Measurement and Correlation of Solubility for Propylene in 2-Propanol-Water Solutions

Transactions of Tianjin UniversityVol.9 No. 3Sep.2003Measurement and Correlation of Solubilityfor Propylene in 2-Propanol-Water SolutionsLIU Guo-zhu(刘国柱) ,REN Yong-li(任永利) ,MI Zhen-tao(米镇涛) ,WU Yu-long(吴玉龙尸( 1. School of Chemical Engineering and Technology ,Tianjin University , Tianjin 300072 ,China ;2. Department of Chemical Engineering , Tsinghua University , Beijing 100084 , China )Abstract :In order to obtain the solubility data of propylene in 2-propanol-water solutions , gas-liquid equilibri-um( GLE ) experiments were carried out at 303. 15- 333.15 K ,0.27- -0. 98 MPa in a static equilibrium sillThe original mass ratio of 2-propanol to water was 9:18:2 7:3 1:0 ,respectively. The equilibrium data werecorrelated with an empirical model and the regression of model parameters was completed by Gauss-Newton non-linear least square( NLS ). The average relative deviation( ARD ) between the experimental and calculated val-ue is 1. 57% , and the maximum relative deviation( MRD ) is 4. 82%. In addition ,a simple approach that cor-related the model parameters with the system composition was also provided.Keywords solubility ; propylene ; 2-propanol- water ; gas-liquid equilibriun( GLE )Article ID :1006-4982( 2003 )03-0180-04From a practical point of view ，the integrated 1.1 Materialsprocess of epoxidation of propylene with hydrogen peroxide2- Propanol ( from Tianjin Chemical Reagent Factoryto prepare propylene epoxide is of considerable interest ，99. 8% in mass ) ;Propylene ( from Tianjin Gas Corpora-not only because of their positive contribution to the envi- tion ，>99. 9% in mass ) ;Distilled water( distilled twice ,ronment , but also their improvements of the oxidation effi-conductance<0.5 S ).ciency of hydrogen peroxide 1-31. In the development of 1.2 Apparatus and analytical techniquesthose processes , the solubility data of propylene in variousThe apparatus used for GLE studies is shown in Fig.solvents for the generation of in situ-hydrogen peroxide play 1. A stainless-gauge with a total volume of 60 cm3 wasan important role + '.used as an equilibrium cell. The temperature in the equi-In our previous papers一, we have reported severallibrium cell was measured by an mercury thermometer withvapor-liquid equilibrium( VLE ) data of propylene in vari-the minimum scale0. 1 K , and the pressure measured by aus solvents. Up to now , the gas-liquid equilibriumprecise piezometer ( Hangzhou Instrument Factory , 0.25( GLE ) data of propylene 2-propanol-water ternary systemgrade ). The pressure fluctuation was regulated to withinhas not been reported. What should be mentioned is that+0.01 MPa. The inner temperature of the vaporizer wasGLE rather than VLE is used in this paper to define thecontrolled by an SR63 temperature-controller( Beijing Shi-property of the system , as suggested by Prausnitzt 81 ,since .maden Institute of Automatics ) and monitored by a thermo-couple connected to a temperature indicator. All pipes andpropylene is a non-condensation gas 9 ]In this research we mainly aim at obtaining such datajoints had passed through the gas leakage test.The components of liquid phase were analyzed on anunder interested conditions , at the same time we try to cor-SP3700 gas chromatograph( GC , Beijing Analysis Instru-relate those data using the empirical model suggested by LiimentFactory).TCDandthecolumn(3.0mxφ3.0X and Hou Y et at10].中国煤化工1 Experimental procedureAcc |MHCNMHGLIU Guo-zhu , born in 1979 , male , doctorate student.E-mail gzhliu@ eyou. comThe solubility of propylene in 2-propanol-water solu-* Supported by National Program of Key Scientific Researchtions was measured by the static cell method.( G2000048005 ).LIU Guo-zhuu et al :Measurement and Correlation of Solubility for Propylene in 2-Propanol- Water Solutionsmm ) packed with GDX-103 were used for this purpose. As 1.3 Procedurecarrier gas , hydrogen was at a flow rate of 40 mL/ min.The equilibrium experiments were conducted atThe temperature of the column was kept at 428. 15 K，303.15- -33.15 K ,0.27- -0.98 MPa in a static equilib-while that of the injector and detector at 433. 15 K. The rium still , in which the mass ratio of 2-propanol to waterquantitative analysis was carried out by the modifed area was9:1 8:2 7:3 ,1:0 , respectively. Firstly , the equilib-normalization method.rium cell was placed in a super-thermostatic bath tank( temperature fluctuation is +0.1 K ). Then it was vacuu-mized by a vacuum pump ( residual pressure <0. 72 Pa ) ,heatlneiectelNitrngenthe 2-propanol and water were injected into the cell fromthe top-inlet. Next , propylene was introduced into the gasdistributor from the gas bomband blistered in the liquidFHydrogen11phase. The equilibrium state was kept for 100 min. At- Phopylerelast , the liquid phase sample was introduced into a vapori-口常zer first and then blown into GC with nitrogen after thVecum pumproughly vaporized. The vaporizer temperature was kept at413.15 K. All the pipes and joints were kept at 403.15 Kby the insulating jacket to avoid condensation of water and用1手|Oatlet ，2- -propanol.1.4 Reliability verification of the apparatusThe reliability of the experimental set-up and tech-1- -equilibrium cell ;2- -gas distributor ; 3- -thermometer ;4- -condenserpipe ;5- -motor stirer ;6- -thermostatic bath tank ; 7- -heating resistor ; .nique was confirmed by comparing the binary GLE data of8- -sampling tube ;9- -sample indicator bottle ; 10- -vaporizer ;11- -six-the propylene-water system obtained with that of the litera-port valve ;12- -thermocouple ;13- buffer container ;14- -vacuum pump ;ture' 10]. Tab. 1 summarizes the experimental and literature15- -gas chromatograph ;16- -integratorGLE data as well as the relative error. Obviously , the ex-Fig. 1 Schematic diagram of experimental apparatusTab.1 Comparison of experimental data with data in literatureValues in literatureExperimental valuesRelative error/%T/Fp/MPaY12/10-3Xx:/10-4 Yexp /10 -X.x:/10 -OX/XmAY/Y;310. 960. 25526. 961.523 626. 0801.594. 35-3. 26310. 980.454 .12.612.976 712. 3012. 91-2.13 .-2. 46310. 930. 640.4. 18058. 7864.02-3. 84-2.38310.960. 8916.395.575 06. 6625.763.263. 6X is molar fraction of propylene in liquid phase ; Y is molar fraction of water in vapor phase ;AX=Xexp -Xxa ;OY=Ygp- Ynaperimental data are consistent with those of literature , fur-Ir( x/p)=A| +A2p +Asp2A4 +Asp+A6p2+thermore , the maximum relative error is smaller than 5% .7(A, +Asp+Aqp2 )In Twhere A- Ag are parameters dependent on the component2 Experimental data and correlationof the solution ;x is the molar fraction of the propylene inthe solution ; T is temperature of the system.2.1 Experimental data2.3 Regression of model parametersTab.2 presents the experimental solubility data of pro-Expression for the objective function( OF )is aspylene in 2-propanol-water solutions with different concen-trations.2.2 Model for correlation中国煤化工nonlinear least squareLi X and Hou Y et at 10] gave a multi-parameter em-(NIS)the model described above. The regression results of differ-MHCNMH Gon of the parameters forpirical model for the solubility of gas in solutions or liquidsent mass ratio solutions are given in Tab. 3.in 1993. It has a form as一181一Transactions of Tianjin UniversityVol.9 No.3 2003Tab.2 Solubility of propylene in 2-propanol-water solutionsTemperature PressureSolubiltySolubility0H/H2O*0H/H20*T/Kp/MPa Sap"RD/%ρ/MPa__ SapSaRD*/%303.150.4100.066 750. 068 252.25305. 15). 3430.025 50 0. 025991. 920.5200.081 930.081 910.020.4300.03766 0. 036542. 97303. 150. 6100.09444 0.095 190. 79305.150.5600.055 11 0. 054620.890.7200.11533 0. 116 060.630. 68(0.07457 0.072 722. 48313. 150.450.0.06061 0. 058 952. 74313.150.350 0. 02067 0. 02044 1. 110.5700.074 400.073 310.470.4400.028 810. 030204.82.0. 6900.091 48 0. 090850.69.0. 5000.035 790.037 11 3. 690. 7300.098 620.097 770. 860. 6200.051 250.053 273.940.8000.11226 0.111 640.550.7700.06930 0.071 633.369:1323. 150. 4400.04560 0. 046451. 8(323.150.4000.021 77 0.021 18 2. 710.5300.055 19 0. 056352.100.034 090. 033481.790.6200.065 940. 067 282.030.600 0.04475 0.042 68 4. 630.7300.082 800.082 720.100.70(0.056740.054503.950.840.0.10037 0. 101 391.02333.150.026940. 027803. 19333. 150.4700.040 820. 040 331.200.04791 0. 048721. 690.600.0.05520 0. 054 860.620. 81(0.065 600. 065 860.400.071 55 0.071 450.140.9600.091830.092 110.300. 8400.087 74 0. 08743 .0.350.9800.110770. 110 850.07333.15 .0.5100.15529 0. 158942.350.5400.16663 0.167 240.370. 3000.01906 0.019 261. 050.18169 0. 184 971. 810.370 0.02448 0.025 022. 21303. 15.0.6500.205 18 0.201 221.90. 4660.033 830. 034241.210.2900.069820.070480.950.520 0.04022 0.04026 0. 100. 3900.088 70 0. 092324. 080.6900.062760.064713.110.133380. 132 031.010.3600.018890.018 760.690.6400.16198 0. 161 490. 300.02559 0. 025 062.070.193590. 190 811.440. 5300.035 280. 034 711.620.7600.20627 0.20129 2. 410.750 0. 06336 0.06358 0.350.8800.251 74 0. 247751. 580. 8600.089 480. 086453.391:00. 970.0.285 720. 287 460.617:30.360.01053 0. 010721. 800.096 700. 099 853. 260.023 640.024 202.370.6100.12298 0. 12453.1.260.5500.02448 0.025 102. 530.7400.16233 0. 161 810.320.6700.03911 0.039 781.710.8100.183 760. 185 050. 700.04244 0. 042480.090.9100.21854 0.223 132. 100.830 0.063 36 0.06535 3. 140.2700.046 800. 046 550.530.3200.00555 0.005 510.720.4200.068 10 0. 068510.600. 4500.01221 0.011 912.460.520.0.085 14 0. 085 020. 140.02025 0.020 200.250.113310.111 69.1.430.039 11 0. 038970.8300.167430.166750.410.06120 0. 060 620.95 .Average relative deviation( ARD )1.57Maximum relative deviation( MRD )4.82Mass ratio of 2-propanol to water ;b Molar fraction of propylene in 2-propanol. water solution obtained in experiments ;Molar fraction of propylene in 2-propanol-water solution obtained from calculation ;d Relative deviation :RD_ lSal -Soxpx 100%中国煤化工SxpMHCNMHGThe values calculated using the model are given inbetween the experimental and calculated value is 1. 57%Tab.2 as well as the relative deviations of each data. As, the maximum relative deviation ( MRD ) is 4. 82%.shown in Tab. 2 , the average relative deviation( ARD )Moreover , Fig. 2 also shows the higher accordance of ex-一182五方数据LIU Guo-zhu et al :Measurement and Correlation of Solubility for Propylene in 2-Propanol- Water Solutionsperimental values and calculated values from the empiri-almost all A; have a larger R2 approaching 1 , thereforecal model.we can use the approach when the compositions are not9:1 8:2 7:3 1:0 and the required precision is not high-Tab.3 Regression result of model parametersr.Para-Mass ratio of 2-propanol to watermetersA;7:39:11:03Conclusions1 969. 028-4 012. 050621.284 - 3 285. 84A2 -3902. 60012 406. 970-1505. 030.9 874. 688A32237. 189 - 10 415. 300733.804.-7307.2001 ) The solubility data of propylene in 2-propanol-A4 -85 989. 90019 0117. 100- 25 026. 100 156 664. 300water solutions under 303. 15- -33.15 K ,0.25-1 MPaAs 172 545. 900 - 582 439. 00062 943. 950 - 464 773. 000are obtained.Ao -99 274.500487859. 000-29 119. 600343 016. 2002 ) An empirical model suggested by Li X and Hou- 295. 499591. 843-94.482484. 474Y et al was used to correlate the obtained data. ResultsAg583. 403-1 834.720226. 635-1 460.090- 334. 0791 540. 940-111. 2581 081.011show that ARD between the experimental and calculatedvalue is 1.57% , MRD is 4.82%.3 ) A simple approach that correlated the model pa-0.300.25。Experimental :rameters with the system composition is also provided.valuesCaleu!latedReferences0.20 t[ 1 ] Clerici M G , Ingllina P. Epoxidation of lower olefins with hydrogen0.15peroxide and titanium slicalie[J]_ J Catal , 1993 ,140( 1 ):71-[2] ShuL ,Shi Y. An fficient ketone-catalyzed asymmeric epoxidation0.05using hydrogen peroxide( H2O2 ) as primary oxidan[ J ] Tetrahed-ron ,2001 57( 24 )5213- -5218.0.10 0.150.200.250.30[3] Laufer W , Meiers R , Holderich W. Propylene epoxidation with hy-Calculated valuesdrogen peroxide over palladium containing titanium silicaliteC J ] JFig. 2 Comparison between the experimental andMol Catal A :Chemical ,1999 ,141( 1-3 ) 215- -221.calculated values[ 4 ] Jenkins J 0. 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