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Fe/BN催化剂的制备及其费托合成性能
Preparation of Fe/BN catalysts and their catalytic performance in Fischer-Tropsch synthesis
- 低碳化学与化工 2024, 49(2): 26-34.
- 作者机构：
1.中国石油化工股份有限公司石油化工科学研究院，北京 100083
2.中国石油化工股份有限公司茂名分公司，广东 茂名 525000
3.安徽大学 化学化工学院，安徽 合肥 230601
4.中国科学院 山西煤炭化学研究所 煤炭高效低碳利用全国重点实验室，山西 太原 030001
- 作者简介：
王宪周（1990—），博士，工程师，研究方向为有机化工和精细化工，E-mail：wangxzh235.mmsh@sinopec.com。
张成华（1975—），博士，正高级工程师，研究方向为工业催化，E-mail：zhangchh@sxicc.ac.cn。
- 基金信息：国家自然科学基金(22179001;91545109)
DOI：10.12434/j.issn.2097-2547.20230319
中图分类号： TQ517.4;O622.1纸质出版日期：2024-02-25，
收稿日期：2023-09-19，
修回日期：2023-10-26，
- 稿件说明：
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王宪周,张成华,相宏伟.Fe/BN催化剂的制备及其费托合成性能[J].低碳化学与化工,2024,49(02):26-34.
WANG Xianzhou,ZHANG Chenghua,XIANG Hongwei.Preparation of Fe/BN catalysts and their catalytic performance in Fischer-Tropsch synthesis[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):26-34.
王宪周,张成华,相宏伟.Fe/BN催化剂的制备及其费托合成性能[J].低碳化学与化工,2024,49(02):26-34. DOI： 10.12434/j.issn.2097-2547.20230319.
WANG Xianzhou,ZHANG Chenghua,XIANG Hongwei.Preparation of Fe/BN catalysts and their catalytic performance in Fischer-Tropsch synthesis[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):26-34. DOI： 10.12434/j.issn.2097-2547.20230319.
摘要
为开发基于高热传导性载体的催化剂，提高费托合成反应性能，以高比表面积的球磨氮化硼（BN）为载体，通过溶剂热法（溶剂热温度分别为120 ℃、160 ℃和200 ℃）制备了系列Fe/BN催化剂（Fe/BN-120、Fe/BN-160和Fe/BN-200），并研究了催化剂对费托合成的催化性能（温度为280 ℃、压力为2.0 MPa、合成气
V
(H
2
):
V
(CO):
V
(Ar) = 16:
8:1且空速为3000 mL/(g·h)，以48 h时的反应结果计）。采用N
2
吸/脱附、电感耦合等离子体-原子发射光谱（ICP-AES）、X-射线衍射（XRD）、透射电子显微镜（TEM）、X-射线电子能谱（XPS）和H
2
/CO程序升温还原（H
2
/CO-TPR）等对催化剂进行了表征。结果表明，与Fe/BN-120相比，Fe/BN-160、Fe/BN-200中
γ
-Fe
2
O
3
的平均粒径分别由7.2 nm增加至13.6 nm、14.7 nm，同时Fe 2p结合能逐渐向低结合能方向偏移。与Fe/BN-120和Fe/BN-160相比，在电子效应和尺寸效应的作用下，Fe/BN-200的还原、碳化得到明显促进。在费托合成的CO
2
和H
2
O气氛中，还原得到的
α
-Fe、Fe
3
O
4
和球磨氮化硼表面的BO
x
在高温条件下发生反应生成硼酸铁。随着溶剂热温度的升高，催化剂的碳化程度逐渐升高，与Fe/BN-120相比（CO转化率为39.1%、CH
4
选择性为24.3%和C
5+
选择性为37.8%），Fe/BN-200的CO转化率提高至68.9%，CH
4
选择性降至12.9%，C
5+
选择性增加至51.1%。在Fe/BN催化剂上，通过改变溶剂热温度可以调控催化活性和产物分布，这为提高氮化硼负载的Fe基催化剂的费托合成反应性能提供了思路。
Abstract
In order to develop catalysts based on high thermal conductivity support and improve the performance of Fischer-Tropsch synthesis
ball milling boron nitride (BN) with high specific surface area was used as support to prepare a series of Fe/BN catalysts (Fe/BN-120
Fe/BN-160 and Fe/BN-200) by solvothermal method (solvothermal temperatures are 120 ℃
160 ℃ and 200 ℃
respectively)
and their catalytic performance in Fischer-Tropsch synthesis was studied (temperature of 280 ℃
pressure of 2.0 MPa
V
(H
2
):
V
(CO):
V
(Ar) = 16:8:1 and space velocity of 3000 mL/(g·h) of syngas
measured by the reaction result at 48 h). The catalysts were characterized by N
2
absorption/desorption
inductively coupled plasma-atomic emission spectrometer (ICP-AES)
X-ray diffraction (XRD)
transmission electron microscopy (TEM)
X-ray photoelectron spectroscopy (XPS) and H
2
/CO temperature programmed reduction (H
2
/CO-TPR). The results show that compared with Fe/BN-120
the average particle size of
γ-
Fe
2
O
3
in Fe/BN-160 and Fe/BN-200 increases from 7.2 nm to 13.6 nm and 14.7 nm
respectively
a
nd the binding energy of Fe 2p gradually shifts towards the lower binding energy. Compared with Fe/BN-120 and Fe/BN-160
the reduction and carbonization of Fe/BN-200 are significantly promoted under the action of electronic effect and size effect. In the atmosphere of CO
2
and H
2
O in Fischer-Tropsch
the reduced
α-
Fe and Fe
3
O
4
react with the BO
x
on the surface of ball milling boron nitride under high temperature conditions to produce iron borate. With the increase of solvothermal temperature
the carbonization degree of catalyst increases gradually. Compared with Fe/BN-120 (CO conversion rate is 39.1%
CH
4
selectivity is 24.3%
C
5+
selectivity is 37.8%)
CO conversion rate of Fe/BN-200 increases to 68.9%
CH
4
selectivity decreases to 12.9% and C
5+
selectivity increased to 51.1%. The catalytic activity and product distribution can be regulated by changing the solvothermal temperature on Fe/BN catalyst
which provides a way to improve the performance of Fe-based catalyst supported by boron nitride.
关键词
费托合成铁基催化剂氮化硼溶剂热法催化活性
Keywords
Fischer-Tropsch synthesisiron-based catalystboron nitridesolvothermal methodcatalytic activity
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