钴、锆共掺杂对铟基催化剂二氧化碳加氢制甲醇性能的影响

朱怡澄; 马宏方; 钱炜鑫; 张海涛; 应卫勇

doi:10.12434/j.issn.2097-2547.20240110

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钴、锆共掺杂对铟基催化剂二氧化碳加氢制甲醇性能的影响

二氧化碳化工与催化转化

- 钴、锆共掺杂对铟基催化剂二氧化碳加氢制甲醇性能的影响
- Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol
- 低碳化学与化工 2024, 49(8): 115-122.
- 作者机构：
  
  1.华东理工大学化工学院大型工业反应器工程教育部工程研究中心化学工程联合国家重点实验室，上海 200237
  2.煤液化气化及高效低碳利用全国重点实验室，上海 200237
- 作者简介：
  
  朱怡澄（1999—），硕士研究生，研究方向为低碳化工，E-mail：y82210052@ecust.edu.cn。
  钱炜鑫（1983—），博士，副教授，研究方向为低碳化工，E-mail：wxqian@ecust.edu.cn。
- 基金信息：
  
  国家自然科学基金(22178113);中央高校基本科研业务费专项(JKA01231712)
- DOI：10.12434/j.issn.2097-2547.20240110
  中图分类号： TQ21
- 纸质出版日期：2024-08-25，
  
  收稿日期：2024-03-18，
  
  修回日期：2024-04-01，
- 稿件说明：
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朱怡澄,马宏方,钱炜鑫等.钴、锆共掺杂对铟基催化剂二氧化碳加氢制甲醇性能的影响[J].低碳化学与化工,2024,49(08):115-122.

ZHU Yicheng,MA Hongfang,QIAN Weixin,et al.Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):115-122.
朱怡澄,马宏方,钱炜鑫等.钴、锆共掺杂对铟基催化剂二氧化碳加氢制甲醇性能的影响[J].低碳化学与化工,2024,49(08):115-122. DOI： 10.12434/j.issn.2097-2547.20240110.

ZHU Yicheng,MA Hongfang,QIAN Weixin,et al.Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):115-122. DOI： 10.12434/j.issn.2097-2547.20240110.

摘要

加氢制甲醇是CO

综合利用的重要途径之一。In基催化剂常用于CO

加氢合成甲醇反应，其甲醇选择性较高，但CO

转化率普遍较低。为研究添加不同比例的Co、Zr对In基催化剂性能的影响，在保持In总物质的量分数不变的情况下，采用共沉淀法制备了不同

(Zr):

(Co)的In基催化剂，通过Ar低温物

理吸附、X射线衍射（XRD）、高分辨率透射电镜（HRTEM）、X射线光电子能谱（XPS）和H

程序升温还原（H

-TPR）对催化剂进行了表征，并在温度为240~300 ℃、压力为3.0 MPa和气体空速为7200 mL/(h·g)的条件下对各催化剂的催化性能进行了测试。结果表明，在一定

(Zr):

(Co)范围内，Co、Zr同时添加的催化剂相对于单独添加Co或Zr的催化剂具有更高的CO

转化率和甲醇时空产率。

(Zr):

(Co)不同会产生不同程度的金属间相互作用，影响催化剂的比表面积、颗粒尺寸和还原性能。当

(Zr):

(Co)为1:3时，催化剂具有最优的甲醇合成性能，甲醇时空产率可达178 mg/(g·h)。催化剂的CO

转化率由高至低依次为Zr

In、Zr

2.5

17.5

In、Zr

7.5

12.5

In、Co

In、Zr

In和In

100

，与氧空位占比变化的趋势一致。Zr

In催化剂具有更小的颗粒尺寸与更大的比表面积，可以暴露更多的有效活性位点，因此具有更高的还原性和更强的金属间相互作用，其CO

转化率可达到13.63%，相比Co

In提升了19.9%，相比Zr

In提升了64.7%。

Abstract

hydrogenation to methanol is one of promising route for CO

utilization. In-based catalysts has high methanol selectivity but low CO

conversion rate for CO

hydrogenation to methanol. In order to investigate the effects of doping different proportions of Co and Zr on the performances of In-based catalysts

In-based catalysts doped with different

(Zr):

(Co) were synthesized by co-precipitation method while keeping the same mole fraction of In in the precursor. The catalysts were characterized by low-temperature Ar physical adsorption

X-ray diffraction (XRD)

high resolution transmission electron microscope (HRTEM)

X-ray photoelectron spectroscopy (XPS) and H

temperature-programmed reduction (H

-TPR). The catalytic performances of each catalyst were tested under the conditions of temperature from 240 ℃ to 300 ℃

pressure of 3.0 MPa and gas space velocity of 7200 mL/(h·g). The results show that the catalysts with Co and Zr at the same time has a higher CO

conversion rate and methanol time-sp

ace yield than the catalysts with Co or Zr alone in a certain

(Zr):

(Co) range.

(Zr):

(Co) will produce different degrees of metal-to-metal interactions

which will affect the specific surface area

particle size and reduction performance of the catalysts. When the doped

(Zr):

(Co) is 1:3

the catalyst has the best methanol synthesis ability and the methanol time-space yield is up to 178 mg/(g·h). The CO

conversion rate decreases in the order: Zr

2.5

17.5

7.5

12.5

In and In

100

which is consistent with the trend of oxygen vacancy ratio. The Zr

In catalyst has a smaller particle size with a larger specific surface area

which can expose more active sites

and has higher reducibility and stronger intermetallic interactions. The CO

conversion rate of Zr

In can reach 13.63%

which is 19.9% higher than Co

In and 64.7% higher than Zr

In.

关键词

甲醇In基催化剂二氧化碳加氢共沉淀

Keywords

methanolIn-based catalystscarbon dioxide hydrogenationco-precipitation

references

YANG P, HE Q, HUANG J, et al. Fluxes of greenhouse gases at two different aquaculture ponds in the coastal zone of southeastern China [J]. Atmospheric Environment, 2015, 115: 269-277.

张臻烨, 胡山鹰, 金涌. 2060中国碳中和——化石能源转向化石资源时代[J].现代化工, 2021, 41(6): 1-5.

ZHANG Z Y, HU S Y, JIN Y. China achieving carbon neutral in 2060, fossil energy to fossil resource era [J]. Modern Chemical Industry, 2021,41(6): 1-5.

MIRPARIZI M, SHAKERIASKI F, SALEHI F, et al. Available challenges and recent progress in carbon dioxide capture, and reusing methods toward renewable energy [J]. Sustainable Energy Technologies and Assessments, 2023, 58: 103365.

SARAVANAN A, SENTHIL-KUMAR P, VO D V N, et al. A comprehensive review on different approaches for CO2 utilization and conversion pathways [J]. Chemical Engineering Science, 2021, 236: 116515.

沈辰阳, 孙楷航, 张月萍, 等. 二氧化碳加氢合成甲醇氧化铟及其负载金属催化剂研究进展[J]. 化工学报, 2023, 74(1): 145-156.

SHEN C Y, SUN K H, ZHANG Y P, et al. Research progresses on In2O3 and In2O3 supported metal catalysts for CO2 hydrogenation to methanol [J]. CIESC Journal, 2023, 74(1): 145-156.

MARTIN O, MARYIN A J, MONDELLI C, et al. Indium oxide as a superior catalyst for methanol synthesis by CO2 hydrogenation [J]. Angewandte Chemie International Edition, 2016, 128(21): 6369-6373.

FREI M S, MONDELLI C, GARCIA-MUELAS R, et al. Atomic-scale engineering of indium oxide promotion by palladium for methanol production via CO2 hydrogenation [J]. Nature Communications, 2019, 10(1): 3377.

BEHRENS M, STUDT F, KASATKIN I, et al. The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts [J]. Science, 2012, 336(6083): 893-897.

ADELUNG S, MAIRES S, DIETRICH R U. Impact of the reverse water-gas shift operating conditions on the Power-to-Liquid process efficiency [J]. Sustainable Energy Technologies and Assessments, 2021, 43: 100897.

SUN K H, FAN Z G, YE J Y, et al. Hydrogenation of CO2 to methanol over In2O3 catalyst [J]. Journal of CO2 Utilization, 2015, 12: 1-6.

WANG J Y, ZHANG G H, ZHU J, et al. CO2 hydrogenation to methanol over In2O3-based catalysts: From mechanism to catalyst development [J]. ACS Catalysis, 2021, 11(3): 1406-1423.

FREI M S, MONDELLI C, CESARINI A, et al. Role of zirconia in indium oxide-catalyzed CO2 hydrogenation to methanol [J]. ACS Catalysis, 2019, 10(2): 1133-1145.

SHI Z S, TAN Q Q, WU D F. A novel core-shell structured CuIn@SiO2 catalyst for CO2 hydrogenation to methanol [J]. AIChE Journal, 2019, 65(3): 1047-1058.

RUI N, WANG Z Y, SUN K H, et al. CO2 hydrogenation to methanol over Pd/In2O3: Effects of Pd and oxygen vacancy [J]. Applied Catalysis B: Environmental, 2017, 218: 488-497.

GARCIA-TRENCO A, REGOUTZ A, WHITE E R, et al. PdIn intermetallic nanoparticles for the hydrogenation of CO2 to methanol [J]. Applied Catalysis B: Environmental, 2018, 220: 9-18.

AKKHARAPHATTHAWON N, CHANLEK N, CHENG C K, et al. Tuning adsorption properties of GaxIn2-xO3 catalysts for enhancement of methanol synthesis activity from CO2 hydrogenation at high reaction temperature [J]. Applied Surface Science, 2019, 489: 278-286.

BAVYKINA A, YARUINA I, AL ABDULGHANI A J, et al. Turning a methanation Co catalyst into an In-Co methanol producer [J]. ACS Catalysis, 2019, 9(8): 6910-6918.

LIN D F, ZHANG Z, CEN Y Y, et al. The Co-In2O3 interaction concerning the effect of amorphous Co metal on CO2 hydrogenation to methanol [J]. Journal of CO2 Utilization, 2022, 65: 102209.

ZHANG H, MAO D L, ZHANG J X, et al. Regulating the crystal structure of layered double hydroxide-derived Co-In catalysts for highly selective CO2 hydrogenation to methanol [J]. Chemical Engineering Journal, 2023, 452: 139144.

JIA X Y, SUN K H, WANG J, et al. Selective hydrogenation of CO2 to methanol over Ni/In2O3 catalyst [J]. Journal of Energy Chemistry, 2020, 50: 409-415.

ZHAO F G, FAN L L, XU K J, et al. Hierarchical sheet-like Cu/Zn/Al nano catalysts derived from LDH/MOF composites for CO2 hydrogenation to methanol [J]. Journal of CO2 Utilization, 2019, 33: 222-232.

GAO J, SONG F J, LI Y, et al. Cu2In nanoalloy enhanced performance of Cu/ZrO2 catalysts for the CO2 hydrogenation to methanol [J]. Industrial & Engineering Chemistry Research, 2020, 59(27): 12331-12337.

GAO P, LI F, ZHAO N, et al. Influence of modifier (Mn, La, Ce, Zr and Y) on the performance of Cu/Zn/Al catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol [J]. Applied Catalysis A: General, 2013, 468: 442-452.

PENZHORN R D, DEVILLERS M, SIRCH M. Storage of tritium in ZrCo alloy: Effect of preexposure to impurities relevant to the fusion fuel cycle [J]. Journal of Nuclear Materials, 1991, 179: 863-866.

MAO D L, ZHANG H, ZHANG J X, et al. The influence of the compositions and structures of Cu-ZrO2 catalysts on the catalytic performance of CO2 hydrogenation to CH3OH [J]. Chemical Engineering Journal, 2023, 471: 144605.

YE J Y, LIU C J, MEI D H, et al. Active oxygen vacancy site for methanol synthesis from CO2 hydrogenation on In2O3(110): A DFT study [J]. ACS Catalysis, 2013, 3(6): 1296-1306.

GUO J X, WANG Z Y, LI J L, et al. In-Ni intermetallic compounds derived from layered double hydroxides as efficient catalysts toward the reverse water gas shift reaction [J]. ACS Catalysis, 2022, 12(7): 4026-4036.

ZHANG P Y, NA W, ZUO J Y, et al. CO2 hydrogenation to methanol over hydrothermally synthesized Inx-Zry catalysts [J]. Molecular Catalysis, 2023, 538: 112977.

ZHANG R, LU Y, WEI L, et al. Synthesis and conductivity properties of Gd0.8Ca0.2BaCo2O5+δ double perovskite by sol-gel combustion [J]. Journal of Materials Science: Materials in Electronics, 2015, 26: 9941-9948.

QIN X F, LI H B, WANG K X, et al. Ornidazole degradation by PMS activated by Co-Zr-TiO2 with abundant oxygen vacancies: Performance, mechanism and degradation pathway [J]. Process Safety and Environmental Protection, 2024, 183: 163-177.

CHEN C B, LIU Y, WANG Q, et al. The role of Zr as promoter in the CoZr catalysts for Fischer-Tropsch synthesis [J]. Fuel, 2024, 359: 130405.

LI W H, ZHANG G H, JIANG X, et al. CO2 hydrogenation on unpromoted and M-promoted Co/TiO2 catalysts (M = Zr, K, Cs): Effects of crystal phase of supports and metal-support interaction on tuning product distribution [J]. ACS Catalysis, 2019, 9(4): 2739-2751.

DANG S S, YANG H Y, GAO P, et al. A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation [J]. Catalysis Today, 2019, 330: 61-75.

ZHONG J W, YANG X F, WU Z L, et al. State of the art and perspectives in heterogeneous catalysis of CO2 hydrogenation to methanol [J]. Chemical Society Reviews, 2020, 49(5): 1385-1413.

KATTLE S, LIU P, CHEN J G. Tuning selectivity of CO2 hydrogenation reactions at the metal/oxide interface [J]. Journal of the American Chemical Society, 2017, 139(29): 9739-9754.

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