JPH02109987A - Method for refining sorbic acid - Google Patents

Abstract

PURPOSE:To make it possible to efficiently obtain sorbic acid by subjecting a sorbic acid-containing aqueous liquid to solvent extraction using at least one kind of aliphatic hydrocarbon, aromatic hydrocarbon, halogen-containing hydrocarbon, ketones and ethers. CONSTITUTION:A culture medium in which a microorganism such as Mycobacterium rhodochrous is cultured or a system dispersing a microorganism collected from the medium into water, common salt water, buffer, etc., is subjected to oxidation reaction by a method, e.g., adding an aqueous liquid containing sorbic acid thereto to provide sorbic acid-containing aqueous liquid, which is then controlled to pH<=4 and subjected to solvent extraction with a solvent such as toluene. Sorbic aid is crystallized by distilling the solvent from the above-mentioned solution, Therefore, the liquid containing the crystal is preferably filtered according to an ordinary method. The crystal of the resultant sorbic acid can be directly sufficiently produced. Thereby sorbic acid can efficiently be isolated from the sorbic acid-containing aqueous liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for isolating nucleic acids from an aqueous solution containing sorbic acid obtained by microbiologically oxidizing sorbaldehyde.

[Prior art] Sorbic acid or its salts have excellent antifungal properties and are used as food preservatives, but the industrial method for producing them is usually by reacting crotonaldehyde and ketene. A method has been practiced in which the polyester is produced via an intermediately formed β-lactone, and then the polyester is decomposed by thermal decomposition, acid decomposition, or ion exchange resin decomposition to produce sorbic acid.

However, in such a method, recovery or purification of sorbic acid after polyester decomposition is troublesome, the process is long, and complicated process control is required, so that it cannot necessarily be said to be advantageous in terms of production or economy.

As a solution to this problem, a method has recently been proposed in which sorbic acid is produced by treating sorbaldehyde with specific microorganisms.
The present applicant is also in the process of filing a patent application.

[Problems to be Solved by the Invention] However, the sorbic acid-containing reaction product liquid produced by the oxidation method using microorganisms contains impurities such as meat extract, culture medium composition such as peptone, and proteins eluted by microorganism decomposition. Therefore, efficiently isolating sorbic acid from this reaction system is a challenge for industrialization. However, until now, there have been few reports on methods for isolating sorbic acid from such systems. The reality is that there is not.

The present inventors have investigated purification operations using membrane separation, crystallization, and distillation methods, but membrane separation has problems with workability such as clogging of the membrane, and crystallization has problems with purity of the obtained sorbic acid. It has been found that the distillation method has drawbacks such as the need to first esterify sorbic acid into methyl ester, etc., and it is difficult to employ both methods industrially.

[Means for Solving the Problems] However, the present inventors have determined that the sorbic acid obtained by oxidizing sorbaldehyde with microorganisms can be used to convert sorbic acid into aliphatic hydrocarbons, aromatic hydrocarbons, halogen-containing hydrocarbons, ketones, and ethers. The present inventors have discovered that sorbic acid can be efficiently obtained when at least one of them is used for solvent extraction.

First, in the present invention, sorbaldehyde is oxidized by microorganisms, but any microorganism can be used as long as it has oxidizing ability. To name a few, Mycobacterium rhodocross (Mycobacterium r.
hod.

chrous, IFO13161), a.
5pberoides, I FO12203L Streptomyces albidoflavus, (Streptos
yces albidoflavus, I F
OI 3010) Acetobacter ascendens (A
cetobacter ascendsns% IF
O3188), Acetobacter basturianus subsp.
pasteurianus 5ubsp, 1ova
Nien, I FO13753), Alcaligenes eut
r.

phus, ATCo 17699), etc.

Of course, the present invention is not limited to these.

The oxidation reaction can be carried out by any method such as adding sorbaldehyde to a medium in which microorganisms have been cultured, or collecting microorganisms from the medium and adding sorbaldehyde to a system in which they are dispersed in water, saline, buffer, etc. implement.

Reaction temperature is 10-70℃, preferably 20-40℃, PH
is 3-10, preferably 4-9, reaction time is 0.1-15
The time is selected from approximately 0 hours.

carrying out such a reaction to obtain an aqueous liquid containing sorbic acid,
The sorbic acid is isolated from this by solvent extraction.

As mentioned above, the reaction is usually carried out at a pH of about 3 to 10, and sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, etc. are used as pH adjusters, so the produced sorbic acid is often converted into a salt. exists in the system in the form of

Therefore, after the reaction, it is first necessary to neutralize the sorbate with any acid such as hydrochloric acid, sulfuric acid, or phosphoric acid. Such manipulations are not necessarily required when sorbic acid is present in the free acid form. In any case, during extraction, the P I-
It is necessary to control so that 1 becomes 4 or less.

The extraction operation can be carried out by any method such as single extraction, parallel current multistage extraction, countercurrent multistage extraction, etc., either batchwise or continuously. Examples of extraction equipment include mixer settlers, perforated plate extraction towers, extraction towers with stirrers (Mixco tower, 5chibel tower, etc.), spray towers, packed towers, centrifugal extraction equipment (Bodobilniak extraction equipment,
cyclone type extraction device), etc.

Extraction solvents include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, benzene, toluene,
Aromatic hydrocarbons such as quinolene, decalin, mesitylene, etc.
Examples include halogen-containing hydrocarbons such as chlorobenzene and dichlorobenzene, ketones such as methyl isobutyl ketone, and ethers such as diethyl ether.

A preferred solvent is toluene.

The temperature during extraction and the amount of extraction solvent used are not particularly limited and are arbitrary.

This operation yields an organic solvent solution containing sorbic acid, from which sorbic acid is isolated.

Usually, when the solvent is distilled off from the above solution, sorbic acid will crystallize, so it can be separated according to a conventional method. Of course, this is possible by adding an azeotropic agent such as water during distillation of the solvent to achieve efficient operation.

The obtained crystals of sorbic acid can be sufficiently commercialized as they are, but if necessary, known purification can be further carried out.

[Function 1] In the present invention, it is possible to efficiently extract sorbic acid with a solvent from a sorbic acid-containing reaction solution obtained by microbial oxidation of sorbaldehyde.

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

(oxidation of sorbaldehyde) Mycobacterium rhodocross (IF
'0 13161) was added to the dry equivalent of 69, P H7,
After adding 500ml of 0,0,1M phosphate buffer to sufficiently suspend the bacterial cells, sorbaldehyde was added and the pH was maintained at 6.8 to 7.1 at 30°C for 24 hours with shaking. A reaction was carried out (potassium hydroxide was used for PHDJi preparation) to obtain an aqueous solution containing potassium sorbate (1).

(This reaction was carried out twice to produce a predetermined amount of sorbic acid reaction solution.) A similar reaction was carried out using different microorganisms to obtain the following sorbic acid-containing aqueous solution.

After extraction with toluene 2209 and branching, the toluene layer was separated.

Water was added to the toluene solution and concentrated under 100+U+Hg, and all of the toluene was distilled off to obtain an aqueous suspension of sorbic acid.

Sorbic acid crystals were separated from the suspension and dried.

Sorbic acid of 23.99% (recovery rate 97%) was obtained.

Examples 2 to 15 Experiments were conducted according to Example 1 using various extraction solvents. The results are shown in the table.

Example 1 1000 g of aqueous liquid containing 32 g of potassium sorbate
Add 25ml of 36% acetic acid to 100O,8) and adjust the pH to 2.
-3 and heated to 75°C. This aqueous liquid at the same temperature. Procedural amendment ■, Indication of the case, 1986 Patent Application No. 262480 2, Name of the invention, Process for purifying sorbic acid 3, Person making the amendment. Relationship with the case. Patent applicant address: Osaka. 9-6 Nozaki-cho, Ichikita-ku (zip code 530)
[Effect] In the present invention, by extraction using a specific solvent,
Sorbic acid can be efficiently isolated from an aqueous solution containing sorbic acid.

4. Detailed explanation of the invention in the specification to be amended Patent applicant Nippon Gosei Kagaku Kogyo Co., Ltd. *! :Pt
h

Claims (1)

[Claims] From a sorbic acid-containing aqueous liquid obtained by oxidizing sorbaldehyde with a microorganism, the sorbic acid is extracted with a solvent using at least one of aliphatic hydrocarbons, aromatic hydrocarbons, halogen-containing hydrocarbons, ketones, and ethers. A method for purifying sorbic acid, characterized by: