WO2018230011A1 - Procédé de production de cristaux d'acide dicarboxylique - Google Patents

Procédé de production de cristaux d'acide dicarboxylique Download PDF

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Publication number
WO2018230011A1
WO2018230011A1 PCT/JP2017/043774 JP2017043774W WO2018230011A1 WO 2018230011 A1 WO2018230011 A1 WO 2018230011A1 JP 2017043774 W JP2017043774 W JP 2017043774W WO 2018230011 A1 WO2018230011 A1 WO 2018230011A1
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Prior art keywords
acid
dicarboxylic acid
less
mass
salt
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PCT/JP2017/043774
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English (en)
Japanese (ja)
Inventor
諒 小船井
将宏 野場
裕 入江
伸吾 小山
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花王株式会社
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Priority claimed from JP2017214415A external-priority patent/JP7053220B2/ja
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to KR1020197035148A priority Critical patent/KR102458994B1/ko
Priority to CN201780091603.9A priority patent/CN110709376A/zh
Publication of WO2018230011A1 publication Critical patent/WO2018230011A1/fr

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    • 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
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/10—Succinic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C07C57/15—Fumaric acid

Definitions

  • the present invention relates to a method for producing a dicarboxylic acid crystal.
  • the C4 dicarboxylic acid (hereinafter also referred to as “C4 dicarboxylic acid”) is used as a raw material for bathing agents as well as a resin raw material and food additive.
  • C4 dicarboxylic acid is mainly used as an acid agent, and the ratio to the bath agent composition is high.
  • C4 dicarboxylic acid is industrially produced by chemical synthesis or microbial fermentation derived from a petrochemical raw material, and is usually purified as a crystal.
  • the crystallization operation of C4 dicarboxylic acid has been studied mainly for the purpose of improving the degree of purification of C4 dicarboxylic acid crystals and controlling the particle size.
  • a crystallizer comprising a cylindrical impeller, a crystallizer wall and a rotatable impeller shaft, at least selected from the group consisting of surfactants, buffer salts, acid salts, or mixtures thereof.
  • the surfactants disclosed in Patent Document 1 are polysorbate Tween 20, polyoxyethylene (6) lauryl ether (the number in parentheses represents the average number of moles of ethylene oxide added), cetyltrimethylammonium bromide, dodecyldimethylammonium bromide.
  • Patent Document 3 discloses that when an organic acid such as fumaric acid blended in the foaming bath agent composition is pulverized, the oil absorbency of the organic acid is increased.
  • Patent Document 3 as a result of measuring the oil absorption capacity of an organic acid using a liquid nonionic surfactant, the oil absorption capacity of fumaric acid having an average particle diameter of 35 ⁇ m is higher than that of fumaric acid having an average particle diameter of 140 ⁇ m. It has been shown.
  • Patent Document 1 JP-T-2003-505441 (Patent Document 2) JP-T-2001-511791 (Patent Document 3) JP-A-2012-158588
  • the present invention includes a step of precipitating crystals of a carbon number 4 dicarboxylic acid from an aqueous solution containing a carbon number 4 dicarboxylic acid or a salt thereof in the presence of an anionic polymer, and the carbon number 4 dicarboxylic acid in the aqueous solution.
  • the present invention provides a method for producing a dicarboxylic acid crystal having 4 carbon atoms, wherein the mass ratio of the anionic polymer content to the acid content is 5 ⁇ 10 ⁇ 4 or more and 0.5 or less.
  • the present inventor actually pulverized commercial fumaric acid as in Patent Document 3 and measured the oil absorption according to JIS K 5101-13-2 (2004), it was 36.6 mL / 100 g. (See Comparative Example 4 below).
  • the oil absorption amount of commercially available C4 dicarboxylic acid is about 25 to 30 mL / 100 g (see Comparative Examples 1 to 3 below).
  • the oil absorption amount of pulverized C4 dicarboxylic acid exceeds this, sufficient oil absorption amount is obtained depending on the pulverization. I could't. Therefore, the present invention relates to a method for producing C4 dicarboxylic acid crystals having a high oil absorption.
  • the present inventor crystallized from an aqueous solution containing C4 dicarboxylic acid or a salt thereof in the presence of an anionic polymer and the concentration of the anionic polymer relative to the concentration of C4 dicarboxylic acid is within a specific range. It has been found that the resulting C4 dicarboxylic acid crystals have a high oil absorption amount that has not been obtained conventionally.
  • the oil absorption amount of C4 dicarboxylic acid crystals can be increased, and a C4 dicarboxylic acid crystal having a high oil absorption amount can be obtained.
  • the C4 dicarboxylic acid crystal of the present invention can be produced by a method including a step of precipitating a C4 dicarboxylic acid crystal in the presence of an anionic polymer from an aqueous solution containing C4 dicarboxylic acid or a salt thereof.
  • the mass ratio of the content of the anionic polymer to the content of C4 dicarboxylic acid in the aqueous solution is 5 ⁇ 10 ⁇ 4 or more and 0.5 or less.
  • C4 dicarboxylic acid examples include fumaric acid, succinic acid, malic acid, tartaric acid, maleic acid, oxaloacetic acid and the like. Fumaric acid or succinic acid is preferable, and fumaric acid is more preferable. Moreover, it is preferable that C4 dicarboxylic acid or its salt is C4 dicarboxylic acid which does not have an amino acid residue, or its salt.
  • C4 dicarboxylic acid or a salt thereof is not particularly limited, and can be obtained by chemical synthesis derived from a petrochemical raw material such as benzene or butane, or by microbial fermentation.
  • Examples of the microorganism that produces C4 dicarboxylic acid or a salt thereof include filamentous fungi such as Rhizopus sp. When obtaining C4 dicarboxylic acid or its salt by microbial fermentation, you may precipitate the crystal
  • the anionic polymer used in the present invention is preferably water-soluble.
  • the anionic polymer include polymers having an anionic group such as a carboxyl group, a sulfuric acid group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group.
  • Specific examples of the natural polymer include xanthan gum, gum arabic, alginic acid, polyglutamic acid, and salts thereof.
  • Synthetic polymers include polymers or copolymers composed of monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, vinyl sulfonic acid, and salts thereof. .
  • carboxyalkyl cellulose and carboxyvinyl polymer such as carboxymethyl cellulose or carboxyethyl cellulose can be mentioned. These may be used alone or in combination.
  • the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, alkyl or alkenyl ammonium salts having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridinium salts having 1 to 22 carbon atoms, and alkanol ammoniums having 1 to 22 carbon atoms. Salt, basic amino acid salt and the like. Alkali metal salts are preferable, and sodium salts and potassium salts are more preferable.
  • the anionic polymer is preferably poly (meth) acrylic acid, polyglutamic acid, carboxyalkylcellulose or a salt thereof, more preferably poly (meth) acrylic, from the viewpoint of crystallizing a high oil absorption C4 dicarboxylic acid. Acid or a salt thereof, or polyglutamic acid, more preferably polyacrylic acid or a salt thereof.
  • the weight average molecular weight of the anionic polymer is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 5,000 or more, from the viewpoint of crystallizing a high oil absorption C4 dicarboxylic acid. , Preferably 2,000,000 or less, more preferably 1,000,000 or less, and still more preferably 500,000 or less.
  • the weight average molecular weight of the anionic polymer is preferably 1,000 or more and 2,000,000 or less, more preferably 2,000 or more and 1,000,000 or less, and further preferably 5,000 or more and 500,000. It is as follows.
  • the weight average molecular weight of the polymer can be measured, for example, by a gel permeation chromatography (GPC) method using sodium polyacrylate as a conversion standard according to the measurement target.
  • GPC gel permeation chromatography
  • the mass ratio of the content of the anionic polymer to the content of C4 dicarboxylic acid in the aqueous solution containing C4 dicarboxylic acid or a salt thereof is 5 ⁇ 10 ⁇ 4 or more and 0.5 or less. From the viewpoint of producing a C4 dicarboxylic acid crystal having a high oil absorption, it is preferably 0.001 or more, more preferably 0.002 or more, still more preferably 0.004 or more, still more preferably 0.01 or more.
  • the mass ratio of the content of the anionic polymer to the content of C4 dicarboxylic acid in the aqueous solution containing C4 dicarboxylic acid or a salt thereof is preferably 0.001 or more, 0.3 or less, more preferably 0.002 or more, It is 0.2 or less, more preferably 0.004 or more and 0.1 or less, further preferably 0.01 or more and 0.1 or less.
  • the content of C4 dicarboxylic acid is the sum of the content of C4 dicarboxylic acid and the content when C4 dicarboxylic acid salt is converted to C4 dicarboxylic acid.
  • the content of the anionic polymer in the aqueous solution containing C4 dicarboxylic acid or a salt thereof is preferably 0.001% by mass or more, more preferably 0.005% by mass from the viewpoint of crystallizing a high oil absorption amount of C4 dicarboxylic acid. % Or more, more preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, and preferably 5% from the viewpoint of industrial productivity and cost.
  • the content of the anionic polymer in the aqueous solution containing C4 dicarboxylic acid or a salt thereof is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.005% by mass or more and 1.5% by mass or less. More preferably, they are 0.01 mass% or more and 1 mass% or less, More preferably, they are 0.05 mass% or more and 0.5 mass% or less.
  • the method for precipitating the C4 dicarboxylic acid crystal is not particularly limited, and can be performed by operations such as a precipitation method by pH adjustment, a precipitation method by cooling, a precipitation method by concentration, and a precipitation method by reaction.
  • the C4 dicarboxylic acid crystal is preferably precipitated while stirring using a reaction vessel having a stirring blade.
  • the stirring blade may have any shape, but is preferably a paddle blade, a turbine blade, a propeller blade, an anchor blade, a large blade paddle blade, or a Max blend blade in order to improve the mixing of crystals.
  • the peripheral speed of stirring is preferably 0.2 m / s or more, more preferably 0.3 m / s or more, and even more preferably 0.5 m / s or more, from the viewpoint of uniformly crystallizing a high oil absorption amount of C4 dicarboxylic acid.
  • the viewpoint of crystallizing a high oil absorption amount of C4 dicarboxylic acid it is preferably 10 m / s or less, more preferably 5 m / s or less, and even more preferably 3 m / s or less.
  • the peripheral speed of stirring is preferably 0.2 m / s or more and 10 m / s or less, more preferably 0.3 m / s or more and 5 m / s or less, and further preferably 0.5 m / s or more and 3 m / s or less. is there.
  • the precipitation method based on pH adjustment can crystallize C4 dicarboxylic acid by liberating C4 dicarboxylic acid from C4 dicarboxylic acid salt by adding acid and increasing the concentration of C4 dicarboxylic acid to be higher than the solubility.
  • the acid used for pH adjustment can be used without particular limitation as long as the pKa is smaller than that of C4 dicarboxylic acid, and an inorganic acid is particularly preferable.
  • the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. Of these, sulfuric acid and hydrochloric acid are preferred.
  • the pH at the time of precipitation is adjusted to 9 or less, preferably 6 or less at the start of crystallization from the viewpoint of the recovery rate of C4 dicarboxylic acid, and is preferably adjusted to 2.5 or less by addition of acid. To do. Moreover, pH 0.5 or more is preferable from a corrosive viewpoint, such as a reaction tank.
  • the pH during crystal precipitation is preferably 0.5 or more and 9 or less, more preferably 0.5 or more and 6 or less, and further preferably 0.5 or more and 2.5 or less.
  • the acid addition rate is preferably 0.1 mmol-acid / L / min or more, more preferably 0.3 mmol-acid / L / min or more, more preferably from the viewpoint of crystallizing a high oil absorption amount of C4 dicarboxylic acid.
  • it is 5 mmol-acid / L / min or less, more preferably 3 mmol-acid / L / min or less, more preferably 2 mmol-acid / L / min or less.
  • the addition rate of acid is preferably 0.1 mmol-acid / L / min or more, 10 mmol-acid / L / min or less, more preferably 0.3 mmol-acid / L / min or more, 5 mmol-acid / L / min or less. More preferably, it is 0.3 mmol-acid / L / min or more and 3 mmol-acid / L / min or less, more preferably 1 mmol-acid / L / min or more and 2 mmol-acid / L / min or less.
  • mmol-acid / L / min indicates the amount of acid mixed per liter in the reaction solution per minute.
  • the temperature at which the precipitation by pH adjustment is carried out is not particularly limited, but is preferably carried out at a low temperature from the viewpoint of the recovery rate of C4 dicarboxylic acid.
  • the crystallization temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, and preferably 0 ° C. or higher, more preferably from the viewpoint of C4 dicarboxylic acid recovery. It is 5 ° C or higher.
  • the crystallization temperature is preferably 0 ° C. or higher and 50 ° C. or lower, more preferably 0 ° C. or higher and 40 ° C. or lower, still more preferably 5 ° C. or higher and 30 ° C. or lower.
  • the concentration of C4 dicarboxylic acid or a salt thereof when performing precipitation by pH adjustment is not particularly limited, but from the viewpoint of the recovery rate of C4 dicarboxylic acid, the amount of solubility at the temperature at the start of precipitation, or a slightly less amount than that Preferably there is.
  • the content of C4 dicarboxylic acid or a salt thereof in an aqueous solution containing C4 dicarboxylic acid or a salt thereof is preferably 45% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass. % Or less, preferably 1% by mass or more, more preferably 2% by mass or more.
  • the content of C4 dicarboxylic acid or a salt thereof in an aqueous solution containing C4 dicarboxylic acid or a salt thereof during precipitation by pH adjustment is preferably 1% by mass or more, 45% by mass or less, more preferably 1% by mass or more. 40 mass% or less, more preferably 2 mass% or more and 20 mass% or less.
  • the precipitation method by cooling can crystallize C4 dicarboxylic acid by cooling the aqueous solution containing C4 dicarboxylic acid or a salt thereof from high temperature to low temperature to increase the C4 dicarboxylic acid concentration to be higher than the solubility. Since C4 dicarboxylic acid has a property of high solubility when the temperature is high, it is preferable to cool after increasing the temperature of the dissolved acid by raising the temperature.
  • the temperature elevation temperature is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and preferably 120 ° C. or lower.
  • the temperature elevation temperature is preferably 60 ° C. or higher and 120 ° C.
  • the cooling temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, and preferably 0 ° C. or higher, more preferably 5 ° C. or higher, from the viewpoint of C4 dicarboxylic acid recovery. is there.
  • the cooling temperature is preferably 0 ° C. or higher and 50 ° C. or lower, more preferably 0 ° C. or higher and 40 ° C. or lower, still more preferably 5 ° C. or higher and 30 ° C. or lower.
  • the average cooling rate calculated from the time required from the temperature rise to the cooling temperature is preferably 0.05 from the viewpoint of the recovery rate of C4 dicarboxylic acid and the crystallization of a high oil absorption amount of C4 dicarboxylic acid.
  • °C / min or more more preferably 0.1 °C / min or more, adhesion of crystals to the reaction vessel, filterability of C4 dicarboxylic acid crystal suspension, moisture content of C4 dicarboxylic acid cake after filtration From this viewpoint, it is preferably 20 ° C./min or less, more preferably 10 ° C./min or less, still more preferably 5 ° C./min or less.
  • the average cooling rate calculated from the time taken from the temperature rising temperature to the cooling temperature is preferably 0.05 ° C./min or more, 20 ° C./min or less, more preferably 0.1 ° C./min or more, 10 ° C / min or less, more preferably 0.1 ° C / min or more and 5 ° C / min or less.
  • the pH in the precipitation method by cooling is preferably adjusted to 4 or less, more preferably 2.5 or less at the start of crystallization from the viewpoint of the recovery rate of C4 dicarboxylic acid. Moreover, pH 0.5 or more is preferable from a corrosive viewpoint, such as a reaction tank.
  • the concentration of C4 dicarboxylic acid or a salt thereof when performing precipitation by cooling is not particularly limited, but from the viewpoint of the recovery rate of C4 dicarboxylic acid, the amount of solubility at the temperature at the start of precipitation, or a little less than that. It is preferable.
  • the content of C4 dicarboxylic acid or a salt thereof in an aqueous solution containing C4 dicarboxylic acid or a salt thereof is preferably 45% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass. % Or less, preferably 1% by mass or more, more preferably 2% by mass or more.
  • the content of C4 dicarboxylic acid or a salt thereof in an aqueous solution containing C4 dicarboxylic acid or a salt thereof when performing precipitation by cooling is preferably 1% by mass or more, 45% by mass or less, more preferably 1% by mass or more, It is 40 mass% or less, More preferably, it is 2 mass% or more and 20 mass% or less.
  • the precipitation method by concentration is to crystallize C4 dicarboxylic acid by evaporating and concentrating the solvent (water) of an aqueous solution containing C4 dicarboxylic acid or a salt thereof, thereby increasing the concentration of C4 dicarboxylic acid beyond its solubility. Can do.
  • the concentration method is not particularly limited, and a reaction vessel or the like may be used, and the solvent (water) may be instantaneously evaporated by a spray dryer such as a spray dryer.
  • the temperature at the time of evaporation is not specifically limited, Preferably it is 300 degrees C or less, More preferably, it is 200 degrees C or less, Preferably it is 5 degrees C or more.
  • the temperature during evaporation is preferably 5 ° C. or higher and 300 ° C. or lower, more preferably 5 ° C. or higher and 200 ° C. or lower. Note that evaporation may be performed under reduced pressure.
  • the concentration of C4 dicarboxylic acid or a salt thereof when performing precipitation by concentration is not particularly limited, but is preferably set to a concentration corresponding to the solubility of each temperature of C4 dicarboxylic acid or slightly lower than that.
  • the content of C4 dicarboxylic acid or a salt thereof in an aqueous solution containing C4 dicarboxylic acid or a salt thereof is preferably 45% by mass or less, more preferably 40% by mass or less. More preferably, it is 20% by mass or less, preferably 1% by mass or more, more preferably 2% by mass or more.
  • the content of C4 dicarboxylic acid or a salt thereof in an aqueous solution containing C4 dicarboxylic acid or a salt thereof when performing precipitation by concentration is preferably 1% by mass or more, 45% by mass or less, more preferably 1% by mass or more, It is 40 mass% or less, More preferably, it is 2 mass% or more and 20 mass% or less.
  • the pH in the precipitation method by concentration is preferably adjusted to 4 or less, more preferably 2.5 or less at the start of crystallization from the viewpoint of the recovery rate of C4 dicarboxylic acid. Moreover, pH 0.5 or more is preferable from a corrosive viewpoint, such as a reaction tank.
  • the precipitation method by reaction can be appropriately set depending on the type of C4 dicarboxylic acid. For example, when fumaric acid is precipitated, fumaric acid is crystallized by increasing the fumaric acid concentration to be higher than its solubility by adding a catalyst to an aqueous solution containing maleic acid or maleic anhydride to produce fumaric acid. be able to.
  • the content of maleic acid or maleic anhydride in the aqueous solution containing maleic acid or maleic anhydride is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, and preferably It is 70 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
  • the temperature during the reaction is not particularly limited, but is preferably 60 ° C to 100 ° C.
  • the catalyst can be used without particular limitation as long as it is a catalyst that promotes the formation reaction of C4 dicarboxylic acid, and examples thereof include thiourea, bromate, and perborate. Moreover, you may add inorganic acids, such as a sulfuric acid and hydrochloric acid, at the time of reaction.
  • precipitation methods may be carried out singly or in combination of a plurality of methods.
  • a method for precipitating C4 dicarboxylic acid crystals an aqueous solution containing C4 dicarboxylic acid or a salt thereof is heated to 80 ° C. or higher, and after confirming dissolution, an average cooling of 0.05 ° C./min or higher is performed. Precipitation by cooling is performed at a rate, and after reaching 30 ° C., an inorganic acid may be added to lower the pH to 2.5 or less.
  • the crystals of C4 dicarboxylic acid can be collected by solid-liquid separation operations such as centrifugation, filtration, and decantation.
  • the crystal separation operation and the like are preferably performed within the above temperature range.
  • the C4 dicarboxylic acid crystal thus obtained may be washed as necessary.
  • C4 dicarboxylic acid crystals can be obtained by drying after washing as necessary.
  • a normal dryer such as a shelf dryer, a conical dryer, a paddle dryer, a nauter mixer, a fluidized bed dryer, a vacuum agitation dryer, a disk dryer, or an airflow dryer can be used.
  • a drying method that does not apply high shear is preferable.
  • the drying temperature is preferably 70 ° C or higher, more preferably 80 ° C or higher, still more preferably 100 ° C or higher, preferably 300 ° C or lower, more preferably 250 ° C or lower, still more preferably 200 ° C or lower, still more preferably. Is 150 ° C.
  • the C4 dicarboxylic acid crystals after drying may be subjected to a treatment such as passing through a sieve, if necessary.
  • C4 dicarboxylic acid crystal A C4 dicarboxylic acid crystal having a high oil absorption is thus obtained.
  • the C4 dicarboxylic acid crystal of the present invention preferably has an oil absorption of 40 mL / 100 g to 200 mL / 100 g measured according to JIS K 5101-13-2 (2004).
  • JIS K 5101-13-2 (2004) is a method for measuring the amount of oil absorbed by the oil method. Details of the measurement method are described in the examples. In the present specification, “the amount of oil absorption measured according to JIS K 5101-13-2 (2004)” is also simply referred to as “the amount of oil absorption”.
  • the oil absorption amount of the C4 dicarboxylic acid crystal is preferably 50 mL / 100 g to 200 mL / 100 g, more preferably 60 mL / 100 g to 200 mL / 100 g, and still more preferably 70 mL / 100 g to 200 mL / 100 g.
  • the highly oil-absorbing C4 dicarboxylic acid crystal is not particularly limited and can be used as a resin raw material, a food additive, and the like, but is particularly suitable as a raw material for a bath agent that is required to carry more oil agent expected to have a moisturizing effect. It is.
  • the present invention further discloses the following manufacturing method regarding the above-described embodiment.
  • a step of precipitating crystals of a carbon number 4 dicarboxylic acid in the presence of an anionic polymer from an aqueous solution containing a carbon number 4 dicarboxylic acid or a salt thereof, and the carbon number 4 dicarboxylic acid in the aqueous solution A method for producing a dicarboxylic acid crystal having 4 carbon atoms, wherein the mass ratio of the content of the anionic polymer to the content of is 5 ⁇ 10 ⁇ 4 or more and 0.5 or less.
  • the weight average molecular weight of the anionic polymer is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 5,000 or more, and preferably 2,000,000 or less. Preferably it is 1,000,000 or less, more preferably 500,000 or less, preferably 1,000 or more and 2,000,000 or less, more preferably 2,000 or more and 1,000,000 or less, More preferably, it is 5,000 or more and 500,000 or less, The manufacturing method as described in ⁇ 1>.
  • the mass ratio of the content of the anionic polymer to the content of the dicarboxylic acid having 4 carbon atoms in the aqueous solution containing the dicarboxylic acid having 4 carbon atoms or a salt thereof is preferably 0.001 or more, more preferably 0.
  • the content of the anionic polymer in the aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.8. 01% by mass or more, more preferably 0.03% by mass or more, further preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1%. % By mass or less, more preferably 0.5% by mass or less, further preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and preferably 0.001% by mass or more and 5% by mass or less.
  • the anionic polymer is preferably poly (meth) acrylic acid or a salt thereof, polyglutamic acid or a salt thereof, carboxyalkyl cellulose or a salt thereof, more preferably polyacrylic acid or a salt thereof ⁇ 1>.
  • ⁇ 6> The method according to any one of ⁇ 1> to ⁇ 5>, wherein the method for precipitating crystals is one or more methods selected from precipitation by pH adjustment, precipitation by cooling, precipitation by concentration, and precipitation by reaction. . ⁇ 7>
  • the pH during crystal precipitation by pH adjustment is preferably 9 or less, more preferably 6 or less, still more preferably 2.5 or less, and preferably pH 0.5 or more.
  • the production method according to ⁇ 6> preferably 0.5 or more and 9 or less, more preferably 0.5 or more and 6 or less, and still more preferably 0.5 or more and 2.5 or less.
  • the acid addition rate at the time of crystal precipitation by pH adjustment is preferably 0.1 mmol-acid / L / min or more, more preferably 0.3 mmol-acid / L / min or more, more preferably 1 mmol.
  • -Acid / L / min or more preferably 10 mmol-acid / L / min or less, more preferably 5 mmol-acid / L / min or less, more preferably 3 mmol-acid / L / min or less, more preferably 2 mmol-acid / L / min or less, preferably 0.1 mmol-acid / L / min or more, 10 mmol-acid / L / min or less, more preferably 0.3 mmol-acid / L / min or more, 5 mmol -Acid / L / min or less, more preferably 0.3 mmol-acid / L / min or more, 3 mmol-acid / L / min or less, more preferably 1 m ol- acid / L / min or more, the production method according to or less 2mmol- acid / L / min ⁇ 6> or ⁇ 7>.
  • the temperature at which crystals are precipitated by adjusting the pH is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, and preferably 0 ° C. or higher, more preferably ⁇ 5> or higher, preferably 0 ° C. or higher and 50 ° C. or lower, more preferably 0 ° C. or higher and 40 ° C.
  • the content of the dicarboxylic acid having 4 carbon atoms or the salt thereof in the aqueous solution containing the dicarboxylic acid having 4 carbon atoms or a salt thereof when performing crystal precipitation by pH adjustment is preferably 45% by mass or less.
  • Preferably it is 40% by mass or less, more preferably 20% by mass or less, preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 1% by mass or more, 45% by mass or less,
  • ⁇ 12> The production method according to ⁇ 6>, wherein the precipitation of the crystal by cooling is preferably performed after the temperature of the aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof is raised.
  • Temperature elevation temperature is preferably 60 ° C.
  • the production method according to ⁇ 12> which is more preferably 70 ° C. or higher and 120 ° C. or lower, further preferably 80 ° C. or higher and 120 ° C. or lower.
  • the cooling temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, preferably 0 ° C. or higher, more preferably 5 ° C.
  • ⁇ 6>, ⁇ 12>, or ⁇ 13> which is 0 ° C or higher and 50 ° C or lower, more preferably 0 ° C or higher and 40 ° C or lower, and further preferably 5 ° C or higher and 30 ° C or lower.
  • the average cooling rate calculated from the time taken from the temperature rise to the cooling temperature is preferably 0.05 ° C./min or more, more preferably 0.1 ° C./min or more, It is preferably 20 ° C./min or less, more preferably 10 ° C./min or less, further preferably 5 ° C./min or less, preferably 0.05 ° C./min or more and 20 ° C./min or less, more preferably 0.
  • the production method according to any one of ⁇ 12> to ⁇ 14> which is from 1 ° C / min to 10 ° C / min, more preferably from 0.1 ° C / min to 5 ° C / min.
  • the pH at which crystals are precipitated by cooling is preferably 4 or less, more preferably 2.5 or less, preferably pH 0.5 or more, and preferably 0.5 or more.
  • the content of the dicarboxylic acid having 4 carbon atoms or the salt thereof in the aqueous solution containing the dicarboxylic acid having 4 carbon atoms or a salt thereof when performing crystal precipitation by cooling is preferably 45% by mass or less, more preferably Is 40% by mass or less, more preferably 20% by mass or less, preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 1% by mass or more and 45% by mass or less.
  • Precipitation of crystals by concentration is performed by evaporating the solvent of an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof, and then concentrating, and the temperature during evaporation is preferably 300 ° C. or less, more preferably Is 200 ° C. or lower, preferably 5 ° C. or higher, and preferably 5 ° C. or higher and 300 ° C. or lower, more preferably 5 ° C. or higher and 200 ° C. or lower.
  • the content of the dicarboxylic acid having 4 carbon atoms or the salt thereof in the aqueous solution containing the dicarboxylic acid having 4 carbon atoms or a salt thereof when performing crystal precipitation by concentration is preferably 45% by mass or less, more preferably Is 40% by mass or less, more preferably 20% by mass or less, preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 1% by mass or more and 45% by mass or less.
  • the pH at which crystals are precipitated by concentration is preferably 4 or less, more preferably 2.5 or less, preferably pH 0.5 or more, and preferably 0.5 or more.
  • Precipitation of crystal is preferably 0.2 m / s or more, more preferably 0.3 m / s or more, more preferably 0.5 m / s or more, more preferably 10 m or more.
  • ⁇ 1> to ⁇ 20> which is performed with stirring at a speed of from / s to 5 m / s, more preferably from 0.5 m / s to 3 m / s.
  • Precipitation of crystals is performed by cooling an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof to 80 ° C. or higher and confirming dissolution, and then cooling at an average cooling rate of 0.05 ° C./min or higher. After the temperature reaches 30 ° C., the production method according to any one of ⁇ 1> to ⁇ 21>, wherein the inorganic acid is added to lower the pH to 2.5 or lower.
  • the C4 dicarboxylic acid crystal is preferably a fumaric acid, succinic acid, malic acid, tartaric acid, maleic acid, or oxaloacetic acid crystal, more preferably a fumaric acid or succinic acid crystal,
  • the dicarboxylic acid crystal having 4 carbon atoms is a fumaric acid crystal, and the crystal is precipitated by a reaction in which a catalyst is added to an aqueous solution containing maleic acid or maleic anhydride to generate fumaric acid ⁇ 6> or ⁇ 21>
  • the content of maleic acid or maleic anhydride in the aqueous solution containing maleic acid or maleic anhydride is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more.
  • the manufacturing method as described in ⁇ 24> which is 70 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
  • ⁇ 26> The production method according to ⁇ 24> or ⁇ 25>, wherein the temperature during the reaction is 60 ° C. or higher and 100 ° C. or lower.
  • ⁇ 27> The production method according to any one of ⁇ 24> to ⁇ 26>, wherein the catalyst is preferably thiourea, bromate, or perborate.
  • the oil absorption of the dicarboxylic acid crystal having 4 carbon atoms measured according to JIS K 5101-13-2 (2004) is preferably 50 mL / 100 g to 200 mL / 100 g, more preferably 60 mL / 100 g to 200 mL. / 100 g, more preferably 70 mL / 100 g to 200 mL / 100 g, the production method according to any one of ⁇ 1> to ⁇ 27>.
  • ⁇ 29> A C4 dicarboxylic acid crystal obtained by the production method according to any one of ⁇ 1> to ⁇ 28>.
  • Comparative Example 4 Fumaric acid manufactured by Nippon Shokubai Co., Ltd. was pulverized by stirring for 20 min at a blade diameter of 140 mm and a speed of 3000 r / min using a super mixer Piccolo SMP2 (manufactured by Kawata Corporation). The oil absorption of the pulverized fumaric acid was measured and found to be 36.6 mL / 100 g. The results of Comparative Examples 1 to 4 are shown in Table 1.
  • Example 1 After mixing 2.14 kg of ion-exchanged water and 105 g of fumaric acid in a 3 L reaction tank (diameter 130 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, after 1.125 g of polyacrylic acid (molecular weight 5000 g / mol) was mixed, fumaric acid was precipitated by cooling from 85 ° C. to 25 ° C. at an average cooling rate of 0.3 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 250 r / min. Next, the precipitated fumaric acid suspension was No. Suction filtration was performed using 2 filter papers.
  • the filtered fumaric acid cake was dried at 105 ° C. with a hot air circulating dryer FS-60WT (manufactured by Tokyo Glass Instruments Co., Ltd.). After drying, a fumaric acid crystal was obtained by passing through a sieve having an opening of 500 ⁇ m. It was 72.0 mL / 100g when the oil absorption of the obtained fumaric acid crystal was measured.
  • FS-60WT hot air circulating dryer
  • Example 2 In the same experiment as in Example 1, the amount of polyacrylic acid added was changed to 0.788 g, and the experiment was conducted. The oil absorption of the obtained fumaric acid crystals was measured and found to be 65.0 mL / 100 g.
  • Example 3 In the same experiment as in Example 1, the amount of polyacrylic acid added was changed to 0.45 g and the experiment was conducted. The oil absorption of the obtained fumaric acid crystals was measured and found to be 65.0 mL / 100 g.
  • Example 4 In the same experiment as in Example 1, the amount of polyacrylic acid added was changed to 0.113 g, and the experiment was conducted. It was 60.0 mL / 100g when the oil absorption amount of the obtained fumaric acid crystal
  • Example 5 After mixing 79.9 kg of ion-exchanged water and 3923 g of fumaric acid in a 100 L reaction tank (diameter 450 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, after mixing 168 g of polyacrylic acid (molecular weight 5000 g / mol), fumaric acid was precipitated by cooling from 85 ° C. to 25 ° C. at an average cooling rate of 0.3 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 405 mm under the condition of 50 r / min. Next, the precipitated fumaric acid suspension was No. Suction filtration was performed using 2 filter papers.
  • the filtered fumaric acid cake was dried at 60 ° C. in a hot air circulating dryer FS-60WT (manufactured by Tokyo Glass Instrument Co., Ltd.). After drying, a fumaric acid crystal was obtained by passing through a sieve having an opening of 500 ⁇ m. It was 60.0 mL / 100g when the oil absorption amount of the obtained fumaric acid crystal
  • Example 6 After mixing 2.14 kg of ion-exchange water and 105.8 g of fumaric acid in a 3 L reaction tank (450 mm in diameter), the temperature was raised to 85 ° C. and dissolved. Subsequently, after 1.13 g of polyacrylic acid (molecular weight 250,000 g / mol) was mixed, fumaric acid was precipitated by cooling from 80 ° C. to 25 ° C. at an average cooling rate of 0.3 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 250 r / min. Next, the precipitated fumaric acid suspension was No. Suction filtration was performed using 2 filter papers.
  • Example 7 After mixing 2.14 kg of ion-exchange water and 105.8 g of fumaric acid in a 3 L reaction tank (450 mm in diameter), the temperature was raised to 85 ° C. and dissolved. Subsequently, after 1.13 g of polyacrylic acid (molecular weight 25000 g / mol) was mixed, fumaric acid was precipitated by cooling from 80 ° C. to 25 ° C. at an average cooling rate of 0.3 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 250 r / min. Next, the precipitated fumaric acid suspension was No. Suction filtration was performed using 2 filter papers.
  • the filtered fumaric acid cake was dried at 105 ° C. with a hot air circulating dryer FS-60WT (manufactured by Tokyo Glass Instruments Co., Ltd.). After drying, a fumaric acid crystal was obtained by passing through a sieve having an opening of 500 ⁇ m. The oil absorption of the obtained fumaric acid crystals was measured and found to be 110.0 mL / 100 g.
  • Example 8 In the same experiment as in Example 1, the type of polyacrylic acid to be added was changed to polyacrylic acid (molecular weight 1800 g / mol). However, since the reagent used was a 63% aqueous solution of polyacrylic acid, the addition amount of the aqueous solution was 1.59 times the addition amount of Example 1. The oil absorption of the obtained fumaric acid crystals was measured and found to be 59.0 mL / 100 g.
  • Example 9 After mixing 2.14 kg of ion-exchange water and 105.8 g of fumaric acid in a 3 L reaction tank (450 mm in diameter), the temperature was raised to 85 ° C. and dissolved. Subsequently, 1.13 g of sodium carboxymethyl cellulose (Tokyo Chemical Industry Co., Ltd.) was mixed, and then fumaric acid was precipitated by cooling from 80 ° C. to 25 ° C. at an average cooling rate of 0.3 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 250 r / min. Next, the precipitated fumaric acid suspension was No. Suction filtration was performed using 2 filter papers.
  • sodium carboxymethyl cellulose Tokyo Chemical Industry Co., Ltd.
  • the filtered fumaric acid cake was dried at 105 ° C. with a hot air circulating dryer FS-60WT (manufactured by Tokyo Glass Instruments Co., Ltd.). After drying, a fumaric acid crystal was obtained by passing through a sieve having an opening of 500 ⁇ m. It was 100.0 mL / 100g when the oil absorption of the obtained fumaric acid crystal was measured.
  • Tables 2 and 3 show the results of Examples 1 to 9 and Comparative Example 5.
  • Example 10 (Crystal crystallization by reaction) [Example 10] After mixing 1.55 kg of ion-exchanged water, 450 g of maleic anhydride, 9.58 g of polyacrylic acid (molecular weight 5000 g / mol) and 24.2 g of 98% sulfuric acid in a 3 L reactor (diameter 130 mm), the temperature was raised to 70 ° C. Warm and dissolve. Subsequently, an isomerization reaction from maleic acid to fumaric acid was advanced by feeding a 6.19% aqueous thiourea solution at a rate of 1.8 ml / min over 120 minutes to precipitate fumaric acid. After 120 minutes, the mixture was held at 70 ° C.
  • Table 4 shows the results of Example 10 and Comparative Example 6.
  • Example 11 After mixing 1.80 kg of ion exchange water and 450.0 g of succinic acid in a 3 L reaction tank (450 mm in diameter), the mixture was heated to 80 ° C. and dissolved. Subsequently, 4.77 g of polyacrylic acid (weight average molecular weight 5000) (Tokyo Kasei Kogyo Co., Ltd.) was mixed and cooled from 80 ° C. to 25 ° C. at an average cooling rate of 0.3 ° C./min. The acid was precipitated. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 250 r / min. Next, the precipitated succinic acid suspension was No.

Abstract

L'invention concerne un procédé de production de cristaux d'acide dicarboxylique en C4 ayant une absorption d'huile élevée. Ce procédé de production de cristaux d'acide dicarboxylique en C4 comprend une étape dans laquelle des cristaux d'acide dicarboxylique en C4 sont précipités à partir d'une solution aqueuse contenant un acide dicarboxylique en C4 ou un sel de celui-ci en présence d'un polymère anionique. Le rapport en masse de la teneur en polymère anionique à la teneur en acide dicarboxylique en C4 dans la solution aqueuse est de 5 x 10-4 à 0,5.
PCT/JP2017/043774 2017-06-15 2017-12-06 Procédé de production de cristaux d'acide dicarboxylique WO2018230011A1 (fr)

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JP2021042191A (ja) * 2019-09-12 2021-03-18 江蘇永星化工股▲ふん▼有限公司 （±）−２，２’−ビス−（２−ヒドロキシエトキシ）−１，１’−ビナフチル結晶及び調製方法

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