JPS61191634A - Method for producing ethanol - Google Patents

Abstract

PURPOSE:To obtain the titled compound economically in high selectivity, by reacting carbon monoxide with hydrogen using a catalyst system consisting of rhodium supported on a carrier and palladium, iron, etc., supported on a carrier. CONSTITUTION:The objective compound can be produced by reacting carbon monoxide with hydrogen preferably under 0-250kg/cm<2>G pressure at 180-350 deg.C using a catalyst system consisting of (A) a catalyst selected from A1 a catalyst obtained by supporting rhodium on a carrier, A2 a catalyst obtained by supporting rhodium, lithium or manganese on a carrier, and A3 a catalyst obtained by supporting rhodium, manganese, iridium and/or lithium on a carrier and (B) a catalyst obtained by supporting palladium, iron and/ or molybdenum on a carrier. The catalysts A and B are used in the form of a mixture, or by setting the catalyst A at the upper layer and the catalyst B at the lower layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] The present invention relates to a method for producing ethanol. More specifically, (a) a catalyst comprising rhodium supported on a carrier, (b) a catalyst comprising rhodium and lithium or manganese supported on a support, and (c) a catalyst comprising rhodium, manganese, iridium and/or lithium supported on a support. The present invention relates to a process for producing ethanol, which comprises reacting carbon monoxide and hydrogen in the presence of a catalyst comprising palladium, iron and/or molypdenoid supported on a carrier.

[Prior art and problems to be solved by the invention] Oxygen-containing compounds having two carbon atoms, such as ethanol and acetaldehyde, have conventionally been produced by a petrochemical method using naphtha as a raw material. However, due to the rise in crude oil prices in recent years, manufacturing prices have risen markedly, necessitating a change in raw materials. On the other hand, various methods of producing an oxygen-containing compound having two carbon atoms using a mixed gas of carbon monoxide and hydrogen, which are abundant and available at low cost, have been studied. In other words, a mixed gas of carbon monoxide and hydrogen is reacted with rhodium as the main component in the presence of a catalyst made of a metal or metal oxide such as manganese, titanium, zirconium, or tungsten to form an oxygen-containing gas containing 2 carbon atoms. Methods for selectively producing compounds are known.

However, this method also produces a large amount of by-product hydrocarbons such as methane, and when the selectivity of oxygen-containing compounds is low or the selectivity of oxygen-containing compounds is high, the selectivity of the main product is low. Rarely. Furthermore, the amount of target compounds produced using rhodium, which is a more expensive precious metal, is still small, and the reality is that no technology has been developed that has been completed economically or in terms of process. Catalyst in which manganese is added to rhodium and its improvement method for the purpose of producing the oxygen-containing compound No. 2 in high yield and with high selectivity (Japanese Patent Application Laid-Open No. 52-14706.56-4
No. 333.56-8334) has been proposed, but both methods use acetaldehyde and acetic acid as the main products and have the disadvantage that the yield and selectivity of ethanol and ethanol are extremely low.

As stated above <1. There has not been provided a method for efficiently and economically producing an oxygen-containing compound containing ethanol as a main component from a gas containing hydrogen, -a-returning element, and hydrogen.

As a result of intensive studies on the method for selectively producing ethanol, the inventors of the present invention found that, as mentioned above, the Cl-Nium catalyst and the Cl-Dium-Mn catalyst, which were known as catalysts for the production of acetaldehyde and acetic acid, and iron and/or The present invention was completed by discovering that jetanol can be produced with high selectivity by combining it with a batidium catalyst containing molybdenum.

[Summary of the invention]

As described above, the present invention produces ethanol by reacting carbon monoxide and hydrogen in the presence of any one of the catalysts (a) to (c) and the catalyst (b).

The main constituents are three types of catalysts. It is necessary to use separate catalysts manufactured by rA for both catalysts.
When used, they can be used by mixing them or by filling the catalysts (a) to (c) in the upper layer and the catalyst in (c) in the lower layer.

In preparing the catalyst, a catalyst in which the above-mentioned components are dispersed on a carrier is usually used, as is the case with noble metal catalysts.

The catalyst used in the present invention can be prepared using conventional noble metal methods. For example, it can be prepared by an impregnation method, a dipping method, an ion exchange method, a coprecipitation method, a kneading method, etc.

The raw material compounds for the chain components constituting the catalyst include oxides, chlorides, inorganic salts such as nitrates and carbonates, acetates, cymetates, acetylacetonate salts, dimethylglyoxime salts, and ethylenediamine acetate salts. organic salts or chelates, carbonyl compounds, cyclopentadienyl compounds,
Compounds commonly used in preparing noble metal catalysts, such as ammine complexes, metal alkoxide compounds, and aluminum metal compounds, can be used.

The method for preparing the catalyst will be explained below by taking the impregnation method as an example.

The above metal compound is dissolved in a solvent such as water, methanol, ethanol, tetrahydrofene, dioxane, normal hexanes, benzene, toluene, etc., a carrier is added to the solution and immersed, the solvent is distilled off, and the mixture is dried. If necessary, treatment such as heating is performed to support the metal compound on the carrier.

Supporting methods include preparing a mixed solution in which the raw material compounds are simultaneously dissolved in the same solvent and supporting them on the carrier at the same time, supporting each component on the carrier sequentially, or reducing and heat-treating each component according to the required JsK. It is possible to use various techniques such as a method of sequentially or stepwise loading while performing processing such as the following.

As described above, the three catalysts are prepared separately using these methods.

Other preparation methods, such as a method of supporting a metal by ion exchange utilizing the ion exchange ability of a carrier, a method of preparing a catalyst by a coprecipitation method, etc., can also be adopted as a method of preparing the catalyst used in the method of the present invention. The catalyst prepared by the above method is usually activated by K by reduction treatment and then subjected to the reaction. It is convenient and preferable to carry out the reduction using a hydrogen-containing gas at an elevated temperature. At this time, the reduction temperature can be the temperature at which rhodium is reduced, that is, about 100°C, but preferably 200υ~
Reduction treatment is performed at a temperature of 600°C. At this time, hydrogen reduction may be carried out from a low temperature while gradually or stepwise raising the temperature in order to sufficiently disperse each component of the catalyst.

Further, reduction can also be carried out chemically using a reducing agent. For example, using carbon monoxide and water,
Reduction treatment may be performed using a reducing agent such as a boron hydride compound or an aluminum hydride compound.

The carrier used in the present invention preferably has a specific surface area of I
L) to 10 Q Orn2/g and a carrier having a pore diameter of 10'A or more and is generally known as a carrier can be used. Specific carriers include Riu, fiMrll salt, silica glu, Moley? -2-7-
Examples include silica-based carriers such as Copper, Quick Carbon, etc., alumina, activated carbon, etc., but silica-based carriers are preferred.

Catalyst (→ - (c) In either case, the concentration and composition ratio of each component in the catalyst can be varied within a wide range.

The ratio of rhodium and cum to the carrier is 0.0001 to 0.5 by weight considering the specific surface area of the carrier.
, 4 L, < 0,001-0.3-16 L. 1
&, (() to (c) In the catalysts, the ratio of the cocatalyst metal to rhodium is in the range of 0.001 to 1 O1, preferably 0.01 to 5, respectively in atomic ratio.Further) In the catalyst, iron The ratio of the atomic ratio of the salt and the salt to the palladium is 0. L) 01-10. Preferably 0.01~
Ruru in the range of 5.

The present invention can be applied to, for example, a fixed bed flow reactor. That is, a reactor is filled with a catalyst, and a raw material gas is introduced to cause a reaction.

It is also possible to separate the product and purify the unreacted raw material gas and recycle it for later use.

Further, the present invention can also be applied to a fluidized bed type reactor. That is, the reaction can also be carried out by bringing the raw material gas and the fluidized catalyst together. 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 in carrying out the present invention are selected by combining various reaction condition factors with the aim of producing oxygen-containing compounds containing ethanol as the main component with high yield and high selectivity. be done. The reaction pressure is normal pressure (i.e. Ok
4/ctn” gauge) with high selectivity for the target compound.
The reaction can be carried out under pressure in order to increase the space-time yield.

Therefore, the reaction pressure is Okg/cm gauge to 350 to 9/α gauge, preferably 0 kg/cm gauge to 250 hog/cm gauge.

Do it under pressure from a mercenary. Reaction temperature is 150υ~45L
)°C, preferably 18U'Q to 350°C. When the reaction temperature is high, the amount of hydrocarbon by-product increases, so it is necessary to increase the feed rate of the raw material. Therefore, the space velocity (raw material gas feed amount x catalyst volume) is under the standard condition (0°0.
1 atm) 5! It is selected as appropriate in the range of 1 Oh=~10'h-' in terms of A and the relationship between 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,
It may contain an inert gas such as methane, or a hydrocarbon, carbon dioxide gas, or water as long as it is in a gaseous state under the reaction conditions. The mixing ratio of carbon monoxide and hydrogen is 0 in terms of CO/H2 ratio.
．． 1 to 1O1, preferably 0.2 to 5 (volume ratio).

The present invention will be explained in more detail with reference to Examples below.

Example 1 Rhodium chloride (Mel, 3H2U) 0.48 L)
Kurikage A/ (Day i sonφ57. Davi
3.7 g (10aZ) (manufactured by Son Co., Ltd.) was added and immersed. Next, ethanol was distilled off to dryness using a rotary evaporator, and after death, the body was further vacuum-dried. After that, the Pyrex reaction tube is filled with a mixed gas of hydrogen and nitrogen (
H2: under ventilation of 6 utd/min, N: 60 utd/min),
Activation treatment was performed at 400℃ for 4 hours, and Rh/8102
A catalyst was prepared. Then, palladium chloride (PdC12
) 0.162 g, ferrous chloride (FeC1z・4H20
) 0.109 g of silica gel was dissolved in the aqueous solution, and 3.7 g (10 g) of calcined and degassed silica gel was added and immersed. Pd-Fe was prepared using the same preparation method and activation treatment as above.
/8i0□ catalyst was prepared. Nine h/8i 0□ catalysts (catalyst 7m) and Pd-Fe catalyst (3m) were obtained in this way.
1) was filled in the reaction tube (titanium m1) K of the high-pressure flow reactor so that it formed the upper and lower layers, and was heated under normal pressure hydrogen gas flow (2).
After re-reduction treatment at 300° C. for about 2 hours, a mixed gas of carbon monoxide and hydrogen was introduced to carry out a reaction under predetermined reaction conditions. For analysis of the reaction products, the liquid products were dissolved in water and collected, and the gaseous products were collected directly and subjected to gas chromatography analysis, qualitative and quantitative analysis, and the distribution of the products was determined. The results are shown in Table 1.

Practical example 2 Rhodium chloride 0.4 [1 g, lithium chloride (LiC1.
Rh-Li/S 7 was obtained by immersing 0.022 g of ethanol solution in which 0.022 g of Rh-Li/S 7
02 catalyst was prepared. l also h-L t /S i 02
Catalyst (7m), Pd-Fe/8 prepared in Example 1
The reaction tube of a high-pressure flow reactor was filled with 4% i02 (3aZ) in the upper and lower layers, and an activity test was conducted in the same manner as in Example 1.

The results are shown in Table 1.

Example 3 Rhodium chloride 0.480 g s Manganese chloride (Bi[
Dissolve 0.361 g of nC12・4H20) and immerse the ethanol solution in a 300°C fired oven. On the other hand, degassed silica calcined at 300°C was immersed in an aqueous solution in which 0.162 gs of palladium chloride and 0.075 g of molybutynone chloride (MoCls) were dissolved at 10 MIK.

Rh-Mn/8i
0z, Pd-Mo/8tO2 was prepared. Rh
-M n/S s 02 catalyst (6d) and Pd-Mo/8
i02 (2 ml) was filled into the upper and lower layers of a reaction tube of a high-pressure flow reactor, and an activity test was conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 4 Logicum chloride 0.480g, manganese chloride υ, 012
g.

An ethanol solution containing 0.033 g of lithium chloride and 0.177 g of palladium chloride and 0.0 g of ferrous chloride.
, IO dissolved in an aqueous solution of 9 g was immersed in the 300°C calcined aerated silica gel lO, and then subjected to the same treatment as in Example 1 to obtain Rh -Mn -Li/S 102, Pd.
-Fe/8102 catalyst was prepared. Rh −M n −
L s /S t 02 catalyst (6R1), I r-Fe
/8i02 (2ia/) was filled into the upper and lower layers of a reaction tube of a high-pressure flow reactor, and an activity test was conducted in the same manner as in Example 1. The results are shown in Table 1VC.

Example 5 Palladium chloride 0.089 g, molybogen chloride u
, 035gt# dissolved aqueous solution was immersed in silica gel 10aZ which had been fired at 300°C. P d -Mo/8 i 02 was prepared by the same treatment as in Example 1. R h -Mn -L t /8 i prepared in Example 4
02 catalyst (6-) and the above P d -Mo/8 t O2
Catalyst (2-) was filled in the upper and lower layers of a reaction tube of a high-pressure flow reactor, and an activity test was conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 6 Rhodium chloride 0.480 g, manganese chloride 0.03
6g.

Iridium chloride b (IrC14-H2O) 0.128g
The dissolved ethanol solution, 0.177 g of palladium chloride, 0.109 g of ferrous chloride, and 0.05 g of molybutin chloride were dissolved in a large aqueous solution at 300°C.
After immersing each 10 dK of calcined silica gel, the same treatment as in Example 1 was carried out to obtain 10 dK of silica gel.
io2, Pd-Fe-NLo/8102 was prepared. R,h -Mn-I r/8i0□Catalyst (6d
) and Pd-Fe-Mo/8i0□ catalyst (2d) were filled in the upper and lower layers of a reaction tube of a high-pressure flow reactor, and Example 1
The activity test was conducted in the same manner as above. The results are shown in Table 1.

Example 7 Rhodium chloride U, 480 g 1 Manganese chloride 0.01
8g.

Iridium chloride 0.064 g, lithium chloride 0.0
An ethanol solution containing 22 g of palladium chloride and an aqueous solution containing 0.266 g of palladium chloride and 0.163 g of ferrous chloride were immersed in silica gel 10-, which had been calcined and degassed at 300°C. Similar treatment
Mn-Ir-Li/5i02 and Pd-Fe/8i02 were prepared.

Rh -Mn-Ir-Li/8i0□Catalyst (7N) and P
d-re/Rh/j9t O2 catalyst (10 iu) prepared in Example 1 was transferred to the reaction tube Kyc of the high-pressure flow reactor.
The activity test was conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 The Rh -L t /8 t 02 catalyst (10*/) prepared in Example 2 was filled into a reaction tube of a high-pressure flow reactor, and an activity test was conducted in the same manner as in Example 1. The results are shown in Table 1K.

Comparative Example 3 The R h -M n/8 i 02 catalyst (10#t/) prepared in Example 3 was packed into a reaction tube of a high-pressure flow reactor, and an activity test was conducted in the same manner as in Example 1. Ta. Show the results in Table 9.

Procedural amendment (voluntary) March 1', 1985 Michibe Uga, Commissioner of the Patent Office1, Indication of the case Patent Application No. 17723 of 19852, Name of the invention Process for producing ethanol3, Amendment Relationship with the case of the person who made the amendment Contents of the amendment in column 5 of “Detailed Description of the Invention” of the specification of the patent applicant 1) rPd-FeJ on page 12, line 13 of the specification of the present application was changed to rP
Corrected to d-Fe/S 1otj.

2) r I r-Fe/S io, J on page 15, line 2
Corrected to 'Pd Fe/510g1.

3) "Example...5iOxJ" on page 18, line 3 of the same page is corrected to "Rh-Mn-Li/S i OzJ prepared in Example 4.

that's all

Claims (3)

[Claims] (1) A method for producing ethanol comprising reacting carbon monoxide and hydrogen in the presence of a catalyst comprising rhodium supported on a carrier and a catalyst comprising palladium, iron and/or molybdenum supported on a support. . (2) Ethanol consisting of reacting carbon monoxide and hydrogen in the presence of a catalyst comprising rhodium and lithium or manganese supported on a carrier and a catalyst comprising palladium, iron and/or molybdenum supported on a support. How to manufacture. (3) A catalyst comprising rhodium, manganese, iridium and/or lithium supported on a carrier, palladium, iron and/or
Or a method for producing ethanol, which comprises reacting carbon monoxide and hydrogen in the presence of a catalyst comprising molybdenum supported on a carrier.