第29卷第5期華北水利水電學(xué)院學(xué)報(bào)Vol 29 No 5008年10月Journal of North China Institute of Water Conservancy and Hydroelectric Power文章編號(hào):1002-5634(2008)05-0083-03秸稈合成氣合成甲醇的催化劑優(yōu)化實(shí)驗(yàn)研究杜磊(華北水利水電學(xué)院,河南郟州40011)摘要:生物質(zhì)能是一種可再生能源,為了研究秸稈類生物質(zhì)(農(nóng)業(yè)廢棄物)轉(zhuǎn)化為燃料甲醇和生物質(zhì)能的有效利用,采用熱化學(xué)方法在下吸式固定床氣化爐中生產(chǎn)了低熱值秸稈燃?xì)?對(duì)該燃?xì)膺M(jìn)行脫硫、脫氧、焦油催分解、純化、配氫等優(yōu)化實(shí)驗(yàn)制備出秸稈合成氣,在直流流動(dòng)等溫積分反應(yīng)器中進(jìn)行了催化合成甲醇的催化實(shí)驗(yàn),在235℃和5MPa條件下進(jìn)行了催化劑種類及粒度對(duì)甲醇合成的影響實(shí)驗(yàn)實(shí)驗(yàn)結(jié)果表明:合成甲醇的適宜催化劑型號(hào)為C301,最優(yōu)化顆粒粒度為0.833mmx0.351mm.該研究為生物質(zhì)(秸稈)氣催化合成甲醇的深人研究提供了基礎(chǔ)數(shù)據(jù)關(guān)鍵詞:催化劑;秸稈;合成氣;粒度;甲醇合成中圖分類號(hào):S216文獻(xiàn)標(biāo)識(shí)碼:A生物質(zhì)作為可再生能源不僅資源豐富、無污染可再生而且是可再生能源中惟一可以轉(zhuǎn)化為液態(tài)1實(shí)驗(yàn)燃料和化學(xué)品的碳資源生物質(zhì)催化合成甲醇等化1.1試驗(yàn)主要儀器及其生產(chǎn)廠家學(xué)品和液態(tài)燃料技術(shù)是生物質(zhì)能高品位開發(fā)利用技JMQ系列秸稈氣化機(jī)組,河南省宏越秸稈氣化術(shù)之一發(fā)達(dá)國家合成甲醇的生物質(zhì)主要是木材碎技術(shù)有限公司;JA-5槽直流流動(dòng)等溫積分反應(yīng)器,片、甘蔗渣等,采用氧氣和水蒸汽為氣化劑,氣化工江蘇海安石油科研儀器廠;zK-50可控硅電壓調(diào)整藝技術(shù)復(fù)雜,設(shè)備昂貴,制備出髙熱值合成氣后再催器,云南儀表廠;TCS-A智能溫度測(cè)控儀(控溫精化合成甲醇].中國是一個(gè)農(nóng)業(yè)大國,生物質(zhì)資源度為±0.1℃),南京攀達(dá)電子儀器廠;GC-900C型極為豐富,僅秸稈一項(xiàng)年產(chǎn)量即達(dá)6億多t,這些秸氣相色譜儀,中科院天樂精密科學(xué)儀器有限公司稈大部分被廢棄或隨意焚燒,嚴(yán)重污染環(huán)境,造成巨(上海);G2v-5/200隔膜壓縮機(jī),北京第一通用機(jī)大的資源浪費(fèi).目前,全國已建成數(shù)百處秸稈氣化械廠站,生物質(zhì)氣化主要設(shè)備為上吸式及下吸式固定床1.2試驗(yàn)材料氣化爐,用空氣做氣化劑,生產(chǎn)工藝技術(shù)及設(shè)備簡(jiǎn)單選用鄭州東郊當(dāng)年新收獲的玉米秸稈為原材價(jià)廉,生物質(zhì)燃?xì)鉃楹倭拷褂偷牡蜔嶂等細(xì)?該氣料,經(jīng)曬干并粉碎至2~3cm,在JMQ系列秸稈氣化體中氮?dú)饧岸趸己枯^高,氫氣含量較低,必須機(jī)組上,以空氣為氣化劑,制備出秸稈原料氣.將原經(jīng)過處理制得合成氣后才能進(jìn)行甲醇合成低熱值料氣經(jīng)脫硫、除氧、分解焦油、凈化、配氫等處理后秸稈燃?xì)庵饕糜谥苯尤紵鲲?少量用于取暖和制備出秸稈合成氣,合成氣組成見表1發(fā)電,生物質(zhì)能利用率較低.為使數(shù)量巨大的生物質(zhì)表1生物質(zhì)合成氣組成資源得到充分、高效的利用,加快實(shí)現(xiàn)生物質(zhì)合成甲COC.H。醇的工業(yè)化步伐筆者進(jìn)行了秸稈合成氣合成甲醇4661-3040120-13.165980.76-1.16327-45.38的催化劑實(shí)驗(yàn)研究注:CH。=CH4,C2H2,C2H4,C2H收稿日期:2008-07-21中國煤化工基金項(xiàng)目:河南省教育廳科技攻關(guān)項(xiàng)目(2007610008)作者簡(jiǎn)介:杜磊(1958-),女河南范縣人,華北水利水電學(xué)院教師,主CNMHG華北水利水電學(xué)院學(xué)報(bào)2008年10月1.3實(shí)驗(yàn)流程與實(shí)驗(yàn)條件選用3種低壓銅基催化劑C301,C302,NC306,其對(duì)如圖1所示,生物質(zhì)合成氣自鋼瓶①經(jīng)穩(wěn)壓閥應(yīng)的實(shí)驗(yàn)條件為:催化劑粒度為16-20目,進(jìn)口合③將壓力控制到主反應(yīng)壓力后進(jìn)入反應(yīng)器②反應(yīng)成氣組成為112%0,5.98%CO2,3273%N2,后氣體經(jīng)冷凝器⑤分離出甲醇和水,不凝氣體經(jīng)減0.76%C,Hn,46.61%H2催化劑粒度優(yōu)化實(shí)驗(yàn)條件壓閥降至常壓由流量計(jì)⑥計(jì)量后,一部分氣體放為:催化劑型號(hào)為C301,催化劑重量為49246g,空另一部分流向氣相色譜儀①,由色譜T作站及電催化劑粒度(目)為16~20,20-40,40-60,60腦⑩自動(dòng)采集和處理數(shù)據(jù)80,進(jìn)口合成氣組成為13.16%CO,9.84%CO245.38%N2,1.16%CH,30.4%H2,催化劑的活化和實(shí)驗(yàn)方法見文獻(xiàn)[10]2結(jié)果分析2.1催化劑的優(yōu)化實(shí)驗(yàn)對(duì)每種催化劑,采用改變進(jìn)口氣流量進(jìn)行實(shí)驗(yàn),結(jié)果見表2.由表2可知:對(duì)C301,C302催化劑,CO轉(zhuǎn)化率隨合成氣進(jìn)口流量的逐漸增大而逐漸變小;器:⑤一冷凝器:⑥—流量計(jì):(一壓縮機(jī):⑧-溫度控制器:⑨一8對(duì)NC306催化劑則是先升高后逐漸降低;對(duì)C301開關(guān):①一溫度顯示器;①氣相色譜僅;⑩一載氣瓶:①一數(shù)據(jù)處催化劑CO2轉(zhuǎn)化率隨著進(jìn)口合成氣流量的不斷增理器;①一計(jì)算機(jī)大的變化趨勢(shì)為由高到低再升高降低是倒S型,而圖1試驗(yàn)裝量系統(tǒng)圖對(duì)C302和NC306催化劑則為由低到高再降低升高生物質(zhì)合成氣在催化劑作用下,可能發(fā)生CO,呈S型變化;甲醇時(shí)空收率隨進(jìn)口合成氣流量的不CO2與H2反應(yīng)合成甲醇的反應(yīng)及生成CO2和H2斷增大各催化劑的變化趨勢(shì)與CO2轉(zhuǎn)化率變化趨的逆反應(yīng)前2個(gè)反應(yīng)分子數(shù)目變小且放熱,最后一勢(shì)相同,且C301催化劑甲醇時(shí)空收率最大,C302催個(gè)反應(yīng)吸熱且反應(yīng)前后分子數(shù)目相同由化學(xué)反應(yīng)化劑次之,NC306催化劑的稍微小些試驗(yàn)結(jié)果表理論可知,增加壓力、降低溫度對(duì)前2個(gè)合成反應(yīng)明:C301,C302,NC3063種催化劑均可作為秸稈類有利,但考慮到設(shè)備投資和催化劑活性,反應(yīng)壓力控生物質(zhì)合成甲醇的催化劑,其中,C301催化劑催化制為5MPa,反應(yīng)操作溫度235℃.催化劑優(yōu)化實(shí)驗(yàn)效果最佳.表2催化劑的活性試驗(yàn)結(jié)果進(jìn)口氣流量c0出口c0出口甲醇c0轉(zhuǎn)化C02轉(zhuǎn)化甲醇時(shí)空收率(mol,b)摩爾分率摩爾分率摩爾分率摩爾分率摩爾分率(kg·(kgnb)“)0.0741620.06l1990.0541630.3982630.0766220.2900222c3011.0523380.0814820.0617610.0421850.3242640.0475720.2648761.3061010.0832980.0603860.0415130.3083430.0676100.3239131.7160850.0896090.0585600.0346980.2464580.0842802.0978130.0938520.0591800.0273060.1997140.0616080.3514332.4690810.0970890.0586640.0231710.1655670.0624440.353767C3020.8992770.0785180.0623360.0458150.3531730.0450982379978c3021.2513970.0855150.0603960.0381280.2854660.0615890.279557C3021.5943400.0935870.0590170.0279570.2029550.0653510.266187C3021.9632080.0941600.0577780.0289693389852.3121120.1002780.0571250.006630.1340060.0826380.28931012C3022.4722040.1020060.0579600.0167680.1124400.0622120.25291613NC3060.9250480.0853040.0623180.0355290.2837690.027030.19604614NC3061.2916440.0837270.0623410.0378900.3000.0309440.29064815Nc306l.8195360.0931550.0598180.020.30194216NC3062.1333220.0962940.0609580.0中國煤化工17Nc3062.4910260.0999400.0590400.01YHSCNMHG0.28049018Nc3062,6919300.0997470.0597280.0175143480.0349980.29101519NC3062.9990900.1002600.0598870.0164940.1271740.0305280.305944第29卷第5期杜磊:秸稈合成氣合成甲醇的催化劑優(yōu)化實(shí)驗(yàn)研究2.2催化劑粒度優(yōu)化實(shí)驗(yàn)不同粒度的催化劑優(yōu)化實(shí)驗(yàn)結(jié)果見表3考文獻(xiàn)[1] Goudeau Jean Claude, Bourreau Alain, Souil Francois. An表3實(shí)驗(yàn)結(jié)果隨催化劑粒度的變化investigation on methanol catalytic synthesis from biomass催化劑粒度/目gases[ J]. Energy Res, 1983(3): 191-202O#R*/% 12. 37 16.98 18. 79 20. 23 [2] Corte P, Lacoste C, Traverse J P. Gasifition and catalyticcO2轉(zhuǎn)化率/%0.300.270.872.01conversion of biomass by flash pyrolysis[ J].J. Anal Appl1046(kKm:b),1023614391610Pyrolysis,1985,7(4):323-325.[3] Baker E G, Brown M D Catalytic steam gasification of ba-gasse for the production of methanol[ J]. Energy Biomass由表3可知,CO轉(zhuǎn)化率及甲醇時(shí)空收率均隨催Wastes,1984,8:651-674.化劑粒度變小而增大,CO2轉(zhuǎn)化率出現(xiàn)相同的變化[4] Beenackers AA C M, Van swaaij W P M. Methanol from趨勢(shì),但20~40目時(shí)例外;甲醇時(shí)空收率隨催化劑ood[ J]. Int. J. Sol. Energy, 1984, 2(5): 349-367.粒度的目數(shù)增大而逐漸變大,但變化幅度較小由于[5] Palmer eric R. Gasification of wood for methanol Produc催化劑粒度越小,目數(shù)越大,使氣體通過單位高度催tion[ J]. Energy Agric., 1984, 3 (4): 363-375化床的壓力降增大,動(dòng)力消耗增大通過綜合考慮,[6] Specht M, Bandi a, Baumgart F,ta, Synthesis of metha催化劑粒度以20-40目為宜,即最佳粒度為nol from biomass/C0, resources[ c]//Greenhouse GasControl Technol. Proc. Int Conf. 4th, 1998: 723-727.0.833mmx0.351mm.[7] Plzak Vojtech, Wendt Hartmut Energetic utilization of bio-3結(jié)語mas[J].Chem.lng.Tech.,1992,64(12):1084-1095[8] Demirbas Ayhan Biomass resources for energy and chemi-1.農(nóng)業(yè)廢棄物——秸稈通過熱化學(xué)轉(zhuǎn)化等處理cal industry[ J]. Energy, Educ. Sci. Technol, 2000, 5(1)后制得的合成氣可直接催化合成燃料甲醇;21-45.2在催化合成反應(yīng)溫度和壓力分別為235℃,[9]房鼎業(yè)姚佩芳朱炳辰甲醇生產(chǎn)技術(shù)及進(jìn)展[M]·上5MPa的條件下,秸稈合成氣催化合成燃料甲醇的海:華東化工學(xué)院出版社,1990適宜催化劑為C301,催化劑顆粒最佳粒度為10]朱靈峰張百良梁庚白等.玉米秸秤熱化學(xué)法合成0.833mmx0.351mm,該研究為生物質(zhì)(秸稈)氣甲醇的研究[]河南農(nóng)業(yè)大學(xué)學(xué)報(bào),2003,37(4):400催化合成甲醇的深入實(shí)驗(yàn)提供了理論數(shù)據(jù)Study on the Optimum Experiments of Methanol Synthesis Catalyst from Cornstalk SyngasDU LeiNorth China Institute of Water Conservancy and Hydroelectric Power, Zhengzhou 450011, China)Abstract: Biomass energy is a renewable and potential resource. In order to research the conversion of cornstalk biomass( the agricultural residues)into the fuel methanol and the effective utilization of biomass energy, the low-heat-value cornstalk gas is produced by themeans of the thermo-chemical method in the down-flow fixed bed gasifier. The comstalk gas is purified and the technical proceduresch as desulfurization, catalytic cracking of tar, deoxygenation, purification and hydrogenation are performed, and the cornstalk synthesisgas is prepared. The catalytic experiments of methanol synthesis with cornstalk syngas are carried out in a tubular flow integral and iso-thermal reactor, the effect of the catalyst types, catalyst particle size is investigated at 235 C under the pressure 5 MPa. The experital results indicat that the proper catalyst for the synthetic reaction is C301 and the optimum catalyst size is 0. 833 mm xO. 351 mmThis study can provide basic data for the further studies of methanol syntheKey words: catalyst; cornstalk; syngas: particle size; methanol synthesisYHE中國煤化工CNMHG