JPH0952908A - Catalyst for producing olefin oligomer and production of olefin oligomer using the same catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst comprising a solid acid catalyst having a specific pore diameter, free from corrosion resistance to reacting apparatus, excellent in polymerization activity against olefin and selectivity to >=30C olefin oligomer and useful as automobile engine oil, etc. SOLUTION: This catalyst comprises a solid acid catalyst having 7-15nm average pore diameter, preferably a solid acid catalyst selected from a silica catalyst on which heteropolyacid is supported, a halogenated alumina catalyst, a catalyst as oxide of the group IV metal of the periodic table on which sulfuric acid is supported, a (halogenated) (non) crystalline silica alumina and a (halogenated) alumina boria, especially preferably a solid acid catalyst selected from a silica catalyst on which tungstophosphoric acid is supported, a fluorinated alumina catalyst and zirconium catalyst on which sulfuric acid is supported. The catalyst is preferably obtained by treating alumina, etc., with ammonia fluoride and then, filtering, drying and baking the treated alumina.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an automobile engine oil,
The present invention relates to a catalyst for producing an olefin oligomer which is preferably used for producing an olefin oligomer which is preferably used as a lubricating oil such as an automatic transmission oil, a gas turbine oil, an aircraft hydraulic oil and an electric insulating oil, and a method for producing an olefin oligomer using the same.

[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 operating oils, and electric insulating oils. Among lubricating oils, in the field of application such as automobile engine oil, it is necessary to remove a fraction having less than 30 carbon atoms in order to suppress evaporation loss, and in order to efficiently produce an olefin oligomer, It is important to improve the selectivity of 30 or more olefin oligomers.

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 polyolefin 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 removed. A disassembly and disposal process is required. Moreover, the disposal of the catalyst causes a problem of environmental pollution. Furthermore, because 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 problems, various production methods using a solid acid as a catalyst have hitherto been studied, but all of them have low activity and low selectivity. If it is strict, the isomerization reaction that competes with the polymerization reaction will proceed, and there is a problem that the properties of the product will deteriorate, and the production method using a solid acid catalyst has not been put to practical use.

[0006]

DISCLOSURE OF THE INVENTION The present invention is not corrosive to a reactor, has an olefin polymerization activity and has 3 carbon atoms.
A catalyst for producing an olefin oligomer having excellent selectivity to 0 or more olefin oligomers, and an olefin oligomer capable of efficiently producing an olefin oligomer having good properties such as a high viscosity index and a low pour point using the catalyst. It aims at providing the manufacturing method of.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that a solid acid catalyst having a pore size of a specific size has no corrosiveness with respect to a reactor, It was found that the polymerization activity of olefins and the selectivity to olefin oligomers having 30 or more carbon atoms are excellent, and that the obtained olefin oligomer also has good properties, and based on this finding, the present invention was completed. I arrived.

That is, the present invention provides a catalyst for producing an olefin oligomer, which comprises a solid acid catalyst having an average pore diameter of 7 to 15 nm.

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

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION It is important that the solid acid catalyst for producing an olefin oligomer of the present invention has an average pore diameter of 7 to 15 nm, preferably 8 to 12 nm. If the average pore diameter is less than 7 nm or more than 15 nm, the conversion rate of the raw material olefin and the selectivity to the oligomer having 30 or more carbon atoms are lowered.

The solid acid catalyst for producing an olefin oligomer of the present invention includes a heteropolyacid-supported silica catalyst such as a phosphotungstic acid-supported silica catalyst, a halogenated alumina catalyst such as a fluorinated alumina catalyst, and a sulfuric acid-supported cycle such as a sulfuric acid-supported zirconia catalyst. Table 4 Group 4 metal oxide catalysts, crystalline or amorphous silica alumina or alumina boria catalysts, and crystalline or amorphous silica alumina or catalysts obtained by halogenating alumina boria are preferably used.

In order to obtain a solid acid catalyst having a specific average pore diameter of the present invention, for example, alumina, zirconia, silica or the like or a precursor thereof is treated with an aqueous solution of ammonium fluoride or diluted sulfuric acid, and then filtered, Prepare by drying and baking. If necessary, after washing with water, drying and baking may be performed.

The pore diameter of the prepared solid acid catalyst for producing an olefin oligomer was measured by an adsorption method (specifically, a multipoint method in which nitrogen is adsorbed by the BJH method, allowed to stand and measured at liquid nitrogen temperature).

By polymerizing an olefin using the above-mentioned solid acid catalyst for producing an olefin oligomer, an olefin oligomer having 30 or more carbon atoms, preferably 80 to 100 carbon atoms can be produced in good yield and selectivity.

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 used as a raw material for polymerization is not particularly limited, and α-olefins, internal olefins, mixtures thereof and the like are used, but olefins having 4 to 20 carbon atoms, preferably olefins having 6 to 14 carbon atoms are 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 a solid acid catalyst per 100 g of olefin, preferably 0 to 200 ° C., more preferably 20 to 180.
The reaction is carried out at a temperature of ° C for preferably 0.5 to 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.

[0019]

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 20 ml of a 33 wt% ammonium fluoride aqueous solution was added dropwise. After the completion of dropping, the mixture was stirred for 30 minutes and filtered. Take the obtained solid in a beaker and add 100 ml.
Water was added and the mixture was stirred for 30 minutes and then filtered again. After predrying this solid under vacuum at room temperature for 12 hours,
The catalyst was obtained by calcining at 500 ° C. for 3 hours. Here, the average pore diameter of the prepared catalyst was measured. The results are shown in Table 1.

After replacing the polymerization flask equipped with a stirrer, a thermometer, a gas introduction pipe and a gas exhaust pipe with dry nitrogen gas,
40 ml of 1-decene was added, and further 2 g of catalyst 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,
The catalyst was filtered off, washed with water and dried, and the 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, the selectivity to the olefin oligomer having 30 or more carbon atoms in the produced oligomer, and the properties.

Comparative Examples 1 and 2 In Comparative Example 1, commercially available alumina (NK324 manufactured by Sumitomo Chemical Co., Ltd.) was used, and in Comparative Example 2, commercially available alumina (NK124 manufactured by Sumitomo Chemical Co., Ltd.) was used. The same operation as in 1 was performed. Table 1 shows the average pore diameter of the catalyst, the olefin conversion rate, and the selectivity of the produced oligomer for the olefin oligomer having 30 or more carbon atoms.

Example 2 3.58 g of phosphotungstic acid 30 hydrate was added to distilled water 15
After dissolving in 0 ml, the silica was classified to 83 mesh or less with stirring (CarrierACT manufactured by Fuji Silysia Chemical Ltd.).
10) was added. After stirring at room temperature for 1 day, water was distilled off at 60 ° C. The generated catalyst is 250 ° C in a muffle furnace,
After firing in air for 2 hours, it was cooled to room temperature in a vacuum desiccator. Here, the average pore diameter of the prepared catalyst was measured. The results are shown in Table 1.

After replacing a polymerization flask equipped with a stirrer, a thermometer, a cooling pipe connected to a gas introduction pipe and an exhaust pipe with dry nitrogen gas, a catalyst addition device filled with a catalyst under a dry nitrogen stream was connected. . 100 ml of 1-decene in this flask
Then, 5 g of a catalyst was added while stirring. After the addition, the mixture was heated in an oil bath and polymerized for 2 hours while maintaining the temperature at 120 ° C. After completion of the polymerization, the catalyst was filtered off, washed with water and dried to distill off unreacted olefin and low molecular weight oligomer having 20 or less carbon atoms to obtain an olefin oligomer. Table 1 shows the olefin conversion rate, the selectivity to the olefin oligomer having 30 or more carbon atoms in the produced oligomer, and the properties.

Comparative Examples 3 and 4 In Comparative Example 3, silica (Carriact Q-6 manufactured by Fuji Silysia Chemical Ltd.) was used, and in Comparative Example 4, silica (Carriact-30 manufactured by Fuji Silysia Chemical Ltd.) was used. The same operation as in Example 2 was carried out except that Table 1 shows the average pore diameter of the catalyst, the olefin conversion rate, and the selectivity of the produced oligomer for the olefin oligomer having 30 or more carbon atoms.

Example 3 20 g of commercially available zirconium oxychloride (octahydrate) was dissolved in 15 g of water, and 5% ammonia water was gradually added to adjust the pH to 10. A solution prepared by dissolving 20 g of the above-mentioned zirconium oxychloride (octahydrate) in 15 g of water was added thereto, and 5% aqueous ammonia was gradually added. This operation was repeated three more times. The resulting precipitate was allowed to stand overnight. This precipitate was filtered, then washed with pure water and dried to obtain a dried product. Put this dried product in 10 volumes of 1N sulfuric acid and
After stirring for 0 minutes, it was filtered and dried. Next, this dried material was calcined at 600 ° C. for 3 hours to obtain sulfuric acid-supported zirconia. Here, the average pore diameter of the prepared catalyst was measured. The results are shown in Table 1.

The sulfuric acid-supported zirconia was further calcined at 500 ° C. under vacuum for 3 hours. Here, the average pore diameter of the prepared catalyst was measured. The results are shown in Table 1.

After replacing the polymerization flask equipped with a stirrer, a thermometer, a gas introduction pipe and a gas exhaust pipe with dry nitrogen gas,
40 ml of 1-decene was added, and further 2 g of catalyst 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,
The catalyst was filtered off, washed with water and dried, and the unreacted olefin and the low molecular weight oligomer having 20 or less carbon atoms were distilled off to obtain an olefin oligomer. Table 1 shows the olefin conversion rate and the selectivity to the olefin oligomer having 30 or more carbon atoms in the produced oligomer.

Comparative Example 5 100 g of a commercially available zirconium oxychloride (octahydrate) was dissolved in 80 g of water, and 5% ammonia water was gradually added thereto to cause precipitation with stirring. This was left to stand overnight. This precipitate was filtered, then washed with pure water and dried to obtain a dried product. The dried product was placed in 10 times the amount of 1N sulfuric acid, stirred for 10 minutes, filtered, and dried. Then
The dried product was calcined at 600 ° C. for 3 hours to obtain sulfuric acid-supported zirconia.

The sulfuric acid-supported zirconia was further calcined at 500 ° C. under vacuum for 3 hours. Here, the average pore diameter of the prepared catalyst was measured. The results are shown in Table 1.

Using this catalyst, the same operation as in Example 3 was performed. Table 1 shows the olefin conversion rate and the selectivity to the olefin oligomer having 30 or more carbon atoms in the produced oligomer.

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 crushed and fired at 550 ° C. for 4 hours. Table 1 shows the average pore diameter of the catalyst at this time.

After replacing the polymerization flask equipped with a stirrer, a thermometer, a gas introduction pipe and a gas exhaust pipe with dry nitrogen gas,
40 ml of 1-decene was added, and further 2 g of catalyst 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,
The catalyst was filtered off, washed with water and dried, and the unreacted olefin and the low molecular weight oligomer having 20 or less carbon atoms were distilled off to obtain an olefin oligomer. Table 1 shows the olefin conversion rate and the selectivity to the olefin oligomer having 30 or more carbon atoms in the produced oligomer.

Comparative Example 6 NKH3-2 manufactured by Sumitomo Chemical Co., Ltd. as silica / alumina
The same operation as in Example 4 was performed except that 4 was used. Table 1 shows the average pore diameter of the catalyst, the olefin conversion rate, and the selectivity of the produced oligomer for the olefin oligomer having 30 or more carbon atoms.

Comparative Example 7 To 1 liter of water was added 62.5 ml of an 8% silica aqueous solution diluted and prepared from water glass JIS No. 3. Next, 62.5 ml of an 8% alumina aqueous solution prepared by diluting aluminum sulfate (14-18 hydrate) was added. Furthermore, the above 8%
62.5 ml of an aqueous silica solution was added, and the addition of the 8% aqueous alumina solution was repeated three times. Finally, 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. Table 1 shows the average pore diameter of the catalyst at this time.

Using this catalyst, the same operation as in Example 4 was performed. Table 1 shows the olefin conversion rate and the selectivity to the olefin oligomer having 30 or more carbon atoms in the produced oligomer.

[0037]

[Table 1]

[0038]

EFFECT OF THE INVENTION The catalyst for producing an olefin oligomer of the present invention is not corrosive to a reactor, and is excellent in olefin polymerization activity and selectivity to an olefin oligomer having 30 or more carbon atoms.

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 (6)

[Claims] 1. A catalyst for producing an olefin oligomer, which comprises a solid acid catalyst having an average pore diameter of 7 to 15 nm. 2. The solid acid catalyst is a heteropolyacid-supported silica catalyst, a halogenated alumina catalyst, a sulfuric acid-supported periodic table group 4 metal oxide catalyst, a crystalline or amorphous silica alumina or an alumina boria catalyst, and a crystalline or non-crystalline catalyst. The catalyst for producing an olefin oligomer according to claim 1, which is a solid acid catalyst selected from the catalysts obtained by halogenating crystalline silica alumina or alumina boria. 3. The catalyst for producing an olefin oligomer according to claim 1, wherein the solid acid catalyst is a solid acid catalyst selected from a phosphotungstic acid-supported silica catalyst, a fluorinated alumina catalyst and a sulfuric acid-supported zirconia catalyst. 4. A method for producing an olefin oligomer, which comprises polymerizing an olefin using the solid acid catalyst according to claim 1. 5. The method for producing an olefin oligomer according to claim 4, wherein the olefin is an α-olefin having 6 to 14 carbon atoms or a mixture thereof. 6. An α-olefin having 6 to 14 carbon atoms is 1-
The method for producing an olefin oligomer according to claim 5, which is decene.