石油學(xué)報(bào)(石油加工2013年6月ACTA PETROLEI SINICA(PETROLEUM PROCESSING SECTION)第29卷第3期文章編號(hào):1001-8719(2013)03-0539-09甲醇制芳烴研究進(jìn)展鄒琥,吳巍,葸雷,朱寧,史軍軍(中國石化石油化工科學(xué)研究院,北京100083)摘要:甲醇制芳烴(MTA)技術(shù)是從甲醇制烴(MTH)技術(shù)發(fā)展而來。根據(jù)甲醇制烯烴(MTO)的機(jī)理研究,MTA的反應(yīng)機(jī)理大致可以分為直接C—C鍵形成機(jī)理和間接C—C鍵形成機(jī)理(碳池機(jī)理)。MTA是一個(gè)酸催化反應(yīng),主要以分子篩,尤其是以HZSM5分子篩為催化劑,再通過其他元素對分子篩進(jìn)行改性以提高芳烴的選擇性。反應(yīng)中生成的稠環(huán)芳烴會(huì)轉(zhuǎn)化為積炭,這是催化劑失活的主要原因。大多數(shù)MTA技術(shù)仍然處于實(shí)驗(yàn)室研究階段,在中國,中國科學(xué)院山西煤炭化學(xué)研究所和清華大學(xué)開發(fā)的MTA技術(shù)已應(yīng)用于中試裝置或示范性工業(yè)裝置關(guān)鍵詞:甲醇;芳烴;甲醇制芳烴(MTA);分子篩催化劑;工藝技術(shù)中圖分類號(hào):TE646文獻(xiàn)標(biāo)識(shí)碼:Adoi:10.3969/j.isn.1001-8719.2013.03.028Review of Methanol to aromaticsZOU Hu, WU Wei, XI Lei, ZHU Ning, SHI JunjunResearch Institute of Petroleum Processing, SINOPEC, Beijing 100083, China)Abstract: Methanol to aromatics(MTA)process is evolved from the technology of methanol tohydrocarbons (MTH). The reaction mechanism of MTA, based on the methanol to olefins (MTo)reaction mechanism, was roughly classified to direct C-C bond formation mechanism and indirectond formation mechanism(carbon pool mechanism). MTAdwhich the molecular sieve, like H-ZSM-5, is used as the catalyst. Modifiers would be added to thecatalysts to improve the selectivity of aromatics. The condensed aromatics formed during MTA canbe converted to coke, which is the reason of catalyst deactivation. Most of the MTA technologiesare still in the research stage. In China, the MTA technologies separately developed by Institute ofCoal Chemistry of Chinese Academy of Sciences and Tsinghua University have been applied in pilotsor demonstration plants.Key words: methanol; aromatics; methanol to aromatics ( MTA); molecular sieve catalysts;process technology甲醇制芳烴( Methanol to aromatics,MTA)是昂,煤炭的運(yùn)輸(火車)費(fèi)用也要占到其總價(jià)的3成指以甲醇為原料直接制備以苯、甲苯和二甲苯為主左右,所以很多甲醇生產(chǎn)廠都建在煤礦附近。例如的芳烴,是甲醇制烴( Methanol to hydrocarbons,2010年國內(nèi)甲醇產(chǎn)能占前5位的內(nèi)蒙古、河南、山TH)中的一部分。MTA生產(chǎn)鏈主要由甲醇原料東、陜西和山西都是煤炭資源較豐富的省,甲醇生(天然氣和煤)、MTA原料(甲醇)和產(chǎn)物(芳烴)3部產(chǎn)占總產(chǎn)能的64%。即使從天然氣和煤的經(jīng)濟(jì)性分分組成。就甲醇原料,即天然氣和煤而言,天然氣析,將它們轉(zhuǎn)化為甲醇也是一個(gè)降低運(yùn)輸成本的有田一般位于較為偏遠(yuǎn)的地區(qū),天然氣的運(yùn)輸費(fèi)用高效方法中國煤化工收稿日期:201209-14CNMHG通訊聯(lián)系人:鄒琥,男,博士,從事增產(chǎn)芳烴新技術(shù)研究;Tel:010-82368815;E-mai540石油學(xué)報(bào)(石油加工)第29卷甲醇的生產(chǎn)技術(shù)已經(jīng)很成熟13,且具有大型化C-C鍵比較困難,密度泛函理論計(jì)算所得反應(yīng)能生產(chǎn)規(guī)模,新建工廠都是百萬噸以上。在中國,甲壘2也否定了直接C—C鍵生成機(jī)理。碳池機(jī)理如醇產(chǎn)能百萬噸以上的生產(chǎn)廠由2009年的2家增加到圖2所示[13,(CH2)為苯環(huán)形式的反應(yīng)活性中心,2010年的5家和2011年的8家。目前,全球甲醇在誘導(dǎo)期它是由微量的不純物,如甲醛、酮或高級(jí)生產(chǎn)的產(chǎn)能和產(chǎn)量都在增加,且甲醇產(chǎn)能遠(yuǎn)高于甲醇反應(yīng)而來;反應(yīng)穩(wěn)定后,活性中心可能是由于乙醇產(chǎn)量,例如,國內(nèi)近3年的甲醇生產(chǎn)開工率均不烯、丙烯等發(fā)生低聚、縮合反應(yīng)形成苯環(huán)14,在此足60%,如果開工率為100%,則供大于求的現(xiàn)象期間的活性中心數(shù)量比較多,芳烴的生成也是由活將會(huì)很嚴(yán)重,多余的甲醇需要開發(fā)新的下游產(chǎn)品。性中心物質(zhì)轉(zhuǎn)化而來。芳烴的大規(guī)模工業(yè)生產(chǎn)是通過芳烴聯(lián)合裝置實(shí)CH -CIC.-C. Olefins現(xiàn),對石油資源有著很強(qiáng)的依賴性。下游產(chǎn)品的需Fast求增長推動(dòng)了芳烴產(chǎn)量的增加,例如從2005至2010年,中國對二甲苯的表觀消費(fèi)量增加了近se/=水168%。這種趨勢要求芳烴生產(chǎn)有一個(gè)穩(wěn)定的原料racking供給,對于石油相對缺乏的中國,必須尋找石油以外的原料,MTA技術(shù)的出現(xiàn)無疑是提供了一條新ArCH3)2→ArCH,Aromatics的芳烴生產(chǎn)路線。近年來,中國煤化工發(fā)展方興未艾,MTA也成為科研機(jī)構(gòu)研究及公司關(guān)注的一個(gè)Ar(CH,h2熱點(diǎn),有關(guān)MTA的研究成果及專利呈現(xiàn)出直線上圖1HZSM5催化甲醇轉(zhuǎn)化反應(yīng)機(jī)理升的趨勢,開發(fā)了相應(yīng)的工藝和建成了示范性工業(yè)Fi1 Mechanism for the methanol reaction over H-ZSMs裝置1MTA的反應(yīng)機(jī)理C2H4CH6目前幾乎沒有研究MTA反應(yīng)機(jī)理的文獻(xiàn)報(bào)道。nH2OnCH. OH(CH,芳烴生成機(jī)理可以從MTH/MTO機(jī)理中引出,有Saturated hydrocarbonsAromatics關(guān)MTH/MTO的反應(yīng)機(jī)理已經(jīng)有很多綜述7,主CH要是C—C鍵的形成機(jī)理。各種機(jī)理可以簡單地分圖2碳池機(jī)理示意圖3為“直接”機(jī)理和“間接”機(jī)理2類。前一類是通過甲Fig2 Schematic of carbon pool mechanism[ 13醇/二甲醚與高能中間體的直接偶聯(lián)反應(yīng)生成產(chǎn)物的機(jī)理,后一類就是碳池機(jī)理。碳池機(jī)理認(rèn)為,在雖說碳池機(jī)理越來越被人們所接受,但是有些催化劑上生成的一些較大相對分子質(zhì)量的芳烴類物問題仍不是很清楚。比如,芳烴作為產(chǎn)物的活性中質(zhì)吸附在催化劑的孔道內(nèi)作為活性中心與甲醇反應(yīng),心是什么?怎么形成1個(gè)活性中心中間體產(chǎn)物(芳在引入甲基基團(tuán)的同時(shí)進(jìn)行脫烷基化反應(yīng),生成乙烴)活性中心的循環(huán)?這些都還需要進(jìn)一步的研究。烯和丙烯等低碳烴物種。2MTA的催化劑在“直接”機(jī)理中,芳烴主要是由低碳烯烴通過活性中間體進(jìn)行碳鍵的增長和環(huán)化而成。 Dessau2.1催化劑的選擇等∞基于碳正離子機(jī)理提出了一個(gè)芳烴生成機(jī)理早在1975年, Chang等(用約束因子如圖1所示。在該機(jī)理中,甲基碳正離子與烯烴反 Constraint index)的概念羅列了適合于MTH反應(yīng)應(yīng)生成更高階碳正離子,C脫氫環(huán)化反應(yīng)生成芳的分子篩催化劑。然而即使如此,催化劑的選擇仍烴;同樣地,通過甲基碳正離子與苯的反應(yīng)生成甲然經(jīng)過了一個(gè)漫長的過程,許多分子篩都被用作為苯和二甲苯MTH的催中國煤化乓化反應(yīng)所用過后來的研究101發(fā)現(xiàn),通過“直接”機(jī)理形成的部分催化CNMHG第3期甲醇制芳烴研究進(jìn)展541表1甲醇轉(zhuǎn)化催化劑及其芳烴選擇性Table 1 Various catalysts used for methanol conversion and the aromatics selectivity (s)CatalystFeedstocke/℃MHsv/h-1x/%s1)/%H-ZSM-5MeOH/DME382AlzO3-H-ZSM-531697.20[17] Al2 O3 or Al2 O3SiO2/Microporous glass400-4500.30100[18]HM(MordeniteMeOh/Water3312.[19]Modified zeoliteMeOh340-41097.00KZ-IZBH(Borosilicate zeolite)MeOH/ DMe1.70[22]Heteropoly acidMeOh13.10-71.6022.80-6.203)[23]Erionite- Offretite[24]HM/HY14.50/5.10[25] Al modified SiOz-B2 O3-NagO glassA zeolite-Alz O3MeoH/ Hydrocar650MeOH/WaterMCM-2292.72MeOh40010035.001)s=y(Aromatics)/y( Hydrocarbons)X100%; 2) Reaction activity after 3 h; 3)Selectivity of C6擇形性是分子篩催化劑的關(guān)鍵,產(chǎn)物分布強(qiáng)烈對于孔徑為0.55nm的ZSM-5,它允許通過的分子地依賴于分子篩的孔結(jié)構(gòu)。如果分子篩孔口太小,的上限為四甲基苯( Durene),所以產(chǎn)物中有許多芳以至于苯環(huán)無法通過,那么芳烴就不能從分子篩籠烴產(chǎn)物;H-Beta分子篩的十二元環(huán)開放孔道允許諸中逃逸出來,意昧著產(chǎn)物中只有C1~C5的烷烴和如六甲基苯的烷基苯自由地出入,只用于研究烯烴;另一方面,如果分子篩的孔徑大到能讓動(dòng)力MTH機(jī)理31。學(xué)直徑大于0.7nm的分子通過,那么在產(chǎn)物中就嘗試了多種分子篩催化劑,ZSM5分子篩最終會(huì)存在許多諸如五甲基苯( PentaMB)和六甲基苯成為MTA最主要的催化劑( HexaMB)的大分子芳烴。 Kvisle等30給出了幾種2.2催化劑改性組分對芳烴選擇性的影響分子篩的拓?fù)浣Y(jié)構(gòu)來分析產(chǎn)物的可能性,如圖3所通過分子篩改性可以增加MTH反應(yīng)中芳烴的示。SAPO分子篩的孔口比較小,只有小于己烯的選擇性,表2列出了含有不同改性組分催化劑催化線性分子能夠通過,所以此分子篩用于烯烴的生產(chǎn);甲醇轉(zhuǎn)化反應(yīng)的芳烴選擇性。改性組分以IB、IB族金屬元素為主,Ga也是常用的改性組分之一。改SAPO-34(CHA)SAPO-17(ERD)性組分在其中所起的作用可以歸納為:(1)提供1個(gè)SAPO-18(AEl)ZSM-5(MFD)Beta(BEA)L酸中心32或類似于Mm+OZ的活性中心3,烯C烴的生成與此L酸中心脫氫活性有關(guān),環(huán)烷烴中間體也可在L酸中心上脫氫生成芳烴,整個(gè)芳構(gòu)化過」口■■程是L酸中心和B酸中心的協(xié)同催化作用;(2)提供了1個(gè)烯烴的脫氫中心,中間產(chǎn)物進(jìn)而在ZSM5810my包張■的酸性位上芳構(gòu)化,如MC"和BG■■■過渡金屬是一類主要的改性元素。 Conte等30圖3分子篩孔籠結(jié)構(gòu)與MTH產(chǎn)物關(guān)系示意圖采用浸漬法考FB3 Schematic illustration of the channel-cage relations MTA活性,H中國煤化工5催化劑的CNMH GCu、Ni、Pd、in relevant topologiesIr和Ru。Ag、Cu和Ni可以提高C6~C1芳烴的選542石油學(xué)報(bào)(石油加工)第29卷擇性達(dá)2倍以上,而Pd、Ir和Ru則沒有這種效果。協(xié)同作用,這是一種金屬氧化物晶體與分子篩之間在反應(yīng)初始階段,所有的金屬都是以氧化物形式存的接觸協(xié)同作用,PdO、IrO2和RuO2與ZSM5晶在,烯烴在金屬離子上配位吸附,進(jìn)而生成芳烴。體間不存在這種相互作用。 Conte等認(rèn)為,丙烯Ag2+、Ni2+和Cu2+具有這種與烯烴配位的能力,是芳烴形成的中間體,具有與丙烯相互配位能力的并且AgO、NO和CuO必須與分子篩的酸性相互金屬氧化物,被認(rèn)為有利于芳烴的生成。表2改性元素對芳烴選擇性的影響Table 2 Effect of modified element on the aromatization of methanolModifierrationzeoliteB/C MHSV/ s/%(Before/After Incrementmodification)of s/%37]ZSM-5/Al2 O33.3Impregnation4625.718.4/25.438.0[38]ZSM-5Mgo11.4pregnat4003.1/14.140.3/67.4[3]ZSM-5Ion exchange42740.3/48.219.6[39] [Si, GaJZSM-5Ga, Si0. 0542) Hydrothermal450Pulse0/11.0.9/51.230.9/26.912.9ZSM-5lon exchange19.130.9/444.730.9/52.3[41]ZSM-5lon exchange9.0140.0/72.635,42]ZSM-5A-Ga: O350.0 Physical mixture 4000.710.4/51.4394.2[43]ZSM-5Impregnation400CuO,Zn07.0,0.5[34]ZSM-5Mo2 CImpregnation1.020.3/62.8209.4ne2.9,4.3/63.7[44ZSM-5mpregnation1)Mass of catalyst charged(g)for per feed rate(mol/h); 2)n(Ga)/n(Ga+Si)通過對HZSM5催化劑的改性,芳烴的選擇于烴的生成,必須有強(qiáng)酸位存在。鐘炳等]利用性得到較大程度的提高,使得甲醇直接轉(zhuǎn)化為芳烴TPSR和GCMS技術(shù)得出,甲醇脫水反應(yīng)主要在L成為可能。在金屬改性的催化劑中,起作用的是金酸中心進(jìn)行,并且在150℃吡啶中毒實(shí)驗(yàn)中,甲醇屬氧化物,清晰地了解改性元素的作用有助于催化TPD脫附物未檢測到芳烴,表明烴類的轉(zhuǎn)化基本被劑的設(shè)計(jì)阻止,所以認(rèn)為C—C鍵的形成和芳烴的生成是在2.3催化劑酸性對芳烴選擇性的影響B(tài)酸中心上進(jìn)行。但是 Akolekar等4認(rèn)為,甲醇一般認(rèn)為,由于烴類的芳構(gòu)化需要強(qiáng)酸催化劑,脫水成低碳烴的反應(yīng)可以在弱酸位上發(fā)生,而不只而MTA反應(yīng)也是要經(jīng)過中間烴類的芳構(gòu)化實(shí)現(xiàn),限于生成二甲醚這一步。 Sinitsyna等0也認(rèn)為,甲所以MTA也是強(qiáng)酸催化反應(yīng)。 Sedran等41用醇在弱酸中心轉(zhuǎn)化為C2~C4烯烴,在中等強(qiáng)度酸無定型酸性SO2-Al2O3催化劑來研究酸性與甲醇轉(zhuǎn)中心轉(zhuǎn)化為Cs~C10脂肪烴,在中等強(qiáng)度和強(qiáng)酸中化的關(guān)系,認(rèn)為反應(yīng)活性與酸強(qiáng)度無關(guān),但隨著酸心上生成C6~C芳烴和C1~C烷烴。量的增加達(dá)到最大產(chǎn)率(約80%),酸量進(jìn)一步增大芳烴的選擇性與酸量也有關(guān)系。 Vedreine等時(shí),產(chǎn)率開始下降。 Mandersloot-等t對此提出質(zhì)用P來改變V凵中國煤化工的加入提高了疑,認(rèn)為烴的生成只與強(qiáng)酸位的數(shù)量有關(guān),而不是低碳烯烴的CNMHG烴的生成;采整個(gè)酸量,弱酸位只能將甲醇脫水生成二甲醚,對用IR和微分吸附量熱技術(shù)聯(lián)用的實(shí)驗(yàn)則表明,P并第3期甲醇制芳烴研究進(jìn)543沒有中和分子篩孔道內(nèi)的最強(qiáng)酸位,只是中和了分基苯的進(jìn)一步聚合和脫氫則會(huì)形成硬炭(I類炭,是子篩孔道口的中等強(qiáng)度和強(qiáng)酸性位,所以認(rèn)為P沒指在370~570℃可燒除的炭),最終導(dǎo)致催化劑失有改變酸強(qiáng)度,芳烴產(chǎn)量與強(qiáng)酸位數(shù)量有關(guān),即酸活。軟炭經(jīng)過熱裂解也會(huì)轉(zhuǎn)化為硬炭強(qiáng)度決定產(chǎn)物的種類,而酸量決定產(chǎn)物的分布。Choudhary等2)考察了HZSM5催化劑的Si/Al原子比和離子交換程度對MTA產(chǎn)物分布的影響發(fā)現(xiàn)活性酸位(吡啶吸附在380℃時(shí)脫附量)越多,Diffusion effectsAlkenes芳烴濃度也越大。 H-GaMFI分子篩催化劑3的甲Dehydrocyclisation醇芳構(gòu)化/脫水活性比隨著其酸性增強(qiáng)而增大,只需要一定量的強(qiáng)酸位,大概0.05mmol/g的強(qiáng)酸就能使甲醇達(dá)到100%的轉(zhuǎn)化,但芳烴的生成隨酸位數(shù)量緩慢增加,在強(qiáng)酸位數(shù)量為0.21mmol/g時(shí)達(dá)到Oligomerisation最大,然后保持不變Dehydrogenation可見,甲醇的轉(zhuǎn)化和芳構(gòu)化都是酸催化過程甲醇轉(zhuǎn)化為二甲醚可以在弱酸位(L酸)上進(jìn)行,芳Thermal構(gòu)化則必須有強(qiáng)酸位(B酸)存在;強(qiáng)酸位越多,越hydrocrackingtreatment有利于芳烴的生成,但催化劑易于積炭Hard cokeracked2.4催化劑失活productsMentzel等54研究了HZSM5和 H-Ga-ZSM5圖4MIG中HZSM5催化劑的積炭過程兩類催化劑的失活。HZSM-5失活主要是因?yàn)榉eFig. 4 Coke formation on H-ZSM-5 during MTG process[ 93炭,可以通過燒焦使催化劑再生;HGa-ZSM5的失活是由于反應(yīng)中產(chǎn)生的水蒸氣使Ga從分子篩結(jié)TPO、DRUV- visible和IR技術(shù)聯(lián)用62被用于構(gòu)上流失,導(dǎo)致B酸位消失,這種失活不可再生,研究烷基苯轉(zhuǎn)化為積炭的過程,DR- UV-visible譜因此, H-Ga-ZSM5不太可能用于工業(yè)生產(chǎn)。中觀測到六甲基或五甲基苯的正離子,IR譜中觀測積炭是MTA催化劑失活的主要原因。XPS研到這些物種長大成焦炭的前驅(qū)體,最后變成類積炭究表明,積炭從ZSM5內(nèi)表面開始,當(dāng)積炭質(zhì)量分物種。 Bjorgen等3由此提出了積炭機(jī)理,即甲醇數(shù)達(dá)到7.0%時(shí)外表面開始積炭,并且在質(zhì)量分?jǐn)?shù)與四甲基苯反應(yīng)生成六甲基苯,六甲基苯經(jīng)過氫轉(zhuǎn)140%時(shí)催化劑開始失活,而此時(shí)內(nèi)部積炭已經(jīng)停移反應(yīng)形成六甲基苯碳正離子,再與甲醇生成七甲止s5,所以外表面的積炭是催化劑失活的真正原基苯碳正離子,通過脫氫和環(huán)化反應(yīng)生成三甲基四因)。但 Rownaghi等認(rèn)為,內(nèi)表面對失活也起氫萘碳正離子,再經(jīng)過脫氫和甲基化反應(yīng)生成非常重要的作用,他用均一中孔分子篩研究MTH2,3,4,6,7,8-六甲基萘,最終形成積炭。因?yàn)橐?jīng)過程,發(fā)現(xiàn)積炭速率較常規(guī)分子篩減緩,他認(rèn)為是過稠環(huán)芳烴形成積炭,所以大孔沸石在MTH過程因?yàn)楫a(chǎn)物在此分子篩孔道內(nèi)更易擴(kuò)散,不易形成稠中失活較快。環(huán)芳烴。反應(yīng)溫度對催化劑積炭的影響很大。例如,綜上所述,催化劑的積炭過程需要經(jīng)過一個(gè)烷375℃時(shí),ZSM5催化劑主要發(fā)生內(nèi)部積炭,在通基苯中間體,然后形成稠環(huán)芳烴,再轉(zhuǎn)化為積炭,道的交叉口的酸位上開始;475℃時(shí),積炭主要發(fā)生一般先從分子篩內(nèi)表面的強(qiáng)酸位上開始,然后擴(kuò)展在外表面。催化劑外表面的積炭主要是甲醇熱分解到外表面。反應(yīng)的結(jié)果。Bauer等通過 TG-FTIR技術(shù)研究MTG中3MTA的生產(chǎn)工藝HZSM5催化劑的積炭過程。如圖460所示,甲醇MTA的生產(chǎn)工藝大多處于實(shí)驗(yàn)室階段。美孚先轉(zhuǎn)化為烯烴,然后通過齊聚和氫轉(zhuǎn)移生成軟炭公司較早開V凵中國煤化工化研究,之后I類炭,是指在170~370℃可燒除的炭),也可能陸續(xù)有日本CNMHG開展了MTA在強(qiáng)酸位上齊聚生成烷基苯,繼而轉(zhuǎn)化為軟炭;烷工藝研究,但都沒有工業(yè)化。近年來,我國的544石油學(xué)報(bào)(石油加工)第29卷MTA研究借助于 MTO/MTP工業(yè)化開始紅火起裝在反應(yīng)器內(nèi)的導(dǎo)管將過熱的催化劑從反應(yīng)器的上來,并且已有中試生產(chǎn)的報(bào)道。如賽鼎公司運(yùn)用與端移到下端,用于將液體原料甲醇?xì)饣?氣化的甲中科院山西煤化所合作開發(fā)的“一種甲醇一步法制取醇與催化劑顆粒一起在反應(yīng)器中往上移動(dòng),這樣的烴類產(chǎn)品的工藝”專利技術(shù),在內(nèi)蒙古建成1套設(shè)計(jì)可以通過催化劑的循環(huán)控制這個(gè)強(qiáng)放熱反應(yīng)的10萬t/aMTA裝置,2012年已經(jīng)試車成功。溫度,從而延長催化劑的壽命。美孚公司8在1985表3對具有代表性的MTA工藝技術(shù)作一比較。年將P改性的ZSM5催化劑用于固定床甲醇芳構(gòu)ATG過程的發(fā)現(xiàn)者 Chang等在1979年開發(fā)了流化。在這一工藝中,C的芳烴所占比例減少,BTX化床反應(yīng)器用于制汽油和芳烴的工藝。通過一系列的選擇性增加。表3MTA工藝小試結(jié)果比較Table 3 Comparison of methanol to aromatics technologies worldwideReaction conditionsProductivity of aromaticsOrganizationReactorCatalystx/%6/℃P/MPa MHSV/h-Is)/%Mobil Fluidized bed H-ZSM-5 371 0.1Fixed bed P/ZSM-5 400-45034,90-36.20Institute of coalFixed bed0.1-3.50.6-6.031.5-33.83)Chemistry, CAsH-ZSM-50.1-4.0192-19202Tsinghua University Fluidized bed Ag/Zn/ZSM-5 4503000297.5072.04)1)Selectivity of aromatics =( Productivity of aromatics/Productivity of hydrocarbons)X100%:2)MHSV3)Yield of aromatics( Methanol mass basis)=(Mass of aromatics in products/Mass of methanol in feedstocks)X100%4)Yield of aromatics( Carbon number basis)=( Carbon number of aromatics in products/ Carbon number of methanol in feedstocks)X100%在我國自主研發(fā)的MTA技術(shù)中,中科院山西化劑以HZSM5為主,通過加入改性組分來提高煤化所最早開發(fā)出固定床兩段法的工藝。該工藝BTX選擇性和催化劑穩(wěn)定性;MTA反應(yīng)機(jī)理分為的第一段以甲醇為原料,經(jīng)過裝有催化劑的固定床“直接”C-C鍵形成機(jī)理和“間接”C—C鍵形成反應(yīng)器,產(chǎn)物經(jīng)過冷卻分離步驟分為氣相低碳烴和機(jī)理液相￠烴;將氣相低碳烴作為原料送入第二段固(2)MTA工藝技術(shù)在我國發(fā)展很快,其中有些定床反應(yīng)器中,同樣得到氣、液兩相產(chǎn)物,分離后技術(shù)已經(jīng)開始中試或應(yīng)用于示范廠階段,但仍有許將液相產(chǎn)物與第一段C烴產(chǎn)物混合,經(jīng)由萃取可多問題有待解決,如反應(yīng)過程的取熱、催化劑失活得目標(biāo)產(chǎn)物芳烴。該工藝的芳烴收率較高。較快和BTX的選擇性較低,必須在催化劑設(shè)計(jì)和反清華大學(xué)0開發(fā)了流化床MTA工藝。通過應(yīng)工藝優(yōu)化的研究方面有較大的突破,才能實(shí)現(xiàn)工個(gè)催化劑再生的流化床與MTA流化床相連,實(shí)現(xiàn)業(yè)化催化劑失活與再生的連續(xù)循環(huán)操作,從而控制催化(3)MTA工業(yè)化歷程同時(shí)受到經(jīng)濟(jì)性的制約。劑的結(jié)焦?fàn)顟B(tài),提高芳烴純度與收率。山西煤化所石油芳烴與甲醇價(jià)格對MTA影響很大,MTA短與清華大學(xué)的工藝都已到了中試或示范廠的程度,期內(nèi)很難與石油芳烴相競爭。從長期來看,在石油表明我國正積極地將MTA推向工業(yè)化,在煤制芳資源緊缺和天然氣/煤炭相對豐富的國家和地區(qū)發(fā)展烴的領(lǐng)域已處于世界領(lǐng)先地位MTA技術(shù)具有較大的可行性,掌握MTA技術(shù)對芳烴工業(yè)將來的發(fā)展具有戰(zhàn)略性意義。4總結(jié)和展望(1)MTA是繼MTG和MTO之后下一個(gè)甲醇[1] LEE S中國煤化工yM.Ford轉(zhuǎn)化的熱點(diǎn),在我國被列為“十二五”期間新型煤化dHCNMHG工行業(yè)重點(diǎn)開發(fā)和應(yīng)用的核心技術(shù)之一。MTA催[2] LANGE J F. Methanol synthesis: A short review第3期甲醇制芳烴研究進(jìn)展545technology improvements [J]. Catalysis Today, 2001, [13] DAHL I M, KOLBOE S. On the reaction mechanism64(1-2):3-8.for hydrocarbon formation from methanol over SAPO-34[3]周士義,李杰.甲醇合成技術(shù)進(jìn)展[].化工科技2 Isotopic labeling studies of the co-reaction of propene2011, 19(5):73-76. (ZHOU Shiyi, LI Jie. Progressand methanol]. Journal of Catalysis, 1996, 161(1)on synthesis technology of methanol [J]. ScienceTechnology in Chemical Industry, 2011, 19(5):73- [14] SONG W, MARCUS D M, FU H, et al. Anoft-studied reaction that may never have been: Direct[4]黃祥俊.對二甲苯市場綜述及營銷策略[].中國石油catalytic conversion of methanol or dimethyl ether to和化工標(biāo)準(zhǔn)與質(zhì)量,2011,12(12):211-212.( HUANGhydrocarbons on the solid acids HZSM-5 or HSAPO-34Xiangjun. Marketing strategy of p-xylene [J].China[J]. Journal of the American Chemical Society, 2002Petroleum and Chemical Standard and Quality, 2011124(15):3844-384512(12):211-212.)[15 CHANG C D, SILVESTRI A, SMITH R L[5] STOCKER M. Methanol-to-hydrocarbons: CatalyticProduction of gasoline hydrocarbons US, 3928483materials and their behavior [J]. Microporous and[P].1975Mesoporous Materials, 1999, 29(1-2):3-48.[16] GB 1446522-1976. Production of aromatic compounds[6] HAW J F, SONG W G, MARCUS D M, et al. TheMechanism of methanol to hydrocarbon catalysis [J]. [17] ROBINSON J G, BAMES D I, CARSWELL A MAccounts of Chemical Research, 2003, 36(5):317-326Improvements in catalysis: EP, 0039996[P].1981[7]邢愛華,林泉,朱偉平,等.甲醇制烯烴反應(yīng)機(jī)理研究[18] SEDDON D, MOLE T, WHITESIDE J A. Methanol進(jìn)展[J].天然氣化工,2011,36(1):59-65.(XINGversion to hydrocarbons with zeolites and cocatalystsAihua, LIN Quan, ZhU Weiping, et al. Advance inWO,8201866[P].1982esearch on reaction mechanism for methanol to olefins [19] MIHAIL R, STRAJA S, MARIA G, et al. A kineti[]. Natural Gas Chemical Industry,2011,36(1):59-model for methanol conversion to hydrocarbons [J].65.)Chemical Engineering Science(9):1581-1591[8] DAHL I M, KOLBOE S. On the reaction mechanism [20] PARKER L M, BIBBY D M. Synthesis and somefor propene formation in the mTo reaction over SAPO-34properties of two novel zeolites, KZ-1 and KZ-2[J][J]. Catalysis Letters, 1993, 20(3-4):329-336Zeolites,1983,3(1):8-11.[9] DESSAU R M, LAPIERRE R B. On the mechanism of [21] HOELDERICH W, MROSS W, SCHWARTZMANN Mmethanol conversion to hydrocarbons over HZSM-5[J]Process for the preparation of aromatic hydrocarboJournal of Catalysis, 1982,78(1):136-14from methanol and/or dimethyl ether: EP, 0090284[10]王仰東,王傳明,劉紅星,等. HSAPO34分子篩上氧[P].1983鑰葉立德機(jī)理的第一性原理研究[].催化學(xué)報(bào),2010,[22]蔡天錫,周永生,王大慶,等.雜多酸催化劑上甲醇轉(zhuǎn)31(1): 33-37.( WANG Yangdong, WANG Chuanming化為烴的研究[J].催化學(xué)報(bào),1984,5(2):180-184.LIU Hongxing, et al. A first-principle study of(CAI Tianxi, ZHOU Yongsheng, WANG Daqing, et al.oxonium ylide mechanism over HSAPO-34 zeolite [J]Chinese Journal of Catalysis, 2010, 31(1): 33-37.heteropoly compounds as catalysts[J]. Chinese Journal[11] HUNTER R, HUTCHINGS G J, PICKL Wof Catalysis,1984,5(2):180-184.)Mechanistic studies on initial C-C bond formation in the [23] CECKIEWICZ S. Conversion of methanol into lightzeolite ZSM-5 catalysed methanol conversion reaction:hydrocarbons on erionite-offretite zeolite[J]. Journal ofEvidence against a radical pathway [J]. Journal of thethe Chemical Society, Faraday Transactions 1, 1984Chemical Society, Chemical Communications, 1987,1184(11):2989-2998(11):843-844.24ITOH H, HIDALGOC V, HATTORI T, et al. Role[12] LESTHAEGHE D, VANS V, MARIN G, et alof acid property of various zeolites in the methanolUnderstanding the failure of direct C-C coupling in theconversionbons[I l. journal of Catalysiszeolite-catalzed methanoi-to-olefin process [J 1.中國煤化工Angewandte Chemie International Edition, 2006, 45 [25] JANOWCNMHGRT D, et al(11):1714-1719.Catalyst and method for producing hydrocarbons boiling546石油學(xué)報(bào)(石油加工)第29卷in the gasoline range from methanol and/or dimethyl [36] CONTE M, LOPEZ-SANCHEZ J, HEether:DD,208735[P].1984.Modified zeolite ZSM-5 for the methanol[26] BITTRICH HH, FELDHAUS R, ANDERS K, et al.reaction[J]. Catalysis Science and Technology, 2012, 2Olefins and aromatic-rich gasoline fractions from(1):105-112.hydrocarbon fractions: DD, 233583[P].1986[37] DWYER F G, SCHWARTZ A B. Catalyst and its use[27] XU Y, GREY C P, THOMAS J M, et al. AnDE,2818831P].1978investigation into the conversion of methanol to [38] KAEDING WW. Methanol conversion to para- xylenehydrocarbons over a SAPo-34 catalyst using magic-using a zeolite catalyst containing an oxide of boronangle-spinning NMR and gas chromatography [J]magnesium, phosphorus, or mixtures: US, 4088706Catalysis Letters, 1990, 4(3): 251-260.P].1978.[28] RAVISHANKAR R, BHATTACHARYA D, JACOB [39] LALIK E, LIU X, KLINOWSKI J. Role of gallium inNE, et al. Characterizationthe catalytic activity of zeolite [Si, GaJ-ZSM-5 forzeolite MCM-22[J]. MicropMaterials, 1995,4methanol conversion[J. Journal of Physical Chemistry(1):83-93.1992,96(2):805-809[29] MIKKELSEN O, KOLBOE S. The conversion of[40]王錦業(yè),王定珠,盧學(xué)棟,等.陽離子改性HZM5沸methanol to hydrocarbons over zeolite H-beta [J]石上低碳醇轉(zhuǎn)化為芳烴[J].催化學(xué)報(bào),1993,14(3):Microporous and Mesoporous Materials, 1999, 29(1234-238. WANG Jinye, WANG Dingzhu, LU):173-184Xuedong, et al. Conversion of lower alcohols into[30] KVISLE S, FUGLERUD T, KOLBOE S, et al.aromatics over cation-modified HZSM-5 zeolites [J]Methanol-to- Hydrocarbons[ MJ//ERTL G, KNOZINGERChinese Journal of Catalysis, 1993, 14(3): 234-238.)H, SCHUTH F, et al. Handbook of Heterogeneous [41] ONO Y, OSAKO K, KIM G, et al. Ag-ZSM-5 as aCatalysis. 2nd Ed. Vol 6. Weinheim: Wiley-VCH.Catalyst for Aromatization of Alkanes, Alkenes, and2008:2950-2965Methanol M //WEITKAMP J, KARGE H G[31] SASSI A, WILDMANPFEifER H, et al. Studies in Surface Science andReactions of butylbenzene isomers on zeolite H Beta:1994,84:1773-1Methanol-to-olefins hydrocarbon pool chemistry and [42] FREEMAN D, WELLS R P K, HUTCHINGSG Jsecondary reactions of olefins [J]. Journal of PhysicalConversion of methanol to hydrocarbons over Ga2 O3/Chemistry B,2002,106(34):8768-8773.H-ZSM-5 and Ga2 O3/wO3 catalysts [J]. Journal of[32]王金英,李文懷,胡津仙,等, ZnHZSM5上甲醇芳構(gòu)Catalysis,2002,205(2):358-365.化反應(yīng)的研究[J.燃料化學(xué)學(xué)報(bào),209,37(5):607-[43] ZAIDI H A, PANT KK. Catalytic conversion of612.( WANG Jinying, LI Wenhuai, HU Jinxian, et al.methanol to gasoline range hydrocarbons [J]. CatalysisStudy of methanol to aromatics on ZnHZSM-5 catalystToday,2004,96(3):155-160[J]. Journal of Fuel Chemistry and Technology,2009,[44許磊,劉中民,李銘芝,等.一種甲醇轉(zhuǎn)化制取對二甲37(5):607-612.)苯的催化劑及其制備方法與應(yīng)用:中國,101767038[33] ONO Y, ADACHI H, SENODASelectiveconversion of methanol into aromatic hydrocarbons over [45] SONG Y, ZHU X, XU L. Study on the process ofzinc-exchanged ZSM-5 zeolites [J]. Journal of thetransformation of olefin into aromatics over HZSMChemical Society, Faraday Transactions, 1988, 84(4):[J]. Catalysis Communication, 2006, 7(4): 218-223.1091-1099.[46] SEDRAN U A, FIGOLI N S. Relation between acidity[34] BARTHOS R, BANSAGI T, SUELI Z T, et al.and activity during the transformation of methanol intoAromatization of methanol and methylation of benzenehydrocarbons on amorphous silica-alumina[J]. Appliedover Moz C/ZSM-5 catalysts[J]. Journal of CatalysisCatalysis,1985,19(2):317-3252007,247(2):368-378[47]MANDERSLOOT W G B, NICOLAIDES C P,[35] FREEMAN D, WELLS R P K, HUTCHINGS G J.SCURRETents on the effect of the acidicMethanol to hydrocarbons: Enhanced aromatic formation中國煤化工ion of methanolusing a composite Ga2 O3-H-ZSM-5CNMHG,1986,27(2)Chemical Communications, 2001, 18(18):1754-1755.393-396第3期甲醇制芳烴研究進(jìn)展547[48]鐘炳,羅慶云,肖有燮,等.甲醇在HZSM5上轉(zhuǎn)化為high resistance to coke formation for methanol烴類的催化反應(yīng)機(jī)理[J].燃料化學(xué)學(xué)報(bào),1986,14Microporous and Mesoporous(1):9-16.( ZHONG Bing, LUO Qingyun, XIAOMaterials,2012,151:26-33Youxie, et al. Reaction mechanism of methanol[58 BIBBY D M, HOWE R F, MCLELLAN G D. Cokehydrocarbons on HZSM-5[J]. Journal of Fuel Chemistryformation in high-silica zeolites [J]. Applied Catalysisand Technology, 1986, 14(1):9-16)A: General,1992,93(1):1-34[49] AKOLEKAR D B, CHOUDHARY VR. Acidity and [59] BAUER F, GEIDEL E, GEYER W, et al. TG-FTIRcatalytic properties of H. Na-ZSM-8 zeolite: Effect ofand isotopic studies on coke formation during the MTGH+ exchange, pretreatment condition, and poisoning ofprocess [J]. Microporous and Mesoporous Materialsstronger acid sites[J]. Journal of Catalysis, 1987, 1051999,29(1-2):109-115.(2):416-431[60 VAUGHAN J S, OCONNOR C T, FLETCHER J C Q[50] SINITSYNA O A, MOSKOVSKAYA I FofopeneROMANOVSkII B V. Correlation between acid andheteropoly acids[j]. Journal of Catalysis, 1994, 147catalytic properties of high-silica zeolites as methanol(2):441-454.conversion catalysts [J]. Kinetikai Kataliz, 1989, 30 [61] BARTHOLOMEW C H. Mechanisms of catalyst(3):761-766deactivation[J]. Applied Catalysis A: General,2001[51] VEDREINE J, AUROUX A, DEJAIFVE P, et al.212(1-2):17-60Catalytic and physical properties of phosphorus-modified [62] PALUMBO L, BONINO F, BEATo P, et aL.ZSM-5 zeolite[J. Journal of Catalysis, 1982, 73(1):Conversion of methanol to hydrocarbons Spectrosco147-160.characterization of carbonaformed[52] CHOUDHARY V R, NAYAK V S. Conversion ofH-ZSM-50J]. Journal of Physical Chemistry Calcohols to aromatics on H-ZSM-5 Influence of112(26):9710-9716silicon/aluminum ratio and degree of cation exchange on [63] BJORGEN M, OLSBYE U, KOLBOE S. Cokeproduct distribution[J]. Zeolites, 1985, 5(5):325-328.precursor formation and zeolite deactivation: Mechanistic[53 CHOUDHARY V R, KINAGE A K. Methanol-to-insights from hexamethylbenzene conversion[J]. Journalaromatics conversion over H-gallosilicate MFI ):of Catalysis,2003,215(1):30-44Influence of Si/Ga ratio, degree of H* exchange, [64 IMAI T, FUJITA H. Aromatic hydrocarbon mixturespretreatment conditions, and poisoning of strong acidJP,57010685[P].1982sites[J. Zeolites,1995,15(8):732-738[65 HOELDERICH W, MROSS W, SCHWARTZMANN M.[54] MENTZEL U V, HOJHOLT K T, HOLM M SProcess for the preparation of aromatic hydrocarbonsConversion of methanol to hydrocarbons overfrom methanol and/or dimethyl ether: EP, 0090284conventional and mesoporous H-ZSM-5 and H-Ga-MFI:[P].1983Major differences in deactivation behavior[J]. Applied [66] KURINA L N, DEMIDOW A V, KOVAL L M.Catalysis A: General, 2012, 417-418: 290-297Aromatic hydrocarbons: SU, 1188159[P]. 1985[55]SEXTON B A, HUGHES A E, BIBBY D M. An XPS [67] CHANG C D, JACOB S M, SILVESTRI A Jstudy of coke distribution on ZSM-5 [J]. Journal oConversion of liquid alcohols and ethers with a fluidCatalysis,1988,109(1):126-131mass of ZSM-5 type catalyst US, 4138440[P]. 1979.[56] BJORGEN M, SVELLE S, JOENSEN F, et al. [68] CHU C C. Aromatization reactions with zeolitesConversion of methanol to hydrocarbons over zeolitecontaining phosphorus oxide: US, 4590321[P]. 1986H-ZSM-5: On the origin of the olefinic species [J]69]李文懷,張慶庚,胡津仙,等.甲醇轉(zhuǎn)化制芳烴工藝及催Journal of Catalysis, 2007, 249(2): 195-207.化劑和催化劑制備方法:中國,1880288P].2006.[57] ROWNAGHI AA, REZAEI F, HEDLUNd J.[70]騫偉中,魏飛,魏彤,等.一種連續(xù)芳構(gòu)化與催化劑再Uniform mesoporous ZSM-5 single crystals catalyst with生的裝置及其方法:中國,101244969[P].2008中國煤化工CNMHG