JP2759376B2 - Method for producing methacrolein and methacrylic acid - Google Patents
Method for producing methacrolein and methacrylic acidInfo
- Publication number
- JP2759376B2 JP2759376B2 JP2249056A JP24905690A JP2759376B2 JP 2759376 B2 JP2759376 B2 JP 2759376B2 JP 2249056 A JP2249056 A JP 2249056A JP 24905690 A JP24905690 A JP 24905690A JP 2759376 B2 JP2759376 B2 JP 2759376B2
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- oxygen
- catalyst
- isobutane
- parts
- 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 - Fee Related
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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はイソブタンを分子状酸素により気相接触酸化
して、メタクロレイン及びメタクリル酸を製造する方法
に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing methacrolein and methacrylic acid by subjecting isobutane to gas-phase catalytic oxidation with molecular oxygen.
従来、イソブチレンのような不飽和炭化水素を原料と
して、気相接触酸化によりメタクロレイン及びメタクリ
ル酸を製造する方法については多くの提案がなされてい
る。Hitherto, many proposals have been made on a method for producing methacrolein and methacrylic acid by gas-phase catalytic oxidation using an unsaturated hydrocarbon such as isobutylene as a raw material.
しかしながら、イソブタンのような飽和炭化水素を気
相接触酸化してメタクロレイン及びメタクリル酸を製造
する方法に関しては、イソブタンが反応性に乏しいた
め、それ程多くは提案されていない。However, as to a method for producing methacrolein and methacrylic acid by subjecting a saturated hydrocarbon such as isobutane to gas-phase catalytic oxidation, not so much is proposed because isobutane has poor reactivity.
イソブタンからメタクロレイン及びメタクリル酸を一
段酸化によつて製造する方法として、特開昭55−62041
号公報には、モリブデン、アンチモン、リンと酸素から
なる触媒を用いて、イソブタンと酸素からメタクロレイ
ンとメタクリル酸を製造する方法が提案されている。A method for producing methacrolein and methacrylic acid from isobutane by one-step oxidation is disclosed in JP-A-55-62041.
In Japanese Patent Application Laid-Open Publication No. H11-264, a method for producing methacrolein and methacrylic acid from isobutane and oxygen using a catalyst comprising molybdenum, antimony, phosphorus and oxygen is proposed.
また、特開昭63−145249号公報、特開平２−42032号
公報にはリンまたはヒ素を中心元素としモリブデン及び
バナジウムを含むヘテロポリ酸またはその塩を触媒とし
て用いて、イソブタンと酸素からメタクロレイン及びメ
タクリル酸を製造する方法が提案されている。Also, JP-A-63-145249 and JP-A-2-42032 disclose methacrolein from isobutane and oxygen using a heteropolyacid containing phosphorus or arsenic as a central element and containing molybdenum and vanadium or a salt thereof as a catalyst. A method for producing methacrylic acid has been proposed.
以上の方法は一般的に活性及び選択性が低い欠点を有
し、改良が望まれている。The above methods generally have the drawback of low activity and selectivity, and improvements are desired.
本発明者らは、イソブタンの構造に着目して反応性を
検討した結果、イソブタンを活性化させるには触媒にあ
る程度の酸量及び酸強度を持たせることが必要であるこ
とを見い出し、本発明を完成させるに至つた。The present inventors have studied the reactivity by focusing on the structure of isobutane, and as a result, have found that it is necessary to impart a certain amount of acid and acid strength to the catalyst in order to activate isobutane. Was completed.
本発明はイソブタンからメタクロレイン及びメタクリ
ル酸を有利に製造する方法の提供を目的としている。An object of the present invention is to provide a method for advantageously producing methacrolein and methacrylic acid from isobutane.
本発明はイソブタンを分子状酸素を用いて気相接触酸
化し、メタクロレイン及びメタクリル酸を製造するにあ
たり、 一般式 PaMobVcXdYeZfOg （式中P,Mo,V及びＯはそれぞれリン、モリブデン、バナ
ジウム及び酸素をあらわし、Ｘはルテニウム、オスミウ
ム及びイリジウムからなる群より選ばれた少なくとも１
種の元素、Ｙはカリウム、ルビジウム、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種の元素、
Ｚはゲルマニウム、ヒ素、アンチモン、ホウ素、セレ
ン、テルル、ビスマス、鉄、亜鉛、クロム、セリウム、
ジルコニウム、銅、ニツケル、コバルト、マンガン、ガ
リウム、ランタン、カルシウム、ストロンチウム、バリ
ウム、銀及びロジウムからなる群より選ばれた少なくと
も１種の元素を示す。ただし、a,b,c,d,e,f及びｇは各
元素の原子比率を表わし、ｂ＝12のときａ＝0.5〜６、
ｃ＝0.1〜３、ｄ＝0.005〜0.5、ｅ＝0.01〜２、ｆ＝０
〜５であり、ｇは前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。）で表される組成を有する触媒
を使用することを特徴とするメタクロレイン及びメタク
リル酸の製造法である。In the present invention, when isobutane is subjected to gas-phase catalytic oxidation using molecular oxygen to produce methacrolein and methacrylic acid, a general formula P a Mo b V c X d Y e Z f O g (where P, Mo, V and O represent phosphorus, molybdenum, vanadium and oxygen, respectively, and X is at least one selected from the group consisting of ruthenium, osmium and iridium.
A species element, Y is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium;
Z is germanium, arsenic, antimony, boron, selenium, tellurium, bismuth, iron, zinc, chromium, cerium,
It represents at least one element selected from the group consisting of zirconium, copper, nickel, cobalt, manganese, gallium, lanthanum, calcium, strontium, barium, silver and rhodium. However, a, b, c, d, e, f and g represent the atomic ratio of each element, and when b = 12, a = 0.5 to 6,
c = 0.1-3, d = 0.005-0.5, e = 0.01-2, f = 0
And g is the number of oxygen atoms necessary to satisfy the valence of each component. A method for producing methacrolein and methacrylic acid, comprising using a catalyst having a composition represented by the following formula:
触媒を調製するための元素の原料としては、酸化物あ
るいは強熱することにより酸化物になり得る塩化物、硫
酸塩、硝酸塩、アンモニウム塩、炭酸塩、水酸化物また
はそれらの混合物が好ましい。As a raw material of an element for preparing the catalyst, an oxide or a chloride, a sulfate, a nitrate, an ammonium salt, a carbonate, a hydroxide, or a mixture thereof, which can be converted to an oxide when heated, is preferable.
触媒の調製に際しては、蒸発乾固法、沈殿法、酸化物
混合法等の既知の方法を用いることができる。In preparing the catalyst, known methods such as an evaporation to dryness method, a precipitation method, and an oxide mixing method can be used.
触媒成分は、担体に担持させて用いることができる。
担体としては、例えばシリカ、アルミナ、シリカ・アル
ミナ、マグネシア等が用いられる。The catalyst component can be used by being supported on a carrier.
As the carrier, for example, silica, alumina, silica / alumina, magnesia and the like are used.
本発明による触媒を気相接触酸化に用いる場合に、原
料物質であるイソブタンは不活性ガスで希釈して用いる
ことが好ましい。また未反応イソブタンは回収して再度
使用できる。When the catalyst according to the present invention is used for gas phase catalytic oxidation, it is preferable to use isobutane as a raw material diluted with an inert gas. Unreacted isobutane can be recovered and reused.
酸素源としては純酸素ガスでも空気でもよいが、工業
的には空気が有利である。Pure oxygen gas or air may be used as the oxygen source, but air is industrially advantageous.
反応を実施する際の供給原料ガス中の酸素濃度は広い
範囲で変えられるが、好ましくは１〜40容量％である。The oxygen concentration in the feed gas at the time of carrying out the reaction can be varied over a wide range but is preferably 1 to 40% by volume.
反応圧力は常圧から数気圧まで、反応温度は250〜450
℃の範囲で変えることができる。Reaction pressure is from normal pressure to several atmospheres, reaction temperature is 250-450
It can be changed in the range of ° C.
反応は流動床でも固定床でも実施できる。 The reaction can be carried out in a fluidized bed or a fixed bed.
以下、本発明による触媒の調製法及びそれを用いての
反応例を具体的に説明する。Hereinafter, a method for preparing a catalyst according to the present invention and a reaction example using the same will be specifically described.
実施例中、イソブタンの反応率、生成するメタクロレ
イン及びメタクリル酸の選択率は以下のように定義され
る。In the examples, the conversion of isobutane and the selectivity of methacrolein and methacrylic acid to be formed are defined as follows.
下記実施例、比較例中の部は重量部であり、分析はガ
スクロマトグラフイーによつた。 Parts in the following Examples and Comparative Examples are parts by weight, and analysis was performed by gas chromatography.
実施例１ モリブデン酸アンモニウム100部、メタバナジン酸ア
ンモニウム2.76部及び硝酸カリウム3.34部を純水100部
に溶解した。これに65％リン酸5.44部を純水10部に溶解
したものを加え、撹拌しながら95℃に昇温した。次に塩
化ルテニウム0.23部を純水10部に溶解したものを加え、
混合液を加熱撹拌しながら蒸発乾固した。得られた固型
物を130℃で16時間乾燥後、加圧成型し、空気流通下に3
80℃で５時間熱処理したものを触媒として用いた。Example 1 100 parts of ammonium molybdate, 2.76 parts of ammonium metavanadate and 3.34 parts of potassium nitrate were dissolved in 100 parts of pure water. A solution prepared by dissolving 5.44 parts of 65% phosphoric acid in 10 parts of pure water was added thereto, and the temperature was raised to 95 ° C. with stirring. Next, a solution prepared by dissolving 0.23 part of ruthenium chloride in 10 parts of pure water is added,
The mixture was evaporated to dryness while heating and stirring. The obtained solid was dried at 130 ° C. for 16 hours, molded under pressure, and dried under air circulation for 3 hours.
A material heat-treated at 80 ° C. for 5 hours was used as a catalyst.
得られた触媒の酸素以外の元素の組成（以下同じ）は
P1Mo12V0.5Ru0.02Ｋ0.7であつた。The composition of elements other than oxygen in the obtained catalyst (the same applies hereinafter)
P 1 Mo 12 V 0.5 Ru 0.02 K 0.7 .
本触媒を反応器に充填し、イソブタン10％、酸素16.8
％、水蒸気10％、窒素63.2％（容量％）の混合ガスを反
応温度320℃、接触時間2.4秒で通じた。生成物を捕集
し、ガスクロマトグラフイーで分析したところ、イソブ
タンの反応率11.2％、メタクロレインの選択率12.1％、
メタクリル酸の選択率54.0％であつた。This catalyst is charged into a reactor, isobutane 10%, oxygen 16.8
%, Water vapor 10%, and nitrogen 63.2% (vol%) were passed at a reaction temperature of 320 ° C for a contact time of 2.4 seconds. When the product was collected and analyzed by gas chromatography, the conversion of isobutane was 11.2%, the selectivity of methacrolein was 12.1%,
The selectivity of methacrylic acid was 54.0%.
実施例２ 三酸化モリブデン100部、五酸化バナジウム3.16部、8
5％リン酸6.67部を純水800部と混合する。これを還流下
で３時間加熱撹拌した後、塩化ルテニウム0.57％を純水
20部に溶解したものと、酸化銅0.46部及び二酸化ゲルマ
ニウム1.21部を加え、再び還流下で２時間加熱撹拌し
た。このスラリーを50℃まで冷却し、重炭酸セシウム5.
61部を純水30部に溶解したものを加え、15分間撹拌す
る。次に硝酸アンモニウム10部を純水30部に溶解したも
のを加え、混合液を100℃に加熱撹拌しながら蒸発乾固
した。得られた固型物を130℃で16時間乾燥後、加圧成
型し、空気流通下に380℃で３時間熱処理したものを触
媒として用いた。Example 2 100 parts of molybdenum trioxide, 3.16 parts of vanadium pentoxide, 8 parts
6.67 parts of 5% phosphoric acid are mixed with 800 parts of pure water. This was heated and stirred under reflux for 3 hours, and then 0.57% of ruthenium chloride was added to pure water.
The solution dissolved in 20 parts, 0.46 part of copper oxide and 1.21 parts of germanium dioxide were added, and the mixture was again heated and stirred under reflux for 2 hours. The slurry was cooled to 50 ° C. and cesium bicarbonate 5.
A solution prepared by dissolving 61 parts in 30 parts of pure water is added and stirred for 15 minutes. Next, a solution prepared by dissolving 10 parts of ammonium nitrate in 30 parts of pure water was added, and the mixture was evaporated to dryness while heating and stirring at 100 ° C. The obtained solid product was dried at 130 ° C. for 16 hours, molded under pressure, and heat-treated at 380 ° C. for 3 hours in an air stream to use as a catalyst.
この触媒の組成は P1Mo12V0.6Ru0.05Cu0.1Ge0.2Cs0.5であつた。The composition of this catalyst was P 1 Mo 12 V 0.6 Ru 0.05 Cu 0.1 Ge 0.2 Cs 0.5 .
本触媒を用いて実施例１と同じ反応条件で反応を行つ
たところ、イソブタンの反応率14.2％、メタクロレイン
の選択率15.3％、メタクリル酸の選択率50.2％であつ
た。The reaction was carried out under the same reaction conditions as in Example 1 using this catalyst. As a result, the conversion of isobutane was 14.2%, the selectivity of methacrolein was 15.3%, and the selectivity of methacrylic acid was 50.2%.
実施例３〜18 実施例２に準じて表１の各触媒を調製し、実施例１と
同一条件で反応し、表１の結果を得た。Examples 3 to 18 Each of the catalysts in Table 1 was prepared according to Example 2, and reacted under the same conditions as in Example 1 to obtain the results shown in Table 1.
比較例１ 実施例１に準じてP1Mo12の組成の触媒を調製し、実施
例１と同一条件で反応したところ、イソブタンの反応率
1.6％、メタクロレインの選択率20.1％であり、メタク
リル酸の生成は認められなかつた。 Comparative Example 1 A catalyst having a composition of P 1 Mo 12 was prepared according to Example 1, and reacted under the same conditions as in Example 1.
1.6%, methacrolein selectivity was 20.1%, and no formation of methacrylic acid was observed.
比較例２ 実施例２に準じてP1Mo12V0.5Ｋ0.7の組成の触媒を調
製し、実施例１と同一条件で反応したところ、イソブタ
ンの反応率9.6％、メタクロレインの選択率15.0％、メ
タクリル酸の選択率53.2％であつた。Comparative Example 2 A catalyst having a composition of P 1 Mo 12 V 0.5 K 0.7 was prepared according to Example 2, and reacted under the same conditions as in Example 1. The conversion of isobutane was 9.6%, and the selectivity of methacrolein was 15.0%. The selectivity of methacrylic acid was 53.2%.
Claims (1)
酸化し、メタクロレイン及びメタクリル酸を製造するに
あたり、 一般式 PaMobVcXdYeZfOg （式中P,Mo,V及びＯはそれぞれリン、モリブデン、バナ
ジウム及び酸素をあらわし、Ｘはルテニウム、オスミウ
ム及びイリジウムからなる群より選ばれた少なくとも１
種の元素、Ｙはカリウム、ルビジウム、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種の元素、
Ｚはゲルマニウム、ヒ素、アンチモン、ホウ素、セレ
ン、テルル、ビスマス、鉄、亜鉛、クロム、セリウム、
ジルコニウム、銅、ニツケル、コバルト、マンガン、ガ
リウム、ランタン、カルシウム、ストロンチウム、バリ
ウム、銀及びロジウムからなる群より選ばれた少なくと
も１種の元素を示す。ただし、a,b,c,d,e,f及びｇは各
元素の原子比率を表わし、ｂ＝12のときａ＝0.5〜６、
ｃ＝0.1〜３、ｄ＝0.005〜0.5、ｅ＝0.01〜２、ｆ＝０
〜５であり、ｇは前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。）で表される組成を有する触媒
を使用することを特徴とするメタクロレイン及びメタク
リル酸の製造法。1. A method of producing methacrolein and methacrylic acid by subjecting isobutane to gas-phase catalytic oxidation using molecular oxygen to produce a general formula P a Mo b V c X d Y e Z f O g (where P, Mo, V and O represent phosphorus, molybdenum, vanadium and oxygen, respectively, and X is at least one selected from the group consisting of ruthenium, osmium and iridium.
A species element, Y is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium;
Z is germanium, arsenic, antimony, boron, selenium, tellurium, bismuth, iron, zinc, chromium, cerium,
It shows at least one element selected from the group consisting of zirconium, copper, nickel, cobalt, manganese, gallium, lanthanum, calcium, strontium, barium, silver and rhodium. However, a, b, c, d, e, f and g represent the atomic ratio of each element, and when b = 12, a = 0.5 to 6,
c = 0.1-3, d = 0.005-0.5, e = 0.01-2, f = 0
And g is the number of oxygen atoms necessary to satisfy the valence of each component. A method for producing methacrolein and methacrylic acid, comprising using a catalyst having a composition represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2249056A JP2759376B2 (en) | 1990-09-19 | 1990-09-19 | Method for producing methacrolein and methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2249056A JP2759376B2 (en) | 1990-09-19 | 1990-09-19 | Method for producing methacrolein and methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04128247A JPH04128247A (en) | 1992-04-28 |
| JP2759376B2 true JP2759376B2 (en) | 1998-05-28 |
Family
ID=17187356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2249056A Expired - Fee Related JP2759376B2 (en) | 1990-09-19 | 1990-09-19 | Method for producing methacrolein and methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2759376B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6747172B1 (en) | 1999-10-12 | 2004-06-08 | Nippon Shokubai Co., Ltd. | Method for preparing methacrylic acid |
-
1990
- 1990-09-19 JP JP2249056A patent/JP2759376B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6747172B1 (en) | 1999-10-12 | 2004-06-08 | Nippon Shokubai Co., Ltd. | Method for preparing methacrylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04128247A (en) | 1992-04-28 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |