1、? AA 9 杜英生 王利东 杜 翔 余国琮 张凤宝 张国亮 (?v ,?300072)(?v“)Chen (1986)4 ZNRTL“ $, L | %T 1 f ,NH3-H2S-H2O8“ A 9 ,| YPitzer #Chen 9 TM1 bT LKMb1oM:? A A NRTLZ ; _ h , Faga 3cac “1s ,ts V !91 9 bd A( ) A( ),? Ai ( A ),7 OAMi Q , PN8“ 9 1 4b1V1949 MVan Krevelen 14 B*9 ? A 9 ZE,5Edwards 2, Wilson 3 , Beuiter 4 ,C
2、hen 5, 6, Berndis 7,E 8, W 9, 10 N “ 9 bNH3-H2S-H2O8“ A 9K,Chen , 9 T M1 L,7 O Pa iS z, 4 E9 u/ z $b1 s Hq/,? A8“M 1“ s,AM=(_) # A M()Wb1. 1AM = 1“NH3-H2S-H2O, NH3-CO2-H2O#NH3-H2S-CO2-H2O8“AM? 3B“ QQ,NH3-H2S-H2O8“,/ :NH3+ H2O NH+4 + OH-K 1 (T) = ANH4+ AOH- / (ANH3AW) ()H2S H+ + HS- K 2 (T) = AH+ AHS
3、- /AH2S ()HS- H+ + S2- K 3 (T) = AH+ AS2- /AHS- ()H2O H+ + OH- K 4 (T) = AH+ AOH- /AW (), K i (T) Q ,W1 T:lnK = A 1/T + A 2lnT + A 3T + A 4(T/K) ( 1)A 1jA 4nD2; ai 0,YV“ C*i 0 imi (mol/kgH2O)1 ,Ai= miC*ibAM 0s0i“ , ZX :mtot, NH3 = mNH3 + mNH+4 ()c37c杜英生等? A A 9 XX M :s q8“9 H,Z()()Z()#()9mtot, H2H2S
4、 = mH2S + mHS- + mS2- ()Z:mH+ + mNH+4 = mOH- + mHS- + 2mS2- ()yN,X8“9( mtot, NH3 )9 ;(mt ot, H2S) i, Z()j() VAM 0 ibY p ZFZE ,BZemaitisRafal 11Newton-Raphson pdLZF/ ; 6BGautamSeider 12GibbsKl1 ?Eb BZE,yZE l y,Ie, iNewtonE1p1 J, B+5,i 4b1. 2 A AMs0 Fs MMFs , A 1“ T:yNH35NH3P = mNH3CNH3H NH3exp VNH3(P
5、 - PSW)RT ()yH2S5H2SP = mH2SCH2SH H2Sexp VH2S( P - PSW)RT ()yH2O5H2OP = mH2OCH2OPSW5SWexp VW(P - PSW)RT ()T,d“ 5iNakamura 134 Z9 ,ZNH3, H2SH2O 8rTzbVNH3, VH2SNH3, H2SK d A :8,Breivi 141 T,sY:VNH3 = 67. 49678 - 0. 284076T + 0. 00052T 2cm3/mol ( 2)VH2S = 67. 964 - 0. 229257T + 0. 0003222T 2+ 2. 6610-
6、7T3cm3/ mol ( 3)VW :8:VW = 0. 0180152(1. 2504422 - 0. 0019092809T+ 0. 3624610- 5T2)cm3/mol ( 4)TH i , 1 T:lnH = B1/T + B2lnT + B3T + B4atm( 5)(1atm = 101. 325kPa) B1jB4nD2b TPSW :PSW =exp(18. 3036 - 3816. 44T - 46. 13)760atm( 6)2. 3“ 9 AM;is0 0, #s0W T ,7 O # 0WT byNsB aV Ad XV :Gibbs1 ? A,9 B il“ 9
7、 AM 0 i1o,V79 9 M Fss1obEdwards 2) 0- 0MTPitzer w 0- 0s0-s0MT , Te,Y ,B = , ?9 i10j20mol/L AbBeutier 4Edwards $ ,9 T , A,t .MbE 8a 9gEdwards $ F T,i L B n“dNH3-H2S-H2O, NH3-CO2-H2O , ZPitzer bBernadis 7a W 9 kDebye-Hiickel Q 0WT ,sYUNI-QUAC #Wilson Qs0 Ad X Db NH3-CO2-H2O8“ AT 1 ,NH3-H2S-H2O#NH3-SO2
8、-H2O8“ A 9 1 ,yN ?z U !99 ,7 4 !99 , CNH3-H2S-H2O8“ ,yNE,9 T9 1 ybChen 5, 6PitzerDebye-Hiickel 0WT bNRTL FsW T ,4 ANRTL , ZPitzer M1 , i# 0 / = V , PS z,9 T1 bChen ZNRTL“ Vr T c38c1998 M26 6 /:lnCi = lnC* , pdhi + lnC* , lci ( 7)T: lnC* ,pdhiV UPitzer-Debye-Hiickel “ ;lnC* , lciV UNRTLZ“ ;lnC* , pdh
9、i = - 1000Ms1/ 2A5 (2Z2i /Q)ln(1 + Q)1/ 2x ) + (Z2iI1/ 2x - 2I 3/ 2x )/ (1 + QI1/ 2x ) ( 8)T, M S : , 0. 018kg/ mol; Ix 0 , Ix= 12 i miZi; Q= 14. 9A 5 1i“ Debye-Hiickel ,Vr T:A 5 = - 1. 306568 + 0. 01328238T - 0. 355080310- 4T 2 + 0. 338196810- 7T 3 ( 9)lnC* , lciVr T:a.s0“ Vr TlnC1cm = j XjGjmSjm k
10、 XkGkm + mXmGmm k X kGkmSmm- k XkGkmSkm k XkGkm+ c aX a aXaX cGmc,ac k XkGkc, ac Smc, ac - k XkGkc, acSkc,ac k XkGkc, ac+ a cX c cXcXaGma, ca k X kGka, ca Sma, ca - k XkGka,caSka, ca k XkGka, ca (10)b. 0“ Vr T1ZclnClcc = aXa kXkGkc, acSkc, ac aXa kXkGkc, ac+ mX mGcm k XkGkm Scm - k XkGkmSkm k XkGkm+
11、 a cX c cX cXaGca, ca k X kGka, ca Sca, ca - k XkGka,caSka, ca k XkGka, ca (11)c. 0“ Vr T1ZalnClc2 = cXc cXc k XkGka, caSka, ca k X kGka, ca + mXmGam k X kGkm Sam - k XkGkmSkm k XkGkm+ c aXa aXcXcGac, ac k XkGkc, ac Sac, ac - k XkGkc,acSkc, ac k X kGkc, ac (12) T(8)j( 12): Xj= xjcj(xj: 0 : i, 0cj= Z
12、j,c39c杜英生等? A A 9 s0cj= 1); Zj: 0 ;Gji= exp (- AjiSji) j; Aji:d 1 , |Aji= 0. 2; Sji: 0jiWT ; Gji, ki= exp (- Aji, kiSji, ki); |Aji,ki= 0. 2;Smc, ac= Sam- Sca, m+ Sm, caSma, ca= Sam- Sca,m+ Sm, caSca, ca= - Sca, caSca, ca= - Sca, ca/S: i, j, k- i 0; a, a, a- 0;c, c, c-| 0; m-s0bChen 6|NH3-H2S-H2O8“ T
13、 SBs1 f , 6Bs% , ,yN L 151 ,|t% 9V Uf btT 1 T/:SNH3,H2O= 0. 7449- 453. 80/TSH2O, NH3= 1. 6707- 932. 83/ TSH2S, H2O= - 3. 674+ 1155. 9/TSH2O, H2S= - 4. 180+ 1617. 74/TSH2O, NH4HS= 20. 05- 4520/TSNH4HS, H2O= - 9. 152+ 1890. 4/TS*NH4HS, NH3= - 4. 058- 233. 43/TS*NH4HS, H2S= - 2. 536+ 140. 9/T S*ca, m=
14、- 4. 07- 229. 1/T;S*m, ca= 19. 85- 4168. 9/TSca, ca= 0 1 T(* ) 1 T b3 9 T1 /V NH3-H2S-H2O“d353. 15K,9a9 ; i/“ 9T L1 bNH3-H2S-H2O8“9 T L41( 353. 15K)Noimol/ kgH2OPNH3/PH2SkPaNH3 H2S L9 Edwards BeutierE Chen1 0.960 0.971 1. 6/ 318. 5 1.546/284. 37 1. 43/304 1.47/317 1. 466/ 314.64 1.452/ 316. 32 1.063
15、 1.452 0.58/ 1140.7 0.568/1218.7 0. 51/1218 0. 58/1227 0. 56/1343. 5 0.56/1358. 33 2.332 1.151 18.1/42. 5 20.22/ 35. 2 18. 47/40. 5 17.0/44. 3 18. 7/ 41.2 18.5/ 42.34 5.112 1.143 76.5/12. 6 70.1/10. 8 65.8/13.5 59.3/12. 5 65. 8/ 12.8 65.7/135 5.538 5.305 9. 68/1618 9.45/ 2084.9 10.4/1339 7. 89/1784
16、9.50/ 1574 9.52/1594. 36 9.245 7.935 27. 7/ 1267.3 23. 46/3060.5 31.3/1282 20.2/1265 26.3/1199. 9 27. 0/1239. 27 10.201 5.983 79. 6/ 255. 4 63.2/329. 2 87.6/248 61.8/229 72. 9/ 232.7 74.8/2448 22.627 5.561 304.6/32. 1 322. 1/ 26. 1 375/ 56.8 312/ 36.1 310.9/38.8 312.6/ 34.05E(%) = Pcal- PexpPexp/N 8
17、. 70/33.37 11. 20/15. 1 13.38/5.73 5.81/ 8. 34 5. 20/ 4. 71V1 V AE 8Edwards $ F T,9 A4, 9 V4 V ,9 , 9 HW9 bYVChen t% 1 ,9 1Chen 4bB4 , Zss0- T SMf ,A MbyN zA ,|tT BB1 p, VB4 A b4 Chen ZNRTL“ $| tT F1 ,A 9 T Chen9 T,i O ZPitzer (Edwards, Beutier,E ) 9 T1 ,?C9 v4b4 A ? ,A V4 E9 T , bWc ; ) ZE 4, !91o
18、9 ,yc40c1998 M26 6 N V 4 T iaS a A E9 ,49 a V L,V7MSv 4 ?r) 7C / !9S B$Tb ID1Van Krevelen, D W, Hoftijzer P J, et al. Rec TravChim Pays-bas, 1949, 68: 191.2Edwards T J, Newman J, etal. AIChE J, 1978, 24:966.3Wilson C M. , API Publication, 1978.4Beuiter,D, Renon H. IndEng Chem Process Des Dev,1978, 1
19、7: 220.5Chen C-C, Britti H I, et al. AIChE J, 1982, 28: 588.6Chen C-C, Evans L B. AIChE J, 1986, 32: 444.7Bernardis M, Carvoli G, et al. AIChE J, 1989, 35:314.8E ,., 1983, 3: 234.9Jia Tieh, Tong Aryu, et al. Proceedings CKCSST95.Tianjin China, 1995. 121.10, C. Fv(1 S), 1993,17: 81.11Zemaitis J F, Ra
20、fal M. Symp 68thAnnual Meeting,LA, 1975.12Gautam R, SeiderW D. AIChE J, 1979, 25: 1006.13Nakamura R, etal. IndEng ChemProcess Des Dev,1976, 15: 557.14Breivi SW, OConell J P. AIChE J, 1972, 18: 1329.15NewmanSA. ACSSymposium Series 133, 1980. 173.c41c杜英生等? A A 9 for both pure fluids and fluid mixtures
21、. Satisfactory results are obtained.Keywords: corresponding states principle, thermodynamic property, predictionEquilibrium Calculation of Aqueous Volatile Weak Electrolyte SystemDu Yingsheng, Wang Lidong, Du Xiang, Yu Guocong(Chemical Engineering Research Center of Tianjin University, Tianjin 30007
22、2)Zhang Fengbao, Zhang Guoliang(Chemical Engineering Department of Tianjin University)Based on the model of extended NRTL by Chen (1986) , modification was made by using experi-mental data to correct some fixed parameters as function of temperature. By calculating the VLE ofNH3-H2S-H2O system, we fo
23、und the calculated results were in good agreement with experimental datain the literature. We also compared the results of modified model with those of other models such asEdwands, Beutier, Chen, et al.Keywords: aqueous volatile, weak electrolyte system, vapor-liquid equililbra, NRTL equation, ammon
24、i-um, hydrogen, sulfide, waterEstimation of Acentric Factor of HydrocarbonsTian Fangren(Fushun Petrochemical Research Institute, Fushun 113009)The acentric factor and critical temperature of hydrocarbons are correlated by using the boilingpoint and molecular weight. The acentric factor values calcul
25、ated by eg. 7. The average absolute erroris 7. 06% based on 104 hydrocarbon compounds and critical temperature values calculated by eg. 6.The average absolute error is 2. 29% based on 119 hydrocarbon compounds.Keywords: hydrocarbons, acentric factor, critical temperatureImprovement of BP Algorithm o
26、n Network Training and Application ofANN in Catalytic Distillation Column SimulationZhao Zhishan, Kuang Ge, Wang Liangen, Zhao Suying(Chemical Engineering Dept. of Fuzhou University, Fuzhou 350002)Liu Jiaqi(Chemical Engineering Department of Tianjin University)A new training method of back-propagation ANN was proposed. We applied it to simulate thec4cCHEMICALENGINEERING ( CHINA)Vol. 26, No. 6, 1998
