Separation butanol

Alternative 3. Figure 5.19 presents a process flow sheet. The reactor feed is a mixture of cmde TBP as the diluent, POCI3 and an excess of butanol to consume POCI3 completely in a single pass. The reactor exit stream is then subjected to two flash distillations, under vacuum if required. The first is to recover HCl and the other is to separate butanol from the TBP. An SDR with a provision for heating could be used in place of flash distillation. The HCl could... 

Figure 6.16. Trajectories of heteroazeotropic distiUation (a) distillate from azeocolumn to decanter for separation toluene(l)-ethanol(2)-water(3) mixture (b) distillate from azeocolumn to decanter and a recycle stream of the entrainer from decanter to azeocolumn for separation benzene(l)-isopropanol(2)-water(3) mixture (c) distillate from azeostripping to decanter and a recycle stream of the entrainer from decanter to azeostripping for separation benzene(l)-isopropanol(2)-water(3) mixture (d) distillate from azeocolumn to decanter and a recycle stream of the entrainer from decanter to azeocolumn for separation acetic add(l)-n-butyl acetate (2)-water(3) mixture (e) bottom from azeocolumn to decanter for separation butanol(l)-acetone(2)-water(3) mixture and (f) side product from azeocolumn to decanter for separation butanol(l)-acetone(2)-water(3) mixture. Regions of two liquid phases Regi,i 1,2 are shaded.

Divide the saturated solution of n-butyl alcohol in water into three approximately equal parts. Treat these respectively with about 2-5 g. of sodium chloride, potassium carbonate and sodium hydroxide, and shake each until the soli have dissolved. Observe the effect of these compounds upon the solubility of n-butanol in water. These results illustrate the phenomenon of salting out of organic compounds, t.e., the decrease of solubility of organic compounds in water when the solution is saturated with an inorganic compound. The alcohol layer which separates is actually a saturated solution of water in n-butyl alcohol. 

Isobutyl alcohol [78-83-1] forms a substantial fraction of the butanols produced by higher alcohol synthesis over modified copper—zinc oxide-based catalysts. Conceivably, separation of this alcohol and dehydration affords an alternative route to isobutjiene [115-11 -7] for methyl /-butyl ether [1624-04-4] (MTBE) production. MTBE is a rapidly growing constituent of reformulated gasoline, but its growth is likely to be limited by available suppHes of isobutylene. Thus higher alcohol synthesis provides a process capable of supplying all of the raw materials required for manufacture of this key fuel oxygenate (24) (see Ethers). 

Purified DBO is mixed with the mother Hquor from the oxaUc acid crystaUi2ation, and hydroly2ed at about 80°C into oxaUc acid and / -butanol. The resultant mixture undergoes phase separation oxaUc acid dihydrate is thus crystaUi2ed from the oxaUc acid solution, and C H OH is purified and recycled to the circulating solution. 

Fusel Oils. The original source of amyl alcohols was from fusel oil which is a by-product of the ethyl alcohol fermentation industry. Refined amyl alcohol from this source, after chemical treatment and distillation, contains about 85% 3-methyl-1-butanol and about 15% 2-methyl-1-butanol, both primary amyl alcohols. Only minor quantities of amyl alcohol are suppHed from this source today. A German patent discloses a distillative separation process for recovering 3-methyl-1-butanol from fusel oil (93). 

However, for the past 30 years fractional separation has been the basis for most asphalt composition analysis (Fig. 10). The separation methods that have been used divide asphalt into operationally defined fractions. Four types of asphalt separation procedures are now in use ( /) chemical precipitation in which / -pentane separation of asphaltenes is foUowed by chemical precipitation of other fractions with sulfuric acid of increasing concentration (ASTM D2006) (2) solvent fractionation separation of an "asphaltene" fraction by the use of 1-butanol foUowed by dissolution of the 1-butanol solubles in... 

The principal commercial source of 1-butanol is -butyraldehyde [123-72-8] obtained from the Oxo reaction of propylene. A mixture of n- and isobutyraldehyde [78-84-2] is obtained in this process this mixture is either separated initially and the individual aldehyde isomers hydrogenated, or the mixture of isomeric aldehydes is hydrogenated direcdy and the n- and isobutyl alcohol product mix separated by distillation. Typically, the hydrogenation is carried out in the vapor phase over a heterogeneous catalyst. For example, passing a mixture of n- and isobutyraldehyde with 60 40 H2 N2 over a CuO—ZnO—NiO catalyst at 25—196°C and 0.7 MPa proceeds in 99.95% efficiency to the corresponding alcohols at 98.6% conversion (7,8) (see Butyraldehydes Oxo process). 

Almost 40 years later the Lummus Co. patented an integrated process involving the addition of chlorine along with the sodium chloride and sodium hydroxide from the cathode side of an electrolytic cell to a tertiary alcohol such as tertiary butanol to produce the tertiary alkyl hypochlorite. The hypochlorite phase separates, and the aqueous brine solution is returned to the electrolytic cells. The alkyl hypochlorite reacts with an olefin in the presence of water to produce a chlorohydrin and the tertiary alcohol, which is returned to the chlorinator. With propylene, a selectivity to the chlorohydrin of better than 96% is reported (52). A series of other patents covering this technology appeared during the 1980s (53—56). 

An example of heterogeneous-azeotrope formation is shown in Fig. 13-13 for the water-normal butanol system at 101.3 kPa. At liquid compositions between 0 and 3 mole percent butanol and between 40 and 100 mole percent butanol, the liquid phase is homogeneous. Phase sphtting into two separate liquid phases (one with 3 mole percent butanol and the other with 40 mole percent butanol) occurs for any overall hquid composition between 3 and 40 mole percent butanol. A miuimum-boihug heterogeneous azeotrope occurs at 92°C (198°F) when the vapor composition and the over l composition of the two liquid phases are 75 mole percent butanol. 

The simplest case of combining T E and LLE is the separation of a binaiy heterogeneous azeotropic mixture. One example is the dehydration of 1-butanol, a self-entraining system, in which butanol (117.7°C) and water form a minimum-boiling heterogeneous azeotrope (93.0°C). As shown in Fig. 13-69, the fresh feed may be added... 

In the last few years, Idemitsu commercialized a 5000 metric ton/year integrated reaction and separation process in SCR isobutene, as shown in Rig. 22-24. The reaction of isobutene and water takes place in the water phase and is acid catalyzed. The product, sec-butanol, is extracted into the isobutene phase to drive the reversible reaction to the right. The. s c-butanol is then recovered from the isobutene by depressurizing the SCR phase, and the isobutene is recompressed and recycled. 

The effect of concentration of cationic (cetylpyridinium chloride, CPC), anionic (sodium dodecylsulfate, SDS) and nonionic (Twin-80) surfactants as well as effect of pH value on the characteristics of TLC separ ation has been investigated. The best separ ation of three components has been achieved with 210 M CPC and LIO M Twin-80 solutions, at pH 7 (phosphate buffer). Individual solution of SDS didn t provide effective separation of caffeine, theophylline, theobromine, the rate of separ ation was low. The separ ation factor and rate of separ ation was increase by adding of modifiers - alcohol 1- propanol (6 % vol.) or 1-butanol (0.1 % vol.) in SDS solution. The optimal concentration of SDS is 210 M. 

Sulfonamides (R2NSO2R ) are prepared from an amine and sulfonyl chloride in the presence of pyridine or aqueous base. The sulfonamide is one of the most stable nitrogen protective groups. Arylsulfonamides are stable to alkaline hydrolysis, and to catalytic reduction they are cleaved by Na/NH3, Na/butanol, sodium naphthalenide, or sodium anthracenide, and by refluxing in acid (48% HBr/cat. phenol). Sulfonamides of less basic amines such as pyrroles and indoles are much easier to cleave than are those of the more basic alkyl amines. In fact, sulfonamides of the less basic amines (pyrroles, indoles, and imidazoles) can be cleaved by basic hydrolysis, which is almost impossible for the alkyl amines. Because of the inherent differences between the aromatic — NH group and simple aliphatic amines, the protection of these compounds (pyrroles, indoles, and imidazoles) will be described in a separate section. One appealing proj>erty of sulfonamides is that the derivatives are more crystalline than amides or carbamates. 

The submitters purchased 2-chloro-2-methylbutane from Eastman Kodak Company. The checkers prepared the halide as follows. A separatory funnel was charged with 21.5 mL (0.2 mol) of 2-methyl-2-butanol and IQO mL of coned hydrochloric acid. The mixture was shaken vigorously with periodic venting for 10 min. The layers were separated and the 2-chloro-2-methylbutane layer (upper) was washed several times with equal volumes of cold water. The product was dried over calcium chloride and distilled, bp 85 C. 

The phenol (Imol) in 5% aqueous NaOH is treated (while cooling) with benzoyl chloride (Imol) and the mixture is stirred in an ice bath until separation of the solid benzoyl derivative is complete. The derivative is filtered off, washed with alkali, then water, and dried (in a vacuum desiccator over NaOH). It is recrystalUsed from ethanol or dilute aqueous ethanol. The benzoylation can also be carried out in dry pyridine at low temperature ca 0°) instead of in NaOH solution, finally pouring the mixture into water and collecting the solid as above. The ester is hydrolysed by refluxing in an alcohol (for example, ethanol, n-butanol) containing two or three equivalents of the alkoxide of the corresponding alcohol (for example sodium ethoxide or sodium n-butoxide) and a few ca 5-10) millilitres of water, for half an hour to three hours. When hydrolysis is complete, an aliquot will remain clear on dilution with four to five times its volume of water. Most of the solvent is distilled off. The residue is diluted with cold water and acidified, and the phenol is steam distilled. The latter is collected from the distillate, dried and either fractionally distilled or recrystalUsed. 

Absorption is widely used as a raw material and/or product recovery technique in separation and purification of gaseous streams containing high concentrations of VOC, especially water-soluble compounds such as methanol, ethanol, isopropanol, butanol, acetone, and formaldehyde. Hydrophobic VOC can be absorbed using an amphiphilic block copolymer dissolved in water. However, as an emission control... 

It has a water solubility of about 55%. It may ba compounded in the form of tablets, for oral administration, or may be prepared in solution for distribution in ampoules. For tha manufacture of solutions for packaging in ampoules. It is more convenient to simply dissolve tha theophylline and tha butanol amine in water, without going through the intermediate step of separating the crystalline salt. 

The oil precipitates and is crystallized after a time. The crystals are separated and dried under vacuum. The pipecolyl-2,6-xylidide produced is alkylated by boiling for 10-20 hours with 0.6 part n-butylbromide in an n-butanol solution in the presence of 0.5 part potassium carbonate. The potassium carbonate Is filtered off and the butanol is distilled off in vacuum. The residue is dissolved In diluted hydrochloric acid and carbon treated, after which the base is precipitated with sodium hydroxide in the form of white crystals, which are filtered off and washed with water. The base obtained, which consists of N-n-butyl-plpecolyl-2,6-xylidide is sufficiently pure for the production of salts. 

The mixture was filtered, the ethyl acetate layer separated and washed with three 100 ml portions of water, dried over Na2S04, filtered and treated with 30 ml of sodium 2-ethyl-hexanoate in n-butanol (34 ml = 0.1 mol). The oil which settled out was scratched to induce crystallization. After stirring for 20 minutes the product, sodium 7-(a-bromoacet-amido)cephalosporanate, was scraped from the sides of the flask and collected. The filter cake was washed with several portions of acetone, air dried, and dried in vacuo over P Os. The yield was 22.5 g and decomposed at 193°C. 

The final purification consists of chromatographic separation of thyroxine and triiodo thyronine on a kieselguhr column using 20% chloroform in n-butanol equilibrated with... 

To make the hydrochloride salt, the bisacetamide or, by another name, 1,11-diphenyl-2,2,3,9,10,10-hexamethyl-4 3hydroxy ethyl )-3,6,9-triazaundecane is dissolved In n-butanol. The solution is chilled and then dry hydrogen chloride gas is passed into the solution causing an oil to separate. To the heavy oil ether is added and then stirred causing crystallization to occur. MP146°Cto 147°C. Analysis for nitrogen calc. 8.3%, found 8.2%. 

Sodium (9.6 parts) was dissolved in butanol (192 parts) and di-n-butyl ethyl 1 -methyl-n-butylmalonate (62,B parts) and urea (14.4 parts) were added to the warm solution with agitation. The mixture was then heated to reflux temperature in three quarters of an hour and maintained for 2 hours. The reaction mass was kept, water (150 parts) added, the aqueous portion separated, and the butanol layer extracted with water (3 x 50 parts). The combined aqueous extracts were then given 3 small extractions with benzene, the aqueous liquors separated, charcoaled,filtered and precipitated with concentrated hydrochloric acid (acid to congo-paper). The solid was collected, washed with water, dissolved in N-sodium hydroxide and reprecipitated with carbon dioxide. On recrystallization, from aqueous alcohol, the pentobarbitone was obtained. 

To this acid was then added 1 g of 4-ethyl-2,3-dioxo-1-piperazinocarbonyl chloride (from the reaction of N-ethylethylenediamine and diethyl oxalate to give 2,3-dioxo-4-ethyl-piperazine which Is then reacted with phosgene) and the resulting mixture was reacted at 15°C to 20°C for 2 hours. After the reaction, a deposited triethylamine hydrochloride was separated by filtration, and the filtrate was incorporated with 0.4 g of n-butanol to deposit crystals. The deposited crystals were collected by filtration to obtain 1.25 g of white crystals of 6-[ D(—l-Ct-(4-ethyl-2,3-dioxo-1 -piperazinocarbonylaminolphenylacetamido] penicillanic acid. Into a solution of these crystals in 30 ml of tetrahydrofuran was dropped a solution of 0.38 g of a sodium salt of 2-ethyl-hexanoic acid in 10 ml of tetrahydrofuran, upon which white crystals were deposited. The deposited crystals were collected by filtration, sufficiently washed with tetrahydrofuran and then dried to obtain 1.25 g of sodium salt of 6-[D(—)-a-(4-ethyl-2,3-di-0X0-1-piperazinocarbonylaminolphenylacetamido] penicillanic acid, melting point 183°C to 185°C (decomposition), yield 90%. 

Preparation of 5-(3-Methylaminopropyl)-5H-Dibenzo[a,d]Cycloheptene from 5-[3-(N-Formyl-N-Methylj-Aminopropyl]SH-Dibenzo[a/i]Cycloheptene 29.5 grams of 5-[3-(N-formyl-N-methyD-aminoprOpyl] -5H-dibenzo[a,d] cycloheptene is refluxed for 24 hours under nitrogen in a solution of 36.3 grams of potassium hydroxide in 378 ml of n-butanol. After cooling to room temperature, the solvent Is evaporated in vacuo, the residue is stirred with 200 ml of water, 300 ml of n-hexane, the layers separated, the water layer extracted with 100 ml of n-hexane and the combined hexane layers washed with water (2 x 100 ml) and then with... 

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