WO1986001797A1 - Process for producing unsaturated carboxylic acids - Google Patents
Process for producing unsaturated carboxylic acids Download PDFInfo
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- WO1986001797A1 WO1986001797A1 PCT/JP1985/000523 JP8500523W WO8601797A1 WO 1986001797 A1 WO1986001797 A1 WO 1986001797A1 JP 8500523 W JP8500523 W JP 8500523W WO 8601797 A1 WO8601797 A1 WO 8601797A1
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- unsaturated carboxylic
- element selected
- catalyst
- carboxylic acid
- oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
Definitions
- the present invention relates to a method for producing an unsaturated carboxylic acid by gas-phase catalytic oxidation of an unsaturated aldehyde, and more particularly to a catalyst used in the production.
- An object of the present invention is to provide a method for advantageously producing methacrylic acid from methacrolein, and the present inventors have developed a catalyst for use in the present invention. After diligent research, they found that the above-mentioned drawbacks could be improved, and that a catalyst with activity, selectivity, life, and practicality could be used. The present inventors have found that the present invention can be applied to a method for producing acrylic acid from lain, and have completed the present invention.
- the present invention relates to a process for producing an unsaturated sulfonic acid by subjecting an unsaturated aldehyde to gas-phase catalytic oxidation with molecular oxygen.
- P, 0, V, Cu, Sb, Ag and 0 are phosphorus, molybdenum, vanadium, ⁇ , antimony, silver and oxygen, respectively.
- X represents at least one element selected from the group consisting of potassium, rubidium, cesium, and talium.
- Y is zinc, titanium, chromium, silicon, germanium, zirconium, tin, selene, tungsten, tantalum, tellurium, nickel, At least one element selected from the group consisting of barium, bismuth, arsenic, boron, magnesium, rhodium and palladium Indicate
- i is the number of oxygen atoms required to satisfy the valence of each of the above components.
- a process for producing unsaturated sulfonic acid characterized by using a catalyst represented by the formula:
- unsaturated carboxylic acids can be obtained from unsaturated aldehydes in high yields and high selectivities, and particularly, high catalytic activity over a long period of time.
- the industrial value is extremely large since the maintenance is maintained.
- the raw material compounds used for preparing the catalyst a combination of nitrates, carbonates, ammonium salts, halogenated compounds, oxides, etc. of each element can be used. Wear .
- the catalyst used in the method of the present invention is extremely effective even without a carrier, it is difficult to use silica, alumina, silica, alumina, silica paper, and the like. It can be used by being supported on an active carrier or diluted with it.
- the catalyst of the present invention is generally used in a fixed bed, but can also be used in a fluidized bed.
- concentration of unsaturated aldehydes in the raw material gas can be varied in a wide range, but a suitable volume is ⁇ to 20%, especially 3 to 10%. No.
- the raw material unsaturated aldehyde may contain a small amount of impurities such as water and lower saturated aldehyde, and these impurities do not substantially affect the reaction.
- the oxygen concentration in the raw material gas is defined by the molar ratio to the unsaturated aldehyde, and this value is preferably 0.3 to 4, particularly preferably 0.4 to 2.5.
- the raw material gas may be diluted by adding an inert gas such as nitrogen, steam, or carbon dioxide.
- the reaction pressure is preferably from normal pressure to several atmospheres.
- the reaction temperature can be selected in the range of 230 to 450, but it is particularly preferably in the range of 250 to 400 ° C.
- parts represent parts by weight
- selectivity of unsaturated carboxylic acid is expressed by the number of moles of unsaturated carboxylic acid generated relative to the number of moles of unsaturated aldehyde reacted. Indicates the ratio (percent).
- Ammonium paramolybdate ⁇ 100 parts, metavanadium 2.8 parts of ammonium phosphate and 4.8 parts of potassium nitrate were dissolved in pure 400 parts.
- 6.5 parts of 85% phosphoric acid dissolved in 50 parts of pure water was added, followed by 3.1 parts of tantalum oxide and 6 parts of antimony trioxide.
- Nine parts were added and the mixture was ripened and stirred.
- the reactor is charged with this catalyst, and a mixed gas of 5% of methacrolein, 10% of oxygen, 30% of steam, and 55% of nitrogen (by volume) is reacted at 290 ° G
- the contact time was 3.6 seconds.
- the reaction rate of methacrolein was 84.1% and the selectivity of methacrylic acid was 8 8 It was 3%.
- Example 2 The following comparative catalysts were adjusted according to Example 1, and reacted under the same conditions as in Example 1 to obtain the results shown in Table 1-2.
- Example 2 Using the catalyst prepared in Example 1, a mixed gas of acrolein 5%, oxygen 10%, steam 30%, and nitrogen 55% (volume%) was reacted at a reaction temperature of 29%. When introduced into the catalyst layer at 0 ° C and a contact time of 3.6 seconds, the reaction rate of acrolein was 92.2% and the selectivity of acrylic acid was 94.1%. .
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A novel catalyst extremely useful for gas phase oxidation reaction of an unsaturated aldehyde, particularly acrolein or methacrolein, to a corresponding unsaturated carboxylic acid, particularly acrylic or methacrylic acid, which is represented by the general formula: PaMobVcCudSbeAgfXgYhOi, wherein X represents at least one element selected from among potassium, rubidium, cesium, and thallium, Y represents at least one element selected from among zinc, sulfur, chromium, silicon, germanium, zirconium, tin, selenium, tungsten, tantalum, tellurium, nickel, barium, bismuth, arsenic, boron, magnesium, rhodium, and palladium, a, b, c, d, e, f, g, h, and i represent atomic ratios of respective elements, provided that a = 0.3 to 3 , c = 0.01 to 3, d = 0.01 to 3, e = 0.01 to 3, f = 0.001 to 2, g = 0.01 to 3 and h = 0.001 to 8, when b = 12, and i represents the number of oxygen atoms necessary for satisfying the valence of each component.
Description
P T/JP85/00523 明 細 書 不飽和 カ ルポ ン 酸の製造法 技術分野 P T / JP85 / 00523 Description Production method of unsaturated carboxylic acid
本発明 は不飽和 アルデ ヒ ド の気相接触酸化 に よ る不飽 和 カ ルポ ン酸の製造法 、 さ ら に 詳細 に はそ の際 に 使用 す る触媒 に 関するもので ある 。 背景技術 The present invention relates to a method for producing an unsaturated carboxylic acid by gas-phase catalytic oxidation of an unsaturated aldehyde, and more particularly to a catalyst used in the production. Background art
従来、 不飽和 アルデ ヒ ド を気相接触酸化 し て 相当 す る 不飽和 力 ルポ ン酸を製造す る方法 に 関 し て 、 極め て 数多 く の特許が提案.さ れて い る 。. こ れ ら は主 と し て ァ ク ロ レ イ ン か ら ア ク リ ル酸を製造す る方法を重点 と す る も ので あ り 、 そ こ に提案さ れて い る触媒を メ タ ク リ ル酸製造用 と し て 使用 す る と副反応が大き い た め選択率が低 く 、 ま た寿命が短か く 実用 的でなかっ た 。 Conventionally, a large number of patents have been proposed for a method for producing a corresponding unsaturated sulfonic acid by subjecting an unsaturated aldehyde to gas phase catalytic oxidation. These are mainly focused on the method of producing acrylic acid from acrolein, and the catalysts proposed there are used as meta-materials. When used for the production of crylic acid, the selectivity was low due to a large side reaction, and the service life was too short to be practical.
一方 、 メ タ ク ロ レ イ ン か ら メ タ ク リ ル酸を製造す る方 法 に 関 し て も多数の触媒が提案'さ れて お り 、 例 え ば On the other hand, many catalysts have been proposed for a method for producing methacrylic acid from methacrolein, for example,
P M o V系触媒 と し て 特公昭 5 3 — 1 2 4 9 5号 、 同 No. 53-124,955 as PMO catalyst
5 6 — 4 8 4 9 7号 、 同 5 5 — 1 9 2 0 6号、 同 5 9 — 2 4 1 4 0号 、 同 5 2 — 3 Ί 3 2 7 号'、 特開 昭 4 9 一 5 6 — 4 8 4 9 7, 5 5 — 9 2 6 6, 5 9 — 2 4 1 4 0, 5 2 — 3 Ί 3 2 7 ′, JP-A-49 1
1 2 6 6 6号な ど多数が知 ら れて い る が 、 いず れも 、 反応成績が充分でな かっ た り 、 触媒活性の経時低下が 大 き かっ た り 、 反応温 が高すぎた り の欠点を有 し 、 工業
触媒 と し て の使用 に際 し て は更 に改良が望ま れて い るの が現状であ る 。 発明 の 開示 Many are known, such as No. 1266666, but in any case, the reaction results are not sufficient, the catalyst activity decreases significantly over time, and the reaction temperature is too high. With many disadvantages, At present, further improvement is desired for use as a catalyst. Disclosure of invention
本発明 はメ タ ク ロ レ イ ン か ら メ タ ク リ ル酸を有利 に 製 造す る方法の提供を 目 的 と し て お り 、 本発明者 ら は こ 、 で用 い る触媒 につ い て鋭意研究 し た と こ ろ 、 上記の欠点 を改良 し 、 活性、 選択性、 寿命 と も に実用 性の髙ぃ触媒 を見い だ し 、 さ ら に 、 こ の触媒が ァ ク ロ レ イ ン か ら ァ ク リ ル酸を製造す る方法 に も適用 し得る こ と を見い 出 し 、 本発明を 完成す る に到っ た 。 An object of the present invention is to provide a method for advantageously producing methacrylic acid from methacrolein, and the present inventors have developed a catalyst for use in the present invention. After diligent research, they found that the above-mentioned drawbacks could be improved, and that a catalyst with activity, selectivity, life, and practicality could be used. The present inventors have found that the present invention can be applied to a method for producing acrylic acid from lain, and have completed the present invention.
本発明 は不飽和 アルデ ヒ ド を分子状酸素で気相接触酸 化 し 不飽和 力 ルポ ン酸を製造す る に あ た り 、 ' 一般式 The present invention relates to a process for producing an unsaturated sulfonic acid by subjecting an unsaturated aldehyde to gas-phase catalytic oxidation with molecular oxygen.
P a M 0 l) V c C S b e A g f X g Y h O i P a M 0 l) V c CS b e A gf X g Y h O i
( こ こで式中 P , 0 , V , C u , S b , A g及び 0 はそ れぞれ リ ン 、 モ リ プデ ン 、 バナ ジ ウ ム 、 鋦 、 ア ン チモ ン 、 銀及び酸素を示 し 、 Xは カ リ ウ ム 、 ル ビ ジ ゥ ム 、 セ シ ウ ム及び タ リ ウ ム か ら な る群 よ り 選ばれた 少 な く と も " 1 種以上の元素を示 し 、 Yは亜鉛 、 ィ 才 ゥ 、 ク ロ ム 、 ケ ィ 素、 ゲルマ ニ ウ ム 、 ジル コ ニ ウ ム 、 スズ 、 セ レ ン 、 タ ングス テ ン 、 タ ン タ ル 、 テルル、 ニ ッ ケル 、 バ リ ウ ム 、 ビ スマ ス 、 ヒ 素、 ホ ウ 素 、 マ グネ シ ウ ム 、 ロ ジ ウ ム及びパラ ジ ウ ムか ら な る群よ り 選ばれた少な く と も 1 種以上の元素を示す 。
た だ し 、 a , b , c , d , e , ΐ , g , h及び i は各 元素の原子比率を表わ し 、 b = 1 2の と き a = 0 . 3 〜 3 , c = 0. C 〜 3 , d = 0. 0 1 〜 3 , e = 0 . 0 ト 3 , f = 0 . 0 0 ト 2 , g = 0 . 0 1 〜 3 , = 0. 0 0 1 〜 8で あ り i 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 。 ） (Where P, 0, V, Cu, Sb, Ag and 0 are phosphorus, molybdenum, vanadium, 鋦, antimony, silver and oxygen, respectively. And X represents at least one element selected from the group consisting of potassium, rubidium, cesium, and talium. , Y is zinc, titanium, chromium, silicon, germanium, zirconium, tin, selene, tungsten, tantalum, tellurium, nickel, At least one element selected from the group consisting of barium, bismuth, arsenic, boron, magnesium, rhodium and palladium Indicate However, a, b, c, d, e, ΐ, g, h and i represent the atomic ratio of each element, and when b = 12, a = 0.3 to 3 and c = 0 C -3, d = 0.01 to 3, e = 0.0 to 3, f = 0.0 to 2, g = 0, 0 to 3, = 0.0 to 1 to 8. Where i is the number of oxygen atoms required to satisfy the valence of each of the above components. )
で表わ さ れる触媒を使用 する こ と を特徴 と する不飽和 力 ルポ ン酸の製造方法で あ る 。 A process for producing unsaturated sulfonic acid, characterized by using a catalyst represented by the formula:
本発明 の方法 に よ れば 、 不飽和 アルデ ヒ ドか ら不飽和 カ ルポ ン酸を髙収率、 髙選択率で得る こ と が可 能であ り 、 特に 長期 に わ たっ て 高い触媒活性が維持さ れる ので 工業 的価値は極め て 大き い 。 According to the method of the present invention, unsaturated carboxylic acids can be obtained from unsaturated aldehydes in high yields and high selectivities, and particularly, high catalytic activity over a long period of time. The industrial value is extremely large since the maintenance is maintained.
本発明 に 用 い ら れる触媒を製造す る方法 と し て は特殊 な方法 に 限定 す る必要は な く 、 成分の著 し い儷在を伴わ な い限 り 、 従来か ら よ く 知 ら れて い る蒸発乾固法 、 沈殿 法等の種々 の方法を用 い る こ と がで き る 。 It is not necessary to limit the method for producing the catalyst used in the present invention to a special method, and it is well known that the method does not involve a significant amount of components. Various methods such as the evaporation to dryness method and the precipitation method can be used.
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 ゥ ム塩、 ハ ロ ゲ ン化物 、 酸化物 な ど を組合せ て 使用 す.る こ と がで き る 。 As the raw material compounds used for preparing the catalyst, a combination of nitrates, carbonates, ammonium salts, halogenated compounds, oxides, etc. of each element can be used. Wear .
本発明 の方法で用 い る触媒 は無担体で も極め て 有効 で あ る が 、 シ リ カ 、 アル ミ ナ 、 シ リ カ ♦ アル ミ ナ 、 シ リ コ ン カ ー パ イ 卜 等の不活性担体に 担持さ せ る か 、 あ る い は こ れで希釈 し て用 い る こ と もでき る 。 Although the catalyst used in the method of the present invention is extremely effective even without a carrier, it is difficult to use silica, alumina, silica, alumina, silica paper, and the like. It can be used by being supported on an active carrier or diluted with it.
本発明 の触媒は一般 に は固定床で用 い ら れる が流動床 でも使用で き る 。
原料ガ ス中 の不飽和 アルデ ヒ ド の濃度 は広い範囲で変 え る こ と ができ る が 、 容量で Ί 〜 2 0 % が適当 で あ り 、 特 に 3 〜 1 0 %が好 ま し い 。 The catalyst of the present invention is generally used in a fixed bed, but can also be used in a fluidized bed. The concentration of unsaturated aldehydes in the raw material gas can be varied in a wide range, but a suitable volume is 容量 to 20%, especially 3 to 10%. No.
原料不飽和 アルデ ヒ ド は水 、 低級飽和 アルデ ヒ ド等の 不純物 を少量含んで いて も よ く 、 こ れ ら の不純物 は反応 に実質的な影響を与えない 。 The raw material unsaturated aldehyde may contain a small amount of impurities such as water and lower saturated aldehyde, and these impurities do not substantially affect the reaction.
酸素源 と し て は空気を用 い る の が経済的で あ るが 、 必 要 ^: ら ば純酸素で富化 し た空気も用 い得る 。 It is economical to use air as an oxygen source, but if necessary ^: air enriched with pure oxygen can be used if necessary.
原料ガス中 の酸素濃度 は不飽和 ア ルデ ヒ ド に対す る モ ル比で規定さ れ、 こ の値 は 0 . 3 〜 4 、 特 に 0 . 4 〜 2 . 5 が好 ま し い 。 The oxygen concentration in the raw material gas is defined by the molar ratio to the unsaturated aldehyde, and this value is preferably 0.3 to 4, particularly preferably 0.4 to 2.5.
原料ガス は窒素、 水蒸気 、 炭酸ガ ス等の不活性ガス を 加えて 希釈 し て も よ い 。 反応圧力 は常圧か ら 数気圧 ま で- が よ い 。 反応温度は 2 3 0 〜 4 5 0 で の範囲 で選ぶ こ と がで き るが 、 特に 2 5 0 〜 4 0 0 °C が好 ま し い 。 発明を実施す る た め の最良の形態 The raw material gas may be diluted by adding an inert gas such as nitrogen, steam, or carbon dioxide. The reaction pressure is preferably from normal pressure to several atmospheres. The reaction temperature can be selected in the range of 230 to 450, but it is particularly preferably in the range of 250 to 400 ° C. BEST MODE FOR CARRYING OUT THE INVENTION
以下 に実施例及び比較例 を挙げて本発明 の方法を更 に 詳 し く 説明 す る 。 Hereinafter, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例 に お ける部 は重量部を表わ し 、 不飽和 カ ルポ ン 酸選択率は不飽和 アルデ ヒ ド の反応 し た モル数 に 対す る 生成 し た不飽和 カ ルポ ン酸のモル数の割合 （ パ ー セ ン 卜 ） を表わ す 。 In the examples, parts represent parts by weight, and the selectivity of unsaturated carboxylic acid is expressed by the number of moles of unsaturated carboxylic acid generated relative to the number of moles of unsaturated aldehyde reacted. Indicates the ratio (percent).
実施例 1 Example 1
パラ モ リ ブデ ン酸 ア ン モ ニ ゥ ム Ί 0 0 部 、 メ タ バ ナジ
ン酸 ア ン モ ニ ゥ ム 2 . 8部及び硝酸 カ リ ウ ム 4 . 8部を 純粋 4 0 0部 に 溶解 し た 。 こ れ に 8 5 %リ ン酸 6. 5部 を純水 5 0部 に 溶解 し た も の を加 え 、 さ ら に 酸化 タ ン タ ル 3 . 1 部及び三酸化 ア ン チモ ン 6 . 9部を加 え加熟攛 拌 し た 。 Ammonium paramolybdate Ί 100 parts, metavanadium 2.8 parts of ammonium phosphate and 4.8 parts of potassium nitrate were dissolved in pure 400 parts. To this, 6.5 parts of 85% phosphoric acid dissolved in 50 parts of pure water was added, followed by 3.1 parts of tantalum oxide and 6 parts of antimony trioxide. Nine parts were added and the mixture was ripened and stirred.
つ ぎ に 、 硝酸銅 9 . 1 部を純水 1 0 0部 に 溶解 し た も の 及び硝酸銀 0. 8部を純水 5 0部 に 溶解 し た も の を加 え 、 混合液を加熱 し な が ら 蒸発乾固 し た 。 得 ら れた 固形 物 を 1 3 0 で 1 6時間乾燥後加圧成形 し 、 空気流通下 に 3 8 0 °Cで 5時間熟処理 し た も の を触媒 と し て 用 いた 。 Next, 9.1 parts of copper nitrate dissolved in 100 parts of pure water and 0.8 part of silver nitrate dissolved in 50 parts of pure water were added, and the mixture was heated. It evaporated to dryness. The obtained solid was dried at 130 for 16 hours, press-molded, and aged at 38 ° C. for 5 hours under an air flow, and used as a catalyst.
得 ら れ fc触媒の酸素以外の元素の組成 （ 以下同 じ ） は P 12M 0 12V 05 C u 08S b 1 A g 01K 1 T a 03で あつ た 。 Resulting et Re compositions of elements other than oxygen in the fc catalyst (hereinafter the same) was filed at P 12 M 0 12 V 05 C u 08 S b 1 A g 01 K 1 T a 03.
本触媒を反応器 に充旗 し 、 メ タ ク ロ レ イ ン 5 % 、 酸素 1 0 % 、 水蒸気 3 0 % 、 窒素 5 5 % ( 容量％ ) の混合ガ ス を反応温度 2 9 0 °G、 接触時間 3 . 6秒で通 じ た 。 生 成物 を捕集 し ガ ス ク ロ マ 卜 グラ フ ィ 一 で分析 し た と こ ろ 、 メ タ ク ロ レ イ ン反応率 8 4 . 1 %、 メ タ ク リ ル酸選択率 8 8 . 3 %で あっ た 。 The reactor is charged with this catalyst, and a mixed gas of 5% of methacrolein, 10% of oxygen, 30% of steam, and 55% of nitrogen (by volume) is reacted at 290 ° G The contact time was 3.6 seconds. When the product was collected and analyzed by gas chromatography, the reaction rate of methacrolein was 84.1% and the selectivity of methacrylic acid was 8 8 It was 3%.
同一条件で約 Ί 0 0 0時簡反応を継続 し た と こ ろ メ タ ク ロ レ イ ン反応率 8 3 . 8 %、 メ タ ク リ ル酸選択率 Under the same conditions, the reaction was continued for about 0.000 hours.
8 8 . 5 %で あっ た 。 It was 88.5%.
実施例 2〜 Ί 5 Example 2 to Ί5
実施例 Ί に 準 じ て 表 一 Ί の各触媒を調整 し 、 実施例 1 と 同一条件で反応 し 表 一 1 の結果を得た 。
Each catalyst shown in Table 1 was prepared according to Example II, and reacted under the same conditions as in Example 1 to obtain the results shown in Table 11.
比較例 1 〜 3 Comparative Examples 1 to 3
実施例 1 に準 じ て 次の各比較触媒を調整 し 、 実施例 1 と 同一条件で反応 し 表一 2 の結果を得た 。
The following comparative catalysts were adjusted according to Example 1, and reacted under the same conditions as in Example 1 to obtain the results shown in Table 1-2.
2 Two
実施例 1 6 Example 16
実施例 1 で調整 し た 触媒を用 い て 、 ァ ク ロ レ イ ン 5 %、 酸素 1 0 % 、 水蒸気 3 0 % 、 窒素 5 5 % ( 容量％ ) の混 合 ガ ス を反応温度 2 9 0 °C、 接触時間 3 . 6秒で触媒層 に 導入 し た と こ ろ 、 ァ ク ロ レ イ ン反応率 9 2 , 2 %、 ァ ク リ ル酸選択率 9 4 . 1 %で あっ た 。 Using the catalyst prepared in Example 1, a mixed gas of acrolein 5%, oxygen 10%, steam 30%, and nitrogen 55% (volume%) was reacted at a reaction temperature of 29%. When introduced into the catalyst layer at 0 ° C and a contact time of 3.6 seconds, the reaction rate of acrolein was 92.2% and the selectivity of acrylic acid was 94.1%. .
産業上の利用 可 能性 Industrial applicability
本発明 に よ り 、 空気酸化 に よ る ァ ク ロ レ イ ン又 は メ タ ク ロ レ イ ン か ら ア ク リ ル酸又 は メ タ ク リ ル酸へ の気相酸 化反応 に 極め て 有用 な触媒が提供さ れる 。
Advantageous Effects of Invention According to the present invention, it is extremely suitable for the gas phase oxidation reaction of acrolein or methacrolein to acrylic acid or methacrylic acid by air oxidation. Thus, a useful catalyst is provided.
Claims
請求の範囲 不飽和 アルデ ヒ ド を分子状酸素で気相接触酸化 し 不飽 和 カ ルボ ン酸を製造 する に あた り 、 Claims In producing gas-phase catalytically oxidized unsaturated aldehyde with molecular oxygen to produce unsaturated carboxylic acid,
一般式 General formula
P a M o b V c C u d S b e A g f X g Y h O i P a M ob b V c C u d S b e A g f X g Y h O i
( こ こで式中 P , M o , V , C u , S b , A g及び 0 はそ れぞれ リ ン 、 モ リ ブデン 、 バ ナ ジ ウ ム 、 鋇 、 ア ン チモ ン 、 銀及び酸素を示 し 、 Xは カ リ ウ ム 、 ル ビ ジ ゥ ム 、 セ シ ウ ム及び タ リ ウ ム か ら な る群よ り 選ばれ た少 な く と も 1 種以上の元素を示 し 、 Yは亜鉛 、 ィ 才ゥ 、 ク ロ ム 、 ケ ィ 素 、 ゲルマニ ウ ム 、 ジル コ ニ ウ ム 、 スズ、 セ レ ン 、 タ ングス テ ン 、 タ ン タ ル 、 テルル 、 ニ ッ ケル 、 . バ リ ウ ム 、 ビスマ ス 、 ヒ 素、 ホ ウ素、 マ グネ シ ウ ム 、 ロ ジ ウ ム及びパラ ジ ウ ムか ら な る群 よ り 選ばれた少な く と も 1 種以上の元素を示す 。 (Where P, Mo, V, Cu, Sb, Ag and 0 are phosphorus, molybdenum, vanadium, 、, antimony, silver and X represents oxygen, and X represents at least one element selected from the group consisting of potassium, rubidium, cesium, and thallium. , Y is zinc, copper, chromium, silicon, germanium, zirconium, tin, selen, tungsten, tantalum, tellurium, nickel,. At least one element selected from the group consisting of barium, bismuth, arsenic, boron, magnesium, rhodium and palladium; Show.
た だ し 、 a， b , c , d , e , f , g , h及び i は各 元素の原子比率を表わ し 、 b = 1 2の と き a = 0. 3 〜 3 , c = 0. 0 1 〜 3 , d = 0. 0 1 〜 3 , e = However, a, b, c, d, e, f, g, h, and i represent the atomic ratio of each element. When b = 12, a = 0.3 to 3 and c = 0 0 1 to 3, d = 0. 0 1 to 3, e =
0. 0 Ί 〜 3 ， f = 0. 0 0 1 〜 2 , g = 0. 0 ト 0.0 Ί to 3, f = 0.01 to 2, g = 0.0
3 , h = 0. 0 0 1 〜 8で あ り 、 i 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 。 ） 3, h = 0.001 to 8, and i is the number of oxygen atoms required to satisfy the atomic valence of each of the above components. )
で表わ される触媒を使用 する こ と を特徴 と する不飽和 力 ルボ ン酸の製造法 。
A process for producing unsaturated carboxylic acid, characterized by using a catalyst represented by the formula:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59/197692 | 1984-09-20 | ||
| JP19769284A JPS6176436A (en) | 1984-09-20 | 1984-09-20 | Production of unsaturated carboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1986001797A1 true WO1986001797A1 (en) | 1986-03-27 |
Family
ID=16378762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1985/000523 WO1986001797A1 (en) | 1984-09-20 | 1985-09-19 | Process for producing unsaturated carboxylic acids |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS6176436A (en) |
| WO (1) | WO1986001797A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2811243A1 (en) * | 2000-07-04 | 2002-01-11 | Atofina | New solid compositions comprising a multimetallic oxide based on molybdenum useful for transformation of acrolein to acrylic acid by a redox reaction |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000072964A1 (en) * | 1999-05-27 | 2000-12-07 | Mitsubishi Rayon Co., Ltd. | Catalyst for methacrylic acid production and process for producing methacrylic acid |
| JP4764174B2 (en) * | 2006-01-16 | 2011-08-31 | 三菱レイヨン株式会社 | Palladium-containing catalyst for liquid phase oxidation, method for producing the same, and method for producing α, β-unsaturated carboxylic acid |
| JP6452169B2 (en) * | 2016-09-14 | 2019-01-16 | 日本化薬株式会社 | Catalyst for producing acrylic acid and method for producing acrylic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS552619A (en) * | 1978-06-21 | 1980-01-10 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and catalyst |
| JPS55122734A (en) * | 1979-03-16 | 1980-09-20 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and its catalyst |
| JPS57177347A (en) * | 1981-04-22 | 1982-11-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidizing catalyst and preparation thereof |
| JPS5867643A (en) * | 1981-10-15 | 1983-04-22 | Mitsubishi Rayon Co Ltd | Preparation of unsaturated acid |
| JPS5879545A (en) * | 1981-11-04 | 1983-05-13 | Mitsubishi Rayon Co Ltd | Calcining method for phosphorus-molybdenum catalyst |
-
1984
- 1984-09-20 JP JP19769284A patent/JPS6176436A/en active Pending
-
1985
- 1985-09-19 WO PCT/JP1985/000523 patent/WO1986001797A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS552619A (en) * | 1978-06-21 | 1980-01-10 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and catalyst |
| JPS55122734A (en) * | 1979-03-16 | 1980-09-20 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and its catalyst |
| JPS57177347A (en) * | 1981-04-22 | 1982-11-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidizing catalyst and preparation thereof |
| JPS5867643A (en) * | 1981-10-15 | 1983-04-22 | Mitsubishi Rayon Co Ltd | Preparation of unsaturated acid |
| JPS5879545A (en) * | 1981-11-04 | 1983-05-13 | Mitsubishi Rayon Co Ltd | Calcining method for phosphorus-molybdenum catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2811243A1 (en) * | 2000-07-04 | 2002-01-11 | Atofina | New solid compositions comprising a multimetallic oxide based on molybdenum useful for transformation of acrolein to acrylic acid by a redox reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6176436A (en) | 1986-04-18 |
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