WO2017159466A1 - 触媒担体用ビニルピリジン樹脂、その製造方法およびメタノールのカルボニル化反応用触媒 - Google Patents
触媒担体用ビニルピリジン樹脂、その製造方法およびメタノールのカルボニル化反応用触媒 Download PDFInfo
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- WO2017159466A1 WO2017159466A1 PCT/JP2017/009057 JP2017009057W WO2017159466A1 WO 2017159466 A1 WO2017159466 A1 WO 2017159466A1 JP 2017009057 W JP2017009057 W JP 2017009057W WO 2017159466 A1 WO2017159466 A1 WO 2017159466A1
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Images
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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Definitions
- the present invention relates to a vinylpyridine resin for a catalyst carrier that can be used as a catalyst carrier for the production of acetic acid by methanol carbonylation reaction.
- Acetic acid is a basic chemical with a wide range of uses, such as raw materials for polyvinyl acetate, acetylcellulose and acetates, and solvents for terephthalic acid production plants.
- “Monsanto method” (Patent Document 1) in which methanol and carbon monoxide are reacted in a water-containing acetic acid solvent in which a rhodium compound and methyl iodide are uniformly dissolved is often used.
- a technique (Patent Documents 2 to 5) in which a reaction is carried out in a heterogeneous system using a catalyst in which rhodium is supported on a porous vinylpyridine resin carrier has been proposed. It is also planned.
- hydroiodic acid is produced by hydrolysis of methyl iodide by reducing the water concentration in the reaction product solution.
- the corrosion of the equipment system and the load of the separation and purification process of product acetic acid can be suppressed, and the reaction rate increases by immobilizing the rhodium complex to achieve a high concentration of the catalyst, and the catalyst is converted into the reactor. It has the further advantage that the cost and load required for separation and recovery can be reduced by reducing the deposition of the catalyst by enclosing the catalyst inside.
- Patent Document 6 discloses vinylpyridine monomer, divinylbenzene as a crosslinking agent, isooctane as a pore-forming agent, and benzoyl peroxide as a polymerization initiator.
- An aqueous phase containing a cellulose-based suspension stabilizer for uniformly dispersing the phase in the aqueous phase is mixed in a polymerization reactor, and the oil phase is dispersed and polymerized at 80 ° C. for 2 hours.
- a vinylpyridine resin produced by heat treatment at 95 ° C. for 5 hours is disclosed.
- Patent Document 7 discloses a vinyl pyridine resin for a catalyst carrier that has improved abrasion resistance and suppressed pulverization by controlling the pore volume ratio of 3 to 5 nm, and a method for producing the same.
- the vinylpyridine resin disclosed in Patent Document 7 has a sufficient specific surface area, pore volume, average pore diameter, heat resistance and abrasion resistance that can be used as a catalyst carrier for methanol carbonylation reaction.
- the relationship between the degree of crosslinking of vinyl pyridine resin and the catalytic activity has been studied in detail in the Examples of Patent Document 5, and the heat resistance of the vinyl pyridine resin is improved when the degree of crosslinking is changed from 17 mol% to 28 mol%. It has been shown that the cracking rate (denitrogenation rate) is greatly reduced, but the catalytic activity drops to about 40%.
- the present invention provides a vinyl pyridine resin for a catalyst carrier having excellent heat resistance, wear resistance and catalytic activity of a rhodium-supported catalyst, a method for producing the same, and a catalyst for methanol carbonylation reaction.
- a vinyl pyridine resin for a catalyst carrier having excellent heat resistance, wear resistance and catalytic activity of a rhodium-supported catalyst, a method for producing the same, and a catalyst for methanol carbonylation reaction.
- the nitrogen content derived from the vinylpyridine group is 3.00% by mass to 8.00% by mass
- the degree of crosslinking is 35% by mol to 70% by mol
- carbon atoms and nitrogen molar ratio C / N with the atom 12.00 or 36.00 or less
- the total pore volume 0.20 cc / g or more 0.45 cc / g or less and a specific surface area of 70.0m 2 / g or more 280.0M 2 / G or less
- the inventors have found that the above object can be achieved with a pyridine resin, and thus completed the present invention.
- the vinyl pyridine resin for a catalyst carrier of the present invention has a nitrogen content derived from a pyridine group of 3.00 mass% to 8.00 mass%, a degree of crosslinking of 35 mol% to 70 mol%, carbon atoms and nitrogen.
- the vinyl pyridine resin for the catalyst carrier is preferably a copolymer of vinyl pyridine and divinyl benzene.
- the method for producing a vinyl pyridine resin for a catalyst carrier according to the present invention is a method for producing a vinyl for a catalyst carrier by subjecting an oily medium containing a vinyl pyridine, a cross-linking agent, a pore-forming agent and a polymerization initiator and an aqueous medium to suspension polymerization.
- the pore forming agent contains two or more organic solvents, and the absolute value of the difference between the SP value of the vinyl pyridine resin for the catalyst carrier and the SP value of the pore forming agent is 1.80 or more and 2.80 or less.
- the main polymerization initiator is preferably 1.50% by mass or less based on the total amount of the monomers.
- the pore forming agent contains an organic solvent having a benzene ring.
- the auxiliary polymerization initiator preferably has a half-life temperature lower than the suspension polymerization temperature, and the main polymerization initiator preferably has a half-life temperature higher than the suspension polymerization temperature.
- the catalyst for methanol carbonylation reaction of the present invention is characterized in that rhodium is supported on the vinylpyridine resin for catalyst support.
- the catalyst for carbonylation reaction of methanol is a thermal decomposition rate under the conditions of 220 ° C. and nitrogen atmosphere in a mixed solution of 86.5% by mass of acetic acid, 8.0% by mass of methyl iodide and 5.5% by mass of water. Is preferably 0.25 mol% or less per hour.
- a vinyl pyridine resin for a catalyst carrier that is excellent in heat resistance, wear resistance and catalytic activity.
- supported rhodium on this vinyl pyridine resin for catalyst carriers is excellent in heat resistance, abrasion resistance, and catalytic activity, it can be used suitably for manufacture of acetic acid.
- the vinyl pyridine resin for a catalyst carrier of the present invention has a nitrogen content derived from a vinyl pyridine group of 3.00 mass% to 8.00 mass%, a degree of crosslinking of 35 mol% to 70 mol%, carbon atoms and nitrogen.
- Such a vinyl pyridine resin for a catalyst carrier of the present invention (hereinafter also simply referred to as “vinyl pyridine resin”) is excellent in heat resistance and wear resistance and supports rhodium, as shown in the examples described later.
- the catalyst is excellent in catalytic activity in methanol carbonylation reaction.
- the catalyst using the vinylpyridine resin of the present invention as a carrier has high wear resistance and the wear resistance hardly decreases to a decomposition rate (nitrogen reduction rate) of about 25%, so that the catalyst flows even at a decomposition rate of about 25%.
- a stirred tank reactor or a bubble column reactor in which the catalyst is brought into contact with carbon monoxide.
- a stirrer In a stirred tank reactor that stirs the reaction solution with a stirrer provided in the reactor to cause the catalyst to flow or a bubble column reactor that stirs the reaction solution by supplying bubbles into the reactor, a stirrer,
- the catalyst is likely to be worn by collision with bubbles and the wall of the reactor or flow of the reaction solution, but the vinylpyridine resin of the present invention is excellent in wear resistance. Can be used in the reactor.
- the catalyst using the vinylpyridine resin of the present invention as a carrier is excellent in heat resistance, it can be used at high temperatures. And since it is excellent also in the catalytic activity of methanol carbonylation reaction, it can be made to react efficiently and acetic acid can be obtained.
- the proportion of the crosslinking agent used is increased in order to increase the degree of crosslinking, for example, when a crosslinking agent having no pyridine group is used, the content ratio of the pyridine group in the vinyl pyridine resin decreases, and iodine (quaternary) Since the molar ratio of pyridine group) / rhodium becomes small, the rhodium complex becomes unstable, which also causes a problem that the catalytic activity is lowered.
- a vinyl pyridine resin that satisfies all the above-mentioned specific requirements, a vinyl pyridine resin with improved heat resistance and wear resistance and improved catalytic activity can be provided.
- the amount of auxiliary polymerization initiator is the total amount of monomers.
- the monomer is polymerized so as not to increase the polymerization rate, and by using a highly pure crosslinking agent with reduced coexisting impurities, the degree of crosslinking is 35 mol.
- the nitrogen content derived from the pyridine group is 3.00% by mass or more and 8.00% by mass or less while the molar ratio C / N of carbon atom to nitrogen atom is 12.00 or more and 36%. .00 or less, the total pore volume of 0.20 cc / g or more 0.45 cc / g or less and a specific surface area of 70.0m 2 / g or more 280.0m 2 / g or less and an average pore diameter of 5.0nm
- the ratio of the volume of pores having a pore diameter of 25.0 nm or less and 10 nm or more to all pores is 4.0% or more and 90.0% or less, improving heat resistance and wear resistance, and catalytic activity Improved vinylpyridine resin.
- the “specific surface area” is a specific surface area calculated from the amount of nitrogen gas adsorbed using a BET (Brunauer-Emmett-Teller) adsorption isotherm, and “AUTOSORB” manufactured by Yuasa Ionics Co., Ltd. -1 "and measured by the three-point method using liquid nitrogen.
- BET Brunauer-Emmett-Teller
- AUTOSORB manufactured by Yuasa Ionics Co., Ltd. -1
- average pore diameter is measured by a three-point method using “AUTOSORB-1” manufactured by Yuasa Ionics Co., Ltd. using liquid nitrogen.
- Total pore volume is the total amount of all pore volumes, and is measured by “three-point method” using “AUTOSORB-1” manufactured by Yuasa Ionics Co., Ltd. using liquid nitrogen.
- “Ratio of volume occupied by pores having a pore diameter of 10 nm or more in all pores” is a value obtained by dividing “total volume of pores having a pore diameter of 10 nm or more” by “total pore volume”. is there. “The total volume of pores having a pore diameter of 10 nm or more” is also measured by a three-point method using “AUTOSORB-1” manufactured by Yuasa Ionics Co., Ltd. using liquid nitrogen.
- “Nitrogen content derived from vinyl pyridine group” is a ratio of the total amount of nitrogen atoms derived from the vinyl pyridine group in the vinyl pyridine resin of the present invention, and derived from the vinyl pyridine group in the vinyl pyridine resin by elemental analysis. The total mass of nitrogen is determined, and the total mass of the nitrogen is divided by the mass of the vinyl pyridine resin. The nitrogen content derived from the vinylpyridine group is measured by a CHN coder.
- Molar ratio C / N of carbon atom and nitrogen atom is a value obtained by calculating the total mole number C of carbon atoms and the total mole number N of nitrogen atoms in vinylpyridine resin by elemental analysis, and dividing C by N. , Measured by a CHN coder.
- the “degree of crosslinking” is a value obtained from the following formula.
- Crosslinking degree (mol%) A / B ⁇ 100
- the nitrogen content derived from the vinylpyridine group in the vinylpyridine resin of the present invention is preferably from 3.00% by mass to 8.00% by mass.
- the degree of crosslinking is preferably 40 mol% or more and 70 mol% or less.
- the molar ratio C / N of a carbon atom and a nitrogen atom is 14.00 or more and 30.00 or less.
- the total pore volume is preferably 0.20 cc / g or more and 0.40 cc / g or less.
- the vinyl pyridine resin of the present invention has a pore volume ratio of 4.0 to 4.0 which has an average pore diameter of 5.0 nm to 25.0 nm and a pore diameter of 10 nm or more to all pores. % Or more and 90.0% or less, and a resin having a predetermined amount of pores having a pore diameter of 2.0 nm or less is preferable.
- the ratio of the specific surface area of only pores having a pore diameter of 2.0 nm or less to the specific surface area of the vinylpyridine resin is 10% to 70%, preferably 12% or more. 60% or less.
- the proportion of the volume of pores having a certain size of pores specifically, pores having an average pore diameter of 5.0 nm or more and 25.0 nm or less and a pore diameter of 10 nm or more in all pores is 4. It is necessary to be 0% or more and 90.0% or less.
- a rhodium carbonylated complex which is an active species of the carbonylation reaction, has been observed as a dimer ( ⁇ 1 nm ⁇ height about 1 nm).
- the effective pore diameter for the reaction is considered to be 2 to 3 times the molecule, that is, approximately 2.0 nm or less. Further, when the pore diameter is 2 to 3 times the molecule, the potential becomes the most stable due to the wall effect, and therefore pores having a pore diameter of 2.0 nm or less are considered to contribute greatly to the activity. Therefore, in the vinylpyridine resin of the present invention, the proportion of the volume of pores having an average pore size of 5.0 nm or more and 25.0 nm or less and 10 nm or more in the total pores is 4.0% or more, 90.0 It is preferable that the ratio of the specific surface area of only the pores having a pore diameter of 2.0 nm or less is 10% or more and 70% or less.
- the vinyl pyridine resin for a catalyst carrier of the present invention is preferably spherical, and the particle diameter is preferably 50 to 1000 ⁇ m, preferably 150 to 750 ⁇ m.
- the particle diameter can be determined by a laser diffraction method.
- the vinyl pyridine resin of the present invention only needs to satisfy the above requirements, and each numerical value may be set to a desired value according to characteristics required within the range of the requirements. For example, when a long life of the catalyst is particularly required, the nitrogen content derived from the pyridine group is lowered to about 3.00% by mass, and C / N is increased as much as possible. Further, when higher catalyst activity is required even if the catalyst life is relatively short, the C / N is set to about 12.00, and the nitrogen content derived from the pyridine group is set to about 8.00% by mass.
- the vinyl pyridine resin for a catalyst carrier of the present invention is prepared by, for example, mixing an oily medium containing a vinylpyridine, a crosslinking agent, a pore-forming agent, and a polymerization initiator with an aqueous medium, and dispersing the droplets of the oily medium in the aqueous medium.
- the polymerization initiator is 0.25% by mass or less based on the total amount of the monomers, the pore forming agent contains two or more kinds of organic solvents, and the resulting SP value of the vinyl pyridine resin for the catalyst carrier and the SP of the pore forming agent.
- the absolute value of the difference from the value is 1.80 or more and 2.80 or less, it can be manufactured.
- Monomers to be subjected to suspension polymerization are vinyl pyridine and a crosslinking agent (crosslinking monomer). If the above physical properties are satisfied, other monomers may be copolymerized in addition to vinylpyridine and a crosslinking agent.
- vinyl pyridine examples include, but are not limited to, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 4-vinyl pyridine derivatives or 2-vinyl pyridine derivatives having a lower alkyl group such as a methyl group or an ethyl group in the pyridine ring.
- 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, 2-methyl-3-ethyl-5- Vinyl pyridine and the like can be used. These monomers may be used alone, or two or more types of monomers may be used.
- Vinyl pyridine is preferably 20 mol% or more and 65 mol% or less based on the total amount of monomers. If it is less than 20 mol%, the molar ratio of iodine (due to quaternization of the pyridine group) / rhodium in the catalyst becomes small, the rhodium complex becomes unstable, and the catalytic activity decreases. This is because the cross-linking structure necessary for obtaining physical stability tends to be insufficient.
- the crosslinking agent is a compound having two or more reactive sites such as vinyl groups, and a compound having two or more vinyl groups is preferable.
- the compound having two or more vinyl groups include aromatic polyvinyl compounds such as divinylbenzene, divinyltoluene, divinylnaphthalene, or trivinylbenzene, butadiene, diallyl phthalate, ethylene glycol diacrylate, or ethylene glycol dimethacrylate.
- examples thereof include compounds that do not contain nitrogen, such as aliphatic polyvinyl compounds, divinylpyridine, trivinylpyridine, and the like.
- the crosslinking agent is used in an amount of 35 mol% to 70 mol%, preferably 40 mol% to 70 mol%, based on the total amount of monomers.
- Other monomers include monomers having one vinyl group such as ethyl vinyl benzene and styrene.
- crosslinking agents such as divinylbenzene
- the cross-linking agent is a compound having two or more reactive sites such as a vinyl group, but a compound having only one cross-linkable site that is generated as an impurity during synthesis together with the cross-linking agent (for example, Other monomers such as ethyl vinyl benzene) generally coexist.
- a cross-linking agent in which impurities coexist in this way increasing the use ratio of the cross-linking agent can increase the degree of cross-linking, but using a high-purity cross-linking agent in which the coexistence amount of impurities is reduced.
- the content ratio of the vinylpyridine group is lower than when the degree of crosslinking is increased. Therefore, in the present invention, in order to increase wear resistance and heat resistance, a high-purity crosslinking agent with reduced coexisting impurities is used, that is, the amount of other monomers is, for example, 3.0 mol relative to the total amount of monomers. %,
- the nitrogen content derived from the pyridine group is set to 3.00 mass% to 8.00 mass% while increasing the degree of crosslinking to 35 mol% or less and 70 mol% or more. Also make it high.
- the vinylpyridine resin produced from these monomers has a nitrogen content derived from a vinylpyridine group of 3.00 mass% to 8.00 mass%, a crosslinking degree of 35 mol% to 70 mol%, and carbon atoms and Mixing is performed so that the molar ratio C / N of nitrogen atoms is 12.00 to 36.00. Then, a pore forming agent (porous agent) and a polymerization initiator are added to the obtained mixture to obtain an oily medium.
- the pore-forming agent in the present invention refers to a solvent that dissolves the monomer but hardly dissolves the polymer formed by polymerizing the monomer.
- the pore-forming agent charged together with the monomer and the polymer produced are phase-separated in droplets of an oily medium, resulting in a large number of networks.
- Crosslinked microgels are produced.
- the size of the microgel that affects the size of the pores of the resulting vinylpyridine resin, the fusion of the microgels, or the distribution of the organic solvent in the gaps between the microgels depends on the phase of the microgel and the pore-forming agent. Significantly affected by solubility.
- the compatibility between the polymer (vinyl pyridine resin) and the pore-forming agent depends on the polarities of the two, and the closer the polarity is, the higher the compatibility is.
- the absolute value of the difference (hereinafter also referred to as “SP absolute difference”) between the SP value of the vinyl pyridine resin (polymer) for the catalyst carrier and the SP value of the pore forming agent represented by the following formula is 1.
- a material having a molecular weight of 80 or more and 2.80 or less is used as a pore forming agent.
- the SP value is a solubility parameter represented by the square root of the cohesive energy density representing the intermolecular bonding force, and is determined by the Fedors method.
- the SP value of the pore-forming agent is obtained by multiplying the SP value of each organic solvent constituting the pore-forming agent by the volume-based content ratio of the organic solvent with respect to the pore-forming agent, and obtaining the value obtained for each organic solvent. It is the total value.
- the pore-forming agent is composed of three types of organic solvents (first organic solvent, second organic solvent, and third organic solvent), it can be generally determined by the following formula.
- SP absolute difference
- SP value of pore forming agent (SP value of first organic solvent ⁇ (volume of first organic solvent / volume of pore forming agent)) + (SP value of second organic solvent ⁇ (volume of second organic solvent) / Volume of pore-forming agent)) + (SP value of third organic solvent ⁇ (volume of third organic solvent / volume of pore-forming agent))
- an organic solvent having a property of swelling a crosslinked copolymer that is, the vinylpyridine resin of the present invention
- a non-swelling organic solvent or the like
- Specific examples include trimethylbenzene, toluene, xylene, 2-ethylhexanol, dioctyl phthalate, octane, nonane and n-dodecane.
- the pore forming agent preferably contains an organic solvent having a benzene ring, such as trimethylbenzene, toluene, xylene.
- the organic solvent contained in the pore-forming agent Due to the compatibility between the benzene ring of the organic solvent contained in the pore-forming agent and the aromatic ring of the copolymer consisting of vinylpyridine, a crosslinking agent and other monomers to be polymerized as necessary, it has the benzene ring. Since the organic solvent is uniformly distributed in the skeleton in the microgel and in the gaps between the microgels, it is possible to eliminate unevenness in the structure of the obtained vinylpyridine resin and to make powdering and thermal decomposition more difficult to occur.
- the pore forming agent uses at least one of trimethylbenzene and toluene and at least one selected from octane, dioctyl phthalate and n-dodecane, and the mass ratio is the total mass of trimethylbenzene and toluene: octane, dioctyl phthalate and The total mass of n-dodecane is preferably 1: 0.1 to 9.0.
- the total amount of the pore forming agent is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less of the oily medium.
- the pore-forming agent is removed by heating, distillation, extraction with a solvent, etc. after the suspension polymerization reaction.
- the polymerization initiator it is necessary to use both a main polymerization initiator and an auxiliary polymerization initiator having a half-life temperature lower than that of the main polymerization initiator.
- the auxiliary polymerization initiator used in the present invention has, for example, a 10-hour half-life temperature of about 10 to 35 ° C. lower than that of the main polymerization initiator and a 10-hour half-life temperature of 40 to 65 ° C. And the quantity of auxiliary polymerization initiator needs to use 0.25 mass% or less with respect to the monomer whole quantity.
- the suspension polymerization reaction performed in the presence of the pore forming agent starts and proceeds relatively gently. That is, the monomer can be polymerized so that the polymerization rate does not increase. For this reason, although the degree of cross-linking is high, a decrease in pore diameter is suppressed, and vinyl pyridine resin having a somewhat large pore contributing to diffusion in the pore, specifically, a pore having a pore diameter of 10 nm or more Can produce a vinylpyridine resin having a volume ratio of 4.0% to 90.0% in all pores.
- the problem of a decrease in catalyst activity due to a decrease in pore diameter does not occur, and a vinylpyridine resin having high heat resistance and wear resistance and excellent catalyst activity is obtained.
- the heat resistance and wear resistance under methanol carbonylation reaction conditions are greatly improved, and the catalyst has sufficient catalytic activity even when decomposition proceeds to the limit of physical strength as a catalyst used in a fluidized bed.
- the main polymerization initiator used in the present invention is not particularly limited, and any of those conventionally used for initiating the reaction of vinyl compounds such as benzoyl peroxide and lauroyl peroxide can be used. . These may be used alone or in combination of two or more.
- the amount of the main polymerization initiator used is not particularly limited, but if it remains, there is a possibility of adversely affecting the catalyst activity and the catalyst life, so that it is preferable to minimize the polymerization. In addition, since the polymerization rate increases, the pore diameter tends to decrease. Therefore, the amount of the main polymerization initiator used is preferably 0.10% by mass or more and 1.50% by mass or less based on the total amount of monomers.
- the auxiliary polymerization initiator used in the present invention is a polymerization initiator having a lower half-life temperature than the main polymerization initiator.
- auxiliary polymerization initiators include azo polymerization initiators such as 2,2′-Azobis (4-methoxy-2,4-dimethylvalerontrile), 2,2′-Azobis (2,4-dimethylvaleronitile), 2,2 ′.
- Azonitrile compounds such as Azobis (isobutyronitrile), 2,2′-Azobis (2-methylbutyronitrile), organic peroxides such as peroxydicarbonates such as diisopropyl peroxycarbonate and di-n-propyl peroxycarbonate, t Peroxyesters such as hexyl peroxypivalate and t-butyl peroxyneodecaoate can be used. These may be used alone or in combination of two or more.
- the usage-amount of an auxiliary polymerization initiator is 0.25 mass% or less with respect to the monomer whole quantity, Preferably it is 0.05 mass% or more and 0.15 mass% or less.
- an auxiliary polymerization initiator having a half-life temperature lower than that of suspension polymerization and a main polymerization initiator having a half-life temperature higher than that of suspension polymerization it is preferable to use an auxiliary polymerization initiator having a half-life temperature lower than that of suspension polymerization and a main polymerization initiator having a half-life temperature higher than that of suspension polymerization.
- an auxiliary polymerization initiator having a half-life temperature lower than the suspension polymerization temperature an oligomer serving as a nucleus can be generated before polymerization starts as a whole. Since the main polymerization initiator has a role to grow the polymer, it is possible to keep generating radicals little by little until the polymerization is completed by using a main polymerization initiator having a half-life temperature higher than the polymerization temperature. it can.
- Two or more kinds of pore forming agents or polymerization initiators may be prepared by mixing in advance, or may be mixed by stirring or the like in the reactor.
- the resulting vinylpyridine resin has a nitrogen content derived from a vinylpyridine group of 3.00% by mass or more and 8.00% by mass or less.
- the crosslinking degree is 35 mol% or more and 70 mol% or less
- the molar ratio C / N between carbon atoms and nitrogen atoms is 12.00 or more and 36.00 or less
- the total pore volume is 0.20 cc / g or more and 0 or less.
- the ratio of the volume occupied in the holes can be 4.0% or more and 90.0% or less.
- a vinyl pyridine resin having a molar ratio C / N, a total pore volume of 10 nm or more, a specific surface area, and an average pore diameter can be produced.
- the average pore diameter can be adjusted by changing the amount of auxiliary polymerization initiator, the combination of pore-forming agents, the amount and ratio, and the molar ratio C / N of carbon atoms and nitrogen atoms can be changed.
- heat resistance can be adjusted with the quantity of an auxiliary polymerization initiator.
- the aqueous medium used in the present invention is not particularly limited as long as it can be mixed with an oily medium and the monomer in the oily medium can be subjected to suspension polymerization.
- a dispersion stabilizer suspension stabilizer
- an interface It is a solution in which an activator, a deradical radical agent, a specific gravity adjuster, a pH adjuster, etc. are dissolved or dispersed in water.
- the dispersion stabilizer that can be used in the present invention is not particularly limited, and conventionally used polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polymethacrylate, sodium polyacrylate, starch, gelatin, styrene / anhydrous Water-soluble polymers such as ammonium salt of maleic acid copolymer, inorganic salts such as calcium carbonate, calcium sulfate, bentonite and magnesium silicate can be used.
- surfactants deradical agents, specific gravity adjusting agents, and pH adjusting agents that can be used in the present invention, and any conventionally used one can be used.
- dodecylbenzenesulfonic acid or the like as a surfactant sodium nitrite or the like as an anti-radical agent
- sodium chloride, sodium carbonate, sodium sulfate or the like sodium hydroxide or the like as a pH adjusting agent
- sodium hydroxide or the like sodium hydroxide or the like
- the temperature for suspension polymerization may be any temperature at which the polymerization proceeds, but if it is too low, the specific gravity adjusting agent and dispersion stabilizer added to the aqueous medium will be insufficiently dissolved. Moreover, when it exceeds 80 degreeC, temperature rises partially by superposition
- an azo polymerization initiator (10-hour half-life temperature 30 to 67 ° C.) is used, 25 to 80 ° C. is preferably used. Specifically, for example, the polymer is polymerized at 50 to 80 ° C. by gradually raising the temperature, and then the temperature is further raised and heat treatment is applied at 85 to 95 ° C. to produce the vinylpyridine resin of the present invention. Can do.
- the reaction time for suspension polymerization is, for example, 2 to 6 hours, and the heat treatment time is 3 to 20 hours.
- the vinyl pyridine resin for a catalyst carrier of the present invention described above is superior in heat resistance and wear resistance as compared with conventional products, and further has pores that allow easy diffusion of substances and stable active species. Since the activity is excellent, the activity of the catalyst supporting rhodium or the like is high. Therefore, the methanol carbonylation reaction rate can be improved, and the life of the catalyst can be extended, so that the economic efficiency of the process can be improved.
- the catalyst for methanol carbonylation reaction of the present invention can be obtained by supporting rhodium on the vinylpyridine resin for catalyst carrier of the present invention.
- the vinyl pyridine resin for a catalyst carrier of the present invention is excellent in heat resistance and wear resistance, and is excellent in catalytic activity. Therefore, a catalyst in which rhodium is supported is also excellent in heat resistance, wear resistance and catalytic activity.
- the thermal decomposition rate under the conditions of 220 ° C. and nitrogen atmosphere in a mixed solution of 86.5% by mass of acetic acid, 8.0% by mass of methyl iodide, and 5.5% by mass of water is 0.25 per hour. It can be made into mol% or less.
- the method for supporting rhodium on the vinylpyridine resin is not particularly limited.
- a vinylpyridine resin and a rhodium halide or a rhodium salt such as rhodium acetate are added under pressure of carbon monoxide in a solution containing methyl iodide.
- rhodium can be supported on the vinylpyridine resin.
- the nitrogen atom of the vinylpyridine group in the vinylpyridine resin is quaternized, and the rhodium complex ion produced by the reaction of rhodium halide, methyl iodide and carbon monoxide, that is, rhodium carbonyl complex [Rh ( CO) 2 I 2 ] ⁇ is adsorbed in an ion exchange manner to obtain a solid catalyst which is a catalyst for carbonylation reaction of methanol of the present invention.
- the supported amount of rhodium is not particularly limited, but can be about 0.2 to 5.0% by mass with respect to the vinylpyridine resin.
- acetic acid can be produced by reacting methanol and carbon monoxide in the reaction solution.
- methanol carbonylation raw material
- carbon monoxide carbon monoxide
- FIG. 1 is a schematic diagram of an acetic acid production apparatus capable of producing acetic acid by methanol carbonylation.
- an acetic acid production apparatus mainly includes a carbonylation reactor 1 as a reaction process, a flasher 2 that performs a flash evaporation process as a distillation process, a light end distillation column 4 that performs a light end separation process, a static process.
- a decanter 5 as a placing step is provided.
- methanol and carbon monoxide as carbonylation raw materials are introduced.
- Acetic acid as a reaction solvent circulates between the carbonylation reactor 1 and the flasher 2.
- the bottoms of the flasher 2 mainly composed of acetic acid are returned to the carbonylation reactor 1.
- a gas phase fraction from the flasher 2 flows into the light end distillation column 4 and is separated inside the light end distillation column 4.
- Acetic acid is separated and recovered from the lower part of the light end distillation column 4, and components other than acetic acid and a part of the acetic acid that has not been recovered are distilled from the top.
- the methanol carbonylation reaction catalyst of the present invention is dispersed in a reaction solvent.
- Methanol reacts with carbon monoxide to produce acetic acid.
- a reaction accelerator such as alkyl iodide (for example, methyl iodide) is preferably added.
- This reaction is usually performed using acetic acid as a reaction solvent.
- acetic acid serves as a reaction solvent as well as a reaction product.
- carbon monoxide gas is blown into the reaction liquid in the carbonylation reactor 1 in which the catalyst for methanol carbonylation reaction of the present invention is dispersed, and the reaction temperature is increased in the presence of the catalyst for methanol carbonylation reaction of the present invention. Under conditions of 100 to 200 ° C.
- methanol reacts with carbon monoxide to produce acetic acid.
- methyl acetate, dimethyl ether, water and the like are produced as reaction by-products, and these are returned to the reaction step as a residual liquid obtained by separating and recovering acetic acid as a product together with a solvent, a reaction accelerator and an unreacted raw material.
- the liquid phase in the reaction process consists of a mixture of all these components.
- the reaction product liquid produced in the reaction process is subjected to a separation operation in the next distillation process, and the produced acetic acid is separated and recovered as a product, and the remaining liquid is partly returned to the reaction process and the rest is static.
- the reaction liquid is taken out from the carbonylation reactor 1 as a reaction process through a screen or the like and flows into the flasher 2.
- the distillation step a part of the reaction solution is first vaporized by the flasher 2 and separated into a gas phase and a liquid phase (flash evaporation step), and then the gas phase fraction is led from the upper part of the flasher 2 to the light end distillation column 4.
- the method of separating and recovering acetic acid from the lower part is used.
- Such a method is adopted because the reaction product liquid is a mixture of various components as described above, and acetic acid is a component having a low volatility among them. This is because acetic acid cannot be recovered from the bottoms as a product because impurities (or non-volatile) are mixed.
- the flasher 2 and the light-end distillation column 4 can be divided as shown in FIG. 1 and configured as separate columns, or can be provided integrally at the bottom of the single column and at the top thereof.
- the carbonylation reaction is generally an exothermic reaction
- the effect of cooling the liquid phase fraction returned to the reaction step can be obtained, and the heated reaction product liquid can be removed from the flasher 2.
- it can function as an evaporator for the light-end distillation column 4.
- the gas phase fraction is separated.
- acetic acid having the lowest volatility among the components constituting the gas phase fraction accumulate in the lower part of the light end distillation column 4
- all other gas phase components are included in the top fraction.
- Acetic acid is taken out from the lower part of the light end distillation column 4 and subjected to a necessary purification treatment, and then separated and recovered as a product.
- the effluent from the top of the column is introduced into the decanter 5.
- the top effluent of the light end distillation column 4 introduced into the decanter 5 is mainly composed of methyl iodide, methyl acetate, and water.
- methyl iodide contained in the effluent is separated as a heavy oil phase, and an aqueous phase is obtained.
- the separated methyl iodide is returned to the carbonylation reactor 1.
- the portion not vaporized by the flasher 2 accumulates at the bottom of the flasher 2 as a liquid phase fraction, and the carbonylation reaction in which the reaction step is performed as the bottoms from the distillation step (that is, the liquid phase fraction from the flasher 2). Returned to vessel 1.
- acetic acid can be produced efficiently in the above-mentioned acetic acid production method.
- the catalyst for methanol carbonylation reaction of the present invention is excellent in abrasion resistance
- a stirred tank reactor or bubble column reactor for flowing the catalyst is used as the carbonylation reactor 1 for performing the reaction step.
- a reactor or a bubble reactor can be used.
- the catalyst for methanol carbonylation reaction of the present invention is excellent in heat resistance, the reaction temperature of the carbonylation reaction can be increased. Therefore, by changing the reaction temperature according to the reaction state, a stable amount of acetic acid can be produced, and the catalyst life can be extended.
- the water concentration of the reaction solution may increase due to equipment troubles in the purification system such as a distillation process, delay in following conditions associated with changes in the reaction conditions of the carbonylation reaction, and the like.
- the solid-liquid equilibrium of rhodium in the catalyst changes, and rhodium tends to elute into the reaction solution, resulting in a decrease in catalytic activity, a decrease in the amount of acetic acid produced, and a by-product.
- Methyl acetate increases, the decomposition rate of the catalyst increases, and the catalyst life is shortened.
- methyl acetate is produced in a side reaction that CH 3 COOH + CH 3 OH ⁇ CH 3 COOCH 3 + H 2 O.
- the reaction temperature can be increased. Specifically, when the water concentration of the reaction liquid increases, the temperature of the reaction liquid is temporarily increased by a heat exchanger or the like installed inside or outside the reactor. Thus, if the reaction temperature is raised when the water concentration of the reaction solution is increased, the catalytic activity is increased. Therefore, a decrease in the production amount of acetic acid is suppressed, and a stable amount of acetic acid can be produced. In addition, increasing the temperature of the reaction solution makes it difficult for rhodium to elute into the reaction solution, and methanol is consumed as the catalyst activity increases, so that hydrolysis of methyl acetate proceeds and water concentration and methyl acetate are reduced.
- the reaction temperature may be lowered and the reaction may be performed under ordinary conditions. That is, when producing acetic acid using the catalyst for methanol carbonylation reaction of the present invention, it may have a step of increasing the temperature of the reaction solution when the water concentration of the reaction solution is increased. After the step of increasing the temperature of the reaction solution when the water concentration of the reaction solution increases, the method may include a step of decreasing the temperature of the reaction solution when the water concentration decreases.
- the temperature of the hot water flowing through the jacket of the reactor was set to 25 ° C., and the liquid in the reactor was cooled to room temperature, followed by solid-liquid separation by filtration to recover the produced resin.
- the recovered resin is washed with warm water, further extracted with methanol at 65 ° C. to remove the pore forming agents toluene, dioctyl phthalate and n-dodecane, and then classified with a sieve.
- the final 4-vinylpyridine resin for catalyst support was obtained.
- the resulting 4-vinylpyridine resin for catalyst support was spherical.
- Examples 2 to 14 and Comparative Examples 1 to 7 A 4-vinylpyridine resin for a catalyst carrier was prepared in the same manner as in Example 1 except that divinylbenzene (crosslinking agent), pore forming agent species and ratio, polymerization temperature, and polymerization initiator addition amount were as shown in Table 1. Obtained. Table 1 also describes the degree of crosslinking and the absolute value (SP absolute difference) of the difference between the SP value of the vinyl pyridine resin for the catalyst support and the SP value of the pore-forming agent.
- the vinyl pyridine resin for catalyst carrier of Comparative Example 1 corresponds to the vinyl pyridine resin described in Patent Document 7.
- the 4-vinylpyridine resin for catalyst support obtained in each of Examples 2 to 14 and Comparative Examples 1 to 7 was spherical.
- the physical properties of the obtained 4-vinylpyridine resin for catalyst support were measured by the following methods. (1) Specific surface area, total pore volume, ratio of volume occupied by pores having a pore diameter of 10 nm or more in total pores, measurement of average pore diameter Specific surface area of the obtained 4-vinylpyridine resin for catalyst support, The total pore volume, the ratio of the volume of pores having a pore diameter of 10 nm or more to the total pores, and the average pore diameter were measured by the above method using AUTOSORB-1 manufactured by Yuasa Ionics Co., Ltd. .
- the specific surface area (Total) of the entire vinylpyridine resin and the specific surface area ( ⁇ 2 nm) of only pores having a pore diameter of 2.0 nm or less are obtained, and further, the 2.0 nm relative to the total specific surface area.
- the ratio (ratio (%)) of the specific surface area of only pores having the following pore diameters was determined. The results are listed in Table 2.
- the quaternized 4-vinylpyridine resin for catalyst carrier was put into a 300 ml cylindrical separable flask (with 4 baffles) and stirred for 18, 72, 144 hours with a 40 mm desk turbine stirring blade and a stirring speed of 1000 rpm.
- the pulverization rate was determined by the ratio between the amount of the pulverized substance obtained and the mass of the 4-vinylpyridine resin for the charged catalyst carrier. Moreover, the pulverization rate was calculated
- the total amount of the catalyst and 80 g of the reaction solution (methanol 25% by mass, acetic acid 62.5% by mass, methyl iodide 12.5% by mass) were charged into a 200 ml zirconium autoclave, and the reaction temperature was 180 ° C. and the CO pressure was 5.0 MPaG for 1 hour.
- the CO consumption rate when 60 mol% of the charged methanol was reacted was defined as the carbonylation reaction rate (STY; mol / L / h).
- the STY of the comparative example 1 was set to 1.00, and the carbonylation reaction rate ratio was calculated
- the obtained 4-vinylpyridine resin for a catalyst carrier was catalyzed by the above-mentioned method, and 100 ml of a solution containing 8.0% by mass of methyl iodide, 5.5% by mass of water, and 86.5% by mass of acetic acid. At the same time, it was charged into a 200 ml zirconium autoclave, the air inside the autoclave was replaced with nitrogen, and then heated to 220 ° C. with stirring. Thereafter, the state of 220 ° C. was maintained while stirring in the autoclave, and after 24 hours, the liquid was sampled and the nitrogen concentration was measured to determine the amount of detached pyridine groups.
- the nitrogen concentration in the obtained 4-vinylpyridine resin for the catalyst support was separately measured, and the ratio with the detached pyridine group obtained by collecting the liquid after 24 hours (the amount of the detached pyridine group (mol) / obtained).
- the amount of nitrogen in the 4-vinylpyridine resin for catalyst support (mol) was determined, and the ratio was divided by the decomposition time (24 hours) to determine the thermal decomposition rate per hour.
- the physical properties of the resulting 4-vinylpyridine resin for catalyst carrier are shown in Tables 1 and 2.
- the purity of divinylbenzene is “DVB purity”
- the nitrogen content derived from the pyridine group is “N content”
- the molar ratio C / N of carbon atom to nitrogen atom is “C / N”.
- N ratio trimethylbenzene as TMB, dioctyl phthalate as DOP, 2,2′-azobis (2,4-dimethylvaleronitrile) as V65, and benzoyl peroxide as BPO.
- Comparative Example 4 and Comparative Example 6 did not cause carbonylation reaction due to low catalytic activity, and Comparative Example 5 had low wear resistance and decomposed and pulverized during the carbonylation reaction. The pyrolysis rate and powdering rate could not be determined.
- Example 1 For the 4-vinylpyridine resin for catalyst carrier obtained in Example 1 and Comparative Example 1, the following operations and evaluations were performed.
- reaction solution methanol 31.3 mass%, methyl iodide 21.6 mass%, acetic acid 47.1 mass
- Rhodium acetate was charged into a 2000 ml zirconium autoclave and reacted at a reaction temperature of 180 ° C. and a CO pressure of 5.0 MPaG for 1 hour to catalyze.
- the obtained catalyst was charged into a 2000 ml zirconium autoclave together with 1000 ml of a solution of 8.0% by mass of methyl iodide, 5.5% by mass of water, and 86.5% by mass of acetic acid, and the air in the autoclave was replaced with nitrogen. Then, it heated at 220 degreeC, stirring. Thereafter, by maintaining the state at 220 ° C. while stirring in the autoclave for a time (described in the “Time (hr)” column) in the table, the target decomposition rate is maintained. A catalyst was obtained. The nitrogen concentration of the liquid was measured, the amount of pyridine group released was determined, and the decomposition rate was confirmed.
- a catalyst having a different decomposition rate obtained by the above method was fractionated in an amount corresponding to 17 g of 4-vinylpyridine resin (based on dry), and placed in a 300 ml cylindrical separable flask (with 4 baffles). Stirring was performed at a speed of 250 rpm for 18, 72, 144 hours. After the stirring, solid-liquid separation was performed with a sieve having an opening of 90 ⁇ m, the passing liquid was received in a 300 ml beaker with a known mass, evaporated to dryness at 90 ° C., and the mass was measured to obtain a powdered product. The pulverization rate was determined by the ratio between the amount of the pulverized substance obtained and the mass of the charged catalyst.
- a catalyst having a different decomposition rate obtained by the above method was fractionated in an amount corresponding to 8.5 g (based on dry) of 4-vinylpyridine resin, and the activity was determined by the reaction test described above to determine the relationship between the catalyst decomposition rate and the catalyst activity. Asked. The results are shown in Table 5 (Example 1) and Table 6 (Comparative Example 1), and FIG.
- the nitrogen content derived from the vinylpyridine group is 3.00% by mass or more and 8.00% by mass or less, the degree of crosslinking is 35% by mol or more and 70% by mol or less, carbon atoms and nitrogen atoms
- the molar ratio C / N is 12.00 to 36.00, the total pore volume is 0.20 cc / g to 0.45 cc / g, the specific surface area is 70 m 2 / g to 280 m 2 / g, average Examples 1 to 14 in which the proportion of the volume occupied by the pores having a pore diameter of 5.0 nm or more and 25.0 nm or less and the pore diameter of 10 nm or more in all pores satisfies 4.0% or more and 90.0% or less
- This vinyl pyridine resin was excellent in heat resistance, wear resistance and catalytic activity. On the other hand, if there is a condition that does not satisfy even one of the above conditions, a vinylpyridine resin excellent in heat resistance
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Abstract
Description
D=4V/A
架橋度(モル%)=A/B×100
A:ビニルピリジン樹脂の合成に用いた架橋剤(ビニル基等の反応性部位を2個以上有する化合物)のモル数
B:ビニルピリジン樹脂の合成に用いたモノマーの合計モル数
SP絶対差=|触媒担体用ビニルピリジン樹脂のSP値-細孔形成剤のSP値|
細孔形成剤のSP値=(第1有機溶媒のSP値×(第1有機溶媒の体積/細孔形成剤の体積))+(第2有機溶媒のSP値×(第2有機溶媒の体積/細孔形成剤の体積))+(第3有機溶媒のSP値×(第3有機溶媒の体積/細孔形成剤の体積))
[実施例1]
10質量%のNaCl(比重調整剤)、0.3質量%のNaNO2(消ラジカル剤)、0.064質量%のゼラチン(分散安定剤)及び0.009質量%のドデシルベンゼンスルホン酸ナトリウム(界面活性剤)をイオン交換水に溶解させて、625gの水性媒体を調製した。
ジビニルベンゼン(架橋剤)、細孔形成剤種及び比率、重合温度、重合開始剤添加量を表1に示すようにした以外は実施例1と同様にして、触媒担体用4-ビニルピリジン樹脂を得た。表1に、架橋度、および、触媒担体用ビニルピリジン樹脂のSP値と細孔形成剤のSP値との差の絶対値(SP絶対差)も記載する。比較例1の触媒担体用ビニルピリジン樹脂が、特許文献7に記載のビニルピリジン樹脂に相当する。各実施例2~14および比較例1~7で得られた触媒担体用4-ビニルピリジン樹脂は、それぞれ球状であった。
得られた触媒担体用4-ビニルピリジン樹脂の物性を以下の方法により測定した。
(1)比表面積、全細孔容積、10nm以上の細孔径を有する細孔が全細孔に占める容積の割合、平均細孔径の測定
得られた触媒担体用4-ビニルピリジン樹脂の比表面積、全細孔容積、10nm以上の細孔径を有する細孔が全細孔に占める容積の割合、平均細孔径を、上記の方法で、ユアサアイオニクス(株)製、AUTOSORB-1を用いて測定した。比表面積に関して、ビニルピリジン樹脂全体の比表面積(Total)、および、2.0nm以下の細孔径を有する細孔のみの比表面積(≦2nm)を求め、さらに、全体の比表面積に対する該2.0nm以下の細孔径を有する細孔のみの比表面積の割合(比率(%))を求めた。結果を表2に記載する。
CHNコーダーにより、樹脂に含まれる炭素、水素、窒素量を分析し、その値から、窒素含有量(N含有量)、炭素原子と窒素原子とのモル比(C/N比)を求めた。結果を表1に示す。
得られた触媒担体用4-ビニルピリジン樹脂を17g(dry)分取し、ヨウ化メチル17質量%メタノール溶液を100g加え、18時間振とうを行い、ピリジン基の4級化を行った。
(i)触媒化
得られた触媒担体用4-ビニルピリジン樹脂8.5g(dry基準)と反応液79.7g(メタノール31.3質量%、ヨウ化メチル21.6質量%、酢酸47.1質量%)及び所定量の酢酸ロジウムを200mlジルコニウム製オートクレーブに仕込み、反応温度180℃、CO圧力5.0MPaGで1時間反応させ、触媒化した。反応終了後の液をICP発光分光法で分析した結果、反応液へのロジウムの残存率は0.2モル%以下(担持率99.8モル%以上)であった。
(ii)反応試験
得られた触媒担体用4-ビニルピリジン樹脂を前記方法で触媒化し、ヨウ化メチル8.0質量%、水5.5質量%、酢酸86.5質量%の溶液100mlと共に200mlジルコニウム製オートクレーブに仕込み、オートクレーブ内の空気を窒素で置換した後、攪拌しながら220℃に加熱した。その後、オートクレーブ内で撹拌しながら220℃の状態を維持し、24時間後に液を採取して窒素濃度を測定し、離脱したピリジン基量を求めた。また、得られた触媒担体用4-ビニルピリジン樹脂中の窒素濃度を別途測定し、上記24時間後に液を採取して求めた離脱ピリジン基との比(離脱ピリジン基量(モル)/得られた触媒担体用4-ビニルピリジン樹脂中の窒素量(モル))を求め、該比を分解時間(24時間)で除することで1時間当たりの熱分解速度を求めた。
2 フラッシャー
4 ライトエンド蒸留塔
5 デカンタ
Claims (8)
- ピリジン基に由来する窒素含有量が3.00質量%以上8.00質量%以下、架橋度が35モル%以上70モル%以下、炭素原子と窒素原子とのモル比C/Nが12.00以上36.00以下、全細孔容積が0.20cc/g以上0.45cc/g以下、比表面積が70.0m2/g以上280m2/g以下、平均細孔径が5.0nm以上25.0nm以下、且つ10nm以上の細孔径を有する細孔が全細孔に占める容積の割合が4.0%以上90.0%以下であることを特徴とする触媒担体用ビニルピリジン樹脂。
- ビニルピリジンとジビニルベンゼンの共重合体であることを特徴とする請求項1に記載する触媒担体用ビニルピリジン樹脂。
- ビニルピリジン、架橋剤、細孔形成剤及び重合開始剤を含む油性媒体と水性媒体とを混合して懸濁重合することによる触媒担体用ビニルピリジン樹脂の製造方法であって、
前記重合開始剤は、主重合開始剤と主重合開始剤よりも半減期温度が低い補助重合開始剤とを含み、前記補助重合開始剤がモノマー全量に対して0.25質量%以下であり、
前記細孔形成剤は2種類以上の有機溶媒を含み、前記触媒担体用ビニルピリジン樹脂のSP値と前記細孔形成剤のSP値との差の絶対値が、1.80以上2.80以下であることを特徴とする触媒担体用ビニルピリジン樹脂の製造方法。 - 前記主重合開始剤が前記モノマー全量に対して1.50質量%以下であることを特徴とする請求項3に記載する触媒担体用ビニルピリジン樹脂の製造方法。
- 前記細孔形成剤が、ベンゼン環を有する有機溶媒を含むことを特徴とする請求項3または4に記載する触媒担体用ビニルピリジン樹脂の製造方法。
- 前記補助重合開始剤は、半減期温度が前記懸濁重合の温度よりも低く、
前記主重合開始剤は、半減期温度が前記懸濁重合の温度よりも高いことを特徴とする請求項3~5のいずれか一項に記載する触媒担体用ビニルピリジン樹脂の製造方法。 - 請求項1または2に記載する触媒担体用ビニルピリジン樹脂に、ロジウムを担持してなることを特徴とするメタノールのカルボニル化反応用触媒。
- 酢酸86.5質量%、ヨウ化メチル8.0質量%、水5.5質量%の混合液中における、220℃、窒素雰囲気の条件での熱分解速度が、1時間当たり0.25モル%以下であることを特徴とする請求項7に記載するメタノールのカルボニル化反応用触媒。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6125731A (ja) | 1984-07-10 | 1986-02-04 | Mitsubishi Heavy Ind Ltd | 熱交換器水室ノズル口部仮蓋取付装置 |
JPS63253047A (ja) | 1987-02-05 | 1988-10-20 | ヘキスト・セラニーズ・コーポレーション | メタノールのカルボニル化による酢酸の製造方法及びそのための触媒 |
JPH05306254A (ja) | 1992-04-24 | 1993-11-19 | Chiyoda Corp | メタノールのカルボニル化による酢酸の製造方法 |
JPH05306253A (ja) | 1992-04-24 | 1993-11-19 | Chiyoda Corp | メタノールのカルボニル化による酢酸の製造方法 |
JPH06315637A (ja) | 1993-04-30 | 1994-11-15 | Chiyoda Corp | カルボニル化反応用固体触媒及びそれを用いる酢酸の製造方法 |
JPH07309800A (ja) * | 1994-03-25 | 1995-11-28 | Chiyoda Corp | 有機カルボン酸の製造方法 |
JPH0892322A (ja) * | 1994-07-28 | 1996-04-09 | Nippon Steel Chem Co Ltd | 樹脂架橋体 |
JP2012081440A (ja) | 2010-10-14 | 2012-04-26 | Chiyoda Kako Kensetsu Kk | 触媒担体用ビニルピリジン樹脂及びその製造方法 |
EP2631010A1 (en) * | 2012-02-27 | 2013-08-28 | Chiyoda Corporation | Vinylpyridine resin for catalyst carriers and method of manufacturing the same |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5310680A (en) | 1976-07-16 | 1978-01-31 | Sumitomo Chem Co Ltd | Preparation of hig-molecular weight compound comprising vinyl pyridine |
US6066762A (en) * | 1996-12-30 | 2000-05-23 | Chiyoda Corporation | Process for the production of carbonyl compound |
CN1117620C (zh) * | 2000-10-24 | 2003-08-13 | 中国科学院化学研究所 | 甲醇羰基化反应铑锂双金属多相催化剂及其制法 |
RU2319689C2 (ru) * | 2003-03-13 | 2008-03-20 | Тийода Корпорейшн | Способ получения уксусной кислоты (варианты), барботажная колонна для осуществления способа |
MY141209A (en) | 2003-03-13 | 2010-03-31 | Chiyoda Corp | Method of manufacturing acetic acid |
ES2363041T3 (es) | 2006-08-03 | 2011-07-19 | Shell Internationale Research Maatschappij B.V. | Proceso para la preparación de carbonato de alquileno. |
NZ588778A (en) | 2008-04-29 | 2012-07-27 | Celanese Int Corp | Methanol carbonylation system having absorber with multiple solvent options |
US9916619B2 (en) * | 2011-02-14 | 2018-03-13 | Paypal, Inc. | Payment system with location restrictions |
JP2013035805A (ja) | 2011-08-10 | 2013-02-21 | National Institute Of Advanced Industrial Science & Technology | グリセリンの液相酸化反応用触媒及びその触媒を用いたグリセリンの酸化反応方法 |
CN102794198A (zh) * | 2012-07-16 | 2012-11-28 | 江苏索普(集团)有限公司 | 用于乙醇羰基化合成丙酸的催化剂的制备方法及其应用 |
CN103071469B (zh) * | 2013-02-06 | 2015-02-18 | 江苏南大金山环保科技有限公司 | 一种含吡啶基团中极性骨架吸附树脂及其制备方法 |
RU2553273C1 (ru) * | 2014-05-15 | 2015-06-10 | Открытое акционерное общество "Приокский завод цветных металлов" | Способ извлечения платины и/или палладия из отработанных катализаторов на носителях из оксида алюминия |
-
2017
- 2017-03-07 WO PCT/JP2017/009057 patent/WO2017159466A1/ja active Application Filing
- 2017-03-07 US US16/084,023 patent/US11065607B2/en active Active
- 2017-03-07 CN CN201780018539.1A patent/CN108778496B/zh active Active
- 2017-03-07 RU RU2018136346A patent/RU2706610C1/ru active
- 2017-03-07 EP EP17766467.9A patent/EP3431177B1/en active Active
- 2017-03-07 JP JP2018505840A patent/JP6957449B2/ja active Active
- 2017-03-07 BR BR112018068819-3A patent/BR112018068819B1/pt active IP Right Grant
- 2017-03-15 TW TW106108575A patent/TWI642480B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6125731A (ja) | 1984-07-10 | 1986-02-04 | Mitsubishi Heavy Ind Ltd | 熱交換器水室ノズル口部仮蓋取付装置 |
JPS63253047A (ja) | 1987-02-05 | 1988-10-20 | ヘキスト・セラニーズ・コーポレーション | メタノールのカルボニル化による酢酸の製造方法及びそのための触媒 |
JPH05306254A (ja) | 1992-04-24 | 1993-11-19 | Chiyoda Corp | メタノールのカルボニル化による酢酸の製造方法 |
JPH05306253A (ja) | 1992-04-24 | 1993-11-19 | Chiyoda Corp | メタノールのカルボニル化による酢酸の製造方法 |
JPH06315637A (ja) | 1993-04-30 | 1994-11-15 | Chiyoda Corp | カルボニル化反応用固体触媒及びそれを用いる酢酸の製造方法 |
JPH07309800A (ja) * | 1994-03-25 | 1995-11-28 | Chiyoda Corp | 有機カルボン酸の製造方法 |
JPH0892322A (ja) * | 1994-07-28 | 1996-04-09 | Nippon Steel Chem Co Ltd | 樹脂架橋体 |
JP2012081440A (ja) | 2010-10-14 | 2012-04-26 | Chiyoda Kako Kensetsu Kk | 触媒担体用ビニルピリジン樹脂及びその製造方法 |
EP2631010A1 (en) * | 2012-02-27 | 2013-08-28 | Chiyoda Corporation | Vinylpyridine resin for catalyst carriers and method of manufacturing the same |
Non-Patent Citations (4)
Title |
---|
DE SANTA MARIA, L. C. ET AL.: "Microscopic analysis of porosity of 2-vinylpyridine copolymer networks: 1. Influence of diluent", MATERIALS LETTERS, vol. 58, no. 5, February 2004 (2004-02-01), pages 563 - 568, XP004483141 * |
HAMID, M. A. ET AL.: "4-Vinylpyridine-Ethylene Glycol Dimethacrylate Copolymers. Formation of Porous Structure by Using Cyclohexanone and Toluene as Diluents in Suspension Polymerization", POLYMER JOURNAL, vol. 28, no. 12, 1996, pages 1052 - 1059, XP000637628 * |
MAILLARD-TERRIER, M.C. ET AL.: "Texture poreuse de copolymeres 4-vinylpyridine divinylbenzene", EUROPEAN POLYMER JOURNAL, vol. 20, no. 2, 1984, pages 113 - 118, XP024056353 * |
MALIK, M. A.: "Macroporous 4-Vinylpyridine- divinylbenzene - Estimation of Pore Volume Surface Area, and Pore Size Distribution", E- POLYMERS, vol. 6, no. 1, 19 July 2006 (2006-07-19), pages 1 - 8, XP002682308, ISSN: 1618-7229 * |
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WO2023167325A1 (ja) * | 2022-03-03 | 2023-09-07 | 国立研究開発法人理化学研究所 | 固定化パラジウム触媒およびその製造方法、並びに同触媒のカップリング反応への応用 |
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