CN110961126B - Catalyst, preparation method and application thereof - Google Patents
Catalyst, preparation method and application thereof Download PDFInfo
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- CN110961126B CN110961126B CN201911309275.2A CN201911309275A CN110961126B CN 110961126 B CN110961126 B CN 110961126B CN 201911309275 A CN201911309275 A CN 201911309275A CN 110961126 B CN110961126 B CN 110961126B
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- 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
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- 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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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Abstract
Catalysts, methods of making and uses thereof are disclosed. The catalyst has the following general formula, wherein Mo, P, V, sb and O respectively represent molybdenum, phosphorus, vanadium, antimony elements and oxygen; d is at least one element selected from iron, cobalt, nickel, manganese, copper, palladium, magnesium; e is at least one element selected from tungsten, bismuth, boron, arsenic, tin; z is a cocatalyst and is at least one compound selected from citric acid, tartaric acid, oxalic acid and maleic acid; a =0.1-3, b =0.01-3, c =0.01-5, d =0.1-3, e =0.01-2, f is the ratio of oxygen atoms required to satisfy valence; β/α =2-30 wt%; the preparation method of the catalyst sequentially comprises the following steps: (i) Providing a dispersion of catalyst precursor containing all of the catalyst ingredients; (ii) adding a cocatalyst compound Z and calcining. Alpha (Mo) 12 P a V b Sb c D d E e O f )/βZ。
Description
Technical Field
The invention relates to a preparation method of a catalyst for preparing methacrylic acid by oxidizing isobutyraldehyde. The catalyst prepared by the method has the advantages of high selectivity and long service life.
Background
Methacrylic acid (MAA) is an important organic chemical raw material and is mainly used for preparing methyl methacrylate, coatings, synthetic rubber, adhesives, fabric treating agents, resins, high polymer material additives, functional high polymer materials and the like. Methyl methacrylate is an important bulk chemical product and has wide application prospect. The MAA production mainly adopts an Acetone Cyanohydrin (ACH) method, but the technique needs to use a virulent substance hydrocyanic acid as a raw material, and a large amount of ammonium bisulfate is generated as a byproduct, thereby causing great pressure on the environment. MAA production can be carried out by an ethylene carbonylation method, a propylene carbonylation method, an isobutylene or t-butyl alcohol (C4) oxidation method, a methacrylonitrile method, and an isobutyraldehyde oxidation method, in addition to the ACH method.
The method for preparing MAA by one-step oxidation by using isobutyraldehyde as a raw material is one of the most economical and competitive processes. It is not only a complement of C4 oxidation method, but also a competitor of C4 oxidation method, and can fully utilize the isobutyraldehyde which is a byproduct of the butanol-octanol device, and can obtain better economic benefit.
The prior art proposes a number of catalysts for the oxidation of isobutyraldehyde to methacrylic acid. "study of synthesizing methacrylic acid by using phosphomolybdic heteropolyacid catalyst" In Wenxin et al (chemical Engineers, no. 6 of 2011) "mentions that different preparation process conditions have great influence on the performance of the catalyst, and the more suitable process conditions are that Mo-V-K-Cs-Cu-In-P-As are sequentially added, the roasting temperature is 390 ℃, and the more suitable reaction process conditions are that: reaction space velocity of 1000h -1 And the reaction temperature was 288 ℃.
CN101175569A discloses a catalyst for the manufacture of methacrylic acid, having the following composition: mo 10 V 0.8 P 1.15 Cu 0.4 Cs 0.3 (NH 4 ) 2.3 Sb 1.0 The conversion rate of methacrolein of the catalyst is about 88%, and the selectivity of methacrylic acid is about 83%.
CN102203040A discloses a catalyst for preparing methacrylic acid by using water or lower alkanol as a binder and Mo in the general formula 10 V a Pb(NH 4 ) c X d Y e O f The catalyst active component dry matter is obtained by coating a spherical carrier with a strength enhancer and a micropore forming agent to form a spherical coated catalyst, and calcining at 100-450 ℃, wherein X represents at least one element selected from K, rb and Cs, Y represents at least one element selected from the group consisting of Sb, as, cu, ag, mg, zn, al, B, ge, sn, pb, ti, zr, cr, re, bi, W, fe, co, ni, ce and Th, and a-f represent the atomic ratio of each element.
Although the prior art suggests a number of catalysts for the production of methacrylic acid, there is still room for further improvement in the activity of such catalysts.
Disclosure of Invention
The invention aims to provide a catalyst for preparing methacrylic acid, which has the advantages of high selectivity and long service life.
Accordingly, one aspect of the present invention is directed to a catalyst for the oxidation of isobutyraldehyde to methacrylic acid having the general formula:
α(Mo 12 P a V b Sb c D d E e O f )/βZ
wherein, mo 12 P a V b Sb c D d E e O f Is a main catalyst; mo, P, V, sb and O respectively represent molybdenum, phosphorus, vanadium, antimony elements and oxygen;
d represents at least one element selected from iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), copper (Cu), palladium (Pd), and magnesium (Mg);
e represents at least one element selected from tungsten (W), bismuth (Bi), boron (B), arsenic (As), and tin (Sn);
z is a cocatalyst and is at least one compound selected from citric acid, tartaric acid, oxalic acid and maleic acid;
a =0.1-3, b =0.01-3, c =0.01-5, d =0.1-3, e =0.01-2, f is the atomic ratio of oxygen required to satisfy the valence of each component described above;
β/α =2 to 30% (weight ratio);
the preparation method of the catalyst sequentially comprises the following steps:
(i) Providing a dispersion of catalyst precursor containing all of the catalyst ingredients;
(ii) Adding a cocatalyst compound, and roasting.
Another aspect of the present invention relates to a method for preparing a catalyst for preparing methacrylic acid by oxidizing isobutyraldehyde, the catalyst having the following general formula:
α(Mo 12 P a V b Sb c D d E e O f )/βZ
wherein, mo 12 P a V b Sb c D d E e O f Is a main catalyst; mo, P, V, sb and O respectively represent molybdenum, phosphorus, vanadium, antimony elements and oxygen;
d represents at least one element selected from iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), copper (Cu), palladium (Pd), and magnesium (Mg);
e represents at least one element selected from tungsten (W), bismuth (Bi), boron (B), arsenic (As), and tin (Sn);
z is a cocatalyst and is at least one compound selected from citric acid, tartaric acid, oxalic acid and maleic acid;
a =0.1-3, b =0.01-3, c =0.01-5, d =0.1-3, e =0.01-2, f is the atomic ratio of oxygen required to satisfy the valence of each component described above;
β/α =2 to 30% (weight ratio);
the method comprises the following steps in sequence:
(i) Providing a dispersion of catalyst precursor containing all of the catalyst ingredients;
(ii) Adding a cocatalyst compound, and roasting.
A further aspect of the invention relates to the use of the catalyst according to the invention for the preparation of methacrylic acid by oxidation of isobutyraldehyde.
Detailed Description
The technical problem to be solved by the invention is to provide a catalyst for synthesizing methacrylic acid by oxidizing isobutyraldehyde. The catalyst provided by the invention contains Mo, V, P and Sb as basic active components, and the service life of the catalyst is prolonged under the condition of improving the activity and selectivity of the catalyst.
Thus, the catalyst composition provided by the present invention can be represented by the formula:
α(Mo 12 P a V b Sb c D d E e O f )/βZ
wherein, mo 12 P a V b Sb c D d E e O f Is a main catalyst; mo, P, V, sb andand O represents molybdenum, phosphorus, vanadium, antimony elements and oxygen, respectively;
d represents at least one element selected from iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), copper (Cu), palladium (Pd), and magnesium (Mg); at least one element selected from copper (Cu), palladium (Pd) and cobalt (Co) is preferable.
E represents at least one element selected from tungsten (W), bismuth (Bi), boron (B), arsenic (As) and tin (Sn). Preferably at least one element selected from tin (Sn), bismuth (Bi) and arsenic (As).
Z is a cocatalyst, and is at least one compound selected from Citric Acid (CA), tartaric Acid (TA), oxalic acid and maleic acid; preferably citric acid, tartaric acid or mixtures thereof.
a =0.1-3, preferably 0.4-2.6, more preferably 0.8-2.2, preferably 1.2-1.8, preferably 1.4-1.6.
b =0.01-3, preferably 0.1-2.6, more preferably 0.3-2.0, preferably 0.5-1.8, preferably 1-1.5.
c =0.01-5, preferably 0.1-4.8, more preferably 0.5-4.2, preferably 1-3.5, preferably 1.5-3.
d =0.1-3, preferably 0.5-2.8, more preferably 0.8-2.3, preferably 1.2-2.0, preferably 1.5-1.8.
e =0.01-2, preferably 0.05-1.8, more preferably 0.1-1.6, preferably 0.5-1.2, preferably 0.8-1.1.
f is an atomic ratio of oxygen required to satisfy the valences of the respective components described above.
β/α =2-30% (by weight), preferably 5-28%, more preferably 8-22%, preferably 10-18%, preferably 12-16%.
In one embodiment of the invention, the catalyst is selected from 95 (Mo) 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/5TA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.4 )/5TA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.8 Bi 0.3 )/5TA、90(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/10TA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/5CA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Cu 0.4 Bi 0.3 )/5TA、95(Mo 12 V 0.8 P 1.5 Sb 0.4 Co 0.6 Bi 0.3 ) /5TA or a mixture of two or more thereof.
The method for preparing the catalyst sequentially comprises the following steps:
(i) Providing a dispersion of the catalyst precursor containing all the catalyst components
The method for providing the catalyst precursor dispersion of the present invention is not particularly limited, and may be a conventional method known in the art. In one embodiment of the present invention, the method for providing a catalyst precursor dispersion comprises dissolving the compounds of the respective constituent elements or adding them as solid powders and mixing the materials at 40 to 80 ℃, preferably 45 to 75 ℃, preferably 50 to 70 ℃ to prepare a suspension dispersion slurry of the catalyst precursor containing all the above-mentioned catalyst components.
In a preferred embodiment of the present invention, the phosphorus-containing solution, the vanadium-containing solution, the antimony-containing solution, the D-containing compound-containing solution and the E-containing compound-containing solution are mixed uniformly in this order at 40 to 80 ℃, and the mixing is usually carried out while stirring, to obtain a uniform suspension slurry.
The solvent and temperature required for dissolving the materials are not particularly limited as long as the compound to be used can be completely dissolved or uniformly mixed, and examples of the solvent include water and ethanol, and water is preferably used. The amount of water is about 100 to 400 parts by weight, preferably 200 to 300 parts by weight, based on 100 parts by weight of the total amount of the compounds for preparing the slurry.
In a preferred embodiment of the invention, the proportion of phosphorus in the catalyst of the invention is from 0.1 to 3, preferably from 1 to 1.5, based on an atomic ratio of molybdenum of 12; the proportion of vanadium is between 0.01 and 3, preferably between 0.1 and 1; the proportion of antimony is from 0.01 to 5, preferably from 0.05 to 0.5; the kind and use ratio of other active components required are determined according to the use conditions of the catalyst, etc., to obtain a catalyst having the best performance. Generally, the proportion of element D is from 0.1 to 3, preferably from 0.5 to 1; the proportion of the element E is from 0.01 to 2, preferably from 0.05 to 0.5.
In one embodiment of the invention, the following compounds may be selected as catalyst precursor compounds:
the molybdenum-containing compound may be selected from molybdenum trioxide, ammonium paramolybdate, phosphomolybdic acid, molybdate or a mixture thereof, preferably ammonium paramolybdate;
the phosphorus-containing compound can be selected from phosphorus pentoxide, phosphoric acid, phosphomolybdic acid, ammonium phosphate, etc., preferably phosphoric acid;
the vanadium-containing compound can be selected from vanadium pentoxide, ammonium metavanadate and the like, and is preferably ammonium metavanadate;
the antimony-containing compound can be selected from antimony trioxide, antimony chloride, antimony pentoxide, etc., preferably antimony trioxide;
the compound containing D can be selected from nitrate, acetate, chloride or oxide of D element, preferably nitrate;
the compound containing E can be selected from nitrate, acetate, chloride or oxide of E element, preferably nitrate.
(ii) Adding a cocatalyst compound, calcining
The inventors of the present invention have found that if the co-catalyst is directly added to the dispersion slurry, the resulting catalyst has improved catalytic activity. The present invention has been completed based on this finding.
Thus, the process for the preparation of the catalyst of the present invention comprises the step of adding the cocatalyst directly to the suspension slurry prepared above. The cocatalyst is at least one compound selected from citric acid, tartaric acid, oxalic acid and maleic acid; preferably citric acid, tartaric acid or mixtures thereof.
The process of the present invention may further comprise the step of drying the mixture of procatalyst and cocatalyst. Suitable drying methods are not particularly limited and may be conventional drying methods known in the art, such as oven drying, spray drying, evaporation drying, drum drying, and the like.
In one embodiment of the invention, the drying comprises heat drying at a temperature of 60 to 120 ℃, preferably 70 to 110 ℃, more preferably 80 to 100 ℃, preferably 85 to 95 ℃.
In one embodiment of the invention, the process of the invention comprises the step of comminuting the dried catalyst precursor.
The process of the present invention may further comprise the step of adding a thermally conductive diluent to the dried mixture. Suitable thermally conductive diluents are not particularly limited and may be those known in the art. In one embodiment of the present invention, the thermally conductive diluent is selected from silicon powder (Si), silicon carbide (SiC), molybdenum oxide (MoO) 3 ) Tungsten oxide (WO) 3 ) Titanium oxide (TiO) 2 ) Or zirconium oxide (ZrO) 2 ) Preferably silicon powder (Si) and zirconium oxide (ZrO) 2 ) One or a mixture of several of them.
In one embodiment of the invention, the method comprises the steps of stirring the catalyst precursor slurry uniformly, adding the cocatalyst Z component, heating to 85-95 ℃, continuing stirring to be viscous, drying, adding the heat-conducting diluent, molding and roasting to obtain the finished catalyst.
The catalyst calcination is carried out in an oxygen-containing atmosphere, and the calcination temperature is selected to be 300-450 ℃, preferably 350-400 ℃. The calcination time is 60 to 600 minutes, preferably 120 to 540 minutes, and more preferably 240 to 480 minutes.
In the oxygen-containing atmosphere of the present invention, the oxygen mass concentration is not less than 10%, preferably not less than 20%. In the roasting process, the temperature needs to be slowly raised, so that the cocatalyst Z can escape from the catalyst in a sublimation form or a slow decomposition form, and the structure of the catalyst is not damaged. In one embodiment of the invention, the temperature rise rate during firing is 5-20 deg.C/min, preferably 6-18 deg.C/min, more preferably 7-16 deg.C/min, preferably 8-14 deg.C/min, and most preferably 9-12 deg.C/min.
The process of the present invention may further comprise the step of shaping the calcined catalyst. The catalyst molding method is not particularly limited, and known dry and wet molding methods such as a tablet molding method, an extrusion molding method, a pellet 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.
In a preferred embodiment of the present invention, the catalyst is prepared by a method comprising the steps of: dissolving a molybdenum precursor compound in water to obtain a solution A, dissolving a vanadium precursor compound in distilled water to obtain a solution B, dissolving a cobalt precursor compound in water to obtain a solution C, and dissolving a bismuth precursor compound in a dilute nitric acid aqueous solution to obtain a solution D. Adding the phosphoric acid solution, the solution B, the antimony trioxide powder, the solution C and the solution D into the solution A in sequence under the condition of rapid stirring to obtain a slurry, and stirring for 2 hours at the temperature of 60 ℃. Adding the promoter powder into the slurry, heating to 80-95 ℃, stirring the slurry to be viscous, and drying in an oven for later use. And crushing the dried materials, adding heat-conducting diluent powder and a proper amount of water, and extruding and molding. And then roasting to obtain the final finished catalyst.
The catalyst of the invention can be used for preparing methacrylic acid by oxidizing isobutyraldehyde. In one embodiment of the present invention, a method for preparing methacrylic acid by oxidizing isobutyraldehyde comprises: the raw materials of isobutyraldehyde, air or a diluted gas mixture containing molecular oxygen and steam are preheated and then introduced into a fixed bed tubular reactor filled with a catalyst to synthesize methacrylic acid through one-step reaction. The molecular oxygen in the diluent gas mixture can be pure oxygen, oxygen-enriched oxygen or air, and the diluent gas can be N 2 、CO、CO 2 Or H 2 O or a mixture of O and O in any proportion.
The oxidation reaction conditions are as follows: the temperature is 250-320 ℃, preferably 280-300 ℃; 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 -1 Preferably 1500 to 2000h -1 (ii) a The molar concentration of isobutyraldehyde is 1 to 20%, preferably 3 to 8%; o is 2 The molar ratio to MAL is 0.5-8, preferably 1-5; the molar ratio of water vapor to isobutyraldehyde is from 1 to 15, preferably from 3 to 10.
The conversion and selectivity of the oxidation of isobutylaldehyde to methacrylic acid was calculated as follows:
the preparation of the catalyst and its performance in catalyzing the selective oxidation of isobutyraldehyde 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
200 g of ammonium paramolybdate was dissolved in 500 g of distilled water at 60 ℃ to obtain a solution A. 8.8 g of ammonium metavanadate was dissolved in 100 g of distilled water at 60 ℃ to obtain a solution B. 16.6 g of cobalt nitrate was dissolved in 50 g of 60 ℃ distilled water to obtain a solution C. 11.3 g of bismuth nitrate was dissolved in 30 g of a dilute aqueous nitric acid solution having a mass concentration of 10% to obtain a solution D.
12.9 g of phosphoric acid solution, solution B, 5.5 g of antimony trioxide powder, solution C and solution D were added to solution A in this order under rapid stirring to obtain a slurry, which was stirred at 60 ℃ for 2 hours.
13 g tartaric acid powder is added into the slurry, the temperature is raised to 90 ℃, the slurry is stirred to be viscous and is put into an oven to be dried at 120 ℃ for standby.
And crushing the dried material, adding 54 g of zirconium oxide powder and a proper amount of water, and performing extrusion molding by using a piston type extrusion molding machine to obtain a cylinder with the outer diameter of 3mm and the length of 5 mm. The final finished catalyst was then calcined in a 380 ℃ air stream for 6 hours to produce the catalyst element composition shown below.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. After 80 hours of reaction, reaction products are collected for gas chromatography analysis, and the selectivity of the MAL is 12.1 percent, and the selectivity of the MAA is 68.4 percent.
Example 2
The elemental composition of the catalyst obtained in example 1 was changed from 11.3 g of bismuth nitrate to 15.1 g of bismuth nitrate under otherwise unchanged preparation conditions, as shown below.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.4 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. After 80 hours of reaction, the reaction product was collected and analyzed by gas chromatography, and the selectivity for MAL was 17.3% and the selectivity for MAA was 64.2%.
Example 3
The elemental composition of the catalyst obtained in example 1 was changed from 16.6 g of cobalt nitrate to 22.1 g of bismuth nitrate under otherwise unchanged preparation conditions, as shown below.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.8 Bi 0.3 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. After 80 hours of reaction, the reaction product was collected for gas chromatography, and the selectivity of MAL was 9.4% and the selectivity of MAA was 69.7%.
Comparative example 1
The tartaric acid addition mode in example 1 was changed to mixing during catalyst formation, and other preparation conditions were unchanged, and the resulting catalyst element compositions were as follows.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. Collecting reaction products after the reaction is carried out for 80 hours for gas chromatography analysis, wherein the selectivity of MAL is13.3% and MAA selectivity 62.8%.
Comparative example 2
The catalyst element composition obtained by changing 11.3 g of bismuth nitrate in example 1 to 1.8 g of boric acid without changing other preparation conditions was as follows.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 B 0.3 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, a selective oxidation reaction is carried out. After 80 hours of reaction, the reaction product was collected for gas chromatography, and the selectivity of MAL was 28.9% and the selectivity of MAA was 42.5%.
Example 4
The composition of the catalyst elements obtained by changing 13 g of tartaric acid to 28 g of tartaric acid in example 1 without changing the other preparation conditions was as follows.
90(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/10TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. After 80 hours of reaction, the reaction product was collected and analyzed by gas chromatography, and the selectivity of MAL was 8.5% and the selectivity of MAA was 70.0%.
Example 5
The composition of the catalyst elements obtained in example 1 was changed from 13 g of tartaric acid to 13 g of citric acid without changing the other preparation conditions, as shown below.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/5CA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 ＝1:34 －1 Then, a selective oxidation reaction is carried out. After 80 hours of reaction, the reaction product was collected for gas chromatography, and the selectivity for MAL was 14.2% and the selectivity for MAA was 67.4%.
Example 6
The elemental composition of the catalyst obtained in example 1 was changed from 16.6 g of cobalt nitrate to 7.1 g of copper nitrate under otherwise unchanged preparation conditions, as shown below.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Cu 0.4 Bi 0.3 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, a selective oxidation reaction is carried out. After 80 hours of reaction, the reaction product was collected and analyzed by gas chromatography, and the selectivity for MAL was 15.7% and the selectivity for MAA was 63.4%.
Example 7
The elemental composition of the catalyst obtained in example 1 was changed from 12.9 g of phosphoric acid to 16.1 g of copper nitrate under otherwise unchanged preparation conditions, as shown below.
95(Mo 12 V 0.8 P 1.5 Sb 0.4 Co 0.6 Bi 0.3 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. After 80 hours of reaction, the reaction product was collected for gas chromatography, and the selectivity of MAL was 12.6% and the selectivity of MAA was 69.7%.
Comparative example 3
The composition of the catalyst elements obtained by replacing 16.6 g of cobalt nitrate in example 1 with 4.2 g of magnesium nitrate under otherwise unchanged preparation conditions was as follows.
95(Mo 12 V 0.8 P 1.2 Sb 0.4 Mg 0.3 Bi 0.3 )/5TA
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. After 80 hours of reaction, reaction products are collected for gas chromatography analysis, and the selectivity of the MAL is 24.6 percent, and the selectivity of the MAA is 44.3 percent.
Comparative example 4
13 g of tartaric acid from example 1 were removed without changing the other preparation conditions, and the elemental composition of the obtained catalyst was as follows.
Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3
The catalyst is loaded into a fixed bed tubular reactor at 290 deg.C (reaction temperature), atmospheric pressure, IBD: O 2 :H 2 O:N 2 3 －1 Then, selective oxidation reaction is carried out. After 80 hours of reaction, reaction products are collected for gas chromatography analysis, and the selectivity of the MAL is 32.1 percent, and the selectivity of the MAA is 42.8 percent.
Claims (12)
1. A catalyst for preparing methacrylic acid by oxidizing isobutyraldehyde has the following general formula:
α(Mo 12 P a V b Sb c D d E e O f )/βZ
wherein, mo 12 P a V b Sb c D d E e O f Is a main catalyst; mo, P, V, sb and O respectively represent molybdenum, phosphorus, vanadium, antimony elements and oxygen;
d represents at least one element selected from iron, cobalt, nickel, manganese, copper, palladium and magnesium;
e represents at least one element selected from tungsten, bismuth, boron, arsenic and tin;
z is a cocatalyst and is at least one compound selected from citric acid, tartaric acid, oxalic acid and maleic acid;
a =0.1-3, b =0.01-3, c =0.01-5, d =0.1-3, e =0.01-2, f is the atomic ratio of oxygen required to satisfy the valence of each component described above;
β/α =2-30 wt%;
the preparation method of the catalyst sequentially comprises the following steps:
(i) Providing a dispersion of catalyst precursor containing all of the catalyst ingredients;
(ii) Adding a cocatalyst compound, heating to 85-95 ℃, continuously stirring to be viscous, and drying;
(iii) Adding heat conducting diluent into the dried mixture, molding and roasting.
2. The catalyst of claim 1 wherein D is selected from at least one element of the group consisting of Cu, pd, co.
3. The catalyst of claim 1 or 2, wherein E is selected from at least one of tin Sn, bismuth Bi, arsenic As.
4. The catalyst of claim 1 or 2, wherein Z is selected from citric acid, tartaric acid or mixtures thereof.
5. The catalyst of claim 1 or 2, wherein: a =0.4-2.6, b =0.1-2.6, c =0.1-4.8, d =0.5-2.8, e =0.05-1.8, β/α =5-28 wt%.
6. The catalyst of claim 1 or 2, wherein: a =0.8-2.2, b =0.3-2.0, c =0.5-4.2, d =0.8-2.3, e =0.1-1.6, β/α =8-22 wt%.
7. The catalyst of claim 1 or 2, wherein: a =1.2-1.8, b =0.5-1.8, c =1-3.5, d =1.2-2.0, e =0.5-1.2, β/α =10-18 wt%.
8. The catalyst of claim 1 or 2, wherein: a =1.4-1.6, b =1-1.5, c =1.5-3, d =1.5-1.8, e =0.8-1.1, β/α =12-16 wt%.
9. The catalyst according to claim 1 or 2, characterized in that the catalyst is selected from 95 (Mo) 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/5TA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.4 )/5TA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.8 Bi 0.3 )/5TA、90(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/10TA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Co 0.6 Bi 0.3 )/5CA、95(Mo 12 V 0.8 P 1.2 Sb 0.4 Cu 0.4 Bi 0.3 )/5TA、95(Mo 12 V 0.8 P 1.5 Sb 0.4 Co 0.6 Bi 0.3 ) /5TA or a mixture of two or more thereof.
10. A process for the preparation of a catalyst as claimed in any one of claims 1 to 9, comprising the following steps in sequence:
(i) Providing a dispersion of catalyst precursor containing all of the catalyst ingredients;
(ii) Adding a cocatalyst compound, heating to 85-95 ℃, continuously stirring to be viscous, and drying;
(iii) Adding heat conducting diluent into the dried mixture, molding and roasting.
11. The method according to claim 10, wherein the thermally conductive diluent is selected from one or more of silicon powder, silicon carbide, molybdenum oxide, tungsten oxide, titanium oxide, and zirconium oxide.
12. Use of a catalyst according to any one of claims 1 to 9 for the preparation of methacrylic acid by oxidation of isobutyraldehyde.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528398A (en) * | 1981-06-08 | 1985-07-09 | The Standard Oil Company (Ohio) | Method for the preparation of unsaturated carboxylic acid with high activity phosphomolybdic acid based catalysts |
| CN101219389A (en) * | 2007-12-26 | 2008-07-16 | 厦门大学 | Solid catalyst for propylene manufacture with propane oxo-dehydrogenation and method for producing the same |
| 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 |
| CN105498795A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst and preparation method thereof |
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| US7649111B2 (en) * | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528398A (en) * | 1981-06-08 | 1985-07-09 | The Standard Oil Company (Ohio) | Method for the preparation of unsaturated carboxylic acid with high activity phosphomolybdic acid based catalysts |
| CN101219389A (en) * | 2007-12-26 | 2008-07-16 | 厦门大学 | Solid catalyst for propylene manufacture with propane oxo-dehydrogenation and method for producing the same |
| 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 |
| CN105498795A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst and preparation method thereof |
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