WO2002076919A1 - Procede de reaction avec catalyseur metallique soluble et resine echangeuse d'ions, procede de recuperation du catalyseur metallique soluble et procede de recyclage - Google Patents
Procede de reaction avec catalyseur metallique soluble et resine echangeuse d'ions, procede de recuperation du catalyseur metallique soluble et procede de recyclage Download PDFInfo
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- WO2002076919A1 WO2002076919A1 PCT/JP2002/002613 JP0202613W WO02076919A1 WO 2002076919 A1 WO2002076919 A1 WO 2002076919A1 JP 0202613 W JP0202613 W JP 0202613W WO 02076919 A1 WO02076919 A1 WO 02076919A1
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- exchange resin
- anion exchange
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- soluble metal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/74—Regeneration or reactivation of catalysts, in general utilising ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a reaction method using a soluble metal catalyst and an anion exchange resin in a liquid phase reaction, a method for recovering the soluble metal catalyst, and a method for reusing the recovered soluble metal catalyst for the liquid phase reaction. is there. Background technology>
- soluble metal catalysts compounds containing metal elements have been used as catalysts for various reactions.
- compounds such as metal salts and metal complexes are often used as catalysts in a state of being dissolved in a reaction solution in a liquid phase reaction (these are hereinafter referred to as “soluble metal catalysts”).
- soluble metal catalysts are generally highly active and highly selective catalysts because they work in a dissolved state, but are difficult to separate from the reaction solution, and are discarded after use or separated and recovered. Costly labor and cost.
- Japanese Unexamined Patent Publication No. Sho 59-444300 discloses a reaction between phthalic acid and an epoxy compound.
- a method is disclosed in which, after performing a reaction using a chromium compound as a soluble metal catalyst, the reaction solution is dissolved in a solvent such as water, and the catalyst is recovered with a cation exchange resin.
- Japanese Patent Application Laid-Open No. 11-152462 discloses a method of recovering a catalyst using a chelate-type anion exchange resin in a method for producing an aromatic sulfonic acid using a cobalt catalyst.
- the catalyst can be efficiently recovered, but a long catalyst adsorption step and a long desorption step are required separately from the reaction step.
- the conventional method of recovering a catalyst using an ion-exchange resin requires labor to reuse the catalyst adsorbed on the ion-exchange resin, and requires a catalyst adsorption step and a desorption step separately from the reaction step.
- the problem is that the process becomes complicated and takes a long time.
- U.S. Pat. No. 4,692,242 discloses a method for producing esters such as 2-hydroxyethyl acrylate.
- a method using a chromium (or iron) compound and an organic amine compound in combination as a catalyst is described.
- the combined effect of this method is the reaction rate and the yield of the target compound.
- No description is given on the separation and recovery of a soluble metal catalyst by an anion exchange resin.
- there is a description of the use of an iron compound and an anion exchange resin in combination but the adsorption of the iron compound to the anion exchange resin is estimated to be less than 50%, and substantial recovery was achieved. The effect is low.
- Soluble metal catalysts are usually disposed of in many cases, but disposal is not desirable in terms of economy and environment, and a method for easy recycling is desired.
- recovering and reusing the soluble metal catalyst has disadvantages in that large labor and equipment are required, and the process is complicated and requires a long time.
- the above-mentioned method of using the soluble metal catalyst and zeolite in combination has a limited range of application due to problems caused by the properties of zeolite and elution of the metal catalyst by washing.
- An object of the present invention is to provide a reaction method using a soluble metal catalyst and an anion exchange resin that can be reused, a method for recovering the soluble metal catalyst, and a method for reusing the same.
- the present inventors have conducted intensive studies and found that in a liquid phase reaction using a soluble metal catalyst, the use of an anion exchange resin under specific conditions makes dissolution very simple, inexpensive, and efficient.
- the present inventors have found that a reusable metal catalyst can be used, recovered, and reused, thereby completing the present invention. That is, the present invention has the following configurations.
- the raw material is introduced into the system containing the anion exchange resin, and the soluble metal catalyst is desorbed from the anion exchange resin. It is released again and can be reused in the reaction, and the soluble metal catalyst can be used repeatedly. That is, a reaction equivalent to the addition of a soluble metal catalyst can be realized by simply using the anion exchange resin on which the soluble metal catalyst is adsorbed for the next reaction.
- the present invention does not require a complicated adsorption step or desorption step, so that the soluble metal catalyst can be used, recovered, and reused easily, inexpensively, and in a simple step. .
- the reaction rate can be controlled by appropriately selecting the amounts of the soluble metal catalyst and the anion exchange resin and changing the ratio of free Z adsorption of the soluble metal catalyst.
- the effect of the present invention is particularly remarkable in the addition reaction of an epoxy compound to a carboxylic acid using a soluble metal catalyst.
- the metal ion of the soluble metal catalyst forms a complex having an anion derived from carboxylic acid as a ligand in a dissolved state.
- the concentration of carboxylic acid in the reaction solution is high, the ligand is present in the reaction solution at a high concentration, so that the complex is present in the reaction solution.
- the exchange group of the anion exchange resin (the counter anion in the case of an exchange group having a salt structure) generally has a coordination property, so that the ligand is contained in the anion exchange resin.
- Factors affecting the adsorption rate of the soluble metal catalyst on the anion exchange resin may be the ligand concentration and the coordination strength.
- the reaction product is easily coordinated, the product also coordinates with the soluble metal catalyst, making it difficult to adsorb, but if the reaction product is difficult to coordinate, Adsorption becomes easier and the catalyst recovery rate is improved.
- the contact between the anion exchange resin and the reaction solution containing the soluble metal catalyst can be carried out by the above mechanism at any time during the start of the reaction or during the reaction, by adsorbing the soluble metal catalyst in the reaction solution. can do.
- the progress of the reaction and the adsorption of the catalyst may be performed simultaneously. Simultaneous reaction and adsorption are significant from the perspective of process simplicity.
- the adsorption rate of the soluble metal catalyst to the anion exchange resin is 50% or more.
- problems for example, an increase in by-products
- the adsorption rate is high.
- by adsorbing 50% or more of the soluble metal catalyst, and recovering and reusing it the cost of the catalyst and the amount of waste can be reduced, and sufficient economic and environmental effects can be obtained.
- the adsorbed tin compound is eluted by hexane extraction, which is considered to be due to the elution of octanoate ions and chloride ions involved in the adsorption.
- the ligands involved in the adsorption The components do not elute because they are ionically or covalently bonded to the anion exchange resin. Therefore, even when washing with a non-coordinating solvent such as hexane, elution of the soluble metal catalyst hardly occurs. The ability to wash without elution makes it easy to use the same catalyst for multi-product production.
- anion exchange resin also acts as a basic catalyst, it functions as a catalyst in the reaction between the carboxylic acid and the epoxy compound, and can accelerate the reaction.
- Side reactions (such as ring-opening polymerization of epoxy compounds) that occur in zeolite do not occur in anion exchange resins.
- the activity can be controlled by changing the basicity of the counter anion.
- ion exchange resins have the advantage of not dissolving in strong acids and bases.
- the soluble metal catalyst can be used, recovered, and reused very easily, inexpensively, and efficiently. It is effective for the recovery and reuse of heavy metal elements and noble metal elements, which are highly demanded. In addition, it is possible to increase the amount of the catalyst, which has been limited for environmental and economic reasons, to improve the reaction selectivity, shorten the reaction time and lower the reaction temperature, which is also effective in the reaction.
- the anion exchange resin that can be used in the present invention is a resin having an anion exchange ability.
- a resin containing an amine and / or a quaternary ammonium salt as an exchange group a resin containing a pyridine and / or a pyridinium salt, and a resin containing a phosphine and / or a quaternary phosphonium salt are included.
- a suitable anion exchange resin can be appropriately selected depending on the reaction to be applied.
- a resin containing a quaternary ammonium salt since the adsorption rate of the soluble metal catalyst is high, a resin containing a quaternary ammonium salt, and It is preferable to use a resin containing a quaternary phosphonium salt, and among them, a resin having high liquid permeability and heat resistance is more preferable.
- a quaternary ammonium salt of an exchange group polymerizes a styrene-based anion exchange resin bonded to the base via an alkylene group having 4 or more carbon atoms, and diaryldimethylammonium chloride. Anion exchange resin obtained by the conversion is preferable.
- the amount of the anion exchange resin used is preferably an amount having an anion exchange capacity equivalent to 1 to 100 times the molar amount of the soluble metal catalyst.
- the volume of the anion exchange resin is preferably in the range of 1% to 70% by volume, more preferably in the range of 5% to 30% by volume of the total volume of the reaction solution.
- the form of the exchange group of the anion exchange resin can be appropriately selected, and may be an acid-neutralized type or a free type (in the case of a salt-structured exchange group, any counter anion may be used). Preferably, no by-product is generated.
- liquid phase reaction to which the present invention can be applied examples include an oxidation reaction, a reduction reaction, a condensation reaction, an esterification reaction, an amidation reaction, an etherification reaction, a carbonylation reaction, an alkylation reaction, and a hydroformylation reaction.
- the present invention is suitably used for a reaction using Brenstead acid as a raw material. More specifically, an esterification reaction for producing a carboxylic acid ester from a carboxylic acid and an alcohol, an epoxy addition reaction for producing a carboxylic acid hydroxy ester from a carboxylic acid and an epoxy compound, a glycol compound from an alcohol and an epoxy compound, or An etherification reaction for producing hydroxyalkyl ethers may be mentioned.
- an epoxy addition reaction for producing a carboxylic acid hydroxyester from a carboxylic acid and an epoxy compound, and furthermore, a (meth) acrylic acid hydroxyester from a (meth) acrylic acid and an alkylenoxide. It is suitably used for a reaction for producing hydroxyethyl (meth) acrylate from (meth) acrylic acid and ethylene oxide.
- examples of the Brnsted acid that can be used include a carboxylic acid compound (for example, alkane mono- or dicarboxylic acid, aromatic mono- or di-carboxylic acid).
- Rubonic acid and those acids substituted with hydroxy or halogen such as formic acid, acetic acid, propionic acid, butyric acid Acid, caproic acid, stearic acid, (meth) acrylic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, itaconic acid, benzoic acid, phenylacetic acid, naphthenic acid, toluic acid, phthalic acid, terephthalic acid Acid, isofluoric acid, ⁇ -promogluconic acid, salicylic acid, ⁇ -chlorobenzoic acid, m-methoxybenzoic acid, hydroxybutyric acid, poly (meth) acrylic acid, etc.), phenolic compounds (for example, : N-nor, bis-phenol, cresol, nonylphenol, xylenol, catechol, ethyl phenol, naphthol, hydroquinone, methoxyphenol, etc., alcohol-based compounds (for
- the soluble metal catalyst referred to in the present invention is a metal catalyst that acts by dissolving in a reaction solution. What is used in the present invention may be selected according to various reactions, but is preferably one containing a metal element which easily forms a complex structure. Specifically, chromium, iron, tin, manganese, cobalt, vanadium, titanium, nickel, zinc, copper, zirconia, molybdenum, tungsten, aluminum, lead, indium, ruthenium, rhodium, palladium, Examples include compounds containing platinum, silver, and gold.
- Specific compounds include known compounds of the above-mentioned metal species such as halides, carboxylates, nitrates, sulfates, oxides, hydroxides, and complex compounds.
- a system using a soluble metal catalyst containing chromium, iron, cobalt, copper, ruthenium, rhodium, and palladium is particularly preferable due to environmental and economic requirements.
- reaction conditions such as reaction temperature, reaction time, raw material composition ratio, amount of catalyst, etc. may be selected according to various reactions.
- a reaction temperature under which the anion exchange resin is hardly thermally degraded and specifically, in the range of 20 ° C. to 140 ° C.
- the method of reacting in the presence of a soluble metal catalyst and an anion exchange resin includes (A) (B) Separately providing a resin tank containing an anion exchange resin and circulating the reaction solution in the tank to perform the reaction and adsorption. No. When a separate resin tank is provided, the tank may be a fixed bed or a suspended bed.
- the coexistence of the anion exchange resin and the reaction solution containing the soluble metal catalyst may be performed from the beginning of the above-described various reactions or may be performed in the middle.
- the coexistence of both may be stopped before the reaction is completed, or may be performed until the reaction is completed.
- the apparatus becomes simple, it is preferable to carry out the reaction and adsorption by coexisting both from the beginning to the end of the reaction by the method (A).
- a reaction having a large heat of reaction is carried out, from the viewpoint of heat removal, it is preferable to carry out adsorption by coexisting the two in the middle of the reaction by the method (B).
- (B) is also advantageous in that the resin and the reaction solution can be easily separated.
- the adsorption rate of the soluble metal catalyst on the anion exchange resin indicates the ratio of the amount of the soluble metal catalyst adsorbed on the anion exchange resin to the total amount of the soluble metal catalyst present in the reaction system.
- the adsorption rate of the soluble metal catalyst to the anion exchange resin must be 50% or more. More preferably, the adsorption rate is 70% or more, and still more preferably 90% or more.
- Methods for improving the adsorption rate of the soluble metal catalyst and the anion exchange resin include increasing the raw material conversion and decreasing the raw material concentration, adding a component that forms a more stable complex, and adding a solvent. Methods can be used, and these can be appropriately combined to achieve a target adsorption rate.
- the preferred raw material conversion rate is 70% or more, and more preferably 90% or more.
- Components that form more stable complexes include low-molecular-weight coordination compounds such as acetic acid and propionic acid, and chelating compounds such as oxalic acid, succinic acid, malic acid, salicylic acid, ethylenediamine, iminodiacetic acid, and ethylenediaminetetraacetic acid.
- Coordination compounds forming a monocyclic ring are preferred.
- an inert solvent is preferable, and specific examples thereof include hexane, cyclohexane, toluene, acetone, methylethylketone, and cyclohexanone.
- a general method is used to measure the adsorption rate.
- the concentration of metal ions released in the reaction solution is measured by ultraviolet-visible absorption measurement, atomic absorption measurement, or ICP emission analysis to determine the adsorption rate. Method. Also, as the reaction progresses, When the rate increases, the degree of reaction progress can be known from the adsorption rate.
- the method of separating the anion exchange resin from the reaction solution is not particularly limited, and examples thereof include filtration using a mesh, a filter cloth, a strainer, etc., decantation, and distillation. It is not always necessary to completely separate the anion exchange resin and the reaction solution, and raw materials may be added except for a part of the reaction solution.
- an anion exchange resin that has adsorbed a soluble metal catalyst When reusing an anion exchange resin that has adsorbed a soluble metal catalyst, it may be used for the next reaction immediately after adding the raw materials after separation from the reaction solution, or after washing with a solvent, You may use for reaction. In the case of washing, a solvent having a relatively low coordinating property such that the soluble metal catalyst does not flow out is preferred. Specific examples include linear alkanes, branched alkanes, aromatic compounds, ester compounds, ketone compounds, and the like.
- the reaction may be started immediately after the raw material is added to the anion exchange resin on which the catalyst is adsorbed, and the raw material is added and the soluble metal catalyst is sufficiently eluted from the anion exchange resin. The reaction may be started after the reaction.
- the reaction is started after eluting 50% or more of the soluble metal catalyst adsorbed on the anion exchange resin, more preferably 80% or more, and even more preferably 90% or more. % Or more.
- the elution method include a method in which an anion exchange resin and a raw material are mixed and eluted in a single reactor, and a method in which the raw material is passed through a resin tank and eluted.
- the method of the present invention is suitable for a reaction for producing a carboxylic acid hydroxyester from a carboxylic acid and an epoxy compound.
- the carboxylic acids as described above can be used in this reaction, and specific examples of the epoxy compound include ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, styrene oxide, cyclohexene oxide, and epichloro compound. These include hydrin, epipido mohydrin, epihydrin, mono- and di- and polyglycidyl ethers. Among them, ethylene oxide and propylene oxide are preferred.
- usable anion exchange resins include a resin containing an amine and / or a quaternary ammonium salt as an exchange group, and a pyridine and / or pyridinium salt. And resins containing phosphine and / or quaternary phosphonium salts. Since an anion exchange resin also acts as a catalyst, it is preferable to use an anion exchange resin having high catalytic activity, and specifically, a resin containing a quaternary ammonium salt and a resin containing a quaternary phosphonium salt are preferable. Among them, those having high heat resistance are more preferable.
- the resin containing a quaternary ammonium salt and the resin containing a quaternary phosphonium salt are also preferable because the adsorption rate of the soluble metal catalyst is high.
- a quaternary ammonium salt of an exchange group polymerizes a styrene-based anion exchange resin bonded to a base via an alkylene group having 4 or more carbon atoms, and diaryldimethylammonium chloride.
- Anion exchange resins obtained by solidification are preferred.
- the form of the exchange group of the anion exchange resin is preferably such that no by-product is generated after the reaction.
- those having an anion generated from the acid of the reaction raw material as a counter ion are preferable.
- the reaction raw material is acrylic acid, it is preferable to use acrylic acid ions as counter anions.
- the reaction temperature is preferably from 20 ° C to 140 ° C, more preferably from 50 ° C to 100 ° C.
- the charged molar ratio of the epoxy compound Z carboxylic acid is preferably 0.5 to 10.0, more preferably 0.9 to 5.0, and still more preferably 0.9 to 1.5.
- a trivalent chromium compound, a trivalent iron compound, or a trivalent ruthenium compound is preferably used. Specifically, chromium acetate, chromium chloride, chromium nitrate, chromium nitrate, iron acetate, iron chloride, nitric acid Iron, ruthenium acetate, ruthenium chloride and ruthenium nitrate are preferred.
- a chromium compound because of its high catalytic activity and high adsorption rate to an anion exchange resin.
- the amount of the catalyst is preferably 0.001 mol% to 5 mol% of the acid component.
- the anion exchange resin is preferably used in an amount having an anion exchange capacity equivalent to 1 to 100 times the molar amount of the soluble metal catalyst. It is more preferably in the range of 1% by volume to 70% by volume of the total liquid volume, more preferably 5 units % By volume to 30% by volume.
- the method of reacting in the presence of a soluble metal catalyst and an anion exchange resin is as follows: (A) —Put both in a single reactor, and carry out the reaction and adsorption; ) A method of separately providing a resin tank and circulating the reaction solution in the tank to carry out the reaction and the adsorption.
- the tank may be a fixed bed or a suspended bed.
- the coexistence of the anion exchange resin and the reaction solution containing the soluble metal catalyst may be carried out from the beginning of the above-mentioned various reactions or may be carried out in the middle.
- the contact between the two is preferably carried out from the start or during the reaction to the end of the reaction. Specifically, the contact is preferably performed at a conversion of carboxylic acid of 0% to 100%, more preferably 50% to 100%, and even more preferably 90% to 1%. It is between 0%. From the viewpoint of removing heat of reaction, it is preferable to separately provide a tank containing an anion exchange resin, and to bring the reaction solution into contact with the tank while the reaction proceeds.
- the form of the tank is preferably a fixed bed.
- the adsorption rate of the soluble metal catalyst must be 50% or more.
- the adsorption rate is 70% or more, more preferably 90% or more.
- Methods for improving the adsorption rate between the soluble metal catalyst and the anion exchange resin include increasing the acid conversion rate to decrease the acid concentration, adding a component that forms a more stable complex, and using a solvent. Addition methods can be mentioned, and these can be appropriately combined to achieve a desired adsorption rate.
- the preferred acid conversion is 70% or more, more preferably 90% or more, and even more preferably 99% or more.
- Components that form more stable complexes include low-molecular acids such as acetic acid, acrylic acid, and propionic acid, and oxalic acid, malonic acid, succinic acid, salicylic acid, malic acid, tartaric acid, citric acid, and iminodiacetic acid.
- an acid which forms a chelate ring such as ethylenediaminetetraacetic acid is preferred, and the amount of the added acid is preferably 10% or less, more preferably 1% or less, of the reaction solution.
- the method of adding the acid it is preferable to add the acid at the end of the reaction because the effect is large, and specifically, it is preferable to add the acid at an acid conversion of 95% or more, and more preferably at an acid conversion of 99%. That is all.
- an inert solvent is preferable. Specific examples thereof include hexane, cyclohexane, toluene, acetone, methylethylketone, and cyclohexanone.
- the amount of the added solvent is preferably 70% or less of the reaction solution, and more preferably 4% or less. 0% or less, more preferably 20% or less.
- the added solvent may be added from the beginning of the reaction or during the reaction. Since the addition of a solvent may improve the reaction selectivity of the target substance, it is preferable to add it from the beginning of the reaction.
- the raw material may be added to the anion exchange resin on which the catalyst has been adsorbed, and the reaction may be started immediately, but the reaction is performed after eluting 50% or more of the adsorbed catalyst. Is preferably started, more preferably at least 80%, even more preferably at least 90%.
- the elution method include a method in which an anion exchange resin and a raw material are mixed and eluted in a single reactor, and a method in which the raw material is passed through a resin tank and eluted.
- a chromium compound for example, chromium (III) acetate
- a quaternary ammonium-type anion exchange resin coexists from the beginning of the reaction
- the chromium (III) ion reacts at the beginning of the reaction. It is present in the free state.
- the reaction proceeds by the catalytic action of chromium ions and anion exchange resin, and as the concentration of acrylic acid decreases, chromium (III) ions are adsorbed on the anion exchange resin. This is because the chromium (III) ion forms a complex whose main ligand is the anion of acrylic acid, and the complex becomes more acrylic as the concentration of acrylic acid in the reaction solution decreases. This is probably because the acid migrates into the anion exchange resin where the acid is present. Chromium ions can be easily recovered from the reaction product only by separating the anion exchange resin from the reaction solution after the reaction.
- Chromium catalyst was added simply by adding A reaction equivalent to the above can be caused. That is, the chromium catalyst can be easily reused.
- the effect of the present invention was examined in the hydroxypropylation reaction of acrylic acid using chromium (III) acetate as a metal ion catalyst.
- an anion exchange resin as the anion exchange resin (disclosed in Example 1 of Japanese Patent Application No. 2000-127664.
- An anion exchange resin obtained by crosslinking a copolymer of diaryldimethylammonium chloride and diarylamine, High heat resistance.
- the absorbance of the reaction solution without addition of anion exchange resin was determined by performing the same reaction without adding anion exchange resin, measuring the absorbance of several reaction solutions having different conversion rates, and using the simple average value. Table 1 shows the obtained reaction results.
- the volume of Resin A after the reaction was 4.9 ml (23 VOL% of the total volume of the reaction solution), and the selectivity of hydroxypropyl acrylate (HPA, target compound) was 5.5 in 5.5 hours. 3 mol% (vs. AA).
- Example 3 An experiment was conducted in exactly the same manner as in Example 1 except that the amount of chromium (III) acetate was 12 Omg, and the results shown in Table 3 were obtained.
- the HPA reaction selectivity at 2.5 hours was 97.3 mol%.
- a dark green colored resin A and a light green reaction solution were obtained.
- Increasing the amount of chromium catalyst shortened the reaction time and improved selectivity.
- the use of an anion exchange resin also enabled the recovery of crion.
- Example 4 An experiment was conducted in exactly the same manner as in Example 2 except that the amount of the resin A was changed to 2. Og, and the results shown in Table 3 were obtained.
- the HPA reaction selectivity at 3 hours was 97.9 mol%.
- the volume of Resin A after the reaction was 14.3 ml.
- the anion exchange resin is Diaion TSA 1200 (Mitsubishi Chemical Corporation, a styrene-based anion exchange resin in which a quaternary ammonium base as an exchange group is bonded to the base via a butylene group. High heat resistance.
- the experiment was performed in exactly the same manner as in Example 2 except that the reaction temperature was changed to 50 ° C, and the experiment was performed. The results shown in Table 3 were obtained.
- the HPA reaction selectivity at 5 hours was 97.4 mol%.
- a dark green colored TSA 1200 and a light green reaction solution were obtained.
- the volume of TSA 1200 after the reaction was 4.9 ml. This indicates that the effect of the present invention can be obtained even with a commercially available quaternary ammonium salt-type anion exchange resin.
- An anion exchange resin is disclosed in Example 1 of Japanese Patent Application No. 2000-181265. Diaryldimethylammonium chloride is copolymerized with a crosslinking agent. Anion exchange resin solidified with and has high heat resistance. (Used for chloride ion type dry body)
- Example 4 Except that the amount was 0.78 g, the same procedure as in Example 4 was carried out, and the results shown in Table 3 were obtained.
- the HPA reaction selectivity at 6 hours was 97.2 mol%.
- the volume of Resin B after the reaction was 5.0 ml.
- the anion exchange resin is a tertiary amine type anion exchange resin C (disclosed in Example 5 of Japanese Patent Publication No. 2000-070724.
- Anion exchange resin obtained by polymerizing triallylamine hydrochloride. Except that the weight was changed to 0.57 g, the same procedure was performed as in Example 4 to obtain the results shown in Table 3.
- the HP A reaction selectivity at 6 hours was 97.2 mol%.
- the reaction mixture was subjected to vacuum filtration, a dark green colored resin C and a light green reaction liquid were obtained.
- the volume of the resin C after the reaction was 5.8 ml. This indicates that the effects of the present invention can be obtained even with a tertiary amine type anion exchange resin.
- Table 3
- the experiment was started exactly as in Example 2. 3.2 hours after the start of the reaction, the AA conversion reached 1000.0%, and the chromium ion adsorption rate was 99%. Next, 15. Og of the reaction solution alone was extracted from the reaction mixture with a pipette, and 7.5 g of acrylic acid (AA) and propylene oxide (PO) were added. When AA was added, the chromion was released and the reaction solution turned green. The reaction was carried out again while shaking this at 60 ° C. The same operation was repeated, and a reuse experiment was performed. The results are shown in Table 5. The progress of the reaction was measured by monitoring the absorbance, and was terminated when the adsorption rate reached 95% or more. This indicates that the chromium catalyst adsorbed on the anion exchange resin can be easily reused. Table 5
- Example 6 A reuse experiment was performed in exactly the same manner as in Example 8, except that the anion exchange resin was changed to Diaion TSA 1200, 1.09 g used in Example 4, and the results in Table 6 were obtained. . As a result, it was found that the chromium catalyst adsorbed on TSA 1200 can be easily reused. Further, when the anion exchange capacity of TSA 1200 after the completion of six batches was measured, it was found that the anion exchange capacity of TSA 1200 was not changed. Table 6
- Example 8 A reuse experiment was conducted in exactly the same manner as in Example 8 except that the anion exchange resin was changed to 0.78 g of the resin B used in Example 6, and the results in Table 7 were obtained. As a result, it was found that the chromium catalyst adsorbed on the resin B can be easily reused. In addition, when the anion exchange capacity of Resin B after 6 patches was measured, it was found that the anion exchange capacity of Resin B did not change.
- Example 2 The experiment was carried out in exactly the same manner as in Example 1 except that the soluble metal catalyst was changed to 84 mg of iron (III) nitrate nonahydrate and the reaction temperature was changed to 70 ° C.
- Example 12 The same experiment as in Example 11 was performed without adding an anion exchange resin. After 4 hours from the start of the reaction, the AA conversion reached 85.0%, and after 7 hours, the AA conversion reached 97.3%, but the absorbance of the reaction solution was 1.10 and the adsorption rate was 0%. Was. The reaction solution after the reaction was dark brown.
- Example 12 The same experiment as in Example 11 was performed without adding an anion exchange resin. After 4 hours from the start of the reaction, the AA conversion reached 85.0%, and after 7 hours, the AA conversion reached 97.3%, but the absorbance of the reaction solution was 1.10 and the adsorption rate was 0%. Was. The reaction solution after the reaction was dark brown.
- Example 12 The same experiment as in Example 11 was performed without adding an anion exchange resin. After 4 hours from the start of the reaction, the AA conversion reached 85.0%, and after 7 hours, the AA conversion reached 97.3%, but the absorbance of the reaction solution was 1.10 and the adsorption rate was 0%.
- Example 13 a hydroxypropylation reaction was performed using carboxylic acid as acetic acid, and the effects of the present invention were examined. That is, an experiment was conducted in Example 1, except that acrylic acid was changed to 8.3 g of acetic acid and the reaction temperature was changed to 70 ° C. Table 8 shows the obtained results. When the reaction mixture was filtered under reduced pressure, a dark green colored resin A and a light green reaction solution were obtained.
- Example 13
- Example 14 The experiment was carried out in exactly the same manner as in Example 12 except that the carboxylic acid was changed to 10.3 g of propionic acid, and the results shown in Table 8 were obtained. When the reaction mixture was filtered under reduced pressure, a dark green colored resin A and a light green reaction solution were obtained.
- Example 14
- Example 15 An experiment was conducted in exactly the same manner as in Example 12 except that n-butyric acid was replaced with 12.2 g of carboxylic acid, and the results shown in Table 8 were obtained. When the reaction mixture was subjected to filtration under reduced pressure, a dark green colored resin A and a light green reaction liquid were obtained.
- Example 15
- Example 16 The experiment was carried out in exactly the same manner as in Example 12, except that the amount of chromium acetate was changed to 4 Omg and the carboxylic acid was changed to 11.9 g of methacrylic acid, and the results shown in Table 8 were obtained.
- Example 16 The experiment was carried out in exactly the same manner as in Example 12, except that the amount of chromium acetate was changed to 4 Omg and the carboxylic acid was changed to 11.9 g of methacrylic acid, and the results shown in Table 8 were obtained.
- Example 12 The experiment was carried out exactly as in Example 12, except that the carboxylic acid was changed to 11.9 g of methacrylic acid and the reaction temperature was changed to 60 ° C., and the results shown in Table 8 were obtained. However, the reaction was performed for 4.5 hours, and when the conversion reached 100%, 110 mg of acetic acid was added to the reaction vessel and the reaction was continued for another 30 minutes. During the 30 minutes, there was no change in the reaction selectivity of hydroxypropyl methacrylate, and the adsorption rate was improved. When the reaction mixture was subjected to filtration under reduced pressure, a dark green colored resin A and a light green reaction solution were obtained. Compared with Example 15, it was found that the addition of acetic acid improved the adsorption rate. Table 8
- Example 17 the experiment was carried out without using chromium acetate as the lg resin and adding the resin A.
- the addition of ethylene oxide (EO) was performed over 4 hours. After a total reaction time of 6.5 hours, the AA conversion reached 100.0%, and the selectivity for HEA was 93 mol%. Naturally, chromium ions could not be recovered, and the reaction solution was dark green.
- EO ethylene oxide
- Example 19 The reaction was carried out exactly as in Example 17. Four hours after the start of the reaction, succinic acid was added to a 1-lg reactor, and the reaction was continued. Table 9 shows the results. Addition of succinic acid increased the chromium ion adsorption rate to 96% at an AA conversion of 100.0%.
- Example 19 The reaction was carried out exactly as in Example 17. Four hours after the start of the reaction, succinic acid was added to a 1-lg reactor, and the reaction was continued. Table 9 shows the results. Addition of succinic acid increased the chromium ion adsorption rate to 96% at an AA conversion of 100.0%. Example 19
- Example 17 1.6 g of chromium acetate, 130 g of acrylic acid (AA), 5.8 g of resin B, and 92 g of methylethylketone as a solvent were charged into an autoclave and heated to 60 ° C. The temperature rose. Subsequently, 84 g of ethylene oxide (EO) was added over 2 hours, and the reaction was continued. Table 9 shows the results. The selectivity for HEA at 7 hours of reaction was 96% molar. From these results, it was found that the addition of the solvent improved the chromium ion adsorption rate and the HEA selectivity at an AA addition rate of 100%. Table 9
- Example 17 acrylic acid (AA) was replaced with methyric acid (MA) 200 and chromium acetate was replaced with 1.4 g, and 9 g of the resin A used in Example 1 as an anion exchange resin
- Ethylene oxide (E 0) 11 Og was added over 3 hours. 5.5 hours after the start of the reaction, the conversion rate of MA reached 100.0%, and the adsorption rate of chromium ions to the anion exchange resin was 65%.
- E 0 Ethylene oxide
- a soluble metal catalyst by using a soluble metal catalyst and an anion exchange resin in combination for a liquid phase reaction, a soluble metal catalyst can be used very easily and inexpensively while using a soluble metal catalyst. Can be recovered from the reaction system. Further, the recovered soluble metal catalyst can be reused without requiring complicated processing. Therefore, since a long and complicated adsorption process and desorption process are not required, a simple catalyst recycling system can be assembled.
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2002576182A JPWO2002076919A1 (ja) | 2001-03-26 | 2002-03-19 | 溶解性金属触媒と陰イオン交換樹脂を用いた反応方法、その溶解性金属触媒の回収方法及び再利用方法 |
EP02705352A EP1382594A4 (en) | 2001-03-26 | 2002-03-19 | PROCESS FOR IMPLEMENTATION WITH SOLUBLE METALLIC CATALYST AND ANION EXCHANGE RESIN, METHOD FOR THE RECOVERY OF THE SOLUBLE METALLIC CATALYST AND RECYCLING METHOD |
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JP2001087846 | 2001-03-26 | ||
JP2001-87846 | 2001-03-26 |
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WO2002076919A1 true WO2002076919A1 (fr) | 2002-10-03 |
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PCT/JP2002/002613 WO2002076919A1 (fr) | 2001-03-26 | 2002-03-19 | Procede de reaction avec catalyseur metallique soluble et resine echangeuse d'ions, procede de recuperation du catalyseur metallique soluble et procede de recyclage |
Country Status (5)
Country | Link |
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US (1) | US6958413B2 (ja) |
EP (1) | EP1382594A4 (ja) |
JP (1) | JPWO2002076919A1 (ja) |
CN (1) | CN1237045C (ja) |
WO (1) | WO2002076919A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1371628A3 (en) * | 2002-06-11 | 2004-02-11 | Nippon Shokubai Co., Ltd. | Production process for hydroxyalkyl (meth)acrylate |
JP2004351415A (ja) * | 2003-05-06 | 2004-12-16 | Nippon Shokubai Co Ltd | クロム系触媒の回収方法 |
US6984751B2 (en) | 2002-08-12 | 2006-01-10 | Nippon Shokubai Co., Ltd. | Production process for hydroxyalkyl (meth) acrylate |
JP2010162006A (ja) * | 2009-01-19 | 2010-07-29 | Akita Univ | 糠臭が取り除かれた米糠浸出物の製造方法、糠臭が取り除かれた米糠浸出物、及びγ−アミノ酪酸の製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8357553B2 (en) * | 2010-10-08 | 2013-01-22 | Guardian Industries Corp. | Light source with hybrid coating, device including light source with hybrid coating, and/or methods of making the same |
TWI468524B (zh) * | 2013-10-22 | 2015-01-11 | China Steel Corp | Recovery of vanadium and tungsten from waste selective catalytic reduction catalyst |
KR20230016250A (ko) * | 2019-07-02 | 2023-02-01 | 니혼 메디피직스 가부시키가이샤 | 226Ra 함유 용액의 정제 방법, 226Ra 타깃의 제조 방법, 및 225Ac의 제조 방법 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54100307A (en) * | 1978-01-13 | 1979-08-08 | Dow Chemical Co | Composition for catalyzing esterification reaction |
JPH09262479A (ja) * | 1996-03-29 | 1997-10-07 | Kuraray Co Ltd | ルイス酸触媒 |
EP1029847A1 (en) * | 1999-02-17 | 2000-08-23 | Nippon Shokubai Co., Ltd. | Process for producing hydroxyalkyl (meth)acrylates |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4069242A (en) * | 1969-02-06 | 1978-01-17 | The Dow Chemical Company | Process for preparation of β-hydroxy esters by reaction of organic carboxylic acids and vicinal epoxides |
US4417077A (en) * | 1980-10-01 | 1983-11-22 | University Of Illinois Foundation | Heterogeneous anionic transition metal catalysts |
-
2002
- 2002-03-19 JP JP2002576182A patent/JPWO2002076919A1/ja not_active Withdrawn
- 2002-03-19 EP EP02705352A patent/EP1382594A4/en not_active Withdrawn
- 2002-03-19 WO PCT/JP2002/002613 patent/WO2002076919A1/ja active Application Filing
- 2002-03-19 CN CNB028073088A patent/CN1237045C/zh not_active Expired - Fee Related
- 2002-03-25 US US10/104,054 patent/US6958413B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54100307A (en) * | 1978-01-13 | 1979-08-08 | Dow Chemical Co | Composition for catalyzing esterification reaction |
JPH09262479A (ja) * | 1996-03-29 | 1997-10-07 | Kuraray Co Ltd | ルイス酸触媒 |
EP1029847A1 (en) * | 1999-02-17 | 2000-08-23 | Nippon Shokubai Co., Ltd. | Process for producing hydroxyalkyl (meth)acrylates |
Non-Patent Citations (1)
Title |
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See also references of EP1382594A4 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1371628A3 (en) * | 2002-06-11 | 2004-02-11 | Nippon Shokubai Co., Ltd. | Production process for hydroxyalkyl (meth)acrylate |
US7045651B2 (en) | 2002-06-11 | 2006-05-16 | Nippon Shokubai Co., Ltd. | Production process for hydroxyalkyl (meth) acrylate |
US6984751B2 (en) | 2002-08-12 | 2006-01-10 | Nippon Shokubai Co., Ltd. | Production process for hydroxyalkyl (meth) acrylate |
JP2004351415A (ja) * | 2003-05-06 | 2004-12-16 | Nippon Shokubai Co Ltd | クロム系触媒の回収方法 |
JP2010162006A (ja) * | 2009-01-19 | 2010-07-29 | Akita Univ | 糠臭が取り除かれた米糠浸出物の製造方法、糠臭が取り除かれた米糠浸出物、及びγ−アミノ酪酸の製造方法 |
JP4537486B2 (ja) * | 2009-01-19 | 2010-09-01 | 国立大学法人秋田大学 | 糠臭が取り除かれた米糠浸出物の製造方法、糠臭が取り除かれた米糠浸出物、及びγ−アミノ酪酸の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US6958413B2 (en) | 2005-10-25 |
JPWO2002076919A1 (ja) | 2004-10-21 |
EP1382594A1 (en) | 2004-01-21 |
CN1237045C (zh) | 2006-01-18 |
EP1382594A4 (en) | 2008-06-25 |
CN1503776A (zh) | 2004-06-09 |
US20020198403A1 (en) | 2002-12-26 |
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