Effect of pyrite removal by chromous chloride on organic matter structure in Huadian oil shale
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摘要: 采用元素分析、13C NMR、XPS和TG-MS技术考察了氯化亚铬（CrCl2）脱除黄铁矿对桦甸油页岩有机质结构的影响。结果表明，CrCl2可有效脱除有机质中的黄铁矿，脱除率为96.19%。CrCl2对有机质的碳骨架结构影响较小，脱除黄铁矿前后有机质中脂碳、芳碳和羧基/羰基碳的相对含量以及有机质的热解特征温度基本保持不变，但CrCl2可破坏有机质中的C-O键，使C-O/C-OH和O=C-O的含量减少，造成0.98%的有机碳损失和12.54%的有机质损失。CrCl2处理后，有机质的C含量显著增加，H含量稍有增加，O含量显著降低，使得H/C略微降低，O/C明显降低。另外，CrCl2处理后，单位质量有机质中脂碳的含量增加了5.28%，使其热解过程中产生了更多的挥发分，残留的氧化铬对有机质的热分解可能也具有促进作用。Abstract: Influence of pyrite removal by chromous chloride (CrCl2) on structure of organic matter in Huadian oil shale was examined using ultimate analysis, 13C NMR, XPS and TG-MS technology. The results show that CrCl2 treatment leads to 96.19% removal of pyrite from oil shale. The relative contents of aliphatic, aromatic, and carboxyl/carbonyl carbons of organic matter remain about the same level after pyrite removal by CrCl2, so does the pyrolysis characteristic temperature, indicating the carbon skeleton of organic matter is less affected by CrCl2. However, the CrCl2 treatment can break C-O bond in organic matter and reduce content of C-O/C-OH and O=C-O, leading to about 0.98% and 12.54% loss for organic carbon and organic matter, respectively. In addition, carbon content of organic matter significantly increases, hydrogen content slightly increases, and oxygen content is markedly reduced after pyrite removal by CrCl2, resulting in a slight decrease of H/C but a marked decrease of O/C in organic matter. The mass loss of organic matter treated by CrCl2 increases during pyrolysis because aliphatic carbon content of unit mass of organic matter increases 5.28%. Besides, the residual chromium oxide may also promote decomposition of organic matter during pyrolysis.
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Key words:
- oil shale /
- pyrite /
- chromous chloride /
- organic matter /
- structure
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图 3 HD-CF和HD-CFCr的XPS C 1s及其分峰拟合谱图
Figure 3 XPS C 1s spectra and their fitting curves of HD-CF and HD-CFCr
图 5 HD-CF和HD-CFCr热解气态产物的析出曲线
Figure 5 Gaseous products evolution curves detected by MS during pyrolysis of HD-CF and HD-CFCr
表 1 桦甸油页岩的工业分析、元素分析及铝甑分析
Table 1 Proximate, ultimate and Fischer assay analyses of Huadian oil shale
Proximate analysis wad /% Ultimate analysis wad /% Fischer assay wad /% M A V FC C H N S char oil water gas 2.83 70.27 22.30 4.51 16.74 2.33 0.32 0.82 86.97 7.21 2.39 3.37 ad: air dry basis; M: moisture; A: ash; V: volatile matter; FC: fixed carbon 
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表 2 HD-CF和HD-CFCr的工业分析
Table 2 Proximate analysis of HD-CF and HD-CFCr
Sample Proximate analysis wad/% M A V FC HD-CF 0.93 13.58 64.08 21.41 HD-CFCr 0.25 1.69 75.95 22.11
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表 3 HD-CF和HD-CFCr的XRF分析
Table 3 XRF analysis of HD-CF and HD-CFCr
Sample Component wad /% SO3 Fe2O3 F Cr2O3 Al2O3 MgO CaO TiO2 SiO2 Cl others HD-CF 20.30 15.48 20.77 0 18.17 7.73 4.02 1.68 0.87 4.49 6.48 HD-CFCr 44.45 3.91 0 26.04 1.73 0.61 2.58 7.25 2.05 10.58 0.81
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表 4 HD-CF和HD-CFCr的灰分组成
Table 4 Ash component of HD-CF and HD-CFCr
Sample wad /% Component wad /% A Fe2O3 Cr2O3 Al2O3 MgO CaO TiO2 SiO2 others HD-CF 13.58 3.86 0 4.53 1.93 1.00 0.42 0.22 1.62 HD-CFCr 1.69 0.15 0.98 0.07 0.02 0.10 0.27 0.08 0.02
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表 5 HD-CF和HD-CFCr的元素分析
Table 5 Ultimate analysis of HD-CF and HD-CFCr
Sample Ultimate analysis wdaf/% Molar ratio C H O* N St H/C O/C HD-CF 66.95 8.44 19.91 1.42 3.28 1.51 0.22 HD-CFCr 75.43 9.30 12.65 1.52 1.10 1.48 0.13 *: by difference; daf: dry and ash free basis
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表 6 HD-CF和HD-CFCr的结构参数
Table 6 Structural parameters of HD-CF and HD-CFCr
Structural parameter Chemical shift δ Mole percentage /% HD-CF HD-CFCr fal 0-90 74.94 76.31 far 90-165 17.73 16.62 fac 165-220 7.33 7.07 fal: fraction of carbon atoms that are sp3 hybridized (aliphatic); far: fraction of carbon atoms that are sp2 hybridized (aromatic); fac: fraction of carbon atoms that are in carboxyl or carbonyl groups
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表 7 HD-CF和HD-CFCr的XPS C 1s分析结果
Table 7 XPS C 1s data of HD-CF and HD-CFCr
Functionality Binding energy E/eV Mole content w/% HD-CF HD-CFCr C-C/C-H 284.75 68.48 76.60 C-O/C-OH 286.15 (±0.05) 16.09 8.01 C=O 287.45 (±0.05) 2.97 8.58 O=C-O 288.65 (±0.05) 12.47 6.81
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