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。     

锡林浩特褐煤的超临界甲醇解研究

在250-330℃温度范围内研究锡林浩特褐煤的超临界甲醇解,考察反应温度、时间、压力、溶煤比和醇解次数等对锡林浩特褐煤在超临界甲醇中可溶物收率的影响,并采用GC/MS对可溶物进行分析表征。结果表明,在310℃下进行超临界甲醇解,锡林浩特褐煤热溶物收率高达39.5%,其可溶物主要由酚类、芳烃、酯类、正构烷烃及含硫和含氮化合物组成。     

联吡啶钌配合物对末端炔烃的催化

以6,6＇-二甲基-2,2＇-联吡啶为配体合成了二水合氯化顺一二氯·二（6,6＇-二甲基-2,2＇联吡啶）合钌（Ⅲ）配合物,进一步用三氟甲基磺酸银脱氯得到三（三氟甲基）磺酸顺一二水·二（6,6＇-二甲基-2,2＇联吡啶）合钌（Ⅲ）配合物．研究了后者对1-己炔、苯乙炔和丙炔酸乙酯环三聚反应的催化作用．实验结果显示环三聚产物具有区域选择性：产物只有1,2,4一三取代苯与1,3,5-三取代苯两种同分异构体,且主要为1,2,4一三取代苯．催化机理研究表明,三（三氟甲基）磺酸顺一二水·二（6,6＇-二甲基-2,2＇联吡啶）合钌（Ⅲ）中的两个水分子配体首先被两分子炔烃取代生成π-炔基配合物,然后通过氧化偶联反应得到钌杂环戊二烯配合物;第三个炔烃分子经由插入反应或双烯加成反应生成钌杂环庚三烯或7一钌杂双环[2．2．1]-2,5-庚二烯中间体,随后发生还原消除反应得到三取代苯．     

弱极性条件下重质碳资源中有机物的光催化氧化转化

对分析纯试剂液体石蜡、苯、甲苯、二甲苯、苯酚、萘、四氢萘、十氢萘等分别进行光催化氧化,反应混合物分离后进行GC-MS分析鉴定。结果表明,光催化氧化产生的自由基是氧化反应发生的动力;支链烷烃的氧化易于正构烷烃;活性氢和给电子基团的存在更有利于正构烷烃或苯环芳烃的解聚;并非光照时间越长就会得到更好的效果,长时间的光辐射可能导致解聚的中间产物重新交联、反应成分更加复杂不利于分离;随着光催化氧化反应的进行,溶液的极性增强,更有利于光解聚反应的进行;稠环芳环化合物较单环化合物更易发生光催化氧化而开环。     

全二维气相色谱 / 飞行时间质谱对微生物降解石油烃产物的分析

采用气相色谱对一株高效石油烃降解菌株微嗜酸寡养单胞菌(Stenotrophomonas acidaminiphila)降解石油烃的产物进行分析,其中 ８０％以上的石油烃被降解,在产物色谱图中,出现了 ＵＣＭ 峰,因而,进一步采用全二维气相色谱/ 飞行时间质谱分析了菌株降解石油烃的产物.结果表明:该菌株能够降解大部分 Ｃ１０-Ｃ２８ 正构烷烃、部分直链烷烃和环烷烃,芳香烃尤其是多环芳烃很难被该菌株降解.由检测到中间产物推断:直链烷烃如十六烷,在微生物作用下,生成中间产物十六烷醇,接着被氧化为十六醛和脂肪酸,脂肪酸被进一步氧化,最终生成 ＣＯ２ 和 Ｈ２Ｏ支链烷烃的降解途径和直链烷烃相似?检测到中间产物２-己基-１-十二醇、２-辛基-１-癸醇、２-甲基-１-辛醇等,环烷烃先被氧化为环醇,接着形成环酮,然后被进一步降解,检测到的中间产物有 １-环己醇、环辛烷甲醇、３-甲基环戊醇、环庚烷甲醇等,烷基芳香烃被氧化成羧酸,芳香烃苯环羟被基化,随后进行芳环裂解。     

Salen-卟啉配合物催化氧化二苯型木素模型物的研究

研究Salen-卟啉配合物催化氧化二苯醚、二苯乙烷、二苯甲烷木素模型物的降解产物.利用红外光谱和气相色谱-质谱(GC-MS)分析二苯型木素模型物在Salen-卟啉配合物催化氧化下的降解产物.通过对比转化数(TON)与转化率(TOF),发现催化剂的存在使反应底物发生转化;Zn PSC6的催化能力强于Co(salen)的催化能力.依据催化氧化后的二苯型木素模型物降解产物,发现Salen-卟啉配合物的催化氧化能使二苯型木素模型物中醚键、Cβ-Cγ、Cα-Cβ联接断裂,并且使苯基减少,产生了苯酚、苯甲酸等降解产物.     

俄罗斯减压渣油在次氯酸钠水溶液中的氧化解聚研究

利用NaClO水溶液对俄罗斯减压渣油（RVR）中的芳烃碳进行选择性氧化降解,用石油醚、二氯甲烷、环己烷、二硫化碳和乙醚对其氧化产物分级萃取,用重氮甲烷-乙醚溶液对二氯甲烷萃取物和乙醚萃取物进行甲酯化处理,采用气相色谱／质谱联用仪对各级萃取物进行分析。考察了与芳环相连的正构烷基侧链和桥接芳环的聚亚甲基链的分布,根据二元到五元一系列苯多甲酸的结构反推出RVR中的缩合芳环结构,根据检测到的舍硫、氮和氧化合物推测了杂原子在重油中的赋存形态,计算出NaClO水溶液对芳烃碳的氧化选择性达6．5％。     

多环芳烃与N—溴代丁二酰亚胺的光化学反应

在可见光照射 ,苯为溶剂 ,氮气气氛中考察了数种多环芳烃与N -溴代丁二酰亚胺的反应。采用气相色谱跟踪了反应过程 ,解释了产物因结构而异的原因。结果表明 :甲基芳烃仅得到单溴代产物 ,氢化芳烃主要生成脱氢产物 ,蒽全部转化为 9,1 0 -二溴代蒽。     

多环芳烃与N-溴代丁二酰亚胺的光化学反应

在可见光照射,苯为溶剂,氮气气氛中考察了数种多环芳烃与N-溴代丁二酰亚胺的反应。采用气相色谱跟踪了反应过程,解释了产物因结构而异的原因。结果表明甲基芳烃仅得到单溴代产物,氢化芳烃主要生成脱氢产物,蒽全部转化为9,10-二溴代蒽。     

过氧化物促进的α-亚胺-N-芳基酰胺的环化反应研究

发现了一种新的过氧化物促进的合成喹喔啉酮类和3-胺基吲哚酮类化合物的方法。在间氯过氧苯甲酸和四丁基碘化铵的作用下,α-亚胺-α-乙氧酰基-N-芳基酰胺可以氧化产生α-(N-芳基氨酰基)亚胺自由基,后者在惰气氛围下可以发生邻位环化,以中等,甚至非常好的产率得到喹喔啉酮类产物。α-亚胺-α-乙氧酰基-N-芳基酰胺还可以被过氧叔丁醇和乙酸钯催化生成3-胺基吲哚酮类产物。     

褐煤超临界醇解影响因素的研究

采用自行开发的褐煤超临界醇解提质装置,研究反应温度、反应压力、醇解时间、醇解次数和醇煤质量比对锡林浩特褐煤在超·临界醇解中反应特性的影响。结果表明,无催化剂条件下,当反应温度为310℃、反应压力为17～18MPa、醇解时间为120min、醇解次数为3次和醇煤质量比为4．5：1时,锡林浩特褐煤的超·临界醇解的醇解率为54．03％（同条件下的单次醇解率为39．5％）,其反应达到最佳效果。     

Pyrolysis and co-pyrolysis of lignite and plastic

The study firstly discusses the pyrolysis characteristics and kinetics by thermogravimetric analysis (TGA), and then investigates the pyrolysis of lignite and co-pyrolysis with plastic (polyethylene or polypropylene) in tube furnace. Meanwhile, the research focuses on the co-pyrolysis products under different mixing ratios as well as pyrolysis products at different testing temperatures and heating rates. The results show that higher final testing temperature and lower heating rate contribute to bond fission in lignite pyrolysis, resulting in less char product. In co-pyrolysis, lignite acts as hydrogen donor, and the yields of char and water rise with increasing amount of plastic in the mixture, while the yields of gas and tar decrease; and a little admixture of plastic will promote the production of gas and tar. Kinetic studies indicate that in temperature range of 530–600 °C, activation energies of lignite are higher than those of lignite/plastic blends, and as plastic mass ratio increases from 0% to 10%, samples need less energy to be decomposed during co-pyrolysis.     

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.     

先锋褐煤热溶残煤的过氧化氢氧化及产物分析

先锋褐煤经四氢萘高温热溶得到热溶残煤,在40℃温和条件下用过氧化氢水溶液氧化热溶残煤,计算氧化残煤和气体产物CO2的收率.结果表明,该条件下热溶残煤氧化反应性很高,产生了大量的水溶性产物;结合元素分析和FTIR等分析手段对热溶和氧解产物进行结构表征,结果表明,热溶过程中脂肪烃易被抽提,得到芳香度更高的热溶残煤,且氧化过程引入了含氧官能团,水溶性产物中含有大量有机羧酸;采用阴离子交换树脂对氧解水溶液进行富集分离,三氟化硼/甲醇衍生化,并进行GC/MS分析,发现水溶性氧解产物中含有大量短链二元羧酸,同时还发现相当含量的N-甲基吡咯烷酮和苯甲酸.     

用褐煤半焦制备磺化煤的研究

针对褐煤生产磺化煤存在的容易过氧化和机械强度差的问题，用正交实验法研究了褐煤经低温热解改质后的褐煤半焦生产磺化煤的可行性及原料性质，磺化温度，磺化时间，原料粒度等因素对所生产磺化煤质量的影响，结果表明，褐煤低温热解改质后的半焦是生产磺化煤的优质原料，其原料性质和磺化温度是磺化煤质量的重要的影响因素。     

Changes in active functional groups during low-temperature oxidation of coal

Using Fourier Transform Infrared (FTIR) combined with an adiabatic oxidation test, temperature-programmed oxidation and gas analysis, we studied the changes of active functional groups during low-temperature oxidation of lignite, gas coal, fat coal and anthracite. During slow low-temperature heat accumulation, aliphatic hydrocarbons, such as methyl and methylene, are attacked by oxygen atoms absorbed by pores on coal surfaces, generating unstable solid intermediate carbon-oxygen complexes, which then decompose into gaseous products (CO, CO2) and stable solid complexes. At the accelerated oxidation stage, the stable complexes begin to decompose in large amounts and provided new active sites for further oxidation, while the aliphatic structures gained energy and fell from the benzene rings to produce CxHy and H2.     

褐煤固体热载体热解-气化耦合工艺流程模拟

为实现褐煤的清洁高效利用,对褐煤固体热载体热解-气化耦合工艺进行了评价.利用流程模拟软件ASPENPLUS建立了该工艺的模拟流程,分析了处理规模为42t/h时褐煤干燥阶段和热解阶段的能耗、固体热载体与煤混合、分离、运输过程的机械能耗及燃烧半焦的比例.结果表明,该工艺可利用褐煤所含外在水分作为气化剂,节约了气化所需水耗,在水煤比为0.7的情况下,可节约水资源12.5t/h,褐煤热解可获得焦油产品2.6t/h,半焦24.3t/h,其中45%的半焦用于燃烧供热,55%用于气化;褐煤热解单元能耗占总能耗70%以上,是直接导致固体热载体用量大、燃烧半焦比例大以及系统辅助能耗大的主要原因.     

褐煤如何达到空气干燥状态试验探讨

通过大量的试验,从干燥温度、干燥时间等方面总结出褐煤达到空气干燥状态所需要的条件,规范了褐煤空气干燥状态试验的具体步骤,更有效地保证褐煤试验数据的准确可靠。     

Bio-solubilization of Chinese lignite Ⅰ: extra-cellular protein analysis

A white rot fungus strain, Trichoderma sp. AH, was isolated from rotten wood in Fushun and used to study the mechanism of lignite bio-solubilization. The results showed that nitric acid pretreated Fushun lignite was solubilized by T. sp. AH and that extracellular proteins from T. sp. AH were correlated with the lignite bio-solubilization results. In the presence of Fushun lignite the extracellular protein concentration from T. sp. AH was 4.5 g/L while the concentration was 3 g/L in the absence of Fushun lignite. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) of the extracelhilar proteins detected at least four new protein bands after the T. sp. AH had sohibilized the lignite. Enzyme color reactions showed that extracelhilar proteins from T. sp. AH mainly consisted of phenol-oxidases, but that lignin decomposition enzymes such as laccase, peroxidase and manganese peroxidases were not present.