JP2005314272A - Manufacturing method of 1-hexene - Google Patents
Manufacturing method of 1-hexene Download PDFInfo
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- JP2005314272A JP2005314272A JP2004133184A JP2004133184A JP2005314272A JP 2005314272 A JP2005314272 A JP 2005314272A JP 2004133184 A JP2004133184 A JP 2004133184A JP 2004133184 A JP2004133184 A JP 2004133184A JP 2005314272 A JP2005314272 A JP 2005314272A
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- 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
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Abstract
Description
本発明はエチレンを三量化する1−ヘキセンの製造方法に関するものである。更に詳しくは、本発明は、タンタル化合物を用いてエチレンを三量化する方法であって、優れた選択性で安定的に1−ヘキセンを製造することができるという特徴を有する1−ヘキセンの製造方法に関するものである。 The present invention relates to a process for producing 1-hexene by trimerizing ethylene. More specifically, the present invention relates to a method for trimerizing ethylene using a tantalum compound, which is characterized in that 1-hexene can be stably produced with excellent selectivity. It is about.
タンタル化合物を用いてエチレンを三量化する方法としては、特許文献1および非特許文献1に、タンタル化合物とアルキル化剤とからなる触媒系を用いる方法が開示されている。 As a method for trimerizing ethylene using a tantalum compound, Patent Document 1 and Non-Patent Document 1 disclose a method using a catalyst system composed of a tantalum compound and an alkylating agent.
上記2件の開示情報では、反応に及ぼすタンタル化合物の濃度が規定されておらず、濃度が高いと反応効率が低下する問題点があった。 In the above two disclosed information, the concentration of the tantalum compound affecting the reaction is not specified, and there is a problem that the reaction efficiency decreases when the concentration is high.
かかる状況において、本発明が解決しようとする課題は、タンタル化合物を用いてエチレンを三量化する方法であって、優れた選択性で安定的に1−ヘキセンを製造することができるという特徴を有する1−ヘキセンの製造方法を提供する点にある。 In such a situation, the problem to be solved by the present invention is a method of trimerizing ethylene using a tantalum compound, and has a feature that 1-hexene can be stably produced with excellent selectivity. The object is to provide a method for producing 1-hexene.
本発明者らは、上記課題を解決するために鋭意検討を行った結果、タンタル化合物の濃度を制御することにより、上記の課題を解決し得ることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by controlling the concentration of the tantalum compound, and have reached the present invention.
すなわち、本発明は、タンタル化合物(A)と金属を含有するアルキル化剤(B)とを含む触媒系を用いてエチレンの三量化反応を実施するに際し、タンタル化合物の濃度を反応液1リットルあたり2ミリモル未満の条件下で実施することを特徴とする1−ヘキセンの製造方法に係るものである。 That is, in the present invention, when conducting a trimerization reaction of ethylene using a catalyst system containing a tantalum compound (A) and a metal-containing alkylating agent (B), the concentration of the tantalum compound is adjusted per liter of the reaction solution. The present invention relates to a method for producing 1-hexene, which is carried out under a condition of less than 2 mmol.
本発明によれば、タンタル化合物(A)と金属を含有するアルキル化剤(B)とからなる触媒を用いてエチレンの三量化反応を実施するに際し、タンタル化合物の濃度を反応液1リットルあたり2ミリモル未満の条件下で実施することにより、優れた選択性で安定的に1−ヘキセンを製造することができる。 According to the present invention, when ethylene trimerization reaction is carried out using a catalyst comprising a tantalum compound (A) and a metal-containing alkylating agent (B), the concentration of the tantalum compound is set to 2 per liter of the reaction solution. By carrying out under the condition of less than millimole, 1-hexene can be produced stably with excellent selectivity.
本発明で使用されるタンタル化合物(A)としては、ハロゲン化タンタルが好ましく、具体例として、五弗化タンタル、五塩化タンタル、五臭化タンタル、五沃化タンタル等が挙げられ、好ましくは五塩化タンタルまたは五臭化タンタルである。ハロゲン化タンタル以外のタンタル化合物を用いた場合には、触媒活性が低下することがある。 The tantalum compound (A) used in the present invention is preferably a tantalum halide, and specific examples include tantalum pentafluoride, tantalum pentachloride, tantalum pentabromide, tantalum pentaiodide, etc. Tantalum chloride or tantalum pentabromide. When a tantalum compound other than tantalum halide is used, the catalytic activity may be reduced.
タンタル化合物と共に使用される金属を含有するアルキル化剤(B)としては、ヒドロカルビル金属、ヒドロカルビル金属ハロゲン化物、アルキルアルミノキサン等が挙げられ、好ましくは、金属種としてスズ、亜鉛、アルミニウム、リチウム、マグネシウムを含む低級アルキル金属化合物であり、好ましくは低級アルキルアリール金属化合物が挙げられ、更に好ましくは、テトラメチルスズ、テトラエチルスズ、ジメチル亜鉛、メチルリチウム、トリメチルアルミニウム、n−ブチルリチウム、アリルトリフェニルスズ、トリエチルアルミニウム、ジメチルアルミニウムクロリド、テトラフェニルスズ、メチルアルミノキサン、メチルマグネシウムブロミド、イソプロピルマグネシウムハライド、イソブチルマグネシウムハライド、sec−ブチルマグネシウムハライド、シクロペンチルマグネシウムハライド、シクロヘキシルマグネシウムハライド、1−フェネチルマグネシウムハライド、2−フェネチルマグネシウムハライド、イソプロピルリチウム、イソブチルリチウム、sec−ブチルリチウム、シクロペンチルリチウム、シクロヘキシルリチウム、1−フェネチルリチウム、2−フェネチルリチウム、トリイソプロピルアルミニウム、トリイソブチルアルミニウム、トリ−sec−ブチルアルミニウム、トリシクロヘキシルアルミニウム、イソブチルアルミニウムジクロライド、ジイソブチルアルミニウムクロライド、ジイソブチルアルミニウムハライド、モディファイドメチルアルミノキサン(メチルアルミノキサンのメチル基の一部がイソブチル基で置換されたアルミノキサン)、イソブチルアルミノキサン、テトライソプロピルスズ、イソプロピルトリメチルスズ、テトライソブチルスズまたはジイソブチルスズジハライド等が例示される。上記以外のアルキル化剤を用いた場合には、三量化反応の触媒活性が低下する場合がある。 Examples of the alkylating agent (B) containing a metal used together with the tantalum compound include hydrocarbyl metal, hydrocarbyl metal halide, alkylaluminoxane, and the like. Preferably, tin, zinc, aluminum, lithium, magnesium is used as the metal species. Lower alkyl metal compounds, preferably lower alkyl aryl metal compounds, more preferably tetramethyltin, tetraethyltin, dimethylzinc, methyllithium, trimethylaluminum, n-butyllithium, allyltriphenyltin, triethyl Aluminum, dimethylaluminum chloride, tetraphenyltin, methylaluminoxane, methylmagnesium bromide, isopropylmagnesium halide, isobutylmagnesium halide, sec Butyl magnesium halide, cyclopentyl magnesium halide, cyclohexyl magnesium halide, 1-phenethyl magnesium halide, 2-phenethyl magnesium halide, isopropyl lithium, isobutyl lithium, sec-butyl lithium, cyclopentyl lithium, cyclohexyl lithium, 1-phenethyl lithium, 2-phenethyl lithium , Triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tricyclohexylaluminum, isobutylaluminum dichloride, diisobutylaluminum chloride, diisobutylaluminum halide, modified methylaluminoxane (part of the methyl group of methylaluminoxane is replaced with isobutyl group) Ta Minokisan), isobutyl aluminoxane, tetraisopropyl tin, isopropyl trimethyltin, tetra isobutyl tin or diisobutyl tin dihalides, and the like. When an alkylating agent other than the above is used, the catalytic activity of the trimerization reaction may decrease.
上記アルキル化剤(B)は単独で使用することもできるが、2種類以上を混合して使用することもできる。 Although the said alkylating agent (B) can also be used independently, 2 or more types can also be mixed and used.
タンタル化合物(A)とアルキル化剤(B)は、最適な1−ヘキセン選択性および最高の触媒活性を得るために最適の割合で混合される。タンタル金属/アルキル化剤のモル比は0.1〜10が好ましく、更に好ましくは0.25〜2であり、更に好ましくは0.5〜2である。該モル比が過小であったり、過大であったりすると、三量化反応の触媒活性が低下する場合がある。 The tantalum compound (A) and the alkylating agent (B) are mixed in an optimal ratio to obtain optimal 1-hexene selectivity and maximum catalyst activity. The tantalum metal / alkylating agent molar ratio is preferably from 0.1 to 10, more preferably from 0.25 to 2, and even more preferably from 0.5 to 2. If the molar ratio is too small or too large, the catalytic activity of the trimerization reaction may be reduced.
タンタル化合物(A)とアルキル化剤(B)の混合およびエチレン三量化反応は通常溶媒の存在下で実施される。溶媒としては、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂肪族炭化水素;ベンゼン、トルエン、キシレン、クメン、エチルベンゼン、モノクロロベンゼン、ジクロロベンゼン等の芳香族炭化水素;ジクロロメタン、クロロホルム、1、1−ジクロロエタン等のハロゲン化炭化水素;1−ブテン、1−ヘキセン、1−オクテン等のオレフィン類等が挙げられる。触媒活性および1−ヘキセンの選択率の観点から、好ましい溶媒としては、芳香族炭化水素が挙げられ、更に好ましくはベンゼン、トルエン、キシレン、モノクロロベンゼンが挙げられる。これらの溶媒は単独で使用してもよいし、2種類以上を混合して使用してもよい。 The mixing of the tantalum compound (A) and the alkylating agent (B) and the ethylene trimerization reaction are usually carried out in the presence of a solvent. Solvents include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, monochlorobenzene, and dichlorobenzene Halogenated hydrocarbons such as dichloromethane, chloroform and 1,1-dichloroethane; olefins such as 1-butene, 1-hexene and 1-octene; From the viewpoint of catalytic activity and 1-hexene selectivity, preferred solvents include aromatic hydrocarbons, and more preferred are benzene, toluene, xylene, and monochlorobenzene. These solvents may be used alone or in combination of two or more.
タンタル化合物(A)とアルキル化剤(B)の混合およびエチレン三量化反応を実施する際、反応液中のタンタル化合物の濃度は、通常反応液1リットルあたり2ミリモル未満である。タンタル化合物の濃度が高すぎると反応効率が低下する場合がある。 When the mixing of the tantalum compound (A) and the alkylating agent (B) and the ethylene trimerization reaction are carried out, the concentration of the tantalum compound in the reaction solution is usually less than 2 mmol per liter of the reaction solution. If the concentration of the tantalum compound is too high, the reaction efficiency may decrease.
本発明のエチレン三量化反応に用いる触媒系は、タンタル化合物(A)と金属を含有するアルキル化剤(B)とを含むものであり、タンタル化合物とアルキル化剤を混合させることにより調製できる。調製方法は特に限定されないが、例えばタンタル化合物とアルキル化剤とを無溶媒もしくは溶媒中で混合させる方法を挙げることができる。タンタル化合物とアルキル化剤の混合を前もって行い、その後エチレンと接触させて三量化反応を実施することができる。また、タンタル化合物とアルキル化剤の混合をエチレン存在下に行い、タンタル化合物とアルキル化剤の混合と同時に三量化反応を開始することも可能である。なお、これら原料の混合順序は特に制限されないが、触媒活性および1−ヘキセンの選択率の観点から、タンタル化合物にアルキル化剤を添加していく方が好ましい。 The catalyst system used in the ethylene trimerization reaction of the present invention contains a tantalum compound (A) and a metal-containing alkylating agent (B), and can be prepared by mixing a tantalum compound and an alkylating agent. Although a preparation method is not specifically limited, For example, the method of mixing a tantalum compound and an alkylating agent in a non-solvent or a solvent can be mentioned. The trimerization reaction can be carried out by mixing the tantalum compound and the alkylating agent in advance and then contacting with ethylene. It is also possible to mix the tantalum compound and the alkylating agent in the presence of ethylene and start the trimerization reaction simultaneously with the mixing of the tantalum compound and the alkylating agent. The mixing order of these raw materials is not particularly limited, but it is preferable to add an alkylating agent to the tantalum compound from the viewpoint of catalytic activity and 1-hexene selectivity.
本反応の三量化反応の温度は、通常−100〜150℃であり、好ましくは−20〜100℃、より好ましくは20〜70℃である。反応温度が低すぎると触媒活性が低下する場合があり、一方反応温度が高すぎると副反応が増加する場合がある。反応圧力は、通常絶対圧力0〜300MPaであり、好ましくは0.1〜30MPaである。反応圧力が低すぎると触媒活性が低下する場合があり、一方反応圧力が高すぎると副反応が増加する場合がある。 The temperature of the trimerization reaction of this reaction is usually −100 to 150 ° C., preferably −20 to 100 ° C., more preferably 20 to 70 ° C. If the reaction temperature is too low, the catalyst activity may decrease, while if the reaction temperature is too high, side reactions may increase. The reaction pressure is usually an absolute pressure of 0 to 300 MPa, preferably 0.1 to 30 MPa. If the reaction pressure is too low, the catalyst activity may decrease, while if the reaction pressure is too high, side reactions may increase.
本発明は反応系内の水分量がタンタル原子の2モル倍以下、好ましくは1モル倍以下、より好ましくは0.5モル倍以下であり、更に好ましくは実質的に無水の条件下で実施される。該全水分量が本発明の範囲を超えると触媒が失活して、三量化反応が進行しなくなる。該水分量とは、触媒、エチレンガス、溶媒等に含まれる反応系の全水分量であり、通常、カールフィッシャー水分計等により測定される。 The present invention is carried out under a condition where the water content in the reaction system is 2 mol times or less, preferably 1 mol times or less, more preferably 0.5 mol times or less, more preferably 0.5 mol times or less, more preferably tantalum atoms. The When the total water content exceeds the range of the present invention, the catalyst is deactivated and the trimerization reaction does not proceed. The moisture content is the total moisture content of the reaction system contained in the catalyst, ethylene gas, solvent, etc., and is usually measured by a Karl Fischer moisture meter or the like.
本反応は、回分式、半連続式、連続式のいずれでも実施しうる。反応終了後、反応液に、例えば水、アルコール、塩酸、水酸化ナトリウム水溶液等の失活剤を添加して反応を停止させる。反応停止後、蒸留や抽出と言った公知の操作により目的とする1−ヘキセンを分離することができる。また、反応を停止させることなく、蒸留によって目的とする1−ヘキセンを分離することもできる。 This reaction can be carried out in any of batch, semi-continuous and continuous systems. After completion of the reaction, a quenching agent such as water, alcohol, hydrochloric acid, or aqueous sodium hydroxide is added to the reaction solution to stop the reaction. After the reaction is stopped, the target 1-hexene can be separated by a known operation such as distillation or extraction. Moreover, the target 1-hexene can be separated by distillation without stopping the reaction.
以下に、本発明を、実施例を用いて更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例1
200ccオートクレーブにアルゴン下で、溶媒であるトルエンを80mL加え、温度を70℃に安定させた後、エチレンを4.6MPaまで加圧し安定させた。ここに五塩化タンタル30mgを脱水トルエン2mLに溶解させた溶液(五塩化タンタルとして80μmol)、トリイソブチルアルミニウム(25mmol/L−トルエン溶液)を2mL(トリイソブチルアルミニウムとして50μmol)を仕込み、反応を開始した(このときの五塩化タンタルの濃度0.95mmol/L)。4時間後、エタノールを1ml加え、反応容器を室温まで冷却し、次いで常圧に戻した。反応液をガスクロマトグラフィーにより分析した。また、反応液に含まれる固体分を、ろ紙を用いて、ろ別し、これを風乾後、減圧下で乾燥してその重量を測定した。結果を表1に示す。
Example 1
To a 200 cc autoclave, 80 mL of toluene as a solvent was added under argon and the temperature was stabilized at 70 ° C., and then ethylene was pressurized to 4.6 MPa and stabilized. A solution prepared by dissolving 30 mg of tantalum pentachloride in 2 mL of dehydrated toluene (80 μmol as tantalum pentachloride) and 2 mL of triisobutylaluminum (25 mmol / L-toluene solution) (50 μmol as triisobutylaluminum) were charged to initiate the reaction. (The concentration of tantalum pentachloride at this time is 0.95 mmol / L). After 4 hours, 1 ml of ethanol was added, the reaction vessel was cooled to room temperature, and then returned to normal pressure. The reaction solution was analyzed by gas chromatography. Moreover, the solid content contained in the reaction solution was filtered using a filter paper, air-dried, dried under reduced pressure, and the weight was measured. The results are shown in Table 1.
比較例1
五塩化タンタル92mgを脱水トルエン2mLに溶解させた溶液(五塩化タンタルとして260μmol)、トリイソブチルアルミニウム(80mmol/L−トルエン溶液)を2mL(トリイソブチルアルミニウムとして160μmol)を仕込み、反応を開始した(このときの五塩化タンタルの濃度3.1mmol/L)以外、実施例1と同様に実験を行った。結果を表1に示す。
Comparative Example 1
A solution of 92 mg of tantalum pentachloride dissolved in 2 mL of dehydrated toluene (260 μmol as tantalum pentachloride) and 2 mL of triisobutylaluminum (80 mmol / L-toluene solution) (160 μmol as triisobutylaluminum) were charged to initiate the reaction (this The experiment was conducted in the same manner as in Example 1 except that the concentration of tantalum pentachloride (3.1 mmol / L). The results are shown in Table 1.
上記の結果から次のことがわかる。本発明による触媒濃度の濃い比較例1に比べて、実施例1は反応効率が良い。
The following can be seen from the above results. Compared with Comparative Example 1 having a high catalyst concentration according to the present invention, Example 1 has better reaction efficiency.
Claims (5)
Alkylating agent (B) is tetramethyltin, tetraethyltin, dimethylzinc, diethylzinc, methyllithium, trimethylaluminum, n-butyllithium, allyltriphenyltin, triethylaluminum, dimethylaluminum chloride, tetraphenyltin, methylaluminoxane Methyl magnesium bromide, isopropyl magnesium halide, isobutyl magnesium halide, sec-butyl magnesium halide, cyclopentyl magnesium halide, cyclohexyl magnesium halide, 1-phenethyl magnesium halide, 2-phenethyl magnesium halide, isopropyl lithium, isobutyl lithium, sec-butyl lithium, Cyclopentyl lithium, cyclohexyl lithium, 1-phenethyl Thium, 2-phenethyllithium, triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tricyclohexylaluminum, isobutylaluminum dichloride, diisobutylaluminum chloride, diisobutylaluminum halide, modified methylaluminoxane (part of methyl group of methylaluminoxane) Is an isobutyl group-substituted aluminoxane), isobutylaluminoxane, tetraisopropyltin, isopropyltrimethyltin, tetraisobutyltin or diisobutyltin dihalide.
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JP2013515601A (en) * | 2009-12-29 | 2013-05-09 | ペトロチャイナ カンパニー リミテッド | Catalyst for synthesis of 1-hexene by trimerization of ethylene and use thereof |
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