CN102167598A - Method for preparing vanadium-titanium functional ceramic by low-temperature fast firing - Google Patents
Method for preparing vanadium-titanium functional ceramic by low-temperature fast firing Download PDFInfo
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- CN102167598A CN102167598A CN2010105996379A CN201010599637A CN102167598A CN 102167598 A CN102167598 A CN 102167598A CN 2010105996379 A CN2010105996379 A CN 2010105996379A CN 201010599637 A CN201010599637 A CN 201010599637A CN 102167598 A CN102167598 A CN 102167598A
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Abstract
The invention discloses a method for preparing vanadium-titanium functional ceramic by low-temperature fast firing, belonging to the technical field of preparation of functional ceramic. A ceramic biscuit substrate is prepared by adopting a direct solidification injection molding process, micro-size vanadium tailing powder is prepared by adopting an advanced air current crushing technology, and the ceramic is prepared by adding aedelforsite into an ordinary ceramic material and firing by adopting a low-temperature fast firing process, so that the energy consumption is lowered. The vanadium-titanium functional ceramic can be applied to the field of manufacturing of solar water heaters, solar ceilings, far infrared radiation elements, building decorating plates, heater radiating fins, solar air channel generating devices, solar heat collecting field generating sets and the like.
Description
Invention field
The invention belongs to the function ceramics preparing technical field, particularly a kind of low temperature fast firing prepares the method for vanadium titanium function ceramics.
Background technology
Vanadium titanium pottery can be used to make solar water heater, sun power roof, far-infrared radiation element (being used for industries such as baking vanish, food, medical treatment, application industry, grocery trade, textile industry, dyeing industry, grain drying), decorative panel for building, heating radiator, solar ventiduct power generation assembly, solar energy heat-collection field power generation assembly etc.Vanadium titanium pottery cost is low, the life-span is long, efficient is high and the scale and the output combination of the existing ceramic industry of China, might develop into the energy and material of large-scale production.
Vanadium titanium function ceramics is with trade waste---and tailings in vanadium extraction is that main raw material(s) is prepared from, be a kind of good optical-thermal conversion material, have water-fast, high strength, corrosion-resistant, anti-aging, life-span length, high sunlight absorption rate, high photo-thermal conversion efficiency, higher low temperature infrared emittance characteristics such as (0.83-0.95).
Vanadium titano-magnetite is smelted through ore dressing and is obtained vanadium-bearing hot metal, and vanadium-bearing hot metal obtains vanadium slag through blowing, and vanadium slag adds auxiliary material and carries out roasting, and roasting material is carried out wet extraction vanadium extraction salt, and the remaining residue as waste is tailings in vanadium extraction behind the extraction vanadic salts.Tailings in vanadium extraction is to be rich in Fe, Cr, Mn, V, the Ti grade in an imperial examination complex compound of phase element all around, mineral composition and crystalline structure are complicated and stablize, under the fused condition, being always ater at normal temperature, high temperature, is a kind of ceramic black colorant very stable and with low cost.
Present vanadium titanium ceramic preparation, mainly be tailings in vanadium extraction to be mixed in according to a certain percentage sinter porcelain in the general ceramic material into, perhaps apply the tailings in vanadium extraction slurry in the conventional ceramic billet surface, reburn and form porcelain, the energy expenditure in the production process is produced identical or slightly high with conventional ceramic.
Summary of the invention
The object of the present invention is to provide a kind of low temperature fast firing to prepare the method for vanadium titanium function ceramics.
The present invention has preparation process:
A. raw materials pretreatment:
Tailings in vanadium extraction is carried out comminution by gas stream, and selecting materials through the ultrasonic vibration screening obtains the micron particle material of 0.1 μ m-5.0 μ m, and the water that adds the 15-40% quality mixes stirring, makes vanadium titanium function ceramics slurry;
B. directly solidify casting:
In the mixture of stupalith after ball mill pulverizing and wollastonite, add the water of 6-15% quality, add the defloculating agent adjusting pH value of 0.06-0.15mol/L to 10-12 then, stirring pulping, slurry heated in 60-70 ℃ of water-bath inject the normal temperature mould after 6-15 minute, the slurry cooling also changes solid-state base substrate into, in air, place the demoulding after 2-8 hour, form ceramic matrix; After the ceramic matrix drying, at the vanadium titanium function ceramics slurry of its surface-coated steps A preparation, glazing protection after the coat drying;
C. low temperature fast firing:
Adopt roller kiln equipment, temperature rise rate is 6-15 ℃/minute, and insulation is 30-50 minute when being warmed up to 1000-1100 ℃, obtains vanadium titanium function ceramics.
In the described steps A before the comminution by gas stream, also add the stupalith of 0.01-30% quality and the mixture of wollastonite in the tailings in vanadium extraction, the quality of wollastonite is the 10%-20% of stupalith, the mixture of stupalith and wollastonite mixes with tailings in vanadium extraction after ball mill pulverizing, carries out comminution by gas stream then.
The nanometer additive that also adds the 0.1-5% quality when adding water in the described steps A.Described nanometer additive is one or more in nano-titanium oxide, nano zine oxide, nano aluminium oxide, the nano-sized iron oxide.
Defloculating agent described in the step B is NH
4NO
3, the quality of wollastonite is the 10%-20% of stupalith among the step B.
The present invention uses wollastonite to replace feldspar, quartz, wollastonite fusing point (1540 ℃) is lower, and thermal expansivity presents the rectilinearity ascendant trend with the temperature increase, combine with the alkali-alkaline earth composition in the ceramic matrix, be very beneficial for easy fired, can be with 80-120 ℃ of the firing temperature decline of vanadium titanium ceramic article, and to dozens of minutes, made the ceramic matrix maturation at tens minutes, firing period is no more than 50 minutes, reduces the energy consumption of unit goods greatly.
When directly solidifying casting, change the pH value of slurries, move it to isopotential point or increase gegenion concentration compression double electric layer, eliminate the electrostatic repulsion between the ceramic particle, form network structure by the Van der Waals'attractive force between the particle and promote that suspensoid directly solidifies, realize of the conversion of liquid slurry, the ceramic matrix of plastic various complicated shapes, density height, good uniformity to the solid-state ceramic matrix, need not organic binder bond, do not need the high temperature degreasing.
Additive is nano-powder, the also process stable modification processing of being made by some particular matter.Change the kind and the ratio of additive, can be made into the vanadium titanium function ceramics plate of different sunlight absorption rate, far-infrared radiation rate, photo-thermal conversion efficiency, be used for different products.Each nanometer additive effect is as follows:
Nano-titanium oxide: nanometer anatase titania has powerful photo-catalysis capability, chemical stability height, nontoxic.Electronics (e on nano titanium oxide valence band under the effect of UV-light, sunlight, fluorescent lamp
-) can be excited transits to conduction band, produces corresponding hole (h on valence band
+), can play the effect of decomposing organic pollutant, automatically cleaning, the conversion of reinforcement photo-thermal;
Nano zine oxide: nano zine oxide can absorb solar ultraviolet very effectively, nontoxic, can reduce simultaneously the sintering temperature of ceramic greatly, make that to burn till product as bright as a sixpence, cut down the consumption of energy, and make ceramic product have the self-cleaning action of antibacterial and deodouring and decomposing organic matter, greatly improve the quality of products;
Nano aluminium oxide: nano aluminium oxide has the far infrared Extinction Characteristic, can absorb far infrared rays earlier and then progressively discharges, and the nano aluminium oxide of handling through modification is significantly strengthened at the infrared photoextinction of far infrared band;
Nano-sized iron oxide: the nano transparent ferric oxide is nontoxic, tasteless, heatproof, acid and alkali-resistance, and is very strong to ultraviolet receptivity, and hertzian wave and sound wave are had good absorption and decay, middle-infrared band had characteristics such as very strong absorption, dissipation, shielding effect.
The vanadium titanium function ceramics of the present invention's preparation can be applicable to make fields such as solar water heater, sun power roof, far-infrared radiation element, decorative panel for building, heating radiator, solar ventiduct power generation assembly, solar energy heat-collection field power generation assembly as good optical-thermal conversion material.
Solar water heater: can make vitrified pipe and be used for tubular type collector, or make the flat case structure pottery of bringing outlet into and be used for flat plate collector;
Sun power roof: can make the black flat ceramic, perhaps bring the flat case structure pottery of outlet into, be used for the sun power roof and make;
Far-infrared radiation element: can make vitrified pipe and be used to replace the metal tube that present far-infrared radiation device generally uses and the coating on surface thereof;
Decorative panel for building: can make forms such as black ceramic tiles and be used for the building materials field;
Heating radiator: can make heating radiator, conduct heat energy by the mode of far-infrared radiation;
Solar ventiduct power generation assembly: can make the glasshouse that the chimney heat collector replaces present solar ventiduct power generation assembly;
Solar energy heat-collection field power generation assembly: can be used for the heat collector of solar energy heat-collection field power generation assembly, improve photo-thermal conversion efficiency and generating efficiency.
Description of drawings
Fig. 1: the present invention prepares the Application Areas of the process flow sheet and the vanadium titanium function ceramics of vanadium titanium function ceramics.
Embodiment
Embodiment 1:
A. raw materials pretreatment:
Tailings in vanadium extraction is carried out comminution by gas stream, and selecting materials through the ultrasonic vibration screening obtains the micron particle material of 0.1 μ m-3.0 μ m, and the water that adds 25% quality mixes stirring, makes vanadium titanium function ceramics slurry;
B. directly solidify casting:
Add the water of 12% quality in the mixture of stupalith after ball mill pulverizing and wollastonite, the quality of wollastonite is 10% of a stupalith, adds the NH of 0.1mol/L then
4NO
3Regulate pH value to 11, stirring pulping heat slurry and to inject the normal temperature mould after 10 minutes in 60 ℃ of water-baths, and the slurry cooling also changes solid-state base substrate into, places the demoulding after 5 hours in air, the formation ceramic matrix; After the ceramic matrix drying, at the vanadium titanium function ceramics slurry of its surface-coated steps A preparation, glazing protection after the coat drying;
C. low temperature fast firing:
Adopt roller kiln equipment, temperature rise rate is 10 ℃/minute, and insulation is 50 minutes when being warmed up to 1000 ℃, obtains vanadium titanium function ceramics.
Embodiment 2:
A. raw materials pretreatment:
Stupalith and the wollastonite mixture that in tailings in vanadium extraction, add 20% quality through ball mill pulverizing, the quality of wollastonite is 15% of a stupalith, mixing laggard promoting the circulation of qi stream pulverizes, select materials through ultrasonic vibration screening and to obtain the micron particle material of 2 μ m-4 μ m, the water that adds 30% quality mixes stirring, makes vanadium titanium function ceramics slurry;
B. directly solidify casting:
Add the water of 10% quality in the mixture of stupalith after ball mill pulverizing and wollastonite, the quality of wollastonite is 20% of a stupalith, adds the NH of 0.12mol/L then
4NO
3Regulate pH value to 10, stirring pulping heat slurry and to inject the normal temperature mould after 12 minutes in 70 ℃ of water-baths, and the slurry cooling also changes solid-state base substrate into, places the demoulding after 8 hours in air, the formation ceramic matrix; After the ceramic matrix drying, at the vanadium titanium function ceramics slurry of its surface-coated steps A preparation, glazing protection after the coat drying;
C. low temperature fast firing:
Adopt roller kiln equipment, temperature rise rate is 8 ℃/minute, and insulation is 40 minutes when being warmed up to 1100 ℃, obtains vanadium titanium function ceramics.
Embodiment 3:
A. raw materials pretreatment:
Tailings in vanadium extraction is carried out comminution by gas stream, and selecting materials through the ultrasonic vibration screening obtains the micron particle material of 0.1 μ m-2 μ m, and the water that adds 35% quality mixes stirring, makes vanadium titanium function ceramics slurry;
B. directly solidify casting:
Add the water of 12% quality, the nano-titanium oxide of 2% quality in the mixture of stupalith after ball mill pulverizing and wollastonite, the quality of wollastonite is 15% of a stupalith, adds the NH of 0.08mol/L then
4NO
3Regulate pH value to 12, stirring pulping heat slurry and to inject the normal temperature mould after 15 minutes in 70 ℃ of water-baths, and the slurry cooling also changes solid-state base substrate into, places the demoulding after 2 hours in air, the formation ceramic matrix; After the ceramic matrix drying, at the vanadium titanium function ceramics slurry of its surface-coated steps A preparation, glazing protection after the coat drying;
C. low temperature fast firing:
Adopt roller kiln equipment, temperature rise rate is 6 ℃/minute, and insulation is 30 minutes when being warmed up to 1000 ℃, obtains vanadium titanium function ceramics.
Embodiment 4:
A. raw materials pretreatment:
Stupalith and the wollastonite mixture that in tailings in vanadium extraction, add 10% quality through ball mill pulverizing, the quality of wollastonite is 10% of a stupalith, mixing laggard promoting the circulation of qi stream pulverizes, select materials through ultrasonic vibration screening and to obtain the micron particle material of 2 μ m-5 μ m, the water that adds 25% quality mixes stirring, makes vanadium titanium function ceramics slurry;
B. directly solidify casting:
In the mixture of stupalith after ball mill pulverizing and wollastonite, add the water of 6% quality, the nano zine oxide of 1% quality, the nano aluminium oxide of 1% quality, the quality of wollastonite is 10% of a stupalith, adds the NH of 0.15mol/L then
4NO
3Regulate pH value to 11, stirring pulping heat slurry and to inject the normal temperature mould after 15 minutes in 70 ℃ of water-baths, and the slurry cooling also changes solid-state base substrate into, places the demoulding after 8 hours in air, the formation ceramic matrix; After the ceramic matrix drying, at the vanadium titanium function ceramics slurry of its surface-coated steps A preparation, glazing protection after the coat drying;
C. low temperature fast firing:
Adopt roller kiln equipment, temperature rise rate is 10 ℃/minute, and insulation is 45 minutes when being warmed up to 1000 ℃, obtains vanadium titanium function ceramics.
Embodiment 5:
A. raw materials pretreatment:
Stupalith and the wollastonite mixture that in tailings in vanadium extraction, add 15% quality through ball mill pulverizing, the quality of wollastonite is 16% of a stupalith, mixing laggard promoting the circulation of qi stream pulverizes, select materials through ultrasonic vibration screening and to obtain the micron particle material of 1 μ m-4 μ m, the water that adds 30% quality mixes stirring, makes vanadium titanium function ceramics slurry;
B. directly solidify casting:
In the mixture of stupalith after ball mill pulverizing and wollastonite, add the water of 15% quality, the nano-sized iron oxide of 1% quality, the nano-titanium oxide of 1% quality, the quality of wollastonite is 20% of a stupalith, adds the NH of 0.12mol/L then
4NO
3Regulate pH value to 11, stirring pulping heat slurry and to inject the normal temperature mould after 15 minutes in 70 ℃ of water-baths, and the slurry cooling also changes solid-state base substrate into, places the demoulding after 8 hours in air, the formation ceramic matrix; After the ceramic matrix drying, at the vanadium titanium function ceramics slurry of its surface-coated steps A preparation, glazing protection after the coat drying;
C. low temperature fast firing:
Adopt roller kiln equipment, temperature rise rate is 10 ℃/minute, and insulation is 45 minutes when being warmed up to 1000 ℃, obtains vanadium titanium function ceramics.
Claims (6)
1. a low temperature fast firing prepares the method for vanadium titanium function ceramics, it is characterized in that, it has preparation process and is:
A. raw materials pretreatment:
Tailings in vanadium extraction is carried out comminution by gas stream, and selecting materials through the ultrasonic vibration screening obtains the micron particle material of 0.1 μ m-5.0 μ m, and the water that adds the 15-40% quality mixes stirring, makes vanadium titanium function ceramics slurry;
B. directly solidify casting:
In the mixture of stupalith after ball mill pulverizing and wollastonite, add the water of 6-15% quality, add the defloculating agent adjusting pH value of 0.06-0.15mol/L to 10-12 then, stirring pulping, slurry heated in 60-70 ℃ of water-bath inject the normal temperature mould after 6-15 minute, the slurry cooling also changes solid-state base substrate into, in air, place the demoulding after 2-8 hour, form ceramic matrix; After the ceramic matrix drying, at the vanadium titanium function ceramics slurry of its surface-coated steps A preparation, glazing protection after the coat drying;
C. low temperature fast firing:
Adopt roller kiln equipment, temperature rise rate is 6-15 ℃/minute, and insulation is 30-50 minute when being warmed up to 1000-1100 ℃, obtains vanadium titanium function ceramics.
2. a kind of low temperature fast firing according to claim 1 prepares the method for vanadium titanium function ceramics, it is characterized in that, in the described steps A before the comminution by gas stream, also add the stupalith of 0.01-30% quality and the mixture of wollastonite in the tailings in vanadium extraction, the quality of wollastonite is the 10%-20% of stupalith, the mixture of stupalith and wollastonite mixes with tailings in vanadium extraction after ball mill pulverizing, carries out comminution by gas stream then.
3. a kind of low temperature fast firing according to claim 1 and 2 prepares the method for vanadium titanium function ceramics, it is characterized in that, also adds the nanometer additive of 0.1-5% quality when adding water in the described steps A.
4. a kind of low temperature fast firing according to claim 3 prepares the method for vanadium titanium function ceramics, it is characterized in that, described nanometer additive is one or more in nano-titanium oxide, nano zine oxide, nano aluminium oxide, the nano-sized iron oxide.
5. prepare the method for vanadium titanium function ceramics according to claim 1,2,4 arbitrary described a kind of low temperature fast firings, it is characterized in that the defloculating agent described in the step B is NH
4NO
3, the quality of wollastonite is the 10%-20% of stupalith among the step B.
6. a kind of low temperature fast firing according to claim 3 prepares the method for vanadium titanium function ceramics, it is characterized in that, the defloculating agent described in the step B is NH
4NO
3, the quality of wollastonite is the 10%-20% of stupalith among the step B.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910892A (en) * | 2012-09-28 | 2013-02-06 | 新嘉理（江苏）陶瓷有限公司 | Black ceramic plate prepared by natural minerals and extracted vanadium tailings and preparation method of black ceramic plate |
| CN106866115A (en) * | 2017-03-20 | 2017-06-20 | 四川大学 | The preparation method of far-infrared anti-biotic ceramics |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386528A (en) * | 2008-10-27 | 2009-03-18 | 佛山欧神诺陶瓷股份有限公司 | Method for producing ceramic tile by metallurgical steel slag |
| CN101482335A (en) * | 2006-05-25 | 2009-07-15 | 山东天虹弧板有限公司 | Composite ceramic solar plate |
-
2010
- 2010-12-13 CN CN2010105996379A patent/CN102167598A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101482335A (en) * | 2006-05-25 | 2009-07-15 | 山东天虹弧板有限公司 | Composite ceramic solar plate |
| CN101386528A (en) * | 2008-10-27 | 2009-03-18 | 佛山欧神诺陶瓷股份有限公司 | Method for producing ceramic tile by metallurgical steel slag |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910892A (en) * | 2012-09-28 | 2013-02-06 | 新嘉理（江苏）陶瓷有限公司 | Black ceramic plate prepared by natural minerals and extracted vanadium tailings and preparation method of black ceramic plate |
| CN106866115A (en) * | 2017-03-20 | 2017-06-20 | 四川大学 | The preparation method of far-infrared anti-biotic ceramics |
| CN106866115B (en) * | 2017-03-20 | 2020-01-31 | 四川大学 | Preparation method of far infrared antibacterial ceramic |
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Application publication date: 20110831 |