JPH08259487A - Production of unsaturated aldehyde - Google Patents
Production of unsaturated aldehydeInfo
- Publication number
- JPH08259487A JPH08259487A JP6448195A JP6448195A JPH08259487A JP H08259487 A JPH08259487 A JP H08259487A JP 6448195 A JP6448195 A JP 6448195A JP 6448195 A JP6448195 A JP 6448195A JP H08259487 A JPH08259487 A JP H08259487A
- Authority
- JP
- Japan
- Prior art keywords
- propionaldehyde
- catalyst
- acrolein
- acetaldehyde
- methacrolein
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アセトアルデヒドまた
はプロピオンアルデヒド（以下、飽和アルデヒドと略す
ことがある。）をメタノールと触媒の存在下、気相で接
触反応させて炭素数の一つ多いアクロレインまたはメタ
クロレイン（以下、不飽和アルデヒドと略すことがあ
る。）を高収率で製造する方法に関する。BACKGROUND OF THE INVENTION The present invention relates to acrolein or propionaldehyde (hereinafter sometimes abbreviated as saturated aldehyde) in the presence of a catalyst in the presence of a catalyst in the gas phase to react acrolein or acrolein having one higher carbon number. The present invention relates to a method for producing methacrolein (hereinafter sometimes abbreviated as unsaturated aldehyde) in high yield.
【０００２】[0002]
【従来の技術】飽和モノカルボン酸から炭素数の一つ多
い不飽和モノカルボン酸を製造する方法については従来
から多数の特許が出願されている。しかしながら、飽和
アルデヒドから炭素数の一つ多い不飽和アルデヒドを製
造する方法については少数の特許が出願されているだけ
である。例えば、特開平４−３３８３５２号公報には飽
和アルデヒドとホルムアルデヒドとをホウ酸化合物と第
一級アミンまたは第二級アミン存在下に反応させてα−
メチレンアルデヒド化合物を製造する方法が、また、特
開平６−１６５８７号公報には飽和アルデヒドとホルム
アルデヒドとを第二級アミンおよび有機カルボン酸の存
在下に反応させてα−メチレンアルデヒド化合物を製造
する方法がそれぞれ提案されているが、いずれの方法も
液相反応のため触媒の分離が煩雑であり、しかも連続生
産に適さない等の欠点を有している。2. Description of the Related Art A number of patents have been filed for a method for producing an unsaturated monocarboxylic acid having one more carbon atom from a saturated monocarboxylic acid. However, only a few patents have been filed for a method for producing an unsaturated aldehyde having one more carbon atom from a saturated aldehyde. For example, in JP-A-4-338352, a saturated aldehyde and formaldehyde are reacted with a boric acid compound in the presence of a primary amine or a secondary amine to form α-
A method for producing a methylene aldehyde compound, and a method for producing an α-methylene aldehyde compound by reacting a saturated aldehyde and formaldehyde in the presence of a secondary amine and an organic carboxylic acid in JP-A-6-16587. However, each method has drawbacks such that the separation of the catalyst is complicated due to the liquid phase reaction and is not suitable for continuous production.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、飽和アルデ
ヒドから不飽和アルデヒドを気相で高収率で製造できる
方法を提供することを目的とし、しかもホルムアルデヒ
ドの製造原料であるメタノールをビニル化の原料として
用い、経済的に有利に不飽和アルデヒドを製造する方法
を提供することを目的としている。DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a method capable of producing an unsaturated aldehyde from a saturated aldehyde in a gas phase in a high yield, and moreover, to convert methanol, which is a raw material for the production of formaldehyde, to vinylation. It is an object of the present invention to provide a method for producing an unsaturated aldehyde that is used as a raw material and is economically advantageous.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明は、アセト
アルデヒドまたはプロピオンアルデヒド及びメタノール
のガスを少なくとも原料ガスとして用い、アセトアルデ
ヒドまたはプロピオンアルデヒドをメタノールと気相接
触反応させてアクロレインまたはメタクロレインを製造
するにあたり、下記一般式（１）で表される触媒を使用
することを特徴とするアクロレインまたはメタクロレイ
ンの製造方法にある。That is, in the present invention, acetaldehyde or propionaldehyde and methanol gas are used as at least raw material gas, and acetaldehyde or propionaldehyde is reacted with methanol in a gas phase to produce acrolein or methacrolein. In the above, there is provided a method for producing acrolein or methacrolein, which comprises using a catalyst represented by the following general formula (1).
【０００５】[0005]
【化２】 ＢｉaＭｏbＸcＯd （１） （式中、Ｂｉ、Ｍｏ及びＯはそれぞれビスマス、モリブ
デン及び酸素を示し、Ｘはアルミニウム、珪素、チタ
ン、鉄、コバルト、銀、タングステン、バナジウム及び
リンからなる群より選ばれた少なくとも１種の元素を示
す。但し、ａ、ｂ、ｃ及びｄは各元素の原子比率を表わ
し、ｂ＝１０のときａ＝１〜３０、ｃ＝０〜２０であ
り、ｄは上記各成分の原子価を満足するのに必要な酸素
原子数である。）本発明の方法において使用する触媒の
調製に用いる原料化合物としては、各元素の硝酸塩、炭
酸塩、アンモニウム塩、ハロゲン化物、酸化物等を組合
せて使用することができる。Embedded image Bi a Mo b X c O d (1) (wherein Bi, Mo and O represent bismuth, molybdenum and oxygen, respectively, and X represents aluminum, silicon, titanium, iron, cobalt, silver, tungsten, At least one element selected from the group consisting of vanadium and phosphorus is shown, provided that a, b, c and d represent the atomic ratio of each element, and when b = 10, a = 1 to 30 and c = 0. Is about 20 and d is the number of oxygen atoms required to satisfy the valences of the above components.) The starting compounds used in the preparation of the catalyst used in the method of the present invention include nitrates and carbonates of the respective elements. A combination of salts, ammonium salts, halides, oxides and the like can be used.
【０００６】本発明の方法において使用する触媒は無担
体でも有効であるが、シリカ、アルミナ、シリカ・アル
ミナ、酸化マグネシウム、酸化チタン等の担体に担持さ
せることもできる。担持方法は特に限定されないが、含
浸法、混練法、共沈法等の種々の方法を用いることがで
きる。The catalyst used in the method of the present invention is effective even without a carrier, but it may be supported on a carrier such as silica, alumina, silica-alumina, magnesium oxide, titanium oxide. The supporting method is not particularly limited, but various methods such as an impregnation method, a kneading method, and a coprecipitation method can be used.
【０００７】本発明の方法において使用する触媒は、一
般には固定床で用いられるが流動床でも使用できる。The catalyst used in the process of the present invention is generally used in a fixed bed, but can also be used in a fluidized bed.
【０００８】本発明の実施に際しては、飽和アルデヒド
の供給量とメタノールの供給量との比率は容積比で１：
１０〜１０：１の範囲、特に１：８〜８：１の範囲が好
ましい。これらの反応出発原料は混合ガス（原料ガス）
として供給され、ガス状で触媒と接触される。この場
合、原料ガスは窒素、炭酸ガス等の不活性ガスを加えて
希釈してもよく、また水蒸気を含んでいてもよい。In the practice of the invention, the ratio of the saturated aldehyde feed rate to the methanol feed rate is 1: by volume.
A range of 10 to 10: 1 is preferable, and a range of 1: 8 to 8: 1 is particularly preferable. These reaction starting materials are mixed gas (raw material gas)
And is contacted with the catalyst in gaseous form. In this case, the source gas may be diluted by adding an inert gas such as nitrogen or carbon dioxide, or may contain water vapor.
【０００９】本発明の実施に際しては、原料ガス中に分
子状酸素を原料ガス中の含有量として０．１〜１０容量
％、特に好ましくは０．５〜６容量％となるように添加
することにより不飽和アルデヒドの収率をより向上させ
ることができるので好ましい方法である。In carrying out the present invention, molecular oxygen is added to the raw material gas so that the content of the molecular oxygen in the raw material gas is 0.1 to 10% by volume, particularly preferably 0.5 to 6% by volume. Is a preferable method because it can further improve the yield of unsaturated aldehyde.
【００１０】本発明においては、原料ガスとは、上述の
ように飽和アルデヒドとメタノールのみの混合ガス、こ
の混合ガスに窒素、炭酸ガス等の不活性ガスや水蒸気を
配合したもの、この混合ガスに分子状酸素を添加したも
の、またはこの混合ガスに前記不活性ガスや水蒸気を配
合したものに分子状酸素を添加したものを指す。In the present invention, the raw material gas is a mixed gas of only a saturated aldehyde and methanol as described above, a mixed gas of this mixed gas with an inert gas such as nitrogen or carbon dioxide, or steam. It refers to the one to which molecular oxygen is added, or the one obtained by adding the above-mentioned inert gas or water vapor to this mixed gas and adding the molecular oxygen.
【００１１】原料ガスの触媒上の空間速度（ＳＶ）は５
０〜５０００ｍｌ／ｈｒ／ｍｌ−触媒の範囲で選ぶこと
ができる。The space velocity (SV) of the source gas on the catalyst is 5
It can be selected in the range of 0 to 5000 ml / hr / ml-catalyst.
【００１２】また、反応温度は１００〜５００℃の温度
範囲で適宜選ぶことができるが、特に１５０〜４５０℃
の温度範囲が好ましい。The reaction temperature can be appropriately selected within a temperature range of 100 to 500 ° C., but particularly 150 to 450 ° C.
Is preferred.
【００１３】ところで、飽和アルデヒドとメタノールの
反応では、反応を長時間行うと炭素質状のものが触媒上
に沈着する場合があり、触媒の活性を長期間安定に維持
することが困難な場合もある。しかしながら、触媒を反
応器内又は反応器外で４００〜７００℃程度の温度範囲
で酸素含有ガス雰囲気下、または酸素含有ガス及び水蒸
気共存下において再生する方法で再生することが可能で
ある。従って、かかる触媒の再生方法を適用することに
より、本発明における反応を長期間行うことができる。By the way, in the reaction of saturated aldehyde with methanol, if the reaction is carried out for a long time, a carbonaceous substance may be deposited on the catalyst, and it may be difficult to maintain the activity of the catalyst stably for a long time. is there. However, it is possible to regenerate the catalyst in the reactor or outside the reactor in a temperature range of about 400 to 700 ° C. in an oxygen-containing gas atmosphere or in the coexistence of the oxygen-containing gas and steam. Therefore, by applying such a catalyst regeneration method, the reaction in the present invention can be carried out for a long period of time.
【００１４】[0014]
【実施例】以下に、実施例及び比較例により本発明を具
体的に説明する。なお、実施例及び比較例における
「部」は重量部を意味し、飽和アルデヒドの転化率、生
成した不飽和アルデヒドの選択率は以下のように定義さ
れる。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In addition, "part" in an Example and a comparative example means a weight part, and the conversion rate of a saturated aldehyde and the selectivity of the produced unsaturated aldehyde are defined as follows.
【００１５】飽和アルデヒドの転化率（％）＝［（反応
した飽和アルデヒドのモル数）／（供給した飽和アルデ
ヒドのモル数）］×１００ 不飽和アルデヒドの選択率（％）＝［（生成した不飽和
アルデヒドのモル数）／（反応した飽和アルデヒドのモ
ル数）］×１００ 実施例１ 硝酸ビスマス２１９．８部に過剰量のアンモニア水を添
加し５分間攪拌した後、濾過・洗浄した（固形物（Ａ−
１））。これとは別に純水１０００部にパラモリブデン
酸アンモニウム４０部を加え加熱溶解したものを（Ｂ−
１）液として調製した。Conversion of saturated aldehyde (%) = [(moles of saturated aldehyde reacted) / (moles of saturated aldehyde fed)] × 100 unsaturated aldehyde selectivity (%) = [( (Mol number of saturated aldehyde) / (mol number of reacted saturated aldehyde)] × 100 Example 1 An excess amount of aqueous ammonia was added to 219.8 parts of bismuth nitrate, and the mixture was stirred for 5 minutes and then filtered and washed (solid matter) (A-
1)). Separately from this, 40 parts of ammonium paramolybdate was added to 1000 parts of pure water and heated and dissolved (B-
1) Prepared as a liquid.
【００１６】（Ｂ−１）液に前記固形物（Ａ−１）を加
え２０時間加熱還流後蒸発乾固し、固形物を得た。得ら
れた固形物を１１０℃で２４時間乾燥後、空気雰囲気下
に５００℃で２時間熱処理したものを触媒とした。The solid (A-1) was added to the liquid (B-1), heated under reflux for 20 hours, and evaporated to dryness to obtain a solid. The obtained solid was dried at 110 ° C. for 24 hours and then heat-treated in an air atmosphere at 500 ° C. for 2 hours to obtain a catalyst.
【００１７】得られた触媒の酸素以外の元素の組成（以
下同じ）はＢｉ20Ｍｏ10であった。The composition of elements other than oxygen in the obtained catalyst (the same applies hereinafter) was Bi 20 Mo 10 .
【００１８】この触媒を反応器に充填し、プロピオンア
ルデヒド０．７容量％、メタノール４．６容量％、窒素
９４．７容量％からなる原料ガスを反応温度２４０℃、
空間速度１０００ｍｌ／ｈｒ／ｍｌ−触媒で供給した。This catalyst was filled in a reactor, and a raw material gas consisting of 0.7% by volume of propionaldehyde, 4.6% by volume of methanol and 94.7% by volume of nitrogen was added at a reaction temperature of 240 ° C.
Space velocity 1000 ml / hr / ml-catalyst feed.
【００１９】１時間経過後の生成物を捕集し、ガスクロ
マトグラフィーで分析したところ、プロピオンアルデヒ
ドの転化率２７．８％、メタクロレインの選択率６７．
４％であった。After 1 hour, the product was collected and analyzed by gas chromatography. As a result, the conversion of propionaldehyde was 27.8% and the selectivity of methacrolein was 67.
4%.
【００２０】実施例２ 実施例１において用いた原料ガスに、窒素の一部を酸素
の含有量が１．０容量％となるように酸素を加えた原料
ガス（プロピオンアルデヒド０．７容量％、メタノール
４．６容量％、窒素９３．７容量％、酸素１．０容量
％）を用いて実施例１と同様に反応を行ったところ、プ
ロピオンアルデヒドの転化率６７．５％、メタクロレイ
ンの選択率８６．６％であった。Example 2 The source gas used in Example 1 was added with oxygen such that a part of nitrogen was added so that the oxygen content was 1.0% by volume (propionaldehyde 0.7% by volume, A reaction was carried out in the same manner as in Example 1 using methanol (4.6% by volume, nitrogen 93.7% by volume, oxygen 1.0% by volume). The rate was 86.6%.
【００２１】実施例３ 実施例１において反応温度を２６０℃に変えた以外は実
施例１と同じ条件で反応を行ったところ、プロピオンア
ルデヒドの転化率３４．３％、メタクロレインの選択率
７３．２％であった。Example 3 The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was changed to 260 ° C., and the conversion of propionaldehyde was 34.3% and the selectivity of methacrolein was 73. It was 2%.
【００２２】実施例４ 硝酸ビスマス２１９．８部に過剰量のアンモニア水を添
加し５分間攪拌した後、濾過・洗浄した（固形物（Ａ−
２））。これとは別に純水１０００部にパラモリブデン
酸アンモニウム４０部及び８５％リン酸０．８部を加え
加熱溶解して（Ｂ−２）液を調製した。Example 4 An excess amount of aqueous ammonia was added to 219.8 parts of bismuth nitrate, and the mixture was stirred for 5 minutes, filtered and washed (solid (A-
2)). Separately from this, 40 parts of ammonium paramolybdate and 0.8 part of 85% phosphoric acid were added to 1000 parts of pure water and dissolved by heating to prepare a solution (B-2).
【００２３】（Ｂ−２）液に固形物（Ａ−２）を加え２
０時間加熱還流後、蒸発乾固した。Solid (A-2) was added to the liquid (B-2), and 2
After heating under reflux for 0 hours, the mixture was evaporated to dryness.
【００２４】得られた固形物を１１０℃で２４時間乾燥
後、空気雰囲気下に５００℃で２時間熱処理したものを
触媒とした。The solid matter obtained was dried at 110 ° C. for 24 hours and then heat-treated in an air atmosphere at 500 ° C. for 2 hours to obtain a catalyst.
【００２５】得られた触媒の組成はＢｉ20Ｍｏ10Ｐ0.3
であった。The composition of the resulting catalyst was Bi 20 Mo 10 P 0.3.
Met.
【００２６】得られた触媒を用いて実施例３と同じ条件
で反応を行ったところ、プロピオンアルデヒドの転化率
３６．５％、メタクロレインの選択率７８．５％であっ
た。When the reaction was carried out using the obtained catalyst under the same conditions as in Example 3, the conversion of propionaldehyde was 36.5% and the selectivity of methacrolein was 78.5%.
【００２７】実施例５〜１１ 実施例４において、８５％リン酸０．８部の替わりに表
１に示される各化合物及び各使用量以外は実施例４に記
載される方法により表２に示した触媒組成を有する各触
媒を調製した。得られた各触媒を用いて、実施例３と同
一条件で反応した。表２に各反応結果を示した。Examples 5 to 11 In Example 4, except that each compound shown in Table 1 and each amount used in place of 0.8 part of 85% phosphoric acid are shown in Table 2 by the method described in Example 4. Each catalyst having different catalyst composition was prepared. Reaction was performed under the same conditions as in Example 3 using each of the obtained catalysts. Table 2 shows the results of each reaction.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】実施例１２ 実施例１において、原料であるプロピオンアルデヒドを
アセトアルデヒドに変更する以外は実施例１と同じ条件
で反応を行ったところ、アセトアルデヒドの転化率１
７．２％、アクロレインの選択率７０．１％であった。Example 12 The reaction was carried out under the same conditions as in Example 1 except that the raw material propionaldehyde was changed to acetaldehyde, and the conversion rate of acetaldehyde was 1
The selectivity was 7.2% and the selectivity for acrolein was 70.1%.
【００３１】比較例１ 実施例１において、（Ｂ−１）液を添加しないでＢｉだ
けからなる比較触媒を調製した。この触媒を用いて、実
施例１と同じ条件で反応したところ、プロピオンアルデ
ヒドの転化率は５．３％であったがメタクロレインは殆
ど得られなかった。Comparative Example 1 In Example 1, a comparative catalyst consisting of Bi alone was prepared without adding the liquid (B-1). When this catalyst was used and reacted under the same conditions as in Example 1, the conversion of propionaldehyde was 5.3%, but methacrolein was scarcely obtained.
【００３２】比較例２ 実施例１において、固形物（Ａ−１）を添加しないでＭ
ｏだけからなる比較触媒を調製した。この触媒を用い実
施例１と同じ条件で反応したところ、プロピオンアルデ
ヒドの転化率１１．９％、メタクロレインの選択率２
５．６％であった。Comparative Example 2 In Example 1, M was added without adding the solid (A-1).
A comparative catalyst consisting only of o was prepared. When a reaction was carried out under the same conditions as in Example 1 using this catalyst, the conversion of propionaldehyde was 11.9% and the selectivity of methacrolein was 2
It was 5.6%.
【００３３】[0033]
【発明の効果】本発明は、ビスマス、モリブデンを含有
する新規な触媒を用い、アセトアルデヒドもしくはプロ
ピオンアルデヒドとメタノールを気相反応させることに
よりアクロレインもしくはメタクロレインを収率高く得
ることができるという優れた効果を有する。INDUSTRIAL APPLICABILITY The present invention has an excellent effect that acrolein or methacrolein can be obtained in high yield by gas phase reaction of acetaldehyde or propionaldehyde with methanol using a novel catalyst containing bismuth and molybdenum. Have.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 27/192 Ｂ０１Ｊ 27/192 Ｘ Ｃ０７Ｃ 45/65 Ｃ０７Ｃ 45/65 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location B01J 27/192 B01J 27/192 X C07C 45/65 C07C 45/65 // C07B 61/00 300 C07B 61/00 300
Claims (2)
ルデヒド及びメタノールのガスを少なくとも原料ガスと
して用い、アセトアルデヒドまたはプロピオンアルデヒ
ドをメタノールと気相接触反応させてアクロレインまた
はメタクロレインを製造するにあたり、下記一般式
（１）で表される触媒を使用することを特徴とするアク
ロレインまたはメタクロレインの製造方法。 【化１】 ＢｉaＭｏbＸcＯd （１） （式中、Ｂｉ、Ｍｏ及びＯはそれぞれビスマス、モリブ
デン及び酸素を示し、Ｘはアルミニウム、珪素、チタ
ン、鉄、コバルト、銀、タングステン、バナジウム及び
リンからなる群より選ばれた少なくとも１種の元素を示
す。但し、ａ、ｂ、ｃ及びｄは各元素の原子比率を表わ
し、ｂ＝１０のときａ＝１〜３０、ｃ＝０〜２０であ
り、ｄは上記各成分の原子価を満足するのに必要な酸素
原子数である。）1. A method of producing acrolein or methacrolein by subjecting acetaldehyde or propionaldehyde to gas phase catalytic reaction of acetaldehyde or propionaldehyde with at least a gas of acetaldehyde or propionaldehyde and methanol as a raw material gas to produce acrolein or methacrolein represented by the following formula A method for producing acrolein or methacrolein, which comprises using the catalyst described above. Embedded image Bi a Mo b X c O d (1) (wherein Bi, Mo and O represent bismuth, molybdenum and oxygen, respectively, and X represents aluminum, silicon, titanium, iron, cobalt, silver, tungsten, At least one element selected from the group consisting of vanadium and phosphorus is shown, provided that a, b, c and d represent the atomic ratio of each element, and when b = 10, a = 1 to 30 and c = 0. Is about 20, and d is the number of oxygen atoms required to satisfy the valences of the above components.)
容量％含有していることを特徴とする請求項１記載のア
クロレインまたはメタクロレインの製造方法。2. A molecular gas containing 0.1 to 10 molecular oxygen.
The method for producing acrolein or methacrolein according to claim 1, wherein the acrolein is contained in a volume percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6448195A JPH08259487A (en) | 1995-03-23 | 1995-03-23 | Production of unsaturated aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6448195A JPH08259487A (en) | 1995-03-23 | 1995-03-23 | Production of unsaturated aldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08259487A true JPH08259487A (en) | 1996-10-08 |
Family
ID=13259460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6448195A Pending JPH08259487A (en) | 1995-03-23 | 1995-03-23 | Production of unsaturated aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08259487A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9828322B2 (en) | 2016-01-28 | 2017-11-28 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta-unsaturated aldehydes over a regenerable anatase titania catalyst |
| US9834501B2 (en) | 2016-01-28 | 2017-12-05 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta—unsaturated aldehydes from methanol and an aldehyde |
-
1995
- 1995-03-23 JP JP6448195A patent/JPH08259487A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9828322B2 (en) | 2016-01-28 | 2017-11-28 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta-unsaturated aldehydes over a regenerable anatase titania catalyst |
| US9834501B2 (en) | 2016-01-28 | 2017-12-05 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta—unsaturated aldehydes from methanol and an aldehyde |
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