烟草废弃物流化床热解转化实验研究

doi:10.3969/j.issn.0253-2417.2022.06.007

摘要/Abstract

摘要：

为了探索烟草废弃物的高值化利用途径，采用热重、热解-气质联用(Py-GC/MS)等仪器对其原料特性及基础热化学转化特性进行探讨。在10 kg/h处理量的流化床热解反应系统开展烟草废弃物的热解转化研究，并对热解得到的气体、固体和液体产物特性进行分析，结果表明：1) 烟草废弃物的堆积密度较小，孔隙率较高，其热解失重区间主要为150~400 ℃，最大失重速率发生在180和315 ℃附近；2) 通过Py-GC/MS分析发现烟草废弃物热解生物油组分主要包括烟碱、烯烃、酮类、醛类、酸类、醇类、芳香烃、酚类、吡啶和吡咯类等；3) 通过流化床中试热解实验发现，随着温度从300 ℃增加到500 ℃，生物油产率在450 ℃时达到最大值32.58%，其中烟碱组分含量最高，其次是酸、酮、酚和含氮杂环化合物；热解气体的产率随热解温度的升高不断增大，其主要成分是CO₂和CO，热解炭产率随热解温度的升高逐渐下降。

关键词: 烟草废弃物, 流化床, 热解, 生物油, 高值化应用

Abstract:

In order to probe the high-value utilization of tobacco waste, the basic physicochemical properties of the feedstock as well as their thermal conversion characteristics were tested using TG, and Py-GC/MS, etc. Then, the pyrolysis experiment of tobacco waste was carried out in a fluidized bed reactor with a feeding rate of 10 kg/h. The results showed that tobacco waste had a very low bulk density and high porosity. The mass loss during tobacco pyrolysis was mainly occurred in the temperature range of 150-400 ℃, and the maximum rate of weight loss occurred near 180 and 315 ℃. The Py-GC/MS analysis of tobacco waste suggested that the bio-oil was mainly composed of nicotine, olefins, ketones, acids, aldehydes, alcohols, aromatics, phenols, pyridines and pyrroles. According to the pyrolysis experiment in the fluidized bed reactor, with the increase of pyrolysis temperature from 300 to 500 ℃, the yield of bio-oil reached its maximum of 32.58% at 450 ℃. The dominant compound in bio-oil was nicotine, followed by acids, ketones, phenols, and N-heterocyclic compounds. In addition, the gas yield increased gradually with the increasing temperature, which was mainly composed of CO₂ and CO, while the yield of solid char residue decreased.

Key words: tobacco waste, fluidized bed reactor, pyrolysis, bio-oil, high-value utilization

中图分类号:

TQ35

蒋健, 胡安福, 王骏, 周国俊, 李允超, 王凯歌, 王树荣. 烟草废弃物流化床热解转化实验研究[J]. 林产化学与工业, 2022, 42(6): 47-54.

Jian JIANG, Anfu HU, Jun WANG, Guojun ZHOU, Yunchao LI, Kaige WANG, Shurong WANG. Experimental Study of Tobacco Waste Pyrolysis in a Fluidized Bed Reactor[J]. Chemistry and Industry of Forest Products, 2022, 42(6): 47-54.

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参考文献 25

1	WU H W, LIU Q Y, MA J, et al. Heavy metal(loids) in typical chinese tobacco-growing soils: Concentrations, influence factors and potential health risks[J/OL]. Chemospher, 2020, 245: 125591[2021-10-11]. https://doi.org/10.1016/j.chemosphere.2019.125591.
2	LIU Y , DONG J X , LIU G J , et al. Co-digestion of tobacco waste with different agricultural biomass feedstocks and the inhibition of tobacco viruses by anaerobic digestion[J]. Bioresource Technology, 2015, 189, 210- 216. doi: 10.1016/j.biortech.2015.04.003
3	WANG S R , DAI G X , YANG H P , et al. Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review[J]. Progress in Energy and Combustion Science, 2017, 62, 33- 86. doi: 10.1016/j.pecs.2017.05.004
4	WANG S R , LIN H Z , ZHANG L , et al. Structural characterization and pyrolysis behavior of cellulose and hemicellulose isolated from softwood pinus armandii Franch[J]. Energy & Fuels, 2016, 30 (7): 5721- 5728.
5	WANG S R , RU B , DAI G X , et al. Mechanism study on the pyrolysis of a synthetic β-O-4 dimer as lignin model compound[J]. Proceedings of the Combustion Institute, 2017, 36 (2): 2225- 2233. doi: 10.1016/j.proci.2016.07.129
6	DAI G X , WANG S R , HUANG S Q , et al. Enhancement of aromatics production from catalytic pyrolysis of biomass over HZSM-5 modified by chemical liquid deposition[J]. Journal of Analytical and Applied Pyrolysis, 2018, 134, 439- 445. doi: 10.1016/j.jaap.2018.07.010
7	于建军. 卷烟工艺学[M]. 北京: 中国农业出版社, 2003.
	YU J J . Cigarette Technology[M]. Beijing: China Agriculture Press, 2003.
8	LIU B , LI Y M , WU S B , et al. Pyrolysis characteristic of tobacco stem studied by PyGC/MS, TG-FTIR, and TG-MS[J]. BioResources, 2013, 8 (1): 220- 230.
9	郑燕. 生物质快速热解制备化学品研究[D]. 合肥: 中国科学技术大学, 2016.
	ZHENG Y. Biomass fast pyrolysis for valuable chemicals[D]. Hefei: University of Science and Technology of China, 2016.
10	夏倩, 刘定超, 夏骏, 等. 烟草废弃物热解制备新型电子烟精油研究[J]. 可再生能源, 2020, 38 (10): 1295- 1300. doi: 10.3969/j.issn.1671-5292.2020.10.003
	XIA Q , LIU D C , XIA J , et al. Research on preparation of new type electronic cigarette oil from pyrolysis of tobacco waste[J]. Renewable Energy Resources, 2020, 38 (10): 1295- 1300. doi: 10.3969/j.issn.1671-5292.2020.10.003
11	KARL J , PRÖLL T . Steam gasification of biomass in dual fluidized bed gasifiers: A review[J]. Renewable and Sustainable Energy Reviews, 2018, 98, 64- 78. doi: 10.1016/j.rser.2018.09.010
12	BORAH R C , GHOSH P , RAO P G . A review on devolatilization of coal in fluidized bed[J]. International Journal of Energy Research, 2011, 35 (11): 929- 963. doi: 10.1002/er.1833
13	王琦, 刘倩, 贺博, 等. 流化床生物质快速热解制取生物油试验研究[J]. 工程热物理学报, 2008, 29 (5): 885- 888. doi: 10.3321/j.issn:0253-231X.2008.05.043
	WANG Q , LIU Q , HE B , et al. Experimental research on biomass flash pyrolysis for bio-oil in a fluidized bed reactor[J]. Journal of Engineering Thermophysics, 2008, 29 (5): 885- 888. doi: 10.3321/j.issn:0253-231X.2008.05.043
14	GAO W H , CHEN K F , XIANG Z Y , et al. Kinetic study on pyrolysis of tobacco residues from the cigarette industry[J]. Industrial Crops and Products, 2013, 44, 152- 157. doi: 10.1016/j.indcrop.2012.10.032
15	WANG S R , RU B , LIN H Z , et al. Degradation mechanism of monosaccharides and xylan under pyrolytic conditions with theoretic modeling on the energy profiles[J]. Bioresource Technology, 2013, 143, 378- 383. doi: 10.1016/j.biortech.2013.06.026
16	WANG S R , RU B , LIN H Z , et al. Pyrolysis behaviors of four lignin polymers isolated from the same pine wood[J]. Bioresource Technology, 2015, 182, 120- 127. doi: 10.1016/j.biortech.2015.01.127
17	郭小义, 戴云辉, 郭紫明, 等. 应用纤维素测定仪测定烟草中的纤维素[J]. 烟草科技, 2009, 53 (1): 43- 45. doi: 10.3969/j.issn.1002-0861.2009.01.009
	GUO X Y , DAI Y H , GUO Z M , et al. Determination of cellulosein tobacco by cellulose test[J]. Tobacco Science & Technology, 2009, 53 (1): 43- 45. doi: 10.3969/j.issn.1002-0861.2009.01.009
18	MADDI B , VIAMAJALA S , VARANASI S . Comparative study of pyrolysis of algal biomass from natural lake blooms with lignocellulosic biomass[J]. Bioresource Technology, 2011, 102 (23): 11018- 11026. doi: 10.1016/j.biortech.2011.09.055
19	LI J , XIONG Z , ZENG K , et al. Characteristics and evolution of nitrogen in the heavy components of algae pyrolysis bio-oil[J]. Environmental Science and Technology, 2021, 55 (9): 6373- 6385. doi: 10.1021/acs.est.1c00676
20	NIU Q, WANG J L, CAO C C, et al. Comparative study of different algae pyrolysis using photoionization mass spectrometry and gas chromatography/mass spectrometry[J/OL]. Journal of Analytical and Applied Pyrolysis, 2021, 155: 105068[2021-10-11]. https://doi.org/10.1016/j.jaap.2021.105068.
21	BA T , CHAALA A , GARCIA-PEREZ M , et al. Colloidal properties of bio-oils obtained by vacuum pyrolysis of softwood bark: Storage stability[J]. Energy & Fuels, 2004, 18 (1): 188- 201.
22	WANG S R , GUO X J , LIANG T , et al. Mechanism research on cellulose pyrolysis by Py-GC/MS and subsequent density functional theory studies[J]. Bioresource Technology, 2012, 104, 722- 728. doi: 10.1016/j.biortech.2011.10.078
23	WANG S R , RU B , DAI G X , et al. Mechanism study on the pyrolysis of a synthetic β-O-4 dimer as lignin model compound[J]. Proceedings of the Combustion Institute, 2017, 36 (2): 2225- 2233. doi: 10.1016/j.proci.2016.07.129
24	YANG H P , YAN R , CHEN H P , et al. Characteristics of hemicellulose, cellulose and lignin pyrolysis[J]. Fuel, 2007, 86 (12): 1781- 1788.
25	WANG S R , GUO X J , WANG K G , et al. Influence of the interaction of components on the pyrolysis behavior of biomass[J]. Journal of Analytical and Applied Pyrolysis, 2011, 91 (1): 183- 189. doi: 10.1016/j.jaap.2011.02.006

温度/℃ temp.	烟碱/% nicotine	烯烃/% olefin	酮类/% ketone	醛类/% aldehyde	酸类/% acid	醇类/% alcohol	酯类/% ester	芳香烃/% aromatic hydrocarbon	酚类/% phenols	吡啶/吡咯类/% pyridine/ pyrrole	CO₂/%
350	32.5	4.0	13.5	11.9	7.7	11.1	2.6	0	4.0	0	2.3
450	26.7	9.0	13.1	13.9	9.6	7.5	3.4	0	4.2	1.5	3.3
550	14.1	20.4	11.8	10.3	4.8	2.7	6.8	2.1	3.5	3.0	7.8
650	5.2	28.6	9.9	9.3	2.6	1.2	4.7	7.7	4.6	5.1	15.1

样品samples	工业分析proximate analysis(ad.)/%				元素分析ultimate analysis(daf.)/%
样品samples	含水率 moisture(M)	灰分 ash(A)	挥发分 volatile(V)	固定碳 fixed carbon(FC)	C	H	N	S	O^*
一级旋风炭 first class cyclone char	10.13	22.21	32.63	35.03	67.02	3.13	2.99	0.90	25.96
二级旋风炭 second class cyclone char	10.52	22.3	32.12	35.06	66.94	3.26	2.10	3.13	24.57

保留时间/min retention time	化合物名称 compounds name	相对峰面积/% relative peak areas
22.064	1-甲基-2-(3-吡啶基)吡咯烷(尼古丁)nicotine	33.53
8.870	柠檬烯limonene	9.39
38.821	正十六烷酸palmitic acid	6.52
37.242	新植二烯neophytadiene	5.83
40.699	9, 12, 15-十八碳三烯酸9, 12, 15-octadecatrienoic acid	3.78
43.025	己二酸二辛酯dioctyl adipate	2.99
7.213	苯酚phenol	2.81
8.778	3-甲基-1, 2-环戊二酮3-methyl-1, 2-cyclopentanedione	2.54
19.319	对苯二酚hydroquinone	1.85
10.675	对甲酚p-cresol	1.82
27.669	烟碱nicotine	1.81
23.764	4-乙基儿茶酚4-ethyl catechol	1.76
5.090	甲基环戊烯醇酮methylcyclopentanol ketone	1.35
9.862	2-甲基-苯酚2-methylphenol	1.35
38.373	十六烷酸甲酯cetane acid methyl ester	1.31
47.253	3-乙基-5-(2-乙基丁基)-十八烷3-ethyl-5-(2-ethylbutyl)-octadecane	1.31
40.902	十八酸octadecanoic acid	1.30
6.741	3-甲基-2, 4, 10-三氧杂三环癸烷3-methyl-2, 4, 10-trioxatricyclodecane	1.25
6.688	甲基环戊烯醇酮methylcyclopentanol ketone	1.16
12.380	乙基环戊烯醇酮ethyl cyclopentenol ketone	1.14
8.610	对薄荷烯p-menthene	1.06
4.271	对二甲苯paraxylene	1.03
9.226	2, 3-二甲基-2-环戊烯-1-酮2, 3-dimethyl-2-cyclopentene-1-one	1.01

工况reaction condition¹⁾	H₂/%	CO₂/%	CH₄/%	CO/%
COS处理前before COS treatment	0.027	3.387	0.115	0.768
COS处理前before COS treatment*	0.640	78.820	2.680	17.860
COS处理后after COS treatment	0.000	4.138	0.013	0.000
COS处理后after COS treatment*	0.000	99.690	0.310	0.000

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