JP2001342152A - Water-soluble organic compound-capturing agent and method for capturing the same compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a capturing method capable of simply and efficiently extracting a trace amount of water-soluble organic compound dissolved in water, etc. SOLUTION: This method for capturing a water-soluble organic compound comprises using a cyclic phenol sulfide sulfonic acid derivative represented by formula (I) [wherein M is hydrogen atom, a metal, ammonium, a lower alkyl ammonium, a lower alkanolamine or pyridines; X is S, SO or SO2; (n) is an integer of 4-6] as a water-soluble organic compound-capturing agent and brining the capturing agent into contact with an aqueous solution of the water- soluble organic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a trapping method for separating and removing an organic compound dissolved in water or the like and a water-soluble organic compound trapping agent used for the trapping method, comprising a cyclic phenol sulfide sulfonic acid derivative. The present invention relates to a water-soluble organic compound trapping agent and a method for trapping the organic compound by contacting the agent.

[0002]

2. Description of the Related Art Many organic compounds released into the environment cause pollution of water systems, and their separation and recovery are demanded from the viewpoints of living and natural environment recovery and conservation. In particular, it has been pointed out that alcohols and ketones have an influence on aquatic organisms, and the removal of water-soluble organic compounds is urgently required, for example, the relationship between cyclic ethers and carcinogenicity has been examined. However, it is difficult to recover highly water-soluble alcohols, ethers, ketones and the like from a dilute aqueous solution, and no definitive and highly efficient recovery method has been found to date. For this reason, a multi-stage separation method is generally used in which the organic compound is transferred to the gas phase by aeration treatment, and then the gas phase is adsorbed using activated carbon or the like. Although this method can use inexpensive activated carbon, it requires a great deal of power related to aeration, and there is a limit to the transfer of organic compounds to the gas phase due to aeration, so a simpler and more efficient separation method. Was required. On the other hand, among these organic compounds that cause environmental pollution, many of them are used as cleaning solvents or chemical reaction solvents, so microorganisms and enzymes have recently been used as a method for producing substances with low environmental burden. Active production of organic compounds is being attempted. These methods are a group of technologies useful for reducing the leakage source of organic compounds because they mainly produce substances in an environment using water as a medium, but it is difficult to recover products from an aqueous medium. In many cases, this was a technical issue.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for separating and recovering a water-soluble organic compound, which has been difficult to separate, from its aqueous solution simply and efficiently. It is in.

[0004]

Under these circumstances, the present inventors have conducted intensive studies and as a result, have found that a phenol sulfide sulfonic acid derivative having a specific cyclic structure allows an organic compound in an aqueous solution to be placed inside its pores. The inventors have found that the capture is performed with high efficiency, and have completed the present invention. That is, the present invention relates to formula (1)

[0005]

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Wherein M is a hydrogen atom, metal, ammonium, lower alkyl ammonium, lower alkanolamine or pyridine, and X is S, SO or SO
₂ and n is an integer of 4 to 6). A water-soluble organic compound scavenger comprising a cyclic phenol sulfide sulfonic acid derivative represented by the formula: Further, the present invention provides the water-soluble organic compound scavenger, wherein the water-soluble organic compound is a water-soluble alcohol, organic acid, ketone, amine, nitroalkane, ether, aldehyde or cyclic ether. Submit. The present invention also provides a method for capturing a water-soluble organic compound, which comprises contacting the water-soluble organic compound-capturing agent with a water-soluble organic compound. Further, the present invention provides the method for trapping a water-soluble organic compound, wherein the method comprises contacting the water-soluble organic compound-trapping agent with the water-soluble organic compound, and then precipitating the reaction product with a salting-out agent. provide. Further, the present invention provides the method for capturing a water-soluble organic compound, wherein the water-soluble organic compound is a water-soluble alcohol, an organic acid, a ketone,
A method for capturing a water-soluble organic compound which is an amine, nitroalkane, ether, aldehyde or cyclic ether is provided. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The water-soluble organic compound scavenger of the present invention comprises a cyclic phenol sulfide sulfonic acid derivative of the formula (1). In the formula (1), M represents a hydrogen atom, a metal,
Ammonium, lower alkyl ammonium, lower alkanolamine or pyridines. A plurality of Ms in one molecule may be single or two or more different types. As the metal, an alkali metal, an alkaline earth metal or the like can be used. Examples of the alkali metal include sodium, potassium, barium, rubidium, cesium, frangium and the like. Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, barium and the like. The plurality of metal species of M in one molecule may be the same or two or more different metal species. Examples of lower alkyl ammonium include methyl ammonium, ethyl ammonium, n-propyl ammonium, iso-propyl ammonium, n-butyl ammonium, dimethyl ammonium, diethyl ammonium, di-iso-
Propyl ammonium, di-iso-butyl ammonium, trimethyl ammonium, triethyl ammonium and the like. The plurality of M lower alkylammoniums in one molecule may be the same or may be two or more different ones.

[0008] The lower alkanolamines include ethanolamine, diethanolamine and triethanolamine. The plurality of M lower alkylammoniums in one molecule may be the same or may be two or more different ones. Examples of pyridines include pyridine and N-methylpyridine. 1
The plurality of M pyridines in the molecule may be the same or two or more different pyridines. In the formula (1), X is S, SO or SO ₂ and 1
A plurality of Xs in the molecule may be the same or two or more different ones. In equation (1),
n is an integer of 4 to 6. The method for producing the cyclic phenol sulfide sulfonic acid derivative represented by the formula (1) is not particularly limited, and any one produced by an arbitrary method can be used. For example, the present inventors have already disclosed. , Equation (2)

[0009]

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Wherein X is S, SO or SO ₂ , Y is a hydrogen atom or an alkyl group, and n is 4 to 6
Is an integer. ) The production method using a cyclic phenol sulfide represented by the following formula (International Publication WO99-296)
83) is available. In this method, the cyclic phenol sulfide of the formula (2) is suspended in sulfuric acid and heated under stirring to induce the cyclic phenol sulfide of the formula (1). In this method, the elimination of the alkyl group represented by Y in the formula (2) and the sulfonation reaction proceed sequentially in one reaction step. The water-soluble organic compound scavenger of the present invention may be only one kind of the cyclic phenol sulfide sulfonic acid of the above formula (1) or a combination of two or more kinds. Further, the water-soluble organic compound scavenger of the present invention may contain other scavengers as necessary, or may contain other components such as an extraction accelerator.

The water-soluble organic compound to be extracted is preferably a water-soluble alcohol, organic acid, ketone, amine, nitroalkane, ether, aldehyde or cyclic ether. Alcohols, organic acids, ketones, amines, nitroalkanes, ethers and aldehydes preferably have 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms. The cyclic ether preferably has a 4- to 6-membered ring skeleton, and the cyclic ether preferably has 5 to 10 carbon atoms, particularly preferably 5 to 8 carbon atoms. Examples of the alcohol include methanol, ethanol, ethylene glycol, 1,4-
Butanediol and the like. Examples of the organic acid include acetic acid and propionic acid. Examples of the ketone include acetone, methyl ethyl ketone, and the like. Examples of the amine include methylamine, ethylamine and the like. Examples of the nitroalkane include nitroethane. As ether,
For example, dimethyl ether, diethyl ether and the like can be mentioned. Examples of the aldehyde include formaldehyde and acetaldehyde. Examples of the cyclic ether include tetrahydroketone, 1,4-dioxane, 1,3-dioxane, and the like. The water-soluble organic compound to be extracted may be a single compound or a mixture of two or more compounds.

The capturing method of the present invention comprises the steps of: adding a water-soluble organic compound-capturing agent represented by the formula (1) and comprising a cyclic phenol sulfide sulfonic acid derivative to an aqueous solution containing a water-soluble organic compound; It can be carried out. The cyclic phenol sulfide sulfonic acid derivative represented by the formula (1) may be used as an aqueous solution or may be used as it is. The concentration of the water-soluble organic compound in the aqueous solution containing the water-soluble organic compound to be extracted is not particularly limited, and it can be extracted over a wide range from a low concentration to a high concentration. For example, extraction can be performed at a low concentration of about 0.1 ppm, and extraction can be performed at about 10% by volume. Further, the amount of the cyclic phenol sulfide sulfonic acid derivative represented by the formula (1) to be used in the aqueous solution to be extracted is not particularly limited.
10 ^{−6 to} 1M. The cyclic phenol sulfide sulfonic acid derivative can be used without being dissolved in the aqueous solution to be extracted. In this case, there is no upper limit on the amount of use. In the case of an aqueous solution causing environmental pollution, the amount of the cyclic phenol sulfide sulfonic acid derivative may be selected so that the concentration of the water-soluble organic compound after the treatment becomes equal to or less than the allowable concentration of environmental pollution. Here, the contact only needs to be able to contact the cyclic phenol sulfide sulfonic acid derivative and the water-soluble organic compound at the molecular level, and includes various contacts. The contact temperature of the two is not particularly limited, but is usually preferably 0 to 60 ° C. and the boiling point of the organic compound to be trapped or lower. The contact between the water-soluble organic compound scavenger and the water-soluble organic compound in the aqueous solution is preferably performed with stirring. By the contact between the two, an inclusion complex can be formed. The molar ratio of the cyclic phenol sulfide sulfonic acid derivative of the formula (1) to the water-soluble organic compound in the inclusion complex varies depending on the former type and the latter type, but is usually from 0.4: 1 to 1: 0.4. Range.

The separation of the water-soluble organic compound from the clathrate complex can be carried out by various separation methods. As a preferable example of the separation method, a salting-out agent is added to the aqueous solution after the two are contacted. Examples of the salting-out agent include hydrochlorides and sulfates of alkali metals and alkaline earth metals. Examples of the alkali metal include sodium, potassium, barium, rubidium, cesium, frangium and the like. Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, barium and the like. Among these salting-out agents, hydrochlorides of sodium, cesium, magnesium and barium are preferable, and sodium chloride is particularly preferable. The salting-out agent may be used alone or in combination of two or more. The addition amount of the salting-out agent may be appropriately selected so that the inclusion complex is precipitated, and is usually 0.5 to 5.0 m per 1 mol of the water-soluble organic compound scavenger.
ol is preferable, and 0.8 to 2.0 mol is particularly preferable. The temperature for salting out is not particularly limited, and may be usually in the range of 0 to 60 ° C. By adding a salting-out agent, an inclusion complex can be precipitated. The precipitated inclusion complex can be separated from the aqueous solution by filtration or the like. Here, the water-soluble organic compound can be recovered from the separated inclusion complex by a general method such as heating or decompression, and the compound represented by the formula (1)
The cyclic phenol sulfide sulfonic acid derivative represented by can be regenerated and recovered. At this time, the inclusion complex may be dissolved in a very small amount of water and heated and decompressed as an aqueous solution.

Further, as a preferable alternative method of the separation method,
An aqueous solution containing an inclusion complex may be passed through a column filled with an anion exchange resin. According to this method, the inclusion complex is ion-exchanged and adsorbed on the column, and thus the water-soluble compound may be separated from the aqueous solution by this method. The temperature at the time of column adsorption is not particularly limited, but is usually 10 to 4
The temperature is preferably 0 ° C. and the boiling point or lower of the organic compound to be captured. After the adsorption to the column, passing a weakly basic aqueous solution through the clathrate complex adsorption column causes anion exchange and a concentrated solution of the clathrate complex to flow out. Organic compounds can be recovered,
It is also possible to regenerate and recover the cyclic phenol sulfide sulfonic acid derivative represented by the formula (1).

[0015]

Next, the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited to these Examples. (Production Example 1) 5,11,17,23-tetra-tert
-Butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathia [1.9.3.1.
1 ^3, 7 ^{1 9, 13} 1 ^{15, 19]} Okutakosa -1 (2
5), 3, 5, 7 (28), 9, 11, 13 (27),
Synthesis of 15, 17, 19 (26), 21, 23-dodecaene (in the formula (2), Y is a tert-butyl group). In a glass flask, 14.4 g of elemental sulfur, 3.0 g of sodium hydroxide, and 7.60 g of tetraethylene glycol dimethyl ether were added to 45.2 g of 4-tert-butylphenol, and stirred under a nitrogen atmosphere.
The mixture was gradually heated to 230 ° C. over time and further stirred for 2 hours. During this time, water and hydrogen sulfide generated by the reaction were removed. The reaction mixture is cooled to room temperature and 500 ml of ether
Was added and dissolved, followed by hydrolysis with a 1N aqueous sulfuric acid solution. The separated ether layer was washed with water and dried over magnesium sulfate. The reaction mixture obtained after the ether was distilled off was further separated by silica gel column chromatography (hexane / chloroform) to obtain a crude product, which was recrystallized from chloroform / acetone to obtain colorless and transparent crystals. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathia [1.
^{9.3.1.1 3, 7 1 9,13 1 15,19} ] Okutakosa -1 (25), 3,5,7 (28), 9,11,1
3 (27), 15, 17, 19 (26), 21, 23
26.5 g of dodecaene were obtained. Yield was 45%.

(Production Example 2) 25,26,27,28-tetrahydroxy-2,8,14,20-tetrathia
^[1.9.3.1.1 3,7 ^{1 9,13} 1 ^15,19] Okutakosa -1 (25), 3,5,7 (28), 9,1
1,13 (27), 15, 17, 19 (26), 21,
23-Dodecaene-5,11,17,23-sodium tetrasulfonate (M = Na, X = S in the formula (1))
It is. ) Synthesis. 5, 11, 1 obtained in Production Example 1
7,23-tetra-tert-butyl-25,26,2
7,28- tetrahydroxy--2,8,14,20- Tetorachia ^[1.9.3.1.1 3,7 ^{1 9,13} 1
^15,19 ] octacosa-1 (25), 3,5,7 (2
8), 9, 11, 13 (27), 15, 17, 19 (2
6), 21,23-dodecaene 152mg, 95% concentrated sulfuric acid 15m
The suspension was heated to 80 ° C. and reacted for 4 hours. After allowing the reaction mixture to cool, it was diluted with 100 ml of ion-exchanged water, the insoluble matter was filtered off, and sodium chloride was added for salting out to give 25, 26, 27, 28-tetrahydroxy-2 as a white solid. , 8,14,20-tetrathia [1.9.3.
1.1 ^3,7 1 ^{9, 13} 1 ^{15, 19]} Okutakosa -1
(25), 3, 5, 7 (28), 9, 11, 13 (2
7), 15,17,19 (26), 21,23-dodecaene-5,11,17,23-203 mg of sodium tetrasulfonate was obtained. The yield was 74%.

Example 1 At room temperature, the formula (1) (where M =
Na, X = S, n = 4), a 55 mM aqueous solution of a cyclic phenol sulfide sulfonic acid derivative and 1 ml of ethanol were mixed to 50 ml, and the mixture was stirred for 1 minute. 16 g was added to precipitate a precipitate. NMR analysis of the molar ratio of ethanol to the cyclic phenol sulfide sulfonic acid derivative in the deposited sediment revealed that the ratio was 1: 1. The precipitated sediment was separated by filtration, the obtained sediment was put into a distillation apparatus, the pressure was reduced to 10 mmHg, and the mixture was heated and distilled at 60 ° C., and 0.9 ml of ethanol was collected as a distillate. The cyclic phenol sulfide sulfonic acid derivative represented by the formula (1) was recovered.

(Example 2) The same procedure as in Example 1 was carried out except that ethanol was replaced with acetic acid. The molar ratio of the acetic acid cyclic phenol sulfide sulfonic acid derivative in the crystal was determined by NMR.
As a result, the ratio was 1: 1.

Example 3 The same operation as in Example 1 was carried out except that nitroethane was used instead of ethanol. NMR analysis of the molar ratio of nitroethane to the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 1.
01: 1.

Example 4 The same operation as in Example 1 was carried out except that ethanol was replaced with ethylamine. NMR analysis of the molar ratio of ethylamine and the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 0.1.
56: 1.

Example 5 The same operation as in Example 1 was carried out except that ethanol was replaced with n-propanol. NMR analysis of the molar ratio of n-propanol and the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 1.04: 1.

Example 6 The same procedure as in Example 1 was carried out except that ethanol was replaced with n-butanol. NMR analysis of the molar ratio of n-butanol and the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 1.04: 1.

(Comparative Example 1) A procedure was performed in the same manner as in Example 6 except that sodium calix [4] arene sulfonate was used instead of the cyclic phenol sulfide sulfonic acid derivative. NMR analysis of the molar ratio of n-butanol and sodium calix [4] arene sulfonate in the crystals revealed that the ratio was 0.05: 1.

Example 7 The same operation as in Example 1 was carried out except that ethanol was replaced with n-pentanol. NMR analysis of the molar ratio between n-pentanol and the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 0.92: 1.

(Comparative Example 2) The same procedure as in Example 7 was carried out except that sodium calix [4] arene sulfonate was used instead of the cyclic phenol sulfide sulfonic acid derivative. NMR analysis of the molar ratio of n-pentanol and sodium calix [4] arene sulfonate in the crystals revealed that the ratio was 0.05: 1.

Example 8 The same operation as in Example 1 was carried out except that ethanol was replaced with allyl alcohol. NMR analysis of the molar ratio of allyl alcohol and cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 1.02: 1.

Example 9 The same operation as in Example 1 was carried out except that ethanol was replaced with ethylene glycol. NMR analysis of the molar ratio between ethylene glycol and the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 1.42: 1.

Example 10 The same operation as in Example 1 was carried out except that ethanol was replaced with propylene glycol.
NMR analysis of the molar ratio of propylene glycol to the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 1.16: 1.

Example 11 The same operation as in Example 1 was carried out except that ethanol was replaced with propionic acid. NMR analysis of the molar ratio of propionic acid to the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 1.08: 1.

Example 12 Example 12 was carried out in the same manner as in Example 1, except that ethanol was replaced with acetone. NMR analysis of the molar ratio of acetone and the cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 0.97:
It was one.

Example 13 The same operation as in Example 1 was carried out except that ethanol was replaced by methyl ethyl ketone. NMR analysis of the molar ratio of methyl ethyl ketone and cyclic phenol sulfide sulfonic acid derivative in the crystals by NMR,
The ratio was 0.96: 1.

Example 14 The same operation as in Example 1 was carried out except that ethanol was replaced with tetrahydrofuran. NMR analysis of the molar ratio of tetrahydrofuran and cyclic phenol sulfide sulfonic acid derivative in these crystals,
The ratio was 1.04: 1.

Example 15 The same operation as in Example 1 was carried out except that ethanol was replaced with 1,3-dioxane. NMR analysis of the molar ratio of 1,3-dioxane and cyclic phenol sulfide sulfonic acid derivative in the crystals by NMR revealed
The ratio was 2.02: 1.

Example 16 The same operation as in Example 1 was carried out except that ethanol was replaced with 1,4-dioxane. NMR analysis of the molar ratio of 1,4-dioxane and cyclic phenol sulfide sulfonic acid derivative in the crystals by NMR revealed
The ratio was 2.09: 1.

Example 17 At room temperature, the formula 1 (where M = Na
Wherein X = SO2, n = 4), and a 55 mM aqueous solution of a cyclic phenol sulfide sulfonic acid derivative and 1 ml of acetonitrile were mixed to 50 ml, and after stirring for 1 minute,
To this, 0.16 g of sodium chloride was added to precipitate a precipitate. NMR analysis of the molar ratio of acetonitrile and the cyclic phenol sulfide sulfonic acid derivative in the precipitated sediment revealed that the ratio was 0.97: 1.

Example 18 The same operation as in Example 17 was carried out except that acetonitrile was replaced with nitroethane. NMR analysis of the molar ratio of nitroethane and cyclic phenol sulfide sulfonic acid derivative in the crystals revealed that the ratio was 0.96: 1.

Example 19 At room temperature, the formula 1 (where M = Na
Wherein X = S and n = 6), a 55 mM aqueous solution of a cyclic phenol sulfide sulfonic acid derivative and 1 m of acetone
After mixing for 1 minute, the mixture was stirred for 1 minute, and 0.16 g of sodium chloride was added thereto to precipitate a precipitate. NMR analysis of the molar ratio of acetone to the cyclic phenol sulfide sulfonic acid derivative in the deposited sediment revealed that the ratio was 0.56: 1.

[0038]

According to the method of the present invention, a trace amount of a dissolved water-soluble organic compound can be easily and efficiently extracted.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 31/20 C07C 31/20 AZ 33/03 33/03 45/81 45/81 49/08 49 / 08 J 49/10 49/10 51/48 51/48 53/122 53/122 201/16 201/16 205/02 205/02 209/90 209/90 211/05 211/05 // C07D 307/06 C07D 307/06 319/06 319/06 319/12 319/12 341/00 341/00 (72) Inventor Haruhiko Takeya 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center ( 72) Inventor Setsuko Miyanari 1134-2, Gongendo, Satte-shi, Saitama, Japan, R & D Center, Kosmo Research Institute, Inc. Inside the Development Center (72) Inventor Hitoshi Kumagai 1134-2 Gongendo, Satte City, Saitama National Institute of Advanced Research and Development Center in the F-term (reference) 4C022 GA20 JA10 4D038 AB09 AB10 AB12 BB20 4H006 AA02 AC93 AD33 BB31 BN10 BR10 BS10 BU22 BU32

Claims (5)

[Claims] (1) Formula (1) (Wherein, M is a hydrogen atom, metal, ammonium, lower alkyl ammonium, lower alkanolamine or pyridines, X is S, SO or SO ₂ , n
Is an integer of 4 to 6. A water-soluble organic compound scavenger comprising a cyclic phenol sulfide sulfonic acid derivative represented by the formula (1). 2. The water-soluble organic compound scavenger according to claim 1, wherein the water-soluble organic compound is a water-soluble alcohol, organic acid, ketone, amine, nitroalkane, ether, aldehyde or cyclic ether. 3. A method for trapping a water-soluble organic compound, comprising bringing the water-soluble organic compound-trapping agent according to claim 1 into contact with the water-soluble organic compound. 4. The method for capturing a water-soluble organic compound according to claim 3, wherein after contacting the water-soluble organic compound-capturing agent with the water-soluble organic compound, the reaction product is precipitated with a salting-out agent. 5. The water-soluble organic compound is a water-soluble alcohol, organic acid, ketone, amine, nitroalkane, ether, aldehyde or cyclic ether.
3. The method for capturing a water-soluble organic compound according to item 1.