Regulation of the rapid pyrolysis products of Shendong coal by MxOy/USY bifunctional catalyst

doi:10.16085/j.issn.1000-6613.2017-1849

Chemical Industry and Engineering Progress ›› 2018, Vol. 37 ›› Issue (08): 3029-3037.DOI: 10.16085/j.issn.1000-6613.2017-1849

Previous Articles Next Articles

Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst

ZHANG Suisui¹, LI Gang¹, MIN Xiaojian², ZHENG Hua'an², FAN Yingjie², ZHANG Nina¹, AN Pu¹, MA Xiaoxun¹

1 International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shaanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Development of Energy and Chemical Industry in Northern Shaanxi, School of Chemical Engineering, Northwest University, Xi'an 710069, Shaanxi, China;
2 Shaanxi Coal Chemical Industry Technology Research Institute Co., Ltd., Xi'an 710070, Shaanxi, China

Received:2017-09-04 Revised:2018-01-30 Online:2018-08-05 Published:2018-08-05

M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控

张穗穗¹, 李刚¹, 闵小建², 郑化安², 樊英杰², 张妮娜¹, 安璞¹, 马晓迅¹

1 西北大学化工学院, 国家碳氢资源清洁利用国际科技合作基地, 陕北能源先进化工利用技术教育部工程研究中心, 陕西省洁净煤转化工程技术中心, 陕北能源化工产业发展协同创新中心, 陕西西安 710069;
2 陕西煤业化工技术研究院有限责任公司, 陕西西安 710070

通讯作者: 马晓迅,教授,研究方向为化石燃料(煤、石油、天然气)和生物质资源的高效清洁转化利用、粉-粒气固流化床/喷动床的基础和开发应用性研究、过程优化与模拟。
作者简介:张穗穗(1992-),女,博士研究生,研究方向为煤热解。E-mail:ss_nwu@163.com。
基金资助:
国家自然科学基金重点项目（21536009）、陕西省科技计划（2017ZDCXL-GY-10-03）及西北大学研究生创新人才培训项目（YZZ15033）。

Abstract

Abstract: Four transition metal oxides of NiO, Fe₂O₃, Co₃O₄ and MoO₃, were respectively supported on USY molecular sieves by equal volume impregnation to prepare M_xO_y/USY bifunctional catalysts. The catalysts, all with 9% transition metal oxides, were characterized by ICP, XRD, BET, TEM, NH₃-TPD, and TG. The rapid pyrolysis experiments of shendong coal were conducted on a self-built powder-particle fluidized bed. The results showed:① M_xO_y/USY bifunctional catalysts increased the yield of the gas product and the amount of carbon deposition, and decreased the yield of the liquid product, but had no effect on the yield of the char. ② M_xO_y/USY increased the production of CH₄ and CO, but decreased the yield of H₂ and C₂. The bifunctional catalysts significantly reduced the content of naphthalene compound and biphenyl (poly) benzene in the tar, while increased the content of aliphatic hydrocarbons,monocyclic aromatic hydrocarbons,phenolic compounds and oxygen compounds. ③ The four M_xO_y/USY bifunctional catalysts showed differences in the regulation of the product and its composition. In addition,Fe₂O₃/USY and Co₃O₄/USY had similar regulatory effect on products and their composition. But Fe₂O₃/USY had a higher gas selectivity,and the total gas yield for Fe₂O₃/USY was as high as 23%. NiO/USY increased both the C₃ yield by 79% and the content of aliphatic hydrocarbons,phenols and oxygen compounds in the tar by 1555%,739%,412%, respectively,but decreased the CO₂ yield by 91% and the content of naphthalenes by 46%. MoO₃/USY increased the content of polycyclic aromatic hydrocarbons by 8%.

Key words: fluidized bed, molecular sieves, transition metals oxide, fast pyrolysis, catalysis, product regulation

摘要： 以USY分子筛为载体，采用等体积浸渍法分别制备了NiO、Fe₂O₃、Co₃O₄、MoO₃负载量均为9%的M_xO_y/USY双功能催化剂，并借助ICP、XRD、BET、TEM、NH₃-TPD、TG等分析手段对催化剂进行表征。使用自建的粉-粒流化床对神东煤进行快速催化热解实验，结果表明：①M_xO_y/USY使气体产物收率提高，液体产物收率降低，催化剂的积炭量增加，对半焦的产率基本没有影响；②M_xO_y/USY使CH₄、CO的收率均不同程度地提高，但H₂、C₂的收率皆有所降低；焦油中脂肪烃、单环芳烃、酚类化合物、含氧化合物的含量大幅增加，萘类化合物、联（多）苯的含量显著减少；③M_xO_y/USY的调控作用存在差异性。其中，Fe₂O₃/USY、Co₃O₄/USY的产物调控作用相似，但Fe₂O₃/USY的气体选择性更高，气体总收率提高23%；NiO/USY使C₃收率提高79%，CO₂收率降低91%，使焦油中脂肪烃、酚类、含氧化合物的含量分别增加1555%、739%、412%，萘类化合物的含量减少46%；MoO₃/USY使稠环芳烃的含量增加8%。

关键词: 流化床, 分子筛, 过渡金属氧化物, 快速热解, 催化作用, 产物调控

CLC Number:

TQ53

ZHANG Suisui, LI Gang, MIN Xiaojian, ZHENG Hua'an, FAN Yingjie, ZHANG Nina, AN Pu, MA Xiaoxun. Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst[J]. Chemical Industry and Engineering Progress, 2018, 37(08): 3029-3037.

张穗穗, 李刚, 闵小建, 郑化安, 樊英杰, 张妮娜, 安璞, 马晓迅. M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控[J]. 化工进展, 2018, 37(08): 3029-3037.

References

[1] 贺永德. 煤炭热解(干馏)及煤焦油加工技术经济分析[J]. 中国经贸导刊, 2010(18):24-25. HE Y D. Technical analysis of coal pyrolysis (dry distillation) and coal tar processing technology[J]. China Economic Trade Herald, 2010(18):24-25.
[2] 曲思建, 王琳, 张飏, 等.我国低阶煤转化主要技术进展及工程实践[C]//中国煤炭学会成立五十周年高层学术论坛.北京:中国煤炭学会, 2012:152-161. QU S J, WANG L, ZHANG Y, et al.Main technical progress and engineering practice of low rank coal conversion in China[C]//China Coal Institute Set up 50th Anniversary High-Level Academic Forum.Beijing:China Coal Society, 2012:152-161.
[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] 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 Q, 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.
[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):1107-1113. ZOU X W, YAO J Z, YANG X M, et al.Catalytic action of Co/ZSM-5 zeolite catalysts in coal pyrolysis in a spouted entrained flow reactor[J].The Chinese Journal of Process Engineering, 2007, 7(6):1107-1113.
[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] 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.
[8] 邓靖, 李文英, 李晓红, 等.橄榄石基固体热载体影响褐煤热解产物分布的分析[J].燃料化学学报, 2013, 41(8):937-942. DENG J, LI W Y, LI X H, et al.Analysis of distribution of pyrolysis products of lignite influenced by solid heat carrier based on olivine[J]. Journal of Fuel Chemistry and Technology, 2013, 41(8):937-942.
[9] SONOYAMA N, NOBUTA K, KIMURA T, et al.Production of chemicals by cracking pyrolytic tar from Loy Yang coal over iron oxide catalysts in a steam atomophere[J].Fuel Processing Technology, 2011, 92(4):771-775.
[10] 王美君, 杨会民, 何秀风, 等.铁基矿物质对西部煤热解特性的影响[J].中国矿业大学学报, 2010, 39(3):426-430. WANG M J, YANG H M, HE X F, et al.Effects of Fe based minerals on pyrolysis properties of western coals[J].Journal of China University of Mining and Technology, 2010, 39(3):426-430.
[11] 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.Progress in selective catalytic reduction of nitrogen oxides over transition metal/zeolite catalysts[J]. Chemical Industry and Engineering Progress, 2012, 31(1):98-106.
[12] 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.
[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] FERRAZ S G A, ZOTIN F M Z, ARAUJO L R R, 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.
[15] HERNANDEZ-HUESCA R, MERIDA-ROBLES J, MAIRELES-TORRES P, et al.Hydrogenation and ring-opening of tetralin on Ni and MiMo supported on alumina-pillared α-zirconium phosphate catalysts. A thiotolerance study[J].Journal of Catalysis, 2001, 203(1):122-132.
[16] 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), 2011, 27(5):668-673. YANG P, XIN J, LI M F, et al.Effects of supported Mo and W oxides on the structure and acidity of Y zeolite[J]. Journal of Petroleum(Petroleum Processing), 2011, 27(5):668-673.
[17] 张增辉, 石磊, 邱泽刚, 等. NiW/USY分子筛催化剂的煤焦油加氢裂化性能[J].石油炼制与化工, 2015, 46(5):76-81. ZHANG Z H, SHI L, QIU Z G, et al.Hydrocracking performance of NiW/USY molecular sieve catalyst for coal tar[J]. Petroleum Processing and Petrochemicals, 2015, 46(5):76-81.
[18] 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.
[19] 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.
[20] KONG X J, BAI Y H, YAN L J.Catalytic upgrading of coal gaseous tar over Y-type zeolites[J].Fuel, 2016, 180:205-210.
[21] CARLSON T R, JAE J, HUBER G W.Mechanistic insights from isotopic studies of glucose conversion to aromatics over ZSM-5[J]. ChemCatChem, 2010, 1(1):107-110.
[22] 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, 2010, 4(1):145-161.
[23] 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, 2013, 49(1):123-131.
[24] CYPRES R. Aromatic hydrocarbons formation during coal pyrolysis[J]. Fuel Processing Technology, 1987, 15:1-15.
[25] WILLIAMS P T, TAYLOR D T.Aromatization of tyre pyrolysis oil to yield polycyclic aromatic hydrocarbons[J]. Fuel, 1993, 72(11):1469-1474.
[26] 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.

Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst

M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHENG Qian, GUAN Xiushuai, JIN Shanbiao, ZHANG Changming, ZHANG Xiaochao. Photothermal catalysis synthesis of DMC from CO₂ and methanol over Ce_0.25Zr_0.75O₂ solid solution [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 319-327.
[2]	WANG Zhengkun, LI Sifang. Green synthesis of gemini surfactant decyne diol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 400-410.
[3]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[4]	GENG Yuanze, ZHOU Junhu, ZHANG Tianyou, ZHU Xiaoyu, YANG Weijuan. Homogeneous/heterogeneous coupled combustion of heptane in a partially packed bed burner [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4514-4521.
[5]	GAO Yanjing. Analysis of international research trend of single-atom catalysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4667-4676.
[6]	LI Dongze, ZHANG Xiang, TIAN Jian, HU Pan, YAO Jie, ZHU Lin, BU Changsheng, WANG Xinye. Research progress of NO _x reduction by carbonaceous substances for denitration in cement kiln [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4882-4893.
[7]	WANG Chen, BAI Haoliang, KANG Xue. Performance study of high power UV-LED heat dissipation and nano-TiO₂ photocatalytic acid red 26 coupling system [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4905-4916.
[8]	HUANG Yufei, LI Ziyi, HUANG Yangqiang, JIN Bo, LUO Xiao, LIANG Zhiwu. Research progress on catalysts for photocatalytic CO₂ and CH₄ reforming [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4247-4263.
[9]	WANG Xiaohan, ZHOU Yasong, YU Zhiqing, WEI Qiang, SUN Jinxiao, JIANG Peng. Synthesis and hydrocracking performance of Y molecular sieves with different crystal sizes [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4283-4295.
[10]	WU Haibo, WANG Xilun, FANG Yanxiong, JI Hongbing. Progress of the development and application of 3D printing catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3956-3964.
[11]	XU Wei, LI Kaijun, SONG Linye, ZHANG Xinghui, YAO Shunhua. Research progress of photocatalysis and co-electrochemical degradation of VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3520-3531.
[12]	WANG Darui, SUN Hongmin, XUE Mingwei, WANG Yiyan, LIU Wei, YANG Weimin. Efficient synthesis of fully crystalline ZSM-5 zeolite catalyst by microwave method and its catalytic performance [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3582-3588.
[13]	GUO Lixing, PANG Weiying, MA Keyao, YANG Jiahan, SUN Zehui, ZHANG Pan, FU Dong, ZHAO Kun. Hierarchically multilayered TiO₂ with spatial pore-structure for efficient photocatalytic CO₂ reduction [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3643-3651.
[14]	LI Yanling, ZHUO Zhen, CHI Liang, CHEN Xi, SUN Tanglei, LIU Peng, LEI Tingzhou. Research progress on preparation and application of nitrogen-doped biochar [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3720-3735.
[15]	DONG Xiaoshan, WANG Jian, LIN Fawei, YAN Beibei, CHEN Guanyi. Exsolved metal nanoparticles on perovskite oxides: exsolution, driving force and control strategy [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3049-3065.

Regulation of the rapid pyrolysis products of Shendong coal by MxOy/USY bifunctional catalyst

MxOy/USY双功能催化剂对神东煤的快速热解产物的调控

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst

M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控