CN108531936B - A kind of method that biomass class compound electrocatalytic oxidation produces 2,5- furandicarboxylic acid - Google Patents
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5- furandicarboxylic acid Download PDFInfo
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Abstract
The present invention relates to a kind of biomass class compound electrocatalytic oxidations to produce 2, the method of 5- furandicarboxylic acid, it is reacted using H-type electrolytic cell, in anode chamber, using loaded catalyst as working electrode, it is dissolved in alkaline solution by reaction substrate of biomass class compound as anolyte；In cathode chamber, platinized platinum is used as to electrode, alkaline solution is as catholyte, it is 30-90 DEG C in temperature, electric current is 5-50 mA, tank voltage is 1-10 V, carry out electrocatalysis oxidation reaction, reaction time 0.5-5 hour, reaction end is post-treated to obtain 2, 5- furandicarboxylic acid, process of the invention, electrocatalysis oxidation reaction process condition is mild, green non-pollution, feed stock conversion is higher, FDCA is selectively preferable, the noble metal catalyst generallyd use compared with the existing technology, the metal vanadium compounds catalyst that the present invention uses is at low cost, avoid the consumption of rare precious metals raw material.
Description
Technical field
The present invention relates to a kind of synthetic method of Organic chemical products, in particular to a kind of biomass class compound electro-catalysis
Aoxidize the method for producing 2,5- furandicarboxylic acid.
Background technique
Contain aromatic rings in the molecular structure of 2,5-furandicarboxylic acid (FDCA), be used for synthesising biological based high molecular material,
It is considered as the ideal substitute of petroleum base monomers terephthalic acid, M-phthalic acid, adipic acid, succinic acid etc. can also be substituted
Synthesis applied to bio-based polymers such as polyester, polyamide, epoxy resin.Therefore, it is chosen as 12 kinds by U.S. Department of Energy
One of most potential biology base platform chemicals are considered " giant being sunk into sleep " by Du Pont and DSM company.In addition, due to close
Year develops the new application of many FDCA, and market demand is caused to be continuously increased.
5 hydroxymethyl furfural (HMF) heterogeneous catalytic oxidation method preparation FDCA is commonly used, there is conversions for the method
Rate is low, poor selectivity, noble metal catalyst, the problems such as environmental pollution is serious.Therefore, finding a kind of can utmostly improve raw material
Conversion ratio, aldehydic acid selectivity, non-precious metal catalyst, and environmentally protective catalysis process is significant.
Biomass resource big, renewable, advantages of environment protection with reserves, it is considered to be the ideal substitution of fossil resource
Product, development and utilization have received widespread attention.Existing document report converts FDCA for HMF under heterogeneous conditions at present
Research.Such as: Zhang et al. is prepared for γ-Fe2O3@HAP-Pd、C-Fe3O4- Pd catalyst is used for HMF oxidation system
Take FDCA(Zehui Zhang, Judun Zhen, Bing Liu, Kangle Lv, Kejian Denga. Selective
aerobic oxidation of the biomass-derived precursor 5-hydroxymethylfurfural to
2,5-furandicarboxylic acid under mild conditions over a magnetic palladium
nanocatalyst. Green Chem., 2015, 17, 1308-1317；Bing Liu, Yongshen Rena, Zehui
Zhang. Aerobic oxidation of 5-hydroxymethylfurfural into 2,5-
furandicarboxylic acid in water under mild conditions. Green Chem., 2015, 17,
1610-1617).However Traditional liquid phase oxidizing process energy consumption is high, needs to carry out at high temperature under high pressure, severe reaction conditions, and cause
Rapid catalyst deactivation.Therefore, it is unfavorable for industrial mass production.
Electro-catalytic oxidation technology has reaction condition mild, easy-regulating, cleaning and economy etc. compared with Traditional liquid phase aoxidizes
Feature shows tempting application prospect, and the research in the field caused the extensive concern of people in recent years.Have pair at present
The electrocatalysis oxidation reaction of HMF studies (Guanqun Han, Yan-Huan Jin, R. Alan Burgess, Nicholas
E. Dickenson, Xiao-Ming Cao, Yujie Sun. Visible-Light-Driven Valorization of
Biomass Intermediates Integrated with H2 Production Catalyzed by Ultrathin
Ni/CdS Nanosheets. J. Am. Chem. Soc., 2017, 139 (44), 15584-15587；Bo You, Nan
Jiang, Xuan Liu, Dr. Yujie Sun. Simultaneous H2 Generation and Biomass
Upgrading in Water by an Efficient Noble‐Metal‐Free Bifunctional
Electrocatalyst. Angew. Chem. Int. Ed., 2016, 55, 9913-9917；Bo You, Xuan Liu,
Nan Jiang, and Yujie Sun. A General Strategy for Decoupled Hydrogen
Production from Water Splitting by Integrating Oxidative Biomass
Valorization. J. Am. Chem. Soc., 2016,138 (41), 13639-13646).However, generally speaking,
There are still problems for the research of the electrocatalytic oxidation generation FDCA of the HMF reported at present, if the reaction time is longer, product selection
The problems such as property is low, and faradic efficiency is low and catalyst life is not long.In addition, noble metal analysis oxygen better performances, and oxygen evolution reaction
As the competitive reaction of electrocatalytic oxidation, it is easy to cause the current efficiency of reaction to decline and even prevents biomass class compound oxygen
Change.
It is used to prepare catalyst about by base metal vanadium compounds at present, and is used for the electrocatalytic oxidation of biomass class compound
Metaplasia has not been reported at the application of FDCA.
Summary of the invention
Raw material and catalyst are used present in current existing FDCA synthesis technology the purpose of the invention is to overcome
The problems such as higher cost, production technology are complicated, environmental pollution is serious, provides a kind of electrocatalytic oxidation furans substituent system 2,5- furan
It mutters the method for dioctyl phthalate (FDCA), technical process is environmentally protective, simple production process, and catalyst is at low cost and reaction efficiency
It is high.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
Voltage and current is controlled by galvanostat, is reacted using H-type electrolytic cell, cathode chamber and anode chamber's volume are 10-100
ML, two electrode chambers are separated by cation-exchange membrane, in anode chamber, using loaded catalyst as working electrode, with biomass
Class compound is that reaction substrate is dissolved in the alkaline solution of 0.1-2.0 mol/L as anolyte；In cathode chamber, platinized platinum conduct
To electrode, the alkaline solution of 0.1-2.0 mol/L as catholyte, in water bath with thermostatic control temperature be 30-90 DEG C, electric current 5-
50 mA, tank voltage are 2-10 V, carry out electrocatalysis oxidation reaction, and reaction time 0.5-5 hour reacts liquid cooling after reaction
But, it is extracted using organic solvent, obtains organic extract liquid, organic layer atmospheric distillation is taken to obtain 2,5-furandicarboxylic acid, reaction side
Formula is as follows:
In formula (I), R1And R2Expression methyl, methylol, aldehyde radical or carboxyl independent.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
Biomass class compound is 5 hydroxymethyl furfural, 2,5- dimethyl furan, 2,5- furyl dimethyl carbinol, 2,5- furans dicarbaldehyde, 5-
Methylol -2- furancarboxylic acid or 5- formylfuran -2- formic acid；The loaded catalyst is by foam metal carrier and is carried on
Base metal vanadium compounds composition on metallic carrier, the load capacity of base metal vanadium compounds are calculated as 1-15 with the quality of metallic carrier
wt%
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
Foam metal carrier is nickel foam, foam copper, foamed aluminium, bubble iron chromium aluminum, foam cobalt-nickel alloy or foam corronil；It is non-expensive
Metal vanadium compounds raw material is ammonium metavanadate, sodium vanadate, sodium metavanadate, potassium metavanadate, vanadium chloride, vanadic anhydride, three oxidations
Two vanadium, hydroxyl vanadium oxide, vanadium nitride or vanadium oxide.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
Cathode chamber and anode chamber's volume are 10-30 mL；The volumetric usage of anolyte is calculated as 5- with the amount of biomass class combinations of materials
50 mmol/L, preferably 10-20 mmol/L.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
The metallic carrier size of loaded catalyst is the cm of 1 × 1 cm -5 × 5, the preferably cm of 2 cm × 2.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
Alkaline solution is potassium hydroxide solution, sodium hydroxide solution, and magnesium hydroxide solution or calcium hydroxide solution, preferably potassium hydroxide are molten
Liquid, concentration are 0.5-1.5 mol/L.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
Electrocatalysis oxidation reaction electric current is 20-40 mA, and tank voltage is 3-6 V, and reaction temperature is 40-80 DEG C, reaction time 0.5-4
Hour；
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
Extraction is toluene, ether, chloroform or ethyl acetate with organic solvent.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that
The preparation method of loaded catalyst includes the following steps:
1) feed ratio is pressed, negated precious metal salt is dissolved in 20-100mL water, is stirred at room temperature 10-30 minutes, referred to as A is molten
Liquid, base metal salt be base metal chloride or base metal salt, preferably ammonium metavanadate, sodium vanadate, sodium metavanadate, partially
Potassium vanadate, vanadium chloride or vanadic anhydride, optimal is ammonium metavanadate；
2) dissolving acid in water and being made into concentration is 0.5-5 mol/L acid solution, referred to as B solution, the acid be hydrochloric acid,
Sulfuric acid, nitric acid, phosphoric acid or perchloric acid, preferably hydrochloric acid, sour concentration are preferably 1-2 mol/L；
3) B solution for taking 1-5mL step 2 to obtain is added drop-wise in the solution A that step 1) obtains, stirring at normal temperature 10-60 points
Clock, referred to as C solution；
4) reducing agent is dissolved in water to the reducing agent solution for being made into that concentration is 0.5-8 mol/L, referred to as solution D；
5) 1-8 mLD solution will be taken to be added drop-wise in the C solution that step 3) obtains, stirring at normal temperature 10-30 minutes, by your non-gold
Belong to salt and be reduced into nano metal vanadium compounds, obtains precursor solution；
6) precursor solution in step 5) and the metallic carrier pre-processed are added in water heating kettle at 100-180 DEG C
Hydro-thermal reaction 2-16 hours, metallic carrier is taken out after being cooled to room temperature, then uses distilled water and ethanol washing, then in 50-100
Vacuum drying obtains loaded catalyst at DEG C；
7) gained loaded catalyst is placed in microwave reactor after will be dry in step 6), carries out microwave treatment, microwave
In 100-300 W, loaded catalyst activates 10-60 minutes power control under the microwave condition；
8) catalyst after microwave treatment in step 7) is placed in tube furnace, is roasted under different atmosphere, maturing temperature
It is 200-700 DEG C, calcining time is 0.5-5 hours, obtains loaded catalyst after reaction.
A kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, feature exist
In:
Sour additional amount is 1-3 mL in step 3), until solution becomes glassy yelloe from colourless；
Reducing agent in step 4) is hydrazine hydrate, sodium borohydride or potassium borohydride, preferably hydrazine hydrate, the preferred 5- of concentration
8 mol/L；
The volume of reducing agent is 2-5 mL in step 5), until solution becomes taupe from glassy yelloe；
Hydrothermal temperature is 120-160 DEG C during step 6), and the hydro-thermal time is 6-12 hours, vacuum drying temperature 50-
60 DEG C, the preprocessing process of foam metal carrier is plus hydrochloric ultrasonic wave washing, ultrasonic time are generally 10 minutes, are washed with water
Completely, dry；
Microwave power is 200-300 W in step 7), and activation time is 20-30 minutes；
Atmosphere in step 8) is ammonia, nitrogen, argon gas, helium or air, and maturing temperature is 200-600 DEG C, when roasting
Between be 1-2 hours.
By using above-mentioned technology, compared with prior art, the beneficial effect that the present invention obtains is:
(1) raw material utilized in the present invention is biomass class compound, derives from agricultural-forestry biomass, and resource is cheap extensively,
Cost is relatively low；
(2) process of the invention, electrocatalysis oxidation reaction process condition is mild, green non-pollution, feed stock conversion
Higher, FDCA is selectively preferable；
(3) present invention uses water as reaction dissolvent, and cost is relatively low, and alkaline reaction liquid is repeatable to be applied, and does not generate nocuousness
Gas and harmful waste liquid, therefore, this method process toxicity are smaller, environmentally protective, and reaction is easy to control；
(4) noble metal catalyst generallyd use compared with the existing technology, the metal vanadium compounds catalyst that the present invention uses
It is at low cost, avoid the consumption of rare precious metals raw material；
(5) catalyst of the invention, during the preparation process, the main purpose that acid solution is added is regulation catalyst morphology,
The diameter of ball is influenced, when acid increases, the diameter of ball becomes smaller；When reducing agent is added, pentavalent vanadium can be reduced by reducing agent
Trivalent vanadium；
(6) catalyst of the invention, not only high catalytic efficiency, and also stability is good.It is used 10-20 times in repetitive cycling
Afterwards, on carrier base metal, the phenomenon that not finding activity component metal vfanadium compound, fall off or assemble, Ke Yiyou
Find out in SEM figure, nothing is substantially change catalyst before the reaction, after reaction；
(7) simple production process of the present invention, raw material are easy to get, and environmental pollution is small, and raw material availability is high, and product yield is high, and
It is high to be computed process faradic efficiency.
Detailed description of the invention
Fig. 1 a is SEM figure of the VOOH/NF catalyst of embodiment 1 under 30 μm；
Fig. 1 b is SEM figure of the VOOH/NF catalyst of embodiment 1 under 1 μm；
Fig. 1 c is SEM figure of the VOOH/NF catalyst of embodiment 1 at 500 nm；
Fig. 1 d is SEM figure of the VOOH/NF catalyst at 500 nm after embodiment 5 is reacted；
Fig. 2 a is the performance test curve of VOOH/NF catalyst, and electrolyte is 1 mol/L KOH aqueous solution；
Fig. 2 b is the performance test curve of VOOH/NF catalyst, and electrolyte is the aqueous solution of HMF and KOH composition,
The concentration of middle HMF is 10mmol/L, and the concentration of KOH is 1mol/L；
Fig. 3 is that the reaction of 5 electrocatalytic oxidation HMF FDCA of embodiment changes with time figure.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, technical scheme of the present invention will be further explained in detail.
Embodiment 1:
It is supported on the preparation that three-dimensional porous hydroxyl vanadium oxide catalyst VOOH/NF is formed in nickel foam, the following institute of method
It states:
(1) 234 mg ammonium metavanadates are dissolved in 40 mL water, nickel foam dipping is added, stirs 10min, at room temperature to urge
The quality of agent active component hydroxyl vanadium oxide is 5% calculating of the quality of carrier foam nickel, the substance of the ammonium metavanadate of addition
Amount is 2mmol；
(2) compound concentration is the hydrochloric acid solution of 1mol/L, prepares the hydrazine hydrate aqueous solution of 8mol/L, spare；
(3) it takes hydrochloric acid solution obtained by 1 mL step (2) to be slowly dropped in step (1) acquired solution, 20min is stirred at room temperature
Afterwards, it is slowly added to reducing agent solution obtained by 2 mL steps (2), continues to stir 30min at room temperature；
(4) by step (3) precursor solution and the foam nickel carrier that has pre-processed of 300 mg (pretreatment is at conventional
Reason method, ultrasound 10 minutes, are washed with water clean, drying in acid condition) it is added in water heating kettle, it is lauched in 160 DEG C of temperature
Thermal response 8h, is cooled to room temperature, and takes out nickel foam, and after alternately being washed 2 times using distilled water and ethyl alcohol, vacuum is dry at 60 DEG C
It is dry；
(5) loaded catalyst of step (4) after dry is placed in plasma reaction furnace, plasma control exists
100W, is passed through nitrogen, vacuum degree 50Pa under vacuumized conditions, catalyst activates in a nitrogen atmosphere by 30 DEG C of reaction temperature
0.3h；
(6) by step (5), treated, and loaded catalyst is placed in tube furnace, under nitrogen atmosphere, in 200 DEG C of temperature
After lower roasting 1h, it is cooled to room temperature to get the foamed nickel supported hydroxyl vanadium oxide catalyst, SEM scanning electron microscope (SEM) photograph is as schemed
Shown in 1a, 1b, 1c.It can be found that hydroxyl vanadium oxide catalyst is in nanosphere pattern from Fig. 1 a, Fig. 1 b, and ball shape is uniform,
Size about 500-600 nm.Fig. 1 c figure is the SEM figure of post catalyst reaction, it is found that post catalyst reaction still remains
Spherical structure is uniformly dispersed, and nothing is significantly built up.
Embodiment 2:
It is supported on foam copper and forms three-dimensional porous nitridation vanadium catalyst (VNx/ CF) preparation, method is as described below:
(1) 488 mg sodium metavanadates are dissolved in 40 mL water, foam copper dipping is added, stirs 10min, at room temperature to urge
The quality of agent active component vanadium nitride is 10% calculating of the quality of carrier foam copper, the amount of the substance of the sodium metavanadate of addition
For 4mmol；
(2) compound concentration is the sulfuric acid solution of 1mol/L, prepares the sodium borohydride aqueous solution of 5mol/L, spare；
(3) it takes sulfuric acid solution obtained by 2 mL steps (2) to be slowly dropped in step (1) acquired solution, 20min is stirred at room temperature
Afterwards, it is slowly added to reducing agent solution obtained by 3 mL steps (2), continues to stir 30min at room temperature；
(4) by step (3) precursor solution and the foam copper carrier that has pre-processed of 600 mg (pretreatment is at conventional
Reason method, ultrasound 10 minutes, are washed with water clean, drying in acid condition) it is added in water heating kettle, it is lauched in 140 DEG C of temperature
Thermal response 10h, is cooled to room temperature, and takes out foam copper, and after alternately being washed 2 times using distilled water and ethyl alcohol, vacuum is dry at 60 DEG C
It is dry；
(5) loaded catalyst of step (4) after dry is placed in plasma reaction furnace, plasma control exists
200W, is passed through argon gas, vacuum degree 80Pa under vacuumized conditions, catalyst activates under an argon atmosphere by 60 DEG C of reaction temperature
1h；
(6) by step (5), treated, and loaded catalyst is placed in tube furnace, under ammonia atmosphere, in 400 DEG C of temperature
After lower roasting 2h, it is cooled to room temperature and loads nitridation vanadium catalyst to get the foam copper.
Embodiment 3:
It is supported on foamed aluminium and forms three-dimensional porous vanadium oxide catalyst (VOx/ AF) preparation, method is as described below:
(1) 1.10 g sodium vanadates are dissolved in 40 mL water, foamed aluminium dipping is added, stirs 10min, at room temperature to urge
The quality of agent active component vanadium oxide is 15% calculating of the quality of carrier foam aluminium, the amount of the substance of the sodium vanadate of addition
For 6mmol；
(2) compound concentration is the nitric acid solution of 1mol/L, prepares the potassium borohydride aqueous solution of 6mol/L, spare；
(3) it takes sulfuric acid solution obtained by 3 mL steps (2) to be slowly dropped in step (1) acquired solution, 20min is stirred at room temperature
Afterwards, it is slowly added to reducing agent solution obtained by 5 mL steps (2), continues to stir 30min at room temperature；
(4) by step (3) precursor solution and the foam alumina supporter that has pre-processed of 900 mg (pretreatment is at conventional
Reason method, ultrasound 10 minutes, are washed with water clean, drying in acid condition) it is added in water heating kettle, it is lauched in 120 DEG C of temperature
Thermal response 12h, is cooled to room temperature, and takes out foamed aluminium, and after alternately being washed 2 times using distilled water and ethyl alcohol, vacuum is dry at 60 DEG C
It is dry；
(5) loaded catalyst of step (4) after dry is placed in plasma reaction furnace, plasma control exists
300W, is passed through helium, vacuum degree 100Pa under vacuumized conditions, catalyst activates under helium atmosphere by 150 DEG C of reaction temperature
1.5h；
(6) by step (5), treated, and loaded catalyst is placed in tube furnace, under air atmosphere, in 500 DEG C of temperature
After lower roasting 2h, it is cooled to room temperature to get the foamed aluminium load vanadium oxide catalyst.
Embodiment 4:
The VOOH/NF catalyst prepared to embodiment 1 is tested for the property, and the specific method is as follows:
Judge VOOH/NF catalyst to biomass class using cyclic voltammetry curve (CV) and linear scan curve (LSV)
Close object electrocatalytic oxidation property；
Using the CHI760E electrochemical workstation of Shanghai Chen Hua, in three-electrode cell system, got ready made
For VOOH/NF catalyst as working electrode (its electrode size is 1cm × 1cm), platinized platinum is to electrode, Ag/AgCl(3 M KCl)
Electrode is reference electrode.Electrolyte A used be 70 mL 1 mol/L KOH solution, electrolyte B used be 70 mL HMF and
The solution of KOH composition, wherein the concentration of HMF is 10 mmol/L, and the concentration of KOH is 1 mol/L.By electrolyte A and electrolyte B
Oxygen evolution reaction (OER) and electrocatalysis oxidation reaction (ECO) test are carried out respectively, and 30 min of oxygen is each led into before test, makes electricity
Solution liquid reaches saturation state, and the scanning speed of cyclic voltammetry is 50 mV/s, and the sweep speed of linear sweep voltammetry is 5
mV/s.Attached drawing 2a, 2b are in three-electrode system, and VOOH/NF catalyst is to HMF electrocatalytic oxidation (2a) CV and (2b) LSV
Figure.It can be seen from CV and LSV figure when HMF is added in 1 mol/L KOH solution (B curve), relative in 1 mol/L
In KOH solution (A curve), there is stronger oxidation peak on B curve, can tentatively judge, VOOH/NF catalyst aoxidizes HMF
Reaction is effective.
Embodiment 5:
Electrocatalytic oxidation HMF FDCA, method and step are as follows:
Voltage and current is controlled by galvanostat, is reacted using H-type electrolytic cell, cathode chamber and anode chamber's volume are 20
It mL and is separated by cation-exchange membrane, using the 1 mol/L KOH of 20 mL as the electrolytic solution of cathode chamber and anode chamber；In electricity
The anode chamber Xie Cao, VOOH/NF catalyst prepared by the embodiment 1 of 2cm × 2cm size are working electrode；In electric tank cathode room,
Platinum electrode is to electrode；
S1: by HMF(5- hydroxymethylfurfural) it is reactant, take 126 mg HMF to be added in anode chamber's electrolytic solution；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 60 DEG C of temperature of reaction system
20mA, control reference voltage 1-3V react 3h；
S3: after the anode chamber step S2 electrolytic solution is cooled to room temperature, through toluene extracting and demixing, toluene mutually evaporates separation,
Up to FDCA product, with the progress in reaction time, reaction result test is as shown in Figure 3.Fig. 3 is the dynamics figure of HMF oxidation, from
On figure it is known that with the reaction time growth, raw material HMF gradually decreasing, and principal product FDCA is being gradually increased.Wherein,
When reaction reaches 3h, the selectivity that the conversion ratio of HMF is 99%, FDCA is 95%, is computed faradic efficiency up to 70%,
SEM scanning electron microscope (SEM) photograph is as shown in Figure 1 d.
Embodiment 6:
Electrocatalytic oxidation DFF FDCA, method and step are as follows:
Voltage and current is controlled by galvanostat, is reacted using H-type electrolytic cell, cathode chamber and anode chamber's volume are 10
It mL and is separated by cation-exchange membrane, using the 1 mol/L KOH of 10 mL as the electrolytic solution of cathode chamber and anode chamber；In electricity
The anode chamber Xie Cao, VN prepared by the embodiment 2 of 2cm × 2cm sizex/ CF catalyst is working electrode；In electric tank cathode room,
Platinum electrode is to electrode；
S1: it is reactant by 2,5-furandaldehyde (DFF), 248 mg DFF is taken to be added in anode chamber's electrolytic solution；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 80 DEG C of temperature of reaction system
25mA, control reference voltage 1-5V react 2h；
S3: after the anode chamber step S2 electrolytic solution is cooled to room temperature, through chloroform extracting and demixing, chloroform mutually evaporates separation,
Up to FDCA product, the selectivity that the conversion ratio of HMF is 97%, FDCA is 95%, is computed faradic efficiency up to 80%.
Embodiment 7:
Electrocatalytic oxidation DMF FDCA, method and step are as follows:
Voltage and current is controlled by galvanostat, is reacted using H-type electrolytic cell, cathode chamber and anode chamber's volume are 30
It mL and is separated by cation-exchange membrane, using the 1.5 mol/L KOH of 30 mL as the electrolytic solution of cathode chamber and anode chamber；In
Electrolyzer anode chamber, VO prepared by the embodiment 3 of 3cm × 3cm sizex/ AF catalyst is working electrode；In electric tank cathode
Room, platinum electrode are to electrode；
S1: it is reactant by 2,5- dimethyl furan (DMF), 480 mg DMF is taken to be added in anode chamber's electrolytic solution；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 50 DEG C of temperature of reaction system
30mA, control reference voltage 2-5V react 4h；
S3: after the anode chamber step S2 electrolytic solution is cooled to room temperature, through chloroform extracting and demixing, chloroform mutually evaporates separation,
Up to FDCA product, the selectivity that the conversion ratio of DMF is 85%, FDCA is 91%, and faradic efficiency is up to 65%.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (13)
1. a kind of method that biomass class compound electrocatalytic oxidation produces 2,5-furandicarboxylic acid, it is characterised in that by constant current
Instrument control voltage and current is reacted using H-type electrolytic cell, and cathode chamber and anode chamber's volume are 10-100 mL, two electricity
Pole room is separated by cation-exchange membrane, in anode chamber, using loaded catalyst as working electrode, is with biomass class compound
Reaction substrate is dissolved in the alkaline solution of 0.1-2.0 mol/L as anolyte；In cathode chamber, platinized platinum is used as to electrode,
The alkaline solution of 0.1-2.0 mol/L is as catholyte, temperature is 30-90 DEG C, electric current is 5-50 mA in water bath with thermostatic control,
Tank voltage is 1-10 V, carries out electrocatalysis oxidation reaction, and reaction time 0.5-5 hour, after reaction, reaction solution are cooling, make
It is extracted with organic solvent, obtains organic extract liquid, take organic layer atmospheric distillation to obtain 2,5-furandicarboxylic acid, reaction equation is such as
Under:
In formula (I), R1And R2Expression methyl, methylol, aldehyde radical or carboxyl independent；
The loaded catalyst is made of foam metal carrier and the base metal vanadium compounds being carried on metallic carrier, non-expensive
The load capacity of metal vanadium compounds is calculated as 1-15 wt% with the quality of metallic carrier；
The preparation method of the loaded catalyst includes the following steps:
1) feed ratio is pressed, negated precious metal salt is dissolved in 20-100mL water, 10-30 minutes, referred to as solution A are stirred at room temperature,
Base metal salt is ammonium metavanadate, sodium metavanadate or sodium vanadate；
2) dissolving acid in water and being made into concentration is 0.5-5 mol/L acid solution, referred to as B solution, and the acid is hydrochloric acid, sulphur
Acid, nitric acid, phosphoric acid or perchloric acid, sour concentration are 1-2 mol/L；
3) B solution for taking 1-5mL step 2 to obtain is added drop-wise in the solution A that step 1) obtains, stirring at normal temperature 10-60 minutes,
Referred to as C solution；
4) reducing agent is dissolved in water to the reducing agent solution for being made into that concentration is 0.5-8 mol/L, referred to as solution D；
5) 1-8 mLD solution will be taken to be added drop-wise in the C solution that step 3) obtains, stirring at normal temperature 10-30 minutes, by base metal salt
Nano metal vanadium compounds are reduced into, precursor solution is obtained；
6) hydro-thermal at 100-180 DEG C is added in water heating kettle in the precursor solution in step 5) and the metallic carrier pre-processed
Reaction 2-16 hours, takes out metallic carrier after being cooled to room temperature, then uses distilled water and ethanol washing, then at 50-100 DEG C
Vacuum drying obtains loaded catalyst, and the metallic carrier is nickel foam, foam copper or foamed aluminium；
7) gained loaded catalyst is placed in microwave reactor after will be dry in step 6), carries out microwave treatment, microwave power
In 100-300 W, loaded catalyst activates 10-60 minutes under the microwave condition for control；
8) catalyst after microwave treatment in step 7) is placed in tube furnace, is roasted under certain atmosphere, maturing temperature is
200-700 DEG C, calcining time is 0.5-5 hours, obtains the three-dimensional porous hydroxyl vanadium oxide of loaded catalyst after reaction
Catalyst/nickel foam, three-dimensional porous nitridation vanadium catalyst/foam copper or three-dimensional porous vanadium oxide catalyst/foamed aluminium, it is described
Certain atmosphere is ammonia, nitrogen, argon gas, helium or air.
2. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that biomass class compound is 5 hydroxymethyl furfural, 2,5- dimethyl furan, 2,5-FDM, 2,5-
Furans dicarbaldehyde, 5- methylol -2- furancarboxylic acid or 5- formylfuran -2- formic acid.
3. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that cathode chamber and anode chamber's volume are 10-30 mL；The volumetric usage of anolyte is with biomass class compound
The amount of substance is calculated as 5-50 mmol/L.
4. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that the volumetric usage of anolyte is calculated as 10-20 mmol/L with the amount of biomass class combinations of materials.
5. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that the metallic carrier size of loaded catalyst is the cm of 1 × 1 cm -5 × 5.
6. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that the metallic carrier size of loaded catalyst is 2cm × 2cm.
7. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that alkaline solution be potassium hydroxide solution, sodium hydroxide solution, magnesium hydroxide solution or calcium hydroxide solution,
Its concentration is 0.5-1.5 mol/L.
8. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that alkaline solution is potassium hydroxide solution.
9. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that electrocatalysis oxidation reaction electric current is 20-40 mA, and tank voltage is 1-6 V, and reaction temperature is 40-80 DEG C, instead
It is 0.5-4 hours between seasonable.
10. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that extraction is toluene, ether, chloroform or ethyl acetate with organic solvent.
11. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that the acid in step 2 is hydrochloric acid.
12. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 1 produces 2,5- furandicarboxylic acid
Method, it is characterised in that:
Sour additional amount is 1-3 mL in step 3), until solution becomes glassy yelloe from colourless；
Reducing agent in step 4) is hydrazine hydrate, sodium borohydride or potassium borohydride, concentration 5-8 mol/L；
The volume of reducing agent is 2-5 mL in step 5), until solution becomes taupe from glassy yelloe；
Hydrothermal temperature is 120-160 DEG C during step 6), and the hydro-thermal time is 6-12 hours, vacuum drying temperature 50-60
DEG C, the preprocessing process of foam metal carrier is plus hydrochloric ultrasonic wave washs；
Microwave power is 200-300 W in step 7), and activation time is 20-30 minutes；
Maturing temperature in step 8) is 200-600 DEG C, and calcining time is 1-2 hours.
13. the side that a kind of biomass class compound electrocatalytic oxidation according to claim 12 produces 2,5- furandicarboxylic acid
Method, it is characterised in that the reducing agent in step 4) is hydrazine hydrate.
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| CN109234754B (en) * | 2018-09-29 | 2020-05-05 | 陕西科技大学 | Synthesis of NH4V4O10Preparation method of/CF water cracking catalyst |
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| CN109837555B (en) * | 2019-04-11 | 2019-12-31 | 浙江工业大学 | Method for preparing 2, 5-furandicarboxylic acid by electrocatalytic oxidation of nickel-vanadium phosphide catalyst |
| CN110205645A (en) * | 2019-04-23 | 2019-09-06 | 电子科技大学 | 5 hydroxymethyl furfural electroxidation is the all-hydrolytic device and reaction method of anode reaction |
| CN110106514B (en) * | 2019-05-13 | 2020-09-29 | 浙江大学 | Method for preparing 2, 5-furandicarboxylic acid by electrochemical oxidation of 5-hydroxymethylfurfural |
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| CN113529113B (en) * | 2020-03-31 | 2022-09-16 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 2, 5-furandicarboxylic acid |
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