水热炭化生物质与煤共热解和共气化特性研究

何清; 程晨; 龚岩; 丁路; 于广锁

doi:10.19906/j.cnki.JFCT.2022002

水热炭化生物质与煤共热解和共气化特性研究

doi: 10.19906/j.cnki.JFCT.2022002

何清^1,,
程晨¹,
龚岩¹,
丁路^1, ,,
于广锁^{1, 2}

1.
华东理工大学洁净煤技术研究所, 上海 200237
2.
宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室, 宁夏银川 750021

基金项目: 国家重点研发计划政府间合作项目(2021YFE0108900)和上海市浦江人才计划 (20PJ1402800)资助

详细信息

通讯作者:
E-mail: dinglu@ecust.edu.cn

中图分类号: TQ530.2
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- 被引次数: 0
出版历程
- 收稿日期: 2021-11-08
- 修回日期: 2022-01-02
- 录用日期: 2022-01-05
- 网络出版日期: 2022-01-18
- 刊出日期: 2022-06-25

Study on co-pyrolysis and co-gasification of hydrothermal carbonized biomass and coal

HE Qing^1
,,
CHENG Chen¹,
GONG Yan¹,
DING Lu^{1
, ,},
YU Guang-suo^{1, 2}

1.
Institute of Clean Coal Technology, East China University of Science and Technology, Shanghai 200237, China
2.
State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering, Ningxia University, Yinchuan 750021, China

Funds: The project was supported by the National Key Research and development (R&D) Project between Governments (2021YFE0108900) and Shanghai Pujiang Talents Plan (20PJ1402800)

摘要

摘要: 煤和生物质共热化学转化有助于当前化石能源系统的低碳化发展。本研究以烟煤和木质生物质为原料，研究煤和生物质共热解和共气化特性，并考察了不同水热炭化温度和生物质掺混比的影响。利用热重分析仪和在线质谱分析共热解和共气化的协同作用和氢气释放特性。采用Model-fitting方法，单独分析热解和气化阶段的整体反应动力学。结果表明，煤和生物质共气化阶段的协同作用显著强于共热解阶段。生物质比例越高，共气化协同作用越明显，水热炭化会削弱共气化的协同作用。共热解过程，H₂的产生受抑制。共气化过程可采用一级模型描述，而共热解过程需遵循n级反应模型。未处理的或轻度水热炭化的生物质与煤的混合物，共热解整体活化能和反应级数大于加权平均值，而其共气化的活化能变化趋势相反。重度水热炭化生物质与煤的混合物，共热解和共气化的活化能均接近加权平均值。
- 共热解 /
- 共气化 /
- 产氢 /
- 动力学 /
- 协同作用
Abstract: The co-thermochemical conversion of coal and biomass can contribute to the low carbonization of current fossil energy system. In this work, the bituminous and lignocellulosic biomass were selected to study the co-pyrolysis and co-gasification of coal and biomass, with the consideration of different hydrothermal carbonization (HTC) temperature and biomass blending ratio. The synergistic effect of co-pyrolysis and co-gasification was analyzed by using the thermogravimetric analyzer, and the H₂ release property was investigated by the online mass spectrometer. The model-fitting method was adopted to analyze the overall kinetics during pyrolysis and gasification stage, respectively. The results showed that the synergistic effect of coal and biomass in co-gasification stage was much stronger than that in co-pyrolysis stage. The gasification synergy was enhanced with the biomass blending ratio, while the HTC pretreatment could weaken the synergy. The H₂ production was inhibited during co-pyrolysis. The first-order reaction model could well describe the co-gasification process, while the n-order reaction model was suitable for the co-pyrolysis process. For the blends of raw or the slight HTC biomass and coal, the overall pyrolysis activation energy (E_a) was greater than that calculated by the weighted average, whereas the overall gasification E_a showed the opposite trend. For the blends of the severe HTC biomass and coal, the E_a of co-pyrolysis and co-gasification were both close to the weighted average value.
- co-pyrolysis /
- co-gasification /
- H₂ generation /
- kinetics /
- synergistic effect

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FIG. 1587. FIG. 1587.

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图 1 煤和生物质单独热解气化反应速率随温度变化

Figure 1 Reaction rate varied with temperature during individual pyrolysis and gasification of coal and biomass

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图 2 煤和生物质单独热解气化的H₂释放特性

Figure 2 H₂ release property during individual pyrolysis and gasification of coal and biomass

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图 3 煤和生物质共热解共气化反应速率随温度变化

Figure 3 Reaction rate varied with temperature during co-pyrolysis and co-gasification of coal and biomass

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图 4 煤和生物质共热解共气化的氢气释放特性

Figure 4 H₂ release property during co-pyrolysis and co-gasification of coal and biomass

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图 5 热解动力学拟合直线 (a) Coats-Redfern (b) Sestak-Berggren (SF-PIW为例)

Figure 5 Pyrolysis kinetics fitting lines (a) Coats-Redfern (b) Sestak-Berggren (SF-PIW as an example)

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图 6 共热解活化能和反应级数随生物质掺混比变化

Figure 6 Activation energy and reaction order varied with biomass blending ratio during co-pyrolysis

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图 7 非等温共气化主体温度区间

Figure 7 Main temperature range for non-isothermal co-gasification

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图 8 气化动力学拟合直线 (Coats-Redfern, SF-PIW为例)

Figure 8 Gasification kinetics fitting lines (Coats-Redfern, SF-PIW as an example)

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图 9 非等温共气化活化能随掺混比变化

Figure 9 Activation energy varied with biomass blending ratio during co-gasification

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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 analysis w_d/%			Ultimate analysis w_daf/%
Sample	A	V	FC	C	H	O^*	N	S
PIW	2.84	81.20	15.96	43.31	5.71	50.59	0.19	0.19
PIW180	1.71	83.79	14.50	46.01	6.14	47.42	0.28	0.15
PIW240	1.69	65.34	32.97	60.14	5.58	33.81	0.32	0.15
POW	9.79	74.33	15.88	40.57	5.49	53.34	0.45	0.15
POW180	7.51	76.20	16.29	43.34	5.69	50.40	0.43	0.14
POW240	11.07	57.00	31.93	50.44	4.81	44.16	0.44	0.15
SF	6.65	30.82	62.53	80.90	4.37	13.06	1.11	0.56
V: volatile; A: ash; FC: fixed carbon; ad: air dry basis; daf: dry ash-free basis; *: by difference

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表 2 样品的灰分组成

Table 2 Ash composition of samples

Sample	Content w/%
Sample	SiO₂	CaO	Al₂O₃	Fe₂O₃	K₂O	MgO	Na₂O	P₂O₅
PIW	35.76	31.45	8.97	6.43	6.05	4.00	3.07	0.73
PIW180	48.69	17.58	15.77	6.91	3.59	3.07	1.61	0.49
PIW240	48.96	13.42	19.20	6.25	4.17	3.04	1.54	0.70
POW	50.57	15.59	14.02	6.32	4.55	4.21	2.19	1.01
POW180	55.00	13.26	14.63	6.95	3.24	3.21	1.35	0.94
POW240	59.23	8.68	17.08	5.82	3.04	2.97	1.31	0.66
SF	29.03	19.20	17.33	6.73	0.78	6.63	1.23	0.07

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表 3 热解气化反应主要参数

Table 3 Main parameters for pyrolysis and gasification

Sample	Pyrolysis			Gasification			H₂ release
Sample	mass fraction^*	t_p/℃	R_p /(%·min⁻¹)	mass fraction	t_g /℃	R_g /(%·min⁻¹)	t_H /℃
PIW	80.6	363	0.184	19.4	894	0.03	372
PIW180	80.6	368	0.241	19.4	867	0.023	381
PIW240	61.9	368	0.099	38.1	1034	0.038	379
POW	79.5	358	0.225	20.5	891	0.032	366
POW180	81.6	371	0.268	18.4	901	0.029	380
POW240	60.8	371	0.114	39.2	979	0.034	384
SF	26.2	456	0.028	73.8	1028	0.088	479
*: ash-free base

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