JP2000300992A - Catalyst for alkylating isoalkane and isoalkane alkylization method using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst suitable for a continuous fixed bed, superior in energy efficiency and alkene conversion, and capable of manufacturing a high branching isoalkane in a good yield by bringing a plurality of specified compounds into contact with a silicon oxide or the like, also bringing water and water vapor into contact with them and then burning them at a specified temperature. SOLUTION: First, a compound represented by R1aME(OR2)z-m is brought into contact with a silicon oxide and/or an aluminum oxide. (R1 and R2 each represent a 1-12C hydrocarbon, Me represents Zr or Ti and Z represents the number of values of Me, and (m) represents O<=M<=Z. Then, water or water vapor is brought into contact with the oxide. Then, a compound having a (c) sulfate group and/or a compound having sulfone is brought into contact with the silicon oxide and/or the aluminum oxide and then burnt ion the temperature range of 100-400 deg.C to prepare the catalyst. As for the isoalkane alkylating method, the isoalkane is reacted with alkene under the presence of the catalyst thus manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst useful for the alkylation of an isoalkane with an alkene, and to a method for alkylating an isoalkane using the catalyst.

[0002]

2. Description of the Related Art Since the preservation of the global environment has been called for, the base material of gasoline, which is an automobile fuel, has also been reduced in gasoline base material containing less alkene components and aromatic components, especially the content of highly branched alkanes. Many alkylates have recently attracted attention as environmentally friendly gasoline base materials. The above alkylate can be produced by alkylating an isoalkane with an alkene having about 3 to 6 carbon atoms, and this alkylation reaction isomerization, polymerization reaction, cracking reaction, disproportionation. Usually, side reactions such as reactions often occur simultaneously. For this reason, in the production of alkylate, in order to suppress side reactions,
It is common to use a strongly acidic acid as the alkylation catalyst, and sulfuric acid and hydrofluoric acid are typical examples.
However, sulfuric acid is not only problematic in its corrosiveness,
In order to generate the desired alkylate, there is a disadvantage that a large amount of energy is required for removing the heat of reaction. Also, hydrofluoric acid has the disadvantage that considerable care must be taken in its handling. Against this background, some solid acid catalysts have been proposed as alkylation catalysts to replace sulfuric acid and hydrofluoric acid. Zeolite, zeolite modified with BF ₃ or the like, or a catalyst in which a Lewis acid and / or Bronsted acid are supported on an inorganic carrier (eg, SO ₄ ²⁻ / Zr
Such as O _2, etc.) and chlorinated alumina are examples. However, the solid acid catalyst has the following disadvantages as an isoalkane alkylation catalyst. One is that the molar ratio of isobutane / alkene must be increased to suppress side reactions, and the other is that the unsaturated oligomers are deposited on the catalytic acid sites and the catalytic activity is easily reduced. To deteriorate,
Frequent regeneration of the catalyst must take place.
When zeolite, which is a weakly acidic solid acid, is used, there is a disadvantage that a high reaction temperature must be employed. WO 94/10106 states that at least one C
An organic sulfonic acid having an -F bond or a CP bond,
There has been proposed a method for producing an alkylate by reacting an alkene and an isoalkane in the presence of a catalyst comprising a Lewis acid. However, since this method uses BF _3, which is highly toxic and corrosive, as the Lewis acid component of the catalyst, it is necessary to pay attention to the handling of the catalyst, and there is no disadvantage in that the handling of the catalyst is troublesome. Absent.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks of the conventional alkylation catalysts, to be able to produce by a simple means and to provide a continuous fixed bed. A catalyst that is suitable and easy to handle, has good energy efficiency and good alkene conversion compared to the conventional method, has few heavy by-products, and can produce highly branched isoalkane in good yield. To provide a method for alkylating isoalkanes.

[0004]

The catalyst according to the present invention, that is, the catalyst for the alkylation of an isoalkane with an alkene, comprises (a) a silicon oxide and / or an aluminum oxide, and (b) R ¹ _m Me (OR ² ) _zm (where R ¹ and R ² each represent a hydrocarbon group having 1 to 12 carbon atoms, and Me represents Zr or T
i, z represents the valence of Me, and m represents 0 ≦ m ≦ z), followed by contact with water or steam, and then (c) a compound having a sulfate group and And / or contact with a compound having a sulfone group, followed by 100
It can be obtained by firing in a temperature range of up to 400 ° C. And the isoalkane alkylation method according to the present invention is characterized by reacting an isoalkane with an alkene in the presence of the catalyst obtained as described above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In preparing the catalyst of the present invention, silicon oxide and / or aluminum oxide (hereinafter referred to as “component
(a) "), where the oxide is
It may be a single oxide or a double oxide. Accordingly, the silicon oxide includes, in addition to silica, a double oxide of at least one metal of Group I to VI of the periodic table and silicon, and the aluminum oxide includes alumina and the periodic table I to VI in addition to alumina. Includes double oxides of aluminum with at least one metal of the group III. If the double oxide of silicon or aluminum that can be used in the present invention is exemplified by a composition formula, Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, Al ₂
O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ ·
MgO.SiO ₂ , Al ₂ O ₃ .CuO, SiO ₂ .Mg
Examples include various natural or synthetic double oxides such as O, Al ₂ O ₃ .Fe ₂ O ₃ , and Al ₂ O ₃ .NiO. The structure and component ratio of the double oxide used in the present invention are not particularly limited. Further, in the present invention, single oxides and multiple oxides can be mixed and used, and multiple oxides and single oxides can be mixed and used. In addition, the above-mentioned component (a) is added with 2
It is preferable to pre-fire at 00 to 800 ° C. In this case, the component (a) may contain a small amount of water (typically adherent water), but the allowable amount is usually 1% by mass or less based on the oxide. desirable. The component (a) can be used without any problem even if it contains a small amount of impurities, and examples of the impurities include oxides of alkali metals such as Na and K. In addition, taking the case of an alkali metal as an example, the allowable amount of the impurity is desirably usually 0.5% by mass or less as the alkali metal. The properties of the component (a) used in the present invention are not particularly limited, but it is desirable to satisfy the following properties (I) to (III). (I) The average particle size is usually 30 to 6000 μm, preferably 250 to 5000 μm, more preferably 500 to 40 μm.
It is desirable to be in the range of 00 μm. The average particle size referred to here is determined by a sieving method. If the average particle size of the component (a) is less than 30 μm, the catalyst obtained by using this may scatter from the reactor or block the reactor. If the average particle size exceeds 6000 μm, the balance between particle strength and pore volume or specific surface area may be reduced. (II) The specific surface area measured by the BET method is usually 150 to
600m ² / g, preferably in 200 to 500 m ² / g, more preferably in the range of 250~450m ² / g. If the specific surface area is less than 150m ² / g, (typically described later component (b), component (c)) This active ingredient may not be able to sufficiently carrying, also, 600 meters ² If it is larger than / g, the strength of the catalyst obtained therefrom may be reduced, and the cost of the catalyst also increases. (III) Pore radius 18 to 1000 measured by mercury intrusion method
The pore volume in the range of Angstroms is typically 0.3
３3.0 cm ³ / g, preferably 0.6-2.5 cm ³ / g,
More preferably, it is in the range of 0.9 to 2.0 cm ³ / g. If the pore volume is less than 0.3 cm ³ / g, the active ingredient may not be sufficiently supported. If the pore volume is more than 3.0 cm ³ / g, the loaded active ingredient may be unevenly distributed. .

The component (b) of the present invention has a general formula: R ¹ _m Me
(OR ² ) is represented by _zm . Here, R ¹ and R ² each represent a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms;
Me represents Zr or Ti, z represents the valence of Me, usually z = 4, and m represents an integer in the range of 0 ≦ m ≦ Z, preferably 0 ≦ m <Z. Most preferably, m = 0. R ¹ ,
The hydrocarbon group for R ² includes an alkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the aryl group include a phenyl group, and examples of the aralkyl group include. R ¹ and R ² are particularly preferably alkyl groups. When specific examples of component (b) are noted, tetramethyl zirconium, trimethyl monomethoxy zirconium, dimethyl dimethoxy zirconium, monomethyl trimethoxy zirconium, tetraethyl zirconium, triethyl monomethoxy zirconium, diethyl dimethoxy zirconium, monoethyl trimethoxy zirconium, tetrapropyl zirconium ,
Tripropyl monomethoxy zirconium, dipropyl dimethoxy zirconium, monopropyl trimethoxy zirconium, tetrabutyl zirconium, tributyl monomethoxy zirconium, dibutyl dimethoxy zirconium, monobutyl trimethoxy zirconium, trimethyl monoethoxy zirconium, dimethyl diethoxy zirconium, monomethyl triethoxy zirconium , Triethyl monoethoxy zirconium, diethyl diethoxy zirconium, monoethyl triethoxy zirconium, tripropyl monoethoxy zirconium, dipropyl diethoxy zirconium, monopropyl triethoxy zirconium, tributyl monoethoxy zirconium, dibutyl diethoxy zirconium, monobutyl triethoxy zirconium ,bird Chill mono propoxy zirconium,
Dimethyl dipropoxy zirconium, monomethyl tripropoxy zirconium, triethyl monopropoxy zirconium, diethyl dipropoxy zirconium, monoethyl tripropoxy zirconium, tripropyl monopropoxy zirconium, dipropyl dipropoxy zirconium, monopropyl tripropoxy zirconium, tributyl monobutoxy zirconium, dibutyl Dibutoxy zirconium, monobutyl tributoxy zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium, tetrapentoxy zirconium, tetrahexyloxy zirconium, tetraheptyloxy zirconium, tetraoctyloxy zirconium,
Tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentoxytitanium, tetrahexyloxytitanium, tetraheptyloxytitanium,
Tetraoctyloxytitanium, tetramethyltitanium, trimethylmonomethoxytitanium, dimethyldimethoxytitanium, monomethyltrimethoxytitanium, tetraethyltitanium, triethylmonomethoxytitanium, diethyldimethoxytitanium, monoethyltrimethoxytitanium, tetrapropyltitanium, tripropylmonomethoxytitanium , Dipropyldimethoxytitanium, monopropyltrimethoxytitanium, tetrabutyltitanium, tributylmonomethoxytitanium, dibutyldimethoxytitanium, monobutyltrimethoxytitanium, trimethylmonoethoxytitanium, dimethyldiethoxytitanium, monomethyltriethoxytitanium, triethylmonoethoxytitanium , Dieci Diethoxytitanium, monoethyltriethoxytitanium, tripropylmonoethoxytitanium, dipropyldiethoxytitanium, monopropyltriethoxytitanium, tributylmonoethoxytitanium, dibutyldiethoxytitanium, monobutyltriethoxytitanium, trimethylmonopropoxytitanium, dimethyl Dipoloxytitanium, monomethyltripropoxytitanium, triethylmonopropoxytitanium, diethyldipropoxytitanium,
Examples include monoethyltripropoxytitanium, tripropylmonopropoxytitanium, dipropyldipropoxytitanium, monopropyltripropoxytitanium, tributylmonobutoxytitanium, dibutyldibutoxytitanium, monobutyltributoxytitanium, and the like. Among these, tetrapropoxyzirconium, tetrabutoxyzirconium, tetraoctyloxyzirconium, tetrapropoxytitanium, and tetrabutoxytitanium are preferred. The compounds represented by the above general formulas can be used as a mixture of two or more thereof.

The component (c) of the present invention comprises a compound having a sulfate group.
Compound and / or a compound having a sulfone group is used.
It is. This component is S0 after firing._Three ^2-Or HSO_Three-Remains
Preferably, the compound is a compound that causes Has sulfate groups
Sulfuric acid, sulfuric anhydride, ammonium sulfate
System, ammonium hydrogen sulfate, tetramethyl ammonium sulfate
Monium and the like are preferred. Also Sur
The compound having a phon group is preferably a compound having 1 to 12 carbon atoms.
More preferably, the aliphatic sulfonic acid hydrocarbon chain is 1 to 6.
A substituted product obtained by substituting all or part of hydrogen with fluorine is preferable.
In addition to those mentioned above, those having 6 to 12 carbon atoms, preferably
Is the hydrogen of the hydrocarbon chain of the aromatic sulfonic acid which is 6 to 8.
A substituted product in which all or a part is substituted with fluorine is preferable.
It is mentioned. Specifically, CF_ThreeSO_ThreeH, CF
_Two(CF_Two) SO_ThreeH, CF_Two(CF_Two)_TwoSO_ThreeH, CF
_Two(CF_Two)_ThreeSO_ThreeFluorine substitution of aliphatic sulfonic acids such as H
Body, C₆FH_FourSO_ThreeH, C₆H_ThreeF_TwoSO_ThreeH, C₆H_TwoF_ThreeS
O_ThreeH, C₆HF_FourSO_ThreeH, C ₆F₆SO_ThreeBenzene such as H
Fluorinated sulfonic acid, C₆H_ThreeF (CH_Three) SO
_ThreeH, C₆H_TwoF_Two(CH_Three) SO_ThreeH, C₆HF_Three(CH_Three)
SO_ThreeH, C₆F_Four(CH_Three) SO_ThreeParatoluene such as H
Examples thereof include a fluorine-substituted product of sulfonic acid. These
In sulfuric acid and CF_ThreeSO_ThreeH is particularly preferred. component
The compounds described above as (c) may be used in combination of two or more.
It is, of course, possible.

[0008] The catalyst of the present invention is prepared using the above components (a) to (c) as basic components. Although the use ratio of each component is not particularly limited, component (b) is usually 10 mol or less, preferably 1 mmol to 1 g of unit mass of component (a).
In the range of 5 moles, more preferably 0.1 mmol to 2
It is used in the molar range, particularly preferably in the range from 0.01 mmol to 1 mol. Incidentally, the catalyst of the present invention, component (b)
Even when the amount of used is relatively small, it exhibits sufficient catalytic activity as an alkylation catalyst. In addition, the amount of component (c) used is usually 1 to 1 per unit mass of component (a) and component (b).
It is selected in the range of 100% by mass, preferably 5 to 75% by mass, more preferably 10 to 50% by mass.

The catalyst according to the present invention is obtained by bringing the component (a) into contact with the component (b) and then with water or steam (hereinafter referred to as steam treatment), followed by the component (c) After contacting with, it can be prepared by a procedure of baking in a temperature range of 100 to 400 ° C. (see below), but in addition, the following preparation procedure can be adopted. Contact component (a) with component (b) ⇒ Steam treatment (preparation of catalyst precursor) ⇒ Contact component (c) ⇒ Firing Contact component (b) with the catalyst precursor ⇒ Steam treatment ⇒ Component
(c) contact ⇒ firing Contact the catalyst precursor with component (b) ⇒ steam treatment ⇒ component
(b) contact ⇒ steam treatment ⇒ contact of component (c) ⇒ calcination Contact component (c) with the catalyst precursor ⇒ calcination ⇒ contact of component (b) ⇒ steam treatment ⇒ calcination Is preferably
Is particularly preferred. Then, it is more desirable to sandwich a drying step after the steam treatment. The contact conditions between the component (a) and the component (b) are not particularly limited, but the conditions under which the component (b) can be immobilized on the component (a), in other words, the component (b) is surely supported on the component (a). It is desirable that the conditions be obtained. As a contact method satisfying this condition, the component (b) is dissolved in a hydrocarbon solvent capable of solubilizing the component (b), and the component (a) is added to the solution under a nitrogen atmosphere.
And mixing while heating. As the above-mentioned hydrocarbon solvent, a saturated aliphatic hydrocarbon having 6 to 16 carbon atoms, for example, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and the like can be used. In addition, aromatic hydrocarbons such as benzene, toluene, and xylene can be used as the solvent. The contact time is not particularly limited, but is usually 10 minutes to 48 hours, preferably 1 minute.
It is selected in the range of about 20 hours to about 20 hours. In addition, the contact temperature can be selected in the temperature range from room temperature to the boiling point of the solvent used, but as long as the boiling point of the solvent is not exceeded,
It is preferred to maintain the temperature as close as possible to the boiling point.
By stirring the component (a) added to the hydrocarbon solvent solution of the component (b) at a desired temperature for a desired time in the solution, the component
The desired amount of (b) is immobilized (supported) on component (a). Thereafter, the component (a) supporting the component (b) is separated from the solution by any means and subjected to the next steam treatment step. The solids separated from the solution can be washed with a hydrocarbon solvent prior to steaming.

The component (a) carrying the component (b) is then subjected to a steam treatment at a predetermined temperature for a predetermined time. In this steam treatment, the component (a) supporting the component (b)
It can be completed by contacting with water vapor at a temperature range of about 0 to 200 ° C. for 10 minutes to 10 hours, or alternatively, the component (a) carrying the component (b) is mixed with water and sealed. In the container, for example, using an autoclave, usually at 150 ° C to 250 ° C, preferably 180 ° C to 200 ° C
The reaction can be carried out by heating the mixture to a temperature of 1 ° C. and reacting it for 1 to 5 hours. The pressure at this time is usually 1.6 MPa or more.
It is desirable to be about 2.3 MPa. Regardless of which method is employed, the above-mentioned steam treatment is preferably performed under the condition that the component (b) supported on the component (a) is hydrolyzed to generate a hydroxyl group. The resulting product obtained by subjecting the component (a) carrying the component (b) to steam treatment (hereinafter, for convenience, referred to as an oxide-modified carrier), is then brought into contact with the component (c). Prior to the contact, the oxide-modified carrier is placed in an air or nitrogen atmosphere for 120 to 20 days.
It is preferable that the carrier is dried in a temperature range of 0 ° C. to remove in advance moisture that may be attached to the carrier. Any method can be employed for contacting the oxide-modified carrier with the component (c). However, generally, a method is used in which the oxide-modified carrier is immersed in the component (c) which is normally in a liquid state or an aqueous solution thereof. The temperature at this time is not particularly limited, but is usually about room temperature, and the immersion time is usually selected in the range of 1 to 10 hours. After completion of the immersion, the oxide-modified carrier is generally recovered from the liquid, washed appropriately with pure water or the like, and then dried. The final stage of the catalyst preparation is a step of calcining the oxide-modified support having been brought into contact with the component (c) in a temperature range of 100 to 400 ° C. This firing step can be performed in an atmosphere of an inert gas such as nitrogen or argon, in air, or in a vacuum. The firing time is usually 1
10 to 10 hours, preferably 2 to 5 hours. The firing may be carried out in a flowing manner while holding the object to be fired on a fixed bed, or may be carried out while maintaining the object to be fired in a stirring state. When the calcination temperature exceeds 400 ° C., not only the alkylation activity of the catalyst decreases, but also, for example, in the reaction of alkylating isobutane with butene-2, the selectivity of the product alkylate to trimethylpentane is reduced. Although high, the amount of the hydrocarbon component having 8 carbon atoms cannot be maintained at a high level. If the firing temperature is lower than 100 ° C., the alkylate obtained using the catalyst may be colored. The thus obtained alkylation catalyst of the present invention can be used in any of a batch method and a continuous method, and is particularly suitable for a continuous method and a continuous fixed bed flow method reaction.

The method for alkylating an isoalkane according to the present invention comprises reacting an isoalkane with an alkene in the presence of the above-described alkylation catalyst. The alkene used in the alkylating agent preferably has 3 to 6 carbon atoms. Propylene, butene-1, tran
s-butene-2, cis-butene-2, isobutylene, pentene-1, pentene-2, 2-methylbutene-1, 2-methylbutene-2, hexene-1, hexene-2,2,3
-Dimethylbutene, 2-methylpentene-1, 4-methylpentene-1 and the like are specific examples of the alkylating agent that can be used in the present invention, and among them, butene-1, trans-butene-2, cis Butenes such as butene-2 and isobutylene are preferred. Two or more alkenes can be used as a mixture in the alkylating agent. On the other hand, the isoalkane to be alkylated has 4 to 6 carbon atoms, preferably 4 to 6 carbon atoms.
5, but isobutane, isopentane, isohexane and the like are specific examples thereof, and isobutane is particularly preferred. The isoalkane to be alkylated, like the alkylating agent, can be a mixture of two or more isoankanes. The object of the alkylation (isoalkane) and the alkylating agent (alkene) do not need to be of high purity, but generally desirably have a purity of 50% or more, preferably 60% or more. The isoalkane and alkene used in the present invention may contain other hydrocarbons and hydrogen. One preferred source of isoalkanes and / or alkenes that can be used in the present invention is a (fluid) catalytic cracker of hydrocarbons. The molar ratio of isoalkane: alkene in the alkylation reaction system is
Although it can be arbitrarily selected, usually 1: 1 to 1000:
1, preferably 1: 1 to 500: 1, more preferably 1: 1 to 100: 1. The reaction temperature is usually from room temperature to 150 ° C, preferably from 20 ° C to 125 ° C.
° C, more preferably in the range of 50 ° C to 100 ° C, and the reaction pressure is usually selected in the range of normal pressure to 6 MPa, preferably 0.3 to 2 MPa. Although any of a liquid phase reaction and a gas phase reaction can be employed for the alkylation reaction of the present invention, it is preferable to employ a liquid phase reaction. As the reaction mode, either a batch type or a flow type can be adopted.
When the reaction is performed in a batch system, the alkene and the isoalkane are generally used in a total amount of 1 to 200 g, preferably 5 to 100 g, per 1 g of the catalyst of the present invention comprising the above-mentioned co-ground product. The alkylation method of is not limited to this. The reaction time can also be arbitrarily selected, but usually the desired alkylation reaction can be completed in about 5 minutes to 5 hours, preferably about 10 minutes to 3 hours.
When the reaction is performed in flow-through is, 0.01～30H ^-1 a feed containing isoalkanes and alkenes, the preferably circulates the catalyst bed at a liquid hourly space velocity of 0.1 to 20 ^-1 (SV) Is common. In the alkylation method of the present invention, it is also possible to add water or a lower alcohol such as methanol to the reaction system, and the addition amount thereof is generally 0.01 to 1 g atom of zirconium or titanium contained in the catalyst. It is in the range of 1.2 mol, preferably 0.1-1 mol. By adding water or lower alcohol,
Effects such as improvement in the conversion of the alkene as the alkylating agent and the yield of the branched isoalkane are obtained. The alkylation reaction product can be recovered from the unreacted raw materials by means such as distillation, and the unreacted raw materials can be recycled to the reactor as needed. According to the alkylation method of the present invention, an isoalkane can be alkylated with an alkene to be converted into a highly branched isoalkane. In particular, when isobutane is used as the isoalkane and butenes are used as the alkene, trimethylpentane, which is useful as a high octane gasoline base material, can be obtained with a particularly high yield. In addition, according to the alkylation method of the present invention, since there are few by-products of heavy substances such that the product turns red, treatment with water or an aqueous alkali solution, which has been performed to obtain a conventional purified alkylate, is used. It does not particularly require an alkylate purification process.

[0012]

The catalyst for alkylation of the present invention is particularly useful for a continuous fixed-bed reactor, and can be prepared by simple means and easily handled. The alkylation method using this catalyst has higher energy efficiency and can maintain both the alkene conversion and the yield of the highly branched isoalkane at a high level as compared with the conventional method.

[0013]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. <Measurement of average particle size> The average particle size was measured by a sieving method. The geometric mean diameter (di) of the sieve (the average diameter of the two sieves) and the weight fraction of the granular material at the geometric mean diameter of the sieve
The arithmetic average diameter (Dp) consisting of (Xi) was determined, and this was defined as the average particle diameter. Dp = ΣXidi Taking silica as an example in Example 1 described later as an example, the average particle diameter is obtained as follows. 50 g of silica was shaken in air for 3 hours using a sieve shaker (an electromagnetic vibration type sieve) composed of 9, 10, 16, 20 and 24 mesh sieves. Table 1 shows the results.

[0014]

[Table 1]

From the data shown in Table 1, the average particle size (Dp) of the silica used in Example 1 is 1270 μm. Example 1 <Preparation of catalyst> The particle size distribution was 850 μm to 1700 μm in a range of 98%, the average particle size was 1270 μm, and the specific surface area was 3
Spherical silica (500 m ² / g, pore volume 1.0 cc / g)
15 g of the mixture calcined in air at 2 ° C. for 2 hours) was placed in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen, and then 100 ml of purified toluene and 7.5 g of zirconium tetraoctanoside were added thereto, followed by reflux. The reaction was carried out for 6 hours. After the completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 2
(00 mm), the container was kept at 190 ° C., and steam was passed for 2 hours together with nitrogen to effect hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours.
13 g of the obtained white carrier was added to 300 ml of a 5N aqueous sulfuric acid solution.
The carrier was collected by filtration, washed twice with 50 ml of pure water, and then naturally dried at room temperature for 48 hours. Put the dried product in a quartz firing tube (inner diameter 100 mm, length 450 mm), and in air at 300 ° C.
For 3 hours to obtain a catalyst. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> 8.5 g of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 160 g of isobutane dehydrated with Molecular Sieve 4A was charged. Further, 4 g of butene-2 was charged.
Further, 0.5 g of n-heptane was charged as an internal standard. When the system is heated to 50 ° C., the pressure of the system is 0.62 MPa.
The alkylation reaction was performed by stirring for 2 hours in this state. When the obtained product was analyzed by gas chromatography, the butene conversion was 130 ma.
ss%, hydrocarbon component with 8 carbon atoms (hereinafter referred to as C8 component)
Was 52%, and the selectivity of trimethylpentane in the C8 component was 81%. Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that the calcination temperature of the dried product in <Preparation of catalyst> in Example 1 was changed from 300 ° C to 500 ° C. The color of the obtained catalyst was white. <Alkylation of isobutane / butene-2> 8.5 g of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 163 g of isobutane dehydrated with molecular sieve 4A was charged. Further, 3.9 g of butene-2 was charged. Further, 0.5 g of n-heptane was charged as an internal standard. After heating the system to 50 ° C., the pressure of the system is 0.62 M
Pa, and the alkylation reaction was performed by stirring for 2 hours in this state. Gas chromatography of the product
According to the analysis, the butene conversion was 10 mass%,
The selectivity of the C8 component was 63%, and the selectivity of trimethylpentane in the C8 component was 82%. Example 2 <Preparation of Catalyst> The range of particle size distribution from 1.7 mm to 4.0 mm is 99%, the average particle size is 3.00 mm, and the specific surface area is 60.
15 g of spherical silica (calcined in air at 500 ° C. for 3 hours) having a m ² / g pore volume of 1.0 cc / g was put into a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen. Next, 100 ml of purified toluene and 4.5 g of zirconium octanoside were added and reacted under reflux for 6 hours. After the completion of the reaction, the toluene was removed. The reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 200 m
m), the container was kept at 190 ° C., and steam was passed for 2 hours together with nitrogen to carry out hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours. 10 g of the obtained white carrier was immersed in 300 ml of a 2N aqueous sulfuric acid solution and allowed to stand for 2 hours. Then, the carrier was recovered by filtration, washed twice with 50 ml of pure water, and then naturally dried at room temperature for 48 hours. went. Dry the product with a quartz firing tube (1 inner diameter)
00 mm, length 450 mm) and calcined in air at 300 ° C. for 3 hours to obtain a catalyst. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> 9.6 g of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 170 g of isobutane dehydrated with Molecular Sieve 4A was charged. Further, 3.2 g of butene-2 was charged. Further, 0.5 g of n-heptane was charged as an internal standard. After heating the system to 50 ° C., the pressure of the system is 0.62 M
Pa, and the alkylation reaction was performed by stirring for 2 hours in this state. When the obtained product was analyzed by gas chromatography, the butene conversion was 72%.
mass%, the selectivity of the C8 component was 48%, and the selectivity of trimethylpentane in the C8 component was 83%. Example 3 <Preparation of Catalyst> The range of the particle size distribution from 500 μm to 1000 μm is 90%, the average particle size is 790 μm, and the specific surface area is 30%.
0 m ² / g, 2.6 cc / g pore volume silica (3
20 g in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen, then add 100 ml of purified toluene and 7.6 g of zirconium tetrabutoxide and reflux for 6 hours under reflux. Reacted. After the completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 200 m
m), the container was kept at 190 ° C., and steam was passed through the container with nitrogen for 2 hours to carry out hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours.
15 g of the obtained white carrier was 300 m in 10 N sulfuric acid aqueous solution.
After being immersed in 1 l for 2 hours, the carrier was recovered by filtration and washed twice with 50 ml of pure water. Then, natural drying was performed at room temperature for 48 hours. Dry the product with a quartz firing tube (1 inner diameter)
00 mm, length 450 mm) and calcined in air at 350 ° C. for 3 hours to obtain a catalyst. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> 10.9 g of the above catalyst component was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Then change the system to -2
After cooling to 0 ° C., 180 g of isobutane dehydrated with Molecular Sieve 4A was charged. 3.8 g of butene-2
I charged. Further, n-heptane was added as an internal standard at 0.5
g. After the system was heated to 50 ° C., the pressure of the system was 0.1.
It was 62 MPa, and an alkylation reaction was performed by stirring for 2 hours in this state. When the product was analyzed by gas chromatography, the butene conversion was 105
mass%, the selectivity of the C8 component was 56%, and the selectivity of trimethylpentane in the C8 component was 87%. Example 4 <Preparation of Catalyst> The particle size distribution was 850 μm to 1700 μm in a range of 98%, the average particle size was 1270 μm, and the specific surface area was 3
Spherical silica (200 m ² / g, pore volume 1.0 cc / g)
20 g of the mixture calcined in air at 2 ° C. for 2 hours) was placed in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen, and then 100 ml of purified toluene and 6.1 g of zirconium tetraoctyl oxide were added.
The reaction was performed at 0 ° C. for 6 hours. After the completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 2
(00 mm), the container was kept at 190 ° C., and steam was passed for 3 hours together with nitrogen to effect hydrolysis. 15 g of the obtained white carrier was placed in a 300 cc three-necked flask equipped with a stirrer under nitrogen, and then 10 ml of concentrated sulfuric acid was added. The reaction was performed at 200 ° C. for 3 hours on an oil bath. The color of the catalyst was black brown. <Alkylation of isobutane / butene-2> 30 ml of the above catalyst component was introduced under nitrogen into a 300 ml autoclave equipped with an electromagnetic induction stirrer. Then, the system is -20
C. and 180 g of isobutane dehydrated with Molecular Sieve 4A and 3.5 g of butene-2 were charged. Further, 0.5 g of n-heptane was charged as an internal standard. After heating the system to 50 ° C., the pressure of the system was 0.62 MPa, and the alkylation reaction was performed by stirring for 2 hours in this state. When the product was analyzed by gas chromatography, the butene conversion was 142 mass%, the selectivity for the C8 component was 58%, and the selectivity for trimethylpentane in the C8 component was 91%. Example 5 <Preparation of Catalyst> The range of particle size distribution from 850 μm to 1700 μm is 98%, average particle size is 1270 μm, specific surface area is 3
Spherical silica (500 m ² / g, pore volume 1.0 cc / g)
20 g of the mixture calcined in air at 300 ° C. for 3 hours) was placed in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen, and then 100 ml of purified toluene and 6.8 g of titanium tetrabutoxide were added thereto. Allowed to react for hours. After the completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. 15 g of the obtained product was put into a 300 ml autoclave equipped with an electromagnetic induction stirrer, then 100 ml of pure water was introduced, and the system was cooled to 190 ml.
C. (system pressure was 1.5 MPa) and reacted for 3 hours. After the system was opened, the solid matter was separated by filtration and the solid was filtered with 50 ml of pure water.
Washed twice. The washed solid was air dried for 48 hours.
15 g of the obtained white carrier was added to 300 ml of a 2 N aqueous sulfuric acid solution.
And then allowed to stand for 2 hours.
After washing twice with 0 ml, the mixture was naturally dried at room temperature for 48 hours. Dry the product with a quartz firing tube (inner diameter 100 mm, length 45
0 mm) and calcined in air at 350 ° C. for 3 hours to obtain a catalyst. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> A 2-liter autoclave equipped with an electromagnetic induction stirrer was heated at -20 ° C.
And 300 g of isobutane were introduced. Then 12.3 g of the above catalyst were added under nitrogen. Further, 0.5 g of n-heptane was charged as an internal standard. Then, change the system to 5
The temperature was raised to 0 ° C., and when the system pressure reached 0.65 Mp, 300 g of isobutane dehydrated with a molecular sieve 4A
And mixed butenes (butene-1: 8% by volume, cis-butene-2: 28% by volume, transbutene-
(2: 64% by volume) from a feed tank filled with 60 g at a rate of 20 g / h by a metering pump for 18 hours to carry out the alkylation reaction. Please check the suitability of the italic characters. Even if the composition of the mixed butene is synthesized, 100
It does not become%. Please check it. When the product was analyzed by gas chromatography, the conversion of butene was 96 mass%, the selectivity of the C8 component was 66%, and the selectivity of trimethylpentane in the C8 component was 88%. Example 6 <Preparation of Catalyst> The range of particle size distribution from 500 μm to 1000 μm is 99%, the average particle size is 790 μm, and the specific surface area is 10%.
Spherical alumina (500 m ² / g, pore volume 1.0 cc / g)
20 g of the mixture calcined in the air at 300 ° C. for 3 hours) was placed in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen, and then 100 ml of purified toluene and 2 g of tetraisopropoxyzirconium were added. Allowed to react for hours. After the completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 200 m
m), the vessel was kept at 190 ° C., and steam was passed for 2 hours together with nitrogen to effect hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours. After immersing 15 g of the obtained white carrier in 5 ml of concentrated sulfuric acid, it was placed in a quartz firing tube (inner diameter 100 mm, length 450 mm) and fired in air at 250 ° C. for 3 hours to obtain a catalyst. The color of the catalyst was black. <Alkylation of isobutane / butene-2> 40 ml of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 170 g of isobutane dehydrated with Molecular Sieve 4A and 4.1 g of butene-2 were charged. Further, 0.5 g of n-heptane was charged as an internal standard. After the system was heated to 70 ° C., the pressure of the system was 1.0 MPa,
An alkylation reaction was performed by stirring for 2 hours in this state. When the product was analyzed by gas chromatography, the butene conversion was 115 mass%, the selectivity for the C8 component was 53%, and the selectivity for trimethylpentane in the C8 component was 89%. Example 7 <Preparation of Catalyst> The particle size distribution was 850 μm to 1700 μm in a range of 95%, the average particle size was 1150 μm, and the specific surface area was 1
Spherical alumina (45 m ² / g, pore volume 0.8 cc / g)
20 g (calcined in air at 0 ° C. for 2 hours) are placed under nitrogen in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser, then 100 ml of purified toluene and zirconium trioctyloxy monobutoxide 4.1.
g was added and reacted for 6 hours under reflux. After the completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is filled in a stainless steel container (inner diameter 20 mm, length 200 mm), and the container is heated to 190 ° C.
, And hydrolysis was carried out by flowing steam together with nitrogen for 2 hours. 15 g of the obtained white carrier was immersed in 300 ml of a 10N aqueous sulfuric acid solution and allowed to stand for 2 hours. Thereafter, the carrier separated by filtration was washed twice with 50 ml of pure water, and then washed at room temperature for 48 hours.
Air dried for hours. Dry the product with a quartz firing tube (10
0mm, 450mm in length) and 350 ° C in air
After calcining for hours, a catalyst was obtained. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> 20 ml of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 180 g of isobutane dehydrated with Molecular Sieve 4A and 3.6 g of butene-2 were charged. Further, 0.5 g of n-heptane was charged as an internal standard. The pressure of the system after heating the system to 50 ° C. was 0.65 MPa, and the alkylation reaction was performed by stirring for 2 hours in this state. When the product was analyzed by gas chromatography, the conversion of butene was 122 mass%, the selectivity of the C8 component was 56%, and the selectivity of trimethylpentane in the C8 component was 85%. Example 8 <Preparation of Catalyst> The particle size distribution in the range of 500 μm to 1000 μm was 95%, the average particle size was 850 μm, and the specific surface area was 20.
30 g of silica-alumina having 0 m ² / g and a pore volume of 1.1 cc / g (alumina content: 24% by mass, calcined in air at 450 ° C. for 2 hours) were mixed with three 300 cc tubes equipped with a stirrer and a cooling condenser. The flask was placed in a flask under nitrogen, and then 100 ml of purified toluene and 3.2 g of tetrabutoxytitanium were added, followed by a reaction at 110 ° C. for 6 hours. After the completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is filled in a stainless steel container (inner diameter 20 mm, length 200 mm), and the container is filled with 1
While maintaining the temperature at 90 ° C., water vapor was passed for 3 hours together with nitrogen to effect hydrolysis. 15 g of the obtained white carrier was put in a 300 cc three-necked flask equipped with a stirrer under nitrogen, and then 5 ml of concentrated sulfuric acid was added with stirring. The reaction was performed at 150 ° C. for 3 hours on an oil bath. The color of the catalyst was black brown. <Alkylation of isobutane / butene-2> 40 ml of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 192 g of isobutane and 3.5 g of butene-2 dehydrated with Molecular Sieve 4A were charged. Further, 0.5 g of n-heptane was charged as an internal standard. System 5
After heating to 0 ° C., the pressure of the system is 0.65 MPa,
An alkylation reaction was performed by stirring for 2 hours in this state. When the product was analyzed by gas chromatography, the conversion of butene was 108 mass%, the selectivity of the C8 component was 45%, and the selectivity of trimethylpentane in the C8 component was 78%. Example 9 <Preparation of Catalyst> The particle size distribution ranged from 800 μm to 1700 μm was 95%, the average particle size was 1080 μm, and the specific surface area was 3
30 g of 20 m ² / g silica (calcined in air at 200 ° C. for 5 hours) having a pore volume of 1.6 cc / g was put in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen. 100 ml of purified toluene and 3.1 g of zirconium tetrahexyl oxide were added, and 110 ° C.
For 6 hours. After the completion of the reaction, the toluene was removed,
The reaction product was washed three times with 30 ml of purified toluene, and then toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 200 m
m), the vessel was kept at 190 ° C., and steam was passed for 2 hours together with nitrogen to effect hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours. 15 g of the obtained white carrier was immersed in 300 ml of a 10 N aqueous solution of sulfuric acid and allowed to stand for 2 hours.
After washing twice with 1 l, the mixture was naturally dried at room temperature for 48 hours. Dry the product with a quartz firing tube (inner diameter 100 mm, length 450 m)
m) and calcined in air at 250 ° C. for 3 hours to obtain a catalyst. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> 30 ml of the above catalyst was introduced under nitrogen into a 300 ml autoclave equipped with an electromagnetic induction stirrer. Subsequently, the system was cooled to −20 ° C., 170 g of isobutane dehydrated with molecular sieve 4A, and 3 g of mixed butene (butene-1: 5% by volume, cisbutene-2: 50% by volume, transbutene-2: 45% by volume). Was charged. Further, 0.5 g of n-heptane was charged as an internal standard. The pressure of the system after heating the system to 50 ° C. was 0.65 MPa, and the alkylation reaction was performed by stirring for 2 hours in this state. When the product was analyzed by gas chromatography, the butene conversion was 116 mass%, the selectivity of the C8 component was 51%, and the
The selectivity of trimethylpentane in the component was 74%.
Please check the suitability of italic characters. Example 10 <Preparation of Catalyst> The range of particle size distribution from 850 μm to 1700 μm was 98%, average particle size was 1270 μm, and specific surface area was 3
Spherical silica (200 m ² / g, pore volume 1.0 cc / g)
30 g of the mixture calcined in air at 5 ° C. for 5 hours) was placed under nitrogen in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser, and 100 ml of purified toluene and 6 g of diethylzirconium dioctyl oxide were added.
The reaction was performed at 0 ° C. for 6 hours. After completion of the reaction, the toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 200
mm), and the vessel was kept at 190 ° C., and steam was passed for 2 hours together with nitrogen to effect hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours. 15 g of the obtained white carrier was immersed in 300 ml of a 10 N aqueous sulfuric acid solution and allowed to stand for 2 hours.
After washing twice with 1 l, the mixture was naturally dried at room temperature for 48 hours. Dry the product with a quartz firing tube (inner diameter 100 mm, length 450 m)
m) and calcined in air at 250 ° C. for 3 hours to obtain a catalyst. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> 15 ml of the above homogeneous catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Then, the system is -20
C. and 160 g of isobutane dehydrated with Molecular Sieve 4A was charged. Further, 4 g of butene-2 was charged. Further, 0.5 g of n-heptane was charged as an internal standard. After heating the system to 50 ° C., the pressure of the system is 0.62 M
Pa, and the alkylation reaction was performed by stirring for 2 hours in this state. Gas chromatography of the product
Analysis showed that the butene conversion was 119 mass
%, The selectivity of the C8 component was 49%, and the selectivity of trimethylpentane in the C8 component was 73%. Example 11 <Preparation of catalyst> The particle size distribution in the range of 850 μm to 1700 μm was 98%, the average particle size was 1270 μm, and the specific surface area was 3
Spherical silica (500 m ² / g, pore volume 1.0 cc / g)
15 g of the mixture calcined in air at 2 ° C. for 2 hours) was placed in a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen, and then 100 ml of purified toluene and 7.5 g of zirconium tetraoctanoside were added thereto, followed by reflux. The reaction was allowed to proceed for 6 hours. After the completion of the reaction, the toluene was removed. The reaction product was washed three times with 30 ml of purified toluene, and then the toluene was blown at 110 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 20).
0 mm), the container was kept at 190 ° C., and steam was passed with nitrogen for 2 hours to carry out hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours. 10 g of the carrier obtained by drying is put in the above 300 cc three-necked flask under nitrogen, and then 100 ml of purified toluene
And 2 g of zirconium tetraoctanoside were added and reacted under reflux for 6 hours. Thereafter, the same treatment as above was performed to obtain a white carrier. 13 g of the obtained white carrier
Was immersed in 300 ml of a 5N sulfuric acid aqueous solution and allowed to stand for 2 hours. Thereafter, the carrier separated by filtration was washed twice with 50 ml of pure water, and then naturally dried at room temperature for 48 hours. Put the dried product in a quartz firing tube (inner diameter 100 mm, length 450 mm)
The catalyst was obtained by calcining in air at 300 ° C. for 3 hours. The color of the catalyst was dark brown. <Alkylation of isobutane / butene-2> 8.5 g of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 160 g of isobutane dehydrated with Molecular Sieve 4A was charged. Further, 4 g of butene-2 was charged.
Further, 0.5 g of n-heptane was charged as an internal standard. The pressure of the system after heating the system to 50 ° C is 0.62MP
a, and an alkylation reaction was performed by stirring for 2 hours in this state. When the product was analyzed by gas chromatography, the conversion of butene was 163 mass%,
The selectivity of the C8 component was 51%, and the selectivity of trimethylpentane in the C8 component was 78.1%. Example 12 <Preparation of catalyst> The range of the particle size distribution from 1.7 mm to 4.0 mm is 99%, the average particle size is 3.00 mm, and the specific surface area is 60.
15 g of spherical silica (calcined in air at 500 ° C. for 3 hours) having a m ² / g and a pore volume of 1.0 cc / g was put into a 300 cc three-necked flask equipped with a stirrer and a cooling condenser under nitrogen. Subsequently, 100 ml of purified toluene and 4.5 g of zirconium octanoside were added thereto, and the mixture was refluxed under reflux.
Allowed to react for hours. After completion of the reaction, toluene was removed, and the reaction product was washed three times with 30 ml of purified toluene, and then toluene was blown at 120 ° C. under a nitrogen stream. The obtained product is placed in a stainless steel container (inner diameter 20 mm, length 200 mm)
, And the vessel was maintained at 190 ° C., and steam was passed for 3 hours together with nitrogen to effect hydrolysis. The hydrolyzed reaction was dried at 120 ° C. in air for 3 hours. 15 g of the obtained white carrier was placed in a 100 ml eggplant-shaped flask, and then 2 ml of trifluoromethanesulfonic acid was added. The mixture was calcined at 200 ° C. for 3 hours while rotating the flask under nitrogen. <Alkylation of isobutane / butene-2> 9.6 g of the above catalyst was introduced into a 300 ml autoclave equipped with an electromagnetic induction stirrer under nitrogen. Subsequently, the system was cooled to −20 ° C., and 170 g of isobutane dehydrated with Molecular Sieve 4A was charged. Further, 3.2 g of butene-2 was charged. Further, 0.5 g of n-heptane was charged as an internal standard. After heating the system to 50 ° C., the pressure of the system is 0.62 M
Pa, and the alkylation reaction was performed by stirring for 2 hours in this state. Gas chromatography of the product
Analysis showed that the butene conversion was 150 mass
%, The selectivity of the C8 component was 65%, and the selectivity of trimethylpentane in the C8 component was 77%.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Mino Mizuno 8 Chidoricho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Nishiishi Mitsui Co., Ltd. Central Research Laboratory F-term (reference) 4G069 AA03 AA08 AA09 BA01A BA01B BA02A BA02B BA03A BA03B BA04A BA04B BA05A BA05B BA21A BA21B BA21C BA42A BB10A BB10B BC50C BC51C BE06C BE22A BE22B CB25 CB62 EB18Y EC03Y EC07Y EC08Y FA01 FB08 FB20 FB30 FC02 FC07 4H006 AA02 AA03 AABA BA33 BA30 BA33 BA09 BA33 CF10

Claims (2)

[Claims] 1. A method according to claim 1, wherein (a) silicon oxide and / or aluminum oxide is added to (b) R ¹ _m Me (OR ² ) _zm (where R ¹
And R ² each represent a hydrocarbon group having 1 to 12 carbon atoms, Me represents Zr or Ti, z represents a valence of Me, and m represents 0 ≦ m ≦ z. And then contacted with water or steam, and then (c) a compound having a sulfate group and / or
Alternatively, a catalyst for alkylation of isoalkane obtained by contacting with a compound having a sulfone group and then calcining in a temperature range of 100 to 400 ° C. 2. The method according to claim 1, wherein (a) silicon oxide and / or aluminum oxide is added to (b) R ¹ _m Me (OR ² ) _zm (where R ¹
And R ² each represent a hydrocarbon group having 1 to 12 carbon atoms, Me represents Zr or Ti, z represents a valence of Me, and m represents 0 ≦ m ≦ z. And then contacted with water or steam, and then (c) a compound having a sulfate group and / or
Alternatively, an alkylation method of an isoalkane, which comprises reacting an isoalkane with an alkene in the presence of a catalyst obtained by bringing the compound into contact with a compound having a sulfone group and then calcining the compound in a temperature range of 100 to 400 ° C.