JP3272386B2 - Alcohol production catalyst and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing alcohols comprising a copper-iron-tertiary metal atom having high activity and high selectivity, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Higher alcohols are produced by reducing higher fatty acid methyl esters with high pressure hydrogen at high temperatures. Conventionally, the catalyst used for this reaction is a copper-chromium oxide catalyst,
It is usually called a copper-chromite catalyst. The process has not significantly advanced from that described in Industrial and Engineering Chemistry, Vol. 26, p. 878 (1936). This catalyst is used for production.
It has a serious disadvantage that a large amount of hexavalent chromium ions are discharged. Due to environmental pollution, these heavy metals are collected in a suitable manner, but the ultimate treatment of the sludge of the heavy metals generated here has not yet been established.

In order to solve this problem, copper-iron-aluminum catalysts produced by various methods have been proposed (JP-A-53-92395, JP-A-55-8820, JP-B-58-1983). No. -50775). However, these catalysts are superior to conventional copper-chromite catalysts in activity, selectivity, and durability, but the filtration speed for filtering the catalyst from the catalyst precipitation slurry during the production of the catalyst is slow, requiring large-scale filtration equipment. (JP-A-53-92395 and JP-A-55-8820). After the reaction, when the reaction product is withdrawn from a high pressure to a normal pressure through a high-pressure valve, the catalyst is remarkably atomized. Since filtration becomes difficult and urea is used as a catalyst precipitant, there is a problem in the production process such as a large load on urea wastewater and ammonia wastewater treatment (Japanese Patent Application Laid-Open No. 58-50775). No.).

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have developed a method for suppressing the atomization of the above-mentioned catalyst in order to establish an industrial production method of a pollution-free catalyst which replaces a copper-chromite catalyst which has a problem of environmental pollution. As a result of intensive studies on rationalization of the catalyst production process, at least one selected from the group consisting of aluminum, silicon, titanium, zirconium, magnesium and iron oxides and hydroxides of the metal, zeolite, and silica-alumina Using one kind as a carrier, using an alkali substance such as an alkali metal or alkaline earth metal hydroxide or carbonate in place of urea as a precipitant, the periodic table IIb, IIIb, IVa, IVb, IVb, VIb By adding at least one metal salt selected from the group consisting of metals of groups IVa and VIIa (excluding aluminum) , atomization of the catalyst can be reduced. The present invention provides a method for producing a copper-iron- third metal- based catalyst in which a catalyst which can be suppressed and whose activity, selectivity, durability and filterability are greatly improved is obtained, and the catalyst production process is greatly simplified. This led to the completion of the present invention.

That is, the present invention provides a carrier comprising at least one member selected from the group consisting of:
The atomic ratio is Cu / Fe / (Group IIb, IIIb, IVa,
Group IVb, Group VIb and Group VIIa (excluding aluminum), at least one metal selected from the group consisting of metals) / (at least one metal selected from the group consisting of alkali metals and alkaline earth metals) = 1 /0.4 to 2.5
/0.5 to 5.0 / 0 to 0.4. Oxides of aluminum, silicon, titanium, zirconium, magnesium and iron Aluminum, silicon, titanium, zirconium, magnesium and iron hydroxide zeolite silica-alumina.

[0006] The copper-iron-third metal catalyst of the present invention comprises the following first step, second step and third step, or the following first step, second step, third step and fourth step: It is manufactured by a manufacturing method performed in this order. (First step) At least one carrier selected from the group consisting of the following, and is suspended in an aqueous medium, and a water-soluble copper salt and a water-soluble iron salt are reacted with an alkali substance in the suspension. Depositing a copper compound and an iron compound on the surface of the carrier. Oxides of aluminum, silicon, titanium, zirconium, magnesium and iron hydroxides of aluminum, silicon, titanium, zirconium, magnesium and iron zeolite silica-alumina (second step) in the suspension obtained in the first step In the Periodic Table IIb group,
Group IIIb, IVa group, IVb group, VIb and Group VIIa metals (for
However, an aqueous solution containing at least one metal selected from the group consisting of aluminum (excluding aluminum) (hereinafter, referred to as a third metal) is reacted with an alkaline substance to obtain a suspension obtained in the first step. Precipitation of the third metal compound one or more times on the surface of the solid particles present in step (a). (Third step) A step of obtaining a precipitate from the suspension obtained in the first step and the second step, washing with water to obtain a slurry or powder,
If the fourth step is not performed, then a step of drying and firing the slurry or the powder. (Fourth step) (A) The slurry or powder obtained in the third step,
(B) mixing with at least one selected from the group consisting of alkali metal salts, alkali metal hydroxides, alkaline earth metal salts and alkaline earth metal hydroxides, drying and sintering the obtained slurry or powder; Process.

The copper-iron-third metal catalyst according to the present invention comprises:
The composition is atomic ratio of Cu / Fe / third metal / (at least one metal selected from the group consisting of alkali metals and alkaline earth metals) = 1 / 0.4-2.5 / 0.5-5.0 / 0
It is important that it is in the 1.0 range. When the atomic ratio is outside these ranges, the activity of the resulting catalyst is lower than that of the copper-chromite catalyst, and at the same time, the amount of by-products increases when used in the hydrogenation reaction. The alkali metal and / or alkaline earth metal may not be used, but when used within the above range, the selectivity of the reaction is improved.

Each step of the method for producing a copper-iron-third metal catalyst of the present invention will be described below.

First Step The first step in the manufacturing method of the present invention is performed as follows.
First, a water-soluble copper salt and a water-soluble iron salt are mixed in atomic ratio of Cu / Fe = 1.
/0.4-2.5, and the carrier is suspended in this aqueous solution so that the atomic ratio of Cu / support metal atom = 1 / 0.1-3.0. The suspension is heated to 60 DEG-120 DEG C., and an aqueous solution of an alkali substance in an amount corresponding to the total equivalent number of copper and iron ions is added to precipitate the copper compound and the iron compound on the surface of the catalyst support. Examples of the water-soluble copper salt used in the present invention include cupric sulfate, cupric chloride, cupric nitrate and the like, and a mixture thereof may be used. The water-soluble iron salt used in the present invention includes ferrous sulfate, ferrous chloride, ferrous nitrate and the like, and a mixture thereof may be used, but ferrous sulfate is used. Is more economical than optimal. Ferric salts can also be used in combination,
It should be noted that excessive addition of the ferric salt deteriorates the catalytic performance, especially the physical properties of the catalyst. Examples of the alkali substance used in the present invention include hydroxides or carbonates of alkali metals or alkaline earth metals. The method of adding the alkali substance to the suspension is not particularly limited, but these alkali substances are usually added in an aqueous solution in consideration of operability. When an alkali metal or alkaline earth metal hydroxide is used as the alkali substance, it is preferable to slowly add the hydroxide in order not to impair the filterability of the precipitation catalyst. In the present invention, it is optimal to use an alkali metal carbonate. The concentration of these alkaline substances can be arbitrarily selected, but in consideration of the productivity of the catalyst, a high-concentration precipitant can be used. For example, in the case of sodium carbonate, an aqueous solution having a concentration of 20 to 23% is suitable. Aluminum, silicon, as a carrier used in the first step,
At least one selected from the group consisting of titanium, zirconium, magnesium and iron oxides and hydroxides of the metal, zeolite, and silica-alumina may be used as it is after preparation in the reaction vessel, A separately prepared product may be used. Examples of the mixture of the carrier metals include silica-alumina, and any compound containing the above metal species, such as zeolite, can be used. It is preferable to use a carrier having a relatively uniform particle size. The carrier has an average particle diameter of 0.1 to 500 μm, preferably 0.4 to 50 μm. If the average particle size is below or above this range, both catalytic activity and filterability cannot be maintained coaxially with the desired level of the present invention. As a method for preparing a carrier in a reaction vessel, an amount of ferric salt used as a carrier, for example, a sulfate, a nitrate, a hydrochloride, or the like, dissolved in water, and then an alkali in an amount corresponding to the equivalent number of iron ions There is a method of neutralizing by dropping a metal oxide, for example, an aqueous solution of sodium carbonate at a temperature of 60 ° C. or higher. In the case of this method, the first step can be continuously performed by charging a copper salt and an iron salt into the slurry without purifying the formed precipitate. Here, when a carrier having uniform physical properties is used, a catalyst with more stable performance can be produced. Therefore, use of a carrier having uniform physical properties is more advantageous for production on an industrial scale.

Second Step The second step in the production method of the present invention is performed as follows.
That is, an aqueous solution of a third metal (however, in this case, the amount of the third metal is an atomic ratio with respect to the water-soluble copper salt used in the first step).
Cu / third metal = 1 / 0.5-5.0, preferably 1 / 0.8-
3.0 amount. ) And an alkali substance in an amount equivalent to the equivalent number of the third metal ion is dropped, and the temperature of the suspension is adjusted to 60
It is carried out by precipitating the third metal compound while maintaining the temperature at 〜100 ° C. If the temperature of the suspension is outside this range, the desired activity and selectivity of the resulting catalyst will not be obtained. The above-mentioned aqueous solution of the third metal is prepared using a salt of the third metal, for example, a sulfate, a chloride, a nitrate, etc. Among them, the sulfate is most preferable. Moreover, you may use these mixtures. Examples of the above-mentioned alkali substance include an alkali substance used in the first step. The addition method is preferably an aqueous solution from the viewpoint of operability. The concentration is not particularly limited, but is 20% by weight for economic reasons.
It is preferable to use an aqueous solution of such a degree. As for the method of adding the alkaline substance, it is desirable to simultaneously add the third metal aqueous solution and the above-mentioned alkaline substance or its aqueous solution to the suspension in order to prevent a sudden change in the pH of the suspension. Further, the second step for improving the activity and selectivity in the hydrogen reduction reaction can be performed in one step or in two or more steps. The pH of the suspension obtained by the method described above
After adjusting to 7.0 or more, aging is performed for 0 to 8 hours.

Third Step The third step in the production method of the present invention is performed as follows.
In the third step, the precipitate obtained in the second step is washed with water by a conventional method to obtain a slurry or powder. If the fourth step is not performed, then a step of drying and firing the slurry or the powder is performed. The firing temperature is usually in the range of 100 ° C to 1200 ° C, preferably 400 ° C to 900 ° C. The firing time is not particularly limited, but is preferably 10 hours or less from an economical point of view. After firing, you may grind it,
It can be used immediately as a catalyst without grinding. Fourth Step In the production method of the present invention, the fourth step may not be carried out in some cases, but the fourth step may be carried out due to the selectivity of the reaction. In this case, the operation is performed as follows. First, (a)
The slurry or powder obtained in the third step, and (b) at least one selected from the group consisting of an alkali metal salt, an alkali metal hydroxide, an alkaline earth metal salt and an alkaline earth metal hydroxide (hereinafter, referred to as , Alkali metal / alkaline earth metal hydroxide, etc.). In this case, the alkali metal / alkaline earth metal hydroxide or the like has an atomic ratio of Cu / (alkali metal and / or alkaline earth metal) = 1/0 to 0.4, preferably 1 / 0.001 to 0.4. Mix. Alkali metal / alkaline earth metal hydroxide etc. may be added in powder or granular form,
Preferably, it is added as an aqueous solution. Examples of the alkali metal / alkaline earth metal hydroxide include Ba (OH) ₂ , Ca (OH)
₂ , BaCO ₃ , NaOH and the like. The slurry or powder thus obtained is dried and fired. The firing temperature is usually in the range of 100 ° C to 1200 ° C, preferably 400 ° C.
℃ to 900 ℃. The firing time is not particularly limited, but is preferably 10 hours or less from an economical point of view. The fired product may be pulverized, but this can be used immediately as a catalyst without pulverization.

The catalyst of the present invention has excellent performance such as activity and selectivity due to the combination of the above metals. However, other metals such as noble metals may be added within a range not to impair the effects of the present invention. It is possible and does not exclude the use of any other metal.

The hydrogen reduction of the higher fatty acid ester using the catalyst of the present invention obtained above is carried out at a temperature of 130 to 350 ° C., preferably 180 to 300 ° C., a hydrogen pressure of 10 to 300 kg / cm ² , preferably 100 It carried out at ~250 kg / cm ^2. The amount of the catalyst used is in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the higher fatty acid ester as the starting material.

As the higher fatty acid ester to be hydrogenated using the catalyst of the present invention, those having a fatty acid having 6 or more carbon atoms and having at least one ester group can be mentioned. As the higher fatty acid ester, any of a straight-chain fatty acid ester, a branched-chain fatty acid ester and an unsaturated fatty acid ester may be used, or a mixture thereof may be used. The alcohol constituting the higher fatty acid ester is preferably a lower alcohol having 1 to 4 carbon atoms, and particularly preferably methanol. Specific examples of higher fatty acid esters include coconut oil fatty acid methyl ester, palm oil fatty acid methyl ester, palm kernel oil fatty acid methyl ester, rapeseed oil fatty acid methyl ester, tallow fatty acid methyl ester, fish oil fatty acid methyl ester, orange rough fatty acid methyl ester and the like. Is mentioned.

[0015]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0016] reactor with a first embodiment reflux condenser, water (300g), CuSO ₄ · 5H
₂ O (48 g), FeSO ₄ .7H ₂ O (59 g) and aluminum hydroxide (Hygilite H-32 manufactured by Showa Denko, 12.14 g) were added, and the temperature was increased to 96 ° C. while stirring. 95 ℃
It was kept for 1 hour while keeping at ± 2 ° C. Then, while maintaining this temperature, a solution of Na ₂ CO ₃ (44.8 g) dissolved in water (150 g) is added dropwise over about 80 minutes. During the reaction, the blue-green precipitate gradually turns brown, and finally turns black.
The pH after completion of the dropwise addition was 8.95. While maintaining the temperature at 95 ° C. ± 2 ° C., a solution of Ti (SO ₄ ) ₂ (40.0 g) dissolved in water (109.2 g) and Na ₂ CO ₃ (41.0 g) dissolved in water (145.4 g). The solution was added dropwise at the same time. The aqueous solution of the metal salt was dropped over 60 minutes, and the aqueous solution of the alkali substance was dropped over 30 minutes. The pH after dropping the aqueous solution of the alkaline substance is 8.71, and the pH after dropping the aqueous metal salt solution is
8.11. Ti (SO ₄ ) ₂ (20.0 g) was added to water (53.5
The solution dissolved in g) was added dropwise over 30 minutes. At this time
pH was 4.12. Next, Na ₂ CO ₃ (16.3 g) was added to water (57.8 g).
The solution dissolved in g) was added dropwise over about 30 minutes. 10 more
% NaOH aqueous solution was added dropwise to adjust the pH to 10.5. Aging was performed for 1 hour while maintaining the pH at 10.5. After completion of the aging, the reaction product was subjected to suction filtration. Filtration was very easy and the filtrate was colorless. After washing the precipitate three times with 450 ml of water each time, Ba (O
H) ₂ (4.21 g) dissolved in water (320 g) was added.
After stirring for 30 minutes, the mixture was evaporated to dryness. Lightly pulverize the dried product 7
Calcination in air at 50 ° C. for 1 hour gave the desired catalyst. The atomic ratio of Cu / Fe / Ti / Ba of this catalyst is 1/1 / 1.09 / 0.063.
Met.

[0017] Example 2~6 Ti (SO ₄₎ in place of the _{2 · H 2 O, Sn (} SO 4) 2 · H 2 O, ZrSO 4 ·
A catalyst was obtained in the same manner as in Example 1, except that 7H ₂ O, ZnSO ₄ .7H ₂ O, MnSO ₄ .7H ₂ O, and Ga ₂ (SO ₄ ) ₃ were used in the same molar ratio. .

Examples 7 to 11 A catalyst was obtained in the same manner as in Example 1 except that titanium oxide, zirconium oxide, zeolite, silica-alumina and ferric oxide were used instead of aluminum hydroxide. . In Example 7 using titanium oxide, Cu / Fe / Ti
The atomic ratio of / Ba was set to 1/1 / 1.81 / 0.063.

Example 12 A catalyst was obtained in the same manner as in Example 1 except that magnesium oxide was used instead of aluminum hydroxide and the atomic ratio of the metal used was as shown in Table 2. .

Examples 13 to 21 Table 3 shows the atomic ratio of Cu / Fe / third metal or the calcination temperature of the catalyst.
A catalyst was obtained in the same manner as in Example 1 except that the ratio was variously changed as shown in Table 1.

Comparative Example 1 Water (400 g), CuSO ₄ .5H were placed in a reactor having a reflux condenser.
_{2 O (40.7g), FeSO 4} · 7H 2 O (45.5g), Ti (SO 4) 2 (6
0.0g) and aluminum hydroxide (Hygilite H-32, manufactured by Showa Denko, 12.14 g).
° C. The temperature was maintained at 95 ° C. ± 2 ° C. for 1 hour. Then, while maintaining this temperature, Na ₂ CO ₃ (76.7
g) dissolved in water (272 g) is added dropwise over about 80 minutes. During the reaction, the blue-green precipitate gradually turns brown, and finally turns black. Further, a 10% aqueous solution of NaOH was added dropwise to adjust the pH to 10.5. Aging was performed for 1 hour while maintaining the pH at 10.5, and thereafter the same operation as in Example 1 was performed to obtain a catalyst.

Comparative Example 2 A catalyst was obtained in the same manner as in Comparative Example 1, except that aluminum hydroxide was not used.

Comparative Examples 3-5 Catalysts were prepared in the same manner as in Comparative Example 1 except that the atomic ratio of Cu / Fe / third metal / (alkali metal and / or alkaline earth metal) was variously changed to the ratio shown in Table 4. I got

Test Example 3.75 g of the catalyst obtained in each of Examples and Comparative Examples was added to 150 g of coconut oil fatty acid methyl ester (hereinafter referred to as ME),
In a ²⁰⁰ ml autoclave, hydrogen pressure 250 kg / cm ² , reaction temperature
At 275 ° C., hydrogen was flowed at 5 liter / min, and the reaction was carried out for 4 hours. During the reaction, sampling was performed at 30, 60, 90, 120, 180, and 240 minutes, and the saponification value was measured. The saponification value of the raw material ME is SV ₀ , the saponification value of the reactant at the time of sampling at t minutes is SV _t , the equilibrium saponification value at 275 ° C., 250 kg / cm ² is SV _e, and the primary reaction rate is determined from this value. Constant k (× 10
The ³ / min), were determined by k = (1 / t) ln (SV 0 -SV e) / (SV t -SV e). The reaction k when using the catalyst of Example 1 is
It was 7.20 × 10 ³ . After the completion of the reaction, the reactor was cooled, the autoclave was released, the reaction solution was withdrawn, and the catalyst was removed by pressure filtration. The composition of the obtained reaction product was analyzed by gas chromatography. Then, in order to measure the filtration rate, 7.50 g of the catalyst was added to 150 g of ME, and in a 500 ml autoclave, the hydrogen pressure was 250 kg / cm ² , and the reaction temperature was 27.
After conducting the reaction at 5 ° C for 1 hour, without cooling, 200kg / cm ²
The whole amount was sampled through a high-pressure valve while the pressure was reduced. The extracted slurry (58 g) was weighed, diluted to 255 g with dodecyl alcohol, and then subjected to constant conditions (filtration pressure 3 kg / cm ² , filtration Filtration is performed at a temperature of 50 ° C., and the filtration rate per unit time F (m ³ / cm ² −
Hr). Tables 1 to 4 show these results.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

Note) * The atomic ratios in Tables 1-4 are all Cu
/ Fe / third metal / (alkali metal and / or alkaline earth metal) ratio.

[0030]

According to the present invention, a copper-iron-third metal-based catalyst having extremely high activity and high selectivity can be obtained, and by using such a catalyst, a very high-purity higher alcohol can be very easily obtained. can get.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C07C 29/149 B01J 23/82 Z // C07B 61/00 300 23/84 311Z (58) Field surveyed (Int.Cl. ⁷ , DB name) ) B01J 21/00-37/36 C07C 29/00, 31/00

Claims (6)

(57) [Claims] 1. A carrier comprising at least one member selected from the group consisting of: and a carrier having an atomic ratio of Cu / Fe /
(At least one metal selected from the group consisting of metals of Group IIb, IIIb, IVa, IVb, VIb and VIIa (excluding aluminum ) / (alkali metal and alkaline earth metal) At least one metal selected from the group consisting of: 1 / 0.4 to 2.5 / 0.5 to 5.0 / 0
A catalyst for producing alcohol, which is from 0.4 to 0.4. Aluminum, silicon, titanium, zirconium, magnesium and iron oxides Aluminum, silicon, titanium, zirconium, magnesium and iron hydroxides zeolite silica-alumina 2. Periodic table IIb, IIIb, IVa, IVb
Group, VIb and VIIa metals, except that aluminum
At least one metal selected from the group consisting of
But titanium, tin, manganese, zirconium, zinc or
The alcohol production catalyst according to claim 1, which is gallium. 3. In producing the catalyst for alcohol production according to claim 1 or 2 , the following first step, second step and third step, or the following first step, second step, and performing a third step and the fourth step in this order, Arco
Of producing a catalyst for the production of steel. (First step) At least one carrier selected from the group consisting of the following, and is suspended in an aqueous medium, and a water-soluble copper salt and a water-soluble iron salt are reacted with an alkali substance in the suspension. Depositing a copper compound and an iron compound on the surface of the carrier. Oxides of aluminum, silicon, titanium, zirconium, magnesium and iron hydroxides of aluminum, silicon, titanium, zirconium, magnesium and iron zeolite silica-alumina (second step) in the suspension obtained in the first step In the Periodic Table IIb group,
Group IIIb, IVa group, IVb group, VIb and Group VIIa metals (for
However, an aqueous solution containing at least one metal selected from the group consisting of aluminum (excluding aluminum) (hereinafter, referred to as a third metal) is reacted with an alkaline substance to obtain a suspension obtained in the first step. Precipitation of the third metal compound one or more times on the surface of the solid particles present in step (a). (Third step) A step of obtaining a precipitate from the suspension obtained in the first step and the second step, washing with water to obtain a slurry or powder,
If the fourth step is not performed, then a step of drying and firing the slurry or the powder. (Fourth step) (A) The slurry or powder obtained in the third step,
(B) mixing with at least one selected from the group consisting of alkali metal salts, alkali metal hydroxides, alkaline earth metal salts and alkaline earth metal hydroxides, drying and sintering the obtained slurry or powder; Process. 4. The reaction temperature in the first step and the second step is 60 to
The method for producing a catalyst for alcohol production according to claim 3 , wherein the temperature is 120 ° C. 5. The sintering temperature in the third step or the fourth step is 100.
The method for producing a catalyst for alcohol production according to claim 3 or 4 , wherein the temperature is from -1200C. 6. The third metal is titanium, tin, manganese,
6. Zirconium, zinc or gallium.
A method for producing the alcohol production catalyst according to any one of the preceding claims.