CN100400416C - Preparation method of expandable graphite with high initial expansion temperature - Google Patents
Preparation method of expandable graphite with high initial expansion temperature Download PDFInfo
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- CN100400416C CN100400416C CNB2006100129361A CN200610012936A CN100400416C CN 100400416 C CN100400416 C CN 100400416C CN B2006100129361 A CNB2006100129361 A CN B2006100129361A CN 200610012936 A CN200610012936 A CN 200610012936A CN 100400416 C CN100400416 C CN 100400416C
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000010439 graphite Substances 0.000 title claims abstract description 98
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 13
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 13
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000001488 sodium phosphate Substances 0.000 claims description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 12
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 12
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 12
- 239000011790 ferrous sulphate Substances 0.000 claims description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 229940073589 magnesium chloride anhydrous Drugs 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000008393 encapsulating agent Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 229920006351 engineering plastic Polymers 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- -1 metallurgy Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000004042 decolorization Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000003483 aging Methods 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000001117 sulphuric acid Substances 0.000 description 13
- 235000011149 sulphuric acid Nutrition 0.000 description 13
- 239000007788 liquid Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of expandable graphite with high initial expansion temperature. The method comprises the steps of soaking natural crystalline flake graphite in a mixed solution of a sealing agent and sulfuric acid, adding an oxidizing agent for reaction under continuous stirring to obtain acidic graphite, adding a reducing agent for decolorization, washing with water to remove acid, aging, washing, drying, expanding and the like to obtain the expandable graphite with the expansion volume of 250-260mL/g, the initial expansion temperature of 300 +/-5 ℃, and the pH value of 6-7. The expandable graphite prepared by the invention has clean product surface, no acidic and alkaline substances, good fluidity, no moisture absorption and stable air, can be used as a flame retardant material for engineering plastics, rubber and other substances, and can be widely applied to the technical fields of steel, metallurgy, petroleum, chemical industry, mechanical manufacturing and aerospace.
Description
Technical field
The present invention relates to a kind of preparation method of expandable graphite with high reference expansion temperature, belong to materials science field.
Expansible black lead is because it has good swellability, and that finished product have is high temperature resistant, radioprotective, thermal insulation, lubricated, plasticity-, and chemical stability and pliable and tough ductility, stopping property, is widely used in fields such as iron and steel, metallurgy, chemical industry, machinofacture.Particularly the Application Areas of expandable graphite with high reference expansion temperature is more extensive.The patent documentation of Chinese patent notification number CN1050340C discloses the technical scheme of a kind of " manufacture method of expandable sulfur-free graphite ", this technical scheme is natural flake graphite to be impregnated in the nitric acid of 65-98% and the organic acid mixed solution carry out oxidizing reaction, through decolouring, washing, the dry expandable sulfur-free graphite that gets, the product that this technical scheme makes can obtain the fine sealing material through further processing.But the initial expansion temperature of this expansible black lead is 150 ℃, can not be as the fire retardant material of engineering plastics.In the prior art, the Preparation of Expansible Graphite method that reaches about 300 ℃ of initial expansion temperature is not appeared in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide a kind of initial expansion temperature height (300 ± 5 ℃), stable performance can be used as the Preparation of Expansible Graphite method of field fire retardant materials such as engineering plastics, rubber.
The object of the present invention is achieved like this.Method of the present invention may further comprise the steps:
(1) oxidation sealing
It is that the sulfuric acid of 80%-95% dissolves that encapsulant is put into massfraction, add graphite then and stir, the vitriolic consumption be the graphite quality 0.8-4 doubly, the consumption of encapsulant be the graphite quality 0.005-0.26 doubly; Afterwards, adding quality under constantly stirring is that graphite quality 0.05-0.25 oxygenant doubly reacts, and reaction times 0.5-2 hour, temperature of reaction was 5-40 ℃, made acid graphite;
Wherein, used encapsulant is selected one of following combination: ferrous sulfate and Sodium hexametaphosphate 99 are that combination in 1.0: 2.5, Calcium Chloride Powder Anhydrous and Sodium hexametaphosphate 99 are that combination in 1.0: 2.0, ferrous sulfate and trisodium phosphate are that combination in 1.0: 2.0, Magnesium Chloride Anhydrous and trisodium phosphate are that combination in 1.0: 2.0, Magnesium Chloride Anhydrous and Sodium hexametaphosphate 99 are that combination in 1.0: 3.0, Calcium Chloride Powder Anhydrous and trisodium phosphate are combination in 1.0: 2.7 with mass ratio with mass ratio with mass ratio with mass ratio with mass ratio with mass ratio;
Used oxygenant is selected one of following material: potassium permanganate, Potcrate, ammonium peroxydisulfate;
(2) decolouring
Adding quality in the acid graphite that makes is graphite quality 0.5-5 water doubly, and adding quality under constantly stirring is graphite quality 0.05-0.3 discoloring agent doubly, decolours 15-50 minute, washes to the pH=6-7 of graphite surface centrifuge dripping with water;
Used discoloring agent is selected one of following material: oxalic acid, formic acid, hydrogen peroxide, Sodium Nitrite;
(3) ageing
Acid graphite after the drying is 20-40 ℃ of placement, ageing 24-72 hour;
(4) washing
The acid graphite that ageing is good is washed with water to pH=6-7, centrifuge dripping;
(5) oven dry
65-80 ℃ of oven dry, the massfraction of water obtains the expandable graphite with high reference expansion temperature finished product less than 1% to the graphite with the graphite after the above-mentioned drying;
(6) expanded
At 950 ℃, expanded 30 seconds, the allowance for expansion of survey expansible black lead product.
Compared with the prior art the present invention has following marked improvement: 1, the beginning expansion temperature of Zhi Bei expansible black lead can be used as the fire retardant material of materials such as engineering plastics and rubber up to 5 ℃ of 300; 2, its pH value=6-7, the product surface cleaning does not contain acid, alkaloid substance; 3, the good fluidity of product, non-hygroscopic in air, to air-stable; 4, present method technology is simple, is easy to realize suitability for industrialized production.
Embodiment
Enumerate specific embodiment below, the invention will be further described, and the graphite of using among the given embodiment is 50 purpose natural flake graphites.
Embodiment 1
It is in 85% the sulphuric acid soln that 0.2g ferrous sulfate and 0.5g Sodium hexametaphosphate 99 are dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stir and add 0.9g potassium permanganate reaction 50 minutes down, after question response was finished, adding 30g water and 1g massfraction were 30% hydrogen peroxide in feed liquid, and decolouring is 20 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% times to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 260mL/g, and initial expansion temperature is 300 ℃.
Embodiment 2
It is in 85% the sulphuric acid soln that the trisodium phosphate of 0.3g Magnesium Chloride Anhydrous and 0.6g is dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the potassium permanganate that adds 0.9g down reacted 50 minutes, after question response was finished, adding 30g water and 1g massfraction were 30% hydrogen peroxide in feed liquid, and decolouring is 20 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 255mL/g, and initial expansion temperature is 301 ℃.
Embodiment 3
It is in 80% the sulphuric acid soln that 0.2g ferrous sulfate and 0.5g Sodium hexametaphosphate 99 are dissolved in the 29g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the potassium permanganate that adds 0.9g down reacted 50 minutes, after question response was finished, adding 30g water and 1g massfraction were 30% hydrogen peroxide in feed liquid, and decolouring is 20 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=7 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 265mL/g, and initial expansion temperature is 295 ℃.
Embodiment 4
It is in 88% the sulphuric acid soln that the Sodium hexametaphosphate 99 of 0.25g Calcium Chloride Powder Anhydrous and 0.5g is dissolved in the 25g massfraction, the massfraction that adds 10g carbon is 95% graphite, in 30 ℃, constantly stirring the potassium permanganate that adds 0.8g down reacted 60 minutes, after question response is finished, add 40g water and 1.2g oxalic acid in feed liquid, decolouring is 30 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6.2 once more, centrifuge dripping 25 ℃ of ageings; Product dried till the massfraction of water is 0.8% to the expansible black lead at 75 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 252mL/g, and initial expansion temperature is 296 ℃.
Embodiment 5
It is in 95% the sulphuric acid soln that 0.3g ferrous sulfate and 0.6g trisodium phosphate are dissolved in the 20g massfraction, the massfraction that adds 10g carbon is 95% graphite, in 25 ℃, constantly stirring the potassium permanganate that adds 0.9g down reacted 70 minutes, after question response is finished, in feed liquid, add 40g water and 1.2g oxalic acid, decolouring is 30 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping, after 70 hours, be washed to graphite surface pH=6 once more, centrifuge dripping 30 ℃ of ageings; Product dried till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 255mL/g, and initial expansion temperature is 305 ℃.
Embodiment 6
It is in 85% the sulphuric acid soln that the trisodium phosphate of 0.3g Magnesium Chloride Anhydrous and 0.6g is dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the Potcrate that adds 1.0g down reacted 50 minutes, after question response is finished, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=7 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 245mL/g, and initial expansion temperature is 302 ℃.
Embodiment 7
It is in 80% the sulphuric acid soln that 0.2g ferrous sulfate and 0.5g Sodium hexametaphosphate 99 are dissolved in the 29g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the ammonium peroxydisulfate that adds 2.0g down reacted 60 minutes, after question response is finished, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping, 20 ℃ of ageings after 48 hours, be washed to graphite surface pH=6 once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 260mL/g, and initial expansion temperature is 298 ℃.
Embodiment 8
It is in 80% the sulphuric acid soln that 0.2g ferrous sulfate and 0.5g Sodium hexametaphosphate 99 are dissolved in the 29g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the potassium permanganate that adds 0.9g down reacted 50 minutes, after question response is finished, add 40g water and 1.3g oxalic acid in feed liquid, decolouring is 20 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 260mL/g, and initial expansion temperature is 297 ℃.
Embodiment 9
It is in 85% the sulphuric acid soln that 0.2g ferrous sulfate and 0.5g Sodium hexametaphosphate 99 are dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the potassium permanganate that adds 0.9g down reacted 50 minutes, after question response is finished, add the Sodium Nitrite of 40g water and 1.0g in feed liquid, decolouring is 30 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6.3 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 264mL/g, and initial expansion temperature is 295 ℃.
Embodiment 10
It is in 85% the sulphuric acid soln that 0.2g Calcium Chloride Powder Anhydrous and 0.54g trisodium phosphate are dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the potassium permanganate that adds 0.9g down reacted 60 minutes, after question response was finished, adding 30g water and 1g massfraction were 30% hydrogen peroxide in feed liquid, and decolouring is 30 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6 once more, centrifuge dripping 20 ℃ of ageings; Product dried till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 267mL/g, and initial expansion temperature is 298 ℃.
Embodiment 11
It is in 85% the sulphuric acid soln that the trisodium phosphate of 0.3g Magnesium Chloride Anhydrous and 0.6g is dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the ammonium peroxydisulfate that adds 1.8g down reacted 60 minutes, after question response is finished, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6.8 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 257mL/g, and initial expansion temperature is 303 ℃.
Embodiment 12
It is in 85% the sulphuric acid soln that the trisodium phosphate of 0.2g Calcium Chloride Powder Anhydrous and 0.54g is dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the Potcrate that adds 1.2g down reacted 60 minutes, after question response is finished, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=7 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 259mL/g, and initial expansion temperature is 300 ℃.
Embodiment 13
It is in 85% the sulphuric acid soln that 0.2g ferrous sulfate and 0.5g Sodium hexametaphosphate 99 are dissolved in the 27g massfraction, the massfraction that adds 10g carbon is 99% graphite, in 20 ℃, constantly stirring the potassium permanganate that adds 0.9g down reacted 50 minutes, after question response is finished, add 30g water and 1.5g formic acid in feed liquid, decolouring is 25 minutes under constantly stirring, the acid graphite of gained is washed with water to graphite surface pH=6, centrifuge dripping; After 48 hours, be washed to graphite surface pH=6.5 20 ℃ of ageings once more, centrifuge dripping is dried product till the massfraction of water is 0.8% to the expansible black lead at 80 ℃, the expansible black lead finished product.At 950 ℃, expanded 30 seconds, recording allowance for expansion was 267mL/g, and initial expansion temperature is 303 ℃.
Claims (2)
1. Preparation of Expansible Graphite method is characterized in that it may further comprise the steps:
(1) oxidation sealing
It is that the sulfuric acid of 80%-95% dissolves that encapsulant is put into massfraction, add graphite then and stir, the vitriolic consumption be the graphite quality 0.8-4 doubly, the consumption of encapsulant be the graphite quality 0.005-0.26 doubly; Then, adding quality under constantly stirring is that graphite quality 0.05-0.25 oxygenant doubly reacts, and reaction times 0.5-2 hour, temperature of reaction was 5-40 ℃, made acid graphite;
Wherein, used encapsulant is selected one of following combination: ferrous sulfate and Sodium hexametaphosphate 99 are that combination in 1.0: 2.5, Calcium Chloride Powder Anhydrous and Sodium hexametaphosphate 99 are that combination in 1.0: 2.0, ferrous sulfate and trisodium phosphate are that combination in 1.0: 2.0, Magnesium Chloride Anhydrous and trisodium phosphate are that combination in 1.0: 2.0, Magnesium Chloride Anhydrous and Sodium hexametaphosphate 99 are that combination in 1.0: 3.0, Calcium Chloride Powder Anhydrous and trisodium phosphate are combination in 1.0: 2.7 with mass ratio with mass ratio with mass ratio with mass ratio with mass ratio with mass ratio;
Used oxygenant is one of following material: potassium permanganate, Potcrate, ammonium peroxydisulfate;
(2) decolouring
Adding quality in the acid graphite that makes is graphite quality 0.5-5 water doubly, and adding quality under constantly stirring is graphite quality 0.05-0.3 discoloring agent doubly, decolours 15-50 minute, washes to the pH=6-7 of graphite surface centrifuge dripping with water;
Used discoloring agent is selected one of following material: oxalic acid, formic acid, hydrogen peroxide, Sodium Nitrite;
(3) ageing
Acid graphite after the drying is 20-40 ℃ of placement, ageing 24-72 hour;
(4) washing
The acid graphite that ageing is good is washed with water to pH=6-7, centrifuge dripping;
(5) oven dry
Graphite after the drying is 65-80 ℃ of oven dry, to the graphite the massfraction of water less than 1%, the expansible black lead finished product;
(6) expanded
At 950 ℃, expanded 30 seconds.
2. by the described Preparation of Expansible Graphite method of claim 1, it is characterized in that graphite is natural flake graphite in the step (1).
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| CNB2006100129361A CN100400416C (en) | 2006-07-11 | 2006-07-11 | Preparation method of expandable graphite with high initial expansion temperature |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102008038411A1 (en) | 2007-09-11 | 2009-03-12 | Basf Se | Thermoplastic molding material, useful e.g. for preparing fibers, foil and molded body, comprises thermoplastic polyamide, flame retardant e.g. expandable graphite and fluorine containing polymer, and additives |
| US8968695B2 (en) | 2009-08-10 | 2015-03-03 | Idt International Co., Ltd. | Method of producing nano-size graphene-based material and an equipment for producing the same |
| CN102897754B (en) * | 2012-09-14 | 2015-03-25 | 中科恒达石墨股份有限公司 | Manufacturing method for high temperature-resistant high-strength flexible graphite material |
| CN108836430B (en) * | 2018-06-11 | 2020-08-21 | 浙江亚通焊材有限公司 | Medical forceps and manufacturing method thereof |
| CN109616668A (en) * | 2018-12-06 | 2019-04-12 | 中国科学院兰州化学物理研究所 | The micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size |
| CN112174132A (en) * | 2020-10-26 | 2021-01-05 | 鸡西市唯大新材料科技有限公司 | Preparation method of expandable graphite with high-temperature expansion |
| CN112723354B (en) * | 2020-12-24 | 2021-07-30 | 鸡西市海盛新能源材料有限公司 | Production process for preparing expandable graphite with high initial temperature |
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| CN1004440B (en) * | 1986-04-14 | 1989-06-07 | 北京市环境保护技术设备中心 | Vertical double stage coal combustion furnace for ventilating warm air |
| JPH05178605A (en) * | 1991-12-27 | 1993-07-20 | Nippon Kasei Chem Co Ltd | Production of thermally expansible graphite |
| CN1096767A (en) * | 1993-06-19 | 1994-12-28 | 李儒臣 | A kind of method of making low-sulfur expansible black lead with chemical method |
| CN1102398A (en) * | 1993-11-05 | 1995-05-10 | 宋克敏 | Manufacturing method of low-sulfur expansible black lead |
| CN1239071A (en) * | 1998-06-17 | 1999-12-22 | 攀枝花大学 | Process for preparing flake-shaped expanded graphite |
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