Theoretical calculation of effect of NiO and Ni catalysts for benzoic acid pyrolysis

LIANG Wensheng; LIU Jiangtao; ZHAO Yue; HUANG Wei; ZUO Zhijun

doi:10.11949/j.issn.0438-1157.20181396

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Theoretical calculation of effect of NiO and Ni catalysts for benzoic acid pyrolysis

Catalysis\, kinetics and reactors | 更新时间：2026-07-24

- Theoretical calculation of effect of NiO and Ni catalysts for benzoic acid pyrolysis
- CIESC Journal Vol. 70, Issue 4, Pages: 1429-1435(2019)
- 作者机构：
  
  太原理工大学煤科学与技术教育部与山西省重点实验室，山西太原 030024
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20181396
  CLC： O 643.36
- Received：22 November 2018，
  
  Revised：2019-01-08，
  
  Online First：15 June 2020，
  
  Published：12 April 2019
- 稿件说明：
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梁文胜, 刘江涛, 赵月, 黄伟, 左志军. NiO和Ni催化剂对苯甲酸热解机理的理论计算[J]. 化工学报, 2019, 70(4): 1429-1435

LIANG Wensheng, LIU Jiangtao, ZHAO Yue, HUANG Wei, ZUO Zhijun. Theoretical calculation of effect of NiO and Ni catalysts for benzoic acid pyrolysis[J]. CIESC Journal, 2019, 70(4): 1429-1435
梁文胜, 刘江涛, 赵月, 黄伟, 左志军. NiO和Ni催化剂对苯甲酸热解机理的理论计算[J]. 化工学报, 2019, 70(4): 1429-1435 DOI： 10.11949/j.issn.0438-1157.20181396.

LIANG Wensheng, LIU Jiangtao, ZHAO Yue, HUANG Wei, ZUO Zhijun. Theoretical calculation of effect of NiO and Ni catalysts for benzoic acid pyrolysis[J]. CIESC Journal, 2019, 70(4): 1429-1435 DOI： 10.11949/j.issn.0438-1157.20181396.

摘要

在煤热解过程中加入特定的催化剂可以改变煤结构中相关化学键的结合能，使热解在相对温和的条件下进行，促使更多的小分子从煤结构上解离成为产物释放，并调节产物的产率和组成，提高转化率及产物的品质。由于煤化学结构的复杂性，从分子水平研究煤的催化热解行为非常困难。基于此，以煤的催化热解为背景，采用煤模型化合物，借助密度泛函理论(DFT)，选取苯甲酸(C

COOH)为煤基模型，以NiO和Ni为催化剂，研究催化热解过程中催化剂价态改变对煤催化剂热解的作用。DFT结果显示，苯甲酸热解的主要路径为：C

COOH

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916063&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916040&type=

7.02733326

2.87866688

和C

COOH

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916065&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916064&type=

7.02733326

2.87866688

COO

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916091&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916054&type=

7.02733326

2.87866688

；在NiO上的分解路径为：C

COOH(g)

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916069&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916076&type=

7.02733326

2.87866688

COO + *H

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916071&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916070&type=

7.02733326

2.87866688

*CO

+ *C

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916080&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916105&type=

7.02733326

2.87866688

(g) + C

(g) ；在金属Ni上的分解路径为：C

COOH(g)

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916083&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916106&type=

7.02733326

2.87866688

COOH

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916123&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916109&type=

7.02733326

2.87866688

COO + *H

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916126&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916102&type=

7.02733326

2.87866688

*CO

+ *C

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916129&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113916113&type=

7.02733326

2.87866688

(g) + C

(g) 。Ni基催化剂的加入能够促进C

COOH的热解，同时改变了苯甲酸的热解路径，但是产物不变。当NiO被还原为金属Ni时，催化效果减弱。

Abstract

The catalyst alters the binding energy of some chemical bonds in coal. It makes the conditions of pyrolysis

milder

and adjusts the yield and composition of the product by promoting the micromolecules dissociation from coal. As a result

the conversion and the quality of product are increased. However

the chemical structure of coal is very complex

the catalytic pyrolysis mechanisms in coal are very difficult to study at the molecular level. Therefore

benzoic acid (C

COOH) is selected as the coal-based model compound to investigate the effect of valence states change of catalysts during catalytic pyrolysis by using density functional theory (DFT) method

in which NiO and Ni are selected as catalysts. The results showed that there are two reaction pathways for C

COOH pyrolysis. One is CO

and C

are directly formed from C

COOH. The other is that C

COO is produced from H migration of C

COOH

then

and CO

are obtained from C

COO decomposition. On NiO(100)

the favorable reaction pathway is that *C

COO and *H are formed from C

COOH dissociative adsorption. Finally

*CO

and *C

are produced from *C

COO decomposition with the assistance of *H. On Ni(111)

the favorable reaction pathway is that *C

COO and *H are formation from *C

COOH decomposition

which C

COOH is nondissociative adsorption. Eventually

*CO

and *C

are obtained. In general

Ni-based catalyst can promote C

COOH pyrolysis and change the pyrolysis pathways of benzoic acid

but the products are still the same. The catalytic effect decreases when NiO is reduced to metallic Ni.

关键词

Keywords

references

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