CN103896774A - Method for producing methyl methoxy acetate - Google Patents
Method for producing methyl methoxy acetate Download PDFInfo
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- CN103896774A CN103896774A CN201210570578.1A CN201210570578A CN103896774A CN 103896774 A CN103896774 A CN 103896774A CN 201210570578 A CN201210570578 A CN 201210570578A CN 103896774 A CN103896774 A CN 103896774A
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- carbon monoxide
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- dimethoxymethane
- methylal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a method for producing methyl methoxy acetate. The method comprises that: a raw material gas containing dimethoxy methane and carbon monoxide is subjected to gas phase carbonylation at a reaction temperature of 80-250 DEG C under a reaction pressure of 1-5.0 MPa at a carbon monoxide gas phase volume space velocity of 4300-26000 h<-1> through a reactor loaded with a solid acid catalyst to produce methyl methoxy acetate, wherein the pressure distribution ratio of the carbon monoxide to the dimethoxy methane in the raw material gas is 30-200. The method has characteristics of easily available catalyst or easy catalyst preparation, mild reaction conditions, simple process and the like, and has industrialization potential.
Description
Technical field
The present invention relates to a kind of method of producing continuously ethylene glycol presoma methoxy menthyl acetate under gas-solid phase condition.
Background technology
Ethylene glycol is a kind of important Organic Chemicals, is the important monomer of synthetic polyester fibers, in addition still a kind of important frostproofer.At present, produce ethylene glycol path and mainly depend on oil.Petroleum naphtha obtains alkene through catalytic cracking, and oxidation of ethylene is produced oxyethane, and oxyethane hydrolysis finally obtains ethylene glycol.Due to petroleum resources shortage and non-renewable, develop non-oil path produce ethylene glycol be very necessary.
People [Angew.Chem.Int.Ed.2009,48, the 4813-4815 such as nearest Bell; J.Catal.2010,274,150-162] new route of a synthesizing glycol has been proposed, shown in (1), this path belongs to C1 synthetic route.Methanol oxidation obtains formaldehyde, formaldehyde and methyl alcohol condensation obtain Methylal(dimethoxymethane) (DMM), DMM carbonylation obtains the methoxy menthyl acetate (MMAc) that contains initial C-C key afterwards, and MMAc is successively by obtaining ethylene glycol after hydrogenation and hydrolysis.
The present invention aims to provide a kind of to produce the non-oil Path Method of ethylene glycol presoma based on coal, Sweet natural gas, biomass through solid acid acid catalysis carbonyl as raw material.The method has catalyzer and easily obtains or preparation, reaction conditions gentleness, and the feature such as technique is simple, has the potentiality of heavy industrialization.
Summary of the invention
The object of the present invention is to provide a kind of vapor phase carbonylation to produce continuously the method for ethylene glycol presoma methoxy menthyl acetate.Particularly, be under highly acidic resin catalysis, Methylal(dimethoxymethane) carbonylation is produced methoxy menthyl acetate.
For achieving the above object, the invention provides a kind of method of producing methoxy menthyl acetate, comprise the unstripped gas that contains Methylal(dimethoxymethane) and carbon monoxide by being loaded with the reactor of solid acid catalyst, at 80～250 DEG C of temperature of reaction, reaction pressure 1～5.0MPa, the volume space velocity of carbon monoxide gas phase is 4300～26000h
-1under, vapor phase carbonylation generates methoxy menthyl acetate; Wherein in unstripped gas, the intrinsic standoff ratio of carbon monoxide and Methylal(dimethoxymethane) is 30～200.
In the method for the invention, described solid acid catalyst is preferably highly acidic resin, particularly perfluorinated resin catalyzer.Described perfluorinated resin catalyzer is perfluorinated resin film catalyst and/or perfluorinated resin solid particle catalyst, preferably naphthols film catalyst and/or naphthols beaded catalyst.In the method for the invention, reaction system is gas-solid two-phase, does not use liquid solvent in reaction.
The reactor using in method of the present invention is the one in fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor.
In a preferred embodiment of the invention, temperature of reaction is 100～180 DEG C, and described reaction pressure is 2～5.0MPa, and carbon monoxide gaseous phase volume air speed is 5200～10400h
-1, in unstripped gas, the intrinsic standoff ratio of carbon monoxide and Methylal(dimethoxymethane) is 50～200.
In technical solution of the present invention perfluorinated resin catalyzer can high efficiency ground catalysis Methylal(dimethoxymethane) carbonylation produce methyl acetate, owing to taking gas-solid phase reaction, methoxy menthyl acetate can be easily and catalyst separating.
Embodiment
By some embodiment, the present invention is made to detailed statement below, but the present invention is not limited to these embodiment.
In embodiment, the transformation efficiency of Methylal(dimethoxymethane) and the selectivity of methoxy menthyl acetate all the carbon mole number based on Methylal(dimethoxymethane) are calculated:
Methylal(dimethoxymethane) transformation efficiency=[(Methylal(dimethoxymethane) carbon mole number in unstripped gas)-(Methylal(dimethoxymethane) carbon mole number in product)] ÷ (Methylal(dimethoxymethane) carbon mole number in unstripped gas) × (100%)
Methoxy menthyl acetate selectivity=(3/4) × (methoxy menthyl acetate carbon mole number in product) ÷ [(Methylal(dimethoxymethane) carbon mole number in unstripped gas)-(Methylal(dimethoxymethane) carbon mole number in product)] × (100%)
The beaded catalyst of naphthols described in the application, naphthols film are purchased from Sigma's aldrich (Sigma-Aldrich)
Embodiment 1
In the fixed-bed reactor that are 8mm at internal diameter, load 0.6g naphthols beaded catalyst, under the atmosphere of nitrogen, 120 DEG C of activation 1h are to remove the water molecules of absorption, cool to afterwards 110 DEG C, in reaction tubes, pass into CO, and boost to 3.0MPa, Methylal(dimethoxymethane) (DMM) carries by CO air-flow, and the saturation vapour pressure of DMM is controlled by temperature.CO/DMM intrinsic standoff ratio is 100.Reactant is analyzed by on-line chromatograph, and DMM transformation efficiency is that 95.2%, MMAc selectivity is 85.6%.
Other reaction process are similar.
Embodiment 2
When different solid acid catalyst, Methylal(dimethoxymethane) vapor phase carbonylation reactivity worth is evaluated, and other conditions are identical with embodiment 1, and reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 1.
Table 1
Embodiment 3
At 100 DEG C, 130 DEG C, 180 DEG C differential responses temperature, evaluate Methylal(dimethoxymethane) vapor phase carbonylation reactivity worth, other conditions are identical with embodiment 1, and reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 2.
Table 2
Embodiment 4
Reaction pressure is respectively in the time of 2.0MPa, 4.0MPa, 5.0MPa different pressures, and to Methylal(dimethoxymethane) vapor phase carbonylation, reaction is evaluated, and other conditions are identical with embodiment 1, and reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 3.
Table 3
Embodiment 5
Carbon monoxide gas volume air speed is respectively 5200h
-1, 6090h
-1, 7830h
-1, 8700h
-1, 10400h
-1time, investigate the impact of air speed on the reaction of Methylal(dimethoxymethane) vapor phase carbonylation, other conditions are identical with embodiment 1, and reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 4.
Table 4
Embodiment 6
The ratio of CO/DMM dividing potential drop 30,80,150,200 o'clock, investigates the impact of CO dividing potential drop on the reaction of Methylal(dimethoxymethane) vapor phase carbonylation, and other conditions are identical with embodiment 1, and reaction effluent adopts on-line chromatograph analysis.Result is as shown in table 5.
Table 5
Claims (8)
1. produce the method for methoxy menthyl acetate for one kind, it is characterized in that, by the unstripped gas that contains Methylal(dimethoxymethane) and carbon monoxide by being loaded with the reactor of solid acid catalyst, at 80～250 DEG C of temperature of reaction, reaction pressure 1～5.0MPa, the volume space velocity of carbon monoxide gas phase is 4300～26000h
-1, vapor phase carbonylation generates methoxy menthyl acetate;
Wherein in unstripped gas, the intrinsic standoff ratio of carbon monoxide and Methylal(dimethoxymethane) is 30～200.
2. method according to claim 1, is characterized in that, described solid acid catalyst is highly acidic resin.
3. method according to claim 1, is characterized in that, described solid acid catalyst is perfluorinated resin catalyzer.
4. method according to claim 3, is characterized in that described perfluorinated resin catalyzer is perfluorinated resin film catalyst and/or perfluorinated resin solid particle catalyst.
5. method according to claim 1, is characterized in that, reaction system is gas, solid two-phase, does not use liquid solvent in reaction.
6. method according to claim 1, is characterized in that, described solid acid catalyst is naphthols film catalyst and/or naphthols beaded catalyst.
7. method according to claim 1, is characterized in that, described reactor can be the one in fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor.
8. method according to claim 1, is characterized in that, described temperature of reaction is 80～180 DEG C, and described reaction pressure is 1～5.0MPa, and carbon monoxide gaseous phase volume air speed is 4300～26000h
-1, in unstripped gas, the intrinsic standoff ratio of carbon monoxide and Methylal(dimethoxymethane) is 50～200.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210570578.1A CN103896774A (en) | 2012-12-25 | 2012-12-25 | Method for producing methyl methoxy acetate |
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| CN201210570578.1A CN103896774A (en) | 2012-12-25 | 2012-12-25 | Method for producing methyl methoxy acetate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481693A (en) * | 2014-09-16 | 2016-04-13 | 中国科学院大连化学物理研究所 | Methyl methoxyacetate production method |
| CN106365999A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院大连化学物理研究所 | Acetal carbonylation product preparation method |
| CN106365993A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院大连化学物理研究所 | Acetal carbonylation product preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049644A1 (en) * | 1999-12-29 | 2001-07-12 | Shell Internationale Research Maatschappij B.V. | Process for the carbonylation of formaldehyde |
| WO2010048300A1 (en) * | 2008-10-23 | 2010-04-29 | The Regents Of The University Of California | Gas-phase catalyzed production of alkyl alkoxyacetates from dialkoxymethanes |
| CN102701977A (en) * | 2012-06-21 | 2012-10-03 | 东莞市同舟化工有限公司 | Continuous synthesis method for methyl methoxyacetate |
-
2012
- 2012-12-25 CN CN201210570578.1A patent/CN103896774A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049644A1 (en) * | 1999-12-29 | 2001-07-12 | Shell Internationale Research Maatschappij B.V. | Process for the carbonylation of formaldehyde |
| WO2010048300A1 (en) * | 2008-10-23 | 2010-04-29 | The Regents Of The University Of California | Gas-phase catalyzed production of alkyl alkoxyacetates from dialkoxymethanes |
| CN102701977A (en) * | 2012-06-21 | 2012-10-03 | 东莞市同舟化工有限公司 | Continuous synthesis method for methyl methoxyacetate |
Non-Patent Citations (1)
| Title |
|---|
| FUAT E. CELIK ET AL: "Vapor-Phase Carbonylation of Dimethoxymethane over H-Faujasite", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481693A (en) * | 2014-09-16 | 2016-04-13 | 中国科学院大连化学物理研究所 | Methyl methoxyacetate production method |
| CN105481693B (en) * | 2014-09-16 | 2017-08-25 | 中国科学院大连化学物理研究所 | A kind of method for producing methoxy menthyl acetate |
| CN106365999A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院大连化学物理研究所 | Acetal carbonylation product preparation method |
| CN106365993A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院大连化学物理研究所 | Acetal carbonylation product preparation method |
| CN106365999B (en) * | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A method of preparing acetal carbonyl compound |
| CN106365993B (en) * | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A method of preparing acetal carbonyl compound |
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Application publication date: 20140702 |