Document b5jgGQJJzRm0pJpyZMV9vEMD0

02/18/97 TUE 10:58 FAX 5178386027 FLAMMABILITY OF R134ar R22, & R123 IN CHLORINE by Dan O'Shaughnesssey Dow Chemical Company Analytical Sciences Midland, Michigan 48667 0OC Presented at the Chlorine Institute CFC Refrigerant Alternatives Seminar February 2nd, 1993 OUTLINE - R22 + CL2 FLAMMABILITY PROJECT - CALCULATIONS TOOLS - R22, 123, 134a CALCS & PLOTS - EXPERIMENTAL RESULTS - INTERPRETATION & CONCLUSIONS DO 073059 NFT OFNTTAI 02/18/97 TUE 10:59 FAX 5176388027 R22 + CL2 FLAMMABILITY PROJECT 81004 - IS R22 FLAMMABLE IN CL2 ? 02 (g) 02 CI2 + organic oil =* heat heat + C12 + R22 * PROPAGATION ? DanOEhaugfmmty DOW CHEMICAL February 2,19S3 DO 073060 CONFIDENTIAL 02/18/97 TOE 10:59 FAX 5176388027 CALCULATIONAL TOOLS 9 00 CALCULATED FLAME TEMPS @ THE LFL FUEL ' Tf <K) CALCULATED Name Formula Air or 02 Acetylene Methane Ethane Chloroethane C2H2 CH4 C2H6 C2H5CL 1300 1440 1530 1630 Dichloroethane lr2-C2H4CL2 1673 Chloroform CHCL3 -- F22 (PREDICTED) CHCLF2 Cl 2 712 824 909 1027 1137 705 890 NASA-CET calcs predict. Tf Pm, & Reaction Products - Tf 8 LFL are ~600* lower in CL2 tlian A1- or 2 Dan (XShaughntwy DOW CHEMICAL February 2,1993 DO 073061 CONFIDENTIAL R22 + CL2 FLAMMABILITY CALCS & PREDICTIONS a oo R22 + CL2 @ 100*C 6 13.6 ATM CALCS PREDICTED THE FOLLOWING: LFL-UFL OF 25-85 VOL% Pm/Pi ~ 3.3 Kg - 10 - 100 MIE < 1 JOULE EXPERIMENTAL CHALLENGES: SAFETY OF CL2 HANDLING NEUT/CLEAN HCL, CL2, HF, C ... TEST @ 100*C & 13.6 ATM 50/50 R22/CL2 (VP, Tc) KEY PURPOSE OF DATA: ANSWER ? OF PROPAGATION CONFIRMATION OF CALC . Pm/Pi, Kg, & MIE Dan CfShaughn*s3ey DOW CHEMICAL February ft, 1993 DO 073062 CONFIDENTIAL. 02/18/97 TOE 10:59 FAX 5176388027 MODIFIED 35 L SYSTEM FOR FREON 22+ CL2 - CONFORMS TO ASTM E-918-83, Calls for 1 lit r Dan (yShaughnesny DOW CHEMICAL February 2,1993 DO 073060 CONFTDFNTTAL 02/18/97 TOE 10:59 FAX 5176388027 EXPERIMENTAL RESULTS a 00 R22 + CL2 DEFLAGRATIONS RON DATA RUN R22 _4_ % l unk CL2 . Ti % c unk 113 *i psla >62 >100 o A P /P ratio Tm dP/dt^ c psi/s COMMENTS >200 >0 ign on R22 int C12 wall toot spot ~180*C 2 48 52 107 208 653 3.1 >400 3 78 22 107 208 208 1.0 107 4 100 0 109 200 200 1.0 109 5 trc bal 115 >60 >60 >1.0 >2S0 6 68 32 111 200 200 1.0 111 7 51 49 27 66 208 3.2 >200 431 fuse wire iga - fuse wire ign - I'hfim ign 10 Kjoules >0 cheiu ign + CL2 rxn - fuse wire ign 317 fuse wire + M103 HOT SPOT OR STATIC COULD IGNITE Dan CrShaughnessty DOW CHEMICAL February 2,1993 Do DO/yp- Tn364 02/18/97 TUE 10:59 FAX 5176386027 EXPERIMENTAL RESULTS 50/50 R?S> + CT.2 DEFLAGRATIONS PRES VS TIME AFTER IGN Slot PHEBSli.- (PS A)I - VERY SLOW FLAME SPEEDS Dan 0'8haugfme**ty DOW CHEMICAL February 2,1993 DO 073065 CONFIDENT TAl 02/18/97 THE 11:00 FAZ 5170386027 0010 CALC & EXP RESULTS FLAMMABILITY DIAGRAM FOR R22, CL2, & HCL @ 100"C & 13.6 ATM -------------- CALC FLAM LIMITS ----- -- ERROR BARS I Positive tests O Negative tests R22 RESULTS (50/50 Freon 22/Cl2) Tir mC eaJ-c eatp 27 27 .gals earn 100 107 Pi, atm 4.4 4.5 13.6 14.1 Em/Pi 3.9 3.2 3.3 3.1 Kg B*M/s 10-100 7.2 10-100 9.7 MXE, j <1 <1 <1 <1 LFL-UFL 24 - 688 60 50 40 chlorine voiume-perctnt SCI Dan OTShaughne&sey DOW CHEMICAL February 2,1993 DO 073066 CONFIDENTIAL 02/18/97 TUE 11:00 FAX 5176388027 8loii NASA-CET CALCULATIONS OF FREONS IN CL2 0 100*C & 13.6 ATM FRBOM 22 (CTOUrai + CL2 CSCLF2 + CL2 CCL4 + Hd + CM + G&Z + HF + C + CCL2F2 + CCLT3 f OCL3F TOT GAS Pf Pf/Pi moles mol mol mol mol mol mol mol mol mol mol moles K tP> ratio 100 0 0.0 15.2 40.2 9.5 24.8 54.7 0.6 4.5 0.1 154.7 1106 62.4 4.6 90 10 0.1 72.1 36.1 15.1 17.9 47.6 0.9 5.3 0.1 147.6 1104 59,4 4.4 ao 20 0.1 67.4 31.8 21.6 12.6 40.8 1.2 5.8 0.2 140.8 1092 56.1 4.1 70 30 0.3 61.5 27.4 28.4 8.5 34.2 1.6 6.1 0.4 134.2 1072 52.5 3.9 60 40 0.6 54.6 22.9 35.5 5.4 21-1 2.0 6.2 0.6 127.7 1044 48,6 3.6 50 50 1.3 46.8 18.3 42.2 3.2 21.1 2.4 5.9 1.0 121.1 1008 44.5 3.3 40 GO 2.6 38.2 13.8 48.0 1.8 14.0 2.8 5.3 1.4 . 114.or 971 40.4 3.0 30 70 3.1 ` 29.1 9.5 52.3 0.9 6.2 2.9 4.4 1.9 106.2 936 36.2 2.7 20 80 6.9 19.6 6.2 60.0 0.4 0 2.2 2.9 1.8 100.0 869 31.7 2.3 10 90 4.2 9.9 3.9 80.0 0.1 0 0.5 0.9 0.5 100.0 664 24.2 1.8 FREON 123 (C2HCL2F31 + CL2 C2HCL2F3 + CL2 * CCL4 + HO. + CF4 + CL2 + HF + C +- CCX2F2 + CCLF3 + CCL3F TOT GAS Tf Pf Ff/Pi moles mol mol ml tool mol mol XK?1 mol mol mol moles __K_ atm ratio 100 0 6.5 98.0 62.4 24.1 2.0 112 4.6 12.4 2.1 212.0 772 59.6 4.4 90 10 7.6 88.3 55.1 26.4 1.7 98.2 4.8 11.9 2.4 198.2 777 56.1 4.1 80 20 8.8 78.5 48.0 28.7 1.5 84.3 4.9 11.3 2.6 184.3 782 52.5 3.9 70 30 10.0 68.8 41.0 31.2 1.2 70.6 5.0 10.6 2.8 170.6 789 49.1 3.6 60 40 11.2 59.0 34.2 33.8 1.0 56.9 5.0 9.8 3.0 156.9 796 45.5 3.5 50 30 12.4 49.2 27.5 36.6 0.8 43.3 4.9 8.7 3.2 143.3 805 42.0 3.2 40 60 13.6 39.3 21.0 39.7 0.6 29.9 4.6 7.5 3.3 129.9 815 38.6 2.9 30 70 14.8 29.5 14.8 43.2 0.5 16.6 4.2 6.1 3.4 116.6 826 35.1 2.7 20 80 16.0 19.7 9.0 47.2 0.3 3.6 3.6 4.4 3.3 103.6 840 31.7 2.4 18 82 16.3 17.7 7.8 48.1 0.3 1.0 3.4 4.1 3.3 101.0 843 31.0 2.4 17 83 16.3 16.8 7.3 49.0 0.2 0 3.3 3.8 3.2 100. 842 30.7 2.3 10 90 10.5 9.9 5.2 70.0 0.1 0 1.2 1.7 1.2 100. 706 25.7 2.0 FREON 134a (C2H2F4) + Ci.2 C2B2F4 + GL2 CCL4 + HGL + CF4 + CL2 + HF + C + CCL2F2 + CCLF3 + C3L3F TOT GAS Tf Pf Pf/Pi moles mol mol mol mol mol mol mol mol 100 0 0 0 50.0 0 200 150 0 mol mol moi*a K atm ratio 0 0 250.0 1351 123 9.4 90 10 0 18.9 49.3 0.2 161 130 0 0.6 0 230.1 1396 117 8.9 80 20 0 35.2 47.6 1.5 125 111 0 1.6 0 210.8 1437 110 8.4 70 30 0 46.6 44.4 4.9 93.4 92.6 0.1 2.8 0 192.7 1464 103 7.8 60 40 0.0 82-4 39.9 11.1 67.6 75.7 0.3 4.0 0. 176.0 1469 94.2 7.2 50 50 0.0 53.6 34.4 19.8 46.4 60.0 0.6 4.9 0.1 160.3 1452 84.8 6.5 40 60 0.0 51.0 28.2 30.4 29.0 45.3 0.9 5.4 0.1 145.6 1409 74.8 5.7 30 70 0.1 44.9 21.4 42.7 15.1 31.4 1.3 5.5 0.3 131.6 1331 63.8 4.9 20 80 0.4 34.8 13.9 56.4 5.2 18.2 1.8 5.0 0.6 118.3 1195 51.5 3.9 10 90 4,1 19.3 5.8 65.7 0.7 2.8 2.4 3.3 1.7 102.8 998 37.4 2.9 9 91 5.0 17.4 5.0 65.6 0.5 0.8 2.3 3.0 1.8 100.8 980 36.0 2.7 8 92 5.2 15.6 4.5 68.0 0.4 0 2.0 2.6 1.7 100, 942 34.3 2.6 6 94 4.3 11.8 3.9 76.0 0.2 0 1.2 1.6 1.0 100. 829 30.2 2.3 Dan OWiaughnettty DOW CHEMICAL February 2.1993 Do 73067 CONF Td^ttal 02/18/97 TUE 11:00 FAZ 5178386027 i CALCULATED PRESSURE RISE RATIOS OF FREONS AND CHLOROFORM IN CL2 a 01 C2H2F4 calculated Pf/Pi CHCIF2 C2HC12F3 CHC13 voi % fuel in chlorine llamtxALaBcTgc& Dan CrShaughnascy DOW CHEMICAL January 28,1991 DO 073068 CONFIDENTIAL 02/18/87 TUE 11:00 FAZ 5176388027 0 01 DO 073069 CONFTDFNTTAL 02/18/97 TUE 11:01 FAI 5178388027 R22, 134a, & 123 EXPERIMENTAL RESULTS FREONS IN CHXiORXSS 8 38 *C a 6.8 AIM (rmleaw noted) RUN t calc calc 130 135 140 146B4 145 146B5 146 147E 147a 148 149 150 160 162 147B 147C 147D R22 _Jg___ 10 20 29.3 35.2 41.2 44.1 45.2 45.9 46.7 47.7 48.0 -48 49.0 50.3 59.7 60.0 46.9 46.8 47.8 _____ S pala 6 sec 93 248 344 338 351 354 .365 344 361 >244 345 247 99 100 178 106 29 20 11.2 3.8 2.5? 2.24 .1.3 2.15 2.09 2.36 3.05 12 20 20 1.72 1.48 1.47 E/gima&s gals. 1.966 2.645 1.01 3.008 2.46 3.225 3.38 3.437 3.40 3.544 3.48 3.584 3.51 3.610 3.63 3.639 3.42 3.676 3.62 3.687 >2.44 3.7 3.39 3.723 2.43 3.771 1.0 4.110 1.0 4.121 3.42 3.? 3.35 3.? 2.42 2.? dP/dtm psi/s 2 68 184 387 274 383 378 205 377 >50 286 50 0 0 147 125 50 Tm *c 38 245 >40 273 291 289 259 263 >200 >240 242 39 37 186 152 61 COMMENTS M M K MF, Ti-19 MF MF, Ti-30i sampled F MF F pre-ign F M M MF pi-52.0, Tl-19 Pi-31.5, Ti-21 Pi=12.0, Ti=21 calc 210 225 227A 228E 229 227B 230 228F 235 240 245 250 calc 228C Rl34a 10 14.0 25.6 28.0 28.7 29.2 30.1 30.4 30.6 35.6 40.0 44.7 50.3 60 28.5 75 472 508 440 501 432 328 >460 141 100 100 102 12 20 2.72 1.96 1.57 2,11 3.34 6.75 1.66 10 10 10 1.27 1.0 4.67 5.08 4.40 4.96 4.15 3.29 >4.4 1.39 1.0 1.0 1.0 2.18 3.119 3.625 4.983 5.239 5.314 5.367 5.463 5.491 5.985 6.403 6.817 7.306 8.064 2.7 0 308 353 563 400 300 200 73 0 0 0 11 38 202 356 320 377 341 282 365 48 38 41 38 31 F MF MF MF MF MF MF mF, sampled MF F F r F=5.5r Ti--19 310 315 318 320 322 340 350 R123 % 9.9 15.1 20.2 22.2 31.2 34.8 49.9 59.4 59.8 91.0 92.3 71.2 72.6 63.6 0.17 0.21 20 20 20 0.05 0.06 1.01 2.1 1.01 2.4 1.0 2.6 1.0 2.7 1.0 2.9 1.003 3.0 1.003 3.5 2 33.9 3 37.3 0 81.0 0 86.5 0 86.3 4 63.7 3 62.2 Pi-59.0, Ti-33.3 Pi-59.2, Ti-36.8 Pi-91.0, Ti--81.0 Pi-92.3, Tl--86.5 Pi-71.2, Ti--86.3 Pi-72.4, Ti--63.3 Pi-63.4, Ti--62.2 - R123 -I- 0*2 IS HON-FIAWM1BLB g PROCESS CONDITIONS Dan OShaughneoey DOW CHEMICAL February 2,1963 DO 073070 CONFIDENTIAL 02/18/97 THE 11:01 FAI 8176386027 Boh COMPRESSION RATIOS (Pm/Pi) vs. FREON IN CL2 @ 38C & 6.8 ATM FREON VOL% IN CHLORINE Dan O'Shaughnemuj dow chemical February 2,1993 DO 073071 CONFIDENTIAL 02/18/97 TUE 11:01 FAI S178386027 a 01( 35 LITER FLAMMABILITY SYSTEM MODIFIED FOR R22, 123, & 134a as LITER FLMMABUTY SYSTEM BUM SEQUEHCE STEP DESCRIPTIONS A 'INTRO A STARTUP BOCYCLB3T1ANTN2/BVAC ___ C-J MINUISHVACUAIJON ACHBCKFR3HBOS D- PRECN LOWPRESSUREPURGWHVAC E-LOADINGCL20aPKB0N f-hre wHENHEAmn I ____ G* CLEANINGcross, N2TO PEED H-aumBAtava/NOTXLSsaxrwm I-SPRAYNEUTRALIZING SOUJTK3NINTOS5L 3-CHKUBHTRANSFERSSLTO OtOCtOUTTANt E.BLOWBAOCDIFfUBBWnHMZ L-VENTING DOWNALLTANKSTOATM U.SDQB CTCLBWOH KZO N - PLANTN2FUKC3NG O- VACUUM DRYING 12;; vW of ai xy' PLANT 51: N2 VACUUM PUMP 33 LITER VESSELknockout TANK PEED TANK CHLORINE FREON DanCrShaughnBstey DOW CHEMICAL February 2,1993 on CoA/p ^TT4L 02/18/97 TOE 11:01 FAX 5178386027 INTERPRETATION & CONCLUSIONS 0018 - PHYSICAL PROPERTIES CAN LIMIT FLAMMABILITY - PEAK PRESSURES ASSUME HOMOGENOUS MIXTURES - STATIC OR HOT SPOT COULD IGNITE - COMBUSTION PRODUCTS AID INERTING - R123 + CL2 NON-FLAMMABLE @ PROCESS CONDITIONS - NASA-CET CALCS PREDICT LFL & Pm/Pi ACKNOWLEDGEMENTS: Rich Chauviere, Joe Downey, Rick Kwatney, MarabethlaBarge, Tom Mcgee, Bruce Powers, Bob Zandlak,... Dan O'Shaughncssey DOW CHEMICAL February 2,1993 Oq COMp l0*HTT4L 02/18/97 TUE 11:02 FAX 5176386027 ft 01 NASA-GET CALCULATIONS OF CHLOROFORM IN CL2 @ 100'C & 6.1 ATM CHCL3 + CL2 moles mol 90 10 80 20 70 30 60 40 50 50 45 55 40 60 38 62 35 65 30 70 20 80 10 90 CCL4 4- HCX. + CL2 mol mol mol 36.1 90.0 27.8 34.5 80.0 30.9 32.9 .70.0 34.2 .31.2 60.0 37.7 29.3 50.0 41.3 27.4 40.0 45.2 25.3 20.0 10.0 30.0 20,0 10.0 49.4 60.0 80.0 + C TOTAL OAS mol ipoles S3.9 153.9 45.4 145.4 37.1 137.1 28.8 128.8 20.7 120.7 12.6 Il2.fi 4.7 104.7 0.0 100.0 0.0 100.0 T K $81 694 708 722 737 753 770 730 578 Pf stan 17.1 16.5 15.9 15.2 14.5 13.9 13.2 11.9 9.5 Pf/Pi ratio 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.0 1.5 Pf/Pi ratio 1.9 2.1 2.1 1.1 1.0 SEE GRAPHICAL PLOTS OF: CALCULATED FLAME TEMPERATURES OF FREONS AND CHLOROFORM IN CL2 CALCULATED PRESSURE RISE RATIOS OF FREONS AND CHLOROFORM IN CL2 Dan CShau^knessty DOW CHEMICAL February 2,1993 no 073074 CONFIDF NTTAl 02/18/97 TUE 11:02 FAX 5176386027 131020 NASA-CET CALCULATIONS OF FREONS IN CL2 @ 38"C & 6.8 ATM naaN 22 ttTMTT.vQ.\ * pt.? CHCLF2 + GL2 * CCL4 + HCL + CF4 + CL2 + HF + C + CCL2F2 + CCLF3 -I- CCL3F TOT GAS T Pf Pf/Pi moles mol mol mol mol mol mol mol mol mol mol iIm _s_ atm ratio 100 0 0.0 75.8 40.8 9.6 24.2 54.8 0.4 3.9 0.0 154.8 1068 36.1 5.3 90 10 0.0 72.7 36.8 15.4 17.3 47.7 0.7 . 4.6 0.1 147.7 1065 34.4 5.1 80 20 0.1 67.9 32.6 23.0 12.1 41.0 1.0 5.2 ' 0.2 141.0 1052 32.4 4.8 70 30 0.2 62.0 28.2 29.1 8.0 34.5 1.3 5.5 0.3 134.5 1030 30.3 4.5 60 40 0.5 55.0 23.6 36.3 5.0 28.2 1.7 S.5 0.5 128.2 999 28.0 4.1 50 50 1.1 . 47.2 19.0 43.2 2.8 21.6 2.0 5.4 0,8 121.6 961 25.5 3.8 40 60 2.5 38.5 14.5 49.1 1.5 14.5 2.4 4.9 1.2 114.5 921 23.1 3.4 30 70 5.1 29.3 10.1 53.1 0.7 6.6 2.5 4.1 1.7 106.6 885 20.6 3.0 20 80 7.2 19.7 6.5 60.0 0.3 0.0 1.9 2.7 1.6 100.0 822 18.0 2.6 10 90 4.4 10-0 4.1 80.0 0.0 0.0 0.4 0.8 0.3 100.0 611 13-3 2.0 7RB0H 123 + CL2 C2HCL2F3 + CL2 - CCL4 + HQi + <3*4 + CL2 + or + C + CL2F2 + CCXF3 + CCL3F tot GAS moles- mol mol mol mol ml mol mol mol >1 mol moles 100 0 7.3 98.5 63.7 23.6 1.5 112. 4.1 11.2 1.9 211.8 90 10 8.5 88.7 56.5 25.3 1.3 98. 4.2 10.8 2.1 197.9 80 20 9.7 78.9 49.3 28.2 1.1 84. 4.3 10.3 2.3 184.1 70 30 10.9 69.1 42.2 30.7 0.9 70. 4.4 9.6 2.5 170.4 60 40 12.1 59.2 35.3 33-4 0.8 57. 4.4 8.9 2.7 156.7 50 50 13.3 49.4 28.5 36.2 0.6 43. 4.3 8.0 2.9 143.1 40 60 14.4 39.5 21.9 39.4 0.5 30. 4.1 6.9 3.0 129.7 30 70 15.6 29.6 15.6 42.9 0.4 16. 3.7 5.6 3.0 116.5 20 80 16.7 19.8 9.5 47.0 0.2 4. 3.2 10 90 10.9 10-0 5.6 70.0 0.0 0. 1.0 4.1 3.0 103.5 1.5 1.0 100. T Pf Pf/Pi K atm ratio 728 33.7 5.0 733 31.7 4.7 739 29.7 4.4 7 45 27.8 4.1 753 25.8 3.8 761 23-8 3.5 771 21.8 3.2 782 19.9 2.9 795 18.0 2.6 655 14.3 2.1 ECTOT ,134 (CZB2F4) + CL2 C2H2F4 + CL2 Cdi4 4- Hdi + CF4 + GL2 + HF + C + CCL2F2 + CCLF3 + CCL3F TOT GAS T Pf Pf/Pi fioles mol mol mol mol 22* mol el B2i 100 0 0 0 50.0 0 200 150 0 mol mol moles __ tm ratio 0 0 250. 1312 71.7 10.5 90 10 0 18.9 49.3 0.2 161 130 0 0.5 0 . 230. 1357 68.2 10.0 80 20 0 35.1 47.7 1.6 125 111 0 1.4 0 211. 1397 64.4 9.5 70 30 0 46.2 44.6 5.3 94 93 0.1 2.5 Q 193. 1421 60.0 8.8 60 40 0 51.9 40.2 11.7 68 76 0.3 3.5 0 176. 1424 54.8 8.0 50 50 0 53.1 34.8 20.5 47 60 0.5 4.3 0 161. 1406 49.5 7.3 40 60 0 50.7 28.7 31.1 29 46 0.7 4.7 0 146. 1363 43.5 6.4 30 70 0.1 44.9 22 * 0 43.5 15 32 1.0 4.9 0.2 132. 1284 37.0 9*5 20 80 0.3 35.1 14.5 57.3 5 19 1.5 4.5 0.5 119. 1145 29.8 4.4 10 90 1.5 19.4 6.2 66.6 1 3 2.1 3.0 1.5 103. 941 21.2 3.1 DanCyShaughnesmy DOW CBEMICAL February 2,1993 00 073075 CONFIDENTIAL