JP2006326418A - DIMERIZATION CATALYST OF alpha-OLEFIN AND MANUFACTURING METHOD OF alpha-OLEFIN DIMER - Google Patents
DIMERIZATION CATALYST OF alpha-OLEFIN AND MANUFACTURING METHOD OF alpha-OLEFIN DIMERInfo
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- JP2006326418A JP2006326418A JP2005150631A JP2005150631A JP2006326418A JP 2006326418 A JP2006326418 A JP 2006326418A JP 2005150631 A JP2005150631 A JP 2005150631A JP 2005150631 A JP2005150631 A JP 2005150631A JP 2006326418 A JP2006326418 A JP 2006326418A
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- olefin
- catalyst
- anhydrous potassium
- graphite
- potassium compound
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 27
- 239000004711 α-olefin Substances 0.000 title claims abstract description 27
- 239000000539 dimer Substances 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 150000003112 potassium compounds Chemical class 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 238000004438 BET method Methods 0.000 claims abstract description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 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 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 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
本発明はα−オレフィン二量化用触媒に関する。 The present invention relates to an α-olefin dimerization catalyst.
４−メチルー１−ペンテンに代表されるα−オレフィンの二量体又は共二量体は、ポリオレフィン製造用の単量体として利用されている。α−オレフィンの二量化反応又は共二量化反応によって相応する二量体又は共二量体を製造するための触媒として多くの塩基性触媒が従来から提案されている。しかし、これらの触媒は活性が低いこと、目的物質への選択性が充分に高くないこと、又初期活性が高くても触媒寿命が充分ではないなどの欠点があった。これらの点を改良した触媒が特開昭５８−１１４７３７号公報で提案されているが、未だ触媒寿命の改良が求められていた（特許文献１）。
本発明の課題は、寿命の改良されたα−オレフィン二量化用触媒を提案することである。 An object of the present invention is to propose an α-olefin dimerization catalyst having an improved lifetime.
本発明は次のα−オレフィン二量化用触媒に関する。
（１）アルカリ金属（A）を、無水カリウム化合物を主成分とする担体（B）に担持した触媒において該担体(B)がＢＥＴ法で測定した比表面積が２０m2/ｇ以上であるグラファイト（ｃ）を含むことを特徴とするα−オレフィン二量化用触媒。
（２）アルカリ金属（A）を、無水カリウム化合物を主成分とする担体（B）に担持した触媒において
(i)該アルカリ金属（A）がナトリウム金属（ａ）８０グラム原子％以上からなること、及び
(ii)該担体(B)が、グラファイト（ｃ）及び無水カリウム化合物（ｄ）から構成され、且つ該グラファイト（ｃ）の含有率が該無水カリウム化合物（ｄ）に対して０．１ないし３重量％の範囲である圧縮成形粒状担体であり、グラファイト（ｃ）のＢＥＴ法で測定した比表面積が２０m2/ｇ以上であること。
を特徴とするα−オレフィン二量化用触媒。
The present invention relates to the following α-olefin dimerization catalyst.
(1) A graphite (c) having a specific surface area of 20 m2 / g or more measured by the BET method in a catalyst in which an alkali metal (A) is supported on a support (B) containing an anhydrous potassium compound as a main component. A catalyst for dimerization of α-olefins.
(2) In a catalyst in which an alkali metal (A) is supported on a support (B) mainly composed of an anhydrous potassium compound
(i) the alkali metal (A) is composed of 80 g atom% or more of sodium metal (a), and
(ii) The carrier (B) is composed of graphite (c) and an anhydrous potassium compound (d), and the content of the graphite (c) is 0.1 to 3 relative to the anhydrous potassium compound (d). It is a compression-molded granular carrier in the range of% by weight, and the specific surface area of graphite (c) measured by the BET method is 20 m2 / g or more.
An α-olefin dimerization catalyst characterized by the above.
本発明のα−オレフィン二量化用触媒は従来の触媒に比べて触媒の寿命が永く、工業的に有用である。 The α-olefin dimerization catalyst of the present invention has a longer catalyst life compared to conventional catalysts and is industrially useful.
本発明の触媒の構成成分の一つであるアルカリ金属(A)は、ナトリウム金属（ａ）８０グラム原子％以上、好ましくはナトリウム金属（ａ）９０原子％以上からなる。ここでアルカリ金属とはイオン化されていない金属である。 The alkali metal (A), which is one of the constituent components of the catalyst of the present invention, comprises sodium metal (a) at 80 g atom% or more, preferably sodium metal (a) at 90 atom% or more. Here, the alkali metal is a metal that is not ionized.
また、担持成分中の該アルカリ金属の担体(B)への担持割合は、担体(B)の構成成分の該無水カリウム化合物（ｄ）に対して通常０．５ないし１０重量％、好ましくは１ないし５重量％の範囲である。 The supporting ratio of the alkali metal to the carrier (B) in the carrier component is usually 0.5 to 10% by weight, preferably 1%, based on the anhydrous potassium compound (d) as a component of the carrier (B). Or in the range of 5% by weight.
本発明の触媒の他の構成成分である担体（B）は、該無水カリウム化合物（ｄ）を主成分とする担体であり、ＢＥＴ法で測定した比表面積が２０m2/ｇ以上であるグラファイト（ｃ）を必須成分として含む。グラファイト（ｃ）のＢＥＴ法で測定した比表面積は好ましくは５０〜３００m2/ｇ、より好ましくは１００〜２００m2/ｇである。担体（B）は無水カリウム化合物（ｄ）とグラファイト（ｃ）を含む圧縮成形粒状担体である。グラファイト（ｃ）のＢＥＴ法で測定した比表面積が２０m2/ｇ未満ではこの担体から調製された触媒は寿命が短くなり、好ましくない。グラファイト（ｃ）平均粒径は特に限定はないが、１０μｍ以下、好ましくは０．１〜５μｍである。 The support (B), which is another component of the catalyst of the present invention, is a support mainly composed of the anhydrous potassium compound (d), and has a specific surface area measured by the BET method of 20 m 2 / g or more (c ) As an essential component. The specific surface area of graphite (c) measured by the BET method is preferably 50 to 300 m2 / g, more preferably 100 to 200 m2 / g. The carrier (B) is a compression-molded granular carrier containing an anhydrous potassium compound (d) and graphite (c). If the specific surface area of the graphite (c) measured by the BET method is less than 20 m2 / g, the catalyst prepared from this support has a short life and is not preferable. The average particle diameter of graphite (c) is not particularly limited, but is 10 μm or less, preferably 0.1 to 5 μm.
この担体（B）に含まれるグラファイト（ｃ）の含有率は該無水カリウム化合物（ｄ）に対して０．１ないし３重量％、好ましくは０．５ないし２重量％である。グラファイト（ｃ）の含有率が０．１重量％未満の場合においては、触媒寿命及びα−オレフィンの二量化への選択率が低下するようになる。また該グラファイト（ｃ）の含有率が３重量％よりも大きくなっても、触媒活性及び二量化生成物の選択性はいずれももはや向上しなくなることの他に、圧縮成形した際に強度のある担体が得難くなり、この担体から調製された触媒は寿命が短くなり、好ましくない。 The content of graphite (c) contained in the carrier (B) is 0.1 to 3% by weight, preferably 0.5 to 2% by weight, based on the anhydrous potassium compound (d). When the content of graphite (c) is less than 0.1% by weight, the catalyst life and the selectivity to the dimerization of the α-olefin are lowered. Further, even if the content of the graphite (c) is larger than 3% by weight, the catalytic activity and the selectivity of the dimerization product are no longer improved, and the strength is high when compression molding. It is difficult to obtain a support, and a catalyst prepared from this support has a short life and is not preferable.
また本発明の触媒の担体（B）の構成成分の無水カリウム化合物（ｄ）は通常の無水カリウム化合物であるが、触媒活性及び目的とする二量化生成物への選択性の向上した触媒を得るためには、適宜の性状を有する無水カリウム化合物の原粉を圧縮成形することにより得られる担体を使用することが好ましい。 The anhydrous potassium compound (d), which is a component of the carrier (B) of the catalyst of the present invention, is an ordinary anhydrous potassium compound, and a catalyst having improved catalytic activity and selectivity to the desired dimerization product is obtained. For this purpose, it is preferable to use a carrier obtained by compression molding a raw powder of an anhydrous potassium compound having appropriate properties.
また本発明の触媒の担体（B）の構成成分の無水カリウム化合物（ｄ）としては具体的には、炭酸カリウム、ケイ酸カリウム、硫酸カリウム、フッ化カリウム、塩化カリウム、臭化カリウムなどの無機カリウム化合物の無水和物を例示することができる。これら無機カリウム化合物のうちでは、無水炭酸カリウムが特に好適である。 Specific examples of the anhydrous potassium compound (d) as a component of the carrier (B) of the catalyst of the present invention include inorganic substances such as potassium carbonate, potassium silicate, potassium sulfate, potassium fluoride, potassium chloride, and potassium bromide. An anhydrate of a potassium compound can be exemplified. Of these inorganic potassium compounds, anhydrous potassium carbonate is particularly preferred.
本発明の触媒は種々の方法によって調製することができる。まず本発明の触媒を構成する該圧縮成形粒状担体（B）は、通常次の方法で調製することができる。
前記グラファイト（ｃ）及び前記無水カリウム化合物（ｄ）からなり、且つ特定の組成の粉末状組成物を、打錠成形機、圧縮成形機、ペレタイザーなどによって圧縮成形することにより、該圧縮成形粒状担体（B）が得られる。この圧縮成形粒状担体の形状は、いかなる形状のものでも差し支えないが、通常、錠剤状、ペレット状、球状などに成形されており、その粒径は、通常０．５ｍｍ以上、好ましくは１ないし１０ｍｍの範囲である。圧縮成形粒状担体（B）の圧縮強度（打錠強度）は通常１〜２０Kg/cm2である。
The catalyst of the present invention can be prepared by various methods. First, the compression-molded granular carrier (B) constituting the catalyst of the present invention can be usually prepared by the following method.
The compression-molded granular carrier comprising the graphite (c) and the anhydrous potassium compound (d) and compression-molding a powdery composition having a specific composition by a tableting machine, a compression molding machine, a pelletizer or the like. (B) is obtained. The shape of the compression-molded granular carrier may be any shape, but is usually formed into a tablet shape, a pellet shape, a spherical shape, and the particle size is usually 0.5 mm or more, preferably 1 to 10 mm. Range. The compression strength (tablet strength) of the compression-molded granular carrier (B) is usually 1 to 20 kg / cm2.
本発明の触媒は前記の方法で調製された該圧縮成形粒状担体（B）に、前記担持成分を担持させることで調製される。該圧縮成形粒状担体（B）に担持させる方法としては種々の方法を採用することができる。ここでいずれの場合にも、担持成分のアルカリ金属としてナトリウム金属（ａ）を使用すると、このナトリウム金属（ａ）は、無水カリウム化合物（ｄ）と加熱下に接触することによりアリカリ金属が交換反応を起こし、カリウム金属及び無水ナトリウム化合物を生成する。担持方法として具体的には、次の方法を例示することができる。 The catalyst of the present invention is prepared by supporting the supporting component on the compression-molded granular carrier (B) prepared by the above method. Various methods can be adopted as a method of supporting the compression-molded granular carrier (B). Here, in any case, when sodium metal (a) is used as the alkali metal of the supporting component, this sodium metal (a) is exchanged with ant potassium metal by contacting with anhydrous potassium compound (d) under heating. To produce potassium metal and anhydrous sodium compounds. Specific examples of the loading method include the following methods.
・ ナトリウム金属（ａ）と前記圧縮成形粒状担体（B）とを、不活性ガス雰囲気下で、加熱下及び攪拌下に接触させる方法。 A method in which sodium metal (a) and the compression-molded granular carrier (B) are brought into contact under heating and stirring in an inert gas atmosphere.
・ ナトリウム金属（ａ）及び必要に応じてその他の担持成分からなる混合物と前記圧縮成形粒状担体（B）とを、不活性ガス雰囲気下で、加熱下及び攪拌下に接触させる方法。 A method in which a mixture of sodium metal (a) and, if necessary, other supporting components and the compression-molded granular carrier (B) are brought into contact with each other under heating and stirring in an inert gas atmosphere.
ここで担持処理の際の温度は通常１５０℃ないし４００℃の範囲であるが、触媒活性、触媒寿命及び二量化生成物への選択性の優れた触媒を得るためには、２００ないし３５０℃の範囲の温度で担持処理を行うのが好ましい。 Here, the temperature during the supporting treatment is usually in the range of 150 ° C. to 400 ° C., but in order to obtain a catalyst having excellent catalytic activity, catalyst life and selectivity to the dimerization product, the temperature is 200 to 350 ° C. The supporting treatment is preferably performed at a temperature in the range.
本発明の触媒は、α−オレフィンの二量化反応または共二量化反応に使用される。α−オレフィンとして具体的には、エチレン、プロピレン、１−ブテン、イソブチレン、１−ペンテンなどの低級α−オレフィンが挙げられる。これらの二量化反応または共二量化反応のうちで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、１−ブテンとエチレンの共二量化による３−メチル−１−ペンテンの製造に本発明の触媒を使用することが好ましい。 The catalyst of the present invention is used for an α-olefin dimerization reaction or co-dimerization reaction. Specific examples of the α-olefin include lower α-olefins such as ethylene, propylene, 1-butene, isobutylene and 1-pentene. Among these dimerization reactions or codimerization reactions, the present invention is concerned with the production of 4-methyl-1-pentene by dimerization of propylene and the production of 3-methyl-1-pentene by codimerization of 1-butene and ethylene. It is preferable to use the catalyst.
本発明の触媒を使用したα−オレフィンの二量化反応または共二量化反応は、加熱下に気相法または液相法で実施されるが、気相法で実施することが好ましい。気相反応で反応を行う場合の温度は、通常０ないし３００℃、好ましくは１００ないし２００℃である。反応の際の圧力は通常常圧ないし２００kg/cm2-G、好ましくは２０ないし１５０kg/cm2-Gの範囲である。反応は固定床方式で行うこともできるし、流動床方式で行うこともできるが、固定床方式で行うことが好ましい。固定床方式で反応を行う場合に、α−オレフィンの液空間速度（LHSV）は通常０．１ないし１０ｈｒ-1、好ましくは０．５ないし７．５ｈｒ-1の範囲である。反応終了後の混合物から定法に従って未反応のα−オレフィン及び生成物を分離し、未反応のα−オレフィンは、反応に循環再利用される。
以下、実施例によって本発明を具体的に説明するが、これに限定されるものではない。
The α-olefin dimerization reaction or co-dimerization reaction using the catalyst of the present invention is carried out by heating in a gas phase method or a liquid phase method, but is preferably carried out by a gas phase method. The temperature when the reaction is carried out by a gas phase reaction is usually 0 to 300 ° C., preferably 100 to 200 ° C. The pressure during the reaction is usually in the range of normal pressure to 200 kg / cm2-G, preferably 20 to 150 kg / cm2-G. The reaction can be carried out in a fixed bed system or a fluidized bed system, but is preferably carried out in a fixed bed system. When the reaction is carried out in a fixed bed system, alpha-olefin liquid hourly space velocity (LHSV) to normally 0.1 to 10 hr -1, preferably in the range of from 0.5 7.5hr -1. Unreacted α-olefin and product are separated from the mixture after completion of the reaction according to a conventional method, and the unreacted α-olefin is recycled in the reaction.
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
[実施例１]
平均粒径０．７μｍ、BET法で測定した比表面積が１５０m2/gのグラファイト０．８５重量部と平均粒径が３００μｍ、嵩密度が０．７g/mlの無水炭酸カリウム９９．１５重量部とを含む直径３ｍｍ、高さ３ｍｍの円筒状の担体を打錠成形した。この担体８７０ｇを窒素気流中３５０℃、2時間乾燥させたのち、窒素雰囲気中で３１ｇのナトリウム金属を加え、230℃で５時間攪拌し、触媒を調製した。続いて、調製した触媒を用いてプロピレンの二量化反応を行った。耐圧気相反応器に触媒を充填し、この反応器の圧力を１００kg/cm2-G及び温度１５７℃に維持しながらプロピレンを液空間速度（LHSV）０．８５ｈｒ-1で供給し、連続反応を行った。8ヶ月後の反応器前後の差圧は０．３kg/cm2であった。
[Example 1]
0.85 parts by weight of graphite having an average particle diameter of 0.7 μm and a specific surface area measured by the BET method of 150 m 2 / g, and 99.15 parts by weight of anhydrous potassium carbonate having an average particle diameter of 300 μm and a bulk density of 0.7 g / ml A cylindrical carrier having a diameter of 3 mm and a height of 3 mm including was tableted. After 870 g of this support was dried in a nitrogen stream at 350 ° C. for 2 hours, 31 g of sodium metal was added in a nitrogen atmosphere and stirred at 230 ° C. for 5 hours to prepare a catalyst. Then, the dimerization reaction of propylene was performed using the prepared catalyst. A pressure-resistant gas phase reactor is filled with a catalyst, and propylene is supplied at a liquid space velocity (LHSV) of 0.85 hr −1 while maintaining the pressure of the reactor at 100 kg / cm 2 -G and a temperature of 157 ° C. went. The differential pressure before and after the reactor after 8 months was 0.3 kg / cm2.
[比較例１]
平均粒径１０μｍ、BET法で測定した比表面積が１０m2/gのグラファイトを用いる以外は実施例１と同様に触媒を調製し、プロピレンの二量化反応を行った。8ヶ月後の反応器前後の差圧は０．７kg/cm2であった。
[Comparative Example 1]
A catalyst was prepared in the same manner as in Example 1 except that graphite having an average particle size of 10 μm and a specific surface area measured by the BET method of 10 m 2 / g was used, and propylene dimerization reaction was performed. The differential pressure before and after the reactor after 8 months was 0.7 kg / cm2.
本発明の方法を用いることで寿命が長い触媒を調製することができる。 A catalyst having a long life can be prepared by using the method of the present invention.
Claims (4)
An α-olefin dimer production method using the α-olefin dimerization catalyst according to claim 1.
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| JP2008149275A (en) * | 2006-12-19 | 2008-07-03 | Mitsui Chemicals Inc | Catalyst for dimerizing alpha-olefin and method for producing alpha-olefin dimer |
| WO2015093378A1 (en) | 2013-12-17 | 2015-06-25 | 三井化学株式会社 | MOLDED BODY, METHOD FOR PRODUCING SAME, CATALYST FOR α-OLEFIN DIMERIZATION, AND METHOD FOR PRODUCING α-OLEFIN DIMER |
| WO2018117247A1 (en) | 2016-12-22 | 2018-06-28 | 三井化学株式会社 | METHOD FOR PRODUCING POROUS MOLDED BODY, METHOD FOR PRODUCING CATALYST FOR α-OLEFIN DIMERIZATION, METHOD FOR PRODUCING α-OLEFIN DIMER, POROUS MOLDED BODY, AND CATALYST FOR α-OLEFIN DIMERIZATION |
| WO2019189636A1 (en) | 2018-03-29 | 2019-10-03 | 三井化学株式会社 | POROUS MOLDED ARTICLE AND METHOD FOR PRODUCING SAME, CATALYST FOR α-OLEFIN DIMERIZATION USE AND METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING α-OLEFIN DIMER |
| WO2023190652A1 (en) * | 2022-03-30 | 2023-10-05 | 三井化学株式会社 | Method for producing olefin dimer, and olefin dimerization catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008149275A (en) * | 2006-12-19 | 2008-07-03 | Mitsui Chemicals Inc | Catalyst for dimerizing alpha-olefin and method for producing alpha-olefin dimer |
| WO2015093378A1 (en) | 2013-12-17 | 2015-06-25 | 三井化学株式会社 | MOLDED BODY, METHOD FOR PRODUCING SAME, CATALYST FOR α-OLEFIN DIMERIZATION, AND METHOD FOR PRODUCING α-OLEFIN DIMER |
| US10500570B2 (en) | 2013-12-17 | 2019-12-10 | Mitsui Chemicals, Inc. | Formed body and method for producing the same, α-olefin dimerization catalyst, and method for producing α-olefin dimer |
| WO2018117247A1 (en) | 2016-12-22 | 2018-06-28 | 三井化学株式会社 | METHOD FOR PRODUCING POROUS MOLDED BODY, METHOD FOR PRODUCING CATALYST FOR α-OLEFIN DIMERIZATION, METHOD FOR PRODUCING α-OLEFIN DIMER, POROUS MOLDED BODY, AND CATALYST FOR α-OLEFIN DIMERIZATION |
| US11247194B2 (en) | 2016-12-22 | 2022-02-15 | Mitsui Chemicals, Inc. | Method for producing porous molded body, method for producing catalyst for α-olefin dimerization, method for producing α-olefin dimer, porous molded body, and catalyst for α-olefin dimerization |
| US11772072B2 (en) | 2016-12-22 | 2023-10-03 | Mitsui Chemicals, Inc. | Method for producing porous molded body, method for producing catalyst for α-olefin dimerization, method for producing α-olefin dimer, porous molded body, and catalyst for α-olefin dimerization |
| WO2019189636A1 (en) | 2018-03-29 | 2019-10-03 | 三井化学株式会社 | POROUS MOLDED ARTICLE AND METHOD FOR PRODUCING SAME, CATALYST FOR α-OLEFIN DIMERIZATION USE AND METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING α-OLEFIN DIMER |
| KR20200126401A (en) | 2018-03-29 | 2020-11-06 | 미쓰이 가가쿠 가부시키가이샤 | Porous molded article and its manufacturing method, α-olefin dimerization catalyst and its manufacturing method, and α-olefin dimer manufacturing method |
| KR20220144414A (en) | 2018-03-29 | 2022-10-26 | 미쓰이 가가쿠 가부시키가이샤 | POROUS MOLDED ARTICLE AND METHOD FOR PRODUCING SAME, CATALYST FOR α-OLEFIN DIMERIZATION USE AND METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING α-OLEFIN DIMER |
| US11759768B2 (en) | 2018-03-29 | 2023-09-19 | Mitsui Chemicals, Inc. | Porous formed body and production method thereof, α-olefin dimerization catalyst and production method thereof, and method of producing α-olefin dimer |
| WO2023190652A1 (en) * | 2022-03-30 | 2023-10-05 | 三井化学株式会社 | Method for producing olefin dimer, and olefin dimerization catalyst |
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