Preparation of hierarchical ZSM-5 zeolites treated by Na2CO3 and its catalytic performance for propane dehydrogenation to propylene

doi:10.16085/j.issn.1000-6613.2016.s2.029

Abstract

Abstract: HZSM-5 zeolites were treated with different concentrations of Na₂CO₃ solutions.The samples were characterized by XRD,N₂ adsorption and XRF.The characterizations showed that under suitable concentrations of Na₂CO₃ solution,the treatment could form meso-micropore channels,which enhanced the external surface area and mesoporous volume.At the same time,the MFI structure of HZSM-5 was not obviously destroyed,therefore better thermal stability was maintained.The Pt-Sn-K/HZSM-5 catalysts were prepared by subjecting HZSM-5 samples to alkali treatment,and their catalytic performances for propane dehydrogenation to propylene were evaluated in a fixed-bed reactor.The results showed that the initial activity of the catalyst increased with increasing Na₂CO₃ solution concentration,while the stability of the catalyst increased at first and then decreased.When Pt-Sn-K/HZSM-5(1.8) zeolite catalyst was used for propane dehydrogenation,it showed better activity and stability:after reacting for 100 hours,the conversion of propane only decreased by 2.8%,resulted in a conversion of 35.53%.The propylene selectivity maintained at 98.4% with no significant change.

Key words: ZSM-5, molecular sieves, mesoporus, alkali solution, propane dehydrogenation, propylene

摘要： 通过不同浓度的Na₂CO₃溶液处理合成的HZSM-5分子筛，并采用X射线衍射、N₂低温物理吸附和X射线荧光光谱分析仪对溶液处理前后的样品进行了表征。表征结果显示，适量浓度的Na₂CO₃溶液处理HZSM-5，能够形成介孔-微孔复合孔道，增加了分子筛介孔容积和外比表面积；同时不会明显破坏HZSM-5的MFI结构，从而保持较好的高温热稳定性。在上述碱处理后的载体上制备了Pt-Sn-K/HZSM-5分子筛催化剂，并在固定床反应器上考察了丙烷脱氢制丙烯的催化活性。结果表明，随着Na₂CO₃溶液浓度的增加，催化剂的初始活性增加，而稳定性先增加后减少。当采用Pt-Sn-K/HZSM-5（1.8）分子筛催化剂用于丙烷脱氢反应，其呈现了良好的脱氢活性和稳定性：反应100h后，其丙烷化率为35.53%，相比初始活性仅下降了2.8个百分点，丙烯选择为98.4%，基本保持不变。

关键词: ZSM-5, 分子筛, 介孔, 碱性溶液, 丙烷脱氢, 丙烯

CLC Number:

TQ031.4

HAN Wei, PAN Xiangmi, TAN Yanan, CHENG Muxi, WU Yanhui, HE Lin, AI Zhen. Preparation of hierarchical ZSM-5 zeolites treated by Na₂CO₃ and its catalytic performance for propane dehydrogenation to propylene[J]. Chemical Industry and Engineering Progree, 2016, 35(S2): 174-178.

韩伟, 潘相米, 谭亚南, 程牧曦, 吴砚会, 何霖, 艾珍. Na₂CO₃处理制备复合孔ZSM-5分子筛及其丙烷脱氢制丙烯的催化性能[J]. 化工进展, 2016, 35(S2): 174-178.

References

[1] 杨英,彭蓉.丙烷脱氢制丙烯工艺及其经济性分析[J].石油化工技术与经济,2014,30(3):6-10.
[2] 杨桂英.2014年聚烯烃市场分析及2015年展望[J].中国石油和化工经济分析,2015,3:36-39.
[3] 曾贤君,孙彦民,李晓云,等.丙烯增产技术进展及国内应用前景[C]//第七届全国工业催化技术及应用年会,南宁:2011.
[4] 谭亚南,韩伟,何霖,等.甲醇制丙烯研究及工业应用最新进展[J].化学工业与工程技术,2012,33(1):28-30.
[5] VU B K,SONG M B,AHN I Y,et al.Pt-Sn alloy phases and coke mobility over Pt-Sn/Al₂O₃ and Pt-Sn/ZnAl₂O₄ catalysts for propane[J].Appl Catal A:General,2011,400(1/2):25-33.
[6] 魏乃新,于国良.丙烷脱氢制丙烯的技术经济性探讨[J].中国石油和化工经济分析,2012(11):42-47.
[7] 刘淑鹤,方向晨,张喜文,等.丙烷脱氢催化反应机理及动力学研究进展[J].化工进展,2009,28(2):259-266.
[8] KUMAR S M,CHEN D,HOLMEN A,et al.Dehydrogenation of propane over Pt-SBA-15 and Pt-Sn-SBA-15:effect of Sn on the dispersion of Pt and catalytic behavior[J].Catalysis Today,2009,142(1/2):17-23.
[9] ZHANG Y,ZHOU Y,SHI J,et al.Comparative study of bimetallic Pt-Sn catalysts supported on different supports for propane dehydrogenation[J]. J. Mol. Catal.A:Chem.,2014,381(1):138-147.
[10] 谢在库.新结构高性能多孔催化材料[M].北京:中国石化出版社,2009.
[11] 邱安定,李恩霞,范以宁.载体组成对负载型PtSn/ZSM-5催化剂上丙烷脱氢反应性能的影响[J].催化学报,2007,28(11):970-974.
[12] 王秀玲.分子筛载体对Pt-Sn-Na三组分丙烷脱氢催化剂性能的影响[J].石油化工,2012,41(12):1346-1350.
[13] 黄镜怡,周钰明,唐梦涵,等.氟对PtSnNaLa/ZSM-5催化剂丙烷脱氢反应性能的影响[J].应用化学,2015,32(2):207-213.
[14] 刘杰,刘昌呈,马爱增,等.铂系丙烷脱氢催化剂助剂研究进展[J].石油学报(石油加工),2015,31(5):1218-1230.
[15] ZHANG Y,ZHOU Y,TANG M,et al.Effect of La calcination temperature on catalytic performance of PtSnNaLa/ZSM-5 catalyst for propane dehydrogenation[J].Chemical Engineering Journal,2012,181-182(1):530-537.
[16] FATHI S,SOHRABI M,FALAMAKI C.Improvement of HZSM-5 performance by alkaline treatments:comparative catalytic study in the MTG reactions[J].Fuel,2014,116:529-537.
[17] 于素霞.多级孔道结构ZSM-5沸石分子筛的合成及其催化应用[M].大连:大连理工大学,2009.
[18] 赵岑,刘冬梅,魏民,等.多级孔ZSM-5分子筛的制备及催化噻吩烷基化性能研究[J].燃料化学学报,2013,40(10):1256-1260.
[19] 常江伟,付廷俊,张洪建,等.碱处理浓度对预脱铝ZSM-5成孔过程及其MTG反应性能的影响[J].无机化学学报,2015,3(11):2119-2127.
[20] 王莹莹.Meso-ZSM-5的制备、表征及催化应用[D].北京:中国石油大学,2015.
[21] YANG S H,CUI Y D,CHEN X J,et al.Development of synthesis and surface modification of ZSM-5 zeolite molecular sieve[J].Advances in Fine Fetrochemicals,2003,4:47-50.
[22] 何霖,韩伟,谭亚南,等.用于甲醇合成丙烯的ZSM-5分子筛、制备方法及其应用:102259014A[P].2011-11-30.
[23] 余长林.丙烷脱氢铂催化剂与反应性能的研究[D].大连:中国科学院大连化学物理研究所,2007.
[24] ARMAROLI T,SIMON L J,DIGNE M,et al.Effects of crystal size and Si/Al ratio on the surface properties of HZSM-5 zeolites[J].Applied Catalyst A,2006,306(6):78-84.
[25] 张一卫,周钰明,邱安定,等.Na对PtSn/ZSM-5催化丙烷脱氢反应性能的影响[J].物理化学学报,2006,22(6):672-678.
[26] 轩庆鲁.丙烷脱氢PtSn催化剂中Pt分散度控制及对催化性能的影响[M].上海:华东理工大学,2013.

Preparation of hierarchical ZSM-5 zeolites treated by Na₂CO₃ and its catalytic performance for propane dehydrogenation to propylene

Na₂CO₃处理制备复合孔ZSM-5分子筛及其丙烷脱氢制丙烯的催化性能

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	YANG Jianping. PSE for feedstock consumption reduction in reaction system of HPPO plant [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 21-32.
[2]	WANG Fu'an. Consumption and emission reduction of the reactor of 300kt/a propylene oxide process [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 213-218.
[3]	WANG Xiaohan, ZHOU Yasong, YU Zhiqing, WEI Qiang, SUN Jinxiao, JIANG Peng. Synthesis and hydrocracking performance of Y molecular sieves with different crystal sizes [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4283-4295.
[4]	WANG Darui, SUN Hongmin, XUE Mingwei, WANG Yiyan, LIU Wei, YANG Weimin. Efficient synthesis of fully crystalline ZSM-5 zeolite catalyst by microwave method and its catalytic performance [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3582-3588.
[5]	REN Zhongyuan, HE Jinlong, YUAN Qing. Research progress on intercrystalline defects control and remediation technologies for zeolite membranes [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2454-2463.
[6]	WANG Zizong, LIU Gang, WANG Zhenwei. Progress and reflection on process intensification technology for ethylene/propylene production [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1669-1676.
[7]	CHANG Xiaoqing, PENG Donglai, LI Dongyang, ZHANG Yanwu, WANG Jing, ZHANG Yatao. Recent progress on mixed matrix membrane for efficient C₃H₆/C₃H₈ separation [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1961-1973.
[8]	LAI Huaidong, CHENG Deshu, WANG Jian, LUO Juxiang. Preparation and application of α-methyl styrene maleic anhydride copolymer microspheres immobilized β-cyclodextrin [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2038-2046.
[9]	NING Shuying, SU Yaxin, YANG Honghai, WEN Nini. Research progress on supported Cu-based zeolite catalysts for the selective catalytic reduction of NO _x with hydrocarbons [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1308-1320.
[10]	ZHANG Mengxu, WANG Hongqin, LI Jin, AN Nihong, DAI Yunsheng, QIAN Yin, SHEN Yafeng. Preparation of PtSn/MgAl₂O₄-sheet catalyst and its PDH reaction performance [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1365-1372.
[11]	ZHOU Hao, ZHANG Heng, WEN Nini, WANG Xurui, XU Lu, LI Wei, SU Yaxin. Preparation and de-NO _x performance of C₃H₆-SCR over Cu-SAPO-44 catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1373-1382.
[12]	HU Zhaoyan, ZHANG Jingxin, HE Yiliang. Catalytic pyrolysis of polypropylene plastics and product properties with Fe-loaded sludge biochar [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 631-640.
[13]	HUO Wentao, LIU Wen, YU Qiang, AN Jie, ZHU Xiangxue, QIN Yucai, LI Xiujie. Oligomerization of isobutene over MWW zeolite based catalysts [J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5205-5212.
[14]	SUN Yiming, RAN Baoqing, BIAN Wuxun, LIU Jinchao, YIN Shaoding, ZHAO Xipo. Preparation and process optimization of polypropylene wax solid-solid phase change material [J]. Chemical Industry and Engineering Progress, 2023, 42(1): 336-345.
[15]	LIU Shulin, YANG Na, ZHANG Longfei, SUN Yongli, JIANG Bin, XIAO Xiaoming, TANTAI Xiaowei, ZHANG Lyuhong. Al-doped Cu/SBA-15 catalysts for the hydrogenation of dimethyl adipate to 1,6-hexanediol [J]. Chemical Industry and Engineering Progress, 2023, 42(1): 289-296.