第33卷第4期計(jì)算機(jī)與發(fā)用化骨2016年4月28日Computers and applied chapril 22如4乙烯氫甲?；瘎恿W(xué)研究楊普,王玲,刁琰琰,李春山,王蕾(中國科學(xué)院過程工程研究所,離子液體清潔過程北京市重點(diǎn)實(shí)驗(yàn)室多相復(fù)雜系統(tǒng)國家重點(diǎn)實(shí)驗(yàn)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?yīng)動力學(xué)進(jìn)行了研究。以反應(yīng)計(jì)量比為11:1的乙烯一氧化碳和氫氣為反應(yīng)混合氣,測定了100℃、93℃和81℃下反應(yīng)壓力隨時(shí)間的變化曲線,通過動力學(xué)方程求解獲得了3種氣體總的反應(yīng)級數(shù)、反應(yīng)速率常數(shù)和活化能,得到反應(yīng)的活化能為550kJ/mo。進(jìn)一步通過一氧化碳和氫氣過量,得到了乙烯的反應(yīng)級數(shù)。然后通過氫氣過量,得到了乙烯和一氧化碳的總反應(yīng)級數(shù),隨后即計(jì)算得到了一氧化碳和氫氣各自的反應(yīng)級數(shù),表明一氧化碳分壓高會抑制反應(yīng)速率,而增加乙烯和氫氣分壓對反應(yīng)速率有促進(jìn)作用。關(guān)鍵詞:乙烯;氫甲?；?動力學(xué)中圖分類號:TQ0159;TP3919;06-39文獻(xiàn)標(biāo)識碼:A文章編號:10014160(2016)044414Dol:10.16866/j.com.appchem2016040121引言2實(shí)驗(yàn)部分氫甲?；磻?yīng)是烯烴與一氧化碳和氫氣反應(yīng)銠膦催化劑為實(shí)驗(yàn)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,氫氣從北京市均相氫甲?；呀?jīng)被廣泛工業(yè)化應(yīng)用3北溫氣體制造廠購買。乙烯氫甲?；磻?yīng)得到丙醛,一般使用銠或鈷反應(yīng)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(yīng)釜,密閉抽真空至低,得到更為廣泛的應(yīng)用。催化反應(yīng)時(shí),原料氣通0085MPa以上,關(guān)閉閥門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(yīng),一般定比例原料氣至一定的壓力后,關(guān)閉進(jìn)氣閥門停溶劑使用甲苯、丙醛及丙醛縮聚物等。反應(yīng)的TOF止進(jìn)氣。開始加熱,攪拌。記錄壓力隨時(shí)間的變化?？稍?0000h以上,反應(yīng)壓力在2MPa左右,反應(yīng)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(jì)壓力傳感器下,可以通過調(diào)節(jié)乙烯、一氧化碳和氫氣的比例對反應(yīng)速率進(jìn)行調(diào)控,從而配合反應(yīng)工藝設(shè)計(jì)和調(diào)控。因此反應(yīng)動力學(xué)研究對于反應(yīng)工藝的模型建立oFH和設(shè)計(jì)等具有重要意義g本研究設(shè)計(jì)建立了間歇式乙烯氫甲?；磻?yīng)Fig 1 Schematic overview of the ethylene hydroformylation kinetics動力學(xué)測定裝置,在該實(shí)驗(yàn)裝置上,以甲苯為溶劑,test setup對原料氣體分壓對乙烯氫甲酰化反應(yīng)速率的影響圖1氫甲?；磻?yīng)裝置示意圖進(jìn)行了研究,通過對實(shí)驗(yàn)數(shù)據(jù)進(jìn)行分析、擬合和計(jì)3動力學(xué)方程算,獲得了乙烯氫甲?；磻?yīng)速度的宏觀動力學(xué)模通過前期的實(shí)驗(yàn)數(shù)據(jù)可知,反應(yīng)溫度對反應(yīng)速型。收稿日期:201601-18;修回日期:201603-24基金項(xiàng)目:國家自然科學(xué)基金資助項(xiàng)目(21476239);中國科學(xué)院戰(zhàn)略性先導(dǎo)科技專項(xiàng)(XDA中國煤化工作者簡介: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(dǎo)師,Emai: yydiaod@ipemyhCNMHG442針?biāo)惴珡U用化2016,334)率較為敏感,溫度升高時(shí)反應(yīng)速率明顯加快。另外催化劑濃度對反應(yīng)速率的影響也比較大,隨著催化d2065931(+64142) De 2069252-p93℃,y==4×267(8)劑濃度增加,反應(yīng)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(yīng)速率的影響,作為一個常數(shù)100°C放在動力學(xué)模型中。研究只考慮反應(yīng)進(jìn)料量對反應(yīng)速率的影響,根據(jù)羰基合成的反應(yīng)規(guī)律,再結(jié)合相8l°關(guān)文獻(xiàn)報(bào)道,對以甲苯為溶劑,乙烯氫甲?；?2.0丙醛的反應(yīng)動力學(xué)進(jìn)行研究。反應(yīng)速率方程為y=ko(Po)(PH, (PR,)k= koe31活化能和反應(yīng)速率常數(shù)乙烯、一氧化碳和氫氣按反應(yīng)計(jì)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(COC2HH2=1:1:1)通入反應(yīng)釜,設(shè)定n=a+b+c,則反應(yīng)速率方程變?yōu)?對 Imy-In P作圖,如圖3所示。r=koPe得出的反應(yīng)速率常數(shù)和總反應(yīng)級數(shù)列于表1測得100℃、93℃和81℃反應(yīng)溫度下,反應(yīng)釜中。反應(yīng)級數(shù)平均為06壓力隨時(shí)間的變化曲線,如圖2所示。表1不同溫度下的反應(yīng)速率常數(shù)和總反應(yīng)級數(shù)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)間的變化曲線對圖2的測試數(shù)據(jù)進(jìn)行擬合,得到3個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81℃,y=027982+16.1007e1642進(jìn)一步得到反應(yīng)速率方程為圖4中直線的斜率K=-66157×103,再由100℃,dP4x21704l855(+1219()k=B1=650,計(jì)算得到活化能E=5009kJ/mol。直線截距l(xiāng)nko=160771,計(jì)算得到k=9.6×105中國煤化工CNMHG2016,33(4)楊普,等:乙烯氫甲?；瘎恿W(xué)研究3乙烯的反應(yīng)級數(shù)33一氧化碳和氫氣的反應(yīng)級數(shù)將CO與H2按1:1配制成混合氣,設(shè)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(yīng)速率方程變?yōu)?氣看成一種氣體,稱其為混合氣N,其級數(shù)為a+by=k(R)(P e a/r(10)之和,將大大過量的氫氣與其混合,反應(yīng)到混合氣因?yàn)榛旌蠚釳大大過量于乙烯氣體,反應(yīng)到乙N完結(jié)時(shí)氫氣的壓力下降不大,可以忽略,此時(shí)氫烯氣完結(jié)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(shù),從而可以求出N的級數(shù)此時(shí)該氣體的影響(PM可視為常數(shù),從而可以求a+b出C2H4的級數(shù)b。100℃下壓力隨時(shí)間的變化曲線,如圖5所示。03ig.7 Plot of pressure vs time at 100C with the reactant gas圖7100℃下,H2過量時(shí),壓力隨時(shí)間的變化曲線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,如圖7所示。圖5100℃下,混合氣M過量時(shí),壓力隨時(shí)間的變化曲線由圖7的數(shù)據(jù)得到擬合方程:由圖5數(shù)據(jù)得到擬合方程x+120239)2y=-0.47921+1.039e48753y=0.01694+0.36535e反應(yīng)速率方程為:則反應(yīng)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過量時(shí),lmy-hP曲線excess H圖8100℃下,H2過量時(shí), Iny-InP曲線計(jì)算得出乙烯的反應(yīng)級數(shù)b=096, Inkc2H4=-121。得出CO中國煤化工003,1nkNy=CNMHG針?biāo)惴c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(jù)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(yīng)級數(shù)為093,氫氣的反應(yīng)級數(shù)為3 Raj Madhukar Deshpande. Bhalchandra Mahadeo Bhanage, SunilSadashiv Divekar, Subbareddiar Kanagasabapathy, Raghunath綜上所述,得到氫甲?；磻?yīng)最終的反應(yīng)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(jié)論2201-22045 Navidi N, Thybaut J W, Marin G B. Experimental investigation of對以甲苯為溶劑時(shí),乙烯氫甲酰化反應(yīng)的動力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(yīng)速率常數(shù)、各反應(yīng)氣體6 Yang Jinghua, Chen Tonghao, Zhou Qizhao, Wei Wende. Kenetics的反應(yīng)級數(shù)和反應(yīng)活化能reaction medium[]. Petrochemical Technology, 1990,(4): 209實(shí)驗(yàn)條件下乙烯氫甲?；磻?yīng)速率方程為7 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(xiàn)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(yīng)動力學(xué)的研究L.以丙醛為反應(yīng)介質(zhì)團(tuán).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(yīng)動力學(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(yīng)介質(zhì)[石油化工,1992,catalyst門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