椰衣微波热解工艺的响应面法优化及液体产物组成分析

doi:10.3969/j.issn.1673-5854.2020.04.007

摘要/Abstract

摘要：

利用Box-Behnken试验设计，采用响应面法对椰衣微波热解工艺进行优化，考察了热解温度、氮气流速、升温速率和热解时间对液体产物产率的影响。试验结果表明：回归方程模型拟合较好且显著。各个因素对液体产物的产率影响的主次顺序为热解温度>氮气流速>热解时间>升温速率。最佳热解条件为热解温度550℃、氮气流速80 mL/min、升温速率20℃/min、热解时间25 min，在此条件下液体产物产率为38.28%。对液体产物的性质和组成分析发现：优化条件下得到的液体产物中含水量为14.32%，pH值为3.78，热值为24.61 MJ/kg。通过GC-MS对液体产物进行分析，最佳条件下得到的液体产物中主要含有酚、醛、酸、酮类化合物，分别为84.35%、6.01%、3.37%、2.05%，其中酚类化合物的量最高，包括苯酚（33.51%）、对甲酚（9.71%）、2-甲氧基苯酚（10.99%）和4-乙基-2-甲氧基苯酚（5.57%）。

关键词: 椰衣, 微波热解, 液体产物, 响应面法

Abstract:

The Box-Behnken experimental design was used to optimize the microwave pyrolysis process of the coconut clothes by response surface method (RSM). The effects of microwave pyrolysis temperature, nitrogen flow rate, heating rate and pyrolysis time on liquid yield were investigated. The results showed that the regression equation model fitted well and was significant. The influence order of various factors on liquid product yield was microwave pyrolysis temperature > nitrogen flow rate > pyrolysis time > heating rate. The optimum conditions were temperature 550℃, nitrogen flow rate 80 mL/min, heating rate 20℃/min and pyrolysis time 20 min. According to this process, the obtained yield of liquid product value was 38.28%. The analyses of properties and composition of liquid product showed that the water content in the liquid product was 14.32%, the pH value was 3.78, and the maximum heating value under the best pyrolysis conditions was 24.61 MJ/kg.By GC-MS analysis of bio-oil, under the optimal conditions, the liquid product was composed of phenols, aldehydes, acids, ketones and so on, and their contents were 84.35%, 6.01%, 3.37%, 2.05%. The phenols included phenol(33.51%), p-cresol(9.71%), 2-methoxyphenol(10.99%) and 4-ethyl-2-methoxyphenol(5.57%).

Key words: coconut clothes, microwave pyrolysis, liquid product, response surface method

中图分类号:

TQ35

代琪琪,魏小翠,汤宏彪,李进,王晋京. 椰衣微波热解工艺的响应面法优化及液体产物组成分析[J]. 生物质化学工程, 2020, 54(4): 42-48.

Qiqi DAI,Xiaocui WEI,Hongbiao TANG,Jin LI,Jinjing WANG. Optimization of Microwave Assisted Pyrolysis of Coconut Clothes by Response Surface Method and Analysis of Liquid Product Composition[J]. Biomass Chemical Engineering, 2020, 54(4): 42-48.

图/表 5

表1

表2

图1

表3

表4

液体产物GC-MS分析"

编号No.	组成composition	分子式molecular formula	不同温度下GC含量/% GC content under different temperature
编号No.	组成composition	分子式molecular formula	500 ℃	550 ℃	600 ℃
1	乙酸acetic acid	C₂H₄O₂	2.49	3.37	2.65
2	3-甲醛3-furmaldehyde	C₅H₄O₂	4.65	6.01	4.95
3	3-呋喃甲醇3-furanmethanol	C₅H₆O₂	1.16	2.11	1.43
4	5-甲基-2-呋喃甲醛2-furancarboxaldehyde, 5-methyl-	C₆H₆O₂	1.17	1.07	1.04
5	苯酚phenol	C₆H₆O	26.96	33.51	27.71
6	2-甲基苯酚phenol, 2-methyl-	C₇H₈O	1.24	3.75	3.85
7	对甲酚p-cresol	C₇H₄O	2.95	9.71	10.32
8	2-甲氧基苯酚phenol, 2-methoxy-	C₇H₈O₂	3.61	10.99	9.94
9	2-甲基苯并呋喃benzofuran, 2-methyl-	C₉H₁₀O	—	—	1.12
10	3，5-二甲基苯酚phenol, 3, 5-dimethyl-	C₈H₁₀O	1.49	3.77	4.21
11	4-乙基苯酚phenol, 4-ethyl-	C₈H₁₀O	2.90	2.49	2.82
12	2, 4-二甲基苯酚phenol, 2, 4-dimethyl-	C₈H₁₀O	2.60	—	—
13	2-甲氧基-5-甲基苯酚phenol, 2-methoxy-5-methyl-	C₈H₁₀O₂	3.91	3.51	3.65
14	邻苯二酚catechol	C₆H₆O₂	2.51	3.09	3.32
15	2, 3-二氢苯并呋喃benzofuran, 2, 3-dihydro-	C₈H₁₀O	0.97	—	1.08
16	4-乙基-2-甲氧基苯酚phenol, 4-ethyl-2-methoxy-	C₉H₁₂O₂	6.66	5.57	5.93
17	1-(2-羟基-5-甲基苯基)-乙酮ethanone, 1-(2-hydroxy-5-methylphenyl)-	C₉H₁₀O₂	2.33	2.05	2.71
18	2, 6-二甲氧基苯酚phenol, 2, 6-dimet hoxy-	C₈H₁₀O₃	4.73	4.44	4.70
19	2-甲氧基-4-丙基苯酚phenol, 2-methoxy-4-propyl-	C₁₀H₁₄O₂	1.02	—	0.91
20	2, 6-二甲氧基-4-甲基苯酚phenol, 2, 6-dimethoxy-4-methyl-	C₉H₁₂O₃	1.19	—	1.14
21	反异丁香酚trans-isoeugenol	C₁₀H₁₂O₂	2.60	2.00	2.52
22	5-叔丁基邻苯三酚5-tert-butylpyrogallol	C₁₀H₁₄O₃	—	1.53	1.92
23	4-羟基-3-甲氧基苯丙酮acetone, 4-hydroxy-3-methoxy-phenyl-	C₁₀H₁₂O₃	1.36	1.04	1.46
24	2, 6-二甲氧基-4-(2-丙烯基)-苯酚phenol, 2, 6-dimethoxy-4-(2-propenyl)-	C₁₁H₁₂0₃	1.04	—	1.00
合计sum up	酮类ketones		2.33	2.05	2.71
	酸类acids		2.18	3.37	2.65
	醛类aldehydes		5.82	6.01	5.63
	酚类phenols		80.40	84.35	82.78

表4

参考文献 19

1	ISAHAK W N R W , HISHAM M W M , YARMO M A , et al. A review on bio-oil production from biomass by using pyrolysis method[J]. Renewable and Sustainable Energy Reviews, 2012, 16 (8): 5910- 5923. doi: 10.1016/j.rser.2012.05.039
2	XIAO R , YANG W . Influence of temperature on organic structure of biomass pyrolysis products[J]. Renewable Energy, 2013, 50, 136- 141. doi: 10.1016/j.renene.2012.06.028
3	GUEDES R E , LUNA A S , TORRES A R . Operating parameters for bio-oil production in biomass pyrolysis:A review[J]. Journal of Analytical and Applied Pyrolysis, 2018, 129, 134- 149. doi: 10.1016/j.jaap.2017.11.019
4	GUPTA G K , MONDAL M K . Bio-energy generation from sagwan sawdust via pyrolysis:Product distributions, characterizations and optimization using response surface methodology[J]. Energy, 2019, 170, 423- 437. doi: 10.1016/j.energy.2018.12.166
5	肖红, 易美华. 椰子的开发利用[J]. 海南大学学报:自然科学版, 2003, 21 (2): 183- 189.
6	XIU S , SHAHBAZI A . Bio-oil production and upgrading research:A review[J]. Renewable and Sustainable Energy Reviews, 2012, 16 (7): 4406- 4414. doi: 10.1016/j.rser.2012.04.028
7	GARCIA-PEREZ M , CHAALA A , PAKDEL H , et al. Characterization of bio-oils in chemical families[J]. Biomass Bioenergy, 2007, 31, 222- 242. doi: 10.1016/j.biombioe.2006.02.006
8	张博, 刘庆玉, 薛志平, 等. 响应面法优化玉米秸秆微波辅助酸预处理条件[J]. 中国沼气, 2017, 35 (12): 51- 55.
9	RAJ K G , JOY P A . Coconut shell based activated carbon-iron oxide magnetic nanocomposite for fast and efficient removal of oil spills[J]. Journal of Environmental Chemical Engineering, 2015, 3 (3): 2068- 2075. doi: 10.1016/j.jece.2015.04.028
10	周腾飞, 刘文金, 郝景新, 等. 响应面法优化微波加热处理杉木弯曲艺研究[J]. 林产工业, 2015, 42 (8): 50- 52. doi: 10.3969/j.issn.1001-5299.2015.08.013
11	YONG S F , LI Z J , WEI J , et al. Microwave-induced carbonization of rapeseed shell for bio-oil and bio-char:Multi-variable optimization and microwave absorber effect[J]. Energy Conversion and Management, 2019, 191, 23- 28. doi: 10.1016/j.enconman.2019.04.020
12	商辉, 路冉冉, 孙晓锋. 微波热解生物质废弃物的研究[J]. 可再生能源, 2011, 29 (3): 25- 29. doi: 10.3969/j.issn.1671-5292.2011.03.007
13	罗爱香, 刘玉环, 万益琴, 等. 竹废料微波裂解的单因素实验研究[J]. 福建林业科技, 2007, 34 (4): 46- 50. doi: 10.3969/j.issn.1002-7351.2007.04.012
14	KILIÇ M , PVTVN E , PVTVN A E . Optimization of Euphorbia rigida fast pyrolysis conditions by using response surface methodology[J]. Journal of Analytical and Applied Pyrolysis, 2014, 110, 163- 171. doi: 10.1016/j.jaap.2014.08.018
15	BHATTACHARJEE N , BISWAS A B . Pyrolysis of Alternanthera philoxeroides(alligator weed):Effect of pyrolysis parameter on product yield and characterization of liquid product and bio char[J]. Journal of the Energy Institute, 2017, 91 (4): 605- 618.
16	MAMAEVA A , TAHMASEBI A , TIAN L , et al. Microwave-assisted catalytic pyrolysis of lignocellulosic biomass for production of phenolic-rich bio-oil[J]. Bioresource Technology, 2016, 211, 382- 389. doi: 10.1016/j.biortech.2016.03.120
17	司慧萍, 武振东, 陈杰, 等. 响应面法优化水稻秸秆炭化工艺参数[J]. 农机化研究, 2016, 38 (8): 222- 226. doi: 10.3969/j.issn.1003-188X.2016.08.047
18	关海宁, 赵晓伟, 刁小琴, 等. 响应面优化微波结合木聚糖酶制备稻壳低聚木糖工艺研究[J]. 中国酿造, 2019, 38 (1): 136- 140.
19	VENDERBOSCH R , PRINS W . Fast pyrolysis technology development[J]. Biofuels Bioproducts & Biorefining, 2010, 4 (2): 178- 208.

来源 source	平方和 sum of square	自由度 degree of freedom	均方 square	F值 F value	P值 P value	显著性¹⁾ significant degree
模型model	254.53	14	18.18	44.63	< 0.0001	**
X₁	175.28	1	175.28	430.30	x0.0001	**
X₂	9.26	1	9.26	22.74	0.0103	*
X₃	0.11	1	0.11	0.28	0.1723
X₄	0.24	1	0.24	0.58	0.1077
X₁X₂	2.66	1	2.66	6.52	0.0229	*
X₁X₃	1.95	1	1.95	4.78	0.0463	*
X₁X₄	2.28	1	2.28	5.6	0.0330	*
X₂X₃	0.00225	1	0.00225	0.00552	0.9816
X₂X₄	1.28	1	1.28	3.13	0.0984
X₃X₄	0.25	1	0.25	0.61	0.4464
X₁²	215.96	1	215.96	530.15	< 0.0001	**
X₂²	22.68	1	22.68	55.69	< 0.0001	**
X₃²	4.01	1	4.01	9.85	0.0073	**
X₄²	3.83	1	3.83	9.41	0.0083	**
残差residual	5.7	14	0.41
失拟项lack of fit	5.33	10	0.53	5.76	0.053
纯误差pure error	0.37	4	0.093
总和cor total	260.23	28
R²	0.9890

热解温度/℃ pyrolysis temperature	含水量/% water content	黏度/ (m²·s^-1) viscosity	pH值 pH value	元素分析elemental analysis/%					n(H)/ n(C)	平均分子式 average molecular formula	高位热值/ (MJ·kg^-1) high heating value
热解温度/℃ pyrolysis temperature	含水量/% water content	黏度/ (m²·s^-1) viscosity	pH值 pH value	C	H	O	N	S	n(H)/ n(C)	平均分子式 average molecular formula	高位热值/ (MJ·kg^-1) high heating value
500	15.21	225.8	3.86	52.27	6.90	27.90	4.42	0	1.58	CH_1.58O_0.40N_0.07	23.63
550	14.32	214.6	3.78	56.11	6.32	23.54	5.73	0	1.35	CH_1.35O_0.31N_0.0₉	24.61
600	14.02	211.0	3.80	53.96	5.95	27.66	6.21	0	1.32	CH_1.32O_0.38N_0.10	22.89

[1]	吴俊, 徐树英, 孟繁蓉, 张洁, 张玉苍, 王敦. 微波辅助液化椰衣的研究[J]. 生物质化学工程, 2018, 52(3): 40-44.
[2]	王燕云, 杨静. 稀碱-Fenton试剂预处理对云南苦竹酶水解得率的影响[J]. 生物质化学工程, 2015, 49(5): 17-22.
[3]	王雪, 刘燕隔, 逯家辉, 王春月, 贾冰璇, 孟庆繁, 张洋, 王迪. 黄芩中抗菌有效成分提取工艺研究[J]. 生物质化学工程, 2015, 49(5): 34-38.
[4]	陶冉, 王成章, 张宇思, 叶建中, 周昊, 陈虹霞. 银杏叶聚戊烯醇纳米乳液的制备研究[J]. 生物质化学工程, 2015, 49(1): 7-12.
[5]	张宗和;闵凡芹;秦清;徐浩;李文君;王成章;. 超声波辅助提取五倍子单宁酸的响应面优化实验[J]. 生物质化学工程, 2012, 46(6): 12-16.