CN104619433B - Oxidation-containing cerium gives up the renovation process of abrasive material - Google Patents
Oxidation-containing cerium gives up the renovation process of abrasive material Download PDFInfo
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- CN104619433B CN104619433B CN201380047642.0A CN201380047642A CN104619433B CN 104619433 B CN104619433 B CN 104619433B CN 201380047642 A CN201380047642 A CN 201380047642A CN 104619433 B CN104619433 B CN 104619433B
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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
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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
- 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)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (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 kind of oxidation-containing cerium give up the renovation process of abrasive material, can effectively remove oxidation-containing cerium to give up the impurity included in abrasive material, and be regenerated as demonstrating suitable particle size distribution and crystal size and the oxidation-containing cerium regenerating abrasive of preferable polishing rate etc. thus brought.Described oxidation-containing cerium gives up the renovation process of abrasive material, comprises the following steps: by oxidation-containing cerium (CeO2) waste slurry is dissolved in the solvent solution comprising highly basic and Fluohydric acid.；Described oxidation-containing cerium waste slurry is carried out, to remove silicon oxide-containing (SiO2) impurity；Described cleaned oxidation-containing cerium waste slurry CD drying machine is dried；And in the presence of the flux comprising ammonium salt, alkali metal salt, metal-oxide, metal oxygen-containing acid or alkali salt, described waste slurry is sintered with the temperature of more than 800 DEG C.
Description
Technical field
The present invention relates to a kind of oxidation-containing cerium give up the renovation process of abrasive material.More specifically, it is involved in the present invention
Oxidation-containing cerium give up the renovation process of abrasive material, that can effectively remove that oxidation-containing cerium gives up included in abrasive material is miscellaneous
Matter, and be regenerated as demonstrating suitable particle size distribution and crystal size and the preferable polishing thus brought
The oxidation-containing cerium regenerating abrasive of rate etc..
Background technology
Generally, as the TFT-LCD glass substrate etc. of teletube or liquid crystal panel, producing
During the bad state such as flatness or the roughness that can become surface, thus be difficult to direct for mother's glass
As teletube or glass substrate of liquid crystal panel.Especially for the TFT-LCD as liquid crystal panel
With face glass, studying various method to improve the brightness of product, visual angle, contrast etc., it is known that
These characteristics also can be by the biggest impact of TFT-LCD glass baseplate surface.Therefore, glass base is produced
The producer of plate makes great efforts to improve the surface of glass substrate, and uses various glass substrate abrasive material.Wherein,
Oxidation-containing cerium (CeO is widely used as conventional abrasive material2) abrasive material.
But, this oxidation-containing cerium abrasive material is after the glass polishing process of certain time, because of polishing effect
Rate reduction goes out of use and becomes waste slurry.This is because, after the polishing process of certain time, institute
The polishing efficiency stating abrasive material reduces, and there will be the cohesion between abrasive grain, results in a large amount of drawing
The risk of trace increases.Furthermore, the impurity being derived from polishing pad produced in polishing process can enter abrasive slurries
In, thus the probability resulting in cut increases further.
Therefore, needing discarded described abrasive material after using certain time in glossing, this can reduce technique
Efficiency or economy.To this end, studying several technology recycling described abrasive material.
But, for recycling and the renovation process of known oxidation-containing cerium abrasive material, due to the abrasive material of regeneration
Particle size distribution or the crystal size of granule are not optimized, so the polishing rate of regenerating abrasive is the most abundant
Or regenerative process produces the cohesion between granule and generates bulky grain etc., thus cause utilizing regeneration mill
The problems such as cut are produced when material is ground.
Summary of the invention
In view of this, the present invention provides the renovation process that a kind of oxidation-containing cerium gives up abrasive material, can effectively remove
Oxidation-containing cerium gives up the impurity included in abrasive material, and is regenerated as demonstrating suitable particle size distribution and crystallization chi
The oxidation-containing cerium regenerating abrasive of preferable polishing rate etc. that is very little and that thus bring.
The present invention provides the renovation process that a kind of oxidation-containing cerium gives up abrasive material, comprises the following steps: will contain oxidation
Cerium (CeO2) waste slurry is dissolved in the solvent solution comprising highly basic and Fluohydric acid.；Described oxidation-containing cerium is given up
Slurry is carried out, to remove silicon oxide-containing (SiO2) impurity；Described cleaned oxidation-containing cerium is given up
Slurry CD drying machine (Compact Di sc dreyer) is dried；And comprising ammonium salt, alkali
In the presence of the flux (flux) of the acid of slaine, metal-oxide, metal oxygen-containing or alkali salt,
Described waste slurry is sintered with the temperature of more than 800 DEG C.
Below, describe oxidation-containing cerium according to embodiments of the present invention in detail to give up the renovation process of abrasive material.
One embodiment of the invention provides the renovation process that a kind of oxidation-containing cerium gives up abrasive material, comprises the following steps:
Oxidation-containing cerium waste slurry is dissolved in the solvent solution comprising highly basic and Fluohydric acid.；Described oxidation-containing cerium is given up
Slurry is carried out, to remove silicon oxide-containing impurity；To described cleaned oxidation-containing cerium waste slurry CD
Drying machine is dried；And comprise ammonium salt, alkali metal salt, metal-oxide, metal oxygen-containing acid or
In the presence of the flux of alkali salt, 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 of useless abrasive material will be derived from
Waste slurry is dissolved in the solvent solution of regulation, uses and dissolves the impurity being derived from glass substrate etc., and passes through
Cleaning and remove after these impurity, drying and the sintering process abrasive material that can be given up by oxidation-containing cerium is regenerated as regeneration
Abrasive material.
Especially, in the renovation process of an embodiment, described drying process is to do in replacement conventional ovens formula
The CD drying machine of dry machine (Oven dryer) is carried out, and in sintering process, uses regulation
Flux carries out high temperature sintering such that it is able to make described oxidation-containing cerium give up abrasive material regeneration.
This dry and sintering process main purpose is to the solvent carried out to remove described impurity
Solution processes and in cleaning, the moisture of use is dried, and recovers the apparent condition of regenerating abrasive, and
Remove further be derived from polishing pad or attach pad (backpad) etc. impurity or metal impurities etc. other
Impurity.The present inventor test result indicate that, controlled as described above described dry and the condition of sintering process, energy
Enough more effectively remove pad (pad) impurity, and make the particle size distribution of regenerating abrasive and crystal size obtain
To optimize such that it is able to suppression regenerative process in abrasive grain between cohesion and thus cause big
Particles generation.
Further, use conventional ovens formula drying machine oven drying mode as step before need into
Row filter-pressing process (filter press), and need to carry out roller broken technique (roll as subsequent step
Crusher), it is thus possible to the cost of technology can be caused to increase and yield reduces.But, in an embodiment
In, substitute this oven drying mode by application CD drying machine, several steps can be merged into one
Step processes, it is also possible to improve yield.
Therefore, according to the renovation process of an embodiment, can effectively remove oxidation-containing cerium and give up abrasive material is wrapped
The impurity contained, and be regenerated as demonstrating suitable particle size distribution and crystal size and thus bringing relatively
Good polishing rate, reduces the oxidation-containing cerium regenerating abrasive of the cut produced because of bulky grain, thus realizes regeneration
And recycling.It can also efficiency and the yield of this regeneration technology is greatly improved.
Below, abrasive material is given up again by the oxidation-containing cerium of each step embodiment more particularly described below referring to the drawings
Generation method.Fig. 1 is to show that give up one of the renovation process of abrasive material of the oxidation-containing cerium of an embodiment shows by each step
The schematic diagram of example.
First, in the renovation process of an embodiment, as regeneration object oxidation-containing cerium give up abrasive material and
Consequent waste slurry, containing for polished glass substrate in manufacturing process that may originate from TFT-LCD etc.
Cerium oxide abrasives.Therefore, described oxidation-containing cerium waste slurry etc. can comprise as major impurity and are derived from glass base
Silicon oxide (the SiO of plate2) and aluminium oxide (Al2O3).And, described waste slurry or useless abrasive material are as miscellaneous
Matter may comprise the polishing pad being derived from through polishing or for supporting the attaching pad of polished glass substrate
Various Organic substances etc., it is also possible to comprise other metals such as ferrum (Fe), chromium (Cr) or nickel (Ni) and become
Point.
Therefore, when described oxidation-containing cerium waste slurry etc. is regenerated, need to carry out following technique: remove
These silicon oxides and aluminium oxide；It is derived from polishing pad described in removal, attaches pad etc. or containing its of metal ingredient
His impurity；And control the surface characteristic of oxidation-containing cerium abrasive material, particle size distribution and crystal size etc..
Refer to Fig. 1, in the renovation process of an embodiment, first can be by oxidation-containing cerium (CeO2) useless
Slurry is dissolved in the solvent solution comprising highly basic and Fluohydric acid..In this process, permissible as described highly basic
Use sodium hydroxide or potassium hydroxide etc., and these can dissolve described in be derived from the silicon oxide of glass substrate
Deng impurity.It addition, described Fluohydric acid. is the composition being mainly used as glass etching liquid, this can also dissolve
The impurity such as the described silicon oxide being derived from glass substrate or aluminium oxide.
Therefore, if described oxidation-containing cerium waste slurry to be scattered in the solvent solution comprising highly basic and Fluohydric acid.
Such as comprise in the solvent aqueous solution of the highly basic such as sodium hydroxide or potassium hydroxide and Fluohydric acid. and process, then
Comprising the impurity being derived from glass substrate such as silicon oxide or the aluminium oxide etc. in described waste slurry will be by solvent
Dissolve such that it is able to separate with described waste slurry.
Now, it is contemplated that the impurity content etc. such as silicon oxide included in described waste slurry or aluminium oxide, can
Suitably control the highly basic in described solvent solution and the concentration of Fluohydric acid..Simply, in order to from conventional LCD
It is miscellaneous with waste slurry used in the polishing of glass substrate removes described silicon oxide or aluminium oxide etc. effectively
The concentration of matter, described highly basic included in solvent solution and/or Fluohydric acid. is the most suitable be about 0.01 to
20M or about 0.1 to 15M or about 1 to 10M.If highly basic described in solvent solution and Fluohydric acid.
Concentration too low, go deimpurity efficiency to reduce.On the contrary, if described highly basic and the concentration of Fluohydric acid.
Too high, the usage amount of raw material will unnecessarily increase.
It addition, after described oxidation-containing cerium waste slurry is dissolved in the solvent solution of regulation, by cleaning this
Plant waste slurry, silicon oxide-containing impurity can be removed from waste slurry.Now, before described cleaning
Or during being carried out technique, it is also possible to include the waste slurry that will process through described solvent solution
By centrifugation, filter or the method such as sedimentation carries out the solid-liquid separation process that processes.
When carrying out this solid-liquid separation process, described waste slurry and the oxygen being dissolved in described solvent solution
The glass substrate impurities such as SiClx or aluminium oxide by solid-liquid separation, and then can will divide from described waste slurry
From and go the removal of impurity, and by carrying out utilizing the cleaning of deionized water, water or other aqueous solvents,
Can the most thoroughly remove described impurity.
Now, described centrifugation, filter or the technique such as sedimentation can be carried out by the following method: pass through
Conventional centrifugal separation process, separates deimpurity oxidation-containing cerium waste slurry and the liquid containing impurity
Composition (centrifugal separation process)；Or go deimpurity oxidation-containing cerium waste slurry to settle described in making, to divide
Separate out the liquid component (sedimentation process) containing impurity；Or use filter etc., go remove impurity from described
The oxidation-containing cerium waste slurry of matter filters and isolates the liquid component (filtering technique) containing impurity.Certainly,
These centrifugations can also be used, filter or settle at least two combination.
Additionally, in the cleaning utilizing described aqueous solvent, in order to more effectively clean and remove dissolving
Impurity in described solvent solution, can use pH value be adjusted to 1 to 4 or pH value be adjusted to 10
To the aqueous solvent of 14.In order to suitably regulate pH value, can by acid or alkali suitably be dissolved in described water or
In deionized water, for use as cleanout fluid.
And, in this cleaning, described waste slurry to be regenerated can add following sintering process
The middle flux that can use.
It addition, as it is shown in figure 1, after carrying out described cleaning, cleaned oxidation-containing cerium can be given up
Slurry CD drying machine is dried.In this drying process, can will be used at described solvent solution
The moisture of science and engineering skill and cleaning goes deimpurity waste slurry to be dried removal from described, is so dried
Technique, can make waste slurry have below about 1 weight % or the moisture content of about 0 to 1 weight %.
Especially, in the renovation process of an embodiment, described drying process can use tray drier it
The CD drying machine of one is dried.This CD drying machine be a kind of on heat supply rotating disk to described useless slurry
The tray drier that material is dried, uses this CD to be dried function and suppresses the abrasive material in described drying process
Cohesion between granule (such as, cerium oxide particle), therefore suppresses oarse-grained generation, and then uses
The generation of cut can be suppressed during the oxidation-containing cerium abrasive material regenerated.And, by using this CD drying machine
Can effectively be dried technique.Because being dried in described CD drying machine, can be to described useless
Slurry is efficient, Transmit evenly heat.
When being dried with described CD drying machine, can be with about 1 to 10rpm or about 5 to 10rpm
Or on the CD drying machine that the speed of about 6 to 9rpm rotates, carry out with the temperature of about 100 to 200 DEG C
About 1 to 30 second.If the rotating speed of described CD drying machine crosses slow or drying time is long, because of granule it
Between occur that cohesion produces the risk of cut and will increase.On the contrary, if rotating speed is too fast or mistake drying time
Short, drying process is it is possible to will not effectively carry out.
During in contrast, be dried with CD drying machine with optimal conditions, the oxidation-containing cerium of regeneration is again
Raw abrasive material can have the suitable particle mean size of about 0.5 to 3.0 μm, and suppresses the big of more than about 6.0 μm
The generation of granule, the risk not only producing cut reduces, and also can effectively be dried, thus can be easy to
Obtain moisture content and be about the regenerating abrasive of below 1 weight %.
It addition, after carrying out described drying process, as shown in Figure 1 can comprise ammonium salt, alkali metal salt,
In the presence of the flux of the acid of metal-oxide, metal oxygen-containing or alkali salt, to described dried useless
Slurry is sintered with the temperature of more than about 800 DEG C.By carrying out this sintering process, it is included in useless slurry
Surface characteristic and the crystallization property of the oxidation-containing cerium abrasive material in material are restored, thus the polishing of regenerating abrasive
Rate can be improved, and can remove other impurity, for example originating from the polishing pad through polishing or use
In support polished glass substrate attach pad various Organic substances, or ferrum (Fe), chromium (Cr) or
Nickel (Ni) etc. are containing metal ingredient impurity etc..
Especially, when using described specific flux, after carrying out described sintering process, described regeneration mill
The surface characteristic of material or crystallization property etc. can control in the range of preferably.As a result, the grain of regenerating abrasive
Degree distribution and crystal size can control in proper range, and can suppress oarse-grained generation.
During it is more preferable that use this flux, use about 1 relative to the weight of described waste slurry
To the described flux of 1.5 weight %, and the temperature of described sintering process is controlled at about 800 to 900 DEG C
Scope, so can make the particle size distribution of regenerating abrasive and crystal size more optimize.More specifically, at this
It is sintered technique, the particle size distribution of described regenerating abrasive and crystal size under the conditions of Zhong will be separately optimized
It is 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,
And oarse-grained generation can be suppressed, thus the polishing rate of regenerating abrasive is controlled as outstanding and permissible
Suppression bulky grain generates the generation of the cut caused.
Accordingly, it is capable to preferably use the regenerating abrasive obtained by the method for an embodiment.
In described sintering process, described flux can be by ammonium fluoride, ammonium chloride, ammonium phosphate or sulphuric acid
The ammonium salts such as ammonium；Sodium chloride, sodium fluoride, sodium hydroxide, potassium hydroxide, potassium chloride, sodium borate or chlorination
The alkali metal salts such as barium or alkali salt；The metal-oxides such as boron oxide；Or boric acid (H3BO3) etc.
Metal oxygen-containing acid forms, it is also possible to be used together at least two in these compounds.Use this
During flux, after carrying out described sintering process, the surface characteristic of described regenerating abrasive or crystallization property
Etc. can control in the range of preferably, and then the particle size distribution of regenerating abrasive and crystal size can be controlled in suitably
In the range of.
And, as it has been described above, described flux can add in the cleaning step carried out before and wet type
Mixing, or dry type mixing can also be given before sintering process, wherein suitable in cleaning step wet type
Mixing.Described sintering step can be carried out about 1 to 4 hour at a temperature of described.
By carrying out the sintering process of described optimization, it is possible to obtain have the crystal size of about 60 to 90nm
And about 0.5 to 3.0 particle mean size of μm, and the oxidation-containing cerium of optimization that oarse-grained formation is inhibited
Regenerating abrasive.If described crystal size or particle mean size are too small, the polishing rate of regenerating abrasive may be not
Fully.On the contrary, if crystal size or particle mean size are excessive, using can in the glossing of regenerating abrasive
Pulverizing and the grading technology that can carry out as required after producing cut, or sintering process may become
Obtain non-efficient activity.Especially, in order to reduce excessive granularity or crystal size, carry out excessively pulverizing and dividing
During level technique, not only the efficiency of regeneration technology can be greatly reduced, and carries out the mistake of this disintegrating process etc.
In journey, the surface characteristic of regenerating abrasive on the contrary can be impaired, and the characteristic being likely to result in regenerating abrasive reduces.
It addition, after carrying out described sintering process, divide to reduce the granularity of regenerating abrasive as required
Cloth or crystal size or remove bulky grain, can carry out pulverizing or grading technology further, and this powder
Broken and grading technology can be carried out by the well-known method of those skilled in the art.Such as, institute
Stating disintegrating process can use jet pulverizer (jet-mill) etc. to carry out, and described grading technology can make
With the wind classification devices such as cyclone separator, dry classification device, utilize two limits or three limits Tip
EJ-ELBO grading plant or the sieve for classification are carried out.
According to described renovation process, can obtain be derived from the impurity of glass substrate etc. substantially by thoroughly, have
Effect ground is removed, and demonstrates crystal size and the particle size distribution of optimization, and oarse-grained generation pulverizing and
Also the oxidation-containing cerium regenerating abrasive being inhibited before grading technology.Therefore, this oxidation-containing cerium regeneration mill
Material can be used alone or is used together with new abrasive material, thus is reused for polishing LCD glass base
Plates etc., the economy and yield that improve technique can be made a significant contribution by this.
Oxidation-containing cerium according to the present invention gives up the renovation process of abrasive material, can effectively remove the useless mill of oxidation-containing cerium
Impurity included in material, and it is regenerated as demonstrating suitable particle size distribution and crystal size and thus
The preferable polishing rate brought, reduces 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 to show that the oxidation-containing cerium of an embodiment gives up one of the renovation process example of abrasive material by each step
Schematic diagram.
It is oxygen-containing that Fig. 2 is shown in being dried with CD drying machine in embodiment 1 and 2 and is regenerated
Change the chart of the particle size distribution of cerium regenerating abrasive.
What Fig. 3 was shown in being dried with baking box drier in comparative example 1 and was regenerated contains oxidation
The chart of the particle size distribution of cerium regenerating abrasive.
Fig. 4 is the SEM photograph of the regenerating abrasive obtained in example 2.
Fig. 5 is the SEM photograph of the regenerating abrasive obtained in comparative example 2.
Detailed description of the invention
Preferred embodiment disclosed below, in order to contribute to understanding the present invention, but the following example is only intended to
Illustrate the present invention, the invention is not limited in this.
Embodiment 1:Oxidation-containing cerium gives up the regeneration of abrasive material
By oxidation-containing cerium (CeO2) waste slurry is dissolved in and comprises Fluohydric acid. and hydrogen-oxygen with the concentration of 10M respectively
Change in the solvent aqueous solution of sodium.Then, to product centrifugal separator (ProductName: Supra22K, HANIL
SCI-MED company) it is centrifuged separation and makes solid-liquid separation, and the deionized water of 7 it is adjusted to pH value
Cleaning described waste slurry, the impurity that silicon oxide and aluminium oxide etc. are derived from glass substrate divides from described waste slurry
From and remove.
Then, use CD drying machine (ProductName: CD500, Geum San technical industry) at 3rpm
Rotating speed under, be dried 10 seconds with the temperature of 120 DEG C.After drying process, confirm containing of waste slurry
Water rate becomes below 1 weight %.It addition, survey with Particle Size Analyzer (ProductName: LA950, Hor iba)
Measure the particle size distribution after being dried technique, and illustrated with the black line of Fig. 2.And, confirm now
Particle mean size measurement result be about 2.28 μm.
Then, ammonium fluoride 1 weight % added in described cleaning is (relative to the most to be regenerated
The weight of waste slurry) in the presence of, described dried waste slurry is sintered 2 hours at 850 DEG C and
Obtain the regenerating abrasive of embodiment 1.
Embodiment 2:Oxidation-containing cerium gives up the regeneration of abrasive material
In addition to the rotating speed of CD drying machine is adjusted to 7rpm, entered by method same as in Example 1
Walk to drying process.After drying process, the moisture content confirming waste slurry becomes below 1 weight %.Separately
Outward, the granularity after being dried technique is measured with Particle Size Analyzer (ProductName: LA950, Horiba)
Distribution, and illustrate with the red line of Fig. 2.And, confirm particle mean size measurement result now and be about 1.73
μm。
Then, it is sintered technique by method same as in Example 1, thus obtains embodiment 2
Regenerating abrasive.
Embodiment 3:Oxidation-containing cerium gives up the regeneration of abrasive material
In addition to sintering temperature is adjusted to 800 DEG C, implemented by method same as in Example 2
The regenerating abrasive of example 3.
Embodiment 4:Oxidation-containing cerium gives up the regeneration of abrasive material
Except cleaning being added ammonium fluoride 1.5 weight % (relative to waste slurry the most to be regenerated
Weight), and be sintered in the presence of ammonium fluoride outside technique, by method same as in Example 2
Obtain the regenerating abrasive of embodiment 4.
Embodiment 5:Oxidation-containing cerium gives up the regeneration of abrasive material
Sodium hydroxide 1.5 weight % is added (relatively except cleaning substitutes ammonium fluoride 1 weight %
Weight in waste slurry the most to be regenerated), and be sintered in the presence of sodium hydroxide outside technique,
The regenerating abrasive of embodiment 5 is obtained by method same as in Example 2.
Embodiment 6:Oxidation-containing cerium gives up the regeneration of abrasive material
KOH1.5 weight % is added (relative to initially except cleaning substitutes ammonium fluoride 1 weight %
The weight of waste slurry to be regenerated), and be sintered in the presence of KOH outside technique, by with enforcement
The method that example 2 is identical obtains the regenerating abrasive of embodiment 6.
Comparative example 1:Oxidation-containing cerium gives up the regeneration of abrasive material
Use baking box drier except substituting CD drying machine and be dried 24 hours at a temperature of 150 DEG C
Outside, carried out to drying process by method same as in Example 1.After drying process, confirm
The moisture content of waste slurry becomes below 1 weight %.It addition, with Particle Size Analyzer (ProductName: LA950,
Horiba) measure the particle size distribution after being dried technique, and illustrate with the red line of Fig. 3.And,
Confirm particle mean size measurement result now and be about 6.34 μm, there is a considerable amount of granularity more than 10
The bulky grain of μm.
Then, ammonium fluoride 2 weight % added in described cleaning is (relative to the most to be regenerated
The weight of waste slurry) in the presence of, described dried waste slurry is sintered 2 hours at 850 DEG C and
Obtain the regenerating abrasive of comparative example 1.
Comparative example 2:Oxidation-containing cerium gives up the regeneration of abrasive material
Except in described cleaning without ammonium fluoride, when fluoride-free ammonium by sintering temperature
Be adjusted to 950 DEG C be sintered outside, obtained the regeneration of comparative example 2 by method same as in Example 2
Abrasive material.
Refer to described embodiment 1,2 and the particle mean size measurement result of comparative example 1 and Fig. 2 and 3,
For being dried the embodiment 1 and 2 of technique in waste slurry regenerative process with CD drying machine, it is dried
After can obtain the regenerating abrasive with fair average granularity, and confirm and can cause the oarse-grained of cut
Generate and be also greatly reduced.Especially, in the embodiment that rotating speed is 7rpm 2 of CD drying machine, granule it
Between cohesion and the oarse-grained generation that causes more reduce, particle mean size can be optimized further.
In contrast, for the comparative example 1 being dried technique with baking box drier, at drying process
Cohesion between the considerable granule of middle generation, particle mean size becomes very large, and deposits as shown in Figure 3
In a considerable amount of granularities more than the bulky grain of 10 μm.Therefore, with the regenerating abrasive obtained in comparative example 1
When being polished, the probability producing cut is high, or needs to carry out excessive pulverizing or grading technology,
To reduce bulky grain.
It addition, for the regenerating abrasive obtained in embodiment 1 to 6, comparative example 1 and 2, pass through Sherrer
equation() method measures crystal size, and with Particle Size Analyzer (ProductName: LA950,
Horiba) measure the particle mean size of each regenerating abrasive, also measure the polishing using described regenerating abrasive
Rate.Polishing rate is by measuring relative to the ratio of polishing rate before regeneration.Crystal size, average particle
The measurement result of degree and polishing rate is as shown in table 1 below.It addition, in embodiment 2 shown in Fig. 4 and Fig. 5
And the SEM photograph of regenerating abrasive that comparative example 2 obtains.
Table 1
* AF: ammonium fluoride
Refer to described table 1, in drying condition and sintering condition obtain the embodiment 1 to 6 optimized
The regenerating abrasive arrived, its particle mean size and crystal size are in the range of preferably, thus it is shown that be equivalent to new
The excellent polishing rate of abrasive material.By contrast, the regenerating abrasive of comparative example 1 and 2 owing to comprising bulky grain,
So particle mean size is excessive or crystal size is excessive, polishing rate reduces on the contrary, and produce cut can
Can property height.
Additionally, refer to Fig. 4 and Fig. 5, sintering temperature is optimized further and is used flux
The regenerating abrasive of embodiment 2, demonstrate 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 does not has
Using flux, it was observed that oarse-grained generation, the probability therefore producing cut is high.
Claims (15)
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 Fluohydric acid.；
Described oxidation-containing cerium waste slurry is carried out, to remove silicon oxide-containing impurity；
Described cleaned oxidation-containing cerium waste slurry CD drying machine is dried；And
Comprising more than one selected from ammonium fluoride, ammonium chloride, sodium chloride, sodium fluoride, sodium hydroxide, hydroxide
The flux of potassium, potassium chloride, boric acid, sodium borate, ammonium phosphate, ammonium sulfate, boron oxide and barium chloride exists
Under, described waste slurry is sintered with the temperature of more than 800 DEG C.
Oxidation-containing cerium the most according to claim 1 gives up the renovation process of abrasive material, wherein,
Oxidation-containing cerium waste slurry contains silica, aluminium oxide as impurity.
Oxidation-containing cerium the most according to claim 1 gives up the renovation process of abrasive material, wherein,
Solvent solution is the aqueous solution comprising highly basic sodium hydroxide or potassium hydroxide and Fluohydric acid..
Oxidation-containing cerium the most according to claim 3 gives up the renovation process of abrasive material, wherein,
Described solvent solution comprises highly basic and Fluohydric acid. with the concentration of 0.01 to 20M respectively.
Oxidation-containing cerium the most 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, by centrifugation, filter or settle and carry out solid-liquid
Separate.
Oxidation-containing cerium the most according to claim 1 gives up the renovation process of abrasive material, wherein,
Described clean use pH value be adjusted to 1 to 4 or pH value be adjusted to the aqueous solvent of 10 to 14 and carry out.
Oxidation-containing cerium the most according to claim 1 gives up the renovation process of abrasive material, wherein,
The CD drying machine of described dry use 1 to 10rpm is carried out 1 to 30 second.
Oxidation-containing cerium the most according to claim 1 gives up the renovation process of abrasive material, wherein,
Described flux adds in cleaning.
Oxidation-containing cerium the most according to claim 1 gives up the renovation process of abrasive material, wherein,
The addition of described flux is 1 to 1.5 weight % relative to the weight of described waste slurry.
Oxidation-containing cerium the most according to claim 1 gives up the renovation process of abrasive material, wherein,
Described sintering is carried out at 800 to 900 DEG C.
11. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, wherein,
Described sintering is carried out 1 to 4 hour.
12. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, wherein,
After described sintering, the waste slurry after described sintering the oxidation-containing cerium regenerating abrasive obtained is carried out powder
Broken and classification.
13. oxidation-containing ceriums according to claim 12 give up the renovation process of abrasive material, wherein,
Described pulverizing is to utilize jet pulverizer to carry out, and described classification is to utilize wind classification device, dry type
Grading plant, utilize the EJ-ELBO grading plant of two limits or three limits Tip or for the sieve of classification
Carry out.
14. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, it is thus achieved that have 60 to 90nm
Crystal size and the oxidation-containing cerium regenerating abrasive of particle mean size of 0.5 to 3.0 μm.
15. oxidation-containing ceriums according to claim 1 give up the renovation process of abrasive material, wherein,
Oxidation-containing cerium waste slurry is derived from the oxidation-containing cerium abrasive material having been used for polished glass substrate.
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| Application Number | Priority Date | Filing Date | Title |
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| KR10-2012-0101731 | 2012-09-13 | ||
| KR20120101731 | 2012-09-13 | ||
| 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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| JPS5310168A (en) * | 1976-07-16 | 1978-01-30 | Daia Shinkuu Giken Kk | Vacuum concentrating or drying machine |
| JP3134189B2 (en) * | 1997-09-18 | 2001-02-13 | 福島県 | How to collect abrasives |
| JP3413394B2 (en) * | 2000-07-18 | 2003-06-03 | 細川 澄男 | Method for recovering cerium oxide from cerium oxide abrasive waste liquid for optical polishing and method for eliminating pollution from cerium oxide abrasive waste liquid for optical polishing |
| CN1433965A (en) * | 2003-02-28 | 2003-08-06 | 张启修 | Method for preparing cerium oxide having defferent shape and graininess by reduction-precipitation stripping |
| JP2004268215A (en) * | 2003-03-10 | 2004-09-30 | Fujitsu Hitachi Plasma Display Ltd | Regenerating method of abrasive |
| JP4729428B2 (en) * | 2006-04-07 | 2011-07-20 | Ａｇｃセイミケミカル株式会社 | Regeneration method of cerium-based abrasive |
| CN101500754A (en) * | 2006-08-16 | 2009-08-05 | 旭硝子株式会社 | Method of recovering abrasive from abrasive slurry waste liquid and apparatus therefor |
| KR101450865B1 (en) * | 2006-10-24 | 2014-10-14 | 동우 화인켐 주식회사 | Reproduction method of spent abrasives for polishing a glass panel for display |
| JP2008228662A (en) * | 2007-03-20 | 2008-10-02 | Kubota Corp | Raising seedling box carrying device |
| JP2008241235A (en) * | 2007-10-29 | 2008-10-09 | Suntory Ltd | Slurry drying machine |
| WO2011099197A1 (en) * | 2010-02-15 | 2011-08-18 | 三井金属鉱業株式会社 | Cerium-based abrasive regeneration method |
| KR101245276B1 (en) * | 2010-03-12 | 2013-03-19 | 주식회사 엘지화학 | Method for recycling Cerium oxide abrasive |
| KR101225746B1 (en) * | 2010-08-03 | 2013-02-15 | 주식회사 랜코 | Method of recycling cerium oxide abrasive material |
| CN101983925B (en) * | 2010-11-08 | 2012-07-18 | 东北大学 | Preparation method of cerium oxide powder |
| KR101051207B1 (en) * | 2011-02-09 | 2011-07-21 | 윤종훈 | Recycling mineral abrasive for lcd and pdp glass panel based on rare earth metal oxides and method for recycling mineral abrasive using sludge disposal |
| JP2013086204A (en) * | 2011-10-17 | 2013-05-13 | Shinryo Corp | Method for reproducing cerium oxide-based abrasive slurry and reproduced cerium oxide-based abrasive slurry |
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| JP5943529B2 (en) | 2016-07-05 |
| KR20140035264A (en) | 2014-03-21 |
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