采用高分子非催化还原脱硝的垃圾焚烧工艺伴生固废含氮污染物特征研究

doi:10.11949/0438-1157.20250226

化工学报 ›› 2025, Vol. 76 ›› Issue (9): 4944-4959.DOI: 10.11949/0438-1157.20250226

• 能源和环境工程 • 上一篇

采用高分子非催化还原脱硝的垃圾焚烧工艺伴生固废含氮污染物特征研究

张茹¹(), 朱传强²(), 张栋¹, 黄政¹, 肖雨果¹, 李明¹, 李长明¹()

^1.北京工商大学轻工科学与工程学院，北京 100048
^2.光大环境科技（中国）有限公司焚烧技术研究所，江苏南京 211100

收稿日期:2025-03-06 修回日期:2025-05-06 出版日期:2025-09-25 发布日期:2025-10-23
通讯作者: 朱传强,李长明
作者简介:张茹（2000—），女，硕士研究生，19861902925@163.com
基金资助:
北京市自然科学基金面上项目(8222042);国家重点研发计划“政府间国际科技创新合作”重点专项(2022YFE0105800)

Characterisation of nitrogenous pollutants in solid wastes associated with waste incineration process using polymer non-catalytic reduction denitrification

Ru ZHANG¹(), Chuanqiang ZHU²(), Dong ZHANG¹, Zheng HUANG¹, Yuguo XIAO¹, Ming LI¹, Changming LI¹()

^1.School of Light Industry Science and Engineering, Beijing Technology and Business University, Beijing 100048, China
^2.Everbright Environmental Technology (China) Co. , Ltd. , Incineration Technology Research Institute, Nanjing 211100, Jiangsu, China

Received:2025-03-06 Revised:2025-05-06 Online:2025-09-25 Published:2025-10-23
Contact: Chuanqiang ZHU, Changming LI

摘要/Abstract

摘要：

以高分子非催化还原（PNCR）脱硝剂及该工艺应用过程中产生的垃圾焚烧底灰和飞灰为对象，研究PNCR脱硝剂热分解过程氮元素释放与残留特征，表征垃圾焚烧底灰和飞灰结构，揭示PNCR脱硝工艺应用后垃圾焚烧的底灰和飞灰含氮污染物特征，探究底灰和飞灰对氨的吸附行为及热解释放特征。结果表明，PNCR脱硝剂在高温条件下，氮元素几乎完全分解和释放，底灰和飞灰残留含氮污染物含量低于0.5%（质量分数）；GCMS和XPS表征结果表明，底灰和飞灰中含氮物质主要以无机氮盐（硝酸盐、铵盐）和有机氮（吡啶类、吡咯类和腈类）形式存在；通过TG-MS和in-situ IR等表征以及直接热脱附实验发现，加热释放的氨含量显著低于其他热脱附气体，热分解产物主要是NO _x，并且飞灰与底灰对游离氨吸附残余容量极低。研究结果将为垃圾焚烧行业固废含氮污染物有效处置提供理论支撑，以促进PNCR脱硝工艺推广和应用。

关键词: 脱硝剂, 高分子非催化还原, 底灰, 飞灰, 含氮污染物, 热解, 垃圾焚烧

Abstract:

Polymer non-catalytic reduction (PNCR) denitrification agent and waste incineration bottom ash and fly ash generated during the application of the process were used as research objects, this study investigated the release and residual characteristics of elemental nitrogen in the thermal decomposition process of PNCR denitrification agent, characterised the structure of waste incineration bottom ash and fly ash, revealed the characteristics of nitrogen-containing pollutants in the bottom ash and fly ash of waste incineration after the application of PNCR denitration process, and probed the adsorption behaviour of the bottom ash and fly ash on ammonia and the characteristics of the release of pyrolysis. The results showed that the PNCR denitrator decomposed and released nitrogen almost completely under high temperature conditions, and the residual nitrogen-containing pollutants in bottom ash and fly ash were less than 0.5% (mass); GCMS and XPS showed that the nitrogen-containing substances in bottom ash and fly ash mainly existed in the form of inorganic nitrogen salts (nitrate, ammonium salts) and organic nitrogen (pyridines, pyrroles, and nitriles). Characterisation by TG-MS and in-situ IR as well as direct thermal desorption experiments revealed that the ammonia content released by heating was extremely low compared to other thermal desorption gases, the thermal decomposition products were mainly NO _x, and the residual capacity of free ammonia adsorption by fly ash and bottom ash was extremely low. The results of the study will provide theoretical support for the effective disposal of nitrogenous pollutants from solid wastes in the waste incineration industry, in order to promote the promotion and application of the PNCR denitrification process.

Key words: denitrator, PNCR, bottom ash, fly ash, nitrogenous pollutant, pyrolysis, waste incineration

中图分类号:

X 705

张茹, 朱传强, 张栋, 黄政, 肖雨果, 李明, 李长明. 采用高分子非催化还原脱硝的垃圾焚烧工艺伴生固废含氮污染物特征研究[J]. 化工学报, 2025, 76(9): 4944-4959.

Ru ZHANG, Chuanqiang ZHU, Dong ZHANG, Zheng HUANG, Yuguo XIAO, Ming LI, Changming LI. Characterisation of nitrogenous pollutants in solid wastes associated with waste incineration process using polymer non-catalytic reduction denitrification[J]. CIESC Journal, 2025, 76(9): 4944-4959.

图/表 17

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热解温度/℃	质量/g	工业分析/%			元素分析/%
热解温度/℃	质量/g	M	A	V	C	H	N	S
PNCR	20.0	2.00	23.84	74.15	25.78	8.98	20.34	0.19
200	18.9	1.13	26.64	72.23	24.12	8.37	18.47	0.25
400	10.3	1.07	52.39	46.54	15.32	5.42	10.55	0.14
600	7.6	0.77	75.76	23.47	9.54	3.33	8.78	0.24
700	6.1	0.87	81.33	17.80	6.21	1.89	4.32	0.34
800	5.3	0.96	94.87	4.17	3.67	1.12	0.49	0.27
900	4.5	0.35	96.46	3.19	2.64	1.42	0.46	0.21

热解温度/℃	质量/g	工业分析/%			元素分析/%
热解温度/℃	质量/g	M	A	V	C	H	N	S
PNCR	20.0	2.00	23.84	74.15	25.78	8.98	20.34	0.19
200	18.9	1.13	26.64	72.23	24.12	8.37	18.47	0.25
400	10.3	1.07	52.39	46.54	15.32	5.42	10.55	0.14
600	7.6	0.77	75.76	23.47	9.54	3.33	8.78	0.24
700	6.1	0.87	81.33	17.80	6.21	1.89	4.32	0.34
800	5.3	0.96	94.87	4.17	3.67	1.12	0.49	0.27
900	4.5	0.35	96.46	3.19	2.64	1.42	0.46	0.21

样品	工业分析/%			元素分析/%
样品	M_ar	A_ar	V_ar	C_ar	H_ar	N_ar	S_ar	C_烧	H_烧	N_烧	S_烧
底灰	1.81	88.60	8.52	1.57	0.84	0.16	1.15	0.17	0.68	0	1.78
飞灰	2.93	86.37	10.84	2.54	1.33	0.37	2.64	0.31	1.32	0.01	3.36

样品	工业分析/%			元素分析/%
样品	M_ar	A_ar	V_ar	C_ar	H_ar	N_ar	S_ar	C_烧	H_烧	N_烧	S_烧
底灰	1.81	88.60	8.52	1.57	0.84	0.16	1.15	0.17	0.68	0	1.78
飞灰	2.93	86.37	10.84	2.54	1.33	0.37	2.64	0.31	1.32	0.01	3.36

样品	质量分数/%
样品	SiO₂	CaO	Al₂O₃	Fe₂O₃	SO₃	MgO	TiO₂	K₂O	Na₂O
底灰	48.46	21.43	12.62	7.67	2.02	2.21	1.14	0.83	0.82
飞灰	42.46	20.13	13.35	8.37	1.94	2.73	1.06	4.41	2.73

采用高分子非催化还原脱硝的垃圾焚烧工艺伴生固废含氮污染物特征研究

Characterisation of nitrogenous pollutants in solid wastes associated with waste incineration process using polymer non-catalytic reduction denitrification

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元素峰	形态分布	相对含量/%
元素峰	形态分布	底灰	飞灰
C 1s	芳香碳和烷烃（C—H、C—C）	74.79	75.99
	碳氧单键碳（C—O）	11.39	14.48
	羰基碳（C=O）	4.14	1.48
	羧基碳（COO—）	9.68	1.32
N 1s	吡啶氮（N-6）	17.78	10.78
	吡咯氮（N-5）	29.78	36.04
	铵盐（NH₄⁺）	17.72	25.58
	硝酸盐（NO₃^-）	34.72	27.6
S 2p	亚砜型硫（R—S=O—R'）	10.92	13.72
S 2p	硫酸盐（SO₄—S）	89.08	86.28

序号	化合物名称	分子式	分子量	底灰	飞灰
1	2-吡咯烷酮	C₄H₇NO	85	√	√
2	1-乙烯基-2-吡咯烷酮	C₆H₉NO	111	√	√
3	十八烷腈	C₁₈H₃₅N	265	√	√
4	十六腈	C₁₆H₃₁N	237	×	√
5	芥酸酰胺	C₂₂H₄₃NO	338	×	√
6	2,4-二叔丁基酚	C₁₄H₂₂O	206	√	×
7	(Z)-十八-9-烯醇	C₁₈H₃₆O	268	√	×
8	6-叔丁基对甲酚	C₂₃H₃₂O₂	340	√	×
9	十五醇	C₁₅H₃₂O	228	×	√
10	1,16-十六烷二醇	C₁₆H₃₄O₂	258	×	√
11	十六醛	C₁₆H₃₂O	240	×	√
12	十八烷醛	C₁₈H₃₆O	268	×	√
13	二碘甲烷	CH₂I₂	268	√	√
14	十二烷	C₁₂H₂₆	170	√	√
15	1,3-二叔丁基苯	C₁₄H₂₂	190	√	√
16	正十五烷	C₁₅H₃₂	212	√	√
17	十四烷	C₁₄H₃₀	198	√	√
18	氯代十六烷	C₁₆H₃₃Cl	261	√	×
19	正十六烷	C₁₆H₃₄	226	√	√
20	正十七烷	C₁₇H₃₆	240	√	√
21	正二十一烷	C₂₁H₄₄	297	√	×
22	十八烯	C₁₈H₃₆	252	√	×
23	正二十四烷	C₂₄H₅₀	339	√	√
24	三十烷	C₃₀H₆₂	423	√	×
25	2,4-二甲基庚烷	C₉H₂₀	128	×	√
26	乙基苯	C₈H₁₀	106	×	√
27	间二甲苯	C₈H₁₀	106	×	√
28	二甲硫基甲烷	C₃H₈S₂	108	×	√
29	2,2-二甲基戊烷	C₇H₁₆	100	×	√
30	3-乙基辛烷	C₁₀H₂₂	142	×	√
31	(+)-柠檬烯	C₁₀H₁₆	136	×	√
32	萘	C₁₀H₈	128	×	√
33	十二烷	C₁₂H₂₆	170	×	√
34	5-甲基十一烷	C₁₂H₂₆	170	×	√
35	2,6-二甲基十一烷	C₁₃H₂₈	184	×	√
36	3,3-二甲基已烷	C₈H₁₈	114	×	√
37	碘十一烷	C₁₁H₂₃I	282	×	√
38	正二十烷	C₂₀H₄₂	283	×	√
39	正十八烷	C₁₈H₃₈	254	×	√
40	正二十烷	C₂₀H₄₂	283	×	√

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