Supercritical carbon dioxid

Fig. 3. Effect of using either liquid or supercritical carbon dioxide on the textural properties of titania aerogels calcined at the temperatures shown. (—), dried with Hquid carbon dioxide at 6 MPa and 283 K (-------), dried with supercritical carbon dioxide at 30 MPa and 323 K. Reproduced from Ref. 36.

Natural Products. Various methods have been and continue to be employed to obtain useful materials from various parts of plants. Essences from plants are obtained by distillation (often with steam), direct expression (pressing), collection of exudates, enfleurage (extraction with fats or oils), and solvent extraction. Solvents used include typical chemical solvents such as alcohols and hydrocarbons. Liquid (supercritical) carbon dioxide has come into commercial use in the 1990s as an extractant to produce perfume materials. The principal forms of natural perfume ingredients are defined as follows the methods used to prepare them are described in somewhat general terms because they vary for each product and suppHer. This is a part of the industry that is governed as much by art as by science. 

Conventional nitrocellulose lacquer finishing leads to the emission of large quantities of solvents into the atmosphere. An ingeneous approach to reducing VOC emissions is the use of supercritical carbon dioxide as a component of the solvent mixture (172). The critical temperature and pressure of CO2 are 31.3°C and 7.4 MPa (72.9 atm), respectively. Below that temperature and above that pressure, CO2 is a supercritical fluid. It has been found that under these conditions, the solvency properties of CO2 ate similar to aromatic hydrocarbons (see Supercritical fluids). The coating is shipped in a concentrated form, then metered with supercritical CO2 into a proportioning airless spray gun system in such a ratio as to reduce the viscosity to the level needed for proper atomization. VOC emission reductions of 50% or more are projected. 

FIG. 22-22 Schematic diagram of the Kraft process for producing decaffeinated coffee using supercritical carbon dioxide (McHugh and Ktukonis, op. cit.). 

THE EFFECT OF PROTON-DONATING MODEFIER ON THE SOLUBILITY ENHANCEMENT OF TRIS(p-DIKETONATO) CHROMIUM(HI) IN SUPERCRITICAL CARBON DIOXIDE... 

Attention should be drawn to a very interesting possibility, viz subjecting drugs before their use as teas to pressure, followed by rapid release of the pressure (so-called PEX procedure), in order to achieve a kind of opening up and thereby improving the liberation of many constituents during the preparation of the tea. The use of supercritical carbon dioxide in this connection is particularly suitable [8]. 

The combination of ionic liquids with supercritical carbon dioxide is an attractive approach, as these solvents present complementary properties (volatility, polarity scale.). Compressed CO2 dissolves quite well in ionic liquid, but ionic liquids do not dissolve in CO2. It decreases the viscosity of ionic liquids, thus facilitating mass transfer during catalysis. The separation of the products in solvent-free form can be effective and the CO2 can be recycled by recompressing it back into the reactor. Continuous flow catalytic systems based on the combination of these two solvents have been reported [19]. This concept is developed in more detail in Section 5.4. 

Above the critical temperature and pressure, a substance is referred to as a supercritical fluid. Such fluids have unusual solvent properties that have led to many practical applications. Supercritical carbon dioxide is used most commonly because it is cheap, nontoxic, and relatively easy to liquefy (critical T = 31°C, P = 73 atm). It was first used more than 20 years ago to extract caffeine from coffee dichloromethane, CH2C12, long used for this purpose, is both a narcotic and a potential carcinogen. Today more than 10s metric tons of decaf coffee are made annually using supercritical C02. It is also used on a large scale to extract nicotine from tobacco and various objectionable impurities from the hops used to make beer. 

The dense fluid that exists above the critical temperature and pressure of a substance is called a supercritical fluid. It may be so dense that, although it is formally a gas, it is as dense as a liquid phase and can act as a solvent for liquids and solids. Supercritical carbon dioxide, for instance, can dissolve organic compounds. It is used to remove caffeine from coffee beans, to separate drugs from biological fluids for later analysis, and to extract perfumes from flowers and phytochemicals from herbs. The use of supercritical carbon dioxide avoids contamination with potentially harmful solvents and allows rapid extraction on account of the high mobility of the molecules through the fluid. Supercritical hydrocarbons are used to dissolve coal and separate it from ash, and they have been proposed for extracting oil from oil-rich tar sands. 

In some cases, the solids themselves are subjected to extraction by a solvent. For example, in one process used to decaffeinate coffee, the coffee beans are mixed with activated charcoal and a high-pressure stream of supercritical carbon dioxide (carbon dioxide at high pressure and above its critical temperature) is passed over them at approximately 90°C. A supercritical solvent is a highly mobile fluid with a very low viscosity. The carbon dioxide removes the soluble caffeine preferentially without extracting the flavoring agents and evaporates without leaving a harmful residue. 

Diels-Alder Reaction in Supercritical Carbon Dioxide (sc-COi)... 

POLYCAPROLACTONEINTO REPOLYMERIZABLE OLIGOMERS IN SUPERCRITICAL CARBON DIOXIDE... 

Details are given of the enzymatic transformation of polycaprolactone into repolymerisable oligomers in supercritical carbon dioxide. The object was to establish a sustainable chemical recycling system for polycaprolactone. 14 refs. 

Leitner W (1999) Reactions in Supercritical Carbon Dioxide (SCCO2). 206 107-132... 

Among the SCFs, supercritical carbon dioxide (SCCO2) provides additional benefits [73], since it is environmentally benign, inexpensive, available in large quantities, nonflammable, and exhibits low toxicity. Its critical pressure is relatively low (73.4 bar) and it has an ambient critical temperature (31.3 °C). CO2 can be easily removed from reaction mixtures by depressurization [74]. 

Studies of reversed micelles dispersed in supercritical fluids have shown their ability to solubihze hydrophihc substances, including biomolecules and dyes, opening the door to many new applications [60,61]. In particular, solutions of reversed micelles in liquid and supercritical carbon dioxide have been suggested as novel media for processes generating a minimum amount of waste and with a low energy requirement [62]. 

Discuss the advantages and disadvantages of using supercritical carbon dioxide and water as solvents in place of organic solvents. 

Polymerization of methyl methacrylate in supercritical carbon dioxide with PDMS based stabilizers A study on the effect of stabilizer anchor groups... 

---