JPH0645561B2 - Styrene-containing material purification method - Google Patents
Styrene-containing material purification methodInfo
- Publication number
- JPH0645561B2 JPH0645561B2 JP3162485A JP3162485A JPH0645561B2 JP H0645561 B2 JPH0645561 B2 JP H0645561B2 JP 3162485 A JP3162485 A JP 3162485A JP 3162485 A JP3162485 A JP 3162485A JP H0645561 B2 JPH0645561 B2 JP H0645561B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- catalyst
- phenylacetylene
- copper
- containing material
- 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.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、スチレン、粗スチレンまたはメチルスチレン
等のスチレン類含有物に含まれるフエニルアセチレンや
アルキルフエニルアセチレン等のフエニルアセチレン類
を、選択的水素添加して除去し、同スチレン類（以下、
スチレン類を単に「スチレン」という）含有物を精製す
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides phenylacetylenes such as phenylacetylene and alkylphenylacetylenes contained in styrene-containing substances such as styrene, crude styrene and methylstyrene, The styrenes (hereinafter,
Styrenes are simply referred to as "styrene").
（従来の技術） エチルベンゼンの脱水素反応によつて得られるスチレン
または粗スチレン等のようなスチレン含有物には、少量
のフエニルアセチレンが含有されていることが多い。該
スチレン含有物に含まれているフエニルアセチレンは、
これを選択的水素添加によつて除去することができる。
しかし、この方法においては、フエニルアセチレンの含
有濃度が低いため、触媒の選択性が悪いと、スチレンの
ビニル基の水素化反応などをひき起し、目的のスチレン
の収率を低下させる。(Prior Art) A styrene-containing material such as styrene or a crude styrene obtained by a dehydrogenation reaction of ethylbenzene often contains a small amount of phenylacetylene. The phenylacetylene contained in the styrene-containing material is
It can be removed by selective hydrogenation.
However, in this method, since the content concentration of phenylacetylene is low, if the selectivity of the catalyst is poor, hydrogenation reaction of the vinyl group of styrene or the like will be caused and the yield of the target styrene will be reduced.
他方、フエニルアセチレンの選択的水素添加に関する方
法は、例えば、特開昭５９−２１６８３８号にpd、Pt、
Ir、RhおよびRuよりなる群から選ばれた１種または２種
以上の金属と、pb、Bi、Ｐ、Sb、As、TeおよびＳよりな
る群から選ばれた１種または２種以上の元素とを含む触
媒を用いて、フエニルアセチレンを選択的に水素添加す
る方法が記載されているが、フエニルアセチレンを経済
的有利に選択的水素化させるには充分とは云えない。On the other hand, a method for selective hydrogenation of phenylacetylene is described in, for example, JP-A-59-216838, pd, Pt,
One or more metals selected from the group consisting of Ir, Rh and Ru, and one or more elements selected from the group consisting of pb, Bi, P, Sb, As, Te and S Although a method for selectively hydrogenating phenylacetylene using a catalyst containing and has been described, it is not sufficient to selectively hydrogenate phenylacetylene economically and advantageously.
（発明が解決しようとする問題点） 前記のように、スチレン含有物に含まれているフエニル
アセチレンを選択的水素添加によつて除去する方法にお
いては、フエニルアセチレンの含有濃度が低いため、触
媒の選択性が悪いと、スチレンのビニル基の水素化反応
などをひき起し、目的のスチレンの収率を低下させるこ
とになり、フエニルアセチレンを経済的有利に選択的水
素化させる方法の出現が望まれていた。(Problems to be solved by the invention) As described above, in the method of removing phenylacetylene contained in the styrene-containing material by selective hydrogenation, the content concentration of phenylacetylene is low, If the selectivity of the catalyst is poor, hydrogenation reaction of the vinyl group of styrene will be caused, and the yield of the target styrene will be reduced, and the method of selective hydrogenation of phenylacetylene will be economically advantageous. Appearance was desired.
（問題点を解決するための手段） 本発明者らは、かかる精製法について鋭意研究した結
果、フエニルアセチレンのみを選択的に水素化でき、し
かも、その触媒活性が高い触媒を見い出し、本発明を成
するに至つた。すなわち、本発明は、担体に担持させた
１価および／または０価の銅を含む触媒を用いることを
特徴とする選択的水素添加によるスチレン類含有物の精
製法である。(Means for Solving Problems) As a result of earnest studies on such a purification method, the present inventors have found a catalyst capable of selectively hydrogenating only phenylacetylene, and having a high catalytic activity. Was reached. That is, the present invention is a method for purifying a styrene-containing product by selective hydrogenation, which comprises using a catalyst containing monovalent and / or zerovalent copper supported on a carrier.
本発明に供することができる触媒は、銅、銅の無機酸
塩、有機酸塩または酸化物の少なくとも１種を担体に担
持させ、適当な還元剤を用いて１価および／または０価
の銅に還元したものである。The catalyst that can be used in the present invention is copper, at least one of an inorganic acid salt, an organic acid salt or an oxide of copper, which is supported on a carrier, and a monovalent and / or zero-valent copper is added using a suitable reducing agent. It has been reduced to.
担体としては、各種金属酸化物、活性炭等を用いること
ができるが、特にアルミナ、シリカ、活性炭などが好ま
しい。組成として担体に対する銅の比は１〜４８重量
％、好ましくは５〜３０重量％の範囲を選ぶことができ
る。触媒の調製法としては特に制限はなく、通常用いら
れる担持方法を適宜利用すればよい。１例を示すと、次
のような方法で調製することができる。アルミナ担体に
塩化銅、硝酸銅、酢酸銅、硫酸銅などの酸または水に可
溶な塩類の溶液を所定量含浸させた後、この銅塩を空気
中または酸素を含有する不活性ガス中で高温加熱する。
次いで、この銅酸化物を水素、ヒドラジン、ホルムアル
デヒド、ギ酸ソーダなどの適当な還元剤を用いて、乾式
または湿式法で１価または金属状銅に還元する。As the carrier, various metal oxides, activated carbon and the like can be used, but alumina, silica, activated carbon and the like are particularly preferable. The composition can be selected such that the ratio of copper to the carrier is 1 to 48% by weight, preferably 5 to 30% by weight. The method for preparing the catalyst is not particularly limited, and a commonly used loading method may be appropriately used. As an example, it can be prepared by the following method. After impregnating a predetermined amount of a solution of an acid such as copper chloride, copper nitrate, copper acetate, copper sulfate, or a salt soluble in water in an alumina carrier, the copper salt is in air or in an inert gas containing oxygen. Heat to high temperature.
Next, the copper oxide is reduced to monovalent or metallic copper by a dry or wet method using a suitable reducing agent such as hydrogen, hydrazine, formaldehyde, sodium formate.
本発明の方法を実施する際の反応条件としては、必ずし
も厳密な制限はないが、一般に、次のような条件下で行
われる。The reaction conditions for carrying out the method of the present invention are not necessarily strictly limited, but generally, the reaction conditions are as follows.
水素添加反応温度は２００℃以下、好ましくは５〜１０
０℃である。反応温度が高くなりすぎると、スチレンの
水素化反応を生起させるので好ましくない。反応圧力は
常圧〜加圧下、好ましくは１〜１０kg／cm2の範囲であ
る。The hydrogenation reaction temperature is 200 ° C or lower, preferably 5 to 10
It is 0 ° C. If the reaction temperature is too high, the hydrogenation reaction of styrene will occur, which is not preferable. The reaction pressure is in the range of normal pressure to increased pressure, preferably 1 to 10 kg / cm 2 .
液空間速度（LHSV）は１〜５００Hr-1、好ましくは１〜
２００Hr-1である。液空間速度が高すぎると、フエニル
アセチレンの転化率が低下し、同速度が低すぎると、ス
チレンの水素添加反応を起し、スチレン収量が低下す
る。Liquid hourly space velocity (LHSV) is 1 to 500 Hr -1 , preferably 1 to
It is 200 Hr -1 . If the liquid hourly space velocity is too high, the conversion rate of phenylacetylene will decrease, and if the liquid velocity is too low, hydrogenation reaction of styrene will occur and the styrene yield will decrease.
水素の供給量は、通常、フエニルアセチレンに対し１倍
量〜１００倍量が用いられる。水素量があまり多すぎる
と、スチレンの水素化によるスチレン収量の減少をまね
くので好ましくない。The supply amount of hydrogen is usually 1 to 100 times that of phenylacetylene. If the amount of hydrogen is too large, hydrogenation of styrene may lead to a decrease in styrene yield, which is not preferable.
（発明の効果） 本発明の精製法は、下記のとおり優れた効果を奏するこ
とができる。(Effects of the Invention) The purification method of the present invention can exhibit excellent effects as described below.
(1)フエニルアセチレンの水素添加反応の選択性が著し
く高く、スチレンの水素添加反応およびベンゼン核の水
素添加反応等の副反応を実質上起さないので、高価なス
チレン等のロスが少ない。(1) The selectivity of the hydrogenation reaction of phenylacetylene is remarkably high, and side reactions such as the hydrogenation reaction of styrene and the hydrogenation reaction of the benzene nucleus do not substantially occur, so that the loss of expensive styrene and the like is small.
(2)炭素結合の分裂反応、ガム質生成反応、炭素質生成
反応等を実質上起さないので、貴重な資源のロスが少な
く、かつ触媒寿命が長い。(2) Since a fission reaction of a carbon bond, a gum-forming reaction, a carbon-forming reaction, etc. do not substantially occur, the loss of valuable resources is small and the catalyst life is long.
(3)本触媒系は、貴金属類を用いた水添触媒より安価な
触媒を提供するものであり、かつ活性が高いため経済性
に優れている。(3) The present catalyst system provides a catalyst that is cheaper than a hydrogenation catalyst using a noble metal, and is highly economical because it has high activity.
（実施例） 以下、本発明の実施例を示すが、本発明は、これに限定
されるものではない。(Examples) Examples of the present invention will be shown below, but the present invention is not limited thereto.
（触媒の調製方法） 触媒Ａ 硝酸銅３水塩２９０ｇを水３１８ｇに溶解し、これにγ
−アルミナ３１８ｇを加え、水浴上で蒸発濃縮した。得
られた銅塩担持物を空気中６００℃で３時間焼成したの
ち、水素気流下２００℃で２時間還元処理を行い、銅担
持型アルミナ触媒Ａを得た。(Catalyst Preparation Method) Catalyst A 290 g of copper nitrate trihydrate was dissolved in 318 g of water, and γ was added thereto.
-318 g of alumina were added and concentrated by evaporation on a water bath. The obtained copper salt-supported material was calcined in air at 600 ° C. for 3 hours and then subjected to reduction treatment in a hydrogen stream at 200 ° C. for 2 hours to obtain a copper-supported alumina catalyst A.
実施例 直径２０mm、長さ５０cmのステンレス製管に調製した触
媒Ａ１００ｇを充填し、これにスチレン９９重量％、エ
チルベンゼン１重量％およびフエニルアセチレン１００
重量ppmを含有するスチレンおよび水素ガスを、温度２
０℃、圧力１kg／cm-1、Ｈ2／フエニルアセチレンモル
比＝７／１、LHSV１１Hr-1の条件で連続的に通過させ
た。その結果は図面に示すとおりであり、非常に高い選
択性を示した。Example A stainless steel tube having a diameter of 20 mm and a length of 50 cm was filled with 100 g of the prepared catalyst A, and 99% by weight of styrene, 1% by weight of ethylbenzene and 100% of phenylacetylene.
Styrene and hydrogen gas containing ppm by weight at a temperature of 2
It was continuously passed under the conditions of 0 ° C., pressure 1 kg / cm −1 , H 2 / phenylacetylene molar ratio = 7/1, and LHSV11Hr −1 . The result is as shown in the drawing, which shows very high selectivity.
比較例 γ−Al2O3にPdを0.3重量％担持したPd−Al2O3に、さら
にPdを0.1重量％担持させた触媒を用い、そのほかは実
施例におけると同様の条件を使用して、同一のスチレン
を水素添加処理した。その結果は図面に示すとおりであ
つた。Comparative Example γ-Al 2 O 3 Pd- Al 2 O 3 was 0.3 wt% Pd-loaded, with further was 0.1 wt% on the Pd catalyst, other uses the same conditions as in Example The same styrene was hydrogenated. The result was as shown in the drawing.
図面は実施例および比較例の結果を示す図表である。 The drawings are charts showing the results of Examples and Comparative Examples.
Claims (1)
チレン類を選択的に水素添加して除去、精製する方法に
おいて、その水素添加触媒として１価および／または０
価の銅を含む触媒を用いることを特徴とするスチレン類
含有物の精製法。1. A method of selectively hydrogenating and removing phenylacetylenes contained in a styrene-containing material to remove and purify it, wherein the hydrogenation catalyst is monovalent and / or 0.
A method for purifying a styrene-containing product, which comprises using a catalyst containing a valent copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3162485A JPH0645561B2 (en) | 1985-02-21 | 1985-02-21 | Styrene-containing material purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3162485A JPH0645561B2 (en) | 1985-02-21 | 1985-02-21 | Styrene-containing material purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61191627A JPS61191627A (en) | 1986-08-26 |
| JPH0645561B2 true JPH0645561B2 (en) | 1994-06-15 |
Family
ID=12336369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3162485A Expired - Fee Related JPH0645561B2 (en) | 1985-02-21 | 1985-02-21 | Styrene-containing material purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0645561B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH085814B2 (en) * | 1987-05-11 | 1996-01-24 | 三菱化学株式会社 | Styrene purification method |
| JPH085815B2 (en) * | 1987-05-13 | 1996-01-24 | 三菱化学株式会社 | Styrene purification method |
| US4822936A (en) * | 1987-08-25 | 1989-04-18 | The Dow Chemical Company | Selective hydrogenation of phenylacetylene in the presence of styrene |
| CN101475439B (en) * | 2008-12-18 | 2012-05-09 | 中国石油化工股份有限公司 | Phenylacetylene selective hydrogenation method using compound bed in the presence of phenylethylene |
| CN101475438B (en) * | 2008-12-18 | 2012-05-23 | 中国石油化工股份有限公司 | Selective hydrogenation method for phenylacetylene in the presence of phenylethylene |
-
1985
- 1985-02-21 JP JP3162485A patent/JPH0645561B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61191627A (en) | 1986-08-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |