CN101153749A - Method for compounding solid netted black porcelain sunlight absorbing layer on ceramic solar panel - Google Patents
Method for compounding solid netted black porcelain sunlight absorbing layer on ceramic solar panel Download PDFInfo
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- CN101153749A CN101153749A CNA2006100686666A CN200610068666A CN101153749A CN 101153749 A CN101153749 A CN 101153749A CN A2006100686666 A CNA2006100686666 A CN A2006100686666A CN 200610068666 A CN200610068666 A CN 200610068666A CN 101153749 A CN101153749 A CN 101153749A
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- mud
- biscuit
- vanadium
- ceramic
- ceramic solar
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Links
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Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/10—Details of absorbing elements characterised by the absorbing material
- F24S70/16—Details of absorbing elements characterised by the absorbing material made of ceramic; made of concrete; made of natural stone
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a method for compounding solid reticular black porcelain sunlight absorbing layer on ceramic solar plate, wherein, industrial waste residues and metal minerals rich in the transition elements in fourth period are used as main raw materials to be ground into slurry; the slurry is sprayed on the dry surface of a green body of a hollow ceramic solar plate through compressed air by adopting a single spray gun or a plurality of spray guns; the pressure and the flow rate of the compressed air and the proportion of the slurry are controlled, so as to lead fog drops in initial contact with the dry green body surface of the ceramic solar plate to form mud particles which have a certain strength, are relatively dry and adhere to the surface of the green body plate because of the fast water absorption of the dry green body and the surface tension of the fog drops; the subsequently sprayed fog drops first meet the mud particles which have a certain moisture absorption ability and protrude from the surface, and then the fog drops adhere to the mud particles, thus the heteropic incontinuous fog drop mud accumulation bodies which are in columnar shapes, steeple shapes, vertical wall shapes, honeycomb shapes or porous shapes, have moisture absorbed and have a certain strength are accumulated in turn; spraying is stopped before the solid accumulation bodies reach to a certain height and lose moisture absorption ability, thereby getting a solid reticular black porcelain green body layer on the surface of the hollow ceramic solar green body plate; the hollow ceramic green body plate having the solid reticular black porcelain green body layer is dried and fired under high temperature; the firing temperature and time are controlled to ensure that the solid reticular black porcelain green body layer and the green body of a hollow ceramic solar plate are simultaneously sintered into a solid reticular black porcelain layer and a porcelain hollow solar.
Description
(1) technical field
The present invention relates to the manufacture method of field of solar energy utilization sunshine absorbed layer, is the method for compound sunlight absorbing layer on ceramic solar plate specifically, is the method for compounding solid netted black porcelain sunlight absorbing layer on ceramic solar plate furtherly.
(2) background technology
The solar energy utilization mainly is divided into solar photovoltaic utilization, solar thermal utilization mode, solar thermal utilization mainly is a solar water heater at present, solar water heater is divided into closing-sunning type and circulating, circulating efficient is higher, its heat collection body mainly adopts board-like heat collection body of metal tube and vacuum glass tubular type heat collection body, and the board-like heat collection body of metal tube is also referred to as flat heat collection body.Both all have the following disadvantages: 1. the board-like heat collection body of metal tube mainly adopts materials such as copper, aluminium, glass tube with vacuum heat collection body structure and manufacturing process relative complex, and the price of calculating both with every square metre of endotherm area is all than higher.2. both all adopt the black sunlight absorbing coating that low temperature applies, and the aging sunlight absorption rate that makes that has under long-term effect of sunlight to a certain degree decays, and is one of reason that causes efficient and life problems.3. be combined as a whole with building owing to reasons such as material, structure and cost are difficult.
The homogeneous ceramic solar panel be meant with tailings in vanadium extraction or (with) other trade waste, natural minerals that are rich in transition elements mix the integral black made the back or the ceramic hollow solar heat-collection plate of grey black look with the conventional ceramic raw material, composite ceramic solar panel is meant with the conventional ceramic to be matrix, with tailings in vanadium extraction or (with) other trade waste, natural minerals that are rich in transition elements mix the black made the back or the mutually compound ceramic hollow solar energy heating body of ceramic blankets of grey black look with the conventional ceramic raw material.Composite ceramic solar panel, homogeneous ceramic solar panel can be referred to as ceramic solar plate.
Usually solar water heater is made up of support, solar thermal collector, storage tank, pipeline, or form by support, glass tube with vacuum, storage tank, pipeline, described heat collector generally is made up of shell, heat preserving and insulating material, metallic solar energy heat collection body, transparent cover plate with black surface.
Produce black ceramic in the past and must add Co, Cr, Ni, Mn, Fe grade in an imperial examination phase transition elements all around, price is very expensive, it is the method that one of raw material is produced various black ceramic goods with the tailings in vanadium extraction that the Chinese invention patent CN85102464 that the inventor declares and obtains " production method and the goods thereof of black ceramic goods raw material ", CN86104984 " a kind of pottery powder " have narrated, and this black ceramic is called vanadium-titanium black ceramic.This invention is that nine external state invention patent certificates are declared and obtained to title with " ceramic powders and goods thereof " (Ceramrc powder and drticles) again, is respectively United States Patent (USP) 4737477, Japan Patent 1736801, English, method, moral, austrian patent (EUROPEAN PATENT OFFICE) 0201179, Australian Patent 578815, Singapore's patent 1009/91, Finnish patent 81336 and Hong Kong patent 1077/1991.The later stage eighties inventor has declared patents such as " black ceramic solar tile ", " black ceramic parapet-type solar thermal collector ", " black ceramic solar energy roof ", " method for forming black porcelain solar heat collecting plate ", and the beginning of this century, the inventor declared patents such as " ceramic solar plate ", " manufacture method of composite ceramics hollow solar heat-collection plate ", " structure and material on a kind of new type solar energy roof ", " manufacturing of ceramic solar board heat collector and installation method ".
Vanadium titano-magnetite obtains vanadium-bearing hot metal through melting, 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 the wet extraction vanadium extraction, and the remaining residue as discarded object is tailings in vanadium extraction behind the extraction vanadium.
China's year output tailings in vanadium extraction is about 300,000 tons at present, and the main place of production is Sichuan, Hebei, Liaoning etc., and representative enterprise is Panzhihua Iron, second chemical plant, Chengde, Jinzhou vanadium industry company etc.Tailings in vanadium extraction is rich in Fe, Cr, Mn, V, Ti grade in an imperial examination phase element complex compound all around, account for about 80% of gross weight, it is a kind of very special trade waste, wherein the extraction of any composition and utilization all can not show a candle to the economy of corresponding natural minerals, and their aggregate is a kind of very stable ceramic black colorant, the manufacturing that the artificial for a long time Co for preparing is ceramic black colorant must be through strict prescription, meticulous, complicated processing just can obtain the ceramic black colorant that is colour-stable, about 200,000 yuan of common prices per ton.Tailings in vanadium extraction is not only stable ceramic black colorant, and itself also is good basalt raw material, and hundred-percent tailings in vanadium extraction just can produce that physicochemical property is good, the exsertile vanadium-titanium black ceramic goods of photo-thermal transformational.
Vanadium-titanium black ceramic was invented in 1984, on April 1st, 1985 began to declare patent, 1986 by technical appraisement, vanadium-titanium black ceramic can be made hollow solar heat-collection plate, far-infrared radiation element, the art work, decorative panel for building etc., wherein the current production rate maximum is the vanadium-titanium black ceramic decorative panel for building, the at present main place of production is Guangdong, Shanghai, and representative enterprise is the great ceramics factory in east, Foshan City, the grand basic special cermacis in Shanghai company etc.China's ceramic building decorative panel (brick) output occupies first place in the world, annual production accounts for world wide production about 50%, because the vanadium-titanium black ceramic decorative panel uses a large amount of tailings in vanadium extraction, takies a large amount of stockyards in the past, the present price of tailings in vanadium extraction that becomes vanadium extraction factory heavy burden has reached 160-300 unit/T.Therefore whole nation tailings in vanadium extraction output factory obtains year tens million of units of net income, and vanadium-titanium black ceramic is decorated the several hundred million units of hair plates annual sales amount, 1 to 3 times of polishing back increment.Early 1990s is with up to ten thousand square metres of 300 * 300 millimeters vanadium-titanium black ceramic hollow solar panels of gypsum mould grouting forming method trial-production, manufacturing and use vanadium-titanium black ceramic solar water heater are more than hundreds of, directly be built in nearly thousand square metres of vanadium-titanium black ceramic solar water heaters on the roof, adopt brick, cement housing, magnesia housing, water vat storage tank and the special ceramic storage tank of making, purpose is progressively to develop into vanadium-titanium black ceramic solar energy roof.0.09 square metre of 300 * 300 millimeters vanadium-titanium black ceramic solar panel veneer area, water capacity 0.9kg, water temperature can reach 100 ℃ during the vexed solarization of single-glass veneer, the vanadium-titanium black ceramic solar water heater obtains the first prize in Shandong Province solar water heater the whole province comparation and assessment in 1986, water quality before and after the heating of vanadium-titanium black ceramic solar water heater is not found visible variation after testing, using solar panel more than 10 years not have fades, corrosion, the aging sign that waits, but gypsum mould grouting moulding vanadium-titanium black ceramic hollow solar panel method, shaping efficiency is low, moulding large scale solar panel yield rate is low, small size plate joint is too much, install loaded down with trivial details, be difficult to develop into the large-scale industrial production method, be difficult to realize the large-scale promotion use.The large scale solar panel with the trial-production of vacuum extrusion molding of inventor's recent development, shaping efficiency exceeds tens of times than gypsum mould grouting method, and scalable several times to tens times of board dimension can develop forming large-scale production and application.
The most important characteristic of vanadium-titanium black ceramic is the photo-thermal transfer characteristic, vanadium-titanium black ceramic is typical energy and material, inventor's more practical large scale vanadium-titanium black ceramic solar panel of research and development and be that superficial layer is the vanadium-titanium black ceramic composite ceramic solar panel of matrix with the conventional ceramic with the vanadium-titanium black ceramic with all strength is used for vanadium-titanium black ceramic solar energy roof for this reason.Whole nation tailings in vanadium extraction quantum of output can be produced about 1,500 ten thousand square metres of practical large scale vanadium-titanium black ceramic solar panel per year, can be and make its annual production of vanadium-titanium black ceramic composite ceramic solar panel above 1,000,000,000 square metres, the photo-thermal transfer process betides body surface, and both performances can accomplish there is no significant difference.
About 600 yuan of the price of present one ton of solid hair plates of common porcelain, about 700 yuan of the solid hair plates of vanadium-titanium black ceramic, about 3000 yuan of cast iron, 4500 yuan of steel, 24000 yuan of aluminiums, 70000 yuan of copper materials, compare its proportion with iron and steel and differ 3 times, promptly the porcelain plate volume bought of identical currency is an iron and steel more than 10 times, and the porcelain corrosion resistance life-span can be longer more than 10 times than iron and steel, can think that ceramic material is more corrosion-resistant than any metal, every square metre of vanadium-titanium black ceramic or composite ceramic solar panel weight can be less than 40kg.Ceramic material is cheap to be because that big, widely distributed, the haul distance of raw material reserves is short, processing temperature can be lower than 1200 ℃, processing technology is simple, it is that these factors are difficult to change because the raw material reserves are few, effective content is low, haul distance is far away, about 1600 ℃ or need electrolysis for production, processing technology complexity of processing temperature that metal material costs an arm and a leg.So conventional ceramic, vanadium-titanium black ceramic or be that the surface is that matrix is fit to make the solar energy heating body and is used for the solar energy roof with the general ceramic material with the vanadium-titanium black ceramic, both are more suitable for making the solar energy heating body and are used for the solar energy roof after outstanding.
Vanadium-titanium black ceramic can a large amount of energy that absorb in the sunlight during by solar radiation, and sunlight absorption rate can reach 0.9, and through test, in latitude 37 degree areas, summer, fine 1 square metre of vanadium-titanium black ceramic solar panel can be heated to 10kg water 100 ℃.Vanadium-titanium black ceramic is good optical-thermal conversion material, is novel energy and material.Vanadium-titanium black ceramic black is pure, physicochemical property is good, at present be used to produce the decorative panel for building of solid surface grinding in a large number, low production cost, about 12 millimeters of vanadium-titanium black ceramic decorative panel thickness, 20～30 yuan every square metre of the hair plates prices of not polishing, its sales volume has reached several hundred million units, the vanadium-titanium black ceramic decorative panel utilizes just that vanadium-titanium black ceramic black is pure, decorative effect is sedate, serious this characteristic, and the photo-thermal transfer characteristic that itself has does not obtain sufficient development and utilization as yet.Vanadium-titanium black ceramic intensity height, rupture strength 45～100MPa, almost double than common Imitation Rock Porcelain Tiles, cheap for manufacturing cost, not burn into do not wear out, do not fade, nontoxic, harmless, "dead", fire through thousands of degree temperature and to form, through accelerated ageing, do not find the sunlight absorption rate attenuation problem, can have almost permanent service life, be fit to very much make the solar energy heating body, easily combine with building, be used for the solar energy roof, its intensity is about ten times on common tile, service time can with the building the same life-span.
40,000,000,000 square metres of China's existing building areas, about 10,000,000,000 square metres of roof area, 2,000,000,000 square metres of annual new buildings, about 500,000,000 square metres of roof, the energy for building enormous amount, be mainly used in summer air-conditioning, warming and life hot water, fossil energy is in short supply, making full use of regenerative resource is general trend, want to utilize on a large scale solar energy, must at first make from the nearest roof of the mankind and possess the function that absorbs solar energy economically, the inevitable main power consumption items that at first is used for human in room and workplace of the solar energy that the roof absorbs: air-conditioning, heating, hot water, next is culinary art, household electrical appliances, illumination, existing solar energy roof and solar energy housing can have been accomplished by 50～80% of the solar energy supply room energy, even accomplish whole power self-supports, yet these experimental solar energy roofs and solar energy housing are based upon on the prior art basis, the quantity of the conventional energy resource that construction and life period are spent surpasses the solar energy that obtains its same period sometimes, vanadium-titanium black ceramic solar energy roof can change this situation, depends primarily on 2 points: 1. propose and realize low cost, large-scale production vanadium-titanium black ceramic solar panel is the method for vanadium-titanium black ceramic composite ceramic solar panel especially; 2. propose and realize can be on common house low-cost build and operation, with the scheme of building with the vanadium-titanium black ceramic solar energy roof in life-span.
In recent years Kai Fa absorption type air-conditioner can be produced the cold wind that temperature is lower than 25 ℃ greater than the power conversion of 65 ℃ hot water with temperature, be used for summer air-conditioning, winter sunlight can with more than the air heat to 30 in the solar heat-collection plate ℃ as the Central Heating Providing heating buildings.Solar energy is unsettled; the thin energy; about about 1 kilowatt of every square metre of power upper limit; the Chinese city resident is about 15 square metres of roof area per family; about 100 square metres of rural area; still developing rapidly at present; utilize solar energy to realize summer air-conditioning; warming; must provide cheap; longevity; efficient; the easy solar energy heating body that combines with building; the vanadium-titanium black ceramic solar panel can be realized this goal; but vanadium-titanium black ceramic is primary raw material with the tailings in vanadium extraction; and the demand and the output of vanadium are all little at present, cause the tailings in vanadium extraction quantum of output that certain limit is arranged, and are superficial layer so develop with the vanadium-titanium black ceramic; be the composite ceramics hollow solar heat-collection plate of matrix with conventional pottery; so that tailings in vanadium extraction is used more effectively, be very important.China produces about 4,000,000,000 square metres of ceramic wall and floor bricks per year, wherein projected area is greater than about 1,000,000,000 square metres of 0.2 square metre Imitation Rock Porcelain Tiles, therefore produce per year more than several hundred million square metres, the surface is a vanadium-titanium black ceramic, matrix may be accomplished for ceramic usually composite ceramics hollow solar heat-collection plate, also is to need very much with necessary.Geothermal power generation in recent years can be adopted 70 ℃ of left and right sides hot water by adopting 90 ℃ of hot water to develop into, and cost of electricity-generating can be lower than the conventional electric power cost, and the low-temperature electricity-generating technology reaches its maturity, also can be used for low-temperature electricity-generating with relative low cost, mass-produced ceramic solar plate.Geothermal power generation generally needs to underground hundreds of rice, goes up the xeothermic rock stratum injection of km depths or extract hot water, usually hot water has certain corrosivity, need take anti-corrosion measure, ceramic solar plate can provide purer hot water, may realize lower cost of electricity-generating.Vanadium-titanium black ceramic composite ceramics hollow solar heat-collection plate is also referred to as the vanadium-titanium black ceramic composite ceramic solar panel, is called for short composite ceramic solar panel.Composite ceramic solar panel, homogeneous ceramic solar panel can be referred to as ceramic solar plate.
Usually the function on roof is windproof, rain, Exposure to Sunlight, insulation, shape is broadly divided into " people " font, plane, Yimianpu type, the roof building is on supporting part, supporting part generally is body of wall, concrete component or house beam (room frame) and purlin, and roof itself is made of structure sheaf, heat-insulation layer, watertight composition usually.
Structure sheaf on China general urban architecture roof is precast slab or cast-in-place concrete, heat-insulation layer is light heat insulation materials such as expanded perlite, vermiculite power or slag, watertight composition is various malthoids, for the globality that keeps heat-insulation layer be convenient to construct and also have one deck cement between common heat-insulation layer and the watertight composition.
General rural area or township construction roof material have diversity, structure sheaf adopts thin large-size glass fibre cement watt, wood lath, wicker, reed etc., heat-insulation layer often adopts the mixture of sawdust and clay, lime etc., watertight composition is used clay shingle more, is also constantly developing to the urbanization direction with economic development rural area, township construction roof material.
Solar energy heat utilization device mainly is flat plate solar water heater and glass tube with vacuum water heater at present, flat plate solar water heater is mainly by support bracket, heat collector and water tank constitute, heat collector is by structure sheaf or be called the heat collector shell, insulation material, the flat heat collecting body, transparent cover plate is formed, the flat heat collecting body is generally by the metal manufacturing, compare with normal-temperature water, hot water below 100 ℃ has stronger corrosivity to metal, be the corrosion-resistant general copper aluminium compound slab heat collection body that adopts that increases the service life, with thicker copper pipe is transverse tube, thinner copper pipe is the passage that the vertical tube welding forms water, about 10 centimeters at interval of vertical tubes, it is one that aluminium sheet occupies spacer area or entire area and copper pipe compound through methods such as extruding, surface coverage selectivity or non-selective solar energy absorbing paint, section from heat collector, heat collector is by structure sheaf, heat-insulation layer, heat collection body, watertight composition is formed, wherein watertight composition is a transparent cover plate, generally be glass or transparent plastic, play waterproof simultaneously, see through sunlight, form the effect that sealing constitutes greenhouse effects.Selective coating and non-selective coating all can degenerate with age, and progressively reduce sunlight absorption rate.
The glass tube with vacuum water heater mainly is made up of support bracket, glass tube with vacuum heat collection body and water tank, the glass tube with vacuum heat collection body is that one thick one thin two coaxial glass blind pipes combine, an opening, a sealing, it between the thickness pipe vacuum, interior tube-surface covers slective solar energy absorbing coating, and water heats in interior pipe, to the water tank delivering hot water.
Solar energy is renewable, inexhaustible, not environmentally hazardous green energy resource, is again unstable, thin, the low-density energy.The roof be the easiest by solar radiation, nearest from the mankind, area is maximum, minimum, the easiest collection of comprehensive utilization ratio at present, the place that utilizes sunlight and space.
Comprising that solar water heater, solar energy roof, solar energy housing are in order to utilize solar energy to save conventional energy resource thereby make, build solar energy equipment, is for energy-conservation.Should to be (seat) solar energy equipment deduct the poor of whole energy that manufacturing, construction, this (seat) of maintenance, repair device consumed at the obtained whole energy of life period to its criterion, this difference can be called the Q value, Q is that positive value specifies is energy-conservation, negative value consumes energy, and loses more than gain.Obtained energy ratio is easier to calculate, the energy that the energy that is consumed should comprise manufactured materials, become energy that other parts consume and manufacturing, maintenance personal and related personnel to live and consumed every day materials processing, as smelt 1 ton of steel and consume conventional energy and amount to about 700 liters of oil, the coal gas that practitioner family expends, electric power energy etc., these energy resource consumptions are difficult to calculate.A kind of fairly simple way is to carry out and adopt the contrast of the related device of conventional energy resource with amount of money, because amount of money has reflected the consumption of the energy to a great extent, it also is the whether economic accounting foundation of social recognition, only be used to provide bath hot water as a solar water heater, 3000 yuan of purchase prices, scrap after average 10 years, maintenance cost is amounted to expensive 500 yuan in 10 years, 3000 yuan 10 annual interests are made as 1000 yuan, then total expenditure is 4500 yuan, use a gas water heater, as also only being used to provide bath hot water, 300 yuan of purchase prices are scrapped after average 10 years, purchase commodity in 10 years, maintenance cost, gas charge and interest add up to a unit, and then reduced value is (a-4500) unit.Therefore all should to make reduced value be on the occasion of just having long-term existence value and development prospect to any (seat) solar energy equipment.
Usually 50 years supreme century-old service life of building requirements, general watertight composition service life is 3～20 years, modern architecture watertight composition maintenance intervals can reach more than 15 years, and the every construction cost per square meter in roof that comprises structure sheaf, heat-insulation layer, watertight composition at present is roughly between hundred yuan of the dozens of yuan to two.
Although the solar energy roof should be at first adopted in the solar energy utilization, but the solar energy roof is very rare at present, and majority is that metallic solar energy heat collector or vacuum glass solar thermal collector are directly installed on the roof of having built, is not the solar energy roof of real meaning.At present generally use on the solar energy roof, we think basic reason be its Q value be difficult to realize big numerical value on the occasion of, have in addition be negative value, concrete reason is analyzed as follows:
1. price height---the board-like and every square metre of price of vacuum glass heat collection body of metal tube is hundreds of units, and only the heat collection body price is exactly several times even tens times of common roof cost.
2. the life-span is short---and metal and glass tube with vacuum heat collection body generally adopt low-temperature solar energy coating, sunlight absorption rate decays easily, the board-like copper pipe soldering opening of metal tube is many, soldering opening corrodes easily, coating performance decay and weld bond corrosion caused the average life span of metallic solar energy heat collector about about 10 years, outside the glass tube with vacuum removing coating is aging, also there is vacuum life, glass tube gas leakage, factors such as fragmentation, China water source mostly is hard water, Ca, the Mg ion is many, be easy to generate scale, problems such as glass blind pipe are stopped up in the scale flocculent deposit, and a variety of causes causes the vacuum glass tube heat collector average life span also about 10 years.Generally also need in time through repeatedly keeping in repair and part exchanging 10 years left and right sides, average life span is meant the separate unit solar water heater of 1～2 square metre of daylighting area about 10 years, be used for the roof as large tracts of land and mean that then needs often repair the roof, this is difficult to accept for 50 years service life to the building more than 100 years.
3. average efficiency is not high---and 1. the low temperature coating began to wear out in several years, and sunlight absorption rate progressively descends, and whole life period average efficiency is not high; 2. copper material costliness, tube pitch be from greatly, and aluminium sheet absorbs lateral transport behind the solar energy and gives medium in the copper pipe, average heat transfer distance 30 millimeter.Because structural limitations, the space is big between the glass tube with vacuum pipe, and the black absorption layer only accounts for structural area about 50%, and noon, sunlight was strong, but a large amount of sunlight pass the space between pipe during noon sunlight direct projection, have influenced collecting efficiency.
4. difficulty combines with building---and the roof is by structure sheaf, heat-insulation layer, watertight composition constitutes, solar thermal collector is by structure sheaf, heat-insulation layer, the thermal-arrest layer, watertight composition (hyaline layer) constitutes, so-called solar energy roof certainly will require both are organically combined, shared as far as possible both functional layer, just can play not only keep the function on original roof but also can obtain therefrom that solar energy is used for building various with can needs, and reduction construction cost, as previously mentioned, because above-mentioned two kinds of heat collection bodies have various deficiencies, its reliability further descends when forming the large tracts of land use, be difficult to design a kind of rational solar house roof construction, following result can occur even design also: 1. the roof cost improves several times to tens times; 2. the roof dependability descends, cause the Q value on this solar energy roof be difficult to become bigger on the occasion of.Therefore, on the basis of existing metallic solar energy heat collection body, vacuum glass tube solar heat-collecting body, be difficult to the solar energy roof that construction can generally be accepted by the user, use in a large number.
The basis on ceramic solar roof is ceramic solar plate and ceramic solar energy collector, is reduced at the installation procedure on the roof, with the assembling of ceramic solar energy collector, install and realize that batch production, modularization are crucial.
The solar energy heating body relies on superficial layer to absorb solar energy, superficial layer is very big to the technical and economic performance influence that solar energy utilizes to the absorbability of solar energy, for the efficient that improves solar energy equipment, reduce cost, various countries' solar energy and material scientific worker attach great importance to research, exploitation solar absorption superficial layer, owing to generally adopted methods such as plating, vacuum coating, anodic oxidation, coating in the past, so generally the solar absorption superficial layer is called solar energy absorbing coating, basic characteristics be mostly be black, rough porous is striven on the surface.
More than the coating of now having developed and having used is hundreds of at least, can classify according to principle of absorption, structure and manufacturing process.
Press principle, structural classification:
1. coated semiconductor---utilize electron transition to absorb energy, mostly be transition metal oxide,, tri-iron tetroxide black etc. as black chromium, black nickel, cupric oxide.
2. interference of light coating---utilize multilayer film to the interference of light principle, reduce the reflection of light rate, increase absorptivity, Al
2O
3-Mox-Al
2O
3(AMA) trilamellar membrane, A/N-Al/Al eight tunics etc.
3. Mie scattering coating---utilize metallic finely divided in the parent that light is carried out repeatedly scattering and internal reflection absorbs it, as Co-Al
2O
3, Al-Al
2O
3, Au-Al
2O
3Coating etc.
4. porous coating---utilize rough surface that light is played the trap effect, make the surface discontinuity size suitable with the visible spectrum peak value, in the shortwave side with black hole form light harvesting, the long wave side is with the plane form radiant light, as the Cu-CuO coating that forms on copper surface with chemical attack, the porosity that the chemical vapor deposition coating of tungsten and coarse black chromium form cellular coating, alumilite process coating reaches 22% etc.
Classify by manufacturing process:
1. electroplated coating---as black nickel, black chromium, black brill, black nickel one tin alloy coat etc.
2. electrochemical conversion coating---as alumilite process coating, CuO conversion coating, Mo melanism conversion coating etc.
3. vacuum coating coating---utilize vacuum evaporation and magnetron sputtering technique to produce, as pbs/Al/Al, AlCN, Ni-Cr, multilayer gradual change aluminium nitrogen aluminium Al-N/Al coating etc.
4. paint coatings---as with MnO
2, Fe
3O
4, Cr
2O
3, PbS, Fe
3CuO
5Deng being black pigment, be the various coatings of binding agent with organic-silicon-modified acrylic acid resin, EP rubbers, fluororesin etc.
The coating kind is a lot, but the ubiquity following problems:
1. under the sunlight long-term irradiation, optical property, the sunlight absorption rate of general coating have relaxation phenomenon.Possible reason be 1. coating in, form in the low temperature, even some coating can high-temperature process, its matrix also is difficult to bear high temperature.2. coating in very short time in addition moment form.
3. include organic compounds etc. in the coating, above-mentioned condition is difficult to form the resistant mineral structure of high bond energy, the temperature that general coating can bear is 150～350 ℃, is difficult to break through 400 ℃, and high bond energy mineral can be about 1000 ℃ in addition higher temperature keep the stable of structure and performance.
2. coating manufacturing process more complicated or prices of raw and semifnished materials costliness cause the coating manufacturing cost higher.
The problems referred to above make common coating price height, Acceptable life short, if with 10 years be service life because performance degradation, average sunlight absorption rate is not high.
(3) summary of the invention
Purpose of the present invention: the objective of the invention is on ceramic hollow sheeting matrix to cover with trade waste or (with) metalliferous mineral is that the black porcelain mud layer of primary raw material becomes solid netted black porcelain sunlight absorbing layer with ceramic hollow sheeting through high temperature sintering, this sunlight absorbing layer integral black, not burn into do not wear out, do not fade, nontoxic, harmless, "dead", low production cost, the stable not decay in time of sunlight absorption rate, long service life.
The present invention is achieved in that
The conventional ceramic pug extruded with porous mold through vacuum pugging becomes the porous ventilating hole plate, through being processed into the hollow sheeting that the termination communicates, with pug plate of the same race shutoff two and tap into outlet, become hollow ceramic solar panel biscuit with import and export, with tailings in vanadium extraction or (with) other be rich in the period 4 transition metal industrial residue or (with) metalliferous mineral that is rich in the period 4 transition metal is that raw material or primary raw material grind into mud, with compressed air mud is sprayed on the dry hollow ceramic solar panel biscuit surface, adopt single spray gun or many spray gun sprayings, control compressed-air actuated pressure, the ratio of flow and mud makes the initial stage and the ceramic solar plate biscuit contacted droplet in surface of drying have certain intensity because the surface tension of the quick suction of dry biscuit and droplet forms, relatively dry, adhere to the mud pellet on biscuit plate surface, the droplet that follow-up spray falls at first runs into these mud pellets that protrudes in the surface with certain wettability power, stick on the mud pellet, be piled into column successively, the steeple shape, the wall shape, cellular, cavernous non-homogeneous, discontinuous, the droplet pug accumulation body that is had certain intensity by moisture absorption, when reaching a certain height, these three-dimensional accumulation bodies stop spraying before losing wettability power, thereby obtain the biscuit layer of solid netted black porcelain on hollow ceramic sun biscuit plate surface, this hollow ceramic biscuit plate with solid netted black porcelain biscuit layer is carried out high-temperature firing after drying, the control firing temperature and the time chien shih solid netted black porcelain biscuit layer and hollow ceramic solar panel biscuit be sintered to solid netted black enamel coating and porcelain hollow ceramic solar panel matrix simultaneously, high temperature sintering makes that solid netted black enamel coating and porcelain hollow ceramic solar panel matrix are sintered combined to be one, or the method that adopts twice firing with both sintered combined be one, its firing temperature makes solid netted black porcelain mud droplet accumulation horizon become ceramic material, spray gun is done relative motion with hollow ceramic solar panel biscuit surface at a certain angle during spraying, when single rifle sprays, single rifle is made the systematicness motion scan in biscuit plate surface, make movement velocity, the mud spouting velocity is corresponding with the biscuit rate of moisture absorption, guarantee that the droplet accumulation body has corresponding wettability power all the time, the accumulation body of large quantity of moisture by relatively dry in the droplet that sticks on the accumulation body is passed in the dry biscuit, make the droplet of new adhesion lose part moisture rapidly and have definite shape and intensity, droplet is poly-to become plane layer for the mud that flows collapses deposit thereby do not make, during the multiple gun spraying, hollow ceramic solar panel biscuit moves below spray gun, make movement velocity, the spray gun spacing distance is corresponding with mud spouting velocity and biscuit rate of moisture absorption, to achieve the above object, adjust the cohesive force between the particle in mud prescription and the moisture decision mud, control compressed-air actuated pressure, the speed and the size of the ratio decision ejection droplet of flow and mud, droplet is that mud and AIR MIXTURES are the mud balls of hollow, when sticking on the deposit, lose part moisture and harden into the hollow duricrust, the fragmentation of part spheroid, form the accumulation body of solid netted porous, the prescription of mud, cohesive force, the average diameter and the height of the speed decision accumulation body that dries out, the accumulation body height is 0.1～3 millimeter, the pore that is full of in the accumulation body is the moisture movement passage that dry biscuit causes when absorbing moisture, form fine hole when burning till, burn till each column of back accumulation body, steeple, wall, be covered with the hole on the honeycomb wall, the aperture is 0.1～50 micron, and solid netted black porcelain sunlight absorbing layer is black.
Described tailings in vanadium extraction is that vanadium titano-magnetite obtains vanadium-bearing hot metal through melting, vanadium-bearing hot metal obtains vanadium slag through blowing, vanadium slag adds auxiliary material and carries out roasting, and roasting material is carried out the wet extraction vanadium extraction, and the remaining residue as discarded object is tailings in vanadium extraction behind the extraction vanadium.
Tailings in vanadium extraction is rich in the period 4 transition metal, as: (Fe2O
3+ FeO) 50-70, TiO 5-9, MnO 4-7, CrO
30.002-3, V
2O
50.2-2 SiO
212-26, Al
2O
32-4, CuO 0.9-2, MgO 0.6-2, Na
2O 2-6, K
2O 0.012-0.12, tailings in vanadium extraction until through melting process, is always black through the high-temperature roasting of different temperatures.
The described industrial residue that is rich in transition elements is meant that the oxide of Fe, Mn based on the period 4 transition elements, Ti, V, Cr, Ni, Cu, Co, Zn, Zr, Nb, Mo, W or total amount of compound surpass 5% or contain the trade waste of a large amount of SiC, elemental silicon, these discarded objects or to be called waste residue normally dark and black comprise ferroalloy industry waste residue, steel industry waste residue, nonferrous metallurgy already waste residue, chemical industry waste residue.Various ferromanganese slags contain MnO 5-50%, FeO 0.2-2.5% in the ferroalloy industry waste residue, and the silicochromium slag contains Cr
2O
30.1-5%, Cr 2-10.5%, SiC 4-22%, Si 7-8%, in, low, chromic carbide iron slag contains Cr
2O
32-7%, FeO 1-3%, ferro-silicon slag contain FeO 3-7%, SiC 20-29%, Si 7-10%, and the ferrotungsten slag contains MnO 20-25%, FeO 3-9%, and molybdenum iron slag contains FeO 13-15%, and the crome metal leached mud contains Cr
2O
32-7%, Fe
2O
38-13%, the crome metal metallurgical slag contains Cr
2O
311-14%, electrolytic manganese residues contains MnSO
4About 15%, Fe (OH)
3About 30%, silicon manganese slag contains MnO 8-18%, FeO 0.2-2%, and the silicomanganese flue dust contains MnO
220-24%, the ferronickel slag contains FeO 40%, Cr
2O
340%.Converter slag contains Fe in the steel industry waste residue
2O
31.4-11%, FeO7-21%, MnO 0.9-4.5%, the open hearth slag contains Fe
2O
31.7-7.4%, FeO 7-36%, MnO 0.6-3.9%, the steel rolling iron scale contains Fe
2O
3Near 100%, vanadium titano-magnetite ironmaking slag contains TiO
210-17%, Fe
2O
3About 4%, vanadium titano-magnetite steel-making slag contains iron oxide 11-13%, MnO 1-1.2%, V
2O
52.3-2.9%, TiO
22-2.9%.The electric furnace copper ashes contains FeO 26-34% in the nonferrous metallurgy industry waste residue, and copper blast-furnace Water Quenching Slag (being commonly called as black sand) contains FeO+Fe
2O
340-50%, wet type copper smelting leached mud contain Fe 50%, Cu 1.13%, Pb 1.05%, Zn 0.2%, Bi 0.15%, Mn 0.04%, plumbous fuming furnace Water Quenching Slag be with the blast-furnace cinder of the plumbous output of refining again the waste after fuming furnace reclaims plumbous, zinc include Fe
2O
338.6-38.7%, Pb0.06-0.37%, Zn 0.8-1.3%, aluminium metallurgy factory makes Al
2O
3In time, discharges the waste red mud and contains Fe
2O
38-10%, TiO
22.5%, the pyrite cinder of output contains Fe when making sulfuric acid with troilite in the chemical industry waste residue
2O
341-49%, FeO 10-10.4%, TiO 0.4-0.5%, MnO 0.1-0.5%, CuO 2-4%.
Metalliferous mineral is meant mineral such as the common iron ore that contains the period 4 transition elements, and maroon contains Fe
2O
330-70%, chromite, kermesinus contains Cr
2O
330-54%, FeO 12-17%, ilmenite, black purple contains TiO 50-60%, FeO 22-35%, Fe
2O
37-15%, MnO 0.5-4%, manganese ore, pitchy, MnO
240-78%, Mn
3O
44-32%, Fe 1-18%, nickel-containing limonite, brown contains Ni 1.2-1.4%, Co 0.1-0.2%, Cr
2O
33%, Fe 35-50%, vanadium titano-magnetite, black contains V 0.4-1.8%, TiO
29-34%, Fe
2O
315-50%, FeO 9-34%, MnO 0.2-6%, Cr
2O
30.1-0.7%, columbite, black contains Nb
2O
59-68%, Ta
2O
51-15%, TiO 1-3%, MnO 1-3%, SnO 2-5%, FeO 12-20%, wolframite, pitchy contain WO
365-67%, FeO 12-15%, MnO 8-12%, Sn 0.17-0.8%.The purpose of selecting these trade wastes that are rich in transition elements and metalliferous mineral for use is to provide painted composition for ceramic solar plate base substrate or superficial layer, makes base substrate or superficial layer present dark color or black, makes it absorb more sunlight.
Described with tailings in vanadium extraction or (with) other be rich in the period 4 transition metal trade waste or (with) metalliferous mineral that is rich in the period 4 transition metal be raw material grind into mud be meant as: adding 0.2% oleic acid in the tailings in vanadium extraction is dispersant, the methylcellulose of adding 3% is binding agent and suspending agent, add the common ball milling of water and became mud in 48 hours, cross 400 mesh sieves, tail over less than 0.1%; Or be meant as tailings in vanadium extraction 50～90% for primary raw material, all the other are the conventional ceramic raw material, with traditional ceramics technology, adding water for ball milling is mud, and other trade waste or alternative above-mentioned tailings in vanadium extraction of metalliferous mineral that are rich in the period 4 transition metal grind described mud.
Compressed-air actuated pressure during described the spraying is 0.4～1.2MPa, when solar panel biscuit horizontal positioned, the gun spraying direction becomes 20～100 degree angles with vertical plane, hollow ceramic solar panel biscuit is 1100～1300 ℃ with the temperature that solid netted black porcelain sunlight absorption biscuit layer burns till jointly, and the thickness of compounding solid netted black porcelain sunlight absorbing layer is 0.1～3 millimeter.
Described in glaze and enameling method the difference that essence is arranged on ceramic or earthenware slab, brick of solid netted black porcelain sunlight absorbing layer compound on the ceramic solar plate and forming method thereof and common ceramics.Glaze is silica (SiO
2) or boric anhydride (B
2O
3) and basic anhydride such as potassium oxide, sodium oxide molybdena, calcium oxide, magnesia, barium monoxide, lead oxide, the mixture of zinc oxide etc., ceramic is when high temperature sintering, glaze is molten for liquid, has good flowability, fill up convex-concave, discharge bubble, make surface smoothing, mellow and full, solidify gradually in the cooling procedure, be hardened to the silicate or the borate of glassy state at last, the glaze layer is a vitreum, and the same with general glass have an isotropism, there is not definite melting point, surface smoothing, have the glass general characters such as gloss, and solid netted black porcelain sunlight absorbing layer the same with the ceramic solar board substrate be ceramic material, be polycrystalline material, the SiO in the glaze
2Account for 60～75%, and in the tailings in vanadium extraction complex oxide total amount of Fe, Cr, Mn, V, Ti near 80%.The glaze layer thickness of general porcelain is 0.1～0.5 millimeter, and the thickness of above-mentioned black enamel coating is 0.1～3 millimeter, even as far as possible, level and smooth, fine and close, the uniform thickness of enameling method requirement glazing layer on biscuit of ceramics, and the spraying method of solid netted black porcelain sunlight absorbing layer just in time in contrast, usually during glazing, the gun spraying direction is vertical with glazing face usually, and when spraying solid netted black porcelain sunlight absorbing layer, when solar panel biscuit horizontal positioned, the gun spraying direction becomes 20～100 degree angles with vertical plane.
Solid netted black porcelain sunlight absorbing layer is compared with traditional solar energy absorbing coating, and both have some something in commons, and very big difference is also arranged.
Both are by something in common: 1. black, and black porcelain is a black, solar energy absorbing coating also mostly is black.2. it is to rely on a large amount of period 4 transition metals to absorb solar energy in the mode of excitation electron transition that transition metal oxide, black porcelain absorb one of sunlight principle, and it also is to rely on this principle to absorb solar energy that the considerable part solar energy absorbing coating is arranged.3. rough surface, nearly all solar energy absorbing coating all wishes to form rough surface to form the sunlight trap, but be subjected to the restriction of raw material, equipment, technology, its degree of roughness has nothing in common with each other, and the micron order of the formation chemically hole that has absorbs sunlight, and its porosity reaches about 22%, black enamel coating can form very high roughness, porosity can reach more than 50%, and surface height difference can reach millimeter level, can be micron-sized by moisture hole that capillary forms on each accumulation body.4. sunlight absorption rate, the sunlight absorption rate of the solar energy absorbing paint of general industry employing is mostly between 0.88～0.93, the sunlight absorption rate of not having the vanadium-titanium black ceramic solar panel of rough surface after measured is about 0.9, solid netted black porcelain sunlight absorbing layer constitutes rough surface and micron hole, its tailings in vanadium extraction ratio also is higher than vanadium-titanium black ceramic solar panel in the past, can have higher sunlight absorption rate.5. selectivity absorbs, the sunlight energy mainly concentrates in wavelength 0.3～2.1 micrometer range, infrared energy mainly concentrates in 2.5～25 micrometer ranges, solar energy absorbing paint utilizes various principles to increase the shortwave absorption, reduce long-wave radiation, be called coating for selective absorption, solid netted black porcelain sunlight absorbing layer utilizes its space network and micron hole can realize the form light harvesting of shortwave side with black hole, trap, the long wave side is with the form radiant light on plane, thereby realizes that to a certain extent selectivity absorbs.
Both distinguish part and are: 1. production cost, the solar energy absorbing coating transition metal oxides that require certain purity that adopt more, its production equipment and technology are relatively expensive and complicated, solid netted black porcelain sunlight absorbing layer adopts industrial waste or contains the metalliferous mineral of a large amount of transition metal oxides, its manufacturing equipment and technology are less expensive and simple, and in the sintering process of matrix, burn till in the lump, what it was shared burns till energy seldom, causes its production cost may be more cheaper than any solar paint that generally adopts at present.2. service life, usually solar energy absorbing paint in, form in the low temperature, or form at short notice even in moment, by forms by organic material, the bond energy of the sunlight absorption mineral of its formation is lower, become the ore deposit reaction inadequately fully, thoroughly, structure is stable inadequately, causes producing the phenomenon that performance decays in time under long-term solar radiation, and the temperature that can bear also has certain limit, usually the highest bearing temperature of solar energy absorbing paint is 350 ℃, is difficult to break through 400 ℃.The sunlight absorption rate of general solar energy absorbing paint began to descend in the several years, and its economic life may be about 10 years, even lower.Solid netted black porcelain sunlight absorbing layer is the ceramic material in the ceramic material, be to form through 1100～1300 ℃ of high-temperature calcinations, the general character with ceramic material, formed sunlight absorbs dark minerals by atomic bond or ionic bond combination, be high bond energy mineral, unless be placed on the above high temperature of thousands of degree and attached other extreme conditions, otherwise these mineral are difficult to destroy and dissociate, black porcelain absorbed layer can bear the temperature more than 1000 ℃ under usual conditions, under the empty hundreds of degree temperature conditions that shine of sunburst, black porcelain structure and performance can not change, vanadium-titanium black ceramic once used the several years in 600 ℃, detect afterwards and do not find performance variation, 300 * 300mm small size solar panel of gypsum mould grouting moulding also once used more than 10 years as the solar energy heating body, did not also find changes of properties.Solid netted black porcelain sunlight absorbing layer was compared with deceive porcelain in the past, and shape changes to some extent, and material and no change are so solid netted black porcelain sunlight absorbing layer has quite long service life.3. average sunlight absorption rate, common solar energy absorbing paint, owing to reasons such as raw material, manufacturing process, sunlight absorption rate can decay in time, its average sunlight absorption rate is not high between the operating period about 10 years, solid netted black porcelain sunlight absorbing layer, 10 years or the longer time in sunlight absorption rate can not decay, its average sunlight absorption rate is higher.
(4) description of drawings
Describe characteristics of the present invention in detail below in conjunction with accompanying drawing:
Fig. 1 represents the mud of the angled ejection atomizing of spray gun and hollow ceramic sun biscuit plate surface.
When Fig. 2 represented that single rifle sprays, single rifle was made motion scan in biscuit plate surface, sprayed the mud of atomizing line by line, progressively formed the biscuit layer of solid netted black porcelain sunlight absorbing layer.
Fig. 3 represents to be compounded in the solid netted black porcelain sunlight absorbing layer on hollow ceramic solar panel surface.
Fig. 4 represents to be compounded in the solid netted black porcelain sunlight absorbing layer on hollow ceramic solar panel surface and the transition binder course between absorbed layer and the solar panel matrix.
Among the figure:
1---spray gun 2---the mud 3 of atomizing---hollow ceramic solar panel biscuit 4---the biscuit layer 5 of solid netted black porcelain sunlight absorbing layer---the fine hole of the solid netted black porcelain sunlight absorbing layer 6 through burning till---the transition binder course 7 that forms between solid netted black porcelain sunlight absorbing layer and the hollow ceramic solar panel when burning till---
(5) specific embodiments
Embodiment
1. tailings in vanadium extraction 65%, Suzhou soil 20%, flint clay 15% (percentage by weight, added water for ball milling 24 hours down together), mud moisture content 40%, with compressed air mud being sprayed on dry length * wide is on 1000 * 500 millimeters the hollow ceramic solar panel biscuit surface, air pressure 0.6Mpa, spray gun becomes spraying under 70 ° of angles with vertical plane, 300 millimeters of spray guns apart from the biscuit surface, single rifle is lined by line scan and was sprayed 2 minutes, the droplet that makes the initial stage ejection is by plate face moisture curing, the accumulation body moisture curing that the follow-up droplet that is sprayed on the accumulation body is had cured, the described solid netted black porcelain sunlight of final formation absorbs the biscuit layer, with whole solar panel biscuit drying, fire for 1240 ℃, 0.9 millimeter of accumulation body height becomes the vanadium-titanium black ceramic composite ceramic solar energy thermal-arrest plate with solid netted black porcelain sunlight absorbing layer, can be called black ceramic composite ceramic solar panel, be called for short ceramic solar plate.
2. as embodiment 1 described method, adopt many spray gun sprayings, shared 12 spray guns, 4 one are arranged in 3 rows, 1 meter of row-to-row distance, the solar panel biscuit passes through from the below, and the speed per minute is advanced 2 meters, 60 square metres of the per hour ceramic coated solar panel biscuits of the method.
3. as embodiment 1 described method, mud adopts tailings in vanadium extraction 70%, and big blue clay 17%, potassic feldspar 10%, lane soil 3% increase feldspar and talc content in hollow ceramic solar panel biscuit prescription, and 1160 ℃ of firing temperatures are made ceramic solar plate.
4. as embodiment 1 described method, spray gun becomes spraying under 30 ℃ of angles, ceramic coated solar panel biscuit with vertical plane.
5. as embodiment 1 described method, spray gun is sprayed with horizontal direction, and droplet falls to the ceramic solar plate biscuit of horizontal positioned along parabola.
6. as embodiment 1 described method, air pressure 10kg/cm
2, 400 millimeters of spray guns apart from the biscuit surface, spray time 4 minutes, accumulation body height are 2.1 millimeters.
7. as embodiment 1 described method, mud adopts tailings in vanadium extraction 96.8%, methylcellulose 3%, oleic acid 0.2%.
8. as embodiment 1 described method, mud adopts tailings in vanadium extraction 50%, camwood knag soil 20%, Datong District's soil 15%, potassic feldspar 7.5%, talcum 7.5%.
9. as embodiment 1 described method, mud adopts electrolytic manganese residues 40%, pyrite cinder 40%, Laiwu soil 15%, potassic feldspar 5%.
10. as embodiment 1 described method, mud adopts wolframite 35%, chromite 20%, vanadium titano-magnetite 15%, Mengyin soil 20%, talcum 6%, Zhangqiu soil 4%.
Claims (10)
1. the method for compounding solid netted black porcelain sunlight absorbing layer on ceramic solar plate, it is characterized in that the conventional ceramic pug extruded with porous mold through vacuum pugging and become the porous ventilating hole plate, through being processed into the hollow sheeting that the termination communicates, with pug plate of the same race shutoff two and tap into outlet, become hollow ceramic solar panel biscuit with import and export, with tailings in vanadium extraction or (with) other be rich in the period 4 transition metal industrial residue or (with) metalliferous mineral that is rich in the period 4 transition metal is that raw material or primary raw material grind into mud, with compressed air mud is sprayed on the dry hollow ceramic solar panel biscuit surface, adopt single spray gun or many spray gun sprayings, control compressed-air actuated pressure, the ratio of flow and mud makes the initial stage and the ceramic solar plate biscuit contacted droplet in surface of drying have certain intensity because the surface tension of the quick suction of dry biscuit and droplet forms, relatively dry, adhere to the mud pellet on biscuit plate surface, the droplet that follow-up spray falls at first runs into these mud pellets that protrudes in the surface with certain wettability power, stick on the mud pellet, be piled into column successively, the steeple shape, the wall shape, cellular, cavernous non-homogeneous, discontinuous, the droplet pug accumulation body that is had certain intensity by moisture absorption, when reaching a certain height, these three-dimensional accumulation bodies stop spraying before losing wettability power, thereby obtain the biscuit layer of solid netted black porcelain on hollow ceramic sun biscuit plate surface, this hollow ceramic biscuit plate with solid netted black porcelain biscuit layer is carried out high-temperature firing after drying, the control firing temperature and the time chien shih solid netted black porcelain biscuit layer and hollow ceramic solar panel biscuit be sintered to solid netted black enamel coating and porcelain hollow ceramic solar panel matrix simultaneously, high temperature sintering makes that solid netted black enamel coating and porcelain hollow ceramic solar panel matrix are sintered combined to be one, or the method that adopts twice firing with both sintered combined be one, its firing temperature makes solid netted black porcelain mud droplet accumulation horizon become ceramic material, spray gun is done relative motion with hollow ceramic solar panel biscuit surface at a certain angle during spraying, when single rifle sprays, single rifle is made the systematicness motion scan in biscuit plate surface, make movement velocity, the mud spouting velocity is corresponding with the biscuit rate of moisture absorption, guarantee that the droplet accumulation body has corresponding wettability power all the time, the accumulation body of large quantity of moisture by relatively dry in the droplet that sticks on the accumulation body is passed in the dry biscuit, make the droplet of new adhesion lose part moisture rapidly and have definite shape and intensity, droplet is poly-to become plane layer for the mud that flows collapses deposit thereby do not make, during the multiple gun spraying, hollow ceramic solar panel biscuit moves below spray gun, make movement velocity, the spray gun spacing distance is corresponding with mud spouting velocity and biscuit rate of moisture absorption, to achieve the above object, adjust the cohesive force between the particle in mud prescription and the moisture decision mud, control compressed-air actuated pressure, the speed and the size of the ratio decision spray mountain droplet of flow and mud, droplet is that mud and AIR MIXTURES are the mud balls of hollow, when sticking on the deposit, lose part moisture and harden into the hollow duricrust, the fragmentation of part spheroid, form the accumulation body of solid netted porous, the prescription of mud, cohesive force, the average diameter and the height of the speed decision accumulation body that dries out, the accumulation body height is 0.1～3 millimeter, the pore that is full of in the accumulation body is the moisture movement passage that dry biscuit causes when absorbing moisture, form fine hole when burning till, burn till each column of back accumulation body, steeple, wall, be covered with the hole on the honeycomb wall, the aperture is 0.1～50 micron, and solid netted black porcelain sunlight absorbing layer is black.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, it is characterized in that described tailings in vanadium extraction is that vanadium titano-magnetite obtains vanadium-bearing hot metal through melting, vanadium-bearing hot metal obtains vanadium slag through blowing, vanadium slag adds auxiliary material and carries out roasting, roasting material is carried out the wet extraction vanadium extraction, and the remaining residue as discarded object is tailings in vanadium extraction behind the extraction vanadium.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, it is characterized in that the described industrial residue that is rich in transition elements is meant that the oxide of Fe, Mn based on the period 4 transition elements, Ti, V, Cr, Ni, Cu, Co, Zn, Zr, Nb, Mo, W or total amount of compound surpass 5% or contain the trade waste of a large amount of SiC, elemental silicon, these discarded objects or to be called waste residue normally dark and black comprise ferroalloy industry waste residue, steel industry waste residue, nonferrous metallurgy already waste residue, chemical industry waste residue.Various ferromanganese slags contain MnO 5-50%, FeO0.2-2.5% in the ferroalloy industry waste residue, and the silicochromium slag contains Cr
2O
30.1-5%, Cr 2-10.5%, SiC 4-22%, Si 7-8%, in, low, chromic carbide iron slag contains Cr
2O
32-7%, FeO 1-3%, ferro-silicon slag contain FeO 3-7%, SiC 20-29%, Si 7-10%, and the ferrotungsten slag contains MnO 20-25%, FeO 3-9%, and molybdenum iron slag contains FeO 13-15%, and the crome metal leached mud contains Cr
2O
32-7%, Fe
2O
38-13%, the crome metal metallurgical slag contains Cr
2O
311-14%, electrolytic manganese residues contains MnSO
4About 15%, Fe (OH)
3About 30%, silicon manganese slag contains MnO 8-18%, FeO 0.2-2%, and the silicomanganese flue dust contains MnO
220-24%, the ferronickel slag contains FeO 40%, Cr
2O
340%.Converter slag contains Fe in the steel industry waste residue
2O
31.4-11%, FeO 7-21%, MnO 0.9-4.5%, the open hearth slag contains Fe
2O
31.7-7.4%, FeO 7-36%, MnO 0.6-3.9%, the steel rolling iron scale contains Fe
2O
3Near 100%, vanadium titano-magnetite ironmaking slag contains TiO
210-17%, Fe
2O
3About 4%, vanadium titano-magnetite steel-making slag contains iron oxide 11-13%, MnO 1-1.2%, V
2O
52.3-2.9%, TiO
22-2.9%.The electric furnace copper ashes contains FeO 26-34% in the nonferrous metallurgy industry waste residue, and copper blast-furnace Water Quenching Slag (being commonly called as black sand) contains FeO+Fe
2O
340-50%, wet type copper smelting soak the mountain slag and contain Fe 50%, Cu 1.13%, Pb 1.05%, Zn 0.2%, Bi 0.15%, Mn 0.04%, plumbous fuming furnace Water Quenching Slag be with the blast-furnace cinder of the plumbous output of refining again the waste after fuming furnace reclaims plumbous, zinc include Fe
2O
338.6-38.7%, Pb 0.06-0.37%, Zn 0.8-1.3%, aluminium metallurgy factory makes Al
2O
3In time, discharges the waste red mud and contains Fe
2O
38-10%, TiO
22.5%, the pyrite cinder of output contains Fe when making sulfuric acid with troilite in the chemical industry waste residue
2O
341-49%, FeO 10-10.4%, TiO 0.4-0.5%, MnO 0.1-0.5%, CuO 2-4%.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, it is characterized in that described metalliferous mineral is meant the mineral that contain the period 4 transition elements, wherein common iron ore, maroon contains Fe
2O
330-70%, chromite, kermesinus contains Cr
2O
330-54%, FeO 12-17%, ilmenite, black purple contains TiO 50-60%, FeO 22-35%, Fe
2O
37-15%, MnO 0.5-4%, manganese ore, pitchy, MnO
240-78%, Mn
3O
44-32%, Fe 1-18%, nickel-containing limonite, brown contains Ni 1.2-1.4%, Co 0.1-0.2%, Cr
2O
33%, Fe 35-50%, vanadium titano-magnetite, black contains V 0.4-1.8%, TiO
29-34%, Fe
2O
315-50%, FeO 9-34%, MnO 0.2-6%, Cr
2O
30.1-0.7%, columbite, black contains Nb
2O
59-68%, Ta
2O
51-15%, TiO 1-3%, MnO 1-3%, SnO 2-5%, FeO 12-20%, wolframite, pitchy contain WO
365-67%, FeO 12-15%, MnO 8-12%, Sn 0.17-0.8%.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, it is characterized in that tailings in vanadium extraction is 50～90% in the described mud, all the other are the conventional ceramic raw material, adding water for ball milling is mud.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, the industrial residue that is rich in the period 4 transition metal or the metalliferous mineral that it is characterized in that not comprising in the described mud tailings in vanadium extraction are 50～90%, all the other are the conventional ceramic raw material, and adding water for ball milling is mud.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, it is characterized in that described compressed-air actuated pressure is 0.4～1.2MPa.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, it is characterized in that when solar panel biscuit horizontal positioned the gun spraying direction becomes 20～100 degree angles with vertical plane.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, it is characterized in that it is 1100～1300 ℃ that described hollow ceramic solar panel biscuit absorbs the temperature that the biscuit layer burns till jointly with solid netted black porcelain sunlight.
According to claim 1 described on ceramic solar plate the method for compounding solid netted black porcelain sunlight absorbing layer, the thickness that it is characterized in that described compounding solid netted black porcelain sunlight absorbing layer is 0.1～3 millimeter.
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| CNB2006100686666A CN100547317C (en) | 2006-09-29 | 2006-09-29 | The method of compounding solid netted black porcelain sunlight absorbing layer on ceramic solar plate |
| US12/302,489 US20090229598A1 (en) | 2006-05-25 | 2007-05-22 | method for making large-sized hollow ceramic plate |
| JP2009511323A JP4991849B2 (en) | 2006-05-25 | 2007-05-22 | Manufacturing method and applied products of large size hollow ceramic plate |
| PCT/CN2007/001653 WO2007137506A1 (en) | 2006-05-25 | 2007-05-22 | A method for making ceramic large-size hollow plate and products thereof |
| AU2007266395A AU2007266395B2 (en) | 2006-05-25 | 2007-05-22 | A method for making ceramic large-size hollow plate and products thereof |
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