CN109292766A - A kind of clean preparation method of Activated Graphite alkene - Google Patents
A kind of clean preparation method of Activated Graphite alkene Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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Abstract
The present invention relates to a kind of clean preparation methods of Activated Graphite alkene, it is characterised in that with HNO3HCL aqueous solution oxidation activity graphite powder prepares active oxidation graphene, with glyoxal reduction activation graphene oxide, two kinds of products of Activated Graphite alkene and glyoxalic acid are produced simultaneously, and technical solution includes intercalation the etching activation, four part of the preparation of active oxidation graphene, the reduction of active oxidation graphene and the preparation of glyoxalic acid of graphite powder.The intercalation etching activation of graphite powder is to mix graphite powder and sylvite, is heated to 760-850 DEG C under nitrogen protection, makes the molecule interlayer of potassium atom gas insertion graphite, while etching aperture activation on the crystal face of graphite linings, convenient for penetrating into for subsequent oxidation agent.The present invention solves the problems, such as that a large amount of spent acid are difficult to dispose in graphene product production, realize the clean manufacturing of graphene product.
Description
Technical field
The present invention relates to a kind of clean preparation method of Activated Graphite alkene, especially a kind of HNO3HCL aqueous solution oxidation is lived
Property graphite powder prepare active oxidation graphene, with glyoxal reduction activation graphene oxide, while producing Activated Graphite alkene and second
The method of two kinds of products of aldehydic acid, belongs to chemical industry and field of new materials.
Technical background
Graphene has light transmission, conduction, thermally conductive, high-intensitive, high tenacity and high-specific surface area as a kind of emerging carbon material
Etc. characteristics, the conversion of catalysis, electronic device and energy with store and the fields such as biological medicine have broad application prospects.Oxygen
Graphite alkene is a kind of important Graphene derivative, has two-dimensional slice structure similar with graphene.The difference is that it draws
A large amount of oxygen-containing group is entered, sheet surfaces are dispersed with hydroxyl and epoxy group, and lamella edge contains carboxyl and carbonyl.Introducing contains
Big pi bond after oxygen groups in graphene molecules is destroyed, and mechanical property and electric property all decline, or even lose electric conductivity.
Oxygen-containing functional group in graphene oxide molecule is taken off using modes such as electronation, hydrothermal reduction, thermal reduction and catalysis reduction
It removes, generates redox graphene, the performance of graphene can have been restored.Graphene oxide is initially as macroscopic preparation of graphene
Presoma, due to its be different from graphene unique physico-chemical property, carried out a large amount of bases as Graphene derivative
And application study.
The preparation method of graphene oxide mainly has chemical oxidization method and electrochemical oxidation process, has industrialized developing prospect
Be chemical oxidization method.Chemical oxidization method is exactly to handle graphite with inorganic acid, strong acid small molecule is inserted into graphite layers, then use
Strong oxidizer aoxidizes it to obtain graphene oxide.The open oxidation stone of United States Patent (USP) US9428394B2 (2016-08-30)
The inorganic acid of black alkene preparation is sulfuric acid, chlorosulfonic acid, fluosulfonic acid and trifluoromethanesulfonic acid and combinations thereof, oxidant be selected from permanganate,
Ferrate, chlorate, chlorite, nitrate, ruthenate and brown lead oxide and combinations thereof.United States Patent (USP) US2018/
0230014A1 (2018-08-16) discloses graphene oxide and graphene Low-cost production method, using potassium permanganate, sulfuric acid
And hydrogen peroxide oxidant, using hydroiodic acid redox graphene.Chinese patent CN105293476A(2016-02-03) it is public
In the graphene oxide and graphene preparation method opened, using persulfate, potassium bichromate, potassium permanganate, potassium ferrate, nitric acid
Salt or concentrated nitric acid are that oxidant prepares graphene oxide, using hydrazine hydrate, hydroiodic acid, lithium aluminium hydride, sodium borohydride, hydroxide
Sodium, sodium citrate or ascorbic acid are that reducing agent prepares graphene.Chinese patent CN102718209A(2012-10-10) it is open
Graphene preparation method in, use potassium permanganate, potassium chlorate or potassium bichromate for oxidant, using divalent iron salt as reducing agent.
Chinese patent CN102583343A(2012-07-18) disclosed in high-volume graphene preparation method, using potassium permanganate, chlorine
Sour potassium or potassium bichromate are oxidant, using acetone, ethyl alcohol or methanol as reducing agent.The graphene oxide and stone of conventional method synthesis
The specific surface area of black alkene is lower, and absorption property is bad, limits its scope of application to a certain extent, especially energy conversion and storage
The application for depositing field is restricted.Chinese patent CN108046242A(2018-05-18) preparation of poroid graphene a kind of is disclosed
Graphene oxide is ultrasonically treated by method in strong base solution, and then electronation obtains poroid graphene.Chinese patent
CN103395779A(2013-11-20) a kind of porous graphene and preparation method thereof, under the action of oxidant, graphite are disclosed
Substance and sulphur heat in a solvent to react, and obtains porous graphene.Chinese patent CN104916446A(2015-09-
16) open be blended in activator in certain temperature range with graphene oxide is restored and is activated, and obtains supercapacitor
With Activated Graphite alkene.The shortcomings that these methods is must to prepare graphene oxide first, and the cost for obtaining Activated Graphite alkene is high,
It is difficult to scale up production application.Although domestic and international chemical method prepares graphene and there are many patent of Activated Graphite alkene, all do not solve
Low yield, high production cost and waste is prepared to be difficult to the problem of disposing, fail industrial applications so far.The master of field of graphene
Wanting problem is to research and develop the preparation method of safety and environmental protection, produces the good graphene product of high yield, low cost and controllability.
Summary of the invention
It is an object of the present invention to provide a kind of clean preparation methods of Activated Graphite alkene, it is characterised in that with HNO3HCl/water is molten
Liquid oxidation Activated Graphite prepares active oxidation graphene, with glyoxal reduction activation graphene oxide, while producing Activated Graphite
Two kinds of products of alkene and glyoxalic acid, a large amount of Waste Sulfuric Acids are difficult to dispose when fundamentally solving existing chemical method preparation graphene product
The problem of, technical solution includes intercalation the etching activation, the preparation of active oxidation graphene, active oxidation graphene of graphite powder
Four part of preparation of reduction and glyoxalic acid.
The intercalation etching activation of graphite powder is to mix graphite powder and sylvite with mass ratio 1:0.1-1.0 in the present invention,
It is heated to 760-850 DEG C under logical nitrogen protection, keeps the temperature 0.5-1h, sylvite thermal reduction is made to decompose the potassium atom gas insertion stone generated
The molecule interlayer of ink supports the big gap of graphitic molecules layers, while aperture activation is etched on the crystal face of graphite linings, increases its ratio
Surface area obtains Activated Graphite powder, then passes to air and is cooled to room temperature, makes graphite linings surface preoxidizing graphitic acid, increases
Wettability of the surface, to facilitate penetrating into for subsequent oxidation agent solution, the sylvite is K2O、KOH、K2CO3、KNO3Or have
One of machine acid potassium salt.
The preparation of active oxidation graphene is that the Activated Graphite powder for obtaining intercalation etching activation is impregnated into HCl in the present invention
Mass percentage concentration is 10%-25% and HNO3Mass percentage concentration is the HNO of 10%-50%3In HCL aqueous solution, at 40-70 DEG C
Oxidation reaction 4-6h is carried out, the HNO that mass percentage concentration is 50% is continuously replenished during the reaction3Solution controls HNO3With work
Property graphite molar feed ratio be 0.6-1.2, Activated Graphite powder by nitryl oxychloride generate active oxidation graphene, active oxidation
C/O molar ratio is 1.6-3 in graphene molecules, and chloro-nitric acid is reduced to nitrosyl chloride, and further hydrolysis generates nitrogen oxide gas,
The nitrogen oxide tail gas generated in reaction recycles after being absorbed with water.
The reduction of active oxidation graphene is the glyoxal quality that oxidation liquid is added portionwise to 40-60 DEG C in the present invention
Percentage concentration is that 15%-25% and HCl mass percentage concentration is control investment HNO in the aqueous solution of 3%-5%3Molal quantity and second
The ratio between molal quantity of dialdehyde is 0.3-0.6, and oxidation liquid adds in 2-4h, then proceedes to insulation reaction 0.5-2h, second two
Aldehyde is oxidized to glyoxalic acid, the HNO in oxidation liquid3It is reduced to nitrogen oxide gas by glyoxal to release, in oxidation liquid
Active oxidation graphene graphene Precipitation is reduced to by glyoxal, make C/O molar ratio 6- in Activated Graphite alkene molecule
9, it is centrifugated Activated Graphite alkene, deionized water cleaning, vacuum drying obtains Activated Graphite alkene product, specific surface area is
500-1500m2/g。
The preparation of glyoxalic acid is that reduction reaction mother liquor is heated to 40-60 DEG C in the present invention, and it is dense to continuously add quality percentage
The HNO that degree is 50%3Oxidant makes the mass percentage concentration of remaining glyoxal in mother liquor less than 0.5%, then vacuum evaporation
Glyoxalic acid reaction liquid is until glyoxalic acid mass percentage concentration is greater than 40%, and cooling glyoxalic acid concentrate is to 0-5 DEG C, Crystallization Separation
The oxalic acid of precipitation is adjusted so as to the glyoxylic acid solution that mass percentage concentration is 40% with deionized water, glyoxal impurity therein
For mass content less than 1.0%, it is dense to evaporate HCl mass in the distillate of recycling less than 1.0% for the mass content of oxalic acid impurity therein
Degree is 10%-15%, HNO3Mass concentration is 0.3%-1.0%, is circularly used for HNO3The preparation of HCL aqueous solution.
The one of the major reasons that graphite powder is not easy to be oxidized to graphene are exactly that oxidant is difficult to penetrate into graphite layers
In gap, it usually needs the concentrated sulfuric acid is added and impregnates intercalation, so that graphite linings expansion is expanded gap, a large amount of Waste Sulfuric Acids is caused to generate.
The present invention is different from existing Activated Graphite alkene preparation method, is not first to prepare graphene oxide reactivation preparation activity
Graphene oxide, but Activated Graphite powder is first prepared, it is active oxidation graphene by Activated Graphite powder direct oxidation, restores
To Activated Graphite alkene.The principle of applied activated carbon preparation in the preparation of Activated Graphite powder, makes the thermal reduction of sylvite high temperature generate potassium atom
Gas has supportted the gap of graphite linings big with atomic volume biggish potassium atom intercalation etching activation graphite linings, increases graphite powder
Specific surface area increases the mass transfer channel of graphite crystal face；The pre-oxidation of hot-air has been carried out to Activated Graphite layer, has made subsequent oxidation
HNO in the process3- HCl oxidant, which is easily wetted and is penetrated into the gap of graphite linings, carries out oxidation reaction.
HNO is used in the present invention3The Activated Graphite powder of HCL aqueous solution oxidation intercalation etching activation prepares active oxygen fossil
Black alkene, HNO3HCL aqueous solution has the characteristics that dilute " chloroazotic acid ", HNO3Chloro-nitric acid (the NO to be formed is reacted with HCl2Cl) the oxygen of molecule
Change ability is much higher than the HNO of same concentration3, the NO of intermediate concentration2Cl aqueous solution just has very strong oxidability, when heated
The part carbon atom in Activated Graphite molecular layer can be made to be oxidized to carbonyl and carboxyl.The introducing of oxygen-containing functional group makes graphite layers
Reaction force attenuation, be easily peeled off generate active oxidation graphene.The nitrogen oxide volume expansion generated on reaction active site can
Promote the active oxidation graphene generated removing.Oxidation reaction generate glyoxalic acid and oxalic acid to Activated Graphite alkene have intercalation and
Suction-operated promotes active oxidation graphene to remove and block it and re-unites.The raising of oxidizing reaction temperature can accelerate oxidant
Infiltration, the oxidation of Activated Graphite and the removing of active oxidation graphene.
Glyoxal is a kind of industrial chemicals and intermediate, it can carry out intercalation and suction to active oxidation graphene molecules
It is attached, promote the splitting of active oxidation graphene to re-unite with it is blocked.Glyoxal has stronger reproducibility, can be by work
Property graphene oxide molecule in oxygen-containing functional group reduction removal revert to Activated Graphite alkene structure.Glyoxal also can be by reaction solution
In chloro-nitric acid (NO2Cl it) is reduced to nitrosyl chloride (NOCl), is further hydrolyzed to nitrogen oxide and HCl removal, itself is oxidized
For glyoxalic acid, reaction process is expressed as follows:
HNO3+HCl→NO2Cl+H2O (1)
GP+ NO2Cl→GO+NOCl(2)
GO+CHOCHO→G+ CHOCOOH (3)
CHOCHO + NO2Cl→CHOCOOH+ NOCl (4)
CHOCOOH+ NO2Cl →COOHCOOH+ NOCl (5)
2NOCl+H2O→ NO2 + NO+2HCl (6)
GP represents Activated Graphite in reaction equation；GO represents active oxidation graphene；G represents Activated Graphite alkene.
Glyoxalic acid is a kind of widely used fine chemicals, and the glyoxalic acid for being usually 40% or 50% with mass concentration is water-soluble
Liquid sale, is mainly used for the medication chemistries productions such as 4-Hydroxyphenyl hydantoin, vanillic aldehyde and hydroxyl phosphine carboxylic acid.Glyoxalic acid industry is raw
Production method mainly has oxidation of glyoxal, oxalic acid reduction method and cis-butenedioic anhydride ozonization method etc..Oxidation of glyoxal can be used various
Oxidant aoxidizes glyoxal water solution in acid condition and prepares glyoxalic acid, common oxidant mainly have nitric acid, nitrogen oxides,
Chlorine, air and combinations thereof.The preparation of Activated Graphite alkene and glyoxalic acid production are combined together by the present invention, solve graphene production
A large amount of spent acid handling problems in product production, while reducing the production cost of glyoxalic acid.
Experimental raw potassium hydroxide, potassium carbonate, potassium nitrate, nitric acid, hydrochloric acid and glyoxal etc. used in the present invention are commercially available
Chemically pure reagent.Graphite powder used be Dongguan, Guangdong pull together Graphite Company offer 5000 mesh flaky graphite powders, carbon content
99%。
The beneficial effects of the present invention are embodied in:
(1) two kinds of high value-added products of Activated Graphite alkene and glyoxalic acid are obtained simultaneously, reduces production cost；
(2) solve the problems, such as that a large amount of spent acid are difficult to dispose in graphene product production, the cleaning for realizing Activated Graphite alkene is raw
It produces；
(3) the intercalation etching activating pretreatment of graphite keeps aqueous oxidizing agent solution readily permeable into graphite linings gap, makes active stone
The aqueous solution chlorination process of ink is able to carry out.
Specific embodiment
Embodiment 1
The flaky graphite powder 12g(1.0mol of 5000 mesh) is mixed with potassium carbonate 6g and is placed in crucible, under nitrogen protection
800 DEG C are heated to, 0.5-1h is kept the temperature, then passes to air furnace cooling, graphite linings are carried out with the pre-oxidation of hot-air.By intercalation
Etching the Activated Graphite powder being activated and being impregnated into HCl mass percentage concentration is 20% and HNO3Mass percentage concentration is 20%
HNO3In HCL aqueous solution 200g, oxidation reaction 4-6h is carried out at 40-70 DEG C, during the reaction additional mass percentage concentration
For 50% HNO3Solution 46g, Activated Graphite powder generate active oxidation graphene, the oxidation generated in reaction by nitryl oxychloride
Nitrogen tail gas recycles after being absorbed with water.It is 20% by the glyoxal mass percentage concentration that oxidation liquid is added portionwise 40-60 DEG C
In the aqueous solution 500g for being 5% with HCl mass percentage concentration, oxidation liquid adds in 2-4h, then proceedes to insulation reaction
0.5-2h, the active oxidation graphene in oxidation liquid are reduced to Activated Graphite alkene Precipitation by glyoxal, are centrifugated
Activated Graphite alkene, deionized water are cleaned, and are dried in vacuo at 60 DEG C, are obtained Activated Graphite alkene product 11.6g, specific surface area is
1200m2/ g, C/O molar ratio is 9 in Activated Graphite alkene molecule.
Reduction reaction mother liquor is heated to 40-60 DEG C, continuously adds the HNO that mass percentage concentration is 50%3Oxidant 63g,
Make the mass percentage concentration of remaining glyoxal in mother liquor less than 0.5%, then vacuum evaporation glyoxalic acid reaction liquid to glyoxalic acid
Until mass percentage concentration is greater than 40%, for cooling glyoxalic acid concentrate to 0-5 DEG C, oxalic acid 46g is precipitated in Crystallization Separation, uses deionization
Water adjusts to obtain the glyoxylic acid solution 240g that mass percentage concentration is 40%, and the mass content of glyoxal impurity therein is less than
1.0%, the mass content of oxalic acid impurity therein is less than 1.0%.
Claims (5)
1. a kind of clean preparation method of Activated Graphite alkene, it is characterised in that with HNO3HCL aqueous solution oxidation activity graphite powder system
Standby graphene oxide with glyoxal reduction activation graphene oxide, while producing two kinds of products of Activated Graphite alkene and glyoxalic acid, from
Fundamentally solve the problems, such as that a large amount of Waste Sulfuric Acids are difficult to dispose when existing chemical method preparation graphene product, technical solution includes stone
The intercalation of ink powder etches activation, the preparation of active oxidation graphene, the reduction of active oxidation graphene, the preparation of glyoxalic acid four
Point.
2. the clean preparation method of Activated Graphite alkene according to claim 1, it is characterised in that the intercalation of graphite powder etches
Activation is to mix graphite powder and sylvite with mass ratio 1:0.1-1.0,760-850 DEG C is heated under logical nitrogen protection, heat preservation
0.5-1h makes sylvite thermal reduction decompose the molecule interlayer of the potassium atom gas insertion graphite generated, supports big graphitic molecules layers
Gap, while aperture activation is etched on the crystal face of graphite linings, increase the specific surface area of graphite powder, obtains Activated Graphite powder, so
After be passed through air and be cooled to room temperature, make graphite linings surface preoxidizing graphitic acid, increase wettability of the surface, to facilitate subsequent oxygen
Agent solution penetrates into, and the sylvite is K2O、KOH、K2CO3、KNO3Or organic acid potassium salt.
3. the clean preparation method of Activated Graphite alkene according to claim 1, it is characterised in that active oxidation graphene
Preparation is that the Activated Graphite powder after intercalation etching activation is impregnated into HCl mass percentage concentration as 10%-25% and HNO3Quality hundred
Dividing concentration is the HNO of 10%-50%3In HCL aqueous solution, oxidation reaction 4-6h is carried out at 40-70 DEG C, during the reaction not
The HNO that disconnected additional mass percentage concentration is 50%3Solution controls HNO3Molar feed ratio with graphite is 0.6-1.2, Activated Graphite
Powder generates active oxidation graphene by nitryl oxychloride, and C/O molar ratio is 1.6-3, chloro-nitric acid in active oxidation graphene molecules
It is reduced to nitrosyl chloride, further hydrolysis generates nitrogen oxide gas, and the nitrogen oxide tail gas generated in reaction follows after being absorbed with water
Ring utilizes.
4. the clean preparation method of Activated Graphite alkene according to claim 1, it is characterised in that active oxidation graphene
Reduction be oxidation liquid is added portionwise 40-60 DEG C glyoxal mass percentage concentration be 15%-25% and HCl mass percentage it is dense
Degree is control investment HNO in the aqueous solution of 3%-5%3Molal quantity and the ratio between the molal quantity of glyoxal be 0.3-0.6, oxidation is anti-
It answers liquid to add in 2-4h, then proceedes to insulation reaction 0.5-2h, glyoxal is oxidized to glyoxalic acid, in oxidation liquid
HNO3It is reduced to nitrogen oxide gas by glyoxal to release, the active oxidation graphene in oxidation liquid is reduced to live by glyoxal
Property graphene Precipitation, be centrifugated Activated Graphite alkene, deionized water cleaning, vacuum drying, obtain Activated Graphite alkene product,
Its specific surface area is 500-1500m2/ g, C/O molar ratio is 6-9 in Activated Graphite alkene molecule.
5. the clean preparation method of Activated Graphite alkene according to claim 1, it is characterised in that the preparation of glyoxalic acid be by
Reduction reaction mother liquor is heated to 40-60 DEG C, continuously adds HNO3Oxidant, until the quality percentage of glyoxal remaining in mother liquor is dense
Degree is less than 0.5%, and then vacuum evaporation glyoxalic acid reaction liquid, makes glyoxalic acid mass percentage concentration be greater than 40%, cooling acetaldehyde
Sour concentrate is to 0-5 DEG C, the oxalic acid that Crystallization Separation is precipitated, and deionized water is added and adjusts to obtain the second that mass percentage concentration is 40%
Aldehydic acid solution, the mass content of glyoxal impurity therein is less than 1.0%, and the mass content of oxalic acid impurity therein is less than 1.0%.
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| CN106028768A (en) * | 2016-05-17 | 2016-10-12 | 国网重庆市电力公司电力科学研究院 | Iron-plated graphene and preparation method |
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| CN102040217A (en) * | 2009-10-26 | 2011-05-04 | 国家纳米科学中心 | Method for preparing graphene |
| WO2014060685A1 (en) * | 2012-10-19 | 2014-04-24 | Arkema France | Method for producing a graphene-based thermosetting composite material |
| CN103641108A (en) * | 2013-12-11 | 2014-03-19 | 江苏科技大学 | Method for preparing graphene oxide by using N-methyl-N-morpholine oxide |
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