JPS63303932A - Production of 4-methyl-1-pentene - Google Patents
Production of 4-methyl-1-penteneInfo
- Publication number
- JPS63303932A JPS63303932A JP62141151A JP14115187A JPS63303932A JP S63303932 A JPS63303932 A JP S63303932A JP 62141151 A JP62141151 A JP 62141151A JP 14115187 A JP14115187 A JP 14115187A JP S63303932 A JPS63303932 A JP S63303932A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- pentene
- carbon atoms
- alkali metal
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 title claims description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 10
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 6
- 230000000447 dimerizing effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- LGAQJENWWYGFSN-PLNGDYQASA-N (z)-4-methylpent-2-ene Chemical compound C\C=C/C(C)C LGAQJENWWYGFSN-PLNGDYQASA-N 0.000 abstract description 7
- 238000006471 dimerization reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 3
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 6
- -1 aliphatic alcohols Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- WTJKUFMLQFLJOT-UHFFFAOYSA-N heptadecan-9-one Chemical compound CCCCCCCCC(=O)CCCCCCCC WTJKUFMLQFLJOT-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はプロピレンの二量化による４−メチル−１−ペ
ンテンの製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing 4-methyl-1-pentene by dimerization of propylene.
４−メチル−１−ペンテンは耐熱性ポリマーの原料、ポ
リオレフィン用のコモノマー等とじて工業的に極めて有
用である。4-Methyl-1-pentene is extremely useful industrially as a raw material for heat-resistant polymers, a comonomer for polyolefins, and the like.
〈従来の技術〉
プロピレンを二量化して４−メチル−ニーペンテンを製
造する方法はよく知られており２種種の触媒が用いられ
ている。またこのプロピレン二量化触媒として無水炭酸
カリウム担体にアルカリ金属を担持した触媒を用いるこ
とも知られている（特公昭４３−２５３４４号公報）。<Prior Art> The method for producing 4-methyl-neepentene by dimerizing propylene is well known, and two types of catalysts are used. It is also known to use a catalyst in which an alkali metal is supported on an anhydrous potassium carbonate carrier as the propylene dimerization catalyst (Japanese Patent Publication No. 43-25344).
しかしながらこれらの方法においては、目的の４−メチ
ル−１−ペンテンの他にかなりの４−メチル−２−ペン
テンが副生ずる。４−メチル−２−ペンテンは４−メチ
ル−１−ペンテンとその沸点が非常に近いために２両者
を分離して４−メチル−１−ペンテンを精製するために
は多段の蒸留塔及び多量のスチームが必要となる。However, in these methods, in addition to the desired 4-methyl-1-pentene, a considerable amount of 4-methyl-2-pentene is produced as a by-product. Since the boiling points of 4-methyl-2-pentene and 4-methyl-1-pentene are very close, it takes multiple distillation columns and a large amount of water to separate the two and purify 4-methyl-1-pentene. Steam is required.
〈発明が解決しようとする問題点〉
本発明はかかる従来の技術の欠点、即ちプロピレンを二
量化して４−メチル−１−ペンテンを製造する方法にお
いて４−メチル−２−ペンテンの副生ヲ抑制し、４−メ
チル−１−ペンテンを選択的に得る工業的に有利な方法
を提供することを目的とするものである。<Problems to be Solved by the Invention> The present invention solves the drawbacks of the conventional techniques, namely, the by-product of 4-methyl-2-pentene in the method of dimerizing propylene to produce 4-methyl-1-pentene. The object of the present invention is to provide an industrially advantageous method for selectively obtaining 4-methyl-1-pentene.
く問題点を解決するための手段〉
本発明者らはプロピレンを三量化して４−メチル−１−
ペンテンを製造する方法において。Means for Solving the Problems〉 The present inventors trimerized propylene to produce 4-methyl-1-
In a method of manufacturing pentene.
４−メチル−２−ペンテンの副生を抑制し、４−メチル
−１−ペンテンを選択性よく得るための工業的に有利な
方法について鋭意研究を行い。We conducted extensive research on an industrially advantageous method for suppressing the by-product of 4-methyl-2-pentene and obtaining 4-methyl-1-pentene with good selectivity.
本発明に到達したものである。This has led to the present invention.
すなわち本発明はプロピレンを三量化し、４−メチル−
１−ペンテンを製造する方法において、無水炭酸カリウ
ム担体にアルカリ金属を担持した後、炭素数１〜１０の
アルコール類、炭素数６〜１０のフェノール類、 炭素
数３〜３０のアミン類、炭素数２〜２０のエーテル類及
び炭素数３〜２０のケトン類から選ばれる少な（とも１
種以上の化合物で処理したものを触媒として用いて反応
を行うことを特徴とする４−メチル−１−ペンテンの製
造法である。That is, the present invention trimerizes propylene to produce 4-methyl-
In the method for producing 1-pentene, after supporting an alkali metal on an anhydrous potassium carbonate carrier, alcohols having 1 to 10 carbon atoms, phenols having 6 to 10 carbon atoms, amines having 3 to 30 carbon atoms, and carbon atoms A small amount selected from ethers having 2 to 20 carbon atoms and ketones having 3 to 20 carbon atoms (both 1
This is a method for producing 4-methyl-1-pentene, characterized in that the reaction is carried out using as a catalyst a product treated with more than one type of compound.
本願発明方法に用いられる担持触媒に使用するアルカリ
金属としてはリチウム、ナトリウム。The alkali metals used in the supported catalyst used in the method of the present invention include lithium and sodium.
カリウム、ルビジウム、セシウム等が挙げられるが、好
ましくはナトリウム、カリウムが用いられる。Examples include potassium, rubidium, cesium, etc., but sodium and potassium are preferably used.
無水炭酸カリウム担体にアルカリ金属を担持する方法と
しては液体アンモニアにアルカリ金属を溶解して担体に
含浸する方法、アルカリ金属を担体に蒸着させる方法な
どが挙げられるが。Examples of methods for supporting an alkali metal on an anhydrous potassium carbonate carrier include a method in which the alkali metal is dissolved in liquid ammonia and impregnated into the carrier, and a method in which the alkali metal is vapor-deposited on the carrier.
好ましい例としてはアルカリ金属の融解する温度で担体
とアルカリ金属を撹拌する方法が挙げられる。A preferred example is a method in which the carrier and the alkali metal are stirred at a temperature at which the alkali metal melts.
アルカリ金属の担持量は好ましくは無水炭酸カリウム担
体に対して０．５〜１０重量％、さらに好ましくは１〜
５重量％である。The amount of alkali metal supported is preferably 0.5 to 10% by weight, more preferably 1 to 10% by weight based on the anhydrous potassium carbonate carrier.
It is 5% by weight.
次に担持物の処理に使用する化合物について説明する。Next, the compounds used for treating the supported material will be explained.
本願発明方法において担持物の処理に使用する化合物は
炭素数１〜１０のアルコール類、炭素数６〜１０のフェ
ノール類、炭素数３〜３０のアミン類、炭素数２〜２０
のエーテル類、炭素数３〜２０のケトン類から選ばれる
少なくとも１種以上の化合物である。The compounds used in the treatment of the supported material in the method of the present invention include alcohols having 1 to 10 carbon atoms, phenols having 6 to 10 carbon atoms, amines having 3 to 30 carbon atoms, and amines having 2 to 20 carbon atoms.
is at least one compound selected from ethers and ketones having 3 to 20 carbon atoms.
炭素数１〜１０のアルコール類としてはエタノール、ブ
タノール、オクタツール等が挙げられるが、好ましくは
炭素数１〜１０の脂肪族アルコール類が用いられる。Examples of alcohols having 1 to 10 carbon atoms include ethanol, butanol, octatool, etc., but aliphatic alcohols having 1 to 10 carbon atoms are preferably used.
炭素数６〜１０のフェノール類としてはフェノール、ク
レゾール、キシレノール等が挙げられるが、好ましくは
フェノールが用いられる。Examples of phenols having 6 to 10 carbon atoms include phenol, cresol, xylenol, etc., and phenol is preferably used.
炭素数３〜３０のアミン類としてはイソブチルアミン、
Ｎ−メチルピペリジン、トリオクチルアミン、アニリン
等が挙げられるが、好ましくは炭素数３〜３０の脂肪族
３級アミンあるいは炭素数３〜３０の脂環式３級アミン
が用いられる。Examples of amines having 3 to 30 carbon atoms include isobutylamine,
Examples include N-methylpiperidine, trioctylamine, aniline, etc., but preferably an aliphatic tertiary amine having 3 to 30 carbon atoms or an alicyclic tertiary amine having 3 to 30 carbon atoms is used.
炭素数２〜２０のエーテル類としてはジブチルエーテル
、ジオクチルエーテル、テトラヒドロフラン、ジフェニ
ルエーテル等が挙げられる。Examples of the ethers having 2 to 20 carbon atoms include dibutyl ether, dioctyl ether, tetrahydrofuran, and diphenyl ether.
炭素数３〜２０のケトン類としてはアセトン。Acetone is a ketone having 3 to 20 carbon atoms.
メチルエチルケトン、ジオクチルケトン、アセトフェノ
ン等が挙げられる。Examples include methyl ethyl ketone, dioctyl ketone, acetophenone, and the like.
さらに好ましくは炭素数１〜１０の脂肪族アルコール、
炭素数３〜３０の脂肪族３級アミン、炭素数３〜３０の
脂環式３級アミンから選ばれる少くとも１種以上の化合
物が用いられる。More preferably, an aliphatic alcohol having 1 to 10 carbon atoms,
At least one compound selected from aliphatic tertiary amines having 3 to 30 carbon atoms and alicyclic tertiary amines having 3 to 30 carbon atoms is used.
これらの化合物は通常単独で用いられるが。Although these compounds are usually used alone.
場合によっては２種以上の化合物を混合して用いてもよ
い。また同一化合物内にヒドロキシル基、アミン基、エ
ーテル基、カルボニル基より選ばれる２種以上の置換基
を有する化合物を用いてもよい。In some cases, two or more compounds may be used in combination. Further, a compound having two or more types of substituents selected from a hydroxyl group, an amine group, an ether group, and a carbonyl group within the same compound may be used.
これらの化合物で担持物を処理する場合は。When treating supports with these compounds.
通常不活性ガス雰囲気下あるいは乾燥した炭化水素など
の溶媒中で行う。不活性ガスの例としては窒素などであ
る。It is usually carried out under an inert gas atmosphere or in a dry solvent such as a hydrocarbon. An example of an inert gas is nitrogen.
炭化水素の例としては、炭素数５〜８の飽和炭化水素あ
るいは原料プロピレンなどが挙げられる。担持物をこれ
らの化合物で処理する方法の例としては、゛前記の炭化
水素溶媒にこれらの化合物を溶解し溶液とした後、一時
的に担持物に含浸させる方法、一時的に通液接触させる
方法、あるいは、溶液で担持物を処理した後間−系内に
プロピレンを仕込んでバッチ反応を行う方法などが挙げ
られる。溶液中のこれらの化合物の濃度の例は好ましく
は０．５〜１００重量％。Examples of hydrocarbons include saturated hydrocarbons having 5 to 8 carbon atoms and raw material propylene. Examples of methods for treating a supported material with these compounds include ``dissolving these compounds in the hydrocarbon solvent described above to form a solution, and then temporarily impregnating the supported material, and temporarily bringing the solution into contact with a liquid. Alternatively, a method may be used in which a supported material is treated with a solution and then propylene is charged into the system to perform a batch reaction. Examples of concentrations of these compounds in solution are preferably 0.5 to 100% by weight.
さらに好ましくは１〜１０重量％である。これらの化合
物の添加量の例としては、無水炭酸カリウム担体に担持
したアルカリ金属のモル数に対して、好ましくは０．０
１〜１．０モル、さらに好ましくは０．０５〜０．５モ
ルである。More preferably, it is 1 to 10% by weight. As an example of the amount of these compounds added, it is preferably 0.0 based on the number of moles of the alkali metal supported on the anhydrous potassium carbonate carrier.
The amount is 1 to 1.0 mol, more preferably 0.05 to 0.5 mol.
次に本発明の実施方法について説明する。反応方法は特
に限定されないが、粉末触媒をオートクレーブに充填し
て行うバッチ反応、あるいは流動床方式、固定床方式の
流通反応などが挙げられる。Next, a method of implementing the present invention will be explained. The reaction method is not particularly limited, but examples include a batch reaction performed by filling an autoclave with a powdered catalyst, and a flow reaction using a fluidized bed system or a fixed bed system.
反応温度は通常５０〜３００°Ｃが採用され、好ましく
は１００〜２００°Ｃが採用される。反応圧力は通常大
気圧〜３００ｋｇ ７ｃｍ２が採用され、好ましくは３
０〜２００ ｋｇ／ａｍ”が採用される。The reaction temperature is usually 50 to 300°C, preferably 100 to 200°C. The reaction pressure is usually atmospheric pressure to 300 kg 7 cm2, preferably 300 kg 7 cm2.
0 to 200 kg/am” is adopted.
バッチ反応において触媒の濃度としては通常１〜５０重
量％が採用され、好ましくは１〜３０重量％が採用され
る。また反応時間は通常１〜１５時間であり、好ましく
は２〜５時間である。In batch reactions, the catalyst concentration is usually 1 to 50% by weight, preferably 1 to 30% by weight. Further, the reaction time is usually 1 to 15 hours, preferably 2 to 5 hours.
流通反応において、プロピレン供給速度は通常ＬＨ３Ｖ
で０．０５〜１５ ｈｒ−’であり、好ましくは０．１
〜５ ｈｒ−１が採用される。In the flow reaction, the propylene feed rate is usually LH3V
from 0.05 to 15 hr-', preferably 0.1
~5 hr−1 is adopted.
以下に実施例によって本発明方法をさらに詳細に説明す
るが２本発明は以下の実施例によって制約されるもので
はない。The method of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples.
〈実施例〉
比較例１
直径４ｍｍの円柱状無水炭酸カリウム２４４ｇを硬質ガ
ラス製フラスコに入れ窒素雰囲気下３５０℃で２時間乾
燥し２次いで金属す）ｌラム６．８ｇを加え、窒素気流
中２５０°Ｃで５時間撹拌し、触媒を調製した。<Example> Comparative Example 1 244 g of cylindrical anhydrous potassium carbonate with a diameter of 4 mm was placed in a hard glass flask and dried at 350° C. for 2 hours under a nitrogen atmosphere. Then, 6.8 g of metal ram was added, and the flask was heated at 250 g in a nitrogen stream. The catalyst was prepared by stirring at °C for 5 hours.
以下（こ、流通反応装置で反応を行った。The following reaction was carried out in a flow reactor.
内径１５ｔｎｍのステンレス製反応管に触媒を９１ｍ１
充填し、窒素雰囲気とする。次いで反応管を加熱し触媒
を温度１５３°Ｃに保った。圧力１０８ｋｇ／ｃｍ２に
おいて液化プロピレンを７０ ｍｌ ／ｈで流通させた
。２１時間後反応液を分析した。分析はガスクロマトグ
ラフィーで行った。反応結果は、プロヒレン転化率２１
％、４−メチル−１−ペンテン（以下４ＭＩＰと記す）
選択率７７．２％、４−メチル−２−ペンテン（以下４
Ｍ２Ｐと記載）選択率１１．０％であった。４ＭＩＰ選
択率と４Ｍ２Ｐ選択率の比は４ＭＩ Ｐ／４Ｍ２Ｐ＝７
であった。さらに１４７．５時間後反応液を分析した。91ml of catalyst was placed in a stainless steel reaction tube with an inner diameter of 15tnm.
Fill with nitrogen atmosphere. The reaction tube was then heated to maintain the catalyst at a temperature of 153°C. Liquefied propylene was flowed at a rate of 70 ml/h at a pressure of 108 kg/cm2. After 21 hours, the reaction solution was analyzed. Analysis was performed by gas chromatography. The reaction result was a prohylene conversion rate of 21
%, 4-methyl-1-pentene (hereinafter referred to as 4MIP)
Selectivity 77.2%, 4-methyl-2-pentene (hereinafter 4
(Described as M2P) The selectivity was 11.0%. The ratio of 4MIP selection rate and 4M2P selection rate is 4MIP/4M2P=7
Met. After a further 147.5 hours, the reaction solution was analyzed.
反応結果は、プロピレン転化率１５％、４ＭＩＰ選択率
７７．０％、４Ｍ２Ｐ選択率１２．６９６であった。４
ＭＩＰ選択率と４Ｍ２Ｐ選択率の比は４ＭＩ Ｐ／４Ｍ
２Ｐ＝ ６であった。The reaction results were a propylene conversion rate of 15%, a 4MIP selectivity of 77.0%, and a 4M2P selectivity of 12.696. 4
The ratio of MIP selection rate and 4M2P selection rate is 4MIP/4M
2P=6.
実施例１ 比較例１と同様にして、触媒を調製した。Example 1 A catalyst was prepared in the same manner as in Comparative Example 1.
比較例１と同様な反応管に触媒を１００ｍ１充填し、窒
素雰囲気とした。次にＮ−メチルピペリジン４．５ｇ、
乾燥へブタン２Ｑｍｌ、プロピレン３００ ｍｌの混合
液を触媒の充填された反応管に注入し、８０°Ｃ、１０
０ｋｇ ７ｃｍ２ ニおいて４時間触媒を処理した。A reaction tube similar to that in Comparative Example 1 was filled with 100 ml of catalyst and set in a nitrogen atmosphere. Next, 4.5 g of N-methylpiperidine,
A mixture of 2 Q ml of dry hebutane and 300 ml of propylene was injected into a reaction tube filled with catalyst, and heated at 80°C for 10
The catalyst was treated for 4 hours at 0 kg 7 cm2.
次いで比較例１と同様にプロピレン二量化反応を行った
。触媒温度を１５１°Ｃに保った。圧力１０３ ｋｇ
７ｃｍ２ において液化プロピレンを６８ ｍｌ ／ｈ
で流通させた。２１時間後反応液を分析した。分析はガ
スクロマトグラフィーで行った。反応結果は、プロピレ
ン転化率３２％４ＭＩＰ選択率８４．１ム ４Ｍ２Ｐ選
択率２．３％であった。Next, a propylene dimerization reaction was carried out in the same manner as in Comparative Example 1. Catalyst temperature was maintained at 151°C. pressure 103 kg
68 ml/h of liquefied propylene in 7 cm2
It was distributed in After 21 hours, the reaction solution was analyzed. Analysis was performed by gas chromatography. The reaction results were a propylene conversion rate of 32%, a 4MIP selectivity of 84.1%, and a 4M2P selectivity of 2.3%.
４ＭＩＰ選択率と４Ｍ２Ｐ選択率の比は４ＭＩＰ／４Ｍ
２Ｐ＝３７であった。さらに１５３時間後反応液を分析
した。The ratio of 4MIP selectivity and 4M2P selectivity is 4MIP/4M
2P=37. After a further 153 hours, the reaction solution was analyzed.
反応結果は、プロピレン転化率３１％、４ＭＩＰ選択率
８３．５％、４Ｍ２Ｐ選択率２．７９６であった。４
ＭＩ Ｐ選択率と４Ｍ２Ｐ選択率の比は。The reaction results were a propylene conversion rate of 31%, a 4MIP selectivity of 83.5%, and a 4M2P selectivity of 2.796. 4
What is the ratio between MI P selectivity and 4M2P selectivity?
４ＭＩ Ｐ／４Ｍ２ Ｐ＝３１であった。4MI P/4M2 P=31.
実施例２〜９
実施例１で用いたＮ−メチルピペリジンのかわりに表１
に記載した化合物を用いる以外は実施例１と同月な方法
で触媒を調製した。ついで実施例１と同じ条件でプロピ
レンの二型化反応を行い２表１に示す結果を得た。Examples 2-9 Table 1 instead of N-methylpiperidine used in Example 1
A catalyst was prepared in the same manner as in Example 1 except that the compound described in Example 1 was used. Next, a dimorphic reaction of propylene was carried out under the same conditions as in Example 1, and the results shown in Table 1 were obtained.
表 １ （注）反応成績は反応開始２０時間後の値である。Table 1 (Note) Reaction results are values 20 hours after the start of the reaction.
以上の実験結果から解るように、高い４ＭＩＰの選択率
を得た。特に４ＭＩＰと４Ｍ２Ｐの選択率の比４ＭＩＰ
／４Ｍ２Ｐが大巾に向上し。As can be seen from the above experimental results, a high selectivity of 4MIP was obtained. Especially the ratio of selectivity between 4MIP and 4M2P 4MIP
/4M2P has been greatly improved.
反応物の蒸留等による分離が容易になることを示してい
る。This indicates that the reaction products can be easily separated by distillation or the like.
〈発明の効果〉
以上の如く本発明によりプロピレンを三量化し、４−メ
チル−１−ペンテンを製造する方法において、４−メチ
ル−２−ペンテンをほとんど副生ずることなく、４−メ
チル−１−ペンテンを高選択率で製造できるようになっ
た。<Effects of the Invention> As described above, in the method of trimerizing propylene to produce 4-methyl-1-pentene according to the present invention, 4-methyl-1-pentene is produced almost without producing 4-methyl-2-pentene as a by-product. Pentene can now be produced with high selectivity.
Claims (1)
造する方法において、無水炭酸カリウム担体にアルカリ
金属を担持した後、炭素数１〜１０のアルコール類、炭
素数６〜１０のフェノール類、炭素数３〜３０のアミン
類、炭素数２〜２０のエーテル類、炭素数３〜２０のケ
トン類から選ばれる少なくとも１種以上の化合物で処理
したものを触媒として用いて反応を行うことを特徴とす
る４−メチル−１−ペンテンの製造法。In a method for producing 4-methyl-1-pentene by dimerizing propylene, after supporting an alkali metal on an anhydrous potassium carbonate carrier, alcohols having 1 to 10 carbon atoms, phenols having 6 to 10 carbon atoms, carbon The reaction is carried out using as a catalyst a compound treated with at least one compound selected from amines having 3 to 30 carbon atoms, ethers having 2 to 20 carbon atoms, and ketones having 3 to 20 carbon atoms. A method for producing 4-methyl-1-pentene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62141151A JP2608722B2 (en) | 1987-06-04 | 1987-06-04 | Method for producing 4-methyl-1-pentene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62141151A JP2608722B2 (en) | 1987-06-04 | 1987-06-04 | Method for producing 4-methyl-1-pentene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63303932A true JPS63303932A (en) | 1988-12-12 |
| JP2608722B2 JP2608722B2 (en) | 1997-05-14 |
Family
ID=15285325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62141151A Expired - Lifetime JP2608722B2 (en) | 1987-06-04 | 1987-06-04 | Method for producing 4-methyl-1-pentene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2608722B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04266834A (en) * | 1991-02-20 | 1992-09-22 | Kobe Steel Ltd | Production of dialkylnaphthalene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993303A (en) * | 1973-01-11 | 1974-09-05 | ||
| JPS60215638A (en) * | 1984-04-11 | 1985-10-29 | Nippon Oil Co Ltd | Preparation of 4-methyl-1-pentene |
| JPS61106526A (en) * | 1984-10-31 | 1986-05-24 | Nippon Oil Co Ltd | Production of 4-methyl-1-pentene |
-
1987
- 1987-06-04 JP JP62141151A patent/JP2608722B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993303A (en) * | 1973-01-11 | 1974-09-05 | ||
| JPS60215638A (en) * | 1984-04-11 | 1985-10-29 | Nippon Oil Co Ltd | Preparation of 4-methyl-1-pentene |
| JPS61106526A (en) * | 1984-10-31 | 1986-05-24 | Nippon Oil Co Ltd | Production of 4-methyl-1-pentene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04266834A (en) * | 1991-02-20 | 1992-09-22 | Kobe Steel Ltd | Production of dialkylnaphthalene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2608722B2 (en) | 1997-05-14 |
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