CN110433845A - Method for preparing 2, 5-furandimethanol by electrocatalytic hydrogenation of carbon-coated copper nitride nanowire catalyst - Google Patents
Method for preparing 2, 5-furandimethanol by electrocatalytic hydrogenation of carbon-coated copper nitride nanowire catalyst Download PDFInfo
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- CN110433845A CN110433845A CN201910778877.6A CN201910778877A CN110433845A CN 110433845 A CN110433845 A CN 110433845A CN 201910778877 A CN201910778877 A CN 201910778877A CN 110433845 A CN110433845 A CN 110433845A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 239000010949 copper Substances 0.000 title claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- -1 copper nitride Chemical class 0.000 title claims abstract description 33
- 239000002070 nanowire Substances 0.000 title claims abstract description 33
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 title abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 49
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 235000004237 Crocus Nutrition 0.000 claims description 4
- 241000596148 Crocus Species 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000012074 organic phase Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 abstract description 36
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005341 cation exchange Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 241000219095 Vitis Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 2, 5-furandimethanol by electrocatalytic hydrogenation of a carbon-coated copper nitride nanowire catalyst, which adopts an H-shaped electrolytic cell for reaction, wherein in an anode chamber, a platinum sheet is used as a counter electrode, and an acidic solution is used as anolyte; in a cathode chamber, directly taking a carbon-coated copper nitride nanowire catalyst as a working electrode, dissolving 5-hydroxymethylfurfural in an acid solution as catholyte, carrying out electrocatalytic hydrogenation reaction at the temperature of 25-80 ℃, the current of 10-100mA and the cell voltage of 1-10V for 1-5h, and after the reaction is finished, carrying out post-treatment on the reaction solution to obtain 2, 5-furandimethanol (BHMF). The process method has the advantages of mild conditions in the electrocatalytic hydrogenation reaction process, greenness, no pollution, high raw material conversion rate and good BHMF (BHMF) selectivity, and the carbon-coated copper nitride nanowire catalyst used in the invention has lower cost compared with the precious metal catalyst generally adopted in the prior art.
Description
Technical field
The present invention relates to a kind of synthetic method of Organic chemical products, in particular to a kind of carbon coating nitridation copper nano-wire is urged
The method that agent electrocatalytic hydrogenation produces 2,5- furyl dimethyl carbinol.
Background technique
2,5-FDM (abbreviation BHMF) is a kind of glycol of high added value, in catalyst preparation, novel function
Can change in the preparation research of the poly-heterocyclic compounds of polyethers, polyurethane and drug has important application.For carbohydrate (mainly Portugal
Grape sugar and fructose) reaction for preparing 2,5-FDM, the multistep reaction architectural study stage is also predominantly stayed at present, thus
Reaction can be related to more separation and purification step, and the organic solvent for not only increasing equipment investment cost, but also using is also at increase
A possibility that managing difficulty and pollution environment.In addition, there is noble metal catalyst, conversion ratio are low, selective for traditional thermocatalytic method
The problems such as poor.Therefore, developing a kind of simple method adds hydrogen BHMF will be with boundless research significance.And it is novel at present
Electro-catalysis technology compared with conventional catalyst technology, have reaction condition it is mild, easy-regulating, cleaning and it is economical the features such as, display
Tempting application prospect out, the research in the field caused the extensive concern of people in recent years.Have at present to biomass original
Research (ACS Catal., 2016,6,1840-1847 in terms of the electrocatalytic hydrogenation of material；ChemSusChem,2015,8,1745-
1751；ChemSusChem,2013,6,1659-1667).However, generally speaking, the 5 hydroxymethyl furfural (HMF) reported at present
Electrocatalytic hydrogenation in terms of research it is less.
Currently, being used to prepare catalyst about by carbon coating copper nitride, and the electro-catalysis for biomass class compound adds
The application that hydrogen generates BHMF has not been reported.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the invention is to overcome current existing 2,5- furans
Present in dimethanol (BHMF) synthesis technology using raw material and catalyst higher cost, production technology is complicated the problems such as, provide
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM, technical process green
Environmental protection, simple production process, catalyst is at low cost and reaction efficiency is high.
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that controlling voltage and current by galvanostat, reacted using H-type electrolytic cell, cathode chamber and anode chamber's volume are equal
For 10-50mL, two electrode chambers are separated by cation-exchange membrane, and in anode chamber, platinized platinum is as anode chamber's electrode, 0.1-
The acid solution of 2.0mol/L is as anolyte；In cathode chamber, by carbon coating copper nitride nano-wire catalyst directly as cathode
Room electrode is dissolved in the acid solution of 0.1-2.0mol/L by reaction substrate of 5 hydroxymethyl furfural as catholyte, in perseverance
In tepidarium temperature be 25-80 DEG C, electric current 10-100mA, tank voltage 1-10V, carry out electrocatalytic hydrogenation reaction, reaction
Time 1-5h, after reaction, reaction solution are cooling；The indoor reaction solution of cathode is extracted using organic solvent, obtains organic extraction
Liquid takes organic layer atmospheric distillation to obtain 2,5-FDM, and reaction equation is as follows:
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that cathode chamber and anode chamber's volume are 10-50mL, preferably cathode chamber and anode chamber's volume is 10-20mL.
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that the volumetric usage of catholyte is calculated as 5-50mmol/L, preferably 10- with the amount of 5 hydroxymethyl furfural substance
30mmol/L；
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that acid solution is sulfuric acid solution, perchloric acid solution, nitric acid solution or hydrochloric acid solution, preferably sulfuric acid solution is dense
Degree is 0.1-1.0mol/L.
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that electrocatalytic hydrogenation kinetic current is 10-50mA, tank voltage 1-7V, reaction temperature is 25-50 DEG C, the reaction time
For 1-3h.
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that extraction is methylene chloride, ether, chloroform or ethyl acetate with organic solvent.
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that the carbon coating copper nitride nano-wire catalyst preparation method includes the following steps:
1) pre-processing foam copper carrier, (pretreatment is conventional treatment method, in acid condition ultrasound 10 minutes, then is distinguished
With ultrasound 30 minutes in acetone, second alcohol and water, clean, drying is finally washed with water), the foam copper carrier size is 1 × 1cm-5
× 5cm, preferably 2cm × 2cm；
2) being dissolved in water alkali and being made into concentration is 1-10mol/L alkaline solution, referred to as solution A, and the alkali is hydroxide
Sodium, potassium hydroxide or barium hydroxide, preferably sodium hydroxide, the concentration of alkali are preferably 2-5mol/L；
3) ammonium persulfate is dissolved in water to the solution for being made into that concentration is 0.1-1.0mol/L, referred to as B solution, the over cure
The concentration of acid ammonium solution is preferably 0.1-0.5mol/L；
4) it is 1:1 according to volume ratio, takes B solution obtained by solution A and step 3) obtained by step 2) respectively, then by two kinds of solution
Mix to solution clarification, referred to as C solution；
5) it takes foam copper carrier obtained by step 1) to be added in the C solution that step 4) obtains to react 30 minutes, foam copper is by tangerine
Yellow becomes blue, obtains forerunner's body catalyst Kocide SD, is denoted as Cu (OH)2/ CF catalyst, what CF was indicated is foam copper；
6) forerunner's body catalyst in step 5) is impregnated 10-30 hours in glucose solution, then the vacuum at 60 DEG C
It is dry, carbon-coated catalyst is obtained, C@Cu (OH) is denoted as2/ CF catalyst；
7) the carbon coating catalyst after will be dry in step 6) is placed in tube furnace, is roasted under ammonia, maturing temperature is
200-500 DEG C, calcining time 1-3h, carbon coating copper nitride nano-wire catalyst is obtained after roasting, is denoted as NC CuN/
CF。
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that the detailed process of pretreatment foam copper carrier are as follows: ultrasound 10 minutes in acid condition, then acetone, second are used respectively
Clean, drying is finally washed with water in ultrasound 30 minutes in alcohol and water.
A kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM,
It is characterized in that the concentration of the glucose solution in step 6) is 0.1-0.5mol/L, preferred concentration 0.1mol/L, in grape
Dip time in sugar juice is 24 hours.
By using above-mentioned technology, compared with prior art, the beneficial effect that the present invention obtains is:
(1) the raw material 5 hydroxymethyl furfural that the present invention uses is biomass class compound, derives from agricultural-forestry biomass, money
Source is cheap extensively, and cost is relatively low；
(2) catalyst of the invention nitrogenizes copper catalyst using carbon coating, and carbon coating structure can be effectively protected nanometer
Cable architecture improves the stability of catalyst；
(3) process of the invention, electrocatalytic hydrogenation reaction process mild condition, green non-pollution, feed stock conversion
Higher, 2,5-FDM is selectively preferable；
(4) present invention uses acid as reaction dissolvent, and cost is relatively low, and acid reaction liquid is repeatable to apply, 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；
(5) noble metal catalyst generallyd use compared with the existing technology, the carbon coating copper nitride nanometer that the present invention uses
Line catalyst is at low cost, avoids a large amount of consumption of rare precious metals raw material；
(6) 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.
Detailed description of the invention
Fig. 1 a is scanning electron microscope diagram of the NC@CuN/CF catalyst of embodiment 1 under 2 μm；
Fig. 1 b is scanning electron microscope diagram of the NC@CuN/CF catalyst of embodiment 1 at 400nm；
Fig. 2 is that the reaction of 1 electrocatalytic hydrogenation HMF BHMF 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.
The synthesis of embodiment 1:NC@CuN/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
(1) compound concentration is the sodium hydroxide of 5mol/L, prepares the ammonium persulfate aqueous solution of 0.25mol/L, spare；
(2) it is 1:1 according to volume ratio, takes 5mol/L sodium hydroxide solution and the step 1) institute of 20mL obtained by step 1) respectively
The 0.25mol/L ammonium persulfate solution of 20mL is obtained, then two kinds of solution are mixed into solution clarification；
(3) take pre-processed foam copper carrier (pretreatment be conventional treatment method, in acid condition ultrasound 10 points
Clock, then clean, drying is finally washed with water with ultrasound 30 minutes in acetone, second alcohol and water respectively) it is added to the solution that step 2) obtains
Middle reaction 30 minutes, foam copper becomes blue from crocus, obtains forerunner's body catalyst Kocide SD, is denoted as Cu (OH)2/ CF is urged
Agent, what CF was indicated is foam copper；
(4) forerunner's body catalyst in step 3) is impregnated 24 hours in the glucose solution of 0.1mol/L, then 60
It is dried in vacuo at DEG C, obtains carbon-coated catalyst, be denoted as C@Cu (OH)2/ CF catalyst；
(5) the carbon coating catalyst after will be dry in step 4) is placed in tube furnace, is roasted under ammonia, maturing temperature is
300 DEG C, calcining time is 3 hours, obtains carbon coating copper nitride nano-wire catalyst after roasting, is denoted as NC CuN/CF
Catalyst.
Electron microscope observation, the result is shown in Figure 1 a, figure are scanned to the NC@CuN/CF catalyst obtained of embodiment 1
1b.As can be seen from figs. 1a and 1b the NC@CuN/CF catalyst obtained of the present embodiment 1 is thorniness shape nanowire structure.
The catalytic performance for the NC@CuN/CF catalyst that embodiment 1 is prepared is tested, the specific method is as follows:
It is about 2 × 2cm that NC@CuN/CF catalyst, which is cut,2Size, directly as working electrode.It is controlled by galvanostat
Electric current is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 10mL and are separated by cation-exchange membrane, with
The 0.5mol/L H of 10mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, using the NC@CuN/CF catalyst prepared as cathode chamber electrode；
S1: it is reactant by 5 hydroxymethyl furfural (abbreviation HMF), 25.2mg HMF is taken to be added to cathode chamber electrolytic solution
In；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 25 DEG C of temperature of reaction system
20mA, control reference voltage 2-5V react 120 minutes；
S3: after step S2 cathode chamber electrolytic solution is taken out, through methylene chloride extracting and demixing, methylene chloride mutually evaporates point
From to get BHMF product, with the progress in reaction time, reaction result test is as shown in Figure 2.Fig. 2 is the dynamics that HMF adds hydrogen
Scheme, HMF is raw material in figure, and BHMF is principal product.From Fig. 2 it is known that with the reaction time growth, raw material HMF is gradually
It reduces, principal product BHMF is being gradually increased.Wherein, when reaction reaches 120 minutes, the conversion ratio of HMF is the selection of 97%, BHMF
Property is 98%.
Embodiment 2:C@Cu (OH)2The synthesis of/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
(1) compound concentration is the potassium hydroxide of 2mol/L, prepares the ammonium persulfate aqueous solution of 0.5mol/L, spare；
(2) it is 1:1 according to volume ratio, takes 2mol/L sodium hydroxide solution and the step 1) institute of 20mL obtained by step 1) respectively
The 0.5mol/L ammonium persulfate solution of 20mL is obtained, then two kinds of solution are mixed into solution clarification；
(3) take pre-processed foam copper carrier (pretreatment be conventional treatment method, in acid condition ultrasound 10 points
Clock, then clean, drying is finally washed with water with ultrasound 30 minutes in acetone, second alcohol and water respectively) it is added to the solution that step 2) obtains
Middle reaction 30 minutes, foam copper becomes blue from crocus, obtains forerunner's body catalyst Kocide SD, is denoted as Cu (OH)2/ CF is urged
Agent；
(4) forerunner's body catalyst in step 3) is impregnated 30 hours in the glucose solution of 0.2mol/L, then 60
It is dried in vacuo at DEG C, obtains carbon-coated catalyst, be denoted as C@Cu (OH)2/ CF catalyst；
The C@Cu (OH) that embodiment 2 is prepared2The catalytic performance of/CF catalyst is tested, and the specific method is as follows:
By C@Cu (OH)2It is about 2 × 2cm that/CF catalyst, which is cut,2Size, directly as working electrode.By constant current instrument control
Electric current processed is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 20mL and are separated by cation-exchange membrane, with
The 0.1mol/L H of 20mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, the C@Cu (OH) that will have been prepared2/ CF catalyst is as cathode chamber electrode；
S1: it is reactant by HMF, 12.6mg HMF is taken to be added in cathode chamber electrolytic solution；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 30 DEG C of temperature of reaction system
10mA, control reference voltage 1-4V react 120 minutes；
S3: after step S2 cathode chamber electrolytic solution is cooled to room temperature, through ethyl acetate extracting and demixing, ethyl acetate phase is steamed
Hair separation is to get BHMF product.Wherein, when reaction reaches 120 minutes, the selectivity that the conversion ratio of HMF is 78%, BHMF is
81%.Embodiment 2 is tested as a comparison, mainly illustrates that catalyst nitriding step is of crucial importance to HMF electrocatalytic hydrogenation BHMF.
Embodiment 3:Cu (OH)2The synthesis of/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
(1) compound concentration is the barium hydroxide of 3mol/L, prepares the ammonium persulfate aqueous solution of 0.1mol/L, spare；
(2) it is 1:1 according to volume ratio, takes 3mol/L sodium hydroxide solution and the step 1) institute of 20mL obtained by step 1) respectively
The 0.1mol/L ammonium persulfate solution of 20mL is obtained, then two kinds of solution are mixed into solution clarification；
(3) take pre-processed foam copper carrier (pretreatment be conventional treatment method, in acid condition ultrasound 10 points
Clock, then clean, drying is finally washed with water with ultrasound 30 minutes in acetone, second alcohol and water respectively) it is added to the solution that step 2) obtains
Middle reaction 30 minutes, foam copper becomes blue from crocus, obtains forerunner's body catalyst Kocide SD, is denoted as Cu (OH)2/ CF is urged
Agent.
The Cu (OH) that embodiment 3 is prepared2The catalytic performance of/CF catalyst is tested, and the specific method is as follows:
By Cu (OH)2It is about 2 × 2cm that/CF catalyst, which is cut,2Size, directly as working electrode.It is controlled by galvanostat
Electric current is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 10mL and are separated by cation-exchange membrane, with
The 1.0mol/L H of 10mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, by the Cu prepared (OH)2/ CF catalyst is as cathode chamber electrode；
S1: it is reactant by HMF, 25.2mg HMF is taken to be added in cathode chamber electrolytic solution；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 40 DEG C of temperature of reaction system
30mA, control reference voltage 3-7V react 120 minutes；
S3: after step S2 cathode chamber electrolytic solution is cooled to room temperature, through ether extracting and demixing, ether mutually evaporates separation,
Up to BHMF product.Wherein, when reaction reaches 120 minutes, the selectivity that the conversion ratio of HMF is 88%, BHMF is 85%.Implement
Example 3 is tested as a comparison, mainly illustrates that two steps of carbon coating and nitridation are to HMF electrocatalytic hydrogenation system in catalyst preparation process
BHMF is of crucial importance.
The synthesis of embodiment 4:NC@CuN/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
NC@CuN/CF catalyst preparation is such as embodiment 1.The catalytic performance of NC@CuN/CF catalyst is tested, is had
Body method is as follows:
It is about 2 × 2cm that NC@CuN/CF catalyst, which is cut,2Size, directly as working electrode.It is controlled by galvanostat
Electric current is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 20mL and are separated by cation-exchange membrane, with
The 1.0mol/L H of 20mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, using the NC@CuN/CF catalyst prepared as cathode chamber electrode；
S1: it is reactant by HMF, 6.3mg HMF is taken to be added in cathode chamber 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
10mA, control reference voltage 1-5V react 60 minutes；
S3: after step S2 cathode chamber electrolytic solution is cooled to room temperature, through methylene chloride extracting and demixing, methylene chloride mutually steams
Hair separation is to get BHMF product.Wherein, when reaction reaches 60 minutes, the selectivity that the conversion ratio of HMF is 65%, BHMF is
87%, the main reason for conversion ratio is low is that the reaction time is short, and raw material HMF has not been converted.
The synthesis of embodiment 5:NC@CuN/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
NC@CuN/CF catalyst preparation is such as embodiment 1.The catalytic performance of NC@CuN/CF catalyst is tested, is had
Body method is as follows:
It is about 2 × 2cm that NC@CuN/CF catalyst, which is cut,2Size, directly as working electrode.It is controlled by galvanostat
Electric current is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 30mL and are separated by cation-exchange membrane, with
The 2.0mol/L H of 30mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, using the NC@CuN/CF catalyst prepared as cathode chamber electrode；
S1: it is reactant by HMF, 63.0mg HMF is taken to be added in cathode chamber 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
50mA, control reference voltage 3-10V react 180 minutes；
S3: after step S2 cathode chamber electrolytic solution is cooled to room temperature, through chloroform extracting and demixing, chloroform mutually evaporates separation,
Up to BHMF product.Wherein, when reaction reaches 120 minutes, the selectivity that the conversion ratio of HMF is 93%, BHMF is 88%.
The synthesis of embodiment 6:NC@CuN/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
NC@CuN/CF catalyst preparation is such as embodiment 1.The catalytic performance of NC@CuN/CF catalyst is tested, is had
Body method is as follows:
It is about 2 × 2cm that NC@CuN/CF catalyst, which is cut,2Size, directly as working electrode.It is controlled by galvanostat
Electric current is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 20mL and are separated by cation-exchange membrane, with
The 0.1mol/L H of 20mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, using the NC@CuN/CF catalyst prepared as cathode chamber electrode；
S1: it is reactant by HMF, 50.4mg HMF is taken to be added in cathode chamber 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 1-5V react 60 minutes；
S3: after step S2 cathode chamber electrolytic solution is cooled to room temperature, through methylene chloride extracting and demixing, methylene chloride mutually steams
Hair separation is to get BHMF product.Wherein, when reaction reaches 60 minutes, the selectivity that the conversion ratio of HMF is 72%, BHMF is
84%.
The synthesis of embodiment 7:NC@CuN/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
NC@CuN/CF catalyst preparation is such as embodiment 1.The catalytic performance of NC@CuN/CF catalyst is tested, is had
Body method is as follows:
It is about 2 × 2cm that NC@CuN/CF catalyst, which is cut,2Size, directly as working electrode.It is controlled by galvanostat
Electric current is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 10mL and are separated by cation-exchange membrane, with
The 0.5mol/L H of 10mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, using the NC@CuN/CF catalyst prepared as cathode chamber electrode；
S1: it is reactant by HMF, 63.0mg HMF is taken to be added in cathode chamber electrolytic solution；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 30 DEG C of temperature of reaction system
20mA, control reference voltage 2-7V react 240 minutes；
S3: after step S2 cathode chamber electrolytic solution is cooled to room temperature, through ethyl acetate extracting and demixing, ethyl acetate phase is steamed
Hair separation is to get BHMF product.Wherein, when reaction reaches 240 minutes, the selectivity that the conversion ratio of HMF is 89%, BHMF is
91%.
The synthesis of embodiment 8:NC@CuN/CF catalyst and its electrocatalytic hydrogenation HMF BHMF
NC@CuN/CF catalyst preparation is such as embodiment 1.The catalytic performance of NC@CuN/CF catalyst is tested, is had
Body method is as follows:
It is about 2 × 2cm that NC@CuN/CF catalyst, which is cut,2Size, directly as working electrode.It is controlled by galvanostat
Electric current is reacted using H-type electrolytic cell, and anode chamber and cathode chamber volume are 20mL and are separated by cation-exchange membrane, with
The 0.1mol/L H of 20mL2SO4Electrolytic solution of the aqueous solution as anode chamber and cathode chamber；In electrolyzer anode chamber, platinum electrode is made
For anode chamber's electrode；In electric tank cathode room, using the NC@CuN/CF catalyst prepared as cathode chamber electrode；
S1: it is reactant by HMF, 25.2mg HMF is taken to be added in cathode chamber electrolytic solution；
S2: electrolytic cell is integrally placed in water bath with thermostatic control to stir, current control is to control 25 DEG C of temperature of reaction system
10mA, control reference voltage 1-5V react 120 minutes；
S3: after step S2 cathode chamber electrolytic solution is cooled to room temperature, through methylene chloride extracting and demixing, methylene chloride mutually steams
Hair separation is to get BHMF product.Wherein, when reaction reaches 120 minutes, the selectivity that the conversion ratio of HMF is 68%, BHMF is
79%, the main reason for conversion ratio is low is that the electric current that applies is smaller, and W-response is slow, and raw material HMF conversion ratio is not high.
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 (9)
1. a kind of method that carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation produces 2,5-FDM, feature exist
In using H-type electrolytic cell as reactor, voltage and current is controlled with galvanostat, is handed among the H-type electrolytic cell by cation
It changes film to separate to form cathode chamber and anode chamber, platinized platinum is anode chamber's electrode, and the acid solution of 0.1-2.0mol/L is as anolyte；
Carbon coating copper nitride nano-wire catalyst is cathode chamber electrode, and reaction substrate 5 hydroxymethyl furfural is dissolved in 0.1-2.0mol/L's
It is used as catholyte in acid solution, is carried out under conditions of temperature is 25-80 DEG C, electric current 10-100mA, tank voltage are 1-10V
Electrocatalytic hydrogenation reaction, reaction time 1-5h, after reaction, the indoor reaction solution of cathode is cooling and is extracted with organic solvent,
Organic phase atmospheric distillation obtains 2,5-FDM, and reaction equation is as follows:
2. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 1 produces 2,5- furans two
The method of methanol, it is characterised in that cathode chamber and anode chamber's volume are 10-50mL, preferable volume 10-20mL.
3. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 1 produces 2,5- furans two
The method of methanol, it is characterised in that the volumetric usage of catholyte is calculated as 5-50mmol/L with the amount of 5 hydroxymethyl furfural substance, excellent
It is selected as 10-30mmol/L.
4. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 1 produces 2,5- furans two
The method of methanol, it is characterised in that acid solution be sulfuric acid solution, perchloric acid solution, nitric acid solution or hydrochloric acid solution, preferably
Sulfuric acid solution, the concentration of acid solution are 0.1-1.0mol/L.
5. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 1 produces 2,5- furans two
The method of methanol, it is characterised in that electrocatalytic hydrogenation kinetic current is 10-50mA, tank voltage 1-7V, reaction temperature 25-50
DEG C, reaction time 1-3h.
6. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 1 produces 2,5- furans two
The method of methanol, it is characterised in that extraction is methylene chloride, ether, chloroform or ethyl acetate with organic solvent.
7. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 1 produces 2,5- furans two
The method of methanol, it is characterised in that the carbon coating copper nitride nano-wire catalyst preparation method includes the following steps:
1) foam copper carrier is pre-processed, the foam copper carrier size is 1 × 1cm-5 × 5cm, preferably 2cm × 2cm；
2) being dissolved in water alkali and being made into concentration is 1-10mol/L aqueous slkali, and the alkali is sodium hydroxide, potassium hydroxide or hydrogen-oxygen
Change barium, preferably sodium hydroxide, the concentration of alkali are preferably 2-5mol/L；
3) ammonium persulfate is dissolved in water to the ammonium persulfate solution for being made into that concentration is 0.1-1.0mol/L, the ammonium persulfate is molten
The concentration of liquid is preferably 0.1-0.5mol/L；
4) it is 1:1 according to volume ratio, takes the resulting aqueous slkali of step 2) and the resulting ammonium persulfate solution mixing of step 3) respectively,
Stirring to solution clarifies to obtain mixed solution；
5) the foam copper carrier of step 1) is added in the mixed solution that step 4) obtains and is reacted 30 minutes, foam copper is by crocus
Become blue, obtains forerunner's body catalyst Kocide SD, be denoted as Cu (OH)2/ CF catalyst, what CF was indicated is foam copper；
6) forerunner's body catalyst Kocide SD in step 5) is impregnated 10-30 hours in glucose solution, then at 60 DEG C
Vacuum drying, obtains carbon-coated catalyst, is denoted as C@Cu (OH)2/ CF catalyst；
7) the carbon coating catalyst after will be dry in step 6) is placed in tube furnace, is roasted under ammonia, maturing temperature 200-
500 DEG C, calcining time 1-3h, carbon coating copper nitride nano-wire catalyst is obtained after roasting, NC CuN/CF is denoted as and urges
Agent.
8. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 7 produces 2,5- furans two
The method of methanol, it is characterised in that the detailed process of pretreatment foam copper carrier are as follows: ultrasound 10 minutes in acid condition, then divide
Not Yong acetone, ultrasound 30 minutes in second alcohol and water, be finally washed with water it is clean, it is dry.
9. a kind of carbon coating copper nitride nano-wire catalyst electrocatalytic hydrogenation according to claim 7 produces 2,5- furans two
The method of methanol, it is characterised in that the concentration of the glucose solution in step 6) is 0.1-0.5mol/L, and preferred concentration is
0.1mol/L, the dip time in glucose solution are 24 hours.
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