JP2011120990A - Composite metal oxide catalyst and method of producing the same - Google Patents
Composite metal oxide catalyst and method of producing the same Download PDFInfo
- Publication number
- JP2011120990A JP2011120990A JP2009279787A JP2009279787A JP2011120990A JP 2011120990 A JP2011120990 A JP 2011120990A JP 2009279787 A JP2009279787 A JP 2009279787A JP 2009279787 A JP2009279787 A JP 2009279787A JP 2011120990 A JP2011120990 A JP 2011120990A
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- composite metal
- oxide catalyst
- acid
- ammoxidation reaction
- 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
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 96
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 17
- 239000013078 crystal Substances 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
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- 239000001301 oxygen Substances 0.000 claims abstract description 18
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- 239000000203 mixture Substances 0.000 claims abstract description 15
- 150000002825 nitriles Chemical class 0.000 claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
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- IIXQANVWKBCLEB-UHFFFAOYSA-N tellurium trioxide Chemical compound O=[Te](=O)=O IIXQANVWKBCLEB-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、特定の組成及び結晶系を有する複合金属酸化物触媒及びその製造方法に関する。 The present invention relates to a composite metal oxide catalyst having a specific composition and crystal system and a method for producing the same.
近年、複合金属酸化物は、その金属の特性と、金属元素が原子レベルで空間特異的に配置された結晶構造の特性からなる協同効果を期待して研究され、注目を集めている。その手法は、多くの触媒材料でも応用され、多種多様な複合金属酸化物触媒が提案されており、その結晶構造、構成金属種、及びその構成金属の結晶構造内における位置は触媒活性に影響を与えることが知られている。モリブデンやバナジウム等の金属を含む複合金属酸化物触媒は、アルカンから不飽和ニトリルを合成するための触媒として注目されている。これらの金属を含む複合金属酸化物触媒の中には、低級炭化水素のアンモ酸化反応の触媒として用いた場合、目的生成物の収率が比較的高いものがあることが報告されている。
特許文献１には、少なくともモリブデン、バナジウム、アンチモン、酸素を含む複合酸化物が、特定のユニットセルパラメータを有し、Ｘ線回折によってある特定の位置にピークを示す複合金属酸化物の結晶体がアルカンの気相接触アンモ酸化反応によるニトリルの製造に用いることができることが記載されている。また、その結晶体は斜方晶型であることも記載されている。
特許文献２には、これまで報告されている斜方晶型ではなく、モリブデンとバナジウムと酸素のみからなる三方晶系の複合金属酸化物が、斜方晶型と同じ金属組成の複合金属酸化物よりも低い温度で、アクロレインを効率的に転化し、アクリル酸を合成できることが記載されている。
In recent years, composite metal oxides have been studied and attracted attention with the expectation of a cooperative effect consisting of the characteristics of the metal and the crystal structure in which metal elements are spatially arranged at the atomic level. The method has been applied to many catalyst materials, and a wide variety of composite metal oxide catalysts have been proposed. The crystal structure, constituent metal species, and position of the constituent metal in the crystal structure have an effect on the catalytic activity. It is known to give. A composite metal oxide catalyst containing a metal such as molybdenum or vanadium has attracted attention as a catalyst for synthesizing an unsaturated nitrile from an alkane. It has been reported that some composite metal oxide catalysts containing these metals have a relatively high yield of the target product when used as a catalyst for ammoxidation of lower hydrocarbons.
Patent Document 1 discloses a composite metal oxide crystal in which a composite oxide containing at least molybdenum, vanadium, antimony, and oxygen has a specific unit cell parameter and exhibits a peak at a specific position by X-ray diffraction. It is described that it can be used for the production of nitriles by gas phase catalytic ammoxidation reaction of alkanes. It is also described that the crystal is orthorhombic.
Patent Document 2 discloses that a trigonal complex metal oxide composed only of molybdenum, vanadium and oxygen is not a orthorhombic type reported so far, but a complex metal oxide having the same metal composition as that of the orthorhombic type. It is described that acrolein can be efficiently converted and acrylic acid can be synthesized at a lower temperature.
本発明者らが検討したところによると、上記特許文献２に記載されたような三方晶系の触媒は、気相接触アンモ酸化反応の触媒として使用する場合、金属成分が同じ斜方晶のものと比較して、原料の転化率が高い傾向にある。しかしながら、特許文献２に記載されたような、モリブデンとバナジウムという金属成分を二成分しか含まない複合金属酸化物の触媒性能は、十分に満足できるものではない。斜方晶の複合金属酸化物同士で比較すると、モリブデンとバナジウムという二成分系と比べて、Ｔｅ、Ｓｂ等の第三の金属成分を含有する複合金属酸化物の中には、気相接触アンモ酸化反応の触媒としてより好適な性能を示すものがある。そこで、モリブデン、バナジウムに加えて第三の金属成分を含有する複合金属酸化物であって、結晶系が三方晶系のものが得られれば、その複合金属酸化物は高いアンモ酸化活性を有する可能性があることに着目した。現在までのところ、結晶系が三方晶系の複合金属酸化物で、且つ、三成分以上の金属を含有するアンモ酸化反応用の触媒は知られていない。
上記事情に鑑み、本発明が解決しようとする課題は、アルカン又はアルケンの気相接触アンモ酸化反応により対応する不飽和ニトリルを製造する際に用いられる複合金属酸化物触媒であって、目的生成物の選択性が高く、性能に優れた触媒を提供することである。
According to a study by the present inventors, a trigonal catalyst as described in Patent Document 2 is an orthorhombic crystal having the same metal component when used as a catalyst for a gas phase catalytic ammoxidation reaction. Compared to the above, the raw material conversion tends to be high. However, the catalytic performance of a composite metal oxide containing only two metal components, molybdenum and vanadium, as described in Patent Document 2, is not fully satisfactory. Compared with orthorhombic complex metal oxides, compared with the binary system of molybdenum and vanadium, some complex metal oxides containing a third metal component such as Te and Sb include gas phase contact ammonia. Some catalysts exhibit more suitable performance as oxidation catalysts. Therefore, if a composite metal oxide containing a third metal component in addition to molybdenum and vanadium and having a trigonal crystal system, the composite metal oxide may have high ammoxidation activity. Focused on the nature. To date, there is no known catalyst for an ammoxidation reaction that is a complex metal oxide having a trigonal crystal system and containing a metal having three or more components.
In view of the above circumstances, the problem to be solved by the present invention is a composite metal oxide catalyst used in the production of a corresponding unsaturated nitrile by a gas phase catalytic ammoxidation reaction of an alkane or alkene, wherein the target product It is to provide a catalyst with high selectivity and excellent performance.
本発明者らは、アルカン又はアルケンから、対応する不飽和ニトリルを製造するためのアンモ酸化反応用触媒について鋭意検討した結果、結晶系が三方晶系であり、且つ、モリブデン、バナジウムからなる複合金属酸化物にＴｅやＳｂ等の第三の金属成分をさらに添加することにより、同じ金属種を用いた斜方晶型複合金属酸化物よりも、高選択的に目的生成物が得られることを見出し、本発明に至った。 As a result of intensive studies on an ammoxidation reaction catalyst for producing a corresponding unsaturated nitrile from alkane or alkene, the present inventors have found that the crystal system is a trigonal system, and a composite metal composed of molybdenum and vanadium. It has been found that by adding a third metal component such as Te or Sb to the oxide, the target product can be obtained with higher selectivity than an orthorhombic complex metal oxide using the same metal species. The present invention has been reached.
即ち、本発明は以下の通りである。
［１］
アルカン又はアルケンのアンモ酸化反応に用いられる触媒であって、下記式（Ｉ）
Ｍｏ1ＶaＺbＯn （Ｉ）
（式中、Ｚは、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｔａ、Ｔｉ、Ｐ、Ｂｉからなる群から選択される少なくとも１種類以上の金属元素を示し、ａ、ｂは、それぞれＭｏ１原子あたりのＶ、Ｚの原子比を示し、０＜ａ≦１、０＜ｂ≦１であり、ｎは構成金属の酸化状態によって決まる酸素の原子比を示す。）
で表される組成を有し、結晶系が三方晶である複合金属酸化物触媒。
［２］
下記式（Ｉ）
Ｍｏ1ＶaＺbＯn （Ｉ）
（式中、Ｚは、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｔａ、Ｔｉ、Ｐ、Ｂｉからなる群から選択される少なくとも１種類以上の金属元素を示し、ａ、ｂは、それぞれＭｏ１原子あたりのＶ、Ｚの原子比を示し、０＜ａ≦１、０＜ｂ≦１であり、ｎは構成金属の酸化状態によって決まる酸素の原子比を示す。）
で表される組成を有し、結晶系が三方晶である複合金属酸化物触媒を製造する方法であって、
（１）Ｍｏ、Ｖを含む原料調合液を調製する工程と、
（２）前記原料調合液を加熱して結晶を生成させる工程と、
（３）前記加熱により生成した結晶に、Ｚを含むスラリー及び／又は溶液を接触させる工程と、
を有し、
前記工程（１）において調製した原料調合液のｐＨを酸性に保つことを含む、複合金属酸化物触媒の製造方法。
［３］
（４）前記工程（２）において生成した結晶を不活性ガス雰囲気下、２００〜８００℃で焼成する工程をさらに有する、上記［２］記載の複合金属酸化物触媒の製造方法。
［４］
上記［１］記載の複合金属酸化物触媒を用いてアルカン又はアルケンをアンモ酸化反応に供し、対応する不飽和ニトリルを製造する方法。
That is, the present invention is as follows.
[1]
A catalyst used for an ammoxidation reaction of an alkane or alkene, which has the following formula (I)
Mo 1 V a Z b O n (I)
(In the formula, Z represents at least one metal element selected from the group consisting of Te, Sb, Nb, W, Ce, Ta, Ti, P, Bi, and a and b are each per Mo atom. (The atomic ratio of V and Z in the formula is 0 <a ≦ 1, 0 <b ≦ 1, and n represents the atomic ratio of oxygen determined by the oxidation state of the constituent metals.)
A composite metal oxide catalyst having a composition represented by:
[2]
Formula (I)
Mo 1 V a Z b O n (I)
(In the formula, Z represents at least one metal element selected from the group consisting of Te, Sb, Nb, W, Ce, Ta, Ti, P, Bi, and a and b are each per Mo atom. (The atomic ratio of V and Z in the formula is 0 <a ≦ 1, 0 <b ≦ 1, and n represents the atomic ratio of oxygen determined by the oxidation state of the constituent metals.)
A method for producing a composite metal oxide catalyst having a composition represented by:
(1) a step of preparing a raw material preparation liquid containing Mo and V;
(2) heating the raw material preparation liquid to generate crystals;
(3) a step of bringing a slurry and / or a solution containing Z into contact with the crystals generated by the heating;
Have
The manufacturing method of a composite metal oxide catalyst including keeping pH of the raw material preparation liquid prepared in the said process (1) acidic.
[3]
(4) The method for producing a composite metal oxide catalyst according to the above [2], further comprising a step of firing the crystals produced in the step (2) at 200 to 800 ° C. in an inert gas atmosphere.
[4]
A method for producing a corresponding unsaturated nitrile by subjecting an alkane or alkene to an ammoxidation reaction using the composite metal oxide catalyst according to the above [1].
本発明により、アルカン又はアルケンの気相接触アンモ酸化反応により対応する不飽和ニトリルを製造する際に用いられる複合金属酸化物触媒であって、目的生成物の選択性が高く、性能に優れた触媒を提供することができる。 According to the present invention, a composite metal oxide catalyst used for producing a corresponding unsaturated nitrile by a gas-phase catalytic ammoxidation reaction of an alkane or alkene, which has high selectivity of the target product and excellent performance Can be provided.
以下、本発明を実施するための形態（以下、「本実施の形態」と略記する。）について詳細に説明する。尚、本発明は、以下の本実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.
［１］複合金属酸化物触媒
本実施の形態の複合金属酸化物触媒は、アルカン又はアルケンのアンモ酸化反応に用いられる触媒であって、下記式（Ｉ）
Ｍｏ1ＶaＺbＯn （Ｉ）
（式中、Ｚは、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｔａ、Ｔｉ、Ｐ、Ｂｉからなる群から選択される少なくとも１種類以上の金属元素を示し、ａ、ｂは、それぞれＭｏ１原子あたりのＶ、Ｚの原子比を示し、０＜ａ≦１、０＜ｂ≦１であり、ｎは構成金属の酸化状態によって決まる酸素の原子比を示す。）
で表される組成を有し、結晶系が三方晶である。
[1] Composite Metal Oxide Catalyst The composite metal oxide catalyst of the present embodiment is a catalyst used for an ammoxidation reaction of an alkane or alkene, and has the following formula (I)
Mo 1 V a Z b O n (I)
(In the formula, Z represents at least one metal element selected from the group consisting of Te, Sb, Nb, W, Ce, Ta, Ti, P, Bi, and a and b are each per Mo atom. (The atomic ratio of V and Z in the formula is 0 <a ≦ 1, 0 <b ≦ 1, and n represents the atomic ratio of oxygen determined by the oxidation state of the constituent metals.)
The crystal system is trigonal.
Ｚは、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｔａ、Ｔｉ、Ｐ、Ｂｉからなる群から選択される少なくとも１種類以上の金属元素を示し、好ましい成分としては、ＭｏやＶと組み合わせることでアルカン及びアルケンのアンモ酸化活性を向上させる有力な金属種として既に報告されている、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｂｉが挙げられる。複合金属酸化物触媒がこれらの金属元素を１種類以上含有する組成を有する場合、複合金属酸化物触媒の結晶構造中の特定部位にこれらの金属元素が挿入されるか、或いは、Ｍｏ及び／又はＶと交換されて、金属元素の構造的な安定性が増すと考えられる。その結果、複合金属酸化物触媒の耐熱安定性が向上し、さらには、原料や目的生成物の分解を抑制する効果を期待できる。 Z represents at least one metal element selected from the group consisting of Te, Sb, Nb, W, Ce, Ta, Ti, P, Bi, and a preferred component is alkane in combination with Mo or V. In addition, Te, Sb, Nb, W, Ce, and Bi, which have already been reported as effective metal species that improve the ammoxidation activity of alkenes, can be mentioned. When the composite metal oxide catalyst has a composition containing one or more of these metal elements, these metal elements are inserted into specific sites in the crystal structure of the composite metal oxide catalyst, or Mo and / or It is considered that the structural stability of the metal element is increased by exchanging with V. As a result, the heat resistance stability of the composite metal oxide catalyst is improved, and further, an effect of suppressing the decomposition of the raw material and the target product can be expected.
Ｍｏ１原子あたりのＶの原子比を示すａは、０＜ａ≦１であり、好ましい範囲は０＜ａ≦０．５である。複合金属酸化物触媒に含まれるＶの比率が上記範囲であると、原料の分解及び燃焼が抑制される。 “A” indicating the atomic ratio of V per Mo atom is 0 <a ≦ 1, and a preferable range is 0 <a ≦ 0.5. When the ratio of V contained in the composite metal oxide catalyst is in the above range, decomposition and combustion of the raw material are suppressed.
Ｍｏ１原子あたりのＺの原子比を示すｂは、０＜ｂ≦１であり、好ましい範囲は０＜ｂ≦０．７である。また、Ｚの酸化物は副反応を促進する可能性があるが、Ｚの比率が上記範囲である複合金属酸化物を合成する場合、仕込みのＺ比率が高すぎないためＺの酸化物が生成し難くなる。 B indicating the atomic ratio of Z per Mo atom is 0 <b ≦ 1, and a preferred range is 0 <b ≦ 0.7. In addition, Z oxide may promote side reactions. However, when synthesizing a composite metal oxide having a Z ratio in the above range, the Z ratio is not too high, so that an oxide of Z is generated. It becomes difficult to do.
本実施の形態の複合金属酸化物触媒の結晶系は三方晶である。本発明者は、式（Ｉ）で表される複合金属酸化物触媒について、同じ組成で結晶相のみ異なる複合金属酸化物触媒と比較した場合、三方晶のものは斜方晶のものよりも目的生成物の選択率が高く、特にプロパンからアクリロニトリルを合成するための触媒として用いた場合に選択率が顕著に高くなることを発見した。 The crystal system of the composite metal oxide catalyst of the present embodiment is a trigonal system. When the present inventors compared the composite metal oxide catalyst represented by the formula (I) with a composite metal oxide catalyst having the same composition but different crystal phases, the trigonal one is more objective than the orthorhombic one. It has been found that the selectivity of the product is high, especially when used as a catalyst for the synthesis of acrylonitrile from propane.
結晶系が三方晶であることは、ＣｕＫα線をＸ線源として得られるＸ線回折図において、２θ＝８．２°±０．２°、９．６°±０．２°、２２．２°±０．２°、２６．８°±０．２°、３０．１°±０．２°、４５．３°±０．２°の位置に主たる回折ピークを示すことによって確認することができる。
以下にＸ線回折の測定条件を示す。
Ｘ線源 ：ＣｕＫα１＋ＣｕＫα２
検出器 ：シンチレーションカウンター
管電圧 ：４０ｋＶ
管電流 ：２００ｍＡ
発散スリット ：１°
散乱スリット ：１°
受光スリット ：０．１５ｍｍ
スキャン速度 ：４°／ｍｉｎ
サンプリング幅 ：０．０２°
スキャン方法 ：２θ／θ法
Ｘ線回折の測定装置としては、ＲＩＧＡＫＵ ＲＩＮＴ２５００ＶＨＦ／ＰＣを用いることができる。
The fact that the crystal system is a trigonal crystal indicates that 2θ = 8.2 ° ± 0.2 °, 9.6 ° ± 0.2 °, 22.2 in an X-ray diffraction diagram obtained using CuKα rays as an X-ray source. It can be confirmed by showing main diffraction peaks at the positions of ± 0.2 °, 26.8 ° ± 0.2 °, 30.1 ° ± 0.2 °, 45.3 ° ± 0.2 °. it can.
The measurement conditions for X-ray diffraction are shown below.
X-ray source: CuKα1 + CuKα2
Detector: Scintillation counter tube voltage: 40 kV
Tube current: 200 mA
Divergent slit: 1 °
Scattering slit: 1 °
Light receiving slit: 0.15 mm
Scanning speed: 4 ° / min
Sampling width: 0.02 °
Scanning method: 2θ / θ method As a measuring apparatus for X-ray diffraction, RIGAKU RINT2500VHF / PC can be used.
［２］複合金属酸化物触媒の製造方法
本実施の形態の複合金属酸化物触媒の製造方法は、
下記式（Ｉ）
Ｍｏ1ＶaＺbＯn （Ｉ）
（式中、Ｚは、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｔａ、Ｔｉ、Ｐ、Ｂｉからなる群から選択される少なくとも１種類以上の金属元素を示し、ａ、ｂは、それぞれＭｏ１原子あたりのＶ、Ｚの原子比を示し、０＜ａ≦１、０＜ｂ≦１であり、ｎは構成金属の酸化状態によって決まる酸素の原子比を示す。）
で表される組成を有し、結晶系が三方晶である複合金属酸化物触媒を製造する方法であって、
（１）Ｍｏ、Ｖを含む原料調合液を調製する工程と、
（２）前記原料調合液を加熱して結晶を生成させる工程と、
（３）前記加熱により生成した結晶に、Ｚを含むスラリー及び／又は溶液を接触させる工程と、
を有し、
前記工程（１）において調製した原料調合液のｐＨを酸性に保つことを含む方法である。
[2] Manufacturing method of composite metal oxide catalyst The manufacturing method of the composite metal oxide catalyst of this Embodiment is
Formula (I)
Mo 1 V a Z b O n (I)
(In the formula, Z represents at least one metal element selected from the group consisting of Te, Sb, Nb, W, Ce, Ta, Ti, P, Bi, and a and b are each per Mo atom. (The atomic ratio of V and Z in the formula is 0 <a ≦ 1, 0 <b ≦ 1, and n represents the atomic ratio of oxygen determined by the oxidation state of the constituent metals.)
A method for producing a composite metal oxide catalyst having a composition represented by:
(1) a step of preparing a raw material preparation liquid containing Mo and V;
(2) heating the raw material preparation liquid to generate crystals;
(3) a step of bringing a slurry and / or a solution containing Z into contact with the crystals generated by the heating;
Have
It is a method including keeping pH of the raw material preparation prepared in the step (1) acidic.
（１）原料調合工程
工程（１）は、Ｍｏ、Ｖを含む原料調合液を調製する工程である。
(1) Raw material preparation step Step (1) is a step of preparing a raw material preparation liquid containing Mo and V.
工程（１）においては、水等の溶媒に、Ｍｏ、Ｖの原料を溶解、混合又は分散させて、原料調合液を得る。原料の溶解手順、混合手順又は分散手順としては特に限定されない。原料を同じ溶媒中で溶解、混合又は分散させてもよく、或いは原料を個別に溶媒中に溶解、混合又は分散させた後に両者を混合してもよい。また、必要に応じて加熱及び／又は攪拌してもよい。このようにして得られる原料調合液は均一な溶液であるか、若しくはスラリーである。 In the step (1), Mo, V raw materials are dissolved, mixed or dispersed in a solvent such as water to obtain a raw material mixture. It does not specifically limit as a melt | dissolution procedure of a raw material, a mixing procedure, or a dispersion | distribution procedure. The raw materials may be dissolved, mixed or dispersed in the same solvent, or both may be mixed after the raw materials are individually dissolved, mixed or dispersed in the solvent. Moreover, you may heat and / or stir as needed. The raw material preparation liquid thus obtained is a uniform solution or a slurry.
モリブデン（Ｍｏ）の原料としては、ヘプタモリブデン酸アンモニウム・６水和物に代表されるようなモリブデンを含有するイソポリ酸、三酸化モリブデン、二酸化モリブデン、リンモリブデン酸アンモニウム、ケイモリブデン酸アンモニウム等の一連のヘテロポリ酸類、及びこれらのアルカリ金属塩等を用いることが可能であるが、中でもヘプタモリブデン酸アンモニウム・６水和物を好適に用いることができる。 As a raw material of molybdenum (Mo), a series of molybdenum-containing isopolyacids such as ammonium heptamolybdate hexahydrate, molybdenum trioxide, molybdenum dioxide, ammonium phosphomolybdate, ammonium silicomolybdate, etc. Heteropolyacids and alkali metal salts thereof can be used, and among these, ammonium heptamolybdate hexahydrate can be preferably used.
バナジウム（Ｖ）の原料としては、オキシ硫酸バナジウム・ｎ水和物、酸化バナジウム類、塩化バナジウム、硫化バナジウム、ヨウ化バナジウム、水酸化バナジウム、水素化バナジウム等を用いることができるが、中でもオキシ硫酸バナジウム・ｎ水和物を好適に用いることができる。 As the raw material of vanadium (V), vanadium oxysulfate.n hydrate, vanadium oxides, vanadium chloride, vanadium sulfide, vanadium iodide, vanadium hydroxide, vanadium hydride and the like can be used. Vanadium · n hydrate can be preferably used.
原料調合工程における具体的な手順の一例としては、初めに（ア）ヘプタモリブデン酸アンモニウム・６水和物を蒸留水に溶解させる。このときのＭｏ含有水溶液の濃度範囲は１０〜１．０×１０-3ｍｏｌ／Ｌであることが好ましい。また、（ア）とは別に（イ）オキシ硫酸バナジウム・ｎ水和物を蒸留水に溶解させる。このときのＶ含有水溶液の濃度範囲は５〜１．０×１０-3ｍｏｌ／Ｌであることが好ましい。次に、（イ）の溶液を（ア）に加え十分に攪拌して原料調合液を調製する。また、ヘプタモリブデン酸アンモニウム・６水和物とオキシ硫酸バナジウム・ｎ水和物を固体の状態で混合した後に蒸留水に溶解させて、攪拌してもよい。また、蒸留水は冷却した状態で、若しくは加熱した状態で原料に加えても何ら問題はない。 As an example of a specific procedure in the raw material preparation step, first, (a) ammonium heptamolybdate hexahydrate is dissolved in distilled water. The concentration range of the Mo-containing aqueous solution at this time is preferably 10 to 1.0 × 10 −3 mol / L. Separately from (a), (b) vanadium oxysulfate.n hydrate is dissolved in distilled water. The concentration range of the V-containing aqueous solution at this time is preferably 5 to 1.0 × 10 −3 mol / L. Next, the solution of (a) is added to (a) and sufficiently stirred to prepare a raw material preparation solution. Alternatively, ammonium heptamolybdate hexahydrate and vanadium oxysulfate n hydrate may be mixed in a solid state and then dissolved in distilled water and stirred. Moreover, there is no problem even if distilled water is added to the raw material in a cooled state or in a heated state.
本実施の形態の製造方法においては、工程（１）で得られた原料調合液に酸を加えて、原料調合液のｐＨを酸性に保つ。このときのｐＨは１．０〜６．０が好ましく、１．７〜２．４がより好ましい。このときに添加する酸は、硫酸、硝酸、塩酸等の強酸水溶液が好ましく、また、強酸と種々の弱酸の混合した酸でｐＨを調整してもよい。こうして得られた溶液を、窒素に代表されるような不活性ガスで十分にバブリングして溶存酸素を系内から追い出し、オートクレーブに移す。オートクレーブは、酸性の水溶液に腐食されないものであり、かつ、後述する（２−１）水熱合成工程の条件に耐えうるものである限り、特に限定されない。例えば、ＳＵＳ３１６製のボトルでもよいし、ＳＵＳ製のボトルの内壁にフッ素コーティングが施されたボトルでもよいし、フッ素系の樹脂からなる容器が内包されたものでもよい。 In the manufacturing method of the present embodiment, an acid is added to the raw material preparation liquid obtained in step (1) to keep the pH of the raw material preparation liquid acidic. The pH at this time is preferably 1.0 to 6.0, and more preferably 1.7 to 2.4. The acid added at this time is preferably a strong acid aqueous solution such as sulfuric acid, nitric acid or hydrochloric acid, and the pH may be adjusted with a mixed acid of a strong acid and various weak acids. The solution thus obtained is sufficiently bubbled with an inert gas typified by nitrogen to drive out dissolved oxygen from the system and transferred to an autoclave. The autoclave is not particularly limited as long as it is not corroded by an acidic aqueous solution and can withstand the conditions of the (2-1) hydrothermal synthesis process described later. For example, it may be a SUS316 bottle, a bottle with a fluorine coating applied to the inner wall of a SUS bottle, or a container containing a fluorine resin.
（２）結晶生成工程
工程（２）は、前記原料調合液を加熱して結晶を生成させる工程であり、主に以下の（２−１）水熱合成工程と、（２−２）精製工程に別けられる。
（２−１）水熱合成工程
工程（１）で得られた原料調合液を１１０〜４５０℃に加熱し、１〜１５０時間程度保持すると、水熱合成反応が進行して、Ｍｏ及びＶを含有する結晶性の固体が生成する。目的とする結晶性固体の純度及び収率を高くするという観点から、水熱合成反応の好ましい反応温度は１１０〜２５０℃である。また、加熱時間が短い場合には結晶の生成が見られず、時間が長すぎる場合には不純物の生成が増大する傾向にあるため、好ましい反応時間は１０〜１２０時間である。反応が十分に進行したことは、Ｘ線回折（ＸＲＤ）により確認することができる。オートクレーブの条件を２００℃で４日間にしても、２５０℃で１日間にしても同じ構造を有する結晶性固体が析出する。
(2) Crystal generation step Step (2) is a step of generating crystals by heating the raw material preparation liquid, and mainly includes the following (2-1) hydrothermal synthesis step and (2-2) purification step. Divided into
(2-1) Hydrothermal synthesis step When the raw material preparation solution obtained in step (1) is heated to 110 to 450 ° C and held for about 1 to 150 hours, the hydrothermal synthesis reaction proceeds, and Mo and V are A crystalline solid containing is produced. From the viewpoint of increasing the purity and yield of the target crystalline solid, the preferred reaction temperature of the hydrothermal synthesis reaction is 110 to 250 ° C. In addition, when the heating time is short, no crystal formation is observed, and when the heating time is too long, the generation of impurities tends to increase. Therefore, the preferred reaction time is 10 to 120 hours. It can be confirmed by X-ray diffraction (XRD) that the reaction has sufficiently progressed. Even if the autoclave conditions are 200 ° C. for 4 days or 250 ° C. for 1 day, a crystalline solid having the same structure is precipitated.
（２−２）精製工程
次に、オートクレーブを室温まで冷却した後、結晶性固体をろ別する。このとき、水溶性ジカルボン酸で結晶性固体を精製してもよい。ジカルボン酸としては、シュウ酸、酒石酸等を好適に用いることができる。具体的な手順の一例としては、得られた結晶性固体１ｇに対して１〜１０ｇ程度のシュウ酸を、シュウ酸１ｇにつき２５ｍＬ程度の水で溶解し、その中に結晶性固体を入れて攪拌する。このとき、シュウ酸水溶液は４０〜８０℃程度に加熱してもよい。その後、ろ過を行い、得られた結晶を３０〜２００℃で、常圧若しくは減圧下で乾燥させる。
(2-2) Purification step Next, the autoclave is cooled to room temperature, and then the crystalline solid is filtered off. At this time, the crystalline solid may be purified with a water-soluble dicarboxylic acid. As the dicarboxylic acid, oxalic acid, tartaric acid or the like can be preferably used. As an example of a specific procedure, about 1 to 10 g of oxalic acid is dissolved in about 25 mL of water per 1 g of oxalic acid, and 1 g of the obtained crystalline solid is stirred. To do. At this time, the oxalic acid aqueous solution may be heated to about 40 to 80 ° C. Thereafter, filtration is performed, and the obtained crystals are dried at 30 to 200 ° C. under normal pressure or reduced pressure.
（４）焼成工程
工程（４）は、前記結晶を不活性ガス雰囲気下、２００〜８００℃で焼成する工程である。
結晶性固体を乾燥した後、結晶を後述する（３）接触工程にそのまま供してもよいが、接触工程の前に結晶性固体を焼成する工程を行うことが好ましい。接触工程前に結晶性固体を焼成しておくと、結晶性固体のより高い結晶化が促進される傾向にある。焼成は、回転炉、固定炉等で行うことが可能である。空気雰囲気下でも焼成することは可能であるが、複合金属酸化物を不飽和ニトリルの製造用触媒として使用する等の目的で金属の還元率を調整したい場合は、不活性ガス雰囲気で焼成することが好ましい。焼成温度は、２００℃〜８００℃が好ましい。十分に焼成するためには、数十分〜１日程度焼成するのが好ましく、１時間〜１６時間がより好ましい。
(4) Firing step Step (4) is a step of firing the crystal at 200 to 800 ° C in an inert gas atmosphere.
After the crystalline solid is dried, the crystal may be subjected to the contact step (3) described later as it is, but it is preferable to perform a step of firing the crystalline solid before the contact step. If the crystalline solid is calcined before the contacting step, higher crystallization of the crystalline solid tends to be promoted. Firing can be performed in a rotary furnace, a fixed furnace, or the like. Although it can be fired in an air atmosphere, if you want to adjust the metal reduction rate for the purpose of using a composite metal oxide as a catalyst for the production of unsaturated nitriles, fire it in an inert gas atmosphere. Is preferred. The firing temperature is preferably 200 ° C to 800 ° C. In order to perform sufficient baking, baking is preferably performed for several tens of minutes to about one day, and more preferably for 1 hour to 16 hours.
（３）接触工程
工程（３）は、前記加熱により生成した結晶に、Ｚを含むスラリー及び／又は溶液を接触させる工程である。
工程（３）においては、結晶性固体を粉砕した後、これを、Ｚ源を含むスラリー及び／又は溶液に接触させる。結晶性固体の粉砕には、メノウ鉢、乳鉢等を使用することができる。なお、本明細書中「接触」とは、固体と液体とが接触状態にあること言い、特に、固体の細孔に液体を入り込ませることを意味する。
(3) Contacting step Step (3) is a step of bringing a slurry and / or a solution containing Z into contact with the crystals generated by the heating.
In step (3), after pulverizing the crystalline solid, it is brought into contact with a slurry and / or solution containing a Z source. An agate mortar, a mortar, etc. can be used for grinding | pulverization of crystalline solid. In the present specification, “contact” means that the solid and the liquid are in contact with each other, and particularly means that the liquid enters the pores of the solid.
ＺがＴｅの場合には、Ｚ源の例として、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸等が挙げられ、中でも、溶解性と得られる触媒性能の観点から、テルル酸が好ましい。 When Z is Te, examples of the Z source include tellurium dioxide, tellurium trioxide, telluric acid, telluric acid, and the like. Among these, telluric acid is preferable from the viewpoint of solubility and obtained catalyst performance.
ＺがＳｂの場合には、Ｚ源の例として、酸化アンチモン（ＩＩＩ）、酸化アンチモン（ＩＶ）、酸化アンチモン（Ｖ）、メタアンチモン酸（ＩＩＩ）、アンチモン酸（Ｖ）、アンチモン酸アンモニウム（Ｖ）、塩化アンチモン（ＩＩＩ）、塩化酸化アンチモン（ＩＩＩ）、硝酸酸化アンチモン（ＩＩＩ）、アンチモンのアルコキシド、アンチモンの酒石酸塩等の有機酸塩等が挙げられ、中でも、塩酸水溶液への溶解性の観点から、酸化アンチモン（ＩＩＩ）が好ましい。 When Z is Sb, examples of the Z source include antimony oxide (III), antimony oxide (IV), antimony oxide (V), metaantimonic acid (III), antimonic acid (V), and ammonium antimonate (V ), Antimony chloride (III), antimony chloride (III) chloride, antimony oxide nitrate (III), alkoxide of antimony, organic acid salt such as antimony tartrate, etc., among others, from the viewpoint of solubility in aqueous hydrochloric acid Therefore, antimony (III) oxide is preferable.
ＺがＮｂの場合には、Ｚ源の例として、ニオブ酸、ＮｂＣｌ5、ＮｂＣｌ3、Ｎｂ（ＯＣ2Ｈ5）5等、が挙げられ、中でも、溶解性の観点から、ニオブ酸をジカルボン酸化合物溶液に溶解させて得られるニオブのジカルボン酸化合物の水溶液が好ましい。 When Z is Nb, examples of the Z source include niobic acid, NbCl 5 , NbCl 3 , Nb (OC 2 H 5 ) 5, etc. Among them, niobic acid is dicarboxylic acid from the viewpoint of solubility. An aqueous solution of a niobium dicarboxylic acid compound obtained by dissolving in a compound solution is preferred.
ＺがＷの場合には、Ｚ源の例として、酸化タングステン、酸化タングステン（ＩＩＩ）、酸化タングステン（ＩＶ）、酸化タングステン（ＶＩ）、メタタングステン酸アンモニウム、リンタングステン酸、ケイタングステン酸、リンタングステン酸、ケイタングステン酸のアンモニウム塩、アルカリ金属塩等が挙げられる。これらのうち好ましいのはメタタングステン酸アンモニウムである。 In the case where Z is W, examples of the Z source include tungsten oxide, tungsten oxide (III), tungsten oxide (IV), tungsten oxide (VI), ammonium metatungstate, phosphotungstic acid, silicotungstic acid, phosphotungsten. Examples include acids, ammonium salts of silicotungstic acid, alkali metal salts, and the like. Of these, ammonium metatungstate is preferred.
ＺがＣｅの場合には、Ｚ源の例として、硝酸セリウム六水和物等の硝酸塩、塩化セリウム７水和物、セリウムの硫酸塩、炭酸塩等が挙げられる。 When Z is Ce, examples of the Z source include nitrates such as cerium nitrate hexahydrate, cerium chloride heptahydrate, cerium sulfate, carbonate, and the like.
ＺがＴａの場合には、Ｚ源の例として、タンタル酸、酸化タンタル、タンタルのアルコキシド、ほう化タンタル、五塩化タンタル、五臭化タンタル、五フッ化タンタル等が挙げられる。 When Z is Ta, examples of the Z source include tantalum acid, tantalum oxide, tantalum alkoxide, tantalum boride, tantalum pentachloride, tantalum pentabromide, tantalum pentafluoride, and the like.
ＺがＴｉの場合には、Ｚ源の例として、四塩化チタン、ほう化チタン、フッ化チタン、水酸化チタン、よう化チタン、酸化チタン（ＩＶ）硫酸塩水和物等が挙げられる。 When Z is Ti, examples of the Z source include titanium tetrachloride, titanium boride, titanium fluoride, titanium hydroxide, titanium iodide, titanium oxide (IV) sulfate hydrate and the like.
ＺがＰの場合には、リン酸、リン酸二水素アンモニウム等が挙げられる。 When Z is P, phosphoric acid, ammonium dihydrogen phosphate and the like can be mentioned.
ＺがＢｉの場合には、Ｚ源の例として、硝酸ビスマス、クエン酸ビスマス、酢酸ビスマス、塩化ビスマス、炭酸酸化ビスマス、次炭酸ビスマス、五フッ化ビスマス等が挙げられる。 When Z is Bi, examples of the Z source include bismuth nitrate, bismuth citrate, bismuth acetate, bismuth chloride, bismuth carbonate, bismuth subcarbonate, and bismuth pentafluoride.
Ｚを含むスラリー又は溶液に用いられる溶媒としては、一般的には水でよいが、Ｚ源が水に対して溶解性が乏しい場合には、有機溶媒でも、酸と水の混合物でもよい。酸性水溶液を調製する場合、添加する酸は、硫酸、塩酸、硝酸等の無機酸でも、シュウ酸、リンゴ酸、コハク酸等の有機酸でも構わない。Ｚ源の種類にも依るが、酸性水溶液のｐＨが１．０〜５．０程度になるように酸の添加量を調整することが好ましい。Ｚ源溶液の濃度は５．０〜１．０×１０-4ｍｏｌ／Ｌが好ましい。 The solvent used in the slurry or solution containing Z is generally water, but when the Z source is poorly soluble in water, it may be an organic solvent or a mixture of acid and water. When preparing an acidic aqueous solution, the acid to be added may be an inorganic acid such as sulfuric acid, hydrochloric acid or nitric acid, or an organic acid such as oxalic acid, malic acid or succinic acid. Although depending on the type of Z source, it is preferable to adjust the amount of acid added so that the pH of the acidic aqueous solution is about 1.0 to 5.0. The concentration of the Z source solution is preferably 5.0 to 1.0 × 10 −4 mol / L.
粉砕した結晶性固体をＺ源を含むスラリー及び／又は溶液に接触させる方法の一つである含浸は、固体と液体を接触させることによって実現できるが、均一にしみ込ませる観点で、接触させる液体の体積は固体の０．１〜１０倍が好ましい。より適切な液体量を求めるためには、固体の細孔体積を計算によって求め、液体量を細孔体積の０．５〜２倍に設定するのが好ましい。なお操作性の観点からは、固体を入れた容器に液体を添加するのが好ましいが、液体中に固体を添加しても差し支えない。含浸は両者の接触によって達成できるが、より多くの細孔に十分な量の液体を入り込ませる観点で、結晶性固体とＺを含むスラリー及び／又は溶液の混合物を撹拌した後、数分〜１時間程度静置するのが好ましい。 Impregnation, which is one of the methods for bringing the pulverized crystalline solid into contact with the slurry and / or solution containing the Z source, can be achieved by bringing the solid into contact with the liquid. The volume is preferably 0.1 to 10 times that of the solid. In order to obtain a more appropriate amount of liquid, it is preferable to obtain the solid pore volume by calculation and set the liquid amount to 0.5 to 2 times the pore volume. From the viewpoint of operability, it is preferable to add a liquid to a container containing a solid, but a solid may be added to the liquid. Impregnation can be achieved by contact between the two, and from the viewpoint of allowing a sufficient amount of liquid to enter more pores, after stirring the slurry of the crystalline solid and Z and / or the solution, several minutes to 1 It is preferable to stand for about an hour.
含浸操作後、得られた複合金属酸化物を乾燥することが好ましい。十分に乾燥できる限り、室温で乾燥しても、加温しても差し支えない。また常圧下で乾燥しても、減圧下で乾燥してもよい。さらに、乾燥した後、不活性ガス雰囲気下、２００〜５００℃の範囲で数時間加熱してもよい。 It is preferable to dry the obtained composite metal oxide after the impregnation operation. As long as it can be sufficiently dried, it may be dried at room temperature or heated. Moreover, it may be dried under normal pressure or may be dried under reduced pressure. Furthermore, after drying, you may heat for several hours in the range of 200-500 degreeC by inert gas atmosphere.
得られた複合金属酸化物触媒の同定は粉末Ｘ線回折によって行うことができる。粉末Ｘ線回折測定を行う際には、得られた結晶性固体をそのまま測定しても問題ないが、好ましくはメノウ鉢等を用いて結晶を細かく砕いた後に測定することが好ましい。 The obtained composite metal oxide catalyst can be identified by powder X-ray diffraction. When performing the powder X-ray diffraction measurement, there is no problem even if the obtained crystalline solid is measured as it is, but it is preferable to perform the measurement after finely pulverizing the crystal using an agate bowl or the like.
［３］不飽和ニトリルの製造方法
本実施の形態における複合金属酸化物触媒は、アルカン又はアルケンをアンモ酸化して対応する不飽和ニトリルを製造する反応において活性を示すが、中でも、プロパン又はイソブタンを気相接触アンモ酸化反応させて不飽和ニトリルを製造する際の触媒として特に好ましく利用することができる。
[3] Method for Producing Unsaturated Nitrile The composite metal oxide catalyst in the present embodiment exhibits activity in a reaction in which an alkane or alkene is ammoxidized to produce a corresponding unsaturated nitrile. Among them, propane or isobutane is used. It can be particularly preferably used as a catalyst when an unsaturated nitrile is produced by a gas phase catalytic ammoxidation reaction.
不飽和ニトリルの製造に用いるアルカン又はアルケンとアンモニアの原料は必ずしも高純度の必要はなく、工業グレードのガスを利用することができる。反応系に供給する酸素源としては、空気、酸素を富化した空気又は酸素を用いることができる。さらに、水蒸気、ヘリウム、アルゴン、炭酸ガス、窒素等を供給してもよい。 The raw material of alkane or alkene and ammonia used for the production of the unsaturated nitrile does not necessarily need to have high purity, and an industrial grade gas can be used. As the oxygen source supplied to the reaction system, air, air enriched with oxygen, or oxygen can be used. Further, water vapor, helium, argon, carbon dioxide gas, nitrogen, or the like may be supplied.
気相接触アンモ酸化反応の場合は、反応系に供給されるアンモニアのアルカン又はアルケンに対するモル比は、好ましくは０．１〜２．０、より好ましくは０．２〜１．２である。反応系に供給される分子状酸素は、アルカン又はアルケンに対するモル比として、好ましくは０．２〜１０、より好ましくは０．４〜４である。反応圧力は、絶対圧で好ましくは０．０１〜１Ｍｐａである。反応温度は、好ましくは３００〜５５０℃、より好ましくは３５０〜５００℃である。接触時間は、好ましくは０．５〜８秒以内、より好ましくは０．５〜３秒以内である。反応は、固定床、流動床、移動床等の従来の方式を採用することができる。 In the case of the gas phase catalytic ammoxidation reaction, the molar ratio of ammonia to the alkane or alkene supplied to the reaction system is preferably 0.1 to 2.0, more preferably 0.2 to 1.2. The molecular oxygen supplied to the reaction system is preferably 0.2 to 10 and more preferably 0.4 to 4 as a molar ratio to the alkane or alkene. The reaction pressure is preferably 0.01 to 1 MPa in absolute pressure. The reaction temperature is preferably 300 to 550 ° C, more preferably 350 to 500 ° C. The contact time is preferably within 0.5 to 8 seconds, more preferably within 0.5 to 3 seconds. For the reaction, a conventional system such as a fixed bed, a fluidized bed, or a moving bed can be adopted.
実際の反応試験は、例えば、以下の手順に従って行うことができる。
触媒０．５ｇを内径４ｍｍの固定床型反応管に充填し、反応温度４４０℃、プロパン：アンモニア：酸素：ヘリウム＝１：１．２：２．８：１０．６の原料混合ガスを流量Ｆ＝２０（ｍＬ／ｍｉｎ）で流す。この時の圧力はゲージ圧で０．０５ｋｇ／ｃｍ2である。接触時間は０．５秒であり、反応ガスの分析はガスクロマトグラフィーによって行う。
The actual reaction test can be performed, for example, according to the following procedure.
A fixed bed type reaction tube having an inner diameter of 4 mm is filled with 0.5 g of catalyst, and a raw material mixed gas of propane: ammonia: oxygen: helium = 1: 1.2: 2.8: 10.6 is supplied at a flow rate F. = 20 (mL / min). The pressure at this time is 0.05 kg / cm 2 in terms of gauge pressure. The contact time is 0.5 seconds, and the reaction gas is analyzed by gas chromatography.
次に、実施例及び比較例を挙げて本実施の形態をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
プロパンの転化率、アクリロニトリルの選択率及び収率は、それぞれ次の定義に従う。
プロパン（Ｐｎ）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（ＡＮ）選択率（％）＝（生成したアクリロニトリルのモル数）／（反応したプロパンのモル数）×１００
アクリロニトリル（ＡＮ）収率（％）＝（生成したアクリロニトリルのモル数）／（供給したプロパンのモル数）×１００
Next, although an Example and a comparative example are given and this Embodiment is demonstrated more concretely, unless this summary is exceeded, this invention is not limited to a following example.
Propane conversion, acrylonitrile selectivity and yield are in accordance with the following definitions, respectively.
Propane (Pn) conversion (%) = (moles of reacted propane) / (moles of propane fed) × 100
Acrylonitrile (AN) selectivity (%) = (number of moles of acrylonitrile produced) / (number of moles of reacted propane) × 100
Acrylonitrile (AN) yield (%) = (Mole number of acrylonitrile produced) / (Mole number of supplied propane) × 100
Ｘ線回折の測定装置としてはＲＩＧＡＫＵ ＲＩＮＴ２５００ＶＨＦ／ＰＣを用いて、以下の条件で測定を行った。
Ｘ線源 ：ＣｕＫα１＋ＣｕＫα２
検出器 ：シンチレーションカウンター
管電圧 ：４０ｋＶ
管電流 ：２００ｍＡ
発散スリット ：１°
散乱スリット ：１°
受光スリット ：０．１５ｍｍ
スキャン速度 ：４°／ｍｉｎ
サンプリング幅 ：０．０２°
スキャン方法 ：２θ／θ法
As an X-ray diffraction measurement apparatus, RIGAK RINT2500VHF / PC was used, and measurement was performed under the following conditions.
X-ray source: CuKα1 + CuKα2
Detector: Scintillation counter tube voltage: 40 kV
Tube current: 200 mA
Divergent slit: 1 °
Scattering slit: 1 °
Light receiving slit: 0.15 mm
Scanning speed: 4 ° / min
Sampling width: 0.02 °
Scanning method: 2θ / θ method
［実施例１］
ヘプタモリブデン酸アンモニウム・６水和物１０．６ｇを蒸留水１００ｍＬに溶解させた（溶液（ア））。また、別にオキシ硫酸バナジウム・ｎ水和物３．７７ｇを蒸留水１００ｍＬに溶解させた（溶液（イ））。次に、溶液（イ）を溶液（ア）に加え、３０分程度攪拌した。得られた原料調合液に２ｍｏｌ／Ｌの硫酸水溶液を加え、ｐＨを２．１に調整した。得られた調合液を、１０００ｃｃ／ｍｉｎで窒素を１０分間バブリングし、調合液中の溶存酸素を系内から追い出した後、テフロン（登録商標）ボトルが内包されたオートクレーブに移した。オートクレーブに入れた調合液を１７５℃で一日間放置した後、室温まで冷却したところ、結晶性固体が析出した。この結晶性固体をろ別した後、減圧下で８０℃に加熱しながら１２時間程度乾燥させた。この結晶性固体を６０℃に加熱した１０質量％のシュウ酸水溶液１００ｍＬ中に入れ、６０℃で３０分攪拌した。次いで、残存した固体を窒素下、４００℃で２時間焼成した。このときの結晶性固体を（Ａ）とする。本操作を繰り返すことにより、合計で５０ｇの結晶性固体（Ａ）を調製した。
その後、得られた結晶性固体（Ａ）のうち０．７ｇに、０．７５ｍＬの水にテルル酸０．１ｇを溶解させたものを含浸させた。そのまま一日間５０℃で保持し、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 1]
10.6 g of ammonium heptamolybdate hexahydrate was dissolved in 100 mL of distilled water (solution (A)). Separately, 3.77 g of vanadium oxysulfate.n hydrate was dissolved in 100 mL of distilled water (solution (I)). Next, the solution (I) was added to the solution (A) and stirred for about 30 minutes. A 2 mol / L aqueous sulfuric acid solution was added to the obtained raw material preparation solution to adjust the pH to 2.1. The obtained preparation liquid was bubbled with nitrogen at 1000 cc / min for 10 minutes to expel dissolved oxygen in the preparation liquid from the system, and then transferred to an autoclave containing a Teflon (registered trademark) bottle. After the preparation liquid put in the autoclave was left at 175 ° C. for one day and then cooled to room temperature, a crystalline solid was precipitated. After filtering this crystalline solid, it was dried for about 12 hours while heating at 80 ° C. under reduced pressure. This crystalline solid was put into 100 mL of a 10% by mass oxalic acid aqueous solution heated to 60 ° C., and stirred at 60 ° C. for 30 minutes. The remaining solid was then calcined at 400 ° C. for 2 hours under nitrogen. Let the crystalline solid at this time be (A). By repeating this operation, a total of 50 g of crystalline solid (A) was prepared.
Thereafter, 0.7 g of the obtained crystalline solid (A) was impregnated with 0.1 g of telluric acid dissolved in 0.75 mL of water. It was kept at 50 ° C. for one day as it was, dried at normal pressure, and further calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折により構造を解析したところ、得られた結晶は、２θ＝８．２°、９．６°、１２．６°、２２．２°、２６．８°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
When the structure was analyzed by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.6 °, 12.6 °, 22.2 °, 26.8 °, 30.1 °, 45. It has a peak at 3 ° and the crystal system is found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパン転化率は５２．２％で、アクリロニトリル選択率は４０．９％、アクリロニトリル収率は２１．３％であった。
<Ammoxidation reaction>
When an ammoxidation reaction of propane was performed using this crystalline composite metal oxide, the propane conversion was 52.2%, the acrylonitrile selectivity was 40.9%, and the acrylonitrile yield was 21.3%. It was.
［比較例１］
ヘプタモリブデン酸アンモニウム・６水和物１０．６ｇを蒸留水１００ｍＬに溶解させた（溶液（ア））。また、溶液（ア）とは別にオキシ硫酸バナジウム・ｎ水和物３．７７ｇを蒸留水１００ｍＬに溶解させた（溶液（イ））。次に、溶液（イ）を溶液（ア）に加え、３０分程度攪拌した。得られた原料調合液に２ｍｏｌ／Ｌの硫酸水溶液を加え、ｐＨを２．１に調整した。得られた調合液を、１０００ｃｃ／ｍｉｎの窒素で１０分間バブリングし、調合液中の溶存酸素を系内から追い出した後、テフロン（登録商標）ボトルが内包されたオートクレーブに移した。次に、１７５℃で一日放置した後、室温まで冷却して結晶性固体を得た。この結晶性固体を６０℃に加熱した１０質量％のシュウ酸水溶液１００ｍＬ中で、３０分攪拌した。残存した固体を窒素下、４５０℃で２時間焼成を行った。
[Comparative Example 1]
10.6 g of ammonium heptamolybdate hexahydrate was dissolved in 100 mL of distilled water (solution (A)). Separately from the solution (A), 3.77 g of vanadium oxysulfate.n hydrate was dissolved in 100 mL of distilled water (solution (A)). Next, the solution (I) was added to the solution (A) and stirred for about 30 minutes. A 2 mol / L aqueous sulfuric acid solution was added to the obtained raw material preparation solution to adjust the pH to 2.1. The obtained preparation liquid was bubbled with nitrogen of 1000 cc / min for 10 minutes to expel dissolved oxygen in the preparation liquid from the system, and then transferred to an autoclave containing a Teflon (registered trademark) bottle. Next, after standing at 175 ° C. for one day, the mixture was cooled to room temperature to obtain a crystalline solid. This crystalline solid was stirred for 30 minutes in 100 mL of a 10% by mass oxalic acid aqueous solution heated to 60 ° C. The remaining solid was calcined at 450 ° C. for 2 hours under nitrogen.
＜物質の同定＞
Ｘ線回折により構造を解析したところ、得られた結晶は、２θ＝８．１°、９．６°、１２．５°、２２．２°、２６．７°、３０．１°、４５．１°にピークを有し、その結晶は三方晶であることがわかった。
<Identification of substance>
When the structure was analyzed by X-ray diffraction, the obtained crystals were 2θ = 8.1 °, 9.6 °, 12.5 °, 22.2 °, 26.7 °, 30.1 °, 45. It has a peak at 1 ° and the crystal is found to be trigonal.
＜アンモ酸化反応＞
得られた結晶性の複合金属酸化物固体を用いてプロパンのアンモ酸化反応を行ったところ、プロパン転化率は５７．１％で、アクリロニトリル選択率は１２．４％、アクリロニトリル収率は７．１％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was performed using the obtained crystalline composite metal oxide solid, the propane conversion was 57.1%, the acrylonitrile selectivity was 12.4%, and the acrylonitrile yield was 7.1. %Met.
［比較例２］
ヘプタモリブデン酸アンモニウム・６水和物１０．６ｇを蒸留水１００ｍＬに溶解させた（溶液（ア））。また、溶液（ア）とは別にオキシ硫酸バナジウム・ｎ水和物３．７７ｇを蒸留水１００ｍＬに溶解させた（溶液（イ））。次に、溶液（イ）を溶液（ア）に加え、３０分程度攪拌した。得られた原料調合液に２ｍｏｌ／Ｌの硫酸水溶液を加え、ｐＨを３．３に調整した。得られた調合液を、１０００ｃｃ／ｍｉｎの窒素で１０分間バブリングし、調合液中の溶存酸素を系内から追い出した後、テフロン（登録商標）ボトルが内包されたオートクレーブに移した。次に、１７５℃で一日放置した後、室温まで冷却して結晶性固体を得た。この結晶性固体を６０℃に加熱した１０質量％のシュウ酸水溶液１００ｍＬ中で、３０分攪拌した。残存した固体を窒素下、４５０℃で２時間焼成を行った。
[Comparative Example 2]
10.6 g of ammonium heptamolybdate hexahydrate was dissolved in 100 mL of distilled water (solution (A)). Separately from the solution (A), 3.77 g of vanadium oxysulfate.n hydrate was dissolved in 100 mL of distilled water (solution (A)). Next, the solution (I) was added to the solution (A) and stirred for about 30 minutes. A 2 mol / L aqueous sulfuric acid solution was added to the obtained raw material preparation solution to adjust the pH to 3.3. The obtained preparation liquid was bubbled with nitrogen of 1000 cc / min for 10 minutes to expel dissolved oxygen in the preparation liquid from the system, and then transferred to an autoclave containing a Teflon (registered trademark) bottle. Next, after standing at 175 ° C. for one day, the mixture was cooled to room temperature to obtain a crystalline solid. This crystalline solid was stirred for 30 minutes in 100 mL of a 10% by mass oxalic acid aqueous solution heated to 60 ° C. The remaining solid was calcined at 450 ° C. for 2 hours under nitrogen.
＜物質の同定＞
Ｘ線回折により構造を解析したところ、得られた結晶は、２θ＝６．５°、７．９°、９．０°、１２．７°、２２．２°、２７．３°、２８．３°にピークを有し、その結晶は斜方晶であることがわかった。
<Identification of substance>
When the structure was analyzed by X-ray diffraction, the obtained crystals were 2θ = 6.5 °, 7.9 °, 9.0 °, 12.7 °, 22.2 °, 27.3 °, 28. It has a peak at 3 ° and the crystal is found to be orthorhombic.
＜アンモ酸化反応＞
得られた結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５５．２％で、アクリロニトリル選択率は１７．０％、アクリロニトリル収率は９．４％であった。
<Ammoxidation reaction>
When the propane ammoxidation reaction was carried out using the obtained crystalline composite metal oxide, the propane conversion was 55.2%, the acrylonitrile selectivity was 17.0%, and the acrylonitrile yield was 9.4%. Met.
［比較例３］
ヘプタモリブデン酸アンモニウム・６水和物１０．６ｇを蒸留水１００ｍＬに溶解させた（溶液（ア））。また、溶液（ア）とは別にオキシ硫酸バナジウム・ｎ水和物３．７７ｇを蒸留水１００ｍＬに溶解させた（溶液（イ））。次に、溶液（イ）を溶液（ア）に加え、３０分程度攪拌した。得られた原料調合液に２ｍｏｌ／Ｌの硫酸水溶液を加え、ｐＨを２．１に調整した。得られた調合液を、１０００ｃｃ／ｍｉｎの窒素で１０分間バブリングし、調合液中の溶存酸素を系内から追い出した後、テフロン（登録商標）ボトルが内包されたオートクレーブに移した。次に、１７５℃で一日放置した後、室温まで冷却して結晶性固体を得た。この結晶性固体を６０℃に加熱した１０質量％のシュウ酸水溶液１００ｍＬ中で、３０分攪拌した。残存した固体を窒素下、４５０℃で２時間焼成を行った。その後、得られた結晶性固体０．７ｇに対して、０．７５ｍＬの水にテルル酸０．１ｇを溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させて複合金属酸化物の結晶を得た。
[Comparative Example 3]
10.6 g of ammonium heptamolybdate hexahydrate was dissolved in 100 mL of distilled water (solution (A)). Separately from the solution (A), 3.77 g of vanadium oxysulfate.n hydrate was dissolved in 100 mL of distilled water (solution (A)). Next, the solution (I) was added to the solution (A) and stirred for about 30 minutes. A 2 mol / L aqueous sulfuric acid solution was added to the obtained raw material preparation solution to adjust the pH to 2.1. The obtained preparation liquid was bubbled with nitrogen of 1000 cc / min for 10 minutes to expel dissolved oxygen in the preparation liquid from the system, and then transferred to an autoclave containing a Teflon (registered trademark) bottle. Next, after standing at 175 ° C. for one day, the mixture was cooled to room temperature to obtain a crystalline solid. This crystalline solid was stirred for 30 minutes in 100 mL of a 10% by mass oxalic acid aqueous solution heated to 60 ° C. The remaining solid was calcined at 450 ° C. for 2 hours under nitrogen. Thereafter, 0.7 g of the obtained crystalline solid was impregnated with 0.1 g of telluric acid dissolved in 0.75 mL of water. The crystals were dried as they were at 50 ° C. and normal pressure for one day to obtain composite metal oxide crystals.
＜物質の同定＞
Ｘ線回折により構造を解析したところ、得られた結晶は、２θ＝６．６°、７．８°、９．１°、１２．７°、２２．２°、２７．４°、２８．３°にピークを有し、その結晶は斜方晶であることがわかった。
<Identification of substance>
When the structure was analyzed by X-ray diffraction, the obtained crystals were 2θ = 6.6 °, 7.8 °, 9.1 °, 12.7 °, 22.2 °, 27.4 °, 28. It has a peak at 3 ° and the crystal is found to be orthorhombic.
＜アンモ酸化反応＞
得られた触媒を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５３．４％で、アクリロニトリル選択率は３３．３％、アクリロニトリル収率は１７．８％であった。
実施例１及び比較例１〜３の結果を表１に示す。
<Ammoxidation reaction>
When an ammoxidation reaction of propane was carried out using the obtained catalyst, the propane conversion was 53.4%, the acrylonitrile selectivity was 33.3%, and the acrylonitrile yield was 17.8%.
The results of Example 1 and Comparative Examples 1 to 3 are shown in Table 1.
表１に示したように、結晶系が三方晶であり、且つ、モリブデン、バナジウムからなる複合金属酸化物に第三の金属成分であるＴｅさらに含む触媒（実施例１）は、目的生成物であるアクリロニトリルの選択率及び収率が高く、触媒性能に優れたものであった。 As shown in Table 1, the catalyst (Example 1) in which the crystal system is trigonal and the composite metal oxide composed of molybdenum and vanadium further includes Te as the third metal component is the target product. The selectivity and yield of a certain acrylonitrile was high, and the catalyst performance was excellent.
［実施例２］
１ｍｏｌ／Ｌの塩酸水溶液０．７ｍＬに三酸化アンチモン０．０２９ｇ（純度９９．５％）を溶解させ、これを実施例１で得られた結晶性固体（Ａ）０．７ｇに含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 2]
0.029 g of antimony trioxide (purity 99.5%) was dissolved in 0.7 mL of 1 mol / L hydrochloric acid aqueous solution, and this was impregnated with 0.7 g of the crystalline solid (A) obtained in Example 1. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．２°、９．６°、１２．６°、２２．２°、２６．８°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.6 °, 12.6 °, 22.2 °, 26.8 °, 30.1 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率４５．２％で、アクリロニトリル選択率は３５．０％、アクリロニトリル収率は１５．８％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 45.2%, the acrylonitrile selectivity was 35.0%, and the acrylonitrile yield was 15.8%. It was.
［実施例３］
実施例１で得られた結晶性固体（Ａ）０．７ｇに、蒸留水０．７ｍＬにシュウ酸Ｎｂ水溶液３．１９２ｇ（純度０．６％：シュウ酸／Ｎｂ＝２．５）を溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 3]
To 0.7 g of the crystalline solid (A) obtained in Example 1, 3.192 g of oxalic acid Nb aqueous solution (purity 0.6%: oxalic acid / Nb = 2.5) was dissolved in 0.7 mL of distilled water. Was impregnated. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．２°、９．７°、１２．６°、２２．２°、２６．９°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.7 °, 12.6 °, 22.2 °, 26.9 °, 30.1 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率４０．３％で、アクリロニトリル選択率は３５．２％、アクリロニトリル収率は１４．２％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 40.3%, the acrylonitrile selectivity was 35.2%, and the acrylonitrile yield was 14.2%. It was.
［実施例４］
実施例１で得られた結晶性固体（Ａ）０．７ｇに、蒸留水０．７ｍＬにメタタングステン酸水溶液０．００１ｇ（純度：５０％）を溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 4]
0.7 g of the crystalline solid (A) obtained in Example 1 was impregnated with 0.001 g (purity: 50%) of an aqueous metatungstic acid solution dissolved in 0.7 mL of distilled water. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．２°、９．６°、１２．７°、２２．３°、２６．８°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.6 °, 12.7 °, 22.3 °, 26.8 °, 30.1 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５５．３％で、アクリロニトリル選択率は１２．８％、アクリロニトリル収率は７．１％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 55.3%, the acrylonitrile selectivity was 12.8%, and the acrylonitrile yield was 7.1%. It was.
［実施例５］
実施例１で得られた結晶性固体（Ａ）０．７ｇに、蒸留水０．７ｍＬに硝酸セリウム六水和物０．００１ｇを溶解させたものを含浸させた（純度９８．０％）。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で二時間焼成することにより複合金属酸化物の結晶を得た。
[Example 5]
0.7 g of the crystalline solid (A) obtained in Example 1 was impregnated with 0.001 g of cerium nitrate hexahydrate dissolved in 0.7 mL of distilled water (purity 98.0%). The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain composite metal oxide crystals.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．１°、９．６°、１２．６°、２２．２°、２６．８°、３０．２°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.1 °, 9.6 °, 12.6 °, 22.2 °, 26.8 °, 30.2 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５３．８％で、アクリロニトリル選択率は１１．２％、アクリロニトリル収率は６．１％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 53.8%, the acrylonitrile selectivity was 11.2%, and the acrylonitrile yield was 6.1%. It was.
［実施例６］
実施例１で得られた結晶性固体（Ａ）０．７ｇに、蒸留水０．７ｍＬにタンタル酸０．００１ｇを添加して９０℃まで加熱したものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 6]
The crystalline solid (A) obtained in Example 1 was impregnated with 0.7 g of distilled water added to 0.001 g of distilled water and heated to 90 ° C. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．２°、９．６°、１２．６°、２２．２°、２６．８°、３０．１°、４５．２°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.6 °, 12.6 °, 22.2 °, 26.8 °, 30.1 °, 45 It had a peak at .2 ° and the crystal system was found to be trigonal.
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率３９．８％で、アクリロニトリル選択率は１０．２％、アクリロニトリル収率は４．１％であった。 When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 39.8%, the acrylonitrile selectivity was 10.2%, and the acrylonitrile yield was 4.1%. It was.
［実施例７］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、蒸留水７０ｍＬに二酸化チタン０．２ｍｇ（純度１００％）を分散させた後、そこから０．７ｍＬ分取したものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 7]
To 0.7 g of the crystalline solid (A) obtained in Example 1, 0.2 mg of titanium dioxide (purity 100%) was dispersed in 70 mL of distilled water, and then 0.7 mL was collected therefrom. Impregnated. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．４°、９．６°、１２．６°、２２．３°、２６．８°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.4 °, 9.6 °, 12.6 °, 22.3 °, 26.8 °, 30.1 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５４．６％で、アクリロニトリル選択率は１３．０％、アクリロニトリル収率は７．１％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 54.6%, the acrylonitrile selectivity was 13.0%, and the acrylonitrile yield was 7.1%. It was.
［実施例８］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、蒸留水７０ｍＬにリン酸０．２ｍｇを溶解させた水溶液から、０．７ｍＬを分取したものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 8]
0.7 g of an aqueous solution obtained by dissolving 0.2 mg of phosphoric acid in 70 mL of distilled water was impregnated with 0.7 g of the crystalline solid (A) obtained in Example 1. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．２°、９．６°、１２．７°、２２．２°、２６．９°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.6 °, 12.7 °, 22.2 °, 26.9 °, 30.1 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５０．０％で、アクリロニトリル選択率は１７．４％で、アクリロニトリル収率は８．７％あった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 50.0%, the acrylonitrile selectivity was 17.4%, and the acrylonitrile yield was 8.7%. It was.
［実施例９］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、蒸留水７０ｍＬにクエン酸ビスマス１ｍｇを溶解させた水溶液から、０．７ｍＬを分取したものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 9]
0.7 g of an aqueous solution prepared by dissolving 1 mg of bismuth citrate in 70 mL of distilled water was impregnated with 0.7 g of the crystalline solid (A) obtained in Example 1. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．３°、９．６°、１２．６°、２２．２°、２６．９°、３０．１°、４５．２°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.3 °, 9.6 °, 12.6 °, 22.2 °, 26.9 °, 30.1 °, 45 It had a peak at .2 ° and the crystal system was found to be trigonal.
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５２．８％で、アクリロニトリル選択率は２０．６％、アクリロニトリル収率は１０．９％であった。 When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 52.8%, the acrylonitrile selectivity was 20.6%, and the acrylonitrile yield was 10.9%. It was.
［実施例１０］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、１ｍｏｌ／Ｌの塩酸水溶液０．７ｍＬにシュウ酸Ｎｂ水溶液３．１９２ｇ（純度０．６％：シュウ酸／Ｎｂ＝２．５）と、三酸化アンチモン０．０２９ｇ（純度９９．５％）を溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 10]
0.7 g of 1 mol / L hydrochloric acid aqueous solution and 3.192 g of oxalic acid Nb aqueous solution (purity 0.6%: oxalic acid / Nb = 2) with respect to 0.7 g of the crystalline solid (A) obtained in Example 1 5) and 0.029 g of antimony trioxide (purity 99.5%) dissolved therein were impregnated. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．２°、９．７°、１２．６°、２２．２°、２６．９°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.7 °, 12.6 °, 22.2 °, 26.9 °, 30.1 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパン転化率４９．８％で、アクリロニトリル選択率は２８．５％、アクリロニトリル収率は１４．２％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was performed using this crystalline composite metal oxide, the propane conversion was 49.8%, the acrylonitrile selectivity was 28.5%, and the acrylonitrile yield was 14.2%. .
［実施例１１］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、蒸留水０．７ｍＬにシュウ酸Ｎｂ水溶液３．１９２ｇ（純度０．６％：シュウ酸／Ｎｂ＝２．５）と、テルル酸０．１ｇ（純度１００％）を溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 11]
To 0.7 g of the crystalline solid (A) obtained in Example 1, 0.792 of distilled water and 3.192 g of oxalic acid Nb aqueous solution (purity 0.6%: oxalic acid / Nb = 2.5) A solution in which 0.1 g (100% purity) of telluric acid was dissolved was impregnated. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．１°、９．６°、１２．６°、２２．２°、２６．８°、３０．２°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.1 °, 9.6 °, 12.6 °, 22.2 °, 26.8 °, 30.2 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率５１．０％で、アクリロニトリル選択率は３４．８％、アクリロニトリル収率は１７．７％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 51.0%, the acrylonitrile selectivity was 34.8%, and the acrylonitrile yield was 17.7%. It was.
［実施例１２］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、１ｍｏｌ／Ｌの塩酸水溶液０．７ｍＬにシュウ酸Ｎｂ水溶液３．１９２ｇ（純度０．６％：シュウ酸／Ｎｂ＝２．５）と、三酸化アンチモン０．０２９ｇ（純度９９．５％）、さらにメタタングステン酸水溶液０．００１ｇ（純度：５０％）を溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 12]
0.7 g of 1 mol / L hydrochloric acid aqueous solution and 3.192 g of oxalic acid Nb aqueous solution (purity 0.6%: oxalic acid / Nb = 2) with respect to 0.7 g of the crystalline solid (A) obtained in Example 1 0.5) and 0.029 g of antimony trioxide (purity: 99.5%) and 0.001 g (purity: 50%) of an aqueous metatungstic acid solution were impregnated. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．２°、９．７°、１２．５°、２２．３°、２６．８°、３０．１°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.2 °, 9.7 °, 12.5 °, 22.3 °, 26.8 °, 30.1 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率４８．０％で、アクリロニトリル選択率は３１．５％、アクリロニトリル収率は１５．１％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was performed using this crystalline composite metal oxide, the propane conversion was 48.0%, the acrylonitrile selectivity was 31.5%, and the acrylonitrile yield was 15.1%. It was.
［実施例１３］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、蒸留水０．７ｍＬにシュウ酸Ｎｂ水溶液３．１９２ｇ（純度０．６％：シュウ酸／Ｎｂ＝２．５）と、テルル酸０．１ｇ（純度１００％）、さらにメタタングステン酸水溶液０．００１ｇ（純度：５０％）を溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 13]
To 0.7 g of the crystalline solid (A) obtained in Example 1, 0.792 of distilled water and 3.192 g of oxalic acid Nb aqueous solution (purity 0.6%: oxalic acid / Nb = 2.5) Then, 0.1 g (purity: 100%) of telluric acid and 0.001 g (purity: 50%) of an aqueous metatungstic acid solution were impregnated. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．１°、９．７°、１２．６°、２２．２°、２６．８°、３０．０°、４５．３°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.1 °, 9.7 °, 12.6 °, 22.2 °, 26.8 °, 30.0 °, 45 It has a peak at .3 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物について、プロパンのアンモ酸化反応を行ったところ、プロパンの転化率５２．０％で、アクリロニトリル選択率は３５．７％、アクリロニトリル収率は１８．５％であった。
<Ammoxidation reaction>
This crystalline composite metal oxide was subjected to propane ammoxidation reaction. As a result, the propane conversion was 52.0%, the acrylonitrile selectivity was 35.7%, and the acrylonitrile yield was 18.5%. .
［実施例１４］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、１ｍｏｌ／Ｌの塩酸水溶液０．７ｍＬにシュウ酸Ｎｂ水溶液３．１９２ｇ（純度０．６％：シュウ酸／Ｎｂ＝２．５）と、三酸化アンチモン０．０２９ｇ（純度９９．５％）、さらにメタタングステン酸水溶液０．００１ｇ（純度：５０％）、硝酸セリウム六水和物０．００１ｇを溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 14]
0.7 g of 1 mol / L hydrochloric acid aqueous solution and 3.192 g of oxalic acid Nb aqueous solution (purity 0.6%: oxalic acid / Nb = 2) with respect to 0.7 g of the crystalline solid (A) obtained in Example 1 .5), 0.029 g of antimony trioxide (purity 99.5%), 0.001 g of metatungstic acid aqueous solution (purity: 50%) and 0.001 g of cerium nitrate hexahydrate were impregnated. I let you. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．１°、９．７°、１２．６°、２２．３°、２６．８°、３０．１°、４５．２°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.1 °, 9.7 °, 12.6 °, 22.3 °, 26.8 °, 30.1 °, 45 It had a peak at .2 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパンの転化率４９．８％で、アクリロニトリル選択率は３７．３％、アクリロニトリル収率は１８．６％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was carried out using this crystalline composite metal oxide, the propane conversion was 49.8%, the acrylonitrile selectivity was 37.3%, and the acrylonitrile yield was 18.6%. It was.
［実施例１５］
実施例１で得られた結晶性固体（Ａ）０．７ｇに対して、蒸留水０．７ｍＬにシュウ酸Ｎｂ水溶液３．１９２ｇ（純度０．６％：シュウ酸／Ｎｂ＝２．５）と、テルル酸０．１ｇ（純度１００％）、さらにメタタングステン酸水溶液０．００１ｇ（純度：５０％）、硝酸セリウム六水和物０．００１ｇを溶解させたものを含浸させた。そのまま一日、５０℃、常圧で乾燥させた後、さらに窒素下、４００℃で２時間焼成することにより複合金属酸化物の結晶を得た。
[Example 15]
To 0.7 g of the crystalline solid (A) obtained in Example 1, 0.792 of distilled water and 3.192 g of oxalic acid Nb aqueous solution (purity 0.6%: oxalic acid / Nb = 2.5) Then, 0.1 g (purity: 100%) of telluric acid, 0.001 g (purity: 50%) of an aqueous metatungstic acid solution, and 0.001 g of cerium nitrate hexahydrate were impregnated. The solid metal oxide was dried as it was at 50 ° C. and normal pressure for one day, and then calcined at 400 ° C. for 2 hours under nitrogen to obtain a composite metal oxide crystal.
＜物質の同定＞
Ｘ線回折による構造を明らかにしたところ、得られた結晶は、２θ＝８．１°、９．６°、１２．５°、２２．３°、２６．８°、３０．１°、４５．２°にピークを有し、結晶系は三方晶であることがわかった。
<Identification of substance>
As a result of clarifying the structure by X-ray diffraction, the obtained crystals were 2θ = 8.1 °, 9.6 °, 12.5 °, 22.3 °, 26.8 °, 30.1 °, 45 It had a peak at .2 ° and the crystal system was found to be trigonal.
＜アンモ酸化反応＞
この結晶性の複合金属酸化物を用いてプロパンのアンモ酸化反応を行ったところ、プロパン転化率５１．２％で、アクリロニトリル選択率は４１．６％、アクリロニトリル収率は２１．３％であった。
<Ammoxidation reaction>
When the ammoxidation reaction of propane was performed using this crystalline composite metal oxide, the propane conversion was 51.2%, the acrylonitrile selectivity was 41.6%, and the acrylonitrile yield was 21.3%. .
本発明は、アルカン又はアルケンをアンモ酸化し、対応する不飽和ニトリルを製造する際の複合金属酸化物触媒としての産業上利用可能性を有する。 The present invention has industrial applicability as a composite metal oxide catalyst in the ammoxidation of alkanes or alkenes to produce the corresponding unsaturated nitriles.
Claims (4)
Ｍｏ1ＶaＺbＯn （Ｉ）
（式中、Ｚは、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｔａ、Ｔｉ、Ｐ、Ｂｉからなる群から選択される少なくとも１種類以上の金属元素を示し、ａ、ｂは、それぞれＭｏ１原子あたりのＶ、Ｚの原子比を示し、０＜ａ≦１、０＜ｂ≦１であり、ｎは構成金属の酸化状態によって決まる酸素の原子比を示す。）
で表される組成を有し、結晶系が三方晶である複合金属酸化物触媒。 A catalyst used for an ammoxidation reaction of an alkane or alkene, which has the following formula (I)
Mo 1 V a Z b O n (I)
(In the formula, Z represents at least one metal element selected from the group consisting of Te, Sb, Nb, W, Ce, Ta, Ti, P, Bi, and a and b are each per Mo atom. (The atomic ratio of V and Z in the formula is 0 <a ≦ 1, 0 <b ≦ 1, and n represents the atomic ratio of oxygen determined by the oxidation state of the constituent metals.)
A composite metal oxide catalyst having a composition represented by:
Ｍｏ1ＶaＺbＯn （Ｉ）
（式中、Ｚは、Ｔｅ、Ｓｂ、Ｎｂ、Ｗ、Ｃｅ、Ｔａ、Ｔｉ、Ｐ、Ｂｉからなる群から選択される少なくとも１種類以上の金属元素を示し、ａ、ｂは、それぞれＭｏ１原子あたりのＶ、Ｚの原子比を示し、０＜ａ≦１、０＜ｂ≦１であり、ｎは構成金属の酸化状態によって決まる酸素の原子比を示す。）
で表される組成を有し、結晶系が三方晶である複合金属酸化物触媒を製造する方法であって、
（１）Ｍｏ、Ｖを含む原料調合液を調製する工程と、
（２）前記原料調合液を加熱して結晶を生成させる工程と、
（３）前記加熱により生成した結晶に、Ｚを含むスラリー及び／又は溶液を接触させる工程と、
を有し、
前記工程（１）において調製した原料調合液のｐＨを酸性に保つことを含む、複合金属酸化物触媒の製造方法。 Formula (I)
Mo 1 V a Z b O n (I)
(In the formula, Z represents at least one metal element selected from the group consisting of Te, Sb, Nb, W, Ce, Ta, Ti, P, Bi, and a and b are each per Mo atom. (The atomic ratio of V and Z in the formula is 0 <a ≦ 1, 0 <b ≦ 1, and n represents the atomic ratio of oxygen determined by the oxidation state of the constituent metals.)
A method for producing a composite metal oxide catalyst having a composition represented by:
(1) a step of preparing a raw material preparation liquid containing Mo and V;
(2) heating the raw material preparation liquid to generate crystals;
(3) a step of bringing a slurry and / or a solution containing Z into contact with the crystals generated by the heating;
Have
The manufacturing method of a composite metal oxide catalyst including keeping pH of the raw material preparation liquid prepared in the said process (1) acidic.
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| WO2014024782A2 (en) * | 2012-08-10 | 2014-02-13 | 日本化薬株式会社 | Catalyst for production of acrylic acid from glycerin, and method for producing same |
| KR20180027790A (en) * | 2016-09-07 | 2018-03-15 | 에쓰대시오일 주식회사 | Catalysts for propane ammoxidation, preparation method thereof and method for producing acrylonitrile using the same |
| US11335958B2 (en) | 2017-08-21 | 2022-05-17 | Murata Manufacturing Co., Ltd. | Battery, battery pack, electronic apparatus, electric vehicle, power storage device and power system |
| CN114950404A (en) * | 2022-05-19 | 2022-08-30 | 中国科学院兰州化学物理研究所 | Wear-resistant ammonia oxidation catalyst and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014024782A2 (en) * | 2012-08-10 | 2014-02-13 | 日本化薬株式会社 | Catalyst for production of acrylic acid from glycerin, and method for producing same |
| JP2014034023A (en) * | 2012-08-10 | 2014-02-24 | Hokkaido Univ | Catalyst for manufacturing acrylic acid from glycerine and manufacturing method of the catalyst |
| WO2014024782A3 (en) * | 2012-08-10 | 2014-11-27 | 日本化薬株式会社 | Catalyst for production of acrylic acid from glycerin, and method for producing same |
| KR20180027790A (en) * | 2016-09-07 | 2018-03-15 | 에쓰대시오일 주식회사 | Catalysts for propane ammoxidation, preparation method thereof and method for producing acrylonitrile using the same |
| KR101937872B1 (en) * | 2016-09-07 | 2019-01-11 | 에쓰대시오일 주식회사 | Catalysts for propane ammoxidation, preparation method thereof and method for producing acrylonitrile using the same |
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| CN114950404A (en) * | 2022-05-19 | 2022-08-30 | 中国科学院兰州化学物理研究所 | Wear-resistant ammonia oxidation catalyst and preparation method and application thereof |
| CN114950404B (en) * | 2022-05-19 | 2023-11-17 | 中国科学院兰州化学物理研究所 | Wear-resistant ammonia oxidation catalyst and preparation method and application thereof |
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