JPH069454A - Production of ethyl acetate and ethyl alcohol - Google Patents
Production of ethyl acetate and ethyl alcoholInfo
- Publication number
- JPH069454A JPH069454A JP4164920A JP16492092A JPH069454A JP H069454 A JPH069454 A JP H069454A JP 4164920 A JP4164920 A JP 4164920A JP 16492092 A JP16492092 A JP 16492092A JP H069454 A JPH069454 A JP H069454A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water
- ethyl alcohol
- ethyl acetate
- catalyst
- 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
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
【０００１】[0001]
【産業上の利用分野】本発明は、エチレンと酢酸及び水
とを原料として効率良く酢酸エチルとエチルアルコール
とを同時に製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing ethyl acetate and ethyl alcohol simultaneously from ethylene, acetic acid and water as raw materials.
【０００２】[0002]
【従来の技術】従来、カルボン酸エステルとアルコール
を併産する方法としては、特公昭４７−４２８０８があ
げられる。即ち、エチレン系不飽和化合物を飽和脂肪族
カルボン酸とリンモリブデン酸もしくは、リンタングス
テン酸の遊離ヘテロポリ酸と水を含有する液体媒質と接
触させる液相法が開示されている。しかしながら、この
特許によれば、エチレンを原料とした場合ブタン−２−
オールが生成しエチルアルコールは生成しない。2. Description of the Related Art Conventionally, as a method for co-producing a carboxylic acid ester and an alcohol, there is JP-B-47-42808. That is, a liquid phase method in which an ethylenically unsaturated compound is contacted with a liquid medium containing a saturated aliphatic carboxylic acid and phosphomolybdic acid or a free heteropolyacid of phosphotungstic acid and water is disclosed. However, according to this patent, butane-2-
All is produced and ethyl alcohol is not produced.
【０００３】又、特開平４−１３９１４８号公報にはケ
イタングステン酸の、及び特開平４−１３９１４９号公
報にはリンタングステン酸のセリウム塩、ルビジウム
塩、タリウム塩、アンモニウム塩及びカリウム塩を使用
し、低級脂肪酸と低級オレフィンから低級脂肪酸エステ
ルを製造する際、少量の水蒸気を添加することによりエ
チルアルコールが生成することがのべられている。Further, cerium tungstic acid is used in JP-A-4-139148, and cerium salt, rubidium salt, thallium salt, ammonium salt and potassium salt of phosphotungstic acid are used in JP-A-4-139149. When producing a lower fatty acid ester from a lower fatty acid and a lower olefin, it is known that ethyl alcohol is produced by adding a small amount of steam.
【０００４】[0004]
【発明が解決しようとする課題】しかし、これらに記載
の触媒及び水蒸気の量の両面から検討したところ生成す
るアルコールの量は、極少量で酢酸エチルとエチルアル
コールを併産する方法としては、実用面から不十分であ
る。本発明は上記の事情に鑑みてなされたもので、本発
明者らは気相反応で或る限定された触媒を使用して、一
定範囲の水蒸気を用いることにより、酢酸エチルとエチ
ルアルコールを併産する実用的な方法を提供することを
目的とする。However, as a result of examining both the amount of catalyst and the amount of water vapor described therein, the amount of alcohol produced is practically small as a method for co-producing ethyl acetate and ethyl alcohol. It is insufficient from the aspect. The present invention has been made in view of the above circumstances, and the present inventors used a limited catalyst in a gas phase reaction and used a certain range of steam to combine ethyl acetate and ethyl alcohol. The aim is to provide a practical way of producing.
【０００５】[0005]
【課題を解決するための手段】本発明の酢酸エチルとエ
チルアルコールを併産する方法においては、ヘテロポリ
酸の酸性塩を触媒とし、気相でエチレンと酢酸及び水を
原料とすることにより、問題解決の手段とした。In the method for co-producing ethyl acetate and ethyl alcohol according to the present invention, there is a problem in that an acidic salt of heteropolyacid is used as a catalyst and ethylene, acetic acid and water are used as raw materials in a gas phase. It was taken as a solution.
【０００６】ヘテロポリ酸としては、リンタングステン
酸、リンモリブデン酸、ケイタングステン酸、ケイモリ
ブデン酸、タングストモリブドリン酸、タングストモリ
ブドケイ酸等の混合配位型ヘテロポリ酸である。本発明
における触媒は、ヘテロポリ酸１モル当り、０．０５〜
２．９グラム原子の水素が周期律表Ｉａ，Ｉｂ族の元
素、カルシウム、ストロンチウム、バリウム、アルミニ
ウム、ガリウム、タリウムおよびアンモニウム基よりな
る群から選ばれた少なくとも１種類の元素または分子に
より置換されたヘテロポリ酸の酸性塩である。The heteropolyacid is a mixed coordination type heteropolyacid such as phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, tungstomolybdophosphoric acid and tungstomolybdosilicic acid. The catalyst in the present invention is 0.05 to 1 mol per 1 mol of heteropolyacid.
2.9 grams of hydrogen have been replaced by at least one element or molecule selected from the group consisting of elements of groups Ia and Ib of the Periodic Table, calcium, strontium, barium, aluminum, gallium, thallium and ammonium groups. It is an acid salt of heteropoly acid.
【０００７】上記の置換値の範囲をはずれると酢酸エチ
ル及びエチルアルコールの収率が著しく悪くなり実用的
でない。望ましくは、０．１〜２．７の範囲である。反
応形式は気相反応である。If the substitution value is out of the above range, the yields of ethyl acetate and ethyl alcohol are significantly deteriorated, which is not practical. It is preferably in the range of 0.1 to 2.7. The reaction type is a gas phase reaction.
【０００８】原料中のエチレンと酢酸のモル比は１〜４
０、好ましくは１０〜３０である。酢酸と水との和に対
する水の割合は１０〜７５wt％、好ましくは２０〜６５
wt％である。勿論この範囲外の水の割合でも酢酸エチル
とエチルアルコールは生成するが水の割合が１０wt％よ
り小さくなるとエチルアルコールの収率が著しく悪くな
り、７５wt％を超えると酢酸エチルとエチルアルコール
の収率が著しく悪くなる。The molar ratio of ethylene and acetic acid in the raw material is 1 to 4
It is 0, preferably 10 to 30. The ratio of water to the sum of acetic acid and water is 10 to 75% by weight, preferably 20 to 65%.
wt%. Of course, even if the proportion of water is outside this range, ethyl acetate and ethyl alcohol are produced, but if the proportion of water is less than 10 wt%, the yield of ethyl alcohol will be extremely poor, and if it exceeds 75 wt%, the yield of ethyl acetate and ethyl alcohol will be great. Becomes significantly worse.
【０００９】反応圧力は、０〜５０ｋｇ／ｃｍ2 Ｇ、好
ましくは０〜１０ｋｇ／ｃｍ2 Ｇの範囲である。反応温
度は、５０〜３００℃、特に１００〜２５０℃の範囲が
好ましい。エチルアルコールを多く生成させる場合は、
温度を高くする方が有利である。The reaction pressure is in the range of 0 to 50 kg / cm 2 G, preferably 0 to 10 kg / cm 2 G. The reaction temperature is preferably 50 to 300 ° C, particularly preferably 100 to 250 ° C. When producing a lot of ethyl alcohol,
It is advantageous to raise the temperature.
【００１０】空間速度は、標準状態において１００〜５
０００hr-1、特に３００〜２０００hr-1で触媒を通すの
が好ましい。本発明に用いられる触媒は、それ自体でも
或いは、担体に担持させて用いても良い。使用される担
体は、一般に担体として用いられる多孔質或いは、多孔
質に造粒できる物質であれば良く例えば、シリカ、ケイ
ソウ土、チタニア、活性炭、アルミナ、シリカアルミナ
等の一種又は一種以上を混合したものが使用される。The space velocity is 100 to 5 in the standard state.
It is preferable to pass the catalyst at 000 hr -1 , particularly 300 to 2000 hr -1 . The catalyst used in the present invention may be used by itself or may be used by being supported on a carrier. The carrier used may be a porous material generally used as a carrier or a substance capable of granulating into a porous material, for example, one or more of silica, diatomaceous earth, titania, activated carbon, alumina, silica-alumina and the like are mixed. Stuff used.
【００１１】[0011]
【実施例】以下に実施例により本発明を更に具体的に説
明する。 実施例１ 市販のリンタングステン酸の７０wt％水溶液に硝酸セシ
ウムをリンタングステン酸１モル当り２モル含んだ水溶
液を少量ずつ撹拌下に添加した。フラスコを湯浴によっ
て大部分の水を蒸発し乾燥器に入れ空気中１５０℃で３
時間、更に２００℃で５時間乾燥した。EXAMPLES The present invention will be described in more detail with reference to the following examples. Example 1 To a commercially available 70 wt% aqueous solution of phosphotungstic acid, an aqueous solution containing 2 mol of cesium nitrate per 1 mol of phosphotungstic acid was added with stirring little by little. Evaporate most of the water from the flask in a hot water bath, put it in a dryer and put it in air at 150 ° C for 3
And dried at 200 ° C. for 5 hours.
【００１２】この触媒２０ｍｌを反応管に充填し、温度
１８０℃、圧力５ｋｇ／ｃｍ2 Ｇでエチレン１６Ｎｌ／
hr、酢酸中の水５４．５wt％の含水酢酸４．７ｇ／hrを
導入し、１hr反応を行なった。生成したガスを冷却し凝
縮した反応捕集液をガスクロマトグラフィーにて分析し
た。その結果酢酸エチル１．７５ｇ、エチルアルコール
０．４９ｇが得られた。20 ml of this catalyst was charged into a reaction tube, and the temperature was 180 ° C. and the pressure was 5 kg / cm 2 G.
hr, 4.7 g / hr of hydrous acetic acid containing 54.5 wt% of water in acetic acid was introduced, and the reaction was carried out for 1 hr. The reaction collected liquid obtained by cooling the generated gas and condensing it was analyzed by gas chromatography. As a result, 1.75 g of ethyl acetate and 0.49 g of ethyl alcohol were obtained.
【００１３】実施例２ 硝酸セシウムの代わりに硝酸銅の３水塩１．２５モルを
用いた以外は実施例１と同じにした。Example 2 Example 1 was repeated except that 1.25 mol of copper nitrate trihydrate was used instead of cesium nitrate.
【００１４】実施例３ 硝酸セシウムの代わりに硝酸カルシウムの４水塩０．７
５モルを用いた以外は実施例１と同じにした。EXAMPLE 3 Calcium nitrate tetrahydrate 0.7 instead of cesium nitrate 0.7
Same as Example 1 except that 5 mol was used.
【００１５】実施例４ 硝酸セシウムの代わりに硝酸ストロンチウム０．５モル
を用いた以外は実施例１と同じにした。Example 4 Example 1 was repeated except that 0.5 mol of strontium nitrate was used instead of cesium nitrate.
【００１６】実施例５ 硝酸セシウムの代わりに硝酸アルミニウムの９水塩０．
６モルを用いた以外は実施例１と同じにした。Example 5 Instead of cesium nitrate, aluminum nitrate nonahydrate.
Same as Example 1 except that 6 mol was used.
【００１７】実施例６ 硝酸セシウムの代わりに硝酸ガリウムの８水塩０．８モ
ルを用いた以外は実施例１と同じにした。Example 6 Same as Example 1 except that 0.8 mol of gallium nitrate octahydrate was used in place of cesium nitrate.
【００１８】実施例７ リンタングステン酸の代わりにリンモリブデン酸を用
い、硝酸セシウムの代わりに硝酸バリウム１．２５モル
を用いた以外は実施例１と同じにした。Example 7 Example 1 was repeated except that phosphomolybdic acid was used instead of phosphotungstic acid and 1.25 mol of barium nitrate was used instead of cesium nitrate.
【００１９】実施例８ リンタングステン酸の代わりにケイタングステン酸を用
い、硝酸セシウムの代わりに硝酸アンモニウム２．６モ
ルを用いた以外は実施例１と同じにした。Example 8 Same as Example 1 except that silicotungstic acid was used instead of phosphotungstic acid and 2.6 mol of ammonium nitrate was used instead of cesium nitrate.
【００２０】実施例９ リンタングステン酸の代わりにケイモリブデン酸を用
い、硝酸セシウムの代わりに硝酸タリウム２．５モルを
用いた以外は実施例１と同じにした。Example 9 Same as Example 1 except that silicomolybdic acid was used instead of phosphotungstic acid and 2.5 mol of thallium nitrate was used instead of cesium nitrate.
【００２１】実施例１０ リンタングステン酸の代わりに１１−タングスト１−モ
リブドリン酸を用い、硝酸セシウム２．５モルを用いた
以外は実施例１と同じにした。Example 10 Example 10 was repeated except that 11-tungsto 1-molybdophosphoric acid was used in place of phosphotungstic acid and 2.5 mol of cesium nitrate was used.
【００２２】比較例１ 硝酸セシウム３モルを用い、エチレン９．２Ｎｌ／hr、
酢酸中の水７９．０wt％の含水酢酸１０．２ｇ／hrを導
入した以外は実施例１と同じにした。Comparative Example 1 Using 3 mol of cesium nitrate, ethylene 9.2 Nl / hr,
Same as Example 1 except that 10.2 g / hr of hydrous acetic acid containing 79.0 wt% of water in acetic acid was introduced.
【００２３】比較例２ 市販のリンタングステン酸１５０ｇを空気中１５０℃で
３時間乾燥し、錠剤に成型し、更に２００℃で５時間乾
燥した触媒を用い、エチレン１９．１Ｎｌ／hr、酢酸中
の水３．６wt％の含水酢酸２．２ｇ／hrを導入した以外
は実施例１と同じにした。Comparative Example 2 150 g of commercially available phosphotungstic acid was dried in air at 150 ° C. for 3 hours, molded into tablets, and further dried at 200 ° C. for 5 hours using a catalyst, ethylene 19.1 Nl / hr, in acetic acid. Same as Example 1 except that 2.2 g / hr of water-containing acetic acid containing 3.6 wt% of water was introduced.
【００２４】上記実施例１〜１０及び比較例１、２の結
果を一括して表１に示す。尚、上記実施例で粉末状とな
る触媒は、錠剤に成型して用いた。The results of Examples 1 to 10 and Comparative Examples 1 and 2 are collectively shown in Table 1. The powdery catalyst used in the above examples was molded into tablets for use.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】以上説明したように、本発明の方法にお
いては、ヘテロポリ酸の特定の酸性塩を触媒とし、特定
の範囲の水の存在下気相で反応させるので酢酸エチルと
エチルアルコールを効率良く併産出来る利点がある。INDUSTRIAL APPLICABILITY As described above, in the method of the present invention, since a specific acidic salt of heteropolyacid is used as a catalyst and the reaction is carried out in the gas phase in the presence of water in a specific range, ethyl acetate and ethyl alcohol are efficiently used. It has the advantage of being able to co-produce well.
───────────────────────────────────────────────────── 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 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location // C07B 61/00 300
Claims (1)
２．９グラム原子の水素が周期律表Ｉａ，Ｉｂ族の元
素、カルシウム、ストロンチウム、バリウム、アルミニ
ウム、ガリウム、タリウムおよびアンモニウム基よりな
る群から選ばれた少なくとも１種類の元素または分子に
より置換されたヘテロポリ酸の酸性塩を触媒として使用
して、エチレンと酢酸及び酢酸と水との和に対する水が
１０〜７５wt％の水とを気相で反応することを特徴とす
る酢酸エチルとエチルアルコールの製造法。1. From 0.05 to 1 mole of heteropolyacid
2.9 grams of hydrogen have been replaced by at least one element or molecule selected from the group consisting of elements of groups Ia and Ib of the Periodic Table, calcium, strontium, barium, aluminum, gallium, thallium and ammonium groups. Production of ethyl acetate and ethyl alcohol, characterized by reacting 10 to 75% by weight of water with respect to the sum of ethylene and acetic acid and acetic acid and water in a gas phase using an acidic salt of heteropolyacid as a catalyst Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16492092A JP3147500B2 (en) | 1992-06-23 | 1992-06-23 | Production method of ethyl acetate and ethyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16492092A JP3147500B2 (en) | 1992-06-23 | 1992-06-23 | Production method of ethyl acetate and ethyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH069454A true JPH069454A (en) | 1994-01-18 |
| JP3147500B2 JP3147500B2 (en) | 2001-03-19 |
Family
ID=15802366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16492092A Expired - Fee Related JP3147500B2 (en) | 1992-06-23 | 1992-06-23 | Production method of ethyl acetate and ethyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3147500B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861530A (en) * | 1995-08-02 | 1999-01-19 | Bp Chemicals Limited | Ester synthesis |
-
1992
- 1992-06-23 JP JP16492092A patent/JP3147500B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861530A (en) * | 1995-08-02 | 1999-01-19 | Bp Chemicals Limited | Ester synthesis |
| USRE41341E1 (en) | 1995-08-02 | 2010-05-18 | Ineos Europe Limited | Ester synthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3147500B2 (en) | 2001-03-19 |
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