超声波条件下煤中不同赋存形态小分子的溶出规律

采用CS2溶剂对童亭亮煤进行索氏萃取和超声萃取,用气相色谱/质谱联用仪(GC/MS)对相关萃取物进行分析.结果表明,超声场的介入明显地缩短了萃取时间,提高了萃取率;长链烯烃是网络态小分子溶出的重要标志;芳烃和含芳环类组分与煤微孔结构亲和性较强,而各类杂原子化合物、环烷烃和异构烷烃更容易以网络嵌入态存在;超声波的振动作用能有效地解开分子间的缠绕及交联,而超声波的空化作用加速了溶剂的传质速率,两者共同将网络嵌入态小分子的溶出时间提前了约600h.     

GC/MS Analysis of Fractional Extraction of Fusain from Tongting Bituminous Coal in CS2

Fusain from Tongting （Huaibei, Anhui Province） bituminous （FTTB） coal was fractionally extracted using Soxhlet extractor with CS2. Then the extracts were analyzed with GC/MS. Comparison of experimental data between FTTB coal and clarain from Tongting bituminous （CTTB） coal was carried out. The results show that the kinds of small molecule components detected by GC/MS of FTTB are less than those of CTTB. Long-chain alkanes exist mostly in the extracts of fusain. Macromolecular networks are predominant in the FTTB coal mainly composed of inertinite in the coal petrography. The size of micropores in the FTTB coal is relatively small, and the development of micropores is relatively low. Thus the content of aromatic compounds with affinity for micropores is relative low in FTTB, while the content of long-chain alkanes with affinity for macromolecule networks is relatively high. Sub-components in exinite determine the distribution of long-chain alkanes extracted in the last stage. Odd-numbered carbon distribution appears when resin is most in exinite, while high carbon alkane distribution appears when exinite is dominant in cutinite. Small aromatic molecules are firstly packed in micropores, and exist in a free state after micropores are saturated.     

添加剂对煤的缔合结构影响

探讨了各种盐类添加剂对煤的缔合结构影响。卤素阴离子能够同煤分子通过酸碱作用而强烈缔合，从而破坏了煤分子的缔合结构，提高了煤在有机溶剂中的抽提率。通过对UF煤在N—甲基2砒咯烷酮／二硫化碳混合溶剂(1：1体积比)抽提物进行溶剂级分得到吡啶不溶物(PI)，对此PI经溶剂处理和添加剂乙酸四丁基胺(TBAA)作用，分别得到几种在混合溶剂中具有不同溶解度的PI，结果表明，TBAA通过改变PI的缔合结构。使所得PI具有不同溶解度，文中对这一过程的机理进行了探讨。     

离子液体溶胀煤体与溶解甲烷研究进展

综述了煤矿瓦斯增抽方法、离子液体溶胀煤、离子液体溶解甲烷的研究现状;分析了目前低透煤层瓦斯增抽主要是采用物理作用破碎煤体来释放CH4,或注CO2或N2置换瓦斯的办法,其效果虽然显著,但对于微孔隙中的甲烷解吸还是存在着局限性．鉴于功能化离子液体溶胀煤及吸收甲烷的协同作用,提出利用离子液体增加煤中孔隙尺寸以吸收煤表面CH4气体的方法,强化抽采过程中的瓦斯解吸,降低了煤层本身的瓦斯含量,提高抽采瓦斯气体的利用效率．最后,阐述离子液体溶胀煤、溶解甲烷的研究进展,以及离子液体应用于瓦斯抽采方面的研究基础．     

Study of Constituents of Fractionated Extraction from Datong Coal

Datong coal was extracted with CS2, n-hexane, benzene, methanol, acetone, tetrahydro-furan（THF） and THF/methanol（1：3,v/v） mixed solvent sequentially. The extracts were analyzed with GC/MS. It is presented that group seperation of soluble organic compounds in the coal can be achieved by fractionated extraction using different solvents. The results show that CS2 was effective for extracting arenes from the coal sample, n-Hexane extractable fraction from Datong coal mainly consists of n-alkanes. A great variety of oxygen-containing compounds are dominant in the components of methanol-soluble fraction. Acyclic isoprenoids, pentecyclic triterpanes and a series of cyclohexanes with long-chain alkyl-substitutes are detected in acetone-soluble fraction. Dicyclic aramatic hydrocarbons are identified in benzene-soluble fraction and 4-6 cyclic condensed aramatic hydrocarbons are identified in THF-soluble fraction. The molecular structures detection of 1,2-dichlorobenzene, 2,4-dibromophnol, 2,4,6-tribromophenol and 4-chlorobenzophenone firstly provide information for existence form of bromine and chlorine in coal.     

两种烟煤CS2溶剂分次萃取物的FTIR分析

为揭示煤中可溶组分的存在方式和溶出行为，以CS2为溶剂对两种烟煤进行了约1000h的索氏萃取，按时间段分批（次）提取萃取物进行了FTIR定性和定量分析，结果表明，CS2可萃取组分的溶出具有明显的时序性、阶段性和某些爆发性的特点，波形曲线是萃取物溶出时一些重要基团吸收峰面积随时间变化的典型特征，曲线形状、生波位置、波峰时刻和波幅大小随煤种而不同，2950～2858，3040，1610，860，815，750cm^-1的吸收峰面积和累积萃取时间分别以AR，AAr1，AAr2，AAr3，AAr4，AAr5和t表示，则AR／AAr2～t曲线的波峰所处时刻反映着萃取物中所合脂链的长短，波幅反映着所含脂链成分的数量；AR/AAr1-t,AAr3/AAr1-t,AAr4/AAr1-t和AAr5/AAr1-t曲线的相互结合还指示出单个氢原子、两个相邻氢原子和4个相邻氢原子被取代芳环的溶出行为．脂链和侧链与煤中其它部分形成非共价键时的多点联结是形成波形溶解曲线的重要原因．     

抚顺镜煤和树脂煤CS2可溶物的族组成和萃取

用CS2对抚顺镜煤和树脂煤进行了索氏萃取，并用柱层析法对萃取物进行了族组分分离，研究了萃取物的族组成和萃取动力学特征。实验结果表明：树脂煤的萃取率远高于镜煤，萃取物中烷烃和芳烃含量较高，而镜煤萃取物主要为非烃；其萃取过程可分为两个阶段，第一阶段速率比第二阶段速率大一个数量级；煤中低分子化合物有游离态、吸附态和共溶态三种赋存形式。     

神府煤萃取物组成结构的特征分析

采用苯、甲醇、丙酮、等体积的CS2与丙酮的混合溶剂和四氢呋喃依次萃取神府煤,得到其萃取物E1E5,并采用钌离子催化氧化法氧化各级萃取物,所得氧化产物经重氮甲烷酯化后再进行GC/MS分析,以产物组成结构的差异来推测各级萃取物组成结构的差异。结果表明,神府煤萃取物所得酯化产物的主要成分是烷酸甲酯和烷二酸二甲酯,推测其萃取物中含有大量的烷基芳烃和α,ω-二芳基烷烃;且随着溶剂极性的增强,其萃取物氧化后的酯化产物中,烷酸甲酯和烷二酸二甲酯的碳链长度呈一定的递增趋势,推测神府煤中长链烷基芳烃和α,ω-二芳基烷烃易溶于极性较强的溶剂;在氧化产物中还检测出19种甾烷酸甲酯、萜烷酸甲酯和霍烷酸甲酯,表明神府煤萃取物中含有与芳环相连的甾烷基、萜烷基和霍烷基结构。     

CS2 extraction and FTIR & GC/MS analysis of a Chinese brown coal

The abundance of low-rank coals in China, such as bituminous and brown coals, makes studies of their composition and structure of great significance to both coal chemistry research and for efficient utilization of the coal. We describe how a Chinese brown coal was ultrasonically extracted with carbon disulfide (CS2) and the raw and extracted coals were characterized by Fourier Transform Infrared Spectroscopy (FTIR). The corresponding extract was analyzed with a coupled gas chromatograph mass spectrometer (GC/MS). The FTIR analysis shows a great abundance of amidocyanogen, carbonyl, aromatic and hetero aromatic rings and single carbon-heteroatom bonds. This suggests the possible occurrence of compounds like alcohols, phenols, amines, esters, carboxylic acids, ethers, aromatics or heteroaromatics. The GC/MS analysis of the CS2 extract detected 62 compounds, among which the non-polar ones were of lower abundance while the polar ones were in higher abundance and were structurally diverse. This demonstrates the compositional and structural complexity of Shengli coal.     

大花细辛叶提取物对小鼠热板致痛的镇痛作用

目的：研究大花细辛叶乙醇提取物的镇痛活性及其镇痛活性组分。方法：通过小鼠热板法,研究大花细辛叶的乙醇提取物以及采用系统溶剂法分离得到的5个组分的镇痛活性。结果：大花细辛叶95％乙醇提取物（500mg／kg）能提高小鼠痛阈值,正丁醇萃取部分（500mg／kg）能显著提高痛阈值且优于对照组阿司匹林（200mg／kg）。结论：大花细辛叶的乙醇提取物有镇痛作用,正丁醇萃取部分是镇痛的主要组分。     

水溶性稻壳热解油的萃取及分析

在超声辐射下用等体积的水萃取稻壳热解油,离心分离后得到水溶物和水不溶物．分别占总稻壳热解油质量分数的81％和19％;依次用石油醚、CS2、CCl4和苯萃取水溶物,分别得到萃取物F1～F4,其中F4约占水溶物质量分数的24％,从F4中共检测出18种有机化舍物,主要成分为苯酚及其衍生物。     

固体酸催化剂催化葛亭煤的加氢裂解

采用TMSOTf、SbCl5和活性炭制备固体酸催化剂。以环己烷为溶剂,对葛亭煤进行非催化和催化加氢裂解,用石油醚对反应混合物进行溶剂萃取,分别得到萃取物E1和E2,并对两种萃取物进行GC/MS分析。在E1和E2中共检测出200种化合物,可以分为以下8类：芳烃、烷烃、烯烃、酚、酯、酮、其他含氧化合物以及含氮化合物,其中芳烃含量最高;E2中8类产物的含量均高于E1中对应产物的含量,其中芳烃含量差别最大;与E1相比,E2中萘、菲和芘及其同系物的含量均有所提高,在E2中还检测出了角鲨烯和几种茚酚。结果表明,所制固体酸催化剂可促进葛亭煤中Car—Calk和Car—O的断裂。     

Separation and analysis of lignite bioconversion products

The bioconversion of coal at ambient conditions is a promising technology for coal processing, although the mechanisms of coal degradation are still not understood fully. In this work, the bioconversion of lignite was studied using a fungus isolated from decaying wood. The lignite samples were oxidized with nitric acid under moderate conditions and then the oxidized samples were placed on a potato medium with isolated fungus for lignite bioconversion. Lignite, oxidized lignite and residual products after bioconversion of lignite were sequentially extracted with petroleum ether, CS₂, methanol, acetone and tetrahydrofuran (THF), and then each extract was characterized by gas chromatography–mass spectrometry (GC/MS). The differences in composition and structure among the samples were inferred by comparing the differences between the extracts. The results show that aromatics with one or several benzene rings and their derivatives; and some long-chain alkanes containing oxygen decreased in the methanol-, acetone-, and THF-soluble fraction from residual lignite, whereas long chain or a few branched alkanes and small quantities of aromatic compounds increased in petroleum ether and CS₂ soluble fractions.     

灵武煤CS2／NMP萃取物的柱层析分离及其馏分的GC／MS分析

室温下用等体积的二硫化碳／N-甲基-2-吡咯烷酮（CS2／NMP）混合溶剂对灵武煤进行超声辐射萃取。依次用正已烷、苯、氯仿和四氢呋喃作为展开剂对萃取物进行柱层析分离,得到馏分F1～F4,用气相色谱／质谱联用仪（GC／MS）分析各馏分。结果表明,烷烃高度富集于F1中,F3中稠环芳烃相对含量最高,F4的主要成分是合氧有机化合物。     

Pore characterization of different types of coal from coal and gas outburst disaster sites using low temperature nitrogen adsorption approach

To characterize the pore features of outburst coal samples and investigate whether outburst coal has some unique features or not, one of the authors, working as the member of the State Coal Mine Safety Committee of China, sampled nine outburst coal samples(coal powder and block) from outburst disaster sites in underground coal mines in China, and then analyzed the pore and surface features of these samples using low temperature nitrogen adsorption tests. Test data show that outburst powder and block coal samples have similar properties in both pore size distribution and surface area. With increasing coal rank, the proportion of micropores increases, which results in a higher surface area. The Jiulishan samples are rich in micropores, and other tested samples contain mainly mesopores, macropores and fewer micropores. Both the unclosed hysteresis loop and force closed desorption phenomena are observed in all tested samples. The former can be attributed to the instability of the meniscus condensation in pores,interconnected pore features of coal and the potential existence of ink-bottle pores, and the latter can be attributed to the non-rigid structure of coal and the gas affinity of coal.     

辣椒红色素纯化方法的研究

以辣椒油树脂为原料,重点研究了其纯化工艺.结果显示:用石油醚和pH10左右、浓度40%的丙酮溶液的混合液对辣椒油树脂进行萃取,萃取次数达到5次以上,即可得到较为优良的辣椒红色素产品.同时此法能有效地利用辣椒素成分,提高辣椒的利用率.     

Microwave-assisted extraction of Shenfu coal and its macromolecule structure

Coals consist of some molecules trapped within an organic matrix from which some organic compounds can be extracted by solvents. The Soxhlet technique has been widely used for extracting organic compounds. Microwave heating methods may be successfully applied in the field of coal science. Acetone extraction yields and the chemical composition of the extract were inves-tigated using a typical Chinese coal, Shenfu coal, with microwave-assisted extraction. The acetone extract and residue were ana-lyzed by GC/MS and carbon-13 nuclear magnetic resonance spectroscopy respectively. The carbon spectra were converted into several numerical parameters, fa, Ha, Xb, which indicate the difference in macromolecular structure between Shenfu coal and its residue. Furthermore, a hybrid genetic algorithm was employed using these parameters to approximate a coal macromolecule by assembling the structural fragments or functional groups into a large and complicated structure.     

龙牙草石油醚提取物中的挥发成分研究

为探讨龙牙草在石油醚中的溶解成分,利用索氏提取器获取了龙牙草石油醚提取物,并利用气相色谱-质谱(GC - MS)联用技术对其进行了分析.研究显示:龙牙草石油醚提取物的收率为3.20%; 在龙牙草石油醚提取物的35个强色谱峰中共鉴定出27个成分,占石油醚提取物总含量的45.28%.27个成分中相对百分含量较高的成分依次为三环[3,5,7]癸烷 -1- 羧酸辛酯(6.42%)、胆酸乙酯(3.87%)、棕榈酸(3.67%)、(E)- 3,7,11,15- 四甲基十六醇 -2- 烯 -1- 醇(3.37%)、α- 姜黄烯(2.93%)、绵马素(2.15%)等.该结果可为龙牙草的药理研究和开发利用提供参考.     

Group separation of coal components and new ideas of coal utilization as petroleum

Four different groups of components were separated from coal under mild conditions of extraction and stripping process. Within these groups, and with pre-separation, individual utilization of all coal components can be realized, similar to petroleum components and enhance the inherent value and utilization value of coal, as well as increase environmental benefits. The characteristics of each component were analyzed with measurements by FTIR, GC/MS, TEM and the establishment of caking properties. The results show that coal can be separated into residues, ultra-pure coal, asphaltene components and light components by adding solvents for stripping into the CS2/NMP mixed extraction solution. Those four groups of components present great differences in the presence of carbon and hydrogen elements, in the structure of functional groups, in their macroscopic structure and micro-morphology and caking properties. Every component possesses its own inherent values and approaches. A new idea of coal processes and utilization, similar to the use of petroleum is proposed.     

童亭亮煤CS2溶剂分次萃取物的GC/MS分析

以CS2为溶剂对童亭亮煤进行了按时间段分次取样的索氏溶剂萃取,采用GC/MS对各次萃取物进行了定性分析.结果表明：长链正构烷烃具有十分明显的低碳（约在C12-C22之间,其主峰碳位多变,但多以C16或C17为主峰）、中碳（多以C26或C27为主峰）和高碳（多以C31或C32为主峰）三大系列分布特征;中低碳正构烷烃在溶出特定阶段（约600 h左右）发生奇碳优势分布;长链烯烃的溶出具有后期性和爆发性特点,且与奇碳优势分布的长链烷烃相伴共生,两者可能有着一致的来源物质并在溶出时集中释放;GC/MS可检测小分子主要以三种形态存在于煤结构中,即处于煤表面或大孔隙中的游离态、嵌于微孔之内的微孔嵌入态和囿于大分子网络或交联网络结构之中的网络嵌入态.