Classifications

• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
  • A61K8/362—Polycarboxylic acids
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/10—Washing or bathing preparations
• • 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 dicarboxylic acid crystal, and further to a C4 dicarboxylic acid crystal and a method for producing the same.
• 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 2012-158588 (Patent Document 4) International Publication No. 2016/083749
• the present invention provides a C4 dicarboxylic acid crystal having an oil absorption measured in accordance with JIS K 5101-13-2 (2004) of 40 mL / 100 g to 200 mL / 100 g.
• the present invention also relates to an (a1) nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less, and (a2) an HLB of less than 15 from an aqueous solution containing a C4 dicarboxylic acid or a salt thereof.
• a method for producing a dicarboxylic acid crystal is provided.
• the present invention provides at least one selected from (b1) a nonionic polymer, (b2) a cationic polymer, and (b3) an amphoteric polymer from an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof.
• the present invention provides a method for producing a C4 dicarboxylic acid crystal, comprising the step of precipitating a C4 dicarboxylic acid crystal in the presence of the above polymer.
• 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 6 below).
• the oil absorption amount of commercially available C4 dicarboxylic acid is about 25 to 30 mL / 100 g (see Comparative Examples 1 to 5 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 providing a C4 dicarboxylic acid crystal having a high oil absorption and a method for producing the same.
• the present inventor among surfactants and polymers, has a C4 dicarboxylic acid in the presence of one or more selected from a predetermined nonionic surfactant, nonionic polymer, cationic polymer and amphoteric polymer. It has been found that C4 dicarboxylic acid crystals obtained by crystallization from an aqueous solution containing an acid or a salt thereof have a high oil absorption amount that has not been obtained conventionally.
• the C4 dicarboxylic acid crystal of the present invention has a high oil absorption. Therefore, the C4 dicarboxylic acid crystal of the present invention can carry more oil agent and can be suitably used as a raw material for bathing agents and the like. Moreover, according to the method of the present invention, the oil absorption amount of the C4 dicarboxylic acid crystal 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 has an oil absorption of 40 mL / 100 g to 200 mL / 100 g measured according to JIS K 5101-13-2 (2004).
• Examples of the C4 dicarboxylic acid in the present invention 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.
• C4 dicarboxylic acid or its salt is C4 dicarboxylic acid or its salt which does not have an amino acid residue.
• 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 of the C4 dicarboxylic acid crystal of the present invention is 40 mL / 100 g to 200 mL / 100 g, preferably 50 mL / 100 g to 200 mL / 100 g, more preferably 60 mL / 100 g to 200 mL / 100 g, still more preferably 70 mL / 100 g. ⁇ 200 mL / 100 g.
• the C4 dicarboxylic acid crystal of the present invention comprises: (a1) a nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less, and (a2) an HLB of less than 15 from an aqueous solution containing C4 dicarboxylic acid or a salt thereof. It can be produced by a method including a step of precipitating C4 dicarboxylic acid crystals in the presence of at least one nonionic surfactant selected from nonionic surfactants having no polyoxyethylene chain.
• the C4 dicarboxylic acid crystal is an at least one kind selected from (b1) a nonionic polymer, (b2) a cationic polymer, and (b3) an amphoteric polymer from an aqueous solution containing C4 dicarboxylic acid or a salt thereof. It can be produced by a method including a step of precipitating C4 dicarboxylic acid crystals in the presence of a polymer.
• the nonionic surfactants (a1) to (a2) may be used singly or in combination.
• the polymers (b1) to (b3) may be used alone or in combination.
• the nonionic surfactants (a1) to (a2) and the polymers (b1) to (b3) may be used in combination.
• the nonionic surfactant and the polymer may be present at the time of precipitation of the C4 dicarboxylic acid crystal, and the timing of adding them to the aqueous solution containing the C4 dicarboxylic acid or a salt thereof is not particularly limited.
• C4 dicarboxylic acid (fumaric acid, succinic acid, malic acid, tartaric acid, maleic acid, oxaloacetic acid, etc.) or a salt thereof is not particularly limited, and is obtained by chemical synthesis derived from a petrochemical raw material such as benzene or butane, or by microbial fermentation. Can do.
• Examples of chemical synthesis derived from petrochemical raw materials include maleic anhydride or maleic acid isomerization reaction (fumaric acid), reduction reaction, hydrogenation reaction (succinic acid), hydration, etc.
• Examples thereof include a reaction (malic acid), maleic anhydride, or a hydration reaction of tartaric acid obtained by epoxidation of maleic acid (tartaric acid).
• 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
• HLB is an index indicating a hydrophilic-lipophilic balance, and is a numerical value calculated from an inorganic value and an organic value by Oda / Teramura et al.
• HLB ( ⁇ inorganic value / ⁇ organic) ⁇ 10.
• organic value and “organic value” corresponding to various atoms or functional groups are set (for example, Yoshio Koda, “Organic Conceptual Diagram-Fundamentals and Applications”, pages 11-17, Sankyo Publishing 1984.
• the HLB of the organic compound is calculated by integrating the “inorganic value” and “organic value” of all atoms and functional groups in the organic compound.
• the HLB of a nonionic surfactant is 1 to 20.
• HLB in the case of being composed of two or more kinds of nonionic surfactants is obtained by averaging the HLB of each nonionic surfactant based on the blending mass ratio as shown in the following formula. is there.
• HLBx HLB of the nonionic surfactant X
• Wx represents the mass (g) of the nonionic surfactant X having a value of HLBx.
• Nonionic surfactant used in the present invention has (a1) a nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less, and (a2) a polyoxyethylene chain having an HLB of less than 15. And at least one selected from nonionic surfactants.
• Nonionic surfactants having a polyoxyethylene chain with an HLB of 10 or less include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxy Propylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene cured Castor oil and the like.
• polyoxyethylene alkyl ether polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil, and polyoxyethylene castor oil are preferable. It is at least one selected from oxyethylene hydrogenated castor oil, more preferably at least one selected from polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitol fatty acid ester, more preferably poly It is at least one selected from oxyethylene alkyl ether and polyoxyethylene sorbitol fatty acid ester.
• the number of moles of ethylene oxide added in the polyoxyethylene chain is shown as an average value, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 60 or less, more preferably 50. Hereinafter, it is more preferably 40 or less, still more preferably 30 or less, still more preferably 25 or less, and even more preferably 20 or less.
• the number of carbon atoms of the fatty acid part, alkyl part and alkenyl part of the nonionic surfactant is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 24 or less, more preferably Is 22 or less, more preferably 20 or less. “Having a polyoxyethylene chain” means a structure in which 1 mol or more of ethylene oxide is added to the molecule of the nonionic surfactant.
• the HLB of the nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less is preferably 1 or more, more preferably 4 or more, from the viewpoint of producing a high oil absorption amount of C4 dicarboxylic acid crystals. More preferably, it is 5 or more.
• Nonionic surfactants having an HLB of less than 15 and having no polyoxyethylene chain include polyglycerin fatty acid ester, glycerin fatty acid ester, ethylene glycol fatty acid ester, propylene glycol fatty acid ester, butylene glycol fatty acid ester Sorbitan fatty acid ester, sucrose fatty acid ester, alkyl glucoside and the like.
• polyglycerin fatty acid ester glycerin fatty acid ester, ethylene glycol fatty acid ester, propylene glycol fatty acid ester, butylene glycol fatty acid ester Sorbitan fatty acid ester, sucrose fatty acid ester, alkyl glucoside and the like.
• at least one selected from sorbitan fatty acid esters and alkyl glucosides is preferred.
• the HLB of the nonionic surfactant having no polyoxyethylene chain having an HLB of less than 15 is preferably 4 or more, more preferably 8 or more, from the viewpoint of crystallizing a high oil absorption amount of C4 dicarboxylic acid. More preferably, it is 10 or more, and preferably 13 or less.
• the HLB of the nonionic surfactant not having a polyoxyethylene chain having an HLB of less than 15 is preferably 4 or more, less than 15, more preferably 8 or more, 13 or less, still more preferably 10 or more, 13 It is as follows. Commercially available nonionic surfactants can be used.
• the concentration of the nonionic surfactant when precipitating C4 dicarboxylic acid crystals is preferably 0.
• an aqueous solution containing C4 dicarboxylic acid or a salt thereof from the viewpoint of crystallizing a high oil absorption amount of C4 dicarboxylic acid.
• 001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and from the viewpoint of industrial operability such as foaming and cost preferably 5% by mass or less, more Preferably it is 1.5 mass% or less, More preferably, it is 1 mass% or less.
• the content of the nonionic surfactant 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 0.01% by mass or more and 1.5% by mass. % Or less, more preferably 0.05% by mass or more and 1% by mass or less.
• the ratio (mass ratio) of the surfactant content is preferably 0.001 to 0.5, more preferably 0.002 to 0.3, and more preferably from the viewpoint of producing a high oil absorption C4 dicarboxylic acid crystal. Preferably, it is 0.01 to 0.3.
• the polymer used in the present invention is at least one selected from (b1) a nonionic polymer, (b2) a cationic polymer, and (b3) an amphoteric polymer. These polymers are preferably water-soluble.
• the nonionic polymer may be a water-soluble synthetic polymer, a water-soluble semi-synthetic polymer, or a water-soluble natural polymer.
• Nonionic polymers include, for example, starch polymers (eg, carboxymethyl starch, soluble starch, methyl starch, etc.), cellulose polymers (eg, alkyl celluloses such as methyl cellulose and ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, etc. Hydroxyalkyl cellulose), vinyl polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether), polyalkylene glycol, and the like.
• the nonionic polymer is preferably a vinyl polymer or hydroxyalkyl cellulose obtained by polymerizing a monomer having a vinyl group, and more preferably polyvinyl alcohol or hydroxyalkyl cellulose, from the viewpoint of crystallizing a high oil absorption C4 dicarboxylic acid.
• Ethyl cellulose is preferably a vinyl polymer or hydroxyalkyl cellulose obtained by polymerizing a monomer having a vinyl group, and more preferably polyvinyl alcohol or hydroxyalkyl cellulose, from the viewpoint of crystallizing a high oil absorption C4 dicarboxylic acid.
• Examples of the cationic polymer include cationized cellulose, cationized starch, cationized guar gum, polyethyleneimine polymer, dicyandiamide polymer, diallylamine polymer, and the like.
• the cationic polymer is preferably cationized cellulose from the viewpoint of crystallizing a high oil absorption amount of C4 dicarboxylic acid.
• amphoteric polymers examples include methacryloyloxyethyl phosphorylcholine-methacrylic acid copolymer, methacryloyloxyethyl phosphorylcholine-stearyl methacrylate copolymer, ethyl betaine methacrylate-acrylic acid copolymer, styrene-acrylic acid-acrylic acid.
• Dialkylamino ester polymer allylamine-maleic acid copolymer, aminoethyl methacrylate-methacrylic acid copolymer, vinylpyridine-maleic acid copolymer, methylaminoethyl methacrylate-acrylic acid copolymer, vinylpyridine-itaconic acid copolymer Examples thereof include a polymer and a methylallylamine-itaconic acid copolymer.
• the amphoteric polymer is preferably a methacryloyloxyethyl phosphorylcholine-stearyl methacrylate copolymer from the viewpoint of crystallizing a high oil absorption C4 dicarboxylic acid.
• the weight average molecular weight of the polymer is preferably 3,000 or more, more preferably 10,000 or more, and still more preferably 30,000 or more from the viewpoint of crystallizing a high oil absorption C4 dicarboxylic acid. From the viewpoint of the filterability of the dicarboxylic acid crystal suspension and the moisture content of the cake after filtration, it is preferably 2,000,000 or less, more preferably 1,000,000 or less, and even more preferably 500,000 or less.
• the weight average molecular weight of the polymer is preferably 3,000 or more and 2,000,000 or less, more preferably 10,000 or more and 1,000,000 or less, still more preferably 30,000 or more and 500,000 or less. is there.
• the weight average molecular weight of the polymer can be measured by, for example, a gel permeation chromatography (GPC) method.
• the concentration of the polymer when precipitating C4 dicarboxylic acid crystals is preferably 0.001% by mass or more in an aqueous solution containing C4 dicarboxylic acid or a salt thereof. , More preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and from the viewpoint of industrial productivity and cost, preferably 5% by mass or less, more preferably 1.5% by mass. Hereinafter, it is more preferably 1% by mass or less, and further preferably 0.5% by mass or less.
• the content of the 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 0.01% by mass or more and 1.5% by mass or less.
• they are 0.05 mass% or more and 1 mass% or less, More preferably, they are 0.05 mass% or more and 0.5 mass% or less.
• the content of the polymer with respect to the content of C4 dicarboxylic acid in the aqueous solution containing C4 dicarboxylic acid or a salt thereof (the sum of the content of C4 dicarboxylic acid and the content when C4 dicarboxylic acid salt is converted to C4 dicarboxylic acid)
• the mass ratio of the amount is preferably 0.001 to 0.5, more preferably 0.002 to 0.3, from the viewpoint of crystallizing a high oil absorption dicarboxylic acid.
• the total content of the nonionic surfactants (a1) to (a2) and the polymers (b1) to (b3) in the aqueous solution containing C4 dicarboxylic acid or a salt thereof is preferably 0.001% by mass or more It is 10 mass% or less, More preferably, it is 0.01 mass% or more, 3 mass% or less, More preferably, it is 0.05 mass% or more, and 2 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 concentration 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 concentration 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 temperature at the time of evaporation is not specifically limited, Preferably it is 100 degrees C or less, More preferably, it is 80 degrees C or less, Preferably it is 5 degrees C or more.
• the temperature during evaporation is preferably 5 ° C. or higher and 100 ° C. or lower, more preferably 5 ° C. or higher and 80 ° 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 concentration 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 mass% or less, Preferably it is 1 mass% or more, More preferably, it is 2 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.
• 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.
• 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 content of maleic acid or maleic anhydride in the aqueous solution containing maleic acid or maleic anhydride when performing precipitation by reaction is preferably 5% by mass or more, 70% by mass or less, more preferably 10% by mass or more, It is 50 mass% or less, More preferably, it is 10 mass% or more and 40 mass% or less, More preferably, it is 20 mass% or more and 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, or a disk 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.
• the C4 dicarboxylic acid crystal obtained by the method of the present invention has a high oil absorption. Therefore, according to the method of the present invention, the oil absorption of C4 dicarboxylic acid crystals can be improved.
• the preferred oil absorption of the C4 dicarboxylic acid crystal is as described above.
• 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 C4 dicarboxylic acid crystal, production method, or improvement method.
• the oil absorption of the dicarboxylic acid crystal having 4 carbon atoms 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 C4 dicarboxylic acid crystal of> 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 C4 dicarboxylic acid crystal of> 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
• the dicarboxylic acid crystal having 4 carbon atoms 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,
• ⁇ 4> From an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof, (a1) a nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less, and (a2) a polyoxyethylene having an HLB of less than 15
• a carbon number 4 dicarboxylic acid crystal comprising a step of precipitating a carbon number 4 dicarboxylic acid crystal in the presence of at least one nonionic surfactant selected from nonionic surfactants having no chain Manufacturing method.
• ⁇ 5> From an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof, (a1) a nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less, and (a2) a polyoxyethylene having an HLB of less than 15
• a carbon number 4 dicarboxylic acid crystal comprising a step of precipitating a carbon number 4 dicarboxylic acid crystal in the presence of at least one nonionic surfactant selected from nonionic surfactants having no chain To improve oil absorption.
• ⁇ 6> The method according to ⁇ 4> or ⁇ 5>, wherein the C4 dicarboxylic acid or a salt thereof is preferably a C4 dicarboxylic acid or a salt thereof obtained by chemical synthesis derived from a petrochemical raw material.
• a nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less is preferably polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene It is at least one selected from castor oil and polyoxyethylene hydrogenated castor oil, more preferably at least one selected from polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitol fatty acid ester More preferably, the method according to any one of ⁇ 4> to ⁇ 6>, which is at least one selected from polyoxyethylene alkyl ether and polyoxyethylene sorbitol fatty acid ester.
• the number of moles of ethylene oxide added in the polyoxyethylene chain is an average value, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 60 or less, more preferably 50. Or less, still more preferably 40 or less, even more preferably 30 or less, even more preferably 25 or less, even more preferably 20 or less, and preferably 2 or more and 60 or less, more preferably 3 or more and 50 or less, More preferably 3 or more and 40 or less, more preferably 3 or more and 30 or less, more preferably 4 or more and 25 or less, and further preferably 4 or more and 20 or less, and any one of ⁇ 4> to ⁇ 7> the method of.
• the number of carbon atoms of the fatty acid part, the alkyl part and the alkenyl part of the nonionic surfactant is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 24 or less. Preferably it is 22 or less, more preferably 20 or less, preferably 6 or more and 24 or less, more preferably 8 or more and 22 or less, and further preferably 10 or more and 20 or less, from ⁇ 4> to ⁇ 8> The method according to any one of the above.
• the HLB of the nonionic surfactant having a polyoxyethylene chain having an HLB of 10 or less is preferably 1 or more, more preferably 4 or more, still more preferably 5 or more, and preferably The method according to any one of ⁇ 4> to ⁇ 9>, which is 1 or more and 10 or less, more preferably 4 or more and 10 or less, and still more preferably 5 or more and 10 or less.
• the nonionic surfactant having no polyoxyethylene chain having an HLB of less than 15 is preferably at least one selected from sorbitan fatty acid esters and alkyl glucosides ⁇ 4> to ⁇ 10> The method according to any one of the above.
• the HLB of the nonionic surfactant not having a polyoxyethylene chain having an HLB of less than 15 is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, Preferably, it is 13 or less, preferably 4 or more and less than 15, more preferably 8 or more and 13 or less, further preferably 10 or more and 13 or less, according to any one of ⁇ 4> to ⁇ 11> Method.
• the content of the nonionic surfactant 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 0.01% by mass or more, and still more preferably.
• the ratio (mass ratio) of the content of the nonionic surfactant to the content of the carbon number 4 dicarboxylic acid in the aqueous solution containing the carbon number 4 dicarboxylic acid or a salt thereof is preferably 0.001 to The method according to any one of ⁇ 4> to ⁇ 13>, which is 0.5, more preferably 0.002 to 0.3, and still more preferably 0.01 to 0.3.
• ⁇ 15> At least one polymer selected from an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof, selected from (b1) a nonionic polymer, (b2) a cationic polymer, and (b3) an amphoteric polymer.
• crystallization including the process of depositing the crystal
• ⁇ 16> at least one polymer selected from (b1) a nonionic polymer, (b2) a cationic polymer, and (b3) an amphoteric polymer from an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof.
• a method for improving the oil absorption of a C4 dicarboxylic acid crystal comprising a step of precipitating a C4 dicarboxylic acid crystal in the presence of.
• the nonionic polymer is preferably at least one selected from a starch polymer, a cellulose polymer, and a vinyl polymer, and more preferably a monomer having a vinyl group is polymerized.
• the weight average molecular weight of the polymer is preferably 3,000 or more, more preferably 10,000 or more, still more preferably 30,000 or more, and preferably 2,000,000 or less, more preferably 1,000,000 or less, more preferably 500,000 or less, preferably 3,000 or more and 2,000,000 or less, more preferably 10,000 or more and 1,000,000 or less, still more preferably
• the content of the polymer in the aqueous solution containing a C4 dicarboxylic acid or a salt thereof is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.05% by mass.
• % Or more preferably 5% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and preferably 0.8% or less.
• 001% by mass or more and 5% by mass or less more preferably 0.01% by mass or more and 1.5% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less, more preferably 0.05% by mass.
• the mass ratio of the polymer content to the content of the carbon number 4 dicarboxylic acid in the aqueous solution containing the carbon number 4 dicarboxylic acid or a salt thereof is preferably 0.001 to 0.5, more preferably The method according to any one of ⁇ 15> to ⁇ 22>, which is 0.002 to 0.3.
• the total content of the nonionic surfactants (a1) to (a2) and the polymers (b1) to (b3) in an aqueous solution containing a dicarboxylic acid having 4 carbon atoms or a salt thereof is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, preferably 10% by mass or less, more preferably 3% by mass or less, and still more preferably 2%.
• % By mass or less preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 3% by mass or less, and further preferably 0.05% by mass or more and 2% by mass.
• the method according to any one of ⁇ 4> to ⁇ 23> which is as follows.
• ⁇ 25> The method according to any one of ⁇ 4> to ⁇ 24>, wherein the method for precipitating the crystal is one or more methods selected from precipitation by pH adjustment, precipitation by cooling, precipitation by concentration, and precipitation by reaction.
• 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 method according to ⁇ 25> 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 rate of acid addition during 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 mol- acid / L / min or more, the method according to at most 2mmol- acid / L / min ⁇ 25> or ⁇ 26>.
• the acid is preferably an inorganic acid, more preferably one or more selected from hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and still more preferably sulfuric acid or hydrochloric acid.
• 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 Is preferably 5 ° C. 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,
• ⁇ 31> The method according to ⁇ 25>, wherein the precipitation of the crystal by cooling is preferably performed after the temperature of the aqueous solution containing a C4 dicarboxylic acid or a salt thereof is raised.
• Temperature rising temperature is preferably 60 ° C. or higher, more preferably 70 ° C.
• the method according to ⁇ 31> 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.
• ⁇ 25>, ⁇ 31>, or ⁇ 32> 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 required 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 pH during crystal precipitation by cooling is preferably 4 or less, more preferably 2.5 or less, and preferably pH 0.5 or more, 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 100 ° C. or less, more preferably Is 80 ° C. or lower, preferably 5 ° C. or higher, and preferably 5 ° C. or higher and 100 ° C. or lower, more preferably 5 ° C. or higher and 80 ° 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 during crystal precipitation 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 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, followed by cooling at an average cooling rate of 0.05 ° C./min or higher.
• the method according to any one of ⁇ 4> to ⁇ 39> which is carried out by adding an inorganic acid and lowering the pH to 2.5 or lower after reaching 30 ° C.
• 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 method according to any one of ⁇ 4> to ⁇ 40> which is preferably a fumaric acid crystal.
• the C4 dicarboxylic acid crystal 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.
• 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 catalyst is preferably thiourea, bromate, or perborate.
• Precipitation of the 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.
• / S or less more preferably a peripheral speed of 5 m / s or less, further preferably a peripheral speed of 3 m / s or less, preferably a peripheral speed of 0.2 m / s or more and 10 m / s or less, more preferably a peripheral speed of 0.3 m.
• the oil absorption of the dicarboxylic acid crystal having 4 carbon atoms measured according to JIS K 5101-13-2 (2004) is preferably 40 mL / 100 g to 200 mL / 100 g, more preferably 50 mL / 100 g to 200 mL.
• ⁇ 4> to ⁇ 45> which is / 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.
• Comparative Example 6 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 6 are shown in Table 1.
• Example 1 In a 35 L reaction tank (diameter 360 mm), ion-exchanged water 16.7 kg, fumaric acid (manufactured by Nippon Shokubai Co., Ltd., hereinafter the same as Comparative Example 13) 817 g, polyoxyethylene (2.5) lauryl ether (Emulgen 102) 17 After mixing 0.5 g, the mixture was heated to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 23 ° C. at an average cooling rate of 0.79 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min.
• the precipitated fumaric acid suspension was No.
• 2 filter paper manufactured by ADVANTEC Co., Ltd., hereinafter the same
• 5.0 kg of ion exchanged water was added to perform filtration and washing.
• the pH of the filtrate was 2.2.
• the filtered fumaric acid cake was dried at 105 ° C. in a hot air circulating dryer FS-60WT (manufactured by Tokyo Glass Instrument Co., Ltd., the same shall apply hereinafter).
• a fumaric acid crystal was obtained by passing through a sieve having an opening of 500 ⁇ m. It was 61.9 mL / 100g when the oil absorption amount of the obtained fumaric acid crystal
• crystallization was measured.
• Example 2 After mixing 16.7 kg of ion-exchange water, 817 g of fumaric acid, and 17.5 g of polyoxyethylene (4) lauryl ether (Emulgen 104) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 23 ° C. at an average cooling rate of 0.63 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. The operation after crystallization was performed in the same manner as in Example 1. It was 69.4 mL / 100g when the oil absorption amount of the obtained fumaric acid crystal was measured.
• Emulgen 104 polyoxyethylene (4) lauryl ether
• Example 3 After mixing 16.7 kg of ion-exchanged water, 817 g of fumaric acid, and 17.5 g of polyoxyethylene (40) sorbite (Reodol 440V) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. did. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 24 ° C. at an average cooling rate of 0.86 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. The operation after crystallization was performed in the same manner as in Example 1. The oil absorption of the obtained fumaric acid crystals was measured and found to be 50.1 mL / 100 g.
• polyoxyethylene (40) sorbite Reodol 440V
• Example 4 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, 2.25 g of polyoxyethylene (6) stearyl ether (Emulgen 306P) was mixed, and then fumaric acid was precipitated by cooling from 85 ° C. to 25 ° C. at an average cooling rate of 0.45 ° 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. After suction filtration using the filter paper of No.
• Emgen 306P polyoxyethylene (6) stearyl ether
• Example 5 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, 2.25 g of polyoxyethylene (6) stearyl ether (Emulgen 306P) was mixed, and then fumaric acid was precipitated by cooling from 85 ° C. to 26 ° C. at an average cooling rate of 0.094 ° C./min. . Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 250 r / min. The operation after crystallization was performed in the same manner as in Example 4. It was 85.6 mL / 100g when the oil absorption of the obtained fumaric acid crystal was measured.
• Emulgen 306P polyoxyethylene (6) stearyl ether
• Example 6 Ion exchange water 2.57 kg, fumaric acid 105 g, 47% sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 50 g, polyoxyethylene (20) sorbitan trioleate (Leodol TW-O320V) in a 3 L reaction tank (diameter 130 mm) ) was mixed and then heated to 80 ° C. to dissolve. Subsequently, fumaric acid was precipitated by cooling from 80 ° C. to 28 ° C. at an average cooling rate of 0.64 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 100 r / min. Next, the precipitated fumaric acid suspension was No.
• Example 7 Ion-exchanged water 2.52 kg, fumaric acid 158 g, sodium fumarate (manufactured by Tokyo Chemical Industry Co., Ltd.) 72.5 g, tetraoleic acid polyoxyethylene (30) sorbite (Leodol 430V) ) was mixed and then heated to 80 ° C. to dissolve. Subsequently, fumaric acid was precipitated by cooling from 80 ° C. to 27 ° C. at an average cooling rate of 0.39 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 150 r / min. Next, the precipitated fumaric acid suspension was No. After suction filtration using the filter paper of No.
• Example 8 After mixing 16.7 kg of ion-exchanged water, 817 g of fumaric acid, and 17.5 g of sorbitan monolaurate (Emazole L-10V) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 22 ° C. at an average cooling rate of 1.06 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. The operation after crystallization was performed in the same manner as in Example 1. It was 79.5 mL / 100g when the oil absorption amount of the obtained fumaric acid crystal
• Example 9 After mixing 16.7 kg of ion-exchanged water, 817 g of fumaric acid, and 17.5 g of sorbitan monostearate (Emazole S-10V) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 24 ° C. at an average cooling rate of 0.89 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. The operation after crystallization was performed in the same manner as in Example 1. It was 49.6 mL / 100g when the oil absorption of the obtained fumaric acid crystal was measured.
• Example 10 After mixing 16.7 kg of ion-exchange water, 817 g of fumaric acid, and 1.75 g of sorbitan monolaurate (Emazole L-10V) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 25 ° C. at an average cooling rate of 0.70 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. Next, the precipitated fumaric acid suspension was No. After suction filtration using the filter paper of No.
• Example 11 After mixing 86.4 kg of ion exchange water, 6.31 kg of fumaric acid, and 86.4 g of lauryl glucoside (Mydol 12) in a 100 L reaction tank (diameter 450 mm), the temperature was raised to 92 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 92 ° C. to 21 ° C. at an average cooling rate of 0.34 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. Next, the precipitated fumaric acid suspension was No. After suction filtration using the filter paper of No.
• Example 12 After mixing 17.5 kg of ion-exchanged water, 817 g of fumaric acid, and 17.5 g of polyvinylpyrrolidone (polyvinylpyrrolidone K30) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 22 ° C. at an average cooling rate of 1.0 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. Next, the precipitated fumaric acid suspension was No. After suction filtration using the filter paper of No.
• Example 13 After mixing 16.7 kg of ion-exchanged water, 817 g of fumaric acid, and 175 g of polyvinylpyrrolidone (polyvinylpyrrolidone K30) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 23 ° C. at an average cooling rate of 0.72 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. Next, the precipitated fumaric acid suspension was No. After suction filtration using the filter paper of No.
• Example 14 After mixing 16.7 kg of ion-exchanged water, 817 g of fumaric acid and 1.75 g of polyvinyl alcohol (molecular weight 100000) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 23 ° C. at an average cooling rate of 0.68 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. Next, the precipitated fumaric acid suspension was No. After suction filtration using the filter paper of No.
• Example 15 After mixing 16.7 kg of ion-exchanged water, 817 g of fumaric acid, and 17.5 g of polyvinyl alcohol (molecular weight 100000) in a 35 L reaction tank (diameter 360 mm), the temperature was raised to 85 ° C. and dissolved. Subsequently, fumaric acid was precipitated by cooling from 85 ° C. to 25 ° C. at an average cooling rate of 0.39 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 150 mm under the condition of 300 r / min. Next, the precipitated fumaric acid suspension was No. After suction filtration using the filter paper of No.
• Example 16 After mixing 2.75 kg of ion exchange water, 105 g of fumaric acid and 2.75 g of hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether (poise C-60H) in a 3 L reaction tank (diameter 130 mm), the temperature was raised to 80 ° C. and dissolved did. Subsequently, fumaric acid was precipitated by cooling from 80 ° C. to 28 ° C. at an average cooling rate of 0.55 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 150 r / min. Next, the precipitated fumaric acid suspension was No. Suction filtration was performed using No. 2 filter paper.
• the pH of the filtrate was 2.2.
• the filtered fumaric acid cake was dried at 105 ° C. in a hot air circulating dryer FS-60WT. 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 50.1 mL / 100 g.
• Example 17 After mixing 2.59 kg of ion exchange water, 105 g of fumaric acid, 55 g of methacryloyloxyethyl phosphorylcholine-stearyl methacrylate copolymer (Lipidure NR) in a 3 L reaction tank (diameter 360 mm), the temperature was raised to 80 ° C. and dissolved. . Subsequently, fumaric acid was precipitated by cooling from 80 ° C. to 30 ° C. at an average cooling rate of 0.68 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 150 r / min. Next, the precipitated fumaric acid suspension was No.
• Example 18 In a 3 L reaction tank (diameter 360 mm), 2.59 kg of ion exchange water, 105 g of fumaric acid, and 1.13 g of hydroxyethyl cellulose (hydroxyethyl cellulose 200-300 mPa ⁇ s) were mixed, and then heated to 80 ° C. to dissolve. Subsequently, fumaric acid was precipitated by cooling from 80 ° C. to 25 ° C. at an average cooling rate of 0.60 ° 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 No. 2 filter paper.
• the pH of the filtrate was 2.2.
• the filtered fumaric acid cake was dried at 105 ° C. in a hot air circulating dryer FS-60WT. After drying, a fumaric acid crystal was obtained by passing through a sieve having an opening of 500 ⁇ m. It was 115.0 mL / 100g when the oil absorption of the obtained fumaric acid crystal was measured.
• the filtered fumaric acid cake was dried at 105 ° C. in a hot air circulating dryer FS-60WT. 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 25.4 mL / 100 g.
• Example 19 (Precipitation method by pH adjustment) [Example 19] In an 80 L reactor, 33.7 kg of ion exchange water, 1.87 kg of fumaric acid (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), 1.89 kg of 48% sodium hydroxide, polyoxyethylene (40) sorbitol tetraoleate (Reodol 440V) 37.5 g was mixed to dissolve fumaric acid. This solution had a pH of 4.0. Subsequently, 47% sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to pH 2.1 at an average acid addition rate of 1.82 mmol-H2SO4 / L / min to precipitate fumaric acid.
• Example 20 (Deposition method by cooling) [Example 20] After mixing 1.81 kg of ion exchange water and 450 g of succinic acid (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) into a 3 L reaction tank, the temperature was raised to 80 ° C. Subsequently, 9.64 g of polyoxyethylene (6) stearyl ether (Emulgen 306P) was mixed, and then succinic acid was precipitated by cooling from 80 ° C. to 26 ° C. at an average cooling rate of 0.27 ° C./min. . Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 150 r / min.
• succinic acid manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter
• the precipitated succinic acid suspension was No.
• Suction filtration was performed using No. 2 filter paper.
• the pH of the filtrate was 2.1.
• the succinic acid cake after filtration was dried at 105 ° C. in a hot air circulating dryer FS-60WT. After drying, succinic acid crystals were obtained by passing through a sieve having an opening of 710 ⁇ m. It was 58.6 mL / 100g when the oil absorption of the obtained succinic acid crystal was measured.
• Example 21 After mixing 1.80 kg of ion-exchange water and 450 g of succinic acid in a 3 L reaction tank, the temperature was raised to 80 ° C. Subsequently, 2.25 g of polyvinyl alcohol (molecular weight 100000) was mixed, and then succinic acid was precipitated by cooling from 80 ° C. to 26 ° C. at an average cooling rate of 0.42 ° C./min. Stirring was performed using a stirring blade having a blade diameter of 121 mm under the condition of 150 r / min. Next, the precipitated succinic acid suspension was No. Suction filtration was performed using No. 2 filter paper. The pH of the filtrate was 2.0.
• the succinic acid cake after filtration was dried at 105 ° C. in a hot air circulating dryer FS-60WT. After drying, succinic acid crystals were obtained by passing through a sieve having an opening of 500 ⁇ m. The oil absorption of the obtained succinic acid crystals was measured and found to be 115.7 mL / 100 g.
• the results of Examples 20 and 21 are shown in Table 6.

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