CN106478416A - A kind of preparation method of methyl formate - Google Patents
A kind of preparation method of methyl formate Download PDFInfo
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- CN106478416A CN106478416A CN201610736346.7A CN201610736346A CN106478416A CN 106478416 A CN106478416 A CN 106478416A CN 201610736346 A CN201610736346 A CN 201610736346A CN 106478416 A CN106478416 A CN 106478416A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of preparation method of methyl formate, generation methyl formate is reacted in the presence of solid-phase catalyst using formic acid and methanol；Described solid catalyst, with modified Nano bentonite as carrier, with copper nitrate as presoma, by the method for dipping, drying, roasting, copper oxide is carried on modified Nano bentonite；Described modified Nano bentonite preparation method is：Taking 30 40 parts of nano-bentonite to be scattered in 45 55 parts of mass fractions is in 5 15% triethylene tetramine, stirs 25 35min, add 5 15 parts of Zn (NO under the conditions of 40 50 DEG C3)2·6H2O, stirs 20 30min, filters, be drying to obtain after cooling.The preparation method that the present invention provides is simply easily operated, high conversion rate；Can repeatedly apply mechanically after solid catalyst separation, and repeatedly apply mechanically catalytic efficiency after repeatedly and no substantially reduce.
Description
Technical field
The invention belongs to chemical field is and in particular to a kind of preparation method of methyl formate.
Background technology
Methyl formate, calls formic acid methyl ester, is colourless dulcet volatile liquid.Miscible with ethanol, it is dissolved in methanol, second
Ether.Easily hydrolyze, the moisture in humid air also can bring it about hydrolysis.There is stronger stimulation to respiratory tract, eye, nose,
Pressure in chest, dyspnea can be caused.Methyl formate is the epochmaking intermediate of carbon geochemistry, and tool has been widely used, can be straight
Connect smoke fumigant and the antibacterial with dealing with Yan grass, dried fruit, corn etc.；Also it is commonly used for nitrocellulose, cellulose acetate
Solvent；In the synthesis material pharmaceutically, being commonly used for the medicines such as sulfonic acid methyl pyrimidine, sulfonic acid Sulfamonomethoxine, anti-tussive agents dromethan.
At present, the method producing methyl formate mainly has：Methanol formic acid esterification method, Liquid Phase Methanol carbonylation method, methanol take off
Hydrogen method, methanol oxydehydro process, formaldehyde dimerization method, synthesis gas direct synthesis technique etc..Wherein industrialized method has methanol first
Esterification method, Liquid Phase Methanol carbonylation method and methanol dehydrogenation method.Methanol dehydrogenation method, because of the also non-full maturity of technology, there is presently no
Promote the use of.Liquid Phase Methanol carbonylation method is the main method of external large-scale production methyl formate.And domestic still with methanol first
Esterification method is main method, but this method technique backwardness existing, high energy consumption, equipment corrosion are serious.
Content of the invention
It is an object of the invention to provide a kind of preparation method of methyl formate.
The above-mentioned purpose of the present invention is achieved by techniques below scheme：
A kind of preparation method of methyl formate, reacts generation formic acid using formic acid and methanol in the presence of solid-phase catalyst
Methyl ester；Described solid catalyst with modified Nano bentonite as carrier, with copper nitrate as presoma, by dipping, dry, roasting
Method copper oxide is carried on modified Nano bentonite；Described modified Nano bentonite preparation method is：Take a nanometer swelling
Native 30-40 part is scattered in the triethylene tetramine that 45-55 part mass fraction is 5-15%, stirs 25- under the conditions of 40-50 DEG C
35min, adds 5-15 part Zn (NO3)2·6H2O, stirs 20-30min, filters, be drying to obtain after cooling.
Preferably, described modified Nano bentonite preparation method is：Take 35 parts of nano-bentonite to be scattered in 50 parts of quality to divide
In the triethylene tetramine for 10% for the number, stir 30min under the conditions of 45 DEG C, add 10 parts of Zn (NO3)2·6H2O, stirring
25min, filters after cooling, is drying to obtain.
Preferably, the concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano bentonite is added in deionized water, modified Nano bentonite and deionization
Water quality is than for 1:10-1:20, ultrasonic disperse 30-60 minute, power 120-240W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 8-12h, wherein copper nitrate with modified
The mass ratio of nano-bentonite is 1:10-1:20；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 80-120 DEG C of drying in baking oven, subsequently
Transfer in tube furnace, be warming up to 400-450 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 3-5h, fall at this temperature
Take out after temperature and obtain final product described solid catalyst.
Preferably, methanol and the mol ratio of formic acid are 1:1.3-1.7.
Preferably, solid-phase catalyst weight is the 10-20% of methanol weight.
Preferably, the temperature of described reaction is 30-50 DEG C, and reaction pressure is 0.08-0.12MPa, reacts 6-10 hour.
Advantages of the present invention：
The preparation method that the present invention provides is simply easily operated, high conversion rate；Solid catalyst can cover after separating repeatedly
With, and repeatedly apply mechanically repeatedly after catalytic efficiency no substantially reduce.
Specific embodiment
Further illustrate the essentiality content of the present invention with reference to embodiment, but present invention protection model is not limited with this
Enclose.Although being explained in detail to the present invention with reference to preferred embodiment, it will be understood by those within the art that, can be right
Technical scheme is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention.
Embodiment 1：The preparation method of methyl formate
Generation methyl formate is reacted in the presence of solid-phase catalyst using formic acid and methanol.Wherein, methanol and formic acid
Mol ratio is 1:1.5, solid-phase catalyst weight is the 15% of methanol weight, 40 DEG C of reaction temperature, pressure 0.10MPa, and reaction 8 is little
When.
Described solid catalyst with modified Nano bentonite as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano bentonite the method for roasting；Described modified Nano bentonite preparation method is：Take nanometer
It is in 10% triethylene tetramine that 35 parts of bentonite is scattered in 50 parts of mass fractions, stirs 30min, add under the conditions of 45 DEG C
10 parts of Zn (NO3)2·6H2O, stirs 25min, filters, be drying to obtain after cooling.
The concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano bentonite is added in deionized water, modified Nano bentonite and deionization
Water quality is than for 1:15, ultrasonic disperse 45 minutes, power 180W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 10h, wherein copper nitrate and modification are received
The bentonitic mass ratio of rice is 1:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 420 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Embodiment 2：The preparation method of methyl formate
Generation methyl formate is reacted in the presence of solid-phase catalyst using formic acid and methanol.Wherein, methanol and formic acid
Mol ratio is 1:1.3, solid-phase catalyst weight is the 10% of methanol weight, 30 DEG C of reaction temperature, and pressure 0.08MPa reacts 10
Hour.
Described solid catalyst with modified Nano bentonite as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano bentonite the method for roasting；Described modified Nano bentonite preparation method is：Take nanometer
It is in 5% triethylene tetramine that 30 parts of bentonite is scattered in 45 parts of mass fractions, stirs 35min, add 5 under the conditions of 40 DEG C
Part Zn (NO3)2·6H2O, stirs 20min, filters, be drying to obtain after cooling.
The concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano bentonite is added in deionized water, modified Nano bentonite and deionization
Water quality is than for 1:10, ultrasonic disperse 30 minutes, power 240W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 8h, wherein copper nitrate and modified Nano
Bentonitic mass ratio is 1:10；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 80 DEG C of drying in baking oven, subsequently shifts
To in tube furnace, it is warming up to 400 DEG C under nitrogen atmosphere or argon gas atmosphere, and keeps 5h at this temperature, taking-up after cooling is
Obtain described solid catalyst.
Embodiment 3：The preparation method of methyl formate
Generation methyl formate is reacted in the presence of solid-phase catalyst using formic acid and methanol.Wherein, methanol and formic acid
Mol ratio is 1:1.7, solid-phase catalyst weight is the 20% of methanol weight, 50 DEG C of reaction temperature, pressure 0.12MPa, and reaction 6 is little
When.
Described solid catalyst with modified Nano bentonite as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano bentonite the method for roasting；Described modified Nano bentonite preparation method is：Take nanometer
It is in 15% triethylene tetramine that 40 parts of bentonite is scattered in 55 parts of mass fractions, stirs 25min, add under the conditions of 50 DEG C
15 parts of Zn (NO3)2·6H2O, stirs 30min, filters, be drying to obtain after cooling.
The concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano bentonite is added in deionized water, modified Nano bentonite and deionization
Water quality is than for 1:20, ultrasonic disperse 60 minutes, power 120W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 12h, wherein copper nitrate and modification are received
The bentonitic mass ratio of rice is 1:20；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 120 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 450 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 3h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Embodiment 4：The preparation method of methyl formate
Generation methyl formate is reacted in the presence of solid-phase catalyst using formic acid and methanol.Wherein, methanol and formic acid
Mol ratio is 1:1.5, solid-phase catalyst weight is the 12% of methanol weight, 40 DEG C of reaction temperature, pressure 0.10MPa, and reaction 8 is little
When.
Described solid catalyst with modified Nano bentonite as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano bentonite the method for roasting；Described modified Nano bentonite preparation method is：Take nanometer
It is in 10% triethylene tetramine that 35 parts of bentonite is scattered in 50 parts of mass fractions, stirs 30min, add under the conditions of 45 DEG C
10 parts of Zn (NO3)2·6H2O, stirs 25min, filters, be drying to obtain after cooling.
The concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano bentonite is added in deionized water, modified Nano bentonite and deionization
Water quality is than for 1:15, ultrasonic disperse 45 minutes, power 180W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 10h, wherein copper nitrate and modification are received
The bentonitic mass ratio of rice is 1:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 420 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Embodiment 5：The preparation method of methyl formate
Generation methyl formate is reacted in the presence of solid-phase catalyst using formic acid and methanol.Wherein, methanol and formic acid
Mol ratio is 1:1.5, solid-phase catalyst weight is the 18% of methanol weight, 40 DEG C of reaction temperature, pressure 0.10MPa, and reaction 8 is little
When.
Described solid catalyst with modified Nano bentonite as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano bentonite the method for roasting；Described modified Nano bentonite preparation method is：Take nanometer
It is in 10% triethylene tetramine that 35 parts of bentonite is scattered in 50 parts of mass fractions, stirs 30min, add under the conditions of 45 DEG C
10 parts of Zn (NO3)2·6H2O, stirs 25min, filters, be drying to obtain after cooling.
The concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano bentonite is added in deionized water, modified Nano bentonite and deionization
Water quality is than for 1:15, ultrasonic disperse 45 minutes, power 180W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 10h, wherein copper nitrate and modification are received
The bentonitic mass ratio of rice is 1:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 420 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Embodiment 6：Comparative example, nano-bentonite is not modified
Generation methyl formate is reacted in the presence of solid-phase catalyst using formic acid and methanol.Wherein, methanol and formic acid
Mol ratio is 1:1.5, solid-phase catalyst weight is the 15% of methanol weight, 40 DEG C of reaction temperature, pressure 0.10MPa, and reaction 8 is little
When.
Described solid catalyst with nano-bentonite as carrier, with copper nitrate as presoma, by dipping, dry, roasting
Method copper oxide is carried on nano-bentonite.
The concrete preparation method of solid catalyst includes：
Step S1：A certain amount of nano-bentonite is added in deionized water, nano-bentonite and deionized water quality ratio
For 1:15, ultrasonic disperse 45 minutes, power 180W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 10h, wherein copper nitrate are swollen with nanometer
The mass ratio of profit soil is 1:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 420 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Embodiment 7：Effect example
Catalytic efficiency fall after respectively the conversion ratio (%) of testing example 1-6 reaction and catalyst apply mechanically 50 times repeatedly
Low percentage value (%), result is as follows.
| Conversion ratio (%) | Catalytic efficiency reduces percentage rate (%) | |
| Embodiment 1 | 99.6 | 3 |
| Embodiment 6 | 90.9 | 36 |
Embodiment 2-5 measurement result is basically identical with embodiment 1, no longer enumerates one by one.
Result shows, the preparation method that the present invention provides is simply easily operated, high conversion rate；Solid catalyst can after separating
Repeatedly to apply mechanically, and repeatedly apply mechanically repeatedly after catalytic efficiency no substantially reduce.
The effect of above-described embodiment indicates that the essentiality content of the present invention, but does not limit the protection of the present invention with this
Scope.It will be understood by those within the art that, technical scheme can be modified or equivalent,
Essence without deviating from technical solution of the present invention and protection domain.
Claims (6)
1. a kind of preparation method of methyl formate is it is characterised in that adopt formic acid and methanol anti-in the presence of solid-phase catalyst
Methyl formate should be generated；Described solid catalyst with modified Nano bentonite as carrier, with copper nitrate as presoma, by leaching
Copper oxide is carried on modified Nano bentonite for stain, drying, the method for roasting；Described modified Nano bentonite preparation method
For：Nano-bentonite 30-40 part is taken to be scattered in the triethylene tetramine for 5-15% for the 45-55 part mass fraction, in 40-50 DEG C of bar
Stir 25-35min under part, add 5-15 part Zn (NO3)2·6H2O, stirs 20-30min, filters, be drying to obtain after cooling.
2. preparation method according to claim 1 is it is characterised in that described modified Nano bentonite preparation method is：Take
It is in 10% triethylene tetramine that 35 parts of nano-bentonite is scattered in 50 parts of mass fractions, stirs 30min under the conditions of 45 DEG C, then
Add 10 parts of Zn (NO3)2·6H2O, stirs 25min, filters, be drying to obtain after cooling.
3. preparation method according to claim 1 is it is characterised in that the concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano bentonite is added in deionized water, modified Nano bentonite and deionized water
Amount ratio is 1:10-1:20, ultrasonic disperse 30-60 minute, power 120-240W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 8-12h, wherein copper nitrate and modified Nano
Bentonitic mass ratio is 1:10-1:20；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 80-120 DEG C of drying in baking oven, subsequently shifts
To in tube furnace, it is warming up to 400-450 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 3-5h at this temperature, after cooling
Taking-up obtains final product described solid catalyst.
4. preparation method according to claim 1 it is characterised in that：Methanol is 1 with the mol ratio of formic acid:1.3-1.7.
5. preparation method according to claim 1 it is characterised in that：Solid-phase catalyst weight is the 10- of methanol weight
20%.
6. preparation method according to claim 1 it is characterised in that：The temperature of described reaction is 30-50 DEG C, reaction pressure
For 0.08-0.12MPa, react 6-10 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610736346.7A CN106478416A (en) | 2016-08-28 | 2016-08-28 | A kind of preparation method of methyl formate |
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| CN201610736346.7A CN106478416A (en) | 2016-08-28 | 2016-08-28 | A kind of preparation method of methyl formate |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230708A (en) * | 2014-10-10 | 2014-12-24 | 徐震霖 | Preparation method of methyl formate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230708A (en) * | 2014-10-10 | 2014-12-24 | 徐震霖 | Preparation method of methyl formate |
Non-Patent Citations (1)
| Title |
|---|
| 罗成刚 等: ""改性膨润土在有机反应中的应用"", 《化工进展》 * |
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