GCA-TR-75-32-G(14) ASSESSMENT OF PHTHALIC ANHYDRIDE AS A POTENTIAL AIR POLLUTION PROBLEM VOLUME XIV FINAL REPORT Contract No. 68-02-1337 Task Order No. 8 Prepared For U.S. ENVIRONMENTAL PROTECTION AGENCY Research Triangle Park North Carolina 27711 January 1976 GCA/TECHNOLOGY DIVISION BEDFORD, MASSACHUSETTS 01730 ------- GCA-TR-75-32-G(14) ASSESSMENT OF PHTHALIC ANHYDRIDE AS A POTENTIAL AIR POLLUTION PROBLEM: Volume XIV by Robert M. Patterson Mark I. Bornstein • Eric Garshick GCA CORPORATION. GCA/TECHNOLOGY.DIVISION Bedford,. 'Massachusetts January 1976 Contract No. 68-02-1337 . Task Order No. 8 EPA Project Officer Michael Jones EPA Task Officer Justice Manning U.S. ENVIRONMENTAL PROTECTION AGENCY Research Triangle Park North Carolina 27711 : ------- This report wns furnished to the U.S. Environmental Protection Agency by the GCA Corporation, GCA/Tcchnology Division, Bedford, Massachusetts 01730, in fulfillment of Contract No. 68-02-1337, Task Order No. 8. The opinions, findings, and conclusions expressed are those of the authors and not neces- sarily those of the U.S. Environmental Protection Agency or of the cooperating agencies. Mention of company or product names is not to be considered as an endorsement by the U.S. Environmental Protection Agency. ------- ABSTRACT This report is one of a series which assesses the potential air pollution impacts of 14 industrial chemicals outside the work environment. Topics covered in each assessment include physical and chemical properties, health and welfare effects, ambient concentrations and measurement meth- ods, emission sources, and emission controls. The chemicals investigated in this report series are: Acetylene Methyl Alcohol Ethylene Dichloride Benzene Acetone Acrylonitrile Cyclohexanone Formaldehyde Methyl Methacrylat** Ortho-Xylene Maleic Anhydride Dimethyl Terephthalate Adipic Acid Phthalic Anhydride. Volume I Volume II Volume III Volume IV Volume V Volume VI Volume VII Volume VIII Volume IX Volume X Volume XI Volume XII Volume XIII Volume XIV iii ------- CONTENTS Page Abstract ill List of Tables v Sections I Summary and Conclusions 1 II Air Pollution Assessment Report 3 Physical and Chemical Properties 3 Health and Welfare Effects 3 Ambient Concentrations and Measurements 6 Sources of Phthalic Anhydride Emissions 9 Phthalic Anhydride Emission Control Methods 12 III References 15 Appendix A Phthalic Anhydride Manufacturers 17 iv ------- TABLES No. Page 1 Significant Properties of Phthalic Anhydride 4 2 Phthalic Anhydride Consumption - 1974 10 3 Sources and Emission Estimates of Phthalic Anhydride - 1974 10 4 Water Scrubber and Incinerator 12 5 Direct Incineration 13 6 Incineration and Waste Heat Boiler 13 ------- SECTION I SUMMARY AND CONCLUSIONS Phthalic anhydride is a white, crystalline solid with a characteristic choking odor. It is produced by the oxidation of either naphthalene or ortho-xylene, and it is a key industrial intermediate in the manu- facture of resins, polyesters, dyes, and plasticizers. The major acute toxic effect of exposure to phthalic anhydride dust or vapor is its irritating action on the skin, eyes, and mucous membranes. 3 A concentration of 25 mg/m (4.2, ppm) will cause mucous membrane irri- tation. There is no record of serious injury due to acute exposure. Phthalic anhydride dust or vapor in contact with moist skin will form free phthalic acid. The U.S. occupational standard for exposure is 3 12 mg/m (2 ppm) for an 8-hour time weighted average. Simple diffusion modeling estimates place the likely maximum 1-hour 3 average ambient concentration at about 0.7 mg/m , with a 24-hour aver- age of about 0.3 mg/m . About 1 billion pounds of phthalic anhydride were produced at 16 loca- tions in 1974, and production is expected to increase 6 percent per year through 1978. The primary end use is the manufacture of plasti- cizers, with polyester resin production second. The major emission sources in descending order are product storage, manufacturing, end product manufacturing, and product handling. Total emissions are estimated to have been about 5 million pounds in 1974. ------- Scrubbers and incinerators are currently being used by industry to con- trol phthalic anhydride emissions wit:h efficiencies of 86 and 99 percent, respectively. The product is stored in the molten state and blanketed with dry nitrogen to prevent fire and hydrolysis to phthalic acid. Cur- rently used practices to control the continuous gaseous effluent are the use of knock-out pots for removal of solid phthalic anhydride and the venting of storage tanks to the main process vent gas incinerator. Based on the results of the health effects research presented in this report, and the ambient concentration estimates, phthalic anhydride as an air pollutant apparently does not pose a threat to the health of the general population. In addition, phthalic anhydride does not appear to pose other environmental insults which would warrant further investiga- tion or restriction of its use at the present time. ------- SECTION II AIR POLLUTION ASSESSMENT REPORT PHYSICAL AND CHEMICAL PROPERTIES Phthalic anhydride is a white, crystalline solid with a characteristic choking odor. It is manufactured by the oxidation of either naphtha- lene or ortho-xylene. Phthalic anhydride is a key industrial interme- diate in the manufacture of resins, polyesters, dyes, and plasticizers. Significant properties are given in Table 1. HEALTH AND WELFARE EFFECTS Effects on Man Acute Poisoning - The major acute toxic effect of exposure to phthalic anhydride dust or vapor results from its marked irritating properties on the skin, eyes, and mucous membranes of the nose and respiratory tract. A concentration of 25 mg/m (4.2 ppm) causes some mucous mem- brane irritation. A concentration of 30 mg/m (5.0 ppm) causes defi- nite conjunctival irritation as well as increased mucous membrane irritation. Symptoms of exposure to such concentrations include coughing, sneezing, a burning sensation in the throat and increased 2 3 mucous secretion. ' Continued exposure or exppsure to higher levels may result in general respiratory tract irritation, nasal ulceration and bleeding, loss of smell, and hoarseness. Pulmonary sensitization 2 and allergic reaction is possible. However, there is no record of 4 serious injury due to short exposures to high concentrations. ------- Table 1. SIGNIFICANT PROPERTIES OF PHTHALIC ANHYDRIDE Synonyms phthalic acid anhydride, phthalandione, 1, 2-benzcnc dicarboxylic acid anhydride Chemical formula Molecular weight Boiling point Melting point Specific gravity Vapor pressure Solubility Minimum explosive concentration Explosive limits Ignition temperature Flash point At 25°C and 760 mm Hg 148.11 284.5°C (sublimes) 130.8°C 1.527 (4°C) 1.4 mm Hg at 110°C 42 mm Hg at 180°C Soluble in ethanol, benzene Slightly soluble in water, ethyl ethers, carbon disulfide 16.5 g/m3 1.77. at 140°C 10.5% at 193°C 584°C 151°C 2 1 ppm vapor = 6.0 mg/m 1 mg/r'3 =0.17 ppm ------- Phthalic anhydride dust and vapor ;irc particularly irritating to moist skin as a result of the formation of free phthalic acid. Contact pro- duces redness and chapping, with urtjcaria possible. It is a skin sen- sitizing agent." The worst symptom of eye irritation is a persistent conjunctivitis, with no permanent injury resulting. Chronic Poisoning - Workers chronically exposed to phthalic anhydride vapors or dust suffered from aggravated, acute exposure symptoms. Clinical findings included atrophy of the nasal mucous membrane (reversible), sometimes with blood-stained discharge, irritation of the larynx, and hoarseness and cough, and sometimes with blood-stained sputum. Bronchitis, irritation of the gastric mucous membrane with loss of appetite and weight, and asthma and allergic rhinitis (inflam- mation of the nose lining) due to sensitization have been seen. The allergy can develop such that lower doses of phthalic anhydride can no longer be tolerated. Direct dose-response data for chronic exposure are lacking in the literature. The U.S. occupational standard for ex- >- I o posure is a 12 mg/m (2 ppm) 8-hour time weighted average, based on human sensory response. Effects on Animals Acute Poisoning - Animal response to acute exposure has not been well documented in the literature. On the basis of available data, mucous membrane irritation, eye irritation and related symptoms would occur in animals at concentrations above 30 mg/m (5.0 ppm). Sensory re- sponse and exposure symptoms would be the same as those seen in humans. Values for the acute oral DD,n in the rat have been reported as high as ' 12 2,500 to 5,000 mg/kg, and as low as 800 to 1,600 mg/kg body weight. ' Death after ingcstion was due to tubular necrosis (cell death) of the kidney. In cats the LD_0 is 800 me/kg, and for guinea pigs it is 100 mg/kg. ------- Chronic Poisoning - Cats exposed to 3,700 nig/m (617 ppm) for 6 hours a day for 7 days became drowsy, showed a loss of appetite, and vomited, Liver and kidney damage was seen. Rats and rabbits exposed to 10,000 4 3 mg/m (1,667 ppm) for 4 hours per day for several days experienced 25 percent fatalities.' Skin scnsitization in guinea pigs has been illustrated by the intracu- taneous injection of 20 mg-of phthalic anhydride dissolved in dioxane and olive oil twice a week for 2 weeks. Animals tested 2 weeks after 0 the last injection were markedly sensitized. Effects on Vegetation The effects of phthalic anhydride on plants have not been documented in the literature. Other Effects The dust and vapors form explosive mixtures with air. The lower explo- sive limit is 1.7 percent and the upper explosive limit is 10.A percent, The flash point by closed cup method is 151 C. AMBIENT CONCENTRATIONS AND MEASUREMENTS Ambient Concentration Estimates The largest emission source of phthalic anhydride is a production facility with a capacity of 130 million pounds per year. This facil- ity is located near Chicago, which IMS a population of over 3 million. The emission factor for phthalic anhydride is 0.0017 pound per pound produced. ------- Hence, the emission rate is (0.0017 emission factor) (130 x 1Q6 Ib/yr) (453.6 g/lb) 3.1536 x 107 sec/yr = 3.2 g/sec of phchalic anhydride. Some assumptions must be made regarding this chemical release to the atmosphere. First of all, the emissions do not all come from one source location, but rather from a number of locations within the plant where phthalic anhydride leaks to the atmosphere. Thus, the emissions can be characterized as coming from an area source which will be taken to be 100 meters on a side. Secondly, the emissions occur at different heights, and an average emission height of 10 meters is assumed. Ground level concentrations can then be estimated at locations downwind of the facility. To do this, a virtual point source of emission is assumed upwind of the facility at a distance where the initial horizontal dispersion coefficient equals the length of a side of the area divided by A.3. In this case: o = 100m/A.3 = 23.3m. yo Assuming neutral stability conditions (Pasquill-Gifford Stability Class D) with overcast skies and light winds, the upwind distance of the virtual point source is approximately 310 meters. With consideration of the plant boundary, it is reasonable to assume that the nearest receptor location is thus 500 meters from the virtual point source. Finally, taking 2 m/sec as an average wind speed, the ground level concentration may be calculated from: ------- -ft)1 3 2 -1/2 or X = (2) ir (36) (18.5) e U8'5 !'0.66 mg/m for a 10-minute average concentration. Over a period of an hour this 3 becomes 0.66 (0.72) = 0.48 mg/m (or 0.08 ppm vapor) 1-hour average concentration. Over a 24-hour period, the average concentration might 3 roughly be expected to be about 0.26 mg/m (0.04 ppm vapor). Phthalic Anhydride Measurement Techniques Phthalic anhydride present as an airborne particulate should be collected on Whatman No. 1 filter paper or on a glass filter. For the collection of vapor or fumes, two gas washing bottles or bubblers in series contain- 3 ing appropriate absorbing solutions such as ethanol or 0.1 N HC1 are used. Three methods are available for the determination of the concentration of phthalic anhydride in air: colorimetric, ultraviolet absorption, and gas chromatography. However, only gas chromatography is suitable for ambient concentrations. In the colorimetric method phthalic anhydride is extracted from the filter paper using benzene. The sample is dried, treated with hydro- quinone and sulfuric acid, left alone for 2 hours, and then diluted with water and benzene. An aliquot of the water layer is treated with potas- sium hydroxide and ascorbic acid. The absorbence of the aqueous layer ------- is then measured on a spcctrophoLomeLer at 560 my and compared to a standard curve. Concentrations in the range of 80 ppm have been de- termined by this method. The ultraviolet absorption method involves the extraction of phthalic anhydride in 0.1 N HC1. The absorbency of the resulting solution is measured at 275 my and compared to a standard calibration curve. Con- centrations detected by this method are similar to those of the colori- metric method. The gas chromatograph method, which is used when small sample volumes are available, is the most accurate of the three methods. Concentra- tions as low as 1 ppb can be detected if used in conjunction with a 12 flame ionization detector. SOURCES OF PHTHALIC ANHYDRIDE EMISSIONS Phthalic Anhydride Production and Consumption The production of phthalic anhydride in 1974 is estimated to have been 1,030 million pounds, and it is expected to increase at 6 percent per year through 1978. Phthalic anhydride is primarily used in the pro- duction of plasticizers, accounting for 50 percent of total production. Alkyd resins and polyester resins account for a major portion of the remaining production. Twelve companies at 16 locations are manufactur- ing phthalic anhydride as listed in Appendix A. The consumption of phthalic anhydride for final produces is shown in Table 2. This table also presents the expected growth r.ites for each sector of the market. ------- Table 2. PHTHALIC ANHYDRIDE CONSUMPTION - 1974 Flastlclzers Alkyd resins Polyester resins Export and miscellaneous Total Million pounds 515.0 195.7 247.2 72.1 1,030.0 % Annual growth 6 0 15 Variable 6% Phthalic Anhydride Sources and Emission Estimates Primary sources of emissions of phthalic anhydride result from phthalic anhydride production, bulk storage and handling, and end product manu- facture. Total emissions from all categories are estimated to be 4.86 million pounds, representing 0.5 percent of total production. See Table 3. Table 3. SOURCES AND EMISSION ESTIMATES OF PHTHALIC ANHYDRIDE - 1974 Source Million pounds Phthalic anhydride manufacturing Product handling Product storage End product manufacturing Total 1.56 0.10 1.64 1.56 4.86 Phthalic anhydride is produced from two raw materials, naphthalene and ortho-xylene. Ortho-xylene account:; for 54 percent of production and 14 naphthalene for the remaining 46 percent. 10 ------- Emissions from Che manufacturing of phthalic anhydride occur from process reactors and vents, product handling, and product storage. A recent study of phthalic anhydride production has estimated losses from reactors and 14 vents. An emission rate of 0.0017 ,md 0.0013 ton of phthalic anhydride per ton of phthalic anhydride produced from the ortho-xylene and naphtha- lene processes, respectively, have been reported. Using these factors, and the corresponding production rate from each process, will result in 0.96 million and 0.60 million pounds, respectively, emitted from the ortho-xylene and naphthalene processes. These emission rates are based on extensive controls already in use by the industry. Product handling losses, estimated from the same report, are based on 90 percent of the product sold in the molten state, and the remaining 10 percent sold as a solid flake. It is estimated that 0.0001 ton of product is lost per ton of phthalic anhydride produced. This results in 0.01 million pounds lost from the bagging operation and 0.09 million pounds lost from truck loading of molten product. Phthalic anhydride is stored in fixed roof storage tanks in the molten state (149°C). The reported emission factor is 0.0016 ton emitted per 14 ton of product stored. There'f< mated to be 1.64 million pounds. ton of product stored. Therefore, losses from bulk storage are esti- The last major source of phthalic anhydride emissions results from the production of end products. The literature does not contain any data on the emission rates from these processes. It is, therefore, estimated that the emission rates are the same as the emission rates for the pro- duction of phthalic anhydride. Emissions from end product manufacturing are estimated to be 1.56 million pounds. 11 ------- PHTHALIC ANHYDRIDE EMISSION CONTROL METHODS Two types of control devices — scrubbers and incinerators — are currently 14 being used by the industry. In a recent study it was reported that these two control methods are used extensively in the manufacture of phthalic anhydride. The main source of emissions from the ortho-xylene process occurs from the main process vent gas stream. The main source of emissions from the naphthalene process occurs from the switch-condenser vent. Depending on the plant, one or two types of control devices may be used: scrubbers and/or incinerators. The water scrubber is reported to have an efficiency of 86 percent, and the incinerator has a reported 14 99 percent efficiency. Cost data for the various systems are presented in Tables 4, 5, and 6. Table 4. WATER SCRUBBER AND INCINERATOR a, 14 Feed gas, Ib/hr Gaseous effluent, Ib/hr Gaseous effluent, SCFM Total capital investment, $ Total operating cost, $ Net annual cost, $ Emission control efficiency Water scrubber 536,962 544,005 122,100 1,398,000 335,000 86% Incinerator 10,460 39,235 9,700 444,800. 198,900 533,900C 99%d Costs updated to first quarter 1975. Includes depreciation, interest charges, maintenance, labor and utilities. £ Combined annual cost: water scrubber with incinerator. Combined efficiency: water scrubber with incinerator. 12 ------- Table 5. DIRECT INCINERATION' ,a,l4 Feed gas, Ib/hr Gaseous effluent, Ib/hr Gaseous effluent, SCFM Total capital investment, $ Total operating cost, $ Net annual cost, $ Emission control efficiency 536,962 540,052 120,200 1,093,000 502,000 502,000 92% Costs updated to first quarter 1975. Includes depreciation, interest charges, mainte- nance, labor and utilities. Table 6. INCINERATION AND WASTE HEAT BOILER' a,14 Feed gas, Ib/hr Gaseous effluent, Ib/hr Gaseous effluent, SCFM Total capital investment, $ Total operating cost, $ f* Steam production (credit), $ Net annual cost, $ Emission control efficiency 536,962 545,767 122,350 1,589,000 1,101,000 591,000 510,000 92% Costs updated to first quarter 1975. Includes depreciation, interest charges, mainte- nance, labor and utilities. C$0.59/thousand pounds (450 psig, 750°F). 13 ------- Most production plants store phthalic anhydride in the molten state and maintain it at 149°C. In several cases, the tanks are blanketed with dry nitrogen to prevent the entry of oxygen (fire) or water vapor (hydrolysis to phthalic acid). Consequently, there is a continuous gaseous effluent. Current control practices are the use of knock-out pots (settling and/or impactor chambers) for removal of solid phthalic anhydride and the venting of storage tanks to the main process vent gas incinerator. No cost data are available for these processes, but it is expected that capital and operating costs would be fairly low. ------- SECTION III REFERENCES 1. Baader, E. W. Illnesses Caused by Phthalic Acid and Its Compounds. Arch f Gewerbepath u Gewerbehyg. 13:419-53, 1955. Summary in Bull Hyg. 30:699-700, 1955; and Pub Health Eng Abstr. 35:9-10, 1955. 2. Fassett, D. W. Organic Acids and Related Compounds. In: Industrial Hygiene and Toxicology, Patty, F. A. (ed.). Vol. 2. New York, Inter- science Publishers, 1963. p. 1822-23. 3. American Industrial Hygiene Association. Hygienic Guide Series: Phthalic Anhydride. Amer Ind Hyg Assoc J. 28:395-98, 1967. 4. Fairhall, L. T. Industrial Toxicology. 2nd Edition. New York, Hafner Publishing Co., 1909. p. 322-23. 5. Kern, R. A. Asthma and Allergic Rhinitis Due to Sensitization to Phthalic Anhydride. J Allergy. 10:164-65, 1939. 6. Gervais, P. Asthma in the Plastics Industry. Connais Plast. 7:20-22, 1966. Cited in: Chemical Abstracts 66:49043t, 1967. 7. The NIOSH Toxic Substances List - 1974 Edition. U.S. Department of Health, Education and Welfare. Publication No. (NIOSH) 74-134. p. 621. 8. Jacobs, J. L., T. S. Golden, J. J. Kelley. Immediate Reactions to Anhydrides, of Wheal and Erythema Type. Proc Exp Biol Med. 43:74-77, 1940. 9. Monsanto Material Data Sheet. Form No. OSHA-20. May 1971. 10. Turner, D. B. Workbook ,of Atmo&pheric Dispersion Estimates. U.S. En- vironmental Protection Agency. Report No. AP-26. April 1973. 11. Kesy, I. The Determination of Phlhalic Anhydride in the Air. In: Proceedings - Thirteenth International Congress on Occupational Health. New York. 1960. 15 ------- 12. Leithe, W. The Analysis of Air Pollution. Ann Arbor-Humphrey Science Publishers, 1970. 13. Chemical Profiles. Schnell Publishing Co., July 1974. 14. Phthalic Anhydride Manufacture from Ortho-xylene. U.S. Environ- mental Protection Agency. Publication No. EPA-450/3-73-006g. 1975. 16 ------- APPENDIX A PHTHALIC ANHYDRIDE MANUFACTURERS 14 Allied Chemical Allied Chemical Allied Chemical BASF Wyandotte Exxon Chemical Co. W. R. Grace Koppers Co. Koppers Co. Monsanto Co. Monsanto Co. Reichhold Chemicals Sherwin-Williams Standard Oil of California Stepan Chemical Co. Union Carbide Corp. United States Steel Corp. Total El Segundo, Calif. Philadelphia, Pa. Ironton, Ohio Kearny, N. J. Baton Rouge, La. Fords, N. J. Bridgeville, Pa. Chicago, 111. Bridgeport, N. J. Texas City, Tex. Morris, 111. Chicago, 111. Richmond, Calif. Millsdale, 111. Institute, W. Va. Pittsburgh, Pa. Capacity, million pounds/year 40 100 33 130 90 75 95 130 80 130 100 20 50 50 75 125 1,323 17 ------- TECHNICAL REPORT DATA (Please read Instructions on the re- crse before completing) i. REPORT NO. 2. 3. RECIPIENT'S ACCESSIOftNO. 4. TITLE AND SUBTITLE Assessment of Phthalic Anhydride as a Potential Air Pollution Problem 5. REPORT DATE January 1976 6. PERFORMING ORGANIZATION CODE 7. AUTHOR(S) Robert M. Patterson Mark I. Bornstein Eric Garshick 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT NO. GCA Corporation GCA/TECHNOLOGY DIVISION Bedford, Massachusetts 11. CONTRACT/GRANT NO. 68-02-1337 12. SPONSORING AGENCY NAME AND ADDRESS Environmental Protection Agency Office of Air and Waste Management Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 13. TYPE OF REPORT AND PERIOD COVERED Final 14. SPONSORING AGENCY CODE 16. SUPPLEMENTARY NOTES 16. ABSTRACT This report is one of a series which assesses the potential air pollution impacts of 14 industrial chemicals outside the work environment. Topics covered in each assessment include physical and chemical properties, health and welfare effects, ambient concentrations and measurement methods, emission sources, and emission controls. The chemicals investigated in this report series are: Volume I Volume II Volume III Volume IV Volume V Volume VI Volume VII Acetylene Methyl Alcohol Ethylene Dichloride Benzene Acetone Acrylonitrile Cyclohexanone Volume VIII Volume IX Volume X Volume XI Volume XII Volume XIII Volume XIV Formaldehyde Methyl Methacrylate Ortho-Xylene Maleic Anhydride Dimethyl Terephthalate Adi pic Acid Phthalic Anhydride 17. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS COSATI Field/Group Phthalic Anhydride Ambient Concentrations Health Effects Measurement Methods Emission Sources Emission Controls Industrial Chemicals Physical Properties Chemical Properties Welfare Effects Phthalic Anhydride Air Pollution Assessment Air Pollution Control Organic Chemicals IB. DISTRIBUTION STATEMENT 19. SECURITY CLASS (Thu Report) 21. NO. OF PAGES Unlimited 20. SECURITY CLASS (Thispage) Unclassified 22. PRICE EPA Form 2220-1 (9-73) ------- |