JPH085815B2 - Styrene purification method - Google Patents
Styrene purification methodInfo
- Publication number
- JPH085815B2 JPH085815B2 JP62116415A JP11641587A JPH085815B2 JP H085815 B2 JPH085815 B2 JP H085815B2 JP 62116415 A JP62116415 A JP 62116415A JP 11641587 A JP11641587 A JP 11641587A JP H085815 B2 JPH085815 B2 JP H085815B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- hydrogenation
- styrenes
- catalyst
- styrene
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title description 27
- 238000000746 purification Methods 0.000 title description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000003440 styrenes Chemical class 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 26
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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 5
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000006116 polymerization 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
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- -1 styrene compound 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
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-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
- 230000007423 decrease Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N 1-ethyl-4-methylbenzene Chemical compound CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000005194 ethylbenzenes Chemical class 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 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
- 150000002898 organic sulfur compounds Chemical class 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
- 238000000926 separation method Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Description
【発明の詳細な説明】 （ｉ）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。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。DETAILED DESCRIPTION OF THE INVENTION (i) Object of the Invention [Field of Industrial Application] The present invention relates to a method for purifying styrenes. More particularly, the present invention relates to a method for selectively hydrogenating and removing highly unsaturated impurities contained in styrene, 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。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り、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。Styrenes are widely used as a polymer raw material. However, when a polymer is produced by polymerizing styrenes, there is a problem in that the polymerization characteristics vary, and a polymer product of stable quality cannot be obtained.
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っ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って、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、ジオレフィン
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
よることが判明した。According to the findings of the present inventors, the cause is that styrenes obtained by the dehydrogenation reaction of ethylbenzenes are highly unsaturated impurities depending on the catalyst characteristics used in the reaction, the reaction format, the operating conditions of the plant, etc. That is, it was found that the contents of acetylenes such as phenylacetylene, diolefins and the like fluctuate widely, and these highly unsaturated impurities act as a polymerization inhibitor during the polymerization of styrenes.
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り見当らないが、特公昭48-16497
号公報には、ニッケル５％以上、及びクロム、マンガ
ン、銅の１種以上をニッケルに対して50％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、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。Conventionally, there are not many documents on removal of highly unsaturated impurities contained in styrenes, but Japanese Patent Publication No.
Japanese Patent Laid-Open Publication No. 2005-242242 discloses a styrene compound obtained by treating a solid multi-component catalyst containing 5% or more of nickel and 50% or less of one of chromium, manganese, and copper with respect to nickel with a specific organic sulfur compound. Is hydrogenated, and the contained phenylacetylene is selectively hydrogenated to be removed.
しかしながら、前記公報に記載された水素添加処理方
法は、液空間速度が僅か５hr-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
加して除くことが出来ても、工業的に有利に実施出来る
方法ではないという問題点がある。However, in the hydrogenation treatment method described in the above publication, the liquid hourly space velocity is only about 5 hr -1 , and therefore, even if such a method can selectively remove phenylacetylene by hydrogenation, There is a problem that this method is not industrially advantageous.
（ii）発明の構成 〔問題点を解決するための手段〕 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等をPdを含有する水素添加触媒
で水素添加処理するに当り、該水素添加反応を液相流通
系で行ない、その際反応系に供給される原料の空塔線速
度を0.08〜5cm/秒の範囲に保つことにより水素添加反応
活性が安定して得られることを見出し、本発明を完成す
るに至った。(Ii) Configuration of the Invention [Means for Solving the Problems] The inventors of the present invention have made further diligent studies to solve the above problems, and as a result, highly unsaturated impurities, particularly acetylene such as phenylacetylene. In performing hydrogenation treatment with a hydrogenation catalyst containing Pd, etc., the hydrogenation reaction is performed in a liquid phase flow system, and the superficial linear velocity of the raw material supplied to the reaction system is 0.08 to 5 cm / sec. It was found that the hydrogenation reaction activity can be stably obtained by keeping the content within the range, and the present invention has been completed.
即ち、本発明のスチレン類の精製方法は、 １）スチレン類をPdを含有する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、該水素添加反応を
液相流通系で且つ反応系に供給される原料の空塔線速度
を0.08〜5cm/秒なる条件下で行なうことを特徴とするス
チレン類の精製方法である。That is, according to the method for purifying styrenes of the present invention, 1) styrene is subjected to a hydrogenation treatment in the presence of a Pd-containing hydrogenation catalyst to selectively hydrogenate and remove highly unsaturated impurities contained therein. In the method, the hydrogenation reaction is carried out in a liquid phase flow system and under the condition that the superficial linear velocity of the raw material supplied to the reaction system is 0.08 to 5 cm / sec.
（発明の具体的説明） 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−メチルスチレン、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びこれらの少なく
とも１種を含有する組成物をいう。(Detailed Description of the Invention) Styrenes Styrenes that are the subject of the purification method of the present invention include styrene, p-methylstyrene, vinyltoluene, pt-
It refers to butylstyrene, divinylbenzene and a composition containing at least one of them.
かかるスチレン類は、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
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、たとえばFe-Ce-Kを
主成分とする触媒（特開昭49-120887号、同49-120888
号、同53-129190号、及び53-129191号の各公報等参
照）、又は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 are usually dehydrogenation catalysts of at least one ethylbenzene such as ethylbenzene, p-methylethylbenzene, ethyltoluene, pt-butylethylbenzene, and diethylbenzene, for example, a catalyst containing Fe-Ce-K as a main component. (JP-A-49-120887 and 49-120888
No. 53-129190 and 53-129191), or by dehydrogenation in the presence of various dehydrogenation catalysts such as Fe-Cr-K-based catalysts. It is a reaction product obtained, or a fraction obtained by distillation separation of the 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10〜1000ppm（重量）程度、ジオレフィ
ン類が５〜500ppm（重量）程度である。The styrenes obtained by the above method include acetylenes such as phenylacetylene and diolefins. The content of such highly unsaturated impurities contained in styrenes varies depending on the production conditions, etc.,
Acetylenes are about 10 to 1000 ppm (weight) and diolefins are about 5 to 500 ppm (weight).
ここで、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含量は2000重量ppm以下、好
ましくは、1700ppm重量以下、最も好ましくは1500重量p
pm以下に抑えることが望ましい。Here, the water content in the raw material containing the styrenes supplied to the hydrogenation reaction system of the present invention is 2000 ppm by weight or less, preferably 1700 ppm by weight or less, and most preferably 1500 ppm by weight.
It is desirable to keep it below pm.
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〜
100倍、好ましくは１〜70倍、最も好ましくは１〜50倍
程度である。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 impurities
It is about 100 times, preferably 1 to 70 times, and most preferably about 1 to 50 times.
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。If the amount of hydrogen supplied is too large, useful components such as styrene will be hydrogenated and will be lost, reducing the yield.
水素添加触媒 本発明の精製方法で使用する水素添加触媒として好ま
しい触媒はPd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
体に担持されているが、本発明の場合、Pdの担持量は通
常、0.01〜１重量％、好ましくは0.05〜0.5重量％であ
る。また、その担体としては、耐熱性の無機化合物担
体、たとえばアルミナ、シリカなどの合成ゲル担体、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。Hydrogenation catalyst A preferred catalyst for the hydrogenation catalyst used in the purification method of the present invention is a catalyst containing Pd as a catalyst component. In this type of hydrogenation catalyst, the catalyst component is usually supported on a suitable carrier, but in the present invention, the supported amount of Pd is usually 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight. is there. Examples of the carrier include heat-resistant inorganic compound carriers, for example, synthetic gel carriers such as alumina and silica, and natural inorganic carrier such as diatomaceous earth and porous clay.
空塔線速度 本発明の精製方法における水素添加反応は液相流通系
で行われ、その際反応系に供給される原料の空塔線速度
を0.08〜5cm/秒、好ましくは0.08〜4cm/秒、最も好まし
くは0.08〜3cm/秒の範囲に規制することが必要である。
空塔線速度が0.08cm/秒より小さくなると触媒表面への
ポリマー類の付着が多くなり、安定した活性が得られ
ず、更に水素添加触媒効率が悪くなる等の問題が生ず
る。また空塔線速度が5cm/秒より大きくなると、触媒層
のΔＰが大きくなるなどの問題が生じ、やはり安定した
活性が得られない。Superficial linear velocity The hydrogenation reaction in the purification method of the present invention is carried out in a liquid phase flow system, and the superficial linear velocity of the raw materials supplied to the reaction system is 0.08 to 5 cm / sec, preferably 0.08 to 4 cm / sec. Most preferably, it is necessary to regulate in the range of 0.08 to 3 cm / sec.
If the superficial linear velocity is less than 0.08 cm / sec, the adhesion of polymers to the catalyst surface increases, stable activity cannot be obtained, and the hydrogenation catalyst efficiency deteriorates. Further, if the superficial velocity of the superficial column is higher than 5 cm / sec, there arises a problem that the ΔP of the catalyst layer becomes large, and stable activity cannot be obtained.
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通
常は200℃以下、例えば０℃〜120℃、好ましくは10℃〜
100℃、最も好ましくは20℃〜90℃の範囲で行なうこと
が望ましい。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、
反応温度が余り低過ぎると目的の高不飽和不純物を有効
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 usually performed at 200 ° C or lower, for example, 0 ° C to 120 ° C, preferably 10 ° C to
It is desirable to carry out at 100 ° C, most preferably in the range of 20 ° C to 90 ° C. If the reaction temperature is too high, useful styrenes such as styrene will be hydrogenated, resulting in loss.
If the reaction temperature is too low, the desired highly unsaturated impurities cannot be effectively hydrogenated and removed.
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〜10kg/cm2Ｇである。反応圧力
が高過ぎるとフェニルアセチレン等の高不飽和不純物の
水素添加反応の選択性が低下して来る。Reaction Pressure The total pressure of the hydrogenation reaction in the present invention is usually atmospheric pressure to
Under pressure, preferably atmospheric pressure to 10 kg / cm 2 G. If the reaction pressure is too high, the selectivity of hydrogenation reaction of highly unsaturated impurities such as phenylacetylene decreases.
以下に、触媒製造例、参考例、実施例及び比較例をあ
げてさらに詳述する。これらの例に記載のppmおよび％
は、特に記載しない限り重量基準による。The catalyst production examples, reference examples, examples and comparative examples will be described in more detail below. Ppm and% listed in these examples
Is by weight unless otherwise specified.
触媒製造例 3mmφ×3mmの円柱型に成形したγ−アルミナに、濃度
0.6重量％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。Example of catalyst production The concentration of γ-alumina molded into a 3 mmφ × 3 mm cylindrical shape was
A 0.6% by weight aqueous palladium chloride solution was impregnated and dried at 110 ° C. for one day.
次いで、その乾燥物を水素気流下で400℃の温度で16
時間還元処理して、組成がPd（0.3％）／γ‐Al2O3の水
素添加触媒を得た。The dried product is then stored under a stream of hydrogen at a temperature of 400 ° C for 16
After the time reduction treatment, a hydrogenation catalyst having a composition of Pd (0.3%) / γ-Al 2 O 3 was obtained.
実施例−１ 上記の様にして調製した触媒20ccを直径20mm長さ1mの
ステンレス製反応管に充填した。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％、エチルベンゼン31％、ベン
ゼン1.5％、トルエン2.5％、フェニルアセチレン50〜15
0ppm含有）を1000cc/Hr、反応圧力4kg/cm2Ｇ、H2／フェ
ニルアセチレン1.5モル／モルの条件で連続的に供給し
た。この時の空塔線速度は0.088cm/秒であった。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
目,100日目の水添率はそれぞれ59％,60％であり、安定
した活性が得られた。Example-1 20 cc of the catalyst prepared as described above was filled in a stainless reaction tube having a diameter of 20 mm and a length of 1 m. This reaction tube was kept at 40 ° C, and the crude styrene fraction obtained by the dehydrogenation reaction of ethylbenzene (styrene 65%, ethylbenzene 31%, benzene 1.5%, toluene 2.5%, phenylacetylene 50-15
(Containing 0 ppm) was continuously supplied under the conditions of 1000 cc / Hr, reaction pressure 4 kg / cm 2 G, and H 2 / phenylacetylene 1.5 mol / mol. The empty tower linear velocity at this time was 0.088 cm / sec. The hydrogenation rate of phenylacetylene 8 hours after the supply was 62%, and the hydrogenation rates on the 20th and 100th days were 59% and 60%, respectively, and stable activity was obtained.
実施例−２ 触媒100ccを充填し、反応管を80℃に保ち、粗スチレ
ンの供給量を12l/Hrにしたほかは実施例−１と同一の条
件で反応を行なった。この時の空塔線速度は1.06cm/秒
であった。供給後８時間目のフェニルアセチレンの水添
率は88％、20日目,100日目の水添率はそれそれ82％,84
％であり、安定した活性が得られた。Example-2 The reaction was carried out under the same conditions as in Example-1, except that 100 cc of the catalyst was charged, the reaction tube was kept at 80 ° C, and the supply amount of crude styrene was 12 l / Hr. The empty tower linear velocity at this time was 1.06 cm / sec. The hydrogenation rate of phenylacetylene 8 hours after the supply was 88%, and the hydrogenation rate on the 20th and 100th days was 82%, 84%.
%, And stable activity was obtained.
比較例−１ 反応管を80℃に保ち、粗スチレンの供給量を0.25l/Hr
にしたほかは実施例−１と同一の条件で反応で行なっ
た。この時の空塔線速度は0.035cm/秒であった。粗スチ
レン供給後８時間目のフェニルアセチレンの水添率は85
％であったが、、30日目,100日目にはぞれぞれ52％,35
％となり活性の低下が明らかであった。Comparative Example-1 The reaction tube was kept at 80 ° C., and the crude styrene supply rate was changed to 0.25 l / hr.
The reaction was carried out under the same conditions as in Example 1 except that The superficial linear velocity at this time was 0.035 cm / sec. The hydrogenation rate of phenylacetylene 8 hours after the supply of crude styrene was 85.
%, But 52% and 35% on days 30 and 100, respectively
%, Indicating a decrease in activity.
比較例−２ 触媒１を直径5cm、長さ2mのステンレス製反応管に
充填し、粗スチレンの供給量を400l/Hrにしたほかは実
施例−１と同一の条件で反応を行なったが、触媒層のΔ
Ｐが大きく安定した運転ができなかった。この時の空塔
線速度は5.7cm/秒であった。Comparative Example-2 The reaction was performed under the same conditions as in Example-1, except that the catalyst 1 was filled in a stainless steel reaction tube having a diameter of 5 cm and a length of 2 m, and the supply amount of crude styrene was 400 l / Hr. Δ of catalyst layer
P was large and stable operation could not be performed. The empty tower linear velocity at this time was 5.7 cm / sec.
（iii）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。従って、本発
明により、重合特性にバラツキがなく、品質の安定した
ポ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。(Iii) 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 a high hydrogenation selectivity, at which time useful styrene and the like are useful. Less consumption due to hydrogen addition of components. Therefore, according to the present invention, it is possible to advantageously produce refined styrenes suitable for obtaining a polymer product having stable quality without variation in polymerization characteristics.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江川 一雄 茨城県鹿島郡神栖町東和田17番地 三菱油 化株式会社鹿島事業所内 (72)発明者 清水 正 茨城県鹿島郡神栖町東和田17番地 三菱油 化株式会社鹿島事業所内 (56)参考文献 特開 昭62−87535（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Egawa 17 Towada, Kamisu-cho, Kashima-gun, Ibaraki Prefecture Kashima Plant, Mitsubishi Petrochemical Co., Ltd. (72) Tadashi Shimizu 17 Towada, Kamisu-cho, Kashima-gun, Ibaraki Mitsubishi Petrochemical Kashima Plant Co., Ltd. (56) References JP-A-62-87535 (JP, A)
Claims (1)
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
加反応を液相流通系で且つ反応系に供給される原料の空
塔線速度を0.08〜5cm/秒なる条件下で行なうことを特徴
とするスチレン類の精製方法。1. A method for selectively hydrogenating and removing highly unsaturated impurities contained by hydrogenating styrenes in the presence of a hydrogenation catalyst containing Pd. A method for purifying styrenes, which is carried out in a phase flow system and under the condition that the superficial linear velocity of the raw material supplied to the reaction system is 0.08 to 5 cm / sec.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62116415A JPH085815B2 (en) | 1987-05-13 | 1987-05-13 | Styrene purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62116415A JPH085815B2 (en) | 1987-05-13 | 1987-05-13 | Styrene purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63280032A JPS63280032A (en) | 1988-11-17 |
| JPH085815B2 true JPH085815B2 (en) | 1996-01-24 |
Family
ID=14686504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62116415A Expired - Lifetime JPH085815B2 (en) | 1987-05-13 | 1987-05-13 | Styrene purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085815B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6013724A (en) * | 1983-07-01 | 1985-01-24 | Mitsubishi Petrochem Co Ltd | Styrene purification method |
| JPH0645561B2 (en) * | 1985-02-21 | 1994-06-15 | 旭化成工業株式会社 | Styrene-containing material purification method |
| JPS6287535A (en) * | 1985-10-15 | 1987-04-22 | Mitsubishi Petrochem Co Ltd | Styrene purification method |
| DE3917064A1 (en) * | 1989-05-26 | 1990-11-29 | Bosch Gmbh Robert | SHOCK ABSORBER II |
-
1987
- 1987-05-13 JP JP62116415A patent/JPH085815B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63280032A (en) | 1988-11-17 |
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