CN1229466A - Device and method for storing thermal energy - Google Patents
Device and method for storing thermal energy Download PDFInfo
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- CN1229466A CN1229466A CN98800585A CN98800585A CN1229466A CN 1229466 A CN1229466 A CN 1229466A CN 98800585 A CN98800585 A CN 98800585A CN 98800585 A CN98800585 A CN 98800585A CN 1229466 A CN1229466 A CN 1229466A
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- 238000001816 cooling Methods 0.000 claims abstract description 35
- 238000005338 heat storage Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 230000005855 radiation Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 35
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- 239000003795 chemical substances by application Substances 0.000 claims description 24
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
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- 239000007787 solid Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 229910052755 nonmetal Inorganic materials 0.000 description 2
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- 238000010899 nucleation Methods 0.000 description 2
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- 230000001052 transient effect Effects 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013659 LiCl—LiOH Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- GARCGFNLRCZFLE-UHFFFAOYSA-L dilithium;chloride;hydroxide Chemical compound [Li+].[Li+].[OH-].[Cl-] GARCGFNLRCZFLE-UHFFFAOYSA-L 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- WGRULTCAYDOGQK-UHFFFAOYSA-M sodium;sodium;hydroxide Chemical compound [OH-].[Na].[Na+] WGRULTCAYDOGQK-UHFFFAOYSA-M 0.000 description 1
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- 230000008646 thermal stress Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
- F28D20/021—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material and the heat-exchanging means being enclosed in one container
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
- F24D11/00—Central heating systems using heat accumulated in storage masses
- F24D11/002—Central heating systems using heat accumulated in storage masses water heating system
- F24D11/003—Central heating systems using heat accumulated in storage masses water heating system combined with solar energy
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
- F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
- F24S23/74—Arrangements for concentrating solar-rays for solar heat collectors with reflectors with trough-shaped or cylindro-parabolic reflective surfaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D2020/0004—Particular heat storage apparatus
- F28D2020/0026—Particular heat storage apparatus the heat storage material being enclosed in mobile containers for transporting thermal energy
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/20—Solar thermal
-
- 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
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
-
- 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
- Y02E70/00—Other energy conversion or management systems reducing GHG emissions
- Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Other Air-Conditioning Systems (AREA)
- Central Heating Systems (AREA)
- Engine Equipment That Uses Special Cycles (AREA)
- Photovoltaic Devices (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
A device (1) for storing thermal energy, possibly solar energy, wherein the thermal energy is collected by a solar energy collection device. The solar heat collector comprises a solar radiation energy gathering assembly (7), a heat source (7a) arranged at the focusing position of the assembly (7), a forward primary pipe (8) and a backward secondary pipe (a) which are connected with the heat source (7a) and a heat container (2) of a heat storage device (1), and a circulating pump (21) connected to the primary pipe (8). The hot container (2) is filled with crystallization materials (3) and is connected to one or more heat exchangers (l) and heat utilization devices (12) through a heating-cooling pipe (4), an inlet-outlet pipe end (5), a valve (6), a primary pipe (8), a cold pipe (9) and a connecting pipe (10). The hot vessel (2) and the main part of the pipe (8) are connected to an expansion tank (l8) filled with inert gas by means of an intermediate connecting pipe (17).
Description
Various energy reserves in the world are not to be unlimited; They, especially crude oil production expense is also more and more expensive.Because the substitution problem of petroleum derivative is still unresolved, so day by day the oil supply of Jian Shaoing becomes the instant problem that may cause serious energy short supply and disorder.Simultaneously, burning mineral fuel has caused the serious environmental pollution.The continuous increase of carbon dioxide content has increased the weight of dangerous greenhouse effects in the atmosphere.The acid rain that sulfur dioxide in the atmosphere causes has worsened biosphere widely.
The high-efficiency and low-cost heat accumulation will mean huge advantage, and particularly in the used heat cohesion field of solar energy utilization and steam power plant and nuclear power plant, this advantage is more obvious.At present, more and more higher to the demand of energy, the utilization of solar energy constantly increases, and it will be most important to the energy supply of the next century.The popularization and application of energy collector makes alternative petroleum derivative become possibility, and its significance is: energy collector construction cost reduces; Can reach its peak efficiency; The benefit of moving in high heat rating serves many purposes it; Advantageous environment protection characteristics; And this free energy in use between on unlimitedness.
Comprise that unique shortcoming of collecting the solar energy utilization of heat energy with amplitude transformer is the periodicity relevant with seasonal variations and the cycle on daytime.The unique way that overcomes the shortcoming that above-mentioned periodicity brings fully is to take effective heat accumulation measure, the solar radiant energy that to collect spring to autumn stores the usefulness in order to winter in some way, thereby realizes for example satisfying the target that all utilize the demand of solar energy heating and hot-water supply.It is to utilize the solar energy or other thermal source that store to be industry, agricultural, food industry and the continuous heat energy of processing industry supply that another kind of heat accumulation is used.
Require the occasion of heating and hot-water supply such as apartment, communal facility at some, operation of office building, industry and processing factory, animal feeding place, tent, greenhouse and some agricultural and food industry (dry, heating process) or the like very likely replaces traditional energy with the energy collecting solar facilities.All these purposes can be promoted the use of solar energy greatly.
Utilize the Waste Heat Recovery of steam power plant and nuclear power plant, portable heat accumulation equipment can solve the problem that is provided with constant heat for the communal facility of industry and processing industry and requirement high heat by following mode, promptly be connected on the energy integration system or be connected on the docking station of other above-mentioned power plant having the mobile device of high heat storage ability or tank body/container, after filling heat rapidly, the thermal capacity of storage is directly discharged with the method for rapid heat release and passes to end user device or pass to another heat accumulation equipment.These portable heat-storing devices can also be connected with heating system with traditional heating, thus shorten effectively heat and the terminal use between distance.
Present known several multi-form heat-storing methods.As for the type of stocking system, sensible heat storage device and latent heat storage device are arranged.Solid material is suitable for storing sensible heat most.Heating and the solid that cooled off can heat accumulations and can not undergo phase transition.Sensible enthalpy decision heat storage capacity.This heat-storing method comprises two kinds of forms: solid itself transports heat from the heat collector the gravel grinding system for example; Perhaps solid is stayed in the heat collector, and by liquid medium or gas transport heat.
If heat-storage medium is a solid and fully launches that so tiltedly temperature effect is easy to realize: in a thin cylinder, the heat transportation medium flows vertically, it is characterized in that heat transportation apart from weak point, and heating surface is big, but thermal conductivity is low.In charging and discharging thermal process, heat has three kinds of distribution modes along the height of heat vessel: in first kind, compare heating surface and heat transfer coefficient low (as examining Pasteur (cowpet)) system with flow; In second kind, situation opposite with first kind (as the gravel process of lapping).Axial heat conduction is all arranged in both cases, and this makes Temperature Distribution more mild.One temporary transient heat scope is arranged in the third, it along with fill, exothermic process and upper and lower float, as the blend range in the liquid juice container with a fixed displacement.Its advantage is that whole exothermic process middle outlet temperature is almost constant; Its shortcoming is, the heat transfer liquids whole system of must flowing through, and when occurring over just narrower temporary transient zone when conducting heat, the pressure of heat transfer liquids descends.
The heat accumulation specific capacity and the thermal change scope thereof of solid dielectric are bigger usually, and still, in most cases, it can not be utilized fully.In metal, cast iron has the highest heat storage capacity, but its big proportion is its shortcoming.Alundum (Al (Al
2O
3) and the heat storage capacity height of magnesia (Mgo), but it costs an arm and a leg.
Utilize the latent heat heat accumulation, do not relate to thermal change, but relate to the phase transformation of storage medium under constant temperature, the latent heat of most of kinds all relates to by the transformation of liquid phase to gas phase.Its shortcoming is, the heat storage capacity of vapour phase medium is quite low, reason that why this heat-storing method that utilizes latent heat can not get using that Here it is.Store latent heat and mean that the fusion of small Volume Changes heat accumulation is only arranged.The advantage of phase-change thermal storage is except latent heat, and the sensible heat of liquid phase and solid-phase media also can utilize.The latent heat container is an a kind of constant pressure and constant matter system, and under higher temperature, its storage capacity is also higher.Use two kinds of compositions or more kinds of mixture of ingredients of two kinds of compositions, especially eutectic points, can under the situation that does not significantly reduce enthalpy of phase change, reduce its fusing point.
Storage medium can be divided into simple substance material and double base and ternary system.
In the simple substance material, lithium fluoride (LiF) has the highest heat of fusion, and the lithium hydroxide (LiOH) with very favorable fusing point then has the good latent heat about the same with LiF.Unique shortcoming of these materials is that its pure matter form is very expensive, but can overcome expensive shortcoming by being mixed into the eutectic point mixture with other material with good heat storage capacity.
The application of double element system is highly beneficial, because its fusing point is in a suitable low scope, thus can obtain high energy density at low relatively fusing point, and can sneak into the good but more expensive material of thermal storage performance and make its heat storage capacity almost constant.This double element system can be divided into eutectic point mixture and non low eutectic azeotropic mixture.The eutectic point mixture is the most suitable because of its favourable characteristic.
The thermal characteristics of ternary system is very similar to the thermal characteristics of double element system, but its fusing point and price are lower, thereby is very suitable for the low and practical heat reservoir of cost.
Also must mention pressed gas heat accumulation and other heat reservoir, as absorption heat accumulation and heat chemistry heat accumulation.
The pressed gas heat accumulation comprises above 100,000m
3Underground compressed air storage system, gas turbine and at full capacity power plant all run on this operating mode.During with the compressed air heat accumulation, exchange heat is arranged, perhaps adopt a latent heat storage system separately, heat release such as just can realize if compressed air discharges slowly and with environment.If can obtain extra heat storage capacity when lower such as the latent heat deposit can not introduced high thermal stress simultaneously when temperature in the dispose procedure drops to, then can improve thermal storage performance.Energy density is along with the raising of pressure store linearly and increases, and this is why in compressed air (greater than 50bar) heat accumulation, the suggestion high pressure.All these situations have hindered the large-scale popularization of this system to use.
Absorption heat accumulation has four kinds of basic skills.First method, heat adds to absorber material, and the desorb material is introduced in the gas container of operation under constant voltage or the adjustable pressure.Gas cooled off to improve heat storage capacity.Its shortcoming is that energy density is low.
Second method, if gas is condensed under environment temperature or similar temperature, then its volume can be littler.The heat of condensation is passed to environment.In the dispose procedure, environment heat makes fluid evaporator again, thereby all energy all lose.
The third method, the fluid heat accumulation has replaced absorption heat accumulation, and the former is with other heat-absorbing medium work and can absorb at ambient temperature or desorption gas.
The 4th kind of method, absorption heat accumulation and thermo-motor associated working.Open air bleeding valve, steam flows into container by steam engine by boiler, generates heat and introduces boiler, thereby continue to produce steam.Its shortcoming is to make energy density also low because the mass density of absorption salt is low, although it is very favourable to absorb calorific value.
The essence of heat chemistry heat accumulation is in the form of the heat energy binding energy that is stored in reversible chemical reaction.This chemical reaction occurs in or does not have under the condition of catalyst, behind the chemical reaction, the material that participates in reaction is separated and store respectively.In this process, still untapped heat of evaporation forms when condensing (filling heat), and makes the heat accumulation decrease in efficiency.Another shortcoming is that the service life of catalyst is very unfavorable.
Comparative result to heat storage capacity shows that in various heat reservoirs, using its energy density of heat reservoir of liquid heat-storage medium is 12.5%; Its energy density of solid heat reservoir that has metal medium is 25%; Its energy density of solid heat reservoir that has nonmetal medium and phase-change thermal storage medium is 37.5%.
The latent heat heat accumulation can obtain the energy density higher than sensible heat heat accumulation.The saturation pressure of pressure system is higher than atmospheric pressure and requires the working pressure closed container, so this system is impracticable.Absorption heat reservoir needs a pressure seal container at least; The heat chemistry heat reservoir then needs the pressure seal container of several different pressures when reactive material stores with fluidised form; These conditions and low energy density thereof are the shortcomings of this type systematic.
The latent heat heat reservoir all is better than above-mentioned several system, because its constant release temperature can provide the sensible heat heat accumulation that descends gradually than temperature higher efficient.Another advantage of latent heat heat reservoir is that the sensible heat of the sensible heat of solid phase, the latent heat of phase transformation and liquid phase needing can both be used for thermal field to close.
In the present invention, basic thought is, phase transformation, the solid heat-storage medium that has highest energy density non-metal carrier and constant release temperature at present known and use in heat reservoir in be best.Yet these heat-storage mediums still can not satisfy the following requirement: under low cost, invertibity, favourable melting temperature and the various situation to the anti-corrosion capability of structure/construction material.Based on the consideration to this fact, the present invention solves the application problem of the following eutectic point medium: NaOH (NaOH), NaOH-sodium nitrate (NaOH-NaNO
3), NaOH-lithium hydroxide (NaIG-LiOH), and lithium chloride-lithium hydroxide (LiCl-LiOH), these eutectic point media demonstrate constant invertibity and have favourable fusing point, high heat storage ability and to the anti-corrosion capability of employed structural material in experiment.
U.S. Patent No. 4,244,350 have described a kind of different solution, and it comprises the thermal capacitance device with the solar energy operation; Wherein realized a kind of heat-transferring method.In servicely in overheated pipe-line system, produce superheated vapor by heating steam.Yet the efficient of this device is low and its structure is unsuitable for long-term heat accumulation.
U.S. Patent No. 4,391,267 have described a kind of heat accumulating; Its main points are that the molten matter of certain liquid crystal spontaneously or by nucleation becomes crystal state artificially at a certain specified temp.In molten matter, add certain additive in the nucleation process, thereby when molten matter melts, just form a kind of mixture.This additive can contain the equivalent salt of sodium hydrogen phosphate, dipotassium hydrogen phosphate or its ammonium salt or sodium.This additive helps to control the size of crystal and growth and prevents that molten matter from crystallizing into wrong form when curing materials.
The essence of this method is that the promptly molten matter of this material stores the required heat of phase transformation when heating, and discharges heat when crystallization again.Yet it has only described certain process of help crystallisation, does not solve the permanent reusable problem of this crystalline material.The another one shortcoming is that it fails to solve problem with the solar energy heating crystalline material, so it can not utilize solar energy to heat, and can not reuse this crystalline material.
U.S. Patent No. 4,355,627 have described a kind of heat reservoir with solar thermal collector or heat pump work.Its main points are that the heat jar that separates of several conventional geometries forms a heat jar heap in a bulk container.The shell of heat storage units contains just like the heat-transfer matcrial of glass, metallic particles and comprises heat accumulating itself.
Its shortcoming be it not utilize the crystallized solute that heated be that the heat of transformation is come heat accumulation, also be unsuitable for long-term heat accumulation so it can not obtain the high heat storage ability.
The heat accumulation that the purpose of this invention is to provide a kind of energy storage method, particularly solar energy or other high temperature heat source such as power plant or nuclear power plant.In this method, store from the heat of thermal source transmission method with phase transformation by heat transfer medium; Thermal capacitance device in the heat-storing device contains the high crystalline material of a kind of heat storage capacity, may be a kind of eutectic point material; This material is full of heat and heat is stored up to the crystalline material of fusing from the heat transfer medium heating of thermal source.When heat release, heat transfer medium circulates then, and molten matter is cooled to finishes the i.e. crystallization again of phase transformation, also is its best state of cooling.The heat that stores is removed by this method, and crystalline material that uses in this process and eutectic point material can guarantee on the whole that its reversible variation repeats repeatedly in phase transition process; Faint reaction only takes place or not reacts in they and used structural material; They corrode not too easily, and its thermal parameter makes it have high phase-change thermal storage ability.
Another characteristics according to thermal energy storage device of the present invention are that the heating-cooling pipe of heat storage can has rib shape surface, thereby has improved heat radiation and heat absorption capacity.On installed device, the water back of heat exchanger also is added with the rib surface to obtain better heat-sinking capability.
Superior characteristics according to thermal energy storage device of the present invention are improved by such fact, i.e. supervision, state-detection and control device are connected to the computing technique device, for example are connected to a computer.
Thermal energy storage device according to removable system of the present invention, its favourable structure form is that the pipe port of its heating-cooling pipe and the pipe port of its thermal capacitance device start-up portion are equipped with certain connector, they can be connected to condenser system or other station of conducting heat of traditional heating system and steam power plant or nuclear power plant, thereby fill heat can for this removable heat-storing device.
Purpose according to heat-storing device of the present invention and method is to overcome the structure of known heat-storing device and the shortcoming of method thereof, and can long term storage be condensed the heat energy of acquisition by the used heat of energy collector and steam power plant and nuclear power plant.By the heat-storing device that adopts this most effective heat-storing method of phase-change thermal storage, and can realize above-mentioned purpose by farthest reducing the heat convection loss.Another purpose is to use the heat of storage by several modes.
Another purpose is need not build the service pipe-line system but be that the consumer directly supplies institute's heat energy of receiving and storing by portable heat-storing device.Like this by utilizing the free energy and using the defeated by the use of thermal means of most economical practicality can obtain extra advantage.
Attached purpose is to utilize this heat-storing method that utilizes the heat of transformation of crystalline material.In technical literature and practical application, this is a kind of best heat-storing method but still has many technical problems.This method should be used by certain mode, so that can utilize some crystalline mixture and eutectic point material to realize stable, efficient, economical and practical ground heat accumulation, and these crystalline mixtures and eutectic point material should have permanent possibility of reversal voltinism (by experiment confirm), favourable fusing point, high heat of fusion and high heat storage ability and to the resistance to corrosion of the structural material that is used for implementing to construct.
According to above-mentioned purpose, heat-storing device of the present invention mainly is applicable to the heat energy of storage from solar energy heat collector.Heat-storing device according to the present invention comprises with the lower part: the sun of one or more collection solar radiant energies is followed the heat collector assembly; Contain heat transfer medium in order to receive the receiver of the solar thermal energy that is gathered, it is set at focusing place of heat collector assembly; The main pipeline of hot heat transfer medium and cold heat transfer medium and secondary pipeline, it connects heat collector assembly and thermal capacitance device and has one or more EGRs (being circulating pump).
Heat-storing device comprises the thermal capacitance device that certain crystalline material that is suitable for phase-change thermal storage is housed.In this container, certain crystalline material or its molten matter are installed and embedded to the heating-cooling pipe that is used for filling heat and extracting stored heat, the exit portion of these pipes is connected on the main pipeline that transports heat-carrying agent and leads on the secondary pipeline of thermal-arrest assembly by valve, one or more (not having sometimes) heat exchanger is connected to one or more with on the thermic devices.
Thermal capacitance device, heat exchanger, the main that transports heat-carrying agent and secondary pipeline, and intermediate connection tube all is covered with heat insulation layer.Thermal capacitance device, various pipeline and heat exchanger all are equipped with state induction and control device, in order to determine or the characteristic of adjusting heat-carrying agent and the temperature of measurement and the above-mentioned heat-carrying agent of detection.
The thermal capacitance device of heat-storing device and the major part that transports the pipeline of heat transfer medium are connected to one by intermediate connection tube and inert gas is housed, is generally on the expansion drum of nitrogen.The quantity of thermal capacitance device and associated component and heat accumulation and consistent with heat demand.
The objective of the invention is to make a cover thermal energy storage device, comprising heat-storing device and as essential part with removable system.It can be carried with vessel form (as the railroad train jar etc.) by vehicle; One or more thermal capacitance devices are equipped with crystalline material, heating and cooling pipeline, outlet connecting pipe port and connector, adiabatic covering and thermometric instrument and state induction and control device.
According to heat-storing device of the present invention and another advantage is that hot-water supply device such as boiler can be connected thereto.
Income according to the application scenario of heat-storing device of the present invention also has, the usefulness thermic devices that links to each other with heat-storing device can satisfy any type of heat demand, for example they can participate in several heating activities simultaneously by heat transfer or defeated thermic devices, when connecting climate device, they participate in its heating-cooling activity; When connecting absorption cooling system, they participate in its heating-cooling activity; When connecting the defeated thermic devices of drier, they participate in dry movable, and except such use, they also can be various industry and processing industry activity and operation heat supply.
To the present invention be described according to the accompanying drawing that shows structure example below.
Fig. 1 has expressed as the thermal capacitance device 2 of the heat-storing device 1 of essential part, has been connected to heat exchanger 11, hot water supply, storage boiler 11a on the thermal capacitance device 2 and the expansion drum 18 that inert gas is housed.
Fig. 1 has expressed the thermal capacitance device 2 of heat-storing device 1; Fill with crystallization heat-storage medium 3 for before the operation thermal capacitance device 2.Be embedded in the heating-cooling tube 4 that transports heat-carrying agent 20 at this crystalline material 3 and molten matter 3a thereof.
As seen from the figure, originate in main pipe 8 that the thermal source 7a of thermal-arrest assembly 7 and being responsible for transports heat-carrying agent is directed to thermal capacitance device 2 by circulating pump 21, valve 6 and import pipe end 5 heating-cooling tube 4.It turns back to the pipe end 5 of heating-cooling tube 4 then, and gets back to the thermal source 7a of thermal-arrest assembly 7 by valve 6 and secondary pipes 9, so the circulation of heat hot container 2 finishes.
Fig. 1 has also expressed heat exchanger 11 and how to be connected on the thermal capacitance device 2 by valve 6 and tube connector 10; Heat exchanger 11 is connected to on the thermic devices 12 by pipe.
Flowing of heat transfer medium 20 flows to heat exchanger 11 by 2 beginnings of thermal capacitance device and by valve 6 and tube connector 10, and then returns thermal capacitance device 2, thereby finishes cooling heat release circulation.
As seen from Figure 1, thermal capacitance device 2, heat exchanger 11 and main pipe 8 and secondary pipes 9 all are covered with heat insulation layer 13.In thermal capacitance device 2, heat-storage medium 3, main pipe 8 and secondary pipes 9, heat exchanger 11 and heat transfer medium 20, provide the temperature monitoring assembly 14 that is used for temperature survey and detection, and the state sensing element 15 and the control device 16 that are used to regulate some ratio characteristic.
Fig. 1 also expresses thermal capacitance device 2 and links to each other with the expansion drum 18 that inert gas is housed by tube connector 17 with the main pipe 8 that transports heat transfer medium.
The figure shows out a kind of favourable structure, wherein the heating tube of the heating-cooling tube 4 of thermal capacitance device 2 and heat exchanger 11 all has a ribbed surface 23, thereby can improve its heat transfer property.
Fig. 1 also expresses the temperature monitoring 14 of heat-storing device 1, and state sensor 15 all is connected as a computer 25 with a computing technique device with control device 16.
Another favourable structure B of the present invention is shown among Fig. 1, and hot water boiler 11a is connected with heat-storing device 1.
Fig. 2 has represented the heat collector 7 of helioplant, and it comprises the absorber thermal source 7a that places on its focal plane.This thermal source fills heat for thermal capacitance device 2 by main pipe 8 and secondary pipes 9, valve 6 and circulating pump 21.
Fig. 3 has represented the heat-storing device 1 in the container 26 that places removable system.As seen, heating-cooling tube 4 is imported in the thermal capacitance device 2 that crystalline material 3 is housed from this figure.Be equipped with outlet pipe end 5, switch 19, heat insulation layer 13, thermometric instrument 14, sensing state 15 and control device 16 on these pipes.
Fig. 3 expresses the another kind of structure of the thermal capacitance device 26 of removable system, and wherein heating-the cooling tube 4 of thermal capacitance device 2 has ribbed surface so that obtain better heat transfer property.
Fig. 3 also expresses temperature monitoring 14, state sensor 15 and control device and controller 24 and a computing technique device and is connected to each other as a computer 25 and is in the same place.
The entrance end 5 that Fig. 3 also expresses the heating-cooling tube on the thermal capacitance device 2 of removable thermal capacitance device 26 is equipped with jockey 27, and this jockey can be connected to that the condenser system of traditional heating system and steam power plant or nuclear power plant or other station of conducting heat are gone up so that fill heat for the thermal capacitance device 26 of removable system.
Fig. 3 a expresses the thermal capacitance device 2 that is connected on climate device and the absorption chiller.
When operation during device of the present invention, solar energy equipment is placed on the top of building to be heated.This solar energy equipment can be a parabolic cylinder energy collector, and wherein, heat transfer medium 20 may be a kind of deep fat, circulates in the endothermic tube at the thermal source 7a of focusing place that places heat collector 7.This heat is gathered as the solar radiant energy on the endothermic tube of thermal source by parabolic mirror to be heated.Hot heat transfer medium 20 is imported in the heating-cooling tube system 4 of thermal capacitance device 2, and is circulated in the basement of building or in a closed room that suits by main pipe 8, valve 6 and import pipe end 5 by circulating pump 21 drivings.In the cyclic process, hot heat transfer medium 20 is with 3 heating of the crystalline material in the thermal capacitance device 2.Cold then heat transfer medium 20 leaves it at that so fill thermal cycle by exporting the thermal source 7a that pipe end 5, valve 6 and secondary pipes 9 flow back to heat collector 7.
When heat release, this device moves as follows: computer 25 will be made comparisons with the pulse data of thermometric instrument on the thermic devices (as drier) or heat regulator and program (software) data of input in advance from placing will heat indoor or being contained in other.Result based on the comparison is when heat transfer medium 20 drives by the tube connector 10 that originates in the heating tube 22 on the heat exchanger 11 circulation time, computer starting heating-heat release program by the circulating pump 21 that links to each other with tube connector.Simultaneous computer is closed the valve 6 on the outlet pipe end 5 that is contained in main pipe 8 and secondary pipes 9.So it is mobile through the heating-cooling tube 4 in the thermal capacitance device 2 that heat transfer medium 20 begins from heat exchanger 11.In flow process, the heat transfer medium 20 of the heating-cooling tube 4 in the thermal capacitance of the flowing through device 2 carries the heat of transformation and crystalline material subsequently 3 by the sensible heat of its molten matter 3a after the solar energy heating.The fluid of heating flows back to its interior water of heat exchanger 11 heating through heating tube 22.Heated water is sent to through main pipe 8a by circulating pump 21a driving and uses thermic devices in the heat exchanger 11, and hot water flows back to heat exchanger 11 and transmits the heat that is transmitted through secondary pipes 9a there, and the while heat cycles finishes.
The hot-water boiler 11a of the system for the distribution of commodities is connected on its thermal capacitance device 2 filling in heat and/or the heating-heat release circulation of heat-storing device 1, perhaps is connected on the heat exchanger 11 with tube connector 10a.In boiler operatiopn, after the pulse of receiving temperature monitoring 14 and after opening thermal switch and valve 6, the heat-carrying agent 20 that circulating pump 21 drives heat flow through tube connector 10a and boiler heating tube and circulate.Water heating in the hot-water boiler 11a, and when opening the water halter that is contained in the apartment, it just leaves system through hot-water line immediately.Simultaneously, the heat-carrying agent 20 of cooling returns its original initial place again behind the heating tube that leaves hot-water boiler 11a.
Heat-storing device 1 is equipped with following thing: the temperature monitoring instrument 14 of measuring and show the temperature of heat-carrying agent 20 and heat accumulating 3; Determine the state sensing element 15 of dielectric property; And the control device 16 of regulating ratio characteristic.These devices are connected on the computer 25 through center processing unit 24, and in service to calculator memory input data continuously.
Computer is made comparisons the data of input and the data of input in advance and is controlled the flow rate of heat transfer medium according to comparative result by activating valve 6 and other control element; Perhaps by partially opening or all open the heat supply that valve 6 is controlled heat exchanger 11 and/or hot-water boiler.
All are above-mentioned all at the row that require, because flow (with the suitable flow velocity) of heat transfer medium 20 prevented its overheated and heating, and can satisfy demand to hot water by the operation of by-pass valve control 6 and circulating pump 21.
The operation of mobile hot container 26 is similar to the operation (fixed) of above-mentioned heat-storing device 1.Its unique difference is in removable type 26, heat exchanger 11 can save, and the import and export pipe end of the heating-cooling tube 4 in the thermal capacitance device 2 is equipped with jockey 27, thereby portable heat-storing device 26 can be connected on condenser system in traditional heating system and steam power plant or the nuclear power plant or other station of conducting heat, so that fill heat to it.
Be in operation, portable heat-storing device is connected on the described thermal source by syndeton 27, and the thermal capacitance device 2 of portable then heat-storing device 26 drives by circulating pump 21 that heat-carrying agents 20 circulate and filled heat.
In the heat release pattern, portable heat-storing device, directly link on the jockey 27 with thermic devices 12 or the thermal capacitance device 2 equipped, the switch of jockey 27 turns to the outlet pipe end 5 of thermal capacitance device 2 separately or interconnection, and thermal capacitance device 2 that separate or interconnection is contained in the container of heat supply or defeated hot part.Open valve 6 and after circulating pump 21 startings, circulate the thermal capacitance device 2 that the heat that stores in the process just is delivered to usefulness thermic devices 21 or equipment at heat-carrying agent 20.
The method according to this invention comprises following operation: have in the thermal capacitance device 2 of heat-storing device 1 favourable heat storage capacity crystalline material 3-may for the eutectic point material by from hot heat transfer medium 20 heating of thermal source 7a until fusion, filled heat and with thermmal storage at phase transition process then.During heat release, the heat-carrying agent 20 of the thermic devices 12 of using by oneself from heat exchanger 11 or in portable heat-storing device is driven and circulates, and it is that recrystallization process finishes that molten matter 3a is cooled up to phase transformation, perhaps meets the requirements of chilling temperature, like this, stored heat just is output.
Be in operation, used some crystalline material or eutectic point material, they are repeatedly repeating to keep its invertibity in the phase transition process; Faint chemical reaction does not take place or only takes place in they and employed structural material; They can not corrode or only slightly corrosion; And their hot property parameter makes it have high phase-change thermal storage ability.
The additional advantage of the method according to this invention is not only can utilize the heat accumulation that is undertaken by latent heat of phase change, and the heat accumulation that can utilize the sensible heat by crystalline phase and liquid phase to carry out.
Claims (12)
1, a kind of heat-storing device that stores solar energy, wherein heat is collected by solar energy heat collector, and it comprises with the lower part: one or more solar radiant energy aggregation component; Belong to and place the receiver (comprising the heat-carrying agent that carries the solar radiation heat of being assembled) of focusing place of said modules; The main pipe is used to transport the hot heat-carrying agent that connects thermal-arrest assembly and thermal capacitance device; And secondary pipes, be used to transport cold heat-carrying agent, this heat-storing device is equipped with the device that one or more driving heat-carrying agents circulate, and promptly is equipped with circulating pump, this circulating pump is connected on the main pipe and/or secondary pipes that transports heat-carrying agent, and this heat-storing device is characterised in that:
Heat-storing device (1) comprises the thermal capacitance device (2) that is filled with the crystalline material of realizing phase transformation, in this thermal capacitance device (2), heating-the cooling tube (4) that transports heat-carrying agent is inlaid in crystalline material (3) or its molten matter (3a), so that fill heat and utilize stored heat to it, the pipe end of above-mentioned heating-cooling tube (5) is connected to one or more with thermic devices (12) through following parts: valve (6), transport the main pipe (8) of heat-carrying agent, link the secondary pipes (9) on the thermal-arrest assembly, tube connector (10), and one or more (or not having sometimes) heat exchanger;
Thermal capacitance device (2), heat exchanger (11), the primary and secondary level pipe (8,9) and the intermediate connection tube (10) that transport heat-carrying agent all are covered with heat insulation layer, state induction and control device (15,16) that thermal capacitance device (2), heat-storage medium, heat-carrying agent, the pipe (8) that transports heat-carrying agent and heat exchanger (11) all are equipped with temperature monitoring instrument (14) and are used for determining or regulate the heat-carrying agent characteristic and survey above-mentioned medium temperature;
The thermal capacitance device (2) of heat-storing device (1) and the main pipe (8) that transports heat transfer medium are connected to by intermediate connection tube (17) inert gas-in most cases on the expansion drum of nitrogen (18) are housed, and the combining form that basic device thermal capacitance device and associated component can somes satisfies heat accumulation and uses heat request.
2, the several sections of heat-storing device is characterized in that, the heat-storing device in the mobile system (1) is provided as basic device, and it can pack a container interior (railcar jar etc.) into by the vehicle conveying, or self drives; One or more thermal capacitance devices (2) are equipped with crystalline material (3), heating and cooling pipe (4), outlet connecting pipe (5), connector (19), adiabatic covering (13), thermometric instrument (14) and sensing state (15) and control device (16).
3,, it is characterized in that in order to heat energy storage, especially store the method for the heat energy of solar energy or other high temperature heat source such as steam power plant or nuclear power plant:
Stored with phase-change method from the heat energy that the thermal source transmission comes by heat transfer medium: in the thermal capacitance device (2) of heat-storing device (1) the good crystalline material of a kind of heat storage capacity (3) being housed, may be a kind of fusible material; This material (3) is filled heat and with thermmal storage from the heating of the hot heat transfer medium (20) of thermal source (7a) up to the crystalline material (3) of fusing, then, in the heat release pattern, heat-carrying agent (20) begins to circulate from heat exchanger (11), molten matter (3a) is cooled, finish i.e. crystallization again up to phase transformation, cooling just reaches best, and stored heat is removed in this way; In this process, used some crystalline material or eutectic point material, they are repeatedly repeating to keep its invertibity generally in the phase transition process; Faint chemical reaction does not take place or only takes place in they and employed structural material; They can not corrode or only slightly corrosion; And their hot property parameter makes it have high phase-change thermal storage ability.
4, according to the heat-storing device of claim 1, it is characterized in that:
Heating-the cooling tube (4) of heat accumulation cylinder (thermal capacitance device) (2) has ribbed surface (23) to improve heat radiation and heat absorption capacity, and the heating tube (22) of heat exchanger (11) also has ribbed surface (23) to obtain better heat-sinking capability.
5, according to the heat-storing device of claim 2, it is characterized in that:
Heating-the cooling tube (4) of heat storage can (thermal capacitance device) (2) has ribbed surface (23) to improve heat radiation and heat absorption capacity.
6, according to claim 1 and 4 the two let alone some part of one device, it is characterized in that:
Temperature monitoring (14), sensing state (15) and control device (16) and controller (24) all are connected to each other as a computer (25) with a computing technique device.
7, according to claim 2 and 5 the two let alone some part of one device, it is characterized in that:
Temperature monitoring (14), sensing state (15) and control device (16) and controller (24) all are connected to each other as a computer (25) with a computing technique device.
But 8,, it is characterized in that according to the removable transport section of the heat-storing device of claim 2:
The pipe end (5) of the Import ﹠ Export Department office of the heating-cooling tube (4) on the thermal capacitance device (2) of heat-storing device (1) is equipped with connector (27), it can be connected on the condenser system or other station of conducting heat of traditional heating system and steam power plant or nuclear power plant, adds heat so that fill for the thermal capacitance device (26) of removable system.
9, according to some part of letting alone one device in the claim 1,4 or 6, it is characterized in that:
Hot-water supply device is hot-water boiler normally, can be connected on the heat-storing device (1).
10, according to some part of letting alone one device in the claim 2,5,7 or 8, it is characterized in that:
Hot-water supply device is hot-water boiler normally, can be connected on the heat-storing device (1).
11, according to some part of letting alone one device in the claim 1,4,6 or 9, it is characterized in that:
The usefulness thermic devices (12) that is connected to heat-storing device (1) can satisfy any heat request of using, for example, by conduct heat or defeated thermic devices they can be used for some heating activities, they can participate in its heating-cooling activity when being connected to climate device, when being connected to absorption cooling system, they can participate in its heating-cooling activity, when being connected to the defeated thermic devices of drier, they can participate in dry movable, and in addition, they give various industry and processing industry activity and operation supply institute calorific requirement.
12, according to some part of letting alone one device in the claim 2,5,7,8 and 10, it is characterized in that:
The usefulness thermic devices (12) that is connected to heat-storing device (1) can satisfy any heat request of using, for example, by conduct heat or defeated thermic devices they can be used for some heating activities, they can participate in its heating-cooling activity when being connected to climate device, when being connected to absorption cooling system, they can participate in its heating-cooling activity, when being connected to the defeated thermic devices of drier, they can participate in dry movable, and in addition, they give various industry and processing industry activity and operation supply institute calorific requirement.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU9700202A HUP9700202A3 (en) | 1997-03-10 | 1997-03-10 | Device ensemble and method for storing heat energy |
| HUP9700202 | 1997-03-10 |
Publications (1)
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|---|---|
| CN1229466A true CN1229466A (en) | 1999-09-22 |
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Family Applications (1)
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|---|---|---|---|
| CN98800585A Pending CN1229466A (en) | 1997-03-10 | 1998-03-09 | Device and method for storing thermal energy |
Country Status (14)
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|---|---|
| JP (1) | JP2001504208A (en) |
| KR (1) | KR20000010920A (en) |
| CN (1) | CN1229466A (en) |
| AU (1) | AU6415498A (en) |
| BR (1) | BR9804892A (en) |
| CA (1) | CA2253928A1 (en) |
| CZ (1) | CZ9804043A3 (en) |
| HU (1) | HUP9700202A3 (en) |
| ID (1) | ID22084A (en) |
| IL (1) | IL126961A0 (en) |
| NO (1) | NO985216D0 (en) |
| PL (1) | PL329948A1 (en) |
| TR (1) | TR199802272T1 (en) |
| WO (1) | WO1998040684A1 (en) |
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| CN113375489B (en) * | 2021-06-29 | 2024-04-30 | 沈阳世杰电器有限公司 | High-stability heat storage and high-efficiency heat release solid heat storage device |
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| DE2551379A1 (en) * | 1974-11-21 | 1976-05-26 | Winfried Josef Werding | Heat storage using latent heat storage mass - devices control volume or pressure changes within storage and circulate heat |
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| US4403645A (en) * | 1978-07-12 | 1983-09-13 | Calmac Manufacturing Corporation | Compact storage of seat and coolness by phase change materials while preventing stratification |
| DE2855911A1 (en) * | 1978-12-23 | 1980-07-10 | Isopag Ag | THERMO-INSULATED HEAT STORAGE |
| US4244350A (en) | 1979-03-26 | 1981-01-13 | The United States Of America As Represented By The Secretary Of The Navy | Solar energy heat-storage tank |
| DE3034608A1 (en) * | 1980-09-13 | 1982-04-29 | Helmut Dr.-Ing. 7261 Gechingen Wiedmann | Heat transfer from source to consumer by melt storage medium - to increase distance covered |
| US4391267A (en) | 1981-04-15 | 1983-07-05 | Kay Laboratories, Inc. | Heat storage material |
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1998
- 1998-03-09 CZ CZ19984043A patent/CZ9804043A3/en unknown
- 1998-03-09 TR TR1998/02272T patent/TR199802272T1/en unknown
- 1998-03-09 AU AU64154/98A patent/AU6415498A/en not_active Abandoned
- 1998-03-09 CN CN98800585A patent/CN1229466A/en active Pending
- 1998-03-09 BR BR9804892-9A patent/BR9804892A/en not_active Application Discontinuation
- 1998-03-09 ID IDW980138D patent/ID22084A/en unknown
- 1998-03-09 IL IL12696198A patent/IL126961A0/en unknown
- 1998-03-09 JP JP53937398A patent/JP2001504208A/en active Pending
- 1998-03-09 WO PCT/HU1998/000021 patent/WO1998040684A1/en not_active Application Discontinuation
- 1998-03-09 KR KR1019980709068A patent/KR20000010920A/en not_active Application Discontinuation
- 1998-03-09 CA CA002253928A patent/CA2253928A1/en not_active Abandoned
- 1998-03-09 PL PL98329948A patent/PL329948A1/en unknown
- 1998-11-09 NO NO985216A patent/NO985216D0/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| AU6415498A (en) | 1998-09-29 |
| PL329948A1 (en) | 1999-04-26 |
| WO1998040684A1 (en) | 1998-09-17 |
| IL126961A0 (en) | 1999-09-22 |
| CA2253928A1 (en) | 1998-09-17 |
| ID22084A (en) | 1999-09-02 |
| HU9700202D0 (en) | 1997-03-28 |
| HUP9700202A3 (en) | 2001-05-28 |
| NO985216D0 (en) | 1998-11-09 |
| JP2001504208A (en) | 2001-03-27 |
| BR9804892A (en) | 2000-01-25 |
| KR20000010920A (en) | 2000-02-25 |
| TR199802272T1 (en) | 1999-07-21 |
| CZ9804043A3 (en) | 2002-01-16 |
| HUP9700202A2 (en) | 1998-12-28 |
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