JPH0254805B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel process for producing 4-methyl-1-pentene by dimerizing propylene.

By polymerizing 4-methyl-1-pentene, a polymer with high transparency and excellent heat resistance, mechanical and electrical properties, and chemical resistance can be obtained. It is a compound that shows particularly excellent performance as a comonomer for improving various physical properties of polyolefin products, such as transparency and environmental stress cracking resistance, when producing polyolefins by polymerizing them.

Conventionally, propylene is dimerized in the presence of alkali metals such as sodium and potassium.
-Methyl-1-pentene is known to be obtained (e.g. J.Org.Chem., 30, 3286 (1965)).
AWShow et al. report).

Furthermore, propylene was dimerized using a catalyst in which an alkali metal was supported on a carrier, and 4-methyl-1
- It is also known that it is possible to obtain pentene. As the carrier in this case, graphite, potassium carbonate, alkali metal silicate, alkali metal halide, magnesium sulfate, talc, etc. are used.

However, these and other known methods have relatively low yields of propylene dimer and selectivity for 4-methyl-1-pentene, and in addition to the desired 4-methyl-1-pentene, cis and
trans 4-methyl-2-pentene, 2-methyl-1-pentene, 2-methyl-2-pentene, 1
-hexene, cis and trans 2-hexene, and cis and trans 3-hexene were produced in large quantities as by-products. Furthermore, these isomers have close boiling points to each other, and in order to obtain the desired 4-methyl-1-pentene with sufficient purity, a precise distillation operation is required, resulting in a large cost for purification. It also had.

In addition, many of the catalysts used in these known methods have a long induction period, which requires a long time to reach their maximum activity, and it takes a long time for the reaction to stabilize, resulting in poor economic efficiency and stable operation. But there were many things that were inferior. In addition, many of these known dimerization catalysts have not only dimerization ability but also polymerization ability, and the polymerization reaction proceeds along with the dimerization reaction, and the generated polymer covers the catalyst surface and gradually becomes active. There were times when I lost my life. In particular, when such a catalyst is used, it has often been observed that the selectivity tends to decrease as the activity decreases. The catalyst that has lost its activity in this way has been solidified by the resinous polymer inside the reactor, but there is still a sufficiently highly active catalyst remaining inside the reactor, and catalyst replacement is possible. Therefore, when extracting this waste catalyst, there is a risk of ignition due to contact with atmospheric oxygen, moisture, etc.
Another disadvantage was that it was inconvenient to handle due to the danger of fire.

The present inventors conducted intensive research to improve the drawbacks of conventionally known methods and catalysts as described above, and as a result, discovered a method using a new catalyst system as disclosed in JP-A-57-126426. Ta. This method uses a compound represented by K ₂ O x Al ₂ O ₃ (1) as a support for the reaction catalyst (in the above formula, x is
0.5≦x≦11, preferably 1≦x≦5) supported with sodium and/or sodium amide, and furthermore, propylene that is previously hydrogen-treated and used as a catalyst. It dimerizes. According to this method, it is not only possible to improve the drawbacks of conventional methods using various catalysts, but also it is possible to increase the amount of sodium supported on the carrier,
It has been found that the reaction rate and the selectivity for 4-methyl-1-pentene can be increased significantly and that this activity and selectivity can be kept at high values for a very long time.

However, as a result of further intensive studies on the above method, the present inventors found that 4-by-4 dimerization of propylene was achieved by an entirely unexpected method.
The present inventors have discovered that the method for producing -methyl-1-pentene can be improved and have completed the present invention.

Alkali metals or organic alkali metal compounds usually decompose on contact with water, oxygen, etc. and their catalytic activity is lost, so contact with these 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. or those that have been treated with hydrogen in advance, or those that have been treated with hydrogen in advance, and those that have been treated with propylene. Surprisingly, when oxygen is brought into contact with a catalytically reacted product by an appropriate method, the catalytic activity is not only deactivated, but also the dimerization activity and 4-methyl It has been found that the selectivity for -1-pentene is improved, or that the selectivity for 4-methyl-1-pentene is significantly improved, although the activity is slightly decreased.

That is, the first method for producing 4-methyl-1-pentene of the present invention is a method for producing 4-methyl-1-pentene by dimerization reaction of propylene, in which the following formula (1) K ₂ O・xAl ₂ O ₃ ...(1) A compound represented by (1) (in the above formula, x is
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 0.5≦x≦11. It is characterized by using as a catalyst a product which has been subjected to hydrogen treatment if desired and then brought into contact with oxygen.

Further, the second production method of the present invention is a method for producing 4-methyl-1-pentene by dimerization reaction of propylene, using the following formula (1) K ₂ O xAl ₂ O ₃ ... A compound represented by (1) (however, in the above formula, x is
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 0.5≦x≦11. The method is characterized in that, after hydrogen treatment if desired, the product is subjected to a contact reaction with propylene, and then brought into contact with oxygen to be used as a catalyst.

Furthermore, the third production method of the present invention is a method for producing 4-methyl-1-pentene by dimerization reaction of propylene, using the following formula (1) K ₂ O.xAl ₂ O ₃ ... A compound represented by (1) (however, in the above formula, x is
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 0.5≦x≦11. The catalyst is characterized in that the catalyst is treated with hydrogen if desired, then brought into contact with oxygen, further brought into contact with propylene, and then brought into contact with oxygen again.

The compound represented by the above formula (1) used as the main component of the carrier in the method of the present invention can be obtained, for example, by the following method. That is,
KOH, KOR ¹ (R ¹ is at least one selected from C ₁ to C ₂₀ linear or branched aliphatic hydrocarbon residues, C ₆ to _{C 30} aryl groups, and aralkyl groups), KHCO ₃ , K ₂ CO ₃ (including those containing water of crystallization), KH ² , KR ² (R ² is C ₁ to C ₂₀ linear or branched aliphatic hydrocarbon residue, C ₆ to C ₃₀ at least one potassium-containing compound such as aryl group or aralkyl group), alumina hydrate such as hydrogillite, vialite, boehmite, diaspor, α- and γ- Alumina, Al
(OR ³ ) ₃ (R ³ is a mixture of at least one selected from C ₁ to C ₂₀ linear or branched aliphatic hydrocarbon residues, C ₆ to C ₃₀ aryl groups, or aralkyl groups) and at least one kind of aluminum-containing compound such as
Preferably, it is obtained by reacting at a temperature of 500 to 1500° C. in the presence or absence of air, nitrogen, etc. for 1 to 20 hours. In the compound represented by formula (1), x preferably takes a value in the range of 1≦x≦5.

The compound constituting this carrier is composed of K ₂ O and Al ₂ O ₃ , but this is a convenient representation of the composition of the carrier produced when the charging composition of the raw reagent changes. However, the compounds of these constituent elements do not exist as they are, but mainly as a double oxide. Therefore, simply mixing K ₂ O and Al ₂ O ₃ is a completely different type of carrier, and it is unlikely that the improvement in activity and selectivity expected when using the above carrier will be achieved. Can not.

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 x < 0.5, A carrier having the same improvement effect as when x in the compound is 0.5≦x≦11 can be obtained. That is, when potassium carbonate is used, an excess amount of potassium carbonate remains unreacted in the carrier, but the compound represented by formula (1) above and potassium carbonate can be handled in exactly the same way. It is something. In other words, the carrier for the catalyst used in the method of the present invention may be the compound represented by the above formula (1) alone, or the compound represented by the above formula (1) may be used as a main component, and the support may be prepared by manufacturing the support. A small amount of unreacted potassium carbonate used as a raw material may also be present.
In this case, the residual amount of potassium carbonate is preferably 30% by weight or less of the compound represented by formula (1) above.

In conventional catalysts for producing 4-methyl-1-pentene, the amount of sodium or potassium supported on the carrier is 5 wt% or less because the carrier itself is inert or has a small porosity. Usually it was about 1 to 3 wt%. If these carriers
When attempting to support more than 5wt% of sodium or potassium, these alkali metals adhere to the surface of the carrier in a muddy form, resulting in the catalyst coagulating into lumps that are difficult to handle industrially. Not only was this difficult, but the dimerization activity was often extremely reduced. Furthermore, in order to adopt a fixed bed continuous flow method as a dimerization reaction method, it is necessary to make the catalyst into a pellet shape, but conventionally, the catalyst carrier for producing 4-methyl-1-pentene was Potassium carbonate, which is used as a raw material, does not have caking properties, so it was not possible to pelletize it. Therefore, in many 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 have the disadvantage of having a short catalyst life because they have low mechanical strength and tend to disintegrate during use. On the other hand, the compound represented by formula (1), which is the carrier used in the method of the present invention, can absorb and carry large amounts of sodium, potassium, their hydrides, amides, etc. very quickly. A catalyst that maintains a very good dispersion state and provides higher activity and selectivity in the dimerization reaction of propylene when used as is or when subjected to oxygen treatment by the method of the present invention described later. can be formed.

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 induction period at the start of the reaction. ,
It is very suitable for fully mixed mode reactions in which the catalyst is introduced continuously with the propylene into a tank reactor.

In addition, unlike potassium carbonate, the compound represented by formula (1), which is the main component of the carrier used in the method of the present invention, is formed by molding a kneaded product of the above-mentioned raw materials by a known method such as extrusion molding or compression molding. By then firing it, it is possible to make pellets with very high strength. The carrier thus obtained in the form of pellets can absorb and support large amounts of sodium, potassium, their hydrides, amides, etc. very quickly, similar to the carrier in the form of powder. Therefore, according to the method of the present invention,
High activity and selectivity are achieved in the propylene dimerization reaction. Further, the catalyst used in the method of the present invention has large pellet strength, high activity, and high selectivity, and is therefore optimal for the production of 4-methyl-1-pentene by 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 mm, or a columnar shape, depending on the reaction mode, the shape and capacity of the reactor, and the like. These can be produced by crushing and classifying the lumps of the compound represented by formula (1) obtained after firing the carrier raw material, or by kneading the raw materials and pelletizing them by extrusion molding, compression molding, etc., and then firing them. , can be manufactured in any 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. Alternatively, a method of stirring and mixing with potassium, a method of depositing vapor of sodium and/or potassium on a carrier, etc. can be adopted. In addition, as a method for supporting sodium amide or potassium amide, the carrier is immersed in an ammonia solution of sodium amide or potassium amide by dissolving sodium or potassium in liquefied ammonia.
A common method is to fully impregnate the material and then evaporate the ammonia to support the material.

The amount of sodium, potassium, sodium amide, potassium amide, etc. supported on the carrier is preferably 0.1 to 20 wt% in terms of sodium atoms and/or potassium atoms. Even at a very high supported amount of 20 wt%, there are almost no tars or resinous by-products, and since the supported amount can be increased, there is no possibility of moisture or other substances entering the reaction system. Shows strong resistance to impurities,
High activity and selectivity can be maintained for very long periods of time. Of course, even if the amount supported is as low as 0.1 to 1 wt%, the activity will only decrease slightly and no particular problem will arise in carrying out the method of the present invention. Generally, it is preferable to use one supported in an amount of about 1 to 15 wt%.

The product obtained in this way includes the catalyst used in the method of JP-A-57-126426 mentioned above, and it already has catalytic activity for the dimerization reaction of propylene. . However, in the method of the present invention, these are treated as catalyst precursors. Prior to oxygen treatment, the catalyst precursor can be made into a good catalyst precursor by optionally hydrogenating it at a temperature range of 150 to 400° C. and a pressure of up to 100 Kg/cm ² for 0.5 to 10 hours. be able to.

In addition, in the second method of the present invention, the obtained catalyst precursor is further subjected to a contact reaction with propylene prior to the contact treatment with oxygen to form supported sodium, potassium, sodium amide, and potassium amide. Alternatively, some or all of these hydrides are converted into organic sodium compounds, organic potassium compounds, etc. The catalytic reaction with propylene herein includes the use of the catalyst precursor itself as a propylene dimerization reaction catalyst by the method of JP-A-57-126426 or the like.

Furthermore, in the third method of the present invention, after the contact treatment with oxygen described below is performed, the contact reaction with propylene is performed, and then the contact treatment with oxygen is performed again.

As a method for causing oxygen to act on the catalyst precursor obtained in this way, regardless of whether the precursor is in the form of powder or pellets, it is possible to directly contain low concentration of oxygen. It can be carried out by a method of contacting with gas. However, this method is difficult to use because of the reactivity of sodium, potassium, sodium amide, potassium amide, or their hydrides supported on a carrier, as well as organic sodium compounds and organic potassium compounds (hereinafter referred to as alkali metals). Since this is extremely high, care must be taken to ensure that the oxygen content is sufficiently low to avoid excessive local oxygen treatment, and that sufficient stirring is performed. As the gas for diluting oxygen during the oxygen treatment, it is preferable to use an inert gas such as nitrogen, helium, or argon, and the appropriate dilution oxygen concentration is 0.001 to 5.0% by volume. In addition, the processing temperature is usually -20 to 400℃,
Preferably it is carried out at a temperature of 0 to 100°C.

Another method for oxygen treatment is to disperse a catalyst precursor in a saturated hydrocarbon liquid and treat the alkali metals with a low concentration of oxygen dissolved in the hydrocarbon by acting on the catalyst precursor with an oxygen-containing gas. There is. This method avoids local reactions, but
Since alkali metals and oxygen react in the presence of combustible materials, care must be taken to keep the oxygen concentration below the explosive limit. The oxygen concentration in this method is preferably 0.1 to 20% by volume, and the diluting gas is preferably nitrogen, helium, or argon. It is also possible to use an economical dilution method of using sufficiently dehumidified dry air without using any of these gases. The saturated hydrocarbon to be used preferably has a boiling point higher than that of heptane.

In the method of the present invention, the amount of oxygen brought into contact with the catalyst precursor to prepare the catalyst varies slightly depending on the method used (the first, second, and third methods); In either method, a compound represented by the formula (1) K ₂ O・xAl ₂ O ₃ (1) (however, in the above formula, x is
0.1 for alkali metals supported on a carrier whose main component is 0.5≦x≦11)
~20 mol%, preferably 0.3-10 mol%. If the amount of oxygen in the contact treatment is less than 0.1 mol %, the effect of the contact treatment with oxygen according to the present invention cannot be sufficiently exhibited. On the other hand, when the amount of oxygen to be catalytically treated exceeds 20 mol %, the selectivity in the dimerization reaction remains high, but the activity decreases and becomes uneconomical.

In addition, in the first method and the second method, the amount of oxygen contact treatment within the above range may be used as is, but in the third method, the amount of oxygen initially acted on and then the amount of oxygen reacted with propylene It is necessary that the total amount of oxygen to be reacted with to produce an organometallic compound and the amount of oxygen to be subjected to contact treatment again be within the above range. There is no limit to the relative proportion of the amount of oxygen in these two treatments, but
If only one of them is present in an extremely large amount, results that are considered to be due to the synergistic effect of this method may not be obtained.

According to the method of the present invention using a catalyst treated with oxygen as described above, depending on the amount of oxygen treated, the activity of propylene dimerization and 4-methyl-1-
Pentene selectivity is significantly improved. The reason for this is not clear so far, but perhaps the oxygen treatment changes the electronic state around the active sites of alkali metals on the carrier, restricting the coordination of propylene and making dimerization more likely to occur. This may also be because isomerization is becoming less likely to occur.

Another important feature of the method of the present invention is that when the reactor is charged with fresh catalyst and propylene is introduced to start the reaction, there is almost no induction period before the reaction starts. It is. It has been known that in conventional catalyst systems, 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 catalytic reaction modes are possible, including batch type using an autoclave,
A semi-batch type or a complete mixing tank type continuous reaction method in which the catalyst and the raw material propylene are continuously supplied to an autoclave, a fixed bed type continuous reaction method in which the catalyst is packed in a reactor and the raw material propylene is circulated therein, etc. can be adopted.

Further, suitable reaction conditions for the propylene dimerization reaction of the present invention are a temperature range of 100 to 250°C, preferably 140 to 180°C, and a suitable pressure range of 20 to 250°C.
~200Kg/ ^cm2 .

When using an autoclave, there is no particular restriction on the amount of catalyst to be used with respect to the raw material propylene, but a range of 0.5 to 20 wt% is practically preferred. In addition,
The amount of catalyst used refers to the total amount of the carrier and supported alkali metals.

Further, the reaction time (in case of batch type or semi-batch type) or residence time (in case of continuous type) is preferably in the range of 1 to 10 hours. In the fixed bed continuous method, the liquid hourly space velocity (LHSV) is 0.1 to 10 (V/
A range of V·hr) is preferable.

The propylene used in the reaction in the method of the present invention does not necessarily have to be of high purity, but other olefins, diolefins, water, air, carbon dioxide gas, etc. are removed to the extent normally industrially possible. It is preferable to use a In addition, ethane, propane,
It is better not to include saturated hydrocarbons such as butane, but there is no problem if they are included. Propylene mixed with a small amount of oxygen can also be effectively used in the method of the present invention. Oxygen can be added to propylene to obtain a desired composition by dissolving oxygen in propylene under pressure. However, it is desirable to increase or decrease the oxygen concentration in propylene depending on the amount of oxygen brought into contact when producing each catalyst. For example, if the catalyst of the first method has been treated with a fairly large amount of oxygen, the amount of oxygen coexisting in the propylene should be 2 to 2.
A value as low as 5 ppm is preferable from the viewpoint of catalyst life. In this case, the cumulative amount of oxygen to the catalyst is
It is preferable to control the amount up to 20 mol%.

In any of these reaction modes, it is not possible to carry out the reaction using an aliphatic hydrocarbon such as heptane, octane, dodecane, a mixture thereof, or a compound that does not cause a side reaction in this reaction as a solvent. It is possible.

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

Example 1 66g of potassium hydroxide pellets (containing 15% moisture) are crushed into fine powder and boehmite 80g
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 60 mesh was used as a carrier.

60 g of this carrier was heated to 150° C. in a 300 ml three-necked flask under a nitrogen gas atmosphere, and 6 g of sodium was added while stirring. Temperature after addition
The temperature was raised to 200°C and stirring was continued for 1 hour to ensure uniform support.

16 g of the catalyst precursor thus obtained was placed in a 1000 ml stainless steel autoclave which had been thoroughly dried and purged with nitrogen, and 100 ml of n-nonane was added thereto as a dispersion medium. The valve of this autoclave was connected to a U-shaped mercury manometer, and air dried with Molecular Sieve 3A was forced into the autoclave until the mercury column reached 150 mmHg. The autoclave was treated with oxygen while rotating the stirrer until the manometer reading fell to 130 mmHg, at which point the air in the autoclave was released and replaced with nitrogen gas.
Through this operation, oxygen was introduced in an amount equivalent to 1.5 mol% of the supported sodium.

A propylene dimerization reaction was carried out using the catalyst thus obtained. That is, 150 g of propylene was placed in the autoclave and a reaction was carried out at 160° C. for 5 hours. After the reaction was completed, the autoclave was quenched with tap water to stop the reaction, and unreacted propylene was collected in a trap in a dry ice-methanol bath. Furthermore, the solvent, reaction products, etc. remaining in the reactor were recovered by vacuum distillation.
After evaporating the propylene previously collected in the trap, the recovered reaction liquid was combined with the remaining portion with a boiling point higher than that of the dimer, and was coated with squalane.
When analyzed by gas chromatography using a long glass capillary column, the reaction rate of propylene was 49%, and the reaction rate of propylene was 49%.
-Selectivity for pentene was 92%. Therefore, the activity per gram of this catalyst per hour is 0.845
(g-4-methyl-1-pentene/g-catalyst/hr)
(Description of units will be omitted in the following examples).

Comparative Example 1 A propylene dimerization reaction was carried out under exactly the same conditions as in Example 1, except that the catalyst was not subjected to oxygen contact treatment. As a result of analysis, the reaction rate of propylene was 34%, the selectivity of 4-methyl-1-pentene was 89%, and the activity of this catalyst was 0.574.
It was hot.

Example 2 (See Example 1 for the chemical reaction formula) Oxygen contact treatment was carried out in the same manner as in Example 1, using 16 g of a catalyst in which 5 wt % of potassium was supported instead of sodium on the carrier used in Example 1. The amount of oxygen introduced by the contact treatment corresponded to 5 mol % of the supported potassium. Next, propylene was dimerized in the same manner as in Example 1. As a result of analysis, the propylene reaction rate was 36%, the 4-methyl-1-pentene selectivity was 91%, and the activity was 0.614.

Example 3 In the same manner as in Example 1, 234 g of aluminum hydroxide manufactured by Wako Pure Chemical Industries and 180 g of potassium hydroxide were heated at 1200°C.
A carrier was obtained by firing in a Matsufuru furnace for 5 hours. The K/Al ratio of this carrier was 0.92. The obtained carrier was pulverized with a centrifugal ball mill, and a carrier of 60 mesh or less was used.

6 g of Na was added to 60 g of this carrier at a temperature of 200 to 220° C. using the same apparatus as in Example 1, and after the addition was completed, stirring was continued for 3 hours to allow Na to be supported. The resulting catalyst was a dark blue powder with very good dispersibility.

16 g of this powder was treated with oxygen in the same manner as in Example 1. However, the amount of oxygen introduced in the contact treatment was 2 mol% of sodium.

Using the catalyst thus obtained, 150 g of propylene was added and the reaction was carried out at 150° C. for 8 hours in the same manner as in Example 1. The same post-treatment as in Example 1 was carried out and analysis by gas chromatography revealed that the propylene reaction rate was 40% and 4-methyl-1
-Selectivity for pentene was 89%. Catalytic activity was 0.417.

Example 4 100g of anhydrous potassium carbonate and aluminum hydroxide
78.0g, each with a particle size smaller than 16mesh,
After mixing the mixture to be sufficiently uniform, the mixture was calcined at a temperature of 1100° C. for 5 hours to prepare a carrier. K/ of this carrier
When the Al ratio was determined by atomic absorption spectrometry, K/Al=
It was 1.45. Also, when calculated from the amount of carbon dioxide gas generated by acid decomposition of the formed carrier, 32g of unreacted potassium carbonate remained, and K ₂ O x Al ₂ O ₃
It was found that x=0.98.

15.0 g of this carrier and 1.0 g of sodium were placed in a stainless steel autoclave, and 30 g of liquefied ammonia was pressurized into the autoclave. After stirring at room temperature for 2 hours, ammonia and hydrogen produced by the reaction were released. Next, 100 ml of n-heptane and 150.0 g of propylene were added to this autoclave.
The reaction was carried out at 160°C for 8 hours. After treatment and analysis in the same manner as in Example 1, the propylene reaction rate was 37% and the 4-methyl-1-pentene selectivity was 87%.
It was %. The activity was 0.377.

100 ml of n-heptane (normal pressure) was added to the reactor, which was under reduced pressure due to the same post-treatment as in Example 1.
was sucked in, and dry air was sucked in until the pressure reached normal pressure, and then the contents were stirred for 30 minutes to perform oxygen treatment. Through this operation, 11.0 mol% of oxygen was introduced relative to the sodium amide supported on the catalyst.

150 g of propylene was added to this autoclave, and the reaction was again carried out at 160°C for 5 hours. Analysis of the product revealed that the propylene conversion rate was 32% and the 4-methyl-1-pentene selectivity was 90%. Moreover, the activity was 0.540.

Comparative Example 2 A propylene dimerization reaction was carried out again under exactly the same conditions as in Example 4, except that the catalyst that had been reacted with propylene for 8 hours in Example 4 was not subjected to oxygen contact treatment. Summer. As a result of analysis, the reaction rate of propylene was 28%, the selectivity of 4-methyl-1-pentene was 86%, and the activity of this catalyst was
It was 0.452.

Example 5 (See Example 4 for chemical reaction formula) Potassium amide was supported on the carrier obtained in Example 4 by using potassium instead of sodium. The amount of potassium used, the conditions for amide formation, etc. were exactly the same as in Example 4. The potassium amide support thus obtained was used and treated with propylene in the same manner as in Example 4. As a result, the reaction rate of propylene was 28%, 4-methyl-1
-Selectivity for pentene was 83%. Thereafter, oxygen treatment was performed in the same manner as in Example 4 (the amount of oxygen introduced was 19.3 mol % with respect to potassium amide). Using this catalyst, a reaction was carried out at 160° C. for 8 hours in the same manner as in Example 4. As a result of the analysis, the propylene reaction rate was 27%, the 4-methyl-1-pentene selectivity was 89%, and the activity was 0.450.

Example 6 (See Example 1 for the chemical reaction formula) A carrier prepared in the same manner as in Example 1 was loaded with 2% sodium. 51 g of the obtained sodium carrier was placed in a glass 300 three-necked flask equipped with a stirrer equipped with blades so that the powder could be sufficiently stirred and mixed in a solvent-free state, and a three-way cap at the gas inlet and outlet. Collected under nitrogen atmosphere,
A mixed gas consisting of 2% oxygen and 98% nitrogen was passed through the container at room temperature for 15 minutes at a rate of 100 ml/min while stirring the contents. When the oxygen concentration in the gas discharged from the flask was measured, it was found to be 0.55%, which means that 2 mol% of the sodium amount was subjected to the oxygen introduction treatment.

15 g of this catalyst, 100 ml of heptane and 150 g of propylene were placed in an autoclave and reacted at 160°C for 7 hours. As a result, the reaction rate of propylene is 29
%, the selectivity of 4-methyl-1-pentene is 68%,
The activity was 0.365.

Example 7 70g of potassium carbonate and 660g of boehmite for 1800
C. for 7 hours to obtain a support with Al/K of 10.7. Although the potassium content is slightly lower than the starting composition, it is thought that it sublimated during firing. Moreover, the presence of α-alumina was not recognized from the X-ray diffraction diagram of this carrier.

Using this carrier, 5 wt% of sodium was supported in the same manner as in Example 1. 55 g of the obtained sodium support was collected and treated with oxygen in the same manner as in Example 6 to obtain a catalyst in which the amount of oxygen introduced was 13 mol % of sodium. 18 g of this catalyst, 100 ml of heptane, and 150 g of propylene were added to an autoclave, and the reaction was carried out at 150° C. for 6 hours. As a result of the analysis, the reaction rate of propylene was 24%, and the selectivity of 4-methyl-1-pentene was
90%, activity was 0.300.

Example 8 The carrier obtained in Example 7 was loaded with 1 wt% of potassium in the same manner as in Example 1. 18 g of catalyst obtained by reacting this with oxygen in an amount of 5 mol% of potassium, 100 ml of heptane and 150 ml of propylene.
g was placed in an autoclave, and the reaction was carried out at 150°C for 15 hours. As a result of the analysis, the reaction rate was 12%, the selectivity for 4-methyl-1-pentene was 91%, and the activity was 0.061.
It was hot.

Comparative Example 3 A propylene dimerization reaction was carried out under exactly the same conditions as in Example 8, except that the catalyst was not subjected to oxygen contact treatment. As a result of analysis, the reaction rate of propylene was 8%, the selectivity of 4-methyl-1-pentene was 85%, and the activity of this catalyst was 0.038%.
It was hot.

Example 9 200 g of potassium hydrogen carbonate and 202 g of γ-alumina were thoroughly mixed and fired at 1000° C. for 7 hours to produce a carrier. 1.5 g of sodium was added to 15 g of this carrier, and the mixture was stirred vigorously at 200° C. for 1 hour to support the carrier. The obtained sodium carrier was placed in a stainless steel autoclave with a total internal capacity of 1, and n-
After adding 100 ml of heptane and raising the temperature to 160°C, the mixture was pressurized to 70 kg/cm ² G with hydrogen and stirred for 3 hours. The pressure drop during this period was 2.3 Kg/cm ² . After cooling and releasing residual hydrogen, 50g of propylene was added and reaction was carried out at 160°C for 8 hours. After removing unreacted propylene, produced dimer, and heptane under reduced pressure in the same manner as the post-treatment in Example 1, 100 ml of heptane was added, and dry air was further added until the pressure inside the autoclave rose by 140 mm in mercury column. ,
Stirring was continued for 1 hour. This operation introduced 2 mol % oxygen of sodium. 150 g of propylene was placed in this autoclave, and the temperature was again raised to 160°C to carry out a reaction for 7 hours. As a result of the analysis, the reaction rate was 76%, and the selectivity of 4-methyl-1-pentene was
86%, activity was 0.849.

Example 10 112g of potassium t-butoxy and aluminum
When 246 g of sec-butoxide is mixed in 200 ml of t-butanol at 70°C under a nitrogen atmosphere, art.
K [Al (OBu ^t ) (OBu ^sec ) ₃ ] which is complex
was deposited as a white precipitate. After distilling off the solvent t-butanol under reduced pressure, the precipitate was heated at 500°C in a nitrogen stream.
The sample was precalcined for 4 hours to decompose all organic residues. Thereafter, the temperature was raised to 1200°C and firing was continued for an additional 3 hours.

3 g of sodium was added to 15 g of the carrier thus obtained under a nitrogen stream, and the mixture was vigorously stirred at 200° C. for 2 hours to carry out sodium loading.

The entire amount of this sodium carrier was placed in a stainless steel autoclave, 100 ml of heptane was added, and oxygen treatment was carried out in the same manner as in Example 1. The oxygen treatment amount was 2 mol% of sodium. Subsequently, 50 g of propylene was added, and the reaction was carried out at 160° C. for 2 hours to effect organometallation. Thereafter, unreacted propylene, the produced dimer, and heptane as a solvent were distilled off, and the mixture was again treated with oxygen using dry air in the same manner as in Example 9. The amount of oxygen was 2 mol% of sodium.

The catalyst thus obtained was used to dimerize propylene. i.e. 100ml heptane
and 150 g of propylene were added, and the reaction was carried out at 150°C for 4 hours. As a result of the analysis, the reaction rate was 37%, the selectivity for 4-methyl-1-pentene was 89%, and the activity was 0.686.
It was hot.

Example 11 138g of anhydrous potassium carbonate and aluminum hydroxide
A small amount of water was added to 156 g, kneaded, and formed into pellets with a diameter of 1.6 mm and a length of 5 to 8 mm using an extruder. This was calcined at 1000°C for 5 hours to obtain a carrier. Sodium was added to the total amount of this carrier at 200° C. to a concentration of 10 wt % under a nitrogen atmosphere, and the mixture was sufficiently stirred for 2 hours to be supported. The temperature was further raised to 400°C and heating was continued for an additional 2 hours. 500ml of 100g of the sodium-supported pellets obtained in this way.
Thoroughly dehydrated in a large capacity glass flask.
- 300 ml of decane was added and oxygen treatment was carried out in the same manner as in Example 1. The amount of oxygen processed is 2 times that of sodium.
It was in mol%. Using the catalyst thus obtained, propylene was dimerized by a fixed bed continuous flow reaction method. That is, the reaction was carried out while maintaining the reaction temperature at 150° C. and the pressure at 90 Kg/cm ² while introducing propylene at a liquid hourly space velocity (LHSV) of 1.4 hr ^-1 . The propylene reaction rate became steady and reached 38% in 20 hours. The content of 4-methyl-1-pentene in the product was 93%. Although the reaction was continued, the half-life of the activity, that is, the time it takes for the propylene conversion rate to decrease by half from its highest value, was 1500.
It was over time.

Claims (1)

[Claims] 1. A method for producing 4-methyl-1-pentene by a dimerization reaction of propylene, which is represented by the following formula (1) K ₂ O.xAl ₂ O ₃ (1). (However, in the above formula, x is
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 0.5≦x≦11. 1. A method for producing 4-methyl-1-pentene, which comprises using as a catalyst a product obtained by subjecting 4-methyl-1-pentene to oxygen treatment after hydrogen treatment if desired. 2. Claim 1, wherein the carrier consists essentially only of the compound represented by the formula (1).
The method described in section. 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. 4 In the method for producing 4-methyl-1-pentene by dimerization reaction of propylene, a compound represented by the following formula (1) K ₂ O x Al ₂ O ₃ (1) (however, the above In the formula, x is
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 0.5≦x≦11. A method for producing 4-methyl-1-pentene, which comprises using as a catalyst a product obtained by subjecting 4-methyl-1-pentene to hydrogen treatment if desired, then contacting it with propylene, and then contacting it with oxygen. 5. Claim 4, wherein the carrier consists essentially only of the compound represented by the formula (1).
The method described in section. 6. The method according to claim 4, wherein the carrier comprises a mixture of the compound represented by formula (1) and a small amount of potassium carbonate. 7 In the method for producing 4-methyl-1-pentene by dimerization reaction of propylene, a compound represented by the following formula (1) K ₂ O xAl ₂ O ₃ (1) (however, In , x is
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 0.5≦x≦11. 4-methyl-1, which is optionally treated with hydrogen, then brought into contact with oxygen, further brought into contact with propylene, and then brought into contact with oxygen again to be used as a catalyst.
- A method for producing pentene. 8. Claim 7, wherein the carrier consists essentially only of the compound represented by the formula (1).
The method described in section. 9. The method according to claim 7, wherein the carrier comprises a mixture of the compound represented by formula (1) and a small amount of potassium carbonate.