栎树皮与玉米秸秆共热解行为及热解产物分析研究

doi:10.13304/j.nykjdb.2023.0880

摘要/Abstract

摘要：

农林废弃物玉米秸秆与栎树皮共热解有助于提高栎树皮热转化效率，将其作为能源物质的规模化应用具有重要意义。为探究栎树皮与玉米秸秆共热解特性，采用热重分析仪和管式炉考察二者共热解的失重行为和产物产率，并对共热解产物的热解气、热解油及焦炭进行分析。结果表明，共热解增加了栎树皮的失重速率峰值，且随着玉米秸秆添加量的增加，350~425 ℃范围内的失重速率峰值逐渐增加，表明共热解过程促进了挥发分的释放。此外，玉米秸秆添加量的增加对热解半焦及气体产物的生成均有促进作用，且气体产物增加速率不断提高，但热解油产率受到抑制，其中热解油中的三环芳烃和四环芳烃产率的下降速率最高可达6.30%和18.49%，而在高玉米秸秆添加量条件下，单环和双环芳烃产率的下降速率较低。除此之外，共热解焦炭产物的拉曼光谱带的面积比（I_{（Gr+Vl+Vr）}/I_D）随着玉米秸秆添加量的增加逐渐降低，且其降低速率逐渐增加，表明芳香化程度逐渐提高。上述现象主要是由于玉米秸秆在热解过程中具有更高的失重速率，且玉米秸秆中的碱金属催化剂促进了高分子碳氢化合物向低分子碳氢化合物的转化，因此在高玉米秸秆添加量条件下，共热解过程中失重速率和气体产率增加，而较高环数的多环芳烃产率显著降低。

关键词: 栎树皮, 玉米秸秆, 共热解, 产物产率, 碱金属

Abstract:

Co-pyrolysis of corn stalk as an agroforestry waste with oak bark helps to improve the thermal conversion efficiency of oak bark， which is of great significance for its large-scale application as an energy substance. In order to investigate the co-pyrolysis characteristics of oak bark and corn stalk， the weight loss behavior， product yield during co-pyrolysis process were investigated by thermogravimetric analyzer and tube furnace， and the pyrolysis gas， pyrolysis oil and char were also analyzed. The results showed that the co-pyrolysis process increased the peak of weight loss rate， and with the increase of addition amount of corn stalk， the peak of weight loss rate in the temperature range of 350~425 ℃ gradually increased， indicating that the co-pyrolysis promoted the volatile release of oak bark. In addition， the increase of corn stalk addition promoted the generation of both pyrolysis char and gas products， and the increase rate of pyrolysis gas was increased. The production rate of pyrolysis oil was suppressed， and the polycyclic aromatic hydrocarbon （PAHs）（tricyclic and tetracyclic） had the highest decreasing rates of 6.30% and 18.49%， respectively. However， at the high addition of corn stalk， the decrease rates of yield of monocyclic and bicyclic PAHs were relatively low. Furthermore， the Raman band area ratio I_{（Gr+Vl+Vr）}/I_D of char gradually decreased with the increase of addition amount of corn stalk， and its decrease rate gradually increased， showing the increase in aromatization of char. The main reason for the above phenomenon was due to the faster weight loss rate of corn stalk during pyrolysis， and the alkali metal catalysts in corn straw promoted the conversion of high molecular hydrocarbons to low molecular hydrocarbons. This leaded to an increase in the weight loss activity of and gas yield during the co-pyrolysis process with high corn stalk additions， as well as a significant decrease in the yield of more cyclic PAHs.

Key words: oak bark, corn stalk, co-pyrolysis, product yield, alkali metal

中图分类号:

段丽君, 丁献华, 李为琴, 闫双堆. 栎树皮与玉米秸秆共热解行为及热解产物分析研究[J]. 中国农业科技导报, 2025, 27(5): 164-172.

Lijun DUAN, Xianhua DING, Weiqin LI, Shuangdui YAN. Investigation of Co-pyrolysis Behavior and Pyrolysis Product Analysis of Oak Bark and Corn Stalks[J]. Journal of Agricultural Science and Technology, 2025, 27(5): 164-172.

图/表 10

表1 蒙古栎树皮和玉米秸秆的工业特性和元素含量

Table 1 Element content and ultimate analyses of Mongolian oak bark and corn stalk

样品Sample	工业分析Proximate analysis/%				元素含量Element content
样品Sample	水分Moisture	灰分Ash	挥发分Volatiles	固定碳Fixde carbon	C/%	H/%	O/%	N/%	S/%	K/（µg·g^-1）
蒙古栎树皮Mongolian oak bark	6.95	3.08	77.50	12.47	47.52	5.86	35.79	0.56	0.24	254
玉米秸秆Corn stalk	3.49	2.50	69.39	24.62	43.41	8.95	32.25	1.10	8.30	41 356

图1 管式炉热解试验系统

Fig. 1 Tube furnace pyrolysis test system

图2 栎树皮和玉米秸秆的TG曲线和DTG曲线

Fig. 2 TG and DTG curves of oak bark and corn stalk

图3 不同配比生物质共热解的TG曲线和DTG曲线

Fig. 3 TG/DTG curves for co-pyrolysis of biomass with different ratios

图4 栎树皮和玉米秸秆共热解下各产物的产率

Fig. 4 Yields of different products of co-pyrolysis of oak bark and corn stalk

图5 栎树皮和玉米秸秆共热解过程中气体的释放特性

Fig. 5 Gas release behavior for co-pyrolysis of oak bark and corn stalk

图6 栎树皮和玉米秸秆共热解过程轻质焦油各类组分含量

Fig. 6 Contents of different components of light tar during the co-pyrolysis of oak bark and corn stalk

图7 栎树皮和玉米秸秆共热解过程焦油UV-F光谱

Fig. 7 UV-F spectra of tar during co-pyrolysis of oak bark and corn stalk

图8 栎树皮和玉米秸秆共热解焦的红外谱图

Fig. 8 Infrared spectra of co-pyrolysis char of oak bark and corn stalk

图9 栎树皮和玉米秸秆共热解焦的拉曼参数I（Gr+Vl+Vr）/ID

Fig. 9 Raman parameters I（Gr+Vl+Vr）/ID of co-pyrolysis char of oak bark and corn stalk

参考文献 21

1	李奇,薛伟,张华超.蒙古栎树皮的热解特性及动力学分析[J].消防科学与技术,2021,40(3):412-415.
	LI Q, XUE W, ZHANG H C.Pyrolysis characteristics and kinetics of Mongolian oak bark [J].Fire Sci.Technol.,2021,40(3):412-415.
2	魏立纲,张丽,徐绍平.原料对自由落下床中生物质与煤共热解行为的影响[J].燃料化学学报,2011,39(10):728-734.
	WEI L G, ZHANG L, XU S P. Effects of feedstock on co-pyrolysis of biomass and coal in a free fall reactor [J]. J. Fuel Chem. Technol., 2011, 39(10):728-734.
3	INGRAM L, MOHAN D, BRICKA M,et al..Pyrolysis of wood and bark in an auger reactor:physical properties and chemical analysis of the produced bio-oils [J].Energy Fuels,2008,22(1):614-625.
4	胡海清,高健,胡同欣.基于热重分析的延边州地区7种常见乔木树种的燃烧性排序[J].中南林业科技大学学报,2020,40(11):1-10.
	HU H Q, GAO J, HU T X. Combustibility ordering of 7 kinds of typical tree species in Yanbian area based on thermogravimetric analysis [J]. J. Cent. South Univ. For. Technol., 2020,40(11):1-10.
5	陈斌,原梦雪,邱禧荷,等.油页岩混合小麦秸秆分级共热解特性[J].江苏大学学报(自然科学版),2022,43(5):580-586.
	CHEN B, YUAN M X, QIU X H,et al..Graded co-pyrolysis characteristics of oil shale mixed wheat straw [J].J.Jiangsu Univ. (Nat. Sci.), 2022,43(5):580-586.
6	陈宏鹏,金光,陈义胜,等.聚丙烯与玉米秸秆共热解的试验研究[J].应用化工,2019,48(5):1038-1042.
	CHEN H P, JIN G, CHEN Y S, et al.. Graded co-pyrolysis charactristics of oil shale mixed wheat straw [J]. Appl. Chem. Ind., 2019, 48(5):1038-1042.
7	霍建宝.污泥与秸秆共热解特性及固体产物的燃烧特性研究[D].吉林:东北电力大学,2023.
	HUO J B. Study on co-pyrolysis charactristics of sludge and straw and combustion characteristics of solid products [D]. Jilin: Northeast Electric Power University, 2023.
8	ZHOU L, ZONG Z M, TANG SR, et al.. FTIR and mass spectral analyses of an upgraded bio-oil [J]. Energ Source Part A, 2010, 32(4):370-375.
9	ASADULLAH M, RASID N S A B, KADIR S A S A,et al..Production and detailed characterization of bio-oil from fast pyrolysis of palm kernel shell [J].Biomass Bioenergy,2013,59:316-324.
10	刘亮, 李文豪, 刘增辉,等. CO₂/H₂O气氛对生物质焦化学结构演化及反应性作用机理研究[J].环境工程,2023,41(4):108-115.
	LIU L, LI W H, LIU Z H, et al.. Study on chemical structure evolution and reactive mechanism of biomass char prepared in CO₂/H₂O [J]. Environ. Eng., 2023, 41(4):108-115.
11	张传佳,李安心,涂德浴.水稻秸秆成型燃料热解特性试验研究[J].中国农业科技导报,2017,19(7):95-100.
	ZHANG C J, LI A X, TU D Y.The experimental study on pyrolysis characteristics of rice straw briquette fuel [J]. J. Agric.Sci. Technol., 2017,19(7):95-100.
12	DEMIRBAŞ A.Yields of hydrogen-rich gaseous products via pyrolysis from selected biomass samples [J].Fuel, 2001,80(13):1885-1891.
13	PIELSTICKER S, GÖVERT B, KREITZBERG T,et al..Simultaneous investigation into the yields of 22 pyrolysis gases from coal and biomass in a small-scale fluidized bed reactor [J].Fuel, 2017,190: 420-434.
14	YANG H P, YAN R, CHEN H P,et al..Characteristics of hemicellulose,cellulose and lignin pyrolysis [J].Fuel,2007,86(12/13):1781-1788.
15	林博文.生物质与煤共热解行为及协同效应研究[D].杭州:浙江大学,2021.
	LIN B W. Study on the thermal behavior and synergistic effect during co-pyrolysis of biomass and coal [D]. Hangzhou: Zhejiang University, 2022.
16	刘鹏.火焰中多环芳香烃(PAHs)的演变机理研究[D].上海:上海交通大学,2019.
	LIU P. The study on the evolution mechanism of polycyclic aromatic hydrocarbons (PAHs) in flames [D]. Shanghai: Shanghai Jiao Tong University, 2019.
17	黄宇,樊啟洲,汪烈,等.闷烧热解及间接加热直立移动床生物质炭化设备设计研究[J].中国农业科技导报,2018,20(11):69-78.
	HUANG Y, FAN Q Z, WANG L,et al.. Design of biomass carbonization equipment for vertical moving bed [J]. J. Agric. Sci. Technol., 2018,20(11):69-78.
18	LI X, HAYASHI J I, LI C Z. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. part VII. Raman spectroscopic study on the changes in char structure during the catalytic gasification in air [J]. Fuel, 2006, 85(10):1509-1517.
19	LI X J, HAYASHI J I, LI C Z.FT-Raman spectroscopic study of the evolution of char structure during the pyrolysis of a Victorian brown coal [J]. Fuel, 2006,85(12/13):1700-1707.
20	LI X, LI C Z. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. part VIII. catalysis and changes in char structure during gasification in steam [J]. Fuel, 2006, 85(10):1518-1525.
21	ZHANG Z Z, ZHU M M, ZHANG Y,et al..Ignition and combustion characteristics of single particles of Zhundong lignite: effect of water and acid washing [J]. Proc. Combust. Inst., 2017,36(2):2139-2146.

[1]	侯赛赛, 仝姗姗, 王鹏企, 谢冰雪, 张瑞芳, 王鑫鑫. 生物炭和秸秆对不同作物生长性状和养分吸收的影响[J]. 中国农业科技导报, 2025, 27(4): 179-191.
[2]	王洪波, 樊志鹏, 乌兰图雅, 王春光, 马哲. 揉碎玉米秸秆螺旋输送仿真离散元模型参数标定[J]. 中国农业科技导报, 2023, 25(3): 96-106.
[3]	高日平, 刘小月, 潘遵天, 张东旭, 沈祥军, 栗艳芳, 黄洁, 景宇鹏. 生物菌剂对玉米秸秆堆沤过程水热状况及酶活性的影响[J]. 中国农业科技导报, 2023, 25(2): 174-181.
[4]	邵东伟, 刘文斌, 栾积毅, 韩平, 钟海涛, 冯海城. 玉米秸秆颗粒燃料层燃特性研究[J]. 中国农业科技导报, 2023, 25(10): 109-118.
[5]	杨梦雅1,闫非凡1,闫美超1,王贺1,朴仁哲1,崔宗均2,赵洪颜1*. 低温木质纤维素分解复合菌系PLC-8对玉米秸秆的分解特性[J]. 中国农业科技导报, 2021, 23(1): 73-81.
[6]	马光路1,吕建波2,曹青2*. 玉米秸秆中木质素、半纤维素和纤维素的组分分离研究[J]. 中国农业科技导报, 2015, 17(6): 70-79.
[7]	杜英1,2,王自强2,3,徐晓娟2,3,张利平1,王云山2*,苏志国2. 利用玉米秸秆酶解液发酵胶质芽胞杆菌WY120的研究[J]. , 2013, 15(2): 179-184.