Solution Properties and Displacement Characteristics of in situ CO2 Foam System for Enhanced Oil Recovery

Carbon dioxide (CO₂) foam flooding has been shown to enhance oil recovery. However, large-scale adoption has been restricted by issues with transportation of CO₂ and equipment corrosion. In situ CO₂ foam generation can possibly overcome these issues. In this article, a CO₂ sustained-release system was first optimized for the CO₂ production rate and production efficiency. Then, the dissolution capacity and plug-removing ability of the sustained-release system were evaluated. Visual experiment and parallel sand pack flooding tests were conducted to verify the formation, propagation of in situ CO₂ foam, and the feasibility of this technique. The results indicated that the sustained-release system had benign ability to lower injection pressure and improve injectability. Moreover, in situ CO₂ foam flooding could obtain high oil recovery due to favorable mobility control ability, interfacial tension reduction capacity, and heterogeneity improvement. All the experiments demonstrated that the in situ CO₂ foam technique has great potential for enhanced oil recovery in the Bohai oilfield.     

Investigation on Foam Self‐Generation Using In Situ Carbon Dioxide (CO2) for Enhancing Oil Recovery

In situ carbon dioxide (CO₂) foam flooding has proved to be economically feasible in the oil field, but its self‐generation behavior in the bulk scale/porous media is far from understood. In this study, the optimum in situ CO₂‐foaming agent was first screened, and then in situ foam was investigated in the bulk. In situ foam flooding was conducted to evaluate the displacement characteristics and enhanced oil recovery of this system. The results showed that the foaming agent comprising 0.5% sodium dodecyl sulfonate (SDS) + 0.5% lauramido propyl hydroxyl sultaine (LHSB) gave the best foam properties and that the in situ CO₂ foam with a slow releasing rate is effective both in bulk scale and in porous media, allowing a considerable enhancement of oil recovery in sand packs with different permeabilities.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Continuous fractionation of used frying oil by supercritical CO<Subscript>2</Subscript>

Fractionation by supercritical carbon dioxide (SC−CO₂) might be a way to purify used frying oils, since a selective separation of the oil components based on their polarity and M.W. can be attained. In this work, we studied the purification of peanut oil used for frying by SC−CO₂ continuous fractionation in a packed column. The influence of pressure (15–35 MPa) and temperature (25–55°C) on the yield and on the composition of products was determined. The composition of the top and bottom products was evaluated by using size-exclusion chromatography and other accepted chemical methods. Process conditions were selected to separate TG from degraded compounds. Experimental results indicated that the operating conditions leading to maximal TG recovery in the extract were 35 MPa, 55°C, and a solvent-to-feed ratio of 53. By operating at these conditions, it was possible to recover 97% of the TG placed on the column and about 52% by weight of the used frying oil. The composition of the purified top stream was very similar to that of fresh frying oil.     

Self-Metathesis of 1-Octene Using Alumina-Supported Re<Subscript>2</Subscript>O<Subscript>7</Subscript> in Supercritical CO<Subscript>2</Subscript>

In this contribution we describe the use of heterogeneous catalysts for the liquid-phase self-metathesis of 1-octene in supercritical CO₂. Our work aims at addressing the mass-transfer problems associated with such reaction systems. By coupling a heterogeneous supported Re₂O₇ catalyst with the use of scCO₂, the self-metathesis of 1-octene takes place by and large much more rapidly than in traditional solvent media, and furthermore, by using scCO₂ the overall efficiency and sustainability of the transformation can be improved.

Dye sensitized CO<Subscript>2</Subscript> reduction over pure and platinized TiO<Subscript>2</Subscript>

TiO₂ thin and thick films promoted with platinum and organic sensitizers including novel perylene diimide dyes (PDI) were prepared and tested for carbon dioxide reduction with water under visible light. TiO₂ films were prepared by a dip coating sol–gel technique. Pt was incorporated on TiO₂ surface by wet impregnation [Pt(on).TiO₂], or in the TiO₂ film [Pt(in).TiO₂] by adding the precursor in the sol. When tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate was used as sensitizer, in addition to visible light activity towards methane production, H₂ evolution was also observed. Perylene diimide derivatives used in this study have shown light harvesting capability similar to the tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate.     

Particle size effects on supercritical CO<Subscript>2</Subscript> extraction of oil-containing seeds

Rosehip seeds were milled, sieved, and extracted with 26.3 g/g substrate/h of supercritical carbon dioxide (CO₂) at 40°C and 300 bar. The extraction kinetics were characterized by an initial solubility-controlled period (8.78 g oil/kg CO₂ at 40°C and 300 bar), followed by a transition period to a final mass transfer-controlled process. The integral yield of oil approached an asymptotic value that was dependent on the particle size of the substrate: 57.1 g oil/kg dry oil-free substrate (large particles), 171.0 g/kg (medium-size particles), or 391.5 g/kg (small particles). Based on gravimetric determinations and microscopic analysis, our size-classification process segregated seed parts having different oil contents. Particles ≥0.85 mm were mainly composed of tough, lignified testa fragments devoid of oil, whereas particles ≤0.425 mm contained mostly brittle, oil-rich germ fragments. The segregation of seed in fractions with different oil contents may be a common occurrence in supercritical extraction experiments, especially for seeds with thick and/or hard testa and small germ, whose fractions can be separated by sieving.     

Simultaneous absorption of CO<Subscript>2</Subscript> and SO<Subscript>2</Subscript> into aqueous AMP/NH<Subscript>3</Subscript> solutions in binary composite absorption system

To enhance the absorption rate for CO₂ and SO₂, aqueous ammonia (NH₃) solution was added to an aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The simultaneous absorption rates of AMP and a blend of AMP+ NH₃ for CO₂ and SO₂ were measured by using a stirred-cell reactor at 303 K. The process operating parameters of interest in this study were the solvent and concentration, and the partial pressures of CO₂ and SO₂. As a result, the addition of NH₃ solution into aqueous AMP solution increased the reaction rate constants of CO₂ and SO₂ by 144 and 109%, respectively, compared to that of AMP solution alone. The simultaneous absorption rate of CO₂/SO₂ on the addition of 1 wt% NH₃ into 10 wt% AMP at a p _A1 of 15 kPa and p _A2 of 1 kPa was 5.50×10⁻⁶ kmol m⁻² s⁻¹, with an increase of 15.5% compared to 10 wt% AMP alone. Consequently, the addition of NH₃ solution into an aqueous AMP solution would be expected to be an excellent absorbent for the simultaneous removal of CO₂/SO₂ from the composition of flue gas emitted from thermoelectric power plants.     

泡沫助采在油田中的现状与发展前景

泡沫作为一种良好的驱油剂已逐渐为人们所认识,它能够极大提高注入流体的表观黏度,增加波及面积,提高采收率,是一种很有发展前途的提高采收率的新方法。本文综述了国内外泡沫驱技术的应用与研究进展,并进一步分析了泡沫驱的驱油机理、影响泡沫稳定的因素以及存在的问题。     

The decomposition of CO<Subscript>2</Subscript> in glow discharge

The energy of the first vibrational level of the N₂ molecule is quite close to the energy of the first level of the asymmetric mode of CO₂. Hence, fast resonance transfer of vibrational energy from N₂ molecules to CO₂, directly populating the necessary level, becomes feasible. As a result of CO₂-CO₂ collision, the population increase of higher vibrational levels of asymmetric mode of CO₂ takes place up to the decomposition of molecules.     

Electrocatalytic oxidation of ethanol on Sn<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Ir<Subscript>(<Emphasis Type="Italic">x</Emphasis>)</Subscript>O<Subscript>2</Subscript> electrodes in acid medium

The electrochemical oxidation of ethanol at Sn_(1−x)Ir _x O₂ electrodes (with x = 0.01, 0.05, 0.1 and 0.3) was studied in 0.1 mol L⁻¹ HClO₄ solution. Electrolysis experiments were carried out and the reaction products were analyzed by Liquid Chromatography. It was found that the amounts of the reaction products depended on the composition of the electrode. In situ infrared reflectance spectroscopy measurements were performed to identify the adsorbed intermediates and to postulate a reaction mechanism for ethanol electrooxidation on these electrode materials. As evidence, acetaldehyde and acetic acid were formed through a successive reaction process. Carbon dioxide was also identified as the end product, showing that the cleavage of the carbon–carbon bond occurred. These results indicate that the synthesized catalysts are able to lead to the total combustion of organic compounds. Analysis of the water bending band at different potentials illustrated its role at the electrode interface.     

Gas Analysis by In Situ Combustion in Heavy‐Oil Recovery Process: Experimental and Modeling Studies

Enormous efforts have been made to facilitate produced‐gas analyses by in situ combustion implication in heavy‐oil recovery processes. Robust intelligence‐based approaches such as artificial neural network (ANN) and hybrid methods were accomplished to monitor CO₂/O₂/CO. Implemented optimization approaches like particle swarm optimization (PSO) and hybrid approach focused on pinpointing accurate interconnection weights through the proposed ANN model. Solutions acquired from the developed approaches were compared with the pertinent experimental in situ combustion data samples. Implication of hybrid genetic algorithm and PSO in gas analysis estimation can lead to more reliable in situ combustion quality predictions, simulation design, and further plans of heavy‐oil recovery methods.     

Performance of Ni catalyst supported on La-hexaaluminate in CO<Subscript>2</Subscript> reforming of CH<Subscript>4</Subscript>

CO₂ reforming of CH₄ was performed using Ni catalyst supported on La-hexaaluminate which has been an well-known material for high-temperature combustion. La-hexaaluminate was synthesized by sol-gel method at various conditions where different amount of Ni (5–20 wt%) was loaded. Ni/La-hexaaluminate experienced 72 h reaction and its catalytic activity was compared with that of Ni/Al₂O₃, Ni/La-hexaaluminate shows higher reforming activity and resistance to coke deposition compared to the Ni/Al₂O₃ model catalyst. Coke deposition increases proportionally to Ni content. Consequently, Ni(5)/La-hexaaluminate(700) is the most efficient catalyst among various Ni/La-hexaaluminate catalysts regarding the cost of Ni in Ni(X)/La-hexaaluminate catalysts. BET surface area, XRD, EA, TGA and TPO were performed for surface characterization. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Hydrolysis of Phosphatidylcholine-Isoprostanes (PtdCho-IP) by Peripheral Human Group IIA,V and X Secretory Phospholipases A<Subscript>2</Subscript> (sPLA<Subscript>2</Subscript>)

Biologically active F- and E/D-type-prostane ring isomers (F₂-IP and E₂/D₂-IP, respectively) are produced in situ by non-enzymatic peroxidation of arachidonic acid esterified to GroPCho (PtdCho-IP) and are universally distributed in tissue lipoproteins and cell membranes. Previous work has shown that platelet-activating factor acetylhydrolases (PAF-AH) are the main endogenous PLA₂ involved in degradation of PtdCho-IP. The present study shows that the PtdCho-IP are also subject to hydrolysis by group IIA, V and X secretory PLA₂, which also have a wide peripheral tissue distribution. For this demonstration, we compared the LC/MS profiles of PtdCho-IP of auto-oxidized plasma lipoproteins after incubation for 1–4 h (37 °C) in the absence or presence of recombinant human sPLA₂ (1–2.5 µg/ml). In the absence of exogenously added sPLA₂ the total PtdCho-IP level after 4 h incubation reached 15.9, 21.6 and 8.7 nmol/mg protein of LDL, HDL and HDL₃, respectively. In the presence of group V or group X sPLA₂ (2.5 µg/ml), the PtdCho-IP was completely hydrolyzed in 1 h, while in the presence of group IIA sPLA₂ (2.5 µg/ml) the hydrolysis was less than 25% in 4 h, although it was complete after 8–24 h incubation. This report provides the first demonstration that PtdCho-IP are readily hydrolyzed by group IIA, V and X sPLA₂. A co-location of sPLA₂ and the substrates in various tissues has been recorded. Thus, the initiation of interaction and production of isoprostanes in situ are highly probable.     

Maximization of total surface area of Pt-SnO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst by the Taguchi method

The maximization of the total surface area of Pt-SnO₂/Al₂O₃ catalyst was studied by using the Taguchi method of experimental design. The catalysts were prepared by sol-gel method. The effects of HNO₃, H₂O and aluminum nitrate concentrations and the stirring rate on the total surface area were studied at three levels of each. L₉ orthogonal array leading nine experiments was used in the experimental design. The parameter levels that give maximum total surface area were determined and experimentally verified. In the range of conditions studied it was found that, medium levels of HNO₃ and H₂O concentration and lower levels of aluminum nitrate concentration and stirring rate maximize the total surface area.     

Selectivity of Supercritical CO<Subscript>2 </Subscript>in the Fractionation of Hake Liver Oil Ethyl Esters

The solubility of different ethyl esters derivatized from hake liver oil in supercritical carbon dioxide was studied. A selectivity factor was used to determine optimal conditions to fractionate the ethyl ester mixture. A strong influence of solvent pressure and temperature was observed within 8.63–18.04 MPa and 40–70 °C. The lowest total solubility of the ethyl ester mixture was obtained when using supercritical carbon dioxide at the lowest density (the lowest pressure and the highest temperatures value tested). The highest discrimination against long-chain polyunsaturated fatty acids (e.g. EPA and DHA) was also obtained at these above conditions. Conversely, higher solubility and lower selectivity were obtained when solvent density increased. Considering this inverse correlation between selectivity and solubility, a single-step batch-fractionation process was designed to increase the 22:6 ethyl ester content from an initial value of 17.5% in the starting material to 55% in the final extract.     

Electrochemical polymerization and characterization of a poly(azulene)-TiO<Subscript>2</Subscript> nanoparticle composite film

A poly(azulene)-TiO₂ composite film (PAz-TiO₂) was synthesized electrochemically by oxidation of azulene in an electrolyte medium containing TiO₂ nanoparticles. Polymerization was performed under magnetic stirring in an acetonitrile solution containing tetrabutylammonium hexafluorophosphate as the electrolyte salt. Influence of the concentration of TiO₂ in the reaction suspension on the electrochemical and optical properties and on the structure of the composite films was studied by cyclic voltammetry, ex situ Raman and FTIR reflection spectroscopy and in situ UV–vis and FTIR spectroelectrochemical techniques. Morphology of the composite films was studied by Scanning Electron Microscopy and the amount and distribution of the TiO₂ nanoparticles within the polymeric matrix by Inductively Coupled Plasma Mass Spectrometry with laser ablation. Addition of TiO₂ in the reaction suspension had a small catalytic activity for the polymerization of Az. Inclusion of TiO₂ nanoparticles in PAz did not affect the voltammetric behavior or the chemical structure of the formed polymer films. However, a different chain conformation and morphology of the film was formed when synthesized in presence of TiO₂ compared to the plain PAz film. It was also found that the film morphology was more homogeneous when the concentration of TiO₂ was ≥10 mM in the polymerization solution than films polymerized without any TiO₂.     

低渗透油藏泡沫驱油机理及应用现状研究

低渗透油气藏在世界范围内分布范围广,储量大,在新探明储量中占得比例越来越大,是全球油气资源增产的主要来源,合理高效的开发低渗透油藏中的油气资源,是未来面临的主要问题。泡沫驱油作为继水驱、气驱之后新的驱油方式,结合了气体和泡沫的优点,以独特的优势越来越得到人们的重视,是低渗透油藏提高采收率的又一个重要途径。分析了泡沫驱相对于其他驱油方式的优势,概述了泡沫驱油的驱油机理,简要分析了空气泡沫驱、氮气泡沫驱各自特点,对泡沫驱油在国内外油田的应用现状做了介绍。对泡沫驱油存在的问题做了阐述,并提出了泡沫驱油的发展方向。     

Interaction Between Atmospheric CO<Subscript>2</Subscript> and Glucosinolates in Broccoli

Total and individual glucosinolate contents of broccoli cv Marathon were assessed at ambient CO₂ (430–480 ppm) and elevated atmospheric CO₂ (685–820 ppm) to determine the ecological relationship between changing atmospheric CO₂ concentrations and phytochemicals. Elevated atmospheric CO₂ concentration had a differing effect on individual glucosinolates and glucosinolate groups. Total glucosinolate content increased at elevated atmospheric CO₂ concentration as a result of a strong increase in both methylsulfinylalkyl glucosinolates glucoraphanin and glucoiberin. In contrast, indole glucosinolates simultaneously decreased, predominantly because of a reduction of glucobrassicin and 4-methoxy-glucobrassicin contents. We conclude that changes in N content and N/S ratios as well as alterations in photochemical processes at elevated atmospheric CO₂ concentration can influence total and individual glucosinolates contents of Brassicaceae, as demonstrated in the greenhouse, for broccoli.