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1、天津大學(xué)碩士學(xué)位論文碳酸酯合成體系中汽液相平衡的測(cè)定與關(guān)聯(lián)姓名:劉新剛申請(qǐng)學(xué)位級(jí)別:碩士專業(yè):化學(xué)工藝指導(dǎo)教師:許根慧;馬新賓20021201摘要碳酸二甲酯和碳酸二苯酯是兩種重要的綠色化工產(chǎn)品。甲醇氧化羰基合成碳酸二甲酯工藝以及草酸二苯酯與苯酚酯交換法合成碳酸二苯酯工藝越來(lái)越受到國(guó)內(nèi)外研究人員的青睞。在反應(yīng)產(chǎn)物的分離設(shè)計(jì)中,需要相關(guān)物系的汽液平衡數(shù)據(jù)。本文將液上自動(dòng)進(jìn)樣器和氣相色譜儀聯(lián)用,采用液上氣相色譜法測(cè)定汽液平衡,用甲醇一苯物系對(duì)其可靠性進(jìn)行了檢驗(yàn),測(cè)定值與標(biāo)準(zhǔn)值吻合良好。實(shí)驗(yàn)測(cè)定了甲醇氧化羰基合成碳酸二甲酯以及酯交換法合成碳酸二苯酯產(chǎn)物中有關(guān)的五組
2、二元物系:甲醇.碳酸二甲酯、甲醇.草酸二甲酯、碳酸二甲酯一草酸二甲酯、甲醇.苯酚、碳酸二甲酯.苯酚分別在不同溫度下的汽液平衡數(shù)據(jù),并用Herington法對(duì)所測(cè)定數(shù)據(jù)進(jìn)行了熱力學(xué)一致性校驗(yàn)。本文研究了數(shù)據(jù)處理中液相組成的校正方法,用非線性最小二乘法對(duì)所測(cè)物系進(jìn)行了活度系數(shù)方程的關(guān)聯(lián),并對(duì)活度系數(shù)方程參數(shù)與溫度的關(guān)系進(jìn)行了回歸,所得結(jié)果令人滿意。同時(shí)對(duì)兩個(gè)三元物系的汽液平衡數(shù)據(jù)進(jìn)行了推算并與實(shí)驗(yàn)值進(jìn)行了比較,兩者符合較好。本文還利用實(shí)驗(yàn)測(cè)定的汽液平衡數(shù)據(jù)對(duì)uNIFAc新基團(tuán)的相互作用參數(shù)進(jìn)行了回歸,擴(kuò)充了UNIFAC模型的應(yīng)用范圍。關(guān)鍵詞:液上氣相色譜法。汽
3、液平衡,UNIFAC模型,碳酸二甲酯,碳酸二苯酯草酸二甲酯,苯酚AbstractDimethylcarbonateanddiphenylcarbonatearetwoimportantgreenchemicalproducts.Theprocessesofdimethylcarbonatesynthesisbyoxidativecarbonylationofmethanolanddiphenylcarbonatesynthesisbytransesterificationofdimethyloxalatewithphenolarepromisingrout
4、es,whichattractmuchattentionofnationalandabroadresearchers.Thevapor—liquidequilibriumdataarerequiredfordesigningproductseparationprocess.Adeviceformeasuringvapor-liquidequilibriumdatabyconnectingaheadspacesamplerandgaschromatographWasset-up.Thereliabilityofthisdeviceandthefeasibil
5、ityformeasuringvapor-liquidequilibriumofthestudiedsystemshavebeenconfirmedbymeasuringmethanol-benzenesystem.Theexperimentalresultsareinagreementwithstandarddata.Thevapor—liquidequilibriumdataOfthefollowingfivebinarysystemshavebeenmeasuredatdifferenttemperatures:methanol-dimethylca
6、rbonate,methanol—dimethyloxalate,dimethylcarbonate-dimethyloxalate,methanol-phenolanddimethylcarbonate—phen01.ThethermodynamicconsistencyofthesedatawasexaminedbytheHeringtonmethod.Themethodforcorrectingliquidcompositionhasbeenstudied.Theparametersinactivitycoefficientequationswere
7、correlatedfromvapor-liquidequilibriumdatabynonlinearleastsquaremethod.Theseparametersoftheactivitycoefficientequationswerecorrelatedwithtemperatureforthefivebinarysystemsandsatisfactoryresultswereobtained.Basedonthesedataandmathematicalmodel,thevapor-liquidequilibriumdataoftwotern
8、arysystemshavebeenpredictedandcom