Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts

doi:10.11949/0438-1157.20230168

Abstract

Abstract:

For the reaction of ethylene catalytic oxidation to ethylene oxide, the finite element method (FEM) is employed to solve the deactivation kinetics and reaction-mass transfer-heat transfer model simultaneously. The convergence of the model and accuracy of calculation results are very well. After the catalyst particles reacted for 16 months, the activity coefficients of the main and side reactions decreased significantly, and the deactivation rate of the side reactions was greater than that of the main reactions. With the deactivation of catalysts, the first kind deactivation internal effectiveness factor increases with time, and the second kind deactivation internal effectiveness factor decreases at first and then increases slightly. It is shown by quantitative calculation that the internal diffusion resistance can “delay” the reduction of apparent reaction rate caused by catalyst deactivation. For ethylene catalytic oxidation system with severe internal diffusion limitations, the apparent deactivation rate is only 50.8% of intrinsic deactivation value. The parameter values of the deactivation kinetic equations by experiments are strongly influenced by internal diffusion, and a distinction must be made between intrinsic and macroscopic deactivation kinetics. When the activity factors are reduced to a certain value, the reaction temperature can be increased to ensure the reaction at a high range. This model can be applied to guide reactor design and optimize the operation parameters with deactivation process.

Key words: deactivation kinetics, deactivation internal effectiveness factor, transient process, irregular-shaped catalysts, finite element method

摘要：

以乙烯催化氧化制环氧乙烷体系为研究对象，采用有限元算法对异形催化剂失活动力学方程与反应-传质-传热方程组同时求解，模型收敛性和计算结果准确性均很好。催化剂颗粒经过16个月反应后，主副反应活性系数均下降明显，且副反应失活速率大于主反应。随着催化剂失活，第一类失活内扩散效率因子随时间增加而上升，第二类失活内扩散效率因子随时间增加先下降然后小幅度上升。通过定量计算表明催化剂内扩散阻力的存在能“延缓”由于失活导致的表观反应速率下降。对于存在强内扩散限制的此反应体系，表观失活速率只有不存在内扩散影响的失活速率的50.8%。内扩散对失活动力学方程实验测量有很大影响，必须区分本征失活动力学和宏观失活动力学。当催化剂活性降低到一定程度，可以提高反应温度以保证反应在高速率区间进行。应用此模型能指导反应器设计和失活状态下反应器的操作参数优化。

关键词: 失活动力学, 失活内扩散效率因子, 非稳态过程, 异形催化剂, 有限元算法

CLC Number:

TQ 021.4

Jipeng ZHOU, Wenjun HE, Tao LI. Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts[J]. CIESC Journal, 2023, 74(6): 2416-2426.

周继鹏, 何文军, 李涛. 异形催化剂上乙烯催化氧化失活动力学反应工程计算[J]. 化工学报, 2023, 74(6): 2416-2426.

Figures/Tables 18

Fig.1 Deactivation curve moving over time in fixed bed reactor

Fig.2 Variable relationship with deactivation process

Fig.3 Geometry and grid map of catalyst

Fig.4 Calculated and experimental values of main reaction activity factor

Fig.5 Distribution of catalyst main reaction activity factor after 16 months

Fig.6 Distribution of catalyst side reaction activity factor after 16 months

Fig.7 Distribution of catalyst main reaction activity factor after 2, 4, 8 and 12 months

Fig.8 Main activity factor under different temperature condition after 16 months

Fig.9 ET concentration distribution after 16 months

Fig.10 Temperature distribution after 16 months

Fig.11 Reaction rate distribution of EO after 16 months

Fig.12 Normalized reaction rate distribution in line B after 16 months

Fig.13 Reaction selectivity after 16 months

Fig.14 The first kind internal effectiveness factor of deactivation

Fig.15 The second kind internal effectiveness factor of deactivation

Fig.16 Influence of temperature on catalyst main reaction activity factor

Fig.17 Influence of temperature on the second kind internal effectiveness factor of deactivation

Fig.18 Influence of temperature on reaction rate

References 30

1	Amin A, Epling W, Croiset E. Reaction and deactivation rates of methane catalytic cracking over nickel[J]. Industrial & Engineering Chemistry Research, 2011, 50(22): 12460-12470.
2	Sengar A, van Santen R A, Steur E, et al. Deactivation kinetics of solid acid catalyst with laterally interacting protons[J]. ACS Catalysis, 2018, 8(10): 9016-9033.
3	Wang A Y, Wang J H, Sheti S, et al. A deactivation mechanism study of phosphorus-poisoned diesel oxidation catalysts: model and supplier catalysts[J]. Catalysis Science & Technology, 2020, 10(16): 5602-5617.
4	Iranshahi D, Pourazadi E, Paymooni K, et al. Modeling of an axial flow, spherical packed-bed reactor for naphtha reforming process in the presence of the catalyst deactivation[J]. International Journal of Hydrogen Energy, 2010, 35(23): 12784-12799.
5	齐国祯, 谢在库, 陈庆龄. SAPO-34催化剂上甲醇制烯烃反应——催化反应失活动力学[J]. 化学反应工程与工艺, 2013, 29(1): 1-6.
	Qi G Z, Xie Z K, Chen Q L. Methanol to olefins (MTO) reaction over SAPO-34 catalyst—deactivation kinetics of catalytic reaction[J]. Chemical Reaction Engineering and Technology, 2013, 29(1): 1-6.
6	Haghlesan A, Alizadeh R, Fatehifar E. Modeling of ethylbenzene dehydrogenation catalyst deactivation on an industrial scale[J]. Petroleum Science and Technology, 2016, 34(6): 499-504.
7	Chen Q Q, Lua A C. Kinetic reaction and deactivation studies on thermocatalytic decomposition of methane by electroless nickel plating catalyst[J]. Chemical Engineering Journal, 2020, 389: 124366.
8	Tian Y, Abed A M, Aljeboree A M, et al. Green process of fuel production under porous γ-Al₂O₃ catalyst: study of activation and deactivation kinetic for MTD process[J]. Arabian Journal of Chemistry, 2022, 15(12): 104287.
9	陆铭, 朱子彬, 陈庆龄, 等. AB-97分子筛催化剂上苯与乙烯烷基化反应(Ⅲ): 失活动力学及失活特征[J]. 石油化工, 2002, 31(5): 329-333.
	Lu M, Zhu Z B, Chen Q L, et al. Study on ethylbenzene synthesis over AB-97 zeolite (Ⅲ): Deactivation kinetics[J]. Petrochemical Technology, 2002, 31(5): 329-333.
10	刘颖, 韩崇仁, 方维平, 等. 催化剂积炭失活宏观反应动力学的研究[J]. 催化学报, 2004, 25(2): 107-109.
	Liu Y, Han C R, Fang W P, et al. Study on reaction kinetics of coke deposition and deactivation of catalysts[J]. Chinese Journal of Catalysis, 2004, 25(2): 107-109.
11	Ostrovskii N M. General equation for linear mechanisms of catalyst deactivation[J]. Chemical Engineering Journal, 2006, 120: 73-82.
12	董青青, 于万金, 程党国, 等. 3-甲基吡啶氯氟化反应积炭失活催化剂的烧炭动力学模型[J]. 高校化学工程学报, 2017, 31(4): 834-840.
	Dong Q Q, Yu W J, Cheng D G, et al. Kinetic models for coke combustion of deactivated CrO-Al from 3-picoline chlorofluorination reaction[J]. Journal of Chemical Engineering of Chinese Universities, 2017, 31(4): 834-840.
13	Wang H M, You C F. Photocatalytic oxidation of SO₂ on TiO₂ and the catalyst deactivation: a kinetic study[J]. Chemical Engineering Journal, 2018, 350: 268-277.
14	Gromotka Z, Yablonsky G, Ostrovskii N, et al. Three-factor kinetic equation of catalyst deactivation[J]. Entropy, 2021, 23(7): 818.
15	Krishnaswamy S, Kittrell J R. Diffusional influences on deactivation rates[J]. AIChE Journal, 1981, 27(1): 120-125.
16	李丰, 支玉珍, 吴指南. 内扩散对苯和乙烯气相烃化反应失活动力学的影响[J]. 石油化工, 1989, 18(1): 1-8.
	Li F, Zhi Y Z, Wu Z N. Effect of pore internal diffusion on deactivating kinetics of gas phase alkylation of benzene with ethylene over AF-5 zeolite catalyst[J]. Petrochemical Technology, 1989, 18(1): 1-8.
17	崔瑞利, 赵愉生, 于双林, 等. 渣油加氢脱残炭催化剂的失活研究[J]. 石油化工, 2013, 42(4): 411-414.
	Cui R L, Zhao Y S, Yu S L, et al. Deactivation of catalyst for removing residue carbon in hydrotreating residual oil[J]. Petrochemical Technology, 2013, 42(4): 411-414.
18	Abbas H F, Daud W M A W. Hydrogen production by thermocatalytic decomposition of methane using a fixed bed activated carbon in a pilot scale unit: apparent kinetic, deactivation and diffusional limitation studies[J]. International Journal of Hydrogen Energy, 2010, 35(22): 12268-12276.
19	Gayubo A G, Valle B, Aramburu B, et al. Kinetic model considering catalyst deactivation for the steam reforming of bio-oil over Ni/La₂O₃-αAl₂O₃ [J]. Chemical Engineering Journal, 2018, 332: 192-204.
20	韩坤鹏, 戴立顺, 聂红. 固定床渣油加氢催化剂运转初期失活规律研究进展[J]. 化工进展, 2017, 36(S1): 211-220.
	Han K P, Dai L S, Nie H. Research progress on deactivation of fixed bed residue hydrogenating catalysts at the initial stage of operation[J]. Chemical Industry and Engineering Progress, 2017, 36(S1): 211-220.
21	Liu X L, Zhang Q F, Ye G H, et al. Deactivation and regeneration of Claus catalyst particles unraveled by pore network model[J]. Chemical Engineering Science, 2020, 211: 115305.
22	Wang Y, Zhang Q F, Liu X L, et al. Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model[J]. Chinese Journal of Chemical Engineering, 2023, 55: 293-303.
23	Zhao L W, Liu G L. Dynamic coupling of reactor and heat exchanger network considering catalyst deactivation[J]. Energy, 2022, 260: 125161.
24	Goh K B, Li Z, Chen X, et al. Reaction-diffusion model to quantify and visualize mass transfer and deactivation within core-shell polymeric microreactors[J]. Journal of Colloid and Interface Science, 2022, 608: 1999-2008.
25	甘霖, 王弘轼, 朱炳辰, 等. 环氧乙烷合成银催化剂宏观动力学及失活分析[J]. 化工学报, 2001, 52(11): 969-973.
	Gan L, Wang H S, Zhu B C, et al. Global kinetics and deactivation of silver catalyst for ethylene oxide synthesis[J]. Journal of Chemical Industry and Engineering(China), 2001, 52(11): 969-973.
26	张杰, 李涛. 甲烷化梅花状催化剂CFD计算及改进[J]. 化工学报, 2018, 69(7): 2985-2992.
	Zhang J, Li T. Application of CFD to improve calculated process of methanation over plum-shaped catalyst[J]. CIESC Journal, 2018, 69(7): 2985-2992.
27	应景涛, 李涛. 费托合成蛋壳型催化剂活性组分厚度的模拟计算[J]. 化工学报, 2019, 70(9): 3404-3411.
	Ying J T, Li T. Simulation of active component thickness of egg-shell catalyst for F-T synthesis[J]. CIESC Journal, 2019, 70(9): 3404-3411.
28	蒋文超, 张海涛, 马宏方, 等. 合成氨催化剂颗粒的多组分反应-扩散模型计算[J]. 华东理工大学学报(自然科学版), 2022, 48(6): 723-729.
	Jiang W C, Zhang H T, Ma H F, et al. Multicomponent reaction-diffusion model calculation of catalyst particles for ammonia synthesis[J]. Journal of East China University of Science and Technology (Natural Science Edition), 2022, 48(6): 723-729.
29	Liu B, Chai Y M, Wang Y J, et al. A simple technique for preparation of presulfided eggshell MoS₂/Al₂O₃ catalysts and kinetics approach for highly selective hydrodesulfurization of FCC gasoline[J]. Applied Catalysis A: General, 2010, 388: 248-255.
30	王庆祺, 张国泰, 吴指南. 多孔催化剂颗粒的内扩散效应对伴有失活的二级反应动力学的影响[J]. 化工学报, 1992, 43(1): 82-90.
	Wang Q Q, Zhang G T, Wu Z N. Effect of intraparticle diffusion on catalyst deactivation kinetics for second order reactions[J]. Journal of Chemical Industry and Engineering(China), 1992, 43(1): 82-90.

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