JPH0597761A - Production of methacrolein and catalyst used for producing methacrolein - Google Patents
Production of methacrolein and catalyst used for producing methacroleinInfo
- Publication number
- JPH0597761A JPH0597761A JP4069791A JP6979192A JPH0597761A JP H0597761 A JPH0597761 A JP H0597761A JP 4069791 A JP4069791 A JP 4069791A JP 6979192 A JP6979192 A JP 6979192A JP H0597761 A JPH0597761 A JP H0597761A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- catalyst
- methacrolein
- producing
- group
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はイソブチレンまた三級ブ
タノールを分子状酸素により気相接触酸化してメタクロ
レインを製造する改良された方法及びこの接触酸化反応
に用いる改良された触媒の製造方法に関する。FIELD OF THE INVENTION The present invention relates to an improved method for producing methacrolein by vapor-phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen, and a method for producing an improved catalyst used in this catalytic oxidation reaction. ..
【０００２】[0002]
【従来の技術】イソブチレン又は三級ブタノールを分子
状酸素により気相接触酸化してメタクロレインを製造す
る際に用いられる触媒に関して、従来から数多くの提案
がなされている。なかでも、Ｍｏ、Ｂｉ及びＦｅを必須
成分として含有する外に、Ｃｏ及びＮｉからなる群から
選ばれた１種以上の元素、およびＫ、Ｒｂ及びＣｓから
なる群から選ばれた１種以上の元素を含有する触媒に関
して、数多くの提案がなされている。最近では、例え
ば、特開昭６３−１０７７４５号、あるいは特開昭６３
−１２２６４２号などのように、前記成分の他にＳｂあ
るいはＭｇなどの成分を加えて触媒の性能を高めるとい
う様な提案もなされている。しかし、これらの従来提案
の触媒は触媒活性、メタクロレインへの選択性、触媒の
安定性、触媒寿命などの触媒性能の点でまだ十分とはい
えず、その改良が望まれていた。2. Description of the Related Art A number of proposals have hitherto been made regarding catalysts used for producing methacrolein by vapor-phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen. Among them, in addition to containing Mo, Bi and Fe as essential components, one or more elements selected from the group consisting of Co and Ni, and one or more elements selected from the group consisting of K, Rb and Cs. Many proposals have been made regarding catalysts containing elements. Recently, for example, JP-A-63-107745 or JP-A-63-107745.
It has been proposed to add a component such as Sb or Mg in addition to the above-mentioned components to enhance the performance of the catalyst, such as No. 122642. However, these conventionally proposed catalysts are still not sufficient in terms of catalytic activity such as catalytic activity, selectivity to methacrolein, stability of the catalyst, and catalyst life, and improvement thereof has been desired.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的はＭｏ、
Ｂｉ及び好ましくは、Ｆｅ、Ｎｉ及びＣｏからなる群か
ら選ばれた１種以上の元素を含有する組成物と、モリブ
デン酸のアルカリ金属塩を含む組成物との混合物である
触媒の存在下でイソブチレン又は三級ブタノールを分子
状酸素により気相接触酸化してメタクロレインを収率よ
く製造する、改良された方法を提供することにある。DISCLOSURE OF INVENTION Problems to be Solved by the Invention
Isobutylene in the presence of a catalyst, which is a mixture of Bi and preferably a composition containing one or more elements selected from the group consisting of Fe, Ni and Co and a composition containing an alkali metal salt of molybdic acid. Another object of the present invention is to provide an improved method for producing methacrolein in good yield by subjecting tertiary butanol to gas-phase catalytic oxidation with molecular oxygen.
【０００４】本発明の別の目的はＭｏ、Ｂｉ及び好まし
くは、Ｆｅ、Ｎｉ及びＣｏからなる群から選ばれた１種
以上の元素を含有する組成物とモリブデン酸のアルカリ
金属塩を含む組成物とを混合し、加熱混合し、蒸発乾涸
し、焼成することによる、触媒活性、メタクロレインへ
の選択性、安定性において改良された、上記メタクロレ
イン製造用触媒の製造方法を提供することにある。Another object of the invention is a composition containing Mo, Bi and preferably one or more elements selected from the group consisting of Fe, Ni and Co and a composition containing an alkali metal salt of molybdic acid. It is intended to provide a method for producing the above-mentioned catalyst for producing methacrolein, which is improved in catalytic activity, selectivity to methacrolein, and stability by mixing with, heating and mixing, evaporating and drying, and calcining. ..
【０００５】[0005]
【課題を解決するため提手段】本発明に従って、一般式
（１）、 （Ｍｏ)a（Ｂｉ)b（Ｆｅ)c（Ｘ)d（Ｚ)f（Ｏ)g （１） ［式中、ＸはＮｉ及びＣｏからなる群から選ばれた１種
以上の元素を表し、ＺはＷ、Ｂｅ、Ｍｇ、Ｓ、Ｃａ、Ｓ
ｒ、Ｂａ、Ｔｅ、Ｓｅ、Ｃｅ、Ｇｅ、Ｍｎ、Ｚｎ、Ｃ
ｒ、Ａｇ、Ｓｂ、Ｐｂ、Ａｓ、Ｂ、Ｐ、Ｎｂ、Ｃｕ、Ｃ
ｄ、Ｓｎ、Ａｌ、Ｚｒ及びＴｉからなる群から選ばれた
１種以上の元素を表し、ａ、ｂ、ｃ、ｄ、ｆ及びｇは各
元素の原子比率を表し、ａを基準にとり、ａ＝１２とし
た時に、ｂ＝０．１〜１０、ｃ＝０〜２０、ｄ＝０〜２
０、ｆ＝０〜４であり、ｇは前記各成分の原子価を満足
するに必要な原子数である。］で示される組成物（１）
と、一般式（２） （Ａ)m（Ｍｏ)n（Ｏ)p （２） ［式中、ＡはＫ、Ｒｂ及びＣｓからなる群から選ばれた
１種以上の元素を表し、ｍ、ｎ及びｐは各元素の原子比
率を表し、ｍを基準にとり、ｍ＝２とした時に、ｎ＝１
〜９、ｐ＝３ｎ＋１である。］で示される組成物（２）
との混合物である触媒の存在下で、イソブチレン又は三
級ブタノールを分子状酸素を用いて気相接触酸化するこ
とを特徴とするメタクロレインの製造方法が提供され、
また、上記組成物（１）と組成物（２）とを加熱混合
し、蒸発乾涸し、焼成することを特徴とする、上記のメ
タクロレインの製造方法に用いる触媒の製造方法が提供
される。According to the present invention, according to the present invention, the general formula (1), (Mo) a (Bi) b (Fe) c (X) d (Z) f (O) g (1) X represents one or more elements selected from the group consisting of Ni and Co, and Z represents W, Be, Mg, S, Ca, S.
r, Ba, Te, Se, Ce, Ge, Mn, Zn, C
r, Ag, Sb, Pb, As, B, P, Nb, Cu, C
d, Sn, Al, Zr, and one or more elements selected from the group consisting of Ti, a, b, c, d, f, and g represent the atomic ratio of each element. = 12, b = 0.1-10, c = 0-20, d = 0-2
0, f = 0 to 4, and g is the number of atoms required to satisfy the valence of each component. ] The composition (1) shown by
And (2) (A) m (Mo) n (O) p (2) [wherein A represents one or more elements selected from the group consisting of K, Rb and Cs, m, n and p represent the atomic ratio of each element, and when m = 2 based on m, n = 1
˜9, p = 3n + 1. ] The composition (2) shown by
A method for producing methacrolein, characterized in that isobutylene or tertiary butanol is subjected to vapor phase catalytic oxidation with molecular oxygen in the presence of a catalyst that is a mixture with
Further, there is provided a method for producing a catalyst used in the above-mentioned method for producing methacrolein, which comprises heating and mixing the composition (1) and the composition (2), evaporating to dryness, and firing.
【０００６】本発明の効果を得るためには、組成物
（１）と組成物（２）とをまず別々に調製することが重
要である。本発明における触媒は、組成物（１）と組成
物（２）とを混合して得られ、その混合物全体の組成は
この分野では公知の組成である。全体の組成が同じであ
るにも拘らず、組成物（１）と組成物（２）を、まず別
々に調製しその後混合して得られる本発明の触媒が、従
来技術の触媒に比べ高い性能を示す理由は明らかではな
いが、組成物（１）と組成物（２）のそれぞれが、本発
明の対象反応に必要な複数の好ましい活性点を提供し、
それらの協奏的効果により高い選択性が発現したものと
考えられる。一方、従来技術の触媒では、組成物（２）
のアルカリ金属元素が、触媒調製の沈殿過程で組成物
（１）を構成する元素群とで本発明の対象反応にとって
好ましくない相、あるいは不要な相を形成するために、
選択性があるレベル以上にならないものと考えられる。In order to obtain the effects of the present invention, it is important to prepare the composition (1) and the composition (2) separately first. The catalyst in the present invention is obtained by mixing the composition (1) and the composition (2), and the composition of the entire mixture is a composition known in the art. Despite having the same overall composition, the catalyst of the present invention obtained by first preparing the composition (1) and the composition (2) separately and then mixing them has higher performance than the prior art catalyst. It is not clear why each of composition (1) and composition (2) provides a plurality of preferable active sites necessary for the subject reaction of the present invention,
It is considered that high selectivity was developed due to their concerted effects. On the other hand, in the catalyst of the prior art, the composition (2)
In order to form an unfavorable phase or an unnecessary phase for the subject reaction of the present invention with the group of elements constituting the composition (1) in the precipitation process of catalyst preparation,
It is considered that the selectivity does not exceed a certain level.
【０００７】また、本発明の効果を得るには、組成物
（１）と組成物（２）の混合割合については好ましい範
囲がある。即ち、組成物（２）のＡ，即ちＫ、Ｒｂ又は
Ｃｓと組成物（１）のＢｉの原子比率Ａ／Ｂｉが０．０
２〜１．０の範囲、より好ましくは０．０５〜０．５の
範囲となるように混合される。組成物（２）のＫ、Ｒｂ
又はＣｓと組成物（１）のＢｉの原子比率が０．０２未
満の場合及び１．０を越える場合には組成物（１）と組
成物（２）の協奏的効果が不十分となり、選択性、酸化
活性が不十分となる。In order to obtain the effects of the present invention, there is a preferable range for the mixing ratio of the composition (1) and the composition (2). That is, the atomic ratio A / Bi of A of the composition (2), that is, K, Rb or Cs and Bi of the composition (1) is 0.0.
It is mixed in a range of 2 to 1.0, and more preferably in a range of 0.05 to 0.5. K, Rb of composition (2)
Alternatively, when the atomic ratio of Cs to Bi of the composition (1) is less than 0.02 or exceeds 1.0, the concerted effect of the composition (1) and the composition (2) becomes insufficient, and thus the selection. Properties and oxidative activity are insufficient.
【０００８】本発明の方法で使用する組成物（１）及び
組成物（２）は、この分野で通常用いられる方法、例え
ば次のような方法で調製することができる：組成物
（１）は、適当なモリブデン酸塩、例えばモリブデン酸
アンモンを純水に加熱溶解し、これにＢｉ化合物の水溶
液を加え、必要に応じて、Ｆｅ、ＣｏおよびＮｉから選
ばれる１種以上の元素の化合物の水溶液を加え、さらに
必要に応じて、Ｗ、Ｂｅ、Ｍｇ、Ｓ、Ｃａ、Ｓｒ、Ｂ
ａ、Ｔｅ、Ｓｅ、Ｃｅ、Ｇｅ、Ｍｎ、Ｚｎ、Ｃｒ、Ａ
ｇ、Ｓｂ、Ｐｂ、Ａｓ、Ｂ、Ｐ、Ｎｂ、Ｃｕ、Ｃｄ、Ｓ
ｎ、Ａｌ、Ｚｒ及びＴｉからなる群から選ばれた１種以
上の元素の化合物を加え、また、必要に応じてＳｉＯ2
などの担体を加え、得られる泥状懸濁液を乾燥し、仮焼
し、２００〜６５０℃の温度範囲で焼成することにより
得られる；組成物（２）は，適当なモリブデン酸塩、例
えば、モリブデン酸アンモンを純水に加熱溶解し、これ
にＫ、Ｒｂ、Ｃｓから選ばれる１種以上の元素の化合
物、例えば、硝酸セシウムをＣｓ：Ｍｏの原子比率２：
１〜９となるように加えたのち、硝酸で中和し、蒸発乾
涸し、仮焼し、２００〜５００℃の温度範囲で焼成して
調製される。The composition (1) and the composition (2) used in the method of the present invention can be prepared by a method commonly used in this field, for example, the following method: The composition (1) is , An appropriate molybdate, for example, ammonium molybdate, is heated and dissolved in pure water, an aqueous solution of a Bi compound is added thereto, and if necessary, an aqueous solution of a compound of one or more elements selected from Fe, Co and Ni. And, if necessary, W, Be, Mg, S, Ca, Sr, B
a, Te, Se, Ce, Ge, Mn, Zn, Cr, A
g, Sb, Pb, As, B, P, Nb, Cu, Cd, S
A compound of one or more elements selected from the group consisting of n, Al, Zr, and Ti is added, and if necessary, SiO 2
And the like, and the resulting mud-like suspension is dried, calcined and calcined in the temperature range of 200 to 650 ° C .; composition (2) comprises a suitable molybdate, for example , Ammonium molybdate is heated and dissolved in pure water, and a compound of one or more elements selected from K, Rb, and Cs, for example, cesium nitrate is added to the Cs: Mo atomic ratio of 2:
It is prepared by neutralizing with nitric acid, evaporating to dryness, calcining, and firing in a temperature range of 200 to 500 ° C.
【０００９】本発明において触媒は次のようにして調製
される。即ち、前記した組成物（１）と組成物（２）
を、組成物（２）のＫ、Ｒｂ又はＣｓと組成物（１）の
Ｂｉの原子比率が０．０２〜１．０の範囲、好ましくは
０．０５〜０．５の範囲となるように混合する。混合す
る際、水を添加することが触媒性能を高める上でより好
ましい。混合は３０℃から３００℃の温度範囲で行われ
る。得られた混合物を３００℃以下の温度で蒸発乾涸
し、３００℃から６５０℃の温度範囲で焼成する。混合
時に水を加える場合の水添加量には特に制限はないが、
混合が充分におこなえる程度のスラリー状態とするのが
好ましい。また、水を添加する場合、加熱混合を自己発
生圧力の下、オートクレーブ中で行うこともできる。触
媒は、粒状あるいは成形体として固定床で使用される
が、移動床あるいは流動床にも使用できる。In the present invention, the catalyst is prepared as follows. That is, the composition (1) and the composition (2) described above.
Such that the atomic ratio of K, Rb or Cs of the composition (2) to Bi of the composition (1) is in the range of 0.02 to 1.0, preferably 0.05 to 0.5. Mix. When mixing, it is more preferable to add water in order to enhance the catalyst performance. Mixing is performed in the temperature range of 30 ° C to 300 ° C. The mixture obtained is evaporated to dryness at a temperature of 300 ° C. or lower and calcined in the temperature range of 300 ° C. to 650 ° C. There is no particular limitation on the amount of water added when water is added during mixing,
It is preferable that the slurry state is such that mixing can be sufficiently performed. When water is added, heating and mixing can be performed in an autoclave under self-generated pressure. The catalyst is used as a granular or shaped body in a fixed bed, but it can also be used in a moving bed or a fluidized bed.
【００１０】本発明において触媒の原料は、触媒調製過
程で酸化物の形に分解され得る化合物であることが望ま
しい。そのような化合物としては、例えば硝酸塩、アン
モニウム塩、有機酸塩、酸化物、金属酸、金属酸アンモ
ニウム塩などがある。またシリカの原料としては、シリ
カゾル、シリカゲル、珪酸エステル、珪酸塩などが用い
られる。In the present invention, the raw material of the catalyst is preferably a compound which can be decomposed into an oxide form during the catalyst preparation process. Examples of such compounds include nitrates, ammonium salts, organic acid salts, oxides, metal acids, ammonium metal acid salts and the like. As a raw material of silica, silica sol, silica gel, silicate ester, silicate or the like is used.
【００１１】本発明による気相接触酸化反応は、原料ガ
ス組成として１〜１０容量％のイソブチレン又は三級ブ
タノール、３〜２０容量％の分子状酸素及び７０〜９６
容量％の希釈ガスからなる混合ガスを前記した触媒上に
２５０〜４５０℃の温度範囲および常圧〜１０気圧の圧
力下、空間速度３００〜５０００／ｈｒで導入すること
で実施される。In the gas-phase catalytic oxidation reaction according to the present invention, the source gas composition is 1 to 10% by volume of isobutylene or tertiary butanol, 3 to 20% by volume of molecular oxygen and 70 to 96.
It is carried out by introducing a mixed gas composed of a volume% of a diluent gas onto the above-mentioned catalyst at a space velocity of 300 to 5000 / hr under a temperature range of 250 to 450 ° C. and a pressure of atmospheric pressure to 10 atm.
【００１２】分子状酸素源としては通常空気が使用され
るが、純酸素を使用してもよい。また希釈ガスとして
は、窒素、炭酸ガスなどの不活性ガスが使用される。反
応ガスに含まれる非凝縮性ガスの一部を循環して希釈ガ
スとして使用してもよい。希釈ガスとして水蒸気を併せ
て使用することが、活性、選択性を高める上で好まし
い。その場合、水蒸気は原料ガス中に通常６０容量％ま
での量で添加される。Air is usually used as the molecular oxygen source, but pure oxygen may be used. An inert gas such as nitrogen or carbon dioxide is used as the dilution gas. A part of the non-condensable gas contained in the reaction gas may be circulated and used as a diluent gas. It is preferable to use water vapor together as a diluent gas in order to enhance activity and selectivity. In that case, steam is usually added to the source gas in an amount of up to 60% by volume.
【００１３】[0013]
【実施例】実施例および比較例によって本発明をさらに
詳細に説明する： 実施例１ 水１２００ｍｌを加熱攪拌しつつ、パラモリブデン酸ア
ンモン１２７．２ｇｒを溶解し、Ａ液とした。水１８０
ｍｌに硝酸コバルト１３９．６ｇｒ、硝酸第二鉄７２．
２ｇｒを溶解し、Ｂ液とした。６０％硝酸１５ｍｌと水
１５０ｍｌとからなる硝酸水溶液に硝酸ビスマス２８．
６ｇｒを溶解し、Ｃ液とした。Ａ液にＢ液、Ｃ液を順次
滴下混合し、得られたスラリー溶液を噴霧乾燥し、仮焼
し、３００℃で焼成して、Ｍｏ／Ｂｉ／Ｆｅ／Ｃｏ原子
比率が１２／１／３／８なる組成物（１）を得た；ま
た、水２００ｍｌを加熱攪拌しつつ、モリブデン酸アン
モン１９．６ｇｒを溶解し、次いで硝酸セシウム３９．
０ｇｒを加え、硝酸で中和した後、蒸発乾涸し、仮焼
し、４００℃で焼成して、Ｃｓ／Ｍｏ原子比率が２／１
なる組成物（２）を得た；Ｃｓ／Ｂｉ原子比率が０．１
となるよう、組成物（１）と組成物（２）を１１６／１
の割合で混合し、水を８０ｗｔ％となるように加え、１
００℃で十分に加熱混合した後、１２０℃で蒸発乾涸
し、４００℃で焼成して触媒を調製した；得られた触媒
１ｍｌを通常の流通式反応器に充填し、イソブチレン
８．３容量％、酸素１６．７容量％、水蒸気８．３容量
％、残り６６．７容量％が窒素という原料ガス組成、反
応温度３４０℃、空間速度３６００／ｈｒという条件で
反応を行い、触媒の性能を評価した。その結果を表１に
示す。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples: Example 1 Ammon paramolybdate 127.2 gr was dissolved while heating and stirring 1200 ml of water to obtain a liquid A. Water 180
Cobalt nitrate 139.6 gr, ferric nitrate 72.
2 gr was dissolved and used as a solution B. Bismuth nitrate 28. was added to a nitric acid aqueous solution consisting of 60% nitric acid 15 ml and water 150 ml.
6 gr was dissolved to obtain a liquid C. Liquid B and liquid C were sequentially added dropwise to liquid A, and the resulting slurry solution was spray-dried, calcined and calcined at 300 ° C., and the Mo / Bi / Fe / Co atomic ratio was 12/1/3. A composition (1) of 8/8 was obtained; and while stirring 200 ml of water with heating, 19.6 gr of ammonium molybdate was dissolved, and then cesium nitrate 39.
After adding 0 gr and neutralizing with nitric acid, it was evaporated to dryness, calcined and baked at 400 ° C., and the Cs / Mo atomic ratio was 2/1.
To obtain a composition (2) having a Cs / Bi atomic ratio of 0.1.
So that the composition (1) and the composition (2) are 116/1.
, And add water to 80 wt% to add 1
The mixture was sufficiently heated and mixed at 00 ° C., evaporated to dryness at 120 ° C., and calcined at 400 ° C. to prepare a catalyst; 1 ml of the obtained catalyst was charged into a usual flow reactor, and isobutylene was 8.3 vol%. , Oxygen 16.7% by volume, water vapor 8.3% by volume, the remaining 66.7% by volume are nitrogen, and the reaction is performed under the conditions of a raw material gas composition, reaction temperature 340 ° C., space velocity 3600 / hr, and catalyst performance is evaluated. did. The results are shown in Table 1.
【００１４】実施例２〜９ 実施例１と同様にして調製した組成物（１）と表１に示
した組成物（２）を表１に示したＡ／Ｂｉ原子比率とな
るように実施例１と同様の方法で触媒を調製した。得ら
れた触媒の性能を実施例１と同様の方法で評価した。そ
の結果を表１に示す。Examples 2 to 9 The composition (1) prepared in the same manner as in Example 1 and the composition (2) shown in Table 1 were used so that the A / Bi atomic ratio shown in Table 1 was obtained. A catalyst was prepared in the same manner as in 1. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００１５】実施例１０ 実施例１の硝酸コバルトに代え硝酸ニッケル６９．６ｇ
ｒを用いた他は実施例１と同様の方法で触媒を調製し
た。得られた触媒の性能を実施例１と同様の方法で評価
した。その結果を表１に示す。Example 10 Nickel nitrate 69.6 g in place of the cobalt nitrate of Example 1
A catalyst was prepared in the same manner as in Example 1 except that r was used. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００１６】実施例１１、１２ 実施例１０と同様にして調製した組成物（１）と表１に
示した組成物（２）を表１に示した原子比率となるよう
に実施例１０と同様の方法で触媒を調製した。得られた
触媒の性能を実施例１と同様の方法で評価した。その結
果を表１に示す。Examples 11 and 12 Composition (1) prepared in the same manner as in Example 10 and composition (2) shown in Table 1 had the same atomic ratio as shown in Table 1 and had the same composition as in Example 10. A catalyst was prepared by the method described in 1. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００１７】実施例１３ 実施例１と同様にして調製した組成物（１）と表１に示
した組成物（２）をＡ／Ｂｉ原子比率が１．２となるよ
うに実施例１と同様の方法で触媒を調製した。得られた
触媒の性能を実施例１と同様の方法で評価した。その結
果を表１に示す。Example 13 The composition (1) prepared in the same manner as in Example 1 and the composition (2) shown in Table 1 were prepared in the same manner as in Example 1 so that the A / Bi atomic ratio was 1.2. A catalyst was prepared by the method described in 1. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００１８】比較例１ 実施例１と同様にして調製した組成物（１）のみを触媒
として使用し、実施例１と同様の方法で評価した。その
結果を表１に示す。Comparative Example 1 Evaluation was carried out in the same manner as in Example 1 except that only the composition (1) prepared in the same manner as in Example 1 was used as a catalyst. The results are shown in Table 1.
【００１９】比較例２ 実施例１と同様にして調製したＣｓ、Ｍｏ比が２／７の
組成物（２）のみを触媒として使用し、実施例１と同様
の方法で評価した。その結果を表１に示す。Comparative Example 2 Only the composition (2) having a Cs / Mo ratio of 2/7 prepared in the same manner as in Example 1 was used as a catalyst and evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００２０】比較例３ 水１２００ｍｌを加熱攪拌しつつ、パラモリブデン酸ア
ンモン１２７．７ｇｒ及び硝酸セシウム１．１７ｇｒを
溶解し、Ａ液とした。水１８０ｍｌに硝酸コバルト１３
９．６ｇｒ、硝酸第二鉄７２．２ｇｒを溶解し、Ｂ液と
した。６０％硝酸１５ｍｌと水１５０ｍｌとからなる硝
酸水溶液に硝酸ビスマス２８．６ｇｒを溶解し、Ｃ液と
した。Ａ液にＢ液、Ｃ液を順次滴下混合し、得られたス
ラリー溶液を噴霧乾燥し、仮焼し、４００℃で焼成し
て、Ｍｏ／Ｂｉ／Ｆｅ／Ｃｏ／Ｃｓ原子比率が１２．０
５／１／３／８／０．１なる触媒、即ち実施例１と同じ
組成をもつ触媒を調製した。得られた触媒の性能を実施
例１と同様の方法で評価した。その結果を表２に示す。Comparative Example 3 While stirring 1200 ml of water with heating, 127.7 gr of ammonium paramolybdate and 1.17 gr of cesium nitrate were dissolved to prepare a solution A. Cobalt nitrate 13 in 180 ml of water
9.6 gr and ferric nitrate 72.2 gr were melt | dissolved and it was set as the B liquid. 28.6 gr of bismuth nitrate was dissolved in a nitric acid aqueous solution containing 15 ml of 60% nitric acid and 150 ml of water to prepare a liquid C. Liquid B and liquid C were sequentially added dropwise to liquid A, and the resulting slurry solution was spray-dried, calcined and fired at 400 ° C., and the Mo / Bi / Fe / Co / Cs atomic ratio was 12.0.
A catalyst of 5/1/3/8 / 0.1, that is, a catalyst having the same composition as in Example 1 was prepared. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００２１】比較例４ 比較例３のパラモリブデン酸アンモン及び硝酸セシウム
の量をそれぞれ１２８．３ｇｒ及び２．３４ｇｒと変え
た他は比較例３と同様の方法で、Ｍｏ／Ｂｉ／Ｆｅ／Ｃ
ｏ／Ｃｓ原子比率が１２．１／１／３／８／０．２なる
触媒、即ち実施例２と同じ組成を持つ触媒を調製した。
得られた触媒の性能を実施例１と同様の方法で評価し
た。その結果を表２に示す。Comparative Example 4 Mo / Bi / Fe / C was prepared in the same manner as in Comparative Example 3 except that the amounts of ammonium paramolybdate and cesium nitrate in Comparative Example 3 were changed to 128.3 gr and 2.34 gr, respectively.
A catalyst having an o / Cs atomic ratio of 12.1 / 1/3/8 / 0.2, that is, a catalyst having the same composition as in Example 2 was prepared.
The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００２２】比較例５ 比較例３のパラモリブデン酸アンモン及び硝酸セシウム
の量をそれぞれ１２９．９ｇｒ及び５．８５ｇｒと変え
た他は比較例３と同様の方法で、Ｍｏ／Ｂｉ／Ｆｅ／Ｃ
ｏ／Ｃｓ原子比率が１２．２５／１／３／８／０．５な
る触媒、即ち実施例３と同じ組成を持つ触媒を調製し
た。得られた触媒の性能を実施例１と同様の方法で評価
した。その結果を表２に示す。Comparative Example 5 Mo / Bi / Fe / C was prepared in the same manner as in Comparative Example 3 except that the amounts of ammonium paramolybdate and cesium nitrate in Comparative Example 3 were changed to 129.9 gr and 5.85 gr, respectively.
A catalyst having an o / Cs atomic ratio of 12.25 / 1/3/8 / 0.5, that is, a catalyst having the same composition as in Example 3 was prepared. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００２３】比較例６ 特開昭６３−１０７７４５の実施例１と同様の方法で触
媒を調製した。即ち、水１０００部にモリブデン酸アン
モン５００部および硝酸セシウム３２．２部を加え加熱
攪拌した（Ａ液）。別に水８５０部に６０％硝酸２５０
部を加え均一にした後、硝酸ビスマス１１４．５部を加
え溶解した。これに硝酸第二鉄２８６．０部及び硝酸コ
バルト４８０．７部を順次加え溶解した（Ｂ液）。Ａ液
にＢ液を加えスラリー状にした後、平均粒径０．０３ミ
クロンの三酸化アンチモン５１．６部を加え加熱攪拌
し、水の大部分を蒸発させた。得られたケーキ状の物質
を１２０℃で乾燥させた後、５００℃で１０時間焼成
し、成形して触媒とした。得られた触媒の性能を実施例
１と同様の方法で評価した。その結果を表２に示す。Comparative Example 6 A catalyst was prepared in the same manner as in Example 1 of JP-A-63-107745. That is, 500 parts of ammonium molybdate and 32.2 parts of cesium nitrate were added to 1000 parts of water and heated and stirred (solution A). Separately, 850 parts of water and 250% of 60% nitric acid
Then, 114.5 parts of bismuth nitrate was added and dissolved. To this, 286.0 parts of ferric nitrate and 480.7 parts of cobalt nitrate were sequentially added and dissolved (solution B). Solution B was added to solution A to form a slurry, 51.6 parts of antimony trioxide having an average particle size of 0.03 micron was added, and the mixture was heated with stirring to evaporate most of the water. The cake-like substance obtained was dried at 120 ° C., and then calcined at 500 ° C. for 10 hours to form a catalyst. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００２４】比較例７ 特開昭６３−１２２６４２の実施例１と同様の方法で触
媒を調製した。即ち、水１０００部にモリブデン酸アン
モン５００部、パラタングステン酸アンモン１８．５
部、硝酸セシウム１８．４部および２０％シリカゲル３
５４．５部を加え加熱攪拌した（Ａ液）。別に水８５０
部に６０％硝酸２５０部を加え均一にした後、硝酸ビス
マス５７．２部を加え溶解した。これに硝酸第二鉄２３
８．４部、硝酸クロム４．７部、硝酸ニッケル４１１．
８部及び硝酸マグネシウム６０．５部を順次加え溶解し
た（Ｂ液）。Ａ液にＢ液を加えスラリー状にした後、三
酸化アンチモン３４．４部を加え加熱攪拌し、水の大部
分を蒸発させた。得られたケーキ状の物質を１２０℃で
乾燥させた後、５００℃で１０時間焼成し、成形して触
媒とした。得られた触媒の性能を実施例１と同様の方法
で評価した。その結果を表２に示す。Comparative Example 7 A catalyst was prepared in the same manner as in Example 1 of JP-A-63-122642. That is, 500 parts of ammonium molybdate, 18.5 parts of ammonium paratungstate in 1000 parts of water.
Part, cesium nitrate 18.4 parts and 20% silica gel 3
54.5 parts was added and the mixture was heated and stirred (Liquid A). Separately water 850
After 250 parts of 60% nitric acid was added to the mixture to make it uniform, 57.2 parts of bismuth nitrate was added and dissolved. Ferric nitrate 23
8.4 parts, chromium nitrate 4.7 parts, nickel nitrate 411.
8 parts and 60.5 parts of magnesium nitrate were sequentially added and dissolved (solution B). Solution B was added to solution A to form a slurry, 34.4 parts of antimony trioxide was added, and the mixture was heated with stirring to evaporate most of the water. The cake-like substance obtained was dried at 120 ° C., and then calcined at 500 ° C. for 10 hours to form a catalyst. The performance of the obtained catalyst was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００２５】[0025]
【表１】 表中の転化率はイソブチレン転化率であり、選択率およ
び収率は、それぞれメタクロレインへの選択率、収率を
意味する。[Table 1] The conversion rate in the table is the isobutylene conversion rate, and the selectivity and yield mean the selectivity and yield for methacrolein, respectively.
【００２６】[0026]
【表２】 表中の転化率はイソブチレン転化率であり、選択率およ
び収率は、それぞれメタクロレインへの選択率、収率を
意味する。[Table 2] The conversion rate in the table is the isobutylene conversion rate, and the selectivity and yield mean the selectivity and yield for methacrolein, respectively.
【００２７】[0027]
【発明の効果】活性、メタクロレインへの選択性、安定
性に優れた新規な触媒を用いることによりメタクロレイ
ンを効率的に製造できる。INDUSTRIAL APPLICABILITY Methacrolein can be efficiently produced by using a novel catalyst excellent in activity, selectivity to methacrolein, and stability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 45/35 45/37 47/22 Ｊ 9049−4Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical indication C07C 45/35 45/37 47/22 J 9049-4H
Claims (8)
以上の元素を表し、ＺはＷ、Ｂｅ、Ｍｇ、Ｓ、Ｃａ、Ｓ
ｒ、Ｂａ、Ｔｅ、Ｓｅ、Ｃｅ、Ｇｅ、Ｍｎ、Ｚｎ、Ｃ
ｒ、Ａｇ、Ｓｂ、Ｐｂ、Ａｓ、Ｂ、Ｐ、Ｎｂ、Ｃｕ、Ｃ
ｄ、Ｓｎ、Ａｌ、Ｚｒ及びＴｉからなる群から選ばれた
１種以上の元素を表し、ａ、ｂ、ｃ、ｄ、ｆ及びｇは各
元素の原子比率を表し、ａを基準にとり、ａ＝１２とし
た時に、ｂ＝０．１〜１０、ｃ＝０〜２０、ｄ＝０〜２
０、ｆ＝０〜４であり、ｇは前記各成分の原子価を満足
するのに必要な原子数である。］で示される組成物
（１）と、一般式（２） （Ａ)m（Ｍｏ)n（Ｏ)p （２） ［式中、ＡはＫ、Ｒｂ及びＣｓからなる群から選ばれた
１種以上の元素を表し、ｍ、ｎ及びｐは各元素の原子比
率を表し、ｍを基準にとり、ｍ＝２とした時に、ｎ＝１
〜９、ｐ＝３ｎ＋１である。］で示される組成物（２）
との混合物である触媒の存在下で、イソブチレン又は三
級ブタノールを分子状酸素を用いて気相接触酸化するこ
とを特徴とするメタクロレインの製造方法。1. General formula (1) (Mo) a (Bi) b (Fe) c (X) d (Z) f (O) g (1) [wherein X is a group consisting of Ni and Co. Represents one or more selected elements, Z is W, Be, Mg, S, Ca, S
r, Ba, Te, Se, Ce, Ge, Mn, Zn, C
r, Ag, Sb, Pb, As, B, P, Nb, Cu, C
d, Sn, Al, Zr, and one or more elements selected from the group consisting of Ti, a, b, c, d, f, and g represent the atomic ratio of each element. = 12, b = 0.1-10, c = 0-20, d = 0-2
0, f = 0 to 4, and g is the number of atoms required to satisfy the valence of each component. ] The composition (1) represented by the formula (1) and the general formula (2) (A) m (Mo) n (O) p (2) [wherein A is 1 selected from the group consisting of K, Rb and Cs. Represents more than one element, m, n and p represent atomic ratios of each element, and when m = 2 based on m, n = 1
˜9, p = 3n + 1. ] The composition (2) shown by
A method for producing methacrolein, which comprises subjecting isobutylene or tertiary butanol to gas-phase catalytic oxidation with molecular oxygen in the presence of a catalyst which is a mixture with.
が、Ａ／Ｂｉの原子比率で表して０．０２〜１．０であ
る請求項１記載の製造方法。2. The production method according to claim 1, wherein the mixing ratio of the composition (1) and the composition (2) is 0.02 to 1.0 expressed by the atomic ratio of A / Bi.
から３００℃の温度範囲で加熱混合し、３００℃以下の
温度で蒸発乾涸し、３００℃から６５０℃の温度範囲で
焼成して得られた触媒を用いる請求項１又は２記載の製
造方法。3. The composition (1) and the composition (2) at 30 ° C.
3. The production method according to claim 1 or 2, wherein the catalyst obtained by heating and mixing in a temperature range of 300 to 300 ° C, evaporating to dryness at a temperature of 300 ° C or less, and calcining in a temperature range of 300 to 650 ° C is used.
合を水の存在下で実施して得られた触媒を用いる請求項
３記載の製造方法。4. The production method according to claim 3, wherein a catalyst obtained by heating and mixing the composition (1) and the composition (2) in the presence of water is used.
以上の元素を表し、ＺはＷ、Ｂｅ、Ｍｇ、Ｓ、Ｃａ、Ｓ
ｒ、Ｂａ、Ｔｅ、Ｓｅ、Ｃｅ、Ｇｅ、Ｍｎ、Ｚｎ、Ｃ
ｒ、Ａｇ、Ｓｂ、Ｐｂ、Ａｓ、Ｂ、Ｐ、Ｎｂ、Ｃｕ、Ｃ
ｄ、Ｓｎ、Ａｌ、Ｚｒ及びＴｉからなる群から選ばれた
１種以上の元素を表し、ａ、ｂ、ｃ、ｄ、ｆ及びｇは各
元素の原子比率を表し、ａを基準にとり、ａ＝１２とし
た時に、ｂ＝０．１〜１０、ｃ＝０〜２０、ｄ＝０〜２
０、ｆ＝０〜４であり、ｇは前記各成分の原子価を満足
するに必要な原子数である。］で示される組成物（１）
と、一般式（２） （Ａ)m（Ｍｏ)n（Ｏ)p （２） ［式中、ＡはＫ、Ｒｂ及びＣｓからなる群から選ばれた
１種以上の元素を表し、ｍ、ｎ及びｐは各元素の原子比
率を表し、ｍを基準にとり、ｍ＝２とした時に、ｎ＝１
〜９、ｐ＝３ｎ＋１である。］で示される組成物（２）
とを加熱混合し、蒸発乾涸し、焼成することを特徴とす
る、メタクロレインの製造方法に用いる触媒の製造方
法。5. General formula (1) (Mo) a (Bi) b (Fe) c (X) d (Z) f (O) g (1) [wherein X is a group consisting of Ni and Co. Represents one or more selected elements, Z is W, Be, Mg, S, Ca, S
r, Ba, Te, Se, Ce, Ge, Mn, Zn, C
r, Ag, Sb, Pb, As, B, P, Nb, Cu, C
d, Sn, Al, Zr, and one or more elements selected from the group consisting of Ti, a, b, c, d, f, and g represent the atomic ratio of each element. = 12, b = 0.1-10, c = 0-20, d = 0-2
0, f = 0 to 4, and g is the number of atoms required to satisfy the valence of each component. ] The composition (1) shown by
And (2) (A) m (Mo) n (O) p (2) [wherein A represents one or more elements selected from the group consisting of K, Rb and Cs, and m, n and p represent the atomic ratio of each element, and when m = 2 based on m, n = 1
˜9, p = 3n + 1. ] The composition (2) shown by
A method for producing a catalyst used in the method for producing methacrolein, which comprises heating and mixing, and evaporating to dryness and firing.
が、Ａ／Ｂｉの原子比率で表して０．０２〜１．０であ
る請求項５記載の触媒の製造方法。6. The method for producing a catalyst according to claim 5, wherein the mixing ratio of the composition (1) and the composition (2) is 0.02 to 1.0 expressed by the atomic ratio of A / Bi.
から３００℃の温度範囲で加熱混合し、３００℃以下の
温度で蒸発乾涸し、３００℃から６５０℃の温度範囲で
焼成する、請求項５又は６記載の触媒の製造方法。7. The composition (1) and the composition (2) at 30 ° C.
7. The method for producing a catalyst according to claim 5 or 6, wherein the mixture is heated and mixed in a temperature range of 300 to 300 ° C, evaporated and dried at a temperature of 300 ° C or lower, and calcined in a temperature range of 300 to 650 ° C.
合を水の存在下で実施する請求項７記載の触媒の製造方
法。8. The method for producing the catalyst according to claim 7, wherein the composition (1) and the composition (2) are heated and mixed in the presence of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06979192A JP3257818B2 (en) | 1991-02-27 | 1992-02-19 | Method for producing methacrolein, catalyst used for producing methacrolein, and method for producing the catalyst |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3271891 | 1991-02-27 | ||
| JP3-32718 | 1991-02-27 | ||
| JP06979192A JP3257818B2 (en) | 1991-02-27 | 1992-02-19 | Method for producing methacrolein, catalyst used for producing methacrolein, and method for producing the catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0597761A true JPH0597761A (en) | 1993-04-20 |
| JP3257818B2 JP3257818B2 (en) | 2002-02-18 |
Family
ID=26371302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06979192A Expired - Fee Related JP3257818B2 (en) | 1991-02-27 | 1992-02-19 | Method for producing methacrolein, catalyst used for producing methacrolein, and method for producing the catalyst |
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| Country | Link |
|---|---|
| JP (1) | JP3257818B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000073109A (en) * | 1999-05-06 | 2000-12-05 | 유현식 | Preparation method of methacrolein |
| JP2004351295A (en) * | 2003-05-28 | 2004-12-16 | Nippon Shokubai Co Ltd | Catalyst for manufacture of unsaturated aldehyde and unsaturated carboxylic acid, preparation method therefor, and method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid |
| JP2019509889A (en) * | 2016-03-14 | 2019-04-11 | エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ | Process for the production of molybdenum-bismuth-cobalt-iron based mixed oxide catalysts by hydrothermal method |
| CN111185186A (en) * | 2020-02-19 | 2020-05-22 | 烟台大学 | Single-phase composite metal oxide catalyst, preparation method and application thereof |
| CN114425355A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing methylacrolein for fixed bed, preparation method and application |
-
1992
- 1992-02-19 JP JP06979192A patent/JP3257818B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000073109A (en) * | 1999-05-06 | 2000-12-05 | 유현식 | Preparation method of methacrolein |
| JP2004351295A (en) * | 2003-05-28 | 2004-12-16 | Nippon Shokubai Co Ltd | Catalyst for manufacture of unsaturated aldehyde and unsaturated carboxylic acid, preparation method therefor, and method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid |
| JP2019509889A (en) * | 2016-03-14 | 2019-04-11 | エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ | Process for the production of molybdenum-bismuth-cobalt-iron based mixed oxide catalysts by hydrothermal method |
| CN111185186A (en) * | 2020-02-19 | 2020-05-22 | 烟台大学 | Single-phase composite metal oxide catalyst, preparation method and application thereof |
| CN114425355A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing methylacrolein for fixed bed, preparation method and application |
| CN114425355B (en) * | 2020-09-27 | 2023-08-15 | 中国石油化工股份有限公司 | Catalyst for preparing methacrolein by fixed bed, preparation method and application |
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| Publication number | Publication date |
|---|---|
| JP3257818B2 (en) | 2002-02-18 |
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