Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C<sub>2+</sub> alcohols

XU Jing; GE Qingjie; SUN Jian

doi:10.12434/j.issn.2097-2547.20230091

您当前的位置：

首页 >

文章列表页 >

Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C₂₊ alcohols

- Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C₂₊ alcohols
- Vol. 49, Issue 1, Pages: 25-32(2024)
- 作者机构：
  
  1.中国科学院大连化学物理研究所洁净能源国家实验室，辽宁大连 116023
  2.中国科学院大学，北京 100049
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20230091
  CLC：
扫描看全文
徐晶,葛庆杰,孙剑.掺杂钙钛矿催化剂的制备及其催化合成气直接转化制C₂₊醇性能研究[J].低碳化学与化工,2024,49(01):25-32.

XU Jing,GE Qingjie,SUN Jian.Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C₂₊ alcohols[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):25-32.
徐晶,葛庆杰,孙剑.掺杂钙钛矿催化剂的制备及其催化合成气直接转化制C₂₊醇性能研究[J].低碳化学与化工,2024,49(01):25-32. DOI： 10.12434/j.issn.2097-2547.20230091.

XU Jing,GE Qingjie,SUN Jian.Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C₂₊ alcohols[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):25-32. DOI： 10.12434/j.issn.2097-2547.20230091.

摘要

由合成气直接转化制C,2+,醇（碳链中含两个及两个以上碳原子的醇类）是目前最有前景的醇类化合物合成路线之一，而钙钛矿结构的催化剂可用于提高该过程中的C,2+,醇合成性能。采用共沉淀法分别制备了Co、Mn掺杂的钙钛矿LFC和LFM催化剂（L、F、C和M分别指金属La、Fe、Co和Mn），系统考察了不同焙烧温度和掺杂元素对钙钛矿催化剂的C,2+,醇合成性能的影响。多种表征结果显示，低焙烧温度可优化LF-600（“-”后的数字指焙烧温度）催化剂的结构和吸附行为，在LF-600催化剂上，CO解离和非解离位点的耦合有助于提高反应的CO转化率和总醇的选择性，分别达16.9%和31.2%（质量分数），且Co和Mn的掺杂可改变LF-600催化剂的产物分布和活性。与LF-600催化剂相比，LFC-600催化剂的H,2,吸附能力低，有利于反应链增长，从而将C,2+,醇在总醇中的比例从60.4%提高至71.6%。LFM-600催化剂具有更多的低温H,2,吸附位点，导致醇类产物以甲醇为主，而Mn掺杂导致的颗粒团聚及Mn和O元素聚集会降低LFM-600催化剂的活性。

Abstract

Direct conversion of syngas to C,2+, alcohols (alcohols with two or more carbon atoms) is currently one of the most promising routes for the synthesis of alcohols, and perovskite-structured catalysts can be used to improve the performance for the synthesis of C,2+, alcohols in this process. Co and Mn doped perovskite LFC and LFM catalysts (L, F, C and M refer to metal La, Fe, Co and Mn, respectively) were prepared by co-precipitation method, respectively, and the effects of different calcination temperatures and doped elements on the catalytic performance of perovskite catalysts were systematically investigated in C,2+, alcohols synthesis. Results of various characterizations show that the low calcination temperature can optimize the structural properties and adsorption behaviors of LF-600 (the numbers after “-” refer to the calcination temperature) catalyst, and the coupling of CO dissociation and non-dissociation sites on LF-600 catalyst helps to increase CO conversion and total alcohol selectivity to 16.9% and 31.2% (mass fraction), respectively. The doping of Co and Mn can change the product distribution and activity of LF-600 catalyst. Compared with LF-600 catalyst, LFC-600 catalyst promotes the chain growth due to the low H,2, adsorption capacity, thereby increasing the proportion of C,2+, alcohols in total alcohols from 60.4% to 71.6%. LFM-600 catalyst has more low-temperature H,2, adsorption sites leading to methanol being the main alcohol product, while particle agglomeration and Mn and O aggregation caused by Mn doping can reduce the activity of LFM-600 catalyst.

关键词

合成气C2+醇钙钛矿催化剂B位掺杂焙烧温度

Keywords

syngasC2+ alcoholsperovskite catalystsB-site dopingcalcination temperature

references

LUK H T, MONDELLI C, FERRE D C, et al. Status and prospects in higher alcohols synthesis from syngas [J]. Chemical Society Reviews, 2017, 46(5): 1358-1426.

XUE X X, WENG Y J, YANG S C, et al. Research progress of catalysts for synthesis of low-carbon alcohols from synthesis gas [J]. RSC Advances, 2021, 11(11): 6163-6172.

刘竞舸, 闫国春, 房克功, 等. 合成气制混合醇催化剂研究进展[J]. 化学试剂, 2021, 43(10): 1369-1375.

LIU J G, YAN G C, FANG K G, et al. Research progress of catalysts for mixed alcohol synthesis from syngas [J]. Chemical Reagents, 2021, 43(10): 1369-1375.

LIU G B, YANG G H, PENG X B, et al. Recent advances in the routes and catalysts for ethanol synthesis from syngas [J]. Chemical Society Reviews, 2022, 51(13): 5606-5659.

AO M, PHAM G H, SUNARSO J, et al. Active centers of catalysts for higher alcohol synthesis from syngas: A review [J]. ACS Catalysis, 2018, 8(8): 7025-7050.

GRIM R G, TO A T, FARBEROW C A, et al. Growing the bioeconomy through catalysis: A review of recent advancements in the production of fuels and chemicals from syngas-derived oxygenates [J]. ACS Catalysis, 2019, 9(5): 4145-4172.

DAMMA D, SMIRNIOTIS P G. Recent advances in the direct conversion of syngas to oxygenates [J]. Catalysis Science & Technology, 2021, 11(16): 5412-5431.

ZHOU W, KANG J C, CHENG K, et al. Direct conversion of syngas into methyl acetate, ethanol, and ethylene by relay catalysis via the intermediate dimethyl ether [J]. Angewandte Chemie International Edition, 2018, 57(37): 12012-12016.

KANG J C, HE S, ZHOU W, et al. Single-pass transformation of syngas into ethanol with high selectivity by triple tandem catalysis [J]. Nature Communications, 2020, 11(1): 827.

熊烨. 合成气制醇类的钼基催化剂的研究进展[J]. 天然气化工—C1化学与化工, 2019, 44(3): 117-121.

XIONG Y. Research process in Mo-based catalysts for synthesis of alcohols from syngas [J]. Natural Gas Chemical Industry, 2019, 44(3): 117-121.

丁云杰. 煤经合成气制乙醇和混合高碳伯醇的研究进展[J]. 煤化工, 2018, 46(1): 1-5.

DING Y J. Research progress in production of ethanol and mixed high carbon primary alcohols from coal through syngas [J]. Coal Chemical Industry, 2018, 46(1): 1-5.

魏晓娜, 李文双, 王闯, 等. 铑基催化剂在合成气制乙醇中的研究进展[J]. 应用化工, 2020, 49(9): 2388-2392.

WEI X N, LI W S, WANG C, et al. Research progress of Rh-based catalysts in the synthesis of ethanol from syngas [J]. Applied Chemical Industry, 2020, 49(9): 2388-2392.

LU Y W, ZHANG R G, CAO B B, et al. Elucidating the copper-hägg iron carbide synergistic interactions for selective CO hydrogenation to higher alcohols [J]. ACS Catalysis, 2017, 7(8): 5500-5512.

LI Y W, GAO W, PENG M, et al. Interfacial Fe5C2-Cu catalysts toward low-pressure syngas conversion to long-chain alcohols [J]. Nature Communications, 2020, 11(1): 61.

CHEN Y P, MA L X, ZHANG R G, et al. Carbon-supported Fe catalysts with well-defined active sites for highly selective alcohol production from Fischer-Tropsch synthesis [J]. Applied Catalysis B: Environmental, 2022, 312: 121393.

XU J, WEI J, ZHANG J X, et al. Highly selective production of long-chain aldehydes, ketones or alcohols via syngas at a mild condition [J]. Applied Catalysis B: Environmental, 2022, 307: 121155.

WANG C T, ZHANG J, QIN G Q, et al. Direct conversion of syngas to ethanol within zeolite crystals [J]. Chem, 2020, 6(3): 646-657.

QIN T T, LIN T J, QI X Z, et al. Tuning chemical environment and synergistic relay reaction to promote higher alcohols synthesis via syngas conversion [J]. Applied Catalysis B: Environmental, 2021, 285: 119840.

ZENG Z, LI Z S, GUO S X, et al. Janus Au-Fe2.2C catalyst for direct conversion of syngas to higher alcohols [J]. ACS Sustainable Chemistry & Engineering, 2021, 9(33): 11258-11268.

ZENG F, XI X Y, CAO H T, et al. Synthesis of mixed alcohols with enhanced C3+ alcohol production by CO hydrogenation over potassium promoted molybdenum sulfide [J]. Applied Catalysis B: Environmental, 2019, 246: 232-241.

XI X Y, ZENG F, CAO H T, et al. Enhanced C3+ alcohol synthesis from syngas using KCoMoSx catalysts: Effect of the Co-Mo ratio on catalyst performance [J]. Applied Catalysis B: Environmental, 2020, 272: 118950.

HE S, WANG W, SHEN Z, et al. Carbon nanotube-supported bimetallic Cu-Fe catalysts for syngas conversion to higher alcohols [J]. Molecular Catalysis, 2019, 479: 110610.

ZHAO Z, LU W, YANG R O, et al. Insight into the formation of Co@Co2C catalysts for direct synthesis of higher alcohols and olefins from syngas [J]. ACS Catalysis, 2017, 8(1): 228-241.

LIN T J, QI X Z, WANG X X, et al. Direct production of higher oxygenates by syngas conversion over a multifunctional catalyst [J]. Angewandte Chemie International Edition, 2019, 58(14): 4627-4631.

CUI W G, LI Y T, ZHANG H, et al. In situ encapsulated Co/MnOx nanoparticles inside quasi-MOF-74 for the higher alcohols synthesis from syngas [J]. Applied Catalysis B: Environmental, 2020, 278: 119262.

HUANG C, ZHU C, ZHANG M W, et al. Design of efficient ZnO/ZrO2 modified CuCoAl catalysts for boosting higher alcohol synthesis in syngas conversion [J]. Applied Catalysis B: Environmental, 2022, 300: 120739.

ZENG Z, LI Z, KANG L, et al. A Monodisperse ε’-(CoxFe1–x)2.2C bimetallic carbide catalyst for direct conversion of syngas to higher alcohols [J]. ACS Catalysis, 2022, 12: 6016-6028.

王欢, 唐浩东, 卢保同, 等. 炭载体对钴基催化剂制混合醇的影响[J]. 天然气化工—C1化学与化工, 2014, 39(5): 7-11.

WANG H, TANG H D, LU B T. Effects of Co-based catalysts supported on different carbons on synthesis of mixed higher alcohols from syngas [J]. Natural Gas Chemical Industry, 2014, 39(5): 7-11.

YANG Q L, CAO A, KANG N, et al. Bimetallic nano Cu-Co based catalyst for direct ethanol synthesis from syngas and its structure variation with reaction time in slurry reactor [J]. Industrial & Engineering Chemistry Research, 2017, 56(11): 2889-2898.

THAO N T ALAMDARI H, ZAHEDI-NIAKI M H, et al. LaCo1-xCuxO3-δ perovskite catalysts for higher alcohol synthesis [J]. Applied Catalysis A: General, 2006, 311: 204-212.

THAO N T. Synthesis of Co-Cu/La2O3 pervoskites for hydrogenation of CO [J]. Asian Journal of Chemistry, 2013, 25(14): 8082-8086.

LIU G L, PAN D M, NIU T, et al. Nanoparticles of Cu-Co alloy supported on high surface area LaFeO3-preparation and catalytic performance for higher alcohol synthesis from syngas [J]. RSC Advances, 2015, 5(40): 31637-31647.

WANG T, ZHANG C, WANG J Y, et al. The interplay between the suprafacial and intrafacial mechanisms for complete methane oxidation on substituted LaCoO3 perovskite oxides [J]. Journal of Catalysis, 2020, 390: 1-11.

BULAVCHENKO O A, CHEREPANOVA S V, MALAKHOV V V, et al. In situ XRD study of nanocrystalline cobalt oxide reduction [J]. Kinetics and Catalysis, 2009, 50(2): 192-198.

XIANG Y Z, KRUSE N. Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins [J]. Nature Communications, 2016, 7: 13058.

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Effect of calcination temperature on structure and catalytic performance of Fe-Mn catalysts for synthesis of light olefins from syngas

Research progress on catalysts for dimethyl oxalate hydrogenation to ethanol via two reaction pathways

Research progress in green synthesis of acetic acid from syngas

Effect of precipitation pH of ZnCr₂O₄ on catalytic performance in directing conversion syngas to light olefins

Related Author

No data

Related Institution

中国科学院山西煤炭化学研究所煤转化国家重点实验室

中国科学院研究生院

College of Chemistry, Taiyuan University of Technology

State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology

(Shaanxi Yanchang Petroleum (Group) Company Limited & Dalian Institute of Chemical Physics Xi’an Clean Energy (Chemical Industry) Research Institute, , , )

Postal code：610225
Tel：028-85964717 Email：dthxyhg@swchem.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：48404 Visits Today：175

⁰

Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C2+ alcohols

DOI：10.12434/j.issn.2097-2547.20230091

摘要

Abstract

关键词

Keywords

references

Preparation of doped perovskite catalysts and their catalytic performance for direct conversion of syngas to C₂₊ alcohols