CN101224431A - Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof - Google Patents
Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof Download PDFInfo
- Publication number
- CN101224431A CN101224431A CNA2008100545436A CN200810054543A CN101224431A CN 101224431 A CN101224431 A CN 101224431A CN A2008100545436 A CNA2008100545436 A CN A2008100545436A CN 200810054543 A CN200810054543 A CN 200810054543A CN 101224431 A CN101224431 A CN 101224431A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- heteropoly acid
- molecular sieve
- acid
- methylal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
A methanol catalyst for the selective oxidation of methylal is composed of heteropoly acid and molecular sieve carrier, wherein, the heteropoly acid takes 3-45% of the catalyst by weight percentage, the metal content takes 0-5% of the catalyst by metal single mass, and remaining is silicon modular sieve. For the preparation of the catalyst, a mechanical mixing method, an immersion method, an in-situ synthesis method, and a surface grafting method are applied. The invention can realize the preparation of methylal by oxidation method in one step, shorten process flow and reduce production cost. Meanwhile, the catalyst is obviously characterized by high selectivity of methylal, good stability and long service life.
Description
Technical field
The invention belongs to a kind of solid catalyst that is used for methanol oxidation to methylal by one step and its production and application.
Technical background
Dimethoxym ethane has another name called dimethoxymethane, is a kind of green Downstream Products of Methanol of high added value, is widely used in cosmetics, medicine, automobile, fields such as rubber.Its outstanding dirt-removing power and volatility makes it become the new generation of environment protection solvent of State Bureau of Environmental Protection's keypoint recommendation; As cleaning agent, dimethoxym ethane can replace chlorinated solvents, reduces the discharging of volatile contaminant; Simultaneously, dimethoxym ethane is the important source material of preparation high-concentration formaldehyde (83.3%).In addition,, can effectively improve the combustion position of diesel oil in engine, improve the thermal efficiency, reduce the discharging of pollutant, be considered to a kind of fuel additive that has application prospect because dimethoxym ethane has higher oxygen content and Cetane number.
At present, the synthetic method of dimethoxym ethane mainly is to be that raw material is synthetic through two-step method with methyl alcohol, promptly at first methanol oxidation is generated formaldehyde, and the further condensation of formaldehyde and methyl alcohol generates dimethoxym ethane then.Wherein first step adopts silver (873-923K) or iron molybdenum (573-703K) catalyst usually, carries out on second common acidic catalyst of step, and acidic catalyst commonly used has inorganic acid, acidic molecular sieve, large hole cation exchanger resin etc.A kind of method of being produced dimethoxym ethane with the HZSM-5 molecular sieve by methyl alcohol and formalin was mutually once disclosed as Chinese patent CN1301688.U.S. Pat 4967014 adopts large hole cation exchanger resin to fill in and produces dimethoxym ethane in the reactor.
The technical matters of two-step method synthesizing dimethoxym ethane is ripe relatively, but its complex process, flow process is tediously long, and high production cost is difficult to realize the large-scale production and the application of dimethoxym ethane, particularly its application of bulk chemical such as additive that acts as a fuel.Therefore, two step building-up processes effectively are coupled,, then can significantly reduce production costs, thereby realize the low-cost production and the scale application of dimethoxym ethane by the direct synthesizing dimethoxym ethane of methanol oxidation.The existing relevant report of the research in this field at present, the patent of more typical methanol oxidation to methylal by one step catalyst aspect has: U.S. Pat 6403841, it adopts SbRe
2O
6The Preparation of Catalyst dimethoxym ethane; U.S. Pat 0154226, it adopts H
3+nVnMo
12-nPO
4Catalyst carries out the methanol oxidation synthesizing dimethoxym ethane; Chinese patent CN1911503A, it adopts ReO
x/ ZrO
2Catalyst carries out methanol oxidation and produces dimethoxym ethane; Chinese patent CN1634655, it adopts the TiO of S modification
2Supported V
2O
5Catalyst carries out methanol oxidation and prepares dimethoxym ethane.From the performance of present catalyst, activity of such catalysts, selectivity and stable aspect remain in bigger deficiency.Wherein, introduced the rhenium element of price comparison costliness in the catalyst formulation described in U.S. Pat 6403841 and the Chinese patent CN1911503A, cause catalysqt deactivation etc. owing to the high oxide of rhenium at high temperature volatilizees easily, limited the practical application of this type of catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of reaction condition gentleness, good stability, the life-span is long, the Catalysts and its preparation method and the application that methanol by one-step method are converted into dimethoxym ethane high to the selectivity of dimethoxym ethane.
Catalyst of the present invention is made up of heteropoly acid and silica-based molecular sieve, also can in heteropoly acid/molecule sieve nest, introduce metal component, wherein to account for the catalyst weight degree be 3～45% to heteropoly acid, it is 0～5% that tenor accounts for the catalyst weight degree in the metal simple-substance amount, and all the other are silica-based molecular sieve.
Aforesaid heteropoly acid is phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid, silicomolybdic acid or phosphorus molybdenum vanadium heteropolyacid.
Aforesaid metal component is vanadium, molybdenum, copper, zinc, iron, manganese, tin or zirconium etc.
Aforesaid silica-based molecular sieve is SBA-15, SBA-16, MCM-41, ZSM-5, X type AK Y zeolite.
One, when catalyst was formed not the containing metal component, the Preparation of catalysts method that heteropoly acid/molecular sieve is formed was as follows:
1, mechanical mixing prepares heteropoly acid/molecular sieve catalyst: heteropoly acid and silica-based molecular sieve ground and mixed are even, at 300～600 ℃ of roasting 5～10h, promptly get heteropoly acid/molecular sieve catalyst.
2, immersion process for preparing heteropoly acid/molecular sieve catalyst: with heteropoly acid with dissolved in distilled water after, add silica-based molecular sieve carrier, become thick presoma behind 20～80 ℃ of dippings, at 60～110 ℃ of drying 5～24h, 300～600 ℃ of roasting 5～10h in air promptly get heteropoly acid/molecular sieve catalyst then.
3, in-situ synthesis prepares heteropoly acid-molecular sieve catalyst:
It is to be carrier with silica-based molecular sieve SBA-15 molecular sieve that in-situ synthesis prepares heteropoly acid-molecular sieve catalyst, typical building-up process is as described below, wherein silica-based molecular sieve SBA-15 is removed the template agent by template agent polyvinylether-polypropylene ether-polyvinylether triblock copolymer and ethyl orthosilicate again and is obtained after reaction, heteropoly acid is introduced in the SBA-15 forming process in the SBA-15 duct, forms heteropoly acid-SBA-15 catalyst.
With template agent polyvinylether-polypropylene ether-polyvinylether triblock copolymer (P
123) add heteropoly acid after being dissolved in deionized water, to add acid is 0.5～2.5 with regulator solution pH value in the dissolving back fully, the back adding ethyl orthosilicate (TEOS) that stirs, the mol ratio that makes each material is P
123: heteropoly acid: TEOS: H
2O=(1～1.28): (0.057～1.10): (46.39～676): (6804～11973), stir 12～24h at 30～50 ℃ of constant temperature, 80～100 ℃ of crystallization 12～48h, behind the suction filtration in 80～110 ℃ of drying 5～24h, roasting 5～12h in 400～600 ℃ of air promptly gets heteropoly acid-SBA-15 catalyst then.
The acid that aforesaid in-situ synthesis prepares heteropoly acid-molecular sieve catalyst adjusting pH value is hydrochloric acid, sulfuric acid or nitric acid.
When catalyst was formed the containing metal component, the preparation method of metal-heteropoly acid/molecular sieve catalyst was as follows:
The metal component salts solution is added in heteropoly acid/molecular sieve catalyst that above-mentioned 1,2 or 3 preparation methods obtain, dipping 2～10h, in 60～110 ℃ of drying 5～24h, in air,, promptly obtain metal-heteropoly acid/molecular sieve catalyst then in 400～600 ℃ of roasting 5～10h.
Aforesaid metal component salt is
Application of Catalyst condition of the present invention is: with catalyst in oxygen-containing atmosphere in 300～600 ℃ handle 1～5h after, cool to 150～250 ℃ of reaction temperatures, feed then and be preheated to 130～150 ℃ the methanol steam and the gaseous mixture of oxygen-containing gas, the percent by volume of methyl alcohol is 1.0～15.0% in the gaseous mixture, and the reaction gas air speed is 1000～10000ml/g
Cat.h, reaction pressure is a normal pressure.
Aforesaid oxygen-containing gas is the gaseous mixture of air, oxygen and nitrogen or the gaseous mixture of oxygen and helium.
Advantage of the present invention:
(1) catalyst has adjustable oxidation-reduction quality and acidity, and can utilize the architectural feature realization of molecular screen material immobilized to the confinement of heteropoly acid and metal, and regulation activity position configuration is realized the Selective Control of oxidation depth;
(2) the present invention can realize that the methanol by one-step method oxidation prepares dimethoxym ethane, simplifies technological process, reduces production costs;
(3) catalyst that the present invention developed is to the selectivity height of dimethoxym ethane, good stability, and the life-span is long.
The specific embodiment
Embodiment 1
0.25g phosphomolybdic acid and the careful ground and mixed of 2.5g SBA-16 molecular sieve is even, 350 ℃ of roasting 5h, getting phosphomolybdic acid content is 7.48wt%, SBA-15 content is the catalyst of 92.52wt%.
With catalyst in 10vol%O
2/ Ar atmosphere is handled 4h for following 350 ℃, drops to 180 ℃, feeds methanol steam and the Ar and the O of 140 ℃ of preheatings
2Gaseous mixture, unstrpped gas consists of CH
3OH/O
2/ Ar=6.3/9.4/84.3, reaction pressure is a normal pressure, the reaction gas air speed is 4000ml/g
Cat.h, the reactivity worth of catalyst sees Table 1.
Embodiment 2
0.13g phosphomolybdic acid and the careful ground and mixed of 2.5g MCM-41 molecular sieve is even, 550 ℃ of roasting 5h, getting phosphomolybdic acid content is 4.03wt%, MCM-41 content is the catalyst of 95.97wt%
With catalyst in 10vol%O
2/ Ar handles 1h down for 550 ℃, drops to 180 ℃, feeds the methanol steam and the air of 140 ℃ of preheatings, and unstrpped gas consists of CH
3OH/O
2/ Ar=6.3/9.4/84.3, reaction pressure is a normal pressure, the reaction gas air speed is 4000ml/g
Cat.h, the reactivity worth of catalyst sees Table 1.
Embodiment 3
The 3.3g phosphotungstic acid is dissolved in the deionized water, adds 5.0g HZSM-5 molecular sieve (Si/Al=60), become thick presoma behind 50 ℃ of dippings, roasting in air is (300 ℃ behind 70 ℃ of dry 24h, 7h), getting phosphotungstic acid content is 36.46wt%, and HZSM-5 content is the catalyst of 63.54wt%.
Catalyst is handled 5h down for following 300 ℃ in air atmosphere, drop to 170 ℃, feed the methanol steam and the air of 140 ℃ of preheatings, unstrpped gas consists of CH
3OH/O
2/ N
2=10.0/18.0/72.0, reaction pressure is a normal pressure, the reaction gas air speed is 2000ml/g
Cat.h, the reactivity worth of catalyst sees Table 1.
Embodiment 4
The 0.38g phosphomolybdic acid is dissolved in the deionized water, add 2.5g SBA-15 molecular sieve, behind 30 ℃ of dippings thick presoma, with presoma (550 ℃ of roastings in air behind 100 ℃ of dry 10h, 5h) getting phosphomolybdic acid content is 10.81wt%, and SBA-15 content is the catalyst of 89.19wt%.
With catalyst in 10vol%O
2Behind 550 ℃ of processing 1h, be cooled to 180 ℃ under the/Ar atmosphere, feed methanol steam and the Ar and the O of 140 ℃ of preheatings
2Gaseous mixture, unstrpped gas consists of CH
3OH/O
2/ Ar=6.3/9.4/84.3, reaction pressure is a normal pressure, the reaction gas air speed is 6000ml/g
Cat.h react, the reactivity worth of catalyst sees Table 1.
Embodiment 5
The 0.5g silico-tungstic acid is dissolved in the deionized water, add 2.5g SBA-15 and MCM-41 molecular sieve mixture (mass ratio of SBA-15 and MCM-41 is 1: 1) and behind 70 ℃ of dippings, get thick presoma, with presoma (400 ℃ of roastings in air behind 90 ℃ of dry 16h, 8h) getting silico-tungstic acid content is 14.81wt%, and MCM-41 and SBA-15 content are the catalyst of 85.19wt%.
With catalyst in 10vol%O
2Behind 400 ℃ of processing 3h, be cooled to 160 ℃ under the/Ar atmosphere, feed methanol steam and the Ar and the O of 140 ℃ of preheatings
2Gaseous mixture, reacting gas consists of CH
3OH/O
2/ Ar=6.3/9.4/84.3, reaction pressure is a normal pressure, the reaction gas air speed is 4000ml/g
Cat.h, the reactivity worth of catalyst sees Table 1.
Embodiment 6
With 4.0g P
123Be dissolved in back adding 0.15g phosphomolybdic acid in the 105ml deionized water, dissolving back drips 37%HCl to make the Ph value is 0.5 fully, back dropping 8.5g TEOS stirs, 40 ℃ of constant temperature stir 24h, 100 ℃ of crystallization 24h, suction filtration, 80 ℃ of dry 20h, 500 ℃ of roasting 5h, getting phosphomolybdic acid content is 4.66wt%, SBA-15 content is the catalyst of 95.94wt%.
With catalyst in 10vol%O
2/ Ar atmosphere is handled 2h down for following 500 ℃, drops to 160 ℃, feeds and is preheated to 150 ℃ methanol steam and Ar and O
2Gaseous mixture, reacting gas consists of CH
3OH/O
2/ Ar=15.0/8.5/76.5, reaction pressure is a normal pressure, the reaction gas air speed is 4000ml/g
Cat.h, the reactivity worth of catalyst sees Table 1.
Embodiment 7
With 4.0g P
123Be dissolved in back adding 0.25g silico-tungstic acid in the 105ml deionized water, dissolving back drips nitric acid to make the pH value is 1.0 fully, back dropping 8.5g TEOS stirs, 40 ℃ of constant temperature stir 12h, 90 ℃ of crystallization 24h, suction filtration, 90 ℃ of dry 10h, 450 ℃ of roasting 8h, getting silico-tungstic acid content is 8.05wt%, SBA-15 content is the catalyst of 91.95wt%.
With catalyst in 10vol%O
2/ Ar atmosphere is handled 3h down for following 450 ℃, drops to 160 ℃, feeds and is preheated to 130 ℃ methanol steam and Ar and O
2Gaseous mixture, reacting gas consists of CH
3OH/O
2/ Ar=15.0/8.5/76.5, reaction pressure is a normal pressure, the reaction gas air speed is 8000ml/g
Cat.h, the reactivity worth of catalyst sees Table 1.
Embodiment 8
With 4.0g P
123Be dissolved in back adding 1.5g phosphomolybdic acid in the 105ml deionized water, dissolving back drips 37%HCl to make the pH value is 2.0 fully, back dropping 8.5g TEOS stirs, 40 ℃ of constant temperature stir 16h, 95 ℃ of crystallization 24h, suction filtration, 110 ℃ of dry 8h, 600 ℃ of roasting 5h, getting phosphomolybdic acid content is 32.80wt%, SBA-15 content is the catalyst of 67.20wt%.
With catalyst in 10vol%O
2/ Ar atmosphere is handled 1h down for following 600 ℃, drops to 220 ℃, feeds and is preheated to 140 ℃ methanol steam and Ar and O
2Gaseous mixture, reacting gas consists of CH
3OH/O
2/ Ar=15.0/8.5/76.5, reaction pressure is a normal pressure, the reaction gas air speed is 5000ml/g
Cat.h, the reactivity worth of catalyst sees Table 1.
Embodiment 9
The 0.3g phosphomolybdic acid is dissolved in the deionized water, adds 2.5g MCM-41 molecular sieve, behind 40 ℃ of dippings, become thick presoma, with presoma (400 ℃ of roastings in air behind 80 ℃ of dry 14h, 4h), getting phosphomolybdic acid content is 8.84wt%, and MCM-41 content is the catalyst of 91.16wt%.The 0.05g copper chloride is dissolved in the deionized water, to add above-mentioned phosphomolybdic acid content be the 8.84wt% catalyst and flood 5h, (400 ℃ of roastings in air behind 100 ℃ of dry 10h then, 4h), promptly getting copper content is 0.86wt%, phosphomolybdic acid content 8.68wt%, MCM-41 content are the catalyst of 90.46wt%.
With catalyst in 10vol%O
2Behind 400 ℃ of processing 3h, be cooled to 180 ℃ under the/Ar atmosphere, feed methanol steam and the Ar and the O of 140 ℃ of preheatings
2Gaseous mixture, unstrpped gas consists of CH
3OH/O
2/ Ar=6.3/9.4/84.3, reaction pressure is a normal pressure, the reaction gas air speed is 4000ml/g
Cat.h react, the reactivity worth of catalyst sees Table 1.
Embodiment 10
With 4.0g P
123Be dissolved in back adding 0.63g phosphomolybdic acid in the 105ml deionized water, dissolving back drips 37%HCl to make the pH value is 1.5 fully, back dropping 8.5g TEOS stirs, 40 ℃ of constant temperature stir 20h, 100 ℃ of crystallization 24h, suction filtration, 100 ℃ of dry 10h, 500 ℃ of roasting 5h, getting phosphomolybdic acid content is 17.06wt%, SBA-15 content is the catalyst of 82.94wt%.In the oxalic acid solution that contains the 0.16g ammonium metavanadate, to add above-mentioned phosphomolybdic acid content be the catalyst of 16.92wt% and flood 5h, roasting in air is (500 ℃ behind 80 ℃ of dry 18h, 5h) promptly obtaining content of vanadium is 2.25wt%, phosphomolybdic acid content is 16.38wt%, and SBA-15 content is the 81.37wt% catalyst.
With catalyst in 10vol%O
2Be cooled to 180 ℃ at 500 ℃ after locating 2h under the/Ar atmosphere, feed methanol steam and the Ar and the O of 140 ℃ of preheatings
2Gaseous mixture, unstrpped gas consists of CH
3OH/O
2/ Ar=6.3/9.4/84.3, reaction pressure is a normal pressure, the reaction gas air speed is 4000ml/g
Cat.h react, the reactivity worth of catalyst sees Table 1.
Table 1 catalyst methanol oxidation system dimethoxym ethane performance
| Embodiment | Methanol conversion (mol%) | Dimethoxym ethane selectivity (C%) | Dimethyl ether selectivity (C%) | Formaldehyde selectivity (C%) | Methyl formate selectivity (C%) | COx selectivity (C%) |
| Embodiment 1 | 12.79 | 52.8 | 15.73 | 16.76 | 12.88 | 1.83 |
| Embodiment 2 | 5.05 | 79.03 | 5.53 | 8.26 | 7.18 | 0.00 |
| Embodiment 3 | 89.0 | 4.05 | 70.03 | 15.45 | 8.92 | 2.55 |
| Embodiment 4 | 23.73 | 53.75 | 20.01 | 10.09 | 15.21 | 1.09 |
| Embodiment 5 | 15.77 | 59.55 | 28.22 | 4.28 | 7.35 | 0.60 |
| Embodiment 6 | 6.55 | 70.14 | 12.08 | 3.84 | 9.93 | 0.00 |
| Embodiment 7 | 12.77 | 30.55 | 28.22 | 14.28 | 18.35 | 8.60 |
| Embodiment 8 | 93.83 | 10.00 | 43.71 | 16.61 | 26.77 | 3.91 |
| Embodiment 9 | 35.05 | 10.05 | 8.79 | 16.00 | 59.67 | 5.49 |
| Embodiment 10 | 45.04 | 28.25 | 33.05 | 17.25 | 19.80 | 1.45 |
Claims (14)
1. the catalyst of a methanol oxidation to methylal by one step, it is characterized in that catalyst is made up of heteropoly acid and silica-based molecular sieve, wherein to account for the catalyst weight degree be 3～45% to heteropoly acid, it is 0～5% that tenor accounts for the catalyst weight degree in the metal simple-substance amount, and all the other are silica-based molecular sieve.
2. the catalyst of a kind of methanol oxidation to methylal by one step as claimed in claim 1 is characterized in that described heteropoly acid is phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid, silicomolybdic acid or phosphorus molybdenum vanadium heteropolyacid.
3. the catalyst of a kind of methanol oxidation to methylal by one step as claimed in claim 1 is characterized in that described metal component is vanadium, molybdenum, copper, zinc, iron, manganese, tin or zirconium.
4. the catalyst of a kind of methanol oxidation to methylal by one step as claimed in claim 1 is characterized in that described silica-based molecular sieve is SBA-15, SBA-16, MCM-41, ZSM-5, X type or Y zeolite.
5. as the Preparation of catalysts method of each described a kind of methanol oxidation to methylal by one step of claim 1-4, when it is characterized in that metal component content is 0 in catalyst is formed, the Preparation of catalysts method that heteropoly acid/molecular sieve is formed is that heteropoly acid and silica-based molecular sieve ground and mixed is even, at 300～600 ℃ of roasting 5～10h, promptly get heteropoly acid/molecular sieve catalyst.
6. as the Preparation of catalysts method of each described a kind of methanol oxidation to methylal by one step of claim 1-4, when it is characterized in that metal component content is 0 in catalyst is formed, the Preparation of catalysts method that heteropoly acid/molecular sieve is formed be with heteropoly acid with dissolved in distilled water after, add silica-based molecular sieve carrier, become thick presoma behind 20～80 ℃ of dippings, at 60～110 ℃ of drying 5～24h, 300～600 ℃ of roasting 5～10h in air promptly get heteropoly acid/molecular sieve catalyst then.
7. as the Preparation of catalysts method of each described a kind of methanol oxidation to methylal by one step of claim 1-4, when it is characterized in that metal component content is 0 in catalyst is formed, the Preparation of catalysts method that heteropoly acid/molecular sieve is formed is that template agent polyvinylether-polypropylene ether-polyvinylether triblock copolymer is added heteropoly acid after being dissolved in deionized water, the adding acid of dissolving back is 0.5～2.5 with regulator solution pH value fully, add ethyl orthosilicate after stirring, the mol ratio that makes each material is P
123: heteropoly acid: TEOS: H
2O=1～1.28: 0.057～1.10: 46.39～676: 6804～11973, stir 12～24h at 30～50 ℃ of constant temperature, 80～100 ℃ of crystallization 12～48h, behind the suction filtration in 80～110 ℃ of drying 5～24h, roasting 5～12h in 400～600 ℃ of air promptly gets heteropoly acid-SBA-15 catalyst then.
8. the Preparation of catalysts method of a kind of methanol oxidation to methylal by one step as claimed in claim 7 is characterized in that the acid of described adjusting pH value is hydrochloric acid, sulfuric acid or nitric acid.
9. as the Preparation of catalysts method of each described a kind of methanol oxidation to methylal by one step of claim 1-4, when it is characterized in that in catalyst is formed, containing metal component, the preparation method of metal-heteropoly acid/molecular sieve catalyst is that heteropoly acid and silica-based molecular sieve ground and mixed is even, at 300～600 ℃ of roasting 5～10h, promptly get heteropoly acid/molecular sieve catalyst, in heteropoly acid/molecular sieve catalyst that the metal component salts solution is obtained, dipping 2～10h, then in 60～110 ℃ of drying 5～24h, in air,, promptly obtain metal-heteropoly acid/molecular sieve catalyst in 400～600 ℃ of roasting 5～10h.
10. as the Preparation of catalysts method of each described a kind of methanol oxidation to methylal by one step of claim 1-4, when it is characterized in that in catalyst is formed, containing metal component, the preparation method of metal-heteropoly acid/molecular sieve catalyst be with heteropoly acid with dissolved in distilled water after, add silica-based molecular sieve carrier, become thick presoma behind 20～80 ℃ of dippings, at 60～110 ℃ of drying 5～24h, 300～600 ℃ of roasting 5～10h in air then, promptly get heteropoly acid/molecular sieve catalyst, the metal component salts solution is added in the heteropoly acid/molecular sieve catalyst that obtains, dipping 2～10h, then in 60～110 ℃ of drying 5～24h, in air,, promptly obtain metal-heteropoly acid/molecular sieve catalyst in 400～600 ℃ of roasting 5～10h.
11. Preparation of catalysts method as each described a kind of methanol oxidation to methylal by one step of claim 1-4, when it is characterized in that in catalyst is formed, containing metal component, the preparation method of metal-heteropoly acid/molecular sieve catalyst adds heteropoly acid with template agent polyvinylether-polypropylene ether-polyvinylether triblock copolymer after being dissolved in deionized water, the adding acid of dissolving back is 0.5～2.5 with regulator solution pH value fully, add ethyl orthosilicate after stirring, the mol ratio that makes each material is P
123: heteropoly acid: TEOS: H
2O=1～1.28: 0.057～1.10: 46.39～676: 6804～11973, stir 12～24h at 30～50 ℃ of constant temperature, 80～100 ℃ of crystallization 12～48h, behind the suction filtration in 80～110 ℃ of drying 5～24h, roasting 5～12h in 400～600 ℃ of air then, promptly get heteropoly acid-SBA-15 catalyst, the metal component salts solution is added in the heteropoly acid-SBA-15 catalyst that obtains, dipping 2～10h, then in 60～110 ℃ of drying 5～24h, in air,, promptly obtain metal-heteropoly acid/molecular sieve catalyst in 400～600 ℃ of roasting 5～10h.
12., it is characterized in that described metal component salt is----as the Preparation of catalysts method of each described a kind of methanol oxidation to methylal by one step of claim 9-11.
13. Application of Catalyst as each described a kind of methanol oxidation to methylal by one step of claim 1-4, it is characterized in that with catalyst in oxygen-containing atmosphere in 300～600 ℃ handle 1～5h after, cool to 150～250 ℃ of reaction temperatures, feed then and be preheated to 130～150 ℃ the methanol steam and the gaseous mixture of oxygen-containing gas, the percent by volume of methyl alcohol is 1.0～15.0% in the gaseous mixture, and the reaction gas air speed is 1000～10000ml/g
Cat.h, reaction pressure is a normal pressure.
14. the Application of Catalyst of a kind of methanol oxidation to methylal by one step as claimed in claim 12 is characterized in that described oxygen-containing gas is the gaseous mixture of air, oxygen and nitrogen or the gaseous mixture of oxygen and helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100545436A CN101224431A (en) | 2008-01-30 | 2008-01-30 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100545436A CN101224431A (en) | 2008-01-30 | 2008-01-30 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101224431A true CN101224431A (en) | 2008-07-23 |
Family
ID=39856761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100545436A Pending CN101224431A (en) | 2008-01-30 | 2008-01-30 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101224431A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110054221A1 (en) * | 2009-02-27 | 2011-03-03 | Peng Yu | Process of oxidative conversion of methanol |
| CN101721991B (en) * | 2008-10-31 | 2012-05-23 | 南京大学 | Method for preparing V-Ti-Si-O composite catalyst used in methanol oxidation for synthesizing methylal |
| CN102500407A (en) * | 2011-10-09 | 2012-06-20 | 南京大学 | Preparation method of bimetal-doped mesoporous material SBA-15 catalyst and bimetal-doped SBA-15 catalyst |
| CN102513148A (en) * | 2011-12-12 | 2012-06-27 | 南京工业大学 | Catalyst and process for coproduction of benzaldehyde and acyl chloride by benzal chloride acidolysis reaction |
| CN102731273A (en) * | 2012-07-09 | 2012-10-17 | 北京大学 | Preparation method of acetal |
| CN103752341A (en) * | 2014-01-24 | 2014-04-30 | 郑州大学 | Keggin type heteropoly acid-silicon oxide catalyst of mesopore structure and preparation method thereof |
| CN103846099A (en) * | 2014-02-20 | 2014-06-11 | 宁波高新区夏远科技有限公司 | Supported polyoxometallate and preparation method thereof |
| CN103880613A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN104043442A (en) * | 2014-05-23 | 2014-09-17 | 天津大学 | Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation |
| CN105536821A (en) * | 2015-12-03 | 2016-05-04 | 渤海大学 | Preparation method of double effect catalyst for high selective oxidation of methane to prepare dimethoxymethane |
| CN105772062A (en) * | 2016-04-07 | 2016-07-20 | 广西新天德能源有限公司 | Method for catalyzing and producing methylal by means of modified molecular sieve supported catalyst |
| CN106362798A (en) * | 2015-07-24 | 2017-02-01 | 中国科学院成都有机化学有限公司 | Catalyst used in liquid phase technology to produce methylal |
| CN107008249A (en) * | 2016-01-28 | 2017-08-04 | 中国科学院上海高等研究院 | A kind of step of methanol one aoxidizes catalyst of dimethoxym ethane processed and its preparation method and application |
| CN107021877A (en) * | 2017-05-09 | 2017-08-08 | 哈尔滨师范大学 | The method of methanol direct oxidation synthesizing dimethoxym ethane |
| WO2019104810A1 (en) * | 2017-11-29 | 2019-06-06 | 西南化工研究设计院有限公司 | Processing system and method for preparing acetal by using monohydric alcohol-air catalytic conversion |
| CN111100214A (en) * | 2020-01-15 | 2020-05-05 | 安徽雪郎生物科技股份有限公司 | Preparation method of oxidized starch with high carboxyl content |
| WO2020124421A1 (en) * | 2018-12-19 | 2020-06-25 | Rhodia Operations | A process for preparing acetals or ketals |
| CN114345294A (en) * | 2022-01-10 | 2022-04-15 | 万华化学集团股份有限公司 | Zinc-manganese-zirconium modified mesoporous molecular sieve, preparation method and application |
-
2008
- 2008-01-30 CN CNA2008100545436A patent/CN101224431A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721991B (en) * | 2008-10-31 | 2012-05-23 | 南京大学 | Method for preparing V-Ti-Si-O composite catalyst used in methanol oxidation for synthesizing methylal |
| US8476477B2 (en) * | 2009-02-27 | 2013-07-02 | China Petroleum & Chemical Corp. | Process of oxidative conversion of methanol |
| US20110054221A1 (en) * | 2009-02-27 | 2011-03-03 | Peng Yu | Process of oxidative conversion of methanol |
| CN102500407A (en) * | 2011-10-09 | 2012-06-20 | 南京大学 | Preparation method of bimetal-doped mesoporous material SBA-15 catalyst and bimetal-doped SBA-15 catalyst |
| CN102513148A (en) * | 2011-12-12 | 2012-06-27 | 南京工业大学 | Catalyst and process for coproduction of benzaldehyde and acyl chloride by benzal chloride acidolysis reaction |
| CN102513148B (en) * | 2011-12-12 | 2013-10-09 | 南京工业大学 | Catalyst and process for coproduction of benzaldehyde and acyl chloride by benzal chloride acidolysis reaction |
| CN102731273B (en) * | 2012-07-09 | 2014-11-26 | 北京大学 | Preparation method of acetal |
| CN102731273A (en) * | 2012-07-09 | 2012-10-17 | 北京大学 | Preparation method of acetal |
| CN103880613A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN103752341A (en) * | 2014-01-24 | 2014-04-30 | 郑州大学 | Keggin type heteropoly acid-silicon oxide catalyst of mesopore structure and preparation method thereof |
| CN103752341B (en) * | 2014-01-24 | 2016-01-20 | 郑州大学 | Keggin-type heteropoly acid-silicon oxide catalyst of a kind of central hole structure and preparation method thereof |
| CN103846099B (en) * | 2014-02-20 | 2015-09-30 | 宁波高新区夏远科技有限公司 | A kind of support type polyoxometallate and preparation method thereof |
| CN103846099A (en) * | 2014-02-20 | 2014-06-11 | 宁波高新区夏远科技有限公司 | Supported polyoxometallate and preparation method thereof |
| CN104043442A (en) * | 2014-05-23 | 2014-09-17 | 天津大学 | Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation |
| CN106362798A (en) * | 2015-07-24 | 2017-02-01 | 中国科学院成都有机化学有限公司 | Catalyst used in liquid phase technology to produce methylal |
| CN105536821B (en) * | 2015-12-03 | 2018-02-23 | 渤海大学 | The preparation method of the dual purpose catalyst of methanol high-selectivity oxidation dimethoxymethane |
| CN105536821A (en) * | 2015-12-03 | 2016-05-04 | 渤海大学 | Preparation method of double effect catalyst for high selective oxidation of methane to prepare dimethoxymethane |
| CN107008249A (en) * | 2016-01-28 | 2017-08-04 | 中国科学院上海高等研究院 | A kind of step of methanol one aoxidizes catalyst of dimethoxym ethane processed and its preparation method and application |
| CN105772062A (en) * | 2016-04-07 | 2016-07-20 | 广西新天德能源有限公司 | Method for catalyzing and producing methylal by means of modified molecular sieve supported catalyst |
| CN107021877A (en) * | 2017-05-09 | 2017-08-08 | 哈尔滨师范大学 | The method of methanol direct oxidation synthesizing dimethoxym ethane |
| WO2019104810A1 (en) * | 2017-11-29 | 2019-06-06 | 西南化工研究设计院有限公司 | Processing system and method for preparing acetal by using monohydric alcohol-air catalytic conversion |
| WO2020124421A1 (en) * | 2018-12-19 | 2020-06-25 | Rhodia Operations | A process for preparing acetals or ketals |
| CN111100214A (en) * | 2020-01-15 | 2020-05-05 | 安徽雪郎生物科技股份有限公司 | Preparation method of oxidized starch with high carboxyl content |
| CN111100214B (en) * | 2020-01-15 | 2022-03-01 | 安徽雪郎生物科技股份有限公司 | Preparation method of oxidized starch with high carboxyl content |
| CN114345294A (en) * | 2022-01-10 | 2022-04-15 | 万华化学集团股份有限公司 | Zinc-manganese-zirconium modified mesoporous molecular sieve, preparation method and application |
| CN114345294B (en) * | 2022-01-10 | 2023-05-26 | 万华化学集团股份有限公司 | Zinc-manganese-zirconium modified mesoporous molecular sieve, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101224431A (en) | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof | |
| CN102068986A (en) | Catalyst used in ring-opening hydrogenation reaction of furan derivative | |
| CN101327444A (en) | Metallic catalyst for synthesizing dimethoxym ethane and methyl formate and production method thereof and use | |
| CN108623437B (en) | Method for continuously producing neopentyl glycol | |
| CN103360224A (en) | Combined process for preparing poly methoxy-dimethyl ether | |
| CN113754540B (en) | Method for co-producing dimethyl carbonate, ethylmethyl carbonate and ethylene glycol | |
| CN106866364A (en) | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol | |
| CN107674195A (en) | A kind of synthetic catalyst and its synthetic method of polyoxyethylene vinyl polymerization thing | |
| CN103664656A (en) | Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid | |
| CN106866331A (en) | A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol | |
| CN101817731B (en) | Method for preparing polymethoxy dimethyl ether by converting methanol | |
| CN106316766B (en) | The method of aromatisation | |
| CN101838256B (en) | Method for synthesizing vinylethylene carbonate | |
| CN108383696B (en) | Method for preparing polymethoxy dimethyl ether | |
| CN103769111B (en) | A kind of preparation method of hydrogenation catalyst | |
| CN107952484B (en) | Preparation method and application of Nafion film loaded rare earth metal catalyst | |
| CN108314617B (en) | Method and device for recovering acetaldehyde in pentaerythritol production | |
| CN102391070B (en) | Method for producing trimethylolpropane by utilizing formaldehyde | |
| CN103755535B (en) | A kind of preparation method of polyoxymethylene dimethyl ether | |
| CN113185407A (en) | Method for synthesizing dimethyl carbonate through ester exchange reaction | |
| CN113372218B (en) | Preparation method of methyl methacrylate | |
| CN113457193B (en) | Device and method for separating methanol-methylal-methyl formate mixture | |
| CN101139266A (en) | Method for preparing ethylene glycol monoethyl ether | |
| CN102614900A (en) | Mesoporous carbon-loaded catalyst for synthesizing diethyl carbonate by gas phase oxidation carbonyl of ethanol and preparation method thereof | |
| CN103664546B (en) | Prepare the method for polymethoxy dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080723 |