无机酸洗脱对胜利褐煤微晶结构及其自燃倾向性的影响

班延鹏; 唐艳花; 王杰; 韩孟欣; 特古斯; 王琰; 何润霞; 智科端; 刘全生

无机酸洗脱对胜利褐煤微晶结构及其自燃倾向性的影响

内蒙古工业大学化工学院内蒙古自治区低阶碳质资源高值化利用重点实验室, 内蒙古呼和浩特 010051

基金项目:

国家自然科学基金 21566029

国家自然科学基金 21566028

国家自然科学基金 21266017

内蒙古自然科学基金 2014MS0220

内蒙古自然科学基金 2015BS0206

内蒙古自然科学基金 2016BS0204

内蒙古工业大学科学研究项目 ZS201138

详细信息

通讯作者:
智科端, E-mail: zhikeduan@gmail.com

刘全生, E-mail: liuqs@imut.edu.cn

中图分类号: TK16
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- 文章访问数: 69
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- PDF下载量: 8
- 被引次数: 0
出版历程
- 收稿日期: 2015-11-23
- 修回日期: 2016-01-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-09-10

Effect of inorganic acid elution on microcrystalline structure and spontaneous combustion tendency of Shengli lignite

Department of Chemical Engineering, Inner Mongolia University of Technology, Inner Mongolia University of Technology, Inner Mongolia Key Laboratory of High-Value Functional Utilization of Low Rank Carbon Resource, Huhhot 010051, China

Funds:

the National Natural Science Foundation of China 21566029

the National Natural Science Foundation of China 21566028

the National Natural Science Foundation of China 21266017

the Natural Science Foundation of Inner Mongolia-China 2014MS0220

the Natural Science Foundation of Inner Mongolia-China 2015BS0206

the Natural Science Foundation of Inner Mongolia-China 2016BS0204

the Science and Research Projects of IMUT-China ZS201138

摘要

摘要: 利用XRD、Raman、XPS和FT-IR表征技术，研究无机酸洗脱（HCl、H₂SO₄、HCl-HF）处理的胜利褐煤微晶结构的变化，采用自行设计的表面吸附仪-GC联用装置，对样品进行不同温度的低温脉冲氧化实验，考察了煤样在不同温度下氧吸附量的变化规律，通过低温脉冲氧吸附规律与TG/DTG和固定床燃烧实验关联，考察了煤样的自燃倾向。结果表明，无机酸洗脱对矿物质的脱除使得煤结构的有序度增加，石墨化程度提高，无机酸洗脱煤样与原煤相比吸氧量明显下降。随着吸附温度的升高，各煤样吸氧量明显增加，且随着脱除矿物质程度的增加，吸氧量呈减小的趋势，导致自燃倾向降低。
- 胜利褐煤 /
- 无机酸洗脱 /
- 微晶结构 /
- 低温氧化 /
- 自燃倾向
Abstract: XRD, Raman, XPS and FT-IR were used to examine microcrystalline structure changes of Shengli lignite eluted by inorganic acid (HCl, H₂SO₄ and HCl-HF). By adopting a designed surface adsorption instrument-GC, the samples were oxidized at low temperature through pulse method to investigate their oxygen adsorption under different temperatures. Via low-temperature oxidation, TG/DTG and fixed bed combustion tests, the spontaneous combustion tendency of coal samples were investigated. The results show that the removal of minerals increases the degree of order and graphitization of the coal structure. Compared with raw coal, oxygen absorption of inorganic acid elution samples decreases obviously. With the increase of adsorption temperature, oxygen absorption capacity increases significantly, but decreases with the increasing level of removed minerals, which reduces spontaneous combustion tendency of the treated coal.
- Shengli lignite /
- inorganic acid elution /
- microcrystalline structure /
- low-temperature oxidation /
- spontaneous combustion tendency

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图 1 低温氧化反应实验流程示意图

1: adsorbed gas; 2: carrier gas; 3: pressure reducing valve4: mass flow meter; 5: triple valve; 6: six-port valve; 7: temperature thermocouple; 8: adsorbor; 9: temperature controller; 10: temperature control thermocouple; 11: ice-bath; 12: cold-hydrazine; 13: purifier; 14: chromatographic; 15: thermal conductivity cell

Figure 1 Experiment flowchart of low temperature oxidation

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图 2 煤样的XRD谱图及SR拟合示意图

Figure 2 XRD spectra of samples and the fitting diagram of SR

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图 3 煤样的拉曼谱图及SR拟合示意图

Figure 3 Raman spectra of samples and the fitting diagram of SR

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图 4 煤样C 1s XPS谱图及SR拟合示意图

Figure 4 XPS C 1s spectra of coal samples and the fitting diagram of SR

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图 5 煤样的红外光谱谱图

Figure 5 FT-IR spectra of coal samples

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图 6 煤样耗氧量随温度的变化

Figure 6 variation tendency of coals' oxygen consumption with the increasing of temperature

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图 7 煤样的TG-DTG曲线

(a)：TG；(b)：DTG

Figure 7 TG-DTG curves of coal samples

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图 8 燃烧过程中CO₂浓度与温度的关系

Figure 8 Relation between CO₂ concentration and temperature in the process of combustion

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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/%
Sample	M_ad	A_d	V_d	FC_d	C	H	N	S	O^*
SR	1.52	13.92	33.37	52.71	57.59	3.58	0.89	1.81	22.21
SC	2.14	7.53	39.77	52.70	61.42	3.34	0.86	1.74	25.10
SS	2.60	5.35	33.26	58.79	58.16	4.21	0.87	1.78	27.03
SFC	2.18	1.14	41.97	56.89	64.90	4.88	0.91	1.69	26.48
^*：by difference

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表 2 洗脱煤样及所对应灰分中主要金属元素含量

Table 2 Metal ion percentage in coal samples and ashes

Coal sample	Coal based/ash based w/%
Coal sample	Al³⁺	Na⁺	Ca²⁺	Si⁴⁺	Feⁿ⁺	K⁺	Mnⁿ⁺
SR	2.40/35.50	0.58/8.59	0.41/6.08	3.11/46.09	0.11/1.69	0.08/1.18	0.06/0.88
SC	0.90/32.94	0.00/0.16	0.01/0.19	2.89/64.58	0.03/0.92	0.03/1.18	0.00/0.03
SS	0.87/31.21	0.00/0.12	0.05/6.01	0.75/61.36	0.04/1.03	0.00/0.12	0.00/0.15
SFC	0.11/41.77	0.00/1.03	0.01/2.10	0.14/53.31	0.00/1.22	0.00/0.13	0.00/0.45

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表 3 煤样的微晶结构参数

Table 3 Microcrystalline structure parameters of coal samples

Coal sample	d₀₀₂ /nm	L_a /nm	L_c /nm	N	f_a
SR	0.366	1.220	0.754	2.062	0.519
SC	0.357	1.471	0.773	2.162	0.531
SS	0.354	1.816	0.802	2.263	0.547
SFC	0.353	2.474	0.853	2.413	0.563

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表 4 煤样的Raman结构参数

Table 4 Raman structure parameters of coal samples

Coal sample	SR	SC	SS	SFC
I_D/I_G	0.921 8	0.885 5	0.857 3	0.843 4
I_S/I_G	0.445 4	0.352 5	0.237 9	0.209 7
I_D/I_{(V_R+V_L+G_R)}	0.463 0	0.721 1	0.739 5	0.750 4

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表 5 煤样的XPS C 1s拟合结果

Table 5 XPS C 1s fitting results of coal samples

E/eV	Carbon form	Content w_mol/%
E/eV	Carbon form	SR	SC	SS	SFC
284.6	C-C, C-H	83.91	84.80	81.77	79.42
286.4	C-O	10.84	8.58	9.29	10.62
287.5	C=O	3.14	3.55	4.98	5.88
289.0	COO-	2.11	3.07	3.96	4.08

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表 6 煤样氧消耗量与氧化温度的关系

Table 6 Relationship between O₂ consumption of coals and oxidation temperature

TEMP t/℃	O₂ consumption/(×10^-2 mmol·g^-1)
TEMP t/℃	SR	SC	SS	SFC
60	0.13	0.19	0.18	0.15
90	0.39	0.73	0.46	0.25
110	0.53	0.86	0.64	0.46
140	1.86	1.53	1.10	0.64
160	8.45	3.09	3.03	2.62

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