碳氧官能团对煤焦低温还原NO的影响

doi:10.11949/0438-1157.20211692

化工学报 ›› 2022, Vol. 73 ›› Issue (5): 2140-2148.doi: 10.11949/0438-1157.20211692

碳氧官能团对煤焦低温还原NO的影响

王佳怡^1,²(),范垂钢^1,²,李松庚^1,³()

^1.中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
^2.中国科学院大学中丹学院，北京 100049
^3.中国科学院大学化学工程学院，北京 100049

收稿日期:2021-11-29 修回日期:2022-01-27 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 李松庚 E-mail:echojiayi@outlook.com;sgli@ipe.ac.cn
作者简介:王佳怡（1996—），女，硕士研究生，echojiayi@outlook.com
基金资助:
国家自然科学基金项目(21978305);山东魏桥创业集团“教育部产学合作协同育人”项目

Role of carbon-oxygen complexes on low temperature reduction of NO by coal char

Jiayi WANG^1,²(),Chuigang FAN^1,²,Songgeng LI^1,³()

^1.State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.Sino Danish College, University of Chinese Academy of Sciences, Beijing 100049, China
^3.School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2021-11-29 Revised:2022-01-27 Published:2022-05-05 Online:2022-05-24
Contact: Songgeng LI E-mail:echojiayi@outlook.com;sgli@ipe.ac.cn

摘要/Abstract

摘要：

在450℃对神木煤制半焦还原NO进行研究，采用Raman、FT-IR、XPS等分析方法探究了半焦脱硝影响因素与其表面碳氧官能团的关系。结果表明：热解制焦温度、烟气中氧气浓度以及负载金属对脱硝效果的影响都与半焦表面碳氧官能团有关，降低热解温度、增大氧气浓度、负载金属均有利于增加C—O官能团。采用XPS表征对金属负载半焦表面的碳氧官能团进行分析，发现热力学相对稳定的C—O官能团含量与脱硝指标之间存在明显的线性关系(R²>0.96)。研究进一步揭示了热力学稳定的C—O官能团在半焦脱硝过程的重要地位。

关键词: 煤焦, 氮氧化物, 还原, 多相反应, 表面, 碳氧官能团

Abstract:

The reduction of NO by Shenmu coal char was studied at 450℃, and the relationship between the influencing factors of coal char denitrification and its surface carbon-oxygen functional groups was explored by Raman, FT-IR, XPS and other analytical methods. Combining the results of isothermal experiments and characterizations, close connection between influencing factors and carbon-oxygen complexes was revealed. The effect of coal char preparation temperature, oxygen concentration in flue gas as well as influence of metallic elements could be in connection with carbon-oxygen complexes on coal char surface. More specifically, lowering pyrolysis temperature, increasing oxygen concentration, and loading metals were all conducive to the retention and formation of thermally stable C—O species on coal char surface. Strong linear relationship was discovered via XPS method between thermally stable C—O species and experimental evaluation indexes (R²>0.96). Carbon-oxygen complexes, especially thermally stable C—O compounds, played a key character in NO reduction by coal char.

Key words: coal char, nitric oxide, reduction, multiphase reaction, surface, C(O) complexes

中图分类号:

TQ 536.9

王佳怡, 范垂钢, 李松庚. 碳氧官能团对煤焦低温还原NO的影响[J]. 化工学报, 2022, 73(5): 2140-2148.

WANG Jiayi, FAN Chuigang, LI Songgeng. Role of carbon-oxygen complexes on low temperature reduction of NO by coal char[J]. CIESC Journal, 2022, 73(5): 2140-2148.

图/表 14

表1

表2

图1

图2

图3

图4

图5

图6

表3

反应前后半焦表面含氧官能团分布"

状态	反应气氛	A_C—O/A_arom	A_C $?$ _O/A_arom
反应前	—	0	0.49
反应后	0%(体积)O₂	0.12	1.76
	1%(体积)O₂	0.43	2.62
	5%(体积)O₂	0.63	2.64

表3

图7

图8

图9

表4

脱硝前后半焦表面含氧官能团分布"

半焦	C—C, C—H		C—O		R₂C $? ?????$ O		O $? ?????$ C—O		C—K
半焦	BE/eV	Prop./ %(mol)	BE/eV	Prop./ %(mol)	BE/eV	Prop./ %(mol)	BE/eV	Prop./ %(mol)	BE/eV	Prop./ %(mol)
SM	284.8	81.92	286.3	12.10	287.5	0.41	289.0	4.61	296.2	0.96
SM-2%MgO	284.8	59.46	286.3	12.14	287.5	23.01	289.0	0.86	296.2	4.53
SM-2%K₂O	284.8	57.42	286.3	17.05	287.5	0.00	289.0	13.96	296.2	11.56
SM-0.5%Na₂O	284.8	74.45	286.3	15.31	287.5	0.49	289.0	8.97	296.2	0.79

表4

表5

C（O）官能团含量与脱硝指标之间关联度分析"

评价指标	C—O	R₂C $? ?????$ O	O $? ?????$ C—O
X	0.9989	0.2921	0.9115
S	0.9999	0.1025	0.6096
CO/CO _x	0.9662	0.1923	0.7920

表5

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工业分析/%(质量，ad)						元素分析/%(质量，ad)					BET表征
M	A	V	FC		C		H	N	O^①	S	比表面积/(m²·g^-1)	孔容/(cm³·g^-1)	平均孔径/nm
0.76	6.64	13.95	78.66		85.38		2.34	1.41	3.35	0.13	14.59	0.018	5.026

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碳氧官能团对煤焦低温还原NO的影响

Role of carbon-oxygen complexes on low temperature reduction of NO by coal char

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