JP2001300311A - Compound metal oxide catalyst and method for catalytic oxidation of hydrocarbon using the same - Google Patents
Compound metal oxide catalyst and method for catalytic oxidation of hydrocarbon using the sameInfo
- Publication number
- JP2001300311A JP2001300311A JP2000125534A JP2000125534A JP2001300311A JP 2001300311 A JP2001300311 A JP 2001300311A JP 2000125534 A JP2000125534 A JP 2000125534A JP 2000125534 A JP2000125534 A JP 2000125534A JP 2001300311 A JP2001300311 A JP 2001300311A
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- oxide catalyst
- niobium
- tellurium
- composite metal
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 5
- 230000003647 oxidation Effects 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 3
- -1 Compound metal oxide Chemical class 0.000 title abstract 3
- 239000010955 niobium Substances 0.000 claims abstract description 33
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 28
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 27
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 26
- 239000011733 molybdenum Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001294 propane Substances 0.000 claims abstract description 6
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 9
- 239000002131 composite material Substances 0.000 claims description 29
- 150000004706 metal oxides Chemical class 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002822 niobium compounds Chemical class 0.000 description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 2
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance 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]
【発明の属する技術分野】本発明はモリブデン、バナジ
ウム、ニオブ及びテルルを含有する改良された複合金属
酸化物触媒に関するものである。本発明に係る複合金属
酸化物触媒は、炭化水素の気相接触酸化反応によるカル
ボン酸やニトリル、特にプロパンの酸化によるアクリル
酸やプロパンのアンモオキシデーションによるアクリロ
ニトリルの製造に優れた触媒能を発揮する。The present invention relates to an improved composite metal oxide catalyst containing molybdenum, vanadium, niobium and tellurium. The composite metal oxide catalyst according to the present invention exhibits excellent catalytic ability in the production of acrylonitrile by ammoxidation of acrylic acid or propane by oxidation of propane, particularly carboxylic acid or nitrile by gas phase catalytic oxidation reaction of hydrocarbon. .
【０００２】[0002]
【従来の技術】モリブデン、バナジウム、ニオブ及びテ
ルルを含有する複合金属酸化物触媒が、炭化水素の気相
接触酸化反応によるカルボン酸やニトリルの製造に優れ
た触媒能を発揮することが知られている。この複合金属
酸化物触媒の最も一般的な製造法は、モリブデン、バナ
ジウム、ニオブ及びテルルの少なくとも１種を含有する
溶液を２種以上混合して、モリブデン、バナジウム、ニ
オブ及びテルルを含有する溶液ないしはスラリーを調製
し、これから溶媒を除去して固形物を取得し、これを熱
分解したのち焼成して複合金属酸化物に転換する方法で
ある。この複合金属酸化物触媒は、その調製法により触
媒能が変化するので、従来から高性能の触媒を目指して
その製法の改良が進められている（特開平５−２０８１
３６、６−２８５３７２、７−１４４１３２、７−２８
９９０７、７−３１５８４２、８−１４１４０１、及び
１１−４７５９８号公報参照）。例えば最終工程である
焼成は、酸素が実質的に存在しない不活性ガス雰囲気中
で３５０〜７００℃、特に６００℃程度で数時間行うの
が好ましいとされている。2. Description of the Related Art It has been known that a composite metal oxide catalyst containing molybdenum, vanadium, niobium and tellurium exhibits excellent catalytic ability in the production of carboxylic acid and nitrile by gas phase catalytic oxidation of hydrocarbons. I have. The most common method for producing this composite metal oxide catalyst is to mix two or more solutions containing at least one of molybdenum, vanadium, niobium and tellurium to form a solution or solution containing molybdenum, vanadium, niobium and tellurium. This is a method in which a slurry is prepared, a solvent is removed therefrom to obtain a solid, which is thermally decomposed, then calcined, and converted to a composite metal oxide. Since the catalytic activity of the composite metal oxide catalyst varies depending on the preparation method, improvement of the production method has been conventionally pursued with the aim of achieving a high-performance catalyst (JP-A-5-2081).
36, 6-285372, 7-144132, 7-28
9907, 7-315842, 8-141401, and 11-47598). For example, it is said that firing in the final step is preferably performed at 350 to 700 ° C., particularly about 600 ° C. for several hours in an inert gas atmosphere substantially free of oxygen.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、同一条
件で焼成を行っても得られる複合金属酸化物触媒の触媒
能は必ずしも同一とはならない。すなわち複合金属酸化
物触媒の触媒能は、焼成より前の段階に相当程度依存し
ている。従って本発明は、焼成に供する前駆体を特定す
ることにより、優れた触媒能を発現する複合金属酸化物
触媒を提供しようとするものである。However, even if the calcination is carried out under the same conditions, the catalytic performance of the composite metal oxide catalyst obtained is not always the same. That is, the catalytic performance of the composite metal oxide catalyst depends to a large extent on the stage before calcination. Accordingly, an object of the present invention is to provide a composite metal oxide catalyst that exhibits excellent catalytic activity by specifying a precursor to be subjected to calcination.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、モリブ
デン、バナジウム、ニオブ及びテルルを含有しており、
かつＣｕ−Ｋα線によるＸ線回析において回析角（２
θ）＝２２．１±０．５°に回析ピークを有する前駆体
を焼成することにより、優れた触媒能を発現するモリブ
デン、バナジウム、ニオブ及びテルルを含有する複合金
属酸化物触媒を調製することができる。そしてこのよう
な前駆体は、最も簡単には、ニオブ化合物を溶解した溶
液と、モリブデン、バナジウム及びテルルの各化合物を
溶解した溶液を、固体が生成しないように速やかに混合
して上記４種の触媒成分を含む溶液とし、この溶液は間
もなく固体が析出してスラリーとなるが、このスラリー
を噴霧乾燥して固形物とし、これを好ましくは４．８℃
／分以上の昇温速度で約３５０℃まで昇温して熱分解す
ることにより調製することができる。According to the present invention, there is provided molybdenum, vanadium, niobium and tellurium,
In addition, in X-ray diffraction by Cu-Kα ray, the diffraction angle (2
θ) = calcining a precursor having a diffraction peak at 22.1 ± 0.5 ° to prepare a composite metal oxide catalyst containing molybdenum, vanadium, niobium, and tellurium that exhibits excellent catalytic activity. be able to. In the simplest case, a solution in which a niobium compound is dissolved and a solution in which molybdenum, vanadium, and tellurium are dissolved are promptly mixed so that a solid is not formed. A solution containing a catalyst component is formed, and this solution will soon precipitate a solid to form a slurry. The slurry is spray-dried to a solid, which is preferably 4.8 ° C.
The temperature can be increased to about 350 ° C. at a rate of temperature increase of not less than / min and thermally decomposed.
【０００５】[0005]
【発明の実施の形態】本発明に係る複合酸化物触媒を調
製するには、先ずその前駆体としてモリブデン、バナジ
ウム、ニオブ及びテルルを含有する固体を調製する。モ
リブデン、バナジウム及びニオブは高沸点なので前駆体
の焼成に際して揮散しないが、テルルは沸点が９９０℃
と低くて揮散し易い。従って前駆体の組成は、目的とす
る複合金属酸化物触媒の組成に、前駆体の焼成に際して
揮散する量のテルルを加えたものとすることが必要であ
る。複合金属酸化物触媒の組成は、通常は原子比でモリ
ブデンを１とするとき、バナジウム、ニオブ及びテルル
はそれぞれ０．０１〜１の範囲であるが、好ましくはバ
ナジウムは０．１〜０．６、ニオブは０．０１〜０．
６、テルルは０．０５〜０．４である。また、前駆体の
焼成に際して揮散するテルル量は、焼成条件により異な
るので、実験により確認する必要がある。BEST MODE FOR CARRYING OUT THE INVENTION To prepare a composite oxide catalyst according to the present invention, first, a solid containing molybdenum, vanadium, niobium and tellurium as its precursor is prepared. Molybdenum, vanadium, and niobium do not volatilize during firing of the precursor because of their high boiling points, but tellurium has a boiling point of 990 ° C.
Low and easy to volatilize. Therefore, it is necessary that the composition of the precursor should be the composition of the target composite metal oxide catalyst plus the amount of tellurium that volatilizes when the precursor is fired. The composition of the composite metal oxide catalyst is generally such that vanadium, niobium and tellurium are each in the range of 0.01 to 1 when molybdenum is 1 in atomic ratio, and preferably vanadium is 0.1 to 0.6. , Niobium is 0.01-0.
6, tellurium is 0.05-0.4. In addition, the amount of tellurium volatilized during the firing of the precursor varies depending on the firing conditions, and thus needs to be confirmed by experiments.
【０００６】前駆体の調製には前述の文献に記載されて
いるような、この複合金属酸化物触媒の調製に常用され
ている原料を用いればよい。例えばモリブデンとしては
パラモリブデン酸アンモニウムが、バナジウムとしては
メタバナジン酸アンモニウムが、ニオブとしてはシュウ
酸ニオブやシュウ酸ニオブアンモニウム、更には酸化ニ
オブゾル等のニオブ化合物をシュウ酸及びアンモニウム
化合物で処理して得たニオブを含む溶液又はスラリー
が、テルルとしてはテルル酸や金属テルルが、それぞれ
好んで用いられる。[0006] For the preparation of the precursor, a raw material commonly used for the preparation of this composite metal oxide catalyst as described in the above-mentioned literature may be used. For example, ammonium paramolybdate as molybdenum, ammonium metavanadate as vanadium, niobium as niobium oxalate or niobium oxalate, and further obtained by treating a niobium compound such as niobium oxide sol with oxalic acid and an ammonium compound. A solution or slurry containing niobium is preferably used as tellurium, and telluric acid and metallic tellurium are each preferably used.
【０００７】前駆体の調製は、モリブデン、バナジウ
ム、ニオブ及びテルルのそれぞれを一旦溶液とする湿式
法で行うのが好ましい。モリブデン、バナジウム、ニオ
ブ及びテルルを粉末状態で混合し、これに溶媒を加えて
も溶液とならずにスラリーとなるので、これらの成分の
少なくとも１種を含有する溶液を先ず調製し、これを所
定の組成となるように混合するのが好ましい。なかでも
モリブデン、バナジウム及びテルルを含む溶液と、ニオ
ブを含む溶液とを調製し、次いでニオブを含む溶液にモ
リブデン等を含む溶液を添加するのが好ましい。モリブ
デン等を含む溶液にニオブを含む溶液を添加するよりも
上記の方法の方が一般により優れた触媒能の複合金属酸
化物触媒が得られる。なお、いずれの場合でも混合はで
きるだけすみやかに行うのが好ましい。両溶液を混合す
ると固体が析出してスラリーとなる。これから溶媒を除
去して所望の組成の固体を取得する。なお、スラリーな
いしはスラリーの調製に用いる溶液中には、所望により
触媒製造に常用されているシリカ、アルミナ、アルミノ
シリケート、チタニア、ジルコニア等の担体やシリカゾ
ル、アルミナゾル等のバインダーなどを添加しておいて
もよい。スラリーからの溶媒の除去は噴霧乾燥によるの
が好ましい。特に最終的に得られる複合金属酸化物触媒
を流動床反応に用いる場合には、球状の触媒を与える噴
霧乾燥によるべきである。噴霧乾燥の条件は、入口ガス
温度が１００〜４００℃、出口ガス温度が８０〜２００
℃程度が好ましい。The preparation of the precursor is preferably carried out by a wet method in which each of molybdenum, vanadium, niobium and tellurium is once dissolved. Even if molybdenum, vanadium, niobium and tellurium are mixed in a powder state, and a solvent is added thereto, a solution is formed instead of a solution, and a slurry containing at least one of these components is first prepared. It is preferable to mix them so as to have the following composition. In particular, it is preferable to prepare a solution containing molybdenum, vanadium, and tellurium and a solution containing niobium, and then add a solution containing molybdenum or the like to the solution containing niobium. The above method generally provides a composite metal oxide catalyst having better catalytic ability than adding a solution containing niobium to a solution containing molybdenum or the like. In any case, the mixing is preferably performed as soon as possible. When both solutions are mixed, a solid precipitates out to form a slurry. From this, the solvent is removed to obtain a solid having a desired composition. Incidentally, the slurry or the solution used for preparing the slurry, silica, alumina, aluminosilicate, titania, a carrier such as zirconia and silica sol, a binder such as alumina sol, etc., which are commonly used in the production of the catalyst, if desired, should be added. Is also good. Removal of the solvent from the slurry is preferably by spray drying. Particularly when the finally obtained composite metal oxide catalyst is used in a fluidized bed reaction, it should be spray-dried to give a spherical catalyst. The spray drying conditions are as follows: the inlet gas temperature is 100 to 400 ° C., and the outlet gas temperature is 80 to 200.
C. is preferred.
【０００８】このようにして得られた固体を熱分解する
と、Ｃｕ−Ｋα線によるＸ線回析において回析角（２
θ）＝２２．１±０．５°にピークを有する前駆体が得
られる。熱分解は実質的に酸素を含まない不活性雰囲気
中で４００℃以下、特に２００〜４００℃に加熱するこ
とにより行うのが好ましい。また、熱分解に際しての昇
温速度は大きい方が好ましく、通常は２．４℃／分以
上、好ましくは４．８℃／分以上で昇温する。特に９℃
／分以上で昇温するのが好ましい。昇温速度は昇温の全
過程で制御するのが好ましいが、少なくとも１００℃以
上の領域では上述の昇温速度で加熱すべきである。３０
０℃以上まで昇温し、かつ少なくとも２００℃以上の領
域を上述の昇温速度で加熱するのが最も好ましい。昇温
速度が遅いと２２．１±０．５°にピークを有する前駆
体が生成しない。When the solid obtained in this manner is thermally decomposed, a diffraction angle (2) is obtained by X-ray diffraction using Cu-Kα ray.
The precursor having a peak at (θ) = 22.1 ± 0.5 ° is obtained. The thermal decomposition is preferably performed by heating to 400 ° C. or lower, particularly 200 to 400 ° C. in an inert atmosphere substantially free of oxygen. Further, it is preferable that the rate of temperature rise during the thermal decomposition is higher, and the temperature is raised usually at 2.4 ° C./min or more, preferably at 4.8 ° C./min or more. Especially 9 ℃
/ Minute or more is preferable. The heating rate is preferably controlled in the entire heating process, but the heating should be performed at the above-mentioned heating rate at least in the region of 100 ° C. or higher. 30
Most preferably, the temperature is raised to 0 ° C. or higher, and at least the region at 200 ° C. or higher is heated at the above-mentioned rate. If the heating rate is low, a precursor having a peak at 22.1 ± 0.5 ° will not be produced.
【０００９】このＣｕ−Ｋα線によるＸ線回析において
回析角（２θ）＝２２．１±０．５°にピークを有する
前駆体を焼成すると、本発明に係る複合金属酸化物触媒
が得られる。焼成は酸素を実質的に含まない不活性雰囲
気中で４５０〜７００℃、特に６００℃程度で行うのが
好ましい。また特開平７−２８９９０７号公報に記載さ
れているように、不活性雰囲気中で焼成したものを冷却
したのち酸素と接触させ、次いで再び不活性雰囲気中で
焼成するのも好ましい。When the precursor having a peak at a diffraction angle (2θ) = 22.1 ± 0.5 ° in the X-ray diffraction by Cu-Kα ray is calcined, the composite metal oxide catalyst according to the present invention is obtained. Can be The calcination is preferably performed at 450 to 700 ° C, particularly about 600 ° C in an inert atmosphere substantially containing no oxygen. Further, as described in JP-A-7-289907, it is also preferable to cool the product fired in an inert atmosphere, contact it with oxygen, and then fire it again in an inert atmosphere.
【００１０】[0010]
【実施例】以下に実施例により本発明を更に具体的に説
明するが、本発明は以下の実施例に限定されるものでは
ない。 実施例１ 温水２９．１Ｌに、パラモリブデン酸アンモニウム・４
水塩７．０９ｋｇ、メタバナジン酸アンモニウム１．４
１ｋｇ、及びテルル酸２．１２ｋｇを溶解し、得られた
溶液にシリカ含有量が２０重量％のシリカゾル５ｋｇを
添加した。EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. Example 1 29.1 L of warm water was added to ammonium paramolybdate / 4
7.09 kg of water salt, ammonium metavanadate 1.4
1 kg and 2.12 kg of telluric acid were dissolved, and 5 kg of a silica sol having a silica content of 20% by weight was added to the obtained solution.
【００１１】温水８．６６Ｌにシュウ酸ニオブアンモニ
ウム２．１６ｋｇを溶解した。シュウ酸ニオブアンモニ
ウムとしては、（ＮＨ4 、Ｈ）3 ＮｂＯ4 (Ｃ2 Ｏ4 )3
と（ＮＨ4 、Ｈ）2 Ｎｂ（ＯＨ）(Ｃ2 Ｏ4 )2 との混合
物で、ニオブ２０．５重量％、シュウ酸根５４．０重量
％、アンモニア５．１重量％を有するものを用いた。上
記で調製したモリブデン等を含む溶液にこのニオブを含
む溶液を１分間で添加した。添加直後の液温は約５０℃
であり、添加から約５分後に析出物が生成してスラリー
となった。このスラリーを２０〜５０℃で１６時間保持
したのち噴霧乾燥した。噴霧乾燥は入口ガス温度２２０
℃、出口ガス温度１６０℃で行った。2.16 kg of ammonium niobium oxalate was dissolved in 8.66 L of warm water. Examples of niobium ammonium oxalate include (NH 4 , H) 3 NbO 4 (C 2 O 4 ) 3
Of (NH 4 , H) 2 Nb (OH) (C 2 O 4 ) 2 having 20.5% by weight of niobium, 54.0% by weight of oxalate, and 5.1% by weight of ammonia Was. The solution containing niobium was added to the solution containing molybdenum and the like prepared above in one minute. Liquid temperature immediately after addition is about 50 ° C
Approximately 5 minutes after the addition, a precipitate formed to form a slurry. This slurry was kept at 20 to 50 ° C. for 16 hours and then spray-dried. Spray drying at inlet gas temperature 220
C. and an outlet gas temperature of 160.degree.
【００１２】噴霧乾燥物を窒素ガス流通下に９．５℃／
分で室温から３５０℃まで昇温し、この温度で１分間保
持したのち冷却した。この前駆体の粉末Ｘ線回析図は図
１の通りであり、回析角（２θ）＝２２．１８°にピー
クを有していた。また組成は原子比でＭｏ：Ｖ：Ｎｂ：
Ｔｅ＝１：０．３：０．１２：０．２３であった。この
前駆体を窒素ガス流通下に６００℃で２時間焼成して複
合金属酸化物触媒を得た。このものの組成は原子比でＭ
ｏ：Ｖ：Ｎｂ：Ｔｅ＝１：０．３：０．１２：０．１５
であった。また平均粒径は約５０μｍであった。[0012] The spray-dried product is heated at 9.5 ° C /
The temperature was raised from room temperature to 350 ° C. in 1 minute, and the temperature was maintained at this temperature for 1 minute, followed by cooling. The powder X-ray diffraction diagram of this precursor was as shown in FIG. 1 and had a peak at a diffraction angle (2θ) = 22.18 °. The composition is Mo: V: Nb:
Te = 1: 0.3: 0.12: 0.23. This precursor was calcined at 600 ° C. for 2 hours under a nitrogen gas flow to obtain a composite metal oxide catalyst. Its composition is M in atomic ratio.
o: V: Nb: Te = 1: 0.3: 0.12: 0.15
Met. The average particle size was about 50 μm.
【００１３】比較例１ 実施例１で得られた噴霧乾燥物を、窒素ガス流通下に
１．６℃／分で室温から３５０℃まで昇温し、この温度
で１分間保持したのち冷却した。この前駆体の粉末Ｘ線
回析図は図２の通りであり、回析角（２θ）＝２２．１
±０．５℃の範囲にピークを有していなかった。また組
成は原子比でＭｏ：Ｖ：Ｎｂ：Ｔｅ＝１：０．３：０．
１２：０．２３であった。Comparative Example 1 The spray-dried product obtained in Example 1 was heated from room temperature to 350 ° C. at 1.6 ° C./min under a nitrogen gas flow, kept at this temperature for 1 minute, and then cooled. The powder X-ray diffraction diagram of this precursor is as shown in FIG. 2, where the diffraction angle (2θ) = 22.1.
There was no peak in the range of ± 0.5 ° C. The composition is Mo: V: Nb: Te = 1: 0.3: 0.
12: 0.23.
【００１４】この前駆体を実施例１と同様に窒素ガス流
通下に６００℃で２時間焼成して複合金属酸化物触媒を
得た。このものは平均粒径約５０μｍで、組成は原子比
でＭｏ：Ｖ：Ｎｂ：Ｔｅ＝１：０．３：０．１２：０．
１８であった。 触媒能の試験；上記で得られた複合金属酸化物触媒１０
０ｍｇを管式反応器に充填し、これにプロパン、アンモ
ニア及び空気の混合ガス（組成はモル比でプロパン：ア
ンモニア：空気＝１．０：１．２：１５）を空間速度１
０００ｈｒ-1で供給し、４２０℃で反応させてアクリロ
ニトリルを生成させた。This precursor was calcined at 600 ° C. for 2 hours under a nitrogen gas flow in the same manner as in Example 1 to obtain a composite metal oxide catalyst. It has an average particle size of about 50 μm and a composition of Mo: V: Nb: Te = 1: 0.3: 0.12: 0.
It was 18. Test of catalytic ability; composite metal oxide catalyst 10 obtained above
0 mg was charged into a tubular reactor, and a mixed gas of propane, ammonia and air (composition: propane: ammonia: air = 1.0: 1.2: 15 in molar ratio) was charged to the space reactor at a space velocity of 1%.
It was supplied at 000 hr -1 and reacted at 420 ° C. to produce acrylonitrile.
【００１５】反応開始から１〜３時間の反応成績は表１
の通りであった。The reaction results for 1 to 3 hours from the start of the reaction are shown in Table 1.
It was as follows.
【００１６】[0016]
【表１】 [Table 1]
【図１】実施例１で調製した前駆体の粉末Ｘ線回析図で
ある。FIG. 1 is a powder X-ray diffraction diagram of a precursor prepared in Example 1.
【図２】比較例１で調製した前駆体の粉末Ｘ線回析図で
ある。FIG. 2 is a powder X-ray diffraction diagram of a precursor prepared in Comparative Example 1.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 牛窪 孝 岡山県倉敷市潮通３丁目10番地 三菱化学 株式会社水島事業所内 Ｆターム(参考） 4G069 AA02 AA08 BB06A BB06B BC24A BC24B BC54A BC54B BC55A BC55B BC59A BC59B CB07 CB17 CB72 CB76 DA06 EA01Y EC25 FB05 FB06 FB34 FC07 4H006 AA02 AC46 AC54 BA12 BA14 BA15 BA30 BA81 BA85 BC13 BC32 BE14 BE30 4H039 CA70 CL50 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Takashi Ushikubo 3-Chome Shiodori, Kurashiki City, Okayama No. 10 Mitsubishi Chemical Corporation Mizushima Plant F-term (Reference) 4G069 AA02 AA08 BB06A BB06B BC24A BC24B BC54A BC54B BC55A BC55B BC59A BC59B CB07 CB17 CB72 CB76 DA06 EA01Y EC25 FB05 FB06 FB34 BA32 BA32 AC02 BE14 BE30 4H039 CA70 CL50
Claims (8)
ン、バナジウム、ニオブ及びテルルを含有する複合金属
酸化物触媒であって、前駆体がＣｕ−Ｋα線によるＸ線
回析において回析角（２θ）＝２２．１±０．５°に回
析ピークを有するものであることを特徴とする複合金属
酸化物触媒。1. A composite metal oxide catalyst containing molybdenum, vanadium, niobium and tellurium prepared by calcining a precursor, wherein the precursor has a diffraction angle (X-ray diffraction in Cu-Kα ray). (2θ) = 22.1 ± 0.5 ° The composite metal oxide catalyst having a diffraction peak at 0.5 °.
ブ及びテルルの各化合物を含有する溶液又はスラリーか
ら溶媒を除去して得られた固形物を、４００℃以下の温
度で熱分解することにより調製されたものであることを
特徴とする請求項１記載の複合金属酸化物触媒。2. A solid precursor obtained by removing a solvent from a solution or a slurry containing a compound of molybdenum, vanadium, niobium and tellurium at a temperature of 400 ° C. or less. 2. The composite metal oxide catalyst according to claim 1, wherein
ブ及びテルルの少なくとも１種を含有する溶液の２種以
上を、生成する混合物がモリブデン、バナジウム、ニオ
ブ及びテルルの全てを含有するように混合し、混合物か
ら溶媒を除去して得た固体を２００〜４００℃の温度で
熱分解することにより調製されたものであることを特徴
とする請求項１記載の複合金属酸化物触媒。3. Mixing two or more of the solutions in which the precursor contains at least one of molybdenum, vanadium, niobium and tellurium, such that the resulting mixture contains all of molybdenum, vanadium, niobium and tellurium; The composite metal oxide catalyst according to claim 1, wherein the catalyst is prepared by thermally decomposing a solid obtained by removing a solvent from a mixture at a temperature of 200 to 400 ° C.
ルルの原子比率が、モリブデンを１とするとき、バナジ
ウム、ニオブ及びテルルがいずれも０．０１〜１である
ことを特徴とする請求項１ないし３のいずれかに記載の
複合金属酸化物触媒。4. The method according to claim 1, wherein, when the atomic ratio of molybdenum, vanadium, niobium and tellurium is 1, molybdenum, vanadium, niobium and tellurium are each 0.01 to 1. The composite metal oxide catalyst according to any one of the above.
ルルの原子比率が、モリブデンを１とするとき、バナジ
ウムが０．１〜０．６、ニオブが０．０１〜０．６、テ
ルルが０．０５〜０．４であることを特徴とする請求項
１ないし３のいずれかに記載の複合金属酸化物触媒。5. An atomic ratio of molybdenum, vanadium, niobium and tellurium, where molybdenum is 1, vanadium is 0.1 to 0.6, niobium is 0.01 to 0.6, and tellurium is 0.05 to 0.05. 4. The composite metal oxide catalyst according to claim 1, wherein the value is 0.4.
とにより調製されたものであることを特徴とする請求項
１ないし５のいずれかに記載の複合金属酸化物触媒。6. The composite metal oxide catalyst according to claim 1, wherein the catalyst is prepared by calcining a precursor at 450 to 700 ° C.
合金属酸化物触媒を用いて炭化水素を気相接触酸化する
ことを特徴とするカルボン酸及び／又はニトリルの製造
方法。7. A method for producing a carboxylic acid and / or nitrile, comprising subjecting a hydrocarbon to gas phase catalytic oxidation using the composite metal oxide catalyst according to claim 1. Description:
合金属酸化物触媒を用いてプロパンとアンモニア及び酸
素を気相接触反応させることを特徴とするアクリロニト
リルの製造方法。8. A process for producing acrylonitrile, comprising reacting propane with ammonia and oxygen in a gas phase using the composite metal oxide catalyst according to claim 1. Description:
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|---|---|---|---|
| JP2000125534A JP2001300311A (en) | 2000-04-26 | 2000-04-26 | Compound metal oxide catalyst and method for catalytic oxidation of hydrocarbon using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9486788B2 (en) | 2012-09-28 | 2016-11-08 | Rohm And Haas Company | Preparation of propane oxidation catalysts |
| US9517451B2 (en) | 2012-09-28 | 2016-12-13 | Rohm And Haas Company | Preparation of propane oxidation catalysts |
-
2000
- 2000-04-26 JP JP2000125534A patent/JP2001300311A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9486788B2 (en) | 2012-09-28 | 2016-11-08 | Rohm And Haas Company | Preparation of propane oxidation catalysts |
| US9517451B2 (en) | 2012-09-28 | 2016-12-13 | Rohm And Haas Company | Preparation of propane oxidation catalysts |
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