JP2947602B2 - Method for producing lower fatty acid ester - Google Patents
Method for producing lower fatty acid esterInfo
- Publication number
- JP2947602B2 JP2947602B2 JP2258233A JP25823390A JP2947602B2 JP 2947602 B2 JP2947602 B2 JP 2947602B2 JP 2258233 A JP2258233 A JP 2258233A JP 25823390 A JP25823390 A JP 25823390A JP 2947602 B2 JP2947602 B2 JP 2947602B2
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- lower fatty
- catalyst
- acid ester
- acid
- 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 - Lifetime
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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、低級脂肪酸と低級オレフィンとを反応さ
せ、効率よく低級脂肪酸エステルを製造する方法に関す
る。The present invention relates to a method for producing a lower fatty acid ester efficiently by reacting a lower fatty acid with a lower olefin.
従来、低級脂肪酸と低級オレフィンとを反応させて低
級脂肪酸エステルを製造する方法としては、強酸性陽イ
オン交換樹脂を触媒として用いる方法、リン酸等の鉱
酸、リンタングステン酸等のヘテロポリ酸を触媒として
用いる方法（特公昭53−6131号公報）、芳香族ジスルホ
ン酸および／またはそのエステルを触媒として用いる方
法（特開昭57−183743号公報）等が知られている。Conventionally, as a method of producing a lower fatty acid ester by reacting a lower fatty acid and a lower olefin, a method using a strongly acidic cation exchange resin as a catalyst, a mineral acid such as phosphoric acid, and a heteropoly acid such as phosphotungstic acid as a catalyst are used. (JP-B-53-6131), a method using aromatic disulfonic acid and / or an ester thereof as a catalyst (JP-A-57-183743), and the like.
しかしながら、上記従来の方法は、いずれも触媒１
による１時間あたりの目的生成物の生産量（以下空時収
率、g/hr・触媒という）も少ないばかりでなく、触媒
寿命も短く、工業的に使用できる方法ではない。However, the conventional methods described above all use the catalyst 1
Not only is the production amount of the target product per hour (hereinafter referred to as space-time yield, g / hr · catalyst) small, but the catalyst life is short, and this is not a method that can be used industrially.
本発明者らは、空時収率が高く、触媒寿命の長い方法
を得べく鋭意研究を行った結果、触媒としてリンタング
ステン酸の塩が有効なことを発見した。The present inventors have conducted intensive studies to obtain a method having a high space-time yield and a long catalyst life. As a result, they have found that a phosphotungstic acid salt is effective as a catalyst.
本発明は上記の発見に基づいてなされたもので、空時
収率が高く、触媒寿命の長い、工業生産に適した低級脂
肪酸エステルの製造方法を提供することを目的とする。The present invention has been made based on the above findings, and has as its object to provide a method for producing a lower fatty acid ester having a high space-time yield, a long catalyst life, and suitable for industrial production.
上記の目的を達成するため、本発明の低級脂肪酸エス
テルの製造方法においては、 リンタングステン酸のセシウム塩、ルビジウム塩、タ
リウム塩、あるいはアンモニウム塩のうち少なくとも一
種類のリンタングステン酸塩を触媒として用いることを
問題解決の手段とした。In order to achieve the above object, in the method for producing a lower fatty acid ester of the present invention, at least one kind of phosphotungstate of a cesium salt, a rubidium salt, a thallium salt, or an ammonium salt of phosphotungstic acid is used as a catalyst. This was the means of solving the problem.
本発明の方法に用いられる低級脂肪酸としては、炭素
数４以下の飽和或は不飽和脂肪酸、例えば、ぎ酸、酢
酸、プロピオン酸、吉草酸、アクリル酸、クロトン酸が
あげられ、低級オレフィンとしては、炭素数４以下のオ
レフィン、例えばエステル、プロピレン、ブテン−１、
ブテン−２があげられる。The lower fatty acid used in the method of the present invention includes a saturated or unsaturated fatty acid having 4 or less carbon atoms, for example, formic acid, acetic acid, propionic acid, valeric acid, acrylic acid and crotonic acid. Olefins having 4 or less carbon atoms, such as esters, propylene, butene-1,
Butene-2.
炭素数が５以上のオレフィンを用いると、脂肪酸エス
テルの生成反応が遅くなり、これを早くするために反応
圧力、或いは反応温度を高くすると、重合物等の副生物
が増大するばかりでなく、触媒寿命が著しく短くなる。When an olefin having 5 or more carbon atoms is used, the production reaction of the fatty acid ester is slowed down. If the reaction pressure or the reaction temperature is increased in order to accelerate the reaction, not only the by-products such as polymers increase, but also the catalyst Life is significantly shortened.
本発明の方法における反応形式は、液相反応、気相反
応のいずれも使用出来るが、特に気相反応が好ましい。In the method of the present invention, any of a liquid phase reaction and a gas phase reaction can be used, but a gas phase reaction is particularly preferable.
気相反応においては低級脂肪酸に対して低級オレフィ
ンを大過剰とする必要がある。反応圧力は０〜10kg/cm2
Gの範囲で、液相反応の場合の圧力10〜150kg/cm2Gより
大幅に低い。In a gas phase reaction, it is necessary to make a large excess of a lower olefin relative to a lower fatty acid. Reaction pressure is 0 to 10 kg / cm 2
In the range of G, it is much lower than the pressure of 10-150 kg / cm 2 G for the liquid phase reaction.
反応温度は、気相、液相いずれにおいても50〜300
℃、特に100〜250℃の範囲が好ましい。反応温度が50℃
未満では、反応速度が遅くなり、空時収率が著しく低下
する。また、300℃を超えると、副生物が増大するとと
もに触媒寿命が短くなる。The reaction temperature is 50 to 300 in both gas phase and liquid phase.
C., preferably in the range of 100 to 250C. Reaction temperature is 50 ℃
If it is less than 1, the reaction rate becomes slow, and the space-time yield is remarkably reduced. On the other hand, when the temperature exceeds 300 ° C., by-products increase and the catalyst life is shortened.
また、気相反応において水が存在するとアルコールが
生成するが、理由は定かではないが原料ガスに容積比で
１％程度の水蒸気を添加すると触媒寿命が長くなる。In addition, alcohol is generated when water is present in the gas phase reaction, but for unknown reasons, the addition of about 1% by volume of steam to the raw material gas prolongs the catalyst life.
気相反応においては、混合ガスを標準状態において、
空間速度（SV）100〜5000h-1、特に300〜2000hr-1で触
媒を通すのが好ましい。In the gas phase reaction, the mixed gas is in a standard state,
It is preferable to pass the catalyst at a space velocity (SV) of 100 to 5000 h -1 , particularly 300 to 2000 hr -1 .
本発明に用いられるリンタングステン酸性塩は、表面
積が大きく、酸強度が強く、かつ酸量が多いもの程よ
く、それ自体でも、或いは担体に担持させて用いてもよ
い。The phosphotungsten acid salt used in the present invention preferably has a large surface area, a high acid strength, and a large amount of acid, and may be used by itself or supported on a carrier.
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よく、例え
ば、シリカ、ケイ草土、チタニア、活性炭等があげられ
る。The carrier to be used may be any porous material generally used as a carrier or a substance capable of granulating into porous material, and examples thereof include silica, diatomaceous earth, titania, and activated carbon.
上記タングステン酸塩触媒の調整は、例えば市販のリ
ンタングステン酸を水に溶解し、これにセシウム、ルビ
ジウム、タリウム、アンモニウムの硝酸塩、炭酸塩を粉
末のまま、或は水溶液として添加混合する。次いで湯浴
によって大部分の水分を蒸発除去し、得られた固形物
を、空気または窒素等の不活性ガス雰囲気下で、50〜35
0℃、好ましくは100〜300℃で加熱処理することによっ
て得られる。温度が50℃未満では、水分の除去が不十分
となり、350℃を超えると、触媒が劣化する。For the preparation of the tungstate catalyst, for example, commercially available phosphotungstic acid is dissolved in water, and cesium, rubidium, thallium, ammonium nitrate and carbonate are added as powder or as an aqueous solution. Then, most of the water is removed by evaporation with a hot water bath, and the obtained solid substance is dried under an inert gas atmosphere such as air or nitrogen in the range of 50 to 35.
It is obtained by heat treatment at 0 ° C, preferably 100 to 300 ° C. If the temperature is lower than 50 ° C., the removal of water becomes insufficient, and if it exceeds 350 ° C., the catalyst deteriorates.
上記触媒は選択率が高くアルカリ酸等の不飽和カルボ
ン酸においては、90％以上を示し、酢酸などの飽和カル
ボン酸においては95％以上を示す。The above catalyst has a high selectivity and shows 90% or more for unsaturated carboxylic acids such as alkali acids and 95% or more for saturated carboxylic acids such as acetic acid.
実施例１ 市販のリンタングステン酸（和光純薬製）150g（約0.
0438モル）と純水60ccを300ccのフラスコに入れ、溶解
した。Example 1 150 g of commercially available phosphotungstic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
0438 mol) and 60 cc of pure water were placed in a 300 cc flask and dissolved.
別に硝酸セシウム（CsNO3）21.5g（0.110モル）を水
に溶解し、これを滴下ロートを用いて、攪拌しながら、
上記リンタングステン酸水溶液中に滴下した。この際、
滴下すると同時にリンタングステン酸セシウム塩の白色
微粒結晶が析出する。この白色微粒子が析出したフラス
コを湯浴によってフラスコ中の水を蒸発させた。水が除
去された塊状物をシャーレ上に取出して乾燥器に入れ、
空気中、150℃で６時間乾燥した。この乾燥物を粉砕
し、篩を用いて径１〜2mmのものを分取し、35ccを反応
管に充填して反応に供した。Separately, 21.5 g (0.110 mol) of cesium nitrate (CsNO 3 ) was dissolved in water, and this was stirred with a dropping funnel while stirring.
It was dropped into the above phosphotungstic acid aqueous solution. On this occasion,
At the same time as the dropwise addition, white fine crystals of cesium phosphotungstate are precipitated. The water in the flask in which the white fine particles were precipitated was evaporated by a hot water bath. Take out the lump from which water has been removed and put it in a drier,
It was dried in air at 150 ° C. for 6 hours. The dried product was pulverized, and a product having a diameter of 1 to 2 mm was collected using a sieve.
反応は、温度180℃、反応圧力5kg/cm2Gに保持しなが
ら、アクリル酸：エステル：水蒸気を容積比1:18:1の割
分に混合したガスを、標準状態で35/hrの流速で流し
た。混合気体を流し始めてから4hr後における流出液と
ガスをサンプリングし、ガスクロマトマトグラフィーで
測定したところ、アクリル酸の転化率は87.1％、アクリ
ル酸エチルのアクリル酸に対する収率は79.3％であっ
た。また得られたアクリル酸エチルの空時収率は191g/h
r・触媒であった。The reaction was carried out at a standard flow rate of 35 / hr with a gas mixture of acrylic acid: ester: steam at a ratio of 1: 18: 1 while maintaining a temperature of 180 ° C. and a reaction pressure of 5 kg / cm 2 G. Flowed away. The effluent and the gas after 4 hours from the start of the flow of the mixed gas were sampled and measured by gas chromatography, and the conversion of acrylic acid was 87.1%, and the yield of ethyl acrylate with respect to acrylic acid was 79.3%. The space-time yield of the obtained ethyl acrylate is 191 g / h
r. It was a catalyst.
実施例２ 硝酸セシウムの代わりに硝酸タリウム（TlNO3）29.3g
（0.110モル）を用いた以外は実施例１と同じにした。Example 2 Instead of cesium nitrate, 29.3 g of thallium nitrate (TlNO 3 )
(0.110 mol), except that Example 1 was used.
実施例３ 硝酸セシウムの代わりに炭酸ルビジウム（RbCO3）12.
7g（0.055モル）を用いた以外は、実施例１と同じにし
た。Example 3 Rubidium carbonate (RbCO 3 ) instead of cesium nitrate 12.
Same as Example 1 except that 7 g (0.055 mol) was used.
実施例４ 硝酸セシウムの代わりに硝酸アンモニウム（NH4NO3）
8.8g（0.110モル）を用いた以外は実施例１と同じにし
た。Example 4 Ammonium nitrate (NH 4 NO 3 ) instead of cesium nitrate
Example 1 was repeated except that 8.8 g (0.110 mol) was used.
比較例１ 市販のリンタングステン酸（和光純薬製）を150℃で
６時間乾燥した後、錠剤に成型し、これを粉砕して篩分
けし、１〜2mmの径のものを分取し、その35ccを触媒と
して使用した他は実施例１と同じにした。Comparative Example 1 A commercially available phosphotungstic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dried at 150 ° C. for 6 hours, formed into tablets, crushed and sieved, and those having a diameter of 1 to 2 mm were collected. The procedure was the same as in Example 1 except that 35 cc was used as a catalyst.
実施例５ エステルの代わりにプロピレンを用いた他は、実施例
１と同じにしてアクリル酸イソプロピルを生成せしめ
た。Example 5 Isopropyl acrylate was produced in the same manner as in Example 1 except that propylene was used instead of the ester.
実施例６ 実施例１において触媒としたリンタングステン酸のセ
シウム塩10.7ccを触媒とし、反応温度150℃、反応圧力
を常圧に保持しながら酢酸：エチレン：水蒸気の容積比
6.8:92.2:1の混合気体を、標準状態で10.7/hrの流速
で流した。混合気体を流し始めてから４時間後、流出液
とガスをサンプリングしてガスクロマトグラフィによっ
て分析したところ、酢酸の転化率は52.6％、酢酸に対す
る酢酸エチルの収率は50.0％であった。この結果より求
めた酢酸エチルの空時収率は134g/hr・触媒であっ
た。Example 6 A volume ratio of acetic acid: ethylene: steam with 10.7 cc of a cesium phosphotungstic acid catalyst used in Example 1 as a catalyst at a reaction temperature of 150 ° C. and a normal reaction pressure.
A 6.8: 92.2: 1 gas mixture was flowed at a standard flow rate of 10.7 / hr. Four hours after the start of flowing the mixed gas, the effluent and the gas were sampled and analyzed by gas chromatography. As a result, the conversion of acetic acid was 52.6%, and the yield of ethyl acetate based on acetic acid was 50.0%. The space-time yield of ethyl acetate determined from this result was 134 g / hr · catalyst.
実施例７ 触媒としてリンタングステン酸のタリウム塩を用いた
以外は実施例６と同じにした。Example 7 Example 7 was the same as Example 6 except that thallium phosphotungstate was used as a catalyst.
実施例８ 触媒としてリンタングステン酸のルビジウム塩を用い
た以外は実施例６と同じにした。Example 8 Example 8 was the same as Example 6, except that a rubidium salt of phosphotungstic acid was used as a catalyst.
実施例９ 触媒としてリンタングステン酸のアンモニウム塩を用
いた以外は実施例６と同じにした。Example 9 Example 9 was the same as Example 6 except that an ammonium salt of phosphotungstic acid was used as a catalyst.
実施例10 反応圧力を5kgG/cm2とした以外は実施例６と同じにし
た。Example 10 The procedure was the same as Example 6 except that the reaction pressure was 5 kgG / cm 2 .
比較例２ 比較例１と同じ触媒を用いた以外は実施例６と同じに
した。Comparative Example 2 The same procedure as in Example 6 was performed except that the same catalyst as in Comparative Example 1 was used.
上記実施例１〜10、比較例1,2の結果を一括して第１
表に示す。なお、実施例１等の結果はすでに示されてい
るが、比較のため再度記載してある。上記実施例１〜10
においては、96時間運転を続けたが、アクリル酸、或は
酢酸に対する目的成分の収率、空時収率は殆んど低下せ
ず、比較例１および２においては、20時間で収率が２〜
５％低下した。The results of Examples 1 to 10 and Comparative Examples 1 and 2 are collectively
It is shown in the table. Although the results of Example 1 and the like have already been shown, they are described again for comparison. Examples 1 to 10 above
, The operation was continued for 96 hours, but the yield of the target component and the space-time yield with respect to acrylic acid or acetic acid hardly decreased. In Comparative Examples 1 and 2, the yield was increased in 20 hours. Two
It decreased by 5%.
実施例11 市販のリンタングステン酸（和光純薬製）150g（約0.
0438モル）と純水60ccを300ccのフラスコに入れ、溶解
した。 Example 11 150 g of commercially available phosphotungstic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
0438 mol) and 60 cc of pure water were placed in a 300 cc flask and dissolved.
別に硝酸セシウム（CsNO3）21.5g（0.110モル）を水
に溶解し、これを滴下ロートを用いて、攪拌しながら、
上記リンタングステン酸水溶液中に滴下した。この際、
滴下すると同時にリンタングステン酸セシウム塩の白色
微粒結晶が析出する。これに１〜2mm径のシリカを500cc
入れ攪拌し、湯浴によって、フラスコ中の水を蒸発させ
た。水が除去された後、乾燥器に入れ、空気中、150℃
で６時間乾燥した。この乾燥した触媒を担持したシリカ
35ccを反応管に充填して反応に供した。Separately, 21.5 g (0.110 mol) of cesium nitrate (CsNO 3 ) was dissolved in water, and this was stirred with a dropping funnel while stirring.
It was dropped into the above phosphotungstic acid aqueous solution. On this occasion,
At the same time as the dropwise addition, white fine crystals of cesium phosphotungstate are precipitated. 500cc of 1-2mm diameter silica
The mixture was stirred, and the water in the flask was evaporated by a hot water bath. After the water is removed, put it in the dryer and in the air at 150 ℃
For 6 hours. Silica carrying this dried catalyst
35 cc was filled in a reaction tube and used for the reaction.
反応は、温度180℃、反応圧力5kg/cm2Gの保持しなが
ら、アクリル酸：エステル：水蒸気を容積比1:18:1の割
分に混合したガスを、標準状態で35/hrの流速で流し
た。混合気体を流し始めてから4hr後における流出液と
ガスをサンプリングし、ガスクロマトマトグラフィーで
測定したところ、アクリル酸の転化率は48.6％、アクリ
ル酸エチルのアクリル酸に対する収率は45.0％であっ
た。また得られたアクリル酸エチルの空時収率は120g/h
r・触媒であった。The reaction was carried out at a temperature of 180 ° C and a reaction pressure of 5 kg / cm 2 G while a gas mixture of acrylic acid: ester: steam at a ratio of 1: 18: 1 by volume was flowed at a standard flow rate of 35 / hr. Flowed away. The effluent and the gas after 4 hours from the start of flowing the mixed gas were sampled and measured by gas chromatography, and the conversion of acrylic acid was 48.6% and the yield of ethyl acrylate to acrylic acid was 45.0%. The space-time yield of the obtained ethyl acrylate is 120 g / h
r. It was a catalyst.
実施例12 耐圧300kg/cm2、内容積300mlの攪拌機付きオートクレ
ーブにアクリル酸100cc、リンタングステン酸のセシウ
ム塩10.0g、および水1.0gを仕込み、エチレンを導入
し、50kg/cm2Gで加圧吸収させ、これを200℃に昇温し、
５時間反応させた。反応後室温まで冷却し、未反応のエ
チレンを放出した後、ガスクロマトグラフィーで分析し
た。その結果、アクリル酸の転化率は15.9％、アクリル
酸に対するアクリル酸エチルの収率は15.4％であった。Example 12 100 cc of acrylic acid, 10.0 g of cesium phosphotungstic acid, and 1.0 g of water were charged into an autoclave with a stirrer having a pressure resistance of 300 kg / cm 2 and an internal volume of 300 ml, ethylene was introduced, and pressure was applied at 50 kg / cm 2 G. Absorb and raise this to 200 ° C,
The reaction was performed for 5 hours. After the reaction, the reaction mixture was cooled to room temperature to release unreacted ethylene, and then analyzed by gas chromatography. As a result, the conversion of acrylic acid was 15.9%, and the yield of ethyl acrylate based on acrylic acid was 15.4%.
以上説明したように、本発明の方法においては、リン
タングステン酸のセシウム塩、ルビジウム塩、アンモニ
ウム塩、あるいはタリウム塩から選ばれた少なくとも一
種類のリンタングステン酸の塩を触媒として用いるの
で、空時収率が高く、また触媒寿命が長いので、アクリ
ル酸エステルや酢酸エステル等の低級脂肪酸エステルを
効率よく生産出来る利点がある。As described above, in the method of the present invention, at least one kind of phosphotungstic acid salt selected from cesium salt, rubidium salt, ammonium salt, and thallium salt of phosphotungstic acid is used as a catalyst. Since the yield is high and the catalyst life is long, there is an advantage that a lower fatty acid ester such as an acrylate ester or an acetate ester can be efficiently produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 若林 正一郎 大分県大分市大字中の洲２ 昭和電工株 式会社大分研究所内 (56)参考文献 特開 昭54−52025（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 69/14 C07C 67/04 C07C 69/54 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (72) Inventor Shoichiro Wakabayashi 2 Onaka-shi, Oita City, Oita Prefecture 2 Showa Denko KK (56) References JP-A-54-52025 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C07C 69/14 C07C 67/04 C07C 69/54
Claims (4)
する低級脂肪酸エステルの製造方法において、リンタン
グステン酸のセシウム塩、ルビジウム塩、タリウム塩、
或いはアンモニウム塩のうち少なくとも一種類のリンタ
ングステン酸塩を触媒として用いて反応せしめることを
特徴とする低級脂肪酸エステルの製造方法。A method for producing a lower fatty acid ester in which a lower fatty acid is esterified with a lower olefin, comprising a cesium salt, a rubidium salt, a thallium salt of phosphotungstic acid,
Alternatively, a method for producing a lower fatty acid ester, wherein the reaction is carried out using at least one kind of ammonium tungstate phosphotungstate as a catalyst.
する低級脂肪酸エステルの製造方法において、該製造方
法を気相反応で行うことを特徴とする請求項１に記載の
低級脂肪酸エステルの製造方法。2. The method for producing a lower fatty acid ester according to claim 1, wherein the method for producing a lower fatty acid ester by esterifying a lower fatty acid with a lower olefin is carried out by a gas phase reaction.
する低級脂肪酸エステルの製造方法において、該製造方
法を液相反応で行うことを特徴とする請求項１に記載の
低級脂肪酸エステルの製造方法。3. The method for producing a lower fatty acid ester according to claim 1, wherein the method for producing a lower fatty acid ester for esterifying a lower fatty acid with a lower olefin is carried out by a liquid phase reaction.
特徴とする請求項１ないし３のいずれかに記載の低級脂
肪酸エステルの製造方法。4. The method for producing a lower fatty acid ester according to claim 1, wherein the catalyst is a catalyst supported on a carrier.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2258233A JP2947602B2 (en) | 1990-09-27 | 1990-09-27 | Method for producing lower fatty acid ester |
| TW81102298A TW226339B (en) | 1990-09-27 | 1992-03-25 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2258233A JP2947602B2 (en) | 1990-09-27 | 1990-09-27 | Method for producing lower fatty acid ester |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11030705A Division JP3020489B2 (en) | 1999-02-08 | 1999-02-08 | Method for producing lower fatty acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04139149A JPH04139149A (en) | 1992-05-13 |
| JP2947602B2 true JP2947602B2 (en) | 1999-09-13 |
Family
ID=17317371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2258233A Expired - Lifetime JP2947602B2 (en) | 1990-09-27 | 1990-09-27 | Method for producing lower fatty acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2947602B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5241106A (en) * | 1991-10-22 | 1993-08-31 | Mitsui Toatsu Chemicals, Inc. | Process for producing ethyl acetate |
| DE69206781T2 (en) * | 1992-03-25 | 1996-08-22 | Showa Denko Kk | Process for making low fatty acid esters |
| EP1200190B1 (en) | 1999-06-03 | 2007-08-15 | Showa Denko K.K. | Process for producing lower fatty acid ester |
| US6818790B1 (en) | 1999-10-05 | 2004-11-16 | Showa Denko K.K. | Process for producing mixed gas of lower olefin and lower aliphatic carboxylic acid, and process for producing lower aliphatic ester using the mixed gas |
| US20110112330A1 (en) | 2008-04-16 | 2011-05-12 | Nippon Kayaku Kabushiki Kaisha | Catalyst for preparing acrolein or acrylic acid by dehydration reaction of glycerin and method for producing the same |
| KR101399376B1 (en) * | 2009-09-18 | 2014-05-27 | 아르끄마 프랑스 | Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin |
-
1990
- 1990-09-27 JP JP2258233A patent/JP2947602B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04139149A (en) | 1992-05-13 |
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