CN105271633A - Preparation method of quartz powder used for producing glass - Google Patents
Preparation method of quartz powder used for producing glass Download PDFInfo
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- CN105271633A CN105271633A CN201510845247.8A CN201510845247A CN105271633A CN 105271633 A CN105271633 A CN 105271633A CN 201510845247 A CN201510845247 A CN 201510845247A CN 105271633 A CN105271633 A CN 105271633A
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Abstract
The invention provides a preparation method of quartz powder used for producing glass. The preparation method comprises the steps of selecting quartz ores with silicon dioxide grade not less than 95% and average diameter of 2-5mm after grinding, firstly carrying out color sorting and impurity removal and then carrying out preliminary ball milling, shaping ball milling, flotation impurity removal, optional acid leaching impurity removal and surface modification successively, thus obtaining the quartz powder, wherein in the step of preliminary ball milling, balls with diameters of 15-45mm are adopted to carry out ball milling on the ores, and the balls used for preliminary ball milling are more than two kinds of balls with different diameters; in the step of shaping ball milling, balls with uniform diameters are adopted and the diameters of the balls are between 8mm and 20mm; a grinding aid containing alcoholic hydroxyl is also added in the step of shaping ball milling; and in the step of surface modification, the dried quartz powder is mixed with aerosil with grain size of 800-2000 meshes. The invention also provides a quartz powder preparation method with the characteristics that iron tailings are used instead of the quartz ores, and a magnetic separation process is added. The obtained quartz powder has high bulk density and low angle of repose under the condition that both the grade and chemical elements reach the standards.
Description
Technical field
The present invention relates to the preparation field of silica powder, be specifically related to a kind of preparation method producing glass silica powder.
Background technology
The ultra-thin flat glass be applied in flat pannel display industry mainly contains cover-plate glass, glass substrate and ITO conductive glass, and ultra-thin flat glass is one of maximum upstream key part and component of flat pannel display industry amount of purchase.The main raw material manufacturing ultra-thin flat glass is silica powder, and its ratio accounting for raw material is greater than 55%.
At present, the manufacturer that worldwide production is applied to the cover-plate glass of display industries is mainly healthy and free from worry, Xiao Te, Asahi Glass etc., and it occupies most of market share.Current cover-plate glass is mainly based on alumina silicate glass, and market is dominated by healthy and free from worry Gorilla glass, and adopt press over system to produce, quartz raw material used is all import.
Patent application 201510372626.X provides a kind of production method of TFT-LCD base plate glass silica powder, comprise the following steps: (1), the white vein quartz ore selecting aluminium sesquioxide content≤0.1% are raw material, clean laggard row artificial hand selection, for subsequent use after rejecting wherein contained impurity ore; (2) after, the ore crusher in crushing after removing impurity in step (1) being become the ore particles of particle diameter≤25 millimeter, with color selector removing variegated impurity particle wherein, then ore particles is sent in pickling tank, with the chlorohydric acid pickling of mass concentration 28 ~ 31%, after at room temperature dynamically leaching 18 ~ 24 hours, bleed off the hydrochloric acid in pickling tank, then with water the ore particles after pickling fully wash dry to neutrality for subsequent use; (3) after, the ore particles after drying being sent into and is calcined 45 ~ 60 minutes in quartzy calcining furnace under the temperature calcination of 900 ~ 950 DEG C, ore particles is put into the watch-quench tank water of 0 ~ 10 DEG C and carry out shrend, after shrend, ore particles is pulled out, then except for subsequent use after impurity elimination; (4), wet milling mortar is carried out by ore particles obtained in step (3) feeding wheel roller, the muller of described wheel roller and mill disc all adopt quartz to make, the liner of the cylindrical shell of milling of wheel roller is quartzite slate, and in whole sand powder process processed of milling, material does not contact with irony; (5) after the magnetic separator being 5000 ~ 7500 Gausses by mortar Surface field intensity obtained in upper step carries out three grades of magnetic separation, then carry out classification, collection cut size be 150 ~ 300 object sand powder as work in-process, with for subsequent use after centrifuge dewatering; (6), by the sand powder after dehydration carry out drying, after dried sand powder carries out magnetic separation with permanent magnetic separators more than 7500 Gausses again, can obtain TFT-LCD base plate glass silica powder, wherein the massfraction of each component is as follows: SiO
2:>=99.7%, Fe
2o
3:≤0.01%, Al
2o
3:≤0.1%, K
2o+Na
2o :≤0.02%, grain size intervals: 150 ~ 400 orders, wherein 200 order ~ 300 order>=65%, below 400 orders≤5%, 150 orders more than be zero, chlorine ion concentration :≤8ppm.
In this area to the standard-required of ultra-thin glass silica powder be: hand-set lid glass and liquid crystal glass base silica powder ingredient requirement fineness median particle diameter are about 230 orders, particles more than 140 orders is less than 3%, 140 ~ 325 orders are greater than 55%, silicon-dioxide grade>=99.5%, Fe
2o
3≤ 0.01%, Al
2o
3≤ 0.3%, Na
2o+K
2o≤0.02%, TiO
2≤ 0.02%, SO
3≤ 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 silica powder raw material energy prepared in above-mentioned patent application is up to standard and use, but it only considered grade and the chemical composition index of silica powder, and do not consider the pattern of powder and the consistence of fineness of powder, cause the bulk density of powder and mobility all bad, and then affect follow-up glass melting.Therefore, there is a need in the field to provide a kind of new preparation method producing glass silica powder.
Summary of the invention
Therefore, the object of the invention is to prepare the good and grade of a kind of bulk density and mobility and dispersed index and chemical composition production ultra-thin glass silica powder up to standard.The bulk density of the silica powder using the method in the present invention to prepare can reach 1.2g/cm
3above, simultaneously the liquidity scale can reach slope of repose and is less than 35 degree.
Therefore, the invention provides a kind of preparation method producing glass silica powder: comprise select silicon-dioxide grade >=95% and after fragmentation mean diameter at the quartz mine of 2-5mm, first adopt color selector removal of impurities that silicon-dioxide grade is improved further, described ore more first after obtain described silica powder through preliminary ball milling, shaping ball milling, optional flotation removal of impurities, optional acidleach removal step and surface modification step; Wherein, described preliminary ball milling refers to and adopts the aluminum oxide or zirconia ball ore described in ball milling in ball mill that diameter is 15 ~ 45mm, and preliminary ball milling ball is the ball of two or more different diameter; Adopt aluminum oxide or the zirconia ball of mono-disperse in shaping ball milling step, and the diameter of ball is between 8 ~ 20mm, in shaping ball milling step, also adds the grinding aid grinding aid of alcoholic hydroxy; Described surface modification refers to the silica powder of oven dry and granularity to be the process of 800 ~ 2000 object micropowder silica gel batch mixings.
The quartz mine selected in the present invention is its silicon-dioxide grade >=97% preferably, and more preferably >=98.5%.Prepare in the process of silica powder at the quartzy raw ore of use, step and the acidleach removal step of flotation removal of impurities are optional step, if the elements such as the iron in raw ore, potassium, sodium, aluminium, titanium are up to standard after shaping ball milling, then do not need to carry out flotation removal of impurities and acidleach removal step.
The present invention also provides the another kind of preparation method producing glass silica powder: comprise the iron tailings selecting silicon-dioxide grade >=55%, first remove the thin mud wherein crossing 350 ~ 550 mesh sieves, gained sand setting enters the preliminary ball milling of ball mill, enter magnetic separator 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 modification step and obtain described silica powder; Wherein, described preliminary ball milling refers to and adopts the aluminum oxide and/or zirconia ball ore described in ball milling in ball mill that diameter is 15 ~ 45mm, and preliminary ball milling ball is the ball of two or more different diameter; Adopt aluminum oxide and/or the zirconia ball of mono-disperse in shaping ball milling step, and the diameter of ball is between 8 ~ 20mm, in shaping ball milling step, also adds the grinding aid grinding aid of alcoholic hydroxy; Described surface modification refers to the silica powder of oven dry and granularity to be the process of 800 ~ 2000 object micropowder silica gel batch mixings.
The iron tailings selected in the present invention is its silicon-dioxide grade >=65% preferably.Preferably, removing thin mud sieve is 400 ~ 500 mesh sieves.In which of the present invention, those skilled in the art can understand ground, after described iron removal by magnetic separation step also can be arranged on shaping ball milling step, also the step namely in the program changes to preliminary ball milling → shaping ball milling → iron removal by magnetic separation by preliminary ball milling → iron removal by magnetic separation → shaping ball milling, and this is that one of the present invention is equal to substitute mode.
In the present invention, described alcoholic extract hydroxyl group is corresponding phenolic hydroxyl group, and described grinding aid is the fluid cpds containing alcoholic extract hydroxyl group.Grinding aid available in shaping mechanical milling process of the present invention is of a great variety, such as, use the grinding aid of the alcoholic hydroxies such as polymerized polyalcohol, polyalcohol amine, trolamine, tri-isopropanolamine, ethylene glycol, Diethylene Glycol.And found through experiments, when wherein using trolamine for grinding aid, the best performance of gained silica powder product is different.
In the present invention, the step removing thin mud is carried out in hydrocyclone, and magnetic separation step is carried out in vertical ring high-gradient magnetic separator.
Those skilled in the art are known, and the molecular formula of micropowder silica gel is mSiO
2-nH
2o, it is a kind of inorganic chemical product of white powder, belongs to fine chemistry industry series products.Its physicochemical property is: nontoxic, tasteless, do not fire, not quick-fried, non-volatile, corrosion-free, pore volume is large, surfactivity is strong.
In a kind of concrete embodiment, preliminary ball milling ball is the ball of three kinds of different diameters, and the diameter of bead is selected from 15 ~ 25mm, and the diameter of middle ball is selected from 25 ~ 35mm, and the diameter of large ball is selected from 35 ~ 45mm.Preferably, the volume of described bead accounts for 40 ~ 60% of total sphere volume, and the volume of middle ball accounts for 20 ~ 40% of total sphere volume, and the volume of large ball accounts for 10 ~ 30% of total sphere volume.In a kind of concrete embodiment, the diameter of described bead is 20mm, and the diameter of middle ball is 30mm, and the diameter of large ball is 40mm.
In a kind of concrete embodiment, include employing 140 ~ 200 object dusting cover in described preliminary ball milling step and shaping ball milling step and ball mill forms loop line, sift out the quartz that can not sieve and return in ball mill and continue ball milling.
In a kind of concrete embodiment, described grinding aid is trolamine.In a kind of concrete embodiment, described Grinding aid dosage is 0.05 ~ 0.5wt% of silica powder total amount, is preferably 0.1 ~ 0.3wt%.
In a kind of concrete embodiment, in preliminary ball milling and shaping ball milling step, sphere volume used accounts for 50 ~ 75% of ball mill cavity volume volume, and the silica powder of ball milling accounts for 25 ~ 38% of total sphere volume; And drum's speed of rotation is 50-70 rev/min in preliminary ball milling, in shaping ball milling, drum's speed of rotation is 20-40 rev/min.
In a kind of concrete embodiment, the granularity of described micropowder silica gel is 1200-2000 order, and the consumption of micropowder silica gel is 0.1 ~ 1.0wt% of silica powder, preferred 0.3-0.7wt%.
In a kind of concrete embodiment, described preliminary ball milling and shaping ball milling step are the wet ball grinding added water, and in preliminary ball milling, the concentration of quartz in ore pulp is 55 ~ 75wt%, is preferably 60 ~ 70wt%.Preferably, the precedence activities slurry concentrating step of shaping ball milling is also comprised in described method, slurry concentrating step is carried out in thickener, be specially the ore pulp that flushes out adding water after preliminary ball milling or by the concentration of the slurry concentrating to 25 after magnetic separation ~ 50wt%, the concentration of preferred 30-40wt%, the ore pulp after concentrated enters shaping ball milling step.Described concentration refers to the mass concentration of silica powder in ore pulp (at least comprising silica powder and water).To be gone out by ore pulp because needing to add water after preliminary ball milling, the concentration of the ore pulp gone out, about 20%, thus needs concentratedly to enter shaping ball milling step again to it.
In the mechanical milling process of prior art, no matter be dry grinding or wet-milling, ball milling ball is and adopts the ball of different diameter to carry out grating ball milling.As provided a kind of preparation method of silica powder in patent 201310083284.0, wherein ball milling step is: utilized by powder ball mill to carry out dry grinding, ball grinder liner and abrading-ball are aluminum oxide material, ratio of grinding media to material is 2 ~ 3:1, employing diameter is that 4 kinds of abrading-balls of 20 ~ 60mm carry out weight grating, Ball-milling Time is 60 ~ 80min, drum's speed of rotation is 30 ~ 50r/min, the tektite sand of to be tektite sand within 3mm and particle diameter by particle diameter when feeding intake be 0.01 ~ 1mm adds ball grinder simultaneously and grinds, the ratio of weight and number of particle diameter to be tektite sand within 3mm and particle diameter the be tektite sand of 0.01 ~ 1mm is 1:0.6 ~ 0.8.
And in the present invention, first adopting the alumina balls of different diameter to carry out preliminary ball milling to quartz, the alumina balls re-using identical mono-disperse carry out shaping ball milling in conjunction with specific grinding aid to silica powder, finally use micropowder silica gel to carry out surface modification to silica powder.The silica powder of gained when grade and chemical element all up to standard, its bulk density is large, and the slope of repose representing silica powder mobility is low.
Accompanying drawing explanation
Fig. 1 is the particle size distribution figure of the silica powder after tentatively grinding;
Fig. 2 is the particle size distribution figure of the silica powder after shaping ball milling;
Fig. 3 is the SEM figure of the silica powder after tentatively grinding, and wherein Fig. 3 a is the SEM figure under 100 μm of scales, Fig. 3 b is that the SEM under 50 μm of scales schemes;
Fig. 4 is the SEM figure of the silica powder after shaping ball milling, and wherein Fig. 4 a is the SEM figure under 100 μm of scales, Fig. 4 b is that the SEM under 50 μm of scales schemes;
Fig. 5 is the SEM figure of the silica powder after surface modification, and wherein Fig. 5 a is the SEM figure under 100 μm of scales, Fig. 5 b is that the SEM under 50 μm of scales schemes.
Embodiment 1
The present embodiment provides a kind of method preparing target silica powder from quartzy raw ore.
First the quartz mine that silicon-dioxide grade is greater than 98.5% is chosen, (Cr≤0.0005%, Co≤0.0005%, Mn≤0.0005%, Ni≤0.0005%, Pb≤0.005%, Cd≤0.005%, Cu≤0.001%, in quartz raw ore, the content of these elements is substantially satisfied), it is 2-5mm that the good quartz mine chosen according to this condition is crushed to median size, is selected the coloring impurity of the inside, make silicon-dioxide grade be greater than 99.5% by color selector.
Look product of hanking enter ball mill and carry out the preliminary ball milling of wet method, ore pulp is primarily of silica powder and water composition, sphere volume accounts for ball mill 2/3rds, the quartz mine of ball milling accounts for 1/3rd of sphere volume, the following 40mm ball of ball proportioning accounts for 20%, 30mm ball and accounts for 30%, 20mm ball and account for 50%, ball milling concentration at 60-70wt% (quartz concentration) in ore pulp, drum's speed of rotation 60 revs/min.Ball mill and 160 order high frequency fine screens form loop line, and substandard product returns ball mill and regrinds, next step technique of product introduction that fineness is qualified, and screen undersize fineness is that to cross the content of 230 mesh sieves be 40 ~ 50wt%.Preliminary mechanical milling process is the process of continuous discharge.
Product ore pulp under sieving after preliminary ball milling is concentrated to the concentration of 30-40% through thickener, feed reshaping ball grinder, sphere volume accounts for ball mill 2/3rds, the silica powder stone of ball milling accounts for 1/3rd of sphere volume, the following 20mm ball of ball proportioning accounts for 100%, or 14mm ball accounts for 100%, or 10mm ball accounts for 100%, drum's speed of rotation 20-40 rev/min, adds the grinding aid trolamine of 0.2%.Ball mill and 160 order high frequency fine screens form closed circuit, and guarantee do not have coarse particles product, substandard product returns ball mill and regrinds, the product introduction hypomere magnetic separation process that fineness is qualified, and screen undersize fineness is that to cross the content of 230 mesh sieves be 50 ~ 55wt%.
Product after shaping ball milling feeds strong magnetic deironing, if the product potassium sodium aluminium titanium foreign matter content after strong magnetic deironing is not up to standard, just enters the further removal of impurities of flotation flowsheet: add the sulfuric acid of 1 ~ 2kg/ ton and the HF of 200 ~ 400g/ ton, and the pH value of adjustment mine tailing is 2 ~ 3; The mixed amine acetate adding 100 ~ 200g/ ton again, as collecting agent, sweeps the quartz concentrate after obtaining removal of impurities through one thick two.After removal of impurities, if above-mentioned ferripotassium sodium aluminium titanium is defective, then enter acidleach flow process, the ratio 9:1 of HCL and HF in acidleach flow process, normal temperature acidleach 2h-3h, the concentration 20-25% of acid, acidleach concentration 40-50%.
By this technique, can produce powder consistency good, microscopic appearance rule, chemical index and fineness meet the silica powder of ultra-thin panel display glass silica powder raw material standard.In the present embodiment, before shaping ball milling with the bulk density of silica powder afterwards by 0.95g/cm
3rise to 1.15g/cm
3, slope of repose is reduced to 35.6 degree by 37.6 degree.
Silica powder after acidleach removal of impurities is dried under the condition of 100 ~ 150 DEG C, carries out being dry mixed mixing and the Process of Surface Modification completed silica powder with necessarily required micropowder silica gel.Particularly, first the present invention carries out drying to micropowder silica gel before interpolation, after 100-150 DEG C of dry 2h, crosses 30-40 mesh sieve to remove the micropowder silica gel of reuniting, and divides three to four batches and add in silica powder, make silica powder and micropowder silica gel batch mixing even.Whole process is dry mixed in spiral mixer.In the present embodiment, before surface modification with the bulk density of silica powder afterwards by 1.15g/cm
3rise to 1.23g/cm
3, slope of repose is reduced to 34.2 degree by 35.6 degree.
Fig. 1 is the particle size distribution figure of the silica powder in embodiment 1 after preliminary grinding; Fig. 2 is the particle size distribution figure of the silica powder in embodiment 1 after shaping ball milling.The SEM figure of Fig. 3 to be the SEM figure of the silica powder in embodiment 1 after preliminary grinding, Fig. 4 be silica powder in embodiment 1 after shaping ball milling, Fig. 5 is the SEM figure of the silica powder in embodiment 1 after surface modification.
From Fig. 1 ~ 5, with more corner angle on the silica powder particle that conventional grinding (only tentatively grind and do not carry out shaping grinding) obtains, and the shape of particle roughly has the different morphologies such as rhombus, rectangle, square and subcircular; And by after concrete shaping ball milling in the present invention, gained silica powder particle rarely has corner angle, and particle shape is mostly in subcircular, and the uniformity coefficient of granular size is further improved.
Embodiment 2
The present embodiment provides a kind of method preparing target silica powder from iron tailings.
Raw material adopts iron tailings, in iron tailings, silicon-dioxide grade is greater 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 meet the demands substantially).
First the thin mud removed in iron tailings (crosses foreign matter content in the thin mud of 400 orders or 500 mesh sieves large, thus first remove), sand setting enters the preliminary ball milling of ball mill, sphere volume accounts for ball mill 2/3rds, and the quartz mine of ball milling accounts for 1/3rd of sphere volume, and the following 40mm ball of ball proportioning accounts for 20%, 30mm ball accounts for 30%, 20mm ball accounts for 50%, ball milling concentration at 60-70%, drum's speed of rotation 60 revs/min.Ball mill and 160 order high frequency fine screens form closed circuit, and substandard product returns ball mill and regrinds, the product introduction shaping process that fineness is qualified, and screen undersize fineness is that to cross the content of 230 mesh sieves be 40 ~ 50wt%.
After preliminary ball milling, screen undersize is under the magnetic field of 1.2T, and carry out one thick two and sweep (one roughing is scanned for twice) deferrization process, the taste of the silica powder after deironing is about 90%.The mine tailing ore pulp of magnetic separation is concentrated to the concentration of 30-40% through thickener, feed reshaping ball grinder, sphere volume accounts for ball mill 2/3rds, the silica powder of ball milling accounts for 1/3rd of sphere volume, the following 20mm ball of ball proportioning accounts for 100%, or 14mm ball accounts for 100%, or 10mm ball accounts for 100%, drum's speed of rotation 20-40 rev/min, adds the grinding aid trolamine of 0.1-0.3%.Ball mill and 160 order high frequency fine screens form closed circuit, and guarantee do not have coarse particles product, substandard product returns ball mill and regrinds, segment process under the product introduction that fineness is qualified, and screen undersize fineness is that to cross the content of 230 mesh sieves be 50 ~ 55wt%.The technique of flotation except potassium, sodium, aluminium, iron, titanium and sulphur is carried out after ball milling.Flotation step is specific as follows: add the sulfuric acid of 8 ~ 10kg/ ton and the HF of 500 ~ 800g/ ton, and the pH value of adjustment mine tailing is 2 ~ 3; The mixed amine acetate adding 300 ~ 500g/ ton again, as collecting agent, is swept (one roughing is scanned for six times) reverse flotation removal of impurities through one thick six and is obtained quartz concentrate, make silicon-dioxide grade be greater than 99.2%.One or more constituent contents that above-mentioned quartz mine is generally understood in iron, potassium, sodium, aluminium, titanium are defective, then enter acidleach flow process.Acidleach is specially the ratio 8:1:1 of HCL, oxalic acid and HF, and the concentration 20-25% of acid, acidleach concentration 40-50%, heats to 80 DEG C of acidleach 2h-3h, and obtain qualified silica powder product, silicon-dioxide grade is greater than 99.5%, and bulk density is greater than 1.10g/cm
3, the liquidity scale is that slope of repose is less than 36 degree.
By this technique, can produce powder consistency good, microscopic appearance rule, chemical index and fineness meet the silica powder of ultra-thin panel display glass silica powder raw material standard.In the present embodiment, before shaping ball milling with the bulk density of silica powder afterwards by 0.92g/cm
3rise to 1.13g/cm
3, slope of repose is reduced to 35.8 degree by 37.8 degree.
Silica powder after acidleach removal of impurities is dried under the condition of 110 DEG C, carries out being dry mixed mixing and the Process of Surface Modification completed silica powder with necessarily required micropowder silica gel.Particularly, first the present invention carries out drying to micropowder silica gel before interpolation, after 150 DEG C of dry 2h, crosses 30-40 mesh sieve to remove the micropowder silica gel of reuniting, and divides three to four batches and add in silica powder, make silica powder and micropowder silica gel batch mixing even.Whole process is dry mixed in spiral mixer.In the present embodiment, before surface modification with the bulk density of silica powder afterwards by 1.13g/cm
3rise to 1.26g/cm
3, slope of repose is reduced to 34.5 degree by 35.8 degree.
The rule identical with embodiment 1 and conclusion can be found out from the particle size distribution figure of embodiment 2 and SEM figure (not shown), not repeat them here.It should be noted that, when using quartz mine to prepare silica powder for raw material, also comprising the process of strong magnetic deironing and magnetic separation after preliminary ball milling step and before slurry concentrating step alternatively, for removing the ferro element brought in quartz mine.And prepare in the process of silica powder at use quartz mine or iron tailings for raw material, selectively can also be included in the successor activities after shaping ball milling step, namely strong magnetic iron removal is carried out once again, to remove the ferro element may brought into because of machinery equipment in shaping ball milling step.
Embodiment 3
In the present embodiment, all the other conditions are all identical with embodiment 1, but grinding aid is changed into the ethylene glycol of 0.2wt% by the trolamine of 0.2wt%.In the present embodiment, before shaping ball milling with the bulk density of silica powder afterwards by 0.95g/cm
3rise to 1.10g/cm
3, slope of repose is reduced to 36.3 degree by 37.6 degree, and before surface modification with the bulk density of silica powder afterwards by 1.10g/cm
3rise to 1.18g/cm
3, slope of repose is reduced to 35.0 degree by 36.3 degree.
And using other grinding aid as polymerized polyalcohol, polyalcohol amine, tri-isopropanolamine and Diethylene Glycol etc., the bulk density of gained silica powder and slope of repose result are that the result of grinding aid is suitable with making spent glycol.Illustrate, in shaping mechanical milling process of the present invention, use the shaping effect that trolamine is best for grinding aid has.
Can select add or do not add grinding aid in preliminary ball milling step of the present invention, but then need to add grinding aid in shaping ball milling step, and selecting of grinding aid can produce certain impact to the bulk density of final silica powder product and slope of repose.
In the present invention, described flotation removal of impurities and acidleach removal step are processing step well known to those skilled in the art.In the present invention, may without the need to the step of acidleach removal of impurities when quartzy raw ore prepares silica powder, and the step of acidleach removal of impurities when preparing silica powder by iron tailings, is needed because foreign matter content is higher.
In the present invention, the diameter of the ball of described shaping ball milling step can be greater than the diameter of minimum ball in preliminary ball milling step, is more often that the diameter of ball in shaping ball milling step is minimum certainly.In preliminary mechanical milling process, more M-ARY is all the ball milling state that a kind of bead fills large ball space; And in shaping mechanical milling process, more M-ARY is the ball milling state that space between each ball filled by a kind of silica powder.
In the present invention, the bulk density of silica powder is higher, then its grating is better, prepare in glass process to found effect just better, thus when meet grade, granularity and elementary composition, the bulk density of silica powder is more high better.And the slope of repose of silica powder is less, then illustrate the mobility of silica powder and dispersiveness better, found more favourable to glass batch mixing and charging in advance.In the present invention, the detection at bulk density and slope of repose also adopts this area universal test method, is manually calculate to obtain as the data at slope of repose.
Silica powder provided by the invention is not compared with making the silica powder of shaping ball milling, its bulk density is higher, slope of repose is less, follow-up for the preparation of the melting process of glass in its good fluidity, reunion or the phenomenon that hardens not easily is produced during high temperature more than 1600 DEG C, uneven when effectively prevent fusing, easily form bubble, bad point and cause glass to occur the phenomenon of quality problems.
In sum, the bulk density of silica powder that the present invention prepares can be greater than 1.2g/cm
3, the liquidity scale is that slope of repose is less than 35 degree.Compared to existing technology, the product performance of this silica powder obtain obvious improvement.
The median particle diameter of the silica powder after shaping ball milling is about 230 orders, and bulk density can reach 1.10g/cm
3above, slope of repose can be less than 36 degree, but the dispersiveness of such silica powder and mobility are still not high enough, still can cause in the melting process of glass batch mixing uneven, reunite and the phenomenon such as bubble is more, affect the quality of glass.Also comprise the step of silica powder being carried out to surface modification in the present invention, the dispersiveness of silica powder and mobility are improved further, and then ensure that various raw material can mix, and be less likely to occur to reunite in melting process.
Silicon-dioxide grade >=96% of the micropowder silica gel used in the present invention, adds a certain amount of micropowder silica gel in silica powder, and it both can be used as anticaking agent, improved the dispersiveness of silica powder, can ensure silica powder before melting in dispersion state; Can glidant being made again, improving the mobility of frit when mixing and when founding feed.After mixing through the pile of grounds density of surface modification by 1.1g/cm
3rise to 1.2g/cm
3above, slope of repose drops to less than 35 degree by 36 degree.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. produce the preparation method of glass silica powder for one kind: comprise select silicon-dioxide grade >=95% and after fragmentation mean diameter at the quartz mine of 2-5mm, first adopt color selector removal of impurities that silicon-dioxide grade is improved further, described ore more first after obtain described silica powder through preliminary ball milling, shaping ball milling, optional flotation removal of impurities, optional acidleach removal step and surface modification step; Wherein, described preliminary ball milling refers to and adopts the aluminum oxide or zirconia ball ore described in ball milling in ball mill that diameter is 15 ~ 45mm, and preliminary ball milling ball is the ball of two or more different diameter; Adopt aluminum oxide or the zirconia ball of mono-disperse in shaping ball milling step, and the diameter of ball is between 8 ~ 20mm, in shaping ball milling step, also adds the grinding aid grinding aid of alcoholic hydroxy; Described surface modification refers to the silica powder of oven dry and granularity to be the process of 800 ~ 2000 object micropowder silica gel batch mixings.
2. produce the preparation method of glass silica powder for one kind: comprise the iron tailings selecting silicon-dioxide grade >=55%, first remove the thin mud wherein crossing 350 ~ 550 mesh sieves, gained sand setting enters the preliminary ball milling of ball mill, enter magnetic separator 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 modification step and obtain described silica powder; Wherein, described preliminary ball milling refers to and adopts the aluminum oxide or zirconia ball ore described in ball milling in ball mill that diameter is 15 ~ 45mm, and preliminary ball milling ball is the ball of two or more different diameter; Adopt aluminum oxide or the zirconia ball of mono-disperse in shaping ball milling step, and the diameter of ball is between 8 ~ 20mm, in shaping ball milling step, also adds the grinding aid grinding aid of alcoholic hydroxy; Described surface modification refers to the silica powder of oven dry and granularity to be the process of 800 ~ 2000 object micropowder silica gel batch mixings.
3. method according to claim 1 or 2, is characterized in that, preliminary ball milling ball is the ball of three kinds of different diameters, and the diameter of bead is selected from 15 ~ 25mm, and the diameter of middle ball is selected from 25 ~ 35mm, and the diameter of large ball is selected from 35 ~ 45mm.
4. method according to claim 3, it is characterized in that, the volume of described bead accounts for 40 ~ 60% of total sphere volume, and the volume of middle ball accounts for 20 ~ 40% of total sphere volume, and the volume of large ball accounts for 10 ~ 30% of total sphere volume.
5. method according to claim 1 or 2, is characterized in that, includes employing 140 ~ 200 object dusting cover and ball mill forms loop line in described preliminary ball milling step and shaping ball milling step, sifts out the quartz that can not sieve and returns in ball mill and continue ball milling.
6. method according to claim 1 or 2, is characterized in that, described grinding aid is trolamine, and Grinding aid dosage is 0.05 ~ 0.5wt% of silica powder total amount, is preferably 0.1 ~ 0.3wt%.
7. method according to claim 1 or 2, is characterized in that, in preliminary ball milling and shaping ball milling step, sphere volume used accounts for 50 ~ 75% of ball mill cavity volume volume, and the silica powder of ball milling accounts for 25 ~ 38% of total sphere volume; And drum's speed of rotation is 50-70 rev/min in preliminary ball milling, in shaping ball milling, drum's speed of rotation is 20-40 rev/min.
8. method according to claim 1 or 2, is characterized in that, the granularity of described micropowder silica gel is 1200-2000 order, and the consumption of micropowder silica gel is 0.1 ~ 1.0wt% of silica powder, preferred 0.3-0.7wt%.
9. method according to claim 1 or 2, is characterized in that, described preliminary ball milling and shaping ball milling step are the wet ball grinding added water, and in preliminary ball milling, the concentration of quartz in ore pulp is 55 ~ 75wt%, is preferably 60 ~ 70wt%.
10. method according to claim 9, it is characterized in that, the precedence activities slurry concentrating step of shaping ball milling is also comprised in described method, slurry concentrating step is carried out in thickener, be specially the ore pulp that flushes out adding water after preliminary ball milling or by the concentration of the slurry concentrating to 25 after magnetic separation ~ 50wt%, the concentration of preferred 30-40wt%, the ore pulp after concentrated enters shaping ball milling step.
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| 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 |
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| CN108975679A (en) * | 2018-09-05 | 2018-12-11 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of TFT-LCD glass substrate silicon powder preparation method |
| 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 |
| CN109996763A (en) * | 2016-11-18 | 2019-07-09 | Ppg工业俄亥俄公司 | Spheric granules and preparation method thereof based on silica |
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| 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 |
| CN111594763A (en) * | 2020-06-03 | 2020-08-28 | 北煤化(北京)科技有限公司 | Method for improving fluidity and concentration of ore pulp |
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