CN107021877A - The method of methanol direct oxidation synthesizing dimethoxym ethane - Google Patents
The method of methanol direct oxidation synthesizing dimethoxym ethane Download PDFInfo
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- CN107021877A CN107021877A CN201710319989.6A CN201710319989A CN107021877A CN 107021877 A CN107021877 A CN 107021877A CN 201710319989 A CN201710319989 A CN 201710319989A CN 107021877 A CN107021877 A CN 107021877A
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Abstract
The process for catalytic synthesis of dimethoxym ethane, it belongs to organic chemical synthesis field.Present invention application transition metal oxide catalysis methanol direct oxidation method synthesizing dimethoxym ethane, it is calcined after quartz sand and metal composite oxide are well mixed, sintering temperature is 400~600 DEG C, 1~5h of roasting time, room temperature is cooled to after roasting, obtained catalyst is placed in reactor, and absolute methanol, oxygen and nitrogen are passed through into reactor, with catalyst haptoreaction, 180~220 DEG C of reaction temperature, reaction pressure 1MPa, 1~9h of reaction time, 0.02~0.2mLmin of intake of methanol‑1, 3~15mLmin of intake of oxygen‑1, 10~80mLmin of intake of nitrogen‑1, obtain dimethoxym ethane.This method reaction condition is gentle, operation is easy；Metal oxide preparation technology is simple, cheap, has no toxic side effect；Feed stock conversion is high, and selectivity of product is high.
Description
Technical field
The invention belongs to organic chemical synthesis field, and in particular to a kind of method of methanol direct oxidation synthesizing dimethoxym ethane.
Background technology
Dimethoxym ethane has excellent physicochemical property, i.e. good dissolubility, low boiling, property compatible with water good, can answer extensively
For cosmetics, medicine, household supplies, industrial automotive articles for use, insecticide, leather polish, cleaning agent, rubber industry, paint,
In the products such as ink.Also due to dimethoxym ethane has good ability of cleaning greasy dirt and volatility, as cleaning agent can replace F11 and
F13 and chlorinated solvents, therefore be to substitute freon, the discharge of volatile organic matter is reduced, the environmental protection to atmosphere pollution is reduced.It
Fuel additive is also used as, the Cetane number of diesel oil can be improved, lifting engine power, promotion Combustion Energy are converted into dynamic
Energy.In addition, under Pt, Ru and Pt, Sn catalysis, dimethoxym ethane can turn into the alternative fuel of promising fuel cell.
Dimethoxym ethane is general to occur condensation reaction preparation by absolute methanol and formaldehyde.Conventional acidic catalyst is realized.But the method is deposited
The substantial amounts of acidic organic wastewater containing formaldehyde is produced in process of production, consersion unit is corrosive, and pollutes the shortcoming of environment.
With methanol one-step oxidation process synthesizing dimethoxym ethane, the producing cost and investment cost of dimethoxym ethane are greatly reduced, is to solve above-mentioned ask
The effective way of topic.CN 201610544029.5 is disclosed applies ruthenic chloride catalysis methanol oxidative synthesis in batch reactor
Dimethoxym ethane technology, applies 1,2- cyclohexanedionedioximes for organic solvent in the reaction.This technology belongs to homogeneous catalytic reaction,
The recovery of its catalyst, using and post-reaction treatment technics comparing it is cumbersome；CN 200810055101.3, which is disclosed, applies V2O5-
TiO2Catalyst methanol oxidation to methylal and methyl formate technology, reaction are carried out in fixed bed reactors, but
Selectivity is there is in course of reaction relatively low, the problem of accessory substance is more and methanol has peroxidating, and catalyst
Preparation is carried out under nitrogen protection, and operating condition is harsh.
The content of the invention
It is an object of the present invention to provide a kind of method of methanol direct oxidation synthesizing dimethoxym ethane.
The present invention is achieved through the following technical solutions：
A kind of method of methanol direct oxidation synthesizing dimethoxym ethane, comprises the following steps：
Step 1, quartz sand, the metal composite oxide for weighing according to parts by weight certain mass, by load weighted quartz
It is calcined after sand and metal composite oxide are well mixed, sintering temperature is 400~600 DEG C, 1~5h of roasting time, roasting
After be cooled to room temperature, obtain catalyst, it is stand-by；
Step 2, the catalyst that step 1 is obtained is placed in reactor, absolute methanol, oxygen and nitrogen are passed through into reactor
Gas, and catalyst haptoreaction, 180~220 DEG C of reaction temperature, reaction pressure 1MPa, 1~9h of reaction time, methanol is passed through
Measure 0.02~0.2mLmin-1, 3~15mLmin of intake of oxygen-1, 10~80mLmin of intake of nitrogen-1；
Step 3, by the reacted gas of step 2 by be equipped with flame ionization detector online gas-chromatography sample
Analysis system, calculates conversion ratio, the selectivity of dimethoxym ethane, the yield of dimethoxym ethane for obtaining absolute methanol.
The parts by weight of quartz sand are 10 in the method for methanol direct oxidation synthesizing dimethoxym ethane of the present invention, step 1
~50 parts, the parts by weight of metal composite oxide are 5~20 parts.
A diameter of the 40~100 of quartz sand in the method for methanol direct oxidation synthesizing dimethoxym ethane of the present invention, step 1
Mesh.
Metal composite oxide in the method for methanol direct oxidation synthesizing dimethoxym ethane of the present invention, step 1 is
ZrO2、Fe2O3、ZnO、CuO、NiO、V2O5、Al2O3、SnO2In any 2 kinds of combination, wherein 2 kinds of different metal oxides
Mass ratio is 5~10：5.
The method of methanol direct oxidation synthesizing dimethoxym ethane of the present invention, described metal oxide a diameter of 40~
100 mesh.
Reactor in the method for methanol direct oxidation synthesizing dimethoxym ethane of the present invention, step 2 is fixed bed reaction
Device.
The method of methanol direct oxidation synthesizing dimethoxym ethane of the present invention, described fixed bed reactors are that internal diameter is
6mm quartz ampoule is made.
Methanol, O in the method for methanol direct oxidation synthesizing dimethoxym ethane of the present invention, step 22、N2Intake ratio
It is worth for 1:100:300.
Gas sky hourly in the method for methanol direct oxidation synthesizing dimethoxym ethane of the present invention, fixed bed reactors
Speed is 1203mlg-1·h-1, the gross mass of described catalyst is 1g.
The method of methanol direct oxidation synthesizing dimethoxym ethane of the present invention, conversion ratio is high with selectivity.With background technology
CN200810055101.3 is compared with CN201610544029.5, the side of methanol direct oxidation synthesizing dimethoxym ethane of the present invention
There was only dimethoxym ethane and dimethyl ether in product prepared by method, the selectivity of dimethoxym ethane is more than 95.0%.
The method of methanol direct oxidation synthesizing dimethoxym ethane of the present invention, catalyst preparation process is simple, raw material is inexpensive
It is easy to get.Compared with background technology CN200810055101.3, the preparation of the catalyst used in this technology need not be in indifferent gas
Body protection is lower to be carried out.
The method of methanol direct oxidation synthesizing dimethoxym ethane of the present invention, preparation condition is gentle, and pressure is normal pressure.With the back of the body
Scape technology CN201610544029.5 is compared, and fixed bed heterogeneous catalysis, which has, can be continuously produced, the advantages of catalyst life is long.
The method of methanol direct oxidation synthesizing dimethoxym ethane of the present invention, technique is simple, and operation is easy.
Embodiment
Embodiment one：
A kind of method of methanol direct oxidation synthesizing dimethoxym ethane, comprises the following steps：
Step 1, quartz sand, the metal composite oxide for weighing according to parts by weight certain mass, by load weighted quartz
It is calcined after sand and metal composite oxide are well mixed, sintering temperature is 600 DEG C, and roasting time 5h is cooled to after roasting
Room temperature, obtains catalyst, stand-by；
Step 2, the catalyst that step 1 is obtained is placed in reactor, absolute methanol, oxygen and nitrogen are passed through into reactor
Gas, with catalyst haptoreaction, 200 DEG C of reaction temperature, reaction pressure 1MPa, reaction time 8h, the intake 0.1mL of methanol
min-1, the intake 10mLmin of oxygen-1, the intake 30mLmin of nitrogen-1；
Step 3, by the reacted gas of step 2 by be equipped with flame ionization detector online gas-chromatography sample
Analysis system, calculates conversion ratio, the selectivity of dimethoxym ethane, the yield of dimethoxym ethane for obtaining absolute methanol.
The parts by weight of quartz sand in the method for methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, step 1
For 10 parts, the parts by weight of metal composite oxide are 10 parts.
A diameter of the 40 of quartz sand in the method for methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, step 1
Mesh.
Metal composite oxide in the method for methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, step 1
For CuO, V2O5Combination, wherein CuO, V2O5Mass ratio be 5：5.
The method of methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, described metal oxide it is a diameter of
40 mesh.
Reactor in the method for methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, step 2 is fixed bed
Reactor.
The method of methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, described fixed bed reactors are internal diameter
It is made up of 6mm quartz ampoule.
Methanol, O in the method for methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, step 22、N2Be passed through
It is 1 to measure ratio:100:300.
The method of methanol direct oxidation synthesizing dimethoxym ethane described in present embodiment, after reaction terminates, the conversion ratio of methanol
For 20%, the selectivity of dimethoxym ethane is 94%.
Embodiment two：
Present embodiment from unlike embodiment one：Metal composite oxide in step 1 is ZrO2、V2O5
Combination, wherein ZrO2、V2O5Mass ratio be 5：6, after reaction terminates, the conversion ratio of methanol is higher up to 38%, dimethoxym ethane
Selectivity 96.2%.
Embodiment three：
Present embodiment from unlike embodiment one or two：Metal composite oxide in step 1 is Fe2O3、
V2O5Combination, wherein Fe2O3、V2O5Mass ratio be 5：7, after reaction terminates, the conversion ratio of methanol is higher up to 21%, first contracting
The selectivity 95.8% of aldehyde.
Embodiment four：
Unlike one of present embodiment and embodiment one to three：Metal composite oxide in step 1 is
SnO2、V2O5Combination, wherein SnO2、V2O5Mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher up to 22%,
The selectivity 93% of dimethoxym ethane.
Embodiment five：
Unlike one of present embodiment and embodiment one to four：Metal composite oxide in step 1 is
Al2O3、V2O5Combination, wherein Al2O3、V2O5Mass ratio be 5：10, after reaction terminates, the conversion ratio of methanol is higher reachable
23%, the selectivity 95.3% of dimethoxym ethane.
Embodiment six：
Unlike one of present embodiment and embodiment one to five：Metal composite oxide in step 1 is
NiO、V2O5Combination, wherein NiO, V2O5Mass ratio be 5：6, after reaction terminates, the conversion ratio of methanol is higher up to 27%,
The selectivity 93.7% of dimethoxym ethane.
Embodiment seven：
Unlike one of present embodiment and embodiment one to six：Metal composite oxide in step 1 is
ZnO、V2O5Combination, wherein ZnO, V2O5Mass ratio be 5：8, after reaction terminates, the conversion ratio of methanol is higher up to 28%,
The selectivity 93.8% of dimethoxym ethane.
Embodiment eight：
Unlike one of present embodiment and embodiment one to seven：Metal composite oxide in step 1 is
CuO、ZrO2Combination, wherein CuO, ZrO2Mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher up to 25%,
The selectivity 96.2% of dimethoxym ethane.
Embodiment nine：
Unlike one of present embodiment and embodiment one to eight：Metal composite oxide in step 1 is
CuO、Fe2O3Combination, wherein CuO, Fe2O3Mass ratio be 5：10, after reaction terminates, the conversion ratio of methanol is higher reachable
20%, the selectivity 94.9% of dimethoxym ethane.
Embodiment ten：
Unlike one of present embodiment and embodiment one to nine：Metal composite oxide in step 1 is
CuO、SnO2Combination, wherein CuO, SnO2Mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher up to 27%,
The selectivity 90% of dimethoxym ethane.
Embodiment 11：
Unlike one of present embodiment and embodiment one to ten：Metal composite oxide in step 1 is
CuO、Al2O3Combination, wherein CuO, Al2O3Mass ratio be 5：6, after reaction terminates, the conversion ratio of methanol is higher reachable
24%, the selectivity 92.8% of dimethoxym ethane.
Embodiment 12：
Present embodiment from unlike embodiment one to one of 11：Metal composite oxide in step 1
For CuO, NiO combination, wherein CuO, NiO mass ratio is 5：7, after reaction terminates, the conversion ratio of methanol is higher up to 25%,
The selectivity 92% of dimethoxym ethane.
Embodiment 13：
Present embodiment from unlike embodiment one to one of 12：Metal composite oxide in step 1
For CuO, ZnO combination, wherein CuO, ZnO mass ratio is 5：9, after reaction terminates, the conversion ratio of methanol is higher up to 26%,
The selectivity 96% of dimethoxym ethane.
Embodiment 14：
Present embodiment from unlike embodiment one to one of 13：Metal composite oxide in step 1
For ZrO2、Fe2O3Combination, wherein ZrO2、Fe2O3Mass ratio be 5：9, after reaction terminates, the conversion ratio of methanol is higher reachable
30%, the selectivity 91% of dimethoxym ethane.
Embodiment 15：
Present embodiment from unlike embodiment one to one of 14：Metal composite oxide in step 1
For ZrO2, SnO combination, wherein ZrO2, SnO mass ratio be 5：6, after reaction terminates, the conversion ratio of methanol is higher reachable
33%, the selectivity 92% of dimethoxym ethane.
Embodiment 16：
Present embodiment from unlike embodiment one to one of 15：Metal composite oxide in step 1
For ZrO2、Al2O3Combination, wherein ZrO2、Al2O3Mass ratio be 5：10, after reaction terminates, the conversion ratio of methanol is higher reachable
33%, the selectivity 95.2% of dimethoxym ethane.
Embodiment 17：
Present embodiment from unlike embodiment one to one of 16：Metal composite oxide in step 1
For ZrO2, NiO combination, wherein ZrO2, NiO mass ratio be 5：7, after reaction terminates, the conversion ratio of methanol is higher reachable
31%, the selectivity 92% of dimethoxym ethane.
Embodiment 18：
Present embodiment from unlike embodiment one to one of 17：Metal composite oxide in step 1
For ZrO2, ZnO combination, wherein ZrO2, ZnO mass ratio be 5：8, after reaction terminates, the conversion ratio of methanol is higher reachable
32%, the selectivity 94% of dimethoxym ethane.
Embodiment 19：
Present embodiment from unlike embodiment one to one of 18：Metal composite oxide in step 1
For Fe2O3、SnO2Combination, wherein Fe2O3、SnO2Mass ratio be 5：9, after reaction terminates, the conversion ratio of methanol is higher reachable
34%, the selectivity 92.5% of dimethoxym ethane.
Embodiment 20：
Present embodiment from unlike embodiment one to one of 19：Metal composite oxide in step 1
For Fe2O3、Al2O3Combination, wherein Fe2O3、Al2O3Mass ratio be 5：10, after reaction terminates, the conversion ratio of methanol is higher can
Up to 33%, the selectivity 90% of dimethoxym ethane.
Embodiment 21：
Present embodiment from unlike embodiment one to one of 20：Metal composite oxide in step 1
For Fe2O3, NiO combination, wherein Fe2O3, NiO mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher reachable
35%, the selectivity 93.4% of dimethoxym ethane.
Embodiment 22：
Present embodiment from unlike embodiment one to one of 21：Composition metal oxidation in step 1
Thing is Fe2O3, ZnO combination, wherein Fe2O3, ZnO mass ratio be 5：6, after reaction terminates, the conversion ratio of methanol is higher reachable
34%, the selectivity 95.3% of dimethoxym ethane.
Embodiment 23：
Present embodiment from unlike embodiment one to one of 22：Composition metal oxidation in step 1
Thing is SnO2、Al2O3Combination, wherein SnO2、Al2O3Mass ratio be 5：7, after reaction terminates, the conversion ratio of methanol is higher can
Up to 35%, the selectivity 93% of dimethoxym ethane.
Embodiment 24：
Present embodiment from unlike embodiment one to one of 23：Composition metal oxidation in step 1
Thing is SnO2, NiO combination, wherein SnO2, NiO mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher reachable
37%, the selectivity 91% of dimethoxym ethane.
Embodiment 25：
Present embodiment from unlike embodiment one to one of 24：Composition metal oxidation in step 1
Thing is SnO2, ZnO combination, wherein SnO2, ZnO mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher reachable
38%, the selectivity 94.5% of dimethoxym ethane.
Embodiment 26：
Present embodiment from unlike embodiment one to one of 25：Composition metal oxidation in step 1
Thing is Al2O3, NiO combination, wherein Al2O3, NiO mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher reachable
35%, the selectivity 96% of dimethoxym ethane.
Embodiment 27：
Present embodiment from unlike embodiment one to one of 26：Composition metal oxidation in step 1
Thing is Al2O3, ZnO combination, wherein Al2O3, NiO mass ratio be 5：5, after reaction terminates, the conversion ratio of methanol is higher reachable
35%, the selectivity 92% of dimethoxym ethane.
Claims (8)
1. a kind of method of methanol direct oxidation synthesizing dimethoxym ethane, it is characterised in that：Comprise the following steps：
Step 1, quartz sand, the metal composite oxide for weighing according to parts by weight certain mass, by load weighted quartz sand and
It is calcined after metal composite oxide is well mixed, sintering temperature is 400~600 DEG C, roasting time 1~5h is cold after roasting
But to room temperature, catalyst is obtained, it is stand-by；
Step 2, the catalyst that step 1 is obtained is placed in reactor, absolute methanol, oxygen and nitrogen is passed through into reactor,
With catalyst haptoreaction, 180~220 DEG C of reaction temperature, reaction pressure 1MPa, 1~9h of reaction time, the intake of methanol
0.02~0.2mLmin-1, 3~15mLmin of intake of oxygen-1, 10~80mLmin of intake of nitrogen-1；
Step 3, by the reacted gas of step 2 by being equipped with the online gas-chromatography sampling analysis of flame ionization detector
System, calculates conversion ratio, the selectivity of dimethoxym ethane, the yield of dimethoxym ethane for obtaining absolute methanol.
2. the method for methanol direct oxidation synthesizing dimethoxym ethane according to claim 1, it is characterised in that：It is quartzy in step 1
The parts by weight of sand are 10~50 parts, and the parts by weight of metal composite oxide are 5~20 parts.
3. the method for methanol direct oxidation synthesizing dimethoxym ethane according to claim 1 or 2, it is characterised in that：Stone in step 1
A diameter of 40~100 mesh of sand.
4. the method for methanol direct oxidation synthesizing dimethoxym ethane according to claim 1 or 2, it is characterised in that：In step 1
Metal composite oxide is ZrO2、Fe2O3、ZnO、CuO、NiO、V2O5、Al2O3、SnO2In any 2 kinds of combination, wherein 2 kinds
The mass ratio of different metal oxides is 5~10：5.
5. the method for methanol direct oxidation synthesizing dimethoxym ethane according to claim 4, it is characterised in that：Described metal oxygen
A diameter of 40~100 mesh of compound.
6. the method for methanol direct oxidation synthesizing dimethoxym ethane according to claim 1, it is characterised in that：It is anti-in step 2
It is fixed bed reactors to answer device.
7. the method for methanol direct oxidation synthesizing dimethoxym ethane according to claim 6, it is characterised in that：Described fixed bed
Reactor is made up of internal diameter of 6mm quartz ampoule.
8. the method for methanol direct oxidation synthesizing dimethoxym ethane according to claim 1, it is characterised in that：First in step 2
Alcohol, O2、N2Intake ratio be 1:100:300.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710319989.6A CN107021877A (en) | 2017-05-09 | 2017-05-09 | The method of methanol direct oxidation synthesizing dimethoxym ethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710319989.6A CN107021877A (en) | 2017-05-09 | 2017-05-09 | The method of methanol direct oxidation synthesizing dimethoxym ethane |
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| WO2020124421A1 (en) * | 2018-12-19 | 2020-06-25 | Rhodia Operations | A process for preparing acetals or ketals |
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| US20050059839A1 (en) * | 2003-09-15 | 2005-03-17 | The Regents Of The University Of California | Process and catalysts for the oxidation of methanol and/or ethanol |
| CN101224431A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
| CN101721991A (en) * | 2008-10-31 | 2010-06-09 | 南京大学 | Method for preparing V-Ti-Si-O composite catalyst used in methanol oxidation for synthesizing methylal |
| CN102000559A (en) * | 2010-11-18 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst |
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| US20050059839A1 (en) * | 2003-09-15 | 2005-03-17 | The Regents Of The University Of California | Process and catalysts for the oxidation of methanol and/or ethanol |
| CN101224431A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
| CN101721991A (en) * | 2008-10-31 | 2010-06-09 | 南京大学 | Method for preparing V-Ti-Si-O composite catalyst used in methanol oxidation for synthesizing methylal |
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| WO2020124421A1 (en) * | 2018-12-19 | 2020-06-25 | Rhodia Operations | A process for preparing acetals or ketals |
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