CN115872851A - Method for preparing formic acid and formaldehyde by synergistic catalytic oxidation of biomass and methanol - Google Patents
Method for preparing formic acid and formaldehyde by synergistic catalytic oxidation of biomass and methanol Download PDFInfo
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Abstract
The invention relates to a method for preparing formic acid and formaldehyde by concerted catalytic oxidation of biomass-based carbohydrate and methanol. The method takes biomass-based carbohydrate and methanol as raw materials, oxygen as an oxidant and water as a solvent, and oxidizes the carbohydrate into formic acid with high selectivity under the action of a vanadium-containing homogeneous catalyst, and simultaneously oxidizes the methanol into formaldehyde mildly. Compared with the traditional method for preparing formic acid, the method takes cheap and rich biomass-based carbohydrate as a raw material, avoids environmental pollution and has sustainability. Compared with other methods for preparing formic acid by catalyzing oxygen to oxidize carbohydrate, the method can obtain higher-yield formic acid under the synergistic action of methanol, and greatly improve the atom utilization rate of carbohydrate. Compared with the traditional method for preparing formaldehyde, the method realizes the preparation of formaldehyde by catalyzing oxygen to oxidize methanol at low temperature (less than 100 ℃), has mild reaction conditions and obviously reduces energy consumption.
Description
Technical Field
The invention relates to a method for preparing formic acid and formaldehyde by catalytic oxidation of biomass and methanol, in particular to a method for preparing formic acid and formaldehyde by concerted catalytic oxidation of biomass-based carbohydrate and methanol.
Technical Field
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 unique properties. In recent years, formic acid has shown great potential in the field of fuel cells and hydrogen storage materials. The formic acid fuel cell has the advantages of high energy density, low cross flux, environmental protection, nonflammability and the like; as a hydrogen production raw material, formic acid has high hydrogen capacity (53.4 g/L) and good transportation and storage safety. There is an approximately 87 million tons of formic acid worldwide per year, with an estimated 3.9% increase in formic acid consumption in the next 5 years. At present, the industrial preparation methods of formic acid mainly comprise a sodium formate method, a methyl formate hydrolysis method and a formamide method, but the methods are all based on a fossil route, cause serious pollution in the production process and can not regenerate raw materials. Based on the requirements of sustainable development and green chemical industry, the development of a novel formic acid production method which has high efficiency and little pollution and takes renewable resources as raw materials is urgent.
Biomass is the only renewable carbon resource on earth, wherein carbon is the CO in the atmosphere generated by plants through photosynthesis 2 Is converted into the protein. The method for preparing chemicals by using biomass as a raw material is a green sustainable method, and not only can the raw material be regenerated, but also the effect of negative carbon emission can be achieved. The plant biomass is also called lignocellulose, can be obtained from plant residues and wastes in the fields of agriculture, forestry, industry and the like, and has wide distribution, 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. At present, there are some reports of using biomass-based carbohydrate to prepare formic acid, for example, chinese patent (application No. 201080019836.6) discloses a production method of formic acid, which involves hydrolyzing carbohydrate-containing material in the presence of inorganic acid to produce formic 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 number 201180054759.2) disclosesA catalytic process for the production of formic acid by catalytic oxidation of carbohydrates at low temperatures in the presence of CO produced by peroxidation 2 Resulting in a problem that the yield of formic acid is limited.
Journal articles have also been reported for the catalytic oxidation of biomass-based carbohydrates to formic acid. Jin et al (F.jin, H.Enomoto. Rapid and high selective conversion of biological in-value-amplified products in hydraulic conversions: chemistry of acid/base-captured and oxidation reactions. Energy&Environmental Science,2011,4 (2): 382-397) uses inorganic base such as NaOH as catalyst and H 2 O 2 As an oxidizing agent, oxidation of cellulose at high temperature of 250 ℃ produced formic acid (sodium salt) in yields of up to 75%. 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.
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From Waters chemical, selective catalytic conversion of biological substrates to molecular oxygen Green Chemistry 2011,13 (10): 2759-2763) with heteropolyacid H 5 PV 2 Mo 10 O 40 As a catalyst, catalyzing glucose at 80 ℃ and 3MPa O 2 Next conversion, formic acid was obtained in 49% yield. Albert et al (J.Albert, D.Luders, A.)>
M. guldi, p.wassers chemical.spectral and electrochemical conversion of hydrolytic acids for the selective application in selective biochemical oxidation to for the green chemical, 2014, 16) found heteropolyacid tables with increasing vanadium substitutionBetter catalytic performance is achieved, wherein H 8 PV 5 Mo 7 O 40 The best performing, glucose was converted to formic acid in 57.3% yield. Li et al (J.Li, D.J.Ding, L.Deng, Q.X.Guo, Y.Fu.catalytic air oxidation of biological-derived catalysts to chemical acid ChemSusChem,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 (T.Lu, M.G.Niu, Y.C.Hou, W.Z.Wu, S.H.ren, F.Yang.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 CO 2 The negative carbon emission effect of biomass preparation chemicals is weakened. Therefore, a more efficient method for preparing formic acid by catalytic oxidation of biomass-based carbohydrates needs to be found, and the yield of formic acid is improved.
Formaldehyde is an important chemical raw material and is used for producing important chemical products such as adhesives, polyformaldehyde, paraformaldehyde, diphenylmethane diisocyanate and the like. In addition, the polymer can also be used as an additive for antiseptic solution and textile industry. Currently, formaldehyde is produced industrially mainly by catalytic oxidation using methanol as a raw material and air as an oxidant, and the method includes a methanol excess oxidation method and an air excess oxidation method, and catalytic oxidation is performed by using a silver or iron-molybdenum catalyst (menglan. The current status of formaldehyde production and the technological progress in China, chemical engineering and equipment, 2010,9, 160-162). However, both methods require reactions at high temperatures (> 320 ℃), and are high in energy consumption; in the aspect of catalyst, the silver catalyst is expensive, and the iron-molybdenum catalyst cannot be recycled. New catalytic oxidation processes are sought that reduce energy consumption and catalyst cost. At present, some reports of methanol oxidation for preparing formaldehyde are available, for example, chinese patent application No. 200910177002.7 discloses a formaldehyde production method, wherein a silver-copper double-layer catalyst is combined to catalyze methanol oxidation for producing formaldehyde, methanol steam, water steam and air are sequentially catalyzed by silver and copper in two steps, and are reacted at 550-700 ℃, and the combined catalyst improves the conversion rate of methanol and the selectivity of formaldehyde. Chinese patent (application No. 201510912816.6) discloses a method for producing formaldehyde by an iron-molybdenum method, which relates to the steps of air intake, mixing, reaction, absorption, tail gas treatment and the like, and solves the problem that a system cannot continue to operate after the production of an iron-molybdenum catalyst containing a special formula of metal chromium is stopped. Chinese patent application No. 201610177243.1 discloses a formaldehyde production method based on tail gas circulation process, wherein quaternary mixed gas (comprising methanol vapor, air, water vapor and tail gas) passes through an electrolytic silver catalyst layer from top to bottom in an oxidizer, and side reactions in the preparation process are reduced by reasonable selection of process parameters in the production process. Chinese patent (application number 201811504619.0) discloses a formaldehyde production method with multiple reactors connected in series, wherein the reactor is formed by connecting a pre-reactor, a first reactor and a second reactor in series, and the reaction temperatures of three-section reactors are respectively 140-150 ℃, 150-270 ℃ and 275-425 ℃. The multistage reactor improves the utilization rate of the iron-molybdenum catalyst and promotes the high-efficiency and low-consumption operation of the system. However, these methods are required to be carried out at a reaction temperature of not lower than 240 ℃ and still have a problem of high energy consumption. Therefore, a method for preparing formaldehyde by methanol oxidation under mild conditions needs to be found, and the energy consumption of the reaction is reduced.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the present invention provides a process for the preparation of formic acid and formaldehyde by the concerted catalytic oxidation of biomass-based carbohydrates with methanol. The method takes biomass-based carbohydrate and methanol as raw materials, oxygen as an oxidant and water as a solvent, and oxidizes the carbohydrate into formic acid with high selectivity under the action of a vanadium-containing homogeneous catalyst, and simultaneously oxidizes the methanol into formaldehyde mildly. The invention discovers that the synergistic oxidation effect exists between the carbohydrate and the methanol, the methanol can obviously improve the selectivity of the carbohydrate converted into the formic acid, and the carbohydrate with stronger reactivity can induce the oxidation of the methanol to generate the formaldehyde. The method is a green, efficient and low-energy-consumption production method of formic acid and formaldehyde, and provides a new technology for industrial application of preparing formic acid by high-selectivity oxidation of biomass and preparing formaldehyde by low-temperature oxidation of methanol.
The invention provides a method for preparing formic acid and formaldehyde by catalyzing oxygen oxidation with cooperation of carbohydrate and methanol. The method comprises the following specific steps:
adding carbohydrate, a methanol raw material, a catalyst and a water solvent into a high-pressure reaction kettle, introducing oxygen or air, stirring and reacting at a given temperature, cooling to finish the reaction after the reaction time is reached, discharging gas and collecting product gas, filtering and separating liquid and solid in the kettle, and collecting residues and filtrate dissolved with formic acid and formaldehyde.
In the above preparation method, the carbohydrate is selected from one of glucose, cellobiose, dextran, sucrose, xylose and xylan.
In the preparation method, the addition amount of the carbohydrate is 0.6wt% -3.0 wt%, preferably 1.2wt% -2.4 wt% based on the mass of the solvent.
In the preparation method, the mass fraction of the methanol is 0.7wt% -11.2 wt%, preferably 1.4wt% -5.6 wt%.
In the above preparation method, the catalyst is selected from H 5 PV 2 Mo 10 O 40 、H 8 PV 5 Mo 7 O 40 、NaVO 3 –H 2 SO 4 And VOSO 4 –H 2 SO 4 Is preferably H 5 PV 2 Mo 10 O 40 。
In the preparation method, the mass of the solvent is taken as a reference, and the addition amount of the catalyst is 0.5-1.9 wt% of mass fraction.
In the preparation method, the oxidant is oxygen or air, and the initial pressure (or partial pressure) of the oxygen is 2MPa to 5MPa.
In the preparation method, the temperature of the oxidation reaction is 80-100 ℃.
In the preparation method, the reaction time is 12 to 60 hours, preferably 36 to 60 hours.
The method for preparing formic acid and formaldehyde by the concerted catalytic oxidation of carbohydrate and methanol has the following principle: (1) mechanism of carbohydrate conversion to formic acid: first of all water-insoluble carbohydrates in a catalyst
Hydrolyzing the soluble carbohydrate under the action of acidity, then reacting the carbohydrate with pentavalent vanadium species of the catalyst, and carrying out continuous C1-C2 oxidation bond breaking at an aldehyde end to generate formic acid, and simultaneously reducing the pentavalent vanadium species into tetravalent vanadium species. (2) mechanism of methanol conversion to formaldehyde: firstly, tetravalent vanadium species of the catalyst reacts with molecular oxygen, and the tetravalent vanadium species is oxidized and recovered into pentavalent vanadium species along with the generation of hydroxyl free radicals (OH free radicals); the OH free radical can initiate the oxidation of methanol to formaldehyde. Through the synergistic catalytic oxidation of the carbohydrate and the methanol, the peroxidation degree caused by the attack of OH free radicals on the carbohydrate can be weakened, the selectivity of formic acid is improved, and the catalytic oxidation of the methanol at low temperature to prepare the formaldehyde can be realized by virtue of the fact that the oxidation of the carbohydrate and the reoxidation of tetravalent vanadium species in heteropoly acid can be carried out at low temperature.
Compared with the methods for preparing formic acid by catalytic oxidation of carbohydrate and preparing formaldehyde by catalytic oxidation of methanol in the literature, the method has the following advantages: (1) The carbohydrate and the methanol are subjected to catalytic oxygen oxidation together, the methanol can eliminate OH free radicals generated in the reoxidation process of the catalyst, the OH free radicals are prevented from being reacted with the carbohydrate to cause peroxidation, and the selectivity of formic acid is improved; (2) The carbohydrate and the methanol are subjected to catalytic oxygen oxidation together, the carbohydrate firstly reduces pentavalent vanadium species into tetravalent vanadium, and then the tetravalent vanadium species can activate molecular oxygen to generate OH free radicals to initiate the oxidation of the methanol, so that the catalytic oxidation of the methanol at low temperature is realized to prepare the formaldehyde; (3) The participation of methanol increases the solubility of oxygen in the aqueous solution and improves the reoxidation rate of the catalyst, thereby accelerating the overall catalytic oxygen oxidation. Compared with the method for industrially preparing formic acid and formaldehyde, the method has the following advantages: (1) The method takes cheap and rich biomass-based carbohydrate as a raw material to prepare formic acid, so that the cost is reduced, and the problem of environmental pollution caused by using fossil resources is avoided; (2) The method realizes the preparation of formaldehyde by the catalytic oxidation of methanol at low temperature, and has mild reaction conditions and low energy consumption; (3) The method uses the vanadium-containing homogeneous catalyst, so that the catalytic activity is high, and the yield of formic acid and the selectivity of formaldehyde in the product are high.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the following examples.
Example 1
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3.0MPa oxygen was charged. Putting the reaction kettle into a pre-heated heating sleeve and starting stirringWhen the reaction temperature reached 90 ℃ and the timer started, after 48 hours of reaction, the reaction vessel was taken out and quenched with a cold water bath to terminate 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 pocket, and determining CO in the gas sample by Gas Chromatograph (GC) 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 liquid product is fixed to 50mL, and the liquid sample is subjected to High Performance Liquid Chromatography (HPLC) and hydrogen Nuclear Magnetic Resonance (NMR) ((R)) 1 H NMR) analysis of the conversion of the starting materials and the composition and yield of the product, the yields of formic acid and methyl formate consisting of 1 H NMR, others by HPLC. 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. The nuclear magnetic resonance spectrometer used was Bruker AVANCE III HD 400, the spectrum range was-1 ppm to 15ppm, the number of scans was 16, acetone was used as the internal standard.
The results show that: the conversion of glucose was 100%, and the carbon yield of the liquid product was 95.0% calculated on the basis of the carbon content of the starting glucose, 91.0% of formic acid and 1.2% of methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), acetic acid 2.8%; the gas phase product is CO 2 The carbon yield was 4.9%. The methanol conversion was 45.1%, the carbon yield of formaldehyde was 36.2%, the carbon yield of methylal was 5.7%, and the carbon yield of methyl formate was 0.8%, based on the initial methanol carbon content (HCOOCH) 3 Here, it is referred to as-OCH 3 Yield of HCO-from formic acid).
Example 2
This example is a comparative experiment to determine the source of the product.
This example uses glucose and 13 methanol marked with C as raw material, oxygen as oxidant and H 5 PV 2 Mo 10 O 40 As catalyst, carbohydrate and methanolThe formic acid and the formaldehyde are prepared by the concerted catalytic oxidation. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose and 0.29g 13 C-labeled methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.9wt% and 1.9 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was replaced with oxygen, and then 3.0MPa 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 90 ℃, taking out the reaction kettle after 48 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 100%, and the carbon yield of the liquid product, calculated based on the carbon content of the starting glucose, was 94.5%, with 90.8% formic acid and 1.1% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), acetic acid 2.6%; the gas phase product is CO 2 The carbon yield was 5.1%. The methanol conversion was 44.9%, the carbon yield of formaldehyde was 36.0%, the carbon yield of methylal was 5.6%, and the carbon yield of methyl formate was 0.8% (HCOOCH) based on the initial methanol carbon content 3 Here, it means-OCH 3 Yield of HCO-from formic acid). The organic matters in the reaction solution are extracted by adopting anhydrous ether, and the gas chromatography-mass spectrometry (GC-MS) analysis is carried out, wherein the used gas chromatography-mass spectrometry instrument is Thermo Fisher ISQ Trace1300. The results showed that no detection was observed 13 And C is marked with formic acid, which indicates that the formic acid in the product is from the raw material glucose. According to the carbon balance analysis, formaldehyde is derived from the starting material methanol.
Example 3
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 The preparation of formic acid by the concerted catalytic oxidation of carbohydrate and methanol as a catalystAnd formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3.0MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours of reaction, and quenching the reaction kettle 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 97.5%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 90.2%, with 76.4% formic acid and 0.9% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 2.1%, arabinose 7.2%, glycolaldehyde 2.0%, acetic acid 1.6%; the gas phase product is CO 2 The carbon yield was 4.2%. The conversion of methanol was 37.6%, the carbon yield of formaldehyde was 30.2%, the carbon yield of methylal was 5.0%, and the carbon yield of methyl formate was 0.6% (HCOOCH) based on the initial methanol carbon content 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 4
This example is a comparative experiment comparing the product yield from catalytic oxygen oxidation of carbohydrates alone without addition of methanol.
In this example, glucose is used as the raw material, oxygen is used as the oxidant, H 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrates are catalyzed and oxidized to prepare formic acid. The catalytic oxidation experiments were carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (where glucose andH 5 PV 2 Mo 10 O 40 relative solvent mass fractions of 1.8wt% and 1.9 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was replaced with oxygen, and then 3.0MPa 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 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and method as in example 1, the conversion of glucose was 100%, and the carbon yield of the liquid phase product calculated based on the carbon content of the starting glucose was 42.7%, wherein formic acid was 42.6%, and glycolic acid was 0.1%; the gas-phase product is CO 2 The carbon yield was 49.8%. Compared with the co-catalytic oxidation of carbohydrate and methanol in example 3, the degree of peroxidation of carbohydrate alone in catalytic oxygen oxidation is significantly higher, and the selectivity of formic acid is lower.
Example 5
This example is a comparative experiment comparing the product yield obtained by catalytic oxygen oxidation of methanol alone without the addition of carbohydrate.
In this example, methanol was used as the raw material, oxygen was used as the oxidant, H 5 PV 2 Mo 10 O 40 The methanol is used as a catalyst to prepare formaldehyde by catalytic oxidation. The catalytic oxidation experiments were carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.28g of methanol and 0.19g of H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (methanol and H therein) 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 2.8wt% and 1.9 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was replaced with oxygen, and then 3.0MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedure as in example 1, the methanol conversion was 0.3% and the carbon yield of formaldehyde was 0.2% based on the initial methanol carbon content. The conversion and product yield were small, indicating that methanol is difficult to catalyze oxygen oxidation at low temperatures without the participation of carbohydrates.
Example 6
In this example, glucose and methanol were used as raw materials, air was used as an oxidant, and H was added 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction vessel, which was then sealed and charged with 14.3MPa of synthetic air. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 48 hours of reaction, and quenching the reaction kettle 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 100%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 94.5%, with 90.6% formic acid and 1.2% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), acetic acid 2.7%; the gas phase product is CO 2 The carbon yield was 5.1%. The methanol conversion was 44.6%, the carbon yield of formaldehyde was 36.1%, the carbon yield of methylal was 5.7%, and the carbon yield of methyl formate was 0.8% (HCOOCH) based on the initial methanol carbon content 3 Here, it is referred to as-OCH 3 Yield of HCO-from formic acid).
Example 7
This example uses glucose and methanol as raw materialsMaterial, oxygen as oxidant, H 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.07g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 0.7wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was displaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 98.5%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 78.5%, with 68.5% formic acid and 0.7% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 1.6%, arabinose 4.3%, glycolic acid 1.4%, acetic acid 2.0%; the gas phase product is CO 2 The carbon yield was 17.2%. The methanol conversion was 79.4%, the carbon yield of formaldehyde was 71.8%, the carbon yield of methylal was 2.2%, and the carbon yield of methyl formate was 1.9% (HCOOCH) based on the initial methanol carbon content 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 8
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, the carbohydrate and the methanol are synergistically catalyzed and oxidized to prepare the formic acid and the formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.14g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 1.4wt% and 1.9 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was displaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 98.0%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 87.9%, with 73.6% formic acid and 0.8% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 1.7%, arabinose 6.5%, glycolaldehyde 1.5%, glycolic acid 1.7%, acetic acid 2.1%; the gas phase product is CO 2 The carbon yield was 7.1%. The methanol conversion was 59.5%, the carbon yield of formaldehyde was 52.4%, the carbon yield of methylal was 3.7%, and the carbon yield of methyl formate was 1.1%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 9
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.56g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 5.6wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3MPa oxygen was charged. Putting the reaction kettle into the preheating chamberStirring is started in a good heating sleeve, timing is started when the reaction temperature reaches 90 ℃, and after 24 hours of reaction, the reaction kettle is taken out and quenched by a cold water bath to stop the reaction. And (5) when the reaction kettle is cooled to room temperature, collecting a sample for analysis.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 97.3%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 90.6%, with 76.2% formic acid and 1.2% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 2.5%, arabinose 7.8%, glycolaldehyde 2.2%, acetic acid 0.7%; the gas-phase product is CO 2 The carbon yield was 3.4%. The conversion of methanol was 30.4%, the carbon yield of formaldehyde was 19.5%, the carbon yield of methylal was 8.5%, and the carbon yield of methyl formate was 0.4% (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 10
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, H 5 PV 2 Mo 10 O 40 As a catalyst, the carbohydrate and the methanol are synergistically catalyzed and oxidized to prepare the formic acid and the formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 1.12g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 11.2wt% and 1.9 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was replaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and methods as in example 1, the conversion of glucose was 97.3%, based on the starting grapeThe carbon yield of the liquid phase product calculated based on the carbon content of the sugar was 93.4%, wherein the formic acid content was 76.1%, and the methyl formate content was 2.2% (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 2.7%, arabinose 9.0%, glycolaldehyde 2.6%, acetic acid 0.8%; the gas phase product is CO 2 The carbon yield was 2.9%. The conversion of methanol was 18.2%, the carbon yield of formaldehyde was 7.7%, the carbon yield of methylal was 9.3%, and the carbon yield of methyl formate was 0.4%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 11
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was displaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 12 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 89.3%, and the carbon yield of the liquid phase product calculated based on the carbon content of the starting glucose was 84.4%, wherein 47.0% of formic acid and 0.4% of methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 6.8%, arabinose 25.1%, glycolaldehyde 4.6%, acetic acid 0.5%; the gas phase product is CO 2 The carbon yield was 2.5%. The conversion of methanol was 23.5%The carbon yield of formaldehyde was 18.4%, the carbon yield of methylal was 3.3%, and the carbon yield of methyl formate was 0.3% (HCOOCH) based on the initial methanol carbon content 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 12
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, H 5 PV 2 Mo 10 O 40 As a catalyst, the carbohydrate and the methanol are synergistically catalyzed and oxidized to prepare the formic acid and the formaldehyde. The concerted catalytic oxidation experiments were carried out in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after reacting for 36 hours, 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 99.2%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 92.6%, with 85.7% formic acid and 1.0% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 1.1%, arabinose 1.0%, glycolaldehyde 1.5%, acetic acid 2.3%; the gas phase product is CO 2 The carbon yield was 4.8%. The conversion of methanol was 42.0%, the carbon yield of formaldehyde was 33.1%, the carbon yield of methylal was 5.3%, and the carbon yield of methyl formate was 0.7%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 13
Book blockExample glucose and methanol as raw materials, oxygen as oxidant, H 5 PV 2 Mo 10 O 40 As a catalyst, the carbohydrate and the methanol are synergistically catalyzed and oxidized to prepare the formic acid and the formaldehyde. The concerted catalytic oxidation experiments were carried out in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after reacting for 60 hours, 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 100%, and the carbon yield of the liquid product, calculated based on the carbon content of the starting glucose, was 92.9%, with 89.2% formic acid and 1.1% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), acetic acid 2.6%; the gas phase product is CO 2 The carbon yield was 6.3%. The conversion of methanol was 46.2%, the carbon yield of formaldehyde was 37.5%, the carbon yield of methylal was 5.8%, and the carbon yield of methyl formate was 0.8%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 14
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.06g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionizationSub-water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 0.6wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 100%, and the carbon yield of the liquid product, calculated based on the carbon content of the starting glucose, was 91.8%, wherein 89.8% of formic acid and 1.1% of methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), acetic acid 0.9%; the gas-phase product is CO 2 The carbon yield was 5.5%. The methanol conversion was 44.2%, the carbon yield of formaldehyde was 36.0%, the carbon yield of methylal was 5.6%, and the carbon yield of methyl formate was 0.3%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 15
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, the carbohydrate and the methanol are synergistically catalyzed and oxidized to prepare the formic acid and the formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.12g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.2wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was displaced with oxygen, and then 3MPa oxygen was charged. Putting the reaction kettle into a pre-heated heating sleeve, starting stirring, timing when the reaction temperature reaches 90 ℃, and reacting for 24 hoursThe reaction vessel was taken out and quenched with a cold water bath to terminate the reaction. And (5) when the reaction kettle is cooled to room temperature, collecting a sample for analysis.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 99.8%, and the carbon yield of the liquid product calculated based on the carbon content of the starting glucose was 92.6%, wherein formic acid was 86.7% and methyl formate was 1.0% (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 0.8%, arabinose 1.4%, glycolaldehyde 1.4%, acetic acid 1.3%; the gas-phase product is CO 2 The carbon yield was 5.1%. The methanol conversion was 42.7%, the carbon yield of formaldehyde was 34.6%, the carbon yield of methylal was 5.5%, and the carbon yield of methyl formate was 0.5%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 16
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.24g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 2.4wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and method as in example 1, the conversion of glucose was 93.1%, and the carbon yield of the liquid phase product calculated based on the carbon content of the starting glucose was 86.4%, wherein 63.5% formic acid was present,Methyl formate 0.7% (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 4.8%, arabinose 14.9%, glycolaldehyde 0.3%, glycolic acid 0.4%, acetic acid 1.8%; the gas phase product is CO 2 The carbon yield was 3.2%. The methanol conversion was 31.3%, the carbon yield of formaldehyde was 24.8%, the carbon yield of methylal was 4.3%, and the carbon yield of methyl formate was 0.6% (HCOOCH) based on the initial methanol carbon content 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 17
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.30g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 The mass fractions of the relative solvents are respectively 3.0wt%, 2.8wt% and 1.9 wt%), the mixture is added into a reaction kettle, the reaction kettle is sealed, the air in the reaction kettle is replaced by oxygen, and then 3MPa oxygen is filled. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 86.6%, and the carbon yield of the liquid product calculated based on the carbon content of the starting glucose was 83.3%, with 45.3% formic acid and 0.4% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 7.2%, arabinose 27.3%, glycolic acid 1.2%, acetic acid 1.9%; the gas phase product is CO 2 The carbon yield was 2.0%. The conversion of methanol was 22.3%, and the carbon yield of formaldehyde was 17.5% based on the initial methanol carbon contentPercent, the carbon yield of methylal was 3.2 percent, and the carbon yield of methyl formate was 0.5 percent (HCOOCH) 3 Here, it is referred to as-OCH 3 Yield of HCO-from formic acid).
Example 18
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 2MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 94.3%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 89.9%, wherein 63.3% of formic acid and 0.6% of methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 4.3%, arabinose 15.1%, glycolaldehyde 3.1%, acetic acid 3.5%; the gas phase product is CO 2 The carbon yield was 2.7%. The conversion of methanol was 31.2%, the carbon yield of formaldehyde was 24.3%, the carbon yield of methylal was 4.2%, and the carbon yield of methyl formate was 0.4%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 19
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 4MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 98.9%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 91.3%, with 82.7% formic acid and 1.1% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 1.6%, arabinose 3.4%, glycolaldehyde 1.1%, acetic acid 1.4%; the gas phase product is CO 2 The carbon yield was 5.3%. The conversion of methanol was 40.7%, the carbon yield of formaldehyde was 33.1%, the carbon yield of methylal was 5.3%, and the carbon yield of methyl formate was 0.7%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 20
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, the carbohydrate and the methanol are synergistically catalyzed and oxidized to prepare the formic acid and the formaldehyde. The concerted catalytic oxidation experiments were carried out in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (whichMedium glucose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 5MPa 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 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 99.6%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 91.4%, wherein formic acid was 85.4% and methyl formate was 1.2% (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 0.7%, arabinose 2.2%, glycolaldehyde 0.6%, acetic acid 1.3%; the gas phase product is CO 2 The carbon yield was 6.1%. The conversion of methanol was 42.0%, the carbon yield of formaldehyde was 33.7%, the carbon yield of methylal was 5.4%, and the carbon yield of methyl formate was 0.8% (HCOOCH) based on the initial methanol carbon content 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 21
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 8 PV 5 Mo 7 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiments were carried out in a 50mL high temperature high pressure autoclave reactor with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.07g H 8 PV 5 Mo 7 O 40 And 10mL of deionized water (wherein glucose, methanol and H 8 PV 5 Mo 7 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 0.7 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3MPa oxygen was charged. Putting the reaction kettle into a pre-heated heating sleeve, starting stirring, and reacting at the reaction temperatureWhen the temperature reaches 90 ℃, timing is started, and after 24 hours of reaction, the reaction kettle is taken out and quenched by a cold water bath to terminate the reaction. And (5) when the reaction kettle is cooled to room temperature, collecting a sample for analysis.
Using the same analytical conditions and procedures as in example 1, the conversion of glucose was 95.8%, and the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 84.0%, with 67.5% formic acid and 0.7% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 2.5%, arabinose 9.1%, glycolaldehyde 1.9%, acetic acid 2.3%; the gas phase product is CO 2 The carbon yield was 10.6%. The conversion of methanol was 27.7%, the carbon yield of formaldehyde was 20.8%, the carbon yield of methylal was 3.6%, and the carbon yield of methyl formate was 0.5%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 22
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, and NaVO was used 3 –H 2 SO 4 As a catalyst, the carbohydrate and the methanol are synergistically catalyzed and oxidized to prepare the formic acid and the formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.024g NaVO 3 、0.026g H 2 SO 4 And 10mL of deionized water (wherein glucose, methanol and NaVO are present) 3 –H 2 SO 4 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 0.5 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was replaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
The same analysis conditions and method as in example 1 were used, wherein the liquid product was filtered first, and then the filtrate was taken out after the volume was made to 50mL for analysis. The results show the conversion of glucose48.9%, the carbon yield of the liquid product, calculated on the basis of the carbon content of the starting glucose, was 45.6%, with 20.6% formic acid and 0.1% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 6.1%, arabinose 12.9%, erythrose 3.1%, glycolaldehyde 2.0%, acetic acid 0.8%; the gas-phase product is CO 2 The carbon yield was 2.6%. The conversion of methanol was 9.1%, the carbon yield of formaldehyde was 6.9%, the carbon yield of methylal was 1.3%, and the carbon yield of methyl formate was 0.1%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 23
In this example, glucose and methanol were used as raw materials, oxygen was used as an oxidant, VOSO 4 –H 2 SO 4 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.18g glucose, 0.28g methanol, 0.033g VOSO 4 、0.026g H 2 SO 4 And 10mL of deionized water (wherein glucose, methanol and VOSO 4 –H 2 SO 4 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 0.6 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours of reaction, and quenching the reaction kettle 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 same analysis conditions and method as in example 1 were used, wherein the liquid product was filtered first, and then the filtrate was taken out after the volume was adjusted to 50mL for analysis. The results showed that the conversion of glucose was 37.7%, and the carbon yield of the liquid-phase product was 33.3% calculated on the basis of the carbon content of the starting glucose, wherein 16.3% of formic acid and 0.1% of methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), fructose 2.2%, arabinose 10.5%, erythrose 3.2% and glycolaldehyde 1.0%; the gas phase product is CO 2 The carbon yield was 4.7%. The conversion of methanol was 11.4%, the carbon yield of formaldehyde was 8.4%, the carbon yield of methylal was 1.6%, and the carbon yield of methyl formate was 0.1%, based on the initial methanol carbon content (HCOOCH) 3 Here, it is referred to as-OCH 3 Yield of HCO-from formic acid).
Example 24
In this example, cellobiose and methanol were used as raw materials, oxygen was used as an oxidizing agent, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.17g of cellobiose, 0.28g of methanol and 0.19g of H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein cellobiose, methanol and H) 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.7wt%, 2.8wt% and 1.9 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was displaced with oxygen, and then 3.0MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 100 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and method as in example 1, the conversion of cellobiose was 63.5%, and the carbon yield of the liquid phase product calculated based on the carbon content of the starting cellobiose was 51.9%, wherein formic acid was 19.5% and methyl formate was 0.2% (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), glucose 13.6%, fructose 6.4%, arabinose 10.6%, glycolaldehyde 1.5%; the gas phase product is CO 2 The carbon yield was 4.2%. The conversion of methanol was 13.1%, the carbon yield of formaldehyde was 9.6%, the carbon yield of methylal was 1.6%, and the carbon yield of methyl formate was 0.2%, based on the initial methanol carbon content (HCOOCH) 3 Here, it is referred to as-OCH 3 Yield of HCO-from formic acid).
Example 25
In this example, dextran and methanol were used as raw materials, oxygen was used as an oxidant, H 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.16g dextran, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (dextran, methanol and H therein) 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.6wt%, 2.8wt% and 1.9 wt%) were added to the reaction vessel, the reaction vessel was sealed, air in the reaction vessel was displaced with oxygen, and then 3.0MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 100 ℃, taking out the reaction kettle after 24 hours 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 (GC) on the gas sample 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. The filtrate was made to a volume of 50mL, and the liquid sample was purified by High Performance Liquid Chromatography (HPLC) and hydrogen Nuclear Magnetic Resonance (NMR) ((R)) 1 H NMR) analysis of the conversion of the starting materials and the composition and yield of the product, the yields of formic acid and methyl formate consisting of 1 H NMR and others by HPLC. 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. The nuclear magnetic resonance spectrometer used was Bruker AVANCE III HD 400, the spectrum range was-1 ppm to 15ppm, the number of scans was 16, acetone was used as the internal standard.
The results show that: the conversion of dextran was 23.2wt%, the carbon yield of the resulting liquid phase product was 17.4% calculated on the basis of the starting dextran carbon content, with 8.3% formic acid, 0.2% methyl formate (HCOOCH @) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), glucose 4.7%, fructose 1.4%, arabinose 2.5%, glycolaldehyde 0.4%; the gas phase product is CO 2 The carbon yield was 2.6%. The conversion of methanol was 6.9%, the carbon yield of formaldehyde was 5.1%, the carbon yield of methylal was 0.8%, and the carbon yield of methyl formate was 0.1%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 26
In this example, sucrose and methanol were used as raw materials, oxygen was used as an oxidant, and H was added 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.17g sucrose, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (sucrose, methanol and H therein) 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.7wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3.0MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and method as in example 1, the conversion of sucrose was 100%, and the carbon yield of the liquid phase product calculated based on the carbon content of the starting sucrose was 81.2%, wherein 59.3% of formic acid and 0.3% of methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), glucose 4.3%, fructose 2.9%, arabinose 7.1%, glycolaldehyde 3.9%,3.4 percent of acetic acid; the gas-phase product is CO 2 The carbon yield was 15.4%. The methanol conversion was 34.0%, the carbon yield of formaldehyde was 27.4%, the carbon yield of methylal was 4.6%, and the carbon yield of methyl formate was 0.2% based on the initial methanol carbon content (HCOOCH) 3 Here, it is referred to as-OCH 3 Yield of HCO-from formic acid).
Example 27
In this example, xylose and methanol were used as raw materials, oxygen was used as an oxidant, and H was 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. 0.18g of xylose, 0.28g of methanol and 0.19g of H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein xylose, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.8wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3.0MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 80 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and procedure as in example 1, the conversion of xylose was 96.8%, and the carbon yield of the liquid-phase product, calculated on the basis of the initial xylose carbon content, was 83.0%, with 75.6% formic acid and 0.5% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), glyoxal 1.2%, glycolaldehyde 1.8%, acetic acid 3.9%; the gas phase product is CO 2 The carbon yield was 10.5%. The conversion of methanol was 34.4%, the carbon yield of formaldehyde was 27.6%, the carbon yield of methylal was 4.6%, and the carbon yield of methyl formate was 0.3%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Example 28
In this example, xylan and methanol were used as raw materials, oxygen was used as an oxidant, and H was added 5 PV 2 Mo 10 O 40 As a catalyst, carbohydrate and methanol are synergistically catalyzed and oxidized to prepare formic acid and formaldehyde. The concerted catalytic oxidation experiment was carried out in a 50mL high temperature high pressure autoclave with magnetic stirring. Mixing 0.16g xylan, 0.28g methanol, 0.19g H 5 PV 2 Mo 10 O 40 And 10mL of deionized water (wherein xylan, methanol and H 5 PV 2 Mo 10 O 40 Relative solvent mass fractions of 1.6wt%, 2.8wt% and 1.9 wt%) were added to the reaction kettle, the reaction kettle was sealed, air in the reaction kettle was replaced with oxygen, and then 3.0MPa oxygen was charged. And (3) putting the reaction kettle into a pre-heated heating sleeve, starting stirring, starting timing when the reaction temperature reaches 90 ℃, taking out the reaction kettle after 24 hours 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.
Using the same analytical conditions and method as in example 1, the conversion of xylan was 99.2%, and the carbon yield of the liquid phase product calculated based on the starting xylan carbon content was 85.6%, with 63.6% formic acid and 0.5% methyl formate (HCOOCH) 3 Here, the yield of-OCH-of HCO-is referred to 3 From methanol), xylose 7.3%, arabinose 3.7%, glyoxal 2.8%, glycolaldehyde 2.2%, acetic acid 5.5%; the gas phase product is CO 2 The carbon yield was 10.2%. The conversion of methanol was 26.8%, the carbon yield of formaldehyde was 21.3%, the carbon yield of methylal was 3.6%, and the carbon yield of methyl formate was 0.3%, based on the initial methanol carbon content (HCOOCH) 3 Here, it means-OCH 3 Yield of HCO-from formic acid).
Claims (5)
1. A method for preparing formic acid and formaldehyde by concerted catalytic oxidation of biomass-based carbohydrates and methanol comprises the following specific steps:
adding carbohydrate, a methanol raw material, a catalyst and a water solvent into a high-pressure reaction kettle, charging oxygen or air, stirring and reacting at a given temperature, cooling to finish the reaction after the reaction time is reached, discharging gas and collecting product gas, filtering and separating liquid and solid in the kettle, and collecting residues and filtrate dissolved with formic acid and formaldehyde;
wherein the carbohydrate raw material in the step is selected from one of glucose, cellobiose, glucan, sucrose, xylose and xylan;
the mass content of the carbohydrate raw material in the water solvent in the step is 0.6-3.0 wt%;
the mass content of the methanol raw material in the water solvent in the step is 0.7wt% -11.2 wt%;
said catalyst in step (ii) is selected from H 5 PV 2 Mo 10 O 40 、H 8 PV 5 Mo 7 O 40 、NaVO 3 –H 2 SO 4 And VOSO 4 –H 2 SO 4 One of (1);
the mass content of the catalyst in the water solvent in the step is 0.5wt% -1.9 wt%;
the initial pressure (or partial pressure) of the oxygen in the step is 2MPa to 5MPa;
the reaction temperature in the step is 80-100 ℃;
the reaction time in the step is 12-60 h.
2. The method according to claim 1, wherein the carbohydrate feedstock is present in the aqueous solvent in an amount of 1.2 to 2.4wt%.
3. The method according to claim 1, wherein the mass content of the methanol raw material in the water solvent is 1.4wt% to 5.6wt%.
4. The process of claim 1 wherein the catalyst is H 5 PV 2 Mo 10 O 40 。
5. The method according to claim 1, wherein the oxidation reaction time is 36 to 60 hours.
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