CIESC Journal ›› 2018, Vol. 69 ›› Issue (2): 674-681.doi: 10.11949/j.issn.0438-1157.20171007

Previous Articles     Next Articles

Microkinetic analysis of acetylene hydrogenation over Pd-Ag/Al2O3 catalyst with different Pd/Ag ratios

ZHANG Jian, HUANG Bangyin, SUI Zhijun, ZHOU Xinggui, YUAN Weikang   

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2017-07-31 Revised:2017-11-17 Online:2018-02-05 Published:2017-11-29
  • Supported by:

    supported by the National Natural Science Foundation of China (21376076).

Abstract:

Selective acetylene hydrogenation is an important purifying reaction in ethylene industry. Pd-Ag/α-Al2O3 catalysts with different Pd/Ag ratios were prepared by stepwise incipient wetness impregnation method and characterized for structure and composition by N2-physisorption,XRD,ICP,XPS,TEM and CO chemisorption. A microkinetic model of acetylene hydrogenation over these catalysts was established from a fractional factorial design of experiment and effects of Ag amount on the hydrogenation kinetics were analyzed through microkinetic simulation and parameter value change. After values for basic parameters used DFT calculation results of C2 hydrogenation over Pt-Ag catalysts and activation energies optimized by adsorption-desorption steps, the microkinetic model could fit kinetic experiment results quite well on acetylene hydrogenation over all catalysts of various Pt-Ag ratios. The study showed that C2H4* was the most abundant surface species and vinyl hydrogenation was rate control step, which did not change with increase of Ag content. However, the increase of Ag greatly reduced activation energy of hydrogen desorption and improved ethylene selectivity. This phenomenon might be correlated to enhancement of electron transfer from Ag to Pd on the catalyst surface upon increase of Ag content.

Key words: acetylene hydrogenation, Pd-Ag catalyst, microkinetic modeling, Ag effect

CLC Number: 

  • TQ032.4

[1] BORODZINSKI A, BOND G C. Selective hydrogenation of ethyne in ethene-rich streams on palladium catalysts (Ⅰ):Effect of changes to the catalyst during reaction[J]. Catalysis Reviews, 2006, 48(2):91-144.
[2] BOS A N R, WESTERTERP K R. Mechanism and kinetics of selective hydrogenation of ethyne and ethene[J]. Chemical Engineering and Processing, 1993, 32(1):1-7.
[3] 李立新. 乙炔前加氢反应器运行稳定性的研究[J]. 化学反应工程与工艺, 2004, 20(1):47-52. LI L X. Analysis on the stability of the front-end acetylene hydrogenation reactor[J]. Chemical Reaction Engineering and Technology, 2004, 20(1):47-52.
[4] PACHULSKI A, SCHÖDEL R, CLAUS P. Performance and regeneration studies of Pd-Ag/Al2O3 catalysts for the selective hydrogenation of acetylene[J]. Applied Catalysis A:General, 2011, 400(1/2):14-24.
[5] KONHOM S, MEKASUWANDUMRONG O, PRASERTHDAM P, et al. Improvement of Pd/Al2O3 catalyst performance in selective acetylene hydrogenation using mixed phases Al2O3 support[J]. Catalysis Communications, 2008, 10(1):86-91.
[6] KIM S K, LEE J H, AHN I Y, et al. Performance of Cu-promoted Pd catalysts prepared by adding Cu using a surface redox method in acetylene hydrogenation[J]. Applied Catalysis A:General, 2011, 401(1/2):12-19.
[7] FENG J, LIU Y, YIN M, et al. Preparation and structure-property relationships of supported trimetallic PdAuAg catalysts for the selective hydrogenation of acetylene[J]. Journal of Catalysis, 2016, 344:854-864.
[8] SMIRNOVA N S, SHLYAPIN D A, SHITOVA N B, et al. EXAFS study of Pd/Sibunit and Pd-Ga/Sibunit catalysts for liquid-phase hydrogenation of acetylene to ethylene[J]. Journal of Molecular Catalysis A:Chemical, 2015, 403:10-14.
[9] 戴伟. 新型碳二馏分选择加氢BC-H-20催化剂的设计与开发[J]. 石油化工, 2004, 33:147-148. DAI W. Design and development of novel C2 fraction selective hydrogenation BC-H-20 catalyst[J]. Petrochemical Technology, 2004, 33:147-148.
[10] ZHU S Y, HOU R J, WANG T F. Effects of supports and promoter Ag on Pd catalysts for selective hydrogenation of acetylene[J]. The Chinese Journal of Process Engineering, 2012, 12(3):489-496.
[11] KUHN M, LUCAS M, CLAUS P. Long-time stability vs deactivation of Pd-Ag/Al2O3 egg-shell catalysts in selective hydrogenation of acetylene[J]. Industrial & Engineering Chemistry Research, 2015, 54(26):6683-6691.
[12] 董文寰, 李斯琴. 新型C2馏分加氢除炔催化剂的制备和应用[J]. 石油化工, 2005, 34(12):1186-1189. DONG W H, LI S Q. Preparation and application of novel C2 fraction selective hydrogenation catalyst[J]. Petrochemical Technology, 2005, 34(12):1186-1189.
[13] DUMESIC J A, TREVINO A A, MILLIGAN B A, et al. A kinetic modeling approach to the design of catalysts:formulation of a catalyst design advisory program[J]. Industrial & Engineering Chemistry Research, 1987, 26(7):1399-1407.
[14] STUDT F, ABILD-PEDERSEN F, BLIGAARD T, et al. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene[J]. Science, 2008, 320(5881):1320-1322.
[15] SELLERS H, GISLASON J. Adsorption and desorption rate constants for small molecules on metal surfaces:an example of Trouton's rule[J]. Surface Science, 1999, 426(2):147-53.
[16] SELLERS H. Entropies of desorption from temperature programmed desorption data:trends and applications to rate constant determinations[J]. Journal of Physical Chemistry B, 2003, 107(37):10206-10208.
[17] MITSUI T, ROSE M K, FOMIN E, et al. Hydrogen adsorption and diffusion on Pd(111)[J]. Surface Science, 2003, 540(1):5-11.
[18] 杜梅西克J A. 多相催化微观动力学[M]. 沈俭一, 译. 北京:国防工业出版社, 1998. DUMESIC J A. The Microkinetics of Heterogeneous Catalysis[M]. SHEN J Y, trans. Beijing:National Defense Industry Press, 1998.
[19] 王新宇, 隋志军, 朱贻安, 等. Pd/α-Al2O3催化乙炔选择性加氢微观反应动力学[J]. 化学反应工程与工艺, 2015, 31(4):322-329. WANG X Y, SUI Z J, ZHU Y A, et al. Microkinetics of acetylene selective hydrogenation over Pd/Al2O3 catalyst[J]. Chemical Reaction Engineering and Technology, 2015, 31(4):322-329.
[20] 庞洪强, 隋志军, 朱贻安, 等. 不同粒径Pd/Al2O3催化乙炔加氢反应微观动力学分析[J]. 化工学报, 2016, 67(9):3692-3698. PANG H Q, SUI Z J, ZHU Y A, et al. The microkinetics analysis of acetylene hydrogenation over Pd/Al2O3 catalyst with different particle sizes[J]. CIESC Journal, 2016, 67(9):3692-3698.
[21] BOND G C, WELLS P B. The hydrogenation of acetylene(Ⅱ):The reaction of acetylene with hydrogen catalyzed by alumina-supported palladium[J]. Journal of Catalysis, 1966, 5(1):65-73.
[22] PEI G X, LIU X Y, WANG A, et al. Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene[J]. ACS Catalysis, 2015, 5(6):3717-3725.
[23] BORODZINSKI A, CYBULSKI A. The kinetic model of hydrogenation of acetylene-ethylene mixtures over palladium surface covered by carbonaceous deposits[J]. Applied Catalysis A:General, 2000, 198(1/2):51-56.
[24] LYNGGAARD H, ANDREASEN A, STEGELMANN C, et al. Analysis of simple kinetic models in heterogeneous catalysis[J]. Progress in Surface Science, 2004, 77(3/4):71-137.
[25] KHAN N A, SHAIKHUTDINOV S, FREUND H J. Acetylene and ethylene hydrogenation on alumina supported Pd-Ag model catalysts[J]. Catalysis Letters, 2006, 108(3/4):159-164.
[26] SHETH P A, NEUROCK M, SMITH C M. First-principles analysis of the effects of alloying Pd with Ag for the catalytic hydrogenation of acetylene-ethylene mixtures[J]. Journal of Physical Chemistry B, 2005, 109(25):12449-12466.
[27] MEI D H, NEUROCK M, SMITH C M. Hydrogenation of acetylene-ethylene mixtures over Pd and Pd-Ag alloys:first-principles-based kinetic Monte Carlo simulations[J]. Journal of Catalysis, 2009, 268(2):181-195.

[1] YE Zhencheng, ZHOU Huanlan, RAO Debao. Hybrid modeling and optimization of acetylene hydrogenation process [J]. CIESC Journal, 2019, 70(2): 496-507.
[2] XIE Fuming, XU Feng, LIANG Zhishan, LUO Xionglin, SHI Fengyong. Full-cycle operation optimization of acetylene hydrogenation reactor [J]. CIESC Journal, 2018, 69(3): 1081-1091.
[3] GUO Jingjing, XU Jinjin, DU Wenli, YE Zhencheng. Self-adaptive iterative hybrid modeling and its application in acetylene hydrogenation process [J]. CIESC Journal, 2018, 69(11): 4814-4822.
[4] PANG Hongqiang, SUI Zhijun, ZHU Yi'an, ZHOU Xinggui. Microkinetics analysis of acetylene hydrogenation over Pd/Al2O3 catalyst with different particle sizes [J]. CIESC Journal, 2016, 67(9): 3692-3698.
[5] HU Baolong, HU Guihua, JIANG Da, QIAN Feng. Simulation and optimization of operating parameters of isothermal reaction process for acetylene hydrogenation [J]. CIESC Journal, 2015, 66(1): 366-372.
[6] TIAN Liang, JIANG Da, QIAN Feng. Reactor system switch strategy for acetylene hydrogenation process [J]. CIESC Journal, 2015, 66(1): 373-377.
[7] YUE Yi,YANG Dong,ZHU Yunxian,DAI Wei. Performance of Pd-Ag/Al2O3 catalyst for hydrogenation of butadiene [J]. Chemical Industry and Engineering Progree, 2013, 32(02): 364-367.
[8] TIAN Liang1,2,JIANG Da1,QIAN Feng1. Simulation and optimization of acetylene converter with decreasing catalyst activity [J]. CIESC Journal, 2012, 63(1): 185-192.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!