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造孔剂诱导合成FeCoCuAl催化剂及其与ZSM-5复合催化CO2加氢制高碳烃性能
Pore-forming agent induced synthesis of FeCoCuAl catalysts and their performance in hydrogenation of CO2 to high carbon hydrocarbons with ZSM-5
- 低碳化学与化工 2024, 49(2): 10-16.
- 作者机构：
成都信息工程大学 资源环境学院 大气环境模拟与污染控制四川省高校重点实验室，四川 成都 610225
- 作者简介：
赵治华（1997—），硕士研究生，研究方向为环境催化和大气污染控制，E-mail：1427085223@qq.com。
徐成华（1972—），博士，教授，研究方向为环境催化和大气污染控制，E-mail：xch@cuit.edu.cn。
- 基金信息：四川省科技厅自然科学基金(2022NSFSC1058);四川省科技厅国际合作项目(2020YFH0133)
DOI：10.12434/j.issn.2097-2547.20230234
中图分类号： TQ426;X51纸质出版日期：2024-02-25，
收稿日期：2023-06-30，
修回日期：2023-07-25，
- 稿件说明：
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赵治华,徐成华,任红等.造孔剂诱导合成FeCoCuAl催化剂及其与ZSM-5复合催化CO2加氢制高碳烃性能[J].低碳化学与化工,2024,49(02):10-16.
ZHAO Zhihua,XU Chenghua,REN Hong,et al.Pore-forming agent induced synthesis of FeCoCuAl catalysts and their performance in hydrogenation of CO2 to high carbon hydrocarbons with ZSM-5[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):10-16.
赵治华,徐成华,任红等.造孔剂诱导合成FeCoCuAl催化剂及其与ZSM-5复合催化CO2加氢制高碳烃性能[J].低碳化学与化工,2024,49(02):10-16. DOI： 10.12434/j.issn.2097-2547.20230234.
ZHAO Zhihua,XU Chenghua,REN Hong,et al.Pore-forming agent induced synthesis of FeCoCuAl catalysts and their performance in hydrogenation of CO2 to high carbon hydrocarbons with ZSM-5[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):10-16. DOI： 10.12434/j.issn.2097-2547.20230234.
摘要
CO
2
加氢制高碳烃（C
5+
）是合成高值化学品和燃料的重要途径之一，这既可以实现碳减排，又有助于缓解能源压力。采用沉淀法和等体积浸渍法制备了K、Na修饰的FeCoCuAl催化剂，考察了造孔剂1
3
5-苯三甲酸（BTA）对其在CO
2
催化加氢制高碳烃反应（温度为300 ℃、压力为2.0 MPa、原料气
n
(H
2
):
n
(CO
2
) = 3:1且空速为3600 h
-1
、时间为6 h）中催化性能的影响。在FeCoCuAl-20.0BTA催化剂（
n
(BTA):
n
(Fe) = 20.0%）中引入ZSM-5分子筛，构建了一系列复合催化剂，并研究了其在CO
2
催化加氢制高碳烃反应中的催化性能。结合N
2
吸/脱附、X射线衍射（XRD）、H
2
-程序升温还原（H
2
-TPR）、CO
2
程序升温脱附（CO
2
-TPD）和H
2
升温脱附（CO
2
-TPD）等对催化剂的理化性质进行了表征，采用GC-MS对产物油相成分进行了分析。结果表明，与FeCoCuAl催化剂相比，FeCoCuAl-BTA催化剂的比表面积、孔容等均增大，并生成了更多的表面活性物种（Fe或Fe-Co合金），从而使得FeCoCuAl-BTA催化剂在CO
2
催化加氢反应中表现出更好的催化性能。FeCoCuAl-20.0BTA催化剂的CO
2
转化率和C
5+
选择性分别可达70%和42%。FeCoCuAl-20.0BTA催化剂催化CO
2
加氢生成的产物以C
2
~C
4
产物为主，而在FeCoCuAl-20.0BTA催化剂与ZSM-5分子筛以质量比为1.0、颗粒机械混合方式构建的复合催化剂上，FeCoCuAl-20.0BTA上生成的C
2
~C
4
产物可在ZSM-5分子筛上发生原位链增长、异构化和芳构化反应，从而提高了CO
2
转化率和C
5+
选择性，分别达到79%和66%。
Abstract
CO
2
hydrogenation to high-carbon hydrocarbons (C
5+
) is one of the important ways to synthesize high-value chemicals and fuels
which can achieve carbon emission reduction as well as help to alleviate energy pressure. K- and Na-modified FeCoCuAl catalysts were prepared by precipitation and iso-volumetric impregnation methods
and the effects of the pore-forming agent 1
3
5-benzenetricarboxylic acid (BTA) on their catalytic performance in CO
2
-catalyzed hydrogenation to high-carbon hydrocarbons reaction(temperature of 300 ℃
pressure of 2.0 MPa
n
(H
2
):
n
(CO
2
) = 3:1 and space velocity of 3600 h
-1
of feed gas
reaction for 6 h) were investigated. ZSM-
5 molecular sieve was introduced into FeCoCuAl-20.0BTA catalyst (
n
(BTA):
n
(Fe) = 20.0%) to construct a series of composite catalysts and their catalytic performance in the reaction of catalytic hydrogenation of CO
2
to high-carbon hydrocarbons was investigated. The physicochemical properties of the catalysts were characterized by combining N
2
adsorption/desorption
X ray diffraction (XRD)
H
2
-temperature programmed reduction (H
2
-TPR)
CO
2
temperature programmed desorption (CO
2
-TPD)
and H
2
temperature programmed desorption (CO
2
-TPD)
and the oil-phase compositions of the products were analyzed by GC-MS. The results show that compared with FeCoCuAl catalysts
the specific surface area and pore volume of FeCoCuAl-BTA catalysts increase
and generate more surface-active species (Fe or Fe-Co alloy)
which lead to better catalytic performance of FeCoCuAl-BTA catalysts in CO
2
catalytic hydrogenation reaction. The CO
2
conversion rate and C
5+
selectivity of FeCoCuAl-20.0BTA catalyst are up to 70% and 42%
respectively
and the products generated from CO
2
hydrogenation catalyzed by FeCoCuAl-20.0BTA catalyst are mainly C
2
~C
4
products
while on the composite catalyst constructed with FeCoCuAl-20.0BTA catalyst and ZSM-5 molecular sieve in the form of mechanical mixing of particles with the mass ratio of 1.0
the C
2
~C
4
products generated on FeCoCuAl-20.0BTA can undergo in situ chain growth
isomerization and aromatization reactions on ZSM-5 molecular sieves
which lead to the improvement of CO
2
conversion rate and C
5+
selectivity
reaching 79% and 66%
respectively.
关键词
造孔剂FeCoCuAl催化剂ZSM-5CO2加氢高碳烃
Keywords
pore-forming agentFeCoCuAl catalystsZSM-5CO2 hydrogenationhigh-carbon hydrocarbons
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