CN101456553A - Chemical processing method for preparing high quality inflatable graphite - Google Patents
Chemical processing method for preparing high quality inflatable graphite Download PDFInfo
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- CN101456553A CN101456553A CNA2007101911914A CN200710191191A CN101456553A CN 101456553 A CN101456553 A CN 101456553A CN A2007101911914 A CNA2007101911914 A CN A2007101911914A CN 200710191191 A CN200710191191 A CN 200710191191A CN 101456553 A CN101456553 A CN 101456553A
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Abstract
The invention discloses a chemical treatment method for preparing high-quality expandable graphite. The method adopts concentrated sulfuric acid as an intercalator and hydrogen peroxide as a catalyst to prepare the high-quality expandable graphite under the vacuum condition. Because water has constant boiling point under the condition of constant vacuum degree, the reaction temperature can be well controlled and simultaneously stable reaction temperature can be maintained by utilizing vacuum to bring away heat exhausted during reaction in time. The method can obtain the high-quality expandable graphite of which the volatile component is less than 12 percent and the sulfur content is less than 1.5 percent, and the sulfur content can be less than 800 ppm after the high-quality expandable graphite is treated for 30 seconds at a high temperature of between 900 and 1,000 DEG C.
Description
Technical field
The present invention relates to a kind of chemical treatment method of graphite, specifically a kind of chemical treatment method for preparing high quality inflatable graphite.
Background technology
Expansible black lead is the emerging a kind of important ceramic of recent two decades, just has been widely used in chemical industry, metallurgy, power machine, aerospace, nuclear industry since the appearance, has shown great vitality and market application foreground.It is mainly used in the static and dynamic sealing of equipment, is the preferred materials that substitutes easily carcinogenic asbestos sealing material.But the expansible black lead volatile matter that traditional method makes is up to 25～30wt%, sulphur content is up to 3.0～4.5wt%, the perishable metallic surface of pyrolysis product with residual sulfuric acid root or sulfuric acid molecule in the sealing material of its manufacturing, prolongation in time, sealing effectiveness can be subjected to very big infringement, even causes the generation of leakage accident.Graphite prolongs the C direction of principal axis and expands rapidly, forms a kind of material with good flexibility, and promptly expanded graphite worm is made flexible graphite material with expanded graphite worm.This soft graphite had both kept the high thermal conductivity of graphite, and had anisotropy, its heat conductivility even surpassed some metal such as steel, aluminium, and therefore the application in the heat conduction industry also will be a more promising field.
Industrial production expansible black lead mainly adopts electrochemical intercalation method and chemical graft process.
The advantage of electrochemical process is not adopt oxygenant, but replaces oxygenant with anodic oxidation.The pollution of production process is little, and production cost is relatively low, and the sulphur content that finally obtains descends to some extent.Shortcoming is that facility investment is bigger, and the easy passivation of electrode, thus need often to handle to safeguard, thus influence production efficiency; In addition, the electric field of electrochemical process is inhomogeneous, and the oxidation capacity difference of each position finally causes product also inhomogeneous.Chemical graft process mainly adopts nitric acid, potassium permanganate, potassium bichromate, hydrogen peroxide is as oxygenant, the vitriol oil is as intercalator, mixing the back reacts with graphite under normal pressure, then through washing and dry, can obtain expansible black lead, shortcoming is that production unit is simple, easy handling, but the price of oxygenant is higher, and most of oxygenant has harmful element, contaminate environment, and the process of chemical graft process production expansible black lead is more violent, is not easy control, the peroxidation phenomenon often occurs, structure to graphite has certain destruction, has greatly influenced the snappiness of product.Like this, a kind of less investment, production are simply polluted the less relatively intercalation method that can produce high quality inflatable graphite, become the technical barrier of expansible black lead.
The Chinese patent publication number is the patent documentation of CN1462724A, the technical scheme of " a kind of preparation method of expanded graphite without sulphur " is disclosed, this technical scheme is that perchloric acid, potassium permanganate, natural flake graphite are blended under 30～70 ℃ of reaction conditionss of temperature, reaction 30～90min, prepare expandable sulfur-free graphite, under 200～1000 ℃ of temperature, expand into high power graphite.The shortcoming of this kind technology is: 1, perchloric acid at high temperature decomposes easily and blasts, and the yellow smog of emitting when decomposing has pungency to skin and mucous membrane, especially corrodes eyes and nasal membrane, operational hazards, to the requirement of equipment than higher; 2, the ash content that adds affiliation increase crystalline flake graphite of potassium permanganate, the purity of reduction product; 3, the price of perchloric acid, potassium permanganate is very high, has increased the cost of product greatly.
The Chinese patent publication number is the patent documentation of CN1623895A, the technical scheme of " using dioxysulfate water to make the method for low-sulfur expansible black lead " is disclosed, this technical scheme is earlier hydrogen peroxide to be mixed with sulfuric acid, cool off under the normal pressure of back and the crystalline flake graphite reaction, just can make low-sulfur expansible black lead through washing, oven dry, the shortcoming of this kind technology is: very exothermic when 1, hydrogen peroxide mixes with sulfuric acid, hydrogen peroxide is heated and easily decomposes, therefore hydrogen peroxide can not fully be participated in reaction, causes certain waste; 2, reaction process is thermopositive reaction, and along with the carrying out of reaction, temperature of reaction constantly raises, and causes the intercalation degree of product uncontrollable.
Summary of the invention
The objective of the invention is under the prerequisite that does not increase raw materials cost, to adhere to principle simple to operate preparation fugitive constituent, low-sulfur content expansible black lead product.
For achieving the above object, the present invention proposes a kind of preparation method of high quality inflatable graphite, it is characterized in that: described high quality inflatable graphite is to be raw material with the crystalline flake graphite, adopts the vitriol oil to prepare under vacuum condition as oxygenant as intercalator, hydrogen peroxide.
The present invention prepares the chemical treatment method of high quality inflatable graphite, specifically may further comprise the steps and condition:
(1) with the vitriol oil injection reactor of volume pump with quantitative 98wt%;
(2) crystalline flake graphite with metering is delivered in the reactor by vacuum feeder, then with the reactor good seal, opens and stirs, and starting vacuum pump provides vacuum for reaction;
(3) open the hydrogen peroxide imported valve, utilize vacuum action that hydrogen peroxide slowly in the sucting reaction still, is opened the water coolant of reactor interlayer simultaneously, the temperature in the control reactor is not higher than 40 ℃;
(4) reaction times is 30～60min, and reaction changes material in the whizzer over to after finishing, centrifugal depickling, and water washes to pH value 4～7, dehydration;
(5) will change in the drying machine through the material after the washing dehydration processing, under 80 ℃～100 ℃ temperature, be dried to water content and be lower than 1%.
Wherein quantitatively the add-on of the 98wt% vitriol oil and the ratio (weight ratio) of graphite are (2.0～3.5): 1; The concentration of hydrogen peroxide is 27.5～35wt%, and the ratio of hydrogen peroxide and graphite (weight ratio) is (0.18～0.30): 1.
Vacuum in the described reaction process reactor is to utilize water ring vacuum pump to be connected on the reactor by surge tank to realize, vacuum degree control is less than 200pa, and is connected with water coolant in the interlayer of reactor.
The purpose that the invention provides vacuum is for controlled temperature preferably, makes reactor temperature keep comparatively constant temp.Vacuum pump can in time be taken away the reaction liberated heat with the form of steam, gas by low-boiling material (water or other) on the one hand, and the acid waste gas that vacuum pump will be taken out of from reactor, through the adsorption treatment of surge tank, slowed down influence to a certain extent to environment; The outer cooling water sandwich of reactor can advance a cooling on the other hand, thereby can keep relatively low and stable temperature of reaction.
Can obtain volatile matter by the inventive method and be lower than 12%, sulphur content is lower than 1.5% expansible black lead, and behind 900～1000 ℃ of pyroprocessing 30s, sulphur content is lower than the high-quality expanded graphite of 800ppm.
Embodiment
Embodiment one
(1) with the vitriol oil injection reactor of volume pump with the 98wt% of 70kg;
(2) 25kg50 order crystalline flake graphite is added in the reactor by feeder, with the reactor sealing, open and stir, open vacuum pump, the vacuum tightness in the control reactor is at 150Pa;
(3) open the charging valve of hydrogen peroxide, utilize vacuum slowly to add the hydrogen peroxide of 5kg30wt% in the reactor;
(4) reaction times 30min;
(5) through depickling, be washed to PH near 7;
(6) change in the drying machine high quality inflatable graphite that after being dried to water content under 100 ℃ the temperature and being lower than 1%, obtain allowance for expansion 250ml/g, fugitive constituent and be 11.5%, sulphur content is 1.2% low-sulfur low-volatile over to through the material after the processed.At 950 ℃ of expansion 30s, obtain sulphur content and only be 0.07% expanded graphite.
Under the constant condition of oxygenant, graphite, intercalator proportioning, do not provide vacuum to reaction, the allowance for expansion of the expansible black lead that reaction obtains under normal pressure is that 243ml/g, fugitive constituent 15.8%, sulphur content are 2.4% expansible black lead.In 950 ℃ of high temperature expansion 30s, still residual 0.15% sulphur content.
Embodiment two
(1) with the vitriol oil injection reactor of volume pump with 75kg98wt%;
(2) 25kg80 order crystalline flake graphite is added in the reactor by feeder, with the reactor sealing, open and stir, open vacuum pump, the vacuum tightness in the control reactor is at 150Pa;
(3) open the charging valve of hydrogen peroxide, utilize vacuum slowly to add the hydrogen peroxide of 6kg30wt% in the reactor;
(4) reaction times 40min;
(5) through depickling, be washed to PH near 7;
(6) change in the drying machine high quality inflatable graphite that after being dried to water content under 100 ℃ the temperature and being lower than 1%, obtain allowance for expansion 220ml/g, fugitive constituent and be 11.0%, sulphur content is 1.3% low-sulfur low-volatile over to through the material after the processed.Expand fully at 1000 ℃, obtain sulphur content and only be 0.08% expanded graphite.
Under the constant condition of oxygenant, graphite, intercalator proportioning, do not provide vacuum to reaction, the allowance for expansion of the expansible black lead that reaction obtains under normal pressure is that 200ml/g, fugitive constituent 14.9%, sulphur content are 2.1% expansible black lead.In 950 ℃ of high temperature expansion 30s, still residual 0.15% sulphur content.
The foregoing description is obtainable expansible black lead under vacuum condition, has low-sulfur content advantage, the expansible black lead sulphur content height that under non-vacuum condition, obtains of comparing, and expansion multiple is but low than vacuum condition end.Vacuum condition is produced expansible black lead down, pollutes little, lower-cost characteristics, can be widely applied to various dynamic and static sealing members such as oil, chemical industry, electric power, metallurgy, machinery, aerospace, nuclear industry, also can be used as the heat radiation sam material to be applied in the electronic industry; And along with the Application Areas of expansible black lead constantly enlarges, this product has broad application prospects.
Claims (6)
1. a chemical treatment method for preparing high quality inflatable graphite is characterized in that, described high quality inflatable graphite is to be raw material with the crystalline flake graphite, adopts the vitriol oil to prepare under vacuum condition as oxygenant as intercalator, hydrogen peroxide.
2. a kind of chemical treatment method for preparing high quality inflatable graphite according to claim 1 is characterized in that described preparation method may further comprise the steps and condition:
(1) with the vitriol oil injection reactor of volume pump with quantitative 98wt%;
(2) crystalline flake graphite with metering is delivered in the reactor by vacuum feeder, then with the reactor good seal, opens and stirs, and starting vacuum pump provides vacuum for reaction;
(3) open the hydrogen peroxide imported valve, utilize vacuum action that hydrogen peroxide slowly in the sucting reaction still, is opened the water coolant of reactor interlayer simultaneously, the temperature in the control reactor is not higher than 40 ℃;
(4) reaction times is 30～60min, and reaction changes material in the whizzer over to after finishing, centrifugal depickling, and water washes to pH value 4～7, dehydration;
(5) will change in the drying machine through the material after the washing dehydration processing, under 80 ℃～100 ℃ temperature, be dried to water content and be lower than 1%.
3, a kind of chemical treatment method for preparing high quality inflatable graphite according to claim 2 is characterized in that, the add-on of the described quantitative 98wt% vitriol oil and the ratio of graphite are (2.0～3.5): 1.
4, a kind of chemical treatment method for preparing high quality inflatable graphite according to claim 2 is characterized in that, the add-on of described quantitative hydrogen peroxide and the ratio of graphite are (0.18～0.30): 1.
5, a kind of chemical treatment method for preparing high quality inflatable graphite according to claim 4 is characterized in that, the concentration of described hydrogen peroxide is 27.5～35wt%.
6, a kind of chemical treatment method for preparing high quality inflatable graphite according to claim 2, it is characterized in that, vacuum in the described reaction process reactor is to utilize water ring vacuum pump to be connected on the reactor by surge tank to realize that vacuum degree control is being lower than 200pa.
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| CN2007101911914A CN101456553B (en) | 2007-12-11 | 2007-12-11 | Chemical processing method for preparing high quality inflatable graphite |
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| CN2007101911914A CN101456553B (en) | 2007-12-11 | 2007-12-11 | Chemical processing method for preparing high quality inflatable graphite |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381699A (en) * | 2011-07-26 | 2012-03-21 | 中科恒达石墨股份有限公司 | Preparation method of expandable graphite |
| CN102779990A (en) * | 2011-05-11 | 2012-11-14 | 三星Sdi株式会社 | Negative active material, method of preparing the same, and lithium battery including the same |
| CN102897753A (en) * | 2012-09-11 | 2013-01-30 | 华侨大学厦门园区 | Preparation method for graphite with high thermal conductivity |
| CN103395777A (en) * | 2013-08-07 | 2013-11-20 | 大同市普朔科技有限责任公司 | Preparation method of nano-graphite carbon powder |
| TWI417240B (en) * | 2009-09-18 | 2013-12-01 | Univ Hungkuang | The Method of Expanding Graphite |
| CN106315577A (en) * | 2016-08-31 | 2017-01-11 | 陈连捷 | Method for removing sulfuric acid from expandable graphite |
| CN106542527A (en) * | 2017-01-06 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of method of mechanical stripping grading system for graphene microchip dispersion liquid |
| CN108069419A (en) * | 2017-12-21 | 2018-05-25 | 浙江山峪科技股份有限公司 | A kind of macroscopic view graphene aerogel and preparation method thereof |
| CN108190882A (en) * | 2018-02-26 | 2018-06-22 | 乌兰察布市大盛石墨新材料股份有限公司 | Conductive graphite paper and preparation method thereof |
| CN108373152A (en) * | 2018-02-26 | 2018-08-07 | 乌兰察布市大盛石墨新材料股份有限公司 | Conductive graphite paper and preparation method thereof |
| CN110127690A (en) * | 2019-06-04 | 2019-08-16 | 新疆弘瑞达纤维有限公司 | A method of expanded graphite is prepared using continuously Hong burst release pressure technology |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1023820C (en) * | 1991-12-26 | 1994-02-16 | 清华大学 | Process for production of expandable graphite |
| GB2367291A (en) * | 2000-08-18 | 2002-04-03 | Graftech Inc | Preparing expandable graphite flake |
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2007
- 2007-12-11 CN CN2007101911914A patent/CN101456553B/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI417240B (en) * | 2009-09-18 | 2013-12-01 | Univ Hungkuang | The Method of Expanding Graphite |
| US9029016B2 (en) | 2011-05-11 | 2015-05-12 | Samsung Sdi Co., Ltd. | Negative active material, method of preparing the same, and lithium battery including the same |
| CN102779990A (en) * | 2011-05-11 | 2012-11-14 | 三星Sdi株式会社 | Negative active material, method of preparing the same, and lithium battery including the same |
| CN102779990B (en) * | 2011-05-11 | 2016-10-05 | 三星Sdi株式会社 | Negative active core-shell material, its preparation method and include its lithium battery |
| CN102381699A (en) * | 2011-07-26 | 2012-03-21 | 中科恒达石墨股份有限公司 | Preparation method of expandable graphite |
| CN102897753A (en) * | 2012-09-11 | 2013-01-30 | 华侨大学厦门园区 | Preparation method for graphite with high thermal conductivity |
| CN103395777A (en) * | 2013-08-07 | 2013-11-20 | 大同市普朔科技有限责任公司 | Preparation method of nano-graphite carbon powder |
| CN103395777B (en) * | 2013-08-07 | 2014-07-30 | 大同市普朔科技有限责任公司 | Preparation method of nano-graphite carbon powder |
| CN106315577A (en) * | 2016-08-31 | 2017-01-11 | 陈连捷 | Method for removing sulfuric acid from expandable graphite |
| CN106542527A (en) * | 2017-01-06 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of method of mechanical stripping grading system for graphene microchip dispersion liquid |
| CN108069419A (en) * | 2017-12-21 | 2018-05-25 | 浙江山峪科技股份有限公司 | A kind of macroscopic view graphene aerogel and preparation method thereof |
| CN108190882A (en) * | 2018-02-26 | 2018-06-22 | 乌兰察布市大盛石墨新材料股份有限公司 | Conductive graphite paper and preparation method thereof |
| CN108373152A (en) * | 2018-02-26 | 2018-08-07 | 乌兰察布市大盛石墨新材料股份有限公司 | Conductive graphite paper and preparation method thereof |
| CN110127690A (en) * | 2019-06-04 | 2019-08-16 | 新疆弘瑞达纤维有限公司 | A method of expanded graphite is prepared using continuously Hong burst release pressure technology |
| CN110127690B (en) * | 2019-06-04 | 2023-02-07 | 新疆弘瑞达纤维有限公司 | Method for preparing expanded graphite by adopting continuous detonation pressure release technology |
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