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INDUSTRIAL HYGIENE REPORT THE DOW CHEMICAL COMPANY department H&ES Analytical & Environmental Chemistry Lab TITUS LABORATORY REPORT CODE HEH2.12-3-5 (27) OATi ISSUED July 31 1986 ACCOUNT NO. PROBLEM number 178-1524021 EFFECTIVENESS OF MONOETHANOLAMINE ATMOSPHERES SEVERAL RESPIRATOR CARTRIDGES IN REMOVING AND DIETHYLENETRIAMINE FROM breathing AUTHQR(S) SIGNATUHEIS) M. W. Spence REVIEWER'S SIGNATURE S. K. Norwood DESCRIPTIVE summary with conclusions J. P. Warriner American Optical R51A (organic vapor), AO-R54A (ammonia), 3M-8712 (organic vapor), 3M-8727 (ammonia), and Scott 282-OAAM-L (organic vapor, acid gas, ammonia combination) respirator cartridges were challenged with 70-108 ppm monoetbanolarnine (MEA) vapor at 20% relative humidity and 46-70 ppm MEA vapor at 61% relative humidity. MEA vapor concentration levels in the challenge and exhaust air streams were . monitored using a Foxboro Corp. MIRAN IB portable infrared ambient air analyzer. No breakthrough of any of the test cartridges at either relative humidity was observed during the 40 hour duration of the test (detection limit - 3 ppm MEA). American Optical R51A and R54A respirator cartridges were challenged with 12-26 ppm diethylenetriamine (DETA) vapor at 47% relative humidity. DETA vapor concentration levels in the challenge and exhaust air streams was monitored using solid sorbent trapping and a fluorescence measurement technique. No break through of either of the test cartridges at 47% relative humidity was observed during the 42 hour duration of the test (detection limit = 0,8 ppm DETA). All cartridges tested would be expected to provide adequate respiratory protection under actual conditions of field use. ch DISTRIBUTION F. D. Axe, Pittsburg, CA R, W. Black, Freeport D, L. Bosatra, Horgen J. P. Cikalo, 53, Sarnia R. Cordellini, Guaruja, Brazil D, E. Cragar, Freeport S. L. Dombrowski, 2020 M. R. Edens, Plaquemine G. W, Engdahl, 1803 S, M. Gorgacz, 474 B. Houtman, 474 B, D. Koblinski, Freeport *Cover sheet only. *J. E. LeBeau, 1803 fCT^r^ceimeT^i^ W, E. Ledford, Plaquemine G. L. Meier, Strongsville C, G. Mendoza, 1701 W. L. Myles, B101, Freeport L. W. Rampy, 1803 J. C. Ramsey, 1701 A. W. Schaffer, 1803 H. K. Tobel, 471, Pittsburg, CA J. J. Twisk, Terneuzen J. R. Vaccaro, 9001 K. C. Wong, 151A,Ft.Saskatchewan rOKM C-t03Q DOW CONFIDENTIAL DO 073974 CONFTDFNTTAL 2- INTRODUCTION Alkanolamines and alkylpolyamines are handled widely by Dow customers. This study is part of Dow's ongoing product stewardship program to insure that these substances are handled safely and with minimum risk to health. Alkanolamines are used in emulsifiers, acid gas scrubbers, and adhesives. Alkyl polyamines find use as epoxy resin hardeners and chelating agents. Low ACGIH TLV values for these amines necessitate the use of respirators in dealing with them in cases of inadequate ventilation or spills. The purpose of this study is to evaluate the effectiveness of several respirator cartridges for use with these amines. Monoethanolamine (MEA) and diethylenetriamine (DETA) were chosen as test compounds representative of each class of amine. Physical Properties Monoethanolamine Molecular weight Boiling point Vapor pressure Saturated air concentration Density^,5 Odor Physical State ho-ch2-ch1-nh1 61.08 17IC 0,4 mm Hg @ 20C 526 ppm 0 20C 1.0117 Slightly ammoniacal @ 3-4 ppm Viscous, colorless liquid Diethylenetriamine HjN-CHj-CHj-NH-CHj-CHj-NHj Molecular weight Boiling point Vapor pressure Saturated air concentration Density^,5 Odor Physical state 103.17 207.1C 0.2mm Hg @ 20C 263 ppm @ 20C 0.955 Amine Viscous, colorless to yellow liquid Potential Health Effects The most significant potential health effects of both test compounds are similar (1): Eye - may cause severe irritations with corneal injury. Skin - a short single exposure may cause skin burns. ACGIH TWA-TLV - 3 ppm (MEA); 1 ppm-skin (DETA) DOW CONFIDENTIAL DO 073975 CONFTDFNTTal -3- EXPERIMENTAL Test Substance The test compounds were obtained from the following sources s MEA -- Gretchen LeBlanc, Plaquemine -- 99.81% pure Lots 851018, P86Q107-55 DETA -- Rick Black, Freeport -- 99.36% pure Lots TA860120-B, TA850802-BNA Test Cartridges The following cartridges were chosen to represent the variety of types which might commonly be used by Dow customers: Type Organic vapor Organic vapor Ammonia Ammonia st-y> one piece disposable dual cartridge one piece disposable dual cartridge Manufacturer 3M American Optical 3M American Optical Model 8712 R51A 8727 R54A In addition, a chin-style organic vapor, acid gas, ammonia combination canister used for escape purposes in the Plaquemine Alkanolamines Plant (Scott 282-- QAAM-L) was evaluated. Test Procedure The testing matrix is shown in Table I. The organic vapor, ammonia, and com bination cartridges were challenged for 40 hours at 64 liters/minute and the concentration ranges and relative humidities indicated. In the case of MEA, duplicate tests were conducted. For DETA, a single test was run because of the time-consuming nature of the concentration monitoring procedure. Test Atmosphere Generation Test atmospheres of the two compounds at the concentration ranges indicated in Table I were generated by bubbling dry air (10% R,H.) from a Miller-Nelson Model 201 flow-temperature-humidity system through a water-jacketed fritted glass bubbler containing the compound and combining the resulting partially saturated air with appropriate amounts of air from a second Miller-Nelson Model 201 system which by-passed the bubbler. The air from the second Model 201 was adjusted to the humidity necessary to give the desired humidity in the final test atmosphere. The schematic design of this apparatus is shown in Figure 1. The^ respirator cartridges were challenged with test concentrations of MEA and DETA at an air flow rate of 64 liters per minute at relative humidities of 20% (MEA), 47% (DETA), and 61% (MEA). The respirator test apparatus shown in Figure 1 was constructed using glass tubing and 1/2 inch O.D, Teflon tubing. DOW CONFIDENTIAL DO 073976 CONFIDENTIAL -4- The respirator test chamber was made of glass. The challenge atmosphere was samplea at the test atmosphere sampling port while the exhaust air stream was tested via Teflon tubing connected to the top of the respirator test chamber. Analytical The protocol specified that a capillary gas chromatograph equipped with flame ionization or nitrogen-phosphorous detector and an automated sampling valve would be used to analyze the challenge and exhaust air streams for MEA and DETA. Investigation of this technique showed it to be not sensitive enough for DETA and not stable enough for monitoring a 40 hour run with MEA. Concentrations of both the challenge and exhaust air streams of MEA were moni tored using the Foxboro Miran IB IR Analyzer (microprocessor controlled) set at the wavelength specified by the manufacturer for MEA (12.93 pm). The detection limit for MEA was determined to be 3 ppm. Concentrations of both the challenge and exhaust air streams of DETA were determined by sampling them at 172 ml/minute (DuPont P125A Portable Air Sampling Pump) onto 1500 mg silica gel sorption tubes (SKC Corp.), desorbing the DETA in 0.2 N aqueous HC1 solution and measuring the fluorescence of the fluoroeseamine--DETA reaction product at pH 9.1 according to the procedure de scribed by the fluorgenic reagent manufacturer (Roche). The detection limit for DETA was determined to be 0.8 ppm, RESULTS AND DISCUSSION There was no breakthrough detected during the 40 hour test for any of the r spirator cartridges tested for either MEA or DETA, Because the test concentrations used in this study probably represent maximum possible concentrations in actual use situations, any of the respirator cartridges tested would be expected to provide adequate protection. DOW CONFIDENTIAL DO 073977 CONFTDFNTIAl Table 1, EXPERIMENTAL TESTING MATRIX: RESPIRATOR CARTRIDGES CHALLENGED WITH MONOETHANOLAMINE (MEA) AND DIETHYLENETRIAMINE (DETA) Respirator Cartridge AO-R51A AO-R54A 3M-8712 3M-8727 Scott~282-0AAM-L Concentration in pptp (v/v) -- Number of Tests 20% RH 47% RH 61% RH 65-108 (MEA)-3 12-26(DETA)-1 46-53 (MEA)-2 80-93(MEA)-2 12-26 (DETA)-l 50-56(MEA)-2 64-84(MEA)-2 55-70 (MEA)-2 74-83 (MEA)-2 53-63(MEA)-2 47-55 (MEA)-2 DOW CONFIDENTIAL DO 07397R OONFTDFNTTAl r FIGURE f. RESPIRATOR TEST APPARATUS CCNF o o o 'OT] u-N)) 2O /7?IV CONFIDENTIAL -t M M vO >