Preparation and structural analysis of humic acid by co-thermal oxidation of wheat straw and Heilongjiang lignite
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摘要: 结合矿源腐植酸(HA)产率高及生化HA活性高的特点,本研究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、FT-IR、13C NMR等分析,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,FT-IR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。Abstract: Combining with the characteristics of high yield of mineral humic acid (HA) and high activity of biochemical HA, co-thermal oxidation of low rank coal and biomass to produce complex HA (MIXHA) was newly proposed. The mixture (MIX) of Heilongjiang lignite (HL) and wheat straw (WS) was co-thermally oxidized in 10% HNO3 solution to prepare MIXHA. This work focused on comparison of the macro morphology and microstructure of MIXHA between HLHA and WSHA by SEM, FT-IR and 13C NMR analyses, and explored the synergistic effect between HL and WS during the co-thermal oxidation process. The results show that MIXHA content is higher than the theoretical value. Decomposition of HNO3 molecular produces active oxygen atoms and nitrogen oxides to attack the molecular structure of WS and HL. Due to hydrogen bond rearrangement, glycosidic bond rupture, and crosslinking, plenty of alkyl radicals generated in WS are combined with the condensation aromatic ring in HL. Thus, the protonated aromatic carbon is changed into aliphatic substituted aromatic carbon. The obtained MIXHA is rich in oxygen-containing functional groups, and has high activity. Obvious characteristic peaks are observed in FTIR spectra of MIXHA. This work would provide a new idea for classification and resource utilization of low-rank coal and agricultural and forestry wastes.
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Key words:
- humic acid /
- biomass /
- lignite /
- co-thermal oxidation /
- 13C NMR
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表 1 原料的工业分析及元素分析
Table 1 Proximate and ultimate analyses of raw materials
Sample Proximate analysis w/% Ultimate analysis wdaf/% Mad Ad Vdaf FCdaf C H N S Oa 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 表 2 OR中
${\varphi}_{{\rm{HA}}}$ 及工业分析、元素分析Table 2 Proximate and ultimate analyses of OR
Sample ${\varphi}_{{\rm{HA}}}$ Proximate analysis w /% Ultimate analysis wdaf/% Mad Ad Vdaf FCdaf C H N S Oa 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 表 3 三种HA的工业分析、元素分析与含氧官能团含量
Table 3 Proximate and ultimate analyses, and contents of O-containing functional groups in HA
Sample Proximate analysis w/% Ultimate analysis wdaf/% O-containing functional groups
wdaf/(mmol·g−1)Mad Ad Vdaf FCdaf C H N S Oa −COOH −ph−OH total acidic
groupsHLHA 4.78 13.63 61.23 38.77 60.40 5.90 3.54 0.18 29.98 2.50 2.91 5.41 WSHA 4.32 7.01 62.51 37.49 50.04 5.68 3.82 0.08 40.38 2.22 3.57 5.79 MIXHA 3.59 14.46 62.82 37.18 59.30 5.71 3.75 0.22 31.03 5.74 6.98 12.72 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 FT-IR spectra
Wavenumber
/cm−1Assignment Area percentage/% HLHA WSHA MIXHA 1690−1720 C−O,ketone,aldehyde and −COOH 16.40 12.73 15.04 1600−1660 conjugated C=O 6.45 15.46 21.87 1450−1600 aromatic C=C 14.56 13.24 3.23 1375−1450 CH3−Ar,CH3 and CH2 11.29 14.97 10.39 1300−1375 CH2−C=O 9.95 6.28 5.83 1100−1300 C−O phenol 21.25 23.12 20.46 1000−1110 ash,alkyl ethers,Si−O and aryl ethers 20.10 14.18 23.18 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 δ Assignment Area percentage/% HLHA WSHA MIXHA 15 fat-methyl carbon 9.62 3.66 1.38 20 aromatic-methyl carbon 12.73 4.34 5.31 25 methylene carbon 9.26 6.31 7.17 31 methylene carbon 8.96 20.90 21.44 42 quaternary carbon, methine carbon − 3.66 2.00 49 quaternary carbon, methine carbon − − 0.83 56 methoxy carbon 1.17 3.64 4.56 75 oxygen to methine carbon 8.59 10.36 5.57 84 oxygen to methine carbon 3.87 3.44 5.76 89 oxygen to methine carbon − − 2.76 107 acetal ketal carbon 3.81 6.59 1.83 111 aromatic proton carbon 2.27 − − 116 aromatic proton carbon 4.18 6.27 4.48 122 aromatic bridgehead carbon − 3.63 − 126 aromatic bridgehead carbon 4.90 − 4.27 132 alkyl aromatic carbon 8.68 3.88 5.93 135 alkyl aromatic carbon − 1.77 − 139 alkyl aromatic carbon − − 2.23 142 alkyl aromatic carbon − − 1.26 151 aryl-O carbon 7.22 11.25 1.96 155 aryl-O carbon − − 4.34 160 carboxyl and amide carbons − − 1.06 167 carboxyl and amide carbons 4.45 − 0.30 176 carboxyl and amide carbons 6.36 9.61 9.19 185 aldehyde and ketone carbons 1.86 − 6.37 202 aldehyde and ketone carbons 2.05 0.69 − 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 δAssignment Area percentage/% HLHA WSHA MIXHA_E MIXHA_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 f COO carboxyl and amide carbons 10.81 9.61 10.55 10.21 180−220 f CO aldehyde and ketone carbons 3.91 0.69 6.37 2.30 f O carbon in oxygen-containing functional groups 35.59 38.99 41.87 37.29 -
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