粒径对不同煤阶煤焦气化反应活性的影响研究

邹晓鹏; 盛羽静; 陆海峰; 郭晓镭; 郭庆华; 龚欣

粒径对不同煤阶煤焦气化反应活性的影响研究

邹晓鹏^{1, 2},
盛羽静^{1, 2},
陆海峰^{1, 2},
郭晓镭^{1, 2},
郭庆华^{1, 2},
龚欣^{1, 2, ,}

1.
上海市煤气化工程技术研究中心, 上海 200237
2.
煤基能源化工协同创新中心, 上海 200237

基金项目:

中国石油化工股份有限公司科技开发项目 415022

中央高校基本科研业务费专项资金 222201414030

详细信息

通讯作者:
龚欣, Tel:021-64252521, Fax:021-64251312, E-mail:gongxin@ecust.edu.cn

中图分类号: TQ541
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- 文章访问数: 101
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- 被引次数: 0
出版历程
- 收稿日期: 2016-12-07
- 修回日期: 2017-02-13
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-04-10

Effect of particle size on gasification of char with different coal ranks

ZOU Xiao-peng^{1, 2},
SHENG Yu-jing^{1, 2},
LU Hai-feng^{1, 2},
GUO Xiao-lei^{1, 2},
GUO Qing-hua^{1, 2},
GONG Xin^{1, 2
, ,}

1.
Shanghai Engineering Research Center of Coal Gasification, Shanghai 200237, China
2.
Collaborative Innovation Center of Chemical Technology for Coal Based Energy, Shanghai 200237, China

Funds:

Sinopec Scientific and Technological Development Projects 415022

the Fundamental Research Funds for the Central Universities 222201414030

摘要

摘要: 选取气流床气化炉所使用不同煤阶的八种煤焦，通过多级筛分制得单分散煤粉样本，利用热重分析仪考察了气化温度、煤焦粒径对不同煤阶煤焦CO₂气化反应的影响。对比了不同碳转化率阶段下的反应差异，并讨论了高碳转化率阶段的情况。研究表明，随着煤阶的升高，煤焦碳微晶结构更为有序，其气化活性也随之降低。煤焦粒径对气化反应的影响与煤阶有关。对于无烟煤，平均粒径300 μm的无烟煤煤焦转化率达到95%所需时间可达40 μm煤焦的7倍；对于褐煤与烟煤，由于其孔隙结构较为发达，粒径变化对煤焦气化活性的影响并不明显。综合煤阶、气化温度、煤焦粒径对气化反应活性的影响发现，相较低阶煤，提高气化温度、减小煤焦粒径能够更有效地提升高阶煤气化反应活性。
- 煤阶 /
- 气化温度 /
- 粒径 /
- CO₂气化
Abstract: Eight coal chars of different coal ranks were prepared to investigate the effects of coal rank, reaction temperature and particle size on char-CO₂ gasification using a thermogravimetric analyzer (TGA). The variation of char-CO₂ gasification rate with carbon conversion was studied, especially at high conversion stage. As a result, the crystalline structures of higher rank chars are more orderly, resulting in a lower gasification rate. For high rank coals like anthracite, the CO₂ gasification rate of char with 40 μm size is about 7 times higher than that with 300 μm size to reach 95% conversion at 1 300℃. For low rank coals, particle size has little effect on the gasification rate. The results indicate that the effect of particle size on char-CO₂ gasification is dependent on coal rank. The specific surface area of high rank coals is much smaller than that of low rank coals, which contributes to the significant effect of particle size on high rank coal gasification. The effect of gasification temperature and particle size on gasification rate for high rank coals is more significant than that for low rank coals.
- coal rank /
- gasification temperature /
- particle size /
- CO₂ gasification

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图 1 不同煤样碳转化率随气化反应时间的变化 (1 300 ℃)

Figure 1 Gasification reaction curves of fine char samples with different ranks

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图 2 不同煤样的气化反应速率随碳转化率的变化

Figure 2 Gasification rate vs. carbon conversion for different ranks of char samples

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图 3 酸洗煤焦碳转化率随气化反应时间的变化 (1 300 ℃)

Figure 3 Gasification carbon conversion vs. time for ash-free char samples

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图 4 煤焦的XRD谱图

Figure 4 XRD spectra of chars with different coal ranks

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图 5 温度对气化反应碳转化率的影响

Figure 5 Gasification reaction curves of chars at different temperatures

(a): NM; (b): SF; (c): ZJX; (d): JC

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图 6 粒径对气化反应碳转化率的影响 (1 300 ℃)

Figure 6 Effect of particle size on char gasification at 1 300 ℃

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图 7 JC煤焦初始反应速率与比表面积的关系 (1 300 ℃)

Figure 7 Initial gasification rate vs specific surface area (1 300 ℃)

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表 1 煤样的工业分析、元素分析及灰熔点

Table 1 Proximate, ultimate analysis and ash fusion temperature of coal samples

Sample	Proximate analysis w_d/%			Ultimate analysis w_d/%					Ash fusion temperature t/℃
Sample	V	FC	A	C	H	N	S	O	DT	ST	HT	FT
YN	55.23	39.86	4.91	59.80	4.86	0.76	0.26	29.41	1 081	1 140	1 151	1 163
NM	49.22	40.33	10.45	74.65	3.32	1.20	0.58	9.80	1 086	1 105	1 121	1 124
SF	35.42	58.29	6.29	79.14	2.32	1.12	0.77	10.36	1 152	1 167	1 175	1 179
SH	32.29	60.89	6.82	77.18	3.73	1.04	0.60	10.63	1 113	1 137	1 143	1 156
ZJX	30.19	51.58	18.23	70.23	4.28	1.19	0.34	5.73	1 458	>1 500	>1 500	>1 500
JC	5.35	78.32	16.33	78.76	1.08	0.91	1.97	0.95	1 440	>1 500	>1 500	>1 500
GZ	8.45	73.76	17.79	74.52	2.00	1.05	4.07	0.57	1 271	1 345	1 359	1 373
GP	7.96	76.81	15.23	74.59	3.03	0.91	3.12	3.12	1 342	>1 500	>1 500	>1 500

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表 2 煤样的灰组分分析

Table 2 Ash compositions of samples

Sample	Composition w/%
Sample	SiO₂	Al₂O₃	Fe₂O₃	CaO	SO₃	MgO	Na₂O	TiO₂	K₂O	SrO
YN	29.17	9.40	15.29	16.17	12.89	14.29	0.47	0.49	0.06	0.09
NM	43.46	14.43	14.13	11.81	10.02	3.04	1.46	0.63	0.32	0.14
SF	44.20	18.19	11.28	15.58	5.63	1.12	1.89	0.60	0.95	0.41
SH	46.68	20.34	6.65	14.39	6.52	1.03	2.20	0.79	0.88	0.12
ZJX	58.06	34.19	2.33	0.85	0.50	0.43	0.58	1.99	0.83	0.19
GZ	50.73	31.36	8.93	1.79	1.46	1.05	0.35	2.29	1.47	0.05
JC	50.22	38.12	5.74	2.07	1.12	0.51	0.41	1.01	0.61	0.02
GP	52.85	35.43	3.95	2.32	2.39	0.72	0.16	1.18	0.75	0.06

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表 3 煤样的粒径分布

Table 3 Particle size distribution of fine samples

Sample	Volume average particle size d/μm	< 10 μm	10-20 μm	20-50 μm	50-80 μm	80-120 μm	120-200 μm	σ_g	R²
YN	40	0	8.16	80.98	10.77	0.09	0	1.30	0.967
NM	40	0	5.56	75.22	17.76	1.47	0	1.29	0.973
SF	40	0	6.93	76.03	16.58	0.44	0	1.31	0.976
SH	40	0	2.69	77.37	18.66	1.28	0	1.29	0.968
ZJX	40	0	8.67	75.41	15.49	0.45	0	1.32	0.967
GZ	40	0	4.58	75.08	19.09	1.27	0	1.32	0.964
JC	40	0	10.65	73.51	15.48	0.33	0	1.30	0.969
GP	40	0	5.56	74.12	18.88	1.45	0	1.31	0.971

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表 4 筛分煤样的σ_g和R²

Table 4 σ_g and R² of sieved samples

Sample	Volume average particle size d/μm	σ_g	R²	Sample	Volume average particle size d/μm	σ_g	R²
NM	40	1.29	0.973	GZ	40	1.32	0.964
	90	1.19	0.988		90	1.21	0.980
	300	1.30	0.967		310	1.29	0.988
SF	40	1.31	0.976	JC	40	1.30	0.969
	100	1.22	0.985		90	1.24	0.976
	310	1.29	0.983		300	1.27	0.981
ZJX	40	1.32	0.967	GP	40	1.32	0.971
	90	1.20	0.985		90	1.20	0.986
	320	1.26	0.982		310	1.24	0.979

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表 5 不同煤样的气化反应参数 (1 300 ℃)

Table 5 Reaction parameters of various chars gasification at 1 300 ℃

Sample	t_0.5/min	t_0.95/min	R_0.5/min^-1	R_0.95/min^-1	r_{0.5, R}^*	r_{0.95, R}^*
YN	0.47	1.19	1.06	0.80	1.00	1.00
NM	0.57	1.42	0.88	0.67	1.21	1.19
SF	0.73	1.87	0.68	0.51	1.55	1.61
SH	0.76	2.12	0.66	0.45	1.62	1.82
ZJX	0.87	3.43	0.57	0.28	1.85	2.88
GZ	1.08	4.80	0.46	0.20	2.30	4.00
JC	1.16	3.60	0.43	0.26	2.47	3.03
GP	1.08	4.27	0.46	0.22	2.30	3.59
^*：r_{0.5, R} and r_{0.95, R} is the ratio of the R_0.5 and R_0.95 of YN char sample to the R_0.5 and R_0.95 of other char, respectively

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表 6 煤焦碳微晶结构参数

Table 6 Crystallite parameters of chars with different coal ranks

Sample	d₀₀₂	L_C	L_C/ d₀₀₂
NM char	0.373 8	0.850 9	2.276 4
SF char	0.368 1	0.878 5	2.386 8
JC char	0.363 7	1.025 3	2.819 5

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表 7 不同煤样的气化反应参数

Table 7 Reaction parameters of chars at different temperatures

Sample	t_0.5/min	t_0.95/min	R_0.5/min	R_0.95/min	r_{0.5, T}^*	r_{0.95, T}^*
NM-1 000 ℃	1.69	4.25	0.30	0.22	3.7	3.2
NM-1 300 ℃	0.45	1.32	1.11	0.72
SF-1 000 ℃	2.89	8.22	0.19	0.12	4.0	5.2
SF-1 300 ℃	0.73	1.87	0.68	0.50
ZJX-1 000 ℃	11.59	43.49	0.04	0.02	13.3	12.7
ZJX-1 300 ℃	0.87	3.43	0.57	0.28
JC-1 000 ℃	21.56	111.42	0.02	0.01	18.4	31.0
JC-1 300 ℃	1.16	3.60	0.43	0.26
^*: r_{0.5, T} and r_{0.95, T} are the ratio of R_0.5 and R_0.95 at 1 300 ℃ to R_0.5 and R_0.95 at 1 000 ℃

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表 8 不同煤样的气化反应参数 (1 300 ℃)

Table 8 Reaction parameters of chars with different particle sizes at 1 300 ℃

Sample	t_0.5/min	t_0.95/min	R_0.5/min	R_0.95/min	r_{0.5, P}^*	r_{0.95, P}^*
NM-40 μm	0.57	1.42	0.88	0.67	1.18	1.20
NM-300 μm	0.67	1.71	0.75	0.56
SF-40 μm	0.65	1.57	0.77	0.61	1.11	1.15
SF-300 μm	0.72	1.80	0.69	0.53
ZJX-40 μm	0.87	3.43	0.57	0.28	2.13	1.88
ZJX-300 μm	1.85	6.44	0.27	0.15
GZ-40 μm	1.08	4.80	0.46	0.20	5.94	6.55
GZ-300 μm	6.42	31.43	0.08	0.03
JC-40 μm	1.17	3.60	0.43	0.26	5.01	7.38
JC-300 μm	5.86	26.56	0.09	0.04
GP-40 μm	1.08	4.27	0.40	0.22	5.06	6.78
GP-300 μm	5.47	28.95	0.09	0.03
^*: r_{0.5, p} and r_{0.95, p} were the ratio of R_0.5 and R_0.95 of 40 μm chars to R_0.5 and R_0.95 of 300 μm chars

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表 9 不同粒径NM焦和JC焦的比表面积

Table 9 Specific surface area of NM chars and JC chars

Sample		40 μm	100 μm	300 μm
NM	A/(m²·g^-1)	108.5	153.9	149.2
	IGR /min^-1	1.13	1.19	0.94
JC	A/(m²·g^-1)	1.96	1.78	1.50
	IGR /min^-1	0.39	0.29	0.13

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表 10 气化反应参数对比

Table 10 Comparison of different kinetic parameters

Sample	r_{0.5, R}	r_{0.95, R}	r_{0.5, P}	r_{0.95, P}	r_{0.5, T}	r_{0.95, T}
NM	1.18	1.20	1.27	1.16	3.76	3.22
SF	1.55	1.61	1.11	1.15	3.96	5.24
ZJX	1.85	2.88	2.13	1.88	13.32	12.68
JC	2.47	3.03	5.01	7.38	18.43	30.95

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