JPH11246454A - Production of unsaturated alcohol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an unsaturated alcohol eluting a small amount of a catalyst component in high yield and high selectivity. SOLUTION: An alkyl or an alkenyl ester of an unsaturated fatty acid or a triglyceride having a long-chain aliphatic unsaturated hydrocarbon group is hydrogenated in the presence of a catalyst composition which is a compound metal oxide composed of (a) zinc oxide, (b) an oxide of at least one metal selected from the group consisting of a group 3A element of the periodic table and (c) orthophosphate ion (PO4 <3-> ) in (1/0.01) to (1/1.2) weight ratio of the components (a)/(b) and (1/0.003) to (1/2.4) weight ratio of the components (a)/(c) [the components (a) and (b) are based on the weight of oxides and the component (c) is based on the weight of PO4 <3-> ] to afford an unsaturated alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an unsaturated alcohol, and more particularly, to a method for producing an unsaturated alcohol with high yield and selectivity by hydrogenating an ester of an unsaturated fatty acid or triglyceride in the presence of a catalyst. How to do it.

[0002]

2. Description of the Related Art In a method for producing an unsaturated alcohol, a production method using an iron-zinc composite oxide catalyst has been proposed. For example, a composite catalyst of iron oxide / zinc oxide = 95/5 is proposed in Industrial Chemistry Magazine, Vol. 44, No. 6, page 740 (1941). Although this catalyst does not have the problem of using harmful substances found in conventionally known catalysts using chromium oxide, cadmium oxide, etc., it is not satisfactory in terms of selectivity with respect to activity and double bond retention performance.

To cope with this problem, Japanese Patent Publication No. 59-106431 discloses an improved selectivity with respect to activity and double bond retention performance by using a three-way catalyst comprising iron oxide, zinc oxide and zirconium oxide. A method for producing an unsaturated alcohol is disclosed. When a three-way catalyst composed of iron oxide-zinc oxide and zirconium oxide is repeatedly used in the reaction, the morphological change of the catalyst composition such as reduction of iron oxide is observed, and the accompanying increase in the amount of by-products of saturated alcohol is caused. From the confirmation, a new problem was found that the selectivity with respect to the retention performance of the double bond was not maintained in a good state for a long time.

[0004] Accordingly, an object of the present invention is to provide a method for producing an unsaturated alcohol having a high yield and a high selectivity and a small elution amount of a catalyst component.

[0005]

Means for Solving the Problems The present inventors have found that the above problems can be solved by using a catalyst having a very selected composition, and have completed the present invention.
That is, the present invention comprises (a) zinc oxide, (b) an oxide of at least one metal selected from the group consisting of elements of Group 3A of the Periodic Table, and (c) orthophosphate ion (PO ₄ ^3- ). A composite metal oxide having a weight ratio of (a) / (b) = 1 /
0.01 / 1.2, with (a) / (c) = 1 / 0.003~1 / 2.4 ((a) and (b) an oxide weight basis, (c) the PO ₄ ^3- by weight, hereinafter the same) Provided is a method for producing an unsaturated alcohol, which comprises hydrogenating an alkyl or alkenyl ester of an unsaturated fatty acid or a triglyceride having a long-chain aliphatic unsaturated hydrocarbon group in the presence of a certain catalyst composition. is there.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The Group 3A elements of the periodic table of (b) used in the present invention are Sc, Y, lanthanoid elements (La, C
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
b, Lu), actinoid elements (Ac, Th, Pa, U, Np, P
u, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr). Among them, Y, La,
Ce and Th are preferred. In the present invention, the periodic table refers to the periodic table described in Revised 4th Edition "Chemical Handbook" Basic Edition II (edited by The Chemical Society of Japan, Maruzen Co., Ltd., published on September 30, 1993).

[0007] The catalyst composition according to the present invention may use any catalyst carrier as long as the effects of the present invention are not impaired.
The method for producing the catalyst composition according to the present invention is not particularly limited, and is prepared by a known method. For example, when a carrier is not used, a water-soluble zinc salt, a powder obtained by drying a precipitate obtained by a coprecipitation method from at least one water-soluble salt selected from the group 3A elements of the periodic table, may be dissolved in a powder. Orthophosphate impregnation method, water-soluble zinc salt, 3A of the periodic table
From at least one water-soluble salt selected from the genus elements,
A coprecipitation method using an aqueous solution of orthophosphate and an aqueous alkaline solution as a precipitant, or a method of converting at least one water-soluble salt selected from Group 3A elements of the periodic table and water-soluble orthophosphate into zinc oxide, zinc hydroxide, zinc carbonate, etc. Impregnation method of impregnating the poorly water-soluble zinc compound of the above, or a precipitation method of precipitating the poorly water-soluble zinc compound with at least one water-soluble salt selected from Group 3A elements of the periodic table and a water-soluble orthophosphate. By preparing a catalyst composition precursor first,
It is manufactured by firing. When a carrier is used, a catalyst carrier of an oxide and / or a hydroxide is used to precipitate a zinc salt, at least one water-soluble salt and a water-soluble orthophosphate selected from Group 3A elements of the periodic table. The catalyst composition is prepared by first preparing a catalyst composition precursor by a method of supporting by a method or impregnating and supporting, and then calcining. In addition, at least one compound selected from Group 3A elements of the periodic table can be used as a diluting carrier by a kneading method in which a zinc compound and an orthophosphate are physically mixed together.

The metal salt used in preparing the catalyst composition precursor by the coprecipitation method, impregnation method or precipitation method may be any water-soluble metal salt. Examples of zinc salts include sulfates, nitrates and chlorides.
Examples of the salt of the Group A element include a sulfate, a nitrate, and a chloride, and examples of the orthophosphate include an ammonium salt, a sodium salt, and a potassium salt. As a precipitant for obtaining a catalyst composition precursor by a coprecipitation method or a precipitation method, ammonia, urea, ammonium carbonate,
An alkaline aqueous solution such as sodium carbonate, potassium hydroxide, and sodium hydroxide is used. When using the coprecipitation method or the precipitation method, the pH of the solution during the formation of the precipitate is 2.0 to 10.5
It is preferable to adjust with.

The catalyst composition precursor thus obtained is calcined to form an oxide and then used as a catalyst composition for producing an unsaturated alcohol. The firing temperature of the catalyst composition precursor is not particularly limited, but is preferably 200
To 900 ° C, more preferably 300 to 700 ° C.

The composition of (a) zinc oxide, (b) an oxide of at least one metal selected from Group 3A elements of the periodic table, and (c) orthophosphate ion, which are active components of the catalyst composition according to the present invention. The range is (a) / (b) = 1 / 0.01 to 1 / 1.2, (a)
/(C)=1/0.003 to 1 / 2.4. In a composition other than this composition range, the activity / selectivity is significantly reduced. A more preferred composition range is (a) / (b) = 1 / 0.03 to 1
/1.0, (a) / (c) = 1 / 0.01 to 1 / 1.0, and particularly preferred composition ranges are (a) / (b) = 1 / 0.07 to 1 / 0.42, (a) /
(c) = 1 / 0.03 to 1 / 0.2. The composition range of (b) and (c) is (b) / (c) = 1 / 0.0025 to 1/240, preferably (b)
/(C)=1/0.01 to 1/34, particularly preferably (b) / (c) =
It is 1 / 0.071 to 1 / 2.9. The catalyst composition having these compositions has a high activity, hardly produces any by-products of hydrocarbons and ethers accompanying the hydrogenation reaction, and has a high level of activity. The double bond is converted to the alcohol with little isomerization from the cis to the trans form. In addition, an effect of significantly reducing the elution amount of the catalyst component was also found.

The catalyst composition according to the present invention can be used without any problem even if a carrier is used. As the carrier, aluminum,
Oxides of titanium and zirconium may, for example, be mentioned. In addition,
Regardless of whether a carrier is used or not, a fourth component such as a molding aid may be added to the catalyst composition as long as the effects of the present invention are not impaired.

The method for producing an unsaturated alcohol of the present invention can be carried out in any of a suspension bed reaction system, a fluidized bed reaction system, and a fixed bed reaction system. Molded into a suitable shape.

Specific reaction conditions for producing an unsaturated alcohol are as follows. In the suspension bed reaction system, the amount of catalyst used is an ester of unsaturated fatty acid used as a raw material,
Alternatively, the content is preferably 5 to 30% by weight based on triglyceride. For the purpose of shortening the cycle time of the reaction, 25 to 30% by weight is more preferable. Reaction temperature is 150 ~
A range of 350 ° C is preferred. If the reaction temperature is higher than this range, the side reaction products of hydrocarbons or ethers increase, and if the reaction temperature is lower, sufficient activity cannot be obtained. However, double bond isomerization at the same conversion is hardly affected by temperature. Hydrogen pressure is preferably 1 to 35 MPa
And more preferably 20 to 30 MPa.

Regarding the catalyst, a catalyst calcined in an oxidizing atmosphere or an inert atmosphere can be charged in the form of an oxide regardless of the reaction system, and can be directly used for the reaction. Alternatively, there is no problem even if a catalyst which has been subjected to an appropriate pre-reduction treatment, for example, a catalyst which has been subjected to a pre-reduction treatment under the above-mentioned reaction conditions in a reaction raw material or a produced alcohol is used for the reaction.

When the unsaturated alcohol is produced by a fixed bed reaction system, the catalyst is formed by a known molding method, for example, extrusion molding or tablet molding. At the time of molding, a pore-imparting agent or a lubricant may be added as long as the effects of the present invention are not impaired. In the case where the catalyst composition precursor is fired to form an oxide, the catalyst may be fired in a powder state and then formed, or may be fired after forming an unfired product. The shaped catalyst can be charged into a reactor and used for the reaction as it is. Alternatively, the reduction treatment may be performed in advance in the reactor or outside the reaction system before the reaction. The conditions for reducing the shaped catalyst are as follows. When performing the reduction treatment in the gas phase, under a hydrogen atmosphere diluted with an inert gas,
Or, in a 100% hydrogen atmosphere, the temperature is 200 to 600
℃, pressure is normal pressure ~ 35MPa, gas space velocity is 0.1 ~ 1000
The condition of 0 [l / Hr] is preferable. Further, the reduction treatment includes:
The reaction can also be performed in the liquid phase in the presence of the reaction raw material and / or the produced alcohol. Reaction temperature and reaction pressure are 1
Conditions selected from the range of 50 to 350 ° C. and 1 to 35 MPa are preferable, but from the viewpoint of suppressing the by-product of by-products of hydrocarbons or ethers and obtaining high productivity, 240 to 320 ° C.
Reaction conditions of 20-35 MPa are more preferred. The supply of the reactants is preferably in the range of 0.1 to 2.0 [l / Hr] at the liquid hourly space velocity.

In the present invention, the flow rate of the hydrogen gas supplied into the continuous reactor affects the reaction rate of the obtained alcohol, and the number of moles of the carbonyl group contained in the ester of unsaturated fatty acid or triglyceride, which is the starting material for the reaction. On the other hand, the molar ratio of the supplied hydrogen gas is preferably in the range of 1: 1 to 1: 200 from the viewpoint of the reaction rate and the economic efficiency, and is preferably 1: 1 to 2
A range of 1: 100 is more preferred.

In the present invention, the reaction raw material is an alkyl or alkenyl ester of an unsaturated fatty acid or a triglyceride having a long-chain aliphatic unsaturated hydrocarbon group.
As the alkyl or alkenyl ester of unsaturated fatty acid, any alkyl or alkenyl ester of unsaturated fatty acid having one or more double bonds in the molecule may be used, and as the alkyl or alkenyl group constituting this ester, Straight or branched ones having 1 to 22 carbon atoms are preferred. Specific examples include groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, decyl, and oleyl. The mixture of the alkyl or alkenyl esters of unsaturated fatty acids can be used without any problem, and such a mixture may contain a saturated fatty acid ester. Further, as the triglyceride having a long-chain aliphatic unsaturated hydrocarbon group, natural fats and oils having a long-chain aliphatic unsaturated hydrocarbon group, for example, tallow, coconut oil, palm oil,
Triglycerides such as palm kernel oil, soybean oil, rapeseed oil and the like can be used.

[0018]

EXAMPLES In the examples, parts and percentages are by weight unless otherwise specified.

Example 1 Preparation of Catalyst 1095.5 g of zinc nitrate hexahydrate [Zn (NO ₃ ) ₂ .6H ₂ O] and 134.00 g of yttrium nitrate hexahydrate [Y (NO ₃ ) ₃ .6H ₂ O] were ionized. It was dissolved in 5000 g of exchanged water and heated to 90 ° C. with stirring.
To this aqueous solution, 4534.0 g of a 10% aqueous sodium carbonate solution was added dropwise over about 1 hour, and the resulting suspension was heated and aged for 1 hour while maintaining the temperature at 90 ° C. Thereafter, the obtained precipitate was separated by filtration, washed with 20 liters of ion-exchanged water, and dried at 110 ° C. all day and night. 50 g of the obtained hydrous zinc oxide / yttrium oxide powder was replaced with 200 g of ion-exchanged water.
And 0.55% ammonium phosphate [(NH ₄ ) ₃ PO ₄ ]
100 g of an aqueous solution was added, and the mixture was aged at room temperature for 2.5 hours. The aged slurry was evaporated to dryness and further dried at 110 ° C. overnight. Sodium carboxymethylcellulose and alumina were added as binder components to the obtained powder, and a tablet having a size of 3 mmφ × 3 mmH was formed by tableting. By firing this molded product at 420 ° C for 2 hours in air,
A shaped catalyst was obtained. The composition of the obtained catalyst was calculated from the content of each element determined by inductively coupled high-frequency plasma spectroscopy (ICP spectroscopy). Part (ZnO / Y ₂ O ₃ / PO ₄ ^3- / Al ₂ O ₃ = 1 / 0.136
/0.035/0.11).

Production of Unsaturated Alcohol 15 g of the above shaped catalyst was charged into a rotary stirring autoclave equipped with a basket for supporting the catalyst, and methyl oleate (Exepearl MO, manufactured by Kao Corporation) was used as a reaction raw material.
L: saponification value: SV = 193, iodine value: IV = 84, hydroxyl value: OHV = 1.5, purity of methyl cis-9-octadecenoate = 67.52% by weight, purity of methyl trans-9-octadecenoate = 8.46% by weight, using cis-9, cis-12-octadecadienoate (purity = 6.24% by weight) and the reaction temperature
The reaction was carried out at 300 ° C. and a hydrogen pressure of 25 MPa for 9 hours. After completion of the reaction, only the oil was extracted and washed / dried to obtain an unsaturated alcohol. The molded catalyst was directly used for the next reaction. This reaction operation was performed three times, and the analytical values of the obtained unsaturated alcohols are shown in Table 1.

The catalytic activity and selectivity were evaluated using the total content of cis-9-octadecenol and trans-9-octadecenol determined by gas chromatography. cis-9-octadecenol and trans-9
The higher the value of the total content of octadecenol, the higher the conversion to unsaturated alcohol. Further, the catalyst activity / selectivity was repeatedly evaluated, and the crushing strength of the catalyst after the recovery reaction was evaluated. For the measurement of the crushing strength, a Kiya type hardness meter was used, and an average value of 20 measured values was adopted. The catalyst Y ₂
The elution amount of the O ₃ component was evaluated by measuring the composition of zinc oxide, yttrium oxide and aluminum oxide of the catalyst before and after the recovery reaction, and calculating the change in the yttrium oxide (Y ₂ O ₃ ) composition of the catalyst by the following formula. The lower the change in Y ₂ O ₃ composition of the catalyst, the better
It shows that the selective elution of Y ₂ O ₃ is low. Here analysis of unsaturated alcohols obtained / catalyst crush strength / catalyst Y ₂ O ₃ compositional change are shown in Table 1.

<Calculation formula for change in Y ₂ O ₃ composition>

[0023]

(Equation 1)

Example 2 The concentration of an aqueous solution of ammonium phosphate [(NH ₄ ) ₃ PO ₄ ] was 1.15.
%, A catalyst was prepared by the method described in Example 1, and an unsaturated alcohol was obtained under the same reaction conditions as in Example 1. The composition of the catalyst prepared here was calculated from the content of each element determined by ICP spectroscopy. As a result, 75.5 parts of zinc oxide, 10.2 parts of yttrium oxide, 5.7 parts of orthophosphate ion, and 8.6 parts of aluminum oxide (ZnO / Y ₂ O ₃ / PO ₄ ^3-
/ Al ₂ O ₃ = 1 / 0.135 / 0.075 / 0.11). The total content of cis-9-octadecenol and trans-9-octadecenol obtained by this reaction was measured, and the catalytic activity / selectivity was evaluated in the same manner as in Example 1. Furthermore, the crushing strength of the catalyst after the recovery reaction was evaluated, the composition before and after the recovery reaction was measured, and the change in the Y ₂ O ₃ composition of the catalyst was evaluated. Table 1 shows the results.

EXAMPLE 3 The concentration of an aqueous solution of ammonium phosphate [(NH ₄ ) ₃ PO ₄ ] was adjusted to 2.87.
%, A catalyst was prepared by the method described in Example 1, and an unsaturated alcohol was obtained under the same reaction conditions as in Example 1. The composition of the catalyst prepared here was calculated from the content of each element determined by ICP spectroscopy. As a result, 73.3 parts of zinc oxide, 9.4 parts of yttrium oxide, 8.9 parts of orthophosphate ion, and 8.4 parts of aluminum oxide (ZnO / Y ₂ O ₃ / PO ₄
^3- / Al ₂ O ₃ = 1 / 0.128 / 0.12 / 0.11). The total content of cis-9-octadecenol and trans-9-octadecenol obtained by this reaction was measured, and the catalytic activity / selectivity was evaluated in the same manner as in Example 1. Furthermore, the crushing strength of the catalyst after the recovery reaction was evaluated, the composition before and after the recovery reaction was measured, and the change in the Y ₂ O ₃ composition of the catalyst was evaluated. Table 1 shows the results.

Comparative Example 1 The hydrous zinc oxide / yttrium oxide powder 50 described in Example 1
To g, a binder component was added in the same manner as in Example 1, molding and firing were performed to prepare a catalyst, and an unsaturated alcohol was obtained under the same reaction conditions as in Example 1. The composition of the catalyst prepared here was calculated from the content of each element determined by ICP spectroscopy. As a result, 80.4 parts of zinc oxide, 10.4 parts of yttrium oxide, and 9.2 parts of aluminum oxide (ZnO / Y ₂ O ₃ / Al ₂
O ₃ = 1 / 0.129 / 0.11). The cis obtained by this reaction
The total content of -9-octadecenol and trans-9-octadecenol was measured, and the catalytic activity / selectivity was evaluated in the same manner as in Example 1. Furthermore, the crushing strength of the catalyst after the recovery reaction was evaluated, the composition before and after the recovery reaction was measured, and the change in the Y ₂ O ₃ composition of the catalyst was evaluated. Table 1 shows the results.

[0027]

[Table 1]

* 1 cis-9-octadecenol and trans
The higher the value of the total content of -9-octadecenol, the higher the conversion to unsaturated alcohol. * 2 The lower the change in the Y ₂ O ₃ composition of the catalyst, the less elution of Y ₂ O ₃ .

As is evident from Table 1, in the examples of the present invention, the catalytic activity and selectivity are good, and the elution of yttrium oxide after repeated use is smaller than that of the comparative example.

[0030]

According to the present invention, no harmful components are contained,
In addition, an unsaturated alcohol can be produced with high yield and high selectivity by using a catalyst having a small amount of components eluted.

Claims (4)

[Claims] 1. An oxide of (a) zinc oxide, (b) an oxide of at least one metal selected from the group consisting of elements belonging to Group 3A of the periodic table, and (c) orthophosphate ion (PO ₄ ³⁻ ). A composite metal oxide having a weight ratio of (a) / (b) = 1 /
0.01 / 1.2, the catalyst composition is (a) / (c) = 1 / 0.003~1 / 2.4 ((a) and (b) an oxide weight basis, (c) the PO ₄ ^3- by weight) A process for hydrogenating an alkyl or alkenyl ester of an unsaturated fatty acid or a triglyceride having a long-chain aliphatic unsaturated hydrocarbon group in the presence of a product. 2. The method according to claim 1, wherein the hydrogen pressure is 1 to 35 MPa. 3. The method according to claim 1, wherein the Group 3A element of the periodic table is Y, La, Ce or Th. 4. Use of a shaped catalyst composition.
4. The method according to any one of items 1 to 3.