CIESC Journal ›› 2018, Vol. 69 ›› Issue (7): 3001-3008.doi: 10.11949/j.issn.0438-1157.20171632

Previous Articles     Next Articles

Effect of ultrasonic alkali treatment on structural, acidic properties and performance of MOR catalyst

HAN Haibo1,2, WANG Youhe1, LI Kang2, LIU Danhe2, HAO Daijun2, YAN Zifeng1   

  1. 1 State Key Laboratory for Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong, China;
    2 Luoyang R & D Center of Technology of Sinopec Engineering(Group) CO., LTD., Luoyang 471003, Henan, China
  • Received:2017-12-12 Revised:2018-01-31 Online:2018-07-05 Published:2018-03-15
  • Supported by:

    supported by the National Natural Science Foundation of China(21776311) and the Fundamental Research Funds for the Central Universities (15CX05030A).

Abstract:

MOR catalyst commonly suffers the poor stability in the catalytic synthesis of methyl acetate. It's difficulty to introduce the hierarchical pores by traditional alkali treatment. To overcome this drawback, an ultrasonic alkali treatment was utilized to generate hierarchical MOR via desilication. Multiple analyzing methods, such as XRD, SEM, TEM, pyridine IR and N2 adsorption-desorption, were used to characterize the catalyst structure and the influence of ultrasonic treatment under different alkali concentration on the MOR framework. Acidity, pore structure and catalytic properties were investigated. The results showed that a proper ultrasonic alkali treatment could significantly improve the number of acidic sites, mesopore volume, surface area, pore size distribution, catalytic activity and stability. The DME conversion increased from 35.3% to 44.8%, and the catalyst lifetime was greatly prolonged. However, an excessive alkali concentration seriously destroyed the MOR framework, leading to a rapid decrease on catalyst activity and stability.

Key words: ultrasonic, alkali treatment, DME carbonylation, hierarchical MOR

CLC Number: 

  • O643

[1] CHEUNG P, BHAN A, SUNLEY G J, et al. Site requirements and elementary steps in dimethyl ether carbon catalyzed by acidic zeolites[J]. Journal of Catalysis, 2007, 245(1):110-123.
[2] CHEUNG P, BHAN A, SUNLEY G J, et al. Selective carbonylation of dimethylether to methyl acetate catalyzed by acidic zeolites[J]. Angewandte Chemie International Edition, 2006, 45(10):1617-1620.
[3] LIU J, XUE H, HUANG X, et al. Dimethyl ether carbonylation to methyl acetate over HZSM-35[J]. Catalysis Letters, 2010, 139(1/2):33-37.
[4] BHAN A, ALIAN A D, SUNLE G J, et al. Specificity of sites within eight-membered ring zeolite channels for carbonylationof methyls to acetyls[J]. Journal of the American Chemical Society, 2007, 129(16):4919-4924.
[5] BHAN A, IGLESIA E. A link between reactivity and local structure in acid catalysis on zeolites[J]. Accounts of Chemical Research, 2008, 41(4):559-567.
[6] SANO T, WAKABAYASHI S, OUMI Y, et al. Synthesis of large mordenite crystals in thepresence of aliphatic alcohol[J]. Micropor. Mesopor. Mater., 2001, 46(1):67-74.
[7] OZIN G A, KUPERMAN A, STEIN A. Advanced zeolite, materials science[J]. Angew. Chem. Int. Ed., 1989, 28(3):359-376.
[8] COX S D, GIER T E, STUCKY G D, et al. Inclusion tuning of nonlinear optical materials:switching the SHG of p-nitroaniline and 2-methyl-p-nitroaniline with molecular sieve hosts[J]. J. Am. Chem. Soc., 1988, 110(9):2986-2987.
[9] BORONAT M, MARTINEZ C, LAW D, et al. Enzyme-like specificity in zeolites:a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO[J]. Journal of the American Chemical Society, 2008, 130(48):16316-16323.
[10] BORONAT M, MARTINEZ C, CORMA A. Mechanistic differences between methanol and dimethyl ether carbonylation in side pockets and large channels of mordenite[J]. Physical Chemistry Chemical Physics, 2011, 13(7):2603-2612.
[11] BLASCO T, BORONAT M, CONCEPCION P, et al. Carbonylation of methanol on metal-acid zeolites:evidence for a mechanism involving a multisite active center[J]. Angewandte Chemie International Edition, 2007, 46(21):3938-3941.
[12] XUE H, HUANG X, ZHAN E, et al. Selective dealumination of mordenite for enhancing its stability in dimethy ether carbonylation[J]. Catalysis Communications, 2013, 37:75-79.
[13] ANA P, CARVALHO D, ANGELA M, et al. Modification of MOR by desilication treatments:structural, textural and acidic characterization[J]. Microporous and Mesoporous Materials, 2010, 131:350-357.
[14] YANG G H, SAN X G, JIANG N, et al. A new method of ethanol synthesis from dimethyl ether and syngas in a sequential dual bed reactor with the modified zeolite and Cu/ZnO catalysts[J]. Catalysis Today, 2011, 164(1):425-428.
[15] LI X G, SAN X G, ZHANG Y, et al. Direct synthesis of ethanol from dimethyl ether and syngas over combined H-mordenite and Cu/ZnO catalysts[J]. ChemSusChem, 2010, 3(10):1192-1199.
[16] 赵娜, 李新刚, 马新宾, 等. 预处理条件及金属离子改性对HMOR分子筛的DME羰基化性能影响[J].化工学报, 2015, 66(9):3504-3510. ZAO N, LI X G, MA X B, et al. Influence of pretreatment and metal cation modification of H-MOR zeolite on performance of DME carbonylation[J]. CIESC Journal, 2015, 66(9):3504-3510.
[17] LIU J L, XUE H F, HUANG X M, et al. Stability enhancement of Hmordenite in dimethyl ether carbonylation to methyl acetate by preadsorption of pyridine[J]. China J. Catal., 2010, 31(7):729-738.
[18] LIU J, XUE H, HUANG X, et al. Dimethyl ether carbonylation to methyl acetate over HZSM-35[J]. Catal. Lett., 2010, 139(1/2):33-37.
[19] MCQUEEN D, CHICHE B H, FAJULA F, et al. A multitechnique characterization of the acidity of dealuminated mazzite[J]. J. Catal., 1996, 161(2):587-596.
[20] KERR G T. Intracrystalline rearrangement of constitutive water in hydrogen zeolite Y[J]. Phys. Chem., 1967, 71(12):4155-4156.
[21] COSTER D, BLUMENFELD A L, FRIPIAT J J. Lewis acid sites and surface aluminum in aluminas and zeolites:a high-resolution NMR study[J]. Phys. Chem., 1994, 98(24):6201-6211.
[22] BOVERI M, MARQUEZ-ALVAREZ C. Steam and acid dealumination of mordenite characterization and influence on the catalytic performance in linear alkylbenzene synthesis[J].Catalysis Today, 2006, 114(2/3):217-225.
[23] VAN LAAK A N C, SAGALA S L. Mesoporous mordenites obtained by sequential acid and alkaline treatments-catalysts for cumene production with enhanced accessibility[J]. J. Catal., 2010, 276:170-180.
[24] VAN LAAK A N C, GOSSELINK R W, SAGALA S L, et al. Alkaline treatment on commercially available aluminum rich mordenite[J]. Appl. Catal. A. Gen., 2010, 382(1):65-72.
[25] BRUNAUER B, DEMING L S, DENIBG W E. On a theory of the van der Waals adsorption of gases[J]. J. Am. Chem. Soc., 1940, 62:1723-1732.
[26] 肖强, 项寿鹤. 碱处理丝光沸石的表征及其催化合成乙基叔丁基醚的性能[J]. 催化学报, 2005, 26(3):243-247. XIAO Q, XIANG S H. Characterization and catalytic performance of alkali-treated mordenite for synthesis of ethyl tertiary butyl ether[J]. Chinese Journal of Catalysis, 2005, 26(3):243-247.
[27] GROEN J C, SANO T, MOULIJN J A, et al. Alkaline-mediated mesoporous mordenite zeolites for acid-catalyzed conversions[J]. J. Catal., 2007, 251(1):21-27.
[28] BARZETTI T, SELLI E, MOSCOTTI D, et al. Pyridine and ammonia as probes for FTIR analysis of solid acid catalysts[J]. J. Chem. Soc. Faraday Trans., 1996, 92(21):1401-1407.
[29] WEI X, SMIRNIOTIS P G. Development and characterization of mesoporosity in ZSM-12 by desilication[J]. Micropor. Mesopor. Mater., 2006, 97(32):97-106.

[1] SU Mingxu, MUHAMMAD Abdul Ahad, JIANG Yong, WU Wei, YANG Huinan. Synchronous thickness measurements of flowing liquid film on horizontal surface by ultrasonic pulse-echo and laser absorption spectroscopy methods [J]. CIESC Journal, 2018, 69(7): 2972-2978.
[2] ZHANG Aiping, FENG Zhuo, DING Quan, XU Zhiming. Simulation study on influential of ultrasonic cavitation on fouling deposition characteristic [J]. CIESC Journal, 2017, 68(S1): 184-190.
[3] KANG Junpei, GE Ting, LIU Sa, YANG Junzhong, REN Li. Effect of different ball milling processes on purity and particle size of β-tricalcium phosphate powders by solid-state synthesis [J]. CIESC Journal, 2017, 68(1): 424-429.
[4] JI Xiaoming, SU Mingxu, WANG Xue, CAI Xiaoshu. Particle size characterization based on ultrasonic impedance spectrum [J]. CIESC Journal, 2016, 67(6): 2284-2290.
[5] SUN Zhicheng, HAN Jin, ZHANG Mingyang, MD. Asadur Rahoman, WANG Youzhao, QI Yuanxin, WANG Min, XIE Yuanhua, ZHU Tong. Disintegration of excess sludge by mechanical rotary disk combination with ultrasonication [J]. CIESC Journal, 2016, 67(12): 5229-5236.
[6] XU Shuying, TAN Wei, ZHANG Yucang. Enzyme degumming process of banana pseudostem fibers andcharacterization of degummed fibers [J]. CIESC Journal, 2015, 66(9): 3753-3761.
[7] ZHANG Lei, LIU Huiling, ZHANG Bo. Mechanism of enhancement ozonation by ultrasound for degradation of polyacrylamide in ASP produced [J]. CIESC Journal, 2015, 66(6): 2242-2247.
[8] LI Zhiwen, FAN Shuanshi, LIU Wenzhong, WANG Yanhong, LANG Xuemei. Effect of ultrasonic on behavior and morphology of calcium carbonate fouling within water boiler [J]. CIESC Journal, 2015, 66(6): 2256-2261.
[9] ZHAO Shengyao, ZHU Bo. Effect of ultrasonic treatment in polyacrylonitrile dissolution [J]. CIESC Journal, 2015, 66(2): 848-855.
[10] TANG Jiguo, YAN Changqi, SUN Licheng. Condensation process and heat transfer of vapor bubbles in ultrasonic field [J]. CIESC Journal, 2015, 66(11): 4359-4365.
[11] LIU Xiufeng, XU Kai, ZHANG Baoquan. Synthesis and surface modification of ZSM-5 and Fe-ZSM-5 zeolite membranes [J]. CIESC Journal, 2014, 65(z2): 304-309.
[12] DU Wenjing, WANG Hongfu, CHENG Lin. Shell side fluid flow characteristics in helical baffled heat exchanger [J]. CIESC Journal, 2014, 65(8): 2970-2975.
[13] ZHANG Wei, SU Mingxu, CAI Xiaoshu. Particle size distribution measurement based on ultrasonic attenuation and phase velocity spectra [J]. CIESC Journal, 2014, 65(3): 898-904.
[14] QI Dongming, ZHAO Xiaoli, CHEN Zhijie, WU Minghua. Preparation of submicron polystyrene particles by micro-suspension polymerization with ultrasonic homogenization [J]. CIESC Journal, 2014, 65(2): 744-751.
[15] YU Tongmin, WU Yongqiang, HUANG Xiaochao. Effects of ultrasonic field on filling quality for micro-column arrays parts [J]. CIESC Journal, 2014, 65(12): 5023-5029.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
[1] CAO Xing,DU Wenjing,CHENG Lin. Analyses on flow and heat transfer performance and entropy generation of heat exchanger with continuous helical baffles[J]. CIESC Journal, 2012, 63(8): 2375 -2382 .
[2] ZHANG Lanhe,LI Jun,GUO Jingbo,JIA Yanping,ZHANG Haifeng. Effect of EPS on activated sludge flocculation Ability , Settleability and surface properties[J]. CIESC Journal, 2012, 63(6): 1865 -1871 .
[3] CHEN Weidong, SUN Yan. EFFECT OF ADSORPTION DENSITY ON PORE DIFFUSIVITY OF PROTEINS IN ION EXCHANGER[J]. CIESC Journal, 2003, 54(2): 215 -220 .
[4] ZHOU Xinjian, CHEN Tingkuan. DETERMINATION OF FLOW RATE COEFFICIENT OF JET EXHAUSTING ATOMIZATION NOZZLE[J]. CIESC Journal, 2002, 53(10): 1092 -1094 .
[5] SUN Qinglei, LI Wen, LI Baoqing. RELATIONSHIP BETWEEN VOLATILE YIELD AND PETROGRAPHIC ANALYSIS DURING PYROLYSIS OF SHENMU MACERALS[J]. CIESC Journal, 2003, 54(2): 269 -272 .
[6] LIU Tang, QIAN Weizhong, WANG Zhanwen, WEI Fei, JIN Yong, LI Juncheng, LI Yongdan. PREPARATION OF HYDROGEN AND CARBON NANOTUBES via METHANE DECOMPOSITION IN FLUIDIZED-BED REACTOR[J]. CIESC Journal, 2003, 54(11): 1614 -1618 .
[7] ZHAO Zongbin, LI Wen, LI Baoqing. EFFECT OF MINERAL MATTER ON RELEASE OF NO DURING COAL CHAR COMBUSTION[J]. CIESC Journal, 2003, 54(1): 100 -106 .
[8] LI Rui, XU Chunjian, ZENG Aiwu, ZHOU Ming. CFD SIMULATION OF DISTILLATION TRAY BASED ON THREE DIMENSIONAL TWO-LAYER MODEL[J]. CIESC Journal, 2003, 54(2): 159 -163 .
[9] ZHAN Shuiqing1,ZHOU Jiemin1,WU Ye2,LI Yuan1,LIANG Yannan1,YANG Ying1. Dynamic measurement of thermophysical properties of molten salt and error correction method[J]. CIESC Journal, 2012, 63(8): 2341 -2347 .
[10] HAN Jiabin, WANG Jingkang. MEASUREMENT AND CORRELATION OF SOLUBILITY OF CAFFEINE IN WATER AND ETHANOL[J]. CIESC Journal, 2004, 55(1): 125 -128 .