JPH03109335A - Production of styrene - Google Patents
Production of styreneInfo
- Publication number
- JPH03109335A JPH03109335A JP1246188A JP24618889A JPH03109335A JP H03109335 A JPH03109335 A JP H03109335A JP 1246188 A JP1246188 A JP 1246188A JP 24618889 A JP24618889 A JP 24618889A JP H03109335 A JPH03109335 A JP H03109335A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ethylbenzene
- reaction
- styrene
- deterioration
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052700 potassium Inorganic materials 0.000 claims description 20
- 239000011591 potassium Substances 0.000 claims description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 230000006866 deterioration Effects 0.000 abstract description 17
- 238000007086 side reaction Methods 0.000 abstract description 2
- 229910002552 Fe K Inorganic materials 0.000 abstract 1
- 229910003110 Mg K Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 230000007423 decrease Effects 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910017086 Fe-M Inorganic materials 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000005194 ethylbenzenes Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000008096 xylene Substances 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】
［産業上の利用分野］
本発明はスチレンの製造方法に関し、詳しくは触媒の劣
化を抑制し、スチレンの生成量の増大を図ることのでき
るスチレンの製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing styrene, and more particularly, to a method for producing styrene that can suppress deterioration of a catalyst and increase the amount of styrene produced. be.
Ｌ従来の技術および発明が解決しようとする課題〕通常
、スチレンはエチルベンゼンを脱水素することによって
製造される。L. Prior Art and Problems to be Solved by the Invention] Styrene is normally produced by dehydrogenating ethylbenzene.
このエチルベンゼンの脱水素反応に用いられる触媒とし
て、たとえば炭酸カリウム含有酸化鉄のごときカリウム
成分を含有する脱水素触媒が知られており（アメリカ特
許第２，３７０，７９７号公報、アメリカ特許第２，４
１４，５８５号公報）、また、この反応系に比較的多量
のスチームを存在させて反応させることも知られている
。As catalysts used in this ethylbenzene dehydrogenation reaction, dehydrogenation catalysts containing a potassium component such as potassium carbonate-containing iron oxide are known (U.S. Pat. No. 2,370,797, U.S. Pat. No. 2, 4
14,585), and it is also known to cause the reaction to occur in the presence of a relatively large amount of steam in the reaction system.
ところで、このようなエチルベンゼンの脱水素によるス
チレンの製造においては、反応を長時間継続するにつれ
て、経時的に触媒の劣化を来たし、エチルベンゼンの転
化率が低下してスチレンの生成量が減少してくるという
不都合があった。このため、スチレンの工業的な製造に
おいて、きわめて重要な解決すべき技術課題となってい
た。By the way, in the production of styrene by such dehydrogenation of ethylbenzene, as the reaction continues for a long time, the catalyst deteriorates over time, the conversion rate of ethylbenzene decreases, and the amount of styrene produced decreases. There was this inconvenience. For this reason, this has become an extremely important technical problem to be solved in the industrial production of styrene.
一般に、前記カリウム成分を含有する触媒の劣化の主な
原因は、
■触媒中の金属のシンタリング
■触媒表面での炭素質の析出
■カリウムの飛散
が挙げられる。Generally, the main causes of deterioration of the catalyst containing the potassium component are: (1) Sintering of metal in the catalyst (2) Precipitation of carbonaceous material on the catalyst surface (2) Scattering of potassium.
これらの中でも、酸化鉄系の触媒は、微量のカリウム成
分の添加によって、著しく脱水素反応活性が向上するが
、高温のスチームの存在下では、■のカリウムの飛散が
生じやすい。Among these, the dehydrogenation reaction activity of iron oxide-based catalysts is significantly improved by adding a small amount of potassium component, but in the presence of high-temperature steam, potassium is likely to scatter (2).
このＩ；め、工業的に使用される触媒の多くは、カリウ
ムの飛散を考慮して、過剰のカリウム成分を含有せしめ
るべく添加されている。For this reason, many of the catalysts used industrially are added to contain an excess potassium component in consideration of scattering of potassium.
しかしながら、このような過剰のカリウム成分の添加は
、カリウムの飛散による触媒の粉化と触媒強度の低下を
招き、ひいては反応器の性能の低下の原因ともなってい
た。However, such addition of an excessive potassium component causes powdering of the catalyst and a decrease in catalyst strength due to scattering of potassium, which in turn causes a decrease in the performance of the reactor.
本発明は、有効に触媒の劣化を抑制し、スチレンの生成
量の増大を図ることのできるスチレンの製造方法を提供
することを目的とする。An object of the present invention is to provide a method for producing styrene that can effectively suppress deterioration of a catalyst and increase the amount of styrene produced.
［課題を解決するための手段］
本発明者らは、前記目的を達成するため、触媒に含有さ
れるカリウムの飛散に着目して鋭意検討を重ねた結果、
反応系に二酸化炭素および／または一酸化炭素を供給し
ながら反応を行うことによって、カリウムの飛散を可及
的に防止でき、触媒の劣化を抑制して、スチレンの生成
量を増大できるということを見い出し、この知見に基づ
いて本発明を完成するに至った。[Means for Solving the Problems] In order to achieve the above object, the present inventors have conducted intensive studies focusing on the scattering of potassium contained in the catalyst.
By conducting the reaction while supplying carbon dioxide and/or carbon monoxide to the reaction system, scattering of potassium can be prevented as much as possible, deterioration of the catalyst can be suppressed, and the amount of styrene produced can be increased. Based on this finding, we have completed the present invention.
すなわち、本発明によれば、カリウム成分を含有する脱
水素触媒およびスチームの存在下、エチルベンゼンを脱
水素反応せしめてスチレンを製造するにあたり、該反応
系に二酸化炭素および／または一酸化炭素を供給するこ
とを特徴とするスチレンの製造方法が提供される。That is, according to the present invention, when producing styrene by dehydrogenating ethylbenzene in the presence of a dehydrogenation catalyst containing a potassium component and steam, carbon dioxide and/or carbon monoxide is supplied to the reaction system. A method for producing styrene is provided.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において用いる原料のエチルベンゼンについては
特に制限はなく、高純度のものが好ましイトハ言工、ベ
ンゼン、トルエン、キシレン等、エチルベンゼンの製造
工程に由来する他の成分を若干含んでいても差し支えな
い。There are no particular restrictions on the raw material ethylbenzene used in the present invention, and it is preferable to use one with high purity, and it may contain a small amount of other components derived from the ethylbenzene manufacturing process, such as benzene, toluene, xylene, etc. .
次に、エチルベンゼンの脱水素反応に用いる触媒として
は、カリウム成分を含有する脱水素触媒が使用される。Next, as a catalyst for the dehydrogenation reaction of ethylbenzene, a dehydrogenation catalyst containing a potassium component is used.
この触媒におけるカリウム成分は、反応活性の促進や熱
安定性の向上に貢献し、微量の添加によってこれらの機
能を発揮するものである。The potassium component in this catalyst contributes to promoting reaction activity and improving thermal stability, and exhibits these functions when added in a small amount.
このカリウム成分を含有する脱水素触媒としては、Ｆｅ
−に系、Ｆｅ−Ｃｒ−に系、Ｆｅ−Ｃｒ−に−Ｖ−Ｃｏ
系、Ｆｅ−Ｃｒ−に−Ｃｅ −Ｍｏ−Ｃｏ系、Ｆｅ−Ｍ
ｇ−に系などの種々のものが挙げられ、中でもＦｅ−に
系やＦｅ−Ｍｇ−に系は好ましい触媒である。As the dehydrogenation catalyst containing this potassium component, Fe
- system, Fe-Cr- system, Fe-Cr- system -V-Co
system, Fe-Cr- to -Ce-Mo-Co system, Fe-M
There are various types of catalysts such as g-type catalysts, and among them, Fe-type catalysts and Fe-Mg-type catalysts are preferable.
これら各県の触媒成分は酸化物として調製され、反応条
件下では金属酸化物として存在し機能する。The catalyst components in each of these prefectures are prepared as oxides, and under reaction conditions exist and function as metal oxides.
鉄成分は酸化物として７０重量％以上含有され、Ｆｅ２
Ｏ３の形態として調製され使用されるが、反応条件下で
は一部還元されてＦｅ３Ｏ４の形態となる。The iron component is contained as an oxide in an amount of 70% by weight or more, and Fe2
It is prepared and used in the form of O3, but under reaction conditions it is partially reduced to the form of Fe3O4.
カリウム成分は酸化カリウムや炭酸カリウムの形態で、
１〜３０重量％添加されるが、反応条件下では一部酸化
カリウムとなる。Potassium components are in the form of potassium oxide and potassium carbonate.
Although it is added in an amount of 1 to 30% by weight, it partially becomes potassium oxide under the reaction conditions.
その他の金属成分は１０重量％以下の量で添加される。Other metal components are added in amounts up to 10% by weight.
酸化マグネシウムは触媒の劣化抑制の効果を有するが、
主として鉄のシンタリングの抑制効果があるとされてい
る。また、酸化クロムは触媒の構造安定化に寄与すると
言われている。Magnesium oxide has the effect of suppressing catalyst deterioration, but
It is said that it mainly has the effect of suppressing sintering of iron. Furthermore, chromium oxide is said to contribute to stabilizing the structure of the catalyst.
これら触媒は、円柱用ベレット、リング等の形状に成形
して使用されることが多いが、本発明における反応系の
ように低圧力の条件下が好ましい場合においては、圧力
損失を低下させる目的で、リブ状とするなど、反応や反
応器に応じて適宜触媒形状を変化させて使用することが
望ましい。These catalysts are often used in the form of cylindrical pellets, rings, etc., but in cases where low pressure conditions are preferred, such as in the reaction system of the present invention, they are used for the purpose of reducing pressure loss. It is desirable to change the shape of the catalyst as appropriate depending on the reaction and reactor, such as a rib shape.
これら触媒は、本発明においては通常、連続流通反応器
に充填して用いられる。In the present invention, these catalysts are usually used by being packed in a continuous flow reactor.
本発明においては、熱源、反応物の分圧低下および炭素
質の生成による触媒の劣化抑制の目的で、比較的多量の
スチームの存在下にて反応を行う。In the present invention, the reaction is carried out in the presence of a relatively large amount of steam for the purpose of reducing the partial pressure of the heat source and reactants and suppressing deterioration of the catalyst due to the production of carbonaceous matter.
このスチームは、通常エチルベンゼン１モルに対し、１
．０〜２０．０モル、好ましくは４．０〜１５．０モル
の範囲で存在させる。This steam is usually 1 mole of ethylbenzene.
．． It is present in a range of 0 to 20.0 moles, preferably 4.0 to 15.0 moles.
本発明におけるエチルベンゼンの脱水素反応においては
、反応器入口温度として４００〜７５０１１０１好まし
くは５５０〜６５０℃、反応器入口圧力として０．３〜
２．Ｏａｔｍ、好ましくは０．４５〜０．８５ａｔｍの
条件が採用される。In the dehydrogenation reaction of ethylbenzene in the present invention, the reactor inlet temperature is 400 to 7501101, preferably 550 to 650°C, and the reactor inlet pressure is 0.3 to
2. A condition of Oatm, preferably 0.45 to 0.85 atm is adopted.
本発明は、前記のとおり、カリウム成分を含有する脱水
素触媒およびスチームの存在下、エチルベンゼンを脱水
素してスチレンを製造するものであるが、この脱水素反
応系に二酸化炭素および／または一酸化炭素を供給する
ことを特徴とするスチレンの製造方法を提供するもので
ある。As described above, the present invention produces styrene by dehydrogenating ethylbenzene in the presence of a dehydrogenation catalyst containing a potassium component and steam, and carbon dioxide and/or monoxide is added to this dehydrogenation reaction system. The present invention provides a method for producing styrene characterized by supplying carbon.
この二酸化炭素および／または一酸化炭素の供給はわず
かの脱水素反応初期活性の低下を生ずるが触媒の劣化抑
制効果があり総合的にはエチルベンゼンの転化率を向上
させる。Although this supply of carbon dioxide and/or carbon monoxide causes a slight decrease in the initial activity of the dehydrogenation reaction, it has the effect of suppressing deterioration of the catalyst, and overall improves the conversion rate of ethylbenzene.
この二酸化炭素および／または一酸化炭素は、通常エチ
ルベンゼン１．０モルに対し、１．０Ｘ１０弓〜２．０
モル、好ましくは１．０ＸｌＯ−”〜２、Ｏｘ１ｇ−ｔ
モルの範囲で供給される。This carbon dioxide and/or carbon monoxide is usually 1.0×10 to 2.0 mol per 1.0 mol of ethylbenzene.
Mol, preferably 1.0XlO-" to 2, Ox1g-t
Supplied in molar range.
１．０Ｘ１０−’モル以下の供給量では、触媒の劣化抑
制の効果は少なく、２モル以上の供給量においては、触
媒の劣化抑制効果は向上するものの、反応初期活性の低
下を促進し、総合的な優位性が低下する。また、過剰の
供給は、エチルベンゼンやスチレンの酸化による分解を
促進し、好ましくない。If the supply amount is less than 1.0 x 10-' moles, the effect of suppressing catalyst deterioration is small, and if the supply amount is more than 2 moles, although the effect of suppressing catalyst deterioration is improved, it promotes a decrease in the initial reaction activity and the overall competitive advantage will decline. Moreover, excessive supply promotes the decomposition of ethylbenzene and styrene by oxidation, which is not preferable.
供給する二酸化炭素または一酸化炭素はそれぞれ単独で
あっても、混合物であってもよい。Carbon dioxide or carbon monoxide may be supplied alone or in a mixture.
本発明においては、副反応により微量の二酸化炭素や一
酸化炭素が生成する。この二酸化炭素や一酸化炭素は、
通常、反応器の下流部において触媒劣化の抑制を果たす
。このため、反応器における触媒の劣化は主として反応
器の入口部において生起する。In the present invention, trace amounts of carbon dioxide and carbon monoxide are produced by side reactions. This carbon dioxide and carbon monoxide are
Usually, catalyst deterioration is suppressed downstream of the reactor. Therefore, deterioration of the catalyst in the reactor mainly occurs at the inlet of the reactor.
したがって、二酸化炭素および／または一酸化炭素は、
反応器の入口部に供給することが好ましく、このように
することにより、反応器全体の触媒の劣化抑制にきわめ
て効果的となる。Therefore, carbon dioxide and/or carbon monoxide
It is preferable to supply it to the inlet of the reactor, and doing so is extremely effective in suppressing deterioration of the catalyst throughout the reactor.
また、副生ずる二酸化炭素や一酸化炭素を含むオフガス
を利用して、反応器に循環して供給することも有効な方
法となる。さらに、必要相当量の二酸化炭素および／ま
たは一酸化炭素を含む炭化水素燃焼ガスを供給源および
熱源とする方法も効果的な方法である。Another effective method is to utilize off-gas containing by-product carbon dioxide and carbon monoxide to circulate and supply it to the reactor. Furthermore, a method using hydrocarbon combustion gas containing a necessary amount of carbon dioxide and/or carbon monoxide as the supply and heat source is also an effective method.
このように、反応系に二酸化炭素および／または一酸化
炭素を供給することにより、触媒の劣化抑制が効果的に
達成され、エチルベンゼンの転化率を向上させると共に
スチレン生産量を増大させることができる。また、本発
明以外の反応系において反応中に生起するカリウムの飛
散に対しても、反応ガス中への二酸化炭素８よび／また
は一酸化炭素の供給による炭酸化によって、触媒の安定
化が期待できる。In this way, by supplying carbon dioxide and/or carbon monoxide to the reaction system, deterioration of the catalyst can be effectively suppressed, and the conversion rate of ethylbenzene can be improved and the amount of styrene produced can be increased. Furthermore, the catalyst can be expected to be stabilized by carbonation by supplying carbon dioxide 8 and/or carbon monoxide to the reaction gas against the scattering of potassium that occurs during the reaction in reaction systems other than those of the present invention. .
本発明における反応は、回分式、半回分式および連続式
のいずれの反応器を用いて行ってもよいが、好ましくは
連続流通式の反応器により行うことが望ましい。The reaction in the present invention may be carried out using any of a batch type, semi-batch type and continuous type reactor, but it is preferable to carry out the reaction using a continuous flow type reactor.
反応終了後は、通常の分離精製工程を経て、目的とする
スチレンを取得する。After the reaction is completed, the target styrene is obtained through normal separation and purification steps.
このスチレンは、ポリスチレン、スチレン共重合体、そ
の他の化成品原料としてきわめて有用な化合物として利
用することができる。This styrene can be used as an extremely useful compound as a raw material for polystyrene, styrene copolymers, and other chemical products.
以下、実施例および比較例を挙げて、本発明をさらに詳
しく説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１〜２および比較例
円筒ダウン７０−を連続流通反応器（内径２８ＷＩ１１
１高さ４５０ ｒａｍ、中央部に外径６ｔａｒａの熱電
対保護管を有する）に、炭酸カリウム添加酸化鉄触媒（
日産ガードラー触媒株式会社製、Ｇ６４１）ペレット７
、Ｏｇを充填し、エチルベンゼン９９．９モル％および
トルエン０．１モル％からなる油分を１ｏＯｒａｔ／ｈ
ｒの供給量にて供給し、エチルベンゼンに対し、重量比
２．０量（モル比１１．８）のスチームの存在下、０．
５８ａｔｍの圧力、６５０°Ｃの温度の条件で、エチル
ベンゼンの脱水素反応を行った。Examples 1 and 2 and Comparative Example cylindrical down 70- were placed in a continuous flow reactor (inner diameter 28WI11
1 450 ram in height, with a thermocouple protection tube with an outer diameter of 6 tara in the center), and a potassium carbonate-added iron oxide catalyst (
Made by Nissan Girdler Catalyst Co., Ltd., G641) Pellet 7
, Og, and oil consisting of 99.9 mol% ethylbenzene and 0.1 mol% toluene was added at 1oOrat/h.
In the presence of steam at a weight ratio of 2.0 (mole ratio 11.8) to ethylbenzene, the steam was supplied at an amount of 0.
The dehydrogenation reaction of ethylbenzene was carried out under the conditions of a pressure of 58 atm and a temperature of 650°C.
この反応の際、府記全供給量に対して、実施例１では０
．１モル％（エチルベンゼン１モルに対して１．２８Ｘ
１０−２モル）、実施例２では０．２モル％（エチルベ
ンゼン１モルに対して２．５６ＸＩＯ−”モル）、そし
て比較例では０．０モル％の二酸化炭素を反応器の入口
部に供給した。During this reaction, in Example 1, 0
．． 1 mol% (1.28X for 1 mol of ethylbenzene
10-2 mol), 0.2 mol% in Example 2 (2.56 did.
反応終了後、エチルベンゼンの転化率を求め、これに基
づいて、触媒の反応活性を評価した。After the reaction was completed, the conversion rate of ethylbenzene was determined, and based on this, the reaction activity of the catalyst was evaluated.
この結果を第１図に示す。The results are shown in FIG.
また、触媒の反応活性の失活までのエチルベンゼン転化
率時間積分値を第１表に示す。Further, Table 1 shows the time-integrated values of the ethylbenzene conversion rate until the reaction activity of the catalyst is deactivated.
第 １ 表
第１図および第１表により、二酸化炭素を供給した場合
としない場合において、触媒の反応活性劣化の抑制に顕
著な差が認められることが明らかである。Table 1 From FIG. 1 and Table 1, it is clear that there is a significant difference in the suppression of reaction activity deterioration of the catalyst between when carbon dioxide is supplied and when carbon dioxide is not supplied.
［発明の効果］
本発明によれば、エチルベンゼンを脱水素してスチレン
を製造する方法において、用いる触媒の劣化抑制が効果
的に達成され、エチルベンゼンの転化率を向上させると
共に、スチレン生産量を増大させることのできるスチレ
ンの製造方法が提供される。[Effects of the Invention] According to the present invention, in a method for producing styrene by dehydrogenating ethylbenzene, deterioration of the catalyst used can be effectively suppressed, improving the conversion rate of ethylbenzene and increasing styrene production. A method for producing styrene is provided.
このため、本発明は、ポリスチレンやその他の合成樹脂
の原料、各種化成品原料として広範な用途をもつスチレ
ンの工業的な製造方法としてきわめて有用である。Therefore, the present invention is extremely useful as an industrial method for producing styrene, which has a wide range of uses as a raw material for polystyrene and other synthetic resins, and as a raw material for various chemical products.
第１図は、実施例および比較例におけるエチルベンゼン
転化率の経時変化を示す。FIG. 1 shows changes in ethylbenzene conversion over time in Examples and Comparative Examples.
Claims (1)
の存在下、エチルベンゼンを脱水素反応せしめてスチレ
ンを製造するにあたり、該反応系に二酸化炭素および／
または一酸化炭素を供給することを特徴とするスチレン
の製造方法。 ２ エチルベンゼン１．０モルに対して１．０〜２０．
０モルのスチームを存在させる請求項１記載のスチレン
の製造方法。 ３ エチルベンゼン１．０モルに対し、１．０×１０＾
−＾５〜２．０モルの二酸化炭素および／または一酸化
炭素を供給する請求項１または２記載のスチレンの製造
方法。[Claims] 1. In producing styrene by dehydrogenating ethylbenzene in the presence of a dehydrogenation catalyst containing a potassium component and steam, carbon dioxide and/or carbon dioxide are added to the reaction system.
Or a method for producing styrene, characterized by supplying carbon monoxide. 2 1.0 to 20.0% per 1.0 mole of ethylbenzene.
The method for producing styrene according to claim 1, wherein 0 mol of steam is present. 3 1.0 x 10^ for 1.0 mole of ethylbenzene
The method for producing styrene according to claim 1 or 2, wherein 5 to 2.0 moles of carbon dioxide and/or carbon monoxide are supplied.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1246188A JPH0639437B2 (en) | 1989-09-21 | 1989-09-21 | Method for producing styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1246188A JPH0639437B2 (en) | 1989-09-21 | 1989-09-21 | Method for producing styrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03109335A true JPH03109335A (en) | 1991-05-09 |
| JPH0639437B2 JPH0639437B2 (en) | 1994-05-25 |
Family
ID=17144825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1246188A Expired - Lifetime JPH0639437B2 (en) | 1989-09-21 | 1989-09-21 | Method for producing styrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0639437B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011524370A (en) * | 2008-06-14 | 2011-09-01 | ラムス テクノロジー インコーポレイテッド | Process for the production of styrene monomer by improving energy efficiency and injection of recycle gas into EB vaporizer |
| JP2011524913A (en) * | 2008-06-19 | 2011-09-08 | ルマス テクノロジー インコーポレイテッド | A combined method of carbon dioxide and oxygen for the dehydrogenation of ethylbenzene to styrene. |
-
1989
- 1989-09-21 JP JP1246188A patent/JPH0639437B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011524370A (en) * | 2008-06-14 | 2011-09-01 | ラムス テクノロジー インコーポレイテッド | Process for the production of styrene monomer by improving energy efficiency and injection of recycle gas into EB vaporizer |
| JP2011524913A (en) * | 2008-06-19 | 2011-09-08 | ルマス テクノロジー インコーポレイテッド | A combined method of carbon dioxide and oxygen for the dehydrogenation of ethylbenzene to styrene. |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0639437B2 (en) | 1994-05-25 |
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