CN1047985A - Produce the catalyzer and the application of methacrylic acid - Google Patents
Produce the catalyzer and the application of methacrylic acid Download PDFInfo
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- CN1047985A CN1047985A CN 90105215 CN90105215A CN1047985A CN 1047985 A CN1047985 A CN 1047985A CN 90105215 CN90105215 CN 90105215 CN 90105215 A CN90105215 A CN 90105215A CN 1047985 A CN1047985 A CN 1047985A
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Abstract
The catalyzer that a kind of heteropolyacid and its esters are formed, the chemical constitution of its active ingredient is:
P
aAs
bMo
cV
dX
fY
gO
x
Wherein: P is a phosphorus, and As is an arsenic, and Mo is a molybdenum, and V is a vanadium:
X is one or more a metallic element such as antimony, bismuth, iron, manganese, copper, cobalt, nickel, zinc, silver;
Y is one or more a metallic element such as sodium, potassium, rubidium, caesium, magnesium, calcium, barium;
O is an oxygen:
A, b, c, b, f, g, x represent the mol ratio between each element; Compound with respective components is a raw material, adopts the coprecipitation method preparation, is carrier with the aluminium carbide, adds the organic reducing material, forms through the certain temperature calcination activation.
Be used for isobutyraldehyde oxidation and produce methacrylic acid, the isobutyric aldehyde transformation efficiency is 100% under the reaction conditions of regulation, and it is more than 67% that the methacrylic acid list is received, and the Methylacrylaldehyde list is received and is 10-20%, and is constant substantially through long-time running catalyst structure.
Description
The present invention relates to a kind of heteropolyacid catalyst, particularly about produce the heteropolyacid catalyst and the preparation thereof of methacrylic acid by isobutyraldehyde oxidation.
Methyl acrylic ester has good physical and chemical performance, is extremely useful industrial chemicals.Methymethacrylate also can be done the properties-correcting agent of polyvinyl chloride except that the polymerization single polymerization monomer that is used as synthetic glass, and produces coating, tackiness agent and senior paint etc.
Producing the commercial run of methymethacrylate, always is to use the acetone cyanohydrin method, uses prussic acid in the production process, big to human body harm, the sulfuric acid of consumption, etching apparatus is arranged again and handle the problems such as producing monoammonium sulfate of paying.
Since the sixties, a lot of producers all carry out the research of the new synthetic method of methacrylic acid, are raw material with propylene, iso-butylene or isobutyric aldehyde, produce methacrylic acid more easily and economically.Wherein, be the route of raw material two-step oxidation legal system methacrylic acid with the isobutyric aldehyde and be the route of raw material two-step oxidation legal system methacrylic acid with the trimethyl carbinol (or iso-butylene), all finished interim test, the latter has also realized industrialization [the peaceful husband's catalyst of pine 25(1) 67(1983)].In two-step approach, earlier isobutyric aldehyde or Oxidation of t-Butanol are got isopropylformic acid (or Methylacrylaldehyde), then isopropylformic acid (or Methylacrylaldehyde) oxydehydrogenation is got methacrylic acid.These two kinds of industrial routes are all superior than the acetone cyanohydrin method.From the comprehensive utilization angle of producing isobutyric aldehyde of paying of propylene oxo process system butyl octanol unit, isobutyraldehyde oxidation system methacrylic acid is most economical.
The route of isobutyric aldehyde two-step method making methacrylic acid, American Cyanamid Company's priorities such as (USP.4.061.673-1977) have been developed the catalyzer of the plumbous phosphate system of iron, and the rate of recovery in crucial one step of isopropylformic acid oxydehydrogenation system methacrylic acid can reach 50%.Domestic many units have also carried out the research of this system.For improving the methacrylic acid yield, Mitsubishi changes into and adopts the phosphorus molybdenum vanadium heteropolyacid catalyzer, and the methacrylic acid once through yield reaches more than 63%.Jilin University has also carried out the catalytic kinetics research department research of this respect, uses heteropolyacid catalyst, and the methacrylic acid yield also reaches (petrochemical complex .13(1) 9(1984 more than 63%)).
But in two-step approach, though the first step isobutyraldehyde oxidation becomes isopropylformic acid easy, yield can only reach 85-90%, has lost 10-15%.Can not all transform when adding second step isopropylformic acid oxydehydrogenation.Isopropylformic acid and methacrylic acid boiling point are very nearly the same, are difficult to separate.In order to overcome above-mentioned shortcoming, Ube (clear 59-160537), catalyst (EP.0.043.100) and USS oil company (EP.0.060.066) adopt heteropolyacid catalyst to carry out the research that the isobutyric aldehyde oxidation step is a methacrylic acid in succession.At 280-350 ℃, the isobutyric aldehyde transformation efficiency is 95-100%, and the methacrylic acid yield is more than 60%, also obtains the small part Methylacrylaldehyde.Methylacrylaldehyde can return and continue reaction generation methacrylic acid in the raw material.Compare with two-step approach, the methacrylic acid total recovery improves 5-10%, does not exist isopropylformic acid to separate difficult problem with methacrylic acid, and flow process is short, and facility investment and investment cost are low, are very attractive industrial routes.
The key of isobutyric aldehyde oxidation step legal system methacrylic acid is to use heteropolyacid catalyst.Multiple elements such as phosphorous in the heteropolyacid catalyst, molybdenum, arsenic, vanadium, copper, contained element and content in above-mentioned patent documentation, raw materials used and preparation process has nothing in common with each other.
Stipulate among the clear 59-160537 of patent that the source of molybdenum must be a phospho-molybdic acid in the heteropolyacid, the source of other element is the oxygen acid of this element, oxide compound, oxyhydroxide or its esters; The Preparation of catalysts method is that phospho-molybdic acid and other element compound water are mixed into solution or serum, adds thermomaturation, adds the organic reducing material again, at 100-300 ℃, heat-treats in air or nitrogen.Such catalyzer can use carrier.
Stipulate that in patent EP.0.060.066 the source of phosphorus is a phosphoric acid in the heteropolyacid catalyst, the source of other element is its corresponding oxide compound, oxyhydroxide, halogenide or nitrate, carbonate etc.; The preparation method is mixed into aqueous mixture with each element compound in the proper ratio, and regulating the pH value is 4-7, dry aqueous slurries, the dry thing of roasting in the presence of air or nitrogen.Can use the carrier blending or the catalyst activity component is coated in the surface of carrier core.
Stipulate that in patent EP.0.043.100 the source of molybdenum is its oxide compound, molybdic acid, molybdate or phospho-molybdic acid; The source of phosphorus is phosphoric acid, ammonium hydrogen phosphate or Sodium phosphate dibasic; The source of vanadium is the vitriol of its oxide compound, vanadate, vanadium or vanadium oxalate etc., and other metallic element compound is its oxide compound, oxyhydroxide, halogenide, carbonate, vitriol, nitrate or its oxygen acid etc.The preparation method is the compound formation molybdovanaphosphoric acid of elder generation with phosphorus, molybdenum and vanadium, water-soluble, add nitrogenous heterogeneous ring compound, and acidifying in addition, obtain water-soluble crystallization, add other metallic element compound again, molded and dry, drying temperature is 100-300 ℃, and high-temperature activation obtains finished catalyst then.
More than the various heteropolyacid catalysts that are used for one-step oxidation process by isobutyric aldehyde system methacrylic acid, though better aspect isobutyric aldehyde transformation efficiency, methacrylic acid selectivity and yield, do not see application in industrial aspect.Particularly, because the heteropolyacid unstable chemcial property, high temperature easily decomposes down, and its life-span is one of key issue.From preparing the viewpoint of practical catalyzer, heteropolyacid is the mouldability and the bad mechanical strength of molybdovanaphosphoric acid catalyzer particularly, and when increasing its intensity with various ways, the productive rate of catalyzer reduces again.So it is difficult obtaining the high strength catalyzer of industrial use and having satisfied yield.Up to the present, still do not see the report that above various heteropolyacid catalyst long-term operation is used.
Find after deliberation to produce methacrylic acid by the isobutyric aldehyde one-step oxidation process, can finish by a fixed bed flowing reactive system, in reaction, adopt the said heteropolyacid catalyst of the present invention, at temperature 280-350 ℃, air speed 500-2000 hour, isobutyric aldehyde concentration was 2-6% in the unstripped gas, when pressure is normal pressure, the isobutyric aldehyde transformation efficiency can reach 100%, and it is more than 68% that the methacrylic acid list is received, and the Methylacrylaldehyde list is received and is 10-20%.
One of purpose of the present invention provides a kind of heteropolyacid catalyst, uses this catalyzer in the isobutyric aldehyde one-step oxidation process, obtains with unprecedented transformation efficiency, selectivity and methacrylic acid yield.This activity of such catalysts component is made up of phosphorus, molybdenum, vanadium, arsenic and other metallic element and oxygen, is that the compound with respective components is a raw material, adopts the coprecipitation method preparation, with the carrier mixing moulding, forms through the certain temperature calcination activation then.
Another object of the present invention provides a kind of method for preparing heteropolyacid catalyst.
Heteropolyacid has specific structure, has strongly-acid and oxidisability; And can usually regulate its acidity and oxidisability by changing counterion, central atom and coordination unit, and not destroy its basic structure.According to these characteristics of heteropolyacid and the characteristics of isobutyraldehyde oxidation system methacrylic acid-respons, in the present invention, the activity of such catalysts component is with following general formula:
PaAsbMocVdXfYgOx
In the formula: P is a phosphorus, and As is an arsenic, and Mo is a molybdenum, and V is a vanadium;
X is one or more a metallic element such as antimony, bismuth, iron, manganese, copper, cobalt, nickel, zinc, silver;
Y is one or more a metallic element such as sodium, potassium, rubidium, caesium, magnesium, calcium, barium;
O is an oxygen.
A, b, c, b, f, g and x represent the mol ratio between each element; Its concrete scope is: a=0.1～0.2, and b=0.001～2.0, c=5.0～20,
, f=0.01～2.0,
G=0.1～5.0, X is a positive number, should satisfy the requirement of each composition valence.
The raw material of heteropolyacid catalyst is among the present invention: phosphorus phospho-molybdic acid, phosphoric acid, phosphoric acid salt or Vanadium Pentoxide in FLAKES (P
2O
5) etc.; Arsenic arsenic molybdic acid, arsenic acid, arsenic powder (As
2O
5) or arsenate etc.; Molybdenum phospho-molybdic acid, molybdate or molybdenum oxide (MoO
3) etc.; Vanadium Vanadium Pentoxide in FLAKES (V
2O
5) or metavanadate etc.; X oxide compound, oxyhydroxide, muriate, vitriol, acetate or the nitrate etc. of respective element; Y oxide compound, oxyhydroxide, vitriol, nitrate or the muriate etc. of respective element.
Catalyzer of the present invention has been carried out structural analysis, and infrared spectra determines that the primary structure of catalyzer is the Koggin structure, and its key band is the ν (1060cm of ρ-ο)
-1, ν (Mo=0) 960cm
-1ν (Mo-o-Mo) 880cm
-1And 790cm
-1X-ray diffraction records the secondary structure of catalyzer, and the α θ value (copper target) of diffraction peak is 48.0 °, and 39.3 °, 36.2 °, 30.5 °, 26.4 °, 21.4 °, 15.1 °, 10.7 °.Skeleton structure is phosphorus, molybdenum, vanadium heteropolyacid and salt thereof basically, and wherein some phosphorus atom is replaced by arsenic.The aerial decomposition temperature of catalyzer that heating differential analysis is determined is 442 ℃; The specific surface area of the catalyzer that the press pump method records is 3-5M
2/ gram, the most probable radius is 600A °, average pore radius is 2500A °.
In catalyst preparation process, the addition sequence of various materials is not specially limited.General at first the compound of the compound of molybdenum and other element, use acidifying, the general pH value remains on 0.1-3.0, stir slaking 1-10 hour at 50-90 ℃ of rare slurry that will obtain down then, then the pH value is transferred to 4-7, be lower than under 100 ℃ its evaporate to dryness in temperature, resulting is the catalyzer work in-process.
Slaking can improve activity of such catalysts and selectivity, but reason is still indeterminate, and the chances are because the effect of slaking helps the formation of heteropolyacid and the crystalline structure of heteropolyacid is changed, and is formed with the crystalline structure that is beneficial to reaction.
Isobutyraldehyde oxidation system methacrylic acid is a strong exothermic reaction, so add carrier life of catalyst and selectivity all is beneficial to.To using carrier, above-mentioned existing document is in addition special stipulation not, just says among clear 59-160537 and the EP.0.060.066 and can use carrier.Catalyzer has strongly-acid and oxidisability among the present invention, does carrier so add which kind of material, and very weight seems.Consider that from the characteristics of catalyzer of the present invention and isobutyraldehyde oxidation system methacrylic acid carrier must be an inert, thermal conductivity will be got well.Add carrier following advantage is arranged: (1) helps the diffusion of heat, thereby improves its selectivity and life-span; (2) intensity behind the raising shaping of catalyst; (3) effective rate of utilization of raising catalyzer reduces cost.
Can α-Al be arranged as the material of support of the catalyst among the present invention
2O
3, quartz sand and silicon carbide etc., but silicon carbide preferably.In the present invention, require the carrier mean particle size greater than 180 orders, specific surface area is 1-5M
2/ gram.
In the present invention, the catalyzer behind the adding carrier, its active ingredient should account for 50% of total catalyst weight at least, preferably more than 70%.
The catalyzer that adds carrier will be through overmolding, and characteristics of the present invention also are, will add a certain amount of organic reducing material in moulding process, and this helps to improve activity of such catalysts and selectivity.The mechanism of action of organic reducing material in catalyzer is also not clear, estimates to have following two aspects, and (1) regulates the oxidation-reduction quality of each component of catalyzer; (2) increased the specific surface area of catalyzer.The organism that can be used as reducing substance has glycolic acid, oxalic dialdehyde acid, polyvinyl alcohol, dimethyl formamide, vinyl ethylene glycol, propenyl ethylene glycol etc.The add-on of organic reducing material will be decided according to different substances, can mix adding by two or more organic reducing material sometimes, only adds a kind of sometimes.In the present invention, the total amount of organic reducing material adding is 1-10%.
Catalyzer after the moulding is activated.Activation temperature needs to decide according to the composition of the volatile matter of raw materials used and generation, is generally 200-420 ℃.Activation needs to carry out in oxygen-containing atmosphere, too is reduced to prevent catalyzer.
Isobutyric aldehyde oxidation step activity of such catalysts, selectivity and study on the stability are finished in fixed bed flowing reactive system.Reactor is that the stainless steel tube of 20 * 2.5 * 450 millimeters of Φ is made, and divides two sections of preheating and reactions, and conversion zone is by the molten heating of tin.Isobutyric aldehyde and water are by micro pump injecting reactor preheating section and oxygen, oxygen mix vaporization and preheating, and gas mixture is gone into the catalytic bed reaction.Reaction is after the condensation recovery.Get condensate recovery liquid respectively and carry out product and by product analysis with discharging gas.
Reaction conditions: temperature of reaction 280-350 ℃, during air speed 1500
-1, isobutyric aldehyde: oxygen: nitrogen: water=1: 2.5: 10: the 7(mol), pressure is normal pressure.Catalyzer is the 10-20 order, 12 milliliters of loading amounts.
Total acid content in the liquid phase is measured by neutralisation.Total acid content reduces the MAA amount and is the HAC amount.
Total two keys in the liquid phase are measured with bromination method.
MAL in liquid phase, the gas phase, ACT are quantitatively made by vapor-phase chromatography.CO and CO
2Also be to make by vapor-phase chromatography.
The value of above gained data all is converted into the molar percentage that the required isobutyric aldehyde of these products accounts for total feed.
Selectivity:
MAA(%)=total two keys (%)-MAL(%)
HAC(%)=total acid-1/2 * MAA(%)
Carbon balance:
∑C（%）＝MAA（%）+MAL（%）+ACT（%）+CO（%）+HAC（%）
(shortenings implication: MAA methacrylic acid
The MAL Methylacrylaldehyde
The IBD isobutyric aldehyde
ACT acetone
HAC acetic acid)
Because isobutyric aldehyde transforms fully, so its yield equals selectivity.
With the catalyzer among the present invention, running is more than 1000 hours in testing apparatus, and catalyst activity, selectivity and structure are constant substantially.Reaction result and more as shown in table 1.
Press table 1, the catalyzer among the present invention, when being used for isobutyraldehyde oxidation system methacrylic acid, the MAA selectivity surpasses existing diplomatic best level, and (MAA+MAL) overall selectivity surpasses existing document best level 3%.
Example 1
63.6 gram ammonium molybdates are water-soluble, in 30-35 ℃ of solution that adds 2.52 gram potassium hydroxide solids and 1.71 gram butter of antimony, add 1.5 gram neutralized verdigriss and 0.9 gram ammonium meta-vanadate again, add 20 milliliters of hydrochloric acid.Temperature is risen to 70 ℃, stirred 3 hours.The mixture that under room temperature, adds 1.05 gram arsenic acids and 4.1 gram phosphoric acid.Add 25 milliliters of ammoniacal liquor again, in being lower than under 80 ℃ with its evaporate to dryness, again in 110 ℃ of oven dry down.
The catalyzer work in-process that obtain add the silicon carbide that accounts for weight 25% in 250 ℃ of oven dry 2 hours, add 4 milliliters of polyvinyl alcohol saturated solutions, are ground into 10-20 order particle after the extrusion molding, in 380 ℃ of roastings 6 hours.
The activity of such catalysts component that obtains is:
P
1.13Mo
12As
0.2V
0.25Cu
0.25K
1.5Ox
Again 12 milliliters of catalyzer are mixed the reactor of packing into 12 milliliters of silicon carbide.In 320 ℃, under the normal pressure, IBD: O: N: HO=1: 2.5: 10: 7, air speed 1500 hours
-1Following reaction the results are shown in table 2.
Example 2
Change the consumption of arsenic acid and phosphoric acid in the example 1 into 1.58 grams and 3.83 grams respectively, other preparation process and test method are with example 1, and gained catalyst activity component is:
P
1.03Mo
12As
0.3V
0.25Sb
0.25Cu
0.25K
1.5Ox
Test-results is listed in table 2.
Example 3
In example 1, change the ammoniacal liquor adding into 20 milliliters, other condition is all identical with example 1, and gained catalyst activity component is:
P
0.03Mo
12As
0.3V
0.25Sb
0.25Cu
0.25K
1.5Ox
Test-results is listed in table 2.
Comparative example 1
6.36 gram ammonium molybdates are water-soluble, in 30-35 ℃ of solution that adds 2.52 gram potassium hydroxide solids and 1.71 gram butter of antimony, add the solution of 1.5 gram neutralized verdigriss and the solution of 0.9 gram ammonium meta-vanadate again, add 20 milliliters of hydrochloric acid.Stirred 3 hours in 70 ℃.Add 4.8 gram phosphoric acid under the room temperature, add 25 milliliters of ammoniacal liquor, in being lower than 80 ℃ of following evaporates to dryness, again in 110 ℃ of oven dry down.The gained solid was in 250 ℃ of following roastings 2 hours, and adding accounts for the silicon carbide of weight 25%, and adds 4 milliliters of polyvinyl alcohol saturated solutions, is ground into 10-20 order particle after the extrusion molding, in 285 ℃ of roastings 6 hours.Gained activity of such catalysts component is:
P
1.33Mo
12V
0.25Sb
0.25Cu
0.25K
1.5Ox
The test method of catalyzer and condition are with example 1, and reaction result is listed in table 3.
Comparative example 2
In comparative example 1, hydro-oxidation potassium not, other condition is all identical, and gained activity of such catalysts component is:
P
1.33Mo
12V
0.25Sb
0.25Cu
0.25Ox
Reaction result is listed in table 3.
Comparative example 3
In comparative example 1, do not add butter of antimony, other condition is all identical, and gained activity of such catalysts component is:
P
1.33Mo
12V
0.25Cu
0.25K
1.5Ox
Reaction result is listed in table 3.
Comparative example 4
Press comparative example 1, do not add neutralized verdigris, other condition is all identical, obtains the activity of such catalysts component to be:
P
1.33Mo
12V
0.25Sb
0.25K
1.5Ox
Reaction result is listed in table 3.
Comparative example 5
Press comparative example 1, do not add ammonium meta-vanadate, other condition is all identical, obtains the activity of such catalysts component to be:
P
1.33Mo
12Sb
0.25Cu
0.25K
1.5Ox
Reaction result is listed in table 3.
Claims (6)
1, a kind of heteropolyacid catalyst that is used for one-step oxidation process by isobutyraldehyde oxidation generation methacrylic acid is characterized in that:
(A) catalyst activity component general formula is:
Wherein: P is a phosphorus, and As is an arsenic, and Mo is a molybdenum, and V is a vanadium;
X is one or more a metallic element such as antimony, bismuth, iron, manganese, copper, cobalt, nickel, zinc, silver;
Y is one or more a element such as sodium, potassium, rubidium, caesium, magnesium, calcium, barium;
O is an oxygen.
A, b, c, b, f, g and x represent the mol ratio between each element; Its concrete scope is: a=0.1～0.2, and b=0.001～2.0, c=5.0～20, d=0.01～2.0, f=0.01～2.0, g=0.1～5.0, x is a positive number, should satisfy the requirement of each composition valence.
(B) Preparation of catalysts process, it is compound with the respective components element, use acidifying, the general pH value remains on 0.1-3.0, under 50-90 ℃ of temperature, stir slaking 1-10 hour then, the pH value is transferred to 4-7, is lower than 100 ℃ of following evaporates to dryness, with the catalyst activity component that obtains more than the inert support dilution in temperature, after the inert support dilution, active ingredient should account for 50% of gross weight at least, with the carried catalyst moulding, adds the organic reducing material in the moulding, its add-on is the 1-10% of catalyst weight, catalyzer after the moulding will pass through calcination activation, and the calcination activation temperature is 200-420 ℃, and calcination activation will carry out in oxygen-containing atmosphere.
2, said catalyzer in the claim 1 is characterized in that preparing used phosphide and comprises phospho-molybdic acid, phosphoric acid, phosphoric acid salt or Vanadium Pentoxide in FLAKES; Arsenide comprises arsenic molybdic acid, arsenic acid, arsenic powder or arsenate; Change thing phospho-molybdic acid, molybdate or molybdenum oxide; Vanadium compounds is with Vanadium Pentoxide in FLAKES or metavanadate; The compound of X comprises oxide compound, oxyhydroxide, muriate, vitriol, acetate or the nitrate of respective element; The compound of Y comprises oxide compound, oxyhydroxide, vitriol, nitrate or the muriate of respective element.
3, said catalyzer in the claim 1 is characterized in that active ingredient preferably accounts for more than 70% of gross weight.
4, said catalyzer in the claim 1 is characterized in that used inert support is a silicon carbide.
5, said catalyzer in the claim 1 is characterized in that the organic reducing material that adds comprises one or both in glycolic acid, oxalic dialdehyde acid, polyvinyl alcohol, vinyl ethylene glycol or the propenyl ethylene glycol.
6, said catalyzer in the claim 1 or 5 is characterized in that the organic reducing material is a polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105215 CN1022608C (en) | 1990-01-10 | 1990-01-10 | Catalyst for the prodn. of methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105215 CN1022608C (en) | 1990-01-10 | 1990-01-10 | Catalyst for the prodn. of methacrylic acid |
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| Publication Number | Publication Date |
|---|---|
| CN1047985A true CN1047985A (en) | 1990-12-26 |
| CN1022608C CN1022608C (en) | 1993-11-03 |
Family
ID=4879044
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|---|---|---|---|
| CN 90105215 Expired - Fee Related CN1022608C (en) | 1990-01-10 | 1990-01-10 | Catalyst for the prodn. of methacrylic acid |
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| CN1098730C (en) * | 1999-05-20 | 2003-01-15 | 暨南大学 | Heteropoly compound catalyst for selective oxidation of low-carbon olefine and its preparation |
| CN100404133C (en) * | 2001-12-28 | 2008-07-23 | 三菱丽阳株式会社 | Method of producing catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid, catalyst produced by this method, and method of synthesizing unsaturated aldehyde and unsaturated ca |
| CN100417446C (en) * | 2006-03-29 | 2008-09-10 | 上海华谊丙烯酸有限公司 | Forming method of methacrylic acid catalyst synthesized by selective oxidation of methylacrolein |
| CN100490973C (en) * | 2004-11-26 | 2009-05-27 | 上海华谊丙烯酸有限公司 | Catalyst for selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid and its use |
| CN102211027A (en) * | 2010-04-07 | 2011-10-12 | 烟台万华聚氨酯股份有限公司 | Catalyst and preparation method thereof as well as method for preparing methylacrolein with catalyst |
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| CN104646056A (en) * | 2013-11-18 | 2015-05-27 | 上海华谊丙烯酸有限公司 | Molybdenum-phosphor series polyoxometalates catalyst, preparation method and application thereof |
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| CN104984768A (en) * | 2015-07-07 | 2015-10-21 | 中国科学院过程工程研究所 | Hollow nanosphere catalyst preparing methacrylic acid through methylacrolein oxidation and preparation method thereof |
| CN111939952A (en) * | 2020-08-21 | 2020-11-17 | 中国科学院兰州化学物理研究所 | Hierarchical pore catalyst and preparation method and application thereof |
| CN112076786A (en) * | 2020-09-01 | 2020-12-15 | 润泰化学（泰兴）有限公司 | Preparation method of catalyst for preparing methacrylic acid by catalyzing isobutyraldehyde |
| CN114160201A (en) * | 2021-12-27 | 2022-03-11 | 中建安装集团有限公司 | Heteropolyacid catalyst and application thereof |
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1990
- 1990-01-10 CN CN 90105215 patent/CN1022608C/en not_active Expired - Fee Related
Cited By (17)
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| CN1098730C (en) * | 1999-05-20 | 2003-01-15 | 暨南大学 | Heteropoly compound catalyst for selective oxidation of low-carbon olefine and its preparation |
| CN100404133C (en) * | 2001-12-28 | 2008-07-23 | 三菱丽阳株式会社 | Method of producing catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid, catalyst produced by this method, and method of synthesizing unsaturated aldehyde and unsaturated ca |
| CN100490973C (en) * | 2004-11-26 | 2009-05-27 | 上海华谊丙烯酸有限公司 | Catalyst for selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid and its use |
| CN100417446C (en) * | 2006-03-29 | 2008-09-10 | 上海华谊丙烯酸有限公司 | Forming method of methacrylic acid catalyst synthesized by selective oxidation of methylacrolein |
| CN102211027A (en) * | 2010-04-07 | 2011-10-12 | 烟台万华聚氨酯股份有限公司 | Catalyst and preparation method thereof as well as method for preparing methylacrolein with catalyst |
| CN102211027B (en) * | 2010-04-07 | 2013-06-12 | 烟台万华聚氨酯股份有限公司 | Catalyst and preparation method thereof as well as method for preparing methylacrolein with catalyst |
| CN103945938B (en) * | 2011-11-17 | 2016-08-24 | 日本化药株式会社 | Methacrylic acid catalyst for producing and use the manufacture method of methacrylic acid of this catalyst |
| 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 |
| CN104646056A (en) * | 2013-11-18 | 2015-05-27 | 上海华谊丙烯酸有限公司 | Molybdenum-phosphor series polyoxometalates catalyst, preparation method and application thereof |
| CN104646056B (en) * | 2013-11-18 | 2017-01-11 | 上海华谊丙烯酸有限公司 | Molybdenum-phosphor series polyoxometalates catalyst, preparation method and application thereof |
| CN104801312A (en) * | 2015-03-17 | 2015-07-29 | 烟台大学 | Composite oxide catalyst and preparation method |
| CN104984768A (en) * | 2015-07-07 | 2015-10-21 | 中国科学院过程工程研究所 | Hollow nanosphere catalyst preparing methacrylic acid through methylacrolein oxidation and preparation method thereof |
| CN111939952A (en) * | 2020-08-21 | 2020-11-17 | 中国科学院兰州化学物理研究所 | Hierarchical pore catalyst and preparation method and application thereof |
| CN111939952B (en) * | 2020-08-21 | 2022-04-19 | 中国科学院兰州化学物理研究所 | Hierarchical pore catalyst and preparation method and application thereof |
| CN112076786A (en) * | 2020-09-01 | 2020-12-15 | 润泰化学（泰兴）有限公司 | Preparation method of catalyst for preparing methacrylic acid by catalyzing isobutyraldehyde |
| CN112076786B (en) * | 2020-09-01 | 2022-11-22 | 润泰化学（泰兴）有限公司 | Preparation method of catalyst for preparing methacrylic acid by catalyzing isobutyraldehyde |
| CN114160201A (en) * | 2021-12-27 | 2022-03-11 | 中建安装集团有限公司 | Heteropolyacid catalyst and application thereof |
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