CO-PYROLYSIS CHARACTERISTICS AND KINETICS ANALYSIS OF PELLETS MADE FROM SEMI-COKE POWDER AND BIOMASS

Zhang Naixin; Zhu Hongyu; Lang Lin; Liu Huacai; Yin Xiuli; Gong Bin

doi:10.19912/j.0254-0096.tynxb.2023-2062

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Acta Energiae Solaris Sinica ›› 2025, Vol. 46 ›› Issue (5) : 678-689. DOI: 10.19912/j.0254-0096.tynxb.2023-2062

CO-PYROLYSIS CHARACTERISTICS AND KINETICS ANALYSIS OF PELLETS MADE FROM SEMI-COKE POWDER AND BIOMASS

Zhang Naixin^1,2, Zhu Hongyu², Lang Lin², Liu Huacai², Yin Xiuli², Gong Bin¹

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Abstract

Semi-coke biomass briquette was prepared by mixing different ratios of fine semi-coke and herb residue, so as to realize the high-efficiency and low-carbon heat conversion and utilization of fine semi-coke. Thermogravimetric analysis revealed synergistic promotional effects during co-pyrolysis under different blending ratios and heating rates. The mechanical blending and briquetting process of semi-coke powder and herb residue partially depolymerized the native crystalline ctracture of cellulose, reducing the cellulose content and crystallinity of the briquettes, thereby lowering the pyrolysis activation energy. The co-pyrolysis kinetics was analyzed by Starink method and the activation energy of the pyrolysis reaction was calculated. The reaction order n and pre-exponential tactor A were determined using the generalized master with the modified Dn-Jader model to obtain the reaction series n and the pre-exponential factor A. It is found that the activation energy of pyrolysis decreased as the proportion of fine semi-coke in the herb residue increased. When the herb residue and fine semi-coke were mixed at a ratio of 2∶1, the pyrolysis activation energy of the formed briquettes is only 162.22 kJ/mol, not only significantly lower than the pyrolysis activation energy of fine semi-coke 386.2 kJ/mol, but also significantly lower than the pyrolysis activation energy of herb residue 174.9 kJ/mol; At other different mixing ratios, the activation energy of co-pyrolysis was less than the theoretical value, which indicated that the co-pyrolysis process of herb residue and fine semi-coke is synergistic. When the proportion of fine semi-coke ≤50%, the heating rate affects the synergistic effect of co-pyrolysis more significantly, and the higher the heating rate, the greater the characteristic index of co-pyrolysis. Finally, it is found that the strength of briquette and coal-char pellets of samples decreases with the increase of the proportion of fine semi-coke in the herb residue increased, and it was found that when the mixing ratio of the herb residue and fine semi-coke was 4∶1, the compressive strength of briquette and coal-char pellets of semi-coke biomass briquette were the highest, reaching 715.5 N and 158.3 N respectively.

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biomass / coal / kinetics / co-pyrolysis / semi-coke

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Zhang Naixin, Zhu Hongyu, Lang Lin, Liu Huacai, Yin Xiuli, Gong Bin. CO-PYROLYSIS CHARACTERISTICS AND KINETICS ANALYSIS OF PELLETS MADE FROM SEMI-COKE POWDER AND BIOMASS[J]. Acta Energiae Solaris Sinica. 2025, 46(5): 678-689 https://doi.org/10.19912/j.0254-0096.tynxb.2023-2062

References

[1] YANG Z Y, NING H L, LIU J P, et al.Surface modification on semi-coke-based activated carbon for enhanced separation of CH₄/N₂[J]. Chemical engineering research and design, 2020, 161: 312-321.
[2] 朱菊芬, 李健, 郑小霞, 等. 兰炭基活性炭负载TiO₂光催化剂的制备及性能研究[J]. 当代化工, 2021, 50(10): 2350-2354.
ZHU J F, LI J, ZHENG X X, et al.Preparation and photocatalytic activity of TiO₂ supported on semi-coke-based activated carbon[J]. Contemporary chemical industry, 2021, 50(10): 2350-2354.
[3] 我的钢铁网,Mysteel年报:2023年国内兰炭市场回顾与2024年展望[R/OL]. 2024-01-08,https://jiaotan.mysteel.com/a/24010815/D9D6727F2EA0E715.html.
My Steel Website. Mysteel annual report: review of China's Semi-Coke Market in2023 and Outlook for 2024[R/OL]. 2024-01-08, https://jiaotan.mysteel.com/a/24010815/D9D6727F2EA0E715.html.
[4] WU L, ZHOU J, YANG R R, et al.Novel approach for enhanced catalytic microwave pyrolysis of low-rank coal[J]. Energy & fuels, 2020, 34(8): 9540-9551.
[5] LAN X Z,YANG Y, SOMG Y H,et al.Energy consumption analysis of carbonization process of semi coke in northern Shaan Xi[J]. Coal conversion, 2009, 32(2) : 18-21.
[6] 蒋绪, 侯党社, 杨磊, 等. 兰炭基型煤共炭化热解动力学初步研究[J]. 云南化工, 2017, 44(6): 28-30.
JIANG X, HOU D S, YANG L, et al.Preliminary study on the co-carbonization pyrolysis kinetics of blue-coke briquettes[J]. Yunnan chemical technology, 2017, 44(6): 28-30.
[7] 李健, 马炜, 闫龙, 等. 兰炭基生物质型煤成型工艺及性能的研究[J]. 当代化工, 2019, 48(8): 1694-1699, 1703.
LI J, MA W, YAN L, et al.Study on molding process and properties of semi-coke biomass briquette[J]. Contemporary chemical industry, 2019, 48(8): 1694-1699, 1703.
[8] 李春桃, 龙建, 蒋伟, 等. 复合生物质型煤粘结剂研究[J]. 中国煤炭, 2010, 36(2): 80-83, 87.
LI C T, LONG J, JIANG W, et al.The preparation process of a compound bio-briquette[J]. China coal, 2010, 36(2): 80-83, 87.
[9] 黄光许, 张如意, 谌伦建. 小麦秸秆作型煤粘结剂的试验研究[J]. 中国煤炭, 2005, 31(3): 52-54.
HUANG G X, ZHANG R Y, CHEN L J.Experimental study on wheat straw as briquette binder[J]. China coal, 2005, 31(3): 52-54.
[10] 路广军, 郭彦霞, 程芳琴, 等. 生物质秸秆作为型煤粘结剂的研究[J]. 节能技术, 2008, 26(2): 107-111.
LU G J, GUO Y X, CHENG F Q, et al.Study on the biomass used as briquette binder[J]. Energy conservation technology, 2008, 26(2): 107-111.
[11] 王明峰, 叶国辉, 蒋恩臣, 等. 桉树木屑热压成型特性研究[J]. 太阳能学报, 2018, 39(10): 2884-2890.
WANG M F, YE G H, JIANG E C, et al.Research of hot press forming characteristics of eucalyptus sawdust[J]. Acta energiae solaris sinica, 2018, 39(10): 2884-2890.
[12] 孙云娟, 蒋剑春, 赵淑蘅, 等. 稻壳与褐煤共热解动力学研究[J]. 太阳能学报, 2016, 37(11): 2747-2753.
SUN Y J, JIANG J C, ZHAO S H, et al.Kinetic analysis of rice husk and lignite during co-pyrolysis[J]. Acta energiae solaris sinica, 2016, 37(11): 2747-2753.
[13] 刘晓锋, 杨攀博, 王健, 等. 麦秆与褐煤共热解特性及动力学分析[J]. 太阳能学报, 2021, 42(9): 410-415.
LIU X F, YANG P B, WANG J, et al.Co-pyrolysis characteristics and kinetic analysis of wheat straw and lignite[J]. Acta energiae solaris sinica, 2021, 42(9): 410-415.
[14] 王燕杰, 应浩, 孙云娟, 等. 烘焙木屑与褐煤共热解特性研究[J]. 太阳能学报, 2015, 36(4): 981-987.
WANG Y J, YING H, SUN Y J, et al.Study on co-pyrolysis characteristics of torrefied sawdust and lignite[J]. Acta energiae solaris sinica, 2015, 36(4): 981-987.
[15] HAYKIRI-ACMA H, YAMAN S.Synergy in devolatilization characteristics of lignite and hazelnut shell during co-pyrolysis[J]. Fuel, 2007, 86(3): 373-380.
[16] HAYKIRI-ACMA H, YAMAN S.Interaction between biomass and different rank coals during co-pyrolysis[J]. Renewable energy, 2010, 35(1): 288-292.
[17] 阎维平, 陈吟颖. 生物质混合物与煤共热解的协同特性[J]. 中国电机工程学报, 2007, 27(2): 80-86.
YAN W P, CHEN Y Y.Interaction performance of co-pyrolysis of biomass mixture and coal of different rank[J]. Proceedings of the CSEE, 2007, 27(2): 80-86.
[18] 王彦顺, 肖瑞瑞, 丛兴顺, 等. 生物质与煤共热解动力学特性研究[J]. 广东化工, 2023, 50(5): 20-21, 16.
WANG Y S, XIAO R R, CONG X S, et al.Study on the kinetics of co-pyrolysis of biomass and coal[J]. Guangdong chemical industry, 2023, 50(5): 20-21, 16.
[19] 何玉远. 煤与生物质共热解共气化过程中硫、氮的迁移规律研究[D]. 郑州: 郑州大学, 2018.
HE Y Y.Research on the transformation of sulfur and nitrogen during co-pyrolysis and co-gasification between coal and biomass[D]. Zhengzhou: Zhengzhou University, 2018.
[20] JIANG Z H, LIU Z J, FEI B H, et al.The pyrolysis characteristics of moso bamboo[J]. Journal of analytical and applied pyrolysis, 2012, 94: 48-52.
[21] ZHAO H, YAN H X, DONG S S, et al.Thermogravimetry study of the pyrolytic characteristics and kinetics of macro-algae Macrocystis pyrifera residue[J]. Journal of thermal analysis and calorimetry, 2013, 111(3): 1685-1690.
[22] AGRAWAL A, CHAKRABORTY S.A kinetic study of pyrolysis and combustion of microalgae Chlorella vulgaris using thermo-gravimetric analysis[J]. Bioresource technology, 2013, 128: 72-80.
[23] WONGSIRIAMNUAY T, TIPPAYAWONG N.Thermogravimetric analysis of giant sensitive plants under air atmosphere[J]. Bioresource technology, 2010, 101(23): 9314-9320.
[24] 林木森, 蒋剑春. 杨木屑热解过程及动力学研究[J]. 太阳能学报, 2008, 29(9): 1135-1138.
LIN M S, JIANG J C.Process and kinetics of poplar sawdust pyrolysis[J]. Acta energiae solaris sinica, 2008, 29(9): 1135-1138.
[25] ÇEPELIOĞULLAR Ö, PÜTÜN A E. Thermal and kinetic behaviors of biomass and plastic wastes in co-pyrolysis[J]. Energy conversion and management, 2013, 75: 263-270.
[26] ZHOU W H, BAI B, CHEN G Y, et al.Study on catalytic properties of potassium carbonate during the process of sawdust pyrolysis[J]. International journal of hydrogen energy, 2018, 43(30): 13829-13841.
[27] DUAN Y, LI J, YANG X, et al.Kinetic analysis on the non-isothermal dehydration by integral master-plots method and TG-FTIR study of zinc acetate dihydrate[J]. Journal of analytical and applied pyrolysis, 2008, 83(1): 1-6.
[28] 秦丽元, 张世慧, 高忠志, 等. 生物炭与木质素混合成型及其燃烧特性研究[J]. 农业机械学报, 2017, 48(4): 276-283.
QIN L Y, ZHANG S H, GAO Z Z, et al.Molding fuel and combustion characteristics of biochar and lignin[J]. Transactions of the Chinese Society for Agricultural Machinery, 2017, 48(4): 276-283.
[29] 李伟振, 姜洋, 王微, 等. 温度对4种典型生物质成型特性的影响[J]. 生物质化学工程, 2019, 53(5): 27-33.
LI W Z, JIANG Y, WANG W, et al.Effects of temperature on pelletization of four typical types of biomass[J]. Biomass chemical engineering, 2019, 53(5): 27-33.
[30] BACH Q V, CHEN W H.Pyrolysis characteristics and kinetics of microalgae via thermogravimetric analysis (TGA): a state-of-the-art review[J]. Bioresource technology, 2017, 246: 88-100.
[31] 邱家用, 居殿春, 殷天颖, 等. 非线性等转化率法木质炭和烟煤共气化动力学[J]. 太阳能学报, 2018, 39(11): 3155-3162.
QIU J Y, JU D C, YIN T Y, et al.Kinetic analysis of co-gasification of woody biochar and bituminite by integral isoconversional non-linear method[J]. Acta energiae solaris sinica, 2018, 39(11): 3155-3162.
[32] STARINK M J.The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods[J]. Thermochimica acta, 2003, 404(1/2): 163-176.
[33] STARINK M J.A new method for the derivation of activation energies from experiments performed at constant heating rate[J]. Thermochimica acta, 1996, 288(1/2): 97-104.
[34] KHAWAM A, FLANAGAN D R.Solid-state kinetic models: basics and mathematical fundamentals[J]. The journal of physical chemistry B, 2006, 110(35): 17315-17328.
[35] KOGA N, CRIADO J M.Kinetic analyses of solid-state reactions with a particle-size distribution[J]. Journal of the American Ceramic Society, 1998, 81(11): 2901-2909.
[36] 孙云娟. 生物质与煤共热解气化行为特性及动力学研究[D]. 北京: 中国林业科学研究院, 2013.
SUN Y J.Study on the charicteristic and kinetic of biomass and coal co-pyrolysis[D]. Beijing: Chinese Academy of Forestry, 2013.
[37] 戴重阳, 田宜水, 胡二峰, 等. 生物质与低阶煤共热解特性研究及其技术进展[J]. 太阳能学报, 2021, 42(12): 326-333.
DAI C Y, TIAN Y S, HU E F, et al.Research on co-pyrolysis characteristics of biomass and low-rank coal and its technical progress[J]. Acta energiae solaris sinica, 2021, 42(12): 326-333.
[38] LIN Y, LIAO Y F, YU Z S, et al.Co-pyrolysis kinetics of sewage sludge and oil shale thermal decomposition using TGA-FTIR analysis[J]. Energy conversion and management, 2016, 118: 345-352.
[39] ZHU H Y, LANG L, FANG G, et al.Thermogravimetric characteristics and kinetics of herb residues catalyzed by potassium carbonate[J]. Journal of analytical and applied pyrolysis, 2021, 156: 105170.
[40] FANG S W, YU Z S, LIN Y S, et al.Thermogravimetric analysis of the co-pyrolysis of paper sludge and municipal solid waste[J]. Energy conversion and management, 2015, 101: 626-631.
[41] 苏秋丽, 蒋剑春, 冯君锋, 等. 木质纤维生物质加压液化制备烷基糖苷类精细化学品过程研究[J]. 太阳能学报, 2018, 39(12): 3483-3489.
SU Q L, JIANG J C, FENG J F, et al.Study on preparation of alkyl glycoside fine chemicals by pressurized liquefaction of lignocellulosic biomass[J]. Acta energiae solaris sinica, 2018, 39(12): 3483-3489.
[42] 张立强, 李凯, 宋飞跃, 等. 黄豆秆两级连续热解特性研究[J]. 太阳能学报, 2019, 40(7): 1989-1996.
ZHANG L Q, LI K, SONG F Y, et al.Research on two-step consecutive pyrolysis characteristics of soybean stalks[J]. Acta energiae solaris sinica, 2019, 40(7): 1989-1996.
[43] 任海伟, 邢雪晔, 周启芬, 等. 中药渣制备微晶纤维素工艺优化及其结构表征[J]. 太阳能学报, 2022, 43(1): 196-204.
REN H W, XING X Y, ZHOU Q F, et al.Optimization of microcrystalline cellulose preparation from Chinese herb residues and structure characterization[J]. Acta energiae solaris sinica, 2022, 43(1): 196-204.
[44] 何文强, 武小芬, 刘云, 等. 甲酸法分离南荻木质纤维素组分及其结构分析[J]. 太阳能学报, 2021, 42(11): 415-420.
HE W Q, WU X F, LIU Y, et al.Fractionation and structural analysis of main components from Triarrhena lutarioriparia by formic acid[J]. Acta energiae solaris sinica, 2021, 42(11): 415-420.
[45] 冷尔唯, 龚勋, 张扬, 等. 纤维素热解机理研究进展: 以中间态纤维素为核心的纤维素演变[J]. 化工学报, 2018, 69(1): 239-248.
LENG E W, GONG X, ZHANG Y, et al.Progress of cellulose pyrolysis mechanism: cellulose evolution based on intermediate cellulose[J]. CIESC journal, 2018, 69(1): 239-248.
[46] XU F X, ZHANG X, ZHANG F, et al.TG-FTIR for kinetic evaluation and evolved gas analysis of cellulose with different structures[J]. Fuel, 2020, 268: 117365.
[47] LI S D, CHEN X L, LIU A B, et al.Co-pyrolysis characteristic of biomass and bituminous coal[J]. Bioresource technology, 2015, 179: 414-420.