二氧化碳在乙醇水溶液中的溶解度

报导一种测定气体在液体中溶解度的实验装置；在３０～４５℃的温度范围内测定了ＣＯ２在乙醇－水混合溶剂中的溶解度。结合ＵＮＩＦＡＣ方法及分子热力学法提出一种理论推算方法，并得出较满意的经验关联式。     

High pressure phase behavior for the binary mixture of pentafluoropropyl methacrylate and poly(pentafluoropropyl methacrylate) in supercritical carbon dioxide and dimethyl ether

Pressure-composition isotherm is obtained for the carbon dioxide+2,2,3,3,3-pentafluoropropyl methacrylate (PFPMA) using static apparatus with a variable volume view cell at temperature range from 40 °C to 120 °C and pressure up to 130 bar. This system exhibits type-I phase behavior with a continuous mixture-critical curve. The experimental result for carbon dioxide+PFPMA mixture was modeled using the Peng-Robinson (P-R) and multi-fluid nonrandom lattice fluid (MF-NLF) equation of state. Experimental cloud-point data of pressure up 470 bar and temperature to 182 °C were reported for the binary mixture of poly(2,2,3,3,3-pentafluoropropyl methacrylate) [Poly(PFPMA)] in supercritical carbon dioxide and dimethyl ether (DME). The Poly(PFPMA)+carbon dioxide and Poly(PFPMA)+DME systems showed LCST behavior.     

Compositional and structural variations of bitumen and its interactions with mineral matters during Huadian oil shale pyrolysis

Thermal bitumen is an important intermediate derived from kerogen decomposition during oil shale pyrolysis. In this study, free bitumen (FB) and bound bitumen (BB) were obtained by extracting oil shale chars (300–550 °C) before and after demineralization, and then analyzed by liquid chromatography fractionation, Fourier transform infrared spectroscopy, and gas chromatography/mass spectrometry. The FB yield first increased and then decreased with increasing temperature, and the maximum value was 2.10% at 400 °C. The decarboxylation of acids and decomposition of esters at 350–450 °C decreased the content of these compounds. Meanwhile, the intense cracking reactions of aliphatic compounds and alkyl chains at 400–450 °C decreased the carbon chain lengths and molecular weights of these compounds. From the analytical results obtained for the BB fractions, we suggest that some carboxylic acids or carboxyl group-containing compounds may be trapped on carbonate particles by the formation of Ca₂₊COO_? bonds, whereas other oxygenated compounds (e.g., esters and phenols) can be adsorbed preferentially by clay minerals through Lewis acid-base interactions.     

Solubility of fish oil fatty acid ethyl esters in suband supercritical carbon dioxide

Mutual solubilities and K-values of fish oil fatty acid ethyl esters, prepared from sand launce oil, and sub- and supercritical carbon dioxide have been measured in an apparatus originally designed for phase equilibrium, density and gasoil ratio measurements of reservoir fluids. The measurements were performed at pressures from 2 to 22 MPa at temperatures of 283.2, 313.2 and 343.2°K. Experimental temperatures, pressures, solubilities, K-values and densities are reported. The K-values of ethyl myristate, palmitate, oleate, eicosapentaenoate and docosahexaenoate are compared with published experimental binary and/or multicomponent data. Because both vapor and liquid solubilities are reported, such data are applicable in the design of supercritical extraction plants.     

High-pressure phase behavior of carbon dioxide in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Phase equilibrium data of carbon dioxide in the ionic liquid 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf₂N]) are presented at high pressures up to about 30 MPa and at temperatures between 298.15 K and 343.15 K. The solubilities at a given temperature were determined by measuring the bubble point pressure of the ionic liquid solution with carbon dioxide dissolved using the high-pressure equilibrium apparatus equipped with a variable-volume view cell. Solubility results are reported for carbon dioxide concentrations ranging from 0.21 up to 0.80 mole fraction. Carbon dioxide gave very high solubilities in the ionic liquid at lower pressures, while the equilibrium pressure increased very steeply at higher concentrations of carbon dioxide. The solubility of carbon dioxide in the ionic liquid decreased with an increase in temperature.     

Hydrocarbons separation with polymer membranes. I. Butadiene–isobutene separation with nitrile rubber membranes

The permeation characteristics and the selectivity of four nitrile rubber films with respect to 1,3-butadiene and isobutene were studied as a function of experimental conditions and the nature of membrane material. A specific research apparatus was developed, allowing the determination of both permeation rate and selectivity, at a temperature varying between 0° and 30°C and under a pressure of from 1 to 3 bars. The inverse proportion of permeation rate to membrane thickness was verified for a thickness of from 12 to 500 microns. An increase in temperature promotes liquid permeation and is detrimental to gas permeation, the latter being facilitated by an increase in pressure. The introduction of an inert gas pressure on the liquid did not bring about an increase in the liquid permeation rate. The permeation rate decreases as a result of an increase in the proportion of acrylonitrile in the rubber, which also affects selectivity; the latter reaches a maximum value when said proportion is about 23%. The effect of the composition of the feed mixture was also studied and curves were determined relating, simultaneously, selectivity and permeation rate to the 1,3-butadiene content. Selectivity is maximal with mixtures having a very high 1,3-butadiene content. The solubilities of 1,3-butadiene and of isobutene in the four types of nitrile rubber were measured at 0°C and at 20°C (68°F). Selectivity can be interpreted in terms of the solubilities of the two hydrocarbons.     

Solubilities of ethane and other gases in normal paraffin solvents

The design of a gas solubility apparatus utilizing the basic principle of the Morrison and Billet apparatus is described. The solubilities at atmospheric pressure of ethane in the normal paraffin solvents, hexane, heptane, octane, dodecane and hexadecane, and also of the same gas in the two-component solvent solutions consisting of hexane and hexadecane are reported. The solubilities of twelve gases were empirically correlated utilizing one constant for each gas. The empirical equations permit an estimate of the solubility in any normal paraffin solvent from hexane to hexadecane and for any temperature between 15°C and 40°C from a single solubility measurement.     

Solubilities of solids in supercritical fluids

The solubilities of several low-volatility compounds in supercritical fluids were measured. The fluids used were pure carbon dioxide or carbon dioxide modified with small amounts of organic liquids. Some enthalpies of solution of solids in carbon dioxide at a density of 0.80 g/mL are presented. The enthalpy of solution of fluoranthene in carbon dioxide was found to be less endothermic at higher CO₂ density. The order of solubilities in the modified fluids was the same as that in the pure liquid modifiers. The same apparatus was used to measure vapor pressures of some substances as well as solubilities.     

Adsorption of gases on microporous carbons

A study has been made of the adsorption of nitrogen at ?195 °C, carbon dioxide at 78 °C and 22 °C and sulphur dioxide at 25 °C on a series of microporous active carbons. The amounts adsorbed were measured using conventional gas adsorption apparatus and the heats of adsorption were determined using the flow microcalorimeter.The nitrogen adsorption data were analysed using the three-parameter B.E.T. equation and the porosity interpreted using the V—t plot.It was found that the carbon dioxide isotherms at 22°C obeyed the Dubinin—Polanyi equation and the sulphur dioxide isotherms conformed to the Langmuir equation.The adsorption potentials calculated from the gradient of the Dubinin—Polanyi plots were shown to be in accord with the measured heats of adsorption. Applying the Clausius—Clapeyron equation to the Dubinin—Polanyi plots gave heats of adsorption very similar to the measured values.     

The hydrolysis of soap solutions. II. The solubilities of higher fatty acids

Summary The solubilities of capric, lauric, myristic, palmitic, and stearic acids in water at 25° and 50°C. were determined by use of conductivity measurements. Correction was made for carbon dioxide; and total solubilities, together with the concentration of dissociated and of undissociated acid were calculated. Their solubilities range from 359×10⁻⁶ M for capric acid to 2.1×10⁻⁶ M for stearic acid at 25°C. The solulility of laric and myristic is approximately doubled by an increase of temperature from 25° to 50°C., that of capric, palmitic, and stearic acids increases by 25 to 40%.     

The relationship between chemical structure and reactivity of alberta bitumens and heavy oils

Long residues (424°C +) from Athabasca, Cold Lake, Lloydminster, and Peace River were hydrocracked over a commercial NilMo on y-alumina catalyst at 430°C, 13.9 MPa (2000 psia). The conversion of residue fraction ranged from 55 to 68%, and was correlated with the concentration of carbon bound to aromatic rings in the feeds. Conversions of sulfur, Micro-Carbon Residue, and metals were all highest for Peace River feed, following the same ranking as residue conversion. Estimates for the breakage of carbon-carbon bonds and the uptake of hydrogen were diagnostic in interpreting the reactor performance.     

Design of a micro glass cell apparatus for pure gas‐nonvolatile liquid phase behaviour study

A micro syringe is used as a constant volume cell for gas–liquid equilibrium (GLE) study. The cell is made of glass and has a volume of <100 µL. It can operate at pressures up to 13 MPa and temperatures up to 115°C. Two different experimental procedures are presented for systems with nonvolatile low and high viscosity liquids. A micro magnetic stir bar is used to mix the gas–liquid mixtures inside the cell. Since the internal volume of the cell is small, a short mixing time is sufficient for the gas–liquid mixtures to reach equilibrium. The solubility values are measured by using the pressure decay method. The experimental procedures are validated by measuring the carbon dioxide (CO₂) solubility in water and highly viscous bitumen. The experimental results are in good agreement with the available literature data which shows that the technique works well. © 2011 Canadian Society for Chemical Engineering     

Diffusivity of CO2, CH4, C2H6 and N2 in athabasca bitumen

Experimental data for the diffusivity of carbon dioxide, methane, ethane and nitrogen in Athabasca bitumen are presented in the range 25–90°C at 4 and 8 MPa. The diffusivity of these gases has been determined as a function of gas concentration in bitumen using a non‐intrusive experim?ental method. The diffusivity of gas in general is found to increase with temperature and pressure, and is a unimodal function of concentration. A correlation is provided for the average diffusivity of these gases as a function of temperature.     

Ternary phase equilibria of the iso-propanol+water+carbon dioxide system at high pressure

Ternary phase diagrams are presented for the system: iso-propanol(IPA)+water+carbon dioxide at temperatures from 15 to 70 °C and pressures from 7 to 17 MPa. The distribution coefficients of IPA between the dense phase carbon dioxide and water changed dramatically with temperature and pressure. In the vicinity of the critical point, distribution coefficients was low, yet at liquid-like densities carbon dioxide had a high affinity for IPA. Selectivity reversal was observed at differing pressures. High selectivity of CO₂ for IPA was achieved in the near-critical liquid and in supercritical carbon dioxide at high pressure.     

Absorption of carbon dioxide into aqueous methyldiethanolamine

Gas absorption rates in a laminar liquid jet were measured for carbon dioxide in methyl- diethanolamine (MDEA) solutions. It was found that for the short contact times (<0.012s) of these absorption experiments there is only a small effect of any reaction between carbon dioxide and MDEA. Solubilities and molecular diffusivities for carbon dioxide in aqueous MDEA are estimated from measurements with nitrous oxide. The absorption rate data are described well using the solubilities and diffusivities measured in this work. Solubilities were measured over the temperature range 15 to 35°C and for MDEA concentrations up to 40%. Diffusion coefficients and viscosities were measured over the same temperature range and MDEA concentrations up to 20%.     

Selective carbon monoxide adsorbent composed of polystyrene resin having amino groups and copper(I) chloride

A carbon monoxide adsorbent composed of 10 g of a polystyrene resin having amino groups and 70 mmol of copper(I) chloride was prepared by refluxing the resin and copper(I) chloride in acetonitrile, followed by evaporation of the liquid phase at 5 mmHg, 80°C. The adsorbent rapidly adsorbs 15.9 mmol of carbon monoxide under 1 atm at 20°C. 11.4 mmol of adsorbed carbon monoxide are desorbed when the adsorbent is subjected to a reduced pressure (5 mmHg) at 80°C for 10 min. In the second and the later adsorptions, the amount of adsorbed carbon monoxide is virtually constant at 11.4 mmol. The amount of carbon dioxide adsorbed by the adsorbent under 1 atm at 20°C is 2.8 mmol, and the value for methane is 0.0 mmol. The prepared adsorbent is applicable to selective separation of carbon monoxide from gas mixtures containing both carbon dioxide and methane.     

Solubility of red pepper (C<Emphasis Type="Italic">apsicum annum</Emphasis>) oil in near- and supercritical carbon dioxide and quantification of capsaicin

Red pepper oil was extracted using near- and supercritical carbon dioxide. Extraction was carried out at pressures ranging from 10 to 35 MPa and temperatures from 30 to 60 °C, with a CO₂ flow rate of 24.01 g/min using a semi-continuous high-pressure extraction apparatus. The duration for extraction was 2 h. The highest oil yield was found at high pressure and temperature. The highest solubility of oil (1.18 mg/g of CO₂) was found at 35 MPa and 60 °C. The solubility data of red pepper oil in near- and supercritical CO₂ were fitted in Chrastil model. The fatty acid composition of red pepper oil was analyzed by gas chromatography (GC). Linoleic acid was found to be the major fatty acid in the oil. Capsaicin was quantified in different extracts by high performance liquid chromatography (HPLC). The highest capsaicin yield was found at 35 MPa and 60 °C.     

Effects of Thermal Treatment on Gas Transport Through Porous Silica Membranes

Abstract

The effects of thermal treatment from 180°C to 1150°C on the gas transport properties of porous silica membranes were systematically studied for various gases. The permeance of all gases, except for CO₂, has a maximum at 800°C. The CO₂ permeance was constant from 180°C to 600°C and then decreased monotonically. Membranes thermally treated at 1150°C did not exhibit any gas permeation because of pore collapse. The gas transport behavior follows a combination of Knudsen diffusion and surface diffusion for all gases tested except for carbon dioxide. The permeation of carbon dioxide is strongly affected by capillary condensation. We propose a new transport model composed of two components; that is, the Knudsen diffusion factor, α, and the surface diffusion factor, β. A transition was observed for α and β at around 800–900°C, which is close to the strain point of the membrane. This transition treatment temperature can be correlated with the changes in gas permeance. The model allows qualitative evaluation of gas transport through porous membranes regardless of their actual microporous structures.     

Separation of Phenantrene from Anthracene Oil using Supercritical Carbon Dioxide

Supercritical fluid extraction (SFE) is a relatively new separation technique that has received much attention in recent years. This process is an alternative to distillation or liquid extraction. Its main advantage over the conventional ones is that the dissolved extract may be completely separated from the supercritical fluid simply by decreasing the pressure. In recent years considerable effort has been devoted to the measurement of equilibrium solubility data for solids in supercritical fluids. A coal tar distillate, anthracene oil, which contains 34.46 mass‐% phenanthrene, 33.8 mass‐% anthracene, 13.89 mass‐% carbazole and other impurities, was used as the model mixture. In this study, an experimental flow‐type apparatus has been designed to determine solubility data for the main components of anthracene oil (phenanthrene, anthracene, and carbazole) as a binary, quaternary, and multi component mixture in supercritical carbon dioxide. The equilibrium solubilities were measured at 45 °C isotherm, over a pressure range of 98–200 bar. The separation of phenanthrene from anthracene oil has been also studied by supercritical carbon dioxide at different temperatures and pressure in an extracting vessel containing 27 sieve trays.     

Equilibrium solubility of H2S and CO2 and their mixtures in a mixed solvent

The solubility of hydrogen sulphide, carbon dioxide, and their mixtures has been measured at 40° and 100°C in a mixed solvent consisting of 20.9 wt% MDEA (methyldiethanolamine), 30.5 wt% sulfolane (tetrahydrothiophene-1, 1-dioxide), and 48.6 wt% water. The results have been compared with those for aqueous 2.0 mol/dm³ MDEA and an analogous mixed solvent, containing AMP (2-amino-2-methyl-1-propanol), which are available in the literature. These data were used to modify the solubility model of Deshmukh and Mather (1981) to account for the mixed solvent effects on the system thermodynamics. Results show that the model is useful as a first approximation in predicting acid gas solubilities; agreement with experiment was generally found to be within £15%.