28天，然氣化工2007年第32卷甲醇制烯烴的新路線研究楊鋒,吳瑛,周小平,吳廷華 *(浙江師范大學(xué)物理化學(xué)研究所,浙江省固體表面反應(yīng)化學(xué)重點實驗室,浙江金華321004)摘要;研究了一條甲醇制烯烴的新路線,即甲醇與氫碘酸水溶液的混合物經(jīng)氣化后通過HZSM-5和10% M, 0,/HZSM-5(M= AI,Zn, Mn, Mg或Cu;x,y=1,23...) 雙催化劑固定床反應(yīng)合成烯烴。研究發(fā)現(xiàn)10% CuO/ HZSM-5是此反應(yīng)的較好催化劑,在150C較低反應(yīng)溫度下,甲醇的轉(zhuǎn)化率達(dá)到98%以上,C2 ~ C,烯烴的選擇性達(dá)到86%以上,且催化劑有較好的穩(wěn)定性。關(guān)鍵詞:MTO;甲醇;烯烴;HZSM-5;10% Cu0/ HZSM-5 ;催化劑;氫碘酸中圖分類號:TQ21.文獻(xiàn)標(biāo)識碼:A文章編號:001-9219(2007 )06-28-03烯烴作為基本有機(jī)化工原料,在現(xiàn)代石油和化1實驗部分學(xué)工業(yè)中具有十分重要的作用。由于近幾年來石油資源的持續(xù)短缺以及可持續(xù)發(fā)展戰(zhàn)略的要求,世界1.1實驗試劑上許多石油公司都致力開發(fā)非石油資源合成低碳烯甲醇,≥99.8%;HI水溶液,w(HI)≥45%;烴的技術(shù)路線,并取得了一些重大的進(jìn)展(1-2]。以HZSM_-5分子篩,硅鋁比( Si02/AL203)≥360;M,0,/天然氣為原料制取烯烴的方法主要有3種:(1)甲HZSM-5(M =Al,Zn, Mn, Mg或Cu;x,y=1,2,..)醇法( MTO);(2)費-托合成法(F-T);(3)甲烷氧化催化劑,自制。偶聯(lián)法( 0CM)。MTO 法是由合成氣經(jīng)過甲醇轉(zhuǎn)化1.2 催化劑制備為烯烴的工藝,是目前天然氣或煤制烯烴的研究開稱取計量量的相應(yīng)金屬M(M = AI,Zn , Mn, Mg,發(fā)中最具備實現(xiàn)工業(yè)化條件的工藝(3-8。Cu)的硝酸鹽配制成溶液,然后浸漬HZSM-5分子篩MTO的反應(yīng)機(jī)理主要是甲醇脫水生成二甲醚.(硅鋁比≥360) ,制得M的摩爾百分含量為10%的(DME) ,然后二甲醚與甲醇的平衡混合物繼續(xù)轉(zhuǎn)化M,O,/HZSM-5催化劑。以CuO/HZSM-5為例，制法為以C2、C3為主的低碳烯烴,少量的低碳烯烴進(jìn)-一如下:將4.468 g的Cu( NO3)2●3H20溶于100ml步通過縮聚、環(huán)化、脫氫、烷基化、氫轉(zhuǎn)移等反應(yīng)生成蒸餾水中,攪拌均勻形成溶液;然后再將稱好的飽和烷烴、芳烴及高級烯烴,且反應(yīng)有積炭。MTO10. Og HZSM-5粉末加人到Cu( NO3)2溶液中,攪拌反應(yīng)的關(guān)鍵之一是催化劑,往往以沸石系催化劑均勻,浸漬12h,再轉(zhuǎn)移到烘箱中120C過夜烘干,最ZSM-5和以SAP0-34為代表的非沸石催化劑為主。后在馬弗爐中以430C焙燒6h。在此反應(yīng)中,由于催化劑結(jié)焦嚴(yán)重，催化劑非常容易1.3 實驗方法失活9111。本文著重研究以甲醇的氫碘酸混合溶實驗裝置如圖1所示。液為原料,經(jīng)過雙催化劑作用使甲醇先碘化然后脫稱取2.000g20目~40 目的10% M,O,/HZSM-去碘化氫生成C2 ~ C4烯烴的新路線。其反應(yīng)機(jī)理5和2.000g20~40目的HZSM-5催化劑依次裝人如下:石英大肚玻璃管(直徑15. 0mm,長350. 0mm,壁厚cate.11. 0mm) ,兩層之間用玻璃纖維隔開。石英玻璃管的CH,OH +HI+CH,1 +H20cata. 2上端和下端分別用20目~40目的石英砂填充,石nCH,1-ar +C.H2。+ nHI(n=2,3,5)英砂與催化劑床層之間也用玻璃纖維隔開,反應(yīng)器的最下端置人一小團(tuán)玻璃纖維托住上面的催化劑和收稿日期:2007-10-12;作者簡介:楊 鋒( 1981-),男，漢石英砂。將裝有催化劑的石英玻璃管裝人加熱裝置族，浙江溫州人，碩土，Tel.: 0579-82283920,' E-mail:中,使催化劑床層的位置位于加熱裝置的中間部位。2005210268@ zjnu. net;'聯(lián)系人。設(shè)定控溫儀程序升溫的各項參數(shù),開啟控溫儀,待溫30天然氣化工2007年第32卷MgO/HZSM-5、10% CuO/HZSM-5 在反應(yīng)溫度較低反應(yīng)溫度下反應(yīng)生成C2 ~C,烯烴。2. 000g負(fù).150C ,反應(yīng)原料(n( MeOH)/n( HI)/n(H20) = 1/載10% Al,Zn, Mn,Mg或Cu的HZSM-5(硅鋁比≥1.2/10.4)液體流速1. 0ml/h(相對于總催化劑量)360)催化劑,甲醇的轉(zhuǎn)化率都達(dá)到了95%以上,但的條件下,考察了其催化性能隨反應(yīng)時間的變化情對烯烴的選擇性存在很大差異。其中, 10% Cu0/況。結(jié)果見圖3。HZSM-5催化性能最好,甲醇的轉(zhuǎn)化率達(dá)到98%以從圖3可見,對于10%CuO/HZSM-5在反應(yīng)進(jìn)上,Cz ~ C,烯烴的選擇性達(dá)到86%以上。10% .行2h后,基本趨于穩(wěn)定,甲醇轉(zhuǎn)化率始終能保持在CuO/HZSM-5催化劑,反應(yīng)進(jìn)行2h后甲醇轉(zhuǎn)化率和95%以上;而對10% Mg0/HZSM-5和10% MnO/C2 ~C。烯烴選擇性基本.上保持穩(wěn)定,且反應(yīng)了12hHZSM-5來說,1h~5h之間甲醇的轉(zhuǎn)化率在逐步升后也依然沒有出現(xiàn)轉(zhuǎn)化率和選擇性下降趨勢,這表高,當(dāng)反應(yīng)進(jìn)行5h以后,才基本趨于穩(wěn)定,甲醇的轉(zhuǎn)明催化劑不易失活,壽命令人滿意。化率達(dá)到了90%以上。參考文獻(xiàn)2.2.2反應(yīng)時間對烯烴選擇性的影響對質(zhì)量均為2.000g的10% MnO/HZSM-5、10%[1]劉紅星,謝在庫，張成芳,等.甲醇制烯烴(MTO)研究Mg0/HZSM-5、10% CuO/HZSM-5 在反應(yīng)溫度新進(jìn)展[J].天然氣化工,2002 ,27(3) :49-56.150C ,反應(yīng)原料(n( MeOH)/n( HI)/n(H20) =1/[2]趙毓璋,景振華. 甲醇制烯烴催化劑及工藝的新進(jìn)展1. 2/10. 4)液體流速1. 0ml/h(相對于總催化劑量)[J].石油煉制與化工,1999 ,30(2) :23-28.的條件下,考察了其C2 ~ C,烯烴的選擇性隨反應(yīng)時[3] 劉克成,李玉玲. 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PSA雙高脫碳技術(shù)應(yīng)用及最新進(jìn)展碳雙高工藝的應(yīng)用[J].小氮肥,2004,11);15-18.[J].湖北化工,2003,(1) :40 -41.[6] 李剛,母榮新,范培水.優(yōu)化變壓吸附脫碳工藝減少4] 寧平,唐曉龍，易紅宏.變壓吸附工藝的研究與進(jìn)展有效氣體損耗[J].小氮肥,2005 ,(6) :8-10.[J].云南化工,2003 ,30(3) :28-31.The Performances of Active Carbons for the Carbon Dioxide Removal By PSACHEN Fei,LIU Xiao-qin( Cllege of Chemistry and Chemical Engineering, Nanjing University of Technology ,Nanjing 210009 ,China)Abstract : One foreign active carbon and three home-made active carbons were characterized and their perform-ances were tested for the separation of CO2 from the mixture gas contained N2 in a single column pressure swing ad-sorption (PSA) installation. Dynamic adsorption breakthrough curves were measured , and the dynamic adsorptionprocesses in different adsorptive pressures as well as the efects of adsorption conditions on the separation of CO2were investigated. The results showed that the performance of the active carbon from HuaiBei, AaHui was close tothe foreign active carbon , and it can be used as a substitute of the foreign active carbon,Key words: pressure swing adsorption ; PSA ;carbon dioxide removal ;active carbon; adsorbent(上接第30頁)formnance of SAP0-34 catalyst for methanol-to-olefn conver-sion[ J]. Appl Catal, 1990 ,64:3140.A Novel Route for Methanol to OlefinsYANG Feng , WU Ying ,ZHOU Xiao-ping, WU Ting-hua(Institute of Physical Chemistry ,Zhejang Key Laboratory for Reactive Chemistry on Solid Surfaces,Zhejiang Normal University ,Jinhua 321004 ,China)Abstract:A novel route for methanol to olefins was studied , in which the mixture of methanol and iodic acid a-queous solution was gasified and passed through a fix bed of the double catalysts of HZSM-5 and 10% M,O,/HZSM-5 (M= Al,Zn ,Mn,Mg or Cu;x,y=1 ,2 ,... to produce olefines. It was found that 10% Cu0/HZSM-5 was a suit-able catalyst for this reaction , and at the low temperature of 150C , the conversion of methanol reached 98% , andthe total selectivity of C2 ~ C, olefins was over 86% . The catalyst had good stability.Key words:MTO;methanol ;olefines ;HZSM-5 ;10% CuO/ HZSM-5 ;catalyst; iodic acid