• 论文
主办单位:煤炭科学研究总院有限公司、中国煤炭学会学术期刊工作委员会
生物质连续式水热预处理及固相产物热解特性研究
  • Title

    Hydrothermal flowthrough pretreatment of biomass and pyrolysis characteristics of residual solid

  • 作者

    刘天龙李琦李中宏杨沛艳庞新博黄鑫赵小燕曹景沛

  • Author

    LIU Tianlong;LI Qi;LI Zhonghong;YANG Peiyan;PANG Xinbo;HUANG Xin;ZHAO Xiaoyan;CAO Jingpei

  • 单位

    中国矿业大学 江苏省碳资源精细化利用工程研究中心重庆大学 低品位能源利用技术及系统教育部重点实验室

  • Organization
    Jiangsu Province Engineering Research Center of Fine Utilization of Carbon Resources, China University of Mining & Technology
    Key Laboratory of Low-grade Energy Utilization Technologies & Systems, Chongqing University
  • 摘要
    生物质复杂的多组分体系和致密交联的化学结构是制约其高值化利用的关键,实现木质纤维组分预分离对生物质分级转化具有重要意义。实验采用连续式水热法预处理稻壳,考察了水热温度和流量对稻壳分解速率以及固相产物化学组成与热解特性的影响。结果表明,稻壳的水热分解符合表面化学反应过程控制的未反应收缩核模型,预处理在180 ℃下能脱除稻壳95%的碱及碱土金属、92%的半纤维素和59%的木质素,极大保留了纤维素组分,这使得稻壳热解产物中以左旋葡聚糖为主的脱水糖的相对含量从9.9%提高至48.2%。
  • Abstract
    The sophisticated multi-components and densed cross-link chemical structures of lignocellulosic biomass are important bottlenecks restricting its value-added utilization. The pre-fractionation of lignocellulose components is of great significance for the fractional conversion of biomass. The present study subjected rice husk (RH) to hydrothermal treatment in a flowthrough mode and investigated the effects of hydrothermal temperature and water flowrate on the decomposition rate of RH, chemical components of residual solids and their pyrolysis characteristics. It is shown that the decomposition of RH under hydrothermal conditions conformed well to the unreacted shrinking core model with phase boundary reactions rate-controlling. The pretreatment at 180 ℃ removed 95% alkali and alkaline-earth metallic species, 92% hemicellulose and 59% lignin from RH and selectively retained most of the cellulose components. As a result of the pretreatment, the relative content of anhydrosugar (mainly levoglucosan) from pyrolysis of RH at a curie-point temperature of 445 ℃ was increased from 9.9% up to 48.2%.
  • 关键词

    稻壳水热预处理脱水糖热解

  • KeyWords

    rice husk;hydrothermal pretreatment;anhydrosugar;pyrolysis

  • 基金项目(Foundation)
    国家自然科学基金(22108294),中国博士后科学基金(2021M693412)和江苏省高校优势学科和陕煤-秦岭基础科学研究五年行动计划资助项目资助
  • DOI
  • 引用格式
    刘天龙, 李琦, 李中宏, 杨沛艳, 庞新博, 黄鑫, 赵小燕, 曹景沛. 生物质连续式水热预处理及固相产物热解特性研究[J]. 燃料化学学报(中英文), 2024, 52(6): 893-904.
  • Citation
    LIU Tianlong, LI Qi, LI Zhonghong, YANG Peiyan, PANG Xinbo, HUANG Xin, ZHAO Xiaoyan, CAO Jingpei. Hydrothermal flowthrough pretreatment of biomass and pyrolysis characteristics of residual solid[J]. Journal of Fuel Chemistry and Technology, 2024, 52(6): 893-904.
  • 相关文章
  • 图表
    连续式水热预处理装置示意图
    连续式水热预处理装置示意图
    不同水热预处理(a)流量和(b)温度下xTOC随时间的变化
    不同水热预处理(a)流量和(b)温度下xTOC随时间的变化
    液相产物的(a)单糖收率和(b)每10 min的单糖和低聚糖收率、xTOC和pH值
    液相产物的(a)单糖收率和(b)每10 min的单糖和低聚糖收率、xTOC和pH值
    稻壳水热预处理前后的扫描电子显微镜表征
    稻壳水热预处理前后的扫描电子显微镜表征
    不同温度下1−(1−xTOC)1/3与时间的关系(a)和Arrhenius曲线(b)
    不同温度下1−(1−xTOC)1/3与时间的关系(a)和Arrhenius曲线(b)
    水热预处理温度、时间和流量对固相产物收率的影响
    水热预处理温度、时间和流量对固相产物收率的影响
    稻壳及固相产物的热重(TG)和微分热重(DTG)曲线
    稻壳及固相产物的热重(TG)和微分热重(DTG)曲线
    稻壳及固相产物的CPy-GC/MS总离子流色谱图
    稻壳及固相产物的CPy-GC/MS总离子流色谱图
    稻壳及固相产物热解产物的(a)峰面积和(b)相对含量
    稻壳及固相产物热解产物的(a)峰面积和(b)相对含量
    稻壳及固相产物的碱及碱土金属含量
    稻壳及固相产物的碱及碱土金属含量
    左旋葡聚糖形成与转化反应路径
    左旋葡聚糖形成与转化反应路径
    固相产物灰分的XRD谱图
    固相产物灰分的XRD谱图

    Table1

    表 1 稻壳及固相产物的工业分析、元素分析和热值
    Samplea Proximate analysis
    wdry/%
    Ultimate analysis
    wdaf/%b
    Atomic ratio HHVg/
    (MJ·kg−1)
    A Vd FCe C H N Of H/C O/C
    RH 19.9 60.6 19.5 49.0 6.4 0.5 44.1 1.5483 0.6752 14.3
    RH-160 19.0 66.2 14.8 50.2 6.2 0.4 43.3 1.4734 0.6475 14.7
    RH-170 16.8 74.7 8.5 51.1 6.0 0.4 42.5 1.3963 0.6239 15.2
    RH-180 11.9 78.9 9.2 54.3 5.4 0.3 40.1 1.1767 0.5542 16.6
    RH-190 9.0 84.2 6.8 55.2 5.1 0.3 39.5 1.0967 0.5372 17.2
    RH-180c 22.1 65.3 12.6 55.5 5.9 0.4 38.2 1.2689 0.5175 15.9
    a: RH-xsamples represent the residual solid, wherexis the temperature for hydrothermal pretreatment;b: daf is the abbreviation of dry-ash-free;c: residual solid prepared by a batch mode under conditions of 180 ℃ for 1 h and 1∶40 mass ratio (RH/water);d: volatile matter;d: fixed carbon;e: calculated by difference;f: higher heating value, calculated byDulong’sformula:Q= 0.3383C+1.442(H−0.125O), where C, H, and O are the contents of carbon, hydrogen, and oxygen, respectively.

    Table2

    表 2 稻壳及固相产物的化学组成分析
    Pretreatment Compositionwsample/% CompositionwRH/%
    ash hemi. cel. lig. extract. ash hemi. cel. lig. extract.
    RH 19.9 19.3 31.8 24.2 4.8 19.9 19.3 31.8 24.2 4.8
    Flow mode 11.9 3.3 63.5 21.3 <0.1 5.5 1.5 29.4 9.9 <0.1
    Batch mode 22.1 7.2 43.2 26.5 1.1 13.8 4.5 27.0 16.5 0.7
    Hemi, cel, lig and extract are abbreviations of hemicellulose, cellulose, lignin and extractives, respectively. Pretreatment conditions for a flow mode are 180 ℃ for 150 min and 5 mL/min water flow and for a batch mode are 180 ℃ for 60 min and 1∶40 of RH/water mass ratio.

    Table3

    表 3 稻壳灰分SiO2纯度和比表面积分析和对比
    Sample no. SiO2puritya
    /%
    Surface areab
    /(m2·g−1)
    Method Ref.
    1 91.17 raw rice husk this study
    2 99.70 216 flow mode, 180 ℃
    3 98.91 207 batch mode, 180 ℃
    4 99.86 218 3% HCl, room temperature
    5 N.A. 164 10% HCl, 100 ℃ [26]
    6 96.89 N.A. water rinsing, room temperature [27]
    7 99.80 N.A. 5% HCl refluxing, 130 ℃
    8 99.52 N.A. ion liquid, room temperature
    9 95.77 116 raw rice husk [28]
    10 99.58 218 0.5 mol/L HCl, 60 ℃
    11 99.08 208 0.5 mol/L H2SO4, 60 ℃
    12 91.25 21 raw rice husk [29]
    13 97.94 134 hydrothermo-baric treatment, 300 ℃
    14 99.77 N.A. 5% citric acid, 80 ℃ [30]
    a: by X-ray fluorescence spectrometry;b: calculated by the Brunauer-Emmett-Taller method; N.A., not available.
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