不同方法制备氧化锌高温煤气脱硫剂的原位再生动力学

doi:10.16085/j.issn.1000-6613.2017-0118

化工进展 ›› 2017, Vol. 36 ›› Issue (08): 2994-3001.DOI: 10.16085/j.issn.1000-6613.2017-0118

不同方法制备氧化锌高温煤气脱硫剂的原位再生动力学

冯宇, 史磊, 张赛赛, 武蒙蒙, 米杰

太原理工大学, 煤科学与技术教育部与山西省重点实验室, 山西太原 030024

收稿日期:2017-01-18 修回日期:2017-03-09 出版日期:2017-08-05 发布日期:2017-08-05
通讯作者: 米杰,教授。
作者简介:冯宇(1991-),男,博士研究生。
基金资助:
国家自然科学基金项目（51272170，21276172）。

Kinetics study of zinc oxide sorbent prepared by different methods for hot coal gas desulfurization

FENG Yu, SHI Lei, ZHANG Saisai, WU Mengmeng, MI Jie

Key Laboratory of Coal Science and Technology of Shanxi Province and Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2017-01-18 Revised:2017-03-09 Online:2017-08-05 Published:2017-08-05

摘要/Abstract

摘要： 分别采用室温固相法和均匀沉淀法原位制备氧化锌脱硫剂前体，并在热天平装置上研究了再生温度及反应中氧气浓度对氧化锌高温煤气脱硫剂的原位再生行为的影响。采用收缩核模型对脱硫剂前体氧化再生过程的动力学进行了描述，并计算其反应级数及表观动力学参数，结果表明：脱硫剂原位再生的过程中动力学控制步骤发生了转移，当再生转化率低于80%时，再生反应主要为表面化学反应控制阶段；当再生转化率高于85%时，再生反应主要是颗粒内扩散控制。室温固相法和均匀沉淀法所制备脱硫剂的表观化学反应速率常数的指前因子k_s0分别为4.45m/s、1.01m/s，化学反应活化能E_a分别为43.12kJ/mol、65.76kJ/mol，有效扩散系数因子D_e0分别为5.42×10^-2m²/s、1.29×10^-3m²/s，内扩散表观活化能E_p分别为38.38kJ/mol、43.29kJ/mol。此外，通过表征发现均匀沉淀法制备的脱硫剂内部活性组分更加分散、粒径更小、孔隙发达，提高了脱硫剂的再生性能。

关键词: 室温固相法, 均匀沉淀法, 氧化锌脱硫剂, 原位, 再生动力学

Abstract: In this paper the different methods,such as ambient solid-state method and homogeneous precipitation method,were used to prepare the precursor of zinc oxide sorbent. The effects of reaction temperature and oxygen concentration on the in-situ regeneration of zinc oxide sorbent were investigated on the thermal balance device. Shrinking core model was employed to describe the kinetics of in-situ regeneration process of the precursor. The result showed that when the regeneration conversion rate was less than 80%,the regeneration reaction was mainly controlled by surface chemical reaction. When the regeneration conversion rate was higher than 85%,the regeneration reaction was mainly controlled by intra-particle diffusion. According to Arrhenius equation,the pre-exponential factors and activation energies of chemical reaction of the apparent reaction rate constant were 4.45m/s,43.12kJ/mol for ambient solid-state method and 1.01m/s,65.76kJ/mol for homogeneous precipitation method,respectively. The effective diffusivity factor and apparent activation energy of internal diffusion of the ambient solid-state method were 5.42×10^-2m²/s and 38.38kJ/mol,and those of homogeneous precipitation method were 1.29×10^-3m²/s and 43.29kJ/mol,respectively.

Key words: ambient solid-state method, homogeneous precipitation method, zinc oxide sorbent, in-situ, regeneration kinetics

中图分类号:

TQ02

冯宇, 史磊, 张赛赛, 武蒙蒙, 米杰. 不同方法制备氧化锌高温煤气脱硫剂的原位再生动力学[J]. 化工进展, 2017, 36(08): 2994-3001.

FENG Yu, SHI Lei, ZHANG Saisai, WU Mengmeng, MI Jie. Kinetics study of zinc oxide sorbent prepared by different methods for hot coal gas desulfurization[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 2994-3001.

参考文献

[1] LIU Z,SHI S,LI Y. Coal liquefaction technologies-development in china and challenges in chemical reaction engineering[J]. Chemical Engineering Science,2010,65(1):12-17.
[2] MUREDDU M,FERINO I,ROMBI E,et al. ZnO/SBA-15 composites for mid-temperature removal of H₂S:synthesis,performance and regeneration studies[J]. Fuel,2012,102:691-700.
[3] CHEAH S,CARPENTER DL,MAGRINI-BAIR KA. Review of mid-to high-temperature sulfur sorbents for desulfurization of biomass-and coal-derived syngas[J]. Energy & Fuels,2009,23(11):5291-5307.
[4] PAN YG,PERALES JF,VELO E,et al. Kinetic behaviour of iron oxide sorbent in hot gas desulfurization[J]. Fuel,2005,84(9):1105-1109.
[5] KARVAN O,ATAKÜL H. Investigation of CuO/mesoporous SBA-15 sorbents for hot gas desulfurization[J]. Fuel Processing Technology,2008,89(9):908-915.
[3] YU J,CHANG L,XIE W,et al. Correlation of H₂S and COS in the hot coal gas stream and its importance for high temperature desulfurization[J]. Korean Journal of Chemical Engineering,2011,28(4):1054-1057.
[4] IKENAGA N,OHGAITO Y,MATSUSHIMA H,et al. Preparation of zinc ferrite in the presence of carbon material and its application to hot-gas cleaning[J]. Fuel,2004,83(6):661-669.
[5] PINEDA M,PALACIOS J M,ALONSO L,et al. Performance of zinc oxide based sorbents for hot coal gas desulfurization in multicycle tests in a fixed-bed reactor[J]. Fuel,2000,79(8):885-895.
[6] FAUTEUX-LEFEBVRE C,ABATZOGLOU N,BLAIS S,et al. Iron oxide-functionalized carbon nanofilaments for hydrogen sulfide adsorption:the multiple roles of carbon[J]. Carbon,2015,95:794-801.
[7] WANG J,LIU L,HAN L,et al. Alumina-supported manganese oxide sorbent prepared by sub-critical water impregnation for hot coal gas desulfurization[J]. Fuel Processing Technology,2013,110:235-241.
[8] REZAEI S,JARLIGO M O D,Wu L,et al. Breakthrough performances of metal-exchanged nanotitanate ETS-2 adsorbents for room temperature desulfurization[J]. Chemical Engineering Science,2015,123:444-449.
[9] ZENG Y,KAYTAKOGLU S,HARRISON D P. Reduced cerium oxide as an efficient and durable high temperature desulfurization sorbent[J]. Chemical Engineering Science,2000,55(21):4893-4900.
[10] GAN L M,ZHANG L H,CHAN H S O,et al. A novel method for the synthesis of perovskite-type mixed metal oxides by the inverse microemulsion technique[J]. Journal of Materials Science,1996,31(4):1071-1079.
[11] NGAMCHARUSSRIVICHAI C,TOTARAT P,BUNYAKIAT K. Ca and Zn mixed oxide as a heterogeneous base catalyst for transesterification of palm kernel oil[J]. Applied Catalysis A:General,2008,341(1/2):77-85.
[12] KIM S,BAJAJ B,CHANG K B,et al. Preparation of flexible Zinc oxide/carbon nanofiber webs for mid-temperature desulfurization[J]. Applied Surface Science,2014,320(320):218-224.
[13] CUI H,ZAYAT M,LEVY D. Sol-Gel Synthesis of nanoscaled spinels using propylene oxide as a gelation agent[J]. Journal of Sol-Gel Science and Technology,2005,35(3):175-181.
[14] AHMAD W,MEHMOOD U,AL-AHMED A,et al. Synthesis of zinc oxide/titanium dioxide (ZnO/TiO₂) nanocomposites by wet incipient wetness impregnation method and preparation of ZnO/TiO₂ paste using poly (vinylpyrrolidone) for efficient dye-sensitized solar cells[J]. Electrochimica Acta,2016,222:473-480.
[15] SRIKANTH C K,JEEVANANDAM P. Effect of anion on the homogeneous precipitation of precursors and their thermal decomposition to zinc oxide[J]. Journal of Alloys & Compounds,2009,486(1):677-684.
[16] YU FENG,TIANQI HU,ZHAOTING PU,et al. Non-isothermal decomposition kinetics of FeC₂O₄·2H₂O prepared by solid-state method aiming at the formation of Fe₂O₃[J]. Journal of Thermal Analysis and Calorimetry,2015,122(2):1-7.
[17] CASSIERS K,LINSSEN T,MATHIEU M,et al. A detailed study of thermal,hydrothermal,and mechanical stabilities of a wide range of surfactant assembled mesoporous silicas[J]. Chemistry of Materials,2002,14(5):2317-2324.
[18] BING Z,HE L,TAO H,et al. Kinetic study on the sulfidation and regeneration of manganese-based regenerable sorbent for high temperature H₂S removal[J]. Industrial & Engineering Chemistry Research,2015,54(4):1179-1188.

不同方法制备氧化锌高温煤气脱硫剂的原位再生动力学

Kinetics study of zinc oxide sorbent prepared by different methods for hot coal gas desulfurization

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