CN103738955A - Expanded graphite environment-friendly material with Kish graphite as raw material as well as preparation method and application thereof - Google Patents
Expanded graphite environment-friendly material with Kish graphite as raw material as well as preparation method and application thereof Download PDFInfo
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- CN103738955A CN103738955A CN201410013920.7A CN201410013920A CN103738955A CN 103738955 A CN103738955 A CN 103738955A CN 201410013920 A CN201410013920 A CN 201410013920A CN 103738955 A CN103738955 A CN 103738955A
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Abstract
The invention provides a preparation method of an expanded graphite environment-friendly material with Kish graphite as a raw material. The preparation method comprises the steps of preparing Kish graphite with fall dust and slag blocks in ladle waste slag of iron and steel enterprises as basic materials; preparing Kish expansible graphite by utilizing Kish graphite; heating the Kish expansible graphite at 800-1000 DEG C to obtain expanded graphite with the expanded volume of 50-250ml/g. The expanded graphite environment-friendly material is characterized by preparing blocks which have density not more than 0.15g/cm<3> and required dimensions by pressing the obtained expanded graphite in a die and wrapping the blocks to prevent the blocks from being dispersed and broken, thus obtaining the expanded graphite environment-friendly material. The material can be used for removing greasy dirt on water surfaces and organic pollution of water bodies through adsorption, and has higher decontamination effects than common activated carbon.
Description
Technical field
The invention belongs to the Carbon Materials field of Materials Science and Engineering and the three wastes of environmental science and technology and process and comprehensive utilization field, particularly a kind ofly take expanded graphite environment-friendly materials and preparation and the application that Kish graphite is raw material.
Background technology
Good environment is the prerequisite of human survival.The environmental problem that modern science and technology and Economic development bring, the pollution of the three wastes to air, water body and soil, the existence that has jeopardized the mankind.The status of the environmental science and technology that protection of the environment, improvement are polluted in the science Sustainable development of human society is more and more important.
Due to the generally use of oil fuel, the oil pollution problem of water body is day by day serious.At present be mainly also the improvement to water pollution to burst oil leak, traditional method is to aspirate oil slick and eliminate greasy dirt with the absorption water surface Residual oils such as asphalt felt, gac, plant ash or employing degreaser after the oil fence encloses oil, after but sorbent material sinks under water, can cause secondary pollution, itself also has pollution to water body degreaser.To a small amount of greasy dirt of residual diffusion after burst accident and a small amount of greasy dirt that the surface facilities such as boats and ships leaks at ordinary times substantially also do not administer.This small amount of greasy dirt spreads on the water surface, and the water surface area of pollution is large, destroys water ecological setting, especially serious on the impact of aquaculture, fishery.
Expanded graphite be some compound between graphite layers (GICs) when rapid heating, inset gasification make graphite along c-axis expand rapidly form take macropore as main vesicular structure graphite.Industrial, expanded graphite is that (raw material of employing is generally expansible black lead also referred to as acidifying graphite to the intermediates of preparing soft graphite, is remaining H
2sO
4-GIC).The liquid phase adsorption excellent performance of expanded graphite, particularly has the adsorptive power of superelevation to oil product and macromolecule organic.Graphite is apolar surfaces, so in water and oily mixed system, the preferential adsorbed oil of expanded graphite.Had a large amount of research work to confirm, expanded graphite can be for the improvement of water body oil pollution and Organic pollutants, its to the removing effect of pollutent far above gac.
The raw material expansible black lead of expanded graphite, adopts large stretch of natural flake graphite preparation, general granularity >=150 μ m conventionally.Large scale natural graphite resource scarcity, cost is high, has restricted the application of expanded graphite as environment-friendly materials.
Kish graphite (also claim: kish graphite, primary graphite, kish, kish etc.) be molten hot metal when cooling, the graphite crystallization body of the carbon of separating out from molten iron due to carbon supersaturation.Under the high temperature of blast-furnace smelting, coke is as reductive agent, and except reduction of iron ore Cheng Tie, its carbon is also dissolved in iron liquid, and smelting temperature is higher, and the meltage of carbon is larger, meltage >=4.0% of carbon conventionally in molten iron under normal smelting temperature.The carbon content of commercial iron is 2-4%, most of below 3.5%.Be that molten iron will separate out approximately 1% or more Kish graphite in condensation process.Within 2012, WORLD PIG IRON PRODUCTION is 1,100,000,000 tons, has separated out the Kish graphite of ten-million-ton scale, this wherein China accounted for over half.Kish graphite is to separate out under high temperature atmosphere environment, most of oxidized burning, even but only have 1/10th retain, also there is the growing amount of megaton every year.Kish graphite is present in the dust fall of iron work and converter steelmaking factory and in slag body in a large number, is the three-waste pollution thing of iron and steel enterprise.If can reclaim a part, as graphite raw material, use, will be " the city mineral products " of producing ten ton graphite per year so.
In the form of sheets, its particle diameter is large for Kish graphite granule, most particle >=150 μ m, the suitable expanded graphite that is prepared into.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide expanded graphite environment-friendly materials and preparation and application that a kind of Kish of take graphite is raw material, comprise collection and the enrichment of Kish graphite; The preparation of Kish expansible black lead; The preparation of Kish expanded graphite; Preparation and the use of Kish expanded graphite environment-friendly materials.
To achieve these goals, the technical solution used in the present invention is:
The expanded graphite environment-friendly materials preparation method that the Kish graphite of take is raw material, comprises the steps:
Take the dust fall of iron and steel enterprise and the clinker in hot metal ladle waste produces Kish graphite as basic material;
Utilize described Kish graphite-made to obtain Kish expansible black lead;
Through 800-1000 ℃ of heating, obtain the expanded graphite that allowance for expansion is 50-250ml/g again.
Collect the clinker of Kish graphite enrichment in hot metal ladle waste, pulverize, utilize acidleach with separated Kish graphite.
The slag body of the dust fall of collecting and pulverizing, acidleach is adopted to the flotation processing treatment in crystalline flake graphite ore deposit, obtain the middle carbon Kish graphite of purity >=80%C, carbon Kish graphite in processing with natural graphite purification techniques again, high-purity Kish graphite of the high-carbon of obtain >=94%C or >99.9%C.
What by described method, be prepared from take the expanded graphite environment-friendly materials that Kish graphite is raw material, utilizes gained expanded graphite to pressurize in mould to be prepared into density for≤0.15g/cm
3desired size block, block has wrap outward in case stops body is fragmentary.
Described wrap hole≤1mm, water can permeate, and wrap directly covers expanded graphite block, or makes casing with wrap, splendid attire expanded graphite.
The expanded graphite environment-friendly materials that the gained Kish graphite of take is raw material can be used for the Organic pollutants of adsorption removal water oil stain and water body.During described expanded graphite environment-friendly materials are directly aborted or be placed in water treatment system.
After processing water oil stain, adopt the fractionation of≤400 ℃ to process, reclaim oil product and regeneration Kish expanded graphite environment-friendly materials, the Kish expanded graphite of regeneration recycles as environmental protection material product.After each regeneration, the absorption soil removability of Kish expanded graphite environment-friendly materials decreases, and general regeneration is no more than 5 times.
Or after processing water oil stain, described expanded graphite environment-friendly materials are directly used as fuel, its calorific value is higher than common coal.
Compared with prior art, Kish expanded graphite environment-friendly materials of the present invention, refer to and take the expanded graphite that Kish graphite prepared as raw material and the density≤0.15g/cm being prepared into by expanded graphite
3the goods that have wrap.The wrap of goods prevents that block is fragmentary and lost.This Kish expanded graphite environment-friendly materials are for the adsorption removal of water body oil pollution and Organic pollutants, and its clean effect is more much higher than common gac.
Embodiment
Below in conjunction with embodiment, describe embodiments of the present invention in detail.
Embodiment 1
The ground dust fall of collecting in certain large-scale iron and steel enterprise's converter steelmaking workshop, by GB/T3521-2008 (GB: graphite chemical analysis method) test, its carbon content is 11.8%.Dust fall adopts the common flotation unit in crystalline flake graphite ore deposit, and a flotation obtains the middle carbon Kish graphite of 81.5%C.Granularity >=150 μ the m of the rear Kish graphite of screening accounts for 88%, XRD test and shows that its degree of graphitization can reach 98%.
Embodiment 2
The desulfurization slag of collecting at certain large-scale iron and steel enterprise ironmaking slag muck, in the slag body through simply breaking into pieces, after acidleach, carbon content is 4.1%.Slag body adopts the common flotation unit in crystalline flake graphite ore deposit, and a flotation obtains the middle carbon Kish graphite of 87.3%C.Granularity >=150 μ the m of the rear Kish graphite of screening accounts for 93%, XRD test and shows that its degree of graphitization reaches 96%.
Embodiment 3
The compound (1:1) of the Kish graphite that embodiment 1,2 is obtained, adopts common H
2sO
4/ H
2o
2method intercalation processing, obtains Kish expansible black lead.950 ℃ obtain the Kish expanded graphite that allowance for expansion is 130ml/g after expanded.
Embodiment 4
The Kish expanded graphite powder (0.008g/cm that embodiment 3 is obtained
3) and be respectively 0.05g/cm by the density of its compacting
3, 0.09g/cm
3block, throw in respectively in heavy oil and gasoline.Measure the saturated extent of adsorption of the Kish expanded graphite of each density.To heavy oil, adsorptive capacity is respectively 40,15,8g/g; To gasoline, be respectively 31,15,6g/g.Adsorptive capacity (5g/g is following) far above gac.
Embodiment 5
At 1m
2the water surface on, shed 10ml diesel oil.By the density of compacting, be 0.04g/cm
310*10*1(cm) Kish expanded graphite block, with general kitchen paper using parcel, make Kish expanded graphite environmental protection material product.Kish expanded graphite environmental protection material product is placed on the water surface of diesel oil, and promotes it and slowly cruise on the water surface.After 30min, on the water surface, floating oil product is clean by the absorption of Kish expanded graphite environmental protection material product.
Embodiment 6
In Mou printing and dyeing mill water treatment system, after its waste water is processed in earlier stage, to entering the waste water before microbiological treatment pond, carry out Kish expanded graphite environment-friendly materials and process.In the hydraulic pipe of its diameter Ф 1.0m, place the net cage by the establishment of 50 orders (aperture 300 μ m) Stainless Steel Cloth, in net cage, place the Kish expanded graphite plate 10kg of density 0.09g/cm3.Stainless Steel Wire net cage is of a size of Ф 1.0*0.5(m).The Kish expanded graphite environmental protection material product that wastewater streams is wrap through Stainless Steel Wire net cage filters, and measures and filters chemical total oxygen demand COD value in the water body of front and back.Process 3500 tons of filtered wastewaters, water body average COD value 95mg/l before filtering, water body average COD value 79mg/l after filtering, clearance rate 17% 10 days.Be disposed, Kish expanded graphite environment-friendly materials also have the ability of depolluting, and now, its adsorptive capacity is 5.6kgCOD/kg, far above the saturated adsorption value of the gac of 0.5kgCOD/kg.
Claims (10)
1. the expanded graphite environment-friendly materials preparation method that the Kish graphite of take is raw material, is characterized in that, comprises the steps:
Take the dust fall of iron and steel enterprise and the clinker in hot metal ladle waste produces Kish graphite as basic material;
Utilize described Kish graphite-made to obtain Kish expansible black lead;
Through 800-1000 ℃ of heating, obtain the expanded graphite that allowance for expansion is 50-250ml/g again.
2. the expanded graphite environment-friendly materials preparation method that the Kish graphite of take is according to claim 1 raw material, is characterized in that, collects the clinker of Kish graphite enrichment in hot metal ladle waste, pulverizes, and utilizes acidleach with separated Kish graphite.
3. the expanded graphite environment-friendly materials preparation method that the Kish graphite of take is according to claim 2 raw material, it is characterized in that, the slag body of the dust fall of collecting and pulverizing, acidleach is adopted to the flotation processing treatment in crystalline flake graphite ore deposit, obtain the middle carbon Kish graphite of purity >=80%C, carbon Kish graphite in processing with natural graphite purification techniques again, high-purity Kish graphite of the high-carbon of obtain >=94%C or >99.9%C.
4. the expanded graphite environment-friendly materials that the Kish graphite of take is raw material, are prepared from by method described in claim 1.
5. a kind of expanded graphite environment-friendly materials that Kish graphite is raw material of take according to claim 4, is characterized in that, utilize gained expanded graphite to pressurize in mould to be prepared into density for≤0.15g/cm
3desired size block, block has wrap outward in case stops body is fragmentary.
6. a kind of expanded graphite environment-friendly materials that Kish graphite is raw material of take according to claim 5, is characterized in that described wrap hole≤1mm, water can permeate, wrap directly covers expanded graphite block, or makes casing with wrap, splendid attire expanded graphite.
7. a kind of expanded graphite environment-friendly materials that Kish graphite is raw material purposes for the Organic pollutants of adsorption removal water oil stain and water body of take according to claim 4.
8. purposes according to claim 7, is characterized in that, during described expanded graphite environment-friendly materials are directly aborted or be placed in water treatment system.
9. purposes according to claim 7, is characterized in that, after processing water oil stain, adopts the fractionation of≤400 ℃ to process, and reclaims oil product and regeneration Kish expanded graphite environment-friendly materials, and the Kish expanded graphite of regeneration recycles as environmental protection material product.
10. purposes according to claim 7, is characterized in that, after processing water oil stain, described expanded graphite environment-friendly materials are directly used as fuel.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084346A (en) * | 2014-05-08 | 2015-11-25 | 国能科技创新有限公司 | Method for preparing multi-layer graphene |
| CN107055683A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | A kind of detersive for being used to remove slick |
| CN108635915A (en) * | 2018-05-30 | 2018-10-12 | 清华大学 | Graphite sorbing material is used for the purposes and method of the toxic inflammable and explosive dangerous chemical leakage of emergency processing liquid |
| CN109745949A (en) * | 2019-03-08 | 2019-05-14 | 清华大学 | A kind of low-density self-forming graphite adsorbent material and its preparation and reclaiming method |
| CN110475747A (en) * | 2017-03-31 | 2019-11-19 | 安赛乐米塔尔公司 | For the method by kish manufacture graphene oxide |
| CN112135792A (en) * | 2018-05-16 | 2020-12-25 | 安赛乐米塔尔公司 | Method for producing pristine graphene from kish graphite |
| US20210230003A1 (en) * | 2018-05-23 | 2021-07-29 | Arcelormittal | A method for the manufacture of reduced graphene oxide from electrode graphite scrap |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404061A (en) * | 1962-03-21 | 1968-10-01 | Union Carbide Corp | Flexible graphite material of expanded particles compressed together |
| JPS6369705A (en) * | 1986-09-12 | 1988-03-29 | Sumitomo Metal Ind Ltd | Production of expanded graphite |
| JPS63112408A (en) * | 1986-10-31 | 1988-05-17 | Sumitomo Metal Ind Ltd | Production of thermally expanded kish graphite |
| JPS63252978A (en) * | 1987-04-07 | 1988-10-20 | 住友金属工業株式会社 | Manufacture of expanded graphite |
| US5672327A (en) * | 1994-09-26 | 1997-09-30 | Indresco Canada, Inc. | Beneficiation of kish graphite |
| CN1579615A (en) * | 2004-05-18 | 2005-02-16 | 清华大学 | Preparation of oil pollution adsorbent and its recovery and regeneration method |
-
2014
- 2014-01-13 CN CN201410013920.7A patent/CN103738955A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404061A (en) * | 1962-03-21 | 1968-10-01 | Union Carbide Corp | Flexible graphite material of expanded particles compressed together |
| JPS6369705A (en) * | 1986-09-12 | 1988-03-29 | Sumitomo Metal Ind Ltd | Production of expanded graphite |
| JPS63112408A (en) * | 1986-10-31 | 1988-05-17 | Sumitomo Metal Ind Ltd | Production of thermally expanded kish graphite |
| JPS63252978A (en) * | 1987-04-07 | 1988-10-20 | 住友金属工業株式会社 | Manufacture of expanded graphite |
| US5672327A (en) * | 1994-09-26 | 1997-09-30 | Indresco Canada, Inc. | Beneficiation of kish graphite |
| CN1579615A (en) * | 2004-05-18 | 2005-02-16 | 清华大学 | Preparation of oil pollution adsorbent and its recovery and regeneration method |
Non-Patent Citations (1)
| Title |
|---|
| 任京成等: "膨胀石墨-一种新型环境材料", 《中国非金属矿工业导刊》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084346A (en) * | 2014-05-08 | 2015-11-25 | 国能科技创新有限公司 | Method for preparing multi-layer graphene |
| CN107055683A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | A kind of detersive for being used to remove slick |
| CN107055684A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | Environment-friendly type is used to remove detersive of slick and preparation method thereof |
| CN107055682A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | It is a kind of to be used to remove detersive of slick and preparation method thereof |
| CN110475747A (en) * | 2017-03-31 | 2019-11-19 | 安赛乐米塔尔公司 | For the method by kish manufacture graphene oxide |
| CN110475747B (en) * | 2017-03-31 | 2023-04-14 | 安赛乐米塔尔公司 | Method for producing graphene oxide from crystalline graphite |
| CN112135792A (en) * | 2018-05-16 | 2020-12-25 | 安赛乐米塔尔公司 | Method for producing pristine graphene from kish graphite |
| CN112135792B (en) * | 2018-05-16 | 2024-01-30 | 安赛乐米塔尔公司 | Method for producing pristine graphene from primary graphite |
| US20210230003A1 (en) * | 2018-05-23 | 2021-07-29 | Arcelormittal | A method for the manufacture of reduced graphene oxide from electrode graphite scrap |
| US11939221B2 (en) * | 2018-05-23 | 2024-03-26 | Arcelormittal | Method for the manufacture of reduced graphene oxide from electrode graphite scrap |
| CN108635915A (en) * | 2018-05-30 | 2018-10-12 | 清华大学 | Graphite sorbing material is used for the purposes and method of the toxic inflammable and explosive dangerous chemical leakage of emergency processing liquid |
| CN109745949A (en) * | 2019-03-08 | 2019-05-14 | 清华大学 | A kind of low-density self-forming graphite adsorbent material and its preparation and reclaiming method |
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Application publication date: 20140423 |