CN103112851A - Preparation method of high-purity crystalline flake graphite - Google Patents
Preparation method of high-purity crystalline flake graphite Download PDFInfo
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- CN103112851A CN103112851A CN2013100882411A CN201310088241A CN103112851A CN 103112851 A CN103112851 A CN 103112851A CN 2013100882411 A CN2013100882411 A CN 2013100882411A CN 201310088241 A CN201310088241 A CN 201310088241A CN 103112851 A CN103112851 A CN 103112851A
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Abstract
The invention discloses a preparation method of high-purity crystalline flake graphite, and relates to a preparation method of high-purity graphite. The invention solves the technical problem that the existing method for preparing high-purity crystalline flake graphite is large in pollution and high in energy consumption. The method comprises the following steps of: 1, placing natural crystalline flake graphite in a quartz tube, heating, introducing nitrogen and insulating; 2, stirring and mixing hydrochloric acid, sulfuric acid, absolute ethyl alcohol and distilled water at room temperature; 3, mixing sodium isopropylate, aluminum isopropylate and potassium isopropylate and placing the mixture in a liquor prepared in step 2, and stirring and mixing at room temperature; and 4, completely mixing the liquor obtained in step 3 with processed natural crystalline flake graphite in step 1 to form a mixture, placing the mixture in a high pressure reaction kettle, and meanwhile, adding ethanol, sealing, releasing ethanol steam, relieving pressure in the high pressure reaction kettle and drying to obtain the crystalline flake graphite after reaction. The method provided by the invention is free from pollution and low in energy consumption. The method provided by the invention is used for extracting crystalline flake graphite.
Description
Technical field
The present invention relates to a kind of preparation method of high purity graphite.
Background technology
High purity graphite is because it has the characteristic of many novelties, as good heat conduction, conductivity, and the characteristics such as good absorption property and heat-shock resistance, thereby cause scholar's very big interest.Utilize supercritical fluid drying to prepare the high-purity natural crystalline flake graphite and given graphite new characteristic, make it have more excellent physics and chemistry characteristic, as high temperature resistant, catalysis and conductance property etc.At present, the preparation method about the high-purity natural crystalline flake graphite mainly concentrates on traditional alkali acid chemical method and high temperature substrate logos.The advantage of tradition alkali acid chemical method is that equipment is simple, easy to operate, but graphite purity is difficult to reach high-purity requirement, and reaction process is seriously polluted, solid by-product is more, be difficult to remove totally, affect quality product, be difficult to control the discharging of " three wastes " in reaction process to the pollution of environment.The high temperature substrate logos is the characteristic of utilizing the impurity in graphite at high temperature to volatilize, adopts and in High Temperature Furnaces Heating Apparatus, graphite raw material heated under protection of inert gas or under vacuum condition, thus the preparation high purity graphite.The purification temperature of existing preparation high purity graphite is up to 3050 ℃, and energy consumption is huge.
Summary of the invention
The objective of the invention is to pollute technical problem large, high energy consumption in order to solve the existing method for preparing crystalline flake graphite, a kind of preparation method of high-purity crystalline flake graphite is provided.
The preparation method of high-purity crystalline flake graphite carries out according to following steps:
One, be that the natural flake graphite of 10～200 μ m is put into silica tube with the 5g particle diameter, silica tube is warming up to 500 ℃ with the speed of 5～10 ℃/minutes, pass into flowing nitrogen with the speed of 5L/min, then be incubated 1h under the condition of 500 ℃;
Two, getting 10～50mL hydrochloric acid, 20～40mL sulfuric acid, 8～16mL dehydrated alcohol and 8～12mL distilled water stirred at ambient temperature, mixes 30 minutes;
Three, with putting into the solution that step 2 is prepared after 5～10mg isopropyl acid sodium, 5～10mg aluminium isopropylate and the mixing of 5～10mg isopropyl acid potassium, stirred at ambient temperature, mix 30 minutes;
Four, the solution with the step 3 gained mixes fully with the natural flake graphite of processing through step 1, form mixture, mixture is put in autoclave, add simultaneously ethanol, amount of alcohol added is 4/5 of reactor volume, and autoclave is sealed, be that 250～300 ℃, pressure are to react 6～10h under 5～10MPa condition in temperature, reaction with alcohol vapour release, autoclave release, drying, namely gets crystalline flake graphite after finishing.
The preparation method of the high-purity crystalline flake graphite of high-purity natural of the present invention forms acidic solution by hydrochloric acid, sulfuric acid, second alcohol and water, utilize isopropyl hydrochlorate active reaction thing that generates under the ethanol super critical condition, in sour environment can with graphite in oxide impurity fully react and generate the soluble salt be soluble in acid, discharging by alcohol vapour, thereby take away by product, and then preparation high-purity natural crystalline flake graphite (graphite purity 〉=99.9%).The inventive method is pollution-free, and energy consumption is low.
The inventive method easily decomposites the acid complex compound with oxidisability under the water surrounding condition under High Temperature High Pressure due to the isopropyl hydrochlorate, and the dirt in natural flake graphite is owing to having complicated crystalline structure, the alkaline complex compound that has reductibility with easy generation under this environment, simultaneously, under super critical condition, acidic substance in solution easily enter the intercalation configuration in crystalline flake graphite, thereby make the impurity in crystalline flake graphite further discharge.Like this, the acid complex compound that the alkaline complex compound that impurity in natural flake graphite generates and isopropyl hydrochlorate decompose is fully reaction under high-temperature and high-pressure conditions, be created on the metasilicate that is soluble in acid under super critical condition, under condition of high voltage along with the abrupt release of gas, thereby reach the purpose of purification.
Description of drawings
Fig. 1 is the three-dimensional optical microphotograph of high-purity crystalline flake graphite of test one preparation;
Fig. 2 is the XRD figure spectrum of test two natural flake graphites, in figure ● expression graphite,
Expression Fe
2O
3, ■ represents Al
2O
3,
Expression CaO,
Expression SiO
2,
Expression MgO;
Fig. 3 is the XRD figure spectrum of high-purity crystalline flake graphite of test two preparations.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of the high-purity crystalline flake graphite of present embodiment carries out according to following steps:
One, be that the natural flake graphite of 10～200 μ m is put into silica tube with the 5g particle diameter, silica tube is warming up to 500 ℃ with the speed of 5～10 ℃/minutes, pass into flowing nitrogen with the speed of 5L/min, then be incubated 1h under the condition of 500 ℃;
Two, getting 10～50mL hydrochloric acid, 20～40mL sulfuric acid, 8～16mL dehydrated alcohol and 8～12mL distilled water stirred at ambient temperature, mixes 30 minutes;
Three, with putting into the solution that step 2 is prepared after 5～10mg isopropyl acid sodium, 5～10mg aluminium isopropylate and the mixing of 5～10mg isopropyl acid potassium, stirred at ambient temperature, mix 30 minutes;
Four, the solution with the step 3 gained mixes fully with the natural flake graphite of processing through step 1, form mixture, mixture is put in autoclave, add simultaneously ethanol, amount of alcohol added is 4/5 of reactor volume, and autoclave is sealed, be that 250～300 ℃, pressure are to react 6～10h under 5～10MPa condition in temperature, after reaction finishes, with alcohol vapour releases, autoclave release, drying, namely high-purity must crystalline flake graphite.
Embodiment two: present embodiment is different from embodiment one is the purity 〉=90% of the natural flake graphite described in step 1.Other is identical with embodiment one.
Embodiment three: present embodiment is different from one of embodiment one or two is in step 1, silica tube to be warming up to 500 ℃ with the speed of 8 ℃/minutes.Other is identical with one of embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that in step 2, the volume ratio of hydrochloric acid and sulfuric acid is 3～4: 4.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four is that in step 2, hydrochloric acid and the mixing acid of sulfuric acid and the volume ratio of dehydrated alcohol are 32～44: 8.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five is to be that 260～290 ℃, pressure are to react 7～9h under 6～9MPa condition in temperature in step 4.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six is to be that 270 ℃, pressure are to react 8h under the 8MPa condition in temperature in step 4.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven is that temperature that in step 4, alcohol vapour discharges is that 250～300 ℃, relief pressure are 5～10MPa.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight is that temperature that in step 4, alcohol vapour discharges is that 280 ℃, relief pressure are 8MPa.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is that in step 4, drying temperature is 60 ℃.Other is identical with one of embodiment one to nine.
Adopt following experimental verification effect of the present invention:
Test one:
The preparation method of high-purity crystalline flake graphite carries out according to following steps:
One, be that the natural flake graphite of 100 μ m is put into silica tube with the 5g particle diameter, silica tube is warming up to 500 ℃ with the speed of 6 ℃/minutes, pass into flowing nitrogen with the speed of 5L/min, then be incubated 1h under the condition of 500 ℃;
Two, getting 10mL hydrochloric acid, 20mL sulfuric acid, 8mL dehydrated alcohol and 8mL distilled water stirred at ambient temperature, mixes 30 minutes;
Three, with putting into the solution that step 2 is prepared after 10mg isopropyl acid sodium, 10mg aluminium isopropylate and the mixing of 10mg isopropyl acid potassium, stirred at ambient temperature, mix 30 minutes;
Four, the solution with the step 3 gained mixes fully with the natural flake graphite of processing through step 1, form mixture, mixture is put in autoclave, add simultaneously ethanol, the add-on of ethanol is 4/5 of reactor volume, and autoclave is sealed, be that 260 ℃, pressure are to react 6h under the 5MPa condition in temperature, reaction with alcohol vapour release, autoclave release, drying, namely gets high-purity crystalline flake graphite after finishing.
Utilize as can be seen from Figure 1 the prepared high-purity natural crystalline flake graphite of supercritical fluid drying to have good integrity, smooth surface, the method for this test that hence one can see that is not destroyed the shape characteristic of graphite.
Test two:
One, be that the natural flake graphite of 150 μ m is put into silica tube with the 5g particle diameter, silica tube is warming up to 500 ℃ with the speed of 8 ℃/minutes, pass into flowing nitrogen with the speed of 5L/min, then be incubated 1h under the condition of 500 ℃;
Two, getting 25mL hydrochloric acid, 25mL sulfuric acid, 10mL dehydrated alcohol and 10mL distilled water stirred at ambient temperature, mixes 30 minutes;
Three, with putting into the solution that step 2 is prepared after 8mg isopropyl acid sodium, 8mg aluminium isopropylate and the mixing of 8mg isopropyl acid potassium, stirred at ambient temperature, mix 30 minutes;
Four, the solution with the step 3 gained mixes fully with the natural flake graphite of processing through step 1, form mixture, mixture is put in autoclave, add simultaneously ethanol, the add-on of ethanol is 4/5 of reactor volume, and autoclave is sealed, be that 270 ℃, pressure are to react 8h under the 7.5MPa condition in temperature, reaction with alcohol vapour release, autoclave release, drying, namely gets high-purity crystalline flake graphite after finishing.
Utilize as can be seen from Figure 2 supercritical fluid drying can prepare the high-purity natural crystalline flake graphite, product purity 〉=99.9% after purifying, the most of impurity in raw material can be removed.
Test three:
One, be that the natural flake graphite of 170 μ m is put into silica tube with the 5g particle diameter, silica tube is warming up to 500 ℃ with the speed of 10 ℃/minutes, pass into flowing nitrogen with the speed of 5L/min, then be incubated 1h under the condition of 500 ℃;
Two, getting 50mL hydrochloric acid, 40mL sulfuric acid, 16mL dehydrated alcohol and 12mL distilled water stirred at ambient temperature, mixes 30 minutes;
Three, with putting into the solution that step 2 is prepared after 6mg isopropyl acid sodium, 6mg aluminium isopropylate and the mixing of 6mg isopropyl acid potassium, stirred at ambient temperature, mix 30 minutes;
Four, the solution with the step 3 gained mixes fully with the natural flake graphite of processing through step 1, form mixture, mixture is put in autoclave, add simultaneously ethanol, the add-on of ethanol is 4/5 of reactor volume, and autoclave is sealed, be that 280 ℃, pressure are to react 10h under the 8MPa condition in temperature, reaction with alcohol vapour release, autoclave release, drying, namely gets high-purity crystalline flake graphite after finishing.
Claims (10)
1. the preparation method of high-purity crystalline flake graphite is characterized in that the preparation method of high-purity crystalline flake graphite carries out according to following steps:
One, be that the natural flake graphite of 10～200 μ m is put into silica tube with the 5g particle diameter, silica tube is warming up to 500 ℃ with the speed of 5～10 ℃/minutes, pass into flowing nitrogen with the speed of 5L/min, then be incubated 1h under the condition of 500 ℃;
Two, getting 10～50mL hydrochloric acid, 20～40mL sulfuric acid, 8～16mL dehydrated alcohol and 8～12mL distilled water stirred at ambient temperature, mixes 30 minutes;
Three, with putting into the solution that step 2 is prepared after 5～10mg isopropyl acid sodium, 5～10mg aluminium isopropylate and the mixing of 5～10mg isopropyl acid potassium, stirred at ambient temperature, mix 30 minutes;
Four, the solution with the step 3 gained mixes fully with the natural flake graphite of processing through step 1, form mixture, mixture is put in autoclave, add simultaneously ethanol, amount of alcohol added is 4/5 of reactor volume, and autoclave is sealed, be that 250～300 ℃, pressure are to react 6～10h under 5～10MPa condition in temperature, reaction with alcohol vapour release, autoclave release, drying, namely gets high-purity crystalline flake graphite after finishing.
2. the preparation method of high-purity crystalline flake graphite according to claim 1 is characterized in that the purity of the natural flake graphite described in step 1 〉=90%.
3. the preparation method of high-purity crystalline flake graphite according to claim 1 is characterized in that in step 1 silica tube is warming up to 500 ℃ with the speed of 8 ℃/minutes.
4. the preparation method of high-purity crystalline flake graphite according to claim 1 is characterized in that in step 2, the volume ratio of hydrochloric acid and sulfuric acid is 3～4: 4.
5. the preparation method of high-purity crystalline flake graphite according to claim 1 is characterized in that in step 2, hydrochloric acid and the mixing acid of sulfuric acid and the volume ratio of dehydrated alcohol are 32～44: 8.
6. the preparation method of high-purity crystalline flake graphite according to claim 1 is characterized in that in step 4 in temperature being that 260～290 ℃, pressure are to react 7～9h under 6～9MPa condition.
7. the preparation method of high-purity crystalline flake graphite according to claim 1 is characterized in that in step 4 in temperature being that 270 ℃, pressure are to react 8h under the 8MPa condition.
8. according to claim 1, the preparation method of 2,3,4,5,6 or 7 described high-purity crystalline flake graphites, it is characterized in that temperature that in step 4, alcohol vapour discharges is that 250～300 ℃, relief pressure are 5～10MPa.
9. the preparation method of high-purity crystalline flake graphite according to claim 8 is characterized in that temperature that in step 4, alcohol vapour discharges is that 280 ℃, relief pressure are 8MPa.
10. according to claim 1, the preparation method of 2,3,4,5,6 or 7 described high-purity crystalline flake graphites, it is characterized in that in step 4, drying temperature is 60 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720727A (en) * | 2016-08-08 | 2018-02-23 | 明道学校财团法人明道大学 | Graphite ore purification process |
| CN109336104A (en) * | 2018-11-23 | 2019-02-15 | 北京航空航天大学 | A kind of low temperature graphite purification method |
-
2013
- 2013-03-19 CN CN2013100882411A patent/CN103112851A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720727A (en) * | 2016-08-08 | 2018-02-23 | 明道学校财团法人明道大学 | Graphite ore purification process |
| CN109336104A (en) * | 2018-11-23 | 2019-02-15 | 北京航空航天大学 | A kind of low temperature graphite purification method |
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Application publication date: 20130522 |