JPH0414653B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" This invention relates to an alcohol separating agent comprising an acetylene alcohol compound. The alcohol separating agent is a compound that, when added to a solution containing alcohol, forms complex crystals with the alcohol in the solution and precipitates, thereby separating the alcohol.

"Prior art" Conventionally, as an acetylene alcohol compound that reacts with alcohol in an alcohol-containing solution such as an ethanol aqueous solution to form a complex compound, 9-(1-propynyl)-9-hydroxyfluorene and 2.5-bis(2.4-dimethylphenyl)hydroquinone represented by Proceedings of the joint conference of the Federation of Academic Societies Research Presentation Meeting and the Autumn Conference of the Chubu Federation of Chemical Associations Branches 2 No.-
1, p. 612, “Special Compounds for Distinguishing Molecules”, Published by the Chemical Society of Japan (1978); Chemistry
Letters, PP.1699-1702 (1983) (published by
the Chemical Society of Japan)].

"Problems to be Solved by the Invention" The properties of the above compound were discovered by the present inventors, and are useful in allowing easy separation of alcohol from a solution containing alcohol. Alcohol separating agents that can easily separate alcohol and are easy to manufacture have a wide range of uses.
Therefore, there is currently a demand for something that has better performance and is cheaper.

"Means for Solving the Problems" Continuing the research and development of the conventional alcohol separating agents mentioned above, the present inventors were further conducting research on this type of alcohol separating agent, and found that an acetyl alcohol-based It has been found that the compound [hereinafter referred to as processed product ()] exhibits good performance as an alcohol separating agent.

That is, the general formula () (In the formula, R ₁ to R ₅ and R ₆ to _{R 10} are hydrogen atoms or lower alkyl groups. However, R ₁ to _{R 5} and R ₆ to
At least one of each of R ₁₀ is a lower alkyl group. ). It is an acetylene alcohol compound.

In the definition of R ₁ -R ₅ and R ₆ -R ₁₀ in the above formula (), the lower alkyl group is a straight or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-
Includes propyl, i-propyl, n-butyl, i-butyl, and the like. From the viewpoint of ease of complex formation with alcohol, stability of the complex, etc., R ₁ is a lower alkyl group, at least one of R ₂ - _{R 4} is a lower alkyl group, R ₅ is a hydrogen atom, and at least one of R ₆ - _{R 10} is a lower alkyl group. one is a lower alkyl group, and at least one of R ₆ and R ₁₀
Particularly preferred are compounds () in which each is a hydrogen atom.

Compound () is the formula () (In the formula, R ₁ - R ₁₀ have the same meanings as above) and a compound (acetylene) represented by the formula () HC≡CH () are reacted in the presence of sodium amide in liquid ammonia. It can be manufactured by Compound()
A small amount of a solvent such as tetrahydrofuran or ethyl ether may be used to dissolve or ().
A suitable reaction temperature is about -40 to -65°C. After the reaction is complete, ammonia is evaporated and neutralized with a mineral acid such as hydrochloric acid to form a compound such as ethyl ether ().
Compound () can be obtained by extracting with a solvent that dissolves but has poor compatibility with water and distilling off the solvent of the extract.

Compound () forms a complex with alcohol in a solution containing various alcohols, and this complex generally has low solubility in water and precipitates as crystals. When this is separated into solid and liquid, washed and dried and then heated, alcohol is liberated and pure alcohol or extremely pure alcohol can be obtained. And the remaining solid is a compound (),
Can be reused.

The alcohols mentioned above include lower alkanols, aliphatic unsaturated alcohols (allyl alcohol, crotyl alcohol, propargyl alcohol, etc.),
Includes alicyclic alcohols (cyclopentanol, cyclohexanol, etc.), aromatic alcohols (benzyl alcohol, cinnamyl alcohol, etc.), heterocyclic alcohols (furfuryl alcohol, etc.), lower alkylene glycols, and the like. The above lower alkanol is a linear or branched alkanol having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, n
-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, n-
Includes hexanol and the like. Lower alkylene glycols include linear or branched alkylene glycols having 1 to 6 carbon atoms, such as ethylene glycol, 1,3-propanediol, propylene glycol, 1,3-butanediol, 1,4-butanediol, etc. include.

The concentration of alcohol in the alcohol-containing solution that is brought into contact with the compound () is not particularly limited, but it is usually 5% or more, particularly 30% or more. Solutions containing alcohol also include alcoholic fermentation broths, reaction solutions for alcohol synthesis, and the like.

Although the contacting method may be to simply throw the compound () into a solution containing alcohol, it is generally more efficient to dissolve or melt the compound by heating if necessary. Alternatively, the compound () may be dissolved in a small amount of a solvent such as ether, and then mixed with a solution containing alcohol.

After contact, the mixture is usually left at room temperature or further cooled to precipitate complex crystals with a ratio of alcohol to hydroxyl groups of 1:1, which undergoes solid-liquid separation and releases alcohol when heated. The heating temperature may normally be higher than the boiling point of the alcohol.

"Effect" Compound () generally has good stability as a complex with alcohol, and there is little or very little loss during drying after filtration. Therefore, according to this compound (), alcohol in a solution containing an extremely high proportion of alcohol can be separated and recovered.

Next, the present invention will be explained in more detail with reference to Examples.

"Example" Add Na (49 g) to liquid ammonia (1.5) containing Fe (NO ₃ ) ₃ 9H ₂ O (0.5 g) to prepare sodium amide (NaNH ₂ ), and cool to -40°C to -65°C. and add acetylene gas (500 ml) while stirring.
ml/min) for about 1 hour. Then the above ()
A solution of 2,2'4,4'-tetramethylbenzophenone (380 g) in anhydrous tetrahydrofuran (300 ml) was gradually added and stirred for about 1 hour. After leaving this at room temperature overnight to evaporate the ammonia, add 300 ml of dilute hydrochloric acid (3N-HCl), and mix this with ether (300 ml).
ml). After washing this ether layer with water and drying, the ether was distilled off, leaving a colorless oil. When petroleum ether (300 ml) was added to this, colorless needle crystals were obtained. When this was identified by IR (Nujol method), it was found that 1,1-bis (2,4-dimethyl
phenyl)-2-propyn-1-ol [formula ()] (line A in the figure). Yield 350g, melting point
61-63℃.

4.0g of this compound and 1.1ml of 80% ethyl alcohol
was added and heated to dissolve, and then left at room temperature for 2 hours.
Complex crystals with a molar ratio of 1 were precipitated. The formation of a complex with ethyl alcohol is shown in the crystal below.
This could be confirmed by IR (Nujol method) (line B in the figure).

The complex crystals were collected by filtration and dried under reduced pressure (200 mmHg,
After heating at room temperature for 30 minutes, colorless prismatic crystals (4.6 g, melting point 40-48°C) were obtained. When this complex crystal (4.6g) was heated at about 100℃ for 10 minutes,
0.56 g of ethyl alcohol was obtained. Therefore,
The alcohol recovery rate using the above alcohol separation agent is
It was 81%.

The above IR identification is based on "Structure Determination of Organic Compounds", Sankyo Publishing, written by Fuzo Toda, November 1971.
This was done based on the issue published on the 25th.

[Brief explanation of drawings]

This figure shows an IR spectrum of an alcohol separating agent (acetylene alcohol compound) of one embodiment of the present invention and a complex formed by this compound with ethyl alcohol.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ to R ₅ and R ₆ to _{R 10} are hydrogen atoms or lower alkyl groups. However, R ₁ to _{R 5} and R ₆ to
At least one of each of R ₁₀ is a lower alkyl group. ) An alcohol separating agent consisting of an acetylene alcohol compound represented by 2 R ₁ is a lower alkyl group, at least one of R ₂ to _{R 4} is a lower alkyl group, R ₅ is a hydrogen atom, R ₆ to _{R 10}
The alcohol separating agent according to claim 1, wherein at least one of R ₆ or R ₁₀ is a lower alkyl group, and at least one of R 6 or R 10 is a hydrogen atom.