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(浙江師范大學物理化學研究所,浙江省固體表面反應(yīng)化學重點實驗室,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HZSM5和10%MO,/HSM5(M=Al,Zn,Mn,Mg或Cu;x,y=1,2,3…)雙催化劑固定床反應(yīng)合成烯烴。研究發(fā)現(xiàn)10%CuO/HZSM是此反應(yīng)的較好催化劑在150℃較低反應(yīng)溫度下,甲醇的轉(zhuǎn)化率達到98%以上,C2~C烯烴的選擇性達到86%以上,且催化劑有較好的穩(wěn)定性。關(guān)鍵詞:MTO;甲醇;烯烴;HZSM5;10%CuO/HZSM5;催化劑;氫碘酸中圖分類號:TQ21文獻標識碼:A文章編號:1001-9219(2007)06280烯烴作為基本有機化工原料,在現(xiàn)代石油和化學工業(yè)中具有十分重要的作用。由于近幾年來石油1實驗部分資源的持續(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(H)≥45%;烴的技術(shù)路線,并取得了一些重大的進展2。以HZSM5分子篩,硅鋁比(SO2/AL2O3)≥360;MO,天然氣為原料制取烯烴的方法主要有3種:(1)甲HZSM5(M=A,Zn,Mn,Mg或Cu;x,y=1,2,3…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(OCM)。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=Al,Zn,Mn,Mg,發(fā)中最具備實現(xiàn)工業(yè)化條件的工藝13-8。Cu)的硝酸鹽配制成溶液,然后浸漬HZSM5分子篩MTO的反應(yīng)機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Mo,/HZSM5催化劑。以CuO/HZSM5為例,制法為以C2C3為主的低碳烯烴,少量的低碳烯烴進一如下:將4.468g的Cu(NO3)2·3H2O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。MTO10.0 g HZSM5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120℃過夜烘于,最ZSM5和以SAP0-34為代表的非沸石催化劑為主。后在馬弗爐中以430℃焙燒6h。在此反應(yīng)中,由于催化劑結(jié)焦嚴重,催化劑非常容易1.3實驗方法失活9。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)機理5和2.000g20~40目的HZSM催化劑依次裝入如下:石英大肚玻璃管(直徑15.0mm,長350.0mm,壁厚CH,OH+H—+CH3I+H2O1.omm),兩層之間用玻璃纖維隔開。石英玻璃管的上端和下端分別用20目~40目的石英砂填充,石HI-C, H,, +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l團玻硫纖維托住上面的催化劑和石英中國煤化工璃管裝人加熱裝置羧翌:2m1板生者:1593:男:中,CNMHG熱裝置的中間部位。2005210268@n.,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,待溫第6期楊鋒等:甲醇制烯烴的新路線硏究度升至設(shè)定值時注入甲醇的氫碘酸混合液(n速1.0m/h(相對于總催化劑量)。發(fā)現(xiàn)負載各種金(MeOH)/n(H)/n(H2O)=1:1.2:10.4)?；罨邔俚腍ZSM5對甲醇的轉(zhuǎn)化都達到了90%以上,見化劑取氣體樣品進行分析。反應(yīng)結(jié)束時,首先停止圖2。對10% ALHZSM5,甲醇全部轉(zhuǎn)化成了CH3I,注射混合液,大約0.5h后關(guān)閉加熱裝置,待反應(yīng)器沒有烯烴產(chǎn)生;對10%Zn/HZSM5,CH3I的選擇性冷卻到室溫后,拆卸反應(yīng)器,清洗實驗裝置。依然還有60%,C2~C4烯烴只占40%;對10%MnHZSM5,C2~C4烯烴選擇性提高到了50%以上;對10%Mg/HZSM5,C4烯烴和乙烯選擇性分別為70.0%和13.7%;10%Cu/HZSM-5的催化性能最好,甲醇轉(zhuǎn)化率達98.4%,C4烯烴選擇性達:°86.7%。a微量注射泵( Micro injector);b.控溫儀( Tempereture control);e.加熱裝置( Heater);d.冷卻裝置( Condenser)圖1催化劑評價反應(yīng)裝置圖Fig I The evaluation device for catalysts1.4產(chǎn)物分析該反應(yīng)的產(chǎn)物定性分析在氣質(zhì)聯(lián)用儀(GCMS,美國 Thermo公司生產(chǎn))上進行;定量分析在氣相色譜儀 agilent GC6890N上進行。氣質(zhì)聯(lián)用儀的載氣0 O/HSMS(MA么M№au為氦氣,色譜柱為DBⅤRX毛細管柱(60.0m×250Reaction temperature150t Feed velocity. Omlhum×1.40μm),離子源(CI、EI);氣相色譜儀A圖2甲醇轉(zhuǎn)化率和各產(chǎn)物選擇性lent6890N配有TCD檢測器,載氣為氫氣,色譜柱為Fig2 Conversion and selectivity of different metal supporgilet HP-molsiy和由化學手冊上查得各種分析物的相對校正因子2.2反應(yīng)時間的影響如下表1所示。2.2.1反應(yīng)時間對甲醇轉(zhuǎn)化率的影響表1幾種化合物的相對校正因子Table 1 Relative response factors of several substances符號分析物相對校正因子-10%MOSs10% CUOHSM-Sf甲醇f 2乙烯丙烯異丁烯碘代甲烷1.042結(jié)果與討論2.1不同金屬的影響在相同條件下,對質(zhì)量為2.000g負載了10%Reaction temperature150C Feed velocity 1. Oml/h不同金屬(A,Zn,Mn,Mg,Cu等)的HZSM5催化劑中國煤化工化的影響進行反應(yīng)評價。反應(yīng)溫度150℃,反應(yīng)原料CNMHGreaction time(n(MeOH)/n(H)/n(H2O)=1/1.2/10.4)液體流對質(zhì)量均為2.000g的10%MnO/HZSM5、10%天然氣化工2007年第32卷MgO/HZSM5、10%CuO/HZSM5在反應(yīng)溫度較低反應(yīng)溫度下反應(yīng)生成C2~C4烯烴。2.000g負150℃,反應(yīng)原料(n(MeOH)/n(HI)/n(H2O)=l載10%A,Zn,Mn,Mg或Cu的HZSM5(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%CuO況。結(jié)果見圖3。HZSM5催化性能最好,甲醇的轉(zhuǎn)化率達到98%以從圖3可見,對于10%CuO/HZM5在反應(yīng)進上,C2~C4烯烴的選擇性達到86%以上。10%行zh后,基本趨于穩(wěn)定,甲醇轉(zhuǎn)化率始終能保持在 CuO/HZSM5催化劑,反應(yīng)進行2h后甲醇轉(zhuǎn)化率和95%以上;而對10%MgO/HZSM5和10%MnO′C2~C4烯烴選擇性基本上保持穩(wěn)定,且反應(yīng)了12hHZSM5來說,Ih~h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,當反應(yīng)進行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?；蔬_到了90%以上。2.2.2反應(yīng)時間對烯烴選擇性的影響參考文獻對質(zhì)量均為2.00g的10%MnO/HZSM5、10%[1]劉紅星,謝在庫,張成芳,等.甲醇制烯烴(MTO)研究MgO/HZSM5、10%CuO/HZSM5在反應(yīng)溫度新進展[J].天然氣化工,2002,27(3):49-56150℃,反應(yīng)原料(n(MeOH)n(H)/n(H20O)=1/[2]趙毓瓊景振華甲醇制烯烴催化劑及工藝的新進展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-C4烯烴的選擇性隨反應(yīng)時[3]劉克成李玉玲.M改性HZSM催化劑上甲醇制間的變化情況。結(jié)果見圖4烯烴反應(yīng)性能研究[J].南陽師范學院學報,2007,6由圖4可見,對于10%CuO/HZSM5在反應(yīng)進(3):33-34.[4]白爾錚.甲醇制烯烴用SAPO34催化劑新進展[J行2h后,C2~C4烯烴選擇性基本趨于穩(wěn)定,始終能工業(yè)催化,2001,9(4):38保持在8%以上;而對10%MgOH△M5和10%[ 5] Patcs F C. The methanol-to-olefins conversion over zeo-MnO/HZSM5,1h-5h之間C2~C4烯烴的選擇性在lite-coated ceramic foams[J]. J Catal, 2005, 231: 194逐步升高,當反應(yīng)進行5h以后,才基本趨于穩(wěn)定,分別達到了60%和65%以上。6] Masuda T, Asanuma T, Shouji M, et al. Methanol to olefins using ZSM-5 zeolite catalyst membrane reactor[J]Chem Eng Sci, 2003, 58: 649-65[7] Dubois D R, Obrzut D L, Liu J, et al. Comethanol to olefins over cobalt - manganese-and nickelincorporated SAPO-34 molecular sieves J]. FuelProcess Technol. 2003.83: 203-218[8] Chen D, Rebo H P, Moljord K, et al. Methanol conver-sion to light olefins over SAPo-34 sorption, diffusion, anecatalytic reactions [J]. Ind Eng Chem Res, 1999, 38[9 Aguayo A T, Gayubo A G, Vivanco R, et al. Role of acid-ity and microporous structure in altemative catalysts forTime on stream/hthe transformation of methanol into olefins [J]. ApplReaction temperature 150C Feed velocity 1. 0ml/hcatal A,2005,283:197207.圖4反應(yīng)時間對C2~C4烯烴選擇性的影響[ 10] Inoue M, Dhupatemiya P, Phatanasri S, et al. SynthesisFig 4 C2-C olefins selectivity vs reaction timecourse of the Ni-SAPO-34 catalyst for methanol-to-olefin3結(jié)論conversion[ J]. Microporous Mesoporous Mater, 1999中國煤化工甲醇的氫碘酸混合溶液經(jīng)氣化通過HzSM5和CNMHG. Characteristics and per10%MO,/HZSM5雙催化劑固定床,能在150℃的(下轉(zhuǎn)第41頁)笫6期陳飛等:活性炭變壓吸附脫除二氧化碳的性能研究1997,38:105-110.5]張杰,穆朝友,曾斌,石江,黃煉,黃凱呂.變壓吸附脫[3]楊曉勤,蔣遠華.PSA雙高脫碳技術(shù)應(yīng)用及最新進展碳雙高工藝的應(yīng)用[J].小氮肥,2004,(11):15-18[J].湖北化工,2003,(1):40-416]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展有效氣體損耗[J].小氮肥,2005,(6):8-10[J].云南化工,2003,30(3):28-31The Performances of Active Carbons for the Carbon Dioxide Removal By PSaCHEN Fei, LU Xiao-qinCollege of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, ChAbstract: One foreign active carbon and three home-made active carbons were characterized and their performances were tested for the separation of CO2 from the mixture gas contained N 2 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 effects of adsorption conditions on the separation of COwere 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 carbonKey words pressure swing adsorption; PSA; carbon dioxide removal; active carbon; adsorbent(上接第30頁)formance of SAPO-34 catalyst for methanol-to-olefin conversion[ J]. Appl Catal, 1990, 64: 31-40A Novel Route for Methanol to olefinsYANG Feng, WU Ying, ZHOU Xiao-ping, wU Ting-huaInstitute of Physical Chemistry, Zhejiang Key Laboratory for Reactive Chemistry on Solid SurfacesNormal 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,/HZSM5(M=Al, Zn, Mn, Mg or Cu; x, y =1, 2, 3. )to produce olefines. It was found that 10%CuO/HZSM-5 was a suitable catalyst for this reaction, and at the low temperature of 150C, the conversion of methanol reached 98%, andthe total selectivity of Cr -Ca olefins was over 86%. The catalyst had good stability.Key words: MTO; methanol; olefines; HZSM-5; 10% CuO/HZSM-5; catalyst; iodic acid中國煤化工CNMHG