CN106518107A - Preparation method of layered high purity zircon refractory material - Google Patents
Preparation method of layered high purity zircon refractory material Download PDFInfo
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Abstract
The invention relates to a preparation method of a layered high purity zircon refractory material. The method includes the steps of: preparation of a high-purity zircon raw material, preparation of a common zircon raw material, layered isostatic pressing and high temperature solid phase sintering. Experiments show that very little transition metal impurity ion contamination is introduced in a glass smelting process of the layered high purity zircon refractory material prepared by the method provided by the invention, a layered molding technology can be employed to control the cost, and also can achieve good anti-glass corrosion effect.
Description
Technical field
The present invention relates to high-purity refractory material, particularly a kind of preparation method for being layered high-purity aircon refractory should
Refractory material is used for the material of high-grade optical glass smelting furnace, laser glass smelting furnace and metal smelting furnace.
Background technology
Refractory material is the indispensable basic material of high-temperature technology, the commercial production mistake of related to high-temperature chemical reaction
Journey, it is necessary to have both high temperature resistants, and a resistant to corrosion, and stress can also be resisted in many cases or temperature is jumpy resistance to
Fiery material.China is refractory material manufacturing country maximum in the world and consumes state.Meanwhile, China researches and develops field in refractory material
Positive role increasingly manifests.With to low-carbon economy and the concern of environmental conservation, and having in the face of natural resourcess in world wide
The difficulty that effect is utilized, Chinese refractories industry must strengthen the innovation work of raw material and basic research, to adjust the product mix,
The increasingly harsher requirement of high temperature new technique is adapted to, the sustainable development of Chinese refractories industry is realized, provides attached with height
Value added, high-temperature behavior is excellent, using effect and economic benefit better meet individual demand high-quality refractory material it is new
Product.
High-grade optical glass will meet image quality and high permeability, it is desirable to its absorptance very little in specific wavelength,
Particularly laser glass will meet high-gain and high-energy-density index, it is desirable to its absorption coefficient of light of optical maser wavelength it is more little more
It is good, using general commercial refractory material because of Fe2O3Impurity content Deng transition metal generally in thousands of ppmw magnitudes, invade by Jing glass
After erosion, these impurity can be entered in glass melt, it is difficult to met high-grade optical glass and be particularly wanting for laser glass low impurity content
Ask, detrimental effects are caused to indexs such as the transmitances and light absorbs of glass.In the urgent need to a kind of not only high temperature resistant, resistance to glass attack but also
Impurity and the economic and practical high-purity refractory material for being suitable to melting top grade optical glass and laser glass are not introduced.
The content of the invention
For above-mentioned not enough and defect present in prior art, it is an object of the invention to provide a kind of layering high purity zirconium English
The preparation method of stone refractory material.The method prepare the high-purity aircon refractory of layering have it is rational in infrastructure, be easy to processing,
High temperature resistant corrodes and does not again pollute glass, and cost it is controllable the characteristics of.
The technology of the present invention solution is as follows：
A kind of preparation method for being layered high-purity aircon refractory, it is characterised in that the method comprises the following steps：
1. the preparation of high-purity zircon raw material：From purity >=99.9%, the ZrO of 66～67.7wt%2, purity >=
99.9%th, the SiO of 32～33wt%2, purity >=99.5%, the TiO of 0.3～2wt%2, it is milled to zirconia balls after mixing
After fineness is 0.1～5 μm >=95%, then Jing >=1100 DEG C high-temperature calcination 20～48 hours synthesizes, plus 0.1～0.2wt% it is excellent
Level pure phosphoric acid, using zirconia balls ball milling into muddy, fineness requirement is 0.1～6 μm >=95%, and described muddy is high
Pure zircon drying, powder body are crushed, and cross 30 mesh vibrosieves, obtain high-purity zircon raw material；
2. the preparation of common zircon raw material：From ZrSiO4>=98.5% common zircon raw material, plus 0.3～
The TiO of 2wt%2, 0.1～0.2wt% phosphoric acid, using zirconia balls ball milling into muddy, fineness is 0.1～6 μm >=95%,
By the described common zircon drying of muddy, powder body is crushed, and crosses 30 mesh vibrosieves, obtains common zircon raw material；
3. it is layered isostatic pressing：It is using isostatic pressing method, first general with described common zircon raw material molding one
Logical zircon layer, then covers simultaneously molding one with described high-purity zircon raw material high-purity on described common zircon layer again
Zircon layer, the thickness >=20mm of described high-purity zircon layer；
4. high temperature solid-phase sintering；Calcining system is：
Temperature-rise period：Room temperature～200 DEG C, heating rate≤8 DEG C/h, 200 DEG C of insulation >=4h；200～1000 DEG C, heat up speed
Rate≤8 DEG C/h, 1000 DEG C of insulation >=4h；1000～>=1550 DEG C, heating rate≤8 DEG C/h, be incubated at >=1550 DEG C >=
12h；
Temperature-fall period：>=1550 DEG C～400 DEG C, rate of temperature fall≤10 DEG C/h, 400 DEG C～room temperature, rate of temperature fall≤6 DEG C/
H, obtains the high-purity aircon refractory of layering after sintering.
The transition metal impurity content requirement of described high-purity zircon raw material：CuO contents≤5ppmw, CuO+Co2O3+
NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤100ppmw.
Described mud drying temperature is 180～350 DEG C, the moisture≤0.2wt% of raw material after drying.
The thickness of described high-purity aircon refractory is be layered refractory material gross thickness 0.9～0.1.
Pressure >=the 200Mpa of the molding isostatic pressed of the described high-purity aircon refractory of layering.
The size of the described high-purity aircon refractory of layering, can make according to smelting furnace design requirement tens of
Millimeter arrives >=1000 millimeters, and it is 0.9～0.1 that high-purity zircon thickness accounts for the ratio of gross thickness, takes into account economic and practical original
Then.
This reality invention advantage be：
1st, the high-purity material of high-purity aircon refractory is layered partly because purity is high, even structure densification, both resistance to height
Temperature, resistance to glass attack do not introduce impurity again and are suitable to melting top grade optical glass and laser glass.
2nd, it is layered high-purity aircon refractory and adopts hierarchy, takes into account economic and practical principle, both may be controlled to
This is easy to design and applies again, and with fine resistant to corrosion effect, its intensity is also no less than general commercial refractory material.
3rd, using the high-purity aircon refractory of this kind of layering in glass melting process, the foreign ion pair such as transition metal
The pollution of glass is few, can ensure high-grade optical glass, particularly have the high-quality and low optical of the laser glass of particular/special requirement
Loss is required.
Description of the drawings
Fig. 1 is that glass melting stove of the present invention is layered high-purity zircon structure of refractory schematic diagram.
1 high-purity zircon refractory masses of label, 2 general commercial refractory masses, the high-purity aircon refractories of D in figure
Thickness degree, L are layered high-purity aircon refractory gross thickness.
Fig. 2 is the trial furnace schematic diagram of the present invention；
Fig. 3 is the XRD diffraction patterns of high-purity aircon refractory and general commercial aircon refractory, and 1 is high purity zirconium
Diamond stone refractory masses, 2 is general commercial aircon refractory layer.
Fig. 4 is the micro-structure diagram of high-purity zircon refractory masses and general commercial aircon refractory layer.
Specific embodiment：
The present invention is further illustrated with reference to the accompanying drawings and examples, but does not limit the protection model of the present invention with this
Enclose.
As shown in figure 1, the glass melting stove of the present invention high-purity aircon refractory of layering, including high-purity zircon fire resisting
Material layer 1, general commercial refractory masses 2.
The preparation method of the high-purity aircon refractory of present invention layering, method comprise the following steps：
1. the preparation of high-purity zircon raw material：From purity >=99.9%, the ZrO of 66～67.7wt%2, purity >=
99.9%th, the SiO of 32～33wt%2, purity >=99.5%, the TiO of 0.3～2wt%2, it is milled to zirconia balls after mixing
After fineness is 0.1～5 μm >=95%, then Jing >=1100 DEG C high-temperature calcination 20～48 hours synthesizes, plus 0.1～0.2wt% it is excellent
Level pure phosphoric acid, using zirconia balls ball milling into muddy, fineness requirement is 0.1～6 μm >=95%, and described muddy is high
Pure zircon drying, powder body are crushed, and cross 30 mesh vibrosieves, obtain high-purity zircon raw material；
2. the preparation of common zircon raw material：From ZrSiO4>=98.5% common zircon raw material, plus 0.3～
The TiO of 2wt%2, 0.1～0.2wt% phosphoric acid, using zirconia balls ball milling into muddy, fineness is 0.1～6 μm >=95%,
By the described common zircon drying of muddy, powder body is crushed, and crosses 30 mesh vibrosieves, obtains common zircon raw material；
3. it is layered isostatic pressing：It is using isostatic pressing method, first general with described common zircon raw material molding one
Logical zircon layer, then covers simultaneously molding one with described high-purity zircon raw material high-purity on described common zircon layer again
Zircon layer, constitutes the high-purity aircon refractory of layering, the thickness >=20mm of described high-purity zircon layer；
4. the high-purity aircon refractory high temperature solid-phase sintering of described layering；Calcining system is：
Temperature-rise period：Room temperature～200 DEG C, heating rate≤8 DEG C/h, 200 DEG C of insulation >=4h；200～1000 DEG C, heat up speed
Rate≤8 DEG C/h, 1000 DEG C of insulation >=4h；1000～>=1550 DEG C, heating rate≤8 DEG C/h, be incubated at >=1550 DEG C >=
12h；
Temperature-fall period：>=1550 DEG C～400 DEG C, rate of temperature fall≤10 DEG C/h, 400 DEG C～room temperature, rate of temperature fall≤6 DEG C/
H, obtains the high-purity aircon refractory of layering after sintering.
The transition metal impurity content requirement of described high-purity zircon raw material：CuO contents≤5ppmw, CuO+Co2O3+
NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤100ppmw.
Described mud drying temperature is 180～350 DEG C, the moisture≤0.2wt% of raw material after drying.
The thickness of described high-purity aircon refractory is be layered refractory material gross thickness 0.9～0.1.
Pressure >=the 200Mpa of the molding isostatic pressed of the described high-purity aircon refractory of layering.
The present embodiment one：500 millimeters of two pieces of refractory material length are made, it is wide 400 millimeters.Its gross thickness L=100 millimeter, its
In high-purity zircon refractory masses thickness be respectively D=90 millimeters (I bricks) and D=50 millimeters (II bricks)；The present embodiment
Two：Make 400 millimeters of two pieces of refractory material length, wide 300 millimeters, its gross thickness L=100 millimeter, wherein high-purity zircon fire resisting
Layer thickness D=50 millimeters (III bricks)；The present embodiment three：300 millimeters of one piece of refractory material length is made, it is wide 300 millimeters,
Its gross thickness L=200 millimeter, it is wherein high-purity zircon refractory masses thickness D=200 millimeters (IV bricks).
Embodiment one：
According to the size of refractory material, the raw material dosage of high-purity zircon and general commercial zircon is estimated.It is high-purity
Zircon raw material needs synthetic.
125 kilograms of high-purity zircon raw material, and making and the follow-up course of processing is needed to need to reserve the remaining of 30wt%
Amount, according to following proportioning：High-purity ZrO2For 66.2wt%, high-purity Si O2For 33wt%, the high-purity Ti O of 0.8wt%2, configuration 162
Kilogram raw material.All material purity >=99.9%, and CuO contents≤5ppmw, CuO+Co2O3+NiO+Cr2O3≤ 10ppmw,
Fe2O3Content≤50ppmw.By zirconium oxide and silicon oxide compound ball milling grind within 36 hours to fineness requirement be 0.1～6 μm >=
95%1 μm, being put in clean mould the Jing solid state reactions Jing after 1350 DEG C of calcinings 30 hours, to generate high-purity zircon raw material stand-by.
54 kilograms of general commercial zircon raw material is needed, making and the allowance of 30wt% will be also reserved, is then needed common
70 kilograms of commercial zircon raw material, plus 0.7 kilogram of TiO2。
General commercial zircon raw material and high-purity zircon raw material are added 0.1～0.2wt% phosphoric acid is individually milled to
Fineness requirement is 0.1～6 μm >=95%, drying.The present embodiment I bricks are in advance with general commercial zircon raw material Jing 200MPa etc.
520 × 420 × 15 millimeters of hydrostatic profile3Blank, then cover the pure zircon raw material of a floor height, then Jing 300Mpa again above
Isostatic pressing is into 520 × 420 × 110 millimeters3Blank.The present embodiment II bricks in advance with general commercial zircon raw material into
520 × 420 × 55 millimeters of type3Blank, then Jing 200MPa isostatic pressings cover the pure zircon of a floor height former again above
Material, Jing 300Mpa isostatic pressings are into 520 × 420 × 110 millimeters3Blank；
The blank of forming is heated up with 5 DEG C/h in down-draft kiln, 200 DEG C of insulation 4h, 200～1000 DEG C, heating rate
5 DEG C/h, 1000 DEG C of insulation 4h；1000～1600 DEG C, 8 DEG C/h of heating rate is incubated 12h at 1600 DEG C；It is down to 8 DEG C/h
400 DEG C, then room temperature is down to 6 DEG C/h, it is machined to the size for needing.
Embodiment two：
According to the size of refractory material, the raw material dosage of high-purity zircon and general commercial zircon is estimated.It is high-purity
Zircon raw material needs synthetic.
53.5 kilograms of high-purity zircon raw material, and making and the follow-up course of processing is needed to need to reserve the remaining of 30wt%
Amount, according to following proportioning：High-purity ZrO2For 66wt%, high-purity Si O2For 32wt%, the high-purity Ti O of 2wt%2, configuration 70 kilograms it is former
Material.All material purity >=99.9%, and CuO contents≤5ppmw, CuO+Co2O3+NiO+Cr2O3≤ 10ppmw, Fe2O3Content
≤50ppmw.It is 0.1～6 μm >=95%1 μm that zirconium oxide and silicon oxide compound ball milling are ground to fineness requirement for 36 hours, is put
Entering in clean mould the Jing solid state reactions Jing after 1100 DEG C of calcinings 20 hours, to generate high-purity zircon raw material stand-by.
53.5 kilograms of general commercial zircon raw material is needed, making and the allowance of 30wt% will be also reserved, is needed general
70 kilograms of zircon raw material of trading, plus 1.4 kilograms of TiO2。
General commercial zircon raw material and high-purity zircon raw material are added 0.1～0.2wt% phosphoric acid is individually milled to
Fineness requirement is 0.1～6 μm >=95%, drying.The present embodiment III bricks use general commercial zircon raw material molding 420 in advance
× 320 × 55 millimeters3Blank, then Jing 200MPa isostatic pressings cover the pure zircon raw material of a floor height again above, then
Jing 300Mpa isostatic pressings are into 420 × 320 × 110 millimeters3Blank；
The blank of forming is heated up with 8 DEG C/h in down-draft kiln, 200 DEG C of insulation 4h, 200～1000 DEG C, heating rate
8 DEG C/h, 1000 DEG C of insulation 4h；1000～1550 DEG C, 8 DEG C/h of heating rate is incubated 12h at 1550 DEG C；It is down to 8 DEG C/h
400 DEG C, then room temperature is down to 6 DEG C/h, it is machined to the size for needing.
Embodiment three：
According to the size of refractory material, the raw material dosage of high-purity zircon and general commercial zircon is estimated.It is high-purity
Zircon raw material needs synthetic.
8 kilograms of high-purity zircon raw material is needed, and makes the surplus for needing reserved 30wt% with the follow-up course of processing,
According to following proportioning：High-purity ZrO2For 67.7wt%, high-purity Si O2For 32wt%, the high-purity Ti O of 0.3wt%2, configure 10.5 public
Jin raw material.Wherein, ZrO2、SiO2Material purity >=99.9%, TiO2Material purity >=99.5%, and CuO contents≤5ppmw,
CuO+Co2O3+NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤50ppmw.By zirconium oxide and silicon oxide compound ball milling 36 hours
It is 0.1～6 μm >=95%1 μm to grind to fineness requirement, is put in clean mould the Jing solid phases Jing after 1350 DEG C of calcinings 24 hours anti-
High-purity zircon raw material should be generated stand-by.
72 kilograms of general commercial zircon raw material is needed, making and the allowance of 30wt% will be also reserved, is needed common
94 kilograms of commercial zircon raw material, plus 0.3 kilogram of TiO2。
General commercial zircon raw material and high-purity zircon raw material are added 0.1～0.2wt% phosphoric acid is individually milled to
Fineness requirement is 0.1～6 μm >=95%, drying.The present embodiment IV bricks in advance with general commercial zircon raw material molding 320 ×
320 × 190 millimeters3Blank, then Jing 200MPa isostatic pressings cover the pure zircon raw material of a floor height, Jing again above
300Mpa isostatic pressings are into 320 × 320 × 215 millimeters3Blank；
The blank of forming is heated up with 5 DEG C/h in down-draft kiln, 200 DEG C of insulation 4h, 200～1000 DEG C, heating rate
5 DEG C/h, 1000 DEG C of insulation 4h；1000～1620 DEG C, 8 DEG C/h of heating rate is incubated 20h at 1620 DEG C；It is down to 8 DEG C/h
400 DEG C, then room temperature is down to 6 DEG C/h, it is machined to the size for needing.In 300 × 300 millimeters of IV bricks2Big face in
The heart bores the through hole IX of 20 millimeters of a Φ.
The crystalline phase of the high-purity aircon refractory of sampling and testing is simultaneously compared such as Fig. 3 institutes with general commercial aircon refractory
Show, all zircon phases of its crystalline phase, microstructure is compared such as Fig. 4, contrasts its compactness with commercial aircon refractory good
Resistant to corrosion is more excellent.
I～IV bricks are assembled into into volume for 300 × 300 × 200 millimeters3Glass melting stove as shown in Fig. 2 contact
The face of glass is high-purity zircon material, around with the light weight alumina insulating brick V, top Fe that one layer of 115mm is thick2O3Content
The mullite of 50ppmw is caping VI, and one 100 × 100mm is opened in side2Charge door VIII, with 10 Φ 25 above charge door
Siliconits VII.Described glass melting stove is warming up to into 1200 DEG C of insulations with 10 DEG C/h, by 30 kilograms of glass batch
Material is added to the glass melting stove with 5 kilograms/20min, and the present embodiment adopts Nd3+Ion concentration 3.5 × 1020Individual/centimetre3's
Phosphate laser glass batch；Melting more than 6 hours after the completion of charging, laser glass melting described in the present embodiment 6 hours, 12
Hour, 24 hours, 48 hours, after 72 hours, sampling Jing inductively coupled plasma atomic emission spectrometers (ICP-AES) test
The transition metal impurity total amounts such as impurity content in glass, its ferrum, copper all≤20ppmw, comply fully with laser glass melting requirement.
Experiment shows, the characteristics of be layered high-purity aircon refractory made by the present invention：Pollute without transition metal impurity,
It is easy to make, is easy to control cost, can be directly applied in high-grade optical glass and laser glass smelting furnace.
Finally, it is noted that the above is only used for explaining the preferred embodiments of the invention, it is not intended to the present invention
Make any pro forma restriction, it will be understood by those of skill in the art that technical scheme can be modified or
Person's equivalent, without deviating from the creation spirit of the present invention, all should cover in protection scope of the present invention.
Claims (5)
1. the preparation method of the high-purity aircon refractory of a kind of layering, it is characterised in that the method comprises the following steps：
1. the preparation of high-purity zircon raw material：From purity >=99.9%, the ZrO of 66～67.7wt%2, purity >=99.9%, 32
The SiO of～33wt%2, purity >=99.5%, the TiO of 0.3～2wt%2, after mixing, fineness is milled to for 0.1 with zirconia balls
After～5 μm >=95%, then Jing >=1100 DEG C high-temperature calcination 20～48 hours synthesizes, plus 0.1～the top grade pure phosphoric acid of 0.2wt%,
Using zirconia balls ball milling into muddy, fineness requirement is 0.1～6 μm >=95%, by the described high-purity zircon of muddy
Drying, powder body are crushed, and cross 30 mesh vibrosieves, obtain high-purity zircon raw material；
2. the preparation of common zircon raw material：From ZrSiO4>=98.5% common zircon raw material, plus 0.3～2wt%
TiO2, 0.1～0.2wt% phosphoric acid, using zirconia balls ball milling into muddy, fineness is 0.1～6 μm >=95%, will be described
The drying of muddy common zircon, powder body is crushed, and crosses 30 mesh vibrosieves, obtains common zircon raw material；
3. it is layered isostatic pressing：Using isostatic pressing method, first with described one common zirconium of common zircon raw material molding
Diamond stone layer, is then covered and one high purity zirconium English of molding with described high-purity zircon raw material on described common zircon layer again
Rock layers, the thickness >=20mm of described high-purity zircon layer；
4. high temperature solid-phase sintering；Calcining system is：
Temperature-rise period：Room temperature～200 DEG C, heating rate≤8 DEG C/h, 200 DEG C of insulation >=4h；200～1000 DEG C, heating rate≤
8 DEG C/h, 1000 DEG C of insulation >=4h；1000～>=1550 DEG C, heating rate≤8 DEG C/h, insulation >=12h at >=1550 DEG C；
Temperature-fall period：>=1550 DEG C～400 DEG C, rate of temperature fall≤10 DEG C/h, 400 DEG C～room temperature, rate of temperature fall≤6 DEG C/h are burnt
The high-purity aircon refractory of layering is obtained after knot.
2. the preparation method of high-purity aircon refractory is layered as claimed in claim 1, it is characterised in that：Described is high-purity
The transition metal impurity content requirement of zircon raw material：CuO contents≤5ppmw, CuO+Co2O3+NiO+Cr2O3≤ 10ppmw,
Fe2O3Content≤100ppmw.
3. the preparation method of high-purity aircon refractory is layered as claimed in claim 1, it is characterised in that：Described mud
Drying temperature is 180～350 DEG C, the moisture≤0.2wt% of raw material after drying.
4. the preparation method of high-purity aircon refractory is layered as claimed in claim 1, it is characterised in that：Described is high-purity
The thickness of aircon refractory is be layered refractory material gross thickness 0.9～0.1.
5. the preparation method of high-purity aircon refractory is layered as claimed in claim 1, it is characterised in that：Described layering
Pressure >=the 200Mpa of the molding isostatic pressed of high-purity aircon refractory.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107117963A (en) * | 2017-04-25 | 2017-09-01 | 山东君道高温材料有限公司 | A kind of manufacturing process of large scale, large span aircon refractory |
| CN116621578A (en) * | 2023-04-26 | 2023-08-22 | 广州市石基耐火材料厂 | Chromium-zirconium refractory material, preparation method thereof and chromium-zirconium electrode brick |
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| CN105174979A (en) * | 2015-08-21 | 2015-12-23 | 淄博裕民基诺新材料有限公司 | Zircon/zirconia multiphase material based on zircon covered zirconium dioxide powder and preparation method thereof |
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| CN101851107A (en) * | 2010-05-06 | 2010-10-06 | 广州市石基耐火材料厂 | Compact zircon brick with low alkali content, hole fusion rate and stress and manufacturing method thereof |
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| CN107117963A (en) * | 2017-04-25 | 2017-09-01 | 山东君道高温材料有限公司 | A kind of manufacturing process of large scale, large span aircon refractory |
| CN116621578A (en) * | 2023-04-26 | 2023-08-22 | 广州市石基耐火材料厂 | Chromium-zirconium refractory material, preparation method thereof and chromium-zirconium electrode brick |
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| CN106518107B (en) | 2019-06-21 |
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