CN104789981A - Preparation method for expanded graphite - Google Patents
Preparation method for expanded graphite Download PDFInfo
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- CN104789981A CN104789981A CN201510150199.0A CN201510150199A CN104789981A CN 104789981 A CN104789981 A CN 104789981A CN 201510150199 A CN201510150199 A CN 201510150199A CN 104789981 A CN104789981 A CN 104789981A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention belongs to the field of chemistry and particularly relates to a preparation method for expanded graphite. The method comprises the following steps: taking sulfate, phosphate or nitrate as an electrolyte solution, taking a simulated spent fuel ball as an anode, and taking an inert electrode as a cathode; performing electrolysis under a condition that the current is 25-70 A. Collected graphite particles have the specific surface area being 20-50 m<2>/g and the expansion volume of 20-70 mL/g. Due to the adoption of electrochemical intercalation and oxidation coupling methods, graphite oxide containing various free radical groups is easily formed under the action of high current, and graphite particles are refined, so that the formation temperature of the expanded graphite is reduced, energy resources are saved, the breakage rate of a simulated fuel core is reduced, reutilization of a large amount of matrix graphite is improved, and disposal space of high-level wastes is reduced.
Description
Technical field
The invention belongs to chemical field, particularly a kind of preparation method of expanded graphite.
Background technology
The energy that nuclear energy is rich reserves on the earth, highly concentrate.Nuclear energy power generation is both economical, clean, and can greatly reduce problem of environmental pollution, 21 century will be the great development period of nuclear energy power generation.
High temperature gas cooled reactor spent fuel element ball warp crosses 300MPa compacting, and 1600 DEG C of calcinings, wherein more than 95wt% is graphite.If most graphite can be peeled off, be prepared into expanded graphite recycling, both decreased Nuclear waste disposal space, and again saved resource.
In graphite, carbon atom arranges with laminate structure, and bonding force is between layers much more weak than bonding force between the carbon atom on layer, therefore a lot of material can insert graphite layers under certain conditions, generate graphite intercalation compound, then can expanded graphite be prepared into through drying heat treated.
Graphite intercalation compound can by the synthesis of the method such as chemical method, electrochemical process.
With sulfuric acid and natural flake graphite for raw material, nitric acid, hydrogen peroxide etc. are oxygenant, the oxidation of oxidized dose of graphite carbon-coating, sulfuric acid is then as main intercalator generation graphite intercalation reaction (Chen Zhigang, Zhang Yong, Yang Juan etc. the structure of expanded graphite, Synthesis and applications. Jiangsu University's journal (natural science edition), 2005,3 (26): 248-251.).Graphite after oxide treatment loses a large amount of π-electron, and negatively charged ion enters graphite layers by intercalation, is combined with graphite carbon atom, forms graphite intercalation compound (GIC).The graphite intercalation compound of generation is carried out washing and drying, then carries out being warmed up to 800 DEG C of heating, finally can generate expanded graphite.
Graphite intercalation compound also can pass through electrochemical production (Yu Renguang, Qiao little Jing, Liu Weihua etc. affect the allowance for expansion Elements research of the expanded graphite of electrochemical production, Speciality Petrochemicals is in progress, 2003,4 (10) 8-10), concrete grammar is by natural flake graphite and supplementary anode composition anolyte compartment, sulfuric acid and acetic acid, as electrolyte solution, make negative electrode with stereotype or platinum plate, more logical direct current.In electrolytic process, there is oxidizing reaction, after electrolysis terminates, after antianode graphite carries out the processes such as depickling, washing, dehydration, drying, then in 600-800 DEG C of heating while puffing.Effectively can control speed of response by controlling anode electrolyte concentration, current density, current potential, oxidization time etc. and obtain expecting expanded graphite, this is the incomparable advantage of other method.
Aforesaid method all adopts strong acid, strong oxidizer etc. to carry out expanded graphite preparation to natural flake graphite, and use strong acid strong oxidizer to carry out intercalation oxidation to high temperature gas cooled reactor spent fuel element ball, unexpected broken coatedparticles is easily made to dissolve in the solution, cause alpha activity and the strong gamma activity of fission product to the pollution of a large amount of matrix graphite, thus cause a large amount of matrix graphites because of pollute can not recycle or can not with in low form of putting keep in, increase Nuclear waste disposal space; Because graphite pebbles is through high temperature high pressure process, existing chemical oxidation and electrochemical process condition can not meet the disintegration of graphite pebbles, and are formed at low temperatures and prepare expanded graphite, are necessary to develop a kind of new technology.
The present invention uses slightly acidic electrolytic solution, adopt electrochemical intercalation method for oxidation, be carry out electrolysis under the condition of 25A ~ 70A at electric current, positive column easily forms the graphite oxide containing multiple free group, refinement graphite granule, thus reduce expanded graphite formation temperature (expanding at 120 DEG C ~ 200 DEG C), save the energy, improve the recycling of a large amount of matrix graphite.
Summary of the invention
For deficiency of the prior art, in conjunction with the constructional feature of high temperature gas cooled reactor graphite pebbles, the invention provides a kind of preparation method of expanded graphite, the method comprises the steps:
1) put into simulation spent fuel element sphere in a cell, using vitriol, phosphoric acid salt or nitrate as electrolytic solution, concentration of electrolyte is 2mol/L ~ 5mol/L, and with nitre acid for adjusting pH to 3 ~ 7;
2) to simulate spent fuel element sphere as anode, using noble electrode as negative electrode; Switch on power, pass into the electric current of 25A ~ 70A, do not carrying out electrolysis higher than under the condition of 40 DEG C;
3) expand at 120 DEG C ~ 200 DEG C, be separated and obtain expanded graphite.
The material of described noble electrode is lead, graphite or titanium.
The electrolysis time of described electrolysis is 1h ~ 5h.
Remained in 3 ~ 7 scopes by automatic pH regulator instrument controlling electrolytic solution pH in electrolytic process.
The Bulking Time of described expansion is 1h ~ 3h.
Beneficial effect of the present invention is:
The present invention uses slightly acidic electrolytic solution, adopt electrochemical intercalation method for oxidation, under big current effect, easy formation contains the graphite oxide of multiple free group, refinement graphite granule, thus reduces expanded graphite formation temperature, save the energy, reduce analog fuel core core percentage of damage, improve the recycling of a large amount of matrix graphite, reduce the disposal space of high-level waste.
Embodiment
The invention provides a kind of preparation method of expanded graphite, be specially: with vitriol, phosphoric acid salt or nitrate for electrolytic solution, to simulate spent fuel ball as anode, using noble electrode as negative electrode; Be 25A ~ 70A at electric current, under the condition of room temperature, carry out electrolysis.Enumerate embodiment to be below explained the present invention further, but do not limit the present invention in any way.
Embodiment 1
Configuration concentration is the KNO of 3mol/L
3electrolytic solution be placed in electrolyzer, and with nitre acid for adjusting pH to 3, using stereotype as negative electrode, diameter be the simulation spent fuel element sphere of Φ 60mm as anode, at room temperature, pass into 25A electric current and carry out constant-current electrolysis.Be 3 by automatic pH regulator instrument controlling pH in electrolytic process, after carrying out 5h, suction filtration electrolytic solution, and be about 7 with deionized water wash filter cake to filtrate pH, seasoning, expand 1h in baking oven at 200 DEG C of temperature, and be separated graphite and analog fuel core core after expanding, the graphite granule specific surface area obtained is 35m
2/ g, allowance for expansion is 44mL/g.
Embodiment 2
Configuration concentration is the Na of 2mol/L
3pO
4electrolytic solution be placed in electrolyzer, and with nitre acid for adjusting pH to 5, using graphite as negative electrode, diameter be the simulation spent fuel element sphere of Φ 60mm as anode, at room temperature, pass into 40A electric current and carry out constant-current electrolysis.Be 5 by automatic pH regulator instrument controlling pH in electrolytic process, after 3h, suction filtration electrolytic solution, and be about 7 with deionized water wash filter cake to filtrate pH, seasoning, expand 2h in baking oven at 150 DEG C of temperature, and be separated graphite and analog fuel core core after expanding, the graphite granule specific surface area obtained after expansion is 23m
2/ g, allowance for expansion is 25mL/g.
Embodiment 3
Configuration concentration is the Na of 2mol/L
2sO
4electrolytic solution be placed in electrolyzer, and with nitre acid for adjusting pH to 7, using titanium net as negative electrode, diameter be the simulation spent fuel element sphere of Φ 60mm as anode, at 40 DEG C of temperature, pass into 60A electric current and carry out constant-current electrolysis.Be 7 by automatic pH regulator instrument controlling pH in electrolytic process, after carrying out 2h, suction filtration electrolytic solution, and be about 7 with deionized water wash filter cake to filtrate pH, seasoning, expand 3h in baking oven at 120 DEG C of temperature, and be separated graphite and analog fuel core core after expanding, the graphite granule specific surface area obtained after expansion is 50m
2/ g, allowance for expansion is 48mL/g.
Embodiment 4
Configuration concentration is the NaNO of 5mol/L
3electrolytic solution be placed in electrolyzer, and with nitre acid for adjusting pH to 3, using graphite as negative electrode, diameter be the simulation spent fuel element sphere of Φ 60mm as anode, at room temperature, pass into 70A electric current and carry out constant-current electrolysis.Be 3 by automatic pH regulator instrument controlling pH in electrolytic process, after carrying out 1h, suction filtration electrolytic solution, and be about 7 with deionized water wash filter cake to filtrate pH, seasoning, expand 3h in baking oven at 120 DEG C of temperature, and be separated graphite and analog fuel core core after expanding, the graphite granule specific surface area obtained after expansion is 50m
2/ g, allowance for expansion is 65mL/g.
Claims (5)
1. a preparation method for expanded graphite, is characterized in that, the method comprises the steps:
1) put into simulation spent fuel element sphere in a cell, using vitriol, phosphoric acid salt or nitrate as electrolytic solution, concentration of electrolyte is 2mol/L ~ 5mol/L, and with nitre acid for adjusting pH to 3 ~ 7;
2) to simulate spent fuel element sphere as anode, using noble electrode as negative electrode; Switch on power, pass into the electric current of 25A ~ 70A, do not carrying out electrolysis higher than under the condition of 40 DEG C;
3) expand at 120 DEG C ~ 200 DEG C, be separated and obtain expanded graphite.
2. the preparation method of a kind of expanded graphite according to claim 1, is characterized in that, the material of described noble electrode is lead, graphite or titanium.
3. the preparation method of a kind of expanded graphite according to claim 1, is characterized in that, the electrolysis time of described electrolysis is 1h ~ 5h.
4. the preparation method of a kind of expanded graphite according to claim 1, is characterized in that, is remained in 3 ~ 7 scopes in electrolytic process by automatic pH regulator instrument controlling electrolytic solution pH.
5. the preparation method of a kind of expanded graphite according to claim 1, is characterized in that, the Bulking Time of described expansion is 1h ~ 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510150199.0A CN104789981A (en) | 2015-03-31 | 2015-03-31 | Preparation method for expanded graphite |
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| CN201510150199.0A CN104789981A (en) | 2015-03-31 | 2015-03-31 | Preparation method for expanded graphite |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111453723A (en) * | 2020-05-28 | 2020-07-28 | 鹰领航空高端装备技术秦皇岛有限公司 | Expandable graphite preparation device and electrochemical intercalation method thereof |
| CN113230913A (en) * | 2021-05-11 | 2021-08-10 | 燕山大学 | Preparation method and application of nitrate-trapped polyethersulfone nanofiltration membrane |
| CN113244794A (en) * | 2021-05-11 | 2021-08-13 | 燕山大学 | Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution |
| CN115215336A (en) * | 2022-07-19 | 2022-10-21 | 内蒙古大学 | Electrolytic reaction device for preparing expanded graphite, electrolytic oxidation method and capacitive desalination method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102444A (en) * | 1994-09-02 | 1995-05-10 | 刘铁铮 | Method preparation of expansible black lead and its apparatus |
| CN1885439A (en) * | 2006-05-26 | 2006-12-27 | 清华大学 | Stripping method for matrix graphite of simulated HTGR spent fuel element sphere |
| CN101252028A (en) * | 2008-03-28 | 2008-08-27 | 清华大学 | Method with nitrates as base to crash high temperature gas cooled reactor spent fuel element basal body graphite |
| CN102616771A (en) * | 2012-03-31 | 2012-08-01 | 黑龙江科技学院 | Method for preparing sulfur-free low-ash expanded graphite |
-
2015
- 2015-03-31 CN CN201510150199.0A patent/CN104789981A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102444A (en) * | 1994-09-02 | 1995-05-10 | 刘铁铮 | Method preparation of expansible black lead and its apparatus |
| CN1885439A (en) * | 2006-05-26 | 2006-12-27 | 清华大学 | Stripping method for matrix graphite of simulated HTGR spent fuel element sphere |
| CN101252028A (en) * | 2008-03-28 | 2008-08-27 | 清华大学 | Method with nitrates as base to crash high temperature gas cooled reactor spent fuel element basal body graphite |
| CN102616771A (en) * | 2012-03-31 | 2012-08-01 | 黑龙江科技学院 | Method for preparing sulfur-free low-ash expanded graphite |
Non-Patent Citations (3)
| Title |
|---|
| LIFANG TIAN等: "Analysis of electrochemical disintegration process of graphite matrix", 《ELECTROCHIMICA ACTA》 * |
| LIFANG TIAN等: "Disintegration of graphite matrix from the simulative high temperature gas-cooled reactor fuel element by electrochemical method", 《ELECTROCHIMICA ACTA》 * |
| 朴楠等: "高温气冷堆模拟石墨球电化学解体影响因素研究", 《第十三届全国核化学与放射化学学术研讨会论文摘要集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111453723A (en) * | 2020-05-28 | 2020-07-28 | 鹰领航空高端装备技术秦皇岛有限公司 | Expandable graphite preparation device and electrochemical intercalation method thereof |
| CN113230913A (en) * | 2021-05-11 | 2021-08-10 | 燕山大学 | Preparation method and application of nitrate-trapped polyethersulfone nanofiltration membrane |
| CN113244794A (en) * | 2021-05-11 | 2021-08-13 | 燕山大学 | Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution |
| CN113244794B (en) * | 2021-05-11 | 2022-04-19 | 燕山大学 | Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution |
| CN113230913B (en) * | 2021-05-11 | 2022-06-28 | 燕山大学 | Preparation method and application of nitrate-trapped polyethersulfone nanofiltration membrane |
| CN115215336A (en) * | 2022-07-19 | 2022-10-21 | 内蒙古大学 | Electrolytic reaction device for preparing expanded graphite, electrolytic oxidation method and capacitive desalination method |
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Application publication date: 20150722 |