el Industrial Manufacturing Process 95.04 (&) Evaluation Series’ « Toxic Pollutant Identification: NITROBENZENE/ANILINE MANUFACTURING at c o U.S. ENVIRONMENTAL PROTECTION AGENCY+ 01/9504 January 1979 EPA ~ IMPQCE Series TOXIC POLLUTANT IDENTIFICATION: NITROBENZENE/ANTLINE MANUFACTURING by W. LOWENBACE J. SCHLESINGER J. KING ‘The MITRE Corporation METREK Division McLean, Virginia 22101 Grant No, 805620 , Technical Advisor: Paul E. desRosiers Project Officer: David R. Watkins, IERL-CI U.S. ENVIRONMENTAL PROTECTION AGENCY INDUSTRIAL AND EXTRACTIVE PROCESSES DIVISION OFFICE OF ENERGY, MINERALS AND INDUSTRY OFFICE OF RESEARCH AND DEVELOPMENT WASHINGTON, D.C. 20460ABSTRACT A detailed description of nitrobenzene/aniline manufacture and pollution control technology is presented. Included is a compre- hensive discussion of the reaction mechanism, with a summary of potential pollutants generated from feedstock impurities and significant side reactions. A generic process configuration is formulated, from which specific point source discharges are identi~ fied. From this perspective, current wastewater treatment and disposal practices, as well as alternative methods of treatment, are reviewed and potential treatment options recomended. iiTABLE OF CONTENTS LIST OF FIGURES vit LIST OF TABLES vid EXECUTIVE SUMMARY z I. INTRODUCTION 1 Legislative and Regulatory Background 1 Objectives and Approach 4 Overview of Nitrobenzene/Aniline Manufacture 8 Process Technology 8 Market Outlook 20 TL, NITROBENZENE/ANILINE MANUFACTURE 4 Reaction Conditions 4 Feedstock Composition “46 Reaction Mechanions a Nitration of Benzene 22 Hydrogenation of Nitrobenzene 25 Catalytic Hydrogenation 30 Dissolving Metal Reductions 34 Mechanism of Catalysis 37 By-Product Formation 42 Significant Side Reactions 44 By-Products from Feedstock Impurities 37 Process Configuration for Nitrobenzene/Aniline Manufacture 65 Generic Nitration Processes 65 Generic Nitrobenzene Reduction Processes 73 Catalytic Processes 2B Batch Processes 79 TIL, INDUSTRIAL WASTEWATER MANAGEMENT 83 Introduction 83 Current Treatment of Wastewater from Nitrobenzene/ Aniline Manufacture 86 Wastewater Characteristics 86 Federal and State Discharge Requirements 88 Current Industrial Practice: 93 Future Regulatory Concerns 96vr. TABLE OF CONTENTS (Concluded) METHODS OF WASTEWATER TREATMENT Introduction Biological Treatment Physical Pretreatment and Separation Practices Liquid-Liquid Extraction Theory and Process Description Application to Nitrobenzene/Aniline Manufacture Gas Liquid Operations Steam Stripping Adsorption on Granular Activated Carbon Theory and Process Description Waste Stream Applications Adsorption on Synthetic Resins Membrane Processes Dialysis Reverse Osmosis (RO) Combination and Alternative Techniques RECOMMENDED TREATMENT ALTERNATIVES Introduction Point Sources of Potential Pollutants Nitration of Benzene Point No. 1 Point No. 2 Point No. 3 Point No. 4 Point No. 5 Reduction of Nitrobenzene Point No. 6 Point No. 7 Point No. 8 Point No. 9 SUMMARY AND CONCLUSIONS REFERENCES BIBLIOGRAPHY vi 99 99 101 107 107 108 110 112 113 us 115 122 125 129 131 135 137 143 143 144 144 144, 145 145 146 146 148 148 149 149 149 isi 155 169Figure Number 1 2 10 uu 12 13 14 15 LIST OF FIGURES Nitrobenzene and Aniline Markets Proposed Reaction Mechanism for the Hydro- genation of Nitrobenzene Over Copper Catalysts Proposed Mechanism for Dissolving Metal Reduction of Nitrobenzene Continuous Liquid Phase Nitration of Benzene Tubular Reactor for Nitrobenzene Manufacture Continuous Vapor Phase Production of Aniline Continuous Liquid Phase Production of Aniline Batch Production of Aniline Significant Pollutants from Nitrobenzene/ Aniline Manufacture Aniline Wastewater Treatment by Steam Stripping Typical Carbon Adsorption Column Configur- ation Primary Adsorption Zone and Resulting Break- through Curve Adsorption of Nitrobenzene and Aniline on Carbon as a Function of Influent Concentration Adsorption of p-Nitrophenol as a Function of pH Potential Treatment Options for Nitro benzene/Aniline Wastewaters by Point Sources vit 35 68 mn 14 78 80 a2 14 118 120 124 128 153Table Numbi Ir Ir Iv vr vit VIIT Ix XI XIE XIE xIV LIST OF TABLES Consumption Pattern of Aniline Analysis of Pure Grade Benzene Product Specifications for Sulfuric and Nitric Acids Typical Compositions of Various Hydrogen Feed and Product Streams Organic By-Product Yield From Mononitration of Aromatic Hydrocarbons Composition of Acidic Organic By-Products From Nitration of Toluene Summary of Pollutants From Nitrobenzene/ Aniline Manufacture Characterization of Raw Waste Loading From Nitrobenzene/Aniline Manufacture BPT Effluent Limitations and New Source Standards of Performance for Aniline Manufacture Major U.S. Nitrobenzene/Aniline Manufacturers Biological Studies of Nitrophenols, Nitro- benzenes, and Aniline-Containing Wastewater Efficiency of Organic Solvents in Removing Phenolic Nitration By-Products Aniline Sorption by Ion Exchange Resins Aniline and Water Transport Through Polymeric Membranes viii Page a 17 18 20 45 60 66 87 OL 94 102 uu 130 133LIST OF TABLES (Concluded) Page Pervaporation Study: Nitrobenzene Permeability Coefficients 134 Summary of Foreign Applications of Physical-Chemical Treatment to Waste- waters Containing Nitrophenols, Nitro- benzenes, and Aniline 42EXECUTIVE SUMMARY The discharge of a toxic substance by an organic chemical manufacturer, may have irreversible effects on the environment. The extent of such effects will depend on the persistence and mobility of the compound. Under the Clean Water Act of 1977, the Environmental Protection Agency (EPA) must establish effluent limitations for 65 toxic pollutants (and/or classes of pollutants) in terms of the best available technology. As the Clean Water Act of 1977 does not preclude consideration of other pollutants, the EPA is currently working fron a list of 129 chemicals (see Appendix III).) However, the establishment of such standards that are not only equitable to industrial manufacturers, but more importantly that will prevent further deterioration of the environment, is an exceedingly difficult task. As a first step, EPA must thoroughly understand the manufactur- ing process and available control technologies so that, ultimately, attainable standards may be set. Because nitrobenzene and aniline are major organic intermediates (the annual nameplate production capacities for aniline and nitroben- zene are 730 and 1010 million pounds, respectively) and in light of current toxicity data, their manufacture potentially represents a significant hazard to both man and his environment. For the above reasons, this study is specifically directed toward the assessment of toxic pollutant generation from the manufacture of nitrobenzene/aniline and possible methods of control. Currently, nitrobenzene production throughout the world is based on nitration of benzene in the liquid phase with a mixture of nitric and sulfuric acid: NO2 HNO3 17804 ‘The bulk of aniline production is based upon nitrobenzene reduction, generally by one of three methods: catalytic hydrogena- tion. in the vapor phase, catalytic hydrogenation in the liquid phase, and by dissolving metal reduction. Of these methods, vapor phase catalytic hydrogenation is most commonly used: NOy NH2 Catalyst + 3Hy +2490Current domestic producers of nitrobenzene/aniline are American Cyanamid Company (Bound Brook, New Jersey, and Willow Island, West Virginia), E.I. duPont de Nemours & Company (Beaumont, Texas, and Gibbstown, New Jersey), First Mississippi Corporation, a subsidiary of First Chemical Corporation (Pascagoula, Mississippi), Mobay Chemical Corporation (New Martinsville, West Virginia), Rubicon Chemical Corporation (Geismar, Louisiana), and Mallinkrodt, Inc. (aniline only-Raleigh, North Carolina). In Section II, a detailed description of nitrobenzene/aniline manufacture has been presented. Included is a comprehensive discus- sion of the reaction mechanism, with a summary of potential pollutants generated from feedstock impurities and significant side reactions. The liquid phase nitration of benzene involves generation and the subsequent attack of the nitronium ion to form the benzenonium ion. This species reacts further with any base present to form nitrobenzene and the protonated base. Alternatively, the benzenonium ion may react with water to form nitrophenols. Catalytic reduction of nitrobenzene involves adsorption on the catalyst surface through both oxygen atoms; by hydrogen addition to an oxygen atom to yield, in a series of rapid steps, water and nitrosobenzene; a second addition of hydrogen to yield an adsorbed nitrene and vater; and finally, reaction of the nitrene with hydrogen to yield aniline. Alternatively, intermediate species may react to form azepins, azoxybenzene, azobenzene, N~phenylaniline, and complex nitrogen- containing polymers. A generic process configuration for nitrobenzene/aniline manu- facture has been formulated, identifying a total of nine point source discharges. Specifically, two major process waste streams are generated; the column overhead product from sulfuric acid recovery during nitrobenzene manufacture and the extraction column bottoms during aniline manufacture. Other significant point sources include the still bottoms from nitrobenzene purification, nitrobenzene wash water, and the still bottoms from aniline purification. A review of current wastewater treatment and disposal practices is presented in Section III, with regard to current discharge require- ments and future regulatory concerns. At this time, there are no effluent limitations specific to point source discharge from nitroben~ zene/aniline manufacture. As a result, a wide variety of treatment techniques are applied to the treatment of nitrobenzene/aniline manufacturing wastes. First Mississippi Corporation, a subsidiary of First Chemical Corporation, completed installation of both steam stripping (allowing for countercurrent extraction) and granular activated carbon columns during 1977. Carbon adsorption is also employed in combination with biological treatment by both duPont xi(Beaumont, Texas, facility) and Mobay Chemical Corporation for removal of dissolved organics. At their Gibbstown, New Jersey, facility, duPont provides both organic extraction and stripping units, while American Cyanamid and Mallinkrodt rely on biological treatment for removal of organic pollutants. Only Rubicon Chemicals practices deep well disposal of nitrobenzene/aniline process waste streams. Section IV consists of a detailed discussion of pollution abate- ment alternatives for nitrobenzene/aniline manufacture. Typically, the treatability of a waste stream is evaluated in terms of its biodegradability. However, as the nature of the organic waste load from nitrobenzene/aniline manufacture is conducive to physical treatment (i.e., activated carbon adsorption, liquid-liquid extrac tion, steam stripping), Section IV is divided into three major subsec~ tions: (1) biological treatment; (2) physical treatment; and (3) combinations of selected treatment technologies. Section V presents a point source-by-point-source summary of potential pollutants from nitrobenzene/aniline manufacture and recommends treatment alternatives for each stream. Major recommenda~ tions (which are based solely on the efficiency of a process to treat a waste stream, and exclude any analyses of capital, operation and maintenance, and energy costs) are directed toward the cleanup of the column overhead product from sulfuric acid recovery during nitrobenzene manufacture and the extraction column bottoms during aniline manufacture. Whatever method is used for acid purification, the toxic effluent stream is best treated by activated carbon adsorp tion. The aniline water is best treated by a counter-current extrac tion with nitrobenzene. Alternatively, the organic contaminants could be recovered by steam stripping techniques. In either case, the final effluent stream should receive further purification by adsorption on activated carbon. In summary, this report outlines some of the steps that must be taken before BAT effluent limitations can be rationally promulgated for nitrobenzene/aniline wastewaters. Recommendations for further studies include: © EPA verification, from sampling of actual process wastewaters, of all pollutant predictions and concentrations. ¢ Extension of this pollution prediction and abatement method- ology to additional compounds exemplifying other unit proces~ ses such as amination, chlorination, oxidation, etc. xiiEPA funding of pilot scale studies for determination of the technical practicability of the recommended treatment alterna- tives. ‘An economic analysis of viable treatment alternatives (with regard to best available technology economically achievable). Demonstration of BAT in an EPA-industry jointly funded proj- ect. addiSECTION I INTRODUCTION LEGISLATIVE AND REGULATORY BACKGROUND While the hazards of certain toxic water pollutants have long been recognized, the Environmental Protection Agency has histori- cally placed priority on controlling conventional water quality para~ meters such as pH, suspended solids and biochemical oxygen demand. Yet specific waterborne pollutants are coming increasingly into Prominence; headlines tell of widespread Kepone contamination of the James River in Virginia, carbon tetrachloride spills in the Ohio River, and contamination of the Hudson River from dumping of poly- chlorinated biphenyls. Furthermore, seventy-eight cities have found significant quantities of industrial chemicals such as PCB's, cyanides, phenols, and carcinogenic chlorinated hydrocarbons in drinking water supplies (Becker, 1977). There is no single comprehensive water pollution control statute; indeed, toxic substances are generally regulated under no less than nine different federal laws - the Clean Water Act of 1977 (PL 95-2174); the Safe Drinking Water Act (PL 93-523); the Marine Protection, Re- search, and Sanctuaries Act (PL 92-532, also known as the Ocean Dumping Act); the Resource Conservation and Recovery Act (PL 94-580, also known as the Solid Waste Act); the Federal Insecticide, Fungi- cide, and Rodenticide Act (PL 92-516); the Toxic Substances Control ‘This act supercedes the Federal Water Pollution Control Act of 1972, PL 92-500.Act (PL 94-469); the Hazardous Materials Transportation Act (PL 93~ 633); the Ports and Waterways Safety Act (PL 92-340); and the Atomic Energy Act of 1954 (PL 83-703). Thus, there is a complex inter- relationship of federal statutes dealing with various aspects of toxie substance control. More significant, perhaps, 1s that because each of these laws takes a somewhat different approach to regulation of water quality, areas of jurisdiction often overlap or intersect. Undoubtedly, the Federal Water Pollution Control Act (PL 92-500) was initially intended as EPA's primary regulatory tool for control of toxic discharges to the aquatic environment. Section 307(a) specifically required that a list of toxic pollutants be published and Limits for the discharge of those pollutants be established, taking only into account the substance's impact on the environment. However, nearly four years after the passage of the Act, Section 307(a) had yet to be implemented. Thus, in June of 1976 as a result of civil actions brought by three environmental interest groups, the EPA signed a consent agreement which required the inmediate establishment of Section 307(a) limitations for six particularly toxic chemicals (four pesticides - aldrin/dieldrin, DDT/DDD/DDE, endrin, and toxaphene, plus benzidine and polychlorinated biphenyls). Additionally the EPA agreed to write effluent limitations for 65 other chemicals (and/or classes of chemicals) into best available technology (BAT) effluent guidelines for NPDES* permits (authorized * ‘National Pollutant Discharge Elimination Systemunder Section 302 and 304 of PL 92-500) for 21 industries (see Appendices I and II); these limitations were to have gone into effect by 1983. As a result of the shortcomings of PL 92-500 for the control of toxic discharges to public waters,* Congress has sought to correct these deficiencies by the Clean Water Act of 1977 which embodies the major points of the consent agreement. Specifically under Section 307 of this legislation, the Administrator must establish effluent limitations for 65 toxic pollutants in terms of the best available technology economically achievable for the applicable category or class of point sources established in accordance with sections 301(b) (2) (A) and 304(b)(2) as soon as practicable, but no later than July 1, 1980 (see Appendices I and II for the list of toxic pollutants and applicable categories respectively). In seeking to provide a rea~ sonable amount of flexibility for the protection of the environment from new and unforseen hazards, Section 307 does not, however, pre- clude consideration of other pollutants. Thus, the EPA is currently working from a list of 129 chemicals (see Appendix III). Irrespective of the number of pollutants, to be able to promulgate these regulations the Environmental Protection Agency must at a minimum: © Predict or otherwise measure discharge rates for each pollutant; © Provide supporting data on each pollutant's health and ecological effect: “yor a brief review of the difficulties encountered by EPA in im plementing Section 307(a) of PL 92-500, see Ward (1977). 3© Evaluate control technology capabilities; and © Recommend ambient water quality criteria levels. OBJECTIVES AND APPROACH Much of the information required by the EPA for promulgation of practicable regulations in accordance with the Clean Water Act of 1977 does not yet exist. Pollutant discharge rates for each of the hundreds of processes in the 21 targeted industries is not readily available; indeed, general analytical protocols have yet to be developed for a substantial number of the specified pollutants. Moreover, effective methods of wastewater treatment for each of the 65 pollutants have yet to be defined, much less demonstrated as BAT. Thus, the first task in meeting the requirements of the Clean Water Act of 1977 4s to develop the data necessary to promulgate practicable regulations. Nonetheless, any data gathering system, whether it is a complex sampling and analysis program or simply a collection of existing wastewater data must be designed, within the existing budgetary constraints, to be both cost and information effective. The current procedures for collecting this pollutant information focus on the list of 65 classes or compounds known to be hazardous to the environment and, as such, involve only a cursory review of manufacturing processes. While this method is probably cost effective, the risk of bypassing unsuspected hazardous materials 4s rather high. An alternate solution is to directly analyze, andevaluate in some manner, each stream individually within a manufac~ turing process without any a priori assumptions as to its composition. Though this scheme is obviously information effective, it is also likely to be prohibitively expensive. Yet another approach to this problem, which represents a com promise between the above extremes is to identify, prior to sampling and analysis in the field, which species are likely to occur at each point source within a process from consideration of the reactants and reaction pathway. Thus the advantages of working from a limited list of discrete species is retained in addition to examining, in detail, each process for potentially toxic emissions to the environment. Because toxic species’ formation is derived solely from the reaction chemistry (and feedstock impurities), this method represents a multi- media approach to this problem. Aniline, the simplest of the primary aromatic amines, is a clear to pale yellow flammable liquid which has a boiling point of 184°C at atmospheric pressure, a vapor pressure of 0.4 mm Hg at 20°C, and a solubility of 3.7 grams/liter at 30°C. Aniline is regarded as a highly toxic chemical. Whether the exposure route is via inhalation, ingestion, or absorption through the skin, the acute toxic effects are the same: decrease or loss of oxygen transport by the blood (cyanosis). More significant, perhaps, are the chronic health effects of aniline exposure: though carcinogenic studies are inconclusive, aniline has been identified as a tumorgenic agent (Brown et al., 1975).Nitrobenzene, the immediate precursor of aniline,* is a pale yellow flammable liquid which has a boiling point of 211°C at atmospheric pressure, a vapor pressure of 0.3 mm Hg at 25°C, and a solubility of approximately 1 gram/liter at 20°C. Nitrobenzene is also regarded as an extrenely toxic chemical, with acute effects similar to those of aniline. It has been shown to affect the blood (causing methemoglobinemia), central nervous system, body metabolism, and cause local skin irritation. Though there are no data regarding the carcinogenicity or mutagenicity of nitrobenzene, it has produced teratogenic changes in rats. Moreover, it 1s relatively persistent in the environment and may bioaccumulate. Thus the Interagency Testing Committee (as established under Section 4 of the Toxic Substances Control Act, PL 94-469) has recommended nitrobenzene be tested for carcinogenicity, mutagenicity, and en- vironmental effects**, Because both chemicals are major chemical intermediates (the annual nameplate production capacities for aniline and nitrobenzene are 730 and 1010 million pounds respectively) and in light of the above toxicity data, nitrobenzene/aniline manufacture potentially represents a significant hazard to both man and his environment. ‘Falthough aniline may be manufactured from other chemical intermediates (e.g-, phenol), production in the United States is based solely on the reduction of nitrobenzene. *#¥or complete details see the Federal Register, 43(21), 4073, January 31, 1978 and the Federal Register 42(197), Part IV, October 12, 1977.Therefore, this study is specifically directed to the assessment of toxic pollutant generation within the manufacture of nitrobenzene/ aniline and possible methods of control. As such, the objectives are fivefold: © Identify the toxic chemicals likely to be present in the aqueous effluent from each process; @ Identify the point sources of these pollutants; e Identify current treatment practices; © Survey alternate treatment technologies; © Indicate practicable methods of pollutant reduction where current treatment has been deemed inadequate. Information has been gathered and generated in the following manner: (1) Through a thorough search of the chemical literature, the reaction mechanism (and thus the reaction inter- mediates) for the formation of nitrobenzene and aniline have been identified. From a knowledge of the reaction intermediates, significant by-products formed during nitrobenzene/aniline manufacture have been predicted. Additionally, the effect of feedstock impurities has been considered. (2) From an extensive patent search, a generic process configuration for nitrobenzene/aniline manufacture has been formulated. Included in this process description are specific point sources for various process opera~ tions. In general, pollutant discharges are considered from a multimedia viewpoint and are not restricted solely to aqueous effluents. (3) The EPA Office of Effluent Guidelines has provided summaries of current wastewater treatment and discharge practices of nitrobenzene/aniline manufacturers, from information gathered under Section 308 of PL 92-500. In addition to these summaries, relevant supplementary information has been provided.(4) From a thorough literature review, "state-of-the-art' wastewater treatment technology for nitrobenzene/aniline manufacture has been identified. Both patented tech- nologies and relevant theoretical studies have’ been included in this review. OVERVIEW OF NITROBENZENE/ANILINE MANUFACTURE Process Technology Nitrobenzene is manufactured exclusively by nitration of benzene, NOz HNO3 7 although there are numerous process variations. Virtually all capacity (greater than 97 percent) is captive to aniline manufacture and indeed, each aniline producer (with the exception of Mallinkrodt, Inc.) manufactures nitrobenzene at the same facilities. Although there are numerous procedures which might conceivably be used for the manufacture of aniline, relatively few have proved to be of commercial interest. These process include: © Vapor phase, catalytic reduction of nitrobenzene in either a fluidized or fixed bed reactor using a variety of catalysts, Nop Nig vapor phase + 3H, ———_— + 2H0 catalyst@ Liquid phase, catalytic reduction of nitrobenzene using a variety of catalysts, NO2 Nig Liquid phase oo +2H20 catalyst 43Hy © Ammonolysis of phenol using an aluminum catalyst, NH. H 2 © Liquid phase reduction of nitrobenzene with metals in mineral acids, e-g., NOg NHg 4 +9Fe +4H,0 ———=4 @ Ammonolysis of chlorobenzene using a copper (I) chloride catalyst, ‘L Nia + N39) +HeL Though each of the first three (and perhaps the fourth) processes are currently being used to produce aniline on a comercial scale, manufacture in the United States is based predominantly on the continuous, vapor phase, catalytic reduction of nitrobenzene. A small, but significant amount (approximately 8 percent based on name- plate capacity) is manufactured by Rubicon Chemicals, Inc., using a liquid phase catalytic reduction process. A smaller amount still is manufactured by Mallinkrodt, Inc., by a liquid phase, batch process. World demand for aniline has been estimated at 1.2 billion pounds in 1976 of which 730 million pounds were manufactured in the United States; by 1980 world demand is anticipated to reach as high as 2.3 9billion pounds per year with U.S. aniline capacity rising to 1 billion pounds per year (Chemical Week, July 20, 1977). Current domestic pro~ ducers of nitrobenzene/aniline are American Cyanamid Company (Bound Brook, New Jersey and Willow Island, West Virginia), E.I. duPont de Nenours & Company (Beaumont, Texas and Gibbstown, New Jersey), First Mississippi Corporation a subsidiary of First Chemical Corpor- ation (Pascagoula, Mississippi), Mobay Chemical Corporation (New Martinsville, West Virginia), Rubicon Chemical Corporation (Geismar, Louisiana), and Mallinkrodt, Inc. (aniline only - Raleigh, North Carolina). Market Outlook” The backbone of aniline demand lies in the production of nethylene diisocyanates, an intermediate used in manufacture of urethanes (see Table 1 and Figure 1), Growth in urethane markets has long been forecast, but slow in developing. The most promising markets are in insulation products and reaction-injection-nolded (RIM) auto parts. Urethane insulation products are regarded as being particularly attractive because of their superior insulation qualities (one anticipated use is urethane board for construction). The sane forecast suggests that use of aniline for RIM materials could rise from 20 million pounds in 1976 to 80 million pounds in 1980 and 160 million pounds in 1985. Other markets, however, are expected to do *as stated previously 97 percent of nitrobenzene production is captive to aniline manufacture. To avoid the redundancy of considering both nitrobenzene and aniline markets, only aniline is discussed in the following section. Nitrobenzene market outlets are, however, shown in Figure 1. 10TABLE I CONSUMPTION PATTERN OF ANILINE vane eat Isocyanates (4,4'-methylenediphenyl isocyanate and polymethylene poly phenylisocyanate) 40 Rubber Chemicals 35 Dyes and Dye Intermediates 6 Hydroquinone 6 Drugs 4 Miscellaneous Applications 9 Source: Lawler, 1977. uno more than match the performance of the general economy. Several U.S. manufacturers have already or are expected to ex- pand in response to anticipated demand. First Mississippi Corpora- tion has recently added 150 million pounds per year capacity which increases capacity of the Pascagoula, Mississippi plant to 250 million pounds per year; an additional 50 million pounds could be provided by increasing the output of the older unit to that of the new unit. Rubicon Chemical Corporation is currently adding a 220 million pounds per year plant which will increase the capacity of the existing Geismar, Louisiana facility to 280 million pounds per year when on- stream in 1978, American Cyanamid is also reactivating an existing plant in Bound Brook, New Jersey. On standby since 1974 and due to come online in 1978, the plant's nameplate capacity was 60 million pounds per year, but with refurbishing the capacity may be somewhat higher. DuPont will add about 15 percent by mid-1978 to its 360 million pounds per year capacity in Beaumont, Texas and Gibbstown, New Jersey. Finally, Mobay Chemical Corporation, will increase capacity by 40 million pounds per year as a by-product when its new pigments plant in New Martinsville, West Virginia comes online in 1981. or)SECTION IT NUTROBENZENE/ANILINE MANUFACTURE REACTION CONDITIONS ‘i The stoichiometric equations describing the reaction of benzene with nitric acid to produce nitrobenzene, and the subsequent reaction with hydrogen to yield aniline, Nog HyS04 50-90°C + HNOg +H wM and NO NH Catalyst, (2) are too often regarded as sufficient description of the industrial synthesis of nitrobenzene/aniline. Yet, any reaction in which a large number of bonds are broken will necessarily require passage through a number of distinct intermediates. Thus, the above equations do not, in any way, account for observed reaction by-products such as nitrophenols (in the case of nitration) or diphenyl hydrazine (in the case of nitrobenzene reduction). Only from careful consideration of (1) reaction conditions, (2) feedstock composition, (3) the reaction mechanisms, and (4) the most probable manufacturing configuration, can formation of such by-products be logically explained and the environmental impact adequately assessed. 1bThe previous section provided a brief overview of the industrial synthesis of nitrobenzene and aniline. While there is only one procedure for nitrobenzene manufacture (in terms of process chemistry only), there are three separate and distinct procedures* in current use for the reduction of nitrobenzene to aniline, which require separate discussion. Specifically, the following reactions will be considered: (1) The heterogeneous nitration of benzene with mixed acid (15 mole percent nitric acid, 30 mole percent sulfuric acid, and 55 mole percent water - see reaction (1)); (2) the gas phase heterogeneous catalytic reduction of nitrobenzene using a copper catalyst, NOg NH 270-475°C + 3H, — Late + 2Hy0 (3) Copper on Silica (3) the liquid phase heterogeneous catalytic reduction of nitroben- zene using a nickel catalyst, NO2 Ny = Lat +342 Mickel on Kieselguhr + 2H,0 3) ¥K fourth procedure, the amination of phenol to yield aniline, is not in current use by U.S. aniline manufacturers, for this reason, this procedure will not be discussed further. isand (4) the liquid phase heterogeneous catalytic reduction of nitro~ benzene with iron in acid solution, No, NH 4 +9Fe + 4H,043%200 6. 4 + 3Fe40, (5) However, because nitrobenzene and aniline are manufactured at the same site (with the exception of Mallinkrodt which does not produce nitrobenzene), all process chemistry will be discussed prior to introduction of any process configuration description. FEEDSTOCK COMPOSITION Accurate prediction of the formation of reaction by-products from nitrobenzene/aniline manufacture necessarily requires identifi- cation of significant (in terms of chemical reactivity, potential toxicity, and quantity present) impurities in all starting materials (benzene, nitric acid, and sulfuric acid). Unfortunately, a truly representative analysis of benzene is difficult to obtain because of varying sources* (thus leading to potentially different impuri- ties). A typical benzene feedstock, however, is likely to contain WBenzene is currently derived from four principal sources: coke ovens, reformate, crackers, and toluene hydrodealkylation, Based on nameplate capacity only, their relative market shares in 1976 were approximately 8, 47, 14, and 31 percent, respectively. In the near future, however, this pattern is expected to alter considerably, the largest growths occurring in production of benzene from crackers and by toluene hydrodealkylation. Thus, Schoeffel and Dmuchovsky (1977) predict the following market in 1981 (again based on nameplate capacity): coke ovens ~ 5 percent, reformate ~ 40 percent, crackers = 24 percent, and toluene hydrodealkylation ~ 31 percent. 16toluene and ethylbenzene with smaller amounts of xylenes, cycloal- kanes, cycloalkenes, and straight chain alkenes as shown in Table II. TABLE II ANALYSIS OF PURE GRADE BENZENE COMPONENT PERCENT BY WEIGHT Benzene 9 Toluene Ethylbenzene 1-Pentenes 2-Pentenes 2-Methyl-1-butene 2-Methy1-2-butene reported impurities Cyclopentane but not measured cyclopentene Cyclohexane cyclohexene lyaken to include isoneric xylenes, SOURCE: Mellan, 1977 Though concentrations are not specified for the majority of impuri- ties shown, their presence should not be precluded; indeed these and similar compounds have been identified in a less pure benzene* (Glick et al., 1960), For the purpose of this study (and consistent with the accuracy of the above data), it is assumed that the sum of these impurities is less than one tenth of 1 percent. Glick and co-workers have identified 20 specific compounds in con- ventionally acid washed, 1° coke oven benzene of 99.30 mole percent purity. 7Similarly, impurities in the other feedstocks are difficult to specify. In general sulfuric and nitric acid are both available in sufficiently pure commercial grades so as to preclude significant contribution (in terms of impurities present in these acids) to pollutant emissions, although each are polluting species in their own right. Product specifications of commercial grades of sulfuric acid and nitric acid are shown in Table III. TABLE IIT PRODUCT SPECIFICATIONS FOR, SULFURIC AND NITRIC ACIDS SULFURIC ACID NITRIC ACID IMPURITY 99% 1402 69-71%. 90%, Hydrogen chloride 5 5 50 0.7 Nitric acid 5 5 - - Sulfur dioxide 150 150 - - Ammon: lo -_ - _ Arsenic 0.5 0.5 0.1 0.3 Tron 150 200 0.2 2 Lead 50 50 0.5 5 Sulfate — - 1 5 1411 concentrations are in mg/l. SOURCE: Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edi- tion, 1966; Reagent Chemicals, 4th Edition; American Chemical Society, 1968. 18Though the concentrations shown are only generic rather than specific to a given manufacturer's product, these values are probably applic~ able to commercial grades because of competitive conditions within the industry. Feedstocks for aniline production are nitrobenzene and hydrogen. By-products of nitrobenzene manufacture (and thus, possible contami- nants of nitrobenzene) will be extensively considered in following sections of this report and will not be discussed further at this point. Hydrogen, required for the industrial manufacture of aniline, in tonnage quantities is obtained from a variety of sources which include (1) natural gas via steam reforming, (2) petroleum via partial oxidation, (3) refinery tail gas, and (4) coke oven gas. The impurities present in hydrogen will be at least somewhat dependent on its source but may be divided into two groups depending upon their boiling point. Low boiling contaminants are nitrogen, carbon monoxide, argon, and methane. Impurities belonging to the high boiling group include acetylene,catbon dioxide, paraffinic and olefinic hydrocarbons, hydrogen sulfide, carbonyl sulfide, mercaptans, and water. Of the two groups, generally only the low boiling contaminants present purification problems. Table IV illustrates typical compositions of several feed and product streams. From the information presented above, the principal impurities most likely to occur in feedstock hydrogen, regardless of its source, are methane, carbon monoxide, and nitrogen, There are no specific: tions stated in the patent literature regarding hydrogen other than a 19oz TABLE IV TYPICAL COMPOSITIONS OF VARIOUS HYDROGEN FEED AND PRODUCT STREAMS? FEED STREAMS PRODUCT STREAMS? PARTIAL COKE, REFORMER OXIDATION OVEN REFINERY METHANE —_-PROPENE COMPONENT Gas GAS cas. GAS ABSORBER ABSORBER PRODUCT Hydrogen 95.6 96.6 55.9 40.0 98.99 99.99 99.9999 Nitrogen 0.4 0.6 44 Ls 30ppm 30ppm Carbon Monoxide 17 2.0 6.8 1.0 10ppm Loppm Argon 0.2 Oxygen Methane 2.3 0.6 26.8 35 1.0 60ppm carbon «lpn Dioxide 1.8. 400ppm —— a Ethane 0.4 14 Ethylene 2.8 0.7 Acetylene 600ppa, on Hydrogen Sulfide a 0.2 - Other 0.2 0.3 Jali concentrations are percent by weight unless otherwise noted. Purification is via cryogenic procedures. Source: Baker and Paul, 1963.purity of greater than 90 percent (Karkalits et al., 1959; Sperber and Poehler, 1964); however, considering the low sulfur specification for nitrobenzene (Karkalits, 1959), it is not unlikely that a similar requirement exists for hydrogen. Other impurities, for example methane and carbon monoxide, though not necessarily inhibitory, may also be detrimental to the yield of aniline and should probably be kept to a minimum, Thus, for the purposes of this document all impurities shown in Table IV are assumed to be present in hydrogen (to a greater or lesser extent) used for aniline manufacture. REACTION MECHANISMS An understanding of the reaction mechanism, specifically the identification of those reactive intermediates which describe the reaction pathway, results in a complete, although qualitative, description of by-products.* Only a limited number of by-products have been explicitly associated with or identified from nitrobenzene/ aniline manufacture in the chemical literature, though a large number of species have been found in the wastewater at such facilitie Known by-products of nitrobenzene/aniline manufacture include p-nitro~ phenol, 2,4-dinitrophenol, 1,3-dinitrobenzene, azobenzene, phenylene~ diamine, nitrates, and sulfates. A detailed examination of the reaction mechanism will provide an indication of which minor side reactions may generate other hazardous or toxic compounds. ‘Finis ie actually the reverse of a wore traditional approach, where the existence of minor products is used to validate a mechanism, 21Nitration of Benzene Nitration chemistry occupies a unique position in organic chem- istry. Industrially, it was among the first unit processes to be operated on a large scale. Equally important has been its role in developing our understanding of. reaction mechanisms, in particular offering an ideal example of electrophilic substitution (see Ingold et al., 1950). Yet despite a relatively long history of industrial application and extensive mechanistic investigations, answers to fundamental questions, especially those which relate to the reaction conditions of industrial nitrations, remain elusive. Before discussing nitration mechanisms per se, it is important to recognize that aromatic nitration as practiced by industry is a heterogeneous reaction, that is the organic substrate and nitro pro- duct form @ separate phase from the aqueous acid. The nitration reactions certainly must occur in the acid phase or at least at the interface between the phases. Thus the organic substrate must be transferred either to acid phase or interface. Depending on reac~ tion conditions, either the intrinsic chemical kinetics or the maj transer process may be rate limiting. The intent here, however, is not to discuss the various mathematical models describing mass trans- fer with chemical reaction*, but rather to indicate only the signifi- cant intermediates of the reaction pathway. That the former may be ‘For a thorough discussion of such models as applicable to’nitration see Schiefferle et al., 1976; Giles et al., 1976; and Strachan, 1976. 22important in terms of pollutant formation is acknowledged, but such considerations have more effect on reactor design and remain beyond the scope of this document. In 1950 Ingold and his co-workers first proposed what is now widely accepted as the schene for the mechanism of aromatic nitration with nitric acid/sulfuric acid systems: initial formation of the nitronium ion, NO,*, followed by attack of this species upon the aromatic substrate. Yet when the nitronium ion was used as the rea~ gent (e.g., nitronium tetrafluoroborate), anomalous results (in terms of partial rate factors) were obtained. In 1968, Coombes and co- workers proposed the following mechanism as the simplest explanation consistent with all observed data: 120 (6) HNO, +H” === NOD + 8 No> + Arh=—===[Artino a” 2 * 4 ‘ArENO,] ===> 8 ‘ 2 * Oxo ° + Hy Base ——__- NO, + Base-H (9) ‘NOD d where the species enclosed in brackets is described as an encounter complex. The principal difference between this mechanism and that of 23Ingold is the formal existence of the encounter complex. For suffi~ ciently reactive substrates (e.g., xylenes), it may be shown that formation of the encounter complex may be rate limiting; for less reactive compounds, for example benzene and toluene, formation of the benzenonium ion (reaction 7) is rate limiting. An additional point of the mechanism which is open to question is the formal existence of the nitric acidium ion, H,NO,”, a known precursor of the nitronium ion, Yet the latter question may be largely one of seman-~ tics in that the nitronium ion in aqueous solution must certainly be co) 4,NO,” === No,+ + #0 ap hydrated to some extent; thus, as Hanson (1976) has pointed out, the differences in the expected kinetics of a hydrated nitronium ion and the nitric acidium ion will depend on the degree of bonding between water and the nitronium ion and the moment in the reaction process at which water 8 lost. For the purposes of this document, the formal existence of the nitric acidium ion will not be assumed, Of considerable interest, however, is the effect of water on the rate and order of a heterogeneous reaction system. In homogeneous systems (i.e., in the absence of water) formation of the nitronium 24sion (reaction 11 or 6) is rate controlling and is independent of the concentration and nature of the aromatic substrate. This results from reaction (7) being faster than the reverse of reaction (6); in other words, nitronium ions react with the substrate as fast as they are produced. In the presence of water the reaction rate is decreased with the eventual result that reaction (8) is rate con- trolling (Hughes et al., 1958, and Hanson et al, 1976). This effect is attributed to water reacting with the nitronium ion, the rate of which becomes comparable or greater than the rate of reaction with the aromatic substrate. Thus, the reactivity of the substrate becomes important and the rate of formation of the nitro product involves both the concentration of the substrate and nitronium ion. In the industrial nitration of benzene, where water is present in high concentration, the rate limiting step is formation of the benzenonium ion, the principal reactive intermed: Hydrogenation of Nitrobenzene To facilitate the discussion of the hydrogenation of nitroben- zene, it is useful to first consider the general relationships existing in heterogeneous processes in the gas or vapor phase over solid catalysts. Whereas simple gas phase reactions are characterized by radical rather than ionic mechanisms, heterogeneous reactions G ¢., reactions occurring in more than one phase), such as those which take place partly in the gas phase and partly on a solid surface, are considerably more complex. In the latter case, radical 25species need not exist explicitly and indeed, neither ionic nor radical species may predominate at the solid-gas interface. Regard- less of the specific species involved, a reaction occurring on a surface may usually be regarded as involving the following five consecutive steps: Diffusion of the reacting molecules to the surface; 2. Adsorption of the gases on the surface; Reaction on the surface; Desorption of the products; 5. Diffusion of the desorbed products into the main body of the gas. For reactions such as the gas phase hydrogenation of nitroben- zene which occur over porous catalysts, the diffusion process, 1, may be the slowest process and, thus, the rate determining step. General- ly, however, either adsorption or desorption, is likely to be rate determining since both commonly have appreciable activation energies. Desorption energies are particularly high and may, for a large number of reactions, be the slow step. In practice, separation of steps 3 and 4 is difficult since product desorption rates are not generally known; therefore, the reaction on the surface, giving the gaseous products, is most often regarded as a single step. Turn now from consideration of any heterogeneous reactions to the main features of hydrogenation reactions from the standpoint of reaction kinetics. As pointed out previously, hydrogenation reac~ tions can only be explained by passage through a series of distinct 26intermediates. Were such reactions to proceed through a single step, the catalyst surface would participate with its free valence electrons in both the formation and decomposition of a single activated complex; not only is this extremely unlikely from a purely theoretical view point, but also contradicted by a large body of experimental evidence (Kiperman, 1978). Moreover, hydrogenation reactions are further complicated by the possibilities of more than one reaction pathway. Such reactions may proceed under steady-state conditions in indepen- dent directions of which some represent different reaction routes to identical products, while others lead to formation of different products. The latter pathways are of paramount importance to the consideration of reaction selectivity and must be considered in any kinetic analysis. Thus, any kinetic model which is formulated to take the above features into account, will necessarily be quite complex. Certainly the same general features of a reaction occurring on a surface must also apply to liquid phase heterogeneous catalysis: diffusion of reactants to the surface; adsorption of the reactants on the surface; reaction on the surface; desorption of the products; diffusion of desorbed products into the main body of the reaction medium, Less clear, however, are their relationships from the standpoint of reaction kinetics. In particular,diffusion (step 1 and/or step 5) in the liquid phase may well be rate limiting as diffusion coefficients are three to five orders of magnitude lower 27than those in the gas phase. (Diffusion is defined as before and includes both external, as well as internal diffusion processes; the latter are rarely taken into account in liquid phase reactions and may be of some importance with small catalyst particles.) Not surprisingly, the kinetics of liquid phase reactions are considerably more complex than the general case of vapor phase hydrogenation. This results for the following reason @ The effects of both the solvent and the liquid reactants them- selves are both diverse and complex. Thus, not only solvation effects for the reactants, catalyst, and activated complex, but also hydrogen bonding, cage effects, as well as ion and dipole interaction must be considered. The influence of such factors is extremely difficult to assess quantitatively; © The same reactant, for example hydrogen, may exist in differ- ent adsorbed states of differing reactivity. Such behavior effects the homogeneity of the surface layer (tending to make the surface heterogeneous), and consequently influences the reaction proce @ The three phase system (interfaces between liquid, solid, and gas) requires that hydrodynamics and transport between these phases be considered. Discussion of the reaction kinetics of a hydrogenation system provides a formal framework in which all reactions may be considered and reconciled with a reaction mechanism. It is more useful, however, for the purposes of this document, to defer such a discussion to a later section and to first identify the reaction intermediates which lead to the formation of products and by-products. With regard to the latter, though the nature of the reacting species is difficult to ascertain with absolute certainty, available experimental evidence i best accounted for in terms of several radical-like intermediates 28derived from nitrobenzene. Less attention has been given to the nature of the adsorbed hydrogen in these particular hydrogenation systems; however, hydrogen adsorption on the thin metallic films (nickel in particular) has been studied extensively, In the case of ee adsorption in the atonic form to adsorption in the molecular form. Where the specific identity of adsorbed hydrogen is not known, such species shall be identified only as [H] but are assumed to exist in atomic form (ives, as a radical). So that the following discussion of the reaction mechanism will be intelligible to a reader with a limited knowledge of organic chemistry, the basic features of the reaction mechanism which lead to the formation of important reaction intermediates (i.e., lead directly to nitrobenzene or significant by-products) are outlined first. Two separate mechanisms, which are directly applicable to all known commercial procedures for nitrobenzene reduction in the United States, are considered: catalytic hydrogenation over copper or nickel catalysts in either the g or the liquid phase and reduction with elemental iron in the liquid phase. The more difficult question of the specific mode of catalysis is discussed in a separate subsec~ tion entitled "Mechanism of Catalysis" and may be omitted without serious loss of continuity. 29Catalytic Hydrogenation Few data are available concerning the catalytic hydrogenation of nitrobenzene to aniline. This situation is no doubt due to the extreme difficulty of considering any heterogeneous reaction system by reaction kinetics alone. Generally, such studies are greatly complicated by a variety of surface effects. In recent years new research and analytical techniques have made the direct. study of the events on a catalyst surface possible, thus eliminating the necessity of drawing conclusions about a mechanism indirectly. Though such techniques have yet to be applied to nitrobenzene/aniline, such studies should firmly establish the mechanism of catalysis in thi: system. Keeping the above points in mind, it is pertinent to note that a small number of kinetic investigations have been made using conmer- 1, supported catalysts, generally with the addition of a pronoter.* Unfortunately, the. majority of investigations performed to date have suffered from serious procedural defects: lack of isothermal condi- tions in the catalyst bed; the use of an integral reactor; and the probable effects of diffusional factors on the reaction kinetics. Because of the above factor interpretation of kinetic results from such studies (which typically have been confusing and contradictory) h been difficult. Moreover, the use of promoters in catalysts ‘¥x promoter may be defined as a substance, which when added to a catalyst in small amounts, enhances (promotes) the reaction selec~ tivity or yield. 30would make the validity of extending the kinetic processes to pure copper doubtful in any case. There are no data in the literature concerning the adsorption of nitrobenzene (or any aromatic nitro compound for that matter) on copper surfaces; however, it is not unreasonable to assume that, upon adsorption, a molecule of nitrobenzene bonds to two atoms of copper through oxygen. Taking into account that ‘molecular hydrogen is not effectively adsorbed below 300°C, together with empirical evidence, Pogorelov (1976) suggests a variation of an impact mechanism similar to that proposed by Twigg (1950). This.variation is shown in Figure 2. Formally, this mechanism may be expressed by the following reactions . ON0, o—_— MO Nd (12) MONO, + Hy ——+ M@NOOH . mH a3) MONOOH . mH ——~ MéNO + HAO (14) MONO + Hy — MONOH . mH qs) MONOH . mH ——~ MON + H)O (6) MON + Hy —- MONH . ait an MONH . mH —~- M+ ONE (8) 3ze AN. Ad ti —» fon —» A? Qh, —> wit, th + aco ——p FIGURE 2 PROPOSED REACTION MECHANISM FOR THE HYDROGENATION OF NITROBENZENE OVER COPPER CATALYSTS + fou,cuwhere M equals 2m denotes an adsorption center consisting of two surface atoms of copper, denoted as m, If the rate limiting step is reaction (13) and nitrobenzene adsorption (reaction 12) is at equilibrium, then the rate equation may be expressed as: “1381 Powo,Pa, ve Bede as) T+ &P, 1" ono, where k,, is the rate constant for reaction 13 and K, the adsorption coefficient for nitrobenzene. It is pertinent to note that where is large (i.e., where is large) this equation reduces P ‘ONO, KP, VeNo, to (20) in accordance with experimental data. This, together with the experi- mental value of the pre-exponential factor of the rate constant for reaction (13) and the large value of K, lend further credence to this mechanism. In summary, the mechanism of catalytic hydrogenation of nitroben- zene to aniline has yet to be conclusively demonstrated, though the scheme proposed by Pogorelov et al., 1976, is the most rational inter- pretation of existing data. For the purposes of this document (i.e., pollutant prediction), the general mechanism as shown in Figure 2 is 33assumed to be applicable to both the vapor and liquid phase hydrogen~ ation processes over copper and nickel catalysts. This assumption should not be interpreted to mean that the preceding processes (reactions 12 through 17) have equal importance in alternate systems, but rather that the same reactive intermediates are suggested to exist and play a greater or lesser role depending on the specific system. By further examination of these intermediates, i.e., gNOOH, ONO, NOH, and ON, together with consideration of their subsequent reactions, additional by-products may be predicted. ving Metal Reductions Not unlike gas and liquid phase hydrogenation processes, dis- solving metal reductions of aromatic nitro compounds have not been extensively studied despite their wide usage in synthetic organic chemistry. Again, this is no doubr due to.the extreme difficulties (as discussed at the beginning of the previous subsection) of studying Liquid phase heterogeneous reactions. Nonetheless there is, from electron spin resonance (ESR) studies with aromatic nitro compounds and other observations (chiefly electro- chemical - see, for example, Wagniere, 1969), general belief in the mechanism shown in Figure 3 as proposed by House (1972). As such, it is useful to identify this mechaniom in terms of the following reactions: Fe ono, ——= ono, (2)ORs, 2 V8 Hg ae, rg Ted ge ; Op a an ° FIGURE 3 PROPOSED MECHANISM FOR DISSOLVING METAL REDUCTION OF NITROBENZENEoho, ~ + x +90, (22) $io,n 2 = 410,87 (23) gio,K” + W——~4no + 4,0 (24) ono Stee to” (25) ono” +e’ ——> $ Row (26) exon ~£2— 6 ow an nou” + Ho nHoH : (28) ‘onHon + HY Fe ONE, + HO (29) ‘The key intermediate step in this mechanism is the formation of stable aromatic radical ions. The protonation of this intermediate with subsequent reduction by the metal (iron) leads first to a nitroso intermediate followed by a hydroxylamine intermediate. Though these intermediates have not been isolated in this particular system (iron/nitrobenzene/nydrochloric acid), their existence is well established in other systems (e.g., zine and tin). Notably the 36oxidation state of iron is not indicated other than at the outset (fe*), and at the end of the reaction scheme (Fe“*/r2* ), as this electron transfer process is not well understood at this time. Furthermore, because there do not appear to have been any rigorous kinetic studies of this system, identification of the rate limiting step is speculative; however, proton transfer reactions are generally very rapid. Therefore an electron tra fer step, perhaps the first, might reasonably be suggested as being rate controlling. Again, as before, the purpose of proposing this mechanism has been solely to provide a rational framework for identification of reactive intermediates which have bearing on by-product formation via significant side reactions. Thus, by further examination of these intermediates, ise., the benzonitroyl radical anion, nitrosobenzene, and hydroxylamine, together with their subsequent reactions, forma- tion of significant pollutants may be predicted in the following sections. Mechanism of Catalysis (Optional Section) By further examining the reactive intermediates at the catalyst surface, a mechanism for the catalytic hydrogenation of nitrobenzene over copper and nickel may be postulated. To do this, however, necessitates detailed consideration of the bonding between metallic (ices, copper or nickel), inorganic (ive., hydrogen), and organic species. Though this bonding is best considered in terms of molecular orbital theory, studies to date have been limited solely to hydrogen 37absorption on copper and nickel (Itoh, 1976; Fassaert et al., 1972; Barclay, 1973, and Takasu and Matsuda, 1976). Thus, the reactive intermediates discussed previously have been identified by kinetic evidence, that is, an indirect method. Because such results, i.e., rate laws, are mathematical descriptions of a physical process, totally different mechanisms may, in fact, be consistent with such descriptions. Physico-chemical methods (e.g., ESR, NMR, IR, UV, low energy electron diffraction (LEED), and mass spectroscopy) which generally allow selection of the authentic varient of the mathematical description, have yet to be applied to elucidation of this mechanism. Kinetic results and a corresponding mechanism for the catalytic reduction of nitrobenzene to aniline in the vapor phase ( 300°C) over a tin (II) oxide were first reported by Tsutsumi and Terada in 1951. Their kinetic investigation suggested that -the presence of two alternate reaction pathways depending on the hydrogen concentration at the catalyst surface. The first pathway, thought to be dominant at low surface concentrations of hydrogen, involves phenylnitrene as the principal reactive intermediate. The second pathway, occurring at high surface concentrations of hydrogen, proceeds through a phenyl- aminyl radical. Thus, catalysis of this reduction process apparently occurs at various oxidative levels. A reasonable interpretation of these results is the initial oxidation of the catalyst by the nitro group, hydrogen addition to the nitrogen atom, and subsequent reduction of the catalyst by hydrogen. 38Two kinetic studies have been reported: concerning reduction of nitrobenzene to aniline in packed beds with various copper catalysts. Rihani et al., 1965, while not succe: ful in elucidating the reaction mechanisms, noted that the reaction velocity could be empirically expressed as: yi2 v= 0.465 (Pyug P, (30) ONO, PH where v is the reaction velocity and Fyyo» Py are the partial pressures of nitrobenzene and hydrogen, respectively. This equation, however, is applicable only over the temperature range of 275 to 350°C and for a specific catalyst: 20 percent copper/nickel alloy (tL by weight) on tos with cadmium as a promoter (15 percent by weight of copper/nickel alloy), Gharda and Sliepcevich (1960) in a separate study, derived a similar relationship and indicated the difficulty of visualizing the rate controlling step as being the surface reaction between molecularly adsorbed hydrogen and nitroben- zene dissoc: ted on two active centers, This difficulty notwith- standing, three general mechanisms have been considered by both groups: the adsorption of reactants is rate controlling; the surface reaction is rate controlling; and desorption of products is rate controlling. Additionally, several other combinations based on hydrogen and nitrobenzene dissociating, and either hydrogen or nitrobenzene not being adsorbed were examined. 39While none of these mechanisms (as derived by Rihani) were con- sistent with the empirical data, a surface reaction may still be rate controlling (based on observed heats’ of adsorption together with the reversible deactivation of the copper catalyst by dinitrobenzene) if surface heterogeneity (in terms of energy) and diffusivity of the reactants are considered, Regarded from this viewpoint, the above empirical data may be interpretable in terms of a simpler pathway than a surface reaction between molecularly adsorbed hydrogen and nitrobenzene dissociated on two active centers. In this regard, Halsey (1949) has shown that a reaction which obeys the rate law as defined by Langmuir adsorption on a homogeneous surface, vez Gan where v is the volume of gas adsorbed, K the adsorption equilibrium constant, and p the pressure of the gas, may obey K V2 ve (-) (32) on an energetically nonuniform surface. This result is particularly interesting, as it may shed light upon the fractional orders found by Garda et al., 1960. 40Many of the questions which the previous studies cited have been recently answered by Pogorelov et al., 1976. Though surface species are not explicitly identified, the design of the experiment (in terms of catalyst purity and identity, variation of the partial pressures of the reactants, and the addition of reaction products to the reaction zone) is excellent. In contrast to the earlier studies, Pogorelev and coworkers found that the rate of reaction does not depend on the partial pressure of nitrobenzene (over the range of 8 x 10% to 2.5 x 10 atm at 260°C) but is directly proportional to the partial pressure of hydrogen. Moreover, addition of water and aniline (varied from approximately 0.002 to 0.06 and 0.002 to 0.02 atm., respectively) to the reaction mixture was without effect indi- cating the lack of inhibition of the reaction by reaction product: Though the reaction rate at low nitrobenzene concentrations (i.e., partial pressures) is dependent only on the partial pressure of hydrogen vek, 2 (20) 13 Pay when variation of all reagent concentrations is taken into account, the kinetics may be more generally described in the following form: (33) a: A ' ee ot where v is the reaction rate in moles aniline/M hr, K', K" are con~ stants; and P,,. and P, are the partial pressures of nitrobenzene NO, 4, and hydrogen, respectively. BY-PRODUCT FORMATION ‘Two possible pathways leading to by-product formation (and hence to process emissions) have been identified*: by-products from alternate reaction routes; and reaction, by either the main or alternate reaction route, of feedstock impurities. With regard to the latter, it is important to realize that, even though a feedstock impurity may be inert under a given set of reaction conditions, the direct discharge of such an impurity to the environment may still represent a significant effluent. Additionally, the identity and quantity of such impurities are difficult to ascertain in many cases because feedstock sources may vary from day to day regardless of the supplier. Clearly, prediction of pollutant formation via either pathway i necessarily of a qualitative rather than quantitative nature; though reactive intermediates may be identified without extensive kinetic measurements, their rate of formation (and thus quantities produced) are impossible to predict without kinetic measurements. Other quanti- tative approaches, for example detailed calculation of an‘ equilibrium Where is, of course, a third possibility: direct discharge of @ reaction mixture to the environment due to a major process upset. Such events, while worthy of serious consideration, are however beyond the scope of the present document. 42composition by minimization of the free energy of a system, require complete specification of all species to be considered. Because such methods necessarily assume equilibrium, the concentrations generated by such methods represent only trends or, perhaps at best, concentra~ tion ratios. Thus, qualitative predictions are extremely useful (if not essential) for initial assessment of environmental hazards associated with a given manufacturing process, development of a rational sampling and analysis program, and identification or design of suitable effluent control technologies, all in a cost effective manner. The following discussion is broken into two general sections; the first will consider by-products which form as a result of alter- nate reaction pathways while the second will consider the effect of feedstock impurities. Moreover, there is obvious overlap between the two sections, the following differentiations are made: (1) no formal distinction is made between by-products arising from nitroben- zene production and aniline production; that is to say, that while relevant reactive intermediates are considered sequentially, there is but one overall proces: (2) by-products which result from alter nate reaction pathways are considered from the viewpoint of reactive intermediates identified as defined in the previous subsection, Reaction Mechansims; (3) regardle: of the source of compound (i.e., whether a feedstock impurity or reaction product), once introduced, the entire reaction course of that compound is considered in that 43subsection; (4) only those impurities identified and defined in the previous subsection, Feedstock Composition, will be considered initially. Significant side Reaction Examination of intermediate species (NO, NOOK, ON:, etc.) together with consideration of the subsequent reactions of these initial products, provides a logical basis for prediction of addi- tional by-products. However, this discussion is based on probable rather than demonstrated reaction pathways and, as such, the exist- ence of predicted pollutant species must be verified experimentally. Side reactions during aromatic nitration are well documented in the literature (Ross and Kirshen, 1976; Titov, 1952; and Bennett and Youle, 1938). The most relevant and comprehensive discussion, how- ever, is that of Hanson and coworkers (1976), who not only charac- terize by-products formed during aromatic nitration, but also consider the rate and extent of formation of such by-products as a function of reaction conditions. In particular, though side reactions of nitro- benzene are minimal, those of other aromatic compounds are not. The average yield of by-products, as compared to the corresponding mononitro compound, is shown in Table V. 4aTABLE V ORGANIC BY-PRODUCT YIELD “FROM MONONITRATION OF AROMATIC HYDROCARBONS Weight % Organic Hydrocarbon By-Products Benzene 0.018 Toluene 1.72 Ethylbenzene 1.63 o-xXylene 6.19 prXylene 3.13 m-Xylene 0.77 Source: Hanson, 1976. The most obvious side reaction of aromatic nitration is simply that of dinitration: Noo Nop HNO HNO 12504 17504 cy NO2 ‘The extent of this reaction is unknown, but is likely to be small in that the first nitro group significantly deactivates the aromatic ring. Less obvious is the formation of nitrophenols during the nitra~ tion of benzene. Though a number of mechanisms have been suggested to account for the occurrence of nitrophenols, only two merit serious consideration, The first, suggested by Bennett (1943; 1945) presup- poses that a nitronium ion becomes attached to the aromatic ring 45through one of the two oxygen atoms instead of the normal nitrogen atom to form an aryl nitrite. This then decomposes to a phenol and a nitrosyl ion: ONO OH . . A phenol so formed will be rapidly nitrated to form either a mono-, di-, or trinitrated phenol. OH OH OH OH + $0, +0 N O No3 Os “O nox 02 102 oe NO 102 NOg The NO” ion formed in reaction (35) ultimately yields nitrous acid by either of the following pathways: — No" + No,” ———=n,0, + #,0————= No, + HNO, an « OH OH HH HNO: No. NO ‘The experimental observation that one mole of nitrous acid is pro- duced for each mole of organic acid by-products (Hanson, 1976) is in accordance with this mechanism, though there is no evidence which suggests that a nitronium ion may react with benzene in this manner. Hanson and coworkers (1976) believe the following mechanism, also. consistent with experimental evidence, to be a more likely explanation: 46initial attack of the nitronium ion, followed by attack of water, with subsequent elimination of nitroys acid. Hy enon Hao, oe O +No} — — — oO + HNO (39) ‘OH Again, the phenol so formed will be rapidly nitrated to form either a mono-, di-, or trinitro phenol (see reaction 35). Hydrogenation of such by-products is relatively straight- forward, although there is a question of the extent of such reductions (Rihani, 1965). Thus, dinitrobenzene is reduced to m-phenylenediamine (presumably through a nitroso intermediate), NOg No NHo +2Hyg ———= + 4H ———> (40) NO2 NO Ng while polynitrophenols are reduced to polyaminophenols (again pre~ sumably through a nitroso intermediate). NO NO NH2 +3Hg— +6Hp— «a Oy! ‘NO on: No HN NH oH OH on Though the reactions shown above indicate complete reduction of all nitro groups, this need not necessarily occur; indeed, it is likely that partially reduced species such as the following may predominate: Nog NOg NH +H4y——— +32 ———— (42) 'NO2 NO NO a7The thermal decomposition of liquid nitric acid may be important in nitrobenzene manufacture since it does decompose at the tempera~ tures used in the liquid phase reactions and yields potential oxi- dizers as products. While a single mechanism has not been agreed upon, there is general agreement that formation of dinitrogen pentox- _ ide is the rate determining step in the decomposition, A reasonable méchanism* would be (Ross and Kirshen, 1976): 2 NO, === 4,0 + N05 43) N05 =— NO, be NO 1/2 0 + 2N0,, (44) The net reaction is simply the equilibrium for production of nitric acid from nitrogen dioxide, water, and oxygen: 2WNO, === 1/20, + H0 + NO, (4s) Nitrogen dioxide evolved in the above sequence is probably the active oxidizer in mixed acid systems. Although such a discussion is some- what premature, a simplified mechanism of oxidation following nitrogen dioxide generation via reaction (45) would be: *ordes et al the step: HNO. 1958, have suggested an alternative sequence involving ——="no, + #0 3 Ross and Kirshen, however, point out that such a step would be far too slow to be consistent with the observed rates of decomposition. 48RH + "NO, ———* — R" + HNO) (46) R' +040 ——~+ R0O-0 (any RO-O" + RH ————= R-OOH + RB” (48) R-OOH ———= Decomposition products (49) In mixed acid systems nitrous acid formed is rapidly protonated and the resulting product dissociates, forming NO": * + wNO, + H No” + H,0 (50) Aside from formation of oxidized by-products, the above mechanism may be of greater environmental significance regarding nitrosamine formation.* ‘while aniline is certain to be present in wastewaters at facilities manufacturing nitrobenzene (recall that 97 percent of nitrobenzene production is captive to aniline manufacture), reaction with nitrous acid yields the reactive benzenediazonium cation; this intermediate may either decompose to benzene and nitrogen or further react with other nucleophiles present (e.g., Hz0 to yield phenol). Amines other than aniline (most importantly secondary amines), however, may be ent in the wastewater of such facilities. An appropriate (EPA, 1976): 2HNO, === N,0, + #0 RIRUNH + NO, —= R'R"N-N=0 + HNO, where R' and R" may represent either alkyl or aryl groups 49While it is clear that the principal intermediates forned during reduction of nitrobenzene ~¢NOOH, $NOH, $N: during catalytic hydro- genation and NO), ONO, SNHOH during dissolving metal reduction ~ lead to aniline, other reaction pathways for each of the above species do exist. Perhaps the easiest and most general deviation from the course of the main reaction, is that of partial reduction (cf, reac~ tion 42): Nog NHOH NO This type of by-product formation may be most important for dissolving metal reductions, Alternatively, reduction of nitrobenzene may not stop at reduction of the nitro group; thus cyclohexylamine, cyclohex- enyl amine (various isomers), and cyclohexadienylamine may be formed. Formation of reduced by-products via this scheme, known to be impor- tant during liquid phase catalytic reduction (Cooke and Thurlow, 1966), is probably important in the vapor phase process as well. NH NH NH NHa Om-Ol"-O-O wn Nitrosobenzene and the immediate precursor of phenyl hydroxyl amine, NOH may undergo an aldol-like condensation on the catalyst surface to yield azoxybenzene soNOH \H a-al-o“ol-o70” Potentially, the Gost reactive, and thus the most interesting oO 2 +B proposed intermediate during catalytic hydrogenation, is an adsorbed phenylnitrene species, [¢N:]. While the properties of such an adsorbed species no doubt differ significantly from that of a "free" nitrene, it is not unreasonable, within the context of this document, to assume an adsorbed phenylnitrene reacts in a manner similar (though not necessarily to the same extent or rate) to that of a free nitrene. Thus, additions to multiple bonds and insertion reactions are assumed to typify the reactions of an adsorbed phenylnitrene.* Certainly the most prevalent molecules present during catalytic hydrogenation, aside from hydrogen, are aniline and nitrobenzene which may react, via insertion reactions, in the following ways: NH N-N + HH (54) NH Na + eal Cys (Gs) 4 Nop NO (36) + —_—- N H WFor a cogent discussion of the reactions of nitrenes, the reader is referred to Lwowski, 1963. 51Subsequent reduction of N-nitrobenzene substituted anilines may reasonably lead to the formation of complex nitrogen-containing FOO” OTD AOS} Were the*substitued nitrene to react at any point along this pathway (s7) with aniline (either by C-H or N-H insertion) the reaction would termi nate; though this pathway apparently does not occur to a large extent during catalytic hydrogentation, such a mechanism does rationally explain the formation of organic tar during the vapor phase process (Karkalits, 1959). In an analogous manner, an insertion reaction may occur intramolecularly: Fe 4 fin, i aaa (58) 1H 4 Nitrenes can also add to aromatic rings to give substitued azepins as ring expansion products: (39) where R represents either an amino or a nitro group. If this sub- stituent is a nitro group, further reduction and subsequent reaction 52may in a manner similar to that shown in reaction 57, lead to com -Olo}ar | As before, polymer termination occurs upon reaction of the nitrene with aniline or a similarly unreactive substrate. Worth noting, is that neither insertion nor addition reactions are mutually exclusive; in fact, any polymer formation is likely to result from both insertion and addition reactions. Another reaction which is likely to be significant during catalytic reduction is dimerization to azo products; arylnitrenes sometimes have sufficient lifetimes for the preparation of mixed azo species. Diazobenzene thus formed, Ne N=N 2 —- (61) may be subsequently reduced to hydrazobenzene: N=N N—N. or a +” ——Cyt Hl (62) 533Other reactions similar to the above may also occur by reac~ tion of impurities which are present in the nitrobenzene feedstock. In general, the interest is not so much that these impurities intro~ duce similar compounds to those shown in reactions (55) through (64) but rather that these impurities may react with an absorbed phenyl nitrene to form new products. Thus nitrotoluene (and other nitroalkyl benzenes), and nitrophenol may react in the following manner (cf reaction 54): ; cn, cH Ne ‘3 a ne ‘N-CH, O-OFO.' OL ‘NOR NO2 No; ind 2 N oH rd (64) O ora + —— NO2 Another type of reaction, of interest in that oxygenated deriv atives may be formed, is as follows (cf reaction 22): Na yh — 1 O Hy) In the presence of suitable acid (or perhaps catalyst), a dienone may rearrange to yield a phenol: ¥fhe small amounts of impurities present together with the minor extent of the above reactions must certainly lead to even smaller amounts of products. 34OH +t —- (66) This type of reaction is probably most prevalent in liquid ph e catalytic hydrogenation procebses. Though the above reactions are assumed to apply to liquid phase catalytic reduction, it is important to note that by-products obtained in liquid phase catalytic processes may be different than those in vapor phase processes for the follow- ing reasons: (1) lower temperatures for reduction; (2) different catalysts; and (3) formation of two liquid phases, if water is not removed as it is formed. Preferential solubility of the product and by-products in one phase may be quite important. Based on the sequence of reactions (25) through (33), generally generally similar side reactions may re: jonably be expected to occur during dissolving metal reduction. Nitrosobenzene and phenyl- hydroxylamine are both reactive intermediates in this scheme and under suitable conditions (i.e. in the presence of a base) react via an aldol-like condensation to yield azoxybenzenes: NOHH aO—O1O » The oxygen can be removed relatively easily to yield azobenzne, which in turn, can add hydrogen and form hydrazobenzene. Further reduction of this system yields aniline: 35lo-z+ "aL CO a . or Cae 2 Under acidic conditions, phenylhydroxylamine rearranges intromolecu- zz larly in aqueous solution to p-aminophenol; the rearrangement involves nucleophilic attack and the following mechanism has been proposed (Pieser and Fieser, 1961): (69) Where nucleophiles other than hydroxide predominate in the reaction media, p-aminophenols are not formed; in the presence of chloride, for example, p-chloroaniline is formed. : Hydrazobenzene, in the presence of a mineral acid, undergoes a double side~chain-to-nucleus rearrangement to form benzidine a a major product: Cpe Prods GO ii <)™ - ducts: Oe x) 56Usually the 4,4'-diaminobiaryl is the principal product except when one or both of the para positions are substituted; however, such substitution does not preclude formation of the 4,4'-diamine. The 2,2'-diaminobiaryl and p-semidine are formed in smaller amounts than the other two side products. Another side reaction which may occur under similar conditions disproportionation (March, 1977): NH HH “OO =O + ou m By-Products From Feedstock Impu: From consideration of the feedstock analyses presented in Tables II through IV, it is readily apparent that the bulk of contam- inants are found in benzene; moreover, those impurities which are present in sulfuric acid, nitric acid and hydrogen may reasonably be expected to be inert. Therefore, only impurities present in benzene will be considered in the following discussion. Contaminants present in the benzene used for production of nitrobenzene have been previously identified, in approximate order of significance, as toluene, ethylbenzene (and probably the isomeric xylenes), various acyclic pentenes, cyclopentane, cyclopentene, cyclohexane, and cyclohexene; though aliphatic species may be present in smaller quantities than aromatic impurities, their presence may nonetheless be important. However, of the eleven species shown in 37Table II (see page ) toluene, ethylbenzene and isomeric xylenes, are of particular importance with regard to by-product formation, in that (on @ mole basis) these compounds produce approximately ninety to three hundred times the amount of side products as does benzene. The most obvious reaction of feedstock impurities is that of simple mono-nitration (ef reaction 1): CHy Hg CH + NO; No; 2 O=-o"-O ™ NOg Though shown only for toluene, the reaction is equally applicable to ethylbenzene and o,m-xylenes. Equally obvious is the dinitration of such substrates (again shown only for toluene, but equally appli- cable to other aromatic substrates; cf reaction 34): CHy cHg nos O2% NO2 NO2 . a + (73) NO2 Other by-products result from both oxidation and water addition to CHg such substrates (cf reactions 39 and 48): CH COOH HNC HNO a cs) 58cg cHg HIN H9804 oH CH 00H HNO. 17804 on The above reactions (72-76) must be rather than comprehensive; the two types of reaction: cHg Nog 75) ON NO2 on COOH Nog Noy Noy Oa! NOz oN NOy (76) on on regarded as being archetypal , oxidation and electrophilic substitution--together with both the number of attacking species and positions su of possible compounds. The composition of of toluene ai eptible to attack--lead to a large nunber organic by-products from the mono-nitration presented in Table VI, may, however, indicate the relative importance of such side reactions. Thus, while space does not permit delineation of the generally similar reactions of ethylbenzene and xyler in the pollutant summary. » such as reaction products are included 59TABLE VI COMPOSITION OF ACIDIC ORGANIC BY-PRODUCTS FROM NITRATION OF TOLUENE! .2 coMPouND PERCENT BY WEIGHT 2,6 dinitro p-cresol 79 4,6 dinitro o-creosol 10 2,4 dinitrophenol 1 prnitrophenol and mono-nitrocresol 4 3 nitro 4 hydroxy benzoic acid 3 lextraction with 2N NaOH; thus, dinitrotoluene would not be recovered by such a procedure. "yixed acid composition: 30 mole percent sulfuric acid, 15 percent nitric acid, and 55 mole percent water. Source: Hanson et al., 1976. Aliphatic impurities present in benzene are presumed to react via a free radical mechanism, to yield either oxidized or nitrated aliphatic species; however, the conditions required for significant free radical production are considerably different and mre severe (generally in the vapor phase at higher temperature and pressures) than the conditions found during nitration of benzene. As such, the formation of species predicted via this scheme, though not necessarily insignificant, must be considered with due caution. The following mechanism has been proposed as being predowinant for nitration of aliphatic species by Lee et al., (1976): 60HNO, Osean eeea tO an RH + ‘OH————» Rv + HO (78) R* + HONO,—————= NO, + HO" (79) It should be noted that the first step of this mechanism is in direct contradiction to that proposed by Ross and Kirschen (1976) in reactions (46) to (49). This contradiction, though of theoretical interest, is not germane to the question at hand; it is enough that both mechanisms indicate a resonable pathway for radical formation. Thus, aliphatic nitrates of the following type may be produced: NOg Ss HNO. CO —t O (80) Gs ENO, GNn B,C = C - CR, - H;—r Hc = C - cH cH, (a) During such free radical processes, oxidation steps also occur and carbon-carbon bonds may be broken. Therefore, not only may oxygenated by-products be produced, 61(J) A 1000 (01) com can , we ENO, :00H om HCH, ——> = H,C=C-CH,CH, but conceivably low molecular weight nitrated products (e.g., nitro- propane) as well. “pollutant formation from hydrogenation of the products (i.e., reactions 72-83) which are presumed to be present* in nitrobenzene is relatively straight forward, if somewhat laborious. Thus, the CHy Cy + 3H, ——~ O (84) NHg cy cy (85) CHy ON. No. HN. NO2 ao a 2 Pe om CY + 3H, following types of products are expected (again shown only for NOg toluene by-products; cf reaction 40 to 42): FImpurities such as those shown in Table VI can be removed by extraction with a base (e.g, Na,C0,); however, only a small portion of nitrobenzene (that which is not used for aniline production) is so treated. 62oH on NO2 NO NOs, Gn eee + Sha > Qu (87) Ost Non NH2 ow NH Hy NH on oH oH HN. Hy 4 The extent of hydrogenation of the above compounds is unknown; hovever, it is not unreasonable to assume that the nitro group may be reduced only partially as shown below: Cg chy + He (88) NO2 NO Furthermore, there is evidence (Rihani et al., 1965) that dinitroben- zene rapidly deactivates copper catalysts rather than being reduced to phenylenediamine. Thus, such by-products may never appear as effluents because of adsorption on, and subsequent regeneration of, the catalyst. Again, via a pathway an analogous to that of reaction (55), the aromatic nucleus may be either partially or completely reduced; thus the following types of by-products may reasonably be expected (again shown only for p-nitrotoluene): 63NH. '2 The hydrogenation of aliphatic nitro compounds are well known and lead to form ion of primary amines (or if reduction is incom plete, nitroso derivatives): NO, NH + aM CO co pe (Ee) wolcnteya, — Laekenee | — aebinte, From the foregoing discussion, by-products from the manufacture of nitrobenzene/aniline have been predicted. The intent of this section, despite the large number of reactions presented, has not been to imply that aniline manufacture results in excessive discharge of environmentally hazardous pollutants, but rather to account for the seemingly infinite number of species which are typically found in process wastewaters. Thus, the reactions shown must be considered exemplary of possible reaction types, rather inclusive of all possible 64reactions. From this standpoint, those pollutants which pose serious environmental threats may be quantified and the requisite control technology designed. To this end, by-products from the preceding reactions, together with feedstock impurities, are summarized in Table VII. PROCESS CONFIGURATION FOR NITROBENZENE/ANILINE MANUFACTURE Although a large number of different process configurations are described in the patent literature, only the general features of nitration processes and three reduction processes--catalytic vapor phase, catalytic liquid phase, and dissolving metal--will be considered explicity. However, it is important to note that any process description derived from the patent literature is likely to be somewhat different than that used in actual practice, and therefore, the following configurations must be regarded as generic rather than specific to any given plant. ¢ Nitration Proces: Ger Nitrobenzene was first manufactured commercially in England in 1856, and thus was one of the first industrial chemicals to become available'on a large scale. This early batch manufacture practiced in five gallon reactors (a glass carboy) cooled with ice-- reflects more the relative ease of aromatic nitration rather than 4 prior existing need, Currently, however, batch reactors (1000 to 1500 1b capacity--2 to 4 hour cycle) are uneconomical for large scale nitrations, as compared to continuous operations. Moreover, 65TABLE VIL SUMMARY OF POLLUTANTS FROM NITROBENZENE/ ANILINE 66 MANUBACTURE Reaction Pollutant Nunber! Acridine 61 Alkyl nitrates 82 Amino cresols 89 Amino phenols 40,72 Amino polymers 60,63 Aniline P Azobenzene 64,74,71 Azoxybenzene 56 Benzene F Benzidine (and related semidines) 72 Benzoic acid 77 Carbon monoxide F Copper salts c Cyelohexane Cyclohexene F Cyclopent ane Cyc lohexadienone 68 Cyclohexadienylamine Cyclohexenylamine 55,56 Cyclohexylamine Dianinotoluene 88 Dinitrobenzene 33 Tphenylhydrazine 57,65 Diphenylhydroxylamine 67 Ethanolamine F Ethylbenzene F Hydroxylamine 54,70 Methane F Methyldiphenylamine 66 N-substituted anilines 59 N-substituted nitrosamines 52 N-phenyl azepin 62 Nickel salts c Nitric Acid F Nitrobenzene PTABLE VII (Continued) Reaction Pollutant Number! Nitrogen oxides 43,1 Nitrous acid 36,38 Nitro cresols 78 Nitro phenols : 35,37 | Pentenes F Phenol 50,67 Phenylenedianine 39 —Fiirie seid aaa one Polycarboxylic acids 85 Sulfuric Aciéd Toluene F Toluidine 87 xylenes F lithe following notations are used for brevity: feedstock impurities : species results from catalyst attrition species results from incineration of waste products product wom 67‘Absorber Nitrobenzene To Aniline Production 3 ‘To Wastewater Treateent Benzene Sulfurse, ierobenzene Product To Exerger Drown Tani Absorber Distillation Colum facrobenzens 4 Still Bottoms 3 ‘To Wastewater & ‘Treatment 2 § steam —o 3 38 5 Mere Ack To Wascovat om ‘To Reactor Stean Galturie Acta concentration Source: Process Research, Inc., 1972. Sulfuric Acta (982) To Reactor FIGURE 4 CONTINUOUS LIQUID PHASE NITRATION OF BENZENE 68because few process changes have been made in batch processes in recent years, and descriptions of such processes have been presented by Groggins (1958) and Urbanski (1964) in considerable detail, only continuous processes are discussed further. Benzene may, in fact, be nitrated directly in either the liquid or vapor phase. The following discussion, however, is predicated upon the prevalance of liquid phase proce: In the most common continuous phase process (Albright, 1966), benzene is nitrated with an aqueous mixture of sulfuric acid (53 to 60 mole percent) and nitric acid (39 to 32 mole percent) at atmos- pheric pressure and temperatures between 45 to 90°C. Yields are typically better than 98 percent. This process (see Figure 4) is carried out in vented stainless steel vessels equipped with high speed agitators and cooling coils. Average residence time is ap- proximately 8 to 10 minutes. Nitrobenzene is continuously drawn from the side of the reactor and separated in a decanter. Once separated, this “crude” nitrobenzene is reportedly used directly in the manufac~ ture of aniline. If pure nitrobenzene is required, the product is washed first with water and subsequently with an alkaline solution (generally either a sodium carbonate or sodium hydroxide solution) in small vessels similar to the nitration vessel (i.e., equipped with high speed mechanical agitators) and then distilled. Alternatively, @ tubular reactor may be used for production of nitrobenzene. Advantages of such systems are somewhat shorter 69residence times, high spaces velocities (pounds of product per hour per gallon of reactor capacity), and lower capital, maintenance, and operating costs. In this sytem, benzene and the mixed acid (as defined for the above system) are rapidly emulsified by impinging the two streams and pumped to the reactor (see Figure 5). The reaction tem perature is controlled by circulating cold water about the outside reactor shell, Products are removed from the top of the reactor to 4 surge tank equipped with a vent. By controlling the recycle ratio from this tank, benzene is nitrated to nitrobenzene in yields better than 99 percent. Nitrobenzene is continuously withdrawn from the surge tank and purified, as described previously and shown in Figure 4. Whatever type of reactor is used for nitrobenzene manufacture, recovery of spent acid is essential, both from tle standpoint of eco- nomical operation and pollution. Generally, unreacted nitric acid is extracted from the spent acid by steam stripping (denitrating tover). The bottom products, dilute sulfuric acid (~60 percent by weight), is then concentrated by distillation (sulfuric acid concentrator) and recycled to the reactor as shown, or used in other manufacturing operations. Nitric acid removed overhead from the denitrating tover bleached with air to remove nitrogen oxides and subsequently recycled to the reactor, The overhead nitrogen oxides from the bleacher are scrubbed with water and recycled to the denitrating tower. Nitrogen oxides generated from the reactor are oxidized with air and water scrubbed, prior to recovery in the denitrating tower. 70Vent To Decanter Reactor Shell Reactor #0 Benzene REACTOR CROSS-SECTION Sulfuric’'Acid Nitric Acid Source: Humphrey and Smoak, 1963. FIGURE 5S TUBULAR REACTOR FOR NITROBENZENE MANUFACTURE nAnother approach to spent acid recovery is the use of feed benzene for nitric acid extraction (Dubois et al., 1956, and Buchanan 1958), In this method benzene, rather than steam is used to strip nitric acid from spent acid in the denitrating tower (see Figure 4). The nitric acid is thus dissolved in the benzene and fed to the reactor. The remaining sulfuric acid is concentrated as before. Advantages of such a system include the elimination of a bleaching tower and a large absorption tover; presumably recovery of nitrobenzene 8 also enhanced. Disadvantages, however, include: indiscriminant extraction of all reaction impurities present in the spent acid which necessitates a bleed stream to prevent buildup of such im- purities; and more importantly, introduction of perhaps significant amounts of benzene into the sulfuric acid to be concentrated. ‘Though relatively few process modifications have been suggested for reduction of effluents during nitrobenzene manufacture, Hanson (1976) has shown that organic by-product is a function of the sul- furic acid concentration in mixed acid systems. Additionally, the rate of aromatic nitration is known to increase with increasing sulfuric acid concentration. Of greater significance, perhaps, is the decrease in both organic by-product and nitrous acid formation with increasing sulfuric acid concentration. Based on studies of the mono-nitration of toluene, if the proportion of sulfuric acid i increased towards the limit of about 37 mole percent sulfuric acid, 15 mole percent nitric acid, and 48 mole percent water, organic by-product formation is decreased by over 25 percent. 72Generic Nitrobenzene Reduction Processes Not suprisingly, aniline, like it's immediate precursor nitro- benzene, was among the first organic chemicals to be manufactured on an industrial scale. Traditionally this was a batch process using agitated reactors, in which iron (generally in the form of turnings), water and 30 percent hydrochloric acid reduced the nitrobenzene to aniline in 90 to 95 percent yield. Drawbacks of this process include: (1) large quantities of iron (11) and iron (IIL) hydroxides are generated which must be disposed of in an environmentally acceptable way; and (2) high labor requirements. Interestingly enough, though largely replaced by continuous catalytic hydrogenation processes, the above method is now used for production of piment grade iron oxides with aniline as a by-product. Thus, three manufacturing configurations will be considered: vapor phase catalytic processes; liquid phase catalytic processes; and the Bechamp process (batch). Catalytic Proc The major portion of the United State aniline capacity is based upon continous vapor phase processes. Typically, nitrobenzene (containing less than 10 ppm thiophene) is vaporized in a stream of hydrogen and introduced into the fluidized bed reactor (see Figure 6). The catalyst, 10 to 20 percent copper by weight on silica, is made by spray-drying a silicic acid matrix (20 to 150 pm) with a cuprammonium compound and activated in situ with hydrogen at 736A Purge TA Volatile Impurities Hydrogen Aniline Nitrobenzene. Separator 8A still Bottoms Distillation Column 9A To Wastewater Treatment Nitrobenzene Column Extraction Source: Karkalits, 1959. FIGURE 6 CONTINUOUS VAPOR PHASE PRODUCTION OF ANILINE 74250°C. The nitrobenzene vapor-hydrogen mixture (300 percent exces: hydrogen) is fed through a porous distribution plate at the bottom of the fluidized bed reactor. Actual reaction conditions have not been publicized but the basic patent (Karkalits, 1959) claims operation at 270°C and 1.5 atm with a contact time of several seconds between catalyst and reaction mixture. The reaction is highly exothermic and heat is removed by circulating a cool fluid (most probably nitroben- zene) through tubes suspended in the fluidized bed. Catalyst fines are removed from the product gas with porous stainless steel filters in the top of the reactor. ‘The crude product mixture (aniline, hydrogen, and water) leaving the reactor is condensed and separated from the gas stream (3.5 per- cent water, 0.5 percent aniline, balance hydrogen); most of this gas stream is compressed and recycled to the reactor, but a small portion is vented to prevent buildup of gaseous impurities introduced with the hydrogen feed. The aqueous and organic phases are separated in a decanter. The organic phase (lower layer), consisting principally of aniline, up to 0.5 percent nitrobenzene, and 5 percent water is purified by two stage distillation. In the crude still, aniline and water are removed overhead, while higher boiling organic impurities, such as nitro- benzene, reasin in the still bottoms. The overhead product from the firet colum, is purified in a finishing still; water is withdrawn 75from the top of the column while aniline is withdrawn in a side~ stream near the bottom of the column. The bottom product is recycled to the crude aniline still. Obviously other separation processes are possible: water may first be removed by distillation from the organic material; this may then be distilled to produce aniline as an overhead product. The waste streams from this separation process are similar to those described previously. Sulfur compounds (e.g., thiophenes) irreversibly poison the catalyst by forming copper sulfide; in addition, dinitrobenzenes are also reported to decrease catalyst activity (Gharda and Sliepcevich, 1960). Since commercial production of aniline is reported to be 1500 grams of aniline per gram of catalyst, deactivation via these mecha~ nisms does not appear to be serious. By burning off the organic materials which deposit during normal operation, the catalyst may be reactivated to near initial activity. Presumably, this regeneration is done in situ, and probably not more than several times a year. Recovery of aniline from the aqueous phase (approximately 3 percent by weight) of the decanter, if not economically justified, required to meet current water quality standards. Aniline may be recovered from this phase by countercurrent extraction with nitro- benzene, for which an extraction efficiency of 98 percent is claimed (sittig, 1974). An alternative technique is to concentrate aniline from this stream using a stream stripper and to then incinerate the enriched aniline water mixture (EPA, 1972). 76Further variants of nitrobenzene reduction processes have been described in the patent literature. Among these are a fixed bed process which uses a nickel sulfide catalyst deposited on alumina (Winstrom, 1958, 1959) and liquid phase processes using supported palladium (Thelen et.al., 1975), rhodium (Iqbal, 1976), or nickel catalysts (Cooke, 1966). Of these liquid phase processes, only the nickel catalyst system is used commercially in the United States and therefore is the only configuration to be considered in the following discussion. The reactor, equipped with suitable heat exchanger and an agitator capable of dispersing hydrogen at high rates, is charged initially with aniline, ethanolamine, and a supported nickel catalyst (both 5 percent by weight based on aniline), As illustrated in Figure 7, nitrobenzene (containing less than 10pm of thiophene) is continuously fed, together with hydrogen, to the reactor at such a rate that the concentration of aniline (by weight) in the liquid phase is 95 percent or greater; product aniline and water are removed as a vapor. The reaction proceeds at temperatures of 160 to 180°C under pressures of 1 to 2 atmospheres. The temperature of the reaction is controlled by circulating a coolant (generally water or low pressure steam) through heat exchangers (which remove approximately 65 percent of the heat of the reaction) and by evaporation of aniline and water from the reactor. The product mixture (hydrogen, aniline, and water) is cooled and separated in a binary separator, Because the reaction is strongly 76B Purge 7B Volatile Impurities Hydrogen: catalyst Aniline itrobenzene Reactor i Ko) Distillation Colum, 8B Still Bottoms 9B To Wastewater Treatment }¢~Nitrobenzene Extraction Column FIGURE 7 CONTINUOUS LIQUID PHASE PRODUCTION OF ANILINE 78exothermic, generally more aniline is evaporated from the reactor than is produced by reduction of nitrobenzene; therefore a portion of the condensed aniline is returned to the reactor. Hydrogen is also recycled from the separator to the reactor, although about 5 percent of this stream is purged to prevent accumulation of volatile impurities. Though the purification procedures are not specified in the basic patent (Cooke, 1966), @ process similar to that shown in umed . Figure 6 Batch Proc The final configuration to be considered is the Bechamp process (see Figure 8). Crude nitrobenzene is charged to a reactor fitted with an efficient reflux condenser and agitator. Cast iron, water, and dilute (30 percent) hydrochloric acid are gradually added to the nitrobenzene. Typically 10 to 20 percent of the total iron is added initially and the mixture heated to reflux temperature ( 200°C). ‘The remaining iron is added at such a rate so as to maintain reflux conditions. ‘The water used in the reaction is generally in the form of aniline water recovered from the separator. Not only does this procedure minimize effluent 4 charges, but the catalytically active iron salts are also recycled. The weight ratio of reactants is approximately 115 parts of iron, 0.27 part of hydrogen chloride and 60 parts of water per 100 parts of nitrobenezene. 79og 7c w Volatile Impurities Water/ 3 + Hydrochloric & ‘Acid = 3 8 Aniline Tron Z 4 Nitrobenzene 3 a 8c Still Bottoms To Wastewater —_Fe,0, Treatment a Extraction Column 10 To Wastewater Treatment FIGURE 8 BATCH PRODUCTION OF ANILINEAt the end of the reaction ( 10 hour for a 2270 kg charge), aniline may be separated from the resulting sludge by any number of methods including steam distillation, vacuum distillation, fil- tration, centrifugation, or syphoning. Typically the product is neutralized with sodium carbonate and allowed to separate. Aniline, along with sone reaction water, is decanted; the remaining aniline may be separated from the sludge by steam distillation. After drying, thie sludge may be used in pigment manufacture. The water- aniline mixture is purified as discussed previously and shown in Figures 6 and 7. Effluent species have been previously identified and summarized in Table VII, This information, together with a generic process configuration of nitrobenzene and aniline” manufacture previously formulated, is presented in Figure 9. “three process configurations have been formulated for aniline manufacture. Because of process similarities and to avoid duplication, only the generic process for vapor phase hydro- genation of aniline is presented. 81ze romna, staan] (i) 0 Sra rte ata : powers Sane ecyete to wesetor) Eacal Froure9. Krtnsen coat Se ae staniicant POLLUTANTS FROM Notte weicnsc sans [NVTAOBENZENE/ADILIVE MANUFACTURESECTION III INDUSTRIAL WASTEWATER MANAGEMENT INTRODUCTION In the first half of this report, potential pollutants from the manufacture of nitrobenzene/aniline were identified. The remainder of the report will discuss specific industrial wastewater practices for handling those waste streams identified, and evaluate alternative treatment practices for removing toxic contaminants from the process effluents prior to discharge to the environment. INDUSTRIAL WASTEWATER TREATMENT PRACTICES In selecting the appropriate mode of treatment for an industrial waste stream, factors other than just the simple reduction of standard wastewater parameters should be examined. Specifically, the following areas merit consideration: © The origin of toxic pollutants, in terms of both reaction chemistry and process configuration; © The identification of inhibitory or refractory components of the waste stream; © The acceptability of current treatment practices; and © The compatability of treatment processes in achieving the effluent requirements. Wastewater management of toxic effluent streams involves both in-plant control technology and end-of-pipe treatment practices. Procedures to reduce the strength and volume of the final effluent stream may include improved housekeeping practices, waste stream 83segregation, and reuse or recycle of process streams. End-of-pipe treatment technology which, for purposes of this report, refers to both pretreatment and final treatment practices, may involve physical chemical treatment techniques, biological treatment, or a combination of the above. Waste disposal by subsurface injection, although widely accepted in the past, is being more closely regulated by Federal and State agencies, and is generally discouraged when alternate treatment and disposal systems are available. ‘The selection of the mode of treatment is largely dependent on the volume of waste to be treated and the pollutants present. Traditionally, the efficiency of a treatment method is measured by the percent removal of 5-day biochemical oxygen demand (BOD,) and total suspended solids (TSS). Chemical oxygen demand (COD), or total organic carbon (TOC) are used to measure the strength of industrial waste. Discharge standards commonly include specific restrictions on the pH range, effluent color, level of ammonia-nitrogen, and total Kjeldahl nitrogen (TKN). Where applicable, other wastewater constit- uents, such as free cyanide, heavy metal, or phenol concentrations may be monitored and controlled. A brief, general review of biolog- ical and physical treatment methods used by industrial dischargers follows. Biological treatment involves the breakdown and stabilization of organic material by aerobic or anaerobic microorganisms. Treatment processes available for industrial application include: variations 84of the activated sludge process, aerated Lagoon systems, oxidation or contact stabilization ponds, trickling filters, rotating biological discs, and anaerobic lagoons or digesters. Historically, the acti- vated sludge process, in which aerobic microorganisms are mixed with the influent wastewater and subsequently removed as a sludge, has had the broadest application to industrial wastes. Detention periods and process configurations may be modified to achieve the desired level of BOD removal, nitrification, and in some cases, denitrification. The toxicity of the waste, the biodegradability of the waste (typically judged by the BOD/COD ratio), and the metabolic rate of the micro~ organisms (i.e., the effective removal rate) all influence process efficiency. Physical-chemical treatment techniques may be used alone or in combination with biological processes to achieve effluent standards. Neutralization and equalization, for example, are commonly used as pretreatment steps prior to activated sludge treatment. Soluble organic compounds not effectively removed by biological treatment may be separated from waste streams by adsorption (generally on either carbon or an ion exchange resin), stripping techniques, distillation, solvent extraction, or membrane processes (i.e., ultrafiltration, reverse osmosis, electrodialysis). Oxidation, acid or alkaline hydrolysis, photolysis, chlorinolysis, or incineration have also been used to degrade organic species in process wastewater streams. a5The selected mode of treatment is determined by the availability of different treatment operations and processes to economically achieve the desired effluent. The design criteria for a specific treatment facility will vary with the strength and volume of the wastewater stream and the final means of effluent disposal. In each case, the process configuration and plant layout should be examined to identify point source discharges and pollutant loadings. Where possible, in-process changes, stream segregation, and solvent reuse should be implemented to reduce the process waste load. CURRENT TREATMENT OF WASTEWATER FROM NITROBENZENE/ANILINE MANUFACTURE Wastewater Characteristi Major process waste streams generated during the manufacture of nitrobenzene/aniline include: the nitrobenzene wash water (Point No. 3), the nitrobenzene distillation colum overhead (Point No. 5) and the aniline recovery colum purge (Point No. 8) (See Figure 9). Major pollutants include aniline, nitrobenzene, aminophenols, nitro- phenols, carboxylic acids, water soluble amines, nitrates, and nitrites. Table VIII lists typical concentrations of selected pollutants found in nitrobenzene/aniline waste streams, as reported by two manufacturers. A point source-by-point source summary, of all significant pollutants predicted from the manufacturing process are presented in Figure 9. 86iz TABLE VIII Characterization of Raw Waste Loading From Nitrobenzene/Aniline Manufacture!» 2 Process Lines Nitrobenzene Aniline ave Min, Max. ave Min. Max. Flow 170-897 110-501 220-1840 73-787 23-471 110-1040 pil 1.8 562-21 8.4 567-7, 10.2-10.5 cop 5.8 8.6 7 - - Toc 1,6-3.5 262-117 7.6 1.8 2765 Tss 0.09 0.18 - - - Aniline - - - 0.067 0.005 0.49 Benzene - - - 0.005 0 0.031 Nitrobenzene - - - 0.002 0 0.012 Ipata reported in units of 1b/1000 1b of ~ product, with the exception of pl. pane Compiliation of data reported by two manufacturers. Source: EPA Organics and Pl tics 1976 308 Response BPT Master File Listing.Data characterizing the combined waste load from an nitrobenzene/ aniline manufacturing facility have been previously published by EPA as part of support material for the development of effluent limita~ tions (Train, 1975). However, as those effluent limitations were remanded in 1976 (questionable procedures were claimed to have been used for the measurement of wastewater parameters), these data are not provided within this report. Federal and State Discharge Requirements The major objective of the Federal Water Pollution Control Act, as amended*, is to restore and maintain the chemical, physical, and biological integrity of the Nation's waters. Among the goals and policies set forth by the Act, the following address industrial point source discharges to navigable streams: @ It is the national goal that the discharge of pollutants into the navigable waters be eliminated by 1985. e@ It is the national goal that wherever attainable, an interim goal of water quality which provides for the protection and propagation of fish, shellfish, and wildlife and provides for recreation in and on the water be achieved by July 1, 1983. @ It is the national policy that the discharge of toxic pollu- tants in toxic amounts be prohibited. @ It is the national policy that a major research and demonstra: tion effort be made to develop technology necessary to elimi- nate the discharge of pollutants into the navigable water: waters of the contiguous zone, and the oceans. Whe Federal Water Pollution Control Act Amendments of 1972 (PL 92-500) further extended the scope of the Federal Water Pollution Control Act of 1965, as previously amended in 1966 and 1970, New amendments to this legislation, The Clean Water Act of 1977 (PL 92-217), were signed into law in December, 1977. 88In committing the nation to meeting these goals and policies, the Act established an implementation schedule for compliance. To this end, Section 301(b) of the Act mandates the following: © Not later than July 1, 1977, effluent limitations for point sources, other than publicly owned treatment works, shall require the implementation of the best practicable control technology currently available (BPT) as defined by Section 304.* ‘Those discharges to publicly owned treatment works shall comply with any applicable pretreatment standards defined under Section 307 of the Act. © Not later than July 1, 1984 effluent limitations for cate~ gories and classes of point sources, other than publicly owned treatment works will require application’ of the best available technology economically achievable (BAT) for the 65 toxic pollutants (as listed in Appendix I), which will result in reasonable further progress toward the national goal of eliminating pollutant discharge.** In the case of the discharges of a pollutant into a publicly owned treatment work, compliance with applicable pretreatment standards i required. © Compliance within 1 to 3 years of issuance for any toxic standard established under Section 307(a). @ Not later than July 1, 1984, effluent limitations for point sources, other than publicly owned treatment works, shall require application of best conventional pollutant control technology (BCT). © Not later than 3 years after the date such limitations are established, but in no case later than July 1, 1987, com pliance with effluent Limitations for all unconventional pollutants (ise., those pollutants not included under toxic regulations or BCT).##* ‘*kn estimated 85 percent of industrial dischargers met this deadline. For those dischargers that have acted "in good faith" the compliance schedule has been extended to April 1, 1979 (Barrett, 1978). ‘**Industry must comply within 3 years of issuance of BAT regulations for any chemical added to the list. *eHUnder Section 304(a) the EPA Administrators directed to publish @ list identifying a list of conventional pollutants. The list, which is to be revised as deemed appropriate, shall include, but is not Limited to, BOD, suspended solids, fecal coliform, and pi. 89Additionally, the Administrator of the EPA, under Section 304(b) of the Act, is directed to promulgate regulations which identify in terms of wastewater characteristics, the degree of effluent reduction attainable through the application of BPT, BCT, and BAT for classes and categories of point sources (other than publicly owed treatment works). These regulations, or effluent limitation guidelines, are to specify those factors related to the establishment of BPT, BCT, and BAT control measures and practices, such as, the process enployed, the age of equipment, process changes, the engineering aspects of the application of various types of control techniques, non-water quality impacts, and the cost of achieving such effluent reduction. The organic chemicals industry is highly complex, covering two Standard Industrial Classification (SIC) Groups in which 260 product- process segments have been identified. Thus, for the purpose of developing effluent regulations, the EPA has categorized selected segnents of the industry into two phases. On April 25, 1974, Part 414 was added to Title 40 of the Code of Federal Regulations, estab 1 hing final effluent limitations for existing sources in 40 product process segments (Phase I). Additionally, performance and pretreat- ment standards for new sources in the organic chemical manufacturing point source category were defined. Interim final regulations for Phase II were published on January 5, 1976, amending 40 CFR to include 27 additional product-process segments and a new subcategory. Chemicals were grouped within four subcategories on the basis of 90similarities of process operations, The manufacture of nitrobenzene/ aniline by the nitration of benzene and its subsequent hydrogenation is included as part of "Subcategory C - Aqueous Liquid Phase Reaction systens." In establishing Phase I and Phase II regulations, the Agency acknowledged the toxicity of certain organic chemical manufacturing wastewaters and the potential hazard to the environment; however, faced with a mammoth task and rapidly approaching deadlines, effluent Limitations were written in terms of the conventional parameters of BOD,, TSS, COD, and pH. Furthermore, since biological treatment was the identified BPT for the organic chemicals point source category, effluent limitations were established for specific pollutants known to be inhibitory to biological treatment and detected in significant concentrations in given waste streams. Table IX presents the BPT regulations and standards of performance for new point sources for aniline manufacture. . TABLE 1X BPT Effluent Limitations and New Source Standards of Performance for Aniline Manufacture Effluent Effluent Limitations kg/kkg (1b/1000 1b) of Product Characteristic Br New Source 30-Day Daily 30-Day Average Maximum. Average BOD, 0.51 0.54 0.62 Tss 0.15 0.68 0.76 0.34 pH 6.0-9.0 os 6.0-9.0 - Source: Federal Register, Vol. 39, No. 81, April 25, 1974, a1As part of the rule making process, the EPA is required to gather information and comments pertinent to proposed and established regulations. Strong opposition to the sampling and analytical tech- niques used by the EPA contractor in developing effluent limitations led to court action in 1976 (after issuance of Phase II regulations on January 5, 1976). As a result, the EPA eventually concluded that the contractor retained by the Agency had used procedures to measure certain parameters of the industry wastewaters "which may have been, in certain instances, faulty" (Federal Register, April 1, 1976). Thus, in accordance with a decision by the U.S. Court of Appeals, the EPA revoked all of 40 CFR 414 regulations concerning organic chemicals with the exception of those concerning butadiene manufacture. At this time, there are no existing federal regulations under Title III of the Federal Water Pollution Control Act governing the point source dis~ charges from the manufacture of nitrobenzene/aniline. Under Title IV of PL 92-500, however, any discharger to navigable waters must be certified by the State in which the discharge originates and issued a permit under the National Pollutant Discharge Elimination System (NPDES). Each NPDES permit defines effluent limitations and monitoring requirements, as well as a schedule of compliance. In the absence of effluent limitation regulations, discharge limitations have been established on a case-by-case basis, as authorized by the State agency and approved by the Regional Water Enforcement Board of the EPA. NPDES permits are to be “revised or modified in accordance with 92toxic effluent standards or prohibition" under Section 307(a) of the Act. While injection wells are not specifically addressed by the NPDES legislation, EPA has established rules and regulations governing waste disposal wells within the framework of the NPDES system. Industrial dischargers are typically required to monitor flow rate, injection and annulus pressure for each well; moreover, no new wells may be put into operation without re-application and subsequent NPDES permit modification. Deep well disposal no longer considered to be a viable disposal method by EPA (Federal Register, January 6, 1977).* Current Industrial Practice: There are five U.S. manufacturers of nitrobenzene/aniline with facilities currently in operation at six locations; a sixth manufac~ turer, Mallinckrodt, Inc. produces aniline from a supplier delivered nitrobenzene feedstock.** Table X presents a listing of these manu~ facturers, indicating nameplate capacities and current wastewater treatment practices. As will be discussed in Section IV, there are several practicable methods by which wastewaters containing nitro- phenols, nitrobenzenes, and aniline may be treated. However, as most ‘Win an effort to control such practices (though short of out- lawing deep well injection), the EPA has required permit holders to submit engineering summaries of disposal practices and "practicable alternatives" to subsurface disposal including evaluation of: (1) process changes and in-plant reductions to alter the nature of the wastes; (2) incineration; (3) biological treatment methods; (4) physical-chemical treatment methods, and (5) combinations of the above. **american Cyanamid's production facilities in Bound Brook, New Jersey, reported to be on stand-by since 1974, are to be reacti- vated in mid 1978. 93nate x Non 0.S. sorioameme/awoie muracromm Caution posn/year) Ce Ds 100 vs ooai7ei | aweraltzacion, equale ‘eciy scipany 2 saerican Cyanania o 0 vw o007e7 | erates 1ngeon, tiotogt= iow" Tang, eat Virgina fel eoneacty elaritiestion, 1. dutons de Xesoure & co. wa 20 rx ooossss | equnltzacton, aesared Beacon, Tosa Iagoony aceive Setorpeion.| atone de nasour & 20 we» vs ooosris | orgie extraction Eisbetoy naw Jerecy ti iietghy Horch earoléen Wobey Chanel Corporation 5, 200 vw oonsiss | weverattzation, clertttee- Sev Mareinevitiey Wane firgiaga Hon, egualieacton, actinoced lutgey aceSoated carbon Rubicon Chenteal, Toe. 8 « 4 o000ss2 | suneurtace stapes. eyentcad Marketing Reporter, Janeasy 7, 1974, May 24, 2971, August 20, 1976 aod commmications vith intuts paca coldected feen BPA Orguaten and Plastice 208 Respoces (2976), APE Master Pile Liat Elon of wastewater creaconat faciiieiee ftom pusltely available Inforaarion impos aaerican cyenanid tactitty 1a toed Brook, How Jersey as been an atand-by since 1974; altrobencene capac: S'etltvon pounte/pear, and saliiee capacity’ 60-stllton pounca/yene” This plant 1a dus to cons on-line io 197 Srroduceion figiten are wnavailable for thia aniliae samufacturer. Yate: Mitrobensene Se oot produced ot (he ‘actliey.manufacturers produce numerous chemical compounds at a particular anufacturing site and historically, have combined product waste lines prior to treatment, it is impossible to sess the efficiency of a treatment scheme specific to nitrobenzene/aniline wastes, Fur- thermore, data resulting from treatability studies on segregated streams have been classified by manufacturers as confidential, and therefore, are unavailable for reference. . At this time, a wide variety of treatment techniques are being applied to nitrobenzene/aniline manufacturing wastewaters. First Mississippi Corporation, a subsidiary of First Chemical Corporation, completed installation of both steam stripping columns and granular activated carbon columns at their Pascagoula, Mississippi plant in 1977. This exemplary operation was designed to achieve zero pollutant discharge; however, wastewater treatment data (e.g, influent/effluent analyses) are not publicly available at this time (desRosiers, 1978). Carbon adsorption is also employed by both duPont (at their Beaumont, Texas facility) and Mobay Chemical Corporation for removal of dis~ solved organics, following pretreatment and activated sludge treat ment of the waste streams.* At their Gibbstovn, New Jersey facility, duPont provides organic extraction and stripping units, while American Cyanamid and Mallinckrodt rely on biological treatment for removal of “¥Only limited information is publicly available indicating the manner in which waste streams are segregated (and/or mixed with waste streams from other process operations) at @ particular manufacturing site.organic pollutants. Only Rubicon Chemicals, Inc. practices deep well disposal of nitrobenzene/aniline process streams.* Future Regulatory Concern In recent years, through court and congressional action, tighter restrictions have been placed on the discharge of hazardous or toxic materials. The four laws which directly affect the manufacture of nitrobenzene/aniline are: (1) The Clean Air Act; (2) The Toxic Sub- stances Control Act; (3) The Resource Recovery and Conservation Act; and (4) The Clean Water Act of 1977. @ The Clean Air Act, PL 91-604 (passed in 1970, and subsequently amended in 1977) requires regulation of specific pollutants under a permit system for point source emissions. Air emissions resulting from nitrobenzene manufacture have been studied in detail (Process Research, Inc., 1972). ® The Toxic Substances Control Act (TOSCA), PL 94-469, which was signed into law in October of 1976, authorizes the EPA to regulate the manufacturing, processing, distribution, use, and disposal of chemical substances or mixtures deemed to represent an “unreasonable risk of injury to health or the environment." The Administrator is directed to control hazardous emissions or discharges to the environment under the Clean Air Act and Federal Water Pollution Control Act, as necessary, unless, it is in the public interest to enforce additional protective measures under TOSCA. ‘WeTn general, proper site selection (i.e., geological conditions suit- able for the emplacement of fluids), well design, and construction techniques used in injection well systems, make contamination of fresh water aquifers remote. However, deep well disposal is not without hazards for extremely toxic and persistent wastes. A serious threat to nearby groundwater supplies is potentially posed by either the failure of the well system or migrations of the wastes. Specifically, in the case of deep well disposal of nitro- benzene/aniline waste streams, nitrobenzene and nitrophenol are deemed "hazardous for deep well injection in any system" (Reeder, et al., 1977 and Water Pollution Control Federation, 1977). 96© The Resource Recovery and Conservation Act (PL 94-580) signed into law in October of 1976, will control the transportation and disposal of solid wastes designated as toxic or hazardous. @ The Clean Water Act of 1977 (PL 95-217) which embodies the major points of the "consent agreement (signed in 1976 by EPA and environmental interest groups), requires stricter regulation of toxic discharges. Aside from establishing effluent limitations for 65 toxic pollutants in terms of BAT, pretreatment standards are required for wastes d charged to publicly owned treatment works (POTW). However, if the treatment by such POTW removes all or any part of the toxic pollutant in question (and discharge of the pollutant does not prevent sludge use or disposal), the pre-treatment requirements for the sources may now be so modified as to reflect the removal rate achieved by the POTW. Although the Safe Drinking Water Act (PL 93-523) enacted in 1974 not explicitly directed toward point source discharges, the EPA is empowered by this legislation "to promulgate regulations which contain minimum requirements for effective programs to prevent underground injection practices which endanger potential or present drinking water sources" (Federal Register, August 31, 1976). The responsibility of enforcement is left to State agencies under a federally approved per- mit program. Thus, the proposed regulations are intended to give maximum flexibility to the States in designing underground injection control programs, in recognition of the large degree of variation in geological conditions, groundwater use, and existing deep well injec- tion operations, While key provisions of this Act have yet to be defined, regulations will, at the very least, require the routine monitoring and inspection of subsurface injection systems (Federal Register, August 1976). 97However, as was the case with Section 307(a) of PL 92-500 and the resulting "consent agreement," judicial interpretation of the laws will undoubtedly play a major role in their enforcement. It is clear, however, that with the passage of The Clean Water Act of 1977, effluent guidelines promulgated by EPA will strike a balance Between controlling the classic water quality parameters (i.e., BOD,, TSS, pH) and specific toxic pollutant 98SECTION IV METHODS OF WASTEWATER TREATMENT INTRODUCTION The quantity and quality of the pollutant waste load from a manu~ facturing facility is dependent on the degree of product purification, by-product separation and recovery, solvent reuse and recycle, and stream segregation practiced. Ideally, the treatment system best suited for a particular manufacturing operation should be approached on an individual bas: » point source-by-point source. However, from a historical perspective, treatment of industrial effluents has been Limited, in most cases, to the application of "end-of-pipe" technolo- gies to combined waste streams.* Typically, the treatability of a waste stream is described in terms of its biodegradability, as biological treatment usually provides the most cost-effective means of treating a high volume, high (organic) strength industrial waste (i.e., minimum capital and operating costs). Furthermore, biodegradability serves as an impor- tant indicator of the toxic nature of the waste load upon discharge to the environment. However, as indicated in Section III, the nature of the organic waste load from nitrobenzene/aniline manufacture is conducive to physical treatment (i.e., activated carbon adsorption, liquid-liquid extraction, steam stripping). Thus, in presenting a Win practice, waste streams from not only a specific manufacturing process, but also from several product lines, may be combined, prior to treatment and discharge. 99general discussion and literature review of wastewater treatment from nitrobenzene/aniline manufacture, this section of the report is divided into three major subsections: (1) biological treatment; (2) physical treatment; and (3) combinations of selected treatment technologies. Furthermore, with the exception of specific treatment Processes, such as counter-current extraction of aniline with nitro- benzene, this section will not be specific to individual process waste streams. O£ the several hundred potential pollutants from nitrobenzene/ aniline manufacture (see Table VII), 10 compounds* are EPA priority pollutants (see Appendix III). In addition, many other pollutants (e.g+, acridine, azepins, diphenylamine, to name but.a few) represent toxic discharges to the environment. However, only those pollutants that were repeatedly cited in the literature as contributing to the refractory, inhibitory, or toxic nature of the waste load (that is nitrobenzene, dinitrobenzene, aniline, nitrophenols, and soluble amines) are considered explicitly in evaluating wastewater treatment alternatives. This decision was based on two major considerations: (1) It is impractical from an engineering standpoint to discuss treatment options on a pollutant-by-pollutant basis. ‘Treatment operations and processes are selected on the basis of their effectiveness in treating a particular wastewater, with many constituents. (2) Without laboratory or pilot test data, a ranking of each treatment operation and process, based on its ability to remove each of the pollutants potentially present, would be speculative. WBenzene, benzidine, nitrobenzene, 2-nitrophenol, 4-nitrophenol, 2,4- dinitrophenol, 2,4-dinitrotoluene, 2,6-dinitrotoluene, phenol, and toluene. 100It is not unreasonable to assume, however, that a treatment method capable of removing nitrobenzene, dinitrobenzene, nitrophenols, and aniline from wastewater, might also be effective for the treatment of other toxic pollutants present in low, or trace concentrations. BIOLOGICAL TREATMENT Water and soil organisms naturally found in the environment have only a limited ability to assimilate synthetic organic chemicals found in an industrial waste stream. However certain compounds which may appear to be resistant to biological degradation in natural waters, may, in fact, be readily oxidized by a microbial population adapted to the waste. Thus, the successful application of biological processes to the treatment of hazardous organic wastes is largely dependent on: (1) the ability to acclimate biological organisms to the waste stream (e.g., activated sludge); (2) the operation of the treatment system at a practicable removal rate (throughout seasonal changes); and (3) the stability of the treatment system during variations in the waste loading (i.e., operation near toxic or inhibitory concentrations). Table XI presents a summary of those studies pertinent to the biological degradation and treatment of nitrobenzene/aniline waste- waters, Although many of the citations are specific to the degrada~ tion pathways (in microbial systems) of pesticide-derived substituted anilines and nitrophenols, these data do provide valuable informa- tion as to the susceptibility of such compounds to biochemical transformation, Furthermore, while only one biological study on 101soak poet Saari AScohccar vsuanat secmare mt | tchimmend, aciate icromaane comet coords to | Saora by ae ecgpag of “| BES a, a esa we tiies + | ite majead ew earan | snniae mncwettie scree iecatty | Sal peerste ofS) Sie | Sendeest tesa] st [option pete yy custo sna daring | Aiton of ltr gre ce STG | Serna ates x site ctf iSce Stipe tetera” | Govagipostne "| atogtan poet Tors pres ot | Teteasee ie alatne ae Beltre [ARI daah, | Ser satiman! ISiES & Se pentcteting s/t trtseropaasal 08 as, aiteeber fe tee ‘Ge i Spee as Sa | ie She | om AP a, 102Saas dni (9 alt) gece ae Soe ne ‘Sty 33 percent sont ton erheses 22) wet | sence a" Sorel alcetnere Mla rsucte a eto, 103Seaactn rcmer Site by epee sect an ae ahamster te oe ite ee co Sree cag semcae ‘Sti “Stcetipas aiy Slee 2p sn sean sve terse 23 af ating cnc 104actual manufacturing wastes has been cited (see Chudoba and Pitter, 1976), the biodegradability and removal rate of nitrobenzenes, nitro phenols, and aniline in acclimated systems have been examined. Thus, Table XI serves @ useful reference point for determination of an optimal treatment scheme for nitrobenzene/aniline manufacturing wastes. As indicated, microbi 1 degradation of nitrobenzene has been reported by Alexander and Lustigman (1966) but neither the pathway nor the degradation products were identified. Cartwright and Cain reported reduction of the nitro group of substituted benzenes (nitro- benzoic acids) to the amino moiety. On the other hand, reduction of prnitrophenol to nitrite was reported by Raymond and Alexander (1971). Environmental degradation of aniline appears to be somewhat better understood than nitrobenzene. Bordeleau and Bartha (1972) studied the susceptibility of substituted anilines to enzymatic transformation by the soil fungus Geotrichum candidum. This research, which was designed to determine molecular configurations of substi- tuted anilines that are conducive to efficient biochemical trans~ formation, found azobenzene and high molecular weight amino polymers to be the principal products of degradation. Furthermore, as electron-density of the amino group increases, the yield of amino polymers increases relative to azobenzene. Aniline utilization by a soil pseudomonad has been reported by Walker and Harris (1969). While the degradation pathway was not determined, ammonia was identified as a product of the bacterial 105oxidation. A possible pathway, however, is direct conversion of aniline to catechol with the liberation of ammonia. In support of this hypothesis, catechol is a well established intermediate in the breakdown of many aromatic substances, which is immediately oxidized by aniline grown* pseudomonads. Malaney (1960) observed that acclimated activated sludge is able to use aniline as a sole source of carbon, Although the ability of the aniline-acclimated activated sludge to oxidize N-substituted anilines and nitroanilines was greatly reduced in Warburg tests, Malaney concluded that the sludge could be adapted to a great variety of compounds related in chemical structure to aniline (e.g., phenyl- diamines, aminophenols, aminobenzoic acids, and aliphatic amines). Furthermore; removal of nitrobenzene and nitrophenols was 98 percent and 95 to 97 percent complete, respectively, in biodegradability studies with adapted, activated sludge. However, the non-biodegrad- ability of dinitrobenzenes, dinitrophenols and trinitrophenols has been documented (Pitter, 1976; Pitter et al., 1974; and Chudoba and Pitter, 1976). These research results are not intended to suggest that effluents suitable for direct discharge to navigable waterways may be achieved solely by biological treatment.** “¥Pseudomonads grown on aniline as its sole source of carbon. **potential drawbacks include limited efficiency in the removal of toxic organic compounds (as compared to physical separation processes) and possible inhibition of nitrification by degradation products (see Tomlinson et al., 1966; Hockenbury and Grady, 1977; and Joel and Grady, 1977). 106Currently, four manufacturers are utilizing biological processes to treat nitrobenzene/aniline manufacturing wastes (see Table X) duPont (at their Beaumont, Texas facility) and Mobay Chemical employ biological treatment in combination with activated carbon adsorption; whereas, American Cyanamid and Mallinkrodt combine biological treatment with physical-chemical pretreatment. PHYSICAL PRETREATMENT AND SEPARATION PRACTICES Physical unit operations are commonly used by industrial manu- facturers as in-process purification steps, for separation of streams (e.g, a decanter), or for removal of constituents from Liquid ph es for recovery or disposal. Such unit operations include: solvent extraction, stripping, aeration, absorption on silica, alumina, a synthetic resin or activated carbon, and azeotropic or extractive distillation. These techniques may be combined or repeated in sequence, as required, to achieve the desired level of treatment of the waste effluent; such separation processes prove most effective when applied to a waste stream at its most concentrated point. Wherever practical, materials such as solvents or adsorption resins are recovered for reuse within the treatment process. Liquid-Liquid Extraction Liquid-liquid extraction, often referred to as solvent extrac- tion, is am transfer operation allowing for the preferential separation of solutes from one solvent to another. Employed by the 107organic and petro-chemicals industries for the separation of aromatic and aliphatic compounds, liquid-liquid extraction has proved useful for removal of phenols from petroleum refinery and coke-oven plant wastewaters. In general, solvent extraction is economically competi- tive with, and often preferable to steam stripping (see subsection on Gas-Liquid Operations) for the treatment of high strength wastewaters (ives, with solute concentrations of several percent).* Solvent (and/or solute) recovery, which is usually vital to the economics of the operation, is typically accomplished by distillation or stripping practices (Hanson, 1968; Lyman, 1976a; and Kiezyk and Mackay, 1971). Theory and Process Description Liquid-Liquid extraction is based on the principle that when a partially miscible or immiscible liquid is added to a solution of a solute(s), the solute will equilibrate between the two phases. ‘The concentration of a solute, A, within each phase depends upon ite relative affinity for the two solvents and may be defined as follows: y, at (92) A where, D is the distribution coefficient; x is the concentration of solute remaining in the raffinate, (created stream); and y is the concentration of the solute in the extract. *Other factors influencing the selection of the treatment operation include: molecular weight of the organic species, energy require- ments, volatility of the solute(s) and the potential for azeotrope formation. 108Preferably, the extracted solute has a distribution coefficient, D,, that is greater than one. Although often considered in terms of removing a single solute, liquid-liquid extraction may be applied to a mixture of species. The ease with which two solutes may be extracted from solutions is measured by the separation factor, q , which under equilibrium condi- tions is defined as: OOF 37 A w “o_ TB (93) B an oR where, @. is the ratio of the two contaminants between the two solvents; is the activity coefficient in the extract phase; and @ is the activity coefficient in the raffinate phase. The phase ratio, or the relative amounts of’ the phases used, together with the separation factor, will determine the maximum separation that can be accomplished between two species in any one equilibr: tion. The application of liquid-liquid extraction to an industrial Wastewater requires bench scale or pilot plant testing to properly select a suitable solvent (i.e., high extraction efficiency, easily recoverable, non-reactive, practical to use from an economic stand- point, and low toxicity) and determine optimum operating conditions (Sandall et al., 1974). In practice, one phase is dispersed in the 109other liquid (continuous) phase; mass transfer rates may be improved by effective mixing or agitation.* After the extraction is complete, the solute is separated from the solvent for disposal and, in most cases, the solvent is re~ covered. Solvent recovery is often accomplished by distillation, but stripping or adsorption processes may be required. In certain instances, where the solute-containing solvent may be used as a feedstock for an industrial manufacturing process (e.g., nitrobenzene extraction of the solute, aniline), the costs of recovery are elimi- nated. Application to Nitrobenzene/Aniline Manufacture Nitrophenols and nitrous acids, which are formed during the nitration of aromatic hydrocarbons, may be removed from process wastes by liquid-liquid extraction techniques. Typically the ni~ trated product is washed first with water and subsequently with dilute sodium hydroxide to remove the free acids. Approximately 60 to 80 percent of the phenols present in this alkaline wash are recovered (for subsequent disposal) by neutralization with a strong acid. A practical modification to this approach, suggested by Hanson et al., (1976), is to acidify the aqueous wash liquor (after alkaline extraction), extract the phenols with an organic solvent, and recover the solvent by distillation. Suitable organic solvents are shown in *For a discussion of mass transfer kinetics and design requirement, the reader is referred to Treybal, 1963; Hanson, 1968; and Bailes et als, 1976. 110Table XII; of these, methyl isobutyl ketone is most efficient for removal of phenolic by-products. TABLE XIT Efficiency of Organic Solvents in Removing Phenolic Nitration By-Products Solvent Extraction Efficiency (%) Benzene 88 Carbon tetrachloride 79 Chloroform 70 Cyclohexane 37 Dichloroethane 78 Diethyl ether 92 Methyl isobutyl ketone 98 Toluene 82 Source: Hat et al. 1976. An alternative treatment process, dissociation extraction, involves contacting the organic phase containing the acidic phenols with a weakly basic solution of phosphate salt (Hanson, 1976). The phenols are extracted into the aqueous phase as the conjugate base: 3: 2 0H + Po; —- 80° + HPO! (94) or a= - — 40H + woz” —~ 40° + #20, (95) In the next step, the aqueous phase is extracted with a suitable organic solvent, Although several countercurrent contact stages may be required to achieve the predetermined level of treatment, the organic phase may be distilled to recover the phenols and subsequently recycled. iuAccording to the "Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for the Major Organic Products Segment of the Organic Chemicals Manufacturing Point Source Category" (EPA, 1973a) aniline is also commonly recovered from the aqueous phase of the separator by extraction with either nitrobenzene or benzene. Specifically, an extraction efficiency of 98 percent has been reported for countercurrent extraction with nitrobenzene. As shown in Figure 9, the solvent stream (containing extracted aniline) may be recycled to the process, thus avoiding solvent recovery costs. Ohkawa and Sawaguri (1976), in a patent assigned to the Sumitomo Chemical Company, report that organic nitro compounds and phenols may be extracted from acidic waste streams by a water immiscible organic solvent solution containing at least one tertiary dibenzylamine. The organic extract is then washed with an aqueous alkali solution to remove acidic compounds; the amine is recovered the organic solution. ‘The concentrated wastewater can then be disposed of by incineration. iquid Operation: G Liquid operations are based on the diffusional interchange which occurs when a gas and liquid phase are contacted. Primary examples of such operations are distillation and steam stripping, both widely used by organic (and petro) chemical manufacturers for separating volatile organic compounds from aqueous waste streams. Whereas distillation is a means of separating the components 12of a solution by creating a new phase (by vaporization or conden: tion), stripping is a form of gas desorption in which the new phase is introduced in the form of a gas, for example, steam or air. Steam Stripping A type of fractional distillation, steam stripping is a means of removing volatile organic contaminants from a dilute solution. As the case with any mass~transfer operation (cf, liquid-liquid extraction), the objective in designing a stripping tower is to maximize the rate of diffusion between the two phases, and is general- ly accomplished by increasing the interfacial surfaces. Commonly employed industrial contactors include bubble-cap tray towers or a packed tover in which stepwise countercurrent contact of gas and Liquid phases takes place (Treybal, 1963). ‘Two nitrobenzene/aniline manufacturers, First Mississippi and duPont (at their Gibbstown, New Jersey, facility) report the use of stripping techniques in treating process wastewaters. The aqueous phase from the product separator (see Figure 9) which contains approximately 3 percent aniline by weight, may be sent to an aniline stripper, as shown in Figure 10.* The overhead product from the stripper, containing 50 percent aniline by weight, would be inciner~ ated 1 wing a bottom product ( 0.2 percent aniline by weight) +EPA reports a 10° 1b/yr aniline plant requires a 2.5' x 40 stripping tover with a feed rate of 17 gpm (EPA, 1973a). 13Aniline/Water to Incineration Aniline Water from Separator (03%) Stripping Colum, Steam Aniline/Water to Wastewater Treatment Source: EPA, 1973a. FIGURE 10 ANILINE WASTEWATER TREATMENT BY STEAM STRIPPING 14requiring additional treatment.* For a discussion of aniline stripper economics, see EPA (1973a). Adsorption on Granular Activated Carbon Adsorption on granular activated carbon** is an effective and, moreover, commercially established means of removing dissolved organic species from aqueous waste streams. Contaminants are removed from solution by a three-step process involving (1) transport to the exterior of the carbon; (2) diffusion within the pores of the activa: ted carbon; and finally (3) adsorption on the interior surfaces bounding the pore and capillary spaces of the activated carbon. Eventually the surface of the carbon will become turated, requiring replacement of the adsorber system with fresh carbon (i.e., virgin or reactivated). Thus, the development of a high surface area carbon that could be reactivated made commercial application of this adsorp tion process economically practical (Rizzo and Shepherd, 1977 and EPA, 1973b) .*** Theory and Process Description ‘The effectiveness of granuler carbon in removing a given waste fron solution is typically discussed in terms of its adsorption isotherm. The adsorption isotherm illustrates the relationship, at constant temperature, between the amount of solute adsorbed per unit weight of adsorbent and its concentration in bulk solution. In Wihe type of additional treatment would depend on the plant facili- ties; ideally, the stream would undergo adsorption on activated carbon. ‘**Treatment of industrial wastewaters with powered activated carbon will be discussed in the subsection, Combination and Alternative. Techniques. ‘**There were an estimated 100 large-scale industrial/municipal waste~ Water treatment systems in the United States in 1976 (Lyman, 1976b). 15theory, @ point must be reached, where the concentration of the solute remaining in solution and the concentration of the solute adsorbed on the surface of the carbon are in equilibrium. The position of the equilibrium (i.e., the distribution ratio) is de~ picted by the adsorption isotherm, which for dilute solutions, can be expressed mathematically by the Freundlich equation: 2 a2 (96) = ke where X is the amount of contaminant adsorbed on the carbon; M is the weight of the system carbon; and € is the residual contaminant concentration and, k and n are constants. By taking the log of both sides, one obtains the linear relation- ship: log X/M = log k +4 log (97) where 4 is the slope of the straight line isotherm whose inter- cept is k at C= 1. By definition, X/M, (where C, is equal to the influene concentration of C) represents the maximum amount of contaminant adsorbed per unit weight of carbon at equilibrium conditions. Thus, from this expression, the theoretical carbon demand of the system can be estimated. (In dealing with complex waste streams with nonlinear isotherms, a theoretical carbon demand can be calculated for each identifiable component of the w: tewater, and summed together.) 116The adsorption capacity of the activated carbon is a function of several factors, including the nature of the organic contaminant and the nature of the solution. In general, adsorptivity increases with the molecular weight of the solute, and decreases with solute polarity, solubility, and branching. Furthermore, adsorption ii maximized at a solution pH corresponding to the minimum ionization of functional groups, vary with the concentration and mixture of con~ taminants present. However, in practice, to realize optimum operating conditions, consideration must be given to the type of carbon selected, the contacting system, and the mode of operation (EPA, 1973b and Rizzo and Shepherd, 1977). As shown in Figure 11, granular activated carbon systems are commonly designed in one of four major adsorber configurations: moving bed, fixed beds in series, fixed beds in parallel, and upflow expanded beds in series. The objective, in any application, is to design a system in which the most economical, yet practicable carbon exhaustion rates can be achieved*. The actual selection of the adsorber configuration is, however, dependent on the required carbon dosage and contact time, requiring bench and/or pilot scale testing to determine the rate of adsorption. By dynamic column testing over a range of contact times, the concentration of solute (contaminant) ‘Whe carbon exhaustion rate can be defined as the pounds of carbon used per unit volume of wastewater treated (Rizzo and Shepard, 1977). 17ett Moving Bed Effluent Influent Carbon to Regeneration Requires suspended solids pretreatment, but provides counter- current carbon use for smaller volume systems. Source: Hager, 1974. TYPICAL CARBON ADSORPTION COLUMN CONFIGURATION Down Flow in Series Down Flow in Parallel Influent Influent Upflow-Expanded in Series Effluent Effluent Effluent Provides counter- Suitable for large current efficiency, volume systems re~ suitable for large quiring both filtration volume systems; each and adsorption capabil- carbon bed is replaced ities; allows for as a separate unit. blending of effluents. FIGURE 11 Influent Requires minimum pretreatment with minimum headloss, provides counter current carbon use with expanded bed capacity.remaining in solution (C/C,) can be plotted versus volune of solution (wastewater) through the column to give the breakthrough curve. Depending on the complexity of the wastewater, the shape of the breakthrough curve may vary but, as shown in Figure 12, it is char- acteristically " “shaped.” The breakpoint represents the point on the curve at which the column is in equilibrium with the influent wastewater, and little additional removal of the contaminant(s) will occur. The movement of the primary adsorption zone along the column in the direction of the flow (see Figure 12) influences the slope of the breakthrough curve and the position of the breakpoint. Generally, time to breakpoint may be extended by increasing the carbon bed depth and lowering the flow rate; however, several other factors, such as: the characteristics and concentration of the solute, the pH of the solution, and the characteristics of the carbon selected influence the overall capacity of the adsorption system (i.e., height and rate of movement of the mass transfer zone, capacity of adsorbent, etc.). For further details concerning process design, see EPA, 1973b; Rizzo and Shepherd, 1977, and Zogorski and Faust, 1976. Another major consideration in the design and operation of a carbon adsorption system is the means of replacing exhausted carbon. This may be accomplished by removing the carbon from the adsorber for permanent disposal (i.e., throwaway carbon), or more typically, for reactivation. Reactivation is any means by which the carbon is restored to its original adsorptive capacity. Organic impurities may 19Influent Ly Adsorption Zone re Adsorption jj: Zone Concentration of Effluent “4+— breakpoint Volume of Water Treated Source: Weber, 1972. FIGURE 12 PRIMARY ADSORPTION ZONE AND RESULTING BREAKTHROUGH CURVE 120be removed by thermal, alkaline acid, hot gas (steam), solvent, or biological regeneration. However, in treating wastewaters containing a mixture of organics, thermal regeneration of the carbon in either multihearth or rotary tube furnaces provides the most reliable reactivation process and, thus, is the most widely applied. Thermal regeneration may be carried out on-site or off-site: according to Hutchins (1975) if carbon regeneration requirements are less than 580 Ibs/day, off-site regeneration is more economical. As a result of handling and reactivation, attrition losses, requiring fresh make-up carbon, will typically range from 5 to 15 percent by weight (Hutchins, 1975; and Rizzo and Shepherd, 1977). Under certain conditions (e.g., the presence of biodegradable organics, favorable pH ranges, etc.) biological activity may occur in the carbon adsorption column. In general, anaerobic growth not only results in H)S production, but reduces the adsorption capacity of the column and therefore should be discouraged. Aerobic bacterial activity, depending on the concentration and composition of the waste loading, may enhance treatment efficiency. In certain cases, biologi- cal degradation of organic contaminants complements the adsorption process, increasing adsorption capacity and providing partial regeneration of the carbon (Argaman and Eckenfelder, 1976).* ¥A discussion of the advantages and disadvantages of combining pow- dered activated carbon with biological treatment can be found in the subsection entitled Combination and Alternative Techniques. 121Waste Stream Applications Carbon has long been recognized as a means of reducing BOD, COD, suspended solids and color at physical-chemical treatment plants receiving municipal wastes (or combination municipal/industrial wastes), and as a means of polishing secondary effluent from a municipal treatment plant. In recent years, the number of industrial applications has increased as attention focuses on the removal of toxic organic pollutants from waste streams. Granular activated carbon systems are currently being used for removal of a wide variety of organic compounds including nitrophenols, phenol, nitrosamines, benzene, toluene, cresol, cyanide, resorcinols (Lyman, 1976b; Hager, 1976; and EPA, 1977). ‘Thus, it was not surprising that the BAT for the organic chemicals manufacturing category was designated as biological treatment followed by adsorption with activated carbon (Federal Register, January 5, 1976). (These proposed effluent li tations and guidelines were later remanded by EPA, see Federal Register, April 1, 1976.) ‘As discussed in the previous section, many factors enter into the design of a carbon adsorption system. In treating waste streams from nitrobenzene/aniline manufacture, the principal pollutants targeted for removal include: nitrobenzene, aniline, dinitrobenzenes, nitrophenols, nitrotoluenes, phenylenediamine, cyclohexylamine, and nitrosamines. Through bench scale/pilot testing (i-e., selection of carbon, system configuration, hydraulic loading, operating pl, etc., 122the optimum conditions for treatment of the combined wasteload can be determined. In any industrial application of carbon adsorption systems, however, it is essential to recognize the vast difference between the treatment of a synthetic wastewater (e.g., a given carbon isotherm for an aniline solution at a known concentration) and a complex waste containing many competing species. Thus, theoretical studies of the surface chemistry of activated carbon and its capacity for adsorption of nitrobenzene and nitrophenols (see Coughlin et al., 1968, and Mattson et al., 1969), in addition to typical Freundlich isotherm constants for aniline and nitrobenzene plotted in Figure 13 (Rizzo and Shepherd, 1977) must be regarded only as background information for laboratory studies Thus, the feasibility of treating the product/process raw waste lines from a particular facility individually, or as @ combined waste load, should be evaluated on a plant-by-plant basis. In some cases, segregation of certain waste streams may be required to optimize treatment conditions. For instance, the adsorption capacity of activated carbon for nitrophenol decreases ignificantly with increasing pH.* Other wastewater constituents, such as soluble amines or specifically nitrosamines, however, are best treated at higher pH's (MacNaughton and Stauffer, 1976). Another fundamental *Whis is partially a result of an increase in the repulsive forces between neighboring anionic species of the sorbate, nitrophenol, and the negatively charged carbon surfaces, see Snoeyink et al., (1969). 123100 90 80 70 60 50 40 30 Quantity Adsorbed, mg/g 20 Source: svrobensec se, pol! 2 3 4 5678910 20 30 405060 80100 Concentration, mg/1 Rizzo and Shepherd, 1977. FIGURE 13 ADSORPTION OF NITROBENZENE AND ANILINE ON CARBON AS A FUNCTION OF INFLUENT CONCENTRATION 124example of waste stream segregation involves the separation of nitration wastes from amination wastes, wherever possible, to avoid secondary reactions and formation of nitrosamines. Currently, three nitrobenzene/aniline manufacturers employ carbon adsorption in conjunction with other treatment techniques Table X). to remove organic contaminants from waste effluent ( However, data on treatment efficiency (on a stream-by-stream basis), as well as process design, and operation and maintenance are not publicly available. Thus, at this time, no further attempt will be made to evaluate the effectiveness of activated carbon adsorption treatment on nitrobenzene/aniline wastewater. Adsorption on Synthetic Ri As an alternative to adsorption on activated carbon, soluble organic species may be removed from aqueous solution by macroreticu~ lar polymeric adsorbents or ion exchange resins. Advances in crore- ticular polymerization techniques, allowing for the manufacture of microporous molecular sieves with a predetermined (average) pore size, pore size distribution, and surface area enable the selection of a synthetic resin with specific adsorption selectivity. For example, nonionic organic compounds are removed from aqueous solutions by nonpolar or intermediate polarity resins (e.g., hydrophobic molecules are attracted to hydrophobic surfaces).* Synthetic resins Whe polarity of a particular adsorbent is typically classified by the dipole moment of its surface functional group(s). 125may be regenerated by a basic or acidic solution, or an organic sol- vent such as methanol, water, or steam, depending on the adsorption characteristics of the solute; in many c recovery of the solute is also practiced (Simpson, 1972; Kim et al., 1976; Breck, 1977; and Lyman, 1976c). Prior to any application of adsorption on synthetic resins to nitrobenzene/aniline manufacture, laboratory and/or pilot tests would be required to screen resins and study, for purposes of design, those parameters which affect adsorptive capacity (i.e., wastewater composi- tion, flow rate, pi, and bed volume). The selection of a regenerant requires examination of stoichionetric requirements, elutant patterns, and regeneration cycles. Burnham et al., (1972) removed aniline (4.0 ppm influent) from an aqueous solution with 100 percent efficiency in a laboratory study utilizing Amberlite KAD-7 resin.* Complete recovery of p- nitrophenol (0.2 ppm) from solution was achieved employing the polystyrene Amberlite XAD-2 (100 to 150 mesh; 1.25 gpm/cu ft). Experimental isotherms for p-nitrophenol adsorption on Duolite A-7** at varying pH values and concentrations were determined by Kim et al., (1977); the effect of pH on adsorption capacity at the equilibrium concentration (107 i) is graphically presented in *XAD-7- groups. ‘**Duolite A-7 is a phenol-formaldehyde resin with amine functional groups. 3 an acrylic base resin with no ion-exchange functional 126Figure 14. As shown, the maximum adsorption capacity is reached in the pH region of 5 to 5.4, a range in which the resin is most likely present as a free base. Therefore, the authors hypothesize that adsorption is taking place predominantly through formation of a hydrogen bond between the free amino group on the resin and the penitrophenol hydroxyl group: q Ry- N +H > M| ——— R (98) where R, is the rei HO-M is p-nitrophenol. Thus, as the pH is lowered and the amine n matrix, R is a hydrogen or alkyl group, and group becomes protonated, the adsorption capacity decreases dramat- ically, The significant decrease in. capacity the pH is increased may be attributed to the increased solubility of p-nitrophenol. For comparison, the variation in adsorption capacity of activated carbon and the nonionic Amberlite XAD-7 are also presented in Figure 14. Under optimum pH conditions, the Duolite A-7 resin capacity approxi- mated that of a conmon granular activated carbon. In general, however, the adsorption of weak organic acids on the weak base resin is much more sensitive to pH (Kim et al., 1976). As part of a study on the recovery of amines from aqueous so- lutions, Sargent (1964) tested aniline sorption on various anion exchange resins. At, or prior to aniline breakthrough, the resin was washed with a mineral acid to elute the aniline salt. (Aniline may 12710" PNP on Activated J Carbon Oba ee bo g * g 104 3 a 3 2 g 8 & 10 3 6 | ! ! 1 | 1 o'r 3 5 7 9 cre 13 pH Source: Kim et al., 1976. FIGURE 14 ADSORPTION OF p-NITROPHENOL AS A FUNCTION OF pH 128 15then be recovered from the regeneration solution by distillation, crystallization, or extraction practices.) From the test results, presented in Table XIII, there are a number of anion exchange resins which have rather high distribution ratios and would be effective for the sorption of aniline and other amines. However, the overall prac- ticability of the process has yet to be demonstrated on nitrobenzene/ aniline manufacturing wastes. Membrane Processes Molecular or ionic species may be separated fron an aqueous stream by a selective membrane, which has high permeability for some species and low permeability for others. The principal driving force across @ membrane in terms of thermodynamics, is a function of the free-energy potential. The major membrane process electrodialy~ sis, reverse osmosis, and ultrafiltration have had varied and large- scale applications to water and wastewater treatment, principally in the desalting of brackish water (in the case of the former two proces- ses), and in the concentration and purification of single phase industrial wastes. With recent advances in the development of synthetic membranes which provide improved selectivity and uniformity of performance, new applications of membrane processes are being investigated (Lacey, 1972; Smith et al., 1976; and Arthur D. Little, 1976), Specifically, the practicability of using dialysis and reverse osmosis for the treatment of nitrobenzene/or aniline-contain- ing wastes has been examined. 129cere ov asin ‘osetia euvscint ara yutttansom Disruapvrice (iotshe vege /oey 8) So0PT108 HUTIO, Ry Percent) Gealoet 8) {200 hus} Poly(vinplbeneyl triaethyl emmatum chloride) a 0.76 ses 5.16 ue Poly(otepibensy) eriaaeayl amon chloride) 2 one 30.2 sn 16 Poly(visylbenayl Cetaathyl ampeiun chloride) 2 aa a sae 3. Poly(vtny2becey! telsethyl amontun chloride) 2 a st mar Poly(otoyibeneyl extaerdyt smoot eoride) 2 ry an ne Poly (vtayibentyL trinettyn ‘ 1s aes 5.15 m2 Poty(oteyibenay) exiaeedy ® 0.96 18. 6.2) 256 Poly(oteyibeasy) diasehyl eehasolamentun chloride) | 2 a3 39.0 00 435 Dover 238 veate 5 3.59 ses saa Pay Poly(vteyibeneyl potyattytene polyanins) 2 wer 0 Cen 58.5) Dower 3X4 resin ‘ 5.30 x8 4 a Yreate performed on 0.1 percent antlisn solution Sources Saiprat, 1966,Dialysis is a diffusion process in which a solution containing two solutes (or permeating species) is separated from a solvent in an adjacent compartment by a membrane, thereby establishing a difference in the chemical potential of the permeant in each compartment. The rate of transport across the membrane (per unit area) can be described in terms of: F = Lde/dx (99) where F is the rate of transport; L is the permeability coefficient, which is a function of the diffusion and partition coefficient of the given solute; and dc/dx is the concentration gradient, which represents the driving force in terms of entropy production. Therefore by definition, the rate of transport, F, is directly propor- tional to de/dx and L at steady state. ‘Thus, in applying conventional dialysis to industrial waste problems, where toxic pollutants may be present in low concentrations, it is essential that the driving force be maximized. This may be accomplished (without necessitating a continual supply of a pure receiving solvent) by contaminant removal downstream of the selective membrane, employing conjugation and pervaporation techniques devel- oped and demonstrated by Smith et al., (1976). Aniline can be effectively removed from solution by combining dialysis through hydrophobic membranes with conjugation downstream of the membrane. The theory behind this practical application is 131.simpl the concentration of aniline in the receiving compartment is reduced to a minimum by formation of a nonpermeating conjugate on the downstream side, thereby maximizing the rate of transport. Smith et al., (1976) studied an aniline system to illustrate the practicability of conjugation in treating dilute waste streams;* as shown in Table XIV, the specific permeability, L, reported for Kraton and XD-7 (polyearbonate-co-silicone) films: are "the same order of magnitude those found in other commercial dialyzing processes and in reverse osmosis." By neutralizing the conjugate acid, recovery of aniline can be accomplished. Pervaporation,-or activated diffusion, is based on a vapor- phase sink downstream of a permselective hydrophobic film, and has been applied to the separation of hydrocarbons and azeotropic ‘mix- tures. This process involves (1) adsorption of the contaminant at the Liquid-menbrane interface, (2) diffusion through the permselec~ tive membrane; and (3) removal of the contaminant from the downstream surface of the permselective membrane by evaporation. As the trans port rate is proportional to the membrane area and vapor pressure of the solute, pervaporation appears feasible when the contaminant to be removed from solution has a relatively high vapor pressure. Nitro- benzene with a solubility of 0.20 wt percent and vapor pressure of initial upstream concentration: 2.98 wt percent aniline; initial downstream concentration 5.33 wt percent sulfuric acid. 132‘TABLE XIV ANILINE AND WATER TRANSPORT THROUGH POLYMERIC MEMBRANES? ect 2 — Tucan: | nec — | coerrictzin, s? | cogrricrr, o* Polyethylene A 20.0 1.16 x 1072? 0.44 x 1077 Polyethylene B 13.6 2.32 x 1922 0.15 x 1077 0.13 1.5 x10 Saran 11.9 5 0.19 x 1077 1.44 1.32 x 108 Kraton 1101 (35.7 3.8 x10 2.5 x107 0.765 32.7 x 10° 0-7 68.3 1.19 x 10% 3.9 x107 2.69 14.5 x 1078 Yteuperature 25°C. 21m en?/sec. 3g _ #.Of solute per untt volume of svollen polyner of solute per unit volume of solution “pittuston cootfictent (ea”/gec) was calculated from the relationship L = DS- Seetsmated to be less than 107! ca?/sec. Source: Smith et al., 1976.0.4 mg (at 25°C) was screened in a pervaporation study at a concen- tration of 600 mg/l; permeability coefficients are presented in Table XV. From experimental tests, the authors concluded that in order to optimize conditions in a commercial application of the pervaporation scheme, (1) membrane thickness should be 25 microns or less, in order to minimize boundary layer resistance; (2) the feed velocity should be maximized, as membrane permeability is directly related to flow rate; and (3) feed temperatures should be elevated to increase feed solute vapor pressure and decrease viscosity (Smith et al., 1976). TABLE XV Pervaporation Study:. Nitrobenzene Permeability Coefficients! ‘Thickness L x10) Membrane (Microns) (en?/see) Polyethylene (low density) 4.7 6.85 Saran 19.4 6.42 Kraton 1101 25.0 9.6 Pliotite 38.0 10.7 Adiprene 59.0 +13 Polyethylene. (Plasticized) 2h. nw \iquid Flow: 0.75 L/min; Air Flow: 12.0 l/min. Source: Smith et al., (1976). 134Reverse Os: (Ro) In reverse osmosis, a semipermeable membrane is utilized to transfer solvent (water) from a more concentrated solution to a more dilute solution, thereby purifying the solvent. Whereas, in dialysis the concentration gradient 9 the driving force, the driving force for this separation process is pressure. For ideal solutions, osmotic pressure, , is defined ar OP m= ing (100) 7 1 e, where P, and P, are the solvent vapor pressure in the solutions on either, side of the membrane, R is the gas constant, T is absolute temperature (Kelvin), and v is the molar volune of the solvent. By definition, "reverse" osmosis occurs when the pressure is greater than on the (concentrated) solution side of the membrane, and the Liquid flow (which is normally from the more dilute solution to the more concentrated), reverses. The actual mechanism by which solute separation takes place is still unclear, but the most widely accepted theory is that of a preferential sorption-capillary flow. The theory suggests that both the chemical nature and the microporous structure of the membrane surface are related to solute separation (Birkett, 1977; Weber, 1972; and Fang and Chian, 1976). In the actual design and operation of a reverse osmosis unit, major considerations include: (1) the module design, which is intended to minimize concentration polarization of the solute on the 135membrane surface while maximizing solvent flux; (2) membrane selec~ tion; and (3) membrane susceptibility to chemical attack or fouling by the wastewater. Prior to scale-up, laboratory or pilot studies should be carried out to fully evaluate membrane selection, module configuration, optimum feed rates, pretreatment requirements (e.g., filtration) and potential problems associated with fouling of the membrane (Birkett, 1976). In 1975, there were nearly 300 large-scale reverse osmosis plants in operation throughout the world, purifying brackish or saline water for both domestic and municipal use (Birkett, 1976). In the treatment of industrial wastewaters, where reuse and/or recovery of materials is desirable (e.g., electroplating industry), RO becomes both a practical and economic process. However, the practicability of applying RO to industrial waste- waters, specifically nitrobenzene/aniline process streams, would be largely dependent on the degree of solute(s) separation achieved, or the efficiency of the process.* To this end, Fang and Chian studied the potential of 12 reverse osmosis membranes to separate polar organic compounds from aqueous waste solutions. Each membrane was characterized by testing with sodium chloride solutions under FRO is ideally suited for the treatment of brine solutions with up to 34,000 ppm TDS (i.e., seawater). As the TDS level of nitroben- zene/aniline manufacturing waste is more typically in the range of 500 ppm (see Table XIII) the advantages of employing this separation technique may be overridden by energy costs. 136standardized conditions. Aniline solution results showed 75 percent or greater solute separation with a cross-linked polyethylenimine membrane (flat sheet and tube configuration) or with a NS-200 membrane (flat sheet). The test data, according to the authors, should represent a conservative assessment of the treatment effectiveness. In treatment of actual wastewaters, the steric and polar effect of the solute would yield a higher degree of separation. Thus, while reverse osmo: remains a potential treatment alternative, the practicability of this process in treating nitrobenzene/aniline wastes hi yet to be demonstrated. COMBINATION AND ALTERNATIVE TECHNIQUES From the preceding review of biological processes and physical separation techniques, it s likely that no single treatment opera~ tion or process is ideally suited and/or could achieve the reduction in-total pollutant loading from nitrobenzene/aniline waste streams necessary for discharge to navigable waters. Thus, the next step in evaluating this wastewater problem is to assess the technical feasi- bility of combining certain treatment techniques for application to combined and/or segregated waste streams. In theory, there are many different approaches in which treatment techniques may be selected and combined to attain the desired level of pollutant reduction. As was discussed, in the section on Current Industrial Practices, physical separation techniques, such as coun- tercurrent extraction of aniline by nitrobenzene and adsorption on 137activated carbon, are combined in practice as part of an overall treatment scheme for the wastewater. However, certain portions of the total waste load, depending on its strength and biodegradability, might be more appropriately treated by biological processes. As specific recommendations will be presented in Section V, the. re~ mainder of. this chapter will be limited to a general discussion of alternative or combination treatment schemes that are either patented inventions or in commercial use. A treatment method for reducing wastes, such as chromophoric compounds, heavy metals, and nitrobenzene, from the manufacture of synthetic dyestuffs and related intermediate chemicals has been patented by Sweeny (1977). The pretreatment procedure involves equalization, chemical treatment to remove heavy metal impurities, addition of a flocculating agent, subsequent clarification, and a second equalization treatment. The mixture is then passed through a carbon adsorption column to lower the nitrobenzene. concentration and remove colored constituents from the wastes. Finally, the effluent is treated with activated sludge containing microorganisms acclimated to the waste. Reviewing the treatment procedure, the patent is a logical application of demonstrated treatment technologies. Chemical pretreatment of the effluent reduces excessive column pressure as a result of sludge accumulation, The activated carbon treatment reduces the nitrobenzene levels in the effluent prior to biological treatment. As noted in the patent, very low levels of nitrobenzene increase the 138respiration rate of bacteria; concentrations over 12.0 mg/l however, are toxic to the bacteria. Thus, the carbon effectively lowers the nitrobenzene concentration in the effluent to a level below which is toxic to the microorganisms. Eli Lilly has patented a pretreatment process for removing nitrophenols and nitroaniline (trifluralin) from manufacturing wastewater (Howe, 1969). The waste stream is acidified to a pH less than 3 and a decolorizing material is added; the preferred adsor~ bent 8 an activated or digested sludge. The following step involves neutralization of the mixture by the addition of a metallic oxide or hydroxide (e.g., calcium hydroxide). After separation of the re~ sulting sludge (or foam), the effluent may undergo conventional biological treatment for further reduction of organic loading. Ac~ cording to the patent, the phenol content of a waste stream (2000 to 2800 ppm) was reduced to a trace amount by these treatment procedures. Alternatively, an organic waste stream may be subjected to bio- logical treatment in the presence of powdered activated carbon (PAC). The powdered carbon is added to the aeration contact basin to enhance bio-oxidation (by removing adsorbable toxic, inhibitory and refractory substances) and reduce color and odor. Furthermore, addition of PAC may improve floc formation, sludge settling, and sludge dewatering. For a more complete process description, including commercial applica~ tions of the process and regeneration schemes the reader is referred to: DeWalle and Chian, 1977; Davis, 1977; Hutton and Robertaccio, 1391978; Grulich et al., 1972; Wilhelmi and Ely, 1976; Pradt, 1976; and Environmental Science and Technology (February), 1977. A treatability and design study performed by Zimpro, Inc. on a high flow waste stream know to be difficult to treat biologically (high organic, as well as a high dissolved solids content) serves to compare conventional activated sludge systems, to the biophysical (carbon/wet-ox) system.* Nitrification was found to be enhanced in the latter system, with a 95.5 percent total Kjeldahl nitrogen (TKN) removal, as opposed to 13.8 percent for the activated sludge. Furthermore, with some modifications and the judicious addition of a carbon source (e.g,, methanol, molasses), denitrification of the waste will occur (Frohlich et. al., 1976). 5CH,OH + 6H" + 6NO, ——~ 5C0, + 3N, + 13H,0 aon A critical factor in adopting any treatment practice is the economics of the operation. Although an economic analysis of each alternative treatment scheme (e.g., a comparison of capital invest- ment, operation and maintenance costs, materials, and energy re- quirements) is beyond the scope of this report, it is, nevertheless, important to acknowledge that activated carbon adsorption was pre- viously selected by EPA as an "economically achievable technology” for the treatment of organic chemicals manufacturing process wastes Wiet-ox, or wet-oxidation, is a means of detoxifying organic wastes in aqueous solution at high pressures and temperatures. 140(Federal Register, January 6, 1976). However, the final selection of any treatment operation, or processes, would be largely dependent on dilution prior to discharge (many plants are capable of combining treated streams with non-contact cooling water, etc.) and binding effluent limitation requirements, A summary of alternative treat- ment systems investigated by foreign researchers appears in Table XVI, @ more detailed discussion of practicable alternatives follows in Section V, Recommended Treatment Alternative: wa.ert SmounY oF FoREIOH APPLICATIONS OF F5YSICAL-CHOMCAL TREATMENT TO WASTEUATERS Teeatacst Procesel Shatter, 1977 the treataent of anivine-soa" efaing wesceusteree frou aqueous saline poluttens, sNiecbaceefree'of sntsopbee Iesctivition of carton bed vith tot ate a€ $220%C wae Sncoo™ plete. Fane (erg. camphor, disethyl phthalate) AaSdine aay be exeracced with diluce Bel, Sorption aechantentSECTION V RECOMMENDED TREATMENT ALTERNATIVES INTRODUCTION As was discussed in Section I, the major objective of thi study is to assess pollution control practices from the manufacture of nitrobenzene/aniline with regard to toxic pollutant generation. Whereas Section II provided the process chemistry and manufacturing configuration necessary for the prediction of toxic pollutants (identifying point source discharges of specific pollutants), Sections ILI and IV reviewed current wastewater practices and alternative control technologies largely in terms of the combined waste load from nitrobenzene/aniline manufacture. Thus, it is the purpose of this section to examine the treatability of the process wastewater in terme of segregated point source discharges. As shown in Figure 9, the most refractory of the waste streams generated during nitrobenzene manufacture is Point No. 5, characterized by high loadings of nitro- phenols, nitrobenzenes, organic acids and heavy polymeric material. In the course of aniline manufacture, the most refractory stream is Point No. 8, characterized by significant concentrations of nitro~ benzene, aniline, and other organic compounds. Also important during aniline manufacture is the disposition of the still bottoms from the aniline distillation column. Detoxification of these streams repre- sent the major obstacles to successful treatment of nitrobenzene/ aniline wastewaters and must be the focal point of any future treat- ability study. 143The discussion that follows will: (1) present a point source- by-point source summary of potential pollutants from nitrobenzene/ aniline manufacture using the generic processes previously formulated; and (2) recommend treatment alternatives for each stream. Recommenda- tions will be based solely on the efficiency of a process to treat a te stream, and exclude any analyses of capital, operation and maintenance, and energy costs. Thus, included in this section are treatment options whose practical application may be only to new sources (ives, existing facilities might require extensive repiping in order to implement a recommended treatment), Furthermore, it is assumed throughout the section that conventional treatment practices (e.g, equalization, neutralization, separation) will be employed, as required, POINT SOURCES OF POTENTIAL POLLUTANTS The following remarks are directed to nitrobenzene manufacture and refer to Figure 9. Nitration of Benzene Point No. 1 The nitration vessel most probably requires venting. Dinitrogen pentoxide, dinitrogen trioxide, nitric oxide, benzene, and nitroben- zene represent the major components of this vent stream. Depending on the volume of this discharge, either wet scrubbing or adsorption with silica gel, activated carbon, etc. is required for control of atmospheric emissions. In the case of wet scrubbing, the effluent 144is combined and treated with the spent acid (the disposition of solid adsorbents is unknown although regeneration may be feasible). Nitrogen oxides, together with benzene and nitrobenzene, are the potentially significant emissions from this point source. Therefore, current control technology (i.e., wet scrubbers) appears adequate. Point No. 2 The nitrogen oxides (principally nitrogen dioxide and dinitro- gen tetroxide) produced in the ‘bleaching tower are extracted with water and recycled to the denitrating tower. Those gases which are not extracted during this process are vented to the atmosphere. As such, the composition of this stream is presumed to be qualitatively similar to that of point number 1; potential contaminants include: dinitrogen pentoxide, dinitrogen tetroxide, dinitrogen trioxide, nitrogen dioxide, nitric oxide, benzene, and nitrobenzene. Though emissions of nitrogen oxides are likely to be minimal, benzene and nitrobenzene may conceivably be vented in environmentally significant amounts from this point. Further study of emissions from this point may be warranted. Point No. 3 Prior to distillation, crude nitrobenzene is washed first with water, then a dilute solution of aqueous base (Na,CO, or NaOH), and finally water once again, To reduce the volume of aqueous effluent, recycle of this water may be assumed; however, even with efficient water reuse, this point may still represent a major discharge point uswithin the process. Nitrophenols and carboxylic acids together with nitrates and nitrites comprise the major portion of toxic effluents from this stream, This stream would be best treated by activated carbon adsorption. Point No. 4 While most nitrobenzene is used directly for aniline production, small amounts are further purified by distillation. This stream is likely to be rather small, but may be toxicologically significant. Nitrobenzene, nitrophenol, dinitrobenzenes, polycarboxylic acids, and high molecular weight polymers, are the principal components of this stream. This stream would also be best treated by activated carbon adsorption. Point No. 5 Purification of spent acid (a mixture of sulfuric and nitric acid) for reuse, 9 not only the most practical method for mini- mization of environmental impact but also economically justified. A number of processes have been used successfully by industry for recovery of dilute sulfuric acid. Conventional methods for removal of volatile impurities such-as nitrogen oxides, benzene, nitro- benzene, and dinitrobenzene, entail heating the spent acid to its boiling point and stripping the acid with hot gases such as steam or air (De La Mater and Milligan, 1974). These compounds may then be removed from the resulting gas stream using conventional scrubbing systems, the aqueous effluent going to wastewater treatment. This 146procedure, while effective in removing essentially all of the volatile organic and inorganic impurities, yields a product which requires further treatment: the stripped acid must be either fortified with oleum or otherwise concentrated (e.g. distilled) prior to reu! * Furthermore, these proces: arily concentrate 8 neces nonvolatile organic impurities, primarily nitrophenols and various organic acids (cf Table VI), and inorganic impurities which must be continually removed; concentrations of 200 ppm or greater within this stream are reported under steady state conditions. This stream obviously presents a waste disposal problem and represents a poten- tially significant environmental hazard. While direct disposal of this stream is possible, other treat- ment methods have been suggested which may result in lower aqueous emissions of toxic substances. Briefly, one procedure involves continuous, in situ oxidation of nonvolatile organic species with strong oxidants such as ozone, hydrogen peroxide, chlorates, or peroxydisulfates at temperatures between 130 to 230°C (De La Mater and Milligan, 1974), An alternative technique is reported by von Plessen et al. (1976, 1977): initial concentration of the spent acid (60 to 70 percent by weight) using the Pauling process** WThis, of course, assumes that the market for dilute sulfuric acid is small; this acid could, in fact, be used for phosphoric acid or fertilizer manufacture. ‘**The Pauling process is a counter-current extraction method in which impure dilute acid is added to the top of a fractionating column under reflux; concentrated (96 percent by weight) acid is withdrawn from the bottom; the distillate, principally water, with only traces of acid, is discarded. 147and then distilling the concentrated, still contaminated acid a second time. Organic impurities are generally degraded in the first concentration step to carbon dioxide, nitrogen oxides, and water; the nitrogen oxides are presumed to be removed by conventional .e+, scrubbing. As with any distillation procedure however, there remains a small, concentrated, highly contaminated acid stream which must be disposed of. Whatever method is used for acid purification, it is apparent that a relatively small, but toxic effluent stream must be treated. Likely contaminants include nitrobenzene, nitrophenols, polycarboxy- lic acids, and high-molecular weight nitrogen containing organic polymers. This stream would be best treated by activated carbon adsorption. Reduction of Nitrobenzene The following point sources have been identified for generic processes for the catalytic reduction of nitrobenzene to aniline as shown in Figure 9. Point No. 6 The crude mixture of aniline after leaving the reactor is condensed and separated from the gas stream. The gas stream, which is principally hydrogen but also contains about 3.5 percent and 0.05 percent of water and aniline respectively, is compressed and recycled to the reactor. A small portion of this stream must be vented to prevent buildup of gaseous. impurities. Hydrogen, 148together with aniline, nitrobenzene, and water, represent the major components of this purge stream. If a.less pure grade of hydrogen is used as a feedstock, carbon monoxide, methane, and ethane may be also present (see Table III). Air emissions may be best controlled by combustion in a properly designed flare. Point No. 7 This point is comprised of the volatile components removed overhead from the distillation column. The major components of this stream are presumed to be cyclohexylamine, cyclohexenyl amine, other volatile amines, and water. This stream would probably. be amenable to dilution and biological treatment; however, incineration of this stream may also be practicable. Point No. 8 A variety of configurations for the distillation of aniline may be envisioned; all proce 9 will however have a purge to Prevent accumulation of high boiling products. Aminophenols, nitrobenzene, phenylenediamine, diphenylamine, azepins, and high molecular weight aminopolymers are likely components of this stream. Because of the high organic content of this stream, disposal by incineration i recommended. Point No. 9 Water saturated with aniline is obtained from the separator and possibly as a top product from the distillation column. Recovery, even if not economically justified, will be required to prevent 149serious degradation of water quality. Again, a wide variety of configurations for aniline recovery are possible; shown in Figure 9 is a scheme based on counter-current extraction with nitrobenzene. Compounds of interest in this stream include aniline, nitrobenzene, aminophenols, phenylenediamine, and other water soluble amines. ‘The aniline water is best treated by a counter-current extrac~ tion with nitrobenzene. Alternatively, the organic contaminants could be recovered by steam stripping techniques. In either case, the final effluent stream should receive further purification by adsorption on activated carbon. In order for the treatment process to effectively reduce the potential formation of nitrosamines, nitration wastes should remain segregated from amine-containing streams. Furthermore, because the ability of activated carbon to remove specific species is pH dependent, the waste streams are most likely treated by carbon columns in series, with pH adjustments as required. A U.S. Air Force study on the treatment of nitrosamine contaminated waste with activated carbon demonstrated higher removal efficiencies in caustic solutions (MacNaughton and Stauffer, 1976). However, as discussed in the subsection on Adsorption on Activated Carbon, the removal of color (e.g., nitroanilines and nitrophenols) is favored under acidic conditions (Howe, 1969; Snoeyink et al., 1969). 150SECTION VI SUMMARY AND CONCLUSIONS The discharge of a toxic substance to the environment by an organic chemical manufacturer, depending on the persistence and mobility of the compound, may have irreversible effects on the environment. Under the Clean Water Act of 1977, EPA must regulate such industrial discharges by the establishment of effluent limita~ tions, defined in terms of the best available technology economi- cally achievable. However, the establishment of such standards for specific toxic species that are not only equitable to industrial manufacturers, but more importantly that will prevent further dete- rioration of the environment, is an exceedingly difficult task. As a first step, EPA must thoroughly understand the manufacturing process and available control technologies so that, ultimately, attainable standards may be set. To this end, a detailed description of nitrobenzene/aniline manufacture and pollution control technology has been presented. Included is a comprehensive ‘discussion of the reaction mechanism, with a summary of potential pollutants generated from feedstock impurities and sigtificant side reactions. Additionally, a generic process configuration for nitrobenzene/aniline manufacture has been formulated, identifying specific point source discharges (see Fig~ ure 10). From this information, current wastewater treatment and asidisposal practices, as well as alternative methods of treatment, were reviewed. Currently, there are no effluent limitations specific to the point source discharge from nitrobenzene/aniline manufacture. As summarized in Table 10, U.S. manufacturers use a variety of waste- water treatment techniques, as in most cases the process wastes are combined with other product lines. However, it is important to note, that despite the vast number of potential pollutants generated from the manufacture of nitrobenzene/aniline, this is basically a "clean" process (that is, the process streams are highly treatable, as compared to the manufacture of other organic compounds). Addition- ally, the wastewater treatment techniques currently employed by certain manufacturers are commendable. Nevertheless, in light of future regulatory concerns, a complete review of alternate treatment technologies (without industry bias) is appropriate. As discussed in detail in Section V, pollution abatement from nitrobenzene/aniline manufacture may be accomplished by in-proces: modifications or end-of-pipe technologies. Practicable methods for pollutant reduction are best examined with regard to the treatability of segregated waste streams, as presented in Figure 15. An economic analysis of the costs of implementing such in-process changes or wastewater treatment options, has not been performed, and furthermore, remains beyond the scope of this report. 152es es qos mserer if a3 sea f ari ' rae POTENTIAL TREATMENT OPTIONS FOR. DNITAOGENZENE/ANILINE WASTEMATERS ‘ev point sounce otatsteThis study has provided, however, a framework for approaching a difficult industrial wastewater treatment problem. As such, it has outlined some of the steps that must be taken before BAT effluent limitations can be rationally promulgated for nitrobenzene/aniline containing wastewaters. Recommendations for further studies (to validate the conclusions reached in Section V) include: © EPA verification, from sampling of actual process waste waters, of all pollutant predictions and concentrations. © Extension of this pollution prediction and abatement metho- dology to additional compounds exemplifying other unit pro~ cesses such as amination, chlorination, oxidation, etc. © EPA funding of pilot scale studies for determination of the technical practicability of the recommended treat~ ment alternatives. © An economic analysis of viable treatment alternatives (with regard to best available technology economically achievable). @ Demonstration of BAT in an EPA-industry jointly funded project. 154REFERENCES Abramovitch, ReA. and B.A. Davis. Preparation and Properties of of Imido Intermediates. Chemical Reviews 64:149-185, 1964. Albright, L.F. Processes for Nitration of Aromatic Hydrocar~ bons. Chemical Engineering, May 9, 1966, pp. 160-164. Albright, L.F., Fel. 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