WO2001034543A1 - Procede servant a preparer des melanges de diols - Google Patents
Procede servant a preparer des melanges de diols Download PDFInfo
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- WO2001034543A1 WO2001034543A1 PCT/JP2000/007757 JP0007757W WO0134543A1 WO 2001034543 A1 WO2001034543 A1 WO 2001034543A1 JP 0007757 W JP0007757 W JP 0007757W WO 0134543 A1 WO0134543 A1 WO 0134543A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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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
Definitions
- the present invention relates to a method for producing a diol mixture. More specifically, the process for producing a diol mixture comprising 1,4-butanediol, 1,5-pentenediol and 1,6-hexanediol comprises the steps of (A) producing adipic acid.
- an aqueous by-product solution containing a dicarboxylic acid mixture including succinic acid, glutaric acid, and adipic acid, which is obtained from a process for producing adipic acid, is used as a raw material, and dicarboxylic acid is used as a starting material.
- 1,4-butanediol, 1,5-pentanediol and 1,4-butanediol can be directly hydrogenated without converting to 6 It is possible to stably produce a diol mixture including monohexanediol for a long period of time.
- Diols are extremely important compounds that are widely used in the industrial field as raw materials for polyester resins, urethane forms, urethane paints, adhesives, etc. Produced.
- the main method used for the production of diols is to hydrogenate dicarboxylic diesters. The method is described using the production of 1,4-butanediol as an example.
- Methods for producing 1,4-butanediol include a method for producing 1,4-butanediol by introducing two hydroxyl groups into n-butane, but this method is not economically viable. It is virtually impossible at this time to implement it on an industrial scale.
- n-butane is air-oxidized to produce succinic acid, maleic acid, or their anhydrides, especially maleic acid or anhydrous maleic acid, and using it as a raw material
- the method of producing 1,4_butanediol is used.
- dicarboxylic acids such as maleic acid can be easily converted to diols by subjecting them to a reduction reaction.
- This reduction reaction is carried out using a suitable reducing agent, but usually requires a strong reducing agent with extremely high reactivity (for example, lithium aluminum hydride).
- a strong reducing agent with extremely high reactivity for example, lithium aluminum hydride.
- Such reducing agents must be handled and stored. It is not suitable for use on an industrial scale because of the special care required for.
- a reduction method (so-called hydrogenation reaction) performed using hydrogen gas as a reducing agent in the presence of an appropriate catalyst is suitable for implementation on an industrial scale.
- hydrogenation is usually not applicable to the reduction of dicarboxylic acids. This is because the catalyst conventionally used in the hydrogenation reaction dissolves in the dicarboxylic acid, so that the activity cannot be maintained in the presence of the acid.
- maleic acid or maleic anhydride obtained by air oxidation of n-butane is further reacted with a suitable alcohol.
- the method is to once convert to diester, and to hydrogenate the resulting maleic ester at high temperature and high pressure in the presence of copper catalyst to convert it to 1,4-butanediol.
- a method for producing an alcohol by hydrogenating an ester at a high temperature and a high pressure in the presence of a catalyst is disclosed in Japanese Patent Publication No. 2000-5100837 (US Pat. No. 6,100,000). , Corresponding to the specification of No. 4110), Japanese Patent Publication No.
- One example of such a method is to produce a diol by hydrogenating a dicarboxylic acid itself without esterification using a catalyst that maintains its activity even in the presence of an acid. Means are being considered.
- the diols can be produced by a two-step reaction of producing a dicarboxylic acid and hydrogenating the dicarboxylic acid.
- the step of esterifying dicarponic acid which was required in the conventional method, is not required, and accordingly, equipment for esterification is not required.
- esters of dicarboxylic acids Since the esterification is not performed, the alcohol used for the esterification is not produced as a by-product at the time of hydrogenation, and a facility for recovering and reusing the by-product alcohol is unnecessary.
- a catalyst containing lute compound tin-platinum supported on a carbonaceous carrier prepared by impregnating a carbonaceous carrier with a solution containing a carbonyl compound having 5 or less carbon atoms and a metal component to be supported. — 1 5 3 8 8);
- Japanese Patent Application Laid-Open No. 7-182190 discloses that a dicarboxylic acid is hydrogenated using a tertiary alcohol as a solvent in the presence of a catalyst composed of palladium and a rhenium compound. A method has been proposed.
- US Pat. No. 5,698,749 discloses that maleic acid is prepared by using a catalyst in which palladium-silver-rhenium is preliminarily oxidized with nitric acid and supported on activated carbon. It is stated that 1,4-butanediol can be obtained in relatively high yield.
- 1,6-hexanediol can be obtained in high yield by using a catalyst in which activated carbon pretreated with ruthenium-tin-platinum is supported on activated carbon.
- Japanese Unexamined Patent Publication No. Hei 11-201623 (corresponding to U.S. Pat. Nos. 5,969,194)) and the like are disclosed.
- adipic acid is produced by oxidizing cycloaliphatic compounds such as cyclohexanone and cyclohexanol with nitric acid
- a by-product aqueous solution is obtained after adipic acid is crystallized and separated.
- This by-product aqueous solution is an aqueous solution containing a dicarboxylic acid mixture containing succinic acid, daltaric acid and adipic acid, which is esterified and used as a solvent.
- the demand for such solvents is not always high, and some of the by-product aqueous solution is discarded without being used. is the current situation.
- a hydrogenation reaction can be carried out using an aqueous solution containing a mixture of dicarboxylic acids, which is a by-product in the production of adipic acid, as a raw material, 1,4-butanediol, 1,5-pentanediol, , 6 — (Polyurethanes such as hexanediols and diols useful as raw materials for polyesters can be advantageously obtained.
- the inventors of the present invention used a by-product aqueous solution containing a dicarboxylic acid mixture obtained during the production of adipic acid as a raw material, and efficiently and efficiently produced diols over a long period of time by hydrogenation.
- the nitric acid content of the by-product aqueous solution containing a mixture of dicarboxylic acids obtained during the production of adipic acid is reduced to a specific concentration or less to form a mixture of dicarboxylic acids and activate ruthenium and tin.
- a main object of the present invention is to hydrogenate a by-product aqueous solution containing a dicarboxylic acid mixture obtained when oxidizing a cycloaliphatic compound having 6 carbon atoms with nitric acid to produce adipic acid as a raw material. Accordingly, an object of the present invention is to provide a method for efficiently producing diols stably for a long period of time.
- a process for producing a diol mixture comprising 1,4-butanediol, 1,5-pentenediol and 1,6-hexanediol.
- the dicarboxylic acid mixture is prepared by denitrifying an aqueous by-product obtained in the process for producing adipic acid, and the process for producing adipic acid comprises at least one carbon atom.
- a method for producing a diol mixture comprising 1,4-butanediol, 1,5-pentanediol and 1,6-monohexanediol, comprising:
- (A) succinic acid, glutaric acid and adipic acid are included, and the nitric acid content is a total of the succinic acid, daltaric acid and adipic acid.
- the dicarboxylic acid mixture is prepared by denitrifying the by-product aqueous solution obtained in the process for producing adipic acid, and the process for producing adipic acid includes at least one type of carbon having at least 6 carbon atoms.
- the cyclic aliphatic compound is subjected to oxidation with nitric acid in an aqueous medium in the presence of an oxidation catalyst to obtain an aqueous reaction solution containing succinic acid, glutaric acid and adipic acid. And isolating the crystals thus obtained from the reaction solution to obtain a by-product aqueous solution.
- the dicarboxylic acid mixture is prepared so as to satisfy at least one condition selected from the group consisting of the following conditions (1) to (3). 2.
- the mixture has a nitric acid content of 0.2% by weight or less based on the total weight of succinic acid, daltaric acid and adipic acid. ;
- the mixture has a copper content and a vanadium content of 10 ppm or less, respectively, based on the total weight of succinic acid, glutaric acid, and adipic acid;
- the mixture has an io content of 200 ppm or less, based on the total weight of succinic acid, dataric acid and adipic acid.
- E is the extinction coefficient at 355 nm
- A is the absorbance at room temperature of an aqueous solution obtained by dissolving the dicarboxylic acid mixture in distilled water
- c is dissolved in 100 g of distilled water.
- the weight (g) of the dicarboxylic acid mixture and b is the length (cm) of the cell used for measuring the absorbance.) 5.
- the method according to the above item 4 wherein an aqueous solution of the dicarboxylic acid mixture dissolved in distilled water has an extinction coefficient of 0.1 or less.
- the compound in which the dicarboxylic acid mixture has an oxygen-nitrogen bond is converted to a weight of nitric acid, and is not more than 2,000 ppm based on the total weight of succinic acid, daltaric acid and adipic acid. 6.
- the active metal species contained in the hydrogenation catalyst is selected from the group consisting of metals of Group 8 of the periodic table other than ruthenium, and metals of Groups 9 and 10 of the periodic table. Any of the preceding clauses 1 to 8, characterized in that they further contain at least one metal.
- the manufacturing method as described.
- At least one metal selected from the group consisting of metals of Group 8 of the periodic table other than ruthenium, and metals of Groups 9 and 10 of the periodic table is platinum. 10. The production method according to the above item 9, wherein:
- the dicarboxylic acid mixture is prepared as an aqueous solution by a first purification process comprising the following steps (a) to (c): Manufacturing method described in Crab
- the first purification process further comprises a step of bringing the aqueous solution of the denitrated dicarboxylic acid mixture into contact with activated carbon.
- step (e) adding an aromatic hydrocarbon having 6 to 14 carbon atoms having a boiling point at normal pressure of 200 ° C. or less to the denitrated dicarboxylic acid mixture obtained in step (d), Heating the mixture obtained at a temperature equal to or lower than the boiling point of the aromatic hydrocarbon, cooling the mixture, and
- the second purification process comprises, after step (a), dissolving the denitrified dicarboxylic acid mixture in the form of an aqueous solution or the aqueous solution obtained by dissolving the denitrified dicarbonic acid mixture in water, 16.
- the production method according to the above item 16 further comprising a step of contacting with an anion-adsorbing substance.
- the aqueous by-product is hydrogenated in the presence of a reduction catalyst containing an active metal species containing at least one metal selected from the group consisting of metals of Groups 7 to 10 of the periodic table.
- a reduction catalyst containing an active metal species containing at least one metal selected from the group consisting of metals of Groups 7 to 10 of the periodic table.
- Contacting with a gas to reduce the compound having nitric acid and oxygen-nitrogen bonds contained in the by-product water solution to obtain the dicarboxylic acid mixture in the form of an aqueous solution.
- the reduction reaction of the compound having a nitric acid and an oxygen-nitrogen bond in the third purification process is performed at a temperature of 50 to 200 and a hydrogen pressure of 0.2 to 5 MPa. 18.
- the active metal species contained in the reduction catalyst used in the third purification process is selected from the group consisting of platinum, rhenium, palladium, rhodium, nickel, iridium and ruthenium. 18. The production method according to the above item 18 or 19, wherein both are one kind of metal.
- the by-product aqueous solution is heated at a temperature of 80 to 130 and a pressure lower than normal pressure, and then further heated at a temperature of 130 to 180 and normal pressure, and water is added thereto.
- Adipic acid oxidizes at least one cycloaliphatic compound having 6 carbon atoms with nitric acid in the presence of an oxidation catalyst that includes copper and vanadium, for example, cyclohexanone and cyclohexanol.
- an oxidation catalyst that includes copper and vanadium, for example, cyclohexanone and cyclohexanol.
- adipic acid in addition to adipic acid, a main reaction product, by-products such as dartalic acid, succinic acid, malonic acid, and oxalic acid are generated, and a trace amount of a coloring substance is generated. Since these by-products have higher solubility in water than adipic acid, adipic acid can be separated by crystallization by cooling the reaction solution to room temperature or lower.
- the crystallized adipic acid is recovered by filtration, but the remaining by-product aqueous solution contains by-products, nitric acid and catalyst. In general, this by-product aqueous solution is concentrated, and an appropriate amount of newly added nitric acid is reused in the production of adipic acid. However, when this operation is repeated, the concentration of by-products contained in the reaction product increases, resulting in a decrease in the purity of the product adipic acid.
- a part of the by-product aqueous solution is discharged out of the system in order to prevent the purity of adipic acid from decreasing.
- other by-products remove the dicarboxylic acid mixture. Collect as a by-product aqueous solution.
- the main components of the by-product aqueous solution containing the dicarboxylic acid mixture are daltaric acid, succinic acid, and unrecoverable adipic acid. These dicarboxylic acids are esterified and used as a solvent or the like. .
- adipic acid is produced by using at least one kind of cycloaliphatic compound having 6 carbon atoms as a raw material, and the by-product obtained after isolating the produced crystals of adipic acid by precipitation.
- the by-product aqueous solution may be an aqueous solution obtained by isolating a product of adipic acid from the reaction solution, or an aqueous solution after further recovering useful components such as nitric acid and a catalyst.
- the concentration of the dicarboxylic acid mixture in the aqueous by-product solution is 5 to 40% by weight, and the dicarboxylic acids contained therein are mainly succinic acid and dartalic acid by-produced, and adipic acid not recovered.
- the concentration of succinic acid, daltaric acid, and adipic acid relative to the total weight of succinic acid, dataric acid, and adipic acid in the aqueous solution is usually about 15 to 35% by weight and about 45 to 75% by weight, respectively. And about 3 to 40% by weight.
- the nitric acid content of the by-product aqueous solution containing copper, vanadium, and other trace impurities derived from the nitric acid that has not been removed and the catalyst used in the oxidation using nitric acid is included in the nitric acid recovery process. Depending on the conditions, it is usually at least about 6% by weight, based on the total weight of succinic acid, glutaric acid and adipic acid. In addition, the by-product aqueous solution is colored yellow, which is considered to be due to impurities contained therein.
- the by-product aqueous solution obtained during the production of adipic acid is used, and its nitric acid content is adjusted to 3% by weight or less based on the total weight of succinic acid, dartural acid and adipic acid.
- a dicarboxylic acid mixture and subject the resulting dicarboxylic acid mixture to a hydrogenation reaction to produce a diol mixture.
- the nitric acid content of the dicarboxylic acid mixture used in the present invention is not more than 3% by weight, preferably not more than 0.2% by weight, based on the total weight of succinic acid, daltaric acid and adipic acid. Preferably, the content is 0.05% by weight or less. Most preferably, the nitric acid in the dicarboxylic acid mixture has been completely removed. It is necessary to repeat the process using the ion exchange resin, so that the operation becomes complicated and not practical. The limit of the nitric acid content to the level of about 0.1 ppm is the limit in the processing usually used.
- nitric acid content of the dicarboxylic acid mixture is more than 3.% by weight, the activity of the hydrogenation catalyst for producing the diol mixture decreases over time, and the diol mixture cannot be stably obtained for a long period of time. .
- nitric acid affects the hydrogenation reaction, but it is believed that the presence of nitric acid causes the catalyst metal to be partially eluted, resulting in reduced catalytic activity.
- the metal is eluted by nitric acid depends on the atmosphere. For example, it is known that a passivation film is formed on the surface of stainless steel and that corrosion does not proceed even in the presence of nitric acid, but hydrogen exists under the hydrogenation reaction conditions used in the present invention. It is thought that the metal is eluted by nitric acid because the passivation film on the metal surface becomes unstable due to the reducing atmosphere.
- a method for removing nitric acid from the by-product aqueous solution obtained from the process for producing adipic acid a known method, for example, under normal pressure to 80 to 80 kPa, under reduced pressure of 80 to 80 kPa, One method is heating at 200 ° C.
- a method of removing by azeotropic distillation with water at 80 to 130 ° C under a reduced pressure of normal pressure to about 80 kPa there is a method of removing by azeotropic distillation with water at 80 to 130 ° C under a reduced pressure of normal pressure to about 80 kPa. In this case, if the amount of water is smaller than that of nitric acid, the concentration of nitric acid in the kettle after water is distilled off by azeotropic distillation will increase.
- Nitric acid concentration It is not necessarily a problem that the water content rises, but in order to continue azeotropic distillation, it is preferable to distill off nitric acid by azeotropic distillation while adding new water to the still.
- Another method is to remove nitric acid by heating at about 100 to 200 ° C., preferably at about 130 to 180 ° C. under almost normal pressure. In this case, nitric acid is removed by azeotropy with water).
- a method of removing using an anion exchange resin and the like can also be mentioned, and these methods can be used alone or in combination.
- the method of heating at 160 to 180 ° C for 1 minute to 1 hour is simple and preferable. Using this method, not only nitric acid but also a part of a compound having an oxygen-nitrogen bond, which will be described later, is decomposed and removed, particularly by heating to 160 to 180.
- the reason why the temperature range is divided into two stages is that the time for keeping the temperature at 100 to 130 ° C and the preferred time for keeping the temperature at 130 to 200 ° C are different.
- the method of removing with an anion exchange resin is also effective, but when the amount of nitric acid that needs to be removed is large, the amount of ion exchange resin required increases, and a great deal of labor is required for the regeneration treatment. Become. However, it is an effective method to remove trace amounts of nitric acid. In addition, when the nitric acid content is several weight% to about 10 weight%, hydroxides, carbonates, bicarbonates of alkaline metal and alkaline earth metal such as caustic soda, etc. Neutralize and remove nitric acid using You can also.
- nitric acid can be removed together with a compound having an oxygen-nitrogen bond by a reduction treatment.
- a by-product aqueous solution is used by using a reduction catalyst containing an active metal species containing at least one metal selected from the group consisting of metals of Groups 7 to 10 of the periodic table.
- nitric acid and a compound having an oxygen-nitrogen bond contained in the by-product aqueous solution can be removed by reduction and Z or decomposition.
- the conditions for the reduction treatment are not particularly limited, but the preferred treatment temperature is 50 to 200 ° C., and more preferably 1 to 200 ° C. 0 to 180.
- the hydrogen pressure used for the reduction treatment is preferably from 0.2 to 5 MPa, and more preferably from 1 to 4 MPa.
- the time required for the reduction treatment is several minutes to several tens of hours, preferably 10 minutes to 5 hours.
- Reduction catalysts for the purpose of removing nitric acid generally contain a hydrogenation reaction containing an active metal species containing at least one metal selected from the group consisting of metals of groups 7 to 10 of the periodic table. And at least one metal whose active metal species is selected from the group consisting of platinum, rhenium, palladium rhodium, nickel, iridium, and ruthenium Catalysts are preferred. Further, from the viewpoint of catalytic activity, a catalyst containing at least one metal whose active metal species is selected from the group consisting of platinum, rhenium, palladium, rhodium and ruthenium is more preferable. In view of durability, a catalyst containing platinum as the active metal species is most preferable.
- the “periodic table” refers to the periodic table proposed by the Inorganic Chemistry Subcommittee of the American Chemical Society in 1985.
- the reduction catalyst can be used by being supported on a carrier.
- a porous carrier such as activated carbon, diatomaceous earth, silica, alumina, titania, and zirconia can be used alone or in combination.
- a method for supporting the metal on the carrier a method generally used for preparing a supported catalyst such as an immersion method or an ion exchange method can be used.
- the raw material of the metal component used in the preparation of the reduction catalyst varies depending on the catalyst preparation method. Use mineral salts such as acid salts, sulfates and hydrochlorides, organic salts such as acetates, hydroxides, oxides, and organometallic compounds.
- the amount of the metal component to be carried is usually 0.5 to 50% by weight of the carrier as the metal.
- the reduction catalyst for removing nitric acid a hydrogenation catalyst containing an active metal species containing ruthenium and tin used for producing a diol mixture, which will be described in detail later, is used. You can.
- the catalyst used for the reduction treatment can be used for hydrogenation.
- reduction in activity due to the use of the catalyst for a long period of time may occur. Therefore, the reduction treatment and the hydrogenation reaction are usually performed using different catalysts.
- the amount of the reduction catalyst is 0.01 to 50 parts by weight with respect to 100 parts by weight of the by-product aqueous solution to be treated. It is preferable to select arbitrarily according to conditions such as processing temperature and processing pressure.
- the dicarboxylic acid mixture used in the present invention preferably further has a content of copper and vanadium of 10 ppm or less, respectively, based on the total weight of succinic acid, daltaric acid and adipic acid. More preferably, it is less than 5 ppm.
- the content of copper and vanadium in the present invention is the content of copper and vanadium as elements. Copper And vanadium are derived from oxidation catalysts for adipic acid production.
- the method for removing copper and vanadium contained in the by-product aqueous solution obtained during the production of adipic acid is not particularly limited, and a known method can be used.However, a method using a cation-exchange resin is simple, At the same time, it is preferable because the amount of waste generated as a by-product is small. Specifically, a by-product aqueous solution is obtained (or an ion-exchanged water is added to the obtained solid-state dicarboxylic acid mixture during purification to form an aqueous solution), and the solution is heated at room temperature to 100 ° C. at the following temperature. Copper and vanadium can be removed by contacting with ion exchange resin.
- cation exchange resin those having a functional group of a sulfonic acid group or a carboxyl group and having a parent structure of a styrene or methacrylyl group can be used. 100 to 100 parts by weight of dicarboxylic acid and 1 to 100 parts by weight of cation exchange resin. It can be mixed with stirring or contacted by a packed tower method.
- the dicarboxylic acid mixture used in the present invention preferably further has an iodide content of not more than 200 ppm, more preferably not more than 200 ppm based on the total weight of succinic acid, daltaric acid and adipic acid. It is 40 ppm or less, particularly preferably 2 O ppm or less.
- zeolite mixture is produced from a dicarboxylic acid mixture having a high zeolite content as a raw material, zeolite accumulates in the active metal species of the hydrogenation catalyst and reduces the surface area of the active metal species. The activity of the medium decreases.
- the limit of the commonly used treatment is to reduce the io content to about 0.2 ppm.
- the zeolite in the dicarboxylic acid mixture exists as a compound having a sulfate group or the like, but it is not always clear. Although the origin of the polymer is not clear, when a sulfonic acid-based cation exchange resin is used to remove copper and vanadium, the sulfonic acid group is eliminated or the polymer chain of the ion exchange resin is removed. It is considered that impurities including zeolite are eluted into the aqueous solution of the dicarboxylic acid mixture due to decomposition and the like. This idea is supported by the fact that the anion exchange resin can remove the dye.
- a method of bringing the by-product aqueous solution into contact with an anion exchange resin is effective.
- ion-exchanged water is added to the dicarboxylic acid mixture to form an aqueous solution of 5 to 50% by weight of dicarboxylic acid.
- the anion exchange resin a styrene-based or acryl-based resin having a quaternary ammonium salt as a functional group is preferable.
- a styrene-based or acryl-based weakly basic ion-exchange resin having a tertiary amine as a functional group can be used as desired.
- the method of using the anion-exchange resin is to stir and mix 1 to 100 parts by weight of the anion-exchange resin with 100 parts by weight of the dicarboxylic acid, or to contact them by a packed tower method. Can be used.
- the extinction coefficient at 365 nm of the aqueous solution in which the dicarboxylic acid mixture is dissolved in distilled water is preferably 0.3 or less, and more preferably 0.1 or less. Very good, especially preferred is less than 0.03.
- the extinction coefficient is a value represented by the following equation.
- E is the extinction coefficient at 355 nm
- A is the absorbance at room temperature of an aqueous solution of the dicarboxylic acid mixture dissolved in distilled water
- c is the solubility in 100 g of distilled water.
- Said dicarbo The weight (g) of the acid mixture, and b is the length (cm) of the cell used for measuring the absorbance.
- the absorption at 355 nm is not due to succinic, daltaric and adipic acids. Thus, this absorption is due to impurities contained in the dicarboxylic acid mixture. Although the present inventors have not yet specified the molecular structure of this impurity, they are described in the literature (Zh. Prikl. Khim. Leningrad Vol. 47, No. 4, pp. 862-865, 1974).
- the extinction coefficient is zero because there is no absorption by the dicarboxylic acid mixture which is the raw material of the dial mixture.However, the extinction coefficient depends on the activated carbon treatment and the anion exchange resin. Processing must be repeated, and the operation is complicated, which is not practical. The limit of the extinction coefficient of a commonly used treatment is to decrease to about 0.001.
- the anion-adsorbing substances are activated carbon, anion-exchange resin and liquid anion exchanger, and the liquid anion exchanger is a water-insoluble primary material having a molecular weight of 200 to 500, One or more amiins selected from secondary and tertiary amiins.
- a method for removing impurities using activated carbon for example, a by-product aqueous solution is obtained, and 1 to 20 parts by weight of powdered activated carbon or granular activated carbon is added to 100 parts by weight of dicarboxylic acid to form a by-product aqueous solution. After mixing and stirring for 5 minutes to 2 hours, the activated carbon can be filtered off.
- the above-described method for removing an iodide compound can be used as a method for removing impurities using an anion-exchange resin.
- a liquid anion exchanger when a liquid anion exchanger is used, 0.1 to 10% by weight of a liquid anion exchanger typified by tri-n—s-octylamine is added to a water-insoluble organic solvent.
- the adsorbed solution is prepared by mixing at an appropriate concentration, and the adsorbed solution is brought into contact with a by-product aqueous solution such that the liquid anion exchanger becomes 1 to 30% by weight based on the weight of dicarboxylic acid.
- the water-insoluble organic solvent specifically, carbon tetrachloride, perclene, trichlorne, liquid paraffin, and the like are appropriate.
- an extraction column or a mixer settler which is a usual liquid-liquid contacting device can be used.
- the dehydrated dicarboxylic acid mixture had a carbon number of 6 to 1 having a boiling point of 200 ⁇ or less at normal pressure.
- the extinction coefficient can also be reduced by adding the aromatic hydrocarbon of Step 4, heating to a temperature below the boiling point of the aromatic hydrocarbon, cooling the mixture to room temperature or lower, and filtering to collect the dicarboxylic acid mixture.
- aromatic hydrocarbons having 6 to 14 carbon atoms and a boiling point of 200: which can be used in this treatment include benzene, toluene, xylene, ethylbenzene, isopropylbenzene, and isopropylbenzene.
- examples include propylbenzene, trimethylbenzene and butylbenzene.
- benzene, toluene and xylene have low boiling points, and even if they remain in the dicarbonic acid mixture collected by filtration, they can be easily removed by a method such as heating under reduced pressure, which is preferable.
- the weight of the aromatic hydrocarbon used is preferably 0.5 to 20 times the total weight of succinic acid, daltaric acid and adipic acid.
- the effect of decolorization tends to increase as the amount used increases.However, when the total weight exceeds 20 times the total weight of succinic acid, daltaric acid, and adipic acid, the decolorizing effect almost reaches a plateau, and This is not preferred because it only increases the amount of aromatic hydrocarbons that must be treated.
- a coloring substance (a compound having an oxygen-nitrogen bond, which will be described later) can be obtained by the same treatment as the above-described reduction treatment for removing nitric acid. ) Can be removed. That is, the by-product aqueous solution is used in the presence of a reduction catalyst containing at least one metal selected from the group consisting of metals of Groups 7 to 10 of the periodic table as an active metal species. By contact with hydrogen gas, coloring substances can be removed by reduction and Z or decomposition.
- the content of the compound having an oxygen-nitrogen bond in the dicarboxylic acid mixture is calculated as the weight of nitric acid, and is 2, 2, OOO It is preferably at most ppm, more preferably at most 1,20 ppm.
- the content of the compound having an oxygen-nitrogen bond is determined by adding NaOH to an aqueous solution of dicarboxylic acid, heating the mixture, removing volatile components such as ammonia, and then adding a debarium alloy to a reduction treatment.
- This is a value obtained by quantifying the produced ammonia and converting it to the amount of nitric acid. Therefore, the compound having an oxygen-nitrogen bond also includes nitric acid.
- Some compounds having an oxygen-nitrogen bond other than nitric acid have an absorption at 355 nm, and these impurities are added by the oxidation reaction with nitric acid during the production of adipic acid. It is thought to be produced.
- the compound having an oxygen-nitrogen bond can be removed by the above-described method for removing nitric acid. That is, a method of heating at 80 to 200 under a reduced pressure of normal pressure to about 80 kPa and at least one kind selected from the group consisting of metals of Groups 7 to 10 of the periodic table. A method of performing a reduction treatment in the presence of a reduction catalyst containing an active metal species containing a metal can be used. According to the research conducted by the present inventors, a method of contacting activated carbon with a by-product aqueous solution is effective as a method for removing organic compounds other than nitric acid, particularly having a functional group containing an oxygen-nitrogen bond. It became clear that it was.
- the removal method using activated carbon the method described in the method for removing impurities having an absorption at 365 nm can be used.
- the dicarbonic acid mixture used as a raw material of the diol mixture is:
- the nitric acid content is 3% by weight or less based on the total weight of the dicarboxylic acid, and further impurities such as coloring substances including copper, vanadium, and a compound having an oxygen-nitrogen bond, which may hinder the hydrogenation reaction.
- First purification process (a) The by-product aqueous solution is heated at a temperature of 80 to 200 and a pressure lower than normal pressure to perform dehydration and denitrification. Water is added to the dehydrated and denitrated dicarboxylic acid mixture to obtain an aqueous solution of the denitrated dicarboxylic acid mixture, and
- Second purification process (a) The by-product aqueous solution is heated at a temperature of 80 to 130 ° C and a pressure of less than normal pressure, and then further heated at a temperature of 130 to 180 and normal pressure. Heating to obtain a mixture of dehydrated and denitrified dicarboxylic acids,
- step (e) adding an aromatic hydrocarbon having 6 to 14 carbon atoms having a boiling point of 200 or less at normal pressure to the denitrated dicarboxylic acid mixture obtained in step (d), Heating the mixture at a temperature below the boiling point of the aromatic hydrocarbons, then cooling, and
- the by-product aqueous solution is produced in the presence of a reduction catalyst containing an active metal species containing at least one metal selected from the group consisting of metals of Groups 7 to 10 of the periodic table.
- the dicarboxylic acid mixture is obtained in the form of an aqueous solution by contacting with hydrogen gas and reducing the compound having a nitric acid and oxygen-nitrogen bond contained in the by-product aqueous solution.
- nitric acid removal is preferably performed at the beginning of the purification process.
- a preferred method for performing nitric acid removal is to heat the by-product aqueous solution at a temperature of 80 to 200 ° C and a pressure lower than normal pressure. After heating for about 10 minutes to 3 hours at a temperature of 0 to 130 and a pressure lower than normal pressure, heating for a further 1 minute to 1 hour at a temperature of 130 to 180 and normal pressure Are mentioned.
- coloring substances including compounds having an oxygen-nitrogen bond can be removed at the same time, at least one metal selected from the group consisting of metals belonging to Groups 7 to 10 of the periodic table.
- a by-product aqueous solution is brought into contact with hydrogen gas in the presence of a reduction catalyst containing an active metal species containing the active metal species to reduce a compound having nitric acid and an oxygen-nitrogen bond contained in the by-product aqueous solution.
- the aqueous by-product solution is heated at a pressure equal to or lower than normal pressure, and further heated at a temperature of 130 to 18 Ot: and normal pressure to partially reduce the dicarboxylic acid mixture. More preferably, water is added to the partially denitrified dicarboxylic acid mixture to obtain a partially denitrated dicarboxylic acid mixture aqueous solution, and then subjected to reduction treatment. .
- a cation exchange resin it is preferable to remove copper and vanadium with a cation exchange resin after the nitric acid removal step.
- an aqueous solution of the denitrated dicarboxylic acid mixture is brought into contact with a cation exchange resin. If nitric acid is removed by heating in the nitric acid removing step, the denitrated dicarboxylic acid mixture can be obtained in the form of a solid.In that case, ion-exchanged water is added to the denitrified dicarboxylic acid mixture to reduce An aqueous solution of a 50% by weight denitrified dicarboxylic acid mixture is prepared, and then the cation exchange resin is brought into contact with the above aqueous solution.
- the dehydration and denitrification steps may be performed again as needed.
- Contacting the anion-adsorbing substance with an aqueous solution of dicarboxylic acid removes and decolorizes the iodide compound (that is, removes the coloring substance containing a compound having an oxygen-nitrogen bond). be able to.
- This step may be omitted if the dicarboxylic acid mixture during purification has a low content and / or has no coloring.
- the treatment with the anion-adsorbing substance is preferably performed after the treatment with the cation-exchange resin.
- the treatment with a cation exchange resin first increases the decolorizing effect of the treatment with an anion adsorbent. Further, by treating the dicarboxylic acid mixture in the middle of purification in this order, it becomes possible to remove the thio compound derived from the sulfonic acid type cation exchange resin.
- the purification step using activated carbon can be performed in a desired order after the nitric acid removal step.
- activated carbon By treatment with activated carbon, not only decolorization but also removal of compounds having an oxygen-nitrogen bond can be performed at the same time.Also, aromatic hydrocarbon is added to the denitrated dicarboxylic acid mixture, heated, cooled, and cooled. Then, the dicarboxylic acid mixture can be recovered by filtration. This step is effective for removing and decolorizing the dioxane, and by performing this step, a dicarboxylic acid mixture containing few impurities that hinder the hydrogenation reaction can be obtained.
- Treatment with aromatic hydrocarbons can be performed after denitrification and removal of copper and vanadium. By performing the treatment using the toxic substance together, a dicarboxylic acid mixture with less impurities can be obtained.
- a method of distillation under reduced pressure heating and a method of steam distillation under reduced pressure are also effective, and can be used in combination with the above-described methods.
- a method for removing each impurity may be appropriately combined, and the method for removing impurities contained in the by-product aqueous solution obtained in the adipic acid production process is almost completely removed.
- the amount of activated carbon used in step (2) can be increased as required without performing step (3) using a liquid anion exchanger.
- the present invention provides a method of purifying an aqueous by-product solution as described above. Water and hydrogen gas and a hydrogenation catalyst containing active metal species consisting of ruthenium and tin Subjecting the reaction to a hydrogenation reaction below to obtain a hydrogenation reaction solution containing a diol mixture including 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. This is the method characterized by this.
- the hydrogenation catalyst used in the present invention contains ruthenium and tin as active metal species.
- At least one metal selected from metals of group 7 of the periodic table and / or metals of group 8 of the periodic table other than ruthenium, and group 9 of the periodic table and A hydrogenation catalyst further containing at least one metal selected from the group consisting of Group 10 metals is preferred because of its high activity. Particularly preferred because of its high activity, it consists of metals of group 8 of the periodic table other than ruthenium, and metals of groups 9 and 10 of the periodic table, and at least 1 selected from the group Platinum is preferred as the species metal because of its particularly high activity.
- the hydrogenation catalyst used in the present invention may be a non-supported catalyst using no carrier or a supported catalyst using a carrier.
- a carrier for supporting the catalyst conventional porous carriers such as activated carbon, alumina, and silica can be used. Among these carriers, activated carbon, titania, and the like are used in view of acid resistance. And zirconia are preferred, more preferably activated carbon.
- the activated carbon either steam activated carbon or chemical activated carbon can be used. Depending on the type of reaction, granular activated carbon or powdered activated carbon is used. I can do it.
- the method for supporting the metal species on the support is not particularly limited, and a method generally used as a method for preparing a supported catalyst such as an immersion method or an ion exchange method can be applied.
- a method generally used as a method for preparing a supported catalyst such as an immersion method or an ion exchange method can be applied.
- the raw material compound of the metal species to be supported is dissolved in a solvent, for example, water to form an aqueous solution of the metal compound, and the separately prepared porous carrier is immersed in the solution to add the metal species to the carrier.
- the order of supporting each metal on the carrier is not particularly limited, and all metal species may be supported simultaneously or each metal species may be supported individually. If desired, each metal species may be carried on a plurality of occasions.
- the raw material of the metal species used in the preparation of the catalyst depends on the preparation method of the catalyst, but is usually a mineral acid salt such as a nitrate, a sulfate, a hydrochloride, an organic acid salt such as an acetate, a hydroxide, Oxides, organometallic compounds such as amine complexes and carbonyl complexes, and the like can be used.
- a mineral acid salt such as a nitrate, a sulfate, a hydrochloride
- an organic acid salt such as an acetate, a hydroxide
- Oxides, organometallic compounds such as amine complexes and carbonyl complexes, and the like can be used.
- Ruthenium raw materials are preferably ruthenium chloride, ruthenium bromide, ruthenium nitrate, ruthenium acetyl acetate, ruthenium carbonyl, ruthenium black, ruthenium powder, ruthenium oxide, nitrous nitrate Silrutam, ammonium oxydecaclodyruthenate, and the like.
- Examples of the raw material for tin include tin chloride ( ⁇ ), sodium stannate, and tin acetate ( ⁇ ).
- Raw materials for rhenium include: rhenium decacarbonyl (rhenium carbonyl), rhenium oxide, perrhenic acid, ammonium perrhenate, and salts.
- Rhenium chloride cyclopentene genyl rhenium tricarbonyl, and the like.
- Examples of the raw material for platinum include chloroplatinic acid, platinum nitrate, platinum acetyl acetate, platinum chloride, platinum bromide, and platinum cyanide.
- the loading amount of ruthenium and tin is 0.5 to 50% by weight, preferably 1 to 10% by weight, based on the carrier.
- the ratio of ruthenium to tin is preferably in the range of 1: 0.1 to 1: 2 in atomic ratio of ruthenium: tin, more preferably in the range of 1: 0.2 to 1: 1.3.
- the amount of the metal (the total amount of the metals in the case of plural kinds) is preferably in the range of 0.01 to 5 in atomic ratio to ruthenium, and more preferably in the range of 0.1 to 2. is there.
- the support supporting the metal species is dried, and then calcined and reduced as necessary to obtain a hydrogenation catalyst. Drying is usually carried out by keeping the carrier under reduced pressure at a temperature from room temperature to less than 200, or by flowing a dry gas such as nitrogen or air. The calcination is usually performed at a temperature of 200 to 600 for 1 to 24 hours while flowing nitrogen, air, and the like.
- the reduction may be performed by either liquid phase reduction or gas phase reduction. Normally, hydrogen is used as a reducing gas, and gas phase reduction is performed at a temperature of 200 to 500 ° C for 30 minutes to 24 hours.
- Unsupported hydrogenation catalysts that do not use a carrier are also metal
- the compound can be prepared by a method of reducing an aqueous solution of a compound with a reducing agent, or by reducing a solid containing an active metal species obtained by a coprecipitation method in a liquid phase or a gas phase.
- an unsupported catalyst it can be produced using the metal raw materials listed above.
- the ratio of ruthenium to tin is preferably such that the atomic ratio of ruthenium: tin is in the range of 1: 0.1 to 1: 2, more preferably 1: 0.2 to: L: 1.3. It is.
- the amount of the metal of the species is preferably in the range of 0.01 to 5 in atomic ratio to ruthenium, more preferably 0. : It is in the range of ⁇ 2.
- the metals of Group 7 of the periodic table represented by ruthenium and tin, and rhenium, and metals of Group 8 of the periodic table other than ruthenium or ruthenium, and Groups 9 and 1 of the periodic table Using a hydrogenation catalyst containing at least one metal selected from the group consisting of Group 0 metals, in the presence of water and hydrogen gas, including succinic acid, glutaric acid, and adipic acid; and A hydrogenation reaction of a dicarboxylic acid mixture having a nitric acid content of 3% by weight or less based on the total weight of succinic acid, glutaric acid and adipic acid is performed.
- Solvents such as alcohols and ethers may be added to the reaction system for hydrogenation, if desired, in addition to water.
- the amount of water present in the reaction system for hydrogenation depends on the temperature at which hydrogenation is performed.
- the amount of water in which the entire amount of the dicarboxylic acid mixture is dissolved is 0.3 to 100 parts by weight, preferably 1 to 20 parts by weight, per 1 part by weight of the dicarboxylic acid mixture. And more preferably 2 to 10 parts by weight.
- the temperature of the hydrogenation reaction is preferably from 100 to 300 t :, and more preferably from 130 to 270 ° C.
- the hydrogen pressure is between 1 and 25 MPa, more preferably between 5 and 20 MPa.
- the amount of the hydrogenation catalyst used is preferably from 0.001 to 10 parts by weight, more preferably from 0.01 to 1 part by weight, based on 1 part by weight of the dicarboxylic acid mixture. .
- the hydrogenation reaction may be carried out either continuously or batchwise, and the reaction may be carried out in either a liquid phase suspension reaction or a fixed bed flow reaction.
- Diols obtained by the production method of the present invention are useful as raw materials for polyester resins, urethane forms, urethane paints, adhesives and the like.
- a raw material of polyurethane it can be used as it is as a chain extender, and it can be used as a polycarbonate polyol / polyester polyol. It can also be used as a tosegment.
- 1, 4 Monobutanediol, 1,5-pentanediol and 1,6-hexanediol can be recovered.
- the method of recovery for example, it is possible to recover 1,4-monobutanediol and a mixture of 1,5-pentanediol and 1,6-hexanediol according to the following method. it can.
- the temperature of the hydrogenation reaction solution containing the diol mixture is adjusted to a temperature from room temperature to less than 100, and gas-liquid separation is performed at a pressure lower than normal pressure to remove hydrogen gas from the hydrogenation reaction solution.
- step (V) The remaining high-boiling mixture obtained in the step (i V) is subjected to further multi-stage distillation to obtain a mixture of 1,5-pentanediol and 1,6-hexanediol as a distillate. Get it.
- the hydrogen gas is removed by gas-liquid separation of the hydrogenation reaction solution containing the diol mixture and hydrogen gas.
- the hydrogenation reaction solution containing the diol mixture was cooled to a temperature from room temperature to less than 100. Thereafter, the pressure is reduced to a pressure at which water does not boil at normal pressure or at a cooling temperature, and the excess hydrogen used in the hydrogenation reaction and the reaction solution containing the diol mixture are separated.
- the gas-liquid separated hydrogen can be reused in the hydrogenation reaction again after removing trace amounts of carbon monoxide and carbon dioxide using an exclusion facility.
- the hydrogenation reaction solution from which the hydrogen gas has been removed is heated to 100 to 120 ° C under normal pressure, and most of the water and the cyclic ethers by-produced in the hydrogenation reaction are added.
- the bottom temperature is 130-: 19 Ot: and the bottom pressure is 5.5-7.0.
- the overhead temperature is 10 to 60
- the overhead pressure is 3.5 to 5.5 kPa
- the remaining water is set using a multistage distillation column with 5 to 15 stages.
- r-butyrolactone by-produced in the hydrogenation reaction is distilled off to obtain a purified diol mixture. It should be noted that, together with arbutyrolactone, trace amounts of pentanol and hexanol are also distilled off.
- the resulting purified diol mixture is subjected to multi-stage distillation to obtain 1,4-butanediol as a low boiling component.
- the conditions for distilling and separating 1,4-butane'diol include, for example, a multi-stage distillation column having 20 to 40 plates and a bottom temperature of 140 to 18 0 ° C, tower bottom pressure 4.0 ⁇ 7 kPa, tower top temperature 30 ⁇ 60 ° (:, top pressure 0.3 ⁇ 1.0 OkPa, and purified diol mixture Distillation and separation can be performed by feeding the mixture from the bottom to about 15 intermediate stages.
- the remaining high-boiling mixture obtained above is further subjected to multistage distillation to obtain a mixture of 1,5-pentanediol and 1,6-hexanediol as a distillate.
- a distillation column having 3 to 15 stages is used, and the bottom temperature is 180 to 220 X: the bottom pressure is 5.5 to 9.0 kPa, the top temperature is Is set to 140 to 180 ° C and the overhead pressure to 4.0 to 7.0 OkPa, and the liquid after the separation of 1,4-butanediol is supplied to the intermediate stage.
- a mixture of 1,5-pentenediol and 1,6-hexanediol is separated by distillation.
- the distillation separation method described above may be performed continuously or in a batch system.
- the purity of 1,4-butanediol obtained by the above separation / recovery process is 98.5% or more, and lactones, hydroxycarboxylic acids, monohydric alcohols and secondary ⁇ H It is preferable that the total content of the diol compound having a OH group and a primary OH group is less than 0.5% by weight '.
- Lactones are ⁇ —butyrolactone, (5—norrelactone, and ⁇ —force prolactone.
- Hydroxycarboxylic acids are hydroxybutyric acid. And hydroxyvaleric acid and hydroxycabronic acid.
- alcohols include propanol, butanol, pentanol, hexanol, etc., and diol compounds having a secondary ⁇ H group and a primary ⁇ H group
- diol compounds having a secondary ⁇ H group and a primary ⁇ H group For example, 1,3-butanediol, 1,4-pentanediol, 1,5-hexanediol and the like.
- 1,4-butanediol obtained by the production method of the present invention is used as a raw material of polyurethan, lactones, hydroxycarboxylic acids, monohydric alcohols, It is preferable that the total content of the diol compound having a secondary OH group and a primary OH group is 0.5% by weight or less. When such an impurity is present in an amount exceeding 0.5% by weight, the polymerization reactivity of 1,4-butanediol is deteriorated, and it becomes difficult to obtain a high-molecular-weight polyurethan. . In addition, lactones and hydroxycarboxylic acids adversely affect the physical properties of polyurethane such as hydrolysis resistance.
- the mixture of 1,5-pentanediol and 1,6-hexanediol obtained by the above-mentioned separation / recovery step is mainly composed of 1,5-pentanediol. Investigation of its impurities revealed that it did not substantially contain 1,5-hexanediol or 1,4-dihydroxycyclohexane, which was contained in conventional 1,5-pentanediol. It was clear. Specifically, conventional 1,5-pentenediol contains 1,5-hexanediol and 1,4-dihydroxycyclohexane each containing 0.2% by weight or more. , These impurities contained in the mixture of 1,5-pentanediol and 1,6-hexanediol of the present invention are each 0.1% by weight or less.
- 1,5-pentanediol has been used to produce dextran hexanone and / or cyclan hexanol by aerial oxidation of cyclohexane to produce daltaric acid, adipic acid, and 6-hydroxy hexanol. It is manufactured using a carboxylic acid mixture containing droxyca bronoic acid as a raw material. Specifically, after esterifying a carboxylic acid mixture containing daltaric acid, adipic acid, and 6-hydroxycabronic acid, hydrogenation using a copper-based catalyst was performed to give 1,5-pentanediol and 1,5-pentanediol.
- 1,5-pentanedidiol obtained by the conventional method contains 0.2 to 1% by weight of 1,5-hexanediol and 1,4-dihydroxycyclohexane, respectively.
- 1,5-Hexanediol is a diol having a secondary ⁇ H group and a primary OH group. The 1,5-pentandiol containing the same is used as a raw material for polycarbonate diols and polyester polyols.
- the secondary 0 H group of 1,5-hexanediol becomes a terminal group of the polyol due to its low reactivity.
- a urethanization reaction is performed using such a polyol, there have been problems such as a low polymerization rate and an insufficient molecular weight.
- 1,5-pentane containing 1,5-hexanediol A similar problem also occurred when diol was used directly as a chain extender in the production of polyurethane.
- 1,4-dihydroxycyclohexane has low reactivity and unreacted two ⁇ H groups of 1,4-dihydroxycyclohexane are all secondary ⁇ H groups. It is not preferable because it remains in the polycarbonate diol as it is.
- a mixture of 1,5-pentenediol and 1,6-hexanediol obtained by the production method of the present invention contains 1,5-hexanediol and 1,4-dihydroxycyclohexane. Since it is not substantially contained, it is suitable as a raw material for a polyurethane chain extender or a polycarbonate diol or a polyester polyol which is a soft segment.
- the copolymerized polycarbonate diol obtained from 1,5-pentanediol and 1,6-hexanediol Japanese Patent Publication No. 5-0926648
- Thermoplastic polyurethane Japanese Patent Publication No.
- thermoplastic polycarbonate obtained by using a polycarbonate diol obtained only from 1,6-hexanediol.
- a mixture of 1,5-pentanediol and 1,6-hexanediol obtained by the production method of the present invention is suitable as a raw material for copolymerized polycarbonate dial.
- a sample solution with a dicarboxylic acid concentration of 2% by weight was prepared (even in the case of a by-product aqueous solution, a sample solution with a dicarbonic acid concentration of 2% by weight was prepared). It was subjected to high-performance liquid chromatography (HPLC) under the conditions. From the obtained analytical values, the nitric acid content relative to the total weight of succinic acid, daltaric acid and adipic acid was determined.
- a sample solution having a dicarboxylic acid concentration of 10% by weight was prepared using ion-exchanged water.
- the sample solution was analyzed using an inductively coupled plasma emission spectrometer (ICP) (manufactured by JOB IN YVON EMISSION Instrument SA, USA).
- ICP inductively coupled plasma emission spectrometer
- the copper content and the vanadium content based on the total weight of succinic acid, dartalic acid and adipic acid were analyzed. The amount and the content were determined.
- Solid dicarboxylic acid mixture 0. 1 8 in distilled water 1 0 8 dissolve to obtain a sample solution.
- a spectrophotometer manufactured by Shimadzu Corporation, Japan
- the absorbance of the sample solution at 365 nm was measured at room temperature using a 1 cm long cell. If the absorbance of the sample solution is less than 0.001, prepare a sample solution in which the concentration of the dicarboxylic acid mixture is 10 times (that is, 1 g of the dicarboxylic acid mixture is dissolved in 10 g of distilled water). The absorbance was measured again.
- the extinction coefficient at 365 nm was calculated from the absorbance according to the following equation.
- E is the extinction coefficient at 355 nm
- A is the absorption at room temperature of an aqueous solution obtained by dissolving a dicarboxylic acid mixture in distilled water.
- c is the weight (g) of the dicarboxylic acid mixture dissolved in 100 g of distilled water
- b is the length (cm) of the cell used for measuring the absorbance.
- An aqueous solution of a dicarboxylic acid mixture having an arbitrary concentration is prepared, and about 50% of an aqueous solution of 1 ⁇ 3 ⁇ 11 is added to the aqueous solution of the dicarboxylic acid mixture at a volume ratio of 13 to 2 times the volume of LZ. Approximately the same amount of methanol as the NaOH aqueous solution was added. The resulting mixture was heated for about 1 hour to reflux methanol. Thereafter, methanol was distilled off, and a basic substance was distilled out together with methanol. An appropriate amount of debar alloy was added to the remaining aqueous solution of dicarboxylic acid, and further methanol was added.
- the aqueous solution of the dicarboxylic acid mixture was added in a volume of 1/3 to 1 times 2 volumes, and heated again to reflux methanol for 1 hour. Thereafter, the ammonia was distilled off together with methanol, and the generated methanol and the ammonia contained therein were subjected to neutralization titration with dilute hydrochloric acid to quantify the generated ammonia. From the quantified amount of ammonia, the compound having an oxygen-nitrogen bond was converted to the weight of nitric acid, and the content of the compound having an oxygen-nitrogen bond relative to the total weight of succinic acid, daltaric acid and adipic acid was determined.
- diol mixture was appropriately diluted with dioxane so that the concentration of the diol mixture was about 1% by weight.
- diethylene darikole getyl ether was added as an internal standard substance so as to have a concentration of about 1% by weight to prepare a sample solution.
- This sample solution was subjected to gas chromatography (GC) under the following conditions, and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,4-butanediol in the diol mixture were used. By-products were analyzed.
- the yield of the diol mixture relative to the dicarbonic acid mixture used as a raw material was calculated.
- Example 1 A hydrogenation catalyst comprising 5% by weight of platinum supported on activated carbon was obtained.
- the above operation was performed three times in total, and 5,000 g of the obtained by-product aqueous solution was heated under normal pressure at about 120 ⁇ for 1 hour to recover most of water and nitric acid.
- Ion exchange water was added to the remaining dicarboxylic acid to obtain an aqueous solution having a water content of 67% by weight.
- 100 g of a sulfonic acid-based cation exchange resin having styrene as a parent structure (trade name: Amberlite IR120B) (manufactured by Organo Corporation, Japan) is added, and the mixture is left at room temperature for 2 hours.
- the mixture was stirred gently to recover copper and vanadium as oxidation catalysts, and then filtered to remove the ion-exchange resin to obtain a by-product aqueous solution after the recovery of nitric acid and the oxidation catalyst.
- the obtained by-product aqueous solution contained 67% by weight of water, and was analyzed by HPLC to have 7% by weight of succinic acid, 18% by weight of glutaric acid, 5% by weight of adipic acid, and 3% by weight of nitric acid. (However, it was confirmed that the nitric acid content was 10% by weight based on the total weight of succinic acid, daltaric acid, and adipic acid).
- the resulting dicarboxylic acid mixture was analyzed by HPLC, and as a result, the composition of the dicarboxylic acid mixture was 23% by weight of succinic acid, 60% by weight of daltaric acid, and 17% by weight of adipic acid.
- the nitric acid content is 0.1% by weight, the copper content, vanadium content and
- the biomass content was 6 ppm, 2111 and 5111, respectively. Further, the extinction coefficient at 365 nm was 0.085, and the content of the compound having an oxygen-nitrogen bond was 1,136 ppm.
- Cyclohexanol was oxidized with nitric acid in the same manner as in Example 1 to obtain an aqueous reaction solution containing succinic acid, daltaric acid and adipic acid.
- the adipic acid contained in the obtained reaction solution was precipitated, and the precipitated crystals were isolated to obtain a by-product aqueous solution.
- the above by-product aqueous solution (5,000 g) was heated under normal pressure at about 120 for 1 hour, and further heated at 170 to 175 for 30 minutes with stirring to dehydrate and remove the dicarboxylic acid mixture. Nitric acid was performed. Ion exchange water was added to the dehydrated and denitrified dicarboxylic acid mixture obtained after cooling to obtain an aqueous solution having a water content of 70% by weight. To this aqueous solution was added 10 g of a sulfonic acid-based ion-exchange resin having styrene as a parent structure (trade name: Amberlite IR120B) (manufactured by Organo Corporation, Japan), and the mixture was added at room temperature.
- a sulfonic acid-based ion-exchange resin having styrene as a parent structure
- the copper and vanadium were removed by stirring. Thereafter, the mixture was filtered to remove the ion-exchange resin, thereby obtaining an aqueous solution of a dicarboxylic acid mixture.
- the obtained aqueous solution of the dicarboxylic acid mixture was 70% water, 7% by weight of succinic acid, 18% by weight of daltaric acid, and 5% by weight of adipic acid.
- the nitric acid content was 0.17% by weight, and the copper, vanadium, and io content were 31 ppm, 20 ppm, and 3 ppm, respectively. Further, the extinction coefficient at 365 ⁇ m was 0.114, and the content of the compound having an oxygen-nitrogen bond was 1,143 ppm.
- Example 1 A hydrogenation reaction was carried out in the same manner as in Example 1 except that the above aqueous solution of the dicarboxylic acid mixture was used instead of the dicarboxylic acid mixture and water used in Example 1, to produce a diol mixture. This was performed 7 times in total, and the activity retention rate was determined. Table 1 shows the results. Comparative Example 1
- a diol mixture was produced using the by-product aqueous solution used in the preparation of the dicarboxylic acid mixture in Example 1 as a raw material of the diol mixture.
- the composition of the by-product aqueous solution used as a raw material was as follows: water 67% by weight, conodic acid 7% by weight, glutaric acid 18% by weight, adipic acid 5% by weight, nitric acid 3% by weight (dicarboxylic acid For the total weight of 10% by weight).
- the copper, vanadium and io content were 6 ppm, 201 and 5111, respectively. Further, the extinction coefficient at 35511111 was 0.051, and the content of the compound having an oxygen-nitrogen bond was 1,147 ppm.
- a hydrogen addition reaction was carried out in the same manner as in Example 1 except that 15.0 g of the by-product aqueous solution was used instead of the dicarboxylic acid mixture and water used in Example 1. After the completion of the reaction, only the hydrogenation reaction solution containing the diol mixture was extracted while the catalyst was kept in the autoclave. When the diol mixture contained in the hydrogenation reaction solution was analyzed by gas chromatography, the yields of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol were found to be 45%. %, 73% and 72%.
- a dicarboxylic acid mixture was prepared using the by-product aqueous solution obtained from the adipic acid production process after isolating adipic acid.
- the composition of the by-product aqueous solution used was 55% by weight of water and 19% by weight of daltaric acid. %, Kono, citric acid 7% by weight, adipic acid 11% by weight, and nitric acid 6% by weight.
- the copper, vanadium and io content were 0.6% by weight, 0.4% by weight and 340 ppm, respectively.
- the extinction coefficient at 35511 was 1.460, and the content of the compound having an oxygen-nitrogen bond was found to be 7,300 ppm.
- 1,000 g of the by-product aqueous solution was heated at about 120 ° C. for 1 hour under normal pressure while stirring in a beaker, and further heated at 170 to 175: 3 for 3 hours.
- the mixture was heated with stirring for 0 minutes to dehydrate and denitrate the dicarboxylic acid mixture.
- the weight of the dehydrated and denitrified dicarboxylic acid obtained after cooling was 380. This was made into a 38% by weight aqueous solution with ion-exchanged water, and insoluble substances were filtered off.
- the dicarboxylic acid mixture was 35% by weight of the aqueous solution, and the composition of the dicarboxylic acid mixture was 20% by weight of succinic acid, 50% by weight of daltalic acid, Adipic acid was 30% by weight.
- the nitric acid content was 0.03% by weight, and the copper content, vanadium content and zeolite content were 4 ppm, 4 ppm and 1 ppm, respectively.
- the extinction coefficient at 365 5 111 is 0.014, and the content of the compound having an oxygen-nitrogen bond is 1,083 ppm.
- the hydrogenation reaction was performed at this pressure for 18 hours. After the completion of the reaction, only the hydrogenation reaction mixture containing the mixture of diols was extracted while leaving the catalyst in the autoclave, and the diol mixture contained in the hydrogenation reaction mixture was analyzed by gas chromatography.
- a sulfonic acid-based cation exchange resin having styrene as a base structure (trade name: Amberlite IR120B) (manufactured by Organo Corporation, Japan) is added, and room temperature is added. The mixture was stirred gently for 3 hours to remove copper and vanadium. Thereafter, the mixture was filtered to remove the ion-exchange resin, and 100 g of powdered activated carbon was added to the obtained filtrate, followed by stirring at room temperature for 3 hours.
- a quaternary ammonium salt-type anion-exchange resin having a styrene matrix structure (trade name: Amber Light IRA900) (Japan) And 300 g of Organo Co., Ltd.) was added, and the mixture was stirred gently at room temperature for 3 hours to remove the water. Thereafter, the mixture was filtered to remove the ion exchange resin, thereby obtaining an aqueous solution of a dicarboxylic acid mixture.
- the dicarboxylic acid mixture was 35% by weight of the aqueous solution.
- the composition of the dicarboxylic acid mixture was 20% by weight of succinic acid, 50% by weight of daltaric acid, and 30% by weight of adipic acid.
- the nitric acid content was 0.03% by weight, and the copper, vanadium, and zeolite contents were 4 ppm, 4 ppm, and 1 ppm, respectively.
- the extinction coefficient at 3551111 was 0.010, and the content of the compound having an oxygen-nitrogen bond was 653 ppm.
- Example 7 A hydrogenation reaction was carried out in the same manner as in Example 1 except that the prepared aqueous solution of the dicarboxylic acid mixture (16.lg) was used instead of the dicarboxylic acid mixture and water used in Example 1, to produce a diol mixture. did. The production of the diol mixture was repeated 10 times, and the activity retention was determined. Table 2 shows the results.
- Example 7 the prepared aqueous solution of the dicarboxylic acid mixture (16.lg) was used instead of the dicarboxylic acid mixture and water used in Example 1, to produce a diol mixture. did. The production of the diol mixture was repeated 10 times, and the activity retention was determined. Table 2 shows the results. Example 7
- a dicarboxylic acid mixture was prepared using the same by-product aqueous solution as in Example 4.
- a sulfonic acid-based cation-exchange resin having styrene as a parent structure (trade name: Amberlite IR120B) (manufactured by Organo Corporation, Japan).
- the mixture was stirred gently at room temperature for 3 hours to remove copper and vanadium. Thereafter, the solution was filtered to remove the ion-exchange resin, thereby obtaining a filtrate containing dicarboxylic acid.
- the obtained filtrate was heated at about 120 for 1 hour while stirring in a beaker for 1 hour to distill off water.After cooling, 3,000 g of xylene was added thereto and a suspension containing dicarboxylic acid was added. A liquid was obtained.
- the resulting suspension was heated to 80 ° C for 20 minutes with vigorous stirring. After cooling with stirring, the denitrated dicarboxylic acid mixture was filtered off. The resulting dicarboxylic acid mixture was kept under vacuum at 60 to remove xylene, yielding 361 g of dicarboxylic acid mixture.
- the resulting dicarboxylic acid mixture was analyzed by HPLC. As a result, the composition of the dicarboxylic acid mixture was 20% by weight of succinic acid, 50% by weight of dallic acid, and 30% by weight of adipic acid. The nitric acid content was 0.02% by weight, and the copper, vanadium and io content were 4 ppm, 4 ppm and 10 ppm, respectively.
- a sulfonic acid-based cation exchange resin having styrene as a parent structure (trade name: Amberlite IR120B) (manufactured by Organo Corporation, Japan), and added 800 g.
- the mixture was stirred gently for 3 hours to remove copper and vanadium. Thereafter, the solution was filtered to remove the ion-exchange resin to obtain an aqueous solution of a dicarboxylic acid mixture.
- the aqueous solution of the obtained dicarboxylic acid mixture was analyzed by HPLC.
- the dicarboxylic acid mixture was 35% by weight of the aqueous solution, and the composition of the dicarboxylic acid mixture was 20% by weight of succinic acid and 50% by weight of daltalic acid.
- the content of adipic acid was 30% by weight.
- the nitric acid content was 0.03% by weight, and the copper, vanadium, and zeolite contents were 3 ppm, 1 pm, and 18 ppm, respectively.
- the extinction coefficient of [355] 1111 was 1.437, and the content of the compound having an oxygen-nitrogen bond was 5,600 ppm.
- a 12-stage multistage distillation column was used, under the conditions of a bottom temperature of 160 :, a bottom pressure of 6 kPa, a top temperature of 25 :, and a top pressure of 3.5 kPa. Then, water and a mixture of carpyllactone, pentanole and hexanol, which were by-produced in the hydrogenation reaction, were distilled off to obtain a purified diol mixture.
- the resulting purified diol mixture was subjected to the following multi-stage distillation.
- a 35-stage multi-stage distillation column was used, at a bottom temperature of 180 :, a bottom pressure of 12 kPa, a top temperature of 95 ", and a top pressure of 3 kPa.
- Multi-stage distillation to reduce 1,4-butanediol to low boiling point Collected as a component.
- the recovered 1,4-butanediol weighed 238 g, was analyzed by gas chromatography to have a purity of 98.5%, and the impurity was 1,5-pentanediol. That was confirmed. No lactones were included.
- the high-boiling mixture remaining after the recovery of the 1,4-butanediol was subjected to multistage distillation.
- the multi-stage distillation uses a 7-stage multi-stage distillation column under the conditions of a bottom temperature of 200, a bottom pressure of 7 kPa, a top temperature of 163 ° C, and a top pressure of 6 kPa.
- a mixture of 1,5-pentanediol and 1,6-hexanediol was recovered as a fraction.
- the recovered mixture of 1,5_pentanediol and 1,6-hexanediol was 8666 g, and the purity was 99.8% based on analysis by gas chromatography. Thus, it was confirmed that the impurity was 1,4-butanediol. 1,5-Hexanediol and 1,4-dihydroxycyclohexane were not contained.
- the adipic acid obtained in the adipic acid production process was isolated, and a dicarbonic acid mixture was prepared using a by-product aqueous solution after nitric acid and a catalyst were also recovered.
- the composition of the aqueous by-product solution used was The content was 19% by weight of phosphoric acid, 6% by weight of succinic acid, 5% by weight of adipic acid, and 4.1% by weight of nitric acid.
- the copper, vanadium and io content were 7 ppm, 5 ppm and 230 ppm, respectively. Further, the content of the compound having an oxygen-nitrogen bond was 6,640 ppm, and the balance was water.
- the extinction coefficient at 365 nm was 0.79.
- the composition of the resulting dicarboxylic acid mixture was 19% by weight of daltaric acid, 6% by weight of cono, citric acid and 5% by weight of adipic acid.
- the nitric acid content was 0.036% by weight, and the copper, vanadium and io content were 7 ppm, 5 ppm and 170 ppm, respectively. Further, the extinction coefficient at 365 nm was 0.043.
- ⁇ Production of diol mixture by hydrogenation reaction> The procedure of Example 1 was repeated except that 15.0 g of the prepared aqueous solution of the dicarboxylic acid mixture was used instead of the dicarboxylic acid mixture and water used in Example 1. A hydrogenation reaction was performed to produce a diol mixture. Production of the diol mixture was performed a total of 10 times, and the activity retention rate was determined. Table 3 shows the results.
- Example 1 1 The procedure of Example 1 was repeated except that 15.0 g of the prepared aqueous solution of the dicarboxy
- a dicarboxylic acid mixture was prepared using the same by-product aqueous solution as used in Example 10.
- the composition of the obtained dicarboxylic acid mixture was 19% by weight of glutaric acid, 6% by weight of cono, citric acid, and 5% by weight of adipic acid.
- the nitric acid content was 0.031% by weight, and the copper, vanadium and io content were 3 ppm, 3 ppm and 3 ppm, respectively. It was 180 ppm. Further, the extinction coefficient at 365 nm was 0.040.
- Example 1 2 A hydrogenation reaction was carried out in the same manner as in Example 1 except that 15.0 g of the prepared aqueous solution of the dicarboxylic acid mixture was used instead of the dicarboxylic acid mixture and water used in Example 1, and the diol mixture was used. Manufactured. Production of the diol mixture was performed a total of 10 times, and the activity retention rate was determined. Table 3 shows the results.
- Example 1 2 A hydrogenation reaction was carried out in the same manner as in Example 1 except that 15.0 g of the prepared aqueous solution of the dicarboxylic acid mixture was used instead of the dicarboxylic acid mixture and water used in Example 1, and the diol mixture was used. Manufactured. Production of the diol mixture was performed a total of 10 times, and the activity retention rate was determined. Table 3 shows the results.
- Example 1 2 A hydrogenation reaction was carried out in the same manner as in Example 1 except that 15.0 g of the prepared aqueous solution of the dicarboxylic acid mixture was
- a dicarboxylic acid mixture was prepared as follows.
- the reduction treatment was performed in the same manner as in Example 10 except that the temperature at which the reduction treatment was performed was 60: the hydrogen pressure was 2.0 MPa, and the treatment time was 6 hours. After the completion of the reduction treatment, the catalyst was separated to obtain an aqueous solution of a dicarboxylic acid mixture.
- the composition of the obtained dicarboxylic acid mixture was 19% by weight of glutaric acid, 6% by weight of succinic acid, and 5% by weight of adipic acid.
- the nitric acid content was 0.18% by weight, and the copper, vanadium and io content were 7 ppm, 5 ppm and 1 ppm, respectively. It was 60 ppm. Further, the extinction coefficient at 365 nm was 0.061.
- Example 13 A hydrogenation reaction was carried out in the same manner as in Example 1 except that 15.0 g of the prepared aqueous solution of the dicarboxylic acid mixture was used instead of the dicarboxylic acid mixture and water used in Example 1, and the diol mixture was used. Was manufactured. The production of the diol mixture was repeated 10 times, and the activity retention was determined. Table 3 shows the results.
- Example 13 A hydrogenation reaction was carried out in the same manner as in Example 1 except that 15.0 g of the prepared aqueous solution of the dicarboxylic acid mixture was used instead of the dicarboxylic acid mixture and water used in Example 1, and the diol mixture was used. Was manufactured. The production of the diol mixture was repeated 10 times, and the activity retention was determined. Table 3 shows the results. Example 13
- a dicarboxylic acid mixture was prepared as follows.
- Sulfonic acid-based cation exchange resin product name: Amberlite IR120B having a parent structure of styrene in 500 g of by-product aqueous solution (organo Co., Ltd., Japan) 120 g was added and stirred gently at room temperature for 3 hours to remove copper and vanadium. Then, the solution is filtered to remove the ion exchange resin, and the obtained by-product aqueous solution is used as a catalyst. Ruthenium catalyst (5% by weight supported on activated carbon) (Nippon Chemcat Co., Ltd., Japan) The same reduction treatment as in Example 10 was carried out, except that was used. After the reduction process, the catalyst is separated Separation gave an aqueous solution of the dicarboxylic acid mixture.
- the composition of the obtained dicarboxylic acid mixture was 19% by weight of daltaric acid, 6% by weight of cono, citric acid, and 5% by weight of adipic acid.
- the nitric acid content was 0.073% by weight, and the copper, vanadium and io content were 5 ppm, 5 ppm, and 190 ppm, respectively. Further, the extinction coefficient at 365 nm was 0.038.
- Example 14 A hydrogenation reaction was carried out in the same manner as in Example 1 except that the prepared aqueous solution of dicarboxylic acid mixture (15.Og) was used instead of the dicarboxylic acid mixture and water used in Example 1, and the diol mixture was obtained. Manufactured. Production of the diol mixture was performed a total of 10 times, and the activity retention rate was determined. Table 3 shows the results.
- Example 14 the prepared aqueous solution of dicarboxylic acid mixture (15.Og) was used instead of the dicarboxylic acid mixture and water used in Example 1, and the diol mixture was obtained. Manufactured. Production of the diol mixture was performed a total of 10 times, and the activity retention rate was determined. Table 3 shows the results. Example 14
- a dicarboxylic acid mixture was prepared using the same aqueous by-product solution used in Example 10.
- the composition of the by-product aqueous solution used was 19% by weight of daltaric acid, 6% by weight of succinic acid, 5% by weight of adipic acid, and 4.1% by weight of nitric acid. Furthermore, the extinction coefficient at 365 nm is 0.79, indicating that the compound has an oxygen-nitrogen bond. The content of the substance was 6,640 ppm.
- 1,000 g of the by-product aqueous solution is heated at about 120 ° C for 1 hour under normal pressure while stirring in a beaker, and further stirred at 170 to 175 ° C for 30 minutes.
- the mixture was heated to dehydrate and denitrate the dicarboxylic acid mixture.
- the weight of the dehydrated and denitrified dicarboxylic acid mixture obtained after cooling was 300 g, and this was made into a 30% by weight aqueous solution with ion-exchanged water.
- 0.15 g of the ruthenium catalyst used in Example 13 was placed in a Hastelloy 100 ml capacity autoclave equipped with an electromagnetic induction type stirrer. I was charged with it.
- the autoclave After replacing the inside of the autoclave with nitrogen, it was further replaced with hydrogen, and hydrogen was injected so that the pressure became 1 MPa at room temperature. The temperature was raised to 140 so that the hydrogen pressure of the autoclave was 1.5 MPa. At this pressure, the remaining compounds having nitric acid and oxygen-nitrogen bonds were reduced for 4 hours. After the completion of the reduction treatment, the catalyst was separated to obtain an aqueous solution of a dicarboxylic acid mixture.
- the composition of the obtained dicarboxylic acid mixture was 19% by weight of daltaric acid, 6% by weight of conodic acid, and 5% by weight of adipic acid.
- the nitric acid content was 0.0005% by weight, and the copper, vanadium and io content were 7 ppm, 5 ppm and 160 ppm, respectively. Further, the extinction coefficient at 365 nm was 0.021.
- succinic acid, daltaric acid, and adipic acid which are obtained from a production process of adipic acid, which have hardly been used for purposes other than solvents, are included.
- 1,4-butanediol and 1,5-pentanediol can be obtained by hydrogenating the dicarboxylic acid without converting it to an ester.
- a diol mixture containing 1,6-hexanediol can be produced stably for a long period of time.
- the diols obtained by the method of the present invention are useful as raw materials for polyurethanes and polyesters.
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00971776.0A EP1243573B1 (en) | 1999-11-05 | 2000-11-02 | Process for the preparation of diol mixtures |
JP2001536494A JP4683807B2 (ja) | 1999-11-05 | 2000-11-02 | ジオール混合物の製造方法 |
US10/129,143 US6706932B1 (en) | 1999-11-05 | 2000-11-02 | Process for the preparation of diol mixtures |
AU10557/01A AU1055701A (en) | 1999-11-05 | 2000-11-02 | Process for the preparation of diol mixtures |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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JP11-315906 | 1999-11-05 | ||
JP31590699 | 1999-11-05 | ||
JP2000014402 | 2000-01-24 | ||
JP2000-14402 | 2000-01-24 | ||
JP2000-129857 | 2000-04-28 | ||
JP2000129857 | 2000-04-28 |
Publications (1)
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WO2001034543A1 true WO2001034543A1 (fr) | 2001-05-17 |
Family
ID=27339504
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PCT/JP2000/007757 WO2001034543A1 (fr) | 1999-11-05 | 2000-11-02 | Procede servant a preparer des melanges de diols |
Country Status (8)
Country | Link |
---|---|
US (1) | US6706932B1 (ja) |
EP (1) | EP1243573B1 (ja) |
JP (1) | JP4683807B2 (ja) |
KR (1) | KR100546986B1 (ja) |
CN (1) | CN1224597C (ja) |
AU (1) | AU1055701A (ja) |
TW (1) | TW538029B (ja) |
WO (1) | WO2001034543A1 (ja) |
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WO2005051875A1 (en) | 2003-10-31 | 2005-06-09 | Davy Process Technology Limited | Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof |
US7005495B2 (en) * | 2000-05-24 | 2006-02-28 | Asahi Kasei Kabushiki Kaisha | Polycarbonate diol having high proportion of primary terminal OH |
JP2007507502A (ja) * | 2003-09-30 | 2007-03-29 | インヴィスタ テクノロジー エスアエルエル | アジピン酸の乾燥 |
WO2009063767A1 (ja) * | 2007-11-16 | 2009-05-22 | Asahi Kasei Chemicals Corporation | ポリカーボネートジオール |
WO2009063768A1 (ja) * | 2007-11-16 | 2009-05-22 | Asahi Kasei Chemicals Corporation | 反応の安定化が容易なポリカーボネートジオール |
JP2013512210A (ja) * | 2009-11-26 | 2013-04-11 | ビーエーエスエフ ソシエタス・ヨーロピア | 1,6−ヘキサンジオールの製造方法 |
JP2018502857A (ja) * | 2015-01-09 | 2018-02-01 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | テトラヒドロフラン、1,4−ブタンジオール又はγ−ブチロラクトンの製造方法 |
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US9108895B2 (en) | 2012-10-26 | 2015-08-18 | Eastman Chemical Company | Promoted ruthenium catalyst for the improved hydrogenation of carboxylic acids to the corresponding alcohols |
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KR102048986B1 (ko) * | 2018-03-22 | 2019-11-26 | 표상현 | ε-카프로락톤의 제조 방법 |
CN110963887B (zh) * | 2018-09-30 | 2022-10-28 | 中国石油化工股份有限公司 | 1,6-己二酸直接制备1,6-己二醇固定床反应工艺 |
KR20220110945A (ko) * | 2021-02-01 | 2022-08-09 | 한화솔루션 주식회사 | 이종금속 수소화 촉매의 제조 방법 |
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- 2000-11-02 EP EP00971776.0A patent/EP1243573B1/en not_active Expired - Lifetime
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US7005495B2 (en) * | 2000-05-24 | 2006-02-28 | Asahi Kasei Kabushiki Kaisha | Polycarbonate diol having high proportion of primary terminal OH |
JP2007507502A (ja) * | 2003-09-30 | 2007-03-29 | インヴィスタ テクノロジー エスアエルエル | アジピン酸の乾燥 |
WO2005051875A1 (en) | 2003-10-31 | 2005-06-09 | Davy Process Technology Limited | Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof |
US7498450B2 (en) | 2003-10-31 | 2009-03-03 | Davy Process Technology Limited | Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof |
US8168728B2 (en) | 2007-11-16 | 2012-05-01 | Asahi Kasei Chemicals Corporation | Polycarbonate diol with ease of reaction stabilization |
WO2009063768A1 (ja) * | 2007-11-16 | 2009-05-22 | Asahi Kasei Chemicals Corporation | 反応の安定化が容易なポリカーボネートジオール |
WO2009063767A1 (ja) * | 2007-11-16 | 2009-05-22 | Asahi Kasei Chemicals Corporation | ポリカーボネートジオール |
JP5123950B2 (ja) * | 2007-11-16 | 2013-01-23 | 旭化成ケミカルズ株式会社 | ポリカーボネートジオール |
JP5132686B2 (ja) * | 2007-11-16 | 2013-01-30 | 旭化成ケミカルズ株式会社 | 反応の安定化が容易なポリカーボネートジオール |
CN101855270B (zh) * | 2007-11-16 | 2014-03-12 | 旭化成化学株式会社 | 聚碳酸酯二醇 |
US8686107B2 (en) | 2007-11-16 | 2014-04-01 | Asahi Kasei Chemicals Corporation | Polycarbonate diol |
JP2013512210A (ja) * | 2009-11-26 | 2013-04-11 | ビーエーエスエフ ソシエタス・ヨーロピア | 1,6−ヘキサンジオールの製造方法 |
JP2018502857A (ja) * | 2015-01-09 | 2018-02-01 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | テトラヒドロフラン、1,4−ブタンジオール又はγ−ブチロラクトンの製造方法 |
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Publication number | Publication date |
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KR100546986B1 (ko) | 2006-01-26 |
EP1243573A1 (en) | 2002-09-25 |
CN1224597C (zh) | 2005-10-26 |
JP4683807B2 (ja) | 2011-05-18 |
TW538029B (en) | 2003-06-21 |
KR20020049024A (ko) | 2002-06-24 |
AU1055701A (en) | 2001-06-06 |
EP1243573B1 (en) | 2014-01-01 |
EP1243573A4 (en) | 2005-03-30 |
US6706932B1 (en) | 2004-03-16 |
CN1391549A (zh) | 2003-01-15 |
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