Synthesis of uniform and dispersive calcium carbonate nanoparticles in a protein cage through control of electrostatic potential

We have synthesized calcium carbonate nanoparticles (Ca-NPs) in the cavity of a cage-shaped protein, apoferritin, by regulating the electrostatic potential of the molecule. The electrostatic potential in the cavity was controlled by pH changes resulting from changes in the dissolved carbon dioxide (CO(2)) concentration in the reaction solution. Recombinant L-apoferritin was mixed with a suspension of calcium carbonate (CaCO(3)), and the mixture was pressurized with gaseous CO(2) at 2 MPa. The pH of the solution decreased from 9.3 to 4.4; the CaCO(3) dissolved during pressurization, and then precipitated after the pressure was reduced to ambient. After repeating the pressurization/depressurization process three times, about 70% of the apoferritin molecules were found to contain nanoparticles with an average diameter of 5.8 ± 1.2 nm in their cavity. Energy-dispersive X-ray spectroscopy and electron diffraction analysis showed that the nanoparticles were calcite, one of the most stable crystal forms of CaCO(3). Electrostatic potential calculations revealed a transition in the potential in the apoferritin cavity, from negative to positive, below pH 4.4. The electrostatic potential change because of the change in pH was crucial for ion accumulation. Since the Ca-NPs synthesized by this method were coated with a protein shell, the particles were stably dispersed in solution and did not form aggregates. These Ca-NPs may be useful for medical applications such as synthetic bone scaffolds.     

Nanofluid in Hydrophilic State for EOR Implication Through Carbonate Reservoir

More than 50% of oil is trapped in petroleum reservoirs after applying primary and secondary recovery methods for removal. Thus, to produce more crude oils from these reservoirs, different enhanced oil recovery (EOR) approaches should be performed. In this research, the effect of hydrophilic nanoparticles of SiO₂ at 12 nm size, in (EOR) from carbonate reservoir is systematically investigated. Using this nanoparticle, we can increase viscosity of the injection fluid and then lower the mobility ratio between oil and nanofluid in carbonate reservoirs. To this end, a core flooding apparatus was used to determine the effectiveness and robustness of nanosilica for EOR from carbonate reservoirs. These experiments are applied on the reservoir carbonate core samples, which are saturated with brine and oil that was injected with nanoparticles of SiO₂ at various concentrations. The output results depict that, with increasing nanoparticle concentration, the viscosity of the injection fluid increases and results in decreased mobility ratio between oil and nanofluid. The results confirm that using the nanoparticle increases the recovery. Also, increasing the nanoparticle concentration up to 0.6% increases the ultimate recovery (%OOIP), but a further increase to 1.0 does not have a significant effect.     

Phase Equilibrium Modeling of Clathrate Hydrates of Carbon Dioxide + 1,4-Dioxine Using Intelligent Approaches

In this work, an adaptive neuro-fuzzy inference system (ANFIS) and a couple of fuzzy logic approach and genetic algorithms are utilized to serve robust inverse-based approaches for determination/prediction of the clathrate hydrate formation pressure of carbon dioxide in the presence of 1,4-dioxine, which is a most-widely implemented water “soluble” organic promoter. The gained outcomes prove the reliability and accuracy of the suggested ANFIS approach with the mean square error of 0.0034 and squared correlation coefficients of 0.9969. Thanks to the results generated by the aforementioned intelligent approaches, the models proposed in the current research contribute to high accuracy for the estimations of the phase equilibria clathrate hydrates of carbon dioxide +1,4-dioxane.      

Micronization of Iron Oxide Particles Using Gas Antisolvent Process

Iron oxide particles were micronized by supercritical carbon dioxide (CO₂) as an antisolvent in a batch gas antisolvent (GAS) process. In the present study, the feasibility of GAS process to micronize the iron oxide particles using dimethyl sulfoxide (DMSO) as a solvent was investigated. In this direction, particle size and morphology changes were investigated with changing solution pressure (80–150 bar), temperature (308.15–328.15 K), and concentration (1.5–6 g/l). Based on the different experimental conditions, the particle size of the original iron oxide was decreased in the range of 17.25 to 4.23 µm, which shows a the success of the GAS process to reduce the particle size of the intact iron oxide particles. Simultaneously, morphology changes were observed starting from the irregular morphology for synthesized particles to more regular shapes that included fused and spherical-fused particles.     

Similarities and Differences of Low Salinity Polymer and Low Salinity LPS (Linked Polymer Solutions) for Enhanced Oil Recovery

Linked polymer solution (LPS) is nano-size particles made of hydrolyzed polyacrylamide (HPAM) cross-linked with aluminum citrate. The propagation of LPS has been compared to non-cross-linked polymers at low brine salinity condition. The possible differences in properties and potentials for oil recovery have been investigated using water-wet and intermediate-wet cores. The target oil for polymer flooding (PF) is assumed to be the portion of the reservoir that has been bypassed by water during waterflooding and not the residual oil saturation in flooded zones. Our recent studies have shown that a positive synergy can be obtained by combining low salinity and PF. It has been claimed in the literature that cross-linking polymer such as colloidal dispersion gels (colloidal dispersion gels (CDG), micron-size aggregates) or LPS (nano-size particles) would extend the application of polymers to also include change in residual oil saturation. The results of this study indicated higher pressure buildup when low salinity LPS was propagated through brine saturated cores compared to low salinity polymer solution. The pressure buildup was even stronger for high salinity LPS injection. In two phase flow experiments, both polymer and LPS under low salinity condition, showed approximately similar propagation and oil recovery potential when injected into water-wet and intermediate-wet cores.     

Stability of Nanoporous Silica Aerogel Dispersion as Wettability Alteration Agent

This work studies the stability of silica aerogel aqueous dispersion for wettability alteration in enhanced oil recovery (EOR) processes. Modified silica aerogel is synthesized with cheap water glass as the precursor, and ambient pressure drying method. Brine composition, brine concentration and temperature of oil reservoirs are the most important parameters for success of wettability alteration processes in EOR. Stability of Silica aerogel aqueous dispersions in NaCl, MgCl₂ and combinations of them are surveyed. Brines at different concentrations, 10000, 20000, 40000 ppm, are used to determine stability conditions. Stability at 30°C and 75°C are surveyed, and the results are reported. DLVO and non-DLVO theories are used for modeling the stability of nanodispersion.     

无机钙材料在石灰岩文物表面防护中的应用

由于碳酸盐矿物的质地特点,石灰岩文物在露天环境中极易发生表面溶蚀,其上赋存文化信息的文字、纹饰和符号等雕刻痕迹也随之湮灭,对其文物价值造成了严重减损。从耐候性和兼容性角度考虑,无机保护材料显然更适合于石灰岩文物的表面防护处理。近年来,基于草酸钙、磷灰石和碳酸钙等钙基材料的石灰岩文物表面防护研究逐渐兴起并开始走向应用。本文就上述钙基保护材料的特点、防护膜制备和应用实践等做了归纳和评述,以期为石灰岩文物保护研究提供参考和借鉴。     

Determination of total carbon dioxide in seawater by capillary type isotachophoresis

Summary A new analytical procedure for total carbon dioxide in seawater was developed: a capillary-type isotachophoresis which applied a tubular microporous PTFE membrane as a preliminary enrichment was used. Carbon dioxide was generated by adding sulfuric acid to seawater samples, permeated through a tubular microporous PTFE membrane and dissolved in sodium hydroxide solution for the separation from large amounts of coexisting anions, such as chloride and sulfate ions. A linear working curve was obtained for artificial seawater samples containing up to 40 mg/l of total carbon dioxide. The proposed method was applied to the determination of total carbon dioxide in surface and bottom seawater samples. Concentrations of the total of free carbon dioxide and carbonic acid, hydrogencarbonate and carbonate ions in these samples were calculated from the concentration of total carbon dioxide, temperature, pH and salinity of samples measured in situ.

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Bestimmung von Gesamtkohlendioxid in Meereswasser durch Capillar-Isotachophorese

     

超临界二氧化碳中无水相涂料的合成与表征

为了减小传统纸张涂布中涂料水分对涂布能耗、涂布质量以及对涂布原纸质量的影响,研究了以超临界二氧化碳为反应介质,制备聚甲基丙烯酸甲酯(PMMA)和碳酸钙颜料混合的粉末涂料粒子.通过FTIR、GPC-十八角度激光光散射联用技术对PMMA组成结构进行了表征,考察了反应体系中引发剂浓度、单体浓度、稳定剂浓度、反应温度和反应时间对聚合反应的转化率和聚合产物的分子量的影响.实验表明,当反应条件为反应压力10MPa,反应温度75℃,反应时间8h,单体浓度0.10g/mL,引发剂浓度0.10×10-2g/mL,稳定剂浓度0.06×10-2g/mL时,其聚合反应的转化率较高,同时PMMA的分子量适中,分子量分布窄.SEM观察到混合涂料粒子颗粒均匀,表明颜料在粉末涂料体系中分散性良好.     

无机钙材料在石灰岩文物表面防护中的应用

由于碳酸盐矿物的质地特点,石灰岩文物在露天环境中极易发生表面溶蚀,其上赋存文化信息的文字、纹饰和符号等雕刻痕迹也随之湮灭,对其文物价值造成了严重减损。从耐候性和兼容性角度考虑,无机保护材料显然更适合于石灰岩文物的表面防护处理。近年来,基于草酸钙、磷灰石和碳酸钙等钙基材料的石灰岩文物表面防护研究逐渐兴起并开始走向应用。本文就上述钙基保护材料的特点、防护膜制备和应用实践等做了归纳和评述,以期为石灰岩文物保护研究提供参考和借鉴。     

Effect of Experimental Variables on the Combustion Characteristics of Water-in-Diesel Emulsion Fuels

Water-in-diesel (W/D) emulsion fuels were prepared through an ultrasonic processor by using high energy emulsification method. Accordingly, the physical and chemical properties were analyzed. A decrease in viscosity was found in the emulsion fuel in contrast to the neat diesel which signifies the enhanced fluidity of the fuel. The emulsion fuel was then used to carry combustion tests in an internal combustion engine. A decrease in exhaust temperature was observed when a high surfactant to water ratio was used, which lead to minimal heat loss. As water is emulsified with diesel, effectiveness of combustion is improved rather than neat diesel fuel. It was also explored that the addition of water-in-diesel is influential in terms of reduction in exhaust gas emission such as carbon dioxide, carbon monoxide, ammonia from the internal combustion engine. Therefore, this type of emulsion fuel would be a useful contribution in the fuel economy, but also in making it environmentally friendly since diesel fuel is now considered one of the leading fuels causing ecological contamination.     

In situ infrared spectroscopic study of brucite carbonation in dry to water-saturated supercritical carbon dioxide

In geologic carbon sequestration, whereas part of the injected carbon dioxide will dissolve into host brine, some will remain as neat to water saturated supercritical CO(2) (scCO(2)) near the well bore and at the caprock, especially in the short term life cycle of the sequestration site. Little is known about the reactivity of minerals with scCO(2) containing variable concentrations of water. In this study, we used high-pressure infrared spectroscopy to examine the carbonation of brucite (Mg(OH)(2)) in situ over a 24 h reaction period with scCO(2) containing water concentrations between 0% and 100% saturation, at temperatures of 35, 50, and 70 °C, and at a pressure of 100 bar. Little or no detectable carbonation was observed when brucite was reacted with neat scCO(2). Higher water concentrations and higher temperatures led to greater brucite carbonation rates and larger extents of conversion to magnesium carbonate products. The only observed carbonation product at 35 °C was nesquehonite (MgCO(3)·3H(2)O). Mixtures of nesquehonite and magnesite (MgCO(3)) were detected at 50 °C, but magnesite was more prevalent with increasing water concentration. Both an amorphous hydrated magnesium carbonate solid and magnesite were detected at 70 °C, but magnesite predominated with increasing water concentration. The identity of the magnesium carbonate products appears strongly linked to magnesium water exchange kinetics through temperature and water availability effects.     

Mechanism of Produced Gas Reinjection During CO2 Flooding by Chromatographic Analysis

CO₂ flooding process has been a proven valuable method that could not only enhance oil recovery but also store greenhouse gas. However, CO₂ source greatly restrict its application in China. In this article, based on the produced oil and gas of Jilin oilfield, slim tube tests were conducted to study the feasibility of the produced gas reinjection without separation. In addition, according to the phenomenon of the experiment, displacement process was divided into three stages. Chromatographic analysis was conducted to study the mechanism of production gas reinjection during CO₂. Results indicate that components of the produced oil change along with CO₂ content, displacement pressure and production stages.     

Mechanistic investigation and reaction kinetics of the low-pressure copolymerization of cyclohexene oxide and carbon dioxide catalyzed by a dizinc complex

The reaction kinetics of the copolymerization of carbon dioxide and cyclohexene oxide to produce poly(cyclohexene carbonate), catalyzed by a dizinc acetate complex, is studied by in situ attenuated total reflectance infrared (ATR-IR) and proton nuclear magnetic resonance ((1)H NMR) spectroscopy. A parameter study, including reactant and catalyst concentration and carbon dioxide pressure, reveals zero reaction order in carbon dioxide concentration, for pressures between 1 and 40 bar and temperatures up to 80 °C, and a first-order dependence on catalyst concentration and concentration of cyclohexene oxide. The activation energies for the formation of poly(cyclohexene carbonate) and the cyclic side product cyclohexene carbonate are calculated, by determining the rate coefficients over a temperature range between 65 and 90 °C and using Arrhenius plots, to be 96.8 ± 1.6 kJ mol(-1) (23.1 kcal mol(-1)) and 137.5 ± 6.4 kJ mol(-1) (32.9 kcal mol(-1)), respectively. Gel permeation chromatography (GPC), (1)H NMR spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry are employed to study the poly(cyclohexene carbonate) produced, and reveal bimodal molecular weight distributions, with narrow polydispersity indices (≤1.2). In all cases, two molecular weight distributions are observed, the higher value being approximately double the molecular weight of the lower value; this finding is seemingly independent of copolymerization conversion or reaction parameters. The copolymer characterization data and additional experiments in which chain transfer agents are added to copolymerization experiments indicate that rapid chain transfer reactions occur and allow an explanation for the observed bimodal molecular weight distributions. The spectroscopic and kinetic analyses enable a mechanism to be proposed for both the copolymerization reaction and possible side reactions; a dinuclear copolymerization active site is implicated.     

非胺类CO2吸收剂的研究进展

针对CO₂所带来的全球气候变化问题,本文综述了可用于捕集CO₂的非胺类吸收剂类型,认为氨基酸盐、氨基酸-碳酸钾体系、离子液体、生物型吸收剂、钙基吸收剂分别具有较高的CO₂循环吸收负荷、低毒性、热稳定性好、较优的生物相容性、钙源易获取的优势,可以弥补胺类吸收剂在吸收-解吸CO₂时腐蚀性强、再生能耗高、对环境产生二次污染等方面的不足。氨基酸盐、氨基酸-碳酸钾体系可应用于具有一定规模的CO₂捕集工业中;离子液体可应用于精准、绿色环保去除CO₂工业中;生物型吸收剂可用于规模小、CO₂浓度低的工业中;钙基吸收剂可运用于CO₂浓度高的工业中。上述吸收剂皆具有一定的工业前景。     

天然气与硫酸盐热化学还原反应的模拟实验研究

为探讨天然气中高含量硫化氢形成的化学机制，利用高温高压反应装置，对天然气与固态硫酸钙反应体系进行了热模拟实验研究。使用气相色谱仪、微库仑仪、傅里叶变换红外光谱仪和X射线衍射仪对产物进行了分析，探讨了硫酸盐热化学还原反应的热力学特征，并进行了反应动力学研究。结果表明，高温下天然气与固态硫酸钙可以发生反应，产物主要为硫化氢、二氧化碳、碳酸钙、水和炭。热力学研究表明，天然气与固态硫酸钙的反应可行，升高温度对反应有利，同一温度下长链烷烃与固态硫酸钙发生反应的可能性要比短链烷烃大。根据动力学模型得到反应活化能为96.824kJ/mol。     

Kinetic and Thermodynamic Studies for the Removal of Nickel Ions from an Aqueous Solution by Adsorption Technique

The kinetics and dynamics of nickel ions adsorption on activated carbon and bentonite were studied. The influence of parameters (pH, amount of adsorbent, adsorbate concentration, solution volume, rotation speed, and temperature) were investigated. Kinetic models of pseudo-first, pseudo-second and Weber-Morris models were applied. The data was better reported by the pseudo-second order model. Freundlich, Langmuir, and D-R models were utilized for the analysis of adsorption equilibrium. Evaluation of thermodynamic parameters reveal that adsorption is spontaneous and endothermic in nature. From the experimental data, it was concluded that bentonite has more efficiency for the adsorption of nickel ions than activated carbon.     

Compositions and Physicochemical Properties of Tween Type Surfactants-Based Microemulsions

The compositions and physicochemical properties of the microemulsion systems consisting of Tween type surfactant (Tween 20, Tween 60, Tween 80)/butan-1-ol/dodecane/brine have been studied using ?-β fishlike phase diagram. From the ?-β fishlike phase diagram, solubility of the alcohol, composition of the interfacial layer, and solubilization ability of the microemulsion systems have been studied. The solubilization parameters of the microemulsion systems, SP* were in the order of magnitude Tween 60>Tween 80>Tween 20. The effects of different oils, alcohols, salinities and temperatures on the compositions and physicochemical properties have been investigated. The solubilization ability of the microemulsion systems increases with increasing salinities or decreasing temperatures. The effects of alcohols and alkanes display opposite patterns of change. By increasing the carbon chain length of the alkanol molecules, or decreasing the carbon chain length of the alkane molecules, the solubilization ability increases.     

Generation of Asphaltene Deposition Envelope Using Artificial Neural Network

The usefulness of the asphaltene deposition envelope (ADE) is that no asphaltene flocculation occurs at conditions outside the envelope. Since artificial neural network (ANN) is best at identifying patterns or trends in data, it is well suited for prediction or forecasting needs. ANN is also capable of addressing case specific problems that may be encountered in the field such as deposition of asphaltene. In this article, the high pressure, high temperature setup used to perform pressure depletion experiments at three different temperatures on one the Iranian live oils and the ADE generated using ANN.