神华煤直接液化残渣结构特性的探讨
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摘要
鉴于煤炭直接液化残渣的性质尚缺少系统全面的研究探讨，为此，本文把“神华煤直接液化残渣结构特性的探讨”作为研究课题，全面系统地分析神华煤直接液化残渣的组成、结构特性等物理、化学性质，为残渣的加工利用作基础性准备工作。
本文选择用溶剂萃取的方法将残渣分成油(HS)、沥青烯(HI-BS)、前沥青烯(BI-THFS)和四氢呋喃不溶物(THFI)四个组分来分别进行分析研究。
本文除了采用元素分析、分子量测定等常规分析方法外，还采用了傅立叶红外光谱法、核磁共振波谱法以及热解色谱—质谱等物理仪器分析方法对三个有机组分进行组成和结构的分析。通过对大量的分析结果的解析，得出三个组分的分子结构的基本特征。重点分析了油和沥青烯分子的官能团的种类和变化情况、分子内部的主要结构单元以及氢碳原子的分布情况。发现油和沥青烯都含有四十种以上的结构形式，不仅包括1～4个(沥青烯达到6个)环的缩合芳香结构单元和部分加氢饱和的氢化芳香结构，而且含有一系列的碳数不等的正构烷烃，这些正构烷烃并不是单独存在于组分中，而是以芳香结构单元键合的侧链形式存在。综合仪器分析的结果，计算出油和沥青烯分子的平均结构参数，从而绘制出油和沥青烯的平均分子结构模型。对前沥青烯也进行了多种分析，得到了部分性质参数。
另外，在沥青烯的热解色谱质谱的分析中发现存在四氢呋喃的聚合体，说明溶剂萃取过程中存在四氢呋喃的聚合现象。
对于四氢呋喃不溶物，本文采用了岩相显微分析法和X射线衍射法(XRD)进行分析。发现原料煤中的矿物质有些转变成了硫酸盐，以及催化剂的活性形态是具有八种晶体结构的磁黄铁矿Fe_((1-X))S。
Coal direct liquefaction will be taken into commercial application, but the properties of residue have been little researched. Therefore, in this paper, the structure characters of Shenhua coal direct liquefaction residue have been studied. In order to deal with and utilize the residue, the systematical study of the physical and chemical properties of the residue could provide basic data for its utilizations in the future.
The residue has been separated into four fractions by using solvent extraction, that is, the oil(HS), asphaltene(HI-BS), preasphaltene(BI-THFS) and the insoluble of tetrahydrofuran (THFI), which have been studied respectively.
In this paper, not only routine analyses, such as elemental, molecule weight etc., but also fourier infrared spectrometry, nuclear magnetic resonance spectrometry and pyrolysis GC-MS and so on have been used. The characters of three organic fractions have been obtained by analyzing the much data and information from above instrumental analyses. The emphasis in this paper is the molecular structure of the oil and asphaltene fractions, including the species and characters of the functional groups, the main structure units of intra-molecule and distributions of carbon and hydrogen atoms. The oil and asphaltene fractions contain more than forty kinds of structure fragments, including 1～4 rings (6 rings for asphaltene) of condensing aromatic and partially hydrogenated aromatic structure units, as well as a series of n-alkane chain that are linked with aromatic structure. Average molecule structure model of the oil and asphaltene fractions have been drawn out, in according to colligating the data of instrumental analysis and calculating average structure parameters of the two fractions. The properties of preasphaltene have been partially studied.
In addition, polymers of tetrahydrofuran have been found in the pyrolysis GC-MS analysis of the asphaltene fraction, which has been shown that polymerization of tetrahydrofuran has occurred in the course of solvent extraction.
For the insoluble of tetrahydrofuran, using microscopy analysis and X-ray diffraction analysis, it has been found out that a part of the mineral substances in feed coal have become sulphates as well as the active forms of catalyst are 8 kinds of crystal structures of Fe_(1-x)S.
本文选择用溶剂萃取的方法将残渣分成油(HS)、沥青烯(HI-BS)、前沥青烯(BI-THFS)和四氢呋喃不溶物(THFI)四个组分来分别进行分析研究。
本文除了采用元素分析、分子量测定等常规分析方法外，还采用了傅立叶红外光谱法、核磁共振波谱法以及热解色谱—质谱等物理仪器分析方法对三个有机组分进行组成和结构的分析。通过对大量的分析结果的解析，得出三个组分的分子结构的基本特征。重点分析了油和沥青烯分子的官能团的种类和变化情况、分子内部的主要结构单元以及氢碳原子的分布情况。发现油和沥青烯都含有四十种以上的结构形式，不仅包括1～4个(沥青烯达到6个)环的缩合芳香结构单元和部分加氢饱和的氢化芳香结构，而且含有一系列的碳数不等的正构烷烃，这些正构烷烃并不是单独存在于组分中，而是以芳香结构单元键合的侧链形式存在。综合仪器分析的结果，计算出油和沥青烯分子的平均结构参数，从而绘制出油和沥青烯的平均分子结构模型。对前沥青烯也进行了多种分析，得到了部分性质参数。
另外，在沥青烯的热解色谱质谱的分析中发现存在四氢呋喃的聚合体，说明溶剂萃取过程中存在四氢呋喃的聚合现象。
对于四氢呋喃不溶物，本文采用了岩相显微分析法和X射线衍射法(XRD)进行分析。发现原料煤中的矿物质有些转变成了硫酸盐，以及催化剂的活性形态是具有八种晶体结构的磁黄铁矿Fe_((1-X))S。
Coal direct liquefaction will be taken into commercial application, but the properties of residue have been little researched. Therefore, in this paper, the structure characters of Shenhua coal direct liquefaction residue have been studied. In order to deal with and utilize the residue, the systematical study of the physical and chemical properties of the residue could provide basic data for its utilizations in the future.
The residue has been separated into four fractions by using solvent extraction, that is, the oil(HS), asphaltene(HI-BS), preasphaltene(BI-THFS) and the insoluble of tetrahydrofuran (THFI), which have been studied respectively.
In this paper, not only routine analyses, such as elemental, molecule weight etc., but also fourier infrared spectrometry, nuclear magnetic resonance spectrometry and pyrolysis GC-MS and so on have been used. The characters of three organic fractions have been obtained by analyzing the much data and information from above instrumental analyses. The emphasis in this paper is the molecular structure of the oil and asphaltene fractions, including the species and characters of the functional groups, the main structure units of intra-molecule and distributions of carbon and hydrogen atoms. The oil and asphaltene fractions contain more than forty kinds of structure fragments, including 1～4 rings (6 rings for asphaltene) of condensing aromatic and partially hydrogenated aromatic structure units, as well as a series of n-alkane chain that are linked with aromatic structure. Average molecule structure model of the oil and asphaltene fractions have been drawn out, in according to colligating the data of instrumental analysis and calculating average structure parameters of the two fractions. The properties of preasphaltene have been partially studied.
In addition, polymers of tetrahydrofuran have been found in the pyrolysis GC-MS analysis of the asphaltene fraction, which has been shown that polymerization of tetrahydrofuran has occurred in the course of solvent extraction.
For the insoluble of tetrahydrofuran, using microscopy analysis and X-ray diffraction analysis, it has been found out that a part of the mineral substances in feed coal have become sulphates as well as the active forms of catalyst are 8 kinds of crystal structures of Fe_(1-x)S.
引文
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