JP2671040B2 - Method for preparing catalyst for producing unsaturated carboxylic acid - Google Patents
Method for preparing catalyst for producing unsaturated carboxylic acidInfo
- Publication number
- JP2671040B2 JP2671040B2 JP1155762A JP15576289A JP2671040B2 JP 2671040 B2 JP2671040 B2 JP 2671040B2 JP 1155762 A JP1155762 A JP 1155762A JP 15576289 A JP15576289 A JP 15576289A JP 2671040 B2 JP2671040 B2 JP 2671040B2
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- JP
- Japan
- Prior art keywords
- catalyst
- unsaturated carboxylic
- carboxylic acid
- preparing
- component
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、不飽和アルデヒドの気相接触酸化による不
飽和カルボン酸を製造する際に使用する触媒に関するも
のである。TECHNICAL FIELD The present invention relates to a catalyst used for producing an unsaturated carboxylic acid by vapor phase catalytic oxidation of an unsaturated aldehyde.
従来、不飽和アルデヒドを気相接触酸化して不飽和カ
ルボン酸を製造する方法及び触媒に関し、数多くの提案
がなされている。特にメタクロレイン酸化用触媒として
ヘテロポリ酸系触媒が見い出されてからは、その改良に
ついて多数の特許が提出されており、例えば特開昭58−
74142号、特開昭60−239439号、特願昭63−172369号等
があるが、反応成績が充分でなかつたり、触媒活性の経
時低下が大きかつたり、触媒調製時に含窒素ヘテロ環化
合物やその他の種々な化合物等を使用するため後処理が
煩雑である等の欠点を有し、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。Hitherto, many proposals have been made regarding a method and a catalyst for producing an unsaturated carboxylic acid by subjecting an unsaturated aldehyde to gas phase catalytic oxidation. In particular, since the discovery of heteropolyacid catalysts as methacrolein oxidation catalysts, a number of patents have been submitted for their improvement.
There are 74142, JP-A-60-239439, Japanese Patent Application No. 63-172369, etc., but the reaction results are not sufficient, the catalytic activity is significantly decreased over time, and a nitrogen-containing heterocyclic compound during catalyst preparation or Since various other compounds and the like are used, they have drawbacks such as complicated post-treatment, and under the present circumstances, further improvement is desired when they are used as industrial catalysts.
本発明は、不飽和アルデヒドから不飽和カルボン酸を
有利に製造する新規な触媒の調製法の提供を目的として
いる。The present invention aims to provide a method for preparing a novel catalyst for advantageously producing an unsaturated carboxylic acid from an unsaturated aldehyde.
本発明者らは従来の触媒調製法を改善すべく、鋭意研
究した結果、従来の方法で調製された触媒を使用する場
合よりも低い反応温度において有効でかつ不飽和カルボ
ン酸が高収率で得られる新規な触媒の調製法を見い出し
た。The present inventors have conducted extensive studies to improve the conventional catalyst preparation method, and as a result, they are effective at a lower reaction temperature and have a higher yield of unsaturated carboxylic acid than when using a catalyst prepared by the conventional method. The method for preparing the resulting novel catalyst has been found.
本発明は、一般式 PaMobVcCedLaeXfYgZhOi （ここで式中Ｐ、Mo、Ｖ、Ce、La及びＯはそれぞれリ
ン、モリブデン、バナジウム、セリウム、ランタン及び
酸素、Ｘは鉄、銅、亜鉛、ビスマス、クロム、マグネシ
ウム、銀、タンタル、ニツケル、マンガン、バリウム及
びカルシウムからなる群より選ばれた少なくとも１種の
元素、Ｙは砒素、アンチモン、ジルコニウム、ホウ素、
ゲルマニウム、テルル及びガ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種の元素を示し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、
ｇ、ｈ及びｉは各元素の原子比率を表し、ｂ＝12のとき
ａ＝0.5〜３、ｃ＝0.01〜３、ｄ＝0.01〜２、ｅ＝0.01
〜２、ｆ＝０〜３（好ましくは0.01〜３）、ｇ＝０〜３
（好ましくは0.01〜３）、ｈ＝0.01〜２であり、ｉ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。）で表わされる組成を有する触媒を使用し、かつCe
成分及びLa成分の混合物をあらかじめ500〜1200℃の温
度で熱処理して得られた複合酸化物及び／又は混合酸化
物を触媒調製時に前記一般式に導入することを特徴とす
る不飽和カルボン酸製造用触媒の調製法である。The present invention has the general formula P a Mo b V c Ce d La e X f Y g Z h O i ( where in the formula P, Mo, V, Ce, La and O represent phosphorus, molybdenum, vanadium, cerium, Lanthanum and oxygen, X is at least one element selected from the group consisting of iron, copper, zinc, bismuth, chromium, magnesium, silver, tantalum, nickel, manganese, barium and calcium, Y is arsenic, antimony, zirconium, Boron,
Germanium, at least one element selected from the group consisting of tellurium and gallium, Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f,
g, h, and i represent the atomic ratio of each element, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0.01
˜2, f = 0 to 3 (preferably 0.01 to 3), g = 0 to 3
(Preferably 0.01 to 3), h = 0.01 to 2, and i is the number of oxygen atoms required to satisfy the valence of each component. ), A catalyst having a composition represented by
Unsaturated carboxylic acid production, characterized in that a complex oxide and / or a mixed oxide obtained by preliminarily heat treating a mixture of a component and a La component at a temperature of 500 to 1200 ° C. is introduced into the above general formula at the time of catalyst preparation. Is a method for preparing a catalyst for use.
本発明においては触媒成分中のCe及びLa源としてCe成
分及びLa成分の混合物をあらかじめ熱処理して得られた
複合酸化物及び／又は混合酸化物を使用することにより
活性、選択性が高くなることは予想外のことである。本
発明の触媒は、活性が高いため、より低い反応温度でも
充分な不飽和カルボン酸収率を達成することができ、そ
の結果、長期にわたつて高い触媒活性が維持されるので
工業的価値が極めて高い。In the present invention, by using a composite oxide and / or a mixed oxide obtained by previously heat-treating a mixture of a Ce component and a La component as a source of Ce and La in the catalyst component, the activity and the selectivity are increased. Is unexpected. Since the catalyst of the present invention has a high activity, it is possible to achieve a sufficient unsaturated carboxylic acid yield even at a lower reaction temperature, and as a result, a high catalytic activity is maintained over a long period of time, which is industrially valuable. Extremely high.
本発明反応の原料として使用する不飽和アルデヒドと
はアクロレイン、メタクロレイン等であり、得られる不
飽和カルボン酸とはアクリル酸、メタクリル酸等であ
る。The unsaturated aldehyde used as a raw material for the reaction of the present invention is acrolein, methacrolein, etc., and the resulting unsaturated carboxylic acid is acrylic acid, methacrylic acid, etc.
本発明に用いられる触媒を製造する方法としてはCe及
びLa源を規定する以外は特殊な方法に限定する必要はな
く、成分の著しい偏在を伴わない限り、従来からよく知
られている蒸発乾固法、沈殿法、酸化物混合法等の種々
の方法を用いることができる。The method for producing the catalyst used in the present invention does not need to be limited to a special method other than defining the Ce and La sources, and as long as there is no significant uneven distribution of the components, it is well known in the art to evaporate to dryness. Various methods such as a method, a precipitation method, and an oxide mixing method can be used.
Ce及びLa以外の触媒の調製に用いる原料としては各元
素の硝酸塩、炭酸塩、アンモニウム塩、ハロゲン化物、
酸化物などを組合せて使用することができる。例えばモ
リブデン原料としてはパラモリブデン酸アンモニウム、
三酸化モリブデン、塩化モリブデン等が使用でき、バナ
ジウム原料としてはメタバナジン酸アンモニウム、五酸
化バナジウム、塩化バナジウム等が使用できる。Raw materials used to prepare catalysts other than Ce and La include nitrates, carbonates, ammonium salts, and halides of each element,
A combination of oxides and the like can be used. For example, as a molybdenum raw material, ammonium paramolybdate,
Molybdenum trioxide, molybdenum chloride or the like can be used, and as the vanadium raw material, ammonium metavanadate, vanadium pentoxide, vanadium chloride or the like can be used.
ランタン及びセリウムの複合酸化物及び／又は混合酸
化物の調製法としては、特殊な方法に限定する必要はな
く、公知の方法例えば硝酸塩混合水溶液の熱分解法、ア
ンモニアで共沈させて熱分解する方法、クエン酸などの
各種有機酸を使用する方法等を用いることができる。ラ
ンタン及びセリウムの原料としては、これらの酸化物、
水酸化物、塩化物、酢酸塩、シユウ酸塩、硫酸塩、硝酸
塩、炭酸塩、硫酸アンモニウム塩又は硝酸アンモニウム
塩等が使用できる。The method for preparing the complex oxide and / or the mixed oxide of lanthanum and cerium does not need to be limited to a special method, and known methods such as a thermal decomposition method of a nitrate mixed aqueous solution and a thermal decomposition by coprecipitation with ammonia can be performed. The method, the method of using various organic acids such as citric acid, and the like can be used. As raw materials for lanthanum and cerium, these oxides,
Hydroxides, chlorides, acetates, oxalates, sulfates, nitrates, carbonates, ammonium sulfates, ammonium nitrates and the like can be used.
熱処理温度は500〜1200℃特に500〜1100℃が好まし
い。Ce/La原子比は特に0.1〜10が好ましい。ランタン及
びセリウムの複合酸化物及び／又は混合酸化物のＸ線回
折によるとCeO2とLa2O3それぞれの単独回折線が検出さ
れる他、CeO2の回折線がシフトすることから一部は固溶
体ないしは複合酸化物を形成しているものと思われる。The heat treatment temperature is preferably 500 to 1200 ° C, particularly preferably 500 to 1100 ° C. The Ce / La atomic ratio is particularly preferably 0.1-10. X-ray diffraction of complex oxides and / or mixed oxides of lanthanum and cerium detected individual diffraction lines of CeO 2 and La 2 O 3 respectively, and partly because CeO 2 diffraction lines were shifted. It is considered to form a solid solution or a complex oxide.
こうして得られたCe成分及びLa成分の複合酸化物及び
／又は混合酸化物を他の触媒成分の水溶液中に加え、加
熱撹拌しながら蒸発乾固することにより、目的の触媒を
調製することが好ましい。It is preferable to prepare the target catalyst by adding the composite oxide and / or mixed oxide of the Ce component and the La component thus obtained to an aqueous solution of another catalyst component and evaporating to dryness with heating and stirring. .
本発明方法により得られる触媒は無担体でもよく、シ
リカ、アルミナ、シリカ・アルミナ、シリコンカーバイ
ト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。The catalyst obtained by the method of the present invention may be carrier-free, may be supported on an inert carrier such as silica, alumina, silica-alumina, and silicon carbide, or may be diluted with this carrier before use.
本発明方法により調製される触媒を使用する場合は、
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１〜20％特に３〜10％が好ま
しい。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
は反応に実質的に影響を与えない。When using the catalyst prepared by the method of the present invention,
The concentration of the unsaturated aldehyde in the raw material gas can be varied over a wide range, but the volume is preferably 1 to 20%, particularly 3 to 10%. The raw material unsaturated aldehyde may contain a small amount of impurities such as water and lower saturated aldehydes, 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
要ならば純酸素で富化した空気も用いうる。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。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。Although it is economical to use air as the oxygen source, air enriched with pure oxygen can be used if necessary. The oxygen concentration in the raw material gas is defined by the molar ratio with respect to the unsaturated aldehyde, and this value is preferably 0.3-4 and particularly 0.4-2.5. The source gas may be diluted by adding an inert gas such as nitrogen, steam, or carbon dioxide.
反応圧力は常圧ないし数気圧が好ましい。反応温度は
230〜450℃の範囲、特に250〜400℃が好ましい。反応は
固定床でも流動床でも行うことができる。The reaction pressure is preferably normal pressure to several atmospheres. The reaction temperature is
The range of 230 to 450 ° C, particularly 250 to 400 ° C is preferable. The reaction can be carried out in a fixed bed or a fluidized 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.
実施例及び比較例中の不飽和アルデヒドの反応率、生
成する不飽和カルボン酸の選択率は以下のように定義さ
れる。The reaction rates of unsaturated aldehydes and the selectivities of unsaturated carboxylic acids produced in Examples and Comparative Examples are defined as follows.
下記実施例及び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によつた。 Parts in the following Examples and Comparative Examples are parts by weight, and analysis was carried out by gas chromatography.
実施例１ 硝酸セリウム2.05部と硝酸ランタン6.13部を純水30部
に溶解した。これを加熱撹拌して水の大部分を蒸発させ
たのち700℃で２時間熱処理し微粉砕した（Ａ粉末）。
別にパラ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4.77部を純水
100部に溶解した。これに85％リン酸8.16部を純水10部
に溶解したものを加え、さらに三酸化アンチモン4.13部
を加え撹拌しながら95℃に昇温した。次に硝酸銅1.14部
を純水30部に溶解した溶液を加えた。これにＡ粉末を加
え加熱撹拌しながら蒸発乾固した。得られた固形物を13
0℃で16時間乾燥後加圧成型し、空気流通下に380℃で５
時間熱処理したものを触媒として用いた。得られた触媒
の酸素以外の元素の組成（以下同じ）は Ｐ1.5Mo12V0.5Ce0.1La0.4Cu0.1Sb0.6K1 であつた。Example 1 2.05 parts of cerium nitrate and 6.13 parts of lanthanum nitrate were dissolved in 30 parts of pure water. This was heated and stirred to evaporate most of the water, then heat-treated at 700 ° C. for 2 hours and finely pulverized (A powder).
Separately, 100 parts of ammonium paramolybdate, 2.76 parts of ammonium metavanadate and 4.77 parts of potassium nitrate are purified water.
It was dissolved in 100 parts. A solution prepared by dissolving 8.16 parts of 85% phosphoric acid in 10 parts of pure water was added thereto, and 4.13 parts of antimony trioxide was further added. The mixture was heated to 95 ° C. while stirring. Next, a solution prepared by dissolving 1.14 parts of copper nitrate in 30 parts of pure water was added. Powder A was added to this, and evaporated to dryness with heating and stirring. 13 solids obtained
After drying at 0 ℃ for 16 hours, press molding and under air flow at 380 ℃ for 5 hours.
What was heat-treated for a while was used as a catalyst. The composition of elements other than oxygen in the obtained catalyst (the same applies hereinafter) was P 1.5 Mo 12 V 0.5 Ce 0.1 La 0.4 Cu 0.1 Sb 0.6 K 1 .
本触媒を反応管に充填し、メタクロレイン５％、酸素
10％、水蒸気30％、窒素55％（容量％）の混合ガスを反
応温度270℃、接触時間3.6秒で通じた。生成物を捕集し
ガスクロマトグラフイで分析したところ、メタクロレイ
ン反応率90.5％、メタクリル酸選択率88.5％であつた。This catalyst is filled in a reaction tube, and methacrolein 5%, oxygen
A gas mixture of 10%, water vapor 30%, and nitrogen 55% (volume%) was passed at a reaction temperature of 270 ° C and a contact time of 3.6 seconds. When the product was collected and analyzed by gas chromatography, the methacrolein conversion was 90.5% and the methacrylic acid selectivity was 88.5%.
比較例１ Ca及びLaを添加しない点を除き実施例１に準じて比較
触媒 Ｐ1.5Mo12V0.5Cu0.1Sb0.6K1 を調製し、この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、メタクロレイン反応率80.5％、メ
タクリル酸選択率80.1％であつた。Comparative Example 1 A comparative catalyst P 1.5 Mo 12 V 0.5 Cu 0.1 Sb 0.6 K 1 was prepared in the same manner as in Example 1 except that Ca and La were not added, and the reaction was performed under the same reaction conditions as in Example 1 using this catalyst. As a result, the reaction rate of methacrolein was 80.5% and the selectivity of methacrylic acid was 80.1%.
比較例２ 実施例１のＡ粉末に変えて酸化セリウム0.81部及び酸
化ランタン3.08部を使用し、その他は実施例１に準じ比
較触媒 Ｐ1.5Mo12V0.5Ce0.1La0.4Cu0.1Sb0.6K1 を調製し、この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、メタクロレイン反応率89.7％、メ
タクリル酸選択率87.7％であつた。Comparative Example 2 In place of the A powder of Example 1, 0.81 part of cerium oxide and 3.08 part of lanthanum oxide were used, and the others were the same as in Example 1. Comparative catalyst P 1.5 Mo 12 V 0.5 Ce 0.1 La 0.4 Cu 0.1 Sb 0.6 K 1 Was prepared and the reaction was carried out using this catalyst under the same reaction conditions as in Example 1. The methacrolein conversion was 89.7% and the methacrylic acid selectivity was 87.7%.
比較例３ 実施例１においてＡ粉末の熱処理温度を700℃から450
℃に変え、その他は実施例１に準じ比較触媒 Ｐ1.5Mo12V0.5Ce0.1La0.4Cu0.1Sb0.6K1 を調製し、この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、メタクロレイン反応率89.1％、メ
タクリル酸選択率87.5％であつた。Comparative Example 3 In Example 1, the heat treatment temperature of the A powder was 700 ° C. to 450 ° C.
The temperature was changed to 0 ° C., and a comparative catalyst P 1.5 Mo 12 V 0.5 Ce 0.1 La 0.4 Cu 0.1 Sb 0.6 K 1 was prepared in the same manner as in Example 1, and the reaction was carried out using this catalyst under the same reaction conditions as in Example 1. However, the methacrolein conversion rate was 89.1% and the methacrylic acid selectivity was 87.5%.
実施例２ 硝酸セリウム6.15部と硝酸ランタン3.07部を純水30部
に溶解した。これに28％アンモニア水5.81部を加え、黄
白色沈殿と無色の溶液を得た。これを加熱撹拌し、水の
大部分を蒸発させたのち120℃で16時間乾燥させた。こ
の乾燥品を800℃で２時間熱処理し微粉砕した（Ｂ粉
末）。Example 2 6.15 parts of cerium nitrate and 3.07 parts of lanthanum nitrate were dissolved in 30 parts of pure water. To this was added 5.81 parts of 28% aqueous ammonia to obtain a yellowish white precipitate and a colorless solution. This was heated and stirred, most of the water was evaporated, and then dried at 120 ° C. for 16 hours. The dried product was heat-treated at 800 ° C. for 2 hours and finely pulverized (B powder).
実施例１のＡ粉末に変えてＢ粉末を使用し、実施例１
に準じ P1Mo12V1Ce0.3La0.2Fe0.2Zn0.1As0.1Ｋ0.5Cs0.5 を調製し、この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、メタクロレイン反応率90.3％、メ
タクリル酸選択率88.6％であつた。The powder A was used in place of the powder A of Example 1, and the powder of Example 1 was used.
P 1 Mo 12 V 1 Ce 0.3 La 0.2 Fe 0.2 Zn 0.1 As 0.1 K 0.5 Cs 0.5 was prepared according to the above, and the reaction was carried out under the same reaction conditions as in Example 1 using this catalyst. The reaction rate of methacrolein was 90.3. %, And the selectivity for methacrylic acid was 88.6%.
実施例３〜12 実施例１に準じて下記表の各触媒を調製し、実施例１
と同一条件で反応させ、次表の結果を得た。Examples 3 to 12 Each catalyst shown in the following table was prepared according to Example 1, and Example 1
The reaction was carried out under the same conditions as above, and the results shown in the following table were obtained.
実施例13 実施例１で調製した触媒を用い、アクロレイン５％、
酸素10％、水蒸気30％、窒素55％（容量％）の混合ガス
を反応温度270℃、接触時間3.6秒で触媒に導入したとこ
ろ、アクロレイン反応率93.6％、アクリル酸選択率95.4
％であつた。４ Example 13 Using the catalyst prepared in Example 1, acrolein 5%,
When a mixed gas of oxygen 10%, water vapor 30% and nitrogen 55% (volume%) was introduced into the catalyst at a reaction temperature of 270 ° C. and a contact time of 3.6 seconds, the acrolein conversion rate was 93.6% and the acrylic acid selectivity was 95.4%.
%. 4
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−150436（ＪＰ，Ａ) 特開 昭60−239439（ＪＰ，Ａ) 特開 昭52−133893（ＪＰ，Ａ) 特開 平２−119942（ＪＰ，Ａ) 特開 平２−22243（ＪＰ，Ａ) 特公 昭59−13259（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-56-150436 (JP, A) JP-A-60-239439 (JP, A) JP-A-52-133893 (JP, A) JP-A-2- 119942 (JP, A) JP-A-2-22243 (JP, A) JP 59-13259 (JP, B1)
Claims (1)
ン、モリブデン、バナジウム、セリウム、ランタン及び
酸素、Ｘは鉄、銅、亜鉛、ビスマス、クロム、マグネシ
ウム、銀、タンタル、ニツケル、マンガン、バリウム及
びカルシウムからなる群より選ばれた少なくとも１種の
元素、Ｙは砒素、アンチモン、ジルコニウム、ホウ素、
ゲルマニウム、テルル及びガ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種の元素を示し、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＝12のと
きａ＝0.5〜３、ｃ＝0.01〜３、ｄ＝0.01〜２、ｅ＝0.0
1〜２、ｆ＝０〜３、ｇ＝0.〜３、ｈ＝0.01〜２であ
り、ｉ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調製する
に際し、Ce成分及びLa成分の混合物をあらかじめ500〜1
200℃の温度で熱処理して得られた複合酸化物及び／又
は混合酸化物を触媒調製時に前記一般式に導入すること
を特徴とする不飽和カルボン酸製造用触媒の調製法。1. A general formula P a Mo b V c Ce d La e X f Y g Z h O i ( where in the formula P, Mo, V, Ce, La and O represent phosphorus, molybdenum, vanadium, cerium , Lanthanum and oxygen, X is at least one element selected from the group consisting of iron, copper, zinc, bismuth, chromium, magnesium, silver, tantalum, nickel, manganese, barium and calcium, and Y is arsenic, antimony, zirconium. , Boron,
Germanium, at least one element selected from the group consisting of tellurium and gallium, Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f,
g, h and i represent the atomic ratio of each element, and when b = 12, a = 0.5-3, c = 0.01-3, d = 0.01-2, e = 0.0
1 to 2, f = 0 to 3, g = 0. To 3 and h = 0.01 to 2 and i is the number of oxygen atoms required to satisfy the valence of each component). When preparing a catalyst having a composition, a mixture of Ce component and La component is preliminarily 500 to 1
A method for preparing a catalyst for producing an unsaturated carboxylic acid, which comprises introducing a composite oxide and / or a mixed oxide obtained by heat treatment at a temperature of 200 ° C. into the above general formula when preparing the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1155762A JP2671040B2 (en) | 1989-06-20 | 1989-06-20 | Method for preparing catalyst for producing unsaturated carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1155762A JP2671040B2 (en) | 1989-06-20 | 1989-06-20 | Method for preparing catalyst for producing unsaturated carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0321346A JPH0321346A (en) | 1991-01-30 |
| JP2671040B2 true JP2671040B2 (en) | 1997-10-29 |
Family
ID=15612856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1155762A Expired - Fee Related JP2671040B2 (en) | 1989-06-20 | 1989-06-20 | Method for preparing catalyst for producing unsaturated carboxylic acid |
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| Country | Link |
|---|---|
| JP (1) | JP2671040B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3000249B2 (en) * | 1993-03-24 | 2000-01-17 | アキヤマ印刷機製造 株式会社 | Double-sided printing sheet-fed offset printing press |
| JPH1110828A (en) * | 1997-06-20 | 1999-01-19 | J M Insatsu Kikai Kk | Double side multicolor printing offset press |
| JP4030740B2 (en) * | 2001-10-11 | 2008-01-09 | ダイヤニトリックス株式会社 | Method for producing ammoxidation catalyst |
-
1989
- 1989-06-20 JP JP1155762A patent/JP2671040B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0321346A (en) | 1991-01-30 |
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