JPS60161935A - Production of oxygen-containing hydrocarbon compound - Google Patents

Abstract

PURPOSE:To improve the selectivity of acetic acid, acetaldehyde and/or ethanol in the reaction of carbon monoxide with hydrogen in the presence of a catalyst, by using a catalyst composed of ruthenium combined with lithium and a specific metal such as platinum. CONSTITUTION:Acetic acid, acetaldehyde and/or ethanol are produced in high selectivity, without using an expensive and scarce rhodium catalyst, by reacting carbon monoxide with hydrogen usually in vapor phase, in the presence of a catalyst comprising (a) ruthenium combined with (b) lithium and (c) one or more metals selected from platinum, palladium, iron, cobalt and nickel. The above catalyst components are supported usually on a carrier having a surface area of preferably 1-1,000m<2>/g, especially a silica-based carrier, and reduced before reaction preferably at 250-550 deg.C to activate ruthenium essentially to a metallic state.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing oxygen-containing hydrocarbon compounds from synthesis gas, and in particular to a method for producing acetic acid, acetaldehyde and/or ethanol by reacting carbon monoxide and hydrogen in the presence of a catalyst. The present invention relates to a method characterized in that ruthenium, lithium, and at least one metal selected from platinum, palladium, iron, cobalt, and nickel are used together as a catalyst.

There are known methods for producing oxygenated hydrocarbon compounds having two carbon atoms, such as acetic acid, acetaldehyde, and ethanol, by reacting synthesis gas, essentially carbon monoxide and hydrogen contained therein. Rhodium (Rh) catalyst is known to be effective as a catalyst. (
For example, JP-A-51-80806, JP-A No. 51-8080
7, No. 52-14706, No. 54-138504, No. 54-141705, No. 55-57527, No. 56-147730, U.S. Pat. No. 4,101,450, etc.) In other words, synthesis gas or carbon oxide and hydrogen gas containing
When a mixture is reacted catalytically, the reaction products vary widely depending on the catalyst used and the reaction conditions, for example,
Various saturated and α-olefin-rich unsaturated aliphatic hydrocarbons ranging from methane to paraffin wax, aromatic hydrocarbons with 6 to 10 carbon atoms, and various alcohols ranging from methanol to higher alcohols with nearly 20 carbon atoms. Other oxygenated hydrocarbon compounds such as aldehydes and fatty acids are produced. In other words, it is extremely difficult to suppress the production of unnecessary compounds from among these vast numbers of various products and selectively produce only the specific desired compound. Various efforts have been made mainly in the search for catalysts, but rhodium catalysts are specific for obtaining the aforementioned oxygenated hydrocarbon compounds with two carbon atoms, such as acetic acid, acetaldehyde, and ethanol, with high selectivity. It is said to be excellent in

However, these methods have the disadvantage of using rhodium, a precious metal that is expensive and produced in low quantities.Therefore, useful alternatives to rhodium such as acetic acid, acetaldehyde,
There is widespread interest in developing catalysts for synthesizing oxygenated hydrocarbon compounds having two carbon atoms, such as ethanol.

In general, one way to improve the activity and selectivity of solid catalysts containing metals, metal oxides, or metal salts as active components is to add other active or auxiliary components to the active component (main catalyst). Various attempts have been made to combine different components (cocatalysts), but it is out of the question to combine components that have nothing to do with improving activity, and those that lead to a decrease in activity and selectivity, contrary to the intended purpose. There are many such compounds, and even if the activity (or selectivity) is improved, there are many that have an adverse effect on the selectivity (or activity) of the target compound, and it is not easy to find a specifically suitable combination.

In order to solve the above-mentioned problems found in conventional methods, the present inventors reacted carbon monoxide with hydrogen to produce oxygenated hydrocarbons having two carbon atoms such as acetic acid, acetaldehyde, and/or ethanol. As a result of extensive research into non-rhodium catalysts that selectively produce compounds, that is, tests using a large number of combinations of catalyst components, and repeated various studies,
Ruthenium, lithium and platinum, radium, iron,
The inventors have discovered that a catalyst containing at least one selected from cobalt and nickel exhibits high selectivity for oxygen-containing compounds having 2 carbon atoms, and have completed the method of the present invention.

The method of the present invention will be explained in more detail below.

As mentioned above, the catalyst of the present invention is a combination of ruthenium, lithium, and at least one selected from platinum, radium, iron, cobalt, and nickel. Although the catalytically active species in the fruit are not necessarily clear, the core of its activity is essentially the metal species that coexist with each other, and therefore the shape of the catalyst itself and the shapes of each component in the catalyst are, in principle, There are no restrictions.

However, in reality, ruthenium, platinum, palladium, iron,
Cobalt and nickel are metals or low-valent salts, and lithium is physically mixed or chemically combined with ruthenium and the like as oxides, inorganic acid salts, complex salts, etc. Further, the above-mentioned catalyst component is usually supported on a carrier, although it may be carried without a carrier. Ruthenium compounds used in catalyst preparation include, for example, inorganic acid salts and oxides such as ruthenium chloride, ruthenium bromide, ruthenium iodide, ammonium ruthenate chloride, potassium ruthenate, ruthenium nitrate, and ruthenium hydroxide, and ruthenium acetate. , organic acid salts such as ruthenium formate and ruthenium oxalate, ammine complex salts, clusters, etc. are used, but there are no particular limitations. In addition, platinum, palladium, iron, cobalt, and nickel compounds used as other catalyst components include, for example, inorganic acid salts such as chlorides, nitrates, and carbonates, oxides, acetates, formates, oxalates, etc. Organic acid salts, ammine complex salts, clusters, etc. are used, but there are no particular limitations. In addition, as the lithium compound, for example, inorganic acid salts such as halogenates, sulfates, nitrates, carbonates, organic acid salts such as hydroxides, acetates, formates, oxalates, etc. can be used, but there are no particular limitations. . However, in order to make it easier to support these catalyst components on the carrier,
Compounds soluble in water or other suitable solvents are preferably used.

As a method for preparing a catalyst in which ruthenium is used in the present invention in combination with at least one selected from lithium and platinum, /yaradium, iron, cobalt, and nickel, the above-mentioned ruthenium, lithium/platinum, palladium, iron,
After dissolving cobalt and nickel compounds in water or an organic solvent such as n-hexane, alcohol, or acetone, adding a diporous inorganic carrier material to this solution and supporting it by impregnation method, ion exchange method, or other conventional method, A supported and fixed target object can be obtained by reduction or heat treatment.

The catalyst components may be supported on the carrier at the same time, or each component may be supported on the carrier sequentially, or each component may be subjected to reduction, heat treatment, etc. as necessary. It is possible to use various techniques such as a method of sequentially or stepwise loading while carrying out. The catalyst prepared by the above-mentioned method is usually subjected to a reduction treatment to activate silthenium to a substantially metallic state, and then subjected to a reaction. The reduction treatment can be carried out under hydrogen gas or under a mixed gas of hydrogen and carbon monoxide, or in some cases under hydrogen gas partially diluted with an inert gas such as nitrogen, helium, argon, etc., or under the above mixed gas. can.

The reduction treatment temperature is 100 to 600°C, preferably 2
It is carried out at a temperature of 50-550°C. At this time, in order to maintain the activation state of each component of the catalyst in an optimal state, the reduction treatment may be performed while raising the temperature gradually or stepwise from a low temperature.

Further, the reduction of the ruthenium compound may be carried out by treatment with a reducing agent such as methanol, hydrazine or formalin.

Although there is no strict limit on the amount of each catalyst component used, under normal conditions, taking into consideration the surface area of the support (approximately 1 rnlP to 1,000 rnlP), the content of ruthenium in the supported catalyst is The ratio of lithium, platinum, palladium, iron, cobalt, nickel and ruthenium is 0.01-15% by weight, preferably 0.1-10% by weight.
LiAu + PtAu + Pd/Ru r Fe71
ur Co/'Ru r Ni/Ru ) each has an atomic ratio of 0.001 to 2, preferably 0.01 to 1.

The carrier used for this catalyst is 1 to 1,000 m2/g.
A carrier having a specific surface area of 2 is preferred, and silica, activated alumina, titanium oxide, thorium oxide, activated carbon, zeolide, etc. can be used, but silica-based carriers are particularly preferred.

These carriers can be used in any shape, such as powder or pellet form. - The reaction is usually carried out in the gas phase, for example, monoxide is added to a fixed bed reactor packed with a catalyst. Conducts raw material gas containing carbon and hydrogen. In this case, the source gas may contain other components other than carbon monoxide and hydrogen, such as carbon dioxide, nitrogen, argon, helium, water vapor, and methane. Further, the catalytic reactor is not limited to a fixed bed type, but may be of other types such as a moving bed type or a fluidized bed type. In some cases, a liquid phase reaction may also be carried out in which the catalyst is suspended in a suitable solvent and the raw material gas is passed through the reactor.

Although the reaction conditions can vary within a wide range, the reaction conditions applicable to a fixed bed flow reactor are shown below as a typical range.

Molar ratio of carbon monoxide and hydrogen: 20:1 to 1:5, preferably 10:1 to 1:3, reaction temperature 150 to 450°C, preferably 200 to 350°C, pressure 1800 atm, preferably 20 to 200 atm, sy:100-106H-
1, preferably about 1,000 to 105H-1.

- Hereinafter, the present invention will be explained in more detail with reference to Examples. However, in order to make it easier to understand the present invention, these examples intentionally show the conditions in a unified manner, and the present invention is not limited in any way by these examples. Of course not.

Catalyst Preparation Example 1 Ruthenium chloride (Ruct3-3H2o) 1. !
530 y, lithium chloride (LiCt) 0.746
? , chloroplatinic acid (H2PtCA6-6H20) 0.5
Silica gel (Fuji Deguison Chemical ■≠57) 20. P was added and uniformly impregnated. The mixture was dried at room temperature for 1 hour and at 80° C. for 20 hours with occasional stirring. This catalyst was placed in a reduction reaction tube made of quartz glass, and hydrogen reduction was carried out at 300°C for 2 hours while flowing a mixed gas of 75 Nt/'Hr at a hydrogen/nitrogen volume ratio of 1/4. The resulting catalyst had the composition shown in Table 1, Example 1.

-Example J1 - Ruthenium chloride (Ru(t3・3H2Q) 1.53
01-1 Chlorination The catalyst of Example 2 in Table 1 was obtained by the same treatment as in Example 1.

Example 3 Ruthenium chloride (RuC43'3H20) 1.530
iP, lithium nitrate (LiNO2) 0.135 j'
, chloroplatinic acid () (2Pt, C76・6H20) 0.
The catalyst of Example 3 in Table 1 was obtained by treating in the same manner as in Example 1 except that 519 was dissolved in 25M pure water.

Example 4 Ruthenium chloride (Ruct5-3H2o) 1.53
oy, lithium chloride (LiCt) 0.250JP,
Palladium chloride (PdC12) 0.354 ii- was completely dissolved in a mixture of 24 ml of pure water and 1 mA of hydrochloric acid, and then dried and reduced in the same manner as in Example 1.
The catalyst of Example 4 in Table 1 was obtained.

Example 5 Ruthenium chloride (RuC43'3H20) 15301
P1 Lithium chloride (LiCA) 0.250? , iron chloride (FeC63.6H20) 0.540. P to pure water 25
After completely dissolving in m/, the catalyst was dried and reduced in the same manner as in Example 1 to obtain the catalyst of Example 5 in Table 1.

Example 6 Ruthenium chloride (RuCl3.3H2O) 1.530g
, 0.250 g of lithium chloride (LiCl), 0.465 g of cobalt chloride (CoCl2.6H2O) in 25 m of pure water.
The catalyst of Example 6 in Table 1 was obtained by performing two drying and reduction treatments in the same manner as in Example 1.

Example 7 Ruthenium chloride (RuC75・3H20) 1.530
f, Lithium chloride (LjCA) 0.250, Nickel chloride (Ns C70・6H20) o, 465
f was completely dissolved in 15 ml of pure water, and then dried and reduced in the same manner as in Example 1 to obtain the catalyst of Example 7 in Table 1.

Reference example 1 Ruthenium chloride (RuCz, '3I(20) 1.53
0y-1 Lithium chloride (LiCA) 0.250y-
The catalyst of Reference Example 1 in Table 1 was obtained in the same manner as in Example 1 except that the catalyst was dissolved in 25 rnA of pure water.

Reference example 2 Ruthenium chloride (RuCt, 3H20) 1.53
0? , chloroplatinic acid (H2Pt, C20.6I (20)
Example 1 except that 1.040y- was dissolved in 25ml of pure water.
The catalyst of Reference Example 2 in Table 1 was obtained in the same manner as above.

Reference example 3 Ruthenium chloride (RuC1, 3H20) 1.020
y-1 Nodium chloride (PdC12) 0.236?
The catalyst of Reference Example 3 in Table 1 was obtained in the same manner as in Example 1, except that the catalyst was dissolved in a mixed solution of 24 ml of pure water and 2 ml of hydrochloric acid.

Reference example 4 Ruthenium chloride (RuCt3-3H20) 1,020
．． P, iron chloride (FeCt3'6H20) 0.36 (
The catalyst of Reference Example 4 in Table 1 was obtained in the same manner as in Example 1 except that 1 was dissolved in 25 m/25 m of pure water.

Reference example 5 Ruthenium chloride (Ru C1s 3H20) 1.0
2'Of, cobalt chloride (COCl2-6H20)
0.310? The catalyst of Reference Example 5 in Table 1 was obtained in the same manner as in Example 1 except that the catalyst was dissolved in 25 mA of pure water.

Reference example 6 Ruthenium chloride (RuCl3-3H20) 1°020
P, dichloride, )r (NiCA2・6H20)
Example 1 except that 0.310y- was dissolved in 25m/25m of pure water.
The catalyst of Reference Example 6 in Table 1 was obtained in the same manner as above.

Activity Evaluation and Results Each of the above catalysts Ion/ was filled into a stainless steel reaction tube, and the raw material gas (coAI2=2/1) was
Feed at a rate of 5 Nl/Hr, and the reaction pressure was 5 kg/d.
G.

The reaction was carried out in The reaction gas was analyzed by chromatography as it was, and the result shown in column 02-0 of Table 1 is the total value of selectivity to acetic acid, acetaldehyde, and ethanol. Those shown in the HC column above C2 are C2H4, C2H6, C3H6゜C3H8, C4H
8, C4H1o, C5H4゜, C5H12, C6H42
゜It is the total value of selectivity to C6H14.

Claims (1)

[Claims] In a method for producing acetic acid acetaldehyde and/or ethanol by reacting carbon monoxide and hydrogen in the presence of a catalyst, the catalyst is selected from ruthenium and lithium and platinum, palladium, iron, cobalt, and nickel. A method characterized in that at least one metal is used in combination.