Novel stationary phases based on asphaltenes for gas chromatography

We present the results of investigations on the possibility of the application of the asphaltene fraction isolated from the oxidized residue from vacuum distillation of crude oil as a stationary phase for gas chromatography. The results of the investigation revealed that the asphaltene stationary phases can find use for the separation of a wide range of volatile organic compounds. The experimental values of Rohrschneider/McReynolds constants characterize the asphaltenes as stationary phases of medium polarity and selectivity similar to commercially available phases based on alkyl phthalates. Isolation of asphaltenes from the material obtained under controlled process conditions allows the production of a stationary phase having reproducible sorption properties and chromatographic columns having the same selectivity. Unique selectivity and high thermal stability make asphaltenes attractive as a material for stationary phases for gas chromatography. A low production cost from a readily available raw material (oxidized petroleum bitumens) is an important economic factor in case of application of the asphaltene stationary phases for preparative and process separations.     

Carbon adsorbents for the sorpting and concentrating nobel metals

Kinetic, sorption and selectivity properties of commercial adsorbents are improved by adding petroleum residues (tar asphaltene concentrates) 13% of whole mass. Obtained adsorbents can be used for selective extraction of nobel metals from multicomponent polymetallic solutions of heavy metals and fro sewages purification for removing arsenic.     

Effect of Asphaltenes and Resins on Asphaltene Aggregation Inhibition,Rheological Behaviour and Waterflood Oil-Recovery

This study presents an investigation about the influence of resins and asphaltenes, extracted from two Mexican crude oils (light and heavy oil samples), on the asphaltene aggregation inhibition, rheological behavior, and waterflood oil-recovery. Resins and asphaltenes were characterized by means of elemental analysis, metals analysis by atomic absorption, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, and electrospray ionization mass spectrometry (ESI-MS) in order to evaluate the effect of their structural parameters on the phenomena studied. Efficiency of the resins fraction as natural inhibitors of asphaltene aggregation was evaluated trough ultraviolet–visible (UV–vis) spectroscopy. Results showed better efficiencies of resins on asphaltene aggregation inhibition at resin/asphaltene (R/A) ratios close to unity and at high temperature. In addition, efficiencies were influenced by structural characteristics of the asphaltene–resin system. Rheological behavior of the heavy crude oil sample was significantly influenced by the presence of asphaltenes and resins. Finally, asphaltenes and resins played an important role on wettability and waterflood oil-recovery.     

Colloidal interactions between asphaltene surfaces in aqueous solutions

Asphaltene at oil/water interfaces plays a dominant role in the recovery of crude oil. In this study, asphaltene monolayer films were deposited on hydrophobic silicon wafers and silica spheres from oil-water interfaces using a Langmuir interfacial trough. The morphology of the deposited asphaltene films was characterized with an atomic force microscope (AFM). The colloidal forces between the prepared asphaltene films in aqueous solutions were measured with AFM to shed light on the stabilization of water or oil droplets coated with asphaltene films. Factors such as solution pH, KCl concentration, calcium addition, and temperature all showed a strong impact on colloidal forces between the prepared asphaltene films. The findings provided a better understanding of asphaltene interfacial films at an oil/water interface in stabilizing bitumen-in-water and water-in-bitumen emulsions.     

沥青质分散剂对沥青质的稳定及缔合的影响

采用紫外－可见光谱法研究了沥青质分散剂对甲苯－正庚烷－沥青质体系中沥青质的稳定作用,通过黏度法考察了沥青质分散剂对沥青质溶液中胶束缔合度的影响。结果表明,十二醇（DAL）、十二烷基苯磺酸（DBSA）、十二烷基苯酚（DP）对沥青质都有一定的稳定作用。三种沥青质分散剂的稳定作用顺序为DBSA>DP>DAL。DAL、DP及DBSA浓度较低时（1%）对沥青质甲苯溶液黏度的影响规律相似,推迟了黏度迅速增加的拐点,即可以抑制沥青质胶束的缔合。DBSA浓度较大时,沥青质胶束没有明显的聚并,同时使得沥青质溶液的相对黏度增加明显。三种沥青质分散剂都能显著降低胶束的聚集数;三种沥青质分散剂抑制沥青质胶团聚并强弱顺序为：DBSA>DP>DAL。这与其头部官能团的酸性顺序一致。     

Effect of Crude Oil Aging on Asphaltene Inhibitor Product Recommendation

Aging refers to the deterioration of hydrocarbon fluids that manifests as changes in the physicochemical characteristics of the fluid upon exposure to ambient conditions. In order to understand the effect of aging of crude oils on asphaltene inhibitor product recommendation, simulated aging studies were performed on a crude oil from Wyoming with known asphaltene issues. The results clearly show that aging of crude oil affects the stability of the oil with respect to asphaltenes and caution must be exercised when recommending asphaltene inhibitor if the evaluations were performed on fluids after long-term storage. A real case study where ambient storage in the lab adversely affects the stability of the crude oil and renders asphaltene inhibitor ineffective further confirms results from simulated aging.     

Effects of nitrate,fulvate, phosphate,phthalate, salicylate and catechol on the sorption of uranyl onto SiO<Subscript>2</Subscript>: a comparative study

We have performed a large number of batch sorption experiments of uranyl onto SiO₂ and examined the effects of nitrate or ionic strength, phosphate, fulvic acid(FA), phthalic acid (PH), salicylic acid (SA), and catechol (CA) on the uranyl sorption onto SiO₂. Three sorption edges and three sorption isotherms at ionic strengths 0.05, 0.1, and 0.5 mol/L KNO₃ were used to investigate the effect of ionic strength or nitrate on the sorption and the Langmuir, Freundlich, and Dubinin-Radushkevich models are used to simulate the sorption isotherms, respectively. Five sorption edges in the presence of phosphate, FA, PH, SA, and CA were compared with that in the absence of complexing ligand. The results suggest that the effect of complexation of uranyl with nitrate on the uranyl sorption can be negligible and the sorption can be described Freundlich and D-R model very well. The positive effect of phosphate on the uranyl sorption was found, though the extent of effect was decreased with increasing pH. The positive effect and the negative effect of FA on the uranyl sorption were found at low pH and high pH ranges, respectively. The sorption edge of uranyl sorption remained unaffected in the presence of PH in the pH 2–10. In the presence of SA, the no effect and the negative effect on the uranyl sorption were, respectively, found at low pH and high pH ranges. The negative effect of CA on the uranyl sorption was found in the pH 2–10.     

沥青质含量对渣油加氢转化残渣油收率和性质的影响

以塔河常渣脱沥青油掺兑不同含量的沥青质为原料,于高压釜反应器内进行加氢转化反应实验,考察沥青质含量对渣油加氢转化残渣油收率和性质的影响。研究结果表明,随原料中沥青质含量的增加,加氢残渣油的收率逐渐降低,加氢残渣油中的沥青质和焦炭产量之和与原料中沥青质含量的比值逐渐减小,在实验选定的条件下,高沥青质含量时沥青质更倾向于发生氢解反应生成小分子组分。与原料相比,反应后所得>350 ℃残渣油的平均相对分子质量、H/C摩尔比减小,密度增大,硫含量降低,氮含量增加,饱和分和沥青质含量增加,芳香分及胶质含量降低。随渣油中沥青质含量的增加,硫、氮脱除率先增加后降低。     

超声波处理对加氢反应前后沥青质单元分子结构的影响

以胜利减渣和沙轻减渣为原料,研究了超声波处理对加氢反应前后沥青质单元分子结构的影响,并结合¹H-NMR数据、沥青质单元分子参数变化和红外光谱分析等结果,用Chem Bio Draw Ultra 2012模拟出不同条件下两种沥青质单元分子的结构。结果表明,超声波处理减少了沥青质的缔合数,使沥青质单元分子发生开环反应和脱烷基侧链反应加剧,改变了沥青质单元分子的结构,对加氢后沥青质单元分子的结构和组成产生重要影响。沥青质单元分子模型可形象体现超声波处理对加氢反应前后沥青质单元分子化学结构的影响,有助于在分子水平上解释超声波处理影响沥青质单元分子的原因。     

Studies of Athabasca asphaltene Langmuir films at air-water interface

Asphaltenes are present in heavy oils and bitumen. They are a mixture of hydrocarbons having complex structures of polyaromatic rings and short side chains. In general, the high-molecular-weight asphaltene is the most aromatic fraction with the highest number of side chains and the low-molecular-weight asphaltene contains the lowest number of side chains, while the number of side chains of the whole asphaltene fraction lies in between. In this study, asphaltenes were extracted and/or fractionated from Athabasca oil sand bitumen. Subfractions of high and low molecular weight and the whole asphaltenes were characterized using a Langmuir trough and complementary techniques such as VPO, FTIR, AFM, and contact angle measurements. At an air-water interface, amphiphilic asphaltene molecules can form a monolayer. Various fractions (high, low, and whole) of the asphaltene molecules behave similarly at the air-water interface, characterized by close resemblance of their surface pressure-area, hysteresis, and relaxation isotherms. The high-molecular-weight asphaltene is the most expanded fraction, while the low-molecular-weight asphaltene fraction is the most condensed, with the whole asphaltene lying in between. At the air-water interface a monolayer of the low-molecular-weight asphaltene relaxes at a faster rate than one of the high-molecular-weight asphaltene.     

胜利超稠油的乳化降黏机理研究

研究了胜利油田滨南超稠油单56-4X4高黏的内在原因。油品性质分析结果表明,影响其高黏度的主要因素有两个:胶质、沥青质的总含量超过30%;有机杂原子O、N、S及过渡金属Ni等形成的配位络合物增加了沥青质分子的内聚力。实验筛选出的降黏剂OP-10对该超稠油降黏率高达99.59%。通过FT-IR、SEM、分子量和偶极矩等分析对比了降黏剂作用前后胶质、沥青质的结构性质变化,结果表明,OP-10使胶质、沥青质的氢键缔合作用减弱,部分拆散沥青质的堆积结构,从而使胶质、沥青质的分子量和偶极矩减小,分析得到降黏剂分子能渗透及分散胶质、沥青质的堆砌聚集体。偏光显微镜对乳状液及蜡晶微观形态的分析表明,降黏剂OP-10使超稠油乳状液由W/O型反相为O/W型而起到降黏作用;使蜡晶的聚集形态由细小均匀转变为尺寸较大的絮凝体,破坏蜡晶的三维网络结构,促进稠油黏度的下降。     

Detecting high-potential conditions of asphaltene precipitation in oil reservoir

Crude oil contains a wide range of components with different chemical natures. Complex molecules consisting of associated groups of polyaromatic sheets and alkyl side chains are known as asphaltene. Asphaltenes are insoluble in solvents such as n-heptane and n-pentane and soluble in benzene and toluene. Asphaltene causes serious damages around the wellbore and the reservoir by reducing permeability and plugging the pores. This paper includes a natural depletion test, performed on the bottom-hole sample and on a carbonate-core sample. The main emphasis is to identify high potentially damaged conditions in the reservoir from the asphaltene precipitation point of view. Stability of asphaltene was investigated by Saturates-Asphaltenes-Resins-Aromatics (SARA) analysis; moreover, asphaltene composition, permeability reduction, and porosity reduction were measured using the natural depletion in 4500, 3000, 2500, and 1450 psig via both static and dynamic approaches. At the pressures above the bubble point, asphaltene precipitation decreases as pressure increases, and the solubility model becomes dominant; on the other hand, below the saturation pressure, decrease in the pressure would decreases asphaltene precipitation and let the colloidal model dominate. It can be concluded that the maximum amount of asphaltene precipitation occurs near the saturation pressure. Asphaltene precipitation was then investigated through the core sample, using a novel scaling equation.     

Experimental study of asphaltene deposition in transparent microchannels using the light absorption method

This study focuses on an experimental investigation of asphaltene deposition in a vertical transparent microchannel. Heptane-induced asphaltene precipitation is utilized to precipitate dissolved asphaltene in crude oil into asphaltene particles at ambient temperature and standard atmospheric pressure. These asphaltene particles deposit gradually on the surface of microchannels. The key parameters that influence the mechanism of asphaltene deposition are the ratio of crude oil to n-heptane and experimental elapsed time. At a constant flowrate, the amount of asphaltene deposited on a transparent channel wall is quantified using a new flow visualization technique based on reflected light intensity and image analysis. Asphaltene precipitation and deposition strongly affect the reflected light intensity through the change of mixture color in the recorded images. Experimental results show that asphaltene deposition process follows three stages, (i) slow asphaltene particle deposition at the beginning of the experiment, (ii) a rapid and continuous deposition occurring after few hours and (iii) a slower deposition (decreasing deposition rate) at the end of the experimentation. The experimental results for different crude oil to n-heptane ratios illustrate that deposition increases with this ratio, i.e. increasing concentration of n-heptane. An empirical equation is developed to correlate the intensity of the light absorption to the thickness of the deposited asphaltene in a transparent microchannel. Non-uniform deposition along the longitudinal direction of the microchannel is characterized. Deposits decrease with increasing longitudinal distance from the inlet. This non-uniform deposition distribution is due to local mass transport limitations and asphaltene aggregation size effect.     

石油沥青质在烃中的稳定性研究

石油是以沥青质为分散相的非水胶体体系[1,2 ] 。研究认为 ,石油中沥青质的沉淀和絮凝 ,对石油开采及输送有十分重要的影响 [3]。提高沥青质在石油中的胶体稳定性 ,可强化石油加工过程中的重油减压蒸馏、催化裂化、减粘裂化及延迟焦化等过程[1,2 ] ,是提高炼厂轻质油收率、改善产品质量、提高综合经济效益的重要途径。国外关于沥青质在烃类介质中的稳定性研究报道较多 ,大多侧重于胶质对沥青质的稳定作用。由于胶质和沥青质均为由多种复杂结构分子组成的混和物 ,探讨胶质对沥青质的稳定机理极端困难 ,Chia-Lu Chang[4 ]等定量讨论了沥青质…     

Mechanism and Kinetics of the Sorption of Platinum, Palladium, and Gold on Activated Carbon from UV-Illuminated Chloride Solutions

The mechanism and kinetics of the sorption preconcentration of gold, platinum, and palladium on activated carbon from solutions exposed to ultraviolet (UV) radiation were studied. The thermodynamic parameters of sorption (sorption capacity and type of adsorption isotherm) were determined; the effect of pH was considered. An explanation of the mechanism of the effect of UV illumination on sorption preconcentration was proposed. It was demonstrated that UV illumination does not change thermodynamic parameters of sorption but significantly affects the kinetics of sorption preconcentration.     

Kinetics and isotherms of asphaltene adsorption in narrow pores

New data relating to the kinetics and adsorption isotherms of asphaltene in consolidated sandstone core samples are reported. The data were obtained from the measurements of electrokinetics of consolidated sandstone core samples in asphaltene/toluene solutions and petroleum oils. The numerical reduction in the (negative) zeta potential of the sandstone samples were attributed to the adsorption of positively charged molecules of asphaltenes. The hydrodynamics thickness δ of adsorption of asphaltene were followed by monitoring the pressure increase that occurred as the adsorbed layer restricted the rock pores and applying Poiseuille's equation. The flow rates indicated a plateau of asphaltene adsorption at a pore blocking thickness of about δ/r = 0.3, which was also the point at which the streaming current reached a plateau. After increasing to about 30% of the pore radius, the adsorbed layer thickness δ stopped growing either with time or with concentration of asphaltene in the flowing liquid. Alternative hypotheses involving asphaltene adsorption isotherms have been investigated. A theoretical treatment advanced describing particle adsorption in the same terms as molecular adsorption and the Langmuir isotherm, with the free energy of asphaltene adsorption on the rock surface (modeled on silica) calculated on the basis of van der Waals attraction. Acceptable agreement was obtained with the electrokinetic measurements.     

Sorption and desorption of phenanthrene onto iron, copper, and silicon dioxide nanoparticles

The sorption and desorption of phenanthrene by three engineered nanoparticles including nanosize zerovalent iron (NZVI), copper (NZVC), and silicon dioxide (NSiO2) were investigated. The sorption of phenanthrene onto NSiO2 was linear and reversible due to the hydrophilic properties of NSiO2. In comparison, sorption of phenanthrene onto NZVI and NZVC was nonlinear and irreversible, which was potentially due to the existence of significantly heterogeneous surface energy distribution patterns detected by a standard molecular probe technique. Naphthalene exerted significant competitive sorption with phenanthrene for NZVI and NZVC, and the isotherm of phenanthrene changed from being significantly nonlinear to nearly linear when naphthalene was simultaneously absorbed. A surface adsorption mechanism was proposed to explain the observed sorption and competition of phenanthrene on both NZVI and NZVC. In contrast, no competition was observed for sorption onto NSiO2. The sorption of phenanthrene on all three nanoparticles significantly decreased with increasing pH. The sorption irreversibility of phenanthrene on NZVI and NZVC were significantly enhanced with decreasing pH. A pH-dependent hydrophobic effect and dipole interactions between the charged surface (electron acceptors) and phenanthrene with electron-rich pi systems (electron donors) were proposed to explain the observed pH-dependent sorption.     

Fractal structure of asphaltene aggregates

A photographic technique coupled with image analysis was used to measure the size and fractal dimension of asphaltene aggregates formed in toluene-heptane solvent mixtures. First, asphaltene aggregates were examined in a Couette device and the fractal-like aggregate structures were quantified using boundary fractal dimension. The evolution of the floc structure with time was monitored. The relative rates of shear-induced aggregation and fragmentation/restructuring determine the steady-state floc structure. The average floc structure became more compact or more organized as the floc size distribution attained steady state. Moreover, the higher the shear rate is, the more compact the floc structure is at steady state. Second, the fractal dimensions of asphaltene aggregates were also determined in a free-settling test. The experimentally determined terminal settling velocities and characteristic lengths of the aggregates were utilized to estimate the 2D and 3D fractal dimensions. The size-density fractal dimension (D(3)) of the asphaltene aggregates was estimated to be in the range from 1.06 to 1.41. This relatively low fractal dimension suggests that the asphaltene aggregates are highly porous and very tenuous. The aggregates have a structure with extremely low space-filling capacity.     

沙特减压渣油临氮热反应过程中沥青质聚集体尺寸变化研究

将沙特轻质原油的减压渣油在395℃临氮条件下进行热反应,利用在线取样装置得到不同热反应时间的样品,借助小角X射线散射(SAXS)技术,测定了各液相残渣油中沥青质聚集体尺寸。结果表明,热反应生焦诱导期的初期沥青质聚集体的尺寸逐渐减小,为29~21 nm;在生焦诱导期后期,其尺寸急剧增大,在热反应进行到150 min时达到43 nm;达到生焦诱导期后,沥青质聚集体尺寸变化较小,在46~42 nm变化。在渣油热反应过程中沥青质聚集体的尺寸受沥青质热裂解、沥青质解缔和缔合等过程的共同影响,与沥青质含量无明显关系。     

Sorption of uranyl ions on silica: Effects of contact time, pH, ionic strength, concentration and phosphate

The sorption of UO₂ ²⁺ and phosphate on silica were simultaneously studied. The effect of contact time between the solid phase and aqueous solution, pH and ionic strength on the UO₂ ²⁺ sorption in the absence and the presence of phosphate was investigated. The effect of contact time between the solid phase and aqueous solution, pH and ionic strength on the phosphate sorption was investigated too. The isotherms of UO₂ ²⁺ and phosphate sorption at different pH values were determined. It was found that as compared with the sorption in the absence of phosphate, the sorption of UO₂ ²⁺ on silica in the presence of phosphate is increased at low pH and decreased at high pH; the abruptly increased with increasing pH in the pH range 3-6; the sorption is gradually decreased with increasing pH in the pH range 2-12; the sorption insensitive and the sorption of phosphate is sensitive to ionic strength.