JPS59216838A - Purification of styrene-containing composition by selective hydrogenation - Google Patents
Purification of styrene-containing composition by selective hydrogenationInfo
- Publication number
- JPS59216838A JPS59216838A JP58090797A JP9079783A JPS59216838A JP S59216838 A JPS59216838 A JP S59216838A JP 58090797 A JP58090797 A JP 58090797A JP 9079783 A JP9079783 A JP 9079783A JP S59216838 A JPS59216838 A JP S59216838A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- phenylacetylene
- hydrogenation
- catalyst
- selective 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.)
- Granted
Links
Classifications
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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
- 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
Abstract
Description
【発明の詳細な説明】
本発明はスチレン、粗スチレン又はメチルスチレン飾の
スチレン類含有物に含まれるフェニルアセチレンやアル
キルフェニルアセチレン等のフェ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 The present invention removes phenylacetylenes such as phenylacetylene and alkylphenylacetylene contained in styrene, crude styrene, or methylstyrene-decorated styrene-containing materials by selectively hydrogenating the styrenes. (Hereinafter, styrenes will be simply referred to as "styrene.") This invention relates to a method for purifying a containing material.
エチルベンゼンの脱水素反応によって得られるスチレン
又は粗スチレン等のようなスチレン含有物には、少量の
フェニルアセチレンが含有されていることが多い。かか
るスチレン含有物に含まれているフェニルアセチレンは
、これを選択的水素添加によって除去することができる
。しかし、その水素添加反応において使用される触媒の
選択性が悪いと、側鎖のアセチレン基を水素化させるは
力蔦りでなく、スチレンのビニル基の水素化反応やベン
ゼン核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。また、過度の水素添加反応による発
熱にもとづく温度上昇によって炭素結合の***反応をひ
き起し、重要な成分の損失をきたすばかりでなく、触媒
寿命を短かくする等の支障が生ずる。Styrene-containing materials such as styrene or crude styrene obtained by dehydrogenation of ethylbenzene often contain a small amount of phenylacetylene. Phenylacetylene contained in such a styrene-containing material can be removed by selective hydrogenation. However, if the selectivity of the catalyst used in the hydrogenation reaction is poor, hydrogenation of the acetylene group in the side chain is not possible, but hydrogenation of the vinyl group of styrene or hydrogenation of the benzene nucleus. This causes a decrease in the yield of the desired styrene. Further, the temperature rise due to heat generated by excessive hydrogenation reaction causes a carbon bond splitting reaction, which not only causes loss of important components but also causes problems such as shortening the catalyst life.
他方、フェニルアセチレンの選択的水素添加に関する文
献等は従来あまり見当らず、わずかに特公昭グｇ−／乙
ｔり７号公報に、ニッケル５％以上、及びクロム、マン
ガン、銅の７種以上をニッケルに対してよ０％以下含有
せしめた固体多元触媒を特定の有機硫黄化合物で処理し
た触媒を用いて、フェ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にすぎず、かつ同公報に記
載された方法における液空間速度けわずかＪ’ｈｒ
程度であり、かかる方法を以てしてはフェニルアセチレ
ンを経済的有利に選択的水素化させることができない。On the other hand, there are not many documents related to selective hydrogenation of phenylacetylene, and there is only one published in Japanese Patent Publication No. 7, which describes the addition of 5% or more of nickel and 7 or more of chromium, manganese, and copper. The publication merely describes a method for selectively hydrogenating phenylacetylene using a solid multi-component catalyst containing less than 0% nickel and treated with a specific organic sulfur compound. The liquid hourly space velocity J'hr in the method described in
phenylacetylene cannot be economically advantageously selectively hydrogenated using such a method.
本発明前等は、フェニルアセチレンの選択的水素添加に
よりスチレン含有物に含オれるフェニルアセチレンを有
利に除去する精製法を開発する目的で、その選択的水素
添加触媒について種々研究を重ねた結果、特定成分の組
合わせによって得られた特定触媒がその目的に適するこ
とを見出し、すなわちフェ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著しく高いことを
見出し、本発明を完成したものである。Prior to the present invention, in order to develop a purification method that advantageously removes phenylacetylene contained in styrene-containing materials by selectively hydrogenating phenylacetylene, we had conducted various studies on selective hydrogenation catalysts. We have discovered that a specific catalyst obtained by combining specific components is suitable for that purpose, that is, it is capable of selectively hydrogenating only phenylacetylene, and has extremely high catalytic activity, and has completed the present invention. be.
すなわち本発明の方法は、スチレン類含有物に含まれる
フェニルアセ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Ｐｄ 、
Ｐｔ 、 Ｉｒ、Ｒｈ及びＲｕよりなる群から選ば
れた／ｆｉ又は２種以上の金属と、Ｐｂ 、 Ｂｉ
、 Ｐ、Ｓｂ、Ａ＋ｓ 、 Ｔｅ及びＳよりなる群
から選ばれた７種又は、２種以上の元素とを含む触媒を
用いると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。That is, the method of the present invention is a method for selectively hydrogenating to remove and purify phenylacetylenes contained in a styrene-containing material, in which Pd,
/fi or two or more metals selected from the group consisting of Pt, Ir, Rh and Ru, and Pb, Bi
A method for purifying a styrene-containing material by selective hydrogenation, characterized by using a catalyst containing seven or more elements selected from the group consisting of , P, Sb, A+s, Te, and S. It is.
本発明における水素添加触媒は、このように触媒活性成
分としてＰｄ、 Ｐｔ 、 Ｉｒ 、Ｒｈ及びＲｕ
よりなる群から選ばれた７種又は２種以上の金属と、Ｐ
ｂ 、 Ｂｌ 、Ｐ、Ｓｂ 、Ａｓ、Ｔｅ及びＳよシ
なる群から選ばれた７種又は２種以上の元素とを含むも
のであシ、これ 。The hydrogenation catalyst in the present invention thus contains Pd, Pt, Ir, Rh, and Ru as catalytically active components.
7 or 2 or more metals selected from the group consisting of;
It contains seven or more elements selected from the group consisting of B, Bl, P, Sb, As, Te, and S.
らの触媒成分は、通常、適壱カ担体に担持される。これ
ら成分の担持量は、前者の金属が３−
Ｏ１θ／〜／、０重量％、好ましくは０．０３〜ＯＪ重
量％、後者の元素が０．００／〜０． ／重量％、好ま
しくはｏ、 ｏ ｏ ｔ −ｏ、 ｏ を重量％である
。また、その担体としては、耐熱性の無機酸化物担体、
たとえばアルミナ、シリカなどのような合成ゲル担体、
或いはケイソウ土、多孔性粘土などの天然無機物担体等
があげられる。These catalyst components are usually supported on an appropriate amount of carrier. The amount of these components supported is 3-O1θ/~/0% by weight for the former metal, preferably 0.03~0J weight%, and 0.00/~0.0% for the latter element. /wt%, preferably o, o ot -o, o is wt%. In addition, as the carrier, a heat-resistant inorganic oxide carrier,
synthetic gel carriers, such as alumina, silica, etc.
Alternatively, natural inorganic carriers such as diatomaceous earth and porous clay may be used.
本発明における水素添加処理をするスチレン含有物は、
フェニルアセチレンを含有するスチレン又は粗スチレン
等である。The styrene-containing material subjected to hydrogenation treatment in the present invention is
Styrene containing phenylacetylene or crude styrene.
本発明の水素添加反応条件については、反応温度は、２
ｏｏｃ以下、好ましくは１０ＯＣ〜室温である。反応温
度が高く々ヤすぎるとスチレンの水素化反応を生部せし
めるし、また低くなりすぎると目的の反応速度がおそく
なるので、いずれも好ましくない。Regarding the hydrogenation reaction conditions of the present invention, the reaction temperature is 2
ooc or less, preferably 10OC to room temperature. If the reaction temperature is too high, the hydrogenation reaction of styrene will proceed, and if the reaction temperature is too low, the desired reaction rate will be slowed down, which are both undesirable.
反応圧力は常圧〜加圧下、好オしくけ常圧近辺である。The reaction pressure is from normal pressure to elevated pressure, preferably around normal pressure.
圧力が高くなりすぎると目的のフェニルアセチレン水添
反応の選択性が悪く一４’ −
なる。If the pressure becomes too high, the selectivity of the target phenylacetylene hydrogenation reaction will be poor, resulting in 14'-.
液空間速度（ＬＨ８Ｖ）は／ 〜、ｔ ００ ｈｒ−’
、好ましくは１０〜３００ ｈｒ−’である。液空間速
度が高すぎるとフェニルアセチレンの転化率が低下する
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。The liquid hourly space velocity (LH8V) is / ~, t 00 hr-'
, preferably 10 to 300 hr-'. If the liquid hourly space velocity is too high, the conversion rate of phenylacetylene will decrease, and if the liquid hourly space velocity is too low, a hydrogenation reaction of styrene will occur, resulting in a decrease in styrene yield.
水素の供給醗はフェニルアセチレンを水素化してスチレ
ンを生成せしめるに必要な量で足りるが、通常、その必
要量の／倍量〜１００倍量が用いられる。水素景があま
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−。It is sufficient to supply hydrogen in an amount necessary to hydrogenate phenylacetylene to produce styrene, but usually an amount from 1 to 100 times the required amount is used. Too much hydrogen content is undesirable because it leads to a decrease in styrene yield due to hydrogenation of styrene.
本発明の精製法は下記のとおりの優れた効果を奏するこ
とができる。The purification method of the present invention can produce the following excellent effects.
（１） フェニルアセチレンの水素添加反応の選択性
が高く、スチレンの水素添加反応及びベンゼン核の水素
添加反応等の副反応を実質上司さないので、高価なスチ
レン等のロスが小力い。(1) The selectivity of the hydrogenation reaction of phenylacetylene is high, and side reactions such as the hydrogenation reaction of styrene and the hydrogenation reaction of benzene nuclei are not substantially affected, so the loss of expensive styrene etc. is small.
（１１）炭素結合の***反応、ガム質生成反応、炭素質
生成反応等を実質上司さないので、貴重な資源のロスが
少なく、かつ触媒寿命が著しく長い。(11) Since carbon bond splitting reactions, gum-forming reactions, carbonaceous-forming reactions, etc. are not substantially promoted, there is little loss of valuable resources and the catalyst life is extremely long.
（Ｈｉ ）触媒活性が高く、シたがって低温、低圧でも
高い通油量を確保でき、設備費及び運転費が少々い。(Hi) Catalytic activity is high, so a high oil flow rate can be ensured even at low temperatures and low pressures, and equipment and operating costs are low.
以下、実施例及び比較例をあげて本発明をさらに詳述す
る。Hereinafter, the present invention will be further explained in detail by giving Examples and Comparative Examples.
実施例／
３ ｍｍφ’ｘ３ｍｍに成形したｒ−アルミナに、濃度
０．２重骨％の塩化パラジウム水溶液を含浸させ、／１
０Ｃで／昼夜乾燥させた。ついで、水素気流下でｔｉｏ
ｏｒ′で／Ａ時間還元した。Example / R-alumina molded into 3 mmφ' x 3 mm was impregnated with a palladium chloride aqueous solution having a concentration of 0.2% heavy bone, /1
Dry at 0C/day/night. Then, under a hydrogen stream, tio
or' was reduced for /A hours.
ついで、これに濃度θ、θ、２重量％の塩化アンチモン
水溶液を含浸させ、／１０ｃで／昼夜乾燥させたのち、
水素気流下で≠ｏｏ″Ｃで７乙時間還元させた。得られ
た触媒の組成はＰｄ（０，１重量％）−ｓｂ（ｏ、ｏｉ
重量％）／γ−ＡＩ、０．であった。Next, this was impregnated with an antimony chloride aqueous solution with a concentration of θ, θ, 2% by weight, and dried at /10c/day and night.
Reduction was carried out for 7 hours at ≠oo''C under a hydrogen stream. The composition of the obtained catalyst was Pd (0.1% by weight)-sb (o,oi
weight%)/γ-AI, 0. Met.
容量２００ｒｒｔｌのＳＵＳ製オートクレーブに、スチ
レン１．０重量％、エチルベンゼンｔＩ０ｔｉ％及びフ
ェニルアセチレンタ、、ｔｔｉｐｐｍを含有する粗スチ
レン留分／ ００ ｍｌを仕込み、これに上記のように
して調製した触媒／グを加え、反応温度を室温（，２０
Ｃ）に保ち、水素ガスの圧入により圧力を、：ｌ ｋｇ
／ ｃｍ ’ Ｑに保って、１時間反応させた。その
結果は第７図に示すとおりであわ、反応２時間後には含
有フェニルアセチレンの大部分が水素添加により除去さ
れだが、スチレンは殆んど水素添加されなかった。A SUS autoclave with a capacity of 200 rrtl was charged with 00 ml of a crude styrene fraction containing 1.0% by weight of styrene, tI0ti% of ethylbenzene, and ttippm of phenylacetylene, and the catalyst/glue prepared as described above was charged. was added, and the reaction temperature was reduced to room temperature (,20
C) and increase the pressure by injecting hydrogen gas: l kg
/cm'Q and allowed to react for 1 hour. The results were as shown in FIG. 7. After 2 hours of reaction, most of the phenylacetylene contained was removed by hydrogenation, but almost no styrene was hydrogenated.
実施例２
塩化アンチモン水溶液の代りに、濃９０．０２重号％の
三塩化ヒ素水溶液を用い、そのほかは実施例／の方法に
準じて、触媒組成がＰｄ（００７重着％） −Ａｓ （
０，０１重量％）／ｒ−Ａ１．ｏ、 ′の触媒
を調製した。Example 2 A concentrated 90.02% arsenic trichloride aqueous solution was used instead of the antimony chloride aqueous solution, and the catalyst composition was Pd (007%) -As (
0.01% by weight)/r-A1. The catalysts o and ' were prepared.
この触媒／ｆｆを用い、そのほかは実施例／７−
に記載した反応におけると同様の条件を用いて同一の粗
スチレン留分の水素添加処理をした。その結果はフェニ
ルアセチレンのり乙％が水素添加されたが、スチレンは
殆んど水素添加されなかった。The same crude styrene fraction was hydrogenated using this catalyst/ff and other conditions similar to those in the reaction described in Example/7-. The results showed that % of phenylacetylene was hydrogenated, but styrene was hardly hydrogenated.
実施例３〜２
実施例／における塩化パラジウムの代りに、塩化白金酸
（実施例３）、塩化イリジウム（実施例ケ）、塩化ロジ
ウム（実施例り、又は塩化ルテニウム（実施例ｔ）をそ
れぞれ使用し、そのほかは実施例／に記載の方法に準じ
て、ｒ−ＡＩ、Ｏ，にＰｔ、 Ｉｒ 、Ｒｈ 、 又
けＲｕをそれぞれ０．７重量％、及びＳｂをいずれも０
．０７７重骨担持した各触媒を調製した。Examples 3 to 2 In place of palladium chloride in Example/, chloroplatinic acid (Example 3), iridium chloride (Example 6), rhodium chloride (Example 1), or ruthenium chloride (Example t) was used, respectively. Other than that, according to the method described in Example/, Pt, Ir, Rh, and Ru were added to r-AI, O, 0.7% by weight, and Sb was added to 0.
．． Each catalyst supported on 077 heavy bones was prepared.
得られた各触媒／９ずつをそれぞれ使用し、そのほか（
叶実雄側／におけると同様の条件を用いて同一の粗スチ
レン留分の水素添加処理を２時間行なわせた。その結果
は第７表に示すとおりであった。Each of the obtained catalysts/9 was used, and the others (
The same crude styrene fraction was hydrogenated for 2 hours using the same conditions as on the Kano Mio side. The results were as shown in Table 7.
−ざ一
実施例７〜／／
実施例１における塩化アンチモンの代りに、硝酸鉛（実
施例７）、硝酸ビスマス（実施例ｇ）、三塩化リン（実
施例り）、四塩化テルル（実施例１０）、又は硫化水素
（実施例／／）をそれぞれ使用し、そのほかは実施例／
に記載の方法に準じて、γ−ＡＩ、Ｏ，にＰｄをいずし
４０． ／重量％、及びＰｂ 、 Ｂｉ、 ｐ、 Ｔｅ
又はＳをそれぞれ０．０７重量％担持した各触媒を調製
した。- Example 7 ~ // Instead of antimony chloride in Example 1, lead nitrate (Example 7), bismuth nitrate (Example g), phosphorus trichloride (Example 1), tellurium tetrachloride (Example 1) 10) or hydrogen sulfide (Example//), respectively, and the others are Example//
Pd was added to γ-AI and O according to the method described in 40. /wt%, and Pb, Bi, p, Te
Alternatively, catalysts each carrying 0.07% by weight of S were prepared.
得られた各触媒／１をそれぞれ使用し、そのほかは実施
例／におけると同様の条件で２時間同一の粗スチレン留
分を水素添加処理した。その結果は第１表に示すとおり
であった。Using each of the obtained catalysts/1, the same crude styrene fraction was subjected to hydrogenation treatment for 2 hours under the same conditions as in Example/1. The results were as shown in Table 1.
比較例／
ｒ−Ａｌ！０．にＰｄを０．３重骨％担持した市販触媒
／グを用い、そのほかは実施例／におけると同様の条件
を使用して同一の粗スチレン留分を２時間水素添加処理
した。Comparative example/r-Al! 0. The same crude styrene fraction was subjected to hydrogenation treatment for 2 hours using a commercially available catalyst carrying 0.3% of Pd on the catalyst and other conditions similar to those in Example.
その結果は第７表に示すとおりであった。The results were as shown in Table 7.
実施例７．２
実施例／において調製した触媒１００ＦＩ−を直径、２
０ｍｍ、長さｊＯｃｍのステンレス製管に充填し、これ
に実施例／において用いたと同一の粗スチレン留分及び
水素ガスを、温度ｒｏｃ、圧力常圧、Ｈ！／フェニルア
セチレンモル比＝ ／、 Ｊ’ ／ ／、ＬＨ８Ｖ１０
０ｈｒ’の条件で連続的に通過させて、３０日間連続的
に水素添加処理した。Example 7.2 The catalyst 100FI- prepared in Example/
A stainless steel tube with a diameter of 0 mm and a length of jOcm was filled with the same crude styrene fraction and hydrogen gas used in Examples/Examples at a temperature of roc, a pressure of normal pressure, and H! /phenylacetylene molar ratio = /, J' / /, LH8V10
Hydrogenation treatment was carried out continuously for 30 days by passing the sample continuously under the condition of 0 hr'.
その結果は第２図に示すとおりであり、連Ｒ３０日運転
後においてもフェニルアセチレンの転化率に殆んど変化
がなく、触媒活性の低下は全く認められなかった。The results are shown in FIG. 2, and even after 30 days of continuous operation, there was almost no change in the conversion rate of phenylacetylene, and no decrease in catalyst activity was observed.
第１図は実施例／の水素添加処理における被処理油中の
フェニルアセチレン濃度及びスチレン濃度の経時変化を
示したものであシ、第２図は実施例／２の水素添加処理
における ゛フェニルアセチレン転化率の経時変化
を示したものである。
（％自重））■４（ｆ述Ｙ
（ｗｄｄ山軍）！！び毛’Ｍｌ（Ｘ兄Figure 1 shows the changes over time in the phenylacetylene concentration and styrene concentration in the treated oil in the hydrogenation treatment of Example/2, and Figure 2 shows the changes over time in the phenylacetylene concentration and styrene concentration in the hydrogenation treatment of Example/2. This figure shows the change in conversion rate over time. (% own weight)) ■4 (f mention Y (wdd mountain army)!! Bige'Ml (X brother
Claims (1)
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Ｐｄ 、 Ｐｔ 、 Ｉｒ
、 Ｒｈ及びＲｕよりなる群から選ばれた７種又は２種
以上の金属と、Ｐｂ、 Ｂｉ 、ＰＸＳｂ 、Ａｓ
、 Ｔｅ及びＳよりなる群から選ばれた７種又は２種以
上の元素と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。A: In a method of selectively hydrogenating and removing and purifying phenylacetylenes contained in a styrene-containing material,
Pd, Pt, Ir as the hydrogenation catalyst
, Rh and Ru, and seven or more metals selected from the group consisting of Pb, Bi, PXSb, As.
A method for purifying a styrene-containing material by selective hydrogenation, characterized by using a catalyst containing seven or more elements selected from the group consisting of Te and S.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58090797A JPS59216838A (en) | 1983-05-25 | 1983-05-25 | Purification of styrene-containing composition by selective hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58090797A JPS59216838A (en) | 1983-05-25 | 1983-05-25 | Purification of styrene-containing composition by selective hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59216838A true JPS59216838A (en) | 1984-12-06 |
| JPH034046B2 JPH034046B2 (en) | 1991-01-22 |
Family
ID=14008572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58090797A Granted JPS59216838A (en) | 1983-05-25 | 1983-05-25 | Purification of styrene-containing composition by selective hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59216838A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277639A (en) * | 1987-05-11 | 1988-11-15 | Mitsubishi Petrochem Co Ltd | Purification of styrenes |
| CN1097480C (en) * | 1999-06-25 | 2003-01-01 | 中国石油化工集团公司 | Catalyst for selective hydrogenation of acetylene hydrocarbon |
| US20120123174A1 (en) * | 2008-09-25 | 2012-05-17 | Sued-Chemie Catalysts Japan, Inc. | Catalyst for selective hydrogenation of acetylene compounds |
| JP2012512189A (en) * | 2008-12-18 | 2012-05-31 | 中国石油化工股▲ふん▼有限公司 | Method for selectively adding hydrogen to phenylacetylene using a composite bed in the presence of styrene. |
| JP2012512188A (en) * | 2008-12-18 | 2012-05-31 | 中国石油化工股▲ふん▼有限公司 | Method for selectively adding hydrogen to phenylacetylene in the presence of styrene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5227704A (en) * | 1975-08-25 | 1977-03-02 | Dainippon Ink & Chem Inc | Process for selective hydrogenation of compounds containing acetylenic unsaturated bonds |
| JPS5564527A (en) * | 1978-11-08 | 1980-05-15 | Shin Etsu Chem Co Ltd | Selective preparation of cis form compound |
| JPS5535368B2 (en) * | 1972-05-26 | 1980-09-12 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535368A (en) * | 1978-09-06 | 1980-03-12 | Kako:Kk | Control device for continuous emission of strobe |
| JPS5653625A (en) * | 1979-10-06 | 1981-05-13 | Japan Synthetic Rubber Co Ltd | Recovery of 1,3-butadiene |
| JPS5751363A (en) * | 1980-09-11 | 1982-03-26 | P S Concrete | Premounting of tile |
-
1983
- 1983-05-25 JP JP58090797A patent/JPS59216838A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535368B2 (en) * | 1972-05-26 | 1980-09-12 | ||
| JPS5227704A (en) * | 1975-08-25 | 1977-03-02 | Dainippon Ink & Chem Inc | Process for selective hydrogenation of compounds containing acetylenic unsaturated bonds |
| JPS5564527A (en) * | 1978-11-08 | 1980-05-15 | Shin Etsu Chem Co Ltd | Selective preparation of cis form compound |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277639A (en) * | 1987-05-11 | 1988-11-15 | Mitsubishi Petrochem Co Ltd | Purification of styrenes |
| CN1097480C (en) * | 1999-06-25 | 2003-01-01 | 中国石油化工集团公司 | Catalyst for selective hydrogenation of acetylene hydrocarbon |
| US20120123174A1 (en) * | 2008-09-25 | 2012-05-17 | Sued-Chemie Catalysts Japan, Inc. | Catalyst for selective hydrogenation of acetylene compounds |
| JP2012512189A (en) * | 2008-12-18 | 2012-05-31 | 中国石油化工股▲ふん▼有限公司 | Method for selectively adding hydrogen to phenylacetylene using a composite bed in the presence of styrene. |
| JP2012512188A (en) * | 2008-12-18 | 2012-05-31 | 中国石油化工股▲ふん▼有限公司 | Method for selectively adding hydrogen to phenylacetylene in the presence of styrene |
| US9084984B2 (en) | 2008-12-18 | 2015-07-21 | China Petroleum & Chemical Corporation | Method for selective hydrogenation of phenylacetylene in the presence of styrene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH034046B2 (en) | 1991-01-22 |
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