基于准东煤的Texaco气化炉灰渣组成结构特征与热转化性能

徐小伟; 莫文龙; 郝呈祥; 刘一波; 魏贤勇; 杨晓勤; 张书培

doi:10.1016/S1872-5813(21)60187-1

基于准东煤的Texaco气化炉灰渣组成结构特征与热转化性能

doi: 10.1016/S1872-5813(21)60187-1

徐小伟^1,,
莫文龙^1, ,,
郝呈祥^{1, 2},
刘一波¹,
魏贤勇^{1, 3, ,},
杨晓勤⁴,
张书培⁴

1.
新疆大学化工学院省部共建碳基能源资源化学与利用国家重点实验室, 煤炭清洁转化与化工过程新疆维吾尔自治区重点实验室, 新疆乌鲁木齐 830046
2.
国能新疆化工有限公司, 新疆乌鲁木齐 831400
3.
中国矿业大学煤炭加工与高效洁净利用教育部重点实验室, 江苏徐州 221116
4.
新疆宜化化工有限公司, 新疆昌吉 831700

基金项目: 新疆维吾尔自治区引进高层次人才天池计划，煤炭加工与高效洁净利用教育部重点实验室开放基金和新疆维吾尔自治区重点实验室开放课题（2018D04008）资助

详细信息

作者简介:
徐小伟（1997-）男，河北邯郸人，在读硕士研究生。Tel: 15690166691，E-mail: 305235242@qq.com

通讯作者:
E-mail: mowenlong@xju.edu.cn

wei_xianyong@163.com

中图分类号: TQ531
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出版历程
- 收稿日期: 2021-10-28
- 修回日期: 2021-12-20
- 录用日期: 2021-12-21
- 网络出版日期: 2022-01-28
- 刊出日期: 2022-07-10

Ash composition, structural characteristics and thermal conversion performance of Texaco gasifier based on Zhundong coal

1.
Key Laboratory of Coal Clean Conversion & Chemical Engineering Process (Xinjiang Uyghur Autonomous Region), College of Chemical Engineer, Xinjiang University, Urumqi 830046, China
2.
Guoneng Xinjiang Chemical Industry Co, Ltd, Urumqi 831400, China
3.
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou 221116, China
4.
Xinjiang Yihua Chemical Industry Co, Ltd, Changji 831700, China

Funds: The project was supported by Tianchi Project for Introducing High-level Talents to Xinjiang Uyghur Autonomous Region (China), Key Laboratory of Coal Processing and Efficient Utilization from Ministry of Education, and Open Project of Key Laboratory of Xinjiang Uygur Autonomous Region (2018D04008)

摘要

摘要: 解析以准东煤为原料的Texaco气化炉所排细渣和粗渣的组成结构特征，分析两者的热化学转化性能。结果表明，粗渣固定碳含量为42.31%，说明粗渣可以作为碳基原料实现高附加值利用。FT-IR分析显示，粗渣和细渣中Si−O的吸收峰更强，且细渣中含有少量的芳香结构。惰性气氛热分解行为发现，粗渣在600 ℃的失重速率最大，而细渣其最大失重速率峰转移到了620 ℃左右。氧化性气氛热分解结果表明，在500−700 ℃条件下，粗渣和细渣均有明显失重，且两者的失重主要源于固定碳的燃烧。采用Coats-Redfern法对惰性气氛和氧化性气氛下粗渣和细渣的失重曲线进行拟合，计算热解/燃烧活化能、相关系数等动力学参数。结果表明，在惰性气氛下，粗渣热解激烈段（560−640 ℃）反应级数设定为3时拟合效果较好，相关系数R²为0.99，活化能E为38.85 kJ/mol。细渣热解激烈段（590−650 ℃）同样在反应级数设定为3时拟合效果较好，相关系数R²为0.97，活化能E为79.09 kJ/mol。在氧化性气氛下，粗渣和细渣燃烧激烈段分别在540−605 ℃和530−605 ℃，反应级数均以n = 1时拟合效果较好，活化能E分别为226.46和154.73 kJ/mol。
- 煤气化 /
- 气化渣 /
- FT-IR /
- 热重分析法 /
- Coats-Redfern模型
Abstract: Composition and structure characteristics of fine slag (FS) and coarse slag (CS) discharged from Texaco gasifier with Zhundong coal as raw material were analyzed, and their thermochemical conversion properties were analyzed. Proximate and ultimate analyses show that the contents of fixed carbon in coarse slag are 42.31%, indicating that it can be used as raw material to realize its high-added utilization. Analysis with Fourier transform infare spectrometer (FT-IR) suggest that the absorption peak of Si−O in coarse slag and fine slag is stronger, and there is a small amount of aromatic structure in fine slag. Thermal decomposition behaviors in inert atmosphere show that the maximum weight loss rate peak of coarse slag is located around 600 ℃, while that of fine slag is transferred to about 620 ℃. Results of thermal decomposition in oxidization atmosphere show that there are obvious weight loss rate peaks derived from combustion of the fixed carbon in 500−700 ℃. The weight loss profiles of fine slag and coarse slag in inert and oxidization atmosphere were fitted by Coats-Redfern method. The kinetic parameters including pyrolysis/combustion activation energy and correlation coefficient were calculated. The results show that the fitting effect is better as the reaction order selected as 3 at the intense pyrolysis section (560−640 ℃) for coarse slag in inert atmosphere, with correlation coefficient R² of 0.99 and activation energy E of 38.85 kJ/mol. Similarly, in the intense pyrolysis stage (590−650 ℃) of fine slag, the fitting effect is better as the reaction order selected 3, with the correlation coefficient R² of 0.97 and the activation energy E of 79.09 kJ/mol. In oxidization atmosphere, at the intense combustion stage of coarse slag (540−605 ℃) and fine slag (530−605 ℃), the fitting effect is better as n=1 for the both slags, with the activation energy E of 226.46 and 154.73 kJ/mol respectively.
- coal gasification /
- gasification slag /
- FT-IR /
- thermogravimetric analysis /
- Coats-Redfern model

HTML全文

FIG. 1676. FIG. 1676.

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图 1 Texaco气化工艺流程示意图

Figure 1 Texaco gasification process flow chart

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图 2 FS和CS的红外光谱谱图

Figure 2 Infrared spectra of FS and CS

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图 3 FS和CS的红外分峰谱图

Figure 3 Infrared peak spectra of FS and CS

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图 4 惰性气氛下FS和CS的TG-DTG曲线

Figure 4 TG-DTG curves of FS and CS in inert atmosphere

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图 5 FS和CS热解转化率随温度的变化

Figure 5 Pyrolysis conversion-temperature relationship of FS and CS

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图 6 FS和CS热解动力学拟合图

Figure 6 Pyrolysis kinetics fitting diagram of FS and CS

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图 7 空气气氛下FS和CS的燃烧TG-DTG曲线

Figure 7 Combustion TG-DTG curves of FS and CS in air atmosphere

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图 8 CS燃烧的热重曲线

Figure 8 Example of thermogravimetric curve analysis

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图 9 FS和CS的燃烧转化率随温度的变化

Figure 9 Combustion conversion-temperature diagram of FS and CS

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图 10 FS和CS的燃烧动力学拟合图

Figure 10 Fitting diagram of combustion kinetics of FS and CS

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表 1 FS和CS的工业和元素分析

Table 1 Proximate and ultimate analyses of FS and CS

Sample	Proximate analysis w_ad/%				Ultimate analysis w/%					H/C	O/C
Sample	M	A	V	FC	$ {{\rm{C}}_{{\rm{daf}}}}$	$ {{\rm{H}}_{{\rm{daf}}}}$	${\rm{O}}_{{\rm{daf}}}^*$	$ {{\rm{N}}_{{\rm{daf}}}}$	$ {{\rm{S}}_{{\rm{t, d}}}}$	H/C	O/C
FS	2.10	66.76	6.09	25.05	28.87	0. 47	> 67.63	2.28	0.75	0.23	2.05
CS	1.71	52.89	3.09	42.31	29.60	0.21	> 67.43	2.30	0.46	0.09	1.71
* by difference

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表 2 FS和CS的红外光谱分峰拟合的各吸收峰面积比例

Table 2 Area ratio of each absorption peak fitted by the infrared spectrum of FS and CS

Wavenumber /cm⁻¹	Functional group	Content area/%
Wavenumber /cm⁻¹	Functional group	CS	FS
3600−3500	OH−π	8.43	21.74
3500−3350	self-associated OH	69.71	42.81
3350−3260	OH−ether O	12.15	24.69
3260−3170	cyclic OH	9.71	10.76
2950−2930	aliphatic −CH₃	9.54	7.42
2930−2900	asymmetric aliphatic −CH₂	47.09	29.54
2900−2870	aliphatic −CH	18.49	37.76
2870−2800	symmetric aliphatic −CH₂	24.88	25.28
1700	carboxylic acids C = O	3.50	9.34
1650	conjugated C = O	12.18	15.00
1600−1480	C = C in AR_s	42.00	33.03
1480−1400	asymmetric −CH₃, −CH₂	22.44	18.75
1400−1240	symmetric deformation −CH₃	8.64	20.97
1240−1160	phenols C−OH	0	0
1160−1090	grease C−O	4.75	0
1090−1030	alkyl ethers	6.50	2.91
900−860	five adjacent H deformation	35.82	12.67
860−810	four adjacent H deformations	20.75	0
810−750	three adjacent H deformations	14.59	61.44
750−720	two adjacent H deformations	28.84	25.89

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表 3 FS和CS热解动力学参数

Table 3 Calculation results of pyrolysis kinetic parameters of FS and CS

Sample	RO	y	R²	E/(kJ · mol⁻¹)	A/min⁻¹	2RT/E
CS at 560−640 ℃	1	−12.17 −1339.77x	0.98641	11.14	6.94 × 10⁻²	1.30
	2	−9.99 −2834.459x	0.99229	23.57	1.29	0.62
	3	−7.38 −4672.564x	0.99328	38.85	20.93	0.37
CS at 640−840 ℃	1	−13.63 −14.5552x	0.00461	0.12	1.74 × 10⁻⁴	146.06
	2	−11.49 −1498.34x	0.89846	12.46	0.15	1.42
	3	−8.81 −3410.567x	0.93575	28.36	5.07	0.62
FS at 590−650 ℃	1	−10 −3121.043x	0.96494	25.95	11.27	0.57
	2	−6.4 −5954.658x	0.96934	49.51	90.88	0.30
	3	−1.8 −9512.826x	0.97026	79.09	1.57 × 10⁴	0.19
FS at 650−840 ℃	1	−13.6 −25.85916x	0.01240	0.21	3.13 × 10⁻⁴	78.73
	2	−11.4 −1544.823x	0.89294	12.84	0.17	1.32
	3	−8.7 −3504.8109x	0.93264	29.14	5.70	0.58

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表 4 FS和CS的燃烧特性指数

Table 4 Combustion characteristic index of FS and CS

Sample	Temp. /℃			DTG/（%·min⁻¹）		S
Sample	t_i	t_f	t_max	DTG_max	DTG_mean	S
CS	530	605	575	−6.14	−3.84	1.39×10⁻⁷
FS	530	615	580	−4.33	−2.73	6.84×10⁻⁸

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表 5 FS和CS燃烧动力学参数

Table 5 Calculation results of combustion kinetic parameters of FS and CS

Sample	RO	y	R²	E/(kJ·mol⁻¹)	A /min⁻¹	2RT/E
CS at 440−540 ℃	1	−7807.17955x − 5.22	0.97621	64.91	4.21 × 10²	0.20
	2	−8392.50029x − 4.39	0.97159	69.78	1.04 × 10³	0.18
	3	−9004.53583x − 3.52	0.96685	74.86	2.65 × 10³	0.17
CS at 540−605 ℃	1	−27238.729x + 18.64	0.98599	226.46	3.41 × 10¹³	0.06
	2	−48397.686x + 44.37	0.93520	402.38	9.06 × 10²⁴	0.03
	3	−75694.658x + 77.51	0.89456	629.33	3.50 × 10³⁹	0.02
FS at 470−530 ℃	1	−5307.40144x − 8.113	0.94235	44.13	12.59	0.29
	2	−6001.65335x − 7.118	0.94055	49.90	40.86	0.26
	3	−6740.69158x − 6.062	0.93875	56.04	1.57 × 10²	0.23
FS at 530−605 ℃	1	−18610.24532x + 8.37	0.99033	154.73	8.03 × 10⁸	0.09
	2	−28925.05712x + 21.1	0.96508	240.48	4.38 × 10¹⁴	0.06
	3	−41849.59542x + 37.1	0.93957	347.94	5.37 × 10²¹	0.04

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