煅烧温度对ZnGaZrO x /SAPO-34催化性能的影响
收稿日期: 2023-04-24
网络出版日期: 2024-02-06
基金资助
贵州省自然科学基金项目(黔科合基础-ZK［2023］重点004);贵州省教育厅创新群体项目(黔教合KY字［2021］010);贵州大学实验室开放项目(SYSKF2023008)
Effect of calcination temperature on catalytic performance of ZnGaZrO x /SAPO-34
Received date: 2023-04-24
Online published: 2024-02-06
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。
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 . DOI: 10.19964/j.issn.1006-4990.2023-0233
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
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