CN102701221A - Method for preparing nano white carbon black from coal gangue - Google Patents
Method for preparing nano white carbon black from coal gangue Download PDFInfo
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- CN102701221A CN102701221A CN2012101587377A CN201210158737A CN102701221A CN 102701221 A CN102701221 A CN 102701221A CN 2012101587377 A CN2012101587377 A CN 2012101587377A CN 201210158737 A CN201210158737 A CN 201210158737A CN 102701221 A CN102701221 A CN 102701221A
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- coal gangue
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Abstract
The invention relates to a method for preparing white carbon black from coal gangue, belongs to the technical field of coal chemical industry, and aims at overcoming the shortcomings of expensive raw materials and high production cost in the process for preparing nano white carbon black by using the traditional method. The method comprises the steps of: based on coal gangue as a raw material, carrying out high-temperature activation, nitric acid dissolution, burning and the like to extract silicon dioxide; corroding extracted silicon dioxide with hydrogen fluoride generated by reacting concentrated sulfuric acid and sodium fluoride so as to generate silicon tetrafluoride gas, reacting the silicon tetrafluoride gas with an aqueous solution with a surfactant dissolved to generate silicon gel, cleaning, drying and burning to remove water so as to produce the required nano white carbon black product. According to the method provided by the invention, the waste recycling of coal gangue is realized, and the cost for preparing nano white carbon black is lowered; and the particle size of the obtained product achieves a nano scale, and the indexes of the obtained product achieve the ministerial standard HG-1-125-64 or enterprise standard.
Description
Technical field
The present invention relates to the method that a kind of coal gangue prepares Nano carbon white, belong to technical field of coal chemical industry.
Background technology
WHITE CARBON BLACK has the characteristics such as aggregate that particle diameter is little, specific surface area big, be prone to form high structure, mainly is used as the reinforcing filler of rubber; In the nonrubber field, also have a wide range of applications like industries such as synthetic resins, plastics and coating.Nano carbon white has particle diameter little (less than 100nm), specific surface area is big (generally greater than 100m
2/ g), characteristic such as chemical purity is high, dispersing property is good; Be used widely at many industrial circles such as rubber, coating, medicine, papermaking with its superior stability, reinforcement property, thickening property and thixotropy; And for the development in its related industries field provides novel material basis and technical guarantee, nano silicon is widely used in every field.Add nano silicon in the coating, functions such as anti-caking, sag prevention, thickening delustring can be provided; In plastics, add nano silicon, can improve transparency, toughness, the intensity of film, water resistance etc.Add nano silicon in sticker and the sealer, can form network-like masonry structure rapidly, suppress colloid and flow, solidification rate is accelerated, and improves bond effect.In medicine, agricultural chemicals, can play the effect of thickening, suspension, carrier.Newest research results shows: in polymeric system, introduce nano silicon and can demonstrate a series of praiseworthy optical properties and mechanical property.Enjoy the good reputation of " industrial monosodium glutamate ", " initial point of Materials science ".At present, Nano carbon white mainly is that raw material adopts vapor phase process production with the silicon tetrachloride, and WHITE CARBON BLACK purity height, particle diameter and ignition loss that vapor phase process is produced are little, but starting material are expensive, production cost is high.Coal gangue is the solid waste that discharges in coal mining process and the coal washing process, be a kind of lower with a kind of carbon content of coal seam association in the coal-forming process, than the hard grey black look rock of coal.Its staple is Al
2O
3, SiO
2, be a kind of further resource of development and use of being badly in need of, its bulk deposition has not only been wasted resource, has also seriously influenced environment.At present, prior art is produced WHITE CARBON BLACK with coal gangue as raw material, and it mainly adopts the precipitator method, and the first step is the preparation water glass earlier, and the second step reprecipitation method prepares active carbon white.The particle diameter of the product that this method is produced is bigger, can't reach Nano grade, and product is active and adsorptive power is less.
Summary of the invention
The objective of the invention is to overcome existing method and prepare the shortcoming that Nano carbon white technology starting material are expensive, production cost is high; Improving prior art coal gangue is produced the technology of WHITE CARBON BLACK as raw material, is the method that raw material gas phase-hydrolysis method is produced the Nano carbon white product and a kind of coal gangue is provided.
The present invention is raw material with the coal gangue, extracts silicon-dioxide through high-temperature activation, nitric acid dissolve, calcination etc.The silicon-dioxide that extracts; Through producing hydrogen fluoride with the vitriol oil and Sodium Fluoride reaction, it is corroded, produce silicon tetrafluoride gas; React through the control silicon tetrafluoride gas and the aqueous solution that is dissolved with tensio-active agent; Generate the silicon gel, anhydrate through cleaning, drying, calcination then, produce needed Nano carbon white product.
The objective of the invention is to realize through following technical scheme:
A kind of coal gangue of the present invention prepares the method for nano white carbon black, comprises the following steps:
1) with coal gangue 700～1000 ℃ of following calcining and activatings 2～4 hours, the gained coal gangue is ground obtain 60～100 order colliery powders again;
2) the 1st colliery powder that obtains of step is carried out acidleach with 3～5mol/L salpeter solution and dissolve, and continuously stirring 1～2 hour; Wherein, the mass ratio of colliery powder and salpeter solution is 1: 5～15;
3), solid is adopted 60 ℃～80 ℃ distilled water wash to pH value to 6～8, in vacuum drying oven dry 6～8 hours again with after the colliery powder solid-liquid separation after the 2nd step gained acidleach;
4) the dried solid of the 3rd step gained is mixed by mass ratio 1: 0.5～1 under closed environment with Sodium Fluoride; Be heated to 100～150 ℃, keep this temperature to drip the vitriol oil, 1～2 of control rate of addition PM; Reaction produces mixed gas and feeds in the vitriol oil dry; Dry back gas imports in the dispersant solution again, under 60～100 ℃, is hydrolyzed and handles 3～10h, and hydrolysis adopts magnetic stirring apparatus constantly to stir simultaneously; And, make hydrating solution pH value remain on 3～5 scopes with the interior reaction that is hydrolyzed through dropping ammonia;
5) with the 4th the step gained hydrating solution ageing 12～24h under 40～60 ℃ of constant temperatures; Gel to obtaining after the ageing carries out suction filtration; Adopt again 60 ℃～80 ℃ zero(ppm) water wash earlier to pH value be 6～8, again with the specific conductivity of absolute ethanol washing to gel in 50 μ s, dry 1～5h under 60～100 ℃ condition then; High temperature sintering 1～3h under 400～600 ℃ condition obtains the Nano carbon white product again.
Described dispersant solution is a kind of in the sodium dodecyl sulfate solution of sodium dodecyl sulfate solution and 5～30g/L of cetyl trimethylammonium bromide solution, 5～30g/L of 5～30g/L or arbitrary proportion blended mixture more than two kinds.
Beneficial effect
The present invention utilizes coal gangue as main raw material; Problem is taken up an area of in the stacking that had both solved these depleted coal gangues; Can make these wastes become useful resource again utilizes again; Greatly reduce the cost of making Nano carbon white; Overcoming existing method is the shortcoming that feedstock production Nano carbon white technology starting material are expensive, production cost is high with the silicon tetrachloride, improve prior art coal gangue is produced the technology of WHITE CARBON BLACK as raw material, and be the method that raw material gas phase-hydrolysis method is produced the Nano carbon white product and a kind of coal gangue is provided.The product cut size that obtains reaches nano level, and each item index has all reached ministerial standard HG-1-125-64 or company standard.
Embodiment
Below in conjunction with embodiment content of the present invention is described further.
Embodiment 1
Earlier coal gangue is dropped in the retort furnace at 750 ℃ of sintering 2h; Nitric acid with gained 50g60-80 purpose colliery powder and 300g 4mol/L carries out acidleach 2h in enamel reactor again; Continue in the acidleach process to stir, after the products therefrom solid-liquid separation, extremely neutral with 60 ℃ of distilled water washs; Drying is 8 hours in vacuum drying oven, obtains the 22.5g silica solid.During adding 10g Sodium Fluoride was packed enamel reactor in the gained solid, oil bath was heated, and temperature is increased to 120 ℃, and constant temperature drips 98% vitriol oil, the control rate of addition, and approximately per second is 1.Reaction produces mixed gas, and gas feeds in the vitriol oil dry, and dry back gas imports in the 5g/L sodium dodecyl sulfate solution again; Hydrolysis temperature is controlled at 80 ℃; And constantly stir with magnetic stirring apparatus, dropping ammonia lets the pH value of solution value remain on 4 left and right sides hydrolysis 3h simultaneously.Put into beaker to hydrolyzed solution, seal rim of a cup, be placed in 40 ℃ of constant temperature water baths, insulation ageing 24h with antistaling film.Resulting gel is carried out suction filtration; Adopt 60 ℃ zero(ppm) water wash earlier to pH value be 6～8, again with the specific conductivity of absolute ethanol washing to gel in 50 μ s, put into 60 ℃ of dry 2h of baking oven then; Be placed on 500 ℃ of high temperature sintering 1h of retort furnace again, obtain the Nano carbon white product.Mainly be distributed in 30～50nm through its particle diameter of laser particle analyzer test.
Embodiment 2
Coal gangue is dropped in the retort furnace at 800 ℃ of sintering 3h,, continue in the acidleach process to stir again with nitric acid acidleach 2h in enamel reactor of gained 60g60-80 purpose colliery powder and 500g 4mol/L; After the products therefrom solid-liquid separation, with 70 ℃ of distilled water washs to neutral, solid in vacuum drying oven dry 6 hours; Obtain the 28.5g silica solid, during adding 13g Sodium Fluoride was packed enamel reactor in the gained solid, oil bath was heated; Temperature is increased to 150 ℃; Drip 98% vitriol oil, the control rate of addition, approximately per second is 1.Reaction produces mixed gas, and gas feeds in the vitriol oil dry, and dry back gas imports in the 10g/L sodium dodecyl sulfate solution again; Hydrolysis temperature is controlled at 80 ℃; And constantly stir with magnetic stirring apparatus, dropping ammonia lets the pH value of solution value remain on 5 left and right sides hydrolysis 2h simultaneously.Put into beaker to hydrolyzed solution, seal rim of a cup, be placed in 50 ℃ of constant temperature water baths with antistaling film; Insulation ageing 18h; Resulting gel carries out suction filtration, adopt 80 ℃ zero(ppm) water wash earlier to pH value be 6～8, again with the specific conductivity of absolute ethanol washing to gel in 50 μ s, put into 60 ℃ of dry 3h of baking oven then; Be placed on 550 ℃ of high temperature sintering 1h of retort furnace again, obtain the Nano carbon white product.Mainly be distributed in 50～80nm through its particle diameter of laser particle analyzer test.
Embodiment 3
Coal gangue is dropped in the retort furnace at 750 ℃ of sintering 2h, and the nitric acid with gained 50g60-80 purpose colliery powder and 500g 4mol/L carries out acidleach 1h in enamel reactor again, continues in the acidleach process to stir; After the products therefrom solid-liquid separation, washing, solid in vacuum drying oven dry 8 hours obtain the 22.5g silica solid; Adding the 10g Sodium Fluoride in the gained solid packs in the enamel reactor; The oil bath heating, temperature is increased to 120 ℃, drips 98% vitriol oil; The control rate of addition, approximately per second is 1.Reaction produces mixed gas, and gas feeds in the vitriol oil dry, and dry back gas imports in the 15g/L sodium dodecyl sulfate solution again; Hydrolysis temperature is controlled at 70 ℃; And constantly stir with magnetic stirring apparatus, dropping ammonia lets the pH value of solution value remain on 4 left and right sides hydrolysis 3h simultaneously.Put into beaker to hydrolyzed solution, seal rim of a cup, be placed in 60 ℃ of constant temperature water baths with antistaling film; Insulation ageing 24h; Resulting gel carries out suction filtration, adopt 70 ℃ zero(ppm) water wash earlier to pH value be 6～8, again with the specific conductivity of absolute ethanol washing to gel in 50 μ s, put into 60 ℃ of oven dry of baking oven then; Be placed on 450 ℃ of high temperature sintering 2h of retort furnace again, obtain the Nano carbon white product.Mainly be distributed in 80～100nm through its particle diameter of laser particle analyzer test.
Claims (1)
1. a coal gangue prepares the method for nano white carbon black, it is characterized in that comprising the following steps:
1) with coal gangue 700～1000 ℃ of following calcining and activatings 2～4 hours, the gained coal gangue is ground obtain 60～100 order colliery powders again;
2) the 1st colliery powder that obtains of step is carried out acidleach with 3～5mol/L salpeter solution and dissolve, and continuously stirring 1～2 hour; Wherein, the mass ratio of colliery powder and salpeter solution is 1: 5～15;
3), solid is adopted 60 ℃～80 ℃ distilled water wash to pH value to 6～8, in vacuum drying oven dry 6～8 hours again with after the colliery powder solid-liquid separation after the 2nd step gained acidleach;
4) the dried solid of the 3rd step gained is mixed by mass ratio 1: 0.5～1 under closed environment with Sodium Fluoride; Be heated to 100～150 ℃, keep this temperature to drip the vitriol oil, 1～2 of control rate of addition PM; Reaction produces mixed gas and feeds in the vitriol oil dry; Dry back gas imports in the dispersant solution again, under 60～100 ℃, is hydrolyzed and handles 3～10h, and hydrolysis adopts magnetic stirring apparatus constantly to stir simultaneously; And, make hydrating solution pH value remain on 3～5 scopes with the interior reaction that is hydrolyzed through dropping ammonia;
5) with the 4th the step gained hydrating solution ageing 12～24h under 40～60 ℃ of constant temperatures; Gel to obtaining after the ageing carries out suction filtration; Adopt again 60 ℃～80 ℃ zero(ppm) water wash earlier to pH value be 6～8, again with the specific conductivity of absolute ethanol washing to gel in 50 μ s, dry 1～5h under 60～100 ℃ condition then; High temperature sintering 1～3h under 400～600 ℃ condition obtains the Nano carbon white product again;
Wherein, the 4th) described dispersant solution of step is a kind of in the sodium dodecyl sulfate solution of sodium dodecyl sulfate solution and 5～30g/L of cetyl trimethylammonium bromide solution, 5～30g/L of 5～30g/L or arbitrary proportion blended mixture more than two kinds.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626191A (en) * | 2013-12-20 | 2014-03-12 | 贵州万方铝化科技开发有限公司 | Preparation method of nano-scale silicon dioxide |
| CN103708472A (en) * | 2013-12-20 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Method for preparing SiO2 powder by using zircon sand |
| CN104743560A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method for preparing silicon/aluminium series product by taking gangue as raw material |
| CN105110344A (en) * | 2015-08-19 | 2015-12-02 | 六盘水师范学院 | Method and apparatus for preparing fumed silica from coal gangue |
| CN106145127A (en) * | 2015-04-21 | 2016-11-23 | 广州凌玮科技股份有限公司 | A kind of preparation method of hollow microsphere silicon dioxide |
| CN106315597A (en) * | 2016-08-23 | 2017-01-11 | 黄冈师范学院 | Fly ash comprehensive treatment and utilization method and device |
| CN109336117A (en) * | 2018-11-09 | 2019-02-15 | 重庆大学 | A method of extracting gas-phase silica from waste and old composite insulator umbrella skirt |
| CN113484209A (en) * | 2021-05-24 | 2021-10-08 | 浦林成山（山东）轮胎有限公司 | Method for identifying white carbon black in vulcanized rubber and application thereof |
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| CN1903727A (en) * | 2005-07-26 | 2007-01-31 | 宁夏大学 | Method of coproducing aluminium oxide, white carbon black and low ash carbon by coal gangue ecological utilization |
| US20080199384A1 (en) * | 2005-06-10 | 2008-08-21 | Evonik Degussa Wellink Silica (Nanping) Co. Ltd. | Process For Producing Silica, Sodium Sulfite and Sodium Hydrogen Sulfite With Sodium Sulfate |
| CN101734698A (en) * | 2009-09-08 | 2010-06-16 | 东北大学 | Method for preparing aluminum oxide from aluminiferous material |
| CN102424392A (en) * | 2011-09-11 | 2012-04-25 | 中国科学院过程工程研究所 | Method for preparing white carbon black cogeneration nanometer calcium carbonate by integrally utilizing micro silicon powder |
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Patent Citations (4)
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| US20080199384A1 (en) * | 2005-06-10 | 2008-08-21 | Evonik Degussa Wellink Silica (Nanping) Co. Ltd. | Process For Producing Silica, Sodium Sulfite and Sodium Hydrogen Sulfite With Sodium Sulfate |
| CN1903727A (en) * | 2005-07-26 | 2007-01-31 | 宁夏大学 | Method of coproducing aluminium oxide, white carbon black and low ash carbon by coal gangue ecological utilization |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626191A (en) * | 2013-12-20 | 2014-03-12 | 贵州万方铝化科技开发有限公司 | Preparation method of nano-scale silicon dioxide |
| CN103708472A (en) * | 2013-12-20 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Method for preparing SiO2 powder by using zircon sand |
| CN103708472B (en) * | 2013-12-20 | 2015-08-05 | 贵州万方铝化科技开发有限公司 | Zircon sand is utilized to prepare SiO 2the method of powder |
| CN104743560A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method for preparing silicon/aluminium series product by taking gangue as raw material |
| CN104743560B (en) * | 2013-12-25 | 2017-06-27 | 贵州大学 | A kind of method for preparing silicon, aluminium series of products as raw material with gangue |
| CN106145127A (en) * | 2015-04-21 | 2016-11-23 | 广州凌玮科技股份有限公司 | A kind of preparation method of hollow microsphere silicon dioxide |
| CN105110344A (en) * | 2015-08-19 | 2015-12-02 | 六盘水师范学院 | Method and apparatus for preparing fumed silica from coal gangue |
| CN106315597A (en) * | 2016-08-23 | 2017-01-11 | 黄冈师范学院 | Fly ash comprehensive treatment and utilization method and device |
| CN109336117A (en) * | 2018-11-09 | 2019-02-15 | 重庆大学 | A method of extracting gas-phase silica from waste and old composite insulator umbrella skirt |
| CN109336117B (en) * | 2018-11-09 | 2022-02-18 | 重庆大学 | Method for extracting fumed silica from waste composite insulator umbrella skirt |
| CN113484209A (en) * | 2021-05-24 | 2021-10-08 | 浦林成山（山东）轮胎有限公司 | Method for identifying white carbon black in vulcanized rubber and application thereof |
| CN113484209B (en) * | 2021-05-24 | 2023-08-18 | 浦林成山（山东）轮胎有限公司 | Identification method of white carbon black in vulcanized rubber and application thereof |
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