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。     

Viscosity Reduction of Heavy Oil during Slurry‐Phase Hydrocracking

The saturates, aromatics, and resins fractions of maltenes from upgraded oils obtained by slurry‐phase hydrocracking (SPH) under low‐severity reaction conditions using analytical‐grade and mineral catalysts were obtained by chromatographic separation. The reactions in the SPH at low severity with the catalysts used occur by free radicals, and their subsequent hydrogenation is from heavier fractions (asphaltenes and resins) to lighter fractions (aromatics, saturates, and light cuts). The degree of conversion depends on the type of catalyst used (Mo > Fe) and is also proportional to the active metal content of the catalyst. The enhanced conversion of aromatics and resins towards the saturates fraction depends on the hydrogenation capacity of the catalyst. The better flow properties of the maltenes are due to the conversion of heavier to lighter fractions and to the upgrading of the resins fraction properties.     

Separation and characterization of bitumen from Athabasca oil sand

Separation and chemical analysis was investigated using bitumen samples from Athabasca oil sand in Alberta. Fractionation according to solubility and polarity has been used to separate bitumen into its fractions. The solvent de-asphaltening was performed by n-pentane solvent (solubility fractionation), and the polarity fractionation using Fuller’s earth allows maltene to separate into SARA components (saturates, aromatics, resins and asphaltenes). The SARA components are analyzed comprehensively using elemental analysis (EA), Fourier-transformed infrared (FTIR), ultraviolet-visible spectroscopy (UV-vis), high performance chromatography (HPLC) and thermogravimetric analysis (TGA). EA (C, H, N, S), heavy metals (Ni, V) concentrations, FT-IR and UV-vis tests provided the explanation of chemical composition. From IR spectra, maltene and saturates/aromatics (sat/aro) contained more aliphatic compounds than resin or asphaltene. Also, IR spectrum of sat/aro was similar to crude oil and VGO (vacuum gas oil). Different UV signal data clearly indicates the contribution of aromatic constituents in the fractions. Using optimized analysis conditions of HPLC, we successfully separated the peaks for bitumen and its fractions. The characteristic peak pattern of SARA (saturates, aromatics, resins, asphaltenes) fractions was observed, and also the peak pattern of sat/aro was similar to that of crude oil and VGO. However, TGA results revealed that thermal behavior for sat/aro was similar to that of crude oil but different from that of VGO. Also, from the comparison between decomposition temperature of TGA and boiling point, their correspondence was found.     

Correlation between feedstock SARA components and FCC product yields

Daqing, Shengli, Liaohe, Gudao, Dagang and Huabei vacuum residua were subjected to deep solvent fractionation by using the supercritical fluid extraction and fractionation, a novel separation technology recently developed by the State Key Laboratory of Heavy Oil Processing. Each residuum was fractionated to produce deasphalted oil (DAO) at four yield levels: 30, 40, 50 and 60 wt%. The saturates, aromatics, resins and asphaltenes (SARA) composition of each DAO sample was determined, indicating that the saturates and aromatic contents of DAO decreases with increased DAO yield.The DAO samples were reacted in a laboratory scale confined fluidized bed, fluid catalytic cracking (FCC) reactor. The results show that most of the gasoline yields originates from the saturate fraction of DAO. The aromatics fraction of DAO contributes to gasoline and diesel yields. Most of the coke yield is from resin fraction of DAO.Generalized empirical correlations were developed for predicting the FCC gasoline, diesel, light oil and coke yields as a function of feedstock SARA composition. These yield correlations can be used to set the upper limit of feedstock resins content for commercial FCC operations. The implications of feedstock properties on FCC products were discussed.     

Solubility Parameter from an Acoustic Method: Temperature Effect and Applications to Petroleum

The thermodynamic information relating cohesive energy and internal pressure is explored in order to calculate the solubility parameter for hydrocarbons, some of its mixtures, and crude oils taking into account the effect of temperature. Single-phase data of pure hydrocarbons and some of their binary and ternary mixtures, such as speed of sound, density, and heat capacity at constant pressure, are used to adjust the proposed models. Finally, the results are compared with an experimental method recently presented by us in a previous publication. This evaluation demonstrates that the proposed methods are robust for highly saturated oils. Moreover, a general expression including SARA (percentage by weight of saturates S, aromatics A, resins R, and asphaltenes As) composition is proposed to predict the solubility parameter of oils with high content of resins and asphaltenes.     

Pyrolysis kinetics of atmospheric residue and its SARA fractions

Thermal analysis of atmospheric residue from heavy crude oil and its SARA fractions was carried out and the tendency of each fraction toward coke formation was determined. The coke yield was 16.3 wt.% for atmospheric residue, 43.1 wt.% for asphaltenes, 4.6 wt.% for resins, 3.8 wt.% for aromatics, and 0.3 wt.% for saturates. Pyrolysis kinetics of residue and its fractions, i.e., asphaltenes, resins and aromatics was also investigated. The TG experiments were conducted at three different heating rates of 8, 12, and 16 °C/min from room temperature up to 800 °C under nitrogen atmosphere to verify the weight variation with reaction temperature. Isoconversional analysis to fit data assuming first order kinetics was employed. Asphaltenes was the fraction that produces coke in higher amount having a range of activation energy of 41.0–58.6 kcal mol⁻¹ whereas activation energy for atmospheric residue ranged from 11.5 to 30.0 kcal mol⁻¹.     

Permeability reduction by asphaltenes and resins deposition in porous media

The deposition of crude oil polar fractions such as asphaltenes and resins in oil reservoir rocks reduce considerably the rock permeability and the oil production. In the present work, a crude oil and various core samples were extracted from Rhourd–Nouss (RN) reservoir rock. Afterwards, core flow experiments were carried out in the laboratory to investigate permeability reduction that causes formation damage. The core permeability damage was evaluated by flooding Soltrol, through the sample and measuring the solvent permeabilities, K_i and K_f, respectively, before and after injection of a given pore volume number of the crude oil.The data indicate that upon flooding the crude oil through the porous medium, considerable permeability reduction, expressed as the ratio (K_i − K_f)/K_i, and ranging from 72.4% to 98.3% were observed. The permeability reduction is found to result from irreversible retention of asphaltenes and resins in the porous core sample. However, no correlations could be established between the depth of the well, the core porosity, the core mineral compositions determined by X-ray analysis, and the permeability damage factors. In addition, effluents flowing away from RN wells were collected and analysed at various periods, after carrying out aromatic solvents squeezes. The amount of saturates, aromatics, resins, and asphaltenes (SARA analysis), of the crude oil, the deposited crude oil fraction, and the effluent’s residues were measured and compared. The asphaltenes weight percent was found to increase from 1.56% for the crude oil to 11.42% for the deposited oil fraction, and was in the range 1.37–2.36% for the effluent’s residues. Such results indicate that the deposited oil fraction and the effluent’s residues consist mainly of asphaltenes and resins.     

再生沥青的热老化研究(Ⅱ)——再生沥青热老化过程中族组成变化的研究

通过对不同老化温度与不同老化时间下薄膜烘箱老化后族组成变化的研究 ,发现再生沥青的族组成随老化的进程发生改变 :老化时间延长 ,饱和分质量分数不变或略有减少 ,芳香分质量分数总是降低 ,胶质质量分数变化复杂 ,沥青质质量分数总是升高。对变化规律与原因进行了详细的讨论     

Evaluation of polyphosphoric acid on the performance of polymer modified asphalt binders

The aim of this research is to evaluate the effect of polyphosphoric acid (PPA) on the mechanical performance of styrene–butadiene–styrene (SBS) and styrene–butadiene–rubber (SBR) modified asphalt. Conventional properties, multiple stress creep recovery (MSCR), bending beam rheometer (BBR), and linear amplitude sweep (LAS) tests were conducted to evaluate the performance characteristics of asphalt at different PPA inclusions. Gel-permeation chromatography (GPC), saturates, aromatics, resins, and asphaltenes (SARA), and Fourier transform infrared (FTIR) were carried to reveal the molecular weight, component and infrared spectra of asphalt. Results showed that PPA hardened the asphalt, improved the rutting and fatigue performances of polymer modified asphalt (PMA) binder, but weakened the anti-cracking performances. Besides, storage stability had a significant improvement as the addition of PPA. The addition of PPA brought more macromolecules into asphalt and led to more high-average molecular weight compounds. Furthermore, PPA changed four component ratios of asphalt. Both PMA with or without PPA have similar absorption peaks. This may be due to absorption peak of PMA covered the changes in PPA modification process as the low content of PPA. 0.8% dosage of PPA may be considered optimum for composite modified binder combining the above experimental results for this binder source.     

［(MoO2)(acac)2］/t-BuOOH/H3PO4催化氧化体系对稠油中重组分的降解作用

针对稠油的重组分，探讨了催化氧化稠油降解反应体系中稠油黏度、平均分子量随反应时间、催化剂及氧化降解体系的变化规律.研究了各种条件下油层矿物在反应中的作用.实验结果表明，［(MoO₂)(acac)₂］催化剂对稠油的氧化降黏是非常有效的，其催化降解反应与氧化剂、氢质子供体以及油层矿物有关.在［(MoO₂)(acac)₂］/t-BuOOH/H₃PO₄/油层矿物体系中，稠油沥青质降解率达到81%，稠油黏度由原始的117.2 Pa·s下降到55.8 Pa·s，下降率为52.4%，平均相对分子质量下降了100.TLC-FID分析证明，稠油中的沥青质减少主要生成胶质、芳烃和饱和烃，这种理化性质的改变促进了稠油体系的稳定，对稠油开采、运输以及后处理工艺将起到推动作用.     

离子液体介质中沥青砂内重组分降解过程

This paper illustrates the reaction pattern of catalytic degradation of macromolecules in asphaltic sands. Such parameters as ionic liquid catalyst system and H^ proton donor, that affect the change of the organic phase and the mass of organic matter in residual phase of asphaltic sands, were investigated. It was found that chloroaluminate (Ⅲ) ionic liquid/H3PO4 systems as reaction medium was an effective catalyst system for asphaltic sands degradation. The catalytic degradation of asphaltic sand swas related to the kinds of chloroaluminate (Ⅲ) ionic liquids and H^ proton donor. In [BMIM] [AlCl4]/H3PO4 reaction catalytic medium, the degradation of asphaltenes in the organic phase reached 16.44 %, the degradation of asphaltenes in the residual phase reached 30.74%. TLC-FID analysis of asphaltic sands showed that the main degradation products were saturates and aromatics, and resin fractions as well. At a temperature close to oil-bearing formation and with absense of oxygen, the yield of H2S reached 74%,which indicated that catalytic degradation of sulphur-containing compounds was easier.     

Effect of low-temperature oxidation on the composition of Athabasca bitumen

The effect of low temperature oxidation on the composition of Athabasca bitumen was examined. Oxidation temperatures in the range 125–135 °C and extents of oxidation up to 100mg $\text{O}{}_2\text{g}$ bitumen were investigated. The aromatics concentration was observed to decline steadily and the concentration of asphaltenes to increase, during oxidation. The saturates were unaffected by low-temperature oxidation. The resins concentration displayed a strange behaviour, first dropping and then increasing to a maximum and again dropping as oxidation proceeded.     

Effect of composition and configuration on hindered diffusion of residue fractions through polycarbonate membranes

Diffusion behavior of narrow fractions of three residues and subfractions of a residue through four polycarbonate membranes was investigated using a diaphragm cell at 308 K. The results show that the diffusivities of fractions with similar molecular weight behaved differently. Comparisons among SAR subfractions (saturates, aromatics, and resins) of the same fraction show that saturates has the largest diffusion coefficient, followed by aromatics, and then resins. The diffusion coefficients of fractions fall among that of their subfractions. The regular variation of diffusivity along with the properties for fractions with similar molecular weight is an indication of the difference in their diffusivities resulting from the difference in their compositions and structures. Hindrance factors of the subfractions through membranes with small pores have a similar variation trend as their diffusion coefficients. The hindrance factors of the feedstocks in 50 and 80 nm pore size membranes are mostly larger than 0.90, but the values in 15 nm membranes range from 0.55 to 0.81. The study not only indicates that the diffusional limitations are significant in pores with the typical hydrotreating catalyst size but composition and configuration have an effect on the hindered diffusion of residue molecules. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1369–1377, 2013     

Knowledge of petroleum heavy residue potential as feedstock in refining process using thermogravimetry

In the petroleum industry, previous knowledge of the feedstock's potential to produce light material is an important aspect of refining. For the evaluation of heavy petroleum fractions, thermogravimetry (TG), a thermal analysis technique, is considered a good analytical tool to determine the thermal behavior of these fractions at high temperatures. In the present work, TG analyses were made of petroleum distillation residues from different Brazilian oils. The apparent cracking activation energy of saturates, aromatics, resins and asphaltenes was also determined by TG. Saturates and aromatics showed values of 80-120 kJmol^− 1 at low conversions (< 0.3) and of 120-220 kJ mol^− 1 at high conversions (> 0.3). The thermal cracking activation energy of resins and asphaltenes occurred between 220-300 kJ mol^− 1, i.e., at higher values than those of aromatic and saturated fractions. This paper discusses the prediction of carbonaceous residue based on thermal analysis.     

有机溶剂萃取加拿大油砂应用研究

介绍了溶剂作为萃取剂分离油砂的技术,溶剂萃取油砂过程包含两个阶段:沥青相向溶剂的溶解过程和沥青、溶剂与砂粒的分离过程。考察了单一溶剂甲苯、丙酮、乙酸乙酯和甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷组成的复合溶剂体系在相同条件下对油砂沥青的萃取率,在此基础上进一步对比了不同溶剂体系对沥青四组分饱和分、芳香分、胶质和沥青质的萃取效果,同时考察了不同浓度的沥青-溶剂溶液的表面张力,结果表明在油砂萃取过程中沥青-溶剂体系的表面张力主要取决于所选溶剂的种类,而沥青的浓度对溶液表面张力的影响不大。混合溶剂体系甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷相比纯溶剂萃取率较高,其沥青溶液表面张力较低,是良好的分离油砂溶剂体系。     

分子水平重油生焦规律研究进展

阐述了重油缩合生焦规律分子水平的研究进展,主要从重油中四组分的分子组成与生焦的关系以及重油模型化合物生焦的研究两方面进行了概述。研究表明,对于重油各族组分来说:适量的饱和分有助于提升生焦质量;芳香分环数越多生焦越明显,生焦质量越差;中、重胶质和沥青质易生焦,生焦质量差;杂原子会降低生焦质量,但各个杂原子的危害程度不同。而对于各个重油模型化合物来说:甲苯极难发生热缩合反应;萘、菲、蒽、芘的热缩合反应难度逐渐降低;二甲基萘由于侧链的作用,生焦质量比萘要差;1,2,4,5-四甲基苯由于其特殊的空间构型较易缩合生焦且生焦质量很好;杂原子模型化合物单独生焦质量越差,则其在加入到芳烃中之后对体系的生焦质量危害越大。随着超高分辨质谱技术的发展,为更加细致深入研究芳烃热缩合反应生焦机理提供了可能。     

Determination of multi-properties of residual oils using mid-infrared attenuated total reflection spectroscopy

Several physical and chemical parameters (such as saturates, aromatics, resins, and asphaltenes, element contents, density, viscosity, and carbon residue) are necessary to characterize residual oils. The combined use of mid-infrared (MIR) attenuated total reflection (ATR) spectroscopy and multivariate calibration allows those parameters to be estimated accurately. In order to improve the prediction results, samples from different processing units require different calibration models relative to the spectral similarities. This paper builds a strategy to classify and discriminate different types of residual oils by use of partial least square regression. The calibration models for the physical and chemical parameters of three types of residual oils were developed, respectively. The consistencies between the MIR predicted and reference values testify to the creditability of the proposed method.     

Liquid Chromatographic fractionation of oil-sand and crude oil asphaltenes

Asphaltenes extracted from Alberta oil sands (Athabasca, Cold Lake, and Peace River) and crude oils (Taber South and Fenn-Big Valley) were fractionated by sequential elution solvent chromatography (SESC) involving 10 organic solvents on a silica column. Athabasca asphaltenes and SESC fractions were further studied by elemental analysis, i.r., u.v., and n.m.r. spectroscopy. Incomplete extraction of maltenes from the oil-sand bitumens increased the yields of the first two SESC fractions, the saturates and aromatics, of oil-sand asphaltenes relative to the crude oil asphaltenes. About 55 wt% of the asphaltenes elute in fractions 3–5. Two distinct molecular types are present in the asphaltenes; namely, lower functionality species with lower heteroatom content and the higher functionality species with higher heteroatom content. Compounds eluting in fractions 3–10 are predominantly polynuclear aromatics with alkyl substituants and probably bridged by cycloalkanes. The extent of bridging as well as the location, number and type of heteroatoms determines the fraction in which each compound appears. Complexity of compounds eluting increases with time: earlier fractions are composed of smaller-size polynuclear aromatic centers and contain heteroatoms in predominantly ring locations, whereas later fractions contain a larger proportion of complex species and more functional heteroatom groups.     

Novel oxidatively drying urea resin. I. Drying properties of urea resins prepared from N,N′-bis(methoxymethyl) urea and alcohols containing allyl ether groups

A new type of urea resin prepared by copolycondensating N,N′-bis(methoxymethyl) urea with an alcohol containing allyl ether groups have been studied and found to have adequate drying properties when used for surface coating purposes. The drying behavior of the resins can be controlled by conventional drier metals, cobalt being an efficient catalyst. Calcium was found to have a synergetic effect with cobalt on drying, zinc and lead had no synergetic effect, and manganese and sodium hydroxide acted as drying inhibitors. Increasing the amount of allylic alcohol in the monomer mixture and higher molecular weight led to the formation of a faster drying resin. The molecular weight distribution of the resins was found to have an effect on the surface coating properties. It was found that for resins having an equal drying rate those with a broader molecular weight distribution had higher solution viscosities. Resins with a narrow molecular weight distribution were also found to be advantageous when formulating coating compositions containing a minimum concentration of solvents.     

Relationship between solvent-derived and compound-class fractions in coal-derived distillates and vacuum still bottoms

High-boiling SRC-1 process-derived distillable liquids and nondistillable vacuum still bottoms (VSB) from Wyodak and Kentucky 9/14 coals were separated into solvent-derived and compound-class fractions using Chromatographic techniques. The fractions were characterized using infrared spectrometry, proton nuclear magnetic resonance spectrometry, field ionization mass spectrometry, and elemental analysis. Emphasis was placed on the determination of the composition of oils and asphaltenes. Results showed that oils and asphaltenes consist of the same compound classes: hydrocarbons, nitrogen compounds, and hydroxyl aromatics. The main differences between the oil and asphaltene fractions are in concentrations of compound classes. It was found that oils are rich in hydrocarbons while asphaltenes are rich in hydroxyl aromatics. Also, oils and asphaltenes contain compounds of the same homologous series, and molecular weight is not a factor which differentiates oils and asphaltenes. Components in VSB oils have higher molecular weights than components in distillate asphaltenes. Molecular structure rather than molecular weight is a major parameter that determines solubility of coal-derived liquids.