EPA/310-R-95-012
Office of Compliance
Office of Enforcement and Compliance Assurance
U.S. Environmental Protection Agency
401 M St., SW (MC 2221-A)
Washington, DC 20460
II. INTRODUCTION TO THE ORGANIC CHEMICALS INDUSTRY
This section provides background information on the size, geographic distribution, employment, production, sales, and economic condition of the organic chemical industry. The type of facilities described within the document are also described in terms of their Standard Industrial Classification (SIC) codes. Additionally, this section contains a list of the largest companies in terms of sales.
II.A. Introduction, Background, and Scope of the Notebook
The industrial organic chemical sector produces organic chemicals (those containing carbon) used as either chemical intermediates or end-products. This categorization corresponds to Standard Industrial Classification (SIC) code 286 established by the Bureau of Census to track the flow of goods and services within the economy. The 286 category includes gum and wood chemicals (SIC 2861), cyclic organic crudes and intermediates, organic dyes and pigments (SIC 2865), and industrial organic chemicals not elsewhere classified (SIC 2869). By this definition, the industry does not include plastics, drugs, soaps and detergents, agricultural chemicals or paints, and allied products which are typical end-products manufactured from industrial organic chemicals. In 1993, there were 987 establishments in SIC 286 of which the largest 53 firms (by employment) accounted for more than 50 percent of the industry's value of shipments. The SIC 286 may include a small number of integrated firms that are also engaged in petroleum refining and manufacturing of other types of chemicals at the same site although firms primarily engaged in manufacturing coal tar crudes or petroleum refining are classified elsewhere.[a]
The industrial organic chemical market has two broadly defined categories, commodity and specialty. Commodity chemical manufacturers compete on price and produce large volumes of small sets of chemicals using dedicated equipment with continuous and efficient processing. Specialty chemical manufacturers cater to custom markets, manufacture a diverse set of chemicals, use two or three different reaction steps to produce a product, tend to use batch processes, compete on technological expertise and have a greater value added to their products. Commodity chemical manufacturers have lower labor requirements per volume and require less professional labor per volume.
[a] Variations in facility counts occur across data sources due to many factors including reporting and definitional differences. This notebook does not attempt to reconcile these differences, but rather reports the data as they are maintained by each source.
The 1992 Census of Manufactures for Industrial Organic Chemicals reports employment of 124,800 and a 1992 value of shipments of $64.6 billion. This value of shipments does not include organic chemicals manufactured for captive use within a facility or the value of other non-industrial organic chemical products manufactured by the same facility. It does, however, include intra-company transfers which are significant in this industry. By comparison, the 1992 value of shipments for inorganic chemicals totaled $27.3 billion with employment of 103,400 people. The 1992 value of shipments for the entire chemical industry (SIC 28) was $292.3 billion and employment totaled 850,000. According to Chemical and Engineering News, the production of industrial organic chemicals has increased by three percent per year between 1983 and 1993 while employment has fallen by one percent per year over the same period indicating an overall increase in productivity for the sector. The same source reports the industry employed 153,000 people in 1993 while shipping products valued at $60.9 billion.
The Department of Commerce reported that output in the industrial organic chemical market grew five percent between 1992 and 1993 and is expected to continue to grow at the same rate partially on the strength of increased demand and production of methyl tert-butyl ether, a fuel oxygenate.
II.B. Characterization of the Organic Chemicals Industry
II.B.1. Industry size and geographic distribution
Industrial organic chemical facilities have an unusual distribution when compared to downstream manufacturing facilities. Most significantly, a small number of very large facilities account for the majority of the industry's value of shipments. The 1992 Census of Manufactures (Exhibit 1) showed that only 113 of the 986 industrial organic chemical facilities (11 percent) had more than 250 employees. However, these facilities accounted for almost 70 percent of the value of shipments for the industry; the largest 16 plants (greater than 1,000 employees) accounted for about 25 percent of the total value of shipments.
Exhibit 1: Small Number of Large Facilities Account for Majority of Shipments
Number of Percent of Percent of Number of Employees Facilities Facilities Shipment Value fewer than 10 259 26% 1% 10 to 49 301 30% 5% 50 to 249 313 32% 27% 250 to 499 60 6% 16% 500 to 999 37 4% 26% 1,000 or more 16 2% 25% Total 986 100% 100% Source: 1992 Census of Manufactures
The industrial organic chemical sector is geographically diverse (Exhibit 2). Gum and wood chemical manufacture (SIC 2861) is concentrated in Missouri, Florida and Virginia. Cyclic crudes and intermediates (SIC 2865) and unclassified industrial organic chemicals (SIC 2869) are concentrated in Texas, Louisiana, New Jersey, Ohio, Illinois and West Virginia. Facility sites are typically chosen for their access to raw materials (petroleum and coal products for SICs 2865 and 2869 and wood for SIC 2861) and to transportation routes. In addition, because much of the market for industrial organic chemicals is the chemical industry, facilities tend to cluster near such end-users.
Exhibit 2: Organic Chemical Manufacturing Facilities (SIC 286)
(Source: U.S. EPA, Toxics Release Inventory Database, 1993)
Ward’s Business Directory of U.S. Private and Public Companies, produced by Gale Research Inc., compiles financial data on U.S. companies including those operating within the organic chemical industry. Ward’s ranks U.S. companies, whether they are a parent company, subsidiary or division, by sales volume within their assigned 4-digit SIC code. Readers should note that: (1) companies are assigned a 4-digit SIC that most closely resembles their principal industry; and (2) sales figures include total company sales, including subsidiaries and operations (not related to organic chemicals). Additional sources of company specific financial information include Standard & Poor’s Stock Report Services, Dun & Bradstreet’s Million Dollar Directory, Moody’s Manuals, and annual reports.
Exhibit 3: Top U.S. Companies with Organic Chemical Operations
Ranka Companyb 1993 Sales (millions of dollars) 1 Exxon Corp., Exxon Chemical Co. 9,591 S. Darien, CT 2 Dow Chemical USA 9,000 Midland, MI 3 Miles, Inc. 5,130 Pittsburgh, PA 4 Union Carbide Corp. 4,877 Danbury, CT 5 Amoco Chemical Co. 4,031 Chicago, IL 6 Chevron Chemical Co. 3,354 San Ramon, CA 7 Quantum Chemical Corp. 2,532 New York, NY 8 Witco Corp. 1,631 New York, NY 9 Ethyl Corp. 1,600 Baton Rouge, LA 10 Texaco Chemical Co. 1,600 Houston, TX Note: a When Ward’s Business Directory lists both a parent and subsidiary in the top ten, only the parent company is presented above to avoid double counting. Not all sales can be attributed to the companies’ organic chemical operations. b Companies shown listed SIC 286 as primary activity. Source: Ward’s Business Directory of U.S. Private and Public Companies - 1993.
II.B.2. Product Characterization
The two-digit SIC code 28, Chemicals and Allied Products, includes facilities classified as industrial organic chemical manufacturers under the three-digit SIC code 286. This includes gum and wood chemicals, cyclic crudes and intermediates and industrial organic chemical not elsewhere classified. The last category is by far the largest and most diverse of the three; however, its size distribution and industry structure are similar to those of the cyclic crudes and intermediates because both use primarily petroleum and coal derived feedstocks. In addition to industrial organic chemicals, seven separate types of product establishments are identified under Chemicals and Allied Products (SIC 28). Many of the other industry sectors within the two-digit SIC code 28, such as plastics materials and synthetics (SIC 282), are downstream users of the products manufactured by the industrial organic chemical industry. Others, such as the inorganic chemical sector, utilize unrelated feedstocks. The following list includes industrial organic chemicals (italicized) as well as other chemicals and allied product SIC codes included within SIC code 28.
SIC Industry Sector 281 Inorganic Chemicals 282 Plastics Materials and Synthetics 283 Drugs 284 Soaps, Cleaners, and Toilet Goods 285 Paints and Allied Products 2861 Gum and Wood Chemicals 2865 Cyclic Organic Chemicals 2869 Industrial Organic Chemicals, n.e.c. 287 Agricultural Chemicals 289 Miscellaneous Chemical Products
The industrial organic chemical industry uses feedstocks derived from petroleum and natural gas (about 90 percent) and from recovered coal tar condensates generated by coke production (about 10 percent). The chemical industry produces raw materials and intermediates, as well as a wide variety of finished products for industry, business and individual consumers. The important classes of products within SIC code 2861 are hardwood and softwood distillation products, wood and gum naval stores, charcoal, natural dyestuffs, and natural tanning materials.
The important classes of products within SIC code 2865 are: (1) derivatives of benzene, toluene, naphthalene, anthracene, pyridene, carbazole, and other cyclic chemical products, (2) synthetic organic dyes, (3) synthetic organic pigments, (4) cyclic (coal tar) crudes, such as light oils and light oil products; coal tar acids; and products of medium and heavy oil such as creosote oil, naphthalene, anthracene and their high homologues.
Important classes of chemicals produced by organic chemical industry facilities within SIC code 2869 include: (1) non-cyclic organic chemicals such as acetic, chloroacetic, adipic, formic, oxalic acids and their metallic salts, chloral, formaldehyde, and methylamine; (2) solvents such as amyl, butyl and ethyl alcohols; methanol; amyl, butyl, and ethyl acetates; ethyl ether, ethylene glycol ether and diethylene glycol ether; acetone, carbon disulfide, and chlorinated solvents such as carbon tetrachloride, tetrachloroethene, and trichloroethene; (3) polyhydric alcohols such as ethylene glycol, sorbitol, pentaerythritol, and synthetic glycerin; (4) synthetic perfumes and flavoring materials such as coumarin, methyl salicylate, saccharin, citral, citronellal, synthetic geraniol, ionone, terpineol, and synthetic vanillin; (5) rubber processing chemicals such as accelerators and antioxidants, both cyclic and acyclic; (6) plasticizers, both cyclic and acyclic, such as esters of phosphoric acid, phthalic anhydride, adipic acid, lauric acid, oleic acid, sebacic acid, and stearic acid; (7) synthetic tanning agents such as sulfonic acid condensates; and (8) esters and amines of polyhydric alcohols and fatty and other acids.
II.B.3. Economic trends
With organic chemicals as the single largest segment of chemical exports (accounting for nearly one-half of total chemical shipments to foreign markets), the industrial organic sector faces a market similar to the petrochemical industry. While the U.S. production is expected to continue to grow at two to four percent annually, there is increasing competition in the export market despite growing demand. World petrochemical demand is projected to increase from 320 million metric tons in 1992 to 575 million metric tons in 2010. The share accounted for by the United States, Western Europe and Japan is expected to drop from 71 to 63 percent. Products from the Gulf Cooperation Council and Pacific Rim countries, including China and Korea, will begin to compete with U.S. products in current export markets as new facilities are brought on-line. The U.S. is expected to maintain a positive trade balance in organic chemicals. Chemical imports of organic chemicals (some representing intra-company transfers) have been steady over the last five years. The reduced trade barriers due to the North American Free Trade Agreement (NAFTA) and the Uruguay Round of the General Agreement on Tariffs and Trade (GATT) have increased competition. Firms are adapting to the increased competition by emphasizing specialty chemicals and higher value-added products.
III. INDUSTRIAL PROCESS DESCRIPTION
This section describes the major industrial processes within the organic chemical industry, including the materials and equipment used, and the processes employed. The section is designed for those interested in gaining a general understanding of the industry, and for those interested in the interrelationship between the industrial process and the topics described in subsequent sections of this profile -- pollutant outputs, pollution prevention opportunities, and Federal regulations. This section does not attempt to replicate published engineering information that is available for this industry. Refer to Section IX for a list of reference documents that are available.
This section specifically contains a description of commonly used production processes, associated raw materials, the by-products produced or released, and the materials either recycled or transferred off-site. This discussion, coupled with schematic drawings of the identified processes, provides a concise description of where wastes may be produced in the process. This section also describes the potential fate (via air, water, and soil pathways) of these waste products.
III.A. Industrial Processes in the Organic Chemicals Industry
Industrial Organic Chemicals - Overview
The industrial organic chemical sector includes thousands of chemicals and hundreds of processes. In general, a set of building blocks (feedstocks) is combined in a series of reaction steps to produce both intermediates and endproducts. The chart and flow diagram below (Exhibits 4 and 5) show the primary organic chemical building blocks (generated principally from petroleum refining), a key subset of the large volume secondary building blocks and a set of large volume tertiary building blocks. The subsequent chart (Exhibit 6) shows the reaction types used to manufacture a sample of organic chemicals, and illustrates the large variety of processes used by the industry.
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Exhibit 4: High Volume Organic Chemical Building Blocks
Primary Building Block Secondary Building Block Tertiary Building Block Ethylene Ethylene dichloride Vinyl chloride Ethylene oxide Ethylene glycol Ethylbenzene Vinyl acetate Propylene Propylene oxide Acrylonitrile Isopropyl alcohol Acetone Benzene Ethylbenzene Styrene Cumene Phenol Acetone Cyclohexane Adipic acid Methanol Acetic acid Vinyl acetate Formaldehyde Methyl t-butyl ether Toluene Xylenes p-isomer Terephthalic acid Butadiene Butylene Source: Szmant, Organic Building Blocks of the Chemical Industry
Exhibit 5: Organic Chemicals and Building Blocks Flow Diagram
The typical chemical synthesis process involves combining multiple feedstocks in a series of unit operations. The first unit operation is a chemical reaction. Commodity chemicals tend to be synthesized in a continuous reactor while specialty chemicals usually are produced in batches. Most reactions take place at high temperatures, involve metal catalysts, and include one or two additional reaction components. The yield of the reaction will partially determine the kind and quantity of by-products and releases. Many specialty chemicals require a series of two or three reaction steps. Once the reaction is complete, the desired product must be separated from the by-products by a second unit operation. A number of separation techniques such as settling, distillation or refrigeration may be used. The final product may be further processed, by spray drying or pelletizing for example, to produce the saleable item. Frequently by-products are also sold and their value may alter the process economics.
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Exhibit 6: Reaction/Process Types by Chemical Category for a Sampling of Organic Chemicals
Nitro-Carbon Phenol Salt Misc. Acid Alcohhols Aledhyde Amine Amide Anhydrides Ester Nitrobenzene p-Aminophenol Sodium Dichlorodiphenyl Benzoate Sulfone Alkoxylation Condensation Halogenation Oxidation Polymerization Hydrolysis Hydrogenation Esterification Pyrolysis Alkylation Dehydrogenation Amination (Ammonolysis) Nitration Sulfonation Ammoxidation Carbonylation Hydrohalogenation Dehydration Dehydrohalogenation Oxyhalogenation Catalytic Cracking Hydrodealkylation Phosgenation Extraction Distillation Other Hydration
Generic Process Ethers Halocarbons Hydrocarbons Ketones Nitrile
Bis-1,2-Chloroisopropyl Ether Ethylene Glycol Monomethyl Ether Epichlorohydrin Methyl Bromide 1,1,1-Trichloroethane Butadiene Hexane Isoamylene Styrene Xylenes Acetone Acetonitrile
Alkoxylation 0 Condensation 0 Halogenation 0 0 Oxidation Polymerization Hydrolysis Hydrogenation Esterification Pyrolysis 0 0 0 Alkylation 0 Dehydrogenation 0 0 Amination (Ammonolysis) Nitration Sulfonation Ammoxidation 0 Carbonylation Hydrohalogenation 0 Dehydration Dehydrohalogenation 0 Oxyhalogenation 0 Catalytic Cracking 0 Hydrodealkylation 0 Phosgenation Extraction 0 0 Distillation 0 0 Other 0 Hydration
CONTINUED
Nitrobenzene P-amino Phenol Sodium Benzoate Dichlorodiphenyl Sulfone Methylene Dyphenyl Diisocyanate Sulfonic Acid n-Butanol 1,6-hexandiol Benzaldehyde Hydroxylamine Formamide Tetracholorprophthalic Anhydride Dimethyl Terephthalate
Alkoxylation Condensation 0 Halogenation 0 Oxidation 0 00 00 Polymerization Hydrolysis 0 Hydrogenation 0 00 Esterification 0 0 Pyrolysis Alkylation Dehydrogenation Amination (Ammonolysis) 0 Nitration 0 Sulfonation 0 Ammoxidation Carbonylation 0 0 Hydrohalogenation Dehydration 0 Dehydrohalogenation Oxyhalogenation Catalytic Cracking Hydrodealkylation Phosgenation 0 Extraction Distillation Other 0 0 Hydration 0
Source: U.S. Development Document for Effluent Limitations, Guidelines and Standards for the Organic Chemicals, Plastics and Synthetic Fibers Point Source Category
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The separation technology employed depends on many factors including the phases of the substances being separated, the number of components in the mixture, and whether recovery of by-products is important. Numerous techniques such as distillation, extraction, filtration, and settling can be used singly or in combination to accomplish separations and are summarized in publications such as Perry’s Chemical Engineers’ Handbook or basic texts on chemical plant design.
Relatively few organic chemical manufacturing facilities are single product/process plants. Additionally, many process units are designed so that production levels of related products can be varied over wide ranges. This flexibility is required to accommodate variations in feedstock and product prices which can change the production rate and processes used, even on a short-term (less than a year) basis. A 1983 survey showed that 59 percent of industrial organic plants had more than one product or process and that seven percent had more than 20 (USEPA Development Document for Effluent Limitations Guidelines and Standards for the Organic Chemicals, Plastics and Synthetic Fibers Point Source Category).
The type of reaction process used to manufacture chemicals depends on the intended product; however, several types of reactions are common: polymerization, oxidation, and addition. Polymerization is a chemical reaction usually carried out with a catalyst, heat or light (often under high pressure) in which a large number of relatively simple molecules combine to form a chainlike macromolecule. Oxidation, in the strict sense, means combining oxygen chemically with another substance although this name is also applied to reactions where electrons are transferred. Addition covers a wide range of reactions where a double or triple bond is broken and a component added to the structure. Alkylation can be considered an addition, as can some oxidation reactions. The following charts list the reactions used to produce a subset of organic chemical products.
Four Specific Industrial Organic Chemicals
This profile examines the reactions of four high-volume chemicals (ethylene, propylene, benzene and vinyl chloride) chosen to illustrate the use of typical chemical feedstocks based on several factors, including the quantity of chemical produced, and the health and environmental impacts of the chemical. Ethylene, propylene, and benzene are all primary building blocks and their reaction products are used to produce still other chemicals. Vinyl chloride is an important tertiary building block.
The four chemicals described below illustrate several key points. First, primary building blocks are typically used in more reactions than the building blocks further down the chain. Second, most feedstocks can participate in more than one reaction and third, there is typically more than one reaction route to an end-product. The end-products of all of these chemicals can be used in numerous commercial applications; Riegel’s Handbook of Industrial Chemistry, listed in the reference section, describes many uses.
Ethylene
The major uses for ethylene are in the synthesis of polymers (polyethylene) and in ethylene dichloride, a precursor to vinyl chloride. Other important products are ethylene oxide (a precursor to ethylene glycol) and ethylbenzene (a precursor to styrene). While ethylene itself is not generally considered a health threat, several of its derivatives, such as ethylene oxide and vinyl chloride, have been shown to cause cancer. The distribution of uses is shown below.
The manufacturing processes that use ethylene as a feedstock are summarized in the table below along with reaction conditions and components. In 1993, 18.8 million metric tons of ethylene were produced in the United States making ethylene the fourth largest production volume organic chemical in the United States. Ethylene dichloride, ethylbenzene, and ethylene oxide (products of ethylene reactions) are all among the top 50 high production volume organic chemicals in the United States (Chemical and Engineering News).
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Exhibit 7: Distribution of Uses for Ethylene Product Percent of Ethylene Use Polyethylene 54 Ethylene dichloride 16 Ethylbenzene-styrene 7 Ethylene oxide-glycol 13 Ethanol 1 Linear olefins-alcohol 3 Vinyl acetate 2 Other 4 Source: Kirk-Othmer Encyclopedia of Chemical Technology
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Exhibit 8: Manufacturing Processes Using Ethylene
Process Conditions Pressure Temperature Catalyst Reaction Process Target Product (MPa) (ºC) Components Other Characteristics Polymerization Low Density 60 - 350 350 Oxygen or Peroxide Polyethylene (LDPE) High Density 0.1 - 20 50 - 300 Molybdenum Polyethylene Chromium oxide Polyethylene Low Aluminum alkyls Titanium oxide Oxidation Ethylene Oxide 1 - 2 250 - 300 Silver 1,2-Dichloro-ethane, 60% is converted to ethylene Oxygen glycol using an acid catalyst Acetaldehyde 0.3 120 - 130 Copper chloride/Oxygen Vapor phase palladium chloride Vinyl acetate 0.4 - 1 170 - 200 Palladium Acetic acid Addition Halogenation\ Ethylene dichloride 60 Iron, aluminum, Chlorine Feedstock for vinyl chloride and hydrohalogenation copper, or antimony trichloroethylene and chlorides tetrachloroethylene Ethyl chloride 0.3 - 0.5 Aluminum or iron HCl Precursor of styrene chlorides Alkylation Ethylbenzene Aluminum, iron, and Benzene boron chlorides Hydroformation Propionaldehyde 4 - 35 60 - 200 Cobalt Synthesis gas (carbon monoxide and hydrogen) Source: Kirk-Othmer Encyclopedia of Chemical Technology
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Propylene
Over half of the U.S. propylene supplies (10.2 million metric tons produced in 1993) are used in the production of chemicals. The primary products are polypropylene, acrylonitrile, propylene oxide, and isopropyl alcohol. Of these, propylene, acrylonitrile and propylene oxide are among the top fifty highvolume chemicals produced in the United States. Acrylonitrile and propylene oxide have both been shown to cause cancer, while propylene itself is not generally considered a health threat. The table below shows the use distribution of propylene.
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Exhibit 9: Distribution of Propylene Use
Product Percent of Propylene Use Polypropylene 36 Acrylonitrile 16 Propylene oxide 11 Cumene 9 Butyraldehydes 7 Oligomers 6 Isopropyl alcohol 6 Other 9 Source: Szmant, Organic Building Blocks of the Chemical Industry
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The important propylene reactions are shown below. The products of the reactions are the feedstocks for numerous additional products.
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Exhibit 10: Manufacturing Processes Using Propylene
Process Conditions Pressure Reaction Process Target Product (MPa) Temperature Catalyst Components Other Characteristics Polymerization Polypropylene Aluminum alkyls/Titanium oxide Oxidation Acrylonitrile 400 Phosphomolybdate Ammonia Commercially valuable byproducts are acetonitrile and hydrogen cyanide Commercially valuable Propylene oxide Oxygen byproduct is tert-butyl alcohol Ethylbenzene Addition Chlorohydrination Propylene oxide 25 37 Tungsten Hypochlorous Hydrolysis Isopropyl alcohol 267 Water Source: Kirk-Othmer Encyclopedia of Chemical Technology
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Benzene
Benzene is an important intermediate in the manufacture of industrial chemicals and over 5.5 million metric tons were produced in the U.S. in 1993 (Chemical and Engineering News). Over 95 percent of U.S. consumption of benzene is for the preparation of ethylbenzene, cumene, cyclohexane, nitrobenzene, and various chlorobenzenes as shown in the table below.
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Exhibit 11: Distribution of Benzene Use
Product Percent of Benzene Use Ethylbenzene 52 Cumene 22 Cyclohexane 14 Nitrobenzene 5 Chlorobenzenes 2 Linear detergent alkylate 2 Other 3 Source: Kirk-Othmer Encyclopedia of Chemical Technology
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The following table summarizes the primary benzene reactions. The products are frequently feedstocks in the synthesis of additional chemicals. Benzene is considered a human carcinogen by the Agency.
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Exhibit 12: Manufacturing Processes Using Benzene
Process Conditions Pressure Temperature Process Target product (MPa) ((C) Catalyst Reaction components Other characteristics Oxidation Phenol 0.6 90-100 Cumene, Oxygen Most important phenol synthesis Maleic anhydride 0.1-0.2 350-400 Vanadium oxide Butane Oxygen Styrene 0.1 580-590 Iron oxide Ethylene benzene Addition Alkylation Ethylbenzene 0.2-0.4 125-140 Aluminum chloride Benzene, Ethylene Precursor to styrene Ethylbenzene 2.0 420-430 Zeolite Benzene, Ethylene Precursor to styrene Cumene 0.3-1.0 250-350 Phosphoric Benzene, Propylene acid/silicate 2,6-Xylenol 0.1-0.2 300-400 Aluminum oxide Phenol, Methanol Hydrogenation Cyclohexanone 0.1 140-170 Palladium Phenol, Hydrogen Cyclohexanol 1.0-2.0 120-200 Nickel/silicon oxide Phenol and aluminum oxide Cyclohexane 2.0-5.0 150-200 Nickel Benzene, Hydrogen Aniline .18 270 Copper Nitrobenzene, Hydrogen Nitration Nitrobenzene 0.1 60 Benzene, sulfuric acid, nitric acid Sulfonation Surfactants 0.1 40-50 Alkylbenezenes/Sulfur trioxide Chlorination Chlorobenzene 0.1 30-40 Aluminum chloride/Benzene, Chlorine Iron chloride Condensation Biphenol A 0.1 50-90 HCl Phenol, Acetone
Source: Franck and Stadelhofer, "Industrial Aromatic Chemistry"
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Vinyl Chloride
Vinyl chloride is one of the largest commodity chemicals in the U.S. with over 6.25 million metric tons produced in 1993. It is also considered a human carcinogen by the EPA. Vinyl chloride polymers are the primary end use but various vinyl ethers, esters, and halogen products can also be made as shown in the table below.
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Exhibit 13: Manufacturing Processes Using Vinyl Chloride
Process Conditions Pressure Temperature Reaction Process Target Product (MPa) ((C) Catalyst components Other characteristics Polymerization Polyvinylchloride 50 Peroxides Substitution at the Vinyl acetates, Palladium Alkyl halides Carbon-Chlorine alcholates, vinyl esters Bond and vinyl ethers Addition Various halogen addition products Source: Kirk-Othmer Encyclopedia of Chemical Technology
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III.B. Raw Material Inputs and Pollution Outputs
Industrial organic chemical manufacturers use and generate both large numbers and quantities of chemicals. The industry emits chemicals to all media including air (through both fugitive and direct emissions), water (direct discharge and runoff) and land. The types of pollutants a single facility will release depend on the feedstocks, processes, equipment in use and maintenance practices. These can vary from hour to hour and can also vary with the part of the process that is underway. For example, for batch reactions in a closed vessel, the chemicals are more likely to be emitted at the beginning and end of a reaction step (associated with vessel loading and product transfer operations), than during the reaction. The potential sources of pollutant outputs by media are shown below.
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Exhibit 14: Potential Releases During Organic Chemical Manufacturing Media Potential Sources of Emissions Air Point source emissions: stack, vent (e.g. laboratory hood, distillation unit, reactor, storage tank vent), material loading/unloading operations (including rail cars, tank trucks, and marine vessels)
Fugitive emissions: pumps, valves, flanges, sample collection, mechanical seals, relief devices, tanks
Secondary emissions: waste and wastewater treatment units, cooling tower, process sewer, sump, spill/leak areas
Liquid wastes (Organic or Aqueous)
Equipment wash solvent/water, lab samples, surplus chemicals, product washes/purifications, seal flushes, scrubber blowdown, cooling water, steam jets, vacuum pumps, leaks, spills, spent/used solvents, housekeeping (pad washdown), waste oils/lubricants from maintenance
Solid Wastes
Spent catalysts, spent filters, sludges, wastewater treatment biological sludge, contaminated soil, old equipment/insulation, packaging material, reaction byproducts, spent carbon/resins, drying aids
Ground Water Contamination
Unlined ditches, process trenches, sumps, pumps/valves/fittings, wastewater treatment ponds, product storage areas, tanks and tank farms, aboveground and underground piping, loading/unloading areas/racks, manufacturing maintenance facilities
Source: Designing Pollution Prevention into the Process- Research, Development and Engineering
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III.C. Management of Chemicals in the Production Process
The Pollution Prevention Act of 1990 (PPA) requires facilities to report information about the management of TRI chemicals in waste and efforts made to eliminate or reduce those quantities. These data have been collected annually in Section 8 of the TRI reporting Form R beginning with the 1991 reporting year. The data summarized below cover the years 1992 through 1995 and are meant to provide a basic understanding of the quantities of waste handled by the industry, the methods typically used to manage this waste, and recent trends in these methods. TRI waste management data can be used to assess trends in source reduction within individual industries and facilities, and for specific TRI chemicals. This information could then be used as a tool in identifying opportunities for pollution prevention compliance assistance activities.
From the yearly data presented below it is apparent that the portion of TRI wastes reported as recycled on-site has remained reasonably constant between 1992 and 1995 (projected). While the quantities reported for 1992 and 1993 are estimates of quantities already managed, the quantities reported for 1994 and 1995 are projections only. The PPA requires these projections to encourage facilities to consider future waste generation and source reduction of those quantities as well as movement up the waste management hierarchy. Future-year estimates are not commitments that facilities reporting under TRI are required to meet.
Exhibit 15 shows that the organic chemical industry managed about 6.3 trillion pounds of production-related waste (total quantity of TRI chemicals in the waste from routine production operations) in 1993 (column B). Column C reveals that of this production-related waste, seven percent was either transferred off-site or released to the environment. Column C is calculated by dividing the total TRI transfers and releases by the total quantity of production-related waste. In other words, about 90 percent of the industry’s TRI wastes were managed on-site through recycling, energy recovery, or treatment as shown in columns E, F and G, respectively. The majority of waste that is released or transferred off-site can be divided into portions that are recycled off-site, recovered for energy off-site, or treated off-site as shown in columns H, I and J, respectively. The remaining portion of the production related wastes (three percent), shown in column D, is either released to the environment through direct discharges to air, land, water, and underground injection, or it is disposed off-site.
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Exhibit 15: Source Reduction and Recycling Activity for the Organic Chemical Industry (SIC 286) as Reported within TRI
A B C D On-Site Off-Site Quantity of Production- % Released Related % Released and E F G H I J Waste and Disposedc Year (106 lbs.)a Transferred b Off-site % % Energy % % Energy Recycled Recovery % Treated Recycled Recovery % Treated
1992 6,313 7% 3% 71% 7% 15% 2% 1% 2% 1993 6,325 7% 3% 71% 7% 15% 2% 1% 1% 1994 6,712 --- 2% 71% 8% 15% 2% 1% 1% 1995 6,645 --- 2% 72% 7% 15% 2% 1% <1%
a Within this industry sector, non-production related waste < 1% of production related wastes for 1993. b Total TRI transfers and releases as reported in Section 5 and 6 of Form R as a percentage of production related wastes. c Percentage of production related waste released to the environment and transferred off-site for disposal.
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IV. CHEMICAL RELEASE AND TRANSFER PROFILE
The following is a synopsis of current scientific toxicity and fate information for the top chemicals (by weight) that facilities within this sector self-reported as released to the environment based upon 1993 TRI data. Because this section is based upon self-reported release data, it does not attempt to provide information on management practices employed by the sector to reduce the release of these chemicals. Information regarding pollutant release reductions over time may be available from EPA’s TRI and 33/50 programs, or directly from the industrial trade associations that are listed in Section IX of this document. Since these descriptions are cursory, please consult the sources referenced below for a more detailed description of both the chemicals described in this section and the chemicals that appear on the full list of TRI chemicals appearing in Section IV.A.
This section is designed to provide background information on the pollutant releases that are reported by this industry. The best source of comparative pollutant release information is the Toxic Release Inventory System (TRI). Pursuant to the Emergency Planning and Community Right-to-Know Act, TRI includes self-reported facility release and transfer data for over 600 toxic chemicals. Facilities within SIC Codes 20 through 39 (manufacturing industries) that have more than 10 employees, and that are above weightbased reporting thresholds are required to report TRI on-site releases and offsite transfers. The information presented within the sector notebooks is derived from the most recently available (1993) TRI reporting year (which then included 316 chemicals), and focuses primarily on the on-site releases reported by each sector. Because TRI requires consistent reporting regardless of sector, it is an excellent tool for drawing comparisons across industries. TRI data provide the type, amount and media receptor of each chemical released or transferred.
Although this sector notebook does not present historical information regarding TRI chemical releases over time, please note that in general, toxic chemical releases have been declining. In fact, according to the 1993 Toxic Release Inventory Data Book, reported releases dropped by 43 percent between 1988 and 1993. Although on-site releases have decreased, the total amount of reported toxic waste has not declined because the amount of toxic chemicals transferred off-site has increased. Transfers have increased from 3.7 billion pounds in 1991 to 4.7 billion pounds in 1993. Better management practices have led to increases in off-site transfers of toxic chemicals for recycling. More detailed information can be obtained from EPA's annual Toxics Release Inventory Public Data Release book (which is available through the EPCRA Hotlines at 800-535-0202), or directly from the Toxic Release Inventory System database (for user support call 202-260-1531).
Wherever possible, the sector notebooks present TRI data as the primary indicator of chemical release within each industrial category. TRI data provide the type, amount and media receptor of each chemical released or transferred. When other sources of pollutant release data have been obtained, these data have been included to augment the TRI information.
TRI Data Limitations
The reader should keep in mind the following limitations regarding TRI data. Within some sectors, the majority of facilities are not subject to TRI reporting because they are not considered manufacturing industries, or because they are below TRI reporting thresholds. Examples are the mining, dry cleaning, printing, and transportation equipment cleaning sectors. For these sectors, release information from other sources has been included.
The reader should also be aware that TRI “pounds released” data presented within the notebooks is not equivalent to a “risk” ranking for each industry. Weighting each pound of release equally does not factor in the relative toxicity of each chemical that is released. The Agency is in the process of developing an approach to assign toxicological weightings to each chemical released so that one can differentiate between pollutants with significant differences in toxicity. As a preliminary indicator of the environmental impact of the industry's most commonly released chemicals, this notebook briefly summarizes the toxicological properties of the top five chemicals (by weight) reported by the organic chemical industry.
Definitions Associated with Section IV Data Tables
General Definitions
SIC Code -- is the Standard Industrial Classification (SIC) is a statistical classification standard used for all establishment-based Federal economic statistics. The SIC codes facilitate comparisons between facility and industry data.
TRI Facilities -- are manufacturing facilities that have 10 or more full-time employees and are above established chemical throughput thresholds. Manufacturing facilities are defined as facilities in Standard Industrial Classification primary codes 20 through 39. Facilities must submit estimates for all chemicals that are on the EPA's defined list and are above throughput thresholds.
Data Table Column Heading Definitions
The following definitions are based upon standard definitions developed by EPA’s Toxic Release Inventory Program. The categories below represent the possible pollutant destinations that can be reported.
RELEASES -- are an on-site discharge of a toxic chemical to the environment. This includes emissions to the air, discharges to bodies of water, releases at the facility to land, as well as contained disposal into underground injection wells.
Releases to Air (Point and Fugitive Air Emissions) -- Include all air emissions from industry activity. Point emissions occur through confined air streams as found in stacks, ducts, or pipes. Fugitive emissions include losses from equipment leaks, or evaporative losses from impoundments, spills, or leaks.
Releases to Water (Surface Water Discharges) -- encompass any releases going directly to streams, rivers, lakes, oceans, or other bodies of water. Any estimates for storm water runoff and non-point losses must also be included.
Releases to Land -- includes disposal of toxic chemicals in waste to on-site landfills, land treated or incorporation into soil, surface impoundments, spills, leaks, or waste piles. These activities must occur within the facility's boundaries for inclusion in this category.
Underground Injection -- is a contained release of a fluid into a subsurface well for the purpose of waste disposal.
TRANSFERS -- is a transfer of toxic chemicals in wastes to a facility that is geographically or physically separate from the facility reporting under TRI. The quantities reported represent a movement of the chemical away from the reporting facility. Except for off-site transfers for disposal, these quantities do not necessarily represent entry of the chemical into the environment.
Transfers to POTWs -- are waste waters transferred through pipes or sewers to a publicly owned treatments works (POTW). Treatment and chemical removal depend on the chemical's nature and treatment methods used. Chemicals not treated or destroyed by the POTW are generally released to surface waters or land filled within the sludge.
Transfers to Recycling -- are sent off-site for the purposes of regenerating or recovering still valuable materials. Once these chemicals have been recycled, they may be returned to the originating facility or sold commercially.
Transfers to Energy Recovery -- are wastes combusted off-site in industrial furnaces for energy recovery. Treatment of a chemical by incineration is not considered to be energy recovery.
Transfers to Treatment -- are wastes moved off-site for either neutralization, incineration, biological destruction, or physical separation. In some cases, the chemicals are not destroyed but prepared for further waste management.
Transfers to Disposal -- are wastes taken to another facility for disposal generally as a release to land or as an injection underground.
IV.A. EPA Toxic Release Inventory for the Organic Chemicals Industry
According to the Toxics Release Inventory (TRI) data, 417 organic chemical facilities released (to the air, water or land) and transferred (shipped off-site or discharged to sewers) a total of 438 million pounds of toxic chemicals during calendar year 1993. That represents approximately 18 percent of the 2.5 billion pounds of releases and transfers from the chemical industry as a whole (SIC 28) and about six percent of the releases and transfers for all manufacturers reporting to TRI that year. By comparison, the inorganic chemical industry’s releases and transfers in 1993 totaled 249.7 million pounds, or sixty percent of the releases and transfers of the industrial organic chemical sector.
The chemical industry’s releases have been declining in recent years. Between 1988 and 1992 TRI emissions from chemical companies (all those categorized within SIC 28, not just organic chemical manufacturers) to air, land, and water were reduced 44 percent, which is average for all manufacturing sectors reporting to TRI.
Because the chemical industry (SIC 28) has historically released more TRI chemicals than any other industry, the EPA has worked to improve environmental performance within this sector. This has been done through a combination of enforcement actions, regulatory requirements, pollution prevention projects, and voluntary programs (e.g. EPA’s 33/50 program). In addition, the chemical industry has focused on reducing pollutant releases. For example, the Chemical Manufacturer’s Association’s (CMA’s) Responsible Care® initiative is intended to reduce or eliminate chemical manufacturers’ wastes. All 185 members of the CMA, firms that account for the majority of U.S. chemical industry sales and earnings, are required to participate in the program as a condition of CMA membership. Participation involves demonstrating a commitment to the program’s mandate of continuous improvement of the environment, health, and safety. In June of 1994, the CMA approved the use of a third-party verification of management plans to meet these objectives. State-level toxics use reduction requirements, public disclosure of release and transfer information contained in TRI, and voluntary programs such as EPA’s 33/50 Program have also been given as reasons for release reductions.
Exhibit 16 presents the number and volumes of chemicals released by organic chemical facilities. The quantity of the basic feedstocks released reflects their volume of usage. The inorganic chemicals among the top ten released (ammonia, nitric acid, ammonium sulfate, and sulfuric acid) are also large volume reaction feedstocks. Inorganic chemicals contained in wastes injected underground on-site account for 58 percent of the industry's releases; ammonia makes up the vast majority of TRI chemicals disposed of via underground injection. Air releases account for 40 percent (61 million pounds), and the remaining approximately 1.5 percent (2.4 million pounds) is discharged directly to water or land disposed.
Exhibit 17 presents the number and volumes of chemicals transferred by organic chemical facilities. Off-site transfers account for the largest amount, 65 percent, of the organic chemical industry's total releases and transfers as reported in TRI. Three chemicals (sulfuric acid, methanol and tert-butyl alcohol) account for over one-half of the 287 million pounds transferred offsite. The 49 million pounds of POTW discharges (primarily methanol and ammonia) account for 17 percent of releases and transfers.
The frequency with which chemicals are reported by facilities within a sector is one indication of the diversity of operations and processes. Many chemicals are released or transferred by a small number of facilities, which indicates a wide diversity of production processes, particularly for specialty organic chemicals -- over one half of the 204 chemicals reported are released by fewer than 10 facilities. However, the organic chemical industry is also characterized by one of the largest numbers of chemicals reported by any manufacturing sector. Of the over 300 chemicals currently listed on TRI, 204 are reported as released or transferred by at least one organic chemical facility.
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Exhibit 16 (cont.): 1993 Releases for Organic Chemical Manufacturing Facilities in TRI, by Number of Facilities Reporting (Releases reported in pounds/year)
# REPORTING FUGITIVE POINT WATER UNDERGROUN LAND TOTAL AVG. RELEASES CHEMICAL AIR AIR DISCHARGES D INJECTION DISPOSAL RELEASES PER FACILITY CHEMICAL NAME DIMETHYL SULFATE 14 1,310 644 0 0 5 1,959 140 TETRACHLOROETHYLENE 14 29,594 17,654 29 0 0 47,277 3,377 CREOSOTE 13 55,110 74,595 5 0 585 130,295 10,023 BUTYL ACRYLATE 12 81,815 45,684 306 0 0 127,805 10,650 CARBON DISULFIDE 12 43,576 10,221 251 0 0 54,048 4,504 EPICHLOROHYDRIN 12 17,289 2,296 292 0 0 19,877 1,656 O-XYLENE 12 102,254 160,275 141 0 0 262,670 21,889 1,2-DICHLOROETHANE 12 220,032 968,026 70 0 0 1,188,128 99,011 BENZOYL CHLORIDE 11 6,087 1,819 0 0 5 7,911 719 BUTYRALDEHYDE 11 34,477 31,689 7 189,447 0 255,620 23,238 CHLOROFORM 11 12,764 62,055 693 74 200 75,786 6,890 COBALT COMPOUNDS 11 0 4,592 80,304 0 18,696 103,592 9,417 DIBENZOFURAN 11 10,880 10,059 10 0 910 21,859 1,987 DIETHYL SULFATE 11 616 17 0 0 5 638 58 ETHYL ACRYLATE 11 46,571 35,631 410 2,400 0 85,012 7,728 HYDROQUINONE 11 188 5 30 190,000 117 190,340 17,304 MANGANESE COMPOUNDS 11 1,760 28,017 131,505 0 61,000 222,282 20,207 METHYL ACRYLATE 11 51,940 49,500 5 0 0 101,445 9,222 METHYL METHACRYLATE 11 76,114 119,538 750 0 250 196,652 17,877 METHYL TERT-BUTYL ETHER 11 143,917 70,795 85 8,772 0 223,569 20,324 TRICHLOROETHYLENE 11 42,619 936 5 0 0 43,560 3,960 VINYL ACETATE 11 166,157 744,939 0 892,698 0 1,803,794 163,981 BENZYL CHLORIDE 10 2,297 432 0 0 58 2,787 279 HYDROGEN CYANIDE 10 10,539 298,141 0 651,815 12 960,507 96,051 M-CRESOL 10 20,937 2,442 406 520,000 0 543,785 54,379 QUINOLINE 10 3,327 17,900 40 63,000 190 84,457 8,446 SEC-BUTYL ALCOHOL 10 15,241 8,310 2,440 0 5 25,996 2,600 ACETONITRILE 9 79,850 64,366 217 3,969,793 13 4,114,239 457,138 ACRYLAMIDE 9 16,503 1,597 0 930,000 160 948,260 105,362 CARBON TETRACHLORIDE 9 55,191 55,130 234 63 0 110,618 12,291 FREON 113 9 23,242 84,780 44 4 406 108,476 12,053 HYDRAZINE 9 7,195 1,551 0 0 0 8,746 972 TRICHLOROFLUOROMETHANE 9 103,857 74,459 50 11 750 179,127 19,903 ALLYL ALCOHOL 8 36,773 6,928 5,100 192,966 0 241,767 30,221 CHLOROACETIC ACID 8 3,786 413 5 0 0 4,204 526 COPPER 8 0 170 1,329 0 4,880 6,379 797 CUMENE HYDROPEROXIDE 8 11,380 5,404 190 380,000 3 396,977 49,622 CYANIDE COMPOUNDS 8 26,142 1,543 7,391 426,890 2,846 464,812 58,102 ISOBUTYRALDEHYDE 8 37,012 16,187 255 34,783 0 88,237 11,030 O-TOLUIDINE 8 8,370 155 5 9,600 7 18,137 2,267 P-CRESOL 8 13,522 2,197 273 260,000 0 275,992 34,499 PROPIONALDEHYDE 8 20,845 13,991 5 31,995 0 66,836 8,355 2-METHOXYETHANOL 8 27,431 3,436 430 0 0 31,297 3,912 4,4'- 8 67,835 8,979 337 43,000 250 120,401 15,050 DI(2-ETHYLHEXYL) 7 270 255 0 0 0 525 75 DIBUTYL PHTHALATE 7 271 505 23 0 0 799 114 DIMETHYL PHTHALATE 7 5,424 1,461 12 1,300 5 8,202 1,172 HYDROGEN FLUORIDE 7 3,894 4,627 0 1 0 8,522 1,217 NICKEL 7 6 250 5 0 113 374 53 PHOSGENE 7 265 293 0 0 0 558 80 PYRIDINE 7 11,229 2,339 0 220,000 0 233,568 33,367 ACROLEIN 6 5,170 10,129 0 82 0 15,381 2,564 TOLUENEDIISOCYANATE 2 5 5 0 0 250 260 13,059 (MIXED ISOMERS) 0 0 0 0 1,2-BUTYLENE OXIDE 2 289 0 0 0 0 289 145 2,4-DIMETHYLPHENOL 0 3,400 160 80 0 0 58,640 29,320 2,3-DINITROPHENOL 2 1 2 110 0 0 117 59 3,3'-DIMETHOXYBENZIDINE 0 0 0 4 0 0 4 2 4,4'-METHYLENEDIANILINE (1) 2,404 5 0 150 0 2,559 1,280 ACETAMIDE 0 2 8 0 89,000 0 89,010 89,010 ALPHA-NAPHTHYLAMINE 0 0 0 0 0 0 0 0 ALUMINUM (FUME OR DUST) 1 115 0 219 0 0 334 334 BENZIOIC TRICHLORIDE 1 1,318 5 0 0 0 1,323 1,323 BIS(2-CHLOROETHYL) ETHER 1 22 0 0 0 0 22 22 BROMOCHLORODIFLUOROMETHANE 1 0 0 0 0 0 0 0 C.I. BASIC RED 1 1 0 0 0 0 0 0 0 C.I. DISPERSE YELLOW 3 1 399 0 28 0 9,199 9,626 9,626 C.I. SOLVENT YELLOW 3 1 0 0 0 0 0 0 0 CADMIUM 1 0 0 0 0 0 0 0 CHLORDANE 1 51 0 15 0 0 66 66 COBALT 1 0 1,800 460 0 1,600 3,860 3,860 CUPFERRON 1 2 23 0 0 0 25 25 ETHYL CHLOROFORMATE 1 250 5 0 0 0 255 255 ETHYLENE THIOUREA 1 5 5 0 0 0 10 10 ETHYLENEIMINE 1 0 0 0 0 0 0 0 HEPTACHLOR 1 31 0 2 0 0 33 33 HEXACHLOROCYCLOPENTADIENE 1 1,342 861 0 0 0 2,203 2,203 HEXACHLOROETHANE 1 1 0 0 0 0 1 1 HYDRAZINE SULFATE 1 0 0 0 0 0 0 0 LEAD 1 5 5 0 0 0 10 10 M-DINITROBENZINE 1 49 7 0 0 0 56 56 METHYL IODIDE 1 6,800 92 0 0 0 6,892 6,892 METHYL ISOCYANATE 1 0 0 0 0 0 0 0 METHYLENE BROMIDE 1 3 13 0 0 0 16 16 O-DINITROBENZENE 1 1 1 0 0 0 2 2 OXY-ALKYLATED ALCOHOL 1 250 5 0 0 0 255 255 P-PHENYLENEDIAMINE 1 1 1 0 0 0 4 4 PHENYL MIXTURE 1 2,600 200 0 0 0 2,800 2,800 PHOSPHORUS (YELLOW OR WHITE) 1 0 0 0 0 0 0 0 SACCHARIN (MANUFACTURING) 1 50 1 0 0 0 51 51 TITANIUM TETRACHLORIDE 1 0 0 0 0 0 0 0 ZINC (FUME OR DUST) 1 0 290 0 0 0 290 290 1,3-DICHLOROBENZENE 1 0 0 0 0 0 0 0 1,3-DICHLOROPROPYLENE 1 3 22 0 0 0 25 25 1,4-DICHLOROBENZENE 1 32 95 0 0 0 127 127 2-NITROPROPANE 1 0 0 0 0 0 0 0 2,4-DIAMINOANISOLE 1 0 13 0 0 0 13 13 2,4-DINITROTOLUENE 1 1 2 0 0 0 3 3 2,6-SYLIDINE 1 53 2 0 0 0 55 55 4-NITROPHENOL 1 290 21 0 0 0 311 311 5-NITRO-O-ANISIDINE 1 5 5 0 0 0 10 10
TOTAL 417 28,256,560 33,222,806 1,415,674 87,698,609 1,027,734 151,621,383 363,600
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Exhibit 17: 1993 Transfers for Organic Chemical Manufacturing Facilities in TRI, by Number of Facilities Reporting (Transfers reported in pounds/year)
# REPORTING POTW ENERGY TOTAL AVG. TRANSFERS CHEMICAL NAME CHEMICAL DISCHARGES DISPOSAL RECYCLING TREATMENT RECOVERY TRANSFERS PER FACILITY
SULFURIC ACID 216 60,857 1,460,275 84,722,700 3,530,520 0 86,596,884 400,912
METHANOL 194 210,007,643 298,453 5,596,077 4,597,065 11,815,643 43,307,981 223,237
HYDROCHLORIC ACID 144 742,576 770,703 7,415 2,680,884 182 4,202,346 29,183
AMMONIA 116 8,351,095 1,263,566 162,738 83,271 930 9,861,610 85,014
TOLUENE 109 13,790 267,107 7,155,414 999,051 9,256,100 17,691,462 162,307
XYLENE (MIXED ISOMERS) 89 19,513 248,470 303,172 205,720 4,912,122 5,688,997 63,921
ETHYLENE GLYCOL 86 2,630,290 291,143 122,260 2,504,914 4,915,874 10,464,481 121,680
CHLORINE 85 30,671 22 0 115,400 2,687 148,780 1,750
ACETONE 84 2,452,706 27,530 182,320 859,366 3,893,746 7,415,668 88,282
FORMALDEHYDE 78 264,163 403 173 102,654 1,055 368,448 4,724
BENZENE 72 596 31,498 705,846 225,803 174,445 1,138,188 158,808
GLYCOL ETHERS 67 2,469,069 82,646 10,170 173,874 254,182 2,989,941 44,626
PHOSPHORIC ACID 67 36,422 11,680 0 2,166 15 50,283 750
PHENOL 62 559,856 96,193 3,300 247,644 466,822 1,373,815 22,158
N-BUTYL ALCOHOL 56 235,678 193,040 210 335,171 2,024,030 2,788,129 49,788
STYRENE 47 9,772 12,738 9,935 714,896 250,703 998,044 21,235
ZINC COMPOUNDS 46 53,120 1,078,844 173,261 62,751 16,914 1,384,890 30,106
COPPER COMPOUNDS 44 46,957 242,892 1,458,665 187,352 0 193,866 43,997
NAPHTHALENE 44 3,853 156,104 56,080 218,493 220,473 655,003 14,886
ETHYLBENZENE 42 331 28,706 4,765 12,484 448,357 494,643 11,777
ETHYLENE 38 0 68 0 0 0 68 2
MALEIC ANHYDRIDE 38 155 7,797 0 2,563 0 10,515 277
DICHLOROMETHANE 36 533 814 539,664 278,008 420,139 1,239,158 34,421
PROPYLENE 35 0 0 0 380,000 0 380,000 10,857
ACRYLIC ACID 31 29,470 26,822 0 73,140 7,855,500 7,984,932 257,578
BIPHENYL 28 265,741 9,922 14,409 92,951 75,951 458,974 16,392
CYCLOHEXANE 28 3,083 1,420 1,034,820 196,873 406,927 1,643,123 58,683
DIETHANOLAMINE 28 123,941 46,624 0 1,428 6,839 178,832 6,387
BARIUM COMPOUNDS 27 80,991 251,349 1,039 22,895 32,435 388,709 14,397
METHYL ETHYL KETONE 27 88,200 14,967 7,402 34,173 1,703,103 1,847,845 68,439
NITRIC ACID 27 355 232,000 0 7,160 0 239,515 8,871
PHTHALIC ANHYDRIDE 27 3,956 46,965 0 34,579 1,774,375 1,859,875 68,884
ANILINE 26 1,309,605 390,621 0 28,201 166,308 1,894,735 72,874
CHLOROMETHANE 25 788 6 0 91,521 47,285 139,600 5,584
CUMENE 25 20,017 5,761 4,511 8,372 68,031 106,692 4,268
CHROMIUM COMPOUNDS 24 4,982 44,909 561,231 110,976 190 722,288 30,095
ETHYLENE OXIDE 24 18,441 1,989 0 0 1 20,431 851
PROPYLENE OXIDE 23 9,409 9,564 0 7 2,660 21,640 941
1,3-BUTADIENE 23 250 550 0 21 81 902 39
1,2,4-TRIMETHYLBENZENE 22 49,994 5,068 4,511 451 60,471 120,495 5,477
ACETALDEHYDE 20 80,071 0 0 264 0 80,335 4,019
METHYL ISOBUTYL KETONE 19 50,988 642 25 856 289,105 341,616 17,980
NICKEL COMPOUNDS 19 5,504 43,454 747,998 211,744 0 1,008,700 53,089
ACRYLONITRILE 18 35,489 0 0 349,878 585,483 970,850 53,936
CHLOROETHANE 18 5 0 151,000 388,895 0 539,900 29,994
ANTHRACENE 17 256 28,683 8,909 2,600 53,834 94,282 5,546
CHLOROBENZENE 16 1,076 915 157 17,904 15,591 35,643 2,228
1,1,1-TRICHLOROETHANE 16 12 0 16,461 620,387 1,591 638,451 39,903
CRESOL (MIXED ISOMERS) 15 250 4,113 6,500 26,725 447 38,035 2,536
DICHLORODIFLUOROMETHANE 15 8 8 0 0 0 16 1
TERT-BUTYL ALCOHOL 15 862,730 255,223 5,324 328,262 29,383,823 30,835,362 2,055,691
AMMONIUM SULFATE 14 5,178,324 250 0 211,000 0 5,389,574 384,970
DIMETHYL SULFATE 14 255 0 39,542 0 0 39,797 2,843
TETRACHLOROETHYLENE 14 447 79 1,126 282,805 11,855 296,312 21,165
CREOSOTE 13 0 700,472 273,000 300 29,220 1,002,992 77,153
BUTYL ACRYLATE 12 279 725 0 7,541 0 8,545 712
CARBON DISULFIDE 12 7,289 279 4,413 7,925 125,206 145,112 12,093
EPICHLOROHYDRIN 12 255 0 0 185 0 440 37
O-XYLENE 12 28 28,557 5,414 10,341 861,637 905,977 75,498
1,2-DICHLOROETHANE 12 731 54,402 1,700,000 402,888 406 2,158,427 179,869
BENZOYL CHLORIDE 11 0 250 0 0 0 250 23
BUTYRALDEHYDE 11 0 1,700 450 0 1,700 3,850 350
CHLOROFORM 11 264 0 3,100 131,685 19,297 154,346 14,031
COBALT COMPOUNDS 11 14 184,500 148,400 7 0 332,921 30,266
DIBENZOFURAN 11 250 25,701 3,609 0 19,988 49,548 4,504
DIETHYL SULFATE 11 10 0 5,370,000 0 0 53,701,010 488,183
ETHYL ACRYLATE 11 500 6,950 0 187,311 1,378,573 1,573,334 143,030
HYDROQUINONE 11 1,210 32,261 0 338 0 33,809 3,074
MANGANESE COMPOUNDS 11 5,019 819,758 11,600 0 0 836,377 76,034
METHYL ACRYLATE 11 2,110 250 0 5,765 10,508 18,633 1,694
METHYL METHACRYLATE 11 563 750 71,000 226,520 10,410 309,243 28,113
METHYL TERT-BUTYL ETHER 11 31 133,320 0 0 237,779 371,130 33,739
TRICHLOROETHYLENE 11 7 0 1,143 310,803 0 311,953 28,359
VINYL ACETATE 11 95,453 390 0 9,341 561,083 666,267 60,570
BENZYL CHLORIDE 10 250 0 0 14 30,980 31,244 3,124
HYDROGEN CYANIDE 10 250 2,053 0 74 250 2,627 263
M-CRESOL 10 9,649 13,336 270,000 51,118 2,923 347,026 34,703
QUINOLINE 10 250 5,482 3,609 2 5,354 14,397 1,470
SEC-BUTYL ALCOHOL 10 2,046 145,000 0 1,682 4,082,657 4,231,385 423,139
ACETONITRILE 9 255 1,601 0 410 263,316 265,582 29,509
ACRYLAMIDE 9 79,559 500 0 20,470 44,330 154,859 17,207
CARBON TETRACHLORIDE 9 1,604 1,366 1,750 136,570 0 141,290 15,699
FREON 113 9 0 12 13,215 64,636 0 77,863 8,651
HYDRAZINE 9 1,400 3,617 0 0 0 5,017 557
TRICHLOROFLUOROMETHANE 9 349 0 750 2,433 0 3,532 392
ALLYL ALCOHOL 8 27,663 4,271 0 28,172 139,592 199,698 24,962
CHLOROACETIC ACID 8 0 250 0 1,026 150 1,426 178
COPPER 8 0 30,937 35,708 21,000 0 86,756 10,845
CUMENE HYDROPEROXIDE 8 0 415 0 3,566 0 3,981 498
CYANIDE COMPOUNDS 8 3,005 3,231 0 3,292 0 9,528 1,191
ISOBUTYRALDEHYDE 8 0 0 200 32,000 655,579 687,779 85,972
O-TOLUIDINE 8 5,819 42 0 0 220 6,081 760
P-CRESOL 8 866,495 7,086 160,000 10,886 41,466 1,085,933 135,742
PROPIONALDEHYDE 8 0 3,167 0 0 0 3,167 396
2-METHOXYETHANOL 8 46,000 16,300 70 0 91,736 154,106 19,263
4,4'-ISOPROPYLIDENEDIPHENOL 8 255 30,767 0 1,231 5,447 37,700 4,713
DI(2-ETHYLHEXYL) PHTHALATE 7 10 250 0 250 1,424 1,934 276
DIBUTYL PHTHALATE 7 256 296 0 658 5,659 6,869 981
DIMETHYL PHTHALATE 7 119,565 825 0 3,967 618 124,975 17,854
HYDROGEN FLUORIDE 7 0 1 0 3,603 0 3,604 515
NICKEL 7 748 3,413 192,295 0 0 196,456 28,065
PHOSGENE 7 0 0 0 0 0 0 0
PYRIDINE 7 24,344 606 3,609 12,457 0 41,016 5,859
ACROLEIN 6 0 0 0 8 5,873 5,881 980
ANTIMONY COMPOUNDS 6 124 2,152 0 2,450 22,055 27,031 4,505
BIS(2-ETHYLHEXYL) ADIPATE 6 250 746 0 5 308 1,309 218
LEAD COMPOUNDS 6 2 53,692 0 213 0 53,907 8,985
M-XYLENE 6 0 237 17,143 794 884 19,058 3,176
N,N-DIMETHYLANILINE 6 52,126 0 0 1,500 120,000 173,626 28,938
P-XYLENE 6 0 1,058 0 5,260 1,402 7,720 1,287
1,2,4-TRICHLOROBENZENE 6 503 3,255 520 5,428 4,400 14,106 2,351
AMMONIUM NITRATE (SOLUTION) 5 28,800 2,530,000 0 0 0 2,558,800 511,760
CADMIUM COMPOUNDS 5 29 21,776 0 3,738 1,128 26,671 5,334
DIETHYL PHTHALATE 5 255 94 0 500 250 1,099 220
MOLYBDENUM TRIOXIDE 5 0 1,897 17,000 19,000 0 37,897 7,579
O-ANISIDINE 5 0 0 0 0 0 0 0
P-CRESIDINE 5 28,223 0 0 1,400 0 29,623 5,925
VINYL CHLORIDE 5 0 1 53,000 1,329 0 54,330 10,866
ALLYL CHLORIDE 4 0 0 0 0 0 0 0
BENZOYL PEROXIDE 4 9,980 0 0 4,620 0 14,600 3,650
BUTYL BENZYL PHTHALATE 4 158 43 0 12,943 0 13,144 3,286
CHROMIUM 4 0 0 0 21,505 0 21,505 5,376
METHYLENEBIS 4 0 0 0 13,270 0 13,270 3,318
(PHENYLISOCYANATE) 11,109 1,301 59,061 14,765
O-CRESOL 4 40,541 6,110 0
1,1,2-TRICHLOROETHANE 4 0 70 57,000 236,101 0 293,171 73,298
1,2-DICHLOROETHYLENE 4 0 0 2,100 10 0 21,110 528
1,4-DIOXANE 4 0 0 8 0 0 8 2
2-ETHOXYETHANOL 4 390,022 0 328,374 11,783 150,875 881,054 220,264
3,3'-DICHLOROBENZIDINE 4 10 5 0 250 0 265 66
4,6-DINITRO-O-CRESOL 4 0 6,630 0 4,422 1,376 12,428 3,107
ASBESTOS (FRIABLE) 3 0 28,894 0 0 0 28,894 9,631
DIAMINOTOLUENE (MIXED ISOMERS) 3 550 0 0 172 1,100 1,822 607
DICHLOROTETRAFLUOROETHANE 3 0 15 0 51 0 66 22
ISOPROPYL ALCOHOL 3 0 0 50 81,000 72,700 153,750 51,250
NITROBENZENE 3 108 420 0 8,620 5,440 14,588 4,863
PICRIC ACID 3 0 0 0 0 0 0 0
SILVER 3 0 590 35,000 0 0 35,590 11,863
SILVER COMPOUNDS 3 0 0 48,230 0 0 48,230 16,077
STYRENE OXIDE 3 0 0 0 0 0 0 0
VINYLIDENE CHLORIDE 3 169 0 0 10,519 0 40,688 13,563
1,1,2,2-TETRACHLOROETHANE 3 0 17 1 10 0 28 9
1,2-DICHLOROBENZENE 3 0 0 860 1,477 12,830 15,167 5,056
2-NITROPHENOL 3 0 0 0 4,216 4,592 8,808 2,936
2,4-DIAMINOTOLUENE 3 0 0 0 882 0 882 294
ANTIMONY 2 8,355 7,657 58,716 0 0 74,728 37,364
BROMOMETHANE 2 0 0 0 0 0 0 0
C.I. BASIC GREEN 4 2 83 0 0 0 0 83 42
C.I.FOOD RED 15 2 1,100 0 0 0 0 1,100 550
CHLOROPRENE 2 0 0 134,800 570 0 135,370 67,685
DICHLOROBENZENE (MIXED ISOMERS) 2 0 0 0 0 128 128 64
HEXACHLORO-1,3-BUTADIENE 2 0 0 0 13,750 0 13,750 6,875
HEXACHLOROBENZENE 2 0 0 1 2,503 0 2,504 1,252
MONOCHLOROPENTAFLUOROEHTANE 2 0 0 0 0 0 0 0
P-ANISIDINE 2 2 0 0 0 0 2 1
PERACETIC ACID 2 0 0 0 0 0 0 0
QUINONE 2 0 0 0 0 0 0 0
TOLUENEDIISOCYANATE 2 0 0 0 9,050 2,700 11,750 5,875
(MIXED ISOMERS)
1,2-BUTYLENE OXIDE 2 0 0 0 0 373,200 373,200 186,600
2,4-DIMETHYLPHENOL 2 0 0 0 13,000 0 17,244 8,622
2,3-DINITROPHENOL 2 0 0 0 9,000 0 9,020 4,510
3,3'-DIMETHOXYBENZIDINE 2 0 635 3,609 0 0 0 0
4,4'-METHYLENEDIANILINE 2 960 20 0 0 2,530 3,490 1,745
ACETAMIDE 1 0 0 0 98 0 98 98
ALPHA-NAPHTHYLAMINE 1 0 0 0 0 0 0 0
ALUMINUM (FUME OR DUST) 1 0 0 0 0 0 0 0
BENZIOIC TRICHLORIDE 1 0 0 0 0 0 0 0
BIS(2-CHLOROETHYL) ETHER 1 0 0 0 0 0 0 0
BROMOCHLORODIFLUOROMETHANE 1 0 0 0 0 0 0 0
C.I. BASIC RED 1 1 24 0 0 0 0 24 24
C.I. DISPERSE YELLOW 3 1 0 1,658 0 0 0 1,658 1,658
C.I. SOLVENT YELLOW 3 1 0 0 0 0 0 0 0
CADMIUM 1 0 0 0 0 0 0 0
CHLORDANE 1 51 0 0 11 0 62 62
COBALT 1 0 21 0 0 0 21 21
CUPFERRON 1 0 0 0 2,300 0 2,300 2,300
ETHYL CHLOROFORMATE 1 0 0 0 0 0 0 0
ETHYLENE THIOUREA 1 0 250 0 0 0 250 250
ETHYLENEIMINE 1 0 0 0 0 0 0 0
HEPTACHLOR 1 42 0 0 77,287 0 77,329 77,329
HEXACHLOROCYCLOPENTADIENE 1 636 0 0 4,810 0 5,446 5,446
HEXACHLOROETHANE 1 0 0 0 0 0 0 0
HYDRAZINE SULFATE 1 0 0 0 0 0 0 0
LEAD 1 0 0 0 0 0 0 0
M-DINITROBENZINE 1 0 0 0 0 0 0 0
METHYL IODIDE 1 0 27 0 230 350 607 607
METHYL ISOCYANATE 1 0 0 0 0 0 0 0
METHYLENE BROMIDE 1 0 0 0 0 0 0 0
O-DINITROBENZENE 1 0 0 0 0 0 0 0
OXY-ALKYLATED ALCOHOL 1 5 0 0 0 0 5 5
P-PHENYLENEDIAMINE 1 0 0 0 0 0 0 0
PHENYL MIXTURE 1 0 0 0 0 11,525 11,525 11,525
PHOSPHORUS (YELLOW OR WHITE) 1 0 0 0 0 0 0 0
SACCHARIN (MANUFACTURING) 1 7 840 0 0 0 847 847
TITANIUM TETRACHLORIDE 1 0 0 0 0 0 0 0
ZINC (FUME OR DUST) 1 0 0 0 0 0 0 0
1,3-DICHLOROBENZENE 1 0 0 860 570 0 1,430 1,430
1,3-DICHLOROPROPYLENE 1 0 0 0 0 0 0 0
1,4-DICHLOROBENZENE 1 0 0 0 4 0 4 4
2-NITROPROPANE 1 0 0 0 12,180 0 12,180 12,180
2,4-DIAMINOANISOLE 1 0 0 0 0 0 0 0
2,4-DINITROTOLUENE 1 0 0 0 0 300 300 300
2,6-SYLIDINE 1 0 0 0 0 0 0 0
4-NITROPHENOL 1 0 0 0 1 0 5 5
5-NITRO-O-ANISIDINE 1 5 0 0 0 0 5 5
TOTAL 417 49,074,289 12,926,499 112,849,737 20,826,187 91,051,060 286,728,608 687,599
The TRI database contains a detailed compilation of self-reported, facilityspecific chemical releases. The top reporting facilities for this sector are listed below (Exhibit 18). Facilities that have reported only the SIC codes covered under this notebook appear on the first list. Exhibit 19 contains additional facilities that have reported the SIC code covered within this report, and one or more SIC codes that are not within the scope of this notebook. Therefore, the second list includes facilities that conduct multiple operations -- some that are under the scope of this notebook, and some that are not. Currently, the facility-level data do not allow pollutant releases to be broken apart by industrial process.
Exhibit 18: Top 10 TRI Releasing Organic Chemical Manufacturing Facilitiesb
Total
TRI Releases
Rank Facility in Pounds
1 Du Pont Victoria Plant - Victoria, TX 22,471,672
2 BP Chemicals Inc. Green Lake - Port Lavaca, TX 20,650,979
3 Zeneca Specialties Mount Pleasant Plant - Mt. Pleasant, TN 13,429,259
4 Hoechst-Celanese Chemical Group Inc. Clear Lake Plant - Pasadena, TX 10,354,443
5 Du Pont Sabine River Works - Orange, TX 9,731,302
6 Merichem Co. - Houston, TX 3,832,980
7 Hoechst-Celanese Chemical Group Inc. - Bay City, TX 3,454,971
8 Union Carbide C & P CO. Institute WV Plant Ops. - Institute, WV 3,082,932
9 Aqualon - Hopewell, VA 3,007,010
10 Aristech Chemical Corp. - Haverhill, OH 2,858,009
Source: U.S. EPA, Toxics Release Inventory Database, 1993
b Being included on this list does not mean that the release is associated with non-compliance with environmental laws.
Exhibit 19: Top 10 TRI Releasing Facilities Reporting Organic Chemical Manufacturing SIC Codes to TRIc
SIC Codes Total TRI
Reported Releases in
Rank in TRI Facility Pounds
1 2819, 2869 Cytec Inc. Inc. Fortier Plant - Westwego, LA 120,149,724
2 2869, 2819, Monsanto Co. - Alvin, TX 40,517,095
2841, 2879
3 2822, 2865, Du Pont Beaumont Plant - Beaumont, TX 36,817,348
2869, 2873
4 2823, 2821, Tennessee Eastman Division - Kingsport, TN 29,339,677
2869, 2824
5 2869, 2865, Sterling Chemicals Inc. - Texas City, TX 24,709,135
2819
6 2869 Du Pont Victoria Plant - Victoria, TX 22,471,672
7 2869 BP Chemicals Inc. Green Lake - Port Lavaca, TX 20,650,979
8 2821, 2869, BP Chemicals - Lima, OH 20,620,680
2873
9 2812, 2869, Vulcan Chemicals - Cheyenne, WY 17,406,218
2813
10 2813, 2819, Coastal Chemicals Inc. - Cheyenne, WY 15,334,423
2869, 2873
Source: U.S. EPA, Toxics Release Inventory Database, 1993.
c Being included on this list does not mean that the release is associated with non-compliance with environmental laws.
IV.B. Summary of Selected Chemicals Released
The brief descriptions provided below were taken from the 1993 Toxics Release Inventory Public Data Release (EPA, 1994), the Hazardous Substances Data Bank (HSDB), and the Integrated Risk Information System (IRIS), both accessed via TOXNET.d Ammoniae (CAS: 7664-41-7)
Toxicity. Anhydrous ammonia is irritating to the skin, eyes, nose, throat, and upper respiratory system.
Ecologically, ammonia is a source of nitrogen (an essential element for aquatic plant growth), and may therefore contribute to eutrophication of standing or slow-moving surface water, particularly in nitrogen-limited waters such as the Chesapeake Bay. In addition, aqueous ammonia is moderately toxic to aquatic organisms.
Carcinogenicity. There is currently no evidence to suggest that this chemical is carcinogenic.
Environmental Fate. Ammonia combines with sulfate ions in the atmosphere and is washed out by rainfall, resulting in rapid return of ammonia to the soil and surface waters.
Ammonia is a central compound in the environmental cycling of nitrogen. Ammonia in lakes, rivers, and streams is converted to nitrate.
Physical Properties. Ammonia is a corrosive and severely irritating gas with a pungent odor.
d TOXNET is a computer system run by the National Library of Medicine that includes a number of toxicological databases managed by EPA, National Cancer Institute, and the National Institute for Occupational Safety and Health. For more information on TOXNET, contact the TOXNET help line at 800-231-3766. Databases included in TOXNET are: CCRIS (Chemical Carcinogenesis Research Information System), DART (Developmental and Reproductive Toxicity Database), DBIR (Directory of Biotechnology Information Resources), EMICBACK (Environmental Mutagen Information Center Backfile), GENE-TOX (Genetic Toxicology), HSDB (Hazardous Substances Data Bank), IRIS (Integrated Risk Information System), RTECS (Registry of Toxic Effects of Chemical Substances), and TRI (Toxic Chemical Release Inventory). HSDB contains chemical-specific information on manufacturing and use, chemical and physical properties, safety and handling, toxicity and biomedical effects, pharmacology, environmental fate and exposure potential, exposure standards and regulations, monitoring and analysis methods, and additional references.
e The reporting standards for ammonia were changed in 1995. Ammonium sulfate is deleted from the list and threshold and release determinations for aqueous ammonia are limited to 10 percent of the total ammonia present in solution. This change will reduce the amount of ammonia reported to TRI. Complete details of the revisions can be found in 40 CFR Part 372.
Nitric Acid (CAS: 7697-37-2)
Toxicity. The toxicity of nitric acid is related to its potent corrosivity as an acid, with ulceration of all membranes and tissues with which it comes in contact. Concentrated nitric acid causes immediate opacification and blindness of the cornea when it comes in contact with the eye. Inhalation of concentrated nitric acid causes severe, sometimes fatal, corrosion of the respiratory tract. Ingestion of nitric acid leads to gastric hemorrhaging, nausea, and vomiting. Circulatory shock is often the immediate cause of death due to nitric acid exposure. Damage to the respiratory system may be delayed for months, and even years. Populations at increased risk from nitric acid exposure include people with pre-existing skin, eye, or cardiopulmonary disorders.
Ecologically, gaseous nitric acid is a component of acid rain. Acid rain causes serious and cumulative damage to surface waters and aquatic and terrestrial organisms by decreasing water and soil pH levels. Nitric acid in rainwater acts as a topical source of nitrogen, preventing "hardening off" of evergreen foliage and increasing frost damage to perennial plants in temperate regions.
Nitric acid also acts as an available nitrogen source in surface water, stimulating plankton and aquatic weed growth.
Carcinogenicity. There is currently no evidence to suggest that this chemical is carcinogenic.
Environmental Fate. Nitric acid is mainly transported in the atmosphere as nitric acid vapors and in water as dissociated nitrate and hydrogen ions. In soil, nitric acid reacts with minerals such as calcium and magnesium, becoming neutralized, and at the same time decreasing soil "buffering capacity" against changes in pH levels.
Nitric acid leaches readily to groundwater, where it decreases the pH of the affected groundwater. In the winter, gaseous nitric acid is incorporated into snow, causing surges of acid during spring snow melt. Forested areas are strong sinks for nitric acid, incorporating the nitrate ions into plant tissues.
Methanol (CAS: 67-56-1)
Toxicity. Methanol is readily absorbed from the gastrointestinal tract and the respiratory tract, and is toxic to humans in moderate to high doses. In the body, methanol is converted into formaldehyde and formic acid. Methanol is excreted as formic acid. Observed toxic effects at high dose levels generally include central nervous system damage and blindness. Long-term exposure to high levels of methanol via inhalation cause liver and blood damage in animals.
Ecologically, methanol is expected to have low toxicity to aquatic organisms.
Concentrations lethal to half the organisms of a test population are expected to exceed one mg methanol per liter water. Methanol is not likely to persist in water or to bioaccumulate in aquatic organisms.
Carcinogenicity. There is currently no evidence to suggest that this chemical is carcinogenic.
Environmental Fate. Liquid methanol is likely to evaporate when left exposed. Methanol reacts in air to produce formaldehyde which contributes to the formation of air pollutants. In the atmosphere it can react with other atmospheric chemicals or be washed out by rain. Methanol is readily degraded by microorganisms in soils and surface waters.
Physical Properties. Methanol is highly flammable
Ethylene Glycol (CAS: 74-85-1)
Sources. Ethylene glycol is used as an antifreeze, heat transfer agent and solvent in industrial organic chemical facilities. The large quantity of ethylene glycol released is due to its ubiquitous use as an antifreeze and because in 1993 it had the 29th largest chemical production volume in the United States (Chemical and Engineering News). While the largest volume is released through underground injection, a substantial release also occurs from air point sources.
Toxicity. Long-term inhalation exposure to low levels of ethylene glycol may cause throat irritation, mild headache and backache. Exposure to higher concentrations may lead to unconsciousness. Liquid ethylene glycol is irritating to the eyes and skin.
Toxic effects from ingestion of ethylene glycol include damage to the central nervous system and kidneys, intoxication, conjunctivitis, nausea and vomiting, abdominal pain, weakness, low blood oxygen, tremors, convulsions, respiratory failure, and coma. Renal failure due to ethylene glycol poisoning can lead to death.
Environmental Fate. Ethylene glycol readily biodegrades in water. No data are available that report its fate in soils; however, biodegradation is probably the dominant removal mechanism. Should ethylene glycol leach into the groundwater, biodegradation may occur.
Ethylene glycol in water is not expected to bioconcentrate in aquatic organisms, adsorb to sediments or volatilize. Atmospheric ethylene glycol degrades rapidly in the presence of hydroxyl radicals.
Acetone (CAS: 67-64-1)
Toxicity. Acetone is irritating to the eyes, nose, and throat. Symptoms of exposure to large quantities of acetone may include headache, unsteadiness, confusion, lassitude, drowsiness, vomiting, and respiratory depression.
Reactions of acetone (see environmental fate) in the lower atmosphere contribute to the formation of ground-level ozone. Ozone (a major component of urban smog) can affect the respiratory system, especially in sensitive individuals such as asthmatics or allergy sufferers.
Carcinogenicity. There is currently no evidence to suggest that this chemical is carcinogenic.
Environmental Fate. If released into water, acetone will be degraded by microorganisms or will evaporate into the atmosphere. Degradation by microorganisms will be the primary removal mechanism.
Acetone is highly volatile, and once it reaches the troposphere (lower atmosphere), it will react with other gases, contributing to the formation of ground-level ozone and other air pollutants. EPA is reevaluating acetone's reactivity in the lower atmosphere to determine whether this contribution is significant.
Physical Properties. Acetone is a volatile and flammable organic chemical.
IV.C. Other Data Sources
The toxic chemical release data obtained from TRI captures the vast majority of facilities in the organic chemicals industry. It also allows for a comparison across years and industry sectors. Reported chemicals are limited however to the 316 reported chemicals. Most of the hydrocarbon emissions from organic chemical facilities are not captured by TRI.1 The EPA Office of Air Quality Planning and Standards has compiled air pollutant emission factors for determining the total air emissions of priority pollutants (e.g., total hydrocarbons, SOx, NOx, CO, particulates, etc.) from many chemical manufacturing sources.2
The EPA Office of Air’s Aerometric Information Retrieval System (AIRS) contains a wide range of information related to stationary sources of air pollution, including the emissions of a number of air pollutants which may be of concern within a particular industry. With the exception of volatile organic compounds (VOCs), there is little overlap with the TRI chemicals reported above. Exhibit 20 summarizes annual releases of carbon monoxide (CO), nitrogen dioxide (NO2), particulate matter of 10 microns or less (PM10), total particulate (PT), sulfur dioxide (SO2), and volatile organic compounds (VOCs).
Exhibit 20: Pollutant Releases (short tons/year) Industry Sector CO NO2 PM10 PT SO2 VOC Metal Mining 5,391 28,583 39,359 140,052 84,222 1,283 Nonmetal Mining 4,525 28,804 59,305 167,948 24,129 1,736 Lumber and 123,756 42,658 14,135 63,761 9,419 41,423 Wood Production Furniture 2,069 2,981 2,165 3,178 1,606 59,426 and Fixtures Pulp and Paper 624,291 394,448 35,579 113,571 541,002 96,875 Printing 8,463 4,915 399 1,031 1,728 101,537 Inorganic Chemicals 166,147 103,575 4,107 39,062 182,189 52,091 Organic Chemicals 146,947 236,826 26,493 44,860 132,459 201,888 Petroleum Refining 419,311 380,641 18,787 36,877 648,155 369,058 Rubber and 2,090 11,914 2,407 5,355 29,364 140,741 Misc. Plastics Stone, Clay and 58,043 338,482 74,623 171,853 339,216 30,262 Concrete Iron and Steel 1,518,642 138,985 42,368 83,017 238,268 82,292 Nonferrous Metals 448,758 55,658 20,074 22,490 373,007 27,375 Fabricated Metals 3,851 16,424 1,185 3,136 4,019 102,186 Computer and Office 24 0 0 0 0 0 Equipment Electronics and Other 367 1,129 207 293 453 4,854 Electrical Equipment and Components Motor Vehicles, 35,303 23,725 2,406 12,853 25,462 101,275 Bodies, Parts and Accessories Dry Cleaning 101 179 3 28 152 7,310 Source: U.S. EPA Office of Air and Radiation, AIRS Database, May 1995.
complete file source: http://es.epa.gov/oeca/sector/sectornote/pdf/organic.pdf 2mar02
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