Effect of mineral matter on product evolution during pyrolysis of Huadian oil shale
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摘要: 对桦甸油页岩进行逐级酸洗并对原样及各级酸洗样品的热解产物进行了碳平衡计算以及气相色谱和傅里叶红外光谱实验, 得到了矿物质对油页岩热解不凝性气体、半焦以及页岩油的影响特性.结果表明, 碳酸盐可以促进有机碳和氢向页岩油中转化, 而硅酸盐对有机碳和氢向页岩油中转化具有抑制作用, 碳酸盐和硅酸盐均可以使得页岩油中氢碳原子比降低.碳酸盐促进了油页岩热解产油并抑制了干酪根向不凝气分解转化, 而硅酸盐抑制了油页岩热解产油但对干酪根向不凝气的分解转化具有促进作用.碳酸盐和硅酸盐均可以促进热解不凝气中CO2和H2的生成, 而对CO的生成具有抑制作用, 碳酸盐可以抑制热解不凝气中碳氢化合物的生成, 而硅酸盐对其生成具有促进作用.碳酸盐和硅酸盐均可以使得页岩油中脂肪链长度变短及异构化程度变大, 并能够提高干酪根热解产物的芳构化程度.Abstract: The effect of mineral matter on pyrolysis and product evolution of oil shale was studied by GC and FT-IR. Hudian oil shale was treated by sequential washing with HCl and HF/HCl. The results show that carbonate has catalytic effect on conversion of organic carbon and hydrogen from Kerogen to shale oil, which is inhibited by silicate. The H/C atomic ratio in shale oil increases in both carbonate-free and silicate-free oil shale. Carbonate enhances gas yield and inhibits oil yield, while silicate is just opposite. The contents of CO2 and H2 decrease but CO increases in both carbonate-free and silicate-free oil shale. Carbonate can inhibit generation of hydrocarbon in gas product while silicate has catalytic effect on it. All the carbonate and silicate can increase the length and degree of branching aliphatic side chains in shale oil and improve aromatization of the solid product from shale.
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Key words:
- demineralization /
- oil shale /
- pyrolysis /
- GC /
- FT-IR
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表 1 桦甸油页岩工业分析及物质组成
Table 1 Proximate analysis and composition of Huadian oil shale
Sample Proximate analysis w/% Composition of oil shale w/% Mad Aad Vad FCad kerogen SOA carbonate silica and clay minerals HD-R-1 3.84 49.12 42.25 4.79 38.18 0.43 26.49 34.90 HD-R-2 3.85 49.07 42.49 4.59 38.42 0.44 26.39 34.75 SOA: soluble organics after acid treatment; kerogen: kerogen and insoluble minerals 表 2 样品碳和氢元素的含量
Table 2 Content of carbon and hydrogen of samples
Sample Ultimate analysis w/% H/C
(atomic ratio)Ctdaf Codaf Ccdaf Hdaf HD-R 70.33 66.09 4.24 9.98 1.812 HCl 61.10 61.01 0.09 9.18 1.806 HF 60.91 60.89 0.02 8.28 1.631 HD-RC 21.48 20.13 1.35 1.24 0.742 HClC 17.63 17.58 0.05 1.18 0.808 HFC 15.76 15.76 0.01 0.64 0.489 HD-RO 38.52 38.52 5.77 1.799 HClO 28.35 28.35 4.48 1.895 HFO 37.91 37.91 6.04 1.911 daf: on a dry ash-free basis;Ctdaf: total of organic and inorganic carbon;Codaf: organic carbon;Ccdaf: inorganic carbon 表 3 各级酸洗样品热解页岩油分峰拟合
Table 3 Curve-fitting FT-IR spectrum results of pyrolysis oil for oil shale after treatment with various acids
Sample Ratio of curve-fitting/% CH CH2 CH3 2-benzene 3-benzene 4-benzene CH3/CH2 ar/al HD-R 9.30 64.46 20.20 4.37 1.54 0.13 31.34 6.43 HCl 18.73 60.45 15.16 4.38 1.19 0.09 25.08 6.00 HF 11.47 69.39 13.67 4.49 0.92 0.06 19.70 5.79 2, 3, 4-benzene:2, 3, 4 adjacent H deformation;ar/al:ratio of aromatic to aliphatic -
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