CN106881128B - Heteropolyacid salt catalyst, preparation method and application thereof - Google Patents
Heteropolyacid salt catalyst, preparation method and application thereof Download PDFInfo
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- CN106881128B CN106881128B CN201510941165.3A CN201510941165A CN106881128B CN 106881128 B CN106881128 B CN 106881128B CN 201510941165 A CN201510941165 A CN 201510941165A CN 106881128 B CN106881128 B CN 106881128B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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Abstract
Heteropolyacid salt catalysts, methods of preparation and uses thereof are disclosed. The catalyst is prepared by the following method: i) dissolving or suspending precursor compounds of the respective component elements in a solvent, and mixing to obtain a solution or slurry, to prepare a suspension dispersion slurry of the catalyst precursor containing all the above-mentioned catalyst components; (ii) drying, wherein the space velocity of the dried catalyst precursor in water vapor is 20-400 h‑1Treating for 60-600 minutes at 200-350 ℃; and (iii) calcining.
Description
Technical Field
The invention relates to a heteropolyacid salt catalyst and a preparation method thereof. The catalyst obtained by the method of the invention can oxidize methacrolein to prepare methacrylic acid with high conversion rate and high selectivity. The invention also relates to the use of said catalyst in the oxidation of methacrolein to methacrylic acid.
Background
The heteropoly acid (salt) catalyst has a unique structure and excellent performance, has a wide application prospect in catalysis, and is widely applied to chemical production, particularly petrochemical production. The gas phase oxidation of methacrolein with heteropoly acid (salt) catalyst to produce methacrylic acid is a widely used method for preparing methacrylic acid in industry. In order to improve the effective utilization rate of the catalyst, a plurality of methods are proposed in the patent.
Chinese patent CN103459022A proposes that a step of drying an aqueous mixed solution containing a raw material compound of a catalyst component to produce a dried product having an apparent density (X) of 1.00 to 1.80kg/L is required in the catalyst preparation process; and a step of molding the dried product or a mixture containing the dried product to produce a molded catalyst having a molded product density (Y) of 1.60 to 2.40kg/L and a ratio (X/Y) of the apparent density (X) to the molded product density (Y) of 0.50 to 0.80, and by this method, an effective pore structure can be formed in the catalyst to improve the catalyst performance.
Chinese patent CN 101980781a proposes to improve the catalyst performance by forming a fine pore structure by a method comprising the following steps: production of a catalyst for methacrylic acid production containing molybdenum and phosphorus as catalyst components:
(1) a step of adding an organic binder (B1) to a mixed solution or slurry of raw material compounds containing a catalyst component, and then drying the mixture;
(2) a step of kneading the obtained dried product, the liquid, and the organic binder (B2); and
(3) and a step of obtaining a molded body by extrusion molding the obtained kneaded product.
US patent US 6624326 proposes to include the following conditions in the aqueous solution prepared:
(1) it contains nitrogen heterocyclic compound, nitrate radical ion and ammonium ion;
(2) the ratio of the molar content of the ammonium ions to the molar content of the nitrate ions is less than 1.7;
(3) the ratio of the molar content of ammonium ions to the atomic content of molybdenum per 12 moles is less than 10, and the method for forming the effective pore structure can improve the performance of the catalyst.
Although these methods improve the selectivity and conversion of the catalyst to some extent, they leave room for further improvement.
Disclosure of Invention
An object of the present invention is to provide a heteropoly-acid (salt) catalyst capable of oxidizing methacrolein with high conversion and high selectivity to produce methacrylic acid.
It is a further object of the present invention to provide a process for the preparation of said catalyst.
Accordingly, one aspect of the present invention is to provide a catalyst represented by the formula:
Mo12PaVbXcYdZeOf
wherein Mo, P, V and O represent molybdenum, phosphorus, vanadium and oxygen, respectively;
x represents at least one element selected from potassium (K), rubidium (Rb) and cesium (Cs);
y represents at least one element selected from copper (Cu), magnesium (Mg), antimony (Sb), bismuth (Bi), zinc (Zn), germanium (Ge), silicon (Si), and tin (Sn);
z represents at least one element selected from iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), tungsten (W) and rhenium (Re);
a. b, c, d, e represent the atomic ratio of each element, wherein:
a＝1～3；
b＝0.1～2；
c＝0.1～3；
d＝0.01～3；
e＝0.01～2；
f is an atomic ratio of oxygen required to satisfy the valences of the respective components described above.
The catalyst is prepared by the following method:
(i) dissolving or suspending precursor compounds of the respective component elements in a solvent, and mixing to obtain a solution or slurry, to prepare a suspension dispersion slurry of the catalyst precursor containing all the above-mentioned catalyst components;
(ii) drying, wherein the space velocity of the dried catalyst precursor in water vapor is 20-400 h-1Treating for 60-600 minutes at 200-350 ℃; and
(iii) and (4) roasting.
Another aspect of the present invention relates to a process for preparing the catalyst of the present invention, comprising the steps of:
i) dissolving or suspending precursor compounds of the respective component elements in a solvent, and mixing to obtain a solution or slurry, to prepare a suspension dispersion slurry of the catalyst precursor containing all the above-mentioned catalyst components;
(ii) drying, wherein the space velocity of the dried catalyst precursor in water vapor is 20-400 h-1The treatment temperature was 20 deg.CTreating for 60-600 minutes at 0-350 ℃; and
(iii) and (4) roasting.
Detailed Description
The catalyst of the present invention is represented by the formula:
Mo12PaVbXcYdZeOf
wherein Mo, P, V and O represent molybdenum, phosphorus, vanadium and oxygen, respectively;
x is at least one element selected from potassium (K), rubidium (Rb), cesium (Cs), preferably at least one element selected from potassium (K) and cesium (Cs), preferably potassium (K);
y is at least one element selected from copper (Cu), magnesium (Mg), antimony (Sb), bismuth (Bi), zinc (Zn), germanium (Ge), silicon (Si), and tin (Sn), preferably at least one element selected from copper (Cu), antimony (Sb), bismuth (Bi), and zinc (Zn), preferably copper (Cu), bismuth (Bi), and/or zinc (Zn);
z represents at least one element selected from iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), tungsten (W) and rhenium (Re), preferably at least one element selected from iron (Fe), cobalt (Co), ruthenium (Ru) and rhenium (Re), preferably iron (Fe) and/or cobalt (Co);
a. b, c, d, e represent the atomic ratio of each element, wherein:
a is 1 to 3, preferably 1.2 to 2.8, more preferably 1.5 to 2.5, and preferably 1.8 to 2.3;
b is 0.1 to 2, preferably 0.3 to 1.8, more preferably 0.5 to 1.5, and preferably 0.8 to 1.2;
c is 0.1 to 3, preferably 0.5 to 2.8, more preferably 0.8 to 2.3, preferably 1 to 2;
d is 0.01 to 3, preferably 0.05 to 2.5, more preferably 0.1 to 2.2, particularly preferably 0.5 to 2.0;
e-0.01-2, preferably 0.05-1.8, more preferably 0.1-1.5, and preferably 0.5-1.2
f is an atomic ratio of oxygen required to satisfy the valences of the respective components described above.
In a preferred embodiment of the present invention, the catalyst is selected from the group consisting of: mo12P1.5V0.6Cs1.5Cu0.3Re0.05、Mo12P1.5V0.6K1.5Cu0.3Re0.05、Mo12P1.5V0.6Cs1.5Zn0.3Co0.05、Mo12P1.5V0.6Cs1.5Cu0.3Fe0.2，Mo12P1.5V0.6Cs1.5Zn0.3Fe0.2，Mo12P1.5V0.6Cs1.5Cu0.3Co0.2，Mo12P1.5V0.6Cs1.5Cu0.25Re0.05，Mo12P1.5V0.6K1.5Zn0.25Re0.05，Mo12P1.5V0.6Cs1.0K0.5Cu0.25Re0.05，Mo12P1.5V0.6Cs1.5Cu0.15Zn0.1Re0.05，Mo12P1.5V0.6Cs1.5Cu0.25Re0.1Or a mixture of two or more thereof.
The preparation method of the catalyst comprises the following steps:
i) dissolving or suspending precursor compounds of the respective component elements in a solvent, and mixing to obtain a solution or slurry, to prepare a suspension dispersion slurry of the catalyst precursor containing all the above-mentioned catalyst components;
the precursor compound of the catalyst element used in the mixed solution or slurry is not particularly limited, and a nitrate, a carbonate, an acetate, an oxide, a halide, an oxide, an oxyacid salt, and the like of each constituent element of the catalyst can be used.
Non-limiting examples of suitable molybdenum precursor compounds include, for example, molybdenum trioxide, ammonium paramolybdate, phosphomolybdic acid, or molybdate, with ammonium paramolybdate being preferred.
Non-limiting examples of suitable phosphorus precursor compounds include, for example, phosphorus pentoxide, phosphoric acid, phosphomolybdic acid, ammonium phosphate, etc., with phosphoric acid being preferred.
Non-limiting examples of suitable vanadium precursor compounds are, for example, vanadium pentoxide, ammonium metavanadate and the like, preferably ammonium metavanadate.
There is no particular requirement for the solvent and temperature required for dissolution of the precursor compound, as long as the compound used is completely dissolved or uniformly mixed. Non-limiting examples of suitable solvents include, for example, water, ethanol, etc., and water is preferably used.
The ratio of each active component in the catalyst is based on the molybdenum atomic ratio of 12, and the ratio of phosphorus is 1-3, preferably 1.2-2; the proportion of vanadium is 0.1-2, preferably 0.3-1.2; the kind and use ratio of other active components required are determined according to the use conditions of the catalyst and the like to obtain a catalyst having the most appropriate performance. Generally, the proportion of the element X is from 0.1 to 3, preferably from 1 to 2; the proportion of the element Y is 0.01 to 3, preferably 0.1 to 1; the proportion of the element Z is from 0.01 to 2, preferably from 0.04 to 1.
(ii) Drying, wherein the space velocity of the dried catalyst precursor in water vapor is 20-400 h-1And the treatment temperature is 200 to 350 ℃ for 60 to 600 minutes
The drying method and temperature of the present invention are not particularly limited, and may be any drying method and drying temperature known in the art. In one embodiment of the invention, spray drying, evaporation drying, drum drying, and the like are selected, with spray drying being preferred.
The dried catalyst precursor may be pulverized as necessary. In one embodiment of the invention, the process of the invention further comprises optionally mixing the resulting dried billet with a thermally conductive diluent. Non-limiting examples of suitable thermally conductive diluents are, for example, SiC, SiO2、MoO3、WO3、TiO2Or ZrO2Preferably SiC, MoO3Or ZrO2One or a mixture of several of them.
In a preferred embodiment of the present invention, the thermally conductive diluent is 10 to 50% by weight, preferably 20 to 40% by weight.
Suitable mixing equipment for mixing with the thermally conductive diluent is not particularly required and may be any mixing equipment known in the art. In a preferred embodiment of the present invention, the mixing device is selected from the group consisting of a double cone mixer, a multi-directional motion mixer, a trough mixer, and the like.
In one embodiment of the present invention, the method further comprises shaping the mixture of catalyst blank and heat absorbent. The molding method is not particularly required, and any molding method known in the art may be used. In one embodiment of the present invention, the mixture is molded by a dry molding method or a wet molding method. For example, a tablet press molding method, an extrusion molding method, a granulation molding method, and the like can be used. The shape of the molded article is not particularly limited, and a desired shape such as a cylindrical shape, a ring shape, or a spherical shape can be selected. In addition, a small amount of a lubricant such as graphite may be added at the time of molding.
The method also comprises the step of carrying out hydrothermal treatment on the catalyst blank or the formed catalyst. The inventors have found that hydrothermal treatment of the catalyst blank helps to improve feedstock conversion and product selectivity and yield.
During the hydrothermal treatment of the catalyst blank, the space velocity of the water vapor is 20-400 h-1Preferably 100 to 300 hours-1(ii) a The treatment temperature is 200-350 ℃, and preferably 250-300 ℃; the treatment time is 60 to 600 minutes, preferably 180 to 360 minutes. The performance of the catalyst can be obviously improved through the hydrothermal treatment process.
(iii) Roasting
The method of the present invention further comprises calcining the hydrothermally treated catalyst blank in an oxygen-containing atmosphere. The roasting temperature is selected to be 300-450 ℃, and preferably 350-400 ℃. The roasting time is 60 to 600 minutes, preferably 180 to 540 minutes.
In the oxygen-containing atmosphere suitable for the calcination step of the present invention, the oxygen mass concentration is not less than 10%, preferably not less than 20%.
The catalyst of the invention is suitable for synthesizing methacrylic acid by gas phase oxidation of methacrolein. In one example of the present invention, the synthesis method comprises:
preheating a mixture of methacrolein feedstock, air (molecular oxygen-containing diluent gas) and water vapor; and
-introducing the preheated mixture into a fixed bed tubular reactor containing the catalyst of the invention for selective oxidation to synthesize methacrylic acid.
Suitable diluent gas containing molecular oxygen can be pure oxygen, oxygen-enriched oxygen or air, and the diluent gas can be N2、CO、CO2Or H2O or a mixture of O and O in any proportion.
In one embodiment of the present invention, the oxidation reaction conditions are:
the temperature is 220-300 ℃, preferably 240-280 ℃;
the pressure is 0.05-0.5 MPa, and the normal pressure is preferred;
the total airspeed of the mixed gas of the reaction raw materials is 1000-5000 h-1Preferably 1200 to 3000 hours-1；
The molar concentration of the methacrylic acid is 1-20%, preferably 3-8%;
O2the molar ratio of the methyl acrolein to the methyl acrolein is 0.5-8, preferably 1-5;
the molar ratio of the water vapor to the methacrolein is 1 to 15, preferably 3 to 10.
The conversion and selectivity of the synthesis of methacrylic acid by the oxidation of methacrolein were calculated as follows:
methacrolein conversion (mol%) < 100 × (moles of methacrolein supplied-moles of methacrolein remaining after reaction)/moles of methacrolein supplied
Methacrylic acid selectivity (mol%) < 100 × (mole of methacrylic acid formed by reaction)/(mole of methacrolein supplied-mole of methacrolein remaining after the reaction)
Methacrylic acid yield (mol%) of 100 × (mol% of methacrylic acid formed by reaction)/mol of methacrolein supplied
The preparation of the high performance catalyst and its performance in catalyzing the selective oxidation of methacrolein to methacrylic acid will now be illustrated by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1
1. Preparation of the catalyst
Dissolving 1500 g of ammonium paramolybdate and 49.7 g of ammonium metavanadate in 4500 g of water with the temperature of 80 ℃ to obtain a solution A; dissolving 207 g of cesium nitrate in 800 g of water to obtain a solution B; dissolving 51.8 g of copper nitrate in 500 g of water to obtain a solution C; solution D was obtained by dissolving 8.6 grams of rhenium oxide in 100 grams of water.
Solution B, C, D was added rapidly to solution A, and after stirring for 10 minutes 121.2 g of phosphoric acid was added to solution A, and stirring was continued at 80 ℃ for 120 minutes to obtain a slurry containing the catalyst precursor.
The slurry was dried at 150 ℃ for 24 hours to give a solid powder. After being crushed, 800 g of solid powder is taken out and evenly mixed with 200 g of silicon carbide, and the cylindrical catalyst with the outer diameter of 5mm and the length of 3mm is obtained after granulation and tabletting molding.
Placing the catalyst in a roasting furnace, introducing steam for hydrothermal treatment, wherein the space velocity of the steam is 150h-1(ii) a The treatment temperature is 250 ℃; the treatment time was 300 minutes. Then the water vapor is switched into air, the mixture is roasted for 5 hours at 380 ℃, and the air space velocity is 600 hours-1(ii) a And preparing the final finished catalyst. The catalyst composition is Mo12P1.5V0.6Cs1.5Cu0.3Re0.05。
2. Oxidation reaction
Filling the catalyst into a reaction tube, and introducing mixed gas consisting of 5 volume percent of methacrolein, 10 volume percent of oxygen, 40 volume percent of nitrogen and 45 volume percent of water vapor to ensure that the catalyst is subjected to normal pressure, reaction temperature of 280 ℃ and space velocity of 1200h-1The reaction is carried out under the conditions of (1). The reaction results are shown in Table 1.
Example 2
The space velocity of the steam in example 1 was adjusted to 300h-1The reaction results are shown in Table 1, except that the other conditions are unchanged.
Example 3
The treatment temperature of the steam in example 1 was adjusted to 300 ℃ and the reaction results are shown in Table 1, except that the conditions were not changed.
Comparative example 1
The steam treatment step of example 1 was eliminated, i.e. the cylindrical form was catalyzedThe agent is directly roasted for 5 hours at 380 ℃ in air atmosphere, and the air space velocity is 600 hours-1(ii) a The final finished catalyst was prepared under otherwise unchanged conditions and the reaction results are shown in table 1.
Example 4
8.6 g of rhenium oxide from example 1 were replaced by 57.8 g of iron nitrate and the catalyst composition was Mo12P1.5V0.6Cs1.5Cu0.3Fe0.2The reaction results are shown in Table 1, except that the other conditions are unchanged.
Example 5
The catalyst composition was Mo by replacing 207 g of cesium nitrate in example 1 with 142.4 g of potassium nitrate12P1.5V0.6K2.0Cu0.3Re0.05The reaction results are shown in Table 1, except that the other conditions are unchanged.
Comparative example 2
The steam treatment step in example 5 was eliminated by calcining the cylindrical catalyst directly in an air atmosphere at 380 ℃ for 5 hours at an air space velocity of 600 hours-1(ii) a The final finished catalyst was prepared under otherwise unchanged conditions and the reaction results are shown in table 1.
Example 6
51.8 g of copper nitrate from example 1 were replaced by 43.2 g of copper nitrate, the catalyst composition being Mo12P1.5V0.6Cs1.5Cu0.25Re0.05The reaction results are shown in Table 1, except that the other conditions are unchanged.
Example 7
8.6 g of rhenium oxide in example 1 were replaced by 17.2 g of rhenium oxide, the catalyst composition being Mo12P1.5V0.6Cs1.5Cu0.25Re0.1The reaction results are shown in Table 1, except that the other conditions are unchanged.
TABLE 1
Claims (12)
1. A catalyst represented by the formula:
Mo12PaVbXcYdZeOf
wherein Mo, P, V and O represent molybdenum, phosphorus, vanadium and oxygen, respectively;
x represents at least one element selected from potassium (K), rubidium (Rb) and cesium (Cs);
y represents at least one element selected from copper (Cu), magnesium (Mg), antimony (Sb), bismuth (Bi), zinc (Zn), germanium (Ge), silicon (Si), and tin (Sn);
z represents at least one element selected from iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), tungsten (W) and rhenium (Re);
a. b, c, d, e represent the atomic ratio of each element, wherein:
a=1～3；
b=0. 1～2；
c=0.1～3；
d=0.01～3；
e=0.01～2；
f is the atomic ratio of oxygen required to satisfy the valences of the above components;
the catalyst is prepared by the following method:
(i) dissolving or suspending precursor compounds of the respective component elements in a solvent, and mixing to obtain a solution or slurry, to prepare a suspension dispersion slurry of the catalyst precursor containing all the above-mentioned catalyst components;
(ii) drying, wherein the space velocity of the dried catalyst precursor in water vapor is 20-400 h-1Treating for 60-600 minutes at 200-350 ℃; and
(iii) and (4) roasting.
2. The catalyst according to claim 1, wherein step (ii) of the preparation process comprises mixing the dried catalyst precursor with a thermally conductive diluent followed by steam treatment.
3. The method of claim 2Catalyst, characterized in that the thermally conductive diluent is selected from the group consisting of SiC, SiO2、MoO3、WO3、TiO2Or ZrO2A mixture of one or more of them.
4. The catalyst according to claim 2 or 3, wherein the thermally conductive diluent is present in an amount of 10 to 50% by weight.
5. The catalyst according to claim 2 or 3, wherein the thermally conductive diluent is 20-40% by weight.
6. The catalyst of claim 1 selected from the group consisting of Mo12P1.5V0.6Cs1.5Cu0.3Re0.05、Mo12P1.5V0.6K1.5Cu0.3Re0.05、Mo12P1.5V0.6Cs1.5Zn0.3Co0.05、Mo12P1.5V0.6Cs1.5Cu0.3Fe0.2，Mo12P1.5V0.6Cs1.5Zn0.3Fe0.2，Mo12P1.5V0.6Cs1.5Cu0.3Co0.2，Mo12P1.5V0.6Cs1.5Cu0.25Re0.05，Mo12P1.5V0.6K1.5Zn0.25Re0.05，Mo12P1.5V0.6Cs1.0K0.5Cu0.25Re0.05，Mo12P1.5V0.6Cs1.5Cu0.15Zn0.1Re0.05，Mo12P1.5V0.6Cs1.5Cu0.25Re0.1Or a mixture of two or more thereof.
7. A process for the preparation of a catalyst having the formula,
Mo12PaVbXcYdZeOf
wherein Mo, P, V and O represent molybdenum, phosphorus, vanadium and oxygen, respectively;
x represents at least one element selected from potassium (K), rubidium (Rb) and cesium (Cs);
y represents at least one element selected from copper (Cu), magnesium (Mg), antimony (Sb), bismuth (Bi), zinc (Zn), germanium (Ge), silicon (Si), and tin (Sn);
z represents at least one element selected from iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), tungsten (W) and rhenium (Re);
a. b, c, d, e represent the atomic ratio of each element, wherein:
a=1～3；
b=0. 1～2；
c=0.1～3；
d=0.01～3；
e=0.01～2；
f is the atomic ratio of oxygen required to satisfy the valences of the above components;
it comprises the following steps:
i) dissolving or suspending precursor compounds of the respective component elements in a solvent, and mixing to obtain a solution or slurry, to prepare a suspension dispersion slurry of the catalyst precursor containing all the above-mentioned catalyst components;
(ii) drying, wherein the space velocity of the dried catalyst precursor in water vapor is 20-400 h-1Treating for 60-600 minutes at 200-350 ℃; and
(iii) and (4) roasting.
8. The process according to claim 7, wherein step (ii) of the process comprises mixing the dried catalyst precursor with a thermally conductive diluent followed by steam treatment.
9. The method of claim 8, wherein the thermally conductive diluent is selected from the group consisting ofFrom SiC, SiO2、MoO3、WO3、TiO2Or ZrO2A mixture of one or more of them.
10. The method for preparing catalyst according to claim 8 or 9, wherein the thermally conductive diluent is 10 to 50% by weight.
11. The method for preparing catalyst according to claim 8 or 9, wherein the thermally conductive diluent is 20-40% by weight.
12. Use of the catalyst according to any one of claims 1 to 6 for the oxidation of methacrolein to methacrylic acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109800A (en) * | 1994-02-22 | 1995-10-11 | Basf公司 | Polymetal oxide materials |
| CN1451478A (en) * | 2002-04-16 | 2003-10-29 | 住友化学工业株式会社 | Method for reactivating catalyst for production of methacrylic acid |
| CN102114427A (en) * | 2010-12-13 | 2011-07-06 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein |
| CN103170362A (en) * | 2011-12-26 | 2013-06-26 | 上海华谊丙烯酸有限公司 | Heteropolyacid catalyst, and preparation method and application thereof |
| CN103831131A (en) * | 2012-11-21 | 2014-06-04 | 上海华谊丙烯酸有限公司 | Catalyst, preparation method and application thereof |
-
2015
- 2015-12-15 CN CN201510941165.3A patent/CN106881128B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109800A (en) * | 1994-02-22 | 1995-10-11 | Basf公司 | Polymetal oxide materials |
| CN1451478A (en) * | 2002-04-16 | 2003-10-29 | 住友化学工业株式会社 | Method for reactivating catalyst for production of methacrylic acid |
| CN102114427A (en) * | 2010-12-13 | 2011-07-06 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein |
| CN103170362A (en) * | 2011-12-26 | 2013-06-26 | 上海华谊丙烯酸有限公司 | Heteropolyacid catalyst, and preparation method and application thereof |
| CN103831131A (en) * | 2012-11-21 | 2014-06-04 | 上海华谊丙烯酸有限公司 | Catalyst, preparation method and application thereof |
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| CN106881128A (en) | 2017-06-23 |
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