CN105271633B - A kind of preparation method for producing glass silica flour - Google Patents
A kind of preparation method for producing glass silica flour Download PDFInfo
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- CN105271633B CN105271633B CN201510845247.8A CN201510845247A CN105271633B CN 105271633 B CN105271633 B CN 105271633B CN 201510845247 A CN201510845247 A CN 201510845247A CN 105271633 B CN105271633 B CN 105271633B
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Abstract
The present invention provides a kind of preparation method for producing glass silica flour：Including from silica grade >=95% and after crushing average diameter 2 5mm quartz mine, first color sorting removal of impurities, then after elder generation it is modified through preliminary ball milling, shaping ball milling, flotation removal of impurities, optional acidleach removal of impurities and surface and obtain the silica flour；Wherein, preliminary ball milling refers to ore described in the ball ball milling using a diameter of 15~45mm, and preliminary ball milling ball is the ball of two or more different-diameters；In shaping ball milling step using mono-disperse ball, and ball diameter between 8~20mm, the grinding aid of alcoholic hydroxy is additionally added in shaping ball milling；It refers to superfine silica gel powder batch mixing by the silica flour of drying and granularity are 800~2000 mesh that surface is modified.The present invention also provides a kind of use iron tailings instead of quartz mine and increases the quartzy powder, preparation method thereof of magnetic separation process., in the case where grade and chemical element are up to standard, its heap density is big and angle of repose is low for gained silica flour of the invention.
Description
Technical field
The present invention relates to the preparation field of silica flour, and in particular to a kind of preparation method for producing glass silica flour.
Background technology
The ultra-thin flat glass being applied in FPD industry mainly has cover-plate glass, glass substrate and ITO conductive
Glass, ultra-thin flat glass is one of maximum upstream key part and component of FPD industry amount of purchase.Manufacture ultra-thin panel glass
The primary raw material of glass is silica flour, and the ratio that it accounts for raw material is more than 55%.
At present, worldwide production be applied to the cover-plate glass of display industry manufacturer is predominantly healthy and free from worry, Xiao Te, Asahi Glass etc.,
It occupies most of market share.Current cover-plate glass is main based on alumina silicate glass, and market is by healthy and free from worry Gorilla glass
Glass is dominated, and is produced using press over system, all imports of quartz raw material used.
Patent application 201510372626.X provides a kind of production method of TFT-LCD base plate glass silica flour, including
Following steps：(1), the white vein quartz ore from alundum (Al2O3) content≤0.1% is raw material, and artificial hand is carried out after cleaning
Choosing, it is standby after rejecting impurity ore contained therein；(2), the ore crusher in crushing after removing impurity in step (1)
Into after the ore particles of particle diameter≤25 millimeter, variegated impurity particle therein is removed with color selector, then send into ore particles
In descaling bath, with the chlorohydric acid pickling of mass concentration 28~31%, after dynamic leaches 18~24 hours at room temperature, descaling bath is bled off
In hydrochloric acid, then the ore particles after pickling are fully washed to neutrality with water dry it is standby；(3), the ore after drying
After being calcined 45~60 minutes under 900~950 DEG C of temperature calcination in the quartzy calcining furnace of particle feeding, ore particles are put into water
Quench and carry out water quenching with 0~10 DEG C of water in groove, pull ore particles out after water quenching, then except standby after impurity elimination；(4), by step (3)
In carry out wet milling mortar in obtained ore particles feeding edge runner, the muller and mill disc of described edge runner are used
Quartz is made, and the liner of the cylinder of milling of edge runner is quartzite slate, during whole emery dust processed of milling material not with
Irony is contacted；(5) obtained mortar in upper step is carried out three with the magnetic separator that Surface field intensity is 5000~7500 Gausses
After level magnetic separation, then be classified, collection cut size be the emery dust of 150~300 mesh as semi-finished product, with standby after centrifuge dewatering；
(6), the emery dust after dehydration is dried, dried emery dust carries out magnetic separation with permanent magnetic separators more than 7500 Gausses again
Afterwards, you can TFT-LCD base plate glass silica flours are obtained, the mass fraction of wherein each component is as follows：SiO2：>=99.7%,
Fe2O3：≤ 0.01%, Al2O3：≤ 0.1%, K2O+Na2O：≤ 0.02%, grain size intervals：150~400 mesh, wherein 200 mesh~
300 mesh >=65%, below 400 mesh≤5%, more than 150 mesh it is zero, chlorine ion concentration：≤8ppm.
It is to the requirement of the standard of ultra-thin glass silica flour in this area：Hand-set lid glass and liquid crystal glass base stone
Particle of the English powder raw material requirement fineness median particle diameter more than 230 mesh or so, 140 mesh is less than 3%, and 140~325 mesh are more than
55%, silica grade >=99.5%, Fe2O3≤ 0.01%, Al2O3≤ 0.3%, Na2O+K2O≤0.02%, TiO2≤
0.02%, SO3≤ 0.03%, Cr≤0.0005%, Co≤0.0005%, Mn≤0.0005%, Ni≤0.0005%, Pb≤
0.005%, Cd≤0.005%, Cu≤0.001%.
Though the quartzy powder raw material prepared in above-mentioned patent application can be up to standard and be used, its grade that only considered silica flour
With chemical composition index, and the pattern of powder and the uniformity of fineness of powder are not considered, cause the heap density of powder and mobility
It is all bad, and then influence follow-up glass melting.Therefore, the new of glass silica flour is produced there is a need in the field to provide a kind of
Preparation method.
The content of the invention
It is therefore an object of the present invention to prepare a kind of heap density and mobility and dispersed index is good and grade and change
Study a point production ultra-thin glass silica flour up to standard.The heap density of the silica flour prepared using the method in the present invention can
Up to 1.2g/cm3More than, while the liquidity scale is less than 35 degree up to angle of repose.
Therefore, the present invention provides a kind of preparation method for producing glass silica flour：Including selection silica grade >=
95% and average diameter, in the quartz mine of 2-5mm, first causes that silica grade enters one using color selector removal of impurities after crushing
Step is improved, the ore again after elder generation through preliminary ball milling, shaping ball milling, optional flotation removal of impurities, optional acidleach removal step, with
And surface modification step and obtain the silica flour；Wherein, the preliminary ball milling refers to using the oxidation of a diameter of 15~45mm
Aluminium or the zirconia ball ore described in ball milling in ball mill, and preliminary ball milling ball is the ball of two or more different-diameters；Shaping
In ball milling step using mono-disperse aluminum oxide or zirconia ball, and ball diameter between 8~20mm, shaping ball milling step
In be additionally added the grinding aid grinding aid of alcoholic hydroxy；Surface silica flour and the granularity for referring to dry that be modified is 800~2000
The process of purpose superfine silica gel powder batch mixing.
The quartz mine selected in the present invention preferably its silica grade >=97%, more preferably >=98.5%.Using
During quartzy raw ore prepares silica flour, optional step is with acidleach removal step the step of flotation removal of impurities, if in raw ore
The element such as iron, potassium, sodium, aluminium, titanium it is up to standard after shaping ball milling, then be not required to carry out flotation removal of impurities and acidleach removal step.
The present invention also provides the preparation method of another production glass silica flour：Including selection silica grade >=
55% iron tailings, first removing can wherein cross the thin mud of 350~550 mesh sieves, and gained sand setting enters the preliminary ball milling of ball mill, tentatively
Enter magnetic separator and the iron removal by magnetic separation under the magnetic field of 0.8~1.5T after ball milling, then carry out shaping ball milling, flotation removal of impurities, acidleach and remove
Miscellaneous step and surface modification step and obtain the silica flour；Wherein, the preliminary ball milling refer to using a diameter of 15~
The aluminum oxide and/or zirconia ball of 45mm ore described in ball milling in ball mill, and preliminary ball milling ball is two or more differences
The ball of diameter；In shaping ball milling step using mono-disperse aluminum oxide and/or zirconia ball, and ball diameter in 8~20mm
Between, the grinding aid grinding aid of alcoholic hydroxy is additionally added in shaping ball milling step；It refers to the silica flour that will be dried that the surface is modified
With the process of the superfine silica gel powder batch mixing that granularity is 800~2000 mesh.
The iron tailings selected in the present invention preferably its silica grade >=65%.Preferably, removing thin mud sieve is 400
~500 mesh sieves.In which of the invention, skilled artisans will appreciate that, the iron removal by magnetic separation step can also set
Put after shaping ball milling step, namely step in the program is changed to just by preliminary ball milling → iron removal by magnetic separation → shaping ball milling
Step ball milling → shaping ball milling → iron removal by magnetic separation, this is a kind of equivalent mode of the invention.
In the present invention, the alcoholic extract hydroxyl group be correspondence phenolic hydroxyl group for, the grinding aid is the fluidization containing alcoholic extract hydroxyl group
Compound.Available grinding aid species is various in shaping mechanical milling process of the present invention, for example, use polymerized polyalcohol, polyalcohol amine, three
The grinding aid of the alcoholic hydroxies such as monoethanolamine, triisopropanolamine, ethylene glycol, diethylene glycol.And be found through experiments that, wherein using three
Monoethanolamine be grinding aid when, gained silica flour product it is most outstanding.
In the present invention, removing thin mud the step of carried out in hydrocyclone, magnetic separation step is in vertical ring high-gradient magnetic separator
Inside carry out.
Skilled person will appreciate that, the molecular formula of superfine silica gel powder is mSiO2-nH2O, it is a kind of white powder
Inorganic chemical product, belongs to fine chemistry industry class product.Its physicochemical property is：It is nontoxic, tasteless, non-ignitable, not quick-fried, non-volatile, without corruption
Lose, pore volume is big, surface-active is strong.
In a kind of specific embodiment, preliminary ball milling ball is three kinds of balls of different-diameter, and bead diameter choosing
From 15~25mm, the diameter of middle ball is selected from 25~35mm, and the diameter of big ball is selected from 35~45mm.Preferably, the body of the bead
Product accounts for the 40~60% of total sphere volume, and the volume of middle ball accounts for the 20~40% of total sphere volume, and the volume of big ball accounts for total sphere volume
10~30%.In a kind of specific embodiment, a diameter of 20mm of the bead, a diameter of 30mm of middle ball, big ball
A diameter of 40mm.
Include using 140 in a kind of specific embodiment, in the preliminary ball milling step and shaping ball milling step
The dusting cover of~200 mesh forms closed-loop path with ball mill, and the quartz that sifting out to sieve continues ball milling in returning to ball mill.
In a kind of specific embodiment, the grinding aid is triethanolamine.In a kind of specific embodiment, institute
State 0.05~0.5wt%, preferably 0.1~0.3wt% that Grinding aid dosage is silica flour total amount.
In a kind of specific embodiment, sphere volume used accounts for ball mill appearance in preliminary ball milling and shaping ball milling step
The 50~75% of cavity volume, the silica flour of ball milling accounts for the 25~38% of total sphere volume；And drum's speed of rotation is 50- in preliminary ball milling
70 revs/min, drum's speed of rotation is 20-40 revs/min in shaping ball milling.
In a kind of specific embodiment, the granularity of the superfine silica gel powder is 1200-2000 mesh, and superfine silica gel powder use
Measure 0.1~1.0wt% for silica flour, preferably 0.3-0.7wt%.
In a kind of specific embodiment, the preliminary ball milling and shaping ball milling step are the wet ball grinding for adding water,
And concentration of the quartz in ore pulp is 55~75wt%, preferably 60~70wt% in preliminary ball milling.Preferably, in methods described
Also include the precedence activities slurry concentrating step of shaping ball milling, slurry concentrating step is carried out in concentrator, specially will be preliminary
Add water the ore pulp or the concentration by the slurry concentrating after magnetic separation to 25~50wt% for flushing out after ball milling, preferably 30-40wt%'s
Concentration, the ore pulp after concentration enters shaping ball milling step.The concentration refer to silica flour ore pulp (comprise at least silica flour and
Water) in mass concentration.Ore pulp is gone out because needing to add water after preliminary ball milling, the concentration of the ore pulp gone out 20% or so, because
And need to concentrate it and enter back into shaping ball milling step.
In the mechanical milling process of prior art, either dry grinding or wet-milling, ball milling ball is using different-diameter
Ball carries out level with ball milling.As provided a kind of preparation method of silica flour in patent 201310083284.0, wherein ball milling step is：
Powder is carried out into dry grinding using ball mill, ball grinder liner and abrading-ball are oxidation aluminium material, and ratio of grinding media to material is 2~3：1, use
4 kinds of abrading-balls of a diameter of 20~60mm carry out heavyweight and match somebody with somebody, and Ball-milling Time is 60~80min, and drum's speed of rotation is 30~50r/
Min, by particle diameter is that tekite sand and particle diameter within 3mm is the tekite sand of 0.01~1mm while adding ball when feeding intake
Grinding jar is ground, and particle diameter is the parts by weight of the tekite sand within 3mm and the tekite sand that particle diameter is 0.01~1mm
Than being 1：0.6~0.8.
And preliminary ball milling is first carried out to quartz using the alumina balls of different-diameter in the present invention, reuse it is identical always
The alumina balls in footpath carry out shaping ball milling with reference to specific grinding aid to silica flour, and silica flour is carried out using superfine silica gel powder finally
Surface is modified., in the case where grade and chemical element are up to standard, its heap density is big, and represents silica flour stream for the silica flour of gained
The angle of repose of dynamic property is low.
Brief description of the drawings
Fig. 1 is the particle size distribution figure through the silica flour after preliminary grinding；
Fig. 2 is the particle size distribution figure of the silica flour after shaped ball milling；
Fig. 3 is to scheme through the SEM of the silica flour after preliminary grinding, and wherein Fig. 3 a are the SEM figures under 100 μm of scales, and Fig. 3 b are
SEM figures under 50 μm of scales；
Fig. 4 is the SEM figures of the silica flour after shaped ball milling, and wherein Fig. 4 a are the SEM figures under 100 μm of scales, and Fig. 4 b are
SEM figures under 50 μm of scales；
Fig. 5 be it is surface-modified after silica flour SEM figures, wherein Fig. 5 a are the SEM figures under 100 μm of scales, and Fig. 5 b are
SEM figures under 50 μm of scales.
Embodiment 1
The present embodiment provides a kind of method that target silica flour is prepared from quartzy raw ore.
Quartz mine of the silica grade more than 98.5%, (Cr≤0.0005%, Co≤0.0005%, Mn are chosen first
≤ 0.0005%, Ni≤0.0005%, Pb≤0.005%, Cd≤0.005%, Cu≤0.001%, in quartzy raw ore these
The content of element will substantially meet), the preferable quartz mine chosen according to the condition is crushed to average grain diameter for 2-5mm,
The coloring impurity of the inside is selected by color selector, silica grade is more than 99.5%.
Color sorting finished product carries out the preliminary ball milling of wet method into ball mill, and ore pulp is mainly made up of silica flour and water, and sphere volume is accounted for
Ball mill 2/3rds, the quartz mine of ball milling accounts for 1/3rd of sphere volume, and ball matches following 40mm balls and accounts for 20%, 30mm balls
Account for 30%, 20mm balls and account for 50%, ball milling concentration in 60-70wt% (concentration of the quartz in ore pulp), 60 turns of drum's speed of rotation/
Point.Ball mill and 160 mesh high frequency fine screens composition closed-loop path, substandard product return to ball mill and regrind, the qualified product of fineness
Into next step process, undersize fineness be can cross 230 mesh sieves content be 40~50wt%.Preliminary mechanical milling process is continuous
The process of discharging.
Product ore pulp under being sieved after preliminary ball milling is concentrated to the concentration of 30-40% through concentrator, feeds reshaping ball grinder, ball
Volume accounts for ball mill 2/3rds, and the silica flour stone of ball milling accounts for 1/3rd of sphere volume, and ball matches following 20mm balls and accounts for
100%, or 14mm balls account for 100%, or 10mm balls account for 100%, 20-40 revs/min of drum's speed of rotation, add 0.2% to help
Grinding agent triethanolamine.Ball mill constitutes closed circuit with 160 mesh high frequency fine screens, it is ensured that do not have coarse granule product, and substandard product is returned
Ball mill is regrinded, the qualified product of fineness enter hypomere magnetic separation process, undersize fineness be can cross 230 mesh sieves content be 50
~55wt%.
Product after shaping ball milling feeds strong magnetic except iron, if strong magnetic does not reach except the product potassium sodium aluminium titanium impurity content after iron
Mark, just into the further removal of impurities of flotation flowsheet：1~2kg/ tons of sulfuric acid and 200~400g/ tons of HF is added, adjustment mine tailing
PH value is 2~3；100~200g/ tons of mixed amine acetate is added as collecting agent, is swept through one thick two after obtaining removal of impurities
Quartz concentrate.After removal of impurities, if above-mentioned ferripotassium sodium aluminium titanium is unqualified, into acidleach flow, the ratio of HCL and HF in acidleach flow
9:1, normal temperature acidleach 2h-3h, the concentration 20-25%, acidleach concentration 40-50% of acid.
By this technique, it is good to produce powder consistency, microscopic appearance rule, and chemical index and fineness meet ultra-thin flat
Plate shows the silica flour of glass silica flour raw material standard.In the present embodiment, with the heap of silica flour afterwards before shaping ball milling
Density is by 0.95g/cm3Rise to 1.15g/cm3, angle of repose is reduced to 35.6 degree by 37.6 degree.
Silica flour after acidleach removal of impurities is dried through under conditions of 100~150 DEG C, is done with necessarily required superfine silica gel powder
Drift along or through even and complete the Process of Surface Modification to silica flour.Specifically, the present invention does to superfine silica gel powder first before addition
It is dry, after 100-150 DEG C dries 2h, 30-40 mesh sieves are crossed to remove the superfine silica gel powder of reunion, and point three to four batches are added to quartz
In powder so that silica flour is uniform with superfine silica gel powder batch mixing.Whole process carries out dry-mixed in spiral mixer.In the present embodiment,
With the heap density of silica flour afterwards by 1.15g/cm before surface is modified3Rise to 1.23g/cm3, angle of repose is by 35.6 degree of drops
As little as 34.2 degree.
Fig. 1 is the particle size distribution figure in embodiment 1 through the silica flour after preliminary grinding；Fig. 2 is shaped ball in embodiment 1
The particle size distribution figure of the silica flour after mill.To scheme through the SEM of the silica flour after preliminary grinding in embodiment 1, Fig. 4 is implementation to Fig. 3
Silica flour in example 1 after shaped ball milling SEM figure, Fig. 5 be embodiment 1 in it is surface-modified after silica flour SEM figure.
From Fig. 1~5, the silica flour that conventional grinding (only carrying out tentatively grinding without carrying out shaping grinding) obtains
More corner angle are carried on grain, and the shape of particle substantially has the different morphologies such as rhombus, rectangle, square and subcircular；And
By after specific shaping ball milling, rarely having corner angle on gained quartz powder particles in the present invention, and grain shape is in mostly subcircular,
And the uniformity of granular size is further improved.
Embodiment 2
The present embodiment provides a kind of method that target silica flour is prepared from iron tailings.
Raw material uses iron tailings, in iron tailings silica grade more than 65% (Cr≤0.0005%, Co≤
0.0005%, Mn≤0.0005%, Ni≤0.0005%, Pb≤0.005%, Cd≤0.005%, Cu≤0.001%, in raw ore
The content of these elements will substantially meet requirement).
Thin mud first in removing iron tailings (is crossed impurity content in the thin mud of 400 mesh or 500 mesh sieves big, thus is gone first
Except), sand setting enters the preliminary ball milling of ball mill, and sphere volume accounts for ball mill 2/3rds, and the quartz mine of ball milling accounts for the three of sphere volume
/ mono-, ball matches following 40mm balls and accounts for 20%, 30mm balls and account for 30%, 20mm balls and accounts for 50%, and ball milling concentration is in 60-70%, ball
60 revs/min of mill speed.Ball mill constitutes closed circuit with 160 mesh high frequency fine screens, and substandard product returns to ball mill and regrinds, and fineness is closed
The product of lattice enters shaping process, and undersize fineness is that to cross the content of 230 mesh sieves be 40~50wt%.
Undersize carries out one thick two and sweeps (one roughing is scanned twice) except iron under the magnetic field of 1.2T after preliminary ball milling
Technique, except the taste of the silica flour after iron is 90% or so.The mine tailing ore pulp of magnetic separation is concentrated to the dense of 30-40% through concentrator
Degree, feeds reshaping ball grinder, and sphere volume accounts for ball mill 2/3rds, and the silica flour of ball milling accounts for 1/3rd of sphere volume, and ball is matched somebody with somebody
100% is accounted for than following 20mm balls, or 14mm balls account for 100%, or 10mm balls account for 100%, 20-40 revs/min of drum's speed of rotation,
Add the grinding aid triethanolamine of 0.1-0.3%.Ball mill constitutes closed circuit with 160 mesh high frequency fine screens, it is ensured that produced without coarse granule
Product, substandard product returns to ball mill and regrinds, and the qualified product of fineness enters lower segment process, and undersize fineness is that can cross 230
The content of mesh sieve is 50~55wt%.Flotation is carried out after ball milling except the technique of potassium, sodium, aluminium, iron, titanium and sulphur.Flotation step is specific
It is as follows：8~10kg/ tons of sulfuric acid and 500~800g/ tons of HF is added, the pH value for adjusting mine tailing is 2~3；Add 300~
500g/ tons of mixed amine acetate sweeps (one roughing, six times scan) reverse flotation removal of impurities as collecting agent, through one thick six and obtains stone
English concentrate, makes silica grade be more than 99.2%.Above-mentioned quartz mine typically understands one or more in iron, potassium, sodium, aluminium, titanium
Constituent content is unqualified, then into acidleach flow.Acidleach is specially the ratio 8 of HCL, oxalic acid and HF:1:1, the concentration 20- of acid
25%, acidleach concentration 40-50%, are heated up to 80 DEG C of acidleach 2h-3h, obtain qualified silica flour product, and silica grade is more than
99.5%, heap density is more than 1.10g/cm3, the liquidity scale is that angle of repose is less than 36 degree.
By this technique, it is good to produce powder consistency, microscopic appearance rule, and chemical index and fineness meet ultra-thin flat
Plate shows the silica flour of glass silica flour raw material standard.In the present embodiment, with the heap of silica flour afterwards before shaping ball milling
Density is by 0.92g/cm3Rise to 1.13g/cm3, angle of repose is reduced to 35.8 degree by 37.8 degree.
Silica flour after acidleach removal of impurities is dried under conditions of 110 DEG C, is carried out with necessarily required superfine silica gel powder dry-mixed mixed
It is even and complete to the Process of Surface Modification of silica flour.Specifically, the present invention is dried to superfine silica gel powder first before addition,
After 150 DEG C dry 2h, 30-40 mesh sieves are crossed to remove the superfine silica gel powder of reunion, and point three to four batches are added in silica flour, make
Obtain silica flour uniform with superfine silica gel powder batch mixing.Whole process carries out dry-mixed in spiral mixer.In the present embodiment, surface is modified
Before with the heap density of silica flour afterwards by 1.13g/cm3Rise to 1.26g/cm3, angle of repose is reduced to 34.5 by 35.8 degree
Degree.
Can find out rule and knot same as Example 1 from the particle size distribution figure and SEM figure (not shown) of embodiment 2
By will not be repeated here.It should be noted that when silica flour is prepared for raw material using quartz mine, in preliminary ball milling step
Also alternatively include strong magnetic afterwards and before slurry concentrating step except iron is the process of magnetic separation, for removing band in quartz mine
The ferro element for entering.And during silica flour is prepared for raw material using quartz mine or iron tailings, it is also an option that ground includes
Successor activities after shaping ball milling step, i.e., carry out strong magnetic iron removal once again, so that remove may in shaping ball milling step
The ferro element brought into by machinery equipment.
Embodiment 3
Remaining condition is same as Example 1 in the present embodiment, but grinding aid is changed to by the triethanolamine of 0.2wt%
The ethylene glycol of 0.2wt%.In the present embodiment, with the heap density of silica flour afterwards by 0.95g/cm before shaping ball milling3Rise
To 1.10g/cm3, angle of repose is reduced to 36.3 degree by 37.6 degree, and before surface is modified with the heap density of silica flour afterwards by
1.10g/cm3Rise to 1.18g/cm3, angle of repose is reduced to 35.0 degree by 36.3 degree.
And other grinding aids such as polymerized polyalcohol, polyalcohol amine, triisopropanolamine and diethylene glycol etc. are used, gained quartz
The heap density and angle of repose result of powder are suitable with using the result that ethylene glycol is grinding aid.Illustrate, finishing ball of the invention is honed
Cheng Zhong, uses the shaping effect that triethanolamine is optimal for grinding aid has.
Can select to add or be added without grinding aid in preliminary ball milling step of the invention, but in shaping ball milling step then
Need to add grinding aid, and selecting for grinding aid can produce certain shadow to the heap density of final silica flour product and angle of repose
Ring.
In the present invention, the flotation removal of impurities and acidleach removal step are processing step well known to those skilled in the art.
In the present invention, when quartzy raw ore prepares silica flour may without acidleach removal of impurities the step of, and when iron tailings prepares silica flour because
Impurity content is higher and the step of needing acidleach removal of impurities.
In the present invention, the diameter of the ball of the shaping ball milling step can be more than the straight of minimum ball in preliminary ball milling step
Footpath, is more often that the diameter of ball in shaping ball milling step is minimum certainly.In preliminary mechanical milling process, more multimode is all a kind of
Bead fills the ball milling state in big ball space；And in shaping mechanical milling process, more multimode is between a kind of silica flour fills each ball
The ball milling state in space.
In the present invention, the heap density of silica flour is higher, then its level founds effect just with better in glass process is prepared
More preferably, thus in the case where grade, granularity and element composition is met, the higher the better for the heap density of silica flour.And silica flour
Angle of repose is smaller, then illustrate that the mobility and dispersiveness of silica flour are better, the advance batch mixing of glass and charging is founded more favourable.This
In invention, the detection at heap density and angle of repose is also adopted by detection method generally in the art, and the data at such as angle of repose are usually
Manually measuring and calculating is obtained.
Compared with the silica flour of shaping ball milling is not made, its heap density is higher, and angle of repose is smaller for the silica flour that the present invention is provided,
Its good fluidity in the fusion process for being subsequently used for prepare glass, reunion or hardened is not likely to produce in 1600 DEG C of high temperature above
Phenomenon, effectively prevent it is uneven during fusing, easily formed bubble, bad point and cause glass the phenomenon of quality problems occur.
In sum, the heap density of the silica flour that the present invention is prepared can be more than 1.2g/cm3, the liquidity scale is for not
Angle till is less than 35 degree.Compared to existing technology, the properties of product of the silica flour are obviously improved.
By the silica flour after shaping ball milling median particle diameter in 230 mesh or so, heap density can reach 1.10g/cm3With
On, angle of repose is smaller than 36 degree, but the dispersiveness and mobility of such silica flour are still not high enough, in the melting process of glass
Remain to cause the phenomenons such as batch mixing is uneven, reunite and bubble is more, influence the quality of glass.Also include to silica flour in the present invention
Carry out the modified step in surface so that the dispersiveness and mobility of silica flour are further improved, and then ensure that various raw materials can
It is well mixed, and be less likely to occur to reunite in melting process.
Silica grade >=96% of the superfine silica gel powder used in the present invention, adds a certain amount of superfine silica gel powder in quartz
In powder, it both can serve as anticaking agent, improve the dispersiveness of silica flour, can guarantee that silica flour is in before melting dispersity；Again
Glidant can be made, improve mobility of the frit in mixing and when founding feed.Surface-modified powder after mixing
Heap density is by 1.1g/cm3Rise to 1.2g/cm3More than, angle of repose drops to less than 35 degree by 36 degree.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (14)
1. a kind of preparation method for producing glass silica flour：Including from silica grade >=95% and average after crushing
Diameter first causes that silica grade is further improved in the quartz mine of 2-5mm using color selector removal of impurities, and the ore is first again
Obtained by preliminary ball milling, shaping ball milling, optional flotation removal of impurities, optional acidleach removal step and surface modification step
To the silica flour；Wherein, the preliminary ball milling refers to aluminum oxide or zirconia ball using a diameter of 15~45mm in ball milling
Ore described in ball milling in machine, and preliminary ball milling ball is the ball of two or more different-diameters；Using homogeneous in shaping ball milling step
The aluminum oxide or zirconia ball of diameter, and ball diameter between 8~20mm, be additionally added alcoholic hydroxy in shaping ball milling step
Grinding aid grinding aid；It refers to superfine silica gel powder batch mixing by the silica flour of drying and granularity are 800~2000 mesh that the surface is modified
Process.
2. a kind of preparation method for producing glass silica flour：Including the iron tailings from silica grade >=55%, first take off
Except the thin mud that can wherein cross 350~550 mesh sieves, gained sand setting enter the preliminary ball milling of ball mill, magnetic separator is entered after preliminary ball milling
And under the magnetic field of 0.8~1.5T iron removal by magnetic separation, then carry out shaping ball milling, flotation removal of impurities, acidleach removal step and surface and change
Property step and obtain the silica flour；Wherein, the preliminary ball milling refers to the aluminum oxide using a diameter of 15~45mm or oxidation
Zirconium ball ore described in ball milling in ball mill, and preliminary ball milling ball is the ball of two or more different-diameters；Shaping ball milling step
The aluminum oxide or zirconia ball of middle use mono-disperse, and ball diameter between 8~20mm, be additionally added in shaping ball milling step
The grinding aid grinding aid of alcoholic hydroxy；It refers to micro mist by the silica flour of drying and granularity are 800~2000 mesh that the surface is modified
The process of silica gel batch mixing.
3. method according to claim 1 or claim 2, it is characterised in that preliminary ball milling ball is three kinds of balls of different-diameter, and small
The diameter of ball is selected from 15~25mm, and the diameter of middle ball is selected from 25~35mm, and the diameter of big ball is selected from 35~45mm.
4. method according to claim 3, it is characterised in that the volume of the bead accounts for the 40~60% of total sphere volume, in
The volume of ball accounts for the 20~40% of total sphere volume, and the volume of big ball accounts for the 10~30% of total sphere volume.
5. method according to claim 1 or claim 2, it is characterised in that in the preliminary ball milling step and shaping ball milling step
Closed-loop path is formed with ball mill including the dusting cover using 140~200 mesh, the quartz that sifting out to sieve returns to ball mill relaying
Continuous ball milling.
6. method according to claim 1 or claim 2, it is characterised in that the grinding aid is triethanolamine, and Grinding aid dosage is
0.05~0.5wt% of silica flour total amount.
7. method according to claim 6, it is characterised in that Grinding aid dosage is 0.1~0.3wt% of silica flour total amount.
8. method according to claim 1 or claim 2, it is characterised in that spheroid used in preliminary ball milling and shaping ball milling step
Product accounts for the 50~75% of ball mill cavity volume volume, and the silica flour of ball milling accounts for the 25~38% of total sphere volume；And ball in preliminary ball milling
Mill speed is 50-70 revs/min, and drum's speed of rotation is 20-40 revs/min in shaping ball milling.
9. method according to claim 1 or claim 2, it is characterised in that the granularity of the superfine silica gel powder is 1200-2000 mesh, and
The consumption of superfine silica gel powder is 0.1~1.0wt% of silica flour.
10. method according to claim 9, it is characterised in that the consumption of superfine silica gel powder is the 0.3-0.7wt% of silica flour.
11. methods according to claim 1 or claim 2, it is characterised in that the preliminary ball milling and shaping ball milling step are and add water
Wet ball grinding, and concentration of the quartz in ore pulp is 55~75wt% in preliminary ball milling.
12. according to claim 11 methods described, it is characterised in that in preliminary ball milling concentration of the quartz in ore pulp for 60~
70wt%.
13. according to claim 11 methods described, it is characterised in that also include the precedence activities ore deposit of shaping ball milling in methods described
Slurry concentration step, slurry concentrating step carries out in concentrator, and will specially add water the ore pulp that flushes out or will after preliminary ball milling
Slurry concentrating after magnetic separation to 25~50wt% concentration, the ore pulp after concentration enters shaping ball milling step.
14. according to claim 13 methods described, it is characterised in that will add water the ore pulp that flushes out or by magnetic separation after preliminary ball milling
Slurry concentrating afterwards to 30-40wt% concentration, ore pulp after concentration enters shaping ball milling step.
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| CN106317967B (en) * | 2016-08-15 | 2018-08-17 | 大连地拓环境科技有限公司 | A method of preparing rubber-reinforcing filler using iron tailings |
| US10486973B2 (en) * | 2016-11-18 | 2019-11-26 | Ppg Industries Ohio, Inc. | Silica-based spherical particulates and methods of preparing the same |
| CN108514951A (en) * | 2018-04-16 | 2018-09-11 | 辽宁万隆科技研发有限公司长沙分公司 | A method of producing glass silica flour using iron tailings as raw material |
| CN108929041A (en) * | 2018-08-15 | 2018-12-04 | 日鸿半导体材料（南通）有限公司 | A kind of fused silica powder and preparation method thereof |
| CN108975679B (en) * | 2018-09-05 | 2021-02-05 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of silica powder for TFT-LCD glass substrate |
| CN109336115A (en) * | 2018-09-30 | 2019-02-15 | 福建省吉康新型建材有限公司 | A kind of glass sand preparation process |
| CN111594763B (en) * | 2020-06-03 | 2021-02-05 | 北煤化(北京)科技有限公司 | Method for improving fluidity and concentration of ore pulp |
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| JP2000239012A (en) * | 1999-02-22 | 2000-09-05 | Shin Etsu Chem Co Ltd | Silica powder, its treatment, and vibratory ball mill |
| CN1317225C (en) * | 2004-12-20 | 2007-05-23 | 武汉理工大学 | Preparation of silica flour or feldspar powder and preparing apparatus thereof |
| CN100368291C (en) * | 2005-07-08 | 2008-02-13 | 中南大学 | Method for producing superfine high-purity silicon dioxide |
| CN103130405B (en) * | 2013-03-15 | 2015-04-22 | 连云港利思特电子材料有限公司 | Preparation method of precision casting fused quartz powder and quartz powder produced by same |
| CN103896285B (en) * | 2014-04-21 | 2017-01-04 | 江苏凯达石英有限公司 | A kind of method preparing high pure and ultra-fine silica flour with waste and old quartz crucible |
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