JPH09104705A - Method for producing catalyst for producing olefin oligomer and method for producing olefin oligomer using the catalyst - Google Patents

Abstract

(57) Abstract: An olefin oligomer having good properties such as a high viscosity index and a low pour point is efficiently produced by using a catalyst for producing an olefin oligomer which is not corrosive to a reactor and has excellent olefin polymerization activity. Manufacture well. SOLUTION: The aluminum-containing metal oxide is subjected to a halogenation treatment, washed with water until the halogen compound does not elute, and then the olefin is polymerized by using the calcined catalyst for producing an olefin oligomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a catalyst for producing an olefin oligomer and a method for producing an olefin oligomer using the catalyst.

[0002]

2. Description of the Related Art Olefins, especially α-olefins having 6 to 14 carbon atoms.
Olefin oligomers obtained by polymerizing olefins are useful as base materials for lubricating oils such as automobile engine oils, automatic transmission oils, gas turbine oils, aircraft hydraulic oils, electric insulating oils, etc. Therefore, it is necessary to efficiently produce an olefin oligomer.

As a method for producing an olefin oligomer used for such a lubricating oil base material, a method for producing a Lewis acid such as aluminum chloride or boron trifluoride as a catalyst has been known so far, and is industrially used. Boron trifluoride having a more preferable product property and having high selectivity for an olefin oligomer having 30 or more carbon atoms is used.

However, boron trifluoride is harmful to the human body, and the polymerization reaction of olefins using boron trifluoride as a catalyst is such that after the reaction is completed, the catalyst is separated, the product is washed, and the separated catalyst is separated. A disassembly and disposal process is required. Further, disposal of the catalyst causes a problem of environmental pollution. Further, since these catalysts are highly corrosive, the production of olefin oligomers requires the use of equipment made of high-grade corrosion-resistant materials.

In order to solve such a problem, various production methods using a solid acid as a catalyst have hitherto been studied. However, all of them have low activity. Since the isomerization reaction that competes with the reaction proceeds, there is a problem that the properties of the product deteriorate, and the production method using a solid acid catalyst has not been put to practical use. There is also a method for improving activity (JP-A-60-44041) in which an inorganic oxide is brought into contact with ammonium fluoride or boron trifluoride and then washed with an aqueous ammonium salt solution such as ammonium nitrate, but it is sufficient for oligomer production. Shows no active activity.

[0006]

The present invention provides a method for producing a catalyst for producing an olefin oligomer which is not corrosive to a reactor and has an excellent olefin polymerization activity, and a high viscosity index and a low pour point using this catalyst. It is an object of the present invention to provide a method for producing an olefin oligomer capable of efficiently producing an olefin oligomer having good properties such as

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors have found that a catalyst for producing an olefin oligomer which has been subjected to a specific treatment is excellent in olefin polymerization activity, The obtained olefin oligomer also has good properties and is not corrosive to the reactor,
The inventors have found that the separation of the catalyst is easy, and have completed the present invention based on this finding.

That is, the present invention provides a method for producing a catalyst for producing an olefin oligomer, which comprises halogenating an aluminum-containing metal oxide, washing with water until the halogen compound is no longer eluted, and calcining. It is a thing.

The present invention also provides a method for producing an olefin oligomer, which comprises polymerizing an olefin using the above-mentioned catalyst for producing an olefin oligomer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION It is important that the catalyst for producing an olefin oligomer of the present invention is subjected to halogenation treatment of an aluminum-containing metal oxide, then washed with water until the halogen compound does not elute, and calcined.

As the aluminum-containing metal oxide, a metal oxide such as alumina or a composite oxide such as crystalline or amorphous silica / alumina or alumina / boria, aluminophosphate, silicoaluminophosphate or the like can be used. Alumina or silica-alumina is preferably used.

A halogen-containing inorganic substance or a halogen-containing organic substance can be used as a halogenating agent when halogenating an aluminum-containing metal oxide. Specifically, ammonium fluoride, hydrogen fluoride, boron trifluoride, halogenated hydrocarbon, or the like can be used.

The treatment with the halogenating agent can be accomplished by contacting the aluminum-containing metal oxide with the halogenating agent. This contact treatment can be performed by various methods and conditions. When using ammonium fluoride, a method of treating in a liquid phase at 0 to 100 ° C. is preferable. The amount of the halogenating agent is not particularly limited as it varies depending on various conditions, but is usually 0.05 g per 100 g of the aluminum-containing metal oxide.
It is sufficient if it is at least the above, preferably 0.05 to 5.0 g. If the amount is less than 0.05 g or more than 5.0 g, the conversion rate of the raw material olefin decreases. When a halogenated hydrocarbon is used, it is preferably treated in the gas phase at 300 to 400 ° C. 40 below 300 ° C
Even if the temperature is higher than 0 ° C, the conversion rate of the raw material olefin is lowered.

In the present invention, the halogenated aluminum-containing metal oxide obtained as described above is washed with water until the halogen compound does not elute. This washing treatment requires washing with water until the halogen compound is no longer eluted. The degree of the elution of the halogen compound can be determined by a change in the content of the halogen compound in the metal oxide after the washing or a change in the content of the halogen compound in the washing water after the washing treatment. For example, chlorine and the like existing in the washing water after the washing treatment can be analyzed by a silver compound, and fluorine and the like can be analyzed by a calcium compound. It can also be analyzed by ion chromatography. Furthermore, the metal oxide after washing can be thermally decomposed and dissolved in water can be analyzed. When washing with water, the state may be liquid or gas, but the liquid state is preferable. The conditions for the cleaning treatment in the liquid state are not particularly limited, but normal temperature and normal pressure are preferable.

When the washing treatment is carried out with liquid water, the washing method is not particularly limited, but it is preferable to use a stirring method or a circulation method. When the stirring method is adopted, it is necessary to perform the stirring for at least 10 minutes in a state where the metal oxide halogenated is substantially uniformly dispersed by stirring. If it is less than 10 minutes, the halogen compound cannot be sufficiently removed. The amount of water used is preferably equal to or more than the amount of the aluminum-containing metal oxide after the halogenation treatment. If the amount is less than the equal amount, the halogen compound cannot be removed sufficiently. The washing treatment by stirring should be performed more than 5 times, preferably 6 times or more, and preferably performed until the elution of the halogen compound is stopped. When the flow method is adopted, water is flowed into the filled metal oxide so as not to cause a non-uniform flow in an upflow or a downflow, and the liquid hourly space velocity (LHSV) is
Below, more than 5 times the amount of metal oxide. Preferably, washing is performed with water six times or more, and the washing is preferably performed until the elution of the halogen compound stops.

In the present invention, the desired catalyst for producing an olefin oligomer can be obtained by calcining the aluminum-containing metal oxide obtained by such a washing treatment. The firing conditions at this time are not particularly limited, but may be 450 to 7 under nitrogen or vacuum conditions.
It may be about 50 ° C. When the temperature is lower than 450 ° C or higher than 750 ° C, the conversion rate of the raw material olefin is lowered.

When the olefin is polymerized using the catalyst for producing an olefin oligomer obtained by the present invention, it has 2 carbon atoms.
An olefin oligomer of 0 or more, preferably 30 to 60 can be produced in good yield.

The olefin oligomer obtained by the production method of the present invention has a high viscosity index, a low pour point, and excellent properties. Further, the method for producing an olefin oligomer of the present invention does not require the use of a reactor for high-grade corrosion-resistant materials, and further comprises steps of catalyst separation, product washing, decomposition of the separated catalyst, and disposal treatment. It has excellent advantages such as not being necessary.

The olefin as a raw material for polymerization is not particularly limited, such as α-olefin, internal olefin or a mixture thereof, but olefin having 4 to 20 carbon atoms, preferably olefin having 6 to 14 carbon atoms is preferably used. To be Specific examples include 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene.

The polymerization reaction is carried out in the presence of 0.1 to 50 g of an olefin oligomer production catalyst based on 100 g of olefin, and the olefin is preferably at a temperature of 0 to 200 ° C., more preferably 20 to 180 ° C., preferably 0. .5-
The reaction is carried out for 24 hours, more preferably 1 to 12 hours.

A solvent is not particularly required for the reaction, but if desired, chain saturated hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon and the like may be used as a solvent.

[0022]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Example 1 20 g of commercially available alumina (N613N manufactured by JGC Chemical Co., Ltd.) was weighed into a flask, and 30 g of 33% by weight ammonium fluoride aqueous solution was added dropwise at 25 ° C. After completion of dropping, 30
It was stirred for minutes and filtered. Take the obtained solid in a beaker, 1
After adding 00 ml of water and stirring at 25 ° C. for 30 minutes, the mixture was filtered again. This washing operation was repeated six times. This solid was pre-dried under vacuum at room temperature for 12 hours, then under vacuum, 5
By calcining at 00 ° C. for 3 hours, a catalyst for producing an olefin oligomer was obtained. In addition, after repeating the washing operation 6 times, the catalyst was decomposed by heating and dissolved in water, and then the analysis value by the ion chromatograph method was compared with the analysis value similarly treated after the washing operation was repeated 7 times. As a result, it was confirmed that there was no change in the fluorine compound and no elution of the fluorine compound. After replacing the polymerization flask equipped with a stirrer, a thermometer, a gas introduction pipe and a gas exhaust pipe with dry nitrogen gas, 1-
40 ml of decene was added, and further 2 g of a catalyst for producing an olefin oligomer was added. Polymerization was carried out for 2 hours while maintaining the temperature at 40 ° C. After completion of the polymerization, 25% ammonia water was added to deactivate the catalyst, and then the catalyst was filtered off, washed with water and dried, and unreacted olefin and low molecular weight oligomer of 20 or less were distilled off to obtain an olefin oligomer. Table 1 shows the olefin conversion rate and properties at this time.

Example 2 The same operation as in Example 1 was carried out except that the catalyst preparation conditions and the washing operation with water in Example 1 were changed from 6 times to 12 times. Table 1 shows the olefin conversion rate and the like by the catalyst for olefin oligomer production obtained by this operation.

Comparative Example 1 Example 1 was repeated except that the commercially available alumina (N613N manufactured by JGC Chemical Co., Ltd.) was not treated with a 33% by weight aqueous solution of ammonium fluoride but was calcined as it was.
The same operation as described above was performed. Table 1 shows the conversion rate and the like by the catalyst for olefin oligomer production obtained by this operation.

Comparative Example 2 The same operation as in Example 1 was carried out except that the catalyst preparation conditions and the washing operation with water in Example 1 were changed from 6 times to 3 times. Table 1 shows the olefin conversion rate and the like by the catalyst for olefin oligomer production obtained by this operation. When the amount of the halogen compound in the catalyst was confirmed by the same method as in Example 1, the halogen compound could not be sufficiently washed by washing three times.

Comparative Example 3 The same operation as in Example 1 was carried out except that the catalyst preparation conditions and the washing operation with water were not carried out. Table 1 shows the olefin conversion rate and the like by the catalyst for olefin oligomer production obtained by this operation.

Example 3 The same operation as in Example 1 was carried out except that the amount of halogenating agent and the firing temperature were changed to the values shown in Table 1. Table 1 shows the olefin conversion rate and the like by the catalyst for olefin oligomer production obtained by this operation.

Comparative Examples 4, 5 and 6 The same operation as in Example 1 was carried out except that the amount of the halogenating agent and the firing temperature were changed to the values shown in Table 1. Table 1 shows the olefin conversion rate and the like of the olefin oligomer-producing catalyst obtained by this operation.

Comparative Example 7 The same operation as in Example 1 was carried out except that in Example 1, washing with water was changed to washing with 1N ammonium nitrate. Table 1 shows the olefin conversion rate and the like by the catalyst for olefin oligomer production obtained by this operation.

Example 4 To 1 liter of water, 250 ml of an 8% silica aqueous solution prepared by diluting water glass JIS No. 3 was added. Next, 250 ml of an 8% alumina aqueous solution prepared by diluting aluminum sulfate (14-18 hydrate) was added. Further, pH was adjusted to 8 by adding 6% aqueous ammonia solution. The solid obtained by filtration was added to a 1% ammonium nitrate aqueous solution, and the mixture was stirred and filtered. This operation was repeated 3 times and then washed with water. After preliminary drying, it was ground and calcined at 550 ° C. for 4 hours. The same operation as in Example 1 was performed except that the obtained silica / alumina was used as a raw material. Table 1 shows the olefin conversion rate and the like of the olefin oligomer-producing catalyst obtained by this operation.

Comparative Example 8 The same operation as in Example 4 was carried out except that in Example 4, the washing operation with water was omitted. Table 1 shows the olefin conversion rate and the like by the catalyst for olefin oligomer production obtained by this operation.

Example 5 5 g of a commercially available alumina (N613N manufactured by JGC Chemical Co., Ltd.) was filled in a quartz tube and baked at 130 ° C. for 2 hours, nitrogen gas was stopped, and 1,2-dichlorotetrafluoroethane was added to each. It heated at 300 degreeC for 1 hour, flowing 50 ml of minutes.
After stopping the supply of 1,2-dichlorotetrafluoroethane,
Further, nitrogen gas was passed for 2 hours at the same temperature. After cooling, the obtained solid was placed in a beaker, 50 ml of water was added, and the mixture was stirred at 25 ° C for 30 minutes and then filtered. This washing operation was repeated six times. This solid is placed under vacuum at room temperature 12
After preliminary drying for an hour, it was calcined under vacuum at 500 ° C. for 3 hours to obtain a catalyst for producing an olefin oligomer. An olefin oligomer was obtained by the same operation as in Example 1 using this catalyst. Table 2 shows the olefin conversion rate and the like at this time.

Example 6 Except that in Example 5, the heat treatment temperature with 1,2-dichlorotetrafluoroethane was changed to 400 ° C.
The same operation as in Example 5 was performed. Table 2 shows the olefin conversion rate and the like obtained by the catalyst for olefin oligomer production obtained by this operation.

Comparative Examples 9 and 10 The same operations as in Examples 5 and 6 were performed, respectively, except that the washing operation with water was not performed in Examples 5 and 6. Table 2 shows the olefin conversion rate and the like obtained by the catalyst for olefin oligomer production obtained by this operation.

Example 7 20 g of commercially available alumina (N613N manufactured by JGC Chemical Co., Ltd.) was weighed into a flask, and 30 g of a 33 wt% ammonium fluoride aqueous solution was added dropwise at 25 ° C. After completion of dropping, 30
It was stirred for minutes and filtered. The obtained solid was packed in a glass column having a diameter of 12 mm, and the liquid space velocity (L
With HSV) 6, 200 ml of water was supplied to wash. The washed solid was pre-dried under vacuum at room temperature for 12 hours and then calcined under vacuum at 500 ° C. for 3 hours to obtain a catalyst for producing an olefin oligomer. An olefin oligomer was produced in the same manner as in Example 1 except that this catalyst for producing an olefin oligomer was used. Table 3 shows the olefin conversion rate and properties at this time.

Comparative Example 11 Example 7 was repeated except that the liquid hourly space velocity (LHSV) was changed to 8. Table 3 shows the olefin conversion rate and the like obtained by the catalyst for olefin oligomer production obtained by this operation.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

EFFECT OF THE INVENTION The catalyst for producing an olefin oligomer of the present invention is not corrosive to a reactor and has an excellent olefin polymerization activity.

Further, according to the method for producing an olefin oligomer of the present invention, an olefin oligomer having good properties such as a high viscosity index and a low pour point can be efficiently produced.

Claims (7)

[Claims] 1. A method for producing a catalyst for producing an olefin oligomer, which comprises halogenating an aluminum-containing metal oxide, washing with water until the halogen compound does not elute, and calcining. 2. The aluminum-containing metal oxide is a metal oxide selected from alumina, crystalline or amorphous silica-alumina or alumina boria, aluminophosphate and silicoaluminophosphate.
A method for producing the catalyst for producing an olefin oligomer as described above. 3. The method for producing a catalyst for producing an olefin oligomer according to claim 1, wherein the washing is carried out under stirring, and washing for 10 minutes or more is repeated 5 times or more. 4. The washing method is a flow method, and the liquid space velocity (L
The method for producing a catalyst for producing an olefin oligomer according to claim 1 or 2, wherein the HSV) is 6 or less, and the amount of washing water is 5 times or more that of the metal oxide. 5. The method for producing a catalyst for producing an olefin oligomer according to claim 1, wherein the calcination temperature is 450 to 750 ° C. 6. The method for producing an olefin oligomer by polymerizing an olefin, wherein the catalyst for producing an olefin oligomer produced by the method according to any one of claims 1 to 5 is used. Process for producing olefin oligomer. 7. The method for producing an olefin oligomer according to claim 6, wherein the olefin is an α-olefin having 6 to 14 carbon atoms.