Effect of alkali treatment on ZnZrOx/SAPO-34 bifunctional catalyst for catalytic synthesis of light olefins from syngas

被引:0
|
作者
Wang Y. [1 ]
Wang X. [1 ]
Xue Z. [1 ]
Mao D. [1 ]
机构
[1] School of Chemical and Environment Engineering, Shanghai Institute of Technology, Shanghai
基金
上海市自然科学基金;
关键词
alkali treatment; bifunctional catalyst; SAPO-34; zeolite; syngas to light olefins;
D O I
10.19906/j.cnki.JFCT.2023053
中图分类号
学科分类号
摘要
A bifunctional catalyst was prepared by physical mixing of ZnZrOx metal oxide and SAPO-34 zeolite for the one-step conversion of synthesis gas to light olefins (STO) reaction. The effects of triethylamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide solutions and different concentrations of triethylamine solution on the texture, structure and acidity of SAPO-34 zeolite were investigated. XRD, SEM, N2 adsorption and desorption, NH3-TPD were used to characterize the SAPO-34 zeolite and the STO reaction performance of the catalyst after alkali treatment was investigated. The results show that all three kinds of organic base with 0.06 mol/L post-treatment can etch some hierarchical channels on the surface of SAPO-34 zeolite, thus accelerating the diffusion of intermediate transition species formed on the surface of metal oxides into the channels of SAPO-34 zeolite in STO reaction, improving the CO conversion rate in STO reaction. At the same time, all three kinds of alkali treatments can reduce the acid amount and acid strength of SAPO-34 zeolite, thereby improving the selectivity for light olefins in the STO reaction. The treatment of SAPO-34 zeolite with 0.02-0.10 mol/L triethylamine resulted in the formation of hierarchical pores etched on the surface of SAPO-34 zeolite, which improved the conversion rate of CO in the STO reaction. Moreover, the acid strength and acidity of SAPO-34 zeolite treated with 0.02 and 0.06 mol/L triethylamine solutions decreased, inhibiting the formation of methane and the hydrogenation of light olefins. Therefore, as the concentration of alkali treatment gradually increased from 0, 0.02 to 0.06 mol/L, the selectivity for light olefins gradually increases. Under the reaction conditions of 400 ℃, 3.0 MPa and GHSV=3600 mL/(g·h), the CO conversion rate increased from 24.0% to 26.4%, and the selectivity of light olefins increased from 78.2% to 84.7% on the bifunctional catalyst composed of 0.06 mol/L triethylamine-treated SAPO-34 compared to untreated SAPO-34 zeolite, and the modified bifunctional catalyst had good catalytic stability. © 2024 Science Press. All rights reserved.
引用
收藏
页码:140 / 149
页数:9
相关论文
共 30 条
  • [1] ZHANG P, MENG F, LI X, Et al., Excellent selectivity for direct conversion of syngas to light olefins over a Mn-Ga oxide and SAPO-34 bifunctional catalyst, Catal Sci Technol, 9, 20, pp. 5577-5581, (2019)
  • [2] FONSECA N, DOS SANTOS L R M, CERQUEIRA H S, Et al., Olefins production from cracking of a Fischer-Tropsch naphtha, Fuel, 95, pp. 183-189, (2021)
  • [3] JOO E, PARK S, LEE M., Pyrolysis reaction mechanism for industrial naphtha cracking furnaces, Ind Eng Chem Res, 40, 11, pp. 2409-2415, (2001)
  • [4] GONG F, YANG Z, HONG C, Et al., Selective conversion of bio-oil to light olefins: Controlling catalytic cracking for maximum olefins[J], Bioresour Technol, 102, 19, pp. 9247-9254, (2011)
  • [5] AL-SHAMMARI A A, ALI S A, AL-YASSIR N, Et al., Catalytic cracking of heavy naphtha-range hydrocarbons over different zeolites structures, Fuel Process Technol, 122, pp. 12-22, (2014)
  • [6] LI Baozhen, MENG Fanhui, WANG Lina, Et al., Study on preparation and catalytic performance of Zn-Al oxides for tandem reaction of syngas conversion into light olefins, J Fuel Chem Technol, 51, 1, pp. 111-119, (2023)
  • [7] SU J, ZHOU H, LIU S, Et al., Syngas to light olefins conversion with high olefin/paraffin ratio using ZnCrO<sub>x</sub>/AlPO-18 bifunctional catalysts, Nat Commun, 10, 1, (2019)
  • [8] VAN DEELEN T W, HERNANDEZ MEJIA C, DE JONG K P., Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity, Nat Catal, 2, 11, pp. 955-970, (2019)
  • [9] LI S, LIU X, LU Y., Fischer-Trospch to olefins over hydrophobic FeMnO<sub>x</sub>@SiO<sub>2</sub> catalysts: The effect of SiO<sub>2</sub> shell content, Appl Catal A: Gen, 635, (2022)
  • [10] GONG K, LIN T, AN Y, Et al., Fischer-Tropsch to olefins over CoMn-based catalysts: Effect of preparation methods, Appl Catal A: Gen, 592, (2020)