CN110407564A - Micro crystal wearable ball brick and its processing method - Google Patents
Micro crystal wearable ball brick and its processing method Download PDFInfo
- Publication number
- CN110407564A CN110407564A CN201910691221.0A CN201910691221A CN110407564A CN 110407564 A CN110407564 A CN 110407564A CN 201910691221 A CN201910691221 A CN 201910691221A CN 110407564 A CN110407564 A CN 110407564A
- Authority
- CN
- China
- Prior art keywords
- equal
- ball
- brick
- content
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3215—Barium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
Abstract
The present invention relates to wear-resistant ball brick technical fields, more particularly to micro crystal wearable ball brick and its processing method, recipe ingredient and mass percent are as follows: No.1 bauxite 44%-58%, No. two bauxites 12%-27%, No. three bauxite 3%-14%, alumina raw material 6%-13%, barium carbonate raw material 1%-5%, Luoyang soil 8%-12%, give up brick 0%-7%, adjustment material 2%-12%；Al in No.1 bauxite2O3Content is more than or equal to 78%, is less than or equal to 84%；Al in No. two bauxites2O3Content is more than or equal to 73%, is less than or equal to 78%；Al in No. three bauxites2O3Content is more than or equal to 67%, is less than or equal to 73%；The purity of barium carbonate raw material is more than or equal to 95%；The purity of alumina raw material is more than or equal to 99.6%；Al in the soil of Luoyang2O3Content is more than or equal to 50%, is less than or equal to 58%；SiO in the soil of Luoyang2Content is more than or equal to 33%, is less than or equal to 38%；Adjustment material is for adjusting Al in this formula2O3Total content is in 70%-79%, and ball brick molding rule, for close structure than great, water imbibition is extremely low, and firm wear-resisting, abrasion is low, has excellent performance.
Description
Technical field
The present invention relates to wear-resistant ball brick technical fields, and in particular to micro crystal wearable ball brick and its processing method.
Background technique
Microcrystalline alumina wear-resistant material particularly may be divided into high aluminium profiles and the big type of middle aluminium profiles two, and high aluminium profiles microcrystalline alumina is resistance to
Mill material refers to Al2O3Content is higher, and sintering temperature is higher, has excellent performance, and is usually used in ceramics, high-temperature crucibles, fire resisting boiler tube
Equal fields；And middle aluminium profiles microcrystalline alumina wear-resistant material refers to Al2O3Content is lower, and sintering temperature is relatively low, performance and height
Aluminium profiles since its manufacturing cost is lower, is also widely used compared to poor, is mainly used for the industries such as mine.
Microcrystalline alumina wear-resistant material is a kind of novel alumina base wear-resistant material, maintains the high rigidity of corundum and wear-resisting
Feature, while the advantages of having very high toughness again, changing the crisp and frangible disadvantage of corundum, aoxidize aluminium material is anti-invades
Corrosion is high, the porosity is low, is widely used in wear-resisting resistance to material and flame-proof thermal insulation material industry, existing alumina brick difficult forming,
Difficulty is fired, not regular enough molded appearance, wearability, corrosion resistance and hardness can not meet the requirement of client,
Specific gravity is small, and usage experience is very poor, and alumina balls brick yield rate is low.
Summary of the invention
The purpose of the present invention is to provide a kind of micro crystal wearable ball brick and its processing methods, pass through exclusive formula and processing
Method, the microcrystalline structure's structure generated inside micro crystal wearable ball brick solve that common wear-resistant ball brick specific gravity is small, and difficult forming is burnt
System is difficult, and appearance molding is not regular enough, wears no resistance, the problem that corrosion resistance and hardness are poor.
In order to solve the above technical problems, the invention adopts the following technical scheme: micro crystal wearable ball brick, recipe ingredient and matter
Measure percentage are as follows: including No.1 bauxite 44%-58%, No. two bauxites 12%-27%, No. three bauxite 3%-
14%, alumina raw material 6%-13%, barium carbonate raw material 1%-5%, Luoyang soil 8%-12%, give up brick 0%-7%, adjustment material 2%-12%；Its
In: the Al in the No.1 bauxite2O3Content is more than or equal to 78%, is less than or equal to 84%；In No. two bauxites
Al2O3Content is more than or equal to 73%, is less than or equal to 78%；Al in No. three bauxites2O3Content is more than or equal to 67%,
Less than or equal to 73%；The purity of the barium carbonate raw material is more than or equal to 95%；The purity of the alumina raw material is more than or equal to
99.6%；Al in the Luoyang soil2O3Content is more than or equal to 50%, is less than or equal to 58%；SiO in the Luoyang soil2Content is big
In being equal to 33%, it is less than or equal to 38%；The adjustment material is for adjusting Al in this formula2O3Total content is in 70%-79%.
1, further technical solution is: including the SiO of 8%-12% in the No.1 bauxite2, the K of 1%-3%2O,
The Na of 0.1%-3%2The miscellaneous material of O and 2%-8%；It include the SiO of 12%-14% in No. two bauxites2, 1.1%-1.7%'s
K2The Na of O, 0.1%-1.7%2The miscellaneous material of O and 8%-12%；It include the SiO of 14%-16% in No. three bauxites2,
The K of 0.6%-1.0%2The Na of O, 0.1%-1.0%2The miscellaneous material of O and 12%-18%.
Further technical solution is: the Luoyang soil includes the K of 1%-3%2The Na of O, 2%-4%2The miscellaneous material of O and 4%-8%.
Further technical solution is: the adjustment material is No. four bauxites, in No. four bauxites
Al2O3Content is greater than 28%.
Further technical solution is: the processing method of micro crystal wearable ball brick, successively the following steps are included:
Raw material is broken: each raw material in above-mentioned micro crystal wearable ball brick formula is crushed, after material was crushed 10 meshes, and each original
Material stores classifiedly；
Feedstock assay: above-mentioned broken each raw material is chemically examined, and identifies ingredient and content；
Ingredient: each raw material after above-mentioned chemical examination carries out ingredient according to the recipe ingredient of the micro crystal wearable ball brick；
It is primary to crush: after ingredient, to be crushed, raw material smashes it through 250 meshes, and it is that crushing is qualified that surplus, which is less than or equal to 4%,；
Primary aging: according to mass percent, it is 35%-40% that primary smashed qualified material, which adds water to water content, uniformly mixed
It is mixture after conjunction, it is 22-26 hours aging；
Separating twice: to it is primary it is aging after mixture carry out separating twice, the mixture after separating twice crosses 500 meshes, sieves
Lower object is qualified mixture；
Secondary aging: the qualified mixture after separating twice carries out secondary 48-52 hours aging；
Finished product is washed and starched: it is secondary it is aging after mixture cross the laggard finished pulp wash pool of 180 meshes, and add the dispersing agent of 3%-10%
With the forming agent of 1%-3%；
Be granulated: the final product mix in finished pulp wash pool enters spray drying tower and is granulated, the temperature control of spray drying tower
At 350 DEG C -450 DEG C；
Gradation: the particle that above-mentioned spray drying tower generates respectively enters feed bin, 20 mesh-of -20 mesh of 10 mesh by classifying screen
The feed bin more than feed bin of 30 mesh and 60 mesh is stored；
Aging three times: the particle in each feed bin is 48-52 hours aging, and pellet moisture is controlled in 8%-12%；
The molding of ball brick: the molding of ball brick: the particle after aging three times enters ball press compacting balling-up embryo, and ball press provides operating pressure
For equal static pressure 50Mpa-70Mpa, the pressure brick time is 35-60 seconds；
Semi-finished product pick up choosing: being screened by ball embryo forming standard, qualified ball embryo is stored in semifinished product warehouse.
Fire: by qualified ball embryo loading of kiln, preheating, firing and cooling three phases are completed to fire；Warm-up phase: kiln temperature
1150-1250 DEG C was risen to by 10.2-12.2 hours；The firing stage: kiln temperature rose to 1350- by 17.5-20.4 hours
1450℃；Cooling stage: kiln temperature was cooled to ambient temperature by 20-22 hours.
Finished product picks up choosing: being screened by ball brick molding standard, qualified ball brick is packed.
Further technical solution is: the semi-finished product pick up the unqualified ball embryo of choosing and the finished product picks up the unqualified ball of choosing
Brick is classified as useless brick.
Further technical solution is: being fired using tunnel oven to the ball base of compression moulding in the firing step.
Compared with prior art, the present invention can at least reach one of following beneficial effect:
1, micro crystal wearable ball brick proposed by the invention, the micro crystal wearable ball brick structure is close, and than great, water imbibition is extremely low,
Microstructure, which can be formed, in inside after raw material is fired keep its firm wear-resisting, wear it is low, by high-temperature process and inner material
Chemical reaction ensure that the corrosion resistance of micro crystal wearable ball brick, and shape molding rule when pressing brick, the micro crystal wearable ball brick is as resistance to
Fiery thermal insulation material is with good performance.
2, the processing method of micro crystal wearable ball brick proposed by the invention, No.1 bauxite, No. two aluminium in this method
Bauxite clinker and No. three bauxites are as primary raw material, convenient for obtaining, and it is at low cost；A small amount of adjustment material aluminium is utilized simultaneously
Bauxite clinker and high purity aluminium oxide adjust Al in this micro crystal wearable ball brick formula material2O3Overall content, saved raw material at
This.After raw material proportioning, powder is worn into, and carries out aging after being mixed, be can be improved, enhance plasticity, reduced molding and burn
Cracking when processed carries out tunnel oven firing after compression moulding, realize micro mist molding, produce the wear-resistant ball with microstructure
Brick, and specific gravity is moderate, the far smaller than common middle aluminium wear-resistant ball brick of abrasion.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
One aspect of the present invention provides micro crystal wearable ball brick:
Micro crystal wearable ball brick, recipe ingredient and mass percent are as follows: including No.1 bauxite 44%-58%, No. two bauxites
Clinker 12%-27%, No. three bauxite 3%-14%, alumina raw material 6%-13%, barium carbonate raw material 1%-5%, Luoyang soil 8%-
12%, give up brick 0%-7%, adjustment material 2%-12%；Wherein: the Al in the No.1 bauxite2O3Content is small more than or equal to 78%
In equal to 84%；Al in No. two bauxites2O3Content is more than or equal to 73%, is less than or equal to 78%；No. three aluminium alum
Al in native clinker2O3Content is more than or equal to 67%, is less than or equal to 73%；The purity of the barium carbonate raw material is more than or equal to 95%；Institute
The purity for stating alumina raw material is more than or equal to 99.6%；Al in the Luoyang soil2O3Content is more than or equal to 50%, is less than or equal to
58%；SiO in the Luoyang soil2Content is more than or equal to 33%, is less than or equal to 38%；The adjustment material is for adjusting in this formula
Al2O3Total content is in 70%-79%.
Each raw material accounting in inventive formulation group:
No.1 bauxite, No. two bauxites and No. three bauxites: internal main for bauxite calcination of chamotte
Ingredient is diaspore and high alumina silica, has good high temperature resistant property, is mainly used for adjusting Al in this formula2O3Content is convenient for
The formation of crystallite when firing.
The typical but non-limiting mass percent of No.1 bauxite is, for example: 44%, 48%, 52%, 55%, 58%；
No. two typical but non-limiting mass percents of bauxite are, for example: 12%, 16%, 20%, 24%, 27%；
No. three typical but non-limiting mass percents of bauxite are, for example: 3%, 6%, 9%, 11%, 14%；
Alumina raw material is mainly high-purity alpha-alumina, is a kind of high hardness compound, and the ion that can be ionized at high temperature is brilliant
Body is mainly used for adjusting Al in this formula in the present invention2O3Content, the formation of crystallite when convenient for firing.
The typical but non-limiting mass percent of alumina raw material is, for example: 6%, 8%, 10%, 12%, 13%；
Barium carbonate raw material is high-pruity barium carbonate, hexagon micro crystal or white powder, is insoluble in water, when processing, be can promote micro-
Crystalline substance is formed, and the wearability of this micro crystal wearable ball brick is promoted.
The typical but non-limiting mass percent of barium carbonate raw material is, for example:
Luoyang soil: Luoyang soil is a kind of domestic hard kaoline in Luoyang City, and the main component in the soil of Luoyang is Al2O3
And SiO2, Al2O3Content is more than or equal to 50%, is less than or equal to 58%；SiO2Content is more than or equal to 33%, is less than or equal to 38%；Favorably
Plastic type, fire resistance, associativity and viscosity when improving the processing of this micro crystal wearable ball brick, while being conducive to crystallite when firing
It is formed, promotes wearability, staff can be with mixing with fluxing raw material and different types of kaolin mixed to the side matched in proportion
Method controls sintering temperature and sintering range.
The Luoyang typical but non-limiting mass percent of soil is, for example: 8%, 9%, 10%, 11%, 12%；
Adjustment material is No. four bauxite calcination of chamotte, for adjusting Al in this formula2O3Total content makes in 70%-80% according to this
It is formulated in the raw material prepared, Al2O3Total content keeps higher Al in 70%-80%2O3Content, the shape of crystallite when convenient for firing
At the wearability of raising ball brick.
Total Al in this formula2O3The typical but non-limiting mass percent of total content is, for example: 70%, 75%, 76%,
77%、80%。
Each raw material internal component accounting in the present invention:
The main composition that No.1 bauxite, No. two bauxites, No. three bauxites and adjustment are expected are as follows: Al2O3、
SiO2、K2O、Na2O and miscellaneous material, miscellaneous material are other substances and impurity for not influencing the production of ball brick in calcination of chamotte.
Al in No.1 bauxite2O3Content is typical but not restrictive mass percent is, for example: 78%, 90%, 91%,
92%,94%；
SiO in No.1 bauxite2Content is typical but not restrictive mass percent is, for example: 8%, 9%, 10%, 11%,
12%；
K in No.1 bauxite2O content is typical but not restrictive mass percent is, for example: 1%, 1.5%, 2%, 2.5%,
3%；
Na in No.1 bauxite2O content is typical but not restrictive mass percent is, for example: 0.1%, 0.8%, 1.9%,
2.6%,3%；
Miscellaneous material content is typical in No.1 bauxite but not restrictive mass percent is, for example: 2%, 4%, 5%, 6%, 8%；
Al in No. two bauxites2O3Content is typical but not restrictive mass percent is, for example: 73%, 74%, 76%,
77%,78%；
SiO in No. two bauxites2Content is typical but not restrictive mass percent is, for example: 12%, 12.5%, 13%,
13.5%,14%；
K in No. two bauxites2O content is typical but not restrictive mass percent is, for example: 1.1%, 1.3%, 1.4%,
1.5%,1.7%；
Na in No. two bauxites2O content is typical but not restrictive mass percent is, for example: 0.1%, 0.5%, 0.9%,
1.3%,1.7%；
Miscellaneous material content is typical in No. two bauxites but not restrictive mass percent is, for example: 8%, 9%, 10%, 11%,
12%；
Al in No. three bauxites2O3Content is typical but not restrictive mass percent is, for example: 67%, 69%, 70%,
71%,73%；
SiO in No. three bauxites2Content is typical but not restrictive mass percent is, for example: 14%, 14.5%, 15%,
15.5%,16%；
K in No. three bauxites2O content is typical but not restrictive mass percent is, for example: 0.6%, 0.7%, 0.8%,
0.9%,1.0%；
Na in No. three bauxites2O content is typical but not restrictive mass percent is, for example: 0.1%, 0.3%, 0.5%,
0.7%,1.0%；
Miscellaneous material content is typical in No. three bauxites but not restrictive mass percent is, for example: 12%, 14%, 15%, 16%,
18%；
The typical but non-limiting mass percent of the purity of aluminium oxide is, for example: 99.6%, 99.7%, 99.8%, 99.9%,.
The typical but non-limiting mass percent of the purity of barium carbonate is, for example: 95%, 96%, 97%, 98%, 99.%.
Al in the soil of Luoyang2O3Content is typical but not restrictive mass percent is, for example: 50%, 52%, 54%, 56%, 58%；
SiO in the soil of Luoyang2Content is typical but not restrictive mass percent is, for example: 33%, 35%, 36%, 37%, 38%；
K in the soil of Luoyang2O content is typical but not restrictive mass percent is, for example: 1%, 1.5%, 2%, 2.5%, 3%；
Na in the soil of Luoyang2O content is typical but not restrictive mass percent is, for example: 2%, 2.5%, 3%, 3.5%, 4%；
Miscellaneous material content is typical in the soil of Luoyang but not restrictive mass percent is, for example: 4%, 4.5%, 6.5%, 7.5%, 8%；
Al in No. 4 bauxites2O3Content is typical but not restrictive mass percent is, for example: 70%, 73%, 75%, 78%,
80%；
Any percentage composition is not fixed value among the above, small range can be changed in bound.
In a preferred embodiment of this invention: a small amount of K for containing in raw material or adding2O and Na2O, the alkali metal made are being burnt
Promote the molding of crystallite during system.
Invention utilizes low aluminium ore in output in conventional bauxite: No.1 bauxite, No. two bauxites and three
Number bauxite is as primary raw material, convenient for obtaining, and it is at low cost；A small amount of adjustment material bauxite and height are utilized simultaneously
Pure alumina adjusts Al in this micro crystal wearable ball brick formula material2O3Overall content, then be aided with a small amount of barium carbonate and alkali gold
Belong to, the molding of crystallite, promotes the wearability of this micro crystal wearable ball brick, while having saved cost of material when being conducive to fire.
Another aspect of the present invention provides the processing method of above-mentioned micro crystal wearable ball brick:
In a preferred embodiment of this invention:
According to above-mentioned micro crystal wearable ball brick formula:
Raw material is broken: each material in above-mentioned micro crystal wearable ball brick formula is crushed, after material was crushed 10 meshes, and each object
Material stores classifiedly；
Feedstock assay: above-mentioned broken each raw material being taken away and is chemically examined, and identifies ingredient and content；
Ingredient: each raw material after above-mentioned chemical examination carries out ingredient according to the recipe ingredient of the micro crystal wearable ball brick, when ingredient, each original
Material percentage is strict controlled in claimed range；
It is primary to crush: after ingredient, raw material being crushed using ball mill, 250 meshes are crossed after crushing material, screen over-size is less than 4%
It is qualified as to crush；
Primary aging: according to mass percent, it is 35%% that primary smashed acceptable material, which adds water to water content, after evenly mixing
For mixture, aging 22 hours；
Separating twice: to it is primary it is aging after mixture carry out separating twice, the mixture after separating twice crosses 500 meshes, sieves
Lower object is qualified mixture；
Secondary aging: the qualified mixture after separating twice carries out secondary aging 48 hours；
Finished product is washed and starched: it is secondary it is aging after mixture cross the laggard finished pulp wash pool of 180 meshes, and add 3% dispersing agent and 1%
Forming agent, dispersing agent and forming agent are ceramics dispersing agent, the forming agent bought on the market, mist projection granulating forming adhesive
02127042957) or 1.3-1.7% or so solid content lotion, the lotion are that Shi De Chemical Company in Shanghai produces
PVA(1788/1799 etc.) solution；
Be granulated: the final product mix in finished pulp wash pool enters spray drying tower and is granulated, the temperature control of spray drying tower
At 350 DEG C；
Gradation: the particle that above-mentioned spray drying tower generates respectively enters feed bin, 20 mesh-of -20 mesh of 10 mesh by classifying screen
The feed bin more than feed bin of 30 mesh and 60 mesh is stored；
Aging three times: aging 48 hours of the particle in each feed bin is controlled pellet moisture 8%% by water drenching or ventilation；
The molding of ball brick: the particle after aging three times enters ball press compacting balling-up embryo, and it is equal static pressure that ball press, which provides operating pressure,
50Mpa, pressure brick time are 35 seconds；
Semi-finished product pick up choosing: being screened by ball embryo forming standard, qualified ball embryo is stored in semifinished product warehouse.
Fire: by qualified ball embryo loading of kiln, ball embryo is completed to fire by preheating, firing and cooling three successive stages；Preheating
Stage: kiln temperature rises to 1150 DEG C in 10.2 hours；The firing stage: kiln temperature rose to 1350- in 17.5 hours
1450℃；Cooling stage: ball brick temperature in 20 hours ventilating and cooling to ambient temperature.
Finished product picks up choosing: being screened by ball brick molding standard, qualified ball brick is packed.Micro crystal wearable after forming by a firing
The performance detection of ball brick are as follows: equivalent abrasion is, less than or equal to 0.01 ‰, water absorption rate are less than or equal to 0.001%, the ball brick of diameter 40mm
Bulk density is more than or equal to 3.2g/cm3, the ball brick bulk density of diameter 50mm or 60mm are more than or equal to 3.35g/cm3。
In a preferred embodiment of this invention:
According to above-mentioned micro crystal wearable ball brick formula:
Raw material is broken: each material investment crusher in above-mentioned micro crystal wearable ball brick formula being crushed, raw material was crushed 10
After mesh, filtered each Classification of materials is stored；
Feedstock assay: chemically examining when above-mentioned broken each raw material is got experiment, identifies ingredient and content, carries out statistics and mark
Note；
Ingredient: each raw material after above-mentioned chemical examination carries out ingredient according to the recipe ingredient of the micro crystal wearable ball brick, when ingredient, each original
Material percentage is strict controlled in claimed range；
Primary to crush: after ingredient, investment ball mill is crushed, and raw material smashes it through 250 meshes, and screen over-size is powder less than 4%
Broken qualification；
Primary aging: according to mass percent, it is 38% that primary smashed acceptable material, which adds water to water content, after evenly mixing
For mixture, aging 24 hours；
Separating twice: to it is primary it is aging after mixture investment ball mill crush and carry out separating twice, after separating twice
Mixture crosses 500 meshes, and screenings is qualified mixture；
Secondary aging: the qualified mixture after separating twice carries out secondary aging 50 hours；6% dispersing agent and 2% molding
Agent；
Be granulated: the final product mix in finished pulp wash pool enters spray drying tower and is granulated, the temperature control of spray drying tower
At 400 DEG C；
Gradation: the particle that above-mentioned spray drying tower generates respectively enters feed bin, 20 mesh-of -20 mesh of 10 mesh by classifying screen
The feed bin more than feed bin of 30 mesh and 60 mesh is stored；
Aging three times: aging 50 hours of the particle in each feed bin, pellet moisture are controlled 10%；
The molding of ball brick: the particle after aging three times enters ball press compacting balling-up embryo, and it is equal static pressure that ball press, which provides operating pressure,
60Mpa, pressure brick time are 50 seconds；
Semi-finished product pick up choosing: being screened by ball embryo forming standard, qualified ball embryo is stored in semifinished product warehouse.
Fire: by qualified ball embryo loading of kiln, preheating, firing and cooling three phases are completed to fire；Warm-up phase: kiln temperature
1200 DEG C were risen to by 11 hours；The firing stage: kiln temperature rose to 1450 DEG C by 19 hours；Cooling stage: ball brick temperature
Ambient temperature was cooled to by 21 hours.
Finished product picks up choosing: being screened by ball brick molding standard, qualified ball brick is packed.Equivalent abrasion are 0.02 ‰, are inhaled
Water rate is 0.005%, and the ball brick bulk density of diameter 40mm is 3.3g/cm3, the ball brick bulk density of diameter 50mm or 60mm is
3.45g/cm3。
In a preferred embodiment of this invention:
According to above-mentioned micro crystal wearable ball brick formula:
Raw material is broken: each material in above-mentioned micro crystal wearable ball brick formula put into respectively in different crushers and is crushed,
After raw material was crushed 10 meshes, each raw material is stored classifiedly；
Feedstock assay: taking laboratory for above-mentioned broken each raw material and chemically examine, and identifies ingredient and content, and in minute book
On remembered data value, carry out designation card and label；
Ingredient: each raw material after above-mentioned chemical examination carries out ingredient according to the recipe ingredient of the micro crystal wearable ball brick, when ingredient, each original
Material percentage is strict controlled in claimed range；
It is primary to crush: after ingredient, mixed raw material investment ball mill to be crushed, raw material smashes it through 250 meshes, and screen over-size is small
It is to crush qualification in 4%；
Primary aging: according to above-mentioned recipe ingredient mass percent, primary smashed acceptable material adds water to water content and is
40%, it is after evenly mixing mixture, aging 26 hours；
Separating twice: to it is primary it is aging after mixture carry out separating twice, the mixture after separating twice crosses 500 meshes, sieves
Lower object is qualified mixture；
Secondary aging: the qualified mixture after separating twice carries out secondary aging 52 hours；
Finished product is washed and starched: it is secondary it is aging after mixture cross the laggard finished pulp wash pool of 180 meshes, and add 10% dispersing agent and
3% forming agent；
Be granulated: the final product mix in finished pulp wash pool enters spray drying tower and is granulated, the temperature control of spray drying tower
At 450 DEG C；
Gradation: the particle that above-mentioned spray drying tower generates respectively enters feed bin, 20 mesh-of -20 mesh of 10 mesh by classifying screen
The feed bin more than feed bin of 30 mesh and 60 mesh is stored；
Aging three times: aging 52 hours of the particle in each feed bin, pellet moisture are controlled 12%；
The molding of ball brick: the particle after aging three times enters ball press compacting balling-up embryo, and it is equal static pressure that ball press, which provides operating pressure,
70Mpa, pressure brick time are 60 seconds；
Semi-finished product pick up choosing: being screened by ball embryo forming standard, qualified ball embryo is stored in semifinished product warehouse.
Fire: by qualified ball embryo loading of kiln, preheating, firing and cooling three phases are completed to fire；Warm-up phase: kiln temperature
1250 DEG C were risen to by 12.2 hours；The firing stage: kiln temperature rose 1450 DEG C by 20.4 hours；Cooling stage: ball brick temperature
Degree was cooled to ambient temperature by 22 hours.
Finished product picks up choosing: being screened by ball brick molding standard, qualified ball brick is packed.Equivalent abrasion are 0.03 ‰, are inhaled
Water rate is 0.01%, and the ball brick bulk density of diameter 40mm is 3.35g/cm3, the ball brick bulk density of diameter 50mm or 60mm is
3.48g/cm3。
In a preferred embodiment of this invention:
In the processing method of above-mentioned micro crystal wearable ball brick, semi-finished product is picked up, unqualified ball embryo in process and finished product is selected to pick up and select work
Unqualified ball brick in sequence is classified as useless brick, by recipe ratio using useless brick as the raw material of production micro crystal wearable ball brick, saves raw material,
Waste is reduced, enterprise's productivity effect is improved.
In the present invention using No.1 bauxite, No. two bauxites and No. three bauxites as crystallite
The primary raw material of wear-resistant ball brick, primary raw material are low aluminium ore in different ore bed outputs in conventional bauxite, in low aluminium ore be convenient for
It obtains, and at low cost, obtains clinker by calcining；It is resistance to adjust this crystallite using a small amount of adjustment material and high purity aluminium oxide simultaneously
Al in abrading-ball brick formula material2O3Overall content, adjustment material is higher No. four bauxites of alumina content, then is aided with
A small amount of barium carbonate and alkali metal, wears into powder, and carries out aging after being mixed, and can be improved, enhances plasticity, reduces molding
It cracks with when firing, tunnel oven firing is carried out after compression moulding, realize micro mist molding, produce with the wear-resisting of microstructure
Ball brick, and specific gravity is moderate, the far smaller than common middle aluminium wear-resistant ball brick of abrasion.
Although reference be made herein to invention has been described for multiple explanatory embodiments of the invention, however, it is to be understood that
Those skilled in the art can be designed that a lot of other modification and implementations, these modifications and implementations will fall in this Shen
It please be within disclosed scope and spirit.It more specifically, within the scope of the present disclosure and claims, can be to master
The building block or layout for inscribing composite configuration carry out a variety of variations and modifications.In addition to building block or layout carry out deformation and
Outside improving, to those skilled in the art, other purposes also be will be apparent.
Claims (9)
1. micro crystal wearable ball brick, it is characterised in that: recipe ingredient and mass percent are as follows: including No.1 bauxite 44%-
58%, No. two bauxite 12%-27%, No. three bauxite 3%-14%, alumina raw material 6%-13%, barium carbonate raw material 1%-
5%, Luoyang soil 8%-12%, give up brick 0%-7%, adjustment material 2%-12%；Wherein: the Al in the No.1 bauxite2O3Content is big
In being equal to 78%, it is less than or equal to 84%；Al in No. two bauxites2O3Content is more than or equal to 73%, is less than or equal to 78%；
Al in No. three bauxites2O3Content is more than or equal to 67%, is less than or equal to 73%；The purity of the barium carbonate raw material is big
In equal to 95%；The purity of the alumina raw material is more than or equal to 99.6%；Al in the Luoyang soil2O3Content is more than or equal to
50%, it is less than or equal to 58%；SiO in the Luoyang soil2Content is more than or equal to 33%, is less than or equal to 38%；The adjustment material is used for
Adjust Al in this formula2O3Total content is in 70%-79%.
2. micro crystal wearable ball brick according to claim 1, it is characterised in that: include 8%- in the No.1 bauxite
12% SiO2, the K of 1%-3%2The Na of O, 0.1%-3%2The miscellaneous material of O and 2%-8%；It include 12%- in No. two bauxites
14% SiO2, the K of 1.1%-1.7%2The Na of O, 0.1%-1.7%2The miscellaneous material of O and 8%-12%；No. three bauxites
In include 14%-16% SiO2, the K of 0.6%-1.0%2The Na of O, 0.1%-1.0%2The miscellaneous material of O and 12%-18%.
3. micro crystal wearable ball brick according to claim 1, it is characterised in that: the Luoyang soil includes the K of 1%-3%2O, 2%-
4% Na2The miscellaneous material of O and 4%-8%.
4. micro crystal wearable ball brick according to claim 1, it is characterised in that: the adjustment material is No. four bauxites,
Al in No. four bauxites2O3Content is greater than 28%.
5. the processing method of micro crystal wearable ball brick described in -6 any one according to claim 1, it is characterised in that: successively include
Following steps:
Raw material is broken: each material in above-mentioned micro crystal wearable ball brick formula is crushed, after raw material was crushed 10 meshes, and each original
Material stores classifiedly；
Feedstock assay: above-mentioned broken each raw material is chemically examined, and identifies ingredient and content；
Ingredient: each raw material after above-mentioned chemical examination carries out ingredient according to the recipe ingredient of the micro crystal wearable ball brick；
It is primary to crush: after ingredient, to be crushed, raw material smashes it through 250 meshes, and screen over-size is to crush qualification less than 4%；
Primary aging: according to mass percent, it is 35%-40% that primary smashed acceptable material, which adds water to water content, uniformly mixed
It is mixture after conjunction, it is 22-26 hours aging；
Separating twice: to it is primary it is aging after mixture carry out separating twice, the mixture after separating twice crosses 500 meshes, sieves
Lower object is qualified mixture；
Secondary aging: the qualified mixture after separating twice carries out secondary 48-52 hours aging；
Finished product is washed and starched: it is secondary it is aging after mixture cross the laggard finished pulp wash pool of 180 meshes, and add the dispersing agent of 3%-10%
With the forming agent of 1%-3%；
Be granulated: the final product mix in finished pulp wash pool enters spray drying tower and is granulated, the temperature control of spray drying tower
At 350 DEG C -450 DEG C；
Gradation: the particle that above-mentioned spray drying tower generates respectively enters feed bin, 20 mesh-of -20 mesh of 10 mesh by classifying screen
The feed bin more than feed bin of 30 mesh and 60 mesh is stored；
Aging three times: the particle in each feed bin is 48-52 hours aging, and pellet moisture is controlled in 8%-12%；
The molding of ball brick: the particle after aging three times enters ball press compacting balling-up embryo, and it is equal static pressure that ball press, which provides operating pressure,
50Mpa-70Mpa, pressure brick time are 35-60 seconds；
Semi-finished product pick up choosing: being screened by ball embryo forming standard, qualified ball embryo is stored in semifinished product warehouse.
6. firing: by qualified ball embryo loading of kiln, preheating, firing and cooling three phases are completed to fire；Warm-up phase: kiln temperature warp
It spends 10.2-12.2 hours and rises to 1150-1250 DEG C；The firing stage: kiln temperature rose to 1350- by 17.5-20.4 hours
1450℃；Cooling stage: kiln temperature was cooled to ambient temperature by 20-22 hours.
7. finished product picks up choosing: being screened by ball brick molding standard, qualified ball brick is packed.
8. the processing method of micro crystal wearable ball brick according to claim 7, it is characterised in that: the semi-finished product pick up choosing not
The unqualified ball brick that qualified ball embryo and the finished product pick up choosing is classified as useless brick.
9. the processing method of micro crystal wearable ball brick according to claim 7, it is characterised in that: used in the firing step
Tunnel oven is fired the ball base of compression moulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910691221.0A CN110407564B (en) | 2019-07-29 | 2019-07-29 | Microcrystal wear-resisting ball brick |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910691221.0A CN110407564B (en) | 2019-07-29 | 2019-07-29 | Microcrystal wear-resisting ball brick |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110407564A true CN110407564A (en) | 2019-11-05 |
| CN110407564B CN110407564B (en) | 2022-07-01 |
Family
ID=68363975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910691221.0A Active CN110407564B (en) | 2019-07-29 | 2019-07-29 | Microcrystal wear-resisting ball brick |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110407564B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533539A (en) * | 2020-04-16 | 2020-08-14 | 山东天汇研磨耐磨技术开发有限公司 | Ceramic corundum abrasive and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187479A (en) * | 1997-09-04 | 1998-07-15 | 赵德胜 | Method for producing corundum ceramics using alumine as main raw material and its products |
| CN101525231A (en) * | 2008-03-05 | 2009-09-09 | 邹平金刚新材料有限公司 | Process or preparing microcrystal wear-resisting alumina ceramic |
| CN101525230A (en) * | 2008-03-05 | 2009-09-09 | 邹平金刚新材料有限公司 | Formulation of microcrystal wear-resisting alumina ceramic |
| CN104072111A (en) * | 2013-03-29 | 2014-10-01 | 北京市理化分析测试中心 | Preparation method of aluminium oxide honeycomb ceramics |
| CN104649655A (en) * | 2015-02-14 | 2015-05-27 | 济南大学 | Preparation method of special low-density grinding ball for cement grinding mill |
| CN106746801A (en) * | 2016-12-26 | 2017-05-31 | 西南石油大学 | A kind of method that utilization red mud prepares crystallite calcium aluminoferrite |
| CN107226684A (en) * | 2016-07-18 | 2017-10-03 | 淄博金石节能新材料科技有限公司 | Wear-resisting zirconium aluminium composite balls and preparation method thereof |
| CN107721388A (en) * | 2017-11-15 | 2018-02-23 | 山西聚义宝鑫新材料有限公司 | A kind of brown environment-friendlyroad road face brick |
| CN108147794A (en) * | 2018-02-08 | 2018-06-12 | 洛阳中伟环保科技有限公司 | A kind of preparation method of high strength ceramic material |
| CN108793976A (en) * | 2018-07-10 | 2018-11-13 | 洛阳鹏飞耐磨材料股份有限公司 | A kind of micro crystal wearable ceramic abrasive body and the preparation method and application thereof |
| CN109400123A (en) * | 2018-10-09 | 2019-03-01 | 广东工业大学 | A kind of fine-grained alumina ceramics and its preparation method and application |
| CN112374868A (en) * | 2020-11-26 | 2021-02-19 | 汝州市小微结构陶瓷有限公司 | Microcrystal high-alumina ball, preparation method thereof and method for grinding ceramic blank by using microcrystal high-alumina ball |
-
2019
- 2019-07-29 CN CN201910691221.0A patent/CN110407564B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187479A (en) * | 1997-09-04 | 1998-07-15 | 赵德胜 | Method for producing corundum ceramics using alumine as main raw material and its products |
| CN101525231A (en) * | 2008-03-05 | 2009-09-09 | 邹平金刚新材料有限公司 | Process or preparing microcrystal wear-resisting alumina ceramic |
| CN101525230A (en) * | 2008-03-05 | 2009-09-09 | 邹平金刚新材料有限公司 | Formulation of microcrystal wear-resisting alumina ceramic |
| CN104072111A (en) * | 2013-03-29 | 2014-10-01 | 北京市理化分析测试中心 | Preparation method of aluminium oxide honeycomb ceramics |
| CN104649655A (en) * | 2015-02-14 | 2015-05-27 | 济南大学 | Preparation method of special low-density grinding ball for cement grinding mill |
| CN107226684A (en) * | 2016-07-18 | 2017-10-03 | 淄博金石节能新材料科技有限公司 | Wear-resisting zirconium aluminium composite balls and preparation method thereof |
| CN106746801A (en) * | 2016-12-26 | 2017-05-31 | 西南石油大学 | A kind of method that utilization red mud prepares crystallite calcium aluminoferrite |
| CN107721388A (en) * | 2017-11-15 | 2018-02-23 | 山西聚义宝鑫新材料有限公司 | A kind of brown environment-friendlyroad road face brick |
| CN108147794A (en) * | 2018-02-08 | 2018-06-12 | 洛阳中伟环保科技有限公司 | A kind of preparation method of high strength ceramic material |
| CN108793976A (en) * | 2018-07-10 | 2018-11-13 | 洛阳鹏飞耐磨材料股份有限公司 | A kind of micro crystal wearable ceramic abrasive body and the preparation method and application thereof |
| CN109400123A (en) * | 2018-10-09 | 2019-03-01 | 广东工业大学 | A kind of fine-grained alumina ceramics and its preparation method and application |
| CN112374868A (en) * | 2020-11-26 | 2021-02-19 | 汝州市小微结构陶瓷有限公司 | Microcrystal high-alumina ball, preparation method thereof and method for grinding ceramic blank by using microcrystal high-alumina ball |
Non-Patent Citations (2)
| Title |
|---|
| 戴金辉等: "《无机非金属材料概论》", 31 July 2018, 哈尔滨工业大学出版社 * |
| 李灿然等: ""压裂支撑剂研究进展及发展趋势"", 《陶瓷学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533539A (en) * | 2020-04-16 | 2020-08-14 | 山东天汇研磨耐磨技术开发有限公司 | Ceramic corundum abrasive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110407564B (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108975923B (en) | Ceramic roller rod with thermal shock resistance and high-temperature volume stability and preparation method thereof | |
| CN109715560A (en) | Spinel powder and its manufacturing method containing magnesia | |
| CN104261848A (en) | Chrome-oxide-containing mullite brick and preparation method thereof | |
| CN101671046B (en) | Method for manufacturing high-purity magnesium-aluminum spinel | |
| CN108083765A (en) | Low heat conduction anti-strip brick and preparation method thereof | |
| CN103833392B (en) | A kind of preparation method of alundum | |
| CN113800895A (en) | Wear-resistant zirconium-aluminum composite ball and preparation method thereof | |
| CN110894162A (en) | Ultrahigh-temperature high-strength ceramic roller and preparation method thereof | |
| CN108059447A (en) | A kind of big crystallization sintering plate corundum and preparation method thereof | |
| CN104692816A (en) | Compact aluminum, magnesium, calcium grog refractory and preparation method thereof | |
| CN104671810A (en) | Compact aluminum-magnesium-calcium fire-resistant clinker and preparation method thereof | |
| CN106145686A (en) | A kind of complicated utilization Pb-Zn tailings, the devitrified glass and preparation method thereof of electrolytic manganese waste residue | |
| CN106336227B (en) | A kind of mineral products waste refractory material and its preparation process | |
| CN110407564A (en) | Micro crystal wearable ball brick and its processing method | |
| CN112897994A (en) | Preparation method of corundum spinel complex phase material | |
| CN112028651A (en) | Chromium corundum material and production method thereof | |
| CN1194931C (en) | Production method of sludge baked brick | |
| CN110002885A (en) | A method of the fused magnesite of zirconium spinel containing magnalium is prepared with electric arc furnaces | |
| CN106396696B (en) | The preparation method of mullite spherical shape aggregate enhancing refractory material | |
| CN107973586A (en) | Handle the method and Ceramic Tiles of ferrochrome slag | |
| CN101654368B (en) | Manufacturing method of high-temperature resistant ceramic particles with golf surface appearance feature | |
| CN104591746B (en) | Cement kiln new A C fire resistant materials and preparation method thereof | |
| CN103936440B (en) | Preparation method of sintered corundum with good wear resistance | |
| CN107311674B (en) | Special sprue pipe for casting and preparation method thereof | |
| CN111377471A (en) | Method for preparing calcium aluminate powder by using low-grade bauxite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |