CN112812000B - Preparation method of maleic acid - Google Patents
Preparation method of maleic acid Download PDFInfo
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- CN112812000B CN112812000B CN202011589488.8A CN202011589488A CN112812000B CN 112812000 B CN112812000 B CN 112812000B CN 202011589488 A CN202011589488 A CN 202011589488A CN 112812000 B CN112812000 B CN 112812000B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a preparation method of maleic acid, which comprises the step of carrying out catalytic oxidation reaction on furfural under the action of a P-doped porous carbon solid acid catalyst to prepare the maleic acid.
Description
Technical Field
The invention relates to the fields of biomass utilization technology and renewable energy, in particular to a preparation method of maleic acid.
Background
With the rapid development of society and the large application of petrochemicals, non-renewable petrochemical resources are increasingly in tension. The development of novel renewable resources to replace non-renewable petrochemical resources by using new technologies and new processes becomes an urgent problem to be solved.
The biomass resource has rich reserves, is a green renewable resource and has great potential utilization value. The development and utilization of biomass resources gradually replace petrochemical resources, and become a main energy strategy in most countries.
Maleic acid is an important raw material in multiple fields of chemical industry, is one of the future 12 important chemical raw materials listed in the united states energy agency, has been widely applied to resins, medicines, plasticizers, copolymers and agrochemicals, and can also be used as an intermediate of other chemical products.
Currently, maleic acid is produced primarily by hydrolysis of fossil fuel maleic anhydride. Maleic anhydride is mainly obtained by oxidation of benzene, butane or butene, which is heavily dependent on traditional fossil resources. Therefore, the production of maleic acid from maleic anhydride not only puts pressure on the environment, but also further deteriorates national energy safety. Therefore, the maleic acid synthesized by using renewable biomass resources or biomass platform compounds as raw materials not only can reduce the dependence on the traditional fossil energy, but also can improve the natural environment, and has great attraction.
The furfural has wide sources, is mainly prepared from renewable biomass serving as a raw material through acid catalytic hydrolysis, and has large-scale industrial production capacity.
At present, although many researches on the preparation of maleic acid by using furfural as a raw material have been made, various problems such as low raw material conversion rate, low product yield, difficult catalyst recovery and the like generally exist in the researches.
Therefore, there is a need for a process for the preparation of maleic acid to at least partially solve the above problems.
Disclosure of Invention
In this summary, concepts in a simplified form are introduced that are further described in the detailed description. This summary of the invention is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
In order to at least partially solve the above problems, the present invention provides a method for producing maleic acid, which comprises subjecting furfural to a catalytic oxidation reaction under the action of a P-doped porous carbon solid acid catalyst to produce maleic acid.
Preferably, the preparation method comprises: reacting furfural with an oxidant in the presence of a solvent and the catalyst, wherein the reaction temperature is 40-120 ℃; the reaction time is 1-36 h.
Preferably, the reaction temperature is 50 to 80 ℃.
Preferably, the reaction temperature is 60 ℃.
Preferably, the first and second electrodes are formed of a metal, the reaction time is 9-12 h.
The reaction can be carried out under normal pressure or under elevated pressure.
Preferably, the solvent is water or a mixture of water and an organic solvent.
Preferably, the organic solvent is one or more of acetonitrile, N Dimethylformamide (DMF), gamma Valerolactone (GVL), gamma Butyrolactone (GBL).
Preferably, the oxidizing agent is hydrogen peroxide.
Preferably, the mass ratio of the catalyst to the furfural is 0.2.
Preferably, the mass ratio of the catalyst to the furfural is 0.6.
Preferably, the mass ratio of the catalyst to the furfural is 0.6.
Preferably, the molar ratio of hydrogen peroxide to furfural is 3:1-16.
Preferably, the molar ratio of hydrogen peroxide to furfural is 6:1-10.
Preferably, the molar ratio of hydrogen peroxide to furfural is 8:1.
Preferably, the solvent is a mixture of water and gamma valerolactone.
Preferably, the volume ratio of water to gamma valerolactone is 1:1-1:5.
Preferably, the volume ratio of water to gamma-valerolactone is 1:1-1.
Preferably, the catalyst is made by calcining a P-containing biomacromolecule or biomass feedstock, or by calcining a phosphoric acid-treated biomass.
Preferably, the P-containing biomacromolecule or biomass feedstock comprises phytic acid and/or nucleic acid.
Preferably, the P-containing biomacromolecule or biomass feedstock is phytic acid.
Preferably, the biomass treated with phosphoric acid comprises at least one of monosaccharides, polysaccharides, lignocelluloses, hemicelluloses, lignin, cellulose.
Preferably, the roasting temperature is 400-1500 ℃; and is carried out under an inert atmosphere.
Preferably, the temperature of the roasting is 400-900 ℃.
Preferably, the temperature of the calcination is 600 ℃.
According to the preparation method of the maleic acid, the furfural is used as the raw material, the raw material is cheap and easy to obtain and can be regenerated, the dependence on the traditional fossil energy is reduced, and the preparation method is beneficial to the improvement of the environment and the sustainable development of resources. The P-doped porous carbon solid acid catalyst can be derived from biomass waste or biomacromolecules, the preparation raw materials are cheap and easily available, the preparation process is simple and environment-friendly, and is harmless to the environment and resources, the catalytic activity is high, the selectivity is strong, the stability is good, the catalyst is easy to recycle, and the recovery process is simple. The invention can use water or the mixture of water and organic solvent as reaction solvent, which is green and environment-friendly; the method has mild reaction conditions, can obtain higher yield of maleic acid at 50-80 ℃, the conversion rate of furfural can reach 100% at 60 ℃, and the yield of maleic acid can reach 74.1% to the maximum; the reaction process is simple, the product is easy to separate, and the reaction system can be recycled, so that the method has potential industrial application value.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
In the following description, a detailed description will be given in order to thoroughly understand the present invention. It is to be understood that these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of these exemplary embodiments to those skilled in the art. It is apparent that the implementation of the embodiments of the invention is not limited to the specific details familiar to those skilled in the art. The following detailed description of the preferred embodiments of the invention, however, the invention is capable of other embodiments in addition to those detailed.
It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular is intended to include the plural unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated elements, conditions, features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other elements, conditions, features, integers, steps, operations, elements, components, and/or groups thereof.
The invention provides a preparation method of maleic acid, which is characterized in that furfural is subjected to catalytic oxidation reaction under the action of a P-doped porous carbon solid acid catalyst to prepare the maleic acid.
Specifically, the above reaction needs to be carried out in a solvent, which is preferably water or a mixture of water and an organic solvent. Among them, the organic solvent is preferably at least one of acetonitrile, N Dimethylformamide (DMF), gamma-valerolactone (GVL) and gamma-butyrolactone (GBL).
Further, the solvent is preferably a mixture of water and gamma-valerolactone, and the volume ratio of the water to the gamma-valerolactone is 1:1-1:5, preferably 1:1-1.
The catalytic oxidation reaction in the above preparation method requires consumption of an oxidizing agent, preferably hydrogen peroxide.
The mass ratio of the catalyst to the furfural can be 0.2. The molar ratio of hydrogen peroxide to furfural can be 3:1-16, preferably 6:1-10.
The reaction temperature of the catalytic oxidation reaction may be 40 to 120 ℃, preferably 50 to 80 ℃. The reaction time may be 1 to 36 hours, preferably 9 to 12 hours.
And, the P-doped porous carbon solid acid catalyst is preferably prepared by roasting a P-containing biomacromolecule or biomass raw material, or by roasting phosphoric acid-treated biomass. The calcination is preferably carried out under an inert atmosphere, and the temperature of the calcination may be 400 to 1500 ℃, preferably 400 to 1000 ℃.
The P-containing biomacromolecule or biomass feedstock may include phytic acid and/or nucleic acids. The biomass treated with phosphoric acid may comprise at least one of monosaccharides, polysaccharides, lignocellulose, hemicellulose, lignin, cellulose.
Examples
Example 1
A reactor (which may be an autoclave) having a capacity of 70mL was charged with 0.24g of furfural (2.5 mmol of furfural), 2.3g of 30% by mass of H 2 O 2 Solution (20 mmol of H 2 O 2 ) 0.15g of P-C-500 catalyst (obtained by calcining phytic acid at 500 ℃ for 4 hours under an argon atmosphere), and 10mL of water (solvent).
After the completion of the charge, the contents of the reactor were heated to 60 ℃ with magnetic stirring at 600r/min and reacted for 9h with stirring.
After the reaction is finished, cooling to room temperature, filtering at normal temperature and normal pressure, and diluting the obtained reaction liquid with water to obtain a product.
And analyzing the maleic acid content and the conversion rate of the furfural in the product by using high performance liquid chromatography. The chromatographic conditions were as follows:
C 18 a reverse phase chromatography column;
mobile phase: acetonitrile and 0.1% volume fraction aqueous sulfuric acid, the volume ratio of the two is 5:95;
flow rate: 0.3mL/min;
column temperature: 30 ℃;
a detector: UA;
detection wavelength: 240nm.
The conversion of furfural was 96.6% and the selectivity of maleic acid was 44.4% for this example as determined by HPLC (High Performance Liquid Chromatography).
Example 2
The catalyst in the embodiment is P-C-600, which is obtained by roasting phytic acid at 600 ℃ for 4 hours in an argon atmosphere. The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was determined by HPLC to be 92.9% and the selectivity to maleic acid was 69.0% for this example.
Example 3
The catalyst in the embodiment is P-C-700, which is obtained by roasting phytic acid at 700 ℃ for 4 hours in an argon atmosphere. The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was 72.5% and the selectivity to maleic acid was 59.0% for this example as determined by HPLC.
Example 4
The catalyst in the embodiment is P-C-800, which is obtained by roasting phytic acid at 800 ℃ for 4 hours in an argon atmosphere. The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was 69.3% and the selectivity to maleic acid was 57.0% for this example as determined by HPLC.
Example 5
The catalyst in this example was PC-400. The preparation method comprises the following steps: 5g of starch was dissolved in 30mL of water, 10g of phosphoric acid was added, and the mixture was treated for 5 hours and then filtered. Then, the mixture was calcined at 400 ℃ for 4 hours under an argon atmosphere.
The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was 80.1% and the selectivity to maleic acid was 17.8% for this example as determined by HPLC.
Example 6
The catalyst in this example was PC-500. The preparation method comprises the following steps: 5g of starch was dissolved in 30mL of water, 10g of phosphoric acid was added, and the mixture was treated for 5 hours and then filtered. Then, the mixture was calcined at 500 ℃ for 4 hours under an argon atmosphere.
The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was determined to be 91.5% and the selectivity to maleic acid was 32.2% by HPLC for this example.
Example 7
The catalyst in this example was PC-600. The preparation method comprises the following steps: 5g of starch was dissolved in 30mL of water, 10g of phosphoric acid was added, and the mixture was treated for 5 hours and then filtered. Then, the mixture was calcined at 600 ℃ for 4 hours under an argon atmosphere.
The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was 99.6% and the selectivity to maleic acid was 41.6% for this example as determined by HPLC.
Example 8
The catalyst in this example was PC-700. The preparation method comprises the following steps: 5g of starch was dissolved in 30mL of water, 10g of phosphoric acid was added, and the mixture was treated for 5 hours and then filtered. Then, the mixture is roasted for 4 hours at the temperature of 700 ℃ under the argon atmosphere.
The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was 99.9% and the selectivity to maleic acid was 47.7% for this example as determined by HPLC.
Example 9
The catalyst in this example was PC-800. The preparation method comprises the following steps: 5g of starch was dissolved in 30mL of water, 10g of phosphoric acid was added, and the mixture was treated for 5 hours and then filtered. Then, the mixture is roasted for 4 hours at the temperature of 800 ℃ under the argon atmosphere.
The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was determined by HPLC to be 92.5% and the selectivity to maleic acid was 54.5% for this example.
Example 10
The catalyst in this example was PC-900. The preparation method comprises the following steps: 5g of starch was dissolved in 30mL of water, 10g of phosphoric acid was added, and the mixture was treated for 5 hours and then filtered. Then, the mixture is roasted for 4 hours at the temperature of 900 ℃ under the argon atmosphere.
The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was 89.3% and the selectivity to maleic acid was 51.5% for this example as determined by HPLC.
Example 11
The catalyst in this example was PC 2 -800. The preparation method comprises the following steps: 20g of corn stalks (which may be pulverized), 50mL of water and 40g of phosphoric acid were reacted for 5 hours, filtered, and then calcined at 800 ℃ for 4 hours under an argon atmosphere.
The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The furfural conversion was determined to be 79.2% and the selectivity to maleic acid was 43.1% by HPLC for this example.
Example 12
The catalyst in this example was P-C-600, and the amount added was 0.15g. The catalyst was the same as in example 2.
The steps and conditions were the same as in example 1 except that the reaction temperature for catalytic oxidation was 100 ℃ and are not described herein again.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 63.5% by HPLC for this example.
Example 13
The catalyst in this example was P-C-600, and the amount added was 0.2g. The catalyst was the same as in example 2.
The steps and conditions were the same as in example 1 except that the reaction time for catalytic oxidation was 12 hours, and thus, detailed description thereof is omitted.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 69% by HPLC for this example.
Example 14
A reactor (which may be an autoclave) having a capacity of 70mL was charged with 0.24g of furfural (2.5 mmol of furfural), 2.3g of 30% by mass of H 2 O 2 Solution (20 mmol of H 2 O 2 ) 0.2g of P-C-600 catalyst (obtained by calcining phytic acid at 600 ℃ C. For 4h under argon atmosphere), and 10mL of a mixture of water and gamma-valerolactone (i.e., a solvent comprising 5mL of water and 5mL of gamma-valerolactone).
After the completion of the charge, the contents of the reactor were heated to 60 ℃ with magnetic stirring at 600r/min and reacted for 12h with stirring.
After the reaction is finished, cooling to room temperature, filtering at normal temperature and normal pressure, and diluting the obtained reaction liquid with water to obtain a product.
And analyzing the maleic acid content and the conversion rate of the furfural in the product by using high performance liquid chromatography. The chromatographic conditions were as follows:
C 18 a reverse phase chromatography column;
mobile phase: acetonitrile and 0.1% volume fraction aqueous sulfuric acid, the volume ratio of the two is 5:95;
flow rate: 0.3mL/min;
column temperature: 30 ℃;
a detector: UA;
detection wavelength: 240nm.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 74.1% by HPLC for this example.
Example 15
The solvent in this example was a mixture of water and gamma valerolactone, 5mL of water was added, and 7.5mL of gamma valerolactone was added.
The rest of the steps and conditions are the same as those in example 14, and are not described herein again.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 72.7% by HPLC for this example.
Example 16
The solvent in this example was a mixture of water and γ -butyrolactone, 5mL of water was added, and 5mL of γ -butyrolactone was added.
The rest of the steps and conditions are the same as those in example 14, and are not described herein again.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 66.4% by HPLC for this example.
Example 17
The steps and conditions in this example are the same as those in example 14 except that the reaction time of the catalytic oxidation is 36 hours, and are not repeated herein.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 72.1% by HPLC for this example.
Example 18
The steps and conditions in this example are the same as those in example 14 except that the reaction time of the catalytic oxidation is 2 hours, and are not described again.
The conversion of furfural was determined to be 100% and the selectivity to maleic acid was 21.7% by HPLC for this example.
Example 19
The catalyst in this example was P-C-600, and the amount added was 0.05g. The catalyst was the same as in example 2.
The rest of the steps and conditions are the same as those in example 14, and are not described herein again.
The furfural conversion was 80% and the selectivity to maleic acid was 41.7% for this example as determined by HPLC.
Example 20
The catalyst in this example was P-C-600, and the amount added was 0.5g. The catalyst was the same as in example 2.
The rest of the steps and conditions are the same as those in example 14, and are not described herein again.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 73.1% by HPLC for this example.
Example 21
In this example, 30% of H is removed 2 O 2 The amount of the solution added was 1g, but the same as in example 14 was used, and the description thereof was omitted.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 24.1% by HPLC for this example.
Example 22
In this example, 30% of H is removed 2 O 2 The same procedure as in example 14 was repeated except that the amount of the solution added was 4.5g, and details thereof were not repeated.
The furfural conversion was determined to be 100% and the selectivity to maleic acid was 71.9% by HPLC for this example.
Comparative example 1
No catalyst was added in this example. The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The comparative example was determined by HPLC to have a furfural conversion of 30.1% and a maleic acid selectivity of 11.0%.
Comparative example 2
The catalyst in this example was C-600, which was obtained by calcining glucose at 600 ℃ for 4h under an argon atmosphere. The rest of the steps and conditions are the same as those in example 1, and are not described herein again.
The comparative example was determined by HPLC to have a furfural conversion of 51.5% and a maleic acid selectivity of 26.0%.
The results of examples 1 to 22 and comparative examples 1 to 2 are shown in the following table.
TABLE 1 test results of examples and comparative examples
The P-C-600 catalyst was subjected to the repeated use test, and the experiment was carried out as described in example 13. After completion of the reaction, the catalyst was recovered by centrifugation, washed well with 75% ethanol, and dried overnight in an air oven at 120 ℃. The experiment according to the method described in example 13 was repeated using the above recovered catalyst (in order to avoid the effect of catalyst loss, the amount of other components was reduced in equal proportion to the amount of the current catalyst in each repetition of the experiment) until the above catalyst was reused 6 times.
The conversion of furfural remained at 100% and the yield of maleic acid was reduced from the initial 69% to 52% after 6 reuses of the P-C-600 catalyst as determined by HPLC.
The PC-800 catalyst (catalyst in example 9) was subjected to the repeated use test under the same experimental conditions as in example 9 except that the added amount thereof was 0.2g. After completion of the reaction, the catalyst was recovered by centrifugation, washed well with 75% ethanol, and dried overnight in an air oven at 120 ℃. The experiment as described in example 9 was repeated using the above recovered catalyst (in order to avoid the influence of catalyst loss, the amount of other components was reduced in equal proportion to the amount of the current catalyst in each repetition of the experiment) until the above catalyst was reused 6 times.
The conversion of furfural remained at 100% and the yield of maleic acid decreased from the initial 59% to 47.5% after 6 reuses of the PC-800 catalyst as determined by HPLC.
The repeated use tests of the two catalysts show that the P-doped porous carbon solid acid catalyst has good stability and can be repeatedly used for many times.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Features described herein in one embodiment may be applied to another embodiment, either alone or in combination with other features, unless the feature is otherwise inapplicable or otherwise stated in the other embodiment.
The present invention has been illustrated by the above embodiments, but it should be understood that the above embodiments are for illustrative and descriptive purposes only and are not intended to limit the invention to the scope of the described embodiments. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications may be made in accordance with the teachings of the present invention, which variations and modifications are within the scope of the present invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of maleic acid is characterized by comprising the steps of carrying out catalytic oxidation reaction on furfural under the action of a P-doped porous carbon solid acid catalyst to prepare maleic acid, wherein the furfural and an oxidant react in the presence of a solvent and the catalyst, the reaction temperature is 40-120 ℃, the reaction time is 1-36 h, the solvent is water or a mixture of water and an organic solvent, the organic solvent is one or more of acetonitrile, N-dimethylformamide, gamma-valerolactone and gamma-butyrolactone, and the oxidant is hydrogen peroxide;
the catalyst is prepared by roasting a P-containing biomass raw material at the temperature of 400-1500 ℃ in an inert atmosphere, wherein the P-containing biomass raw material is selected from phytic acid; or
The catalyst is prepared by roasting phosphoric acid-treated biomass at 400-1500 ℃ in an inert atmosphere, wherein the phosphoric acid-treated biomass is selected from at least one of lignocellulose, hemicellulose, lignin and cellulose.
2. The production method according to claim 1,
the reaction temperature is 50-80 ℃; the reaction time is 9-12 h.
3. The production method according to any one of claims 1 to 2, wherein the mass ratio of the catalyst to the furfural is from 0.2.
4. The preparation method according to claim 3, wherein the mass ratio of the catalyst to the furfural is 0.6.
5. The process of any one of claims 1-2, wherein the molar ratio of oxidant to furfural is 3:1-16.
6. The method of claim 5, wherein the molar ratio of oxidant to furfural is 6:1-10.
7. The method of claim 1, wherein the solvent is a mixture of water and gamma valerolactone.
8. The method of claim 7, wherein the volume ratio of water to gamma valerolactone is 1:1-1:5.
9. The method of claim 8, wherein the volume ratio of water to gamma valerolactone is 1:1-1.
10. The method of claim 1, wherein the firing temperature is 400 to 900 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011589488.8A CN112812000B (en) | 2020-12-29 | 2020-12-29 | Preparation method of maleic acid |
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| CN202011589488.8A CN112812000B (en) | 2020-12-29 | 2020-12-29 | Preparation method of maleic acid |
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| CN112812000A CN112812000A (en) | 2021-05-18 |
| CN112812000B true CN112812000B (en) | 2023-04-07 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105111170A (en) * | 2015-09-14 | 2015-12-02 | 中国科学技术大学 | Preparation method for furan compound |
| CN109331847A (en) * | 2018-11-16 | 2019-02-15 | 合肥能源研究院 | A kind of catalysis oxidation furfural prepares catalyst and its application of maleic acid |
| CN109395760A (en) * | 2018-11-16 | 2019-03-01 | 合肥能源研究院 | Catalysis oxidation furfural prepares catalyst of maleic acid and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111170A (en) * | 2015-09-14 | 2015-12-02 | 中国科学技术大学 | Preparation method for furan compound |
| CN109331847A (en) * | 2018-11-16 | 2019-02-15 | 合肥能源研究院 | A kind of catalysis oxidation furfural prepares catalyst and its application of maleic acid |
| CN109395760A (en) * | 2018-11-16 | 2019-03-01 | 合肥能源研究院 | Catalysis oxidation furfural prepares catalyst of maleic acid and its preparation method and application |
Non-Patent Citations (1)
| Title |
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| 李谦.第一节 多糖.《生物化学》.中国医药科技出版社,2019,(第4版),第86-87页. * |
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