不同性质褐煤催化裂解热解产物提质及机理分析
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摘要
采用双层固定床反应器对比研究了原煤单独热解、催化热解,并对热解产物的分布、轻质焦油产率及质量分数、半焦中残留焦油组分的组成进行了考察和表征。结果表明,当热解终温达到500℃时,单独脱灰煤热解焦油产率略大于原煤.催化提质过程中,焦油产率降低,轻质焦油质量分数及气体产物产率增大.下置床层原煤和脱灰煤添加比例分别为40%、半焦添加比例为30%,此时焦油催化裂解轻质化效果达到最佳。焦油产率:脱灰煤催化>原煤催化>半焦催化,而轻质焦油产率和质量分数:原煤催化>半焦催化>脱灰煤催化.催化脱灰煤床层单环、双环以及三环的芳香烃类化合物高于其他两床层,而四环芳香类化合物产率略低于催化原煤和催化半焦床层.
The individual pyrolysis of raw coal and demineralized coal and the catalytic pyrolysis of raw coal in a dual-stage fixed-bed reactor over raw coal, demineralized coal and char were investigated.The distributions of pyrolysis products, the yield of tar, light tar and its mass fraction were also measured, and the components of residual tar in the catalytic bed was characterized. The results show that when the pyrolysis temperature reaches 500℃, the yield of tar produced by individual pyrolysis of demineralized coal was slightly higher than that of raw coal. In the process of catalytic upgrading,tar yield was decreased, and the light tar mass fraction and gas product yield were increased. The effect of tar upgrading by catalytic cracking is the best when the addition proportion of raw coal and demineralized coal were 40%, and the addition proportion of char is 30%. The tar yield of catalytic pyrolysis increased in the order are as follows: demineralized coal catalytic bed > raw coal catalytic bed > char catalytic bed. While the yield and mass fraction of light tar increased in the order are as follows: raw coal catalytic bed > char catalytic bed > demineralized coal catalytic bed. The content of single aromatic ring, two aromatic rings and three aromatic compounds in the demineralized coal catalytic bed was higher than that of the other two beds, and tetracyclic aromatic compounds yield slightly lower than that of raw coal catalytic bed and char catalytic bed.
The individual pyrolysis of raw coal and demineralized coal and the catalytic pyrolysis of raw coal in a dual-stage fixed-bed reactor over raw coal, demineralized coal and char were investigated.The distributions of pyrolysis products, the yield of tar, light tar and its mass fraction were also measured, and the components of residual tar in the catalytic bed was characterized. The results show that when the pyrolysis temperature reaches 500℃, the yield of tar produced by individual pyrolysis of demineralized coal was slightly higher than that of raw coal. In the process of catalytic upgrading,tar yield was decreased, and the light tar mass fraction and gas product yield were increased. The effect of tar upgrading by catalytic cracking is the best when the addition proportion of raw coal and demineralized coal were 40%, and the addition proportion of char is 30%. The tar yield of catalytic pyrolysis increased in the order are as follows: demineralized coal catalytic bed > raw coal catalytic bed > char catalytic bed. While the yield and mass fraction of light tar increased in the order are as follows: raw coal catalytic bed > char catalytic bed > demineralized coal catalytic bed. The content of single aromatic ring, two aromatic rings and three aromatic compounds in the demineralized coal catalytic bed was higher than that of the other two beds, and tetracyclic aromatic compounds yield slightly lower than that of raw coal catalytic bed and char catalytic bed.
引文
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[12] LI Liuyun, MORISHITA kayoko, MOGI Haruto, et al.Low-temperature Gasification of a Woody Biomass Under a Nickel-loaded Brown Coal Char[J]. Fuel Processing Technology, 2010, 91:889-894
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[23] ZHU Tingyu, ZHANG Shouyu, HUANG Jiejie, et al. Effect of Calcium Oxide on Pyrolysis of Coal in a Fluidized Bed[J]. Fuel Processing Technology, 2000, 64(1):271-284
[24] SONOYAMA N,SONOYAMA N,KIMURA T,et al. Production of Chemicals by Cracking Pyrolytic tar From Loy Yang Coal over Iron Oxide Catalysts in a Steam Atmosphere[J]. Fuel Processing Technology, 2011, 92(4):771-775
[25]赵洪宇,任善普,贾晋炜,等.钙、镍离子3种不同负载方式对褐煤热解-气化特性影响[J].煤炭学报,2015, 40(7):1660-1669ZHAO Hongyu, REN Shanpu, JIA Jinwei, et al. Effects of Calcium and Nickel Ions by Three Different Load Methods on Pyrolysis and Gasification Characteristics of Lignite[J]. Journal of China Coal Society, 2015, 40(7):1660-1669
[26]赵洪宇.难选铁矿石促进富油煤热解及铁矿物回收技术研究[D].北京:中国矿业大学(北京),2016ZHAO Hong-yu. Study on the Refractory Iron ore Promotes Tar-rich Coal Pyrolysis and on the Recovery Technology of Iron Minerals[D]. Beijing:China University of Mining and Technology(Beijing), 2016
[27] MA K O, SONOYAMA N, OHTSUBO E, et al. Examination of Catalytic Roles of Inherent Metallic Species in Steam Reforming of Nascent Volatiles from the RapidPyrolysis of a Brown Coal[J]. Fuel Processing Technology,2007, 88:179-185
[28] ROETS L, STRYDOM C A, BUNT John R, et al. The Effect of Acid Washing on the Pyrolysis Products Derived from a Vitrinite-rich Bituminous Coal[J]. Journal of Analytical and Applied Pyrolysis, 2015, 116:142-151
[29] Han JZ, Wang X, Yue J, et al. Catalytic Upgrading of Coal Pyrolysis Tar Over Char-based Catalysts[J]. Fuel Processing Technology, 2014, 122(1):98-106
[30] SHI Lei, LIU Qingya, LIU Zhenyu, et al. Oils and Phenols-and-Water-Free Tars Produced in Pyrolysis of 23Chinese Coals in Consecutive Temperature Ranges[J].Energy&Fuels, 2013, 27(10):5816-5822
[31] LI Chunzhu,Sathe C, Kershaw JR, et al. Fates and Roles of Alkali and Alkaline Earth Metals During the Pyrolysis of a Victorian Brown Coal[J]. Fuel, 2000, 79:427-438
[2] ZHAO Hongyu, LI Yuhuan, SONG Qiang, et al. Effects of Iron Ores on the Pyrolysis Characteristics of a Low-Rank Bituminous Coal[J]. Energy&Fuels, 2016, 30:3831-3839
[3]赵洪宇,李玉环,舒元锋,等.CaO对褐煤和无烟煤热解产物分布及煤焦结构的影响[J].煤炭科学技术,2016, 44(3):177-183ZHAO Hongyu, LI Yuhuan, SHU Yuanfeng, et al. Effect of Calcium Oxide on Pyrolysis Products Distribution and Char Structure of Lignite and Anthracite[J]. Coal Science and Technology, 2016, 44(3):177-183
[4]赵洪宇,任善普,贾晋炜,等.褐煤经四氢化萘处理后的结构及热解-气化特性分析[J].化工学报,2015, 66(10):4193-4201ZHAO Hongyu, REN Shanpu, JIA Jinwei, et al. Analysis of Structure and Pyrolysis and Gasification Characteristics of Lignite after Tetrahydronaphthalene Treatment[J].CIESC Journal, 2015, 66(10):4193-4201
[5] WANG Nan, YU Jianglong, TAHMASEBI Arash, et al.Experimental Study on Microwave Pyrolysis of an Indonesian Low-rank Coal[J]. Energy&Fuels, 2014, 28(1):254-263
[6] LI Xianchun, RATHNAM Renu K, YU Jianglong, et al.Pyrolysis and Combustion Characteristics of an Indonesian Low-Rank Coal under O_2/N2 and O_2/CO_2 Conditions[J]. Energy&Fuels, 2010, 24(1):160-164
[7] LIANG Peng, WANG Zhifeng, BI Jicheng. Process Characteristics Investigation of Simulated Circulating Fluidized Bed Combustion Combined with Coal Pyrolysis[J].Fuel Processing Technology, 2007, 88(1):23-28
[8] ZENG Xi, WANG Yin, YU Jian, et al. Coal Pyrolysis in a Fluidized Bed for Adapting to a Two-stage Gasification Process[J]. Energy&Fuels, 2011, 25(3):1092-1098
[9] ZENG Xi, WANG Yin, YU Jian, et al. Gas Upgrading in a Downdraft Fixed-Bed Reactor Downstream of a Fluidized-Bed Coal Pyrolyzer[J]. Energy&Fuels, 2011,25(11):5242-5249
[10] ZHAO Hongyu, SUN Tichang, SUN Chunbao, et al.Strengthening the Results of Destroying the Caking Property of CBC in Weak Oxygen and Upgrading Pyrolysis Products[J]. Fuel, 2017, 205:90-99
[11] ZHAO Hongyu, SUN Tichang, SUN Chunbao, et al.Effects of Coal Pretreatment on the Products of Copyrolysis of Caking Bituminous Coal and Corn Stalks Mixed in Equal Proportion[J]. Applied Thermal Engineering, 2017, 125:470-479
[12] LI Liuyun, MORISHITA kayoko, MOGI Haruto, et al.Low-temperature Gasification of a Woody Biomass Under a Nickel-loaded Brown Coal Char[J]. Fuel Processing Technology, 2010, 91:889-894
[13] AMIN Nadeem-muhammad, LI Yi, RAZZAQ Rauf, et al.Pyrolysis of Low Rank Coal by Nickel Based Zeolite Catalysts in the Two-staged Bed Reactor[J]. Journal of Analytical&Applied Pyrolysis, 2016, 118(3):54-62
[14] LI Shuaishuai, MA Xiaoqian. Catalytic Characteristics of the Pyrolysis of Lignite over Oil Shale Chars[J]. Applied Thermal Engineering, 2016, 106:865-874
[15]杨景标,蔡宁生,张彦文.金属催化剂对褐煤热解气体产物析出影响的实验研究[J].工程热物理学报,2009, 30(1):161-164YANG Jingbiao, CAI Ningsheng, ZHANG Yanwen. Experimental Study for the Effect of Catalysts on the Release of Gaseous Products During Pyrolysis of Lignite[J]. Journal of engineering thermophysics, 2009, 30(1):161-164
[16] OZTASNA, YURUM Y. Effect of Catalysts on the Pyrolysis of Turkish Zonguldak Bituminous Coal[J]. Energy&Fuels, 2000, 14:820-827
[17] ZOU Xianwu, YAO Jianzhong, YANG Xuemin, et al.Catalytic Effects of Metal Chlorides on the Pyrolysis of Lignite[J]. Energy&Fuels, 2007, 21(2):619-624
[18] MIN Zhenhua, YIMSIRI Piyachat, ASADULLAH Mohammad, et al. Catalytic Reforming of Tar During Gasification. Part II. Char as a Catalyst or as a Catalyst Support for Tar Reforming[J]. Fuel, 2011, 90(7):2545-2552
[19]王兴栋,韩江则,陆江银,等.半焦基催化剂裂解煤热解产物提高油气品质[J].化工学报,2012, 63(12):3897-3905WANG Xingdong, HAN Jiangze, LU Jiangyin, et al. Catalytic Cracking of Coal Pyrolysis Product for Oil and Gas Upgrading over Char-based Catalysts[J]. Journal of Chemical Industry and Engineering, 2012, 63(12):3897-3905
[20]刘殊远,汪印,武荣成,等.热态半焦和冷态半焦催化裂解煤焦油研究[J].燃料化学学报,2013, 41(9):1041-1049LIU Shuyuan, WANG Yin, WU Rongcheng, et al. Research on Coal Tar Catalytic Cracking Over Hot In-situ chars[J]. Journal of Fuel Chemistry and Technology, 2013,41(9):1041-1049
[21]王芳,曾玺,孙延林,等.两段流化床中半焦催化脱除焦油特性[J].化工学报,2017(10):3762-3769WANG Fang, Zeng Xi, SUN Yanlin, et al. Characteristics of Char Catalytic Reforming of Tar in Two-stage Fluidized Bed[J]. Journal of Fuel Chemistry and Technology,2017(10):3762-3769
[22] CHAREONPANICH M,TAKEDA T,YAMASHITA H,et al. Catalytic Hydrocracking Reaction of Nascent Coal Volatile Matter Under High Pressure[J]. Fuel, 1994, 73(5):666-670
[23] ZHU Tingyu, ZHANG Shouyu, HUANG Jiejie, et al. Effect of Calcium Oxide on Pyrolysis of Coal in a Fluidized Bed[J]. Fuel Processing Technology, 2000, 64(1):271-284
[24] SONOYAMA N,SONOYAMA N,KIMURA T,et al. Production of Chemicals by Cracking Pyrolytic tar From Loy Yang Coal over Iron Oxide Catalysts in a Steam Atmosphere[J]. Fuel Processing Technology, 2011, 92(4):771-775
[25]赵洪宇,任善普,贾晋炜,等.钙、镍离子3种不同负载方式对褐煤热解-气化特性影响[J].煤炭学报,2015, 40(7):1660-1669ZHAO Hongyu, REN Shanpu, JIA Jinwei, et al. Effects of Calcium and Nickel Ions by Three Different Load Methods on Pyrolysis and Gasification Characteristics of Lignite[J]. Journal of China Coal Society, 2015, 40(7):1660-1669
[26]赵洪宇.难选铁矿石促进富油煤热解及铁矿物回收技术研究[D].北京:中国矿业大学(北京),2016ZHAO Hong-yu. Study on the Refractory Iron ore Promotes Tar-rich Coal Pyrolysis and on the Recovery Technology of Iron Minerals[D]. Beijing:China University of Mining and Technology(Beijing), 2016
[27] MA K O, SONOYAMA N, OHTSUBO E, et al. Examination of Catalytic Roles of Inherent Metallic Species in Steam Reforming of Nascent Volatiles from the RapidPyrolysis of a Brown Coal[J]. Fuel Processing Technology,2007, 88:179-185
[28] ROETS L, STRYDOM C A, BUNT John R, et al. The Effect of Acid Washing on the Pyrolysis Products Derived from a Vitrinite-rich Bituminous Coal[J]. Journal of Analytical and Applied Pyrolysis, 2015, 116:142-151
[29] Han JZ, Wang X, Yue J, et al. Catalytic Upgrading of Coal Pyrolysis Tar Over Char-based Catalysts[J]. Fuel Processing Technology, 2014, 122(1):98-106
[30] SHI Lei, LIU Qingya, LIU Zhenyu, et al. Oils and Phenols-and-Water-Free Tars Produced in Pyrolysis of 23Chinese Coals in Consecutive Temperature Ranges[J].Energy&Fuels, 2013, 27(10):5816-5822
[31] LI Chunzhu,Sathe C, Kershaw JR, et al. Fates and Roles of Alkali and Alkaline Earth Metals During the Pyrolysis of a Victorian Brown Coal[J]. Fuel, 2000, 79:427-438