地层原油及其族组分的氧化反应特性研究

为了考察油藏注空气过程中地层原油的氧化反应规律,采用柱层析方法将地层原油组分分离为饱和烃、芳香烃、胶质和沥青质。采用热重和差示扫描量热仪,研究了原油和其不同族组分的氧化反应特性。结果表明,中原油田该区块原油差示扫描量热曲线第一放热区间峰值热流高于第二放热区间峰值热流,饱和烃和芳香烃的第一放热区间的峰值高于第二放热区间峰值,胶质和沥青质的第二放热区间峰值高于第一放热区间峰值,原油中饱和烃和芳香烃的含量较高时,有利于轻质油藏注空气过程中原油自燃现象的发生。原油的族组成对原油的氧化特性有决定性影响。     

1，1，1，3，3，3—六氟丙烷的提纯方法

1,1,1,3,3,3－六氟丙烷和含至少一种不饱和氟烃的混合物经蒸馏后再提纯得到1,1,1,3,3,3－六氟丙烷含量超过99.9%、不饱和氟烃含量低于0.01%的产物。该方法为：（1）混合物与氯反应对不饱和氟烃进行饱和;（2）水洗反应混合物脱除乘余的盐酸和氯;（3）除水;（4）对反应混合物进行蒸馏得到1,1,1,3,3,3－六氟丙烷纯度超过99.9%、不饱和氟烃含量低于0.01%的产物。     

除去原料烃中不饱和化合物的加氢法和吸附净化法的分析比较

<正> 原料烃中除去有害杂质的深加工问题非常迫切。生产聚烯烃和提取食物油时,使用的轻质石油溶剂中的不饱和芳香烃;已内酰胺生产中为氧化成环已酮而送入的环己烷中杂质苯;供微生物工业用的液态正构烷烃中的芳香化合物等是这类杂质。待精制原料中的所谓杂质,通常含量为百分之一到百分之几(重量)。为除去杂质所采用的吸附法和加氢法,各具一定的优越性。选择除去杂质保证所需净化深度的方法,应该依据每一个具体情况而抉择。在催化加氢的情况下,有害的不饱和烃杂质被转变为饱和烃而除去。在低浓度条件下,加氢反应速度依据朗缪拉-希恩舍尔武达反应机理,可按被加氢物质的一级动力学     

金属盐和油层矿物存在下的稠油水热裂解反应动力学

根据金属盐和油层矿物存在下的稠油水热裂解反应实验结果,建立包括气体、饱和烃、芳香烃、胶质和沥青质在内的五集总动力学模型,并求取模型中的反应速率常数和活化能.计算结果表明,胶质作为主要反应中心,是气体、芳香烃和饱和烃等轻组分含量增长的主要来源.沥青质主要转化成胶质,裂化产物较少.实验数据与计算结果较吻合,所提出的五集总动力学模型可用来描述金属盐和油层矿物存在下的稠油水热裂解反应规律.     

环丁砜在石油炼制中的萃取应用研究进展

首先介绍了环丁砜的特点,综述了近几年国内外环丁砜在石油炼制中对饱和烃与芳香烃的萃取及其液液相平衡的研究现状。环丁砜在萃取提取重整油中的苯、甲苯和二甲苯等芳香烃表现出了很好的性能。环丁砜萃取工艺在工业上的应用已经很普遍,但也存在一些问题。因此,需要进一步研发完善环丁砜萃取剂,针对环丁砜在工业萃取方面的应用进行了详细阐述。     

溶剂萃取法分离氢化可的松和表氢化可的松

针对工业上现有结晶分离工艺的缺点,提出了分离氢化可的松及其光学异构体表氢化可的松的新方法——溶剂萃取法。实验发现,在常规醇类、酮类、酯类、醚类、氯代烃类和芳香烃等溶剂中,乙酸丁酯具有较好的萃取分离性能,以乙酸丁酯为萃取剂用溶剂萃取法分离氢化可的松粗品可获得纯度为９８％以上的氢化可的松,已达到工业生产水平。文中还研究了乙醇含量、温度、盐析效应和ｐＨ对分配的影响。     

金属有机框架材料对烃分离的研究进展

在工业中,烃混合物的分离对于原料的制备和最终产品生产都是非常重要的。碳氢化合物成分是脂肪族或芳香族的,饱和或不饱和的,碳原子数目有很大的变化。利用微孔金属有机框架材料,一些不同分离策略能实现优异的分离性能,这些策略包含与金属的选择性结合,有序孔结构内分子封装效率的差异,柔性框架的"呼吸效应"的选择性和分子筛分效应。本文讨论了各种轻质烃分离策略,并提出了未来研究和发展的前景,以提高分离性能。     

精炼气中微量不饱和烃对微量CO,CO2控制监测影响的探讨

本文叙述了合成氨厂精炼气中微量不饱和烃的存在,会导致铜洗微量CO分析虚高。试验用加有NaCl和NaBr的饱和溴水吸收液,成功地除去了原料气中的不饱和烃,从而消除了微量CO虚高的现象。     

煤制油有机废水的处理方法

本发明提供一种煤制油有机废水的处理方法,该处理方法包括以下步骤:将含烃气体和煤制油有机废水的原水经过预热后分别通过饱和塔的下部和上部送入饱和塔,在饱和塔中实现含烃气体对有机废水进行一次汽提,经一次汽提后的有机废水从塔底排出,富集有机物的含烃气体则从塔顶排出;将水蒸气和饱和塔塔底排出的一次汽提后的有机废水经过预热后分别通过汽提塔的下部和上部送入汽提塔,在汽提塔中实现水蒸气对有机废水的二次汽提;经二次汽提后的有机废水从塔底排出,富集有机物的水蒸气则从塔顶排出。该处理方法流程短、设备简单,能够有效地解决煤制油过程中有机废水难以处理和利用的问题,实现了有机废水的资源化利用。     

超声空化效应降解焦化废水中有机物的研究

报道了将超声空化效应应用于降解焦化废水中有机物的方法,考查了饱和气体的存在与否、有机物(CODCr)的初始浓度、超声波的声能密度、废水的初始pH值以及废水的温度对超声空化效应降解废水中有机物效果的影响。通过测定自由基清除剂正丁醇对有机物超声降解过程的影响,提出了废水中有机物超声降解的作用机理可能是由超声空化效应在水中产生的·OH自由基使水中的有机物被氧化的过程,有机物的超声降解过程遵循表观一级反应动力学规律。     

Evaluation of olefinic block copolymer blends with amorphous polyolefins—effect of different unsaturated and saturated hydrocarbon tackifier resins on blend miscibility

Blends of ethylene–octene based olefinic block copolymer (OBC) with two amorphous polyolefin (APO) polymers [atactic propylene homopolymer (PP) and ethylene–propylene copolymer (PE–PP)] were evaluated at three different ratios. Dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM) evaluations were performed to determine the blend miscibility characteristics. Viscoelastic properties of both OBC blends with PP polymer, and OBC blends with PE–PP copolymer showed incompatibility. Analysis revealed that both blends formed two phase morphologies. The effect of three unsaturated aliphatic hydrocarbon resins with varying aromatic content and two saturated hydrocarbon resins with different chemistries were evaluated as compatibilizing agent for OBC/PP and OBC/PE–PP blends. A 1 : 1 polymer blend ratio of OBC/PP and OBC/PE–PP was selected to better understand the influence of resin addition at three different levels 20, 30, and 40 wt %. The fully aliphatic unsaturated resin seems to improve the miscibility of the OBC/PP blends at higher resin addition levels, but reduced the miscibility as the aromatic content of the resin increases. However, OBC/PE–PP blends showed improved miscibility with increasing aromatic content. A ternary phase morphology was particularly observed for both OBC/PP and OBC/PE–PP blends with highly aromatic (14%) unsaturated hydrocarbon resin, in which OBC formed the continuous phase, and PP, PE–PP, and unsaturated hydrocarbon resins formed the dispersed phase. Interestingly, we did not observe much difference in miscibility characteristics between the two saturated resin chemistries in both blend systems (OBC/PP and OBC/PE–PP). The Harkins spreading coefficient concept was used to better understand the ternary blend dispersed phase morphology. Spreading coefficients indicate that the free hydrocarbon resins (both unsaturated and saturated) were encapsulated by the amorphous PP or amorphous PE–PP polymer in the dispersed phase for the respective blend compositions. Overall OBC–PP and OBC/PE–PP blends showed better miscibility characteristics with both saturated aliphatic hydrocarbon resins, irrespective of the difference in resin chemistries. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2624–2644, 2013     

Composition of oily components in the liquid products of the supercritical fluid extraction of oil shale from the Chim-Loptyugskoe deposit

The compositions of hydrocarbon and heteroorganic compounds in the oily components of the liquefaction products of oil shale sampled from the Chim-Loptyugskoe deposit have been investigated in benzene under supercritical conditions in temperature ranges up to 200, 200–300, and 300–400°C. It has been found that they consisted of normal and branched-chain alkanes, including unsaturated isoprenoids; alkenes, saturated and unsaturated naphthenes; mono-, bi-, tri-, tetra-, and pentacyclic aromatic hydrocarbons; compounds from the thiophene and benzo-, dibenzo-, and naphthobenzothiophene series; and aliphatic esters and ketones.     

Method for determining the olefinic content of the saturated and aromatic fraction of petroleum distillates by hydroboration

This study was prompted by a perceived need for a reliable method for determining olefin content in petroleum distillate fractions. An improved analytical method for the determination of olefin content in naphtha and higher boiling distillate fractions is described. The procedure comprises quantitative addition of diborane that specifically converts the olefins in the saturated and aromatic portion of the petroleum to alcohols. The reaction mixture is chromatographed on alumina, and alcohols are eluted with dichloromethane. The procedure was applied to two hydrocarbon mixtures of 20 saturated, olefinic and aromatic hydrocarbons in the investigated boiling range. Naphtha (ibp–200 °C) and light gas oil (200–350 °C) fractions from the Lloydminster oil were also analysed. Results are compared with the standard FIA method, and a method utilizing both the FIA and proton magnetic resonance spectrometry.     

轻质原油注空气低温氧化反应动力学研究

采用室内静态反应釜实验,研究了三种不同类型的原油静态氧化反应特性,通过阿雷尼厄斯方程的分析方法,并对该模型进行了改进。结果发现,随着油藏含水饱和度的上升,饱和度零阶反应速率的假设已不再适用,地层水的存在对反应动力学参数有较大影响,原油芳香烃含量大小对反应速率有较大影响。A、B、C三种油样的饱和度指数n分别为0.276 5,0.297 9,0.218 8,该数值可以综合反映原油中各组分含量对低温氧化反应效果的影响;并且C原油参与低温氧化反应的持续时间长,氧化耗氧效果好,惰性气体CO2的转化率也较高,适宜于进行注空气开发。     

注蒸汽条件下供氢催化改质稠油及其沥青质热分解性质

利用CWYF-Ⅰ型高压反应釜模拟热采条件下,以甲酸作为供氢体.以自制的油溶性有机镍盐为催化剂进行的稠油水热裂解反应.考察了供氢体的加入对催化水热裂解反应前后稠油黏度、族组成及硫含量的影响,并采用TG-DTA分析法对供氢催化改质反应前后稠油中沥青质的热转化行为进行了分析.结果表明,随着加入供氢体质量分数增加,供氢催化水热裂解后稠油降黏率增大,饱和烃、芳香烃含量增加,胶质,沥青质含量降低,同时硫含量下降.供氢催化水热裂解反应后的稠油中沥青质TG-DTA曲线分析表明,供氢催化水热裂解反应后稠油中沥青质失重量高于催化水热裂解反应前稠油中含有的沥青质的失重量.经过供氢催化水热裂解反应,稠油中沥青质的稳定性下降.     

柴油吸附脱硫工艺条件影响

研究了吸附工艺条件对柴油中硫化物,特别是对二苯并噻吩（DBT）的脱除效果。实验在常压下,采用静态吸附法,以FCC柴油和DBT模型物为原料,用燃灯法测定脱硫前后油品的硫含量,考察了模型物溶剂、油品中含有的芳烃以及吸附温度对吸附剂脱硫率的影响。得出溶剂黏度越大吸附脱硫率越差;油品中含有芳烃时,吸附剂脱硫率减小,温度对脱硫率的影响不大。考察了高温氮气、有机溶剂和水蒸汽这3种再生方法对吸附剂的再生效果,结果表明,水蒸汽600℃再生4h和有机溶剂苯洗涤24h的再生效果较好,基本可以恢复吸附剂的吸附性能。     

油浆糠醛抽提与产品应用

渣油催化油浆经双溶剂抽提后的抽余油,其饱和烃含量及Ｈ／Ｃ比得到提高,芳烃含量降低,可大大改善催化裂化进料质量,抽出的重质芳烃可作为橡胶软化剂、针状焦及增塑剂等原料,该工艺的实施能带来可观的经济效益     

糠醛抽出油制取橡胶填充油的研究

为了研制符合一定标准的橡胶填充油,以糠醛为溶剂对大庆石化减二线糠醛抽出油进行再抽提。本研究采用单级抽提方法进行了一系列条件实验,考察研制橡胶填充油的应用可行性。主要考察了抽提温度和剂油比对橡胶填充油的质量和收率的影响。研究结果表明：当剂油比一定时,随着温度的升高,产品收率上升,芳香烃含量下降;当温度一定时,随着剂油比增大,产品收率先上升后下降,芳香烃含量先上升后下降。综合考虑产品的质量和收率,本实验范围内较适宜的操作条件为：抽提温度60℃,质量剂油比2.0。在此条件下,产品收率为52.3%,芳香烃组分的含量为80.6%,符合某些企业橡胶填充油的使用标准。     

Evaluation of disposable diaper construction hot melt pressure‐sensitive adhesives using blends of olefinic block copolymer and amorphous polyolefin polymers—Adhesive performance,sprayability, and viscoelastic characteristics

Pressure‐sensitive adhesives (PSAs) used in disposable diaper construction have been formulated using blends of olefinic block copolymer (OBC) and an ethylene–propylene (PE‐PP) amorphous polyolefin (APO) polymer, with three different unsaturated hydrocarbon resins (with varying aromatic content), and also with two different saturated aliphatic hydrocarbon resin (with varying cycloaliphaticity). The viscoelastic properties of theses PSA formulations were studied using dynamic mechanical analysis (DMA). Viscosity profiles at five different temperatures were generated to better understand the application window for the resulting adhesive formulation. Rheology master curves were generated using time–temperature–superposition analysis and correlated with the processability characteristics. Adhesives used in disposable diaper construction were applied between a polyethylene backing and a nonwoven substrate with an air‐assisted spiral spray application technique on an Acumeter Spray Coater. After the adhesive was applied, peel adhesion testing on the samples was performed. It has been observed that the OBC/PE–PP‐based disposable diaper construction PSA has a lower application temperature along with wider tolerance for hydrocarbon resin chemistries, especially for the saturated aliphatic resin‐based PSA formulations. Based on the coating parameters used, it has been learned that the adhesive formulations seem to show a higher shear rate at the nozzle, but Reynolds number calculated indicated no major turbulence occurring at the nozzle during spraying. Very good spray patterns were obtained for the olefinic polymer‐based PSA formulations. Disposable diaper construction article showed good adhesive peel properties, especially for the adhesive formulations containing saturated aliphatic hydrocarbon resin, which were comparable to the SBS‐based control. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3311–3318, 2013     

Influence of Some Herbicides on the Physical and Chemical Characteristics of Soybean Oil

The effect of some herbicides on the soybean oil quality and quantity has been studied. Herbicides caused a highly significant increase in soybean oil content. Statistical analysis showed that there was no and highly significant differences in acid value; unsaponifiables and saponification value and iodine value respectively of soybean oil extracted from plants subjected to various herbicides. The increase of herbicides application rates exhibited profound effects on the physical and chemical characters of soybean oil. The application of herbicides leads to the following changes on soybean oil fatty acids: decrease the concentrations of 13:0, 15:0, 18:0 and 20:0; increase the quantity of 16:0 and the appearance of 10:0, 11:0, UC15, 16:1 and 17:0 as new synthetically fatty acids. The total unsaturated to total saturated fatty acid ratios showed that cobex and linuron at low application rates caused desaturation some of 18:1 to form 18:2. On the contrary, these herbicides at high application rates exhibited the reverse effect.