由乙烯焦油制备碳质前驱体的氧化反应机理及其反应动力学

GUO Tian-rui; CHEN Rong-qi; GAO Wei; WANG Yan-li; ZHAN Liang

doi:10.1016/S1872-5805(22)60597-3

由乙烯焦油制备碳质前驱体的氧化反应机理及其反应动力学

doi: 10.1016/S1872-5805(22)60597-3

华东理工大学化学工程联合国家重点实验室，上海 200237

详细信息

通讯作者:
詹亮. E-mail：zhanliang@ecust.edu.cn

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出版历程
- 收稿日期: 2021-01-01
- 网络出版日期: 2022-01-05

Oxidation reaction mechanism and kinetics of ethylene tar for preparation of carbonaceous precursor

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China

Funds: This work was financially supported by the National Natural Science Foundation of China (No.51472086, 51002051, U1710252, 50730003, 50672025, 20806024 and 22075081)

More Information

Corresponding author: ZHAN Liang, Prof., E-mail: zhanliang@ecust.edu.cn

摘要

摘要: 为了得到优质的碳质前驱体，研究了乙烯焦油在空气中的氧化反应机理及其反应动力学。根据热重曲线将乙烯焦油的氧化过程分成350–550 K、550–700 K和700–900 K三个阶段，并采用质谱和红外技术对不同反应温度下的尾气成份进行在线分析以揭示乙烯焦油在空气中的氧化反应机理；根据不同反应温度下乙烯焦油与氧气的热失重曲线将整个反应过程分为四个部分，并采用Coats-Redfern等转化率法通过分析17种常用反应动力学模型与实验数据的拟合度，筛选出最适宜于表达乙烯焦油与氧气的反应动力学模型。实验结果表明：（1）在乙烯焦油的氧化过程中，芳香化合物的支链先与氧气反应生成醇类、醛类小分子化合物和含有过氧自由基的芳香化合物，然后含有过氧自由基的芳香化合物进行热缩聚反应形成分子量更大的芳香族化合物；（2）可采用四级反应模型描述乙烯焦油的前三部分反应动力学，活化能分别为47.330 kJ·mol⁻¹、18.689 kJ·mol⁻¹和9.004 kJ·mol⁻¹，可采用三维扩散模型描述第四部分的反应动力学，其活化能为88.369 kJ·mol⁻¹。
- 乙烯焦油 /
- 氧化反应机理 /
- 反应动力学
Abstract: To obtain excellent carbonaceous precursors, the oxidation reaction mechanism and kinetics of ethylene tar were investigated. The oxidation process of ethylene tar was divided into three stages (350-550 K, 550-700 K and 700-900 K) according to the thermogravimetric curve. To reveal the oxidation reaction mechanism of ethylene tar, the components of evolved gases at different stages were further analyzed online by mass spectrometry and infrared technology. Then, based on the thermogravimetric curve of ethylene tar at different reaction temperatures, the whole reaction process was divided into four parts to perform kinetics simulation calculation. With the help of the iso-conversional method (Coats-Redfern) to analyze the linear regression rates (R²) between 17 common reaction kinetics models and experimental data, the optimal reaction kinetics model for expressing oxidation process of ethylene tar was determined. The results show that: (1) In the oxidation process, the side chains of aromatic compounds firstly react with oxygen to form alcohols and aldehydes, leaving peroxy-radicals to aromatic rings. After that, the aromatic compounds with peroxy-radicals undergo polymerization/condensation reaction to form larger molecular. (2) The fourth-order of reaction model is adopted to describe the first three parts of the oxidation process, and the activation energies are 47.330 kJ·mol⁻¹, 18.689 kJ·mol⁻¹ and 9.004 kJ·mol⁻¹ respectively. The three-dimensional diffusion model is applied to the fourth part of the oxidation process, and the activation energy is 88.369 kJ·mol⁻¹.
- Ethylene tar /
- Oxidation reaction mechanism /
- Reaction kinetics

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Figure 1. (a) GC-MS and (b) LDI TOF/MS spectrogram of ET-HR.

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Figure 2. TG、DTG and DSC curves of ET-HR.

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Figure 3. Possible reactions to generate H₂.

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Figure 4. Possible reactions to generate CH₄, H₂O and HCHO.

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Figure 5. Possible reactions to generate CH₃CHO and CO₂.

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Figure 6. (a) Ion current intensity of various mass units in the temperature range from 300 K to 900 K (b-d) Mass spectra of m/z=2, 44 and 128 amu.

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Figure 7. (a) 3D FTIR spectra of evolved gaseous products from oxidation process of ET-HR (b) FTIR spectrum of evolved gases recorded at 450 K.

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Figure 8. (a) Function of ln[G(a)/T²] with respect with 1/T for the first part of oxidation (b) the second part of oxidation (c) the third part of oxidation (d) the fourth part of oxidation.

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Table 1. A series of frequently-used mechanism models defining G(α)^{[33, 34]}.

Mechanisms		Symbol	$ f\left(\alpha \right) $	$ G\left(\alpha \right) $
Order of reaction	First order	$ {\mathrm{F}}_{1} $	$ 1-\alpha $	$ -\mathrm{l}\mathrm{n}\left(1-\alpha \right) $
	Second order	$ {\mathrm{F}}_{2} $	$ {\left(1-\alpha \right)}^{2} $	$ {\left(1-\alpha \right)}^{-1}-1 $
	Third order	$ {\mathrm{F}}_{3} $	$ {\left(1-\alpha \right)}^{3} $	$ \left[{\left(1-\alpha \right)}^{-2}-1\right]/2 $
	Fourth order	$ {\mathrm{F}}_{4} $	$ {\left(1-\alpha \right)}^{4} $	$ \left[{\left(1-\alpha \right)}^{-3}-1\right]/3 $
Diffusion	One-way transport	$ {\mathrm{D}}_{1} $	$ 0.5\alpha $	$ {\alpha }^{2} $
	Two-way transport	$ {\mathrm{D}}_{2} $	$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{-1} $	$ \alpha +\left(1-\alpha \right)\mathrm{l}\mathrm{n}\left(1-\alpha \right) $
	Three-way transport	$ {\mathrm{D}}_{3} $	$ 1.5{\left(1-\alpha \right)}^{2/3}{\left[1-{\left(1-\alpha \right)}^{1/3}\right]}^{-1} $	$ {\left[1-{\left(1-\alpha \right)}^{1/3}\right]}^{2} $
Contracting geometry	Contracting cylinder	$ {\mathrm{R}}_{2} $	$ 2{\left(1-\alpha \right)}^{1/2} $	$ 1-{\left(1-\alpha \right)}^{1/2} $
Contracting geometry	Contracting sphere	$ {\mathrm{R}}_{3} $	$ 3{\left(1-\alpha \right)}^{2/3} $	$ 1-{\left(1-\alpha \right)}^{1/3} $
Random nucleation and nuclei growth	Avrami-Erofeev	$ {\mathrm{A}}_{3/2} $	$ 1.5\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/3} $	$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{3/2} $
Random nucleation and nuclei growth	Avrami-Erofeev	$ {\mathrm{A}}_{2} $	$ 2\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/2} $	$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/2} $
	Avrami-Erofeev	$ {\mathrm{A}}_{3} $	$ 3\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{2/3} $	$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/3} $
	Avrami-Erofeev	$ {\mathrm{A}}_{4} $	$ 4\left(1-\alpha \right){\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{3/4} $	$ {\left[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)\right]}^{1/4} $
Exponential nucleation	Power law	$ {\mathrm{P}}_{3/2} $	$ 2/3{\alpha }^{-1/2} $	$ {\alpha }^{2/3} $
Exponential nucleation	Power law	$ {\mathrm{P}}_{2} $	$ 2{\alpha }^{1/2} $	$ {\alpha }^{1/2} $
	Power law	$ {\mathrm{P}}_{3} $	$ 3{\alpha }^{2/3} $	$ {\alpha }^{1/3} $
	Power law	$ {\mathrm{P}}_{4} $	$ 4{\alpha }^{3/4} $	$ {\alpha }^{1/4} $

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Table 2. The fundamental properties of ethylene tar and ET-HR.

	Elemental analysis (wt. %)					C/H ²	TS ³ (wt. %)	Four components				SP ⁸ (℃)	CV ⁹ (wt. %)
	C	H	N	S	O ¹	C/H ²	TS ³ (wt. %)	S ⁴	Ar ⁵	R ⁶	As ⁷	SP ⁸ (℃)	CV ⁹ (wt. %)
ET	92.28	7.324	0	0.027	0.369	1.05	100	5.633	90.501	3.423	0.443	<25	7.74
ET-HR	92.82	6.869	0	0.022	0.289	1.13	100	0	91.911	7.162	0.927	<25	14.1
¹ SP: By difference. ² C/H: Atomic ratio. ³ TS: Toluene soluble components. ⁴ S: Saturated fraction.
⁵ Ar: Aromatic fraction. ⁶ R: Resin. ⁷ As: Asphaltene. ⁸ SP: Softening point. ⁹ CV: Coking value.

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Table 3. Possible compounds distinguished by GC-MS in ET-HR.

Peak No.	Names or types	Retention time (min)	Area percentage (%)
1	(Z)-1-Phenylpropene	8.14	2.689
2	Indene	9.015	6.919
3	Naphthalene,1,2-dihydro-	10.708	3.874
4	Cycloprop[a]indene,1,1a,6,6a-tetrahydro-	10.798	3.095
5	Benzene, (1-methylene-2-propenyl)-	10.94	1.143
6	Naphthalene	11.332	42.252
7	Benzocycloheptatriene	12.909	12.971
8	Benzocycloheptatriene	13.154	8.688
9	Naphthalene,2-ethenyl-	14.023	2.430
10	Naphthalene,2-ethyl-	14.222	1.167
11	Naphthalene, 1-ethyl-	14.274	0.844
12	Naphthalene,1,6-dimethyl-	14.57	1.651
13	Naphthalene,2-ethenyl-	14.699	1.066
14	Biphenylene	14.982	1.395
15	1,1’-Biphenyl,4-methyl-	15.374	0.970
16	Naphthalene,2-ethenyl-	15.426	1.780
17	Fluorene	16.63	1.987
18	Phenanthrene	18.895	4.355
19	Anthracene	18.985	0.724

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Table 4. Evolved gases analysis.

Fragment (amu)	Molecular formula	Molecule
2	H₂	hydrogen
16	CH₄	methane
18	H₂O	water
26	C₂H₂	acetylene
28	C₂H₄	ethylene
30	HCHO	formaldehyde
44	CH₃CHO/CO₂	acetaldehyde/carbon dioxide
64	SO₂	sulfur dioxide
128	C₁₀H₈	naphthalene

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Table 5. Linear regression rates (R²) of different models of four parts in the process of oxidation.

Model	$ {{R}^{2}}_{stage1} $ (323-400 K)	$ {{R}^{2}}_{stage2} $ (400-605 K)	$ {{R}^{2}}_{stage3} $ (605-750 K)	$ {{R}^{2}}_{stage4} $ (750-860 K)
$ {\mathrm{F}}_{1} $	0.99195	0.92258	NA	0.9674
$ {\mathrm{F}}_{2} $	0.99372	0.97629	NA	0.91237
$ {\mathrm{F}}_{3} $	0.99525	0.98949	0.77979	0.89775
$ {\mathrm{F}}_{4} $	0.99653	0.99102	0.92887	0.89578
$ {\mathrm{D}}_{1} $	0.99152	0.9389	NA	0.94713
$ {\mathrm{D}}_{2} $	0.99211	0.95419	NA	0.97933
$ {\mathrm{D}}_{3} $	0.99268	0.9667	NA	0.98793
$ {\mathrm{R}}_{2} $	0.99097	0.85181	NA	0.9839
$ {\mathrm{R}}_{3} $	0.99131	0.88105	NA	0.98385
$ {\mathrm{A}}_{3/2} $	0.99283	0.96561	NA	0.97099
$ {\mathrm{A}}_{2} $	0.98835	NA	NA	0.95101
$ {\mathrm{A}}_{3} $	0.98236	NA	NA	0.91699
$ {\mathrm{A}}_{4} $	0.97154	NA	NA	0.82846
$ {\mathrm{P}}_{3/2} $	0.99103	0.90477	NA	0.92539
$ {\mathrm{P}}_{2} $	0.99103	0.90477	NA	0.92539
$ {\mathrm{P}}_{3} $	0.97785	NA	NA	NA
$ {\mathrm{P}}_{4} $	0.96399	NA	NA	NA

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Table 6. Oxidation kinetics parameters of ET-HR.

Reaction section	Model	$ k $	$ b $	$ {E}_{a}\left(kJ\bullet {mol}^{-1}\right) $	$ A\left({min}^{-1}\right) $	$ {R}^{2} $
ET-HR_part1	$ {\mathrm{F}}_{4} $	−5692.77928	0.84939	47329.76693	66554.85476	0.99653
ET-HR_part2	$ {\mathrm{F}}_{4} $	−2247.94165	−7.74028	18689.38688	4.888708542	0.99102
ET-HR_part3	$ {\mathrm{F}}_{4} $	−1083.02397	−9.46354	9004.261287	0.420382735	0.92887
ET-HR_part4	$ {\mathrm{D}}_{3} $	−10628.96641	−1.51215	88369.22673	11715.00931	0.98793

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