JPS6116510B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to (a) rhodium, iridium,
A metal cluster selected from the group consisting of um-cobalt.
Star compounds (b) zinc oxide, magnesium oxide
Calcium oxide, Beryllium oxide, Ran oxide
Tan, cerium oxide, thorium oxide, titanium oxide
selected from the group of silica, zirconium oxide and silica.
Carbon monoxide or carbon dioxide fixed on a metal oxide
Oxygen-containing compound having 1 to 2 carbon oxides
Relating to a catalyst for reducing . To explain the manufacturing method of the catalyst, rhodium,
Selected from the group consisting of lydium, rhodium-cobalt.
Carbonyl cluster compounds of discovered metals (hereinafter referred to as
It is called a metal carbonyl cluster compound. )of
Chemically inert solvents such as chloroform, di
Chloromethane, tetrahydrofuran, dimethyls
Polar solvents such as sulfoxide or hexane, pentane
Dissolved in non-polar solvents such as hydrocarbons at a specified dilution rate.
and add metal oxide to this solution to impregnate it.
After removing the solvent, remove the solvent under an inert atmosphere or with hydrogen gas.
It can be manufactured by subjecting it to preliminary heat treatment. Made of this
When carrying out heat treatment in the final step of the manufacturing method,
The active atmosphere is under reduced pressure (10^-Five~Ten^-1About mmHg
) or an inert gas such as nitrogen, helium, or argon.
The hydrogen gas atmosphere is hydrogen.
Gases as well as hydrogen-containing gases, such as synthetic
Under gas or oxo gas atmosphere. this
The reaction temperature is the metal carbonyl cluster compound.
Depending on its stability, 50 to 350℃, preferably
The temperature range is 100-250℃. Metal carbonyl cluster compound used in the present invention
As a product, Rh obtained by conventional methods_Four(CO)₁₂,
Rh₆(CO)₁₆, Rh₂Cp₂(CO)₃, R.H.₃C.P.₃(CO)₃,
Ir_Four(CO)₁₂,Ir.₆(CO)₁₆,Co₂Rh₂(CO)₁₂,
RhCo₃(CO)₁₂,Co₂Rh_Four(CO)₁₆[In the formula, Cp is
It is a clopentadienyl group. ] etc. and Rh₆
(CO)₁₄4M, Rh₆(CO)₁₅2M, Rh₇(CO)₁₆3M,
Rh₁₂(CO)₃₀2M, Rh₁₃(CO)_{twenty three}H_3pr22M, Ir.₆
(CO)₁₅2M, Ir.₈(CO)₁₇2M [In the formula, M is alkali
metal or quaternary alkyl amine. ]
Also mentioned are metal carbonyl cluster salts etc.
I can do it. Also, gold used as the other raw material
Genus oxides include zinc oxide, magnesium oxide,
Calcium oxide, beryllium oxide, lantha oxide
cerium oxide, titanium oxide, zirconium oxide
Examples include aluminum, thorium oxide, and silica.
Ru. The shapes of these metal oxide supports are powder, paste, etc.
Letts, porous particles, or composites with other carriers, etc.
Can be used for any shape
Ru. For the carrier of the obtained cluster immobilization material
In principle, the supported amount ratio of metal clusters can be adjusted to any range.
It can be applied to the supported amount of the surrounding area, but the surface area of the carrier
(1m³/g～1000m³/g) Metal cluster considering
-The supported weight ratio is 50 to 0.0001%, which is a good supported range.
be. Cluster of the present invention formed in this way
The fixed substances are (a) water, tetrahydrofuran, and acetic acid.
Polar solvents such as hexane, pentane, ben
In non-polar solvents such as zene, the class is supported and fixed.
300℃ under inert atmosphere without solvent peeling
No sublimation release due to heating was observed. (B)
The carbonyl of the carbonyl cluster during preparation is
Stoichiometrically desorbed, partially or completely bare metal crystals
Supported and fixed on metal oxide as a raster
Ru. This indicates that the infrared absorption indicates a carbonyl bond state.
The yield peak decreases or disappears under the preparation conditions.
This is clear from the fact that fixed cluster
This patent specification indicates the structural specificity of
Fixed on zinc oxide used in the examples
Infrared spectroscopic considerations for rhodium clusters
According to the investigation, Rh₆(CO)₁₆and acid
CO on Rh cluster immobilized prepared from zinc chloride
2000cm when gas was introduced^-1and 1795cm^-1Strong against
Although strong carbonyl absorption peaks were obtained, these positions
The position and shape of the starting cluster carbonyl compound is
Some Rh₆(CO)₁₆Carbonyl peak of 2040, 1800
cm^-1was extremely similar. On the other hand, the conventional method
When aluminum oxide or zinc oxide contains
Supported rhodium metal obtained by soaking and hydrogen reduction
The adsorbed carbonyl above is 2108, 2100cm^-1and 1860cm
^-1These carbonyl adsorption
From the viewpoint of properties, the cluster immobilization material according to the present invention is
The specificity is obvious. The present invention provides the metal cluster compound with the metal cluster compound.
Carbon monoxide or carbon dioxide fixed in oxides
Reducing element to oxygen-containing compound having 1 to 2 carbon atoms
It provides a catalyst for this purpose. Conventional monoacid
Oxygenated organic compounds from carbon or carbon dioxide and hydrogen
Manufacture of products (synthesis gas method; general
Synthesis method) has been widely researched and has been adopted industrially.
It has been. For example, carbon monoxide and hydrogen are 4:1~
Synthesis gas with a ratio within the range of 1:4 is iron group or noble metal.
Temperatures from 150 to 450℃ with genus group hydrogenation catalysts
and various acids under pressures of 1 to about 700 atmospheres.
Can synthesize elementary organic compounds and hydrocarbons
Ru. [F.Fischer, H.Tropsch, Ber,59,830,
832.923 (1926), R.B.Anderson, “Catalysis”,
p371 (1956) NewYorK, H.Pichler, Adv.
Catalysis， , 271 (1952). ]. However, this person
The method has little selectivity in product distribution and
Recovery of the product is complicated and it is difficult to obtain sufficient conversion.
To achieve this, the reaction must be carried out under conditions of high temperature and high pressure.
This is something that must be improved industrially.
Ru. In addition, as a method for synthesizing methanol, synthetic gas
and zinc oxide-chromium oxide at 300 to 350 atmospheres,
Method for obtaining German Pat in the temperature range of 300 to 400℃
Nos. 415686 and 462837 (1923). ] or suboxide
Lead-chromium oxide-copper at 50-250 atm, 250-300
ICI and Mitsubishi Gas Chemical method obtained in the temperature range of °C [Yamamoto
Written by Tamechika “Methanol and Formalin” Seibundo Shinko
(1962), Special Publication No. 30-8266] is known.
There is. These methods are currently industrialized reactions.
We need to improve the reaction to a milder one from the viewpoint of conditions.
It won't happen. Carbonization containing olefins from synthesis gas
The method for synthesizing hydrogen and oxygen-containing compounds is based on metallic iron.
and iron-supported catalyst, 20-50 atm, 300-350℃
Hydrocol method carried out in the temperature range of
[H.Pichler, Adv・Catalysis, ,271
(1952)], 70-250 atmospheres, 300-400℃
Synthol method [F.Fischer, H.Tropsch,
Brennstoff-Chem.4, 276 (1923),5，
201, 217 (1964),7, 97, 299 (1926),8,65
(1927). ] is already known, but it has poor selectivity.
It is advantageous for producing olefins with a large number of carbon atoms.
Not only that, but also improves the selectivity of olefins.
The molar ratio of carbon monoxide to hydrogen must be large enough to
Low
A method for selectively obtaining grade olefins has not been developed.
The current situation is that there is no such thing. Furthermore, is it from the perspective of reusing carbon resources?
Consisting of carbon dioxide and hydrogen, which are considered important by
A method for obtaining oxygen-containing organic compounds from synthesis gas has been developed.
hydrides, such as lithium, are strong reducing agents.
Stoichiometrically synthesized with aluminum hydride
It is known that carbon dioxide catalytically
A method for synthesizing it from and hydrogen has not been developed. Under such circumstances, the inventor of the present invention has discovered that iridium,
A metal selected from the group consisting of rhodium-cobalt
A cluster compound is defined as a group of metal compounds mentioned above.
Using a substance fixed to a metal oxide selected from
The temperature range is from 100 to 350 degrees Celsius.
Under mild conditions, carbon oxides are reduced and metals,
Oxygenated organic compounds having 2 carbon atoms, e.g.
Ethanol, acetaldehyde and acetic acid and lower
A novel synthesis gas catalyst for selectively synthesizing olefins
This led to the discovery of a medium and the completion of the present invention.
Ru. The selectivity of the reaction depends on the cluster compound and metal used.
How to combine oxides, the mixing ratio of carbon oxide and hydrogen, etc.
However, in each case the product is
Target compound obtained with 60-99% selectivity and total consumption
40-95% of the total amount of carbon oxide is converted to products and by-products
It is characterized by having few things. Regarding reaction conditions and catalysts in the conventional synthesis gas method
When compared with this method, rhodium and iridium
Reduced pressure to normal pressure, 200 to 400 using metal-supported catalysts such as
When attempting to reduce carbon oxide at ℃, the main product is
Methane (80-95%) and small amounts of carbon atoms of 2 or more
It was a hydrocarbon [M.V.Vannic, J.Cat.,37，
449, 462 (1975)], etc., are completely different from the constituent elements of the present invention.
It is objective. In this way, the catalyst of the present invention is different from conventional metal-supported catalysts.
This is a new catalyst that is completely different in terms of composition and catalytic activity.
Yes, and it works extremely effectively in the synthesis gas method.
I understood. Furthermore, this catalyst has a long catalytic activity.
No decrease in activity was observed even after continuous experiments.
No leakage of active metals such as rhodium was observed.
Katta. Carbon monoxide or carbon dioxide reduction catalyst of the present invention
When attempting a reaction, the reaction operation is a closed cycle reaction.
reactor, flow circulation reactor, normal pressure and pressurized flow fixed bed
A type reactor is filled with a catalyst to generate carbon monoxide (or carbon dioxide).
Mix a mixture of gas (carbon) and hydrogen at a predetermined mixing ratio.
After introduction under reduced pressure or increased pressure (1 to about 150 atmospheres),
space velocity 10¹~Ten^Five(1/hr)
Qualitative temperature of 50-450℃, preferably 100-350℃
The reaction is carried out in a temperature range and the product is collected.
Depending on the shape of the catalyst, the catalyst can be dispersed in a solvent.
It can also be applied to a batch type reactor. Synthetic gas
The mixing ratio of the gases can be varied widely and is usually
Carbon: hydrogen = 20:1 to 1:20, preferably
It is within the range of 5:1 to 1:5. Based on experimental results
and to adjust the ratio of carbon monoxide or carbon dioxide to hydrogen.
Higher selectivity of target object and conversion rate of carbon oxide
can be done. In addition, the catalyst of the present invention also has metal carboxylic acid as described above.
Part or all of the carbonyl cluster compound
detaches the group and coordinating organic residue and fixes it on the metal oxide.
However, carbonyl groups and coordinating organic residues
The presence of the group substantially affects the catalytic activity of this reaction.
It's not something you can earn. Below, the method for producing the cluster-fixing substance and its
Examples of synthesis gas method using catalysts
Further, the invention will be explained in detail. Example 1 Rh₆(CO)₁₆0.10gr Tetrahydrofuran 150ml
Dissolved in the solution and preheated it at 320℃ for 10 hours.
Zinc oxide treated with air (Kadox 25N.J.Co.,)
Add 20g and distill off the solvent while stirring.
A light brown powder was obtained. 400Kg/
cm²Pressure molding was performed to obtain pellets of 2 to 4 mm square. Ga
In a flow circulation reactor made of glass (total volume 280ml)
Filled. Heat exhaust treatment was performed at 150-160℃ for 2 hours.
After CO and H₂While circulating the mixed gas of
I responded. The circulation rate was 100ml per minute. Dry ice-acetone coolant in the middle of the circulatory system
The product was collected using a collector using a collector. Generate
For analysis of objects, use Polabacs Q2^m200℃He carrier
and triacetin 4^m90℃He carrier gask
Quantitative measurement was carried out using the secondary analysis method. Reduction of Examples 1-8
CO and H under pressure₂Production of methanol from mixed gas
The results showing the activity are shown in Table 1. Meta in the table
What is the conversion rate of carbon monoxide to methane in total consumed carbon monoxide?
It shows the rate. Example 2 Rh_Four(CO)₁₂Dissolve 0.12gr in 100ml of n-hexane
and heat exhaust treatment (320℃, 10 hours) beforehand.
20g of powdered zinc oxide (manufactured by Kishida Chemical)
After adsorption and loading, the solvent was removed by distillation. this
Pelletize with a tablet molder and transfer to a flow circulation reactor.
(280ml). Vacuum and heat exhaust at 160℃ for 1 hour
After, CO and H₂Introducing a mixed gas of 100ml per minute
When the reaction was carried out at a circulation rate, the reaction temperature was 190 to 240.
Methanol was selectively obtained at ℃. Example 3 Rh_Four(CO)₁₂Dissolve 0.12gr in n-hexane
The oxidized magne- sium has been subjected to heat exhaust treatment in advance.
Add 20g of powder (manufactured by Hanui Chemical) at room temperature and charge.
While stirring for several minutes, remove the solvent by distillation to form a pale red powder.
I got it. Pressure mold this using a tablet press to form pellets.
I made it to Glass flow circulation reactor (280ml)
Fill with pellets and evacuate for 30 minutes at room temperature.
Thereafter, heat exhaust treatment was performed at 150 to 160°C for 40 minutes. child
CO and H₂of mixed gas is introduced, circulating at a rate of 100ml per minute.
When circulated at a ring speed, the reaction temperature was 140℃.
Methanol was obtained at ~240°C. very small amount
It was found that tanol was produced as a by-product, but methanol
The selectivity was 98-99%. Example 4 Rh synthesized by known methods₂Cp₂(CO)₃0.12g
Dissolved in 100ml of n-hexane and degassed.
Added 20gr of zinc oxide powder (Kadox 25 N.J.Co.,)
did. While stirring vigorously, distill off the solvent to remove the pale orange color.
A colored powder was obtained. This is made into pellets using a tablet machine.
and fill it into a glass flow circulation reactor (280ml).
did. 0.8 atm H₂Introduce gas and reduce at 140℃~180℃
After processing, H₂After exhausting the gas, CO and H₂
Do not introduce a mixed gas and circulate the mixed gas.
The reaction took place. Meta in the temperature range of 150℃~270℃
It was found that nol was synthesized. Example 5 Rh_Four(CO)₁₂Dissolve 0.12gr in 150ml of n-hexane.
This solution was subjected to heat evacuation treatment in advance.
Added 20g of calcium oxide powder (manufactured by Merck & Co.)
However, Rh_Four(CO)₁₂was completely adsorbed and supported.
removing the solvent by decantation and vacuum distillation;
A pale orange powder was obtained. This powder is passed through a closed circulation system.
Fill the reaction vessel (volume 420ml) and add 10^-3under torr vacuum
Heat exhaust treatment at 150-165℃ for 30 minutes and 55cmHg at 192℃
H₂Reduction treatment was performed for 35 minutes in the presence of CO and H₂mixture of
Introduce gas and circulate at 190-270℃ at a circulation rate of approximately 100ml per minute
When the reaction was carried out at
Nol and water were collected. A small amount of meta in the gas phase
was generated. Methanol synthesis activity is reproducible
Progresses well and methanol remains even after long repeated reactions.
Synthetic activity and selectivity were retained. Example 6 Rh_Four(CO)₁₂Dissolve 0.12gr in 150ml of n-hexane.
This solution is then added to the previously heat-treated oxidized base.
20g of Lilium (Kishida Chemical GR) powder under reduced pressure
added. While thoroughly stirring, remove the solvent by distillation under reduced pressure.
A supported powder was obtained. This is N₂atmosphere
Fill a closed circulation reactor (400ml) under 160~
After vacuum evacuation at 170℃ for 25 minutes, heat at 190℃ for 40 minutes.₂give back
Ivy. CO and H₂Introducing a mixed gas of about 100ml per minute
When the reaction was carried out at a circulation rate of
alcohol and a small amount of ethanol are obtained, and the gas phase contains
Methane was being produced. Example 7 Ir_Four(CO)₁₂0.10gr to 500ml tetrahydrofura
The mixture was stirred and dissolved in a tube, which had been heat-treated in advance.
Add 20g of zinc oxide (Kishida Chemical) and stir while stirring.
The solvent was removed by vacuum distillation to obtain a supported powder.
Ta. This supported powder is made into pellets using a tablet press.
Filled into a glass flow circulation reactor (280ml)
Ta. After heat exhaust treatment at 190℃ for 2 hours, 200℃ for 30 minutes
H₂I made a return. CO and H₂Introduce a mixed gas of
When the reaction was carried out at 240-270℃, the consumption of CO was
Some methanol and a small amount of water were collected. air
Methane was produced in the phase. Example 8 Ir_Four(CO)₁₂0.10gr of large amount of tetrahydrofuran
Zirconium oxide powder (Hani
Add 20gr of chemical GR) and dissolve the solvent while stirring thoroughly.
was removed by vacuum distillation. The obtained supported powder
Make pellets (2 to 4 mm square) using a tablet press.
A flow circulation reactor (280 ml) was filled. 170-180
℃ After heat exhaust treatment for 30 minutes, CO and H₂conducts a mixed gas of
The reaction was carried out at a circulation rate of approximately 100ml per minute.
It is known that methanol is generated at 200 to 250℃.
Katta. Methane was produced as a by-product in the gas phase. Example 9 Rh_Four(CO)₁₂0.36gr [0.48mmol] in 150ml n-
Dissolve in hexane and pre-heat evacuate the solution.
Treated Magnesium Oxide [Hani Chemical GR] 35gr
Add Rh_Four(CO)₁₂was adsorbed and supported. solvent
The supported powder obtained by removing the powder is pelleted using a tablet press.
A normal pressure flow reaction tube (approx. 2 x 4 mm) (φ20 mm)
×500mm). Pellet-like carrier at 150℃
Evacuate for 20 minutes at₂:CO=2
- Flow a 4:1 mixed gas at normal pressure to start the reaction.
did. Publish the exit gas into a 4.0ml water trap.
to absorb the generated methanol.
Ta. After a certain period of time, methanol and
The amount of ethanol was measured using FID gas chromatography (Hitachi F6, PQ color).
mmφ3mm×4mm, 200℃N₂Carrier)
For gas phase analysis, a certain amount of gas is sampled and activated carbon is added.
Ram 1m room temperature, He carrier and DMF-aluminum
Analyzes were made using a Nacolumn 4m 0°C He Chiraria. So
The experimental results are shown in Table 2.

【table】

【table】

[Table] Example 10 Rh ₄ (CO) ₁₂ 0.12gr synthesized by a known method
-Dissolve in 100ml of hexane and add in advance
20g of titanium oxide powder (manufactured by Merck & Co., Ltd.) that had been deaerated at 320°C for 12 hours was added at room temperature, and the solvent was distilled off while thoroughly stirring to obtain a pale red powder. This was molded into pellets using a tablet molding machine, and filled in a glass flow circulation reactor (280 ml) in air.
After vacuum evacuation treatment at 160℃ for 1 hour, 180℃ with H ₂ 45cmHg
Reduction treatment was performed for 1 hour. When a mixed gas of CO and H ₂ was circulated at a circulation rate of approximately 100 ml per minute, 140
Rapid consumption of CO was observed between ℃ and 220℃, and liquid material was collected in a dry ice-methanol collector in the circulation system. The liquid content was analyzed using a Polapak Q2m column at 200°C He carrier, and it was observed that the product consisted of methanol and ethanol as well as small amounts of acetaldehyde and water. Gas phase components were analyzed using a 1 m room temperature He carrier column of activated carbon for CO, methane, and H ₂ and a 4 m 0° C. column of Al ₂ O ₃ -DMF 35% wt supported for C ₂ to C ₄ hydrocarbon components. All analytical results of the post-reaction products of Examples 10-23 are shown in Table 3. The relative molar ratio of methanol and ethanol in oxygenated compounds can be determined by changing the reaction temperature and the mixing ratio of CO and _H2 .
Although the reaction conditions varied somewhat, reproducible results were obtained when the reaction conditions were set. The methanation rate in Table 3 indicates the proportion of the total consumed carbon monoxide that was converted to methane. Examples 11, 12 Rh ₆ (CO) ₁₆ 0.12gr in tetrahydrofuran 150ml
A burnt brown solution was obtained. Apart from Rh ₂ Cp ₂
0.11 gr of (CO) ₃ was dissolved in 100 ml of n-hexane to obtain a red solution. Add 20g of titanium oxide powder that has been heat-exhausted to each solution at room temperature, and while thoroughly stirring, remove the solvent by distillation to form titanium oxide.
A powder supporting Rh ₆ (CO) ₁₆ or Rh ₂ Cp ₂ (CO) ₃ was obtained. Each of these was molded into pellets using a tablet molding machine, and a glass flow circulation reactor (280ml) was used.
It was filled with. Rh ₆ (CO) _{16 -} For TiO ₂ pellets, heat exhaust treatment at 160 to 180℃ for 1 hour. Rh ₂ Cp ₂
(CO) ₃ -TiO ₂ pellets were subjected to reduction treatment at 180°C for 2 hours in a 0.8 atm H ₂ gas atmosphere.
A mixed gas of CO and H ₂ was introduced and the reaction was carried out while circulating, and the products were analyzed. Example 13 Rh ₄ (CO) ₁₂ 0.11gr from n-hexane solution,
It was diluted and added to zirconium oxide powder (previously heat-exhausted at 320°C for 15 hours), and the solvent was distilled off while stirring to obtain a pale red powder. This was press-molded using a tablet molding machine to form pellets. After filling the glass flow circulation reactor (280ml), the temperature was 160℃.
Vacuum evacuation treatment was performed for 1 hour. Thereafter, a mixed gas of CO and H ₂ was circulated at a rate of about 100 ml per minute under a total pressure of about 0.75 atmospheres, and the reaction was carried out in a temperature range of 130° to 220°C, and the products were analyzed. Example 14 Rh ₄ (CO) ₁₂ 0.11gr was dissolved in 100ml of n-hexane, and this solution was subjected to heat exhaust treatment (320℃ 12
time). Lanthanum oxide 20g (manufactured by Kishida Chemical)
The powder was added and removed by distillation while stirring. The obtained supported powder was molded into 2-4 mm square pellets using a tablet molding machine under a pressure of 400 kg/cm ² . Fill this into a flow circulation reactor (280ml) and heat at 160-170℃ for 30 minutes.
50 after heat evacuation treatment for 30 minutes under reduced pressure of 10 ^-3 Torr
Reduction was performed at 190°C for 1 hour with _H2 at cmHg. Then with CO
When a mixed gas of H ₂ was introduced and the reaction was carried out at a circulation rate of about 100 ml per minute, a liquid product containing methanol and ethanol as main components was obtained. Example 15 0.11 gr of Rh ₄ (CO) ₁₂ was dissolved in 100 ml of n-hexane, 20 gr of cerium oxide powder (Kishida Chemical Co., Ltd.) which had been subjected to heat exhaust treatment in advance was added to this solution, and the solvent was removed by vacuum distillation while stirring. The supported powder was formed into pellets and filled into a flow circulation reactor (280 ml). After heat exhaust treatment (10 ^-3 Torr) at 160-170°C for 30 minutes, hydrogen reduction was performed at 180°C for 40 minutes with H ₂ at 61 cmHg. After that, a mixed gas of CO and H ₂ was introduced and reacted while being circulated. Example 16 When 0.12gr of Rh ₄ (CO) ₁₂ was dissolved in 100ml of n-hexane and 25gr of preheated thorium oxide (Kishida Chemical GR) powder was added to this solution, Rh ₄ (CO) ₁₂ was dissolved well. Supported by adsorption. The solvent was removed by vacuum distillation while stirring. The obtained pale orange powder was made into pellets using a tablet press, filled into a flow circulation reactor (280ml), and heated at 160°C.
After evacuation for 35 min, _H2 reduction was performed at 160-190 °C. When a mixed gas of CO and H ₂ was introduced at 100-190°C and reacted, a liquid product was obtained with a significant decrease in gas pressure. In the temperature range of 100 to 180°C, the liquid products were methanol and ethanol;
At reaction temperatures above 180°C, a significant amount of _C5 is present in the product.
A ~ _C8 hydrocarbon was obtained as an oil. Example 17 Rh ₄ (CO) ₁₂ 0.11gr was dissolved in 250ml of n-hexane, and heat exhaust treatment (320°C 15 hours) was performed in advance.5gr of silica gel (AEROSIL, 300m ² /gr Yokohama Aerosil) was added. It was adsorbed and the solvent was distilled off with vigorous stirring.The resulting pale orange powder was loaded into a glass closed circulation reactor (total volume 420 ml) under _N2.After carefully evacuating at room temperature, Heat exhaust for 15 min at °C, then
Reduction treatment was performed at 190° C. for 1 hour in an atmosphere of H ₂ gas at 0.68 atm. Mixed gas of CO and H ₂ at a total pressure of approximately 60cm
When Hg (0.78 atm) was circulated over the powdered catalyst at a circulation rate of about 150 ml per minute, methanol and ethanol and a small amount of acetaldehyde were obtained. The catalytic ability of this catalyst is such that as the reaction between CO and H ₂ is repeated, the amount of methanol and ethanol produced gradually increases, and the methanation rate tends to decrease, resulting in a continuous reaction for approximately 50 hours. After reaching the steady-state activity value. Example 18 Known method [S. Martinengo, P. Chini, UG
Albano, F. Cariati, J. Organometallic
Chem., 59, 379 (1973)]
Dissolve 0.125gr of RhCo ₃ (CO) ₁₂ in n-hexane,
20g of zinc oxide (manufactured by Kishida Chemical Co., Ltd.) was added to this, and while stirring, the solvent was removed by vacuum distillation to obtain a light cream-colored powder. This was made into pellets and filled into a glass flow circulation reactor (total volume: 280 ml). After heat exhaust treatment at 160°C for 1 hour, a mixed gas of CO-H ₂ was introduced and the reaction was carried out in the temperature range of 160 to 210°C. A liquid product was collected, and an oxygen-containing compound consisting of methanol and ethanol was collected. It turned out to be water. As a result of gas phase analysis, methane and _C2
~ _C4 carbon hydrogen was produced as a by-product. Example 19 0.13 gr of Rh ₂ Co ₂ (CO) ₁₂ synthesized by a known method was supported on 20 gr of zinc oxide powder from an n-hexane solution, and after removing the solvent, the powder was press-molded into pellets and distributed. A circulation reactor (total volume 280 ml) was charged. When a mixed gas of CO and _H2 was introduced, 180
The reaction started at 10°C, and then with constant CO consumption, a liquid product of oxygenated compounds containing approximately equimolar ratios of methanol and ethanol and water was obtained. Example 20 0.18 gr of Rh ₂ CO ₂ (CO) ₁₂ was added to 20 gr of zirconium oxide powder by impregnation from an n-hexane solution, and the solvent was removed by distillation while stirring. this
Under _N2 , a glass closed circulation reactor (total volume 420
ml). Introducing a mixed gas of CO and _H2 ,
The reaction was carried out at a circulation rate of about 100 ml per minute, and methanol containing ethanol as the main component and a small amount of acetaldehyde were obtained. Small amounts of methane and _C2 in the gas phase
~ _C4 hydrocarbons were being produced. Example 21 0.18gr of RhCo ₃ (CO) ₁₂ was dissolved in 100ml of n-hexane, 20gr of zirconium oxide that had been heat-evacuated in advance (evacuated at 320°C for 10 hours) was added, and the solvent was removed by vacuum distillation while stirring. Removed. The obtained supported powder was charged into a closed circulation reactor (total volume 420 ml) under _N2 atmosphere. Evacuate at room temperature and then evacuate at 160℃ for 20 minutes, then 50cm
Hg was reduced in the presence of _H2 for 37 min. A mixed gas of H ₂ and CO was introduced onto the prepared catalyst and reacted at a circulation rate of about 100 ml per minute in a temperature range of 150°C to 250°C. Analysis of the collected liquid material revealed that the main components were methanol and ethanol. Example 22 Dissolve 0.12gr of Rh ₂ Co ₂ (CO) ₁₂ in 100ml of n-hexane, and add lanthanum oxide (Kishida Chemical) to this solution.
20 gr of powder were added and the solvent was removed by vacuum distillation while stirring. The obtained supported powder was charged into a closed circulation reactor (total volume 400 ml). supporting powder
After heat exhaust treatment at 170-180°C for 30 minutes, hydrogen reduction was performed at 190°C in _H2 gas at 50 cmHg. A mixed gas of CO and H ₂ was introduced and reacted while being circulated at 140-200°C, and methanol and ethanol were collected. Example 23 0.10 gr of RhCo ₃ (CO) ₁₂ synthesized by a known method was dissolved in 150 ml of n-hexane, 20 gr of lanthanum oxide powder was added to the solution, and the solvent was removed with stirring to obtain a supported powder. This was filled into a closed circulation reactor (total volume: 400 ml), heated at 160-170°C for 25 minutes, and then subjected to hydrogen reduction at 190°C for 2 hours in the presence of 50 cmHg of _H2 . Introducing a mixed gas of _H2 and CO
When the reaction was carried out in a temperature range of 140° to 200°C, products such as methanol were obtained. Example 24 0.38gr of Rh ₄ (CO) ₁₂ was dissolved in 150ml of n-hexane, 40gr of titanium oxide (Merck Co., GR) powder that had been heat-treated in advance was added to this solution, and the solvent was distilled under reduced pressure while stirring vigorously. was removed to obtain a supported powder [Rh supported rate: 0.5%wt]. This supported powder was formed into pellets, and the pelletized support was placed in a reaction tube (φ20 mm x 500 mm) in a normal pressure flow reactor (made of Px glass).
mm) and heat treated at 150℃ (10 ^-3 Torr under reduced pressure)
After 190℃ H2 _reduction (SV = approx. _200H2 in air flow)
A flow reaction was carried out under the conditions of CO 15 ml/min and H ₂ 40 ml/min. While bubbling the outlet gas into a 40 ml water trap, the produced alcohol and aldehyde were absorbed and collected, and after a certain period of time, a calibration analysis was performed using the FID (Hitachi F6 gas chromatography; PQ column φ 3 mm x 5 mm N ₂ carrier) gas chromatography method. Gas phase methane and _C2 - _C4
Analysis of hydrocarbons was carried out by gas chromatography using an activated carbon column with a 1 m room temperature He carrier and a DMF-Al ₂ O ₃ column with a 4 m 0 °C He carrier. Table 4 shows the reaction results of synthesis gas by the normal pressure flow method under different reaction conditions. Example 25 Rh ₄ (CO) ₁₂ Add 38 gr of lanthanum oxide powder (Kishida Chemical GR) to 0.30 gr of n-hexane solution,
The solvent was removed by vacuum distillation while stirring thoroughly. The obtained supported powder was formed into pellets and filled into a glass reactor similar to that used in Example 8.
After heat exhaust treatment at 150°C for 20 minutes (10 ^-3 Torr), a mixed gas of CO and H ₂ was passed through at normal pressure to start the reaction. (CO15
ml/min, H ₂ at a flow rate of 40 ml/min, SV≒330 hr ^-1 . ) The reaction was carried out at 150° to 190°C. The single flow yield and selectivity of outlet oxygenated compounds, methanation rate, etc. were investigated. The results are shown in Table 5. It was found that the ethanol selectivity increases significantly as the reaction temperature increases. Syngas reaction activity and selectivity were maintained with good reproducibility even after a long period of time.

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【table】

【table】

[Table] In Example 24, C ₂ to _{C 4} hydrocarbons were not detected by TCD.

[Table] Example 26 A reddish-orange solution obtained by dissolving 0.12gr of Rh ₄ (CO) ₁₂ in 100ml of n-hexane was heated at 320°C in advance.
20g of magnesium oxide powder (manufactured by Hanui Chemical Co., Ltd.) that had been heat-exhausted for 12 hours was added at room temperature, and the solvent was distilled off while thoroughly stirring to obtain a pale red powder. This was press-molded using a tablet molding machine to form pellets. Glass flow circulation reactor (280ml)
The tube was filled with pellets, first evacuated at room temperature for 30 minutes, and then heated at 150 to 160°C for 40 minutes. When a mixed gas of CO and H ₂ and a mixed gas of CO ₂ and H ₂ were introduced into this and circulated at a circulation rate of 100 ml per minute, methanol was catalytically synthesized.
When a mixed gas of CO ₂ and H ₂ was circulated, methanol, water, and a considerable amount of CO were produced as by-products from the early stage of the reaction. The methanol synthesis activity from a mixed gas of CO ₂ and H ₂ persisted for a long time even in continuous operation.
Next, in Table 6, the results of the methanol synthesis activity using a mixed gas of CO ₂ +H ₂ when using this catalyst are illustrated. CO on the same catalyst as a reference example
The methanol production activity from a mixed gas of H 2 and H ₂ is added. Example 27 0.12 gr of Rh ₄ (CO) ₁₂ was dissolved in 150 ml of n-hexane, and 20 gr of beryllium oxide (Kishida Chemical GR) powder, which had been heat-treated in advance, was added to this solution under reduced pressure. While sufficiently stirring, the solvent was removed by vacuum distillation to obtain a supported powder. This was charged into a closed circulation reactor (400ml) under an _N2 atmosphere and
After evacuation at 170°C for 25 minutes, H ₂ reduction was performed at 190°C for 40 minutes. Introducing a mixed gas of CO ₂ and H ₂ , approximately 100% per minute
ml circulation rate, a significant amount of CO was produced in the methanol and gas phase at 190°C to 250°C.
The product analysis results of Examples 27 and 28 are shown in Table 7. Example 28 Rh ₄ (CO) ₁₂ 0.11gr was dissolved in 100ml of n-hexane, and this solution was preheated (320℃).
12hr) Lanthanum oxide (Kishida Chemical GR) powder
20 gr was added and the solvent was distilled off while stirring. The obtained supported powder was molded into 2-4 mm square pellets using a tablet molding machine under pressure of 400 kg/cm. Fill this into a flow circulation reactor (280ml) and
After heat evacuation treatment at 170°C for 30 minutes under a reduced pressure of 10 ^-3 Torr for 30 minutes, reduction was performed at 190°C for 1 hour with H ₂ at 50 cmHg. After that, a mixed gas of CO ₂ and H ₂ was introduced and the reaction was carried out at a circulation rate of 100 ml per minute, and as the pressure decreased, a liquid product mainly composed of methanol and ethanol was collected. CO was generated in the gas phase.

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[Table] Example 29 The catalyst was prepared by dissolving 0.40 g of Rh ₄ (CO) ₁₂ in 200 ml of hexane under vacuum, and preheating it (320°C, 15 ml).
40 g of lanthanum oxide powder (99.9%, manufactured by Kishida Chemical Co., Ltd.) that had been subjected to a heat treatment (time) was added thereto, and the mixture was adsorbed and supported. Hexane was removed by vacuum distillation, and after being left under N ₂ for 1 day, it was made into pellets using a tablet molding machine and filled into a pressurized reactor (40φ x 500mm) made of SUS3200 stainless steel (Hastelloy C inner burr). The upper and lower catalyst layers were filled with glass beads. The catalyst was heated at 160°C for 45 min in a 1 atm hydrogen flow (1000ml/min), then at 200°C.
The mixture was heated and reduced at ℃ for 2 hours. Next, the reaction was started by switching to one atmosphere of synthesis gas (CO/H ₂ =0.5, flow rate 800 ml/min). Heat generation was observed when the reaction gas was introduced. Table 8 shows part of the results of sequentially examining reaction activity and selectivity under pressurized conditions of 10, 20 and 40 Kg/cm ² . In addition, the analysis method for oxygen-containing compounds is 200
The outlet gas was bubbled and absorbed into two absorption towers containing 1 ml of water, and a portion was collected and calibrated using FID gas chromatography (Polapack Q column). In addition, gas phase hydrocarbons are TCD gas chromatography (activated carbon, alumina)
DMF and Polapack Q column) were used for calibration. The outlet flow rate was measured using a wet integrating flowmeter.

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[Table] Example 30 The catalyst was prepared by dissolving 0.25 g of Rh ₄ (CO) ₁₂ in hexane under vacuum, and pre-heat exhaust treatment (320°C, 15 hours).
30g of zirconium oxide (99.9% manufactured by Hanui Kagaku Co., Ltd.) was added and adsorbed and supported. This product was treated in the same manner as in Example 29 and charged into a pressurized reactor. The reduction heat treatment was carried out in the same manner as in Example 29, and the reaction was carried out. The results obtained for conversion activity and selectivity for the syngas reaction under various pressurized conditions are shown in Table 9.

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[Table] Example 31 Magnesium oxide powder (99.9% manufactured by Hani Chemical Co., Ltd.)
The process was carried out in the same manner as in Example 29 except that 40 g was used, and the reactor was filled. The reduction treatment was carried out in the same manner as in Example 29, except that it was carried out at 250°C for 5 hours. The results obtained for conversion activity and selectivity towards synthesis gas under various pressurized conditions are shown in Table 10.

【table】

[Table] Reference example: Dissolve 1.25 g of rhodium chloride (RhCl ₃ 3H ₂ O) in distilled water (100 ml) and add silica powder (Wakogel C-
200 (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred and dried under reduced pressure to obtain a supported powder. (Catalyst A). This was made into pellets (4 mm square) using a tablet press and filled into the reactor used in Example 29. The catalyst layer was heated with a one-atmosphere hydrogen flow (1000
ml/min). After the treatment, the reaction was started by switching to synthesis gas, and when steady activity was obtained, the single flow conversion product distribution was examined. The results are shown in Table 11. Acetaldehyde and acetic acid were produced as oxygenated compounds. In addition, a catalyst was prepared in which 1.25 g of rhodium chloride was adsorbed and supported using 20 g of silica (pellet form) manufactured by JGC Corporation as a silica carrier (catalyst B). Perform the same reduction process as above. The results of the reaction are shown in Table 11. When this catalyst is used, the single flow conversion rate of CO--H ₂ reaction decreases as the reaction progresses, and the oxygen-containing compound composition decreases in the proportions of acetaldehyde and acetic acid, while the proportion of ethanol increases. Admitted.

【table】

【table】

Claims (1)

[Claims] (1) A metal cluster compound selected from the group consisting of rhodium, iridium, and rhodium-cobalt (b) Zinc oxide, magnesium oxide, calcium oxide, beryllium oxide, lanthanum oxide, cerium oxide, thorium oxide, titanium oxide, and zirconium oxide. A catalyst for reducing carbon monoxide or carbon dioxide to an oxygen-containing compound having 1 to 2 carbon atoms, which is fixed to a metal oxide selected from the group consisting of silica and silica.