磷改性Mo/Al_2O_3-SiO_2催化剂对神府煤催化热解产物的影响
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摘要
在常压固定床反应器及温度为750℃的氢气气氛下开展了神府煤催化热解研究,讨论了磷改性催化剂对热解气组成和焦油产率的影响。结果表明:10%-Mo/3%-P-Al_2O_3-SiO_2催化剂使得煤热解焦油的收率提升了9.6%,热解气热值提高,催化剂对热解气体产物组成影响较小,其中CH_4的相对含量占到50%以上。焦油的GC-MS分析表明,催化热解可以使焦油中各组分的相对含量有不同程度的变化,证明磷改性催化剂能在一定程度上调整加氢热解产物的分布。
Shenfu coal was catalyzed and pyrolyzed in a fixed bed reactor under hydrogen atmosphere at temperature of 750℃.The effects of phosphorus-modified catalyst on the component of pyrolysis gas and the yield of tar were discussed.The results show that under this condition,10%-Mo/3%-P-Al_2O_3-SiO_2 catalyst increases the tar yield of coal pyrolysis by 9.6%,and the calorific value of pyrolysis gas increases to some extent.The catalyst has little influence on the composition and distribution of pyrolysis gas products,in which CH_4 accounts for more than 50%.In addition,GC-MS analysis of tar shows that catalytic pyrolysis can change the relative content of each component in tar to different degree,which proves that phosphorus modified catalyst can adjust the distribution of hydrogenation pyrolysis products to some extent.
Shenfu coal was catalyzed and pyrolyzed in a fixed bed reactor under hydrogen atmosphere at temperature of 750℃.The effects of phosphorus-modified catalyst on the component of pyrolysis gas and the yield of tar were discussed.The results show that under this condition,10%-Mo/3%-P-Al_2O_3-SiO_2 catalyst increases the tar yield of coal pyrolysis by 9.6%,and the calorific value of pyrolysis gas increases to some extent.The catalyst has little influence on the composition and distribution of pyrolysis gas products,in which CH_4 accounts for more than 50%.In addition,GC-MS analysis of tar shows that catalytic pyrolysis can change the relative content of each component in tar to different degree,which proves that phosphorus modified catalyst can adjust the distribution of hydrogenation pyrolysis products to some extent.
引文
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[2]张春田,张渤,田浩,等.我国清洁煤技术的应用现状及存在问题初探[J].煤质技术,2017(增刊1):48-51.ZHANG Chuntian,ZHANG Bo,TIAN Hao,et al.The Application Circumstances and Existing Problems Research of Chinese Clean Coal Technology[J].Coal Quality and Technology,2017(Supplement 1):48-51.
[3]CHEN Fuxin,GONG Pin,ZHANG Huikuan,et al.Biomass Pyrolysis of Helianthus annuus Stems:Qualitative and Quantitative Study Based on Py-GC/MS[J].Bioresources,2016,11(4):8589-8614.
[4]LI Shuang,CHEN Jingsheng,HAO Ting,et al.Pyrolysis of Huangtu Miao Coal over Faujasite Zeolite and Supported Transition Metal Catalysts[J].Journal of Analytical and Applied Pyrolysis,2013,102(7):161-169.
[5]JIN Lijun,ZHOU Xun,HE Xinfu,et al.Integrated Coal Pyrolysis with Methane Aromatization over Mo/HZSM-5for Improving Tar Yield[J].Fuel,2013,114:187-190.
[6]HAN Jiangze,WANG Xindong,YUE Junrong,et al.Catalytic Upgrading of Coal Pyrolysis Tar over Char-based Catalysts[J].Fuel Processing Technology,2014,122:98-106.
[7]LI Wen,WANG Na,LI Baoqing.Product Analysis of Catalytic Multi-stage Hydropyrolysis of Lignite[J].Fuel,2003,82(5):569-573.
[8]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.
[9]张娇玉,祝晓琳,廖丽东,等.磷改性对ZSM-5分子筛催化甲苯甲醇烷基化反应性能的影响[J].石化技术与应用,2018,36(5):286-290.ZHANG Jiaoyu,ZHU Xiaolin,LIAO Lidong,et al.Effect of Phosphorus Modification on ZSM-5Molecular Sieve for Reaction Performance of Toluene Alkylation with Methanol[J].Petrochemical Technology and Application,2018,36(5):286-290.
[10]刘丽芝,宋君辉,金吉海,等.磷改性USY分子筛催化剂上四氢萘选择性开环反应性能[J].工业催化,2018,26(6):34-38.LIU Lizhi,SONG Junhui,JIN Jihai,et al.Phosphorus Modified USY Zeolite Catalyst for Selective Ring-opening of Tetralin[J].Industrial Catalysis,2018,26(6):34-38.
[11]柳娜,赵丹丹,雷艳艳,等.纳米Al2O3负载Ru催化剂用于CO2加氢合成甲酸研究[J].化学工程,2014(12):55-58.LIU Na,ZHAO Dandan,LEI Yanyan,et al.Ru Supported on Nano-alumina for CO2 Hydrogenation to Formic Acid[J].Chemical Engineering,2014(12):55-58.
[12]张轩,牛梦龙,潘柳依,等.F改性NiW/Al2O3-SiO2催化剂煤焦油加氢性能研究[J].石油化工,2018,47(9):936-942.ZHANG Xuan,NIU Menglong,PAN Liuyi,et al.Hydroprocessing of Coal Tar on Fluorine Modification NiW/Al2O3-SiO2Catalysts[J].Petrochemical Technology,2018,47(9):936-942.
[13]任秀彬,辛文辉,周安宁.煤与生物质固定床共热解产物分布及热解动力学研究[J].应用化工,2017,46(8):1644-1649.REN Xiubin,XIN Wenhui,ZHOU Anning.Co-pyrolysis Characteristics and Kinetics of Coal and Sunflower Stalk Blends in Fixed Bed[J].Applied Chemical Industry,2017,46(8):1644-1649.
[14]BERTEAU P,DELMON B.Modified Aluminas:Relationship Between Activity in 1-butanol Dehydration and Acidity Measured by NH3-TPD[J].Catalysis Today,1989,5(2):121-137.
[15]石垒,张增辉,邱泽刚,等.P改性对Mo-Ni/Al2O3煤焦油加氢脱氮性能的影响[J].燃料化学学报,2015,43(1):74-80.SHI Lei,ZHANG Zenghui,QIU Zegang,et al.Effect of Phosphorus Modification on the Catalytic Properties of Mo-Ni/Al2O3in the Hydrodenitrogenation of Coal Tar[J].Journal of Fuel Chemistry and Technology,2015,43(1):74-80.
[16]梁晓彤,谢良才,徐龙,等.改性ZSM-5对神东煤热解行为的影响[J].煤炭转化,2017,40(3):21-27.LIANG Xiaotong,XIE Liangcai,XU Long,et al.Pyrolysis Characteristics of Shendong Coal on Modified ZSM-5Catalyst[J].Coal Conversion,2017,40(3):21-27.
[17]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 Jingsheng,MA Xiaoxun,LI Shuang,et al.TG-FTIR Study on Huangtumiao Coal Pyrolysis on CoMoP/13XCatalyst[J].Coal Conversion,2012,35(1):4-8.
[18]位艳宾,季剑波,徐彦红,等.微波辐射下神木-府谷烟煤有机质的溶出规律及组成结构[J].河南师范大学学报(自然科学版),2016,44(6):91-95.WEI Yanbin,JI Jianbo,XU Yanhong,et al.Dissolved Law and Chemical Composition of Organic Matter in Shenmu-Fugu Coal Under Microwave Irradiation[J].Journal of He’nan Normal University(Natural Science Edition),2016,44(6):91-95.
[19]赵立祥,张智慧,苏晓云,等.制备条件对MoP/HZSM-5催化剂临氢芳构化性能的影响[J].石化技术与应用,2012,30(2):143-148.ZHAO Lixiang,ZHANG Zhihui,SU Xiaoyun,et al.Effect of Preparation Condition of MoP/HZSM-5 Catalyst on Its Hydroaromatization Performance[J].Petrochemical Technology and Application,2012,30(2):143-148.
[20]MICKELSON G.Hydrogenative Desulfurization:US3755150[P].1973-08-28.