乙烯氫甲?；瘎?dòng)力學(xué)研究

第33卷第4期計算機與發(fā)用化骨2016年4月28日Computers and applied chapril 22如4乙烯氫甲?；瘎?dòng)力學(xué)研究楊普,王玲,刁琰琰,李春山,王蕾(中國科學(xué)院過(guò)程工程研究所,離子液體清潔過(guò)程北京市重點(diǎn)實(shí)驗室多相復雜系統國家重點(diǎn)實(shí)驗室,北京,100190)摘要:固定甲苯、催化劑及配體用量,對乙烯在甲苯溶劑中的氫甲?；磻獎?dòng)力學(xué)進(jìn)行了研究。以反應計量比為11:1的乙烯一氧化碳和氫氣為反應混合氣,測定了100℃、93℃和81℃下反應壓力隨時(shí)間的變化曲線(xiàn),通過(guò)動(dòng)力學(xué)方程求解獲得了3種氣體總的反應級數、反應速率常數和活化能,得到反應的活化能為550kJ/mo。進(jìn)一步通過(guò)一氧化碳和氫氣過(guò)量,得到了乙烯的反應級數。然后通過(guò)氫氣過(guò)量,得到了乙烯和一氧化碳的總反應級數,隨后即計算得到了一氧化碳和氫氣各自的反應級數,表明一氧化碳分壓高會(huì )抑制反應速率,而增加乙烯和氫氣分壓對反應速率有促進(jìn)作用。關(guān)鍵詞:乙烯;氫甲?；?動(dòng)力學(xué)中圖分類(lèi)號:TQ0159;TP3919;06-39文獻標識碼:A文章編號:10014160(2016)044414Dol:10.16866/j.com.appchem2016040121引言2實(shí)驗部分氫甲?；磻窍N與一氧化碳和氫氣反應銠膦催化劑為實(shí)驗室自制,甲苯溶劑和三苯基生成醛,進(jìn)一步可生產(chǎn)醇、酸等重要的化學(xué)品,用膦為國藥化學(xué)試劑有限公司生產(chǎn)。乙烯、一氧化碳于藥品、香料、聚合單體等的生產(chǎn)。其中低碳烯烴從北京兆格氣體科技有限公司購買(mǎi),氫氣從北京市均相氫甲?；呀?jīng)被廣泛工業(yè)化應用3北溫氣體制造廠(chǎng)購買(mǎi)。乙烯氫甲?；磻玫奖?一般使用銠或鈷反應裝置示意圖如圖1所示。將適量催化劑、配位化合物作為催化劑,其中銠催化劑使用壓力配體及10mL甲苯置入高壓反應釜,密閉抽真空至低,得到更為廣泛的應用。催化反應時(shí),原料氣通0085MPa以上,關(guān)閉閥門(mén)5,停止抽真空。通入入含ppm級催化劑和配體的溶液中進(jìn)行反應,一般定比例原料氣至一定的壓力后,關(guān)閉進(jìn)氣閥門(mén)停溶劑使用甲苯、丙醛及丙醛縮聚物等。反應的TOF止進(jìn)氣。開(kāi)始加熱,攪拌。記錄壓力隨時(shí)間的變化?？稍?0000h以上,反應壓力在2MPa左右,反應壓力表選擇性接近100%,少量副產(chǎn)物為乙烷、丙酸、丙混醛縮聚物等。在催化劑、配體和溶劑量固定的條件質(zhì)量流量計壓力傳感器下,可以通過(guò)調節乙烯、一氧化碳和氫氣的比例對反應速率進(jìn)行調控,從而配合反應工藝設計和調控。因此反應動(dòng)力學(xué)研究對于反應工藝的模型建立oFH和設計等具有重要意義g本研究設計建立了間歇式乙烯氫甲?；磻狥ig 1 Schematic overview of the ethylene hydroformylation kinetics動(dòng)力學(xué)測定裝置,在該實(shí)驗裝置上,以甲苯為溶劑,test setup對原料氣體分壓對乙烯氫甲?；磻俾实挠绊憟D1氫甲?；磻b置示意圖進(jìn)行了研究,通過(guò)對實(shí)驗數據進(jìn)行分析、擬合和計3動(dòng)力學(xué)方程算,獲得了乙烯氫甲?；磻俣鹊暮暧^(guān)動(dòng)力學(xué)模通過(guò)前期的實(shí)驗數據可知,反應溫度對反應速型。收稿日期:201601-18;修回日期:201603-24基金項目:國家自然科學(xué)基金資助項目(21476239);中國科學(xué)院戰略性先導科技專(zhuān)項(XDA中國煤化工作者簡(jiǎn)介:楊普(1982-),男,寧夏人,碩士研究生,Ema:py@ Ipeac cn聯(lián)系人:刁琰琰(1982-),女,山東人,博土,副研究員,碩土生導師,Emai: yydiaod@ipemyhCNMHG442針算帆廢用化2016,334)率較為敏感,溫度升高時(shí)反應速率明顯加快。另外催化劑濃度對反應速率的影響也比較大,隨著(zhù)催化d2065931(+64142) De 2069252-p93℃,y==4×267(8)劑濃度增加,反應速率加快。在本研究中,催化劑81℃dP4x16.10072(t+734255)e=EP(9)用量與配體用量為一固定值,將不討論三苯基膦濃d7641922度與催化劑濃度對反應速率的影響,作為一個(gè)常數100°C放在動(dòng)力學(xué)模型中。研究只考慮反應進(jìn)料量對反應速率的影響,根據羰基合成的反應規律,再結合相8l°關(guān)文獻報道,對以甲苯為溶劑,乙烯氫甲?；?2.0丙醛的反應動(dòng)力學(xué)進(jìn)行研究。反應速率方程為y=ko(Po)(PH, (PR,)k= koe31活化能和反應速率常數乙烯、一氧化碳和氫氣按反應計量摩爾比1:1:1Fg3 Plot of lmy vs In P with the reactant gas of CO: C2H4: H2=111圖3 Imy-ln P曲線(xiàn)(COC2HH2=1:1:1)通入反應釜,設定n=a+b+c,則反應速率方程變?yōu)?對 Imy-In P作圖,如圖3所示。r=koPe得出的反應速率常數和總反應級數列于表1測得100℃、93℃和81℃反應溫度下,反應釜中。反應級數平均為06壓力隨時(shí)間的變化曲線(xiàn),如圖2所示。表1不同溫度下的反應速率常數和總反應級數Table 1 Reaction rate constant and total reaction series at different2.0-100°354.1500754064366.150.1296069373.150.1981063對hnk-1T作圖,如圖4所示。Y=1607705-661578Xt/mintime with the reactant gas of CO: C2H4: H圖2氣體(COC2H4H2=1:1:1)壓力隨時(shí)間的變化曲線(xiàn)對圖2的測試數據進(jìn)行擬合,得到3個(gè)溫度下的擬合方程如下:100℃,y=009727+21704ex+6414293℃,y=006067+26347e2069Fig 4 Plot of Ink vs 1/T.2x+742s3圖4lnk-lT曲線(xiàn)81℃,y=027982+16.1007e1642進(jìn)一步得到反應速率方程為圖4中直線(xiàn)的斜率K=-66157×103,再由100℃,dP4x21704l855(+1219()k=B1=650,計算得到活化能E=5009kJ/mol。直線(xiàn)截距lnko=160771,計算得到k=9.6×105中國煤化工CNMHG2016,33(4)楊普,等:乙烯氫甲?；瘎?dòng)力學(xué)研究3乙烯的反應級數33一氧化碳和氫氣的反應級數將CO與H2按1:1配制成混合氣,設定為混合將CO與C2H4按1:1配制成混合氣,將該混合氣M,則反應速率方程變?yōu)?氣看成一種氣體,稱(chēng)其為混合氣N,其級數為a+by=k(R)(P e a/r(10)之和,將大大過(guò)量的氫氣與其混合,反應到混合氣因為混合氣M大大過(guò)量于乙烯氣體,反應到乙N完結時(shí)氫氣的壓力下降不大,可以忽略,此時(shí)氫烯氣完結時(shí),混合氣M的壓力下降不大,可以忽略氣的影響4可視為常數,從而可以求出N的級數此時(shí)該氣體的影響(PM可視為常數,從而可以求a+b出C2H4的級數b。100℃下壓力隨時(shí)間的變化曲線(xiàn),如圖5所示。03ig.7 Plot of pressure vs time at 100C with the reactant gas圖7100℃下,H2過(guò)量時(shí),壓力隨時(shí)間的變化曲線(xiàn)Fig 5 Plot of pressure vs time at 100C with the reactant gascomprising excess CO and H100℃下壓力隨時(shí)間的變化曲線(xiàn),如圖7所示。圖5100℃下,混合氣M過(guò)量時(shí),壓力隨時(shí)間的變化曲線(xiàn)由圖7的數據得到擬合方程:由圖5數據得到擬合方程x+120239)2y=-0.47921+1.039e48753y=0.01694+0.36535e反應速率方程為:則反應速率方程為dP4x1.039r+O.dP4×0.36535d48735+1.20239ed8:64919(t+0.07451(12)(14)對lmy-nP作圖,如圖6所示。對lmy-nP作圖,如圖8所示。16y120:189543x18R09941.35￥1.300800255X.6Fig 6 Plot of Iny vs In P at 100C with the reactant gas comprisingexcess CO and HFig8 Plot of Iny ws InP at 100C with the reactant gas comprising圖6100℃下,混合氣M過(guò)量時(shí),lmy-hP曲線(xiàn)excess H圖8100℃下,H2過(guò)量時(shí), Iny-InP曲線(xiàn)計算得出乙烯的反應級數b=096, Inkc2H4=-121。得出CO中國煤化工003,1nkNy=CNMHG針算帆與用化嚳2016,33(4)-1.30Arellano-Garcia H, Seidel-Morgenstern A, Hamel C. Kinetics of1-dodecene hydroformylation in a theriomorphic solvent system根據b=096,a+b=003,a+b+c=0.66,得出using a rhodium-biphephos catalyst[J]. Chemical EngineeringScience,2014,115:3148.氧化碳的反應級數為093,氫氣的反應級數為3 Raj Madhukar Deshpande. Bhalchandra Mahadeo Bhanage, SunilSadashiv Divekar, Subbareddiar Kanagasabapathy, Raghunath綜上所述,得到氫甲?；磻罱K的反應速率Vitthal Chaudhari. Kinetics of hydroformylation of ethylene in ahomogeneous medium: comparison in organic and aqueous方程為systems[]. Industrial Engineering Chemistry Research, 1998,y=(P(P,)(2)e37:2391-2396.(15)4 Li Chuanzhao, Guo Liangfeng, Marc Garland. Homogeneous96x10(0)°(2x)(1)° e-a (MPa.mir)hydroformylation of ethylened by rh(co)z. theplication of BTEM to identifytra:RCORh(CO)(0-C2H)[]. Organometallics, 2004,4結論2201-22045 Navidi N, Thybaut J W, Marin G B. Experimental investigation of對以甲苯為溶劑時(shí),乙烯氫甲?；磻膭?dòng)力ethylene hydroformylation to propanalon Rh and Co basedcatalysts[]. Applied Catalysis A: General, 2014, 469: 357-366學(xué)進(jìn)行了研究,獲得了反應速率常數、各反應氣體6 Yang Jinghua, Chen Tonghao, Zhou Qizhao, Wei Wende. Kenetics的反應級數和反應活化能reaction medium[]. Petrochemical Technology, 1990,(4): 209實(shí)驗條件下乙烯氫甲?；磻俾史匠虨? Yang Jinghua, Chen Tonghao, Zhou Qizhao, Wei Wende Keneticsstudy of ethylene hydroformylation ii. using propanaly=k(PCo)(.(B, )e a/rrcondensation products as reaction medium[]. PetrochemicalTechnology,1992,(4):21922296×10(P)(Pm,)"(P中文參考文獻活化能為Ea=550 kJ/mol6楊靜華,陳同豪,周啟昭,魏文德.乙烯氫甲酞化反應動(dòng)力學(xué)的研究L.以丙醛為反應介質(zhì)團.石油化工,1990References:(4):209-2147楊靜華,陳同豪,周啟昭,魏文德.乙烯氫甲酞化反應動(dòng)力學(xué)Dmitry Yu. MuraiBermas, Tapio Salmi. Mechanisticmodel for kineticspene hydroformylation with Rh的研究Ⅱ以丙醛縮聚物為反應介質(zhì)[石油化工,1992,catalyst門(mén)AChE地2012,58(7)2192-2201(4)219-2222 Kiedorf G Hoang D M, Maller A, Jorke A, Markert J,Studies on kinetics of ethylene hydroformylationYang Pu, Wang Ling, Diao Yanyan, Li Chunshan and Wang Lei( Beijing Key Laboratory of lonic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing100190, China)Abstract: Kinetics of ethylene hydroformylation using toluene as solvent was investigated by changing the temperature and molar ratio of C2H, Coand H2 with fixed amounts of toluene, catalyst, and ligand. The reaction pressure changing with time with the reactant gas of C2H4 CO: H2=1: 1: I wasdetermined at 100 C. 93C, and 81C. The sum reaction order of three gases, constant rate constant and activation energy were calculated. Theactivation energy of the reaction was 55.0 kJ/mol. By overdosing CO and H2, the reaction order of C2H, was gotten. And by overdosing H2, the sumreaction order of C2 H and Co was obtained, then the respective reaction order of C2H and Co was calculated. The results showed that high partialpressure of Co was not good for the reaction rate, and the reaction rate increased with the partial pressure increasing of C2H4 or H2(Received: 2016-01-18: Revised: 2016-03-24)中國煤化工CNMHG