JPH0639390B2 - Liquid phase catalytic reaction method - Google Patents
Liquid phase catalytic reaction methodInfo
- Publication number
- JPH0639390B2 JPH0639390B2 JP60228526A JP22852685A JPH0639390B2 JP H0639390 B2 JPH0639390 B2 JP H0639390B2 JP 60228526 A JP60228526 A JP 60228526A JP 22852685 A JP22852685 A JP 22852685A JP H0639390 B2 JPH0639390 B2 JP H0639390B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- solid catalyst
- raw material
- liquid
- catalyst layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006555 catalytic reaction Methods 0.000 title claims description 21
- 239000007791 liquid phase Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 18
- 239000011949 solid catalyst Substances 0.000 claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000006227 byproduct Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 13
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229940049953 phenylacetate Drugs 0.000 claims description 10
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 10
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical group CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000012494 Quartz wool Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Description
【発明の詳細な説明】 発明の技術分野 本発明は固定触媒を用いた液層触媒反応方法に関し、さ
らに詳しくは、触媒劣化が防止される固体触媒を用いた
液相触媒反応方法に関する。TECHNICAL FIELD OF THE INVENTION The present invention relates to a liquid layer catalytic reaction method using a fixed catalyst, and more particularly to a liquid phase catalytic reaction method using a solid catalyst capable of preventing catalyst deterioration.
発明の技術的背景ならびにその問題点 液状原料化合物を固体触媒と接触させて目的とする反応
生成物を製造する液相触媒反応は広く用いられている。
これらの液相触媒反応としては、一般に、液状原料化合
物と固体触媒とを反応器に充填した後一定時間両者を接
触させて反応終了まで反応器内にとどめておく回分方式
と、液状原料化合物が固体触媒と一定の接触時間が保て
るような速度で液状原料化合物を連続的に固体触媒上に
供給しながら反応生成物を回収する連続方式とが知られ
ている。TECHNICAL BACKGROUND OF THE INVENTION AND PROBLEMS THEREOF A liquid-phase catalytic reaction for producing a desired reaction product by bringing a liquid starting material compound into contact with a solid catalyst is widely used.
As these liquid-phase catalytic reactions, generally, a batch method in which a liquid raw material compound and a solid catalyst are charged in a reactor and then kept in contact with each other for a certain period of time until the reaction is completed, and a liquid raw material compound is used. A continuous system is known in which a liquid raw material compound is continuously supplied onto a solid catalyst at a rate such that a constant contact time with the solid catalyst can be maintained, and a reaction product is recovered.
ところが液相触媒反応では、回分方式であろうと連続方
式であろうと、一般的に液状原料化合物よりも高沸点で
ある反応生成物が固体触媒表面に付着するなどして固体
触媒の活性が時間の経過とともに低下することが多い。However, in the liquid phase catalytic reaction, regardless of whether it is a batch system or a continuous system, the reaction product, which generally has a higher boiling point than the liquid raw material compound, adheres to the surface of the solid catalyst and the activity of the solid catalyst is delayed. Often decreases with time.
このような触媒の失活が問題となる液相触媒反応の代表
的な例としては、イオン交換型層状粘土触媒などの固体
触媒の存在下にフェノール類とカルボン酸類とを反応さ
せてアシルフェノール類を製造する反応が挙げられる。
すなわち、イオン交換型層状粘土触媒などの固体触媒の
存在下にフェノール類とカルボン酸類とを反応させる
と、１段でアシルフェノール類が得られるという大きな
利点があるが、反応の進行とともに上記固体触媒表面に
反応生成物であるアシルフェノールあるいは未同定の高
沸点反応生成物が付着するなどして触媒活性が急激に低
下してしまうという問題点があった。As a typical example of the liquid phase catalytic reaction in which the deactivation of the catalyst is a problem, acylphenols are obtained by reacting phenols with carboxylic acids in the presence of a solid catalyst such as an ion-exchange type layered clay catalyst. The reaction for producing
That is, when a phenol and a carboxylic acid are reacted in the presence of a solid catalyst such as an ion-exchange type layered clay catalyst, there is a great advantage that an acylphenol can be obtained in one step. There is a problem that the catalytic activity is drastically reduced due to the attachment of the reaction product acylphenol or unidentified high boiling point reaction product to the surface.
本発明者らは、上記のような液相触媒反応における固体
触媒の失活を解決すべく鋭意検討したところ、特定の方
法を採用することによって上記の問題点が解決されるこ
とを見出して本発明を完成するに至った。The present inventors have made extensive studies to solve the deactivation of the solid catalyst in the liquid phase catalytic reaction as described above, and found that the above problems can be solved by adopting a specific method. The invention was completed.
発明の目的 本発明は、上記のような従来技術に伴なう問題点を解決
しようとするものであって、アシルフェノール合成反応
に代表される液相触媒反応において、用いられる固体触
媒の失活を防止することにより反応生成物を高収率で得
ることができるような液相触媒反応方法を提供すること
を目的としている。An object of the present invention is to solve the problems associated with the conventional techniques as described above, and to deactivate a solid catalyst used in a liquid phase catalytic reaction represented by an acylphenol synthesis reaction. It is an object of the present invention to provide a liquid phase catalytic reaction method in which a reaction product can be obtained in a high yield by preventing the above.
発明の概要 本発明に係る液相触媒反応方法は、液状原料化合物を固
体触媒層に通過させることによって、原料化合物より高
沸点の反応生成物と未反応原料化合物とからなる反応混
合物を回収する液相触媒反応において、回収された反応
混合物を未反応原料化合物などの低沸点化合物のみが蒸
発する温度に加熱し、発生した蒸気を固体触媒層の上部
に導いて冷却し、得られた凝縮液を固定触媒部に循環さ
せて固体触媒層に付着した反応生成物を除去することを
特徴としている。SUMMARY OF THE INVENTION A liquid-phase catalytic reaction method according to the present invention is a liquid for recovering a reaction mixture composed of a reaction product having a boiling point higher than that of a raw material compound and an unreacted raw material compound by passing a liquid raw material compound through a solid catalyst layer. In the phase catalytic reaction, the recovered reaction mixture is heated to a temperature at which only low-boiling compounds such as unreacted raw material compounds evaporate, the generated vapor is guided to the upper part of the solid catalyst layer and cooled, and the obtained condensate is It is characterized in that the reaction product adhered to the solid catalyst layer is removed by circulating it to the fixed catalyst part.
本発明に係る液相触媒反応方法によれば、反応混合物を
加熱して未反応原料化合物などの低沸点化合物のみを蒸
発させてこの蒸気を固体触媒層上部に導いて冷却し、得
られた凝縮液を固定触媒層に循環しているため、固体触
媒に付着した高沸点反応生成物を除去することができ、
したがって固体触媒の失活が防止されて反応生成物を高
収率で得ることができる。According to the liquid-phase catalytic reaction method of the present invention, the reaction mixture is heated to evaporate only low-boiling compounds such as unreacted raw material compounds, and this vapor is guided to the upper portion of the solid catalyst layer to be cooled, and the resulting condensation is obtained. Since the liquid is circulated in the fixed catalyst layer, it is possible to remove the high boiling point reaction product attached to the solid catalyst,
Therefore, the deactivation of the solid catalyst is prevented and the reaction product can be obtained in a high yield.
本発明に係る液相触媒反応方法では、特に、イオン交換
型層状粘土触媒などの固体触媒の存在下にフェノール類
とカルボン酸類との反応によるアシルフェノール類の製
造反応に用いると良好な結果が得られる。In the liquid phase catalytic reaction method according to the present invention, particularly good results are obtained when used in the production reaction of acylphenols by the reaction of phenols and carboxylic acids in the presence of a solid catalyst such as an ion-exchange type layered clay catalyst. To be
発明の具体的説明 以下本発明に係る液相触媒反応方法を、本発明に用いら
れる反応装置の実施例を参照しながら詳細に説明する。DETAILED DESCRIPTION OF THE INVENTION The liquid phase catalytic reaction method according to the present invention will be described in detail below with reference to the examples of the reaction apparatus used in the present invention.
まず本発明に係る液相触媒反応方法に用いられる反応装
置について説明する。この反応装置は、下部に反応混合
物を収容する貯槽１を有し、上部に液状原料化合物の供
給管２ａ，２ｂを有する反応塔本体３からなり、この反
応塔本体３の上側部には反応中に生成する水などを除去
する副生成物除去部４を有する。またこの反応塔本体３
の中央部には、ガラスビーズ層５および石英ウール６で
上下を保持された固体接触媒層７が設けられている。First, a reactor used in the liquid phase catalytic reaction method according to the present invention will be described. This reactor comprises a reaction tank main body 3 having a storage tank 1 for containing a reaction mixture in the lower part thereof and liquid source compound supply pipes 2a, 2b in the upper part thereof. It has a by-product removing unit 4 for removing water and the like produced in the above. Also, this reaction tower body 3
A solid contact catalyst layer 7 held up and down by a glass bead layer 5 and a quartz wool 6 is provided in the central portion of the.
反応混合物を収容する貯槽１は、オイルバスなど加熱手
段８によって所望温度に加熱することができるようにな
っており、またマグネッテクスタラーなどの攪拌子９よ
り攪拌されるようになっている。この貯槽１には、内容
物の温度を測定する熱電対１０および反応生成物を外部
に取出すための取出口１１が設けられている。この取出
口１１から取出された反応生成物はポンプ１２を径て容
器１３に回収される。The storage tank 1 containing the reaction mixture can be heated to a desired temperature by a heating means 8 such as an oil bath, and is agitated by an agitator 9 such as a magnetic stirrer. The storage tank 1 is provided with a thermocouple 10 for measuring the temperature of the contents and an outlet 11 for taking out the reaction products to the outside. The reaction product taken out from the take-out port 11 passes through the pump 12 and is collected in the container 13.
反応塔本体３の上部には、前述のように液体原料化合物
の供給管２ａ，２ｂが設けられているが、この供給管２
ａ，２ｂにはそれぞれの液体原料化合物がポンプ１４
ａ，１４ｂを介して供給されるようになっており、この
液体原料化合物を加熱状態で固体触媒層７に供給できる
ように第１サーモウェル１５が供給管付近に設けられて
いる。As described above, the liquid source compound supply pipes 2a and 2b are provided on the upper portion of the reaction tower body 3.
Each of the liquid source compounds is pumped in a and 2b.
The first thermowell 15 is provided near the supply pipe so that the liquid raw material compound can be supplied to the solid catalyst layer 7 in a heated state.
また、反応塔本体３の外壁と固体触媒層７との間の上部
には、反応生成物である水などの副生成物の蒸気が反応
塔本体３の上部に上昇できるよう孔２０が設けられてい
る。Further, a hole 20 is provided in an upper portion between the outer wall of the reaction tower body 3 and the solid catalyst layer 7 so that vapor of a by-product such as water, which is a reaction product, can rise to the upper portion of the reaction tower body 3. ing.
反応塔本体３の上側部には、前述のように反応中に生成
する水などの副生成物を除去するための副生成物除去部
４が設けられているが、この副生成物除去部４は、反応
混合物から発生する各種の混合蒸気から水などの特定の
副生成物を除去できるよう多段の蒸溜塔１６から構成さ
れており、この蒸溜塔１６の最上部には分離された水な
どの副生成物が凝結して反応系に還流しないように第２
サーモウェル１７が設けられている。このようにして反
応混合物から分離された水などの副生成物は、冷却器１
８ａ，１８ｂによって冷却されて容器１９に回収される
ようになっている。As described above, the by-product removing unit 4 for removing by-products such as water generated during the reaction is provided on the upper side of the reaction tower main body 3, and the by-product removing unit 4 is provided. Is composed of a multi-stage distillation tower 16 so that specific by-products such as water can be removed from various mixed vapors generated from the reaction mixture. At the top of the distillation tower 16, separated water etc. The second by-product should be prevented from condensing and refluxing into the reaction system.
A thermowell 17 is provided. By-products such as water separated from the reaction mixture in this way are cooled by the cooler 1.
It is cooled by 8a and 18b and collected in the container 19.
次に上記のような反応装置を用いた本発明に係る液相触
媒反応方法について、固体触媒としてイオン交換型層状
粘土触媒を用いてフェノールと酢酸とからヒドロキシア
セトフェノンを製造する反応を例にとって説明する。な
おフェノールと酢酸とからのヒドロキシアセトフェノン
への反応は次式のように進行する。Next, the liquid phase catalytic reaction method according to the present invention using the above-described reaction apparatus will be described by taking as an example a reaction for producing hydroxyacetophenone from phenol and acetic acid using an ion exchange type layered clay catalyst as a solid catalyst. . The reaction of phenol and acetic acid to hydroxyacetophenone proceeds according to the following equation.
まず液状原料化合物であるフェノールと酢酸とを、それ
ぞれポンプ１４ａ，１４ｂを介して反応塔本体３の上部
に供給管２ａ，２ｂにより供給する。この際フェノール
および酢酸は、加熱された状態で固体触媒層７に達する
よう第１サーモウェル１５によって加熱される。 First, phenol and acetic acid, which are liquid raw material compounds, are supplied to the upper portion of the reaction tower main body 3 by supply pipes 2a and 2b via pumps 14a and 14b, respectively. At this time, the phenol and acetic acid are heated by the first thermowell 15 so as to reach the solid catalyst layer 7 in a heated state.
供給管２ａ，２ｂにより反応塔本体３に供給されたフェ
ノールと酢酸とは、ガラスビーズ層５および石英ウール
６を経て混合された後にイオン交換型層状粘土触媒層７
に達し、ここで両者の反応が進行し、得られた反応生成
物であるヒドロキシアセトフェノン、水などと、未反応
原料たるフェノール、酢酸とからなる反応混合物が貯層
１に達する。Phenol and acetic acid supplied to the reaction tower body 3 through the supply pipes 2a and 2b are mixed via the glass bead layer 5 and the quartz wool 6 and then the ion exchange type layered clay catalyst layer 7
Then, the reaction of the both proceeds, and the reaction mixture composed of the obtained reaction products, such as hydroxyacetophenone and water, and the unreacted raw materials, phenol and acetic acid, reaches the storage layer 1.
なお、液状原料化合物は反応塔本体３に予じめ充填して
おいてもよく、この場合には、たとえばフェノールのみ
予じめ反応塔本体３の貯槽１に充填しておき、酢酸のみ
を供給管２ｂにより固体触媒槽７に供給するようにして
もよい。The liquid raw material compound may be preliminarily packed in the reaction tower main body 3. In this case, for example, only phenol is preliminarily packed in the storage tank 1 of the reaction tower main body 3 and only acetic acid is supplied. You may make it supply to the solid catalyst tank 7 by the pipe 2b.
反応混合物が収容された貯槽１は、攪拌子９により攪拌
されながらオイルバスなどの加熱手段８により、フェノ
ール、水、酢酸、酢酸フェニルなどの低沸点化合物のみ
が蒸発する温度（具体的には２２５〜２３０℃）にコン
トロールしながら加熱されて、低沸点化合物の蒸気が発
生する。この蒸気は上昇して反応塔本体３の上部に設け
られた孔２０を通過する。The storage tank 1 containing the reaction mixture is heated by a heating means 8 such as an oil bath while being stirred by a stirrer 9 to a temperature at which only low-boiling compounds such as phenol, water, acetic acid and phenyl acetate evaporate (specifically, 225 The heating is performed while controlling the temperature to 230 ° C), and the vapor of the low boiling point compound is generated. This vapor rises and passes through a hole 20 provided in the upper portion of the reaction tower body 3.
このようにして上昇した蒸気は、反応塔本体３を上昇中
に冷却されて、たとえばフェノール、酢酸フェニール、
酢酸などの蒸気は一部凝縮して液状となり、固体触媒層
７に循環される。またフェノール、酢酸フェニル、酢酸
などの蒸気の残部は、反応塔本体３の側壁に設けられた
副生成物除去部４に達し、ここで多段蒸溜塔１６によっ
て凝縮し、得られた凝縮液は固体触媒層７に循環され
る。一方水は反応混合物中に含まれる成分では最も低沸
点であるため、反応塔本体３の側壁に設けられた副生成
物除去部４に達し、ここで多段蒸溜塔１６によってフェ
ノール、酢酸フェニル、酢酸と分離され、第２サーモウ
ェル１７、冷却器１８ａ，１８ｂを介して容器１９に回
収される。The vapor thus raised is cooled while the reaction tower main body 3 is being raised, and is cooled by, for example, phenol, phenyl acetate,
Part of the vapor such as acetic acid is condensed into a liquid state and circulated in the solid catalyst layer 7. The remaining vapor of phenol, phenyl acetate, acetic acid, etc. reaches the by-product removing section 4 provided on the side wall of the reaction tower body 3, where it is condensed by the multi-stage distillation tower 16, and the obtained condensate is a solid. It is circulated to the catalyst layer 7. On the other hand, since water has the lowest boiling point among the components contained in the reaction mixture, it reaches the by-product removal section 4 provided on the side wall of the reaction tower main body 3, and here, the multi-stage distillation tower 16 causes phenol, phenyl acetate, acetic acid. And is collected in the container 19 via the second thermowell 17 and the coolers 18a and 18b.
一方生成した目的化合物であるヒドロキシアセトフェノ
ンは、貯槽１に設けられた取出口１１からポンプ１２を
経て容器１３に回収される。On the other hand, the produced target compound, hydroxyacetophenone, is collected in the container 13 from the outlet 11 provided in the storage tank 1 via the pump 12.
このように反応生成物を取出口１１から回収すると、こ
の回収された量に見合う量の新たな液体原料化合物すな
わちフェノールと酢酸とが供給管２ａ，２ｂを介して固
定触媒層７に供給される。When the reaction product is collected from the outlet 11 in this manner, a new liquid raw material compound, that is, phenol and acetic acid in an amount commensurate with the recovered amount is supplied to the fixed catalyst layer 7 via the supply pipes 2a and 2b. .
発明の効果 本発明では、上記のようにして反応混合物を加熱して、
フェノール、酢酸フェニル、酢酸などの低沸点化合物の
みを蒸発させてこの蒸気を固体触媒層上部に導いて冷却
し、得られた凝縮液を固定触媒層上に循環しているた
め、固体触媒に付着した高沸点反応生成物を洗い流すよ
うにして除去することができ、したがって固体触媒の失
活が防止されて反応生成物を高収率で得ることができ
る。また反応中に生成する水などの副生成物は、反応混
合物を加熱する際に同時に蒸発し、副生成物除去部を介
して反応系外に除去されるため、この点からも反応生成
物を高収率で得ることができる。Effects of the Invention In the present invention, the reaction mixture is heated as described above,
Only low-boiling compounds such as phenol, phenylacetate, and acetic acid are evaporated and this vapor is guided to the upper part of the solid catalyst layer for cooling, and the resulting condensate circulates on the fixed catalyst layer, so it adheres to the solid catalyst. The high boiling point reaction product can be removed by washing out, and thus the deactivation of the solid catalyst is prevented, and the reaction product can be obtained in a high yield. In addition, by-products such as water generated during the reaction are evaporated at the same time when the reaction mixture is heated and removed to the outside of the reaction system through the by-product removal section. It can be obtained in high yield.
以下本発明を実施例により説明するが、本発明はこれら
の実施例に限定されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例 １ 固体触媒としてのアルミニウム交換型合成雲母２ｇを、
その上下部にガラスビーズ、石英ウールを設けて反応塔
本体に充填した。次いで貯槽に予じめフェノール１４１
ｇを仕込み、オイルバスの温度を２２５〜２３０℃に調
節しながら発生するフェノール蒸気を固体触媒層の上方
で凝縮させ、その凝縮液が固体触媒層上に還流するよう
にリフラックスさせながら、酢酸を供給管により第１サ
ーモウェルで加熱しながら固体触媒層上に連続的に供給
して反応を５時間行なった。Example 1 2 g of an aluminum exchange type synthetic mica as a solid catalyst,
Glass beads and quartz wool were provided on the upper and lower parts of the reaction tower to fill the reaction tower body. Next, pre-store phenol 141 in the storage tank.
g, and the phenol vapor generated while adjusting the temperature of the oil bath to 225 to 230 ° C. is condensed above the solid catalyst layer, and the condensate is refluxed so as to reflux onto the solid catalyst layer. Was continuously supplied onto the solid catalyst layer while being heated by the first thermowell through the supply tube, and the reaction was carried out for 5 hours.
得られたヒドロキシアセトンフェノンの生成量は固体触
媒１ｇ当り１１ｇであった。The produced amount of hydroxyacetonephenone was 11 g per 1 g of the solid catalyst.
実施例 ２ 実施例１において、フェノールの仕込み量を７０５ｇに
した以外は実施例１と同様にして反応を４２時間行なっ
た。Example 2 The reaction was carried out for 42 hours in the same manner as in Example 1 except that the charged amount of phenol was changed to 705 g.
得られたヒドロキシアセトンフェノンの生成量は固体触
媒１ｇ当り５５ｇであった。The produced amount of hydroxyacetone phenone was 55 g per 1 g of the solid catalyst.
実施例 ３ 本発明に係る液相触媒反応方法を、固体触媒としてアル
ミニウム交換型合成雲母を用い、フェノールと酢酸フェ
ニルとからヒドロキシアセトンフェノンを合成する反応
について適用した。Example 3 The liquid phase catalytic reaction method according to the present invention was applied to a reaction for synthesizing hydroxyacetone phenone from phenol and phenyl acetate using aluminum exchange type synthetic mica as a solid catalyst.
まず固体触媒としてのアルミニウム交換型合成雲母２ｇ
を、その上下部にガラスビーズ、石英ウールを設けて反
応塔本体に充填し、貯槽にフェノール９４ｇおよび酢酸
フェニル６８ｇを仕込み、オイルバスの温度を２２５〜
２３０℃に調節しながら、発生するフェノールおよび酢
酸フェニルの蒸気を固体触媒層の上方で凝縮させ、その
凝縮液が固体触媒層上に還流するようにリフラックスさ
せながら反応７時間行なった。First, 2 g of aluminum exchange type synthetic mica as a solid catalyst
Glass beads and quartz wool were provided on the upper and lower parts of the reactor to fill the reaction tower body, 94 g of phenol and 68 g of phenyl acetate were charged in the storage tank, and the temperature of the oil bath was set to 225 to 225.
While adjusting the temperature to 230 ° C., the generated vapors of phenol and phenyl acetate were condensed above the solid catalyst layer, and the reaction was carried out for 7 hours while refluxing so that the condensate refluxed on the solid catalyst layer.
得られたヒドロキシアセトンフェノンの生成量は、固体
触媒１ｇ当り１０ｇであった。The amount of hydroxyacetone phenone obtained was 10 g per 1 g of the solid catalyst.
比較例 １ 固体触媒としてのアルミニウム交換型合成雲母１．０
ｇ、フェノール１４．１ｇ、酢酸フェニル６．８ｇをす
べて還流機付きフラスコ内に仕込み、フラスコを２２５
〜２３０℃に加熱されたオイルバス内に浸漬して、原料
化合物をリフラックスさせながらバッチ方式で反応を７
時間行なった。Comparative Example 1 Aluminum exchange type synthetic mica 1.0 as a solid catalyst
g, phenol 14.1 g, and phenyl acetate 6.8 g were all charged into a flask equipped with a reflux machine, and the flask was set to 225.
Immerse in an oil bath heated to ~ 230 ° C to reflux the raw material compounds and carry out the reaction in batch mode.
I went on time.
得られたヒドロキシアセトフェノンの生成量は、固体触
媒１ｇ当り１．０ｇであった。The produced amount of hydroxyacetophenone was 1.0 g per 1 g of the solid catalyst.
比較例 ２ 固体触媒としてのアルミニウム交換型合成雲母１．０
ｇ、フェノール１４．１ｇ、酢酸３ｇを比較例１と同様
にフラスコ内に仕込み、原料化合物をリフラックスさせ
ながらバッチ方式で反応を７時間行なった。Comparative Example 2 Aluminum Exchange Synthetic Mica as Solid Catalyst 1.0
g, phenol 14.1 g, and acetic acid 3 g were charged into the flask in the same manner as in Comparative Example 1, and the reaction was carried out in a batch system for 7 hours while refluxing the raw material compound.
得られたヒドロキシアセトフェノンの生成量は、固体触
媒１ｇ当り０．９ｇであった。The produced amount of hydroxyacetophenone was 0.9 g per 1 g of the solid catalyst.
比較例 ３ 比較例２において、酢酸を１２ｇ仕込んだ以外は比較例
２と同様にして反応を行なった。Comparative Example 3 The reaction was performed in the same manner as in Comparative Example 2 except that 12 g of acetic acid was charged in Comparative Example 2.
得られたヒドロキシアセトフェノンの生成量は、固体触
媒１ｇ当り２．０ｇであった。The produced amount of hydroxyacetophenone was 2.0 g per 1 g of the solid catalyst.
図は本発明に係る液相触媒反応方法を行なう際に用いら
れる反応装置である。 １……貯槽、２……供給管、３……反応塔本体、 ４……副生成物除去部、７……固体触媒層。The figure shows a reactor used when performing the liquid phase catalytic reaction method according to the present invention. 1 ... Storage tank, 2 ... Supply pipe, 3 ... Reaction tower main body, 4 ... By-product removal section, 7 ... Solid catalyst layer.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 29/38 9343−4Ｇ Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location B01J 29/38 9343-4G
Claims (4)
ことによって、原料化合物より高沸点の反応生成物と未
反応原料化合物とからなる反応混合物を回収する液相触
媒反応において、回収された反応混合物を未反応原料化
合物などの低沸点化合物のみが蒸発する温度に加熱し、
発生した蒸気を固体触媒層の上部に導いて冷却し、得ら
れた凝縮液を固体触媒層に循環させて固体触媒層に付着
した反応生成物を除去することを特徴とする液相触媒反
応方法。1. A recovered reaction in a liquid-phase catalytic reaction for recovering a reaction mixture consisting of a reaction product having a boiling point higher than that of the raw material compound and an unreacted raw material compound by passing the liquid raw material compound through a solid catalyst layer. The mixture is heated to a temperature at which only low boiling point compounds such as unreacted starting compounds evaporate,
A liquid-phase catalytic reaction method characterized in that the generated vapor is guided to the upper part of the solid catalyst layer to be cooled, and the resulting condensate is circulated through the solid catalyst layer to remove reaction products adhering to the solid catalyst layer. .
液状原料化合物がフェノールと、酢酸または酢酸フェニ
ルとであり、反応生成物がヒドロキシアセトフェノンで
あることを特徴とする特許請求の範囲第１項に記載の方
法。2. The solid catalyst is an ion exchange type layered clay,
The method according to claim 1, wherein the liquid raw material compound is phenol and acetic acid or phenyl acetate, and the reaction product is hydroxyacetophenone.
に取出されることを特徴とする特許請求の範囲第２項に
記載の方法。3. The method according to claim 2, wherein the produced water is taken out of the reaction system from the by-product removing section.
化合物を反応系に供給することを特徴とする特許請求の
範囲第１項に記載の方法。4. The method according to claim 1, wherein the liquid raw material compound is supplied to the reaction system in an amount commensurate with the recovered amount of the reaction product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60228526A JPH0639390B2 (en) | 1985-10-14 | 1985-10-14 | Liquid phase catalytic reaction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60228526A JPH0639390B2 (en) | 1985-10-14 | 1985-10-14 | Liquid phase catalytic reaction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6287549A JPS6287549A (en) | 1987-04-22 |
| JPH0639390B2 true JPH0639390B2 (en) | 1994-05-25 |
Family
ID=16877794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60228526A Expired - Fee Related JPH0639390B2 (en) | 1985-10-14 | 1985-10-14 | Liquid phase catalytic reaction method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0639390B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19540304A1 (en) * | 1995-10-28 | 1997-04-30 | Braun Ag | Device connector for electrical devices |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7566429B2 (en) * | 2005-06-14 | 2009-07-28 | Sandia Corporation | Catalytic reactive separation system for energy-efficient production of cumene |
-
1985
- 1985-10-14 JP JP60228526A patent/JPH0639390B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19540304A1 (en) * | 1995-10-28 | 1997-04-30 | Braun Ag | Device connector for electrical devices |
| DE19540304C2 (en) * | 1995-10-28 | 1998-07-30 | Braun Ag | Device connector for electrical devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6287549A (en) | 1987-04-22 |
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