Extraction of boric acid from colemanite mineral by supercritical carbon dioxide

The use of H₂SO₄ in boric acid production from colemanite mineral has several problems, related to product impurities, corrosion and environmental discharge limits. To overcome these problems and to increase extraction efficiency of boric acid, heterogeneous reaction between colemanite and CO₂ dissolved in H₂O was studied at and above supercritical CO₂ conditions. Supercritical conditions enhanced the extraction efficiency of boric acid from colemanite mineral, with 96.9% boric acid extraction efficiency being obtained from CO₂–colemanite reaction at 60 °C, for 2 h of reaction time for particles in the range of +20–40 μm. A powder crystallized from filtrate of reaction was determined as H₃BO₃ and the solid formed at the end of reaction was characterized mostly as CaCO₃ according to FTIR, XRD, TGA and SEM analyses. The use of supercritical CO₂ as a leaching agent in colemanite does not only produce boric acid but also helps to reduce the amount of CO₂ in the atmosphere. Based on these facts, supercritical CO₂ as extractant makes this process green and sustainable for recovering boric acid from boron minerals.     

Off-flavor removal from soy-protein isolate by using liquid and supercritical carbon dioxide

The efficacy of liquid carbon dioxide (L-CO₂), supercritical carbon dioxide (SC-CO₂), and SC-CO₂ containing 5% ethanol in the removal of off-flavors from soybean protein isolate was studied. Medium-chain aldehydes:n-butanal,n-pentanal, andn-hexanal; ketones: 2-butanone, 2-pentanone, and 2-hexanone; and alcohols: 1-butanol and 2-butanol; were the major compounds extracted. The extractions were performed at a constant fluid density of 901 kg/m³ with 100, 500, and 1000 standard liter of carbon dioxide. None of the treatments had a detrimental effect on soy-protein functionality. Headspace gas chromatography (GC) and sensory analysis of the treated samples were compared with the untreated soy isolate (control). In general, L-CO₂ was the least effective, and SC-CO₂ was the most effective in removing the off-flavor volatiles. Addition of ethanol as an entrainer did not improve the efficiency of off-flavor removal by SC-CO₂. The results of sensory analysis correlated well with the GC analysis. Sensory analysis of a 33% (wt/vol) slurry of treated soy-protein isolate had more off-flavor notes than the dry soy isolate. Dry and slurried treated soy-protein isolates had significantly less off-flavors and significantly more acceptability than the untreated control.     

超临界CO_2萃取水冬瓜油

研究了用超临界ＣＯ２流体从水冬瓜果实中提取油品的工艺,探索了操作压力、温度、流量及时间对水冬瓜油的萃取率的影响。分析了萃取条件与油品质量的关系,并综合得出了超临界ＣＯ２萃取水冬瓜油的最佳萃取条件。     

Extraction of phospholipids from canola with supercritical carbon dioxide and ethanol

The potential use of supercritical (SC)-CO₂/ethanol mixture for the extraction and fractionation of phospholipids (PL) from flaked canola seeds, canola meal, and acetone insolubles (AI) was investigated. PL extraction was possible when ethanol was used as a cosolvent in SC-CO₂. PL recovery of 20.8% was achieved when canola flakes were extracted at 70°C and 55.2 MPa with SC-CO₂/10%EtOH after iol removal with neat SC-CO₂. Soaking of canola meal with ethanol prior to SC-CO₂/EtOH extraction increased PL recovery to 30.4%. PL content of the extracts increased with decreasing triglyceride concentration in the feed material and increasing amounts of ethanol added to SC-CO₂ or used for soaking. Fractionation of Al gums resulted in extracts containing 50% PL, of which 90% was phosphatidylcholine (PC); but yields were low, even after soaking treatment, due to caking. SC-CO₂/EtOH mixture may be used to extract PC-enriched PL from flaked canola seeds, canola meal, and AI. However, further research is needed to improve extraction efficiency.     

The absorption of carbon dioxide by a quiescent liquid

An interferometric technique is described by which the absorption of carbon dioxide into quiescent water has been examined. There is no measurable resistance at the interface to solution of the gas into pure water, the rate of absorption into the liquid being governed by molecular diffusion. A measurable interfacial resistance is found when carbon dioxide is absorbed by solutions of surface-active agents.     

Viscosity reduction of polymeric liquid by dissolved carbon dioxide

The viscosities of polydimethylsiloxane (PDMS)/CO₂ solutions were measured over the range of pressures of 1–3 MPa and at the ambient temperature. The viscosities were measured by using a specially designed falling ball viscometer (FBV). The Stokes equation was used to determine the viscosities and the Stokes force expressing the viscous drag of the sphere was corrected for the effect of the lateral cylindrical wall. The Kelley-Bueche (KB) free-volume treatment of the viscosities of polymeric solutions was modified to account for the gas solvent and applied to interpret our data on PDMS/CO₂ systems. It was shown that the theoretical equation, based on the assumption of the additivity of free volumes of the components, was capable of predicting with remarkable accuracy the concentration and pressure dependence of the viscosities of the investigated polymeric solutions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 459–466, 1997     

A crossover multi-fluid nonrandom lattice fluid model for pure hydrocarbons and carbon dioxide near to and far from the critical region

The multi-fluid nonrandom lattice fluid model with the local composition concept is capable of describing thermodynamic properties for complex systems, but this model cannot represent the singular behavior of fluids near the critical region. In this research, the multi-fluid nonrandom lattice fluid model for pure fluids is combined with a crossover theory to obtain a crossover multi-fluid nonrandom lattice fluid model which incorporates the critical scaling laws valid asymptotically close to the critical point and reduces to the original classical multi-fluid nonrandom model far from the critical point. The crossover multi-fluid nonrandom lattice fluid model shows a great improvement in prediction of the thermodynamic properties of pure compounds near the critical region.     

Electricity,methane and liquid carbon dioxide production from landfill gas

Landfill gas, which has a typical composition of 40–60% methane, 40–50% carbon dioxide, and a wide range of impurities, has historically been recovered solely for its heating value. After only minor impurity removal, landfill gas has been used as medium Btu industrial fuel or to generate electricity; after significant impurity and carbon dioxide removal, landfill gas has been used as a source of pipeline quality methane. For both cases, the value of the substantial amount of contained carbon dioxide has not been realized. This has been due to the impurities which present a significant obstacle to the economic production of merchant grade carbon dioxide.This paper presents two processes¹ which make use of an oxygen fed combustion step to reduce both the quantity and variety of impurities which must be removed to meet carbon dioxide product specifications. The two processes produce carbon dioxide and electricity or carbon dioxide and pipeline quality methane, respectively. In both oxygen based coproduction processes, the combustion step is integrated into the overall process to maximize energy efficiency. The two processes are described and anticipated net liquid carbon dioxide manufacturing costs are presented.     

Extraction of lipids and cholesterol from squid oil with supercritical carbon dioxide

The oil obtained from waste squid viscera consists of multi-compounds such as EPA, DHA and other valuable polyunsaturated fatty acids. The refining of this squid oil, using supercritical carbon dioxide plus ethanol, was performed in a semi-continuous flow extractor at 8 to 17 MPa and 25 to 50 °C. When 1.5% w/w ethanol was added to the solvent, the solubility of lipids was increased by up to 50% over the neat CO₂ value. The extraction curves indicated mass transfer to be solubility limited. Cholesterol was co-extracted with the lipids but, with its lower solubility, less than 54% appeared in the refined oil. The results of the carbon dioxide/multi-compound squid oil system at applied to the extraction conditions were correlated with the mole fraction of the cholesterol and the density of the pure solvent.     

Extraction of woolgrease with supercritical carbon dioxide

Supercritical carbon dioxide was used to extract unrefined woolgrease. The resulting product had no color and little odor, resembling high-grade commercial lanolin. The amounts of woolgrease extracted for fixed volumes of supercritical fluid solvent were measured at 60, 70 and 80°C and at pressures from 200–520 bar. In this study, the highest recoveries were obtained at 80°C and pressures in excess of 380 bar. Analysis of the extracts by capillary supercritical-fluid chromatography and thin-layer chromatography indicated that the composition of the extract changed with extraction time. The earliest fractions were enriched in cholesterol and contained relatively small amounts of species with higher molecular weight. The results suggest that supercritical fluid extraction may be used to obtain an enriched cholesterol fraction from wool-grease.     

Use of liquid carbon dioxide to remove hexane from soybean oil

Liquid carbon dioxide (L-CO₂) was investigated as a means to separate hexane from the mixture of soybean oil (SBO) and hexane resulting from the hexane extraction of soybeans. Using a fractionation tower, 5 vol of CO₂ (i.e., 100, 200, 300, 500, and 1000 L expanded gas) were passed through 50 mL of two concentrations of n-hexane (i.e., 10 and 25% w/w) in SBO. After passing through the hexane/SBO mixture, the expanded CO₂ was passed through a chilled collection flask to capture extracted hexane and SBO. The raffinate SBO was removed from the column and analyzed for residual hexane using International Organization for Standardization Method 9832:2002. Residual hexane decreased as the amount of L-CO₂ used increased and was less than 20 ppm after 200 L of CO₂. The amount of SBO extracted increased with the volume of CO₂ used. Significantly more SBO and hexane were collected from the 25% sample than the 10% sample. During the extraction of the mixture, the CO₂ selectively carried over TG with lower M.W. This research demonstrates the ability to use L-CO₂ to remove haxane from mixtures of hexane and SBO at both low pressures and temperatures.     

Extraction of caffeine from tea stalk and fiber wastes using supercritical carbon dioxide

The purpose of this study was to investigate obtaining of caffeine from tea plant wastes by supercritical carbon dioxide extraction. Experiments were carried out with tea stalk and fiber wastes of Turkish tea plants that has no economical value. Stalk and fiber wastes were supplied from tea factories. These wastes were ground, sieved and dried at 105 °C temperature in an oven. Parameters affecting caffeine leaching from tea wastes were determined to be, extraction time, extraction temperature, carbon dioxide flow rate, process pressure and particle size. The maximum yield of caffeine from tea stalk wastes and fiber wastes were 14.9 mg/g tea stalk and 19.2 mg/g tea fiber, respectively. The yield increase had been recorded as 61.9% and 65.5%, respectively, in comparison with the chloroform extraction of tea stalk and fiber wastes.     

Extraction of caffeine from tea stalk and fiber wastes using supercritical carbon dioxide

The purpose of this study was to investigate obtaining of caffeine from tea plant wastes by supercritical carbon dioxide extraction. Experiments were carried out with tea stalk and fiber wastes of Turkish tea plants that has no economical value. Stalk and fiber wastes were supplied from tea factories. These wastes were ground, sieved and dried at 105 °C temperature in an oven. Parameters affecting caffeine leaching from tea wastes were determined to be, extraction time, extraction temperature, carbon dioxide flow rate, process pressure and particle size. The maximum yield of caffeine from tea stalk wastes and fiber wastes were 14.9 mg/g tea stalk and 19.2 mg/g tea fiber, respectively. The yield increase had been recorded as 61.9% and 65.5%, respectively, in comparison with the chloroform extraction of tea stalk and fiber wastes.     

Quality of wheat germ oil extracted by liquid and supercritical carbon dioxide

The extraction of wheat germ oil by liquid and supercritical CO₂ is described from the point of view of both operative method and pretreatment of raw material. The best conditions for wheat germ oil extraction are: pressure, 150 bar; temperature, 40°C; and solvent flow rate, 1.5 L/min at standard temperature and pressure. The yields and fatty acid compositions obtained are very similar to those resulting from the conventional extraction process using hexane as solvent (8.0 wt%), although a higher-quality oil is obtained by using CO₂ as solvent (free fatty acids, 12.4%; tocopherol content, 416.7 mg tocopherol/g wheat germ oil). These factors lead to the conclusion that the extraction process using CO₂ could be economically competitive with the conventional process, since it considerably simplifies the oil refinement stages and completely eliminates the solvent distillation stage, which are the most costly processing steps in terms of energy consumption.     

Extraction of transition metals from wood pulp fibers using supercritical carbon dioxide

The supercritical fluid extraction of manganese and iron from solid matrix (wood pulp) is demonstrated experimentally. Supercritical carbon diodixe is used together with lithium bis(trifluoroethyl) dithiocarbonate (FDDC) as the ion-pairing reagent. The metal content of the pulp samples was determined by inductively couple plasma atomic emission spectroscopy (ICP-AES). Optimum conditions were determined to be 30 min each of static and dynamic extraction with 200 atm pressure at 40 °C. Thermomechanical pulp (TMP) extracted under these parameters exhibits an 80% decrease in manganese content, and 91% after a second, sequential extraction. The simultaneous removal of iron was found to be only 6% and supports evidence that it is much more strongly bound to the TMP matrix than manganese.     

液态和超临界态二氧化碳的非线性声学性质

根据美国国家标准局提供的二氧化碳在液态和超临界态下的声速、密度、比定压热容、膨胀系数等物理参数数据库中数据,计算了二氧化碳在液态和超临界状态下的声速压力系数、声速温度系数和非线性声参量几个非线性声学参数。分析归纳了液态二氧化碳和超临界二氧化碳的非线性声学特性,对比分析了液态二氧化碳、超临界二氧化碳和一般有机液的非线性声学特性。详细分析了二氧化碳在临界点附近的非线性声学特性。研究表明,液态二氧化碳表现出类似于一般液体在常温常压下的非线性声学特性;超临界二氧化碳的声速压力系数、声速温度系数和非线性声参量值可为正值或负值,其值随压力或温度的变化具有一定的规律性。压力越大温度越低,超临界二氧化碳的非线性声学特性越接近液态二氧化碳或一般液体。在临界点附近区域,3个参量值随压力或温度的变化出现正负最大值间的跳跃变化。     

Hydrogenation of carbon dioxide by hybrid catalysts,direct synthesis of aromatics from carbon dioxide and hydrogen

Direct synthesis of aromatics from carbon dioxide hydrogenation was investigated in a single stage reactor using hybrid catalysts composed of iron catalysts and HZSM-5 zeolite. Carbon dioxide was first converted to CO by the reverse water gas shift reaction, followed by the hydrogenation of CO to hydrocarbons on iron catalyst, and finally the hydrocarbons were converted to aromatics in HZSM-5. Under the operating conditions of 350°C, 2100 kPa, and CO₂/H₅ = 1/2, the maximum aromatic selectivity obtained was 22% with a CO₂ conversion of 38% using fused iron catalyst combined with the zeolite. Together with the kinetic studies, thermodynamic analysis of the CO₂ hydrogenation was also conducted. It was found that unlike Fischer Tropsch synthesis, the formation of hydrocarbons from CO₂ may not be thermodynamically favored at higher temperatures.     

Extraction from a polydisperse granular layer of milled oilseeds with supercritical carbon dioxide

A mathematical model of the supercritical fluid extraction of oil from a polydisperse granular layer of milled oilseeds is proposed. An experiment on the extraction of a polydisperse layer of white lupin seeds with different realizations of the size distribution function of the grains was carried out. The results of the laboratory experiment were used for the adaptation of the mathematical model; a fair agreement between the calculated and experimental curves of the oil yield was achieved.     

Extraction of methane hydrate energy by carbon dioxide injection-key challenges and a paradigm shift

Significant effort including field work has been devoted to develop a natural gas extraction technology from natural gas hydrate reservoirs through the injection of carbon dioxide. Natural gas hydrate is practically methane hydrate. The hypothesis is that carbon dioxide will be stored as hydrate owing to its favorable stability conditions compared to methane hydrate. Although the dynamics of the CO₂/CH₄ exchange process are not entirely understood it is established that the exchange process is feasible. The extent is limited but even if the CH₄ recovery is optimized there is a need for a CH₄/CO₂ separation plant to enable a complete cyclic sequence of CO₂ capture, injection and CH₄ recovery. In this paper we propose an alternative paradigm to the Inject (CO₂)/Exchange with (CH₄)/Recover (CH₄) one namely Recover (CH₄) first and then Inject (CO₂) for Storage.