CN101746768A - Coal-series hard kaolinite stripping method capable of keeping crystal form of kaolinite - Google Patents
Coal-series hard kaolinite stripping method capable of keeping crystal form of kaolinite Download PDFInfo
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- CN101746768A CN101746768A CN200910265857A CN200910265857A CN101746768A CN 101746768 A CN101746768 A CN 101746768A CN 200910265857 A CN200910265857 A CN 200910265857A CN 200910265857 A CN200910265857 A CN 200910265857A CN 101746768 A CN101746768 A CN 101746768A
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- kaolinite
- kaolin
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- series hard
- coal
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052622 kaolinite Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000013078 crystal Substances 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000000138 intercalating agent Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 63
- 235000012211 aluminium silicate Nutrition 0.000 claims description 62
- 239000003245 coal Substances 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- -1 methane amide Chemical class 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 description 17
- 230000002687 intercalation Effects 0.000 description 17
- 239000010410 layer Substances 0.000 description 12
- 238000000227 grinding Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000011435 rock Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 102220190691 rs201046901 Human genes 0.000 description 4
- 238000001238 wet grinding Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- NDQKGYXNMLOECO-UHFFFAOYSA-N acetic acid;potassium Chemical class [K].CC(O)=O NDQKGYXNMLOECO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The invention discloses a coal-series hard kaolinite stripping method. The method comprises the following steps of: crushing the coal-series hard kaolinite, mixing the crushed coal-series hard kaolinite with water and an intercalator to obtain intercalated compound pulp, striping the intercalated compound pulp by using medium spheres of three types grain sizes, and performing filtration washing and spray-drying to obtain the finished product. By the method, the hexagonal sheet-shaped crystal form of the kaolinite is kept relatively complete, and the content of hexagonal sheet-shaped kaolinite crystals is 30 to 60 percent.
Description
Technical field
The present invention relates to a kind of ultra tiny kaolin preparation method, belong to inorganic superfine powder body technical field of material.
Background technology
Tax has abundant kaolinite resource in China's coal stratum, and its stock number prediction reaches more than 180 hundred million tons.General dirt band or the roof and floor that has the coal seam of composing of this kind mineral products, it is discarded to be taken as ore in the past.In order fully to carry out the comprehensive utilization of coal resources, develop a circular economy, over year, started the upsurge of one exploitation coal series kaolin rock in the China's coal-mine district surplus in the of nearly ten.In the big and small coal series kaolin rock processing enterprise that sets up family surplus in the of 50 of coal field in provinces such as China Shanxi, Inner Mongol, Henan, Shandong, Hebei, whole nation accumulation annual production reaches ten thousand tons of 60-80 at present.Coal series kaolin rock is the distinctive a kind of coal measures of a China associated minerals resource altogether, abroad generally owing to thin thickness does not have the heavy industrialization exploitation.
Superfine grinding is a main direction of China's coal series kaolin rock exploitation.Superfine grinding is in the world at present mainly carried out by means of various grinding attachments (for example airflow milling, ball mill, disintegrating machine etc.).Utilize ultra-fine airflow milling, generally can only produce 1250-2500 purpose product, and energy consumption is higher, and yields poorly.In order to obtain thinner product, generally take the method for wet milling.
The equipment of wet milling generally takes wet type to stir mill, the machine of delaminating, sand mill, colloidal mill, vibration mill etc.Kaolinic wet type superfine grinding is called again delaminates, and meaning is about to thicker stromatolithic kaolin stripping and is divided into thin small thin slices.The method of delaminating has wet grinding, extruding.
Polishing is the relative movement by means of grinding medium, kaolin particle is produced shear, impact and mill stripping effect, makes it along splitting flakiness shape subparticle.Equipment commonly used is to grind delaminate machine, agitating ball mill, sand mill etc.Grinding medium is used granulated glass sphere, alumina bead, corundum pearl, zirconium oxide bead, natural siliceous sand etc. always, and hardness is at the grinding charge(of mill) material more than 3 grades, particle diameter 0.8～3mm.The grinding medium particle diameter is more little, and product is thin more.
The equipment that extrusion process is used is the equal pulp grinder of high pressure.Its principle of work is to make the kaolin paste in the pressure-even pulp crusher barrel be pressurized to 20～60MPa by piston pump, and the high pressure slip squeezes ejection from the nozzle (surface is through the very narrow slit of hardening treatment) of pressure-even pulp crusher with the linear velocity phase attrition greater than 950m/s.Because pressure sharply reduces suddenly, thereby the interior laminated generation of kaolin crystal of slip " is become flexible ", the slip of ejection is mapped on the impeller of atmospheric area at a high speed, and flip-flop direction of motion produces very strong cavitation pitting effect.Loosening crystal is laminated to be issued to along splitting in the cavitation pitting effect.This kind equipment is owing to the problem that exists in technology and the design, the application of never succeeding.
Coal series kaolin rock is different from southern soft kaolin, and it is a kind of rock of hard and compact.Because the formation epoch are remote, and experienced the long-term compaction and the Diagn of overlying strata, thereby connect between the kaolinite particle closely, be difficult for disperseing.Therefore traditional mechanical process superfine grinding and stripping method is easy to make kaolinic crystal habit to be damaged, thereby is difficult to obtain the good kaolinite wafer of crystalline form.And the good kaolin of crystalline form has great application advantage, for example is used for papermaking paint, printing ink and building coating etc., can improve its flowability and hiding rare etc.
Application number be 200610110567.X patent disclosure a kind of nano stripping method for coal series hard kaolinite.Selecting hard kaolinite micro mist (granularity is: 10～20 microns) for use is raw material, add entry and dispersion agent slurrying, the oxidizer de-carbon is purified again, add then in the saturated acetic acid potassium solution, make intercalator with Potassium ethanoate, make its intercalation enter the kaolinite interlayer, form " kaolinite-Potassium ethanoate " intercalation complex body, utilize the acoustic cavitation effect of power ultrasonic, kaolinite behind the intercalation is delaminated, add tensio-active agent again the kaolinite of delaminating is carried out finishing, dry at last and break up and be the nanometer kaolinite.Kaolinic wafer mean thickness 20～60 nanometers of nanometer, wafer median size 300～500 nanometers.
Application number is 03115823 patent, has introduced a kind of preparation method of ultrafine kaolin sheet layer material.Its method is to use Potassium ethanoate as sandwich agent, direct and kaolin mixed grinding, and intercalation leaves standstill certain hour, and washing is centrifugal then, removes Potassium ethanoate, and kaolin is delaminated, and oven dry is at last ground a little, makes finished product.Finished product grain size is less than the ultrafine kaolin sheet layer material of 2 μ m.In fact, discover that very easily slough after the flushing of Potassium ethanoate water, the kaolin lamella is easy to the former state that returns to.Be difficult to carry out suitability for industrialized production with this method.
Application number is that 200810195869 patent has been introduced a kind of preparation of superfine nano-kaoline.Disclose a kind of preparation of superfine nano-kaoline, comprised pre-treatment step and ultrasonic method intercalation step, specifically may further comprise the steps: (1) is mixed kaolin powder, basic cpd, water and is stirred, and reacts 2 to 10 hours; (2) add Glacial acetic acid again, continue reaction 2 to 10 hours, reaction after-filtration, washing, oven dry obtain the white powder solid; (3) get the white powder of above-mentioned steps (2) gained, add intercalator and tensio-active agent, mix, add entry, the ultrasonic method intercalation react 1.5 hours to 3 hours, filtered, washing, oven dry, and acquisition white powder solid is described nano kaoline.The present invention had carried out pre-treatment to the kaolin powder before ultrasonic method intercalation kaolin soil, and in the step of ultrasonic method intercalation kaolin soil, added tensio-active agent, what the final kaolin powder particle size range that obtains was in 100 Nano grades reaches 90%, and is uniformly dispersed.
Application number is 01128449 patent, has introduced a kind of mechanical and chemical stripping process for preparing superfine kaolin.Kaolin powder (45 μ m), intercalator, water and the sodium-chlor (NaCl) of preliminary working are mixed in certain proportion, adopt wet grinding, make intercalator enter the kaolin interlayer, under this machinery and chemical dual effect, repeat 3 to 4 times (promptly repeatedly peeling off), the granule content of-1 μ m in the kaolin powder (45 μ m) of preliminary working is reached more than 90%, and wherein nano level kaolin (100nm is following) content accounts for 20%.
Above-mentioned relevant invention method therefor is and grinds after intercalation or ultrasonication, and complex process, and crystalline form is difficult to remain intact, and is not easy to carry out large-scale industrial production.Do not find to keep the coal series kaolin rock stripping method of better crystalline form at present as yet.
Summary of the invention
The objective of the invention is to, a kind of industrialized method that the coal series hard kaolinite mill is shelled the sheet layer material that becomes to have complete crystalline form that is easy to is provided.
Kaolinite is a layer silicate mineral, and its basic structure layer is by forming Si-O tetrahedron and octahedra connection of Al-O, and thickness is 0.7nm.On vertical, kaolin crystal is exactly to be piled up by tens or such basic structural unit layers up to a hundred to form, and connects by hydrogen bond or Van der Waals force between its layer and the layer, and structure is tight, thereby the formation size is crystal several or tens microns.
The present invention is based on such principle: enter the kaolinite interlayer as intercalator by the inorganic or organic compound that one or more are suitable, enlarge its interlamellar spacing, weaken the connecting forces between the kaolinite crystal layer, under the effect of high shear force, kaolin crystal is peeled off into the lamella of nanometer scale then.Thereby can obtain the intact kaolin lamella of crystalline form.
Ultra tiny kaolin preparation technology of the present invention is as follows:
Coal series hard kaolinite-be crushed to 325 orders-slurrying-immersion intercalation processing-high-shear is delaminated-is washed and removes medicament and concentrate-centrifugal atomizing drying-kaolin powder.
Now describe summary of the invention of the present invention in detail, step is as follows:
The present invention is raw materials used to be coal series hard kaolinite, and this raw material is generally grown in coal seam dirt band, roof and floor, or non-conterminous and be independent ore bed with the coal seam, rock is general become thick-fine crystallization is granular, or becomes phanerocrystalline-adiagnostic, or becomes chiltern.First-selected dirt band type is thick-the granular kaolinite of fine crystallization.
The first step: coal series hard kaolinite is crushed to the 200-325 order.
Second step: the kaolin after will pulverizing mixes with water and intercalator, obtains the intercalated compound slurry.
The mass ratio of described kaolin and water is: 1: 10～1: 1, its first-selection was 1: 4～1: 2;
The mass ratio of described kaolin and intercalator is: 1: 0.05～0.40, and its first-selection is 1: 0.15～1: 0.3.
Described intercalator is hydrazine hydrate, methane amide, ethanamide, acrylamide, Potassium ethanoate, dimethyl sulfoxide (DMSO), hexadecyl trimethyl ammonium bromide, cetyl chloride amine, urea, Repone K.Select wherein one or more, preferred two kinds of combinations.
With kaolin, intercalator, the water of above-mentioned dosage, put into steel basin, mix.Can be that the three puts into together, after also back two kinds can being mixed, add kaolin again.Heat 30～80 ℃, first-selected 40-60 ℃.Obtain the kaolin intercalation mixture after slowly stirring 5～40h.Can not heat yet, but need to stir the longer time.
The 3rd step: mill stripping equipment is prepared
The zirconium silicate mill that particle diameter is respectively 0.8～1.2mm, 1.5～2.0mm, 2.0～2.5mm is shelled medium ball, puts into mill stripping bucket according to 3: 2: 1 ratio of mass ratio.
The 4th step: the second intercalated compound slurry that prepare of step poured in ready mill stripping of the 3rd step bucket grind stripping.
The mass ratio of medium ball and intercalated compound slurry is 1: 1～1: 2.Adjust the disintegrating machine rotating speed at 1000～3000 rev/mins, preferred 1000～1500 rev/mins.Mill stripping 0.5～3h, preferred 0.5～1.5h.
The 5th step: the slurries filtration that the 4th step mill is stripped also washs.
Its filtering solution is recyclable.The bath water amount is 2～5 times of kaolin weight.
The 6th step: the kaolin behind the filtration washing is made slurry again, carry out spraying drying, obtain finished product.
It is simple that this invented technology has operation of equipment, low production cost, advantage such as it is effective to delaminate.Be suitable for preparing the ultrafine kaolin sheet layer material.Technology of the present invention is lighter to the destructiveness of kaolin crystal, can keep relatively complete hexagonal flake kaolinite crystalline form, generally possesses the hexagonal flake kaolin crystal and accounts for 30-60%.The radius-thickness ratio of kaolin crystal is between 10: 1～30: 1.The kaolinite wafer thickness is generally less than 100～200nm, D97≤2 μ m.
Utilize the product of this prepared to have following beneficial effect:
(1) keeps more intact kaolinite hexagonal flake crystalline form
In the technology of the present invention, owing to taked intercalation processing in advance, some compounds are entered in the middle of the kaolinite crystal layer, slackened the reactive force between the kaolinite synusia.Add owing to being raw material with coal measures coarse-grain to thin brilliant kaolinite, in the kaolinite of this type, kaolinite mainly exists with the form of vermiform or books shape aggregate, and its crystalline form is better.Therefore in mill stripping process, medium ball is lighter to the destructiveness of kaolin crystal.Can keep relatively complete hexagonal flake kaolinite crystalline form.As tool hexagonal flake kaolin crystal account for 30-60%.
(2) keep bigger radius-thickness ratio
Because having taked the medium ball collocation of different-grain diameter in the technology of the present invention uses, and linear velocity and the surging force of the medium ball of different-grain diameter in the high speed rotating process has nothing in common with each other, thereby cause the different-grain diameter spheroid to produce the great shearing force of microcosmic each other, quicken dissociating of the kaolinite crystal layer behind the intercalation, can form the thick lamella as thin as a wafer of 100～200nm.Keep big kaolinite radius-thickness ratio.The radius-thickness ratio of utilizing the kaolin crystal that prepared of the present invention goes out is between 10: 1～30: 1.
Description of drawings
The scanning electron microscope diagram of Fig. 1 embodiment 1.
The scanning electron microscope diagram of Fig. 2 embodiment 2.
The scanning electron microscope diagram of Fig. 3 embodiment 3.
The scanning electron microscope diagram of Fig. 4 embodiment 4.
Embodiment
Embodiment 1:
Choose the coarse-grain kaolinite and it is ground into 325 orders.In quality than kaolin: water: the ratio preparation intercalation compound system slurries of hydrazine hydrate=1: 2: 0.15, slowly stirred 12 hours.The kaolin slurry for preparing is poured in the mill stripping bucket that fills medium ball, and (0.8～1.2mm, 1.5～2.0mm, 2.0～2.5mm) mass ratio are 3: 2: 1 to the different-grain diameter medium ball, and the mass ratio of slurries and medium ball is 1: 1.Adjusting the disintegrating machine rotating speed is 1200 rev/mins, mill stripping 1.5 hours.Filter, and, make 45% mud at last, carry out spraying drying then and get product with 3 times water washing.Products obtained therefrom D97=1.9 μ m, wafer thickness≤200nm, about 30% has hexagonal crystal shape, and radius-thickness ratio is 10: 1.See accompanying drawing 1.
Embodiment 2:
Brilliant kaolinite and it is ground into 325 orders in choosing.In quality than kaolin: water: the ratio preparation intercalation compound system slurries of methane amide=1: 1.5: 0.2, slowly stirred 15 hours.The medium ball that diameter is respectively 0.8～1.2mm, 1.5～2.0mm, 2.0～2.5mm is good by 3: 2: 1 mixed of mass ratio, pours in the mill stripping bucket, pours kaolin mud then into, and the mass ratio that makes mud and medium ball is 1: 1.2.Adjusting the disintegrating machine rotating speed is 1300 rev/mins, mill stripping 1.0 hours.Filter, and, make 45% mud at last, carry out spraying drying then and get product with 5 times water washing.Products obtained therefrom D97=1.5 μ m, wafer thickness≤100nm, about 60% has hexagonal crystal shape, and radius-thickness ratio is 20: 1.See accompanying drawing 2.
Embodiment 3:
Choose thin brilliant kaolinite and it is ground into 250 orders.In quality than kaolin: water: the ratio preparation intercalation compound system slurries of dimethyl sulfoxide (DMSO)=1: 3: 0.3, heating 70 degree also slowly stirred 30 hours.The medium ball that diameter is respectively 0.8～1.2mm, 1.5～2.0mm, 2.0～2.5mm mixes by 3: 2: 1 mass ratio, pours in the mill stripping bucket, pours kaolin mud then into, and the mass ratio that makes mud and medium ball is 1: 1.5.Adjusting the disintegrating machine rotating speed is 1500 rev/mins, mill stripping 1.5 hours.Filter, and, make 40% mud at last, carry out spraying drying then and get product with 5 times water washing.Products obtained therefrom D97=1.0 μ m, wafer thickness≤50nm, about 60% has hexagonal crystal shape, and radius-thickness ratio is 10: 1.See accompanying drawing 3.
Embodiment 4:
Choose the cryptocrystal kaolinite and it is ground into 200 orders.In quality than kaolin: water: the ratio preparation intercalation compound system slurries of Potassium ethanoate=1: 1.5: 0.3, slowly stirred 12 hours.The medium ball that diameter is respectively 0.8～1.2mm, 1.5～2.0mm, 2.0～2.5mm is good by 3: 2: 1 mixed of mass ratio, pours in the mill stripping bucket, pours kaolin mud then into, and the mass ratio that makes mud and medium ball is 1: 1.Adjusting the disintegrating machine rotating speed is 1200 rev/mins, mill stripping 1.0 hours.Filter, and, make 45% mud at last, carry out spraying drying then and get product with 4 times water washing.Products obtained therefrom D97=0.9 μ m, wafer thickness≤50nm, about 30% has hexagonal crystal shape, and radius-thickness ratio is 20: 1.See accompanying drawing 4.
Claims (5)
1. a coal series hard kaolinite stripping method that keeps the kaolinite crystalline form is characterized in that, comprises the following steps:
The first step: coal series hard kaolinite is crushed to the 200-325 order;
Second step: the kaolin after will pulverizing mixes with water and intercalator, obtains the intercalated compound slurry;
The mass ratio of described kaolin and water is: 1: 10～1: 1, the mass ratio of described kaolin and intercalator was: 1: 0.05～0.40;
Described intercalator be selected from following one or more: hydrazine hydrate, methane amide, ethanamide, acrylamide, Potassium ethanoate, dimethyl sulfoxide (DMSO), hexadecyl trimethyl ammonium bromide, cetyl chloride amine, urea, Repone K;
The 3rd step: mill stripping equipment is prepared
The zirconium silicate mill that particle diameter is respectively 0.8～1.2mm, 1.5～2.0mm, 2.0～2.5mm is shelled medium ball, puts into mill stripping bucket according to 3: 2: 1 ratio of mass ratio;
The 4th step: the second intercalated compound slurry that prepare of step poured in ready mill stripping of the 3rd step bucket grind stripping;
The mass ratio of described medium ball and intercalated compound slurry is 1: 1～1: 2;
The 5th step: the slurries filtration that the 4th step mill is stripped also washs;
The 6th step: the kaolin behind the filtration washing is made slurry again, carry out spraying drying, obtain finished product.
2. according to the coal series hard kaolinite stripping method of claim 1, it is characterized in that the coal series hard kaolinite described in the first step is the thick or granular kaolinite of fine crystallization of dirt band type.
3. according to the coal series hard kaolinite stripping method of claim 1, it is characterized in that the medium ball of three kinds of particle diameters also can use separately in the 3rd step.
4. according to the coal series hard kaolinite stripping method of claim 1, it is characterized in that the bath water amount described in the 5th step is 2～5 times of kaolin weight.
5. according to the coal series hard kaolinite stripping method of claim 1, it is characterized in that products obtained therefrom possesses the hexagonal flake kaolin crystal and accounts for 30-60%, the radius-thickness ratio of kaolin crystal is between 10: 1～30: 1, the kaolinite wafer thickness is less than 100～200nm, D97≤2 μ m.
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| CN2009102658575A CN101746768B (en) | 2009-12-29 | 2009-12-29 | Coal-series hard kaolinite stripping method capable of keeping crystal form of kaolinite |
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| CN2009102658575A CN101746768B (en) | 2009-12-29 | 2009-12-29 | Coal-series hard kaolinite stripping method capable of keeping crystal form of kaolinite |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101857242A (en) * | 2010-06-25 | 2010-10-13 | 华东师范大学 | Method for preparing Y-type molecular sieve by using kaolin |
| CN103289447A (en) * | 2012-02-24 | 2013-09-11 | 中国矿业大学(北京) | Dissociation method of coal-series hard kaolinite rock lamella |
| CN103288096A (en) * | 2012-03-02 | 2013-09-11 | 中国矿业大学(北京) | Coal series kaolinite rock calcining method capable of reducing calcining temperature |
| CN103926119A (en) * | 2014-02-19 | 2014-07-16 | 中国矿业大学(北京) | Method for preparing kaolinite with high radius-thickness ratio, and measuring and calculating radius-thickness ratio of kaolinite |
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| CN110745837A (en) * | 2019-12-08 | 2020-02-04 | 太原理工大学 | Method for stripping coal-series kaolin sheet layer |
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- 2009-12-29 CN CN2009102658575A patent/CN101746768B/en not_active Expired - Fee Related
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| CN101857242B (en) * | 2010-06-25 | 2011-11-02 | 华东师范大学 | Method for preparing Y-type molecular sieve by using kaolin |
| CN101857242A (en) * | 2010-06-25 | 2010-10-13 | 华东师范大学 | Method for preparing Y-type molecular sieve by using kaolin |
| CN103289447B (en) * | 2012-02-24 | 2014-12-24 | 中国矿业大学(北京) | Dissociation method of coal-series hard kaolinite rock lamella |
| CN103289447A (en) * | 2012-02-24 | 2013-09-11 | 中国矿业大学(北京) | Dissociation method of coal-series hard kaolinite rock lamella |
| CN103288096A (en) * | 2012-03-02 | 2013-09-11 | 中国矿业大学(北京) | Coal series kaolinite rock calcining method capable of reducing calcining temperature |
| CN103288096B (en) * | 2012-03-02 | 2015-08-12 | 中国矿业大学(北京) | A kind of calcining coal-series kaolinite method reducing calcining temperature |
| CN104004241A (en) * | 2013-02-21 | 2014-08-27 | 河南理工大学 | Method for preparing coal-based functional reinforcing powder material |
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| CN103926119B (en) * | 2014-02-19 | 2016-04-06 | 中国矿业大学(北京) | The measuring method of the kaolinic preparation of a kind of high radius-thickness ratio and radius-thickness ratio thereof |
| CN108275688A (en) * | 2018-02-08 | 2018-07-13 | 山西恒源高岭土有限公司 | A kind of high oil absorption amount kleit preparation method |
| CN108275688B (en) * | 2018-02-08 | 2021-05-25 | 山西恒源高岭土有限公司 | Preparation method of kaolin with high oil absorption |
| CN110745837A (en) * | 2019-12-08 | 2020-02-04 | 太原理工大学 | Method for stripping coal-series kaolin sheet layer |
| CN115784249A (en) * | 2022-12-19 | 2023-03-14 | 中南大学 | Preparation method of large-size ultrathin kaolin nanosheet |
| CN115784249B (en) * | 2022-12-19 | 2024-04-12 | 中南大学 | Preparation method of large-size ultrathin kaolin nanosheets |
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