Document Ex05BQ40ORaEzoZne3MZe54oV

s c ^Oo c>J*y Lu^ht*' PROCESS EMISSIONS OF PLASTIC OPERATIONS Protocols for Source Sampling of Organic Gases Generated during Plastic Processes FINAL REPORT TO: The Society of the Plastics Industry, Inc. Nick R. Schott, Ph.D. Rafael Moure-Eraso, Ph-D., CIH Michael J. Ellenbecker, Sc.DM CIH Jan Chang Huang, Pb.D. University of Massachusetts Lowell Work Environment Department Plastics Engineering Department July 18, 1992 ULRF Project No. 09-5381 21574001 BFG15301 1 TABLE OF CONTENTS Executive Summary I. Introduction A. Objectives and scope of the study B. Review of the Literature 1 1 3 II. Materials and Methods 5 A. Description of Machinery and Operating Conditions 5 B. Description of Plastic Raw Materials Used 6 C. Description of Collection and Analytical Methods 6 1. GC/MS 2. Aldehydes 3. Organic Acids fl 4. Aerosols 5. Hydrochloric Add 7 8 8 9 11 III. Results 12 A. Organic Emissions Identified byProcess 12 B. Organic Emissions Identified by Polymer 13 1. Polystyrene 2. Polyethylene 3. Aaylonitrile-butadiene-styrene 4. Polyvinyl Chloride 5. Unsaturated Polyester 15 16 18 18 19 C Aerosol Emissions Identified by Polymer 19 IV. Conclusions 21 ^ BFG15302 V. References VI. Tables VII. Appendixes Appendix A Appendix B Appendix C Appendix D Figures 1-8 (Sampling Locations) ESA Analysis/Detection Limits Analytical Methods Calibration Methods 22 25 48 21574003 BFG15303 EXECUTIVE SUMMARY The objective of these experiments was to identify the best collection and analytical techniques available to conduct source sampling during plastics processing, and use them to prepare sampling protocols. Source samples of emissions from polymers in various processes were obtained in order to choose a set of target substances that would be representative of emissions in industrial settings. The study of previously published reports and the detection of emissions from seven plastic processes and five polymers permitted a reasonable basis to choose the target substances. The target substances recommended to be routinely sampled from five commercial grade plastic materials studied were : for polystyrene (PS): styrene, ethylbenzene, toluene and benzene; for polyethylene (PE): formaldehyde, formic acid and benzene; for acrvlonitrile-butadiene-stvrene (ABS): styrene, xylene, toluene and acrylonitrile; for polyvinyl chloride (PVC): `vinyl chloride, "hydrochloric acid, benzene and toluene; and for unsaturated polyester bulk molding compound (BMC): styrene. Solid condensation aerosols were also measured in most experiments, therefore total aerosols were also recommended for routine sampling of process emissions. Criteria for selection of target substances were: positive identification, being present above ten times the detection limit of the analytical method and having regulatory interest (Note: compounds marked with an asterisk were sampled but not detected in these experiments but are nonetheless recommended for routine sampling). These initial procedures represent the necessary preliminary steps to be the basis for a complete protocol to quantify emissions to be used by the plastics industrial processor. The methods of collection were standard industrial hygiene sampling methods. Analysis was conducted by a commercial analytical laboratory accredited by the American Industrial Hygiene Association (AIHA) and the Commonwealth of Massachusetts. Samples were taken for seven basic plastic processes and one compounding operation as follows: Extrusion processes: strand ; sheet; blown film and extrusion coating. Injection molding. Thermoforming and Compression Molding, (including a compounding operation). The focus of the process emissions evaluated in this project is the emissions generated by the melting of the polymer per se. Emissions originated from additives (e.g., stabilizers, chain transfer additives, plasticizers and colorants) may appear in the results but are not the focus of this study. The methods described here are only suitable to evaluate emissions of thermoplastic processes where the polymers are melted in a normal steady state operation or the compounding and cure of the thermoset polyester. Non-steady state operations, such as purging may generate additional decomposition products of industrial hygiene interest. Their generation during plastic production should be evaluated but their collection and analysis were beyond the scope of this study. BFG15304 21^ /4004 A. Objectives, and Scope I. INTRODUCTION This report presents the results of the first phase of the development of a protocol to characterize emissions generated during plastic processes. The initial task in this project was to identify and perform quantitative analysis on selected organic vapors and measure gravimetrically aerosols generated from some plastic processes. The emissions were collected at the peak off-gassing stage of the plastic production cycle. The sampling strategy consisted of the collection of source sampling using industrial hygiene sampling collection equipment on industrial size plastics production machinery at the University of Massachusetts Lowell. The collection and analytical methods described here could be generalized and applied to the identification and relative quantification of organic vapors and aerosols originated from a plastic melt Once a broad spectrum of organic chemicals was identified and their relative concentrations determined, a decision was made to choose target substances suitable for quantification of emissions. These choices were based on two criteria; i.e., the relative amounts produced and the regulatory interest of the substances identified. This initial work is the necessary preliminary steps to be the basis for a complete protocol to quantify emissions to be used by the plastics processor. The methods of collection were standard industrial hygiene sampling methods. Analyses were conducted by a commercial analytical laboratory accredited by the American Industrial Hygiene Association (AIHA) and the Commonwealth of Massachusetts. The objective of this arrangement was to make these procedures available to any plastics processor on a routine basis. 1 21574005 BFG15305 Samples were taken for seven basic plastic processes and one compounding operation as follows: Extrusion processes: strand ; sheet; blown film and extrusion coating, Injection molding. Thermoforming and Compression Molding (including a compounding operation). Five commercially available plastic materials were used for different processes. They were: polystyrene (PS), polyethylene (PE) (high density polyethylene (HDPE) and linear low density polyethylene (LLDPE)), aciylonitrile-butadiene-styrene (ABS), polyvinyl chloride (PVC) and unsaturated polyester BMC (UP). A total of 30 sample sets were collected to identify organic chemicals through gas chromatography/mass spectrometry (GC/MS) methods. These identified a grand total of 76 quantifiable analytes (relative to a MS calibrating chemical). Two additional sample sets were collected to identify oxygenated compounds from PE extrusion. The analytical technique for these two last sets was High Pressure Liquid Chromatography /Ultra Violet (HPLC/UV). Eight quantifiable aldehydes and organic acids were identified. Aerosols generated from some processes were measured gravimetrically as total aerosols (15 samples) and benzene soluble aerosols (17 samples) for a total of 32 aerosol samples. The focus of this project was the emissions generated by the melting of the polymer per se. Emissions originated from additives (e.gn stabilizers, chain transfer additives, plasticizers and colorants) may appear in the results but are not the focus of this study. Their generation is not discussed in this report, since their chemical nature and purpose was not identified to the researchers in any of the commercial grade polymers used in the experiments. The methods described here are suitable to evaluate emissions of thermoplastic processes where the polymers are melted in a normal steady state operation 2 BFG15306 74006 Table X Mass Percentages of Vapors Collected Based on Amounts of Selected1 PVC Organics Steady State Material Flow Rate (kg/hr) Highest Operating Temperature (F) Effluents Identified Benzaldehyde Trimethyldecane Acetic Acid-ethyl hexyl ester Benzene Ethylbenzene Tetrachloroethylene Toluene Xylenes (total) 1-Octanol Decane,2,9-Dixnethyl Undecane,2,10-Dimethyl Octacosane Styrene Trichloroethylene Oxirane {(2-Ethyl Hexyl) oxy) Methyl)} l-Pentanol,23. Dimethyl Extrusion Strand 15 355 % nd nd nd 0.4 0.1 nd nd 0.1 nd nd nd nd 0.5 8.4 03 Thermoforming Injection Molding 3.48 03 320 --JLJ--J------4k0"0|| |-.-i --I, %% 63 nd 23 nd 14.9 nd 23 5.4 13 * 0.2 nd 17.4 393 3.7 13 nd 113 nd 3.7 nd 4.8 nd 4.0 nd 263 nd 1.0 51.0 nd nd nd 42 BFG15346 Cyclopropane, Pentanol 1-Nonanol 5-Octadecane 9-Octadecane 1-Hexadecane Total % Selected1 Organics Quantified | % Organics not Identified 18.7 173 233 263 4.4 99.9 0.1 nd nd nd nd nd 99.7 03 nd nd nd nd nd 97.9 2.1 Notes to Table X: 1 = The compounds selected for this table were positively identified and were present at levels 10X the analytical detection limit of the GC/MS ( > 0.001 ugm). Background organic vapors in the laboratory air were substracted from the concentrations found in the sample. The collection tube used for all experiments was Carbotrap 300. nd * Not Detected * = Compound identified but no accurate quantification could be made because of the very small amount of the organic vapor collected from the process. 21574045 43 BFG15347 Table XI Mass Percentages of Vapors Collected Based on Amounts of Selected1 Emissions of Polyesters (BMC) 1 | Material Flow (kg/Cycle) Highest Operating Temperature (F) Effluents Identified Styrene Dimethyl-nonane Tri-methyl-decane Tetra-methyl-butane Isopropyl-benzene Benzaldehyde Total % of Selected1 Organica Quantified % Organics not Quantified vtorvct (Hi Compression Molding 1.50 270 % 97.5 nd 03 1.8 * 03 99.9 0.1 Material Mixing 130 270 % 91.8 23 1.6 nd nd nd 95.6 4.4 1 - The compounds selected for this table were positively identified and were present at levels 10X the analytical detection limit of the GC/MS (>0.001 ugm). Background organic vapors in the laboratory air were substracted from the concentrations found in the sample. The collection tube used for all experiments was Carbotrap 300. nd " Not Detected " * Compound identified but no accurate quantification could be made because of the very small amount of the organic vapor collected from the process. 21574046 44 BFG15348 i Table Xn 1 Aerosol Concentrations in mg/m3 (Total Particulate) Measured during Process Emissions Experiments Polystyrene | Polyethylene 1 ABS 1 PVC Strand Extrusion Processes Sheet Blow Film 14.00 1.12 - - 0.48 7.66 1.79 - ND Injection lfolding and Thennofcinning Paper Coating - 5.19 - 1 | ----------- i----------- Polystyrene | Polyethylene ABS Polyester PVC Injection 0.41 ND ND ND Thermoforming ND - ND BMC ND - Mixing (BMC) - - - ND - Notes on Table XII: Samples were collected in a tared 37-mm, 5um PVC filter for one hour at 2 L/minute. The filters were weighed in an exact balance with a 0.01 mg sensitivity. This method is NIOSH Method 0500 . ND = Sampled but non detected. - = Not sampled, experiment not run. 45 BFG15349 21574047 Table Xm Benzene Soluble Particulate Concentrations in mg/m3 Measured during Process Emissions Experiments Extrusion Processes 1 Polystyrene Polyethylene ABS PVC Strand 632 - 31.91 ND Sheet 0.08 - 2030 Blown Film 5.58 - Paper Coating - 736 - Polystyrene Polyethylene ABS Polyester 1 pvc Injection Molding and Thennoforming Injection 0.17 ND ND ND Thermoforming ND ND ND BMC . - - ND - Mixing (BMC) | -1 - jj i ND | Samples were collected in a tared 37-mm, 2um PTFE membrane filter for one hour at a sampling rate of 2 L/minute. The filters without desiccation were extracted with benzene and weighed in an exact balance with a 0.01 mg sensitivity. This is NIOSH Method 5023. ND = Sampled but not detected. * Not sampled, experiment not run. 46 BFq15350 Table XIV Recommended Target Substances Generated During Steady State Plastic Processes Experiments j Plastic Target Substance Polystyrene1 Polyethylene1 ABS1 PVC BMC Styrene, Ethylbenzene, Toluene, Benzene3 Formaldehyde, Formic Acid Benzene3 Styrene, Xylene Toluene, Acrylonitrile Vinyl Chloride2, Hydrochloric Acid2 Benzene3, Toluene Styrene Note on Table, XIV: | ) j | | 1 = Polystyrene, Acrylonitrile-butadiene-styrene (ABS) and Polyethylene generate solid condensation particulate during process melting. Total Particulate sampling is also recommended for these plastics as an indicator of emissions. 2 = Not detected in these experiments but recommended as target substance because of regulatory interest. 3 = Present in very small amounts but recommended as a target substance because of regulatory interest. 47 BFG15351 APPENDIX C Analytical Methods for 1. Organic Vapors EPA - 624 (8240 A) Z Aldehydes EPA - TO 5 3. Organic Acids OSHA - 38 (as Acrylic Acid) Dow Chemical Modifications 4. Aerosol Sampling Total Dust NIOSH - 0600 Benzene Soluble Particulate NIOSH - 5023 Lead NIOSH - 7082 5. Inorganic Acids Hydrochloric Acid NIOSH 7903 ZLM L Z IZ BFG15376 TABLE 7. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION Parameter Accuracy, as recovery, x' (M9/L) Single analyst Overall precision, sr' precision, (M9/L) S' (M9/L) Benzene Bromod1 chioromethane Bromoform Bromomethane Carbon tetrachloride Chlorobenzene Chloroethane 2-Chloroethylvinyl ether* Chloroform Chioromethane Dibromochloromethane 1,2-Dichlorobenzene6 1,3-D1chlorobenzene 1,4-Dichlorobenzene6 1,1-Dichloroethane 1,2-Dichloroethane 1,1-Dichloroethene trans-1,2,-Diehloroethene 1,2-Diehloropropane* cis-l,3-Dichloropropene* trans-l,3-Dichloropropene* Ethyl benzene Methylene chloride 1,1,2,2-Tetrachloroethane Tetrachloroethene Toluene 1,1,1-Trichloroethane 1,1,2-Trichloroethane Trichloroethene Trichiorof1uoromethane Vinyl chloride 0.93C+2.00 1.03C-1.58 1.18C-2.35 1.00C 1.10C-1.68 0.98C+2.28 1.18C+0.81 1.00C 0.93C+0.33 1.03C-1.81 1.01C-0.03 0.94C+4.47 1.06C+1.68 0.94C+4.47 1.05C+0.36 1.02C+0.45 1.12C+0.61 1.05C+0.03 1.00C 1.00C 1.00C 0.98C+2.48 0.87C+1.88 0.93C+1.76 1.06C+0.60 0.98C+2.03 1.06C+0.73 0.95C+1.71 1.04C+2.27 0.99C+0.39 1.00C 0.26X-1.74 0.15X40.59 0.12x40.34 0.43X 0.12x40.25 0.16X-0.09 0.14x42.78 0.62x 0.16X40.22 0.37x42.14 0.17X-0.18 0.22X-1.45 0.14X-0.48 0.22X-1.45 0.13X-0.05 0.17X-0.32 0.17x41.06 0.14x40.09 0.33x 0.38x 0.25X 0.14x41.00 0.15x41.07 0.16x40.69 0.13X-0.18 0.15X-0.71 0.12X-0.15 0.14X40.02 0.13x40.36 0.33X-1.48 0.48x 0.25X-1.33 0.20X41.13 0.17x41.38 0.53x 0.11x40,37 0.26X-1.92 0.29x41.75 0.84x 0.18X40.16 0.58x40.43 0.17x40.49 0.30X-1.20 0.18X-0.82 0.30X-1.20 0.16X40.47 0.21X-0.38 0.43x-0i22 0.19x40.17 0.45x 0.52X 0.34x 0.26X-1.72 0.32X44.00 0.20x40.41 0.16X-0.45 0.22X-1.71 0.21X-0.39 0.18X40.00 0.12x40.59 0.34X-0.39 0.65x x' - Expected recovery for one or more measurements of a sample containing a concentration of C, in nq/L. s/ - Expected single analyst standard deviation of measurements at an average concentration of x, In nq/l. S' Expected Interlaboratory standard deviation of measurements at an average concentration found of x, in jig/L. C - True value for the concentration, in vq/l. x - Average recovery found for measurements of samples containing a concentration of C, in jig/L. a Estimates based upon the performance in a single laboratory. b Due to chromatographic resolution problems, performance statements for these isomers are based upon the sums of their concentrations. * 8240A - 33 Revision 1 November 1990 21574112 BFG15416