CN101108357A - Application method of dimethyl ether oxo-synthesis formal catalyzer - Google Patents
Application method of dimethyl ether oxo-synthesis formal catalyzer Download PDFInfo
- Publication number
- CN101108357A CN101108357A CNA2007101375103A CN200710137510A CN101108357A CN 101108357 A CN101108357 A CN 101108357A CN A2007101375103 A CNA2007101375103 A CN A2007101375103A CN 200710137510 A CN200710137510 A CN 200710137510A CN 101108357 A CN101108357 A CN 101108357A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dimethyl ether
- reaction
- acid
- heteropoly acid
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an application method for a methylal catalyst prepared by oxidizing and synthesizing dimethyl enther. The mole ratio of dimethyl to oxygen is controlled to be 1-3:1-3, reaction is carried out in a fixed bed reactor, the air speed of the reaction is 1500-200h-1, the reaction temperature is 250 to 400 DEG C, the reaction pressure is 1 to 3 MPa, and the reaction time is 10 minutes to 10 hours, finally the methylal is obtained. The weight percentage of the modified component in the catalyst is 9.90-35.71%, heteropoly acid 9.90-35.71%, and the carrier component 35.71-89.11%. The invention has the advantages of the high stability, the simple process, the easy operation, the high dimethyl transformation rate and the high methylal yield rate.
Description
Technical field
The invention belongs to a kind of application process of dimethyl ether oxo-synthesis formal catalyzer.
Background technology
Dimethoxym ethane is a kind of important chemical material, and purposes is very extensive.It can be used as the diesel fuel additives with broad prospect of application, also can oxidizedly produce the formaldehyde of high concentration.Also can be used as the intermediate of other organic syntheses.In addition, it also is widely used in the products such as cosmetics, medicine, household supplies, industrial Automobile Products, rubber industry, paint, printing ink; Because it has good ability of cleaning greasy dirt and volatility can substitute F11 and F113 and chlorinated solvents as cleaning agent, be replacement fluorine Lyons therefore, reduce volatile organic matter (VOCs) discharging, reduce environment-friendly products to atmosphere pollution.
The deficiency of aspects such as at present, the synthesizing dimethoxym ethane mature methods is methyl alcohol and the condensation method of formaldehyde under acid catalysis, if adopt inorganic acid as catalyst, exists catalyst separation to reclaim difficulty, and corrosivity is strong; And the employing cationic ion-exchange resin, solid acid catalysts such as crystalline aluminosilicate then have conversion ratio lower, weakness such as poor selectivity; Another kind is exactly the methanol oxidation method, and the dimethoxym ethane concentration that adopts this method to obtain is low, is not suitable for dimethoxym ethane and produces on a large scale.(J.Phys.Chem.B 2003 for LiuHaichao, 107,10840-10847) loading catalyst (0.1-0.3g) on microreactor such as grade adopts the dimethyl ether oxidizing process to produce dimethoxym ethane, but has deficiencies such as dimethyl ether conversion rate very low (0.5-2.5%) and dimethoxym ethane yield hang down.
Summary of the invention
The purpose of this invention is to provide a kind of dimethyl ether conversion rate height, the application process of the dimethyl ether oxo-synthesis formal catalyzer that the yield of dimethoxym ethane is high.
Catalyst agent of the present invention is adopted through the heteropoly acid of modification and silica gel, lanthana, aluminium oxide, zirconia, titanium oxide or molecular sieve carrier and is formed, one or more modified components that add in the compound that contains potassium, caesium, manganese, vanadium, nickel, zinc, cadmium, tin, iron, lanthanum, copper, zirconium or cobalt element in heteropoly acid carry out modification, it is 0.99-28.58% that the weight of modified component accounts for the catalyst weight degree, it is 9.90-35.71% that heteropoly acid accounts for the catalyst weight degree, and it is 35.71-89.11% that carrier component accounts for the catalyst weight degree.
Method for preparing catalyst: at first, heteropoly acid is impregnated on the carrier after with dissolved in distilled water, left standstill 2-8 hour, 100-130 ℃ of oven dry, 300-700 ℃ following roasting 2-6 hour, heteropoly acid/carrier; Secondly, to contain in the compound of potassium, caesium, manganese, vanadium, nickel, zinc, cadmium, tin, iron, lanthanum, copper, zirconium or cobalt element one or more is impregnated on the good heteropoly acid/carrier of roasting after with dissolved in distilled water, left standstill 2-6 hour, 100-130 ℃ of oven dry, 300-700 ℃ following roasting 2-6 hour, can make the required catalyst of reaction.
Aforesaid heteropoly acid is phosphotungstic acid, silico-tungstic acid or phosphomolybdic acid.
Application of Catalyst method of the present invention is: the mol ratio of raw material dimethyl ether and oxygen is controlled at 1-3: between the 1-3, react reaction velocity 1500-200h in fixed bed reactors
-1, reaction temperature is 250-400 ℃, and reaction pressure is 1-3MPa, and the reaction time is 10 minutes-10 hours, promptly gets dimethoxym ethane.
Advantage of the present invention is as follows:
1, because the heteropoly acid of modification has highly acid and the difunctional effect of oxidation-reduction quality, so oxidation is produced dimethoxym ethane and is had catalytic action preferably for dimethyl ether catalysis, the stablizing of catalyst.
2, technology of the present invention is simple, and is easy to operate.
3, the dimethoxym ethane selectivity that makes with this method is between 15-50%.
Dimethyl ether conversion rate height, the yield height of dimethoxym ethane.
The specific embodiment
Embodiment 1:
1, preparation catalyst: take by weighing the 4.0g silico-tungstic acid and be dissolved in the distilled water, be impregnated on the 6.0g silica gel, left standstill 4 hours, 110 ℃ of oven dry, 400 ℃ of roastings 4 hours, silico-tungstic acid/silica gel; Take by weighing the 1.9g manganese chloride then and be dissolved in the distilled water, be impregnated in the silico-tungstic acid/silica gel that bakes, left standstill 3 hours, 120 ℃ of oven dry, 400 ℃ of roastings 3 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 5% manganese, 38% silico-tungstic acid and 57% silica gel;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 1: 1 mole of proportioning of oxygen; Reaction pressure is 1MPa, reaction velocity 400h
-1, reaction temperature is 340 ℃, and the reaction time is 2 hours, can make selectivity at 35.50% dimethoxym ethane, and the dimethyl ether conversion rate is 9.04%.
Embodiment 2:
1, preparation catalyst: take by weighing the 6.0g alundum (Al, the 4.0g silico-tungstic acid is dissolved in and is impregnated in the distilled water on the alundum (Al, left standstill 6 hours, 110 ℃ of oven dry, 450 ℃ of roastings 6 hours, silico-tungstic acid/alundum (Al; Take by weighing the 1.9g manganese chloride then and be dissolved in the distilled water, be impregnated in the silico-tungstic acid/alundum (Al that bakes, left standstill 4 hours, 130 ℃ of oven dry, 400 ℃ of roastings 4 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 5% manganese, 38% silico-tungstic acid and 57% alundum (Al;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 1: 1 mole of proportioning of oxygen; Reaction pressure is at 1.5MPa; Reaction velocity is 500h
-1Reaction temperature is 320 ℃, and the reaction time is 15min, can make selectivity and be 36.20% dimethoxym ethane, and the dimethyl ether conversion rate is 6.11%.
Embodiment 3,
1, preparation catalyst: take by weighing 10.0g silica gel, the 6.7g silico-tungstic acid is dissolved in and is impregnated in the distilled water on the silica gel, left standstill 4 hours, 120 ℃ of oven dry, 400 ℃ of roastings 4 hours, silico-tungstic acid/silica gel; Take by weighing the 2.1g butter of tin then and be dissolved in the distilled water, be impregnated in the silico-tungstic acid/silica gel that bakes, left standstill 3 hours, 130 ℃ of oven dry, 400 ℃ of roastings 3 hours can make the catalyst of the synthesizing dimethoxym ethane that contains 5% tin, 38% silico-tungstic acid and 57% silica gel;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 3: 2 moles of proportionings of oxygen; Reaction pressure is 1MPa; Reaction velocity is 800h
-1Reaction temperature is 360 ℃, and the reaction time is 15min, and obtaining the dimethoxym ethane selectivity is 15%, and the dimethyl ether conversion rate is 16%.
Embodiment 4,
1, preparation catalyst: take by weighing 10.0g silica gel, the 6.7g silico-tungstic acid is dissolved in and is impregnated in the distilled water on the silica gel, left standstill 5 hours, 110 ℃ of oven dry, 420 ℃ of roastings 5 hours, silico-tungstic acid/silica gel; Take by weighing the 6.68g manganese chloride then and be dissolved in the distilled water, be impregnated in the silico-tungstic acid/silica gel that bakes, left standstill 4 hours, 130 ℃ of oven dry, 420 ℃ of roastings 4 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 10% manganese, 36% silico-tungstic acid and 54% silica gel;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 1: 1 mole of proportioning of oxygen; Reaction pressure is 1.5MPa; Reaction velocity is 600h
-1Reaction temperature is 360 ℃, and reaction time 15min gets final product to such an extent that selectivity is 20% dimethoxym ethane, and the dimethyl ether conversion rate is 25%.
Claims (2)
1. the Application of Catalyst method of a dimethyl ether oxo-synthesis formal is characterized in that the mol ratio of raw material dimethyl ether and oxygen is controlled at 1-3: between the 1-3, react reaction velocity 1500-200h in fixed bed reactors
-1Reaction temperature is 250-400 ℃, reaction pressure is 1-3MPa, reaction time is 10 minutes-10 hours, promptly get dimethoxym ethane, wherein catalyst adopts heteropoly acid and the silica gel through modification, lanthana, aluminium oxide, zirconia, titanium oxide or molecular sieve carrier are formed, in heteropoly acid, add and contain potassium, caesium, manganese, vanadium, nickel, zinc, cadmium, tin, iron, lanthanum, copper, one or more modified components in the compound of zirconium or cobalt element carry out modification, it is 0.99-28.58% that the weight of modified component accounts for the catalyst weight degree, it is 9.90-35.71% that heteropoly acid accounts for the catalyst weight degree, and it is 35.71-89.11% that carrier component accounts for the catalyst weight degree.
2. the Application of Catalyst method of a kind of dimethyl ether oxo-synthesis formal as claimed in claim 1 is characterized in that described heteropoly acid is phosphotungstic acid, silico-tungstic acid or phosphomolybdic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710137510 CN100471564C (en) | 2005-12-21 | 2005-12-21 | Application method of dimethyl ether oxo-synthesis formal catalyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710137510 CN100471564C (en) | 2005-12-21 | 2005-12-21 | Application method of dimethyl ether oxo-synthesis formal catalyzer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510048219XA Division CN100528349C (en) | 2005-12-21 | 2005-12-21 | Catalyst for oxo-synthesis of dimethyl ether to produce methylal, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101108357A true CN101108357A (en) | 2008-01-23 |
| CN100471564C CN100471564C (en) | 2009-03-25 |
Family
ID=39040733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710137510 Expired - Fee Related CN100471564C (en) | 2005-12-21 | 2005-12-21 | Application method of dimethyl ether oxo-synthesis formal catalyzer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100471564C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786008A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Load-type heteropolyacid catalyst for aldolization and preparation method thereof |
| CN102500419A (en) * | 2011-11-28 | 2012-06-20 | 上海工程技术大学 | Supported catalyst for synthesizing benzaldehyde dimethylacetal and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465436A (en) * | 2002-06-26 | 2004-01-07 | 中国科学院大连化学物理研究所 | Catalyst for normal paraffin isomerization and use thereof |
| US6956134B2 (en) * | 2004-01-08 | 2005-10-18 | The Regents Of The University Of California | Oxidation of methanol and/or dimethyl ether using supported molybdenum-containing heteropolyacid catalysts |
-
2005
- 2005-12-21 CN CN 200710137510 patent/CN100471564C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786008A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Load-type heteropolyacid catalyst for aldolization and preparation method thereof |
| CN102500419A (en) * | 2011-11-28 | 2012-06-20 | 上海工程技术大学 | Supported catalyst for synthesizing benzaldehyde dimethylacetal and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100471564C (en) | 2009-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| WO2011033689A1 (en) | Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin | |
| CN105330523A (en) | Method for preparing cyclopentanone by taking biomass resource as raw material | |
| CN100528349C (en) | Catalyst for oxo-synthesis of dimethyl ether to produce methylal, preparation method and application thereof | |
| Dumeignil et al. | Biomass-derived platform molecules upgrading through catalytic processes: Yielding chemicals and fuels | |
| CN106111173B (en) | A kind of method for preparing pyruvate | |
| JP2017520511A (en) | Process for the production of alkenol and its use for the production of 1,3-butadiene | |
| CN101199939B (en) | Catalyst for synthesizing methanol and formaldehyde from methane oxidation and preparation and application thereof | |
| WO2011138643A4 (en) | A process for preparation of hydroxyacetone or propylene glycol | |
| CN101898950A (en) | Process for the conversion of ethanol to acetic acid | |
| CN112473709A (en) | Catalyst for synthesizing succinic acid by aqueous phase catalytic hydrogenation and application thereof | |
| CN102746129A (en) | Process method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butanal with heteropoly acid | |
| CN110818566A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN106866360A (en) | A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD | |
| CN103044367B (en) | Production method of gamma-butyrolactone | |
| CN103664587B (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN100471564C (en) | Application method of dimethyl ether oxo-synthesis formal catalyzer | |
| CN103240095A (en) | Methyl acetate hydrogenation catalyst and preparation method thereof | |
| CN102824906B (en) | Loaded type molybdenum oxide catalyst for selectively oxidizing methanol to synthesize dimethoxymethane (DMM) and application | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN103664586B (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN101993353A (en) | Method for preparing 3-methyl-3-butene-1-alcohol | |
| CN116162023A (en) | Method for preparing ethyl acetate by alcohol dehydrogenation condensation | |
| CN113831312B (en) | Method for preparing delta-cyclopentalactone | |
| CN101176850B (en) | Catalyzer for preparing ethylene by ethanol dehydration as well as preparation method and usage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090325 Termination date: 20191221 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |