CN115806537A - Method for preparing furoic acid - Google Patents
Method for preparing furoic acid Download PDFInfo
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- CN115806537A CN115806537A CN202111069255.XA CN202111069255A CN115806537A CN 115806537 A CN115806537 A CN 115806537A CN 202111069255 A CN202111069255 A CN 202111069255A CN 115806537 A CN115806537 A CN 115806537A
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- noble metal
- bismuth
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- activated carbon
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000002253 acid Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 51
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 49
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 48
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 23
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 13
- 229960000583 acetic acid Drugs 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910001451 bismuth ion Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 furoate ester Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
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Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing furoic acid from furfural, which comprises the following steps: reacting furfural with oxygen in an aqueous solution in the presence of an oxidation catalyst to obtain the furoic acid; wherein the oxidation catalyst is a supported catalyst comprising bismuth and a noble metal. The invention catalyzes furfural to prepare furoic acid by a catalytic oxidation method, the adopted catalyst can realize the high-efficiency conversion of furfural under mild conditions to obtain the high-selectivity furoic acid, and the operation method is simple.
Description
Technical Field
The invention relates to the field of preparation of oxygen-containing compounds, and in particular relates to a method for preparing furoic acid.
Background
At present, fuels and chemicals needed by the society are mainly derived from fossil fuels, but the increase of the cost of the fossil fuels, the reduction of the supply amount and the influence on the environment lead people to generate wide interest in sustainable alternative energy and chemical raw materials, and the biomass resources are utilized to prepare high molecular materials and bulk chemicals to replace petroleum resources, thereby having important significance. Furoic acid (also known as 2-furancarboxylic acid) is used as an organic synthesis intermediate to be converted into derivatives such as ester, acyl chloride, anhydride, amide and the like, and is widely used as an intermediate for paint additives, medicines, perfumes and the like. Furoic acid is used in synthesizing methyl furan, furoamide, furoate ester and salt. In the plastics industry, for plasticizers, thermosetting resins, etc.; are used as preservatives in the food industry. Therefore, the development of a green synthetic method of the bio-based furoic acid has important application value and biomass sustainable utilization significance.
Furoic acid can be prepared by oxidizing furfural through three modes of Cannizzaro reaction (Cannizzaro), an oxidant oxidation method and a catalytic oxidation method, wherein the Cannizzaro method is characterized in that furfural is subjected to disproportionation reaction under a strong alkali condition to generate the same amount of furoic acid and furfuryl alcohol, and the prior furfuryl alcohol preparation process is mature, so the utilization rate of raw materials adopting the method is low; the oxidant method usually adopts potassium permanganate, hydrogen peroxide and the like as oxidants, and certain corrosion or potential safety hazards exist; the catalytic oxidation method adopts molecular oxygen as an oxidant and a metal compound as a catalyst, so that the reaction process is more green and efficient, and is more suitable for industrial production. However, in the prior art, an alkaline compound is often required to be added, furoic acid is salified in an alkaline environment, and a product is obtained after acidification, for example: CN 109485624A discloses a method for preparing furoic acid by furfural oxidation, which adopts a catalyst to catalyze furfural in a sodium hydroxide alkaline solution to synthesize furoic acid, however, the product needs to be acidified by concentrated hydrochloric acid, and the problems of corrosion and waste water and waste residue exist.
Therefore, it is desirable to provide a novel method for preparing furoic acid to solve the above problems in the prior art.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provide a method for preparing furoic acid by selective oxidation of furfural, which adopts a catalyst with high activity, high product yield, environment-friendly reaction process and easy product separation, and solves the problems in the traditional furoic acid preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of making furoic acid comprising: reacting furfural with oxygen in an aqueous solution in the presence of an oxidation catalyst to obtain the furoic acid; wherein the oxidation catalyst is a supported catalyst containing bismuth and a noble metal.
According to one embodiment of the invention, the reaction conditions are as follows:
the molar ratio of the noble metal to the furfural in the supported catalyst containing bismuth and noble metal is 1 to 1000, preferably 1 to 500, more preferably 1 to 250.
The oxygen can be pure oxygen, air or a mixed gas of oxygen and nitrogen, and the partial pressure of the oxygen is 1MPa to 5MPa, preferably 1MPa to 3MPa.
The reaction temperature of the oxidation reaction is 50 ℃ to 170 ℃, and preferably 90 ℃ to 150 ℃.
The mass percentage content of the furfural in the aqueous solution is 0.1-30%, preferably 0.5-20%, and more preferably 1-10%.
The support of the supported catalyst containing bismuth and the noble metal is selected from carbonaceous materials including one or more of activated carbon, carbon nanotubes, graphene or graphene oxide, preferably activated carbon. When the carrier is active carbon, the specific surface area of the active carbon is 1000m 2 /g～1500m 2 /g。
In the supported catalyst containing bismuth and the noble metal, the noble metal is selected from one or more of Ru, pt and Au. The loading amount of the noble metal is 0.1-10%, preferably 1-5% based on the total mass of the carrier.
In the supported catalyst containing bismuth and a noble metal, the molar ratio of the noble metal to bismuth is 1.
The preparation method of the supported catalyst containing bismuth and noble metal comprises the following steps:
(1) Dispersing a supported noble metal catalyst in water, stirring to obtain a suspension, continuously introducing hydrogen into the suspension, and adding an acid solution to adjust the pH value to acidity;
(2) Dissolving a precursor containing bismuth in an acid solution to prepare an acid solution containing bismuth, adding the acid solution into the suspension obtained in the step (1), and filtering and drying to obtain the supported catalyst containing bismuth and noble metal.
In the step (1), the supported noble metal catalyst comprises a carrier and a noble metal supported on the carrier, and the supported amount of the noble metal is 0.1-10%, preferably 1-5%, based on the total mass of the carrier.
In the step (1), the carrier of the supported noble metal catalyst is selected from a carbon-containing material, including one or more of activated carbon, carbon nanotubes, graphene or graphene oxide, and is preferably activated carbon. Wherein, when the carrier is activated carbon, the specific surface area of the activated carbon is 1000m 2 /g～1500m 2 /g。
In the step (1), the system is kept in a hydrogen-rich environment, and the preferred ventilation rate of hydrogen is 10-100 mL/min.
In the step (2), the precursor containing bismuth is selected from one or more of bismuth nitrate, bismuth trichloride and bismuth acetate.
The acid solution in the steps (1) and (2) is nitric acid, hydrochloric acid, acetic acid or an aqueous solution prepared from one or more of nitric acid, hydrochloric acid and acetic acid.
The supported noble metal catalyst can be prepared according to the existing method, such as an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method, a vacuum impregnation method and the like. During the specific preparation, after the deposition of the noble metal, the solid powder is dried in an oven at 100-140 ℃ for about 6-24 hours, the obtained supported catalyst precursor is firstly calcined in nitrogen at 300-800 ℃ for a period of time, and then in a reducing atmosphere (such as H) 2 Or H 2 And N 2 Mixed atmosphere of (b) at a temperature of 200 to 500 ℃ for about 6 to 24 hours to obtain a supported noble metal catalyst.
According to the technical scheme, the invention has the beneficial effects that:
the invention uses the supported catalyst containing bismuth and noble metal to efficiently catalyze and oxidize the furfural to prepare the furoic acid, and the bismuth component is introduced on the surface of the supported noble metal catalyst by a specific method, thereby further improving the oxidation efficiency of the catalyst. The adopted catalyst can realize the high-efficiency conversion of the furfural under mild conditions to obtain high-selectivity furoic acid, and the operation method is simple; in addition, in the process of preparing the furoic acid, water is used as a solvent, and oxygen or air is used as an oxygen source, so that the furoic acid is low in cost, green, environment-friendly, pollution-free and good in industrial application prospect.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Wherein the source of the furfural is Beijing YinuoKa science and technology Limited; the source of the active carbon is Beijing vigorous macro-industry science and technology Limited company, and the specific surface area is 1286m 2 (ii) in terms of/g. Kabot (China) investment Limited (brand: VXC 72) with a specific surface area of 258m 2 /g。
Preparation example 1
Initial impregnation method preparation of supported noble metal catalyst 2% pt/C:
0.05g/mL of H was taken 2 PtCl 6 Mixing 1.1mL of the solution with 10.0mL of deionized water, stirring uniformly, then adding 0.98g of activated carbon carrier into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and then drying for 12 hours in an oven at 110 ℃ to obtain a catalyst precursor. The loading of Pt was 2% (mass%). Placing the precursor prepared in the above steps in a quartz tube, calcining at 500 deg.C for 4h in nitrogen, and further 20% 2 +N 2 Reducing at medium 500 ℃ for 3h to obtain a supported 2% Pt/C catalyst.
Preparation of Ru and Au catalysts with different loadings on activated carbon support in a similar manner 5% Ru/C and 1% Au/C.
Preparation example 2
Preparing the supported catalyst containing bismuth and noble metal 2%:
(1) Weighing bismuth acetate (Bi (CH) 3 COO) 3 ) 36.9mg, adding 2mL of glacial acetic acid, fully stirring to completely dissolve the bismuth acetate, and adding 10mL of water to prepare an acetic acid aqueous solution containing the bismuth acetate; (2) Weighing 1.0g of 2 percent Pt/C catalyst, adding 150mL of deionized water, fully stirring to obtain a suspension, and continuously introducing hydrogen (the flow rate is 10 mL/min) into the suspension for 0.5h; (3) Adding a certain amount of glacial acetic acid into the suspension obtained in the step (2), adjusting the pH to be approximately equal to 2, dropwise adding the aqueous acetic acid solution containing the bismuth acetate prepared in the step (1) into the suspension, fully stirring for 1h, keeping the continuous introduction of hydrogen gas in the process (flow rate is 10 mL/min), filtering the suspension, and drying at room temperature to obtain the supported catalyst 2 containing bismuth and precious metal, wherein the supported amount of Bi is 2% (mass fraction), and the molar ratio of Pt to Bi is approximately 1.
In a similar manner, on the basis of the supported Pt catalyst obtained in preparation example 1, supported catalysts containing bismuth and a noble metal having different molar ratios of Pt to Bi were prepared by 1% Bi-2% Pt/C (the molar ratio of Pt to Bi is about 1.
Preparation example 3
Preparation of supported catalyst containing bismuth and noble Metal according to the method of preparation example 2 5% Bi-5% Ru/C, except that the precursor of Bi used was bismuth trichloride (BiCl) 3 ) The acid solution used was dilute hydrochloric acid, the loading of Bi was 5% (mass fraction), and the molar ratio of Ru to Bi was 1.
Preparation example 4
Preparation of supported catalyst containing bismuth and noble Metal 2% Bi-1% Au/C according to the method of preparation example 2, except that the precursor of Bi used was bismuth nitrate (Bi (NO) 3 ) 3 ) The acid solution used was dilute nitric acid, the loading of Bi was 2% (mass fraction), and the molar ratio of Au to Bi was 1.
Comparative preparation example 1
Preparing a supported catalyst containing bismuth and noble Metal in one step using an initial impregnation method 2%Weighing bismuth acetate (Bi (CH) 3 COO) 3 ) 36.9mg, 2mL of glacial acetic acid was added, the mixture was sufficiently stirred to completely dissolve bismuth acetate, 10mL of water was added to prepare an aqueous acetic acid solution containing bismuth acetate, and 0.05g/mL of H was added to the solution 2 PtCl 6 1.1mL of the solution is uniformly stirred, 0.98g of activated carbon carrier is added into the mixed solution, the mixed solution is stirred and soaked for 10 hours at room temperature, the water is evaporated, and then the mixed solution is dried for 12 hours in a 110 ℃ oven to obtain a catalyst precursor. The supported amount of Bi was 2% (mass fraction), and the supported amount of Pt was 2% (mass fraction). Placing the precursor prepared in the above steps in a quartz tube, calcining at 500 deg.C in nitrogen for 4h, and then 20% 2 +N 2 Reduction at medium 500 ℃ for 3h to obtain an initial impregnation method a supported catalyst containing bismuth and noble metal was prepared in one step 2% Bi-2% Pt/C (labeled 2% Bi-2% Pt/C1) with a molar ratio of Pt to Bi of about 1.
Comparative preparation example 2
The initial impregnation method was used to prepare the supported catalyst containing bismuth and noble metals 2% Bi-2% Pt/C in steps, i.e., the supported 2% Pt/C catalyst was first prepared according to the method of preparation example 1. Then weighing bismuth acetate (Bi (CH) 3 COO) 3 ) 36.9mg of bismuth acetate was dissolved completely by adding 2mL of glacial acetic acid thereto, stirring the mixture sufficiently to dissolve the bismuth acetate, adding 10mL of water to prepare an aqueous acetic acid solution containing bismuth acetate, adding 1.0g of a 2% pt/C catalyst to the solution, stirring the solution at room temperature for immersion for 10 hours, evaporating the water content, and drying the solution in an oven at 110 ℃ for 12 hours to obtain a catalyst precursor. The supported amount of Bi was 2% (mass fraction). Placing the precursor prepared in the above step in a quartz tube at 20% H 2 +N 2 Reduction at 300 ℃ for 3h to obtain an initial impregnation method the supported catalyst containing bismuth and precious metal was prepared 2% Bi-2% Pt/C (labeled 2% Bi-2% Pt/C2%) in steps with a Pt to Bi molar ratio of about 1.
In contrast, in preparation example 2, hydrogen gas is continuously introduced into a bismuth-containing solution to reduce bismuth ions in the solution in situ on the surface of Pt to form a Pt — Bi alloy, while in comparative preparation example 2, bismuth ions are deposited on the surface of a PtC catalyst (not necessarily in contact with Pt) by an impregnation method, and are reduced in a hydrogen atmosphere after drying, so that Bi and Pt cannot well interact with each other on the prepared catalyst.
Comparative preparation example 3
Preparing a supported catalyst containing bismuth and a noble metal on a low specific surface area activated carbon support 2%
Preparation of a supported catalyst containing bismuth and noble Metal on a Low surface area activated carbon support according to the method of preparation example 2 The 2% Bi-2% Pt/C3 except that the catalyst support used was a low surface area activated carbon (Carbot VXC72, specific surface area 258 m) 2 /g)。
Example 1
This example illustrates the process for furfural synthesis according to the present invention.
A50 mL autoclave was charged with 0.5g of furfural, 0.2g of the 2-Bi-2 Pt/C oxidation catalyst prepared in preparation example 2, 10g of water, the autoclave was closed, then charged with 1MPa of oxygen to displace the residual air in the autoclave, and the reaction was repeated three times, then charged with 1MPa of oxygen, the autoclave was heated in a heating furnace to a reaction temperature of 100 ℃ and stirred at 700rpm for 10 hours. And after the reaction is finished, taking the reaction kettle out of the heating furnace, cooling to room temperature, filtering, washing a filter cake by using a mixed solvent which is the same as the reaction solvent, finally fixing the volume to 100mL, and taking a liquid sample for high performance liquid chromatography analysis. The reaction results are shown in Table 1.
Example 2
The procedure of example 1 was followed except that the oxidation catalyst used was 0.2g of the 1-The Bi-2% by weight Pt/C catalyst prepared in preparation example 2, and the reaction results are shown in Table 1.
Example 3
The procedure of example 1 was followed except that the oxidation catalyst used was 0.2g of the 8-th-Bi-2% Pt/C catalyst prepared in preparation example 2, and the reaction results are shown in Table 1.
Example 4
The procedure of example 1 was followed except that the oxidation catalyst used was 0.2g of the 5-th-Bi-5-th-Ru/C catalyst prepared in preparation example 3, and the reaction results are shown in Table 1.
Example 5
According to the method of example 1, except that the oxidation catalyst used was 2% Bi-1%.
Example 6
The procedure of example 1 was followed except that the pressure of oxygen charged in the reaction vessel at the start of the reaction was 1MPa, and the reaction results are shown in Table 1.
Example 7
The procedure of example 1 was followed except that the pressure of oxygen charged in the reaction vessel at the start of the reaction was 3MPa, and the reaction results are shown in Table 1.
Example 8
The procedure of example 1 was followed except that the reaction temperature was 120 ℃ and the reaction results were shown in Table 1.
Example 9
The procedure of example 1 was followed except that the reaction temperature was 140 ℃ and the reaction results were shown in Table 1.
Comparative example 1
The procedure of example 1 was followed, except that the oxidation catalyst used was 0.2g of 2% Pt/C catalyst prepared in preparation example 1, and the reaction results are shown in Table 1.
Comparative example 2
The procedure of example 1 was followed except that the oxidation catalyst used was 0.2g of the 2-th bi-2%.
Comparative example 3
The procedure of example 1 was followed, except that the oxidation catalyst used was 0.2g of the 2% Bi-2% Pt/C2 catalyst prepared in comparative preparation 2, and the reaction results are shown in Table 1.
Comparative example 4
The procedure of example 1 was followed except that the oxidation catalyst used was 0.2g of the 2-th bi-2-th%.
TABLE 1 catalyst composition and Performance in examples 1-9 and comparative examples 1-4
From the data in table 1, from examples 1-3, it is seen that the molar ratio of Pt to bismuth in the supported Pt catalyst containing bismuth affects the performance of the catalyst, but that the molar ratio of noble metal to bismuth is in the range of 1; 2. from examples 4 and 5, it can be known that the supported Ru or Au catalyst containing bismuth shows higher activity of oxidizing furfural to furoic acid under the test conditions of the method, the conversion rate of furfural reaches 100%, and the yield of furoic acid is higher than 90%; 3. from examples 6-9, it is clear that the partial pressure of oxygen and the reaction temperature also affect 2% of the performance of the Bi-2% Pt/C oxidation catalyst, too high a partial pressure of oxygen and a reaction temperature would cause a certain reduction in the yield of furoic acid; 4. as can be seen from comparative example 1, compared with the catalyst containing bismuth prepared by the method, the catalyst containing no bismuth has obviously reduced furfural oxidation activity and yield of furoic acid, which indicates that the catalyst performance can be significantly improved after bismuth is modified on the surface of the catalyst; 5, as can be seen from comparative examples 2 and 3, compared with the bismuth-containing catalyst prepared by the method, the supported catalyst containing bismuth and noble metal prepared by a conventional catalyst preparation method, such as an impregnation method, in one step or step by step has the same obvious lower furfural oxidation activity and yield of furoic acid, which indicates that the catalyst preparation method used by the method can better promote the promotion effect of bismuth element on the catalyst oxidation activity and effectively improve the yield of furoic acid; as can be seen from comparative example 4, the specific surface area of the carrier significantly affects the activity of the catalyst, and when the specific surface area of the carrier decreases, the yield of furoic acid significantly decreases.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (16)
1. A method of making furoic acid comprising: reacting furfural with oxygen in an aqueous solution in the presence of an oxidation catalyst to obtain the furoic acid; wherein the oxidation catalyst is a supported catalyst containing bismuth and a noble metal.
2. The method according to claim 1, wherein the mass percentage of the furfural in the aqueous solution is 0.1-30%, preferably 0.5-20%, and more preferably 1-10%.
3. The process according to claim 1, wherein the molar ratio of the noble metal to the furfural in the supported catalyst comprising bismuth and noble metal is from 1.
4. The method according to claim 1, wherein the oxygen is derived from pure oxygen, air or a mixed gas of oxygen and nitrogen, and the partial pressure of the oxygen is 1 to 5MPa, preferably 1 to 3MPa.
5. A process according to claim 1, wherein the temperature of the oxidation reaction is from 50 ℃ to 170 ℃, preferably from 90 ℃ to 150 ℃.
6. The process according to claim 1, wherein the support of the supported catalyst comprising bismuth and a noble metal is selected from carbonaceous materials comprising one or more of activated carbon, carbon nanotubes, graphene or graphene oxide, preferably activated carbon.
7. The process according to claim 6, wherein when the carrier is activated carbon, the activated carbon has a specific surface area of 1000m 2 /g～1500m 2 /g。
8. The method according to claim 1, wherein in the supported catalyst containing bismuth and the noble metal, the noble metal is selected from one or more of Ru, pt and Au.
9. The process according to claim 1, wherein the supported catalyst comprising bismuth and a noble metal is supported at a noble metal content of 0.1 to 10%, preferably 1 to 5%, based on the total mass of the support.
10. The process according to claim 1, wherein the molar ratio of noble metal to bismuth in the supported catalyst comprising bismuth and noble metal is from 1.
11. The process of claim 1, wherein the supported catalyst comprising bismuth and a noble metal is prepared by a process comprising:
(1) Dispersing a supported noble metal catalyst in water, stirring to obtain a suspension, continuously introducing hydrogen into the suspension, and adding an acid solution to adjust the pH value to acidity;
(2) Dissolving a precursor containing bismuth in an acid solution to prepare an acid solution containing bismuth, adding the acid solution into the suspension liquid obtained in the step (1), and filtering and drying to obtain the supported catalyst containing bismuth and noble metal.
12. The process according to claim 11, wherein in the step (1), the supported noble metal catalyst comprises a carrier and a noble metal supported on the carrier, and the supported amount of the noble metal is 0.1 to 10%, preferably 1 to 5%, based on the total mass of the carrier.
13. The process according to claim 11, wherein in step (1), the support of the supported noble metal catalyst is selected from carbonaceous materials including one or more of activated carbon, carbon nanotubes, graphene or graphene oxide, preferably activated carbon.
14. The method according to claim 13, wherein when the carrier is activated carbon, the activated carbon has a specific surface area of 1000m 2 /g～1500m 2 /g。
15. The method according to claim 11, wherein in step (1), the system is maintained in a hydrogen-rich environment, preferably with a hydrogen aeration of 10 to 100mL/min.
16. The method according to claim 11, wherein in the step (2), the precursor containing bismuth is selected from one or more of bismuth nitrate, bismuth trichloride and bismuth acetate.
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