MeMo/USY催化剂对神东煤热解产物的调控
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摘要
以USY分子筛为载体,通过等体积浸渍MoO_3、Fe_2O_3、Co_3O_4、NiO四种过渡金属氧化物,制备了Mo/USY、FeMo/USY、CoMo/USY、NiMo/USY催化剂,并借助ICP、XRD、BET、NH_3-TPD、TG等手段对催化剂进行表征。使用粉-粒流化床进行神东煤的催化热解实验,考察了过渡金属氧化物对USY的改性作用及其对热解产物的影响。结果表明:不同催化剂作用下,半焦收率基本保持在65%左右;与SiO_2相比,USY分子筛使焦油中酚类化合物含量从36.95%减少到5.08%,萘类化合物含量从8.24%增加到72.76%;与USY相比,Mo/USY使气体、液体产物的收率分别降低了4.4个百分点、30.0个百分点,萘类含量减少了18.5个百分点;Fe_2O_3、Co_3O_4、NiO对Mo/USY的改性作用明显,降低了催化剂的积炭率,提高了CH4、C2、C3、CO_2的收率和气体总收率;FeMo/USY促进了产物的芳构化和萘类的生成;CoMo/USY促进了产物的芳构化反应,抑制了萘类的生成反应;NiMo/USY抑制了产物的芳构化反应、萘类的生成反应。
Four transition metal oxides, MoO_3, Fe_2O_3, Co_3O_4, and NiO, were supported on USY molecular sieves by equal volume impregnation to prepare Mo/USY, FeMo/USY, CoMo/USY and NiMo/USY catalysts, and characterized by ICP, XRD, BET, NH_3-TPD, TG. The pyrolysis experiments of Shendong coal were conducted in a powder-particle fluidized bed reactor. The results showed that the yield of the semi coke was basically around 65% with different catalysts. Compared with SiO_2, the content of phenols was reduced from 36.95% to 5.08%, and the content of naphthalenes was increased from 8.24% to72.76% in tar by USY molecular sieve. Compared with USY molecular sieve, gas product yield, liquid product yield, and content of naphthalenes was decreased by 4.4%, 30.0% and 18.5% by Mo respectively. The effects of Fe_2O_3, Co_3O_4 and NiO on the modification of Mo/USY were obvious, which reduced the carbon accumulation rate of the catalyst and increased the yield of CH4, C2, C3, CO_2 and the total gas. The aromatization of the products and the formation of naphthalenes were enhanced by FeMo/USY. The aromatization reaction of the product was enhanced, but the formation reaction of naphthalenes was inhibited by CoMo/USY. The aromatization reaction of the products and the formation reaction of naphthalenes were inhibited by NiMo/USY.
Four transition metal oxides, MoO_3, Fe_2O_3, Co_3O_4, and NiO, were supported on USY molecular sieves by equal volume impregnation to prepare Mo/USY, FeMo/USY, CoMo/USY and NiMo/USY catalysts, and characterized by ICP, XRD, BET, NH_3-TPD, TG. The pyrolysis experiments of Shendong coal were conducted in a powder-particle fluidized bed reactor. The results showed that the yield of the semi coke was basically around 65% with different catalysts. Compared with SiO_2, the content of phenols was reduced from 36.95% to 5.08%, and the content of naphthalenes was increased from 8.24% to72.76% in tar by USY molecular sieve. Compared with USY molecular sieve, gas product yield, liquid product yield, and content of naphthalenes was decreased by 4.4%, 30.0% and 18.5% by Mo respectively. The effects of Fe_2O_3, Co_3O_4 and NiO on the modification of Mo/USY were obvious, which reduced the carbon accumulation rate of the catalyst and increased the yield of CH4, C2, C3, CO_2 and the total gas. The aromatization of the products and the formation of naphthalenes were enhanced by FeMo/USY. The aromatization reaction of the product was enhanced, but the formation reaction of naphthalenes was inhibited by CoMo/USY. The aromatization reaction of the products and the formation reaction of naphthalenes were inhibited by NiMo/USY.
引文
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[17]王苗,李云,王毅,等.基于热分析法的神府粉煤低温热解影响因素研究[J].煤炭转化,2017,40(3):15-20.WANG M,LI Y,WANG Y,et al.Study on the influence factors of low temperature pyrolysis of Shenfu pulverized coal based on thermal analysis method[J].Coal Conversion,2017,40(3):15-20.
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[19]杨平,辛靖,李明丰,等.负载Mo、W氧化物对Y型分子筛结构及酸性的影响[J].石油学报(石油加工),2010,27(5):668-673.YANG P,XIN J,LI M F,et al.Effects of Mo and W oxides on the structure and acidity of Y zeolites[J].Journal of Petroleum Engineering(Petroleum Processing),2010,27(5):668-673.
[20]薛全民,张永春,宋伟杰.钴离子改性的Y型分子筛对低浓度NO吸附性能的研究[J].离子交换与吸附,2004,20(3):254-259.XUE Q M,ZHANG Y C,SONG W J.Low-concentration NOadsorption capabiliy on co-containing Y-zeolite[J].Ion Exchange and Adsorption,2004,20(3):254-259.
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[22]OLIVEIRA M L M,MIRANDA A A L,BARBOSAC M B M,et al.Adsorption of thiophene and toluene on NaY zeolites exchanged with Ag(Ⅰ),Ni(Ⅱ)and Zn(Ⅱ)[J].Fuel,2009,88(10):1885-1892.
[23]SHEILA G A F,FATIMA M Z Z,LUCIA R R A,et al.Influence of support acidity of NiMoS catalysts in the activity for hydrogenation and hydrocracking of tetralin[J].Applied Catalysis A:General,2010,384(1/2):51-57.
[24]SALAMA T M,OTHMAN I,SIRAG M,et al.Comparative study of molybdeum oxide in NaY zeolite prepared by conventional impregnation and vapor-phase deposition techniques[J].Microporous and Mesoporous Materials,2006,95(1/2/3):312-320.
[25]张玲,蒋忠祥,王海彦.多级孔ZSM-5分子筛的制备及芳构化研究[C]//2016化工新材料暨环氧树脂和聚氨酯技术交流研讨会,2016,上海.ZHANG L,JIANG Z X,WANG H Y.Study on the preparation and aromatization of multistage ZSM-5 molecular sieves[C]//2016Symposium on New Chemical Materials and Technology Exchange of Epoxy Resin and Polyurethane,2016,Shanghai.
[26]姜建清,潘华,孙国金,等.过渡金属/分子筛催化剂上选择性催化还原氮氧化物的研究进展[J].化工进展,2012,31(1):98-106.JIANG J Q,PAN H,SUN G J,et al.Progress in selective catalytic reduction of nitrogen oxides over transition metal/zeolite catalysts[J].Chemical Industry and Engineering Progress,2012,31(1):98-106.
[27]MORTENSEN P M,GRUNWALDT J D,JENSEN P A,et al.A review of catalytic upgrading of bio-oil to engine fuels[J].Applied Catalysis A:General,2011,407(1/2):1-19.
[28]闫伦靖.煤焦油气相催化裂解生成轻质芳烃的研究[D].太原:太原理工大学,2016.YAN L J.Coal tar vapor phase catalytic cracking light aromatic hydrocarbon production studies[D].Taiyuan:Taiyuan University of Technology,2016.
[29]CARLSON T R,JAE J,HUBER G W.Mechanistic insights from isotopic studies of glucose conversion to aromatics over ZSM-5[J].ChemCatChem,2009,1(1):107-110.
[30]CARLSON T R,CHENG Y T,JAE J,et al.Production of green aromatics and olefins by catalytic fast pyrolysis of wood sawdust[J].Energy&Environmental Science,2011,4(1):145-161.
[31]GAYUBO A G,VALLE B,AGUAYO A T,et al.Olefin production by catalytic transformation of crude bio-oil in a two-step process[J].Industrial and Engineering Chemistry Research,2010,49(1):123-131.
[32]CYPRES R.Aromatic hydrocarbons formation during coal pyrolysis[J].Fuel Processing Technology,1987,15:1-15.
[33]WILLIAMS P T,TAYLOR D T.Aromatization of tyre pyrolysis oil to yield polycyclic aromatic hydrocarbons[J].Fuel,1993,72(11):1469-1474.
[34]LIU T L,CAO J P,ZHAO X Y.In situ upgrading of Shengli lignite pyrolysis vapors over metal-loaded HZSM-5 catalyst[J].Fuel Processing Technology,2017,160(6):19-26.
[35]VICHAPHUND S,AHT-ONG D,SRICHAROENCHAIKUL V,et al.Catalytic upgrading pyrolysis vapors of Jatropha waste using metal promoted ZSM-5 catalysts:an analytical Py-GC/MS[J].Renewable Energy,2014,65:70-77.
[2]国家统计局.中国2016年国民经济和社会发展统计公报[EB/OL].2017.http://www.stats.gov.cn/tjsj/zxfb/201702/t20170228_1467424.html.National Bureau of Statistics.China 2016 national economic and social development bulletin[EB/OL].February 2017.http://www.stats.gov.cn/tjsj/zxfb/201702/t20170228_1467424.html.
[3]谢克昌.中国煤炭清洁高效可持续开发利用战略研究[M].北京:科学出版社,2014:2-5.XIE K C.Study on clean,efficient and sustainable development and utilization strategy of coal in China[M].Beijing:Science Press,2014:2-5.
[4]MORENO B M,QUACH A L,MERVES M N,et al.Discrimination between free-radical and concerted pyrolysis mechanisms[J].Energy&Fuels,2014,28(7):4256-4259.
[5]邹献武,姚建中,杨学民,等.喷动-载流床中Co/ZSM-5分子筛催化剂对煤热解的催化作用[J].过程工程学报,2007,7(6):1107-1112.ZOU X W,YAO J Z,YANG X M,et al.Catalytic action of Co/ZSM-5zeolite catalysts in coal pyrolysis in a spouted entrained flow reactor[J].The Chinese Journal of Process Engineering,2007,7(6):1107-1112.
[6]TAKARADA T,ONOYAMA Y,TAKAYAMA K,et al.Hydropyrolysis of coal in a pressurized powder-particle fluidized bed using several catalysts[J].Catalysis Today,1997,39(1):127-136.
[7]梁丽彤,黄伟,张乾,等.低阶煤催化热解研究现状与进展[J].化工进展,2015,34(10):3617-3622.LIANG L T,HUANG W,ZHANG Q,et al.Present status and progress of catalytic pyrolysis of low rank coals[J].Chemical Industry and Engineering Progress,2015,34(10):3617-3622.
[8]何选明,方嘉淇,潘叶.Fe2O3/CaO对低阶煤低温催化干馏的影响[J].化工进展,2014,33(2):363-367.HE X M,FANG J Q,PAN Y.Effect of Fe2O3/CaO on low temperature catalytic carbonization of low rank coals[J].Chemical Industry and Engineering Progress,2014,33(2):363-367.
[9]熊杰,周志杰,许慎启,等.碱金属对煤热解和气化反应速率的影响[J].化工学报,2011,62(1):192-198.XIONG J,ZHOU Z J,XU S Q,et al.Effect of alkaline metal on rate of coal pyrolysis and gasification[J].CIESC J.,2011,62(1):192-198.
[10]MA Z C,MA X X,LUO J C,et al.Catalytic hydropyrolysis of five Chinese coals[J].Energy&Fuels,2011,26(1):511-517.
[11]LIU L L,KUMAR S,WANG Z H,et al.Catalytic effect of metal chlorides on coal pyrolysis and gasification part I.Combined TG-FTIRstudy for coal pyrolysis[J].Thermochimica Acta,2017,655:331-336.
[12]LI Q,FENG X Y,WANG X,et al.Pyrolysis of Yulin coal over ZSM-22 supported catalysts for upgrading coal tar in fixed bed reactor[J].Journal of Analytical and Applied Pyrolysis,2017(126):390-396.
[13]陈静升,马晓迅,李爽,等.CoMoP/13X催化剂上黄土庙煤热解特性研究[J].煤炭转化,2012,35(1):4-8.CHEN J S,MA X X,LI S,et al.Study on pyrolysis characteristics of Huang Tu Miao coal on CoMoP/13X catalyst[J].Coal Conversion,2012,35(1):4-8.
[14]LI S,CHEN J S,HAO T,et al.Pyrolysis of Huang Tu Miao coal over faujasite zeolite and supported transition metal catalysts[J].Journal of Analytical and Applied Pyrolysis,2013,102(7):161-169.
[15]侯彩霞,张帅,梁英华,等.碱酸处理对褐煤结构的影响[J].煤炭转化,2016,39(3):19-22.HOU C X,ZHANG S,LIANG Y H,et al.The effect of alkali acid treatment on the structure of lignite[J].Coal Conversion,2016,39(3):19-22.
[16]ZHU H L,YU G S,GUO Q H,et al.In situ Raman spectroscopy study on catalytic pyrolysis of a bituminous coal[J].Energy Fuels,2017,31(6):5817-5827.
[17]王苗,李云,王毅,等.基于热分析法的神府粉煤低温热解影响因素研究[J].煤炭转化,2017,40(3):15-20.WANG M,LI Y,WANG Y,et al.Study on the influence factors of low temperature pyrolysis of Shenfu pulverized coal based on thermal analysis method[J].Coal Conversion,2017,40(3):15-20.
[18]曹大盼,何瑞玉,马晓迅.神东煤粉粒流化床催化热解特性研究[J].西北大学学报,2017,47(5):717-723.CAO D P,HE R Y,MA X X.The catalytic pyrolysis of Shendong pulverized coal particle fluidized bed[J].Journal of Northwestern University,2017,47(5):717-723.
[19]杨平,辛靖,李明丰,等.负载Mo、W氧化物对Y型分子筛结构及酸性的影响[J].石油学报(石油加工),2010,27(5):668-673.YANG P,XIN J,LI M F,et al.Effects of Mo and W oxides on the structure and acidity of Y zeolites[J].Journal of Petroleum Engineering(Petroleum Processing),2010,27(5):668-673.
[20]薛全民,张永春,宋伟杰.钴离子改性的Y型分子筛对低浓度NO吸附性能的研究[J].离子交换与吸附,2004,20(3):254-259.XUE Q M,ZHANG Y C,SONG W J.Low-concentration NOadsorption capabiliy on co-containing Y-zeolite[J].Ion Exchange and Adsorption,2004,20(3):254-259.
[21]RICHARD W B,YOUNG H K,ANNE H,et al.Structure and density of Mo and acid sites in Mo-exchanged H-ZSM5 catalysts for nonoxidative methane conversion[J].Journal of Physical Chemistry B,1999(103):5787-5796.
[22]OLIVEIRA M L M,MIRANDA A A L,BARBOSAC M B M,et al.Adsorption of thiophene and toluene on NaY zeolites exchanged with Ag(Ⅰ),Ni(Ⅱ)and Zn(Ⅱ)[J].Fuel,2009,88(10):1885-1892.
[23]SHEILA G A F,FATIMA M Z Z,LUCIA R R A,et al.Influence of support acidity of NiMoS catalysts in the activity for hydrogenation and hydrocracking of tetralin[J].Applied Catalysis A:General,2010,384(1/2):51-57.
[24]SALAMA T M,OTHMAN I,SIRAG M,et al.Comparative study of molybdeum oxide in NaY zeolite prepared by conventional impregnation and vapor-phase deposition techniques[J].Microporous and Mesoporous Materials,2006,95(1/2/3):312-320.
[25]张玲,蒋忠祥,王海彦.多级孔ZSM-5分子筛的制备及芳构化研究[C]//2016化工新材料暨环氧树脂和聚氨酯技术交流研讨会,2016,上海.ZHANG L,JIANG Z X,WANG H Y.Study on the preparation and aromatization of multistage ZSM-5 molecular sieves[C]//2016Symposium on New Chemical Materials and Technology Exchange of Epoxy Resin and Polyurethane,2016,Shanghai.
[26]姜建清,潘华,孙国金,等.过渡金属/分子筛催化剂上选择性催化还原氮氧化物的研究进展[J].化工进展,2012,31(1):98-106.JIANG J Q,PAN H,SUN G J,et al.Progress in selective catalytic reduction of nitrogen oxides over transition metal/zeolite catalysts[J].Chemical Industry and Engineering Progress,2012,31(1):98-106.
[27]MORTENSEN P M,GRUNWALDT J D,JENSEN P A,et al.A review of catalytic upgrading of bio-oil to engine fuels[J].Applied Catalysis A:General,2011,407(1/2):1-19.
[28]闫伦靖.煤焦油气相催化裂解生成轻质芳烃的研究[D].太原:太原理工大学,2016.YAN L J.Coal tar vapor phase catalytic cracking light aromatic hydrocarbon production studies[D].Taiyuan:Taiyuan University of Technology,2016.
[29]CARLSON T R,JAE J,HUBER G W.Mechanistic insights from isotopic studies of glucose conversion to aromatics over ZSM-5[J].ChemCatChem,2009,1(1):107-110.
[30]CARLSON T R,CHENG Y T,JAE J,et al.Production of green aromatics and olefins by catalytic fast pyrolysis of wood sawdust[J].Energy&Environmental Science,2011,4(1):145-161.
[31]GAYUBO A G,VALLE B,AGUAYO A T,et al.Olefin production by catalytic transformation of crude bio-oil in a two-step process[J].Industrial and Engineering Chemistry Research,2010,49(1):123-131.
[32]CYPRES R.Aromatic hydrocarbons formation during coal pyrolysis[J].Fuel Processing Technology,1987,15:1-15.
[33]WILLIAMS P T,TAYLOR D T.Aromatization of tyre pyrolysis oil to yield polycyclic aromatic hydrocarbons[J].Fuel,1993,72(11):1469-1474.
[34]LIU T L,CAO J P,ZHAO X Y.In situ upgrading of Shengli lignite pyrolysis vapors over metal-loaded HZSM-5 catalyst[J].Fuel Processing Technology,2017,160(6):19-26.
[35]VICHAPHUND S,AHT-ONG D,SRICHAROENCHAIKUL V,et al.Catalytic upgrading pyrolysis vapors of Jatropha waste using metal promoted ZSM-5 catalysts:an analytical Py-GC/MS[J].Renewable Energy,2014,65:70-77.
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