Influence of demineralization on minerals and organic structure in Huadian oil shale
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摘要: 基于FT-IR和XRD技术研究了逐级酸洗对桦甸油页岩矿物质以及有机结构的影响。结果表明，采用HCl/HF酸洗方法可以有效去除黄铁矿以外的矿物质，但盐酸处理破坏油页岩中高岭石的立体框架结构。油页岩中有机质以脂肪族结构为主，存在形式为无序非晶态聚合体且变质程度较低。酸洗处理对油页岩有机大分子结构影响很小，但对有机结构产生了一定的影响。盐酸处理主要影响含氧官能团和苯环结构，会生成大量羧酸并破坏苯环的多环结构，但对脂肪族化合物的影响较小。氢氟酸处理主要对脂肪族化合物产生影响，破坏脂肪链的桥键结构，脂肪链断裂变短，进而使样品中脂肪族化合物含量降低。盐酸和氢氟酸处理均会破坏油页岩的羟基官能团，尤其对自缔合羟基氢键影响最大。Abstract: Effect of demineralization on minerals and organic structure of Huadian oil shale treated by HCl and HF/HCl sequentially was examined using FT-IR and XRD technology. The results show that HCl/HF treatment can effectively remove minerals except pyrite, but HCl can damage the space frame structure of kaolinite. Organic matter structure with the form of disordered amorphous polymers are mainly composed of aliphatic structure in lower metamorphic grade. Acid treatment effect on shale organic macromolecular structure is very low, but has certain influence on the organic structure. HCl treatment mainly influences oxygen containing functional group and benzene ring structure, generates a large amount of carboxylic acid and destroys the polycyclic structure of benzene ring, but has less effect on aliphatic compounds. HF treatment main affects aliphatic compounds, it can destroy the fat chain bridge bond structure fracture, makes fat chain length shorter and decreases content of aliphatics in the samples. Both HF and HCl treatment can destroy the hydroxyl groups of shale, especially for the associated hydroxyl hydrogen bond.
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Key words:
- demineralization /
- FT-IR /
- minerals /
- organic structure /
- oil shale
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图 4 逐级酸洗油页岩的XRD谱图
Figure 4 XRD spectra of oil shale before and after acid treatment
K:Kaolinite; S:Serpentine; Q:Quartz; C:Calcite; M:Muscovite; P:Prite; FS:Soda felspar
图 5 样品羟基红外光谱原图与分峰拟合图
Figure 5 Raw and curve-fitting FT-IR spectra of hydroxyl before and after acid treatment in samples
图 6 样品含氧官能团红外光谱原图与分峰拟合图
Figure 6 Raw and curve-fitting FT-IR spectra of oxygen-containing functional groups in samples
图 7 样品脂肪族官能团红外光谱原图与分峰拟合图
Figure 7 Raw and curve-fitting FT-IR spectra of aliphatic in samples
表 1 桦甸油页岩的工业分析和物质组成分析
Table 1 Proximate analyses and composition of Huadian oil shale
Proximate analyses wad/% Composition of oil shale w/% M 3.84 kerogen 35.18 A 49.12 carbonate 27.18 V 42.25 silica and clay minerals 34.89 FC 4.79 ignition loss 92.16 
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表 2 油页岩中矿物质和有机官能团的红外光谱吸收峰
Table 2 Absorption peak for FT-IR spectra of minerals and organic functional groups in oil shale
Functional group Absorption bands σ/cm-1 Kaolinite 3 699, 3 621, 1 100a, 1 032, 1 008a, 937a, 913a, 752a, 526, 695, 470, 421 Quartz 1 166a, 797, 778 Muscovite 832a, 713, 412a Serpentine 980a, 565a, 504a, 448a Calcite 1 799, 1 422, 875 As ￡.CH3 1 385 ￡.CH2 1 430 Aromatic C=C 1 600 Carboxylic acids 1 709 ￡：deformation vibration；as：asymmetric；a：hidden absorption peaks detected by second derivative spectra
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表 3 样品羟基物质红外光谱分峰拟合各吸收峰参数
Table 3 Parameters of curve-fitting FT-IR spectrum of hydroxyl in samples
Part Position σ/cm-1 Assignment Area percentage/% HD HDA HDB 1# 3 107 OH-N 3.17 7.33 7.27 2# 3 208 ring hydroxyl 12.94 10.95 13.19 3# 3 298 OH-O 10.92 13.00 22.43 4# 3 428 OH-OH 37.43 35.41 28.95 5# 3 559 OH-π 17.02 14.67 14.76 6# 3 624 free OH 18.49 18.61 13.37
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表 4 样品含氧官能团红外光谱分峰拟合各吸收峰参数
Table 4 Parameters of curve-fitting FT-IR spectrum of oxygen-containing functional groups in samples
Part Position σ/cm-1 Assignment Area percentage/% HD HAD HDB 1# 1 491 aromatic C=C 18.85 14.39 13.66 2# 1 514 aromatic ring stretch 16.98 3.27 2.36 3# 1 541 aromatic ring stretch 13.06 13.65 9.87 4# 1 569 aromatic ring stretch 10.61 10.02 11.89 5# 1 597 aromatic C=C 10.36 10.65 13.45 6# 1 630 highly conjugated C=O 12.97 17.78 19.55 7# 1 667 conjugated C=O 9.02 12.12 14.67 8# 1 709 COOH 7.43 16.08 16.55 9# 1 730 esters 1.68 1.92 4.77
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表 5 样品脂肪族物质的定量峰面积以及结构参数
Table 5 Quantitative peak areas and structure parameters of aliphatic in samples
Type HD HAD HDB Original area 10.04 14.85 17.12 Correct area 22.32 21.16 18.41 A2920/(A2860+ A2950) 1.32 1.30 0.71
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表 6 样品脂肪族物质红外光谱分峰拟合各吸收峰参数
Table 6 Parameters of curve-fitting FT-IR spectrum of aliphatic in samples
Part Position σ/cm-1 Assignment Area percentage/% HD HAD HDB 1# 2 851.775 sym. R2CH2 21.57 20.85 21.82 2# 2 873.61 sym. R2CH2 6.75 6.41 8.47 3# 2 894.901 -R3CH 8.23 9.71 6.79 4# 2 922.813 asym. R2CH2 48.89 48.09 35.24 5# 2 949.803 asym. RCH3 15.54 14.94 27.65
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