emissions to air due to storage of imported aniline was: (1 kkg) x (4 10° kkg/kkg stored) = 4x 107° kkg. Based on the uncertainties of the production data and the emission factor, the estimated uncertainty of the amount emitted during storage was +702, -45%. 2.5.2.2 Emissions To Water Emissions to water can occur during storage and transport of imported aniline. These releases are due to spills and leaks during transfer between containers. No data were available on emissions of aniline to water by these routes. It was estimated that the emissions of aniline to water during transport of imported aniline were 6.3 x 107° kkg in 1978, The enission factor used to estimate the enissions due to transport was 6.3 x 107° keg/kkg transported. This value was estimated by using as a model a study of spill/release risk in the petroleum industry (U.S. Coast Guard, 1973- 19765 U.S. Arny Corps of Engineers, 1973-1976; Science Applications, Inc., 19775 Science Applications, Inc., 1978; U.S. Department of Energy, 1978). The bases for this application were: 1) The modes of transportation for ofl and aniline are basically the same (pipe, barrels, tank cars). 1) The petroleum industry studies cited above predicted that approximately 7 x 10°6z of the total product moved would be lost during transport and handling. 3) This loss was estimated to be divided 10% to air and 90% to water because of aniline's lov vapor pressure, noderate water solubility, and the likelihood that most spills would be cleaned up by hosing don the area before significant evaporation occurred. The anount of emissions to water during transport of imported anfline was: (1 kkg) x (7 x 1078 kkg/kkg) x (0.9 fraction to water) = 6.3 x 107 kkg. This value was a lov- side estimate because aniline is less viscous than ofl and vould therefore leak and spill aore rapidly. We estinated the uncertainty for the release of inported aniline to water during transport to be +500%, -50%.2.5.2.3 Emissions Due to Disposal of Solid Residues It was estimated that the anount of solid residues accumulated as a result of aniline import was negligible, and that the release of aniline due to disposal of solid residues was zero. 2.5.3 Summary Table Table 2.3 (end of chapter) summarizes the estinated emissions for years other than 1978, No import data were available for 1976, 2.6 CONSUMPTION AND USE OF ANILINE Aniline 1s used in industry for the production of a variety of chemical substances. In all cases, it is a chemical intermediate (the starting point for further synthesis) rather than an end product itself. In general, there are three areas to exanine for aniline emissions: 1) direct enissions during consumptive use, 2) carry-over as impurities in manufactured products, and 3) indirect emissions due to degradation of sanufactured products. 2.6.1 Total Consumption Data were available on the percentage of aniline production that was used in each of six major categories of use. In addition, the amount (kkg) of consumption by some categories was available. This permitted calculation of total consumption by the operation: (kkg used by a category) + (fraction of total used by that category) = total consumption (kg). The total con sumption of aniline in 1978 was 296,000 kkg, based on the fact that the 148,000 kkg consumed in isocyanate synthesis represented 50% of total con sumption (Chemical Marketing Reporter, 1979). The total consumption value estimated in this way is in parentheses in Figure 2.1, Above it is the amount of total available aniline. This amount was obtained by the process: (domestic production) - (emissions) - (exports) + (imports) = kkg aniline available for use. Possible explanations for the difference between the nunbers (276,000 kkg available vs. 296,000 kkg consumed) are: 1) underestimation of imports, 2) overestimation of exports, 3) simple statistical variance: a change in the % contribution of isocyanate synthesis from 50% to 51% would lover the total aniline consumption by 6,000 kkg.2.6.2 Categories of Use The categories of aniline use, consuming companies, and anounts used for the past five years are presented in Table 2.4, The data were obtained from the footnoted references; we had no criterion on which to base an uncertainty estimate, Isocyanate synthesis was the largest use category, and the trend was toward increasing aniline use by this category. Increases in isocyanate synthesis accounted for most of the increase in total aniline consumption over the past five years. 2.6.3 Use Within Bach Category Tables 2.5 - 2.9 (end of chapter) provide a further breakdown of aniline use within the major categories. In the absence of direct data on use within each category, we estimated the breakdowns shown in the tables based on quali~ tative statements made in the chemical marketing literature. These estimates are described in the footnotes to the tables. Since emissions were calculated only for the major use categories, uncertainities in the breakdown percentages did not affect the emissions estimates. ‘An even more detailed listing of the derivatives of aniline, how they were produced, and how they were used is found in Appendix B. 2.6.4 Emissions by Category of Use 2.6.4.1 Emissions Due to Isocyanate Synthesis Isocyanates can be formed by the reaction of amines with phosgene, Cl, Aniline is used to synthesize the bifunctional isocyanate p, p' = methylene-bis (phenylisocyanate), MDI. The reaction sequence is (WcCaleb, 1979): ora. a a . orc=n Neceo 2-16ue TABLE 2.4 INDUSTRIAL CONSUMPTION OF ANILINE, 1974-1978 (kkg/yr) Category of % of Anili 1 5 Use Consumption’ Company Product Classes Year Amount Used (kkg) isocyanate 50% Mobay Chemical polymeric isocyanates 1979 148,000 synthesis Corp. urethane foams : Rubicon Chemicals, 197 132, 000° Inc. Upjohn Co. 1976 101,000° Jefferson Chemical Co. 1975 78,000° 1974 97,0008 Preparation 1978 80,0007 of rubber accelerators chemicals 27% American Cyanamtd antioxidants 197 83,000" Co. antiozanants e 1976 84,000 1975 65,000° 1974 90,0008 manufacture 6x American Cyanamid dyes and dye 1978 18,000 of dyes co. intermediates . 1977 13, 000 1976 14, 000° 1975 11, 000° 1974 15, 000°el-z TABLE 2.4 INDUSTRIAL CONSUMPTION OF ANLINE, 1974-1978 (continued) Category of X of Aniline 1 Use Consumption Company Product classes Year Amount Used _(kka) hydroquinone st Tennessee Eastnan Co. antioxidants 1978 15,000? production photodevelopers 7 1977 13,000 1976 12, 000° 1975 9,000° 197% 15,0008 drug manufacture 3% sulfa drugs 1978 9,007 1977 8, 0004 1976 7,008 1975 6,000° 197% 10,000° miscellaneous 9% fibers 1978 27,0007 (herbicides and herbicides : (Ethers) other 1977 13, 000! 1976 22,000° 1975 17,000° 1974 22,0008Footnotes (Table 2.4) Partial list of larger users, Source: McCaleb, 1979. 2. Chemical Marketing Reporter, 1979 3. Hahn, 1970. Chemical Purchasing, 1977. 5. Chemical Marketing Reporter, 1976. 6. Chemical and Engineering News, 1974. 2-19MOI polymerizes to form polyurethanes. 2.6.4.1.1 Emission to Air Direct data were not readily available on aniline emissions to air during Jeocyanate synthesis. A best-judgenent estimate was made on aniline emissions during this process. ‘The estimated anount of generated aniline emissions to air during MDI synthesis in 1978 was 19 kkg. This value was obtained in the absence of data on emission factors during MDI synthesis by using the estinated emission factor 1,25 x 107% kkg/kkg aniline consumed. The bases for estimating this emission factor were: 1) Only the first (anf{line-consuming) step in YOT synthesis was considered. 2) As with many industrial reactions, the yield in the first step was considered to be 95%. 3) Of the unreacted 5% of input aniline, 50% was recovered for re-use. 4) The renaining 2.5% of input aniline was released 0.5 part to air, 99.5 parts to water--consistent with aniline's physical properties, The emission factor obtained was: (0.05 fraction of aniline unreacted) x (0.5 fraction of unreacted not recovered) x (0.005 fraction to air) = 1.25 x 10™ kkg/kkg. We estimated the uncertainty of this release to be +5002, -80% based on the following: 4) The estimated emission would be an over-estimate if the synthesis processes were wore efficient than the estimates used. 2) The allotment of total losses to air and water could be as much as 5~ fold off in either direction. 2.6.4.1.2 Emissions to Water Direct data were not readily available on aniline enissions to vater during MDI synthesis. A best-judgenent estimate vas made of aniline enissions during this process. The estimated anount of generated aniline emissions to water during isocyanate synthesis in 1978 was 3700 kkg. This value was obtained in the absense of data on emission factors during MDI synthesis by using the estimated emission factor 2.5 x 107 kkg/kkg aniline used. The basis for estimating this enission factor was given in section 2.6.4.1.1. It was calculated as follows: (0.05 fraction of unused aniline) x (0.5 fraction of unused aniline not recovered) x (0,995 fraction of unrecovered aniline in water stream) = 2.5 x 107? kkg/kkg. The amount of aniline emissions generated was (148,000 kkg consumed) x (2.5 x 107 ickg/kkg) = 3700 kkg aniline enissions to water generated due to isocyanate synthesis in 1978. 2-20Based on the reasoning described in section 2.6.4.1,1, the uncertainty of this emission value was estimated to be +5002, -80%. 2.6.4.1.3 Emissions Due to Disposal of Solid Residues No direct data nor data on emission factors was available to permit estimation of emissions due to disposal of solid, aniline-containing residues formed during isocyanate synthesis. In order to be able to estimate enissions to air, land, and water due to this disposal, the following information would be needed: 1) process engineering information on the sources of residues during isocyanate synthesis; 2) quantitative analysis of the residues produced; 3) information on waste disposal methods at each plant (i.e., landfill, incineration, activated sludge treatment, stack gas scrubbers, etc.). 2.6.4.1. Carry-over of Aniline as Impurities in Products No data were available to permit estimation of aniline emissions due to aniline impurities in isocyanates or polyurethanes derived from them. In order to estimate these emissions, the following information would be needed: 1) proprietary information on chemical analyses of the two predominant isocyanates manufacture 2) chemical analyses of consuner goods containing aniline-based polyurethanes; 3) production data on the isocyanates and polymers involved. 2,6.4.1.5 Summary of Aniline Emissions Due to Isocyanate Synthesis Table 2.10 (end of chapter) summarizes estimated emissions to air and water generated during isocyanate synthesis for the years 1974-1978. The table also breaks down total emissions into those due to MDI production and those due to polymethylene polyphenyldiisocyanate synthesis according to the estimated percent contribution shown in Table 2.5. 2.6.4.2 Emissions Due to Rubber Chemical Synthesis Rubber chemicals synthesis utilized an estimated 80,000 kkg of aniline in 1978, This was 27% of total aniline usage (Table 2.4). Specific compounds and process flow schemes were not available for this category. Therefore, of rubber chenicals enissions were estimated for the generalized "proces: production by the operation: (kkg aniline consumed) x (emission factor, kkg emissions/kkg aniline consumed) = kkg total generated enissions. 2-21In the absence of data on either amounts of emissions or experimentally- determined emission factors, an overall best-judgement emission factor for generated emissions due to rubbet chemicals synthesis was estimated. The value estimated was 5 x 10 kkg/kkg. This enission factor was for the sum of generated air emissions + generated water emissions. It was based on the following considerations: 1) In any chemical-synthesizing process, only the first (1.e., aniline-consuming) step was of interest. 2) On the average, this first reaction would utilize 90% of the aniline feedstock. 3) Of the remaining 10% of input aniline, half was reclaimed and recycled. 4) The generated emissions of aniline were therefore 0.05 (or 5%) of aniline consumed: (0.10 fraction not used) x (0.50 fraction of unused not reclaimed) = 0.05 kkg generated/kkg aniline used. 2.6.4.2.1 Generated Emissions to Air In the absence of data on air emissions or enission factors during rubber chemical synthesis, we used the estimated emission factor above (5 x 10 kkg/kks) to estimate the generated emissions to air during this process. The additional assumption required vas: 1) Total generated enissions were distributed 0.5 part (80,000 keke, aniline used) x (5 x 10 kkg/kkg used) x (0.005 fraction to air) = 20 kkg generated for release to air during rubber chemicals production in 1978, to air and 99.5 parts to water. The estimated emissions wer ‘The uncertainty of this value was estimated to be +5002, ~80%, based on the analysis presented in section 2.6.4.1.1, 2,6.4.2,2 Generated Emissions to Water The method of estimating generated emissions to water during rubber chemical synthesis was the one described in section 2.6.4.2.1 (above) with the following exception: since 99.5% of total emissions were estimated to enter water waste, the value 0.995 replaces 0.005 in the calculation. The estimated emissions were: (80,000 kig aniline used) x (5 x 10” kkg/kkg used) x (0.995 fraction to water) = 4000 kkg generated for release to water during rubber chemicals production in 1978, The uncertainty is estimated to be +5002, -80% (see section 2.6.4.1.1). 2-222.6.4.2.3 Emissions Due to Disposal of Solid Residues No direct data nor data on emission factors were available to permit estimation of emissions due to disposal of solid, aniline-containing residues formed during rubber chenicals synthesis. In order to be able to estinate emissions to air, land, and water due to this disposal, the following information would be needed: 1) process engineering information on the sources of residues during specific synthesis steps utilizing aniline as a feedstock; 2) data on the percent contributions of the individual processes to the total for the rubber chemicals category; 3) quantitative analysis of residues produced; 4) rate of production of residues; 5) information on waste disposal methods at each plant (i.e., landfill, incineration, activated sludge treatment, stack gas scrubbers, etc.). 2.6.4.2.4 Carry-over of Aniline as Impurities in Products No data were available to permit estimation of aniline emissions due to aniline impurities in rubber chemicals. In order to estimate these emissions, the following information would be needed: 1) identities and anounts of rubber chemicals derived from aniline; 2) chemical analyses of these rubber chemical batches. 2,6.4.2.5 Summary of Aniline Emissions Due to Rubber Chemicals Synthesis Table 2.11 (end of chapter) summarizes estimated emissions to air and water generated during rubber chemicals synthesis for the years 1974-1978, The table also breaks down total emissions into subcategories: accelerators, antioxidants, antiozonants, and curing agents by using the estimated percent contributions shown in Table 2.6 2.6.4.3 Emissions Due to Manufacture of Dyes and Dye Intermediates Dye and dye intermediate synthesis consumed an estimated 18,000 kkg of aniline in 1978, This was 6% of total aniline usage (Table 2.4). Specific products and process flow schemes were not available for this category. Therefore, emissions were estimated for the generalized "process" of dye and dye intermediate synthesis by the operation: (kkg aniline consumed) x (emission factor, kkg emissions/kkg aniline consumed) = kkg total generated emissions. 2-23In the absence of data on either anounts of emissions or experimentally- determined emission factors, an overall best-judgement emission factor for generated emissions due to dye synthesis was estinated. The value estimated vas 5x 107 kkg/kkg. This emission factor was for the sum of generated air emissions + generated water emissions. It was based on the following con- siderations: 1) In any chemical-synthesizing process, only the first (1.e., aniline-consuming) step was of interest. 2) On the average, this first reaction would utilize 90% of the aniline feedstock. 3) Of the remaining 10% of input aniline, half was reclaimed and recycled. 4) The generated emissions of aniline were therefore 0.05 (of 5t) of aniline consumed: (0,10 fraction not used) x (0.05 fraction of unused not reclaimed) = 0.05 kkg generated/kkg aniline used. 2.6.4.3.1 Generated Emissions to Air Im the absence of data on air emissions or enission factors during dye synthesis, we used the estimated emission factor above (5 x 107 kkg/kkg) to estimate the generated emission to air during this process. The additional assunption required was: 1) Total generated emissions were distributed 0.5 part to air and 99.5 parts to water. The estimated emissions were: (17,800 kkg aniline used) x (5 x 107 kkg/kkg used) x (0.005 fraction to air) = 4 kkg generated for release to air during dye production in 1978. The uncertaintiy of this value was estimated to be +5002, -80%, based on the analysis presented in section 2.6.4.1.1. 2.6.4.3.2 Generated Emissions to Water The method of estimating generated emissions to water during dye synthesis was the one described in section 2.6.4.3.1 (above) with the following exception: since 99.5% of total emissions were estimated to enter water waste, the value 0.995 replaced 0.005 in the calculation. The estimated emissions were: (17,800 kkg aniline used) x (5 x 107 kkg/kkg used) x (0.995 fraction to water) = 900 kkg generated for release to water during dye production in 1978, The uncertainty was estimated to be +500%, -80% (see section 2.6.4.1.1). 2-242.6.4.3.3 Emissions Due to Disposal of Solid Residues No direct data nor data on emission factors were available to permit estimation of emissions due to disposal of solid, aniline-containing residues formed during dye synthesis. In order to be able to estimate emissions to air, land, and water due to this disposal, the following information would be needed: 1) process engineering information on the sources of residues during specific synthesis steps utilizing aniline as a feedstock; 2) data on the percent contributions of the individual processes to the total for the dyes category; 3) quantitative analysis of residues produced; 4) rate of pro- duction of residues; 5) information on waste disposal methods at each plant (4.e., landfill, incineration, activated sludge treatment, stack gas scrubbers, ete.). 2.6.4.3.4 Carry-Over of Aniline as Impurities in Products No data were available to permit estimation of aniline emissions due to aniline impurities in dyes and dye intermediates. In order to estimate these emissions, the following information would be needed: 1) identities and amounts of dye chemicals derived from antline; 2) chemical analyses of these dye chemical batches. 2.6.4.3.5 Summary of Aniline Emissions Due to Dye and Dye Intermediate Synthesis Table 2,12 (end of chapter) summarizes estimated emissions to air and water generated during dye chemical synthesis for the years 1974-1978. The table also breaks down total emissions into subcategories: azoic, indigotd, stilbene, and triarylmethane dyes, and pre-dye treatments by using the estimated percent contributions shown in Table 2.7. 2.6.4.4 Emissions Due to Hydroquinone Production liydroquinone synthesis consumed an estimated 15,000 kkg of aniline in 1978, This was 5% of total aniline usage (Table 2.4). Hydroquinone is produced from aniline in a two-step process (Kirk-Othmer, 1968): the first step is the oxidation of aniline to quinone and the second step is the 2-25reduction of quinone to hydroquinone, Further production details were not available. Therefore, emissions vere estimated by the operation: (kkg aniline used) x (emission factor, kkg emission/kkg aniline used) = kkg total generated emissions. In the absence of data on either anounts of enissions or experinentally- determined emission factors, a best-judgenent emission factor for generated emissions die to hydroquinone production was estimated. The value estinated was 5 x 107 kkg/kkg. ‘This emission factor was for the sum of generated air emissions + generated water enissions, It was based on the following con~ siderations: 1) In the two-step process aentioned above, the an{line-oxidizing step was Judged to utilize 90% of aniline input, 2) Of the renaining 10% of aniline feedstock, half was reclained and recycled. 3) The generated emissions of aniline vere therefore 0.05 (52) of aniline consumed: (0.10 fraction not used) x (0.50 fraction of unused not reclained) = 0.05 kkg generated/kkg aniline used. 2.6.4.4.1 Generated Emissions to Air In the absence of data on air emissions or emission factors during hydroquinone synthesis, ve used the estimated emission factor above (5 x 10) kkg/kkg) to estimate the generated emissions to air during this process. The additional assumption required was: 1) Total generated emissions were distributed 0.5 part to air and 99.5 parts to water. The estimated emissions ver (14,800 kkg aniline used) x (5 x 10™ Kkg/kkg used) x (0.005 fraction to air) = 4 kkg generation for release to air during hydroquinone production in 1978, The uncertainty of this value was estimated to be +500%, -80%, based on the analysis presented in section 2.6.4.1. 1. 2.6.4.4.2 Generated Emissions to Water The method of estimating generated emissions to water during hydro~ quinone synthesis was the one described in section 2.6.4.4.1 (above) with the following exception: since 99.5% of total emissions are estimated to enter water waste, the value 0.995 replaces 0.005 in the calculation, The estimated 2-26(14,800 kkg aniline used) x (5 x 107? kkg/kkg used) x (0.995 fraction to water) = 700 kkg generated for release to water during hydroquinone production in 1978, The uncertainty is estimated to be +500%, -80% (see section 2.6.4.1.1). emissions were: 2.6.4.4.3 Emissions Due to Disposal of Solid Residues No direct data nor data on emission factors were available to permit estimation of emissions due to disposal of solid, aniline-containing residues formed during hydroquinone synthesis. In order to be able to estimate emissions to air, land, and water due to this disposal, the following information would be needed: 1) process engineering information on the sources of residues during the synthesis step utilizing aniline as a feedstock; 2) quantitative analysis of residues produced; 3) rate of production of residues; 4) information on waste disposal methods at each plant (1.e., landfill, incineration, activated sludge treatment, stack gas scrubbers, etc.). 2.6.4-4.4 Carry-Over of Aniline as Impurities in Products No data were available to permit estimation of aniline emissions due to aniline impurities in hydroquinone. In order to estimate these emissions, the following information would be needed: 1) chemical analyses of hydroquinone batches. 2.6.4.4.5 Summary of Aniline Emissions Due to Hydroquinone Synthesis Table 2.13 (end of chapter) summarizes estimated emissions to air and water generated during hydroquinone synthesis for the years 1974-1978. 2.6.4.5 Emissions Due to Drug Manufacture Drug manufacture utilized an estimated 8900 kkg of aniline in 1978. ‘This vas 3% of total aniline usage (Table 2.4). With the exception of acetanilide synthesis, specific compounds and process flow schenes were not available for this category. Therefore, emissions vere estimated for the generalized "process" of drug manufacture, excluding acetanilide-based drugs. In both 2-27cases, the estimation was obtained by the operation: (kg aniline consuned) x (emission factor, kkg enissions/kkg aniline consuned) = kkg total generated emission: Im the absence of data on eithet anounts of emissions or experimental ly- derived emission factors, an overall best-judgenent emission factor for generated emissions due to non-acetanilide-based drug synthesis was estimated. The value estimated vas 9 x 10°? kkg/kkg. This emission factor was for the sun of air emissions + water emissions. It was based on the following considerations: 1) Only the first (aniline-consuming) step in a multi-step drug synthesis was of interest. 2) In the drug industry, purity of product would be more important than recovery of yield. Therefore, the eniline~ derivatizing reaction would be run in such a way as to minimize unused aniline accompanying the product. We estimated that 1% unused aniline vas possible. 3) Of this 1% of input, ali but 0.1% would be removed by subsequent puri- fications and enitted to waste streans, 4) The estimated overall enission factor was therefore (0.01 fraction of aniline unused) x (0.9 fraction of unused emitted) = 9 x 10> kkg/kkg aniline used. ‘The emission factor for acetanilide-based drug synthesis was estimated to be 1 x 107 kkg/kkg. ‘This emission factor was for the sum of air emissions + water emissions. It as based on the following considerations: 1) Acetani~ lide synthesis would be made to use at least 99% of input aniline. 2) Analysis of technical grade acetanilide showed 0.2% aniline carryover (Kirk-Othmer, 1968). This corresponds to (0.2%) x ( a ) = 0.3% of input aniline (135 and 93 are the respective molecular weights of acetanilide and aniline). 3) Therefore, 0.7% of input aniline was emitted to water and air, 4) The 0.3% input aniline occurring as an impurity in technical grade acetanilide vas renoved during production of USP acetanilide, which contained no aniline (Kirk-Othmer, 1968). Tt was tabulated as an additional emission, The estimated overall emission factor was 1 x 10™* kkg/kkg aniline used. 2.6.4.5.1 Emissions to Air It was estimated that emissions to air were negligible during drug synthesis. This was because we judged that: 1) each aniline-derivatizing reaction would 2-28take place efficiently in aqueous solution, and 2) purification of drug intermediates often would involve crystallization of the desired compound and discarding of the separated impurities in the aqueous nother liquor. 2.6.4.5.2 Emissions to Water As described in section 2.6.5.5. (above), all aniline emissions due to drug synthesis were considered to be aqueous emissions. The total aqueous enissions were the sum of emissions due to non-acetanilide synthesis plus acetanilide synthesis. In the absence of data on the relative contributions of these two processes to the total, we used a distribution of 50% aniline consumption by each route. ‘The total emissions were estimated to be: {(0.50 fraction contribution) x (8900 kkg total aniline used) x (9 x 10~ kkg/kkg used)] + [(0.50) x (8900 kkg) x (1 x 10 kkg/kkg)] = 40 kkg (non— acetanilide) + 45 kkg (acetanilide) = 85 kkg aniline generated for emission to vater during drug synthesis. ‘The uncertainty of this emission was estimated to be +100%, -50% based fon the following: 1) The emissions were relatively insensitive to changes in allocation between acetanilide and non-acetanilide drugs because the emission factors were similar in size. 2) The emission factors were estimated to be accurate to within a factor of 2 in each direction. 2.6.4.5.3 Emissions Due to Disposal of Solid Residues No direct data on emission factors were available to permit estimation of emissions due to disposal of solid, aniline-containing residues formed during drug synthesis. In order to be able to estimate emissions to air, land, and water due to this disposal, the following information would be needed: 1) process engineering information on the sources of residues during specific synthesis steps utilizing aniline as a feedstock; 2) data on the percent contributions of the individual processes to the total for the drug category; 3) quantitative analysis of residues produced; 4) rate of production of residues; 5) information on waste disposal methods at each plant (1.e., landfill, incineration, activated sludge treatment, stack gas scrubbers, etc.). 2-292.6.4.5.4 Carry-Over of Aniline as Impurities in Products It was estimated that aniline content in drugs derived from aniline would be zero, based on purity controls required in the pharmaceuticals industry. 2.6.4.5.5 Summary of Aniline Emissions Due to Drug Synthesis Table 2.14 (end of chapter) summarizes estimated emissions to air and water generated during drug synthesis for the years 1974-1978. 2.6.4.6 Emissions Due to Miscellaneous Consumption Synthesis of miscellaneous compounds consumed an estimated 27,000 kkg of aniline in 1978, This was 9% of total aniline usage (Table 2.4), With the exception of p-nitroaniline synthesis via acetanilide, specific compounds and process flow schemes were not available for this category. Therefore, emissions were estimated for the generalized "process" of miscellaneous chemicals production by the operatios (kkg aniline consumed) x (emission factor, kkg emissions/kkg aniline consumed) = kkg total generated emissions. In the absence of data on either anounts of eaissions or experimentally- determined emission factors, an overall best-judgement emission factor for generated emissions due to non-acetanilide-based miscellaneous chemicals synthesis was estimated. The value estimated was 5 x 107? kkg/kkg. This emission factor was for the sum of generated air emissions + generated water emissions. It was based on the following considerations: 1) In any chenical- synthesizing process, only the first (1.e., an{line consuming) step vas of interest. 2) On the average, this first reaction vould utilize 90% of the aniline feedstock. 3) Of the remaining 10% of input aniline, half was reclaimed and recycled, 4) The generated emissions of aniline were therefore 0.05 (or 5%) of aniline consumed: (0.10 fraction not used) x (0,50 fraction of unused not reclaimed) = 5 x 10°* kkg generated/kkg aniline used. The enission factor for acetanilide-based-p-nitroaniline synthesis was estimated to be 0.7 x 107? kkg/kkg. This emission factor was for the sum of air emissions + water emissions, Tt was based on the following considerations: 1) Acetanilide synthesis would be made to use at least 99% of input aniline. 2-302) Analysis of technical grade acetanilide shoved 0.2% aniline carry-over (Kirk-Othmer, 1968). This corresponds to (0.2%) x ( 423.) = 0.3% of Anput aniline (135 and 93 are the respective mlecular weights of acetanilide and aniline). 3) Therefore, 0.7% of input aniline was enitted to water and air. 4) The 0.3% dnput aniline occurring as an impurity in technical grade acetanilide was removed as nitroaniline during subsequent nitration of the acetanilide. This would also be true of hydrolyzed acetanilide forned by the strongly acidic conditions of nitration. These were not tabulated as additional emissions. The estimated emission factor for the acetanilide synthesis step was 0.7 x 10 kkg/kkg aniline used. 2.6.4.6.1 Generated Emissions to Air Emissions to air due to synthesis of miscellaneous chemicals were estimated to total 3 kkg in 1978, This estimate was obtained using the emission factors derived above (section 2.6.4.6) plus the following considerations: 1) In the absence of data on breakdown of consumption within the miscellaneous category, we assuned that 50% of the 27,000 kkg was used in non-acetanilide-based syntheses and 50% was used to synthesize p-nitroaniline via acetanilide. 2) Total emissions were distributed 0.5 parts to air and 99.5 parts to water. 3) For the reasons discussed in section 2.6.4.5.1, emissions to air during acetanilide synthesis were estinated to be zero. The estimated emissions to air were: (13,500 kkg aniline used) x (5 x 10 kkg/kkg) x (0.005 fraction to air) = 3 kkg of aniline emissions generated for release to air during miscellaneous chemicals synthesis in 1978. ‘The uncertainty of this value was estimated to be +500%, -80% based on the analysis presented in section 2.6.4.1.1. 2.6.4.6.2 Generated Emissions to Water Total generated emissions to water were the sum of emissions due to non— acetanilide-based miscellaneous chemicals synthesis plus those due to p~ nitroaniline synthesis via acetanilide. The bases for estimation of emissions are given in section 2.6.4.6.1. (above), The estimated emissions wer (13,500 kkg aniline used) x (0.05 kkg/kkg) x (0.995 fraction to water) = 700 kkg due to non-acetanilide-based miscellaneous chemicals syntheses; and 2-31(13,500 kkg used) x (0.7 x 10° kkg/kkg) x (1,00 fraction to water) = 900 kkg due to acetanilide-based p-nitroaniline synthesis. The sum was 700 kkg + 900 kkg = 1600 kkg generated emissions to water during miscellaneous chenicals synthesis in 1978. ‘The uncertainty of each of these values was estinated to be +500%, -80% based on the analysis presented in section 2.6.4.1.1. 2.6.4.6.3 Emissions Due to Disposal of Solid Residue No direct data nor data on emission factors was available to permit estimation of emissions due to disposal of solid, aniline-containing residues formed during miscellaneous chemicals synthesis. In order to be able to estimate emissions to air, land, and water due to this disposal, the following information would be needed: 1) process engineering information on the sources of residues during specific synthesis steps utilizing aniline as a feedstock; 2) data on the percent contributions of the individual processes to the total for the miscellaneous chemicals category; 3) quantitative analysis of residues produced; 4) rate of production of residues; 5) in- formation on waste disposal methods at each plant (i.e., landfill, inciner- ation, activated sludge treatment, stack gas scrubbers, etc.). 2.6.4.6.4 Carry-Over of Aniline as Impurities in Product With the exception of acetanilide, no data were available to permit estimation of aniline emissions due to aniline impurities in miscellaneous chemicals. In order to estimate these emissions, the following information would be needed: 1) identities and anounts of miscellaneous chemicals derived from aniline; 2) chemical analyses of these miscellaneous chemical batches. In the case of acetanilide, it was estimated that the anount of aniline emissions due to carry-over would be sero. This was based on the Judgement that even though technical grade aniline carries 0.2% aniline as an impurity (Kirk-Othmer, 1968), this aniline would not survive the subsequent nitration step and would be quantitatively converted to nitroantlines. 2-322.6.4.6.5 Summary of Aniline Emissions Due to Miscellaneous Chemicals Synthesis Table 2.15 (end of chapter) summarizes estimated emissions to air and water generated during miscellaneous chemicals synthesis for the years 1974-1978. The table also breaks down total emissions into subcategories: pesticides, herbicides, resins, corrosion inhibitors, petroleum additives, and other uses by using the estimated percent contributions shown in Table 2.9. 2.6.4.7 Generated Emissions Due to Exports 2.6.4.7.1 Amount of Exports Data were not available on the anount of aniline exported in 1978. NeCaleb (1979) cites industry sources as estimating exports to be 1% of pro- duction in 1968, In the absence of contrary or confirmatory data, it was assumed that exports were 1% of production in 1978, also, The amount exported would be (279,000) x (0.01) = 2800 kkg. No eriteria were available to aid in estimating the uncertainty of this value. 2.6.4.7.2 Emissions to Air Emissions to air due to export were considered to be due entirely to transport of aniline. No data were available on amounts of emissions or on emission factors. Therefore, a best-judgement estimate was nade using the operation: (kkg exported) x (emission factor, kkg released/kkg exported) emissions to air due to export. In the absence of data on enission factors, the eaission factor for air emissions due to transport during export was estimated to be 7 x 107? kkg/kkg. It was estinated by using as a aodel a study of spill/release risk in the petroleun industry (U.S. Coast Guard, 1973-1976; U.S. Arny Corps of Engineers, 1973-1976; Setence Applications, Inc., 19773 Sefence Applications, Inc., 1978; U.S. Departaent of Energy, 1978). The bases for this application were: 1) The modes of transportation for ofl and aniline are basically the same (pipes, barrels, tank cars), 2) The petroleum industry studies efted above predicted that approximately 7 x 10° of the total product moved would be 2-33lost during transport and handling. 3) This loss was estimated to be divided 10% to air and 90% to water because of aniline's low vapor pressure, moderate solubility in water, and the likelihood that most spills would be cleaned up by hosing down the area before significant evaporation occurred. The anount of emissions released to air due to transport of exported aniline was: (2,800 kkg transported) x (7 x 107° kkg/kkg) x (0.10 fraction to air) = 2 x 10° kekg in 1978, 2.6.4.7.3 Emissions to Water As described in section 2.6.4.7.2, transport of aniline was considered to be the only source of emissions during export. The amount of emissions was calculated as described in that section: (2800 kkg exported) x (7 x 10™ kkg/kkg) x (0.90 fraction to water) = 2x 107 kkg emissions to water during export in 1978. 8 2234senz TABLE 2.3 EMISSIONS DUE TO IMPORTS OF ANILINE (kkg)? Year Releases to Air During - Releases to Water During - Storage ‘Transport Storage ‘Transport 1978 4 x 107% 7x 10° 1977 2x 104 4x 107 4x 10" 1976 1975 4x 10% 7x 107 6 x 10% 1974 400 x 1074 600 x 1077 600 x 107% \caiculation methods discussed in sections 2.5.2.1 and 2,5,2.2,9e- TABLE 2.5 ANILINE: CONSUMPTION BY ISOCYANATE vanuracture* Isocyanate _—X of Aniline Used Synthesis _Within Category 1978 (ekg) 197 (kp) «1976 (ekg) 1975 (kkg) 1974 (kg) Dipheny1methane~ 4,4-diisocyanate 60 89,000 79,000 61,000 47,000 58,000 Polymethy lene 40 59,000 53,000 40,000 31,000 39,000 Polypheny1. Isocyanate TOTAL 148, 000 132,000 101,000 78,000 97,000 (isocyanate Production) 1, review of references (MeCaleb, 19793 Hancock, 19753 Hahn, 1970; Kirk-Othmer, 1968; Simonds and Church, 1967) indicated that diphenylmethane-i, 4-ditsocyanate used to be the dominant isocyanate; hovever, within the last five years polymethylene polyphenyl isocyanate has becone commercially prominent, Therefore, it was estinated that diphenyimethane-4, 4-d{isocyanate now only makes up 60 percent of the isocyanates manufactured fron aniline, It was assumed that the manufactured anounts of these two Lsocyanates did not vary relative to each other over the five year period. Also, it was assuned that no other aniline-derived isocyanate had been manufactured on a connercial scale during this five year period.e-z ‘TABLE 2.6 ANILINE: CONSUMPTION DURING PRODUCTION OF RUBBER CHEMICALS! Rubber % of Aniline Used Chemicals Within Category 1978 (kkg) 1977 (kkg) «1976 (ekg) 1975 (kg) 1974 (kg). Accelerators 40 32,000 33,000 34,000 26,000 36,000 Antioxidants 30 24,000 25,000 25,000 20,000 27,000 Ant4ozonants 20 16,000 17,000 17,000 13,000 18,000 Curing Agents 10 8,000 8,000 8,000 7,000 9,000 TOTAL 80,000 83,000 84,000 65,000 90,000 (Rubber Chemical Production) 1h review of the references (Hancock, 19753 Hahn, 1970; Lowenheim and Moran, 1975; Kirk-Othmer, 1968; Snell and Hilton, 1967) indicated that rubber accelerators make up the greatest percentage of the use of aniline as a aingle use in rubber chenicals industry. However, antidegradants, which is composed of anti- oxidants and antiozonants, appeared to have the greatest usage as a group of aniline in the manufacture of rubber chemicals, (Lovenheim and Moran, 19753 Kirk-Othner, 1968.) The curing agents vhich are composed primarily of stabilizers, agents and retardera appeared to be produced in amaller quantities than antioxidants and antiozonants, (Lovenheim and Horan, 1975; Kirk-Othaer, 1968.) A review of aniline derivatives based on nunber, apparent quantities commercially manufactured, and uses also supported the estimated percent breakdown of aniline consumption in the rubber chenical industry (Hancock, 1975; Hahn, 1970; Lovenhein and Moran 1975; Kirk-Othaer, 1968; Snell and Hilton, 1967). No indication was obtained from the literature that would indicate a change in the percent of usage of aniline anong the rubber chemicals or with changes in the total production of rubber chemicals over a five year period.ge-z TABLE 2.7 ANILINE: CONSUMPTION BY THE CHEMICAL DYE CATEGORY! Types of % of Aniline Used Dye Chemicals _Within Category 1978 (kkg) 1977 (kg) 1976 (kkg) «1975 (kg) 1974 (kg) Dyes & Intermediates Azote 58 10,000 8,000 8,000 6,000 8,000 Indigota 4 700 500 600 400 600 StLtbene 2 6,000 4,000 4,000 3,000 5,000 Triarylmethane 5 1,000 800 900 700 300 Pre Dye Fiber Treatment 1 200 1,000 100 100 100 TOTAL 17,900 14,300 13,600 10,200 14, 600 (Dye Chemicals Produced) Tcatculation of the aniline usage by Chemical Class and year was based upon Benzenoid Dye production (uancock, 1975). The Chemical Classes were selected by using process descriptions from (EPA, 1977) and compilation of dyes mentioned in (Kirk-Othmer, 1968; Snell and Hilton, 19673 Hancock, 1975).” The production of each of the four chemical types of dyes was totaled and a percent of the total for each type of dye was calculated. Based on a review of the references (TRH, 1973a; Hancock, 19753 Kirk-Othmer, 1968; TRH, 1973c5, Snell and Wilton, 1967; EPA, 1977) it was felt that these percents reflect the aniline production percent usage in these chemical classes. Also based on the preceding references it was assumed that pre dye fiber treatment does not use more than one percent of the aniline production. It was assumed based on references (Hancock, 19753 Kirk-Othmer, 1968; Snell and Hilton, 1967; EPA, 1977) that percent usage of aniline per chemical’ dye class will not’ change drastically over the five year period 1974 to 1978.6e-z TABLE 2.8 ANILINE: CONSUMPTION DURING THE PRODUCTION OF DRUGS!*? Type of Drug % of Aniline Used Manufacture By Category 1978 (kkg) 1977 (ekg) 1976 (kkg) 1975 (kg), 1974 (ek). Sulfa Drugs 70 6,000 6,000 5,000 4,000 7,000 Antipyretic 1“ 1,000 1,000 1,000 800 1,000 Analgeste “ 1,000 1,000 1,000 800 1,000 Local Anesthetic 2 200 200 100 100 200 TOTAL 8,000 (8,000)! 7,000 6,000 10,000 Drug Manufacture 'the 1977 miscellaneous category included drugs, hydroquinone, herbicides, Fibers, and other compounds. This category used 34,000 kkg of aniline, The 1976 and 1978 figures were averaged to arrive at a realistic estimate for use of aniline in the Drug Manufacture. *netermination of the quantity of aniline utilized in the production of drugs was arrived at by analyzing (USITC, 1976-1979; Kirk-Othmer, 1968; Snell and Hilton, 1967). Prior to the late 1960's antifebrin (acetanilide) was widely used as an antipyretic and analgesic hence representing the major usage of aniline in the drug industry. After the late 1960's antifebrin vas replaced by another compound, hence reducing the aniline usage as an antipyretic and analgesic product (Snell and Hilton, 1967). During the late 1960's, the sulfa drugs became a dominant end product consunet of aniline in the drug industry. In the last five years it has maintained its dominant position hile the anitpyretic and analgesic aniline based compounds have been relegated to secondary consuners of aniline. With the demise of the antipyretic and analgesic aniline compounds, aniline based local anesthetic compounds have become a minimal consuner of aniline (Kirk-Othner, 1968).ov-z TABLE 2.9 ANILINE: CONSUMPTION DURING PRODUCTION OF THE MISCELLANEOUS comPoNzNTs”*? types of Miscellaneous % of Aniline Used 7 Compounds Within Category 1978 (ekg) 1977 (kkg)' 1976 (kg) 1975 (ekg) 1974 Ckkp) Pesticides 30 8,000 4,000 6,000 5,000 7,000 Herbicides 30 8,000 4,000 6,000 5,000 7,000 Resins 15 4,000 2,000 3,000 3,000 3,000 Corrosion Inhibitors 10 3,000 1,000 2,000 2,000 2,000 Petroleum Additives 5 1,000 600 1,000 800 1,000 Other Uses 10 3,000 1,000 2, 000 2,000 2,000 TOTAL 27,000 13,000 22,000 17,000 22,000 Miscellaneous Production Tthe miscellaneous category included drugs, hydroquinone, herbicides, fibers and other compounds. This category used 34,000 kkg of aniline. The annual aniline usage figures for 1976 and 1978 in the Drugs and hydroquinone product groups were averaged to determine the potential use of aniline in these product areas. These figures were subtracted from the 1977 reported miscellaneous aniline consumption category. The renain- ing quantity of aniline is the aniline consumed in the miscellaneous products grouping for 1977. re two dominant consuers in the miscellaneous category are Pesticides and Herbicides. (MeCaleb, 19793 Lowenheim and Moran, 1975; Kirk-Othmer, 1968; Snell and Hilton, 1967). Based on the number of references that cited a particular usage and the significance attributed to that usage by each reference, the endproduct uses of aniline in the miscellaneous category were selected (McCaleb, 1979; Lowenheim and Moran, 1975; Kirk-Othmer, 1968; Snell and Hilton, 1967; Hancock, 1975). 5No definitive ordering of the endproducts was attainable in those uses cited under OTHER USES heading in the miscellaneous uses of aniline, These products include: catalysts, explosives, organic synthesis, rocket fuel, and synthetic sweetening agents.wet TABLE 2.10 ANILINE: Isocyanate Synthesized Diphenylmethane~ 4, 4-ditsocyanate Polymethylene polypheny] diisocyanate Total Emissions Per Year 1978 Emissions air water 2200 8 1500 19-3700 EMISSIONS GENERATED DURING PRODUCTION OF ISOCYANATES (kke) 1977 Enissions air water 10 2000 7 1900) 17-3300 1976 Emissions air water 8 1500 5 1000 13. 2500 1975 Emissions air water 6 1200 4 800 10-2000 1974 Emissions air water 7 1400 5 1000 12 2400ze TABLE 2.11 ANILINE: EMISSIONS GENERATED DURING PRODUCTION OF RUBBER CHEMICALS (kkg) 1978 1977 1976 1975 1974 Rubber Chemicals Emissions Emissions Emissions Emissions Emissions air vater air water air water air water air water Accelerators 8 1600 8 1600 9 1700 7 1300 9 1800 Antioxidants 6 1200 6 1200 6 1200 5 1000 7 1300 Antiozonants 4 700 4 800 4 800 3 600 5 900 Curing Agents 2 400 2 400 2 400 2 300 2 400 Total Loss Per Year 20 3900 20 4000 21 4100 7 3200 23 4400ere TABLE 2.12 ANILINE: EMISSIONS GENERATED DURING PRODUCTION OF DYES AND INTERMEDIATES (kkg) 1978 1977 1976 1975 1974 Dyes and Emissions Emissions Emissions Emissions Emissions Intermediates air water air water air water air water air water Azoic 3 500 2 400 2 400 3 300 2 400 Indigotd 0 40 0 30 0 30 0 20 0 30 Stilbene 1 300 1 200 1 200 1 200 1 200 Triarylmethane 0 50 0 40 0 40 0 30 ° 40 Pre Dye~ Treatment 0 9 0 6 0 7 o 5 o 7 Total Loss Per Year 4 900 3 680 3 680 3 550 3 680TABLE 2.13 ANILINE: EMISSIONS GENERATED DURING PRODUCTION OF HYDROQUINONE (kkg) Emissions Year Aue water 1978 4 700 1977 3 600 1976 3 600 1975 2 400 197% 4 700 24mTABLE 2.14 ANILINE: EMISSIONS GENERATED DURING DRUG MANUFACTURE (kkg) Emissions Year a Mater 1978 ° 85 1977 ° 76 1976 oO 67 1975 ° 33 197% o 92 245on-z TABLE 2.15 ANILINE: 1978 Miscellaneous Emissions Compounds air water Pesticides 1 200 Herbicides 1 200 Resins 0.5 100 Corrosion Inhibitors 0.4 80 Petroleum Additives oO. 20 Other Uses 0.4 80 Total Emissions Per Year 3.4 680 GENERATED EMISSIONS DURING MANUFACTURE OF THOSE COMPOUNDS IN THE MISCELLANEOUS CATEGORY 1977 Emissions air water 0.5 100 0.5 100 0.3 50 0.1 30 0.05 10 0.1 30 1.6 320 1976 Emissions air vater 0.8 150 (ose) 150) 0.4 70 0.3 50 0.1 25 0.3 50 237) = 1500) 1975 Emissions air water -9 170 +9 170 0.3 50 0.3 50 o.1 25, 0.3 50 2.8 520 1974 Emissions air water 0.6 © 120 0.9 170 0.4 70 0.3 50 oO. 25 0.3 50 2.6 4903.0 ANILINE HYDROCHLORIDE, m-CHLOROANILINE HYDROCHLORIDE 3.1 PHYSICAL PROPERTIES OF ANILINE HYDROCHLORIDE AND m-CHLOROANILINE RYDROGHLORIDE Chenical Formula CgHN-HCL Cet gClN-HCL Chemical Structure + ma cl a Molecular Weight 128.60 164.04 Melting Point 198°C 221.5°C Boiling Point 265°C at 760 Tore none available Solubility 1,070 g/1 of #,0 very soluble Vapor Pressure none available none available Density 1,22 g/ee none available ‘The physical properties were abstracted from Stecher, 1968 and Weast, 1972. ‘Two physical properties of aniline hydrochloride aid in determining the environmental medium to which aniline hydrochloride may be released. The high solubility of aniline hydrochloride in water (1,070 g/l of H,0) suggests that much of the aniline hydrochloride lost during the manufacturing process and its application waild probably be lost to the environmental water medium, If the vapor pressure were known for aniline hydrochloride, it would aid in estinating the quantity of aniline hydrochloride that could be released to the air during production and consumption. 343.2. MATERIALS BALANCE FOR ANILINE HYDROCHLORIDE Figure 3.1 shows the materials balance for aniline hydrochloride for the year 1978. The purpose of the following text is to explain the basis of our estimates and calculations that yielded the values reported in the figure. 3.3 DIRECT PRODUCTION OF ANILINE HYDROCHLORIDE 3.3.1 Production Processes, Producers and Locations Aniline hydrochloride is produced by the direct reaction of aniline with hydrochloric acid. (Kirk-Othmer, 1968) . WH, cl a) = The Literature cited two methods by which the direct reaction occurs: dry hydrogen chloride gas is passed through an ethereal solution of aniline; and concentrated hydrochloric acid is used to neutralize aniline which has been heated to 100°C with the mixture then being allowed to crystallize (Hawley, 1977). ‘The literature did not indicate which of the methods was the dominant one used in commercial production nor was there any discussion of the production process. From discussions with American Cyanamid it was learned that their produc tion process for aniline hydrochloride consisted of liquid aniline plus as aqueous solution of hydrochloric acid in the presence of a metallic catalyst (Personal Communication). The ratio of the reactants was not disclosed, Similar information about the production of aniline hydrochloride was not revealed by Tennessee Eastman Chemical. USITC and EPA (1977) reported the following production information. The aniline hydrochloride report was confirmed by company spokesmen. 3-2Fioure 3,1 1978 HATERIALS BALANCE FOR ANILINE HYDROCHLORIDE Cxxs) [DOIROONTAL RELEASES (hig) ounces ' \ {rs aN PxPonTS . ema | rial Ae ware toe? f > ixtot sxit exit > 0 nasi ~o =o Contaninante | > 9g ° ° ° Production ~ , “ - of reports aa >} concantnanes - 6 . . ° To, ° ° ° Inpores. ° an woYears Listed Production Compound Company, Location as Producer (ekg) aniline American Cyanamid Bound Brook, NJ 1974-1978 nd. hydro" Tennessee Eastman Kingsport, TN 1974-1978 nae chloride Chen. m-chloro- Alliance Chem. Newark, NI 1977 ° aniline sc 1977 0.5¢5 fydeon —Blackman-UhLer Spartanburg, 5 Chem. Div. chloride No other information on producers and locations was available. 3.3.2 Amounts of Aniline Hydrochloride Produced No production or capacity figures were available in the references reviewed. Discussions with American Cyanamid and Tennessee Fastman Chemical suggested that the production of aniline hydrochloride was somewhere between 4.6 kkg and 100 kkg. The lower estimate was derived from the fact that companies are required to report to USITC when production exceeds 2.3 kkg or $5,000. Two companies reported production of aniline hydrochloride, indicating that at least 4.6 kkg of this were manufactured. ‘The higher value was selected based on discussions with American Cyanamid about the plant capacity at Bound Frook, New Jersey. The source indicated that the aniline hydrochloride capacity was considerably below the aniline plant capacity of 30,000 kkg, yet above 30 kkg. From this conversation it was deter- mined that the production of aniline hydrochloride may be as high as 77 kkg. Information vas obtained on the production of aniline hydrochloride from Tennessee Eastman Chemical. The USITC reports from 1974 through 1978 indicate that Tennessee Eastman Chenical did not report the production of aniline. Since aniline hydrochloride was made fron aniline, it would be nore economical to manufacture large quantities of aniline and captively consune then in aniline hydrochloride production than to buy it from an outside source. Based on this reasoning, and discussions with a spokesnan from Tennessee Eastman Chemical, it was estinated that the Eastman production of aniline hydrochloride constitutes a range from 2.3 kkg to 23 kkg. Thus, the total production of aniline hydro~ chloride was estimated to fall within the range 4.6-100 kkg/yr. 3-43.3.3 Emissions of Aniline Hydrochloride Due to Direct Production Based on a conversation with American Cyanamid, it was learned that the only waste from the production of aniline hydrochloride is in the form of a Liquid waste stream. A spokesperson for Tennessee Eastman Chemical stated that no Liguid or solid residues were produced during manufacture. He also felt no emissions to air occurred during productions. These assertions should be tested vhen further data are available. 3.3.3.1 Air Emission Personal communication with Anetican Cyanamid revealed that there 1s pro- bably no release of aniline hydrochloride to the air pathway during production. If the vapor pressure and more information about the production process machi- nery were available a numerical estimate might be calculated. We believe that releases of aniline hydrochoride to the air during production were minute. 3.3.3.2 Water Emissions Conversations with American Cyanamid indicated that the manufacture of aniline hydrochloride does produce a liquid waste stream. No information as to the character, constituents, and quantity of the Liquid wastestream was obtained. However, the waste stream was treated by a central treatment plant at the American Cyanamid, Bound Brook (NJ) plant. The central treatment plant consists of a primary, secondary-biological, and tertiary-activated carbon treatment facilities. The loss of aniline hydrochloride to the environmental water medium was probably very small at this plant due to the treatment facilities. It was estimated that 0.1% of the total aniline hydrochloride was lost to the water pathway: 0.1% x 4.6 kkg! (low production parameter) = 4.6 x 10? kkg kg 0.1% x 100 kkg! (high production parameter) = 1 x 107 Tnhe aniline hydrochloride production figures were derived in section 3.3.2. 3.3.3.3 Disposal of Solid Waste An American Cyanamid source stated that no solid waste was created during the production of aniline hydrochloride, However, it is believed that some ani- 35Line hydrochloride would be found in the sludge of the first treatment process of the plant water treatment facility. Based on the primary treatment process which was probably some type of settling method, it was estimated that 0.5% of the annual aniline hydrochloride was lost to the water pathway. 0.5% x 4.6 kkg (low estimate of production) = 2.3 x 107 kkg 0.5% x 100 kkg (high estimate of production) = 5 x 107! kkg ‘The annual production values were derived in Section 3.3.2 of this report. 3.4 INDIRECT PRODUCTION OF ANILINE HYDROCHLORIDE Aniline hydrochloride will be produced in the environment if the pH of the surrounding water 1s below aniline's pka value. If chloride ions are present, then aniline hydrochloride would result. No estimates of the quantity of aniline hydrochloride formed in this way were possible because of the lack of data on pi and aniline concentration in environmental water samples, We estinated that very small quantities of aniline hydrochloride would be produced in this manner. 3,5. IMPORTS OF ANILINE HYDROCHLORIDE 3.5.1 Quantity Imported ‘The USITC report on Imports of Benzenoid Chemicals and Products for 1974 through 1978 did not cite any import data for aniline hydrochloride. These reports did indicate that less than 1 x 10? kkg of aniline hydrochloride could be imported and this figure would not be reported in the USITC reports. Secondly, those values used in the USITC reports were only taken from the major east and Gulf coast ports of entry. Therefore they represent a statistical coverage value, depending on the year, from 76 to 99 percent. It was estimated that the average annual taports of aniline hydrochloride during 1974 to 1978 was 1 x 10~ kg. This figure was determined by calculating the average statistical coverage value for "intermediates" and then multiplying the average times the maximum amount of chemical that was not reported. USITC statistical covera hydrochloride that could bel value imported without appearing in the USITC reports four year average of the : ‘maximum amount of aniline 84x, ge] x 1 x 107? kg 1x 107 kkg [estimated four year average annual] aniline hydrochloride inports 3-63.5.2 Emissions Due to Imports The estimated quantities imported were very small; therefore the contribu- tion of aniline hydrochloride to the environmental media would be exceedingly saall, 3.6 CONSUMPTION AND USE OF ANILINE HYDROCHLORIDE The literature reviewed suggested several commercial uses for aniline hydrochloride: synthesis of diphenylamine dyes, N-ethylaniline, diethylaniline, and 2,4,6-tribromoaniline (Hahn, 1970; Hancock, 1975; Hawley, 1977; Kirk-Othmer, 1975; Snell and Hilton, 1967). An American Cyanamid official stated that all of the aniline hydrochloride produced at its Bound Brook (NJ) plant between 1974 through 1978 was used in the manufacture of dyes and related products. The source further stated that all of the alkyl anilines are manufactured from aniline rather than aniline hydrochloride for economic reasons. The aniline hydrochloride produced at the Tennessee Eastman Chemical was a transitory product in a long series of steps to produce photographic chemicals. (Personal communication with Tennessee Eastman Chemical.) Based on the economic premise that the alkyl anilines were manufactured from aniline, it was felt that almost all of the annual aniline hydrochloride vas used to manufacture dyes and related products, and photographic chemicals. The spokespersons for American Cyanamid and Tennessee Eastman stated that the demand for aniline hydrochloride has not changed significantly for the period 1974 through 1978. 3.6.1 Emissions of Antline Hydrochloride Due to the Manufacture of Dye and Related Products ‘The amounts and types of constituents used to manufacture dyes are so varied anong dye classes and within the same dye class that it was impossible to estimate releases to air and water. The calculations and estimates below represented very broad emissions figures of aniline hydrochloride to the environmentalpathways. Discussions with an industry expert on dyes and dyestuffs revealed the manufacturing process for mono-azo dyestuffs. (Personal Conmunication.) This information provided the background information for the estimates on emissions. To get the dye out of its manufacturing solution, the solution is heated and then sodium choride is added. The dye precipitates out of solution with sodium chloride as a contaminant in ppb. The dye precipitate is filtered and pressed to form a dye cake. ‘The dye cake is air dried down to a three to four percent water content. This process suggests three points where emissions can occur: 1) After the dye was precipitated from the solution, the mother liquid was probably pretreated and then released to the municiple sewage system. Because of the high solubility of aniline hydrochloride in water it was conceivable that one percent of the annual production of aniline hydrochloride could enter the environmental water medium. 1% x 2.3 kkg (low estimated production) = 2.3 x 10” kkg 1% x 77 kkg (high estimated production) 7.7 x 107) kkg ‘The production estimates for aniline hydrochloride were calculated in section 3.3.2. 2) The quantity of aniline hydrochloride lost to the air pathway during drying was unknown, because the vapor pressure of aniline hydrochloride was not stated in the literature. However, we feel that it was probably insignificant. 3) The free aniline hydrochloride that may contaminate the dye was esti- mated to be insignificant. This premise was based on a discussion with an in~ dustrial dyestuff expert. 3.6.2 Emissions of Aniline Hydrochloride Due to the Manufacture of Photographic Chemicals In the absence of process flow diagrams or data on emissions or emission factors, it was difficult to estimate the types and quantities of emissions.Tt was estimated that insignificant emissions to air and water media occur during the manufacturing process. This was based on the following: 1) Aniline hydrochloride was a transitory compound in a long series of processes. 2) A spokesperson at Tennessee Eastman stated that there was no liquid wastes and probably no emissions to air during the use of aniline hydrochloride. 3.6.3 Summary of Aniline Hydrochloride Emissions Due to Its Uses Table 3. 1 summaries the estimated emissions to air and water generated during the manufacture of products. 3.7 EMISSIONS DUE 10 EXPORTS ‘An investigation conducted by the Foreign Trade Commision consisting of a search of the July 1978 invoices revealed no exports of any of the aniline ‘compounds.ore TABLE 3,1 ANILINE HYDROCHLORIDE: EMISSIONS GENERATED DURING CONSUMPTION 1978 1977 1976 1975 1974 Product Manufactured Emissions kkg Emissions kkg Emissions kkg Emissions kkg Emissions kkg from air water air water air water air water air water Dyes and Dye Intermediates?” 7.7 x 107) 7.7 «107 7.7 x 107 7.7 x 107 7.7 x 10 Photographic Chemicals ‘TOTAL The high estimated production value was used to calculate the losses in water. The formula used for the caluclations is derived in section 3.6.1. 21 wae assumed that the production of aniline hydrochloride and dyes did not change over the time period.4.0 ANILINE HYDROBROMIDE No infornantion and data were found either in the literature or contacts with industry which suggest that aniline hydrobromide was commercially manufactured or used to produce end products in the United States. To ascertain if aniline hydrobromide was manufactured, a canvassing of the organic chemical industry must be undertaken. In the absence of any data, we estimated that an insignificant quantity of aniline hydrobromide may be produced as a speciality chemical.5.0 o-NITROANILINE 5.1 PHYSICAL PROPERTIES ‘The physical properties of o-nitroaniline are summarized below (Havley, 1977; Weast, 1977-78; Strecher, 1968). Quantitative data on water solubility were not available; qualitative information is presented instead as a general guide. No, g-nitroantline mol. wt. 138,12 Melting point 71.5°C Boiling point 284°C Solubility in cold H,0 slight Solubility in boiling H,0 soluble Temp. at which vapor pressure = 1 Torr 104°C pka g-Nitroaniline is a solid at room temperature. It is characterized as soluble in hot water and has a vapor pressure lower than that of aniline (section 2.1). 5.2. MATERIALS BALANCE FOR o-NITROANILINE Figure 5.1 shows the materials balance for o-nitroaniline. It points out the sources of o-nitroaniline (production, imports), the uses of the compound (consumption categories), and the estimated emissions to air, land, and water due to each process, when possible. This figure describes the most recent year for which data were available: 1978. The purpose of this chapter is to explain the assumptions and calculations that yielded the values reported in the materials balance.Fioune 5.1. MATERIALS BALANCE FOR Q - NITROANILINE (xs) conserve wonconsmerive gatas oF wctnensrton sounces on mt Euo-reonucrs aunties essere eee Predvecton Drew be] Inport ae as E5.3. DIRECT PRODUCTION OF o-NITROANILINE 5.3.1 Production Process, Producers, and Locations Nitroaniline was reported to be synthesized by high-pressure ammonolysis of g-chloronitrobenzene (Hancock, 1975): No, NE. NO, ———— 175°C, 40 Atm 2 5.3.2 Amounts Produced Only Monsanto and duPont were listed as producers in 1978 (Catalytic, Inc., 1978). Producers in years previous to 1978 are listed in Table 5.1 (end of chapter). The amounts of o-nitroaniline produced in 1978 by duPont and Monsanto, respectively, are shown in Table 5.2. These results were reported in Catalytic, Inc., 1978, with no information on the method used to obtain them or an estimate of their accuracy. TABLE 5.2 PRODUCTION OF o- HITROANTLINE, 1978 (kkg) Producer and Location Reported Production (% of total) E, I, duPont de Nemours 248 aD Deepwater, NJ Monsanto Chem. Co. 3393 (932) Sauget, IL su 3641 The total production for 1978 was reported to be 3641 kkg, with Monsanto producing the vast majority of that anount. 5-35.3.3 Emissions Due to Production 5.3.3.1 Emission to Air An industrial process flow chart was not available for the anmonolysis of grehloronitrobenzene, nor were data on emissions or emission factors during production of o-nitroaniline. Therefore, it was not possible to reasonably estimate air emissions due to this process. To fill this data gap, the follow ing information is needed: 1) air monitoring data, especially near the major production facility in Sauget, I1lino1s; 2) process information to permit pinpointing of emission sources; 3) information on waste treatment at Monsanto (incinerators, scrubbers, etc.). 5.3.3.2 Emissions to Water Emissions to water can occur during synthesis (process water). Direct data were not available on o-nitroaniline emissions during this step. A dest judgement estimate was made. 69 kkg o-nitroaniline were estimated to be released to water during production in 1978, This value was obtained by the operation: (kkg o- nitroaniline produced) x (emission factor, kkg/kkg) = kkg emission. In the absence of data on emission factors, we estimated an enission factor for this process to be 1.9 x 10” kkg/kkg. This value was estimated using the following steps: 1) Fed. Reg. (1976) lists proposed rules for effluent limita tions guidelines as limiting the 30-day average for o-nitroaniline to 27 kg CoD/kkg product. 2) This effluent guideline measured in kg COD was converted to kg g-nitroaniline by assuming that (a) all of the COD was due to o-nitroaniline and (b) the o-nitroaniline was quantitatively oxidized to 6 CO, in the COD measurement. Therefore, 6 (32) = 192 g. (6 moles) of oxygen was equivalent to 138 g. (1 mole) of o-nitroaniline, The effluent limitation was expressed as (27 kg COD/kkg product) x ( SS an 4.) + 19 kg qrnitroantline released/kkg grnitroaniline produced. 3) This value was considered to be the maxinum emission factor for aqueous discharge of o-nitroaniline by assuming that production facilities obeyed the effluent guidelines. The enisssion factor was thus 0.019 kkg/kkg. 54The uncertainty of this emission factor was estimated to be +50%, -90% based on the following: 1) It was an overestimate if (as seems likely) less than 100% of the COD was due to o-nitroaniline, 2) It was an underestimate if the chromic acid oxidation did not stotchionetrically degrade all of the o-nitroantline in a COD measurement. Application of this emission factor yielded: (3641 kkg produced) x (1.9 x 107? kkg/kkg) = 69 kkg g-nitroaniline generated for release to water during production in 1978, 5.3.3.3 Emissions Due to Disposal of Solid Residues Wo direct data on emissions nor data on emission factors were available to permit estimation of emissions due to disposal of solid, o-nitroaniline-containing residues formed during production. In order to be able to estimate emissions to air, land, and water due to this disposal, the following information would be neede 1) process engineering information on the sources of residues during the synthesis process; 2) quantitative analysis of residues produced; 3) rate of production of residues; 4) information on waste disposal methods at each plant (i.e., landfill, incineration, activated sludge treatment, stack gas scrubbers, etc.), Since -nitroaniline is a solid and is only slightly water- soluble at room temperature, the chance of having solid o-nitroaniline residues is substantial, 5.4 INDIRECT PRODUCTION Although opportunities for indirect production of g-nitroantline undoubtedly exist, no information was available in this area, 5.5. IMPORTS OF o-NITROANILINE 5.5.1 Amounts Table 5.3 shows available data on imports of o-nitroaniline for the past five years.TABLE 5.3. IMPORTS OF o-NITROANTLINE (keg)! 1978 1977 1976 1975 1974 nea. mas 16 na ou Isource: USITC, Imports ofBenzenoid Chemicals and Products, na, = not available ‘A datum was not available for 1978 imports, so the 1976 value was used in the Materials Balance (Figure 5.1). 5.5.2 Emissions Due to Imports Data were not available on emissions due to transport and storage of imported o-nitroaniline, Furthermore, the ofl spill/risk model described in section 2.5.2.1 was not considered applicable to a solid compound like o-nitro- aniline, Therefore, estimates of emissions must avait the availability of the folloving information: 1) more complete inportation statistics; 2) monitoring data or a measured emission factor applicable to air, water, or total ssions. 5.6 CONSUMPTION AND USE 5.6.1 Categories of Use g-Nitroantline had two major industrial uses: 1) It was a starting reactant 4m the synthesis of o-phenylenediamine; and 2) It was used in the formation of dyes an dye intermediates, Table 5.4 (end of chapter) lists companies associated with each category. Of the two categories, o-phenylenediamine production was reported to be predominant (Hancock, 1975) but no percentage breakdown was given. 5.6.2 Amounts of Use No data vere available on amounts of -nitroaniline consumed either in toto or by each of the major categories of use. Exports were estimated (NcCaleb, 1979) to account for 1% of production, or 36 kkg in 1978. We had no criterion to evaluate the uncertainty of this value. 5-65.6.3 Emissions by Category of Use Data on emissions during o-nitroaniline use were not readily available. In order to be able to report these emissions, one or sore of the following would be needed: 1) Previously estimated emissions values from the literature; 2) Quantitative data on consumption of o-nitroaniline (total or by plant); 3) Process flow diagrams for consumption steps; 4) Measured effluent data on air and water waste streams at each consumption site; 5) Information on solid residue handling procedures at each consumption site; 6) Chenical analyses of solid residues containing 9-nitroanilin. synthesized using o-nitroantline. 7) Chemical analyses of productsTABLE 5.1 PRODUCERS OF o-NITROANILINE BY YEAR! 1978 1977 1976 1975 1974 duPont duPont Synalloy Corp. duPont Monsanto Deepwater, NJ Blackman-Unler Chen, Div. Monsanto Monsanto (450-4500 ekg) Monsanto: i Monsanto Sauget, IL Salsbury Labs Leland, NC GAF Corp. Rennselaer, NY (5-450 kkg) Blackman-Unler Chen. Div. Spartanburg, SC (5-450 kkg) \sources: Catalytic, Inc., 1978; USITC, 1976-1978; EPA, 1977 2yanufacturer declined to be identified. 5-8TABLE 5.4 INDUSTRIAL CONSUMPTION OF ORTHO-NITROANILINE MANUFACTURING : e PROCESS COMPANY. PRODUCTS PRODUCED’ production of E. I, du Pont de dyestuffs ‘o-phenylene~ Nemours & Co., pharmaceutical products ‘@amine Inc. rubber chemicals Sherwin Williams veterinary products Co. ‘Tons River Chemical Co. preparation Alliance Chemical dyes and dye of azo and Corp. intermediates anthroquinone American Color and ayes Chemical Corp. GAF Corp., Chem. Division Synalloy Corp. , Blacknan-Unler Chemical Div. \ysrre » 1976-79, photo anitfogging agents 2rRw, 1973a3 Hancock, 1975; Snell & Snell, 19625 Patty, 1963.6.1 PHYSICAL PROPERTIES OF meta-NITROANILINE Chemical Formula CGN Mi, a Chemical Structure NO. 2 Wolecular Weight 138.12 Melting Point Boiling Point 306° Solubility Water 11 g/liter Alcohol 50 g/liter Ether 56 g/liter Methanol 87 g/liter Vapor Pressure Density 1.43 glee at 4 The physical properties were extracted from Stecher, 1968, and Weast, 1972. Two physical properties of m-nitroantline my be useful in estimating the quantity and medium by which m-aitroantline may be released. The slight solubility of genitroaniline in water suggests that only small emissions could be accommodated dissolved in liquid wastestreans from manufacture and consuaption. The low vapor pressure of mnitroaniline suggest that spontaneous sublimation would be slow. 6.2 MATERIALS BALANCE FOR neta-NTTROANILINE Figure 6.1 shows the materials balance for m-nitroaniline for the year 1978. ‘The following text explains the assumptions and calculations.ELGURE 6.1 MATERIALS BALANCE FOR -NITROANILINE (xs) ENVIRONMENTAL RELEASES (RKC) S3E5°Rto Eaonrs conTaninanrs onconsunerive Soup sources A ne i » uBes ' nie, MATER wAStES Lom, So , , , racer 3 or 39 ,foves ano oe META-HITRO- INTERMEDIATES [CONTAMING wo ~o 10.3, > 2 no 2 Jo svwrneric 1 CCONTAMLHANTS SWEETENERS | > , : womnecr , pnooger ton % > 6 ° ° ° muorogpammae |__+ aerogenes afecrraminas 777 , : IwroRts }ofo-ruenveene ]__2 > CONTAMINANTS. 5 1 ML aa , [2s coccroiosrarig——of conrarinanrs , : , 1. [renon r fof eat Piven conraninanrs an , ESSE | 1 1 Loot carom es een >, : ' C=" , 16.3. DIRECT PRODUCTION OF met@-NITROANILINE 6.3.1 Production Process, Producers and Locations ‘The literature revealed three methods by which m-nitroaniline may be manufactured. E, G, Hancock stated that the normal production process was the partial reduction of m-dinitrobenzene with sulfides: 0 Na, Ways 0, (reduction) we A second method of production vas from m-nitrobenzoic acid, but the chemical aiitroaniline steps were not available from the literature (Stecher, 1968). meta- is produced from aniline by nitration after acetylation. The acetyl group is removed by hydrolysis yielding mnitroantline (Hawley, 1977). No mention was made in the literature as to the quantity of mnitroaniline manufactured by the respective processes. ‘The USITC reports for 1974 through 1978 indicated that there was one producer of mnitroaniline for 1974, 1976 and 1977. The producer was unknown because they requested not to be identified in the USITC reports. Further attempts at identifying the producer have been unsuccessful. 6.3.2 Quantity Produced ‘The anount of m-nitroaniline produced during the years 1974, 1976, and 1977 was not reported in the USITC due to its policy of not revealing production Figures of an individual producer. However, the quantity produced during these years had to be greater than 2.3 kkg because companies are required to report production of products that exceed 2.3 kkg or $5,000.00. 6-3‘The upper limit on the production of mnitroaniline was difficult to estimate. Since only one company reported production, it was probably a small use commodity. Therefore, it was roughly estimated that no more than 45 kkg were produced. Although production was not reported to the USITC during 1975 and 1978, this did not necessarily indicate that no m-nitroaniline was produced. It did suggest that from 0 kkg to 2.3 kkg was produced during these years. 6.3.3 Emissions Due to Direct Production No information was available in the literature reviewed nor was it possible to create a production model on which emission estimates could be formulated. 6.4 INDIRECT PRODUCTION OF meta-NITROANILINE No method of indirect production was stated or could be inferred from the references reviewed. 6.5. IMPORTS OF meta-NITROANILINE 6.5.1 Amounts Imported Statistical Coverage Year Value Quantity keg 1978 76% 47 1977 ax 15 1976 80% 95 1975 94% 48 1974 99% 86 ‘These values were calculated based on the USITC Imports of Benzenotd Chemicals and Products for 1974 through 1978. Each of these reports contained a “statistical coverage value" which represented an estimate of the percentage of the imports that were actually reported. The values in the table have been corrected to represent the total imports, The calculation to arrive at the 6-4corrected value is shown below: = USITC imported quantity x 100% Import compound at 100% value = istrC-statistical coverage value in % ‘The corrected import figures did not reflect imports due to air transportation (personal communication with U.S. Department of Commerce). 6.5.2 Emissions Due to Imports The quantity of emissions to air, land, and water of mnitroantline was difficult to assess due to the dearth of information in the literature reviewed. Releases to air and water would occur during the storage and transportation of imported mnitroaniline, These emissions would be due to spills and damaged containers. Losses to the water medium probably made up 80 percent of the loss and 20 percent was lost to the air medium. Spills were probably cleaned up by shoveling the chemical back into the container or hosing the area down. Losses to the air were probably in the form of particulate matter. Air movements near spills would cause the crystals to become airborne. In the absence of any data on emissions during transportation an overall best-judgement indicated that the loss was insignificant. This was based on the premise the mnitroantline was shipped in metal 55 gallon drums requiring very little subsequent transfer or handling of contents. 6.6 CONSUMPTION AND USE OF meta-NITROANILINE A review of the Literature indicates that the prodominant use of mnitro~ aniline was as a dye intermediate (Hancock, 1975; Hawley, 1977; Strecher, 1968; and TRW Systens Group, 1973). m-Nitroaniline has also been used to manufacture photographic antifogging agents, coccidostatics, interior paint pigments and synthetic sweeteners (Hawley, 1977; Kirk Othmer, 1968; Snell, 1963; and Snell and Hilton, 1964). There are two areas to examine for w-nitroaniline emissions: 1) direct emissions during consumptive use and 2) carry-over as impurities in the manufactured products. 6-56.6.1 Total Consumption Data were not available on the breakdown of the consumptive use of mnitroaniline, Therefore, estimates of m-nitroaniline production were made based on the criteria used by USITC in reporting production and a general definition of what "small amounts" of production were to industry. These two Limits were discussed in Section 6.3.2 of this report. ‘The major source of m-nitroaniline was imports. The total w-nitroaniline available for consumption is presented in Table 6.1. It was assumed that the g-nitroaniline produced and imported was consumed during that calendar year. TABLE 6.1 INDUSTRIAL CONSUMPTION OF meta-NITROANILINE (kkg) Year Estimated Inports Total Domestic Production Low High Low High 1978 2a) a7 a7 49.3 1977 2.3 45 1s 17.3 60 1976 0 23 95 95 97.3 1975 2.3 45 48 50.3 93 1974 ars) A] 86 47.3 131 6.6.2 Emissions Due to Dye Manufacture The predominant consumer of w-nitroaniline was probably the manufacture of dyes. The basis for this assumption was the literature reviewed. Several references cited the manufacture of dyes as the only use of m-nitroaniline 6-6(Hancock, 19755 Patty, 1963; Snell, Snell, 1962; and Stecher, 1968). In the absence of any data on the consumption by the different endproducts, our best estimate was that 80 percent of the mnitroaniline was used in dye manufacture. The renaining 20 percent was used to manufacture all other products sade from genitroaniline. In the absense of data on the amounts of emissions or emission factors, an overall best-judgenent emission factor for euissions generated during dye synthesis was estimated. The value estimated was 5 x 107? kkg/kkg. This emission factor represented the sum of the air and water enisssions. It was based on the following considerations: 1) In any chemical synthesizing process, only the introduction and initial chemical reaction of s-nitroantline was significant. 2) The average initial reaction would utilize 90% of the menitroaniline feedstock. 3) Of the remaining 10% of w-nitroantline; 5% was reclaimed and recycled and the other 5% was lost to water and air media as emissions. Therefore, the emission factor for mnitroantline emissions generated during dye manufacture vas calculated as follows: (0.10 fraction not used) x (0,50 fraction of unused not reclaimed) = 0.05 kkg generated/kkg m-nitroantline consuned. 6.6.2.1 Generated Emissions to Air Due to lack of data on air emissions or emission factors during dye manufacture, the estimated factor derived in the preceding section (5 x 10°) kkg/kkg) was applied to estinate the generated emissions to air during dye manufacture. To determine the emissions to air, it was estimated that 95% of emissions of mrnitroantline were through the water medium and 5% of the air medium. The loss to air would be in the form of particulate matter. The loss would primarily occur during the emptying of the drums containing the crystals of m-nitroantline into the dye manufacturing vessel. The calculations for enissions to air are presented below: (49 kkg wrnitroaniline, high estimate use) x (5 x 10° kkg/kkg used) x (0,5 Eraction to air) = 1.1 x 107 kkg generated for release to air during dye production in 1978, ‘The calcualted emission to air did not change significantly when the low estimate of wnitroantline usage for 1978 was used. 6-7No data were available on the make up of the 20% of m-nitroaniline production that was not used in dye manufacture, Therefore, no attempts at estimating the emissions of m-nitroaniline to the air, land and water media vere made. In order to estimate emissions accurately the following data would be necessary: 1) The percent of the total mnitroaniline annual production consumed by each product, 2) Diagrams of the manufacturing processes with explanation on how these processes work and sources of emissions within the process. 3) The types, quantities, and compositions of wastes from the manufacturing processes. 4) The waste treatment facilities at each plant and their efficiencies. 5) The final disposition of the wastes. 6.6.2.2 Generated Emissions to Water The approach to estimating emissions generated during dye manufacture was described in Section 6.6.2.1 (above). The only value which changed in the calculation was the percent loss: From 5% air to 95% water, The emissions to the water medium vere calculated as follows: (49.3 kkg m-nitroaniline, high estimate) x (5 x 107 kkg/kkg consumed) x (0.95 fraction to water) = 2.3 kkg generated for release to water during dye production in 1978, 6.6.2.3 Emissions Due to Disposal of Solid Wastes No data nor emissions factors were available to permit an estimate of emissions due to solid, mnitroaniline-containing residues formed during dye synthesis. For an accurate estimate of emissions to air, land and water media as a result of this disposal, the following would be needed: 1) Process engineering information on the sources of residues during each process utilizing m-nitroanilines 2) Information on the present contributions of the individual processes to the total for that dye class: 3) Quantitative analysis of residues produced; quantities of residue produced; 4) The waste treatment facilities and their efficiency; 5) The disposition of the solid residue (landfill, incineration, etc.). 6-86.6.3 Emissions Due to Manufacture of Other Products from mNitroantline ‘The consumption of m-aitroaniline for manufacture of other products was estimated to be 20% of annual production. Refer to Section 6.6.2 of this report for the basis of this estimate. Other products manufactured from mnitroaniline included: photographic antifogging agents; o-phenylenediamine; coccidiostatics; interior paint pigments; and synthetic sweeteners (Hawley, 1977, Kirk-Othmer, 1968; and Snel1-Hilton, 1967). 6.7 EMISSIONS DUE TO EXPORTS OF meta-NITROANILINE ‘An davestigation conducted by the Foreign Trade Commission consisting of a search of the July 1978 invoices revealed no exports of wnitroaniline.7.0 para-NITROANILINE 7.1 PHYSICAL PROPERTIES OF para-NITROANILINE para-Nitroaniline is also known as para-nitraniline and 1-amino-4-nitrobenzene, Tt 4s a fine needle yellow powder at room temperature, (Hawley, 1977). Its physical properties are summarized below: Chemical Structure Chemteal Formula Molecular Weight Melting Point Boiling Point Solubility in: cold #0 varm 10 alcohol ether Density Temp at which vapor pressure = 1 Torr faa) 0, WO,C i NH No, 138.13 146" 332% 0.8 g/l 22 g/l 40 g/1 33 g/l 1.424 g/ee at 4° 142.4°C ‘The physical properties that were of particular value in estimating emissions were the solubility in cold water and the vapor pressure.7.2 MATERIALS BALANCE FOR para-NITROANILINE Figure 7.1 depicts the materials balance for p-nitroaniline for che year 1978. It shows the sources of p-nitroaniline (production and imports), the consuaptive uses and exports, and the estinated emissions to air, water, and land due to each process. 7.3. DIRECT PRODUCTION OF para-NITROANILINE 7.3.1 Production Processes, Producers, and Locations Literature indicated five methods for the synthesis of p-nitroaniline. E. G. Hancock (1975) stated that it was manufactured under pressure by the annonolysis of p-chloronitrobenzene. The production process may be either batch or continuous (Hahn, 1970, Hawley, 1977 and Snell-Hiiton, 1967). ; NK, No, No, An alternate procedure was by the nitration of acetanilide followed by hydrolysis (Hancock, 1975; Snell and Hilton, 1967; and Stecher, 1968). The other three methods were: 1) nitration of aniline and then acetylation; 2) reaction of p-dinitrobenzene with alcoholic ammonia; and 3) acid-catalyzed addition of hydrazoic acid to carboxylic acids (Hawley, 1977; Snell, Snell, 1962; and Stecher, 1968). These methods were probably not used to any great extent in the commercial synthesis of p-nitroaniline. ‘The first method mentioned (anmonolysis) was estimated to produce 80 percent and the second method (nitration) 20 percent of the annual domestic p-nitroantline production. 7-2Froune 7.1. MATERIALS BALANCE FOR e-HITROANILINE (rxe) prvtnoororan aELesses (4) , , ca aa tot uw ~o wn [ ¥ ee ee eo fo UG > © soo ~o a0 fax [Sia Fo [oere ea = oo oO a ,. . = ea oe 7 oss; : . : ape] spores Jand Veterinary [contaminants sf a ° 1 = —_ : : ; anit © 850 10 a 1 7 LOM ntseedtancove —. Contaainants 1 , 1 7 oo as 5 | ; , ;7.3.2, Amounts Produced Data on the production of p-nitroaniline were difficult to obtain. There were four producers of prnitroaniline in 1978. The production for only two of these companines was reported, and it was 6534 kkg for 1978 (Table 7.1), No production figures were available for the other tvo, The actual production was probably about twice this value or 13,000 kkg. The two companies for which no production was available were estinated to be similar in size to those that did supply data. Therefore, the estimated value represented twice the known value. Refer to Table 7.1 for a list of the producers, and quantities produced where known from 1974 to 1978. TABLE 7.1 PRODUCERS OF para-NITROANTLINE BY YEAR, INCLUDING PRODUCTION WHERE AVATLABLE! Compound 1978 197 1976 1975 1974 poNitro= aniline duPont duPont Monsanto American American Deepwater, NI Color & Color & Chemical Chemical American Monsanto Color & 4500-23,000 kkg, Chemical duPont duPont Lockhaven, PA 1825 kkg Salsbury Labs Monsanto Monsanto produced Leland NC Monsanto Process Div., Sauget, 11 UOP Inc. 4709 kg, Shreveport, LA produced Signal Companies Shreveport, La Tine manufacturing process used was the anmonolysis of p-nitrochlorobenzene. 7.3.3 Emissions Due to Direct Production The lack of data on production, processes, manufacturing flow diagrams, and emission data and factors prevented calculation of precise estimates. However, in an attempt to provide some guidance, rough estimates were calculated for air and water emissions. 747.3.3.1 Generated Emissions to Air Emission figures of p-nitroantline to air during production were the sum of emissions due to: production, product storage, and product transport. We estimated the anounts of emissions generated to air by the following equation: (estimated kkg produced, stored and transported) x (emission factor in percent of annual production) = kkg released due to production, storage or transport. The estimated emissions to air are calculated below: 13,000 kkg/yr x 1 x 10> = 1.3 x 107 kkg loss of p-nitroaniline for 1978. The loss might be in the form of particulate matter due to the small size of the p-nitroaniline crystals. The emission factor of 1 x 10° percent represented our best estimate of the likely loss to the air by a powdery substance, during production, storage and transport in closed containers. 7.3.3.2 Generated Emissions to Water Emission figures of p-nitroaniline to water during production, product storage, and product transport were not readily available. The primary loss was estimated to be due to the production liquid waste stream, with minor amounts occurring due to spillage and container damage. The effluent limitation guidelines for p-nitroaniline were used to estimate the loss to water. The proposed effluent limitation for p-nitroaniline (30 day average) is 13 kg COD/kkg of product. (Environmental Protection Agency, Organic Chemicals Manufacturing Paint Source Category, 1976.) The COD value was converted to kg penitroaniline by making the following assumptions; 1) All of the COD was due to prnitroaniline. 2) The p-nitroaniline was quantitatively oxidized to 6 CO, in the COD measurement. The resulting equivalence of oxygen was 6(32) = 192 g oxygen and 138 g of p-nitroaniline, With an effluent Limitation of 9 kg penitroaniline/kkg product (0.9% release), the maximum allowable emission factor would be calculated as: (13,000 kkg annual production) x (9 kg/kkg release factor based on COD) = 117 kkg of penitroaniline lost to the water mediun during production, storage and transport. 7-5The uncertainties of the estimate were: 1) it would be an overestimate 1f less than 100% of the COD were due to p-nitroaniline; 2) it would be understated if the chromic acid oxidation did not completely degrade all of the nitroaniline during COD measurements; 3) it assumed compliance with the guidelines by producers. ‘The emission figure's uncertainty was estimated at +502, -902. The ponitroaniline lost to the liquid waste stream of the manufacturing plant was probably treated by a central treatment facility. In the worst instance, it would be treated only by a gross filtering or settlement treatnent procedure removing at most 40% of the chemical waste. The liquid vaste stream would then be released to a municipal sewage systen. Table 7.2 summarizes the estimated emissions (calculated as described above) due to production for the years 1974-1978, TABLE 7.2 EMISSIONS OF p-NITROANILINE DURING SYNTHESIS EMISSIONS (kkg) YEAR AIR WATER 1978 chee 107? 17 1977 98x 107 85 1976 47x 107 42 1975, 1.2 x 107 LoL 1974 LL.2 x 107 lol Ithe production estimates upon which the enissions estimates vere based are tabulated and footnoted in Table 7.1. 71-67.3.3.3 Disposal of Solid Residue The lack of available data and emission factors prevented estimates of solid residue disposal. The information needed for an estimate on solid waste disposal would be: the quantity, type, and character of wastes generated during manufacture and waste treatment, and the methods used by each p-nitroaniline-producing plant. 7.4 INDIRECT PRODUCTION OF para-NITROANILINE Analysis of the accessible literature and chemical synthesis possibilities did not indicate any indirect production method. 7.5 IMPORTS OF para-NITROANILINE 7.5.1 Amounts of para-Nitroantline Imported YEAR STATISTICAL COVERAGE VALUE QUANTITY, kg 1978 76% 795 1977 ax 1620 1976 soz 984 1975 94% 1310 1974 99% 857 USITC Imports of Benzenotd Chemicals and Products for 1974 through 1978 was the source used to calculate the values above. By applying the statistical coverage value to the reported USITC value, the corrected import value was obtained. Import Compound at _ USITC imported quantity x 100% 100% Value USITC statistical coverage value in % ‘The import values in the table above do not reflect air transported imports (Personal Communication with U.S. Department of Commerce).7.5.2 Emission Due to Imports Data on emissions and emission factors were not available for the determin- ation of emissions to air, water and land sedi. Emissions to air and water could occur during the storage and transportation of imported p-nitroaniline. These releases would be due to spills and leaks from damaged containers. Of the total loss, 80 percent was estimated to be lost to water and 20 percent lost to air. Spills would probably be cleaned up by shoveling the compound back into the container and hosing the area down. Emissions to the air would probably be in the form of particulate matter because penitroaniline is a crystalline solid. p-Nitroaniline was probably imported in 55 gallon drums or similar container which would limit the amount of emissions, In the absence of any data on spills or container damage, it was estimated that the emissions fro imports would be insignificant. 7,6 CONSUMPTION AND USE OF p-NITROANILINE Current data on the consumption and uses of p-nitroaniline were not available. Therefore, the following assumptions are made, in an effort to provide estinates on quantities consumed by consumption categories: 1) In lieu of more recent figures, the consumption apportionment for 1969 was applied to 1974 through 1978 total prattroaniline donestic production and imports: rubber chemicals, 40%; dyes and internediates, 20) veterinary, 7%; agricultural chemicals, 3%; and miscellaneous, 10% (TRW Systens Group, 1973a). 2) There were no significant consumption changes among the product groups during this time period. 3) All of the prnitroaniline produced and imported during a given calendar year was used during that year. gasoline additives, 20%; pharmaceuticals and 7.6.1 Total Consumption Complete consumption and use figures were not available for the period 1974 through 1978. In order for estimates to be calculated, the folloving assumptions were necessary: 1) Consumption = production for the years under consideration. 2) The production of p-nitroaniline has remained constant from1974 through 1978, 3) The Monsanto production for 1978 of 4709 kkg also represents the estimated amount produced by duPont. 4) The American Color and Chemical Company production for 1978 of 1825 kkg also represents the estimated anount produced by Signal Companies. The estimated domestic production for 1978 is 13,000 kkg + 795 kkg imports = 13,795 kkg the total available p-nitroaniline for consusption. Refer to Table 7.3 for consumption estimates 1974 through 1978. 7.6.2 Categories of Use ‘The categories of p-nitroaniline use, consuming companies, and amounts used for the past five years are presented in Table 7.4. The data were obtained from the footnoted references; we had no criterion on which to base an uncertainty estimate. ‘The rubber chemicals will probably increase the market share of p-nitro- aniline, vile dyes and dye intermediates and agricultural chemicals demand will steadily decrease. A detailed Listing of the production processes, derivatives and uses are cited in Appendix B. 7.6.3 Emissions by Category of Use 7.6.3.1 Emissions Due to Rubber Chemicals The estimate of emissions of p-nitroaniline from the production of rubber chemicals was based on the following assumptions: 1) para-Phenylenediamine was the feedstock for all the rubber chemicals. 2) The yield of p-phenylenediamine from penitroaniline was 90%. 3) para-Nitroaniline synthesis of para-phenylene~ diamine was a single step process. 4) para-Phenylenediamine contained no nitroaniline as impurity. 5) The 10% difference in actual and theoretical yield represented the p-nitroaniline lost to the environment. 6) Of the 10% lost to the environment, 90% was emitted to the water and 10% was emitted to the air. The emissions to air and water were calculated to be: (6000 kkg, 1978 p-nitroaniline used to manufacture p-phenylenediamine) x (0,10 loss due to production of p-phenylenedianine) x (0.90 loss to the water) = 500 kkg lost to the water media during 1978. (6000 kkg, 1978 p-nitroaniline used to manu- facture p-phenylenediamine) x (0.10 loss due to production of p-phenylenediamine) x (0.10 loss to air) = 60 kkg, lost to the air media during 1978.TABLE 7.3 INDUSTRIAL CONSUMPTION OF PARA-NITROANILINE (kkg) Estimated Donestic Year Production Imports Total 1978 13,000" 795 13,795 1977 9,400 1620 11,020 1976 4,703 984 5,684 1975 11,0004 1310 12,310 1974 11, 000 857 11,857 Icgieulations: Producer Quantity kg, duPont 4709 (estimated) Monsanto 4709 Anerican Color ‘and Chemical 1825 Signal Companies 1825 (estimated) 13,068 2calevlations: Producer Quancity lees duPont 4709 (estimated) Monsanto 4709 3418 calculations: Producer Quantity ekg, Monsanto 4709 Scatculations Producer Quantity keg, Anerican Color ‘and Chemical (1825 duPont 14709 (estimated) Monsanto 4709 1,243 7-10ue TABLE 7.4 CATEGORIES AND AMOUNTS OF para-NITROANILINE CONSUMPTION 1974-1978 (kkg/year) % of Para Manufacturing Nitroaniline A Process Consumed Company! Products Produced Year Amount Used Several (Wo Users Different 40 Cited) rubber chemicals 1978 6000 Compounds 1977 4000 1976 2000 1975 5000 1974 5000 Several 20 Allied dyes and dye 1978 3000 Different Chemical intermediates Compounds Corp. 1977 2000 American Color & Chemical Corp. 1976 1000 Atlantic Chemical Corp. 1975 3000 E.1. duPont de Nemours & Co., Inc. 1974 2000 Fabricolor Manu- facturing Corp. GAF Corp. Warshay Chenical Co., Div. of Kewanee O11 Co. Mobay Chemical Corp. Southern Dyestufé Co.ak TABLE 7.4 CATEGORIES AND AMOUNTS OF para-NITROANILINE CONSUMPTION (continued) % of Para~ Manufacturing Nitroaniiine A Process Consumed, Company! Products Produced Year Amount Used Several 20 (io Users agricultural chemicals 1978 3000 Different Cited) Compounds 1977 2000 1976 1000 1975 3000 1974 2000 Several 7 (Wo Users gasoline additives 1978 1000 Different Cited) Compounds 1977 1000 1976 400 1975 1000 1974 1000 Several 3 Qo Users pharmaceuticals and 1978 400 Different Cited) veterinary products Compounds 1977 300 1976 200 1975 400 1974 400ere TABLE 7.4 CATEGORIES AND AMOUNTS OF para-NITROANILINE CONSUMPTION (continued) % of Par Manufacturing, Nitroaniline fe Process Consumed, Company Products Produced Year Amount Used Several to (Wo Users miscellaneous 1978 1000 Different cited) Compounds 1977 1000 1976 600 1975 1000 1974 1000 USITC, 1976-79; TRW, 1973a,The 500 kkg was considered generated emissions instead of actual emissions, because the aqueous waste stream would be at least primary-treated before release to environmental waters. The quantity of solid waste generated from the manufacture of rubber chemicals was unknown. Accurate estimates of emissions can be calculated only with the following knowledgs product; 2) emissions data or factors from manufacturing plants; 3) accurate 1) production processes and descriptions of the processes for each production figures; 4) the types, character, and amounts of waste streams generated; 5) the types, efficiency and final disposition of waste treatment. 7.6.3.2 Emissions Due to Dyes and Dye Intermediates Data were not available on air and water emissions or emission factors during dye synthesis, Estimates were calculated based on the following considerations: 1) The step that introduces p-nitroaniline into the multi-step process was the only step considered. 2) The yield was 90%, based on general engineering and economic considerations. 3) Of the remaining 10% of p-nitroaniline, 5% was reclaimed and recycled and the other 5% was lost to water and air media as emissions. Therefore, the emissions factor for p-nitroaniline emissions generated during dye manufacturing was calculated as follows: (0.10 fraction not used) x (0.05 fraction of unused not reclaimed) = 0.05 kkg generated/kkg p-nitroaniline consumed. 7.6.3.2.1 Generated Emissions to Air In the absence of data on air emissions or enission factors during dye nanufacture, the emission factor derived in the preceding section (5 x 10 kkg) was applied to determine the emissions to air during dye manufacture. It was estimated that 95% of the emissions of p-nitroaniline were to the water mediun and 5% to the air medium. The loss to air would be mostly in the form of particulate matter and would occur during the euptying of druns into the dye reaction vessel. The calculations for entesions to air are presented below (3000 kkg p-nitroaniline used to make dyes) x (5 x 10 kkg/kkg used) x (.05 fraction to air) = 8 kkg generated for release to air during dye production in 1978,7.6.3.2.2 Generated Emissions to Water ‘The approach to estimating emissions generated during dye manufacture was described in section 7.6.3.2.1 (above). The only value which changed in the calculation was the percent loss to water: 95%, The emissions to the water medium vere calculated as follows: (3000 kkg p-nitroaniline) x (5 x 10 kkg/kkg consumed) x (0.95 fraction to water) = 100 kkg generated for release to water during dye production in 1978, 7.6.3.2.3 Emissions Due to Disposal of Solid Wastes No data nor emissions factors were available to permit an estimate of emissions due to solid, prnitroaniline containing residues formed during dye synthesis. For an accurate estimate of emissions to air, land and water media as a result of this disposal, the following is needed: 1) Process engineering information on the sources of residues during each process utilizing mnitro- aniline; 2) Information on the percent contributions of the individual Processes to the total for that dye class; 3) Quantitative analysis of residues produced; quantities of residue produced; 4) The waste treatment facilities and their efficiency; 5) The disposition of the solid residue (landfill, incineration, etc.). 7.6.3.3 Emissions Due to Agricultural Chemicals No data on emissions or emission factors were readily obtainable. Refer to section 7.6.3.7 for further remarks. 7.6.3.4 Emissions Due to Gasoline Additives No data on emissions or emission factors were readily obtainable. Refer to section 7.6.3.7 for further remarks. 7.6.3.5 Emissions Due to Pharmaceuticals and Veterinary Products In the absence of data on emissions and emission factors no estimates were made. Refer to section 7.6.3.7 for further remarks. 7-157.6.3.6 Emissions Due to Miscellaneous Uses In the absence of data on emissions and emission factors no estimates vere made, Refer to section 7.6.3.7 for further remarks. 7.6.3.7 Summary of p-Nitroaniline Emissions Refer to Table 7.5 for a summary of the emissions during manufacture of the products from p-nitroantline. Emissions for those products manufactured from p-nitroantline could be calculated if the following data were available: 1) Consumption data on pruitroaniline for each of the products. 2) ‘The production flow diagram with explanation of each of the processes and product yields. 3) Data on the types, character, and quantity of waste streams. 4) The type and efficiency of the waste treatuent facilities. 7.7 EMISSIONS DUE TO EXPORTS OF para-NITROANILINE An investigation conducted by the Foreign Trade Conmission consisting of a search of the July 1978 invoices revealed no exports of p-nitroaniline, 7-16ure ‘TABLE 7.5 pata-NITROANILINE EMISSIONS GENERATED DURING ITS USE Product 1978 1977 1976 Manufactured from para-nitro- aniline by category air Emissions kkg Emissions kkg Emissions kkg water = air water air water Rubber Chemicals 60 500 40 400 20 200 byes and Dye Intermediates 8 100 6 100 3 50 Agricultural Chemicals Gasoline Additives Pharmaceuticals and Veterinary Products Miscellaneous 1975 Emissions kkg air 50 water 500 100 1974 Emissions kkg air water 50 400 6 100 ‘TOTAL 68 600 46 500 23 250 56 600 56 5008.0 OTHER NITROANILINES This materials balance also reported readily available information on sixteen nitroanilines in addition to the three mononitroanilines considered separately in Chapters 5, 6, and 7. For the purposes of the present chapter, a nitroaniline was defined as any aniline containing a nitro group, whether or not a halogen was present in addition. The haloanilines are considered in Chapter 9. 8.1 PROPERTIES Table 8.1 summarizes the physical properties of the nitroanilines being considered, Neither data on vapor pressures nor quantitative data on solu- bilities vere availabl. qualitative characterizations of solubility are pre- sented only as a general guideline, These compounds are solids at room tenp- erature and exhibit almost no solubility in cold water. 8.2 MATERIALS BALANCE FOR NITROANTLINES In view of the lack of data available on the nitroanilines of interest here, neither individual nor a composite materials balance diagram was constructed. 8.3 PRODUCTION OF OTHER NITROANILINFS 8.3.1 Producers and Locations Figure 8.1 shows the locations and names of the producers of nitroanilines considered in this chapter. The producers are located in the eastern half of the country, mostly along the east coast and gulf coast. Table 8.2 (end of chapter) lists producers for the past five years. In 1974 and 1975, capacity Figures were presented for three compounds, but not by individual producer. These total capacities figures are also presented in Table 8.2. 8-1‘TABLE 8.1 PHYSICAL PROPERTIES OF NITROANILINES! GLASS compouND WP. BLP. SOLUBILITY IN H,0 Dinitro- 2,4-dinitro- 188° insol anilines 2, 6-dinitro~ 141-142° insol Chloronitro- 4-chloro-2-nitro- 116.3° insol ‘anilines -2-chlore~4~nitro— 107° slight 4-chloro-3-nitro~ 95-97° partial 2-chloro-6-nitro~ 76° 3-chloro-4-nitro—- 156-157" S-chloro-2-nitro- 126.5° 3-chlore-5-nitro- 2-chloro-5-nitro- 4-chloro-2,6-dinitro- sol (hot) 3-chloro-2, 6-dinitro— sol (hot) 2,6-dichloro~s-nitro- Brouonitro- 2, 6-dibromo~4-nitro- 207° slight anilines 2bromo~4,6-dinitro- ——153-154° Bromochloro- 2-bromo-6-chloro- nitroaniline 4-nitro Ieources: Hawley, 1977; Weast, 1977-78. 8-28.3.2 Amounts Produced Data were not available on current production of any of the nitroanilines considered here. These data are needed for any useful calculation of emissions due to production. 8.4 IMPORTS OF NITROANILINES 8.4.1 Amounts Table 8.3 shows the data available on imports of nitroanilines. It was not known what fraction of domestic production these values represent. 8.4.2 Emissions Due to Imports Data were not available on either emission amounts or emission factors attributable to nitroaniline imports, Furthermore, the ofl spill/risk model deseribed in Section 2.5.2.1 was not considered applicable to solid compounds Like nitroanilines. Therefore, estimates of emissions must avait the avail- ability of the following information: 1) wore complete importation statistics; 2) monitoring data or a measured emission factor applicable to air, water, or total emissions. 8.5 CONSUMPTION AND USE No quantitative data were available on consumption processes for nitro- antlines, This would appear to be an important area for future study.Compound 2,4-dinitro- aniline 2, 6-dibromo- 4-nitroaniline 2, 6-dichloro~ 4-nitroaniline 2-chloro~4, 6— dinitroaniline TABLE 8.2 1978 American Koechst Coventry, RI Martin-Marietta Sodyeco, NC American Hoechst Martin-Martetta Salsbury Labs Charles City, 1A Upjohn Co. North Haven, CT BASF Wyandotte Rensselaer, NY PRODUCERS OF NITROANILINES, 1977 1976 ‘American Hoechst Coventry, RI Martin-Marietta Sodyeco, NC Chentronics, Inc. Swannanoa, NC (40.5 ka) American Hoechst Martin-Marietta Salsbury Labs Upjohn Co. carroll Prod. Wood River Jet., RI Drake Chem. Lockhaven, PA 1974-1978! 1975 1974 Amer. Color and Chem. Amer, Hoechst Martin-Marietta ‘Toms River Chem Co. Toms River, NJ Total Capacities = 262 kekg/yr American Hoechst Martin-Marietta Salsbury Labs Total Capacities = 20 kkg/yr Upjohn Co.TABLE 8.2 PRODUCERS OF NITROANILINES, 1974-1978! (continued) Compound 1978 1977 1976 1975 1974 2-chloro-4— Allegheny Ludlan duPont Co. duPont! Co, duPont Co. nitroaniline Industries Deepwater, NJ Huntington, WV 4-chloro-2- Mobay Corp. Amer. Cyanania duPont Co. duPont nitroaniline Bushy Park, SC Bound Brook, NJ (5-45. kkg) G.F, Smith Chen, Columbus, OH duPont Co. (45-450 kg) Carroll Prod. 2-bromo-6- American Hoechst American Hoechst American Color chloro~4-nitro~ and Chen. aniline duPont 2-bromo-4, 6- American Hoechst American Hoechst American Color Amer. Color Amer Color dinitro— and Chen. and Chen. and Chem. aniline Martin-Marietta Mart in-Marietta Toms River Chen. Co. ‘Toms River Chem. Co. GAF corp. Rensselaer, NY ICI Americas Dighton, MA American Hoechst Martin-Marietta American Hoechst Martin-Marietta Tans River Chem. Co. American Hoechst Martin-Marietta ‘Toms River Chen Co. ‘Total Capacities 932 kkg/yrce TABLE 8.2 PRODUCERS OF NITROANILINES, 1974-1978! (continued) Compound 1978 4-chloro-3- nitroaniline 4-chloro-2,6= dinitroaniline 2-chloro-5- nitroaniline 1, Source: USITC, 1976-1979; EPA, 1977 1976 1975 Tennessee Eastman Kingsport, TN (45-450 kkg) Kodak Park Div. Rochester, NY Tennessee Fastnan Kingsport, TN (45-450 kg) 1977es TABLE 8.3 IMPORTS OF NITROANILINE COMPOUNDS 1974 to 1978 (kkg/year)! Compound 97a 197776 ars? 1974 2,4-dinitroaniline 100 170 170 54 270 2-chloro-t-nitroant Line 2300880 d-chioro-S-nitroant tee ~ 5 30 2 0.7 d-choro-2-nitroant tine 50 - rr 1 _ 5 2-bromo-2, 6~dinitroaniline 10 ~ ~ 40 lyntted States International Trade Commission (1974-1978). Imports of Benzenoid Chemicals and Products. The deport figures do not reflect any imports fron air transportation. See footnote 3. ‘Those places in the table where dashes occur indicate that no imports were reported for the compound during that year. ‘The USITC Imports of Benzenoid Chemicale and Products and tables for 1974, 75, 76, 77, and 78 do not reflect the entire import anount, Each report states a “statistical coverage": the estimated fraction of the total imports that was actually reported. The statistical coverage values used for the compounds in this table were the ones that applied to the category, "intermediates." Statistical Coverage Year ue 1978 76 percent 1977 81 percent 1976 80 percent 1975 94 percent 1974 99 percent6-8 Footnotes to Table 8.3 continued. ‘The values in the table have been corrected for less-than-total reporting using the statistical coverage value, This was attained by applying the following formula to each value in the table: Import Compound at _ USITC Reported 1 wantity x 100% 100% Value Ustte Sentistioal Covereee Value G)- Pane import figures for 1975 were not readily available and attempts to obtain these figures were unsuccessful. Srersonal communications between Ron Burger, JRB Associates, Inc., McLean, Virginia, and Mr. Magnusson, Office of Rubber and Chemicals, U.S. Department of Commerce.9.0 CHLORO- AND BROMOANILINES 9.1 PHYSICAL PROPERTIES ‘The physical properties of the chloro- and bromoanilines to be reviewed in this chapter are shown in Table 9.1. Quantitative solubility data were unavailable; qualitative characterizations are presented as a general guideline. TABLE 9.1 PHYSICAL PROPERTIES OF CHLORO- AND BROMOANTLINES! MELTING BOILING SOLUBILITY TEMPERATURE AT CLASS coMPOUND POINT _ POINT IN H0 V.P. of 1 Torr Monochloro- _o-chloro 208-210° insol 463°C anilines mchloro 228-231" insol 63.5 pechloro- 229-233 sol (hot) 59.3°C Dichloro- 2,3-dichloro- anilines 2,4-dichloro- 2,5-dichloro- 47-50° 251-252" slight 3,4-dichloro- 68-72° 272° slight 3, 5-dichloro- Trichloro- _2,4,6-trichloro 78.5" 262° insol 134°C anilines Tetrachloro- 2,3,4,5-tetrachloro~ 118-120° anilines 2,3,4,6-tetrachloro- 2,3,5,6-tetrachloro- 108° insol Pentachloro~ 2,3,4,5,6-penta~ antlines chloro- 232° Monobromo- —_p-bromo- 66.4" insol anilines ‘Tribromo- 2,4,6-tribromo- 122° 300° insol anilines "sources: Hawley, 19773 Weast, 1977-78. 9.2. MATERIALS BALANCE FOR CHLORO- AND BROMOANTLINES In view of the lack of information available on the chloro- and bromo- anilines of interest, neither individual materials balance diagrams nor @ composite diagram was constructed.9.3. DIRECT PRODUCTION OF CHLORO- AND BROMOANILINES 9.3.1 Production Processes, Producers, and Locations Figure 9,1 collects the available data on the producers of chloro- and bromo~ anilines, their locations, and the organic synthetic reactions used. 9.3.2 Amounts Produced No quantitative data were available on anounts of chloro= or brosoanilines produced. This information may be available from the following sources: 1) Chemical Marketing Reporter or other trade periodicals; 2) By a complete analysis, starting with anounts of end-products (e.g., specific dyes) utilizing a particular haloaniline and working backwards to account for all consumption by either importation or domestic production. 9.3.3 Emissions Due to Direct Production In the absence of production data, it was not possible to calculate useful emissions values due to production. 9.4 INDIRECT PRODUCTION 9.4.1 Chlorination of Waste Anilines Chlorination is sometimes applied to waste stream in order to disinfect. It has long been known that Cl, reacts with activated aromatic rings to produce chloro- aromatics, The classic example is the chlorination of phenol (Morris, 1975) to produce mono-, di-, and trichlorophenols. It is quite possible that a similar reaction would take place on aniline, which is also quite susceptible to electro- philic attack (note, however, that nitroanilines would be deactivated and would probably not chlorinate). We suggest that this might be a mechanism for production of chloroanilines from aniline in waste streams. The physical result could be settling out of less-soluble chloroanilines, Additional research is needed in this area to evaluate the contribution of this reaction to the overall aniline materials balance, and the relative toxicities of aniline and chloroanilines. 9-2FIGURE 9.1 GHLORO- AND SROWOAKILIRE PRODBETION lp-chioro-, Btndienioro= Sytsetenioro-, ~! (xs ‘PRODUCERS, LOCATIONS, CHEMISTRY — me fees BNE ~ ‘Monsanto Bofors Lakeway, Monsanto, eer cans Oey ae visa oa eee mn 3s ar ty ao fo pavienmtioe 4, sont souseran tee * wh ‘Monsanto, (45-450 kkkg) Monsanto Monsanto, Monsanto A A S oe t som ns a © nos a Ore a oe . duPone Nonasneoeen eye Seertehtoro 14, 6-trsbeonoanttine 2,4-dtentoroansiine 2,todtchlorcanttine Source: Sms aractiow PRODUCERS, LOCATIONS, CREXISTRY 978 197 Plastifax, Tne. Tenn Gulfport, Mt eastaan (45-250 es) Columbia Org. Upjoia Cor Noreh Faven ct Pike Chenteals stro, 3 Plastitax, Toe. Carroll Prod, Chen, Systens te. Sen Jos (S450 kis) Draka Chen. Aldrich chea, Meteaukes eae Lafayecte, 1H ‘Tenne Kingsport, TY (o.s3 ep) Taling, 1A duront Deepwater, 0 USITC, 1976-79: Hancock, 1975; U.S. EPA, 1977 Lis dupont hea. co: Helena, AR Monsanto 19% Kodak9.5. IMPORTS OF CHLORO- AND BROMOANILINES 9.5.1 Amounts Table 9.2 summarizes the information on imports of chloro- and brono- anilines that was readily available. missions due to importation of o- chloroaniline and m-chloroaniline could be estimated by applying the of1 spill/risk model described in section 2.3.2.1. The estimated enissions which are obtained by multiplying a small amount of imported anilines x a very small emission factor (7 x 10.” kkg/kkg transported), would be very small. Useful emissions estimates for the solid chloro- and bromoanilines were not possible. 9.6 CONSUMPTION AND USE Table 9.3 summarizes qualitative data available on consumption and uses of haloanilines, No quantitative data were available, so no useful estimates of emissions could be made. TABLE 9.3 CONSUMPTION AND USES OF CHLOROANILINES? comeounp uses o-chloroaniline Dye intermediate, colorimetric standard, petroleum solvents, fungicides m-chloroaniline Azo dyes and pigments, pharmaceuticals, insecticides, agricultural chemicals prehloroaniline Dye interneidate, pharmaceuticals, agricultural chemicals 2,5-dichloroaniline Dye intermediate 3,4-dichloroaniline Dye intermediate, biologically active compounds "source: Hawley, 1977.TABLE 9,2 IMPORTS OF CHLORO- AND BROMOANILINE COMPOUNDS Compound o-chloroaniline m-chloroaniline p-chloroaniline 2,3-dichloroaniline 2,4-dichloroaniline 2,5-dichloroaniline 2,4, 6-trichloroaniline p-bromoaniline 1974-1978 (kkg/year)* aye as? 976 20 = 2101990 _ 60 50 60 40 0 4 6 - 10 190150 10 5 6 a . \uattea States International Trade Commission (1974-1978). Benzenoid Chemicals and Product: ‘imports from air transportation. 197s 974 63 40 2 1 33 no oo 56 - - 100 Iaports of The import figures do not reflect any See footnote 3. ‘Those places in the table where dashes occur indicate that no imports were reported for the compound during that year. ‘The USITC Imports of Benzenoid Chemicals and Products and tables for 1974, Each report 75, 76, intermediates." Year 1978 1977 1976 1975 1974 ‘and 78 do not reflect the entire import amount. states a "statistical coverage’ that was actually reported. Statistical Coverage Value 76 percent 81 percent 80 percent 94 percent 99 percent the estimated fraction of the total imports The statistical coverage values used for the compounds in this table were the ones that applied to the category, ‘The values in the table have been corrected for less-than-total reporting using the statistical coverage value. following formula to each value in the table: Inport Compound at 100% Value SITC Reported Import Quantity x 100% = [Site Seatisticel-covevage Value = Coverage Value CZ This was attained by applying theFootnotes for Table 9.2 continued *the import figures for 1975 were not readily available and attempts to obtain these figures vere unsuccessful. 3personal communications between Ron Burger, JRB Associates, Inc., Mclean, Virginia, and Mr. Magnusson, Office of Rubber and Chemicals, U.S. Department of Commerce. 9-710. LOCATIONS OF EMISSIONS This chapter will collect the information already presented on locations of producers of anilines in order to identify sites with a large point source or multiple sources. The results are shown in table form (Table 10,1). The table shows that the only locations with multiple compounds produced were Bound Brook, NJ (two producers making three products); Deepwater, NJ (one producer making three products); and Sauget, IL (one producer making two products). Bound Brook, NJ, is the only eity with two separate producers (American Cyananid and Blue Spruce Co.). It is important to note, however, that this analysis will not be complete until consumption sites - the major points of estimated enissions ~ can be tabulated and analyzed in the sane way. 10-1z-01 Location Aniline Aniline HCL TABLE 10.1 Andlines Aniline HBr er-nitro~ genitro- LOCATIONS OF EMISSIONS penitro Other nitro Chloro- & bromo- Bound Brook, NJ Deepwater, NJ Gibbstown, NI Linden, NJ Toms River, NJ Coventry, RI North Haven, CT Renssalaer, NY Rochester, NY Huntington, WV New Martinsville, WX Willow Island, WV Lock Haven, PA Sodyeco, NC Bushy Park, SC Gulfport, MS Pascagoula, MS Geismar, LA Luling, LA Shreveport, LA Beaumont, 1X Helena, AR Kingsport, TW Charles City, TA Milwaukee, WI Sauget, IL Ht oe11.0. DATA Gaps During the preparation of this report, a series of significant data gaps were identified, Several of these have been mentioned in earlier chapters, and they will be summarized here. 11,1 PRODUCERS AND AMOUNTS PRODUCED FOR LESS-WIDELY-PRODUCED ANILINES It was not possible to calculate emissions due to production for the com- pounds aniline hydrochloride, g-nitroaniline, and the grouped nitroanilines and haloanilines because of the absence of production data, Since the actual product- ion figures are proprietary, an estimate based on another approach (1ike plant capacity analysis or back-calculation starting with consumption data) might be needed. 11.2 CONSUMPTION AND USE INFORMATION FOR LESS-WIDELY-USED ANILINES Consumption data are necessary to the estimation of emissions due to consump- tion, These data were lacking for the compounds aniline hydrochloride, m-nitro- aniline, and the grouped nitroanilines and haloanilines. It might be possible to obtain this information from a plant-by-plant analysis of 1) products marketed, 2) ch istry of a particular product's synthesis, and 3) how much of the product was made per year. This might be feasible in a Level II or Level ITT materials balance. Another important question about consumption is: how much of the in~ put aniline was carried over into the product? Chemical analyses of products would be necessary to answer the question. 11,3. DATA ON EFFLUENT ANALYSIS OR EMISSION FACTORS FOR ANILINE PRODUCTION Because the estimation of emissions to water during aniline production is a key value to obtain, it should be calculated at least two ways. More data are needed concerning waste stream analyses and waste treatment procedures, preferably on a plant-by-plant basis.11.4 ACCESS TO IMPORT AND EXPORT DATA WITHIN THE 'BASKET' CATEGORIES Information on relevant imports and exports are sometimes available but hidden within the USTTC's "all other" category. It would be helpful if there were a procedure for obtaining information from these "basket" categories on short notice.REFERENCE LIST American Chemical Society, 1978. "Chemical and Engineering News," July 17, 1978. Washington, DC. Cagarett, L. J., and Doull, J. (eds.), 1975. Toxicology, The Basic Science of Potsons, McMillan Pub. Co. Catalytic, Inc., 1978. Bnvironmental Protection Agency Guidelines Report: Plants by Product Process, U.S. Environmental Protection Agency, Washington, te eye Chemical and Engineering News, Sept. 9, 1974. Chemical Marketing Reporter, August 30, 1976. Chenical Marketing Reporter, June 11, 1979. Chemical Purchasing, June 1977. Chemical Weekly, August 11, 1976. Directory of Chemical Producers, USA, 1979. Stanford Research Institute, Menlo Park, CA. Federal Register 1976. Environmental Protection Agency, Organic Chemicals Manufacturing Point Source Category, Title 40, Part 414, Jan. 5, Vol. 41, No. 2., pi 925, Washington, D.C. Hahn, A. V., 1970. The Petrochemtcal Industry Market and Economics, McGraw-Hill Book Co., New York, WY. Hancock, E. G. (ed.), 1975. Benzene and Its Industrial Derivatives, John Wiley and Sons, New York, Nf. Hawley, G. G., 1977. The Condensed Chemical Dictionary, 9th ed., Van Nostrand Reinhold Co., New York, WY. Howard, P. H., Santodonato, Joseph, et al., 1976, Investigation of Selected Potential Environmental Contaminants: Nitroaromatics, U.S. Environmental Protection Agency (Office of Toxic Substances), Washington, DC. [PB-275-078] Hydroscience, Inc. 1977. Emissions Control Options for the Synthetic Organic Chemicals Manufacturing Industry: Aniline Trip, Report for E. I. duPont de Nemours, Beaumont, TK, Sept. 7-8, 1977, U.S, Environmental Protection Agency (Office of Air Quality Planning Standards), Research Triangle Park, NC. Kirk-Othmer, 1966, Encyclopedia of Chemical Technology, 2nd ed., Vol. XI, Interscience Publishers, New York, NY. Lowenheim, F. A., and Moran, M. K. 1975, Faith, Keyes and Clark's Industiral Chemicals, 4th ed., Wiley~Interscience, New York, NY.Mastendrea, J. R., and Simmons, J. A., 1978. Deepwater Port Inspection Methods and Procedures, Science Applications, Inc., (DOT=CG-60670-A), November 1978. MeCaleb, K. E., 1979. Chemical Ecnonomics Handbook, "Aniline and Nitrobenzene," Stanford Research Institute, Menlo Park, CA. Morris, J. C., 1975, Formation of Halogenated Organics by Chlorination of Water Supplies, U.S. Environmental Protection Agency, [P5-01-1805-J]. Ottinger, R. S. and Blumenthal, et al. 1973, Recommended Methods of Reduction, Neutralization, Recovery or Disposal of Hazardous Waste, Volume X, Industrial ‘and Municipal Disposal Candidate Waste Strean Constituent Profile Reports = ‘Organic Compounds, U.S. Environmental Protection Agency (Office of Research ‘and Development), Cincinnati, OH [68-03-0089]. Patty, Frank (ed.) 1963, Industrial Hygiene and Toxicology, Vol. II, Interscience Pub., New York, WY. Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia and Mr. Magnusson, Organic and Rubber Chemicals Branch, U.S. Department of Connerce, Washington, DC, October 24, 1979. Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia and Mr. Ed Cappuccilli, Energy and Chemical Branch, U.S. International Trade Commission, Washington, DC, October 24 and 25, 1979. Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia and Mrs, Hardy, Chemicals and General Manufacturing Branch, Foreign Trade Division, Bureau of the Census, October 29, 1979. Personal Communication between Mr, Ron Burger, JRB Associates, McLean, Virginia and Mr. Fred Dorf, Manager of Manufacturing Polymer Additives, Anerican Gyanamid, Wayne, NJ, October 29, 1979. Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia and Mr. Rick Johnson, Clean Environment Program, Tennessee Eastman Chemical, Kingsport, TN, October 30, 1979. Sax, NE. (ed.) 1975, Dangerous Properties of Industrial Materials Reinhold Pub, Co. Science Applications, Inc. 1977, The Programatic ETS for the Strategic Petroleun Reserve Progran Supplenent, (Graft report for Department of Energy)e Decenber, 1977. Science Applications, Inc. 1978. Development of Environmental Criteria and Guidelines to Assess the Environmental Plan Submitted as Part of the O11 Purchase - Transport Contract, (DOE, CR-13-70174), June 1978.Simmonds, H. R. and Church, J. M. 1967. The Encyclopedia of Basic Materials for Plastics, Reinhold Pub. Co. Snell, F, P. and Hilton, C. L., (ed.) 1967. Encyclopedia of Industrial Chemical Analysis, Interscience, New York, NY. Snell, Snell 1962. Dictionary of Commercial Chemicals, 3rd ed. Van Nostrand Co., Princeton, NJ. Shreve, R. N. 1967, Chemical Process Industries, 3rd ed., McGraw-Hill, New York, NY. Steednan, Thomas and Helper, Eleanor, 1977, Industrial Process Profiles for Environmental Use, Ch.'7, "Organic Dyes and Pigments Industry,” U.S. Environmental Protection Agency, (Office of Research and Development), Cincinnati, OH (EPA-600/2-77-023g). Stecher, P, G. (ed.) 1968. The Merck Index, 8th ed., Merck and Co., Inc., Rahway, NJ. ‘TRH Systems Group, 1973. Recommended Methods of Reduction, Neutralization, Recovery of Hazardous Waste, Vol. XI, Industrial and Municipal Disposal Candidate Waste Stream Constituant Profile Reports, Organic Compounds (Continued) U.S. EPA, Washington, DC [PB-224-590]. U.S. Army Corps of Engineers, Waterborne Conmerce in the United States, 1973-1976. U.S. Coast Guard, Pollution Incident Reporting System (PIRS) 1973-1976. U.S. Department of Energy, Draft EIS, Crude O11 Storage in Salt Domes in Southwestern Mississippi and Nofthern Louisiana, Departuent oF Enerky, ha United States International Commission. 1974-1978. Imports of Benzenoid Chemicals and Products, USITC Publications 762, 806, 828, 900, 990, Washington, DC. U.S. Environmental Protection Agency, 1979, Computer Printout of the Nonconfidential Portion of the TOSCA Inventory, Chemical Information Division, Office of Pesticides and Toxic Substances, May, 1979. U.S. International Trade Commission 1975-1979, Synthetic Organic Chemicals United States Production and Sales, Publications 776, 804, 833, 920, Washington, DC. Verschueren, K., 1977. Handbook of Environmental Data on Organic Chemicals, Van Nostrand Reinhold Co., New York, NY. Weast, R. C. (ed.) 1977. Handbook of Chemistry and Physics, 58th ed., GRC Press, Inc., Cleveland, OH.APPENDIX A Description of Aniline Production by Catalytic Vapor-Phase Hydrogenation of Nitrobenzene Source: Lowenheim, F. A., and Moran, M. K. (eds), 1975, Faith, Keyes, and Clark's Industrial Chemicals, 4th ed. ¢ 1975 by John Wiley and Sons, Inc. Re~ printed by permission, Nitrobenzine containing less than 10 ppm thiophene 1s vaporized in a stream of hydrogen and passed into a reactor containing a fluidized bed of copper catalyst. The catalyst 1s made by spray-drying a silica hydrogel upon which cuprannoniua nitrate has been adsorbed. The catalytic powder (10 to 20% copper) (20 to 150 a) is activated in place in the reactor by treatment with hydrogen at 250°C. The nitrobenzene vapor-hydrogen mixture (300% excess hydrogen) 1s fed through a porous distributor plate in the bottom of the fluidized bed reactor held at 270°C and 5 psi (34.5 kPa). Excess heat of reaction is removed by circulating a cool heat-transfer flutd through tubes suspended in the catalyst bed, Exit gasses are filtered free of catalyst fines on porous stainless-steel filters in the top of the reactor. The filtered product gasses are condensed, further cooled, and sent to a Liquid separator or decanter. Excess hydrogen is recycled. The lower layer of liquid in the separator (crude aniline containing less than 0.5% nitrobenzene and 5% water) is distilled to remove high botlers. The water and aniline vapors that pass overhead are separated by further distillation. ‘The upper (aniline water) layer from the separator is pumped to an extraction column, where it passes countercurrent to cold nitrobenzene for recovery of dissolved aniline. A yield of 98% 4s claimed for the process. The catalyst will produce 1500 kg antline/kg of catalyst before regeneration is required. Regeneration is accomplished in place by flushing the system with an inert gas, and then passing air through the catalyst at 250 to 350°C to burn off organic deposits. AlSeveral different catalysts have been patented for use in aniline processes similar to that described. Operating procedures will of course vary with the activity and ruggedness of the catalyst used. An effective catalyst for a fixed-bed hydrogenation is nickel sulfide deposited on alunina. Ao“APPENDIX B= PRODUCTS DERIVED FRUM aNrLine? PRODUCTION PROCESS DERIVATIVE USES a Aniline + acetic anhydride or aniline + glacial acetic acid (27) ACETANILIDE (27) Manufacture of p-nitroaniline and o-nitro- ‘aniline (27) Sulphonamide Intermediate (27) lydrogen Peroxide Stabilizer Cellulose Ester Lacquers Manufacture of Dyes and Intermediates Analgesic and Antipyretic Manufacture (36) Sulfa Drugs (33) Local Anesthetic (33) Aniline + ethylacetoacetate Aniline + diketene (36) ACETOACETANILIDE (27) Dye Intermediate Manufacture of Benzidine Yellow Pigments (27) Aniline + phosgene vapor or organic solvents (27) PHENYL ISOCYANATES (27) Manufacture of Tsocyanates urethanes. disubstituted ureas Insecticides and Herbicides (27) Methanol + aniline + sulphuric acid under heat and pressure (27) Aniline + formaldehyde reduced by zine and sodium hydroxide (27) N-MBTHYLANILINE N,N-METHYLANILINE (27) Brdimethylaminobenzaidehyde manufacture (27) Aniline + excess methanol + acid catalyst under heat and pressure @) N,N-DIMETHYLANILINE (27) Dye Intermediate (33)APPENDIX B PRODUCTS DERIVED FRuM ANILINE? PRODUCTION PROCESS DERIVATIVE, USES a Aniline + hydrochloride + ethanol under heat and pressure (27) N-ETHYLANTLINE (27) Manufacture of Stabilizer For Explosives (27)| Vuleanization Accelerator (36) Aniline + sulphuric acid (27) SULPHANILIC ACTD (27) Manufacture of Three Sulphonilic Acids Intermediate in Azo Dyestuffs and a Component) in 91 Dyes (27) Aniline + carbon disulphide + sulphur heated in an autoclave (27) 2-MERCAPTOBENZOTHIZOLES (27) Manufacture of Vulcanization Accelerators Qn Sulphonamide Vulcanization! Accelerators (27) Aniline + aldehydes + organic acid as a catalyst (27) ALDEHYDE~AMINE REACTION PRODUCTS (27) * Manufacture of Vuleanization Accelerators @1) Cyanogen chloride + hot aqueous aniline (27) 1,3-DIPHENYLGUANTDINE, (27) Manufacture of Vuleanization Accelerators Q7) Aniline + carbon disulphite (27) THIOCARBANTLIDE (27) Accelerator for Specific Rubbers (27) Aniline + hydrochloric acid as a catalyst or substituted aniline with] ketones + hydrochloric acid (27) 2,2, 4-TRIMETHYL-1, 2-DIIYDROQUINOLINE @Q7) Rubber Antioxidant (27) Condensation of hydroquinone and two moles of aniline + acid catalyst! @7) N,N-DIPHENYL~P-PHENYLENEDIAMINE. (27) Rubber Chemicals antiozonant (28) antioxidant (28)APPENDIX B PRODUCTS DERTVuy HOM ANILINE? PRODUCTION PROCESS DERIVATIVE, USES ea Liquid phase catalytic hydrogenation of aniline under pressure at 135° 170°C and under 50 - 500 atmospheres in the presence of a catalyst (27) oD \ CYCLOHEXYLAMINE (27) Major Use: Manufacture of Sodium and Calcium Cyclohexyl-Sulphamates used in the Manufacture of Synthetic Sweetening Agents Qn Derivatives Used in the Manufacture: Rubber Chemicals: vulcanization accelerators antioxidants antiozonanta Corrosion Inhibitors - ferric metals Plastic Resins Intermediate in Dyestuffs (27) Used Directly in Boiler Vater Linit Scaling and Corrosion Dyestuff Intermediates (27) Vapor phase reaction with nickel catalyst of aniline DICYCLOHEXYLAMINE (27) Corrosion Inhibitors Ferrous Metal Articles Derivatives: Form Sulphonamides Used as Rubber Acceierators Salts and Metal Compounds Used in Textile, Paint and Varnish Industry (27) Aniline ts oxidized by manganese dioxide or sodiun dichromate in sulfuric acid to quinone. Quinone 4a reduced by fron in water (31) HYDROQUIONONE (31) Photographic Developer (28) Polymerization Inhibitors in Monomers (28) Manufactures of BHA Food Antioxidant (28)ra APPENDIX B PRODUCTS DERIVED FROM ANILINE! PRODUCTION PROCESS DERIVATIVE USES ANILINE (REFER TO FOOTNOTE 2) Rubber Chemicals: accelerators (36) antioxidants (28) antidegradant (33) curing agents (33) elastomers (33) MDI Production (33) Dyes: Intermediate: (39) stilbene triarylmethane azine dyes indigoid dyes Dyes (33) Predye Fiber Treatment (33)(34) Catalyste: (33) polymerization reactions organic reactions organonetallic reactions metallurgical industry Patina production Resins: (33) production of epoxy resins and harding agents production plastics (38) aniline formaldehyde resins (33) Petroleum: (33) antiknock ~ gasoline knock suppressor aviation fuelAPPENDIX B PRODUCTS DERIVED FkOH ANILINE PRODUCTION PROCESS DERIVATIVE. USES ‘The table presents ANILINE and references, ‘The reference list The referenced resources stated production process. directly. Therefore, ANILINE (continued) ts Derivatives, their method of producti that applies to this appendix only is a luses for “aniline and derivatives" but 4 luses stated under aniline may be from fe: Rocket Fuels: (33) ignition fuels self-flanmable fuel mixture Explosives: (38) detonator constituent for gunpowder Agriculture Uses: (33) intermediate for peat sprays Reagent (33) qualitative detection of metals Papermaking process Electronic Industry: (33) polishing diode and transistors Solvent for Organic Reactions (33) In and uses tached. 2 gleaned from readily available jd not etate the aniline compound nor the ivatives of aniline rather than anilineAPPENDIX B PRODUCTS DERIVED FRUH ANILINE HYDROCHLORIDE PRODUCTION PROCESS DERIVATIVE USES Heating aniline. and aniline hydro- | DIPHENYLAMINE (1, 28, 31, 33) Rubber Industry chloride at 210°-240°C at 90 pat in the absence of a catalyst, 30 to 35 hours (33) antioxidants (28) antiozonants (27) retarder (28) stabilizer (36) Agriculture antihelminthtes (28) insecticides (31) fungicide (33) Dye Industry Preparation of azo dyes (31) printing (1, 30) dyestuff intermediate (36) Miscellaneous : stabilizer for explosives (28, 36) metallurgy ~ plating baths (33) organic synthesis: Heating aniling hydrochloride with ethanol at 180°C, refluxing with ethanol over Raney (33) N-BTHYLANILINE (33) Rocket Fuel (33) Dye Intermediate (31) Neating aniline hydrochloride with excess ethanol at 180°C under pressure (31) DIETHYLANILINE (31) Herbicide (10) Aniline hydrochloride plus excess bromide (27) 1, The category "organic synethests" 2,4,6-TRIBROMOANILINE (27) refers to’ the use of diphenylamine in thi synthesis of numerous organic compounds.APPENDIX B PRODUCTS DERIVED FROM ortho-NITROANILINE PRODUCTION PROCESS DERIVATIVE, uses Reduction of o-nitroaniline with sodium sulphide under pressure (28, 36) ‘O-PHENYLENEDTAMINE (27, 36) Antioxidants Anhibicor of copper corrosion (27) antifreeze preparations (27) lubricating oils (27) polishes detergents (27) Rubber Chemicals and Intermediates (27) byes €.1. Oxidation Base 16 (27) hair dyes (36) optical bleaches (27) dyestuff intermediate (27) Pharmaceutical Products (27) Veterinary Products antihelminthics (27) Miscellaneous tedox indicator (27) chemical detection of metals (27) O-NITROANILINE byes Preparation of azo and anthraquinone dyes (1, 3, 27) azoic diazo componeit 6 (27) Photographic Antifogging Agents (1, 36) Coceidostatis (1) Interior Paint Pigments (1) N-CYCLOALKENIC (27) Insecticides and Intermediates (27)APPENDIX B PRODUCTS DERIVED FROM meta-NITROANIL. PRODUCTION PROCESS DERIVATIVE USES Reduction of mnitroaniline with iron] m-TOLUIDINE (31) Dye Preparation (1) tnd dilute acid or catalytic hydro- genation (31) m-NITROANILINE (27) Organte Synthesis (3, 31) bye Intermediate (3, 27, 31, 36) Synthetic Sweeteners (31, 33)APPENDIX B PRODUCTS DERIVED FROM para-NITROANILINE PRODUCTION PROCESS DERIVATIVE usES Reduction of p-nitroaniline by iron or sulfide (27) N-SUBSTITUTED p-PHENYLENEDIAMINES Antioxidants and Antiozonants (27, 28, 31) Hair and Fur Dye, Azo, Azine, Sulfur, and Cyanine Dyestuffs (27) Dye Intermediate (27) Reduction of p-aitroantline with iron and dilute acid or catalytic hydrogenation (31) BATOLULDINE (31) bye Production (31) Organic Synthesis (31) Diazotization of p-nitroaniLine with! UCL and sodium nitrite (31) B-NITROANTLINE HYDROCHLORIDE (31) nyes (31) Mitration of p-nitroantline (27) 2,4,6-TRINITROANILINE (PICRAMIDE) (27) Direct chlorination of p-nitro~ aniline in benzene solution at 20°C with tert-butyl hypochlorite (33) 2, 6-DICHLORO-4-NITROANILINE. (33) _B-NITROANTLINE \ Corrosion Inhibitor (1) Veterinary and Pharmaceutical Products (1, 3)| Agricultural Chemicals (3) byes and Dye Intermediates (1, 31) Gasoline Additives (1, 3) Rubber Chemicals antioxidants (1) Fungicides Botran (28)o1-e 28. 31. 33. 36. Snell, Snb11, Dictionary of Commercial Chemicals, 3rd ed., Van Nostrand Co., Princeton, NJ. 2 38. 39. REFERENCES FOR APPENDIX B ONLY Hancock, E.G. (ed.), Benzene and Its Industrial Derivatives, Joha Wiley and Son, NY, 1975. Hahn, A.V., The Petrochemical Industry Market and Economics, ! McGraw-Hill Book Co., NY, 1970, i Kirk-Othner, Encyclopedia of Chemical Technology, 2nd ed., Interscience Publishers, NY, 1968. Snell-Hilton, Encyclopedia of Industriel Chemical Analysis, Interscience i Publishers, 1967. | Simonds, H.R. and Church, J.M., The Encyclopedia of Basic Materials | for Plastics, Reinhold Pub., Co., 1967. t Industrial Process Profiles for Environmental Use, Ch. 7, "Organic Dyes and Pigments Industry,” prepared for Office of Research and Development,’ U.S. Environmental Protection Agency, Cincinnati, OH, 1977. Hawley, G.G., The’ Condensed Chemical Dictionary, 9th ed., : Van Nostrand Reinhold Go., New York, 1977.-; G ippel ‘TRW Systems Group, Recommended Methods of Reduction, Neutralization,Recovery, or L Disposal of Hazardous Wastle, Vol. X, organic compounds. Prepared for U.S.Environmental! Protection Agency, Washington, D.C.TECHNICAL REPORT DATA (lease read Vssractos on the reverse Before comnlting) RETGAT AS B Pr REGIMENTS ACESSTON WO EPA-560/13-80-013 Level I Materials Balance: Anilines bri Saas SeaamenrON cone braormoma js: PERFOR ING ORGANTEATION REPORT WO Robert L. Hall, Ronald Burger, and Karen Slimak ‘PERFORMING GRGANIZATIGN NAME AND ADDRESS 15, PROGRAW ELEMENT NO. JRB Associates, Inc. 8400 Westpark Drive Fr WS: McLean, VA 22102 eas : 12, SPONSORING AGENCY NAME AND ADDRESS 5, FWPE OF REPORT AND PERIOD COVERED Survey and Analysis Division (TS-793) Final Report, Office of Pesticides and Toxic Substances [Fé SPONSORING AGENCY COOE U.S. Environmental Protection Agency Washington, DC_20460 Fs, SUPPLEMENTARY NOTES Project Officer ~ Michael Callahan This report presents a Level I materials balance study of a group of anilines speci- fied in a Task Order from the Office of Toxic Substances, U.S. Environmental Protec- tion Agency. The compounds studied were aniline, aniline hydrochloride, aniline hydrobromide, o-, m-, and p-nitroanilines, 16 other nitroanilines, and 15 other chloro- and bronoanflines. Areas of major interest were production quantities, producers, consumption quantities, and emissions to air, land, and water related to these processes. The estimated anounts of 1978 production (where available) were as follows: aniline, 279,000 kkg; aniline hydrochloride, 4.6 - 100 kkg; o-nitro- aniline, 3641 kkg; m-nitroaniline, 0 - 2.3 kkg} p-nitroaniline, 13,000 kkg. Emissions vere estimated when direct data were unavailable. The results (in kkg/year) ver: aniline, 20 kkg to air, 0.08 - 5.6 kkg to water; p-nitroaniline, 0.13 kkg to air, 117 kkkg’ to water. Throughout the report, estimates and assumptions were made where justified, in lieu of direct data. Types of information required for future studies are noted. FE Descnirvons p.ceNTiriens/OreN eNOEO TEAMS |e coSATI Fed/Group a OISFRIGOFIOH STATEMENT FB-ECORTY COAG PRE Rapar] NS OF PAGE Release Unlimited a oo 7 Fa SECURITY CLASS (TH pape] AE PRICE Unclassified EPA Form 37203 (973)