JP2005170903A - Method for producing bicyclo [2.2.1] heptane derivative - Google Patents
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Abstract
【課題】機能性モノマーやトラクションドライブ用流体の基油製造原料などとして有用なビシクロ［２．２．１］ヘプタン誘導体の製造に際し、ビシクロ［２．２．１］ヘプテン類の異性化の長期連続運転を可能とし、ビシクロ［２．２．１］ヘプタン誘導体を高収率で安定して得られる方法を提供する。
【解決手段】プロピレン又はブテンとシクロペンタジエン又はジシクロペンタジエンとをディールス・アルダー反応させて得られた反応生成物を、異性化触媒の存在下で異性化してビシクロ［２．２．１］ヘプタン誘導体を製造するに際し、異性化触媒として、好ましくは固体酸触媒を不活性ガスの存在下、５０〜５００℃の温度で前処理した触媒を用い、異性化反応を液相で行う。
【選択図】なし
Long-term continuous isomerization of bicyclo [2.2.1] heptenes in the production of bicyclo [2.2.1] heptane derivatives useful as base monomers for production of functional monomers and traction drive fluids Provided is a method that enables operation and stably obtains a bicyclo [2.2.1] heptane derivative in a high yield.
Bicyclo [2.2.1] heptane derivatives are obtained by isomerizing a reaction product obtained by subjecting propylene or butene and cyclopentadiene or dicyclopentadiene to Diels-Alder reaction in the presence of an isomerization catalyst. In the production of, the isomerization catalyst is preferably a catalyst obtained by pretreating a solid acid catalyst at a temperature of 50 to 500 ° C. in the presence of an inert gas, and the isomerization reaction is performed in a liquid phase.
[Selection figure] None
Description
本発明は、ビシクロ［２．２．１］ヘプタン誘導体の製造方法の改良に関し、さらに詳しくは、本発明は、機能性モノマーやトラクションドライブ用流体の基油製造原料などとして有用なビシクロ［２．２．１］ヘプタン誘導体を、効率よく製造する方法に関するものである。 The present invention relates to an improvement in a method for producing a bicyclo [2.2.1] heptane derivative. More specifically, the present invention relates to a bicyclo [2. 2.1] A method for efficiently producing a heptane derivative.
自動車用トラクション式ＣＶＴ（無段変速機）は、大型車から小型車まで搭載可能で、燃費が良い上、加速が鋭く、変速ショックがない快適な変速機として、今後の自動変速機の主流を占めるものと予測されている。このＣＶＴには、動力伝達のために、高温（約１４０℃）においてトラクション係数が高く、かつ低温始動性のために、低温（約−４０℃）においても低い粘度をもつ優れた性能を有するトラクションオイルが必要である。 The traction CVT (continuously variable transmission) for automobiles can be mounted from large vehicles to small vehicles, and it will be the mainstream of future automatic transmissions as a comfortable transmission with good fuel efficiency, sharp acceleration, and no shift shock. It is predicted. This CVT has a high traction coefficient at high temperature (about 140 ° C) for power transmission, and has excellent performance with low viscosity at low temperature (about -40 ° C) for low temperature startability. Oil is needed.
この高温でのトラクション係数と低温粘度とは、相反する性能であって、この相反する性能を高い次元で両立させた優れたトラクションオイル基油が開示されている（例えば、特許文献１、特許文献２参照）。また、これらの特許文献には、上記基油の中間体として、２−メチレン−３−メチルビシクロ［２．２．１］ヘプタン、２，３−ジメチルビシクロ［２．２．１］ヘプト−２−エンなどのビシクロ［２．２．１］ヘプタン誘導体が開示されている。
一方、シクロペンタジエンと２−ブテンをディールス・アルダー反応させて、５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エンを得、それを異性化させることにより、２−メチレン−３−メチルビシクロ［２．２．１］ヘプタン及び２，３−ジメチルビシクロ［２．２．１］ヘプト−２−エンを製造する方法が開示されている（例えば、特許文献３参照）。さらに、前半のディールス・アルダー反応において、炭素数３若しくは４の非環状オレフィンの一種又は二種以上とシクロペンタジエン又はジシクロペンタジエンを気相あるいは超臨界状態の条件で反応を行うことにより、ビシクロ［２．２．１］ヘプテン類を高選択率で得ることができる製造方法も開示されている（例えば、特許文献４参照）。
The high temperature traction coefficient and the low temperature viscosity are contradictory performances, and excellent traction oil base oils in which the contradictory performances are compatible at a high level are disclosed (for example, Patent Document 1 and Patent Documents). 2). Moreover, these patent documents include 2-methylene-3-methylbicyclo [2.2.1] heptane and 2,3-dimethylbicyclo [2.2.1] hept-2 as intermediates of the above base oil. Bicyclo [2.2.1] heptane derivatives such as -ene are disclosed.
On the other hand, cyclopentadiene and 2-butene are subjected to Diels-Alder reaction to obtain 5,6-dimethylbicyclo [2.2.1] hept-2-ene, which is isomerized to give 2-methylene-3. -A method for producing methylbicyclo [2.2.1] heptane and 2,3-dimethylbicyclo [2.2.1] hept-2-ene is disclosed (for example, see Patent Document 3). Furthermore, in the first half of the Diels-Alder reaction, by reacting one or more acyclic olefins having 3 or 4 carbon atoms with cyclopentadiene or dicyclopentadiene in a gas phase or supercritical state, bicyclo [ 2.2.1] A production method capable of obtaining heptenes with high selectivity is also disclosed (see, for example, Patent Document 4).
ビシクロ［２．２．１］ヘプタン誘導体は上記のように５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エンなどのビシクロ［２．２．１］ヘプテン類を異性化することにより製造される。特許文献３においては固体酸触媒を用いた気相異性化が行われているが、触媒活性の低下が著しく、安定した連続運転ができないという問題がある。
本発明は、このような状況下で、機能性モノマーやトラクションドライブ用流体の基油製造原料などとして有用なビシクロ［２．２．１］ヘプタン誘導体の製造に際し、ビシクロ［２．２．１］ヘプテン類の異性化の長期連続運転を可能とし、ビシクロ［２．２．１］ヘプタン誘導体が高収率で安定して得られる方法を提供することを目的とするものである。 Under such circumstances, the present invention provides bicyclo [2.2.1] bicyclo [2.2.1] heptane derivatives useful as functional monomers and raw materials for producing base oils for traction drive fluids. It is an object of the present invention to provide a method that enables a long-term continuous operation of isomerization of heptenes and can stably obtain a bicyclo [2.2.1] heptane derivative in a high yield.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、ビシクロ［２．２．１］ヘプテン類の異性化を液相で行うことにより触媒活性を安定に保つことができること、原料であるビシクロ［２．２．１］ヘプテン類中の水分量を抑えることにより初期活性の急激な低下を抑えることができること、触媒を特定の方法で前処理することにより初期活性をコントロールできること、従って、これらの操作を組み合わせることにより、異性化反応の長期間連続運転ができ、ビシクロ［２．２．１］ヘプタン誘導体が高収率で安定して得られること見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to achieve the above object, the present inventors can maintain the catalytic activity stably by performing isomerization of bicyclo [2.2.1] heptenes in the liquid phase. The ability to control the initial activity by pretreating the catalyst in a specific manner, by suppressing the water content in the raw material bicyclo [2.2.1] heptenes, Therefore, it has been found that by combining these operations, the isomerization reaction can be continuously operated for a long period of time, and the bicyclo [2.2.1] heptane derivative can be stably obtained in a high yield. The present invention has been completed based on such findings.
すなわち、本発明は以下のビシクロ［２．２．１］ヘプタン誘導体の製造方法を提供するものである。
（１） プロピレン又はブテンとシクロペンタジエン又はジシクロペンタジエンとをディールス・アルダー反応させて得られた反応生成物を、異性化触媒の存在下で異性化してビシクロ［２．２．１］ヘプタン誘導体を製造するに際し、異性化反応を液相で行うことを特徴とするビシクロ［２．２．１］ヘプタン誘導体の製造方法。
（２） 異性化触媒として、固体酸触媒を不活性ガスの存在下、５０〜５００℃の温度で前処理した触媒を用いる（１）のビシクロ［２．２．１］ヘプタン誘導体の製造方法。
（３） 異性化触媒が、アルミナボリアである（２）のビシクロ［２．２．１］ヘプタン誘導体の製造方法。
（４） 異性化反応器に供するディールス・アルダー反応生成物が、水分含有量５００ｐｐｍ以下である（１）〜（３）のいずれかのビシクロ［２．２．１］ヘプタン誘導体の製造方法。
（５） 異性化反応を、反応温度２０〜４００℃、圧力０．１ＭＰａ以上で行う（１）〜（４）のいずれかのビシクロ［２．２．１］ヘプタン誘導体の製造方法。
（６） ２−ブテンとシクロペンタジエン又はジシクロペンタジエンとをディールス・アルダー反応させて得られた反応生成物を異性化させる（１）〜（５）のいずれかのビシクロ［２．２．１］ヘプタン誘導体の製造方法。
That is, the present invention provides the following method for producing a bicyclo [2.2.1] heptane derivative.
(1) A reaction product obtained by Diels-Alder reaction of propylene or butene with cyclopentadiene or dicyclopentadiene is isomerized in the presence of an isomerization catalyst to obtain a bicyclo [2.2.1] heptane derivative. A method for producing a bicyclo [2.2.1] heptane derivative, wherein the isomerization reaction is carried out in a liquid phase during production.
(2) The method for producing a bicyclo [2.2.1] heptane derivative according to (1), wherein a catalyst obtained by pretreating a solid acid catalyst at a temperature of 50 to 500 ° C. in the presence of an inert gas is used as the isomerization catalyst.
(3) The method for producing a bicyclo [2.2.1] heptane derivative according to (2), wherein the isomerization catalyst is alumina boria.
(4) The method for producing a bicyclo [2.2.1] heptane derivative according to any one of (1) to (3), wherein the Diels-Alder reaction product used in the isomerization reactor has a water content of 500 ppm or less.
(5) The method for producing a bicyclo [2.2.1] heptane derivative according to any one of (1) to (4), wherein the isomerization reaction is performed at a reaction temperature of 20 to 400 ° C. and a pressure of 0.1 MPa or more.
(6) Biisomer [2.2.1] according to any one of (1) to (5), wherein 2-butene and cyclopentadiene or dicyclopentadiene are subjected to Diels-Alder reaction to isomerize the reaction product. A method for producing a heptane derivative.
本発明によれば、ビシクロ［２．２．１］ヘプテン類の異性化における触媒の活性低下や急激な劣化が抑制されて長期連続運転が可能となり、機能性モノマーやトラクションドライブ用流体の基油製造原料などとして有用なビシクロ［２．２．１］ヘプタン誘導体を高収率で安定して製造することができる。 According to the present invention, it is possible to suppress long-term continuous operation by suppressing a decrease in catalyst activity and rapid deterioration in the isomerization of bicyclo [2.2.1] heptenes, and a functional monomer or a base oil for a traction drive fluid. Bicyclo [2.2.1] heptane derivatives useful as production raw materials can be stably produced in high yield.
本発明のビシクロ［２．２．１］ヘプタン誘導体の製造方法においてディールス・アルダー反応に供される原料としてはプロピレン又はブテンとシクロペンタジエン又はジシクロペンタジエンが用いられる。ブテンとしては１−ブテン及び２−ブテンが好ましく、これらの中で特に２−ブテンが好ましい。この２−ブテンはシス体、トランス体のいずれを用いてもよいし、その混合物を用いてもよい。
このディールス・アルダー反応において、原料のオレフィンとしてプロピレンを用いた場合には５−メチル−ビシクロ［２．２．１］ヘプト−２エンが、原料に１−ブテンを用いた場合には５−エチル−ビシクロ［２．２．１］ヘプト−２エンが、原料に２−ブテンを用いた場合には５，６−ジメチル−ビシクロ［２．２．１］ヘプト−２エンが製造される。
In the production method of the bicyclo [2.2.1] heptane derivative of the present invention, propylene or butene and cyclopentadiene or dicyclopentadiene are used as raw materials to be subjected to Diels-Alder reaction. As butene, 1-butene and 2-butene are preferable, and 2-butene is particularly preferable among these. As this 2-butene, either a cis isomer or a trans isomer may be used, or a mixture thereof may be used.
In this Diels-Alder reaction, 5-methyl-bicyclo [2.2.1] hept-2ene is used when propylene is used as the starting olefin, and 5-ethyl is used when 1-butene is used as the starting material. When bicyclo [2.2.1] hept-2ene is used as the starting material and 2-butene is used, 5,6-dimethyl-bicyclo [2.2.1] hept-2ene is produced.
ディールス・アルダー反応のもう一方の原料である共役二重結合をもつ化合物としては、シクロペンタジエンそのものを用いてもよく、ジシクロペンタジエンを用いてもよい。ジシクロペンタジエンは加熱により容易に熱分解してシクロペンタジエンを生成し、実質的にシクロペンタジエンが反応に供されることになる。
プロピレン又はブテンとシクロペンタジエン又はジシクロペンタジエンの比率は、プロピレン又はブテン／シクロペンタジエンのモル比が通常１以上である。この原料比が１以上であれば目的物以外の重質物の生成を抑制することができる。この原料比は２〜２０がより好ましく、４〜１５が特に好ましい。
ディールス・アルダー反応の温度は、通常約２０〜４００℃、好ましくは１００〜３５０℃である。
As the compound having a conjugated double bond, which is another raw material for the Diels-Alder reaction, cyclopentadiene itself or dicyclopentadiene may be used. Dicyclopentadiene is easily pyrolyzed by heating to produce cyclopentadiene, and cyclopentadiene is substantially subjected to the reaction.
As for the ratio of propylene or butene to cyclopentadiene or dicyclopentadiene, the molar ratio of propylene or butene / cyclopentadiene is usually 1 or more. If this raw material ratio is 1 or more, the generation of heavy substances other than the target product can be suppressed. The raw material ratio is more preferably 2 to 20, and particularly preferably 4 to 15.
The temperature of the Diels-Alder reaction is usually about 20 to 400 ° C, preferably 100 to 350 ° C.
本発明において、ディールス・アルダー反応によるプロピレンからの反応生成物である５−メチル−ビシクロ［２．２．１］ヘプト−２エンを異性化することにより２−メチレンビシクロ［２．２．１］ヘプタンおよび／または２−メチルビシクロ［２．２．１］ヘプト−２−エンが製造され、１−ブテンからの反応生成物である５−エチル−ビシクロ［２．２．１］ヘプト−２−エンを異性化することにより２−エチリデンビシクロ［２．２．１］ヘプタンおよび／または２−エチルビシクロ［２．２．１］ヘプト−２−エンが製造され、２−ブテンからの反応生成物である５，６−ジメチル−ビシクロ［２．２．１］ヘプト−２−エンを異性化することにより２−メチレン−３−メチルビシクロ［２．２．１］へプタンおよび／または２，３−ジメチルビシクロ［２．２．１］へプト−２−エンが得られる。本発明のビシクロ［２．２．１］ヘプタン誘導体には、上記のようなビシクロ［２．２．１］へプタン類とビシクロ［２．２．１］へプテン類を包含する。
以下に、最も一般的である２−ブテンを原料に用いた場合、すなわち５，６−ジメチル−ビシクロ［２．２．１］ヘプト−２−エンを異性化する場合について説明するが、原料に１−ブテンおよびプロピレンを用いた場合にも同様に適用することができる。
In the present invention, 2-methylenebicyclo [2.2.1] is obtained by isomerizing 5-methyl-bicyclo [2.2.1] hept-2ene, which is a reaction product from propylene by Diels-Alder reaction. Heptane and / or 2-methylbicyclo [2.2.1] hept-2-ene is produced and the reaction product from 1-butene, 5-ethyl-bicyclo [2.2.1] hept-2-ene Isomerization of ene produces 2-ethylidenebicyclo [2.2.1] heptane and / or 2-ethylbicyclo [2.2.1] hept-2-ene, reaction product from 2-butene By isomerizing 5,6-dimethyl-bicyclo [2.2.1] hept-2-ene which is 2-methylene-3-methylbicyclo [2.2.1] heptane and / or 2 3-dimethyl-bi hept-2-ene to [2.2.1] can be obtained. Bicyclo [2.2.1] heptane derivatives of the present invention include bicyclo [2.2.1] heptanes and bicyclo [2.2.1] heptenes as described above.
The case where 2-butene, which is the most common, is used as a raw material, that is, a case where 5,6-dimethyl-bicyclo [2.2.1] hept-2-ene is isomerized is described below. The same applies to the case of using 1-butene and propylene.
異性化触媒としては、酸の性質を持つ固体触媒、いわゆる固体酸触媒が好ましい。具体的には、アルミナ，シリカ，チタニア，ジルコニア，クロミア，酸化亜鉛，シリカアルミナ，シリカマグネシア，アルミナボリア，シリカボリア，シリカジルコニアなどの金属酸化物類：リン酸カルシウム，リン酸ジルコニウム，カルシウムヒドロキシアパタイトなどの金属リン酸塩類：硫酸マグネシウム，硫酸カルシウム，硫酸アルミニウムなどの金属硫酸塩類：ベントナイト，モンモリロナイト，カオリンなどの層状シリケート類：活性白土，酸性白土などの白土類：固体リン酸や硫酸をシリカやアルミナに含浸させた固型化酸類：その他イオン交換樹脂、ゼオライトなどが挙げられる。これら固体酸触媒で酸強度が高いものには、シリカアルミナ，アルミナボリア，ゼオライトなど、中程度のものには、チタニア、モンモリロナイトなど、また、酸強度が低いものには、アルミナ，シリカなどがある。
本発明における異性化触媒には酸強度が高いものがより好ましく、特にアルミナボリアが好ましい。異性化触媒にアルミナボリアを用いる場合のボリア濃度は０．１〜５０重量％が好ましく，特に１〜２０重量％が好ましい。ボリア濃度を０．１〜５０重量％とすることにより、高い活性が得られ、かつ、副生成物の生成量を少なくすることができる。
The isomerization catalyst is preferably a solid catalyst having acid properties, so-called solid acid catalyst. Specifically, metal oxides such as alumina, silica, titania, zirconia, chromia, zinc oxide, silica alumina, silica magnesia, alumina boria, silica boria, silica zirconia: metals such as calcium phosphate, zirconium phosphate, calcium hydroxyapatite Phosphate: Metal sulfate such as magnesium sulfate, calcium sulfate, aluminum sulfate: Layered silicates such as bentonite, montmorillonite, kaolin: White clay such as activated clay, acid clay, etc .: Solid phosphoric acid or sulfuric acid impregnated with silica or alumina Solidified acids: Other examples include ion exchange resins and zeolites. Among these solid acid catalysts, those having high acid strength include silica alumina, alumina boria, zeolite, etc., medium ones such as titania and montmorillonite, and those having low acid strength include alumina, silica and the like. .
As the isomerization catalyst in the present invention, those having high acid strength are more preferable, and alumina boria is particularly preferable. When alumina boria is used as the isomerization catalyst, the boria concentration is preferably 0.1 to 50% by weight, particularly preferably 1 to 20% by weight. By setting the boria concentration to be 0.1 to 50% by weight, high activity can be obtained and the amount of by-products generated can be reduced.
本発明において、異性化反応に供するのディールス・アルダー反応生成物（５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エンなど）中の水分濃度は５００ｐｐｍ以下が好ましく，特に１００ｐｐｍ以下が好ましい。原料中の水分を５００ｐｐｍ以下とすることにより，触媒の初期活性の低下を抑制することができ，安定な運転が可能となる。原料中の水分を低減させる方法は一般的な方法であれば，特に制限はないが，モレキュラーシーブ３Ａを用いる方法が特に好ましい。
本発明はディールス・アルダー反応生成物の異性化反応を液相で行うことを特徴とするものである。この異性化反応は有機溶剤の存在下でも無溶媒下であっても進行する。異性化反応の反応温度は通常約２０〜３００℃，特に５０〜２５０℃が好ましい。異性化反応の反応温度が２０℃以上では異性化反応が良好に進行し，３００℃以下であれば原料及び生成物の熱分解を抑制することができる。反応圧力は，反応温度において液相を維持するのに必要な圧力以上であれば，特に制限はないが、通常は０．１ＭＰａ以上、好ましくは０．３〜３ＭＰａである。反応場が気相の場合には活性は安定することなく低下し続けるのでビシクロ［２．２．１］ヘプタン誘導体を安定して製造することができないが、本発明により反応器を加圧し反応場の液相を保つことにより，初期活性の低下後，活性は安定し，長期連続運転が可能となる。
異性化反応の反応器の形式は固定床型管型反応器，連続攪拌槽型反応器等，いかなる反応器の形式も採用できるが，固定床型管型反応器が特に好ましい。
異性化触媒に対する原料の供給量は、重量空間速度ＷＨＳＶが、通常０．０１〜２０ｈ-1，好ましくは０．１〜１０ｈ-1になるようにする。
In the present invention, the water concentration in the Diels-Alder reaction product (5,6-dimethylbicyclo [2.2.1] hept-2-ene etc.) used for the isomerization reaction is preferably 500 ppm or less, particularly 100 ppm or less. Is preferred. By setting the water content in the raw material to 500 ppm or less, a decrease in the initial activity of the catalyst can be suppressed, and a stable operation becomes possible. The method for reducing moisture in the raw material is not particularly limited as long as it is a general method, but a method using molecular sieve 3A is particularly preferable.
The present invention is characterized in that the isomerization reaction of the Diels-Alder reaction product is performed in a liquid phase. This isomerization reaction proceeds in the presence or absence of an organic solvent. The reaction temperature of the isomerization reaction is usually about 20 to 300 ° C, particularly preferably 50 to 250 ° C. If the reaction temperature of the isomerization reaction is 20 ° C. or higher, the isomerization reaction proceeds well, and if it is 300 ° C. or lower, thermal decomposition of the raw materials and products can be suppressed. The reaction pressure is not particularly limited as long as it is equal to or higher than the pressure necessary for maintaining the liquid phase at the reaction temperature, but is usually 0.1 MPa or higher, preferably 0.3 to 3 MPa. In the case where the reaction field is a gas phase, the activity continues to decrease without being stable, so that the bicyclo [2.2.1] heptane derivative cannot be stably produced. By maintaining this liquid phase, the activity stabilizes after the initial activity declines, enabling long-term continuous operation.
As the type of the reactor for the isomerization reaction, any type of reactor such as a fixed bed type tubular reactor or a continuous stirred tank type reactor can be adopted, but a fixed bed type tubular reactor is particularly preferable.
The feed rate of the raw material to the isomerization catalyst is such that the weight space velocity WHSV is usually 0.01 to 20 h −1 , preferably 0.1 to 10 h −1 .
本発明において、異性化反応で使用する触媒は，Ｎ2やアルゴン等の不活性ガスを流通させながら加熱前処理を行うことが好ましい。前処理温度は，５０〜５００℃が好ましく，特に１００〜３００℃が好ましい。この温度が５０℃以上であれば，触媒上に吸着している水の脱離が容易であり、また，５００℃以下であれば，触媒の結晶構造が変化するのを抑制することができる。前処理時間は不活性ガス流量及び温度によって変わるため，限定できないが，前処理時の出口ガス中の水分量が一定になるまで行う。出口ガス中の水分量測定方法としては，露点計を利用する方法が好適に用いられる。 In the present invention, the catalyst used in the isomerization reaction is preferably subjected to pretreatment with heating while circulating an inert gas such as N 2 or argon. The pretreatment temperature is preferably 50 to 500 ° C, particularly preferably 100 to 300 ° C. If this temperature is 50 ° C. or higher, desorption of water adsorbed on the catalyst is easy, and if it is 500 ° C. or lower, it is possible to suppress a change in the crystal structure of the catalyst. The pretreatment time varies depending on the inert gas flow rate and temperature, so it cannot be limited, but is performed until the moisture content in the outlet gas during pretreatment becomes constant. As a method for measuring the amount of water in the outlet gas, a method using a dew point meter is preferably used.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
実施例１
内径１４ｍｍ，長さ４００ｍｍのステンレス製反応管にアルミナボリア触媒（触媒化成工業（株）製 Ｃ−１５、ボリア濃度５重量％）２９．６ｇを充填した。これを常圧下、窒素４００ｍｌ／ｍｉｎを流しながら，１５０℃で１２時間前処理を行った。前処理終了は出口ガスの露点が−３６℃以下（水分量２００ｐｐｍ以下）で一定となることを確認した。
液相異性化反応は、モレキュレーシーブ３Ａで水分を１０ｐｐｍ以下に脱水した５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エンを６９．０ｍｌ／ｈｒ（ＷＨＳＶ＝２．０ｈ-1）で反応器に連続供給し，液相を保つために圧力０．５ＭＰａＧで反応を行った。転化率がほぼ一定になるように反応開始時は反応温度１００℃，その後触媒活性の低下にともない徐々に温度を上げ，約３０日で活性がほぼ安定した。活性安定後の運転開始後６０日目，反応温度２１３℃の反応成績は５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝９０．６％，ビシクロ［２．２．１］ヘプタン誘導体への選択率＝９９．３％であった。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
A stainless steel reaction tube having an inner diameter of 14 mm and a length of 400 mm was charged with 29.6 g of an alumina boria catalyst (C-15 manufactured by Catalyst Chemical Industry Co., Ltd., boria concentration 5 wt%). This was pretreated at 150 ° C. for 12 hours while flowing 400 ml / min of nitrogen under normal pressure. At the end of the pretreatment, it was confirmed that the dew point of the outlet gas was constant at −36 ° C. or less (water content 200 ppm or less).
The liquid phase isomerization reaction was carried out using 69.0 ml / hr (WHSV = 2.0 h) of 5,6-dimethylbicyclo [2.2.1] hept-2-ene dehydrated to 10 ppm or less with molecular sieve 3A. -1 ) was continuously supplied to the reactor, and the reaction was carried out at a pressure of 0.5 MPaG in order to maintain the liquid phase. The reaction temperature was 100 ° C. at the start of the reaction so that the conversion rate was almost constant, and then the temperature was gradually raised as the catalyst activity decreased, and the activity became almost stable in about 30 days. On the 60th day after the start of operation after stabilization of the activity, the reaction performance at a reaction temperature of 213 ° C. was 5,6-dimethylbicyclo [2.2.1] hept-2-ene conversion = 90.6%, bicyclo [2.2 .1] Selectivity to heptane derivative = 99.3%.
実施例２
実施例１において，反応条件を３４．５ｍｌ／ｈｒ（ＷＨＳＶ＝１．０ｈ-1），２０３℃に変更したところ，実施例１と同様に活性が安定していることを確認した。運転開始後８６日目の反応成績は５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝９０．４％，選択率＝９９．２％であった。
Example 2
In Example 1, when the reaction conditions were changed to 34.5 ml / hr (WHSV = 1.0 h −1 ) and 203 ° C., it was confirmed that the activity was stable as in Example 1. On the 86th day after the start of operation, the reaction results were 5,6-dimethylbicyclo [2.2.1] hept-2-ene conversion = 90.4% and selectivity = 99.2%.
実施例３
実施例１と同様に，内径１４ｍｍ，長さ４００ｍｍのステンレス製反応管にアルミナボリア触媒（触媒化成工業（株）製 Ｃ−１５、ボリア濃度５重量％）２７．６ｇを充填した。これを常圧下，窒素４００ｍｌ／ｍｉｎを流しながら，３００℃，２時間で前処理を行った。原料はモレキュラーシーブ３Ａによる脱水処理を行っていない５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン（水分量２００ｐｐｍ）を用いて，実施例１と同様に反応を行った。
運転開始後３６日目，２０５℃，ＷＨＳＶ＝１．０ｈ-1で５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝８０．８％，選択率＝９９．３％。供給量を変更し，運転開始後４０日目，２０５℃，ＷＨＳＶ＝０．６７ｈ-1で、５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝９１．１％，選択率＝９９．０％であった。
Example 3
In the same manner as in Example 1, 27.6 g of an alumina boria catalyst (C-15 manufactured by Catalytic Chemical Industry Co., Ltd., boria concentration 5 wt%) was packed in a stainless steel reaction tube having an inner diameter of 14 mm and a length of 400 mm. This was pretreated at 300 ° C. for 2 hours while flowing 400 ml / min of nitrogen under normal pressure. The reaction was carried out in the same manner as in Example 1 using 5,6-dimethylbicyclo [2.2.1] hept-2-ene (water content 200 ppm) that had not been dehydrated by molecular sieve 3A.
On the 36th day after the start of operation, conversion to 5,6-dimethylbicyclo [2.2.1] hept-2-ene at 205 ° C. and WHSV = 1.0 h −1 = 80.8%, selectivity = 99.3 %. On the 40th day after the start of operation at 205 ° C., WHSV = 0.67 h −1 , conversion of 5,6-dimethylbicyclo [2.2.1] hept-2-ene = 91.1% The selectivity was 99.0%.
実施例４
実施例３で，原料をモレキュレーシーブ３Ａで水分を１０ｐｐｍ以下に脱水した５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エンに交換したところ，活性が向上することを確認した。
この結果、２０５℃，ＷＨＳＶ＝１．０ｈ-1の条件で，運転開始後４４日目で原料切替前の反応成績は５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝７３．６％，選択率＝９９．３％であり、原料切替後１３日目（運転開始後５７日目）の反応成績は５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝９１．９％，選択率＝９９．３％であった。
Example 4
In Example 3, it was confirmed that the activity was improved when the raw material was replaced with 5,6-dimethylbicyclo [2.2.1] hept-2-ene which was dehydrated to 10 ppm or less with molecular sieve 3A. did.
As a result, the reaction results before starting material switching on the 44th day after starting operation under the conditions of 205 ° C. and WHSV = 1.0 h −1 were 5,6-dimethylbicyclo [2.2.1] hept-2-ene conversion. The rate of reaction was 73.6%, the selectivity was 99.3%, and the reaction performance on the 13th day after starting material switching (57th day after starting operation) was 5,6-dimethylbicyclo [2.2.1] hept- The conversion rate of 2-ene was 91.9% and the selectivity was 99.3%.
比較例１
内径１０ｍｍ，長さ１５０ｍｍのステンレス製反応管にアルミナボリア触媒（触媒化成工業（株）製 Ｃ−１５、ボリア濃度５重量％）５．４ｇを充填した。これを常圧下，窒素１００ｍｌ／ｍｉｎを流しながら，３００℃で２時間前処理を行った。
気相異性化反応は，５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エンを３．４ｍｌ／ｈｒ（ＷＨＳＶ＝１．８ｈｒ-1）で１５０℃の予備加熱器を通した後，反応器に供給した。圧力は常圧で行った。反応開始時の反応温度は１８０℃，その後触媒活性の低下にともない徐々に温度を上げ，２８０℃まで昇温したが，活性は低下し続け，安定するには至らなかった。運転開始後２０日目の反応成績はＷＨＳＶ＝０．２ｈｒ-1，反応温度２４０℃で５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝７０．２％，選択率＝９２．９％，運転開始後４０日目の反応成績は，ＷＨＳＶ＝０．２ｈｒ-1，反応温度２８０℃で５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝５１．３％，選択率＝７５．５％であった。
Comparative Example 1
A stainless steel reaction tube having an inner diameter of 10 mm and a length of 150 mm was charged with 5.4 g of an alumina boria catalyst (C-15 manufactured by Catalyst Chemical Industry Co., Ltd., boria concentration 5 wt%). This was pretreated at 300 ° C. for 2 hours while flowing 100 ml / min of nitrogen under normal pressure.
In the gas phase isomerization reaction, 5,6-dimethylbicyclo [2.2.1] hept-2-ene was passed through a preheater at 150 ° C. at 3.4 ml / hr (WHSV = 1.8 hr −1 ). After that, it was fed to the reactor. The pressure was normal pressure. The reaction temperature at the start of the reaction was 180 ° C., and then gradually increased with a decrease in catalyst activity, and the temperature was increased to 280 ° C. However, the activity continued to decrease and did not stabilize. On the 20th day after the start of operation, the reaction results are WHSV = 0.2 hr −1 , conversion temperature of 5,6-dimethylbicyclo [2.2.1] hept-2-ene at a reaction temperature of 240 ° C. = 70.2%, selection Rate = 92.9%, Reaction results on the 40th day after the start of operation are WHSV = 0.2 hr −1 , conversion of 5,6-dimethylbicyclo [2.2.1] hept-2-ene at a reaction temperature of 280 ° C. The rate was 51.3% and the selectivity was 75.5%.
実施例５
内径１０ｍｍ，長さ４００ｍｍのステンレス製反応管にアルミナボリア触媒（触媒化成工業（株）製 Ｃ−１５、ボリア濃度５重量％）１４．４ｇを充填した。これを窒素置換し，触媒の前処理を行わずに，実施例３と同様に脱水処理を行っていない５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン（水分量２００ｐｐｍ）を用いて，液相を保つために圧力０．５ＭＰａＧで実施例１と同様に反応を行った。反応温度１６０℃以下では反応が進行しなかった。反応温度を２１０℃に上げたところ，反応は進行し，運転開始後２日目の反応成績は，ＷＨＳＶ＝１．０ｈ-1で５，６−ジメチルビシクロ［２．２．１］ヘプト−２−エン転化率＝６０．１％、選択率＝９９．１％であった。
以上の各実施例と各比較例の操作条件の概要と反応成績を第１表に示す。
Example 5
A stainless steel reaction tube having an inner diameter of 10 mm and a length of 400 mm was charged with 14.4 g of an alumina boria catalyst (C-15 manufactured by Catalyst Chemical Industry Co., Ltd., boria concentration 5 wt%). This was replaced with nitrogen, and 5,6-dimethylbicyclo [2.2.1] hept-2-ene (water content 200 ppm) was not subjected to dehydration treatment as in Example 3 without performing catalyst pretreatment. Was used in the same manner as in Example 1 at a pressure of 0.5 MPaG to maintain the liquid phase. The reaction did not proceed at a reaction temperature of 160 ° C. or lower. When the reaction temperature was raised to 210 ° C., the reaction proceeded, and the reaction results on the second day after the start of operation were as follows: 5,6-dimethylbicyclo [2.2.1] hept-2 at WHSV = 1.0 h −1. -Conversion of ene = 60.1%, selectivity = 99.1%.
Table 1 shows an overview of the operating conditions and reaction results of the above Examples and Comparative Examples.
Claims (6)
The bicyclo [2.2.1] heptane derivative according to any one of claims 1 to 5, wherein a reaction product obtained by subjecting 2-butene and cyclopentadiene or dicyclopentadiene to Diels-Alder reaction is isomerized. Production method.
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