藻渣热解特性及动力学分析

doi:10.3969/j.issn.1673-5854.2022.06.006

生物质化学工程 ›› 2022, Vol. 56 ›› Issue (6): 36-42.doi: 10.3969/j.issn.1673-5854.2022.06.006

藻渣热解特性及动力学分析

李斯¹^,², 蒋绍坚¹, 李昌珠²^,³^,⁴, 刘旭东²^,³^,⁴, 张爱华²^,³^,⁴^,⁵, 肖志红²^,³^,⁴^,*()

1. 中南大学能源科学与工程学院, 湖南长沙 410083
2. 省部共建木本油料国家重点实验室, 湖南省林业科学院, 湖南长沙 410004
3. 油脂分子构效湖南省重点实验室, 湖南长沙 410004
4. 南方木本油料利用科学国家林业和草原局重点实验室, 湖南长沙 410004
5. 湖南湘纯农业科技有限公司, 湖南长沙 410008

收稿日期:2022-01-17 出版日期:2022-11-30 发布日期:2022-11-18
通讯作者: 肖志红 E-mail:xiaozhihong@hnlky.cn
作者简介:肖志红, 研究员, 硕士生导师, 研究领域: 木本油料资源的开发和利用; E-mail: xiaozhihong@hnlky.cn
李斯(1996—), 男, 安徽阜阳人, 硕士生, 主要从事生物质热化学转化的研究
基金资助:
湖南省科技特派员创新创业计划项目(2020NK4138);湖南省林业局杰青培养科研项目(XLK202108-2);长沙市功能油脂技术创新中心(KH2101007)

Pyrolysis Characteristics and Kinetics Analysis of Algae Residue

Si LI¹^,², Shaojian JIANG¹, Changzhu LI²^,³^,⁴, Xudong LIU²^,³^,⁴, Aihua ZHANG²^,³^,⁴^,⁵, Zhihong XIAO²^,³^,⁴^,*()

1. School of Energy Science and Engineering, Central South University, Changsha 410083, China
2. State Key Laboratory of Woody Oil, Hunan Academy of Forestry, Changsha 410004, China
3. Hunan Provincial Key Laboratory of Oils & Fats Molecular Structure and Function, Hunan Academy of Forestry, Changsha 410004, China
4. Key Laboratory of National Forestry and Grassland Administration on Utilization Science for Southern Woody Oil Resources, Hunan Academy of Forestry, Changsha 410004, China
5. Hunan Xiangchun Agricultural Technology Co., Ltd., Changsha 410008, China

Received:2022-01-17 Online:2022-11-30 Published:2022-11-18
Contact: Zhihong XIAO E-mail:xiaozhihong@hnlky.cn

摘要/Abstract

摘要：

通过热重实验研究N₂气氛下升温速率对索氏提脂后的小球藻热解特性的影响，利用管式炉在N₂气氛下快速热解实验得出：在400℃时，小球藻热解转化率最高，生物油产率达57.6%，热解气为10%。采用等转化率方法FWO和KAS法对藻渣热解动力学进行分析和比较，结果表明：藻渣热解的主要热解阶段为25~800℃，可分为3个阶段，藻渣的DTG曲线存在两个失重峰，且随着升温速率提高，TG和DTG曲线都向高温区偏移，最大失重速率和残余固体质量都增加。N₂气氛条件下藻渣的主要热解阶段表观活化能和指前因子分别为228.46 kJ/mol和2.49×10²¹ min^-1，此阶段下FWO法和KAS法均能很好模拟藻渣热解数据，线性拟合相关系数（R²）均在0.96以上，最佳热解函数为dα/dT=2.49×10²¹/β exp（-228.46/（RT））（1-α）⁸。

关键词: 藻渣, 热解, 活化能, 动力学

Abstract:

The effect of heating rate in N₂ atmosphere on the pyrolysis characteristics of chlorella after Soxhlet fat extraction was studied by thermogravimetric experiment. The rapid pyrolysis experiment in tubular furnace under N₂ atmosphere showed that at 400℃, the pyrolysis conversion rate was the highest, where the yield of biooil and the pyrolysis gas were 57.6% and 10% respectively. The pyrolysis kinetics of algal residue was analyzed and compared by equal conversion methods of FWO and KAS. The results showed that the pyrolysis curve of algal residue could be divided into three stages, where the main pyrolysis stage was 155-800℃. There were two weight loss peaks in the DTG curve of algal residue. With the increase of heating rate, TG and DTG curves shifted to the high temperature zone, and the maximum weight loss rate and residual solid mass increased. Under N₂ atmosphere, the apparent activation energy and pre-exponential factor of the main pyrolysis stage of algal residue were 228.46 kJ/mol and 2.49×10²¹ min^-1, respectively. At this stage, the pyrolysis data of algal residue was well simulated using FWO and KAS method, and the linear fitting correlation coefficient (R²) was above 0.96. The best pyrolysis function was dα/dT=2.49×10²¹/β exp(-228.46/(RT))(1-α)⁸.

Key words: algal residue, pyrolysis, activation energy, kinetics

中图分类号:

TQ35
TK6

李斯, 蒋绍坚, 李昌珠, 刘旭东, 张爱华, 肖志红. 藻渣热解特性及动力学分析[J]. 生物质化学工程, 2022, 56(6): 36-42.

Si LI, Shaojian JIANG, Changzhu LI, Xudong LIU, Aihua ZHANG, Zhihong XIAO. Pyrolysis Characteristics and Kinetics Analysis of Algae Residue[J]. Biomass Chemical Engineering, 2022, 56(6): 36-42.

图/表 8

表1

表2

图1

图2

表3

图3

表4

图4

参考文献 29

1	李光朕, 孙家君, 马莉, 等. 藻类资源化利用研究现状[C]//2014中国环境科学学会学术年会论文集, 2014: 1-4.
2	邓春芳, 崔岩, 章莹颖, 等. 不同溶藻菌对小球藻破碎及油脂提取效果的影响[J]. 中国油脂, 2017, 42 (7): 106- 110. doi: 10.3969/j.issn.1003-7969.2017.07.023
3	付云. 螺旋藻渣发酵及其发酵产物抗菌活性研究[D]. 南宁: 广西大学, 2020.
4	罗祎青, 王雪, 袁希钢. 微藻生物柴油生命周期的能量平衡与碳平衡分析[J]. 清华大学学报(自然科学版), 2018, 58 (3): 324- 329. doi: 10.16511/j.cnki.qhdxxb.2018.25.009
5	王浚浩, 张雨, 杨优优, 等. 微藻种类对其热解质量损失规律和产物及动力学的影响[J]. 农业工程学报, 2018, 34 (19): 239- 247. doi: 10.11975/j.issn.1002-6819.2018.19.031
6	袁松, 黄艳琴, 刘华财, 等. 低温水热预处理对高蛋白小球藻N分布和藻渣热解特性的影响[J]. 燃料化学学报, 2019, 47 (1): 39- 52. doi: 10.3969/j.issn.0253-2409.2019.01.006
7	陈昊. 以科技赋能"碳中和"微藻固碳暨干冰转化项目在粤开建[J]. 环境, 2021, (7): 65. doi: 10.3969/j.issn.0257-0300.2021.07.024
8	阳需求. 微藻高效利用氨氮和无机碳源的条件优化及应用研究[D]. 福州: 福州大学, 2018.
9	唐紫玥, 陈伟, 胡俊豪, 等. 微藻与塑料混合热解制备低氮低氧富烃液体油[J]. 燃料化学学报, 2021, 49 (12): 1860- 1866. doi: 10.19906/j.cnki.jfct.2021070
10	VO T K , LY H V , LEE O K , et al. Pyrolysis.characteristics and kinetics of microalgal Aurantiochytrium sp. KRS101[J]. Energy, 2017, 118, 369- 376. doi: 10.1016/j.energy.2016.12.040
11	WANG X , SHENG L , YANG X . Pyrolysis characteristics and pathways of protein, lipid and carbohydrate isolated from microalgae Nannochloropsis sp.[J]. Bioresource Technology, 2017, 229, 119- 125. doi: 10.1016/j.biortech.2017.01.018
12	MOHAN D , PITTMAN C U , STEELE P H . Pyrolysis of wood/biomass for bio-oil: A critical review[J]. Energy & Fuels, 2006, 20 (3): 848- 889.
13	CHEN W , YANG H , CHEN Y , et al. Algae pyrolytic poly-generation: Influence of component difference and temperature on products characteristics[J]. Energy, 2017, 131, 1- 12. doi: 10.1016/j.energy.2017.05.019
14	LI J , LIU Y W , SHI J Y , et al. The investigation of thermal decomposition pathways of phenylalanine and tyrosine by TG-FTIR[J]. Thermochimica Acta, 2008, 467 (1/2): 20- 29.
15	LIN S L , ANIZA R , LEE Y Y , et al. Reduction of traditional pollutants and polychlorinated dibenzo-p-dioxins and dibenzofurans emitted from a diesel engine generator equipped with a catalytic ceramic fiber filter system[J]. Clean Technologies and Environmental Policy, 2018, 20 (6): 1297- 1309. doi: 10.1007/s10098-018-1559-6
16	LIU H , HONG R , XIANG C , et al. Thermal decomposition kinetics analysis of the oil sludge using model-based method and model-free method[J]. Process Safety and Environmental Protection, 2020, 141, 167- 177. doi: 10.1016/j.psep.2020.05.021
17	LU H, YU X, LI H, et al. Lipids extraction from wet Chlorella pyrenoidosa sludge using recycled[BMIM] Cl[J/OL]. Bioresource Technology, 2019, 291: 121819[2022-01-10]. http://doi.org/10.1016/j.biortech.2019.121819.
18	FRANCAVILLA M , KAMATEROU P , INTINI S , et al. Cascading microalgae biorefinery: Fast pyrolysis of Dunaliella tertiolecta lipid extracted-residue[J]. Algal Research, 2015, 11, 184- 193. doi: 10.1016/j.algal.2015.06.017
19	PATWARDHAN P R , SATRIO J A , BROWN R C , et al. Product distribution from fast pyrolysis of glucose-based carbohydrates[J]. Journal of Analytical and Applied Pyrolysis, 2009, 86 (2): 323- 330. doi: 10.1016/j.jaap.2009.08.007
20	LIU X , BOUXIN F P , FAN J , et al. Recent advances in the catalytic depolymerization of lignin towards phenolic chemicals: A review[J]. ChemSusChem, 2020, 13 (17): 4296- 4317. doi: 10.1002/cssc.202001213
21	HO S H , HUANG S W , CHEN C Y , et al. Characterization and optimization of carbohydrate production from an indigenous microalga Chlorella vulgaris FSP-E[J]. Bioresource Technology, 2013, 135, 157- 165. doi: 10.1016/j.biortech.2012.10.100
22	OBEID S , BEAUFILS N , CAMY S , et al. Supercritical carbon dioxide extraction and fractionation of lipids from freeze-dried microalgae Nannochloropsis oculata and Chlorella vulgaris[J]. Algal Research, 2018, 34, 49- 56. doi: 10.1016/j.algal.2018.07.003
23	CHOI S S , KO J E . Analysis of cyclic pyrolysis products formed from amino acid monomer[J]. Journal of Chromatography A, 2011, 1218 (46): 8443- 8455. doi: 10.1016/j.chroma.2011.09.055
24	HUSSAIN F, SHAH S Z, AHMAD H, et al. Microalgae an ecofriendly and sustainable wastewater treatment option: Biomass application in biofuel and bio-fertilizer production. A review[J/OL]. Renewable and Sustainable Energy Reviews, 2021, 137: 110603[2022-01-10]. http://doi.org/10.1016/j.rser.2020.110603.
25	LI F, SWEENEY D J, DAI Y, et al. Effect of novel Ni₂P-loaded catalysts on algal pyrolysis bio-oil[J/OL]. Renewable & Sustainable Energy Reviews, 2021, 151(14): 111575[2022-01-10]. http://doi.org/1016/j.rser.2021.111575.
26	WU L , WANG Y , ZHENG L , et al. Design and optimization of bio-oil co-processing with vacuum gas oil in a refinery[J]. Energy Conversion and Management, 2019, 195, 620- 629.
27	仲晓星, 候飞, 曹威虎, 等. 基于等转化率法的煤氧化自热动力学参数测试方法[J]. 煤炭学报, 2021, 46 (6): 1727- 1737.
28	郭先华, 张建育, 湛方栋, 等. 茶梗的热解特性及动力学研究[J]. 林产化学与工业, 2018, 38 (2): 119- 125.
29	杨红美, 徐威, 高李璟, 等. NaOH处理ZSM-5催化香茅草残渣甲醇气氛中热解实验研究[J]. 林产化学与工业, 2020, 40 (5): 50- 56.

原料 raw material	元素分析ultimate analysis/%					工业分析proximate analysis/%				高位热值/(MJ·kg^-1) high calorific value
原料 raw material	N	C	H	S	O	M	V	A	FC	高位热值/(MJ·kg^-1) high calorific value
藻渣algal residue	9.28	51.37	7.37	0.70	31.28	1.89	79.83	5.24	13.05	22.44

机理 mechanism	函数符号 symbol	f(α)	G(α)
一级反应first order reaction	F₁	1-α	-ln(1-α)
n级反应n-order reaction	F_n	(1-α)ⁿ	[(1-α)^1-n-1]/(n-1)
一维扩散one dimensional diffusion	D₁	0.5α	α²
二维扩散two dimensional diffusion	D₂	[-ln(1-α)]^-1	α+(1-α)ln(1-α)
相界反应，圆柱形对称phase boundary reaction, cylindrical symmetry	R₂	2(1-α)^1/2	1-(1-α)^1/2
相界反应，球形对称phase boundary reaction, spherical symmetry	R₃	3(1-α)^2/3	1-(1-α)^1/3

升温速率/ (℃·min^-1) heating rate	起始热解温度(T_s)/℃ initial pyrolysis temperature	第一个失重峰对应温度(T_f)/℃ temperature corresponding to first weight loss peak	第二个失重峰对应温度(T_d)/℃ temperature corresponding to second weight loss peak	主要热解结束温度(T_e)/℃ main pyrolysis end temperature	质量损失率% mass loss rate
10	150.3	280.4	321.3	498.8	71.29
20	155.3	290.3	334.4	509.2	71.13
30	160.5	299.5	342.5	521.5	70.92

α	FWO			KAS
α	拟合曲线fitting curve	R²	E/(kJ·mol^-1)	拟合曲线fitting curve	R²	E/(kJ·mol^-1)
0.2	y=-24 968.89x+48.83	0.991 26	197.41	y=23 884.05x+34.24	0.990 48	198.57
0.3	y=-24 950.13x+47.10	0.996 98	197.26	y=23 823.48x+32.43	0.996 71	198.07
0.4	y=-26 219.98x+47.76	0.979 95	207.30	y=25 054.25x+33.03	0.978 12	208.30
0.5	y=-27 398.50x+48.28	0.981 73	216.61	y=26 194.12x+33.48	0.980 07	217.78
0.6	y=-31 165.95x+52.93	0.968 36	246.40	y=29 923.32x+38.07	0.965 79	248.78
0.7	y=-37 783.17x+61.07	0.981 59	298.72	y=36 843.45x+46.68	0.977 84	306.32

[1]	周昀, 杨海平, 邹俊, 刘紫灏, 陈汉平. 中药固废原料特性与热解失重特性关联性分析[J]. 生物质化学工程, 2022, 56(6): 8-16.
[2]	杨跃三, 薛伟, 张华超. 长白松热解特性及热解动力学研究[J]. 生物质化学工程, 2022, 56(6): 24-30.
[3]	邓星立, 蒋绍坚, 肖志红, 李昌珠, 刘旭东, 李颖. 油茶果蒲与聚丙烯共热解特性及动力学分析[J]. 生物质化学工程, 2022, 56(5): 37-42.
[4]	吴松. 发酵性丝孢酵母处理精炼大豆油废水的工艺优化及动力学分析[J]. 生物质化学工程, 2022, 56(5): 51-57.
[5]	师晓鹏, 张忠峰, 王小茹, 李攀, 方书起, 常春. 炭基催化剂应用于热转化过程的研究进展[J]. 生物质化学工程, 2022, 56(5): 72-78.
[6]	赵欢欢, 邢文听, 宋香琳, 李亚科, 张利亚, 王留成. 玉米秸秆热解特性及动力学分析[J]. 生物质化学工程, 2022, 56(4): 9-14.
[7]	赵建兵, 朱俊波, 庄长福, 郑志锋, 李双庆, 李雪梅. 玉米秸秆生物炭对水中铅、镉的去除性能及作用机理研究[J]. 生物质化学工程, 2022, 56(4): 15-24.
[8]	林琦璇, 刘昕昕, 李理波, 彭锋, 任俊莉. 木质纤维生物质半纤维素分子模拟应用研究进展[J]. 生物质化学工程, 2022, 56(3): 47-58.
[9]	龙锋, 蒋霞, 曹新诚, 刘朋, 徐俊明. 碱土金属氧化物催化裂解酸化油及动力学研究[J]. 生物质化学工程, 2022, 56(2): 33-39.
[10]	纪青松, 李海朝. KOH作用下甲壳素的热解特性和动力学研究[J]. 生物质化学工程, 2021, 55(6): 21-25.
[11]	李洋, 李凯, 张镇西, 冯时宇, 胡斌, 陆强. 碱土金属氧化物基催化剂催化热解生物质研究进展[J]. 生物质化学工程, 2021, 55(6): 39-48.
[12]	付延春, 高腾飞, 张利平, 孟瑞红, 杨阳, 李雄威. 糠醛的生物炼制技术研究进展[J]. 生物质化学工程, 2021, 55(6): 59-66.
[13]	胡炳涛, 李志健. PET和关中麦秆共热解特性及其动力学研究[J]. 生物质化学工程, 2021, 55(5): 1-7.
[14]	纪东骅, 李红岩, 雷振东, 缪高健, 赵明, 王志和. 葵花杆的热解特性及热解产物分析[J]. 生物质化学工程, 2021, 55(4): 1-6.
[15]	朱启林, 曹明, 张雪彬, 陶凯, 柯用春, 孟磊. 不同热解温度下禾本科植物生物炭理化特性分析[J]. 生物质化学工程, 2021, 55(4): 21-28.

藻渣热解特性及动力学分析

Pyrolysis Characteristics and Kinetics Analysis of Algae Residue

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们