Analysis of catalytic cracking of sludge gasification tar over palygorskite nickel-based catalyst

doi:10.16085/j.issn.1000-6613.2017-2416

Abstract

Abstract: Various nickel-based catalysts were prepared by equal volume impregnation method with palygorskite as the carrier. The catalytic performance of the nickel-based catalysts to crack the sludge gasification tar model compound toluene was analyzed in a fixed-bed reactor. The effects of reaction temperature, steam/carbon molar ratio(S/C), residence time, additives and Ni content on the toluene conversion were investigated. The experimental results showed that with the increase of reaction temperature, steam/carbon molar ratio(S/C), residence time and adding additives, the toluene conversion clearly increased. However, the catalytic reactivity of catalysts and toluene conversion decreased when excess of additives were added. Among the four additives of Fe, Ce, Cu and Ca, the increase of Fe content led to an improvement of toluene conversion. When the amounts of Ce, Cu and Ca were over 3%, the conversion of toluene decreased obviously, even lower than that without additives.

Key words: catalyst support, fix-bed, additives, catalysis, sludge gasification

摘要： 以凹凸棒石为催化剂载体，采用等体积浸渍法制备了多种镍基催化剂，并对催化剂进行了XRD、SEM、BET、EDS等特性分析。在固定床反应器中对催化剂催化裂解污泥气化焦油模型化合物的特性进行了实验研究。考察了反应温度、水碳比（S/C）、气相停留时间、助剂等因素对模型化合物催化裂解特性的影响。结果表明，提高反应温度、增加S/C、延长停留时间、添加助剂均能提高催化剂的催化活性，模型化合物转化率明显增加。但是助剂含量过高反而导致催化剂催化裂解的能力减弱，模型化合物转化率下降。对比Fe、Ce、Cu、Ca 4种助剂发现，在实验范围内，增加Fe的含量，模型化合物转化率上升。当Ce、Cu、Ca助剂质量分数达到3%及以上时，转化率下降明显，甚至低于未添加助剂时的转化率。

关键词: 催化剂载体, 固定床, 助剂, 催化, 污泥气化

CLC Number:

O643
TK09

WANG Yantao, LIANG Cai, ZHOU Qun, YANG Xujun, SONG Lian, ZHU Ge, CHEN Xiaoping, ZHAO Changsui. Analysis of catalytic cracking of sludge gasification tar over palygorskite nickel-based catalyst[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3895-3902.

王延涛, 梁财, 周群, 杨叙军, 宋联, 朱葛, 陈晓平, 赵长遂. 凹凸棒石镍基催化剂对污泥气化焦油催化裂解的特性分析[J]. 化工进展, 2018, 37(10): 3895-3902.

References

[1] 张辉, 胡勤海, 吴祖成, 等. 城市污泥能源化利用研究进展[J]. 化工进展, 2013, 32(5):1145-1151. ZHANG Hui, HU Qinhai, WU Zucheng, et al. An overview on utilization of municipal sludge as energy resources[J]. Chemical Industry and Engineering Progress, 2013, 32(5):1145-1151.
[2] 杨修春, 韦亚南, 李伟捷.焦油裂解用催化剂的研究进展[J].化工进展, 2007, 26(3):326-330. YANG Xiuchun, WEI Yanan, LI Weijie. Research progress of catalysts for tar cracking[J]. Chemical Industry and Engineering Progress, 2007, 26(3):326-330.
[3] 宋磊, 陈天虎, 陈冬, 等.凹凸棒石催化重整生物质焦油中的二甲苯[J]. 硅酸盐学报, 2011, 39(7):1135-1139. SONG Lei, CHEN Tianhu, CHEN Dong, et al. Catalytic steam reforming of xylene in biomass gasification by palygorskite[J]. Journal of the Chinese Ceramic Society, 2011, 39(7):1135-1139.
[4] 何立模, 胡松, 汪一, 等.改性镍基催化剂催化甲苯重整与积碳特性研究[J]. 工程热物理学报, 2016, 37(5):1093-1099. HE Limo, HU Song, WANG Yi, et al. Catalytic performance of coke characterization over modified Ni-based catalysts for steam reforming of toluene[J]. Journal of Engineering Thermophysics, 2016, 37(5):1093-1099.
[5] KIMURA T, MIYAZAWA T, NISHIKAWA J, et al. Development of Ni catalysts for tar removal by steam gasification of biomass[J]. Applied Catalysis B:Environmental, 2006, 68(3):160-170.
[6] 张艳敏, 邹达, 赵渊, 等.双金属催化剂对煤焦油模型化合物催化裂解行为的影响[J]. 化工学报, 2017, 68(10):3805-3815. ZHANG Yanmin, ZOU Da, ZHAO Yuan, et al. Effect of bimetallic catalysts on cracking behavior of coal tar model compounds[J]. CIESC Journal, 2017, 68(10):3805-3815.
[7] BERMÚDEZ J M, FIDALGO B, ARENILLAS A, et al. CO₂ reforming of coke oven gas over a Ni/γ-Al₂O₃ catalyst to produce syngas for methanol synthesis[J]. Fuel, 2012, 94(1):197-203.
[8] ZHANG Jianguo, WANG Hui, DALAI A K. Development of stable bimetallic catalysts for carbon dioxide reforming of methane[J]. Journal of Catalysis, 2007, 249(2):300-310.
[9] ZHANG Ruiqin, WANG Huajian, HOU Xiaoxue. Catalytic reforming of toluene as tar model compound:effect of Ce and Ce-Mg promoter using Ni/olivine catalyst[J]. Chemosphere, 2014, 97(1):40-46.
[10] 胡万勇, 王训, 杨娉, 等. Ni/钙铝石催化剂对焦油模拟物甲苯的催化研究[J].环境工程, 2017, 37(7):116-125. HU Wanyong, WANG Xun, YANG Ping, et al. Catalytic cracking of toluene as biomass tar mimics based on Ni/mayenite[J]. Environmental Engineering, 2017, 37(7):116-125.
[11] 陈天虎, 施培超, 张先龙, 等. Ni/凹凸棒石催化裂解生物质焦油组分甲苯[J]. 太阳能学报, 2011, 32(10):1506-1510. CHEN Tianhu, SHI Peichao, ZHANG Xianlong, et al. Catalytic cracking of biomass tar on Ni/palygorskite[J]. Acta Energiae Solaris Sinica, 2011, 32(10):1506-1510.
[12] SHI Yingying, YANG Zewei, WANG Bing, et al. Adsorption and photocatalytic degradation of tetracycline hydrochloride using a palygorskite-supported Cu₂O-TiO₂ composite[J]. Applied Clay Science, 2016, 119(2):311-320.
[13] JESS A. Mechanisms and kinetics of thermal reactions of aromatics hydrocarbons from pyrolysis of solid fuel[J]. Fuel, 1996, 75(12):1441-1448.
[14] ASHOK J, KAWI S. Steam reforming of toluene as a biomass tar model compound over CeO₂ promoted Ni/CaO-Al₂O₃ catalytic systems[J]. International Journal of Hydrogen Energy, 2013, 38(32):13938-13949.
[15] LIU Haibo, CHEN Tianhu, CHANG Dongyin, et al. Catalytic cracking of tars derived from rice hull gasification over goethite and palygorskite[J]. Applied Clay Science, 2012, 70(7):51-57.
[16] 侯晓雪. MgO和CeO₂对Ni/olivine催化剂蒸气转化甲苯的催化性能的影响研究[D]. 郑州:郑州大学, 2015. HOU Xiaoxue. Study on the effect of MgO and CeO₂ on Ni/olivine catalysts for steam reforming of toluene[D]. Zhengzhou:Zhengzhou University, 2015.
[17] CHOUDHARY V R, UPHADE B S, MAMMAN A S. Oxidative conversion of methane to syngas over nickel supported on commercial low surface area porous catalyst carriers precoated with alkaline and rare earth oxides[J]. Journal of Catalysis, 1997, 172(2):281-293.
[18] 刘海波, 陈天虎, 张先龙, 等. 助剂对镍基催化剂催化裂解生物质气化焦油性能的影响[J]. 催化学报, 2010, 31(4):409-414. LIU Haibo, CHEN Tianhu, ZHANG Xianlong, et al. Effect of additives on catalytic cracking of biomass gasification tar over nickel-based catalyst[J]. Chinese Journal of Catalysis, 2010, 31(4):409-414.
[19] 彭书传, 宋磊, 张先龙, 等. 凹凸棒石粘土催化裂解生物质焦油模型化合物的实验研究[J]. 矿物学报, 2010, 30(3):338-342. PENG Shuchuan, SONG Lei, ZHANG Xianlong, et al. A study on catalytic cracking experiment of the model compound of biomass tar with palygorskite[J]. Acta Mineralogica Sinica, 2010, 30(3):338-342.
[20] 周劲松, 王铁柱, 骆仲泱, 等. 生物质焦油催化裂解研究[J]. 燃料化学学报, 2003, 31(2):144-148. ZHOU Jinsong, WANG Tiezhu, LUO Zhongyang, et al. Catalytic cracking of biomass tar[J]. Journal of Fuel Chemistry and Technology, 2003, 31(2):144-148.
[21] LIU Wenge, GUO Deyong, XU Xin. Research progress of palladium catalysts for methane combustion[J]. China Petroleum Processing and Petrochemical Technology, 2012, 14(3):1-9.
[22] ZOU Xuehua, CHEN Tianhu, LIU Haibo, et al. An insight into the effect of calcination conditions on catalytic cracking of toluene over 3Fe₈Ni/palygorskite:catalysts characterization and performance[J]. Fuel, 2017, 190:47-57.
[23] CHEN L C, LIN S D. The ethanol steam reforming over Cu-Ni/SiO₂ catalysts:effect of Cu/Ni ratio[J]. Applied Catalysis B:Environmental, 2011, 106(3):639-649.