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麦秸秆与黑龙江褐煤共热氧化法制备腐植酸及其结构分析

李艳玲 陈曦 张翠清 李晓峰 刘鹏 陈文轩 任素霞 雷廷宙

李艳玲, 陈曦, 张翠清, 李晓峰, 刘鹏, 陈文轩, 任素霞, 雷廷宙. 麦秸秆与黑龙江褐煤共热氧化法制备腐植酸及其结构分析[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60033-1
引用本文: 李艳玲, 陈曦, 张翠清, 李晓峰, 刘鹏, 陈文轩, 任素霞, 雷廷宙. 麦秸秆与黑龙江褐煤共热氧化法制备腐植酸及其结构分析[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60033-1
LI Yan-ling, CHEN Xi, ZHANG Cui-qing, LI Xiao-feng, LIU Peng, CHEN Wen-xuan, REN Su-xia, LEI Ting-zhou. Preparation and structural analysis of humic acid by co-thermal oxidation of wheat straw and Heilongjiang lignite[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60033-1
Citation: LI Yan-ling, CHEN Xi, ZHANG Cui-qing, LI Xiao-feng, LIU Peng, CHEN Wen-xuan, REN Su-xia, LEI Ting-zhou. Preparation and structural analysis of humic acid by co-thermal oxidation of wheat straw and Heilongjiang lignite[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60033-1

麦秸秆与黑龙江褐煤共热氧化法制备腐植酸及其结构分析

doi: 10.1016/S1872-5813(22)60033-1
基金项目: 国家重点研发计划项目(2021YFC2101604)、国家自然基金(51906021)、国家能源投资集团科技创新项目(GJNY-21-95)资助。
详细信息
    通讯作者:

    Email: liupeng@cczu.edu.cn

    china_newenergy@163.com

  • 中图分类号: TQ536.1

Preparation and structural analysis of humic acid by co-thermal oxidation of wheat straw and Heilongjiang lignite

Funds: The project was supported by the National Key Research and Development Program of China (2021YFC2101604), National Natural Science Foundation of China (51906021), and Technology Innovation Project of CHN ENERGY (GJNY-21-95).
  • 摘要: 结合矿源腐植酸(HA)产率高及生化HA活性高的特点,本文首次提出将低阶煤与生物质共热氧化制备复合型HA(MIXHA)的想法。将黑龙江褐煤(HL)及麦秸秆(WS)的混合物(MIX)在10%的HNO3溶液中进行了共热氧化,制备了MIXHA。通过SEM、FTIR、13CNMR等分析,本文重点从HA的宏观形貌及微观结构对比了MIXHA与HL、WS分别单独制备的矿源HA、生化HA,分析HL与WS在共热氧化过程的协同作用。结果表明:MIXHA含量高于理论值, HNO3分子的分解产生的活性氧原子、氮氧化物进攻HL与WS的分子结构,由于氢键重排、糖苷键断裂、交联等作用,WS纤维素与半纤维素产生的大量烷基自由基结合在HL缩合芳环上被氧化产生的醌基、羧基的邻对位,从而将芳香环上的质子碳转化为脂肪取代碳。得到的MIXHA含氧官能团丰富、活性高,FTIR谱图具有明显的特征峰。本研究为低阶煤与农林废弃物的分级、资源化利用提供了一种新思路。
  • 图  1  原料、OR、ER的SEM图像

    Figure  1  SEM images of raw materials, OR, and ER

    图  2  HA产品图

    Figure  2  HA product image

    图  3  不同HA的M值

    Figure  3  M values of different HA

    图  4  不同HA的FTIR光谱谱图

    Figure  4  FTIR spectra of different HA

    图  5  不同HA的 FTIR光谱的拟合曲线图

    Figure  5  Fitting curves of FTIR spectra of different HA

    图  6  不同HA的13C NMR分峰拟合模拟

    Figure  6  Peak fitting simulation of 13C NMR spectra of different HA

    表  1  原料的工业分析及元素分析

    Table  1  Industrial analysis and elemental analysis of raw materials

    SampleProximate analyses w/%Ultimate analyses wdaf%
    MadAdVdafFCdafCdafHdafNdafSdafOdafa
    HL 24.82 21.10 49.75 50.25 72.39 5.50 0.70 0.62 26.29
    WS 10.55 10.43 79.63 20.37 50.05 7.30 0.57 0.02 42.06
    下载: 导出CSV

    表  2  OR中$ {\mathit{\varphi }}_{\mathit{H}\mathit{A}} $及工业分析、元素分析(%)

    Table  2  Industrial analysis and elemental analysis of OR and ER of raw materials

    Sample${\varphi }_{HA}$Proximate analysisUltimate analysis
    ${\rm{M}}_{{\rm{daf}}} $${\rm{A}}_{{\rm{daf}}} $${\rm{V}}_{{\rm{daf}}} $${\rm{FC}}_{{\rm{daf}}} $${\rm{C}}_{{\rm{daf}}} $${\rm{H}}_{{\rm{daf}}} $${\rm{N}}_{{\rm{daf}}} $${\rm{S}}_{{\rm{daf}}} $${\rm{O}}_{{\rm{daf}}}^{\rm{a}} $
    HLOR 51.65 4.89 49.57 72.79 27.21 71.58 6.53 5.16 0.31 16.41
    WSOR 13.84 7.62 0.87 83.81 16.19 42.88 5.40 0.97 0.00 50.75
    MIXOR 37.46 6.44 24.89 75.62 24.38 49.22 5.38 2.06 0.00 43.35
    下载: 导出CSV

    表  3  三种HA的工业分析、元素分析与含氧官能团含量

    Table  3  Industrial analysis and elemental analysis of humic acid products

    SampleProximate analysis % Ultimate analysis % O-containing functional groups
    daf/mmol·g−1
    MadAdVdafFCdafCdafHdafNdafSdafOdafa−COOH−ph−OHTotal acidic groups
    HLHA4.7813.6361.2338.77 60.405.903.540.1829.982.502.915.41
    WSHA4.327.0162.5137.4950.045.683.820.0840.382.223.575.79
    MIXHA3.5914.4662.8237.18 59.305.713.750.2231.03 5.746.9812.72
    下载: 导出CSV

    表  4  不同HA中各含氧官能团面积百分比

    Table  4  Area percentage of oxygen-containing functional groups in FTIR spectra

    Wavenumber
    /cm−1
    AssignmentArea percentage/%
    HLHAWSHAMIXHA
    1690−1720C−O,ketone,aldehyde and
    −COOH
    16.4012.7315.04
    1600−1660conjugated C=O6.4515.4621.87
    1450−1600aromatic C=C14.5613.243.23
    1375−1450CH3−Ar,CH3 and CH211.2914.9710.39
    1300−1375CH2-C=O9.956.285.83
    1100−1300C−O phenol21.2523.1220.46
    1000−1110Ash,alkyl ethers,
    Si−O and aryl ethers
    20.1014.1823.18
    下载: 导出CSV

    表  5  HA中不同结构的碳在13C NMR谱中对应的化学位移及相对含量

    Table  5  Chemical shift and relative content of different types of carbons in HA

    Chemical shift (10−6)AssignmentArea percentage/%
    HLHAWSHAMIXHA
    15Fat-methyl Carbon9.623.661.38
    20Aromatic-methyl Carbon12.734.345.31
    25Methylene Carbon9.266.317.17
    31Methylene Carbon8.9620.9021.44
    42Quaternary Carbon, Methine Carbon-3.662.00
    49Quaternary Carbon, Methine Carbon--0.83
    56Methoxycarbon1.173.644.56
    75Oxygen to Methine Carbon8.5910.365.57
    84Oxygen to Methine Carbon3.873.445.76
    89Oxygen to Methine Carbon--2.76
    107Acetal Ketal Carbon3.816.591.83
    111Aromatic Proton Carbon2.27--
    116Aromatic Proton Carbon4.186.274.48
    122Aromatic Bridgehead Carbon-3.63-
    126Aromatic Bridgehead Carbon4.90-4.27
    132Alkyl Aromatic Carbon8.683.885.93
    135Alkyl Aromatic Carbon-1.77-
    139Alkyl Aromatic Carbon--2.23
    142Alkyl Aromatic Carbon--1.26
    151Aryl-O Carbon7.2211.251.96
    155Aryl-O Carbon--4.34
    160Carboxyl and Amide Carbons--1.06
    167Carboxyl and Amide Carbons4.45-0.30
    176Carboxyl and Amide Carbons6.369.619.19
    185Aldehyde and Ketone Carbons1.86-6.37
    202Aldehyde and Ketone Carbons2.050.69-
    下载: 导出CSV

    表  6  不同HA的不同类型碳的分布

    Table  6  Distribution of different types of carbon in HA

    Chemical
    shift (10−6)
    AssignmentArea percentage/%
    HLHAWSHAMIXHA-EMIXHA_T
    15 fal3 Aliphatic Methyl Carbon 9.62 3.66 1.38 6.64
    20 fal3a Aromatic Methyl Carbon 12.73 4.34 5.31 8.54
    25−31 fal2 Methylene Carbon 18.22 27.21 28.61 22.72
    35−50 fal1 fal* Quaternary Carbon, Tertiary Carbon 0 3.66 2.83 1.83
    50−95 falO Aliphatic Carbon attached to O 13.64 17.44 18.65 15.54
    95−110 falOO Acetal Ketal Carbon 3.81 6.59 1.83 5.20
    110−120 faH Aromatic Proton Carbon 6.45 6.27 4.48 6.36
    120−130 faB Aromatic Bridgehead Carbon 4.90 3.63 4.27 4.27
    130−150 faS Alkyl Aromatic Carbon 8.68 5.65 9.42 7.17
    150−160 faO Aromatic Carbon attached to O 7.22 11.25 6.30 9.24
    160−180 fCOO Carboxyl and Amide Carbons 10.81 9.61 10.55 10.21
    180−220 fCO Aldehyde and Ketone Carbons 3.91 0.69 6.37 2.30
    fO Carbon in Oxygen-containing functional groups 35.59 38.99 41.87 37.29
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-03-20
  • 录用日期:  2022-05-09
  • 修回日期:  2022-05-06
  • 网络出版日期:  2022-06-09

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