催化剂表面Cu0含量对二氧化碳加氢合成C2+醇性能的影响

doi:10.7503/cjcu20200061

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (6): 1297.doi: 10.7503/cjcu20200061

催化剂表面Cu⁰含量对二氧化碳加氢合成C₂₊醇性能的影响

张维中¹,温月丽^1,^*(),宋镕鹏¹,王斌²,张倩¹,黄伟^2,^*()

^1. 太原理工大学环境科学与工程学院, 太原 030024
^2. 煤科学与技术教育部和山西省重点实验室, 太原 030024

收稿日期:2020-02-05 出版日期:2020-06-10 发布日期:2020-03-17
通讯作者: 温月丽,黄伟 E-mail:wenyueli@tyut.edu.cn;huangwei@tyut.edu.cn
基金资助:
国家科技支撑计划项目(2013BAC14B04);国家自然科学基金(21336006);山西省重点研发计划项目(201803D421099);山西省重点研发计划项目(201803D121043);山西省留学基金委资助项目(2017-035)

Effect of Surface Cu⁰ Content of the Catalysts on CO₂ Hydrogenation to C₂₊ Alcohols ^†

ZHANG Weizhong¹,WEN Yueli^1,^*(),SONG Rongpeng¹,WANG Bin²,ZHANG Qian¹,HUANG Wei^2,^*()

^1. College of Environmental Science and Engineering, Taiyuan 030024, China
^2. Key Laboratory of Coal Science and Technology of Education Ministry and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China

Received:2020-02-05 Online:2020-06-10 Published:2020-03-17
Contact: Yueli WEN,Wei HUANG E-mail:wenyueli@tyut.edu.cn;huangwei@tyut.edu.cn
Supported by:
† National Key Technology Research & Development Program, China(2013BAC14B04);National Natural Science Foundation of China(21336006);Shanxi Province Key Research & Development Program, China(201803D421099);Shanxi Province Key Research & Development Program, China(201803D121043);Research Project Supported by Shanxi Scholarship Council of China(2017-035)

摘要/Abstract

摘要：

通过在空气气氛下焙烧Cu@Fe-MIL-88B MOF材料制备了CuFe组分均匀分散的催化剂前驱物, 该前驱物经过不同温度下的预还原制得表面具有不同Cu和Fe价态分布的系列催化剂. 将所制备的催化剂用于固定床反应器上CO₂加氢合成C₂₊醇的性能研究, 并结合催化剂的X射线衍射(XRD)、 X射线光电子能谱(XPS)、氢气程序升温还原(H₂-TPR)、氮气吸附-脱附、扫描电子显微镜(SEM) 和高分辨率透射电子显微镜(HRTEM)等表征结果发现, 较高的还原温度增加了催化剂表面低价态的Cu和Fe的含量; 当还原温度为350 ℃时, 催化剂表面Cu⁰/(Cu⁺+Cu⁰)摩尔比为73.9%, 单质Fe摩尔分数为0.40%, 催化效果最好, CO₂转化率达到6.82%, 总醇选择性为39.4%, 其中C₂₊醇的摩尔比达到95.1%.

关键词: Fe-MIL-88B, 铜铁催化剂, 还原温度, 低碳醇, 二氧化碳加氢

Abstract:

Pyrolyzing metal organic framework(MOF) material Fe-MIL-88B loaded with Cu in air atmosphere, uniformly dispersed CuFe based catalysts with different Cu and Fe valence distribution were gained at different reduction temperatures. The structure of the catalysts were characterized by means of X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), H₂ temperature program reduction(H₂-TPR), N₂ adsorption-desorption(BET), scanning electron microscopy(SEM), and high resolution transmission electron microscopy(HRTEM). The catalytic performances of CO₂ hydrogenation to C₂₊ alcohols were investigated on a fixed-bed reactor. It was found that the higher the reduction temperature was, the more percentage of Cu and Fe with lower valence state was on the surface of the catalysts. When the reduction temperature was 350 ℃, Cu⁰/(Cu⁺+Cu⁰) was 73.9 %, and 0.4% Fe ⁰ appeared, the catalytic performance was the best, where the CO₂ conversion rate was 6.82%, the total alcohol selectivity was 39.4%, and the molar percentage of C₂₊ alcohol was 95.1%.

Key words: Fe-MIL-88B, CuFe Catalyst, Reduction temperature, C₂₊ Alcohol, CO₂ Hydrogenation

中图分类号:

O643.3

TrendMD:

张维中,温月丽,宋镕鹏,王斌,张倩,黄伟. 催化剂表面Cu⁰含量对二氧化碳加氢合成C₂₊醇性能的影响. 高等学校化学学报, 2020, 41(6): 1297.

ZHANG Weizhong,WEN Yueli,SONG Rongpeng,WANG Bin,ZHANG Qian,HUANG Wei. Effect of Surface Cu⁰ Content of the Catalysts on CO₂ Hydrogenation to C₂₊ Alcohols ^†. Chem. J. Chinese Universities, 2020, 41(6): 1297.

图/表 9

Fig.1 XRD patterns of the R-N and R-T series of catalysts

Fig.2 HRTEM images of R-N(A) and R-350(B—D)

Fig.3 STEM images of R-N(A) and R-350(E) and corresponding of elemental mapping images of Cu(B, F), Fe(C, G), O(D, H) of R-N(A—D) and R-350(E—H)

Fig.4 N2 adsorption and desorption isotherms curve(A) and pore size distributions(B) of R-N and R-T catalysts

Fig.5 XPS spectra of Fe2p(A) and Cu2p(B), and Cu LMM XAES(C) for R-N and R-T series of catalysts

Table 1 Percentage of copper and iron species in R-T series of catalysts derived from peak fittings of Cu LMM XAES and Fe2p XPS

Catalyst	Surface molar fraction(%)
Catalyst	Cu⁺	Cu⁰	Fe³⁺	Fe²⁺	Fe or Fe₃C
R-250	34.4	65.6	48.6	51.4	——
R-350	26.1	73.9	46.5	53.1	0.4
R-450	28.3	71.7	41.2	55.1	3.7

Fig.6 Catalytic performance of R-T series of catalysts (A) Products selectivity; (B) alcohols selectivity; (C) alcohol STY of R-T. (A) ROH means total alcohol, C1OH, C2OH, C3OH, C4OH refer to methanol, ethanol, propanol, butanol, respectively.

Table 2 Distribution(%) of C1—C4 alcohols

Catalyst	C₁OH	C₂OH	C₃OH	C₄OH
R-N	5.48	62.8	16.1	15.6
R-250	3.71	56.6	16.7	23.0
R-350	4.94	61.5	22.3	11.3
R-450	5.80	59.3	13.0	21.9

Fig.7 XRD patterns of A-N and A-T series of catalysts

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催化剂表面Cu⁰含量对二氧化碳加氢合成C₂₊醇性能的影响

Effect of Surface Cu⁰ Content of the Catalysts on CO₂ Hydrogenation to C₂₊ Alcohols ^†

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