JPH0975743A - Method for producing hydrogenation catalyst - Google Patents

Abstract

(57) Abstract: A method for efficiently producing a catalyst for hydrogenating carbon monoxide to produce a branched hydrocarbon having 6 or more carbon atoms with high selectivity is provided. SOLUTION: The Y-type zeolite is subjected to an ion-exchange treatment and a de-alumina treatment until the ion exchange rate is at least 60% and the dealuminated rate from the inside of the crystal to the outside of the crystal is at least 10% to obtain NH ₄ type or H type. After obtaining a type-dealuminized Y-type zeolite, this is impregnated with a cobalt salt solution, dried and subjected to hydrogen reduction treatment to produce a hydrogenation catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing a hydrogenation catalyst. More specifically,
TECHNICAL FIELD The present invention relates to a method for efficiently producing a catalyst for hydrogenating carbon monoxide to produce a branched hydrocarbon having 6 or more carbon atoms with high selectivity.

[0002]

2. Description of the Related Art Conventionally, a method for producing a hydrocarbon compound by hydrogenating carbon monoxide in the presence of a catalyst is known, and a carrier used for this catalyst is, for example, ZS.
M-5 type zeolite, Y type zeolite, mordenite type zeolite and the like are known. As a method for preparing the catalyst, for example, a method of carrying a metal salt on a carrier and then carbonylating [[J. Chem. Soc., Che.
m. Commun. Pp. 458 (1988)
)], A method of directly supporting a carbonyl compound on a carrier [“J. Mol. Catal.”, Vol. 55, page 361 (1989)] and the like. However, although the catalysts prepared by these methods have high reactivity, they have a drawback that the supported carbonyl compound is extremely easily oxidized and is easily poisoned by oxygen in the air and deactivated. Further, in the method of directly supporting the carbonyl compound on the carrier, the carbonyl compound is expensive, and it is necessary to operate in a condition isolated from oxygen in the air in all steps of catalyst preparation.

Further, ZSM-5 type zeolite, Y type zeolite (without dealuminizing treatment) and mordenite type zeolite used as a carrier have a small crystal pore size and an extremely high branched hydrocarbon production rate. Low. Further, amorphous silica is also often used as a carrier, but this has a wide pore size distribution and is inferior to zeolite in shape selectivity.

On the other hand, ruthenium-supported niobium pentoxide or tantalum pentoxide was used as a carbon monoxide hydrogenation catalyst.
A method using a mixture of ZSM-5 type zeolite, Y type zeolite, γ-alumina, etc. has been proposed (Japanese Patent Laid-Open No. 62-109888). However,
This method is not a practical method because it uses an expensive metal salt as a catalyst raw material.

[0005]

Under these circumstances, the present invention provides a catalyst for hydrogenating carbon monoxide to produce a branched hydrocarbon having 6 or more carbon atoms with high selectivity. The purpose of the invention is to provide a method for efficient production.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the ion exchange rate and the dealumination rate of NH ₄ type or H type having a specific value or more are higher than a specific value. It was found that the objective can be achieved by impregnating alumina-treated Y-type zeolite with a cobalt salt solution, followed by drying and hydrogen reduction treatment, and the present invention has been completed based on this finding.

That is, the present invention relates to a Y-type zeolite,
The NH ₄ type or H type dealuminized Y-type zeolite is subjected to ion exchange treatment and dealumina treatment until the ion exchange rate is at least 60% and the dealumina rate from the inside of the crystal to the outside of the crystal is at least 10%. The present invention provides a method for producing a hydrogenation catalyst, which comprises impregnating the obtained solution with a cobalt salt solution, drying and then performing hydrogen reduction treatment.

[0008]

In the process of the present invention DETAILED DESCRIPTION OF THE INVENTION, Y-type zeolite used as a carrier for the hydrogenation catalyst has the general formula _{M 2 / n O · Al 2} O 3 · xSiO 2 · yH 2 O (I) ( wherein Is an alkali metal or alkaline earth metal, n is a valence of M, x is 2 to 10, and y is a number of 2 to 7), and is a crystalline aluminosilicate (Al, S
i) It is a cubic crystal having a structure in which an alkali metal, an alkaline earth metal, and water molecules are contained in the pores of the three-dimensional network structure in which the O ₄ tetrahedra share the vertices.

In the above general formula (I), the one in which M is Na is called a sodium type, and this M is ion-exchangeable, and those ion-exchanged by NH ₄ ion and H ion are NH ₃ ion and NH ₃ ion, respectively. Type ₄ and H type.

In the present invention, first, the Y-type zeolite is subjected to an ion exchange treatment and a dealumina treatment to obtain N-type zeolite.
An H ₄ type or H type dealuminized Y type zeolite is prepared. The order of the ion exchange treatment and the dealumina treatment is not particularly limited, and the ion exchange treatment may be followed by the dealumina treatment, or the dealumina treatment may be followed by the ion exchange treatment. Good.

There are no particular restrictions on the methods of ion exchange treatment and dealumination treatment, and conventionally known methods can be used. For example, in order to obtain NH ₄ type Y-type zeolite by ion exchange, a method of heating the Y-type zeolite in an ammonium salt solution having an appropriate concentration, preferably under reflux, can be used.
Further, as the alumina treatment, for example, a steam treatment method,
Although any method selected from an acid treatment method, a chelate extraction method, a silicon tetrachloride treatment method, a fluorination method and the like can be used, among them, the steam treatment method and the acid treatment method are easy to operate. It is preferable from the point of being present. As the steam treatment method, for example, a method of treating the Y-type zeolite with steam at about 500 to 800 ° C. is used. According to this steam treatment method, the alumina inside the crystal of the Y-type zeolite partially moves to the outside of the crystal and is dealuminized. Alumina transferred to the outside of the crystal, without removing it from the zeolite, it is possible to use the zeolite adhered alumina as it is as a carrier, but it is used as a carrier, which is obtained by removing the alumina transferred to the outside of the crystal from the zeolite, It is preferable in terms of catalyst performance. To remove the alumina that has migrated to the outside of the crystal from the zeolite, an alkali extraction method using a sodium hydroxide aqueous solution or the like, or an acid extraction method using a mineral acid aqueous solution or the like is used. In addition, when the dealumina treatment with water vapor is repeated and the unit extraction of Y-type zeolite contracts by 1.3% or more and the acid extraction method with an aqueous mineral acid solution is applied, it is easy to remove all of the alumina that has migrated to the outside of the crystal. Alumina remaining inside the crystal can be extracted in addition to being extracted.

In the method of the present invention, the Y-type zeolite is subjected to ion exchange treatment and dealumination treatment until the ion exchange rate is at least 60% and the dealumination rate from inside the crystal to outside the crystal is at least 10%. is necessary. When the ion exchange rate is less than 60% or the dealuminated rate from the inside of the crystal to the outside of the crystal is less than 10%, it is difficult to obtain a catalyst having desired performance. From the viewpoint of catalytic performance, the preferable ion exchange rate is 80% or more, and the preferable dealumination rate from the inside of the crystal to the outside of the crystal is 20% or more.
The ion exchange rate can be easily calculated from the chemical analysis value of zeolite. The dealumination rate from the inside of the crystal to the outside of the crystal can be determined by the method described below.

That is, the positions (2θ values) of the 533 and 642 diffraction lines of Y-type zeolite were determined by the X-ray powder diffraction method,
From this value, the size (a ₀ ) of the unit cell is calculated using the following equation.

[0014]

[Equation 1]

Here, λ is the wavelength of the X-ray used, that is, 1.5405981 angstroms, and h, k and l are 5, 3, 3 or 6, 4, 2, respectively. The following relationship holds between the size a ₀ of the unit cell and the number N _Al of aluminum atoms in the unit cell. a ₀ = 0.00868N _Al +24.191 (Angstrom) (1) [1967, published by Society of Chemical Industry, London, "Molecular Sieves (m
molecular Sieves ", page 53].

Assuming that the number of aluminum atoms in the unit cell of the starting Y-zeolite is N _Al S and the number of aluminum atoms in the unit cell of the dealuminized Y-zeolite is N _Al D, the inside of the crystal is outside the crystal. The dealumination rate is as follows.

[0017]

[Equation 2]

In the method of the present invention, the ion exchange rate is 6
It is advantageous to repeatedly subject the Y-type zeolite to treatment with an ammonium salt solution and steam in order to achieve a alumina removal rate of 0% or more and from the inside of the crystal to the outside of the crystal of 10% or more. In this case, the order of the treatment with the ammonium salt solution and the steam is not particularly limited as described above, but when the method in which the final treatment is the steam treatment is adopted, it is possible to obtain ion exchange by the treatment with the ammonium salt solution. The thus obtained NH ₄ type Y-type zeolite is substantially converted into the H-type Y-type zeolite, and the catalytic performance is further improved, which is preferable.

After the steam treatment, when the alkali extraction method is used to remove the alumina that has migrated from the inside of the crystal to the outside of the crystal, the H-type Y-type zeolite is partially converted to the alkali metal-type Y-type zeolite. It may be converted and the desired ion exchange rate may not be reached. Therefore, it is desirable to sequentially perform the treatment with the ammonium salt solution and the steam after the alkali extraction treatment.

Next, the thus prepared NH ₄ type or H type dealuminized Y-type zeolite is impregnated with a cobalt salt solution. Examples of the cobalt salt solution include divalent, trivalent, and tetravalent cobalt ions, or cobalt complex ions (cobalt charges are plus divalent, plus trivalent,
An aqueous solution containing (plus tetravalent) is included. Examples of the cobalt salt used for preparing the aqueous solution include water-soluble cobalt salts such as cobalt nitrate and various water-soluble cobalt complex salts. In order to impregnate the carrier zeolite with the cobalt salt solution, a method of immersing the carrier zeolite in the cobalt salt solution is usually used. The amount of the cobalt salt solution impregnated is 1 to cobalt metal as a carrier.
It is advantageous to choose to be 10% by weight.

In this way, a desired hydrogenation catalyst is obtained by impregnating the zeolite of the carrier with the cobalt salt solution, drying and then subjecting it to hydrogen reduction treatment. The hydrogen reduction treatment is carried out, for example, in a hydrogen stream of 350 to 450.
It is performed by heating at a temperature of about ℃.

In the present invention, the hydrogenation catalyst thus obtained is suitably used for the hydrogenation reaction of carbon monoxide. As the method for hydrogenating carbon monoxide, for example, a fixed bed reactor is charged with the hydrogenation catalyst, and
A mixed gas containing carbon monoxide and hydrogen in a molar ratio of 2: 3 to 1: 4 and containing an inert gas such as argon or nitrogen in an amount of about 0.5 to 1 mole times that of carbon monoxide, Preferably pressure is 5 to 50 bar, temperature is 200 to 300 ° C., L
A method of continuously supplying under a condition of HSV (liquid hourly space velocity) of ¹ to 10 hr ⁻¹ and contacting with a catalyst is preferable. In this way, branched hydrocarbons having 6 or more carbon atoms are produced with high selectivity from carbon monoxide and hydrogen.

[0023]

According to the present invention, the Y-type zeolite is subjected to ion exchange treatment and dealumina treatment, impregnated with a cobalt salt solution, dried and then subjected to hydrogen reduction treatment to hydrogenate carbon monoxide to obtain carbon. A catalyst for producing a branched hydrocarbon of several 6 or more with high selectivity can be efficiently produced.

[0024]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of hydrogenation catalyst In a three-necked flask, 200 g and 0 of Y-type zeolite [NaY, sodium-type Y-type zeolite, manufactured by Catalyst Kasei Kogyo Co., Ltd.] having sufficiently absorbed moisture was used. After adding 4 liters of 1N ammonium chloride aqueous solution and heating under reflux for 2 hours for ion exchange, the solid matter (ammonium-type Y-type zeolite) was filtered on a Buchner funnel. Then, the filter cake is washed with 2 liters of distilled water at about 90 ° C.,
Dried. This ammonium-type Y-zeolite 8
Divide each 7g into 2 parts, put each into a stainless steel container with an internal volume of 160ml, and keep at 40 ° C at 650 ° C.
After heat treatment for 1 minute, they were combined and about 168 g of dealuminized Y-type zeolite was obtained. This sample is designated as DAY-1.

Next, to this DAY-1 was added 4 liters of a 1N ammonium chloride aqueous solution, which was heated under reflux for 2 hours for ion exchange, and then filtered and dried in the same manner as above. Then, this re-ion-exchanged Y-type zeolite 77.5
g in a stainless steel container similar to the above, 750
Heat treatment was performed at 40 ° C. for 40 minutes to obtain dealuminized Y type zeolite. This sample is designated as DAY-2. The chemical analysis values of this product are shown in Table 1.

The dealumination rate and the ion exchange rate from this DAY-2 zeolite were 0.55% and 88%, respectively, based on the chemical analysis values. The dealumination rate and ion exchange rate from the zeolite were determined by the following equations. De-alumina rate (%) from zeolite = [(AB) /
A] × 100 ion exchange ratio (%) = [(C- D) / C] × 100 A: NaY of Al ₂ O ₃ / SiO ₂ weight ratio of B: Al ₂ samples O ₃ / SiO ₂ weight ratio C: NaY of Na ₂ O / SiO ₂ weight ratio of D: Na ₂ O / SiO ₂ weight ratio of the sample addition, dealumination rate from the crystal inside to the outside of the crystal is calculated 43.4% from the formula (1).

2 g of DAY-2 thus obtained
Was placed in a two-necked eggplant-shaped flask connected to a vacuum system, and was degassed by a rotary pump while being heated at 200 ° C. for 2 hours for dehydration. Next, 0.4938 g of cobalt nitrate hexahydrate [Co (NO ₃ ) ₂ 6H ₂ O] and 2.5 ml of distilled water were placed in a glass tube with a cock attached to one mouth of the eggplant-shaped flask, and cobalt nitrate was added. Was completely dissolved and then introduced into a vacuum eggplant-shaped flask. The dealuminized Y-type zeolite absorbed the cobalt nitrate solution and formed a slightly viscous lump. Next, the eggplant-shaped flask was separated from the vacuum system, heated to 60 ° C. with an evaporator, and the contents were evaporated to dryness to obtain a cobalt-supporting Y-type zeolite. This sample is Co-DAY-
Let it be 2.

(2) Hydrogenation of carbon monoxide Cobalt-supporting Y-type zeolite (C) obtained in (1) above
o-DAY-2) 1 g of dried product, inner diameter 10 mm, length 3
Quartz wool was held in the center of a 00 mm stainless steel reaction tube, attached to a carbon monoxide hydrogenation reactor, and heated at 400 ° C. for 2 hours in a hydrogen stream for reduction treatment. Next, a mixed gas containing argon, hydrogen and carbon monoxide in a molar ratio of 1: 6: 3 was added to the catalyst layer at a temperature of 249.
The hydrogenation reaction of carbon monoxide was carried out under the conditions of a temperature of 20 ° C., a pressure of 20 bar and a flow rate of 6 liters / hour. The produced gas was analyzed by a gas chromatography method. The analysis results are shown in Table 2.

Example 2 (1) Preparation of hydrogenation catalyst 50 g of DAY-2 prepared in Example 1 and 5 liter of 0.1N sodium hydroxide aqueous solution were mixed and the mixture was mixed at 24 ° C. for 3 hours.
After standing still for 0 minutes, filtration, washing, drying and moisture absorption treatment were performed. Then, this alkali-treated DAY-2 46.8
g in 1N ammonium chloride aqueous solution 3.12 liters under reflux for 40 minutes for ion exchange, filtration,
It was washed and dried. 40g of this ion-exchange processed product
Was placed in a stainless steel reaction tube and heat-treated at 750 ° C. for 40 minutes. This sample is designated as DAY-3. The chemical analysis values of this product are shown in Table 1.

The dealumination rate and the ion exchange rate from this DAY-3 zeolite were 23% and 96%, respectively, from the chemical analysis values. Further, the dealumination rate from the inside of the crystal to the outside of the crystal is estimated to be 57.4% or more. Next, 1 g of DAY-3 thus obtained was placed in a two-necked flask connected to a vacuum system, and 0.2471 g of cobalt nitrate hexahydrate was carried and dried in the same manner as in Example 1. This cobalt-supported Y-type zeolite is Co-DA
Y-3.

(2) Hydrogenation of carbon monoxide Cobalt-supported Y-type zeolite (C) obtained in (1) above
o-DAY-3) Using the dried product, a hydrogenation reaction of carbon monoxide was carried out in the same manner as in Example 1, and the produced gas was analyzed by a gas chromatography method. The analysis results are shown in Table 2.

Comparative Example 1 (1) Preparation of hydrogenation catalyst Sodium-type Y-type zeolite (Na
Cobalt nitrate hexahydrate was supported in the same manner as in Example 1 without subjecting Y) to ion exchange treatment and dealumina treatment to prepare a cobalt-supporting Y-type zeolite. This sample is designated as Co-NaY. The chemical analysis values of NaY are shown in Table 1.

(2) Hydrogenation of carbon monoxide The cobalt-supporting Y-type zeolite (C) obtained in (1) above.
O-NaY) dried product was used to carry out a hydrogenation reaction of carbon monoxide in the same manner as in Example 1, and the produced gas was analyzed by a gas chromatography method. The analysis results are shown in Table 2.

Comparative Example 2 (1) Preparation of hydrogenation catalyst 50 g of DAY-2 prepared in Example 1 was mixed with 5 liter of 0.1N sodium hydroxide aqueous solution, and the mixture was mixed at 24 ° C. for 3 hours.
After standing still for 0 minutes, filtration, washing, drying and moisture absorption treatment were performed. This sample is designated as DAY-4. The chemical analysis values of this product are shown in Table 1. The dealumination rate and ion exchange rate from the zeolite of DAY-4 were 24% and 46%, respectively, from the chemical analysis values. In addition, the dealumination rate from the inside of the crystal to the outside of the crystal is estimated to be 37.7%.
Next, cobalt nitrate hexahydrate was supported on thus obtained DAY-4 in the same manner as in Example 1 to prepare a cobalt-supporting Y-type zeolite. This sample is Co-DA
Y-4.

(2) Hydroxylation of carbon monoxide The cobalt-supporting Y-type zeolite (C) obtained in (1) above.
o-DAY-4) Using the dried product, a carbon monoxide hydroxylation reaction was carried out in the same manner as in Example 1, and the produced gas was analyzed by a gas chromatography method. The analysis results are shown in Table 2.

[0037]

[Table 1]

[0038]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ira Maiyanen Finland, Espoo, Biorosinkya 7, Viti Tea Chemical Technology

Claims (6)

[Claims] 1. A Y-type zeolite is subjected to ion-exchange treatment and de-alumina treatment until the ion exchange rate is at least 60% and the dealumination rate from the inside of the crystal to the outside of the crystal is at least 10%, and NH ₄ -type or A method for producing a hydrogenation catalyst, comprising obtaining a H-type dealuminized Y-type zeolite, impregnating it with a cobalt salt solution, drying and then performing a hydrogen reduction treatment. 2. The method according to claim 1, wherein the Y-type zeolite is repeatedly subjected to treatment with an ammonium salt solution and steam to carry out an ion exchange treatment and a dealumina treatment. 3. The production method according to claim 1, wherein the Y-type zeolite is subjected to steam treatment, and then extracted with an alkali or an acid to be treated for dealumination. 4. The production method according to claim 1, 2 or 3, wherein 1 to 10% by weight of cobalt is loaded on the NH ₄ type or H type dealuminized Y-type zeolite in terms of metal. 5. The production method according to claim 1, wherein the hydrogenation catalyst is for hydrogenation of carbon monoxide. 6. A hydrogenation catalyst hydrogenates carbon monoxide,
The production method according to claim 5, which is for producing a branched hydrocarbon.