Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory

您当前的位置：

首页 >

文章列表页 >

Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory

更新时间：2025-07-09

- Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory
- Vol. 43, Issue 7, Pages: 30-35(2009)
- 作者机构：
  
  东南大学热能工程研究所,南京,210096
- 作者简介：
- 基金信息：
- DOI：
  CLC： TK61
- Online First：10 July 2009，
  
  Published：2009
- 稿件说明：
移动端阅览
Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory[J]. 2009, 43(7): 30-35.
DOI：

Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory[J]. 2009, 43(7): 30-35. DOI：

摘要

采用密度泛函方法(B3LYP)在6-311+g(3df

2p)基组水平上研究了甲酸在超临界水中分解的微观反应机理.研究结果表明:甲酸在超临界水中的分解反应存在多条反应通道

反应历程复杂

其中通道R〖FY1〗IM1〖FY1〗TS4〖FY1〗IM4〖FY1〗TS5〖FY1〗P1和R〖FY1〗IM3〖FY1〗TS14〖FY1〗P2为主通道

分别对应甲酸脱羧反应和脱羰反应; H

O作为催化剂参与了甲酸分解反应

使得脱羧反应和脱羰反应的反应势垒明显降低

促进了甲酸分解

且对脱羧反应的促进作用更为明显.利用传统过渡态理论

分别计算出2条主通道的速控步骤在压力为25 MPa、温度为700～1 500 K范围内的速率常数表达式分别为k

=4.68×10

exp(-22 231.46/T)s

-1

和k

=5.34×10

exp(-24 587.05/T)s

-1

Abstract

The reaction mechanism of formic acid decomposition in supercritical water was investigated theoretically at the B3LYP/6-311+g(3df

2p)level. The results show that there are several reaction channels in the decomposition of formic acid

and the channels

R〖FY1〗IM1〖FY1〗TS4〖FY1〗IM4〖FY1〗TS5〖FY1〗P1 and R〖FY1〗IM3〖FY1〗TS14〖FY1〗P2

are the main reaction channels

corresponding to decarboxylation and dehydration reactions

respectively. H

O takes part in the formic acid decomposition reaction as a catalyst

which lowers the energy barrier heights of both decarboxylation and dehydration reactions and accelerates the decomposition of formic acid. The rate constants of decarboxylation(k

)and dehydration(k

)were obtained using the transition state theory(TST)at the pressure of 250 MPa and in the temperature range of 700-1500 K: k

=4.68×10

exp(-22 231.46/T)s

-1

and k

=5.34×10

exp(-24 587.05/T)s

-1

关键词

Keywords

references

郝小红, 郭烈锦. 超临界水中湿生物质催化气化制氢研究评述[J]. 化工学报, 2002, 53(3): 221-227.

HAO Xiaohong, GUO Liejin. A review on investigation of hydrogen production by biomass catalytic gasification in supercritical water [J]. Journal of Chemical Engineering, 2002, 53(3): 221-228.

ASGHARI F S, YOSHIDA H. Acid-catalyzed production of 5-hydroxymethyl furfural from D-fructose in subcritical water [J]. Ind Eng Chem Res, 2006, 45(7): 2163-2173.

KABYEMELA B M, ADSCHIRI T, MALALUAN R M, et al. Glucose and fructose decomposition in subcritical and supercritical water: detailed reaction pathway, mechanisms, and kinetics [J]. Ind Eng Chem Res, 1999, 38(8): 2888-2895.

OSADA M, WATANABE M, SUE K, et al. Water density dependence of formaldehyde reaction in supercritical water [J]. J of Supercritical Fluids, 2004, 28(2): 219-224.

OSADA M, SATO O, WATANABE M, et al. Water density effect on lignin gasification over supported noble metal catalysts in supercritical water [J]. Energy Fuels, 2006, 20(3): 930-935.

SINAG A, KRUSE A, SCHWARZKOPF V. Key compounds of the hydropyrolysis of glucose in supercritical water in the presence of K2CO3 [J]. Ind Eng Chem Res, 2003, 42(15): 3516-3521.

YOSHIDA K, WAKAI C, MATUBAYASI N, et al. NMR spectroscopic evidence for an intermediate of formic acid in the water-gas-shift reaction [J]. J Phys Chem: A, 2004, 108(37): 7481-7482.

张国妮, 张军, 徐益谦. 超临界水中甲醛气化的实验研究[J]. 西安交通大学学报, 2008, 42(3): 372-376.

ZHANG Guoni, ZHANG Jun, XU Yiqian. Experimental research on formaldehyde gasification in supercritical water [J]. Journal of Xi'an Jiaotong University, 2008, 42(3): 372-376.

YU J, SAVAGE P E. Decomposition of formic acid under hydrothermal conditions [J]. Ind Eng Chem Res, 1998, 37(1): 2-10.

吕友军, 冀承猛, 郭烈锦. 农业生物质在超临界水中气化制氢的实验研究[J]. 西安交通大学学报, 2005, 39(3): 238-242.

LÜ Youjun, JI Chengmeng, GUO Liejin. Experimental investigation on hydrogen production by agricultural biomass gasification in supercritical water [J]. Journal of Xi'an Jiaotong University, 2005, 39(3): 238-242.

毛肖岸, 郝小红, 郭烈锦, 等. 超临界水中纤维素气化制氢的实验研究[J]. 工程热物理学报, 2003, 24(3): 388-390.

MAO Xiaoan, HAO Xiaohong, GUO Liejin, et al. Experimental study of hydrogen production by cellulose gasification in supercritical water [J]. Journal of Engineering Thermophysics, 2003, 24(3): 388-390.

闫秋会, 郭烈锦, 梁兴, 等. 煤与生物质共超临界水催化气化制氢的实验研究[J]. 西安交通大学学报, 2005, 39(5): 454-457.

YAN Qiuhui, GUO Liejin, LIANG Xing, et al. Hydrogen production from co-gasification of coal and biomass in supercritical water by continuous flow thermal catalytic reaction system [J]. Journal of Xi'an Jiaotong University, 2005, 39(5): 454-457.

KRUSE A, HENNINGSEN T, SINAG A, et al. Biomass gasification in supercritical water: influence of the dry matter content and the formation of phenols [J]. Ind Eng Chem Res, 2003, 42(16): 3711-3717.

LEE I G, KIM M S, IHM S K. Gasification of glucose in supercritical water [J]. Ind Eng Chem Res, 2002, 41(5): 1182-1188.

CHANG J-G, CHEN H-T, XU S. Computational study on the kinetics and mechanisms for the unimolecular decomposition of formic and oxalic acids [J]. J Phys Chem: A, 2007, 111(29): 6789-6797.

刘朋军, 潘秀梅, 赵岷, 等. NCS 自由基与NO 反应动力学的理论研究[J]. 高等学校化学学报, 2004, 25(4): 685-688.

LIU Pengjun, PAN Xiumei, ZHAO Min, et al. Theoretical studies on kinetics reaction for the reaction of NCS radical and NO [J]. Chemical Journal of Chinese Universities, 2004, 25(4): 685-688.

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Study on the Thermodynamic Properties in the Anomalous Region of Supercritical Water

Study on the Electrochemical Oxidation of Ampicillin Using Ti/TiHx-NiCo2O4Anode

Study on the Corrosion Mechanisms of Nickel-Based Alloys in Hydrogen-Containing Supercritical Water

Reaction Mechanism and Hydrogen Production Efficiency of Aluminum-Water Reaction in Sub- and Supercritical Water

Research on the Electrohydrodynamic Effects of Ionic Liquid-Modified Fuels

Related Author

LIU Jinqi

YIN Wei

WANG Guoxiang

LI Dong

WANG Yueshe

CHEN Bin

SHI Jinwen

ZHANG Yuanyuan

Related Institution

Department of Mechanical Engineering，The University of Akron，Akron

State Key Laboratory of Multiphase Flow in Power Engineering，Xi'an Jiaotong University

西安交通大学能源动力与工程学院，710049，西安School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China

Northwest Institute of Nuclear Technology

BYD Automotive Limited Company

⁰