基于热力学计算的CO<sub>2</sub>催化加氢制二甲醚流程分析

郑泽宇; 崔灵瑞; 刘操; 黄成; 马宏方; 曹发海

doi:10.12434/j.issn.2097-2547.20230417

您当前的位置：

首页 >

文章列表页 >

基于热力学计算的CO₂催化加氢制二甲醚流程分析

二氧化碳捕集与利用

- 基于热力学计算的CO₂催化加氢制二甲醚流程分析
- Process analysis of catalytic hydrogenation of CO₂ to dimethyl ether based on thermodynamic calculation
- 低碳化学与化工 2024, 49(10): 103-109.
- 作者机构：
  
  1.华东理工大学化工学院上海 200237
  2.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上海 200237
- 作者简介：
  
  郑泽宇（1997—），硕士研究生，研究方向为二氧化碳利用工艺开发，E-mail：zyzheng_2052@163.com。
  崔灵瑞（1992—），博士，助理研究员，研究方向为重质油加工与二氧化碳利用，E-mail：cuilr@ecust.edu.cn。
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20230417
  中图分类号： TQ51;O642
- 纸质出版日期：2024-10-25，
  
  收稿日期：2023-12-20，
  
  修回日期：2024-01-31，
- 稿件说明：
移动端阅览
郑泽宇,崔灵瑞,刘操等.基于热力学计算的CO₂催化加氢制二甲醚流程分析[J].低碳化学与化工,2024,49(10):103-109.

ZHENG Zeyu,CUI Lingrui,LIU Cao,et al.Process analysis of catalytic hydrogenation of CO₂ to dimethyl ether based on thermodynamic calculation[J].Low-carbon Chemistry and Chemical Engineering,2024,49(10):103-109.
郑泽宇,崔灵瑞,刘操等.基于热力学计算的CO₂催化加氢制二甲醚流程分析[J].低碳化学与化工,2024,49(10):103-109. DOI： 10.12434/j.issn.2097-2547.20230417.

ZHENG Zeyu,CUI Lingrui,LIU Cao,et al.Process analysis of catalytic hydrogenation of CO₂ to dimethyl ether based on thermodynamic calculation[J].Low-carbon Chemistry and Chemical Engineering,2024,49(10):103-109. DOI： 10.12434/j.issn.2097-2547.20230417.

摘要

二甲醚是一种理想的发动机清洁燃料，在碳中和背景下，国内外积极开展了以二氧化碳（CO

）为原料制备二甲醚的研究。CO

催化加氢制二甲醚的方法主要包括一步法和两步法，对基于不同方法的工艺流程展开热力学分析，可为工艺流程优化和相关催化剂开发提供参考。基于一步法构建了流程一，基于两步法分别构建了流程二（以甲醇为中间体）和流程三（以CO为中间体），在原料气组成为

(CO

) = 3:1的条件下，对反应温度（150~350 ℃）与反应压力（1.0~9.0 MPa）对各流程中相应的平衡常数、CO

平衡转化率和二甲醚收率的影响进行了研究。结果表明，在150 ℃、9.0 MPa下，与其他两种流程相比，流程一更具优势，其CO

平衡转化率为94.61%，二甲醚收率为85.31%。对于以CO为中间体的两步法工艺，未来需加强高效逆水煤气低温催化剂的开发。对于一步法工艺，将反应体系与分离体系进行耦合的复合体系是未来主要的研究方向。

Abstract

Dimethyl ether is an ideal engine clean fuel. Under the background of carbon neutrality

the preparation of dimethyl ether from CO

has been actively carried out at home and abroad. The methods of catalytic hydrogenation of CO

to dimethyl ether mainly include one-step and two-step method. The thermodynamic analysis of the processes based on different methods can provide reference for process optimization and related catalyst development. Process one was constructed based on the one-step method

and process two (with methanol as the intermediate) and process three (with CO as the intermediate) were respectively constructed based on the two-step method. Under the condition that the composition of raw gas is

(CO

) = 3:1

the effects of reaction temperatures (from 150 ℃ to 350 ℃) and reaction pressures (from 1.0 MPa to 9.0 MPa) on the corresponding equilibrium constants

equilibrium conversion rates and dimethyl ether yields in each process were studied. The results show that at 150 ℃ and 9.0 MPa

the process one is superior to the other two processes

with CO

equilibrium conversion rate of 94.61% and dimethyl ether yield of 85.31%. For the two-step method process with CO as the intermediate

the development of high efficiency reverse water gas low temperature catalyst should be strengthened in the future. For the one-step

method process

the composite system coupling reaction system and separation system is the main research direction in the future.

关键词

二氧化碳催化加氢二甲醚流程分析热力学计算

Keywords

carbon dioxidecatalytic hydrogenationdimethyletherprocess analysisthermodynamic calculation

references

刘畅, 刘忠文. CO2加氢一步制二甲醚展望[J]. 化工进展, 2022, 41(3): 1115-1120.

LIU C, LIU Z W. Perspective on the one-step CO2 hydrogenation to dimethyl ether [J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1115-1120.

VAN KAMPEN J, BOON J, VAN SINT ANNALAND M, et al. Separation enhanced methanol and dimethyl ether synthesis [J]. Journal of Materials Chemistry A, 2021, 9(26): 141627-14629.

冯文华. GaZrOx双金属氧化物催化CO2加氢制甲醇和二甲醚的协同机理研究[D]. 兰州: 兰州大学, 2021.

FENG W H. Insights into bimetallic oxide synergy during CO2 hydrogenation to methanol and dimethyl ether over GaZrOx oxide catalysts [D]. Lanzhou: Lanzhou University, 2021.

ATEKA A, RODRIGUEZ V P, CORDERO-LANZAC T, et al. Model validation of a packed bed LTA membrane reactor for the direct synthesis of DME from CO/CO2 [J]. Chemical Engineering Journal, 2021, 408: 127356.

陈舒瑶. 改性CuZnZr催化剂CO2加氢高选择性合成甲醇/二甲醚的研究[D]. 合肥: 中国科学院大学, 2020.

CHEN S Y. Study on the highly selective synthesis of methanol/dimethyl ether by CO2 hydrogenation of modified CuZnZr catalyst [D]. Hefei: University of Chinese Academy of Sciences, 2020.

秦霏, 颜万鑫, 纳薇, 等. 活性形貌对CuO/ZnO/Al2O3催化加氢反应的影响[J]. 精细化工, 2019, 36(5): 905-912.

QIN F, YAN W X, NA W, et al. Effect of active morphology on catalytic hydrogenation of CuO/ZnO/Al2O3 [J]. Fine Chemicals, 2019, 36(5): 905-912.

薛茹君, 朱峰. Zr掺杂Cu-Mn-Al/HZSM-5催化剂上CO2加氢一步制取二甲醚[J]. 天然气化工—C1化学与化工, 2018, 43(6): 53-57.

XUE R J, ZHU F. Zr-doped Cu-Mn-Al/HZSM-5 catalyst for direct synthesis of DME from CO2 hydrogenation [J]. Natural Gas Chemical Industry, 2018, 43(6): 53-57.

FAN X, JIN B T, REN S J, et al. Roles of interaction between components in CZZA/HZSM-5 catalyst for dimethyl ether synthesis via CO2 hydrogenation [J]. AIChE Journal, 2021, 67(11): 17353.

郭永乐. 新型铜基核壳双功能催化剂制备及COx加氢直接制二甲醚研究[D]. 大连: 大连理工大学, 2021.

GUO Y L. Studies in preparation of Cu-based core-shell bifunctional catalysts and their catalytic properties for direct synthesis of dimethyl ether through COx hydrogenation [D]. Dalian: Dalian University of Technology, 2021.

GRAAF G H, SIJTSEMA P J J M, STAMHUIS E J, et al. Chemical equilibria in methanol synthesis [J]. Chemical Engineering Science, 1986, 41(11): 2883-2890.

BENNEKOM J G V, WINKELMAN J G M, VENDERBOSCH R H, et al. Modeling and experimental studies on phase and chemical equilibria in high-pressure methanol synthesis [J]. Industrial & Engineering Chemistry Research, 2012, 51(38): 12233-12243.

BANSODE A, URAKAWA A. Towards full one-pass conversion of carbon dioxide to methanol and methanol-derived products [J]. Journal of Catalysis, 2014, 309: 66-70.

GAILWAD R, BANSODE A, URAKAWA A. High-pressure advantages in stoichiometric hydrogenation of carbon dioxide to methanol [J]. Journal of Catalysis, 2016, 343: 127-132.

LI H Z, REN S J, ZHANG S X, et al. The high-yield direct synthesis of dimethyl ether from CO2 and H2 in a dry reaction environment [J]. Journal of Materials Chemistry A, 2021, 9(5): 2678-2682.

LI H Z, QIU C L, REN S J, et al. Na+-gated water-conducting nanochannels for boosting CO2 conversion to liquid fuels [J]. Science, 2020, 367(6478): 667-671.

YUE W Z, WAN Z, Li Y H, et al. Synthesis of Cu-ZnO-Pt@HZSM-5 catalytic membrane reactor for CO2 hydrogenation to dimethyl ether [J]. Journal of Membrane Science, 2022, 660.

YUE W Z, LI Y H, WEI W, et al. Highly selective CO2 conversion to methanol in abifunctional zeolite catalytic membrane reactor [J]. Angewandte Chemie-Internationa Edition, 2021, 60(33): 18289-18294.

CHEN C J, SUN X F, YAN X P, et al. Boosting CO2 electroreduction on N,P-co doped carbon aerogels [J]. Angewandte Chemie-International Edition, 2020, 59(27): 11123-11129.

MA J P, XIONG X, WU D, et al. Band position-independent piezo-electrocatalysis for ultrahigh CO2 conversion [J]. Advanced Materials, 2023, 35(21): 2300027.

POLSHETTIWAR V, BELGAMWAR R, VERMA R, et al. Defects tune the strong metal-support interactions in copper supported on defected titanium dioxide catalysts for CO2 reduction [J]. Journal of the American Chemical Society, 2023, 145 (15): 8634-8646.

浏览量

下载量

CNKI被引量

文章被引用时，请邮件提醒。

提交

工具集

关联资源

二氧化碳催化加氢制高级醇催化剂研究进展

不同合成工艺的二氧化碳催化加氢制甲醇装置经济性分析

基于热力学计算的CO2催化加氢制二甲醚流程分析

Process analysis of catalytic hydrogenation of CO2 to dimethyl ether based on thermodynamic calculation

DOI：10.12434/j.issn.2097-2547.20230417

摘要

Abstract

关键词

Keywords

references

基于热力学计算的CO₂催化加氢制二甲醚流程分析

Process analysis of catalytic hydrogenation of CO₂ to dimethyl ether based on thermodynamic calculation