JP2552160B2 - How to remove acrolein - Google Patents
How to remove acroleinInfo
- Publication number
- JP2552160B2 JP2552160B2 JP63023595A JP2359588A JP2552160B2 JP 2552160 B2 JP2552160 B2 JP 2552160B2 JP 63023595 A JP63023595 A JP 63023595A JP 2359588 A JP2359588 A JP 2359588A JP 2552160 B2 JP2552160 B2 JP 2552160B2
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- JP
- Japan
- Prior art keywords
- acrolein
- acetic acid
- allyl acetate
- gas
- condensed
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はプロピレン、酸素及び酢酸を気相で反応させ
ることによって酢酸アリルを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing allyl acetate by reacting propylene, oxygen and acetic acid in a gas phase.
さらに詳しくは、原料を循環使用することにより反応
系に混合されて供給されてくるアクロレインの濃度を一
定値以下にコントロールするためのアクロレインの除去
方法に関する。More specifically, the present invention relates to a method for removing acrolein for controlling the concentration of acrolein mixed and supplied to a reaction system by circulating the raw material to a certain value or less.
酢酸アリルは重合性の２重結合を有するモノマーであ
り、他のモノマーと共重合させるために用いたり、また
は加水分解することによりアリルアルコールを合成する
ための原料として用いられる。Allyl acetate is a monomer having a polymerizable double bond, and is used for copolymerizing with another monomer or used as a raw material for synthesizing allyl alcohol by hydrolysis.
パラジウム触媒の存在下にプロピレン、酸素及び酢酸
を気相で反応させることによって酢酸アリルを製造する
方法は公知であり、たとえば，特公昭44−29046,特公昭
48−23408,特公昭50−28934号公報などが知られてい
る。これらの公報にはアルミナ，シリカ，活性炭，スピ
ネル類，軽石または酸化チタンなどの担体にパラジウム
を0.1〜10重量％，アルカリ金属，アルカリ土類金属の
酢酸塩を１〜20重量％および他の金属を担持させた触媒
の存在下にプロピレン，酸素，酢酸を気相で反応させる
ことによって酢酸アリルを製造する方法が開示されてい
る。A method for producing allyl acetate by reacting propylene, oxygen and acetic acid in the gas phase in the presence of a palladium catalyst is known, and is disclosed, for example, in JP-B-44-29046.
48-23408 and Japanese Patent Publication No. 50-28934 are known. In these publications, palladium is contained in a carrier such as alumina, silica, activated carbon, spinels, pumice or titanium oxide in an amount of 0.1 to 10% by weight, acetates of alkali metals and alkaline earth metals in an amount of 1 to 20% by weight, and other metals. There is disclosed a method for producing allyl acetate by reacting propylene, oxygen and acetic acid in the gas phase in the presence of a catalyst on which is supported.
しかしながら，これらの技術によると酢酸アリルの収
率，および選択率が低く，触媒活性の経時低下が大き
い。However, according to these techniques, the yield and selectivity of allyl acetate are low, and the catalyst activity is greatly reduced with time.
これらの欠点を改良した技術として特開昭61−238759
号公報に記載された方法がある。Japanese Patent Application Laid-Open No. 61-238759 discloses a technique for improving these disadvantages.
There is a method described in the publication.
この公報に開示されている技術によれば、触媒として
シリカからなる担体にパラジウム及びアルカリ金属の酢
酸塩，たとえば，酢酸カリを担持させたものを用い、プ
ロピレンガス12容量％、酸素７容量％、ガス状の酢酸９
容量％及び希釈ガスである酸素72容量％からなる混合ガ
スを仕込み、５気圧，温度140℃で反応させ，酢酸アリ
ルを空時収率3.8T/m2日で得ている。According to the technique disclosed in this publication, a catalyst comprising palladium and an alkali metal acetate, for example, potassium acetate supported on a carrier made of silica, is used as a catalyst. Propylene gas is 12% by volume, oxygen is 7% by volume, Gaseous acetic acid 9
A mixed gas consisting of vol.% And 72 vol.% Oxygen as a diluent gas was charged and reacted at 5 atm and a temperature of 140 ° C., and allyl acetate was obtained at a space-time yield of 3.8 T / m 2 days.
工業的に効率良く酢酸アリルを得るためには、上記の
従来法においてこれらプロピレンガス及び酢酸ガスの未
反応物をリサイクル使用してオーバーオールの転化率を
高めて，原料の使用率を高めることが好ましい。In order to industrially efficiently obtain allyl acetate, it is preferable to increase the conversion rate of overalls by recycling the unreacted products of propylene gas and acetic acid gas in the above-mentioned conventional method to increase the usage rate of raw materials. .
本発明者らはパラジウム触媒存在下，プロピレン，酸
素，および酢酸を気相で反応させることによって酢酸ア
リルを製造する際，各原料から目的物質への見掛けの転
化率を向上させるために未反応原料をリサイクル使用す
る製法に於いて上記パラジウム触媒の活性が低下するの
を防止できる方法を提供する。When producing allyl acetate by reacting propylene, oxygen, and acetic acid in the gas phase in the presence of a palladium catalyst, the present inventors have attempted to improve the apparent conversion of each raw material to a target substance, in order to improve the unreacted raw material. It is intended to provide a method capable of preventing the activity of the above-mentioned palladium catalyst from being lowered in the production method of recycling and using
本発明者らは、上記目的を達成するため、プロピレ
ン、酸素及び酢酸から気相反応により酢酸アリルを製造
し，次いでアリルアルコールを工業的に有利に製造する
ための方法を鋭意検討した結果、リサイクルされた原料
と新しく供給される原料ガスとの混合されたトータル原
料ガス中に副生物であるアクロレインが一定量以上存在
すると触媒活性が低下することを見出し，このアクロレ
インの除去方法を開発し，本発明に至った。In order to achieve the above-mentioned object, the present inventors have diligently studied a method for producing allyl acetate from propylene, oxygen and acetic acid by a gas phase reaction, and then industrially producing allyl alcohol. It was found that the catalytic activity decreases when the by-product acrolein is present in a certain amount or more in the total raw material gas mixed with the prepared raw material and the newly supplied raw material gas, and the method for removing this acrolein was developed. Invented.
すなわち、本発明は、 パラジウム触媒の存在下、プロピレン、酸素及び酢酸
を気相で反応させることによって酢酸アリルを製造する
方法において、 （ａ）得られた反応生成ガスを冷却して非凝縮成分と凝
縮成分とに分離し、該非凝縮成分中に含有されるアクロ
レインを酢酸または酢酸水溶液に吸収させて除去した後
一部系外に排出し、大部分の非凝縮成分を酢酸アリル製
造工程に循環し、 （ｂ）該凝縮成分を蒸留し、塔底より本質的に酢酸また
は酢酸水溶液からなる液を回収し、この大部分を前記酢
酸アリル製造工程に循環し、一部を前記（ａ）工程にお
けるアクロレイン吸収液として使用し、アクロレインを
吸収した酢酸または酢酸水溶液を前記凝縮液と混合し、
蒸留することにより蒸留塔の塔頂より酢酸アリル、アク
ロレインを得る ことを特徴とする酢酸アリルの製造工程におけるアクロ
レインの除去方法 である。That is, the present invention provides a method for producing allyl acetate by reacting propylene, oxygen and acetic acid in a gas phase in the presence of a palladium catalyst, wherein (a) the reaction product gas obtained is cooled to obtain a non-condensed component. It is separated into condensed components, acrolein contained in the non-condensed components is absorbed into acetic acid or acetic acid aqueous solution and removed, and then partially discharged to the outside of the system, and most of the non-condensed components are circulated to the allyl acetate production step. (B) The condensed component is distilled to recover a liquid consisting essentially of acetic acid or an acetic acid aqueous solution from the bottom of the column, and most of this is circulated to the allyl acetate production step, part of which is used in the step (a). Used as acrolein absorption liquid, acetic acid or acetic acid aqueous solution absorbing acrolein is mixed with the condensate,
A method for removing acrolein in the process for producing allyl acetate, which comprises obtaining allyl acetate and acrolein from the top of a distillation column by distillation.
以下に本発明のアクロレインの除去方法を詳細に説明
する。The method for removing acrolein of the present invention will be described in detail below.
まず，プロピレン、酸素及び酢酸からなる混合ガスを
パラジウム触媒の存在下，気相のまま通過させ、酢酸ア
リルを製造する場合，以下のようにプロピレンが直接酸
化され，副生物としてアクロレインが生成する。First, in the case of producing allyl acetate by passing a mixed gas of propylene, oxygen and acetic acid in the gas phase in the presence of a palladium catalyst, propylene is directly oxidized as described below and acrolein is produced as a by-product.
CH2＝CHCH3＋O2 →CH2＝CHCHO＋H2O また、酢酸アリルにもう一分子の酢酸が付加する副反
応により生成するジアセテート類（アリリデンジアセテ
ート、１、３ジアセトキシブロペエンなど）が反応で生
成した水により加水分解されることによってもアクロレ
インが生成するが，これらの副生したアクロレインが、
リサイクル使用されるプロピレンおよび酢酸中に含有さ
れることによって前記のように触媒活性を低下させる。CH 2 ＝ CHCH 3 ＋ O 2 → CH 2 ＝ CHCHO ＋ H 2 O Also, diacetates (allylidene diacetate, 1,3 diacetoxy bropeene, etc.) produced by the side reaction of addition of another molecule of acetic acid to allyl acetate. Is also hydrolyzed by the water produced in the reaction to produce acrolein, but these by-produced acroleins are
By being contained in propylene and acetic acid used for recycling, the catalytic activity is lowered as described above.
反応生成物中のアクロレイン濃度は条件によって変動
するが、200〜1000ppmの範囲である。The acrolein concentration in the reaction product varies depending on the conditions, but is in the range of 200 to 1000 ppm.
一般に空時収率を増加させる目的で反応温度、反応圧
力を上昇させたり酸素濃度を増加させた条件を選択した
場合、および反応系に不活性ガスとして水を添加した場
合はアクロレインの副生量が増加する。In general, when the reaction temperature and reaction pressure are increased or the oxygen concentration is increased for the purpose of increasing the space-time yield, and when water is added as an inert gas to the reaction system, the amount of acrolein by-product Will increase.
逆に、反応温度、反応圧力を低下させたり酸素濃度を
減少させた条件を選択した場合はアクロレインの副生を
抑制することはできるが、空時収率が低下するので好ま
しくない。On the contrary, when the reaction temperature and the reaction pressure are lowered or the oxygen concentration is reduced, by-product of acrolein can be suppressed, but the space-time yield is lowered, which is not preferable.
また、生成したアクロレインを積極的に除去しない場
合はリサイクル使用されるプロピレン、酸素、酢酸中に
アクロレインが含有されるため系内にアクロレインが蓄
積され、触媒活性を著しく低下させるので好ましくな
い。Further, when the produced acrolein is not positively removed, acrolein is contained in propylene, oxygen and acetic acid used for recycling, acrolein is accumulated in the system, and the catalytic activity is remarkably lowered, which is not preferable.
本発明者はアクロレインを含有するリサイクルガスを
含んだトータルの仕込みガス中のアクロレイン濃度と触
媒活性について検討した結果、アクロレイン濃度が高く
なると触媒活性の低下が著しいが、新しく供給される原
料ガスとリサイクルガスとのトータルの混合ガス中のア
クロレインの濃度が100ppm以下ならば触媒活性に対して
実質的に影響を及ぼさないことが判明し、本発明者は昭
和63年２月３日出願の願書に添付した明細書（発明の名
称：酢酸アリルの製造法）に開示した。As a result of examining the acrolein concentration and the catalytic activity in the total charge gas containing the recycled gas containing acrolein, the present inventor has found that the catalytic activity is remarkably reduced when the acrolein concentration is high, but the newly supplied raw material gas and the recycled gas are recycled. It was found that if the concentration of acrolein in the total mixed gas with the gas was 100 ppm or less, it had no substantial effect on the catalytic activity, and the present inventor attached the application filed on February 3, 1988. (The title of the invention: a method for producing allyl acetate).
プロピレン、酸素、酢酸を気相で反応させることによ
って、酢酸アリルを製造する一般的な方法は反応生成ガ
スを冷却などの方法により非凝縮成分と凝縮成分とに分
離後，非凝縮成分中の生成炭酸ガスを吸収除去または炭
酸ガスの蓄積を防止する目的で非凝縮成分の一部ととも
に炭酸ガスを系外に排出した後、反応仕込み系に循環
し、未反応のプロピレン、酸素を再利用する。A general method for producing allyl acetate by reacting propylene, oxygen, and acetic acid in the gas phase is to separate the reaction product gas into non-condensed components and condensed components by a method such as cooling, and then to generate in the non-condensed components. After the carbon dioxide gas is discharged out of the system together with a part of the non-condensed components for the purpose of absorbing and removing the carbon dioxide gas or preventing the accumulation of the carbon dioxide gas, it is circulated to the reaction charging system to reuse the unreacted propylene and oxygen.
凝縮成分は蒸溜により本質的に酢酸アリル、水、およ
びアクロレインまたは酢酸アリル、水、アクロレインお
よび酢酸からなる液を得て、さらに蒸溜することにより
酢酸アリルを得る。The condensed component is distilled to obtain a liquid consisting essentially of allyl acetate, water, and acrolein or allyl acetate, water, acrolein, and acetic acid, and further distilled to obtain allyl acetate.
一方、塔底において、本質的に酢酸、酢酸−水からな
る液を得て、この酢酸を酢酸アリル製造用の原料として
再利用する。On the other hand, a liquid consisting essentially of acetic acid and acetic acid-water is obtained at the bottom of the column, and this acetic acid is reused as a raw material for the production of allyl acetate.
副生したアクロレインは反応生成ガスを非凝縮成分と
凝縮成分とに分離する条件に応じてある一定の比率に分
離されるが、非凝縮成分中のアクロレインを反応に悪影
響を与えない程度の量まで低減させることは困難であ
る。Acrolein produced as a by-product is separated into a certain ratio according to the conditions for separating the reaction product gas into the non-condensable component and the condensed component, but the amount of acrolein in the non-condensed component does not adversely affect the reaction. It is difficult to reduce.
本発明者は非凝縮成分中に含有されているアクロレイ
ンを工業的に有利な方法で除去する手段として以下の方
法を提供する。The present inventor provides the following method as means for removing acrolein contained in the non-condensed component by an industrially advantageous method.
すなわち、凝縮成分中から酢酸アリル、アクロレイン
を除去した本質的には酢酸または酢酸−水からなる液を
アクロレインの吸収液として使用し本質的にはアクロレ
インを含有しない非凝縮成分を得る。That is, a liquid consisting essentially of acetic acid or acetic acid-water obtained by removing allyl acetate and acrolein from the condensed component is used as an acrolein absorption liquid to obtain a non-condensed component essentially containing no acrolein.
一方、アクロレインを吸収した酢酸は凝縮液と混合し
蒸溜によりアクロレインを含有しない液としてリサイク
ル使用される。On the other hand, acetic acid that has absorbed acrolein is mixed with a condensate and distilled to be recycled as a liquid not containing acrolein.
本発明の酢酸アリルの製造法に用いられる触媒は、プ
ロピレン、酸素及び酢酸から酢酸アリルを製造する一般
的なパラジウム触媒が使用される。As the catalyst used in the method for producing allyl acetate of the present invention, a general palladium catalyst for producing allyl acetate from propylene, oxygen and acetic acid is used.
さらに好ましくは，パラジウム触媒にアルカリ金属の
酢酸塩を添加したものを使用するのが良い。More preferably, a palladium catalyst to which an alkali metal acetate is added is used.
プロピレン、酸素および酢酸の混合割合、窒素、炭酸
ガスなどによる希釈率、仕込み速度などは触媒の活性、
および製造能力などで決定すべきものであり、本願とは
直接には関係ない。The mixing ratio of propylene, oxygen and acetic acid, the dilution ratio of nitrogen, carbon dioxide, etc., the charging rate, etc.
It should be determined by the manufacturing capability and the like, and is not directly related to the present application.
本発明の方法に用いられる触媒の形状は特に規定され
ず，球状，タブレット状またはペレット状などいずれで
もよい。The shape of the catalyst used in the method of the present invention is not particularly limited, and may be spherical, tablet, pellet, or the like.
反応器に充填し100〜200℃の温度で、反応圧力は１〜
30気圧の圧力下で反応を行なわれる。第１図は本発明に
よる酢酸アリルを製造する場合の一実施態様を示した概
略ブロック図であり、これに基づいて説明する。Fill the reactor at a temperature of 100-200 ℃, the reaction pressure is 1-
The reaction is carried out under a pressure of 30 atm. FIG. 1 is a schematic block diagram showing one embodiment for producing allyl acetate according to the present invention, and description will be given based on this.
本発明の方法は、まず、触媒の存在下にプロピレン、
酸素および酢酸を反応器１−１において,100〜200℃の
温度,1〜30気圧の圧力下で気相で反応させる。The method of the present invention comprises first of all, in the presence of a catalyst, propylene,
Oxygen and acetic acid are reacted in the reactor 1-1 in the gas phase at a temperature of 100 to 200 ° C. and a pressure of 1 to 30 atm.
酢酸アリルの合成反応によって得られた反応生成ガス
を冷却器２−２で冷却し、非凝縮成分と凝縮成分とに分
離する。The reaction product gas obtained by the synthesis reaction of allyl acetate is cooled by the cooler 2-2 and separated into a non-condensed component and a condensed component.
冷却温度が低い場合はアクロレインなどの低沸点物の
凝縮量は増加するが、有用なプロピレンの溶解量が増加
するため、次工程の蒸溜においてプロピレンの損失量が
増加するので得策ではない。When the cooling temperature is low, the amount of condensed low-boiling substances such as acrolein is increased, but the amount of useful propylene dissolved is increased, so that the amount of propylene lost in the distillation in the next step is not good.
冷却温度は操作圧力と関係するが、10〜90℃が良い。 The cooling temperature is related to the operating pressure, but 10 to 90 ° C is good.
非凝縮成分はアクロレイン吸収塔３−３に導き、塔頂
より冷却した酢酸、酢酸−水を仕込み、非凝縮成分中の
アクロレインを吸収除去し、アクロレインを除去した非
凝縮成分は酢酸アリル合成反応工程に循環する。The non-condensed component is led to the acrolein absorption tower 3-3, acetic acid and acetic acid-water are charged from the top of the tower, the acrolein in the non-condensed component is absorbed and removed, and the non-condensed component from which acrolein is removed is the allyl acetate synthesis reaction step. Circulate to.
吸収された酢酸、または酢酸−水の液温度は10〜40℃
程度にするのが好ましい。Liquid temperature of absorbed acetic acid or acetic acid-water is 10-40 ℃
It is preferable to set the degree.
凝縮成分はアクロレインを吸収した酢酸、または酢酸
−水の液と混合し、蒸溜塔４−４に導き、塔底より酢
酸、または酢酸−水の液を得る。The condensed component is mixed with acetic acid which has absorbed acrolein, or acetic acid-water liquid, and is introduced into the distillation column 4-4 to obtain acetic acid or acetic acid-water liquid from the bottom of the column.
塔底より得た酢酸、または酢酸−水の混合液の一部を
前記３−３の吸収液として利用し、残りの液は酢酸アリ
ル合成反応工程に循環して使用する。A part of acetic acid or a mixed solution of acetic acid-water obtained from the bottom of the column is used as the absorbing solution of 3-3, and the remaining solution is recycled to the allyl acetate synthesis reaction step.
なお,5−５は脱気塔であり，これは加圧系から常圧系
に移動した液体中に発生した気泡を除去するためのもの
である。In addition, 5-5 is a deaeration tower, which is for removing the bubbles generated in the liquid that has moved from the pressurized system to the atmospheric system.
塔頂液より酢酸アリル、アクロレイン、水の混合液を
得る。A mixed solution of allyl acetate, acrolein and water is obtained from the top liquid.
以下に実施例及び比較例を挙げて本発明の効果を詳細
に説明する。Hereinafter, the effects of the present invention will be described in detail with reference to Examples and Comparative Examples.
（実施例１） 市販の5mmΦのシリカ担体（表面積96m2/g,細孔容積0.
7ml/g,平均細孔半径150A,嵩密度540g/）１当たりパ
ラジウム3.3g,および酢酸カリウム30gを担持させた触媒
2.6を反応器に充填し、反応圧力4.0kg/cm2（ゲージ
圧）、温度140℃でプロピレン12％、酸素7.5％、酢酸9.
0％、水6.0％、および炭酸ガス、プロパン、窒素からな
るガスが65.5％になるように調節し、4.6Nm3/hrの速度
で供給することによって酢酸アリルの合成反応を行っ
た。Example 1 Commercially available 5 mmΦ silica carrier (surface area 96 m 2 / g, pore volume 0.
7ml / g, average pore radius 150A, bulk density 540g /) Catalyst supporting 3.3g of palladium and 30g of potassium acetate per 1
2.6 was charged into a reactor, reaction pressure was 4.0 kg / cm 2 (gauge pressure), temperature was 140 ° C, propylene 12%, oxygen 7.5%, acetic acid 9.
The reaction of synthesizing allyl acetate was carried out by adjusting the amount of 0%, water 6.0%, carbon dioxide gas, propane, and nitrogen gas to 65.5% and supplying them at a rate of 4.6 Nm 3 / hr.
得られた反応生成ガスを50℃に冷却し、非凝縮成分と
凝縮成分とに分離した。The obtained reaction product gas was cooled to 50 ° C. and separated into a non-condensed component and a condensed component.
非凝縮成分が3.8Nm3/hrで、この中にアクロレインを2
46ppm含有していた。The non-condensed component is 3.8 Nm 3 / hr, in which acrolein is 2
It contained 46 ppm.
このガスをアクロレイン吸収塔（吸収部内径42mm、長
さ140cmで、充填物として磁製の5mmΦ×5mm長のラッシ
ヒリングを充填した塔）の下部より供給し、次工程の蒸
溜で塔底より回収した83％酢酸水溶液を16℃に冷却し、
吸収塔の塔頂より814g/hrの速度で供給してアクロレイ
ンを吸収させた。This gas was supplied from the lower part of the acrolein absorption tower (column with an absorption part inner diameter of 42 mm, length of 140 cm, and filled with porcelain 5 mmΦ x 5 mm long Raschig rings as a packing material), and was recovered from the bottom by distillation in the next step. Cool the 83% acetic acid aqueous solution to 16 ° C,
The acrolein was absorbed at a rate of 814 g / hr from the top of the absorption tower.
この結果、塔頂よりアクロレインを81ppm含有したガ
スを得た。As a result, a gas containing 81 ppm of acrolein was obtained from the top of the tower.
このガスから一部を炭酸ガスの蓄積を防止する目的で
系外へパージし、残りのガスを酢酸アリル反応工程に循
環する。A part of this gas is purged out of the system for the purpose of preventing the accumulation of carbon dioxide gas, and the remaining gas is circulated in the allyl acetate reaction step.
凝縮成分はアクロレインを吸収した吸収液と混合した
後、脱気槽５−５で非凝縮成分をパージし、酢酸アリル
19.8％、水20.0％、酢酸57.4％、アクロレイン0.04％、
炭酸ガスなど2.72％を含有した液を得た。After condensing the mixed components with the absorbing liquid that has absorbed acrolein, purge the non-condensed components in the degassing tank 5-5 and add allyl acetate.
19.8%, water 20.0%, acetic acid 57.4%, acrolein 0.04%,
A liquid containing 2.72% of carbon dioxide gas was obtained.
脱気槽５−５でパージした非凝縮成分をアクロレイン
吸収塔に導き、有効成分を回収することも可能である。It is also possible to introduce the non-condensed component purged in the degassing tank 5-5 to the acrolein absorption tower and recover the active component.
この脱気槽５−５で得られた液を蒸溜し、83％酢酸水
溶液を得てこの液の一部を前記アクロレイン吸収液とし
て用い、残りの液は酢酸アリル合成反応工程に循環して
再利用した。The liquid obtained in this degassing tank 5-5 was distilled to obtain an 83% acetic acid aqueous solution, a part of this liquid was used as the acrolein absorption liquid, and the remaining liquid was circulated to the allyl acetate synthesis reaction step and re-used. used.
なお、プロピレン、酸素、酢酸を所定の反応仕込み組
成になるように追加する。In addition, propylene, oxygen, and acetic acid are added so that a predetermined reaction charge composition is obtained.
反応仕込み原料ガス中のアクロレインの濃度は66ppm
であり，この場合の酢酸アリルの生成速度は毎時563gで
あった。Concentration of acrolein in the reaction feed gas is 66ppm
The production rate of allyl acetate in this case was 563 g / h.
（比較例１） アクロレイン吸収工程を省略した以外は実施例１と全
く同一の反応を行なった。(Comparative Example 1) The same reaction as in Example 1 was performed except that the acrolein absorption step was omitted.
その結果，非凝縮成分中のアクロレイン濃度は1300pp
mまでの濃度に蓄積され、反応仕込み原料ガス中のアク
ロレインの濃度は1070ppmであり，酢酸アリルの生成速
度は毎時93gであった。As a result, the acrolein concentration in the non-condensed component was 1300 pp.
The acrolein concentration in the raw material gas charged to the reaction was 1070 ppm, and the production rate of allyl acetate was 93 g / hr.
第１図は本発明による酢酸アリルを製造する場合の一実
施態様を示した概略ブロック図であり,1−１は反応器,2
−２は冷却器,3−３はアクロレイン吸収塔,4−４は蒸溜
塔,5−５は脱気塔である。FIG. 1 is a schematic block diagram showing an embodiment for producing allyl acetate according to the present invention, 1-1 is a reactor, 2
Reference numeral -2 is a cooler, 3-3 is an acrolein absorption tower, 4-4 is a distillation tower, and 5-5 is a deaeration tower.
Claims (1)
素及び酢酸を気相で反応させることによって酢酸アリル
を製造する方法において、 （ａ）得られた反応生成ガスを冷却して非凝縮成分と凝
縮成分とに分離し、該非凝縮成分中に含有されるアクロ
レインを酢酸または酢酸水溶液に吸収させて除去した後
一部系外に排出し、大部分の非凝縮成分を酢酸アリル製
造工程に循環し、 （ｂ）該凝縮成分を蒸留し、塔底より本質的に酢酸また
は酢酸水溶液からなる液を回収し、この大部分を前記酢
酸アリル製造工程に循環し、一部を前記（ａ）工程にお
けるアクロレイン吸収液として使用し、アクロレインを
吸収した酢酸または酢酸水溶液を前記凝縮液と混合し、
蒸留することにより蒸留塔の塔頂より酢酸アリル、アク
ロレインを得る ことを特徴とする酢酸アリルの製造工程におけるアクロ
レインの除去方法。1. A method for producing allyl acetate by reacting propylene, oxygen and acetic acid in a gas phase in the presence of a palladium catalyst, comprising: (a) cooling the reaction product gas obtained to condense non-condensed components. Separated into components, acrolein contained in the non-condensed components is absorbed in acetic acid or acetic acid aqueous solution and then removed, and then partially discharged to the outside of the system, and most non-condensed components are circulated to the allyl acetate production step, (B) The condensed component is distilled to recover a liquid consisting essentially of acetic acid or an aqueous solution of acetic acid from the bottom of the column, most of which is circulated to the allyl acetate production step, and part of which is acrolein in step (a). Used as an absorption liquid, acetic acid or acetic acid aqueous solution having absorbed acrolein is mixed with the condensate,
A method for removing acrolein in a process for producing allyl acetate, characterized in that allyl acetate and acrolein are obtained from the top of a distillation column by distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023595A JP2552160B2 (en) | 1988-02-03 | 1988-02-03 | How to remove acrolein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023595A JP2552160B2 (en) | 1988-02-03 | 1988-02-03 | How to remove acrolein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01197456A JPH01197456A (en) | 1989-08-09 |
| JP2552160B2 true JP2552160B2 (en) | 1996-11-06 |
Family
ID=12114945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63023595A Expired - Lifetime JP2552160B2 (en) | 1988-02-03 | 1988-02-03 | How to remove acrolein |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2552160B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8309758B2 (en) * | 2009-12-17 | 2012-11-13 | Lyondell Chemical Technology, L.P. | Allyl acetate purification |
-
1988
- 1988-02-03 JP JP63023595A patent/JP2552160B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01197456A (en) | 1989-08-09 |
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