WO2010035837A1 - Succinic acid and process for producing same - Google Patents
Succinic acid and process for producing same Download PDFInfo
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- WO2010035837A1 WO2010035837A1 PCT/JP2009/066800 JP2009066800W WO2010035837A1 WO 2010035837 A1 WO2010035837 A1 WO 2010035837A1 JP 2009066800 W JP2009066800 W JP 2009066800W WO 2010035837 A1 WO2010035837 A1 WO 2010035837A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/44—Polycarboxylic acids
- C12P7/46—Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
Definitions
- the present invention relates to succinic acid and a method for producing the same.
- the present invention relates to high-purity succinic acid purified from a fermentation broth obtained by microbial conversion such as glucose, sucrose, and cellulose derived from biomass resources, and a method for producing the same.
- Aliphatic dicarboxylic acids such as succinic acid and adipic acid are widely used as raw materials for polymers such as polyester and polyamide, and as synthetic raw materials for foods, pharmaceuticals and other chemicals.
- a dicarboxylic acid is used as a polymer raw material
- a high-purity dicarboxylic acid is required to maintain the polymerization activity of the polymer and to obtain a high-quality polymer with little coloring.
- succinic acid when using succinic acid as a food material, it is required that the succinic acid produced does not contain odor components that impair the flavor.
- a raw material In the production of aliphatic dicarboxylic acid by fermentation, a raw material is generally a saccharide, such as glucose, sucrose, or cellulose.
- a saccharide such as glucose, sucrose, or cellulose.
- polysaccharides are contained as impurities in the aliphatic dicarboxylic acids, or that the raw material saccharides are not completely assimilated by microorganisms and remain mixed.
- amino acids are also produced as impurities, and it has been difficult to remove these from aliphatic dicarboxylic acids by an efficient and inexpensive method.
- Patent Document 1 As a method for purifying an aliphatic dicarboxylic acid produced by fermentation, for example, a method using an ion exchange resin (for example, Patent Document 1) and a method using electrodialysis (for example, Patent Document 2) are known.
- Patent Document 2 As a salt exchange method, a method of producing a dicarboxylic acid and ammonium sulfate by mixing and reacting ammonium salt of dicarboxylic acid with ammonium hydrogen sulfate and / or sulfuric acid at a sufficiently low pH has been proposed (for example, Patent Document 3).
- the present invention is an aliphatic dicarboxylic acid produced from a fermentation broth or the like obtained by microbial conversion of glucose, sucrose, cellulose or the like derived from biomass resources, and is a raw material for food materials, polymers and dicarboxylic acid derivatives It is an object of the present invention to provide a high-purity, aliphatic dicarboxylic acid succinic acid useful as a method and a method for producing the same.
- the inventors of the present invention made extensive studies to solve the above problems. As a result, the present inventors have obtained a high-purity succinic acid useful as a food material, and as a raw material for polymers and dicarboxylic acid derivatives, which is an aliphatic dicarboxylic acid obtained by a fermentation method using microorganisms. In order to achieve this, it has been found that a method of hydrotreating a solution containing the succinic acid in the presence of a catalyst is effective, and particularly when used as a raw material for a polymer, it is in the ultraviolet region. The present inventors have obtained the knowledge that it is useful to reduce impurities that are absorbed in a specific region to a specific amount or less, thereby completing the present invention.
- the present invention is as follows.
- a method for producing succinic acid derived from biomass resources comprising a step of hydrotreating at least a solution containing the succinic acid in the presence of a catalyst.
- a succinic acid derived from biomass resources is subjected to a hydrogen treatment in the presence of a catalyst after at least one of an adsorption treatment using activated carbon in a solution and a crystallization treatment.
- succinic acid which is a high-purity aliphatic dicarboxylic acid that is a raw material for a polymer that is not only colored as a food material but has little coloration and excellent mechanical properties and can be used in various applications
- succinic acid derivative As a raw material for the dicarboxylic acid derivative, it is possible to provide succinic acid which is a high-purity aliphatic dicarboxylic acid with little catalyst poisoning during the conversion reaction.
- the development of the present invention can greatly contribute to the solution of environmental problems, fossil fuel resource depletion problems, and the like.
- the present invention is a method for producing succinic acid derived from biomass resources, and the production process includes a step of hydrotreating at least a solution containing the succinic acid in the presence of a catalyst.
- the present invention relates to a method for producing succinic acid.
- succinic acid derived from biomass resources characterized in that the average absorbance in the ultraviolet region of 250 to 300 nm is 0.05 or less and a method for producing succinic acid, wherein succinic acid is derived from biomass resources
- the present invention relates to a method for producing succinic acid, wherein impurities are removed from the succinic acid so that an average absorbance in the ultraviolet region of 250 to 300 nm of the succinic acid is 0.05 or less.
- the succinic acid of the present invention can be derived from a biomass resource with a very high carbon yield.
- succinic acid is derived from biomass resources.
- Biomass resources include, for example, wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil scum, persimmon, buckwheat, soybean, fat, waste paper, papermaking residue , Marine product residue, livestock excrement, sewage sludge, food waste and the like.
- plant resources such as wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil residue, buckwheat, soy, oil, waste paper, paper residue More preferred are wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, straw, oil and fat, waste paper, papermaking residue, and most preferred are corn, sugar cane, cassava, sago palm.
- These biomass resources generally contain a large amount of alkali metals and alkaline earth metals such as nitrogen element, Na, K, Mg, and Ca.
- biomass resources are not particularly limited, but are induced to carbon sources through known pretreatment and saccharification processes such as chemical treatment with acids and alkalis, biological treatment with microorganisms, physical treatment, and the like. Is done.
- the process is not particularly limited, but includes, for example, a refinement process by pretreatment such as chipping, scraping, or crushing biomass resources. If necessary, a grinding step with a grinder or a mill is further included.
- the biomass resources thus refined are further guided to a carbon source through pretreatment and saccharification processes. Specific methods include acid treatment with strong acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, and alkali treatment.
- Carbon sources derived from the above biomass resources usually include hexoses such as glucose, mannose, galactose, fructose, sorbose and tagatose, pentoses such as arabinose, xylose, ribose, xylulose and ribulose, maltose, sucrose, lactose and trehalose.
- succinic acid is derived from a carbon source derived from these biomass resources.
- fermentation methods by microbial conversion chemical conversion methods including reaction steps such as hydrolysis, dehydration reaction, hydration reaction, oxidation reaction, reduction reaction, and these fermentation methods
- succinic acid is synthesized by a combination of chemical conversion methods, and among these, fermentation methods based on microbial conversion using microorganisms having succinic acid-producing ability are preferable.
- Microorganisms capable of producing succinic acid are not particularly limited as long as they are microorganisms capable of producing succinic acid, but include intestinal bacteria such as Escherichia coli, Bacillus bacteria, coryneform bacteria, aerobic microorganisms, facultative It is preferable to use anaerobic microorganisms or microaerobic microorganisms.
- Examples of aerobic microorganisms include Coryneform Bacterium, Bacillus genus bacteria, Rhizobium genus bacteria, Arthrobacter genus bacteria, Mycobacterium genus bacteria, Rhodococcus cc Examples include genus bacteria, Nocardia bacteria, and Streptomyces bacteria, and coryneform bacteria are more preferable.
- the coryneform bacterium is not particularly limited as long as it is classified as such, and examples thereof include bacteria belonging to the genus Corynebacterium, bacteria belonging to the genus Brevibacterium, and bacteria belonging to the genus Arthrobacter. Examples include those belonging to the genus Corynebacterium or Brevibacterium, more preferably, Corynebacterium glutamicum, Brevibacterium flavum, Brevibacterium ammoniagenes (Brevibaterium). Amoniagenes) or Brevibacterium lactofermentum And the like.
- Reaction conditions such as reaction temperature and pressure in microbial conversion will depend on the activity of microorganisms such as selected cells and fungi, but suitable conditions for obtaining succinic acid should be selected in each case. That's fine.
- neutralizing agents are usually used because the metabolic activity of microorganisms decreases or the activity of microorganisms stops when pH decreases, and the production yield deteriorates or the microorganisms die.
- the pH in the reaction system is measured by a pH sensor, and the pH is adjusted by adding a neutralizing agent so as to be in a predetermined pH range.
- the pH value is adjusted to a range where the activity is most effectively exhibited according to the type of microorganisms such as fungus bodies and molds to be used.
- Examples of the neutralizing agent include ammonia, ammonium carbonate, urea, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, and alkaline earth metal carbonate. Ammonia, ammonium carbonate and urea are preferred.
- Examples of the alkali (earth) metal hydroxide include NaOH, KOH, Ca (OH) 2 , Mg (OH) 2 , or a mixture thereof.
- Examples of the alkali (earth) metal carbonate include is, Na 2 CO 3, K 2 CO 3, CaCO 3, MgCO 3, NaKCO 3 etc., or the like and mixtures thereof.
- the fermentation broth after microbial conversion may be appropriately concentrated in consideration of operability and efficiency in the subsequent purification step.
- concentration method The method of distribute
- the concentration operation may be performed by a batch operation or a continuous operation.
- the fermented liquid in the method of this invention it is preferable to use the fermented liquid after removing microorganisms.
- the method for removing the microorganisms is not particularly limited, and sedimentation separation, centrifugation, filtration separation, a combination thereof, and the like are used.
- centrifugal separation it is performed by a method such as centrifugal separation or membrane filtration separation.
- centrifugation centrifugal sedimentation, centrifugal filtration, or the like can be used.
- the operating conditions are not particularly limited, but the separation is usually performed with a centrifugal force of 100 G to 100,000 G.
- the operation can be performed continuously or batchwise.
- membrane filtration separation microfiltration and / or ultrafiltration can be used.
- the material of the film is not particularly limited, and for example, an organic film such as polyolefin, polysulfine, polyacrylonitrile, polyvinylidene fluoride, or a film made of an inorganic material such as ceramic can be used.
- either a dead end type or a cross flow type can be used.
- membrane filtration separation since microorganisms often clog the membrane, a method of performing membrane filtration after roughly removing the microorganisms by centrifugation or the like is also used.
- a succinic acid salt is obtained, and the obtained succinic acid salt is converted into the desired succinic acid.
- the succinic acid may be converted to succinic acid by a reaction crystallization method using a weakly acidic organic acid having a higher acid dissociation constant (pKa) than the target succinic acid.
- pKa acid dissociation constant
- An example of such an organic acid is acetic acid.
- the succinic acid salt obtained as described above may be converted to succinic acid with an inorganic acid.
- examples of the inorganic acid used include sulfuric acid, hydrochloric acid, carbonic acid, phosphoric acid, and nitric acid.
- succinic acid fermentation when fermentation is performed while neutralizing the produced succinic acid with ammonia or magnesium hydroxide, ammonium succinate or magnesium succinate is produced in the fermentation broth.
- a fermented solution containing ammonium succinate or magnesium succinate is treated with sulfuric acid or the like, an aqueous solution containing succinic acid is obtained.
- the solution or aqueous solution containing succinic acid is a solution or aqueous solution mainly containing succinic acid derived from biomass resources. Accordingly, a solution or an aqueous solution mainly containing a succinate such as ammonium succinate or magnesium succinate is referred to as a solution or aqueous solution containing succinate.
- the term “contained as the main component” as used herein means that the weight of the component relative to the weight of all components excluding the solvent is usually 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably The state of 90% by weight or more is shown.
- the aqueous solution converted into succinic acid with the inorganic acid is not particularly limited, but succinic acid may be extracted from the aqueous solution using an organic solvent.
- the organic solvent used in this method usually has an inorganic value / organic value ratio (I / O value) of 0.2 or more and 2.3 or less, and has a boiling point of 40 ° C. at normal pressure (1 atm). More preferably, the organic solvent is an organic solvent having an I / O value of 0.3 or more and 2.0 or less and a boiling point of 40 ° C. or more at normal pressure, and more preferably I / O. An organic solvent having a value of 0.3 or more and 2.0 or less and a normal pressure and a boiling point of 60 ° C. or more.
- succinic acid can be selectively extracted and efficiently separated from saccharides and amino acids.
- an organic solvent having a boiling point of 40 ° C. or higher at normal pressure there is a risk that the solvent vaporizes and ignites, a problem that the solvent vaporizes and the extraction efficiency of succinic acid decreases, and the solvent is recycled. The problem of difficulty can be avoided.
- Organic solvents having an I / O value of 0.2 or more and 2.3 or less and a boiling point of 40 ° C. or more at normal pressure include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, and ether solvents such as tetrahydrofuran and dioxane.
- Examples include solvents, ester solvents such as ethyl acetate, nitrile solvents such as acetonitrile, and alcohols having 3 or more carbon chains such as propanol, butanol, and octanol.
- I O I / O Boiling point tetrahydrofuran 30 80 0.375 66.0 Methyl ethyl ketone 65 60 1.083 79.6 Methyl isobutyl ketone 65 120 0.542 94.2 Acetone 65 40 1.625 56.1 Acetonitrile 70 40 1.750 81.1 Ethyl acetate 85 80 1.063 77.2 Propanol 100 60 1.667 97.2 Isobutanol 100 70 1.429 108.0 Octanol 100 160 0.625 179.8 Dioxane 40 80 0.500 101.3
- the organic solvent is preferably added in a volume of 0.5 to 5 with respect to volume 1 of the aqueous solution containing succinic acid, and in a volume of 1 to 3 with respect to volume 1 of the aqueous solution containing succinic acid. More preferably, it is added.
- the temperature of the extraction step may be any temperature at which succinic acid is extracted, but is preferably 10 to 90 ° C, more preferably 20 to 85 ° C.
- succinic acid is recovered in an organic solvent, and in addition to saccharides and nitrogen elements derived from fermentation, impurities such as ammonia derived from fermentation bacteria, sulfur-containing impurities and metal cations are separated to some extent.
- impurities such as ammonia derived from fermentation bacteria, sulfur-containing impurities and metal cations are separated to some extent.
- the extraction process with an organic solvent may be repeated a plurality of times, or countercurrent extraction may be performed.
- the present invention it is possible to reduce the amount of many impurities such as nitrogen element derived from fermentation bacteria, ammonia, sulfur-containing impurities and metal cations in addition to nitrogen element contained in biomass resources by purification from fermentation broth containing succinic acid. Although it is important, especially the content of odorous components contained in succinic acid is reduced, or the amount of impurities that absorb in the ultraviolet region of 250 to 300 nm is reduced until the average absorbance is 0.05 or less. Is essential.
- a deodorizing method using an adsorbent such as activated carbon As a method for removing odor components, a deodorizing method using an adsorbent such as activated carbon, a washing and removing method using an organic solvent, a crystallization method, an aeration method, and the like are known.
- a catalyst As a method for removing odor components, a deodorizing method using an adsorbent such as activated carbon, a washing and removing method using an organic solvent, a crystallization method, an aeration method, and the like are known.
- hydrotreating in the presence of a catalyst is particularly effective for removing odorous components.
- a small amount of fumaric acid may be contained in the succinic acid-containing liquid derived from biomass resources by fermentation or the like.
- succinic acid in order to reduce impurities having absorption in the ultraviolet region of 250 to 300 nm contained in this succinic acid to an average absorbance of 0.05 or less, it is usually produced as described above.
- the succinic acid must be subjected to hydrogen treatment and further combined with purification treatment such as crystallization treatment and activated carbon treatment.
- the hydrogen treatment in the present invention may be either a batch type or a continuous type, and can be performed according to a conventionally known method.
- a solution containing succinic acid and a hydrogenation catalyst are allowed to coexist in a pressurized reactor, hydrogen gas is introduced while stirring the mixture, and hydrogen treatment is performed.
- known homogeneous and heterogeneous noble metal-containing hydrogenation catalysts can be used. Specific examples include, but are not limited to, hydrogenation catalysts containing noble metals such as ruthenium, rhodium, palladium and platinum. Among these, hydrogenation catalysts containing palladium and platinum, particularly palladium, are preferred. These hydrogenation catalysts can be used with the above compounds containing noble metals as they are or in the presence of a ligand such as an organic phosphine, but heterogeneous noble metal-containing catalysts for reasons of ease of catalyst separation. Is preferred.
- a compound containing these noble metals can be subjected to hydrogen treatment in the presence of a metal oxide such as silica, titanium, zirconia, activated alumina, or a composite metal oxide thereof, or activated carbon.
- a metal oxide such as silica, titanium, zirconia, activated alumina, or a composite metal oxide thereof, or activated carbon.
- the amount of the noble metal supported is usually 0.1 to 10% by weight of the carrier, but the carrier is not particularly limited, but silica or activated carbon, especially activated carbon is used for the reason that the amount of eluted metal during the hydrogen treatment is small. preferable.
- the embodiment in which the hydrogen treatment is performed with a hydrogenation catalyst in which a noble metal is supported on a metal oxide such as silica, titanium, zirconia, activated alumina, or a composite metal oxide thereof, or a support such as activated carbon is the present invention.
- a hydrogenation catalyst in which a noble metal is supported on a metal oxide such as silica, titanium, zirconia, activated alumina, or a composite metal oxide thereof, or a support such as activated carbon.
- a hydrogenation catalyst in the presence of any adsorbent selected from the group of metal oxide, silica and activated carbon any adsorbent selected from the group of metal oxide, silica and activated carbon.
- Solvents containing succinic acid derived from biomass resources during hydrogen treatment are water, organic acids such as acetic acid and propionic acid, esters such as ethyl acetate, methanol, ethanol, propanol, isopropanol, butanol, 2-ethyl Alcohols such as 1-hexanol and isobutanol, ethers such as diethyl ether, di-n-butyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and diethyl ketone, acetonitrile Nitriles such as these, and mixed solvents thereof can be used, but water is most preferred among them.
- succinic acid is crystallized from the succinic acid-containing reaction solution in the subsequent step after the hydrogenation reaction.
- the solution after filtration can be used repeatedly.
- the succinic acid concentration in the solution may be equal to or lower than the saturation solubility at the liquid temperature.
- the content of fumaric acid contained in the succinic acid subjected to hydrotreating is usually 0.01% by weight or more, preferably 0.05% by weight or more, and the upper limit is 10% by weight, based on the weight of succinic acid. Hereinafter, it is preferably 5% by weight or less. If the content of fumaric acid is too low, the purification process up to the hydrotreating step becomes complicated. On the other hand, if the content of fumaric acid is too high, fumaric acid has a long time for hydrotreating or has low solubility. This causes a problem that the succinic acid solution having a high concentration cannot be prepared.
- Hydrogen used may be pure hydrogen, but hydrogen diluted with an inert gas such as nitrogen, helium or argon can also be used.
- the carbon monoxide concentration in the hydrogen gas is usually 10000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less because there is concern about the influence on the hydrogen treatment efficiency.
- the lower limit of the hydrogen pressure during the hydrogen treatment is usually 0.1 MPa or more, and the upper limit is usually 5 MPa or less, preferably 3 MPa or less, more preferably 1 MPa or less. If the hydrogen pressure is too low, the reaction rate is slow and it takes time to complete the reaction. On the other hand, if it is too high, succinic acid hydrides such as butanediol and tetrahydrofuran may be produced as a by-product depending on the catalyst and reaction conditions. It is not preferable.
- the lower limit of the temperature during the hydrogen treatment is usually 30 ° C or higher, preferably 50 ° C or higher, and the upper limit is usually 150 ° C or lower, preferably 120 ° C or lower.
- reaction temperature is too low, the reaction rate is slow and it takes time to complete the reaction. If the reaction temperature is too high, by-products such as succinic acid hydride and when using water as a solvent, by-products such as malic acid are not produced. It is not preferable because it increases.
- the crystallization solvent in the crystallization treatment for removing impurities includes water, organic acids such as acetic acid and propionic acid, esters such as ethyl acetate, methanol, ethanol, propanol, isopropanol, butanol, and 2-ethyl.
- Alcohols such as 1-hexanol and isobutanol, ethers such as diethyl ether, di-n-butyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and diethyl ketone, acetonitrile Nitriles such as these, and mixed solvents thereof can be used, but water is most preferred among them. Usually, deionized water, distilled water, river water, well water, tap water, etc. are used for water.
- the crystallization temperature can be selected from the range of about 0 to 90 ° C., preferably about 0 to 85 ° C.
- the cooling rate can be selected from the range of about 1 to 120 ° C./hr, preferably about 5 to 60 ° C./hr. It is performed under reduced pressure (for example, about 1 atm), reduced pressure or increased pressure.
- the aging time can be appropriately selected from the range of about 0.1 to 5 hours, preferably about 0.5 to 4 hours, more preferably about 0.5 to 2 hours.
- the above crystallization treatment alone, activated carbon treatment alone, or a combination of crystallization treatment and activated carbon treatment is used to average the amount of impurities that absorb in the ultraviolet region of 250 to 300 nm contained in succinic acid. It is preferable to reduce the absorbance until it becomes 0.05 or less.
- any known ones such as coal-based, wood-based, coconut-based, and resin-based can be used.
- use activated carbon activated by various methods such as gas activation method, water vapor activation method, chemical activation method such as zinc chloride and phosphoric acid, etc. Can do.
- Hakuho KL Hakuho W2c, Hakuho WH2c, Hakuho W5c, Hakuho WH5X, Hakuho XS7100H-3, Calaburafin, Hakuho A, Hakuho C, Hakuho M, Ajinomoto Fine Techno Co., Ltd.
- Hokuetsu CL-K Hokuetsu Hs, Hokuetsu KS, etc. Is mentioned.
- coconut charcoal and woody charcoal are preferable because impurities that absorb in the ultraviolet region of 250 to 300 nm contained in the aliphatic dicarboxylic acid can be efficiently removed.
- activated carbon activated by a method such as a gas activation method, a water vapor activation method, a chemical activation method such as zinc chloride or phosphoric acid is preferred, and among them, the water vapor activation method, Chemical activated carbon such as zinc chloride or phosphoric acid is preferred, and activated carbon activated by chemicals such as zinc chloride or phosphoric acid is particularly preferred.
- the shape of the activated carbon used may be any of powdered coal, crushed coal, formed coal, and fibrous activated carbon. When packed in a column and used, granular and granular activated carbon is preferable for the reason of suppressing tower pressure.
- the treatment time is usually 5 minutes to 5 hours, preferably 10 minutes to 2 hours in the case of a batch system, and is usually 0.1 to 20 hr ⁇ 1 as SV (space velocity) in the case of a packed bed system.
- the treatment temperature is usually 20 to 90 ° C.
- a purification operation such as ion exchange column treatment may be used in combination.
- the ion exchange column treatment is to remove ions by passing a liquid to be treated through a column filled with an ion exchange resin.
- the ion exchange resin should be selected according to the ions contained in the liquid to be treated and the required purity of succinic acid.
- anion exchange resins are used to remove anions such as sulfate ions and chloride ions.
- a cation exchange resin (H type) can be used, but both of them may be used if necessary.
- Ion exchange resins are classified into strongly acidic cation exchange resins, weakly acidic cation exchange resins, strongly basic anion exchange resins, and weakly basic anion exchange resins depending on the strength of the functional group as an acid or base. Although it is classified into a gel type and a porous type, the ion exchange resin used here is not particularly limited. However, in consideration of the efficiency of ion exchange, it is preferable to use a strongly acidic cation exchange resin or a strongly basic anion exchange resin having a stronger strength as an acid or a base. Further, it is desirable to use a more versatile and inexpensive gel type without any special reason that the shape is also porous. Specifically, Diaion SK1B (H type) is exemplified as a cation exchange resin, and Diaion SA10A is exemplified as an anion exchange resin.
- the ion exchange column treatment can be performed within a temperature range that is equal to or higher than the temperature at which succinic acid is dissolved in the liquid to be treated and lower than the heat resistant temperature of the ion exchange resin.
- the cation exchange resin is usually treated at 20 to 100 ° C. depending on the succinic acid concentration in the solution to be treated.
- anion exchange resins are usually treated at 10 to 80 ° C. because they have lower heat resistance than cation exchange resins. In the case of using anion exchange column treatment from the viewpoint of treatment temperature, a step where the succinic acid concentration is low and the column treatment is possible at a low temperature is desirable.
- the liquid flow treatment method is not particularly limited, but the treatment is usually performed at a space velocity (SV) of 0.1 to 10 hr ⁇ 1 and a superficial velocity of 1 to 20 m / hr. If the processing speed is too high, pressure loss before and after the column becomes large, and ion exchange becomes insufficient. Conversely, if the processing speed is unnecessarily slow, the column becomes unnecessarily large.
- the ion concentration is measured regularly or periodically at the column outlet, and if ion leakage is observed at the column outlet, the ion exchange resin is regenerated.
- the regeneration of the ion exchange resin can be carried out in accordance with a normal method, using an acid such as sulfuric acid or hydrochloric acid for a cation exchange resin, or an alkali such as caustic soda for an anion exchange resin.
- the obtained succinic acid when used as a polymer raw material, it is essential to reduce the amount of impurities that absorb in the ultraviolet region of 250 to 300 nm to an average absorbance of 0.05 or less.
- the average absorbance is preferably 0.03 or less, and particularly preferably 0.01 or less.
- succinic acid having a high average absorbance is markedly colored when used as a raw material for polyester.
- the absorbance in the present invention is a value measured with an ultraviolet-visible absorption spectrophotometer after placing a 3.0 wt% (wt%) aqueous succinic acid solution in a quartz cell having an optical path length of 1 cm.
- the absorbance was measured using an ultraviolet-visible absorption spectrophotometer (Hitachi spectrophotometer UV-3500), but can be measured using a commercially available ultraviolet-visible absorption spectrophotometer.
- the absorbance (A) is the absorbance when measured at an optical path length of 1 cm, and is a value calculated according to the following definition.
- the impurities that absorb in the ultraviolet region of 250 to 300 nm are not particularly limited, and examples thereof include compounds having a nitrogen element and compounds having aromaticity.
- examples of such compounds include oxygen-containing heteroaromatic compounds such as furan, nitrogen-containing heteroaromatic compounds such as pyrrole, pyridine, and pyrazine, and benzene aromatic compounds such as phenol, benzaldehyde, and benzoic acid.
- these impurity removal methods include a method of combining a plurality of activated carbon species, activated carbon treatment, and the above-described hydrogen treatment and crystallization treatment. The method of combining these is mentioned.
- the insoluble component may be mixed in the succinic acid solution derived from fermentation. Such an insoluble component is a factor that reduces the efficiency of the above-described impurity removal by activated carbon and the subsequent purification process, so it is preferable to remove the insoluble component in advance.
- Insoluble components are removed from the succinate produced by the fermentation method to succinic acid, and the process from the succinic acid solution to the activated carbon treatment process is performed using a known membrane permeabilization process. Is preferred.
- the powdered activated carbon is allowed to coexist to adsorb insoluble components to improve the permeability of the membrane permeation treatment, or the above-mentioned impurities are simultaneously adsorbed and removed together with the insoluble components using appropriate powdered activated carbon.
- the powdered activated carbon is allowed to coexist to adsorb insoluble components to improve the permeability of the membrane permeation treatment, or the above-mentioned impurities are simultaneously adsorbed and removed together with the insoluble components using appropriate powdered activated carbon. are also preferably used.
- a process in which the crystallization or / and activated carbon treatment step is performed before is preferably used.
- the succinic acid recovered by crystallization can be dried by a conventional method, depending on its use.
- the succinic acid water content is dried to 0.1 to 2% by weight, preferably 0.2 to 1% by weight.
- the drying method is not particularly limited, and a direct heating method in which heating is performed directly with warm air, an indirect heating method using steam, or the like can be used.
- box dryers, band dryers, rotary dryers and the like are used as dryers using hot air
- drum dryers and disk dryers are used as dryers using indirect heating.
- the operating pressure may be normal pressure or reduced pressure.
- the operation method may be batch operation or continuous operation.
- the hot air temperature is usually 20 to 200 ° C., preferably 50 to 150 ° C., as the heating surface temperature. If the temperature is too low, a high pressure reduction is required for drying. Conversely, if the temperature is too high, succinic acid is dehydrated and succinic anhydride is generated, which is not preferable.
- the succinic acid produced in the present invention is usually one that has little absorption in the visible light region and little coloring.
- the upper limit of the yellowness (YI value) of the succinic acid of the present invention is usually 10 or less, preferably 6 or less, more preferably 4 or less, while the lower limit is not particularly limited, but usually ⁇ It is 10 or more, preferably -5 or more, more preferably -1 or more.
- Succinic acid exhibiting a high YI value has a drawback that when used as a polymer raw material, coloring of the produced polymer becomes remarkable.
- the YI value is a value measured by a method based on JIS K7105.
- the succinic acid of the present invention may contain nitrogen element as an impurity due to a biomass resource-derived, fermentation process and a purification process including an acid neutralization step.
- nitrogen elements such as amino acids, proteins, ammonium salts, urea, and fermenting bacteria may be included.
- the upper limit of the nitrogen atom content contained in the succinic acid of the present invention is usually 2000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or less, and most preferably 20 ppm or less in terms of atoms in dicarboxylic acid.
- the lower limit is usually 0.01 ppm or more, preferably 0.05 ppm or more, more preferably 0.1 ppm or more, and still more preferably 1 ppm or more for reasons of economic efficiency of the purification step.
- the nitrogen atom content is measured by a known method such as elemental analysis or an amino acid analyzer and a method of separating amino acids and ammonia in a sample under biological amino acid separation conditions and detecting them by ninhydrin color development. Value.
- succinic acid having a nitrogen atom content in the above range is used as a polyester raw material, it is advantageous in reducing the coloration of the resulting polyester. It also has the effect of suppressing the delay of the polyester polymerization reaction.
- the succinic acid of the present invention may contain sulfur atoms due to a purification treatment including a neutralization step with an acid.
- examples of the impurities containing sulfur atoms include sulfuric acid, sulfate, sulfurous acid, organic sulfonic acid, and organic sulfonate.
- the sulfur atom content contained in the succinic acid of the present invention is usually 100 ppm or less, preferably 20 ppm or less, more preferably 10 ppm or less, and particularly preferably the upper limit as succinic acid in terms of atoms. Is 5 ppm or less, and most preferably the upper limit is 0.5 ppm or less.
- the lower limit is usually 0.001 ppm or more, preferably 0.01 ppm or more, more preferably 0.05 ppm or more, and particularly preferably 0.1 ppm or more.
- the sulfur atom content is a value measured by a known elemental analysis method.
- the succinic acid of the present invention may contain an alkali metal element.
- the content of the alkali metal contained in the aliphatic dicarboxylic acid is usually 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less, and particularly preferably 5 ppm or less. If the content is too high, when used as a polymer raw material, it not only reduces thermal stability and hydrolysis resistance, but also causes severe polymerization inhibition during polymerization and high polymerization with sufficient mechanical properties for practical use. Degree of polymer may not be obtained.
- the polyester of the present invention contains succinic acid units and diol units as essential components.
- the succinic acid constituting the succinic acid unit is a dicarboxylic acid containing high-purity succinic acid derived from the biomass resource. Therefore, in the present invention, a mixture of an aliphatic and / or aromatic dicarboxylic acid derived from a fossil resource and succinic acid derived from the biomass resource is also preferably used.
- the diol unit is derived from an aliphatic diol, and a known compound can be used.
- the aliphatic diol is not particularly limited as long as it is an aliphatic and alicyclic compound having two OH groups, but the lower limit of the carbon number is 2 or more, and the upper limit is usually 10 or less, preferably 6 The following aliphatic diols are mentioned.
- aliphatic diol examples include, for example, ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-butanediol and 1,4- And cyclohexanedimethanol. These may be used alone or as a mixture of two or more.
- ethylene glycol, 1,4-butanediol, 1,3-propylene glycol and 1,4-cyclohexanedimethanol are preferred, and among them, ethylene glycol and 1,4-butanediol, and these
- a mixture containing 1,4-butanediol as a main component or 1,4-butanediol is particularly preferable.
- the main component here means that the component is usually at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, particularly preferably at least 90 mol%, based on all diol units. Show.
- both terminal hydroxy polyethers may be mixed with the above aliphatic diols.
- the lower limit is usually 4 or more, preferably 10 or more
- the upper limit is usually 1000 or less, preferably 200 or less, more preferably 100 or less.
- both terminal hydroxy polyethers include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly 1,3-propanediol, and poly 1,6-hexamethylene glycol. .
- a copolymerized polyether of polyethylene glycol and polypropylene glycol can be used.
- the use amount of these both terminal hydroxy polyethers is an amount calculated as a content in the polyester of usually 90% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less.
- a copolymer component may be added to the polyester in addition to the diol component and the dicarboxylic acid component.
- the copolymer component include a bifunctional oxycarboxylic acid, an unsaturated dicarboxylic acid, a trifunctional or higher polyhydric alcohol and a trifunctional or higher polyhydric carboxylic acid or an anhydride thereof for forming a crosslinked structure.
- at least one polyfunctional compound selected from the group consisting of trifunctional or higher functional oxycarboxylic acids are added, the effect of significantly improving the polymerization rate during the production of the polyester is exhibited.
- oxycarboxylic acids are preferably used because polyesters having a high degree of polymerization tend to be easily produced.
- bifunctional oxycarboxylic acid examples include lactic acid, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyiso
- examples thereof include caproic acid, and these may be esters of oxycarboxylic acid, lactones, or derivatives of oxycarboxylic acid polymers.
- These oxycarboxylic acids can be used alone or as a mixture of two or more. When optical isomers exist in these, any of D-form, L-form, and racemic form may be sufficient, and a form may be a solid, a liquid, or aqueous solution. Of these, readily available lactic acid or glycolic acid is particularly preferable.
- a 30-95% aqueous solution is preferable because it can be easily obtained.
- the amount of oxycarboxylic acid used is usually 0.02 mol% or more, preferably 0.5 mol% or more, more preferably 1.0 mol% or more, with respect to the raw material monomer.
- the upper limit is usually 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less.
- the unsaturated dicarboxylic acid examples include itaconic acid, aconitic acid, fumaric acid, maleic acid and the like, and these can be used alone or as a mixture of two or more. Since the amount of unsaturated dicarboxylic acid used is a cause of gel generation, it is usually 5 mol% or less, preferably 0.5 mol% or less, more preferably based on all monomer units constituting the polyester. 0.05 mol% or less.
- trifunctional or higher polyhydric alcohol examples include glycerin, trimethylolpropane, pentaerythritol, and the like. These can be used alone or as a mixture of two or more.
- tri- or higher functional polycarboxylic acid or anhydride thereof examples include propanetricarboxylic acid, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, and the like. It can also be used as a mixture of two or more.
- tri- or higher functional oxycarboxylic acid examples include malic acid, hydroxyglutaric acid, hydroxymethylglutaric acid, tartaric acid, citric acid, hydroxyisophthalic acid, hydroxyterephthalic acid, and the like. It can also be used as a mixture of In particular, malic acid, tartaric acid, and citric acid are preferable because of easy availability.
- the amount of the trifunctional or higher functional compound is a cause of gel generation, it is usually 5 mol% or less, preferably 0.5 mol% or less, based on all monomer units constituting the polyester. More preferably, it is 0.2 mol% or less.
- a conventionally known method can be used. For example, after performing an esterification reaction and / or a transesterification reaction between the aliphatic dicarboxylic acid component containing succinic acid and a diol component. It can also be produced by a general method of melt polymerization such as a polycondensation reaction under reduced pressure, or a known solution heating dehydration condensation method using an organic solvent. From the viewpoint, a method of producing a polyester by melt polymerization performed in the absence of a solvent is preferable.
- the reaction temperature of the esterification reaction and / or transesterification reaction of the aliphatic dicarboxylic acid component containing succinic acid and / or the diol component is usually 150 ° C. or higher, preferably 180 ° C. or higher, and preferably 260 ° C. or lower, preferably upper limit. It is 250 degrees C or less.
- the reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon.
- the reaction pressure is usually from normal pressure to 10 kPa, but normal pressure is preferred.
- the reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.
- the pressure is usually 0.01 ⁇ 10 3 Pa or more at the lower limit, preferably 0.01 ⁇ 10 3 Pa or more, and the upper limit is usually 1.4 ⁇ 10 3 Pa or less, preferably 0.4. It is performed under a vacuum degree of ⁇ 10 3 Pa or less. If the pressure at the time of polymerization production is too high, the polymerization production time of the polyester becomes long, and accordingly, molecular weight reduction and coloration due to thermal decomposition of the polyester are caused, and it tends to be difficult to produce a polyester having practically sufficient characteristics. .
- the method of producing using an ultra-high vacuum polymerization equipment is a preferred embodiment from the viewpoint of improving the polymerization rate, but it requires not only a very expensive equipment investment, but still requires a long polymerization production time for polyester. Since there is a tendency, there is a concern about molecular weight reduction or coloring due to thermal decomposition of polyester.
- the lower limit of the reaction temperature is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 280 ° C. or lower, preferably 260 ° C. or lower. If this temperature is too low, particularly in the present invention, the polymerization reaction rate becomes extremely slow, and not only does it take a long time to produce a polyester with a high degree of polymerization, but also requires a high-powered stirrer, which is economically disadvantageous. It is. On the other hand, when the reaction temperature is too high, the polymerization rate is improved, but at the same time, thermal decomposition of the polymer during production is caused, and as a result, it becomes difficult to produce polyester having a high degree of polymerization.
- the lower limit of the reaction time is usually 2 hours or more, and the upper limit is usually 15 hours or less, preferably 8 hours or less, more preferably 6 hours or less.
- the reaction time is too short, a polyester with a low degree of polymerization is obtained, the tensile elongation at break is low, the terminal amount of the carboxyl group is large, and the tensile elongation at break is significantly deteriorated. There are many.
- the reaction time is too long, the molecular weight drop due to thermal decomposition of the polyester becomes significant, and not only the tensile elongation at break is reduced, but also the amount of carboxyl group terminals that affect the durability of the polymer increases due to thermal decomposition. There is.
- the molar ratio of the diol component to the aliphatic dicarboxylic acid component for obtaining the polyester having the desired degree of polymerization differs in the preferred range depending on the purpose and the type of raw material, but the diol component relative to 1 mol of the acid component.
- the lower limit is usually 0.8 mol or more, preferably 0.9 mol or more, and the upper limit is usually 3.0 mol or less, preferably 2.7 mol or less, particularly preferably 2.5 mol or less. .
- the polycondensation reaction is preferably performed in the presence of a polymerization catalyst.
- the addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.
- Examples of the polymerization catalyst include compounds containing a Group 1 to Group 14 metal element excluding hydrogen and carbon in the periodic table. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. Examples thereof include compounds containing an organic group such as carboxylate, alkoxy salt, organic sulfonate, or ⁇ -diketonate salt, and inorganic compounds such as metal oxides and halides described above and mixtures thereof. These catalyst components may be contained in a polyester raw material derived from biomass resources for the reasons described above.
- the raw material may be used as it is as a raw material containing a metal without purification.
- a polyester having a high degree of polymerization may be easier to produce as the content of a group 1 metal element such as sodium or potassium contained in the polyester raw material is smaller.
- purified to the grade which does not contain a group 1 metal element substantially is used suitably.
- the catalyst is preferably a compound that is liquid at the time of polymerization or that dissolves in an ester low polymer or polyester because the polymerization rate increases when it is melted or dissolved at the time of polymerization.
- the titanium compound is preferably a tetraalkyl titanate, specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Examples include benzyl titanate and mixed titanates thereof.
- tetra-n-propyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium bis (ammonium lactate) dihydroxide, polyhydroxytitanium stearate
- rate titanium lactate, butyl titanate dimer, titanium oxide, titania / silica composite oxide, tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, polyhydroxy titanium stearate, titanium lactate Butyl titanate dimer and titania / silica composite oxide are more preferable, especially tetra-n-butyl titanate, polyhydroxy titanium stearate, titanium (oxy ) Acetylacetonate, titanium tetraacetyl acetonate, titania / silica composite oxide
- zirconium compound examples include zirconium tetraacetate, zirconium acetylate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium potassium oxalate, and polyhydroxyzirconium.
- zirconium oxide and composite oxides containing, for example, zirconium and silicon are also preferably used.
- germanium compound examples include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium.
- germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferable, and germanium oxide is particularly preferable.
- the amount of the catalyst used in the case of using a metal compound as these polymerization catalysts is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30000 ppm or less, preferably 1000 ppm or less, as the amount of metal relative to the produced polyester. More preferably, it is 250 ppm or less, Especially preferably, it is 130 ppm or less. If too much catalyst is used, it is not only economically disadvantageous but also lowers the thermal stability of the polymer. Conversely, if it is too little, the polymerization activity is lowered, and as a result, the polymer decomposes during polymer production. Is more likely to be triggered.
- the polyester produced by the method of the present invention is usually characterized by a small amount of terminal carboxylic acid that significantly adversely affects the thermal stability of the polymer. Therefore, the polyester is excellent in thermal stability and has little deterioration in quality during molding. In the melt molding, there are few side reactions such as cleavage of terminal groups and cleavage of the main chain. Therefore, the number of terminal COOH groups of the preferred polyester produced in the present invention is usually 100 equivalents / ton (eq / ton) or less, preferably 60 eq / ton or less, more preferably 40 eq / ton, although it depends on the degree of polymerization of the polyester. Or less, particularly preferably 30 eq / ton or less.
- the lower limit of the number of terminal COOH groups of the polyester is usually 0.1 eq / ton or more, more preferably 1 eq / ton.
- the polyester produced in the present invention is usually preferably a polyester with little coloring.
- the upper limit of the yellowness (YI value) of the polyester of the present invention is usually 50 or less, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less.
- the lower limit is not particularly limited, but is usually ⁇ 20 or more, preferably ⁇ 10 or more, more preferably ⁇ 5 or more, particularly preferably ⁇ 3 or more, and most preferably ⁇ 1 or more.
- Polyesters exhibiting high YI values have the disadvantage that their use applications such as films and sheets are limited.
- polyester showing a low YI value is a more preferable form, but there are economical disadvantages such as manufacturing a polymer such that the manufacturing process is complicated and an extremely high capital investment is required.
- the YI value is a value measured by a method based on JIS K7105.
- the reduced viscosity ( ⁇ sp / C) value of the polyester produced according to the present invention is 0.5 or more, and preferably 1.6 or more, in view of obtaining practically sufficient mechanical properties. 0 or more is more preferable, and 2.3 or more is particularly preferable.
- the upper limit of the reduced viscosity ( ⁇ sp / C) value is usually 6.0 or less, preferably 5.0 or less, from the viewpoint of operability such as ease of pulling out after polyester polymerization and ease of molding. Preferably it is 4.0 or less.
- the reduced viscosity as used in the present invention is measured under the following measurement conditions.
- Viscosity tube Ubbelohde viscosity tube Measurement temperature: 30 ° C
- Solvent Phenol / tetrachloroethane (1: 1 weight ratio) solution
- Polyester concentration 0.5 g / dl
- various additives such as a heat stabilizer, an antioxidant, a crystal nucleating agent, a difficulty are added to the reaction system in the course of the production method of the polyester of the present invention or to the obtained polyester.
- a flame retardant, an antistatic agent, a release agent, an ultraviolet absorber and the like may be added during polymerization.
- a reinforcing agent such as glass fiber, carbon fiber, titanium whisker, mica, talc, CaCO 3 , TiO 2 , silica, and the like are added and molded. You can also.
- the polyester obtained by the production method of the present invention is excellent in heat resistance and color tone, in addition, excellent in hydrolysis resistance and biodegradability, and can be produced at low cost, so it is suitable for various film applications and injection molded product applications. ing.
- the molded product of the present invention can be obtained by molding the polyester of the present invention.
- a normal method can be adopted as the forming method.
- the obtained molded product is shown below together with its use.
- Specific applications include injection molded products (for example, fresh food trays, fast food containers, outdoor leisure products, etc.), extruded products (films, sheets, etc., for example fishing lines, fishing nets, vegetation nets, water retaining sheets, etc.) , Hollow molded products (bottles, etc.), and other agricultural films, coating materials, fertilizer coating materials, laminate films, plates, stretched sheets, monofilaments, multifilaments, non-woven fabrics, flat yarns, staples, crimps Fiber, striped tape, split yarn, composite fiber, blow bottle, foam, shopping bag, garbage bag, compost bag, cosmetic container, detergent container, bleach container, rope, binding material, surgical thread, sanitary cover stock material It can be used for a cold box, a cushion material film, a synthetic paper, and the like.
- LC was used for quantitative analysis of acids, saccharides, and cations, and amino acid quantitative analysis was performed using an amino acid analyzer under the following conditions.
- ⁇ Nitrogen atom content> A 10 mg sample was taken into a quartz boat, and the sample was burned using a total nitrogen analyzer (TN-10 model manufactured by Mitsubishi Chemical Corporation), and determined by a chemiluminescence method.
- ICS-1000 type manufactured by Dionex
- ⁇ YI value> It measured based on the method of JISK7105.
- ⁇ Polyester terminal carboxyl group amount> This is a value obtained by dissolving the obtained polyester in benzyl alcohol and titrating with 0.1 N NaOH, and is equivalent to a carboxyl group per 1 ⁇ 10 6 g.
- a medium [urea 2 g, (NH 4 ) 2 SO 4 7 g, KH 2 PO 4 0.5 g, K 2 HPO 4 0.5 g, MgSO 4 .7H 2 O 0.5 g, FeSO 4 ⁇ 7H 2 O 6 mg, MnSO 4. 4-5H 2 O 6 mg, biotin 200 ⁇ g, thiamine 100 ⁇ g, yeast extract 1 g, casamino acid 1 g, glucose 20 g, dissolved in 1 L distilled water]
- the Brevibacterium flavum MJ233 strain was cultured until the late logarithmic growth phase. The cells were collected by centrifugation (10000 g, 5 minutes).
- the obtained cells were suspended in 0.15 mL of a 10 mM NaCl / 20 mM Tris buffer solution (pH 8.0) / 1 mM EDTA ⁇ 2Na solution containing lysozyme at a concentration of 10 mg / mL.
- proteinase K was added to the suspension so that the final concentration was 100 ⁇ g / mL, and the mixture was incubated at 37 ° C. for 1 hour.
- sodium dodecyl sulfate was added to a final concentration of 0.5%, and the mixture was incubated at 50 ° C. for 6 hours for lysis.
- (B) Construction of plasmid for replacing PC gene promoter The DNA fragment of the N-terminal region of the pyruvate carboxylase gene derived from Brevibacterium flavum MJ233 strain was obtained using the DNA prepared in (A) above as a template, This was performed by PCR using synthetic DNA (SEQ ID NO: 1 and SEQ ID NO: 2) designed based on the reported sequence of the gene of Corynebacterium glutamicum ATCC13032 strain (Cg0689 of GenBank Database Accession No. BA00000036). The DNA of SEQ ID NO: 1 used was phosphorylated at the 5 ′ end.
- reaction solution Template DNA 1 ⁇ L, PfxDNA polymerase (manufactured by Invitrogen) 0.2 ⁇ L, 1 ⁇ concentration attached buffer, 0.3 ⁇ M each primer, 1 mM MgSO 4 , 0.25 ⁇ M dNTPs were mixed to make a total volume of 20 ⁇ L.
- Reaction temperature conditions DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle of 94 ° C. for 20 seconds, 60 ° C. for 20 seconds, and 72 ° C. for 1 minute was repeated 35 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute 20 seconds, and the heat retention at 72 ° C. in the final cycle was 4 minutes.
- the TZ4 promoter fragment constitutively highly expressed from Brevibacterium flavum MJ233 strain is a PCR using the plasmid pMJPC1 (Japanese Patent Laid-Open No. 2005-95169) as a template and the synthetic DNA described in SEQ ID NO: 3 and SEQ ID NO: 4. It was prepared by. The DNA of SEQ ID NO: 4 was phosphorylated at the 5 ′ end.
- reaction solution 1 ⁇ L of template DNA, 0.2 ⁇ L of Pfx DNA polymerase (manufactured by Invitrogen), 1 ⁇ concentrated buffer, 0.3 ⁇ M each primer, 1 mM MgSO 4 , 0.25 ⁇ M dNTPs were mixed to make a total volume of 20 ⁇ L.
- Reaction temperature conditions DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle of 94 ° C. for 20 seconds, 60 ° C. for 20 seconds, and 72 ° C. for 30 seconds was repeated 25 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute 20 seconds, and the heat retention at 72 ° C. in the final cycle was 3 minutes.
- the amplification product was confirmed by separation by 1.0% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis and visualization by ethidium bromide staining, and a fragment of about 0.5 kb was detected. Recovery of the target DNA fragment from the gel was performed using QIAQuick Gel Extraction Kit (manufactured by QIAGEN), and this was used as the TZ4 promoter fragment.
- the PC gene N-terminal fragment prepared above and the TZ4 promoter fragment were mixed, and ligation kit ver. 2 (manufactured by Takara Shuzo), cleaved with the restriction enzyme PstI, separated by 1.0% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis, and a DNA fragment of about 1.0 kb was extracted using QIAQuick Gel Extraction Kit. (Manufactured by QIAGEN) was used as a TZ4 promoter :: PC gene N-terminal fragment. Further, this DNA fragment and E.
- coli plasmid pHSG299 (Takara Shuzo) were mixed with DNA prepared by cutting with PstI, and ligation kit ver. 2 (Takara Shuzo) were used for connection.
- Escherichia coli DH5 ⁇ strain
- the recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 ⁇ g / mL kana machine and 50 ⁇ g / mL X-Gal. Clones that formed white colonies on this medium were subjected to liquid culture by a conventional method, and then plasmid DNA was purified.
- the obtained plasmid DNA was cleaved with the restriction enzyme PstI, whereby an inserted fragment of about 1.0 kb was recognized, and this was named pMJPC17.1.
- the DNA fragment in the 5 ′ upstream region of the pyruvate carboxylase gene derived from Brevibacterium flavum MJ233 strain was obtained using the DNA prepared in Example 1 (A) as a template and the entire genome sequence reported. It was carried out by PCR using synthetic DNA (SEQ ID NO: 5 and SEQ ID NO: 6) designed based on the sequence of the gene of Glutamicum ATCC13032 strain (GenBank Database Accession No. BA00000036).
- reaction solution Template DNA 1 ⁇ L, PfxDNA polymerase (manufactured by Invitrogen) 0.2 ⁇ L, 1 ⁇ concentration attached buffer, 0.3 ⁇ M each primer, 1 mM MgSO 4 , 0.25 ⁇ M dNTPs were mixed to make a total volume of 20 ⁇ L.
- Reaction temperature conditions DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds, 60 ° C. for 20 seconds and 72 ° C. for 30 seconds was repeated 35 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute 20 seconds, and the heat retention at 72 ° C.
- the amplification product was confirmed by separation by 1.0% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis and visualization by ethidium bromide staining, and a fragment of about 0.7 kb was detected.
- the DNA fragment of interest was recovered from the gel using a QIAQuick Gel Extraction Kit (manufactured by QIAGEN). The recovered DNA fragment was phosphorylated at the 5 ′ end with T4 polynucleotide kinase (T4 Polynucleotide Kinase: manufactured by Takara Shuzo), and then ligated kit ver.
- the obtained plasmid DNA was subjected to a PCR reaction using the synthetic DNAs shown in SEQ ID NO: 7 and SEQ ID NO: 6 as primers.
- Composition of reaction solution 1 ng of the above plasmid, Ex-Taq DNA polymerase (manufactured by Takara Shuzo Co., Ltd.) 0.2 ⁇ L, 1 ⁇ concentration attached buffer, 0.2 ⁇ M each primer, 0.25 ⁇ M dNTPs were mixed to make a total volume of 20 ⁇ L.
- Reaction temperature condition DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds, 60 ° C. for 20 seconds and 72 ° C.
- a plasmid that recognized an amplification product of about 0.7 kb was selected and named pMJPC5.1.
- pMJPC17.1 and pMJPC5.1 were cut with restriction enzyme XbaI and mixed, and ligation kit ver. 2 (Takara Shuzo) were used for connection.
- the DNA fragment cleaved with restriction enzyme SacI and restriction enzyme SphI was separated by 0.75% agarose (SeaKem GTG agarose: manufactured by FMCBioProducts) gel electrophoresis, and a DNA fragment of about 1.75 kb was manufactured by QIAQUICK Gel Extraction Kit (QIAGEN Kit) ).
- a DNA fragment in which the TZ4 promoter is inserted between the 5 ′ upstream region and the N-terminal region of this PC gene, and a DNA prepared by cleaving the plasmid pKMB1 (JP-A-2005-95169) containing the sacB gene with SacI and SphI Mixed and ligation kit ver. 2 (Takara Shuzo) were used for connection.
- Escherichia coli DH5 ⁇ strain
- the recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 ⁇ g / mL kana machine and 50 ⁇ g / mLX-Gal.
- Plasmid DNA was purified. By cutting the obtained plasmid DNA with restriction enzymes SacI and SphI, an insert fragment of about 1.75 kb was observed, which was named pMJPC17.2 (FIG. 1).
- LBG agar medium [tryptone 10 g, yeast extract 5 g, NaCl 5 g, glucose 20 g, and agar 15 g dissolved in 1 L of distilled water] was smeared.
- the strain grown on this medium is a plasmid in which pMJPC17.2 is a plasmid that cannot be replicated in Brevibacterium flavum MJ233 strain, so the PC gene of the plasmid and the same gene on the genome of Brevibacterium flavum MJ233 strain As a result of homologous recombination with the kanamycin, the kanamycin resistance gene and sacB gene derived from the plasmid should be inserted on the genome.
- the homologous recombination strain was subjected to liquid culture in an LBG medium containing 25 ⁇ g / mL kanamycin. A portion equivalent to about 1 million cells of this culture was smeared on a 10% sucrose-containing LBG medium.
- the enzyme activity was measured using 100 mM Tris / HCl buffer (pH 7.5), 0.1 mg / 10 ml biotin, 5 mM magnesium chloride, 50 mM sodium bicarbonate, 5 mM sodium pyruvate, 5 mM adenosine triphosphate, 0.32 mM NADH.
- the reaction was carried out at 25 ° C. in a reaction solution containing 20 units / 1.5 ml malate dehydrogenase (manufactured by WAKO, derived from yeast) and the enzyme.
- 1 U was defined as the amount of enzyme that catalyzes the decrease of 1 ⁇ mol NADH per minute.
- the specific activity in the cell-free extract with enhanced pyruvate carboxylase expression was 0.1 U / mg protein.
- the Brevibacterium flavum MJ233 / PC-4 / ⁇ LDH strain was used as an organic acid-producing bacterium for microbial cell preparation and organic acid production reaction.
- Ammonium sulfate 1.0 g, monopotassium phosphate: 1.5 g, dipotassium phosphate 1.5 g, potassium chloride: 1.67 g, magnesium sulfate heptahydrate: 0.5 g, ferrous sulfate, heptahydrate
- Product 40 mg, manganese sulfate / hydrate: 40 mg
- D-biotin 1.0 mg
- thiamine hydrochloride 1.0 mg
- yeast extract 10 g antifoaming agent (CE457: manufactured by NOF Corporation): 1.0 g and distilled water: 400 mL of 1000 mL of medium was placed in a 1 L fermentor and sterilized by heating at 120 ° C.
- Example 1 The culture solution prepared according to the reference example was concentrated under reduced pressure heating. While stirring the concentrated culture solution, 47% sulfuric acid was added dropwise to the culture solution to adjust the pH of the solution to 2. A volume of methyl ethyl ketone (MEK) equal to that of the culture broth was added as an organic solvent to the culture broth added with sulfuric acid, and the mixture was stirred at 25 ° C. for about 30 minutes. The liquid obtained was allowed to stand, then divided into an organic layer and an aqueous layer, MEK having a volume half the volume of the aqueous layer was added to the separated aqueous layer, and the mixture was stirred at 25 ° C. for 30 minutes.
- MEK methyl ethyl ketone
- MEK was distilled off from the obtained MEK extract at 70 ° C. while adjusting the degree of vacuum from 400 mmHg to 100 mmHg, and the MEK extracted organic layer was concentrated. Thereafter, the obtained solution was cooled from 70 ° C. to 40 ° C. over 30 minutes, and then stirred at 40 ° C. for 1 hour. The precipitated crystals were filtered and rinsed with cold water to obtain crude crystals. On the other hand, the filtrate was further cooled from 40 ° C. to 10 ° C. over 30 minutes and stirred at 10 ° C. for 1 hour. The precipitated crystals were filtered and rinsed with cold water to obtain crude crystals. In this step, 98% of the succinic acid extracted in the MEK organic layer was recovered.
- Succinic acid at this stage was light brown and had a strong odor.
- the hydrogenation reaction of a small amount of fumaric acid contained in 150 g of crude succinic acid obtained as described above was carried out using SUS316 500 ml induction stirring autoclave in 5% Pd / C in 282 g of distilled water. (Wako catalog 326-81672, catalyst amount: 1 wt% with respect to succinic acid), hydrogen pressure was 0.2 MPa, reaction temperature was 100 ° C., and reaction time was 2 hours.
- All trace amounts of fumaric acid contained in the crude succinic acid (containing 0.3% by weight based on succinic acid) were all derived into succinic acid.
- Distilled water was added to the succinic acid solution after completion of the reaction to form a 19 wt% aqueous succinic acid solution, and then the catalyst was filtered off.
- the hydrogen treatment liquid had almost no odor.
- activated carbon (the amount of activated carbon used: 10 wt% with respect to succinic acid, Hokuetsu CL-K (activated carbon previously washed with a 5 wt% aqueous succinic acid solution at 65 ° C.) for 1 hour) was added to the solution.
- the activated carbon treatment of the succinic acid aqueous solution was performed under a condition of stirring at 65 ° C. for 1 hour. After the activated carbon was separated by filtration, the same treatment was performed by newly adding 10 wt% of activated carbon to the obtained succinic acid aqueous solution with respect to succinic acid. This activated carbon treatment was carried out five times in total.
- the absorbance at 280 nm decreased from 0.861 to 0.220 and the absorbance at 260 nm decreased from 1.258 to 0.298 after 5 times of activated carbon treatment.
- aqueous solution of succinic acid treated with activated carbon is diluted with distilled water to a concentration of 50 g / L, and a cation is contained in a trace amount by ion exchange treatment (cation exchange resin (Diaion SKT20L (Mitsubishi Chemical Corporation): H type)). Was removed.
- ion exchange resin Diaion SKT20L (Mitsubishi Chemical Corporation): H type
- the concentrations of Na, K, Mg, Ca, and NH 4 ions were all less than 1 ppm, the sulfur atom content was less than 1 ppm, and the nitrogen atom content was 8 ppm.
- a 3.0 wt% succinic acid aqueous solution of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured using Hitachi spectrophotometer Hitachi UV-3500 was 0.008. ( Figure 3).
- polyester (yellowness YI is 6) was obtained.
- the polyester obtained had a reduced viscosity ( ⁇ sp / c) of 2.3.
- the terminal carboxyl group amount of the polyester was 24 equivalents / ton.
- the obtained polyester was uniformly dissolved in chloroform at room temperature. When chloroform was distilled off from the chloroform solution, a uniform film was formed.
- Example 2 In the same manner as in Example 1, the culture solution prepared according to the reference example was concentrated under reduced pressure and heating. While stirring the concentrated culture solution, 47% sulfuric acid was added dropwise to the culture solution to adjust the pH of the culture solution to 2. A volume of methyl ethyl ketone (MEK) equal to that of the culture broth was added as an organic solvent to the culture broth added with sulfuric acid, and the mixture was stirred at 25 ° C. for about 30 minutes. The obtained liquid was allowed to stand, then divided into an organic layer and an aqueous layer, MEK having an equal volume of the aqueous layer was added to the separated aqueous layer, and the mixture was stirred at 25 ° C. for 30 minutes.
- MEK methyl ethyl ketone
- the liquid was allowed to stand, and then divided into an organic layer and an aqueous layer. The same operation was repeated once more, and all the organic layers were combined.
- LC liquid chromatography
- 97.9% amount of succinic acid contained in the broth used was extracted from the organic layer.
- MEK was distilled off under reduced pressure of about 50 mmHg while the organic layer was heated to 90 ° C., concentrated, cooled with ice water, and allowed to stand for 2 hours. The precipitated crystals were filtered and rinsed with cold water to obtain crude crystals.
- 96% of the succinic acid extracted in the MEK organic layer was recovered. Succinic acid at this stage was light brown and had a strong odor.
- the concentrations of Mg, Ca and NH 4 ions are all less than 1 ppm, the sulfur atom content is less than 1 ppm, the concentrations of Na and K ions are 4 ppm and 2 ppm, respectively, and the nitrogen atom content is 9 ppm. there were. Further, a 3.0 wt% succinic acid aqueous solution of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured using Hitachi spectrophotometer Hitachi UV-3500 was 0.055. (FIG. 4).
- Yellow polyester (yellowness YI is 23) was obtained.
- the polyester obtained had a reduced viscosity ( ⁇ sp / c) of 2.4.
- the amount of terminal carboxyl groups of the polyester was 25 equivalents / ton.
- the obtained polyester was uniformly dissolved in chloroform at room temperature. When chloroform was distilled off from the chloroform solution, a uniform film was formed.
- Example 3 The culture solution prepared according to the reference example was protonated with concentrated sulfuric acid in the same manner as in Example 1, and further extracted and crystallized to recover crude succinic acid. Succinic acid at this stage was light brown and had a strong odor.
- 100 g of crude succinic acid having a strong odor obtained as described above was treated with 5% Pd / C (Wako catalog 326) in 222 g of demineralized water. ⁇ 81672, catalyst amount: 1 wt% with respect to succinic acid), hydrogen pressure was 0.2 MPa, reaction temperature was 100 ° C., and reaction time was 2 hours.
- the hydrogen treatment liquid had almost no odor.
- the catalyst was separated from the treatment liquid by hot filtration at 70 ° C.
- the hot filtrate was cooled to 20 ° C. with stirring for about 90 minutes, and further kept at 20 ° C. for 1 hour to precipitate crystals, and solid-liquid separation was performed with Nutsche to obtain hydrous succinic acid crystals.
- the obtained succinic acid crystals had a white color, and no specific odor was felt from the succinic acid crystals.
- Example 4 The culture solution prepared according to the reference example was protonated with concentrated sulfuric acid in the same manner as in Example 1, and further extracted and crystallized to recover crude succinic acid. Succinic acid at this stage was light brown and had a strong odor. Next, after preparing 30 wt% crude succinic acid aqueous solution at 80 degreeC, the activated carbon Kuraray Coal GW made from Kuraray Chemical Co. of 5 wt% with respect to succinic acid was added. The activated carbon treatment was carried out for 3 hours using a constant temperature shaker kept at 80 ° C. Thereafter, the activated carbon was filtered off at 80 ° C. Even at this stage, a unique odor remained in the aqueous succinic acid solution.
- the obtained aqueous succinic acid solution was charged into a 500 ml induction stirring autoclave made of SUS316, and the hydrogen pressure was 0.8 MPa in the presence of 5% Pd / C (Wako catalog 326-81672, catalyst amount: 0.06 wt% with respect to succinic acid).
- the hydrogen treatment was carried out under conditions of a reaction temperature of 80 ° C. and a reaction time of 3 hours. As a result, all fumaric acid contained in the crude succinic acid in an amount of 1.8% by weight based on succinic acid was derived into succinic acid. After completion of the reaction, the catalyst was filtered off. The hydrogen treatment liquid had almost no odor.
- ion exchange treatment cation exchange resin (Diaion SK1B-H (manufactured by Mitsubishi Chemical Corporation): H type)
- the concentrations of Na, K, Mg, Ca, and NH 4 ions were all 1 ppm or less, the sulfur atom content was less than 1 ppm, and the nitrogen atom content was 2 ppm. Further, a succinic acid aqueous solution having a concentration of 3.0 wt% of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured with a Hitachi spectrophotometer Hitachi UV-3500 was the succinic acid of Example 1. (0.01 or less).
- This mixed solution was transferred to a 1000 cm 3 eggplant-shaped flask and concentrated in an oil bath at 60 ° C. under reduced pressure using an evaporator. After 1 hour, most of the ethanol was distilled off, leaving a translucent viscous liquid. The temperature of the oil bath was further increased to 80 ° C., and further concentration was performed under a reduced pressure of 5 Torr. The viscous liquid gradually changed from the surface to a powder form, and was completely powdered after 2 hours. Then, it returned to normal pressure using nitrogen, and it cooled to room temperature, and obtained 108 g of pale yellow powder.
- the amount added was 50 ppm as titanium atoms per polyester resin obtained.
- the reaction temperature is gradually raised to 250 ° C., and the pressure is reduced to 0.06 ⁇ 10 3 Pa at the same time over 2 hours.
- the reaction is further performed for 2.5 hours at the same reduced pressure, and the polymerization is completed.
- Polyester yellowness YI is 2
- the polyester obtained had a reduced viscosity ( ⁇ sp / c) of 2.3.
- the terminal carboxyl group amount of the polyester was 24 equivalents / ton.
- Example 5 The culture solution prepared according to the reference example was protonated with concentrated sulfuric acid in the same manner as in Example 1, and further extracted and crystallized to recover crude succinic acid. Succinic acid at this stage was light brown and had a strong odor. Next, a 30 wt% crude succinic acid aqueous solution was prepared at 80 ° C., and then 0.3 wt% of powdered chemical activated charcoal diamond hop 8ED (Mitsubishi Chemical Calgon Co., Ltd.) was added to succinic acid. . The activated carbon treatment was performed at 80 ° C. for 2 hours while stirring at 200 rpm using a three-one motor.
- powdered chemical activated charcoal diamond hop 8ED Mitsubishi Chemical Calgon Co., Ltd.
- the obtained aqueous succinic acid solution was charged into a 500 ml induction stirring autoclave made of SUS316, 5% Pd / C (Wako catalog 326-81672, catalyst amount: 0.06 wt% with respect to succinic acid)
- hydrogen treatment was carried out under the conditions of a hydrogen pressure of 0.8 MPa, a reaction temperature of 80 ° C., and a reaction time of 3 hours.
- all fumaric acid contained in the crude succinic acid in an amount of 1.3% by weight based on succinic acid was derived into succinic acid.
- the catalyst was filtered off.
- the hydrogen treatment liquid had almost no odor.
- the hydrogenated succinic acid aqueous solution was subjected to ion exchange treatment (cation exchange resin (Diaion SK1B-H (manufactured by Mitsubishi Chemical Corporation): H type)) at 80 ° C. to remove cations contained in a trace amount.
- ion exchange treated succinic acid aqueous solution was cooled to 20 ° C. with stirring for about 90 minutes, and further kept at 20 ° C. for 1 hour to precipitate crystals.
- the concentrations of Na, K, Mg, Ca, and NH 4 ions were all 1 ppm or less, the sulfur atom content was less than 1 ppm, and the nitrogen atom content was 2 ppm. Further, a succinic acid aqueous solution having a concentration of 3.0 wt% of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured with a Hitachi spectrophotometer Hitachi UV-3500 was the succinic acid of Example 1. (0.01 or less).
- polyester Production Example 4 A polyester was produced using the same method as in Polyester Production Example 3 except that the succinic acid produced in Example 5 was used as a raw material.
- a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer and a vacuum outlet 100 parts by weight of succinic acid produced in Example 5 as a raw material, 99.2 parts by weight of 1,4-butanediol, 0.38 parts by weight of malic acid (total malic acid amount 0.33 mol% with respect to succinic acid) was charged, and the system was placed in a nitrogen atmosphere by nitrogen-vacuum substitution. Next, the temperature in the system was raised to 230 ° C.
- Polyester Production Example 3 The catalyst solution described in Polyester Production Example 3 was added. The amount added was 50 ppm as titanium atoms per polyester resin obtained.
- the reaction temperature is gradually raised to 250 ° C., and the pressure is reduced to 0.06 ⁇ 10 3 Pa at the same time over 2 hours.
- the reaction is further carried out for 2.4 hours at the same reduced pressure, and the polymerization is completed.
- Polyester (yellowness YI is 3) was obtained.
- the polyester obtained had a reduced viscosity ( ⁇ sp / c) of 2.3.
- the terminal carboxyl group amount of the polyester was 24 equivalents / ton.
- Comparative Example 1 The same operation as in Example 3 was performed except that the heat treatment was performed under a pressure of 0.2 MPa as the nitrogen pressure instead of performing the hydrogen treatment under a pressure of 0.2 MPa as the hydrogen pressure.
- heat treatment 100 g of crude succinic acid of the same lot as that used in Example 3 which exhibits a light brown color and exhibits a strong odor was performed in 222 g of demineralized water with 5% Pd. / C (Wako catalog 326-81672, catalyst amount: 1 wt% with respect to succinic acid), nitrogen pressure was 0.2 MPa, reaction temperature was 100 ° C., and reaction time was 2 hours.
- the treatment liquid had a strong odor.
- the catalyst was separated from the treatment liquid by hot filtration at 70 ° C.
- the hot filtrate was cooled to 20 ° C. with stirring for about 90 minutes, and further kept at 20 ° C. for 1 hour to precipitate crystals, and solid-liquid separation was performed with Nutsche to obtain hydrous succinic acid crystals.
- the obtained succinic acid crystal had a white color, but the succinic acid crystal had a strong odor peculiar to it.
- a characteristic odor remained in the succinic acid crystals.
- the concentrations of Na, K, Mg, Ca, NH 4 ions are all less than 1 ppm
- the sulfur atom content is less than 1 ppm
- the nitrogen atom content is 3 ppm
- the fumaric acid content is 0. 0.08% by weight.
- a 3.0 wt% aqueous succinic acid solution of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured using Hitachi spectrophotometer Hitachi UV-3500 was 0.059. .
- succinic acid is manufactured from petrochemical-derived raw materials and used in a wide variety of applications.
- Succinic acid derived from bioresources is also preferably used for such applications, as described in Microbiol. Biotechnol., 2007, 76, 727 and Plastic Swage, 2009, Aug., ⁇ 86 etc. can do.
- succinic acid esters such as dimethyl succinate and diethyl succinate, pyrrolidone, N-methylpyrrolidone, etc.
- polymer compounds and products such as polyester, polyurethane, polyamide, etc., acidulants, seasonings, brewing chemicals, Processed food additives, food additives, foaming bath ingredients, plant growth inhibitors, herbicides, antibacterial agents, resident mosquito attractants, etc.
- raw materials and ingredients for products, etc. raw materials for products used for photography and printing, etc.
- Raw materials and components for metal processing such as high-temperature welding agents and anodized surface adhesives as ingredients, and raw materials and components for adhesives and sealants, such as powdered nickel production, steel polishing baths, metal processing washing solvents, metal sintering binders, etc.
- welding flux porous titanium oxide production, boehmite production, photocatalyst coating agent, porous ceramic production, etc.
- raw materials and components such as bleaching agents as raw materials and components such as dyeing assistants, as raw materials and components such as electrolyte solvents and plating baths, as raw materials and components such as deodorizers and air cleaning agents
- raw materials for bioabsorbable compounds such as bioabsorbable sutures
- raw materials and ingredients for processing fiber products and softeners As raw materials and components of solvents, solvents, etc.
- raw materials and components of water-soluble paint solvents as raw materials and components of biodegradable resins, as odorless sealants, etc.
- sealant raw materials and components steel products, copper products, alloy products As a raw material and ingredients for anticorrosives, such as coating, anti-freezing, metal processing, lead for perchloric acid, boiler water treatment, synthetic lubricants, lubricants for heat-resistant plastics, lubricants for electrical contacts, etc.
- raw materials and components such as cement admixtures and treating agents as raw materials and components such as engine purifiers, as raw materials and components such as petroleum refining solvents, as well as proppant resuscitation, precipitation filter cake removal, petroleum and natural
- raw materials and components for gas mining aids, natural gas dehydration solvents, etc. as raw materials and components for products related to natural gas production, as low-dust concrete flooring, asphalt pavement, etc., as raw materials and components for building materials, for ink It can be used as raw materials and components such as solvents and deinking agents.
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Abstract
Description
(1)バイオマス資源から誘導されるコハク酸の製造方法であって、少なくとも該コハク酸を含む溶液を触媒存在下で水素処理を行う工程を含むことを特徴とするコハク酸の製造方法。
(2)水素処理の温度が30℃以上、150℃以下、水素圧が0.1MPa以上、5MPa以下であることを特徴とする(1)に記載のコハク酸の製造方法。
(3)金属酸化物、シリカ及び活性炭の群から選ばれるいずれかの吸着剤存在下、水素化触媒により水素処理を行うことを特徴とする(1)又は(2)のいずれかに記載のコハク酸の製造方法。
(4)コハク酸を含む溶液が水溶液であることを特徴とする(1)~(3)のいずれかに記載のコハク酸の製造方法。
(5)水素処理を行うコハク酸を含む溶液にフマル酸が含まれていることを特徴とする(1)~(4)のいずれかに記載のコハク酸の製造方法。 That is, the present invention is as follows.
(1) A method for producing succinic acid derived from biomass resources, comprising a step of hydrotreating at least a solution containing the succinic acid in the presence of a catalyst.
(2) The method for producing succinic acid according to (1), wherein the hydrogen treatment temperature is 30 ° C. or higher and 150 ° C. or lower, and the hydrogen pressure is 0.1 MPa or higher and 5 MPa or lower.
(3) The agglutination according to either (1) or (2), wherein hydrogen treatment is performed with a hydrogenation catalyst in the presence of any adsorbent selected from the group consisting of metal oxide, silica and activated carbon Acid production method.
(4) The method for producing succinic acid according to any one of (1) to (3), wherein the solution containing succinic acid is an aqueous solution.
(5) The method for producing succinic acid according to any one of (1) to (4), wherein fumaric acid is contained in a solution containing succinic acid to be subjected to hydrogen treatment.
(7)コハク酸の250~300nmの紫外線領域の平均吸光度が0.05以下になるように、該コハク酸を含む溶液から不純物を除去することを特徴とする(1)~(6)のいずれかに記載のコハク酸の製造方法。
(8)該不純物の除去が活性炭を用いた吸着除去によることを特徴とする(7)に記載のコハク酸の製造方法。
(9)該不純物の除去が溶媒を用いた晶析によることを特徴とする(7)又は(8)に記載のコハク酸の製造方法。
(10)水素処理工程より前の工程でコハク酸を含む溶液中の不溶成分を膜透過処理により除去することを特徴とする(1)~(9)のいずれかに記載のコハク酸の製造方法。
(11)水素処理工程より前の工程でコハク酸を含む溶液中の不溶成分を吸着剤により除去することを特徴とする(1)~(9)のいずれかに記載のコハク酸の製造方法。
(12)バイオマス資源から誘導されるコハク酸に、溶液中での活性炭を用いた吸着処理又は晶析処理の少なくともいずれかの処理を経た後に、触媒存在下で水素処理を行うことを特徴とする(1)~(11)のいずれかに記載のコハク酸の製造方法。
(13)バイオマス資源が植物資源であることを特徴とする(1)~(12)のいずれかに記載のコハク酸の製造方法。
(14)該コハク酸の黄色度(YI)が10以下であることを特徴とする(1)~(13)のいずれかに記載のコハク酸の製造方法。 (6) The production of succinic acid according to (5), wherein the content of fumaric acid in the solution containing succinic acid to be subjected to hydrogen treatment is 0.01 to 10% by weight based on the weight of succinic acid. Method.
(7) Any one of (1) to (6), wherein impurities are removed from the solution containing succinic acid so that the average absorbance in the ultraviolet region of 250 to 300 nm of succinic acid is 0.05 or less. A method for producing succinic acid according to
(8) The method for producing succinic acid according to (7), wherein the impurities are removed by adsorption removal using activated carbon.
(9) The method for producing succinic acid according to (7) or (8), wherein the impurities are removed by crystallization using a solvent.
(10) The method for producing succinic acid according to any one of (1) to (9), wherein insoluble components in the solution containing succinic acid are removed by membrane permeation treatment in a step before the hydrogen treatment step .
(11) The method for producing succinic acid according to any one of (1) to (9), wherein an insoluble component in the solution containing succinic acid is removed by an adsorbent in the step before the hydrogen treatment step.
(12) A succinic acid derived from biomass resources is subjected to a hydrogen treatment in the presence of a catalyst after at least one of an adsorption treatment using activated carbon in a solution and a crystallization treatment. (1) The method for producing succinic acid according to any one of (11) to (11).
(13) The method for producing succinic acid according to any one of (1) to (12), wherein the biomass resource is a plant resource.
(14) The method for producing succinic acid according to any one of (1) to (13), wherein the yellowness (YI) of the succinic acid is 10 or less.
(16)該不純物が芳香族化合物であることを特徴とする(7)~(9)のいずれかに記載のコハク酸の製造方法。
(17)(1)~(16)のいずれかに記載の方法により製造されたコハク酸。
(18)250~300nmの紫外線領域の平均吸光度が0.05以下であることを特徴とするバイオマス資源から誘導されたコハク酸。
(19)黄色度(YI)が10以下であることを特徴とする(18)に記載のコハク酸。
(20)(17)~(19)のいずれかに記載のコハク酸を原料として用いて得られたポリエステル。
(21)カルボキシル基末端濃度が100当量/トン以下であることを特徴とする(20)に記載のポリエステル。
(22)ポリエステルの還元粘度(ηsp/c)が0.5以上であることを特徴とする(20)又は(21)に記載のポリエステル。
(23)(20)~(22)のいずれかに記載のポリエステルを成形してなる成形体。 (15) The method for producing succinic acid according to any one of (7) to (9), wherein the impurity is a compound containing nitrogen.
(16) The method for producing succinic acid according to any one of (7) to (9), wherein the impurity is an aromatic compound.
(17) Succinic acid produced by the method according to any one of (1) to (16).
(18) Succinic acid derived from biomass resources, wherein the average absorbance in the ultraviolet region of 250 to 300 nm is 0.05 or less.
(19) The succinic acid according to (18), wherein the yellowness (YI) is 10 or less.
(20) A polyester obtained using the succinic acid according to any one of (17) to (19) as a raw material.
(21) The polyester as described in (20), wherein the carboxyl group terminal concentration is 100 equivalent / ton or less.
(22) The polyester according to (20) or (21), wherein the reduced viscosity (ηsp / c) of the polyester is 0.5 or more.
(23) A molded product obtained by molding the polyester according to any one of (20) to (22).
本発明は、バイオマス資源から誘導されるコハク酸の製造方法であって、その製造工程には、少なくとも該コハク酸を含む溶液を触媒存在下で水素処理を行う工程が含まれることを特徴とするコハク酸の製造方法に関するものである。また、250~300nmの紫外線領域の平均吸光度が0.05以下であることを特徴とするバイオマス資源から誘導されたコハク酸、ならびにコハク酸の製造方法であって、バイオマス資源からコハク酸を誘導し、該コハク酸の250~300nmの紫外線領域の平均吸光度が0.05以下になるように、該コハク酸から不純物を除去することを特徴とするコハク酸の製造方法に関するものである。 Hereinafter, the present invention will be described in detail.
The present invention is a method for producing succinic acid derived from biomass resources, and the production process includes a step of hydrotreating at least a solution containing the succinic acid in the presence of a catalyst. The present invention relates to a method for producing succinic acid. In addition, succinic acid derived from biomass resources characterized in that the average absorbance in the ultraviolet region of 250 to 300 nm is 0.05 or less, and a method for producing succinic acid, wherein succinic acid is derived from biomass resources Further, the present invention relates to a method for producing succinic acid, wherein impurities are removed from the succinic acid so that an average absorbance in the ultraviolet region of 250 to 300 nm of the succinic acid is 0.05 or less.
本発明のコハク酸としては、特にバイオマス資源から非常に高い炭素収率で誘導できる。
本発明において、コハク酸は、バイオマス資源から誘導されるものである。バイオマス資源としては、例えば、木材、稲わら、籾殻、米ぬか、古米、とうもろこし、サトウキビ、キャッサバ、サゴヤシ、おから、コーンコブ、タピオカカス、バガス、植物油カス、芋、そば、大豆、油脂、古紙、製紙残渣、水産物残渣、家畜排泄物、下水汚泥、食品廃棄物等が挙げられる。この中でも木材、稲わら、籾殻、米ぬか、古米、とうもろこし、サトウキビ、キャッサバ、サゴヤシ、おから、コーンコブ、タピオカカス、バガス、植物油カス、芋、そば、大豆、油脂、古紙、製紙残渣等の植物資源が好ましく、より好ましくは、木材、稲わら、籾殻、古米、とうもろこし、サトウキビ、キャッサバ、サゴヤシ、芋、油脂、古紙、製紙残渣であり、最も好ましくはとうもろこし、サトウキビ、キャッサバ、サゴヤシである。これらのバイオマス資源は、一般に、窒素元素やNa、K、Mg、Ca等の多くのアルカリ金属、アルカリ土類金属を含有する。 <Succinic acid>
The succinic acid of the present invention can be derived from a biomass resource with a very high carbon yield.
In the present invention, succinic acid is derived from biomass resources. Biomass resources include, for example, wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil scum, persimmon, buckwheat, soybean, fat, waste paper, papermaking residue , Marine product residue, livestock excrement, sewage sludge, food waste and the like. Among them, plant resources such as wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil residue, buckwheat, soy, oil, waste paper, paper residue More preferred are wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, straw, oil and fat, waste paper, papermaking residue, and most preferred are corn, sugar cane, cassava, sago palm. These biomass resources generally contain a large amount of alkali metals and alkaline earth metals such as nitrogen element, Na, K, Mg, and Ca.
尚、本発明の方法において発酵液を用いる場合、微生物を除去した後の発酵液を用いることが好ましい。微生物の除去方法は特に限定は無いが、沈降分離、遠心分離、ろ過分離ならびにそれらを組み合わせた方法などが用いられる。工業的には遠心分離、膜ろ過分離などの方法で行われる。遠心分離においては、遠心沈降、遠心ろ過などを用いることができる。遠心分離において、その操作条件は特に限定されるものではないが、通常100G~100,000Gの遠心力で分離される。またその操作は連続式でも、バッチ式でも使用できる。
また膜ろ過分離においては、精密ろ過および/または限外ろ過等を使用することが出来る。膜の材質は特に限定は無く、例えばポリオレフィン、ポリスルフィン、ポリアクリロニトリル、ポリフッ化ビニリデン等の有機膜でも、セラミック等の無機材質の膜でも使用できる。また操作方法として、デッドエンド型、クロスフロー型いずれでも用いることができる。膜ろ過分離では、微生物が膜に目詰まりすることが多いので、遠心分離などで微生物を粗取りを行ってから膜ろ過を行うなどの方法も用いられる。 In the present invention, the fermentation broth after microbial conversion may be appropriately concentrated in consideration of operability and efficiency in the subsequent purification step. Although it does not specifically limit as a concentration method, The method of distribute | circulating an inert gas, the method of distilling off water by heating, the method of distilling off water by pressure reduction, the method of combining these, etc. are mentioned. Further, the concentration operation may be performed by a batch operation or a continuous operation.
In addition, when using a fermented liquid in the method of this invention, it is preferable to use the fermented liquid after removing microorganisms. The method for removing the microorganisms is not particularly limited, and sedimentation separation, centrifugation, filtration separation, a combination thereof, and the like are used. Industrially, it is performed by a method such as centrifugal separation or membrane filtration separation. In centrifugation, centrifugal sedimentation, centrifugal filtration, or the like can be used. In the centrifugation, the operating conditions are not particularly limited, but the separation is usually performed with a centrifugal force of 100 G to 100,000 G. The operation can be performed continuously or batchwise.
In membrane filtration separation, microfiltration and / or ultrafiltration can be used. The material of the film is not particularly limited, and for example, an organic film such as polyolefin, polysulfine, polyacrylonitrile, polyvinylidene fluoride, or a film made of an inorganic material such as ceramic can be used. As an operation method, either a dead end type or a cross flow type can be used. In membrane filtration separation, since microorganisms often clog the membrane, a method of performing membrane filtration after roughly removing the microorganisms by centrifugation or the like is also used.
ここでいう「主体として含む」状態とは、溶媒を除く全成分の重量に対する該成分の重量が、通常50重量%以上、好ましくは60重量%以上、より好ましくは70重量%以上、特に好ましくは90重量%以上含まれる状態を示す。 In the present invention, the solution or aqueous solution containing succinic acid is a solution or aqueous solution mainly containing succinic acid derived from biomass resources. Accordingly, a solution or an aqueous solution mainly containing a succinate such as ammonium succinate or magnesium succinate is referred to as a solution or aqueous solution containing succinate.
The term “contained as the main component” as used herein means that the weight of the component relative to the weight of all components excluding the solvent is usually 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably The state of 90% by weight or more is shown.
この方法で使用される有機溶媒は、通常、無機性値/有機性値の比(I/O値)が0.2以上2.3以下であり、常圧(1気圧)で沸点が40℃以上の有機溶媒であるが、より好ましくは、I/O値が、0.3以上2.0以下であり、常圧で沸点が40℃以上の有機溶媒であり、更に好ましくは、I/O値が0.3以上2.0以下であり、常圧で沸点が60℃以上の有機溶媒である。このような有機溶媒を用いることにより、コハク酸を選択的に抽出して、効率よく糖類やアミノ酸と分離できる。また、常圧で沸点が40℃以上の有機溶媒を用いることにより、溶媒が気化して引火する危険性や、溶媒が気化してコハク酸の抽出効率が低下するという問題や溶媒のリサイクルがしにくいといった問題を回避することができる。 In the present invention, the aqueous solution converted into succinic acid with the inorganic acid is not particularly limited, but succinic acid may be extracted from the aqueous solution using an organic solvent.
The organic solvent used in this method usually has an inorganic value / organic value ratio (I / O value) of 0.2 or more and 2.3 or less, and has a boiling point of 40 ° C. at normal pressure (1 atm). More preferably, the organic solvent is an organic solvent having an I / O value of 0.3 or more and 2.0 or less and a boiling point of 40 ° C. or more at normal pressure, and more preferably I / O. An organic solvent having a value of 0.3 or more and 2.0 or less and a normal pressure and a boiling point of 60 ° C. or more. By using such an organic solvent, succinic acid can be selectively extracted and efficiently separated from saccharides and amino acids. In addition, by using an organic solvent having a boiling point of 40 ° C. or higher at normal pressure, there is a risk that the solvent vaporizes and ignites, a problem that the solvent vaporizes and the extraction efficiency of succinic acid decreases, and the solvent is recycled. The problem of difficulty can be avoided.
I/O値が0.2以上2.3以下であり、常圧で沸点が40℃以上の有機溶媒としては、メチルエチルケトン、メチルイソブチルケトン、アセトン等のケトン系溶媒、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、酢酸エチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、プロパノール、ブタノール、オクタノール等の炭素鎖3以上のアルコールが例示される。 Inorganic values and organic values have been proposed by organic conceptual diagrams ("systematic organic qualitative analysis", Satoshi Fujita, Kazama Shobo (1974)) and have been set in advance for functional groups constituting organic compounds. The organic value and the inorganic value are calculated based on the numerical values, and the ratio is obtained.
Organic solvents having an I / O value of 0.2 or more and 2.3 or less and a boiling point of 40 ° C. or more at normal pressure include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, and ether solvents such as tetrahydrofuran and dioxane. Examples include solvents, ester solvents such as ethyl acetate, nitrile solvents such as acetonitrile, and alcohols having 3 or more carbon chains such as propanol, butanol, and octanol.
I O I/O 沸点
テトラヒドロフラン 30 80 0.375 66.0
メチルエチルケトン 65 60 1.083 79.6
メチルイソブチルケトン 65 120 0.542 94.2
アセトン 65 40 1.625 56.1
アセトニトリル 70 40 1.750 81.1
酢酸エチル 85 80 1.063 77.2
プロパノール 100 60 1.667 97.2
イソブタノール 100 70 1.429 108.0
オクタノール 100 160 0.625 179.8
ジオキサン 40 80 0.500 101.3 The I / O value and boiling point of each solvent are shown below.
I O I / O Boiling point tetrahydrofuran 30 80 0.375 66.0
Methyl ethyl ketone 65 60 1.083 79.6
Methyl isobutyl ketone 65 120 0.542 94.2
Acetone 65 40 1.625 56.1
Acetonitrile 70 40 1.750 81.1
Ethyl acetate 85 80 1.063 77.2
Propanol 100 60 1.667 97.2
Isobutanol 100 70 1.429 108.0
Octanol 100 160 0.625 179.8
Dioxane 40 80 0.500 101.3
また、本発明においては、このコハク酸中に含まれる250~300nmの紫外線領域に吸収を示す不純物を平均吸光度が0.05以下にまで低減させる為には、通常、上記のようにして製造されたコハク酸を、水素処理を行うとともに晶析処理や活性炭処理等の精製処理を更に組み合わせて実施する必要がある。 When hydrogen treatment of a succinic acid-containing liquid derived from biomass resources by fermentation or the like as in the present invention is performed, not only odor components in succinic acid can be easily removed, but fumaric acid is contained as described above. In this case, succinic acid is produced from fumaric acid, and the yield improvement of succinic acid is achieved at the same time. Therefore, the hydrotreating method is a particularly excellent technique that has not been conventionally used as a deodorizing method for succinic acid. Therefore, in the present invention, hydrotreating of a solution containing succinic acid derived from fermentation in the presence of a catalyst is an important step in the purification process.
Further, in the present invention, in order to reduce impurities having absorption in the ultraviolet region of 250 to 300 nm contained in this succinic acid to an average absorbance of 0.05 or less, it is usually produced as described above. The succinic acid must be subjected to hydrogen treatment and further combined with purification treatment such as crystallization treatment and activated carbon treatment.
これら水素化触媒は上記の貴金属を含む化合物をそのまま使用したり、有機ホスフィンなどの配位子を共存させて使用することができるが、触媒分離の容易性の理由から不均一系の貴金属含有触媒が好ましい。 As the hydrogenation catalyst, known homogeneous and heterogeneous noble metal-containing hydrogenation catalysts can be used. Specific examples include, but are not limited to, hydrogenation catalysts containing noble metals such as ruthenium, rhodium, palladium and platinum. Among these, hydrogenation catalysts containing palladium and platinum, particularly palladium, are preferred.
These hydrogenation catalysts can be used with the above compounds containing noble metals as they are or in the presence of a ligand such as an organic phosphine, but heterogeneous noble metal-containing catalysts for reasons of ease of catalyst separation. Is preferred.
使用する水素は、純水素でもよいが、窒素、ヘリウム、アルゴンなどの不活性ガスで希釈させたものも使用できる。水素ガス中の一酸化炭素濃度は、水素処理効率への影響が懸念される為、通常、10000ppm以下、好ましくは、2000ppm以下、より好ましくは1000ppm以下である。 The content of fumaric acid contained in the succinic acid subjected to hydrotreating is usually 0.01% by weight or more, preferably 0.05% by weight or more, and the upper limit is 10% by weight, based on the weight of succinic acid. Hereinafter, it is preferably 5% by weight or less. If the content of fumaric acid is too low, the purification process up to the hydrotreating step becomes complicated. On the other hand, if the content of fumaric acid is too high, fumaric acid has a long time for hydrotreating or has low solubility. This causes a problem that the succinic acid solution having a high concentration cannot be prepared.
Hydrogen used may be pure hydrogen, but hydrogen diluted with an inert gas such as nitrogen, helium or argon can also be used. The carbon monoxide concentration in the hydrogen gas is usually 10000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less because there is concern about the influence on the hydrogen treatment efficiency.
水素処理時の温度の下限は、通常30℃以上、好ましくは50℃以上であり、その上限は、通常150℃以下、好ましくは120℃以下である。反応温度が低すぎると反応速度が遅く、反応完結までに時間がかかり、一方高すぎるとコハク酸の水素化物の副生や、溶媒として水を使用する際には、リンゴ酸などの副生物が多くなる為好ましくない。 The lower limit of the hydrogen pressure during the hydrogen treatment is usually 0.1 MPa or more, and the upper limit is usually 5 MPa or less, preferably 3 MPa or less, more preferably 1 MPa or less. If the hydrogen pressure is too low, the reaction rate is slow and it takes time to complete the reaction. On the other hand, if it is too high, succinic acid hydrides such as butanediol and tetrahydrofuran may be produced as a by-product depending on the catalyst and reaction conditions. It is not preferable.
The lower limit of the temperature during the hydrogen treatment is usually 30 ° C or higher, preferably 50 ° C or higher, and the upper limit is usually 150 ° C or lower, preferably 120 ° C or lower. If the reaction temperature is too low, the reaction rate is slow and it takes time to complete the reaction.If the reaction temperature is too high, by-products such as succinic acid hydride and when using water as a solvent, by-products such as malic acid are not produced. It is not preferable because it increases.
具体的には、三菱化学カルゴン株式会社製のカルゴンCPG、カルゴンCAL、カルゴンSGL、ダイアソーブW、ダイアホープMS10、ダイアホープM010、ダイアホープMS16、ダイアホープ6MD、ダイアホープ6MW、ダイアホープ8ED、ダイアホープZGN4、Centur、日本ノリット株式会社製のGAC、GAC PLUS、GCN PLUS、C GRAN、RO、ROX、DARCO、CN、SX、SX PLUS、sa、SX、PK、W、クラレケミカル株式会社製のGW、GWH、GLC、4GC、KW、PW、PK、株式会社ツルミコール社製のHC-30S、GL-30S、4G-3S、PA、PC、フタムラ化学株式会社製のP、W、CW、SG、SGP、S、GB、CA、K、日本エンバイロケミカルズ株式会社製の白鷺KL、白鷺W2c、白鷺WH2c、白鷺W5c、白鷺WH5c、白鷺WH5X、白鷺XS7100H-3、カルボラフィン、白鷺A、白鷺C、白鷺M、味の素ファインテクノ株式会社社製のホクエツ CL-K、ホクエツHs、ホクエツKSなどが挙げられる。
これらの中では、脂肪族ジカルボン酸中に含まれる250~300nmの紫外線領域に吸収を示す不純物を効率的に除くことができる理由から、ヤシ穀炭、木質炭が好ましい。一方、コハク酸の着色成分を効率よく除去する観点からは、ガス賦活法、水蒸気賦活法、塩化亜鉛やリン酸などの薬品賦活法などの方法により賦活した活性炭が好ましく、その中でも水蒸気賦活法、塩化亜鉛やリン酸などの薬品賦活した活性炭が好ましく、特に塩化亜鉛やリン酸などの薬品賦活した活性炭が好ましい。使用する活性炭の形状は、粉末炭、破砕炭、成形炭、繊維状活性炭のいずれでもよい。カラムに充填して使用する場合には塔圧抑制の理由から粒状、顆粒状の活性炭が好ましい。 As the activated carbon used in the present invention, any known ones such as coal-based, wood-based, coconut-based, and resin-based can be used. Also, use activated carbon activated by various methods such as gas activation method, water vapor activation method, chemical activation method such as zinc chloride and phosphoric acid, etc. Can do.
Specifically, Calgon CPG, Calgon CAL, Calgon SGL, Diasorb W, Diamond Hope MS10, Diamond Hope M010, Diamond Hope MS16, Diamond Hope 6MD, Diamond Hope 6MW, Diamond Hope 8ED, Diamond Hope ZGN4, Centur, Japan Norit Stock, manufactured by Mitsubishi Chemical Calgon Co., Ltd. Company-made GAC, GAC PLUS, GCN PLUS, C GRAN, RO, ROX, DARCO, CN, SX, SX PLUS, sa, SX, PK, W, Kuraray Chemical Co., Ltd. GW, GWH, GLC, 4GC, KW , PW, PK, HC-30S, GL-30S, 4G-3S, PA, PC, manufactured by Tsurumi Co., Ltd., P, W, CW, SG, SGP, S, GB, CA, K, manufactured by Futamura Chemical Co., Ltd. Hakuho KL, Hakuho W2c, Hakuho WH2c, Hakuho W5c, Hakuho WH5X, Hakuho XS7100H-3, Calaburafin, Hakuho A, Hakuho C, Hakuho M, Ajinomoto Fine Techno Co., Ltd. Hokuetsu CL-K, Hokuetsu Hs, Hokuetsu KS, etc. Is mentioned.
Among these, coconut charcoal and woody charcoal are preferable because impurities that absorb in the ultraviolet region of 250 to 300 nm contained in the aliphatic dicarboxylic acid can be efficiently removed. On the other hand, from the viewpoint of efficiently removing the coloring component of succinic acid, activated carbon activated by a method such as a gas activation method, a water vapor activation method, a chemical activation method such as zinc chloride or phosphoric acid is preferred, and among them, the water vapor activation method, Chemical activated carbon such as zinc chloride or phosphoric acid is preferred, and activated carbon activated by chemicals such as zinc chloride or phosphoric acid is particularly preferred. The shape of the activated carbon used may be any of powdered coal, crushed coal, formed coal, and fibrous activated carbon. When packed in a column and used, granular and granular activated carbon is preferable for the reason of suppressing tower pressure.
イオン交換樹脂は、その官能基の酸または塩基としての強度により強酸性カチオン交換樹脂、弱酸性カチオン交換樹脂、強塩基性アニオン交換樹脂、弱塩基性アニオン交換樹脂に分類され、さらにその形状により、ゲル型、ポーラス型に分類されるが、ここでは用いるイオン交換樹脂は特に限定されるものではない。ただイオン交換の効率を考慮すると、より酸または塩基としての強度が強い強酸性カチオン交換樹脂、強塩基性アニオン交換樹脂を用いることが好ましい。またその形状もポーラス型である特別な理由もなく、より汎用的で安価なゲル型を用いることが望ましい。具体的には、カチオン交換樹脂としてダイヤイオンSK1B(H型)など、アニオン交換樹脂としてダイヤイオンSA10Aなどが例示される。 Furthermore, in the present invention, for the purpose of removing impurities in succinic acid, a purification operation such as ion exchange column treatment may be used in combination. Here, the ion exchange column treatment is to remove ions by passing a liquid to be treated through a column filled with an ion exchange resin. The ion exchange resin should be selected according to the ions contained in the liquid to be treated and the required purity of succinic acid. For example, anion exchange resins are used to remove anions such as sulfate ions and chloride ions. In order to remove cations such as metal ions and ammonium ions from (OH type), a cation exchange resin (H type) can be used, but both of them may be used if necessary.
Ion exchange resins are classified into strongly acidic cation exchange resins, weakly acidic cation exchange resins, strongly basic anion exchange resins, and weakly basic anion exchange resins depending on the strength of the functional group as an acid or base. Although it is classified into a gel type and a porous type, the ion exchange resin used here is not particularly limited. However, in consideration of the efficiency of ion exchange, it is preferable to use a strongly acidic cation exchange resin or a strongly basic anion exchange resin having a stronger strength as an acid or a base. Further, it is desirable to use a more versatile and inexpensive gel type without any special reason that the shape is also porous. Specifically, Diaion SK1B (H type) is exemplified as a cation exchange resin, and Diaion SA10A is exemplified as an anion exchange resin.
またその通液処理方法は、特に限定するものではないが、通常空間速度(SV)0.1~10hr-1、空塔速度1~20m/hrで処理する。処理速度が大きすぎるとカラム前後における圧力損失が大きくなったり、またイオン交換が不十分となる。逆に不必要に処理速度が遅くすると不必要にカラムが大きくなる。
通常カラム処理は、カラム出口においてイオン濃度を常時または定期的に測定し、カラム出口にイオンのリークが認められれば、イオン交換樹脂を再生処理する。イオン交換樹脂の再生は通常の方法に従い、カチオン交換樹脂では硫酸、塩酸などの酸を、アニオン交換樹脂では苛性ソーダなどのアルカリにより行うことができる。 The ion exchange column treatment can be performed within a temperature range that is equal to or higher than the temperature at which succinic acid is dissolved in the liquid to be treated and lower than the heat resistant temperature of the ion exchange resin. In other words, the cation exchange resin is usually treated at 20 to 100 ° C. depending on the succinic acid concentration in the solution to be treated. On the other hand, anion exchange resins are usually treated at 10 to 80 ° C. because they have lower heat resistance than cation exchange resins. In the case of using anion exchange column treatment from the viewpoint of treatment temperature, a step where the succinic acid concentration is low and the column treatment is possible at a low temperature is desirable.
The liquid flow treatment method is not particularly limited, but the treatment is usually performed at a space velocity (SV) of 0.1 to 10 hr −1 and a superficial velocity of 1 to 20 m / hr. If the processing speed is too high, pressure loss before and after the column becomes large, and ion exchange becomes insufficient. Conversely, if the processing speed is unnecessarily slow, the column becomes unnecessarily large.
Usually, in the column treatment, the ion concentration is measured regularly or periodically at the column outlet, and if ion leakage is observed at the column outlet, the ion exchange resin is regenerated. The regeneration of the ion exchange resin can be carried out in accordance with a normal method, using an acid such as sulfuric acid or hydrochloric acid for a cation exchange resin, or an alkali such as caustic soda for an anion exchange resin.
A=log10(I0/I)(ここで、I0=入射光強度、I=透過光強度を表す。) Here, the absorbance (A) is the absorbance when measured at an optical path length of 1 cm, and is a value calculated according to the following definition.
A = log 10 (I 0 / I) (where I 0 = incident light intensity and I = transmitted light intensity)
平均吸光度=(250~300nm間の1nm毎の吸光度の総和)/51 The average absorbance in the ultraviolet region of 250 to 300 nm is a value obtained by dividing the total absorbance measured every 1 nm between 250 and 300 nm by 51.
Average absorbance = (sum of absorbances every 1 nm between 250 and 300 nm) / 51
また、発酵由来のコハク酸溶液には、溶媒として水を使用する際には水に不溶な成分が混入している場合がある。このような不溶成分の混入は、活性炭による上記の不純物除去やその後の精製工程の効率を低下させる要因となる為に、予め不溶成分を除去することが好ましい。不溶成分の除去は、発酵法により生成するコハク酸塩からコハク酸に誘導した後から活性炭処理工程に至る迄の間の工程で発酵由来のコハク酸溶液を公知の膜透過処理を使用して実施する方法が好ましい。また、別法として、粉末状の活性炭を共存させて不溶成分を吸着させて膜透過処理の透過性を向上させたり、適切な粉末活性炭を用いて不溶成分とともに上記の不純物を同時に吸着除去する方法も好適に使用される。
更に、本発明においては、晶析又は/及び活性炭処理と水素処理とを組み合わせて不純物除去を実施する際には、特に限定はされないが、効率的に不純物が除去される為、水素処理工程の前に晶析又は/及び活性炭処理工程を実施するプロセスが好適に使用される。 In the present invention, since the impurity species to be removed differ depending on the type of activated carbon as described above, these impurity removal methods include a method of combining a plurality of activated carbon species, activated carbon treatment, and the above-described hydrogen treatment and crystallization treatment. The method of combining these is mentioned.
Moreover, when using water as a solvent, the insoluble component may be mixed in the succinic acid solution derived from fermentation. Such an insoluble component is a factor that reduces the efficiency of the above-described impurity removal by activated carbon and the subsequent purification process, so it is preferable to remove the insoluble component in advance. Insoluble components are removed from the succinate produced by the fermentation method to succinic acid, and the process from the succinic acid solution to the activated carbon treatment process is performed using a known membrane permeabilization process. Is preferred. As another method, the powdered activated carbon is allowed to coexist to adsorb insoluble components to improve the permeability of the membrane permeation treatment, or the above-mentioned impurities are simultaneously adsorbed and removed together with the insoluble components using appropriate powdered activated carbon. Are also preferably used.
Furthermore, in the present invention, when removing impurities by combining crystallization or / and activated carbon treatment and hydrogen treatment, although not particularly limited, since impurities are efficiently removed, A process in which the crystallization or / and activated carbon treatment step is performed before is preferably used.
本発明のポリエステルは、コハク酸単位およびジオール単位を必須成分とする。本発明においてコハク酸単位を構成するコハク酸は上記のバイオマス資源から誘導された高純度のコハク酸を含有するジカルボン酸である。従って、本発明においては、化石資源から誘導された脂肪族及び/又は芳香族ジカルボン酸と上記のバイオマス資源から誘導されたコハク酸との混合物も好適に使用される。 <Manufacture of polyester>
The polyester of the present invention contains succinic acid units and diol units as essential components. In the present invention, the succinic acid constituting the succinic acid unit is a dicarboxylic acid containing high-purity succinic acid derived from the biomass resource. Therefore, in the present invention, a mixture of an aliphatic and / or aromatic dicarboxylic acid derived from a fossil resource and succinic acid derived from the biomass resource is also preferably used.
本発明においてジオール単位とは、脂肪族ジオールから誘導されるものであり、公知の化合物を用いることができる。 <Diol unit>
In the present invention, the diol unit is derived from an aliphatic diol, and a known compound can be used.
本発明においては、ポリエステルの製造において上記のジオール成分とジカルボン酸成分に加えて、共重合成分を加えてもよい。
共重合成分の具体的な例としては、2官能のオキシカルボン酸、不飽和ジカルボン酸、架橋構造を形成するために3官能以上の多価アルコール及び3官能以上の多価カルボン酸またはその無水物および3官能以上のオキシカルボン酸からなる群から選ばれる少なくとも1種の多官能化合物が挙げられる。これらの共重合成分を添加するとポリエステル製造時の重合速度を著しく向上する効果が発現する。これらの共重合成分の中では、高重合度のポリエステルが容易に製造できる傾向があるためオキシカルボン酸が好適に使用される。 <Other copolymer components>
In the present invention, a copolymer component may be added to the polyester in addition to the diol component and the dicarboxylic acid component.
Specific examples of the copolymer component include a bifunctional oxycarboxylic acid, an unsaturated dicarboxylic acid, a trifunctional or higher polyhydric alcohol and a trifunctional or higher polyhydric carboxylic acid or an anhydride thereof for forming a crosslinked structure. And at least one polyfunctional compound selected from the group consisting of trifunctional or higher functional oxycarboxylic acids. When these copolymer components are added, the effect of significantly improving the polymerization rate during the production of the polyester is exhibited. Among these copolymer components, oxycarboxylic acids are preferably used because polyesters having a high degree of polymerization tend to be easily produced.
本発明におけるポリエステルの製造方法としては、従来の公知の方法が使用でき、例えば、上記のコハク酸を含む脂肪族ジカルボン酸成分とジオール成分とのエステル化反応及び/又はエステル交換反応を行った後、減圧下での重縮合反応を行うといった溶融重合の一般的な方法や、有機溶媒を用いた公知の溶液加熱脱水縮合方法によっても製造することができるが、経済性ならびに製造工程の簡略性の観点から、無溶媒下で行う溶融重合でポリエステルを製造する方法が好ましい。 <Production method of polyester>
As a method for producing the polyester in the present invention, a conventionally known method can be used. For example, after performing an esterification reaction and / or a transesterification reaction between the aliphatic dicarboxylic acid component containing succinic acid and a diol component. It can also be produced by a general method of melt polymerization such as a polycondensation reaction under reduced pressure, or a known solution heating dehydration condensation method using an organic solvent. From the viewpoint, a method of producing a polyester by melt polymerization performed in the absence of a solvent is preferable.
コハク酸を含む脂肪族ジカルボン酸成分とジオール成分とのエステル化反応及び/又はエステル交換反応の反応温度は、下限が通常150℃以上、好ましくは180℃以上、上限が通常260℃以下、好ましくは250℃以下である。反応雰囲気は、通常、窒素、アルゴン等の不活性ガス雰囲気下である。反応圧力は、通常、常圧~10kPaであるが、常圧が好ましい。
反応時間は、通常1時間以上であり、上限が通常10時間以下、好ましくは、4時間以下である。 Conventionally known ranges can be adopted for conditions such as temperature, time, and pressure.
The reaction temperature of the esterification reaction and / or transesterification reaction of the aliphatic dicarboxylic acid component containing succinic acid and / or the diol component is usually 150 ° C. or higher, preferably 180 ° C. or higher, and preferably 260 ° C. or lower, preferably upper limit. It is 250 degrees C or less. The reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon. The reaction pressure is usually from normal pressure to 10 kPa, but normal pressure is preferred.
The reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.
本発明の方法で製造されたポリエステルは、通常、ポリマーの熱安定性に著しく悪影響を与えるカルボン酸末端量が少ない特徴があるため、熱安定性に優れ、成形時の品質の低下が少ない、即ち、溶融成形時に末端基の切断や、主鎖の切断等の副反応が少ないという特徴を有する。従って、本発明において製造される好ましいポリエステルの末端COOH基数は、ポリエステルの重合度にもよるが、通常、100当量/トン(eq/トン)以下、好ましくは60eq/トン以下、より好ましくは40eq/トン以下、特に好ましくは30eq/トン以下である。一方、カルボキシル基末端量が極端に少なくなると、重合速度が極めて遅くなり、高重合度のポリマーが製造できない。そのような理由から、ポリエステルの末端COOH基数の下限は、通常、0.1eq/トン以上、より好ましくは1eq/トンである。
本発明で製造されるポリエステルは、通常、着色の少ないポリエステルであることが好ましい。本発明のポリエステルの黄色度(YI値)は、その上限が、通常、50以下、好ましくは30以下、より好ましくは20以下、更に好ましくは15以下、特に好ましくは10以下であり、一方、その下限は、特には限定されないが、通常-20以上、好ましくは、-10以上、より好ましくは、―5以上、特に好ましくは-3以上、最も好ましくはー1以上である。高いYI値を示すポリエステルは、フィルムやシート等の使用用途が制限される欠点を有する。一方、低いYI値を示すポリエステルは、より好ましい形態ではあるが、このようなポリマーを製造するには製造プロセスが煩雑で極めて高額の設備投資を要するなど経済的に不利な点がある。本発明において、YI値は、JIS K7105に基づく方法で測定される値である。 <Polyester and its use>
The polyester produced by the method of the present invention is usually characterized by a small amount of terminal carboxylic acid that significantly adversely affects the thermal stability of the polymer. Therefore, the polyester is excellent in thermal stability and has little deterioration in quality during molding. In the melt molding, there are few side reactions such as cleavage of terminal groups and cleavage of the main chain. Therefore, the number of terminal COOH groups of the preferred polyester produced in the present invention is usually 100 equivalents / ton (eq / ton) or less, preferably 60 eq / ton or less, more preferably 40 eq / ton, although it depends on the degree of polymerization of the polyester. Or less, particularly preferably 30 eq / ton or less. On the other hand, when the carboxyl group terminal amount becomes extremely small, the polymerization rate becomes extremely slow, and a polymer having a high degree of polymerization cannot be produced. For such reasons, the lower limit of the number of terminal COOH groups of the polyester is usually 0.1 eq / ton or more, more preferably 1 eq / ton.
The polyester produced in the present invention is usually preferably a polyester with little coloring. The upper limit of the yellowness (YI value) of the polyester of the present invention is usually 50 or less, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less. The lower limit is not particularly limited, but is usually −20 or more, preferably −10 or more, more preferably −5 or more, particularly preferably −3 or more, and most preferably −1 or more. Polyesters exhibiting high YI values have the disadvantage that their use applications such as films and sheets are limited. On the other hand, polyester showing a low YI value is a more preferable form, but there are economical disadvantages such as manufacturing a polymer such that the manufacturing process is complicated and an extremely high capital investment is required. In the present invention, the YI value is a value measured by a method based on JIS K7105.
〔還元粘度(ηsp/C)測定条件〕
粘度管:ウベローデ粘度管
測定温度:30℃
溶媒:フェノール/テトラクロロエタン(1:1重量比)溶液
ポリエステル濃度:0.5g/dl The reduced viscosity as used in the present invention is measured under the following measurement conditions.
[Reduced viscosity (ηsp / C) measurement conditions]
Viscosity tube: Ubbelohde viscosity tube Measurement temperature: 30 ° C
Solvent: Phenol / tetrachloroethane (1: 1 weight ratio) solution Polyester concentration: 0.5 g / dl
具体的な用途としては、射出成型品(例えば、生鮮食品のトレーやファーストフードの容器、野外レジャー製品など)、押出成型品(フィルム、シート等、例えば釣り糸、漁網、植生ネット、保水シートなど)、中空成型品(ボトル等)等が挙げられ、更にその他農業用のフィルム、コーティング資材、肥料用コーティング材、ラミネートフィルム、板、延伸シート、モノフィラメント、マルチフィラメント、不織布、フラットヤーン、ステープル、捲縮繊維、筋付きテープ、スプリットヤーン、複合繊維、ブローボトル、発泡体、ショッピングバッグ、ゴミ袋、コンポスト袋、化粧品容器、洗剤容器、漂白剤容器、ロープ、結束材、手術糸、衛生用カバーストック材、保冷箱、クッション材フィルム及び合成紙などに利用可能である。 The molded product of the present invention can be obtained by molding the polyester of the present invention. A normal method can be adopted as the forming method. The obtained molded product is shown below together with its use.
Specific applications include injection molded products (for example, fresh food trays, fast food containers, outdoor leisure products, etc.), extruded products (films, sheets, etc., for example fishing lines, fishing nets, vegetation nets, water retaining sheets, etc.) , Hollow molded products (bottles, etc.), and other agricultural films, coating materials, fertilizer coating materials, laminate films, plates, stretched sheets, monofilaments, multifilaments, non-woven fabrics, flat yarns, staples, crimps Fiber, striped tape, split yarn, composite fiber, blow bottle, foam, shopping bag, garbage bag, compost bag, cosmetic container, detergent container, bleach container, rope, binding material, surgical thread, sanitary cover stock material It can be used for a cold box, a cushion material film, a synthetic paper, and the like.
カラム;信和加工(株)製 ULTRON PS-80H 8.0mmI.D.× 30cm
溶離液:水(過塩素酸)(過塩素酸60%水溶液1.8ml/1L-H2O)
温度:60℃ <Analysis of acids and sugars>
Column: ULTRON PS-80H 8.0 mmI. D. × 30cm
Eluent: water (perchloric acid) (perchloric acid 60% aqueous solution 1.8 ml / 1 L-H 2 O)
Temperature: 60 ° C
装置:日立アミノ酸分析計 L-8900
分析条件:生体アミノ酸分離条件-ニンヒドリン発色法(570nm,440nm)
標準品:PF(和光アミノ酸混合液ANII型0.8ml+B型0.8ml→10ml)
注入量:10μl
定量計算:Proは、440nm、他のアミノ酸は570nmのピークの面積から、一点外部標準法にてアミノ酸含有を算出 <Amino acid analysis>
Equipment: Hitachi Amino Acid Analyzer L-8900
Analysis conditions: biogenic amino acid separation conditions-ninhydrin coloring method (570 nm, 440 nm)
Standard product: PF (Wako amino acid mixture ANII type 0.8 ml + B type 0.8 ml → 10 ml)
Injection volume: 10 μl
Quantitative calculation: Pro is calculated from the peak area of 440 nm for other amino acids and 570 nm for other amino acids by the single point external standard method.
カラム;GL-IC-C75(4.6mmI.D × 150mm)
溶離液;3.5mmol/L硫酸
カラム温度:40℃
一方、その他の特性値は、次の方法により測定した。 <Cation>
Column: GL-IC-C75 (4.6 mm ID × 150 mm)
Eluent: 3.5mmol / L sulfuric acid
Column temperature: 40 ° C
On the other hand, other characteristic values were measured by the following methods.
試料数10mgを石英ボートへ採取して、全窒素分析計(三菱化学社製TN-10型)を用いて試料を燃焼し、化学発光法により決定した。 <Nitrogen atom content>
A 10 mg sample was taken into a quartz boat, and the sample was burned using a total nitrogen analyzer (TN-10 model manufactured by Mitsubishi Chemical Corporation), and determined by a chemiluminescence method.
試料約0.1gを白金製ボートに採取して石英管管状炉(三菱化学社製AQF-100(濃縮システム))で燃焼し、燃焼ガス中の硫黄分を0.1%-過酸化水素水で吸収させた。その後、吸収液中の硫酸イオンをイオンクロマトグラフ(Dionex社製 ICS-1000型)を用いて測定した。 <Sulfur atom content>
About 0.1 g of a sample is collected in a platinum boat and burned in a quartz tube tubular furnace (AQF-100 (concentration system) manufactured by Mitsubishi Chemical Corporation). The sulfur content in the combustion gas is 0.1% hydrogen peroxide solution Absorbed. Thereafter, sulfate ions in the absorbing solution were measured using an ion chromatograph (ICS-1000 type, manufactured by Dionex).
JIS K7105の方法に基づいて測定した。
<ポリエステル還元粘度>
ポリエステルを濃度0.5g/dLとなるようにフェノール/テトラクロロエタン(1/1(質量比)混合液)に溶解し、溶液が30℃の恒温槽中で粘度管を落下する時間t(sec)を測定した。また溶媒のみの落下する時間t0(sec)を測定し30℃での還元粘度ηsp/C(=(t-t0)/t0・C)を算出した(Cは溶液の濃度)。 <YI value>
It measured based on the method of JISK7105.
<Polyester reduced viscosity>
The time t (sec) during which the polyester is dissolved in phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) to a concentration of 0.5 g / dL, and the solution drops in the viscosity tube in a 30 ° C. thermostat. Was measured. Further, the time t 0 (sec) during which only the solvent falls was measured, and the reduced viscosity η sp / C (= (t−t 0 ) / t 0 · C) at 30 ° C. was calculated (C is the concentration of the solution).
得られたポリエステルをベンジルアルコールに溶解し0.1N NaOHにて滴定した値であり、1×106g当たりのカルボキシル基当量である。 <Polyester terminal carboxyl group amount>
This is a value obtained by dissolving the obtained polyester in benzyl alcohol and titrating with 0.1 N NaOH, and is equivalent to a carboxyl group per 1 × 10 6 g.
<ピルビン酸カルボキシラーゼ(PC)増強株の作製>
(A)ブレビバクテリウム・フラバムMJ233株ゲノムDNAの抽出
ブレビバクテリウム・フラバムMJ233は、1975年4月28日に通商産業省工業技術院微生物工業技術研究所(現独立行政法人 産業技術総合研究所 特許生物寄託センター)(〒305-8566 日本国茨城県つくば市東1丁目1番地1 中央第6)に受託番号FERM P-3068として寄託され、1981年5月1日にブダペスト条約に基づく国際寄託に移管され、FERM BP-1497の受託番号で寄託されている。
A培地[尿素 2g、(NH4)2SO4 7g、KH2PO4 0.5g、K2HPO4 0.5g、MgSO4・7H2O 0.5g、FeSO4・7H2O 6mg、MnSO4・4-5H2O6mg、ビオチン 200μg、チアミン 100μg、イーストエキストラクト 1g、カザミノ酸 1g、グルコース 20g、蒸留水1Lに溶解]10mLに、ブレビバクテリウム・フラバムMJ233株を対数増殖期後期まで培養し、遠心分離(10000g、5分)により菌体を集めた。得られた菌体を10mg/mLの濃度にリゾチームを含む10mM NaCl/20mMトリス緩衝液(pH8.0)/1mM EDTA・2Na溶液0.15mLに懸濁した。次に、上記懸濁液にプロテナーゼKを、最終濃度が100μg/mLになるように添加し、37℃で1時間保温した。さらにドデシル硫酸ナトリウムを最終濃度が0.5%になるように添加し、50℃で6時間保温して溶菌した。この溶菌液に、等量のフェノール/クロロフォルム溶液を添加し、室温で10分間ゆるやかに振盪した後、全量を遠心分離(5,000×g、20分間、10~12℃)し、上清画分を分取し、酢酸ナトリウムを0.3Mとなるように添加した後、2倍量のエタノールを加え混合した。遠心分離(15,000×g、2分)により回収した沈殿物を70%エタノールで洗浄した後、風乾した。得られたDNAに10mMトリス緩衝液(pH7.5)-1mM EDTA・2Na溶液5mLを加え、4℃で一晩静置し、以後のPCRの鋳型DNAに使用した。 Reference Example <Preparation of pyruvate carboxylase (PC) enhanced strain>
(A) Extraction of genomic DNA of Brevibacterium flavum MJ233 strain Brevibacterium flavum MJ233 was established on April 28, 1975 at the Institute of Microbial Industrial Technology, Ministry of International Trade and Industry (currently National Institute of Advanced Industrial Science and Technology). Patent Biological Deposit Center) (deposited as FERM P-3068 at Tsukuba 1-1, Higashi 1-chome, Ibaraki, Japan, 305-8586 Japan) and deposited on May 1, 1981 as an international deposit under the Budapest Treaty It has been transferred and deposited with the accession number of FERM BP-1497.
A medium [urea 2 g, (NH 4 ) 2 SO 4 7 g, KH 2 PO 4 0.5 g, K 2 HPO 4 0.5 g, MgSO 4 .7H 2 O 0.5 g, FeSO 4 · 7H 2 O 6 mg, MnSO 4. 4-5H 2 O 6 mg,
ブレビバクテリウム・フラバムMJ233株由来ピルベートカルボキシラーゼ遺伝子のN末端領域のDNA断片の取得は、上記(A)で調製したDNAを鋳型とし、全ゲノム配列が報告されているコリネバクテリウム・グルタミカム ATCC13032株の該遺伝子の配列(GenBank Database Accession No.BA000036のCgl0689)を基に設計した合成DNA(配列番号1および配列番号2)を用いたPCRによって行った。尚、配列番号1のDNAは5’末端がリン酸化されたものを用いた。反応液組成:鋳型DNA1μL、PfxDNAポリメラーゼ(インビトロジェン社製) 0.2μL、1倍濃度添付バッファー、0.3μM各々プライマー、1mM MgSO4、0.25μMdNTPsを混合し、全量を20μLとした。反応温度条件:DNAサーマルサイクラー PTC-200(MJResearch社製)を用い、94℃で20秒、60℃で20秒、72℃で1分らなるサイクルを35回繰り返した。但し、1サイクル目の94℃での保温は1分20秒、最終サイクルの72℃での保温は4分とした。増幅産物の確認は、0.75%アガロース(SeaKem GTG agarose:FMCBioProducts製)ゲル電気泳動により分離後、臭化エチジウム染色により可視化することにより行い、約0.9kbの断片を検出した。ゲルからの目的DNA断片の回収は、QIAQuick Gel Extraction Kit(QIAGEN製)を用いて行い、これをPC遺伝子N末端断片とした。 (B) Construction of plasmid for replacing PC gene promoter The DNA fragment of the N-terminal region of the pyruvate carboxylase gene derived from Brevibacterium flavum MJ233 strain was obtained using the DNA prepared in (A) above as a template, This was performed by PCR using synthetic DNA (SEQ ID NO: 1 and SEQ ID NO: 2) designed based on the reported sequence of the gene of Corynebacterium glutamicum ATCC13032 strain (Cg0689 of GenBank Database Accession No. BA00000036). The DNA of SEQ ID NO: 1 used was phosphorylated at the 5 ′ end. Composition of reaction solution:
ブレビバクテリウム・フラバムMJ233/ΔLDH(ラクテートデヒドロゲナーゼ遺伝子破壊株:特開2005-95169)の形質転換に用いるプラスミドDNAは、pMJPC17.2のプラスミドDNAを用いて塩化カルシウム法(Journal of Molecular Biology,53,159,1970)により形質転換した大腸菌JM110株から再調製した。ブレビバクテリウム・フラバムMJ233/ΔLDH株の形質転換は電気パルス法(Res.Microbiol.、Vol.144, p.181-185, 1993)によって行い、得られた形質転換体をカナマイシン 25μg/mLを含むLBG寒天培地[トリプトン10g、イーストエキストラクト5g、NaCl 5g、グルコース 20g、及び寒天15gを蒸留水1Lに溶解]に塗抹した。この培地上に生育した株は、pMJPC17.2がブレビバクテリウム・フラバムMJ233株菌体内で複製不可能なプラスミドであるため、該プラスミドのPC遺伝子とブレビバクテリウム・フラバムMJ233株ゲノム上の同遺伝子との間で相同組み換えを起こした結果、ゲノム上に該プラスミドに由来するカナマイシン耐性遺伝子およびsacB遺伝子が挿入されているはずである。次に、上記相同組み換え株をカナマイシン25μg/mLを含むLBG培地にて液体培養した。この培養液の菌体数約100万相当分を10%ショ糖含有LBG培地に塗抹にした。結果、2回目の相同組み換えによりsacB遺伝子が脱落しショ糖非感受性となったと考えられる株を数十個得た。この様にして得られた株の中には、そのPC遺伝子の上流にpMJPC17.2に由来するTZ4プロモーターが挿入されたものと野生型に戻ったものが含まれる。PC遺伝子がプロモーター置換型であるか野生型であるかの確認は、LBG培地にて液体培養して得られた菌体を直接PCR反応に供し、PC遺伝子の検出を行うことによって容易に確認できる。TZ4プロモーターおよびPC遺伝子をPCR増幅するためのプライマー(配列番号8および配列番号9)を用いて分析すると、プロモーター置換型では678bpのDNA断片を認めるはずである。上記方法にてショ糖非感受性となった菌株を分析した結果、TZ4プロモーターが挿入された株を選抜し、該株をブレビバクテリウム・フラバムMJ233/PC-4/ΔLDHと命名した。 (C) Preparation of PC-enhanced strain Plasmid DNA used for transformation of Brevibacterium flavum MJ233 / ΔLDH (lactate dehydrogenase gene-disrupted strain: Japanese Patent Laid-Open No. 2005-95169) was obtained by the calcium chloride method using plasmid DNA of pMJPC17.2. (Journal of Molecular Biology, 53, 159, 1970) was re-prepared from E. coli JM110 strain transformed. The Brevibacterium flavum MJ233 / ΔLDH strain was transformed by the electric pulse method (Res. Microbiol., Vol. 144, p.181-185, 1993), and the resulting transformant contained 25 μg / mL of kanamycin. LBG agar medium [tryptone 10 g, yeast extract 5 g, NaCl 5 g, glucose 20 g, and agar 15 g dissolved in 1 L of distilled water] was smeared. The strain grown on this medium is a plasmid in which pMJPC17.2 is a plasmid that cannot be replicated in Brevibacterium flavum MJ233 strain, so the PC gene of the plasmid and the same gene on the genome of Brevibacterium flavum MJ233 strain As a result of homologous recombination with the kanamycin, the kanamycin resistance gene and sacB gene derived from the plasmid should be inserted on the genome. Next, the homologous recombination strain was subjected to liquid culture in an LBG medium containing 25 μg / mL kanamycin. A portion equivalent to about 1 million cells of this culture was smeared on a 10% sucrose-containing LBG medium. As a result, sacB gene was removed by the second homologous recombination and sucrose-insensitive sucrose strains were obtained. Among the strains thus obtained, those in which the TZ4 promoter derived from pMJPC17.2 is inserted upstream of the PC gene and those that have returned to the wild type are included. Confirmation of whether the PC gene is promoter-substituted type or wild type can be easily confirmed by subjecting the cells obtained by liquid culture in LBG medium to direct PCR reaction and detecting the PC gene. . When analyzed using primers (SEQ ID NO: 8 and SEQ ID NO: 9) for PCR amplification of the TZ4 promoter and PC gene, a 678 bp DNA fragment should be observed in the promoter-substituted form. As a result of analyzing the strain that became insensitive to sucrose by the above method, a strain into which the TZ4 promoter was inserted was selected, and the strain was named Brevibacterium flavum MJ233 / PC-4 / ΔLDH.
上記(C)で得られた形質転換株ブレビバクテリウム・フラバムMJ233/PC-4/ΔLDH株をグルコース2%、カナマイシン25mg/Lを含むA培地100mLで終夜培養を行った。得られた菌体を集菌後、50mM リン酸カリウム緩衝液(pH7.5)50mLで洗浄し、同組成の緩衝液20mLに再度懸濁させた。懸濁液をSONIFIER 350(BRANSON製)で破砕し、遠心分離した上清を無細胞抽出液とした。得られた無細胞抽出液を用いピルベートカルボキシラーゼ活性を測定した。酵素活性の測定は100mM Tris/HCl緩衝液(pH7.5)、 0.1mg/10mlビオチン、5mM 塩化マグネシウム、50mM 炭酸水素ナトリウム、5mM ピルビン酸ナトリウム 、5mM アデノシン3リン酸ナトリウム、0.32 mM NADH、20units/1.5mlリンゴ酸デヒドロゲナーゼ(WAKO製、酵母由来)及び酵素を含む反応液中で25℃で反応させることにより行った。1Uは1分間に1μmolのNADHの減少を触媒する酵素量とした。ピルベートカルボキシラーゼの発現を強化した無細胞抽出液における比活性は 0.1U/mg蛋白質であった。尚、親株であるMJ233/△LDH株を同様に培養した菌体では、本活性測定方法検出限界以下であった。
以下、ブレビバクテリウム・フラバムMJ233/PC-4/ΔLDH株を有機酸生産菌として菌体調製用培養、および有機酸生産反応に用いた。 (D) Measurement of pyruvate carboxylase enzyme activity The transformed strain Brevibacterium flavum MJ233 / PC-4 / ΔLDH strain obtained in (C) above was overnight in 100 mL of A medium containing 2% glucose and 25 mg / L kanamycin. Culture was performed. The obtained cells were collected, washed with 50 mL of 50 mM potassium phosphate buffer (pH 7.5), and resuspended in 20 mL of the same composition. The suspension was crushed with SONIFIER 350 (manufactured by BRANSON), and the centrifuged supernatant was used as a cell-free extract. The pyruvate carboxylase activity was measured using the obtained cell-free extract. The enzyme activity was measured using 100 mM Tris / HCl buffer (pH 7.5), 0.1 mg / 10 ml biotin, 5 mM magnesium chloride, 50 mM sodium bicarbonate, 5 mM sodium pyruvate, 5 mM adenosine triphosphate, 0.32 mM NADH. The reaction was carried out at 25 ° C. in a reaction solution containing 20 units / 1.5 ml malate dehydrogenase (manufactured by WAKO, derived from yeast) and the enzyme. 1 U was defined as the amount of enzyme that catalyzes the decrease of 1 μmol NADH per minute. The specific activity in the cell-free extract with enhanced pyruvate carboxylase expression was 0.1 U / mg protein. In addition, in the cells cultured in the same manner as the parent strain MJ233 / ΔLDH strain, it was below the detection limit of this activity measurement method.
Hereinafter, the Brevibacterium flavum MJ233 / PC-4 / ΔLDH strain was used as an organic acid-producing bacterium for microbial cell preparation and organic acid production reaction.
<種培養>
尿素:4g、硫酸アンモニウム:14g、リン酸1カリウム:0.5g、リン酸2カリウム0.5g、硫酸マグネシウム・7水和物:0.5g、硫酸第一鉄・7水和物:20mg、硫酸マンガン・水和物:20mg、D-ビオチン:200μg、塩酸チアミン:200μg、酵母エキス:5g、カザミノ酸:5g、及び蒸留水:1000mLの培地100mLを500mLの三角フラスコにいれ、120℃、20分加熱滅菌した。これを室温まで冷やし、あらかじめ滅菌した50%グルコース水溶液を4mLを添加し、上記で構築したブレビバクテリウム・フラバムMJ233/PC-4/ΔLDHを接種して24時間30℃にて種培養した。 [Preparation of succinate-containing culture medium]
<Seed culture>
Urea: 4 g, ammonium sulfate: 14 g, monopotassium phosphate: 0.5 g, dipotassium phosphate 0.5 g, magnesium sulfate heptahydrate: 0.5 g, ferrous sulfate heptahydrate: 20 mg, sulfuric acid Manganese hydrate: 20 mg, D-biotin: 200 μg, thiamine hydrochloride: 200 μg, yeast extract: 5 g, casamino acid: 5 g, and distilled water: 100 mL of a medium of 1000 mL are placed in a 500 mL Erlenmeyer flask at 120 ° C. for 20 minutes. Heat sterilized. This was cooled to room temperature, 4 mL of 50% glucose aqueous solution sterilized in advance was added, and Brevibacterium flavum MJ233 / PC-4 / ΔLDH constructed above was inoculated and seed-cultured at 30 ° C. for 24 hours.
硫酸アンモニウム:1.0g、リン酸1カリウム:1.5g、リン酸2カリウム1.5g、塩化カリウム:1.67g、硫酸マグネシウム・7水和物:0.5g、硫酸第一鉄・7水和物:40mg、硫酸マンガン・水和物:40mg、D-ビオチン:1.0mg、塩酸チアミン:1.0mg、酵母エキス10g、消泡剤(CE457:日本油脂製):1.0g及び蒸留水:1000mLの培地400mLを1Lの発酵糟に入れ、120℃、20分加熱滅菌した。これを室温まで冷やした後、あらかじめ滅菌した72%グルコース水溶液:20mLを添加し、これに前述の種培養液を20mL加えて、30℃に保温した。pHは9.3%アンモニア水を用いて7.0以下にならないように保ち、通気は毎分300mL、攪拌は毎分600回転で24時間本培養を行った。溶存酸素濃度は培養開始直後から徐々に低下し、培養開始後4時間でほぼ0となった。その後、培養開始後15時間で溶存酸素濃度が上昇したため、あらかじめ滅菌した72%グルコース水溶液を380μL添加したところ、再び急速に低下し、ほぼ0となった。約13分後同様に溶存酸素濃度の上昇が観察されため、あらかじめ滅菌した72%グルコース水溶液を380μL添加し再び低下させた。以後、約13分毎に同様の上昇が見られたが、その都度同様の方法で低下させた。培養24時間後のOD660は87.3であった。 <Main culture>
Ammonium sulfate: 1.0 g, monopotassium phosphate: 1.5 g, dipotassium phosphate 1.5 g, potassium chloride: 1.67 g, magnesium sulfate heptahydrate: 0.5 g, ferrous sulfate, heptahydrate Product: 40 mg, manganese sulfate / hydrate: 40 mg, D-biotin: 1.0 mg, thiamine hydrochloride: 1.0 mg, yeast extract 10 g, antifoaming agent (CE457: manufactured by NOF Corporation): 1.0 g and distilled water: 400 mL of 1000 mL of medium was placed in a 1 L fermentor and sterilized by heating at 120 ° C. for 20 minutes. After cooling to room temperature, 20 mL of 72% aqueous glucose solution sterilized in advance was added, and 20 mL of the above seed culture solution was added thereto, and the mixture was kept at 30 ° C. The pH was kept at 7.0% or less using 9.3% aqueous ammonia, main culture was performed at aeration of 300 mL / min, and stirring at 600 rpm for 24 hours. The dissolved oxygen concentration gradually decreased immediately after the start of the culture, and became almost zero 4 hours after the start of the culture. Thereafter, since the dissolved oxygen concentration increased 15 hours after the start of culture, when 380 μL of 72% glucose aqueous solution sterilized in advance was added, it rapidly decreased again and became almost zero. Since an increase in dissolved oxygen concentration was observed after about 13 minutes, 380 μL of a 72% aqueous glucose solution sterilized in advance was added and lowered again. Thereafter, a similar increase was observed about every 13 minutes, but it was reduced by the same method each time. The OD660 after 24 hours of culture was 87.3.
リン酸1アンモニウム:84.4mg、リン酸2アンモニウム:75.8mg、塩化カリウム149.1mg、硫酸マグネシウム・7水和物:0.2g、硫酸第一鉄・7水和物:8mg、硫酸マンガン・水和物:8mg、D-ビオチン:80μg、塩酸チアミン:80μg及び蒸留水:200mLの培地を500mLの三角フラスコに入れ、120℃、20分加熱滅菌した。室温まで冷やした後、1Lのジャーファーメンターに入れた。この懸濁液200mLに上記の本培養により得られた培養液90mL、あらかじめ滅菌した72%グルコース溶液:40mL、滅菌水:125mLを添加して混合し、35℃に保温した。pHは炭酸アンモニウム:154g、28%アンモニア水:239ml、蒸留水:650mLの水溶液を用いて7.6に保ち、毎分200回転で攪拌しながら有機酸生産反応を行った。反応開始後21時間における生産コハク酸濃度は34.8g/Lであり、少量のフマル酸が含有されていた。
このようにして調整したコハク酸発酵液を遠心分離(10,000G、10分)処理して得られた上澄み液を以下の実施例、比較例に供した。 <Organic acid production culture>
Monoammonium phosphate: 84.4 mg, diammonium phosphate: 75.8 mg, potassium chloride 149.1 mg, magnesium sulfate heptahydrate: 0.2 g, ferrous sulfate heptahydrate: 8 mg, manganese sulfate Hydrate: 8 mg, D-biotin: 80 μg, thiamine hydrochloride: 80 μg, and distilled water: 200 mL of medium was placed in a 500 mL Erlenmeyer flask and sterilized by heating at 120 ° C. for 20 minutes. After cooling to room temperature, it was placed in a 1 L jar fermenter. To 200 mL of this suspension, 90 mL of the culture solution obtained by the above main culture, 72% glucose solution sterilized in advance: 40 mL, and sterilized water: 125 mL were added and mixed, and kept at 35 ° C. The pH was maintained at 7.6 using an aqueous solution of ammonium carbonate: 154 g, 28% aqueous ammonia: 239 ml, distilled water: 650 mL, and an organic acid production reaction was performed while stirring at 200 rpm. The production succinic acid concentration at 21 hours after the start of the reaction was 34.8 g / L, and a small amount of fumaric acid was contained.
The supernatant obtained by subjecting the succinic acid fermentation broth thus prepared to centrifugation (10,000 G, 10 minutes) was subjected to the following Examples and Comparative Examples.
参考例に準じて調製した培養液を減圧加温下で濃縮を行った。濃縮された培養液を攪拌しながら、47%硫酸を培養液に滴下して溶液のpHを2とした。硫酸を添加した培養液に有機溶媒として培養液と等容量のメチルエチルケトン(MEK)を添加し、25℃で、約30分攪拌した。得られた液を静置後、有機層と水層とに分け、分液された水層に水層の体積の半分の容量のMEKを加え、25℃で、30分攪拌した。同様に液を静置後、有機層と水層とに分けた。同様の操作を更に3回繰り返し、全有機層をあわせた。有機層を液体クロマトグラフィー(LC)で分析した結果、有機層には、使用ブロス中に含有していた97.9%量のコハク酸が抽出された(図2)。 Example 1
The culture solution prepared according to the reference example was concentrated under reduced pressure heating. While stirring the concentrated culture solution, 47% sulfuric acid was added dropwise to the culture solution to adjust the pH of the solution to 2. A volume of methyl ethyl ketone (MEK) equal to that of the culture broth was added as an organic solvent to the culture broth added with sulfuric acid, and the mixture was stirred at 25 ° C. for about 30 minutes. The liquid obtained was allowed to stand, then divided into an organic layer and an aqueous layer, MEK having a volume half the volume of the aqueous layer was added to the separated aqueous layer, and the mixture was stirred at 25 ° C. for 30 minutes. Similarly, the liquid was allowed to stand, and then divided into an organic layer and an aqueous layer. The same operation was repeated three more times, and all the organic layers were combined. As a result of analyzing the organic layer by liquid chromatography (LC), 97.9% amount of succinic acid contained in the broth used was extracted from the organic layer (FIG. 2).
次に、SUS316製500ml誘導攪拌オートクレーブを用いて、上記のようにして得られた150gの粗コハク酸中に含まれる微量のフマル酸の水添反応を282gの蒸留水中で、5%Pd/C(和光カタログ326-81672、触媒量:コハク酸に対して1wt%)存在下、水素圧が0.2MPa、反応温度が100℃、反応時間が2時間の条件下で実施した。その結果、粗コハク酸中に含有されていた微量のフマル酸(コハク酸に対して0.3重量%含有)はすべてコハク酸へ誘導された。反応終了後のコハク酸溶液に蒸留水を加えて19wt%のコハク酸水溶液とした後に、触媒を濾別した。水素処理液には臭気は殆ど無かった。 Next, MEK was distilled off from the obtained MEK extract at 70 ° C. while adjusting the degree of vacuum from 400 mmHg to 100 mmHg, and the MEK extracted organic layer was concentrated. Thereafter, the obtained solution was cooled from 70 ° C. to 40 ° C. over 30 minutes, and then stirred at 40 ° C. for 1 hour. The precipitated crystals were filtered and rinsed with cold water to obtain crude crystals. On the other hand, the filtrate was further cooled from 40 ° C. to 10 ° C. over 30 minutes and stirred at 10 ° C. for 1 hour. The precipitated crystals were filtered and rinsed with cold water to obtain crude crystals. In this step, 98% of the succinic acid extracted in the MEK organic layer was recovered. Succinic acid at this stage was light brown and had a strong odor.
Next, the hydrogenation reaction of a small amount of fumaric acid contained in 150 g of crude succinic acid obtained as described above was carried out using SUS316 500 ml induction stirring autoclave in 5% Pd / C in 282 g of distilled water. (Wako catalog 326-81672, catalyst amount: 1 wt% with respect to succinic acid), hydrogen pressure was 0.2 MPa, reaction temperature was 100 ° C., and reaction time was 2 hours. As a result, all trace amounts of fumaric acid contained in the crude succinic acid (containing 0.3% by weight based on succinic acid) were all derived into succinic acid. Distilled water was added to the succinic acid solution after completion of the reaction to form a 19 wt% aqueous succinic acid solution, and then the catalyst was filtered off. The hydrogen treatment liquid had almost no odor.
攪拌装置、窒素導入口、加熱装置、温度計及び減圧用排気口を備えた反応容器に、実施例1で製造したコハク酸100重量部、三菱化学社製工業グレードの1,4―ブタンジオール88.5重量部、リンゴ酸0.37重量部ならびに触媒として二酸化ゲルマニウムを予め0.98重量%溶解させた88%乳酸水溶液5.4重量部を仕込み、窒素―減圧置換によって系内を窒素雰囲気下にした。
次に、系内を撹拌しながら220℃に昇温し、この温度で1時間反応させた。次に、30分かけて230℃まで昇温し、同時に1.5時間かけて0.07×103Paになるように減圧し、同減圧度で2.8時間反応を行い、重合を終了し、白色のポリエステル(黄色度YIは6)を得た。
得られたポリエステルの還元粘度(ηsp/c)は2.3であった。ポリエステルの末端カルボキシル基量は24当量/トンあった。得られたポリエステルはクロロホルムに室温で均一に溶解した。そのクロロホルム溶液からクロロホルムを留去すると均一なフィルムが作成された。 [Polyester Production Example 1]
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer and a vacuum outlet, 100 parts by weight of succinic acid produced in Example 1,
Next, the temperature in the system was increased to 220 ° C. while stirring, and the reaction was performed at this temperature for 1 hour. Next, the temperature was raised to 230 ° C. over 30 minutes, and at the same time, the pressure was reduced to 0.07 × 10 3 Pa over 1.5 hours, and the reaction was performed at the same reduced pressure for 2.8 hours to complete the polymerization. As a result, white polyester (yellowness YI is 6) was obtained.
The polyester obtained had a reduced viscosity (ηsp / c) of 2.3. The terminal carboxyl group amount of the polyester was 24 equivalents / ton. The obtained polyester was uniformly dissolved in chloroform at room temperature. When chloroform was distilled off from the chloroform solution, a uniform film was formed.
実施例1と同様に、参考例に準じて調製した培養液を減圧加温下で濃縮を行った。濃縮された培養液を攪拌しながら、47%硫酸を培養液に滴下して培養液のpHを2とした。硫酸を添加した培養液に有機溶媒として培養液と等容量のメチルエチルケトン(MEK)を添加し、25℃で、約30分攪拌した。得られた液を静置後、有機層と水層とに分け、分液された水層に水層の体積の等容量のMEKを加え、25℃で、30分攪拌した。同様に液を静置後、有機層と水層とに分けた。同様の操作を更に1回繰り返し、全有機層をあわせた。有機層を液体クロマトグラフィー(LC)で分析した結果、有機層には、使用ブロス中に含有していた97.9%量のコハク酸が抽出された。
次に有機層を90℃に加温しながら50mmHg程度の減圧下でMEKを留去して濃縮後、氷水で冷やし、2時間静置した。析出した結晶を濾過後、冷水でリンスして、粗結晶を得た。この工程では、MEK有機層に抽出されたコハク酸の96%量のコハク酸が回収された。この段階でのコハク酸は、薄褐色を呈し且つ、強い臭気を有していた。 Example 2
In the same manner as in Example 1, the culture solution prepared according to the reference example was concentrated under reduced pressure and heating. While stirring the concentrated culture solution, 47% sulfuric acid was added dropwise to the culture solution to adjust the pH of the culture solution to 2. A volume of methyl ethyl ketone (MEK) equal to that of the culture broth was added as an organic solvent to the culture broth added with sulfuric acid, and the mixture was stirred at 25 ° C. for about 30 minutes. The obtained liquid was allowed to stand, then divided into an organic layer and an aqueous layer, MEK having an equal volume of the aqueous layer was added to the separated aqueous layer, and the mixture was stirred at 25 ° C. for 30 minutes. Similarly, the liquid was allowed to stand, and then divided into an organic layer and an aqueous layer. The same operation was repeated once more, and all the organic layers were combined. As a result of analyzing the organic layer by liquid chromatography (LC), 97.9% amount of succinic acid contained in the broth used was extracted from the organic layer.
Next, MEK was distilled off under reduced pressure of about 50 mmHg while the organic layer was heated to 90 ° C., concentrated, cooled with ice water, and allowed to stand for 2 hours. The precipitated crystals were filtered and rinsed with cold water to obtain crude crystals. In this step, 96% of the succinic acid extracted in the MEK organic layer was recovered. Succinic acid at this stage was light brown and had a strong odor.
攪拌装置、窒素導入口、加熱装置、温度計及び減圧用排気口を備えた反応容器に、実施例2で製造したコハク酸100重量部、三菱化学社製工業グレードの1,4―ブタンジオール88.5重量部、リンゴ酸0.37重量部ならびに触媒として二酸化ゲルマニウムを予め0.98重量%溶解させた88%乳酸水溶液5.4重量部を仕込み、窒素―減圧置換によって系内を窒素雰囲気下にした。
次に、系内を撹拌しながら220℃に昇温し、この温度で1時間反応させた。次に、30分かけて230℃まで昇温し、同時に1.5時間かけて0.07×103Paになるように減圧し、同減圧度で3時間反応を行い重合を終了し、淡黄色のポリエステル(黄色度YIは23)を得た。
得られたポリエステルの還元粘度(ηsp/c)は2.4であった。ポリエステルの末端カルボキシル基量は25当量/トンあった。尚、得られたポリエステルはクロロホルムに室温で均一に溶解した。そのクロロホルム溶液からクロロホルムを留去すると均一なフィルムが作成された。 [Polyester Production Example 2]
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and a vacuum outlet, 100 parts by weight of succinic acid produced in Example 2,
Next, the temperature in the system was increased to 220 ° C. while stirring, and the reaction was performed at this temperature for 1 hour. Next, the temperature was raised to 230 ° C. over 30 minutes, and at the same time, the pressure was reduced to 0.07 × 10 3 Pa over 1.5 hours, and the reaction was carried out at the same reduced pressure for 3 hours to complete the polymerization. Yellow polyester (yellowness YI is 23) was obtained.
The polyester obtained had a reduced viscosity (ηsp / c) of 2.4. The amount of terminal carboxyl groups of the polyester was 25 equivalents / ton. The obtained polyester was uniformly dissolved in chloroform at room temperature. When chloroform was distilled off from the chloroform solution, a uniform film was formed.
参考例に準じて調製した培養液を実施例1と同様に濃硫酸にてプロトン化し、さらに抽出、晶析を行い、粗コハク酸を回収した。この段階でのコハク酸は、薄褐色を呈し且つ、強い臭気を有していた。
次に、SUS316製500ml誘導攪拌オートクレーブを用いて、上記のようにして得られた強い臭気を示す100gの粗コハク酸の水素処理を222gの脱塩水中で、5%Pd/C(和光カタログ326-81672、触媒量:コハク酸に対して1wt%)存在下、水素圧が0.2MPa、反応温度が100℃、反応時間が2時間の条件下で実施した。水素処理液には臭気は殆ど無かった。処理液は70℃の熱濾過で触媒を分離した。該熱濾液は攪拌下約90分で20℃まで冷却し、さらに20℃で1時間保持することで結晶を析出させ、ヌッチェで固液分離して含水コハク酸の結晶を得た。得られたコハク酸結晶は白色を呈しており、コハク酸結晶からは特有の臭気は感じられなかった。 Example 3
The culture solution prepared according to the reference example was protonated with concentrated sulfuric acid in the same manner as in Example 1, and further extracted and crystallized to recover crude succinic acid. Succinic acid at this stage was light brown and had a strong odor.
Next, using a SUS316 500 ml induction stirring autoclave, 100 g of crude succinic acid having a strong odor obtained as described above was treated with 5% Pd / C (Wako catalog 326) in 222 g of demineralized water. −81672, catalyst amount: 1 wt% with respect to succinic acid), hydrogen pressure was 0.2 MPa, reaction temperature was 100 ° C., and reaction time was 2 hours. The hydrogen treatment liquid had almost no odor. The catalyst was separated from the treatment liquid by hot filtration at 70 ° C. The hot filtrate was cooled to 20 ° C. with stirring for about 90 minutes, and further kept at 20 ° C. for 1 hour to precipitate crystals, and solid-liquid separation was performed with Nutsche to obtain hydrous succinic acid crystals. The obtained succinic acid crystals had a white color, and no specific odor was felt from the succinic acid crystals.
参考例に準じて調製した培養液を実施例1と同様に濃硫酸にてプロトン化し、さらに抽出、晶析を行い、粗コハク酸を回収した。この段階でのコハク酸は、薄褐色を呈し且つ、強い臭気を有していた。
次に、30wt%の粗コハク酸水溶液80℃で調製した後、コハク酸に対して5wt%量のクラレケミカル株式会社製の活性炭クラレコールGWを加えた。活性炭処理は、80℃に保温した恒温式振盪器を用いて3時間実施した。その後、80℃で活性炭を濾別した。この段階においてもコハク酸水溶液には特有の臭気が残存した。
得られたコハク酸水溶液をSUS316製500ml誘導攪拌オートクレーブに仕込み、5%Pd/C(和光カタログ326-81672、触媒量:コハク酸に対して0.06wt%)存在下、水素圧が0.8MPa、反応温度が80℃、反応時間が3時間の条件下で水素処理を実施した。その結果、粗コハク酸中にコハク酸に対して1.8重量%量含有されていたフマル酸はすべてコハク酸へ誘導された。反応終了後、触媒を濾別した。水素処理液には臭気は殆ど無かった。
続いて、この水素処理したコハク酸水溶液を80℃でイオン交換処理(陽イオン交換樹脂(ダイヤイオンSK1B-H(三菱化学株式会社製):H型)により微量含まれたカチオンを除去した。
更に、イオン交換処理されたコハク酸水溶液を攪拌下約90分で20℃まで冷却し、さらに20℃で1時間保持することで結晶を析出させた。析出したコハク酸を濾過により回収し、冷水で結晶を洗浄後、70℃、12時間真空乾燥を行い、白色の無臭のコハク酸を得た(YI=-1)。得られたコハク酸中には、Na、K、Mg、Ca、NH4イオンの濃度はいずれも1ppm以下、硫黄原子含有量は1ppm未満、窒素原子含有量は2ppmであった。また、得られたコハク酸の3.0wt%濃度のコハク酸水溶液を調製し、日立分光光度計日立UV-3500を用いて測定したスペクトルの250-300nmの平均吸光度は、実施例1のコハク酸と同様(0.01以下)であった。 Example 4
The culture solution prepared according to the reference example was protonated with concentrated sulfuric acid in the same manner as in Example 1, and further extracted and crystallized to recover crude succinic acid. Succinic acid at this stage was light brown and had a strong odor.
Next, after preparing 30 wt% crude succinic acid aqueous solution at 80 degreeC, the activated carbon Kuraray Coal GW made from Kuraray Chemical Co. of 5 wt% with respect to succinic acid was added. The activated carbon treatment was carried out for 3 hours using a constant temperature shaker kept at 80 ° C. Thereafter, the activated carbon was filtered off at 80 ° C. Even at this stage, a unique odor remained in the aqueous succinic acid solution.
The obtained aqueous succinic acid solution was charged into a 500 ml induction stirring autoclave made of SUS316, and the hydrogen pressure was 0.8 MPa in the presence of 5% Pd / C (Wako catalog 326-81672, catalyst amount: 0.06 wt% with respect to succinic acid). The hydrogen treatment was carried out under conditions of a reaction temperature of 80 ° C. and a reaction time of 3 hours. As a result, all fumaric acid contained in the crude succinic acid in an amount of 1.8% by weight based on succinic acid was derived into succinic acid. After completion of the reaction, the catalyst was filtered off. The hydrogen treatment liquid had almost no odor.
Subsequently, the hydrogen-treated succinic acid aqueous solution was subjected to ion exchange treatment (cation exchange resin (Diaion SK1B-H (manufactured by Mitsubishi Chemical Corporation): H type)) at 80 ° C. to remove cations contained in a trace amount.
Further, the aqueous solution of succinic acid subjected to the ion exchange treatment was cooled to 20 ° C. in about 90 minutes with stirring, and further maintained at 20 ° C. for 1 hour to precipitate crystals. The precipitated succinic acid was collected by filtration, and the crystals were washed with cold water and then vacuum-dried at 70 ° C. for 12 hours to obtain white odorless succinic acid (YI = −1). In the obtained succinic acid, the concentrations of Na, K, Mg, Ca, and NH 4 ions were all 1 ppm or less, the sulfur atom content was less than 1 ppm, and the nitrogen atom content was 2 ppm. Further, a succinic acid aqueous solution having a concentration of 3.0 wt% of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured with a Hitachi spectrophotometer Hitachi UV-3500 was the succinic acid of Example 1. (0.01 or less).
[重縮合用触媒の調製]
撹拌装置付き500cm3のガラス製ナス型フラスコに酢酸マグネシウム・4水和物を62.0g入れ、更に250gの無水エタノール(純度99重量%以上)を加えた。更にエチルアシッドホスフェート(モノエステル体とジエステル体の混合重量比は45:55)を35.8g加え、23℃で撹拌を行った。15分後に酢酸マグネシウムが完全に溶解したことを確認後、テトラ-n-ブチルチタネートを75.0g添加した。更に10分間撹拌を継続し、均一混合溶液を得た。この混合溶液を、1000cm3のナス型フラスコに移し、60℃のオイルバス中でエバポレーターによって減圧下で濃縮を行った。1時間後に殆どのエタノールが留去され、半透明の粘稠な液体が残った。オイルバスの温度を更に80℃まで上昇させ、5Torrの減圧下で更に濃縮を行った。粘稠な液体は表面から粉体状へと徐々に変化し、2時間後には完全に粉体化した。その後、窒素を用いて常圧に戻し、室温まで冷却し、淡黄色粉体108gを得た。得られた触媒の金属元素分析値は、チタン原子含有量が10.3重量%、マグネシウム原子含有量が6.8重量%、リン原子含有量が7.8重量%であり、モル比としては、T/P=0.77,M/P=1.0であった。更に、粉体状の触媒を1,4-ブタンジオールに溶解させ、チタン原子として34,000ppmとなるように調製した。 [Polyester Production Example 3]
[Preparation of catalyst for polycondensation]
62.0 g of magnesium acetate tetrahydrate was placed in a 500 cm 3 glass eggplant-shaped flask equipped with a stirrer, and 250 g of absolute ethanol (purity 99% by weight or more) was further added. Further, 35.8 g of ethyl acid phosphate (mixing weight ratio of monoester and diester was 45:55) was added and stirred at 23 ° C. After confirming that magnesium acetate was completely dissolved after 15 minutes, 75.0 g of tetra-n-butyl titanate was added. Stirring was further continued for 10 minutes to obtain a uniform mixed solution. This mixed solution was transferred to a 1000 cm 3 eggplant-shaped flask and concentrated in an oil bath at 60 ° C. under reduced pressure using an evaporator. After 1 hour, most of the ethanol was distilled off, leaving a translucent viscous liquid. The temperature of the oil bath was further increased to 80 ° C., and further concentration was performed under a reduced pressure of 5 Torr. The viscous liquid gradually changed from the surface to a powder form, and was completely powdered after 2 hours. Then, it returned to normal pressure using nitrogen, and it cooled to room temperature, and obtained 108 g of pale yellow powder. The metal element analysis value of the obtained catalyst was as follows: titanium atom content was 10.3 wt%, magnesium atom content was 6.8 wt%, and phosphorus atom content was 7.8 wt%. T / P = 0.77 and M / P = 1.0. Further, a powdery catalyst was dissolved in 1,4-butanediol to prepare 34,000 ppm as titanium atoms.
攪拌装置、窒素導入口、加熱装置、温度計及び減圧用排気口を備えた反応容器に、原料として実施例4で製造したコハク酸100重量部、三菱化学社製工業グレードの1,4-ブタンジオール99.2重量部、リンゴ酸0.38重量部(コハク酸に対して総リンゴ酸量0.33mol%)を仕込み、窒素-減圧置換によって系内を窒素雰囲気下にした。
次に、系内を撹拌しながら1時間かけて230℃まで昇温し、この温度で1時間反応させた。その後、上記の触媒溶液を添加した。添加量は得られるポリエステル樹脂あたりチタン原子として50ppmとなる量とした。反応温度を250℃まで徐々に昇温し、同時に2時間かけて0.06×103Paになるように減圧し、更に同減圧度で2.5時間反応を行い、重合を終了し、白色のポリエステル(黄色度YIは2)を得た。
得られたポリエステルの還元粘度(ηsp/c)は2.3であった。ポリエステルの末端カルボキシル基量は24当量/トンあった。 [Production of aliphatic polyester resin]
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and a vacuum outlet, 100 parts by weight of succinic acid produced in Example 4 as a raw material,
Next, the temperature in the system was raised to 230 ° C. over 1 hour while stirring, and the reaction was carried out at this temperature for 1 hour. Thereafter, the above catalyst solution was added. The amount added was 50 ppm as titanium atoms per polyester resin obtained. The reaction temperature is gradually raised to 250 ° C., and the pressure is reduced to 0.06 × 10 3 Pa at the same time over 2 hours. The reaction is further performed for 2.5 hours at the same reduced pressure, and the polymerization is completed. Polyester (yellowness YI is 2) was obtained.
The polyester obtained had a reduced viscosity (ηsp / c) of 2.3. The terminal carboxyl group amount of the polyester was 24 equivalents / ton.
参考例に準じて調製した培養液を実施例1と同様に濃硫酸にてプロトン化し、さらに抽出、晶析を行い、粗コハク酸を回収した。この段階でのコハク酸は、薄褐色を呈し且つ、強い臭気を有していた。
次に、30wt%の粗コハク酸水溶液を80℃で調製した後、コハク酸に対して0.3wt%量の粉末状の薬液賦活した活性炭ダイヤホープ8ED(三菱化学カルゴン株式会社製)を加えた。活性炭処理は、スリーワンモーターを用いて200rpmで攪拌しながら80℃で2時間実施した。
80℃で活性炭を濾別後、得られたコハク酸水溶液をSUS316製500ml誘導攪拌オートクレーブに仕込み、5%Pd/C(和光カタログ326-81672、触媒量:コハク酸に対して0.06wt%)存在下、水素圧が0.8MPa、反応温度が80℃、反応時間が3時間の条件下で水素処理を実施した。その結果、粗コハク酸中にコハク酸に対して1.3重量%含有されていたフマル酸はすべてコハク酸へ誘導された。反応終了後、触媒を濾別した。水素処理液には臭気は殆ど無かった。
この水素処理したコハク酸水溶液を80℃でイオン交換処理(陽イオン交換樹脂(ダイヤイオンSK1B-H(三菱化学株式会社製):H型)により微量含まれたカチオンを除去した。
イオン交換処理されたコハク酸水溶液を攪拌下約90分で20℃まで冷却し、さらに20℃で1時間保持することで結晶を析出させた。析出したコハク酸を濾過により回収し、冷水で結晶を洗浄後、70℃、12時間真空乾燥を行い、白色の無臭のコハク酸を得た(YI=-1)。得られたコハク酸中には、Na、K、Mg、Ca、NH4イオンの濃度はいずれも1ppm以下、硫黄原子含有量は1ppm未満、窒素原子含有量は2ppmであった。また、得られたコハク酸の3.0wt%濃度のコハク酸水溶液を調製し、日立分光光度計日立UV-3500を用いて測定したスペクトルの250-300nmの平均吸光度は、実施例1のコハク酸と同様(0.01以下)であった。 Example 5
The culture solution prepared according to the reference example was protonated with concentrated sulfuric acid in the same manner as in Example 1, and further extracted and crystallized to recover crude succinic acid. Succinic acid at this stage was light brown and had a strong odor.
Next, a 30 wt% crude succinic acid aqueous solution was prepared at 80 ° C., and then 0.3 wt% of powdered chemical activated charcoal diamond hop 8ED (Mitsubishi Chemical Calgon Co., Ltd.) was added to succinic acid. . The activated carbon treatment was performed at 80 ° C. for 2 hours while stirring at 200 rpm using a three-one motor.
After filtering off the activated carbon at 80 ° C., the obtained aqueous succinic acid solution was charged into a 500 ml induction stirring autoclave made of SUS316, 5% Pd / C (Wako catalog 326-81672, catalyst amount: 0.06 wt% with respect to succinic acid) In the presence, hydrogen treatment was carried out under the conditions of a hydrogen pressure of 0.8 MPa, a reaction temperature of 80 ° C., and a reaction time of 3 hours. As a result, all fumaric acid contained in the crude succinic acid in an amount of 1.3% by weight based on succinic acid was derived into succinic acid. After completion of the reaction, the catalyst was filtered off. The hydrogen treatment liquid had almost no odor.
The hydrogenated succinic acid aqueous solution was subjected to ion exchange treatment (cation exchange resin (Diaion SK1B-H (manufactured by Mitsubishi Chemical Corporation): H type)) at 80 ° C. to remove cations contained in a trace amount.
The ion exchange treated succinic acid aqueous solution was cooled to 20 ° C. with stirring for about 90 minutes, and further kept at 20 ° C. for 1 hour to precipitate crystals. The precipitated succinic acid was collected by filtration, and the crystals were washed with cold water and then vacuum-dried at 70 ° C. for 12 hours to obtain white odorless succinic acid (YI = −1). In the obtained succinic acid, the concentrations of Na, K, Mg, Ca, and NH 4 ions were all 1 ppm or less, the sulfur atom content was less than 1 ppm, and the nitrogen atom content was 2 ppm. Further, a succinic acid aqueous solution having a concentration of 3.0 wt% of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured with a Hitachi spectrophotometer Hitachi UV-3500 was the succinic acid of Example 1. (0.01 or less).
原料として実施例5で製造したコハク酸を使用した以外はポリエステル製造例3と同様の方法を用いてポリエステルの製造を行った。
攪拌装置、窒素導入口、加熱装置、温度計及び減圧用排気口を備えた反応容器に、原料として実施例5で製造したコハク酸100重量部、1,4-ブタンジオール99.2重量部、リンゴ酸0.38重量部(コハク酸に対して総リンゴ酸量0.33mol%)を仕込み、窒素-減圧置換によって系内を窒素雰囲気下にした。
次に、系内を撹拌しながら1時間かけて230℃まで昇温し、この温度で1時間反応させた。その後、ポリエステル製造例3に記載の触媒溶液を添加した。添加量は得られるポリエステル樹脂あたりチタン原子として50ppmとなる量とした。反応温度を250℃まで徐々に昇温し、同時に2時間かけて0.06×103Paになるように減圧し、更に同減圧度で2.4時間反応を行い、重合を終了し、白色のポリエステル(黄色度YIは3)を得た。
得られたポリエステルの還元粘度(ηsp/c)は2.3であった。ポリエステルの末端カルボキシル基量は24当量/トンあった。 [Polyester Production Example 4]
A polyester was produced using the same method as in Polyester Production Example 3 except that the succinic acid produced in Example 5 was used as a raw material.
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer and a vacuum outlet, 100 parts by weight of succinic acid produced in Example 5 as a raw material, 99.2 parts by weight of 1,4-butanediol, 0.38 parts by weight of malic acid (total malic acid amount 0.33 mol% with respect to succinic acid) was charged, and the system was placed in a nitrogen atmosphere by nitrogen-vacuum substitution.
Next, the temperature in the system was raised to 230 ° C. over 1 hour while stirring, and the reaction was carried out at this temperature for 1 hour. Thereafter, the catalyst solution described in Polyester Production Example 3 was added. The amount added was 50 ppm as titanium atoms per polyester resin obtained. The reaction temperature is gradually raised to 250 ° C., and the pressure is reduced to 0.06 × 10 3 Pa at the same time over 2 hours. The reaction is further carried out for 2.4 hours at the same reduced pressure, and the polymerization is completed. Polyester (yellowness YI is 3) was obtained.
The polyester obtained had a reduced viscosity (ηsp / c) of 2.3. The terminal carboxyl group amount of the polyester was 24 equivalents / ton.
水素圧として0.2MPa加圧下で水素処理を行う代わりに窒素圧として0.2MPa加圧下で熱処理を行った以外は実施例3と同一の操作を行った。
SUS316製500ml誘導攪拌オートクレーブを用いて、薄褐色を呈し且つ、強い臭気を示す実施例3で使用したコハク酸と同一ロットの100gの粗コハク酸の熱処理を222gの脱塩水中で、5%Pd/C(和光カタログ326-81672、触媒量:コハク酸に対して1wt%)存在下、窒素圧が0.2MPa、反応温度が100℃、反応時間が2時間の条件下で実施した。処理液は強い臭気を有していた。処理液は70℃の熱濾過で触媒を分離した。該熱濾液は攪拌下約90分で20℃まで冷却し、さらに20℃で1時間保持することで結晶を析出させ、ヌッチェで固液分離して含水コハク酸の結晶を得た。得られたコハク酸結晶は白色を呈していたが、コハク酸結晶には特有の強い臭気が残留した。 Comparative Example 1
The same operation as in Example 3 was performed except that the heat treatment was performed under a pressure of 0.2 MPa as the nitrogen pressure instead of performing the hydrogen treatment under a pressure of 0.2 MPa as the hydrogen pressure.
Using a 500 ml induction stirring autoclave made of SUS316, heat treatment of 100 g of crude succinic acid of the same lot as that used in Example 3 which exhibits a light brown color and exhibits a strong odor was performed in 222 g of demineralized water with 5% Pd. / C (Wako catalog 326-81672, catalyst amount: 1 wt% with respect to succinic acid), nitrogen pressure was 0.2 MPa, reaction temperature was 100 ° C., and reaction time was 2 hours. The treatment liquid had a strong odor. The catalyst was separated from the treatment liquid by hot filtration at 70 ° C. The hot filtrate was cooled to 20 ° C. with stirring for about 90 minutes, and further kept at 20 ° C. for 1 hour to precipitate crystals, and solid-liquid separation was performed with Nutsche to obtain hydrous succinic acid crystals. The obtained succinic acid crystal had a white color, but the succinic acid crystal had a strong odor peculiar to it.
参考例に準じて調製した培養液を実施例2と同様に濃硫酸にてプロトン化し、さらに抽出、晶析を行い、粗コハク酸を回収した。この段階でのコハク酸は、薄褐色を呈し且つ、強い臭気を有していた。
次に、20wt%の粗コハク酸水溶液を80℃で調製した後、イオン交換処理(陽イオン交換樹脂(ダイヤイオンSKT20L(三菱化学株式会社製):H型)により含有されるカチオンを除去した。
イオン交換処理されたコハク酸水溶液から実施例2と同じ手順で晶析、乾燥を行い白色のコハク酸を得た(YI=6)。コハク酸結晶中には特有の臭気が残留した。得られたコハク酸中の、Na、K、Mg、Ca、NH4イオンの濃度はいずれも1ppm未満、硫黄原子含有量は1ppm未満、窒素原子含有量は3ppmであり、フマル酸含有量は0.08重量%であった。また、得られたコハク酸の3.0wt%濃度のコハク酸水溶液を調製し、日立分光光度計日立UV-3500を用いて測定したスペクトルの250-300nmの平均吸光度は、0.059であった。 Comparative Example 2
The culture solution prepared according to the reference example was protonated with concentrated sulfuric acid in the same manner as in Example 2, and further extracted and crystallized to recover crude succinic acid. Succinic acid at this stage was light brown and had a strong odor.
Next, after preparing a 20 wt% crude succinic acid aqueous solution at 80 ° C., cations contained by ion exchange treatment (cation exchange resin (Diaion SKT20L (manufactured by Mitsubishi Chemical Corporation): H type)) were removed.
Crystallization and drying were carried out from the ion exchange-treated succinic acid aqueous solution in the same procedure as in Example 2 to obtain white succinic acid (YI = 6). A characteristic odor remained in the succinic acid crystals. In the obtained succinic acid, the concentrations of Na, K, Mg, Ca, NH 4 ions are all less than 1 ppm, the sulfur atom content is less than 1 ppm, the nitrogen atom content is 3 ppm, and the fumaric acid content is 0. 0.08% by weight. In addition, a 3.0 wt% aqueous succinic acid solution of the obtained succinic acid was prepared, and the average absorbance at 250-300 nm of the spectrum measured using Hitachi spectrophotometer Hitachi UV-3500 was 0.059. .
攪拌装置、窒素導入口、加熱装置、温度計及び減圧用排気口を備えた反応容器に、比較例2で製造したコハク酸100重量部、三菱化学社製工業グレードの1,4―ブタンジオール88.5重量部、リンゴ酸0.37重量部ならびに触媒として二酸化ゲルマニウムを予め0.98重量%溶解させた88%乳酸水溶液5.4重量部を仕込み、窒素―減圧置換によって系内を窒素雰囲気下にした。
次に、系内を撹拌しながら220℃に昇温し、この温度で1時間反応させた。次に、30分かけて230℃まで昇温し、同時に1.5時間かけて0.07×103Paになるように減圧し、同減圧度で3時間13分反応を行い重合を終了し、淡黄色のポリエステル(黄色度YIは34)を得た。
得られたポリエステルの還元粘度(ηsp/c)は2.2であった。ポリエステルの末端カルボキシル基量は35当量/トンあった。尚、得られたポリエステルはクロロホルムに室温で均一に溶解した。そのクロロホルム溶液からクロロホルムを留去すると均一なフィルムが作成された。 [Polyester production comparative example 1]
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer and a vacuum outlet, 100 parts by weight of succinic acid produced in Comparative Example 2,
Next, the temperature in the system was increased to 220 ° C. while stirring, and the reaction was performed at this temperature for 1 hour. Next, the temperature was raised to 230 ° C. over 30 minutes, and at the same time, the pressure was reduced to 0.07 × 10 3 Pa over 1.5 hours, and the reaction was performed at the same degree of pressure for 3 hours and 13 minutes to complete the polymerization. Pale yellow polyester (yellow degree YI was 34) was obtained.
The reduced viscosity (ηsp / c) of the obtained polyester was 2.2. The amount of terminal carboxyl groups of the polyester was 35 equivalents / ton. The obtained polyester was uniformly dissolved in chloroform at room temperature. When chloroform was distilled off from the chloroform solution, a uniform film was formed.
本出願は、2008年9月29日出願の日本特許出願(特願2008-249740号)に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2008-249740) filed on Sep. 29, 2008, the contents of which are incorporated herein by reference.
Claims (23)
- バイオマス資源から誘導されるコハク酸の製造方法であって、少なくとも該コハク酸を含む溶液を触媒存在下で水素処理を行う工程を含むことを特徴とするコハク酸の製造方法。 A method for producing succinic acid derived from biomass resources, comprising a step of hydrotreating at least a solution containing the succinic acid in the presence of a catalyst.
- 水素処理の温度が30℃以上、150℃以下、水素圧が0.1MPa以上、5MPa以下であることを特徴とする請求項1に記載のコハク酸の製造方法。 2. The method for producing succinic acid according to claim 1, wherein the hydrogen treatment temperature is 30 ° C. or more and 150 ° C. or less, and the hydrogen pressure is 0.1 MPa or more and 5 MPa or less.
- 金属酸化物、シリカ及び活性炭の群から選ばれるいずれかの吸着剤存在下、水素化触媒により水素処理を行うことを特徴とする請求項1又は2のいずれかに記載のコハク酸の製造方法。 3. The method for producing succinic acid according to claim 1, wherein hydrogen treatment is performed with a hydrogenation catalyst in the presence of any adsorbent selected from the group consisting of metal oxide, silica and activated carbon.
- コハク酸を含む溶液が水溶液であることを特徴とする請求項1~3のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 1 to 3, wherein the solution containing succinic acid is an aqueous solution.
- 水素処理を行うコハク酸を含む溶液にフマル酸が含まれていることを特徴とする請求項1~4のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 1 to 4, wherein fumaric acid is contained in the solution containing succinic acid to be subjected to hydrogen treatment.
- 水素処理を行うコハク酸を含む溶液中のフマル酸の含有量がコハク酸重量に対して0.01~10重量%であることを特徴とする請求項5に記載のコハク酸の製造方法。 6. The method for producing succinic acid according to claim 5, wherein the content of fumaric acid in the solution containing succinic acid to be subjected to hydrogen treatment is 0.01 to 10% by weight based on the weight of succinic acid.
- コハク酸の250~300nmの紫外線領域の平均吸光度が0.05以下になるように、該コハク酸を含む溶液から不純物を除去することを特徴とする請求項1~6のいずれかに記載のコハク酸の製造方法。 The succinic acid according to any one of claims 1 to 6, wherein impurities are removed from the solution containing succinic acid so that the average absorbance in the ultraviolet region of 250 to 300 nm of succinic acid is 0.05 or less. Acid production method.
- 該不純物の除去が活性炭を用いた吸着除去によることを特徴とする請求項7に記載のコハク酸の製造方法。 The method for producing succinic acid according to claim 7, wherein the impurities are removed by adsorption removal using activated carbon.
- 該不純物の除去が溶媒を用いた晶析によることを特徴とする請求項7又は8に記載のコハク酸の製造方法。 The method for producing succinic acid according to claim 7 or 8, wherein the removal of the impurities is performed by crystallization using a solvent.
- 水素処理工程より前の工程でコハク酸を含む溶液中の不溶成分を膜透過処理により除去することを特徴とする請求項1~9のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 1 to 9, wherein insoluble components in the solution containing succinic acid are removed by membrane permeation treatment in a step prior to the hydrogen treatment step.
- 水素処理工程より前の工程でコハク酸を含む溶液中の不溶成分を吸着剤により除去することを特徴とする請求項1~9のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 1 to 9, wherein an insoluble component in the solution containing succinic acid is removed by an adsorbent in a step prior to the hydrogen treatment step.
- バイオマス資源から誘導されるコハク酸に、溶液中での活性炭を用いた吸着処理又は晶析処理の少なくともいずれかの処理を経た後に触媒存在下で水素処理を行うことを特徴とする請求項1~11のいずれかに記載のコハク酸の製造方法。 The succinic acid derived from biomass resources is subjected to a hydrogen treatment in the presence of a catalyst after at least one of an adsorption treatment using activated carbon in a solution and a crystallization treatment. The method for producing succinic acid according to any one of 11.
- バイオマス資源が植物資源であることを特徴とする請求項1~12のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 1 to 12, wherein the biomass resource is a plant resource.
- 該コハク酸の黄色度(YI)が10以下であることを特徴とする請求項1~13のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 1 to 13, wherein the yellowness degree (YI) of the succinic acid is 10 or less.
- 該不純物が窒素を含有する化合物であることを特徴とする請求項7~9のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 7 to 9, wherein the impurity is a compound containing nitrogen.
- 該不純物が芳香族化合物であることを特徴とする請求項7~9のいずれかに記載のコハク酸の製造方法。 The method for producing succinic acid according to any one of claims 7 to 9, wherein the impurity is an aromatic compound.
- 請求項1~16のいずれかに記載の方法により製造されたコハク酸。 Succinic acid produced by the method according to any one of claims 1 to 16.
- 250~300nmの紫外線領域の平均吸光度が0.05以下であることを特徴とするバイオマス資源から誘導されたコハク酸。 Succinic acid derived from biomass resources, characterized by having an average absorbance in the ultraviolet region of 250 to 300 nm of 0.05 or less.
- 黄色度(YI)が10以下であることを特徴とする請求項18に記載のコハク酸。 The succinic acid according to claim 18, wherein the yellowness (YI) is 10 or less.
- 請求項17~19のいずれかに記載のコハク酸を原料として用い得られたポリエステル。 A polyester obtained using the succinic acid according to any one of claims 17 to 19 as a raw material.
- カルボキシル基末端濃度が100当量/トン以下であることを特徴とする請求項20に記載のポリエステル。 21. The polyester according to claim 20, wherein the carboxyl group terminal concentration is 100 equivalents / ton or less.
- ポリエステルの還元粘度(ηsp/c)が0.5以上であることを特徴とする請求項20又は21に記載のポリエステル。 The polyester according to claim 20 or 21, wherein the polyester has a reduced viscosity (ηsp / c) of 0.5 or more.
- 請求項20~22のいずれかに記載のポリエステルを成形してなる成形体。 A molded body obtained by molding the polyester according to any one of claims 20 to 22.
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