【作者】 鞠彩霞；

【导师】 张洪；

【作者基本信息】 中国矿业大学 ， 化学工艺， 2020， 博士

【摘要】 山东枣庄煤炭资源丰富,但多采用炼焦、燃烧等传统方式利用,从分子水平上系统分析研究枣庄煤有机质组成,探索枣庄煤炭资源利用新方法,有利于提高煤炭利用附加值并减少环境污染和温室气体排放。鉴于两种枣庄烟煤（大兴煤和田陈煤）复杂的分子组成,很难根据某种单一的方法得到其完整的组成信息,故本研究分别采用四种萃取（索氏萃取、超声萃取、微波萃取和二氧化碳超临界萃取）工艺和一种萃取协同氧化解聚（UAE/H₂O₂）相结合的工艺将有机质从煤中分离出来,详细分析了五种分离工艺条件下枣庄煤提取产物的分子结构组成,为枣庄烟煤进行非燃料利用提供了新思路。索氏萃取（SE）从两种煤中萃取得到的物质种类最少,但SE获得的含氯化合物比重最多;大兴煤（DX）SE含氯化合物占主要地位（76.3%）,其中六氯乙烷的相对含量占22.95%。田陈煤（TC）萃取物中含氯化合物为主（76.4%）,其中六氯乙烷的含量占25.54%。从萃取机理角度解释并分析了含氯化合物在SE中为主要产物的原因。六氯乙烷的生成可以证明萃取过程中有自由基生成,同时为六氯乙烷的制备提供了一种新思路。超声萃取（UAE）DX煤的萃取物中能够检测到的化合物有37种,其中脂肪烃和芳香化合物各12种,六氯乙烷的含量为10%,五氯丙烷含量为10.6%。而TC煤CCl₄萃取液检出有机化合物共有26种,其中肪烃和芳香化合物各10种,六氯乙烷约占19%。微波萃取（MAE）对枣庄煤CCl₄溶剂下最佳操作条件是80℃,8 h,800 W。DX煤的MAE萃取物中能够检测到的化合物有75种,萃取物中肪烃化合物20种,含氧化合物22种,萃取物中C₂Cl₆占11.77%,含硫化合物占0.68%。微波萃取TC煤的萃取物中能够检测到的有机化合物共有53种。其中肪烃化合物17种,含氧化合物20种;三种含氯化合物中,六氯乙烷占19%。萃取物含硫化合物占3.2%。两种煤在萃取物中都鉴定出一些生物标记化合物。二氧化碳超临界萃取（SCCO₂）进行协同CCl₄萃取,DX的SCCO₂萃取物中共检测出48种有机化合物。其中19种烷烃,7种芳烃类。TC煤SCCO₂的萃取物检测到52种有机化合物。其中包括20种烷烃,14种芳烃类。生物标记化合物可以推测枣庄煤是成煤植物在较强的还原环境下形成的。采用了FT-IR、XRD和电镜等检测手段,对四种萃取工艺得到的萃余煤进行了表征,枣庄两种煤的CCl₄萃取工艺中,四种萃取方法均未破坏（弱破坏）煤的大分子结构。但煤的微晶结构有所改变。四种萃取分离机理的共性是在萃取条件下CCl₄被诱导产生了自由基,四种萃取工艺得到的CCl₄萃取产物中都检测到氯代烃,CCl₄萃取同一种煤所得萃取物分析表明,不同的萃取工艺可以得到不同的萃取产物,进一步证明了萃取手段也是影响萃取结果的因素。枣庄煤的超声/H₂O₂氧化系统有利于萃取。PE、乙醚、CS₂对氧化后的水相有较好萃取效果,初步实现分离出以烷烃为主的石油醚萃取物,以醇类为主的乙醚萃取物。采用PE、CS₂、苯、甲醇和丙酮/CS₂溶剂对枣庄煤H₂O₂氧化残余煤进行分级萃取,利用极性不同的溶剂可以有效富集不同种类的有机化合物,不仅为煤氧化残余煤中有机化合物的精细分离创造了有利条件,为煤的大分子结构研究提供一定信息,还为氧化残余煤的有效利用提供参考,该研究对煤非燃料利用有着重要意义。对萃取物进行柱层析分离,可分离出相应的族类化合物。枣庄煤超声/H₂O₂氧化残煤的红外光谱显示了C-Cl键的存在,SEM-EDS检测到氧化残煤中Cl重量百分含量为0.37%以上,说明与煤的作用可能有氯化煤的生成。本论文有参考文献205篇,56幅图,32个表。更多还原

【Abstract】 Coal resources are rich in Zaozhuang,Shandong Province,but most of them are used in coking,combustion and other traditional ways.In order to improve the added value of coal utilization and reduce the environmental pollution and greenhouse gas emissions,it is necessary to systematically analyze and study the organic matter composition of Zaozhuang Coal and explore new methods for the utilization of Zaozhuang Coal resources.In this paper,Because of the complex molecular composition of two kinds of Zaozhuang bituminous coal（Daxing coal and Tianchen coal）,it is difficult to get its complete composition information according to a single method,so organic matter was respectively separated from coal by four extraction processes（Soxhlet extraction,ultrasonic extraction,microwave extraction and carbon dioxide supercritical extraction）and an extraction combined with oxygen de-polymerization（UAE/H₂O₂）,and the molecular structure of the products extracted from Zaozhuang Coal under five separation conditions was analyzed in detail,which provided a new idea for the further development of non-fuel use of Zaozhuang Coal.Soxhlet extraction（SE）obtained the least kinds of substances from coal,but SE obtained the most chlorine-containing compounds.The extract of SE from Daxing coal（DX）is mainly composed of chlorinated compounds（76.3%）,among which the relative content of hexachloroethane is 22.95%.Chlorinated compounds（76.4%）were the main content in the extraction of Tianchen coal（TC）,and among which the content of hexachloroethane accounted for 25.54%.The main reason of chlorine-containing compounds in SE was explained and analyzed from the Angle of extraction mechanism.The detected hexachloroethane can prove the free radical formation in the extraction process and provide a new idea for the preparation of hexachloroethane.There are 37 compounds detected from DX in Ultrasonic extraction（UAE）,including 12 aliphatic hydrocarbons and 12 aromatic compounds.The content of hexachloroethane and pentachloropropane in the extract was 10%and10.6%respectively.26 organic compounds were detected in the CCl₄ extraction from TC,including 10 hydrocarbons and 10 aromatic compounds.The content of hexachloroethane in the extract accounted for about 19%.The optimum operating conditions of Microwave extraction（MAE）for Zaozhuang coal under CCl₄ solvent are 80℃,8 h,800 W.There are 75 compounds detected in MAE extraction of DX coal.There are 20 hydrocarbon compounds and 22 oxygen-containing compounds in the extraction,and C₂Cl₆ accounted for 11.77%and sulphur compounds for 0.68%.There are 53 kinds of organic compounds that can be detected in the extraction of TC by microwave.Among them,there were 17 pyrenees and 20 oxygen-containing compounds.Hexachloroethane accounts for 19%of the three chlorine-containing compounds.Some biomarker compounds were identified in the extracts of both coals by MAE.A total of 48 organic compounds were detected from DX by SCCO₂extraction with collaborative CCl₄ extraction.Among them,there are 19 alkanes and 7aromatics.The extraction of TC detected 52 organic compounds by SCCO₂.It includes 20 alkanes and 14 aromatics.The biomarkers can be inferred that zaozhuang coal was formed by coal-forming plants in a strong reducing environment.FT-IR、XRD and electron microscopy were used to characterize the residual coal extracted by four extraction processes.In the CCl₄ extraction process of Zaozhuang Coal,the four extraction methods did not destroy the macromolecular structure of the coal.But the microcrystalline structure of coal has changed.The commonality of the four extraction mechanisms is that CCl₄ is induced to generate free radicals under the extraction conditions.The common feature of the four extraction and separation mechanisms is that CCl₄ is induced to produce free radicals under extraction conditions.Chlorohydrocarbons were detected in all CCl₄ extraction products obtained by four extraction processes.The extraction analysis of CCl₄ extraction from the same coal showed that different extraction processes could produce different extraction products,which further proved that the extraction method was also a factor affecting the extraction results.The ultrasonic/H₂O₂ oxidation system of Zaozhuang Coal is favorable for extraction.PE,ether and CS₂ have good extraction effect on the water phase from oxidized,and the petroleum ether extract mainly composed of alkanes and ether extract mainly composed of alcohols has been preliminarily separated.By using PE,CS₂,benzene,methanol and acetone/CS₂ solvents to hierarchical extract the residual coal oxidized by H₂O₂ from Zaozhuang Coal,different solvents with different polarity can effectively enrich different kinds of organic compounds,which not only creates favorable conditions for the fine separation of organic compounds in the residual coal oxidized by coal,but also provides certain information for the study of the macromolecular structure of coal and the effective oxidation of residual coal This study is of great significance to the utilization of non-fuel coal.The existence of C-Cl bond was shown by the infrared spectrum of ultrasonic/H₂O₂ oxidized residual coal in Zaozhuang coal.The weight percentage of Cl in oxidized residual coal is more than 0.37%in SEM-EDS,which indicates that The interaction with coal may involve the formation of chlorinated coal.This paper has 205 references,56 pictures,28 tables.更多还原