污泥与高硫煤共水热碳化过程中硫氮形态转化规律

doi:10.11949/0438-1157.20220848

摘要/Abstract

摘要：

采用高温高压反应釜进行了污泥(SS)和高硫煤(CS)的共水热碳化实验。分别考察了混合比和温度对水热炭中硫氮元素形态转化规律的影响。研究结果表明，经过水热处理后，SS中蛋白质氮(N-A)转化为杂环类氮，CS中吡咯氮(N-5)和吡啶氮氧化物(N-X)转化为吡啶氮(N-6)和季氮(N-Q)；SS与CS中硫元素逐渐转化为噻吩硫和硫酸盐。随着CS混合比例和温度的升高，水热炭中含氮芳族杂环(例如N-6、N-5和N-Q)占比增加。另外，随着CS混合比例和温度升高，水热炭中噻吩硫含量分别逐渐增加至22.61%和24.98%；升高温度提高了水热炭中硫酸盐含量，而增加CS混合比例却降低了硫酸盐含量。本研究可为后续SS和CS的资源化清洁利用提供理论基础。

关键词: 污泥, 高硫煤, 共水热碳化, 水热炭, 硫氮元素, 赋存形态

Abstract:

Co-hydrothermal carbonization experiments of sewage sludge and high-sulfur coal were carried out using a high temperature and high pressure reactor. The results showed that protein nitrogen (N-A) of sewage sludge was converted into heterocyclic nitrogen after hydrothermal treatment, and pyrrole (N-5) and pyridine oxynitride (N-X) of high sulfur coal were converted into pyridine (N-6) and quaternary nitrogen (N-Q). The sulfur of sewage sludge and high sulfur coal were converted into thiophene and sulfate. The increase in the proportion of nitrogen-containing aromatic heterocycles (e.g., N-6, N-5, and N-Q) in the hydrochar was attributed to the increase of the proportion of high-sulfur coal blends and temperature. Furthermore, the thiophene content of hydrochar increased to 22.61% and 24.98% gradually with increasing of high-sulfur coal blending ratio and temperature; and the sulfate content increased at higher temperature, however it decreased when increasing proportion of high-sulfur coal blend ratio. This study could provide the theoretical basis for the clean utilization of sewage sludge and high-sulfur coal efficiently.

Key words: sewage sludge, high-sulfur coal, co-hydrothermal carbonization, hydrochar, sulfur and nitrogen elements, occurrence form

中图分类号:

X 705

杨晓阳, 王宝凤, 宋旭涛, 杨凤玲, 程芳琴. 污泥与高硫煤共水热碳化过程中硫氮形态转化规律[J]. 化工学报, 2022, 73(11): 5211-5219.

Xiaoyang YANG, Baofeng WANG, Xutao SONG, Fengling YANG, Fangqin CHENG. Migration of sulfur and nitrogen during co-hydrothermal carbonization process of sewage sludge and high-sulfur coal[J]. CIESC Journal, 2022, 73(11): 5211-5219.

图/表 8

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Sample	Ultimate analysis/% (d)					H/C	O/C	Proximate analysis/% (d)
Sample	N	C	H	S	O^①	H/C	O/C	Ash	VM	FC
SS-Raw	3.51±0.09	20.38±0.47	3.04±0.06	1.92±0.07	16.87±0.01	1.79±0.07	0.62±0.01	54.28±0.26	45.59±0.24	0.13±0.02
CS-Raw	1.07±0.05	53.70±0.30	2.83±0.04	2.93±0.04	12.96±0.06	0.63±0.01	0.18±0.01	26.51±0.37	18.79±0.56	54.70± 0.19
S10C0-240	1.65±0.04	9.99±0.06	1.18±0..06	0.59±0.07	6.65±0.15	1.42±0.06	0.50±0.01	79.94±0.38	17.34±0.79	2.72±0.41
S7C3-240	1.06±0.03	26.40±0.57	1.84±0.07	1.73±0.04	5.84±0.01	0.84±0.01	0.17±0.01	63.13±0.72	16.87±0.74	20.00±0.02
S5C5-240	0.98±0.05	34.84±0.81	2.15±0.11	2.17±0.05	6.61±0.99	0.74±0.06	0.14±0.02	53.25±0.39	15.85±0.73	30.90±0.34
S3C7-240	0.83±0.02	41.91±0.44	2.51±0.06	2.43±0.05	6.68±0.56	0.72±0.02	0.12±0.01	45.64±0.21	15.09±0.57	39.27±0.36
S0C10-240	0.66±0.04	55.03±0.83	2.20±0.06	2.38±0.06	10.18±2.89	0.48±0.01	0.14±0.04	29.55±0.56	13.63±0.88	56.82±1.44
S5C5-160	1.07±0.03	34.15±0.27	2.28±0.06	1.66±0.05	11.58±0.30	0.80±0.01	0.25±0.01	49.26±0.71	18.55±0.35	32.19±0.36
S5C5-200	1.06±0.03	34.70±1.46	2.03±0.14	1.53±0.05	7.69±2.03	0.07±0.08	0.17±0.05	52.99±0.63	17.08±0.27	29.93±0.36
S5C5-280	0.90±0.03	34.47±0.38	1.85±0.07	1.83±0.04	5.59±0.06	0.64±0.02	0.12±0.01	55.36±0.38	13.80±0.21	30.84±0.59

Sample	Ultimate analysis/% (d)					H/C	O/C	Proximate analysis/% (d)
Sample	N	C	H	S	O^①	H/C	O/C	Ash	VM	FC
SS-Raw	3.51±0.09	20.38±0.47	3.04±0.06	1.92±0.07	16.87±0.01	1.79±0.07	0.62±0.01	54.28±0.26	45.59±0.24	0.13±0.02
CS-Raw	1.07±0.05	53.70±0.30	2.83±0.04	2.93±0.04	12.96±0.06	0.63±0.01	0.18±0.01	26.51±0.37	18.79±0.56	54.70± 0.19
S10C0-240	1.65±0.04	9.99±0.06	1.18±0..06	0.59±0.07	6.65±0.15	1.42±0.06	0.50±0.01	79.94±0.38	17.34±0.79	2.72±0.41
S7C3-240	1.06±0.03	26.40±0.57	1.84±0.07	1.73±0.04	5.84±0.01	0.84±0.01	0.17±0.01	63.13±0.72	16.87±0.74	20.00±0.02
S5C5-240	0.98±0.05	34.84±0.81	2.15±0.11	2.17±0.05	6.61±0.99	0.74±0.06	0.14±0.02	53.25±0.39	15.85±0.73	30.90±0.34
S3C7-240	0.83±0.02	41.91±0.44	2.51±0.06	2.43±0.05	6.68±0.56	0.72±0.02	0.12±0.01	45.64±0.21	15.09±0.57	39.27±0.36
S0C10-240	0.66±0.04	55.03±0.83	2.20±0.06	2.38±0.06	10.18±2.89	0.48±0.01	0.14±0.04	29.55±0.56	13.63±0.88	56.82±1.44
S5C5-160	1.07±0.03	34.15±0.27	2.28±0.06	1.66±0.05	11.58±0.30	0.80±0.01	0.25±0.01	49.26±0.71	18.55±0.35	32.19±0.36
S5C5-200	1.06±0.03	34.70±1.46	2.03±0.14	1.53±0.05	7.69±2.03	0.07±0.08	0.17±0.05	52.99±0.63	17.08±0.27	29.93±0.36
S5C5-280	0.90±0.03	34.47±0.38	1.85±0.07	1.83±0.04	5.59±0.06	0.64±0.02	0.12±0.01	55.36±0.38	13.80±0.21	30.84±0.59

Sulphur species	Binding energy/eV
mercaptan	162.2±0.2
sulfide	163.3±0.2
thiophene	164.1±0.2
sulfoxide	166.0±0.2
sulfone	168.5±0.5
sulfate	170.0±0.5

Sulphur species	Binding energy/eV
mercaptan	162.2±0.2
sulfide	163.3±0.2
thiophene	164.1±0.2
sulfoxide	166.0±0.2
sulfone	168.5±0.5
sulfate	170.0±0.5

Nitrogen functionality	Form	Binding energy/eV
pyridine-N	N-6	398.7±0.4
protein-N	N-A	399.8±0.2
pyrrole-N	N-5	400.4±0.2
inorganic-N	Inorg-N	402.0±0.5
quaternary-N	N-Q	402.0±0.5
nitrogen oxide	N-X	403.5±0.5