CN109731592B - Catalyst for preparing methacrylic acid by selective oxidation of methacrolein and preparation method and application thereof - Google Patents
Catalyst for preparing methacrylic acid by selective oxidation of methacrolein and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing methacrylic acid by selective oxidation of methacrolein, a preparation method and application thereof; the composition of the catalyst is PaMobVcXxYyZz1HhOg1‑Zz2Og2X comprises a combination of at least two of sodium, potassium, rubidium, or cesium, Y comprises any one or a mixture of at least two of calcium, magnesium, chromium, manganese, iron, cobalt, copper, nickel, zinc, aluminum, silicon, germanium, antimony, bismuth, lanthanum, or cerium, and Z comprises titanium and/or zirconium; compared with the traditional phosphomolybdic vanadate heteropoly acid salt catalyst, the catalyst provided by the invention has higher activity for catalyzing the selective oxidation of methacrolein to prepare methacrylic acid, and in the process of catalyzing the selective oxidation of methacrolein to prepare methacrylic acid, when the conversion rate of methacrolein is 90%, the selectivity of methacrolein to methacrylic acid can reach 93% at most, thereby meeting the requirements of actual industrial production.
Description
Technical Field
The invention relates to the field of catalytic materials, in particular to a catalyst for preparing methacrylic acid by selectively oxidizing methacrolein, a preparation method and application thereof.
Background
Japanese catalytic chemistry and Mitsubishi rayon realized the industrialization of a technique for synthesizing methyl methacrylate by two-step catalytic oxidation and one-step esterification using isobutylene or tert-butyl alcohol as a raw material in 1982. Wherein, the oxidation of methacrolein to methacrylic acid is a key reaction in the process route, and phosphomolybdic acid or phosphomolybdic vanadate heteropoly acid salt is generally adopted as the catalyst.
CN1750878A discloses a process for reacting methacrolein, isobutyraldehyde or isobutyraldehydeCatalyst for the production of methacrylic acid by gas-phase catalytic oxidation of acids, comprising as active component a heteropolyacid salt comprising Mo, V, P, Cu, Cs and NH, and method for the production and use thereof4As essential active components, the catalyst can use cesium weak acid salt or cesium hydroxide as a cesium raw material of the catalyst active component and NH with ammonium acetate as the catalyst active component4Obtaining a raw material; the catalyst obtained by the scheme has low selectivity on methacrylic acid, more byproducts and high separation cost in the process of catalyzing selective oxidation of methacrolein.
CN104001542A discloses a heteropoly acid and oxide composite catalyst for preparing methacrylic acid by oxidizing methacrolein; the catalyst is prepared by mixing phosphomolybdic acid and metal oxides (such as vanadium pentoxide, ferric oxide, copper oxide, nickel dioxide, manganese dioxide, cobalt oxide, titanium dioxide and zinc oxide) in a liquid phase step by step to form more active sites on the surface of heteropolyanions, and adding cesium; the catalyst prepared by the scheme has the advantages of low conversion rate of methacrolein and high production cost.
CN104001543A discloses a heteropoly acid catalyst for preparing methacrylic acid by oxidizing methacrolein and a preparation method thereof, wherein the catalyst takes cesium phosphomolybdate or ammonium phosphomolybdate vanadate with strong thermal stability as an inner core, ammonium phosphomolybdate or cesium phosphomolybdate vanadate as a secondary outer layer, and phosphomolybdate vanadate with catalytic activity sites is wrapped on the outermost layer; the catalyst prepared by the scheme has low methacrolein conversion rate, and the preparation process adopts liquid phase reaction, so that the preparation process is difficult to control.
Although the above documents provide some catalysts for selective oxidation of methacrolein and methods for preparing the same, there are still problems that the preparation processes all adopt liquid phase reaction, the difficulty of parameter control is high, and the conversion rate of methacrolein and the selectivity of methacrylic acid of the prepared catalysts are insufficient, so that it is still of great importance to develop a catalyst having high methacrolein conversion rate and methacrylic acid selectivity, and a preparation method in which the parameters of the catalyst preparation process are easily controlled.
Disclosure of Invention
The invention aims to provide a catalyst for preparing methacrylic acid by selectively oxidizing methacrolein, a preparation method and application thereof; compared with the traditional phosphomolybdic vanadate heteropoly acid salt catalyst, the catalyst provided by the invention has higher activity for catalyzing the selective oxidation of methacrolein to prepare methacrylic acid, and in the process of catalyzing the selective oxidation of methacrolein to prepare methacrylic acid, the highest selectivity of methacrolein to methacrylic acid can reach 93% when the conversion rate of methacrolein is 90%.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst for the selective oxidation of methacrolein to methacrylic acid, said catalyst having the composition PaMobVcXxYyZz1HhOg1-Zz2Og2。
Wherein X is at least two of sodium, potassium, rubidium, or cesium, and illustratively includes a combination of potassium and sodium, a combination of potassium and cesium, a combination of sodium and cesium, or a combination of potassium, sodium, rubidium, and cesium, or the like; y is at least one of calcium, magnesium, chromium, manganese, iron, cobalt, copper, nickel, zinc, aluminum, silicon, germanium, antimony, bismuth, lanthanum, or cerium, and illustratively includes mixtures of calcium, magnesium, copper, calcium, and magnesium, chromium and manganese, iron and cobalt, copper and nickel, zinc and aluminum, silicon and germanium, antimony and bismuth, or lanthanum and cerium, and the like; z is titanium and/or zirconium.
Y is at least one of calcium, magnesium, chromium, manganese, iron, cobalt, copper, nickel, zinc, aluminum, silicon, germanium, antimony, bismuth, lanthanum or cerium, and the elements added into the catalyst can play a positive role in adjusting the oxidation-reduction property and acidity of the catalyst, adjusting the microstructure and specific surface area of the catalyst and the like.
Z is titanium and/or zirconium, and has positive effects on the activity and stability of the final catalyst.
a is 1.0-1.2, such as 1.0, 1.1 or 1.2, etc., b is 10-12, such as 10, 11 or 12, etc., c is 0.1-2, such as 0.1, 0.5, 0.7, 1, 1.5 or 2, etc., x is 0.01-3, such as 0.01, 0.1, 1, 2 or 3, etc., y is 0.01-0.5, such as 0.01, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., z1 is 0.001-0.5, such as 0.001, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., z2 is 0.001-0.5, such as 0.001, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., h is the atomic ratio of hydrogen needed to satisfy electrical neutrality, g and g is the atomic ratio of oxygen needed to satisfy 2 g.
Compared with the traditional phosphomolybdic vanadate heteropoly acid salt catalyst, the catalyst has higher activity in the process of catalyzing the selective oxidation of methacrolein to prepare methacrylic acid, and in the process of catalyzing the selective oxidation of methacrolein to prepare methacrylic acid, the selectivity of methacrolein to methacrylic acid can reach 93 percent at most when the conversion rate of methacrolein is 90 percent, thereby meeting the requirements of actual industrial production.
Preferably, the composition of the catalyst is P1.1Mo11V1XxYyZz1HhOg1-Zz2Og2。
Preferably, Y is any one of copper, cobalt, nickel or bismuth or a mixture of at least two of them, including a mixture of copper and cobalt, a mixture of copper and nickel, a mixture of copper and bismuth, or a mixture of copper, cobalt and nickel, and the like.
In a second aspect, the present invention provides a process for the preparation of a catalyst as described in the first aspect, the process comprising the steps of:
(1) adding a phosphorus source, a molybdenum source and a vanadium source into water, and reacting to obtain a first solution;
(2) adding an alkali source containing nitrogen elements into the first solution, reacting to obtain a second solution, and drying to obtain a first solid;
(3) mixing the first solid, the X source, the Y source and the Z source with any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea to obtain a second solid;
(4) and roasting the second solid in a nitrogen and/or air atmosphere to obtain the catalyst.
According to the preparation method of the catalyst, phosphomolybdic acid with a Keggin structure as a main body structure is prepared in the step (1), an alkali source containing nitrogen elements is added in the step (2), the physicochemical property of the first solution is adjusted, and NH can occur in the subsequent roasting process of preparation of the alkali source containing nitrogen elements4 +The decomposition reaction has the functions of reducing and adjusting the acidity of the catalyst, and is beneficial to finally forming a microstructure with higher catalytic activity; and (3) solid-phase reaction is adopted, specific cations and specific oxides are introduced into phosphomolybdic acid, and any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea is added, so that the performance of the prepared catalyst can be promoted to be improved. Compared with the traditional process of preparing the catalyst by the liquid phase reaction, the solid phase reaction is easier to realize process control and easier to regulate and control the performance of the catalyst, so that the catalyst with higher activity is obtained; the conditions of the roasting process in the step (4) have great influence on the solid-phase reaction process, so that the solid-phase reaction can be adjusted by adjusting the roasting conditions, and the catalyst with optimal catalytic activity is obtained. Compared with the traditional liquid phase reaction, the solid phase reaction reduces the influence caused by incomplete reactant precipitation, and improves the preparation efficiency of the catalyst and the activity of the prepared catalyst. The method of the invention combines the steps, so that the activity of the prepared catalyst and the selectivity of methacrylic acid are obviously improved.
Preferably, the phosphorus source of step (1) comprises phosphoric acid.
Preferably, the molybdenum source of step (1) comprises molybdenum oxide.
Preferably, the source of vanadium of step (1) comprises vanadium oxide.
Preferably, the temperature of the reaction in step (1) is 60-120 ℃, such as 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, etc.
Preferably, the reaction time in step (1) is 2-10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc.
Preferably, stirring is also included in the reaction process of the step (1).
Preferably, the nitrogen-containing alkaline source in step (2) includes any one or a mixture of at least two of ammonia water, ammonium carbonate, ammonium bicarbonate or urea, and the mixture exemplarily includes a mixture of ammonia water and ammonium carbonate, a mixture of ammonium bicarbonate and urea, or a mixture of ammonia water and urea, and the like.
Preferably, the nitrogen-containing alkaline source of step (2) is added in an amount such that the molar ratio of nitrogen element to phosphorus element is 0.001-2, e.g., 0.001, 0.01, 0.1, 1, 1.5, or 2, etc.
Preferably, the temperature of the reaction in step (2) is 10-100 deg.C, such as 10 deg.C, 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C or 100 deg.C.
Preferably, the reaction time in step (2) is 1-20h, such as 1h, 3h, 5h, 7h, 10h, 15h, 17h or 20h, etc.
Preferably, the drying method in step (2) comprises spray drying or evaporation drying.
Preferably, the X source in step (3) comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing X element; the mixture exemplarily includes a mixture of a nitrate containing the element X and a carbonate containing the element X, a mixture of a nitrate containing the element X and a hydroxide containing the element X, or a mixture of a carbonate containing the element X and a hydroxide containing the element X, and the like.
Preferably, the Y source in step (3) comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing Y element; the mixture exemplarily includes a mixture of a nitrate containing the Y element and a carbonate containing the Y element, a mixture of a nitrate containing the Y element and a hydroxide containing the Y element, or a mixture of a carbonate containing the Y element and a hydroxide containing the Y element, and the like.
Preferably, the Z source in step (3) comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing Z element; the mixture exemplarily includes a mixture of a nitrate containing the Z element and a carbonate containing the Z element, a mixture of a nitrate containing the Z element and a hydroxide containing the Z element, or a mixture of a nitrate containing the Z element and an oxide containing the Z element, and the like.
Preferably, the mixing method of step (3) comprises dry mixing or wet mixing.
Preferably, the mass of any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea added in step (3) is 0.001-2% of the mass of the second solid, such as 0.001%, 0.01%, 0.1%, 0.5%, 1%, 1.5% or 2% and the like.
Preferably, the temperature of the calcination in the step (4) is 250-.
The roasting condition of the invention has great influence on the solid phase reaction, when the roasting temperature is 250-400 ℃, the activity and the selectivity of the obtained catalyst are both high, the roasting temperature is preferably 350-360 ℃, and the selectivity of the obtained catalyst on the methacrylic acid can reach 93 percent at most when the conversion rate of the methacrolein of the obtained catalyst is 90 percent.
Preferably, the roasting time in the step (4) is 3-24h, such as 3h, 6h, 9h, 12h, 15h, 16h, 20h, 22h or 24h, etc.
Preferably, the second solid is shaped before the firing in step (4).
Preferably, the calcined product is shaped after the calcination in the step (4).
Preferably, the forming method includes any one of tablet forming, extrusion molding or coating.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) adding phosphoric acid, molybdenum oxide and vanadium oxide into deionized water, and stirring and reacting for 2-10h at 60-120 ℃ to obtain a first solution;
(2) adding an alkaline source containing nitrogen elements into the first solution, reacting for 1-20h at 10-100 ℃ to obtain a second solution, and then drying to obtain a first solid, wherein the alkaline source containing nitrogen comprises any one or a mixture of at least two of ammonia water, ammonium carbonate, ammonium bicarbonate or urea, and the adding amount of the alkaline source containing nitrogen is 0.001-2 mol ratio of the nitrogen elements to the phosphorus elements;
(3) mixing a first solid, an X source, a Y source, a Z source and any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea to obtain a second solid, wherein the X source comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing an X element; the Y source comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing Y element; the Z source comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing Z element; the mass of any one or the mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea is 0.001-2% of the mass of the second solid;
(4) and roasting the second solid for 3-24h at the temperature of 250-400 ℃ in the atmosphere of nitrogen and/or air to obtain the catalyst.
In a third aspect, the present invention also provides the use of a catalyst as described in the first aspect for catalyzing the selective oxidation of methacrolein to methacrylic acid.
Preferably, the catalytic process is carried out in a fixed bed reactor.
Preferably, the concentration of methacrolein in the catalytic process is 1-10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., the temperature of the catalytic reaction is 250-400 ℃, such as 250 ℃, 270 ℃, 300 ℃, 350 ℃, 360 ℃, 370 ℃, or 400 ℃, etc., the pressure gauge pressure of the catalytic reaction is 0-0.1MPa, such as 0.01MPa, 0.03MPa, 0.05MPa, 0.07MPa, or 0.1MPa, etc., and the space velocity under standard conditions is 600-1800h-1E.g. 600h-1、700h-1、800h-1、900h-1、1000h-1、1200h-1、1500h-1、1600h-1Or 1800h-1And the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional phosphomolybdic vanadate heteropoly acid catalyst, the activity of the catalyst for catalyzing the selective oxidation of methacrolein to prepare methacrylic acid has higher activity, and in the process of catalyzing the selective oxidation of methacrolein to prepare methacrylic acid, when the conversion rate of methacrolein is 90%, the selectivity of methacrolein to methacrylic acid can reach 93% at most, thereby meeting the requirements of actual industrial production;
(2) compared with the traditional liquid phase reaction, the solid phase reaction adopted by the preparation method of the catalyst reduces the influence caused by incomplete reactant precipitation, and improves the preparation efficiency of the catalyst and the activity of the prepared catalyst;
(3) the method of the invention obtains the optimal catalyst preparation condition by controlling the conditions (including temperature) of the solid phase reaction in the preparation process, so that the activity of the prepared catalyst is obviously improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the catalyst comprises the following steps:
(1) 2643.5g of molybdenum oxide and 167.1g of vanadium oxide are added into 31kg of deionized water, 233g of phosphoric acid (with the concentration of 85%) is diluted into 15% phosphoric acid, a phosphoric acid solution is slowly added into a solution containing molybdenum oxide and vanadium oxide under the condition of stirring, after the phosphoric acid is added, the temperature is raised to 100 ℃, and stirring reaction is continued for 6 hours to obtain a first solution;
(2) adding 12.5g of ammonium carbonate into the first solution, stirring and reacting for 1h at 25 ℃ to obtain a second solution, and then carrying out spray drying to obtain a first solid;
(3) mixing the first solid, 333.2g of cesium nitrate, 4.9g of sodium nitrate, 42.5g of copper nitrate, 28.7g of bismuth nitrate, 23.3g of zirconium oxide and 29.3g of ammonium carbonate to obtain a second solid;
(4) and adding graphite into the second solid, tabletting and forming, and roasting at 360 ℃ in an air atmosphere for 16h to obtain the catalyst.
Example 2
This example is different from example 1 in that the firing atmosphere in step (4) was replaced by a mixed gas of air and nitrogen in which the oxygen concentration was 13%, and the other conditions were completely the same as those in example 1.
Example 3
This example is different from example 1 in that the baking atmosphere in step (4) is replaced by a mixed gas of air and nitrogen, the concentration of oxygen in the mixed gas is 5%, and other conditions are completely the same as those in example 1.
Example 4
This example is different from example 1 in that the baking atmosphere in step (4) is replaced by a mixed gas of air and nitrogen, the concentration of oxygen in the mixed gas is 2%, and other conditions are completely the same as those in example 1.
Example 5
This example is different from example 1 in that the firing atmosphere in step (4) was replaced with nitrogen gas from air, and other conditions were exactly the same as those in example 1.
Example 6
The preparation method of the catalyst comprises the following steps:
(1) identical to step (1) of example 1;
(2) adding 20g of ammonium carbonate into the first solution, stirring and reacting for 1h at 25 ℃ to obtain a second solution, and then carrying out spray drying to obtain a first solid;
(3) mixing the first solid, 251.4g of cesium carbonate, 4.3g of potassium carbonate, 18.1g of copper nitrate, 25.4g of cobalt nitrate, 28.2g of nickel nitrate, 5.8g of titanium oxide and 29.3g of ammonium bicarbonate to obtain a second solid;
(4) and adding graphite into the second solid, tabletting and forming, and roasting at 360 ℃ in an air atmosphere for 16h to obtain the catalyst.
Example 7
This example was conducted under exactly the same conditions as in example 6 except that the calcination temperature in step (4) in example 6 was changed from 360 ℃ to 370 ℃.
Example 8
This example was conducted under exactly the same conditions as in example 6 except that the calcination temperature in step (4) in example 6 was changed from 360 ℃ to 350 ℃.
Example 9
This example was conducted under exactly the same conditions as in example 6 except that the calcination temperature in step (4) in example 6 was changed from 360 ℃ to 250 ℃.
Example 10
This example was conducted under exactly the same conditions as in example 6 except that the calcination temperature in step (4) in example 6 was changed from 360 ℃ to 400 ℃.
Example 11
The preparation method of the catalyst comprises the following steps:
(1) identical to step (1) of example 1;
(2) adding 20g of ammonium carbonate into the first solution, stirring and reacting for 1h at 25 ℃ to obtain a second solution, and then carrying out spray drying to obtain a first solid;
(3) the first solid, 251.4g of cesium carbonate, 4.3g of potassium carbonate, 18.1g of copper nitrate, 25.4g of cobalt nitrate, 28.2g of nickel nitrate, 10.2g of zirconium nitrate, 2.5g of titanium oxide and 29.3g of ammonium bicarbonate were mixed, and 100g of a mixture of 1: 1, to obtain a second solid;
(4) and drying the second solid at 100 ℃ in an air atmosphere for 10h, then roasting at 360 ℃ in the air atmosphere for 16h, and tabletting and molding the obtained solid product to obtain the catalyst.
Comparative example 1
This comparative example is different from example 1 in that cesium nitrate and sodium nitrate were not added in step (3), and other conditions were completely the same as those in example 1.
Comparative example 2
This comparative example is different from example 1 in that no sodium nitrate was added in step (3) and the other conditions were completely the same as those in example 1.
Comparative example 3
This comparative example is different from example 1 in that copper nitrate and bismuth nitrate were not added in step (3) and other conditions were completely the same as those in example 1.
Comparative example 4
This comparative example is different from example 1 in that zirconia was not added in step (3) and other conditions were completely the same as those in example 1.
Comparative example 5
This comparative example is different from example 1 in that ammonium carbonate is not added in step (2) and step (3), and other conditions are completely the same as those in example 1.
Comparative example 6
This comparative example is different from example 1 in that zirconia was not added in step (3) and other conditions were completely the same as those in example 1.
Comparative example 7
The preparation process of the catalyst of the comparative example was carried out using a liquid phase process, which was as follows:
(1) the preparation process is completely the same as that of the step (1) in the example 1;
(2) 333.2g of cesium nitrate, 4.9g of sodium nitrate, 42.5g of copper nitrate, 28.7g of bismuth nitrate, 23.3g of zirconium oxide and 41.8g of ammonium carbonate are added into the product obtained in the step (1), mixed and reacted, and then spray-dried;
(3) and (3) adding graphite into the product obtained in the step (2), tabletting and forming, and roasting at 360 ℃ for 16h in an air atmosphere to obtain the catalyst.
The activity of the catalysts prepared in examples 1 to 11 and comparative examples 1 to 7 for preparing methacrylic acid by catalyzing selective oxidation of methacrolein was tested as follows:
crushing and screening the prepared catalyst, weighing 0.8g of the catalyst with 30-40 meshes, and filling the catalyst into a reaction tube with the inner diameter of 6 mm; reaction gas composition: the volume concentration of the methacrolein is 4%; the oxygen-aldehyde ratio was 2.5,the carrier gas is nitrogen, and the volume space velocity under the standard condition is 1350h-1The reaction temperature was 330 ℃ and the reaction pressure was normal pressure.
The catalytic activity data of the catalysts prepared in examples 1 to 11 and comparative examples 1 to 7 are shown in table 1.
TABLE 1
As can be seen from the above table, when the conversion rate of methacrolein of the catalyst of the present invention is 90%, the selectivity to methacrylic acid can be up to 93%, and it can be seen from comparative examples 1 to 5 that the oxygen content of the calcination atmosphere is properly reduced, the conversion rate of methacrolein is improved, the selectivity is reduced, the optimum treatment atmosphere is a mixed gas of air and nitrogen, and the oxygen concentration in the mixed gas is 13%; as can be seen from comparison of examples 6-10, the optimum calcination temperature is 350-. Comparing examples 6 and 11, it can be seen that dry mixing and wet mixing are used in step (3) of the preparation process, and the obtained catalyst has higher activity and the activity of the wet mixing is higher.
As can be seen by comparing example 1 with comparative examples 1-2, the activity of the catalyst is obviously reduced without adding cesium nitrate and sodium nitrate or adding sodium nitrate in the preparation process; as can be seen by comparing example 1 with comparative example 3, the activity and selectivity of the catalyst are obviously reduced without adding copper nitrate and bismuth nitrate in the preparation process; as can be seen by comparing example 1 with comparative example 4, the catalytic activity and selectivity of the catalyst are obviously reduced without adding zirconia in the preparation process; as can be seen by comparing example 1 with comparative example 5, the activity of the catalyst prepared without adding ammonium carbonate is significantly deteriorated; comparing example 1 with comparative example 6, it can be seen that, compared with the method of not adding the element Z in the preparation process, the method of adding the element Z in the preparation process of the catalyst of the present invention obviously improves the activity of the catalyst; as can be seen by comparing example 1 with comparative example 7, the activity of the catalyst prepared by the solid phase reaction of the present invention is significantly better than that of the catalyst prepared by the pure liquid phase method. Therefore, the catalyst and the preparation method thereof have good application prospects.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (30)
1. A catalyst for preparing methacrylic acid by selectively oxidizing methacrolein is characterized in that the composition of the catalyst is PaMobVcXxYyZz1HhOg1-Zz2Og2；
Wherein X is at least two of sodium, potassium, rubidium or cesium; y is at least one of calcium, magnesium, chromium, manganese, iron, cobalt, copper, nickel, zinc, aluminum, silicon, germanium, antimony, bismuth, lanthanum or cerium; z is titanium and zirconium;
a is 1.0 to 1.2, b is 10 to 12, c is 0.1 to 2, x is 0.01 to 3, y is 0.01 to 0.5, z1 is 0.001 to 0.5, z2 is 0.001 to 0.5, h is the atomic ratio of hydrogen required to satisfy electroneutrality, g1 and g2 are the atomic ratio of oxygen required to satisfy valence;
the preparation method of the catalyst comprises the following steps:
(1) adding a phosphorus source, a molybdenum source and a vanadium source into water, and reacting to obtain a first solution;
(2) adding an alkali source containing nitrogen elements into the first solution, reacting to obtain a second solution, and drying to obtain a first solid;
(3) mixing the first solid, the X source, the Y source and the Z source with any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea to obtain a second solid;
(4) roasting the second solid in nitrogen and/or air atmosphere to obtain the catalyst;
the alkali source containing the nitrogen element in the step (2) comprises any one or a mixture of at least two of ammonia water, ammonium carbonate, ammonium bicarbonate or urea.
2. The catalyst of claim 1, wherein the catalyst has a composition of P1.1Mo11V1XxYyZz1HhOg1-Zz2Og2。
3. The catalyst of claim 1, wherein Y is any one or a mixture of at least two of copper, cobalt, nickel, or bismuth.
4. A method for preparing a catalyst according to any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) adding a phosphorus source, a molybdenum source and a vanadium source into water, and reacting to obtain a first solution;
(2) adding an alkali source containing nitrogen elements into the first solution, reacting to obtain a second solution, and drying to obtain a first solid;
(3) mixing the first solid, the X source, the Y source and the Z source with any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea to obtain a second solid;
(4) roasting the second solid in nitrogen and/or air atmosphere to obtain the catalyst;
the alkali source containing the nitrogen element in the step (2) comprises any one or a mixture of at least two of ammonia water, ammonium carbonate, ammonium bicarbonate or urea.
5. The method of claim 4, wherein the phosphorus source of step (1) comprises phosphoric acid.
6. The method of claim 4, wherein the molybdenum source of step (1) comprises molybdenum oxide.
7. The method of claim 4, wherein the source of vanadium of step (1) comprises vanadium oxide.
8. The process of claim 4, wherein the temperature of the reaction of step (1) is 60-120 ℃.
9. The method of claim 4, wherein the reaction time in step (1) is 2 to 10 hours.
10. The method of claim 4, wherein the reaction of step (1) further comprises stirring.
11. The method according to claim 4, wherein the alkali source containing nitrogen element in the step (2) is added in an amount such that the molar ratio of nitrogen element to phosphorus element is 0.001 to 2.
12. The method of claim 4, wherein the temperature of the reaction of step (2) is 10-100 ℃.
13. The method of claim 4, wherein the reaction time of step (2) is 1-20 hours.
14. The method of claim 4, wherein the drying of step (2) comprises spray drying or evaporative drying.
15. The method of claim 4, wherein the X source in step (3) comprises a mixture of at least two or any one of nitrates, carbonates, hydroxides or oxides of the X element.
16. The method of claim 4, wherein the Y source in step (3) comprises a mixture of at least two or any one of nitrates, carbonates, hydroxides or oxides of the Y element.
17. The method of claim 4, wherein the Z source of step (3) comprises a mixture of at least two or any of nitrates, carbonates, hydroxides or oxides of the Z element.
18. The method of claim 4, wherein the mixing of step (3) comprises dry or wet mixing.
19. The method of claim 4, wherein the mass of any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea added in step (3) is 0.001-2% of the mass of the second solid.
20. The method as claimed in claim 4, wherein the temperature of the calcination in the step (4) is 250-400 ℃.
21. The method as claimed in claim 20, wherein the temperature of the calcination in the step (4) is 350-.
22. The method as claimed in claim 21, wherein the temperature of the calcination in the step (4) is 350-.
23. The method of claim 4, wherein the calcination time in step (4) is 3-24 hours.
24. The method of claim 4, wherein the second solid is shaped prior to the firing of step (4).
25. The method of claim 4, wherein the fired product is shaped after the firing of step (4).
26. The method of claim 25, wherein the forming comprises any one of tablet forming, extrusion, or coating.
27. The method of claim 4, wherein the method comprises the steps of:
(1) adding phosphoric acid, molybdenum oxide and vanadium oxide into deionized water, and stirring and reacting for 2-10h at 60-120 ℃ to obtain a first solution;
(2) adding an alkali source containing nitrogen elements into the first solution, reacting for 1-20h at 10-100 ℃ to obtain a second solution, and then drying to obtain a first solid, wherein the alkali source containing the nitrogen elements comprises any one or a mixture of at least two of ammonia water, ammonium carbonate, ammonium bicarbonate or urea, and the adding amount of the alkali source containing the nitrogen elements is 0.001-2 of the molar ratio of the nitrogen elements to the phosphorus elements;
(3) mixing a first solid, an X source, a Y source, a Z source and any one or a mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea to obtain a second solid, wherein the X source comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing an X element; the Y source comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing Y element; the Z source comprises any one or a mixture of at least two of nitrate, carbonate, hydroxide or oxide containing Z element; the mass of any one or the mixture of at least two of ammonium carbonate, ammonium bicarbonate or urea is 0.001-2% of the mass of the second solid;
(4) and roasting the second solid for 3-24h at the temperature of 250-400 ℃ in the atmosphere of nitrogen and/or air to obtain the catalyst.
28. Use of a catalyst according to any one of claims 1 to 3 for catalysing the selective oxidation of methacrolein to methacrylic acid.
29. Use of the catalyst according to claim 28, wherein the catalysed process is carried out in a fixed bed reactor.
30. The use of the catalyst as claimed in claim 28, wherein the volume concentration of methacrolein in the catalytic process is 1-10%, the catalytic reaction temperature is 250-400 ℃, the catalytic reaction pressure is 0-0.1MPa, and the volume space velocity under the standard condition is 600-1800h-1。
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| CN103945938A (en) * | 2011-11-17 | 2014-07-23 | 日本化药株式会社 | Catalyst for production of methacrylic acid and method for producing methacrylic acid using same |
| CN104001542A (en) * | 2014-06-09 | 2014-08-27 | 中国科学院过程工程研究所 | Preparation method of catalyst for preparing methacrylic acid through oxidation of methylacrolein |
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| CN104302391A (en) * | 2012-05-18 | 2015-01-21 | 日本化药株式会社 | Catalyst for use in production of methacrylic acid, method for producing said catalyst, and method for producing methacrylic acid using said catalyst |
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