JPS6011442A - Production of vinyl acetate - Google Patents
Production of vinyl acetateInfo
- Publication number
- JPS6011442A JPS6011442A JP58119799A JP11979983A JPS6011442A JP S6011442 A JPS6011442 A JP S6011442A JP 58119799 A JP58119799 A JP 58119799A JP 11979983 A JP11979983 A JP 11979983A JP S6011442 A JPS6011442 A JP S6011442A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- reaction
- acetic acid
- acetic anhydride
- water
- 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.)
- Pending
Links
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】
本発明は、エチレン、酢酸及び酸素を原料として気相法
により酢酸ビニルを連続的に製造する方法に関し、特に
従来法に比べて反応生成物の分離製精が容易で、効率よ
く酢酸ビニルを得る連続的製造法の改善に関する。Detailed Description of the Invention The present invention relates to a method for continuously producing vinyl acetate by a gas phase method using ethylene, acetic acid, and oxygen as raw materials, and in particular, the separation and purification of the reaction product is easier than in conventional methods. , relating to improvements in continuous production methods for efficiently obtaining vinyl acetate.
エチレン、酢酸及び酸素を反応原料として、例えば金属
パラジウムと酢酸カリウムを７リカやアルミナなどの担
体に担持させた触媒の存在下に、気相で反応させて酢酸
ビニルを製造することは知られている。しかし、一般に
固体触媒は触媒毒の作用を受けやすく、副反応物などに
よる活性の経時的低下が大きく、また本反応における金
属パラジウムの触媒活性はそれはど大きくないので、そ
の活性を増大させるための担体、助触媒等についての研
究や、初期活性の低下を防止する研究が、現在、主とし
て行われている。It is known that vinyl acetate can be produced by reacting ethylene, acetic acid, and oxygen as reaction raw materials in the gas phase in the presence of a catalyst in which, for example, metallic palladium and potassium acetate are supported on a carrier such as 7-lika or alumina. There is. However, in general, solid catalysts are susceptible to the effects of catalyst poisons, and their activity decreases significantly over time due to side-reactants.Also, the catalytic activity of metal palladium in this reaction is not very large, so it is difficult to increase its activity. Research on carriers, cocatalysts, etc., and research on preventing a decrease in initial activity are currently being conducted.
また、現在、／工業的に行われている酢酸ビニルの気相
法による連続的製造方法は、反応生成物のあと処理、特
に共沸蒸留の蒸留負荷が極めて太きく、多大なエネルギ
ーを必要とするという大きな欠点がおる。この解決こそ
気相法による酢酸ビニルの連続的製造法に切望されると
ころであり、特に工業的に克服さるべき技術的課題であ
った。In addition, the continuous gas-phase production method of vinyl acetate that is currently being used industrially requires an extremely heavy distillation load for post-treatment of the reaction product, especially azeotropic distillation, and requires a large amount of energy. There is a big drawback. This solution is desperately needed for a continuous production method of vinyl acetate using a gas phase method, and has been a technical problem that must be overcome in particular industrially.
エチレンを反応原料として気相法により酢酸ビニルを製
造する従来公知の方法は、例えば、添付図面の第１図に
示されるようなフローシートの１例によって説明するこ
とができる。A conventionally known method for producing vinyl acetate by a gas phase method using ethylene as a reaction raw material can be explained, for example, by an example of a flow sheet as shown in FIG. 1 of the accompanying drawings.
第１図において、原料成分である酢酸、エチレン及び酸
素は、それぞれの導入管を通って触媒を充てんした反応
器１に、通常その頂部から供給される。反応器ｌは５０
〜２００℃の温度及び當圧ないし２０気圧の圧力の反応
条件に保たれ、原料混合成分は触媒表面において接触的
に反応して、次式（１）によシ酢酸ビニルを生成し、同
時に等モルの水を生成する。In FIG. 1, raw material components acetic acid, ethylene and oxygen are fed through their respective inlet pipes to a reactor 1 filled with a catalyst, usually from the top thereof. Reactor l is 50
The reaction conditions are maintained at a temperature of ~200°C and a pressure of between 20 and 20 atm, and the raw material mixture reacts catalytically on the catalyst surface to produce vinyl cyanoacetate according to the following formula (1), and at the same time Produces moles of water.
０２ Ｈ４＋ ＣＨｓ Ｃ０ＯＨ＋ ｔ／２０２−→Ｃ
ＨｓＣＯＯＣｘＨｓ＋Ｈ２０（１）
また、この反応とともにエチレンと酸素が反応して、次
式（ｎ） Ｉｃ示すように炭酸ガスと水を生成する。02 H4+ CHs C0OH+ t/202-→C
HsCOOCxHs+H20 (1) Also, along with this reaction, ethylene and oxygen react to generate carbon dioxide gas and water as shown in the following formula (n) Ic.
ＣＨｘ ＝ Ｃｆ（ｚ ＋３Ｑｚ→２ＣＯｚ ＋２Ｈ２
０（１１）その結果、反応器１において得られる粗酢酸
ビニル含有反応生成物中には、これらの反応によって生
成する水が５重量％前後存在する。このが成シの量の水
の混在は、副次的な反応に関与して酢酸ビニルの回収及
び収率に悪影響を与えるだけでなく、酢酸ビニルの単離
や循環使用のための酢酸の回収操作を厄介にし、特に共
沸蒸留に大きな蒸留負荷がかかり、そのために多大のエ
ネルギーを必要とする。CHx = Cf(z +3Qz→2COz +2H2
0(11) As a result, the crude vinyl acetate-containing reaction product obtained in reactor 1 contains approximately 5% by weight of water produced by these reactions. The presence of this amount of water not only takes part in side reactions and adversely affects the recovery and yield of vinyl acetate, but also impairs the isolation of vinyl acetate and the recovery of acetic acid for recycling. This makes the operation complicated, especially azeotropic distillation, which imposes a heavy distillation load and requires a large amount of energy.
反応器１から出る反応混合物は、コンデンサー２によシ
冷却されて、気液分離器３に導かれ、その頂部からは未
反応のエチレンガス及び酸素ガスが回収され、底部から
は多量の未反応酢酸と反応によって生成した水を含む粗
酢酸ビニル液が取シ出され、受器４に−たん入れられた
後、その一定量ずつが共沸蒸留塔５に導入されて共沸蒸
留処理される。この共沸蒸留塔５においては、酢酸ビニ
ルと水とが共沸蒸留によって塔頂から共沸留分として留
出し、塔内には酢酸が残留する。共沸蒸留塔５の頂部か
ら留出した酢酸ビニルと水の共沸混合物は、冷却されて
上層の酢酸ビニルと下層の水とに分液され、上層の酢酸
ビニルは、脱水蒸留塔６に導かれて低佛点不純物の留去
及び脱水処理が行わｙｔ、次いで酢酸ビニル蒸留塔７で
精製される。The reaction mixture coming out of the reactor 1 is cooled by a condenser 2 and led to a gas-liquid separator 3, where unreacted ethylene gas and oxygen gas are recovered from the top, and a large amount of unreacted gas is recovered from the bottom. A crude vinyl acetate liquid containing water produced by the reaction with acetic acid is taken out and put into a receiver 4, and then a certain amount of it is introduced into an azeotropic distillation column 5 where it is subjected to azeotropic distillation treatment. . In this azeotropic distillation column 5, vinyl acetate and water are distilled out as an azeotropic fraction from the top of the column by azeotropic distillation, and acetic acid remains in the column. The azeotropic mixture of vinyl acetate and water distilled from the top of the azeotropic distillation column 5 is cooled and separated into an upper layer of vinyl acetate and a lower layer of water, and the upper layer of vinyl acetate is introduced into the dehydration distillation column 6. The resulting product is subjected to distillation and dehydration treatment to remove low-temperature impurities, and then purified in a vinyl acetate distillation column 7.
また、その蒸留塔７の塔底に残留する高沸点留分け、分
離されずに残存している酢酸ビニルを回収するために、
共沸蒸留塔５に戻されて、次の共沸蒸留にかけられる粗
酢酸ビニル液と共に共沸蒸留される。共沸蒸留処理が行
われた塔５の底部に残留する液は、酢酸蒸留塔８に導か
れて精留され、その酢酸留分は、反応原料成分として反
応器１へ循環される。蒸留塔８において塔底から取シ出
される高沸点成分液は、分離塔９に導かれて酢酸が回収
されて、前記粗酢酸ビニル受器４に加えられ塔底の高沸
点不純物は廃棄される。In addition, in order to recover the high-boiling point fraction remaining at the bottom of the distillation column 7 and the vinyl acetate remaining without being separated,
It is returned to the azeotropic distillation column 5 and azeotropically distilled together with the crude vinyl acetate liquid to be subjected to the next azeotropic distillation. The liquid remaining at the bottom of the column 5 that has been subjected to the azeotropic distillation treatment is led to the acetic acid distillation column 8 where it is rectified, and the acetic acid fraction is circulated to the reactor 1 as a reaction raw material component. The high-boiling component liquid taken out from the bottom of the distillation column 8 is led to a separation column 9 where acetic acid is recovered and added to the crude vinyl acetate receiver 4, where high-boiling impurities at the bottom of the column are discarded. .
荷が極めて犬さく、その負荷をできるだけ軽減すること
が連続的酢酸ビニルの製造における大きな改善課題であ
った。The load was extremely heavy, and reducing that load as much as possible was a major improvement issue in continuous vinyl acetate production.
本発明者らは、上記のようなエチレン、酢酸及び酸素を
気相反応させて連続的に酢酸ビニルを製造する方法にお
いて、特に蒸留負荷の軽減について研究を行い、反応後
の粗酢酸ビニル受器４及び／又は共済蒸留塔５に無水酢
酸を供給して、副生じた水と反応きせることにより、効
率よく目的を達成しうろことを見出し、さきに提案した
（特願昭５７−２１６４７５号）。The present inventors have conducted research on reducing the distillation load in the method for continuously producing vinyl acetate by subjecting ethylene, acetic acid, and oxygen to a gas-phase reaction as described above. We discovered that the objective could be achieved efficiently by supplying acetic anhydride to 4 and/or the mutual aid distillation column 5 and allowing it to react with the by-produced water, and proposed it earlier (Japanese Patent Application No. 57-216475). .
しかし、本発明者らは、酢酸ビニル全一層効果的に製造
する改善法にりいてさらに研究を重ねた結果、エチレン
、酸素及び酢酸を原料として気相法で酢酸ビニルを連続
的に製造する方法において、連続的に補給される酢酸の
全部又は一部に代えて、特定の条件を満足させるようＫ
、無水酢酸を用いるとき、酢酸ビニルの生成を阻害する
ことなく、共沸蒸留負荷を大幅に＠減しうることを見出
した。However, as a result of further research into an improved method for producing vinyl acetate more effectively, the present inventors discovered a method for continuously producing vinyl acetate using a gas phase method using ethylene, oxygen, and acetic acid as raw materials. In place of all or part of the continuously replenished acetic acid, K is used to satisfy specific conditions.
have found that when acetic anhydride is used, the azeotropic distillation load can be significantly reduced without inhibiting the production of vinyl acetate.
すなわち、本発明は、エチレン、酢酸及び酸素を、周期
表第１１族金属触媒の存在下に、常圧ないし２０気圧の
圧力及び５０〜２００℃の温度で気相反応させて酢酸ビ
ニルを連続的に製造する方法において、反応区域に供給
される酢酸をｙ（重量部／時）、水を２（重量部／時）
とした場合、無水酢酸供給ｉＸ（重量部／時）が次式
１式％
を満足するように無水酢酸を供給することを特徴とする
連続的酢酸ビニルの製造方法を提供する。That is, the present invention continuously produces vinyl acetate by subjecting ethylene, acetic acid, and oxygen to a gas phase reaction in the presence of a metal catalyst from Group 11 of the periodic table at a pressure of normal pressure to 20 atm and a temperature of 50 to 200°C. In this method, y (parts by weight/hour) of acetic acid and 2 (parts by weight/hour) of water are supplied to the reaction zone.
In this case, there is provided a continuous method for producing vinyl acetate, characterized in that acetic anhydride is supplied so that the acetic anhydride supply iX (parts by weight/hour) satisfies the following formula 1 %.
本発明は、酢酸ビニルの合成反応に本質的に関与せず、
また、反応区域に多量存在すると酢酸ビニルの形成に悪
影響を及ぼす無水酢酸を、反応区域において酢酸ビニル
の合成反応の間に実質的に完全に加水分解しうる特定範
囲量条件で、補給される酢酸の少くとも一部に代えて添
加するとき、工業的に望ましい改善効果が得られること
の発見に基いている。本発明は、無水酢酸が水の存在下
に容易に加水分解して反応原料である酢酸となる現象を
利用するものであるが、従来反応域に存在させるとき酢
酸ビニルの形成を著しく阻害するという技術概念にもか
かわらず、逆にこれを反応区域に特定の蓋範囲条件で加
えるとき、酢酸ビニルの生成を伺ら阻害せず、しかも連
続的酢酸ビニルの製造に望ましい反応液の顕著な蒸留負
荷の軽減が達成されたことは篤くべき発見であった。The present invention is not essentially involved in the synthesis reaction of vinyl acetate,
In addition, acetic acid is replenished in a specific range of amount conditions that can substantially completely hydrolyze acetic anhydride, which if present in large quantities in the reaction zone has a negative effect on the formation of vinyl acetate, in the reaction zone during the synthesis reaction of vinyl acetate. This is based on the discovery that industrially desirable improvement effects can be obtained when added in place of at least a portion of The present invention utilizes the phenomenon that acetic anhydride easily hydrolyzes in the presence of water to form acetic acid, which is a reaction raw material. Despite the technical concept, on the contrary, when added to the reaction zone under certain lid range conditions, it does not interfere with the production of vinyl acetate, yet it has a significant distillation load on the reaction liquid, which is desirable for continuous vinyl acetate production. It was a serious discovery that the reduction of
またこのような反応方法において、反応区域に／ｉｆ定
のｈｔ範囲を越えて過剰に無水酢酸が供給された場合は
、酢酸ビニルの生成が著しく阻害され、粗酢酸ビニル液
中に無水酢酸が残存することもわかった。In addition, in such a reaction method, if an excess of acetic anhydride is supplied to the reaction zone beyond the specified ht range, the production of vinyl acetate will be significantly inhibited, and acetic anhydride will remain in the crude vinyl acetate solution. I also found out that it does.
従って、本発明の方法において、反応区域に供給される
無水酢酸は特定の量範囲条件下で加えることが重要であ
シ、具体的には反応器に供給される無水酢酸の割合は、
反応器に供給される循環酢酸をぼむ酢酸に対］−て、１
３．８ｗ％以内であることがＭ要である。このように、
本発明の方法は、反応区域に水と反応性の無水酢酸を加
えるので、反応原料中にある程度の水が含まれていても
、それに見合う一部の無水酢酸の過量を供給すればよい
から、循環使用される原料類中にいくらかの水が含まれ
ることは例ら差し支えない。この場合、反応区域に供給
された水は反応区域で無水酢酸と直ちに反応するので、
この場合の無水酢酸の供給可能数は、水を供給しない場
合の対酢酸１３．８ｗ％より多くなる。Therefore, in the process of the present invention, it is important that the acetic anhydride fed to the reaction zone is added under specific amount range conditions, specifically, the proportion of acetic anhydride fed to the reactor is
[to the acetic acid containing circulating acetic acid supplied to the reactor]-, 1
M is required to be within 3.8w%. in this way,
In the method of the present invention, acetic anhydride reactive with water is added to the reaction zone, so even if a certain amount of water is contained in the reaction raw materials, it is only necessary to supply a proportionate excess amount of acetic anhydride. It is acceptable for some water to be included in the recycled materials. In this case, the water fed to the reaction zone immediately reacts with acetic anhydride in the reaction zone, so
In this case, the number of acetic anhydrides that can be supplied is greater than 13.8 w% based on acetic acid when water is not supplied.
本発明の方法において、反応区域に供給できる無水酢酸
の量は、反応区域に供給される無水酢酸、酢酸、及び水
の量を、それぞれＸ（重量部／時）。In the method of the present invention, the amount of acetic anhydride that can be fed to the reaction zone is the amount of acetic anhydride, acetic acid, and water that are fed to the reaction zone, respectively, by X (parts by weight/hour).
ｙ（重量部／時）、２（重量部／時）とすると、次式で
表わされる。When y (parts by weight/hour) and 2 (parts by weight/hour), it is expressed by the following formula.
すなわち、Ｘ≦０．１３８１ ＋ ６．５９ ｚとなシ
、無水酢酸供給量Ｘは、上記不等式を満足することが必
要である。That is, X≦0.1381 + 6.59 z, and the acetic anhydride supply amount X needs to satisfy the above inequality.
本発明の方法においては、エチレン、酢酸及び酸素を原
料として１周期表第）１族の金屑触媒の存在下に酢酸ビ
ニルを製造する従来法と実質的に同一の反応温度条件及
び圧力条件が好都合に採用される。反応温度は５０〜２
５０’Ｃの範囲であり、好ましくは１００〜２００ ℃
である。また、反応圧力は常圧〜２０気圧、好ましくは
５〜１５気圧の範囲でおる。触媒は、周期表第種族の貴
金属でらって１代表的なものとしては例えばパラジウム
を挙げることができる。また触媒の調製は、従来知られ
た方法を採用することができる。本発明の方法に４１利
に用いられる触媒は、例えば次のようにして準備される
。The method of the present invention uses substantially the same reaction temperature and pressure conditions as the conventional method of producing vinyl acetate using ethylene, acetic acid, and oxygen as raw materials in the presence of a metal scrap catalyst of Group 1 of the periodic table. Adopted conveniently. The reaction temperature is 50-2
50'C range, preferably 100-200°C
It is. The reaction pressure is in the range of normal pressure to 20 atm, preferably 5 to 15 atm. The catalyst is one of the noble metals of the periodic table group, for example, palladium can be cited as a representative example. Further, the catalyst can be prepared by a conventionally known method. The catalyst used in the method of the present invention is prepared, for example, as follows.
まず、表面積１４０〜１６０ｍ／、！ｉ’、直径５朋の
シリカ球をテトラクロロ−パラジウム酸のナトリウム塩
の水溶液に浸漬した後、これにホルマリン、水素等圧よ
り通常の還元処理を施す。更にこれを酢酸カリウムの水
溶液に浸漬した後、１２０′Ｃで数時間乾燥させて調製
する。このようにして得た触媒Ｐｄ６度は約０．５Ｗ％
、酢酸カリウム濃度は約５Ｗ％である。First, the surface area is 140-160m/! i': After immersing a silica sphere with a diameter of 5 mm in an aqueous solution of sodium salt of tetrachloropalladate, it is subjected to a usual reduction treatment using formalin and hydrogen isobarically. Further, this is prepared by immersing it in an aqueous solution of potassium acetate and then drying it at 120'C for several hours. The catalyst Pd6 degree obtained in this way is about 0.5W%
, the potassium acetate concentration is about 5W%.
また、反応原料として用いられるエチレンと酸素ガスは
、いずれも９９％以上の可及的高純度のものであって、
両ガス成分の割合は、エチレン：酸素が９９〜７０：１
〜３０容＃チ、好ましくは９８〜８０ ：、２〜２０容
量チである。また、反応原料として用いられる酢酸は、
含有不純物の少い可及的高濃度のものが好適に用いられ
るが、その量は酸素１モル当シ１〜１００モル、好まし
くは２〜２０モルである。In addition, the ethylene and oxygen gas used as reaction raw materials are both of the highest possible purity of 99% or more,
The ratio of both gas components is ethylene:oxygen 99-70:1
~30 volumes, preferably 98 to 80 volumes, and 2 to 20 volumes. In addition, acetic acid used as a reaction raw material is
A compound containing as few impurities as possible is preferably used, and the amount thereof is 1 to 100 mol, preferably 2 to 20 mol, per mol of oxygen.
本発明の方法によれば、反応容器から取−シ出された反
応生成液は、溶存するエチレンや酸素と分離されたのち
、共沸蒸留塔で酢酸ビニルと水の共沸混合物と未反応酢
酸とに容易に分離することができる。この反応液のあと
処理は、従来の気相法酢酸ビニルの連続的製造における
蒸留負荷に比べて顕著に軽減され、工業的画値は極めて
高い。According to the method of the present invention, the reaction product liquid taken out from the reaction vessel is separated from dissolved ethylene and oxygen, and then passed through an azeotropic distillation column to form an azeotropic mixture of vinyl acetate and water and unreacted acetic acid. and can be easily separated. The post-processing of this reaction solution is significantly reduced compared to the distillation load in the conventional gas phase continuous production of vinyl acetate, and the industrial resolution is extremely high.
以下、実施例及び比較例により、本発明を更に詳細に説
明する。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
なお、以下の具体例においては、第２図の７０−シート
に示すような小型実験用製造装置を用いた。図中の反応
器１は、内径２．５４の、長さ２００儂の反応管で付帯
する各種設備は、すべてこれに対応するスケールのもの
である。In the following specific example, a small experimental manufacturing apparatus as shown in sheet 70 in FIG. 2 was used. The reactor 1 in the figure is a reaction tube with an inner diameter of 2.54 mm and a length of 200 degrees Fahrenheit, and all of the accompanying equipment is of a scale corresponding to this.
実施例１
第２図に示すような気相法酢ビ合成反応装置の反応管に
、通常酢酸ビニル合成用に用いられる固体触媒（担体ニ
ジリカ球、Ｐｄ濃度：０．５ ｗチ。Example 1 A solid catalyst (Nijirica spheres as carrier, Pd concentration: 0.5 w), which is usually used for vinyl acetate synthesis, was placed in the reaction tube of a vapor phase vinyl acetate synthesis reaction apparatus as shown in FIG.
酢酸カリウム濃度：５Ｗ％） ０．９６を充てん１−１
反応圧力を８ ｋｇ ／ ｃＩｔＧ反応温度を１４０℃
に保って、エチレンを１３００ Ｎｌ１時、酸素をｃｉ
ｏＮ／／時、酢酸を７９０ｇ／時、無水酢酸を８５ｇ／
時の割合で供給し／ヒ。無水酢酸の酢酸罠対する割合は
ｌ （１，８ｗ係であり、本発明の要件の不等式を満足
する。Fill with potassium acetate concentration: 5W%) 0.96 1-1
Reaction pressure: 8 kg/cItG reaction temperature: 140°C
ethylene at 1300 Nl 1 hour and oxygen at ci
oN//hour, acetic acid 790g/hour, acetic anhydride 85g/hour
Supply at the rate of time. The ratio of acetic anhydride to acetic acid traps is 1.8w, which satisfies the inequality requirement of the present invention.
相二輻１−． ｙｔ−ｒａｔ反応液を粗反応液受器より
採取し、ガスクロマトグラフィーで分析した。phase two convergence 1-. The yt-rat reaction solution was collected from the crude reaction solution receiver and analyzed by gas chromatography.
その結４４４ 、粗反応液の組成は、酢酸７５，９ｗ％
。As a result, the composition of the crude reaction solution was 75.9 w% acetic acid.
.
酢酸ビニル２０．９ ＜ｖ％、水４．ＩＷ俤であり無水
酢酸は検出されなかった。酢酸ビニルの空時収縫は２５
４．５’／ｃａｔ−ｄｘ時であった。Vinyl acetate 20.9 <v%, water 4. IW was observed, and acetic anhydride was not detected. The space-time convergence of vinyl acetate is 25
It was 4.5'/cat-dx.
また副生水の酢酸ビニルに対する割合は１９．６Ｗ％で
あった。The ratio of by-product water to vinyl acetate was 19.6 W%.
比較例１
実施例１の反応において、７９０ｇ／時の酢酸および８
５’９７時の無水酢酸に代えて８６：ｌ／時の酢酸を供
給したところ、粗反応液の組成は、酢酸７２．４Ｗ％、
酢酸ビニル２１．７Ｗチ、水５．７Ｗ％であシ、酢酸ビ
ニルの空時収率は２６２ｇ／ｃａｔ−７Ｘ時であった。Comparative Example 1 In the reaction of Example 1, 790 g/h of acetic acid and 8
When acetic acid was supplied at 86:1/hour in place of acetic anhydride at 5'97, the composition of the crude reaction solution was 72.4W% acetic acid,
The space-time yield of vinyl acetate was 262 g/cat-7X hour.
また副生水の酢酸ビニルに対する割合は２６．３ｗ％で
あ２．つた。The ratio of by-product water to vinyl acetate was 26.3 w%. Ivy.
実施例２
実施例１の反応において無水酢酸の供給量を１０２．９
／時に増し、反応温度を１５０＝Ｃにした以外は同一に
して反応させた。この場合の無水酢酸の酢酸に対する割
合は１２．９Ｗ％であシ、本発明の要件を満足する。Example 2 In the reaction of Example 1, the amount of acetic anhydride supplied was 102.9
The reaction was carried out in the same manner except that the reaction temperature was increased to 150=C. In this case, the ratio of acetic anhydride to acetic acid was 12.9 W%, which satisfies the requirements of the present invention.
得られた。粗反応液を分析した結果、その組成は酢酸６
９．３ｗ％、酢酸ビニル２５．９ｗ％、水４．８Ｗチで
多シ、無水酢酸は検出されなかった。Obtained. As a result of analyzing the crude reaction solution, its composition was acetic acid 6
At a concentration of 9.3 w%, vinyl acetate 25.9 w%, and water 4.8 W, no acetic anhydride was detected.
酢酸ビニルの空時収量は３７５９ ／ Ｃａｔ４Ｘ時で
あった。The space-time yield of vinyl acetate was 3759/Cat4X hours.
副生水の酢酸ビニルに対する割合は１８．５ｗ％であつ
プヒ。The ratio of by-product water to vinyl acetate was 18.5 w%.
比較例２
実施例１の反応において、酢酸供給量を７５７ｙ／時、
無水酢酸を１２５ｇ／時で供給したほかは同一に（−で
反応させた（無水酢酸の酢酸に対する割合は１ａｓｗ％
）。しかしこの場合、凝縮液の組成は酢酸が８６．８Ｗ
％、無水酢酸が１０．９Ｗチ、水は極少量であった。Comparative Example 2 In the reaction of Example 1, the amount of acetic acid supplied was 757 y/hour,
The reaction was carried out in the same manner as (-) except that acetic anhydride was supplied at a rate of 125 g/hour (the ratio of acetic anhydride to acetic acid was 1 asw%).
). However, in this case, the composition of the condensate is 86.8W acetic acid.
%, acetic anhydride was 10.9W, and water was extremely small.
酢酸ビニルはわずか２．３Ｗ％しかなく、その空時収量
は２２ ｊｉ／ ｃａｔ−ｄ ｘ時でめった。Vinyl acetate was only 2.3 W% and its space-time yield was 22 ji/cat-d x hours.
実施例３
比較例２において、水を１１／時で供給したほかは同一
にして反応させた。（ｘ＝ｔｚ５（ｇ／時） ＜Ａ＝ｏ
、ｔ ３８ Ｘ ７５７ （ｇ／時）ｘ６．５９Ｘ８Ｕ
’／時）＝１５７（９／時）であり、無水酢酸供給量東
件を満足する。）
分析の結果、粗反応液の組成は酢酸が７５．０Ｗチ、酢
酸ビニルが２１．４．Ｗ％、水が３，６ｗ％であシ、酢
酸ビニルの空時収量は２３９９／ ｃａｔ−１ｘ時であ
った。Example 3 The reaction was carried out in the same manner as in Comparative Example 2 except that water was supplied at a rate of 11/hour. (x=tz5(g/hour) <A=o
, t 38 x 757 (g/hr) x 6.59 x 8U
'/hour) = 157 (9/hour), which satisfies the acetic anhydride supply amount requirement. ) As a result of analysis, the composition of the crude reaction solution was 75.0W of acetic acid and 21.4W of vinyl acetate. W%, water was 3.6 w%, and the space-time yield of vinyl acetate was 2399/cat-1x hour.
また副生水の酢酸ビニルに対する割合は１７．ＩＷチで
あった。The ratio of by-product water to vinyl acetate is 17. It was IW Chi.
上記実施例１〜３は比較例１と比較Ｌ ”７ｍ明らかな
ように、酢酸ビニルに対する水の割合がそれぞＡ２５〜
３５ｗ％も減少しており、蒸留負荷が大幅に軽減される
ことが理解できる。The above Examples 1 to 3 are compared with Comparative Example 1.As is clear, the ratio of water to vinyl acetate is A25~7m.
It can be seen that the distillation load has been reduced significantly by 35 w%.
第１図は、通常の酢酸ビニル製造方法のフローシートで
あシ、第２図は、本発明の実施例及び比較例で用いたフ
ローシートである。
図中の符号：
１・・・反応器、２・・・コンデンサー、３・・・気液
分離器、 ４・・・受器、 ５・・・共沸蒸留塔、 ７
・・・酢酸ビニル蒸留塔、１０・・・酢酸蒸発器、１１
・・・酢！＃過熱器。
特許出願７ベ 信越酢酸ビニル株式会社信越化学工業株
式会社FIG. 1 is a flow sheet of a normal vinyl acetate manufacturing method, and FIG. 2 is a flow sheet used in Examples and Comparative Examples of the present invention. Symbols in the diagram: 1... Reactor, 2... Condenser, 3... Gas-liquid separator, 4... Receiver, 5... Azeotropic distillation column, 7
... Vinyl acetate distillation column, 10 ... Acetic acid evaporator, 11
···vinegar! #Superheater. Patent application 7 Shin-Etsu Vinyl Acetate Co., Ltd. Shin-Etsu Chemical Co., Ltd.
Claims (1)
下に、常圧ないし２０気圧の圧力及び５０〜ＺＯＯ℃の
温度で気相反応させて酢酸ビニルを連続的に製造する方
法において、反応区域に供給される酢酸をｙ（重量部／
時）、水を２（重量部／時）とした場合、無水酢酸供給
量Ｘ（重量部／時）が、次式 ％式％ を満足するように無水酢酸を供給することを特徴とする
連続的酢酸ビニルの製造方法。[Claims] Vinyl acetate is continuously produced by a gas phase reaction of ethylene, acetic acid and oxygen in the presence of a metal catalyst from Group I of the periodic table at a pressure of normal pressure to 20 atm and a temperature of 50 to ZOO°C. In the method for producing acetic acid fed to the reaction zone, y (parts by weight/
A continuous method characterized in that acetic anhydride is supplied such that when water is 2 (parts by weight/hour) and water is 2 (parts by weight/hour), the acetic anhydride supply amount A method for producing vinyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58119799A JPS6011442A (en) | 1983-06-30 | 1983-06-30 | Production of vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58119799A JPS6011442A (en) | 1983-06-30 | 1983-06-30 | Production of vinyl acetate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6011442A true JPS6011442A (en) | 1985-01-21 |
Family
ID=14770510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58119799A Pending JPS6011442A (en) | 1983-06-30 | 1983-06-30 | Production of vinyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011442A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011518209A (en) * | 2008-04-24 | 2011-06-23 | ワッカー ケミー アクチエンゲゼルシャフト | Method for producing unsaturated carboxylic acid ester |
| CN102218340A (en) * | 2010-04-16 | 2011-10-19 | 天华化工机械及自动化研究设计院 | Preparation method for synthesizing vinyl acetate catalyst by using acetylene gas phase method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4875511A (en) * | 1972-01-14 | 1973-10-11 |
-
1983
- 1983-06-30 JP JP58119799A patent/JPS6011442A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4875511A (en) * | 1972-01-14 | 1973-10-11 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011518209A (en) * | 2008-04-24 | 2011-06-23 | ワッカー ケミー アクチエンゲゼルシャフト | Method for producing unsaturated carboxylic acid ester |
| CN102218340A (en) * | 2010-04-16 | 2011-10-19 | 天华化工机械及自动化研究设计院 | Preparation method for synthesizing vinyl acetate catalyst by using acetylene gas phase method |
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