Metallohydride pair of alloys for thermal pump

FIELD: metallurgy; metallohydride alloys for thermal pumps, air-conditioners, cold generators.

SUBSTANCE: proposed metallohydride pair of alloys contains low-temperature and high-temperature alloys; low-temperature alloy has composition mm1-xLaxNi4CO(0.1≤x≤0.999) and high-temperature alloy has composition LaNi5-xAlx (0.001≤x≤0.5).

EFFECT: increased cold generating capacity of thermal pump at pressure in system not below atmospheric.

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The invention relates to the field of hydrogen energy, namely the alloys used in heat pumps.

It is known that alloys drives hydrogen (start) type AB5are promising for use in teplopreobrazovaniya devices, for example, heat pumps because they have a relatively high hydrogen capacity and specific heat of education, and is easily activated and low hydrogen purity in comparison with alloys of the type AB2and AB3.

It is known that the efficiency of the heat pump in the first place depends on its intensity and temperature levels of conversion of heat /Hydrogen in metals, Ed. by Hanefeld and Italics. - M.: Publishing House. Mir, 1981/. The practical application of heat pumps is significantly enhanced if the energy transfer to the high temperature part of the pump is due to the supply thereto of low-grade waste heat source is not higher than +100° C.

Known systems based on chemical compounds, mode of heat pumps due to the energy produced in the process of chemical interaction. So, the system

NaBr+nNH3↔ NaBr· nNH3+Q

where Q is the heat during the reaction, has an operating temperature range from -30... +45° C, the efficiency of 24.5 kJ/kg and is used for air-condit is the planning of buildings. The disadvantages of this system are increased demands on corrosion resistance design and the need for periodic renewal of the stock of reagents for their feed to the reactor /see Dual temperature thermal storage with complex compounds. Uwe Rockenfeller, Martin James F. "21stIntersoc. Energy Convers. Eng. Conf., San Diego, Calif., Aug.25-29, 1986, vol.2". Washington, D.C., 1986, 755-759 (eng.)/.

Known systems using the hydrates of the salts with melting-solidification from +15... +32° such as Na2SO4·10 H2O, l2·6 H2About etc. /see Salt hydrates used for latent heat storage: corrosion of metals and reliability of thermal performance. Porisini F.C. "Sol. Energy, 1988, 41, No. 2, R-197 (eng.) Thermal energy storage some views on some problems. "Hahne " E. "Heat Transfer 1986: Proc. 8thInt. Conf., San Francisco, Calif., Aug. 17-22, 1986, vol.1". Washington, D.C., 1986, 279-292 (eng.)/. The maximum efficiency of these systems does not exceed 255-390 kJ/DM3. The disadvantage of such systems is the limited number of cycles of melting-solidification due to the separation of liquid and solid components of the hydrates and corrosion impact on the effective from the point of view of heat transfer materials of construction.

Known systems using industrial adsorbents, such as activated carbon, which is paired with methanol scheme of a heat pump with an efficiency of not higher than 110-130 kJ/DM3that is 5 times lower than that of metal hydride heat is Anosov (testing of 550-640 kJ/DM 3) /see Shalashov S.A. abroad. Solar energy use in domestic refrigeration. Magazine “Refrigeration technology”, No. 2, 1990, p.20/. The disadvantage of this system are the large size, due to the low bulk density of the layer of coal (5-7 times less than vodorodomobili alloys). In addition, during long-term operation of these systems there is a potential risk of nutkani from the outside due to the low vapor pressure of methanol in the field of operating temperatures.

Know the use of metal hydride alloy Mm1-xLaxNi4Co (0,1≤ x≤ 0,999) as a low-temperature alloy for the heat pump (see RF patent №2214470, Ál7With 22 19/00, Ál7With 22 28/00 priority from 27.05.2002). In the patent there is no information about the system HT-W alloys, allowing to obtain improved performance of the heat pump.

Known metallogenica pair alloys for the heat pump, including low-temperature (HT) Zrfor 0.9Tia 0.1Crfor 0.6Fe1,4and high temperature (W) Zrfor 0.9Tia 0.1CrFe /see Fateev GA, Shilenkov M.A., Kim, K.-j. Experimental investigation of propagation of thermal wave energy conversion blown in porous media. - Engineering-physical journal, volume 73, No. 5, s-1108/ and ensuring the interaction of these alloys in the heat pump. This system is used as a prototype.

The main disadvantage of metal hydrides of zirconium is low system pressure (below atmospheric in 1,5-2 times) upon transfer of hydrogen from the low-temperature (HT) alloy in high-temperature (VT) in the process of getting a cold at a temperature below 0° C. During long-term operation of the heat pump it can cause nationem from the environment and ultimately to the loss of his health. Another disadvantage of this structure is the high demands on the purity of hydrogen introduced into the system from the outside for charging a heat pump. Such impurities as oxygen, nitrogen, water vapor lead to the poisoning of alloys and losing their health. Preliminary fine purification of hydrogen increases the production of heat pumps and will require the creation of appropriate infrastructure. This system alloys show low cooling capacity when the system pressure above atmospheric.

Task to be solved by the claimed invention is the creation of a metal hydride system (HT-W) alloys for the heat pump, providing better efficiency than previously known.

The technical result of the invention is to achieve a high cooling capacity of the heat pump in comparison with the system of the OI-a prototype for the system pressure below atmospheric.

The technical result is achieved in that the metal hydride is used, the pair, in which the low-temperature alloy used Mm1-xLaxNi4Co (0,1≤ x≤ 0,999), and as a high temperature alloy - LaNi5-xAlx(0,001≤ x≤ 0,5).

The invention consists in the composition of the alloy W and the new combination of compositions of high-temperature and low-temperature alloys of type AB5containing rare-earth metals and Nickel for the formation of metal hydride pairs, providing an optimal combination of technical and operational characteristics of the heat pump formed by the couple and not demanding purity hydrogen.

Substantiation of the PARAMETERS

We offer metal hydride vapour Mm1-xLaxNi4Co-LaNi5-xAlxin comparison with the known Zrfor 0.9Tia 0.1Crfor 0.6Fe1,4-Zrfor 0.9Tia 0.1CrFe better meets the technical and operational requirements that allows you to extend the field of application of metal hydride heat pump.

These requirements include mild hydrogenation HT and W alloys; a large number of absorbed and emitted by the fusion of hydrogen atoms on the plateau of the isotherm; small slope of the isotherm; pressure on the plateau of the isotherm sorption W alloy should be close to atmospheric in the range of the temperature is ambient to +30° With, but below the pressure on the plateau desorption isotherms HT alloy in the range of temperatures not lower than -15° C; pressure on the plateau of the isotherm desorption W alloy at temperatures up to +100° should be minimal, but higher pressure sorption isotherms HT alloy at ambient temperature; the minimum possible degree of poisoning HT and W metal hydride hydrogen impurities.

Composition W alloy was determined with a focus on the characteristics of the HT alloy Mm1-xLaxNi4With. Experimental results are presented in table 1 and 2.

1,35
Table 1

The average pressure on the plateau of the isotherm of adsorption (desorption) of the investigated alloys
AlloyThe average pressure on the plateau of the isotherm of adsorption (desorption), P, ATA
T=+100° (desorption)T=-15° (desorption)T=+25° (sorption)
Mmfor 0.9Laa 0.1Ni4Co 3,60is 18.40
Mmfor 0.6Lafor 0.4Ni4Co 0,885,85
Mm0.001La0.999Ni4Co 0,50
LaNi4,999Al0.00119,90 2,30
LaNi4,7Alfor 0.37,5 0,7
LaNi4,5Al0,53,1 0,2
Table 2

The cooling capacity of the heat pump for the three pairs of NT-W alloys system Mm1-xLaxNi4Co-LaNi5-xAlx
A pair of NT-WCooling capacity in W/kg
Mmfor 0.9Laa 0.1Ni4Co-LaNi4,999Al0,001273
Mmfor 0.6Lafor 0.4Ni4Co-LNi4,7Alfor 0.3300
Mm0.001La0.999Ni4Co-LaNi4,5Al0,5252

Table 1 presents the average pressure on the plateau of the isotherm of adsorption (desorption) of NT and W alloys, which combine to form a metal hydride pair (HT) Mm1-xLaxNi4Co (0,1≤ x≤ 0,999)-(W) LNi5-xAlx(0,001≤ x≤ 0,5), effective for use in a heat pump. In the interaction of the proposed hydride Mm1-x LaxNi4Co-LaNi5-xAlxin heat pump mode can be achieved by the following technical specifications: Cooling capacity up to 500 W/kg when applying the coolant to the high temperature capsule with LaNi5-xAlxat a temperature, for example up to +100° in the process of its regeneration and +30° in the production process of cold.

Data the baseline data for the three pairs of NT-W alloys system Mm1-xLaxNi4Co-LaNi5-xAlxare shown in table 2. Work metal hydride heat pump is in a closed loop, i.e. without feeding the working fluid (hydrogen) in the circuit of the device.

EXAMPLE

The alloys of the claimed composition was obtained by fusion of the components of the charge in electric arc furnaces with a non-consumable electrode in an argon atmosphere. To obtain alloys used mischmetall brand MCG, lanthanum brand L-0, the Nickel brand H-4, cobalt brand K-0, aluminium brand A99 motorway. When calculating hanging the amount of REM were taken with a 3% surplus. Crystallization of the alloys was carried out in the same water-cooled copper molds as their melting. After a few cycles of "melting-crystallization furnace was opened, the ingots were crushed in a jaw crusher and subjected to separation to obtain a material particle size is not more than 3.0 mm, the Heat pump operating on the cold, schematically, not only is em a device, containing two sealed retort, interconnected pipelines, which were loaded with equal amount of NT and W alloy with a particle size of ≤ 3 mm, Then the installation was evacuated and created excess pressure of hydrogen. During the activation process occurred saturation alloys by hydrogen, which makes them more grinding and formation of hydrides HT and W alloy. After activation alloys installation was filled with hydrogen to the working pressure. In the operation of the heat pump distinguish the charge cycle and a discharge cycle. First were charging. This was heated hydride W alloy to a temperature of +90÷ +100° using waste heat sources. In the main part of the hydrogen passes from hydride W alloy hydride HT alloy. The process of discharge of the heat pump is working cycle. To begin cooling the hydride W alloy liquid with a temperature no higher than +30° C. In the cooling process W hydride began to absorb hydrogen, which gave the NT hydride at the stage of charging. When the flow of hydrogen from NT hydride alloy in W hydride alloy first began to cool. Measured value falling temperature of the cooled fluid and the time of its fall. On the basis of these values was calculated cooling capacity of the heat pump.

In financial p is Tata, metal hydride heat pump using the proposed system alloys allows to achieve a cooling capacity of up to 500 W per 1 kg of low-temperature alloy when it is low for 6-8 min in the temperature range of the cooled fluid (liquid) to -10° using waste heat sources with temperatures up to +100° and a cooling circuit with a temperature no higher than +30° in the process of regeneration of the heat pump.

Thus, the claimed invention allows to expand the scope and efficiency of heat pumps for the production of cold, such as air conditioners, where there is a waste heat source (in steel plants for cooling jobs in electronic equipment for cooling of fuel elements). Effectively heat pumps applicable for heat generation in places where there is the bargain of the cold source, for example, for space heating in cold climates.

Metal hydride pair alloys for heat pump containing a low-temperature and high-temperature alloys, characterized in that as a low-temperature alloy contains an alloy composition Mm1-xLaxNi4Co (0,1≤x≤0,999), and as a high temperature alloy composition LaNi5-xAlx(0,001Ȧ x≤0,5).



 

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FIELD: metallurgy; metallohydride alloys for thermal pumps, air-conditioners, cold generators.

SUBSTANCE: proposed metallohydride pair of alloys contains low-temperature and high-temperature alloys; low-temperature alloy has composition mm1-xLaxNi4CO(0.1≤x≤0.999) and high-temperature alloy has composition LaNi5-xAlx (0.001≤x≤0.5).

EFFECT: increased cold generating capacity of thermal pump at pressure in system not below atmospheric.

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