过渡金属氧化物担载型USY分子筛对神东煤催化热解行为的影响
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摘要
利用粉-粒流化床热解实验装置,研究了过渡金属氧化物改性的USY分子筛对神东煤热解行为的影响。结果表明:过渡金属氧化物改性后USY分子筛骨架结构未发生变化,酸量变化显著。催化剂对神东煤一次热解挥发分的催化作用明显,半焦收率基本保持在66%左右;在实验所选五种催化剂作用下热解挥发分的脱氧反应都增强,热解气中CO和CO_2的收率明显增加,液体产物收率下降,强酸性导致积碳严重,双金属改性后积碳情况改善。USY分子筛对轻质芳烃的形成具有较高的催化活性,其酸性中心能促进焦油中含氧化合物、稠环芳烃和脂肪烃向萘类芳烃转化,负载WO_3后会抑制焦油中萘类芳烃的生成,NiO引入后催化剂的双金属活性导致此抑制作用更为明显,且NiO的裂解性和脱氢性能会显著增加焦油中脂肪烃的含量和气体中H2的收率。
USY zeolite modified by transition metal oxides was used as catalyst in a fluidized bed reactor to study the effects of catalysts loaded with different transition metal oxides on the pyrolysis behavior of Shendong coal.The results show that the skeleton structure of USY zeolite hasn't changed when modification by transition metal oxides,and the acidity has changed obviously.The catalyst mainly catalyzes the volatile matter of the first pyrolysis product of Shendong coal,and the yield of semi-coke is about 66%.The catalyst can enhance deoxygenation of volatile so that the yield of CO and CO_2 obviously increases,and the yield of liquid product decreases.Strong acidity leads to serious carbon deposition but it is improved after bimetallic modification.USY zeolites have high catalytic activity for light aromatics formation,and its acidic center can promote the conversion of oxygenates,polycyclic aromatic hydrocarbons and aliphatic hydrocarbons to naphthalene aromatics in tar.The modified transition metal oxides can inhibit the formation of naphthalene aromatic hydrocarbons in tar,and NiO can inhibit the formation of naphthalene aromatic hydrocarbons more obviously.At the same time,the cracking and dehydrogenation performance of NiO can significantly increase the content of aliphatic hydrocarbon in tar and the yield of H_2 in gas.
USY zeolite modified by transition metal oxides was used as catalyst in a fluidized bed reactor to study the effects of catalysts loaded with different transition metal oxides on the pyrolysis behavior of Shendong coal.The results show that the skeleton structure of USY zeolite hasn't changed when modification by transition metal oxides,and the acidity has changed obviously.The catalyst mainly catalyzes the volatile matter of the first pyrolysis product of Shendong coal,and the yield of semi-coke is about 66%.The catalyst can enhance deoxygenation of volatile so that the yield of CO and CO_2 obviously increases,and the yield of liquid product decreases.Strong acidity leads to serious carbon deposition but it is improved after bimetallic modification.USY zeolites have high catalytic activity for light aromatics formation,and its acidic center can promote the conversion of oxygenates,polycyclic aromatic hydrocarbons and aliphatic hydrocarbons to naphthalene aromatics in tar.The modified transition metal oxides can inhibit the formation of naphthalene aromatic hydrocarbons in tar,and NiO can inhibit the formation of naphthalene aromatic hydrocarbons more obviously.At the same time,the cracking and dehydrogenation performance of NiO can significantly increase the content of aliphatic hydrocarbon in tar and the yield of H_2 in gas.
引文
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[19]FAN Liangliang,CHEN Paul,ZHOU Nan,et al.In-situ and Ex-situ Catalytic Upgrading of Vapors from Microwave-assisted Pyrolysis of Lignin[J].Bioresource Technology,2018,247:851-858.
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[24]李刚.基于过渡金属氧化物/USY催化剂的神东煤催化热解研究[D].西安:西北大学,2018.LI Gang.Study on Catalytic Pyrolysis of Shendong Coal Based on Transition Metal Oxide/USY Catalysts[D].Xi’an:Northwest University,2018.
[25]李昱,张英强,刘娜,等.低碳烯烃芳构化催化剂与工艺进展[J].抚顺石油学院学报,2002,22(1):23-28.LI Yu,ZHANG Yingqiang,LIU Na,et al.Development of Process and Catalyst of Low Olefin Aromatization[J].Journal of Fushun Petroleum Institute,2002,22(1):23-28.
[26]孔晓俊.USY分子筛对煤热解气态焦油的催化改质[D].太原:太原理工大学,2016.KONG Xiaojun.Catalytic Upgrading of Coal Gaseous Tar over USY Zeolites[D].Taiyuan:Taiyuan University of Technology,2016.
[27]MA Zhiqiang,TROUSSARD Ekaterina,VAN BOKHOVEN J A.Controlling the Selectivity to Chemicals from Lignin via Catalytic Fast Pyrolysis[J].Applied Catalysis A:General,2012,423/424(18):130-136.
[28]闫伦靖,孔晓俊,白永辉,等.Mo和Ni改性HZSM-5催化剂对煤热解焦油的改质[J].燃料化学学报,2016,44(1):30-36.YAN Lunjing,KONG Xiaojun,BAI Yonghui,et al.Catalytic Upgrading of Gaseous Tar from Coal Pyrolysis over Mo and Nimodified HZSM-5[J].Journal of Fuel Chemistry and Technology,2016,44(1):30-36.
[2]XIE Kechang,LI Wenying,ZHAO Wei.Coal Chemical Industry and Its Sustainable Development in China[J].Energy,2010,35(11):4349-4355.
[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 Kechang.Study on Clean,Efficient and Sustainable Development and Utilization Strategy of Coal in China[M].Beijing:Science Press,2014:2-5.
[4]王兴栋,陆江银.催化热解调控热解产物的研究进展[J].山东化工,2012,41(5):29-33.WANG Xingdong,LU Jiangyin.Research Advancement on Catalytic Pyrolysis Control of Pyrolysis Products[J].Shandong Chemical Industry,2012,41(5):29-33.
[5]LI Liuyun,MORISHITA K,MOGI H,et al.Low-temperature Gasification of a Woody Biomass Under a Nickel-loaded Brown Coal Char[J].Fuel Processing Technology,2010,91(8):889-894.
[6]YAN Lunjing,KONG Xiaojun,ZHAO Ruifang,et al.Catalytic Upgrading of Gaseous Tars over Zeolite Catalysts During Coal Pyrolysis[J].Fuel Processing Technology,2015,138:424-429.
[7]杨霈霖.新疆煤(催化)热解特性研究[D].西安:西北大学,2016.YANG Peilin.Study on the(Catalytic)Pyrolysis Characteristics of Xinjiang Coal[D].Xi’an:Northwest University,2016.
[8]孟欣欣,邱泽刚,郭兴梅,等.不同金属含量Ni-W催化剂的煤焦油加氢脱硫脱氮性能研究[J].燃料化学学报,2016,44(5):570-578.MENG Xinxin,QIU Zegang,GUO Xingmei,et al.Hydrodenitrogenation and Hydrodesulfurization of Coal Tar on Ni-WCatalysts with Different Metal Loadings[J].Journal of Fuel Chemistry and Technology,2016,44(5):570-578.
[9]LI Guanlong,YAN Lunjing,ZHAO Ruifang,et al.Improving Aromatic Hydrocarbons Yield from Coal Pyrolysis Volatile Products over HZSM-5and Mo-modified HZSM-5[J].Fuel,2014,130(7):154-159.
[10]SHEN Dekui,ZHAO Jing,XIAO Rui.Catalytic Transformation of Lignin to Aromatic Hydrocarbons over Solid-acid Catalyst:Effect of Lignin Sources and Catalyst Species[J].Energy Conversion and Management,2016,124:61-72.
[11]ZAKARIA Z Y,LINNEKOSKI J,AMIN N A S.Catalyst Screening for Conversion of Glycerol to Light Olefins[J].Chemical Engineering Journal,2012,207/208:803-813.
[12]LIU Tianlong,CAO Jingpei,ZHAO Xiaoyan,et al.In Situ Upgrading of Shengli Lignite Pyrolysis Vapors over Metal-loaded HZSM-5Catalyst[J].Fuel Processing Technology,2017,160:19-26.
[13]VESES A,PURTOLAS B,CALLN M S,et al.Catalytic Upgrading of Biomass Derived Pyrolysis Vapors over Metalloaded ZSM-5Zeolites:Effect of Different Metal Cations on the Bio-oil Final Properties[J].Microporous and Mesoporous Materials,2015,209:189-196.
[14]ZHOU Xiaozhao,LIU Yan,MENG Xiangju,et al.Synthesis and Catalytic Cracking Performance of Fe/Ti-ZSM-5Zeolite from Attapulgite Mineral[J].Chinese Journal of Catalysis,2013,34(8):1504-1512.
[15]刘宗宽,张磊,江健,等.煤焦油加氢精制和加氢裂化催化剂的研究进展[J].化工进展,2012,31(12):2672-2677.LIU Zongkuan,ZHANG Lei,JIANG Jian,et al.Advances in Coal Tar Hydro-refining and Hydro-cracking Catalysts[J].Chemical Industry and Engineering Progress,2012,31(12):2672-2677.
[16]孔鹏飞.改性USY催化纤维素醇解至乙酰丙酸乙酯的试验研究[D].郑州:郑州大学,2016.KONG Pengfei.Research on the Alcoholysis of Cellulose to Ethyl Levulinate Catalyzed by Modified USY in Ethanol Medium[D].Zhengzhou:Zhengzhou University,2016.
[17]王桂云,温健,张晔,等.过渡金属改性USY催化低浓度乙醇脱水制乙烯[J].煤炭转化,2011,34(2):82-85.WANG Guiyun,WEN Jian,ZHANG Ye,et al.Catalytic Dehydration of Hydrous Ethanol to Ethylene on USY Zeolite Modified by Transition Metals[J].Coal Conversion,2011,34(2):82-85.
[18]SALMAN Raza Naqvi,YOSHIMITU Uemura,SUZANA Yusup,et al.The Role of Zeolite Structure and Acidity in Catalytic Deoxygenation of Biomass Pyrolysis Vapors[J].Energy Procedia,2015,75:793-800.
[19]FAN Liangliang,CHEN Paul,ZHOU Nan,et al.In-situ and Ex-situ Catalytic Upgrading of Vapors from Microwave-assisted Pyrolysis of Lignin[J].Bioresource Technology,2018,247:851-858.
[20]KURNIA I,KARNJANAKOM S,BAYU A,et al.In-situ Catalytic Upgrading of Bio-oil Derived from Fast Pyrolysis of Lignin over High Aluminum Zeolites[J].Fuel Processing Technology,2017,167:730-737.
[21]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.
[22]LI Yuping,LI Bosong,ZHANG Xinghua,et al.Continuous Pyrolysis and Catalytic Upgrading of Corncob Hydrolysis Residue in the Combined System of Auger Reactor and Downstream Fixed-bed Reactor[J].Energy Conversion and Management,2016,122:1-9.
[23]MEESUK S,CAO Jingpei,SATO K,et al.The Effects of Temperature on Product Yields and Composition of Bio-oils in Hydropyrolysis of Rice Husk Using Nickel-loaded Brown Coal Char Catalyst[J].Journal of Analytical and Applied Pyrolysis,2012,94(3):238-245.
[24]李刚.基于过渡金属氧化物/USY催化剂的神东煤催化热解研究[D].西安:西北大学,2018.LI Gang.Study on Catalytic Pyrolysis of Shendong Coal Based on Transition Metal Oxide/USY Catalysts[D].Xi’an:Northwest University,2018.
[25]李昱,张英强,刘娜,等.低碳烯烃芳构化催化剂与工艺进展[J].抚顺石油学院学报,2002,22(1):23-28.LI Yu,ZHANG Yingqiang,LIU Na,et al.Development of Process and Catalyst of Low Olefin Aromatization[J].Journal of Fushun Petroleum Institute,2002,22(1):23-28.
[26]孔晓俊.USY分子筛对煤热解气态焦油的催化改质[D].太原:太原理工大学,2016.KONG Xiaojun.Catalytic Upgrading of Coal Gaseous Tar over USY Zeolites[D].Taiyuan:Taiyuan University of Technology,2016.
[27]MA Zhiqiang,TROUSSARD Ekaterina,VAN BOKHOVEN J A.Controlling the Selectivity to Chemicals from Lignin via Catalytic Fast Pyrolysis[J].Applied Catalysis A:General,2012,423/424(18):130-136.
[28]闫伦靖,孔晓俊,白永辉,等.Mo和Ni改性HZSM-5催化剂对煤热解焦油的改质[J].燃料化学学报,2016,44(1):30-36.YAN Lunjing,KONG Xiaojun,BAI Yonghui,et al.Catalytic Upgrading of Gaseous Tar from Coal Pyrolysis over Mo and Nimodified HZSM-5[J].Journal of Fuel Chemistry and Technology,2016,44(1):30-36.
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