JPS63162639A - Production of ethanol - Google Patents

Abstract

PURPOSE:To obtain ethanol readily in high selectivity and in high yield, by reacting CO with H2 by the use of a specific compounded catalyst. CONSTITUTION:CO is reacted with H2 in a blending ratio of 0.1-10 (volume ratio) in the presence of a catalyst obtained by supporting rhodium, lithium, copper, indium and/or at least one of scandium, magnesium, yttrium, ytterbium, lutecium, vanadium and chromium on a carrier such as silica gel, etc., and a catalyst comprising copper or copper, zinc and/or chromium at 150-450 deg.C under 0-350kg/cm<2> gauge pressure at 10-10<6>h<-1> space velocity calculated as standard state (0 deg.C, 1atm.) to give ethanol. The two catalysts used are individually and separately prepared, ordinarily the above-mentioned components are dispersed on the carrier as carried out in a noble metal catalyst and the catalysts are prepared by impregnation method, immersion method, ion exchange method, coprecipitation method, kneading method, etc.

Description

[Detailed description of the invention] The present invention relates to a method for producing ethanol.

More specifically, (a) at least one element selected from rhodium, lithium, copper, iridium and/or scandium, magnesium, yttrium, ytterbium, lutetium, vanadium, and chromium (hereinafter abbreviated as other additive elements) is supported on a carrier. (b) (1)
A method for producing ethanol comprising reacting carbon monoxide with hydrogen in the presence of copper or (2) a catalyst comprising copper, zinc and/or chromium.

(Problems to be solved by the prior art and the invention) Oxygenated compounds having two carbon atoms, such as ethanol and acetaldehyde, have traditionally been produced by petrochemical methods using naphtha as a raw material.However, in recent years, the demand for crude oil has increased rapidly. Considering price fluctuations, supply instability, and the limited amount of carbon resources, there is a need to develop alternative carbon resources.

On the other hand, various methods of producing an oxygen-containing compound having 2 carbon atoms from a mixed gas of carbon monoxide and hydrogen, which is available in abundance and at low cost, have been studied. That is, by reacting a mixed gas of carbon monoxide and hydrogen in the presence of a catalyst containing rhodium as a main component and consisting of a metal or metal oxide such as manganese, titanium, zircon, or iron, an oxygen-containing compound having two carbon atoms is produced. The method of selectively producing
No. 6, No. 51-14706, No. 56-147730, etc.).

However, even with this method, the amount of by-product hydrocarbons, such as methane, is large, and when the selectivity of oxygen-containing compounds is low or the selectivity of oxygen-containing compounds is high, the amount produced is extremely low. Ta.

The reality is that the amount of the target compound produced based on rhodium, which is an expensive noble metal, is still small, and a technology that has been completed economically and process-wise has not been provided.

Furthermore, lithium (Japanese Unexamined Patent Application Publication No. 1983-1995
-8334), iron (JP 51-80807), magnesium (JP 54-138504), vanadium (JP 57-62232), yttrium, ytterbium (JP 57-62233) , chromium (Japanese Unexamined Patent Publication No. 55-143918), rhodium and lithium and magnesium or vanadium, etc. (Japanese Unexamined Patent Publication No. 57-109)
No. 734), etc. have been proposed, but all of these methods use acetaldehyde, acetic acid, or methanol as the main products, and have the disadvantage that the yield and selectivity of ethanol are extremely low.

Recently, a method for selectively synthesizing ethanol (especially 1988-178939, JP-A 61-17
8940, JP-A-61-178941, JP-A-61-1
78942), but the selectivity of ethanol is not a satisfactory result for a practical process.

In addition, a synthesis method using a multi-element catalyst containing metals, rhodium, alkali metals, etc. has been proposed (US Pat. No. 4,537,909), but the ethanol selectivity is low, the ratio of methanol and propatool is high, and other , a method for producing ethanol using a catalyst containing rhodium, vanadium, and copper (Sho 6O-32734) has been shown, but the selectivity and production activity of ethanol were quite low.

As described above, a method for efficiently (economically) producing an oxygen-containing compound mainly composed of ethanol from a gas containing carbon monoxide and hydrogen has not been provided.

The present inventors discovered that from a gas containing carbon monoxide and hydrogen,
When producing an oxygen-containing compound, while improving the selection of the above-mentioned oxygen-containing compound having two carbon atoms, the distribution in the oxygen-containing compound having two carbon atoms produced by the reaction is shifted to ethanol, and the hydrocarbon It discloses a catalytic system that makes it possible to minimize the formation of a large number of promoter component combinations. ! ! As a result of repeated studies, we found that (a) a catalyst comprising at least one element selected from rhodium, lithium, copper, iridium and/or scandium, magnesium, yttrium, ytterbium, lutetium, vanadium, and chromium supported on a carrier; ) Copper or (2) Copper, zinc and/or chromium catalyst in combination, an unexpected effect is expressed and ethanol can be obtained in a favorable yield and high selectivity, and the present invention has been completed. I ended up doing it.

[Summary of the invention]

As described above, the present invention comprises (a) a catalyst comprising at least one element selected from rhodium, lithium, copper, iridium and/or scandium, magnesium, yttrium, ytterbium, lutetium, vanadium, and chromium supported on a carrier; b> Ethanol is produced by reacting carbon monoxide and hydrogen in the presence of a catalyst consisting of (1) copper or (2) copper, zinc and/or chromium.

The present invention will be explained in detail below.

As mentioned above, the catalyst used in the present invention has (a) at least one element selected from the group consisting of rhodium, lithium, copper, iridium and/or scandium, magnesium, yttrium, ytterbium, lutetium, vanadium, and chromium supported on a carrier. a catalyst and (b)(1)w
4 or (2) A catalyst consisting of copper, zinc and/or chromium as the main components.0 Both catalysts can be used separately prepared, and when used, they may be mixed or mixed. One of the catalysts in (a) is placed in the upper layer (
One of the catalysts in b) can be used by filling the lower layer. In preparing the catalyst (a), the above-mentioned components are usually dispersed on a carrier as is done for noble metal catalysts.

The catalyst (a) used in the present invention can be prepared according to a conventional method used when using noble metals. For example, it can be prepared by an impregnation method, a dipping method, an ion exchange method, a coprecipitation method, a kneading method, etc. .

Raw materials for rhodium, which is a component of the catalyst, include halides such as chlorides and bromides, inorganic salts such as nitrates and carbonates, acetates, oxalates, and acetylacetic compounds. can be used. Raw material compounds that can be used for iridium, lithium, steel, scandium magnesium, yttrium, ytterbium, lutetium, vanadium, and chromium used as promoters include halides, inorganic acid salts such as nitrates and chlorates, hydroxides, and formic acid. salts, organic acid salts such as nitrates,
Metal alkoxide compounds, alkyl metal compounds, etc. can be used as appropriate.

The catalyst (b) can be used by dispersing and supporting the above components on a carrier in the same way as the preparation method of the catalyst (a), or it can be used after preparing the metal component and the carrier component by a precipitation method, kneading method, etc. You can also. As raw material compounds that can be used as lR1 zinc and chromium, organic acid salts such as halides, halogenates, nitrates, hydroxides, formates, acetates, and oxalates can be used as appropriate. In order to facilitate the loading of these catalyst components onto a carrier, a compound with a high tea content in ethanol, water or other suitable solvent is preferably used.

The method for preparing the catalyst will be explained below by taking the impregnation method as an example. The above metal compounds can be mixed with water, methanol, ethanol, acetone,
Tetrahydrofuran, dioxane, normal hexane,
Dissolved in a single or mixed solvent such as benzene or toluene,
A carrier is added to the solution and immersed, the solvent is distilled off, the carrier is dried, and if necessary, treatments such as heating and gas treatment are performed to support the metal compound on the carrier.

<a> or (b) As a method of supporting the catalyst, a method of preparing a mixed solution in which the raw material compounds are simultaneously dissolved in the same solvent and supporting the same on the carrier at the same time, a method of sequentially supporting each component on the carrier, or Various methods can be used, such as a method of supporting each component sequentially or stepwise while performing treatments such as reduction and heat treatment as necessary.

Other preparation methods, such as a method of supporting a metal by ion exchange using the ion exchange ability of a carrier, a method of preparing a catalyst by a coprecipitation method, a method of kneading, etc., can also be used as a preparation method for the catalyst used in the method of the present invention. Can be adopted.

The catalysts (a) and (b) prepared by the above-mentioned method are usually activated by reduction treatment and then subjected to reaction. In order to carry out the reduction, it is convenient and preferable to carry out the reduction using a hydrogen-containing gas at an elevated temperature.

As the reduction temperature of the catalyst in (a), the reduction temperature of rhodium is the temperature at which rhodium is reduced, that is, the reduction treatment can be carried out under a temperature condition of about 100°C, but preferably 200°C.
The reduction treatment is carried out at a temperature of ℃ to 600℃. At this time, in order to sufficiently disperse each component of the catalyst, the reduction treatment is carried out gradually from a low temperature.
Alternatively, the hydrogen reduction may be carried out while raising the temperature in stages, or the reduction may be carried out chemically using a reducing agent. For example, reduction treatment may be performed using carbon monoxide and water, or using a reducing agent such as hydrazine, a boron hydride compound, or an aluminum hydride compound.

Further, the catalyst (b) can be reduced in the same manner as the catalyst (a).

The carrier used in the present invention preferably has a specific surface area of 1
'! -1000r+(/g, pore size of 10A or more) that is commonly known as a carrier can be used.Specific carriers include silica, various silicates, alumina, activated carbon, and various other carriers. Metal oxides (e.g. zirconium oxide, titanium oxide, magnesia, etc.),
Molecule sieve, diatomaceous earth, etc. can be mentioned.
A silica-based carrier is preferred.

The ratio of each component in the catalyst (a) above is as follows.

The ratio of rhodium to the carrier is 0.0001 to 0.5 by weight, preferably o, o, considering the specific surface area of the carrier.
ot~0.3. Lithium and rhodium -2', +
+“- The ratio is lithium/rhodium (atomic ratio) o, jOiW ~
It is in the range of 0.1. The ratio of other additive elements to rhodium is other additive elements X/rhodium (atomic ratio): 0.00
It is in the range of 1 to IO1, preferably 0.005 to 3. Further, the ratio of each component in the catalyst (b) above is as follows. The ratio of tR to carrier and the weight ratio is 0.0
01-50, preferably 0.01-20. The ratio of m to zinc (zinc/w4 (atomic ratio)) is in the range of 0.01 to 50, preferably 0.1 to 10. The ratio of copper to chromium is chromium/copper (atomic non-pressure): 0. It ranges from O1 to 50, preferably from 0.1 to 10.

The present invention can be applied to, for example, a fixed bed flow reactor. That is, one of the catalysts of (a) is packed on top of one of the catalysts of (b) in the reactor, or one of the catalysts of (a) and the catalyst of (b) are charged. One of them is mixed and filled, and the raw material gas is introduced to carry out the reaction.

It is also possible to separate the product and recycle and reuse the unreacted raw material gas after purifying it if necessary.

Further, the present invention can also be applied to a fluidized bed type reactor. That is, the raw material gas, one of the catalysts in (a) above, and (b)
) The reaction can also be carried out by mixing and fluidizing one of the catalysts. Furthermore, the present invention can also be applied to a liquid phase heterogeneous reaction in which a catalyst is dispersed in a solvent and a raw material gas is introduced to carry out the reaction.

The conditions adopted when carrying out the method of the present invention are various reaction conditions for the purpose of producing oxygen-containing compounds containing ethanol as the main component with high yield and high selectivity while minimizing the production of hydrocarbons. are selected by organically combining these factors.

Although the target compound can be produced with high selectivity and high yield even under normal pressure (i.e., 0 kg/-gauge), the reaction can be carried out under pressure in order to increase the space-time yield. Therefore, the reaction temperature is 150° C. to 450° C., preferably 180° C. to 350° C. The reaction temperature is 150° C. to 450° C., preferably 180° C. to 350° C. It is ℃. The reaction temperatures of catalyst (a) and catalyst (b) may be the same, but it is preferable to set them to different reaction temperatures in order to obtain high ethanol selectivity and production activity. Since the amount of hydrocarbon by-products increases, it is necessary to increase the feed rate of raw materials or change the composition ratio of hydrogen and carbon monoxide. Therefore, the space velocity (raw material gas feed amount/catalyst volume) is the standard fin (0°C, 1 atm)
It is appropriately selected from the range of i oh-' to 10' h-1 in terms of the relationship with the reaction pressure, reaction temperature, and raw material gas composition.

The composition of the raw material gas is a gas mainly containing carbon monoxide and hydrogen, and nitrogen, argon, helium,
Gases such as methane, or hydrocarbons, carbon dioxide, generated oxygen-containing compounds, and water may be contained in the gaseous state under the reaction conditions.The mixing ratio of hydrogen and carbon monoxide is hydrogen/- carbon monoxide volume ratio) o, t-to,
Preferably it is 0.25-5, and the total proportion of carbon monoxide and hydrogen in the raw material gas is 20-100% by volume, preferably 60-100% by volume.

The present invention will be explained in more detail with reference to Examples below, but these Examples are shown to facilitate understanding of the present invention, and it goes without saying that the present invention is not limited thereto.

Example 1 Rum (Rh Cl s-3HsO) 0.48
0 g, lithium chloride (LICI・HtO) 0.022
g, cupric chloride (CuC1/2HtO) 0.006
g (0,037 mmo 1) and scandium chloride (
Silica gel (Davlson #5
L Davlson &amp; 3.7g (10m1
) was added and immersed, then ethanol was distilled off using a rotary evaporator, and the mixture was further vacuum-dried. after that,
Fill a Pyrex reaction tube and perform activation treatment at 450°C for 4 hours under hydrogen (50 ml/min).
-Cu-3c/Sin, a catalyst was prepared.

In addition, nitric acid IR (Cu (NOx) rich 3 HsO) 1
．． 763g, zinc nitrate (Z n (NOs)t・6H
3.7 g of calcined and degassed silica gel (Davison #57) was added and immersed in an aqueous solution in which 1.085 g of tO) was dissolved. After drying in the same manner as above, in the air,
It was baked at 350°C for 3 hours. After that, a mixed gas of hydrogen and nitrogen (H*: 2 ml/min, N8: 50 ml/min.
Activation treatment was performed at 350°C for 3 hours under aeration of
A u-Zu/SIOz catalyst was prepared.

Activity test and results Two titanium reaction tubes with an inner diameter of 14 mm each having a thermocouple protection tube with an outer diameter of 4 mm were connected in series, and the upper reaction tube was heated with the above R.
Filled with 2 ml of h-Li-Cu-3c/5iOz catalyst,
3 m of the above Cu-Zn/5 lot catalyst was placed in the lower reaction tube.
Filled with l. Under normal pressure hydrogen gas flow (100ml/min)
, after re-reduction at 200°C for 1 hour, a mixed gas of hydrogen/carbon monoxide -1.5 (volume ratio) was fed at 5 ONl/hour, reaction pressure was 30 kg/cd, Rh L l -Cu -S
c/SIO as catalyst and Cu-Zn/5lot
Among the reaction products obtained by carrying out the reaction at a catalyst reaction temperature of 265°C and 275°C, liquid products were collected by absorption in water, and gaseous products were directly collected and analyzed by gas chromatography. , the product distribution was determined. In addition, when calculating the product distribution, since carbon dioxide gas showed a tendency to decrease economically, its production amount was excluded. The results are shown in Table 1.

Example 2 Rhodium chloride 0.480g, lithium chloride 0.022g
, fernic chloride 0.006g, scandium chloride 0.02
4g, iridium chloride (I rcl- HxO) 0.0
The Rh L
After adding 10 ml of silica gel described in the catalyst preparation method and immersing the i Cu-S e / S I O, Rh-Ll-Cu-3c I was prepared in the same manner as in Example 1.
r/S! An Ot catalyst was prepared.

In addition, copper nitrate 1.763g, zinc nitrate 1.085g, chromium nitrate (Cr (NOx) t・9HtO) 1.46
After adding and immersing 10 ml of silica gel described in the preparation method of the Cu-Zn/5iot catalyst into an aqueous solution containing 0 g of Cu-Zn-Cr/S 10 in the same manner as in Example 1.
g catalyst was prepared.

The above Rh-Li-Cu-
3e -I r/S I Ot catalyst 2 ml was packed in the upper layer, Cu-Zn-Cr/S IOHOH catalyst 3 mol Nl
After filling, a reaction was carried out under the same conditions as in Example 1.

The results are shown in Table 1.

Example 3 Rhodium chloride 0.480g, lithium chloride 0.022g
, cupric chloride 0.006g, magnesium chloride (MnC
i!・Rh-L 1-Cu-3c/S i Ox of Example 1 in an ethanol solution containing 0.019 g of 6HtO)
After adding and immersing 10 ml of silica gel described in the catalyst preparation method, Rh L 1-
A catalyst was prepared using CuMg/SIO.

In addition, 10 ml of silica gel described in the method for preparing a Cu-Zn/Slow catalyst in Example 1 was added to an aqueous solution containing 1.763 g of copper nitrate, and the mixture was immersed. Prepared.

The above Rh-Li-Cu-
Fill the upper layer with 2ml of Mg/5lot catalyst, and
After filling the lower layer with 4 ml of the Cu/SI Ox catalyst, a reaction was carried out under the same conditions as in Example 1 except that the reaction temperature of the Cu/SI Ox catalyst was changed to 280°C. The results are shown in Table 1.

Example 4 Rhodium chloride 0.480g, lithium chloride 0.022g
, chloride w4o, oo6g, magnesium chloride 0.0
Rh-Li-Cu-3c/Sin of Example 1 was added to an ethanol solution containing 19g of iridium chloride and 0.064g of iridium chloride.
After adding and immersing 10 ml of silica gel described in the catalyst preparation method, Rh-Li-Cu was added in the same manner as in Example 1.
-Mg-Xiar/SiOx catalyst was prepared.

The above Rh-Li-Cu was placed in the same reactor as in Example 1.
The upper layer was filled with 2 ml of the M g -1r / S I Og catalyst, and the Cu Z n /
After filling the lower layer with 3 ml of SIO catalyst, Example 1
The reaction was carried out under the same conditions. The results are shown in Table 1.

Example 5 Rhodium chloride 0.480g, lithium chloride 0.022g
, cupric chloride 0.006g, ytterbium chloride (Yb
Rh-L 1-Cu-3c/310 of Example 1 in an ethanol solution containing 0.035 g of Rh-L 1-Cu-3c/310! After adding 10 ml of silica gel described in the catalyst preparation method and immersing it, Rh-L l -C was prepared in the same manner as in Example 1.
A u-Yb/SIOz catalyst was prepared.

In addition, Example I Cu-Zn/S was added to an aqueous solution containing 1.763 g of copper nitrate and 2.189 g of chromium nitrate.
After adding and immersing 10 ml of silica gel described in the method for preparing iOz catalyst, Cu-Cr was added in the same manner as in Example 1.
-3IO* catalyst was prepared.

The above Rh-Li-Cu was added to the same reaction apparatus as in Example 1.
After filling 2 ml of -Y b/S l O* catalyst and filling 3 ml of the above-mentioned Cu Cr / S t O catalyst, a reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example 6 Rhodium chloride 0.480g, lithium chloride 0.022g
, chloride 1if0.006 g, indolium chloride (
Rh-L 1-Cu-5c1510 of Example 1 was added to an ethanol solution containing 0.028 g of YCI, 68*O).
After adding and immersing silica gel lOm+ described in the catalyst preparation method, Rh-Ll-Cu-
A Yb-1r/5iOs catalyst was prepared.

The above Rh-LICu was placed in the same reaction apparatus as in Example 1.
After filling the upper layer with 2 ml of the Y b I r / SIO catalyst and filling the lower layer with 3 ml of the Cu-Zn/5loz catalyst prepared in Example 1, the reaction was carried out under the same conditions as in Example 1. . The results are shown in Table 1.

Example 7 Rhodium chloride 0.4130 g, lithium chloride 0.02
2g1 chloride mO,006g, lutetium chloride (Lu
After adding 10 ml of silica gel described in the method for preparing Rh-L 1-Cu-3c/S lot catalyst in Example 1 to an aqueous solution containing 0.036 g of CIs' 6H*Q) and immersing it, the same procedure as in Example 1 was carried out. Rh~L l -Cu by the method of
-L u /SI Os catalyst was prepared.

The above Rh-Ll-Cu was added to the same reaction apparatus as in Example 1.
The upper layer was filled with 2 ml of L u /S I Oi catalyst, and 3 ml of Cu-Zn/5 lot catalyst prepared in Example 1.
After filling the lower layer, a reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example 8 Rhodium chloride 0.480g, lithium chloride 0.022g
, second chloride! jio, 006 g, lutetium chloride 0.
After adding and immersing 10 ml of silica gel described in the preparation of Rh-Li-Cu-3c/Smu0□ catalyst in Example 1 into an aqueous solution containing 0.064 g of iridium chloride, the same method as in Example 1 was carried out. Rh-Li-Cu-Lu-1
An r/5iOt catalyst was prepared.

The above Rh-L t-Cu was added to the same reaction apparatus as in Example 1.
-Lu-r r/SiOx catalyst 2ml catalyst 2 sills charged,
After filling the lower layer with 3 ml of the Cu-Zn-Cr/Slam catalyst prepared in Example 2, a reaction was carried out under the same conditions as in Example I. Results Example 9 Rhodium chloride 0.480g, lithium chloride 0.022g
, cupric chloride 0.006g, vanadium chloride (VC1s
) Rh- of Example 1 in an aqueous solution containing 0.014 g
After adding and immersing the silica gel loml described in the preparation of Ll-Cu-3c/Slow catalyst, a Rh-Ll-Cu-V/SIO catalyst was prepared in the same manner as in Example 1.

The above Rh-Li-Cu was placed in the same reactor as in Example 1.
- 2 ml of V/S I Ox catalyst was packed in the upper layer and 4 m of Cu/S I O gold catalyst prepared in Example 3
After filling the lower layer with 1, the reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example 10 Rhodium chloride 0.480g, lithium chloride 0.022g
, cupric chloride 0.006g, chromium chloride (Cr Cl
s ・6H,O) 0.024 g, iridium chloride 0.
Rh-Ll-Cu of Example 1 in an aqueous solution containing 064 g
After adding and immersing 10 ml of silica gel described in Preparation of -3c/S i O* Catalyst, a Rh-Li-Cu-Cr-1r/5lot catalyst was prepared in the same manner as in Example 1.

The above Rh-L 1-Cu was added to the same reactor as in Example 1.
-1r/S lot catalyst 2 ml layer of catalyst was packed, and in Example 5! A reaction was carried out under the same conditions as in Example 1 after filling the lower layer with a catalyst of Cu-Cr/SIO prepared by III. The results are shown in Table 1.

Comparative Example 1 Rh-L 1-Cu-5c1510 prepared in Example 1
, the catalyst has an outer diameter of 4 mm and an inner diameter of 14 m with a thermocouple protection tube.
The inside of the 0 reaction tube filled with 2 ml in a titanium reaction tube of 1.0 m was replaced with nitrogen, and after being heated with hydrogen gas at 200°C for 1 hour under normal pressure, carbon monoxide/hydrogen-1,5 (volume ratio) The reaction product was analyzed in the same manner as in Example 1 by introducing a mixed gas of 5ON1/special and carrying out the reaction at a reaction pressure of 30 kg/cd and a reaction temperature of 265°C. The results are shown in Table 1.

Comparative Example 2 Rh-Ll-Cu-M prepared in Example 3 instead of Rh-Ll-Cu-3C/Slow catalyst of Comparative Example 1
The reaction was carried out under the same conditions as in Comparative Example 1 except that 2 ml of the catalyst was used.

The results are shown in Table 1.

Comparison 913 Rh LI C+x-5c/S 10 of Comparative Example 1
Rh-Li-Cu prepared in Example 5 instead of g catalyst
The reaction was carried out under the same conditions as in Comparative Example 1 except that 2 ml of Y b /S i O was used as a catalyst.

The results are shown in Table 1.

Comparative Example 4 Rh-Li-Cu-3c/5lot catalyst prepared in Example 6 was replaced with Rh-Li-Cu-3c/5lot catalyst in Comparative Example 1.
/SiO* The reaction was carried out under the same conditions as in Comparative Example 1, except for using 2 ml of catalyst and 2 liters of catalyst.

The results are shown in Table 1.

Comparative Example 5 Rh-Ll-Cu-L prepared in Example 7 instead of Rh-Ll-Cu-3c/SiOm catalyst of Comparative Example 1
The reaction was carried out under the same conditions as in Comparative Example 1 except that u/Sin and 2 ml of the catalyst were used.

The results are shown in Table 1.

Comparative Example 6 Rh-Ll-Cu-3c/Slow catalyst prepared in Example 9 was used instead of the Rh-Ll-Cu-3c/Slow catalyst of Comparative Example 1.
The reaction was carried out under the same conditions as in Comparative Example 1, except that the V/SI Os catalyst was used.

The results are shown in Table 1.

Comparative Example 7 Rh-L'i Cu S C/S of Comparative Example 1
Rh tuaed in Example 10 with I O instead of catalyst
-L, 1-Cu-Cr -1r/S IO*catalyst 2
The reaction was carried out under the same conditions as in Comparative Example 1 except that ml was used. The results are shown in Table 1.

Selectivity - Consumed carbon monoxide standard excluding carbon dioxide production C"10) EtOH": Ethanol content in ethanol + ethyl acetate AcH: Acetaldehyde AcOH": Acetic acid content CHa in acetic acid + acetate ester
'methane

Claims (1)

[Claims] A catalyst comprising at least one element selected from rhodium, lithium, copper, iridium and/or scandium, magnesium, yttrium, ytterbium, lutetium, vanadium, and chromium supported on a carrier;
2) A method for producing ethanol consisting of reacting carbon monoxide and hydrogen in the presence of a catalyst consisting of copper, zinc and/or chromium.