酸洗对龙口油页岩化学结构的影响分析
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(哈尔滨工业大学 能源科学与工程学院, 哈尔滨 150001)

作者简介:

刘辉(1972—),男,教授,博士生导师

通讯作者:

刘辉,liuhui@hit.edu.cn

中图分类号:

TQ536.9

基金项目:

国家自然科学基金(51476045); 国家科技支撑计划(2014BAA02B01)


Analysis of effects of demineralization on Longkou oil shale chemical structure
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(School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, China )

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    摘要:

    为研究脱灰对龙口油页岩的影响,采用HCl→HF→HNO3三级酸洗法脱灰,用XRD以及FT-IR法分别分析酸洗前后矿物质和化学结构的变化.结果表明:油页岩含氧官能团主要包含醚氧、羧基、羟基和羰基4类,酸洗制得的有机质纯度较高,酸洗后油页岩灰分的质量分数低于1%.酸洗对油页岩的化学结构产生影响,酸洗过程发生了水解反应,油页岩烷基醚、芳基醚含量减少;酸洗破坏了含氧官能团与无机盐之间的离子交联作用,将有机盐转化为有机酸,羧酸和酚羟基含量显著上升;羟基结构在酸洗前后都以环羟基、OH—O和OH—OH这3种形式为主,酸洗对环羟基、OH—O影响较大,对OH—OH影响很小;脂肪族在酸洗后部分CH伸缩振动和不对称的CH3伸缩振动转变成不对称的CH2伸缩振动,脂肪链长度增加.

    Abstract:

    To investigate the effect of demineralization on Longkou oil shale, the oil shale was acid demineralised in three steps with HCl→HF→HNO3, XRD and FT-IR was respectively used to analysis the compounds of minerals the change of chemical structure information before and after acid-treatment. The results show that oil shale mainly contains four oxygen-containing function groups, ether oxygen, carboxyl, hydroxyl and carbonyl, organic matter made by acid-treatment is really pure, the ash weight percentage is less than 1% after acid-treatment. acid-treatment has effect on the chemical structure in oil shale, hydrolysis reaction is occurred during the acid-treatment, alkyl ether and aromatic ether in the oil shale is decreased after acid-treatment; Carboxylic acid and phenolic hydroxyl are obviously increased, this is because acid-treatment breaks the ion exchange interaction between oxygen-containing groups and inorganic salts, then organic salts convert into organic acid; Hydroxyl structure both mainly contains structures of ring hydroxyl, OH-O and OH-OH before and after the acid-treatment, The acid-treatment has obvious effect on ring hydroxyl, OH-O, and has little effect on OH-OH; To the aliphatic structure, Acid-treatment makes the CH stretching vibration and CH3 asymmetric stretching vibration convert to CH2 asymmetric stretching vibration, the aliphatic chain is becoming longer.

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刘辉,闫永宏,方航,韩冰,曹庆喜,吴少华.酸洗对龙口油页岩化学结构的影响分析[J].哈尔滨工业大学学报,2018,50(1):68. DOI:10.11918/j. issn.0367-6234.201607104

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  • 收稿日期:2016-07-25
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  • 在线发布日期: 2018-01-11
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