常壓下環(huán)己烯環(huán)氧環(huán)己烷二元汽液平衡數(shù)據(jù)的測(cè)定和關(guān)聯(lián)_圖文

1、第23卷第3期 2009年6月高?；⒐こ屉?bào)Journal ofChemical Engineering ofChinese UniversitiesNo.3、,01.23 June 2009文章編號(hào):10039015(200903-036504常壓下環(huán)己烯.環(huán)氧環(huán)己烷二元汽液平衡數(shù)據(jù)的測(cè)定和關(guān)聯(lián)王學(xué)猛,蔣登高,耿再新(鄭州大學(xué)化工學(xué)院,河南鄭州450001摘要:用分子氧對(duì)環(huán)己烯直接進(jìn)行環(huán)氧化涉及到的內(nèi)容之一是環(huán)己烯與環(huán)氧環(huán)己烷的分離。為了為二者的分離提供基礎(chǔ)物性數(shù)據(jù),采用了改進(jìn)的EC.2型汽液平衡釜測(cè)定了常壓下(101.33kPa環(huán)己烯(1環(huán)氧環(huán)己烷(2二元體系的汽液平衡數(shù)據(jù).所得結(jié)果經(jīng)檢

2、驗(yàn)符合熱力學(xué)一致性。用Wilson方程對(duì)所測(cè)的汽液平衡數(shù)據(jù)進(jìn)行了關(guān)聯(lián),求出了Wilson方程 交互作用參數(shù),并對(duì)汽液平衡的計(jì)算值與實(shí)驗(yàn)值進(jìn)行了比較,發(fā)現(xiàn)二者偏差較小,可以滿足工程上環(huán)己烯、環(huán)氧環(huán)己烷分離設(shè)計(jì)的需要。關(guān)鍵詞:汽液平衡;環(huán)己烯:環(huán)氧環(huán)己烷:Wilson方程中圖分類號(hào):0642.42;0624.12;TQ231.14文獻(xiàn)標(biāo)識(shí)碼:AMeasurement and Correlation of Vapor Liquid Equilibrium Data forCyclohexene-l,2-epoxycyclohexane Binary System under Normal Press

3、ureWANG Xuemeng,JIANG Deng-gao,GENG Zai-xin(School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,ChinaAbstract:Using dioxygen叢oxidizing agent to conduct the green oxidation of eyclohexene is highly desirabIe because of its environmental compatibility and economic impact.Separation of

4、 the cyclohexene oxidation products depends on the reliable vapor-liquid equilibrium(vLEdata of relevant components,which are still lacking.Thc VLE data of cyclohexene and 1,2-epoxycyclohexane binary system under ambient pressure were measured by using an improved VLE equipment of EC-2stilI in tIlis

5、 work.The results show that thisbinary system Ilas no azeotropic point.Furthermore,the experimental VLE data were correlated with the Wilson thermodynamic model and the corresponding binary interaction parameters of the model were Obmined.Thecalculation shows that the VLE data agree well with the mo

6、del and all experiment data pass the thermodynamic consistency test of Herrington.Key words:vapor-liquid equilibrium;eyclohexene;1,2-epoxycyclohexane;Wilson equation1引 言2實(shí)驗(yàn)部分2.1試劑和儀器環(huán)氧環(huán)己烷,山東銀鷹化纖有限公司,99.3%:環(huán)己烯ACl的S ORGANICS,99%。所用試劑的收穡日期:2008-07-1l:修訂日期t 2008-12.19.南?；⒐こ虒W(xué)報(bào) 2009年6月主要物性數(shù)據(jù)見(jiàn)表l。改進(jìn)的EC-2汽液

7、平衡釜,見(jiàn) 圖l:氣相色譜儀,GC.900A上海科創(chuàng)色譜儀器有 限公司,帶FID檢測(cè)器;1/10溫度計(jì)(50-100(2, 100150C各一只,使用中已進(jìn)行零點(diǎn)、刻度及露 頸校正。2.2分析用帶FID檢測(cè)器的氣相色譜來(lái)分析汽液兩相平衡 組成,以式(I歸一化法來(lái)進(jìn)行定量計(jì)算。ml=flAl/(fiAl+A2x 100(1襄l所用試劑的主要物性參數(shù)Table I Bssic properties of relative substances墜匹墮墮 盟!墜!型:蘭 !:;蘭侖!型!匹!塑鯉坐! r。,K 560.3560780Pcf kPa 43464021.0K10。/mmol1292329*

8、C -49046-64912Note:Iog圖1BC-2型汽液平衡數(shù)據(jù)測(cè)定裝置示意圈1Fig.1Sketch ofEC2VIE equipment 圖2常壓下苯(1-甲苯(2二元物系1.heating rod 2.temperature point的汽液平衡值的比較3.1iquid sample connection 4.glass VLE b礎(chǔ)e Fig.2Comparison bctwccn mq把runent and literature7.vapor phase smnple connection trader normal pressure2.3驗(yàn)證性實(shí)驗(yàn)為了檢驗(yàn)所用儀器、設(shè)備的可靠

9、性,首先測(cè)試了十組常壓下苯(1-甲苯(2二元汽液平衡的數(shù)據(jù),并 對(duì)實(shí)驗(yàn)值與文獻(xiàn)值【ll】進(jìn)行了比較,結(jié)果見(jiàn)圖2。其中相對(duì)偏差粕和如見(jiàn)式(2和(3。式中下腳標(biāo)exp粕=OJ鋤JlJjt詹JJjl100(2 yfl毗yIlit陟l墩x 100(3 和lit分別表示實(shí)驗(yàn)值和文獻(xiàn)值。數(shù)據(jù)分析表明,在驗(yàn)證性實(shí)驗(yàn)中液相摩爾分?jǐn)?shù)的相對(duì)誤差札9.1%,氣相 摩爾分?jǐn)?shù)誤差yd_4.2%。由此可以說(shuō)明,實(shí)驗(yàn)值與文獻(xiàn)值吻合良好,利用本裝置進(jìn)行常壓下(101.33kPa 汽液平衡數(shù)據(jù)的測(cè)試是可行的。2.4汽液平衡數(shù)據(jù)的測(cè)取將二元混合溶液裝入平衡釜后,在常壓下(101.33kPa下緩慢加熱使溶液沸騰,沸騰一段時(shí)間后,用

10、 氣相色譜連續(xù)檢測(cè)汽液相組成,直至汽、液相組成不再變化時(shí),此時(shí)確認(rèn)汽液兩相達(dá)到平衡,記下相應(yīng) 的溫度,并分別取汽液兩相的樣品,進(jìn)行檢測(cè),每個(gè)點(diǎn)連續(xù)檢測(cè)三次,取其平均值作為該溫度及組成下 的汽液平衡數(shù)據(jù)。不斷改變二元混合溶液的組成,便可測(cè)得常壓下環(huán)己烯(1-環(huán)己烯環(huán)氧環(huán)己烷(2的二 元物系的系列汽液平衡組成。第23卷第3期 王擘猛等:常壓下環(huán)己烯.環(huán)氟環(huán)己烷二元汽液平衡數(shù)據(jù)的測(cè)定和關(guān)聯(lián) 3673結(jié)果與討論3.I測(cè)得的汽液平衡數(shù)據(jù)常壓下,所測(cè)環(huán)己烯(1.環(huán)氧 環(huán)己烷(2二元物系的汽液平衡數(shù) 據(jù)見(jiàn)表2,相圖見(jiàn)圖3。由圖3及表2知,常壓下環(huán)氧 環(huán)己烷的沸點(diǎn)為404.65K,這與文 獻(xiàn)【10】所報(bào)道的4

11、04.87K基本一 致。環(huán)己烯的沸點(diǎn)為356.12K,這 與文獻(xiàn)值【9】所報(bào)道的356.13K值 十分接近。3.2熱力學(xué)一致性檢驗(yàn)采用Herrington等面積檢驗(yàn) 法【1習(xí)對(duì)所得的數(shù)據(jù),進(jìn)行熱力學(xué)一 致性檢驗(yàn),其結(jié)果如表3和圖4所 示。其中,0=T2一T-為二組分的沸 點(diǎn)差,K;死為體系的最低沸點(diǎn),K。 d=警;1=JcoIn銣2; 2=一 ; 2田而 o m ,=Elh糾;。=跏。表2常壓下環(huán)己烯(1環(huán)氧環(huán)己烷(2二元物系的汽液平衡數(shù)據(jù)Table 2VLE data of eyclohexene(1-l,2-epoxyeyelohexane(2binary system !璺堅(jiān)!翌!竺!1

12、21111竺堡T/K里!堡翌四!墜 型!熊!鯉 n Y2Note:母弓缸。,礙xl,Yl represent molar fraclJon of cyclobcxene in licIuid and vapor phase五,五 磚珥刪。驢刨I(mǎi)T茸吐越曲毋coc婦丘ch岱of毋d ol】日螄鋤d l-2-cpoxy撇,respecuvdy由表3數(shù)據(jù)可以看出,D“證明所測(cè)數(shù)據(jù)符合熱力 學(xué)一致性。3.3數(shù)據(jù)關(guān)聯(lián)文獻(xiàn)【13,14】的作者,分別用UNIQUAC、NRTL、 Wilson方程對(duì)各自的研究體系進(jìn)行了關(guān)聯(lián),結(jié)果表明計(jì) 算值與實(shí)驗(yàn)值的偏差較小,可以滿足工程設(shè)計(jì)的需要。 考慮到本研究體系是在常壓

13、下(i01.33kPa的汽液平 衡,汽相可以當(dāng)作理想氣體,液相的活度系數(shù)用Wilson 方程關(guān)聯(lián)。另外,在本體系中,兩物質(zhì)的沸點(diǎn)差為 48.53K,溫差不大,Wilson參數(shù)可以當(dāng)作常數(shù)。為此,月, 、2選定目標(biāo)函數(shù)為:F=(咒叫一,下角標(biāo)cal表,;J。J示計(jì)算值,exp表示實(shí)驗(yàn)值。通過(guò)非線性回歸分析, 得到Wilson參數(shù)A12=1.1985A2l=0.3544。然后用求得 的Wilson參數(shù),計(jì)算相應(yīng)溫度下的氣相組成,并將計(jì) 算結(jié)果實(shí)驗(yàn)值進(jìn)行比較。結(jié)果見(jiàn)表2。由表2知,計(jì) 算值與實(shí)驗(yàn)值吻合良好。其中,在30組檢測(cè)數(shù)據(jù)中 襲3熱力學(xué)平衡數(shù)據(jù)一致性檢驗(yàn)塾絲!三!竺!璺Z璺!磐生!竺呈!堡絲!

14、塑!墜曼k工l o.1圈3環(huán)己烯(1肼氧環(huán)己烷(2二元體系的置于丁圖 Fig.3x-y-Tdiagram ofcyclohexene(1-1,2-_eIxxyeyclohexene(2binary systemk一弋II圈4Xl-ln(7m/721曲線圈Fi94Diagram ofxl-ln Ol饑 曹一368高校化學(xué)工程學(xué)報(bào) 2009年6月緲較大的僅有兩個(gè),分別僅為0.0191、0.0171,其余均較小,誤差最小者僅為一0.0001,其中平均誤差B 為:q=去蕪M 2o.o懈 (4 這說(shuō)明可以用Wilson方程對(duì)常壓下環(huán)己烯與環(huán)氧環(huán)己烷的二元體系汽液平衡數(shù)據(jù)進(jìn)行關(guān)聯(lián),結(jié)果可以滿 足工程上分離

15、設(shè)計(jì)的要求。4結(jié) 論(1常壓下(101.33kPai9lJ定了30組環(huán)己烯(1-環(huán)氧環(huán)己烷(21拘-元汽液平衡數(shù)據(jù),經(jīng)熱力學(xué)一致性 檢驗(yàn),所得數(shù)據(jù)符合熱力學(xué)一致性。(2所測(cè)數(shù)據(jù)用Wilson方程進(jìn)行關(guān)聯(lián),求出了Wilson交互作用參數(shù)和汽相平衡組成的計(jì)算值,計(jì)算 值與實(shí)驗(yàn)值之間的偏差較小,可以滿足工程上分離設(shè)計(jì)的要求。參考文獻(xiàn):【l】Niaasary M S,Farameh FOhandi M et a1.Oxidation of cyclohexene with tcn-butylhydroperoxide catalyzed by manganesII complexes included

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