CO<sub>2</sub>气氛对煤热解过程中硫逸出的影响

郭慧卿; 付琦; 王鑫龙; 刘粉荣; 胡瑞生; 张浩

CO₂气氛对煤热解过程中硫逸出的影响

郭慧卿^{1, 2},
付琦¹,
王鑫龙¹,
刘粉荣^1, ,,
胡瑞生¹,
张浩¹

1.
内蒙古大学化学化工学院, 内蒙古呼和浩特 010021
2.
内蒙古医科大学药学院, 内蒙古呼和浩特 010110

基金项目:

国家自然科学基金 21466025

详细信息

通讯作者:
刘粉荣, E-mail：fenrongl@163.com

中图分类号: TQ530.2
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- 文章访问数: 120
- HTML全文浏览量: 23
- PDF下载量: 11
- 被引次数: 0
出版历程
- 收稿日期: 2016-11-11
- 修回日期: 2017-03-22
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-05-10

Effect of CO₂ atmosphere on sulfur release during coal pyrolysis

1.
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China
2.
College of Pharmacy, Inner Mongolia Medical University, Hohhot 010110, China

Funds:

the National Natural Science Foundation of China 21466025

摘要

摘要: 采用热解-质谱（Py-MS）与热解-气相色谱（Py-GC）相结合的方法对平朔（PS）和义马（YM）原煤、脱灰煤及其脱黄铁矿煤进行了热解实验，考察了CO₂气氛对煤热解过程中硫逸出行为的影响。并采用质谱在线分析H₂S、COS和SO₂的逸出曲线，利用气相色谱分析H₂S、COS和SO₂在气相中的逸出量。结果表明，CO₂气氛有利于H₂S、COS和SO₂进入气相，且逸出量增加，而COS增加幅度更大。同时，CO₂气氛有利于H₂S和SO₂最大逸出峰温提前。另外，CO₂气氛对原煤的H₂S、COS和SO₂逸出温度影响较大，但对脱灰煤的影响较小。在较高的温度下，CO₂有利于煤中稳定有机硫的分解。这进一步验证了在较高温度下COS形成与CO相关，而在较低温度下与CO无关。
- CO₂气氛 /
- 煤热解 /
- 硫释放 /
- 热解-质谱 (Py-MS) /
- 热解-气相色谱 (Py-GC)
Abstract: Yima (YM) coal and Pingshuo (PS) coal as well as their deashed coals and depyrited coals were used to investigate the effects of CO₂ and Ar on the sulfur release behavior during coal pyrolysis by pyrolysis connected with mass spectrometer (Py-MS) and pyrolysis connected with gas chromatogram (Py-GC). It is found that CO₂ atmosphere can promote the release of H₂S, COS and SO₂, especially the remarkable releasing of COS. In addition, CO₂ atmosphere can decrease the maximum release peak temperature of H₂S, COS and SO₂ for raw coals, while there is no obvious effect for their deashed coals. At the same time, CO₂ is beneficial to the decomposition of organic sulfur at higher temperature. That the COS formation is related to CO at higher temperatures and has nothing to do with CO at lower temperatures is validated.
- CO₂ atmosphere /
- coal pyrolysis /
- sulfur release /
- Py-MS /
- Py-GC

HTML全文

图 1 Ar气氛下义马原煤COS、H₂S和SO₂逸出曲线

Figure 1 Releasing peaks of COS, H₂S and SO₂ for YM raw coal pyrolysis under Ar atmosphere

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图 2 不同气氛下热解过程中H₂S逸出曲线

Figure 2 H₂S release lines of coal samples during pyrolysis under different atmospheres

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图 3 不同气氛下热解过程中COS逸出曲线

Figure 3 COS release curves during coal pyrolysis under different atmospheres

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图 4 CO₂气氛下热解过程中原煤COS与CO逸出曲线

Figure 4 COS and CO release curves during coal pyrolysis under CO₂ atmosphere

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图 5 不同气氛下热解过程中SO₂逸出曲线

Figure 5 SO₂ release curves during coal pyrolysis under different atmospheres

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表 1 煤样的工业分析和元素分析

Table 1 Proximate and ultimate analysis of coal samples

Sample	Proximate analysis w/%				Ultimate analysis w_ad/%
Sample	M_ad	A_ad	V_daf	FC_daf	C	H	O^*	N	S
YM-raw coal	8.15	17.38	39.40	60.60	51.85	3.3	16.36	0.81	2.15
YM-deashed	6.29	4.68	38.45	61.55	63.59	3.75	16.85	1.08	3.76
YM-depyrited	10.16	1.09	40.11	59.89	64.46	3.03	18.47	1.07	0.82
PS-raw coal	1.83	22.96	42.02	57.98	56.22	3.88	11.62	0.96	2.53
PS-deashed	2.62	1.64	36.86	63.14	74.59	4.53	12.19	1.39	3.07
PS-depyrited	3.81	1.34	37.36	62.64	73.33	4.49	12.78	1.32	2.93
note: ad is air-dried basis; d is dried basis; daf is dried and ash-free basis; ^*: by difference

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表 2 煤样的硫形态分析

Table 2 Sulfur forms analysis of coal samples

Sample	Sulfur forms in coal w_ad/%				Sulfur form ratio in total S w/%
Sample	S_t	S_s	S_p	S_o^*	S_s	S_p	S_o^*
YM-raw coal	2.15	0.18	0.89	1.08	8.37	41.40	50.23
YM-deashed	3.76	0.10	2.95	0.71	2.66	78.46	18.88
YM-depyrited	0.82	0.05	0.03	0.74	6.10	3.66	90.24
PS-raw coal	2.53	0.20	0.06	2.27	7.91	2.37	89.72
PS-deashed	3.07	0.04	0.06	2.97	1.30	1.95	96.75
PS-depyrited	2.93	0.06	0.01	2.86	2.05	0.34	97.61
note: S_t is the total sulfur; S_s is the sulfate sulfur; S_p is the pyrite sulfur; S_o is the organic sulfur; ^*: by difference

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表 3 煤样的灰成分分析

Table 3 Ash analysis of coal samples

Sample	Content w/%										R_B/A
Sample	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	TiO₂	SO₃	K₂O	Na₂O	P₂O₅	R_B/A
YM	53.18	17.26	14.1	2.16	1.50	3.42	5.55	1.70	0.86	0.26	0.275
PS	57.26	25.60	1.24	4.21	0.20	2.98	7.43	0.25	0.29	0.17	0.072

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表 4 不同气氛下半焦产率与脱硫率

Table 4 Char yields and sulfur removal ratios of coal pyrolysis under different atmospheres

Sample	Ar/%			CO₂/%
Sample	S_t in the char (1 000 ℃)	char yields	sulfur removal ratios	S_t in the char (1 000 ℃)	char yields	sulfur removal ratios
YM-raw coal	1.81	57.19	51.75	2.58	32.80	60.70
YM-deashed	1.53	53.38	78.22	2.01	28.40	84.85
YM-depyrited	0.63	50.31	61.35	0.70	36.80	68.59
PS-raw coal	1.53	61.81	62.59	1.33	42.00	77.97
PS-deashed	2.24	56.56	58.66	1.99	31.20	79.74
PS-depyrited	2.13	51.69	62.35	2.00	21.20	85.56

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表 5 不同气氛下含硫气体总逸出量

Table 5 sulfur-containing gases release during pyrolysis under different conditions

Coal sample	Ar/(g·g_coal^-1)			CO₂/(g·g_coal^-1)			Release ratio (CO₂/Ar)
Coal sample	H₂S	COS	SO₂	H₂S	COS	SO₂	H₂S	COS	SO₂
YM-raw coal	4.42×10^-3	1.08×10^-3	1.14×10^-3	3.80×10^-3	4.33×10^-3	1.86×10^-3	0.86	4.00	1.63
YM-deashed	4.65×10^-3	1.54×10^-3	1.69×10^-3	4.86×10^-3	4.15×10^-3	2.09×10^-3	1.04	2.68	1.24
YM-depyrited	2.22×10^-3	4.09×10^-4	1.60×10^-4	2.40×10^-3	1.12×10^-3	5.69×10^-4	1.08	2.75	3.56
PS-raw coal	4.64×10^-3	8.33×10^-4	2.77×10^-4	6.36×10^-3	3.78×10^-3	9.82×10^-4	1.37	4.53	3.56
PS-deashed	6.22×10^-3	5.44×10^-4	1.67×10^-3	6.53×10^-3	3.52×10^-3	2.50×10^-3	1.05	6.50	1.50
PS-depyrited	6.18×10^-3	6.14×10^-4	1.57×10^-3	6.80×10^-3	3.28×10^-3	2.76×10^-3	1.10	5.33	1.76

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