神华煤直接液化残渣超临界溶剂萃取研究

利用甲苯、苯和乙醇三种溶剂在反应釜中对神华煤直接液化残渣进行了超临界溶剂萃取,考察了压力、温度、萃取时间、溶剂/残渣比等对萃取产物收率和重质液体萃取组成的影响。结果表明,以甲苯为溶剂进行萃取时,萃取时间对重质液体产率及HS和A收率的影响不大,而温度、压力以及溶剂/残渣质量比都会影响萃取产物的产率及组成。溶剂超临界萃取过程中,有其他组分向HS组分转化,提高了HS的收率。三种溶剂中,苯显示了和甲苯相似的萃取性能,而乙醇的萃取性能相比苯和甲苯则较差,但乙醇萃取得到的重质液体中轻质组分含量高于苯和甲苯。萃取过程中,残渣中的灰分和硫分主要富集至萃取残渣中。     

胜利褐煤在合成气/复合溶剂体系下液化性能研究

在合成气(H_2+CO)/复合溶剂(THN+H_2O)体系和氢气/四氢萘(H_2/THN)体系下考察了胜利褐煤液化性能,并对液化产物沥青烯和前沥青烯进行了红外光谱分析。结果表明,合成气/复合溶剂体系下胜利褐煤液化转化率和油产率显著高于H_2/THN体系,当反应条件为H_2∶CO=1∶1(体积比)、THN∶H_2O=1∶1(体积比)、反应温度400℃、初压4 M Pa、时间30 min、催化剂添加量3%(Fe的质量计)和硫铁原子比1.2时,胜利褐煤液化转化率和油产率分别为88.79%和55.47%,比H_2/THN体系分别高出8.00%和7.54%。据此表明,在合成气/复合溶剂体系下,水煤气变换反应产生的氢活性更高,对煤和液化产物前沥青烯具有更好的加氢效果,同时四氢萘的存在稳定了煤热解自由基和溶解分散液化重质产物沥青烯和前沥青烯,这些因素的协同作用提高了煤液化转化率和油产率。实验表明,合成气/复合溶剂体系是一种新的褐煤直接液化技术。     

褐煤亚临界—超临界水萃取研究

在半连续实验装置上，采用非等温实验技术，以水为溶剂，对大雁、昌宁两种褐煤进行了萃取。结果表明，在适宜条件下可得到高的转化率和较高的萃取物产率；萃取物中 主要馏分为预沥青烯，为原煤中的富氢组分；过程中产生的气体主要分为CO2；萃取物和气体生成速率随温度而变，在400℃左右存在极大值；萃取后褐煤（即残渣）具有比原煤低的水分、低氧含量、高的碳含量及一定的挥发分。本文对对萃取过程进行了宏观动力学处理，结果表明，萃取过程要用一级反应方程式来描述；在萃取的主要温度区间，活化能约为120kJ/mol.     

东北泥炭亚临界—超临界萃取研究

在半连续装置上进行了中国东北几种泥炭非等温亚临界-超临界萃取研究。以甲苯作溶剂时最佳条件是:压力10MPa,温度330—350℃;以甲醇、乙醇作溶剂时最佳条件是:压力10MPa,温度300—320℃。萃取结果表明,生成萃取物的温度范围宽(180—420℃),主要集中在250—320℃温度区。选用灰分低、(H+N-O)/C原子比高的泥炭对萃取有利。动力学处理表明,主要萃取过程可用三级动力学方程描述,表观活化能为50—185KJ/mol。     

霍州和兴和褐煤的热溶解聚及其有机氧的赋存形态

依次采用石油醚、二硫化碳、甲醇、丙酮和等体积的丙酮/二硫化碳混合溶剂对霍州（HZ）和兴和（XH）褐煤进行分级萃取得到萃取物（E₁-E₅）和萃取残渣（ER₁-ER₅）,利用甲醇、甲苯、等体积甲醇/甲苯混合溶剂和丙酮等溶剂分别对ER₅在320℃进行热溶得到热溶物（SPs）。HZ和XH的累积萃取物产率分别为7.03%和7.86%,其中,E₃的产率最高;萃取残渣在甲醇/甲苯混合溶剂中的热溶物产率最高,ER_5,HZ和ER_5,XH的热溶物产率分别为45.76%和40.14%。E₁-E₅的傅里叶变换红外光谱（FT-IR）谱图中均有较强的脂肪C-H的伸缩振动峰,而SPs的FT-IR谱图中具有较强的C=C、C=O和缔合羟基的吸收峰。气相色谱质谱联用（GC/MS）分析表明,E₁-E₅中含氧化合物（OCOCs）以醇、醚和酮类化合物为主,而SPs中OCOCs以醇、酚和酮类化合物为主,且极性较强的溶剂有利于褐煤中OCOCs的溶出。与原煤FT-IR谱图相比,萃取残渣和热溶残渣的FT-IR谱图中缔合羟基、C=O和C-O-C的伸缩振动峰强度明显减弱。X射线光电子能谱（XPS）分析表明,两种褐煤中不同形态氧的相对含量为C-O > C=O > COO-,并且HZ具有更高的C-O和COO-含量。     

胜利褐煤液化沥青烯光谱表征

以胜利褐煤为原料,通过不同条件下加氢液化制备了相应的沥青烯,利用元素分析、红外光谱、紫外可见光谱和荧光光谱等分析技术对所制备的沥青烯进行了结构表征,探讨了氢气初压和液化温度对沥青烯结构的影响。结果表明,胜利褐煤液化活性高,沥青烯和前沥青烯等重质中间物收率较低。胜利褐煤沥青烯中芳香体系主要以2~3环缩合芳环及联苯类芳香结构为主。提高氢气初始压力,可以促进煤的加氢裂解及AS脱羟基。高温、高氢压有利于AS中芳环取代基的加氢裂解。相对而言,荧光光谱是沥青烯芳香结构的有效表征手段,其荧光光谱特征结果与元素分析、H/C原子比间存在明显的相关性。     

高效液相色谱法测定煤沥青中16种多环芳烃

建立了煤沥青中苯并[a]蒽、苯并[a]芘等16种多环芳烃(PAHs)的高效液相色谱分离检测方法。以甲苯为溶剂对煤沥青进行萃取,萃取液处理后经柱层析分离,层析洗脱液分组回收,然后进行液相色谱分析。采用ZORBAX Eclipse PAH柱分离,以乙腈-水为流动相进行梯度洗脱,紫外检测器进行测定。结果表明,16种PAHs的线性范围为0.5~20 mg/L,相关系数(r)均大于0.999,检出限为0.0031~0.035μg/L,方法的回收率为97.2%~108.3%,相对标准偏差(RSD)为0.18%~3.5%。方法用于两种不同煤沥青中16种PAHs含量的测定,两种煤沥青中16种PAHs的含量分别为107.86 g/kg和103.71 g/kg,其中苯并[a]芘的含量分别为11.86 g/kg和13.82 g/kg。     

泥炭超临界气体抽提研究

在半连续抽提装置上,用甲苯作溶剂在超临界条件下,对黑龙江省宝清泥炭及四川省诺尔盖泥炭进行了试验。抽出油具有较高的H/C原子比(1.2—1.8),接近石油原油水平(1.45—1.95),比褐煤抽出油(H/C原子比为1.1—1.3)高。抽出油收率最高达31.6%(重量,m.a.f.基),略低于褐煤抽提结果(37.8%)。抽提压力20MPa下,两种泥炭气体生成率均低于10MPa下的气体生成率,但组份含量明显不同。文中利用氢转移理论对试验结果进行了讨论。     

混合溶剂超临界萃取大柳塔煤的研究

在一半连续装置上考察了以甲苯为主体的混合溶剂在超临界状态下对神府煤田大柳塔煤的萃取结果，得到了萃取物和气体生成速率随温度的变化关系，并与甲苯为溶剂时的萃取结果作了比较。实验结果表明，萃取过程中萃取物生成速率随温度的变化与煤热分解时失重速率变化相似。煤在各溶剂中的膨润比与其对应的萃取转化率无明确的相关关系。动力学处理结果表明，甲苯及其混合溶剂对大柳塔煤的萃取过程在宏观上都可分两段用二级反应来描述，其分界点在３３０℃左右。低温区表观活化能为２～２８ｋＪ／ｍｏｌ，高温区为１２０～１８５ｋＪ／ｍｏｌ。     

神府煤Ni-Mo-S/Al_2O_3催化液化动力学研究

对煤液化产物进行溶剂的分级处理,采用集总的方法得到Ni-Mo-S/Al2O3催化神府煤液化动力学模型。该模型包括了煤、前沥青烯、沥青烯和油气之间的相互转化,考虑了连串反应、平行反应和逆向转化以及结焦反应的影响,可以较好地模拟Ni-Mo-S/Al2O3催化神府煤液化过程。基于建立的Ni-Mo-S/Al2O3催化神府煤的动力学模型,求得神府煤催化液化的表观活化能为125~244 kJ/mol。通过对计算得到的模型参数分析表明,在高温阶段存在明显的油气向沥青烯以及沥青烯向前沥青烯的逆向转化。当温度高于420℃时,出现前沥青烯和沥青烯结焦反应现象。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.