TG-FTIR研究煤油共热解产物逸出行为

周晓东; 吴浩; 刘景梅; 黄雪莉; 刘婷; 钟梅; 马凤云

doi:10.1016/S1872-5813(23)60393-7

TG-FTIR研究煤油共热解产物逸出行为

doi: 10.1016/S1872-5813(23)60393-7

周晓东^1,,
吴浩^2,,
刘景梅^1, ,,
黄雪莉^2,,
刘婷^1,,
钟梅^2, ,,
马凤云^2,

1.
新疆大学化学学院省部共建碳基能源资源化学与利用国家重点实验室, 新疆乌鲁木齐 830017
2.
新疆大学化工学院新疆煤炭清洁转化与化工过程重点实验室, 新疆乌鲁木齐 830017

基金项目: 碳基能源资源化学与利用国家重点实验室重点专项，国家自然科学基金（22279110）和中央引导地方科技发展专项资助

详细信息

通讯作者:
E-mail: liujm@xju.edu.cn

zhongmei0504@126.com

中图分类号: TQ536.1
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出版历程
- 收稿日期: 2023-07-25
- 修回日期: 2023-09-30
- 录用日期: 2023-10-04
- 网络出版日期: 2023-11-10
- 刊出日期: 2024-04-03

TG-FTIR study on escape behavior of products from co-pyrolysis of coal and residuum

ZHOU Xiaodong^1
,,
WU Hao^2
,,
LIU Jingmei^{1
, ,},
HUANG Xueli^2
,,
LIU Ting^1
,,
ZHONG Mei^{2
, ,},
MA Fengyun^2
,

1.
College of Chemistry, Xinjiang University, State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, Xinjiang University, Urumqi 830017, China
2.
Xinjiang Key Laboratory of Coal Clean Conversion & Chemical Engineering Process, School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830017, China

Funds: The project was supported by the Special Project for State Key Laboratory of Chemistry and Utilization of Carbon-Based Energy Resources, National Natural Science Foundation of China (22279110), and Special Fund Project for the Local Development of Science and Technology Guiding by the Central Government.

摘要

摘要: 煤油共液化过程中煤与重油先发生共热解，而后加氢转化为小分子产品。因此，阐明重油对煤热解逸出产物的影响规律是调控共液化产物组成的重要热化学基础。本研究采用TG-FTIR对比研究塔河渣油（AR）和淖毛湖煤（NMH）单独热解及其共热解过程，结合热解活化能计算，探索共热解过程中塔河渣油（AR）对淖毛湖煤（NMH）热解产物逸出产物的影响。结果表明，单独热解时AR先于NMH发生热解反应。两者1∶1（质量比）混合共热解时，相比于单独热解计算的理论值，最大失重峰温度前移7 ℃，失重率增加约3%，共热解平均活化能降低23.6 kJ/mol，表明AR率先热解会诱发NMH热解，降低热解反应能垒。TG-FTIR结果显示，AR产生的烷烃类自由基会与NMH热解产生的含氧自由基结合，形成醇、醚等烷基类含氧有机化合物，从而抑制煤中羧基转化为CO₂的过程。研究结果有助于揭示共液化反应过程中重油对煤液化产物组成的影响。
- 塔河渣油 /
- 淖毛湖煤 /
- 共热解 /
- 含氧官能团 /
- 诱导促进
Abstract: Coal and residuum are first co-pyrolyzed, and then hydrogenated into small molecule products during co-liquefaction. Therefore, clarifying influence of residuum on coal pyrolysis performance is an important thermochemical basis for regulating the process. The co-pyrolysis behavior of atmospheric residuum (AR) and Naomaohu coal (NMH) were investigated by TG, TG-FTIR and distributed activation energy model. The results showed that the peak temperature of the maximum rate of weight loss for the co-pyrolysis process was reduced by 7 °C compared with the theoretical value calculated by weighted average of AR and NMH pyrolysis alone, while the weight loss increased by 3%, the average activation energy decreased by 23.6 kJ/mol. In addition, the peak area of alkyl O-containing functional groups such as alcohols and ethers increased, whereas those of CO and CO₂ decreased, suggesting that AR had a positive effect on NMH pyrolysis. Meanwhile, alkyl radicals from AR decomposition would combine with O-containing radicals generated from coal pyrolysis, thus resulting in a decrease of CO and CO₂ by inhibiting breakage of carboxyl groups. This work will provide a scientific evaluation basis for revealing the influence of residuum on composition of coal liquefaction product during co-liquefaction.
- Tahe residuum /
- Naomaohu coal /
- co-pyrolysis /
- O-containing functional groups /
- promotion effect

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FIG. 3076. FIG. 3076.

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图 1 热重平行实验

Figure 1 Comparison of TG parallel experiments

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图 2 A50样品主要逸出峰面积

Figure 2 Comparison of peak area for pyrolytic products of A50

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图 3 五种样品的表面形貌（放大倍数100倍）

Figure 3 Surface morphology of five samples

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图 4 NMH与AR(a)、A25(b)、A50(c)和A75(d)的TG实验与计算曲线

Figure 4 Exp. and calc. of TG curves of NMH and AR (a), A25 (b), A50 (c) and A75 (d)

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图 5 NMH、AR和A50的TG-FTIR谱图(a)为TG-DTG谱图，(b)、(c)和(d)分别为NMH、AR和A50的TG-FTIR三维谱图

Figure 5 TG-FTIR analysis of NMH, AR and A50, (a) is the TG-DTG curve, (b), (c) and (d) are the TG-FTIR 3D spectra for pyrolysis of NMH, AR and A50 respectively

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图 6 第一类逸出峰的峰面积

Figure 6 Peak area of first type characteristic peak

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图 7 第一类逸出峰的影响因子分布

Figure 7 Distribution of F_Y for first type of characteristic peak

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图 8 第二类逸出峰的峰面积分布

Figure 8 Peak area of second type characteristic peak

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图 9 第二类逸出峰的影响因子

Figure 9 Distribution of F_Y for second type of characteristic peak

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图 10 不同转化率下NMH（a）、A25（b）、A50（c）、A75（d）和AR（e）的阿伦尼乌斯图

Figure 10 Arrhenius diagram of NMH (a), A25 (b), A50 (c), A75 (d) and AR (e) at different conversion rate

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图 11 NMH与AR（a）、A25（b）、A50（c）和A75（d）热解活化能随转化率的变化

Figure 11 Curve of pyrolysis activation energy for NMH and AR (a), A25 (a), A50 (a), and A75 (d) changing with conversion

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表 1 NMH基本性质分析

Table 1 Proximate and ultimate analyses of NMH

Proximate analysis w/%			Ultimate analysis w_daf/%					H/C	Petrographical analysis/%
M_ad	A_d	V_daf	C	H	N	S	O^a	H/C	vitrinite	inertinite	exinite
10.36	9.45	52.12	74.65	5.96	1.29	0.35	17.75	0.96	67.7	2.9	29.4
^a: by difference.

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表 2 AR常规分析

Table 2 Basic properties of AR

Mechanical impurities/%	Viscosity (mm²/s, 100 ℃)	Carbon residue/%	Aromaticity	SARA fraction/%				Elemental analysis (%, daf)
Mechanical impurities/%	Viscosity (mm²/s, 100 ℃)	Carbon residue/%	Aromaticity	Sa	Ar	Re	As	C	H	N	S	O^a
0.03	154.4	13.70	0.27	45.36	17.79	21.45	15.40	85.86	11.34	0.53	2.09	0.18
SARA fractions: The saturates (Sa), aromatics (Ar), resins (Re), and asphaltenes (As) fractions. ^a: by difference.

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表 3 五种样品的TG-DTG参数

Table 3 TG-DTG parameters of five samples

Sample/ F_Y	Total weight loss/ %	Degassing 25−170 ℃			Slow pyrolysis 170−360 ℃			Fast pyrolysis 360−560 ℃			Polycondensation 560−800 ℃
Sample/ F_Y	Total weight loss/ %	peak temp./ ℃	weight loss rate/ (%·℃⁻¹)	weight loss/ %	peak temp./ ℃	weight loss rate/ (%·℃⁻¹)	weight loss/ %	peak temp./ ℃	weight loss rate/ (%·℃⁻¹)	weight loss/ %	weight loss/ %
NMH	47.2	59.7	0.09	6.4	−	−	4.6	440	0.28	26.8	9.4
A25_Exp.	59.9	60.1	0.09	9.2	−	−	14.6	441	0.32	29.5	6.6
A25_Calc.	56.4	58.5	0.08	8.2	−	−	13.6	445	0.29	28.2	6.4
F_Y	0.06	0.03	0.13	0.12	−	−	0.07	−0.009	0.10	0.05	0.1
A50_Exp.	69.2	91.2	0.33	13.0	−	−	21.9	442	0.33	29.8	4.2
A50_Calc.	66.6	50.2	0.09	9.4	−	−	22.4	449	0.30	29.5	5.3
F_Y	0.04	0.82	2.67	0.38	−	−	−0.02	−0.02	0.1	0.01	−0.21
A75_Exp.	78.4	108.0	0.14	14.0	286	0.19	31.2	445	0.36	30.5	2.7
A75_Calc.	76.5	49.5	0.11	12.5	277	0.18	31.1	450	0.34	29.9	3.2
F_Y	0.02	1.18	0.27	0.12	0.03	0.06	0.00	−0.01	0.06	0.02	−0.16
AR	86.3	51.5	0.12	14.6	274.5	0.23	39.8	451	0.36	29.9	2.2

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