JP2000037623A5 - - Google Patents
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- JP2000037623A5 JP2000037623A5 JP1998209543A JP20954398A JP2000037623A5 JP 2000037623 A5 JP2000037623 A5 JP 2000037623A5 JP 1998209543 A JP1998209543 A JP 1998209543A JP 20954398 A JP20954398 A JP 20954398A JP 2000037623 A5 JP2000037623 A5 JP 2000037623A5
- Authority
- JP
- Japan
- Prior art keywords
- niobium
- catalyst
- preparing
- unsaturated carboxylic
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 claims description 17
- 239000010955 niobium Substances 0.000 claims description 14
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 230000003197 catalytic Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002822 niobium compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- AXIFGFAGYFPNFC-UHFFFAOYSA-I 2-hydroxy-2-oxoacetate;niobium(5+) Chemical compound [Nb+5].OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O AXIFGFAGYFPNFC-UHFFFAOYSA-I 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
すなわち、本発明は
（１）アルカンを気相接触酸化反応させて不飽和カルボン酸を製造するために用いられる、ニオブを含む触媒の調製方法であって、シュウ酸とニオブ化合物を含む水溶液または水性懸濁液を冷却して懸濁液を得、該懸濁液から固形分を分離除去して得られるニオブ含有液を、シュウ酸／ニオブのモル比２〜４に調整し、ニオブ原料液として用いることを特徴とするニオブ含有触媒の調製方法、
（２）該ニオブ化合物がニオブ酸およびシュウ酸水素ニオブから選ばれる少なくとも１種類以上である（１）に記載の触媒の調製方法、
（３）該触媒が次の一般式（Ｉ）で示される化合物であることを特徴とする（１）または（２）に記載の触媒の調製方法、
Ｍｏ１ＶａＮｂｂＸｃＺｄＯｎ （Ｉ）
（式中成分ＸはＴｅおよびＳｂから選ばれる少なくとも１種類以上の元素を表し、成分ＺはＷ、Ｃｒ、Ｔａ、Ｔｉ、Ｚｒ、Ｈｆ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ａｇ、Ｚｎ、Ｂ、Ａｌ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、Ｐｂ、Ｐ、Ｂｉ、Ｙ、希土類元素およびアルカリ土類元素から選ばれる少なくとも１種類以上の元素を表し、ａ、ｂ、ｃ、ｄ、ｎはＭｏ１原子当たりの原子比を表し、
０．１≦ａ≦１．０
０．０１≦ｂ≦１．０
０．０１≦ｃ≦１．０
０≦ｄ≦１．０
であり、またｎは他の元素の酸化状態によって決まる数である。）
（４）該触媒がシリカに担持されていることを特徴とする（１）〜（３）のいずれかに記載の触媒の調製方法、
（５）シリカの含有量が該触媒成分とシリカから成るシリカ担持触媒の全重量比の２０〜６０重量％であることを特徴とする（４）に記載の触媒の調製方法、
（６）該シリカ担体の原料がアンモニウムイオンで安定化したゾルであることを特徴とする（４）または（５）に記載の触媒の調製方法、
（７）アルカンを気相接触酸化反応させて不飽和カルボン酸を製造するに際して、（１）〜（６）のいずれかに記載の調製方法によって調製されたニオブ含有触媒を用いることを特徴とする不飽和カルボン酸の製造方法に関するものである。
That is, the present invention is (1) a method for preparing a catalyst containing niobium, which is used for producing an unsaturated carboxylic acid by subjecting alkane to a vapor phase catalytic oxidation reaction, and is an aqueous solution or an aqueous solution containing niobium and a niobium compound. The suspension is cooled to obtain a suspension, and the niobium-containing liquid obtained by separating and removing solids from the suspension is adjusted to a oxalic acid / niobium molar ratio of 2 to 4 to prepare a niobium raw material liquid. A method for preparing a niobium-containing catalyst, which is characterized by being used.
(2) The method for preparing a catalyst according to (1), wherein the niobium compound is at least one selected from niobium acid and niobium hydrogen oxalate.
(3) The method for preparing a catalyst according to (1) or (2), wherein the catalyst is a compound represented by the following general formula (I).
Mo1VaNbbXcZdOn (I)
(Component X in the formula represents at least one element selected from Te and Sb, and component Z is W, Cr, Ta, Ti, Zr, Hf, Mn, Re, Fe, Ru, Co, Rh, Ni, Represents at least one element selected from Pd, Pt, Ag, Zn, B, Al, Ga, In, Ge, Sn, Pb, P, Bi, Y, rare earth elements and alkaline earth elements, a, b. , C, d, n represent the atomic ratio per Mo1 atom,
0.1 ≤ a ≤ 1.0
0.01 ≤ b ≤ 1.0
0.01 ≤ c ≤ 1.0
0 ≦ d ≦ 1.0
And n is a number determined by the oxidation state of other elements. )
(4) The method for preparing a catalyst according to any one of (1) to (3), wherein the catalyst is supported on silica.
(5) The method for preparing a catalyst according to (4), wherein the content of silica is 20 to 60% by weight based on the total weight ratio of the silica-supported catalyst composed of the catalyst component and silica.
(6) The method for preparing a catalyst according to (4) or (5), wherein the raw material of the silica carrier is an ammonium ion-stabilized sol.
(7) When producing an unsaturated carboxylic acid by subjecting an alkane to a vapor-phase catalytic oxidation reaction, a niobium-containing catalyst prepared by the preparation method according to any one of (1) to (6) is used. It relates to a method for producing an unsaturated carboxylic acid.
【００３９】
【比較例３】
（ニオブ原料液の調製）比較例１と同様にしてシュウ酸／ニオブのモル比５．５のニオブ原料液を得た。
（触媒の調製）組成式がＭｏ1Ｖ0.32Ｎｂ0.06Ｓｂ0.16Ｏnで示される触媒を、上記のニオブ原料液を用い、その使用量を３５８．１ｇとした他は実施例７と同様にして調製して触媒を得た。
（プロパンの酸化反応）得られた触媒を用いて、実施例７と同じ条件でプロパンの酸化反応を行った。結果を表１に示す。
[0039]
[Comparative Example 3]
(Preparation of Niobium Raw Material Solution) A niobium raw material solution having a molar ratio of oxalic acid / niobium of 5.5 was obtained in the same manner as in Comparative Example 1.
A catalyst composition formula (Preparation of catalyst) are shown in Mo 1 V 0.32 Nb 0.06 Sb 0.16 O n, using the above-mentioned niobium raw material liquid, except that the amount thereof and 358.1g in the same manner as in Example 7 Prepared to obtain a catalyst.
(Oxidation reaction of propane) Using the obtained catalyst, an oxidation reaction of propane was carried out under the same conditions as in Example 7. The results are shown in Table 1.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20954398A JP4166334B2 (en) | 1998-07-24 | 1998-07-24 | Method for preparing oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20954398A JP4166334B2 (en) | 1998-07-24 | 1998-07-24 | Method for preparing oxidation catalyst |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000037623A JP2000037623A (en) | 2000-02-08 |
| JP2000037623A5 true JP2000037623A5 (en) | 2005-10-27 |
| JP4166334B2 JP4166334B2 (en) | 2008-10-15 |
Family
ID=16574557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20954398A Expired - Lifetime JP4166334B2 (en) | 1998-07-24 | 1998-07-24 | Method for preparing oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4166334B2 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114278A (en) * | 1998-11-16 | 2000-09-05 | Saudi Basic Industries Corporation | Catalysts for catalytic oxidation of propane to acrylic acid, methods of making and using the same |
| JP4809532B2 (en) * | 1999-11-15 | 2011-11-09 | サウディ ベーシック インダストリーズ コーポレイション | Catalyst for catalytic oxidation of propane to acrylic acid, its production and use |
| DE10051419A1 (en) | 2000-10-17 | 2002-04-18 | Basf Ag | Production of acrolein or acrylic acid involves absorption of propane and propene from a gas mixture followed by desorption and oxidation, with no catalytic dehydrogenation of propane and no added oxygen |
| DE10118814A1 (en) | 2001-04-17 | 2002-10-24 | Basf Ag | Production of acrolein or acrylic acid involves absorption of propane and propene from a gas mixture followed by desorption and oxidation, with no catalytic dehydrogenation of propane and no added oxygen |
| AU2001278449A1 (en) | 2000-06-14 | 2001-12-24 | Basf Aktiengesellschaft | Method for producing acrolein and/or acrylic acid |
| EP1301457B1 (en) | 2000-07-18 | 2008-03-26 | Basf Se | Method for producing acrylic acid by the heterogeneously catalysed gas-phase oxidation of propane |
| US6407031B1 (en) | 2000-09-28 | 2002-06-18 | Rohm And Haas Company | Promoted multi-metal oxide catalyst |
| US6734136B2 (en) | 2000-09-28 | 2004-05-11 | Rohm And Haas Company | IR and/or SM promoted multi-metal oxide catalyst |
| US6461996B2 (en) | 2000-09-28 | 2002-10-08 | Rohm And Haas Company | Halogen promoted multi-metal oxide catalyst |
| US6403525B1 (en) | 2000-09-28 | 2002-06-11 | Rohm And Haas Company | Promoted multi-metal oxide catalyst |
| US6589907B2 (en) | 2000-09-28 | 2003-07-08 | Rohm And Haas Company | Zn and/or Ga promoted multi-metal oxide catalyst |
| JP4878684B2 (en) * | 2001-01-24 | 2012-02-15 | 旭化成ケミカルズ株式会社 | Low specific gravity silica supported catalyst |
| US6943135B2 (en) | 2001-04-12 | 2005-09-13 | Rohm And Haas Company | NOx treated mixed metal oxide catalyst |
| TW548133B (en) | 2001-04-12 | 2003-08-21 | Rohm & Haas | NOx treated mixed metal oxide catalyst |
| US6645906B2 (en) | 2001-04-30 | 2003-11-11 | Rohm And Haas Company | High temperature mixing |
| EP1266688A3 (en) | 2001-06-14 | 2003-07-09 | Rohm And Haas Company | Mixed metal oxide catalyst doped by vapor depositing a metal and mixed metal oxide catalyst prepared by depositing a plurality of films of different elements using physical vapor deposition |
| ZA200208247B (en) | 2001-10-26 | 2003-05-14 | Rohm & Haas | Treatment of mixed metal oxide catalyst. |
| ZA200209470B (en) | 2001-12-04 | 2003-06-03 | Rohm & Haas | Improved processes for the preparation of olefins, unsaturated carboxylic acids and unsaturated nitriles from alkanes. |
| BRPI0500615B1 (en) | 2004-03-10 | 2015-07-14 | Rohm & Haas | Modified Catalyst and Modified Catalyst System |
| US20060122055A1 (en) * | 2004-12-06 | 2006-06-08 | Gaffney Anne M | (Amm)oxidation catalyst and catalytic (amm)oxidation process for conversion of lower alkanes |
| US7875571B2 (en) | 2006-09-07 | 2011-01-25 | Rohm And Haas Company | Activated mixed metal oxide oxidation catalysts |
-
1998
- 1998-07-24 JP JP20954398A patent/JP4166334B2/en not_active Expired - Lifetime
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