JPS6044042A - Preparation of catalyst for preparing methacrylic acid - Google Patents
Preparation of catalyst for preparing methacrylic acidInfo
- Publication number
- JPS6044042A JPS6044042A JP58152521A JP15252183A JPS6044042A JP S6044042 A JPS6044042 A JP S6044042A JP 58152521 A JP58152521 A JP 58152521A JP 15252183 A JP15252183 A JP 15252183A JP S6044042 A JPS6044042 A JP S6044042A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- methacrylic acid
- acid
- ammonium molybdate
- pyridine
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
この発明は、メタクリル酸を高い収率で製造することが
できるリン、モリブデン、銅およびヒ素を触媒成分元素
として含有するヘテロポリ酸系のメタクリル酸製造用触
媒の新規製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a heteropolyacid-based catalyst for producing methacrylic acid containing phosphorus, molybdenum, copper, and arsenic as catalyst component elements, which can produce methacrylic acid in high yield. It is something.
リン、モリブデン、銅およびヒ素を触媒成分元素として
含有するヘテロポリ酸系触媒の存在下にメタクロレイン
を分子状酸素と高温気相で反応させてメタクリル酸を製
造する方法は、すでに知られており、ヘテロポリ酸系触
媒は、一般に触媒成分元素を含有する化合物２例えば酸
化物やリン酸塩など適当な化合物を出発片オ」とし、必
要に応じて担体を加え、これらを水などの存在下に混合
し。A method for producing methacrylic acid by reacting methacrolein with molecular oxygen in a high-temperature gas phase in the presence of a heteropolyacid catalyst containing phosphorus, molybdenum, copper, and arsenic as catalyst component elements is already known. Heteropolyacid catalysts are generally produced by starting with a compound containing the catalyst component elements, such as an oxide or a phosphate, adding a carrier if necessary, and mixing these in the presence of water. death.
溶液状またはスラリー状にいこれを乾燥、一般には蒸発
乾固し、成形あるいは成形せずに、必要に応じて焼成す
ることによって製造されている（特開昭５３−５０１１
６号公報＝ＵＳＰ４１１０３６９ 。It is produced by drying the liquid or slurry, generally evaporating it to dryness, and baking it as necessary without shaping or molding (Japanese Patent Application Laid-Open No. 53-5011).
Publication No. 6 = USP4110369.
特開昭５３−５１１９４号公報、特開昭５０−４１８１
１号公報など）。JP-A-53-51194, JP-A-50-4181
Publication No. 1, etc.).
また一般にリンおよびモリブデンを含むヘテロポリ酸（
またはその塩）は、骨格構造としてケギン構造をとり、
その骨格の周りはプロトンまたはカチオン、および結晶
水によってかこまねていると云われており、ヘテロポリ
酸の結晶水は０〜３０分子の範囲にある。It also commonly contains phosphorus and molybdenum (
or its salt) has a Keggin structure as its skeletal structure,
It is said that the skeleton is surrounded by protons or cations and water of crystallization, and the water of crystallization of heteropolyacids ranges from 0 to 30 molecules.
この発明者らは、リン、モリブデン、銅およびヒ素を触
媒成分として含有するヘテロポリ酸系触媒によるメタク
リル酸の製造について鋭意研究を行外っだ結果、触媒の
製法を改良することによって、従来のへテロポリ酸系触
媒の製法で得られた触媒を使用した場合よりもメタクリ
ル酸の収率を高めうることができることを知り、この発
明に到った。The inventors conducted intensive research on the production of methacrylic acid using a heteropolyacid catalyst containing phosphorus, molybdenum, copper, and arsenic as catalyst components, and as a result, they succeeded in improving the production method of the catalyst. The present invention was based on the discovery that the yield of methacrylic acid can be increased compared to when a catalyst obtained by a method for producing a telopolyacid catalyst is used.
この発明は、メタクロレインを触媒の存在下に分子状酸
素と高温気相で反応させてメタクリル酸を製造するため
に用いるリン、モリブデン、銅およびヒ素を触媒成分元
素として含有するヘテロポリ酸系のメタクリル酸製造用
触媒を製造する方法において、モリブデン酸アンモニウ
ムおよび他の触媒成分元素を含有する化合物を水の存在
下に混合し、１（１られる溶液またはスラリーにピリジ
ンおよび硝酸を加えて濃縮または乾燥し、濃縮物または
乾燥物を１００〜４００’Ｃの温度で熱処理することを
特徴とするメタクリル酸製造用触媒の製法に関するもの
である。This invention relates to a heteropolyacid-based methacrylic acid containing phosphorus, molybdenum, copper, and arsenic as catalyst component elements, which is used to produce methacrylic acid by reacting methacrolein with molecular oxygen in the presence of a catalyst in a high-temperature gas phase. In a method for producing a catalyst for acid production, compounds containing ammonium molybdate and other catalyst component elements are mixed in the presence of water, pyridine and nitric acid are added to the resulting solution or slurry, and the mixture is concentrated or dried. , relates to a method for producing a catalyst for producing methacrylic acid, which comprises heat-treating a concentrate or a dried product at a temperature of 100 to 400'C.
この発明は、リン、モリブデン、銅およびヒ素 ′を触
媒成分元素として含有するヘテロポリ酸系のメタクリル
酸製造用触媒の製造に有効であり、リン、モリブデン、
銅およびヒ素のほかに従来この種の触媒系に加えられて
いるタングステン、鉄。This invention is effective for producing a heteropolyacid-based catalyst for producing methacrylic acid containing phosphorus, molybdenum, copper, and arsenic as catalyst component elements.
In addition to copper and arsenic, tungsten and iron are traditionally added to this type of catalyst system.
ビスマス、アンチモン、コバルト、亜鉛、ジルコニウム
、カルシウム、クロム、ホウ素、スズ、チタン、パラジ
ウム、タンタル、セリウム、バナジウム、マグネシウム
、銀、アルミニウム、カワラムなどの触媒成分元素を含
むメタクリル酸製造用触媒の製造に適用でき、なかでも
この発明を次の一般組成式。For the production of catalysts for the production of methacrylic acid containing catalyst component elements such as bismuth, antimony, cobalt, zinc, zirconium, calcium, chromium, boron, tin, titanium, palladium, tantalum, cerium, vanadium, magnesium, silver, aluminum, and kawaram. Among others, this invention can be applied to the following general composition formula.
Ｍｏ１２ Ｐａ ０ｕ１） Ａｓ（！ ＸｄＯ（３〔式
中、 Ｍｏはモリブデン、Ｐはリン、 Ｃｕは銅。Mo12 Pa 0u1) As(!
Ａｓ Ｉｄ、ヒ素、ｘはタングステン、鉄、ビスマス。As Id, arsenic, x is tungsten, iron, bismuth.
アンチモノ、コバルト、亜鉛、ホウ素、クロム。antimono, cobalt, zinc, boron, chromium.
ジルコニウム、バナジウム、チタンおよびスズよりなる
群から選択された１種以上の元素、および０は酸素を示
し、添字のａ −ｅは原子数を示し。One or more elements selected from the group consisting of zirconium, vanadium, titanium, and tin, and 0 represents oxygen, and the subscripts a to e represent the number of atoms.
ＭＯの原子数を１２とすると、ａ−０，９〜２．好まし
くは１〜１゜６．ｂ、＝０．００５〜３．好ましくは０
．０１〜１．ｃ＝０．０１〜２．好ましくは０．１〜１
．５．ｄ、＝０〜２．好ましくは０．００１〜１゜θは
前記各成分の原子価によって定まる値である。〕で表わ
されるメタクリル酸製造用触媒の製造に適用すると、（
１）比較的に低い反応温度で、（２）短い接触時間で、
（３）メタクリル酸を長期にわたって著しく高い収率で
製造することができる触媒が得られる。When the number of atoms of MO is 12, a-0.9 to 2. Preferably 1-1°6. b, =0.005-3. Preferably 0
．． 01-1. c=0.01~2. Preferably 0.1-1
．． 5. d,=0-2. Preferably, 0.001 to 1° θ is a value determined by the valence of each component. ] When applied to the production of a catalyst for the production of methacrylic acid, (
1) relatively low reaction temperatures; (2) short contact times;
(3) A catalyst is obtained that allows methacrylic acid to be produced over a long period of time in a significantly high yield.
この発明においては、モリブデン源としてモリブデン酸
アンモニウムを使用する必要がある。モリブデン源をモ
リブデン酸アンモニウム以外のモリブデンを含有する化
合物１例えば酸化モリブデン、モリブデン酸などを使用
した場合は、安定なリンモリブデン酸化合物を生成する
のに長時間を要ｊ〜、充分な触媒性能を示す触媒を得る
のが困難である。In this invention, it is necessary to use ammonium molybdate as the source of molybdenum. When a molybdenum-containing compound other than ammonium molybdate (1), such as molybdenum oxide or molybdic acid, is used as the molybdenum source, it takes a long time to produce a stable phosphomolybdic acid compound, and sufficient catalytic performance is required. It is difficult to obtain the catalyst shown.
この発明で使用するモリブデン源のモリブデン酸アンモ
ニウムは２例えば（ＮＨ４）６Ｍｏ７０２４・４Ｈ２０
の化学式で示されるものが好適であるが、これ以外のも
のを使用することもできる。The molybdenum source used in this invention, ammonium molybdate, is 2, for example (NH4)6Mo7024.4H20.
Those represented by the chemical formula are preferred, but others can also be used.
この発明においては、まずモリブデン酸アンモニウムお
よび他の触媒成分元素を含有する化合物を水の存在下に
混合して溶液またはスラリーを調製する。他の触媒成分
元素を含有する化合物の代表的なものとしては、リン酸
、ヒ酸、酸化ヒ素。In this invention, first, a solution or slurry is prepared by mixing a compound containing ammonium molybdate and other catalyst component elements in the presence of water. Typical compounds containing other catalytic elements include phosphoric acid, arsenic acid, and arsenic oxide.
酸化銅などをはじめ、そのほかの触媒成分元素の酸化物
、水酸化物、炭酸塩などを挙げることができる。Examples include copper oxide, as well as oxides, hydroxides, and carbonates of other catalyst component elements.
モリブデン酸アンモニウムをはじめ、触媒成分元素を含
有する化合物を水の存在下に混合するにあたっての混合
順序は特に制限されないが、できればモリブデン酸アン
モニウムを最初に溶解させ。The order of mixing ammonium molybdate and other compounds containing catalyst component elements in the presence of water is not particularly limited, but if possible, ammonium molybdate is dissolved first.
次いで他の触媒成分元素を含有する化合物を混合するの
が望ましい。It is then desirable to mix compounds containing other catalyst component elements.
この発明においては、混合後、得られる溶液またはスラ
リーにピリジンと硝酸を加えて攪拌下に２０〜１００°
Ｃ好ましくは３０〜８０°Ｃの温度でろ時間以上、好１
しくけ５〜６０時間混合溶液またはスラリーを熟成させ
るのが好適である。熟成させることによって、熟成させ
ない場合よりもさらに高いメタクリル酸収率を示す触媒
が得られる。In this invention, after mixing, pyridine and nitric acid are added to the resulting solution or slurry and heated at 20 to 100° while stirring.
C Preferably at a temperature of 30 to 80°C for a period of time or more, preferably 1
It is preferable to age the mixed solution or slurry for 5 to 60 hours. By aging, a catalyst is obtained which exhibits a higher yield of methacrylic acid than without aging.
熟成させることによってメタクリル酸収率が高められる
原因は十分明らかではないが、ヘテロポリ酸の結晶構造
に変化が生じ、他の触媒成分元素を含んだ新しいヘテロ
ポリ酸が形成されるためではないかと推考される。The reason why the yield of methacrylic acid is increased by aging is not fully clear, but it is thought that the crystal structure of the heteropolyacid changes and a new heteropolyacid containing other catalyst components is formed. Ru.
またこの発明においては、上記混合溶液またはスラリー
に、ピリジンおよび硝酸を添加すると。Moreover, in this invention, when pyridine and nitric acid are added to the above mixed solution or slurry.
リンモリブデン酸の塩が完成し、高い活性を示す構造を
Ｊ）え、しかも触媒の再現性が改善され、触媒性能も向
−ヒする。ピリジンおよび硝酸は、熱処理によって得ら
れる触媒に対してピリジンが０．０１〜１．０重ＪＡ′
係、好１しくけ０．１５〜０．９重量％になるような計
で、１だ硝酸は０．０１〜１．０重量％、好ましくは０
．１５〜０．９重量％になるような量で使用Ｖるのが適
当である。ピリジンおよび硝酸の使用量が多すぎても棟
だ少なすぎてもメタクリル酸収率が低くなる。使用する
硝酸の濃度は特に制限されないが、一般には濃度が１０
０重量％上、好ましくは３００重量％上のものが適当で
ある。The phosphomolybdic acid salt has been completed and has a structure exhibiting high activity, and the reproducibility of the catalyst is improved, and the catalytic performance is also improved. Pyridine and nitric acid contain 0.01 to 1.0 weight JA' of pyridine to the catalyst obtained by heat treatment.
The amount of nitric acid is preferably 0.01 to 1.0% by weight, preferably 0.15 to 0.9% by weight.
．． It is appropriate to use an amount of 15 to 0.9% by weight. If the amounts of pyridine and nitric acid used are too large or too small, the yield of methacrylic acid will be low. The concentration of nitric acid used is not particularly limited, but generally the concentration is 10
Above 0% by weight, preferably above 300% by weight are suitable.
この発明においては、モリブデン酸アンモニウムおよび
他の触媒成分元素を含有する化合物を水の存在下に混合
し、得られる溶液またはスラリーにピリジンおよび硝酸
を加えて濃縮または乾燥して濃縮物または乾燥物を得る
にあたっては１例えばロータリーエバポレーターで濃縮
する方法、蒸発乾固法、噴霧乾燥法などを採用するのが
便利である。濃縮物または乾燥物は、これを成形あるい
は成形せずに、１００〜３００°Ｃ２好ましくは１６０
〜２５０°Ｃの温度で熱処理する。In this invention, compounds containing ammonium molybdate and other catalyst component elements are mixed in the presence of water, pyridine and nitric acid are added to the resulting solution or slurry, and concentrated or dried to obtain a concentrate or dry product. In order to obtain it, it is convenient to employ methods such as concentration using a rotary evaporator, evaporation to dryness, and spray drying. Concentrates or dried products are heated at 100 to 300°C, preferably at 160°C, with or without shaping.
Heat treatment at a temperature of ~250°C.
この発明において、熱処理は前記温度で行なう必要があ
るが、熱処理を効果的に行なうためには濃縮物または乾
燥物を、あらかじめｉｏｏ〜４００°Ｃに加熱された加
熱器中で急激に熱処理するのが望ましい。熱処理時間は
、一般には１時間具−ヒ。In this invention, it is necessary to carry out the heat treatment at the above-mentioned temperature, but in order to carry out the heat treatment effectively, it is necessary to heat the concentrate or dried product rapidly in a heater preheated to io~400°C. is desirable. The heat treatment time is generally 1 hour.
さらには１〜２０時間が適当であり、熱処理は一般には
酸素含有ガス、例えば空気雰囲気下に行なうのが適当で
ある。Furthermore, 1 to 20 hours is appropriate, and the heat treatment is generally carried out under an atmosphere of an oxygen-containing gas, such as air.
熱処理することによって、従来の製法で製造されたリン
、モリブデン、銅およびヒ素を触媒成分元素として含有
するヘテロポリ酸系の触媒による場合よりも高いメタク
リル酸収率を示す目的とする触媒が得られる。メタクリ
ル酸収率が向上する原因は十分明らかではないが、ヘテ
ロポリ酸の結晶構造に変化が生じ、これが触媒活性を一
段と高めていると思われる。By heat treatment, it is possible to obtain a target catalyst that exhibits a higher yield of methacrylic acid than a heteropolyacid-based catalyst containing phosphorus, molybdenum, copper, and arsenic as catalyst component elements produced by a conventional method. Although the reason for the improvement in methacrylic acid yield is not fully clear, it is thought that a change occurs in the crystal structure of the heteropolyacid, which further increases the catalytic activity.
この発明によって得られる触媒中の各触媒成分元素は、
リンモリブデン酸のピリジン塩およびアンモニウム塩な
とのへテロポリ酸塩およびそれらの銅塩の混合物をはじ
め、複数の触媒成分元素が酸素とともに結合した複合酸
化物、各触媒成分元素単独の酸化物などの混合物として
存在している３この発明においては、触媒製造時に相体
を加えて目的とする触媒を製造しても差支えない。また
この発明によって得られた触媒をメタクリル酸の製造に
使用する際に担体と一緒に使用しても差支えない。Each catalyst component element in the catalyst obtained by this invention is
In addition to heteropolyacid salts of phosphomolybdic acid such as pyridine salts and ammonium salts, and mixtures of their copper salts, composite oxides in which multiple catalyst component elements are combined with oxygen, and oxides of each catalyst component element alone, etc. In the present invention, the desired catalyst may be produced by adding a phase during catalyst production. Furthermore, when the catalyst obtained according to the present invention is used in the production of methacrylic acid, it may be used together with a carrier.
担体としては、従来アクリル酸、メタクリル酸などの製
造用触媒の担体として公知のものがいずれも使用でき１
例えばけいそう土、アルミナ、シリカ、シリカゾル、シ
リコンカーバイド、グラファイトなどを挙げることがで
きる。As the carrier, any of those conventionally known as carriers for catalysts for producing acrylic acid, methacrylic acid, etc. can be used.
Examples include diatomaceous earth, alumina, silica, silica sol, silicon carbide, and graphite.
この発明によって得られた触媒の存在下にメタクロレイ
ンを分子状酸素と高温気相で反応させてメタクリル酸を
製造するにあたり２反応に使用する分子状酸素としては
、純酸素ガスでもよいが。When producing methacrylic acid by reacting methacrolein with molecular oxygen in the high temperature gas phase in the presence of the catalyst obtained according to the present invention, pure oxygen gas may be used as the molecular oxygen used in the two reactions.
特に高純度である必要もないので、一般には空気を使用
するのが経済的で便利である。また反応においては分子
状酸素およびメタクロレインとともに希釈ガスを使用す
るのがよい。希釈ガスとしてはこの反応に悪影響を及ぼ
さないもの２例えば窒素ガス、炭酸ガス、水蒸気などが
使用でき、なかでも水蒸気はメタクリル酸の選択率を向
上させる作用があるだけでなく、触媒活性を持続させる
作用があるので、水蒸気を存在させて反応を行なうのが
よい。It is generally economical and convenient to use air since it does not need to be particularly pure. Further, in the reaction, it is preferable to use a diluent gas together with molecular oxygen and methacrolein. As the diluent gas, it is possible to use gases that do not have a negative effect on this reaction, such as nitrogen gas, carbon dioxide gas, water vapor, etc. Among them, water vapor not only has the effect of improving the selectivity of methacrylic acid, but also maintains the catalytic activity. Because of this effect, it is best to carry out the reaction in the presence of water vapor.
また反応に使用するメタクロレインとしても分子状酸素
と同様に特に高純度である必要はなく。Also, like molecular oxygen, methacrolein used in the reaction does not need to be of particularly high purity.
例えばイソブチレンの酸化反応によって得られたものを
その丑ま使用してもよい。For example, those obtained by oxidation reaction of isobutylene may be used as is.
この発明によって得られた触媒は、流動床、移動床２固
定床反応器などいずれの反応器でも使用できるが、この
発明で得られた触媒は、比較的低い反応温度、短い接触
時間でメタクロレインの反応率およびメタクリル酸の選
択率が高く、長期間にわたって触媒活性を持続させるこ
とができるという利点があるので、一般には固定床反応
器で使用するのが有利である。The catalyst obtained by this invention can be used in any reactor such as a fluidized bed reactor, a moving bed 2 fixed bed reactor, etc., but the catalyst obtained by this invention can be used at a relatively low reaction temperature and a short contact time. It is generally advantageous to use a fixed bed reactor because it has the advantages of high reaction rate and high selectivity to methacrylic acid, and the ability to maintain catalytic activity over a long period of time.
捷だ反応は、常圧、加圧、減圧下などいずれで行なって
もよいが、一般には常圧で行なうのが便利である。また
反応温度は２００〜４００°Ｃ２好ましくは２５０〜３
５０°Ｃ２特に２６０〜３２０°Ｃが好適である。また
接触時間は０．１〜１０秒。The straining reaction may be carried out under normal pressure, increased pressure, reduced pressure, etc., but it is generally convenient to carry out the reaction under normal pressure. The reaction temperature is 200-400°C, preferably 250-30°C.
50°C2, especially 260-320°C is suitable. Further, the contact time is 0.1 to 10 seconds.
好捷しくけ０．５〜５秒が適当である。反応にはメタク
ロレインおよび分子状酸素、一般には空気に。A suitable time is 0.5 to 5 seconds. The reaction involves methacrolein and molecular oxygen, generally air.
さらに水蒸気を加えた混合ガスを使用するのが好適であ
り、混合ガスの組成はメタクロレイン１モルに対して２
分子状酸素が０．５〜７モル、好１しくは１〜５モルで
、水蒸気が００５〜３０モル、好ましくは１〜１０モル
であることが好適である。It is preferable to use a mixed gas to which water vapor is further added, and the composition of the mixed gas is 2 to 1 mole of methacrolein.
It is suitable that the molecular oxygen is 0.5 to 7 mol, preferably 1 to 5 mol, and the water vapor is 0.5 to 30 mol, preferably 1 to 10 mol.
また生成した目的生成物であるメタクリル酸の回収には
、従来一般に知られた方法５例えば凝縮。In addition, methacrylic acid, which is the desired product, can be recovered by conventionally known methods such as condensation.
溶剤抽出などの方法が適用される。Methods such as solvent extraction are applied.
次に実施例および比較例を示す。例中の反応率（係）２
選択率（チ）および収率（φ）は次の定義に従う。Next, Examples and Comparative Examples will be shown. Reaction rate (person) 2 in the example
Selectivity (chi) and yield (φ) follow the following definitions.
実施例１
〔触媒の製造〕
モリブデン酸アンモニウムＣ（ＮＨ４）ｓＭＯｒ ０２
４・４ Ｈ２０）２２６．５７を５０°Ｃの水４５０ｍ
＃に溶解させた。Example 1 [Production of catalyst] Ammonium molybdate C(NH4)sMOr 02
4.4 H20) 226.57 in 450m of water at 50°C
It was dissolved in #.
これに８５チリン酸［Ｈ３ＰＯ４〕１１．９６グ、６０
乃ヒ酸ＣＨ３ＡＳ０４〕２２．３ｑ？＋硝酸鋼（Ｃ！ｕ
（ＮＯ３）２・ろＨ２０’ｌ ２．５１ ｆを水１０扉
ｅに溶解させた溶液、ピリジン〔Ｃ５Ｈ５Ｎ′ｌｌ乙０
１および６０係硝酸９０ｍ１！を順次加えて混合し、５
０°Ｃで２０時間攪拌下に熟成させた。To this, 85 tyrinic acid [H3PO4] 11.96 g, 60
Arsenic acid CH3AS04] 22.3q? + Nitric acid steel (C!u
(NO3) 2・filtration H20'l 2.51 f solution dissolved in water 10 door e, pyridine [C5H5N'll Otsu0
1 and 60 nitric acid 90ml! Add and mix sequentially, 5
The mixture was aged at 0°C for 20 hours with stirring.
次いで、このスラリーを１３０°Ｃに保持したオイルバ
ス−にで蒸発乾固し、乾固物を２００°Ｃにイ呆持した
加熱器に投入して１８時間、空気雰囲気下に熱処理した
後、グラファイト２重量係をカロえて５ ｍｍ ｌ Ｘ
５ ＨＩＢ Ｈのペレットに成形し、モリフ゛デン：
リン：銅：ヒ素の原子比が１２ ： １ ： ０．１
： ０．６の触媒を得た。Next, this slurry was evaporated to dryness in an oil bath kept at 130°C, and the dried product was put into a heater kept at 200°C and heat-treated in an air atmosphere for 18 hours. Add graphite 2 weight to 5 mm l
5 Molded into HIB H pellets, molybdenum:
The atomic ratio of phosphorus: copper: arsenic is 12: 1: 0.1
: A catalyst of 0.6 was obtained.
上記触媒９．３ｍｅ（９，Ｏｆ／ ）を内径８ ｔｔａ
ｎ ｌのガラス製Ｕ字型反応管に充填し、これに容量で
メタクロレイン４係、酸素１ｏ％、水蒸気３０チおよび
窒素５６係の混合ガスを４００ ｍｌ ／ ｍｉｎの流
量で流し９反応温度２９０°Ｃで接触反応を１時間行な
った。その時の接触時間は１．４秒である。The above catalyst 9.3me (9, Of/ ) has an inner diameter of 8 tta
A mixed gas of 4 parts of methacrolein, 1% of oxygen, 30 parts of water vapor, and 56 parts of nitrogen was poured into it at a flow rate of 400 ml/min, and the reaction temperature was 290. The contact reaction was carried out for 1 hour at °C. The contact time at that time was 1.4 seconds.
接触反応の結果は第１表に示す。The results of the contact reaction are shown in Table 1.
比較例１
ピリジンおよび硝酸を加えなかったほかは、実施例１と
同様にして触媒を製造し、実施例１と同様の反応条件で
接触反応を行なった。Comparative Example 1 A catalyst was produced in the same manner as in Example 1, except that pyridine and nitric acid were not added, and a catalytic reaction was carried out under the same reaction conditions as in Example 1.
接触反応の結果は第１表に示す。The results of the contact reaction are shown in Table 1.
比較例２
実施例１のモリブデン酸アンモニウムのかわりに、三酸
化モリブデン（ＭＯＯ３）を使用したほかは。Comparative Example 2 Example 1 except that molybdenum trioxide (MOO3) was used instead of ammonium molybdate.
実施例１と同様にして触媒を製造し、実施例１と同様の
反応条件で接触反応を行なった。A catalyst was produced in the same manner as in Example 1, and a catalytic reaction was carried out under the same reaction conditions as in Example 1.
接触反応の結果は第１表に示す。The results of the contact reaction are shown in Table 1.
第 １ 表
（１４）
実施例２
〔触媒の製造〕
モリブデン酸アンモニウム［（ＮＨ４）ｓＭＯ７０２ｃ
４Ｈ＋０：）２２３．３ｙを５０゛Ｃの水４４０ｍ１に
溶解させた。Table 1 (14) Example 2 [Production of catalyst] Ammonium molybdate [(NH4)sMO702c
4H+0:)223.3y was dissolved in 440 ml of water at 50°C.
これに８５係リン酸［Ｈ３ＡＯ４］ １２．１５ ｇ＋
６０ ’％ヒ酸［Ｈ３ＡｓＯ４］ ２２．７５９ ＋
硝酸銅５．０９ ｆを水２０ｍｅに溶解させたもの、三
酸化アンチモン１．５Ｂ６９． ピリジン２９．６ ’
ｊおよび６０係硝酸８９ｍ１３を順次加えて混合し、攪
拌下に６０′ｃで１５時間熟成させた。Add to this 12.15 g of 85th phosphoric acid [H3AO4]
60'% arsenic acid [H3AsO4] 22.759 +
Copper nitrate 5.09 f dissolved in water 20 me, antimony trioxide 1.5 B69. Pyridine 29.6'
and 89 ml of 60% nitric acid were sequentially added and mixed, and the mixture was aged at 60'C for 15 hours with stirring.
次いでこのスラリーを１３０’Ｃに保持したオイルバス
上で蒸発乾固し、乾固物を２００’Ｃに保持した加熱器
に投入して、１８時間空気雰囲気下に熱処理した後、グ
ラファイト２重量係を加えて５重１ｍｌ×５ｔｎｍＨの
ベレットに成形し、モリブデンニリン：銅：ヒ素：アン
チモンの原子比が１２：１：０．２ ： ０．６ ：
０．１の触媒を得た。Next, this slurry was evaporated to dryness on an oil bath kept at 130'C, and the dried product was put into a heater kept at 200'C and heat-treated in an air atmosphere for 18 hours. was added and formed into a 5-layer pellet of 1 ml x 5 tnmH, and the atomic ratio of molybdenum-niline: copper: arsenic: antimony was 12:1:0.2:0.6:
A catalyst of 0.1 was obtained.
上記触媒を使用し、実施例１と同様の反応条件で接触反
応を行なった。A catalytic reaction was carried out under the same reaction conditions as in Example 1 using the above catalyst.
接触反応の結果は第２表に示す。The results of the contact reaction are shown in Table 2.
実施例６〜６
実施例２と同様の触媒製造法で触媒成分元素が第２表に
記載の原子比になるようにかえたほかは。Examples 6 to 6 The catalyst manufacturing method was the same as in Example 2, except that the catalyst component elements were changed to have the atomic ratios listed in Table 2.
実施例２と同様にして触媒を製造し、実施例１と同様の
反応条件で接触反応を行なった。なお触媒製造の出発原
料として実施例２に記載の原料のほかに、クロム源とし
て硝酸クロム［ａｒ（ＮＯ３）ａ・９Ｉ（２０：）。A catalyst was produced in the same manner as in Example 2, and a catalytic reaction was carried out under the same reaction conditions as in Example 1. In addition to the raw materials described in Example 2 as starting materials for catalyst production, chromium nitrate [ar(NO3)a.9I(20:)] was used as a chromium source.
ホウ素源としてホウ酸［ＨｓＢＯａ）を使用した。接触
反応の結果は第２表に示す。Boric acid [HsBOa] was used as the boron source. The results of the contact reaction are shown in Table 2.
Claims (1)
で反応させてメタクリル酸を製造するために用いるリン
、モリブデン、銅およびヒ素を触媒成分元素として含有
するヘテロポリ酸系のメタクリル酸製造用触媒を製造す
る方法において、モリブデン酸アンモニウムおよび他の
触媒成分元素を含有する化合物を水の存在下に混合し、
得られる溶液またはスラリーにピリジンおよび硝酸を加
えて濃縮または乾燥１〜．濃縮物または乾燥物を１００
〜４００°Ｃの温度で熱処理することを特徴とするメタ
クリル酸製造用触媒の製法。A heteropolyacid-based catalyst for producing methacrylic acid containing phosphorus, molybdenum, copper, and arsenic as catalyst component elements, which is used to produce methacrylic acid by reacting methacrolein with molecular oxygen in the presence of a catalyst in a high-temperature gas phase. In the method of manufacturing, a compound containing ammonium molybdate and other catalyst component elements is mixed in the presence of water,
Pyridine and nitric acid are added to the resulting solution or slurry and concentrated or dried. 100% concentrate or dry
A method for producing a catalyst for producing methacrylic acid, characterized by heat treatment at a temperature of ~400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58152521A JPS6044042A (en) | 1983-08-23 | 1983-08-23 | Preparation of catalyst for preparing methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58152521A JPS6044042A (en) | 1983-08-23 | 1983-08-23 | Preparation of catalyst for preparing methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6044042A true JPS6044042A (en) | 1985-03-08 |
| JPH052374B2 JPH052374B2 (en) | 1993-01-12 |
Family
ID=15542252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58152521A Granted JPS6044042A (en) | 1983-08-23 | 1983-08-23 | Preparation of catalyst for preparing methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6044042A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0424900A2 (en) * | 1989-10-25 | 1991-05-02 | Mitsubishi Rayon Co., Ltd. | Process for preparing catalysts for producing methacrylic acid |
| KR100497173B1 (en) * | 2002-11-29 | 2005-06-28 | 주식회사 엘지화학 | Method for preparing of catalyst for partial oxidation of acrolein |
| US7045482B2 (en) * | 2002-06-04 | 2006-05-16 | Korea Institute Of Science And Technology | Method for preparing a heteropolyacid catalyst from basic solvent treatments and method for preparing methacrylic acid using thererof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5712830A (en) * | 1980-06-26 | 1982-01-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidation catalyst and its preparation |
| JPS57177347A (en) * | 1981-04-22 | 1982-11-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidizing catalyst and preparation thereof |
| JPS57177348A (en) * | 1981-04-24 | 1982-11-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidizing catalyst and preparation thereof |
| JPS5827255A (en) * | 1981-08-12 | 1983-02-17 | Hitachi Ltd | Controlling system of file used for plural electronic computers in common |
-
1983
- 1983-08-23 JP JP58152521A patent/JPS6044042A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5712830A (en) * | 1980-06-26 | 1982-01-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidation catalyst and its preparation |
| JPS57177347A (en) * | 1981-04-22 | 1982-11-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidizing catalyst and preparation thereof |
| JPS57177348A (en) * | 1981-04-24 | 1982-11-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidizing catalyst and preparation thereof |
| JPS5827255A (en) * | 1981-08-12 | 1983-02-17 | Hitachi Ltd | Controlling system of file used for plural electronic computers in common |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0424900A2 (en) * | 1989-10-25 | 1991-05-02 | Mitsubishi Rayon Co., Ltd. | Process for preparing catalysts for producing methacrylic acid |
| US7045482B2 (en) * | 2002-06-04 | 2006-05-16 | Korea Institute Of Science And Technology | Method for preparing a heteropolyacid catalyst from basic solvent treatments and method for preparing methacrylic acid using thererof |
| KR100497173B1 (en) * | 2002-11-29 | 2005-06-28 | 주식회사 엘지화학 | Method for preparing of catalyst for partial oxidation of acrolein |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH052374B2 (en) | 1993-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3142549B2 (en) | Iron / antimony / molybdenum-containing oxide catalyst composition and method for producing the same | |
| EP0484792B1 (en) | Fluidized-bed catalyst for preparing acrylonitrile | |
| JP4280797B2 (en) | Method for producing composite oxide catalyst | |
| JPS58112050A (en) | Preparation of catalyst for production of methacrylic acid | |
| JPS5811416B2 (en) | Method for producing methacrylic acid | |
| US4273676A (en) | Process for producing methacrylic acid and a catalyst | |
| JPS5826329B2 (en) | Seizouhou | |
| JPS5827255B2 (en) | Method for producing unsaturated fatty acids | |
| US4014927A (en) | Process for production of unsaturated acids from corresponding unsaturated aldehydes | |
| JPS6044042A (en) | Preparation of catalyst for preparing methacrylic acid | |
| JPH05177141A (en) | Preparation of methacrylic acid | |
| JP3995381B2 (en) | Catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| JP3209778B2 (en) | Preparation of catalyst for methacrylic acid production | |
| JP3316881B2 (en) | Method for producing catalyst for producing methacrylic acid | |
| US3600443A (en) | Process for the catalytic oxidation of lower olefins to carbonyls and acids | |
| JP3146486B2 (en) | Method for producing catalyst for producing methacrylic acid | |
| JP4629886B2 (en) | Catalyst for producing methacrolein and / or methacrylic acid, method for producing the same, and method for producing methacrolein and / or methacrylic acid | |
| JPH0840969A (en) | Production of acrolein and catalyst | |
| JPS5851943A (en) | Preparation of catalyst for preparing methacrylic acid | |
| JP2671040B2 (en) | Method for preparing catalyst for producing unsaturated carboxylic acid | |
| JPH0691172A (en) | Preparation of catalyst for production of methacrylic acid | |
| JP3859397B2 (en) | Catalyst for production of methacrolein and methacrylic acid | |
| JPS6154013B2 (en) | ||
| JPS59160537A (en) | Preparation of catalyst for manufacturing methacrylic acid | |
| JPH03167152A (en) | Production of methacrylic acid |