JPH07265708A - Catalyst carrier - Google Patents

Abstract

(57) [Summary] [Object] To provide a catalyst carrier composed of a vinylpyridine resin, which has excellent durability and abrasion resistance. In a catalyst carrier composed of a vinyl pyridine-based resin having a porous cross-linked structure, the vinyl pyridine-based resin has a degree of crosslinking of 30 to 60%, a pore volume of 0.2 to 0.4 cc / g and a volume ratio of 20 to 20. A catalyst carrier having an average pore diameter of 100 nm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst carrier.

[0002]

2. Description of the Related Art Conventionally, in order to produce acetic acid, a vinylpyridine resin having a porous crosslinked structure supporting a rhodium complex has been used as a catalyst for carbonylation reaction in the presence of alkyl iodide in a reaction solvent. A method of reacting methanol and carbon monoxide is known (Japanese Patent Laid-Open No. 63-25 / 1988).
No. 3047). In this publication, vinyl pyridine-based resin used as a catalyst carrier is referred to as Reilly tar and chemical (Reilly tar and chemical).
chemical) (Indianapolis, IN, USA).
5 "(trademark) is described as the most preferred. This catalyst carrier resin has a degree of crosslinking of 33% and a pore volume of 0.
The metal catalyst for carbonylation reaction obtained from this resin having a porous cross-linking structure of 71 cc / g has high carbonylation reaction activity, but the resin used as a catalyst carrier has poor durability and abrasion resistance, When carrying out a carbonylation reaction using this, there is a problem that the resin is partially decomposed, and the pyridine ring contained in the resin is gradually desorbed. Includes the problem of producing fines. The elimination of the pyridine ring from the resin destabilizes the catalytic activity and shortens the catalyst life. On the other hand, the surface abrasion of the resin reduces the activity of the catalyst, and the catalyst fine powder generated by the surface abrasion of the catalyst is mixed in the reaction liquid, which has a great adverse effect on the treatment of the reaction liquid that separates the reaction solvent and acetic acid from the reaction liquid. give.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst carrier composed of a vinyl pyridine type resin which is excellent in durability and abrasion resistance.

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, in a catalyst carrier comprising a vinyl pyridine-based resin having a porous cross-linked structure,
The vinyl pyridine-based resin has a crosslinking degree of 30 to 60%,
Pore volume of 0.2-0.4 cc / g and 20-100 n
Provided is a catalyst support having an average pore size of m.

The vinyl pyridine type resin having a porous cross-linking structure (hereinafter also simply referred to as VP resin) used as a catalyst carrier in the present invention is 30 to 60%, preferably 35.
~ 60% degree of crosslinking, 0.2-0.4 cc / g, preferably 0.3-0.4 cc / g pore volume and 20-100.
nm, preferably 30-90 nm average pore size. VP resin is based on the Rayleigh Ter.
Although various products are commercially available from And Chemicals, those having the above-mentioned characteristics specified in the present invention are not commercially available. The VP resin having the above-mentioned specific degree of crosslinking, pore volume and average pore diameter according to the present invention has excellent durability and abrasion resistance, and overcomes the drawbacks of the conventional catalyst carrier composed of vinylpyridine resin. It is a thing.

Next, the catalyst carrier comprising the VP resin of the present invention and examples of its use will be described in detail. When the VP resin is used as a catalyst carrier, if the degree of crosslinking of the VP resin is smaller than the above range, it is not preferable because it causes problems such as an increase in depyridine rate and reduction in abrasion resistance. On the other hand, if it is larger than the range, It is not preferable because it causes a problem of deterioration of catalytic activity. On the other hand, if the pore volume of the VP resin is smaller than the above range, it is not preferable because it causes a problem of deterioration of catalyst activity, while if it is larger than the above range, it is not preferable because problems such as deterioration of abrasion resistance occur. Further, if the average pore size of the VP resin is smaller than the above range, the problem of reduction in catalytic activity occurs, which is not preferable.
On the other hand, when it is larger than the above range, problems such as deterioration of wear resistance occur, which is not preferable.

[0007] In the present specification, the degree of crosslinking referred to for the VP resin is defined as follows. Further, the pore volume and surface area of the VP resin are measured as follows. Furthermore, the average pore diameter referred to for the VP resin is calculated as follows. (Crosslinking degree) Crosslinking degree (%) = A / B × 100 A: weight of crosslinking agent contained in resin B: weight of vinylpyridine-based monomer contained in resin (pore volume) Mercury pressure porosity The measurement was performed by a method using a meter model 70 (manufactured by Carlo Erba Co., Milan, Italy) (so-called mercury injection method). In this case, the surface tension of mercury is 474 at 25 ° C.
Dyne / cm, the contact angle used was 140 degrees, and the absolute mercury pressure was varied from 1 to 200 kg / cm ² for measurement. (Surface area) B. E. It was measured by the T method. (Average Pore Diameter) Using the respective measured values of the pore volume and surface area measured as described above, it was calculated by the following formula. Average pore diameter (nm) = 4 (C / D) × 10 ³ C: Pore volume (cc / g) D: Surface area (m ² / g)

The VP resin is composed of vinyl pyridine type monomer,
It is produced by copolymerizing an aromatic compound having two vinyl groups as a crosslinking agent. This copolymerization method itself for obtaining the VP resin is a conventionally known method, and for example, (1) a precipitant addition method, (2) a linear polymer addition method,
(3) Swelling agent / precipitant addition method, (4) Diluent / line polymer addition method, etc. A preferred method for producing the VP resin used in the present invention is described in detail in JP-B-61-25731. That is, according to this method, the VP resin is
Produced by polymerizing a mixture of a vinyl pyridine-based monomer, a cross-linking agent having two vinyl groups, and optionally a vinyl monomer in the presence of a radical polymerization reaction catalyst. . In this case, as the polymerization reaction, an aqueous suspension polymerization using water as a medium is adopted. A suspension stabilizer and a precipitant are added to the polymerization reaction system. Suspension stabilizers include polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polymethacrylate, sodium polyacrylate, starch, gelatin, water-soluble polymers such as ammonium salts of styrene / maleic anhydride copolymers, calcium carbonate. Inorganic salts such as calcium sulfate, bentonite, and magnesium silicate are used. Further, sodium chloride or sodium nitrite can be added to the reaction system. As the precipitating agent, an organic solvent that acts as a solvent for the monomer but a poor solvent for the produced polymer, for example,
In addition to C5-10 hydrocarbons such as isooctane, alcohols, esters and the like are used. In such a method for producing a VP resin, the degree of crosslinking of the obtained VP resin can be controlled by the addition amount of the crosslinking agent, and the pore volume and the average pore diameter are determined by the type of the precipitating agent and the addition amount thereof. The amount can be controlled mainly by controlling the type of suspension stabilizer, the addition amount thereof, the reaction temperature and the like.

The vinylpyridine-based monomer used to obtain the VP resin is 4-vinylpyridine, 2-vinylpyridine, a 4-vinylpyridine derivative having a lower alkyl group such as a methyl group or an ethyl group in the pyridine ring, or 2-vinyl pyridine derivative etc. are mentioned. Further, other vinyl monomers, for example, aromatic vinyl monomers such as styrene and vinyltoluene can be mixed in the vinylpyridine-based monomer. The amount of these aromatic vinyl monomers mixed is 30 mol% or less, preferably 2 mol% or less based on the total amount of all monomers.
It is preferable to set it to 0 mol% or less. The cross-linking agent copolymerized with the vinyl pyridine-based monomer is a compound having two vinyl groups. Examples of such compounds include aromatic compounds such as divinylbenzene and divinyltoluene, and aliphatic compounds such as budadiene. The amount of the crosslinking agent used is appropriately determined according to the desired degree of crosslinking of the VP resin.

The particle size of the VP resin is 0.01 to 4 mm, preferably 0.1 to 2 mm, more preferably 0.4 to 2 m.
It is used as a granular material of m, and its preferred shape is a spherical body.

In the present invention, when a rhodium complex is supported on a VP resin, the rhodium complex is represented by a supported form of a rhodium complex ion, for example, [Rh (C
O) ₂ I ₂ ] ^- . Examples of the method for supporting the rhodium complex on the VP resin include the following methods. (1) A method of supporting a rhodium ion on a nitrogen atom of a pyridine ring of a VP resin in an aqueous solution, and then converting it into a rhodium complex in the presence of an alkyl iodide and carbon monoxide in an organic solvent. The reaction between the pyridine ring and rhodium in this method is represented by the following formula. In addition, as the reaction conditions,
Generally, the loading of rhodium should be performed under normal temperature and pressure conditions.
For the complexation of the supported rhodium, the same conditions as the carbonylation conditions of methanol can be used.

[0012]

[Chemical 1] In the above formula, R represents a lower alkyl group.

(2) A method of bringing a VP resin into contact with a rhodium salt in a solvent containing alkyl iodide under pressure of carbon monoxide. In the case of this method, generally, the rhodium salt and the VP resin may be contacted with each other under the carbonylation reaction condition of methanol. The catalyst thus obtained is
The pyridine ring contained in the VP resin is quaternized with an alkyl iodide to form a pyridinium salt, and this pyridinium salt is formed by a reaction of a rhodium salt, an alkyl iodide, and carbon monoxide with a rhodium carbonyl complex [Rh (C
O) ₂ I _2] ^- has a ionically bonded structure.

Examples of the rhodium salt include rhodium chloride and rhodium halides such as rhodium bromide and rhodium iodide. Examples of the alkyl iodide include those having a lower alkyl group having 1 to 6 carbon atoms such as methyl iodide, ethyl iodide and propyl iodide.
The use of methyl iodide is particularly preferred. The use ratio of alkyl iodide to rhodium salt is 2-2000 mol of alkyl iodide, preferably 50 per mol of rhodium salt.
˜500 mol. Further, the carbon monoxide pressure when contacting the rhodium salt and the alkyl iodide is 7 to 30 k.
g / cm ² G, preferably 10 to 20 kg / cm ² G.

When the rhodium complex is supported on the catalyst carrier of the present invention, the amount of the rhodium complex supported is 0.2 to 2% by weight, preferably 0.5 to 1 based on the metal rhodium based on the VP resin. It is preferable to set it in the range of 0.0% by weight.
When the supported amount of the rhodium complex is larger than the above range, the catalytic activity per mol of rhodium metal becomes low, and the product yield per mol of rhodium metal (mol / molRh · h
It is not preferable because r) is decreased and the amount of dissociation of the rhodium complex from the catalyst is increased when the catalyst is used.
Further, in the case of a catalyst in which the amount of rhodium complex supported is constant, the concentration of rhodium existing in the reaction solution after being dissociated from the catalyst does not change much even if the amount of the catalyst used is increased. Therefore, in order to effectively use rhodium, it is preferable to reduce the supported amount of the rhodium and increase the amount of the catalyst used. However, if the amount of the rhodium complex supported is too low, the amount of the catalyst used for obtaining the desired reaction rate is decreased. It is not preferable because the amount becomes too large, stirring in the reactor becomes difficult, and the surface wear of the catalyst easily occurs. From this point, the lower limit of the amount of the rhodium complex supported is preferably 0.2% by weight.

The catalyst of the present invention having a structure in which a rhodium complex is supported on a catalyst carrier is advantageously used as a carbonylation reaction catalyst, for example, a catalyst for acetic acid production by carbonylation of methanol. Generally, a carbonyl of a lower alcohol is used. It can be used as a catalyst for chemical reaction. In the production of acetic acid by the carbonylation reaction of methanol using such a carbonylation reaction catalyst, the catalyst and alkyl iodide are present in the reaction solvent, and methanol and carbon monoxide are introduced into the reaction solvent and reacted. It is carried out by The carbonylation reaction of methanol in this case can be carried out using various reactors. Examples of the type of such a reactor include a fixed bed, a mixing tank, an expanded bed and the like. Further, the catalyst filling amount in the reactor is generally 2 to 40 wt% with respect to the solution in the reactor,
In the case of a mixing tank reactor, it is preferable to select 2 to 25 wt%.
Further, it is preferable to select 20 to 40 wt% for the fixed bed reactor and 2 to 25 wt% for the expanded bed reactor.

As the reaction solvent, various conventionally known ones can be used, but generally, one containing a carbonyl group-containing organic solvent having 2 or more carbon atoms is used. Examples of such a reaction solvent include carboxylic acids such as acetic acid and methyl acetate, and carboxylic acid esters. Further, the reaction solvent may contain water. In this case, the content of water in the reaction solvent is 0.05 to 50 wt%, preferably 0.1 to 20 wt%. As alkyl iodide,
Alkyl iodides having 1 to 6 carbon atoms are used, and in particular,
The use of methyl iodide is preferred.

The amount of reaction solvent in the reactor is preferably 0.30 parts by weight or more per 1 part by weight of methanol. The preferred amount of reaction solvent is 2.40 parts by weight or more relative to 1 part by weight of methanol. By keeping the amount of the reaction solvent in the reaction solution within the above range, the reaction activity of the rhodium carbonyl complex, which is the active center of the catalyst, is increased, and the bond stability between the rhodium carbonyl complex and the pyridinium salt is also improved, which is high. The dissociation of rhodium from the VP resin can be effectively prevented at the reaction rate, and the carbonylation reaction of methanol can proceed smoothly. More importantly, by keeping the amount of the reaction solvent in the reactor within the above range, the rhodium carbonyl complex is stably present even under an extremely low CO partial pressure of 7 kg / cm ² , and the reaction rate is high. The carbonylation reaction of methanol can proceed. This means that it is not necessary to use a special pressure vessel as a reactor, the reactor cost can be largely saved, and a practicable economical acetic acid process can be obtained.

The CO partial pressure (carbon monoxide partial pressure) when carrying out the carbonylation reaction of methanol may be 7 kg / cm ² or more, preferably 10 kg / cm ² or more. Even if the CO partial pressure is made particularly high, the reaction rate does not improve so much and no particular reaction advantage is obtained. From the economical viewpoint, the upper limit of the CO partial pressure is preferably about 30 kg / cm ^2. . Therefore, the CO partial pressure is preferably specified in the range of 7 to 30 kg / cm ² , preferably 10 to 20 kg / cm ² . By keeping the CO partial pressure within such a range, the total reaction pressure is economically 15 to 60 kg / cm ² G, particularly 15 to 40 kg / cm ² G, and more preferably 15 to 3 kg.
It is possible to maintain a low pressure of 0 kg / cm ² G or less.

The reaction temperature in the carbonylation reaction is 140 to 250 ° C., preferably 160 to 230 ° C., but the upper limit thereof is appropriately selected depending on the heat resistance of the VP resin used. The amount of alkyl iodide present in the reaction system is 1 to 40% by weight, preferably 5 to 30% by weight in the solution in the reactor. Further, the rhodium concentration in the reaction system is 50 wtppm or more, preferably 300 wtppm or more, more preferably 400 w in the solution in the reactor.
It is at least tppm. The rhodium concentration referred to here is wt% of the amount of rhodium metal with respect to the solution obtained by removing the VP resin from the reactor.

The amount of the reaction solvent in the reactor is defined according to the type of the reactor as follows. In a batch type reactor, the amount of reaction solvent is based on the amount of methanol in the raw material liquid charged in the reactor. Since the methanol concentration decreases as the reaction progresses, the concentration of the reaction solvent in the reactor becomes higher than the charged raw material. In the mixing tank flow type reactor, the solution in the reactor is uniformly mixed and has substantially the same composition as the reaction product liquid extracted from the outlet of the reactor. That is, in this case, the definition of the amount of the solvent in the reactor is substantially the amount of the reaction solvent with respect to methanol in the reaction product extracted from the outlet of the reactor. In a piston flow type reactor, it is defined as the amount of reaction solvent with respect to methanol in the total feed liquid fed to the reactor. In this case, since the methanol concentration decreases and the amount of the reaction solvent increases from the reactor inlet to the outlet, the amount of the reaction solvent with respect to methanol increases as it advances to the reactor outlet. Therefore, the amount of the reaction solvent is defined as the amount of the reaction solvent with respect to methanol in the total feed liquid supplied to the inlet of the reactor.

In the carbonylation reaction of methanol, side reactions of the following reaction formulas (2) and (3) occur together with the main reaction of the following reaction formula (1). CH ₃ OH + CO → CH ₃ COOH (1) CH ₃ COOH + CH ₃ OH → CH ₃ COOCH ₃ + H ₂ O (2) 2CH ₃ OH → CH ₃ OCH ₃ + H ₂ O (3)

In order to produce acetic acid in good yield, it is necessary to suppress the side reactions (2) and (3) and to selectively proceed the carbonylation reaction (1) of methanol. For this purpose, it is effective to use a reaction solvent containing methyl acetate or water. When methyl acetate is present in the reaction system to increase the yield of acetic acid, it is preferable to add methyl acetate to methanol in advance and supply it to the reaction system. Methyl acetate is 1.
It is preferable to add 5 wt parts or more, preferably 3 wt parts or more, whereby the by-product of methyl acetate can be suppressed and the acetic acid yield can be increased. Further, when the added water is present in the reaction system to increase the yield of acetic acid, the added water is preferably added to methanol in advance and supplied to the reaction system. The added water was 0.
It is preferable to add it in a proportion of 3 wt parts or more, preferably 0.5 wt parts or more, whereby the by-product of methyl acetate and dimethyl ether can be suppressed and the acetic acid yield can be increased.

Even if methyl acetate or acetic acid solvent containing no water is used as a reaction solvent, methyl acetate and dimethyl ether can be obtained by carrying out carbonylation of methanol until the conversion of methanol becomes 96% or more, preferably 99% or more. It is possible to increase the acetic acid yield by suppressing the by-product of. In this case, the concentration of methanol in the reaction product solution is 0.
It is advisable to adjust the methanol conversion rate to 3 wt% or less, preferably 0.2 wt% or less.

The carbonylation reaction of methanol is advantageously carried out using a flow reactor. The flow reactor includes a mixing tank flow reactor and a piston flow reactor. Hereinafter, an example of acetic acid production by carbonylation of methanol using these reactors will be described in detail. FIG. 1 shows an example of a flow sheet of an acetic acid production method using a mixing tank flow reactor. In FIG. 1, R-1 is a mixing tank flow reactor, 7 is a cooler, and S is a separation system.

Reactor R-1 was charged with acetic acid as a reaction solvent, rhodium complex-supporting VP resin as a catalyst, and methyl iodide as a reaction accelerator. It is stirred and mixed uniformly by a stirrer attached to the. To this reactor R-1, methanol containing methyl iodide was introduced from the bottom through lines 1 and 2, and carbon monoxide was introduced from line 3 through a gas disperser attached to the inside of the reactor. To introduce. In this case, water or methyl acetate can be added to methanol as needed. The methanol and carbon monoxide introduced into the reactor R-1 react here in the presence of the rhodium complex-supporting VP resin and methyl iodide to produce acetic acid. A reaction product liquid containing acetic acid produced by this reaction is extracted through a line 4, a part thereof is introduced into a separation system S through a line 5, and another part is cooled through a line 6. After being cooled here through reactor 7, it is circulated to reactor R-1 through line 2. By circulating a part of the reaction product solution through the cooler to the reactor in this way, the heat of reaction generated in the reactor can be removed. The gaseous matter containing unreacted carbon monoxide is withdrawn through line 8 and discharged through flow valve 9 and line 10. From this gaseous substance, low-boiling substances such as methyl iodide contained therein are separated and circulated to the reactor.

The reaction product liquid containing acetic acid introduced into the separation system S is subjected to a separation treatment including distillation here, acetic acid is recovered through a line 11, and a side product after separating acetic acid from the reaction product liquid is obtained. Reaction product residual liquid containing organisms is the line 12,13
Is introduced into the methanol line 1 and is circulated to the reactor R-1 through the line 2. A part of the residual liquid is discharged to the outside of the system through the line 14 as needed. This circulating liquid contains by-products such as methyl iodide, water, hydrogen iodide, methyl acetate and dimethyl ether, as well as unreacted methanol and methyl acetate. Further, a part of the separated acetic acid can be mixed in this circulating liquid.

In the carbonylation reaction of methanol using this mixing tank flow reactor, the ratio of the reaction solvent to methanol may be maintained at a high value of 50 parts by weight or more, preferably 150 to 1000 parts by weight per 1 part by weight of methanol. Since it is easy, the carbonylation reaction of methanol can be carried out rapidly while keeping the catalyst stable and highly active.

When carrying out the carbonylation reaction of methanol as described above, the amounts of methanol and the circulating liquid supplied into the reactor R-1 are adjusted so that the composition of the solution in the reactor falls within the above-specified range. It is preferable to maintain the carbon monoxide partial pressure at 7 to 30 kg / cm ² and the reaction temperature at 140 to 250 ° C. while maintaining the temperature. By carrying out the carbonylation reaction of methanol under such conditions, the reaction pressure is 15 to
60kg / cm ² G, it is possible to quickly perform the carbonylation reaction of methanol with particular 15~40kg / cm ² G the lowered pressure of.

The carbonylation reaction of methanol is an exothermic reaction, and in order to keep the reaction temperature at a predetermined temperature, it is necessary to remove the heat of reaction. As a typical method for removing this heat of reaction, as shown in FIG. 1, a method of extracting a part of the solution in the reactor to the outside, indirectly cooling it with a cooler, and then returning it to the reactor is used. Can be shown. In addition to this method, various methods are possible for removing the heat of reaction. For example, it is also possible to introduce the solution in the reactor into a flasher, vaporize a part of the solution, adiabatically cool the solution, and circulate the cooled solution in the reactor.

The solution in the reactor R-1 can be stirred by a method other than the stirrer. For example, the solution in the reactor is fluidized and stirred by carbon monoxide gas introduced into the reactor. Alternatively, the fluid can be agitated by using a circulating liquid flow into the reactor.

Next, a method for producing acetic acid by a carbonylation reaction of methanol using a piston flow type reactor will be described. FIG. 2 shows an example of a flow sheet of an acetic acid production method using a piston flow type reactor. In FIG. 2, R-2 is a piston flow type reactor, 21 is a gas-liquid separator, and S is a separation system.

The piston flow type reactor R-2 has a structure in which a plurality of catalyst tubes are erected inside. In this case, the catalyst tube has a rhodium complex-supporting VP as a catalyst therein.
It may have a structure filled with resin and may be of a fixed bed type in which the catalyst does not flow or may be of an expanded bed type in which the catalyst flows.

The catalyst tube in the reactor R-2 is cooled by bringing a refrigerant into contact with the outer surface of the reactor tube. Steam is preferably used as the refrigerant. Steam is extracted from the reactor and used as a heat source for the distillation column. Raw material methanol containing methyl iodide is introduced into the inlet of the reactor R-2 through the line 1, the circulating liquid circulated from the line 13 and the carbon monoxide supplied through the line 3. In this case, methyl acetate or water can be added to methanol as needed. A gas-liquid mixture consisting of carbon monoxide introduced into the bottom of the inlet of the reactor R-2 and a liquid containing methanol and acetic acid has a gas-liquid sufficiently dispersed at the inlet of the reactor, and a plurality of catalyst tubes are provided. Liquid and gas are supplied uniformly.

In the catalyst tube, methanol and carbon monoxide react in acetic acid as a reaction solvent in the presence of a catalyst and methyl iodide to be converted to acetic acid. The reaction product liquid containing acetic acid is withdrawn through a line 20 and introduced into a gas-liquid separator 22, where the gaseous substance containing unreacted carbon monoxide is withdrawn through a line 23, and a flow valve 24 and It is discharged through the line 25. Low boiling substances such as methyl iodide are separated from this gaseous substance and circulated to the reactor R-2. The reaction product solution after separating the unreacted carbon monoxide-containing gaseous matter is introduced into the separation system S through a line 22, where acetic acid is separated, and the separated acetic acid is passed through a line 26. Be recovered.

In the separation system S, the residual liquid after separating acetic acid from the reaction product liquid is introduced into the methanol line 1 through lines 12 and 13, and is introduced into the reactor R- through line 2.
It is circulated to 2. A part of this circulating residual liquid is discharged to the outside of the system through the line 14 as needed. This circulating fluid is
It contains by-products such as methyl iodide, hydrogen iodide and water, methyl acetate and dimethyl ether, and unreacted methanol and methyl acetate. Further, a part of the separated acetic acid can be mixed in this.

When carrying out the carbonylation reaction of methanol as described above, the amounts of methanol, acetic acid and the circulating liquid supplied into the reactor R-2 are adjusted to determine the composition of the solution in the reactor as specified above. While maintaining the range, the partial pressure of carbon monoxide is 7 to 30 kg / cm ² , and the reaction temperature is 140 to 2
It is preferable to keep at 50 ° C. By carrying out the carbonylation reaction of methanol under such conditions, the reaction pressure is 15 to 60 kg / cm ² G, especially 15 to 40 kg /
With a lowered pressure of cm ² G, the carbonylation reaction of methanol can be carried out rapidly.

[0038]

EFFECTS OF THE INVENTION The catalyst carrier of the present invention comprises a VP resin having a cross-linking degree, a pore volume and an average pore diameter defined in specific ranges, and has excellent durability and abrasion resistance, and its carrier life is remarkably extended. It was done. The catalyst carrier of the present invention has high durability and effectively prevents the elimination of the pyridine ring from the resin. Further, the catalyst carrier of the present invention has high wear resistance, and the generation of fine powder due to surface wear of the resin is effectively prevented. The catalyst carrier of the present invention is made into a solid catalyst by supporting a catalyst metal component such as rhodium on it. In such a solid catalyst, a catalytic action based on the supported catalytic metal component can be obtained.

[0039]

EXAMPLES The present invention will now be described in more detail with reference to Examples.

Example 1 (1) Preparation of catalyst and catalytic activity test 6.7 g part (dry weight) of vinylpyridine resin, 0.15 g of rhodium chloride, 62.3 g of methanol and 6 of acetic acid.
It was added to a mixed solution consisting of 5.2 g and 11.1 g of methyl iodide, and this was placed in an autoclave equipped with a stirrer to obtain 190
The temperature is raised to 0 ° C., and the inside of the autoclave is pressurized with carbon monoxide until the total pressure reaches 50 kg / cm ^2, and under these conditions, the contents of the autoclave are stirred at 600 rpm for 3 minutes.
Stir for 0 minutes. Then, the content was taken out from the autoclave and washed with methanol to obtain a catalyst composed of a vinylpyridine-based resin supporting a rhodium complex. next,
The catalyst obtained as described above was placed in an autoclave as it was, and further, 65.2 g of acetic acid and 62.
A mixed solution of 3 g and 11.1 g of methyl iodide was charged, heated to 190 ° C., pressurized with carbon monoxide until the total pressure in the autoclave became 50 kg / cm ² , and stirred at 600 rpm. The reaction was carried out for 1 hour. Next, analyze the composition of the reaction solution obtained by the above reaction,
The amount of CO involved in the reaction was measured, and the reaction amount per hour (liter) per 1 liter (Space Time Yield =
STY) was calculated.

(2) Abrasion resistance test of VP resin: 500 g of acetic acid and 25 g (dry weight) of vinylpyridine resin were put into a 1 liter glass container, and a stainless stirring blade having a width of 3.2 cm and a height of 1.2 cm was used. 1000 rpm
The mixture was stirred at room temperature for 1000 hours, and after the stirring was stopped, fine particles of about 10 μm or less floating in the liquid were filtered with a filter having a pore size of 0.2 μm, and the weight A of the fine particles collected by the filter was measured. From this fine particle weight A, a fine particle weight B similarly measured before the test was started was subtracted, and the value was taken as the amount of fine particles generated in the test. The pulverization rate of the resin was calculated from the amount of the fine particles.

(3) Depyridine Decomposition Test A vinylpyridine resin was added to a solution of 90 wt% acetic acid / 10 wt water in a boiling state at 110 ° C., and after 140 hours, the nitrogen concentration in the solution was measured to remove it from the resin. Converted to pyridine ring speed.

Table 1 shows the characteristics of the vinyl pyridine resin used in the above test, and Table 2 shows the test results.

The specific contents of the vinyl pyridine-based resin indicated by the symbols in Tables 1 and 2 are as follows. (Raylex 402) A commercial product from Rayleigh Ter & Chemical, under the trade name "Reillex".
x) 402 ", average particle size: 0.2 mm or less (powdered) (Raylex 425), a commercial product from Rayleigh Ter & Chemical, trade name" Raylex 425 ", average particle diameter: 0.55 mm (KEX316 ) A commercial product from Koei Chemical Co., Ltd., product name "K
EX316 ", average particle size: 0.65 mm (KEX212), a commercial product from Koei Chemical Co., Ltd., trade name" K "
EX212 ", average particle diameter: 0.1 mm (VP resin A) 77 parts by weight of vinyl pyridine and 38 parts by weight of divinylbenzene (containing 40 wt% of ethylvinylbenzene) were added by a precipitating agent addition method (Japanese Patent Publication No. 61-25731).
No.), a copolymer obtained by copolymerization according to
0.5 mm (VP resin B) 72 parts by weight of vinyl pyridine and 47 parts by weight of divinyl benzene (containing 40 wt% of ethyl vinyl benzene) were added by a precipitating agent addition method (Japanese Patent Publication No. 61-25731).
No.), a copolymer obtained by copolymerization according to
0.50 mm (VP resin C) 67 parts by weight of vinyl pyridine and 56 parts by weight of divinyl benzene (containing 40 wt% of ethyl vinyl benzene) were added by a precipitant addition method (Japanese Patent Publication No. 61-25731).
No.), a copolymer obtained by copolymerization according to
0.60 mm (VP resin D) 63 parts by weight of vinyl pyridine and 63 parts by weight of divinyl benzene (containing 40 wt% of ethyl vinyl benzene) were added by a precipitating agent addition method (Japanese Patent Publication No. 61-25731).
No.), a copolymer obtained by copolymerization according to
0.70 mm (VP resin E) 60 parts by weight of vinyl pyridine and 67 parts by weight of divinyl benzene (containing 40 wt% of ethyl vinyl benzene) were added by a precipitating agent addition method (Japanese Patent Publication No. 61-25731).
No.), a copolymer obtained by copolymerization according to
0.65 mm

[0045]

[Table 1]

[0046]

[Table 2] * 1 Cannot be measured because it is a powdery resin

Example 2 In the preparation of the catalyst and the test of catalytic activity in Example 1, catalysts having various amounts of rhodium complex supported on resin B of VP were prepared, and these catalysts were prepared in the same manner. The catalytic activity and the concentration of Rh desorbed in the reaction solution were examined. The results are shown in Table 3.

[0048]

[Table 3]

Example 3 In the catalyst activity test of Example 1, the catalyst of No. 2 shown in Example 2 was used. 2, No. The same experiment was conducted except that the catalyst of No. 4 was used and the amount of the catalyst used was changed variously. In this case, STY and the Rh concentration desorbed in the reaction solution are shown in Table 4 in relation to the amount of catalyst used. The amount of catalyst used is wt% with respect to the raw material mixed liquid charged in the autoclave.

[0050]

[Table 4]

From the results shown in Table 4 above, it is understood that the concentration of Rh desorbed in the reaction solution depends on the amount of Rh supported, but not on the amount of catalyst used.

Example 4 The carbonylation reaction of methanol was continuously carried out using the apparatus system shown in FIG. The reaction conditions in this case were as follows. Further, as the catalyst, a catalyst in which a rhodium complex was loaded as metal Rh in an amount of 0.8 wt% on the VP resin of B in the same manner as in Example 1 was used. In this carbonylation reaction of methanol, even if the reaction was continuously carried out for 4000 hours, almost no catalyst life was observed. (1) Line 2 (component composition) Methanol: 40 wt% Methyl iodide: 10 wt% (flow rate) 200 parts by weight / hr (2) Line 3 (Component composition) CO: 100 mol% (flow rate) 16 parts by weight / hr ( 3) Reaction conditions Temperature: 190 ° C. CO pressure: 15 kg / cm ² Total pressure: 45 kg / cm ² Catalyst filling amount: 10 wt% / Reaction solution Rhodium concentration: 800 wtppm / Reaction solution Stirring speed: 300 rpm (4) From line 4 Reaction liquid (component composition) Methanol: 0.5 wt% Acetic acid: 65 wt% Methyl iodide: 10 wt% Others: 24.5 wt% (Flow rate) 225 parts by weight / hr

[Brief description of drawings]

FIG. 1 shows an example of a flow sheet of an acetic acid production method using a mixing tank flow reactor.

FIG. 2 shows an example of a flow sheet of a method for producing acetic acid using a piston flow type reactor.

[Explanation of symbols]

 R-1 Mixing tank flow type reactor R-2 Piston flow type reactor S Separation system

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location C07C 51/12 53/08 9450-4H (72) Inventor Kazuhiko Hamado Tsurumi-ku, Tsurumi-ku, Yokohama-shi, Kanagawa Chuo 2-12-1 Chiyoda Kakoh Construction Co., Ltd. (72) Inventor Yoshimi Shirato Tsurumi-ku Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture Chiyoda Kakoh Construction Co., Ltd. (72) Inventor Noriyuki Yoneda Yokohama Kanagawa Prefecture 2-12-1, Tsurumi Chuo, Tsurumi-ku, Yokohama-shi Chiyoda Corporation

Claims (3)

[Claims] 1. A catalyst carrier comprising a vinylpyridine resin having a porous crosslinked structure, wherein the vinylpyridine resin has a crosslinking degree of 30 to 60% and 0.2 to 0.4 cc /
A catalyst carrier having a pore volume of g and an average pore diameter of 20 to 100 nm. 2. The catalyst carrier according to claim 1, wherein the vinyl pyridine-based resin contains styrene as a monomer component. 3. The catalyst carrier according to claim 1, wherein the vinyl pyridine-based resin contains divinylbenzene as a cross-linking agent component.