煅烧温度对ZnGaZrO x /SAPO-34催化性能的影响

doi:10.19964/j.issn.1006-4990.2023-0233

摘要/Abstract

摘要：

在CO₂加氢制低碳烯烃（C₂⁼-C₄⁼）中，双功能催化剂的煅烧温度对其催化性能具有显著影响。基于此，采用共沉淀法制备了ZnGaZrO _x 氧化物，水热法制备了SAPO-34分子筛，然后对两者进行研磨制得ZnGaZrO _x /SAPO-34双功能催化剂，并考察煅烧温度对ZnGaZrO _x 和SAPO-34物化性质及催化性能的影响。通过XRD、XPS、H₂/CO₂/NH₃-TPD、SEM、N₂吸附-脱附和原位DRIFTS表征发现，在制备ZnGaZrO _x 过程中，当煅烧温度为650 ℃时，ZnGaZrO _x 具有最强的H₂和CO₂吸附活化能力，能有效提高HCOO*和CH₃O*的生成速率和浓度，促进甲醇产物生成；在制备SAPO-34过程中，当煅烧温度为450 ℃时，分子筛比表面积最大、晶粒尺寸最小、强酸位点的酸性最弱，能有效避免低碳烯烃发生二次加氢，从而获得较高的低碳烯烃选择性。最佳条件下合成的ZnGaZrO _x /SAPO-34双功能催化剂在反应温度为390 ℃、压力为3 MPa、空速为3 600 mL/（g∙h）条件下，CO₂转化率为28.3%，CO选择性仅为44.6%，C₂⁼-C₄⁼选择性为84.4%，C₂⁼-C₄⁼产率高达13.2%，且在反应100 h内催化性能无明显衰减。该工作为双功能催化剂的改性提供了新的研究思路。

关键词: CO₂加氢, 低碳烯烃, 煅烧温度, 氧空位, 酸性

Abstract:

In the hydrogenation of CO₂ to low-carbon olefins（C₂⁼-C₄⁼），the calcination temperature of the bifunctional catalyst has significant effects on its catalytic performance.Based on this，ZnGaZrO _x oxides were prepared by co-precipitation method and SAPO-34 molecular sieves were prepared by hydrothermal method，and then both of them were milled to produce ZnGaZrO _x /SAPO-34 bifunctional catalysts，and the effects of calcination temperature on the physicochemical properties and catalytic performance of ZnGaZrO _x and SAPO-34 were investigated.It was found by XRD，XPS，H₂/CO₂/NH₃-TPD，SEM，N₂ adsorption-desorption and in situ DRIFTS characterization that during the preparation of ZnGaZrO _x，when the calcination temperature was 650 ℃，ZnGaZrO _x had the strongest activation ability of H₂ and CO₂ adsorption，and it could effectively increase the rate and concentration of the generation of HCOO* and CH₃O* to promote the methanol product generation.During the preparation of SAPO-34，when the calcination temperature was 450 ℃，the molecular sieve had the largest specific surface area，the smallest grain size，and the weakest acidity of the strong acid site，which could effectively avoid the secondary hydrogenation of low-carbon olefins，thus obtaining higher selectivity of low-carbon olefins.The ZnGaZrO _x /SAPO-34 bifunctional catalysts synthesized under the optimal conditions showed a CO₂ conversion of 28.3%，a CO selectivity of only 44.6%，a C₂⁼-C₄⁼ selectivity of 84.4%，a C₂⁼-C₄⁼ yield of as high as 13.2% at a reaction temperature of 390 ℃，a pressure of 3 MPa，and an airspeed of 3 600 mL/（g∙h）.And the catalytic performance did not decay significantly within 100 h of reaction.This work provided a new research idea for the modification of bifunctional catalysts.

Key words: CO₂ hydrogenation, light olefins, calcination temperature, oxygen vacancy, acidity

中图分类号:

TQ426

杨坤, 任启霞, 董永刚, 刘飞, 姚梦琴, 曹建新. 煅烧温度对ZnGaZrO _x /SAPO-34催化性能的影响[J]. 无机盐工业, 2024, 56(2): 136-145.

YANG Kun, REN Qixia, DONG Yonggang, LIU Fei, YAO Mengqin, CAO Jianxin. Effect of calcination temperature on catalytic performance of ZnGaZrO _x /SAPO-34[J]. Inorganic Chemicals Industry, 2024, 56(2): 136-145.

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催化剂	D_size/nm	S_BET/（m^2.g^-1）	V_mirco/（cm^3.g^-1）	d_size/nm
SAPO-34-450 ℃	30.4	570	0.281	1.98
SAPO-34-550 ℃	33.0	566	0.280	2.00
SAPO-34-650 ℃	34.6	535	0.267	1.96

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