JPS6178736A - Production of 4-methyl-1-pentene - Google Patents

Abstract

PURPOSE:To produce the titled compound by the dimerization of propylene, using a catalyst prepared by supporting Na, K, Na amide, etc. on a carrier composed of K2O and Al2O3, optionally hydrogenating the product, and contacting with an ester. CONSTITUTION:The titled compound is produced by the dimerization of propylene, using a catalyst prepared by supporting Na, K, Na amide, K amide, etc. on a carrier composed mainly of the compound of formula I (0.5<=x<=11) and preferably containing a small amount of potassim carbonate, optionally treating the product with hydrogen and/or oxygen, and contacting with the ester of formula II (R<1> is 1-15C chain or cyclic aliphatic hydrocarbon residue, 6-20C aryl, or aralkyl; R<2> is aliphatic hydrocarbon residue). EFFECT:The catalyst has short induction period, high dimerization activity, high selectivity, and long catalytic life.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to bilayering propylene to produce 4-methyl-1
- Concerning a new method for producing penteno.

By polymerizing 4-methyl-1-pentene, it has high transparency, #thermal properties, mechanical and electrical properties,
# A polymer with excellent chemical properties is obtained, and ethylene,
When manufacturing polyolefins by polymerizing α-olefins such as propylene, the transparency of polyolefin products,
It is also a compound that can be used as a comonomer to improve various physical properties such as stress cracking properties in the environment, and particularly reduces crushing performance.

[Conventional technology]

Conventionally, propylene is duplexed in the presence of alkali metals such as sodium and potassium to form 4-methyl-1-
It is known that pair ten can be obtained (for example, J, O
tg, Ches, 30.3288 (1965), W. Shaw et al.).

Furthermore, it is also known that 4-methyl-1-peatene can be obtained by duplexing probylene using a catalyst in which an alkali metal is supported on a carrier. In this case, graphite, potassium carbonate, alkali metal silicate, alkali metal halide, magnesium && acid, talc, etc. are used as the carrier.

However, these and other known methods have relatively low yields of propylene dimer and selectivity for 4-methyl-1-be/tene, and in addition to the desired 4-methyl-1-peatene, cis and trans 4-methyl-2-pentene, 2-methyl-1-penteno, 2-methyl-2-penote/l-hexene, cis and t
rams 2-hexeno pleasure in cis and trans
It had the disadvantage that 3-hexene was produced as a by-product in multiple plantings. In general, these isomers have similar boiling points to each other, and in order to obtain the desired 4-methyl-1-pentene with sufficient purity, precise distillation operations are required, which increases the cost of purification. It also had its shortcomings.

In addition, many of the catalysts used in these known methods have long induction periods that require a long time to reach their maximum activity.
It took a long time for the reaction to become steady, and many of them were inferior in terms of economic efficiency and stable operation. In addition, many of these known Nito-forming catalysts have not only Nito-forming ability but also polymerization ability, and can perform a single polymerization reaction in addition to Nito-forming reaction.
The generated polymer sometimes covered the catalyst surface and gradually lost its activity. In particular, when such a catalyst is used, it has often been observed that the selectivity tends to decrease as the activity decreases. Although the catalyst that has lost its activity in this way has been solidified by the resin-like polymer in one reactor, there is still a catalyst with tXi activity within the reactor, and the catalyst is When removing the spent catalyst for replacement, there is a drawback that handling is inconvenient because there is a risk of ignition or fire due to contact with oxygen, moisture, etc. in the atmosphere.

Furthermore, in conventional catalysts for the production of 4-methyl-1-pentene, the support of sodium or potassium on the carrier is difficult because the carrier itself is inert or has a small porosity. 5wL% or less.

Usually it was about 1 to 5%. If you try to support 5wt% or more of sodium or potassium on these carriers, these alkali metals will adhere to the surface of the carrier in the form of mud, and as a result, the catalyst will collect in ai and become lumps, making it difficult to handle industrially. Not only was this difficult, but the activity of duplication was often extremely reduced. Furthermore, in order to adopt a fixed bed continuous flow method as a method for the decontamination reaction, it is necessary to make the catalyst into pellets, but conventionally, the catalyst for producing 4-methyl-1-pentene was Potassium carbonate, which is used as a carrier, does not have caking properties, so it was not possible to pelletize it. Therefore, in most of the known catalysts, pellets are manufactured using graphite or the like as a binder, and sodium or potassium is supported on the pellets. However, such pellets also have the disadvantage of having a short catalyst life because they have low mechanical strength and tend to disintegrate during use.

The present inventors conducted intensive research to improve the drawbacks of the conventionally known methods and catalysts as described above, and as a result, they discovered a method using a new catalyst system as disclosed in JP-A-57-128428. . In this method, a compound represented by 20*x^l 203・=・= (1) is used as a carrier for the reaction catalyst (in the above formula, X is 0.5≦X≦11,
(preferably takes a value in the range 4, l≦X≦5) on which sodium and/or sodium amide is supported;
Furthermore, this is hydrogen-treated in advance and used as a catalyst to convert propylene into di-SI. According to this method, it is possible not only to improve the drawbacks of conventional methods using various catalysts, but also to increase the amount of sodium supported on the carrier, thereby improving the reaction rate and 4-methyl- It has been found that it is possible to obtain very high 1-penteno selectivities and to maintain this activity and selectivity at high values for very long periods of time.

However, as a result of further in-depth investigation into the above method, the present inventors discovered that the method for producing 4-methyl-1-pentene by trimerization of propylene could be improved by a completely unexpected method, and the present invention I was able to complete it.

Alkali metals or organic alkali metal compounds usually react with water, oxygen, and oxygen-containing compounds such as alcohols and esters, and their catalytic activity is lost, so contact with these substances is avoided. However, the present inventors found that the compound represented by formula (1) above was used as a carrier for the reaction catalyst, and in some cases, an excessive amount of potassium carbonate, which was used as a raw material for producing the carrier, was mixed in the compound without reacting. A patent application filed in 1982, which supports at least one element or compound selected from the group of sodium, potassium, sodium amide, and potassium amide, or which has been subjected to hydrogen treatment in advance. -Contact treated to remove ugliness by the method disclosed in No. 203508.

What is quite surprising is that contacting certain esters does not deactivate their catalytic activity, but rather increases their di-catalytic activity and 4-methyl-
It has been found that the selectivity for 1-pentene is improved, or that the selectivity for 4-methyl-l-pentene is significantly improved, although the activity is slightly decreased.

[Problem that the invention seeks to solve]

The object of the present invention is to improve the drawbacks of the previously known methods and catalysts as described above, and to use a catalyst with improved propylene dimerization activity and 4-methyl-1-pente selectivity. -Providing a method for producing methyl-1-pentene.

[Means for solving problems]

That is, the method for producing 4-methyl-1-pentene of this A IjI is a method for producing 4-methyl-1-pentene by dimerization reaction of propylene, in which the following formula (1
) %Formula %(1) (However, in the above formula, X is 0.5
≦X≦11) on which at least one element or compound selected from the group consisting of sodium, potassium, sodium amide, and potassium amide is supported. , optionally subjected to hydrogen treatment and/or m-substance treatment, to form an ester R' GOOR2 (2) represented by the following formula (2) (wherein R1 is a chain or cyclic ct=cts is used as a catalyst in contact with an aliphatic hydrocarbon residue or a C6-C2° aryl group or aralkyl group, R2 represents a C, #C6 chain or cyclic aliphatic hydrocarbon residue. It is characterized by

[Preferred embodiment for carrying out the invention] (The compound represented by the above formula (1) used as the main component of the carrier in the method of the present invention is obtained, for example, by the following method. Namely, KOH , KOH3 (R3 is CI"C
20 linear or branched aliphatic hydrocarbon residues or C6 to C7 aryl groups or aralkyl groups)
, KHCO3, K2 (:03 (including those containing crystal water), KH.

at least one potassium-containing compound such as KR'(R' represents a C1-C20 linear or branched aliphatic hydrocarbon residue or a C6-C heptaryl group or an aralkyl group); and hydrogillite. Alumina hydrates, α- and γ-alumina, such as , viate, boehmite, diaspor, etc.

AI(OR5)3 (R5 represents at least one company selected from C, -C2° direct or branched aliphatic hydrocarbon residue and C6-C 7-aryl group or 7-ralkyl group), etc. of at least 18i of an aluminum-containing compound such that the K/Al ratio becomes the above-mentioned predetermined
In the compound represented by formula (1), which is obtained by reacting for 1 to 20 hours in the presence or absence of air, nitrogen X, etc. at a temperature of o-tsoo°C,
Preferably, X takes a value in the range of 1≦X≦5.

The compound constituting this carrier has K2O and Al2O as constituent elements, but this is a convenient representation of the composition of the carrier produced when the charging composition of the raw reagent changes. However, these constituent compounds do not exist as they are, but mainly as complex compounds. Therefore, in the car, O and A I
Even if it is mixed with 203, it is a completely different type of carrier, and the improvement in activity and selectivity that is expected when using the above carrier cannot be achieved.

When potassium carbonate is used as a potassium-containing compound that is a raw material for the catalyst support used in the method of the present invention, even if potassium carbonate is used so that the above-mentioned X is x<0.5,
In the compound represented by formula (1), X is 0,5≦X
When using iR ugly potassium, the excess potassium carbonate remains unreacted in this carrier. However, the compound represented by the above formula (1) and potassium carbonate can be handled in exactly the same way. In other words, as the carrier for the catalyst used in the method of the present invention, the compound represented by the formula (1) above may be used alone, or the compound represented by the formula (1) above may be used as the main component, and the carrier may be manufactured by A small amount of unreacted potassium carbonate used as a raw material may be mixed in. In this case, the residual amount of potassium carbonate is preferably 30% by weight or less of the compound represented by formula (1).

The compound represented by the formula (1), which is a carrier used in the method of the present invention, can absorb and carry a large amount of sodium, potassium, their hydrides, 7-bute, etc. very quickly, and is therefore very good. It maintains a dispersed state and is an excellent catalyst precursor either as it is or after being subjected to hydrogen treatment or oxygen treatment if desired. By contacting with an ester, a catalyst can be formed that provides higher activity and selectivity in the dimerization reaction of propylene.

As mentioned above, this catalyst system has the following characteristics: the catalyst has good dispersibility and does not aggregate, has high activity and selectivity, and has almost no observed phase at the start of the reaction. , is very suitable for a fully mixed mode reaction in which the catalyst is continuously mixed with propylene in 4 reactors in 16!1.

In addition, unlike potassium carbonate, the compound represented by the formula (1), which is the main component of the carrier used in the method of the present invention, is produced by a known method such as extrusion molding or pressure molding of a mixture of the aforementioned raw materials. By molding and firing, a pellet with extremely high strength can be obtained. The pellet strength of the carrier mainly composed of the compound of the formula (1) obtained in the form of pellets is also reduced by contact treatment with the ester of the formula (2) according to the method of the present invention. Ij! has high activity and selectivity in the neating reaction of probire/Ij! Therefore, it is ideal for the production of 4-methyl-1-pentene using a fixed bed continuous flow system.

The shape of the carrier used in the method of the present invention can be selected from any shape, such as a fine powder, a sphere of about 10 m, or a columnar shape, depending on the reaction mode, the shape and capacity of the reactor, etc. These are the formulas (1) written after firing the carrier raw material.
) methods for crushing and classifying lumps of compounds shown in
By kneading the raw materials, pelletizing them by extrusion molding, compression molding, etc., and then firing them, it is possible to manufacture them into a desired shape and size.

The method for supporting sodium and/or potassium on the above carrier can be carried out in exactly the same manner whether the carrier is a powder or a pellet, and can be carried out in the same manner without a solvent.
A method of stirring and mixing the carrier and sodium and/or potassium at a temperature of 0.degree. C., a method of depositing sodium and/or potassium vapor on the carrier, etc. can be employed. In addition, as a method for supporting sodium abite or potassium amide, the carrier is immersed in an ammonia solution of sodium amide or potassium abite by dissolving sodium or potassium in liquefied ammonia, and after sufficient impregnation, the ammonia is evaporated. A common method is to allow the particles to be supported.

The amount of catalytically active species sodium, potassium, sodium amide, and potassium amide (hereinafter referred to as alkali metals) added to the carrier is calculated in terms of the sodium atom and/or potassium atom of the alkali metal. 0.1-20wt% is preferable, supported amount is 20vt%
Even at this extremely high value, there are almost no side effects of tar or resinous substances, and the supported amount can be increased to a large extent, so it is highly effective against moisture and other impurities that enter the reaction system. It also shows strong resistance and can maintain high activity and selectivity for a very long period of time. Of course 0.
Even if the loading amount is as low as 1 to 1 wt%, the activity will only slightly decrease, but there will be no particular problem in carrying out the method of the present invention.In general, a loading of about 15 wt% Supported substances can be preferably used.

What was obtained in this way was the above-mentioned JP-A-57-
This includes the catalyst used in the method of No. 1284211, which itself already has catalytic activity for the dimerization reaction of propylene. However, in one method of the present invention, they are treated as catalyst precursors. The catalyst precursor is optionally heated to 100K in a temperature range of 150 to 400C, for example, prior to treatment with the ester described below.
A good catalyst precursor can also be obtained by hydrogen treatment for 0.5-10 hours at pressures up to g/c+s2. Furthermore, those without hydrogen treatment or those subjected to hydrogen treatment and brought into contact with oxygen by the method disclosed in Japanese Patent Application No. 58-203508 can also be used as good catalyst precursors.

The ester represented by the formula (2) that is applied to the catalyst precursor thus obtained may be a saturated ester or an unsaturated ester, and specific examples thereof include ethyl formate,
Examples include ethyl formate, ethyl acetate, isopropyl acetate, pentyl acetate, methyl propionate, ethyl propionate, butyl butyl, ethyl acrylate, ethyl methacrylate, methyl benzoate, and ethyl benzoate.

The above esters are applied to the catalyst precursor.

Regardless of whether the catalyst precursor is in the form of powder or pellets, esterification can be carried out using a liquid such as an aliphatic hydrocarbon that does not react with alkali metals or a gas such as an inert gas. This can be carried out by diluting and contacting. However, in this method, the reactivity of the alkali metals supported on the carrier is extremely high, so the ester concentration must be kept sufficiently low and sufficient stirring must be carried out to avoid locally reacting with excess ester. Take measures such as
Care must be taken to ensure uniform ester treatment. The diluent used in this case is preferably an aliphatic hydrocarbon having 6 or more carbon atoms such as hexane, heptane, octane, or dodecane, or an inert gas such as nitrogen, helium, or argon. The appropriate concentration is 0.005 to 20% by volume, and the treatment temperature is 0 to 300°C, preferably 20 to 200°C.
A range of is appropriate.

In the method of the present invention, the amount of ester brought into contact with the catalyst precursor to prepare the catalyst is relative to the alkali metal supported on the carrier containing the compound represented by formula (1) as a main component. 0.5 to 80 mol%, preferably 1
It is in the range of 50 mol%. Ester processing amount is 0.5
If the amount of contact with the ester is less than 80 mol%, the effect of the contact treatment with the ester according to the present invention cannot be sufficiently exhibited.On the other hand, if the amount of contact with the ester exceeds 80 mol%, the selectivity remains high in the dimerization reaction. Although it is maintained, the activity decreases,
In addition, the catalyst life is shortened, making it uneconomical.

According to the method of the present invention using the catalyst treated with ester as described above, the propylene duplexing activity and the selectivity of 4-methyl-1-pentene are significantly improved depending on the amount of ester treated.

The reason for this is not clear so far, but perhaps the ester treatment changes the electronic state around the active sites made of alkaline earth metals on the carrier, restricts the coordination of propylene, and makes it more likely to occur. It is presumed that this is because isomerization is less likely to occur.

Another r! in the method of the invention! An important feature is that when the reactor is filled with new catalyst and propylene is introduced to start the reaction, there is almost no induction period until the start of one reaction. In the catalyst systems known so far,
It was known that the induction period can be as short as 10 to 15 hours, and as long as several days or more.

In carrying out the propylene dimerization reaction by the method of the present invention, various contact fL reaction modes are possible, but
Batch type, semi-batch type using an autoclave, complete mixing tank type system reaction method in which the catalyst and raw material propylene are continuously supplied to the autoclave, and fixed bed type in which the catalyst is packed into a reactor and the raw material propylene is distributed therein. A conventional reaction method etc. may be adopted.

In any of these reaction modes, the reaction is carried out using an aliphatic hydrocarbon such as hepta/octane, dodecane, or a mixture thereof, or a compound that does not cause side reactions in the reaction. It is possible.

Furthermore, suitable reaction conditions for the propylene dimerization reaction of the present invention include a temperature range of 100 to 250°C, preferably
The temperature range is 0 to 180℃, and the appropriate pressure range is 20 to 200℃.
g/CrrI'.

When using an autoclave, there is no particular limit to the amount of catalyst to be used relative to the raw material propylene, but practically it is 0.
The range of 5 to 201% by weight is preferable, and the amount of catalyst used refers to the total amount of the carrier and the supported alkali metals.

In addition, the reaction time (in the case of a batch type or semi-batch type) or residence time (in the case of a ml type) is preferably in the range of 1 to 10 hours. ISV) is 0.1-10 (V/V -ht
) is preferred.

The raw material propylene used in the reaction does not necessarily have to be of high purity, but other olefins, diolefins, wood, air, charcoal gases, etc. must be removed to the extent that is normally industrially possible. It is preferable to use ethane,
It is better not to include saturated hydrocarbons such as propane and butane, but there is no problem if they are included.

〔Effect of the invention〕

According to the method for producing 4-methyl-1-pentene of the present invention, the induction period is short, the propylene dimerization activity is high, and the 4-methyl-1-pentene production method has a short induction period and a high propylene dimerization activity.
Good results are obtained with high selectivity for methyl-1-pentene and long catalyst life.

[Example of the present invention]

The present invention will be explained in more detail below using Examples.

Example 1 KOH+boehmite-X20 jar x AI20 (x m
O,98) Potassium hydroxide Perev) 68g (Water 15
%) is crushed into fine powder and boehmite 8
0 g was mixed well, placed in an alumina crucible, and fired at 1200° C. for 5 hours in an air atmosphere. After cooling, the fired product was taken out, placed in an alumina pot, and ground in a centrifugal ball mill for 2 hours.

A material finer than 80Il@sb was used as a carrier. The Ni/AI ratio of the coating carrier was determined by atomic absorption spectrometry.
K/A1 was 0.98.

80 g of this tU body was placed in a 300-capacity three-necked flask.
The mixture was heated to 150° C. under a nitrogen gas atmosphere, and 8 g of sodium was added while stirring. After the addition, the temperature was raised to 200°C, and the mixture was stirred for 1 hour and then supported on a homogeneous layer to obtain a catalyst precursor.

18 g of the catalyst precursor obtained in this manner was thoroughly dried and tested with nitrogen (W), and placed in a stainless steel autoclave containing 0.83131% ethyl acetate. After adding
The mixture was stirred at 100°C for 1 hour. After cooling the autoclave,
When a part of the liquid was sampled and analyzed by gas chromatography, it was found that almost all of the charged ha mini chill was J! ! lvI, and was contacted with ethyl acetate of H,+ corresponding to 10 mol% of the sodium supported by this operation.

Using the catalyst thus obtained, a disulfidation reaction of propylene was carried out. That is, 150 g of propylene was placed in the above autoclave and reacted at 180°C for 5 hours. After the reaction was completed, the autoclave was rapidly cooled with tap water to stop the reaction, and unreacted propylene was captured in a trap in a dry ice-methanol bath. collected. Furthermore, the solvent, reaction products, etc. remaining in the reactor were recovered by vacuum distillation.

After evaporating the propylene previously collected in the Trap-7 in the recovered reaction solution, the remaining parts having a boiling point higher than the dimer were combined and subjected to gas chromatography using a 50 m long glass capillary column coated with squalane. According to the analysis, the reaction rate of propylene was 37%.
The selectivity of 4-methyl-1-pentene was 33%. Therefore, the activity per gram of this catalyst per hour is:

It was 0.894 (g-dimer/g-catalyst unit hr) (description of units is omitted in the following examples).

Example 2 0.1? n-hebuta 7100 containing li% ethyl acetate
As a result of an analysis in which a propylene dimerization reaction was carried out under exactly the same conditions as in Example 1, except that the ethyl acetate treatment of the catalyst precursor was changed to 2 mol% of sodium using The reaction rate was 35%, the selectivity for 4-methyl-1-pentene was 93%, and the activity of this catalyst was:
It was o,ess.

Example 3 n-heptane too containing 4.131% by weight of ethyl acetate
ml, and the propylene dimerization reaction was carried out under the same conditions as in Example 1, except that the amount of ethyl acetate treated as a catalyst precursor was 50 mol% of sodium.As a result of the analysis, the reaction of propylene was The selectivity for 4-methyl-1-pentene is 32%, and the activity of this catalyst is:
It was o, eoo.

Comparative Example 1 A propylene disulfide reaction was carried out under exactly the same conditions as in Example 1, except that the catalyst precursor was used as a catalyst without being treated with ethyl acetate. As a result of zero analysis, the reaction rate of propylene was is 34%, the selectivity of 4-methyl=1-pentene is 88%, and the activity of this catalyst is 0.838.
Met.

Example 4 (See Example 1 for the chemical reaction formula) Ethyl acetate was prepared in the same manner as in Example 1 using the supported catalyst precursor leg in which 5 wt% of potassium was supported instead of sodium on the carrier used in Example 1. Processing was carried out. The amount of ethyl acetate subjected to the contact treatment was equivalent to 5 mol% of the supported potassium.Next, a disulfide reaction of propylene was carried out in the same manner as in Example 1.As a result of analysis, the reaction rate of propylene was 3.
6%, the selectivity for 4-methyl-1-pentene was 82%, and the activity was 0.875.

Example 5 The catalyst precursor was treated using n-hebutane 300 containing 0.48 fl 7g% methyl acetate instead of the n-hebutane containing ethyl acetate used in Example 1, and the reaction A propylene disulfide reaction was carried out under exactly the same conditions as in Example 1, except that the time was changed to 3 hours. The contact treatment amount of methyl acetate was equivalent to 20 mol% of the supported sodium.As a result of the analysis, the reaction rate of propylene was 4.
2%, the selectivity for 4-methyl-1-hentene was 91%, and the activity of this catalyst was 1.313.

Example 6 The treatment of the catalyst precursor was carried out using 100 aj of n-hebutane containing 0.84% by weight of cyclohexyl acetate instead of the n-hebutane containing ethyl acetate used in Example 1. A propylene disulfide reaction was carried out under exactly the same conditions as in Example 1. The contact treatment amount of cyclohexyl acetate was equivalent to 5 mol% of the supported sodium.As a result of analysis, the reaction rate of propylene was 40%, 4-methyl-1-
The selectivity of Beaten is 82%, and the activity of this catalyst is
Example 7 The catalyst precursor was replaced by 100aj of n-hebutane containing 1.41i1 (i% of ethyl benzoate) in place of the n-hebutane containing ethyl acetate used in Example 1. The reaction of propylene to 2 and 1 was carried out under the same conditions as in Example 1, except that the treatment was carried out. As a result of the analysis, the anti-E of propylene, -J It 31%, 4
The selectivity for -methyl-1-penotene was 90%, and the activity of this catalyst was 0.581.

Comparative Example 2 In place of the n-hebutane containing ethyl acetate used in Example 1, the catalyst precursor was treated with n-hebutane/100aj containing 1.821% n-octyl acetate. Except for this, a propylene duplication reaction was carried out under exactly the same conditions as in Example 1. The contact treatment amount of n-octyl acetate is
The reaction rate of propylene was 20%, 4-methyl-1-
The penteno selectivity is 44%, and the activity of this catalyst is
It was 0.400. The results showed that the activity and selectivity were significantly inferior compared to Examples 1 to 7.

Example 8 HCO3 + Al2O3 → 0 ψ x Al2O3
(x = 1.0) a -Na supported with 20" 202 g of γ-Full strain was thoroughly mixed and baked at 1000°C for 7 hours to produce a carrier. 15 g of sodium was added to 15 g of this carrier, and the mixture was heated at 200″C.
The mixture was vigorously stirred for 1 hour to support the particles.

The entire amount of the obtained sodium carrier was placed in a stainless steel autoclave with a 1 liter bottle, 100% of n-hebutane was added as a solvent, the temperature was raised to 180°C, the pressure was increased to 70 kg/cm2G with hydrogen, and the mixture was stirred for 3 hours. did. After cooling and releasing residual hydrogen, 750aj of n-buta containing 2.251% by volume of ethyl acetate was added and stirred at 100°C for 1 hour. 10 of the sodium supported by this operation
Tatami ethyl acetate corresponding to mol% was contact treated.

150 g of propylene was added to this autoclave, the temperature was raised to 180°C again, and the reaction was carried out for 5 hours. As a result of analysis, the reaction rate of propylene was 37%, and the selectivity of 4-methyl-1-penote was 93%. Yes, the f occupancy of this catalyst is 0
．． It was 873.

Example 9 L-BuOK+ (to sea-8uO)! AIK (
AI(08uL) (OBu”)3)2K(AI(OBu”)
u') (08usIC)3)-20-^120.
+ 4BuOBua K2Om Al2O3→Na carrying X20 ・A1203
02 Ethyl acetate → -1--→Cat, -9 (-butquine potassium 112g and aluminum -5ec
- Butquint 246g in 200aj (7) t-butanol under a nitrogen atmosphere at 70°C produces Artco/Plex 7K (AI(OBuL) (OBu
slc)3) was deposited as a white precipitate. After the solvent L-butanol was distilled off under reduced pressure, the precipitate was preliminarily calcined at 500° C. for 4 hours in a nitrogen stream to decompose all organic residues. Thereafter, the temperature was raised to 1200°C and baking was continued for an additional 3 hours.

8 g of sodium was added to the carrier Bog thus obtained under a nitrogen stream, and the mixture was vigorously stirred at 200°C for 2 hours to support sodium.

18 g of the catalyst precursor thus obtained was dried upward and placed in a stainless steel autoclave with a content i of 1000, which was purged with nitrogen, and 100 sj of n-hebutane was added thereto as a dispersion medium. The valve of this autoclave was connected to a U-shaped mercury manometer, and air dried with a molecular sieve 3A was forced into the autoclave until the mercury column reached 150 Hg. The autoclave was treated with oxygen while rotating the stirrer until the reading on the manometer dropped to +30 mdg, at which time the air inside the autoclave was released and replaced with nitrogen gas. By this operation, 1 of the supported sodium
Oxygen in an amount corresponding to 5 mol% was contact-treated with zero-order
．． N-buta 150- containing 83% by weight of ethyl acetate was added and stirred at 100°C for 1 hour. By this operation, ethyl acetate corresponding to 5 mol % of the supported sodium was contacted.

Add 150 gt of propi9 to this autoclave,
As a result of one analysis in which the reaction was carried out at 0°C for 5 hours, the reaction rate of propylene was 40%, the selectivity of 4-methyl-1-pentene was 93%, and the activity was 0.750.Example IO K, C: 03+^I (0)1)3→20・X Al
2O3(x = 0.98)2Na +2Nl-1, →
2NaNH2+ H2aNH2 20 ・x Supported on Al2O3NaNJ -xA
l2O3 Isoprobyl formate 11111110ab-10 100 g of anhydrous potassium carbonate and 78 g of aluminum hydroxide
．． After adjusting the particle size to be smaller than 18 mesh and mixing them sufficiently uniformly, they were fired at a temperature of 1100° C. for 5 hours to prepare a carrier. When the Ni/Al ratio of the wood carrier was determined by atomic absorption spectrometry, K/A I = 145.
Met. Also, when calculated from the amount of carbon dioxide gas generated by acid decomposition of the generated carrier, unreacted potassium carbonate was 32
g remains, and K2O fist x Al2O3 is x = 0.
It turned out to be 98.

This carrier 15. Og and sodium 1. Put Og into a stainless steel autoclave and add 3 liters of liquefied ammonia to it.
After 0 g was injected and stirred at room temperature for 2 hours, ammonia and hydrogen produced by the reaction were released.
0.28 in this autoclave. 100% of n-hebutane containing % isopropyl formate was added to the mixture, and the mixture was stirred at 100°C for 1 hour. By this operation, an amount of isopropyl formate corresponding to 5 mol % of the supported sodium amide was subjected to contact treatment.

Using the catalyst thus obtained, a trimerization reaction of propylene was carried out. That is, as a result of an analysis in which 150 g of propylene was placed in the above autoclave and the reaction was performed at 150°C for 5 hours, the reaction rate of propylene was 21%, 4-
The J refraction index of methyl-1-penteno is 93% and the activity is 0.3.
It was 94.

Example (See Example 1O for chemical reaction formula) Potassium amide was supported on the carrier obtained in Example 10 by using potassium instead of sodium. The amount of potassium used, the conditions for amide formation, etc. were exactly the same as in Example 10. Using the thus obtained potassium amide-supported product, it was treated with ethyl acetate in the same manner as in Example 10, and an amount of ethyl acetate corresponding to 20 mol % of the supported potassium amide was contacted with the product.

Using this catalyst, the same procedure as in Example 1 was carried out at 180°C.
As a result of the time 0 analysis of the trimerization reaction of propylene, the reaction rate of propylene was 34%, the selectivity of 4-methyl-1-pentene was 83%, and the activity was Q, [i38].

Comparative Example 3 100 g of potassium carbonate dried at 500°C for 5 hours
Add 2g of sodium to the solution under nitrogen gas atmosphere and heat to 200°C.
The solution was stirred vigorously to support sodium.

38 g of this catalyst was placed in a stainless steel autoclave with an internal capacity of 1 t under a nitrogen gas atmosphere, and 150 g of propylene was added.
along with 100 aJ of n-heptane as solvent,
As a result of zero analysis conducted at 160"C for 20 hours, the conversion rate of propylene was 43%, the selectivity of 4-methyl-1-pentene was 75%, and the activity of this catalyst was 0.
It was 090.

Comparative Example 4 Potassium carbonate obtained in Comparative Example 3 with 27% sodium content was used as a catalyst precursor, and 28 g of this precursor was used.
was thoroughly dried and placed in a stainless steel autoclave with a nitrogen jet exchange content of 1 tz, to which was added 100 aj of n-hebutane containing 0.06% by weight of ethyl acetate, and the mixture was stirred at 100 °C for 1 hour. . Through this operation, an amount of ethyl acetate corresponding to 2 mol % of the supported sodium was contacted. Using the catalyst thus obtained, a trimerization reaction of propylene was carried out. That is, 150 g of propylene was placed in the above autoclave and heated to 160°C.
As a result of 0 analysis conducted for 300 hours, the reaction rate of propyleno was 32%, and the refractive index of 4-methyl-1-penote/ was 7.
7%, activity was 0.057.

As is clear from comparison with Comparative Example 3, when the carrier is changed to potassium carbonate, no effect of contact treatment with ethyl acetate is observed, and the activity is rather lowered.

Example 12 2CO3+ At(OH)3→20 ・xAl
03 (x = 1.0)Ha
Ethyl acetate-Ha supported 20-xAI Os-
(:aL, -138 g of anhydrous hydrium carbonate and 158 g of aluminum hydroxide are mixed with a small amount of water, mixed well, and made into pellets with a diameter of 1.6 cm and a length of 5 to 8 cm using an extrusion molding machine. This was placed in an alumina crucible and fired at 1000°C in an air atmosphere for 5 hours to obtain a carrier. Sodium was added to the entire carrier at 200°C in a nitrogen gas atmosphere to give a lobe%. , further 400℃
The temperature was raised to , and heating was continued for 2 hours.

Sodium-supported peref) l obtained in this way
ong into a 500aj glass flask,
1. Hi i% ethyl acetate in n-hebutane 300
aj was added, stirred at 100°C for 1 hour, and treated with ethyl acetate. The amount of ethyl acetate treated was 10 mol% of sodium. Using the catalyst thus obtained, propylene was subjected to a dihydrogenation reaction using a fixed bed continuous flow reaction method. That is, z/a at a reaction temperature of 150°C and a pressure of 30
While maintaining the propylene at liquid hourly space velocity (LH5V
) 2. The reaction was carried out while introducing Ohr'. The reaction rate of propylev reached a standard 41% in 20 hours. The content of 4-methyl-1-pe/tene in the product is 9
The half-life of the activity, that is, the time required for the conversion of propylene to decrease by half from the highest level of I1, was over 1,500 hours.

Claims (1)

[Claims] 1) By dimerization reaction of propylene, 4-methyl-1
- In the method for producing pentene, a compound represented by the following formula (1) K_2O.xAl_2O_3 (1) (in the above formula, x is 0.5≦x≦
If desired, at least one element or compound selected from the group consisting of sodium, potassium, sodium amide, and potassium amide is supported on a carrier whose main component is After hydrogen treatment and/or oxygen treatment, the following formula (
2) Ester R^1COOR^2... (2) (However, R^1 is a chain or cyclic aliphatic hydrocarbon residue of C_1 to C_1_5 or an aryl group of C_6 to C_2_0. Aralkyl group, R^2 is C_1-C
_6 (representing a chain or cyclic aliphatic hydrocarbon residue) is used as a catalyst. 2) The method according to claim 1, wherein the carrier consists essentially only of the compound represented by the formula (1). 3) The method according to claim 1, wherein the carrier comprises a mixture of the compound represented by formula (1) and a small amount of potassium carbonate.