CN111153788A - Method for preparing organic acid through organic alcohol dehydrogenation reaction and method for thermodynamically controlling organic alcohol dehydrogenation reaction - Google Patents
Method for preparing organic acid through organic alcohol dehydrogenation reaction and method for thermodynamically controlling organic alcohol dehydrogenation reaction Download PDFInfo
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Abstract
The application discloses a method for preparing organic acid by organic alcohol dehydrogenation reaction and a method for thermodynamically controlling and adjusting the organic alcohol dehydrogenation reaction; wherein the method for preparing organic acid comprises the following steps: obtaining the basic pK of the basebCorrelation with thermodynamic parameters of the reaction; selecting alkali according to the incidence relation and the target thermodynamic parameter to perform target reaction; wherein the reaction is carried out in the presence of a base. The method disclosed by the application can be used for controllably adjusting the Gibbs free energy change of the reaction according to the linear relation between alkalinity and the Gibbs free energy change of the reaction, so that the process of the reaction is controlled; can be applied to reversible liquid organic hydrogen storage materialsAnd (4) material system.
Description
Technical Field
The application relates to a method for preparing organic acid by organic alcohol dehydrogenation reaction and a method for thermodynamically controlling and adjusting organic alcohol dehydrogenation reaction, belonging to the field of catalytic dehydrogenation.
Background
The chemical hydrogen storage mode is mainly divided into inorganic hydride and organic hydride hydrogen storage, and the inorganic hydride hydrogen storage material comprises metal hydride, composite hydride, chemical hydride and the like. The metal hydride has good thermodynamic and kinetic properties and strong safety, but has the defect of low mass energy density of hydrogen. The complex hydride has high hydrogen storage capacity, but has poor kinetics and thermodynamics, and is not suitable for practical application. Although chemical hydride has a high hydrogen storage capacity, it is an irreversible hydrogen storage material, and is also not suitable for vehicle-mounted or large-scale utilization. The organic hydride hydrogen storage is mainly liquid organic hydrogen storage, the hydrogen storage amount is high (can reach 6% -8%), the performance is stable, the safety is high, the existing gasoline conveying mode and the existing gas station framework can be directly utilized, a lot of resources are saved in the aspect of engineering, and the liquid organic hydrogen storage is more suitable for large-scale and long-distance hydrogen transportation. However, the dehydrogenation enthalpy of the liquid organic hydride is very high, so that dehydrogenation at higher temperature is required, and the liquid organic hydride is not suitable for practical application. Therefore, the development of a novel liquid organic hydrogen storage system is one of effective approaches for solving the hydrogen storage problem.
Many researches on hydrogenation reaction of organic acid have been carried out, and at present, an industrial device is used for hydrogenation of organic acid to prepare organic alcohol. However, the reverse reaction is organic alcohol dehydrogenation which is a strong endothermic reaction, a higher dehydrogenation temperature is required, and thermodynamics is not ideal, so that the reaction is not taken into consideration as a circulating hydrogen storage system, and the dehydrogenation reaction in the prior art is not suitable for being used as the hydrogen storage system.
Disclosure of Invention
According to one aspect of the application, a method for preparing organic acid by organic alcohol dehydrogenation is provided, and the method can be used for realizing dehydrogenation of organic alcohol under mild conditions by taking a linear relation between alkalinity and thermodynamics as an effective reference for modulating thermodynamic parameters of organic alcohol dehydrogenation, and controllably adjusting thermodynamic data of the organic alcohol dehydrogenation.
In the application, alkali with different alkalities is selected to react with acid, so that the thermodynamic property of the reaction of the methanol-formic acid system can be effectively adjusted. The final aim is to optimize the Gibbs free energy change of the dehydrogenation reaction to be about zero by using proper alkali, so that the hydrogenation-dehydrogenation cycle under mild conditions can be theoretically realized, and the hydrogen storage and discharge cycle efficiency is improved.
The method for preparing the organic acid by the organic alcohol dehydrogenation reaction is characterized by comprising the following steps:
(1) obtaining the basic pK of the basebCorrelation with thermodynamic parameters of the reaction;
(2) selecting alkali according to the incidence relation and the target thermodynamic parameter to perform target reaction;
wherein the reaction is carried out in the presence of a base.
Optionally, the thermodynamic parameter is gibbs free energy change of reaction;
the pK isbAnd the change of the Gibbs free energy is in a linear relation.
Optionally, a base is selected according to the correlation to obtain/adjust the direction of the reaction.
Alternatively, the base mainly includes an organic base, an inorganic base, and the like.
Optionally, the base is selected from at least one of an organic base and an inorganic base.
Optionally, the reaction comprises: reacting the solution containing organic alcohol in the presence of a catalyst and a base to obtain the organic acid.
Alternatively, the reaction is as shown in formula R1:
RCH2OH+H2O＝RCOOH+2H2formula R1.
Alternatively, the organic alcohol includes monohydric alcohol, dihydric alcohol, polyhydric alcohol, etc., preferably methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, butylene glycol, etc.
Optionally, the organic alcohol comprises one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, and butylene glycol.
The propanol comprises n-propanol and isopropanol; the propylene glycol comprises 1, 2-propylene glycol and 1, 3-propylene glycol; the butanediol comprises 1, 2-propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol and 2, 4-butanediol.
Alternatively, the dehydrogenation reaction needs to be carried out in solution, preferably in aqueous solution.
Optionally, the solvent of the organic alcohol-containing solution is water.
Alternatively, the base is used in an amount of between 0.1 and 100 times, preferably between 0.5 and 3 times the amount of organic alcohol used.
Alternatively, the catalyst may be a homogeneous catalyst or a heterogeneous catalyst.
Alternatively, the catalyst may comprise primarily noble and non-noble metal catalysts, such as binary or multi-element catalysts of Pt, Pd, Ru, Rh, Ir, Fe, Co, Ni, Cu and combinations thereof.
Optionally, the catalyst is at least one selected from metals, binary compounds of metals and multi-component compounds of metals.
Optionally, the molar ratio of the base to the organic alcohol is 0.1 to 100: 1.
Optionally, the molar ratio of the catalyst to the organic alcohol is 0.001 to 0.1.
Optionally, the temperature of the reaction is 0 ℃ to 300 ℃.
Optionally, the reaction time is no more than 100 hours.
Optionally, the molar ratio of the base to the organic alcohol is 0.5 to 3: 1.
Optionally, the metal comprises at least one of Pt, Pd, Ru, Rh, Ir, Fe, Co, Ni, Cu.
Alternatively, the temperature of the reaction is from room temperature to 100 ℃.
Optionally, the reaction time is no more than 20 hours.
Optionally, the upper temperature limit of the reaction is selected from 10 ℃, 30 ℃,50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃; the lower limit is selected from 0 deg.C, 10 deg.C, 30 deg.C, 50 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 150 deg.C, 200 deg.C or 250 deg.C.
The method for preparing the organic acid by the organic alcohol dehydrogenation reaction can realize the technical scheme within the condition ranges of the temperature (0-300 ℃), the time (not more than 100 hours) and the proportion (the molar ratio of the alkali to the organic alcohol is 0.1-100: 1), so that the technical effect is achieved.
The present application establishes basicity (pK)b) The relationship between the free energy of Gibbs and the dehydrogenation reaction of the organic alcohol is utilized, and the linear relationship is utilized to select proper alkali to carry out experiments on the dehydrogenation reaction of the organic alcohol.
The method utilizes alkali to modulate the thermodynamic parameters of the organic alcohol dehydrogenation reaction, and establishes the linear relation between alkalinity and thermodynamics, so that the linear relation can be used as an effective reference for modulating the thermodynamic parameters of the organic alcohol dehydrogenation reaction, the thermodynamic data can be controllably adjusted, and the dehydrogenation of the organic alcohol under the mild condition is realized; this application relates to the fields of catalytic dehydrogenation, catalytic decarboxylation, hydrogen storage materials, and the like.
In another aspect of the present application, there is provided a method for thermodynamically controlling the dehydrogenation reaction of an organic alcohol, comprising:
(a) obtaining the basic pK of the basebCorrelation with thermodynamic parameters of the reaction;
(b) and selecting different alkalis according to the incidence relation to obtain different reaction thermodynamic parameters, namely, the organic alcohol dehydrogenation reaction thermodynamic parameters can be controlled and adjusted.
Optionally, the thermodynamic parameter is gibbs free energy change of reaction;
the pK isbAnd the change of the Gibbs free energy is in a linear relation.
Alternatively, the organic alcohol dehydrogenation reaction comprises any of the methods described above for producing organic acids by an organic alcohol dehydrogenation reaction.
Alternatively, the organic alcohol dehydrogenation reaction is a method for producing an organic acid by the organic alcohol dehydrogenation reaction described in any one of the above.
Alternatively, the reaction is expected to have applications in the fields of hydrogen storage materials, hydrogen production, decarboxylation, and the like.
According to still another aspect of the present application, there is provided a method for preparing organic acid by organic alcohol dehydrogenation reaction and/or a method for thermodynamically controlling regulation of organic alcohol dehydrogenation reaction in any one of the above fields of hydrogen storage material, hydrogen production and decarboxylation.
The application establishes a method for thermodynamically controlling the dehydrogenation reaction of organic alcohol. In particular to a method for regulating Gibbs free energy change of organic acid generation reaction of organic alcohol aqueous solution dehydrogenation by using alkali. The invention finds the linear relation between the alkalinity and the Gibbs free energy change of the reaction, so that the Gibbs free energy change of the reaction can be controllably adjusted by means of the linear relation, thereby controlling the reaction process. The invention can be applied to reversible liquid organic hydrogen storage material systems. The organic alcohol selected includes monohydric alcohol, dihydric alcohol, and polyhydric alcohol, and the base selected includes common organic base or inorganic base. The beneficial effects that this application can produce include:
1) the method for preparing organic acid by organic alcohol dehydrogenation and/or the method for thermodynamically controlling and adjusting organic alcohol dehydrogenation are/is applied to a reversible liquid organic hydrogen storage material system.
2) According to the method for thermodynamically controllably adjusting the organic alcohol dehydrogenation reaction, the Gibbs free energy change of the reaction is controllably adjusted according to the linear relation between alkalinity and the Gibbs free energy change of the reaction, so that the reaction process is controlled.
3) According to the method for thermodynamically controllable adjustment of the organic alcohol dehydrogenation reaction, alkali with different alkalities is selected to react with acid, so that the thermodynamic property of the methanol-formic acid system reaction can be effectively adjusted, the Gibbs free energy change of the dehydrogenation reaction is optimized to be about zero by using proper alkali, hydrogenation-dehydrogenation circulation under mild conditions can be theoretically realized, and the hydrogen storage and release circulation efficiency is improved.
Drawings
FIG. 1 is a graph showing the relationship between the degree of basicity and the Gibbs free energy change of reaction in a base-modified methanol-formic acid reaction (R4) according to one embodiment of the present invention.
FIG. 2 is a graph showing the relationship between the degree of basicity and the Gibbs free energy of reaction in the base-modified ethylene glycol-oxalic acid reaction (R5) according to one embodiment of the present application.
FIG. 3 is a reaction process of a Pt/C catalyst catalyzing dehydrogenation of 1, 4-butanediol in the presence of NaOH in one embodiment of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
quantitative analysis of the product was performed using nuclear magnetism (Bruker Advance 3, 500M).
The conversion, selectivity, in the examples of the present application were calculated as follows:
conversion ═ initial amount of reactant-remaining amount of reactant)/initial amount of reactant × 100%
Selectivity is the amount of target product substance/total product substance × 100%
According to one embodiment of the application, a method for controllably adjusting the dehydrogenation thermodynamic parameter of the organic alcohol is established, the method can adjust the dehydrogenation thermodynamic parameter of the organic alcohol by using the alkali, and the alkalinity of the alkali is associated with the thermodynamic parameter, namely, the thermodynamic parameter can be controllably adjusted by changing the alkali.
In one embodiment, the organic alcohol dehydrogenation reaction is mainly a reaction in which an organic alcohol reacts with water to generate an organic acid and hydrogen, and is shown in the following reaction formula. The organic alcohol includes monohydric alcohol, dihydric alcohol, polyhydric alcohol, etc., especially methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, butanediol, etc.
RCH2OH+H2O＝RCOOH+H2R1
As one embodiment, the base mainly includes an organic base, an inorganic base, and the like.
In one embodiment, the amount of the base is between 0.1 and 100 times, preferably between 0.5 and 3 times the amount of the organic alcohol used.
In one embodiment, the relationship between basicity and thermodynamics is a linear relationship. The required alkalinity of the base can be calculated according to the linear relationship, so that the base can be controllably selected.
As one of the embodiments, the dehydrogenation reaction is carried out in a solution, preferably in an aqueous solution.
As one embodiment, the dehydrogenation reaction is carried out over a catalyst, wherein the catalyst mainly comprises noble metal and non-noble metal catalysts, such as Pt, Pd, Ru, Rh, Ir, Fe, Co, Ni, Cu and binary or multi-element catalysts composed of Pt, Pd, Ru, Rh, Ir, Fe, Co, Ni and Cu.
As one embodiment, the catalyst may be a homogeneous catalyst or a heterogeneous catalyst.
In one embodiment, the dehydrogenation is carried out at a temperature of between 0 ℃ and 300 ℃, preferably between room temperature and 100 ℃.
In one embodiment, the dehydrogenation time is between 0 hour and 100 hours, preferably between 0 hour and 20 hours.
As one embodiment, the reaction is expected to be applied to the fields of hydrogen storage materials, hydrogen production, decarboxylation and the like.
Example 1 establishment of a Linear relationship for a base-modified methanol-formic acid System
Using methanol and formic acid (the simplest organic alcohols and organic acids), for example, as shown in formula R4, by adding different bases (NaOH, Na)2CO3，NaHCO3，Na3PO4，Na2HPO4) The gibbs free energy change of the reaction under standard conditions (1 atm, 25 ℃) was calculated as shown in table 1 below. pK of the base of choicebThe values were correlated with the gibbs free energy change of the reaction and were found to be in a linear relationship, as shown in figure 1. As can be seen from FIG. 1, the pK isbThe values are linear with respect to the gibbs free energy change of the above reaction. By utilizing the linear relation, the Gibbs free energy change of the reaction can be controllably adjusted, so that the reaction direction of the reaction can be adjusted.
CH3OH+H2O+Base-＝HCOO-+H-Base+2H2R4
Wherein, Base is alkali.
TABLE 1 Gibbs free energy Change of different base-modified methanol-formic acid reactions
Example 2 establishment of the Linear relationship of the base-modified ethylene glycol-oxalic acid System
Using ethylene glycol and oxalic acid as examples, as shown in formula R5, by adding different bases (NaOH, Na)2CO3，NaHCO3，Na3PO4，Na2HPO4，NaH2PO4) The Gibbs free energy change of the reaction under standard conditions (1 atm, 25 ℃) was calculated as shown in Table 2 below. pK of the base of choicebThe values were correlated with the gibbs free energy change of the reaction and found to be a linear relationship, as shown in figure 2. As can be seen from FIG. 2, the pK isbThe values are linear with respect to the gibbs free energy change of the above reaction. By utilizing the linear relation, the Gibbs free energy change of the reaction can be controllably adjusted, so that the reaction direction of the reaction can be adjusted.
HOCH2CH2OH+2H2O+2Base-＝-OOCCOO-+2(H-Base)+4H2R5
Wherein, Base is alkali.
TABLE 2 Gibbs free energy Change of different base-modified ethylene glycol-oxalic acid reactions
EXAMPLE 3 catalytic dehydrogenation of NaOH-modified 1, 4-butanediol with Pt/C catalyst
10 wt.% Pt/C catalyst at 10 vol.% H2Reducing the mixture in an Ar mixed gas at 250 ℃ for 2 hours, and keeping the mixture in a dryer for standby. In a three-necked flask, 4ml of deionized water, 1mmol of 1, 4-butanediol (89.2uL), 97.5mg of 10% Pt/C catalyst, 5mmol of NaOH (200mg) and a molar ratio of Pt to alcohol of 1:20 were measured in this order. One opening of the three-opening flask is provided with condensed water, the set temperature is 10 ℃, and the other two openings are used for argon protective gas. After argon was passed through the flask for 1 hour, the flask was put in an oil bath, and the temperature was raised to 150 ℃ to start refluxing the reaction solution.The reaction solution was taken at different time stages of the reaction (0 hour, 2 hours, 4 hours, 6 hours, 10 hours, 24 hours), and subjected to nuclear magnetic characterization to determine the progress of the reaction, and the results are shown in fig. 3. The argon flow is maintained continuously throughout the reaction.
As can be seen from FIG. 3, 1, 4-butanediol decreased rapidly after the start of the reaction, while the concentration of the intermediate sodium 4-hydroxybutyrate increased rapidly, and after 4 hours, 1, 4-butanediol substantially disappeared and the maximum concentration of sodium 4-hydroxybutyrate was reached. Finally, after 24 hours, the selectivity of the target product succinic acid was 85%, while the intermediate product disappeared, with the selectivity of the by-product propionic acid being 15%.
EXAMPLE 4 Pt/C catalyst catalysis of Na2CO3Modified 1, 4-butanediol dehydrogenation reaction
10 wt.% Pt/C catalyst at 10 vol.% H2Reducing the mixture in an Ar mixed gas at 250 ℃ for 2 hours, and keeping the mixture in a dryer for standby. In a three-necked flask, 4ml of deionized water, 1mmol of 1, 4-butanediol (89.2uL), 97.5mg of 10% Pt/C catalyst and 2mmol of Na were measured in this order2CO3The molar ratio of Pt to alcohol was 1: 20. One opening of the three-opening flask is provided with condensed water, the set temperature is 10 ℃, and the other two openings are used for argon protective gas. And (3) after argon flows for 1 hour, placing the three-neck flask into an oil bath, heating to 150 ℃, starting reflux of reaction liquid, and after the reaction is finally carried out for 48 hours, sampling for nuclear magnetic characterization to determine a reaction product. The argon flow is maintained continuously throughout the reaction.
After analyzing the products, the conversion rate of the 1, 4-butanediol is 100%, wherein the selectivity of the target product succinic acid is 12.6%, and the selectivity of other products, namely, sodium 4-hydroxybutyrate, propionic acid and propanol, is 48.7%, 30.7% and 8.0% in sequence.
EXAMPLE 5 Ru/C catalyst catalysis of NaOH-modified 1, 4-butanediol dehydrogenation
5 wt.% Ru/C catalyst at 10 vol.% H2Reducing the mixture in an Ar mixed gas at 250 ℃ for 2 hours, and keeping the mixture in a dryer for standby. In a three-necked flask, 4ml of deionized water, 1mmol of 1, 4-butanediol (89.2uL), 101mg of 5% Ru/C catalyst and 2mmol of NaOH are weighed in sequence, and the molar ratio of Ru to alcohol is 1: 20. One opening of the three-neck flask is condensed water with set temperatureThe temperature is 10 ℃, and the other two ports are used for argon protective gas. And after argon flows for 1 hour, placing the three-neck flask into an oil bath, heating to 150 ℃, starting reflux of reaction liquid, and after the reaction is finally carried out for 24 hours, sampling for nuclear magnetic characterization to determine a reaction product. The argon flow is maintained continuously throughout the reaction.
After analyzing the products, the conversion rate of the 1, 4-butanediol is 100%, wherein the selectivity of the target product succinic acid is 4.0%, and the selectivity of other products, namely, sodium 4-hydroxybutyrate and propionic acid, is 62.4% and 33.6% in sequence.
EXAMPLE 6 Pd/C catalyst catalysis of NaOH-modified 1, 4-butanediol dehydrogenation reaction
10 wt.% Pd/C catalyst at 10 vol.% H2Reducing the mixture in an Ar mixed gas at 250 ℃ for 2 hours, and keeping the mixture in a dryer for standby. In a three-necked flask, 4ml of deionized water, 1mmol of 1, 4-butanediol (89.2uL), 53.2mg of 10% Pt/C catalyst, 5mmol of NaOH (200mg) and a ratio of Pd to alcohol XX of 1:20 were measured in this order. One opening of the three-opening flask is provided with condensed water, the set temperature is 0 ℃, and the other two openings are provided for argon protective gas. After argon was passed through the flask for 1 hour, the flask was put in an oil bath, and the temperature was raised to 150 ℃ to start refluxing the reaction solution. After the final reaction for 24 hours, a sample was taken for nuclear magnetic characterization to determine the reaction product. The argon flow is maintained continuously throughout the reaction.
After analyzing the products, the conversion rate of the 1, 4-butanediol is 69%, wherein the selectivity of the target product succinic acid is 16.2%, and the selectivity of other products sodium 4-hydroxybutyrate is 83.8%.
Example 7
Succinic acid was prepared in a similar manner to that in example 3 except that the temperature was raised to 80 ℃ and the reaction time was 24 hours, and product analysis was performed under the same conditions as in example 3. After analyzing the product, the conversion rate of 1, 4-butanediol is 69.9%, wherein the selectivity of the target product succinic acid is 2.4%, and the selectivity of other products, namely, sodium 4-hydroxybutyrate, is 97.6%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing organic acid by organic alcohol dehydrogenation reaction is characterized by comprising the following steps:
(1) obtaining the basic pK of the basebCorrelation with thermodynamic parameters of the reaction;
(2) selecting alkali according to the incidence relation and the target thermodynamic parameter to perform target reaction;
wherein the reaction is carried out in the presence of a base.
2. The method for preparing organic acid by organic alcohol dehydrogenation reaction according to claim 1, wherein the thermodynamic parameter is Gibbs free energy change of reaction;
the pK isbAnd the change of the Gibbs free energy is in a linear relation.
3. The method for producing organic acids by dehydrogenation reaction of organic alcohols according to claim 1, wherein the base is selected according to the correlation to obtain/adjust the reaction direction.
4. The method of claim 1, wherein the reacting comprises: reacting the solution containing organic alcohol in the presence of a catalyst and a base to obtain the organic acid.
5. The method of claim 4, wherein the organic alcohol comprises one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, and butylene glycol.
6. The method according to claim 4, wherein the solvent of the solution containing the organic alcohol is water;
the catalyst is at least one of metal, binary compound consisting of metal and multi-element compound consisting of metal;
the molar ratio of the alkali to the organic alcohol is 0.1-100: 1;
the reaction temperature is 0-300 ℃;
the reaction time is not more than 100 hours;
preferably, the molar ratio of the base to the organic alcohol is 0.5-3: 1;
preferably, the temperature of the reaction is from room temperature to 100 ℃;
preferably, the reaction time does not exceed 20 hours.
7. A method for thermodynamically controlling the dehydrogenation reaction of organic alcohol, which is characterized by comprising the following steps:
(a) obtaining the basic pK of the basebCorrelation with thermodynamic parameters of the reaction;
(b) and selecting different alkalis according to the incidence relation to obtain different reaction thermodynamic parameters, namely, the organic alcohol dehydrogenation reaction thermodynamic parameters can be controlled and adjusted.
8. The method of claim 7, wherein the thermodynamic parameter is gibbs free energy change of reaction;
the pK isbAnd the change of the Gibbs free energy is in a linear relation.
9. The method for thermodynamically controlled adjustment of organic alcohol dehydrogenation reaction thermodynamics according to claim 7, wherein the organic alcohol dehydrogenation reaction comprises the method for producing organic acid by organic alcohol dehydrogenation reaction according to any one of claims 1 to 6.
10. The method for preparing organic acid by organic alcohol dehydrogenation reaction according to any one of claims 1 to 6 and/or the method for thermodynamically controlling regulation of organic alcohol dehydrogenation reaction according to any one of claims 7 to 9 is applied to the fields of hydrogen storage materials, hydrogen production and decarboxylation.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292936A (en) * | 1993-04-12 | 1994-03-08 | Monsanto Company | Process to prepare amino carboxylic acid salts |
| CN1156419A (en) * | 1994-07-01 | 1997-08-06 | 孟山都公司 | Process for preparing carboxylic acid salts and catalysts useful in such process |
| CN1318047A (en) * | 1998-09-14 | 2001-10-17 | 道农业科学公司 | Process for preparing carboxylic acids |
| CN102530858A (en) * | 2011-04-29 | 2012-07-04 | 中国科学技术大学 | Method for preparing hydrogen by alcohol |
| CN106810436A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation glycerine prepares lactic acid |
-
2018
- 2018-11-08 CN CN201811325516.8A patent/CN111153788A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292936A (en) * | 1993-04-12 | 1994-03-08 | Monsanto Company | Process to prepare amino carboxylic acid salts |
| CN1156419A (en) * | 1994-07-01 | 1997-08-06 | 孟山都公司 | Process for preparing carboxylic acid salts and catalysts useful in such process |
| CN1318047A (en) * | 1998-09-14 | 2001-10-17 | 道农业科学公司 | Process for preparing carboxylic acids |
| CN102530858A (en) * | 2011-04-29 | 2012-07-04 | 中国科学技术大学 | Method for preparing hydrogen by alcohol |
| CN106810436A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation glycerine prepares lactic acid |
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Application publication date: 20200515 |