灰分在印染污泥热解气化中的协同催化机理

doi:10.11949/0438-1157.20210123

摘要/Abstract

摘要：

印染污泥中含有大量的金属基组分。选取其中的主要金属氧化物组分，分别进行单组分与多组分添加开展催化热解实验，采用X射线衍射、傅里叶变换红外光谱、热解-气质联用、热质联用分析手段，研究金属基组分对印染污泥的催化热解效应，探索了各金属基组分在热解过程中的协同催化作用机理。结果表明，不同金属基化合物在热解过程中显示了不同的催化热解温度区间和催化性能，对热解的催化协同效应是Fe₂O₃、ZnO、CaO和Na₂CO₃四种组分共同作用的效果。协同作用可以分为两个阶段：250~500℃为主热解区，各金属基组分都发挥着催化剂的作用，促进大分子化合物的裂解；在600℃之后的高温热解区间，Fe₂O₃等组分可与原料中的碳成分发生还原反应，造成热重曲线明显失重峰，进一步提升残渣的裂解特性。

关键词: 印染污泥, 热解, 气化, 灰分, 催化, 协同机理

Abstract:

The printing and dyeing sludge contains a large amount of metal-based components. In order to explore the synergistic effect of metal base components in sludge ash during pyrolysis process, the main metal oxides contained in the ash of textile dyeing sludge were selected, and the catalytic pyrolysis experiments were carried out after the addition of single component and multi-component respectively. The effects of these metal-based components in the ash on the catalytic pyrolysis of the textile dyeing sludge was analyzed by X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) and thermogravimetric mass spectrometry (TG-MS). The results showed that each metal-based component exhibited their temperature range and catalytic performance during pyrolysis. Moreover, the synergistic effect on pyrolysis is the combined effect of Fe₂O₃, ZnO, CaO and Na₂CO₃. Further, the synergistic effect can be divided into two stages: 250—500℃ was the main pyrolysis zone, and each metal-based component plays the role of catalyst to promote the pyrolysis of macromolecular compounds. In the pyrolysis zone after 600℃, Fe₂O₃ and other components can react with the carbon in the raw material, resulting in a significant weight loss peak in the thermogravimetric curve, which further improved the cracking characteristics of the residue.

Key words: textile dyeing sludge, pyrolysis, gasification, ash, catalysis, synergistic mechanism

中图分类号:

TQ 028.8

杨丽, 孙赟冬, 焦勇, 杨烨, 陈建标, 廖传华. 灰分在印染污泥热解气化中的协同催化机理[J]. 化工学报, 2021, 72(9): 4718-4729.

Li YANG, Yundong SUN, Yong JIAO, Ye YANG, Jianbiao CHEN, Chuanhua LIAO. Synergistic catalytic mechanism of ash in pyrolysis and gasification of textile dyeing sludge[J]. CIESC Journal, 2021, 72(9): 4718-4729.

图/表 15

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样品	工业分析/%(质量)
样品	M_ad	V_ad	A_ad	FC_ad	C_ad	H_ad	N_ad	S_ad	O_ad
印染污泥	1.59	55.45	42.2	0.76	15.82	2.79	1.6	5.09	30.91
锯末	5.21	68.84	3.19	22.76	48.66	5.81	0.3	0.20	36.63

样品	工业分析/%(质量)
样品	M_ad	V_ad	A_ad	FC_ad	C_ad	H_ad	N_ad	S_ad	O_ad
印染污泥	1.59	55.45	42.2	0.76	15.82	2.79	1.6	5.09	30.91
锯末	5.21	68.84	3.19	22.76	48.66	5.81	0.3	0.20	36.63

参数	印染污泥	模拟灰分	Fe₂O₃	ZnO	CaO	Na₂CO₃
T_max/℃	801	793	861	912	707	902
DTG_max/(%/min)	-2.37	-2.32	-0.91	-3.94	-1.40	-2.87
ΔML	12.23	12.80	9.69	23.25	6.57	16.67

参数	印染污泥	模拟灰分	Fe₂O₃	ZnO	CaO	Na₂CO₃
T_max/℃	801	793	861	912	707	902
DTG_max/(%/min)	-2.37	-2.32	-0.91	-3.94	-1.40	-2.87
ΔML	12.23	12.80	9.69	23.25	6.57	16.67

化合物	停留时间/min	峰面积×10^-6	化合物	停留时间/min	峰面积×10^-6
苯系化合物			链状化合物
甲苯	4.42	2.73	醋酸	2.39	22.35
苯并环丁烯	7.49	1.33	2-甲基丙醇	4.65	3.82
邻甲氧基苯酚	13.53	5.26	正戊醛	13.71	1.83
2-甲氧基-4-甲基苯酚	16.58	2.44	壬醛	13.93	3.97
4-乙烯基-2-甲氧基苯酚	19.95	10.17	2-乙基己酸	14.66	10.35
3-甲氧基-4-羟基苯甲醛	22.43	7.36	酯类^*	16.91	0.53
(E)-2-甲氧基-4-(1-丙烯基苯酚)	23.47	13.09	壬酸	18.82	2.15
苯系	24.17	3.65	1-十三烯	19.27	0.79
苯炔	24.35	0.83	2-甲氧基-4-烯丙基酚	21.11	3.27
苯酯	32.80	2.88	酯类^*	21.51	0.71
脂环化合物			三乙二醇单丁醚	23.95	2.83
右旋萜二烯	11.61	14.94	十七烯	24.42	0.70
脂环烯烃	31.70	4.74	十五烷	24.61	1.24
含氧杂环			正十二酸	26.21	8.68
糠醛	6.13	1.98	烯烃^*	26.79	1.39
糠醇	8.63	1.23	2,2,4-三甲基-1,3-戊二醇二异丁酸酯	26.98	1.92
呋喃酮	10.47	12.21	己二酸二异丁酯	28.92	0.95
某含氧环烃^*	14.25	4.71	十四酸	30.57	0.76
含氮杂环			十六酸	34.60	12.02
某含氮胺类^*	5.10	3.83	酮类^*	35.54	0.35
某含氮环烃^*	9.71	0.91	马来酸二乙基己酯	37.37	7.06
3-甲胺基丙腈	13.77	0.87	十八烷酸	37.49	7.25
N-丁基乙酰胺	15.92	1.43
十四胺	15.96	1.02