JPS63277639A - Purification of styrenes - Google Patents
Purification of styrenesInfo
- Publication number
- JPS63277639A JPS63277639A JP62114187A JP11418787A JPS63277639A JP S63277639 A JPS63277639 A JP S63277639A JP 62114187 A JP62114187 A JP 62114187A JP 11418787 A JP11418787 A JP 11418787A JP S63277639 A JPS63277639 A JP S63277639A
- Authority
- JP
- Japan
- Prior art keywords
- styrenes
- reaction
- styrene
- hydrogenation
- catalyst
- 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
- 150000003440 styrenes Chemical class 0.000 title claims abstract description 31
- 238000000746 purification Methods 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 30
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract description 26
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 abstract description 7
- 150000001993 dienes Chemical class 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- -1 that is Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000005194 ethylbenzenes Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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
【発明の詳細な説明】 （１）発明の目的 〔産業上の利用分野〕 本発明は、スチレン類の精製方法に関するものである。[Detailed description of the invention] (1) Purpose of the invention [Industrial application field] The present invention relates to a method for purifying styrenes.
詳しくは、本発明は、スチレン類中に含有される高不飽
和不純物、即ち、フェニルアセチレン等のアセチレン類
及びジオレフィン類を選択的に水素添加して除去する方
法に関するものである。Specifically, the present invention relates to a method for selectively hydrogenating and removing highly unsaturated impurities contained in styrenes, that is, acetylenes such as phenylacetylene and diolefins.
スチレン類はポリマー原料として広く用いられている。 Styrenes are widely used as polymer raw materials.
しかし、スチレン類を重合させてポリマーを製造する場
合に、重合特性にバラツキがあシ、安定した品質の／
ＩＪママ−品が得られない問題点があった・
その原因は、本発明者等の知見によれば、エチルベンゼ
ン類の脱水素反応によりて得られるスチレン類について
は、その反応において用いた触媒特性、反応形式、プラ
ントの運転条件等によりて、高不飽和不純物、すなわち
フェニルアセチレン等のアセチレン類、ジオレフイア類
などの含有量が大巾に変動し、これらの高不飽和不純物
がスチレン類の重合時に重合抑制剤として働くことによ
ることが判った。However, when producing polymers by polymerizing styrenes, there are variations in polymerization properties, and stable quality /
There was a problem in which IJ mom products could not be obtained.According to the findings of the present inventors, the styrenes obtained by the dehydrogenation reaction of ethylbenzenes are due to the characteristics of the catalyst used in the reaction. , the content of highly unsaturated impurities, i.e. acetylenes such as phenylacetylene, diolephias, etc., varies widely depending on the reaction type, plant operating conditions, etc., and these highly unsaturated impurities are It was found that this is due to its action as a polymerization inhibitor.
従来、スチレン類に含有される高不飽和不純物の除去に
関する文献等はあまシ見当らないが、特公昭４８−１６
４９７号公報には、ニッケル５俤以上、及びクロム、マ
ンガン、鋼の１種以上を二ブチルに対して５０％以下含
有せしめ次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、スチレン類を水素添加処理し、含有
されているフェニルアセチレンを選択的に水素添加して
除く記載がある。しかし、同公報に記載の水素添加処理
は、液空間速度がわずか５ ｈｒ−１程度であることか
らして、かかる方法はフェニルアセチレンを選択的に水
素添加して除くことができても、工業的に有利に実施で
きる方法ではない。Until now, there has been no literature on the removal of highly unsaturated impurities contained in styrenes, but
Publication No. 497 discloses that a solid multi-component catalyst containing 50% or more of nickel and at least 50% of chromium, manganese, and steel based on dibutyl is treated with a specific organic sulfur compound. There is a description of hydrogenating styrenes and selectively hydrogenating and removing the phenylacetylene contained therein. However, since the hydrogenation treatment described in the same publication has a liquid hourly space velocity of only about 5 hr-1, even if such a method can selectively hydrogenate and remove phenylacetylene, it is not suitable for industrial use. This is not a method that can be implemented advantageously.
本発明者等は、即に、スチレン類を水素添加触媒の存在
下で水素添加処理をして含有される高不飽和不純物を選
択的に水素添加して除去する方法において、該水素添加
反応における反応温度を６０〜１２０℃に保つことを特
徴とするスチレン類の精製方法を発明し、特許出願して
いる（％許出願 昭６０−２９１０１５号）。しかしな
がら、この方法では、反応温度を６０℃よシ低くして反
応を行なうと、反応液中に含まれる水分によシ触媒が被
毒され、全く失活してしまうという問題点がある。The present inventors immediately discovered a method for selectively hydrogenating and removing highly unsaturated impurities contained in styrenes by hydrogenating them in the presence of a hydrogenation catalyst. He invented a method for purifying styrenes characterized by maintaining the reaction temperature at 60 to 120°C, and has filed a patent application (% Patent Application No. 1987-291015). However, this method has the problem that if the reaction is carried out at a reaction temperature lower than 60° C., the catalyst will be poisoned by the water contained in the reaction solution and will be completely inactivated.
（１１）発明の構成
〔問題点を解決する次めの手段〕
本発明者等は、前記の問題点を解決するために更に鋭意
検討を重ねた結果、高不飽和不純物、特にフェニルアセ
チレン等のアセチレン類を水素添加処理するに当シ、該
水素添加反応系に供給する液中の水分量をｚｏｏｏｗｔ
−ｐｐｍ以下に規制して反応を行なえば、反応温度が６
０℃よシ低い条件においても触媒は失活することなく、
安定した活性が得られることを見出し、本発明を完成す
るに至しン類を水素添加触媒の存在下で水素添加処理し
て含有される高不飽和不純物を選択的に水素添加して除
去する方法において、該水素添加反応系に供給される該
スチレン類を含む原料中の水分含量を２０００重量ｐｐ
ｍ以下に保ち且つ該水素添加反応における反応温度ｔ−
ｏ”ｃ〜１２０℃の範囲に保つととｔ−’ＩＩ徴とする
スチレン類の精製方法である。(11) Structure of the Invention [Next Means to Solve the Problems] As a result of further intensive studies to solve the above problems, the present inventors have discovered that highly unsaturated impurities, especially phenylacetylene, etc. When hydrogenating acetylenes, the amount of water in the liquid supplied to the hydrogenation reaction system is
If the reaction is carried out under -ppm or less, the reaction temperature will be 6.
The catalyst does not deactivate even under conditions as low as 0℃,
It was discovered that stable activity could be obtained, and the present invention was completed by hydrogenating the resins in the presence of a hydrogenation catalyst to selectively hydrogenate and remove the highly unsaturated impurities contained therein. In the method, the water content in the raw material containing the styrenes supplied to the hydrogenation reaction system is reduced to 2000 pp by weight.
m or less and the reaction temperature in the hydrogenation reaction t-
This is a method for purifying styrenes in which the temperature is maintained within the range of 120°C to 120°C.
スチレン類
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ｆルスチレン、ビニルトルエン、ｐ−ｔ−ブ
チルスチレン、ジビニルベンゼン及ヒこれらの少なくと
も１種を含有する組成物をいう。Styrenes The styrenes targeted by the purification method of the present invention refer to styrene, p-methylstyrene, vinyltoluene, p-t-butylstyrene, divinylbenzene, and compositions containing at least one of these. .
かかるスチレン類は、Ａ常、エチルベンゼン、−一メチ
ルエチルベンゼン、エチルトルエン、ｐ−ｔ−ブチルエ
チルベンゼン、ジエチルベンゼン等の少なくとも１種の
エチルベンゼン類を脱水素触媒、九とえばＦｅ−Ｃ・−
に？主成分とする触媒（特開昭４９−１２０８８７号、
同４９−１２０８８８号、同５３−１２９１９０号、及
び同５３−１２９１９１号の各公報等参照）、又はＦｅ
−Ｃｒ−Ｋ１主成分とする触媒等の徨々の脱水素触媒の
存在下で脱水素反応をさせて得られる反応生成物、又は
同反応生成物の蒸留分離によって得られる留分等である
。Such styrenes can be used as dehydrogenation catalysts, such as Fe-C.
To? Catalyst as main component (JP-A-49-120887,
49-120888, 53-129190, and 53-129191), or Fe
These include a reaction product obtained by carrying out a dehydrogenation reaction in the presence of various dehydrogenation catalysts such as a catalyst containing -Cr-K1 as a main component, or a fraction obtained by distillation of the same reaction product.
上記のような方法で得られるスチレン類には、フェニル
アセチレン等のアセチレン類、及びジオレフィン類が含
まれている。スチレン類中に含有されるかかる高不飽和
不純物の含有量は、製造条件等によっても異なるが、ア
セチレン類が１０〜ｉｏ００ｐｐｍ（重−ｊ／ｉｋ）程
度、ジオレフィン類が５〜５００ ｐＰｆｆｌ （重量
）程度である。The styrenes obtained by the above methods include acetylenes such as phenylacetylene and diolefins. The content of highly unsaturated impurities contained in styrenes varies depending on the manufacturing conditions, etc., but it is about 10 to io00 ppm (by weight) for acetylenes and 5 to 500 pPffl (by weight) for diolefins. ).
ここで１本発明の水素添加反応系に供給される該スチレ
ン類を含む原料中の水分台ｉ′Ｆｉ２０００重量ｐｐｍ
以下、好ましくは１７００重量ｐｐｍ以下、最も好まし
くは１５００重量ｐｐｍ以下に抑えることが必要である
。原料中の水分含量が２０００重量ｐｐｍを越えると触
媒が被毒され、短期間にアセチレン類を水素添加する能
力が著しく低下し、実用に耐えなくなる。Here, 1) the moisture level i'Fi in the raw material containing styrenes supplied to the hydrogenation reaction system of the present invention is 2000 ppm by weight.
Below, it is necessary to suppress the content to preferably 1,700 ppm by weight or less, most preferably 1,500 ppm by weight or less. If the water content in the raw material exceeds 2000 ppm by weight, the catalyst will be poisoned, and the ability to hydrogenate acetylenes in a short period of time will be significantly reduced, making it unusable.
その理由につｂての詳細は、完全には明らかになってい
ないが、
■ 触媒表面への水の親和力が強く、触媒表面を水が覆
ってしまうこと
■ 触媒が水によシ酸化されてしまうことなどが考えら
れている。The details of the reasons for this are not completely clear, but include: ■ The affinity of water to the catalyst surface is strong and the water covers the catalyst surface; ■ The catalyst is oxidized by water. The idea is to put it away.
なお、該スチレン類をそのまま原料として反応系へ供給
する場合には、該スチレン類中の水分含Ｊｉｆ上記の値
に規制することが必要であるが、該スチレン類を他の炭
化水素等で希釈して反応系へ供給する場合には炭化水素
等を含めた原料全体の水分含量全上記の値に規制するこ
とが必要である。In addition, when the styrenes are supplied as raw materials to the reaction system, it is necessary to control the water content in the styrenes to the above value, but if the styrenes are diluted with other hydrocarbons, etc. When supplying the raw material to the reaction system, it is necessary to control the moisture content of the entire raw material, including hydrocarbons, to the above value.
水素
本発明における水素添加反応系への水素の供給量は、目
的の高不飽和不純物の水素添加に必要な水素量の１〜１
００倍量程度である。供給する水素量が多すぎるとスチ
レン等の有用成分が水素添加されてロスとなり、その収
量が低下する。Hydrogen The amount of hydrogen supplied to the hydrogenation reaction system in the present invention is 1 to 1 of the amount of hydrogen required for hydrogenation of the target highly unsaturated impurity.
It is about 00 times the amount. If the amount of hydrogen supplied is too large, useful components such as styrene are hydrogenated and lost, resulting in a decrease in yield.
本発明の精製方法で使用する水素添加触媒は、水素添加
触媒能を有するものであればよい。好ましいその触媒は
白金族金属を触媒成分として含有する触媒である。この
種の水素添加触媒は、通常、その触媒成分が適当な担体
に担持されておシ、その触媒成分の担持量は通常、０．
０ｌ−１１３ｉＪｉｌＪ、好ましくは０．０５〜０．５
重量％である。ま九、その担体としては、耐熱性の無機
化合物担体、友とエバアルミナ、シリカな°どの合成ｒ
ル担体、或イはケイソウ土、多孔性粘土などの天然無機
物担体等があげられる。The hydrogenation catalyst used in the purification method of the present invention may be any catalyst as long as it has hydrogenation catalytic ability. Preferred catalysts are those containing platinum group metals as catalyst components. In this type of hydrogenation catalyst, the catalyst component is usually supported on a suitable carrier, and the amount of the catalyst component supported is usually 0.
0l-113iJilJ, preferably 0.05-0.5
Weight%. As the carrier, heat-resistant inorganic compound carriers, synthetic materials such as alumina and silica can be used.
or natural inorganic carriers such as diatomaceous earth and porous clay.
反応温度
本発明の精製方法においては、その水素添加反応をＯ℃
〜１２０℃、好ましくは１０℃〜ｌＯ０℃、最も好まし
くは２０°Ｃ〜９０℃の範囲で行なうことが必要である
。反応温度が高過ぎると、スチレン等の有用なスチレン
類迄が水素添加されてロスとなるし、一方、反応温度が
余シ低過ぎると目的の高不飽和不純物全有効に水素添加
して除くことが出来なくなる。Reaction temperature In the purification method of the present invention, the hydrogenation reaction is carried out at 0°C.
It is necessary to carry out the reaction at a temperature of -120°C, preferably 10°C - 100°C, most preferably 20°C - 90°C. If the reaction temperature is too high, even useful styrenes such as styrene will be hydrogenated and lost. On the other hand, if the reaction temperature is too low, all of the target highly unsaturated impurities will be effectively hydrogenated and removed. becomes impossible.
又、上記反応温度域においても、反応系へ供給する原料
中の水分含量が２０００！量ｐｐｍｋ越えると、触媒が
被毒され、活性を失う。Also, even in the above reaction temperature range, the water content in the raw materials supplied to the reaction system is 2000! If the amount ppmk is exceeded, the catalyst will be poisoned and lose its activity.
反応圧力
本発明における水素添加反応の全圧は、通常、常圧〜加
圧下、好ましくは常圧〜１０ ｋｇ／ａｒｔ２Ｇである
。Reaction Pressure The total pressure of the hydrogenation reaction in the present invention is usually normal pressure to pressurized, preferably normal pressure to 10 kg/art2G.
空間速度
本発明の水素添加反応は、パッチ方式によシ行なわせる
ことができるし、所定温度に保たれた触媒層ヘスチレン
類及び水素を連続的に供給して反応させる連続方式によ
っても実施することができる。連続方式で反応させる場
合の触媒層へのスチレン類の供給速度は、液空間速度（
ＬＨ８Ｖ）で１〜５００ ｈｒ−’ 、好ましくは１０
〜３００ ｈｒ−’である。同速度が高すぎるとフェニ
ルアセチレン等の高不飽和不純物の転化率が低下して、
充分に除去できなくなるし、同速度が低くすぎるとスチ
レン等の有用なスチレン類が水素添加されてロスになる
。Space Velocity The hydrogenation reaction of the present invention can be carried out by a patch method, or can be carried out by a continuous method in which hestyrenes and hydrogen are continuously supplied to a catalyst layer kept at a predetermined temperature. Can be done. In the case of continuous reaction, the supply rate of styrene to the catalyst layer is determined by the liquid hourly space velocity (
LH8V) from 1 to 500 hr-', preferably 10
~300 hr-'. If the same rate is too high, the conversion rate of highly unsaturated impurities such as phenylacetylene will decrease,
If the rate is too low, useful styrenes such as styrene will be hydrogenated and will be lost.
以下に、触媒製造例、実施例及び比較例ｔ−あげてさら
に詳述する。これらの例に記載のｐｐｍ及び係は特に記
載しない限り重量基準による。The following is a detailed description of catalyst production examples, examples, and comparative examples. The ppm and percentages given in these examples are by weight unless otherwise specified.
触媒製造例
３ｆｌφＸ３露の円柱型に成形したγ−アルミナに、濃
度０．６重−ｊｉ−％の塩化パラジウム水溶液を含浸さ
せ、１１０℃で１昼夜乾燥させた。Catalyst Production Example 3 A γ-alumina molded into a cylindrical shape of fl φ x 3 yen was impregnated with an aqueous palladium chloride solution having a concentration of 0.6 wt-ji-% and dried at 110° C. for one day and night.
次いで、その乾燥物を水素気流下で４００℃の温度で１
６時時間光処理して、組成がＰｄ （０，３１） ／γ
−Ａｔ２ｏ３の水素添加触媒を得九。Next, the dried product was heated at a temperature of 400°C under a hydrogen stream for 1 hour.
After 6 hours of light treatment, the composition was Pd(0,31)/γ
- Obtaining a hydrogenation catalyst for At2o3.
実施例−１
上記の様にして調製し次触媒５０ｇを直径２０ｎ、長さ
５０ｃｒＫのステンレス反応管に充填した。Example 1 50 g of the catalyst prepared as described above was packed into a stainless steel reaction tube with a diameter of 20 nm and a length of 50 crK.
この反応管を４０℃に保ち、これにエチルベンゼンの脱
水素反応で得られた粗スチレン留分（スチレン６５ ｗ
ｔｌ 、エチルベンゼン３１ ｗｔｌ、ベンゼン１．５
ｗｔ壬、トルエン２．５ ｗｔｌ、）、ニルアセチレ
：／ ５０〜１５０ ｗｔ ｐｐｍ 、水１００〜２５
０ ｗｔｐｐｍ含有） ｋ ｌ ０００ ｃｃ／ ｈｒ
１反応圧力４ ｋｇ／ｃｒＩＬ２Ｇ 。This reaction tube was kept at 40°C, and a crude styrene fraction (styrene 65 w
tl, ethylbenzene 31 wtl, benzene 1.5
wt 壬, toluene 2.5 wtl,), nylacetylene: / 50-150 wt ppm, water 100-25
(contains 0 wtppm) k l 000 cc/hr
1 reaction pressure 4 kg/crIL2G.
Ｈ２／フェニルアセチレン１．５モル１モルの条件で連
続的に供給した。供給後８時間目のフェニルアセチレン
の水添率は６２％、２０日自重１００日目０水添率はそ
れぞれ５９チ、６０％であシ、安定し比活性が得られ九
〇
実施例−２
反応管を２０℃に保った以外は実施例−１と同様の条件
で反応全行なっ念。粗スチレンの供給後８時間目のフェ
ニルアセチレンの水添率は５７チ、２０日０．４０日日
月水添率はそれぞれ５９％、５７憾と安定した活性が得
られた。H2/phenylacetylene was continuously supplied under the conditions of 1.5 mol and 1 mol. The hydrogenation rate of phenylacetylene at 8 hours after supply was 62%, and the zero hydrogenation rate at 100th day after 20 days was 59% and 60%, respectively, and a stable specific activity was obtained.90 Example-2 The entire reaction was carried out under the same conditions as in Example-1, except that the reaction tube was kept at 20°C. The hydrogenation rate of phenylacetylene 8 hours after the supply of crude styrene was 57%, and the hydrogenation rates on the 20th and 0.40th days were 59% and 57%, respectively, indicating stable activity.
比較例
粗スチレン留分中の水分ｉ’１２５００Ｗｔｐｐｒｒｌ
にし、たこと以外は実施例−２と同一の条件で反応を行
なりた。粗スチレンの供給後６時間目にはフェニルアセ
チレンの水添率は６３％であったが２４時間目、４８時
間目にはそれぞれ２０チ、０係となシ、著しい活性低下
が認められ九〇
６１ｉ）発明の効果
本発明の精製方法によれば、スチレン類中に含まれるフ
ェニルアセチレン等の不純物を、高い水素添加選択率で
安定して除去することができ、その際にスチレン等の有
用成分の水素添加による消耗が少ない。Comparative example Moisture in crude styrene fraction i'12500Wtpprrl
The reaction was carried out under the same conditions as in Example 2, except for the following. Six hours after supplying crude styrene, the hydrogenation rate of phenylacetylene was 63%, but at 24 hours and 48 hours, it was 20% and 0%, respectively, and a significant decrease in activity was observed.90 61i) Effects of the Invention According to the purification method of the present invention, impurities such as phenylacetylene contained in styrenes can be stably removed with high hydrogenation selectivity, and at this time, useful components such as styrene can be removed. Less consumption due to hydrogenation.
従って、本発明によシ、重合特性にバラツキがなく、品
質の安定した？リマー製品を得るのに適する精製スチレ
ン類を有利に製造することが出来る。Therefore, according to the present invention, there is no variation in polymerization properties and stable quality. Purified styrenes suitable for obtaining remer products can advantageously be produced.
Claims (1)
して含有される高不飽和不純物を選択的に水素添加して
除去する方法において、該水素添加反応系に供給される
該スチレン類を含む原料中の水分含量を２０００重量ｐ
ｐｍ以下に保ち且つ該水素添加反応における反応温度を
０℃〜１２０℃の範囲に保つことを特徴とするスチレン
類の精製方法。1) In a method of hydrogenating styrenes in the presence of a hydrogenation catalyst to selectively hydrogenate and remove highly unsaturated impurities contained, the styrenes supplied to the hydrogenation reaction system are The water content in the raw materials containing 2000 p
A method for purifying styrenes, characterized by keeping the temperature at pm or less and keeping the reaction temperature in the hydrogenation reaction in the range of 0°C to 120°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114187A JPH085814B2 (en) | 1987-05-11 | 1987-05-11 | Styrene purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114187A JPH085814B2 (en) | 1987-05-11 | 1987-05-11 | Styrene purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63277639A true JPS63277639A (en) | 1988-11-15 |
| JPH085814B2 JPH085814B2 (en) | 1996-01-24 |
Family
ID=14631375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62114187A Expired - Fee Related JPH085814B2 (en) | 1987-05-11 | 1987-05-11 | Styrene purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085814B2 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103428A (en) * | 1977-02-21 | 1978-09-08 | Uop Inc | Method of dehydrogenating alkyl aromatic hydrocarbon |
| JPS59196742A (en) * | 1983-04-22 | 1984-11-08 | Showa Denko Kk | Regeneration of selectively hydrocracking catalyst |
| JPS59216838A (en) * | 1983-05-25 | 1984-12-06 | Mitsubishi Petrochem Co Ltd | Purification of styrene-containing composition by selective hydrogenation |
| JPS604139A (en) * | 1983-06-22 | 1985-01-10 | Showa Denko Kk | Selective hydrogenation process |
| JPS6013724A (en) * | 1983-07-01 | 1985-01-24 | Mitsubishi Petrochem Co Ltd | Purification of styrenes |
| JPS60132652A (en) * | 1983-12-22 | 1985-07-15 | Showa Denko Kk | Regeneration of selective hydrogenating catalyst |
| JPS61191627A (en) * | 1985-02-21 | 1986-08-26 | Asahi Chem Ind Co Ltd | Purification of composition containing styrene compound |
| JPS6287535A (en) * | 1985-10-15 | 1987-04-22 | Mitsubishi Petrochem Co Ltd | Purification of styrene or such |
| JPH034046A (en) * | 1989-05-26 | 1991-01-10 | Robert Bosch Gmbh | Damper |
-
1987
- 1987-05-11 JP JP62114187A patent/JPH085814B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103428A (en) * | 1977-02-21 | 1978-09-08 | Uop Inc | Method of dehydrogenating alkyl aromatic hydrocarbon |
| JPS59196742A (en) * | 1983-04-22 | 1984-11-08 | Showa Denko Kk | Regeneration of selectively hydrocracking catalyst |
| JPS59216838A (en) * | 1983-05-25 | 1984-12-06 | Mitsubishi Petrochem Co Ltd | Purification of styrene-containing composition by selective hydrogenation |
| JPS604139A (en) * | 1983-06-22 | 1985-01-10 | Showa Denko Kk | Selective hydrogenation process |
| JPS6013724A (en) * | 1983-07-01 | 1985-01-24 | Mitsubishi Petrochem Co Ltd | Purification of styrenes |
| JPS60132652A (en) * | 1983-12-22 | 1985-07-15 | Showa Denko Kk | Regeneration of selective hydrogenating catalyst |
| JPS61191627A (en) * | 1985-02-21 | 1986-08-26 | Asahi Chem Ind Co Ltd | Purification of composition containing styrene compound |
| JPS6287535A (en) * | 1985-10-15 | 1987-04-22 | Mitsubishi Petrochem Co Ltd | Purification of styrene or such |
| JPH034046A (en) * | 1989-05-26 | 1991-01-10 | Robert Bosch Gmbh | Damper |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH085814B2 (en) | 1996-01-24 |
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