神府烟煤焦与城市固体废弃物水热炭焦共气化反应特性的实验研究

何清; 卫俊涛; 龚岩; 丁路; 于广锁

神府烟煤焦与城市固体废弃物水热炭焦共气化反应特性的实验研究

何清¹,
卫俊涛¹,
龚岩¹,
丁路²,
于广锁^1, ,

1.
华东理工大学煤气化及能源化工教育部重点实验室, 上海 200237
2.
东京工业大学环境社会理工学院, 东京 1528550

基金项目:

国家自然科学基金 21676091

国家自然科学基金 21376081

中央高校基本科研业务费 222201717004

详细信息

通讯作者:
于广锁, Tel:021-64252974, Fax:021-64251312;E-mail:gsyu@ecust.edu.cn

中图分类号: TQ541
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- 文章访问数: 99
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- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2017-06-24
- 修回日期: 2017-08-16
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-10-10

Experimental study on co-gasification reactivity of Shenfu bituminous coal char and MSW-based hydrochar

1.
Key Laboratory of Coal Gasification and Energy Chemical Engineering of Ministry of Education, East China University of Science & Technology, Shanghai 200237, China
2.
School of Environment and Society, Tokyo Institute of Technology, Tokyo 1528550, Japan

Funds:

the National Nature Science Foundation of China 21676091

the National Nature Science Foundation of China 21376081

the Fundamental Research Funds for the Central Universities 222201717004

摘要

摘要: 基于常压热重分析仪（TG）开展了神府烟煤焦（SF char）、水热炭焦（HTC char）及其混合物等温CO₂气化实验以研究气化温度（800-950℃）、掺混比（3：1、1：1、1：3）对共气化特性的影响，并探讨了气化反应活化能及其影响因素。结果表明，HTC因其较大的比表面积和较多的灰分而具有较强的气化活性。低HTC掺混比的混合物气化活性对温度变化敏感。低温下混合物的气化活性受HTC掺混影响显著。反应活化能随着反应转化率的增大而逐渐增大并趋于稳定。进一步研究表明，混合物的活化能与其掺混比以及活性矿物（K+Na）/Ca的物质的量比均存在近似线性关系。
- 共气化 /
- 煤 /
- 水热炭 /
- 反应特性 /
- 活化能
Abstract: The influences of gasification temperature (800-950℃) and blending ratio (3:1, 1:1, 1:3) on the isothermal CO₂ co-gasification reactivities of Shenfu bituminous coal char (SF char) and HTC char were investigated using an atmospheric thermogravimetric analyzer (TGA). Moreover, the activation energy of char gasification and its influence factors were explored. The results show that the greater surface area and the higher ash content are the main reasons for the high gasification reactivity of HTC char. The reactivities of mixtures with low HTC char proportion are more sensitive to temperature at low temperature range. The activation energy increases with the increase of carbon conversion, and the activation energy correlates well with the blending ratio and the molar ratio of active (K+Na)/Ca in the char.
- co-gasification /
- coal /
- hydrochar /
- reactivity /
- activation energy

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图 1 不同焦样等温气化转化率随时间的变化

Figure 1 Curves of carbon conversion versus gasification time for the different chars

■: SF-800P; ●: SF:HT-3:1-800P; ▲: SF:HT-1:1-800P; $\blacktriangledown$ : SF:HT-1:3-800P; $\blacktriangleleft$ : HTC-800P

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图 2 焦样的电镜照片

Figure 2 SEM of samples

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图 3 样品的比表面积

Figure 3 Specific surface areas of samples

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图 4 lnt~1/T关系图

Figure 4 Relationship between lnt and 1/T under different conversions

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图 5 共气化反应的温度效应

Figure 5 Influence of temperature on co-gasification

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图 6 共气化反应混合比例的影响

Figure 6 Influence of blending ratio on co-gasification

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图 7 活化能与转化率的关系

Figure 7 Variation of activation energy under different conversions

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图 8 活化能与掺混比的关系

Figure 8 Relationship between activation energy and char blending ratio

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图 9 活化能与活性AAEM关系

Figure 9 Relationship between activation energy and active AAEM

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表 1 样品的工业分析和元素分析

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

Sample	Proximate analysis w_d/%			Ultimate analysis w_d/%
Sample	V	FC	A	C	H	N	O^*	St
SF	35.42	58.29	6.29	79.14	2.32	1.12	10.36	0.77
SF char	6.48	82.255	10.27	87.17	0.91	0.54	1.01	0.10
HTC	69.71	11.38	18.91	47.36	8.56	1.78	23.01	0.38
HTC char	8.65	54.99	36.36	56.71	0.77	1.03	4.98	0.15
d：dry basis;^*：by difference

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表 2 样品的灰成分分析

Table 2 Ash composition of samples

Sample	Ash composition w/%
Sample	SiO₂	Al₂O₃	K₂O	Na₂O	CaO	Fe₂O₃	MgO
SF	33.36	12.44	0.67	1.73	27.78	9.11	1.34
HTC	20.22	8.07	3.58	4.40	37.43	5.14	2.06

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表 3 热解前后样品质量及混合比例变化

Table 3 Quality and blending ratio change of samples during pyrolysis

	SF m/g	HTC m/g	Mixing ratio (SF:HTC)
Raw material	20.00	20.00	3:1	1:1	1:3
Char	13.44	7.17	0.85:0.15	0.65:0.35	0.38:0.62

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表 4 SF半焦表面的元素组成

Table 4 Element composition on the surface of AF semi-char

	Content w /%
	Na	Mg	Al	Si	K	Ca	Fe
Co-gasification^{a, b}	5.66	0.99	2.08	3.70	2.64	2.36	0.83
Individual gasification	1.33	0.49	1.62	2.24	0.32	1.84	0.83
^a：SF semi-char was obtained from the mixture SF:HTC-1:1-800P ^b：At the same gasification time, the conversions were x_SF_:HTC_-1:1-800P=0.9 and x_SF-800P=0.67 respectively

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表 5 不同转化率活化能拟合的校正决定系数

Table 5 The Adj. R. Square (R²) of activation energy under different conversion

Sample	R²
Sample	0.1	0.2	0.3	0.4	0.5	0.6	0.7	0.8	0.9
SF-800P	0.978	0.983	0.986	0.989	0.993	0.995	0.997	0.998	0.999
SF:HTC-3:1-800P	0.979	0.987	0.991	0.993	0.994	0.994	0.995	0.995	0.996
SF:HTC-1:1-800P	0.970	0.986	0.992	0.995	0.995	0.996	0.996	0.996	0.996
SF:HTC-1:3-800P	0.960	0.981	0.988	0.991	0.993	0.995	0.994	0.994	0.994
HTC-800P	0.986	0.982	0.985	0.987	0.988	0.990	0.991	0.990	0.989

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表 6 气化反应的活化能

Table 6 Gasification activation energy

Conversion	Gasification activation energy E_A/(kJ·mol^-1)
Conversion	SF-800P	SF-HTC-3:1-800P	SF-HTC-1:1-800P	SF-HTC-1:3-800P	HTC-800P
0.1	192.34	176.16	149.62	133.11	114.43
0.2	201.85	187.42	163.05	142.04	126.83
0.3	207.31	195.00	169.71	147.46	133.91
0.4	210.08	199.28	177.10	150.39	137.06
0.5	211.30	201.22	182.80	152.48	139.89
0.6	211.73	201.95	185.28	158.17	141.48
0.7	211.85	202.31	186.04	163.59	140.86
0.8	211.63	203.10	186.07	164.66	139.94
0.9	211.15	204.30	185.35	162.75	139.80
Average value	207.69	196.75	176.11	152.74	134.91

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表 7 焦活性AAEM含量

Table 7 Content of active AAEM in char

	AAEM w/(mmol·g^-1)
		SF-800P	SF-HTC-3:1-800P^*	SF-HTC-1:1-800P^*	SF-HTC-1:3-800P^*	HTC-800P
K	0.0015	0.0472	0.1082	0.1904	0.3062
Na	0.0061	0.0441	0.0948	0.1632	0.2596
Ca	0.5000	0.5705	0.6646	0.7916	0.9703

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