JPS60132924A - Production of 4-methyl-1-pentene - Google Patents

Abstract

PURPOSE:To obtain the titled substance in high selectivity, by dimerizing propylene in the presence of a catalyst prepared by supporting Na, etc. on a carrier consisting essentially of a compound consisting of K2O and Al2O3, hydrogenating the resultant carrier supporting the compound, and bringing the hydrogenated catalyst precursor into contact with oxygen. CONSTITUTION:Propylene is dimerized to give the titled substance. In the process, the reaction is carried in the presence of a catalyst prepared by supporting Na, K or Na amide or K amide on a carrier consisting essentially of a compound expressed by the formula (0.5<=x<=11), if desired hydrogenating the carrier supporting the compound, and bringing the hydrogenated catalyst precursor into contact with oxygen or subjecting the resultant hydrogenated catalyst precursor to contact reaction with the propylene, and bringing the reacted carrier into contact with oxygen or bringing the carrier supporting the compound into contact with oxygen and then subjecting the resultant catalyst precursor to contact reaction with the propylene, and further bringing the reacted catalyst precursor into contact with oxygen at 140-180 deg.C under 20-200kg/cm<2>. The carrier is preferably a mixture of the compound expressed by the formula with a small amount of K2CO3. USE:A raw material for polymers having improved transparency, heat resistance, mechanical and electrical properties and chemical resistance.

Description

Detailed Description of the Invention The present invention dimerizes propylene to produce 4-methyl-1
- Concerning a new method for producing pentene.

By polymerizing 4-methyl-1-pentene, it has high transparency, heat resistance, mechanical and electrical properties,
A polymer with excellent chemical resistance is obtained, and it is also possible to obtain a polymer with excellent chemical resistance.
When manufacturing polyolefins by polymerizing α-olefins such as propylene, the transparency of polyolefin products,
It is a compound that exhibits particularly excellent performance as a comonomer for improving various physical properties such as environmental stress cracking resistance.

Conventionally, propylene is converted into 4-methyl-1 in the presence of alkali metals such as sodium and potassium.
- It is known that pentenes can be obtained (e.g. J,
Org, Ches, 30.3286 (1985), A. W. Shaw et al.

Furthermore, it is also known that 4-methyl-1-pentene can be obtained by dimerizing propylene using a catalyst in which an alkali metal is supported on a carrier. As carriers in this case, blephite, potassium carbonate, alkali metal silicates, alkali metal halides, magnesium sulfate, talc, and the like 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 t tans 4-methyl-2-pentene, 2-methyl'l-pentene, 2-methyl-2-pentene, l'hexeno, cis and tra
2-hexeno of ns and 3 of cis and trans
- It had the disadvantage that a large amount of hexeno was produced as a by-product. Furthermore, these isomers have similar 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 high cost of purification.
It also had the disadvantage of a large amount of damage.

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 stabilize, and many of them were inferior in terms of economic efficiency and stable operation. In addition, many of these known trimerization 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. There was a gradual loss of 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 the reactor, there is still a highly active catalyst remaining inside the reactor, and it is necessary to replace the catalyst. When removing this waste catalyst, 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.

The present inventors conducted intensive research to improve the t-defect in the conventionally known methods and catalysts as described above, and as a result, a method using a new catalyst system as disclosed in Japanese Patent Application Laid-Open No. 57-12F1426 was developed. I found it. In this method, a compound represented by 0.xAl2O3 (1) is used as a carrier for the reaction catalyst (wherein,
．． Propylene is trimerized by using as a catalyst a material on which sodium and/or sodium amide is supported (preferably in the range of l≦X≦5), and furthermore, a material which has been hydrogen-treated in advance. It is something that makes you 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 the selectivity for 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 discovered that the method for producing 4-methyl-1-pentene by trimerizing propylene could be improved by a completely unexpected method, and completed the present invention. I ended up doing it.

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, in the present invention, the compound represented by formula (1) is 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, is mixed in the compound without reacting. A material supported with at least one element or compound selected from the group of sodium, potassium, sodium amide, and potassium amide, or a material that has been subjected to hydrogen treatment in advance,
Furthermore, when oxygen is brought into contact with propylene and the like, surprisingly, the catalytic activity is not deactivated, but depending on the amount of oxygen in contact, the trimerization activity is reduced. and 4-methyl-1-
It has been found that the selectivity for 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 difluorination reaction of propylene.
) %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. It is characterized in that, after hydrogen treatment if desired, a catalyst is used which is brought into contact with oxygen.

Further, the second production method of the present invention is a method for producing 4-methyl-1-pentene by a dimerization reaction of propylene, in which the following formula (+)K20eXAI203...
... Sodium, potassium, sodium amide, A catalyst is prepared by carrying at least one element or compound selected from the group consisting of potassium amide, optionally treated with hydrogen, and then brought into contact with propylene, and then brought into contact with oxygen. It is characterized by being used as

Furthermore, the third production method of the present invention is a method for producing 4-methyl-1-pentene by difluorination reaction of propylene, in which a compound represented by F description (1) % formula % (1) (However, in the above formula, X is 0.5
≦X≦II) on which at least one element or compound selected from the group consisting of sodium, potassium, sodium amide, and potassium amide is supported. It is characterized in that, after hydrogen treatment if desired, it is 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.

The compound represented by the L-temperature 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, OH', KOR (
R1 is at least one selected from c, a linear or branched aliphatic hydrocarbon residue, a C6 to G30 aryl group, and an aralkyl group), KHCO3,
K2CO2 (including those containing crystal water), KH
”, KH2 (R2 is at least one selected from C1 to C2o linear or branched aliphatic hydrocarbon residues, C6 to C3O aryl groups, or aralkyl groups). seeds and alumina hydrates such as hydrogillite, bi7lite, boehmite, diaspor, α- and γ-alumina,
AI(OR3)3 (R' is a mixture of at least one selected from C3 to C20 linear or branched aliphatic hydrocarbon residues, C6 to C1O aryl groups or aralkyl groups), etc. and at least one aluminum-containing compound with a K/A I ratio of the predetermined X
Formula 9 (which is obtained by mixing the mixture so that In the compound represented by 1), X preferably takes a value in the range l≦X≦5.

The compound constituting the wood carrier is composed of Ni20 and Al2O3, but this is a convenient representation of the composition of the carrier produced when the charging composition of the raw reagent changes. , these constituent compounds do not exist as they are, but mainly as isolated compounds. Therefore, simply 2Q and Al2
Even if mixed with O3, it is a completely different type of carrier,
It is not possible to achieve the expected improvement in activity 1 selectivity when using the above carrier.

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,
X in the compound represented by formula (1) is 0.5≦X
A carrier having the same improvement effect as in the case of ≦11 can be obtained. In other words, when potassium carbonate is used, the excess! Although the first potassium carbonate remains unreacted in this carrier, the compound represented by the formula (1) and potassium carbonate can be handled in exactly the same way. In other words, as a carrier for the catalyst used in the method of the present invention, the compound represented by the above formula (1) may be used alone, or the compound represented by the above formula (1) may be used as a main component, A small amount of unreacted potassium carbonate used as a raw material for manufacturing the carrier may be mixed in. In this case, the remaining amount of potassium carbonate is equal to 3% of the compound represented by formula (1) above.
It is preferably 0% by weight or less.

In conventional catalysts for producing 4-methyl-1-pentene, the amount of sodium or potassium supported on the carrier is
Because the carrier itself is inert or has a small porosity, it is less than 5 wt%, usually about 1 to 3 wt%. If an attempt is made to support 5 wt% or more of sodium or potassium on these carriers, these alkali metals will adhere to the carrier surface in the form of mud, which will cause the catalyst to coagulate into lumps, which will be difficult to use industrially. Not only was it difficult to handle, but the activity of construction work was often extremely reduced. Furthermore, in order to adopt the fixed bed continuous flow method as a method for industrial reaction, it is necessary to make the catalyst into pellets, but conventionally, 4
Potassium carbonate, which is used as a phase in the catalyst for the production of methyl-1-pentene, cannot be pelletized because it does not have caking properties. Therefore, in most of the known catalysts, pellets are produced using graphite or the like as a paint, 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. On the other hand, the carrier used in the method of the present invention is of the formula (
The compound shown in 1) can absorb and carry large amounts of sodium, potassium, their hydrides, amides, etc. very quickly, so it maintains a very good dispersion state and can be used as is or as described below. Oxygen treatment according to the method of the present invention makes it possible to form catalysts that provide higher activity and selectivity in the trimerization 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 induction period at the start of the reaction.

It is very suitable for fully mixed mode reactions where the catalyst is introduced continuously with the propylene into the seed reactor.゛Also, 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 produced by mixing the above-mentioned raw materials by a known method such as extrusion molding or compression molding. By molding and firing, it is possible to make extremely strong pellets. The carrier thus obtained in the form of pellets can absorb and carry 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 trimerization reaction of propylene.

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 to a spherical shape of approximately LOSG+, a columnar shape, etc., depending on the shape and capacity of the reaction mode 1 reactor. These are the above formulas (
A method of crushing and classifying the lumps of the compound shown in 1), or kneading the raw materials, converting them into belenium by extrusion molding, compression molding, etc., and then firing them to produce products of the desired shape and size. be able to.

The method of supporting sodium and/or potassium on the above carrier can be carried out in exactly the same manner regardless of whether the carrier is powder or pellets, and can be carried out in the same manner without 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 on the carrier in vapor form, etc. can be employed. 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, and after being impregnated for 1 minute, the ammonia is evaporated. A common method is to allow the particles to be supported.

Sodium, potassium, sodium amide to carrier,
The supported amount of potassium amide, etc. is 0.1 to 20 wt% in terms of sodium atoms and/or potassium atoms.
is preferable; even if the supported amount is as high as 20w%, there are almost no side effects of tar or resinous substances, and since the supported amount can be increased, they will not be mixed into the reaction system. It exhibits strong resistance to moisture and other impurities, and can maintain high activity and selectivity for very long periods of time. Of course, even if the supported amount is as low as 0.1 to 1 wt%, the activity will only slightly decrease, and there will be no particular problem in implementing the method of the present invention.Generally, it is about 1-15 wt%. It is preferable to use a material supported in an amount of .

What was obtained in this way was the above-mentioned JP-A-57-
This includes the catalyst used in the method of No. 128428, which itself already has catalytic activity for the trimerization reaction of propylene. However, in the method of the present invention, these are treated as catalyst precursors. The catalyst precursor is optionally added to 1 e.g. 15 prior to oxygen treatment.
A good catalyst precursor can also be obtained by hydrogen treatment at a temperature range of 0 to 400° C. and a pressure of up to 100 Kg/cm 2 for 0.5 to 10 hours.

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, and the supported sodium, potassium,
Part or all of sodium amide, potassium amide, or their hydrides are converted into organic sodium compounds, organic potassium compounds, and the like. The catalytic reaction with propylene herein includes the use of the catalyst precursor itself as a propylene trimerization reaction catalyst by the method of JP-A-57-126428.

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, in this method, sodium supported on a carrier,
Potassium, sodium amide, potassium amide, or their hydrides, as well as organic sodium compounds and organic potassium compounds (hereinafter referred to as alkali metals), have extremely high reactivity, so they cannot be treated locally with excessive oxygen. Care must be taken to keep the oxygen content sufficiently low and to provide sufficient agitation to avoid damage. As the gas for diluting oxygen during oxygen treatment, it is preferable to use an inert gas such as nitrogen, helium, or argon.
The diluted oxygen concentration at that time is suitably 0.001 to 5.0% by volume. In addition, the processing temperature is usually -20 to 40
It is carried out at a temperature of 0°C, preferably 0 to 1O0°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 method of using dehumidified dry air. The saturated hydrocarbon to be used preferably has a boiling point higher than that of hebutane.

In the method of the present invention, the amount of oxygen brought into contact with the catalyst precursor in order to adjust the catalyst is determined by the method used (the first method described above).
．． (2nd and 3rd methods), the compound represented by formula (1) (1) (however, in the above formula, is 0.5
≦x6≦11)) is in the range of 0.1 to 20 mol %, preferably 0.3 to 10 mol %, based on the alkali metal supported on the carrier having as a main component. If the amount of oxygen treated through contact is less than 0.1 mol%, the effect of the contact treatment with oxygen according to the present invention cannot be fully exhibited.On the other hand, if the amount of oxygen treated through contact exceeds 20 mol%. Although the selectivity remains high in the engineering reaction, the activity decreases and becomes uneconomical.

In addition, in the first method and the second method, the oxygen contact treatment amount in the above range may be used as is,
In the third method, it is necessary that the sum of the amount of oxygen that is initially acted upon and the amount of oxygen that is then reacted with propylene to produce an organometallic compound and then subjected to contact treatment again is within the above range. There is no limit to the relative proportions 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, the propylene engineering activity and 4-methyl-1-pentene selectivity are significantly improved depending on the treated oxygen acid. The reason for this is not clear so far, but the oxygen treatment probably changes the electronic state around the active sites of alkali metals on the carrier, restricting the coordination of propylene and making it easier to engineer. This is probably because isomerization is 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 a point. It has been known that in conventional catalyst systems, the induction period is 10 to 15 hours even when it is short, and is several days or more when it is long.

In carrying out the propylene construction reaction 1 according to the method of the present invention, various catalytic reaction modes are eliminated, but a batch method using an autoclave, a semi-batch method, or a complete method in which a catalyst and raw propylene are continuously supplied to an autoclave are used. Mixed tank type rapid reaction method, the catalyst is packed in the reactor,
A fixed bed continuous reaction method or the like may be used in which the raw material propylene is passed therethrough.

In addition, suitable reaction conditions for the propylene conversion reaction of the present invention include a temperature range of 100 to 250°C, preferably 140 to 180°C, and a suitable pressure range of 20 to 250°C.
00Kg/crn'. - 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.

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

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, charcoal residue, etc. can be used within the range that is normally industrially possible. It is preferable to use the one removed by
Although it is better not to contain saturated hydrocarbons such as ethane, propane, and butane, there is no problem even if they are contained, and propylene mixed with a small amount of oxygen can also be used in the method of the present invention. It can be used effectively in some cases. Oxygen can be added to propylene to obtain a desired composition by dissolving oxygen in propylene under pressure. but,
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 # element coexisting in propylene is 2
A low A1 of ~5 ppm is preferable from the viewpoint of catalyst life. In this case, the cumulative amount of oxygen to the catalyst is 20m0
! % or less.

In any of these reaction modes, the reaction must be carried out using an aliphatic hydrocarbon such as hebutane, octane, dodecane, a mixture thereof, or a compound that does not cause side reactions in this reaction as a solvent. = T ability.

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

Example 1 KO)l + boehmite + 20 − x A120
3 (x = 0.H) 2G ・x Al2O3-+Cat, -1a on Ha 02 Na support
t-1 2C3H6+ C=G-C-C, -C 86 g of potassium hydroxide pellets (containing 15% water) were ground into fine powder, mixed well with 80 g of hemite, and placed in an alumina crucible. 12 under air atmosphere
Firing was performed at 00°C for 5 hours. After cooling, the fired product was taken out, placed in an alumina pot, and heated in a centrifugal ball mill for 2
Time pulverization was carried out, and a material finer than 60 eSh was used as a carrier.

This carrier Hg was placed in a three-necked flask containing 300 mJn.
The mixture was heated to 100° C. under a nitrogen gas atmosphere, and 6 g of sodium was added while stirring. After the addition, the temperature was raised to 200° C. and stirred for 1 hour to ensure uniform support.

The catalyst precursor leg obtained in this way is thoroughly dried and placed in a 1000aj capacity stainless steel autoclave that is purged with nitrogen, and to which n-nonane 1001 is to be added as a dispersion medium. It was connected to a tubular mercury manometer, and air dried with molecular sieve 3A was injected until the mercury column was 150 sag. The autoclave was treated with oxygen while rotating the stirrer until the reading on the manometer dropped to 130 mmHg, at which point the air in the autoclave was released and replaced with nitrogen gas.

Through this operation, an amount of oxygen corresponding to 1.5 mol % of the supported sodium was introduced.

Using the catalyst thus obtained, a propylene conversion reaction was carried out. 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 are recovered by distillation under reduced pressure, and the recovered reaction liquid has a boiling point higher than that of the remaining dimer after evaporating the propylene previously collected in the trap. When the parts were combined and analyzed by gas chromatography using a 50 m long glass capillary column coated with squalane, the propylene reaction rate was 49%.
and the selectivity for 4-methyl, -, l-pentene is 82
．． It was in %. Therefore, the activity per gram of this catalyst-per hour is:

0.84.5 (g -4-methyl-1-pentene/g
-Catalyst/hr) (Description of units will be omitted in the following examples).

, Comparative Example 1 The conversion reaction of propylene was carried out under 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 for 4-methyl-1-pentene was 89%, and the activity of this catalyst was 0.574.

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 113 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 was equivalent to 5 mol% of the supported potassium.Then, as in Example 1, the conversion of propylene was carried out.As a result of the analysis, the reaction rate of propylene was 38%, Selectivity for 4-methyl-1-pentene is 81%, activity is 0.814
Met.

Example 3 KOH+ AI<0jl)s K2O・XA1203(
X = 0.92) 20 @ XAl2O, -El on Na-Na support. at, -
3Ca't-3'' 2C386C=C-C-C-C In the same manner as in Example 1, 234 g of aluminum hydroxide manufactured by Wako Tsumugi and 180 g of potassium hydroxide were added to a body at 1200°C. The ratio was 0.82.The obtained carrier was pulverized in a centrifugal ball mill, and 80 esh or less pieces were used.

The mixture was added at a temperature of 200 to 220°C, and after the addition was completed, stirring was continued for 3 hours to allow Ha to be supported. The produced catalyst was a dark blue powder with very good dispersibility.

1'8 g of this powder was treated with oxygen in the same manner as in Example 1. However, the amount of oxygen introduced in the catalytic treatment was 2 mol % on the sodium scale.

, Using the catalyst thus obtained, Example 1,
In the same manner as above, 150 g of propylene was added and the reaction was carried out at 150°C for 8 hours. Perform the same □ post-treatment as in Example 1 and analyze by gas chromatography! □, the propylene reaction rate was 40%, and the 4-methyl-1-pentene selectivity was 89%. Catalytic activity was 0.40.

Example 4 2CO3+ Al(OH)3 →l(, o 11 x
Al2O3 (x=0.98)Na+ NH3+ NaI
20 on O3 @xAlO3! ! j Nap) 12
20 ・xAl2O302' 11 → Cat, -4 203H &""c-c-c-:5-)c 100 g of anhydrous potassium carbonate and 78.0 g of aluminum hydroxide were each added with particle size smaller than 16■esh.゛After mixing to make it sufficiently homogeneous, heat it at a temperature of 50°C.
The K/Al ratio of the 0-ice phase body obtained by baking for a time and preparing the carrier was determined by atomic absorption spectrometry, and it was found that K/AI=1.45. In addition, when calculated from the amount of carbon dioxide gas generated by acid decomposition of the formed carrier, 32g of unreacted potassium carbonate remained.
It was found that K2O*xAl2O3 is X=0.98.

15.0 g of this carrier and 1.0 g of sodium were placed in a stainless steel autoclave, into which 30 g of liquefied ammonia was removed under pressure, and after stirring at room temperature for 2 hours, ammonia and hydrogen produced by the reaction were released. 100 d of n-hebutane and 150.0 g of propylene were added to this autoclave, and the reaction was carried out at 180°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%. Activity was 0.377.

N-hebutane tootx (normal pressure) was sucked into the reactor, which was under reduced pressure due to the same post-treatment as in Example 1, and then dry air was sucked in until the pressure reached normal pressure. Oxygen treatment was performed by stirring for 30 minutes. 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 180° C. for 5 hours. Analysis of the product revealed that the propylene conversion rate was 32% and the 4-methyl-1-pentene selectivity was 80%. Also, the activity is 0.540
Met.

Comparative Example 2 A propylene conversion reaction was performed 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. . As a result of analysis, the reaction rate of propylene was 28%.
The selectivity for 4-methyl-1-pentene was 86%, and the activity of this catalyst 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 phase obtained in this way was used and treated with propylene as in Example 4. As a result, the propylene reaction rate was 28%, and the 4-methyl-1-pentene selectivity 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 180°C for 8 hours in the same manner as in Example 4. As a result of analysis, the reaction rate of propylene was 27%.
, the selectivity for 4-methyl-1-pentene was 88%, and the activity was 0.450.

Example 6 (See Example 1 for chemical reaction formula) Example 1. ! - 2% sodium was added to a carrier prepared in the same manner. 51 g of the obtained sodium support was placed in a glass 300 three-necked flask equipped with a stirrer equipped with blades that could sufficiently stir and mix the powder in a solvent-free state, and a three-way cock at the gas inlet and outlet, respectively. Collected in a nitrogen atmosphere F, a mixed gas consisting of 2% oxygen and 98% nitrogen was added at room temperature to 100% while stirring the contents.
The flow was carried out for 15 minutes at a rate of d/sin. The oxygen concentration in the gas discharged from the flask was measured and found to be 0.55.
%, it means that 2 mol% of the sodium amount was subjected to the oxygen introduction treatment.

15 g of this catalyst, 7100 ml of hebuta, and 150 g of propylene were placed in an autoclave and reacted at 160° C. for 7 hours. As a result, the propylene reaction rate was 29%.
, the selectivity for 4-methyl-1-pentene was 68%, and the activity was 0.385.

Example 7 2GO3+boehmite→, 0*xA1203(x=10.7)=20exA12°3-only for Na support. at, -7a 70g of potassium carbonate and 880g of boehmite are 18
After firing at a temperature of 00°C for 7 hours, a carrier having an AI/K of 10.7 was obtained. 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, sodium was added to 5% in the same manner as in Example 1.
wt% loading. 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. This catalyst 18
g, hebutane 1001, and propylene 150 g were added to an autoclave and reacted at 150°C for 6 hours. As a result of analysis, the reaction rate of propylene was 24%, 4-methyl-1
- Selectivity for pentene was 80%, activity 0.300.

Example 8 The carrier obtained in Example 7 was made to support 1 wt% of potassium in the same manner as in Example 1. 18 g of a catalyst obtained by reacting 5 mol % of potassium with oxygen, 100 ml of hebutane, and 150 g of propylene were placed in an autoclave, and the reaction was carried out at 150° C. for 15 hours.

As a result of analysis, the reaction rate was 12%, the selectivity for 4-methyl-1-pentene was 81%, and the activity was 0.01 (1).

Comparative Example 3 The conversion reaction of propylene was carried out under 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%, 4%.
-The selectivity of methyl-1-pentene was 85%, and the activity of this catalyst was 0.038. Example 9 KHCO3+Al2O3+ was mixed with O*
= 1.0) Na - → 20 x Al for Na support, 03 Town → Hydrogenated product 2 Cat, -9 Cat-9 2C3H,, C=C-C-C, -C 200 g of potassium carbonate and γ - 202 g of alumina were thoroughly mixed and fired at 1000°C for 7 hours to produce a carrier. Add 1.5 g of sodium to 15 g of this carrier and add 20
Support was carried out by stirring vigorously for 1 hour at 0°C. The total content of the obtained sodium carrier is 1! Put it in a stainless steel autoclave, add 100ml of n-hebutane as a solvent, raise the temperature to 180℃, and then hydrogen tear 0kg/c.
The mixture was pressurized to tn'G and stirred for 3 hours.

The pressure drop during this period was 2.3 kg/c rn'. After letting it cool and releasing the residual hydrogen, add 50g of propylene.
and the reaction was carried out at 180°C for 8 hours. After distilling off unreacted propylene, the two bottles produced, and hebutane under reduced pressure in the same manner as in the post-treatment of Example 1, 100 ml of fresh hebutane was added.
ml of dry air was added until the pressure inside the autoclave rose by 140 layers of mercury, and stirring was continued for 1 hour. This operation introduced 2 mol% oxygen of sodium. Propylene 15 in this autoclave
The reaction rate was 7B%, 4-methyl-1-
The selectivity for pentene was 86% and the activity was 0.849. 7 Example 10 t-BuOK+ C5ec Buo)3 A1,,,+
-K (AI(OBut) (OBu Town 3) 2K (A
I (OBut) (OBLIgt)3 )-2
0 @, Al2O3+4BuOBuK2(] ++ A
12O3 suspended-Na carrier 20 @ A1203-hGa
t, -10' 4 3 Cat, -10 When 112 g of t-butoxypotassium and 248 g of aluminum-5ec-butoxide are mixed at 70°C under a nitrogen atmosphere in 2001 t-butanol, Art-Comple/let is obtained.
Ste To6 K (AI (OBut) (OBII-
)3) Precipitated as a solid precipitate. After t-butanol as a solvent 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 firing was continued for an additional 3 hours.

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

Example 1
Oxygen treatment was performed in the same manner as above. The oxygen treatment amount was 2 mol% of sodium. Continuing with propylene 50
g was added thereto, and reaction was carried out at 1Ei at 0° C. for 2 hours to perform organometallation. Thereafter, unreacted propylene, the produced dimer, and the solvent hebutane 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 commercialize propylene. That is, 1ocal of hebutane and 150 g of propylene were added and the reaction was carried out at 150°C for 4 hours. As a result of analysis, the reaction rate was 37%, the selectivity for 4-methyl-1-pentene was 88%, and the activity was 0.688.

Example II K, C: 03+Al(OH)3→20·x Al,,
O3 (x = 1.0) a -Na supported 20 ・xAl2O3 2 1 → Cat, -11 138 g of anhydrous potassium carbonate and 158 g of aluminum hydroxide
A small amount of water was added to the mixture, and the mixture was kneaded and formed into pellets with a diameter of 1.8mm and a length of 5 to 8 inches using an extruder. This was baked at 1000° C. for 5 hours to obtain a carrier. Add 10% sodium to the entire amount of this carrier at 200°C in a nitrogen atmosphere f.
It was added so that it became ut% and was sufficiently stirred for 2 hours to make it support. The temperature was further raised to 400°C and heating was continued for an additional 2 hours. Sodium-loaded Pey obtained from Konyo
) 100g wo50 (N-Deca 73001, which had been sufficiently dehydrated, was placed in a glass flask made by Laj Yongkei, and was treated with oxygen in the same manner as in Example 1.The amount of oxygen treated was 2 mol% of sodium. Using the catalyst obtained in this way, we carried out a fixed-bed continuous flow reaction method for producing ribrobylene.That is, while maintaining the reaction temperature +50'' and the pressure 90 Kg/crn', propylene was heated at a liquid hourly space velocity ( LHSV) The reaction was carried out while introducing at 1.4 hr'. The reaction rate of propylene became steady in 20 hours and reached 38%. 4-Methyl-1 in the product
- Although the zero reaction was carried out continuously with a pentene content of 93%, the half-life of the activity, that is, the time required for the propylene conversion to decrease by half from the highest value, exceeded 1500 hours.

Patent Applicant Nippon Oil Co., Ltd. 1 Procedure Supplement JE (Method) 1. Indication of Case 1981 Patent Application No. 2035o8
Gin 2. Name of the invention 4. Process for producing methyl-1-hentene 3. Person making the amendment 4. Agent address 5-9-20 1-9 Akasaka, Minato-ku, Tokyo. Date of amendment order.

Claims (1)

[Claims] (1) In a method for producing 4-methyl-1-pentene by dimerization reaction of 7'robilene, the following formula (1
) %Compound represented by the formula %() (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. A method for producing 4-methyl-1-pentene, which is characterized in that, after optional hydrogen treatment, a catalyst is used in contact with oxygen. (2) The method according to claim 1, wherein the carrier consists essentially only of the compound represented by the formula (1). (3) The carrier is represented by the formula (1). The method according to claim 1, which comprises a mixture of a compound containing 4-methyl-1 and a small amount of potassium carbonate.
- In the method for producing pentene, a compound represented by F description (1) % formula % (1) (however, in the above formula, X is 0.5
≦X≦II) on which at least one element or compound selected from the group consisting of sodium, potassium, sodium amide, and potassium amide is supported. A method for producing 4-methyl-1-pentene, which comprises using as a catalyst a catalyst obtained by subjecting the product to hydrogen treatment if desired, followed by contact reaction with propylene, and then contact with oxygen. (5) The method according to claim 4, wherein the carrier consists essentially only of the compound represented by the formula (1). (6) The carrier is represented by the formula (1). In the method (7) for producing 4-methyl-l-pentene by a dimerization reaction of propylene, the method according to claim 4 is a method comprising a mixture of a compound of A compound represented by the following formula (1) % formula % (1) (However, in the above formula, X is 0.5
≦X≦11), in which at least one element or compound selected from the group consisting of sodium, potassium, sodium amide, and potassium amide is supported. 4-Methyl-1-, which is characterized in that, after hydrogen treatment if desired, contact with oxygen, further contact reaction with propylene, and then contact with oxygen again is used as a catalyst.
Method of manufacturing pentene. (8) The method according to claim 7, wherein the carrier consists essentially only of the compound represented by the formula (1). (9) The MiJ carrier is represented by the formula (1). A method according to claim 7, consisting of a mixture of the indicated compound and a small amount of potassium carbonate.