减压渣油超临界萃取分离与结构研究

减压渣油结构复杂,其合理利用应以充分了解其结构为基础.采用超临界流体萃取分馏技术,将伊朗和沙轻减压渣油混合油分离成6个窄馏分和1个萃余残渣,测定各窄馏分的性质和组成,为沸腾床加氢原料的结构表征提供重要基础数据.结果表明,随着窄馏分产率的增加,残炭值、S和N及金属元素含量逐渐增加,饱和分质量分数减小,胶质质量分数增大,芳香分质量分数逐渐增大,各窄馏分中基本不含沥青质.用改进的Brown-Ladner法计算了各个原料和窄馏分的结构参数,对窄馏分的二次加工性能进行了预测.     

反气相色谱法与汉森溶解度参数软件测定原煤的三维溶解度参数

采用反气相色谱法（IGC）研究原煤在温度433.15、443.15、453.15、463.15和473.15 K时的三维溶解度参数（HSP）,并使用外推法得到原煤室温（298.15 K）时HSP的色散力分量（δ_d）、极性力分量（δ_p）、氢键力分量（δ_h）以及校正溶解度参数（δ_t）分别为δ_d=20.83（J·cm^-3）^1/2,δ_p=11.95（J·cm^-3）^1/2,δ_h=11.08（J·cm^-3）^1/2,δ_t=26.44（J·cm^-3）^1/2。同时,采用汉森三维溶解度参数软件（HSPiP）模拟原煤在室温下的HSP,得到δ_d=19.92（J·cm^-3）^1/2,δ_p=11.18（J·cm^-3）^1/2,δ_h=11.47（J·cm^-3）^1/2,δ_t=25.56（J·cm^-3）^1/2。IGC与HSPiP得出的数据一致,研究结果为煤的热力学性质研究及其溶胀剂的选择等应用提供了参考。     

液相色谱柱外效应对分离的影响

在同一型号不同配置的两台高效液相色谱仪上做对比实验，考察了柱外效应对色谱分离的影响。柱外效应的降低将会减少色谱扩散，提高色谱分离效果。     

姜黄色素的简易提取与柱色谱分离研究

利用丙酮-甲苯混合溶剂从姜黄中提取姜黄色素及姜黄油树脂.以体积比为38:1:1的氯仿-乙酸乙酯-甲醇混合溶剂作为洗脱剂,硅胶柱色谱分离10 g姜黄色素,纯物质的收率为:姜黄素45 %,脱甲氧基姜黄素为13 %,二脱甲氧基姜黄素为24 %,纯色素的总收率为82 %.     

气相色谱单柱快速分离多种菊酯类农药的研究

本文介绍了单填充柱快速分离四种菊酯类农药的方法，在同一柱子上，四种农药的分离度分别达到１．５、１．０、０．９３、０．９０。而且对药物蚊帐中的溴氰菊酯残留量进行了测定，回收率在９５．８￣１０１．６％之间，变异系数为３．１％。     

柱色谱分离提纯叔戊基蒽醌

叔戊基蒽醌作为一种有机中间体,被广泛的运用在合成、催化等各领域,其作为过氧化氢的催化剂不仅催化效率高,且催化剂不易中毒。本文就叔戊基蒽醌的分离做了初步研究,主要利用了薄层色谱定性,柱色谱分离的方法,使叔戊基蒽醌得到了分离提纯,经高效液相色谱内标法测定,纯度达到了90%左右。     

我国几种稠油减压渣油的组成结构及使用性能研究

对胜利油田单家寺稠油、辽河油田高升地区稠油以及新疆九区稠油的减压渣油进行了组成结构和作为轻质化原料时性质的研究。     

影响Porapak Q色谱柱分离能力差的原因及解决方法

通过改变进样系统、载气系统、分离系统、检测系统中的参数来探究Porapak Q色谱柱对乙烯乙烷分离能力差的原因,确认了原色谱填充柱分离效果差的原因在于固定相与柱内径不匹配,采用的1/8in柱内径80/100目粒径固体填料过大,不适合目前的分析。通过使用2m乃至1m柱长、3mm柱内径、80/100目粒径的固体填料的填充柱,可以实现低级烃类组分的有效分离。     

反相气相色谱法测定丁苯橡胶的溶解度参数

试验研究反相气相色谱法测定丁苯橡胶(SBR)的溶解度参数.结果表明:正辛烷和正壬烷是SBR的一般溶剂,三氯甲烷是SBR的良溶剂,正庚烷、正己烷、丙酮和乙酸乙酯是SBR的不良溶剂;利用相互作用参数与温度的关系,外推可得到室温时SBR的溶解度参数为17.8(J·cm-3)0.5.     

正相干柱和反相柱色谱组合快速分离纯化长春瑞滨技术研究

采用正相干柱硅胶色谱与反相聚苯乙烯(MCI-GELCHP-20)柱色谱相结合的方法,将化学半合成抗癌药物长春瑞滨粗产物进行快速分离纯化。结果显示绝大部分粗原料中长春碱衍生物、反应中间产物、以及产物伴生杂质可快速与长春瑞滨分离,产物纯度达98%以上。该法具有快速、节省溶剂、分离效果好、回收率高等优点。     

Study on molecular structure and association behaviour of heavy subfractions of vacuum residue by an improved separation method

Vacuum residue (VR) is the most complex component of crude oil. Due to the special structure of heavy subfractions, physical aggregation and chemical coking reactions easily occur through molecular force, which affects the normal processing. Therefore, in-depth study and analysis of their composition, structure and association behaviours are particularly important. In view of the shortcomings of the traditional separation method in terms of separation accuracy, mainly including the purification of asphaltenes and the poor separation of resins. In this paper, a reasonably improved separation method is adopted, and the multi-stage asphaltene extraction and the multi-stage silica gel coupling separation are carried out innovatively, which achieves a high yield of 99% while ensuring the separation accuracy. The samples were characterized by elemental analysis (EA), gel permeation chromatography (GPC), Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance spectroscopy (¹H-NMR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscope (SEM) to study their structural characteristics and association behaviours. The results show that the main forms of heteroatoms in asphaltene and resin surface are C-O-C, C-OH, pyridine, pyrrole, and thiophene, and the content of these substances is higher in asphaltene. Compared with resins, asphaltenes contain a more peri-condensed aromatic structure and shorter alkyl substituent side chains. By studying the hydrogen bond and acid–base interaction, it is found that asphaltene and resin mainly contain OH-OH, OH-π, and OH-ether O, of which the content of OH-OH is the highest. Asphaltene and resin have more neutral and basic substances. These hydrogen bonds and acid–base interactions caused by heteroatoms are the main forces for the association of the heavy subfractions of the VR.     

Methods to determine solubility parameters of polymers at high temperature using inverse gas chromatography

Experimental values of Flory–Huggins parameters, χ, between polymers and probes, are frequently used to determine the solubility parameters of the polymers by the method of DiPaola–Baranyi and Guillet. The solubility parameters of probes were usually estimated by using heat of vaporization. When χ is measured at a temperature near the critical temperature of the probes and used to determine the solubility parameter of polymers, the departure of enthalpy of the probe vapor from the ideal gas state should be considered. This study discussed the method to make the correction and its effect on the determination solubility parameter of polymers. Without correction in the vapor phase enthalpy, the solubility parameters of the probes and polymer tend to be underestimated and the error increases when the critical temperature is approaching. Analytical expressions for the effect of correction on the solubility parameter of probes and parameters of polymers were derived. By use of probes with a range of solubility parameters on both sides of the solubility parameter of polymers, the correlation between parameters of polymers was shown to be reduced. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1547–1555, 2004     

Evaluation of solubility parameters for nonvolatile branched hydrocarbons by inverse gas chromatography

Flory‐Huggins interaction parameters determined by inverse gas chromatographic (IGC) technique have been used for the estimation of solubility parameters of nonvolatile branched hydrocarbon solvents. A family of isosteric branched hydrocarbons consists of one apolar stationary phase, 19,24‐dioctadecyldotetracontane (C78), and four polar stationary solvents formed by replacing one of the ? CH₃ groups of C78 by ? OH (POH), ? CN (PCN), ? SH (PSH), ? CF₃ (MTF), and two other polar solvents formed by replacing four ? CH₃ groups of C78 with four ? CF₃ (TTF) and ? OCH₃ (TMO) are investigated. The three‐dimensional Hansen solubility parameters of the solvents have been estimated following the approaches of Voelkel and the method of Huang at five different temperatures. In the three components estimated by Voelkel method, the dispersion component is decreasing rapidly, whereas the polar, and hydrogen bonding components of the solubility parameters are increasing with temperature. In the components of solubility parameter estimated by Huang method, the dispersion and hydrogen bonding components are slowly decreasing with temperature, however, the polar components are almost constant with temperature. The components of solubility parameters for different solvents have been discussed in terms of solvent polarity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

渣油分离方法的研究进展

主要阐述了渣油分离方法在加工工艺中的重要性,重点介绍了目前渣油分离方法中的实沸点蒸馏、分子蒸馏、超临界流体萃取分馏法(SFEF)和色谱法的原理、特点和工艺流程,指出了不同分析方法的优缺点,并对其在国内外发展的概况和应用现状作了评述。针对渣油自身的特点,指出以超临界流体技术和色谱相结合的方法为基础,结合先进的分析测试手段,能系统地揭示渣油的组成、结构和物理化学性质之间的内在关系,可从分子层次描述渣油分子在催化剂上的扩散、吸附及转化规律,突破集总动力学的局限性,是目前渣油分离方法的主要趋势,为渣油轻质化催化剂的研究和加工处理新工艺的发展提供强有力的理论指导,在石油化工中的应用前景广阔。     

渣油掺炼煤焦油的减压蒸馏过程

为提高资源利用率,考察了掺炼煤焦油对渣油减压蒸馏的影响。结果表明,在渣油中掺炼一定比例的煤焦油可以提高其减压蒸馏的拔出率,为后续加工提供更多的原料。相比较于纯渣油,在550℃对渣油掺炼20%的煤焦油进行蒸馏,可多获得近15个百分点的催化裂化加工原料。扣除煤焦油馏分油后,渣油的拔出率也提高5个百分点。同时,蒸馏残渣的软化点有一定的提高,更适合用做沥青原料。最后探讨了煤焦油对渣油蒸馏过程的强化机理。     

The estimation of the solubility parameter of low volatile compounds from gas chromatography data

By applying the regular solution model to the solution processes that take place in gas chromatography, equations are obtained, which relate the retention volume of solutes with their molar volume and latent heat of vaporization. From these equations, solubility parameters of monomeric stationary phases are obtained and their values compared with those obtained by other methods.     

减压渣油中重金属钒、镍的脱除研究

用一种酯类脱金属剂脱除辽河和委内瑞拉混炼减压渣油中的重金属钒和镍,考察了反应温度、脱金属剂加入量、反应时间和静置时间对金属脱除率的影响。结果表明,适宜的操作条件为:反应温度210℃,脱金属剂加入量2%,反应时间20 min,静置时间20 min。在此条件下,钒和镍的脱除率分别为75.36%和40.05%。     

Three‐dimensional solubility parameters of poly(ε‐caprolactone)

The three‐dimensional solubility parameter model was applied to analyze solution thermodynamic data of 27 solutes in poly(ε‐caprolactone) (PCL) between 70 and 110 °C. A linear regression method was compared with a nonlinear least square regression method, which searches solubility parameter components by minimization of the sum of error squares. The parameters of polymers were the same by both methods. When compared with the error in predicting χRT/V, the data showed a different slope from the simple three‐dimensional model. These deviations were reduced by a different model using a smaller weight on the polar and hydrogen bonding components. In the new model, the solubility parameter components were closer to the value of a structure analogue of PCL. The confidence intervals for the parameters were estimated from a linearized equation based on the sum of error squares. The solubility parameter components obtained were different from the average values of the five solutes with the smallest χ. The inclusion of solutes with high hydrogen bonding components contributed to the increase of the component in the nonlinear regression method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2002–2009, 2006     

Measurement of diffusivity and solubility of olefins in polypropylene by gas chromatography

The classical gas chromatographic technique is applied to measure the solubility and diffusivity of ethylene and propylene in polypropylene. The polymer particles were used as supplied by the producers to pack the chromatographic columns. This allows a direct measurement of the interested properties in a particle with the same morphology obtained at the reactor outlet. Moreover, the apparatus was adapted to carry out measurements at pressures and temperatures close to those typical of the reaction conditions. The measured values of solubility and diffusivity compare favorably with those predicted by literature relationships for semicrystalline polymeric matrices. Moreover, the estimated diffusivities indicate the diffusion in the polymer microparticles as the rate determining step and a diffusive characteristic length comparable with the particle diameter, i.e., larger than expected in the frame of a multigrain particle schematization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 464–473, 2000