CN106083559B - A method of preparing formic acid - Google Patents
A method of preparing formic acid Download PDFInfo
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- CN106083559B CN106083559B CN201610396681.7A CN201610396681A CN106083559B CN 106083559 B CN106083559 B CN 106083559B CN 201610396681 A CN201610396681 A CN 201610396681A CN 106083559 B CN106083559 B CN 106083559B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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Abstract
The present invention provides a kind of methods for preparing formic acid, it includes the following steps: after mixing carbon dioxide or carbonate, raney copper catalyst and water, adjusting pH value is 8~12, in nitrogen atmosphere, it is reacted at 120~200 DEG C, to after reaction, be separated by solid-liquid separation, filtrate is collected, aqueous formic acid is obtained.Compared with prior art, the present invention have it is following the utility model has the advantages that 1, utilize thunder Buddhist nun's copper catalytic hydrogenation CO2And the method that carbonate prepares formic acid, raw material sources are extensively (such as industrial waste gas, vehicle exhaust), cheap, nontoxic without consuming fossil energy, can effectively reduce CO2Discharge；2, make reaction dissolvent using water, it is nontoxic, it is environmentally protective.3, reactant, nontoxic solvent are harmless, environmentally protective, and pollution on the environment is small；4, the raney copper catalyst used is cheap, is easy preparation；5, formic acid maximum output is up to 86.1%, selectively good, reactionless by-product.
Description
Technical field
The present invention relates to a kind of methods for preparing formic acid, belong to field of energy and chemical technology.
Background technique
The crisis of face of mankind nowadays global warming, energy shortage and environmental degradation, fossil energy consume excessively,
Great amount of carbon dioxide has been discharged, has caused global carbon unbalance and global warming.And CO2Itself be a kind of cheap, cleaning,
Nontoxic, safe carbon resource, therefore to CO2Resource utilization produce chemical products with high added-value, can not only effectively reduce
CO2Discharge, can also reduce the dependence to fossil energy, promote the harmonious circulation of carbon resource.In recent years, CO2Catalyzed conversion
It is subjected to people more and more to pay close attention to, CO2Catalytic hydrogenation is CO2The conventional means of recycling, and commonly used catalyst
Such as Pd, Rh, Ir, Ru noble metal catalyst, complex manufacturing technology and at high cost.Therefore exploitation preparation is simple environmental-friendly
Cheap metal catalyst promotes CO2Hydrogen is added to produce chemical products with high added-value (such as formic acid) imperative.Utilize sodium hydroxide solution
Absorb CO2Corresponding carbonate can be obtained, using carbonate as CO2Source is come to produce chemical products be a kind of common method.
Summary of the invention
The purpose of the present invention is to provide a kind of thunder Buddhist nun copper catalytic hydrogenation CO2And the method that carbonate prepares formic acid.The party
Method high conversion efficiency, good product selectivity is easy to operate without using the noble metal catalyst of complicated difficult preparation, is made using water
Solvent environmental pollution is small, and low energy consumption, is conducive to industrialized production.Product formic acid is important industrial chemicals, can be answered extensively
It is a kind of important intermediate chemical and change for producing pesticide, preservative, disinfectant, making natural rubber flocculating agent, pharmacy etc.
Work raw material.
The present invention is achieved by the following technical solutions:
The present invention provides a kind of methods for preparing formic acid comprising following steps:
After carbon dioxide or carbonate, raney copper catalyst and water are mixed, adjusting pH value is 8~12, in nitrogen atmosphere,
It is reacted at 120~200 DEG C, to after reaction, be separated by solid-liquid separation, collects filtrate, obtain aqueous formic acid.
Preferably, the carbonate is at least one of sodium carbonate, sodium bicarbonate, saleratus.
Preferably, the pressure of the nitrogen atmosphere is 1.5~7.5MPa.
Preferably, the molar ratio of the carbon dioxide and raney copper catalyst is 1:(0.47~1.10).Thunder Buddhist nun
The molal quantity of copper catalyst is subject to the substance of copper.
Preferably, the raney copper catalyst is corrode to CuAlZn alloy by sodium hydroxide solution
It arrives.
Preferably, the concentration of the sodium hydroxide solution is 10~30wt%.
Preferably, in the CuAlZn alloy, the mass ratio of Cu, Al, Zn are 50:45:5.
Preferably, the filling rate of the water is 10%.
Preferably, the method for the separation of solid and liquid is filtering.
In the present invention, the surface of raney copper catalyst has porous structure, can effectively adsorbed hydrogen, using hydrogen come
The C=O bond of bicarbonate ion is activated, dehydration obtains formic acid, and reaction principle is shown below:
Therefore, compared with prior art, the present invention have it is following the utility model has the advantages that
1, thunder Buddhist nun's copper catalytic hydrogenation CO is utilized2And the method that carbonate prepares formic acid, extensive (such as Industry Waste of raw material sources
Gas, vehicle exhaust etc.), it is cheap, it is nontoxic without consuming fossil energy, CO can be effectively reduced2Discharge；
2, make reaction dissolvent using water, it is nontoxic, it is environmentally protective；
3, reactant, nontoxic solvent are harmless, environmentally protective, and pollution on the environment is small；
4, the raney copper catalyst used is cheap, is easy preparation；
5, formic acid maximum output is up to 86.1%, selectively good, reactionless by-product.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the HPLC spectrogram of the product of embodiment 1 in the present invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The raney copper catalyst that each embodiment uses in the present invention is the sodium hydrate aqueous solution pair by 20wt%
CuAlZn alloy is corroded.
Embodiment 1
The present embodiment is related to a kind of thunder Buddhist nun copper catalytic hydrogenation CO2The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by CO2(1mmol), Lei Nitong (50mg) are fitted into the autoclave of Teflon liner, and water is added to make to react
Device filling rate is 10%, and adjusting above-mentioned pH value of solution with sodium hydroxide is 8.3, and reaction kettle is sealed to and is filled with 3MPa hydrogen, is reacted
Temperature is 200 DEG C, reaction time 120min, and mixture is taken out after reaction and filters formates.Resulting formates can pass through acid
Solution, distillation can obtain formic acid.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows as shown in Figure 1, formic acid is main produce
Object, quantitative analysis show that yield reaches as high as 77.2%.Suitable autoclave is used in industrial application on demand, it can be with
Controlling reaction temperature is 120~200 DEG C, and water filling rate reacts 60~420min 10%.It is reacted by this, it can be by CO2Largely
It is converted into formic acid, easy to operation and selectivity is good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Embodiment 2
The present embodiment is related to a kind of thunder Buddhist nun copper catalytic hydrogenation CO2The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by CO2(1mmol), Lei Nitong (50mg) are fitted into the autoclave of Teflon liner, and water is added to make to react
Device filling rate is 10%, and adjusting above-mentioned pH value of solution with sodium hydroxide is 8.3, and reaction kettle is sealed to and is filled with 6MPa hydrogen, is reacted
Temperature is 170 DEG C, reaction time 120min, and mixture is taken out after reaction and filters formates.Resulting formates can pass through acid
Solution, distillation can obtain formic acid.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield reaches as high as 37.4%.Suitable autoclave is used in industrial application on demand, can control reaction temperature
It is 120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by CO2It largely is converted into formic acid,
Easy to operation and selectivity is good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Embodiment 3
The present embodiment is related to a kind of thunder Buddhist nun copper catalytic hydrogenation NaHCO3The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by NaHCO3(1mmol), Lei Nitong (60mg) are fitted into the autoclave of Teflon liner, and water is added to make instead
Answering device filling rate is 10%, and reaction kettle is sealed to and is filled with 3MPa hydrogen, and reaction temperature is 200 DEG C, reaction time 120min, instead
Should after take out mixture filtering formates.Resulting formates can obtain formic acid by acidolysis, distillation.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield reaches as high as 69.2%.Suitable autoclave is used in industrial application on demand, can control reaction temperature
It is 120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by NaHCO3Largely it is converted into first
Acid, easy to operation and selectivity are good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Embodiment 4
The present embodiment is related to a kind of thunder Buddhist nun copper catalytic hydrogenation NaHCO3The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by NaHCO3(1mmol), Lei Nitong (50mg) are fitted into the autoclave of Teflon liner, and water is added to make instead
Answering device filling rate is 10%, and reaction kettle is sealed to and is filled with 6MPa hydrogen, and reaction temperature is 200 DEG C, reaction time 120min, instead
Should after take out mixture filtering formates.Resulting formates can obtain formic acid by acidolysis, distillation.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield reaches as high as 82.4%.Suitable hydrothermal reactor is used in industrial application on demand, can control reaction temperature
It is 120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by NaHCO3Largely it is converted into first
Acid, easy to operation and selectivity are good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Embodiment 5
The present embodiment is related to a kind of thunder Buddhist nun copper catalytic hydrogenation NaHCO3The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by NaHCO3(1mmol), Lei Nitong (50mg) are fitted into the autoclave of Teflon liner, and water is added to make instead
Answering device filling rate is 10%, and reaction kettle is sealed to and is filled with 6MPa hydrogen, and reaction temperature is 200 DEG C, reaction time 240min, instead
Should after take out mixture filtering formates.Resulting formates can obtain formic acid by acidolysis, distillation.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield reaches as high as 86.1%.Suitable hydrothermal reactor is used in industrial application on demand, can control reaction temperature
It is 120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by NaHCO3Largely it is converted into first
Acid, easy to operation and selectivity are good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Embodiment 6
The present embodiment is related to a kind of thunder Buddhist nun copper catalytic hydrogenation Na2CO3The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by Na2CO3(1mmol), Lei Nitong (50mg) are fitted into the autoclave of Teflon liner, and water is added to make instead
Answering device filling rate is 10%, and reaction kettle is sealed to and is filled with 6MPa hydrogen, and reaction temperature is 200 DEG C, reaction time 240min, instead
Should after take out mixture filtering formates.Resulting formates can obtain formic acid by acidolysis, distillation.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield reaches as high as 42.5%.Suitable hydrothermal reactor is used in industrial application on demand, can control reaction temperature
It is 120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by Na2CO3Largely it is converted into first
Acid, easy to operation and selectivity are good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Embodiment 7
The present embodiment is related to a kind of thunder Buddhist nun copper catalytic hydrogenation KHCO3The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by KHCO3(1mmol), Lei Nitong (50mg) are fitted into the autoclave of Teflon liner, and water is added to make instead
Answering device filling rate is 10%, and reaction kettle is sealed to and is filled with 6MPa hydrogen, and reaction temperature is 200 DEG C, reaction time 240min, instead
Should after take out mixture filtering formic acid.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield reaches as high as 83.7%.Suitable hydrothermal reactor is used in industrial application on demand, can control reaction temperature
It is 120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by KHCO3Largely it is converted into first
Acid, easy to operation and selectivity are good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Comparative example 1
The present embodiment is related to a kind of copper powder catalytic hydrogenation NaHCO3The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by NaHCO3(1mmol), copper powder (50mg) are fitted into the autoclave of Teflon liner, and water is added to make to react
Device filling rate is 10%, and reaction kettle is sealed to and is filled with 6MPa hydrogen, and reaction temperature is 200 DEG C, reaction time 120min, reaction
Mixture is taken out afterwards filters formates.Resulting formates can obtain formic acid by acidolysis, distillation.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield is up to 2.8%.Suitable hydrothermal reactor is used in industrial application on demand, can control reaction temperature is
120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by NaHCO3It largely is converted into formic acid,
Easy to operation and selectivity is good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
Comparative example 2
The present embodiment is related to a kind of Ru/C catalytic hydrogenation NaHCO3The method for preparing formic acid, reaction equation are as follows:
Described method includes following steps:
Successively by NaHCO3(1mmol), Ru/C (10mg) are fitted into the autoclave of Teflon liner, and water is added to make to react
Device filling rate is 10%, and reaction kettle is sealed to and is filled with 6MPa hydrogen, and reaction temperature is 200 DEG C, reaction time 120min, reaction
Mixture is taken out afterwards filters formates.Resulting formates can obtain formic acid by acidolysis, distillation.
Qualitative and quantitative analysis will be carried out to product after reaction, qualitative analysis shows that formic acid is primary product, quantitative analysis
Show that yield is up to 20.9%.Suitable hydrothermal reactor is used in industrial application on demand, can control reaction temperature is
120~200 DEG C, water filling rate reacts 60~420min 10%.It is reacted by this, it can be by NaHCO3It largely is converted into formic acid,
Easy to operation and selectivity is good.
Wherein, it after thunder Buddhist nun copper after the recovery is washed with deionized, may be reused, to further reduced into
This.
In conclusion the present invention utilizes thunder Buddhist nun copper catalytic hydrogenation CO2And the method that carbonate prepares formic acid, raw material sources are wide
It is general (such as industrial waste gas, vehicle exhaust), cheap, it is nontoxic without consuming fossil energy, CO can be effectively reduced2Discharge；Make
Make reaction dissolvent with water, it is nontoxic, it is environmentally protective；Reactant, nontoxic solvent are harmless, environmentally protective, the dirt caused by environment
It contaminates small；The raney copper catalyst used is cheap, is easy preparation；Formic acid maximum output is up to 86.1%, selectively good, reactionless pair
Product.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of method for preparing formic acid, which comprises the steps of:
After carbon dioxide or carbonate, raney copper catalyst and water are mixed, adjusting pH value is 8~12, in nitrogen atmosphere, in
It is reacted at 120~200 DEG C, to after reaction, be separated by solid-liquid separation, collects filtrate, obtain aqueous formic acid.
2. as described in claim 1 prepare formic acid method, which is characterized in that the carbonate be sodium carbonate, sodium bicarbonate,
At least one of saleratus.
3. as described in claim 1 prepare formic acid method, which is characterized in that the pressure of the nitrogen atmosphere be 1.5~
7.5MPa。
4. the method for preparing formic acid as described in claim 1, which is characterized in that the carbon dioxide and raney copper catalyst
Molar ratio is 1:(0.47~1.10).
5. the method as described in claim 1 or 4 for preparing formic acid, which is characterized in that the raney copper catalyst is to pass through hydrogen
Sodium hydroxide solution corrodes CuAlZn alloy.
6. the method for preparing formic acid as claimed in claim 5, which is characterized in that in the CuAlZn alloy, Cu, Al, Zn's
Mass ratio is 50:45:5.
7. as claimed in claim 5 prepare formic acid method, which is characterized in that the concentration of the sodium hydroxide solution be 10~
30wt%.
8. the method for preparing formic acid as described in claim 1, which is characterized in that the filling rate of the water is 10%.
9. the method for preparing formic acid as described in claim 1, which is characterized in that the method for the separation of solid and liquid is filtering.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265148A (en) * | 2008-04-28 | 2008-09-17 | 同济大学 | Method for preparing formic acid, methanol and methane by using metal hydro-thermal to reduce CO2 |
| CN105367404A (en) * | 2015-10-13 | 2016-03-02 | 大连理工大学 | Method for preparing formate through carbon dioxide catalytic hydrogenation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19963409A1 (en) * | 1999-12-28 | 2001-07-12 | Basf Ag | Process for the regeneration of catalysts |
| JP6289310B2 (en) * | 2014-08-27 | 2018-03-07 | 一般財団法人電力中央研究所 | Catalyst or precursor thereof, method for hydrogenating carbon dioxide using these, and method for producing formate |
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2016
- 2016-06-06 CN CN201610396681.7A patent/CN106083559B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265148A (en) * | 2008-04-28 | 2008-09-17 | 同济大学 | Method for preparing formic acid, methanol and methane by using metal hydro-thermal to reduce CO2 |
| CN105367404A (en) * | 2015-10-13 | 2016-03-02 | 大连理工大学 | Method for preparing formate through carbon dioxide catalytic hydrogenation |
Non-Patent Citations (5)
| Title |
|---|
| CO2加氢合成甲酸适宜工艺条件的研究;曾娓 等;《应用化工》;20110731;第40卷(第7期);第1156-1158页 |
| CO2合成甲酸研究进展;魏文英，尹燕华;《舰船防化》;20081231(第1期);第8页左栏第2-3段 |
| Highly efficient and autocatalytic H2O dissociation for CO2 reduction into formic acid with zinc;Fangming Jin等;《Scientific reports》;20140328;第1-8页 |
| Highly efficient water splitting and carbon dioxide reduction into formic acid with iron and copper powder;Heng Zhong等;《Chemical Engineering Journal》;20150602;第280卷;第215-221页 |
| The Hydrogenation of Carbon Dioxide and a Correction of the Reported Synthesis of Urethans;Mark W.Farlow，Homer Adkins;《Journal of the American Chemical Society》;19351130;第57卷;第2222-2223页 |
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