EDTA辅助制备高活性费托合成催化剂

doi:10.16085/j.issn.1000-6613.2021-0522

化工进展 ›› 2022, Vol. 41 ›› Issue (2): 759-769.DOI: 10.16085/j.issn.1000-6613.2021-0522

EDTA辅助制备高活性费托合成催化剂

赵潇(), 陈中顺, 唐忠强, 石轩, 代成义(), 马晓迅()

西北大学化工学院，国家碳氢资源清洁利用国际科技合作基地，陕北能源先进化工利用技术教育部工程研究中心，陕西省洁净煤转化工程技术研究中心，陕北能源化工产业发展协同创新中心，陕西西安 710069

收稿日期:2021-03-15 修回日期:2021-05-21 出版日期:2022-02-05 发布日期:2022-02-23
通讯作者: 代成义,马晓迅
作者简介:赵潇（1995—），男，硕士研究生，研究方向为合成气转化。E-mail：1421274879@qq.com。
基金资助:
国家重点研发计划(2018YFB0604901);国家自然科学基金(21706210)

EDTA-assisted preparation of highly active catalysts for Fischer-Tropsch synthesis

ZHAO Xiao(), CHEN Zhongshun, TANG Zhongqiang, SHI Xuan, DAI Chengyi(), MA Xiaoxun()

School of Chemical Engineering, Northwest University, International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Shanbei Energy and Chemical Industry Development, Xi’an 710069, Shaanxi, China

Received:2021-03-15 Revised:2021-05-21 Online:2022-02-05 Published:2022-02-23
Contact: DAI Chengyi,MA Xiaoxun

摘要/Abstract

摘要：

费托合成（FTS）对天然气、煤炭和生物质向清洁运输燃料和增值化学品的转化至关重要。传统上，用于FTS的负载型铁催化剂主要是以氧化铝和二氧化硅为载体。然而，金属与载体的相互作用阻碍了活性相碳化铁的形成，使得催化剂活性较低。本文通过乙二胺四乙酸（EDTA）络合浸渍制备了Fe/Al₂O₃催化剂，通过带正电荷的羟基（OH $2 +$ ）与[Fe(EDTA)]^-配合物阴离子之间的库仑相互作用来提高氧化铝载体上铁物种的分散度。采用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、比表面积（BET）、原位红外（In-situ IR）等手段进行表征分析。结果表明，添加EDTA有助于增强Fe的抗烧结性。在煅烧络合浸渍制备样品的过程中，EDTA可以分解为具有还原性质的有机小分子，将催化剂中的铁物种还原为Fe²⁺，有利于催化剂的还原；更多活性中心增强了催化剂对CO的吸附量。原位红外实验表明，EDTA辅助制备的催化剂更容易富集活性物种，从而提高CO的转化率。调节体系中碱金属钠的含量改善了烃内产物分布。在较低的氢碳比（H₂/CO=1/1）下，EDTA络合制备的Fe-Na/Al₂O₃催化剂显示出高的CO转化率（88.5%）以及最大的C₂~C₄=和C₅~C₁₁选择性，总选择性达71.2%。

关键词: 固定床, 合成气, 费托合成, 催化剂, 碳氢化合物, 乙二胺四乙酸

Abstract:

Fischer-Tropsch synthesis (FTS) is crucial for the conversion of natural gas, coal and biomass to clean fuels and value-added chemicals. Traditionally, the iron catalysts for FTS are mainly supported on alumina and silica. However, the interaction between metal and support hindered the formation of active phase iron carbide, resulting in low activity of the catalyst. In this study, Fe/Al₂O₃ catalyst was prepared by EDTA complex impregnation and the dispersion of iron species on alumina support was improved by coulomb interaction between positively charged hydroxyl (OH₂⁺) and [Fe(EDTA)]^- complex anion. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), specific surface area (BET), in situ infrared (in-situ IR) and other means were used. The results showed that the addition of EDTA could enhance the sintering resistance of Fe. In the calcining process, EDTA can be decomposed into small organic molecules, which can reduce the iron species in the catalyst to Fe²⁺ and thus is conducive to the reduction of the catalyst. Besides, more active centers enhanced the CO adsorption capacity of the catalyst. In-situ IR experiments showed that the catalyst prepared with EDTA enriched the active species easier, which improved the conversion of CO. The product distribution in hydrocarbons was improved by adjusting the content of alkali metal sodium in the system. The Fe-Na/Al₂O₃ catalyst prepared by EDTA complexation showed high CO conversion (88.5%) and high selectivity of C₂~C $4 =$ and C₅~C₁₁ (total of 71.2%) at a low hydrogen carbon ratio (H₂/CO=1/1).

Key words: fixed-bed, syngas, Fischer-Tropsch synthesis, catalyst, hydrocarbons, EDTA

中图分类号:

O643.3

赵潇, 陈中顺, 唐忠强, 石轩, 代成义, 马晓迅. EDTA辅助制备高活性费托合成催化剂[J]. 化工进展, 2022, 41(2): 759-769.

ZHAO Xiao, CHEN Zhongshun, TANG Zhongqiang, SHI Xuan, DAI Chengyi, MA Xiaoxun. EDTA-assisted preparation of highly active catalysts for Fischer-Tropsch synthesis[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 759-769.

图/表 22

表1 样品代码和意义

样本代码	Fe/mol	EDTA/mol	EDTA-2Na/mol	NaNO₃/mol
10Fe/Al₂O₃	M	0	0	0
10Fe2.5E/Al₂O₃	M	0.25M	0	0
10Fe5E/Al₂O₃	M	0.5M	0	0
10Fe7.5E/Al₂O₃	M	0.75M	0	0
10Fe10E/Al₂O₃	M	M	0	0
10Fe10Na/Al₂O₃	M	0	0	M
10Fe10E5Na/Al₂O₃	M	0.75M	0.25M	0
10Fe5E10Na/Al₂O₃	M	0	0.5M	0
10Fe7.5E10Na/Al₂O₃	M	0.25M	0.5M	0
10Fe10E10Na/Al₂O₃	M	0.5M	0.5M	0
10Fe10E15Na/Al₂O₃	M	0.25M	0.75M	0
10Fe10E20Na/Al₂O₃	M	0	M	0

图1 EDTA辅助制备催化剂的示意图

表2 浸渍溶液的pH

催化剂	水溶液	pH
10Fe/Al₂O₃	Fe（NO₃）₃	0.02
10Fe10E/Al₂O₃	Fe（NO₃）₃+EDTA	-0.63
10Fe10Na/Al₂O₃	Fe（NO₃）₃+NaNO₃	0.01
10Fe10E10Na/Al₂O₃	Fe（NO₃）₃+EDTA+EDTA-2Na	-0.62

图2 Fe与EDTA摩尔比对CO加氢反应性能的影响

图3 10FexEyNa/Al2O3催化剂的XRD图谱

图4 10Fe/Al2O3和10Fe10E/Al2O3催化剂反应后的TEM图

图5 10Fe/Al2O3与10Fe10E/Al2O3催化剂在8h内的CO转化率

图6 10FexE/Al2O3催化剂的化学吸附

表3 10FexE/Al2O3催化剂的CO吸附量

催化剂	CO吸附量/μmol·g^-1
10Fe/Al₂O₃	1.44
10Fe2.5E/Al₂O₃	1.45
10Fe5E/Al₂O₃	1.55
10Fe7.5E/Al₂O₃	1.62
10Fe10E/Al₂O₃	1.71

图7 Fe、EDTA和Na摩尔比对CO加氢反应性能的影响

表4 10FexE10Na/Al2O3催化剂对CO加氢的催化性能

催化剂	CO转化率/%	CO₂选择性/%	烃类选择性/%					总选择性/%	O/P
催化剂	CO转化率/%	CO₂选择性/%	CH₄	C₂~C $40$	C₂~C $4 =$	C₅~C₁₁	C $12 +$	总选择性/%	O/P
10Fe10Na/Al₂O₃	56.5	36.4	11.2	6.0	25.8	43.8	13.2	69.6	4.3
10Fe5E10Na/Al₂O₃	73.5	39.9	11.7	4.6	23.8	46.1	13.8	69.9	5.2
10Fe7.5E10Na/Al₂O₃	77.6	34.7	10.9	6.1	23.1	44.8	15.1	67.9	3.8
10Fe10E10Na/Al₂O₃	88.5	36.3	9.7	5.0	24.8	46.4	14.1	71.2	5.0

表4 10FexE10Na/Al2O3催化剂对CO加氢的催化性能

催化剂	CO转化率/%	CO₂选择性/%	烃类选择性/%					总选择性/%	O/P
催化剂	CO转化率/%	CO₂选择性/%	CH₄	C₂~C $40$	C₂~C $4 =$	C₅~C₁₁	C $12 +$	总选择性/%	O/P
10Fe10Na/Al₂O₃	56.5	36.4	11.2	6.0	25.8	43.8	13.2	69.6	4.3
10Fe5E10Na/Al₂O₃	73.5	39.9	11.7	4.6	23.8	46.1	13.8	69.9	5.2
10Fe7.5E10Na/Al₂O₃	77.6	34.7	10.9	6.1	23.1	44.8	15.1	67.9	3.8
10Fe10E10Na/Al₂O₃	88.5	36.3	9.7	5.0	24.8	46.4	14.1	71.2	5.0

图8 10FexEyNa/Al2O3催化剂的XRD图谱

图9 10Fe10E10Na/Al2O3催化剂反应前的TEM图和STEM EDS元素分布

图10 10Fe10Na/Al2O3和10Fe10E10Na/Al2O3催化剂反应后的TEM图

图11 10FexEyNa/Al2O3催化剂的化学吸附

表5 10FexEyNa/Al2O3催化剂的CO吸附量

催化剂	CO吸附量/μmol?g^-1
10Fe10Na/Al₂O₃	1.69
10Fe10E5Na/Al₂O₃	1.54
10Fe10E10Na/Al₂O₃	1.76
10Fe10E15Na/Al₂O₃	1.97
10Fe10E20Na/Al₂O₃	2.29

图12 10Fe/Al2O3、10Fe10E/Al2O3、10Fe10Na/Al2O3和10Fe10E10Na/Al2O3催化剂的Fe 2p XPS能谱

图13 10Fe10Na/Al2O3和10Fe10E10Na/Al2O3催化剂的HRTEM图

图14 氮气吸附-脱附等温线

图15 孔径分布

表6 催化剂的结构特性

催化剂	ICP		BET比表面积 /m²?g^-1	总孔容 /cm³?g^-1	孔径 /nm
催化剂	铁负载量（质量分数）/%	钠负载量（质量分数）/%	BET比表面积 /m²?g^-1	总孔容 /cm³?g^-1	孔径 /nm
Al₂O₃	—	—	147	0.89	31.3
10Fe/Al₂O₃	9.1	—	123	0.59	17.7
10Fe10E/Al₂O₃	9.0	—	137	0.54	17.7
10Fe10Na/Al₂O₃	8.8	3.6	118	0.62	17.5
10Fe10E10Na/Al₂O₃	8.9	3.8	155	0.40	18.1

图16 催化剂在0.1MPa、H2/CO=1、350℃的条件下CO加氢的原位红外光谱

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EDTA辅助制备高活性费托合成催化剂

EDTA-assisted preparation of highly active catalysts for Fischer-Tropsch synthesis

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