微波辅助脱除煤中有机硫的机理研究

李梅; 金权; 孙功成; 程雪云; 李佳佳; 徐荣声

微波辅助脱除煤中有机硫的机理研究

李梅^{1, 2, 3, ,},
金权¹,
孙功成¹,
程雪云¹,
李佳佳¹,
徐荣声¹

1.
北方民族大学化学与化学工程学院, 宁夏银川 750021
2.
北方民族大学宁夏太阳能化学转化技术重点实验室, 宁夏银川 750021
3.
北方民族大学国家民委化工技术基础重点实验室, 宁夏银川 750021

基金项目:

国家自然科学基金 21666001

北方民族大学校级科研项目 2017HG04

北方民族大学校级重大专项 ZDZX201803

北方民族大学科研平台项目 201707

北方民族大学研究生创新项目 YCX19114

详细信息

通讯作者:
LI Mei, Tel: 15009663719, E-mail: echolimei@126.com

中图分类号: TQ530.2
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- 被引次数: 0
出版历程
- 收稿日期: 2019-05-20
- 修回日期: 2019-07-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-10-10

Removal mechanism of organic sulfur in coal assisted by microwave irradiation

1.
School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, China
2.
Ningxia Key Laboratory of Solar Chemical Conversion Technology, North Minzu University, Yinchuan 750021, China
3.
Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan 750021, China

Funds:

the National Science Foundation of China 21666001

Scientific Research Project of North Minzu University 2017HG04

Major Research Project of North Minzu University ZDZX201803

Research Platform Project of North Minzu University 201707

Graduate Innovation Project of North Minzu University YCX19114

摘要

摘要: 为阐明微波场联合过氧乙酸（PAA）脱除煤中有机硫的机理，选取山西临汾（LF）、宁夏宁东（ND）、山西灵石（LS）和河南洛阳（LY）脱矿物质煤及三种含硫模型化合物苄硫醇（Benzyl mercaptan，BM）、苯并（b）噻吩（Benzo（b）thiophene，BT）和二苯基亚砜（Diphenyl sulfoxide，DS）作为研究对象。微波功率为100 W，并联合PAA，辐照1-5 min，通过X射线光电子能谱仪（X-ray photoelectron spectroscopy，XPS）分析固相中硫形态的变化；通过离子色谱仪（Ion chromatography，IC）分析脱硫后液相中SO₄^2-的浓度；通过气相色谱-质谱联用仪（Gas chromatography/mass spectrometry，GC/MS）分析萃取物中硫形态的变化。结果表明，有机硫化物硫的含量高，脱硫率大，LY和LS最大脱硫率分别高达55.06%和45.78%，ND和LF最大脱硫率分别为31.24%和28.21%，煤中的硫醇比噻吩和亚砜更易脱除，且脱硫过程中硫形态逐渐向高价态转化，含硫键在微波场中断裂，最终可被PAA氧化为SO₄^2-。
- 脱硫 /
- 微波 /
- 有机硫 /
- GC/MS /
- 含硫模型化合物
Abstract: In order to clarify the effect of microwave field combined with peracetic acid (PAA) on the removal of organic sulfur in coal, four demineralized coals including Shanxi Linfeng (LF), Ningxia Ningdong (ND), Shanxi Lingshi (LS) and Henan Luoyang (LY) coal were selected, and three sulfur-containing model compounds including benzyl mercaptan (BM), benzo(b) thiophene (BT) and diphenyl sulfoxide (DS) were used as well. Each test, the microwave with the power of 100 W irradiated coal for 1-5 min combined with PAA. The change of sulfur form in the solid phase was analyzed by X-ray photoelectron spectroscopy (XPS). The concentration of SO₄^2- in the liquid phase after desulfurization was analyzed by ion chromatography (IC), and the change of sulfur form in the extract was analyzed by gas chromatography/mass spectrometry (GC/MS). The results show that the higher the organic sulfur content, the greater the desulfurization rate. The maximum desulfurization rates of LY and LS are as high as 55.06% and 45.78%, respectively, and the maximum desulfurization rates of ND and LF are 31.24% and 28.21%, respectively. It is found that the organic sulfur as mercaptan in coal is easier to remove than that as thiophene and sulfoxide, and the sulfur form gradually transforms to a high valence state during desulfurization. The sulfur-containing bond is broken in the microwave field and the sulfur can be oxidized to SO₄^2- by PAA finally.
- desulfurization /
- microwave /
- organic sulfur /
- GC/MS /
- sulfur-containing model compound

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图 1 微波辐照脱灰煤样的脱硫率

Figure 1 Desulfurization rate of microwave irradiated deashed coal samples

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图 2 微波辐照模型化合物的脱硫率

Figure 2 Desulfurization rate of microwave irradiation model compound

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图 3 微波作用前后四种脱灰煤的S 2p谱图

Figure 3 S 2p spectra of four demineralized coals before and after microwave action

(a): ND; (b): LY; (c): LF; (d): LS; (e): ND-M; (f): LY-M; (g): LF-M; (h): LS-M

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图 4 微波辐照不同时间含硫模型化合物的S 2p谱图

Figure 4 Microwave irradiation of S 2p spectra of sulfur-containing model compounds at different times

a: raw; b: 1min; c: 5min

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图 5 微波辐照不同时间含硫模型化合物中硫形态的变化

Figure 5 Changes of sulfur form in sulfur-containing model compounds irradiated by microwave at different times

(a): benzyl mercaptan; (b): benzo[b]thiophene; (c): diphenyl sulfoxide

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图 6 DMF萃取模型化合物的总离子流色谱图

Figure 6 Total ion chromatogram of DMF extraction model compounds

(a): BM; (b): BT; (c): DS

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图 7 BM脱除机理示意图

Figure 7 BM removal mechanism diagram

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图 8 BT脱除机理示意图

Figure 8 BT removal mechanism diagram

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图 9 DS脱除机理示意图

Figure 9 DS removal mechanism diagram

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表 1 活性炭、原煤及脱灰煤的工业分析和元素分析

Table 1 Proximate and ultimate analyses of activated charcoal, raw coal and demineralized coal

Sample	Approximate analysis w_ad/%				Ultimate analysis w_daf/%
Sample	M	A	V	FC	C	N	O^*	H	S_t
AC	5.91	6.57	14.40	73.12	92.70	0.86	6.27	0.13	0.04
LF raw	0.94	20.67	23.62	54.77	70.57	1.16	18.45	4.41	5.41
ND raw	4.94	13.96	30.12	50.98	76.28	0.74	17.16	3.59	2.23
LS raw	0.92	57.00	13.05	29.03	60.08	1.64	26.04	2.28	9.96
LY raw	0.70	30.94	10.86	57.50	86.34	1.43	3.18	4.18	4.87
LY	0.61	1.57	15.36	82.46	85.13	1.61	3.52	5.62	4.12
ND	1.59	1.20	27.58	69.63	75.82	0.78	15.84	4.62	2.94
LS	0.70	1.86	22.63	74.81	60.92	1.69	26.64	3.26	7.49
LF	0.72	1.40	25.07	72.81	70.96	1.28	16.46	5.71	5.59

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表 2 原煤及脱灰煤的形态硫分析

Table 2 Sulfur forms of raw coal and demineralized coal

Sample	S_{p, ad/}%	S_{s, ad}/%	S_{o, ad}^*/%
LF raw	0.97	0.04	3.23
ND raw	0.78	0.12	0.91
LS raw	2.05	0.34	1.80
LY raw	0.96	0.09	2.28
LF	0.07	0.01	5.40
ND	0.07	0.01	2.78
LS	0.10	0.01	7.19
LY	0.08	0.01	3.94
S_p: pyrite; S_s: sulphate; S_o: organic sulfur; ^*: by difference

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表 3 不同辐照时间下模型化合物萃取液中SO₄^2-含量

Table 3 SO₄^2- content in model compound extracts under different irradiation time

Sample	Time t/min	Retain time t/min	SO₄^2- content w/(μg·mL^-1)
BM	1	13.42	70.30
	5	13.62	185.90
BT	1	13.39	30.25
	5	13.58	85.90
DS	1	13.43	20.11
	5	13.69	66.17

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表 4 萃取物的GC/MS可检测含硫化合物分布

Table 4 Sulfur compounds detected by GC/MS in the extracts

Sample	Peak	Name	Structure
BM	1	benzyl mercaptan
	2	benzyl sulfide
	3	bis-phenylmethy disulfide
	4	benzyl sulfone
BT	1	benzyl[b]thiophene
	2	benzene ethyl sulfonate
	3	benzyl[b]thiophene sulfoxide
	4	benzyl[b]thiophene sulfone
DS	1	diphenyl sulfoxide
	2	diphenyl sulfone

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