依据热模拟实验动态建立煤成烃模式

依据构成煤岩端元组分(壳质组、镜质组和惰质组)热模拟实验的生烃潜力和甲烷同位素组成数据,结合已建立的煤成油有效排出门限(30mg/gTOC),建立了煤成烃模式,该模式表明:只有富氢的显微组分才有利于煤岩生油,且壳质组含量最低为5.0%,而镜质组最高含量为95.0%;当壳质组含量高于22.9%时,煤成油不受镜质组和惰质组二端元组成的影响。同时,按照煤成烃模式计算了不同端元组分在不同热演化阶段甲烷碳同位素组成的变化,结果表明:构成煤岩的显微组分含量能够引起烷烃气碳同位素组成的变化;在同一热演化阶段,甲烷碳同位素组成最大差异可达2.3‰。认为煤成气甲烷碳同位素组成不仅受热成熟度控制,而且也受煤岩显微组分相对含量的影响。

用KVO_3催化剂催化裂解正戊烷制取低级烯烃的实验研究

用ＫＶＯ３作活性组分，用不同载体采用浸渍法制备出一系列ＫＶＯ３／载体催化剂．在连续性微反活性评价装置上，以正戊烷为原料，对空白载体和催化剂分别进行了活性考察．结果表明，催化剂均比相应的空白载体具有高得多的活性，这说明ＫＶＯ３是比较理想的活性组分．活性数据和物相分析表明，载体中含有ＺｒＯ２和ＣａＡｌ４Ｏ７对催化剂的活性比较有利．而含有Ｌａ２Ｏ３的高铝水泥物相对催化裂解的活性有不利影响，董青石（ＭｇＯ·Ａｌ２Ｏ３·ＳｉＯ２）不宜作为该类催化剂的载体．

烯烃配位聚合复合载体催化剂研究进展

自从Ziegler-Natta催化剂发现以来,人们已对该类催化剂作了许多的研究,以MgCl_2为载体的高效催化剂的巨大成功,引起了人们对载体和过渡金属元素的相互作用的浓厚兴趣,近年来许多文献和专利报道了对复合载体催化剂的大量的研究成果,似有可能出现具有更优特性的高效催化剂. 本文就复合载体催化剂的研究现状作一综述.

重整生成油及抽余油加氢脱烯烃生产溶剂油的新技术

以重整生成油或其中的抽余油为原料,采用我国自己开发的加氢脱烯烃技术,生产苯类产品及溶剂油。该技术在国内8套工业装置上推广使用,年创利税约1亿元;可满足环保要求,有良好的社会效益。

α-卤代反应和历程分析及应用

卤代反应是一个重要而又特殊的反应 ,本文包括有机化学中常涉及的几个α卤代反应 .对反应原理、原因作出理论分析 ,解释理解上的难点 ,并指明易出错和易混淆的地方 ,简述了它们在合成上的应用 .

大庆萨南深冷装置的分析

采用工程分析方法,对大庆引进的萨南深冷装置进行了测试数据的分析。依据分析结果,对装置改进完善后再次分析,结果表明,分析能准确地辩识工艺装置的用能薄弱环节,为装置的节能改造提供可靠依据。

罐顶气轻烃录井技术在胜利油田油气层评价中的应用

罐顶气轻烃色谱录井技术作为一项轻烃录井技术,在油气层评价中得到了广范应用。利用罐顶气录井参数可以对储层的含油气丰度、流体性质等方面进行初步评价,在胜利油田的生产实际中,取得了良好的应用效果,对于气层的发现与评价及低孔低渗集层的评价效果尤为突出。

Elucidating the dominant reaction mechanism of methanol-to-olefins conversion in H-SAPO-18: A first-principles study

The reaction mechanism of zeolite- or zeotype-catalyzed methanol-to-olefins（MTO） conversion is still a subject of debate. Employing periodic density functional theory calculations, the olefin-based cycle was studied using tetramethylethene（TME） as a representative olefinic hydrocarbon pool in H-SAPO-18 zeotype. The overall free energy barrier at 673 K was calculated and found to be less than 150 kJ/mol in the TME-based cycle, much lower than those in the aromatic-based cycle（〉 200 kJ/mol）, indicating that olefins themselves are the dominant active hydrocarbon pool species in H-SAPO-18. The similarity of the intermediates involved between the aromatic-based cycle and the olefin-based cycle was also highlighted, revealing that both cycles were pattern-consistent. The selectivity related to the distribution of cracking precursors, such as higher olefins or carbenium ions, as a result of the olefin-based cycle for the MTO conversion. The enthalpy barrier of the crack-ing step scaled linearly with the number of carbon atoms of cracking precursors to produce ethene or propene with ethene being much less favored than propene for cracking of C7 and higher pre-cursors. This work highlighted the importance of the olefin-based cycle in H-SAPO-18 for the MTO conversion and established the similarity between the olefin-based and aromatic-based cycles.

Effect of Operating Conditions on Olefin Distribution in FCC Gasoline as Part of an Olefin Reduction Process

The effects of operating conditions on the distribution of olefins in the FCC gasoline, obtained during catalytic cracking reaction in the presence of the GOR-Q catalyst and conventional MLC-500 catalyst, have been studied in detail. The test results showed that the GOR-Q catalyst could obviously reduce the content of several kinds of olefins in FCC gasoline. Olefins in the FCC gasoline consist mainly of C5- C7 compounds, that are composed of C=C bond with normal or mono- branched chains. The reduction of gasoline olefin content could be achieved by decreasing the content of above-mentioned olefins. Lower reaction temperature, lower weight hourly space velocity （WHSV） and higher catalyst to oil ratio would help to reduce the content of olefins with a C = C double bond, normal olefins, mono-branched-chain olefins and diolefins. To decrease the loss of gasoline octane number, the operation for olefin reduction should be firstly focused on increasing the catalyst to oil ratio.

Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir_(2)S_(3)/ZnIn2S4:Role of Ir_(2)S_(3)

The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C‒S bonds.Here Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposites with varied Ir_(2)S_(3)loadings were obtained by one-pot solvothermal method from ZnCl_(2),InCl_(3)and thioacetamide with IrCl_(3).The loading of Ir_(2)S_(3)on the surface of ZnIn_(2)S_(4)promoted the hydrothiolations of alkenes and alkynes,with an optimum performance observed over 0.5 mol%Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite.Based on the studies on the performance of several other cocatalysts(MoS2,NiS and Pd)loaded ZnIn_(2)S_(4)and the EIS analyses,it was proposed that the superior performance over Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite can be ascribed to an improved efficiency on the photogeneration of the thiyl radicals by loading Ir_(2)S_(3)as well as its inactivity for photocatalytic hydrogen evolution,a side reaction in the light initiated hydrothiolation reaction over ZnIn_(2)S_(4).This study not only demonstrates an efficient and green strategy to synthesize thiolated products under visible light based on semiconductor photocatalysis,but also provides some guidances for the design and development of photocatalytic systems for light induced organic syntheses.

Organic petrology and hydrocarbon generation of potential source rocks in Permian formation of Junggar Basin,Northwest in China

From the outcrops in the Yaomoshan and Hongyanchi sections, oil shales, deep dark mudstones or black mudstones with better organic richness were found. Through the analysis of the samples in the organic petrology method, the microscope features of the sedimentary organic matter were studied. The results indicate that three types of kerogens present in the measured samples. Kerogen type I consists of the laminate algainite, abundant sporinite and only little content of cutinite, which can mainly generate oil. The generation hydrocarbon components of the type II kerogen are dominated by the sporinite, cutinite and little the exinite debris. The type III kerogen is comprised of the sporinite and debris of the exinite with some components of gas generation. Through the analysis of the experiments, the organic kerogen of the Lucaogou formation is mostly comprised of the type I, partially type II, and particularly type III. In Hongyanchi formation, the organic type is mixed by the types II and III. The plot of the （$1＋$2） or TOC value and the content of exinite show two trends. From the evolution of burial and the Permian source rocks in Changji Depression, the Permian formation source rock has ended the generation of hydrocarbon. A significant difference in constituents of the organic macerals among three kerogens in these samples leads to the distinction of the potential hydrocarbon generation. The Lucaogou formation for kerogen type I has better potential hydrocarbon generation. It can reach the oil peak with Ro ratio Of 0.9%. For the kerogen II, the oil peak of the source rocks comes late with the Ro ratio of 1.0% with less quantity of the generation hydrocarbon than the kerogen I. For type III, it can mainly generate gas and reach the gas peak with the Ro ratio of 1.3%. In a word, the Lucaogou formation and Hongyanchi formation source rocks with high organic richness in Permian source rocks have well exploration prospects.

The expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients

Objective:The coal-fired pollution in Xuanwei area has been considered to be local main reason for high incidence of female lung cancers.The aim of the study was to investigate the expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients, and to explore the relationship between the large number of coal-fired pollution PAHs materials and the high incidence of Xuanwei female lung cancers.Methods:We totally collected each 20 cases of Xuanwei female lung cancer patients, Xuanwei male lung cancer patients, non-Xuanwei female lung cancer patients and collected each 10 cases of Xuanwei, non-Xuanwei female patients with benign lung lesions.The cancer tissues, adjacent cancer tissues and normal lung tissues were collected in lung cancer patients and only the normal tissues were collected in benign lung lesion patients.There were total 80 cases and 200 tissues.Using immunofluorescence, we detected the expression of PAH-DNA adducts in each group.Image pro-plus 6.0 software was used to analyze the images and did part quantified analysis.SPSS 13.0 statistical software was used to analyze the data.Results:The positive expressions of PAH-DNA adducts in lung cancer tissues, adjacent cancer tissues and normal lung tissues of Xuanwei female lung cancer patients were 90%, 80% and 65%, respectively.They were higher than the positive expressions of PAH-DNA adducts in Xuanwei male lung cancer patients (35%, 30% and 30%) and non-Xuanwei female lung cancer patients (20%, 15% and 10%; P<0.01).The expression of PAH-DNA adducts in lung tissues of Xuanwei female benign lung lesion patients (70%) was higher than that in non-Xuanwei female benign lung lesion patients (10%).With the direction changing from cancer tissues, adjacent cancer tissues to normal lung tissues, the expression of PAH-DNA adducts was decreased but had no statistical difference (P>0.05).Conclusion:The expression of PAH-DNA adducts in lung tissues of Xuanwei females was higher than that in Xuanwei males and non-Xuanwei females.

Process Design for Separating C4 Mixtures by Extractive Distillation

C4 components are useful in industry and should be separated as individuals. A new process was proposed to separate them by extractive distillation, with the advantages of low equipment investment, energy consumption and liquid load in the columns. One principle to improve the extractive distillation process was put forward. Moreover, the analysis of operation state of the new process was done. There were eight operation states found for the whole process, but only one operation state was desirable. This work provides a way to effectively separate C4 mixtures and helps the reasonable utilization of C4 resource.

Correlation of Viscosities for Alkane, Aromatic and Alcohol Family at High Pressure by Modified Tait Equation

A new model was proposed to calculate the viscosity of fluids under the pressure ranging from 0.1 to 110MPa by improving the Tait equation, in which the viscosity μ of liquids was linked with activation volume V. The model with two adjustable parameters a and fl was applied in calculating viscosities for alkane, aromatic and alcohol family at high pressure. Results show that calculated values of viscosity are in good agreement with the experimental ones, and the average relative deviations for alkanes, aromatics and alcohols are 0.56%, 0.31% and 0.66%, respectively. Besides, the errors correlated by the model proposed in this paper were equivalent to the ones from the pure empirical Tait equation, and obviously superior to those from Eyring equation.

Catalytic Cracking of Cycloparaffins Admixed with Olefins:2. Single-Event Microkinetic(SEMK) Assessment

The developed SEMK model is used to provide an insight into the contribution of individual reactions in the cracking of methylcyclohexane as well as the site coverage by various carbenium ions. The preferred reaction pathways for the conversion of methylcyclohexane are hydride transfer reactions followed by PCP-isomerizations, deprotonation and endocyclic β-scission, accounting for 61%, 22% and 12% of its disappearance, respectively, at 693 K and 30% conversion of methylcyclohexane. Protolysis plays a minor role in the cracking of methylcyclohexane. Once cyclic diolefins are formed, all of them can be instantaneously transformed to aromatics, which are easily interconverted via disproportionation. Judging from the carbenium ion concentrations it is evident that, at the investigated operating conditions, less than 5% of the acid sites are covered by carbenium ions, less than 2% of which corresponds to cyclic type species including allylic ones.

Methanol-to-olefin induction reaction over SAPO-34

The methanol-to-olefin induction reaction over the SAPO-34 was performed using a fluidized-bed system.We found that the whole induction period could be divided into three reaction stages.Further investigation of the reaction kinetics revealed that this induction reaction behavior was different from that over H-ZSM-5 catalyst.Compared with the H-ZSM-5,the generation of initial active centers is easier over SAPO-34 because of its limited diffusivity and the spatial confinement effect of the cages.However,the autocatalysis reaction stage is difficult over SAPO-34 because of the continuous formation of inactive methyladamantanes.

Removal of Trace Olefins from Aromatics Catalyzed by[bmim]Br-AlCl_3 Ionic Liquid

1-Butyl-3-methylimidazolium bromochloroaluminate （[bmim]Br-AlCl3） ionic liquid was used as an acid catalyst for removal of trace olefins from the aromatic hydrocarbons. The influence of various reaction parameters such as reaction time, temperature, dosage and acid strength of catalyst was investigated. The experimental results demonstrated that the ionic liquid exhibited excellent activity under mild reaction conditions, with the conversion of olefins reaching 98.84% and the bromine index of the aromatics varying from 1129 to 13. On the basis of the results obtained, thereof, a possible reaction mechanism was proposed.

Industrial Production of Catalyst for Removing Trace Olefins from Aromatics

A novel additive incorporated into the catalyst for removing trace olefins from aromatics was proposed, and under the laboratory conditions the lifetime of the catalyst was increased from 5 h to 8 h upon specifying the conversion of the olefins equating to more than 55% as a criterion. Catalyst production, which was named ROC, has been successfully scaled up from laboratory formulations to commercial scale manufacture and over 100 tons of catalyst had been produced. The superiority in catalytic activity was identified by the evaluation tests of the ROC catalyst based on whatever kind of feedstocks (with their bromine index ranging from 400 mgBr/100g to 1 200 mgBr/100g) being used as the feedstock. The X-ray diffraction patterns had verified that the additive was highly dispersed on the surface of catalyst; the GC-FID analysis results showed that the ROC catalyst could increase the xylene content; the pyridine-FTIR spectroscopic analyses suggested that the additive could increase the amount of the weak L acids, which was the main cause leading to enhancement of the catalyst activity.

In situ Synthesis of SAPO-34 Zeolites in Kaolin Microspheres for a Fluidized Methanol or Dimethyl Ether to Olefins Process

SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study,we developed the in situ synthesis technology to prepare SAPO-34 zeolite in kaolin micro-spheres as a catalyst for fluidized methanol or dimethyl ether to olefins process. The silicoaluminophosphate zeolite was first time reported to be synthesized in kaolin microspheres. The SAPO-34 content of synthesized catalyst was about 22% as measured by three different quantitative methods(micropore area,X-ray fluorescence and energy dispersive spectroscopy element analysis) . Most of the SAPO-34 zeolites were in nanoscale size and distributed uniformly inside the spheres. The catalytic performance was evaluated in fixed bed and fluidized bed reactors. Compared with the conventional spray-dry catalyst,SAPO/kaolin catalyst showed superior catalytic activities,bet-ter olefin selectivities(up to 94%,exclusive coke) ,and very good hydrothermal stability. The in situ synthesis of SAPO-34 in kaolin microspheres is a facile and economically feasible way to prepare more effective catalyst for fluidized MTO/DTO(methanol to olefins/dimethyl ether to olefins) process.

A 200-Year Record of Polycyclic Aromatic Hydrocarbons Contamination in an Ombrotrophic Peatland in Great Hinggan Mountain, Northeast China

Peat bogs are regarded as one of the faithful archives of atmospheric polycyclic aromatic hydrocarbons(PAHs) deposition, and a large number of studies on PAHs accumulation in peatlands have been reported in Europe and North America. Comparatively little information is available on peat chronological records of atmospheric PAHs flux in China. We investigated the concentrations and historical accumulation rates of PAHs(AR PAHs) through geochemical analysis of three 210Pb-dated ombrotrophic peat cores from Great Hinggan Mountain, northeast China. Eight USEPA priority PAHs were detected and they are naphthalene(Nap), acenaphthylene(Acl), acenaphthene(Ace), fluorence(Flu), phenanthrene(Phe), anthracene(Ant), fluoranthene(Fla) and pyrene(Pyr), respectively. The average total eight PAHs(tPAHs) concentrations are 135.98- 262.43 μg kg-1 and the average AR tPAHs over the last two centuries are 96.45- 135.98 μg m-2 yr-1. The Ace, Acl and Phe account for 30.93- 54.04%, 25.29- 35.81%, and 9.14- 19.84% of the tPAHs, respectively, and have significant positive correlations with the tPAH. As a result, they are regarded as the iconic compounds of PAHs pollution in this area. A ca.200-yr atmospheric PAHs contamination history was reconstructed from the temporal sequences of bothconcentration and AR tPAHs, suggesting the variation of local environmental pollution. The main sources of the PAHs are identified by two isomer ratios as petrogenic origin including oil extraction and refining process as well as their combustions for industrial development. In addition, the contribution of coal combustion for industrial activities and resident heating could not be ignored. But prior to 1860, the undeveloped industry and most of agricultural activities might mainly account for the low level of PAHs, although it could infer a long-range input of atmospheric PAHs from other industrial areas. Therefore, there is a global implication to study longterm PAHs pollution records and all the results will provide practical significance in formulating policies to achieve sustainable and healthy development.