CN112341415A - Method for preparing 5-hydroxymethyl-2-furancarboxylic acid by photocatalytic oxidation - Google Patents
Method for preparing 5-hydroxymethyl-2-furancarboxylic acid by photocatalytic oxidation Download PDFInfo
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- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 64
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- -1 sodium halide Chemical class 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000013032 photocatalytic reaction Methods 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002699 waste material Substances 0.000 abstract description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 44
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 44
- 239000003054 catalyst Substances 0.000 description 32
- 239000012295 chemical reaction liquid Substances 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for preparing 5-hydroxymethyl-2-furancarboxylic acid by photocatalytic oxidation, which comprises the following steps: dissolving HMF raw material in a solvent, and carrying out a light catalytic reaction in the presence of an oxidant and a photocatalyst to obtain the HMF material; the structural formula of the photocatalyst is as follows: bi24O31X10(OH)a(ii) a Wherein X is halogen and a is a natural number. The invention also provides a photocatalyst for preparing the 5-hydroxymethyl-2-furancarboxylic acid. According to the invention, the HMF is subjected to selective photocatalytic oxidation by using the improved photocatalyst to prepare the HMFCA, so that the danger and waste caused by the traditional oxidation mode are effectively prevented, and more environment-friendly oxygen can be used as an oxygen source, so that the complexity of post-treatment is greatly reduced; the photocatalyst used by the invention introduces a basic group on the basis of a common bismuth photocatalyst so as to better catalyze and oxidize HMF.
Description
Technical Field
The invention belongs to the field of catalyst preparation and application, and particularly relates to synthesis of a basic bismuth-based catalyst and application of the basic bismuth-based catalyst in HMF catalytic oxidation reaction.
Background
For centuries, the petroleum energy industry has contributed greatly to the development of human economy and society, and is still the most widely used energy at present. However, due to the increasing demand for energy caused by the growing population, petroleum, which is a non-renewable resource, is limited and is expected to be exhausted in the next decades, and the greenhouse effect caused by the combustion of a large amount of petroleum also has a great influence on environmental problems. Therefore, it is an urgent matter to find new green and environment-friendly energy sources. Biomass, a globally available, renewable, natural carbon resource, has been used as a feedstock for the production of bio-based chemicals since ancient times and is also expected to be an ideal alternative feedstock for the production of bulk and fine chemicals, with 5-Hydroxymethylfurfural (HMF), levulinic acid and gamma valerolactone being the most critical and widespread intermediates. Among these platform molecules, HMF can be derived from carbohydrates such as biomass-derived sugars, lignin, etc., and has attracted considerable attention in recent years. Various products can be obtained by selective oxidation of HMF, such as 2, 5-Diformylfuran (DFF), 5-formyl-2-furancarboxylic acid (FFCA), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), furandicarboxylic acid (FDCA), which have wide applications in pharmaceutical intermediates, macrocyclic ligands, and polymeric materials.
The oxidation of alcoholic hydroxyl group is a common reaction in organic reaction, the traditional oxidation method usually uses expensive metal catalyst, and the used oxidant is mostly strong oxidant such as hydrogen peroxide, potassium permanganate, nitric acid and the like, so that the reaction process is dangerous, and therefore, the search of a new catalytic oxidation method becomes urgent need of researchers. Since 1972, semiconductor photocatalysis has shown its promising prospects in a variety of fields. Long-term research shows that the photocatalyst can be applied to the thorough mineralization removal of water and gas-phase inorganic and organic pollutants, and can achieve the effect of deep purification on environmental pollution. Photocatalytic reactions are one of the many ways in which light and substances interact, being a fusion of light and catalytic reactions. The band structure of a semiconductor material generally consists of a valence band filled with electrons and having low energy and an empty conduction band having high energy, and a forbidden band exists between the valence band and the conduction band. When irradiated with light having an energy greater than or equal to the forbidden bandwidth, the semiconductor absorbs photon energy, electrons in the valence band are excited to transit to the conduction band, and accordingly holes are generated in the valence band, thereby generating electron-hole pairs inside the semiconductor. Holes generated by irradiating a semiconductor with light have strong electron-gaining ability and thus strong oxidizing property, and generated electrons have strong reducing ability and can undergo a reduction reaction with dissolved oxygen to generate oxygen radicals. The photo-generated electrons and holes can migrate to the surface of the semiconductor particles adsorbed with organic or inorganic substances, combine with oxygen and hydroxyl groups to generate active free radicals, and induce a photocatalytic degradation reaction.
Bismuth-based catalysts have attracted much attention in the recent years, often have a narrow energy band width and excellent photocatalytic performance, and are widely used for photocatalytic water decomposition and degradation of organic and inorganic pollutants. At present, researchers use common photocatalysts such as TiO2 and C3N4 to catalyze the oxidation of HMF, but a catalytic method dominated by a basic bismuth-based catalyst has not been reported in related patents in China.
Disclosure of Invention
The technical problem is as follows: in order to solve the defects of high price, high risk degree and the like of the traditional hydroxymethyl oxidation, the invention provides a method for generating HMFCA by utilizing a catalyst to perform photocatalytic oxidation on HMF and a preparation method of the catalyst, and the catalyst has the advantages of environmental friendliness, easiness in recovery and the like.
The technical scheme is as follows: the technical scheme of the invention is as follows:
a method for preparing 5-hydroxymethyl-2-furancarboxylic acid by photocatalytic oxidation comprises the following steps: dissolving HMF raw material in a solvent, and carrying out a light catalytic reaction in the presence of an oxidant and a photocatalyst to obtain the HMF material; the structural formula of the photocatalyst is as follows: bi24O31X10(OH)a(ii) a Wherein X is halogen and a is a natural number.
Preferably, the preparation method of the photocatalyst comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution for reaction at room temperature, and adding a potassium hydroxide aqueous solution to adjust the pH value to be alkaline; stirring the suspension of the reaction system, and heating at the temperature of 180-220 ℃ for reaction; filtering and washing to obtain the product.
Preferably, the preparation method of the photocatalyst comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution at room temperature for 5-20min to react, and adding a potassium hydroxide aqueous solution to adjust the pH to be alkaline to obtain a white suspension; stirring the suspension of the reaction system for 20-40min, and heating and reacting at the temperature of 180-220 ℃ for 10-14 h; filtering, washing the precipitate with deionized water and ethanol for 3 times, and oven drying.
Preferably, the sodium halide is sodium chloride, sodium bromide or sodium iodide.
Preferably, adding potassium hydroxide aqueous solution to adjust the pH to 9-12; different pH means that the catalyst has different alkalinity and affects the photocatalytic reaction.
Preferably, the solvent is any one of water, acetonitrile, trifluoroacetic acid, methanol and ethanol.
Preferably, the wavelength of the light source used in the photocatalytic reaction is 400-500 nm.
Preferably, in the photocatalytic reaction, the oxidant is any one of oxygen, 30% hydrogen peroxide and TBHP.
Preferably, the reaction temperature in the photocatalytic reaction is 20-70 ℃.
Preferably, after the photocatalytic reaction, the product is obtained by extraction, and the extraction steps are as follows: unreacted HMF starting material was separated from the reaction solution with ethyl acetate.
The invention also provides a photocatalyst (basic bismuth photocatalyst) for preparing 5-hydroxymethyl-2-furancarboxylic acid, and the structural formula of the photocatalyst is as follows: bi24O31X10(OH)a(ii) a Wherein X is halogen and a is a natural number.
The photocatalyst is a bismuth-based photocatalyst with basic hydroxyl, has a porous nano structure and consists of flower-shaped grids with the size of about 2 mm.
Preferably, the preparation method of the photocatalyst comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution for reaction at room temperature, and adding a potassium hydroxide aqueous solution to adjust the pH value to be alkaline; stirring the suspension of the reaction system, and heating at the temperature of 180-220 ℃ for reaction; filtering and washing to obtain the product.
The invention also provides a preparation method of the photocatalyst for preparing 5-hydroxymethyl-2-furancarboxylic acid, which comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution for reaction at room temperature, and adding a potassium hydroxide aqueous solution to adjust the pH value to be alkaline; stirring the suspension of the reaction system, and heating at the temperature of 180-220 ℃ for reaction; filtering and washing to obtain the product.
Has the advantages that: according to the invention, the HMF is subjected to selective photocatalytic oxidation by using the improved photocatalyst to prepare the HMFCA, so that the danger and waste caused by the traditional oxidation mode are effectively prevented, and more environment-friendly oxygen can be used as an oxygen source, so that the complexity of post-treatment is greatly reduced; the photocatalyst used by the invention introduces a basic group on the basis of a common bismuth photocatalyst so as to better catalyze and oxidize HMF.
Specifically, compared with the prior art, the invention has the following advantages:
1. the invention uses the self-made bismuth catalyst to catalyze the oxidation reaction, the raw material of the catalyst is low in price, the preparation is simple, and the catalyst is more suitable for mass production than the traditional noble metal catalyst. And a large number of basic groups are introduced into the catalyst, so that the oxidation reaction can be better promoted.
2. The oxidant used in the method is oxygen, the oxygen is convenient to obtain, the product post-treatment process is simple and convenient, and the method is safer than the hydrogen peroxide or potassium permanganate used in the traditional oxidation method.
3. The reaction environment required by the invention is mild, and is safer and more easily available than the traditional harsh environment with high temperature and high pressure.
Drawings
FIG. 1 is a graph showing the effect of the number of times of using the photocatalyst for preparing 5-hydroxymethyl-2-furancarboxylic acid prepared according to the present invention on the catalytic activity.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1
Preparation of basic bismuth-based photocatalyst: bismuth nitrate pentahydrate and sodium bromide were placed in an aqueous nitric acid solution at room temperature. The mixture was stirred for 10 minutes, then an aqueous potassium hydroxide solution was added dropwise to adjust the pH of the solution to 11 and the resulting white suspension was stirred vigorously for 30 minutes, then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heated at 200 ℃ for 12 hours. The yellow precipitate formed was then collected by filtration, washed 3 times with deionized water and ethanol each, and finally dried in an oven for use.
Example 2
Preparation of basic bismuth-based photocatalyst: bismuth nitrate pentahydrate and sodium chloride were placed in an aqueous nitric acid solution at room temperature. The mixture was stirred for 5 minutes, and then an aqueous solution of potassium hydroxide was added dropwise to adjust the pH of the solution to 12. The resulting white suspension was stirred vigorously for 20 minutes and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heated at 180 ℃ for 14 hours. The yellow precipitate formed was then collected by filtration, washed 3 times with deionized water and ethanol each, and finally dried in an oven for use.
Example 3
Preparation of basic bismuth-based photocatalyst: bismuth nitrate pentahydrate and sodium iodide were placed in an aqueous nitric acid solution at room temperature. The mixture was stirred for 20 minutes, and then an aqueous solution of potassium hydroxide was added dropwise to adjust the pH of the solution to 9. The resulting white suspension was stirred vigorously for 40 minutes and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and heated at 220 ℃ for 10 hours. The yellow precipitate formed was then collected by filtration, washed 3 times with deionized water and ethanol each, and finally dried in an oven for use.
Example 4
Weighing 12.6mg of HMF and 5.1mg of catalyst in turn in a reaction tube with a glass throttle, vacuumizing the reaction tube, introducing oxygen, adding 1ml of acetonitrile to dissolve the HMF, putting the reaction tube into an oil bath pan with the preset temperature of 60 ℃, setting the stirring speed of the experiment to be 500rpm, and reacting for 24 hours under the irradiation of blue light.
After the reaction is finished, cooling the reaction tube to room temperature, recovering the catalyst by filtering, taking a small amount of reaction liquid, diluting the reaction liquid by a certain multiple by using deionized water, and measuring the contents of HMF and HMFCA by using HPLC (high performance liquid chromatography), wherein the conversion rate of HMF is 56% and the selectivity of HMFCA is 46%. And extracting and separating unreacted HMF from the residual reaction liquid, and then performing rotary evaporation to obtain the product HMFCA.
Example 5
Weighing 12.8mg of HMF, 5.3mg of catalyst and 0.4ml of 30% hydrogen peroxide in turn into a reaction tube with a glass throttle, adding 1ml of acetonitrile to dissolve the HMF, then placing the reaction tube into an oil bath pan which reaches the preset temperature of 50 ℃, setting the experimental stirring speed to be 500rpm, and reacting for 24 hours under the irradiation of blue light.
After the reaction is finished, cooling the reaction tube to room temperature, recovering the catalyst by filtering, taking a small amount of reaction liquid, diluting the reaction liquid by a certain multiple by using deionized water, and measuring the contents of HMF and HMFCA by using HPLC (high performance liquid chromatography), wherein the conversion rate of the HMF is 70% and the selectivity of the HMFCA is 52%. And extracting and separating unreacted HMF from the residual reaction liquid, and then performing rotary evaporation to obtain the product HMFCA.
Example 6
Weighing 12.2mg of HMF, 4.9mg of catalyst and 0.4ml of TBHP in turn in a reaction tube with a glass throttle, adding 1ml of acetonitrile to dissolve the HMF, then placing the reaction tube in an oil bath kettle which reaches the preset temperature of 70 ℃, setting the stirring speed of the experiment to be 500rpm, and reacting for 24 hours under the irradiation of blue light.
After the reaction is finished, cooling the reaction tube to room temperature, recovering the catalyst by filtering, taking a small amount of reaction liquid, diluting the reaction liquid by a certain multiple by using deionized water, and measuring the contents of HMF and HMFCA by using HPLC (high performance liquid chromatography), wherein the conversion rate of HMF is 82% and the selectivity of HMFCA is 48%. And extracting and separating unreacted HMF from the residual reaction liquid, and then performing rotary evaporation to obtain the product HMFCA.
Example 7
Weighing 12.6mg of HMF and 5.2mg of catalyst in turn in a reaction tube with a glass throttle, vacuumizing the reaction tube, introducing oxygen, adding 1ml of water to dissolve the HMF, putting the reaction tube into an oil bath pan with the preset temperature of 60 ℃, setting the experimental stirring speed to be 500rpm, and reacting for 24 hours under the irradiation of blue light.
After the reaction is finished, cooling the reaction tube to room temperature, recovering the catalyst by filtering, taking a small amount of reaction liquid, diluting the reaction liquid by a certain multiple by using deionized water, and measuring the contents of HMF and HMFCA by using HPLC (high performance liquid chromatography), wherein the conversion rate of HMF is 54% and the selectivity of HMFCA is 34%. And extracting and separating unreacted HMF from the residual reaction liquid, and then performing rotary evaporation to obtain the product HMFCA.
Example 8
Weighing 12.9mg of HMF and 5.4mg of catalyst in turn in a reaction tube with a glass throttle, vacuumizing the reaction tube, introducing oxygen, adding 1ml of trifluoroacetic acid to dissolve the HMF, putting the reaction tube into an oil bath pan with the preset temperature of 60 ℃, setting the stirring speed of the experiment to be 500rpm, and reacting for 24 hours under the irradiation of blue light.
After the reaction is finished, cooling the reaction tube to room temperature, recovering the catalyst by filtering, taking a small amount of reaction liquid, diluting the reaction liquid by a certain multiple by using deionized water, and measuring the contents of HMF and HMFCA by using HPLC (high performance liquid chromatography), wherein the conversion rate of the HMF is 55% and the selectivity of the HMFCA is 46%. And extracting and separating unreacted HMF from the residual reaction liquid, and then performing rotary evaporation to obtain the product HMFCA.
Example 9
Weighing 12.6mg of HMF and 5.3mg of catalyst in turn in a reaction tube with a glass throttle, vacuumizing the reaction tube, introducing oxygen, adding 1ml of acetonitrile to dissolve the HMF, putting the reaction tube into an oil bath pan with the preset temperature of 30 ℃, setting the stirring speed of the experiment to be 500rpm, and reacting for 24 hours under the irradiation of blue light.
After the reaction is finished, cooling the reaction tube to room temperature, recovering the catalyst by filtering, taking a small amount of reaction liquid, diluting the reaction liquid by a certain multiple by using deionized water, and measuring the contents of HMF and HMFCA by using HPLC (high performance liquid chromatography), wherein the conversion rate of the HMF is 38% and the selectivity of the HMFCA is 54%. And extracting and separating unreacted HMF from the residual reaction liquid, and then performing rotary evaporation to obtain the product HMFCA.
Example 10
The influence of the using times of the basic bismuth-based catalyst on the catalytic activity.
The catalyst filtered in example 6 was washed several times with water and ethanol, and then placed in a vacuum oven at 100 ℃ for drying for 12 hours, before being used for the next cycle of reaction. This cycle was used 5 times, and the results are shown in fig. 1 for each cycle comparing the HMF conversion and HMFCA selectivity calculations.
The results show that: when the circulation times exceed three times, the conversion rate of HMF and the selectivity of HMFCA are obviously reduced, because a plurality of times of circulation use can adsorb and accumulate some byproducts in the pore channels of the catalyst, and a plurality of times of washing can also destroy basic groups contained in the catalyst, so that the pH value of the catalyst gradually tends to be neutral.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for preparing 5-hydroxymethyl-2-furancarboxylic acid by photocatalytic oxidation is characterized in that: the method comprises the following steps: dissolving HMF raw material in a solvent, and carrying out a light catalytic reaction in the presence of an oxidant and a photocatalyst to obtain the HMF material; the structural formula of the photocatalyst is as follows: bi24O31X10(OH)a(ii) a Wherein X is halogen and a is a natural number.
2. The photocatalytic oxidation process for preparing 5-hydroxymethyl-2-furancarboxylic acid according to claim 1, wherein: the preparation method of the photocatalyst comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution for reaction at room temperature, and adding a potassium hydroxide aqueous solution to adjust the pH value to be alkaline; stirring the suspension of the reaction system, and heating at the temperature of 180-220 ℃ for reaction; filtering and washing to obtain the product.
3. The photocatalytic oxidation process for preparing 5-hydroxymethyl-2-furancarboxylic acid according to claim 2, wherein: the preparation method of the photocatalyst comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution at room temperature for 5-20min to react, and adding a potassium hydroxide aqueous solution to adjust the pH to be alkaline to obtain a white suspension; stirring the suspension of the reaction system for 20-40min, and heating and reacting at the temperature of 180-220 ℃ for 10-14 h; filtering, washing the precipitate with deionized water and ethanol for 3 times, and oven drying.
4. The process for the photocatalytic oxidation of 5-hydroxymethyl-2-furancarboxylic acid according to claim 2 or 3, wherein: the sodium halide is sodium chloride, sodium bromide or sodium iodide; aqueous potassium hydroxide solution was added to adjust the pH to 9 to 12.
5. The photocatalytic oxidation process for preparing 5-hydroxymethyl-2-furancarboxylic acid according to claim 1, wherein: the solvent is any one of water, acetonitrile, trifluoroacetic acid, methanol and ethanol; the wavelength of a light source used in the photocatalytic reaction is 400-500 nm; in the photocatalytic reaction, the oxidant is any one of oxygen, 30% hydrogen peroxide and TBHP.
6. The photocatalytic oxidation process for preparing 5-hydroxymethyl-2-furancarboxylic acid according to claim 1, wherein: in the photocatalytic reaction, the reaction temperature is 20-70 ℃.
7. The photocatalytic oxidation process for preparing 5-hydroxymethyl-2-furancarboxylic acid according to claim 1, wherein: after the photocatalytic reaction, extracting to obtain a product, wherein the extraction step is as follows: unreacted HMF starting material was separated from the reaction solution with ethyl acetate.
8. A photocatalyst for preparing 5-hydroxymethyl-2-furancarboxylic acid, which is characterized in that: the structural formula of the photocatalyst is as follows: bi24O31X10(OH)a(ii) a Wherein X is halogen and a is a natural number.
9. The photocatalyst for preparing 5-hydroxymethyl-2-furancarboxylic acid according to claim 9, wherein: the preparation method of the photocatalyst comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution for reaction at room temperature, and adding a potassium hydroxide aqueous solution to adjust the pH value to be alkaline; stirring the suspension of the reaction system, and heating at the temperature of 180-220 ℃ for reaction; filtering and washing to obtain the product.
10. A preparation method of a photocatalyst for preparing 5-hydroxymethyl-2-furancarboxylic acid is characterized by comprising the following steps: the method comprises the following steps: stirring bismuth nitrate pentahydrate and sodium halide in a nitric acid solution for reaction at room temperature, and adding a potassium hydroxide aqueous solution to adjust the pH value to be alkaline; stirring the suspension of the reaction system, and heating at the temperature of 180-220 ℃ for reaction; filtering and washing to obtain the product.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103265076A (en) * | 2013-06-07 | 2013-08-28 | 南京信息工程大学 | Preparation method of sheet-like bismuth oxychloride photocatalyst |
CN106565647A (en) * | 2016-10-29 | 2017-04-19 | 华东理工大学 | Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural |
CN108568303A (en) * | 2018-04-10 | 2018-09-25 | 青岛农业大学 | A kind of TiO2/Bi24O31Br10The preparation method of/BiOBr composite photocatalyst materials |
CN110102350A (en) * | 2019-06-10 | 2019-08-09 | 湖南师范大学 | Catalyst and its preparation method and application for oxidative synthesis 2,5- furandicarboxylic acid |
CN111250114A (en) * | 2020-02-04 | 2020-06-09 | 江苏大学 | Superfine bismuth-rich bismuth oxybromide nanotube prepared by hydrothermal method and application thereof |
-
2020
- 2020-10-28 CN CN202011169416.8A patent/CN112341415A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103265076A (en) * | 2013-06-07 | 2013-08-28 | 南京信息工程大学 | Preparation method of sheet-like bismuth oxychloride photocatalyst |
CN106565647A (en) * | 2016-10-29 | 2017-04-19 | 华东理工大学 | Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural |
CN108568303A (en) * | 2018-04-10 | 2018-09-25 | 青岛农业大学 | A kind of TiO2/Bi24O31Br10The preparation method of/BiOBr composite photocatalyst materials |
CN110102350A (en) * | 2019-06-10 | 2019-08-09 | 湖南师范大学 | Catalyst and its preparation method and application for oxidative synthesis 2,5- furandicarboxylic acid |
CN111250114A (en) * | 2020-02-04 | 2020-06-09 | 江苏大学 | Superfine bismuth-rich bismuth oxybromide nanotube prepared by hydrothermal method and application thereof |
Non-Patent Citations (1)
Title |
---|
YITAO DAI ET AL.: "Solid Base Bi24O31Br10(OH)δ with Active Lattice Oxygen for the Efficient Photo-Oxidation of Primary Alcohols to Aldehydes", 《ANGEWANDTE CHEMIE》 * |
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