不同气流床气化工艺炭黑的氧化反应特性

高明; 陶迅; 丁路; 陈哲坤; 代正华; 于广锁; 王辅臣

doi:10.1016/S1872-5813(21)60116-0

不同气流床气化工艺炭黑的氧化反应特性

doi: 10.1016/S1872-5813(21)60116-0

高明^{1, 2,},
陶迅^{1, 2},
丁路^{1, 2},
陈哲坤^{1, 2},
代正华^{1, 2},
于广锁^{1, 2},
王辅臣^{1, 2, ,}

1.
华东理工大学洁净煤技术研究所，上海 200237
2.
水煤浆气化及煤化工国家工程研究中心（上海），上海 200237

基金项目: 国家自然科学基金（21776086，21776087）资助

详细信息

作者简介:
高明：gaom510@163.com

通讯作者:
E-mail：wfch@ecust.edu.cn

中图分类号: TQ541
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- 被引次数: 0
出版历程
- 收稿日期: 2021-03-16
- 修回日期: 2021-05-12
- 网络出版日期: 2021-06-16
- 刊出日期: 2022-01-25

Oxidation characteristics of soot in different entrained flow gasification processes

GAO Ming^{1, 2
,},
TAO Xun^{1, 2},
DING Lu^{1, 2},
CHEN Zhe-kun^{1, 2},
DAI Zheng-hua^{1, 2},
YU Guang-suo^{1, 2},
WANG Fu-chen^{1, 2
, ,}

1.
Institute of Clean Coal Technology, East China University of Science and Technology, Shanghai 200237, China
2.
National Engineering Research Center of CWS Gasification and Coal Chemical Industry (Shanghai), Shanghai 200237, China

Funds: The project was supported by National Natural Science Foundation of China (21776086, 21776087)

摘要

摘要: 利用高分辨透射显微镜分别对煤和生物质快速热解炭黑、天然气非催化部分氧化小试装置炭黑和工业装置炭黑、商业天然气炉法炭黑和煤焦油炉法炭黑等六种样品的形貌结构进行了表征；基于常压热重分析仪非等温法（50−800 ℃）对炭黑的着火点、氧化反应速率进行了研究，获得了炭黑的氧化反应动力学参数。研究表明，不同的炭黑理化性质差异较大，煤和生物质快速热解炭黑的球形度更高，粒径较大；天然气非催化部分氧化小试装置炭黑在较低温度下形成，呈现被碳囊包裹的形态；天然气非催化部分氧化工业装置炭黑呈现中空结构，粒径较小。非催化部分氧化小试装置和工业装置炭黑的氧化反应性接近，是天然气炉法炭黑的3.1倍，是煤焦油炉法炭黑的3.2倍；非催化部分氧化炭黑的反应性是煤快速热解炭黑的9.0倍，是生物质快速热解炭黑的26.6倍。两种非催化部分氧化炭黑和两种商业炉法炭黑的活化能随温度变化呈现分段形式；两种快速热解炭黑的活化能随温度升高基本不变。
- 炭黑 /
- 快速热解 /
- 非催化部分氧化 /
- 结构 /
- 反应性 /
- 动力学
Abstract: The morphological structure of six samples including the rapid pyrolysis soot of solid fuels (coal, biomass), the soot from non-catalytic partial oxidation (NCPOX) of natural gas in a laboratory pilot plant and an industrial plant, the commercial carbon black in natural gas furnace/coal tar furnace, were characterized by using a transmission electron microscope. Based on atmospheric thermogravimetric analyzer, the non-isothermal method (50–800 ℃) was adopted to study the ignition point and the oxidation reaction rate of soot, and the oxidation reaction kinetic parameters of soot was obtained. Studies showed that the physical and chemical properties of various soot were quite different. The soot from the rapid pyrolysis of coal and biomass presented a higher sphericity and a larger particle size. The Lab-NCPOX-soot was formed at a lower temperature which caused the particle being wrapped by a carbon capsule. The Ind-NCPOX-soot had a hollow structure and a small particle size. The reactivity of the Lab-NCPOX-soot is close to that of the Ind-NCPOX-soot, which is 3.1 times that of the commercial natural gas furnace carbon black and 3.2 times that of the commercial coal tar furnace carbon black; the reactivity of NCPOX-soot is 9.0 times of the rapid pyrolysis soot of coal, and 26.6 times of the rapid pyrolysis soot of biomass. The activation energy of 2 kinds of NCPOX-soot and 2 kinds of commercial carbon blacks present staged forms with increasing temperature. The activation energy of the 2 rapid pyrolysis soot was basically unchanged with increasing the temperature.
- soot /
- rapid pyrolysis /
- non-catalytic partial oxidation /
- structure /
- reactivity /
- kinetic

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FIG. 1234. FIG. 1234.

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图 1 炭黑样品的形貌对比

Figure 1 Morphologies of soot samples

(a): NG-furnace-CB; (b): Tar-furnace-CB; (c): Coal-RP-soot; (d): Biomass-RP-soot; (e): Lab-NCPOX-soot; (f): Ind-NCPOX-soot

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图 2 炭黑样品O₂气氛下非等温气化过程的TGA曲线

Figure 2 TGA curves of non-isothermal gasification process of soot samples under O₂atmosphere

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图 3 GC-MS测定的炭黑表面吸附物的主要成分

Figure 3 Soot surface adsorbent composition measured by GC-MS

①: C₁₄H₁₀; ②: C₁₅H₁₀; ③: C₁₆H₁₀; ④: C₁₆H₁₀; ⑤: C₁₈H₁₀

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图 4 炭黑样品O₂气氛下非等温气化过程的DTG曲线

Figure 4 DTG curves of non-isothermal gasification process of soot samples under O₂atmosphere

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图 5 炭黑样品的动力学特性曲线

Figure 5 Kinetic characteristic curves of soot samples

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图 6 炭黑的氧化模型示意图

Figure 6 Oxidation models of soot

(a): IOM; (b): HRM

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表 1 煤和生物质的性质^{[14, 15]}

Table 1 Properties of coal and saw dust^{[14, 15]}

Sample	Proximate analysis w_d/%			Ultimate analysis w_d/%
Sample	V	FC	A	C	H	N	S	O
Coal	35.48	59.06	5.46	76.85	4.63	1.23	1.34	10.49
Saw dust	90.92	7.74	1.34	42.39	5.64	0.79	0.44	49.40

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表 2 天然气非催化部分氧化实验的反应工况

Table 2 Reaction conditions of the NCPOX experiment of natural gas

O₂/CH₄	CH₄ flow rate/ (L∙min⁻¹)	O₂ flow rate/ (L∙min⁻¹)	CH₄ velocity/ (m∙s⁻¹)	O₂ velocity/ (m∙s⁻¹)	Residence time/s
0.80	18.89	15.11	123.34	142.51	0.929

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表 3 炭黑的氧化反应特性参数

Table 3 Oxidation reaction characteristic parameters of soot

Sample	T_i0/℃	Temperature of w_max/℃	T_f/℃	Reaction time/ min	w_max/ (%·min⁻¹)	w_mean/ (%·min⁻¹)	S/ (× 10⁻⁹·%²·min⁻²·℃⁻³)
NG- furnace-CB	496.7	559.9	584.3	8.76	3.51	1.09	26.6
Tar-furnace-CB	488.6	548.3	588.4	9.98	3.87	0.93	25.5
Coal-RP-soot	518.6	580.7	614.5	9.59	1.70	0.88	9.1
Biomass-RP-soot	460.8	531.2	572.0	11.12	0.79	0.47	3.1
Lab-NCPOX-soot	453.7	493.7	503.3	4.96	5.18	1.63	81.5
Ind-NCPOX-soot	531.6	550.9	594.6	6.30	9.63	1.12	63.9

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表 4 炭黑样品的氧化动力学参数

Table 4 Oxidation kinetic parameters of soot samples

Sample		Temperature range/℃	b	a	E/(kJ·mol⁻¹)	A/min⁻¹	R²
NG-furnace-CB	stage 1	496.7−542.8	11.42	−21924	182	2.15 × 10¹⁰	0.9926
	stage 2	542.8−577.3	71.65	−70943	590	9.53 × 10³⁶	0.9970
	stage 3	577.3−584.3	4.98	−14327	119	2.36 × 10⁷	0.9759
Tar-furnace-CB	stage 1	488.6−533.8	5.49	−16575	138	4.41 × 10⁷	0.9851
	stage 2	533.8−558.7	76.08	−73433	611	8.23 × 10³⁸	0.9978
	stage 3	558.7−588.4	10.00	−18630	155	4.49 × 10⁹	0.9932
Coal-RP-soot		518.6−614.5	18.41	−26972	224	2.83 × 10¹³	0.9789
Biomass-RP-soot		460.8−572.0	1.17	−11222	93	4.14 × 10⁵	0.9654
Lab-NCPOX-soot	stage 1	453.7−483.9	−2.47	−9144	76	9.21 × 10³	0.9941
Lab-NCPOX-soot	stage 2	483.9−503.3	91.53	−80272	667	4.62 × 10⁴⁵	0.9509
Ind-NCPOX-soot	stage 1	531.6−547.6	5.37	−16459	137	3.91 × 10⁷	0.9981
	stage 2	547.6−556.3	201.19	−177362	1475	4.25 × 10⁹³	0.9874
	stage 3	556.3−594.6	16.06	−24071	200	2.44 × 10¹²	0.9777

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参考文献(31)

[1]	UMEMOTO S, KAJITANI S, MIURA K, WATANABE H, KAWASE M. Extension of the chemical percolation devolatilization model for predicting formation of tar compounds as soot precursor in coal gasification[J]. Fuel Process Technol,2017,159:256−265. doi: 10.1016/j.fuproc.2017.01.037
[2]	MIURA K, NAKAGAWA H, NAKAI S-I, KAJITANI S. Analysis of gasification reaction of coke formed using a miniature tubing-bomb reactor and a pressurized drop tube furnace at high pressure and high temperature[J]. Chem Eng Sci,2004,59(22/23):5261−5268. doi: 10.1016/j.ces.2004.08.025
[3]	GÖKTEPE B, UMEKI K, GEBART R. Does distance among biomass particles affect soot formation in an entrained flow gasification process?[J]. Fuel Process Technol,2016,141:99−105. doi: 10.1016/j.fuproc.2015.06.038
[4]	王辅臣, 李伟锋, 代正华, 陈雪莉, 刘海峰, 于遵宏. 天然气非催化部分氧化制合成气过程的研究[J]. 石油化工,2006,1:47−51. WANG Fu-chen, LI Wei-feng, DAI Zheng-hua, CHEN Xue-li, LIU Hai-feng, YU Zun-hong. Preparation of syngas from natural gas by non-catalytic partial oxidation[J]. Petrochem Technol,2006,1:47−51.
[5]	王辅臣, 代正华, 刘海峰, 龚欣, 于广锁, 于遵宏. 焦炉气非催化部分氧化与催化部分氧化制合成气工艺比较[J]. 煤化工,2006,34(2):4−9. doi: 10.3969/j.issn.1005-9598.2006.02.002 WANG Fu-chen, DAI Zheng-hua, LIU Hai-feng, GONG Xin, YU Guang-suo, YU Zun-hong. COG based syngas production process with catalytic and non- catalytic partial oxidation[J]. Coal Chem Ind,2006,34(2):4−9. doi: 10.3969/j.issn.1005-9598.2006.02.002
[6]	VERMA P, PICKERING E, SAVIC N, ZARE A, BROWN R, RISTOVSKI Z. Comparison of manual and automatic approaches for characterisation of morphology and nanostructure of soot particles[J]. J Aerosol Sci,2019,136:91−105. doi: 10.1016/j.jaerosci.2019.07.001
[7]	UMEMOTO S, KAJITANI S, HARA S, KAWASE M. Proposal of a new soot quantification method and investigation of soot formation behavior in coal gasification[J]. Fuel,2016,167:280−287. doi: 10.1016/j.fuel.2015.11.074
[8]	CHANG Q, GAO R, GAO M, YU G, WANG F. The structural evolution and fragmentation of coal-derived soot and carbon black during high-temperature air oxidation[J]. Combust Flame,2020,216:111−125. doi: 10.1016/j.combustflame.2019.11.045
[9]	SEPTIEN S, VALIN S, PEYROT M, DUPONT C, SALVADOR S. Characterization of char and soot from millimetric wood particles pyrolysis in a drop tube reactor between 800 °C and 1400 °C[J]. Fuel,2014,121:216−224. doi: 10.1016/j.fuel.2013.12.026
[10]	TRUBETSKAYA A, JENSEN P A, JENSEN A D, GARCIA LLAMAS A D, UMEKI K, GARDINI D, KLING J, BATES R B, GLARBORG P. Effects of several types of biomass fuels on the yield, nanostructure and reactivity of soot from fast pyrolysis at high temperatures[J]. Appl Energy,2016,171:468−482. doi: 10.1016/j.apenergy.2016.02.127
[11]	TRUBETSKAYA A, LARSEN F H, SHCHUKAREV A, STÅHL K, UMEKI K. Potassium and soot interaction in fast biomass pyrolysis at high temperatures[J]. Fuel,2018,225:89−94. doi: 10.1016/j.fuel.2018.03.140
[12]	TRUBETSKAYA A, BROWN A, TOMPSETT G A, TIMKO M T, KLING J, BROSTRöM M, ANDERSEN M L, UMEKI K. Characterization and reactivity of soot from fast pyrolysis of lignocellulosic compounds and monolignols[J]. Appl Energy,2018,212:1489−1500. doi: 10.1016/j.apenergy.2017.12.068
[13]	袁帅. 煤、生物质及其混合物的快速热解及过程中氮的迁移[D]. 上海: 华东理工大学, 2012. YUAN Shuai. Rapid pyrolysis of coal, biomass, and coal/biomass blends, and nitrogen evolution during rapid pyrolysis[D]. Shanghai: East China University of Science and Technology, 2012.
[14]	CHANG Q, GAO R, LI H, YU G, LIU X, WANG F. Understanding of formation mechanisms of fine particles formed during rapid pyrolysis of biomass[J]. Fuel,2018,216:538−547. doi: 10.1016/j.fuel.2017.12.036
[15]	CHANG Q, GAO R, LI H, YU G, WANG F. Effect of CO₂ on the characteristics of soot derived from coal rapid pyrolysis[J]. Combust Flame,2018,197:328−339. doi: 10.1016/j.combustflame.2018.05.033
[16]	李炳炎主编. 炭黑生产与应用手册[M]. 北京: 化学工业出版社, 2000. LI Bing-yan. Carbon Black Production and Application Manual[M]. Beijing: Chemical Industry Press, 2000.
[17]	WANG X, JIN Q, WANG L, BAI S, MIKULČIĆ H, VUJANOVIĆ M, TAN H. Synergistic effect of biomass and polyurethane waste co-pyrolysis on soot formation at high temperatures[J]. J Environ Manage,2019,239:306−315. doi: 10.1016/j.jenvman.2019.03.073
[18]	吕建燚, 石晓斌. 生物质燃烧碳烟的物化特性及生成机理研究[J]. 燃料化学学报,2013,41(10):1184−1190. LÜ Jian-yi, SHI Xiao-bin. Physicochemical properties and formation mechanism of soot during biomass burning[J]. J Fuel Chem Technol,2013,41(10):1184−1190.
[19]	AL-OMARI S B, KAWAJIRI K, YONESAWA T. Soot processes in a methane-fueled furnace and their impact on radiation heat transfer to furnace walls[J]. Int J Heat Mass Transf,2001,44:2567−2581. doi: 10.1016/S0017-9310(00)00288-X
[20]	BELTRAME A, PORSHNEV P, MERCHAN-MERCHAN W, SAVELIEV A, FRIDMAN A, KENNEDY L A, PETROVA O, ZHDANOK S, AMOURI F, CHARON O. Soot and NO formation in methane-oxygen enriched diffusion flames[J]. Combust Flame,2001,124(1):295−310.
[21]	SHI Y, MURR L E, SOTO K F, LEE W Y, GUERRERO P A, RAMIREZ D A. Characterization and comparison of speciated atmospheric carbonaceous particulates and their polycyclic aromatic hydrocarbon contents in the context of the paso del norte airshed along the U. S. -mexico border[J]. Polycycl Aromat Compd,2007,27(5):361−400. doi: 10.1080/10406630701624333
[22]	谢广录, 范卫东, 徐宾, 章明川. 天然气炭黑燃烧特性的热天平研究[J]. 热能动力工程,2005,5:521−526, 554−555. doi: 10.3969/j.issn.1001-2060.2005.05.018 XIE Guang-lu, FAN Wei-dong, XU Bin, ZHANG Ming-chuan. Thermogravimetric study of the combustion characteristics of natural-gas soot[J]. J Eng Therm Energy Power,2005,5:521−526, 554−555. doi: 10.3969/j.issn.1001-2060.2005.05.018
[23]	范卫东, 谢广录, 徐宾, 于娟, 章明川. 氧体积分数对炭黑燃烧特性影响的热天平研究[J]. 燃料化学学报,2005,33(5):550−555. FAN Wei-dong, XIE Guang-lu, XU Bin, YU Juan, ZHANG Ming-chuan. Thermogravimetric study of the effect of oxygen concentrations on combustion characteristics of natural gas soot[J]. J Fuel Chem Technol,2005,33(5):550−555.
[24]	杨冬. 柴油机颗粒氧化动力学特性研究[D]. 成都: 西华大学, 2015. YANG Dong. Investigation on the oxidation kinetics of diesel particulate[D]. Chengdu: Xihua University, 2015.
[25]	唐子君, 岑超平, 方平. 城市污水污泥与煤混烧的热重试验研究[J]. 动力工程学报,2012,32(11):878−884, 897. doi: 10.3969/j.issn.1674-7607.2012.11.010 TANG Zi-jun, CEN Chao-ping, FANG Ping. Thermogravimetric experiment on co-firing characteristics of coal with municipal sewage sludge[J]. J Chin Soc Power Eng,2012,32(11):878−884, 897. doi: 10.3969/j.issn.1674-7607.2012.11.010
[26]	HE Q, HUANG Y, DING L, GUO Q, GONG Y, YU G. Effect of partial rapid pyrolysis on bituminous properties: From structure to reactivity[J]. Energy Fuels,2020,34(5):5476−5484.
[27]	周志杰, 范晓雷, 张薇, 王辅臣, 于遵宏. 非等温热重分析研究煤焦气化动力学[J]. 煤炭学报,2006,2:219−222. doi: 10.3321/j.issn:0253-9993.2006.02.019 ZHOU Zhi-jie, FAN Xiao-lei, ZHANG Wei, WANG Fu-chen, YU Zun-hong. Char gasification kinetics using non-isothermal TGA[J]. J China Coal Soc,2006,2:219−222. doi: 10.3321/j.issn:0253-9993.2006.02.019
[28]	梁斌, 冯强, 白浩隆, 武琼, 宋华, 杨晓辉, 蓝天. 煤泥干粉在流化床中燃烧特性的实验研究[J]. 煤炭学报,2018,43(z2):560−567. LIANG Bin, FENG Qiang, BAI Hao-long, WU Qiong, SONG Hua, YANG Xiao-hui, LAN tian. Combustion characteristics of dry coal slime powders in a fluidized bed[J]. J China Coal Soc,2018,43(z2):560−567.
[29]	DING L, ZHOU Z, GUO Q, WANG Y, YU G. In situ analysis and mechanism study of char-ash/slag transition in pulverized coal gasification[J]. Energy Fuels,2015,29(6):3532−3544. doi: 10.1021/acs.energyfuels.5b00322
[30]	CHANG Q, GAO R, GAO M, YU G, MATHEWS J P, WANG F. Experimental analysis of the evolution of soot structure during CO₂ gasification[J]. Fuel,2020,265:111−125.
[31]	YE D P, AGNEW J B, ZHANG D K. Gasification of a South Australian low-rank coal with carbon dioxide and steam: Kinetics and reactivity studies[J]. Fuel,1998,77(11):1209−1219. doi: 10.1016/S0016-2361(98)00014-3