CN110142063B - Catalyst for preparing methacrylic acid by selective oxidation of isobutane and preparation method thereof - Google Patents
Catalyst for preparing methacrylic acid by selective oxidation of isobutane and preparation method thereof Download PDFInfo
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- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- 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
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Abstract
The invention aims to provide a catalyst for preparing methacrylic acid by selective oxidation of isobutane and a preparation method thereof, wherein the catalyst is phosphomolybdic heteropoly acid with different vanadium-containing precursors doped in Keggin structures and secondary structures, and the general formula of the phosphomolybdic heteropoly acid is CsxVyPMo11VO40Wherein x is 0 to 2.5 and y is 0 to 0.5. The preparation method comprises the following steps: different vanadium-containing precursors are doped into a Keggin structure or a secondary structure of the cesium phosphomolybdate by adopting a precipitation method, a complexation method and the like to prepare CsxVyPMo11VO40And (3) calcining a catalyst (x is 0-2.5 and y is 0-0.5) powder material at 300 ℃ for 3-10 hours in different atmospheres, and crushing the calcined material into 20-60 meshes to obtain the catalyst. The synthesized catalyst shows higher methacrylic acid selectivity and high stability in a hydrocarbon-rich system, and shows a certain industrial application prospect. Catalyst preparation method repetitionGood in performance and simple in synthesis process.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a catalyst for preparing methacrylic acid by selective oxidation of isobutane and a preparation method thereof.
Background
The methacrylic acid product chain is a high-technology and high-added-value product and has wide market application prospect. Methyl Methacrylate (MMA) synthesized therefrom is mainly used for the synthesis of organic glass and is an important resin monomer. In recent years, MMA is also used in high-tech fields such as optical fibers, optical disks, and lenses.
At present, about 83 percent of methacrylic acid in the world is produced by an acetone cyanohydrin process developed by Rohm & Haas company, HCN with high toxicity and high corrosivity is used as a raw material, and a large amount of NH4HSO4 which is difficult to treat is generated as a byproduct, so that serious health and environmental problems are caused, and the development mode of green chemistry at present is not met. In all newly developed methacrylic acid production processes, the process for producing methacrylic acid by oxidizing isobutane as a raw material in one step shows strong competitiveness due to low price of the raw material and relatively simple production flow. Particularly, China has abundant C4 resources, and oilfield butane usually contains 20-40% of isobutane. However, the chemical utilization rate of C4 hydrocarbon in China is only 7.8%, which is far behind developed countries, and most of the C4 hydrocarbon is burned as fuel, thus causing huge waste of resources.
At present, aiming at selective oxidation reaction of isobutane, particularly in a hydrocarbon-rich system with steam, the activity or product selectivity of a catalyst reported in documents or patents is not ideal, the selectivity of methacrylic acid is lower than 60%, and the conversion rate of isobutane is not more than 15%. The patent provides a cesium phosphomolybdate catalyst with a proper amount of V element doped in the primary structure and the secondary structure of heteropoly compound, and the selectivity of methacrylic acid on the catalyst is obviously improved.
Disclosure of Invention
The invention aims to provide a catalyst for preparing methacrylic acid by selective oxidation of isobutane and a preparation method thereof, and the specific technical scheme is as follows:
a catalyst for preparing methacrylic acid by selective oxidation of isobutane is phosphomolybdic heteropoly acid with different vanadium-containing precursors doped in Keggin structure and secondary structureSalts of the general formula CsxVyPMo11VO40Wherein x is 0 to 2.5 and y is 0 to 0.5.
The doped vanadium-containing precursor is mainly vanadyl sulfate, vanadyl oxalate, vanadium acetylacetonate and V2O5Or one or more of vanadyl nitrate.
A preparation method of a catalyst for preparing methacrylic acid by selective oxidation of isobutane comprises the following steps: (1) precipitating and complexing different vanadium-containing precursors (vanadyl sulfate, vanadyl oxalate, vanadium acetylacetonate and V)2O5Vanadyl nitrate, etc.) into the Keggin structure (primary structure) or secondary structure (counter cation) of cesium phosphomolybdate to prepare CsxVyPMo11VO40The catalyst, wherein x is 0-2.5 and y is 0-0.5.
Preparing H with the concentration of 0.01-0.05 mol/L3PMo12O40Or H4PMo11VO40Heating, refluxing and stirring deionized water solution at 50-100 ℃, and then adding vanadium-containing precursor (V/phosphomolybdate acid radical stoichiometric ratio is 0.1-0.5) into H3PMo12O40Or H4PMo11VO40Continuously heating, refluxing and stirring the solution for 30-100 min, and finally adding the Cs2CO3Adding the solution (the stoichiometric ratio of the Cs/phosphomolybdate radical is 0.1-0.25) into the mixed solution to generate a precipitate, heating, refluxing and stirring at 50-100 ℃ for 1-10 h, and completely evaporating the solution by adopting a rotary evaporation method to obtain CsxVyPMo11VO40A catalyst.
(2) The prepared CsxVyPMo11VO40Catalyst in air, N2Or H2Roasting the mixture for 3 to 10 hours at 300 ℃ under different atmospheres such as a/Ar mixed gas and the like, and crushing the mixture into 20 to 60 meshes to prepare the catalyst.
The application of a catalyst for preparing methacrylic acid by selective oxidation of isobutane comprises the following steps: the reaction temperature is 320-400 ℃, the reaction pressure is normal pressure, and the propane reaction space velocity is 700-2000L Kg-1h-1。
The catalyst synthesized by the method has high methacrylic acid selectivity and high stability in a hydrocarbon-rich system, and has a certain industrial application prospect.
The catalyst provided by the invention is simple to prepare, low in cost and good in repeatability, and shows good catalytic activity, product selectivity and excellent catalytic stability in the reaction of preparing methacrylic acid by selective oxidation of isobutane in the presence of steam and in a hydrocarbon-rich system.
Drawings
FIG. 1 is a Fourier-IR spectrum of a catalyst,
FIG. 2 is a Raman spectrum of the catalyst,
FIG. 3 is a UV-visible diffuse reflectance spectrum of the catalyst.
Detailed Description
In the reaction of preparing methacrylic acid by selective oxidation of isobutane, the reaction product is divided into gas phase and liquid phase. The gas phase product comprises CO and CO2、C2H6And C2H4. The liquid phase product comprises target product methacrylic acid, byproduct acetic acid, methacrolein, acetone and acrylic acid.
The conversion and selectivity as well as the yield were calculated as follows:
yield (%). conversion. times. selectivity. times.100
(Mi: the number of moles of a product; ni: the number of carbon atoms contained in a molecule of a product)
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1
Adopts vanadyl sulfate as vanadium-containing precursor to prepare Cs by precipitation method2.0V0.3PMo12O40Catalyst: preparing H with the concentration of 0.04mol/L4PMo11O40Deionized water solution, heating at 80 deg.C under reflux, stirring, and adding vanadyl sulfate to H4PMo12O40Heating, refluxing and stirring the solution (the stoichiometric ratio of V/phosphomolybdate radical is 0.3) for 30min, and finally adding Cs2CO3Adding the solution (the stoichiometric ratio of Cs/phosphomolybdate radical is 2.0) into the mixed solution to generate precipitate, heating and refluxing at 80 ℃ for 3h, completely evaporating the solution by adopting a rotary evaporation method, and roasting the obtained powder at 300 ℃ for 3h in an air atmosphere.
Fourier-Infrared Spectroscopy (FIG. 1b)1035cm-1Vibration peak at 850cm, Raman spectrum (FIG. 2b)-1The characterization results of vibration peaks and the like show that the V species enter the secondary structure of the cesium phosphomolybdate, and the characterization results of X-ray photoelectron spectroscopy (Table 1) show that the Mo on the surface of the catalyst is5+/Mo5++Mo6+And V4+/V4++V5+The ratio is moderate. The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, contact time 4.8s, isobutane conversion 8.8%, methacrylic acid selectivity 50.8% (table 2).
Example 2
Adopts vanadyl sulfate as vanadium-containing precursor to prepare Cs by precipitation method2.0V0.5PMo12O40Catalyst: preparing H with the concentration of 0.03mol/L4PMo11O40Deionized water solution, heating at 100 deg.C under reflux, stirring, and adding vanadyl sulfate to H4PMo12O40Heating, refluxing and stirring the solution (the stoichiometric ratio of V/phosphomolybdate radical is 0.5) for 50min, and finally adding Cs2CO3Adding the solution (the stoichiometric ratio of Cs/phosphomolybdate radical is 2.0) into the above mixed solution to generate precipitate, heating at 50 deg.C under reflux and stirring for 10 hr, completely evaporating the solution by rotary evaporation method to obtain powderRoasting at 300 deg.c for 3 hr in air atmosphere.
The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, the contact time is 4.8s, the conversion rate of the isobutane is 5.7 percent, and the selectivity of the methacrylic acid is 47.3 percent.
Example 3
Adopts vanadyl oxalate as vanadium-containing precursor to prepare Cs by precipitation method2.0V0.3PMo12O40The catalyst is calcined for 3 hours at 300 ℃ in an air atmosphere.
The specific procedure was the same as in example 1.
Fourier-Infrared Spectroscopy (FIG. 1c)1035cm-1Vibration peak at 850cm, Raman spectrum (FIG. 2a)-1The characterization results of the vibration peak and the like show that the V species enter the secondary structure of the cesium phosphomolybdate, and Mo is 650-750 nm in the ultraviolet-visible diffuse reflection spectrum (figure 3a)6+→Mo5+The results of the characterization of the electron exchange peak and the X-ray photoelectron spectrum (Table 1) show that the catalyst contains Mo in a reduced state5+High content of Mo in catalyst6+Is excessively reduced into Mo by vanadyl oxalate precursor5+The lattice oxygen in the catalyst is consumed in excess. The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, the contact time is 4.8s, the conversion rate of the isobutane is 6.3 percent, and the selectivity of the methacrylic acid is 50.4 percent.
Example 4
Adopts vanadium acetylacetonate as vanadium-containing precursor, and prepares Cs by precipitation method2.0V0.3PMo12O40The catalyst is calcined for 3 hours at 300 ℃ in an air atmosphere. The specific procedure was the same as in example 1.
Fourier-Infrared Spectroscopy (FIG. 1a)1080cm-1Vibration peak at, Raman spectrum (FIG. 2c)1032cm-1The characterization results of vibration peaks and the like show that the V species enter the primary structure of the cesium phosphomolybdate, and the characterization results of X-ray photoelectron spectroscopy (Table 1) show that the V species on the surface of the catalyst4+/V4++V5+Lower, V5+The content is higher. The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, the contact time is 4.8s, the conversion rate of the isobutane is 16.3 percent, and the selectivity of the methacrylic acid is 35.4 percent.
Example 5
Adopts vanadyl sulfate as vanadium-containing precursor to prepare Cs by precipitation method2.0V0.3PMo11VO40Catalyst: preparing H with the concentration of 0.05mol/L4PMo11VO40Deionized water solution, heating at 50 deg.C under reflux, stirring, and adding vanadyl sulfate to H4PMo11VO40Heating, refluxing and stirring the solution (the stoichiometric ratio of V/phosphomolybdate radical is 0.3) for 100min, and finally adding Cs2CO3Adding the solution (the stoichiometric ratio of Cs/phosphomolybdate radical is 2.0) into the mixed solution to generate precipitate, heating and refluxing at 100 ℃ for stirring for 1h, completely evaporating the solution by adopting a rotary evaporation method, and roasting the obtained powder at 300 ℃ for 3h in an air atmosphere.
Fourier-Infrared Spectroscopy (FIG. 1d)1035cm-1And 1080cm-1Vibration peak at 850cm, Raman spectrum (FIG. 2e)-1And 1032cm-1The characterization results of vibration peaks and the like show that V species enter into the primary structure and the secondary structure of the cesium phosphomolybdate, and the characterization results of an X-ray photoelectron spectrum (Table 1) show that Mo on the surface of the catalyst5+/Mo5++Mo6+And V4+/V4++V5+The ratio is moderate. The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, contact time 4.8s, isobutane conversion 18.9%, methacrylic acid selectivity 67.3% (table 2).
Example 6
Adopts vanadyl sulfate as vanadium-containing precursor to prepare Cs by precipitation method2.0V0.3PMo12O40Catalyst and in H2Roasting at 300 ℃ for 3h in the atmosphere of/Ar mixed gas. Is prepared byThe procedure is as in example 1.
The characterization results of Fourier-infrared spectroscopy, Raman spectroscopy and the like show that V species enter the secondary structure of cesium phosphomolybdate, and the characterization results of X-ray photoelectron spectroscopy (Table 1) show that Mo in the reduction state of the surface of the catalyst5+High content of Mo in catalyst6 +Quilt H2Over-reduction of the/Ar gas mixture to Mo5+The lattice oxygen in the catalyst is consumed in excess. The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, contact time 4.8s, isobutane conversion 5.8%, methacrylic acid selectivity 53.4% (table 2).
Example 7
Preparation of Cs by precipitation method without vanadium-containing precursor doping2.0HPMo12O40The catalyst is calcined for 3 hours at 300 ℃ in an air atmosphere. The specific procedure was the same as in example 1.
The characterization result of the X-ray photoelectron spectrum (Table 1) shows that Mo is on the surface of the catalyst5+/Mo5++Mo6+And V4+/V4++V5+The ratio is moderate. The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, contact time 4.8s, isobutane conversion 8.5%, methacrylic acid selectivity 43.6% (table 2).
Example 8
Adopts vanadyl sulfate as vanadium-containing precursor to prepare Cs by a complexation method2.0V0.3PMo12O40Catalyst: preparing H with the concentration of 0.01mol/L4PMo11O40Deionized water solution, adding 0.01mol/L Ethylene Diamine Tetraacetic Acid (EDTA) to form heteropoly acid-EDTA complex, heating under reflux and stirring at 60 deg.C, adding 0.13g vanadyl sulfate into the complex solution, heating under reflux and stirring for 70min, and adding 0.6g Cs2CO3The aqueous solution of (2) is added to the above mixed solution. Heating, refluxing and stirring at 60 deg.C for 3 hr, and evaporating by rotary evaporationAnd (4) obtaining solid powder. The obtained powder is roasted for 3 hours at 300 ℃ in the air atmosphere.
The catalyst is used in selective oxidation reaction of isobutane, wherein the reaction temperature is 350 ℃, and the reaction temperature is isobutane: o is2：H2O：N227: 13.5: 10: 49.5, the contact time is 4.8s, the conversion rate of the isobutane is 4.8 percent, and the selectivity of the methacrylic acid is 42.8 percent.
TABLE 1 catalyst X-ray photoelectron spectroscopy data
TABLE 2 methacrylic acid production by selective oxidation of isobutane with catalyst
AcA acetic acid, AA acrylic acid, MA methacrolein, MAA methacrylic acid
Claims (5)
1. A catalyst for preparing methacrylic acid by selective oxidation of isobutane is characterized in that: the catalyst is a phosphomolybdic heteropoly acid salt with different vanadium-containing precursors doped in a Keggin structure and a secondary structure, and the general formula of the phosphomolybdic heteropoly acid salt is CsxVyPMo11VO40Wherein x is more than 0 and less than or equal to 2.5, and y is more than 0 and less than or equal to 0.5;
the vanadium-containing precursor is vanadyl sulfate, vanadyl oxalate, vanadium acetylacetonate or V2O5Or one or more of vanadyl nitrate.
2. The process according to claim 1 for preparing a catalyst for selective oxidation of isobutane to methacrylic acid, characterized by the following steps:
(1) doping a vanadium-containing precursor into a Keggin structure and a secondary structure of cesium phosphomolybdate by adopting a precipitation method and a complexation method to prepare CsxVyPMo11VO40The catalyst has x =0 and x is less than or equal to 2.5, and y is more than 0 and less than or equal to y0.5；
(2) The prepared CsxVyPMo11VO40Catalyst in air, N2Or H2300 under the atmosphere of/Ar mixed gasoAnd roasting the C for 3-10 hours to obtain the catalyst for selectively oxidizing isobutane to prepare methacrylic acid at high selectivity.
3. The method for preparing the catalyst for preparing methacrylic acid by selective oxidation of isobutane according to claim 2, wherein the vanadium-containing precursor is vanadyl sulfate, vanadyl oxalate, vanadium acetylacetonate, V2O5Or one or more of vanadyl nitrate.
4. The method for preparing the catalyst for preparing methacrylic acid by selective oxidation of isobutane according to claim 3, wherein the step (1) is specifically as follows:
preparing H with the concentration of 0.01-0.05 mol/L4PMo11VO40Deionized water solution at 50-100 deg.CoC, heating, refluxing and stirring, and then adding the vanadium-containing precursor into H4PMo11VO40Continuously heating, refluxing and stirring the solution for 30-100 min, and finally adding the Cs2CO3Adding the solution into the mixed solution to generate a precipitate, wherein the precipitate is 50-100%oHeating, refluxing and stirring for 1-10 h under C, and completely evaporating the solution by adopting a rotary evaporation method to obtain CsxVyPMo11VO40A catalyst;
the molar ratio of V/phosphomolybdate in the vanadium-containing precursor is = 0.1-0.5;
the Cs2CO3The molar ratio of Cs/phosphomolybdate in the solution is = 0.1-0.25.
5. Use of a catalyst according to claim 1 for the selective oxidation of isobutane to methacrylic acid, characterized in that: the catalyst is used for reaction for preparing methacrylic acid by selective oxidation of isobutane: the reaction temperature is 320-400 ℃, the reaction pressure is normal pressure, and the space velocity of isobutane reaction is 700-2000L Kg-1 h-1。
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| Cs+取代的Keggin 型杂多酸上丙烷选择氧化制丙烯酸的研究;李秀凯等;《天然气化工》;20040530;第29卷(第5期);第6-9页 * |
| Direct Oxidation of Isobutane into Methacrylic Acid over Cs, Ni,and V-substituted H3PMo12040 Heteropoly Compoundst;Noritaka. Mizuno et al.;《Studies in Surface Science and Catalysis》;19960101;第1001-1010页 * |
| Nikolaos Dimitratos et al..Effect of Brønsted acidity in propane oxidation over Cs2.5H1.5PV1Mo11-xWxO40 polyoxometallate compounds.《Catalysis Communications》.2006,第7卷第811-818页. * |
| Study of Ga modified Cs2.5H1.5PV1Mo11O40 heteropolyoxometallates for propane selective oxidation;Nikolaos Dimitratos et al.;《Journal of Molecular Catalysis A: Chemical》;20060515;第255卷;第184-192页 * |
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