CN1055947C - Heat-accumulating material and use thereof - Google Patents

Heat-accumulating material and use thereof Download PDF

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Publication number
CN1055947C
CN1055947C CN93103490A CN93103490A CN1055947C CN 1055947 C CN1055947 C CN 1055947C CN 93103490 A CN93103490 A CN 93103490A CN 93103490 A CN93103490 A CN 93103490A CN 1055947 C CN1055947 C CN 1055947C
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heat
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cha
temperature
storing material
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CN1091456A (en
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E·A·莱维斯基
V·N·帕蒙
E·M·莫罗兹
S·V·波格丹诺瓦
N·E·波格丹奇库瓦
O·N·科瓦兰库
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Ekateriram Ltd Liability Stock Co
Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences
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Ekateriram Ltd Liability Stock Co
Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences
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Priority claimed from SU904839454A external-priority patent/RU2042695C1/en
Priority to PCT/SU1991/000173 priority Critical patent/WO1993004137A1/en
Priority to AU84317/91A priority patent/AU667289B2/en
Priority to ZA931128A priority patent/ZA931128B/en
Priority to DE4305264A priority patent/DE4305264A1/en
Priority to FR9302000A priority patent/FR2701958B1/en
Application filed by Ekateriram Ltd Liability Stock Co, Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences filed Critical Ekateriram Ltd Liability Stock Co
Priority to CN93103490A priority patent/CN1055947C/en
Publication of CN1091456A publication Critical patent/CN1091456A/en
Priority claimed from US08/410,401 external-priority patent/US5585174A/en
Publication of CN1055947C publication Critical patent/CN1055947C/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • 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
    • F28D20/023—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 being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
    • 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

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  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
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  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Sorption Type Refrigeration Machines (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
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Abstract

The present invention relates to a heat storage material composed of a thermal inertia matrix and a heat sensitivity operation material, wherein the thermal inertia matrix is a substance with open small holes, and the operation material is a hydroscopic substance capable of carrying out dehydration-hydration reversible processes. The heat storage material of the present invention can be used as a reagent for the cooling and heating gas (air) media, or a reagent for preserving heat and preventing equipment or buildings from being heated, and can also be used as fire-extinguishing apparatus.

Description

Heat-storing material and uses thereof
The present invention relates to utilize the field of salt hydrate, say more truely, relate to a kind of thermal lag matrix and heat-storing material of containing as the crystalline hydrate salt of operation material as heat-storing material.
The task that the present invention will solve is the temperature control of air-flow and solid matter; The present invention can be used for daily life and technological process, for example, air conditioning machinery and heating system and working space, some do not wish the thermostatic equipment that heats and the purpose that is used to put out a fire.
The simplest and prevailing heat-storing material is a water.The very high thermal capacity (1Cal/g. ℃) of water has guaranteed the heat storage capacity of water heat-storage agent and equal mass, for example is the heat-storage agent of base is compared with sandy soil, exceed one times.But when converting by unit volume, then the two becomes almost, because the density of water and sandstone is different.Following narration will show that when relating to concrete heat-storing material, for example when those materials that can undergo phase transition (PCM), the advantage that solid system had is also wanted obviously.In a large amount of patent documents, study and utilized the heat storage performance of solid matter.At U.S. Patent No. 4708812 (J.C.Hatfield ﹠amp; A.W.Va) in, carried out detailed research for those theory and practical problemss based on relevant accumulation of heat in the PCM system of the fusing of solid matter and crystallisation process.
In these systems, used the material of forming by crystalline hydrate salt.The data of drawing relevant crystalline hydrate fusing point in handbook in table 1, have been listed.
The fusing point of some crystalline hydrate of table 1 and the latent heat of fusion
Salt Fusing point ℃ Latent heat of fusion cal/ ℃ The source
Na 2CaO 4.10H 2O Na 2SO 4.10H 2O Na 2S 2O 4.5H 2O Na 2HPO 4.10H 2O CaCl 2.6H 2O 23 31 48 36 29 39 51.3 47.8 66.8 40.7 Handbook Chemistry and Physics 33ed，P.1916-17 Chemical Rubber Publishing Co.， Cleaveland，Ohic
From the table data as can be seen, in most of the cases, these fusing points all are higher than the temperature (20 ℃) that the people is felt comfortably cool significantly.In all cases, the latent heat of fusion of these salt is all little, therefore allows the heat few (being about dozens of kcal/kg quality) that stores in the accumulation of energy operation material of per unit.
We enumerate EP0034710 as an example, and the composition of wherein being put down in writing that is used for accumulation of heat is used close with us.In this patent document, crystalline hydrate salt is comprising crystalline hydrate CaCl 26H 2O is scattered in pottery (cement) matrix of the hydraulicity.
With the cement matrix is that example-this is a kind of by particle diameter relatively large (about 10 3-10 4Nm) cement granules, the porous material that forms after hydration, the kapillary that forms between these cement granules also almost are same sizes, and the coarse-grained salt that crystallizes out in these kapillaries also almost is same size.When aperture that such size is arranged and particle, cement matrix can retain the melt of salt (preventing its outflow) by means of the effect of capillary force, but this effect can not produce any influence to the character of accumulation of heat operation material.
Therefore, be exemplary with accumulation of energy agent based on phase transition process (PCM), for the patent of great majority based on this principle, this accumulation of energy agent all has its merits and demerits.
In those production capacities and the nonsynchronous any power system of power consumption, the accumulation of energy agent is a kind of requisite integral part (referring to W.Twidell, A.D.Weir, Renawable Energy resources, London 1986).In heating system, there are these three key elements of thermal source (u), heat-storage agent (a) and user (n).For this system, what often have following forward concerns tu＞ta＞tn.In order to adapt to this purposes of heat-storage agent, heat-storage agent should have following several characteristic:
1. The temperature that stores,
Think that at first approx said this temperature (ta) is low more, then the quality of heat-storage agent high more (investing few more big more) with feasibility heat-storage agent.But, because ta＞tn, so should consider heat energy user's character.Ta considers these users' diversity, so should be an adjustable parameter.Those working temperatures that the most interesting is are near 20 ℃ hold over system, and this temperature it is to approach the temperature that feels comfortably cool on physiology.This class heat-storage agent can be used as those capital construction facilities in conjunction with the constant temperature function (play cooling effect when height optimum temps, and play the heating effect when being lower than optimum temps).This moment, these remaining heats were stored in the heat-storage agent, can heat with it when air turns cold.
2. Compare stored energy capacitance
The ratio stored energy capacitance of heat-storage agent also is an one basic feature.The heat that can store in the material of the per unit volume (or quality) of heat-storage agent has determined working cycle perdurability, size and the stored energy capacitance of this device.
3. Deposit the hot time
Because (weather) each different steps at nature, the height of temperature has very big difference along with the time, therefore must make heat-storage agent store heat (in the scheme that is the work period, be a few hours with the sky, and in the scheme that with the season is the work period for round the clock many) for a long time.
4. Stability, nontoxicity, price
Important requirement to heat storage material is their stability, nontoxicity, feasibility and not high prices in the multiplex (MUX) does the cycle.Comprehensive above-mentioned various requirement can be estimated the carrying out horizontal of Technology and technical solution two aspects to this task of being advised.
Now we according to the viewpoint discussion of the relevant heat-storage agent performance index of above pointing out in prior art and the result that similarly reached in the method.
1. utilize heat-storage agent can successfully solve the task of regulating transformation temperature (ta) based on the PCM-system.For this reason, use can form the mixing salt of eutectic mixture.The mixture that uses so in the prior art is Na 2SO 4.10H 2O and NaCl.H 2O.By change in the mixture each components in proportions can make ta from+7 ℃ change to+22 ℃.
2. shown in as above showing, the latent heat of fusion of these crystalline hydrates all very little (tens of cal/g), the size that this increases necessary heat-storing material quantity significantly and has determined hold over system.
3. village's little caused other consequences of material PCM regenerative capacity that are used for accumulation of heat are to be restricted the shelf time of savings heat.The actual shelf time of heat is depended on the speed of cooling of PCM, and speed of cooling depends on heat and the insulation effect of savings in this material.Because the restriction of these two factors, so the storage life of heat in heat-storage agent can not be very long.
Therefore, according to these two leading indicators (shelf time of regenerative capacity and accumulation of heat), do not meet the heat-storing material requirement based on the heat-storing material of PCM.These reasons have limited numerous PCM-system practical applications in every respect just.
Should be noted that these shortcomings are that the reason by the effect of PCM-system itself is determined, and, in known accumulation of heat system,, also can't overcome these shortcomings no matter take improvement measure on any structure.
In order to solve this task, require the endothermic effect of (for example with the order of magnitude) raising when accumulation of heat significantly.Any endothermic effect all will be by destroyed the deciding whether of the associative key between each particle in the solid matter.Its size depends on the energy of these keys.If ruined in the PCM-system is weak intermolecular key, this has just determined that the numerical value of the latent heat of fusion of this material must be little so.
In order to improve the quantity of accumulation of heat significantly, just must manage to destroy strong intramolecular key, for example, dehydration (from crystalline hydrate salt, partially or even wholly removing the water of chemical bonding) (table 1).
An object of the present invention is to provide a kind of heat-storing material, than the prior art material it when increasing the shelf time of accumulation of heat significantly (order of magnitude) improve heat-sinking capacity.
Another object of the present invention is a heat-storing material as the purposes of the reagent of cooling and heated air medium, can be used for the insulation of goods or buildings or fire extinguishing etc.
Below narration be used to solve the means of this task-propose some based on the new system of material chemical transformation and obtained to be referred to as the respective substance (agent of CHA-chemical heat accumulation) of chemical heat accumulation agent.
A kind of chemical decomposition process of salt takes place in the operation material of CHA-system.For example, at crystalline mixture CaCl 26H 2Under the situation of o, this reaction is
This is the decomposition course of a heat absorption.The heat that is consumed and water remove and follow-up evaporation relevant.Certainly, the heat that is absorbed is proportional to the size of the mole number of the water that is removed, every mole of material endothermic effect and the mole number of the operation material that exists in the CHA of unit volume or unit weight.For CaCl 2.6H 2O, this numerical value can calculate at an easy rate.
Calculate according to the data of quoting, be equivalent to 1mol H 2The mean value of the variation (endothermic effect) of the generation heat of the crystalline hydrate of O is 74kcal/molH 2O.Because this numerical value comprises the hot Δ H of the generation of water molecules itself H2O=-58kcal/mol, thus must calculate the difference 74-58=16kcal/mol of this this two numerals, promptly at crystalline hydrate [Ca (OH 2) 6] ++Synergistic energy (bond energy) between the middle water molecules.When sloughing water molecules, also should add the mole vaporization heat of 9Kcal-water to this numerical value.
Amount to q=16+9=25kcal/mol.
At each mole CaCl 2.6H 2O (about 220g) emits 4mol water when decomposing, and promptly total heat effect is
25×4＝100kcal/mol CaCl 2.6H 2O。
Therefore, the latent heat of CHA-system is at least than the high order of magnitude of latent heat (referring to example) of known PCM-system.
The temperature of dehydration is usually above the temperature of fusing point.Because reaction Carry out 31-45 ℃ temperature range, therefore surpassed the working temperature of heat-storage agent significantly.
In order to solve the task of proposition, must reduce the heat sensitization compound significantly, crystalline hydrate salt for example, the decomposition temperature.
In the present invention, said task is to utilize a kind of what is called " dimensional effect " to finish, and just changes the structure and the character of this material when being distributed to microscopic size by the group's material with crystal form.
As everyone knows, for thick particle, atom number n → ∽ wherein, some thermodynamical coordinates, for example fusing point or vapour pressure, its numerical values recited all is constant (when the P=constant, the T=constant).When the particulate size changes to, D＜10 for example -5During cm (100nm), this rule is just destroyed.Fusing point is obtained with the authentic data that particle size changes.Under the very small situation of particle size, α＜10nm for example, this relation just become significantly and substantially be non-linear (referring to, H.H.3e Л И Н Γ for example, φ TT7, No.3,881 (1965)).The analysis expression of relevant fusing point of deriving on the basis of experimental data and particle radius R relation is: TR = T o exp ( - 2 αΩ RQ ) ≈ T o ( 1 - 2 αΩ RQ ) Wherein:
The fusing point of To-macrocrystalline (R=∽)
α-coefficient of surface tension,
Ω-atomic volume,
The Q-latent heat of fusion.
This analysis expression is drawn by the basic equation of TOMCOH (κ e л ь в и н а): P = α R . Ω KT Po This equation has determined surplus pressure on the drop (particle) in final size (referring to Я .E. Г e г у з и н, φ и з и к а с л e к α н и я, " Н α у к α ", М., 1967), above-mentioned relevant molecule can explain so approx in the physical significance of structure and qualitative variation, and that part of energy (forming the surface of molecule) that promptly is used for dissemination and is consumed is stored in its three-dimensional arrangement.This point can show fully from the following fact, and just in small particle, it is very big to have a shared relative share of the surface atom of greater activity and free energy.Tested abundant confirmed theoretical relationship from these and can draw in wide wide particle size range (for example from 100nm to 5nm), the variation of " entropy " (fusing point of material reduces, and vapour pressure raises) is preponderated; Simultaneously, as " enthalpy " effect, for example, the reduction that interatomic distance increases or material generates heat only appears in the scope that particle size is 1-5nm (referring to, for example, the monograph of the Я Е Г e г у з и н that above quotes).We have proposed a kind of hypothesis, according to this hypothesis, for any thermo-sensitivity crystalline material, generating heat haply under the constant situation, in being the scope of 5-10nm, particle size should observe the substantive dependence of decomposition temperature to particle size:
T=f (R), Δ H (R)=constant
The experimental study that utilizes physical method (x radiography, calorimetry) to finish shows, for example, and for crystalline hydrate CaCl 2.6H 2O is when the particle size of salt exists
D=10-100nm (10 -7-10 -5Cm) in the time of in the scope, there is above-mentioned relation really.
Lift some below about CaCl 2.6H 2The important results that the decomposition temperature of O changes with crystalline particle dimension D (nm)
The decomposition temperature of particle size salt
D, the CaCl of nm ℃ of 1. standards 26H 2O＞100 292. sample No.1,50～253. sample No.2 10 13
Result of study shows, the reducing of salt particle size not only can change the temperature that crystalline mixture decomposes, and also changes the mechanism of its Decomposition simultaneously, according to reported in literature, and crystalline hydrate CaCl 2.6H 2O resolves into CaCl in 31-45 ℃ temperature range 2.4H 2O also loses 2 water moleculess simultaneously, loses two water moleculess again at 50-60 ℃ then, becomes CaCl 22H 2O.Process is opposite therewith, under the situation that temperature reduces and temperature raises of environment, can observe CaCl 22H 2O is transformed into 6 original hydrate CaCl fully 26H 2O.This working process is based on the result that the CHA-material of being recommended is furtherd investigate.
When realizing this process, run into the difficulty aspect the natural condition: in fact can't carry out manual operations with the particle of microscopic size (less than 100nm).
In addition, the abundant uneven system of these energy is condensed rapidly and is formed coarse particles (R=∽).In order to solve this task, we have studied the method that the particle of salt is placed porous ceramics matrix.The porous matrix of our research, for example be the matrix that a kind of oxide compound by silicon (silica dioxide gel) is formed, different with the matrix of prior art, it has the micropore (10-50nm) that much is of the required size, and the particle of the salt that crystallizes out in these apertures also has same (micro-) size.
Like this, has the crystalline hydrate that particle size is D＜100nm (CaCl for example at 1kg 26H 2O) in the operation material, potential is about 450kcal/kg salt.Utilizing a kind of pore volume to be about 1cm 3/ g (this is equivalent to about 0.5L hole/1L apparent volume) and crystalline hydrate density are 1.7g/cm 3The situation of silica dioxide gel under, the potential in the particulate CHA of 1L apparent volume material is 400kcal/l.
In a large amount of known crystal class compounds, it selects possibility to depend on following factors:
A) for a large amount of known crystalline hydrates, press 1mol H 2The generation heat that O calculates is a constant and the energy variation range delta H～16 ± 2Kcal/molH that accords with following formula haply 2O.
B) be through repeatedly still keeping its stability after hydration/spin cycle to a most important requirement of operation material.At this moment main restriction is relevant with the partial hydrolysis that salt might take place when crystalline hydrate decomposes.Having this stability, at first is strong acid salt and highly basic salt.In the transition process of the element that forms amphoteric substance and oxyhydroxide, separating out acid.The salt that the acid of thermo-sensitivity (nitric acid, acetate, oxalic acid etc.) forms also can utilize;
C) avirulent salt;
D) cheap and easy to get.
CaCl is preferably used in comprehensive above-mentioned every requirement 26H 2O, it has thermo-chemical stability, owing in 1mol salt, can emit 4mol water, and have very big potential, there are not toxicity and (calcium chloride is the main byproduct when producing soda ash with CO л ь в e method, and its utilization of waste material also is a problem) cheap and easy to get.
For selected crystalline hydrate, in fact can be used as that matrix uses be those pore volumes therein meet many property material of the orifice size of recommending (less than 100nm) carrying opening aperture, comprise that particulate state or pulverous particle diameter are the porous particle of 1 to 5000 μ m, belong to having of this class material: porous glass and similarly ceramic-like materials, porous metal and polymkeric substance, gac and other have the matrix of pore.
In order to realize the potential possibility of CHA-system, the most important thing is to utilize so-called " opening wide system ", in this system, can realize heat exchange with surrounding environment, also can realize the exchange of material (moisture).
By purposes and the meaning of itself, any accumulation of heat system is all opened wide heat, because carry out the necessary condition of application that heat exchange is any heat-storage agent with surrounding environment.
If make heat-storage agent suction heat (Ψ=100%) there from damp atmosphere by making air be cooled to 10 ℃ from 20 ℃, so, the heat that heat-storage agent seizes from dry air when being cooled to 10 ℃ only is equivalent to 1/1.5 of when temperature is reduced to same 10 ℃ water vapor condensation institute liberated heat.Therefore, under the situation of damp atmosphere, main energy gesture is with to be present in this airborne moisture relevant.There have a large amount of water vapour (transpiring moisture is a main method of utilizing sun power at occurring in nature) and regulate airborne moisture when temperature is higher than 0 ℃ in air to be quite easy, these have just determined can use especially effectively the water-absorbent heat-storing material as operation material in the accumulation of heat system, comprising the crystalline hydrate salt of describing among the application.In order between CHA-village material and gaseous media, to realize " opening wide " exchange of moisture process, must make that said steam (having the absorbent material of thermo-sensitivity therein) is " opening wide " and can freely exchange with gas (air) medium.
Be stored in the heat energy in the CHA-material, be present in this material with a kind of potential form that can react with.Different with the PCM-system, the CHA-material can have any temperature (it equals the temperature of surrounding environment usually).But, even when the t of t＜surrounding environment, any Decomposition of CHA-material also can not take place.No matter be accumulation of heat or heat release, all change relevant with the chemical constitution of this system.Therefore, if heat-storing material can not effectively contact with reagent (water vapour), wherein the heat of Chu Cuning just can not emitted.Under the situation that lacks this contact, energy stored can be preserved the time of endless in the CHA-system.
The enforcement of CHA system has solved restriction, and to be widely used in promising on the principle be two basic problems-raisings energy storage capacity and the prolongation heat shelf time that the accumulation of heat of base can system with crystalline hydrate salt.
Like this, advised based on crystalline mixture CaCl 26H 2The CHA-material of O is characterised in that, very high accumulation of heat energy storage capacity, and its working temperature approaches optimum temps (feeling comfortable temperature).The extraordinary of this performance has determined in conjunction with (having high stored energy capacitance under not high temperature), when needing rapidly and effectively the heating of airborne heat of venting or needs in department, the application of CHA-material in traditional and the most modern technical field has very wide wide prospect.
When the salt particle size is reduced to microscopic size (less than 100nm), the material decomposition temperature be reduced in the character that not only depends on salt on the little degree, also be decided by the character of porous matrix simultaneously, this is the basic effect of the inventive method as basis.Between temperature-sensitive character and body material, can not there be specific chemical action.For example, because between matrix and heat-sensitive substance, there is the intensive ion exchange process, and the possibility of using zeolite is restricted.
The direction and the speed of the groundwork process of CHA-material depend on the reversible thermal chemical reaction.
Equilibrium state in this system not only depends on temperature, also depends on the humidity of surrounding environment.Therefore, according to the importance and the meaning of the controlling factor of accumulation of heat and heat release in the CHA-material, the humidity of air is deputy.Utilize CHA-material of the present invention can make those are used for keeping comfortable (optimum to body) temperature (being generally 20 ± 2 ℃) in the volume of sealing device.It is this that we are referred to as " comfortable device " with temperature adjustment function and the device that combines of heating function.Effect that should " comfortable device " is based on the reversible thermochemical cycle of the accumulation of heat of low latent heat in the chemical heat accumulation agent (CHA-system) and heat release.In conditioner, lack for example this automatization energy, will limit the possibility of using this comfortable device as heat pump.The application of this energy storage technology is towards the little place of volume (for example about 50m 3) and in the scheme (not having warm air or freezing air to flow into from outside atmosphere) of enclosed space, use as attemperation.But, these advantages of " comfortable device ", for example simple, reliable, minimum power consumption and pollution of ecological environment (without fluorine Lyons) not make it have competitive power to vast human consumer.
This rare performance of CHA-material-approaching under the condition of room temperature is put aside a large amount of heat energy and (is reached 1kcal/cm 3) ability, having enlarged these materials significantly may Application Prospect on technology.In this application, except being used in the room, regulating the main application of air themperature (comfortable device), also recommended two kinds of unorthodox methods of using heat-storing material:
1. the part and the device that the time have been heated in work of cooling.For wide technical field, at first, for the element and the various electronics equipment of the wireless apparatus that is called as Э BM, and in order to prevent that buildings from suffering fire, above-mentioned cooling task is necessary.
2. other are unconventional, but the application direction of reasonably drawing from the special property of CHA-material be used to stamp out a fire-promptly put out uncontrollable combustion processes.
Because the CHA-material can absorb the heat of about 1kcal/g in 20-40 ℃ temperature range, be a kind of effectively fire-fighting medium therefore, as long as use MIN quantity can in fact put out any fire.
For above-mentioned range of application, the zeolite of hydrated form has the character very approaching with the CHA-material, and it can absorb heat effectively under being heated to 80-100 ℃ temperature and the moisture that will absorb originally is discharged in the surrounding environment.Therefore, in order to prevent the overheated and fire extinguishing of various goods and buildings,, also can use the zeolite of hydrated form or they and CHA-mixtures of material according to spirit of the present invention.Under many circumstances, because natural zeolite is cheap and easy to get, therefore more welcome.
The CHA-preparation methods is based on a series of traditional steps: with the solution impregnation matrix of salt, separate solvent and carry out the crystallization of crystalline hydrate salt simultaneously.
Behind specific embodiment and the accompanying drawing, other purposes of the present invention and advantage will become clearer below reference, provide the x x ray diffration pattern x that the sample that uses the inventive method to obtain is photographed in the accompanying drawings.The position corresponding of lines is in synthetic phase CaCl 26H 2O.Because crystalline small-sized (100_) is so diffraction fringe broadens.
Δ H fusing＜＜Δ H decomposition
=-74kCal/mol H 2O Δ H decomposition=Δ H generates H 2O+ Δ H bond energy Δ H bond energy=Δ H decomposition-Δ H generates H 2O74-58=16kcal/mol16kcal/mol+9kcal/mol (evaporation)=25kcal/mol
Embodiment of the present invention
Provide the specific embodiment A and the B of preparation CHA-material below.
Embodiment A
1kg a kind of had about 1cm 3/ g porosity, aperture are 10-15nm, pelletized silica gel (granularity 3-7 μ m) to impregnated in 1000ml concentration be 40% CaCl 2In the solution.Then impregnated material drying also then is placed on 240 ℃ of roasting temperatures and desolvates in (water) to removing fully, the result obtains a kind of anhydrous salt in the matrix aperture.After obtaining material cooled, be placed in the moist atmosphere and and control reaction process according to the variation of weight, it is hydrolyzed into consists of CaCl 26H 2The crystalline hydrate salt of O.
Embodiment B
With a kind of dispersity of 1kg is 1-100 μ m, and total pore volume is 2.8cm 3/ g, the aperture is that to impregnated in 2800ml concentration be 40% CaCl to the Powdered silica dioxide gel of 10-15nm 2Solution in, then by the step similar to embodiment A with obtaining material drying and roasting.And then this material be impregnated in the same solution for the second time saturated to water content, and carry out drying and the roasting second time, be placed on then and carry out hydration reaction in the moist environment until obtaining a kind of CaCl of consisting of 26H 2Till the crystalline hydrate salt of O.The x ray diagram that provides is consistent with the sample according to embodiment A and material that B obtains.These data show, have generated crystallization phases CaCl in the aperture of these matrixes really 26H 2O.
In embodiment 1-4, explain CaCl below with various different-grain diameters 26H 2Crystallization of O salt and operation material filling substrate aperture are in various degree.
Embodiment 1
Heat-storing material is the CaCl of 50nm by a kind of median size 26H 2The O crystal is formed.(grain contains the crystalline hydrate of 400g (about 2mol) to this village material in φ=3-7mm) in the matrix of 1 liter of apparent volume.According to calculated value (seeing above), the energy storage of this thermophore is about 200kcal/L apparent volume or about 300kcal/L true volume (not considering intergranular space in packing box).Be transition temperature ta=25 ° ± 1 ℃ that records by experiment under the condition of Ψ=65% in relative humidity.
Embodiment 2
Heat-storing material is the CaCl of 10-15nm by a kind of particle diameter 26H 2The O crystal is formed.This material contains the crystalline hydrate of 400g (about 2mol) in the matrix of 1 liter of apparent volume.The heat storage capacity of this heat-storing material also correspondingly is the material of 200-300kcal/L apparent volume or true volume.The relative humidity Ψ of environment=65% o'clock around, the decomposition temperature of salt is 13.5 ℃.
Embodiment 3
Heat-storing material is the CaCl of D=10-15nm by a kind of particle diameter 26H 2The O crystal is formed.As embodiment 2, the decomposition temperature of salt also is 13.5 ℃, but the salts contg in 1 liter of apparent volume is 800g.Therefore, the heat storage capacity of 1 liter of material is 400-600kcal/L.
Embodiment 4
Similar in heat-storing material and embodiment 2 and 3, difference is, is about 1cm without total pore volume 3The pelletized silica gel of/g and be to use and a kind ofly have same aperture but total pore volume is 2.8cm 3The powder of the highly porous property of/g.Owing to have much bigger pore volume, so obtained a kind ofly in 1 liter of volume, to contain 1.53kg CaCl 26H 2The Powdered heat-storing material of O.The heat storage capacity that this sample has under same regenerator temperature (13 ℃) is about 700kcal/L.
The embodiment 5-8 that lists below explains the application of CHA-system aspect the adjusting air themperature.
Embodiment 5
In a vertical cylindrical adiabatic reactor, a kind of granularity φ=3-7mm that packs into, the CHA-material 1L of the about 500kcal/L apparent volume of stored energy capacitance (seeing embodiment 3) presses 1m 3The flow of/h infeeds a kind of moisture content less than 1g/m in reactor 3Dry air, when the drying air temperature of ingress is 15-20 ℃, because crystalline hydrate decomposes the cooling effect cause under adiabatic condition, make that the air themperature in the CHA layer descends, so that be 0-5 ℃ (Δ t=-15 ℃) in the temperature of reactor exit.Airborne water content is elevated to 4g/m simultaneously 3, the Ψ when this numerical value approaches t=+5 ℃=100%.Obviously, this simple and be that the practical significance of the method for cleaning is to obtain the required cooling effect of daily life (0-5 ℃ temperature range is equivalent to the working temperature of home freezer) for ecology.It is more suitable to preserving vegetables to use this high-moisture cooling air.Different with common refrigerator, system described herein does not require uses fluorine Lyons, and the energy that is consumed is equivalent to 1/10 (needs use in order to make air pass through the low power ventilator of CHA-material layer to replace the compressor in compression fluorine Lyons) of general refrigerator.The energy expenditure of replenishing can obtain by means of the exsiccant air, still, and known some otherwise effective technique solutions in addition.
Embodiment 6
Experimental technique is similar to embodiment 5, but the speed of air by CHA-material particle layer is 1m 3/ h, the t of this material begin=and 30 ℃, Ψ=50%/(exchange velocity 1000L/hh/).When air contacted with particle, dehydration took place owing to having absorbed heat in crystalline hydrate.Owing to carried out heat exchange with particle, air is cooled to+and 20 ℃ and its absolute humidity brings up to 2g/m 3The data that obtain in the experimental period of work period (about 200 hours) approach the calculated value under specified stored energy capacitance (500kcal/L particle).
Embodiment 7
Experimental technique is similar to embodiment 6, but the airflow through-rate is increased to 2m 3/ h, exchange velocity 2000L (hh).In the working hour of 200h chemical heat-storage agent guarantee the air cooling of ingress+25 ℃ to outlet+20 ℃.
Embodiment 5,6 and 7 has explained that (dehydration) absorbed heat in the accumulation of heat cycle of heat-storage agent.Embodiment 8 finishes explanation the condition of reversing process.
Embodiment 8
Use the reactor identical, but the CHA-material granule in the reactor of packing into contains the operation material (CaCl of dewatering state with embodiment 5-8 22H 2O).Feeding starting temperature be+15 ℃ the air contained water (hydration (heat release) of generation heat-storage agent during Ψ=50-60%).The air themperature in exit is+25 ℃, and absolute humidity is reduced to 1g/m 3
Embodiment 9-12 explains the result who is used to the basic skills of the task that solves and uses this method to obtain.
Experimentation is carrying out in typical lab setup, in this device, with the element (plane metal sheet) of thermal source electrical isolation with have same area (6 * 6=36cm 2) hot plate carry out mechanical contact.As (0.05v/cm 2Sec) electric current is when the hot-plate, and hot-plate has same area and thickness is the test board of 2mm with regard to being heated and the heat of itself being passed to.On the other hand, have epoxy resin layer on the test board, this resin layer contains finely divided (less than the 100u) powder as the CHA-material of weighting agent, for example, and the powder described in the embodiment of the present application 4.
Embodiment 9
The contrast experiment, in this experiment, test board is the tectum of tape tree fat and CHA-material not.After energising one hour, the temperature of lower floor's test board reaches 95 ℃ (temperature rise 95-20=75 ℃).
Embodiment 10
Experimental technique and embodiment 9 are similar, are scattered in tectum in the Resins, epoxy but have one deck on the free surface (a not side that contacts with the electric heating agent) of test board by the CHA-material powder, and the thickness 1mm of covering is (at 1cm 20.1cm is arranged on the test board approximately 3Powder).After energising one hour, test board still keeps temperature to approach original (room temperature) 20-30 ℃.
Embodiment 11
Experimental technique and embodiment 10 are similar, but the tectal thickness of accumulation of heat is increased to 3mm (at 1cm 20.25cm is arranged on the test board approximately 3Powder) this tectum can guarantee that keeping temperature in 2 hours processes is 20-30 ℃.
Embodiment 12
Experimental technique and embodiment 10 and 11 are similar, but the tectal thickness of accumulation of heat is increased to 5mm (at 1cm 20.4cm is arranged on the surface of test board approximately 3Powder).This tectum can guarantee to keep the temperature of test board in the process in 20-40 ℃ scope at 4 hours.
From embodiment 9-12 as can be seen, using the synthetic resins that has weighting agent (powder of CHA-material) is in working order down by metal or the exothermic effective ways of other heating surface.Simultaneously, the effective accumulation of heat effect of weighting agent (powder of CHA-material) has guaranteed that temperature can remain on and has been lower than polymkeric substance significantly in conjunction with key destructive temperature (fail temperature of Resins, epoxy is about 100 ℃).Compositions for use is made up of finely divided (less than 100 μ m) CHA powder and Resins, epoxy in embodiment 10-12.(the strong cohesive force between the porousness base matter of CHA allows to prepare the composition of (the reaching 80% quality) heat-storing material that has high-content for resin and silicon-dioxide.Application of epoxy is right-on in this based composition, because they combine the performance of two kinds of preciousnesses, i.e. high resistance and medium thermal conductivity pass to the powder of CHA-material in order to make heat from heating surface, and this capacity of heat transmission is necessary.
Embodiment 13-15 explains that using the CHA-material stamps out a fire.
Embodiment 13
Toward a diameter is 5cm, highly for adding 2.5cm in the flattened cylindrical shape shallow bid of 1cm 3Kerosene (the about 1mm of kerosene layer thickness) is also lighted it.The time that kerosene burns down under selected condition is about 200 seconds, and this numerical value accords with the heat release 125cal/sec or the 2000cal/8sec of calculating.Burning is stable, and can reproduce the combustion time of experiment, is 200 ± 10 seconds in a series of repeated experiments.
Embodiment 14
Method by embodiment 13 experimentizes, but during 50 seconds after lighting, and spreads down the CHA-material powder (seeing embodiment 4) with high heat storage capacity on the kerosene flame of toward burn steadily.(-Yue 10 seconds joining day) flame is put out fully when adding about 1g powder.But, owing to have quite a few finely divided powder to leave the combustion zone and deposit to (in the shallow bid of kerosene is housed) around the container.This has increased the consumption of fire-fighting medium significantly.
Embodiment 15
Experimental technique is similar to embodiment 13 and 14 to carry out, but the CHA-material uses with particle form (granularity 1-3mm).These particles have enough quality, enable to be deep in the combustion zone of kerosene.The consumption of CHA-material is about 0.3g, it seems that this numerical value accords with the true consumption of fire-fighting medium when putting out a fire.
Therefore, for the CHA-material being effectively applied to fire extinguishing, must under the condition of the about 0.3kg extinguish material of every 1000kcal thermal discharge consumption, guarantee it is applied on the incendiary surface.
Should emphasize that the CHA-material only just has above-mentioned performance under the state of hydration.Therefore, must guarantee to get rid of the storage requirement (temperature, stopping property) that the uncontrollable ground of generation (spontaneously) decomposes (dehydration) possibility.
The advantage that the material of being recommended is different from most of similar substances is its validity, intensive and emits any deleterious material at the Shi Buhui that is heated.
The most effectual way of using type of recommendation solid phase fire-fighting medium be with machinery fire-fighting medium is spread on the material incendiary surface-Sa is to more unsettled conflagration area, in this zone, the interaction energy of minimum is received the most significant effect.According to embodiment 13-15, for the consumption of the necessary fire-fighting medium that stamps out a fire, at 1m 2Burning surface on be 0.15-0.5kg, this numeral approaches the preferred example of known fire-fighting medium in worldwide practice.
It seems, the most effective during regional presence of fire that being applied in of this fire-extinguishing agent is difficult to enter, for example hill fire, and at the fire of carrier.
Compare with the known heat-storage agent based on the phase transformation effect, the heat-storing material that the application provides has two basic differences:
-heat storage capacity is wanted for example 10 times of height,
-heat-retaining the shelf time is actually unlimited.These qualitative differences make it can solve some new technical assignments, are insurmountable under the situation of these tasks production solid phase in the past heat storage material and composition.
1. build general " seasonality " heat supply circulation in house, utilize the heat that is stored in the heat-storage agent material to regulate the temperature in summer and the winter that needs heating.Have the area of moderate climate at great majority, this circulation all is feasible and effective.
2. substantially be to have solved thermoregulator problem on the new basis, this point is urgent especially for high-speed electronic computer and various electronic machine.The efficient collection dense body system of draining heat that contains that the polymer resin of CHA-weighting agent makes can simplify the structure of electronic machine significantly and improve its reliability.
3. utilize the CHA-material to stamp out a fire can to reduce significantly the demand to fire-fighting medium, this point is urgent especially under geographic gloomy fire that is difficult to enter and the situation at the fire of haulage system.

Claims (10)

1. heat-storing material, this material is made up of the matrix of thermal lag and the operation material of thermo-sensitivity, it is characterized in that containing the material of carrying opening aperture as matrix, described material as the carrying opening aperture comprises that particulate state or pulverous particle diameter are the porous particles of 1 to 5000 μ m, be selected from inorganic materials, polymeric material, carbon or metallic substance, contain as operation material and can dewater-hygroscopic matter of the reversing process of hydration, described hygroscopic matter comprises the crystalline hydrate of the particle diameter of crystalline form less than 100nm, and said crystalline hydrate its chemical constitution when temperature variation also changes.
2. according to the heat-storing material of claim 1, the diameter that it is characterized in that described open aperture is 10nm.
3. according to the heat-storing material of claim 1, it is characterized in that operation material is CaCl 26H 2O, matrix is silica gel.
4. each heat-storing material of claim 1-3 is as the purposes of the cooling and the reagent of heated air medium.
5. according to the purposes of claim 4, wherein said gas is air.
6. each heat-storing material of claim 1-3 is as insulation with prevent the purposes of the reagent that goods or buildings are heated.
7. according to the purposes of claim 6, wherein said goods are the wireless apparatus element.
8. according to the purposes of claim 6, wherein heat-storing material mixes use with zeolite.
9. each heat-storing material of claim 1-3 is as the purposes of fire-fighting medium.
10. according to the purposes of claim 9, wherein heat-storing material mixes use with zeolite.
CN93103490A 1990-06-15 1993-02-24 Heat-accumulating material and use thereof Expired - Fee Related CN1055947C (en)

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PCT/SU1991/000173 WO1993004137A1 (en) 1990-06-15 1991-08-26 Heat accumulating material and its use
AU84317/91A AU667289B2 (en) 1990-06-15 1991-08-26 Heat accumulating material and its use
ZA931128A ZA931128B (en) 1990-06-15 1993-02-18 Heat accumulating material and use thereof.
DE4305264A DE4305264A1 (en) 1990-06-15 1993-02-20 Heat-accumulating material and its application
FR9302000A FR2701958B1 (en) 1990-06-15 1993-02-22 Heat storage material and its applications.
CN93103490A CN1055947C (en) 1990-06-15 1993-02-24 Heat-accumulating material and use thereof

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SU904839454A RU2042695C1 (en) 1990-06-15 1990-06-15 Heat accumulating material and a method of its production
PCT/SU1991/000173 WO1993004137A1 (en) 1990-06-15 1991-08-26 Heat accumulating material and its use
AU84317/91A AU667289B2 (en) 1990-06-15 1991-08-26 Heat accumulating material and its use
ZA931128A ZA931128B (en) 1990-06-15 1993-02-18 Heat accumulating material and use thereof.
DE4305264A DE4305264A1 (en) 1990-06-15 1993-02-20 Heat-accumulating material and its application
FR9302000A FR2701958B1 (en) 1990-06-15 1993-02-22 Heat storage material and its applications.
CN93103490A CN1055947C (en) 1990-06-15 1993-02-24 Heat-accumulating material and use thereof
PT101203A PT101203A (en) 1990-06-15 1993-02-24 HEAT ACCUMULATOR MATERIAL AND ITS USE
US08/410,401 US5585174A (en) 1990-06-15 1995-03-27 Heat-accumulating material and use thereof

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Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09143461A (en) * 1995-11-24 1997-06-03 Toyota Central Res & Dev Lab Inc Heat storage material
DE19621846A1 (en) * 1996-05-30 1997-12-11 Ralf Dr Kinkeldey Method and device for influencing the indoor climate
DE19734924C1 (en) 1997-08-12 1999-01-07 Saskia Solar Und Energietechni Solar thermal system with a solar collector and a heat store
EP0978696B1 (en) 1998-08-03 2003-06-25 Bürger, Heinz-Dieter Vakuum- und Verfahrenstechnik Heating or refrigerating machine with evaporable heat transfer fluid
RU2142596C1 (en) * 1998-11-30 1999-12-10 Институт катализа им.Г.К.Борескова СО РАН Thermal protective composite coat material
CN1079108C (en) * 1998-12-21 2002-02-13 中国科学院广州化学研究所 Energy storing composite material by phase changing
DE10049509A1 (en) * 2000-10-06 2002-04-25 Heinz Ploechinger System for cooling sealed space e.g. for switch cabinets, uses cooling medium to take up heat from waste-heat generators
WO2006005275A1 (en) 2004-07-09 2006-01-19 Fuesting, Bernd Shaped bodies made of powders or granulated metal, method for the production thereof and their use
DE102005000022A1 (en) 2005-03-16 2006-09-28 Füsting, Bernd Sorbent molding, method of manufacture and use
DE102006039343A1 (en) * 2006-08-22 2008-03-20 Geilich-Paetzold, Klaus, Dr. Heat storage material based on a hydrated salt is stabilized with silica and/or pyrogenic alumina
DE102007026970A1 (en) * 2007-06-05 2008-12-11 Techno-Physik Engineering Gmbh Shaped part for fire protection and method for producing a molded part
MX339872B (en) * 2010-01-12 2016-06-15 Sylvan Source Inc Heat transfer interface.
CN101812286A (en) * 2010-04-16 2010-08-25 北京大学 Mesoporous material-based composite phase change heat storage material and preparation method thereof
CN104629691A (en) * 2015-01-13 2015-05-20 天津市建筑科学研究院有限公司 Stabilized phase change material for floor heating heat storage
CN106317445B (en) * 2015-06-29 2019-01-15 北京化工大学 A kind of supported crystalline hydrate foaming agent, preparation method and application
DE102016013415A1 (en) * 2016-11-10 2018-05-17 Rainer Busch Method for producing a dimensionally stable, leak-proof phase Change Material System (PCM-S)
CN106761897B (en) * 2016-12-02 2018-08-07 中国矿业大学 A kind of phase-change material temperature-control afterbirth retardant preparation system and its method
DE102018008491A1 (en) * 2018-10-30 2020-04-30 Franz Wilhelm Cremer Protective agents for electrochemical energy stores, in particular for energy stores that contain lithium

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1584559A (en) * 1977-06-10 1981-02-11 Calor Group Ltd Thermal energy storage materials
EP0011357A1 (en) * 1978-09-29 1980-05-28 National Research Development Corporation The use of a collocation containing hydrates to store heat at a steady temperature, and a heat storage device containing this collocation
US4288338A (en) * 1979-05-16 1981-09-08 Phillips Hugh J Static solar heat storage composition
US4277357A (en) * 1980-01-31 1981-07-07 Boardman Energy Systems Incorporated Heat or cold storage composition containing a hydrated hydraulic cement
NL183657C (en) * 1980-08-21 1988-12-16 Mitsubishi Electric Corp CALCIUM CHLORIDE HYDRATE MATERIAL FOR STORING HEAT.
US4421661A (en) * 1981-06-19 1983-12-20 Institute Of Gas Technology High-temperature direct-contact thermal energy storage using phase-change media
DE3142096A1 (en) * 1981-10-23 1983-05-11 Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim Fire-retarding insulating materials and process for producing them
FR2522009A1 (en) * 1982-02-23 1983-08-26 Solvay MIXTURE FOR THE PREPARATION OF COMPOSITIONS FOR THE ABSORPTION AND ACCUMULATION OF CALORIES
DE3413169C1 (en) * 1984-04-07 1985-09-05 Kali-Chemie Ag, 3000 Hannover Process for utilising/storing energy
WO1994012587A1 (en) * 1992-12-01 1994-06-09 Harot Technology Inc. Heat accumulating material, method of and equipment for the use thereof

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