CN103950921B - A kind of method of graphite oxide high efficiency separation purifying - Google Patents
A kind of method of graphite oxide high efficiency separation purifying Download PDFInfo
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- CN103950921B CN103950921B CN201410164165.2A CN201410164165A CN103950921B CN 103950921 B CN103950921 B CN 103950921B CN 201410164165 A CN201410164165 A CN 201410164165A CN 103950921 B CN103950921 B CN 103950921B
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Abstract
A kind of method of graphite oxide high efficiency separation purifying is by being separated removing clear liquid by the graphite oxide stoste synthesized, collect solid materials, in solid materials, add mixed organic solvents be mixed with graphite oxide dispersion, by dispersion liquid separated and collected solid materials, by underpressure distillation or cryodesiccated method, the mixed organic solvents in the slurry of solids of finally collecting is removed, obtain high purity oxygen graphite.It is high that the present invention has separation efficiency, the advantage that energy consumption is low, simple.
Description
Technical field
The present invention relates to a kind of method of graphite oxide high efficiency separation purifying.
Background technology
Graphene has excellent power, heat, optical, electrical performance, has wide practical use at numerous areas such as lithium ion battery, ultracapacitor, catalysis and coating.Graphene mass-producing controlled synthesis is the prerequisite of its commercial applications and basis.At present, chemical stripping legal system has the advantages such as raw material is easy to get, with low cost, technical maturity for Graphene, as one of the main technological route of Graphene mass production.
Prepare Graphene operational path for oxidation intercalation stripping method, the purifying of intermediate oxidation graphite is the speed limit link of this technique, directly affects production efficiency and the product purity of Graphene industrialization.At present, the purifying process of graphite oxide mainly uses deionized water as purification solvent, and the maximum bottleneck that this technique runs into is along with H in the graphite oxide water-sol
+, Na
+, K
+, Mn
2+the reduction of plasma concentration, the Swelling of graphite oxide is more serious, and its viscosity acutely increases, and the production efficiency of the purifying process such as sedimentation, centrifugal and filtration is sharply declined, and graphite oxide solid-liquid separation effect also seriously reduces.
Researchist improves this washing purifying process for the problems referred to above, and it is after 5% ~ 20% hydrochloric acid soln washing that patent CN102145887B provides a kind of massfraction that adopts, and re-uses the sulfuric acid of 18mol/L: H
2o
2mass ratio is that the mixed aqueous solution of 3 ~ 10:1 carrys out purification of graphite oxide alkene as washing composition.Patent CN103153854A provides the method for the mixture of a kind of alkaline solution treatment graphite oxide and impurity, makes the magazins' layout of graphene oxide and alkalization.The alkali used in the method is the metal carbonate of the 1st race, supercarbonate, oxyhydroxide and metal alkoxide etc.CN103172056 also provides a kind of method adopting alkaline solution treatment graphite oxide dispersion.Above-mentioned several method improves the solid-liquid separation efficiency of graphite oxide all to a certain extent, but new foreign ion can be introduced in purge process, need after having washed by purification solvent additionally to increase deionized water removes the new foreign ion introduced step as washing composition, this can increase the water loss of whole purge process.In addition, the chlorion introduced as washing composition of hydrochloric acid has corrosive nature for the purifier apparatus of stainless steel, adding of alkaline solution serves reductive action to graphite oxide, oxygen-containing functional group quantity on graphite oxide is decreased, and this will affect the chemically reactive of graphite oxide and the application in catalysis etc. thereof.
Provide a kind of employing single organic solvent not of the same race in patent CN102626591A and wash graphite oxide as purifying agent, this method largely solves graphite oxide swelling problem in aqueous, improve the solid-liquid separation efficiency of graphite oxide suspension to a certain extent, but its solid-liquid separation efficiency is still lower.
Summary of the invention
The object of the invention is to overcome the weak point that above-mentioned several purification solvent is brought, provide a kind of solid-liquid separation efficiency high, the method for the graphite oxide high efficiency separation purifying that energy consumption is low, simple.
The present invention realizes the technical scheme that above-mentioned purpose adopts:
1) by the graphite oxide stoste that synthesizes by sedimentation, centrifugal or filter type removing clear liquid, collect solid materials;
2) in the solid materials collected, add mixed organic solvents, make it dispersed, be mixed with the dispersion liquid that graphite oxide concentration is 1-20g/L, by dispersion liquid sedimentation, centrifugal or filter type removing clear liquid, collect solid materials;
3) repeating step 2, until the pH value of clear liquid reaches 5.5-6.5;
4) by underpressure distillation or cryodesiccated method, the mixed organic solvents in the slurry of solids of finally collecting is removed, obtain high purity oxygen graphite;
Wherein, mixed organic solvents used is made up of methyl alcohol, ethanol, acetone and dimethyl formamide, and the volume ratio of contained methyl alcohol is 0.5-98.5%, and the volume ratio of ethanol is 0.5-98.5%, the volume ratio of acetone is 0.5-98.5%, and the volume ratio of dimethyl formamide is 0.5-98.5%.
Compared with the technique that the present invention and purifying used at present wash, the purifying agent that the present invention uses is mixed organic solvents, and solvent molecule polarity is little, less with the intermolecular interaction of graphite oxide, easily realize solid-liquid separation, and separation efficiency is high.Therefore, the problem that the viscosity solving the swelling and colloidal sol of graphite oxide in washing process acutely increases, thus to significantly improve in graphite oxide washing process that the settling time is long, centrifugal separating effect is poor and many situations such as filter media surface blocking, the method is simple, energy consumption is low, production efficiency is high, meets the demand of mass production.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail:
Comparative example
1, the graphite oxide stoste synthesized by 5L removes clear liquid by the mode of sedimentation, collects oxidation graphite solid material.
2, in the oxidation graphite solid material collected, add 50L ethanol, being mixed with concentration is 1g/L dispersion liquid.Uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.
3, repeat 4 steps 2, the pH value of clear liquid reaches 5.0.
4, removed by the ethanol in the slurry of solids of finally collecting by the method for underpressure distillation, the purity obtaining graphite oxide is 99.2%.
Embodiment 1
1. the graphite oxide stoste synthesized by 5L removes clear liquid by centrifugal mode, collects oxidation graphite solid material.
2. add 5L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 10mg/mL dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 50%, ethanol 5%, acetone 40%, dimethyl formamide 5%.
3. repeat 2 steps 6 time, until the pH value of clear liquid reaches 5.6.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.45%.
Embodiment 2
1. the graphite oxide stoste synthesized by 5L removes clear liquid by the mode of filtering, and collects oxidation graphite solid material.
2. add 2.5L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 20g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 5%, ethanol 94%, acetone 0.5%, dimethyl formamide 0.5%.
3. repeat 2 steps 8 time, until the pH value of clear liquid reaches 5.5.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.37%.
Embodiment 3
1. the graphite oxide stoste synthesized by 5L removes clear liquid by centrifugal mode, collects oxidation graphite solid material.
2. add 3L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 16.7g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 0.5%, ethanol 10%, acetone 4.5%, dimethyl formamide 85%.
3. repeat 2 steps 7 time, until the pH value of clear liquid reaches 5.7.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.52%.
Embodiment 4
1. the graphite oxide stoste synthesized by 5L removes clear liquid by the mode of filtering, and collects oxidation graphite solid material.
2. add 10L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 5g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 5%, ethanol 80%, acetone 5%, dimethyl formamide 10%.
3. repeat 2 steps 5 time, until the pH value of clear liquid reaches 5.8.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.64%.
Embodiment 5
1. the graphite oxide stoste synthesized by 5L removes clear liquid by the mode of sedimentation, collects oxidation graphite solid material.
2. add 20L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 2.5g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 98.5%, ethanol 0.5%, acetone 0.5%, dimethyl formamide 0.5%.
3. repeat 2 steps 4 time, until the pH value of clear liquid reaches 5.9.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.71%.
Embodiment 6
1. the graphite oxide stoste synthesized by 5L removes clear liquid by centrifugal mode, collects oxidation graphite solid material.
2. add 20L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 2.5g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 0.5%, ethanol 98.5%, acetone 0.5%, dimethyl formamide 0.5%.
3. repeat 2 steps 4 time, until the pH value of clear liquid reaches 5.9.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.72%.
Embodiment 7
1. the graphite oxide stoste synthesized by 5L removes clear liquid by the mode of filtering, and collects oxidation graphite solid material.
2. add 25L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 2g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 0.5%, ethanol 0.5%, acetone 98.5%, dimethyl formamide 0.5%.
3. repeat 2 steps 4 time, until the pH value of clear liquid reaches 6.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.95%.
Embodiment 8
1. the graphite oxide stoste synthesized by 5L removes clear liquid by centrifugation, collects oxidation graphite solid material.
2. add 12.5L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 4g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 0.5%, ethanol 0.5%, acetone 0.5%, dimethyl formamide 98.5%.
3. repeat 2 steps 6 time, until the pH value of clear liquid reaches 5.8.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.65%.
Embodiment 9
1. the graphite oxide stoste synthesized by 5L removes clear liquid by the mode of filtering, and collects oxidation graphite solid material.
2. add 4L mixed organic solvents by the oxidation graphite solid material of collection, being mixed with concentration is 12.5g/L dispersion liquid, uniform dispersion is removed clear liquid by centrifugal mode and collects solid materials.The volume proportion of mixed organic solvents used is methyl alcohol 0.5%, ethanol 9.5%, acetone 80%, dimethyl formamide 10%.
3. repeat 2 steps 8 time, until the pH value of clear liquid reaches 5.5.
4. removed by the mixed organic solvents in the slurry of solids of finally collecting by underpressure distillation or cryodesiccated method, the purity obtaining graphite oxide is 99.40%.
Claims (1)
1. a method for graphite oxide high efficiency separation purifying, is characterized in that comprising the steps:
1) by the graphite oxide stoste that synthesizes by sedimentation, centrifugal or filter type removing clear liquid, collect solid materials;
2) in the solid materials collected, add mixed organic solvents, make it dispersed, be mixed with the dispersion liquid that graphite oxide concentration is 1-20g/L, by dispersion liquid sedimentation, centrifugal or filter type removing clear liquid, collect solid materials;
3) repeating step 2, until the pH value of clear liquid reaches 5.5-6.5;
4) by underpressure distillation or cryodesiccated method, the mixed organic solvents in the slurry of solids of finally collecting is removed, obtain high purity oxygen graphite;
Wherein, mixed organic solvents used is made up of methyl alcohol, ethanol, acetone and dimethyl formamide, and the volume ratio of contained methyl alcohol is 0.5-98.5%, and the volume ratio of ethanol is 0.5-98.5%, the volume ratio of acetone is 0.5-98.5%, and the volume ratio of dimethyl formamide is 0.5-98.5%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626591A (en) * | 2012-04-10 | 2012-08-08 | 上海交通大学 | Method and device for purifying graphene oxide/graphite solution |
| CN103539108A (en) * | 2013-10-22 | 2014-01-29 | 泰山医学院 | Method for preparing graphene oxide |
| CN103693638A (en) * | 2013-12-09 | 2014-04-02 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene by electrochemical swelling of graphite |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626591A (en) * | 2012-04-10 | 2012-08-08 | 上海交通大学 | Method and device for purifying graphene oxide/graphite solution |
| CN103539108A (en) * | 2013-10-22 | 2014-01-29 | 泰山医学院 | Method for preparing graphene oxide |
| CN103693638A (en) * | 2013-12-09 | 2014-04-02 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene by electrochemical swelling of graphite |
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