CN115745776A - Method for preparing formic acid by catalyzing oxygen to oxidize biomass carbohydrate - Google Patents
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Abstract
The invention relates to a method for preparing formic acid by catalytic oxygen oxidation of carbohydrates through a mode of catalyst reduction and reoxidation separation. The method uses Keggin type vanadium-containing heteropoly acid H 8 PV 5 Mo 7 O 40 As a catalyst, a carbohydrate is first selectively oxidized in water to produce ultra-high yields of formic acid, while the catalyst is reduced. Then, the catalyst in the reduction state is regenerated by taking oxygen as an oxidant for the next round of carbohydrate oxidation. Compared with the traditional method for preparing formic acid, the method takes biomass carbohydrate as a raw material, avoids environmental pollution and has sustainability; the reaction condition is mild, and the yield of the formic acid is high. Selection of H 8 PV 5 Mo 7 O 40 The catalyst has high oxidation activity, good selectivity and re-oxidation activityThe performance is very high. Compared with the common method for preparing the formic acid by catalyzing the oxygen to oxidize the carbohydrate, the method can obviously improve the selectivity of the formic acid and improve the utilization rate of the carbon atom of the carbohydrate.
Description
Technical Field
The invention relates to a method for preparing formic acid by catalytically oxidizing biomass, in particular to a method for preparing formic acid by catalytically oxidizing biomass carbohydrate with oxygen in a separated mode of reduction and reoxidation of a catalyst.
Technical Field
With the rapid development of global economy and the increasing population, the problems of resource shortage, greenhouse effect, environmental pollution and the like increasingly attract people's attention, and the replacement of fossil resources by renewable resources becomes a research hotspot of sustainable development. While renewable energy sources such as hydroelectric, wind, solar, etc. can relieve the pressure of fossil fuels, they do not address the production of chemicals. Biomass, as the only renewable carbon source present in large quantities on earth, offers the possibility of a sustainable supply of chemicals and transportation fuels.
Formic acid is an important chemical raw material, and is widely applied to the fields of textile, tanning, medicine, agriculture, chemical industry and the like due to the unique property of the formic acid. In the aspect of biomass conversion, formic acid can replace inorganic acid to be used as an acid catalyst, so that equipment corrosion and the influence on subsequent reaction are avoided; formic acid can also serve as a hydrogen donor to provide in situ hydrogen during hydrogenolysis of biomass. In recent years, formic acid plays an increasingly important role in the field of energy, and has a wide application prospect in fuel cells and hydrogen production. The formic acid fuel cell has the advantages of high energy density, low cross flux, environmental protection, nonflammability and the like. And as a hydrogen production raw material, formic acid has high hydrogen capacity (53.4 g/L) and good transportation and storage safety. At present, the industrial preparation methods of formic acid mainly comprise a sodium formate method, a methyl formate hydrolysis method, a formamide method and the like, but raw materials of the methods are all derived from fossil fuels. Although the traditional methods can produce formic acid in large quantities, the factors of serious pollution, non-renewable production raw materials and the like in the production process restrict the high-efficiency sustainable production of formic acid. Based on the requirements of sustainable development and green chemical industry, a novel formic acid production process with high efficiency, low pollution and good sustainability is urgently developed.
Biomass-based carbohydrates are a widely distributed, renewable source of carbon. The lignocellulose can be obtained from plant residues and wastes in the fields of agriculture, forestry, industry and the like, and has rich content and low price. Lignocellulose contains 50-90 wt% carbohydrates (including cellulose and hemicellulose), and has high oxygen content, and is suitable for converting oxygen-containing chemicals such as formic acid.
Currently, there are some reports of using carbohydrates to prepare formic acid, for example, chinese patent (application No. 201080019836.6) discloses a production method of formic acid, which involves producing formic acid by hydrolyzing carbohydrate-containing materials in the presence of an inorganic acid, but the yield of formic acid (carbon yield, the same applies hereinafter) is low and a large amount of inorganic acid needs to be consumed. Chinese patent application No. 201110099183.3 discloses a method for preparing acetone and calcium formate from biomass waste, wherein biomass is converted into formic acid and acetic acid under severe reaction conditions, but the yield of the product formic acid is low and the reaction energy consumption is high. Chinese patent application No. 201180054759.2 discloses a method for producing formic acid by catalytic oxidation of carbohydrate at low temperature, which obtains formic acid under mild conditions, but has a problem that yield of formic acid is limited due to generation of carbon dioxide by peroxidation.
Journal articles have also been reported for the catalytic oxidation of carbohydrates to formic acid. Jin et al (Jin F, enomoto H.Rapid and high selective conversion of biological in products in thermal conversions: chemistry of acid/base-analyzed and oxidation reactions. Engineer&Environmental Science,2011,4 (2): 382-397) uses inorganic base such as NaOH as catalyst and H 2 O 2 As an oxidizing agent, the cellulose was oxidized at high temperature of 250 ℃ to produce formic acid (sodium salt) in up to 75% yield. However, the method has high operation temperature and large alkali consumption in reaction, and is limited in industrial application. Researchers have also proposed catalytic oxidation of carbohydrates in acidic aqueous solutions to formic acid.
Etc. (
R,Taccardi N,
A,Wasserscheid P.Selective catalytic conversion of biobased carbohydrates to formic acid using molecular oxygen.Green Chemistry,2011,13(10):2759-2763) With heteropoly acid H 5 PV 2 Mo 10 O 40 As a catalyst, catalyzing glucose at 80 ℃ and 3MPa O 2 Conversion to yield 49% formic acid. Albert et al (Albert J, laders D,
a, guldi D M, waters chemical P.Spectroscopic and electrochemical conversion of hydrolytic acids for the selective biochemical oxidation of acids for the green Chemistry,2014, 16-226-237) found that heteropolyacids exhibit better catalytic properties with increasing degree of vanadium substitution, where H 8 PV 5 Mo 7 O 40 The best performing, glucose was converted to formic acid in 57.3% yield. Li et al (Li J, ding D J, deng L, guo Q X, fu Y. Catalytic air oxidation of biological-derived carbohydrates to chemical acid. ChemSus chem,2012,5 (7): 1313-1318) by H 5 PV 2 Mo 10 O 40 The yield of formic acid is increased from 3% to 30% after the cellulose is catalytically oxidized and a small amount of inorganic acid is added. Lu et al (Lu T, niu M G, hou Y C, wu W Z, ren S H, yang F. Catalytic oxidation of cellulose to form acid in H 5 PV 2 Mo 10 O 40 +H 2 SO 4 Green Chemistry,2016,18 (17): 4725-4732) is reported in H 5 PV 2 Mo 10 O 40 -H 2 SO 4 The system catalyzes oxygen to oxidize cellulose to prepare formic acid, and the yield of the formic acid reaches 61 percent. The method for preparing the formic acid by oxidizing the carbohydrate in the acidic catalytic system can obtain the formic acid under a milder condition, but the method still has the problem of low formic acid selectivity, the yield of the formic acid reported at present is not more than 70 percent, and more than 30 percent of organic carbon in the raw material is converted into a byproduct CO 2 . Thus, not only the utilization rate of carbon atoms of raw materials is not high, but also a large amount of CO is generated 2 Not facilitating the achievement of the dual carbon goal as quickly as possible. To inhibit CO 2 The formation of formic acid, the yield of formic acid was increased, and the solvent composition (Lu, T.; hou Y.C.; wu, W.Z.; niu, M.G.; ren, S.H.; lin Z.Q.; ramani, V.K.catalytic oxidation of biomas) was varied by the researcherss to oxygenated chemicals with exceptionally high yields using H 5 PV 2 Mo 10 O 40 Fuel 2018,216, 572-578), also investigators added dimethyl sulfoxide to a catalytic oxidation system (Guo, y.j.; li, s.j.; sun, y.l.; wang, l.; zhang, w.m.; zhang, p.; lan, y.; li, Y.practical DMSO-catalyzed selective hydrogenation-oxidation to carboxylic acid bound. Green chem.2021,23, 7041-7052), but these processes consume additional organic solvents or additives and increase the difficulty of subsequent product purification. Therefore, there is a need to find a novel method for carbohydrate oxidation to suppress CO by-product without introducing organic CO-agent 2 The yield of formic acid is improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing formic acid by circularly catalyzing and oxidizing carbohydrate with Keggin type vanadium-containing heteropoly acid, wherein the reduction and reoxidation of a heteropoly acid catalyst are separated to realize the high-selectivity preparation of formic acid by catalyzing and oxidizing carbohydrate. The method takes biomass carbohydrate as a raw material, water as a solvent and Keggin type vanadium-containing heteropoly acid H 3+n PV n Mo 12 -nO 40 (HPA-n, n = 2-6) is a catalyst, and oxygen is an oxidant. The carbohydrate is first oxidized with high selectivity to formic acid by using heteropolyacid in oxidation state (HPA-n), the heteropolyacid is reduced, and then the reduced heteropolyacid (HPA-n) is oxidized with oxygen red ) Reoxidize to HPA-n for the next round of carbohydrate oxidation (as shown in FIG. 1). The method for catalyzing oxygen to oxidize the carbohydrate by separating the reduction and reoxidation of the catalyst is an efficient and reproducible formic acid production method, can obviously improve the yield of the formic acid without adding an organic auxiliary agent, improves the atom utilization rate of biomass, and provides a new technology for industrial application of preparing the formic acid by high-selectivity oxidation of the carbohydrate.
The invention provides a method for preparing formic acid by circulating catalytic oxidation of Keggin type vanadium-containing heteropoly acid, which comprises 3 steps: (a) Oxidation of carbohydrates to HPA-n in aqueous solventsFormic acid; (b) Extracting with extractant to obtain formic acid product rich in HPA-n red An aqueous solution of (a); (c) Providing oxygen or air atmosphere, adding HPA-n red Reoxidize to HPA-n for the next round of carbohydrate oxidation.
In the step (a), the carbohydrate is selected from one of glucose, arabinose, erythrose, glyceraldehyde, glycolaldehyde, cellulose and xylan.
In the step (a) of the preparation method, the addition amount of the carbohydrate is 0.18wt% -3.6 wt% of the mass fraction based on the mass of the solvent.
In step (a) of the above production method, the HPA-n is one selected from HPA-2, HPA-3, HPA-4, HPA-5 and HPA-6, preferably HPA-5.
In step (a) of the above production method, the molar ratio of the V atom in HPA-n to the C atom in the carbohydrate is 1 to 4, preferably 3 to 4, based on the number of C atoms in the carbohydrate.
In the step (a) of the preparation method, the temperature of the carbohydrate oxidation reaction is 120-180 ℃.
In the step (a) of the preparation method, the time of the carbohydrate oxidation reaction is 1min to 60min, preferably 10min to 60min.
In the step (b), the extractant is diethyl ether or ethyl acetate, the volume ratio of the extractant to the reaction solution is 10, and the extraction is carried out for 3 to 7 times.
In step (c) of the preparation method, the oxidant is pure oxygen or air, and the initial partial pressure of the oxygen is 0.5 to 2.5MPa, preferably 1.5 to 2.5MPa.
In step (c) of the above production method, HPA-n red The reaction temperature for reoxidation is 30 to 70 ℃, preferably 50 to 70 ℃.
In step (c) of the above production method, HPA-n red The reaction time for reoxidation was 10min.
The principle of the method for preparing the formic acid by oxidizing the carbohydrate with high selectivity of the invention is as follows: insoluble carbohydrates (such as cellulose) are hydrolyzed under the acidic action of catalyst to obtainSoluble carbohydrate, which generates high-selectivity C-C bond breaking to generate formic acid under the oxidation of an oxidation state catalyst HPA-n. When HPA-n oxidizes carbohydrates, oxygen atoms are transferred from the catalyst to the oxidation products of the carbohydrates, and pentavalent vanadium in the catalyst is reduced to tetravalent vanadium with concomitant electron transfer. Reduced catalyst HPA-n red In step (c), reoxidized by oxygen to be recovered as HPA-n, oxygen atoms are transferred from the oxygen to the catalyst, and tetravalent vanadium in the catalyst is oxidized to pentavalent vanadium with electron transfer. Wherein the reoxidation process of the catalyst generates hydroxyl free radicals which have high oxidation-reduction potential and low selectivity to formic acid during oxidation, and the action of carbohydrates can lead to peroxidation to generate CO 2 . This is the generation of a large amount of CO when carbohydrates are subjected to catalytic oxygen oxidation in an aqueous HPA-n solution 2 The cause of the by-products. If the oxidation of the carbohydrate (i.e., the reduction of the catalyst) and the reoxidation of the catalyst are performed separately, the contact of hydroxyl radicals with the carbohydrate can be avoided, thereby greatly reducing peroxidation and improving the selectivity of formic acid.
Compared with the method for preparing formic acid by catalyzing oxygen to oxidize carbohydrate in the literature, the method has the following advantages: (1) Under the condition of not adding any organic auxiliary agent, the selectivity of the formic acid product is greatly improved, and the by-product CO is inhibited 2 The method has high atom utilization rate; (2) Organic auxiliary agents are not consumed, the solvent is water, and the safety is high; (3) The product is formic acid solution without further hydrolysis or acidification. (4) The heteropoly acid has high concentration, can provide strong acidity for the hydrolysis of insoluble carbohydrate, and does not need additional acid.
Compared with the method for industrially preparing formic acid, the method has the following advantages: (1) The method takes cheap and abundant biomass-based carbohydrate as a raw material, not only can reduce the cost, but also avoids the problem of environmental pollution caused by using fossil energy, and is established on the basis of renewable biomass resources, so that the method has sustainability; (2) The method has the advantages of mild reaction conditions, simple process and high yield of formic acid, and can be expected to have high application potential; (3) The method selects the vanadium-containing heteropoly acid HPA-n which is soluble in water as a catalyst, and has high oxidation activity and selectivity in an oxidation state; the reoxidation activity is very high in a reduction state, and the regeneration can be realized under mild conditions.
Drawings
FIG. 1 is a schematic diagram of a process for the catalytic oxygen oxidation of carbohydrates to formic acid by separate means of reduction and reoxidation of the catalyst.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
This example includes three steps, carbohydrate oxidation, product extraction and catalyst reoxidation.
(a) Oxidation of carbohydrates: uses glucose as raw material and HPA-5 as catalyst to oxidize carbohydrate to prepare formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. 0.018g of glucose, 0.42mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product.
(b) And (3) product extraction: transferring the reaction liquid in the step (a) into a separating funnel, extracting a formic acid product in the reaction liquid by using diethyl ether as an extracting agent, wherein the volume ratio of the diethyl ether to the reaction liquid is 10, and extracting for 5 times. Then, nitrogen is used for purging raffinate phase for 10min, ether introduced in the raffinate phase is removed, and the reduced catalyst HPA-5 is obtained red Transferring the aqueous solution to a measuring cylinder to determine the volume, and takingA volume of sample is analyzed.
(c) Catalyst reoxidation: HPA-5 of step (b) red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling 2.0MPa of oxygen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 60 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, exhausting the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, taking a sample with a certain volume for analysis, and using other reaction liquid for the next round of oxidation of the carbohydrate.
And (3) analysis: determination of CO in gas samples by gas chromatograph 2 The amount of production of (c). The gas chromatograph used was an Agilent 7890A, the column was a 50/80Porapak Q column, the detector was TCD, and the carrier gas was helium. And analyzing the composition and content of each product by using high performance liquid chromatography on the liquid sample. The high performance liquid chromatograph used is Waters 2695, the detector is a differential detector, the chromatographic column is a Shodex SH 1011 carbohydrate chromatographic column, the column temperature is 55 ℃, the mobile phase is a sulfuric acid aqueous solution with the mass fraction of 0.1wt%, and the flow rate of the mobile phase is 0.5mL/min. In addition, a sample of the liquid after reoxidation of the catalyst was subjected to uv-vis spectroscopy to analyze the degree of reoxidation of the reduced catalyst. The ultraviolet visible spectrometer is TU-1901, the wavelength range is 400 nm-900 nm, and the specification of the cuvette is 10mm multiplied by 5mm. According to the absorbance at 750nm (HPA-5) red Characteristic response strength) to determine the degree of reoxidation.
The results show that:
(a) Oxidation of carbohydrates: the conversion rate of glucose is 100 percent, the liquid phase product only contains formic acid, and the carbon yield of the formic acid calculated by taking the organic C content of the initial glucose as the reference is 95.4 percent; the gas-phase product is CO 2 The yield was 2.7%.
(b) Product extraction: the extraction efficiency of ethyl ether to formic acid was calculated to be 98.3% based on the formic acid content in the reaction solution before extraction.
(c) Reoxidation of the catalyst: catalyst solution after reoxidation inThe absorbance at 750nm of the UV-visible spectrum was 0.0, indicating HPA-5 in the catalyst solution red Has been totally reoxidized to HPA-5.
Example 2
This example is a cycle experiment of the oxidation process. In the first cycle, the reaction solution obtained by reoxidizing the catalyst in the step (c) of example 1 was used as a catalyst solution, and glucose was used as a raw material to oxidize carbohydrates to produce formic acid. The carbohydrate oxidation experiment was performed in substantially the same manner as in step (a) of example 1, without the addition of additional deionized water; the conditions were such that the molar ratio of V atoms in HPA-5 to C atoms in glucose was kept constant at 3.5. The subsequent product extraction and catalyst reoxidation steps were as in example 1, steps (b) and (c). And performing second to fourth cycles according to the method of the first cycle, wherein the reaction solution obtained after the catalyst is reoxidized in each cycle is used as the catalyst solution.
The analysis conditions and method were the same as in example 1.
The results show that: the conversion rate of glucose in each circulation is 100%, the liquid phase product only contains formic acid, and the carbon yield of the formic acid obtained in the first circulation to the fourth circulation is respectively 93.9%, 94.4%, 92.3% and 93.6% by taking the initial organic glucose content as a reference; the gas phase product is CO 2 First to fourth cycles of CO 2 The yields were 2.8%, 2.7%, 3.5% and 2.9%, respectively.
Example 3
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. 0.018g of glucose, 0.24mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 2), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid-phase product was 91.8% calculated on the basis of the initial organic C content of glucose, wherein formic acid was 85.2%, acetic acid was 0.9%, glycolic acid was 4.0%, glyceric acid was 1.3%, 5-hydroxymethylfurfural was 0.1%, and fructose was 0.3%; the gas phase product is CO 2 The yield was 3.0%.
Example 4
This example is a comparative experiment comparing the yield of formic acid and CO obtained by a typical catalytic oxygen oxidation 2 Yield.
The method takes glucose as a raw material, HPA-5 as a catalyst and oxygen as an oxidant to catalyze the oxygen to oxidize carbohydrates to prepare formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. 0.018g of glucose, 0.24mmol of HPA-5 and 10mL of deionized water were added to a reaction vessel (the mass content of glucose therein was 0.18 wt%), the reaction vessel was closed, the air in the reaction vessel was replaced with oxygen, and then 2.0MPa of oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion rate of glucose is 100%, the liquid phase product only contains formic acid, and the carbon yield of the formic acid calculated by taking the organic C content of the initial glucose as a reference is 57.3%; the gas-phase product is CO 2 The yield was 39.4%. In contrast to the oxidation process of example 3, which separates carbohydrate oxidation and catalyst reoxidation, CO, which catalyzes oxygen oxidation in general 2 The yield is obviously higher, and the selectivity of formic acid is higherLower.
Example 5
In this example, glucose was used as a raw material, HPA-2 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.6mmol of HPA-2 and 10mL of deionized water were placed in a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-2 to C atoms in glucose was 2), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product was 89.2% calculated on the basis of the initial glucose organic C content, wherein formic acid was 78.2%, acetic acid was 2.6%, glycolic acid was 4.5%, glyceric acid was 1.3%, 5-hydroxymethylfurfural was 0.5%, fructose was 0.8%, and gluconic acid was 1.3%; the gas-phase product is CO 2 The yield was 3.0%.
Example 6
In this example, glucose was used as a raw material, HPA-3 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.4mmol of HPA-3 and 10mL of deionized water were charged into a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-3 to C atoms in glucose was 2), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product was 87.1% calculated on the basis of the initial glucose organic C content, wherein formic acid was 75.3%, acetic acid was 2.4%, glycolic acid was 5.8%, glyceric acid was 1.6%, 5-hydroxymethylfurfural was 0.2%, fructose was 0.8%, and gluconic acid was 1.0%; the gas phase product is CO 2 The yield was 3.9%.
Example 7
In this example, glucose was used as a raw material, HPA-4 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.3mmol of HPA-4 and 10mL of deionized water were placed in a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-4 to C atoms in glucose was 2), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product, calculated based on the initial glucose organic C content, was 89.3%, wherein formic acid was 77.6%, acetic acid was 2.5%, glycolic acid was 5.6%, glyceric acid was 0.7%, 5-hydroxymethylfurfural was 0.2%, fructose was 1.2%, and gluconic acid was 1.5%; the gas phase product is CO 2 The yield was 2.8%.
Example 8
In this example, glucose was used as a raw material, HPA-6 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.2mmol of HPA-6 and 10mL of deionized water were charged into a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-6 to C atoms in glucose was 2), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product was 93.6% calculated on the basis of the initial organic C content of glucose, wherein formic acid was 83.2%, acetic acid was 0.7%, glycolic acid was 6.9%, glyceric acid was 1.9%, and fructose was 0.9%; the gas phase product is CO 2 The yield was 2.8%.
Example 9
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.12mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 1), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: of glucoseConversion of 100%, and organic carbon yield of 88.6% of the resulting liquid phase product, calculated on the basis of the initial glucose organic C content, of 52.7% formic acid, 4.9% acetic acid, 10.2% glycolic acid, 9.0% glyceric acid, 0.6% 5-hydroxymethylfurfural and 11.2% fructose; the gas phase product is CO 2 The yield was 2.3%.
Example 10
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.18mmol of HPA-5 and 10mL of deionized water were charged into a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 1.5), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid-phase product was 89.3% calculated on the basis of the initial organic C content of glucose, wherein formic acid was 75.4%, acetic acid was 2.0%, glycolic acid was 6.2%, glyceric acid was 2.9%, 5-hydroxymethylfurfural was 0.6%, and fructose was 2.2%; the gas phase product is CO 2 The yield was 2.4%.
Example 11
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.3mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (wherein the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 2.5), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product was 93.9% calculated based on the initial organic C content of glucose, with 93.0% formic acid and 0.9% glycolic acid; the gas-phase product is CO 2 The yield was 3.0%.
Example 12
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.36mmol of HPA-5 and 10mL of deionized water were charged into a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 3), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion rate of glucose is 100 percent, the liquid phase product only contains formic acid, and the carbon yield of the formic acid calculated by taking the organic C content of the initial glucose as the reference is 94.4 percent; the gas phase product is CO 2 The yield was 2.9%.
Example 13
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.48mmol of HPA-5 and 10mL of deionized water were charged into a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 4), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion rate of glucose is 100 percent, the liquid phase product only contains formic acid, and the carbon yield of the formic acid calculated by taking the organic C content of the initial glucose as the reference is 93.6 percent; the gas phase product is CO 2 The yield was 2.8%.
Example 14
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glucose, 0.42mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after the reaction is carried out for 1min, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion rate of the glucose is 100 percent,the organic carbon yield of the resulting liquid phase product was 96.7% calculated on the basis of the initial glucose organic C content, with 95.0% formic acid and 1.7% glycolic acid; the gas phase product is CO 2 The yield was 2.4%.
Example 15
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.09g of glucose, 2.1mmol of HPA-5 and 10mL of deionized water were added to a reaction vessel (wherein the mass content of glucose was 0.9wt%, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after reacting for 1min, and quenching by using a cold water bath to terminate the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product, calculated based on the initial glucose organic C content, was 94.9%, with 92.8% formic acid and 2.1% glycolic acid; the gas phase product is CO 2 The yield was 2.8%.
Example 16
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.18g of glucose, 4.2mmol of HPA-5 and 10mL of deionized water were added to a reaction vessel (wherein the mass content of glucose was 1.8wt%, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after the reaction is carried out for 1min, and quenching by using a cold water bath to stop the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product, calculated based on the initial glucose organic C content, was 93.6% with 91.3% formic acid and 2.3% glycolic acid; the gas phase product is CO 2 The yield was 4.8%.
Example 17
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. 0.36g of glucose, 8.4mmol of HPA-5 and 10mL of deionized water were added to a reaction vessel (wherein the mass content of glucose was 3.6wt%, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after the reaction is carried out for 1min, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 100%, and the organic carbon yield of the resulting liquid phase product was 92.2% calculated on the basis of the initial organic C content of glucose, wherein formic acid was 89.6%, and glycolic acid was 2.6%; the gas-phase product is CO 2 The yield was 6.1%.
Example 18
In this example, glucose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. 0.018g of glucose, 0.42mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (the mass content of glucose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glucose was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 120 ℃, taking out the reaction kettle after reacting for 60min, and quenching the reaction kettle by using a cold water bath to terminate the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glucose was 98.4%, and the organic carbon yield of the resulting liquid phase product, calculated on the basis of the initial glucose organic C content, was 91.5%, with 88.3% formic acid, 1.2% arabinose, 2.0% glycolaldehyde; the gas-phase product is CO 2 The yield was 1.2%.
Example 19
In this example, arabinose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to prepare formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. 0.018g of arabinose, 0.42mmol of HPA-5 and 10mL of deionized water were charged into a reaction vessel (the mass content of arabinose was 0.18wt%, and the molar ratio of V atoms in HPA-5 to C atoms in arabinose was 3.5), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 120 ℃, taking out the reaction kettle after the reaction is carried out for 1min, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of arabinose was 79.8% and the organic carbon yield of the resulting liquid phase product was 76 calculated based on the organic C content of the starting arabinose.1 percent, wherein the formic acid is 69.5 percent, and the glycolaldehyde is 6.6 percent; the gas-phase product is CO 2 The yield was 0.5%.
Example 20
In the embodiment, erythrose is used as a raw material, HPA-5 is used as a catalyst, and carbohydrate is oxidized to prepare formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of erythrose, 0.42mmol of HPA-5 and 10mL of deionized water were added to a reaction vessel (wherein the mass content of erythrose was 0.18wt%, and the molar ratio of V atoms in HPA-5 to C atoms in erythrose was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 120 ℃, taking out the reaction kettle after reacting for 1min, and quenching by using a cold water bath to terminate the reaction. And (3) when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion rate of erythrose is 100%, the organic carbon yield of the obtained liquid-phase product is 99.0% by taking the organic C content of the initial erythrose as a reference, wherein the content of formic acid is 91.6%, and the content of glycolaldehyde is 7.4%; the gas phase product is CO 2 The yield was 0.6%.
Example 21
In this example, glyceraldehyde was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of glyceraldehyde, 0.42mmol of HPA-5 and 10mL of deionized water were put into a reaction vessel (wherein the mass content of glyceraldehyde was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in glyceraldehyde was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 120 ℃, taking out the reaction kettle after the reaction is carried out for 1min, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion of glyceraldehyde was 100%, and the organic carbon yield of the resulting liquid phase product, calculated on the basis of the initial aldohexose organic C content, was 98.9%, wherein formic acid was 90.1%, and glycolaldehyde was 8.8%; the gas-phase product is CO 2 The yield was 0.5%.
Example 22
In the embodiment, glycolaldehyde is used as a raw material, HPA-5 is used as a catalyst, and carbohydrate is oxidized to prepare formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. 0.018g of glycolaldehyde dimer, 0.42mmol of HPA-5 and 10mL of deionized water are added into a reaction kettle (wherein the mass content of glycolaldehyde is 0.18wt%, and the molar ratio of V atoms in HPA-5 to C atoms in glycolaldehyde is 3.5), the reaction kettle is sealed, and the air in the reaction kettle is replaced by nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 120 ℃, taking out the reaction kettle after reacting for 1min, and quenching by using a cold water bath to terminate the reaction. And when the reaction kettle is cooled to room temperature, discharging the gas product into the air bag, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a certain volume of sample for analyzing the gas product and the liquid product. The analysis conditions and method were the same as in example 1.
The results show that: the conversion rate of the glycolaldehyde is 92.0 percent, the liquid phase product only contains formic acid, and the carbon yield of the obtained formic acid is 90.9 percent by taking the organic C content of the initial glycolaldehyde as a reference; the gas phase product is CO 2 The yield was 0.2%.
Example 23
In the embodiment, xylan is used as a raw material, HPA-5 is used as a catalyst, and carbohydrate is oxidized to prepare formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of xylan, 0.48mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (the mass content of xylan was 0.18wt%, and the molar ratio of V atoms in HPA-5 to C atoms in xylan was 3.5), the reaction vessel was sealed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 160 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And (5) when the reaction kettle is cooled to room temperature, collecting a sample for analysis.
Discharging the gas product into an air bag, and determining CO by gas chromatography 2 The amount of production of (c). The gas chromatograph used was an Agilent 7890A, the column was a 50/80Porapak Q column, the detector was TCD, and the carrier gas was helium. The reaction solution was filtered to obtain a residue and a filtrate. Drying and weighing the residues to calculate the mass conversion rate of the raw materials. Transferring the filtrate to a measuring cylinder to determine the volume, and sampling to perform high performance liquid chromatography analysis on the composition. The HPLC is Waters 2695, the detector is a differential detector, the chromatographic column is a Shodex SH 1011 sugar chromatographic column, the column temperature is 55 ℃, the mobile phase is a sulfuric acid aqueous solution with the mass fraction of 0.1wt%, and the flow of the mobile phase is 0.5mL/min.
The results show that: the mass conversion of xylan was 100wt%, and the organic carbon yield of the resulting liquid phase product, calculated on the basis of the organic C content of the starting xylan, was 97.3%, with 93.9% formic acid and 3.4% acetic acid; the gas phase product is CO 2 The yield was 2.7%.
Example 24
In this example, cellulose was used as a raw material, HPA-5 was used as a catalyst, and a carbohydrate was oxidized to produce formic acid. Carbohydrate oxidation experiments were performed in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.018g of cellulose, 0.47mmol of HPA-5 and 10mL of deionized water were placed in a reaction vessel (wherein the mass content of cellulose was 0.18% by weight, and the molar ratio of V atoms in HPA-5 to C atoms in cellulose was 3.5), the reaction vessel was closed, and the air in the reaction vessel was replaced with nitrogen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 180 ℃, taking out the reaction kettle after reacting for 60min, and quenching by using a cold water bath to terminate the reaction. And (5) when the reaction kettle is cooled to room temperature, collecting a sample for analysis. The analysis conditions and method were the same as in example 23.
The results show that: the mass conversion of the cellulose was 82.7% by weight, and the formic acid yield, calculated on the basis of the organic C content of the starting cellulose, was 75.1%; the gas phase product is CO 2 The yield was 8.8%.
Example 25
This example is a product extraction step after carbohydrate oxidation. The reaction solution after glucose oxidation was obtained by repeating the step (a) of example 1, and then formic acid product in the reaction solution was extracted with ethyl acetate as an extractant at a volume ratio of ethyl acetate to the reaction solution of 10 by 5 times. Then, nitrogen is used for purging raffinate phase for 10min to remove the introduced ethyl acetate, and the reduced catalyst HPA-5 is obtained red The aqueous solution is transferred to a measuring cylinder to determine the volume, and a certain volume of sample is taken for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the extraction efficiency of ethyl acetate with respect to formic acid was calculated to be 93.6% based on the formic acid content in the reaction liquid before extraction.
Example 26
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red The aqueous solution was transferred to a 50mL high-temperature high-pressure reactor, which was sealed and then charged with 9.5MPa of synthetic air (oxygen partial pressure: 2 MPa). And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 60 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, exhausting the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the reoxidized catalyst solution at 750nm in the UV-visible spectrum was 0.0, indicating that HPA-5 was present in the catalyst solution red Has been totally reoxidized to HPA-5.
Example 27
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling oxygen of 0.5 MPa. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 60 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, evacuating the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the catalyst solution after reoxidation at 750nm in the ultraviolet-visible spectrum was 0.9, indicating that HPA-5 was also present in the catalyst solution red Not reoxidized.
Example 28
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling 1MPa of oxygen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 60 ℃, taking out the reaction kettle after 10min of reaction, and quenching the reaction kettle by using a cold water bath to terminate the reaction. And when the reaction kettle is cooled to room temperature, exhausting the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the reoxidized catalyst solution at 750nm in the UV-visible spectrum was 0.6, indicating that HPA-5 was also present in the catalyst solution red Not reoxidized.
Example 29
This example is a catalyst reoxidation step after product extraction. Is first repeatedly implementedEXAMPLE 1 Steps (a) and (b) give the catalyst HPA-5 in reduced form red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling 1.5MPa of oxygen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 60 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, exhausting the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the reoxidized catalyst solution at 750nm in the UV-visible spectrum was 0.2, indicating that HPA-5 was also present in the catalyst solution red Not reoxidized.
Example 30
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling 2.5MPa of oxygen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 60 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, evacuating the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the reoxidized catalyst solution at 750nm in the ultraviolet-visible spectrum is 0.0, which indicates that HPA-5 is present in the catalyst solution red Has been totally reoxidized to HPA-5.
Example 31
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, and using oxygenThe air in the reaction vessel was replaced, and then 2.0MPa of oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 30 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, exhausting the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the catalyst solution after reoxidation at 750nm in the UV-visible spectrum was 1.2, indicating that HPA-5 was also present in the catalyst solution red Not reoxidized.
Example 32
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling 2.0MPa of oxygen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 40 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, evacuating the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the catalyst solution after reoxidation at 750nm in the ultraviolet-visible spectrum was 0.8, indicating that HPA-5 was also present in the catalyst solution red Not reoxidized.
Example 33
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling 2.0MPa of oxygen. Putting the reaction kettle into a pre-heated heating sleeve, starting stirring, and when the reaction temperature reaches 50 DEGThe time was counted at the time of reaction at 10min, and after the reaction, the reaction vessel was taken out and quenched with a cold water bath to terminate the reaction. And when the reaction kettle is cooled to room temperature, exhausting the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the catalyst solution after reoxidation at 750nm in the ultraviolet-visible spectrum was 0.4, indicating that HPA-5 was also present in the catalyst solution red Is not reoxidized.
Example 34
This example is a catalyst reoxidation step after product extraction. Example 1 Steps (a) and (b) were repeated to obtain catalyst HPA-5 in a reduced state red Transferring the aqueous solution into a 50mL high-temperature high-pressure reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and then filling 2.0MPa of oxygen. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 70 ℃, taking out the reaction kettle after 10min of reaction, and quenching by using a cold water bath to stop the reaction. And when the reaction kettle is cooled to room temperature, exhausting the gas in the kettle, transferring the reaction liquid to a measuring cylinder to determine the volume, and taking a sample with a certain volume for analysis. The analysis conditions and method were the same as in example 1.
The results show that: the absorbance of the reoxidized catalyst solution at 750nm in the ultraviolet-visible spectrum is 0.0, which indicates that HPA-5 is present in the catalyst solution red Has been totally reoxidized to HPA-5.
Claims (6)
1. A method for preparing formic acid by catalyzing oxygen to oxidize biomass carbohydrate comprises the following specific steps:
(a) Oxidation of carbohydrates: adding a carbohydrate raw material, an oxidation state catalyst and water into a high-pressure reaction kettle, stirring and reacting at a given temperature, and cooling to terminate the reaction after the reaction time is reached;
(b) Product extraction: extracting a formic acid product in the reaction solution by using an extracting agent, wherein an extraction raffinate is an aqueous solution of a reduced catalyst;
(c) Reoxidation of the catalyst: transferring the reduced catalyst aqueous solution into another high-pressure reaction kettle, filling oxygen or air, stirring and reacting at a given temperature, and taking out a reaction solution after the reaction time is reached, wherein the reaction solution is the aqueous solution of the oxidized catalyst and is used for the oxidation of carbohydrates in the next round;
wherein, the carbohydrate in the step (a) is selected from one of glucose, arabinose, erythrose, glyceraldehyde, glycolaldehyde, cellulose and xylan;
the mass content of the carbohydrate raw material in the aqueous solution in the step (a) is 0.18-3.6 wt%;
the catalyst in step (a) is selected from H 5 PV 2 Mo 10 O 40 、H 6 PV 3 Mo 9 O 40 、H 7 PV 4 Mo 8 O 40 、H 8 PV 5 Mo 7 O 40 、H 9 PV 6 Mo 6 O 40 One of (1);
the molar ratio of the V atoms in the catalyst in the step (a) to the C atoms in the carbohydrate is 1-4;
the temperature of the carbohydrate oxidation reaction in the step (a) is 120-180 ℃;
the time of the carbohydrate oxidation reaction in the step (a) is 1 min-60 min;
extracting the extractant in the step (b) for 3-7 times, wherein the extractant is selected from diethyl ether or ethyl acetate, and the volume ratio of the extractant to the reaction solution is 10;
the initial partial pressure of the oxygen in the step (c) is 0.5MPa to 2.5MPa;
the reaction temperature of the catalyst reoxidation in the step (c) is 30-70 ℃;
the reaction time for reoxidation of the catalyst in step (c) was 10min.
2. The process of claim 1 wherein the catalyst is H 8 PV 5 Mo 7 O 40 。
3. The process of claim 1, wherein the molar ratio of V atoms in the catalyst to C atoms in the carbohydrate is 3 to 4.
4. The method of claim 1, wherein the carbohydrate oxidation reaction time is 10min to 60min.
5. The method of claim 1, wherein the initial partial pressure of oxygen for the catalyst reoxidation reaction is in the range of 1.5MPa to 2.5MPa.
6. The method of claim 1, wherein the reaction temperature for the catalyst reoxidation reaction is between 50 ℃ and 70 ℃.
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