CN104619433A - Method for regenerating spent ceria-containing polishing agent - Google Patents
Method for regenerating spent ceria-containing polishing agent Download PDFInfo
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- CN104619433A CN104619433A CN201380047642.0A CN201380047642A CN104619433A CN 104619433 A CN104619433 A CN 104619433A CN 201380047642 A CN201380047642 A CN 201380047642A CN 104619433 A CN104619433 A CN 104619433A
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- oxidation
- abrasive material
- containing cerium
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- waste slurry
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
- B24B57/02—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents for feeding of fluid, sprayed, pulverised, or liquefied grinding, polishing or lapping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B7/00—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
- B24B7/20—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground
- B24B7/22—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain
- B24B7/24—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain for grinding or polishing glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C11/00—Selection of abrasive materials or additives for abrasive blasts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Grinding-Machine Dressing And Accessory Apparatuses (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention relates to a method for regenerating spent ceria-containing polishing agent, the method allowing regeneration as a regenerated ceria-containing polishing agent, having suitable granular distribution and crystal size and exhibiting an accordant desirable polishing rate, while effectively discarding impurities contained in the spent ceria-containing polishing agent. A method for regenerating the spent ceria-containing polishing agent comprises the steps of: dissolving spent ceria (CeO2)-containing sludge in a solvent comprising strong alkali and hydrofluoric acid; cleaning the spent ceria-containing sludge and discarding impurities containing silica (SiO2); drying the cleaned spent ceria-containing sludge by means of a compact disc (CD) dryer; and, in the presence of a flux comprising ammonium salt, alkali metallic salt, metal oxide, metal oxygen acid or alkaline earth metal, sintering the spent sludge at a temperature of 800 DEG C or higher.
Description
Technical field
The present invention relates to a kind of oxidation-containing cerium to give up the renovation process of abrasive material.More specifically, oxidation-containing cerium involved in the present invention gives up the renovation process of abrasive material, effectively can remove oxidation-containing cerium to give up the impurity comprised in abrasive material, and be regenerated as the oxidation-containing cerium regenerating abrasive demonstrating suitable size distribution and crystal size and the better polishing rate that brings thus etc.
Background technology
Usually, as the TFT-LCD glass substrate etc. of kinescope or liquid crystal panel, the state that surperficial flatness or roughness etc. are bad can be become in process of production, be thus difficult to female glass to be directly used as kinescope or glass substrate of liquid crystal panel.Especially, for the TFT-LCD face glass being used as liquid crystal panel, studying various method to improve the brightness, visual angle, contrast etc. of product, these characteristics known also can be subject to the very large impact of TFT-LCD glass baseplate surface.Therefore, the producer producing glass substrate is making great efforts the surface of improving glass substrate, and uses various glass substrate abrasive material.Wherein, oxidation-containing cerium (CeO is widely used as conventional abrasive material
2) abrasive material.
But this oxidation-containing cerium abrasive material, after the glass polishing process of certain hour, becomes waste slurry because polishing efficiency reduction goes out of use.This is because after the polishing process of certain hour, the polishing efficiency of described abrasive material reduces, and there will be the cohesion between abrasive grain, causes the risk producing a large amount of cut to increase.Moreover the impurity being derived from polishing pad produced in polishing process can enter in abrasive slurries, thus the possibility producing cut is caused to increase further.
Therefore, need discarded described abrasive material use certain hour in glossing after, this can reduce process efficiency or economy.For this reason, several technology of the described abrasive material of recycling are being studied.
But, for recycling and the renovation process of known oxidation-containing cerium abrasive material, because the size distribution of abrasive grain of regeneration or crystal size are not optimized, so the polishing rate of regenerating abrasive is abundant not or produce the cohesion between particle in regenerative process and generate bulky grain etc., thus produce the problems such as cut when causing utilizing regenerating abrasive to grind.
Summary of the invention
In view of this, the invention provides a kind of oxidation-containing cerium to give up the renovation process of abrasive material, effectively can remove oxidation-containing cerium to give up the impurity comprised in abrasive material, and be regenerated as the oxidation-containing cerium regenerating abrasive demonstrating suitable size distribution and crystal size and the better polishing rate that brings thus etc.
The invention provides a kind of oxidation-containing cerium to give up the renovation process of abrasive material, comprise the following steps: by oxidation-containing cerium (CeO
2) waste slurry is dissolved in the solvent solution comprising highly basic and hydrofluoric acid; Described oxidation-containing cerium waste slurry is cleaned, to remove silicon oxide-containing (SiO
2) impurity; Drying is carried out to described cleaned oxidation-containing cerium waste slurry CD drying machine (Compact Di sc dreyer); And comprise ammonium salt, alkali metal salt, metal oxide, metal oxygen-containing acid or alkali salt flux (flux) exist under, described waste slurry is sintered with the temperature of more than 800 DEG C.
Below, the renovation process of the abrasive material that to give up according to the oxidation-containing cerium of the embodiment of the present invention is described in detail.
The renovation process that one embodiment of the invention provides a kind of oxidation-containing cerium to give up abrasive material, comprises the following steps: oxidation-containing cerium waste slurry is dissolved in the solvent solution comprising highly basic and hydrofluoric acid; Described oxidation-containing cerium waste slurry is cleaned, to remove silicon oxide-containing impurity; Drying is carried out to described cleaned oxidation-containing cerium waste slurry CD drying machine; And comprise ammonium salt, alkali metal salt, metal oxide, metal oxygen-containing acid or alkali salt flux exist under, described waste slurry is sintered with the temperature of more than 800 DEG C.
Give up in the renovation process of abrasive material at the oxidation-containing cerium of an embodiment, the oxidation-containing cerium waste slurry being derived from useless abrasive material is dissolved in the solvent solution of regulation, use the impurity dissolving and be derived from glass substrate etc., and removed after these impurity by cleaning, drying and the sintering process abrasive material that oxidation-containing cerium can be given up is regenerated as regenerating abrasive.
Especially, in the renovation process of an embodiment, described drying process carries out in the CD drying machine of alternative conventional ovens formula drying machine (Oven dryer), and in sintering process, use regulation flux carry out high temperature sintering, thus can make described oxidation-containing cerium give up abrasive material regeneration.
The main purpose of this drying and sintering process carries out drying in order to remove the moisture used in solvent solution process and cleaning that described impurity carries out, recover the surface state of regenerating abrasive, and remove further and be derived from polishing pad or attach other impurity such as the impurity of pad (backpad) etc. or metal impurities.The experimental result of the present inventor shows, as above the condition of described drying and sintering process is controlled, more effectively can remove pad (pad) impurity, and the size distribution of regenerating abrasive and crystal size are optimized, thus the bulky grain generation that can suppress the cohesion between the abrasive grain in regenerative process and cause thus.
Further, the oven drying mode of conventional ovens formula drying machine is used to need to carry out filter-pressing process (filter press) as step before, and need to carry out the broken technique of roller (rollcrusher) as subsequent step, the cost of technology therefore may be caused to increase and yield reduction.But, in one embodiment, carry out alternative this oven drying mode by application CD drying machine, several step can be merged into a step and process, can also yield be improved.
Therefore, according to the renovation process of an embodiment, effectively can remove oxidation-containing cerium to give up the impurity comprised in abrasive material, and be regenerated as the better polishing rate demonstrating suitable size distribution and crystal size and bring thus, reduce the oxidation-containing cerium regenerating abrasive of the cut produced because of bulky grain, thus realize regeneration and recycling.And, significantly can also improve efficiency and the yield of this regeneration technology.
Below, give up by the oxidation-containing cerium that each step more specifically describes an embodiment with reference to accompanying drawing the renovation process of abrasive material.Fig. 1 is that the oxidation-containing cerium showing an embodiment by each step gives up the schematic diagram of one of renovation process example of abrasive material.
First, in the renovation process of an embodiment, the oxidation-containing cerium as regeneration object gives up abrasive material and consequent waste slurry, can be derived from the oxidation-containing cerium abrasive material for polished glass substrate in the manufacturing process of TFT-LCD etc.Therefore, described oxidation-containing cerium waste slurry etc. can comprise as major impurity the silica (SiO being derived from glass substrate
2) and aluminium oxide (Al
2o
3).And, described waste slurry or useless abrasive material may comprise as impurity and be derived from the polishing pad through polishing or the various organic matters etc. for the attaching pad that supports polished glass substrate, also may comprise other metal ingredients such as iron (Fe), chromium (Cr) or nickel (Ni).
Therefore, when regenerating described oxidation-containing cerium waste slurry etc., need to carry out following technique: remove these silica and aluminium oxide; Other impurity of polishing pad, attaching pad etc. or containing metal composition are derived from described in removal; And the surface characteristic of control oxidation-containing cerium abrasive material, size distribution and crystal size etc.
Refer to Fig. 1, in the renovation process of an embodiment, first can by oxidation-containing cerium (CeO
2) waste slurry is dissolved in the solvent solution comprising highly basic and hydrofluoric acid.In this process, can NaOH or potassium hydroxide etc. be used as described highly basic, and these can dissolve described in be derived from the impurity such as the silica of glass substrate.In addition, described hydrofluoric acid is mainly used as the composition of glass etching liquid, this also can dissolve described in be derived from the impurity such as the silica of glass substrate or aluminium oxide.
Therefore, if described oxidation-containing cerium waste slurry is scattered in the solvent solution comprising highly basic and hydrofluoric acid such as to comprise in the solvent aqueous solution of the highly basic such as NaOH or potassium hydroxide and hydrofluoric acid and process, the impurity being derived from glass substrate such as silica or the aluminium oxide etc. then comprised in described waste slurry will be fallen by dissolution with solvents, thus can be separated with described waste slurry.
Now, consider the impurity content etc. such as silica or aluminium oxide comprised in described waste slurry, suitably can control the concentration of highly basic in described solvent solution and hydrofluoric acid.Just, in order to effectively remove the impurity such as described silica or aluminium oxide with in the waste slurry crossed in the polishing of the LCD glass substrate from routine, the described highly basic comprised in solvent solution and/or the concentration of hydrofluoric acid are suitably about 0.01 to 20M or about 0.1 to 15M or about 1 to 10M respectively.If the concentration of highly basic described in solvent solution and hydrofluoric acid is too low, deimpurity efficiency is gone to reduce.On the contrary, if the excessive concentration of described highly basic and hydrofluoric acid, the use amount of raw material will unnecessarily increase.
In addition, after described oxidation-containing cerium waste slurry is dissolved in the solvent solution of regulation, by cleaning this waste slurry, silicon oxide-containing impurity can be removed from waste slurry.Now, before described cleaning or carry out in the process of cleaning, the solid-liquid separation process being undertaken by methods such as centrifugation, filtration or sedimentations by the waste slurry through described solvent solution process processing can also be comprised.
When carrying out this solid-liquid separation process, described waste slurry and the glass substrate impurities such as the silica be dissolved in described solvent solution or aluminium oxide will by Separation of Solid and Liquid, and then can be separated from described waste slurry and remove impurity, and by carrying out the cleaning utilizing deionized water, water or other aqueous solvents, can thoroughly remove described impurity further.
Now, the techniques such as described centrifugation, filtration or sedimentation are undertaken by following methods: by the centrifugal separation process of routine, separate deimpurity oxidation-containing cerium waste slurry and the liquid component (centrifugal separation process) containing impurity; Or go the sedimentation of deimpurity oxidation-containing cerium waste slurry described in making, to isolate the liquid component (sedimentation process) containing impurity; Or use filter etc., from the described liquid component (filtering technique) going deimpurity oxidation-containing cerium waste slurry to filter and isolate containing impurity.Certainly, at least two kinds of combinations in these centrifugations, filtration or sedimentation can also be adopted.
In addition, in the cleaning utilizing described aqueous solvent, in order to more effectively clean and remove the impurity be dissolved in described solvent solution, can use pH value be adjusted to 1 to 4 or pH value be adjusted to 10 to 14 aqueous solvent.In order to suitably adjust ph, can acid or alkali be suitably dissolved in described water or deionized water, to be used as cleaning fluid.
And, in this cleaning, in described waste slurry to be regenerated, the flux that can use in following sintering process can be added.
In addition, as shown in Figure 1, after carrying out described cleaning, drying can be carried out to cleaned oxidation-containing cerium waste slurry CD drying machine.In this drying process, can the drying of deimpurity waste slurry be gone to remove from described the moisture being used for described solvent solution treatment process and cleaning, so carry out drying process, waste slurry can be made to have the moisture content of less than about 1 % by weight or about 0 to 1 % by weight.
Especially, in the renovation process of an embodiment, the CD drying machine of one of tray drier can be used to carry out drying at described drying process.This CD drying machine is a kind of tray drier described waste slurry being carried out to drying on heat supply rotating disk, the dry function of this CD is used to suppress abrasive grain in described drying process (such as, cerium oxide particle) between cohesion, therefore suppress oarse-grained generation, and then use the generation that can suppress cut during the oxidation-containing cerium abrasive material of regeneration.And, effectively can carry out drying process by using this CD drying machine.Because carry out drying in described CD drying machine, can, Transmit evenly heat efficient to described waste slurry.
When carrying out drying with described CD drying machine, on the CD drying machine rotated with the speed of about 1 to 10rpm or about 5 to 10rpm or about 6 to 9rpm, can carry out for about 1 to 30 second with the temperature of about 100 to 200 DEG C.If the rotating speed of described CD drying machine crosses slow or drying time is long, the risk producing cut because there is cohesion between particle will increase.On the contrary, if rotating speed is too fast or drying time is too short, drying process just may can not carry out effectively.
Relative to this, when carrying out drying with CD drying machine with optimal conditions, the oxidation-containing cerium regenerating abrasive of regeneration can have the suitable particle mean size of about 0.5 to 3.0 μm, and suppress the oarse-grained generation of more than about 6.0 μm, the risk not only producing cut reduces, also effectively can carry out drying, thus can be easy to obtain the regenerating abrasive that moisture content is less than about 1 % by weight.
In addition, after carrying out described drying process, as shown in Figure 1 can comprise ammonium salt, alkali metal salt, metal oxide, metal oxygen-containing acid or alkali salt flux exist under, described dried waste slurry is sintered with the temperature of more than about 800 DEG C.By carrying out this sintering process, the surface characteristic and the crystallization property that are included in the oxidation-containing cerium abrasive material in waste slurry are restored, thus the polishing rate of regenerating abrasive can be improved, and other impurity can be removed, such as be derived from the polishing pad through polishing or the various organic matters for the attaching pad that supports polished glass substrate, or the containing metal constituent impurity etc. such as iron (Fe), chromium (Cr) or nickel (Ni).
Especially, when using described specific flux, after carrying out described sintering process, the surface characteristic of described regenerating abrasive or crystallization property etc. can control in preferable range.As a result, the size distribution of regenerating abrasive and crystal size can control in proper range, and can suppress oarse-grained generation.
More preferably, when using this flux, use the described flux of about 1 to 1.5 % by weight relative to the weight of described waste slurry, and the temperature of described sintering process is controlled about 800 to 900 DEG C of scopes, the size distribution of regenerating abrasive and crystal size so can be made more to optimize.More specifically, carry out sintering process under these conditions, the size distribution of described regenerating abrasive and crystal size will be optimized for about 0.5 to 3.0 μm or about 1.0 to 3.0 μm and about 60 to 90nm or about 70 to 90nm respectively, and oarse-grained generation can be suppressed, thus control the polishing rate of regenerating abrasive for outstanding, and bulky grain can be suppressed to generate the generation of the cut caused.
Therefore, the regenerating abrasive obtained by the method for an embodiment can be used better.
In described sintering process, described flux can by ammonium salts such as ammonium fluoride, ammonium chloride, ammonium phosphate or ammonium sulfate; Alkali metal salt or the alkali salts such as sodium chloride, sodium fluoride, NaOH, potassium hydroxide, potassium chloride, Boratex or barium chloride; The metal oxides such as boron oxide; Or boric acid (H
3bO
3) etc. metal oxygen-containing acid composition, also can use at least two kinds that are selected from these compounds together.When using this flux, after carrying out described sintering process, the surface characteristic of described regenerating abrasive or crystallization property etc. can control in preferable range, and then the size distribution of regenerating abrasive and crystal size can be controlled in proper range.
And as mentioned above, described flux can add and wet mixed in the cleaning step carried out before, or also can give dry type mixing before sintering process, wherein be suitable in cleaning step wet mixed.Described sintering step can carry out about 1 to 4 hour at described temperature.
By carrying out the sintering process of described optimization, the particle mean size of crystal size and about 0.5 to 3.0 μm with about 60 to 90nm can be obtained, and the oxidation-containing cerium regenerating abrasive of optimization that oarse-grained formation is inhibited.If described crystal size or particle mean size too small, the polishing rate of regenerating abrasive may be abundant not.On the contrary, if crystal size or particle mean size excessive, use in the glossing of regenerating abrasive and may produce cut, or the pulverizing carried out as required after sintering process and grading technology may become non-efficient activity.Especially, in order to reduce excessive granularity or crystal size, carry out excessively pulverizing and grading technology time, not only the efficiency of regeneration technology can significantly reduce, and in the process of carrying out this disintegrating process etc., the surface characteristic of regenerating abrasive on the contrary can be impaired, and the characteristic of regenerating abrasive may be caused to reduce.
In addition, after carrying out described sintering process, in order to reduce size distribution or the crystal size of regenerating abrasive as required or remove bulky grain, can carry out further pulverizing or grading technology, and this pulverizing and grading technology be undertaken by the well-known method of those skilled in the art.Such as, described disintegrating process can use jet pulverizer (jet-mill) etc. to carry out, and described grading technology can use the wind classification devices such as cyclone separator, dry classification device, utilizes the EJ-ELBO grading plant of two limits or three limit Tip or carry out for the sieve of classification.
According to described renovation process, the impurity being derived from glass substrate etc. can be obtained thoroughly, effectively removed in fact, demonstrate crystal size and the size distribution of optimization, and oarse-grained be created on pulverizing and grading technology before the oxidation-containing cerium regenerating abrasive that is also inhibited.Therefore, this oxidation-containing cerium regenerating abrasive can be used alone or uses together with new abrasive material, thus is reused for polishing LCD glass substrate etc., and this can make a significant contribution to the economy and yield improving technique.
Oxidation-containing cerium according to the present invention gives up the renovation process of abrasive material, effectively can remove oxidation-containing cerium to give up the impurity comprised in abrasive material, and be regenerated as the better polishing rate demonstrating suitable size distribution and crystal size and bring thus, reduce the oxidation-containing cerium regenerating abrasive of the cut produced because of bulky grain, thus realize regeneration and recycling.
Accompanying drawing explanation
Fig. 1 is that the oxidation-containing cerium showing an embodiment by each step gives up the schematic diagram of one of renovation process example of abrasive material.
Fig. 2 is presented to carry out drying with CD drying machine in embodiment 1 and 2 and the chart of the size distribution of the oxidation-containing cerium regenerating abrasive regenerated.
Fig. 3 is presented to carry out drying with bake oven type c drying machine in comparative example 1 and the chart of the size distribution of the oxidation-containing cerium regenerating abrasive regenerated.
Fig. 4 is the SEM photo of the regenerating abrasive obtained in example 2.
Fig. 5 is the SEM photo of the regenerating abrasive obtained in comparative example 2.
Detailed description of the invention
Disclose preferred embodiment below, to contribute to understanding the present invention, but the following example is just for illustrating the present invention, and the present invention is not limited thereto.
embodiment 1:oxidation-containing cerium gives up the regeneration of abrasive material
By oxidation-containing cerium (CeO
2) waste slurry is dissolved in and comprises in the solvent aqueous solution of hydrofluoric acid and NaOH with the concentration of 10M respectively.Then, to product centrifugal separator (ProductName: Supra22K, HANILSCI-MED company) carry out centrifugation and make Separation of Solid and Liquid, and waste slurry described in the washed with de-ionized water being adjusted to 7 by pH value, impurity silica and aluminium oxide etc. being derived from glass substrate is separated from described waste slurry and removes.
Then, use CD drying machine (ProductName: CD500, Geum San technical industry) under the rotating speed of 3rpm, with the temperature of 120 DEG C dry 10 seconds.After drying process, the moisture content confirming waste slurry becomes less than 1 % by weight.In addition, measure the size distribution after carrying out drying process with Particle Size Analyzer (ProductName: LA950, Hor iba), and illustrate with the black line of Fig. 2.And the particle mean size measurement result confirmed now is about 2.28 μm.
Then, described dried waste slurry sinters 2 hours and obtains the regenerating abrasive of embodiment 1 under existing by the ammonium fluoride 1 % by weight (weight relative to waste slurry initially to be regenerated) added in described cleaning at 850 DEG C.
embodiment 2:oxidation-containing cerium gives up the regeneration of abrasive material
Except being adjusted to except 7rpm by the rotating speed of CD drying machine, proceed to drying process by the method identical with embodiment 1.After drying process, the moisture content confirming waste slurry becomes less than 1 % by weight.In addition, measure the size distribution after carrying out drying process with Particle Size Analyzer (ProductName: LA950, Horiba), and illustrate with the red line of Fig. 2.And the particle mean size measurement result confirmed now is about 1.73 μm.
Then, carry out sintering process by the method identical with embodiment 1, thus obtain the regenerating abrasive of embodiment 2.
embodiment 3:oxidation-containing cerium gives up the regeneration of abrasive material
Except sintering temperature being adjusted to except 800 DEG C, obtained the regenerating abrasive of embodiment 3 by the method identical with embodiment 2.
embodiment 4:oxidation-containing cerium gives up the regeneration of abrasive material
Except adding ammonium fluoride 1.5 % by weight (weight relative to waste slurry initially to be regenerated) in cleaning, and carry out, outside sintering process, being obtained the regenerating abrasive of embodiment 4 by the method identical with embodiment 2 under ammonium fluoride exists.
embodiment 5:oxidation-containing cerium gives up the regeneration of abrasive material
NaOH 1.5 % by weight (weight relative to waste slurry initially to be regenerated) is added except substituting ammonium fluoride 1 % by weight in cleaning, and carry out, outside sintering process, being obtained the regenerating abrasive of embodiment 5 by the method identical with embodiment 2 under NaOH exists.
embodiment 6:oxidation-containing cerium gives up the regeneration of abrasive material
KOH1.5 % by weight (weight relative to waste slurry initially to be regenerated) is added except substituting ammonium fluoride 1 % by weight in cleaning, and carry out, outside sintering process, being obtained the regenerating abrasive of embodiment 6 by the method identical with embodiment 2 under KOH exists.
comparative example 1:oxidation-containing cerium gives up the regeneration of abrasive material
Use bake oven type c drying machine except alternative CD drying machine and at the temperature of 150 DEG C except dry 24 hours, proceed to drying process by the method identical with embodiment 1.After drying process, the moisture content confirming waste slurry becomes less than 1 % by weight.In addition, measure the size distribution after carrying out drying process with Particle Size Analyzer (ProductName: LA950, Horiba), and illustrate with the red line of Fig. 3.And the particle mean size measurement result confirmed now is about 6.34 μm, there is the bulky grain of a considerable amount of granularity more than 10 μm.
Then, described dried waste slurry sinters 2 hours and obtains the regenerating abrasive of comparative example 1 under existing by the ammonium fluoride 2 % by weight (weight relative to waste slurry initially to be regenerated) added in described cleaning at 850 DEG C.
comparative example 2:oxidation-containing cerium gives up the regeneration of abrasive material
Except not adding ammonium fluoride in described cleaning, under the state of fluoride-free ammonium, sintering temperature is adjusted to 950 DEG C sinter outside, obtained the regenerating abrasive of comparative example 2 by the method identical with embodiment 2.
Refer to particle mean size measurement result and Fig. 2 and 3 of described embodiment 1,2 and comparative example 1, for the embodiment 1 and 2 of carrying out drying process in waste slurry regenerative process with CD drying machine, the regenerating abrasive with fair average granularity can be obtained after drying, and confirm the oarse-grained generation of cut can be caused also greatly to reduce.Especially, be in the embodiment 2 of 7rpm at the rotating speed of CD drying machine, the cohesion between particle and the oarse-grained generation caused reduce more, and particle mean size can be optimized further.
In contrast, for the comparative example 1 carrying out drying process with bake oven type c drying machine, produce the cohesion between considerable particle in drying process, particle mean size becomes very large, and there is the bulky grain of a considerable amount of granularity more than 10 μm as shown in Figure 3.Therefore, when carrying out polishing with the regenerating abrasive obtained in comparative example 1, the possibility producing cut is high, or needs to carry out excessive pulverizing or grading technology, to reduce bulky grain.
In addition, for the regenerating abrasive obtained in embodiment 1 to 6, comparative example 1 and 2, by Sherrerequation (
) method measures crystal size, and measure the particle mean size of each regenerating abrasive with Particle Size Analyzer (ProductName: LA950, Horiba), also measures the polishing rate using described regenerating abrasive.Polishing rate is by measuring relative to the ratio of polishing rate before regeneration.The measurement result of crystal size, particle mean size and polishing rate is as shown in table 1 below.In addition, the SEM photo of the regenerating abrasive obtained in embodiment 2 and comparative example 2 shown in Fig. 4 and Fig. 5.
Table 1
* AF: ammonium fluoride
Refer to described table 1, the regenerating abrasive obtained in the embodiment 1 to 6 that drying condition and sintering condition are optimized, its particle mean size and crystal size, in preferable range, therefore demonstrate the polishing rate of the excellence being equivalent to new abrasive material.By contrast, the regenerating abrasive of comparative example 1 and 2 is owing to comprising bulky grain, so particle mean size is excessive or crystal size is excessive, polishing rate reduces on the contrary, and the possibility producing cut is high.
In addition, refer to Fig. 4 and Fig. 5, sintering temperature be optimized further and use the regenerating abrasive of the embodiment 2 of flux, demonstrating the preferred surface shape as abrasive material, and do not observe oarse-grained generation.By contrast, for the regenerating abrasive of comparative example 2, sintering temperature is higher and do not use flux, and observe oarse-grained generation, the possibility therefore producing cut is high.
Claims (16)
1. oxidation-containing cerium gives up a renovation process for abrasive material, comprises the following steps:
Oxidation-containing cerium waste slurry is dissolved in the solvent solution comprising highly basic and hydrofluoric acid;
Described oxidation-containing cerium waste slurry is cleaned, to remove silicon oxide-containing impurity;
Drying is carried out to described cleaned oxidation-containing cerium waste slurry CD drying machine; And
Comprise ammonium salt, alkali metal salt, metal oxide, metal oxygen-containing acid or alkali salt flux exist under, described waste slurry is sintered with the temperature of more than 800 DEG C.
2. oxidation-containing cerium according to claim 1 gives up the renovation process of abrasive material, wherein,
Oxidation-containing cerium waste slurry contains silica, aluminium oxide as impurity.
3. oxidation-containing cerium according to claim 1 gives up the renovation process of abrasive material, wherein,
Solvent solution is the aqueous solution comprising highly basic NaOH or potassium hydroxide and hydrofluoric acid.
4. oxidation-containing cerium according to claim 3 gives up the renovation process of abrasive material, wherein,
Described solvent solution comprises highly basic or hydrofluoric acid with the concentration of 0.01 to 20M respectively.
5. oxidation-containing cerium according to claim 1 gives up the renovation process of abrasive material, further comprising the steps of:
Before described cleaning or in described cleaning process, carry out Separation of Solid and Liquid by centrifugation, filtration or sedimentation.
6. oxidation-containing cerium according to claim 1 gives up the renovation process of abrasive material, wherein,
Described cleaning use pH value be adjusted to 1 to 4 or the pH value aqueous solvent that is adjusted to 10 to 14 carry out.
7. oxidation-containing cerium according to claim 1 gives up the renovation process of abrasive material, wherein,
The CD drying machine of described Dryly use 1 to 10rpm carried out for 1 to 30 second.
8. oxidation-containing cerium according to claim 7 gives up the renovation process of abrasive material, wherein,
Described flux comprises at least one be selected from ammonium fluoride, ammonium chloride, sodium chloride, sodium fluoride, NaOH, potassium hydroxide, potassium chloride, boric acid, Boratex, ammonium phosphate, ammonium sulfate, boron oxide and barium chloride.
9. oxidation-containing cerium according to claim 1 gives up the renovation process of abrasive material, wherein,
Described flux adds in cleaning.
10. oxidation-containing cerium according to claim 1 gives up the renovation process of abrasive material, wherein,
The addition of described flux is 1 to 1.5 % by weight relative to the weight of described waste slurry.
11. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, wherein,
Described sintering carries out at 800 to 900 DEG C.
12. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, wherein,
Described sintering carries out 1 to 4 hour.
13. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, wherein,
After described sintering, the oxidation-containing cerium regenerating abrasive obtained by the waste slurry after described sintering is pulverized and classification.
14. oxidation-containing ceriums according to claim 13 give up the renovation process of abrasive material, wherein,
Described pulverizing utilizes jet pulverizer to carry out, and described classification utilizes wind classification device, dry classification device, utilizes the EJ-ELBO grading plant of two limits or three limit Tip or carry out for the sieve of classification.
15. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, obtain the oxidation-containing cerium regenerating abrasive with the crystal size of 60 to 90nm and the particle mean size of 0.5 to 3.0 μm.
16. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, wherein,
Oxidation-containing cerium waste slurry is derived from for the oxidation-containing cerium abrasive material of polished glass substrate.
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| KR10-2013-0108822 | 2013-09-11 | ||
| PCT/KR2013/008221 WO2014042430A1 (en) | 2012-09-13 | 2013-09-11 | Method for regenerating spent ceria-containing polishing agent |
| KR1020130108822A KR101539420B1 (en) | 2012-09-13 | 2013-09-11 | Regenaration method of spent abrasives containing ceria |
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| KR101539420B1 (en) | 2015-08-06 |
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| JP5943529B2 (en) | 2016-07-05 |
| KR20140035264A (en) | 2014-03-21 |
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