Full Text:   <3092>

Summary:  <2084>

CLC number: TQ221.2

On-line Access: 2024-08-27

Received: 2023-10-17

Revision Accepted: 2024-05-08

Crosschecked: 2017-02-22

Cited: 0

Clicked: 4432

Citations:  Bibtex RefMan EndNote GB/T7714

 ORCID:

Xiao-yi Li

http://orcid.org/0000-0002-9133-6321

-   Go to

Article info.
Open peer comments

Journal of Zhejiang University SCIENCE A 2017 Vol.18 No.3 P.225-233

http://doi.org/10.1631/jzus.A1600295


Dual bed catalyst system for oxidative dehydrogenation of mixed-butenes: a synergistic mechanism


Author(s):  Xiao-yi Li, Dang-guo Cheng, Feng-qiu Chen, Xiao-li Zhan

Affiliation(s):  Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou 310027, China; more

Corresponding email(s):   fqchen@zju.edu.cn

Key Words:  Mixed-butenes, Dual bed catalyst, Oxidative dehydrogenation (ODH), Synergistic effect


Xiao-yi Li, Dang-guo Cheng, Feng-qiu Chen, Xiao-li Zhan. Dual bed catalyst system for oxidative dehydrogenation of mixed-butenes: a synergistic mechanism[J]. Journal of Zhejiang University Science A, 2017, 18(3): 225-233.

@article{title="Dual bed catalyst system for oxidative dehydrogenation of mixed-butenes: a synergistic mechanism",
author="Xiao-yi Li, Dang-guo Cheng, Feng-qiu Chen, Xiao-li Zhan",
journal="Journal of Zhejiang University Science A",
volume="18",
number="3",
pages="225-233",
year="2017",
publisher="Zhejiang University Press & Springer",
doi="10.1631/jzus.A1600295"
}

%0 Journal Article
%T Dual bed catalyst system for oxidative dehydrogenation of mixed-butenes: a synergistic mechanism
%A Xiao-yi Li
%A Dang-guo Cheng
%A Feng-qiu Chen
%A Xiao-li Zhan
%J Journal of Zhejiang University SCIENCE A
%V 18
%N 3
%P 225-233
%@ 1673-565X
%D 2017
%I Zhejiang University Press & Springer
%DOI 10.1631/jzus.A1600295

TY - JOUR
T1 - Dual bed catalyst system for oxidative dehydrogenation of mixed-butenes: a synergistic mechanism
A1 - Xiao-yi Li
A1 - Dang-guo Cheng
A1 - Feng-qiu Chen
A1 - Xiao-li Zhan
J0 - Journal of Zhejiang University Science A
VL - 18
IS - 3
SP - 225
EP - 233
%@ 1673-565X
Y1 - 2017
PB - Zhejiang University Press & Springer
ER -
DOI - 10.1631/jzus.A1600295


Abstract: 
oxidative dehydrogenation (ODH) of mono and mixed-butenes to 1,3-butadiene (BD) was conducted using individual and dual bed catalyst systems, consisting of ZnFe2O4, Co9Fe3Bi1Mo12O51 or both. The dual bed catalyst system gave improved catalytic performance. A mechanism based on synergy between the catalysts is proposed to explain the improved overall butene conversion. The proportion of the reactants differed between the catalyst beds in the dual bed system, making better use of the catalytic activity of the second bed. The existence of all butene isomers inhibited isomerization, leading to a higher proportion of ODH reactions and thus improved the conversion of butene and the yield of BD. The packing sequences and the volume ratio of the catalysts in the bed were optimized. The results indicated that the sequence with ZnFe2O4 on top and a catalyst packing ratio of between 4:6 and 6:4 led to better activity.

This manuscript reports on an investigation of a dual catalysts bed system for the Oxidative Dehydrogenation of mixtures of butenes to 1,3 butadiene. The topic is of interest and the amount of work is substantial.

混合丁烯氧化脱氢双层床催化剂体系的协同作用机理

目的:通过对混合丁烯氧化脱氢过程进行反应表征,对由ZnFe2O4和Co9Bi1Fe3Mo12O51组成的双床层催化剂体系中存在的协同机理进行解释;将异构化反应过程纳入反应体系,得出混合丁烯转化率和丁二烯收率上升的原因。
创新点:1. 提出基于丁烯异构体在床层之间浓度重分布和异构化效应抑制作用的协同作用机理;2. 设计验证实验,从直观角度证实机理,并优化了催化剂的装填量和装填顺序。
方法:1. 通过单一丁烯和混合丁烯的氧化脱氢反应,对单一催化剂和双床层催化剂进行反应评估,得到相关反应数据;2. 通过设计对比实验,从改变参加反应物质的直观角度对协同机理进行验证和解释;3. 对参加反应的双层床催化剂中两种催化剂的装填量和装填顺序进行优化,为进一步研究组合型催化剂提供实验基础。
结论:1. ZnFe2O4对两种2-丁烯有更优的催化效果,而Co9Bi1Fe3Mo12O51对1-丁烯有更优的催化效果,由两者组成的双层床催化体系对单一丁烯和混合丁烯的反应效果都有所提升,证明两种催化剂之间存在协同效应。2. 双层床催化剂体系中,两种催化剂之间的协同作用机理是:催化剂不同活性导致丁烯异构体在床层之间的浓度发生重分布,同时由于多种异构体同时存在抑制了异构化反应。3. 对双层床催化剂体系的装填顺序和装填量的优化结果表明,ZnFe2O4装填在上层,CCo9Bi1Fe3Mo12O51装填在下层,且两者比例处于4:6到6:4之间时催化效果最佳。

关键词:混合丁烯;氧化脱氢;双层床催化剂体系;协同作用

Darkslateblue:Affiliate; Royal Blue:Author; Turquoise:Article

Reference

[1]Ali, S.A., Aitani, A.M., Čejka, J., et al., 2015. Selective production of xylenes from alkyl-aromatics and heavy-reformates over dual-zeolite catalyst. Catalysis Today, 243:118-127.

[2]Arpornwichanop, A., Wasuleewan, M., Patcharavorachot, Y., et al., 2011. Investigation of a dual-bed autothermal reforming of methane for hydrogen production. Chemical Engineering Transactions, 25:929-934.

[3]Batist, P.A., Lippens, B.C., Schuit, G.C.A., 1966. The catalytic oxidation of 1-butene over bismuth molybdate catalysts: II. Dependence of activity and selectivity on the catalyst composition. Journal of Catalysis, 5(1):55-64.

[4]Batist, P.A., Kapteijns, C.J., Lippens, B.C., et al., 1967. The catalytic oxidation of 1-butene over bismuth molybdate catalysts: III. The reduction of bismuth oxide, molybdenum oxide, bismuth molybdate, and of some nonstoichiometric molybdenum oxides with 1-butene. Journal of Catalysis, 7(1):33-49.

[5]Batist, P.A., Der Kinderen, A.H.W.M., Leeuwenburgh, Y., et al., 1968. The catalytic oxidation of 1-butene over bismuth molybdate catalysts: IV. Dependence of activity on the structures of the catalysts. Journal of Catalysis, 12(1):45-60.

[6]Batist, P.A., Prette, H.J., Schuit, G. C. A., 1969. The catalytic oxidation of 1-butene over bismuth molybdate: V. The kinetics of the oxidation: B. Experiments with continuous flow and recirculation; reduction and reoxidation of Bi–Mo. Journal of Catalysis, 15(3):267-280.

[7]Cares, W.R., Hightower, J.W., 1971. Ferrite spinels as catalysts in the oxidative dehydrogenation of butenes. Journal of Catalysis, 23(2):193-203.

[8]Gawade, P., Alexander, A.M.C., Clark, R., et al., 2012. The role of oxidation catalyst in dual-catalyst bed for after-treatment of lean burn natural gas exhaust. Catalysis Today, 197(1):127-136.

[9]Hong, F., Yang, B.L., Schwartz, L.H., et al., 1984. Crystallite size effect in the selective oxidation of butene to butadiene on iron oxide. 1. Moessbauer, x-ray and magnetization characterization of the catalysts. Journal of Physical Chemistry, 88(12):2525-2530.

[10]Ji, S.F., Wang, W.H., 2012. Particle/Cordierite monolithic catalysts dual-bed reactor with beds-interspace supplementary oxygen and performance for oxidative coupling of methane. International Journal of Chemical Reactor Engineering, 10(1):1-11.

[11]Jung, J.C., Lee, H., Park, S., et al., 2008a. Effect of reaction conditions on the catalytic performance of Co9Fe3Bi1Mo12O51 in the oxidative dehydrogenation of n-butene to 1,3-butadiene. Korean Journal of Chemical Engineering, 25(6):1316-1321.

[12]Jung, J.C., Lee, H., Chung, Y.M., et al., 2008b. Oxidative dehydrogenation of C4 raffinate-3 to 1,3-butadiene in a dual-bed reaction system comprising ZnFe2O4 and Co9Fe3Bi1Mo12O51 catalysts: a synergistic effect of ZnFe2O4 and Co9Fe3Bi1Mo12O51 catalysts. Catalysis Letters, 123(3):239-245.

[13]Kung, H.H., Kundalkar, B., Kung, M.C., et al., 1980. Selectivity in the oxidative dehydrogenation of butene on zinc-iron oxide catalyst. Journal of Physical Chemistry, 84(4):382-388.

[14]Kung, H.H., Kung, M.C., Yang, B.L., 1981. The effect of additives to iron oxide in the selective oxidative dehydrogenation reactions. Journal of Catalysis, 69(2):506-510.

[15]Li, G., Zhu, X.B., Song, W., et al., 2011. Annealing effects on semitransparent and ferromagnetic ZnFe2O4 nanostructured films by Sol–Gel. Journal of the American Ceramic Society, 94(9):2872-2877.

[16]Massoth, F.E., Scarpiello, D.A., 1971. Catalyst characterization studies on the Zn-Cr-Fe oxide system. Journal of Catalysis, 21(3):294-302.

[17]Rennard, R.J., Kehl, W.L., 1971. Oxidative dehydrogenation of butenes over ferrite catalysts. Journal of Catalysis, 21(3):282-293.

[18]Toledo, J.A., Valenzuela, M.A., Armendáriz, H., et al., 1995. Oxidative dehydrogenation of 1-butene to butadiene on α-Fe2O3/ZnAl2O4 and ZnFexAl2-xO4 catalysts. Catalysis Letter, 30(1):279-288.

[19]Toledo, J.A., Bosch, P., Valenzuela, M.A., et al., 1997. Oxidative dehydrogenation of 1-butene over Zn-Al ferrites. Journal of Molecular Catalysis A: Chemical, 125(1):53-62.

[20]Toledo, J.A., Armendariz, H., López-Salinas, E., 2000. Oxidative dehydrogenation of n-butene: a comparative study of thermal and catalytic reaction using Fe–Zn mixed oxides. Catalysis Letter, 66(1):19-24.

[21]Tong, G.C.M., Flynn, J., Leclerc, C.A., 2005. A dual catalyst bed for the autothermal partial oxidation of methane to synthesis gas. Catalysis Letter, 102(3-4):131-137.

[22]Tu, W.H., Li, J., 2012. Utilizing MTO plant’s byproduct-mixed C4 to produce 2-propyl-heptanol. M-Sized Nitrogenous Fertilizer Progress, 5:1-3.

[23]Wan, C., Cheng, D.G., Chen, F.Q., et al., 2015a. Characterization and kinetic study of BiMoLax oxide catalysts for oxidative dehydrogenation of 1-butene to 1,3-butadiene. Chemical Engineering Science, 135:553-558.

[24]Wan, C., Cheng, D.G., Chen, F.Q., et al., 2015b. Oxidative dehydrogenation of 1-butene over vanadium modified bismuth molybdate catalyst: an insight into mechanism. RSC Advances, 5(53):42609-42615.

[25]Wan, C., Cheng, D.G., Chen, F.Q., et al., 2016a. Effects of zirconium content on the catalytic performance of BiMoZrx in the oxidative dehydrogenation of 1-butene to 1,3-butadiene. Journal of Chemical Technology and Biotechnology, 91(2):353-358.

[26]Wan, C., Cheng, D.G., Chen, F., et al., 2016b. The role of active phase in Ce modified BiMo catalysts for oxidative deydrogenation of 1-butene. Catalysis Today, 264:180-184.

[27]Yang, B.L., Hong, F., Kung, H.H., 1984. Crystallite size effect in the selective oxidation of butene to butadiene on iron oxide. 2. Reaction studies. Journal of Physical Chemistry, 88(12):2531-2534.

[28]Yu, D., Liu, Y., Wu, Z.B., 2011. Screening study of transition metal oxide catalysts supported on ceria-modified titania for catalytic oxidation of toluene. Journal of Zhejiang University-SCIENCE A (Applied Physics & Engineering), 12(6):461-469.

[29]Zhang, M., Lan, R., Liu, J., et al., 1992. Phase cooperation between the ZnFe2O4 and α-Fe2O3 phases of ferrite catalysts in the oxidative dehydrogenation of n-butenes. Journal of the Chemical Society, Faraday Transactions, 88(4):637-644.

[30]Zhang, R., Shi, X., Zhang, D.Y., et al., 1985. Application of extended kinetic isotope method: comparison of kinetic behavior of Bi-Mo and ferrite catalysts toward butene oxidative dehydrogenation and isomerization. Chinese Journal of Catalysis, 6:1-7.

[31]Zhou, W.Y., Chen, X.C., Li, Q., et al., 1983. Reaction mechanism of oxidative dehydrogenation of butenes on ferrite catalysts. Chinese Journal of Catalysis, 3:167-176.

[32]Zohour, B., Noon, D., Senkan, S., 2014. Spatial concentration and temperature profiles in dual-packed-bed catalytic reactors: oxidative coupling of methane. ChemCatChem, 6(10):2815-2820.

Open peer comments: Debate/Discuss/Question/Opinion

<1>

Please provide your name, email address and a comment





Journal of Zhejiang University-SCIENCE, 38 Zheda Road, Hangzhou 310027, China
Tel: +86-571-87952783; E-mail: cjzhang@zju.edu.cn
Copyright © 2000 - 2024 Journal of Zhejiang University-SCIENCE