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PFTS改性Fe3O4@SiO2催化剂对费托合成产物分布的影响
Effect of PFTS modified Fe3O4@SiO2 catalysts on product distribution in Fischer-Tropsch synthesis
- 低碳化学与化工 2025, 50(5): 93-100.
- 作者机构：
1.宁夏大学 化学化工学院 省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏 银川 750021
2.宁夏大学 材料与新能源学院，宁夏 银川 750021
- 作者简介：
张雪建（2001—），硕士研究生，研究方向为CO加氢定向转化，E-mail：zxj010804@163.com。
王康洲（1992—），博士，副教授，研究方向为低碳资源催化转化，E-mail：kangzhou_wang@163.com；
张建利（1980—），博士，研究员，研究方向为碳一化学，E-mail：zhangjl@nxu.edu.cn。
- 基金信息：国家自然科学基金(22368041);中央引导地方科技发展专项(2023FRD05030)
DOI：10.12434/j.issn.2097-2547.20240400
中图分类号： TQ426收稿日期：2024-09-26，
修回日期：2024-10-26，
纸质出版日期：2025-05-25
- 稿件说明：
移动端阅览
张雪建,王舜,张帅等.PFTS改性Fe3O4@SiO2催化剂对费托合成产物分布的影响[J].低碳化学与化工,2025,50(05):93-100.
ZHANG Xuejian,WANG Shun,ZHANG Shuai,et al.Effect of PFTS modified Fe3O4@SiO2 catalysts on product distribution in Fischer-Tropsch synthesis[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(05):93-100.
张雪建,王舜,张帅等.PFTS改性Fe3O4@SiO2催化剂对费托合成产物分布的影响[J].低碳化学与化工,2025,50(05):93-100. DOI： 10.12434/j.issn.2097-2547.20240400.
ZHANG Xuejian,WANG Shun,ZHANG Shuai,et al.Effect of PFTS modified Fe3O4@SiO2 catalysts on product distribution in Fischer-Tropsch synthesis[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(05):93-100. DOI： 10.12434/j.issn.2097-2547.20240400.
摘要
经费托合成路线，通过CO加氢制取高附加值化学品是实现煤炭清洁高效利用的重要途径之一。然而在生成烃类的同时，会副产大量的H
2
O。H
2
O氧化活性中心导致反应速率降低，同时会促进水煤气变换（WGS）反应正向进行，产生大量CO
2
，碳利用效率降低。且费托合成产物中初级烯烃易再吸附发生二次加氢反应，导致烯烃选择性下降。基于费托合成产物分布的特点，通过调节Fe基催化剂的表面亲疏性，可以实现对产物的调控。采用溶剂热法、Stöber法制备了不同壳层厚度的Fe
3
O
4
@SiO
2
催化剂并以全氟癸基三乙氧基硅烷（PFTS）为改性剂制备了具有疏水疏油（以下简称“双疏”）性质的Fe
3
O
4
@SiO
2
-3-PFTS催化剂，探究了表面壳层厚度和双疏改性对催化剂活性和产物分布的影响。采用SEM、TEM、FT-IR、XRD和H
2
-TPR等方法对催化剂进行了表征，并在300 ℃、1.5 MPa、气体空速3000 h
-1
、
V
(H
2
):
V
(CO) ＝ 2:1条件下进行了催化剂催化性能测试。结果表明，制备的催化剂核壳结构完整，壳层厚度均匀，Fe
3
O
4
@SiO
2
-3-PFTS催化剂具备良好的双疏性。随着SiO
2
壳层厚度增大，初级烯烃二次加氢反应增强，显著抑制了重烃生成，碳原子数为2~4的烷烃（
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3.21733332
~
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）选择性从21.5%（Fe
3
O
4
）增大至46.8%（Fe
3
O
4
@SiO
2
-3），碳原子数大于等于5的烃（C
5+
）选择性从47.7%（Fe
3
O
4
）减小至21.5%（Fe
3
O
4
@SiO
2
-3）。Fe
3
O
4
@SiO
2
-3-PFTS催化剂抑制了WGS反应正向进行以及初级烯烃二次加氢反应，反应12 h后CO
2
选择性为14.2%，碳原子数为2~4的烯烃（C
2
=~C
4
=）选择性为19.7%，C
2
~
C
4
产物烯烷选择性比为0.68，产物分布得到了调控。
Abstract
One of important ways to achieve clean and efficient utilization of coal is through Fischer-Tropsch synthesis (FTS) to prepare high value-added chemicals via CO hydrogenation. However
while generating hydrocarbons
a large amount of H
2
O is also produced as by-product. H
2
O will oxidize the active center
leading to a decrease in reaction rate
and promote the water gas shift (WGS) reaction
generating a large amount of CO
2
and reducing the efficiency of carbon utilization. At the same time
the primary olefins in the FTS products are easy to be re-adsorbed for secondary hydrogenation reactions
decreasing the selectivity of olefins. Based on the characteristics of the FTS product distribution
the control of products can be achieved by adjusting the surface hydrophilicity of Fe-based catalysts. Fe
3
O
4
@SiO
2
catalysts with different shell thicknesses were produced by solvothermal me
thod and Stöber methods
and Fe
3
O
4
@SiO
2
-3-PFTS catalyst with hydrophobic and oleophobic (hereinafter referred to as “amphiphobic”) properties were prepared by perfluorodecyltriethoxysilane (PFTS) as a modifier. The effects of the shell thickness and amphiphobic modification on the catalyst activity and FTS product distribution were investigated. The catalysts were characterized by SEM
TEM
FT-IR
XRD
H
2
-TPR and so on
and their catalytic performances were tested under the conditions of 300 ℃
1.5 MPa
gas space velocity of 3000 h
-1
and
V
(H
2
):
V
(CO) = 2:1. The results show that the prepared catalysts have complete core-shell structures and uniform shell thickness. Fe
3
O
4
@SiO
2
-3-PFTS catalyst exhibits good amphiphobic properties. With the increase of the thickness of SiO
2
shell layer
the secondary hydrogenation reaction of primary olefins is enhanced
and the generation of heavy hydrocarbons is significantly inhibited. The selectivity of alkanes with two to four carbon atoms (
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~
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) increases from 21.5% (Fe
3
O
4
) to 46.8% (Fe
3
O
4
@SiO
2
-3)
and the selectivity of hydrocarbons with five or more carbon atoms (C
5+
) decreases from 47.7% (Fe
3
O
4
) to 21.5% (Fe
3
O
4
@SiO
2
-3). Fe
3
O
4
@SiO
2
-3-PFTS catalyst inhibits the WGS reaction and secondary hydrogenation of primary olefins. After reaction for 12 h
the selectivity of CO
2
is 14.2%
and the selectivity of olefins with two to four carbon atoms (C
2
=~C
4
=) is 19.7%
and selectivity ratio of olefins and alkanes in C
2
~C
4
products is 0.68. The product distribution is regulated.
关键词
Keywords
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