Distillation from other solvents

Many alkaloids may be only sparingly soluble in ether but, with the exception of pentane and hexane, their purification is more readily effected from this solvent than from any other. It is possible to prepare ether solutions of these bases of a concentration far in excess of their equilibrium value which then often yield a crystalline solid in reattaining a state of equilibrium. A supersaturated ethereal solution of these bases is readily prepared as follows The relatively dilute aqueous acid solution of the alkaloids, in a separatory funnel, is covered with a layer of ether, and a layer of water interposed between the two layers by the cautious addition of water down the side of the funnel. Aqueous ammonia is run in, in a like manner, the stopper inserted in the funnel, and the mixture shaken very vigorously. Often the more insoluble alkaloids will crystallize from the ether layer before it can be separated. In any case the wet turbid ethereal solution can be brought to brilliant clarity by treatment with charcoal. Removal of the ether leaves a residue which is now amenable to fractional crystallization from other solvents, to fractional distillation, or to salt formation. 

Beckmann rearrangement of benzophenone oxime to benz-anilide. Dissolve 2 g. of benzophenone oxime in 20 ml. of anhydrous ether in a small conical flask and add 3 g. of powdered phosphorus pentachloride (or 3 ml. of pure tbionyl chloride). Distil off the solvent and other volatile products on a water bath CAUTION ether), add 25 ml. of water, boil for several minutes and break up any lumps which may be formed. Decant the supernatant liquid, and recrystallise, in the same vessel, from boiling alcohol. The product is benzanilide, m.p. 163° confirm this by a mixed m.p. determination with an authentic specimen. 

The component C in the separated extract from the stage contact shown in Eigure 1 may be separated from the solvent B by distillation (qv), evaporation (qv), or other means, allowing solvent B to be reused for further extraction. Alternatively, the extract can be subjected to back-extraction (stripping) with solvent A under different conditions, eg, a different temperature again, the stripped solvent B can be reused for further extraction. Solvent recovery (qv) is an important factor in the economics of industrial extraction processes. 

Butadiene Separation. Solvent extraction is used in the separation of butadiene (qv) [106-99-0] from other C-4 hydrocarbons in the manufacture of synthetic mbber. The butadiene is produced by catalytic dehydrogenation of butylene and the Hquid product is then extracted using an aqueous cuprammonium acetate solution with which the butadiene reacts to form a complex. Butadiene is then recovered by stripping from the extract. Distillation is a competing process. 

Manufacture. Cyanoacetic acid and cyanoacetates are iadustrially produced by the same route as the malonates starting from a sodium chloroacetate solution via a sodium cyanoacetate solution. Cyanoacetic acid is obtained by acidification of the sodium cyanoacetate solution followed by organic solvent extraction and evaporation. Cyanoacetates are obtained by acidification of the sodium cyanoacetate solution and subsequent esterification with the water formed being distilled off. Other processes reported ia the Hterature iavolve the oxidation of partially oxidized propionittile [107-12-0] (59). Higher esters of cyanoacetic acid are usually made through transesterification of methyl cyanoacetate ia the presence of alumiaiumisopropoxide [555-31-7] as a catalyst (60). 

Some alkylphenols in commercial production have low vapor pressures and/or low thermal decomposition temperatures. Eor these products, the economics of distillation are poor and other recovery processes are used. Crystallisation from a solvent is the most common nondistUlation method for the purification of these alkylphenols. 

Analytical Techniques. Sorbic acid and potassium sorbate are assayed titrimetricaHy (51). The quantitative analysis of sorbic acid in food or beverages, which may require solvent extraction or steam distillation (52,53), employs various techniques. The two classical methods are both spectrophotometric (54—56). In the ultraviolet method, the prepared sample is acidified and the sorbic acid is measured at 250 260 nm. In the colorimetric method, the sorbic acid in the prepared sample is oxidized and then reacts with thiobarbituric acid the complex is measured at - 530 nm. Chromatographic techniques are also used for the analysis of sorbic acid. High pressure Hquid chromatography with ultraviolet detection is used to separate and quantify sorbic acid from other ultraviolet-absorbing species (57—59). Sorbic acid in food extracts is deterrnined by gas chromatography with flame ionization detection (60—62). 

Economic considerations in the 1990s favor recovering butadiene from by-products in the manufacture of ethylene. Butadiene is a by-product in the C4 streams from the cracking process. Depending on the feedstocks used in the production of ethylene, the yield of butadiene varies. Eor use in polymerization, the butadiene must be purified to 994-%. Cmde butadiene is separated from C and C components by distillation. Separation of butadiene from other C constituents is accomplished by salt complexing/solvent extraction. Among the solvents used commercially are acetonitrile, dimethyl acetamide, dimethylform amide, and /V-methylpyrrolidinone (13). Based on the available cmde C streams, the worldwide forecasted production is as follows 1995, 6,712,000 1996, 6,939,000 1997, 7,166,000 and 1998, 7,483,000 metric tons (14). As of January 1996, the 1995 actual total was 6,637,000 t. 

Separation and Purification. Separation and purification of butadiene from other components is dominated commercially by the extractive distillation process. The most commonly used solvents are acetonitrile and dimethylformarnide. Dimethylacetamide, furfural, and... 

Pharmaceuticals. Pharmaceuticals account for 6% of the Hquid-phase activated carbon consumption (74). Many antibiotics, vitarnins, and steroids are isolated from fermentation broths by adsorption onto carbon foUowed by solvent extraction and distillation (82). Other uses in pharmaceutical production include process water purification and removal of impurities from intravenous solutions prior to packaging (83). 

Black, viscous residuum direc tly from the still at 410 K (390°F) or higher serves as fuel in nearby furnaces or may be cooled and blended to make commercial fuels. Diluted with 5 to 20 percent distillate, the blend is No. 6 fuel oil. With 20 to 50 percent distillate, it becomes No. 4 and No. 5 fuel oils for commercial use, as in schools and apartment houses. Distillate-residual blends also serve as diesel fuel in large stationaiy and marine engines. However, distillates with inadequate solvent power will precipitate asphaltenes and other high-molecular-... 

Solvents are recovered from the oil stream through distillation and steam stripping in a fractionator. The stream extracted from the solvent contains high concentrations of hydrogen sulfide, aromatics, naphthenes and other hydrocarbons, and is often fed to the hydrocracking unit. 

As a general procedure, a mixture of the steroidal ketone (50 mg) and lithium aluminum deuteride (20 mg) in dry ether (5 ml, freshly distilled from lithium aluminum hydride) is heated under reflux until the reduction is complete according to thin layer chromatography test. The excess deuteride is then decomposed by the careful addition of a few drops of water and the reaction mixture is worked up by the usual procedure. For hindered ketones or esters the use of other solvents, such as tetrahydrofuran or dioxane, may be preferable to allow higher reaction temperatures. 

Liquid solvents are used to extract either desirable or undesirable compounds from a liquid mixture. Solvent extraction processes use a liquid solvent that has a high solvolytic power for certain compounds in the feed mixture. For example, ethylene glycol has a greater affinity for aromatic hydrocarbons and extracts them preferentially from a reformate mixture (a liquid paraffinic and aromatic product from catalytic reforming). The raffinate, which is mainly paraffins, is freed from traces of ethylene glycol by distillation. Other solvents that could be used for this purpose are liquid sulfur dioxide and sulfolane (tetramethylene sulfone). 

Following the same procedures described in the above-mentioned study, additional extractive data were obtained for the epoxy phenolic enamel that was irradiated at 4.7-7.1 Mrad at 25 and — 30 °C in the presence of distilled water, 3% acetic acid, and n-heptane. The changes in the amount of extractives resulting from the irradiation treatment are shown in Table IX. In the case of the water and acetic acid extractives, there was no change in either the chloroform-soluble fractions or the chloroform-insoluble fractions. In the case of the n-heptane extractives, the amount of extractives decreased when the irradiation temperature was reduced from +25 to — 30°C. Infrared spectra of the chloroform-soluble residues from the water and acetic acid extractives of the unirradiated and irradiated enamel were identical to the chloroform-soluble residues from the solvent blanks. In other words, the epoxy phenolic... 

The submitters used THF that was freshly distilled over Na/K alloy NMP was distilled over CaH2. The checkers used commercially available anhydrous THF and NMP obtained from Aldrich Chemical Co. There appears to be a slight increase in yield when THF distilled from sodium/benzophenone ketyl is used instead of the commercial THF. All other solvents used were of reagent grade quality and were used without further purification. 

All other reagents and solvents were obtained from Kodak Laboratory Chemicals. All monomers were purified by distillation under an inert atmosphere. They were distilled from and collected over 3 A molecular sieves just prior to the polymerizations (11). TMSI was distilled under an inert atmosphere and stored over copper powder. 

The cooled reaction mixture is separated in a separatory funnel, and the aqueous phase is extracted with three 50-ml. portions of benzene. These extracts are combined with each other but kept separate from the original organic phase each wash solution is used first with the original organic phase, then the extracts. The washes are 150 ml. of water (Note 4), 100 ml. of 10% sodium carbonate solution, 100 ml. of water, and finally 50 ml. of saturated sodium chloride solution (Note 5). Solvent is distilled from the combined extracts, and the residue is distilled at reduced pressure in a Claisen flask. The yield of a-tetralone, b.p. 135-137°/15 mm., 1.5671-1.5672, is 75-80 g. (85-91%). 

Solvents. water was doubly-distilled from an all-Pyrex apparatus. All the other solvents were supplied by BDH and mostly used as supplied, except that tetrahydrofuran (THF) was first distilled from lithium "aluminium hydride and then from a sodium/naphthalene mixture (the green coloration of the latter being indicative of the absence of water). 

The petroleum ether solvents are a specific-boiling-range naphtha, as is ligroin. Thus, the term petroleum solvent describes a special liquid hydrocarbon fraction obtained from naphtha and used in industrial processes and formulations (Weissermel and Arpe, 1978). These fractions are also referred to as industrial naphtha. Other solvents include white spirit, which is subdivided into industrial spirit [distilling between 30 and 200°C (86 to 392°F)] and white spirit [light oil with a distillation range of 135 to 200°C (275 to 392°F)]. The special value of naphtha as a solvent lies in its stability and purity. 

There is an alternate process for recovering toluene from the reformate stream called azeotropic distillation. It also can be used to split toluene from the other hydrocarbons that have boiling points near toluene. Azeotropic distillation is like solvent extraction with an extra twist. The process can be more efficient than extraction when the toluene concentration is high. 

Tetrahydrofuran (THE) and oxepane (OXP) were distilled from CaH2 prior to use. All other reagents and solvents are commercially available in reagent grade purity and were used without further purification. 

---