CN105289675A - Nanometer heteropolyacid catalyst used for preparing methacrylic acid through oxidation of methacrolein - Google Patents
Nanometer heteropolyacid catalyst used for preparing methacrylic acid through oxidation of methacrolein Download PDFInfo
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Abstract
The invention relates to a nanometer heteropolyacid catalyst prepared through a soft template method and used for preparing methacrylic acid through oxidation of methacrolein and a preparing method of the nanometer heteropolyacid catalyst. According to the catalyst, quaternary ammonium salt surfactant serves as a template and reacts with heteropolyacid, then relevant elements are added, and the nanometer heteropolyacid catalyst of a mesoporous structure is obtained through roasting, wherein the nanometer heteropolyacid catalyst is obtained through self-assembly of nanoscale particles, the diameter of the nanometer heteropolyacid catalyst ranges from 0.5 micrometer to 5 micrometers, the pore diameter ranges from 2 nanometers to 5 nanometers, and the specific surface area ranges from 20 m<2>/g to 200 m<2>/g. The catalyst is used for oxidizing methacrolein into methacrylic acid, and compared with other kinds of catalysts, activity is increased by more than 5 times, and a long catalyzing life is achieved.
Description
Technical field
The present invention relates to a kind of high-specific area nano heteropolyacid catalyst and preparation method thereof, belong to catalyst preparing and application.
Background technology
As a kind of excellent catalyst, the investigation and application of heteropoly acid receives to be paid close attention to widely.It all has application in reactions such as oxidation, esterification and shape selective catalysis.Catalyst methacrolein (MAL) selective oxidation wherein based on phosphomolybdic acid and molybdovanaphosphoric acid is that methacrylate (MAA) successfully realizes industrialization.It is the key reaction of producing methylmethacrylate (MMA) C2, C4 new technology that MAL is oxidized to MAA.Need the strong sulfuric acid of hypertoxic hydrogen cyanide, corrosivity with Acetone cyanohydrin method and produce compared with a large amount of ammonium hydrogen sulfate, C2, C4 new technology atomic efficiency is high, and waste discharge amount is little, the requirement of composite green chemistry.
1987, prepared by MotomuOh-Kita etc. took molybdovanaphosphoric acid as parent, added the catalyst of the element such as copper, iron, and the conversion ratio obtaining MAL is the selective of 80% ~ 97%, MAA is 80 ~ 87% (US4803302A).It with the addition of zinc again in US4804778, has allocated the ratio of copper, iron, and the conversion ratio obtaining MAL is the selective of 88 ~ 89%, MAA is 86 ~ 89%.But because such specific surface area of catalyst is little, therefore catalytic efficiency is low, and phosphomolybdic acid, molybdovanaphosphoric acid price are higher, therefore need the catalytic efficiency improving catalyst.Expanding its specific area, is the Main Means improving catalytic efficiency.Load is the main mode improving catalyst efficiency, bibliographical information (CatalysisCommunications13 (2011) 59 – 62; AppliedCatalysisA:General325 (2007) 263 – 269), phosphomolybdic acid and molybdovanaphosphoric acid are loaded to the SiO of ammonification
2after class carrier, its TOF is significantly improved, but thermal decomposition and inactivation easily occur the catalyst after load in course of reaction.Having patent report (CN101980781A) in addition, improving duct and the specific area of catalyst by adding the organic polymers such as polyethylene glycol in catalyst preparation process, but the catalyst pore passage structure obtained is random and uncontrollable.Therefore need to develop a kind of new heteropolyacid catalyst, make that the catalytic efficiency of catalyst is high, specific area, pore passage structure are controlled, and catalyst can be made to overcome the shortcoming of the inactivation because of thermal decomposition.
Summary of the invention
The present invention relates to a kind of nanometer heteropolyacid catalyst with even duct prepared by soft template method and preparation method thereof, comprise the operations such as the synthesis of catalyst and catalyst, drying and roasting, this catalyst take quaternary ammonium salt surface active agent as soft template, heteropolyacid salt can be made diameter is 1 ~ 5 micron, have 2 ~ 5 mesoporous nanos, specific area is 20 ~ 200m
2the nano-scale particle of/g, because its specific area is large, the oxidation-reduction quality of quaternary ammonium salt adjustable catalyst in roasting process, therefore can significantly improve catalyst activity.Its duct size regulates by the kind changing quaternary ammonium salt, and specific area regulates by the concentration of reconciliation statement surface-active agent.It can be used for the reaction of catalyzing iso-butane olefine aldehydr oxidation preparing isobutene acid.
The chemical expression of this catalyst is:
X
aY
bZ
cP
dMo
12-eV
eO
f
Wherein, X is be the ammonium ion of 8 to 20 carbochains containing carbon number; Y is one or both in K, Rb, Cs, and Z is one or more in Ti, Fe, Co, Cu, Zn, As, Se, Mn, Sn, Ce; A is the atom number of X in a catalytic clusters, and the atom number that to be 1 ~ 2, b be in Y element catalytic clusters is 1 ~ 2; C is the atom number of Z element in a catalytic clusters, is 0.05 ~ 1; D is the number of P atom in a catalytic clusters, is 1 ~ 2; E is the V atomicity replacing Mo in structure with Keggin, is 0 ~ 3; F is for meeting the atomicity of the oxygen required for chemical valence.
The preparation method of such heteropolyacid catalyst comprises following operation:
A quaternary ammonium salt surface active agent that () gets containing X ion is some, and add in a certain amount of deionized water at a certain temperature, stirring and dissolving, obtains colourless transparent solution;
B () gets a certain amount of heteropoly acid, be dissolved in certain deionized water, in uniform temperature, when stirring, be added drop-wise in the colourless transparent solution that operation (a) obtains, after being added dropwise to complete, stir a period of time, obtain the suspension of fluffy solid;
C () is got a certain amount of compound containing Y and Z in proportion and is dissolved in deionized water, wiring solution-forming, is then slowly added drop-wise in the suspension that operation (b) obtains, after dropwising at a certain temperature by this solution, reaction a period of time, obtain slurry A;
D slurry A is carried out drying by (), obtain catalyst precursor;
E () by the catalyst precursor that obtains in operation (d) at a certain temperature, in oxygen-enriched atmosphere, roasting certain hour, obtains heteropolyacid catalyst.
Surfactant in operation (a) can be containing carbon number the quaternary ammonium salt of the ammonium ion being 8 to 20 carbochains, as octyl trimethyl ammonium ion, nonyl trimethyl ammonium ion, decyl trimethyl ammonium ion, undecyl trimethyl ammonium ion, dodecyl trimethyl ammonium ion, tridecyl trimethyl ammonium ion, ammonium ion, pentadecyl trimethyl ammonium ion, cetyltrimethylammonium ion heptadecyl trimethyl ammonium ion, the villaumite of octadecyltrimethylammonium ion and two dodecyl dimethyl ammonium ion, sulfate, carbonate and nitrate.
In operation (a), the solution temperature of surfactant is 10 ~ 100 DEG C, and a surfactant dissolves is in 3 ~ 56 parts of deionized waters, and be wherein preferably 30 ~ 80 DEG C, the ratio of surfactant and deionized water is 1:5 ~ 10.
In operation (b), heteropoly acid is phosphomolybdic acid or molybdovanaphosphoric acid, the ratio added water is that a heteropoly acid is dissolved in 1 thousand to one ten thousand part of deionized water, the ratio of heteropoly acid and surfactant is 1:1 ~ 1:2.5, reaction temperature is 20 ~ 110 DEG C, reaction time is 1 ~ 24h, is wherein preferably molybdovanaphosphoric acid, and acid and surfactant are than being 1:1 ~ 2, reaction temperature is 50 ~ 90 DEG C, and the reaction time is 5 ~ 12h.
The compound containing Y, Z described in operation (c) is the one in the nitrate of respective metal element, carbonate, chloride or oxide, reaction temperature is 60 ~ 110 DEG C, reaction time is 2 ~ 24h, and wherein preferable reaction temperature is 80 ~ 95 DEG C, and the preferred reaction time is 6 ~ 12h.
In operation (d), drying mode is atmospheric agitation evaporation drying, evaporation drying is stirred in decompression, reduce pressure rotary evaporation drying, spraying dry, baking temperature is 80 ~ 200 DEG C, wherein preferably drying mode is for stirring evaporation drying, and preferred baking temperature is 80 ~ 100 DEG C.
In operation (e), sintering temperature is 300 ~ 400 DEG C; In oxygen-enriched atmosphere, oxygen content percent by volume is 20% ~ 50%; Roasting time is 5 ~ 48h, and wherein preferably sintering temperature is 320 ~ 370 DEG C, and oxygen ratio is 25 ~ 35%, and roasting time is 6 ~ 12h.
Catalyst involved in the present invention be used for fixed bed by the molecular oxygen in air in the gas phase catalysis MAL be oxidized to MAA.
The conversion ratio computational methods of methacrolein are as follows:
The selective calculation of methacrylate is as follows:
This catalyst take quaternary ammonium salt as template, phosphato-molybdic heteropolyacid salt is that active component has prepared the heteropoly acid saline catalyst with bigger serface, meso-hole structure, compared with traditional heteropoly acid, its specific area is large, catalyst has the active sites participating in reacting more, it has meso-hole structure, and mass transfer effect is better, and therefore catalytic efficiency is higher.Quaternary ammonium salt surface active agent, in roasting process, contained hydrocarbonly and amino can to regulate the oxidation-reduction quality of catalyst, therefore has high catalytic performance.In the reaction for methacrolein oxidation being methacrylate, the conversion ratio of methacrolein is high, the selective height of methacrylate, long catalytic life (Absorbable organic halogens runs more than 500 hours).Compared with other such catalyst, TOF improves more than 5 times.
Accompanying drawing explanation
The SEM figure of Fig. 1 catalyst
Detailed description of the invention
With embodiment, the present invention is described below, but scope of the present invention is not by the restriction of embodiment.
Embodiment 1
Take 10g softex kw (CTAB), be at room temperature dissolved in 200mL deionized water.Take 49g molybdovanaphosphoric acid, be dissolved in 75mL deionized water, the molybdovanaphosphoric acid solution prepared slowly is added drop-wise in CTAB solution when agitating heating (40 DEG C), after dropwising, reaction 6h.
Take 5.36gCsNO
3, 0.259gCu (NO
3)
2, 1.17gH
3asO
4with 0.666gFe (NO
3)
3be dissolved in 50mL deionized water, under stirring state at 80 DEG C, be slowly added drop-wise in above-mentioned suspension, after dropwising, reaction 6h.After having reacted, stir evaporate to dryness.By the solid 80 DEG C of dried overnight in air dry oven obtained, obtain catalyst precursor.
Evaporate to dryness when being mixed by reactant liquor, obtains pressed powder, and by the granulation of pressed powder compressing tablet, in the air atmosphere of flowing, 350 DEG C of roasting 12h, removing surfactant, obtains the catalyst with catalytic activity.
Consisting of of catalyst
CsCu
0.05As
0.3Fe
0.1VMo
11PO
40
The ratio of 1ml catalyst granules according to 2:1 mixed with quartz sand, then loading diameter is 8mm, and length is in the fixed bed reactors of the stainless-steel pipe of 40cm.300 DEG C, react under normal pressure, methacrolein: oxygen: nitrogen: water mol ratio is 1:2.5:15:4, time of contact is 2s.Start sample analysis after 6h is carried out in reaction, liquid-like gas-chromatography fid detector detects, and gas sample gas-chromatography TCD detector detects, and the conversion ratio of MAL is the selective of 85%, MAA is 95.5%.After continuous operation 1000h, it is more than 90% that the conversion ratio of MAL still remains on the selective of more than 80%, MAA.
Embodiment 2
Take 10g Cetyltrimethylammonium bromide, be at room temperature dissolved in 200mL deionized water.Take 45g molybdovanaphosphoric acid, be dissolved in 70mL deionized water, the molybdovanaphosphoric acid solution prepared slowly is added drop-wise in Cetyltrimethylammonium bromide solution when agitating heating (40 DEG C), after dropwising, reaction 8h.
Take 4.924gCsNO
3, 0.231gCo (NO
3)
2, 0.475gCu (NO
3)
2, 0.366gH
2seO
4, 0.096gZn (NO
3)
2be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned suspension under 85 DEG C of stirring states, after dropwising, vigorous stirring reaction 3h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain yellow green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
CsCo
0.05Cu
0.1Se
0.1Zn
0.02VMo
11PO
40
The conversion ratio obtaining MAL is the selective of 89.2%, MAA is 93.6%.
Embodiment 3
Take 10g DTAB, be at room temperature dissolved in 200mL deionized water.Take 64.3g phosphomolybdic acid (anhydrous), be dissolved in 70mL deionized water, the phosphorus molybdenum acid solution prepared slowly is added drop-wise in DTAB solution when agitating heating (40 DEG C), after dropwising, reaction 5h.
Take 3.433gCsNO
3, 1.70gFe (NO
3)
3, 0.533gMn (NO
3)
4, 0.061gTi (NO
3)
2, 0.186gCe (NO
3)
2be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned suspension under 80 DEG C of stirring states, after dropwising, vigorous stirring reaction 3h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain bottle green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
Cs
0.5Fe
0.2Mn
0.05Ti
0.01Ce
0.02PMo
12O
40
The conversion ratio obtaining MAL is the selective of 85%, MAA is 91.2%.
Embodiment 4
Take 10g DTAB, be at room temperature dissolved in 200mL deionized water.Take 57.1g molybdovanaphosphoric acid (anhydrous), be dissolved in 70mL deionized water, the molybdovanaphosphoric acid solution prepared slowly is added drop-wise in DTAB solution when agitating heating (40 DEG C), after dropwising, reaction 5h.
Take 3.232gKNO
3, 0.3gCu (NO
3)
2, 0.606gZn (NO
3)
2, 0.077gSn (NO
3)
2, 0.155gFe (NO
3)
3be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned suspension under 80 DEG C of stirring states, after dropwising, vigorous stirring reaction 5h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain bottle green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
KCu
0.05Fe
0.2Zn
0.1Sn
0.01VMo
11PO
40
The conversion ratio obtaining MAL is the selective of 82.1%, MAA is 90.8%.
Embodiment 5
Take 10g TTAB, be at room temperature dissolved in 200mL deionized water.Take 52.4g molybdovanaphosphoric acid, be dissolved in 70mL deionized water, the molybdovanaphosphoric acid solution prepared slowly is added drop-wise in TTAB solution when agitating heating (40 DEG C), after dropwising, reaction 5h.
Take 2.969gKNO
3, 2.505gH
3asO
4, 0.557gZn (NO
3)
2, 0.276gCu (NO
3)
2, 2.134gFe (NO
3)
3be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned suspension under 80 DEG C of stirring states, after dropwising, vigorous stirring reaction 5h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain bottle green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
KCu
0.05Fe
0.3As
0.6Zn
0.1VMo
11PO
40
The conversion ratio obtaining MAL is the selective of 87.6%, MAA is 93.2%.
Embodiment 6
Take 10g octyl trimethylammonium bromide, be at room temperature dissolved in 200mL deionized water.Take 69.6g molybdovanaphosphoric acid, be dissolved in 70mL deionized water, the molybdovanaphosphoric acid solution prepared slowly is added drop-wise in octyl trimethyl ammonium bromide solution when agitating heating (40 DEG C), after dropwising, reaction 5h.
Take 7.625gCsNO
3, 0.741gZn (NO
3)
2, 1.47gCu (NO
3)
2, 2.839gFe (NO
3)
3be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned suspension under 80 DEG C of stirring states, after dropwising, vigorous stirring reaction 5h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain bottle green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
CsCu
0.2Zn
0.1Fe
0.3VMo
11PO
40
The conversion ratio obtaining MAL is the selective of 92.6%, MAA is 87.5%.
Comparing embodiment 1
Take 49g molybdovanaphosphoric acid, be dissolved in 275mL deionized water, take 5.36gCsNO
3, 0.259gCu (NO
3)
2, 1.17gH
3asO
4with 0.666gFe (NO
3)
3be dissolved in 50mL deionized water, under stirring state at 80 DEG C, be slowly added drop-wise in above-mentioned solution, after dropwising, reaction 6h.After having reacted, stir evaporate to dryness.By the solid 80 DEG C of dried overnight in air dry oven obtained, obtain catalyst precursor.
Evaporate to dryness when being mixed by reactant liquor, obtains pressed powder, and by the granulation of pressed powder compressing tablet, in the air atmosphere of flowing, 350 DEG C of roasting 12h, removing surfactant, obtains the catalyst with catalytic activity.
Consisting of of catalyst
CsCu
0.05As
0.3Fe
0.1VMo
11PO
40
The roasting evaluation method of catalyst is as embodiment 1.
The conversion ratio obtaining MAL is the selective of 75.6%, MAA is 70.6%.
Comparing embodiment 2
Take 45g molybdovanaphosphoric acid, be dissolved in 270mL deionized water.Take 4.924gCsNO
3, 0.231gCo (NO
3)
2, 0.475gCu (NO
3)
2, 0.366gH
2seO
4, 0.096gZn (NO
3)
2be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned solution under 85 DEG C of stirring states, after dropwising, vigorous stirring reaction 3h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain yellow green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
CsCo
0.05Cu
0.1Se
0.1Zn
0.02VMo
11PO
40
The conversion ratio obtaining MAL is the selective of 70.5%, MAA is 81.7%.
Comparing embodiment 3
Take 64.3g phosphomolybdic acid (anhydrous), be dissolved in 270mL deionized water.Take 3.433gCsNO
3, 1.70gFe (NO
3)
3, 0.533gMn (NO
3)
4, 0.061gTi (NO
3)
2, 0.186gCe (NO
3)
2be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned solution under 80 DEG C of stirring states, after dropwising, vigorous stirring reaction 3h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain bottle green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
Cs
0.5Fe
0.2Mn
0.05Ti
0.01Ce
0.02PMo
12O
40
The conversion ratio obtaining MAL is the selective of 72%, MAA is 74.8%.
Comparing embodiment 4
Take 57.1g molybdovanaphosphoric acid (anhydrous), be dissolved in 270mL deionized water.Take 3.232gKNO
3, 0.3gCu (NO
3)
2, 0.606gZn (NO
3)
2, 0.077gSn (NO
3)
2, 0.155gFe (NO
3)
3be dissolved in 50mL deionized water.The solution prepared slowly is dropped in above-mentioned solution under 80 DEG C of stirring states, after dropwising, vigorous stirring reaction 5h, reaction terminate rear stirring evaporate to dryness, by the solid obtained in air dry oven 80 DEG C spend the night, obtain bottle green catalyst precursor.
Catalyst roasting evaluation method as embodiment 1, consisting of of catalyst
KCu
0.05Fe
0.2Zn
0.1Sn
0.01VMo
11PO
40
The conversion ratio obtaining MAL is the selective of 70.6%, MAA is 75.8%.
In table 1 embodiment MAL conversion ratio and MAA selective
Claims (10)
1. the heteropolyacid catalyst for the acid of methacrolein oxidation preparing isobutene prepared of soft template method, is characterized in that this catalyst is soft template with quaternary ammonium salt, prepares that diameter is 0.5 ~ 5 micron, mesoporous pore size is 2 ~ 5 nanometers, specific area is 20 ~ 100m
2the heteropolyacid catalyst of/g, it consists of:
X
aY
bZ
cP
dMo
12-eV
eO
f
Wherein, X is be one or more in the ammonium ion of 8 to 20 carbochains containing carbon number; Y is one or both in K, Rb, Cs, and Z is one or more in Ti, Fe, Co, Cu, Zn, As, Se, Mn, Sn, Ce; A is the atom number of X in a catalytic clusters, be 1 ~ 2, b is the atom number of Y element in a catalytic clusters; Be 1 ~ 2, c being the atom number of Z element in a catalytic clusters, is 0.05 ~ 1; D is the number of P in a catalytic clusters, is 1 ~ 2; E is the V atomicity replacing Mo in structure with Keggin, is 0 ~ 3; F is for meeting the atomicity of the oxygen required for chemical valence.
2. method according to claim 1, is characterized in that comprising following operation:
A quaternary ammonium salt surface active agent that () gets containing X ion is some, adds in a certain amount of deionized water at a certain temperature, stirring and dissolving, obtains water white transparency sol solution;
B () gets a certain amount of heteropoly acid, be dissolved in certain deionized water, in uniform temperature, when stirring, be added drop-wise in the colourless transparent solution that operation (a) obtains, after being added dropwise to complete, stir a period of time, obtain the suspension of fluffy solid;
C () is got a certain amount of compound containing Y and Z in proportion and is dissolved in deionized water, wiring solution-forming, is then slowly added drop-wise in the suspension that operation (b) obtains, after dropwising at a certain temperature by this solution, reaction a period of time, obtain slurry A;
D slurry A is carried out drying by (), obtain catalyst precursor;
E () by the catalyst precursor that obtains in operation (d) at a certain temperature, in oxygen-enriched atmosphere, roasting certain hour, obtains heteropolyacid catalyst.
3. method according to claim 2, it is characterized in that the surfactant in operation (a) can be containing carbon number the quaternary ammonium salt of the ammonium ion being 8 to 20 carbochains, as octyl trimethyl ammonium ion, nonyl trimethyl ammonium ion, decyl trimethyl ammonium ion, undecyl trimethyl ammonium ion, dodecyl trimethyl ammonium ion, tridecyl trimethyl ammonium ion, ammonium ion, pentadecyl trimethyl ammonium ion, cetyltrimethylammonium ion heptadecyl trimethyl ammonium ion, the villaumite of octadecyltrimethylammonium ion and two dodecyl dimethyl ammonium ion, sulfate, carbonate and nitrate.
4. method according to claim 2, is characterized in that in operation (a), surfactant solution preparation condition is that 1 part of surfactant dissolves is in 3 ~ 56 parts of deionized waters at 10 ~ 100 DEG C.
5. method according to claim 2, it is characterized in that in operation (b), heteropoly acid is phosphomolybdic acid or molybdovanaphosphoric acid, the ratio of heteropoly acid and surfactant is 1:1 ~ 1:2.5.
6. method according to claim 2, it is characterized in that in operation (b) that preparation condition is temperature is 20 ~ 110 DEG C, and the time is 1 ~ 24h.
7. method according to claim 2, the compound that it is characterized in that containing described in operation (c) Y, Z is one or more in the nitrate of respective metal element, carbonate, chloride or oxide.
8. method according to claim 2, it is characterized in that in operation (c) that preparation condition is temperature is 60 ~ 110 DEG C, and the time is 2 ~ 24h.
9. method according to claim 2, is characterized in that the one that in operation (d), drying mode is atmospheric agitation evaporation drying, decompression is stirred evaporation drying, reduced pressure in rotary evaporation drying or spraying dry.
10. catalyst according to claim 2, is applied to catalyzing iso-butane olefine aldehydr and prepares methacrylate through molecular oxygen oxidation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109513446A (en) * | 2018-12-05 | 2019-03-26 | 中国科学院过程工程研究所 | A kind of preparation method of isobutene or Oxidation of t-Butanol synthesizing methyl methacrylaldehyde catalyst |
| CN112237934A (en) * | 2019-07-19 | 2021-01-19 | 中国科学院大连化学物理研究所 | Mo-P series catalyst and preparation method and application thereof |
| CN115245840A (en) * | 2021-12-03 | 2022-10-28 | 平顶山学院 | Keggin structure heteropoly acid nano catalyst for cyclohexane molecular oxygen selective oxidation reaction and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407961A (en) * | 1999-12-24 | 2003-04-02 | 三星综合化学株式会社 | Preparation method of methacrylic acid |
| CN104001543A (en) * | 2014-06-09 | 2014-08-27 | 中国科学院过程工程研究所 | Catalyst for preparing methacrylic acid by oxidation of methylacrolein and preparation method of catalyst |
| WO2014157040A1 (en) * | 2013-03-28 | 2014-10-02 | 日本化薬株式会社 | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid |
-
2015
- 2015-10-21 CN CN201510689085.3A patent/CN105289675A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407961A (en) * | 1999-12-24 | 2003-04-02 | 三星综合化学株式会社 | Preparation method of methacrylic acid |
| WO2014157040A1 (en) * | 2013-03-28 | 2014-10-02 | 日本化薬株式会社 | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid |
| CN104001543A (en) * | 2014-06-09 | 2014-08-27 | 中国科学院过程工程研究所 | Catalyst for preparing methacrylic acid by oxidation of methylacrolein and preparation method of catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 丁彤等: "《中国化工产品大全 下》", 31 October 1994 * |
| 刘玉荣等: "《介孔碳材料的合成及应用》", 30 June 2012, 北京：国防工业出版社 * |
| 钱伯章等: "《石油化工技术进展与市场分析》", 31 October 2004, 北京：石油工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109513446A (en) * | 2018-12-05 | 2019-03-26 | 中国科学院过程工程研究所 | A kind of preparation method of isobutene or Oxidation of t-Butanol synthesizing methyl methacrylaldehyde catalyst |
| CN112237934A (en) * | 2019-07-19 | 2021-01-19 | 中国科学院大连化学物理研究所 | Mo-P series catalyst and preparation method and application thereof |
| CN112237934B (en) * | 2019-07-19 | 2021-12-07 | 中国科学院大连化学物理研究所 | Mo-P series catalyst and preparation method and application thereof |
| CN115245840A (en) * | 2021-12-03 | 2022-10-28 | 平顶山学院 | Keggin structure heteropoly acid nano catalyst for cyclohexane molecular oxygen selective oxidation reaction and preparation method thereof |
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