低阶烟煤热解过程中氯的迁移释放特性研究

赵宁; 刘东; 郭中山; 周家顺; 龚鑫; 于冉; 王峰

低阶烟煤热解过程中氯的迁移释放特性研究

赵宁¹,
刘东^1, ,,
郭中山²,
周家顺¹,
龚鑫¹,
于冉¹,
王峰²

1.
中国石油大学(华东)化学工程学院重质油国家重点实验室, 山东青岛 266580
2.
神华宁夏煤业集团有限责任公司煤制油分公司, 宁夏银川 751410

基金项目:

国家重点研发计划项目 2017YFB0602500

详细信息

中图分类号: TQ530.2
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- 文章访问数: 135
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- 被引次数: 0
出版历程
- 收稿日期: 2019-04-23
- 修回日期: 2019-06-12
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-09-10

Investigation on transferring and release characteristics of chlorine during pyrolysis of low rank coal

1.
State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University Of Petroleum(East China), Qingdao 266580, China
2.
CTL Chemical of SNCG, Yinchuan 751410, China

Funds:

the National Key Research and Development Project of China 2017YFB0602500

More Information

Corresponding author: LIU Dong, Tel: 0532-86980381, E-mail: liudong@upc.edu.cn

摘要

摘要: 为探明氯元素在低阶烟煤热解过程中的释放机制行为，采用热重红外光谱质谱（TG-IR-MS）联用技术和管式热解炉，考察热解温度、粒径等级、升温速率对陕北低阶烟煤热解过程中氯的迁移转化行为特性的影响，并建立氯迁移释放动力学模型。红外光谱和质谱分析结果表明，陕北低阶烟煤热解气体产物中含氯组分主要为HCl和微量的Cl₂。管式炉热解过程中，相比于粒径和升温速率而言，氯的释放率受温度影响最为显著。在300-800 ℃，随着温度升高，煤中氯的释放率迅速增大，800 ℃时氯的释放率为49.5%；半焦中氯的分布率逐渐减小，焦油和热解气中氯的分布率逐渐增大。煤样粒径为3.0-4.0 mm时，氯的释放率达到最大值35.8%；粒径的变化也会一定程度影响热解产物中氯的分布率。提高热解升温速率有利于挥发分的释放，升温速率为15-25 ℃/min时，煤中氯的释放率变化趋势明显，但过高的升温速率不利于煤中氯的释放。热解焦油中氯元素主要以无机含氯化合物的形式存在，超纯水萃取可明显降低焦油中氯的含量。低阶烟煤中低温热解过程中，氯释放的活化能均在20 kJ/mol左右。
- 低阶烟煤 /
- 热解 /
- 焦油 /
- TG-IR-MS /
- 动力学
Abstract: In order to reveal the release mechanism of chlorine(Cl) in low rank coal during pyrolysis process, a low rank coal from northern Shaanxi was pyrolyzed at different temperatures, particle sizes and heating rates in a tubular reactor and a Thermo Gravimetric-Infrared-Mass spectrometry (TG-IR-MS) to investigate the transferring and release characteristics of Cl during pyrolysis process. The dynamic model of Cl transferring and release was built based on the process of coal pyrolysis. The results show that the chloric species from the pyrolysis of low rank coal is HCl and little Cl₂, and the temperature strongly influences the release rate of Cl during pyrolysis in the tubular reactor. With the pyrolysis temperature increasing from 300 to 800 ℃, the release rate of Cl increases significantly, reaching to 49.5% at 800 ℃, while the fraction of Cl in the char decreases and the fraction of Cl in coal tar and pyrolysis gas increases gradually. The release rate of Cl has a maximum of 35.8% as the particle size is 3.0-4.0 mm. The particle size also affects the distribution of Cl in pyrolysis products. Moreover, increasing the heating rate is beneficial to the devolatilization, and the release rate of Cl in coal changes obviously as the heating rate is 15-25 ℃/min, but much higher heating rate will result in the decrease of the release rate of Cl in coal. Most Cl species in the coal tar is in form of water-soluble inorganic chlorides, and therefore the ultrapure water can present a better performance to remove chlorides. The release activation energy of chlorine in pyrolysis is about 20 kJ/mol.
- low rank coal /
- pyrolysis /
- coal tar /
- TG-IR-MS /
- dynamics

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图 1 热解实验装置示意图

Figure 1 Pyrolysis experimental system

1: N₂ cylinder; 2: flowmeter; 3: pyrolysis device; 4: pyrolytic reaction tube; 5: silica wool; 6: low & constant temperature bath; 7: gas washing bottle with acetone; 8: gas collection bag

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图 2 煤样热解的TG-DTG曲线

Figure 2 TG-DTG curves during coal pyrolysis

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图 3 煤样热解气体产物的质谱曲线

Figure 3 MS curves of gases released during coal pyrolysis

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图 4 煤样热解气体产物的FT-IR光谱谱图

Figure 4 FT-IR 3D spectra of gases released during coal pyrolysis

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图 5 温度对半焦产率和氯释放率的影响

Figure 5 Effect of temperature on char yield and chlorine release

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图 6 温度对热解产物中氯分布率的影响

Figure 6 Effect of temperature on content of chlorine in pyrolysis products

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图 7 萃取前后焦油中氯元素的含量变化

Figure 7 Content variation of chlorine in coal tar before and after extraction

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图 8 粒径对半焦产率和氯释放率的影响

Figure 8 Effect of particle size on char yield and chlorine release

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图 9 粒径对热解产物中氯分布率的影响

Figure 9 Effect of particle size on distribution of chlorine in pyrolysis products

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图 10 升温速率对半焦产率和氯释放率的影响

Figure 10 Effect of heating rate on char yield and chlorine release

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图 11 升温速率对热解产物中氯分布率的影响

Figure 11 Effect of heating rate on distribution of chlorine in pyrolysis products

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图 12 煤样热解过程中氯释放动力学曲线

Figure 12 Kinetic curve of chlorine release during coal pyrolysis

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表 1 煤样的工业分析和元素分析

Table 1 Proximate and ultimate analyses of coal sample

d/mm	Proximate analysis w_d/%			Ultimate analysis w_daf/%				w_{d, Cl}^* /(μg·g^-1)
d/mm	A	V	FC	C	H	N	S	w_{d, Cl}^* /(μg·g^-1)
＜6	5.74	32.23	62.03	81.62	4.97	0.97	0.29	710
0.0-1.0	7.24	31.88	60.88	79.98	4.81	1.00	0.38	793
1.0-2.0	4.68	32.58	62.74	80.51	4.91	1.04	0.26	688
2.0-3.0	5.15	32.66	62.19	81.05	5.00	1.00	0.25	636
3.0-4.0	5.22	32.62	62.16	80.74	4.99	1.00	0.27	600
4.0-5.0	5.12	32.20	62.68	81.16	5.00	1.04	0.25	569
5.0-6.0	5.16	32.40	62.44	80.86	4.99	1.02	0.26	565
^*: By ECS3000

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表 2 不同升温速率下氯释放动力学参数

Table 2 Kinetic parameters of chlorine evolution at different heating rates

Heating rate/(℃·min^-1)	Activation energy E_a/(kJ·mol^-1)	Frequency factor A/min^-1	Relative coefficient R²
5	18.59	0.0459	0.9774
10	19.07	0.1007	0.9802
15	19.15	0.1381	0.9564
20	19.62	0.1949	0.9573

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表 3 不同粒径下氯释放动力学参数

Table 3 Kinetic parameters of chlorine evolution at different particle sizes

Particle size d/mm	Activation energy E_a/(kJ·mol^-1)	Frequency factor A/min^-1	Relative coefficient R²
0.0-1.0	21.42	0.2794	0.9973
1.0-2.0	20.62	0.2215	0.9400
2.0-3.0	20.33	0.1238	0.9764
3.0-4.0	20.16	0.1921	0.9638
4.0-5.0	20.25	0.1866	0.9736
5.0-6.0	20.38	0.2132	0.9783

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