JP2003164763A - Method for manufacturing composite oxide catalyst for oxidizing propylene - Google Patents
Method for manufacturing composite oxide catalyst for oxidizing propyleneInfo
- Publication number
- JP2003164763A JP2003164763A JP2001368874A JP2001368874A JP2003164763A JP 2003164763 A JP2003164763 A JP 2003164763A JP 2001368874 A JP2001368874 A JP 2001368874A JP 2001368874 A JP2001368874 A JP 2001368874A JP 2003164763 A JP2003164763 A JP 2003164763A
- Authority
- JP
- Japan
- Prior art keywords
- component
- catalyst
- composite oxide
- oxide catalyst
- propylene
- 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
-
- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、プロピレンを酸
化触媒の存在下に分子状酸素又は分子状酸素含有ガスに
より気相酸化してアクロレイン及びアクリル酸を製造す
る際に使用するモリブデン−ビスマス−鉄−コバルト及
び／又はニッケル含有複合酸化物触媒の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a molybdenum-bismuth-iron used for producing acrolein and acrylic acid by vapor-phase oxidizing propylene with molecular oxygen or a gas containing molecular oxygen in the presence of an oxidation catalyst. A method for producing a cobalt- and / or nickel-containing composite oxide catalyst.
【０００２】[0002]
【従来の技術】プロピレンを分子状酸素により気相接触
酸化して、アクロレイン及びアクリル酸を合成する触媒
に関し、従来から数多くの提案がなされており、その触
媒系は一般に同一系として取り扱われることが多い。そ
のなかで、鉄の導入に関してモリブデン成分と鉄成分を
あらかじめ混合することが、特開平９−１０５８８号公
報に、モリブデン化合物と特定の金属化合物を特定の条
件下で混合し、しかる後、鉄化合物を混合して触媒を調
製することが、特開２０００−３７６３１号公報に、鉄
−モリブデートとして添加する方法が、特開平１−１６
８３４４号公報に開示されている。2. Description of the Related Art Many proposals have hitherto been made regarding catalysts for synthesizing acrolein and acrylic acid by vapor-phase catalytic oxidation of propylene with molecular oxygen, and the catalyst system is generally treated as the same system. Many. Among them, for introducing iron, premixing the molybdenum component and the iron component is described in JP-A-9-10588, in which the molybdenum compound and the specific metal compound are mixed under specific conditions, and then the iron compound is mixed. To prepare a catalyst, and in JP-A 2000-37631, a method of adding as iron-molybdate is disclosed in JP-A 1-16.
It is disclosed in Japanese Patent No. 8344.
【０００３】[0003]
【発明が解決しようとする課題】この発明は、特にプロ
ピレンからアクロレイン及びアクリル酸を有利に製造す
るための活性及び目的生成物の選択性が優れた触媒の新
規な製造方法を提供することを課題としている。DISCLOSURE OF THE INVENTION The object of the present invention is to provide a novel method for producing a catalyst having excellent activity and selectivity for a desired product, particularly for advantageously producing acrolein and acrylic acid from propylene. I am trying.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、特にプロピレンか
らアクロレイン及びアクリル酸を製造する際に使用する
モリブデン−ビスマス−鉄−コバルト及び／又はニッケ
ル含有複合酸化物触媒を製造するに際し、特定の条件下
で鉄とコバルト及び／又はニッケルを含む出発原料を予
め特定の比率で混合し、しかる後、モリブデン化合物を
混合して複合酸化物触媒を調製することにより、高活性
で、且つ目的とする酸化生成物を高い収率で与える複合
酸化物触媒が得られるという知見を見いだし、この発明
に到達したのである。Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that molybdenum-bismuth-iron-cobalt and / or / used in the production of acrolein and acrylic acid from propylene. Alternatively, when producing a nickel-containing composite oxide catalyst, starting materials containing iron and cobalt and / or nickel are mixed in a specific ratio in advance under specific conditions, and then a molybdenum compound is mixed to mix the composite oxide catalyst. The present inventors have found that a complex oxide catalyst having a high activity and giving a desired oxidation product in a high yield can be obtained by preparing the above, and have reached the present invention.
【０００５】すなわち、本発明は、触媒成分として
（１）モリブデン、（２）ビスマス、（３）コバルト及
び／又はニッケル、（４）鉄を必須成分として含むプロ
ピレン酸化用複合酸化物触媒を製造する方法において、
前記成分（３）と前記成分（４）を同一溶液として混合
し、その後、少なくとも一部の前記成分（１）を含む溶
液に混合する際に、成分（３）と成分（４）の比
（（４）／（３））が、０．０５以上０．２以下になる
ように規定して、モリブデン−ビスマス−鉄−コバルト
及び／又はニッケル含有複合酸化物触媒を調製するよう
にしたものである。That is, the present invention produces a composite oxide catalyst for propylene oxidation containing (1) molybdenum, (2) bismuth, (3) cobalt and / or nickel, and (4) iron as essential components as catalyst components. In the method
When the component (3) and the component (4) are mixed in the same solution and then mixed in a solution containing at least a part of the component (1), the ratio of the component (3) and the component (4) ( (4) / (3)) is specified to be 0.05 or more and 0.2 or less so that a molybdenum-bismuth-iron-cobalt and / or nickel-containing composite oxide catalyst is prepared. is there.
【０００６】その際、前記成分（３）及び（４）の溶解
及び混合を５０〜８０℃で行い、前記成分（１）の溶解
を５０〜８０℃で行い、かつ成分（３）及び成分（４）
の混合液と成分（１）の混合を両液の温度差が１０℃以
内の条件にて行い、且つ混合後６０〜９０℃での加熱を
少なくとも１時間以上行うことが好ましい。In this case, the components (3) and (4) are dissolved and mixed at 50 to 80 ° C., the component (1) is dissolved at 50 to 80 ° C., and the components (3) and ( 4)
It is preferable that the mixed liquid of (1) and the component (1) are mixed under the condition that the temperature difference between both liquids is within 10 ° C., and that the mixture is heated at 60 to 90 ° C. for at least 1 hour or more.
【０００７】この発明において製造する複合酸化物触媒
は、下記一般式（１）で示されるものである。
ＭｏaＢｉbＣｏcＮｉdＦｅeＸfＹgＺhＳｉiＯj （１）
式中、Ｍｏ、Ｂｉ、Ｃｏ，Ｎｉ、Ｆｅ、Ｓｉ及びＯはモ
リブテン、ビスマス、コバルト、ニッケル、鉄、珪素及
び酸素を表し、Ｘはマグネシウム（Ｍｇ）、カルシウム
（Ｃａ）、亜鉛（Ｚｎ）、セリウム（Ｃｅ）及びサマリ
ウム（Ｓｍ）からなる群から選ばれる少なくとも１種の
元素であり、Ｙはナトリウム（Ｎａ）、カリウム
（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタ
リウム（Ｔｌ）からなる群から選ばれる少なくとも１種
の元素であり、Ｚはホウ素（Ｂ）、リン（Ｐ）、砒素
（Ａｓ）及びタングステン（Ｗ）からなる群から選ばれ
る少なくとも１種の元素である。また、ａ〜ｊはそれぞ
れの元素の原子比を表わし、ａ＝１２のとき、ｂ＝０．
５〜７、ｃ＝０〜１０、ｄ＝０〜１０（但しｃ＋ｄ＝１
〜１０）、ｅ＝０．０５〜２、ｆ＝０〜１、ｇ＝０．０
１〜１、ｈ＝０〜３、ｉ＝０〜４８、の範囲にあり、ま
たｊは他の元素の酸化状態を満足させる数値である。こ
のようにして得られた触媒は、プロピレンを気相酸化し
て、アクロレイン及びアクリル酸を製造するのに有効に
用いることができる。The composite oxide catalyst produced in the present invention is represented by the following general formula (1). Mo a Bi b Co c Ni d Fe e X f Y g Z h Si i O j (1) In the formula, Mo, Bi, Co, Ni, Fe, Si and O are molybdenum, bismuth, cobalt, nickel, iron, Represents silicon and oxygen, X is at least one element selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce) and samarium (Sm), and Y is sodium ( Na), potassium (K), rubidium (Rb), cesium (Cs) and at least one element selected from the group consisting of thallium (Tl), Z is boron (B), phosphorus (P), arsenic ( At least one element selected from the group consisting of As) and tungsten (W). Further, a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.
5-7, c = 0-10, d = 0-10 (however, c + d = 1
-10), e = 0.05-2, f = 0-1, g = 0.0
It is in the range of 1-1, h = 0 to 3, i = 0 to 48, and j is a numerical value satisfying the oxidation states of other elements. The catalyst thus obtained can be effectively used for gas phase oxidation of propylene to produce acrolein and acrylic acid.
【０００８】[0008]
【発明の実施の形態】この発明においては、触媒を構成
する各元素の出発原料は特に制限されるものではない。
例えばモリブデン成分の原料としては三酸化モリブデン
のようなモリブデン酸化物、モリブデン酸、パラモリブ
デン酸アンモニウムのようなモリブデン酸又はその塩、
リンモリブデン酸、ケイモリブデン酸のようなモリブデ
ンを含むヘテロポリ酸又はその塩などを用いることがで
きる。ビスマス成分の原料としては硝酸ビスマス、次炭
酸ビスマス、硫酸ビスマス、酢酸ビスマスなどのビスマ
ス塩、三酸化ビスマス、金属ビスマスなどを用いること
ができる。鉄成分、コバルト、ニッケル及びその他の元
素の原料としては通常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硝酸塩、炭酸塩、有機酸塩、水酸
化物等又はそれらの混合物を用いることができる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the starting materials for each element constituting the catalyst are not particularly limited.
For example, as a raw material for the molybdenum component, molybdenum oxide such as molybdenum trioxide, molybdic acid, molybdic acid such as ammonium paramolybdate or a salt thereof,
A heteropoly acid containing molybdenum such as phosphomolybdic acid or silicomolybdic acid or a salt thereof can be used. As a raw material for the bismuth component, bismuth nitrate, bismuth subcarbonate, bismuth sulfate, bismuth acetate, and other bismuth salts, bismuth trioxide, metal bismuth, and the like can be used. As a raw material for the iron component, cobalt, nickel and other elements, it is usual to use an oxide or a nitrate, a carbonate, an organic acid salt, a hydroxide or the like or a mixture thereof which can be converted into an oxide by igniting. it can.
【０００９】この発明における触媒の調製方法は、前記
特定の条件を除けば、特に制限はない。例えば、鉄とコ
バルト及び／又はニッケルを特定比率で５０〜８０℃の
条件下にて溶解混合し、５０〜８０℃の条件下にて溶解
した少なくとも１部のモリブデンと両液の温度差を１０
℃以内の条件にて混合し、６０〜９０℃の条件下にて１
時間以上加熱撹拌した後、その他の成分と添加し、加熱
混合し、蒸発乾固、必要に応じ短時間の熱処理を施し、
粉砕した後、得られた粉体を押出し成型、打錠成型、造
粒成型などの成型方法により任意の形状に成型して得ら
れる。この際、触媒の強度、粉化度を改善する効果があ
るとして一般に知られているガラス繊維などの無機繊
維、各種ウィスカーなどを添加してもよい。また、触媒
物性を再現よく制御するために、硝酸アンモニウム、セ
ルロース、デンプン、ポリビニルアルコール、ステアリ
ン酸など一般に粉体結合剤として知られている添加物を
使用することもできる。The method for preparing the catalyst in the present invention is not particularly limited except the above specific conditions. For example, iron and cobalt and / or nickel are dissolved and mixed in a specific ratio under the condition of 50 to 80 ° C., and the temperature difference between at least 1 part of molybdenum dissolved under the condition of 50 to 80 ° C. and the temperature of the two liquids is 10.
Mix under the condition of less than ℃ 1
After heating and stirring for more than an hour, add the other ingredients, mix by heating, evaporate to dryness, and subject to heat treatment for a short time if necessary,
After crushing, the obtained powder is molded into an arbitrary shape by a molding method such as extrusion molding, tablet molding, granulation molding, or the like. At this time, inorganic fibers such as glass fibers and various whiskers, which are generally known to have the effect of improving the strength and pulverization degree of the catalyst, may be added. Further, in order to control the physical properties of the catalyst with good reproducibility, additives generally known as powder binders such as ammonium nitrate, cellulose, starch, polyvinyl alcohol and stearic acid can be used.
【００１０】この発明において得られる一般式（１）で
表される複合酸化物をそれ自体単独で触媒として使用す
ることができるが、アルミナ、シリカ、シリカ−アルミ
ナ、シリコンカーバイド、酸化チタン、酸化マグネシウ
ム、アルミニウムスポンジ、シリカ−チタニアなど一般
に不活性担体として知られている担体に担持して使用し
てもよい。この際もまた、触媒の強度などを改善するた
めに前記の無機繊維などを添加しても、あるいは触媒物
性を再現よく制御するために前記の硝酸アンモニウムな
どの添加剤を使用することもできる。The composite oxide represented by the general formula (1) obtained in the present invention can be used alone as a catalyst, but alumina, silica, silica-alumina, silicon carbide, titanium oxide, magnesium oxide can be used. , Aluminum sponge, silica-titania, or any other carrier generally known as an inert carrier may be used. Also in this case, the above-mentioned inorganic fiber or the like may be added to improve the strength of the catalyst, or the above-mentioned additive such as ammonium nitrate may be used to control the physical properties of the catalyst with good reproducibility.
【００１１】また、この発明において得られる複合酸化
物を触媒として使用する場合、その形状、大きさなどに
ついても特に制限はなく、公知の形状、大きさなどから
適宜選ぶことができる。例えば、形状についていえば、
球状、円柱状、リング状などのいずれでもよい。When the composite oxide obtained in the present invention is used as a catalyst, its shape and size are not particularly limited and can be appropriately selected from known shapes and sizes. For example, regarding the shape,
It may be spherical, cylindrical, ring-shaped or the like.
【００１２】これら成型体あるいは担持体を、例えば、
空気流通下に３００〜６００℃の温度で１〜１０時間程
度焼成することにより、プロピレン酸化用の複合酸化物
触媒が得られる。[0012] These molded bodies or carriers are
A composite oxide catalyst for propylene oxidation is obtained by calcining at a temperature of 300 to 600 ° C. for about 1 to 10 hours under air circulation.
【００１３】この発明によって得られる複合酸化物触媒
を使用するプロピレン接触気相酸化反応は、原料ガス組
成として１〜１０容量％のプロピレン、５〜１８容量％
の分子状酸素、０〜６０容量％の水蒸気及び２０〜７０
容量％の不活性ガス、例えば窒素、炭酸ガスなどからな
る混合ガスを前記のようにして調製された触媒上に２５
０〜４５０℃の温度範囲及び常圧〜１０気圧の圧力下、
０．５〜１０秒の接触時間で導入することによって遂行
される。The propylene-catalyzed gas-phase oxidation reaction using the composite oxide catalyst obtained according to the present invention is carried out with a raw material gas composition of 1 to 10% by volume of propylene and 5 to 18% by volume.
Molecular oxygen, 0-60% by volume water vapor and 20-70
A mixed gas consisting of vol.% Inert gas, such as nitrogen, carbon dioxide, etc., is added to the catalyst prepared as described above by 25
Under a temperature range of 0 to 450 ° C. and a normal pressure to 10 atmospheres,
It is carried out by introducing with a contact time of 0.5 to 10 seconds.
【００１４】[0014]
【実施例】この発明に係る複合酸化物触媒のより具体的
な製造方法と、得られた複合酸化物触媒を用いてプロピ
レンの酸化反応を実施した結果を以下に示す。EXAMPLES A more specific method for producing a composite oxide catalyst according to the present invention and the results of carrying out an oxidation reaction of propylene using the obtained composite oxide catalyst are shown below.
【００１５】実施例１
（複合酸化物触媒の調製）パラモリブデン酸アンモニウ
ム１０５．５gを６０℃に加温した純水５００ｍｌに溶
解させる。次に硝酸第二鉄１２．３ｇ、硝酸コバルト４
８．５ｇ及び硝酸ニッケル４８．５ｇを６０℃に加温し
た純水１００ｍｌに溶解させる。これらの溶液を、充分
に撹拌しながら徐々に混合する。混合後、７０℃に温度
を上げ、２時間混合を継続した。次に、純水４０ｍｌに
ホウ砂０．９６ｇ及び硝酸カリウム０．５１ｇを加温下
に溶解させて、上記スラリーに加える。次に、シリカ７
２．９ｇを加えて、充分に撹拌する。続いて純水２０ｍ
ｌに硝酸２．７ｍｌを加えてさらに硝酸ビスマス２４．
１ｇを加えて、撹拌混合する。このスラリーを加熱乾燥
して得られた粒状固体を小型成形機にて径５ｍｍ、高さ
４ｍｍの錠剤に打錠成型し、次に４８０℃／８時間の焼
成を行って、触媒とした。仕込み原料から計算される触
媒は、次の原子比を有する複合酸化物である。
（（４）／（３））＝０．０９
Ｍｏ：Ｂｉ：Ｃｏ：Ｎｉ：Ｆｅ：Ｎａ：Ｂ：Ｋ：Ｓｉ
＝１２：１：３．３：３．３：０．６：０．１：０．
２：０．１：２４Example 1 (Preparation of complex oxide catalyst) 105.5 g of ammonium paramolybdate is dissolved in 500 ml of pure water heated to 60 ° C. Next, ferric nitrate 12.3 g, cobalt nitrate 4
8.5 g and 48.5 g of nickel nitrate are dissolved in 100 ml of pure water heated to 60 ° C. These solutions are gradually mixed with thorough stirring. After mixing, the temperature was raised to 70 ° C. and mixing was continued for 2 hours. Next, 0.96 g of borax and 0.51 g of potassium nitrate are dissolved in 40 ml of pure water under heating and added to the above slurry. Next, silica 7
Add 2.9 g and stir well. 20m of pure water
2.7 ml of nitric acid was added to 1 ml of bismuth nitrate.
Add 1 g and mix with stirring. A granular solid obtained by heating and drying this slurry was tablet-molded by a small molding machine into tablets having a diameter of 5 mm and a height of 4 mm, and then calcined at 480 ° C./8 hours to obtain a catalyst. The catalyst calculated from the charged raw materials is a complex oxide having the following atomic ratio. ((4) / (3)) = 0.09 Mo: Bi: Co: Ni: Fe: Na: B: K: Si
= 12: 1: 3.3: 3.3: 0.6: 0.1: 0.
2: 0.1: 24
【００１６】（プロピレンの酸化反応）上記のようにし
て調製した複合酸化物触媒を使用して、プロピレンの酸
化反応を実施し、プロピレン転化率、アクロレイン収
率、アクリル酸収率を計算した。複合酸化物触媒２０ｍ
ｌを内径１５ｍｍのステンレス鋼製ナイタージャケット
付反応管に充填し、プロピレン８容量％、空気６７容量
％、水蒸気２５容量％の混合ガスを空間速度（ＳＶ）１
５００ｈｒ-1で導入し、プロピレンの酸化反応を実施し
た。反応浴温３１０℃にて表１に示す結果が得られた。(Propylene Oxidation Reaction) The propylene oxidation reaction was carried out using the composite oxide catalyst prepared as described above, and the propylene conversion rate, acrolein yield and acrylic acid yield were calculated. Complex oxide catalyst 20m
1 was filled in a reaction tube with an inner diameter of 15 mm and made of a stainless steel niter jacket, and a mixed gas of 8% by volume of propylene, 67% by volume of air and 25% by volume of water vapor was supplied at a space velocity (SV) of 1
It was introduced at 500 hr -1 , and the oxidation reaction of propylene was carried out. The results shown in Table 1 were obtained at a reaction bath temperature of 310 ° C.
【００１７】比較例１
実施例１において硝酸第二鉄を５．５ｇとした以外は同
様に調製した。仕込み原料から計算される触媒は、次の
原子比を有する複合酸化物である。
（（４）／（３））＝０．０４
Ｍｏ：Ｂｉ：Ｃｏ：Ｎｉ：Ｆｅ：Ｎａ：Ｂ：Ｋ：Ｓｉ
＝１２：１：３．３：３．３：０．２７：０．１：０．
２：０．１：２４
実施例１と同一条件にてプロピレンの酸化反応を実施し
た。結果を表１に示した。Comparative Example 1 A sample was prepared in the same manner as in Example 1 except that the amount of ferric nitrate was changed to 5.5 g. The catalyst calculated from the charged raw materials is a complex oxide having the following atomic ratio. ((4) / (3)) = 0.04 Mo: Bi: Co: Ni: Fe: Na: B: K: Si
= 12: 1: 3.3: 3.3: 0.27: 0.1: 0.
2: 0.1: 24 The propylene oxidation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.
【００１８】比較例２
実施例１において硝酸第二鉄を２７．７ｇとした以外は
同様に調製した。仕込み原料から計算される触媒は、次
の原子比を有する複合酸化物である。
（（４）／（３））＝０．２１
Ｍｏ：Ｂｉ：Ｃｏ：Ｎｉ：Ｆｅ：Ｎａ：Ｂ：Ｋ：Ｓｉ
＝１２：１：３．３：３．３：１．３５：０．１：０．
２：０．１：２４
実施例１と同一条件にてプロピレンの酸化反応を実施し
た。結果を表１に示した。Comparative Example 2 A sample was prepared in the same manner as in Example 1 except that the amount of ferric nitrate was changed to 27.7 g. The catalyst calculated from the charged raw materials is a complex oxide having the following atomic ratio. ((4) / (3)) = 0.21 Mo: Bi: Co: Ni: Fe: Na: B: K: Si
= 12: 1: 3.3: 3.3: 1.35: 0.1: 0.
2: 0.1: 24 The propylene oxidation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】ここで、プロピレン転化率、アクロレイン
収率、アクリル酸収率の定義は、次の通りである。
プロピレン転化率（モル％）＝（反応したプロピレンの
モル数／供給したプロピレンのモル数）×１００
アクロレイン収率（モル数）＝（生成したアクロレイン
のモル数／供給したプロピレンのモル数）×１００
アクリル酸収率（モル数）＝（生成したアクリル酸のモ
ル数／供給したプロピレンのモル数）×１００The definitions of propylene conversion, acrolein yield and acrylic acid yield are as follows. Propylene conversion rate (mol%) = (mol number of reacted propylene / mol number of propylene fed) × 100 Acrolein yield (mol number) = (mol number of acrolein produced / mol number of propylene fed) × 100 Acrylic acid yield (moles) = (moles of acrylic acid produced / moles of propylene fed) × 100
【００２１】[0021]
【発明の効果】以上のように、この発明によれば、特に
プロピレンからアクロレイン及びアクリル酸を有利に製
造するための活性及び目的生成物の選択性が優れた触媒
を得ることができる。INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to obtain a catalyst which is excellent in activity for producing acrolein and acrylic acid from propylene, and which is excellent in selectivity of a target product.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 57/05 Ｃ０７Ｃ 57/05 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 岩倉 具敦 三重県四日市市東邦町１番地 三菱化学株 式会社内 Ｆターム(参考） 4G069 AA03 AA08 BA03B BB06A BB06B BC02B BC03B BC25B BC59A BC59B BC66B BC67B BC68B BD03B CB07 CB10 CB17 DA06 EA02Y FB05 FB64 4H006 AA02 AC45 AC46 BA02 BA06 BA07 BA09 BA13 BA14 BA15 BA18 BA19 BA30 BA31 BE30 BS10 4H039 CA62 CA65 CC40 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C07C 57/05 C07C 57/05 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Iwakura tool 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. F-term within the company (reference) 4G069 AA03 AA08 BA03B BB06A BB06B BC02B BC03B BC25B BC59A BC59B BC66B BC67B BC68B BD03B CB07 BA02 BA06 BA02 BA06 BA02 BA06 A02 BA06 A02 BA06 A02 BA006 A02 BA06 A02 BA06 A02B06A02B006A02B06A02 BA13 BA14 BA15 BA18 BA19 BA30 BA31 BE30 BS10 4H039 CA62 CA65 CC40
Claims (4)
（２）ビスマス、（３）コバルト及び／又はニッケル、
（４）鉄を必須成分として含むプロピレン酸化用複合酸
化物触媒を製造する方法において、前記成分（３）と前
記成分（４）を同一溶液として混合し、その後、少なく
とも一部の前記成分（１）を含む溶液に混合する際に、
成分（３）と成分（４）の比（（４）／（３））が、
０．０５以上０．２以下であることを特徴とするプロピ
レン酸化用複合酸化物触媒の製造方法。1. A catalyst component comprising (1) molybdenum,
(2) bismuth, (3) cobalt and / or nickel,
(4) In the method for producing a composite oxide catalyst for propylene oxidation containing iron as an essential component, the component (3) and the component (4) are mixed in the same solution, and then at least a part of the component (1) is mixed. ) Is mixed with the solution containing
The ratio of the component (3) and the component (4) ((4) / (3)) is
A method for producing a composite oxide catalyst for propylene oxidation, which is 0.05 or more and 0.2 or less.
合を５０〜８０℃で行い、前記成分（１）の溶解を５０
〜８０℃で行い、かつ成分（３）及び成分（４）の混合
液と成分（１）の混合を両液の温度差が１０℃以内の条
件にて行い、且つ混合後６０〜９０℃での加熱を少なく
とも１時間以上行うことを特徴とする請求項１記載のプ
ロピレン酸化用複合酸化物触媒の製造方法。2. The components (3) and (4) are dissolved and mixed at 50 to 80 ° C., and the component (1) is dissolved 50 times.
To 80 ° C., and the mixture of component (3) and component (4) and component (1) are mixed under the condition that the temperature difference between both liquids is within 10 ° C., and at 60 to 90 ° C. after mixing. The method for producing a composite oxide catalyst for propylene oxidation according to claim 1, wherein the heating is performed for at least 1 hour or more.
で示される組成を有するものであることを特徴とする請
求項１〜３に記載のプロピレン酸化用複合酸化物触媒の
製造方法。 ＭｏaＢｉbＣｏcＮｉdＦｅeＸfＹgＺhＳｉiＯj （１） 式中、Ｍｏ、Ｂｉ、Ｃｏ，Ｎｉ、Ｆｅ、Ｓｉ及びＯはモ
リブテン、ビスマス、コバルト、ニッケル、鉄、珪素及
び酸素を表し、Ｘはマグネシウム（Ｍｇ）、カルシウム
（Ｃａ）、亜鉛（Ｚｎ）、セリウム（Ｃｅ）及びサマリ
ウム（Ｓｍ）からなる群から選ばれる少なくとも１種の
元素であり、Ｙはナトリウム（Ｎａ）、カリウム
（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタ
リウム（Ｔｌ）からなる群から選ばれる少なくとも１種
の元素であり、Ｚはホウ素（Ｂ）、リン（Ｐ）、砒素
（Ａｓ）及びタングステン（Ｗ）からなる群から選ばれ
る少なくとも１種の元素である。また、ａ〜ｊはそれぞ
れの元素の原子比を表わし、ａ＝１２のとき、ｂ＝０．
５〜７、ｃ＝０〜１０、ｄ＝０〜１０（但しｃ＋ｄ＝１
〜１０）、ｅ＝０．０５〜２、ｆ＝０〜１、ｇ＝０．０
１〜１、ｈ＝０〜３、ｉ＝０〜４８、の範囲にあり、ま
たｊは他の元素の酸化状態を満足させる数値である。3. The composite oxide catalyst is represented by the following general formula (1):
The method for producing a composite oxide catalyst for propylene oxidation according to any one of claims 1 to 3, wherein the method has the composition shown in. Mo a Bi b Co c Ni d Fe e X f Y g Z h Si i O j (1) In the formula, Mo, Bi, Co, Ni, Fe, Si and O are molybdenum, bismuth, cobalt, nickel, iron, Represents silicon and oxygen, X is at least one element selected from the group consisting of magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce) and samarium (Sm), and Y is sodium ( Na), potassium (K), rubidium (Rb), cesium (Cs) and at least one element selected from the group consisting of thallium (Tl), Z is boron (B), phosphorus (P), arsenic ( At least one element selected from the group consisting of As) and tungsten (W). Further, a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.
5-7, c = 0-10, d = 0-10 (however, c + d = 1
-10), e = 0.05-2, f = 0-1, g = 0.0
It is in the range of 1-1, h = 0 to 3, i = 0 to 48, and j is a numerical value satisfying the oxidation states of other elements.
酸素又は分子状酸素含有ガスにより気相酸化してアクロ
レイン及びアクリル酸を製造するに当たり、触媒として
請求項１〜３記載の方法により製造された複合酸化物触
媒を用いることを特徴とするアクロレイン及びアクリル
酸の製造方法。4. Producing acrolein and acrylic acid by gas phase oxidation of propylene with molecular oxygen or a gas containing molecular oxygen in the presence of an oxidation catalyst, the catalyst being produced by the method according to any one of claims 1 to 3. A method for producing acrolein and acrylic acid, which comprises using the above complex oxide catalyst.
Priority Applications (1)
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|---|---|---|---|
| JP2001368874A JP2003164763A (en) | 2001-12-03 | 2001-12-03 | Method for manufacturing composite oxide catalyst for oxidizing propylene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001368874A JP2003164763A (en) | 2001-12-03 | 2001-12-03 | Method for manufacturing composite oxide catalyst for oxidizing propylene |
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| Publication Number | Publication Date |
|---|---|
| JP2003164763A true JP2003164763A (en) | 2003-06-10 |
Family
ID=19178382
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|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP2003164763A (en) |
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| JP2007175600A (en) * | 2005-12-27 | 2007-07-12 | Mitsubishi Rayon Co Ltd | Method for manufacturing oxide catalyst |
| WO2014181839A1 (en) | 2013-05-09 | 2014-11-13 | 日本化薬株式会社 | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid, method for manufacturing same, and method for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid |
| KR20170125827A (en) | 2015-02-27 | 2017-11-15 | 닛뽄 가야쿠 가부시키가이샤 | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid and manufacturing method of same, and manufacturing method of unsaturated aldehyde and/or unsaturated carboxylic acid |
| WO2019198763A1 (en) | 2018-04-10 | 2019-10-17 | 日本化薬株式会社 | Method for producing at least one of unsaturated aldehyde and unsaturated carboxylic acid, and catalyst for production of at least one of unsaturated aldehyde and unsaturated carboxylic acid |
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2001
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|---|---|---|---|---|
| JP2007175600A (en) * | 2005-12-27 | 2007-07-12 | Mitsubishi Rayon Co Ltd | Method for manufacturing oxide catalyst |
| WO2014181839A1 (en) | 2013-05-09 | 2014-11-13 | 日本化薬株式会社 | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid, method for manufacturing same, and method for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid |
| US9656248B2 (en) | 2013-05-09 | 2017-05-23 | Nippon Kayaku Kabushiki Kaisha | Catalyst for producing unsaturated aldehyde and/or unsaturated carboxylic acid, method for producing same, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| KR20170125827A (en) | 2015-02-27 | 2017-11-15 | 닛뽄 가야쿠 가부시키가이샤 | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid and manufacturing method of same, and manufacturing method of unsaturated aldehyde and/or unsaturated carboxylic acid |
| US10300463B2 (en) | 2015-02-27 | 2019-05-28 | Nippon Kayaku Kabushiki Kaisha | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid and manufacturing method of same, and manufacturing method of unsaturated aldehyde and/or unsaturated carboxylic acid |
| WO2019198763A1 (en) | 2018-04-10 | 2019-10-17 | 日本化薬株式会社 | Method for producing at least one of unsaturated aldehyde and unsaturated carboxylic acid, and catalyst for production of at least one of unsaturated aldehyde and unsaturated carboxylic acid |
| US11254634B2 (en) | 2018-04-10 | 2022-02-22 | Nippon Kayaku Kabushiki Kaisha | Method for producing at least one of unsaturated aldehyde and unsaturated carboxylic acid and catalyst for producing at least one of unsaturated aldehyde and unsaturated carboxylic acid |
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| CN114289031A (en) * | 2021-11-12 | 2022-04-08 | 中海油天津化工研究设计院有限公司 | Annular coating catalyst for preparing acrolein through propylene oxidation and preparation method thereof |
| CN114289031B (en) * | 2021-11-12 | 2023-11-07 | 中海油天津化工研究设计院有限公司 | Annular coating catalyst for preparing acrolein by propylene oxidation and preparation method thereof |
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