CN1462724A - Method for preparing expanded graphite without sulphur - Google Patents
Method for preparing expanded graphite without sulphur Download PDFInfo
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- CN1462724A CN1462724A CN 03124260 CN03124260A CN1462724A CN 1462724 A CN1462724 A CN 1462724A CN 03124260 CN03124260 CN 03124260 CN 03124260 A CN03124260 A CN 03124260A CN 1462724 A CN1462724 A CN 1462724A
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Abstract
A process for preparing expansive non-sulfur graphite includes mixing natural flake graphite, potassium permanganate and perchloric acid in mass ratio of 1:(0.05-0.5):(1-7) and reaction at 30-70 deg.C for 30-90 min. It can be expanded at 200-1000 deg.C to become high-multiple graphite.
Description
Technical field:
The invention belongs to a kind of raw material of wood-charcoal material-Preparation of Expanded Graphite method, relate in particular to the no sulphur that a kind of low temperature can be expanded, the preparation method of highly expanded graphite.
Background technology:
Expanded graphite has another name called acidifying graphite, at high temperature can be puffed to a kind of loose similar vermiform material usually, so the name graphite worm.It is the intermediates of preparation soft graphite, and very application prospects is arranged in fields such as oil, machinery, chemical industry, nuclear industry, aerospace.Be mainly used in the sealing material aspect now, have the title of " king of sealing material ", the trend that replaces the asbestos seal material is fully arranged greatly.Since U.S. combinating carbide company invention in 1963, because its unique physicochemical property, be subjected to the researchist's in fields such as physics, chemistry, material very big favor, to its research and exploration of having carried out comprehensive multi-angle, make it to become an important branch field of new carbon.
The starting material of preparation expanded graphite are natural flake graphites, because it has the netted deck structure of hexagonal, combine with more weak Van der Waals force between layer and the layer, so can generate a kind of compound between graphite layers with the artificial method with insertion such as foreign peoples's molecule, atom or ion graphite layers.This intercalation compound removes the original physicochemical property that has kept graphite, simultaneously because the interaction of carbon atomic layer and interposed layer has produced many new characteristics again, as high conductivity, supraconductivity, battery behavior, specificity of catalyst, hydrogen storage property etc.Therefore, compound between graphite layers in fact is the matrix material on a class atom, the molecular scale, itself belongs to the nano material category.Up to the present, various compound between graphite layers have been synthesized.Interaction type by object between interposed layer and main body graphite can be divided into two big classes: 1. inset and graphite layers have charge transfer, produce electrostatic attraction (electric charge mobile model) between the two; 2. inset and carbon atom form covalent linkage (covalent bond type).With regard to electric charge mobile model (most compound between graphite layers belong to the type), when inset and main body graphite during for the sub-property of power supply, the subtype compound between graphite layers is referred to as to power; When being subjected to electronics, then be referred to as to be subjected to the electron type compound between graphite layers.All cause the increase of interlamellar spacing under two kinds of situations owing to the insertion of reactant, but the sp that the carbon atom in the graphite aspect forms
2Track is constant, does not lose its planarity.The constitutional features of these compounds is that interposed layer and graphite linings are arranged regularly perpendicular to graphite bedding angle (C direction of principal axis) in the edge, and arranges inset in the face that is parallel to the graphite aspect regularly.The compound between graphite layers of this type mainly contains basic metal-graphite mould, halogen-graphite mould, metal halide-graphite mould, acid-graphite mould etc.
The method of synthetic acid-graphite mould expansible black lead mainly contains two kinds: chemical method and electrochemical process.Most of vitriol oil of easy intercalation that adopts is made intercalating agent, generally all prepare acidifying graphite through several technological processs such as peroxidation, acidifying intercalation, washing, dryings, then through the expanded system graphite worm of high temperature (900-1100 ℃), further various flexible graphite materials of die mould system again.In the various application facet of soft graphite, sulfur impurity is not for desirable.And the sulphur content in the soft graphite derives from two sides and: the one, the sulphur content of raw material natural flake graphite itself.Sulphur content seldom generally is less than 200ppm in the high-carbon natural flake graphite, the not even sulfur-bearing that has.The 2nd, bring in the technological process.Particularly adopt sulfuric acid to make intercalating agent, a part of sulfocompound residues in the final graphite worm behind high temperature puffing, causes sulphur content Chang Gaoda 3-4% wherein.At Journal of Inorganic Materials, 1997,12 (2): adopt nitric acid-diacetyl oxide-potassium permanganate-natural flake graphite to do the work of a little no sulphur expanded graphite aspects in 252 1 articles, but expanding volume is generally less than 320ml/g, and must is to expand down at high temperature 900-1100 ℃.
The purpose of this invention is to provide the no sulphur Preparation of Expanded Graphite method that a kind of low temperature can be expanded.
Preparation method of the present invention comprises the steps:
1. after perchloric acid, potassium permanganate, natural flake graphite being mixed, at temperature of reaction 30-70 ℃
Under the condition, reacted 30-90 minute, prepare expandable sulfur-free graphite;
2. expandable sulfur-free graphite will be prepared and under 200-1100 ℃, high power graphite can be expand into.
Wherein the each component mass ratio is:
Natural flake graphite: potassium permanganate: between perchloric acid=1: 0.05-0.5: 1-7.
Aforesaid perchloric acid concentration is 70-72Wt%.
The fineness of aforesaid natural flake graphite＜50 orders
The expansible black lead of this patent preparation can expand into high power graphite under 200-1000 ℃, expansion multiple reaches 330-700ml/g.
The present invention has following advantage:
1. technology is simple, and is easy to operate.
2. Zhi Bei expanded graphite sulfur-bearing not.
3. Zhi Bei expanded graphite can expand into the high power graphite worm under 200 ℃, and expansion multiple reaches 350ml/g, also can be expanded under the high temperature.With the raising of swelling temperature, expanding volume improves thereupon.Like this, in the swelling temperature scope of broad 200-1000 ℃ can select different expanding volumes.
4. under 200 ℃ of low temperature, can expand into the high power graphite worm, can make the design simplification of puffing furnace, save the energy, reduce cost, improve operating environment.
Embodiment: embodiment 1
Concentration 70Wt% perchloric acid, potassium permanganate, fineness＜50 purpose natural flake graphites are pressed natural flake graphite: potassium permanganate: between perchloric acid=after 1: 0.05: 1 mass ratio mixes, under 30 ℃ of conditions of temperature of reaction, reacted 30 minutes, and prepared expandable sulfur-free graphite; The expansible black lead of preparing is expanded under 200 ℃, and expanding volume reaches 330ml/g.Expanded under 300 ℃, expanding volume reaches 350ml/g, and expanded under 400 ℃, expanding volume reaches 360ml/g, and expanded under 600 ℃, expanding volume reaches 400ml/g, and expanded under 800 ℃, expanding volume reaches 450ml/g.Expanded under 1000 ℃, expanding volume reaches 650ml/g
Embodiment 2
Concentration 71Wt% perchloric acid, potassium permanganate, fineness＜50 purpose natural flake graphites are pressed natural flake graphite: potassium permanganate: between perchloric acid=after 1: 0.1: 3 mass ratio mixes, under 50 ℃ of conditions of temperature of reaction, reacted 60 minutes, and prepared expandable sulfur-free graphite; The expansible black lead of preparing is expanded under 200 ℃ at graphite, and expanding volume reaches 320ml/g.Expanded under 300 ℃, expanding volume reaches 340ml/g, and expanded under 400 ℃, expanding volume reaches 370ml/g, and expanded under 600 ℃, expanding volume reaches 410ml/g, and expanded under 800 ℃, expanding volume reaches 430ml/g.Expanded under 1000 ℃, expanding volume reaches 610ml/g
Embodiment 3
Concentration 72Wt% perchloric acid, potassium permanganate, fineness＜50 purpose natural flake graphites are pressed natural flake graphite: potassium permanganate: between perchloric acid=after 1: 0.2: 7 mass ratio mixes, under 70 ℃ of conditions of temperature of reaction, reacted 90 minutes, and prepared expandable sulfur-free graphite; The expansible black lead of preparing is expanded under 200 ℃ at graphite, and expanding volume reaches 350ml/g.Expanded under 300 ℃, expanding volume reaches 370ml/g, and expanded under 400 ℃, expanding volume reaches 390ml/g, and expanded under 600 ℃, expanding volume reaches 480ml/g, and expanded under 800 ℃, expanding volume reaches 650ml/g.Expanded under 1000 ℃, expanding volume reaches 700ml/g.
Claims (3)
1. the preparation method of an expanded graphite without sulphur is characterized in that comprising the steps:
(1) with after perchloric acid, potassium permanganate, the natural flake graphite mixing, under temperature of reaction 30-70 ℃ condition, reacted 30-90 minute, prepare expandable sulfur-free graphite;
(2) prepare expandable sulfur-free graphite and under 200-1000 ℃, can expand into high power graphite.Wherein the each component mass ratio is:
Natural flake graphite: potassium permanganate: between perchloric acid=1: 0.05-0.5: 1-7.
2. the preparation method of a kind of expanded graphite without sulphur as claimed in claim 1 is characterized in that described perchloric acid concentration is 70-72Wt%.
3. the preparation method of a kind of expanded graphite without sulphur as claimed in claim 1 is characterized in that fineness＜50 orders of described natural flake graphite.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320596A (en) * | 2011-07-13 | 2012-01-18 | 武汉理工大学 | Preparation method of fine-flake expanded graphite |
| CN102335600A (en) * | 2011-07-12 | 2012-02-01 | 哈尔滨工业大学 | Preparation method of expandable graphite catalyst and method for treating ozonized water of catalysis |
| CN102963884A (en) * | 2012-11-02 | 2013-03-13 | 宜昌贝特石墨新材料有限公司 | Preparation method of reinforced flexible graphite |
| CN102126719B (en) * | 2010-01-14 | 2013-04-17 | 河北农业大学 | Preparation method of expandable graphite with low starting expansion temperature |
| CN104157863A (en) * | 2014-08-22 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of micro-expansive graphite anode material |
| CN104401978A (en) * | 2014-10-30 | 2015-03-11 | 宜昌新成石墨有限责任公司 | Preparation method for sulfur-free expandable graphite |
| CN104828818A (en) * | 2015-05-27 | 2015-08-12 | 北京鼎臣超导科技有限公司 | Efficient intercalation stripping method of micrometer graphite flakes and low-order graphite intercalation compounds and micrometer thin-wall porous expanded graphite |
| CN105460924A (en) * | 2015-12-25 | 2016-04-06 | 中国人民解放军后勤工程学院 | Preparation method of sulfur-free nano graphite |
| CN105502360A (en) * | 2015-12-25 | 2016-04-20 | 燕山大学 | Preparation method of sulfur-free expansible graphite |
| CN107840321A (en) * | 2016-09-21 | 2018-03-27 | 北京化工大学 | A kind of graphene oxide with fold, preparation method and the usage |
| CN107934954A (en) * | 2017-11-23 | 2018-04-20 | 孙川平 | A kind of pure graphite Far infrared thermal radiation heating film and preparation method thereof |
| CN110219017A (en) * | 2019-06-06 | 2019-09-10 | 燕山大学 | Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode preparation method |
| CN110902676A (en) * | 2019-12-26 | 2020-03-24 | 洛阳森蓝化工材料科技有限公司 | Preparation method of expanded graphite |
| CN113735111A (en) * | 2021-10-08 | 2021-12-03 | 黑龙江哈工石墨科技有限公司 | Preparation process method of low-sulfur expandable graphite |
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| CN101275036B (en) * | 2007-03-28 | 2011-04-20 | 南京理工大学 | Preparation for polymer conductive nanometer compound material |
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2003
- 2003-04-30 CN CN 03124260 patent/CN1212971C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126719B (en) * | 2010-01-14 | 2013-04-17 | 河北农业大学 | Preparation method of expandable graphite with low starting expansion temperature |
| CN102335600A (en) * | 2011-07-12 | 2012-02-01 | 哈尔滨工业大学 | Preparation method of expandable graphite catalyst and method for treating ozonized water of catalysis |
| CN102320596A (en) * | 2011-07-13 | 2012-01-18 | 武汉理工大学 | Preparation method of fine-flake expanded graphite |
| CN102963884A (en) * | 2012-11-02 | 2013-03-13 | 宜昌贝特石墨新材料有限公司 | Preparation method of reinforced flexible graphite |
| CN102963884B (en) * | 2012-11-02 | 2015-04-29 | 宜昌贝特石墨新材料有限公司 | Preparation method of reinforced flexible graphite |
| CN104157863B (en) * | 2014-08-22 | 2016-06-01 | 东莞市长安东阳光铝业研发有限公司 | The preparation method of a kind of microdilatancy graphite cathode material |
| CN104157863A (en) * | 2014-08-22 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of micro-expansive graphite anode material |
| CN104401978A (en) * | 2014-10-30 | 2015-03-11 | 宜昌新成石墨有限责任公司 | Preparation method for sulfur-free expandable graphite |
| CN104401978B (en) * | 2014-10-30 | 2015-08-05 | 宜昌新成石墨有限责任公司 | A kind of preparation method of expandable sulfur-free graphite |
| CN104828818A (en) * | 2015-05-27 | 2015-08-12 | 北京鼎臣超导科技有限公司 | Efficient intercalation stripping method of micrometer graphite flakes and low-order graphite intercalation compounds and micrometer thin-wall porous expanded graphite |
| CN105502360A (en) * | 2015-12-25 | 2016-04-20 | 燕山大学 | Preparation method of sulfur-free expansible graphite |
| CN105460924A (en) * | 2015-12-25 | 2016-04-06 | 中国人民解放军后勤工程学院 | Preparation method of sulfur-free nano graphite |
| CN107840321A (en) * | 2016-09-21 | 2018-03-27 | 北京化工大学 | A kind of graphene oxide with fold, preparation method and the usage |
| CN107840321B (en) * | 2016-09-21 | 2019-11-22 | 北京化工大学 | A kind of graphene oxide with fold, preparation method and the usage |
| CN107934954A (en) * | 2017-11-23 | 2018-04-20 | 孙川平 | A kind of pure graphite Far infrared thermal radiation heating film and preparation method thereof |
| CN110219017A (en) * | 2019-06-06 | 2019-09-10 | 燕山大学 | Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode preparation method |
| CN110902676A (en) * | 2019-12-26 | 2020-03-24 | 洛阳森蓝化工材料科技有限公司 | Preparation method of expanded graphite |
| CN113735111A (en) * | 2021-10-08 | 2021-12-03 | 黑龙江哈工石墨科技有限公司 | Preparation process method of low-sulfur expandable graphite |
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