Selective Removal of H2S from Petroleum Refinery Gases. III. A Study on the Corrosion in Desulfurizer–H2S–CO2–H2O System

Abstract

Corrosion in desulfurizer–H₂S–CO₂–H₂O system was investigated by static weight loss test. The corrosion data for JPE-7 system were compared with those for MDEA and MEA system under the same conditions. The results indicated that the new desulfurizer JPE-7 system was generally less corrosion to carbon steel than MDEA and MEA system. The order of corrosivity of the desulfurizer system is JPE-7<MDEA<MEA. With the acid gas loading, especially the CO₂ loading increase, the corrosion rate increases. The chloride anion in desulfurizer solution contributes greatly to corrosion. The higher the solution temperature, the more the corrosivity of desulfurizers.     

Hybrid connectionist model determines CO_2–oil swelling factor

In-depth understanding of interactions between crude oil and CO_2 provides insight into the CO_2-based enhanced oil recovery(EOR) process design and simulation. When CO_2 contacts crude oil, the dissolution process takes place. This phenomenon results in the oil swelling, which depends on the temperature, pressure, and composition of the oil. The residual oil saturation in a CO_2-based EOR process is inversely proportional to the oil swelling factor. Hence, it is important to estimate this influential parameter with high precision. The current study suggests the predictive model based on the least-squares support vector machine(LS-SVM) to calculate the CO_2–oil swelling factor. A genetic algorithm is used to optimize hyperparameters(у and б~2) of the LS-SVM model. This model showed a high coefficient of determination(R~2= 0.9953) and a low value for the mean-squared error(MSE = 0.0003) based on the available experimental data while estimating the CO_2–oil swelling factor. It was found that LS-SVM is a straightforward and accurate method to determine the CO_2–oil swelling factor with negligible uncertainty. This method can be incorporated in commercial reservoir simulators to include the effect of the CO_2–oil swelling factor when adequate experimental data are not available.     

Characterization of Al2O3–ZrO2 Mixed Oxide Supported Mo Hydrotreating Catalyst

Abstract

A series of molybdenum catalysts supported on Al₂O₃–ZrO₂ mixed oxide containing 50% ZrO₂ and 50% Al₂O₃ were prepared by incipient wetness technique and characterized by BET surface area, X-ray diffraction, temperature programmed reduction and oxygen chemisorption. The catalytic activities for hydrodesulphurization (HDS), hydrogenation (HYD), and hydrocracking (HYC) were determined using thiophene, cyclohexene, and cumene as model compounds, respectively. Results indicate that up to 8 wt% Mo loading, the catalyst is well dispersed and crystallite growth occurred beyond this loading. Also both oxygen uptake and catalytic activities increase with Mo loading up to 8 wt% and then decreases at higher loading. A linear correlation was obtained between oxygen uptake and all catalytic activities and the correlation coefficients obtained suggest that the order of catalytic activities for HDS, HYD, and HYC is: HDS > HYD > HYC. Furthermore, the catalytic activities of the mixed oxide supported catalyst for HDS, HYD, and HYC were higher than those supported on pure alumina and pure zirconia. The incorporation of 3% Co on 8% Mo catalyst was determined to result in enhanced activity for HDS, HYD, and HYC.     

南堡35–2油田馆陶组沉积相识别及储层展布特征

南堡35–2油田馆陶组沉积特征复杂,储层成因认识不清,严重影响了对储层展布特征的认识。依据沉积学理论,对岩性特征、岩石结构、沉积构造及砂体分布四个方面进行了综合分析,认为南堡35–2油田馆陶组沉积相类型为辫状河相,细分为辫状河道、滞留沉积、心滩及泛滥平原四种沉积微相;根据地震相与沉积相的对应关系,并类比现代辫状河沉积,明确了研究区馆陶组沉积时期辫状河储层的空间展布特征,结果表明,研究区馆陶组辫状河沉积主要沿北东–南西向发育,河道宽约310 m,心滩砂体长度平均为1 747 m,宽度平均为1 002 m。     

Hybrid connectionist model determines CO2–oil swelling factor

In-depth understanding of interactions between crude oil and CO₂ provides insight into the CO₂-based enhanced oil recovery (EOR) process design and simulation. When CO₂ contacts crude oil, the dissolution process takes place. This phenomenon results in the oil swelling, which depends on the temperature, pressure, and composition of the oil. The residual oil saturation in a CO₂-based EOR process is inversely proportional to the oil swelling factor. Hence, it is important to estimate this influential parameter with high precision. The current study suggests the predictive model based on the least-squares support vector machine (LS-SVM) to calculate the CO₂–oil swelling factor. A genetic algorithm is used to optimize hyperparameters (γ and σr2) of the LS-SVM model. This model showed a high coefficient of determination (R² = 0.9953) and a low value for the mean-squared error (MSE = 0.0003) based on the available experimental data while estimating the CO₂–oil swelling factor. It was found that LS-SVM is a straightforward and accurate method to determine the CO₂–oil swelling factor with negligible uncertainty. This method can be incorporated in commercial reservoir simulators to include the effect of the CO₂–oil swelling factor when adequate experimental data are not available.     

A novel La3+–Zn2+–Al3+–MoO42− layered double hydroxides photocatalyst for the decomposition of dibenzothiophene in diesel oil

A new type of photocatalyst, La³⁺-Zn²⁺-Al³⁺-MoO₄^2? layered double hydroxide (LDH) (La:Zn:Al = 1:7:2), was prepared by a complexing agent-assisted homogeneous precipitation technique. The LDHs were used as catalysts for the desulfurization of diesel oil under UV irradiation. As revealed by the results, the catalyst showed superior desulfurization efficiency and recycling performance. Under UV irradiation, the desulfurization efficiency was 84% in 60 min. In La³⁺–Zn²⁺–Al³⁺–MoO₄^2? LDHs, the introduction of MoO₄^2? increased the interlayer space for promoting the adsorption of dibenzothiophene, and MoO₄^2? might act as the active sites for the oxidation of dibenzothiophene, resulting in the high desulfurization efficiency.     

A compositional model for CO_2 ooding including CO_2 equilibria between water and oil using the Peng–Robinson equation of state with the Wong–Sandler mixing rule

This paper presents a three-dimensional, three-phase compositional model considering CO_2 phase equilibrium between water and oil. In this model, CO_2 is mutually soluble in aqueous and hydrocarbon phases, while other components, except water,exist in hydrocarbon phase. The Peng–Robinson(PR) equation of state and the Wong–Sandler mixing rule with non-random two-liquid parameters are used to calculate CO_2 fugacity in the aqueous phase. One-dimensional and three-dimensional CO_2 flooding examples show that a significant amount of injected CO_2 is dissolved in water. Our simulation shows 7% of injected CO_2 can be dissolved in the aqueous phase, which delays oil recovery by 4%. The gas rate predicted by the model is smaller than the conventional model as long as water is undersaturated by CO_2, which can be considered as "lost" in the aqueous phase. The model also predicts that the delayed oil can be recovered after the gas breakthrough, indicating that delayed oil is hard to recover in field applications. A three-dimensional example reveals that a highly stratified reservoir causes uneven displacement and serious CO_2 breakthrough. If mobility control measures like water alternating gas are undertaken, the solubility e ects will be more pronounced than this example.     

Modeling of the Fischer–Tropsch process using a Fe–Cu–K catalyst

In a bid to increase Fischer–Tropsch product selectivity, inorganics substances, such as copper, potassium, and others, were added to the catalyst. Although this approach in Fischer–Tropsch synthesis is very important, it has not been discussed widely. Isothermal product models in this type of synthesis and effective parameters are the same as pressure, while the H₂/CO feed ratio and space velocity have been studied over the spray-dried Fe–Cu–K catalyst by using statistical methods with experimental data. P = 1.0–2.5 MPa, H₂/CO feed ratio = 0.6–2.0, and space velocity = 0.07–0.1 1/h are the range of operating conditions in the spinning basket reactor. The experiment was carried out at a constant temperature of 523 K. The models can predict the reaction's product. Through these the optimal conditions in the reactor models can be determined, while the maximum and minimum amounts of products for oil, wax, and water are obtained under the optimized conditions. The models showed that the interaction between parameters played a key role. The main interactions for products are pressure and space velocity.     

Optimization of reaction condition on the product selectivity of Fischer–Tropsch synthesis over a Co–SiO2/SiC catalyst using a fixed bed reactor

The Fischer–Tropsch (FT) synthesis is an important method for producing valuable key raw materials such as heavy and light hydrocarbons in various industries. The effects of process conditions (temperature of 503–543 K, pressure of 10–25 bar, and gas hourly space velocity (GHSV) of 1,800–3,600 Nml g _cat^?1 h^?1) on the FT product distribution using Co–SiO₂/SiC catalyst in a fixed bed reactor were studied by the design of experimental procedure and the Taguchi method. The optimization of the reaction conditions for the production selectivity of C₂–C₄ and heavy hydrocarbon (C₅₊) that has not been completely indicated elsewhere was investigated. The effect of operating conditions on the average carbon number distribution, dispersion, and skewness was also studied. Data analysis indicated the highest selectivity for the light hydrocarbons at a pressure of 20 atm, GHSV of 2,400 Nml g _cat^?1 h^?1, and temperature of 543 K resulting in a highest selectivity for heavier hydrocarbons (C₅₊) and the minimum amount of methane in the reaction products that is optimal at the pressure of 10 atm, GHSV of 1,800 Nml g _cat^?1 h^?1, and a temperature of 503 K. Furthermore, based on the surface plot, temperature has more significant effects than the other parameters. In addition, the obtained results indicated that the maximum average number of carbon was obtained in a pressure of 10 atm and a temperature of 503 K.     

A compositional model for CO2 flooding including CO2 equilibria between water and oil using the Peng–Robinson equation of state with the Wong–Sandler mixing rule

This paper presents a three-dimensional, three-phase compositional model considering CO₂ phase equilibrium between water and oil. In this model, CO₂ is mutually soluble in aqueous and hydrocarbon phases, while other components, except water, exist in hydrocarbon phase. The Peng–Robinson (PR) equation of state and the Wong–Sandler mixing rule with non-random two-liquid parameters are used to calculate CO₂ fugacity in the aqueous phase. One-dimensional and three-dimensional CO₂ flooding examples show that a significant amount of injected CO₂ is dissolved in water. Our simulation shows 7% of injected CO₂ can be dissolved in the aqueous phase, which delays oil recovery by 4%. The gas rate predicted by the model is smaller than the conventional model as long as water is undersaturated by CO₂, which can be considered as “lost” in the aqueous phase. The model also predicts that the delayed oil can be recovered after the gas breakthrough, indicating that delayed oil is hard to recover in field applications. A three-dimensional example reveals that a highly stratified reservoir causes uneven displacement and serious CO₂ breakthrough. If mobility control measures like water alternating gas are undertaken, the solubility effects will be more pronounced than this example.     

FLUID–FLUID AND SOLID–FLUID INTERFACIAL INTERACTIONS IN PETROLEUM RESERVOIRS

The distribution and flow behavior of crude oil, gas and brine in the porous rock medium of petroleum reservoirs are controlled largely by the interactions occurring at the interfaces within the various fluids and by the interactions between the fluids and the rock surface. With an objective to correlate the macroscopic multiphase flow behavior with fundamental interfacial interactions, the recent developments in the field of fluid–fluid and solid–fluid interactions and their applications in petroleum engineering are presented in this contribution.

A computerized drop shape analysis technique and its application to the measurement of fluid–fluid interfacial tension at elevated pressures and temperatures are discussed. A recently developed technique that is capable of measuring dynamic (advancing and receding) contact angles at realistic conditions encountered in petroleum reservoirs is presented. Its effectiveness in making reproducible and rapid measurements relative to the conventional techniques is demonstrated with several reservoir case studies.

Attempts are made to correlate the interfacial phenomena of adhesion and spreading in solid–liquid–liquid systems with dynamic contact angles as well as to extend the applicability of the critical surface tension concept from the conventional solid-liquid-vapor systems to the rock-oil-brine systems of interest in petroleum engineering. These interfacial concepts have been applied to the practical problems of asphaltene destabilization from crude oils and the effect of temperature on wettability alteration in heavy oil fields. A simple procedure is outlined to enable the estimation of interfacial adhesion forces and to demonstrate the significant role they play relative to the capillary forces in retaining the fluids within the porous rock medium.     

页岩油藏压裂水平井压–闷–采参数优化研究

目前在页岩油藏的多段压裂水平井压–闷–采过程中,缺乏系统完善的水平井压裂参数优化方法,为此,基于动态反演理论,建立了压裂参数优化方法.首先,根据页岩油藏压裂后形成的复杂缝网,采用数值理论和离散裂缝方法,建立了考虑页岩油储层特征和复杂天然裂缝的多段压裂水平井数值模型(EDFM-NM),得到了含离散天然裂缝的油藏压力解及多...     

页岩气储层自吸–水化损伤–离子扩散相关性试验研究

压裂液与页岩气储层接触后，诱发自吸、水化损伤及离子扩散等水岩反应，导致压裂液返排率低、矿化度高，对压裂改造效果与页岩气产出均有显著影响。目前对上述水岩反应已经开展了针对性研究，但自吸、水化损伤及离子扩散同步产生，对三者之间相关性的研究较缺乏，难以准确认识压裂液与页岩的相互作用，不利于压裂优化设计。为此，立足于室内试验手段，明确了不同条件下的页岩自吸、水化损伤及离子扩散规律及影响因素，系统分析了页岩自吸、水化损伤及离子扩散之间的定量相关性以及相互作用机制。研究结果显示：自吸、水化损伤及离子扩散具有同步响应特征，均在自吸前期发展显著，后续逐渐趋于稳定；自吸与水化损伤相互促进，使页岩吸水量增大；随页岩吸水量增大，离子扩散程度加剧，更多盐离子扩散进入压裂液，使压裂液活度降低，减弱页岩自吸与水化程度。研究成果深化了对压裂液与页岩相互作用的认识，为实现页岩气储层高效水力压裂改造提供了理论支撑。     

南海莺–琼盆地复杂地层套管–井眼间隙优化

南海莺–琼盆地地质构造复杂,存在高温高压地层,钻井液安全密度窗口窄,为预防下套管作业过程中产生的波动压力可能诱发的井漏、溢流甚至井喷等井下故障,在充分调研南海莺–琼盆地常用井身结构的基础上,建立了下套管过程中井筒内波动压力计算模型,分析了套管–井眼间隙等不同因素对下套管和注水泥过程中环空压力的影响,对套管–井眼间隙进行了优化。该方法在LD10–2–x井进行了应用,该井五开井段的套管–井眼间隙进优化结果为15.00～19.55 mm,其实际的套管–井眼间隙为17.45 mm,在设计的合理间隙范围内,该井套管下入安全,注水泥过程中未发生井漏、溢流等井下故障。这说明可以根据下套管过程中井筒内波动压力和下套管及注水泥过程中的环空压力优化套管–井眼间隙,为南海莺–琼盆地井身结构设计提供依据。      

南海东部荔湾22–1–1超深水井钻井关键技术

荔湾22–1–1超深水井位于南海东部海域,作业水深2 619.35 m,是目前国内作业水深最深的超深水井。针对该井钻井中存在的水深、海底低温、安全密度窗口极窄、浅部地层成岩性差、隔水管及钻柱力学行为复杂等技术难点,采取了周密的钻井工程设计和现场精细化管理,并应用了喷射下导管技术、FLAT-PRO恒流变合成基钻井液、低温早强水泥浆表层套管固井技术、钻井液当量循环密度随钻监测技术等关键技术措施,安全高效地完成了钻井作业,创造了国内外相同水深钻井周期最短纪录,工程质量全优。荔湾22–1–1超深水井的成功标志着我国超深水钻井技术取得重大突破,不但为我国超深水井钻井积累了宝贵的经验,也对国内外超深水钻井技术的发展具有一定的促进和借鉴作用。      

Study of the productivity of MWCNT over Fe and Fe–Co catalysts supported on SiO2, Al2O3 and MgO

In the present study, multi-walled carbon nanotubes (MWCNT) were prepared in good quality and quantity, MWCNT were produced using the catalytic chemical vapor deposition (CCVD) technique and the carbon source was acetylene. Different catalysts were synthesized based on iron and a mixture of iron and cobalt metal supported on SiO₂, Al₂O₃ or MgO. The effect of parameters such as iron concentration, support type, bimetallic catalyst and the method of catalyst preparation has been investigated in the production of MWCNT. The quality of as-made nanotubes was investigated by the high-resolution transmission electron microscopy (HRTEM) and thermogravimetric analysis (TGA). The best yield of MWCNT was 30 times of the amount of the used catalyst. The high yield of MWCNT was gained by 40 wt.% Fe on alumina support which was prepared by the sol–gel method. TEM analysis was done for the carbon deposit, which revealed that the walls of the MWCNT were graphitized, with regular inner channel and uniform diameter. It reflected a reasonable degree of purity. The TGA showed that MWCNT was decomposed at 635 °C by a small rate indicating a high thermal stability and well crystalline formation of the produced MWCNT.     

Enhancement of the Fischer–Tropsch process for producing long-chain hydrocarbons on a cobalt–alumina–silica gel catalyst

The effects of the H₂/CO ratio, pressure, temperature, and the reaction-gas recycle ratio on the selectivity for hydrocarbons (HCs), including long-chain C₃₅₊ HCs, in the Fischer–Tropsch synthesis over a supported industrial cobalt–silica gel catalyst have been studied. The synthesis parameters have been as follows: a pressure of 2.0 or 6.0 MPa, an H₂/CO ratio of 1–5, a recycle ratio of 2–6, a temperature of 150–240°C, and a gas hourly space velocity of 1000 h^?1. It has been shown that gas recycling provides thermal stability in the catalyst bed, significantly increases the yield of C₃₅₊ HCs, and makes it possible to control the group and fractional composition of the synthesis products.     

Gasification property of coal–oilfield wastewater–slurry and microscopic mechanism analysis

Oilfield wastewater was used to prepare coal slurry, which is called coal–oilfield wastewater–slurry. The gasification properties of coal–oilfield wastewater–slurry and coal water slurry were studied by using the thermogravimetry method, and the promoting effect of oilfield wastewater on gasification was also determined at the micro level. Results showed that coal–oilfield wastewater–slurry and coal water slurry both exhibited a similar gasification process. However, compared with coal water slurry, all the gasification parameters of coal–oilfield wastewater–slurry were better, thereby suggesting that oilfield wastewater play a positive role in promoting gasification. Sodium ions and potassium ions were distributed on the coal particle surfaces and also in the pores, and they provided active sites and enhanced the gasification activity.     

Study on the characteristics of palm oil–biodiesel–diesel fuel blend

Palm oil/palm oil methyl esters are blends with diesel fuel, the blends were characterized as an alternative fuels for diesel engines. Density, kinematic viscosity, and flash point were estimated according to ASTM as key fuel properties. Palm oil and palm oil biodiesel were blended with diesel. The properties of both blends were estimated. The results showed that the fuel properties of the blends were very close to that of diesel till 30% unless other characteristics are within the limits. The experimental data were correlated as a function of the volume fraction of oil/biodiesel in the blend. Different correlations were developed to predict the properties of the oil/bio-oil-diesel blends based on our experimental results. The developed correlations were validated by comparing the correlation prediction with experimental data in literature. A good agreement was found between modeled equations prediction and experimental data in literature. The developed equations can be used as a guide for determining the best blending mixture to be used for diesel engines.