Determination of asphaltene precipitation using a CPA equation of state

Asphaltene precipitation during natural depletion and miscible gas injection is a common problem in oilfields throughout the world. Therefore, predicting asphaltene phase behavior through thermodynamic modeling may help to control its precipitation and reduce the associated problems. In this work, a new modified CPA equation of state (EoS) was used to model asphaltene precipitation. This equation is based on a combination of a new physical part and the Wertheim association term.

The results of the new model were compared with the experimental data of five oil samples. The results showed that this modified CPA EoS can predict asphaltene precipitation with good accuracy.     

Implementation of CPA EoS for simultaneous solubility modeling of CO2 and H2S in ionic liquid [OMIM][Tf2N]

In this study, solubility of pure CO₂ and H₂S and their mixture in [OMIM][Tf₂N] modeled applying CPA EoS. CPA combines the SRK equation with an advanced association term, which is similar to that of SAFT. From a practical point of view, the target in the CPA project was to develop a thermodynamic model capable of describing complex equilibria of mixtures containing polar/associating chemicals through a simple procedure with respect to the SAFT.

The AAD% for binary systems, including H₂S+ IL and CO₂+ IL are 6.81, 5.21 respectively. Moreover, AAD% equal to 13.89 was achieved for the ternary system.     

Modeling of acid gases solubility in ionic liquid [BMIM][MeSO4] using CPA EoS

This work follows the thermodynamically modeling procedure to correlate the solubility of pure CO₂ and H₂S in [BMIM][MeSO₄]. Moreover, solubility of acid gases mixture was predicted. The bubble point pressure calculation method was applied in which CPA EoS is responsible for fugacity coefficients calculation of the components. The CPA EoS combines SRK and Wertheim's association term to handle non-ideal behavior of the polar and associating components.

The AADs% of H₂S+IL and CO₂+IL binary subsystems were calculated as 18.4 and 17.36 respectively. Moreover, AADs% equal to 27.26 and 6.74 were obtained for predicted partial pressures of CO₂ and H₂S, respectively.     

The CPA EoS application to model CO2 and H2S simultaneous solubility in ionic liquid [C2mim][PF6]

The CPA EoS was utilized for solubility modeling of pure CO₂ and H₂S and their mixture in [C₂MIM][PF₆]. The model is comprised of SRK EoS in addition to Wertheim's association term. Up to now, several associating models such as SAFT variants have been successfully applied to such systems. Considering the complexity and time consuming nature of SAFT EoSs, CPA can be a good alternative due to its accuracy and simplicity with respect to the SAFT.

The AAD % for binary systems including H₂S+ IL and CO₂+ IL are 11.78, 10.40 respectively. Moreover, the ternary system show AAD% equal to 16.51.     

Feasibility study on application of the recent enhanced heavy oil recovery methods (VAPEX,SAGD, CAGD and THAI) in an Iranian heavy oil reservoir

Enhanced oil recovery (EOR) methods assisted by gravity drainage mechanism and application of sophisticated horizontal wells bring new hope for heavy oil extraction. Variety of thermal and non-thermal EOR techniques inject an external source of energy and materials such as steam, solvent vapor, or gas through a horizontal well at the top of the reservoir to reduce in-situ heavy oil viscosity. So, the diluted oil becomes mobile and flows downwards by gravity drainage to a horizontal producer located at the bottom of the reservoir.

In this paper, a sector model of an Iranian fractured carbonate heavy oil reservoir was provided to simulate and evaluate capability of some EOR techniques such as Vapor Extraction (VAPEX), Steam Assisted Gravity Drainage (SAGD), Combustion Assisted Gravity Drainage (CAGD), and Toe to Heel Air Injection (THAI) at its reservoir conditions and fluid properties. The simulation results demonstrated that wet CAGD in comparison with other nominated methods could improve heavy oil recovery factor to around 19% much more than each of SAGD, THAI, and VAPEX techniques. It could also reduce the total energy to produced oil ratio index up to 82% with respect to SAGD process in a year.

Although lower oil recovery has been gained by VAPEX process, but using a proper vaporized solvent could produce a kind of de-asphalted and upgraded oil with increased API gravity up to 29°API with no considerable solvent loss.     

Treatment and restoration of used Mineral-Oil-Based hydraulic fluids from different machines. Part 1: Dewatering,filtration and effect of viscosity modifier

In this work, characterization and treatment of used hydraulic oil samples were performed in three steps. In the first step, the physical and the chemical properties of fresh and used hydraulic mineral oil samples from various centrifugal casting and pipe drawing machines were investigated according to ASTM D 6158. Results show that water content, solid particles count and depletion of additives have considerably affected most of the oil properties. Used oil samples failed in the appearance, thermal stability, oxidation stability, foaming tendency, water content and particles count.

In the second step, a simple methodology for dewatering and filtration was adopted. This methodology involved settling, followed by dry-air bubbling for oil dehydration and finally vacuum filtration. Such process successfully removed considerable portion of solid particles and water in used oil samples. Appearance, pour point, water content, particles count, and acid number were restored to the allowable limits. While water separability, oxidation stability, thermal stability and foaming tendency still failed the limits after treatment. It is obvious that additives will be needed to restore the latter properties.

In the third step, viscosity modifier additive was added to the oil samples to enhance viscous properties. A linear increase in kinematic viscosity was witnessed at 100°C, while at 40°C, an initial linear increase at low viscosities was followed by lower slopes at higher viscosities.     

A new approach for optimizing productivity/injectivity in naturally fractured reservoirs based on fracture network detection using Fourier – wavelet transform analysis

Fracture detection is a key step for characterization and modeling of reservoirs for optimizing production by shooting to the casing right in fracture muster points. Actually, fractures play crucial role in production of oil and gas by introducing super conductive paths to the porous medium and the challenge is finding where they are.

Many approaches took advantage of sharp changes of rock physical properties in the presence of fractures for fracture detection. Likewise, wavelet transform analysis (WTA) is sensitive to changes in the inlet signal and can be employed for this purpose. Considering petrophysical data as input, fractures can be highlighted with change in near wellbore resistivity in the fairly fixed lithology. Decomposition of such signals after removing high frequency noises shows very valuable data hidden in the low frequency part of the original signal.

In this research, WTA is employed for finding fracture muster points in one of Middle Eastern carbonates. MSFL profile is de-noised and results show good match with interpreted FMI of under studied interval in highlighting open fractures. Application of this approach can help for finding hot spots for perforation or well path design of directional wells and also can eliminate running of image logs.     

Predicting the compressibility factor of natural gas

Knowing compressibility factor (z-factor) values of natural gases is the basis of most petroleum engineering calculations. Shortage of available experimental data for the specified composition, temperature, and pressure conditions encourages researchers to propose efficient equations for calculating z-factor values.

This investigation presents a useful empirical model for determining natural gases compressibility factor values. The advantages of this correlation are that it is explicit in terms of z-factor and the results of calculating compressibility factor values by this method reveal the supremacy of the new equation over the other widely used correlations.     

Evaluation of possible source rocks and extracts characteristics from Safir-1x well,North Western Desert,Egypt

The pyrolysis and vitrinite reflectance estimations for fifteen shale rock tests and additionally, geochemical burial history, and gas chromatography – mass spectrometry parameters were talked about to explore the hydrocarbon generation and maturation level and time, type of hydrocarbon produced of rock units of Safir-1x well. The results assign that the Bahariya Formation is poor to great source rock to create oil and gas, with a lower thermal maturation degree than the Khatatba and Alam El Bueib formation. Alam El Bueib is viewed as good to excellent source rock for oil and gas age, having marginally high level of thermal maturation at oil window at around 40 million years. Khatatba formation achieved the oil and gas generation window at about 80 and 50 million years separately and considered excellent source rock.

The molecular gas chromatography and mass spectrometry parameters demonstrated that the extracts of source rocks reflected that the Bahariya and Alam El Bueib extracts have a mixed sources formed under transitional conditions at low grad of thermal maturation. Khatatba source rock extracts originated from marine sources formed under reducing conditions at high grade of maturation.     

原油热裂解过程中的红外光谱演化特征及其主控因素

原油的红外光谱能够反映原油中各种分子基团的信息,对于简单、快速识别原油的成因类型和热演化程度有很大的应用潜力。通过对两个不同有机相来源的原油样品开展热解实验,初步研究了原油热解过程中红外光谱的演化特征及其主控因素。结果表明,随着原油热解程度的增加,不同类型原油的红外光谱具有相似的演化模式,可近似划分为两个阶段。在早期阶段(实验温度<370℃),热解油中甲基/亚甲基吸光度比值(A_CH3/A_CH2)变化不明显,而芳环分子基团吸光度(A_aro)及其与烷基分子基团吸光度比值(A_aro/A_sat)减小,这主要是由于原油中部分热稳定性低的化合物发生脱支链作用,形成了饱和烃组分,降低了芳烃/饱和烃比值。在晚期阶段(实验温度>370℃),热解油中A_CH3/A_CH2,A_aro和A_aro/A_sat     

鄂尔多斯盆地长7段有机地球化学参数对致密油动用效果的响应

致密油层压裂效果及油气动用情况的评价指标和判识手段一般具有地区适用性。选取热解参数S ₁/S _T、PI值与饱和烃分子组成参数 \sum {\mathrm{C}}_{{\mathrm{20}}^{-}} / \sum {\mathrm{C}}_{{\mathrm{21}}^{+}} 、∑三环/∑五环、Pr/nC₁₇、Ph/nC₁₈对水平井开发目标层位长7₂亚段及相邻层位长7₁亚段和长7₃亚段进行比对,分析其实施压裂后致密油的动用效果。结果显示,参数 \sum {\mathrm{C}}_{{\mathrm{20}}^{-}} / \sum {\mathrm{C}}_{{\mathrm{21}}^{+}} 、∑三环/∑五环的比值存在明显分异;Pr/nC₁₇、Ph/nC₁₈参数也敏感地反映了原油直链和支链烷烃分子的差异渗流特征,表现为分子结构简单的轻组分相对含量在目标层位中明显降低。综合各有机地球化学指标特征,认为目标层位长7₂亚段的致密油受到优先动用,但采出程度不大。研究结果为鄂尔多斯盆地致密储层油气动用层位的精细判识提供了有效的敏感参数。     

The direct,one-step process for synthesis of dimethyl ether from syngas. III. DME as a chemical feedstock

In Parts I & II of this Series, we illustrated the process research studies on a new, trendsetting indirect syngas conversion process, the direct, one-step LPDME^tm process, which is now a shining example of “dual catalysis” or “cooperative/adaptive” catalysis and also of thermodynamic/kinetic coupling in series-parallel reactions.

In this part III, we take a look at several processes on the research and pilot scale that employ methanol and DME as chemical feedstocks for further conversion to value-added chemicals. A most rational and cogent argument for the use of DME as a feedstock is that the unit production cost of DME from the direct, one-step DME processes, most notably the LPDME^tm process, can be lower than methanol (from LPMeOH^tm), on a methanol-equivalent basis. DME also has inherently more benign physical and chemical properties, contains 1 less mole of water, and results in a substantially similar product distribution, as methanol, for the methanol-to-gasoline (MTG) and methanol-to-olefins (MTO) process. DME can also be converted to several other important chemicals; some of these include dimethoxymethane, dimethoxyethane, methylal, formaldehyde, acetic acid, methyl acetate, and polyoxymethylene ethers. In this report, we offer a critical assessment of the current status of these processes and a projected path to commercialization. Considering the trendsetting and impactful nature of DME as a chemical entity and as a chemical feedstock, along with its “free” cost, we are of the opinion that the future of DME, and of its chemical conversions, as so-called “DME economy”, is very bright.     

The direct dimethyl ether (DME) synthesis process from syngas I. Process feasibility and chemical synergy in one-step LPDMEtm process

A novel one-step process for co-production of dimethyl ether (DME) and methanol, in the liquid phase, was conceived as an advance over the liquid phase methanol synthesis process (LPMeOH^tm). This direct, one-step DME process (LPDME^tm) is based on the application of “dual catalysis”, where 2 functionally different yet compatible catalysts are used as a physical mixture, well-dispersed in the inert liquid phase. Three different reactions, methanol synthesis (via CO and CO₂), water-gas shift, and methanol dehydration (to form DME) take place over the 2 catalysts, Cu/ZnO/Al₂O₃ and typically γ-Al₂O₃. The thermodynamic and kinetic coupling of methanol dehydration reaction (very fast and at/near thermodynamic equilibrium) with the methanol synthesis reaction (slower kinetics and highly thermodynamic) leads to the observed “chemical synergy”. This synergy helps overcome the limitation on thermodynamic equilibrium conversion, and increases the per-pass syngas conversion and reactor productivity. The catalyst deactivation phenomena in LPDME^tm proess is also greatly alleviated compared to methanol alone; the increase in syngas conversion and methyl equivalent productivity (MEP) are sustained over a longer on-stream time.

Here, in this review, we survey the salient developments in the LPDME^tm process since its inception, first at UA research laboratories and elsewhere including Air Products and Chemicals, Inc. We demonstrate the rationale of the LPDME^tm process, and then outline briefly the research studies in the two processes, that illustrate the chemical synergy in the LPDME^tm process. This successful example of “cooperative catalysis” can be adapted in principle to many other organic reactions.     

The direct dimethyl ether (DME) synthesis process from syngas II. Intrinsic kinetics and catalyst deactivation in one-step LPDMEtm process

In Part I of this series, it was seen that the favorable thermodynamic and kinetic coupling in the one-step LPDME^tm process – of methanol dehydration reaction (very rapid kinetics and at/near thermodynamic equilibrium) with the methanol synthesis reaction (slower kinetics and under thermodynamic limitation) – leads the beneficial “chemical synergy”.

In this part II of Series, we briefly discern the intrinsic kinetics of the LPMeOH^tm and LPDME^tm systems, and also shed light of the catalyst deactivation phenomena in these processes. Among the many reports on intrinsic kinetics of the one-step LPMeOH^tm and LPDME^tm processes, two illustrative kinetic studies, from the groups of University of Akron and Air Products and Chemicals, Inc. are highlighted and discussed further. For development of intrinsic kinetic models of LPMeOH^tm and LPDME^tm systems, a detailed thermodynamic framework has been developed which allows one to compute the liquid phase concentrations of reactive species, at phase equilibria and at chemical reaction equilibria. The intrinsic kinetic models of the LPDME^tm system are mainly based on the independent, component kinetic models of methanol synthesis (van den Bussche and Froment, 1996) and methanol dehydration (Bercic & Levec, 1992). From an overarching analysis of the deactivation of supported copper catalysts for methanol synthesis and other reactions (methanol decomposition and methanol steam reforming), we propose that thermal sintering, i.e., increase in Cu particle size and loss of metal surface area, is the only cause of catalyst deactivation in methanol synthesis reactions over Cu/ZnO/Al₂O₃ industrial-type methanol catalysts.     

The Application of a New Association Equation of State (AEOS) for Prediction of Asphaltenes and Resins Deposition During CO2 Gas Injection

Abstract

Asphaltene deposition is a serious problem that can cause fouling in the reservoir, well, pipeline, and the oil production and processing facilities. An association equation of state (AEOS) is one of the most useful models used to predict asphaltene phase behavior and asphaltene deposition conditions. For an AEOS, it is assumed that the total compressibility factor consists of physical and chemical parts. The authors apply the conventional form of compressibility factor developed by G. Soave (1972) Soave, G. 1972. Equilibrium constants from a modified Redlich-Kwong equation of state. Chem. Eng. Sci., 27: 1197–1203. [Crossref], [Web of Science ®] , [Google Scholar] to the physical compressibility factor. However, for the chemical compressibility factor a new form is proposed. The total compressibility factor obtained is then used to calculate the asphaltene and resin deposits. The amounts of deposited asphaltenes calculated through the proposed model along with the experimental results are used to calculate resin deposit. A comparison with the experimental results shows that the new proposed model can be used to predict the amounts of deposited resins and asphaltenes within an acceptable range of accuracy.     

A Thermodynamic Model for the Prediction of Asphaltene Precipitation

Abstract

Asphaltene precipitation in reservoirs, wells, and facilities can have a severe and detrimental impact on the oil production. Due to the extreme chemical complexity of the asphaltene and crude oil and the lack of comprehensive experimental data, the modeling of asphaltene precipitation in crude oil remains as a challenging task. In this article, a compositional thermodynamic model was developed to predict asphaltene precipitation conditions. The proposed model is based on a cubic equation of state with an additional term to describe the association of asphaltene molecules. Extensive testing against the literature data, including asphaltene precipitation from crude oil and solvent injection systems, concludes that the proposed model provides reasonable predictive results.