阅读说明：本技术 一种双金属催化剂催化1,3-二羟基丙酮协同制备甲酸和乙醇酸的方法 (Method for preparing formic acid and glycolic acid by catalyzing 1,3-dihydroxyacetone with bimetallic catalyst ) 是由 王金岭 杨雪晶 汪华林 李剑平 刘洪来 施王庆 于 2021-01-18 设计创作，主要内容包括：本发明公开了一种双金属催化剂催化1,3-二羟基丙酮协同制备甲酸和乙醇酸的方法,属于化学品合成与生物质多相催化转化技术领域。具体步骤为：将双金属催化剂、1,3-二羟基丙酮、溶剂置于反应容器中,最后加入氧化剂,密闭反应容器开始反应,制得所述的甲酸和乙醇酸化合物,初始1.3-二羟基丙酮的浓度不低于0.1mol/L,初始的反应pH为0.5-9,反应温度为20-100℃,反应时间为1-72小时,可以实现甲酸和乙醇酸的高效协同生产。甲酸的产率为91.06％,乙醇酸的产率为82.46％,碳原子利用率为85.33％,具有极高的碳原子利用率。本方法反应条件温和、无碱,催化剂廉价、制备简便,具有广阔的应用前景。(The invention discloses a method for preparing formic acid and glycollic acid by catalyzing 1,3-dihydroxyacetone to synergistically react with a bimetallic catalyst, and belongs to the technical field of chemical synthesis and biomass heterogeneous catalytic conversion. The method comprises the following specific steps: putting a bimetallic catalyst, 1,3-dihydroxyacetone and a solvent into a reaction container, finally adding an oxidant, closing the reaction container to start reaction to prepare the formic acid and glycollic acid compound, wherein the concentration of the initial 1.3-dihydroxyacetone is not lower than 0.1mol/L, the initial reaction pH is 0.5-9, the reaction temperature is 20-100 ℃, and the reaction time is 1-72 hours, so that the high-efficiency synergistic production of the formic acid and the glycollic acid can be realized. The yield of formic acid was 91.06%, the yield of glycolic acid was 82.46%, the carbon atom utilization rate was 85.33%, and the carbon atom utilization rate was extremely high. The method has the advantages of mild reaction conditions, no alkali, cheap catalyst, simple preparation and wide application prospect.)

1. A method for preparing formic acid and glycolic acid by catalyzing 1,3-dihydroxyacetone synergistically by a bimetallic catalyst is characterized in that the bimetallic catalyst, 1,3-dihydroxyacetone and a solvent are placed in a reaction container, an oxidant is added, the reaction container is closed to start reaction, and the formic acid and the glycolic acid are prepared; the concentration of the initial 1,3-dihydroxyacetone is not less than 0.1mol/L, the pH of the reaction system in the initial reaction is 0.5-7, the reaction temperature is 20-100 ℃, and the reaction time is 1-72 hours, wherein: the mass ratio of the 1,3-dihydroxyacetone to the catalyst is (200:1) - (1:1), and the molar ratio of the 1,3-dihydroxyacetone to the oxidizing agent is (1:1) - (1: 10).

2. The process for preparing formic and glycolic acid according to claim 1, wherein said oxidizing agent is one or more selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, dibenzoyl peroxide, methyl ethyl ketone peroxide, peracetic acid, lithium peroxide, sodium peroxide, magnesium peroxide, calcium peroxide, nickel peroxide.

3. The process for the preparation of formic and glycolic acid according to claim 1, characterized in that said solvent is one or more of water, benzene, toluene, acetonitrile, petroleum ether.

4. The process for the preparation of formic and glycolic acid according to claim 1, characterized in that said bimetallic catalyst is prepared from M1: namely a simple substance of a metal component X1 or one of insoluble sulfide, phosphate, carbonate, oxide, hydroxide and oxyhydroxide of X1, and M2: the other metal component is composed of a simple substance of X2 or one of insoluble sulfide, phosphate, carbonate, oxide, hydroxide and oxyhydroxide of X2; the molar ratio of the metal elements of X1 and X2 in the bimetallic component is 2:1-2000:1, the metal in X1 is selected from titanium, vanadium, iron, molybdenum and tungsten, and the metal in X2 is selected from manganese, cobalt, iridium, palladium and platinum.

5. The method for preparing formic acid and glycolic acid according to claim 1, 2 or 3, wherein said oxidizing agent is added to said reaction vessel, wherein said liquid oxidizing agent is first prepared in a concentration ranging from 1mol/L to the maximum allowable concentration in said solvent and is added to said reaction vessel at a rate ranging from 0.1mL/min to 10 mL/min; grinding the solid oxidant to powder of more than 200 meshes and adding the powder.

6. The process for the preparation of formic and glycolic acid according to claims 1 or 4, characterized in that said bimetallic catalyst is prepared by mixing M1 directly with M2 or by loading M2 on M1, in particular by the following steps:

(1) prepared by direct mixing of M1 with M2: uniformly mixing M1 and M2 in a solvent-free mechanical mixing mode to obtain a bimetallic catalyst;

(2) prepared by loading M2 onto M1: dissolving soluble salt of X2 as precursor of M2 in water or ethanol, adding M1, stirring the mixture at 20-100 deg.C under the operation condition of atmospheric pressure or less until the solvent is completely volatilized, and calcining at 200-1000 deg.C for 2-24 hr under the atmosphere of air, nitrogen, argon or hydrogen sulfide to obtain the bimetallic catalyst.

Technical Field

The invention relates to a method for synergistically preparing formic acid and glycolic acid by catalyzing 1,3-dihydroxyacetone through a bimetallic catalyst, and particularly relates to a method for synergistically preparing formic acid and glycolic acid by efficiently catalyzing selective C-C bond cleavage of 1,3-dihydroxyacetone through a bimetallic catalyst. Belongs to the technical field of chemical synthesis and biomass heterogeneous catalytic conversion.

Background

Formic acid, also known as formic acid, of the chemical formula HCOOH, is a typical C1 organic acid and has wide applications in chemistry, agriculture, leather industry, pharmaceutical industry and rubber industry. Because of the characteristics of no toxicity and easy biodegradation, the formic acid can replace some inorganic acids in a plurality of chemical reaction processes. In addition, formic acid is also considered to be a promising material for hydrogen and carbon monoxide storage, based on its easy to control dehydrogenation, dehydration process. In recent years, the global demand for formic acid has been increasing year by year due to the above factors, and the price has also been increasing year by year. The conventional formic acid production mainly adopts a carbon monoxide route, namely, carbon monoxide is firstly produced by taking natural gas or coal as a raw material, the carbon monoxide reacts with methanol under the conditions of high pressure (about 4MPa) and strong base (sodium methoxide) to generate methyl formate, and then the methyl formate is hydrolyzed to prepare formic acid. The main disadvantage of the method is that the alkali metal methoxide catalyst has strong corrosivity and is very sensitive to moisture and carbon dioxide, and sodium formate or sodium carbonate is easily formed by reaction with impurities in materials in actual use to cause blockage of the device. In addition, carbon monoxide is toxic and it is produced using non-renewable fossil feedstocks, and these disadvantages have limited further development of the carbon monoxide route. In addition to the carbon monoxide route, there are also methanol and methane as raw materials and cellulose and lignin as biomass raw materials, but most of these routes have the disadvantages of expensive catalyst, severe reaction conditions, low product yield and selectivity, etc., and currently, they are still mainly in the laboratory stage, and further industrial application is difficult.

Glycolic acid, of the formula HOCH2COOH, is a typical C2 organic acid and has wide applications in the textile industry, food processing and the production of personal skin care products. In addition, it is also widely used as an important intermediate for producing polyglycolic acid (PGA) material having good biodegradability. The basic hydrolysis method of chloromandelic acid is a traditional method for producing glycolic acid, the core reaction of the method is to use chloroacetic acid as a carbonyl methylation reagent in a strong alkaline environment, substitute chlorine atoms on chloroacetic acid through nucleophilic attack of hydroxide ions, and prepare glycolic acid through steps of acidification, filtration extraction and the like. In addition, a cyaniding method and a formaldehyde carbonylation method are also main methods for producing glycolic acid at present, but the former method needs to use highly toxic cyanide as a raw material, so that the safety problem in operation is increased; the latter requires operating conditions at high pressure (30-90MPa), increasing the construction and maintenance costs of the plant.

From the above description, the existing methods for producing formic acid and glycolic acid have obvious defects, and the development of a novel method for producing formic acid and glycolic acid, which is low in cost and environmentally friendly, is a problem to be solved urgently in academia and industry.

Glycerol (glycerol) is the simplest triol, a low value-added by-product in biodiesel production. In recent years, with the gradual expansion of the global biodiesel industry scale, the yield of glycerol is increasing, which causes the glycerol production to be excessive in the world, and the price is sharply reduced. Therefore, the production of high value-added chemicals from glycerol has a very promising economic prospect and has received more and more attention in recent years. In current research, the process route for converting glycerol to certain C3 chemicals, such as 1,3-dihydroxyacetone, in low cost and high yield has become more established. In the further conversion of 1,3-dihydroxyacetone as a raw material, the current research mainly focuses on the direction of preparing lactic acid, methyl lactate and ethyl lactate by catalyzing dehydration and rearrangement of the raw material by using a solid acid catalyst. However, since 1,3-dihydroxyacetone contains 3 carbon atoms, it can be considered that 1,3-dihydroxyacetone as a raw material realizes the synergistic production of glycolic acid (containing 2 carbon atoms) and formic acid (containing 1 carbon atom) through the selective cleavage of C-C bonds, and the route has high carbon atom utilization rate and is a feasible and industrially valuable route.

Subject set (NEUMANN G.,Nonenzymatic reaction of dihydroxyacetone with hydrogen peroxide enhanced via a fenton reaction[J]The Annals of the New York Academy of Sciences,2005,1048(1): 461-465) and the Jung topic group (Pullanikat P., Jung S., Yoo K., Jung K.Oxidate degradation of reducing carbohydrates to ammonium formaldehyde with H₂O₂ and NH₄OH[J]Tetrahedron letters,2010,51(47):6192-₂O₂The method for preparing formic acid and glycolic acid by oxidizing 1,3-dihydroxyacetone with an oxidizing agent needs to be carried out under alkaline conditions, the obtained oxidation products are formate and glycolate firstly, and formic acid and glycolic acid need to be obtained through acidification, which increases the separation and purification cost. CN 108484383B discloses a method for preparing a compound with 1,3-A process for producing glycolic acid from dihydroxyacetone as a starting material by using a composite catalyst and an oxidizing agent under alkali-free conditions, which process, however, does not achieve the synergistic production of glycolic acid and formic acid. Shi task force developed the Cu/Al₂O₃As catalyst, with H₂O₂As an oxidant, H is activated by Fenton-like reaction under alkali-free condition₂O₂Method for the selective cleavage of the C-C bond of 1,3-Dihydroxyacetone with the formation of highly oxidizing hydroxyl radicals (HO.) (Dai X., Adoit S., Rabeah J., Kreyenschute C., Bruckner A., Wang H., Shi F., Sustainable Co-Synthesis of Glyconic Acid, formalides and formats from 1, 3-Dihydroxyracetone by a Cu/Al₂O₃ Catalyst with a Single Active Sites[J]Angewandte Chemie International Edition,2019,58(16):5251-5255.) that can achieve the production of glycolic acid but due to the activation of H by a mono-active metal Cu catalyst₂O₂The ability of generating HO & is too strong, most formic acid can be deeply oxidized into carbon dioxide and water, and the utilization rate of carbon atoms of the system is greatly reduced.

As is clear from the above description, the conventional selective C — C bond cleavage system using 1,3-dihydroxyacetone as a raw material can only achieve efficient production of glycolic acid, but cannot achieve efficient synergistic production of glycolic acid and formic acid, which significantly reduces the carbon atom utilization rate of this reaction. Heretofore, in the art, a method capable of synergistically producing formic acid and glycolic acid from 1,3-dihydroxyacetone as a raw material under mild and alkali-free conditions has not been developed, and therefore, there is a strong need in the art for a method capable of synergistically producing formic acid and glycolic acid from 1,3-dihydroxyacetone as a raw material under mild and alkali-free conditions.

Disclosure of Invention

The invention aims to provide a method for preparing formic acid and glycolic acid by efficiently catalyzing selective C-C bond cutting of 1,3-dihydroxyacetone through a novel bimetallic catalyst, which can realize efficient catalytic oxidation of 1,3-dihydroxyacetone under mild and alkali-free conditions.

The invention is realized by the following technical scheme:

a method for preparing formic acid and glycolic acid by catalyzing 1,3-dihydroxyacetone synergistically by a bimetallic catalyst is characterized in that the bimetallic catalyst, the 1,3-dihydroxyacetone and a solvent are placed in a reaction container, finally an oxidant is added, the reaction container is closed to start reaction, the formic acid and the glycolic acid are prepared, the concentration of the initial 1.3-dihydroxyacetone is not lower than 0.1mol/L, the pH of a reaction system in the initial reaction is 0.5-7, the reaction temperature is 20-100 ℃, and the reaction time is 1-72 hours, wherein: the mass ratio of the 1,3-dihydroxyacetone to the catalyst is (200:1) - (1:1), and the molar ratio of the 1,3-dihydroxyacetone to the oxidizing agent is (1:1) - (1: 10).

The oxidant is one or more of hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide, methyl ethyl ketone peroxide, peracetic acid, lithium peroxide, sodium peroxide, magnesium peroxide, calcium peroxide and nickel peroxide.

The solvent is one or more of water, benzene, toluene, acetonitrile and petroleum ether.

The bimetallic catalyst is compounded by M1, namely one of simple substance of a metal component X1 or insoluble sulfide, phosphate, carbonate, oxide, hydroxide and oxyhydroxide of X1, and M2, namely the simple substance of another metal component X2 or one of insoluble sulfide, phosphate, carbonate, oxide, hydroxide and oxyhydroxide of X2; the molar ratio of the metal elements of X1 and X2 in the bimetallic component is 2:1-2000:1, the metal in X1 is selected from titanium, vanadium, iron, molybdenum and tungsten, and the metal in X2 is selected from manganese, cobalt, iridium, palladium and platinum.

When the oxidant is added into the reaction vessel, the liquid oxidant is prepared into a solution with the concentration range of 1 mol/L-the maximum allowable concentration under the solvent in advance, and the solution is added into the reaction vessel at the speed of 0.1mL/min-10 mL/min; grinding the solid oxidant to powder of more than 200 meshes and adding the powder.

The bimetallic catalyst can be prepared by directly mixing M1 and M2 or loading M2 on M1.

The bimetallic catalyst is prepared by directly mixing M1 with M2: and (3) uniformly mixing the M1 and the M2 in a solvent-free mechanical mixing mode to obtain the bimetallic catalyst.

The bimetallic catalyst was prepared by loading M2 onto M1: dissolving a soluble salt of metal X2 as a precursor of M2 in water or ethanol, adding M1, stirring the mixture at the temperature of 20-100 ℃ under the operation condition that the temperature is less than or equal to the atmospheric pressure until the solvent water or ethanol is completely volatilized, and roasting at the temperature of 200-1000 ℃ for 2-24 hours under the atmosphere of air, nitrogen, argon or hydrogen sulfide to obtain the bimetallic catalyst.

Compared with the prior art, the invention has the advantages that:

1. the invention takes 1,3-dihydroxyacetone as a raw material, utilizes the synergistic catalytic action of bimetallic species to regulate and control the oxidation capacity of the system, can realize the high-yield synergistic production of formic acid and glycollic acid, inhibits the generation of deep oxidation products of carbon dioxide, and has high carbon atom utilization rate in the whole system.

2. The bimetallic catalyst used in the invention has the advantages of simple preparation method, low price, no toxicity, no harm, and convenient separation and reutilization.

3. The method is operated under the alkali-free condition, the reaction condition is mild, and the problems of difficult product separation under the alkali condition, equipment cost, safety and the like caused by high temperature and high pressure are solved.

Drawings

FIG. 1 is a reaction scheme for the synergistic preparation of formic acid and glycolic acid by selective C-C bond cleavage of 1,3 dihydroxyacetone in examples 1-5.

FIG. 2 shows the conversion of 1,3-dihydroxyacetone, the yield of formic acid, the yield of glycolic acid and the utilization of carbon atoms for examples 1 to 5.

FIG. 3 is a graph showing the conversion of 1,3-dihydroxyacetone, the yield of formic acid, the yield of glycolic acid and the utilization of carbon atoms, corresponding to example 6.

Detailed Description

The bimetallic catalyst is applied to the process of catalyzing selective C-C bond cutting of 1,3-dihydroxyacetone to synergistically prepare formic acid and glycolic acid. The reaction process is as follows: the catalytic performance evaluation of the bimetallic catalyst was carried out in a stainless steel reactor with a teflon liner. Adding a bimetallic catalyst, 1,3-dihydroxyacetone, a solvent and an oxidant in sequence, sealing the reaction kettle, setting the reaction temperature (20-100 ℃), heating to start reaction, cooling to stop reaction after reacting for a certain time (1-72 hours), transferring the reacted liquid to a volumetric flask for constant volume, filtering the reaction liquid by a filter after constant volume to remove the catalyst, obtaining the reaction liquid which is a mixed solution of the 1,3-dihydroxyacetone and the product, and determining the yield of formic acid and glycolic acid by using liquid chromatography.

1,3-dihydroxyacetone conversion (%) - (amount of 1,3-dihydroxyacetone material before reaction-amount of 1,3-dihydroxyacetone material after reaction)/amount of 1,3-dihydroxyacetone material before reaction × 100%.

Formic acid yield (%) — amount of formic acid substance after reaction/amount of 1,3-dihydroxyacetone substance before reaction × 100%.

Glycolic acid yield (%) — amount of glycolic acid substance after reaction/amount of 1,3-dihydroxyacetone substance before reaction × 100%.

The total carbon atom utilization rate (%) (amount of formic acid substance after reaction × 1+ amount of glycolic acid substance after reaction × 2)/(amount of 1,3-dihydroxyacetone substance before reaction × 3) × 100%.

The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.

Preparation of example 1

This example is the preparation of a catalyst.

Using alpha-FeOOH (from Sigma Aldrich) and beta-MnO₂Weighing 500mg of alpha-FeOOH as components M1 and M2 of the catalyst (from Michelin corporation), and weighing beta-MnO with corresponding mass according to the molar ratio of Fe to Mn of 100/1₂The two components were carefully ground using an agate mortar for 10 minutes to mix well to give the catalyst, designated catalyst a.

Preparation of example 2

This example is the preparation of a catalyst.

The overall scheme for this example is the same as for preparative example 1 except that the molar ratio of Fe to Mn was changed to 10/1 to give a catalyst designated catalyst B.

Preparation of example 3

This example is the preparation of a catalyst.

The overall scheme for this example is the same as that for preparative example 1 except that the M2 component was changed to elemental iridium (Ir) powder (available from Afahisaka) having a molar ratio of Fe to Ir of 100/1 to give a catalyst designated as catalyst C.

Preparation of example 4

This example is the preparation of a catalyst.

Weighing 500mg of alpha-FeOOH, mixing the alpha-FeOOH with 10mL of deionized water, weighing manganese nitrate tetrahydrate (purchased from Michelin company) with corresponding mass according to the molar ratio of Fe to Mn of 100/1, adding the manganese nitrate tetrahydrate into the mixed solution, performing rotary evaporation on the mixed solution at 60 ℃ until the deionized water is completely evaporated, and roasting the obtained solid at 800 ℃ for 6 hours in an air atmosphere to obtain a catalyst, which is marked as catalyst D.

Example 1

6mg of catalyst A was weighed into a 10mL stainless steel reaction vessel with a Teflon liner, after which 180mg (2mmol) of 1,3 dihydroxyacetone (available from Michael corporation) and 0.16mL deionized water were added in sequence, followed by 0.24mL (4mmol) of H₂O₂(50 mass% aqueous solution available from Michael corporation) was pumped into the reaction vessel at a rate of 0.1mL/min by a peristaltic pump. Then the reaction kettle is closed, the reaction is stirred at 25 ℃ for 24 hours, after the reaction is finished, the reaction solution is transferred to a volumetric flask and is subjected to volume constant to 10mL by using deionized water, after the volume constant, the reaction solution is filtered by using a filter to remove the catalyst, the obtained reaction solution is a mixed solution of 1,3-dihydroxyacetone and the product, the yield of formic acid and glycolic acid is determined by liquid chromatography, and the conversion rate of the 1,3-dihydroxyacetone is 91.37%, the yield of the formic acid is 91.06%, the yield of the glycolic acid is 82.46% and the total utilization rate of carbon atoms is 85.33%.

Example 2

The overall procedure of this example was the same as example 1 except that catalyst a was changed to catalyst C. The conversion of 1,3-dihydroxyacetone was found to be 83.58%, the yield of formic acid was 76.06%, the yield of glycolic acid was 80.21%, and the total carbon atom utilization was 78.83%.

Example 3

The overall procedure of this example was the same as example 1 except that catalyst a was changed to catalyst D. The conversion of 1,3-dihydroxyacetone was found to be 80.21%, the yield of formic acid was 68.21%, the yield of glycolic acid was 77.46%, and the total carbon atom utilization was 74.38%.

Example 4

The overall procedure of this example was the same as example 1 except that catalyst a was changed to catalyst E. The conversion of 1,3-dihydroxyacetone was found to be 88.77%, the yield of formic acid was found to be 89.97%, the yield of glycolic acid was found to be 80.19%, and the total carbon atom utilization was found to be 83.45%.

Example 5

This example is a recycle of the catalyst.

Catalyst B was used as the evaluation material. The overall flow of this example was the same as that of example 1, after the reaction was completed, the catalyst was filtered, washed with deionized water 3 times, dried under vacuum at 60 ℃ and reused 3 times under the above conditions, and the measured conversion of 1.3-dihydroxyacetone was 86.51%, 84.22%, 83.17%, the yield of formic acid was 83.21%, 80.69%, 81.33%, the yield of glycolic acid was 78.96%, 80.44%, 76.11%, and the total carbon utilization was 80.38%, 80.52%, 77.85%, respectively.