JP2002292284A - Compound metal oxide catalyst and method for gaseous phase catalytic oxidizing reaction using the same - Google Patents
Compound metal oxide catalyst and method for gaseous phase catalytic oxidizing reaction using the sameInfo
- Publication number
- JP2002292284A JP2002292284A JP2001104145A JP2001104145A JP2002292284A JP 2002292284 A JP2002292284 A JP 2002292284A JP 2001104145 A JP2001104145 A JP 2001104145A JP 2001104145 A JP2001104145 A JP 2001104145A JP 2002292284 A JP2002292284 A JP 2002292284A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- metal oxide
- composite metal
- oxide catalyst
- less
- 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.)
- Pending
Links
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- 230000003197 catalytic effect Effects 0.000 title claims description 16
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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】本発明は複合金属酸化物触媒に関
するものである。より詳しくはアルカンの気相接触酸化
により不飽和ニトリル及び／又は不飽和カルボン酸を製
造するのに用いる複合金属酸化物触媒に関するものであ
る。The present invention relates to relates to a composite metal oxide catalyst. More particularly, to a composite metal oxide catalyst used for producing an unsaturated nitrile and / or unsaturated carboxylic acids by vapor phase catalytic oxidation of alkanes.
【０００２】[0002]
【従来の技術】気相接触酸化によるアルカンからの不飽
和ニトリル製造において使用される触媒についてはこれ
まで多くの報告がある。例えば、プロパンとアンモニア
との気相接触酸化反応によるアクリロニトリルの製造に
対しては、本発明者が提案するＭｏ、Ｖ、Ｔｅを必須成
分とした複合金属酸化物触媒（特開平２−２５７号公
報、特開平５−１４８２１２号公報、特開平５−２０８
１３６号公報）、およびＭｏ、Ｖ、Ｓｂを必須成分とし
た複合金属酸化物触媒（特開平９−１５７２４１号公
報）は優れた性能を示す。2. Description of the Related Art There have been many reports on catalysts used in the production of unsaturated nitriles from alkanes by gas phase catalytic oxidation. For example, for the production of acrylonitrile by a gas phase catalytic oxidation reaction of propane and ammonia, a composite metal oxide catalyst containing Mo, V, and Te as essential components proposed by the present inventor (JP-A-2-257) JP-A-5-148212, JP-A-5-208
136) and a composite metal oxide catalyst containing Mo, V, and Sb as essential components (JP-A-9-157241) exhibit excellent performance.
【０００３】アルカンの気相接触酸化反応は、発熱量が
大きいため、工業的に実施するには除熱効率の高い流動
層反応器が有利である。しかしながら、上記のＭｏ−Ｖ
−Ｔｅおよび／またはＳｂを含む酸化物触媒は、流動触
媒としたときの強度に問題があり、強度を改善するため
にＳｉＯ2含有量を増やすと逆に収率が低下することが
知られている。The gas phase catalytic oxidation reaction of alkanes generates a large amount of heat, so that a fluidized bed reactor having high heat removal efficiency is advantageous for industrial implementation. However, the above Mo-V
Oxide catalysts containing -Te and / or Sb have a problem in strength when used as a fluidized catalyst, and it is known that when the content of SiO 2 is increased in order to improve the strength, the yield is reduced. I have.
【０００４】例えば、特開平８−１４１４０１号公報に
は、ＳｉＯ2含有量を増やすと触媒の圧壊強度が増大す
ることが開示されており、圧壊強度３０ＭＰａ以上を得
るにはＳｉＯ2が少なくとも３０重量％必要であるとし
ている。しかしながら、ＳｉＯ2含有量が増大すると、
逆にアクリロニトリル（ＡＮ）の収率が低下するため、
その低下を抑制する方法として触媒をシュウ酸水溶液で
洗浄し、再び焼成するという複雑な工程を必要としてい
る。また、触媒の流動性をもたせるためには、触媒の充
填密度を低くする必要があることが記載されている。[0004] For example, Japanese Patent Laid-Open No. 8-141401 is disclosed that crushing strength of the catalyst increasing the SiO 2 content increases, SiO 2 is at least 30 weight to obtain a higher crushing strength 30MPa % Is required. However, as the SiO 2 content increases,
Conversely, the yield of acrylonitrile (AN) decreases,
As a method of suppressing the decrease, a complicated process of washing the catalyst with an oxalic acid aqueous solution and calcining again is required. Further, it is described that it is necessary to lower the packing density of the catalyst in order to give the fluidity of the catalyst.
【０００５】特開平１１−４７５９８号公報，特開平１
１−２５３８０１号公報には、特定のニオブ原料を用い
ることにより、ＳｉＯ2含有率を増やした場合でも収率
低下の少ない触媒が調製できるとされている。また、特
開２０００−１２６５９９号公報、特開２０００−１７
８２４２号公報には、ＳｉＯ2に担持された強度に優れ
た触媒でスズ、ジルコニウム等を含む場合に更に高い収
率が得られるとされている。上述したいずれの従来技術
においても、ＳｉＯ2含有量を３０％以上として触媒に
強度を持たせる方法が開示されている。[0005] JP-A-11-47598, JP-A-11-47598
According to Japanese Patent Application Laid-Open No. 1-253801, it is possible to prepare a catalyst with a small decrease in yield by using a specific niobium raw material even when the content of SiO 2 is increased. Also, JP-A-2000-126599, JP-A-2000-17
In 8242 discloses the tin excellent catalytic strength supported on SiO 2, has higher yields when containing zirconium and the like are to be obtained. In any of the above-described prior arts, a method is disclosed in which the content of SiO 2 is set to 30% or more to impart strength to the catalyst.
【０００６】[0006]
【発明が解決しようとする課題】上記の如く、Ｍｏ−Ｖ
−Ｎｂ−Ｔｅおよび／またはＳｂを含む公知の酸化物触
媒は、良好な性能を示すが、流動触媒としたときの強度
に問題があり、強度を持たせるためにＳｉＯ2含有量を
増やすと逆に収率が低下するという性質がある。このよ
うな収率低下を改善する従来の方法としては、触媒の酸
処理工程を必要としたり、新たな金属成分を必要とする
等、工業的に採用するには工程が煩雑であったり再現性
が不十分であるという問題点があった。As described above, Mo-V
Known oxide catalyst containing -Nb-Te and / or Sb show good performance, there is a problem with strength when formed into a fluidized catalyst, increasing the SiO 2 content in order to provide strength inverse the property that the yield is reduced to. Conventional methods for improving the yield loss include a step of treating the catalyst with an acid and a step of requiring a new metal component. Was insufficient.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の課
題を考慮しつつ、ＳｉＯ2含有量が２５重量％以下と比
較的低いＭｏ−Ｖ−Ｎｂ−Ｔｅおよび／またはＳｂを含
む公知の酸化物触媒について鋭意検討した。従来、流動
床反応用の触媒を使用する場合には、流動性が悪くなる
ため、嵩密度を高くすることは好ましくないとされてい
た。しかし、本発明者らはＳｉＯ2含有量の低い酸化物
触媒について、あえて嵩密度を上げたところ、意外にも
触媒の嵩密度がある特定の比較的高い範囲の触媒が、触
媒の流動性を低下させることなく、高い触媒性能を示し
且つ強度に優れることを見いだし本発明の完成に至っ
た。Means for Solving the Problems In view of the above-mentioned problems, the present inventors have proposed a known method containing Mo-V-Nb-Te and / or Sb having a relatively low SiO 2 content of 25% by weight or less. After intensive investigations about the oxide catalyst. Conventionally, when using a catalyst for fluidized bed reaction, the fluidity is deteriorated, it has been considered it is not preferable to increase the bulk density. However, the present inventors dared to increase the bulk density of the oxide catalyst having a low SiO 2 content, and unexpectedly, a specific relatively high range of catalysts having a bulk density of the catalyst reduced the fluidity of the catalyst. It has been found that the catalyst exhibits high catalytic performance and excellent strength without lowering, and the present invention has been completed.
【０００８】即ち、本発明の要旨は、下記組成式（１）
で表される複合金属酸化物と２５重量％以下（全触媒に
対して）のＳｉＯ2を含む触媒であり、且つ、この触媒
の見かけ嵩密度（ＡＢＤ）が１．２０g/ml以上であるこ
とを特徴とする複合金属酸化物触媒。That is, the gist of the present invention is that the following compositional formula (1)
And a catalyst containing 25 wt% or less (based on the total catalyst) of SiO 2 and having an apparent bulk density (ABD) of 1.20 g / ml or more. composite metal oxide catalyst, wherein.
【０００９】[0009]
【化３】 ＭｏaＶbＮｂcＸdＹfＯn （１） （式（１）において、Ｘはテルルおよび／またはアンチ
モンを表し、Ｙは周期表の１〜１６族の元素で、Ｍｏ，
Ｖ，Ｎｂ、Ｔｅ、Ｏ以外から選ばれる１以上の元素を表
し、ａ＝１．０、０．０１＜ｂ≦１、０．０５＜ｃ≦
０．５、０＜ｄ≦１、０≦ｆ＜１、ｎは他の元素の酸化
状態によって決まる値である。）Embedded image in Mo a V b Nb c X d Y f O n (1) ( Formula (1), X represents a tellurium and / or antimony, Y is 1 to 16 group elements of the periodic table, Mo ,
Represents one or more elements selected from elements other than V, Nb, Te, and O, and a = 1.0, 0.01 <b ≦ 1, 0.05 <c ≦
0.5, 0 <d ≦ 1, 0 ≦ f <1, and n are values determined by the oxidation state of other elements. )
【００１０】[0010]
【発明の実施の形態】以下、本発明を詳細に説明する。 （複合金属酸化物触媒の説明）本発明の複合酸化物触媒
は、下記組成式（１）で表され、ＳｉＯ2含有量が全触
媒に対して２５重量％以下である公知の触媒において、
見かけ嵩密度（ＡＢＤ）が１．２０g/ml以上であること
を特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Composite description of the metal oxide catalyst) composite oxide catalyst of the present invention are represented by the following composition formula (1), in known catalysts SiO 2 content is 25 wt% or less based on the total catalyst,
It is characterized by having an apparent bulk density (ABD) of 1.20 g / ml or more.
【００１１】[0011]
【化４】 ＭｏaＶbＮｂcＸdＹfＯn （１） （式（１）において、Ｘはテルルおよび／またはアンチ
モンを表し、Ｙは周期表の１〜１６族の元素で、Ｍｏ，
Ｖ，Ｎｂ、Ｔｅ、Ｏ以外から選ばれる１以上の元素を表
し、ａ＝１．０、０．０１＜ｂ≦１、０．０５＜ｃ≦
０．５、０＜ｄ≦１、０≦ｆ＜１、ｎは他の元素の酸化
状態によって決まる値である。＞ 本発明において、見かけ嵩密度（ＡＢＤ）とは、静止し
た一定容積のセルに規定の条件で試料を注ぎ、擦り切り
を行い、充填された試料の重量から求められた密度であ
る。また、充填嵩密度（ＣＢＤ）とは規定のタッピング
を行った後のサンプルの容積とサンプルの重量から求め
られた密度である。具体的は測定方法は下記実施例に記
載の方法に従うものとする。Embedded image in Mo a V b Nb c X d Y f O n (1) ( Formula (1), X represents a tellurium and / or antimony, Y is 1 to 16 group elements of the periodic table, Mo ,
Represents one or more elements selected from elements other than V, Nb, Te, and O, and a = 1.0, 0.01 <b ≦ 1, 0.05 <c ≦
0.5, 0 <d ≦ 1, 0 ≦ f <1, and n are values determined by the oxidation state of other elements. In the present invention, the apparent bulk density (ABD) is a density obtained by pouring a sample into a stationary fixed-volume cell under specified conditions, performing abrasion, and filling the sample. In addition, the filling bulk density (CBD) is a density obtained from the volume of the sample and the weight of the sample after performing a specified tapping. Specifically, the measuring method is in accordance with the method described in the following example.
【００１２】本発明の複合酸化物触媒は、上述した見か
け嵩密度（ＡＢＤ）が１．２０g/ml以上であり、好まし
くは１．２２g/ml以上、更に好ましくは１．２５g/ml以
上である。また、上限は好ましくは２．０g/ml以下、更
に好ましくは１．８g/ml以下、特には１．５g/ml以下で
ある。また、充填嵩密度（ＣＢＤ）は、１．３５g/ml以
上であり、好ましくは１．４０g/ml以上であり、更に好
ましくは１．４２g/ml以上である。上限は好ましくは
２．０g/ml以下、更に好ましくは１．８g/ml以下、特に
は１．６g/ml以下である。[0012] composite oxide catalyst of the present invention, the above-mentioned apparent bulk density (ABD) is not less 1.20 g / ml or more, preferably 1.22 g / ml or more, more preferably 1.25 g / ml or higher . The upper limit is preferably 2.0 g / ml or less, more preferably 1.8 g / ml or less, and particularly preferably 1.5 g / ml or less. The bulk density (CBD) is at least 1.35 g / ml, preferably at least 1.40 g / ml, and more preferably at least 1.42 g / ml. The upper limit is preferably not more than 2.0 g / ml, more preferably 1.8 g / ml or less, particularly equal to or less than 1.6 g / ml.
【００１３】本発明の酸化物触媒は、高い強度を有する
ものであるが、本発明において触媒の強度とは、以下に
説明する圧縮強度により表すものとし、具体的には後述
する実施例に記載の方法に従うものとする。球状試料の
圧縮強度：σは平松の方法（日本鉱業会誌 Ｖｏｌ．８
１、Ｎｏ．９３２，Ｐ．１０２４、１９６５、「非整形
試験片による岩石の引っ張り強さの迅速試験」）による
と、σ＝２．８Ｆ／π／Ｄ2で表される。（ここで、
Ｄ：積荷点間の距離であり、Ｆは圧裂時の応力であ
る。） そこで、本発明の圧縮強度Ｉ（ＭＰａ）は、ＪＩＳ２８
８４１−１９９３「圧縮強度」に従い、市販の微少圧縮
試験器を用い、ある粒径範囲の触媒粒子１００個（粒
径：ｄ（μｍ））に２点載荷を行い、粒子が破砕したと
きの応力：ｆ（ｇｆ）の平均値から、式（３）により計
算される。[0013] The oxide catalyst of the present invention are those having a high strength, the strength of the catalyst in the present invention, it is assumed to represent the compressive strength to be described below, according to the embodiments specifically described below Shall be followed. The compressive strength of the spherical sample: σ is the Hiramatsu method (Nippon Mining Journal Vol.8
1, No. 923, p. 1024,1965, according to "rapid test of tensile strength of the rock due to unshaped specimens"), represented by σ = 2.8F / π / D 2 . (here,
D: the distance between the load point, F is a stress at 圧裂. ) Therefore, compressive strength I of the present invention (MPa) is, JIS28
According to the "compression strength" of 841-1993, two points were loaded on 100 catalyst particles (particle diameter: d (μm)) in a certain particle size range using a commercially available micro compression tester, and the stress when the particles were crushed. : from the average value of f (gf), it is calculated by the equation (3).
【００１４】[0014]
【数１】 Ｉ＝８７４０ｆ／ｄ2 （３） 本発明の複合酸化物触媒は、上述した圧縮強度が３０Ｍ
Ｐａ以上、好ましくは３３ＭＰａ以上、更に好￥ましく
は３５〜５０ＭＰａの強度を示すことが可能となる。I = 8740f / d 2 (3) The composite oxide catalyst of the present invention has the above-mentioned compressive strength of 30M.
Pa or more, preferably at least 33 MPa, still good ¥ Mashiku it becomes possible to indicate the strength of 35～50MPa.
【００１５】元素Ｙは、周期表（IUPAC無機化学命名法1
990年規則）の１〜１６族の元素であり、Ｍｏ，Ｖ，Ｎ
ｂ、Ｔｅ、Ｏ以外から選ばれる１以上の元素であれば特
に限定されないが、具体的には、希土類（スカンジウ
ム、イットリウム、ランタノイド）、ビスマス，タンタ
ル、ガリウム、ゲルマニウム、コバルト，マンガン，ニ
ッケル，鉄、鉛、タングステン、レニウム、ルテニウ
ム、ロジウム、亜鉛、スズ、チタン、ジルコニウム，ホ
ウ素，インジウム，クロム、リン、アルミニウム、アル
カリ、アルカリ土類金属から選ばれる１種以上の元素を
表し、好ましくはジルコニウム及び希土類から選ばれる
１種以上の元素であり、更に好ましくはイットリウムま
たはセリウムである。The element Y is represented by a periodic table (IUPAC inorganic chemical nomenclature 1).
It is a 1 to 16-group elements of the 990-year rule), Mo, V, N
The element is not particularly limited as long as it is at least one element selected from elements other than b, Te, and O. Specifically, rare earths (scandium, yttrium, lanthanoids), bismuth, tantalum, gallium, germanium, cobalt, manganese, nickel, iron represents lead, tungsten, rhenium, ruthenium, rhodium, zinc, tin, titanium, zirconium, boron, indium, chromium, phosphorus, aluminum, alkali, one or more elements selected from the alkaline earth metals, preferably zirconium and at least one element selected from rare earth, more preferably yttrium or cerium.
【００１６】本発明の複合金属酸化物触媒の各元素の組
成について説明する。Ｍｏに対するＶのモル比（ｂ）
は、通常０．０１よりも大きく、好ましくは０．１以上
であり、更に好ましくは０．２以上である。また上限は
通常１未満であり、好ましくは０．６以下、更に好まし
くは０．５以下である。Ｍｏに対するＮｂのモル比
（ｃ）は、通常０．０５より大きく、好ましくは０．０
８よりも大きく、更に好ましくは０．１よりも大きい。
また、上限は通常０．５以下であり、好ましくは０．３
以下、更に好ましくは０．２以下、特に好ましくは０．
１８以下の値である。Ｍｏに対するＸのモル比（ｄ）
は、通常０よりも大きく、好ましくは０．０３よりも大
きく、更に好ましくは０．０５よりも大きい。上限は通
常１以下であり、好ましくは０．５以下であり、更に好
ましくは０．３以下、特に好ましくは０．２以下であ
る。Ｍｏに対するＹのモル比（ｆ）は、通常０以上であ
り、好ましくは０．０１以上、更に好ましくは０．０３
以上であり、上限は通常１未満、好ましくは０．５未
満、好ましくは０．２０未満である。[0016] For the composition of each element in the composite metal oxide catalyst of the present invention will be described. Molar ratio of V to Mo (b)
Is usually larger than 0.01, preferably 0.1 or more, and more preferably 0.2 or more. The upper limit is usually less than 1, preferably 0.6 or less, more preferably 0.5 or less. The molar ratio (c) of Nb to Mo is usually greater than 0.05, preferably 0.0
Greater than 8, more preferably greater than 0.1.
The upper limit is usually 0.5 or less, preferably 0.3
Or less, more preferably 0.2 or less, particularly preferably 0.
It is a value of 18 or less. Molar ratio of X to Mo (d)
Is typically greater than 0, preferably greater than 0.03, and more preferably greater than 0.05. The upper limit is usually 1 or less, preferably 0.5 or less, more preferably 0.3 or less, and particularly preferably 0.2 or less. The molar ratio (f) of Y to Mo is usually 0 or more, preferably 0.01 or more, and more preferably 0.03 or more.
The upper limit is usually less than 1, preferably less than 0.5, and preferably less than 0.20.
【００１７】ＳｉＯ2は、触媒の強度向上と、触媒粒子
が互いに凝集するのを防ぐ目的で添加するが、全触媒中
のＳｉＯ2の含有量は、焼成後の酸化物全体に対する重
量比で２５重量％以下であり、好ましくは３〜１５重量
％、更に好ましくは５〜１２重量％以下である。 （複合金属酸化物触媒の製造方法）本発明の複合金属酸
化物触媒を製造する方法は通常次のようである。所定量
のＭｏ原料、Ｖ原料、Ｔｅ原料、Ｎｂ原料、Ｘ原料、Ｙ
原料およびSiO2ゾル溶液を含有する溶液またはスラリ−
を、各々の金属元素の原子比が所定の割合となるような
量比で調合し、次いで溶媒を乾燥させ、最後に、残った
乾燥物を熱分解工程に供した後、焼成して目的の複合金
属複合金属酸化物触媒とする。SiO 2 is added for the purpose of improving the strength of the catalyst and preventing the catalyst particles from aggregating with each other. The content of SiO 2 in all the catalysts is 25 wt. % By weight, preferably 3 to 15% by weight, more preferably 5 to 12% by weight. (Method for Producing Composite Metal Oxide Catalyst) A method for producing the composite metal oxide catalyst of the present invention is generally as follows. Predetermined amount of Mo raw material, V raw material, Te raw material, Nb raw material, X raw material, Y raw material
The solution or slurry containing the raw material and SiO2 sol solution -
Are prepared in a quantitative ratio such that the atomic ratio of each metal element becomes a predetermined ratio, then the solvent is dried, and finally, the remaining dried product is subjected to a pyrolysis step, and then calcined to obtain the desired product. A composite metal composite metal oxide catalyst.
【００１８】本発明の特定の嵩密度を有する酸化物触媒
を調製するためには、特に、ニオブ原料として、酸化ニ
オブ（Ｎｂ2Ｏ5）ゾルを使用する必要がある。上記の触
媒原料のうち、モリブデン（Ｍｏ）原料としては、パラ
モリブデン酸アンモニウム塩、ＭｏＯ3、ＭｏＣｌ5、Ｍ
ｏ（ＯＲ）5、（Ｒは炭素数１から５のアルキル基）、
モリブデニルアセチルアセトナート等が使用可能であ
る。In order to prepare the oxide catalyst having a specific bulk density of the present invention, it is particularly necessary to use a niobium oxide (Nb 2 O 5 ) sol as a niobium raw material. Among the above catalyst raw materials, molybdenum (Mo) raw materials include ammonium paramolybdate, MoO 3 , MoCl 5 , M
o (OR) 5 , (R is an alkyl group having 1 to 5 carbon atoms),
Molybdenyl acetylacetonate and the like can be used.
【００１９】バナジウム（Ｖ）原料としては、メタバナ
ジン酸アンモニウム塩、ＶＯＳＯ4、Ｖ2Ｏ5 ，Ｖ2Ｏ
3 ，ＶＣｌ4 ，ＶＯＣｌ3、 ＶＯ（ＯＲ）3（Ｒは炭素
数１から５のアルキル基）、等が使用可能である。Ｘ原
料のテルル（Ｔｅ）原料としては、テルル酸、Ｔｅ
Ｏ2、単体のＴｅ等が使用可能である。また、アンチモ
ン（Ｓｂ）原料にもＴｅと同様に単体のＳｂ粉末、酸化
物原料が使用可能である。テルルとアンチモン原料は、
必要に応じて、特開平１１−２２６４０８に記載されて
いるオキソメタレートによる溶解法を用いても良い。Vanadium (V) raw materials include ammonium metavanadate, VOSO 4 , V 2 O 5 and V 2 O.
3 , VCl 4 , VOCl 3 , VO (OR) 3 (R is an alkyl group having 1 to 5 carbon atoms), and the like can be used. As the tellurium (Te) raw material of X raw material, telluric acid, Te
O 2, single Te or the like can be used. Further, antimony (Sb) Sb powder alone as with Te in the raw material, the oxide material can be used. Tellurium and antimony raw material,
If necessary, a dissolution method using oxometalate described in JP-A-11-226408 may be used.
【００２０】ニオブ（Ｎｂ）原料としては、酸化ニオブ
（Ｎｂ2Ｏ5）ゾル等の水に可溶またはコロイド状態とな
るものが好ましく、使用するＮｂ源の少なくとも一部は
カルボン酸が配位していないＮｂ原料である必要があ
る。具体的にはシュウ酸Ｎｂアンモニウム等と酸化ニオ
ブゾルとを同時に用いることも可能である。ここで、シ
ュウ酸ニオブアンモニウムとは、市販のものが使用で
き、例えばＸ3ＮｂＯ（Ｃ2Ｏ4）3とＸ2ＮｂＯ（ＯＨ）
（Ｃ2Ｏ4）2の混合物 ［ここで、Ｘ＝ＮＨ4＋又はＨ
＋］などが使用可能である。シュウ酸ニオブアンモニウ
ムの代わりに含水酸化ニオブ等を、アンモニウムイオン
の共存あるいは非共存下、シュウ酸などのジカルボン酸
水溶液に溶解して用いることも可能である。これらシュ
ウ酸ニオブアンモニウム等に代表される、ジカルボン酸
により溶解されたＮｂ原料の特徴は、ニオブの大半がシ
ュウ酸等のジカルボン酸基および水酸基等が結合した錯
体として存在していることに存する。The niobium (Nb) raw material is preferably a water-soluble or colloidal one such as a niobium oxide (Nb 2 O 5 ) sol. At least a part of the Nb source used is a carboxylic acid coordinated carboxylic acid. It is necessary that the Nb raw material not be used. Specifically, it is also possible to simultaneously use Nb ammonium oxalate and the like and niobium oxide sol. Here, commercially available niobium oxalate can be used, for example, X 3 NbO (C 2 O 4 ) 3 and X 2 NbO (OH)
(C 2 O 4 ) 2 [where X = NH 4 + or H
+], Or the like can be used. Instead of niobium ammonium oxalate, it is also possible to use niobium hydrate or the like dissolved in an aqueous solution of a dicarboxylic acid such as oxalic acid in the presence or absence of ammonium ions. Typified by those of ammonium niobium oxalate and the like, the characteristics of Nb raw material which is dissolved by the dicarboxylic acid consists in the majority of niobium is present as complexes which dicarboxylic acid and hydroxyl group is bonded, such as oxalic acid.
【００２１】一方、酸化ニオブゾルは、酸化ニオブ（Ｎ
ｂ2Ｏ5）の微粒子が水溶液などの媒質中に分散した分散
コロイドの一種であり、酸化ニオブの平均粒子径が１ｎ
ｍから１００ｎｍのものが利用可能であるが、ゾルとし
ての長期安定性、入手の容易さから平均粒径が３〜８ｎ
ｍ、特には５ｎｍ±１ｎｍのものが最も好ましい。この
酸化ニオブゾルの特徴は、水等の媒質中に均質に分散
し、半透明を呈しているものの、ニオブの大半がシュウ
酸等のジカルボン酸基が結合していない状態にあること
に存する。[0021] On the other hand, niobium oxide sol is, niobium oxide (N
b 2 O 5 ) is a kind of dispersed colloid in which fine particles of niobium oxide are dispersed in a medium such as an aqueous solution.
While those from m of 100nm is available, long-term stability as a sol, average particle size from easy availability 3~8n
m, especially 5 nm ± 1 nm. The characteristic of this niobium oxide sol is that although it is homogeneously dispersed in a medium such as water and is translucent, most of the niobium is in a state where a dicarboxylic acid group such as oxalic acid is not bonded.
【００２２】Ｙ原料は、通常水中で分散性が良ければ特
に水溶性である必要はなく、これらの元素の酸化物ゾ
ル、水酸化物、水溶性オキソ酸またはその塩、カルボン
酸塩、硫酸塩、カルボン酸アンモニウム塩、アルコキシ
ド、アセチルアセトナート、等が使用可能である。好ま
しくは酸化物ゾル、または水酸化物、酸化物等の微粉末
が用いられる。Ｙ原料を他の触媒成分を含むスラリーに
添加する様式については様々な方法が選択しうる。しか
しながら、工業的に流動層で使用する平均粒径４０〜６
０μｍの球状の触媒を得るには、触媒成分を含むスラリ
ーを噴霧乾燥により微少球状の乾燥粒子に造粒する方法
がもっとも好適に実施される。このような工業的使用の
見地に立つならば、噴霧乾燥に供されるスラリー中に酸
素を除く触媒構成元素が全て含まれていることが好まし
い。The Y raw material does not need to be particularly water-soluble as long as it has good dispersibility in water. Oxide sols, hydroxides, water-soluble oxo acids or salts thereof, carboxylate salts, sulfate salts of these elements are usually used. , Ammonium carboxylate, alkoxide, acetylacetonate and the like can be used. Preferably oxide sol or hydroxide, fine powder such as oxide. Various methods for manner of addition of Y raw material slurry containing the other catalyst components can be selected. However, the average particle size for industrial use in a fluidized layer 40-6
To obtain a spherical catalyst 0 .mu.m, a method of granulating a slurry containing catalyst components to dry particles of fine spherical by spray drying is most suitably implemented. From the standpoint of such industrial use, it is preferable that the slurry to be subjected to spray drying contains all the catalyst constituent elements except oxygen.
【００２３】Ｙ成分は、他の触媒成分と共存することに
よって、有用なニトリルの収率を向上させる効果を有す
るが、添加の様式によってはスラリー中で他の成分との
望ましくない相互作用の結果、効果を充分に発揮しない
こともあり得る。このようなスラリーとＹ成分との望ま
しくない相互作用を抑制する必要がある場合には、混合
後のスラリーをある温度以下に管理する、あるいは混合
から乾燥工程までの時間を短縮するラインミキシング等
の方式も採用できる。あるいは、添加するＹ成分とし
て、５００℃以上、好ましくは１０００℃以上の高温で
焼成された酸化物微粒子を用いる方法、平均粒径が０．
１μｍ以上４０μｍ以下の酸化物粒子を用いる方法、あ
るいはＢＥＴ法で測定した比表面積が０．１ｍ2ｇ-1以
上２００ｍ2ｇ-1以下、好ましくは０．１ｍ2ｇ-1以上５
ｍ2ｇ-1以下の原料を用いる方法、灼熱減量が５％以
下、好ましくは１％以下である原料を用いる方法など、
媒質への分散性さえ満足されれば、Ｙ成分として化学的
に不活性なものを選択することも可能である。ここで灼
熱減量とは大気中１０００℃ ３０分間保持した場合の
重量減少率である。The Y component has the effect of improving the yield of useful nitriles by coexisting with other catalyst components, but depending on the mode of addition, may result in undesirable interaction with other components in the slurry. , it may be not sufficiently effective. When it is necessary to suppress such an undesired interaction between the slurry and the Y component, it is necessary to control the slurry after mixing to a certain temperature or lower, or to reduce the time from mixing to the drying step, such as line mixing. A method can also be adopted. Alternatively, as the Y component to be added, a method using oxide fine particles fired at a high temperature of 500 ° C. or higher, preferably 1000 ° C. or higher, with an average particle diameter of 0.1 μm.
A method using oxide particles having a size of 1 μm or more and 40 μm or less, or a specific surface area measured by a BET method of 0.1 m 2 g −1 or more and 200 m 2 g −1 or less, preferably 0.1 m 2 g −1 or more 5
a method using a raw material of m 2 g −1 or less, a method of using a raw material having a loss on ignition of 5% or less, preferably 1% or less,
If even dispersibility in the medium is satisfactory, it is also possible to select the one which is chemically inert as the Y component. Here, the loss on ignition is the rate of weight loss when kept at 1000 ° C. for 30 minutes in the atmosphere.
【００２４】SiO2ゾルとしては、得られた酸化物触媒全
体に対するSiO2含有量が２５ｗｔ％以下となるような量
を使用する。上述したこれらの各原料を水等の溶媒中で
混合して溶液またはスラリーを得る。原料として用いる
各元素成分の比率は、テルルを除いて、通常、上述した
ような最終的に得られる複合金属酸化物触媒の組成比と
同じとなるように配合される。各原料の混合時の温度は
通常３０〜８０℃であり、好ましくは４０〜５０℃であ
る。Examples of the SiO 2 sol, SiO 2 content to the total obtained oxide catalyst is used in an amount such that less 25 wt%. These raw materials described above are mixed in a solvent such as water to obtain a solution or slurry. The ratio of each element component used as a raw material, except for tellurium, is usually blended so as to be the same as the composition ratio of the composite metal oxide catalyst finally obtained as described above. Temperature during mixing of the raw material is usually 30 to 80 ° C., preferably from 40 to 50 ° C..
【００２５】各金属元素の原料化合物を含むスラリーに
は、スラリー状態、または熱分解工程あるいは焼成工程
において還元作用をもつ物質を含有させる。還元作用を
有する物質としては、シュウ酸、クエン酸、酒石酸、リ
ンゴ酸、アスコルビン酸等の有機酸またはその塩、脂肪
族アルデヒド、芳香族アルデヒドのようなアルデヒド
類、ブタノール、ベンジルアルコールのようなアルコー
ル類あるいは、ブドウ糖のような還元糖類、ヒドロキシ
ルアミンのような無機アミン類およびその塩、有機アミ
ン類あるいはその塩、ヒドラジン類やその塩あるいはジ
イミドが用いられるが、好ましくは有機酸またはアルデ
ヒド、アルコールであり、更に好ましくはシュウ酸また
はクエン酸、最も好ましくはシュウ酸である。[0025] The slurry containing the starting compound of the respective metal elements, slurry, or to contain a substance having a reducing action in the thermal decomposition step or sintering step. Examples of the substance having a reducing action include organic acids such as oxalic acid, citric acid, tartaric acid, malic acid, and ascorbic acid or salts thereof, aldehydes such as aliphatic aldehyde and aromatic aldehyde, and alcohols such as butanol and benzyl alcohol. Or reducing sugars such as glucose, inorganic amines such as hydroxylamine and salts thereof, organic amines or salts thereof, hydrazines and salts thereof or diimides, and preferably organic acids or aldehydes or alcohols. And more preferably oxalic acid or citric acid, most preferably oxalic acid.
【００２６】これら還元作用を有する物質は、たとえば
シュウ酸ニオブアンモニウムにおけるシュウ酸根のよう
に、触媒構成元素の原料物質に含有される、あるいは化
合していても、別途シュウ酸二水和物のような形態で添
加してもよい。この還元作用を有する物質の量は、目的
とする複合金属酸化物の平均価数、原料化合物の平均価
数および還元剤の利用効率の兼ね合いにより決定される
ため、その好適な使用量は一概には決定できないが、通
常、Ｓｉ等の担体成分を除く仕込みの金属元素合計モル
数に対して０．０１〜１０モル倍である。ここで平均価
数とは、元素の価数にその存在割合を乗じて加算した値
をいう。還元剤としてシュウ酸根を含有させる場合、シ
ュウ酸根のモル数は、仕込みの金属モル数に対して、通
常０．０５〜１倍、好ましくは０．１〜０．５倍であ
る。These substances having a reducing action include, for example, oxalic acid radicals in niobium ammonium oxalate, even if they are contained in the raw material of the catalyst constituent element or are compounded, such as oxalic acid dihydrate. it may be added in a form. The amount of substance having the reduction action, the average valence of the intended double metal oxide, because it is determined by the balance of the utilization efficiency of the average valence and a reducing agent of the starting compounds, the preferred amount is sweepingly Although not be determined, it is 0.01 to 10 moles per mol of the normal metal element total number of moles of charged excluding carrier component such as Si. Here, the average valence refers to a value obtained by adding by multiplying the existing ratio to the valence of the element. Case of containing the oxalic acid radical as the reducing agent, the number of moles of oxalic acid radical, relative to metal molar number of charged, usually 0.05 to 1 times, preferably 0.1 to 0.5 times.
【００２７】還元剤が作用した後の各構成元素の価数
は、Ｍｏが平均５以上６未満、Ｖが平均４以上５未満、
Ｔｅが平均４以上６未満、Ｓｂは平均３以上５未満、Ｎ
ｂは５価であり、Ｓｉ等の担体成分を除く構成元素の平
均価数は通常４以上６未満、好ましくは４．５以上５．
９以下、特に好ましくは５以上５．８以下である。本発
明において、還元剤は、スラリー状態、熱分解、焼成の
いずれの工程で作用しても良いが、通常、熱分解あるい
は焼成工程において還元剤が作用し、原子価の調節が行
われるのが好ましく、主に熱分解工程でこの調節が行わ
れるのが特に好ましい。As for the valence of each constituent element after the action of the reducing agent, Mo has an average of 5 or more and less than 6, V has an average of 4 or more and less than 5,
Te is less than an average of 4 or more 6, Sb less than the average 3 or more 5, N
b is pentavalent, and the average valence of the constituent elements excluding the carrier component such as Si is usually 4 or more and less than 6, preferably 4.5 or more and 5.
9 or less, particularly preferably 5 or more 5.8 or less. In the present invention, the reducing agent may act in any of the steps of slurry state, thermal decomposition, and calcination. However, usually, the reducing agent acts in the thermal decomposition or calcination step to adjust the valence. It is particularly preferred, and particularly preferred, that this adjustment takes place mainly in the pyrolysis step.
【００２８】得られた溶液又はスラリーは、次いで溶媒
除去のための乾燥工程に送り、溶媒を除去して固形物と
する。乾燥工程に至るまでに溶液又はスラリーを保持す
る温度は、高温にすると生成した触媒の性能が低下する
傾向があるため、保持温度は通常８０℃以下、好ましく
は６０℃以下とする。またスラリーを低温で保持すると
結晶状固体が析出し生成した触媒性能を悪化させる傾向
があるので、保持温度は通常１０℃以上、好ましくは３
０℃以上である。The resulting solution or slurry is then sent to a drying step to remove the solvent, where the solvent is removed to a solid. The temperature at which the solution or slurry is held before the drying step tends to lower the performance of the formed catalyst when the temperature is increased. Therefore, the holding temperature is usually 80 ° C. or lower, preferably 60 ° C. or lower. When the slurry is held at a low temperature, a crystalline solid tends to precipitate and the generated catalyst tends to deteriorate, so the holding temperature is usually 10 ° C. or higher, preferably 3 ° C.
0 ° C. or higher.
【００２９】溶液又はスラリーからの溶媒除去のための
乾燥は、蒸発乾固法、噴霧乾燥法、真空乾燥法等の常法
に従えばよい。最終的に得られる複合金属酸化物触媒を
流動床用触媒として用いる場合には、上述したように噴
霧乾燥するのが好ましい。噴霧乾燥は常法に従って行え
ばよい。噴霧乾燥中はスラリーから固形分が沈降しない
ように絶えずスラリーの撹拌を行うのがよい。噴霧乾燥
法によれば、レーザー回折散乱式粒度分布測定装置で測
定して、平均粒径４０〜６０μｍ程度の、流動床用触媒
として好適な球状触媒を容易に得ることが出来る。噴霧
乾燥工程の第一段階では、噴霧乾燥に供されるスラリー
は適当なアトマイザーを通過して、液状混合物の噴霧体
すなわち液滴を生じる。アトマイザーとしては、ディス
ク回転式あるいはノズル式アトマイザーが好適に用いら
れる。本発明のような平均粒径４０〜６０μｍ程度の球
状の触媒を得るには、ディスク回転式アトマイザーがよ
り好ましい。ディスク回転式アトマイザーを用いた場合
には、あるスラリーをある送液速度で噴霧して生じる液
滴の粒径はディスク回転数により概ね制御される。Drying for removing the solvent from the solution or slurry may be carried out by a conventional method such as an evaporation to dryness method, a spray drying method, and a vacuum drying method. When the composite metal oxide catalyst finally obtained is used as a catalyst for a fluidized bed, it is preferable to spray-dry as described above. Spray drying may be performed according to a conventional method. During spray drying, the slurry should be constantly stirred so that solids do not settle out of the slurry. According to the spray drying method, measured by a laser diffraction scattering particle size distribution measuring apparatus, an average particle diameter of about 40 to 60 [mu] m, it can be easily obtained a suitable spherical catalyst as a fluidized bed catalyst. In the first stage of the spray-drying process, the slurry subjected to spray-drying passes through a suitable atomizer to produce sprays or droplets of the liquid mixture. As the atomizer, a disk rotary type or a nozzle type atomizer is preferably used. To obtain the average particle diameter 40~60μm about spherical catalyst as in the present invention, a disk rotary atomizer is more preferable. When a disk rotary atomizer is used, the particle diameter of droplets generated by spraying a certain slurry at a certain liquid sending speed is generally controlled by the disk rotation speed.
【００３０】噴霧乾燥を行う温度は、液滴に接触するガ
スの温度、流量によって概ね決定され、噴霧乾燥生成物
の物理的性質に大きな影響を及ぼす。乾燥温度が高すぎ
ると、空洞があったり、割れた球状でない粒子が生じや
すく、乾燥温度が低すぎると液滴が噴霧乾燥装置の壁面
あるいは排出点に到達する前に乾燥が完了せず、回収率
が低くなったり、液滴同士の合体により、球状でない粒
子が生じる。噴霧乾燥機に導入されるガス温度は入り口
で通常１００〜４００℃、好ましくは１５０〜３００
℃、より好ましくは１８０〜２８０℃であり、出口ガス
温度は通常８０〜２００℃、好ましくは９０〜２５０
℃、より好ましくは１００〜２００℃である。乾燥時間
は、通常０．０１秒〜１０分であり、好ましくは０．０
１秒〜５分であり、更に好ましくは０．０５秒〜１分で
ある。The temperature at which the spray-drying is carried out is largely determined by the temperature and flow rate of the gas in contact with the droplets, and has a great influence on the physical properties of the spray-dried product. If the drying temperature is too high, cavities or broken non-spherical particles are liable to be generated.If the drying temperature is too low, the drying does not complete before the droplets reach the wall or discharge point of the spray-drying device and is collected. Non-spherical particles are produced due to low rates or coalescence of droplets. Gas temperature to be introduced into the spray dryer is usually 100 to 400 ° C. at the inlet, preferably 150 to 300
° C., more preferably 180 to 280 ° C., the outlet gas temperature is usually 80 to 200 ° C., preferably 90 to 250
° C, more preferably 100-200 ° C. The drying time is usually 0.01 seconds to 10 minutes, preferably 0.0
It is 1 second to 5 minutes, and more preferably 0.05 second to 1 minute.
【００３１】流動層触媒としての強度、および流動性の
観点から、中空ではなく、中実球の乾燥粒子が得られる
よう、送液量、入り口／出口ガス温度、乾燥ガス流量等
が選択される。通常、噴霧乾燥により得られた乾燥粒子
を含むガスは、サイクロン等に代表される分級装置へ導
かれ、粒子の捕集、分級が行われる。サイクロン内での
ガスの線速等の運転条件は、流動層での使用に適した平
均粒子径、粒径分布となるよう選択される。From the viewpoints of the strength and fluidity of the fluidized bed catalyst, the flow rate, inlet / outlet gas temperature, dry gas flow rate, etc. are selected so as to obtain solid, not hollow, dry particles. . Normally, a gas containing dried particles obtained by spray drying is led to a classifier represented by a cyclone or the like, where the particles are collected and classified. The operating conditions such as the linear velocity of the gas in the cyclone are selected so as to have an average particle size and a particle size distribution suitable for use in a fluidized bed.
【００３２】乾燥工程で得られた固形物は、常法により
熱分解してアンモニアや炭酸ガス等の揮発性ガスを放出
させ、固体を得た後に焼成して複合金属酸化物とする。
熱分解の方法は各種の形態が採用可能であるが、工業的
にはロータリーキルン等によって連続的に行うのが有利
である。熱分解温度は１５０℃〜４００℃が好適である
が、さらに好ましくは２００〜３００℃である。熱分解
工程の滞在時間は数秒から数十分の範囲で行うのが好適
である。ここでいう滞在時間とは、キルンの例でいうな
らば、触媒前駆体がキルンのレトルト上を移動する際
に、分解中の触媒前駆体の温度が、最高到達温度とそれ
より５℃低い温度の間であるような領域を通過していた
時間である。この滞在時間は更に好ましくは、２分から
１０分の範囲である。 熱分解の際の触媒前駆体の昇温
速度は、触媒粒子の強度を再現性良く、高い値に保つた
め、２℃／ｍｉｎ以上、４０℃／ｍｉｎ以下とするのが
好ましい。この場合の昇温速度とは、キルンを例にとる
と、キルン入り口のある点にあって分解が実質的に進行
しない１００℃程度以下のある温度の触媒前駆体が、キ
ルンのレトルトを移動してより高温にさらされ分解が進
行する熱分解最高到達温度のある温度に到達するまでの
時間で、この間の温度差を除した値であり、代表的には
（前駆体の最高到達温度−キルン入り口での温度）／
（その間の前駆体の平均移動時間）である。この昇温速
度は好ましくは２〜３０℃／ｍｉｎであり、更に好まし
くは１０〜２０℃／ｍｉｎである。熱分解の昇温速度は
得られる触媒の強度に大きな影響を与える。熱分解の昇
温速度が速すぎると、粒子内部での急激な分解ガスの発
生により粒子が破砕したり、亀裂が生じたりして強度が
低下する傾向がある。熱分解の昇温速度が遅すぎると、
触媒の活性が損なわれる他、触媒を生産する際の能率が
低くなる傾向がある。熱分解工程は、発生した分解ガス
の除去を迅速に行うため、通常はガス流通下で行う。The solid obtained in the drying step is thermally decomposed by a conventional method to release volatile gases such as ammonia and carbon dioxide, and after obtaining the solid, is fired to obtain a composite metal oxide.
Although various forms can be adopted for the method of thermal decomposition, it is advantageous industrially to carry out the method continuously using a rotary kiln or the like. Although the thermal decomposition temperature is preferably 0.99 ° C. to 400 ° C., more preferably from 200 to 300 [° C.. The residence time of the pyrolysis step is preferably in the range of several seconds to tens of minutes. The residence time referred to here is, in the case of the kiln, the temperature of the catalyst precursor during decomposition when the catalyst precursor moves on the retort of the kiln, and the temperature reached by the maximum attainment temperature and 5 ° C lower than that. It is the time during which it has passed through an area that is between This dwell time is more preferably in the range of 2 minutes to 10 minutes. The rate of temperature rise of the catalyst precursor during the thermal decomposition is preferably 2 ° C./min or more and 40 ° C./min or less in order to keep the strength of the catalyst particles high with good reproducibility. In this case, the heating rate is, for example, in the case of a kiln, a catalyst precursor at a certain point at the entrance of the kiln and at a temperature of about 100 ° C. or less at which decomposition does not substantially proceed moves through the retort of the kiln. in more time to be exposed to high temperature degradation reaches a temperature at which a thermal decomposition peak temperature of progress Te, a value obtained by dividing the temperature difference during this time, the maximum temperature of typically (precursor - kiln the temperature at the entrance) /
(Average transit time of the precursor during that time). This rate of temperature rise is preferably 2 to 30 ° C / min, more preferably 10 to 20 ° C / min. The heating rate of the thermal decomposition has a great influence on the strength of the obtained catalyst. If the temperature rise rate of the thermal decomposition is too high, the particles tend to be crushed or cracked due to rapid generation of decomposition gas inside the particles, and the strength tends to decrease. When the temperature rising rate of thermal decomposition is too slow,
In addition to impairing the activity of the catalyst, the efficiency in producing the catalyst tends to be low. The thermal decomposition step is usually performed under a gas flow in order to quickly remove generated decomposition gas.
【００３３】熱分解工程の雰囲気は、通常空気よりも酸
素濃度の低い雰囲気、好ましくは酸素濃度500ppm以下、
さらに好ましくは酸素濃度100ppm以下、もっとも好まし
くは実質上酸素を含まない窒素、アルゴン、ヘリウム、
ＣＯ2などの不活性ガス雰囲気である。ガスの流速は、
連続的に熱分解工程を行う場合は、供給前駆体１ｋｇあ
たり、５００〜１００００Ｎｌのガスを流通させる。好
ましくは１０００〜６０００Ｎｌである。固定床で分解
を行う場合は、空間速度として通常 １００〜１０００
００ｈｒ-1が採用され、好ましくは、５００〜８０００
ｈｒ-1、更に好ましくは１０００〜６０００ｈｒ-1であ
る。流速・空間速度が大きすぎても触媒粒子の物理的性
質に悪影響はないが、経済的には好ましくない。The atmosphere for the pyrolysis step is usually an atmosphere having an oxygen concentration lower than that of air, preferably an oxygen concentration of 500 ppm or less.
More preferably the oxygen concentration 100ppm or less, nitrogen and most preferably substantially free of oxygen, argon, helium,
An atmosphere of an inert gas such as CO 2 . The flow rate of the gas,
When the thermal decomposition step is performed continuously, a gas of 500 to 10,000 Nl per 1 kg of the supplied precursor is passed. Preferably it is 1000-6000 Nl. If disassembly in a fixed bed is usually 100 to 1000 as space velocity
00 hr -1 is employed, preferably 500 to 8000
hr -1, more preferably from 1000~6000hr -1. If the flow velocity / space velocity is too high, there is no adverse effect on the physical properties of the catalyst particles, but it is economically undesirable.
【００３４】焼成方法は、固定床方式、流動層方式、ロ
ータリーキルン、トンネル炉等各種の形態を取りうる
が、工業的には流動層、ロータリーキルン等が有利であ
る。焼成温度は通常３００〜７００℃であり、好ましく
は５５０〜６５０℃、更に好ましくは５８０〜６３０℃
である。焼成時間は、通常５分〜２０時間、好ましくは
３０分〜６時間、特に好ましくは１〜３時間である。室
温から所定の焼成温度まで到達するのに要する時間は通
常３時間以下、好ましくは２時間以下である。焼成雰囲
気は、通常空気よりも酸素濃度の低い雰囲気、好ましく
は酸素濃度500ppm以下、さらに好ましくは酸素濃度100p
pm以下、もっとも好ましくは実質上酸素を含まない窒
素、希ガス、ＣＯ2などの不活性ガス雰囲気である。不
活性ガスは、好ましくは窒素、希ガス、更に好ましくは
窒素、アルゴン、ヘリウムである。また、特開平７−２
８９９０７号公報に記載されているように焼成後に冷却
して酸素と接触させた後に再度酸素が５００ｐｐｍ以下
の窒素、アルゴン、ヘリウム、ＣＯ２等の不活性雰囲気
下で焼成するのも好ましい。The calcination process is a fixed bed system, a fluidized bed system, a rotary kiln, but may take the form of a tunnel furnace and various, for industrial fluidized bed, rotary kiln or the like is advantageous. The firing temperature is usually 300 to 700 ° C, preferably 550 to 650 ° C, more preferably 580 to 630 ° C.
It is. Calcination time is usually 5 minutes to 20 hours, 6 hours preferably 30 minutes, particularly preferably 1 to 3 hours. The time required to reach a predetermined firing temperature from room temperature is usually 3 hours or less, preferably 2 hours or less. The firing atmosphere is an atmosphere having an oxygen concentration lower than that of ordinary air, preferably an oxygen concentration of 500 ppm or less, more preferably an oxygen concentration of 100 p.
pm or less, and most preferably is an inert gas atmosphere of nitrogen, noble gases, such as CO 2 substantially free of oxygen. The inert gas is preferably nitrogen, a noble gas, more preferably nitrogen, argon, helium. Also, Japanese Patent Laid-Open No. 7-2
Again oxygen 500ppm or less nitrogen after contact with oxygen and cooled after the sintering, as described in 89907 JP, argon, helium, and preferably calcined in an inert atmosphere such as CO2.
【００３５】ガスの空間速度（ＳＶ）は、通常１００〜
１００００ｈｒ-1であり、好ましくは５００〜６０００
ｈｒ-1であり、更に好ましくは５００〜６０００ｈｒ-1
である。流動層方式で焼成する場合には、触媒層の温度
分布を計測するなどして触媒が流動状態にあることを確
認する。その際、不活性ガスの流速は、触媒が流動状態
にあり、かつ焼成装置で触媒が回収可能な範囲で選択さ
れる。通常、ガス流速は、焼成容器内でガスの線速（Ｌ
Ｖ）が所定の焼成温度において２ｃｍ／ｓｅｃ程度ある
いはそれ以上となるよう調節される。The space velocity (SV) of the gas is usually 100 to
10,000 hr -1 , preferably 500 to 6000
a hr -1, more preferably 500～6000Hr -1
It is. In the case of firing in a fluidized bed method, it is confirmed that the catalyst is in a fluidized state by measuring the temperature distribution of the catalyst layer. At that time, the flow rate of the inert gas is selected within a range where the catalyst is in a fluidized state and the catalyst can be recovered by the calcination device. Usually, the gas flow rate is determined by the linear velocity (L
V) is adjusted to be about 2 cm / sec or more at a predetermined firing temperature.
【００３６】焼成装置から触媒の飛散を防止するため
に、サイクロン等の分離装置を設置することも可能であ
る。焼成装置全体を加熱するなどして、器壁に付着した
揮発成分が触媒に落下して、触媒に混入しないようにす
ることもできる。乾燥、熱分解の工程の間に触媒を冷却
することも出来るし、冷却せず速やかに分解工程に移送
してもよい。移送、保存等に際し、熱分解前の固体が１
００℃以上の温度で３０分以上保持されることは好まし
くない。熱分解後の固体は、焼成工程までに冷却するこ
とも可能である。焼成前の固体、あるいは触媒を、３０
０℃以上の温度で、酸素濃度が５００ｐｐｍ以上である
雰囲気に３０分以上保持することは好ましくない。焼成
に際しては、昇温開始までに、焼成装置内が不活性ガス
で充分置換され、残存酸素濃度が３００ｐｐｍ以下であ
ることが好ましい。In order to prevent the catalyst from scattering from the firing device, it is possible to install a separating device such as a cyclone. By heating the entire sintering apparatus, it is possible to prevent the volatile components adhering to the vessel wall from dropping onto the catalyst and from mixing into the catalyst. Drying, also to be able to cool the catalyst during the pyrolysis step may be transferred promptly to degradation step without cooling. When transferring, storing, etc., 1 solid before pyrolysis
00 ° C. to be retained for 30 minutes or more at temperatures above undesirable. The solid after pyrolysis can be cooled before the firing step. The solid or catalyst before calcining is
At 0 ℃ or higher, the oxygen concentration is not preferable to hold more than 30 minutes to an atmosphere at 500ppm or more. At the time of baking, it is preferable that the inside of the baking apparatus is sufficiently replaced with an inert gas before the start of temperature rise, and that the residual oxygen concentration is 300 ppm or less.
【００３７】（気相接触酸化反応の説明）本発明の製造
方法により得られる複合金属酸化物触媒は、アルカンの
接触酸化反応による有機化合物の製造に利用される。ア
ルカンとしては、炭素数１〜１０，好ましくは炭素数２
〜６のアルカンが挙げられる。アルカンの気相接触酸化
反応とは、アルカンを酸素と気相接触酸化させるもので
あるが、酸素の他にアンモニアや尿素等の窒素源や水蒸
気が反応系に存在する反応も含まれ、含酸素有機化合
物、脱水素化有機化合物、ニトリル類等の各種の有機化
合物の製造に利用される。(Explanation of Gas-Phase Catalytic Oxidation Reaction) The composite metal oxide catalyst obtained by the production method of the present invention is used for producing an organic compound by a catalytic oxidation reaction of an alkane. The alkane has 1 to 10 carbon atoms, preferably 2 carbon atoms.
To 6 alkanes. The gas phase catalytic oxidation reaction of alkanes is a reaction in which an alkane is oxidized in gas phase with oxygen, and also includes a reaction in which a nitrogen source such as ammonia or urea or water vapor is present in the reaction system in addition to oxygen. It is used for the production of various organic compounds such as organic compounds, dehydrogenated organic compounds, and nitriles.
【００３８】本発明により得られた複合金属酸化物触媒
は、特に低級アルカンの気相酸化触媒またはアンモ酸化
触媒としてきわめて高い性能を有する。たとえば、ｎブ
タンから無水マレイン酸、プロパンからアクリル酸、プ
ロパンからアクリロニトリル、プロパンからアクリル酸
とアクリロニトリル、エタンからエチレンを製造する反
応における触媒として有用である。The composite metal oxide catalyst obtained according to the present invention has extremely high performance especially as a gaseous oxidation catalyst or an ammoxidation catalyst for lower alkanes. For example, it is useful as a catalyst in a reaction for producing maleic anhydride from n-butane, acrylic acid from propane, acrylonitrile from propane, acrylic acid and acrylonitrile from propane, and ethylene from ethane.
【００３９】本発明の製造方法で得られる複合金属酸化
物触媒は５００℃以下の比較的低温下においてもアルカ
ンの選択酸化活性が高いという特性を有するので、反応
温度は通常３００〜５００℃、好ましくは３５０〜４８
０℃であり、ガス空間速度（ＳＶ）は通常１００〜１０
０００ｈｒ-1、好ましくは３００〜６０００ｈｒ-1の範
囲である。反応の圧力はとくに制限されないが、通常１
気圧から３気圧、好ましくは１気圧から２気圧である。
また希釈ガスとして、窒素、ヘリウム、アルゴン、ＣＯ
2等の不活性ガスを用いることもできる。[0039] Since the composite metal oxide catalyst obtained by the process of the present invention has a characteristic that is highly selective oxidation activity of alkanes even at relatively low temperature below 500 ℃, the reaction temperature is generally 300 to 500 ° C., preferably Is 350-48
0 ° C. and the gas hourly space velocity (SV) is usually 100 to 10
000hr -1, preferably in the range of 300~6000hr -1. The pressure of the reaction is not particularly restricted, usually 1
3 atmospheres pressure, preferably 2 atm 1 atm.
In addition, nitrogen, helium, argon, CO
It is also possible to use an inert gas 2.
【００４０】反応は、固定床、流動層のいずれも採用で
きるが、流動層がより温度制御が容易であり好ましい。
また、反応に不活性な酸化物粒子を反応系内に存在させ
ることにより、流動層における反応熱の除去を更に容易
にすることができる。本発明の複合金属酸化物触媒は、
中でも、特にプロパンからのアクリロニトリルの製造に
有効である。この場合、反応供給ガスにおいて、酸素は
プロパンに対して０．２〜４モル倍、アンモニアはプロ
パンに対し０．１〜３倍モルの範囲が好適である。The reaction is a fixed bed, but may employ either of the fluidized bed, preferably is easy more temperature control fluid layer.
In addition, the removal of heat of reaction in the fluidized bed can be further facilitated by the presence of oxide particles inert to the reaction in the reaction system. The composite metal oxide catalyst of the present invention,
Among them, it is particularly effective for the production of acrylonitrile from propane. In this case, in the reaction feed gas, oxygen is preferably in a range of 0.2 to 4 moles per mole of propane, and ammonia is preferably in a range of 0.1 to 3 moles per mole of propane.
【００４１】本発明では、原料転化率を低く押さえ、高
い生成物選択率を実現する場合には反応器出口の未反応
原料を分離してリサイクルし、再び原料として使用する
方法も採用することができる。本発明複合金属酸化物触
媒は、アルカンの部分酸化により不飽和カルボン酸、特
にプロパンの部分酸化反応により高収率でアクリル酸を
得ることもできる。反応原料ガスとしては、プロパン、
酸素含有ガスを使用するが、更に水蒸気を用いるのが好
ましく、炭酸ガス等の生成を抑制しアクリル酸の選択率
を更に高めることができる。アクリル酸は、プロパン／
水蒸気／酸素／窒素のモル比が、1.0/0.1〜20/0.1〜10.
0/0〜50.0である反応ガスを、上述した空間速度ＳＶの
条件で反応装置に供給することにより製造される。In the present invention, when the conversion of the raw material is kept low and a high product selectivity is realized, it is also possible to adopt a method of separating and recycling the unreacted raw material at the outlet of the reactor and reusing it as a raw material. it can. In the composite metal oxide catalyst of the present invention, acrylic acid can be obtained in a high yield by a partial oxidation reaction of an unsaturated carboxylic acid, particularly propane by partial oxidation of alkane. Propane,
Using the oxygen-containing gas, but may further further increase the selectivity of it is preferable to use water vapor, acrylic acid suppresses the formation of such carbon dioxide gas. Acrylic acid is propane /
The molar ratio of water vapor / oxygen / nitrogen, 1.0 / 0.1 to 20 / 0.1 to 10.
It is manufactured by supplying a reaction gas of 0/0 to 50.0 to the reactor under the condition of the space velocity SV described above.
【００４２】更には、本発明明の複合金属酸化物触媒
は、アンモニア存在下でのプロパンの部分酸化反応の反
応条件、特にプロパンに対するアンモニア、酸素のモル
比、反応温度などを制御することによりアクリロニトリ
ルとアクリル酸を同時に製造することも可能であり、プ
ロパン／アンモニア／酸素／窒素のモル比が、通常1.0/
0.1〜3.0/0.1〜10.0/0〜50.0である反応ガスを、上述し
た空間速度ＳＶの条件で反応装置に供給することにより
製造される。Further, the composite metal oxide catalyst of the present invention can be used for controlling acrylonitrile by controlling the reaction conditions for the partial oxidation of propane in the presence of ammonia, in particular, the molar ratio of ammonia and oxygen to propane, and the reaction temperature. And acrylic acid can be simultaneously produced, and the molar ratio of propane / ammonia / oxygen / nitrogen is usually 1.0 /
It is manufactured by supplying a reaction gas having a space velocity of 0.1 to 3.0 / 0.1 to 10.0 / 0 to 50.0 to the reactor under the condition of the space velocity SV described above.
【００４３】[0043]
【実施例】以下、本発明を実施例、および比較例を挙げ
てさらに詳細に説明するが、本発明はその趣旨を越えな
い限り、これらの実施例に限定されるものではない。プ
ロパン（ＰＰＡ）転化率、アクリロニトリル（ＡＮ）収
率、ＷＷＨは次のように計算する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist. Propane (PPA) conversion, acrylonitrile (AN) yield, and WWH are calculated as follows.
【００４４】[0044]
【数２】プロパン転化率（％）：反応したプロパンのモ
ル数/供給したプロパンのモル数×１００ アクリロニトリル収率（％）：生成アクリロニトリルの
モル数/供給プロパンのモル数×１００ ＷＷＨ（ｈｒ−１）：１時間あたりプロパン供給量（ｋ
ｇ）／触媒量（ｋｇ） （実施例１）Ｍｏ1Ｖ0.25Ｎｂ0.16Ｔｅ0.125Ｃｅ0.04Ｏｎ／ＳｉＯ2
−１０ｗｔ％の製造 イオン交換水 ２１７４０ｇを７５℃に加温し、パラモ
リブデン酸アンモニウム ５７８２ｇ、メタバナジン酸
アンモニウム ９５８ｇ、テルル酸 １５０４ｇをこの
順番で投入し撹拌して溶解させた。この溶液を７０℃に
放冷し、シリカゾル（触媒化成工業 Ｓ−２０Ｌ：Ｓｉ
Ｏ2 ２０ｗｔ％） ４１１９ｇを加えて撹拌し、６０
℃に保った。これをＡ液とする。別にイオン交換水５２
９２ｇを５０℃に加温し、シュウ酸ニオブアンモニウム
（スタルク社製Ｌｏｔ．９９０７０７；Ｘ3ＮｂＯ（Ｃ2
Ｏ4）3とＸ2ＮｂＯ（ＯＨ）（Ｃ2Ｏ4）2の混合物［ここ
で、Ｘ＝ＮＨ4 +又はＨ+］，Ｎｂ：２０．１ ｗｔ％，
Ｃ2Ｏ4：５１．８ ｗｔ％，ＮＨ3：５．０ ｗｔ％）
１３２２．９ｇを加えて７０℃まで加熱しながら撹拌し
て溶解させた。この溶液を５０℃まで放冷し、酸化ニオ
ブゾル［多木化学製 Ｎｂ2Ｏ5：１０ｗｔ％、（ＮＨ3 +
ＮＨ4 +）の含有量：Ｎ／Ｎｂ＝０．４４（ｍｏｌ／ｍｏ
ｌ）、（ＣＯＯＨ）2／Ｎｂ＝０．３３８（ｍｏｌ／ｍ
ｏｌ）］ ３１５７ｇとイオン交換水 ８７２ｇを加
え、６０℃まで加熱し１０分間撹拌した後、４０℃に保
った。これをＢ液とする。Ｂ液とＡ液を速やかに混合
し、直ちにＢＥＴ比表面積 １．３ ｍ2ｇ-1の酸化セ
リウム（ＣｅＯ2：新日本金属化学工業 酸化セリウム
−１００ Ｌｏｔ．４３３９９，１１００℃焼成、酸化
物中のＣｅＯ2純度：９９．９％以上、平均粒径：６μ
ｍ、灼熱減量：１％以下）２２５．５ｇを加え、酸化セ
リウム粒子が沈降しないように１５分間撹拌した後、噴
霧乾燥した（ディスク型スプレードライヤー使用、ディ
スクの回転数：６６００ｒｐｍ、送液量：７Ｌ／ｈｒ、
乾燥ガス（空気）入口温度：２２０℃、出口温度：１６
０℃）。噴霧乾燥後の固体は、直ちに室温に冷却され
た。## EQU2 ## Propane conversion (%): moles of reacted propane / moles of supplied propane × 100 Acrylonitrile yield (%): moles of acrylonitrile formed / moles of supplied propane × 100 WWH (hr− 1): Propane supply per hour (k
g) / amount of catalyst (kg) (Example 1) Mo 1 V 0.25 Nb 0.16 Te 0.125 Ce 0.04 On / SiO 2
21740 g of -10 wt% production ion-exchanged water was heated to 75 ° C., and 5782 g of ammonium paramolybdate, 958 g of ammonium metavanadate, and 1504 g of telluric acid were charged in this order and dissolved by stirring. It was allowed to cool this solution to 70 ° C., silica sol (manufactured by Catalysts & S-20L: Si
O 2 20 wt%) was stirred with 4119g, 60
C. This is designated as solution A. Separately, ion-exchanged water 52
92 g was heated to 50 ° C., and niobium ammonium oxalate (Stark Corp., Lot. 990707; X 3 NbO (C 2
O 4 ) 3 and a mixture of X 2 NbO (OH) (C 2 O 4 ) 2 [where X = NH 4 + or H + ], Nb: 20.1 wt%,
C 2 O 4: 51.8 wt% , NH 3: 5.0 wt%)
1322.9 g was added, and the mixture was stirred and dissolved while heating to 70 ° C. The solution was allowed to cool to 50 ° C., niobium oxide sol [Taki Chemical Ltd. Nb 2 O 5: 10wt%, (NH 3 +
NH 4 + ) content: N / Nb = 0.44 (mol / mo)
1), (COOH) 2 /Nb=0.338 (mol / m
ol)] 3157 g and ion-exchanged water 872 g were added, heated to 60 ° C., stirred for 10 minutes, and kept at 40 ° C. This is referred to as B solution. Rapidly mixing the solution B and solution A immediately cerium oxide having a BET specific surface area of 1.3 m 2 g -1 (CeO 2 : Shin Nippon Metal Chemical Industry cerium oxide -100 Lot.43399,1100 ℃ calcined, oxide CeO 2 purity: 99.9% or more, average particle size: 6μ
m, ignition loss: 1% or less) 225.5 g was added, and the cerium oxide particles was stirred for 15 minutes so as not to settle, and spray-dried (disk-type spray dryer used, the rotation speed of the disk: 6600Rpm, feed rate: 7L / hr,
Dry gas (air) inlet temperature: 220 ° C, outlet temperature: 16
0 ° C). The solid after spray drying was immediately cooled to room temperature.
【００４５】次いで、噴霧乾燥によって得られた固体を
キルン（２５９ｍｍφｘ２１７０ｍｍ）に １ｋｇ／ｈ
ｒの速度で供給し、レトルト回転数：１ｒｐｍ、窒素：
２５８０ＮＬ／ｈｒ流通下、２５０℃に保持された時
間：８ ｍｉｎ、昇温速度２０℃／ｍｉｎで熱分解処理
した。熱分解終了後、固体は直ちに室温に冷却された。
次に、得られた触媒前駆体を以下の操作を３回繰り返す
ことにより焼成した。円筒形の流動焼成装置（１５０ｍ
ｍφＸ５２０ｍｍ）に触媒前駆体３ｋｇを充填し、酸素
濃度が３００ｐｐｍ以下である窒素気流中、室温から６
００℃まで２時間で昇温し、６００℃で２時間保持し、
その後室温まで放冷した。窒素の流速は、６００℃にお
いて、流動焼成装置内で線速（ＬＶ）が２ｃｍ／ｓｅｃ
となるようにした。蛍光Ｘ線分析（ＸＲＦ）により測定
したところ、得られた触媒の組成は、Ｍｏ1Ｖ0.25Ｎｂ
0.16Ｔｅ0.125Ｃｅ0.04Ｏｎ／ＳｉＯ2−１０ｗｔ％であ
った。[0045] Next, 1 kg of solid obtained by spray drying kiln (259mmφx2170mm) / h
It was fed at a rate r of, retort number of revolutions: 1rpm, nitrogen:
Under a flow of 2580 NL / hr, a thermal decomposition treatment was carried out at 250 ° C. for 8 minutes and at a temperature increasing rate of 20 ° C./min. After completion of the pyrolysis, the solid was immediately cooled to room temperature.
Then, the obtained catalyst precursor was calcined by repeating 3 times the following operations. Cylindrical fluidized firing device (150m
mφX 520 mm) with 3 kg of the catalyst precursor, and from room temperature to 6 in a nitrogen stream having an oxygen concentration of 300 ppm or less.
The temperature was raised to 00 ° C. in 2 hours, kept at 600 ° C. for 2 hours,
Then, it was allowed to cool to room temperature. Flow rate of nitrogen at 600 ° C., a linear velocity in a fluidized calciner (LV) is 2 cm / sec
It was made to become. Was measured by X-ray fluorescence analysis (XRF), the composition of the resulting catalyst, Mo 1 V 0.25 Nb
0.16 was Te 0.125 Ce 0.04 On / SiO 2 -10wt%.
【００４６】得られた触媒について、下記の方法に従
い、見かけ嵩密度（ＡＢＤ）と充填嵩密度（ＣＢＤ）及
び圧縮強度を測定した。密度測定に用いたメスシリンダ
ーはＪＩＳ規格品を容量補正したものを用いた。秤量は
感量０．０１ｇの上皿天秤を用い、数値の表示方法はＪ
ＩＳＺ８４０１に従った。［見かけ嵩密度（ＡＢＤ）の測定］ 触媒を磁性るつぼ
（Ｂ−４型 容積１５０ｍｌ）に１００ｍｌ採取した。
重量のわかっている容積２５ｍｌのメスシリンダー（内
径約２０ｍｍ×約８４ｍｍ）を、スタンドに固定した漏
斗（上部内径１０２ｍｍ、下部内径９．５ｍｍ×１０４
ｍｍ）の真下に設置した。メスシリンダー上端から、漏
斗の下端までは１９ｍｍとした。触媒がメスシリンダー
を完全に満たして、外に溢れるまで触媒をるつぼから一
定の速度で約３０秒かけて漏斗に注いだ。次にメスシリ
ンダーに振動を加えずに、メスシリンダー上部の触媒を
ステンレス製スパチュラで擦りきった。刷毛を用いてメ
スシリンダー外側に付着した触媒を除去し、その重量測
定値から求めた触媒重量（２回の測定値の平均値）、お
よびメスシリンダーの容積から見かけ嵩密度（ＡＢＤ）
を算出したところ、１．３５ｇ／ｍｌであった。結果を
表１に示す。［充填嵩密度（ＣＢＤ）の測定］ 触媒を重量の分かって
いるシャーレに採取し、秤量（触媒：Ｂ／ｇ）後、触媒
の厚みを均一にして室温で飽和水蒸気圧としたデシケー
タ内で約３０分間放置した。その後、重量を測定（放置
後触媒重量：Ｄ／ｇ）した。この触媒を重量の分かって
いる静止した容積２５ｍｌのメスシリンダー（内径約２
０ｍｍ×約８４ｍｍ）に約２５ｍｌ充填し、バイブレー
タ上で５分間振とう後、触媒の体積を測定（ｖ／ｍｌ）
した。次に、触媒重量を測定（ｗ／ｇ）した。次いで式
（３）により、充填嵩密度（ＣＢＤ）：ｄ（ｇ／ｍｌ）
を算出した。The apparent bulk density (ABD), packed bulk density (CBD) and compressive strength of the obtained catalyst were measured according to the following methods. Graduated cylinder used for density measurements used was volume corrected JIS standard products. The weighing was performed using a 0.01 g sensitive balance, and the display method of the numerical value was J
According to ISZ8401. [Measurement of Apparent Bulk Density (ABD)] 100 ml of the catalyst was collected in a magnetic crucible (B-4, volume 150 ml).
A 25 ml graduated cylinder (inner diameter of about 20 mm x about 84 mm) with a known weight was fixed to a funnel (upper inner diameter: 102 mm, lower inner diameter: 9.5 mm x 104).
mm). The distance from the upper end of the measuring cylinder to the lower end of the funnel was 19 mm. The catalyst was poured from the crucible into the funnel at a constant speed for about 30 seconds until the catalyst completely filled the graduated cylinder and overflowed. Next, the catalyst above the graduated cylinder was rubbed with a stainless spatula without applying vibration to the graduated cylinder. The catalyst was removed adhered to the graduated cylinder outside using a brush, the catalyst weight was calculated from the weight measurement value (average of two measurements), and bulk density apparent from the volume of the graduated cylinder (ABD)
Was calculated to be 1.35 g / ml. Table 1 shows the results. [Measurement of Filled Bulk Density (CBD)] The catalyst was sampled in a petri dish of known weight, weighed (catalyst: B / g), and the thickness of the catalyst was made uniform. It was allowed to stand for 30 minutes. Thereafter, the weight was measured (after-standing catalyst weight: D / g). The catalyst was placed in a stationary 25 ml graduated cylinder of known weight (approximately 2
About 25ml filled to 0 mm × about 84 mm), shaken for 5 minutes on a vibrator, measuring the volume of the catalyst (v / ml)
did. Was then measured catalyst weight (w / g). Then the equation (3), packing bulk density (CBD): d (g / ml)
Was calculated.
【００４７】[0047]
【数３】 ｄ＝ ｗ／ｖ × Ｂ／Ｄ （３） 上記の方法により、充填嵩密度を測定したところ、１．
５４ ｇ／ｍｌであった。結果を表１に示す。［圧縮強度の測定］ 触媒の圧縮強度：Ｉ（ＭＰａ）は、ＪＩＳ２８８４１−
１９９３「圧縮強度」に従い、以下のように測定した。
篩分した５３〜６３μｍの触媒から任意に採取した１０
０個の粒子について、島津製作所製「微少圧縮試験器
ＭＣＴＭ−５００型」を用い、下記の条件で測定し、そ
の平均値を圧縮強度の測定値とした。 上部加圧圧子：ダイヤモンド製 直径５００μｍ平面圧
子、下部加圧板：ステンレス鋼製、負荷速度：０．７９
ｇｆ／ｓｅｃ 具体的には、上記の試験器を用いて、粒径 ｄ／μｍの
触媒粒子に２点載荷を行い、粒子が破砕したときの応
力：ｆ／ｇｆを測定し、平松の方法（日本鉱業会誌 Ｖ
ｏｌ．８１、Ｎｏ．９３２，Ｐ．１０２４、１９６５
「非整形試験片による岩石の引っ張り強さの迅速試
験」）に従い、式（３）により算出される値を粒子１０
０個について平均した値を圧縮強度とした。Equation 3] d = w / v × B / D (3) by the methods described above, it was measured packing bulk density, 1.
It was 54 g / ml. Table 1 shows the results. [Measurement of Compressive Strength ] The compressive strength of the catalyst: I (MPa) is in accordance with JIS28841.
According to 1993 "compression strength", it was measured as follows.
10 were arbitrarily taken from sieved the 53~63μm catalyst
About 0 particles, "Micro compression tester manufactured by Shimadzu Corporation"
Using MCTM-500 Model ", measured under the following conditions, and the average value and the measured value of the compression strength. Upper pressing indenter: diamond 500 μm flat indenter, lower pressing plate: stainless steel, load speed: 0.79
gf / sec Specifically, using the tester described above, two-point loading was performed on the catalyst particles having a particle size of d / μm, and the stress when the particles were crushed: f / gf was measured. Nippon mining Journal V
ol. 81, No. 923, p. 1024, 1965
According to the “rapid test for tensile strength of rock using an unshaped specimen”, the value calculated by the equation (3)
The value averaged for 0 pieces was taken as the compressive strength.
【００４８】[0048]
【数４】 Ｉ＝８７４０ｆ／ｄ2 （３） 上記の方法により、圧縮強度を測定したところ、３７．
９ ＭＰａであった。結果を表１に示す。プロパンのアンモ酸化反応 上記のように製造した触媒５５０ｍｇを、内径が６ｍｍ
であるパイレックス（登録商標）ガラス管に充填し、Ｐ
ＰＡ／ＮＨ3／Ｏ2／Ｎ2＝１／１．２／３．１５／１
１．８５である混合ガスを、常圧、５００Ｎｍｌ／ｈｒ
（ＷＷＨ＝０．０８２ ｋｇ-ＰＰＡ／ｋｇ−ｃａｔ／
ｈｒ、空間速度 ＳＶ約１０００ｈ-1）の流速で供給
し、反応温度４４０℃でプロパンのアンモ酸化反応を行
った。アクリロニトリル（ＡＮ）の収率は５２．２％、
プロパン（ＰＰＡ）の転化率は８３．５％であった。結
果を表１に示す。 （実施例２）Ｍｏ1Ｖ0.25Ｎｂ0.16Ｔｅ0.11Ｏｎ／ＳｉＯ2−１０ｗｔ
％の製造 酸化セリウムを添加しない以外は実施例１と同様にし
て、触媒を製造した。実施例１と同様に組成を分析した
ところ、Ｍｏ1Ｖ0.25Ｎｂ0.16Ｔｅ0.11Ｏｎ／ＳｉＯ2−
１０ｗｔ％であった。I = 8740f / d 2 (3) The compressive strength was measured by the above method.
It was 9 MPa. Table 1 shows the results. Ammoxidation reaction of propane 550 mg of the catalyst produced as described above was treated with an inner diameter of 6 mm.
In a Pyrex (registered trademark) was charged into a glass tube, P
PA / NH 3 / O 2 / N 2 = 1 / 1.2 / 3.15 / 1
The mixed gas is 1.85 atmospheric pressure, 500Nml / hr
(WWH = 0.082 kg-PPA / kg-cat /
hr, space velocity SV was supplied at a flow rate of about 1000 h -1 ), and an ammoxidation reaction of propane was performed at a reaction temperature of 440 ° C. 52.2% and the yield of acrylonitrile (AN),
Conversion of propane (PPA) was 83.5%. Table 1 shows the results. (Example 2) Mo 1 V 0.25 Nb 0.16 Te 0.11 On / SiO 2 -10 wt
% The production of a catalyst was carried out in the same manner as in Example 1 except that cerium oxide was not added. When the composition was analyzed in the same manner as in Example 1, Mo 1 V 0.25 Nb 0.16 Te 0.11 On / SiO 2 −
It was 10 wt%.
【００４９】実施例１と同様に密度、強度を測定したと
ころ、ＡＢＤ：１．３１ｇ／ｍｌ、ＣＢＤ：１．４９ｇ
／ｍｌ、圧縮強度：３８．８ ＭＰａであった。結果を
表１に示す。プロパンのアンモ酸化反応 上記のように製造した触媒を使用したこと以外は、実施
例１と同様にプロパンのアンモ酸化反応を行った。反応
温度４２０℃でのアクリロニトリル（ＡＮ）の収率は４
９．１％、プロパン（ＰＰＡ）の転化率は７３．９％で
あった。結果を表１に示す。 （実施例３）Ｍｏ1Ｖ0.30Ｎｂ0.16Ｔｅ0.14Ｏｎ／ＳｉＯ2−１０ｗｔ
％の製造 メタバナジン酸アンモニウムの量を１１５０ｇとした以
外は、実施例２と同様に触媒を製造した。触媒の組成を
ＸＲＦにより分析したところ、Ｍｏ1Ｖ0.30Ｎｂ0.16Ｔ
ｅ0.14Ｏｎ／ＳｉＯ2−１０ｗｔ％であった。実施例１
と同様に密度、強度を測定したところ、ＡＢＤ：１．３
２ｇ／ｍｌ、ＣＢＤ：１．４９ｇ／ｍｌ、圧縮強度：４
３．４ ＭＰａであった。結果を表１に示す。プロパンのアンモ酸化反応 上記のように製造した触媒を用いたこと以外は、実施例
１と同様に反応を行った。反応温度を４２０℃でのアク
リロニトリル（ＡＮ）の収率は５０．０％、プロパン
（ＰＰＡ）の転化率は７７．１％であった。結果を表１
に示す。 （実施例４）Ｍｏ1Ｖ0.27Ｎｂ0.16Ｔｅ0.12Ｏｎ／ＳｉＯ2−１０ｗｔ
％の製造 メタバナジン酸アンモニウムの量を１０３４ｇとした以
外は、実施例２と同様に触媒を製造した。ＸＲＦ法によ
り組成を分析したところ、Ｍｏ1Ｖ0.27Ｎｂ0.1 6Ｔｅ
0.12Ｏｎ／ＳｉＯ2−１０ｗｔ％であった。実施例１と
同様に密度、強度を測定したところ、ＡＢＤ：１．２６
ｇ／ｍｌ、ＣＢＤ：１．４２ｇ／ｍｌ、圧縮強度：４
４．７ ＭＰａであった。結果を表１に示す。プロパンのアンモ酸化反応 上記のように製造した触媒を用いたこと以外は、実施例
１と同様に反応を行った。反応温度を４２０℃でのアク
リロニトリル（ＡＮ）の収率は４９．２％、プロパン
（ＰＰＡ）の転化率は７４．６％であった。結果を表１
に示す。 （実施例５）Ｍｏ1Ｖ0.30Ｎｂ0.12Ｔｅ0.138Ｏｎ／ＳｉＯ2−１０ｗ
ｔ％の製造 イオン交換水 １４３９９ｇを７５℃に加温し、パラモ
リブデン酸アンモニウム ３５３１ｇ、メタバナジン酸
アンモニウム ７０１．９ｇ、テルル酸 ９１８．６ｇ
をこの順番で投入し撹拌して溶解させた。この溶液を７
０℃に放冷し、シリカゾル（触媒化成工業 Ｓ−２０
Ｌ：ＳｉＯ2 ２０ｗｔ％） ２４６３ｇを加えて撹拌
し、４０℃まで放冷し、シュウ酸二水和物 ４３８ｇを
加えて溶解させ、４０℃に保った。これをＡ液とする。
Ａ液に酸化ニオブゾル（実施例１で使用したものと同
じ） ３１９０ｇを速やかに加え、４０℃に保った。こ
れを１５分間撹拌した後、実施例１と同様に乾燥、熱分
解、焼成を経て触媒を得た。実施例１と同様に分析した
ところ、触媒の組成はＭｏ1Ｖ0.30Ｎｂ０.12Ｔｅ０.138
Ｏｎ／ＳｉＯ2−１０ｗｔ％であった。The density and strength were measured in the same manner as in Example 1.
Roller, ABD: 1.31 g / ml, CBD: 1.49 g
/ Ml, compressive strength: 38.8 MPa. The result
It is shown in Table 1.Ammoxidation of propane Except for using the catalyst prepared as described above, embodiments
Examples were carried out ammoxidation reaction of similarly propane 1. reaction
The yield of acrylonitrile (AN) at a temperature of 420 ° C is 4
9.1%, the conversion of propane (PPA) in 73.9%
there were. Table 1 shows the results. (Example 3) Mo 1 V 0.30 Nb 0.16 Te 0.14 On / SiO 2 -10wt
%Manufacturing of The amount of ammonium metavanadate was changed to 1150 g.
Except for the above, a catalyst was produced in the same manner as in Example 2. The composition of the catalyst
Analysis by XRF showed that Mo1V0.30Nb0.16T
e0.14On / SiOTwoIt was -10wt%. Example 1
When the density and strength were measured in the same manner as in the above, ABD was 1.3.
2g / ml, CBD: 1.49g / ml, compressive strength: 4
It was 3.4 MPa. Table 1 shows the results.Ammoxidation of propane Examples except that the catalyst prepared as described above was used
1 The reaction was performed in the same manner. Reaction temperature at 420 ° C
The yield of rilonitrile (AN) is 50.0%, propane
The conversion of (PPA) was 77.1%. Table 1 shows the results
Shown in (Example 4)Mo 1 V 0.27 Nb 0.16 Te 0.12 On / SiO 2 -10 wt
%Manufacturing of The amount of ammonium metavanadate was changed to 1034 g.
Except for the above, a catalyst was produced in the same manner as in Example 2. XRF method
Analysis of the composition1V0.27Nb0.1 6Te
0.12On / SiOTwoIt was -10wt%. Example 1 and
When the density and strength were measured in the same manner, ABD: 1.26
g / ml, CBD: 1.42 g / ml, compressive strength: 4
It was 4.7 MPa. Table 1 shows the results.Ammoxidation of propane Except for using catalyst prepared as described above, Example
The reaction was carried out as in 1. Reaction temperature at 420 ° C
The yield of Rironitoriru (AN) 49.2% propane
Conversion of (PPA) was 74.6%. Table 1 shows the results
Shown in (Example 5)Mo 1 V 0.30 Nb 0.12 Te 0.138 On / SiO 2 -10w
Production of t% Warm 14399 g of ion-exchanged water to 75 ° C.
3531 g of ammonium ribate, metavanadic acid
701.9 g of ammonium, 918.6 g of telluric acid
Were added in this order and stirred to dissolve. This solution is
After cooling to 0 ° C, the silica sol (Catalyzed Chemical Industry S-20
L: SiOTwo (20 wt%) Add 2463 g and stir
And allowed to cool to 40 ° C., oxalic acid dihydrate 438g
In addition to dissolve, and kept at 40 ° C.. This is designated as solution A.
Same as that used in the niobium oxide sol (Example 1 A solution
3190 g was quickly added and kept at 40 ° C. This
After stirring for 15 minutes, the mixture was dried and heated in the same manner as in Example 1.
After dissolving and calcining, a catalyst was obtained. Analyzed in the same manner as in Example 1.
However, the composition of the catalyst is Mo1V0.30Nb0.12Te0.138
On / SiOTwoIt was -10wt%.
【００５０】実施例１と同様に密度、強度を測定したと
ころ、ＡＢＤ：１．３３ｇ／ｍｌ、ＣＢＤ：１．５０ｇ
／ｍｌ、圧縮強度：４５．２ ＭＰａであった。結果を
表１に示す。プロパンのアンモ酸化反応 上記のように製造した触媒を用いたこと以外は、実施例
１と同様に反応を行った。反応温度４３０℃でのアクロ
ニトリル（ＡＮ）の収率は４４．１％、プロパン（ＰＰ
Ａ）の転化率は８２．３％であった。結果を表１に示
す。 （比較例１）Ｍｏ1Ｖ0.30Ｎｂ0.12Ｔｅ0.17Ｏｎ／ＳｉＯ2−１０ｗｔ
％の製造 イオン交換水 ２１７４０ｇを７５℃に加温し、パラモ
リブデン酸アンモニウム ５７８２ｇ、メタバナジン酸
アンモニウム １１５０ｇ、テルル酸 １７２９ｇをこ
の順番で投入し撹拌して溶解させた。この溶液を７０℃
に放冷し、シリカゾル（実施例１と同じものを使用）
４０７６ｇを加えて撹拌し、６０℃に保った。これをＡ
液とする。別にイオン交換水５８９６ｇを５０℃に加温
し、シュウ酸ニオブアンモニウム（実施例１と同じもの
を使用） １７６６ｇを加えて７０℃まで加熱しながら
撹拌して溶解させ、４０℃に保った。これをＢ液とす
る。Ｂ液とＡ液を速やかに混合し、直ちに１５分間撹拌
した後、キルン処理の温度を３５０℃、昇温速度４０℃
／ｍｉｎとした以外は、実施例１と同様に乾燥、熱分
解、焼成を行い触媒を得た。得られた触媒の組成をＸＲ
Ｆ法により分析したところ、Ｍｏ1Ｖ0.30Ｎｂ0.12Ｔｅ
0.17Ｏｎ／ＳｉＯ2−１０ｗｔ％であった。When the density and strength were measured in the same manner as in Example 1, the ABD was 1.33 g / ml and the CBD was 1.50 g.
/ Ml, compressive strength: 45.2 MPa. Table 1 shows the results. Ammoxidation reaction of propane The reaction was carried out in the same manner as in Example 1 except that the catalyst produced as described above was used. The yield of acronitrile (AN) at a reaction temperature of 430 ° C. was 44.1%, and that of propane (PP
The conversion of A) was 82.3%. Table 1 shows the results. (Comparative Example 1) Mo 1 V 0.30 Nb 0.12 Te 0.17 On / SiO 2 -10 wt
21740 g of the prepared ion-exchanged water was heated to 75 ° C., and 5782 g of ammonium paramolybdate, 1150 g of ammonium metavanadate, and 1729 g of telluric acid were charged in this order and dissolved by stirring. 70 ° C
And then cooled to silica sol (use the same one as in Example 1)
Added, stirred 4076G, it was maintained at 60 ° C.. This is A
Liquid. Separately deionized water 5896g was heated to 50 ° C., (the same as used in Example 1) of ammonium niobium oxalate 1766g and stirred to dissolve while heating to 70 ° C. was added and was kept at 40 ° C.. This is referred to as B solution. Solution B and Solution A were immediately mixed and immediately stirred for 15 minutes.
Except for / min, drying, thermal decomposition and calcination were carried out in the same manner as in Example 1 to obtain a catalyst. The composition of the resulting catalyst XR
Analysis by the F method showed that Mo 1 V 0.30 Nb 0.12 Te
0.17 On / SiO 2 -10 wt%.
【００５１】実施例１と同様に密度、強度を測定したと
ころ、ＡＢＤ：１．０３ｇ／ｍｌ、ＣＢＤ：１．１５ｇ
／ｍｌ、圧縮強度：１２．３ ＭＰａであった。結果を
表１に示す。プロパンのアンモ酸化反応 上記のように製造した触媒を用いたこと以外は、実施例
１と同様に反応を行った。反応温度を４２０℃でのアク
リロニトリル（ＡＮ）の収率は５２．０％、プロパン
（ＰＰＡ）の転化率は８６．３％であった。結果を表１
に示す。 （比較例２）キルンでの熱分解処理温度：２５０℃、昇
温速度：２０℃／ｍｉｎとした以外は比較例１と同様に
触媒を製造した。比較例１と同様に分析を行ったとこ
ろ、触媒組成はＭｏ1Ｖ0.30Ｎｂ0.12Ｔｅ0.13Ｏｎ／Ｓ
ｉＯ2−１０ｗｔ％であった。実施例１と同様に密度、
強度を測定したところ、ＡＢＤ：１．１９ｇ／ｍｌ、Ｃ
ＢＤ：１．３４ｇ／ｍｌ、圧縮強度：２５．８ ＭＰａ
であった。結果を表１に示す。プロパンのアンモ酸化反応 上記のように製造した触媒を用いたこと以外は実施例１
と同様に反応を行った。反応温度４２０℃でアクリロニ
トリル（ＡＮ）の収率は５２．３％、プロパン（ＰＰ
Ａ）の転化率は８３．７％であった。結果を表１に示
す。When the density and strength were measured in the same manner as in Example 1, ABD: 1.03 g / ml, CBD: 1.15 g
/ Ml, compressive strength: was 12.3 MPa. Table 1 shows the results. Except for using the resulting catalyst as ammoxidation above propane were reacted in the same manner as in Example 1. At a reaction temperature of 420 ° C., the yield of acrylonitrile (AN) was 52.0%, and the conversion of propane (PPA) was 86.3%. Table 1 shows the results
Shown in (Comparative Example 2) A catalyst was produced in the same manner as in Comparative Example 1, except that the temperature of the thermal decomposition treatment in the kiln was 250 ° C and the heating rate was 20 ° C / min. Was analyzed in the same manner as in Comparative Example 1, the catalyst composition Mo 1 V 0.30 Nb 0.12 Te 0.13 On / S
iO 2 -10 wt%. Density as in Example 1,
When the strength was measured, ABD: 1.19 g / ml, C
BD: 1.34 g / ml, compressive strength: 25.8 MPa
Met. Table 1 shows the results. Except for using the resulting catalyst as ammoxidation above propane Example 1
The reaction was carried out in the same manner as described above. At a reaction temperature of 420 ° C., the yield of acrylonitrile (AN) was 52.3%, and propane (PP
The conversion of A) was 83.7%. Table 1 shows the results.
【００５２】[0052]
【表１】 [Table 1]
【００５３】表１から明らかなように、SiO2含有量が少
ない本発明の複合酸化物触媒の場合は、ＡＢＤ及び／又
はＣＢＤが特定値以上に大きい場合は、ＡＮ収率を大幅
に低下させることなく、良好な強度を示すことが分か
る。[0053] As apparent from Table 1, in the case of complex oxide catalyst of the present SiO 2 content is less invention, when the ABD and / or CBD larger than a specific value, greatly reduce the AN yield It can be seen that a good strength is exhibited without using the same.
【００５４】[0054]
【発明の効果】本発明の複合酸化物触媒は、低いＳｉＯ
2含有量でも高い触媒強度を有する。The composite oxide catalyst of the present invention has a low SiO 2 content.
Even with 2 content, it has high catalyst strength.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 展 神奈川県横浜市青葉区鴨志田町1000番地 三菱化学株式会社横浜総合研究所内 Ｆターム(参考） 4G069 BA02A BA02B BB06A BB06B BC01A BC08A BC15A BC16A BC17A BC18A BC20A BC21A BC22A BC23A BC24A BC25A BC26A BC30A BC34A BC35A BC38A BC39A BC40A BC41A BC43B BC49A BC50A BC51A BC53A BC54A BC54B BC55A BC55B BC56A BC57A BC58A BC59A BC59B BC60A BC61A BC62A BC64A BC65A BC66A BC67A BC68A BC69A BC70A BC71A BD03A BD07A BD10A BD10B CB07 CB10 CB17 CB53 CB54 CB74 DA08 EA01X EB18Y EC21X EC21Y ED03 FC08 4H006 AA02 AB46 AC54 BA09 BA12 BA14 BA15 BA30 BA55 BA56 BA80 BA81 BC13 BE14 BE30 QN24 4H039 CA70 CC10 CL50 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Noboru Watanabe No. 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Laboratory F-term (reference) 4G069 BA02A BA02B BB06A BB06B BC01A BC08A BC15A BC16A BC17A BC18A BC20A BC21A BC22A BC23A BC24A BC25A BC26A BC30A BC34A BC35A BC38A BC39A BC40A BC41A BC43B BC49A BC50A BC51A BC53A BC54A BC54B BC55A BC55B BC56A BC57A BC58A BC59A BC59B BC60A BC61A BC62A BC64A BC65A BC66A BC67A BC68A BC69A BC70A BC71A BD03A BD07A BD10A BD10B CB07 CB10 CB17 CB53 CB54 CB74 DA08 EA01X EB18Y EC21X EC21Y ED03 FC08 4H006 AA02 AB46 AC54 BA09 BA12 BA14 BA15 BA30 BA55 BA56 BA80 BA81 BC13 BE14 BE30 QN24 4H039 CA70 CC10 CL50
Claims (13)
化物と２５重量％以下（全触媒に対して）のＳｉＯ2を
含む触媒であり、且つ、この触媒の見かけ嵩密度（ＡＢ
Ｄ）が１．２０g/ml以上であることを特徴とする複合金
属酸化物触媒。 【化１】 ＭｏaＶbＮｂcＸdＹfＯn （１） （式（１）において、Ｘはテルルおよび／またはアンチ
モンを表し、Ｙは周期表の１〜１６族の元素で、Ｍｏ，
Ｖ，Ｎｂ、Ｔｅ、Ｏ以外から選ばれる１以上の元素を表
し、ａ＝１．０、０．０１＜ｂ≦１、０．０５＜ｃ≦
０．５、０＜ｄ≦１、０≦ｆ＜１、ｎは他の元素の酸化
状態によって決まる値である。）1. A catalyst containing a composite metal oxide represented by the following composition formula (1) and SiO 2 in an amount of 25% by weight or less (based on the total catalyst), and having an apparent bulk density (AB)
D) is 1.20 g / ml or more. ## STR1 ## In Mo a V b Nb c X d Y f O n (1) ( Formula (1), X represents a tellurium and / or antimony, Y is 1 to 16 group elements of the periodic table, Mo ,
Represents one or more elements selected from elements other than V, Nb, Te, and O, and a = 1.0, 0.01 <b ≦ 1, 0.05 <c ≦
0.5, 0 <d ≦ 1, 0 ≦ f <1, and n are values determined by the oxidation state of other elements. )
２．０g/mlである請求項１に記載の複合金属酸化物触
媒。2. An apparent bulk density (ABD) of 1.25 to 2.
2.0 g / ml a composite metal oxide catalyst according to claim 1.
g/ml以上である請求項１又は２に記載の複合金属酸化物
触媒。3. The catalyst has a packed bulk density (CBD) of 1.35.
Composite metal oxide catalyst according to claim 1 or 2 g / ml or more.
０g/mlである請求項１〜３のいずれかに記載の複合金属
酸化物触媒。4. A packing bulk density (CBD) of 1.40 to 2.
The composite metal oxide catalyst according to any one of claims 1 to 3, which is 0 g / ml.
請求項１〜５のいずれかに記載の複合金属酸化物触媒。5. The composite metal oxide catalyst according to claim 1, wherein the content of SiO 2 is 15% by weight or less.
０、０．１＜ｂ≦０．８、０．０５＜ｃ≦０．３ 、
０．０３＜ｄ≦０．５、０≦ｆ＜０．５である請求項１
〜３のいずれかに記載の複合金属酸化物触媒。6. The oxide of the formula (1) wherein a = 1.
0, 0.1 <b ≦ 0.8, 0.05 <c ≦ 0.3,
2. The relationship of 0.01 <d ≦ 0.5 and 0 ≦ f <0.5.
4. The composite metal oxide catalyst according to any one of claims 1 to 3.
０、０．１＜ｂ≦０．６、０．０５＜ｃ≦０．３ 、
０．０５＜ｄ≦０．３、０≦ｆ＜０．２である請求項６
に記載の複合金属酸化物触媒。7. The oxide of the formula (1), wherein a = 1.
0, 0.1 <b ≦ 0.6, 0.05 <c ≦ 0.3,
7. The relationship of 0.05 <d ≦ 0.3 and 0 ≦ f <0.2.
3. The composite metal oxide catalyst according to item 1.
である請求項１〜７のいずれかに記載の複合金属酸化物
触媒。8. The composite metal oxide catalyst according to claim 1, wherein X is tellurium in the oxide of the formula (1).
元素である請求項１〜８のいずれかに記載の複合金属酸
化物触媒。In oxide 9. formula (1), Y is a composite metal oxide catalyst according to claim 1 which is a rare earth element.
１〜９のいずれかに記載の複合金属酸化物触媒。10. The composite metal oxide catalyst according to claim 1, which is used for a gas phase catalytic oxidation reaction.
酸化物と２５重量％以下（全触媒に対して）のＳｉＯ2
を含む触媒であり、且つ、この触媒の見かけ嵩密度（Ａ
ＢＤ）が１．２０g/ml以上である複合金属酸化物触媒の
存在下、アルカンを窒素源と気相接触酸化反応させるこ
とを特徴とする気相接触酸化反応方法。 【化２】 ＭｏaＶbＮｂcＸdＹfＯn （１） （式（１）において、Ｘはテルルおよび／またはアンチ
モンを表し、Ｙは周期表の１〜１６族の元素で、Ｍｏ，
Ｖ，Ｎｂ、Ｔｅ、Ｏ以外から選ばれる１以上の元素を表
し、ａ＝１．０、０．０１＜ｂ≦１、０．０５＜ｃ≦
０．５、０＜ｄ≦１、０≦ｆ＜１、ｎは他の元素の酸化
状態によって決まる値である。）11. A composite metal oxide represented by the following composition formula (1) and 25% by weight or less (based on all catalysts) of SiO 2
A catalyst comprising, and an apparent bulk density (A in this catalyst
The presence of a complex metal oxide catalyst BD) is 1.20 g / ml or more, gas-phase catalytic oxidation reaction wherein the to nitrogen source and the gas phase catalytic oxidation reaction of alkanes. ## STR2 ## In Mo a V b Nb c X d Y f O n (1) ( Formula (1), X represents a tellurium and / or antimony, Y is 1 to 16 group elements of the periodic table, Mo ,
Represents one or more elements selected from elements other than V, Nb, Te, and O, and a = 1.0, 0.01 <b ≦ 1, 0.05 <c ≦
0.5,0 <d ≦ 1,0 ≦ f <1, n is a value determined by the oxidation states of the other elements. )
に記載の気相接触酸化反応方法。12. The method of claim 11, wherein the alkane is propane.
2. The gas phase catalytic oxidation reaction method described in 1. above.
化することによりα、β不飽和ニトリル化合物が生成す
る請求項１１又は１２に記載の気相接触酸化反応方法。13. The gas phase catalytic oxidation reaction method according to claim 11, wherein an α, β unsaturated nitrile compound is produced by subjecting the alkane to gas phase catalytic oxidation together with a nitrogen source.
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