WO2009110384A1 - Procédé et dispositif pour récupérer des substances organiques dans l'eau - Google Patents

Procédé et dispositif pour récupérer des substances organiques dans l'eau Download PDF

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WO2009110384A1
WO2009110384A1 PCT/JP2009/053702 JP2009053702W WO2009110384A1 WO 2009110384 A1 WO2009110384 A1 WO 2009110384A1 JP 2009053702 W JP2009053702 W JP 2009053702W WO 2009110384 A1 WO2009110384 A1 WO 2009110384A1
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organic
alcohol
substance
organic substance
carbon atoms
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PCT/JP2009/053702
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English (en)
Japanese (ja)
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悦子 門脇
哲雄 工藤
哲夫 中條
修 小林
吉邦 奥村
寅吉 東
大輔 柳生
千博 乙川
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昭和電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • C07C51/493—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification whereby carboxylic acid esters are formed
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds

Definitions

  • the present invention relates to a method and apparatus for recovering an organic substance from an organic substance-containing aqueous solution. More specifically, the present invention relates to a method and apparatus for efficiently recovering an organic substance from an aqueous layer by reacting the organic substance in the organic substance-containing aqueous solution with an alcohol having 8 or more carbon atoms.
  • an activated sludge method for biologically treating an organic substance in an aqueous solution is common and widely used.
  • this method is a method that consumes relatively little energy, there is a problem that it is difficult to control and maintain the treatment conditions of activated sludge (microorganisms) for treating organic matter.
  • activated sludge microorganisms
  • a processing facility becomes large sized and the processing cost of the excess sludge generated after a process further increases.
  • Patent Document 2 Japanese Patent Laid-Open No. 2004-351259; Patent Document 2. This method is effective when the concentration of organic substances in the aqueous solution is high, but there is a problem that carbon dioxide is generated by combustion. Moreover, when the organic substance density
  • Patent No. 4104232 Patent Document 4, JP-A-60- No. 25949; Patent Document 5 (EP0134650); JP-A-63-44539; Patent Document 6).
  • Patent Document 6 Patent No. 4104232; Patent Document 4, JP-A-60- No. 25949; Patent Document 5 (EP0134650); JP-A-63-44539; Patent Document 6).
  • Patent Document 4 Patent Document 4, JP-A-60- No. 25949; Patent Document 5 (EP0134650); JP-A-63-44539; Patent Document 6
  • FIG. 1 is a flowchart of a Wacker acetaldehyde production plant using ethylene and oxygen as raw materials in a reactor (1) containing a mixed aqueous solution of palladium (II) chloride (PdCl 2 ) and copper (II) chloride. Ethylene and oxygen are reacted, and the produced acetaldehyde and the like are absorbed in water by the absorption tower (2), and then acetaldehyde is recovered by the purification tower (3).
  • the wastewater discharged from the absorption tower (2) of this plant contains acetic acid as a by-product in the reaction at a concentration of approximately 2% by mass or less, but because the acetic acid concentration is low and the amount of wastewater is large, the treatment costs are high. There was a problem that it took.
  • An object of the present invention is to provide a method and an apparatus for recovering an organic substance from an organic substance-containing aqueous solution that generates less industrial waste such as excess sludge and can reduce the size of the apparatus.
  • the present inventors have intensively studied to solve the above problems. As a result, a method for efficiently recovering organic substances in an organic substance-containing aqueous solution using an alcohol having 8 or more carbon atoms was found, and the present invention was completed.
  • the present invention relates to the following [1] to [18] organic matter recovery method and apparatus.
  • [1] The organic substance in an aqueous solution in which the organic substance is dissolved is reacted with an alcohol having 8 or more carbon atoms to convert the organic substance into a hydrophobic substance, and the organic layer containing the hydrophobic substance is removed from the aqueous layer.
  • An organic matter recovery method characterized by comprising: [2] The organic material recovery method according to [1], wherein the organic material is a compound having a functional group capable of binding to an alcohol having 8 or more carbon atoms.
  • the alcohol having 8 or more carbon atoms is 1-octanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, 1-tetracosanol, 1-hexacosanol, 2-octyl-1-dodecanol , Trans-2-dodecenol, trans-2-tridecen-1-ol, trans-9-octadecenol, oleyl alcohol, cis, cis-9,12-octadecadien-1-ol, cis-13-docosenol, and diphenyl At least selected from the group consist
  • the compound having a functional group capable of binding to the alcohol having 8 or more carbon atoms is at least one selected from the group consisting of aldehyde, ketone, carboxylic acid, thiol, sulfoxide, amine, imide, and nitrile.
  • [6] The organic substance recovery method according to [5], wherein the compound having a functional group capable of binding and reacting with an alcohol having 8 or more carbon atoms is a carboxylic acid.
  • a wastewater purification apparatus comprising the organic matter recovery apparatus as described in 14 above.
  • the organic substance recovery method according to any one of the above.
  • the organic substance recovery method according to any one of the above.
  • the present invention it is possible to recover organic matter under conditions with low energy cost using a small apparatus.
  • the method of the present invention can also be applied to recovering low-concentration organic substances, which has been difficult in the past.
  • the present invention can also be applied to wastewater treatment that removes organic matter from wastewater in which a small amount of organic matter is dissolved. As a result, because it cannot be collected so far, it has been forced to use biological wastewater treatment, and it is possible to reduce excess sludge that has been generated in large quantities without profit, and to reduce the environmental burden by reducing industrial waste. It becomes.
  • an organic substance dissolved in water is converted into a hydrophobic substance, and separated and recovered as an organic layer from the aqueous layer.
  • the organic substance is a carboxylic acid
  • it reacts with an alcohol having 8 or more carbon atoms to form an ester.
  • This ester becomes hydrophobic due to the influence of an alcohol having 8 or more carbon atoms and hardly dissolves in water.
  • an organic layer is formed and separated from the aqueous layer.
  • This organic layer also contains an unreacted alcohol having 8 or more carbon atoms.
  • the organic substance that can be recovered from the aqueous solution in which the organic substance is dissolved is not limited to carboxylic acid, and is not particularly limited as long as it is a compound that reacts with an alcohol having 8 or more carbon atoms to be converted into a hydrophobic substance.
  • the organic compound that can be bonded to alcohol by reaction include aldehyde, ketone, carboxylic acid, thiol, sulfoxide, amine, imide, and nitrile.
  • these organic compounds may have a plurality of functional groups.
  • the carboxylic acid includes thiocarboxylic acid, hydroxycarboxylic acid and the like. At this time, when other organic substances that do not react with alcohol having 8 or more carbon atoms are contained, they remain in water as they are.
  • organic compounds to be recovered by the method of the present invention include carboxylic acid compounds such as formic acid, acetic acid, propionic acid, and butyric acid, and aldehyde compounds such as acetaldehyde, propionaldehyde, 1-butanal, chloroacetaldehyde, dichloroacetaldehyde, and the like. Is mentioned. These may be a mixture.
  • the method of the present invention is particularly useful for recovering acetic acid contained in the wastewater of an acetaldehyde production plant.
  • the alcohol having 8 or more carbon atoms used in the present invention is not particularly limited. However, in the present invention, an organic substance dissolved in water is converted into a hydrophobic substance and separated from the aqueous layer. Therefore, a highly hydrophobic alcohol is preferable. . Specifically, those having one hydroxyl group and no other hydrophilic group are preferred, and in particular, monohydric alcohols having a straight or branched structure having 8 to 50 carbon atoms, preferably 11 to 50 carbon atoms, And a monohydric alcohol having an aromatic ring is preferred.
  • the saturated alcohol having a linear alkyl structure includes 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1 -Hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-henecosanol, 1-docosanol, 1-tetracosanol, 1-hexacosanol, etc.
  • Examples of the saturated alcohol having a branched chain structure include 2-octanol, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 2-octyl-1-dodecanol and the like.
  • Examples of unsaturated alcohols include trans-2-dodecenol, trans-2-tridecen-1-ol, trans-9-octadecenol, oleyl alcohol, cis, cis-9,12-octadecadien-1-ol, cis -13-docosenol and the like, and examples of the alcohol having an aromatic ring include 3-phenylpropanol and diphenylcarbinol.
  • Preferred saturated alcohols having a straight chain structure include 1-octanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1 -Heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, 1-tetracosanol, 1-hexacosanol, etc.
  • Examples of preferable saturated alcohols include 2-octyl-1-dodecanol.
  • Preferred unsaturated alcohols include trans-2-dodecenol, trans-2-tridecen-1-ol, trans-9-octadecenol, oleyl alcohol, cis, cis-9,12-octadecadien-1-ol, Cis-13-docosenol and the like, and preferred alcohols having an aromatic ring include diphenylcarbinol and the like.
  • 2-octyl-1-dodecanol, 1-decanol, and 1-octanol are particularly preferable because they have a melting point of not more than room temperature, are easy to handle and have low solubility in water.
  • the alcohol having 8 or more carbon atoms may be used alone or in combination of two or more. Moreover, if it is a range which does not impair the effect of this invention, the C8 alcohol may be mixed.
  • the alcohol having 8 or more carbon atoms is preferably liquid at room temperature in terms of handling. In order to use in a distribution process, the alcohol needs to be in a liquid state, and therefore, it is necessary to select an alcohol having 8 or more carbon atoms having a melting point lower than the process temperature.
  • the melting point of the alcohol having 8 or more carbon atoms is preferably 100 ° C. or less, more preferably 50 ° C. or less, and most preferably 10 ° C. or less.
  • the hydrophobic substance produced by the reaction with an alcohol having 8 or more carbon atoms is a substance having low solubility in water, and is a substance that separates into an aqueous layer and an organic layer.
  • the solubility in water is 1% by mass or less at 20 ° C., preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. .
  • the total organic carbon (TOC) in the present invention is the amount of carbon obtained by measuring carbon dioxide generated when a sample solution is burned with a non-dispersive infrared gas analyzer, and the content of organic matter in the aqueous solution. Used as an indicator of The TOC can be measured by a method defined in JIS K400.
  • the method of the present invention is characterized in that organic substances can be efficiently recovered in a dilute concentration where the TOC concentration in the aqueous solution is 10 mass ppm or more and 30,000 mass ppm or less.
  • the effect is exhibited when recovering dilute organic substances having a TOC concentration in the aqueous solution of 10,000 ppm by mass, more preferably 5,000 ppm by mass or less.
  • the TOC concentration exceeds 30,000 mass ppm, the energy cost of the distillation method or the like is lower, and when the TOC concentration is less than 10 mass ppm, the alcohol itself having 8 or more carbon atoms is dissolved in water by about 10 mass ppm. It cannot be recovered.
  • a catalyst is preferably used when an organic substance in water reacts with an alcohol having 8 or more carbon atoms. Although it is possible to carry out the reaction without using a catalyst, it is necessary to increase the reaction temperature or the reaction time. There is no restriction
  • homogeneous catalysts using organic acids such as p-dodecylbenzenesulfonic acid and p-toluenesulfonic acid
  • inorganic acids such as sulfuric acid and phosphoric acid, sulfonic acid type ion exchange resins, silica gel, celite, alumina, zirconia
  • Any of heterogeneous catalysts using a supported acid in which phosphoric acid, sulfuric acid or the like is supported on a carrier such as can be used.
  • a catalyst having a surfactant type structure has a hydrophobic group having an affinity for a solvent having a low polarity and a hydrophilic group having a high affinity for a solvent having a high polarity such as water.
  • the portion has the catalytic action of the present invention.
  • the hydrophobic group structure include hydrocarbon-based, fluorine-based, organometallic, and polymer structures.
  • Examples of the hydrophilic group structure exhibiting a catalytic action include Bronsted acids such as sulfonic acid, carboxylic acid and phosphoric acid, and Lewis acids such as metals, with Bronsted acid being particularly preferred.
  • alkylbenzene sulfonic acid such as p-dodecylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid,
  • the amount of catalyst when the reaction is carried out using a homogeneous catalyst is preferably in the range of 0.1 to 20% by mass with respect to the organic layer containing an alcohol having 8 or more carbon atoms. If it is less than 0.1% by mass, a preferable reaction rate cannot be obtained, and even if 20% by mass is used more, the yield is not greatly improved.
  • examples of the reaction method include stirring, a method using a line mixer, and a countercurrent contact method. Since water and alcohol having 8 or more carbon atoms are easily separated, it is preferable to take a reaction system that increases contact efficiency when the reaction is carried out batchwise. The process of continuously reacting by the countercurrent contact method is economically advantageous by continuously separating an organic layer containing a converted hydrophobic substance and an unreacted alcohol having 8 or more carbon atoms and an aqueous layer. Can be implemented.
  • the temperature at which the organic substance reacts with the higher alcohol having 8 or more carbon atoms is not particularly limited.
  • the reaction temperature can be set according to the purpose, but it is preferably in the range of room temperature to 150 ° C, more preferably in the range of 20 ° C to 120 ° C. If the temperature is too low, the reaction rate is slow, and if it exceeds 150 ° C., energy costs are increased, which is not preferable.
  • the reaction pressure is not particularly limited, but from the viewpoint of energy cost, a range from normal pressure to 0.4 MPaG (gauge pressure) is preferable, and a range from normal pressure to 0.1 MPaG is more preferable.
  • the reaction time is not particularly limited. The reaction time can be selected according to the purpose, but is preferably 60 minutes or less, more preferably 30 minutes or less.
  • the method for separating the organic layer containing the hydrophobic substance and the unreacted alcohol having 8 or more carbon atoms after the reaction treatment can be selected from industrially used methods such as stationary separation and distillation separation.
  • recovery The method used industrially can be used. For example, recovery by distillation of unreacted alcohol, recovery of the converted hydrophobic substance by, for example, hydrolysis or transesterification, and the like can be mentioned.
  • the method of the present invention is also useful for recovering acetic acid contained in the wastewater of an acetaldehyde production plant by the Wacker method.
  • acetaldehyde is produced by reacting raw material ethylene and oxygen with an aqueous hydrogen chloride solution containing palladium (II) chloride and copper (II) chloride as shown in the following three reaction formulas. To do. In general, as a side reaction in a series of these reactions, oxygen oxidation of acetaldehyde using palladium as a catalyst occurs, and acetic acid is by-produced.
  • Fig. 1 is a flow chart of the acetaldehyde production process by the Wacker method.
  • an aqueous hydrogen chloride solution containing palladium (II) chloride and copper (II) chloride, which are catalysts is placed in a reactor (1), and ethylene, oxygen, and an absorption tower (2 ) Bubbling unreacted ethylene and oxygen-containing circulating gas from the top of the column to react ethylene to produce acetaldehyde.
  • the gas containing acetaldehyde, unreacted ethylene and oxygen and acetic acid by-products such as oxygen and acetic acid that exits from the top of the reactor (1) is supplied to the bottom of the absorption tower (2) and is contacted with a large amount of water.
  • By-products such as acetaldehyde and acetic acid are absorbed by water.
  • Water containing by-products such as acetaldehyde and acetic acid coming out from the bottom of the absorption tower (2) is supplied to the purification tower (3) and rectified.
  • Acetaldehyde is obtained from the top of the purification tower (3), and water containing by-products such as acetic acid is discharged from the bottom of the tower.
  • the concentration of acetic acid in the wastewater is generally 2% by mass or less, although it depends on operating conditions and reaction conditions.
  • Waste water and an alcohol having 8 or more carbon atoms such as 2-octyl-1-dodecanol are reacted to form 2-octyl-1-dodecyl acetate.
  • the 2-octyl-1-dodecyl acetate and unreacted 2-octyl-1-dodecanol are separated into two layers as an organic layer and the wastewater from which acetic acid has been removed is separated into two layers. Unreacted acetic acid is partitioned into organic and aqueous layers.
  • Unreacted 2-octyl-1-dodecanol in the organic layer is separated by a known method such as distillation, and can be used again for the reaction with an alcohol having 8 or more carbon atoms.
  • 2-octyl-1-dodecyl acetate extracted and recovered in the organic layer can be hydrolyzed back to acetic acid and 2-octyl-1-dodecanol
  • waste water containing acetic acid is used because water is used. Will occur.
  • water is not used excessively, which is advantageous from the viewpoint of energy cost required for distillation.
  • Ethyl acetate and 2-octyl-1-dodecanol can be separated by a known method (distillation or the like) with lower energy than water distillation.
  • the obtained 2-octyl-1-dodecanol can be used again for recovering organic substances in water.
  • Ethyl acetate can be recovered as a product.
  • FIG. 2 shows an example of a recovery process flow diagram comprising a reaction step (esterification step) of an aqueous solution containing acetic acid as an organic substance and 2-octyl-1-dodecanol, a transesterification step, and a purification step.
  • An aqueous solution containing acetic acid as an organic substance is subjected to countercurrent contact with an organic layer containing 2-octyl-1-dodecanol and a catalyst and subjected to an esterification reaction (esterification step).
  • the organic layer and the aqueous layer are separated, and the organic layer contains 2-octyl-1-dodecyl acetate and unreacted 2-octyl-1-dodecanol, and the next 2-octyl-1-dodecyl acetate is It is converted into ethyl acetate by a transesterification reaction with ethanol by a reactive distillation method (transesterification step).
  • a solution of ethyl acetate and unreacted ethanol obtained by transesterification is purified and separated (purification step).
  • the separated unreacted ethanol is reused in the transesterification step.
  • Ethyl acetate can also be shipped as a product. Unreacted 2-octyl-1-dodecyl obtained from the bottom of the transesterification step is returned to the esterification step and reused.
  • the organic substance recovery method of the present invention is intended to recover an organic substance from an aqueous solution in which the organic substance is dissolved, but can also be used for the purpose of removing the organic substance from the aqueous solution.
  • Gas chromatography measurement conditions Capillary column: DB-WAX (length 30 m, inner diameter 0.32 mm, film thickness: 0.25 ⁇ m) manufactured by Agilent Technologies, Column temperature: The initial temperature is raised from 70 ° C. to 220 ° C. at a rate of 10 ° C./min. Inlet temperature: 300 ° C Detector temperature: 300 ° C Split analysis: split ratio 1:20, Carrier gas flow rate (He): 0.5 mL / min.
  • recovery rate of organic matter in the water layer (sometimes simply referred to as the recovery rate) defined by the following formula is converted to a hydrophobic substance by reacting with an alcohol having 8 or more carbon atoms in the organic matter in the aqueous layer. It indicates the ratio of being transferred to the organic layer as it is extracted or left unreacted.
  • Example 1 Charge 5 g of 0.2 mass% acetic acid aqueous solution and 5 g of 2-octyl-1-dodecanol into a 120 ml portable reactor containing an inner cylinder, add 0.053 g of p-dodecylbenzenesulfonic acid, and constantly stir at 80 ° C. The reaction was carried out for 30 minutes, and the acetic acid was esterified and converted to the hydrophobic substance 2-octyl-1-dodecyl acetate. The obtained reaction solution was separated into an aqueous layer and an organic layer with a separatory funnel. Each component analysis of the water layer and the organic layer was conducted. As a result, the yield of 2-octyl-1-dodecyl acetate was 62.9%, and the recovery rate of acetic acid from the aqueous layer to the organic layer was 75.3%.
  • Example 2 The same procedure as in Example 1 was performed except that the reaction temperature of Example 1 was changed to 60 ° C. and the reaction time was changed to 3 hours. As a result, the yield of 2-octyl-1-dodecyl acetate was 61.0%, and the recovery rate of acetic acid from the aqueous layer to the organic layer was 73.0%.
  • Example 3 5 g of 5% acetic acid aqueous solution and 5 g of 2-octyl-1-dodecanol were charged into a 120 ml portable reactor containing an inner cylinder, 0.112 g of p-dodecylbenzenesulfonic acid was added, and the mixture was stirred at 60 ° C. for 5 times at 60 ° C. Time reaction was performed. The reaction solution was separated into a water layer and an organic layer with a separatory funnel, and each component analysis of the water layer and the organic layer was performed. As a result, the yield of 2-octyl-1-dodecyl acetate was 67.1%, and the recovery rate of acetic acid from the aqueous layer to the organic layer was 82.5%.
  • Example 4 5 g of an aqueous solution in which acetic acid, chloroacetaldehyde and acetaldehyde are dissolved as organic substances and 5 g of 2-octyl-1-dodecanol were charged into a 120 ml portable reactor containing 0.053 g of p-dodecylbenzenesulfonic acid. The reaction was carried out at 60 ° C. for 5 hours while stirring. At this time, the organic matter in the aqueous solution in which the organic matter was dissolved was 2,000 ppm of acetic acid, 600 ppm of chloroacetaldehyde, and 100 ppm of acetaldehyde.
  • the reaction solution was separated into an aqueous layer and an organic layer with a separatory funnel. Each component analysis of the water layer and the organic layer was conducted. As a result, the yield of 2-octyl-1-dodecyl acetate was 62.9%, the recovery rate of chloroacetaldehyde was 65.1%, and the recovery rate of acetaldehyde was 67.1%.
  • Example 5 30 g of 0.2% by mass acetic acid aqueous solution and 30 g of 2-octyl-1-dodecanol were charged into a 300 ml separable flask equipped with a condenser, and 0.30 g of p-dodecylbenzenesulfonic acid was added. The reaction was carried out at 30 ° C. for 30 minutes, and acetic acid was esterified to convert it into 2-octyl-1-dodecyl acetate, which is a hydrophobic substance. The reaction solution was separated into a water layer and an organic layer with a separatory funnel, and each component analysis of the water layer and the organic layer was performed. As a result, the yield of 2-octyl-1-dodecyl acetate was 30.1%, and the acetic acid recovery rate was 41.2%.
  • Example 6 The same procedure as in Example 5 was performed except that the reaction temperature was changed to 70 ° C. As a result, the yield of 2-octyl-1-dodecyl acetate was 15.4%, and the acetic acid recovery rate was 31.5%.
  • Example 7 The same procedure as in Example 5 was performed except that the reaction temperature was changed to 94 ° C. As a result, the yield of 2-octyl-1-dodecyl acetate was 37.3%, and the acetic acid recovery rate was 53.1%.
  • Example 8 The same procedure as in Example 5 was performed except that the reaction time was changed to 10 minutes. As a result, the yield of 2-octyl-1-dodecyl acetate was 11.2%, and the acetic acid recovery rate was 27.9%.
  • Example 9 The same procedure as in Example 5 was performed except that the reaction time was changed to 180 minutes. As a result, the yield of 2-octyl-1-dodecyl acetate was 70.8%, and the acetic acid recovery was 82.8%.
  • Example 10 The same procedure as in Example 5 was performed except that the reaction time was changed to 300 minutes. As a result, the yield of 2-octyl-1-dodecyl acetate was 73.4%, and the acetic acid recovery rate was 83.4%.
  • Example 11 The same procedure as in Example 5 was repeated except that the amount of 2-octyl-1-dodecanol used was changed to 15 g. As a result, the yield of 2-octyl-1-dodecyl acetate was 29.2%, and the acetic acid recovery rate was 40.2%.
  • Example 12 The same operation as in Example 5 was conducted except that the amount of p-dodecylbenzenesulfonic acid used was changed to 0.15 g. As a result, the yield of 2-octyl-1-dodecyl acetate was 15.3%, and the acetic acid recovery rate was 34.8%.
  • Example 13 The same procedure as in Example 5 was performed except that the amount of p-dodecylbenzenesulfonic acid used was changed to 0.6 g. As a result, the yield of 2-octyl-1-dodecyl acetate was 43.9%, and the acetic acid recovery rate was 52.8%.
  • Example 14 30 g of 0.2% by mass acetic acid aqueous solution and 30 g of 2-octyl-1-dodecanol were charged into a 300 ml separable flask equipped with a condenser and heated to 80 ° C. with constant stirring. Thereafter, 0.30 g of p-dodecylbenzenesulfonic acid was added and reacted for 10 minutes to esterify acetic acid to convert it into 2-octyl-1-dodecyl acetate which is a hydrophobic substance. The reaction solution was separated into an aqueous layer and an organic layer with a separatory funnel. Each component analysis of the water layer and the organic layer was conducted. As a result, the yield of 2-octyl-1-dodecyl acetate was 30.7%, and the acetic acid recovery rate was 50.4%.
  • Example 15 The same operation as in Example 14 was performed except that a 0.5 mass% acetic acid aqueous solution was used as the acetic acid aqueous solution. As a result, the yield of 2-octyl-1-dodecyl acetate was 22.0%, and the acetic acid recovery rate was 36.7%.
  • Example 16 The same operation as in Example 14 was performed except that a 2.0 mass% acetic acid aqueous solution was used as the acetic acid aqueous solution. As a result, the yield of 2-octyl-1-dodecyl acetate was 20.5%, and the acetic acid recovery rate was 36.5%.
  • Comparative Example 1 The same procedure as in Example 16 was performed except that p-dodecylbenzenesulfonic acid was not used. As a result, 2-octyl-1-dodecyl acetate was not produced. At this time, the acetic acid recovery rate was 17.8%. Unreacted acetic acid dissolved in 2-octyl-1-dodecanol is only about half of 2-octyl-1-dodecyl acetate and unreacted acetic acid dissolved in 2-octyl-1-dodecanol of Example 16. It was.
  • Example 17 60 mL of 4N hydrochloric acid was added to 35.3 g of Perex NBL (aqueous sodium alkylnaphthalenesulfonate (containing 34%); manufactured by Kao), and the mixture was shaken well, followed by extraction using diisopropyl ether. The separated organic layer was concentrated under reduced pressure to obtain 11.1 g of a brown oily product (alkylnaphthalenesulfonic acid) (conversion of Na-type catalyst to H-type catalyst). The same procedure as in Example 5 was performed except that 0.28 g of this brown oily product was used instead of p-dodecylbenzenesulfonic acid. As a result, the yield of 2-octyl-1-dodecyl acetate was 22.5%, and the acetic acid recovery rate was 34.5%.
  • Perex NBL aqueous sodium alkylnaphthalenesulfonate (containing 34%); manufactured by Kao
  • Example 18 The same procedure as in Example 5 was performed except that 0.16 g of p-toluenesulfonic acid was used instead of p-dodecylbenzenesulfonic acid. As a result, the yield of 2-octyl-1-dodecyl acetate was 17.2%, and the acetic acid recovery rate was 38.2%.
  • Example 19 The same procedure as in Example 5 was performed except that 0.63 g of p-toluenesulfonic acid was used instead of p-dodecylbenzenesulfonic acid, and the reaction time was 10 minutes. As a result, the yield of 2-octyl-1-dodecyl acetate was 37.1%, and the acetic acid recovery rate was 48.8%.
  • Example 20 The same procedure as in Example 5 was performed except that 0.46 g of perfluorooctanesulfonic acid was used instead of p-dodecylbenzenesulfonic acid. As a result, the yield of 2-octyl-1-dodecyl acetate was 33.1%, and the acetic acid recovery was 41.1%.
  • Example 21 The same procedure as in Example 5 was performed except that 1.84 g of perfluorooctanesulfonic acid was used in place of p-dodecylbenzenesulfonic acid, and the reaction time was 10 minutes. As a result, the yield of 2-octyl-1-dodecyl acetate was 59.0%, and the acetic acid recovery rate was 60.3%.
  • Example 22 A reaction tower (inner diameter: 10 mm, length: 300 mm) filled with a packing (HELIPAK 0.9 mm (W) ⁇ 1.8 mm (D) ⁇ 1.8 mm (H)) was used, and warm water was allowed to flow through the jacket part to 80 While maintaining a temperature of 0 ° C., 0.2 mass% acetic acid aqueous solution (aqueous layer) was introduced from the top, and 2-octyl-1-dodecanol (organic layer) in which p-dodecylbenzenesulfonic acid (1 mass%) was dissolved was introduced from the bottom. The aqueous layer and the organic layer were reacted in a counter flow.
  • HELIPAK 0.9 mm (W) ⁇ 1.8 mm (D) ⁇ 1.8 mm (H) a packing
  • warm water was allowed to flow through the jacket part to 80 While maintaining a temperature of 0 ° C., 0.2 mass% acetic acid aqueous
  • the flow rate is 1.00 mL / min for both the aqueous layer and the organic layer.
  • the aqueous layer flowing out from the lower part and the organic layer flowing out from the upper part were collected, and the respective components were analyzed.
  • the yield of 2-octyl-1-dodecyl acetate was 9.7%
  • the acetic acid recovery rate was 18.8%.
  • Example 23 The same procedure as in Example 22 was performed except that 2-octyl-1-dodecanol in which p-dodecylbenzenesulfonic acid (4% by mass) was dissolved was used as the organic layer to be introduced. As a result, the yield of 2-octyl-1-dodecyl acetate was 27.3%. The concentration of 2-octyl-1-dodecyl acetate in the organic layer was 0.37% by mass, and the acetic acid recovery rate was 28.6%.
  • Example 24 Using a reaction tower (inner diameter 10 mm, length 300 mm) packed with packing (McMahon 6 mm ⁇ 6 mm), warm water was allowed to flow through the jacket to 80 ° C., and 0.2 mass% acetic acid aqueous solution (aqueous layer) from the top From the bottom, 2-octyl-1-dodecanol (organic layer) in which p-dodecylbenzenesulfonic acid (8% by mass) was dissolved was introduced, and the aqueous layer and the organic layer were reacted in a counterflow. The flow rate is 1.00 mL / min for both the aqueous layer and the organic layer.
  • Example 25 The same procedure as in Example 24 was performed except that 2-octyl-1-dodecanol in which p-dodecylbenzenesulfonic acid (12% by mass) was dissolved was used as the organic layer to be introduced. As a result, the yield of 2-octyl-1-dodecyl acetate was 43.2%, and the acetic acid recovery rate was 46.4%.
  • Example 25 Example 25 except that 2-octyl-1-dodecanol containing no p-dodecylbenzenesulfonic acid was used in place of 2-octyl-1-dodecanol in which p-dodecylbenzenesulfonic acid (12% by mass) was dissolved. As well as. As a result, 2-octyl-1-dodecyl acetate was not produced. At this time, the recovery rate of acetic acid was 3.0%.
  • Example 26 The same operation as in Example 23 was performed except that the flow rates of the aqueous layer and the organic layer were both 0.10 mL / min. As a result, the yield of 2-octyl-1-dodecyl acetate was 69.2%, and the acetic acid recovery rate was 81.5%.
  • Example 27 The same operation as in Example 25 was performed except that the flow rates of the aqueous layer and the organic layer were both 4.00 mL / min. As a result, the yield of 2-octyl-1-dodecyl acetate was 26.7%, and the acetic acid recovery rate was 26.9%.
  • Example 28 The same procedure as in Example 23 was performed except that the flow rates of the aqueous layer and the organic layer were changed to 1.00 mL / min for the aqueous layer and 0.33 mL / min for the organic layer. As a result, the yield of 2-octyl-1-dodecyl acetate was 25.1%. The concentration of 2-octyl-1-dodecyl acetate in the organic layer was 1.01% by mass, and the acetic acid recovery rate was 30.4%. Compared to Example 23, it can be seen that the concentration of 2-octyl-1-dodecyl acetate in the organic layer can be further increased by reducing the flow rate of the organic layer.
  • Example 29 An experiment for recovering acetic acid as ethyl acetate from a dilute acetic acid aqueous solution (acetic acid concentration: 1.0% by mass) corresponding to the wastewater of the acetaldehyde production plant was performed as follows.
  • the flow rate is 0.33 mL / min of the organic layer and 0.33 mL / min of the aqueous layer.
  • the water layer flowing out from the lower part and the organic layer flowing out from the upper part were collected, and the respective components were analyzed.
  • the concentration of 2-octyl-1-dodecyl acetate in the organic layer was 3.2% by mass
  • the concentration of unreacted acetic acid in the aqueous layer was 0.42% by mass
  • the concentration of 2-octyl-1-dodecanol was 160 ppm by mass.
  • the yield of 2-octyl-1-dodecyl acetate was 47.6%
  • the acetic acid recovery rate was 58.0%.
  • Ethyl acetate purification step The discharged organic layer was continuously treated by the purification process shown in FIG. Effluent from the condenser tube in the transesterification step (11) (reactive distillate after transesterification; ethyl acetate 10.5% by mass, ethanol 89.5% by mass) 1000 g (value per hour; value of other substances) The same applies to the amount.) From the top of the distillation column A (5) having a theoretical plate number of 37 to the 24th, 127 g of the top liquid (19) of the distillation column C (8) (44.8% by mass of ethyl acetate, ethanol 51.6% by mass and water 3.6% by mass) were supplied to the third stage from the top of the distillation column A (5) and purified by distillation.
  • the distillate (12) was extracted from the top of the distillation column A (5) (top temperature 77 ° C.).
  • the composition of the distillate (12) was 68.8% by mass of ethyl acetate, 29.3% by mass of ethanol, and 1.9% by mass of water.
  • the liquid (13) extracted from the bottom of the distillation column A (5) (ethyl acetate 0.3 mass%, ethanol 99.7 mass%) is returned to the reactor (4) and reused in the transesterification reaction. Is done.
  • the distillate (12) was supplied to an extraction column (6) having 8 theoretical plates, and 250 g of distillate (12) and water (14) were extracted in a counter-current manner at 40 ° C.
  • the composition of the extract (15) extracted from the top of the extraction tower was ethyl acetate 96.0% by mass, ethanol 0.0% by mass, and water 4.0% by mass.
  • the extract (15) is supplied to the 12th stage from the top of the distillation column B (7) having a theoretical plate number of 25 and purified by distillation.
  • a 100% ethyl acetate solution (18) is obtained from the column bottom (column bottom temperature: 98 ° C.).
  • Extracted (ethyl acetate recovery rate 97.7%, azeotrope of ethyl acetate (92%) and water (8%) is 70.5 ° C, so ethyl acetate (boiling point 77 ° C) is obtained from the bottom of the column. ).
  • the distillate from the top of the distillation column B (7) is separated into an aqueous layer and an organic layer by an oil / water separator (not shown), and the organic layer is returned to the top of the distillation column B (7).
  • the aqueous layer (17) 4.3 g (ethyl acetate 6.6% by mass, ethanol 0.0% by mass, water 93.4% by mass) was refluxed, and the aqueous layer (16) 373 g exited from the extraction tower (6). Together with (ethyl acetate 15.2% by mass, ethanol 17.7% by mass, water 67.2% by mass), the residue was purified by distillation in a distillation column C (8) having 25 theoretical plates.
  • Example 30 30 g of 0.2% by weight aqueous formic acid solution and 30 g of 2-octyl-1-dodecanol were charged into a 300 ml separable flask equipped with a condenser, and 1.2 g of p-dodecylbenzenesulfonic acid was added.
  • the formic acid was esterified and converted to 2-octyl-1-dodecyl formate, a hydrophobic substance.
  • the reaction solution was separated into a water layer and an organic layer with a separatory funnel, and each component analysis of the water layer and the organic layer was performed. As a result, the yield of 2-octyl-1-dodecyl formate was 42.1%, and the recovery rate of formic acid was 57.5%.
  • Example 31 30 g of 0.2% by mass aqueous propionic acid solution and 30 g of 2-octyl-1-dodecanol were charged into a 300 ml separable flask equipped with a condenser, and 1.2 g of p-dodecylbenzenesulfonic acid was added. The reaction was carried out at 30 ° C. for 30 minutes to esterify propionic acid and convert it into a hydrophobic substance 2-octyl-1-dodecyl propionate. The reaction solution was separated into a water layer and an organic layer with a separatory funnel, and each component analysis of the water layer and the organic layer was performed. As a result, the yield of 2-octyl-1-dodecyl propionate was 55.3%, and the recovery rate of propionic acid was 74.9%.
  • Example 32 30 g of 0.2 mass% acetic acid aqueous solution and 30 g of 1-octanol were charged into a 300 ml separable flask equipped with a cooling tube, 1.2 g of p-dodecylbenzenesulfonic acid was added, and constantly stirred at 80 ° C. for 30 minutes. Reaction was carried out, and acetic acid was esterified to convert it to 1-octyl acetate, which is a hydrophobic substance. The reaction solution was separated into a water layer and an organic layer with a separatory funnel, and each component analysis of the water layer and the organic layer was performed. As a result, the 1-octyl acetate yield was 60.0%, and the acetic acid recovery rate was 72.5%.
  • Example 33 Charge 30 g of 0.2 mass% acetic acid aqueous solution and 30 g of 1-decanol into a 300 ml separable flask equipped with a condenser, add 1.2 g of p-dodecylbenzenesulfonic acid, and react at 80 ° C. for 30 minutes with constant stirring.
  • the acetic acid was esterified and converted to 1-decyl acetate, which is a hydrophobic substance.
  • the reaction solution was separated into a water layer and an organic layer with a separatory funnel, and each component analysis of the water layer and the organic layer was performed. As a result, the 1-decyl acetate yield was 67.2%, and the acetic acid recovery was 71.9%.
  • Example 34 Using a reaction tower (inner diameter: 10 mm, length: 300 mm) packed with a packing (McMahon 6 mm ⁇ 6 mm), an aqueous solution (aqueous layer) in which organic substances are dissolved from the upper part while flowing warm water to the jacket part at 80 ° C. Then, 2-octyl-1-dodecanol (organic layer) in which p-dodecylbenzenesulfonic acid (8% by mass) was dissolved was introduced, and the aqueous layer and the organic layer were reacted in a counter flow.
  • the organic substance in the aqueous solution (aqueous layer) in which the organic substance introduced from the upper part is dissolved is acetic acid 12,900 mass ppm, acetaldehyde 18,600 mass ppm, crotonaldehyde 110 mass ppm, chloroacetaldehyde 5,530 mass ppm, dichloroacetaldehyde.
  • the amount was 1,510 mass ppm and the mass of 2-chloroethanol was 430 ppm.
  • the flow rate is 1.00 mL / min for both the aqueous layer and the organic layer.
  • the aqueous layer flowing out from the lower part of the reaction and the organic layer flowing out from the upper part were collected and analyzed for each component.
  • the yield of 2-octyl-1-dodecyl acetate was 31%, and the organic substance recovery rate was 48% acetic acid, 73% acetaldehyde, 61% crotonaldehyde, 58% chloroacetaldehyde, 78% dichloroacetaldehyde, 2- Chloroethanol was 60%.
  • FIG. 29 is a flowchart showing an example of the ethyl acetate recovery and purification process of Example 29.

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Abstract

L'invention porte sur un procédé de récupération de substances organiques, une substance organique et un alcool avec au moins huit atomes de carbone étant mis à réagir dans une solution aqueuse dans laquelle ladite substance organique est dissoute pour convertir ladite substance organique en une substance hydrophobe, la phase organique comportant ladite substance hydrophobe étant éliminée de la phase aqueuse. L'invention porte également sur un dispositif de récupération de substances organiques qui possède au moins un moyen pour faire réagir ladite substance organique dans la solution aqueuse dans laquelle la substance organique est dissoute avec un alcool d'au moins huit atomes de carbone pour la convertir en une substance hydrophobe, et un moyen pour séparer la phase organique comportant ladite substance hydrophobe et la phase aqueuse. Le procédé et le dispositif de récupération de substances organiques de cette invention ne génèrent pas beaucoup de produits de déchets industriels, tels qu'une boue excessive, et la taille du dispositif peut être réduite. Cette invention est particulièrement utile pour récupérer de l'acide acétique qui est contenu dans de l'eau résiduaire provenant du procédé de fabrication de l'acétaldéhyde.
PCT/JP2009/053702 2008-03-03 2009-02-27 Procédé et dispositif pour récupérer des substances organiques dans l'eau WO2009110384A1 (fr)

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JP2011148740A (ja) * 2010-01-22 2011-08-04 Univ Of Tokyo 水中の有機酸回収方法
JP2012196593A (ja) * 2011-03-18 2012-10-18 Sanwa Yuka Kogyo Kk 含浸液含有洗浄廃水のリサイクル方法
JP2022000631A (ja) * 2020-06-17 2022-01-04 国立研究開発法人産業技術総合研究所 水溶性有機酸の定量分析方法、エステル化試薬及び分析キット
CN115490286A (zh) * 2022-11-16 2022-12-20 北京惠宇乐邦环保科技有限公司 一种精细化工高浓废水中极性有机物的分离方法

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JPH029836A (ja) * 1986-04-03 1990-01-12 Nissan Chem Ind Ltd アルカリ廃水からの有用なカルボン酸の回収方法
JP2003511433A (ja) * 1999-10-08 2003-03-25 エー．イー．ステイレー マニュファクチャリング カンパニー 酸回収方法
JP2002126722A (ja) * 2000-10-26 2002-05-08 Hayaji Shibata 複数の酸が混合された廃液からの酸の分離回収方法
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011148740A (ja) * 2010-01-22 2011-08-04 Univ Of Tokyo 水中の有機酸回収方法
JP2012196593A (ja) * 2011-03-18 2012-10-18 Sanwa Yuka Kogyo Kk 含浸液含有洗浄廃水のリサイクル方法
JP2022000631A (ja) * 2020-06-17 2022-01-04 国立研究開発法人産業技術総合研究所 水溶性有機酸の定量分析方法、エステル化試薬及び分析キット
CN115490286A (zh) * 2022-11-16 2022-12-20 北京惠宇乐邦环保科技有限公司 一种精细化工高浓废水中极性有机物的分离方法

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