JP2000191557A - Purification of styrenes - Google Patents
Purification of styrenesInfo
- Publication number
- JP2000191557A JP2000191557A JP11033355A JP3335599A JP2000191557A JP 2000191557 A JP2000191557 A JP 2000191557A JP 11033355 A JP11033355 A JP 11033355A JP 3335599 A JP3335599 A JP 3335599A JP 2000191557 A JP2000191557 A JP 2000191557A
- Authority
- JP
- Japan
- Prior art keywords
- styrenes
- reaction
- phenylacetylenes
- hydrogen
- hydrogenation
- 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.)
- Pending
Links
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、スチレン類の精製
方法、特に、含有されるフェニルアセチレン類を除去・
精製する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying styrenes, and more particularly to a method for removing phenylacetylenes contained therein.
It relates to a method for purification.
【０００２】[0002]
【従来の技術】スチレン類はポリマー原料として広く用
いられている。しかし、エチルベンゼン類の脱水素反応
によって得られるスチレン類を重合させてポリマーを製
造する場合に、該スチレン類に含まれるフェニルアセチ
レン類が重合抑制剤として働くことにより、スチレン類
の重合特性にバラツキが生じて安定した品質のポリマー
製品が得られない問題点があった。2. Description of the Related Art Styrenes are widely used as raw materials for polymers. However, when a polymer is produced by polymerizing styrenes obtained by a dehydrogenation reaction of ethylbenzenes, the phenylacetylenes contained in the styrenes act as a polymerization inhibitor, causing variations in the polymerization characteristics of the styrenes. There was a problem that a polymer product of stable quality could not be obtained.
【０００３】従来、スチレン類に含まれるフェニルアセ
チレン類を除去する方法として、スチレン類を水素添加
触媒の存在下で、含有されるフェニルアセチレン類を選
択的に水素添加反応して除去する方法が提案されている
（米国特許第３，６３４，５３１号、特開昭６０−１３
７２４号公報、特開昭６２−７２６３４号公報、特開昭
６２−１４９６３４号公報、特公平８−５８１４号公
報、特公平８−５８１５号公報、特公平３−４０４６号
公報）。しかし、これらの方法においては、水素添加反
応系の外部から、水素含有ガスを反応系に供給する必要
があり、しかも、水素含有ガスを供給するために煩雑な
操作と複雑な分離反応装置を必要とするものであった。
さらに、安価な水素源を用いるフェニルアセチレン類の
除去方法として、エチルベンゼン類の脱水素反応で生成
したガス留分を用いる方法が提案されている。（特公平
７−４５４１９号報）。しかし、同公報に記載の方法は
エチルベンゼン類の脱水素反応で生成した反応生成物か
らガス留分を分離、回収し、さらに、この回収ガス留分
をスチレン類の精製系に供給するといった煩雑な操作と
複雑な分離反応装置を必要とするものであり、このため
に、上記の方法は工業的に有利に実施できるスチレン類
の精製方法とはいえないものであった。Conventionally, as a method for removing phenylacetylenes contained in styrenes, there has been proposed a method for selectively removing hydrogenated phenylacetylenes in the presence of a hydrogenation catalyst. (U.S. Pat. No. 3,634,531, JP-A-60-13)
724, JP-A-62-72634, JP-A-62-149634, JP-B-8-5814, JP-B-8-5815, and JP-B-3-4046. However, in these methods, it is necessary to supply a hydrogen-containing gas to the reaction system from outside the hydrogenation reaction system, and furthermore, complicated operations and complicated separation reactors are required to supply the hydrogen-containing gas. It was to be.
Further, as a method for removing phenylacetylenes using an inexpensive hydrogen source, a method using a gas fraction generated by a dehydrogenation reaction of ethylbenzenes has been proposed. (Japanese Patent Publication No. 7-45419). However, the method described in this publication separates and recovers a gas fraction from a reaction product generated in the dehydrogenation reaction of ethylbenzenes, and further collects and supplies the recovered gas fraction to a styrene purification system. Operation and a complicated separation reaction apparatus are required, and therefore, the above-mentioned method cannot be said to be a method for purifying styrenes which can be industrially advantageously carried out.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、スチレン類
に含有されるフェニルアセチレン類を工業的に有利に除
去できるスチレン類の精製方法を提供することを目的と
する。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for purifying styrenes which can industrially and advantageously remove phenylacetylenes contained in styrenes.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記の課
題を解決するために鋭意検討を重ねた結果、エチルベン
ゼン類の脱水素反応で生成したスチレン類を精製するに
当たり、スチレン類に含有されるフェニルアセチレン類
を水素添加触媒の存在下で水素添加反応して除去する方
法において、水素源として該スチレン類中に溶存する水
素により水素添加反応を行えば、外部から水素含有ガス
を供給することなく、フェニルアセチレン類のみが選択
的に水素添加されることを見出し、本発明を完成するに
至った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, when purifying styrenes produced by the dehydrogenation reaction of ethylbenzenes, the styrenes contained in the styrenes were purified. In the method of removing the phenylacetylenes to be subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst, a hydrogen-containing gas is supplied from the outside if the hydrogenation reaction is carried out with hydrogen dissolved in the styrenes as a hydrogen source. Without having found that only phenylacetylenes were selectively hydrogenated, the present invention was completed.
【０００６】すなわち、本発明は、エチルベンゼン類の
脱水素反応後、ガス留分と分離して得たスチレン類を、
該スチレン類に含まれるフェニルアセチレン類を水素添
加触媒の存在下で選択的に水素添加反応することにより
除去して精製する方法において、該スチレン類を水素添
加反応系に供給して水素添加反応する際、該スチレン類
中に溶存する水素を水素源として利用し、外部から水素
を供給することなく水素添加反応してフェニルアセチレ
ン類を除去することを特徴とするスチレン類の精製方法
である。エチルベンゼン類の脱水素反応生成物であるス
チレン類中に溶解している水素を利用する本発明の利点
はつぎのとおりである。 １）選択的にフェニルアセチレン類を水素添加反応して
除去できること、 ２）エチルベンゼン類の脱水素反応で生成したスチレン
類には水素が溶解しており、この溶存水素のみでフェニ
ルアセチレン類を水素添加反応して除去できるから、ス
チレン類の精製において、外部から水素を供給する必要
がなく、したがって装置や反応操作が単純であり、かつ
経済的にも有利である。That is, according to the present invention, styrenes obtained by separating a gas fraction after the dehydrogenation reaction of ethylbenzenes are
In a method of removing and purifying phenylacetylenes contained in the styrenes by selectively performing a hydrogenation reaction in the presence of a hydrogenation catalyst, the styrenes are supplied to a hydrogenation reaction system to perform a hydrogenation reaction. In this case, a method for purifying styrenes is characterized in that hydrogen dissolved in the styrenes is used as a hydrogen source, and phenylacetylenes are removed by a hydrogenation reaction without supplying hydrogen from the outside. The advantages of the present invention utilizing hydrogen dissolved in styrenes, which are dehydrogenation products of ethylbenzenes, are as follows. 1) that phenylacetylenes can be selectively removed by hydrogenation reaction; 2) hydrogen is dissolved in styrenes generated by the dehydrogenation reaction of ethylbenzenes, and phenylacetylenes are hydrogenated only with this dissolved hydrogen. Since it can be removed by reaction, it is not necessary to supply hydrogen from the outside in the purification of styrenes, so that the apparatus and the reaction operation are simple and economically advantageous.
【０００７】以下、本発明を詳細に説明する。本発明の
精製方法の対象となるスチレン類とは、スチレン、ｐ−
メチルスチレン、ビニルトルエン、ｐ−ｔ−ブチルスチ
レンおよびジビニルベンゼン等のスチレン類、およびこ
れらの少なくとの１種類を含有する組成物である。Hereinafter, the present invention will be described in detail. The styrenes targeted for the purification method of the present invention include styrene, p-
A composition containing styrenes such as methylstyrene, vinyltoluene, pt-butylstyrene and divinylbenzene, and at least one of these.
【０００８】該スチレン類は、通常、エチルベンゼン、
ｐ−メチルエチルベンゼン、エチルトルエン、ｐ−ｔ−
ブチルベンゼン、ジエチルベンゼン等の少なくとも１種
類のエチルベンゼン類を脱水素触媒、例えばＦｅ−Ｃｅ
−Ｋ及びＦｅ−Ｃｅ−Ｍｏ−Ｋを主成分とする触媒、ま
たはＦｅ−Ｃｒ−Ｋを主成分とする触媒等の種々の脱水
素触媒の存在下で脱水素反応させて得ることができる。
上記の方法で得られるスチレン類には、フェニルアセチ
レン類が含まれている。フェニルアセチレン類とは、フ
ェニルアセチレン、メチルフェニルアセチレン、エチル
フェニルアセチレン、ｐ−ｔ−ブチルフェニルアセチレ
ン、フェニルビニルアセチレン、フェニルジアセチレン
等をいう。スチレン類に含有されるフェニルアセチレン
類の含有量は、製造条件等によっても異なるが、通常、
フェニルアセチレン類が１０〜１０００ｐｐｍ（重量）
程度である。The styrenes are usually ethylbenzene,
p-methylethylbenzene, ethyltoluene, pt-
At least one kind of ethylbenzenes such as butylbenzene and diethylbenzene is converted to a dehydrogenation catalyst such as Fe-Ce
It can be obtained by performing a dehydrogenation reaction in the presence of various dehydrogenation catalysts such as a catalyst mainly containing -K and Fe-Ce-Mo-K, or a catalyst mainly containing Fe-Cr-K.
The styrenes obtained by the above method include phenylacetylenes. Phenylacetylene means phenylacetylene, methylphenylacetylene, ethylphenylacetylene, pt-butylphenylacetylene, phenylvinylacetylene, phenyldiacetylene and the like. The content of phenylacetylenes contained in styrenes varies depending on production conditions and the like, but is usually
Phenylacetylene is 10 to 1000 ppm (weight)
It is about.
【０００９】本発明の水素添加系に供給されるスチレン
類に含まれる水分量はフェニルアセチレン類の水素添加
反応が選択的に進行すればよく、その範囲は特に限定さ
れないが、水素添加触媒の活性安定性の点から、２，０
００重量ｐｐｍ以下が好適である。The amount of water contained in the styrene supplied to the hydrogenation system of the present invention is not particularly limited as long as the hydrogenation reaction of phenylacetylene proceeds selectively, and the range is not particularly limited. From the point of stability, 2,0
It is preferably at most 00 ppm by weight.
【００１０】本発明の該スチレン類に溶解している水素
濃度は、製造条件や水素添加反応の圧力等によっても異
なるが、通常、１〜１２重量ｐｐｍ程度である。水素濃
度が低すぎるとフェニルアセチレン類の除去が不充分と
なる。The concentration of hydrogen dissolved in the styrenes of the present invention varies depending on the production conditions, the pressure of the hydrogenation reaction and the like, but is usually about 1 to 12 ppm by weight. If the hydrogen concentration is too low, the removal of phenylacetylenes will be insufficient.
【００１１】本発明の精製方法で使用する水素添加触媒
は、水素添加反応の触媒機能を有するものであればよ
く、特に限定されるものでないが、例えばＶＩＩＩ族の
金属、とくに、Ｐｄ、Ｎｉ、Ｐｔなどを触媒成分とする
水素添加触媒等が好適に使用できる。通常、触媒成分は
適当な担体に担持されており、その触媒成分の担持量は
０．０１〜１重量％程度である。また、担体としては、
耐熱性の無機化合物担体、例えば、アルミナ、シリカ等
の合成ゲル担体、あるいは、ケイソウ土、多孔性粘土等
の天然無機担体等が挙げられる。担体はとくに成形され
たものである必要はないが、後処理工程の利便性、ある
いは連続方式の場合は反応相における圧力損失防止のた
めに適当な径に成形されたものが好ましく、たとえば数
ｍｍ径の小塊状に成形したものが好適である。The hydrogenation catalyst used in the purification method of the present invention is not particularly limited as long as it has a catalytic function for the hydrogenation reaction. Examples of the hydrogenation catalyst include, but are not limited to, Group VIII metals, particularly Pd, Ni, A hydrogenation catalyst containing Pt or the like as a catalyst component can be suitably used. Usually, the catalyst component is supported on a suitable carrier, and the amount of the catalyst component supported is about 0.01 to 1% by weight. In addition, as a carrier,
Heat-resistant inorganic compound carriers, for example, synthetic gel carriers such as alumina and silica, and natural inorganic carriers such as diatomaceous earth and porous clay are exemplified. The support does not need to be particularly formed, but preferably is formed into an appropriate diameter for the convenience of the post-treatment step or, in the case of a continuous system, to prevent pressure loss in the reaction phase, for example, several mm. The one molded into a small lump having a diameter is preferable.
【００１２】本発明の水素添加における反応圧力は特に
限定されないが、操作性の点で、１０ｋｇ／ｃｍ２以下
が好適である。The reaction pressure in the hydrogenation of the present invention is not particularly limited, but is preferably 10 kg / cm 2 or less from the viewpoint of operability.
【００１３】本発明の水素添加における反応温度はフェ
ニルアセチレン類の水素添加反応が選択的に進行すれば
よく、その範囲は特に限定されないが、反応速度と反応
選択性の点から、２０〜１００゜Ｃが好ましい。反応温
度が高すぎるとスチレン等の有用成分が水素添加されて
損失となり、反応温度が低すぎるとフェニルアセチレン
類の水素添加反応が遅くなり、工業的実施上に支障をき
たす。The reaction temperature in the hydrogenation of the present invention is not particularly limited as long as the hydrogenation reaction of phenylacetylene proceeds selectively, but the range is not particularly limited. C is preferred. If the reaction temperature is too high, useful components such as styrene are hydrogenated and lost, and if the reaction temperature is too low, the hydrogenation reaction of phenylacetylenes is slowed down, which hinders industrial implementation.
【００１４】本発明の水素添加反応は、選択的にフェニ
ルアセチレン類を水素添加反応して除去できる反応方式
であれば特に限定されないが、例えば、バッチ方式、Ｃ
ＳＴＲ連続方式（連続式かくはん槽反応器方式）、触媒
層へ該スチレン類を連続的に供給して反応させるカラム
連続方式等が適用できる。The hydrogenation reaction of the present invention is not particularly limited as long as it can selectively remove phenylacetylene by hydrogenation reaction.
A STR continuous system (continuous stirred tank reactor system), a column continuous system in which the styrenes are continuously supplied to the catalyst layer and reacted, and the like can be applied.
【００１５】触媒層を用いる連続方式で反応させる場合
の触媒層への該スチレン類の供給速度は、特に限定され
ないが、通常、液空間速度（ＬＨＳＶ）で１〜５００ｈ
ｒ−１程度である。同速度が高すぎるとフェニルアセチ
レン等のフェニルアセチレン類の水素添加反応における
転化率が低下し、フェニルアセチレン類の除去が不充分
となり、同速度が低すぎるとスチレン等の有用成分が水
素添加され損失になる。When the reaction is carried out in a continuous mode using a catalyst layer, the supply rate of the styrene to the catalyst layer is not particularly limited, but it is usually 1 to 500 h at a liquid hourly space velocity (LHSV).
It is about r −1 . If the rate is too high, the conversion in the hydrogenation reaction of phenylacetylene such as phenylacetylene decreases, and the removal of phenylacetylene becomes insufficient.If the rate is too low, useful components such as styrene are hydrogenated and loss occurs. become.
【００１６】[0016]
【実施例】次に実施例をもって本発明を更に説明する
が、本発明はこれらの例によって限定されるものではな
い。これらの例に記載のｐｐｍおよび％は特に記載しな
いかぎり重量基準による。The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Ppm and% given in these examples are by weight unless otherwise indicated.
【００１７】（実施例１）３ｍｍΦ×３ｍｍの円柱型に
成形したγ−アルミナを、濃度０．６％の塩化パラジウ
ム水溶液に含浸させ、１００°Ｃで１昼夜乾燥させた。
次いで、その乾燥物を水素気流下で４００°Ｃの温度で
１６時間還元処理して組成がＰｄ（０．３％）／γ−Ａ
ｌ２Ｏ３の水素添加触媒を得た。上記の水素添加触媒６
ｇを管型反応器に充填し、この触媒の温度を８０°Ｃに
保ちながら、Ｆｅ−Ｃｅ−Ｍｏ−Ｋを主成分とする触媒
を用いてエチルベンゼンを脱水素反応して生成した反応
液（粗スチレン）を精製前のスチレンとして用い、表１
の反応条件で水素添加反応を行った。なおこのとき水素
源として粗スチレン中の溶存水素濃度は３ｐｐｍであっ
た。精製前のスチレン組成を表２に、水素添加反応の反
応生成物の組成を表３に示した。反応生成物の組成から
求めたフェニルアセチレンの除去率（ＰＡ除去率）、フ
ェニルアセチレンの水素添加選択率（Ｈ２選択率）を下
記の式１、式２に基づき求めたところ、それぞれ３９
％、３８％であった。Example 1 γ-alumina molded into a 3 mmΦ × 3 mm cylindrical shape was impregnated with a 0.6% palladium chloride aqueous solution and dried at 100 ° C. for one day.
Next, the dried product was subjected to a reduction treatment at a temperature of 400 ° C. for 16 hours under a stream of hydrogen to obtain a composition of Pd (0.3%) / γ-A
1 2 O 3 hydrogenation catalyst was obtained. The above hydrogenation catalyst 6
g in a tubular reactor, and while maintaining the temperature of the catalyst at 80 ° C., a reaction solution formed by dehydrogenating ethylbenzene using a catalyst mainly composed of Fe—Ce—Mo—K ( Crude styrene) was used as styrene before purification.
The hydrogenation reaction was performed under the following reaction conditions. At this time, the dissolved hydrogen concentration in the crude styrene as a hydrogen source was 3 ppm. Table 2 shows the styrene composition before purification, and Table 3 shows the composition of the reaction product of the hydrogenation reaction. Removal of the phenyl acetylene obtained from the composition of the reaction product (PA removal rate), the hydrogenation selectivity of phenyl acetylene (H 2 selectivity) Equation 1 below were determined based on equation 2, respectively 39
% And 38%.
【００１８】[0018]
【数１】 (Equation 1)
【００１９】[0019]
【数２】 (Equation 2)
【００２０】（比較例１）実施例１で使用した粗スチレ
ンから溶存水素を除去したものを精製前のスチレンとし
て用い、エチルベンゼンの脱水素反応で生成したガス留
分を５ｋｇ／ｃｍ２で反応系に導入した以外は実施例１
と同じ操作を行った。なお、導入したガス留分中の水素
濃度は９１ｖｏｌ％であった。精製前のスチレン組成を
表２に、水素添加反応の反応生成物の組成を表３に示し
た。反応生成物の組成から求めたフェニルアセチレンの
除去率（ＰＡ除去率）、フェニルアセチレンの水素添加
選択率（Ｈ２選択率）を上記の式１、式２に基づき求め
たところ、それぞれ４０％、２９％であった。該比較例
は、本願発明に比べて、フェニルアセチレン除去率は同
等であるが、水素添加選択率に劣った。Comparative Example 1 The crude styrene used in Example 1 from which dissolved hydrogen was removed was used as styrene before purification, and a gas fraction produced by the dehydrogenation reaction of ethylbenzene was reacted at 5 kg / cm 2 to obtain a reaction system. Example 1 except that it was introduced in
The same operation was performed. The hydrogen concentration in the introduced gas fraction was 91 vol%. Table 2 shows the styrene composition before purification, and Table 3 shows the composition of the reaction product of the hydrogenation reaction. Removal of the phenyl acetylene obtained from the composition of the reaction product (PA removal rate), the hydrogenation selectivity of phenyl acetylene (H 2 selectivity) Equation 1 above, and was determined based on equation 2, 40% respectively, 29%. The comparative example had the same phenylacetylene removal rate as the present invention, but was inferior in hydrogenation selectivity.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【表３】 [Table 3]
【００２４】[0024]
【発明の効果】エチルベンゼン類の脱水素反応によって
得られる粗スチレン類に含まれるフェニルアセチレン類
を水素添加反応で除去する方法において、従来、反応系
の外部から水素を供給して反応していたが、本発明のス
チレン類の精製方法では、該スチレンに溶存する水素を
利用するため外部から水素を供給する必要がなく、した
がって装置、操作性が簡単になり、かつ経済的にも有利
である。According to the method of removing phenylacetylenes contained in crude styrenes obtained by dehydrogenation of ethylbenzenes by hydrogenation, hydrogen has been conventionally supplied from outside the reaction system to carry out the reaction. In the method for purifying styrenes of the present invention, since hydrogen dissolved in the styrene is used, there is no need to supply hydrogen from the outside, so that the apparatus and operability are simplified and economically advantageous.
Claims (4)
留分と分離して得たスチレン類に含まれるフェニルアセ
チレン類を、水素添加触媒の存在下で該スチレン類中に
溶存する水素により外部から水素を供給することなく選
択的に水素添加反応して除去することを特徴とするスチ
レン類の精製方法。Claims: 1. After dehydrogenation of ethylbenzenes, phenylacetylenes contained in styrenes obtained by separating from a gaseous fraction are separated from the outside by hydrogen dissolved in the styrenes in the presence of a hydrogenation catalyst. A method for purifying styrenes, comprising selectively removing by hydrogenation reaction without supplying hydrogen.
チレン、ビニルトルエン、ｐ−ｔ−ブチルスチレンおよ
びジビニルベンゼンから選ばれた少なくとも１種類以上
であることを特徴とする請求項１記載のスチレン類の精
製方法。2. The styrene according to claim 1, wherein the styrene is at least one selected from styrene, p-methylstyrene, vinyltoluene, pt-butylstyrene and divinylbenzene. Purification method.
チレン類がフェニルアセチレン、メチルフェニルアセチ
レン、エチルフェニルアセチレン、ｐ−ｔ−ブチルフェ
ニルアセチレン、フェニルビニルアセチレン、およびフ
ェニルジアセチレンから選ばれた少なくとも１種類以上
であることを特徴とする請求項１記載のスチレン類の精
製方法。3. The phenylacetylene to be removed by hydrogenation reaction is at least one selected from phenylacetylene, methylphenylacetylene, ethylphenylacetylene, pt-butylphenylacetylene, phenylvinylacetylene, and phenyldiacetylene. 2. The method for purifying styrenes according to claim 1, wherein:
存水素が１〜１２ｐｐｍであることを特徴とする請求項
１記載のスチレン類の精製方法。4. The method for purifying styrenes according to claim 1, wherein the dissolved hydrogen in the styrenes used for the hydrogenation reaction is 1 to 12 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11033355A JP2000191557A (en) | 1999-01-01 | 1999-01-01 | Purification of styrenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11033355A JP2000191557A (en) | 1999-01-01 | 1999-01-01 | Purification of styrenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000191557A true JP2000191557A (en) | 2000-07-11 |
Family
ID=12384287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11033355A Pending JP2000191557A (en) | 1999-01-01 | 1999-01-01 | Purification of styrenes |
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| Country | Link |
|---|---|
| JP (1) | JP2000191557A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005225916A (en) * | 2004-02-10 | 2005-08-25 | Fuji Xerox Co Ltd | Method for producing organic functional material, organic functional material and organic electroluminescent element using the same |
| WO2014192562A1 (en) * | 2013-05-29 | 2014-12-04 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrogen production method and hydrogen production system |
| WO2017122295A1 (en) * | 2016-01-13 | 2017-07-20 | デンカ株式会社 | Process for producing (olefin/aromatic vinyl)-based copolymer and process for producing cross-copolymer |
-
1999
- 1999-01-01 JP JP11033355A patent/JP2000191557A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005225916A (en) * | 2004-02-10 | 2005-08-25 | Fuji Xerox Co Ltd | Method for producing organic functional material, organic functional material and organic electroluminescent element using the same |
| WO2014192562A1 (en) * | 2013-05-29 | 2014-12-04 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrogen production method and hydrogen production system |
| JP2014231461A (en) * | 2013-05-29 | 2014-12-11 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrogen production method and hydrogen production system |
| WO2017122295A1 (en) * | 2016-01-13 | 2017-07-20 | デンカ株式会社 | Process for producing (olefin/aromatic vinyl)-based copolymer and process for producing cross-copolymer |
| CN108779206A (en) * | 2016-01-13 | 2018-11-09 | 电化株式会社 | The manufacturing method of alkene-aromatic ethenyl compound based copolymer and the manufacturing method for intersecting copolymer |
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