含油污泥与配合煤共热解煤焦的微观结构与气化反应特性

邹涛; 朱春鹏; 张瑜; 林益安; 刘军; 杜彦学

含油污泥与配合煤共热解煤焦的微观结构与气化反应特性

邹涛^{1, 2, ,},
朱春鹏^{1, 2},
张瑜^{1, 2},
林益安^{1, 2},
刘军^{1, 2},
杜彦学^{1, 2}

1.
西北化工研究院有限公司, 陕西西安 710061
2.
陕西省煤化工工程技术研究中心, 陕西西安 710061

基金项目:

陕西省重点研发计划项目 2019GY-143

国家重点研发计划项目 2018YFB0604604

详细信息

中图分类号: TQ546
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- 文章访问数: 301
- HTML全文浏览量: 80
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- 被引次数: 0
出版历程
- 收稿日期: 2019-09-30
- 修回日期: 2019-12-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-02-10

Characteristics of microstructures and gasification reactivity of co-pyrolysis coal char with oily sludge and blended coal

ZOU Tao^{1, 2
, ,},
ZHU Chun-peng^{1, 2},
ZHANG Yu^{1, 2},
LIN Yi-an^{1, 2},
LIU Jun^{1, 2},
DU Yan-xue^{1, 2}

1.
Northwest Research Institule of Chemical Industry Co., Ltd., Xi′an 710061, China
2.
Shaanxi Coal Chemical Engineering Technology Research Center, Xi′an 710061, China

Funds:

The project was supported by Shaanxi Provincial Key Research and Development Program of China 2019GY-143

National Key Research and Development Project of China 2018YFB0604604

More Information

Corresponding author: ZOU Tao Tel: 029-89129836, E-mail: zoutao@aliyun.com

摘要

摘要: 以含油污泥与配合煤为原料在850-1150 ℃热解制得焦样, 采用N₂吸附-脱附和X射线衍射(XRD)分析煤焦孔隙结构及碳微晶结构, 并运用热重分析(TGA)考察热解温度和含油污泥添加量对煤焦气化反应活性的影响。结果表明, 提高热解温度和添加含油污泥能促进煤焦形成更加丰富的孔隙结构, 强化煤焦-CO₂气化反应接触并抑制煤焦石墨化进程, 从而提高煤焦气化反应活性；然而, 热解温度过高或添加油泥量过多则会致使煤焦结构致密或孔隙堵塞, 气化反应活性反而降低。
- 含油污泥 /
- 共热解 /
- 煤焦 /
- 微观结构 /
- 反应性
Abstract: Char samples were prepared by pyrolysis of oily sludge and blended coal at 850-1150 ℃. The pore structure and crystallite structure of chars were analyzed by N₂ adsorption-desorption and X-ray diffraction (XRD). Effects of pyrolysis temperature and amount of oily sludge on gasification reactivity of the char was investigated by thermogravimetric analysis (TGA). The results show that increasing pyrolysis temperature and adding oily sludge can promote the formation of more abundant pore structure of chars, strengthen chars-CO₂ gasification reaction and inhibit graphitization process of chars, thus improving gasification reactivity of the chars. However, too high pyrolysis temperature or too much sludge will also result in dense structure or pore plugging of coal char, and reduce gasification reactivity of the char.
- oily sludge /
- co-pyrolysis /
- char /
- microstructures /
- gasification reactivity

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图 1 实验装置流程示意图

Figure 1 A schematic diagram of the experimental apparatus

1: N₂ cylinder; 2: mass flowmeter; 3: one-way valve; 4: gas preheater; 5: high temperature reactor; 6: condenser; 7: tar tank; 8: acetone washing bottle; 9: ice bath; 10: indicator bottle; 11: wet flowmeter; 12: gas bag; 13: gas chromatography

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图 2 不同热解温度下制得煤焦的XRD谱图

Figure 2 XRD patterns of chars at different pyrolysis temperatures

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图 3 不同油泥添加量煤焦的XRD谱图

Figure 3 XRD patterns of chars at different DOS contents

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图 4 制焦温度对煤焦碳转化率的影响

Figure 4 Impact of pyrolysis temperature on char carbon conversion

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图 5 污泥添加量对煤焦碳转化率的影响

Figure 5 Impact of sludge addition on char carbon conversion

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图 6 含油污泥煤焦样品的Arrhenius曲线

Figure 6 Arrhenius curves of char samples with and without DOS

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表 1 样品的工业分析和元素分析

Table 1 Proximate and ultimate analyses of samples

Sample	Proximate analysisw_ad/%				Ultimate analysisw/%
Sample	M	A	V	FC	C_ad	H_ad	N_ad	S_{c, ad}	O_ad
CYM	4.77	5.69	31.40	58.14	69.84	5.18	0.78	0.87	12.87
QM	2.12	7.42	31.89	58.57	71.42	4.94	0.86	0.94	12.3
JM	3.07	60.67	6.57	29.69	72.56	4.42	0.97	3.77	8.64
DOS(105 ℃)	-	12.26	80.35	7.39	64.86	8.27	0.59	2.96	11.06

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表 2 含油污泥灰组成的X射线荧光光谱分析

Table 2 Composition of solids in DOS measured by XRF

Sample	Composition w/%
Sample	Fe₂O₃	SiO₂	CaO	Al₂O₃	Na₂	K₂O	ZnO	SO₃	TiO₂	MgO	MnO
DOS	30.24	17.05	12.56	6.78	6.38	4.27	3.35	3.08	2.01	1.54	0.79

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表 3 配合煤添加含油污泥制焦煤焦的孔隙结构特性

Table 3 Pore structure characteristics of char from pyrolysis of mixed coal loaded with oily sludge

Sample and pyrolysis temperature		BET A_total/(m²·g^-1)	Pore volume v_total/(mL·g^-1)	Average aperture D_a/nm
char	temperature t/℃	BET A_total/(m²·g^-1)	Pore volume v_total/(mL·g^-1)	Average aperture D_a/nm
CQJ	850	51.204	0.0425	5.904
DOS3		57. 142	0.0487	5.517
DOS8		65.637	0.0512	4.246
DOS15		64.892	0.0503	4.231
CQJ	950	69.025	0.0472	5.036
DOS3		74.217	0.0517	4.819
DOS8		90.417	0.0585	4.587
DOS15		85.057	0.0551	4.425
CQJ	1050	81.015	0.0503	5.003
DOS3		104.223	0.0529	4.224
DOS8		115.453	0.0592	4.087
DOS15		108.012	0.0576	4.425
CQJ	1150	78.705	0.0473	4.891
DOS3		87.227	0.0498	4.224
DOS8		88.415	0.0517	4.087
DOS15		70.004	0.0509	4.425

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表 4 煤焦样品的动力学参数

Table 4 Kinetic parameters of char samples

Sample	CQJ	DOS3	DOS8	DOS15
E/(kJ·mol^-1)	263.22	237.04	164.02	246.42
A	20.07	18.52	12.25	20.43

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