第31卷第4期應(yīng)用化學(xué)Vol.31 Iss.42014年4月CHINESE JOURNAL OF APPLIED CHEMISTRYApr. 2014甲醇制烯烴催化劑失活模型李志孫啟文*劉繼森張宗森(.上海兗礦能源科技研發(fā)有限公司;煤液化及煤化工國(guó)家重點(diǎn)實(shí)驗(yàn)室上海 201203)摘要在固定床反應(yīng)器中,研究了甲醇制烯烴反應(yīng)中當(dāng)SAP0-34分子篩處于失活期時(shí)催化劑活性的變化情況,主要考察催化劑活性隨反應(yīng)溫度、空速和運(yùn)行時(shí)間的變化，通過(guò)對(duì)實(shí)驗(yàn)數(shù)據(jù)的分析擬合,得到了催化劑活性與失活時(shí)間、反應(yīng)溫度、空速的經(jīng)驗(yàn)關(guān)聯(lián)式(失活模型) ,對(duì)失活模型的檢驗(yàn)表明,該模型與實(shí)驗(yàn)數(shù)據(jù)較為吻合,表明了該式的準(zhǔn)確性。通過(guò)對(duì)失活模型的分析,獲得了當(dāng)失活速率達(dá)到最大時(shí)的失活時(shí)間與反應(yīng)時(shí)間、空速的關(guān)聯(lián)式,失活過(guò)程應(yīng)服從不均勻表面失活機(jī)理,并且當(dāng)催化劑處于失活區(qū)時(shí),失活時(shí)間對(duì)活性的影響要大于空速和溫度。關(guān)鍵詞甲醇制烯烴 ,失活模型,SAPO-34,催化劑中圖分類號(hào):0643文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):00005018(2014 )04-0394-06DOI:10. 3724/SP. J. 1095. 2014.30297低碳烯烴尤其是乙烯和丙烯作為基本化工原料,在現(xiàn)代石油和化學(xué)工業(yè)中起著至關(guān)重要的作用。甲醇制烯烴( MTO)工藝是由合成氣經(jīng)甲醇轉(zhuǎn)化為低碳烯烴的方法,被視為最有希望替代石油路線生產(chǎn)低碳烯烴的工藝" ,反應(yīng)的關(guān)鍵之-是催 化劑,自美國(guó)聯(lián)合碳化物公司開(kāi)發(fā)了磷酸硅鋁系列分子篩以來(lái),SAP0-34分子篩因其對(duì)乙烯和丙烯的高選擇性而被認(rèn)為是MTO最佳催化劑，目前已有較多關(guān)于SAPO-34制備、改性及其反應(yīng)性能的報(bào)道[24)。SAP0-34極易因積碳而失活，因此充分考慮反應(yīng)失活期催化劑活性的變化成為正確描述MTO反應(yīng)的重要問(wèn)題。Qi等[51發(fā)現(xiàn)當(dāng)溫度為623 ~823 K時(shí),在MTO反應(yīng)初期SAPO-34積碳較快,之后變得較為平緩,并構(gòu)建了可以估算不同條件下積碳量的模型。邢愛(ài)華等[綜述了MTO工藝中不同催化劑和工藝開(kāi)發(fā)階段的積碳行為,包括積碳動(dòng)力學(xué)和MTO催化劑燒焦動(dòng)力學(xué)等方面的研究。Chen等[]考慮因積碳而引起的失活,對(duì)SAP0-34.上的MTO反應(yīng)動(dòng)力學(xué)進(jìn)行了研究,該動(dòng)力學(xué)模型可以用來(lái)模擬因積碳而引起的催化劑活性和選擇性的變化。Ali 等[8] 認(rèn)為受Si/Al比影響的SAP0-34結(jié)晶度是影響催化劑積碳的重要因素,從而影響催化劑的活性,高結(jié)晶度的SAP0-34具有更長(zhǎng)的壽命,齊國(guó)禎等[9]充分考慮水和積碳對(duì)反應(yīng)過(guò)程的影響,考察了SAP0-34催化劑的失活規(guī)律,建立了5集總反應(yīng)和失活動(dòng)力學(xué)模型。文獻(xiàn)報(bào)道中的MTO反應(yīng)和失活動(dòng)力學(xué)均是包含較多參數(shù)的常微分方程組的形式，而缺乏形式簡(jiǎn)單并且易于應(yīng)用的關(guān)聯(lián)式,本文對(duì)SAP0-34積碳的催化劑在失活期內(nèi)的活性變化進(jìn)行了研究,基于實(shí)驗(yàn)結(jié)果得到活性與運(yùn)行時(shí)間、反應(yīng)溫度和甲醇質(zhì)量空速(以下簡(jiǎn)稱空速)的關(guān)聯(lián)式,旨在為MTO反應(yīng)器的設(shè)計(jì)以及操作條件的選擇提供依據(jù)。1實(shí)驗(yàn)部分1.1 儀器和試劑MRT-6212型固定床反應(yīng)器(中國(guó)北京欣航盾公司); PK564AN-TG10-A2型微量注射泵(日本精密科學(xué)株式會(huì)社) ;Model5850E型質(zhì)量流量計(jì)(美國(guó)Brooks 公司) ;T7890型氣相色譜儀(美國(guó)Agilent公司,HP-PL0TAL203毛細(xì)管柱),用于測(cè)定氣體產(chǎn)物中乙烯、丙烯等低碳烴類摩爾組成; YET-MT0-02型SAPO-34分子篩催化劑(上海兗礦能源科技研發(fā)有限公司) ,其顆粒密度2.7 g/cm' ,堆密度0.98 g/cm' ,比表面積420 m2/g, 孔容0. 32 cm'/g,平均孔徑0.48 nm;甲醇(國(guó)藥集團(tuán)化學(xué)試劑有限公司) ,分析純。2013-06-17 收稿,2013-08-14修回,2013-11-13接受國(guó)家高技術(shù)研究發(fā)展計(jì)劃(863計(jì)劃)項(xiàng)目(2011AA05A204) ;國(guó)家重點(diǎn)基礎(chǔ)研究發(fā)展計(jì)劃(973計(jì)劃)項(xiàng)目(2012CB723603)通訊聯(lián)系人:孫啟文,研究員; Tel:021-61620108 ; Fax :021 61620109; E-mil:etech@ ye-ech. com;研究方向:煤間接液化技術(shù)第4期李志等:甲醇制烯烴催化劑失活模型3951.2 實(shí)驗(yàn)操作將SAP0-34分子篩催化劑壓片后粉碎至0. 4 ~0. 8 mm ,裝填2 g催化劑到反應(yīng)器后,采用微量注射泵向反應(yīng)器中通人甲醇,采用質(zhì)量流量計(jì)控制甲醇流量,在設(shè)定的操作條件下進(jìn)行實(shí)驗(yàn)。用N2氣作為稀釋氣,流量為80 mL/ min。反應(yīng)產(chǎn)物用氣相色譜儀分析。2結(jié)果與討論2.1失活模型的建立2.1.1 MTO反應(yīng)特點(diǎn)及失活時(shí)間的定義 MTO反應(yīng)產(chǎn)物較為復(fù)雜,主要產(chǎn)物為C5以下的烯烴,其中乙烯和丙烯為目標(biāo)產(chǎn)物。以SAP0-34為催化劑的MTO反應(yīng)在溫度T和甲醇質(zhì)量空速0均相對(duì)較低的情況下,隨著運(yùn)行時(shí)間(TOS)的增加反應(yīng)共經(jīng)歷誘. Xcnyou導(dǎo)期、穩(wěn)定期和失活期3個(gè)階段(如圖1所示,常壓，0.8-、MT=673. 15 K,o=1.5 h-1)。誘導(dǎo)期內(nèi)，甲醇的轉(zhuǎn)化率、乙烯丙烯選擇性并沒(méi)有達(dá)到最大,而且出現(xiàn)明顯的波動(dòng);穩(wěn)定期內(nèi),甲醇轉(zhuǎn)化率和乙烯丙烯總選擇性,PC;H4達(dá)到最大,而且保持穩(wěn)定,可認(rèn)為此時(shí)催化劑活性最高;失活期內(nèi),甲醇轉(zhuǎn)化率迅速下降,而乙烯丙烯的e0stabilityinductiondeactivation選擇性則會(huì)一段時(shí)間內(nèi) 保持與穩(wěn)定期相同,之后也言7one開(kāi)始出現(xiàn)下降趨勢(shì)?？梢?jiàn)反應(yīng)運(yùn)行一段時(shí)間t后,6催化劑開(kāi)始失活,可將t視為反應(yīng)由穩(wěn)定區(qū)進(jìn)入失TOS/h活區(qū)的時(shí)間分界點(diǎn),為討論的簡(jiǎn)便,定義失活時(shí)間圖1甲醇轉(zhuǎn) 化率(X)和乙烯丙烯選擇性(φ)隨運(yùn)行時(shí)間的變化tp =TOS -to,即tp =0時(shí),反應(yīng)進(jìn)入失活區(qū)。Fig. 1 Changes of the conversion of methanol(X) , the通過(guò)實(shí)驗(yàn)觀察可知,在恒溫恒壓條件下,空速增selectivities of ethylene and propylene(φ) with time on大,反應(yīng)會(huì)更快地進(jìn)人失活期，當(dāng)空速>5 h-'時(shí),由stream于失活速率太快,導(dǎo)致很難捕捉催化劑開(kāi)始失活的準(zhǔn)確時(shí)間點(diǎn),因而本文采用的空速≤5 h-'。2.1.2催化劑相對(duì)活性的定義及實(shí)驗(yàn)結(jié)果催化劑的相對(duì)活性一 般可定義為:相對(duì)活性=某一時(shí)刻反應(yīng)物在失活催化劑上反應(yīng)速率/反應(yīng)物在新鮮催化劑上的反應(yīng)速率。由于MTO反應(yīng)存在較為明顯的誘導(dǎo)期,新鮮催化劑的活性不是最高,而是反應(yīng)運(yùn)行- - 段時(shí)間后進(jìn)入穩(wěn)定期,催化劑的活性達(dá)到最高并且保持穩(wěn)定,因此定義MTO催化劑SAPO-34的相對(duì)活性a為: .。= 某一時(shí)刻甲醉的摩爾轉(zhuǎn)化率(1)穩(wěn)定區(qū)內(nèi)甲醇的摩爾轉(zhuǎn)化率在常壓，反應(yīng)溫度T為673 ~748 K,空速v為1~5 h-'的操作條件下進(jìn)行實(shí)驗(yàn),結(jié)果見(jiàn)表1。表1不同溫度、空速條件下SAPO-34催化劑活性隨失活時(shí)間的變化Table 1 Changes of activity of the SAPO-34 catalyst with temperature and airspeed1=1 h-10=2 h-1tp/hT=673K r=698K r=723K T=748K T=673K T=698K T=723K T=748 K0.000.99890.99760.98240.96420.997 40.99840.9950.92830. 700.99140.987 90.935 70.77400.99030. 98070.885 90.67401.050.98430.89600.69270.42480.95920. 829 50.5830.33751.400.84270.60270.35130.21450.758 50.49220.281 60.18781.750.511 10.29230.191 60.157 80. 4080.23960.17320. 15232.100.24740. 17580.153 10. 14640.209 20.1630.14940.14532.450. 16510. 14990.14550. 14420. 15670.14740. 14482. 800. 14780. 14490. 14400. 143 80. 146 20. 14440.14390. 14383.150. 14450.143 80.1445.14420.14380. 14460. 1437Continued on next page396應(yīng)用化學(xué)第31卷continued from previous pagev=3h-1v=5h-1lp/hT=673K T=698 KT=723 KT=748K T=673K T=698 NT=723 K T=748 K0.0010.350.99570.989 10.97680.875 10.99240. 98680. 90320.75640.700.98240.95360.81560. 56340.61730. 36211.050. 92080.741 70.47360.27160. 78660.52550.30070. 19471.400.65600. 39260.23220. 17080.43860. 25370. 17800. 1531. 750.32500.20400. 161 70. 14890.21930. 16660. 15030.145 62. 100. 18430.15560. 14710. 14470. 15890. 14810. 14490. 14412.450.15160. 14590. 14430. 14390. 14660.14450. 14382.800. 14520. 144 10. 14320.14310.14410. 143 13. 150. 14400.14350. 14360. 14340. 143 80.14330.14362.1.3失活模型參數(shù)的計(jì)算 盡 管目前已有一些關(guān)于SAP0-34分子篩失活研究的報(bào)道[711 ,但是由于其失活速率較快以及失活機(jī)理的復(fù)雜性,難以采用形式較為簡(jiǎn)單的冪函數(shù)型失活動(dòng)力學(xué)方程對(duì)活性隨運(yùn)行時(shí)間的變化進(jìn)行準(zhǔn)確描述。通過(guò)對(duì)a ~t,關(guān)系曲線形狀(如圖3所示)的觀察,與y=exp( -x)函數(shù)圖形較為相似，因而可通過(guò)對(duì)函數(shù)通過(guò)a= exp( -t,) 進(jìn)行- -定的平 移伸縮而得到適宜的a~tp關(guān)聯(lián)式，通過(guò)對(duì)實(shí)驗(yàn)結(jié)果的分析和對(duì)a = exp( -l,) 的不斷修正,可知a與t,的關(guān)系可由式(2)較好的關(guān)聯(lián),稱該式為失活模型:Ca= 1 +exp(C,t。-C,) +C2(2)式中,C、C2、Cg和C為模型參數(shù),其中C,量綱為h-' ,其余參數(shù)量綱均為1。采用式(2)對(duì)表1中的實(shí)驗(yàn)數(shù)據(jù)進(jìn)行最小二乘擬合,獲取的相關(guān)參數(shù)列于表2(r為相關(guān)系數(shù))。表2失活模型參數(shù)Table 2 The deactivation model parametersu=2 h-1ParametersT=673K__ T=698K_ T=723K T=748K T=673K T=698K T=723K T=748 K_C10. 85630. 85900.85750. 87000.85650.861 80.86 790. 8760C20.14620.145 20.14480.14420.14510.14460.1439C35.06845.01234. 9594. 90245.04135.00834. 94324. 8403C&8.58377. 16645.84184.40618.006 86.625 35.22333. 81980.99970. 9990. 99980. 99990.99980.999 80.9999o=3 h-1o=5 h-' .ParanetersT=673 KT=698 KT=723K T=748K T=673K T=698 KTr=723K T=748 K0.8550. 85930. 86870.891 00. 859 80.87700.882 10.92830. 14530. 14480.14500. 14450.14375.02345. 00204.92324. 72904.93754.79185. 19437.448 66.09594.67993.18996. 36274.94703.502 02. 46890.999 9從表2中可以發(fā)現(xiàn),當(dāng)溫度和空速發(fā)生變化時(shí),參數(shù)C、C2和C;幾乎不變,因此取其算數(shù)平均值作為失活模型的參數(shù)值,可得C =0.8704, Cz =0.1447, Cz = 4. 9643(3)而溫度和空速對(duì)C,的影響較為明顯,可將C.表示成關(guān)于溫度和空速的二元函數(shù),即C, =f(T,v),從圖2中觀察可知,C隨著溫度和空速的變化,分別呈現(xiàn)線性變化,因此C.滿足下列偏微分方程組,p8C.aT =a(4)aC,=ar第4期李志等:甲醇制烯烴催化劑失活模型3970廠10十T=673.15 KB→v=1h-'8--v=2h-1- T=748.15K→-v=3h-1十v=5h-'心6心e6606800720 74060圖2參數(shù)C,隨溫度和甲醇空速的變化Fig.2 Changes of parameter Cs with temperature and space velocity of CH,OH其通解為.C4(T,) = aT +a20 +a3(5)式(4)、(5)中,an、a2 a3均為常數(shù)。按照表2中C.數(shù)據(jù)對(duì)式(5)進(jìn)行最小二乘擬合,可以得到a, =-0.0551, ar =-0.5434, az = 46.2017(6)C。的表達(dá)式為:C4==0.0551T-0.5434v+46.2017(7)將式(3)、(7)代人式(2)中,可得到失活模型為:0. 8704 _“1 + exp(4. 9643tp + 0.0551T7 + 0.5445v- 46.2017)+0.1447(8)2.1.4失活模型的檢驗(yàn) 由失活 模型式(8)可以得到失活區(qū)內(nèi)催化劑相對(duì)活性隨失活時(shí)間的變化曲線,并與實(shí)驗(yàn)值進(jìn)行對(duì)比,結(jié)果如圖3所示。從圖3可以看出,由失活模型得到計(jì)算值與實(shí)驗(yàn)值吻合較好,證明了該失活模型的準(zhǔn)確性。1.2.2-T=673.15KT-698.15 K1.0.8.8-=3a口0.6v=0.4-sht.40..82.4.63.26/h/h.2廠:2廠T-723.15KT=748.15 K=10.4-v=21.6圖3失活模型計(jì)算值與實(shí)驗(yàn)值的比較Fig.3 Comparison of calculated data and experimental data for the activity of SAP0-34 catalyst.398應(yīng)用化學(xué)第31卷2.1.5失活速率的極值 催化劑的失活速率為:84 = C,CzeGyp-C/(1 +eCyp-C4)2(9)dtp由于失活曲線為反s型曲線,隨著t。的增加,曲線斜率絕對(duì)值經(jīng)歷一個(gè)先增大后減小的過(guò)程,說(shuō)明在溫度和空速一定的條件下 ,存在- -個(gè)時(shí)間點(diǎn)1, =tw ,此時(shí)失活速率呈現(xiàn)極大值,此時(shí)滿足式(10):da=0dtlp=o由式( 10)解得,tm與溫度和空速的關(guān)聯(lián)式:tm = C:/C3 =-0.0111T - 0. 1095v + 9. 3068(11)2.1.6與失活機(jī)理的關(guān) 系由 失活模型可知,隨著ti,的增加,a逐漸趨近于C2,為此定義活性另外- -種形式:Cai=a-C2=1+exp(Ct,-C)(12)取其失活速率:a =4.9643a*(1 -1. 1489a*)∞a°(1 - 1. 1489a*)(13)從上式可以看出,失活速率近似正比于a*(1 -a° ),符合該規(guī)律的失活反應(yīng)可推斷其失活機(jī)理為不均勻表面失活,表面能量呈指數(shù)分布[12]。2.1.7操作條件對(duì)活性影響從式(8) 可以看出,失活時(shí)間越長(zhǎng)、溫度越高、空速越大,活性越低,但是這3個(gè)操作條件對(duì)催化劑活性的影響程度不同,a對(duì)1、T、o的敏感度可由a對(duì)1。、T、o的一階偏導(dǎo)表示:da0a =C;:(-a):(-a2) = 906:1:10 .(14)可見(jiàn),反應(yīng)處于失活區(qū)時(shí)，活性對(duì)于失活時(shí)間最為敏感,在很短的運(yùn)行時(shí)間內(nèi),催化劑會(huì)迅速失活;而溫度對(duì)催化劑的活性影響相對(duì)較弱。3結(jié)論1)得到了失活區(qū)內(nèi)催化劑活性與失活時(shí)間、反應(yīng)溫度.空速的關(guān)聯(lián)式即失活模型:0. 8704.a=1 + exp(4. 96431。+0. 0551 +0.5445 - 46.2017) +0.14472)通過(guò)對(duì)失活模型的分析計(jì)算,得到失活速率最大時(shí)對(duì)應(yīng)的時(shí)間值與反應(yīng)溫度和空速的關(guān)聯(lián)式:t_ =-0. 0111T -0.1095v + 9. 30683) MTO催化劑SAP0-34的失活機(jī)理應(yīng)為不均勻表面失活。4)失活區(qū)內(nèi)催化劑活性對(duì)操作條件的敏感性:失活時(shí)間>空速>反應(yīng)溫度。參考文獻(xiàn)[1] DAI Bingxin, WANG Xinsheng. 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Beijing: Chemical Industry Press, 2003: 567-568 ( inChinese).郭漢賢，應(yīng)用化工動(dòng)力學(xué)[ M].北京:化學(xué)工業(yè)出版社,2003 :567 -568.Deactivation Model of the CatalystUsed in Methanol to Olefin ProcessLI Zhi, SUN Qiwen' , LIU Jisen, ZHANG Zongsen(Shanghai Yankuang Research and Development Company of Energy Science and Technology ,Lid. ;State Key Laboratory of Coal Liqufacion and Coal Chemical Industry , Shanghai 201203 , China)Abstract The change of activity of the SAPO 34 zeolite catalyst in the methanol to olefin process( MTO) wasstudied after the catalyst started to lose activity in the fixed-bed isothermalintegral reactor. The effect oftemperature, space speed and time on stream on the change of catalyst activity was investigated. Thedeactivation function showed a good agreement with the experimental data. By analyzing the deactivationfunction, the relations between time when the deactivation speed was fast and both temperature and spacevelocity were obtained. The deactivation process obeyed the deactivation mechanism on the inhomogeneoussurface. After the SAPO-34 zeolite started to lose activity, the effect of deactivation time was greater than theeffect of space speed and reaction temperature.Keywords methanol to olefin , deactivation function , SAP0-34 , catalystReveived 2013-06-17; Revised 2013-08-14; Accepted 2013-11-13Supported by the National High Technology Research and DevelopmentProgram( 863 Program) of China ( No. 2011AA05A204) and theNational Basie Research Program(973 Program) of China( No. 2012CB723603)Corresponding author :SUN Qiwen, professor; Tel :021 -61620108 ; Fax:021 -61620109; E-mail: yetech@ ye tech. com; Research interests:indirect coal liquefaction technology.