JPS6120341B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oxo reaction catalyst comprising a rhodium cluster or a mixed cluster of cobalt and rhodium and carbon, and a method for producing the same. Conventional catalysts for oxo (hydroformylation) that are commercially practiced include iron or cobalt carbonyl compounds and basic compounds (e.g. alkyl or arylphosphines and nitrogen compounds) to remove some or all of the carbonyl groups. (under pressure of 125 to 200 atmospheres) using a so-called iron group metal group organometallic compound in which
Homogeneous oxo synthesis method carried out at 150-250℃, and rhodium carbonyl complex (general structural formula Rh(CO) _4-x
(PR ₃ ) xx=1 to 4, R: alkyl and aryl substituent) under pressure of 50 to 150 atm, 50° to 200
A homogeneous oxo synthesis method carried out at °C is known and has already been developed as a process for synthesizing aldehydes and alcohols from olefins, carbon monoxide, and hydrogen. Recently, a heterogeneous oxo method has also been published in which a rhodium organometallic complex is substituted and immobilized on an insoluble polymer having a basic group [WOHaag.DDWhitehurst.Belgium Patent No. 721686]
cf. French Patent No. 760,556]. The homogeneous oxo method has the disadvantage that the separation and recovery process of the effective metal catalyst is complicated and expensive, and it requires high pressure. Process improvements remain, such as the need to operate at high temperatures, the power costs for compression and circulation of the reactant gas, and the expensive reactor materials. Further, in order to increase the selectivity of the oxo reaction, it is necessary to add a considerable amount of a basic compound. Recently developed catalysts with immobilized rhodium carbonyl complexes on functional polymers prevent the effective metal catalyst from leaking out and also make it easy to separate the products from the catalyst, but insolubilization technology is not always sufficient. However, the oxo activity under gas phase oxo conditions is extremely small, and even under liquid phase oxo conditions, the activity and selectivity are lower than that of homogeneous oxo catalysts. Functional polymers are expensive as carriers and have low chemical and thermal stability. The present inventor has completed the present invention as a result of intensive studies on the development of highly active and highly selective catalysts for carrying out oxo reactions under milder conditions. The catalyst of the present invention is produced by impregnating rhodium carbonyl clusters or mixed carbonyl clusters of cobalt and rhodium with carbon in an inert solvent, and after removing the solvent, heat-treating the clusters under an inert atmosphere or a hydrogen gas atmosphere. The metal carbonyl clusters used in the method of the present invention have general structural formulas Rh ₄ (CO) ₁₂ , Rh ₆
Rhodium carbonyl cluster compounds represented by (CO) ₁₆ , etc. and Rh ₆ (CO) ₁₅ 2M ⁺ , Rh ₆
(CO) ₁₄ 4M ⁺ , Rh ₇ (CO) ₁₆ 3M ⁺ , Rh ₁₂
(CO) ₃₀ 2M ⁺ , Rh ₁₃ (CO) ₂₃ H _3-x 2M ⁺ [wherein M is an alkali metal or quaternary alkylammonium,
x is a rhodium carbonyl cluster salt represented by 1 to 2], and cobalt and rhodium mixed cluster compounds include RhCO ₃ (CO) ₁₂ ,
Examples include Rh ₂ CO ₂ (CO) ₁₂ and Rh ₄ CO ₂ (CO) ₁₆ . Examples of the carbon used in the present invention include porous carbon such as activated carbon, carbon fiber, graphite, carbon beads, and carbon black, which are common names. Although any shape can be used, it is preferable to have a large effective surface area and a relatively large uniform pore size distribution of 10 Å to 150 Å. The production of catalysts requires the use of inert solvents, such as hydrocarbons such as hexane and heptane, ethers, alcohols, acetone, and water. Heat treatment under an inert atmosphere is also a requirement of the present invention as a treatment after removing the solvent, but the establishment of an inert atmosphere is achieved by vacuum evacuation of 10 ^-5 to 10 ^-1
This can be established by reducing the pressure to about mmHg or by using an inert gas such as nitrogen, helium, or argon. Heat treatment is generally 50-250°C. Furthermore, establishment of a hydrogen gas atmosphere can be achieved not only with hydrogen gas but also with a hydrogen-containing gas such as oxo gas, and in this case, the heating temperature is 50 to 250℃.
°C is preferred. There are no particular restrictions on the weight ratio of metal carbonyl clusters to carbon, but generally the weight ratio of carbon to metal carbonyl clusters is 0.1 to 1.
100,000, preferably in the range of 1 to 10,000. In principle ^, the supported amount ratio of metal carbonyl clusters to carbon can be applied to any range of supported amounts;
1000 m ² /gr), the preferred loading range is 50 to 0.0001% by weight. In the cluster-immobilized substance of the present invention formed in this way, (a) the supported and immobilized clusters cannot be dissolved and peeled off in polar solvents such as water, tetrahydrofuran, and acetone, and non-polar solvents such as hexane, pentane, and benzene; 300℃ under inert atmosphere
No sublimation release due to heating was observed. (b) During preparation, the carbonyl of the metal carbonyl cluster is stoichiometrically eliminated and is supported and fixed on carbon as a partially or completely naked metal cluster. This is also evident from the fact that the infrared absorption peak indicating the carbonyl bond state decreases or disappears under the preparation conditions. Furthermore, a metal cluster carbonyl compound simply adsorbed and dispersed on a carbon carrier exhibits extremely low oxo activity below the decomposition temperature of the metal cluster carbonyl compound. In the production of aldehydes using the catalyst of the present invention, the catalyst is packed in a closed circulation reactor, a flow circulation reactor, a normal pressure and pressurized flow fixed bed reactor, and olefin, carbon monoxide, etc. A mixed gas of hydrogen and hydrogen is introduced under normal pressure or pressure, and the temperature is substantially room temperature to
The reaction is carried out at 250°C and the oxo product is collected. Depending on the shape of the catalyst, it can be applied to a fluidized bed flow reactor or a batch reactor in which the catalyst is dispersed in a polar or nonpolar solvent. As the olefin which is a raw material for producing aldehydes (and alcohols) of the present invention, monoolefins such as ethylene, propylene, butene, and hexene, diolefins such as butadiene, and cyclic olefins such as cyclohexene can be used.
The mixing ratio of olefin: carbon monoxide: hydrogen is not particularly limited, but it is usually olefin: carbon monoxide = 1:10 to 10:1 and carbon monoxide: hydrogen = 1:10 to 10:1. The molar ratio is preferred. Furthermore, the catalyst of the present invention is characterized by not only being able to synthesize linear aldehydes with high selectivity, but also producing a small amount of by-product paraffin. Further, the oxo reaction activity continued for a long time, and no outflow or volatilization of rhodium and cobalt was observed. In addition, as mentioned above, the catalyst of the present invention is one in which the carbonyl of the metal carbonyl cluster is stoichiometrically eliminated during preparation and is supported and fixed on carbon as a partially or completely naked metal cluster. The presence of does not substantially affect the catalytic activity of this reaction. Next, the catalytic ability for oxo synthesis using a catalyst comprising a rhodium cluster or a cobalt rhodium cluster and a carbon support will be further explained using examples. Example 1 0.11 gr of Rh ₄ (CO) ₁₂ was dissolved in 150 ml of n-hexane, and 7 gr of activated carbon (pellet-shaped 4-6 mesh Yukishida Chemical), which had been subjected to heat exhaust treatment, was added to the resulting red-orange solution under reduced pressure. The solvent was removed by distillation under reduced pressure while stirring. This was transferred to a glass flow circulation reactor (total volume 280 ml) under nitrogen gas, heated and exhausted at 160-170°C under a reduced pressure of 10 ^-3 torr for 30 minutes, and then heated at 190°C under hydrogen gas for 1 hour. I did a time reduction process. A mixed gas of ethylene: carbon monoxide: hydrogen (1:1:1, total pressure 0.6 to 0.8 atm) and propylene: carbon monoxide: hydrogen (1:1:1, total pressure 0.8 atm) is circulated at a rate of 100 ml per minute. When reacted at a high rate, propionaldehyde and butyraldehyde were produced at 50-170°C. Product analysis was performed using a Polapack Q4 ^m column (200°C helium carrier) and PEG15002 ^m column (80°C helium carrier), and gas phase analysis was performed using a gas chromatogram using DMF-alumina 4 ^m (0°C helium carrier). It was done according to the law. Tables 1 and 2 show the results regarding the oxo catalyst activity when the reaction conditions were changed. Example 2 0.10gr of Rh ₆ (CO) ₁₅ was dissolved in 150ml of tetrahydrofuran, and 7gr of activated carbon (4 to 6 meshes of granular pellets) that had been subjected to heat exhaust treatment was added to the resulting dark brown solution, and the solvent was dissolved with stirring. was removed by vacuum distillation. In the air, this is transferred to a flow circulation reactor (total volume 280
After evacuation at room temperature for 10 minutes, heat evacuation treatment was performed at 180 to 190°C for 20 minutes under reduced pressure of 10 ^-3 torr, and then a mixed gas of propylene:CO:H ₂ =1:1:1 was introduced. Oxo synthesis activity was investigated in the temperature range of 100-180℃. The circulation rate of the gas mixture averaged about 100 ml/min. Table 3 shows the amount of butyraldehyde produced and the normal and iso isomer ratios when the reaction conditions were changed. In addition, 0.10gr of Rh ₆ (CO) ₁₆ was simply adsorbed and supported on 7gr of activated carbon, which was then charged into a similar flow-through closed circulation reactor, and then heated at 60°C in the form of propylene:CO: _H2 = 1:1:
1. After 15 hours of circulating a mixed gas at a total pressure of 60 cmHg, no production of butyraldehyde or propane was observed to the extent that it could be analyzed. Example 3 Known method [S. Martinengo, P. Chini, VG
Albano, F. Cariati, J. Organometallic chem.,
59 , 379 (1973) _]
(CO) ₁₂ 0.10gr was dissolved in 150ml of n-hexane,
After adding 7 grams of activated carbon that had been previously subjected to heat evacuation treatment, the solvent was distilled off while stirring. This was heated under a nitrogen atmosphere in a flow circulation reactor (total volume 280
ml) and evacuated the residual solvent at room temperature.
Evacuation treatment was carried out under a reduced pressure of 10 ^-3 torr for 45 minutes at 160 to 170°C, and then hydrogen reduction was performed at 190°C for 1 hour. A mixed gas of ethylene: carbon monoxide: hydrogen = 1:1:1 and propylene: carbon monoxide: hydrogen = 1:1:1 was introduced and the reaction was carried out at a circulation rate of 100 ml per minute. Aldehydes were obtained in the temperature range. The ratio of normal to iso forms of butyraldehyde produced in the propylene oxo reaction was 80%, which was characterized by high selectivity for linear products. Furthermore, the molar ratio of by-product paraffin to the amount of oxo produced was extremely low at 0.1 to 0.2. The results of oxo activity are shown in Tables 4 and 5. Example 4 A mixed gas of carbon monoxide:hydrogen = 1:2 was introduced onto the RhCO ₃ supported catalyst prepared in Example 3 and reacted at a total pressure of about 0.8 atm and a circulation rate of 100 ml per minute. As carbon monoxide was consumed in the 270°C temperature range, liquid products were collected in the dry ice acetone cooling section provided in the circulation system. When this was analyzed by gas chromatography using a Polapack Q column (4 ^m , 200°C helium carrier) and a PEG1500 column (2 ^m , 80°C helium carrier), oxygenated compounds consisting of methanol, ethanol, and acetaldehyde were obtained. I realized that I had been told. The amount produced is shown in Table 6. In addition, methane and C ₂ to C ₄ hydrocarbons were generated in the gas phase. Example 5 Rh ₂ CO ₂ (CO) ₁₂ 0.11gr synthesized by known method
was dissolved in 100 ml of n-hexane, and activated carbon (4 to 6 mesh pellets) which had been subjected to heat evacuation treatment under reduced pressure was added thereto to adsorb and support the solution, and then the solvent was removed by distillation under reduced pressure. Activated carbon adsorbing and supporting Rh ₂ CO ₂ (CO) ₁₂ was packed into a flow circulation reactor (total volume: 280 ml) under a nitrogen atmosphere. After heat evacuation treatment under reduced pressure of 10 ^-3 torr for 30 minutes at 160 to 170°C, reduction treatment was performed at 190°C for 40 minutes in the presence of hydrogen at 50 cm and 50 Hg. A mixed gas of propylene (or ethylene): carbon monoxide: hydrogen = 1:1:1 was introduced and reacted at a circulation rate of about 100 ml per minute. The product was collected in a dry ice acetone cooling section in the circulation system. Tables 7 and 8 show the amount of aldehyde produced and the selectivity of aldehyde when the reaction conditions were changed. Example 6 0.32gr of RhCO ₂ (CO) ₁₂ was dissolved in 150ml of n-hexane, and 14gr of activated carbon pellets (4-6 meshes, Wako Pure Chemical Industries, Ltd.), which had been previously degassed and heated, were added to the solution for adsorption and loading. After that, the solvent was removed by vacuum distillation. Activated carbon supporting RhCO ₂ (CO) ₁₂ was placed in a glass reaction tube (φ20 mm) of a normal pressure flow reactor under a nitrogen atmosphere.
x 500 mm) and heated at 150°C for 20 minutes and treated with exhaust (under reduced pressure of 10 ^-3 torr), then propylene:
A mixed gas of carbon monoxide and hydrogen was subjected to a flow reaction.
The outlet gas is bubbled through a 40ml water trap, and after a certain period of time, the absorbed produced butyraldehyde and butyl alcohol are analyzed using FID gas chromatography [Hitachi
Quantitative analysis was performed using F6D, Polapack Q column 4 ^m , 200°C, nitrogen carrier method. For gas phase analysis, use DMF−
Al ₂ O ₃ 4 ^m Analyzed by gas chromatography using a helium carrier at 0°C. The results are shown in Table 9 with respect to the outlet oxo single flow yield, the normal percent of butyraldehyde, and the paraffinization rate under different reaction conditions. Example 7 Rh ₂ CO ₂ (CO) ₁₂ 0.11gr synthesized by known method
was dissolved in 100 ml of n-hexane, 7 grams of activated carbon pellets that had been heated and exhausted were added under reduced pressure, and the solvent was removed by vacuum distillation while stirring. Activated carbon pellets adsorbing and supporting Rh ₂ CO ₂ (CO) ₁₂ were packed into a flow circulation reactor (total volume: 280 ml) under a nitrogen atmosphere. After heat exhaust treatment at 160-170℃ for 30 minutes, heat to 190℃ in the presence of 50cmHg hydrogen.
Reduction treatment was performed for 40 minutes. A mixed gas of propylene (or ethylene): carbon monoxide: hydrogen = 1:1:1 was introduced and reacted at a circulation rate of about 100 ml per minute. The product was collected in a dry ice acetone cooler located in the circulation system. Tables 11 and 12 show the amount of aldehyde produced and the selectivity of aldehyde when the reaction conditions were changed. Example 8 0.32gr of RhCO ₃ (CO) ₁₂ was dissolved in 150ml of n-hexane, and 14gr of activated carbon pellets (4-6 mesh manufactured by Wako Pure Chemical Industries, Ltd.) that had been previously degassed and heated were added to the solution for adsorption and loading. After that, the solvent was removed by vacuum distillation. Activated carbon supporting RhCO ₃ (CO) ₁₂ was packed in a fixed bed in a glass reaction tube (diameter 20 mm x length 500 mm) of a normal pressure flow device under a nitrogen atmosphere, and 150
After heat evacuation (10 ^-3 torr) for 20 minutes at °C, propylene: carbon monoxide: hydrogen = 15 ml/while flowing hydrogen.
Min: 16 ml/min: The reaction was started by switching to a mixed gas of 16 ml/min. Quantitative analysis of the output product was performed using an FID Hitachi gas chromatograph analyzer (Polapack Q column 4 ^m , 200℃ nitrogen carrier) after absorption into a water trap.
I went there. Gas phase analysis was performed using a DMF-Al ₂ O ₃ 4 ^m 0°C column. Table 13 shows the single-stream yield of gas-phase normal pressure propylene oxo activity, linear chain ratio and paraffinization ratio of the aldehyde produced using the RhCO ₃ (CO) ₁₂ -activated carbon cluster-supported catalyst. Example 9 Rh ₂ CO ₂ (CO) ₁₂ Activated carbon (4~
6 mesh (Wako Pure Chemical) 15gr was adsorbed and supported, and the solvent was removed by vacuum distillation. Activated carbon pellets supporting Rh ₂ CO ₂ (CO) ₁₂ were packed into a normal pressure flow reactor under nitrogen atmosphere and heated at 150℃20.
After heating for a minute and evacuation (under reduced pressure of 10 ^-3 torr), hydrogen reduction was performed (180°C for 30 minutes), and oxo gas was passed through, and butyraldehyde was generated. Table 14 shows the single flow yield, aldehyde linear chain rate, and propane production rate under different reaction conditions. Example 10 Using the catalyst used in Example 10, ethylene: carbon monoxide: hydrogen = 20:40:47 as a reaction gas
Propionaldehyde production single flow yield and aldehyde selectivity when oxo gas flows at ml/min,
Table 15 shows the results of examining the ethane production rate.

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[Table] Example 11 0.17gr of Rh ₂ CO ₂ (CO) ₁₂ was adsorbed and supported on 7g of activated carbon (10 to 20 mesh Wako Pure Chemical, preheated at 320°C for 15 hours) from an n-hexane solution. After vacuum distillation of He at room temperature,
Of that, 6gr was transferred to a stainless steel reactor (φ15mm x 220
mm, SUS32). The height of the catalyst layer is approximately 8cm
The top and bottom of the catalyst layer were filled with φ2mm glass beads. While flowing hydrogen gas at a flow rate of 1 atm and approximately 9/hr, the temperature was 80°C for the first 50 minutes and 150°C for the next 40 minutes.
℃, and after further heat treatment at 170℃ for 15 minutes C ₃ H ₆ :
A mixed gas of CO:H ₂ ≒1:1:1 was passed through to start the reaction. After 10 hours, when steady activity was obtained, a pressurized propylene oxo mixed gas of 5Kg/cm ² , 10Kg/cm ² , and 20Kg/cm ² was reacted to determine the oxo conversion rate at the outlet, the paraffinization rate, and the linear chain of the butyraldehyde produced. I checked the rate. Gas phase analysis is alumina-DMF4 ^m
The analysis was carried out using TCD gas chromatography using a column He carrier at room temperature.The liquid product was absorbed into two absorption bottles each containing 200 ml of distilled water, and then the liquid product was absorbed into two absorption bottles containing 200ml of distilled water ^.
Quantitative analysis was performed using FID gas chromatography using column _N2 carrier. No by-products were detected other than butyraldehyde and a trace amount of butyraldehyde. Table 16 shows the results of the oxo reaction activity test under pressures of 0 ^k , 5 ^k , 10 ^k , and 20 ^k . The composition of pressurized propylene oxo gas is approximately
The ratio of C ₃ H ₆ :CO:H ₂ was 1:1:1. ^5k ,
Pressurized oxo gas at 10 ^k and 20 ^k is autoclaved
It was prepared by mixing propylene, CO and H ₂ (1:1) at 100°C and then introduced into the reactor via a heated stainless steel pipe.

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[Table] Note that no outflow of metal from the catalyst layer after the pressurized reaction was observed based on test results such as ammonium rhodanate color reaction. Example 12 Rh ₂ Co ₂ (CO) ₁₂ 0.70gr was added to activated carbon from a hexane solution (10-20 meshes Wako Pure Chemical, 320g in advance).
℃, heat exhaust treatment for 15 hours) was adsorbed and supported on 27gr. After the solvent was distilled under reduced pressure, it was packed into a stainless steel reactor (φ20 mm×500 mm SUS32) at room temperature under nitrogen. The height of the catalyst layer was approximately 15 cm, and 2 mm diameter glass beads were packed above and below the catalyst layer. While flowing hydrogen gas at a flow rate of 1 atm approximately 60/hr, heat treatment was performed at 80°C for the first 50 minutes and at 150°C for the next 40 minutes, and then ethylene:CO:H ₂ =1 :1:1
The reaction was started at 1 atm.
After 10 hours, when steady activity was obtained, 5Kg/
cm ² , 10Kg/cm ² , 20Kg/cm ² , 33Kg/cm ² , and 35Kg/cm ² of pressurized ethylene oxo mixed gas were reacted, and the outlet oxo conversion rate, aldehyde production amount, ethanization rate, and aldehyde selectivity were measured. Examined. Gas phase analysis was performed by TCD gas chromatography using a Polapack Q2m column at 45℃ and a helium carrier.The liquid product was passed through two absorption bottles containing 200 ml of distilled water, and after being completely absorbed. , Polapatsk
Quantitative analysis was performed using FID gas chromatography using a Q4m column and nitrogen carrier. 0Kg/ ^cm2 , 5Kg/
Table 17 shows the results of the pressurized propionaldehyde synthesis activity test at ^cm2 , 10Kg/ ^cm2 , 20Kg/ ^cm2 , 33Kg/ ^cm2 , and 35Kg/ ^cm2 . The composition of the pressurized ethylene oxo gas is C ₂ H ₄ :CO:H ₂ = 1:1:1, and the pressurized gas is adjusted by accumulating pressure of each component in a pressure cylinder using a gas compressor. Ta. After a certain period of time had elapsed, the mixture was introduced into the reactor via a heated stainless steel pipe and after adjusting the pressure with the primary and secondary pressure regulating valves.
The flow rate and flow rate of the mixed gas were calculated using a wet integrated flowmeter. In addition, when we conducted a continuous experiment for 100 hours under the conditions of 146-195℃ and 10-35 atm regarding the pressurized propionaldehyde synthesis activity using this catalyst, we found that 100
Both the aldehyde space-time yield and oxo selectivity before and after the continuous time test maintained constant results, confirming that the catalyst activity was sustained. A pressurized propionaldehyde synthesis activity test was conducted in the same manner as in Example 12 using 0.40 gr of Rh ₂ Co ₂ (CO) ₁₂ and 15 gr of activated carbon, and the results are listed in Table 18.

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These are the values derived from [Table].

Claims (1)

[Claims] 1. An oxo reaction catalyst comprising a rhodium cluster or a mixed cluster of cobalt and rhodium and carbon. 2. Production of a catalyst for oxo reaction, characterized by impregnating rhodium carbonyl clusters or mixed carbonyl clusters of cobalt and rhodium with carbon in an inert solvent, removing the solvent, and heat-treating in an inert atmosphere or hydrogen gas atmosphere. Method.