CN109859868B - Hot trap system for purifying high-temperature lithium loop - Google Patents
Hot trap system for purifying high-temperature lithium loop Download PDFInfo
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- CN109859868B CN109859868B CN201910024947.9A CN201910024947A CN109859868B CN 109859868 B CN109859868 B CN 109859868B CN 201910024947 A CN201910024947 A CN 201910024947A CN 109859868 B CN109859868 B CN 109859868B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 107
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000746 purification Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000003860 storage Methods 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 49
- 229910052726 zirconium Inorganic materials 0.000 claims description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 42
- 229910052727 yttrium Inorganic materials 0.000 claims description 41
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 30
- 239000012535 impurity Substances 0.000 claims description 29
- 238000011049 filling Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 16
- 238000005485 electric heating Methods 0.000 claims description 11
- 238000003466 welding Methods 0.000 claims description 7
- 241000446313 Lamella Species 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000000712 assembly Effects 0.000 description 8
- 238000000429 assembly Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000003749 cleanliness Effects 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a heat trap system for purifying a high-temperature lithium loop, which comprises a lithium storage tank for containing liquid lithium, a lithium recovery tank for recovering and purifying the lithium, a pipeline connected between the lithium storage tank and the lithium recovery tank, an electromagnetic pump arranged on the pipeline, and a group of heat trap devices at least arranged on the pipeline and used for purifying the lithium; the beneficial technical effect that this scheme had is: the device is suitable for online purification of a lithium loop, and works stably and reliably; the whole heat trap system has small volume: the device does not contain special structural parts and is convenient to process and manufacture; the purifying effect of the system is far better than that of other purifying means in the current stage.
Description
Technical Field
The invention relates to the technical field of non-metallic element impurity removal, in particular to a hot trap system for purifying a high-temperature lithium loop.
Background
A series of novel nuclear power units taking liquid metal as a coolant are being greatly developed in China. Liquid metal coolants may introduce various metallic and non-metallic impurities during raw material production, loop construction, plant operation, and the like. In comparison, the influence of nonmetallic impurity elements such as oxygen, hydrogen, nitrogen, carbon and the like is more remarkable, and the nonmetallic impurity elements are also more difficult to remove. The compounds formed by the impurities may be crystallized out in the low-temperature part of the loop, so that the flow channel is blocked, the heat exchange effect of the loop is reduced, and the local temperature of the pipeline is overhigh. The existence of nonmetallic impurities can accelerate the corrosion of structural materials, thereby generating potential safety hazards and causing major safety accidents. Therefore, the lithium loop has a severe requirement on the cleanliness of working media, and the perfecting of the purifying means is also a prerequisite for developing the research of the high-temperature lithium loop.
At present, the liquid metal loop mostly uses sodium and sodium-potassium alloy as coolant, and the main impurity is oxygen. Oxygen solubility decreases with decreasing temperature, and oxygen content can be reduced to 10ppm or less by purifying with cold trap method (cold trap) based on cooling crystallization. With the development of atomic energy technology and the widening of application fields, the operating temperature of a loop is further improved, and metallic lithium with lower saturated vapor pressure is generally adopted at the temperature of above 600 ℃.
TABLE 1 solubility of impurities in different working substances
According to the solubility of a part of impurities in alkali metal given in table 1, since the melting point of lithium is about 180 ℃, the working temperature of cold trap in lithium loop needs to be kept at 200-210 ℃ slightly higher than the melting point, and at this time, the solubility of nitrogen, oxygen and hydrogen in lithium is still far higher than 10ppm, and impurities can not be completely removed only by cold trap. It can be seen that the cold trap method which is relatively mature in the prior art can only realize preliminary filtration and purification on lithium, but cannot reach the cleanliness standard used as a coolant. The research of the lithium loop in China is still in a starting stage, and no experience of building the high-temperature lithium loop (> 900K) exists at present, so that no hot trap example for purifying the high-temperature lithium loop exists.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a hot trap system for purifying a high-temperature lithium loop, which can effectively purify nonmetallic impurities of the lithium loop, and the whole system is stable and reliable in operation and obvious in purifying effect.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The utility model provides a high temperature lithium is hot trap system for return circuit purifies, this hot trap system is including holding the lithium storage tank of liquid lithium, be used for retrieving the lithium recovery tank after purifying, connect the pipeline between lithium storage tank and the lithium recovery tank, set up electromagnetic pump on the pipeline and set up at least one set of hot trap device that is used for carrying out the purification operation to lithium on the pipeline, every set of hot trap device is including the jar body, set up outlet pipe, the inlet pipe in the jar body and be used for carrying out at least one set of getter subassembly of purification operation to liquid lithium, every set of getter subassembly is including the getter that is used for carrying out the absorption to the nonmetallic impurity in the liquid lithium and be used for with getter fixed mounting is in the supporting mechanism of the internal portion of jar, wherein outlet pipe and inlet pipe respectively with the pipeline is linked together for liquid lithium flows in jar body and jar internal liquid lithium outflow.
Further, when the heat sink devices are plural sets, plural sets of the heat sink devices are installed between the pipes in a serial or parallel manner.
Further, the getter is one or more of titanium, yttrium and zirconium.
Further, when the getter is titanium, the supporting mechanism for supporting the titanium getter in the getter assembly comprises a filling material layer formed by using titanium sponge as the getter, a wire mesh arranged on the outer surface of the filling material layer, a positioning pipe vertically arranged in the middle of the filling material layer and a supporting disc arranged at the bottom end of the wire mesh, wherein the wire mesh is fixedly connected with the positioning pipe and the inner wall of the tank body through welding.
Further, the sponge titanium is made of sponge titanium materials with national standard zero-order granularity not smaller than 30 mm.
Further, when the getter is yttrium, the supporting mechanism for supporting the yttrium getter in the getter assembly comprises a filling material layer formed by yttrium balls or yttrium wires serving as the getter, a wire mesh arranged on the outer surface of the filling material layer, a positioning pipe vertically arranged in the middle of the filling material layer and a supporting disc arranged at the bottom end of the wire mesh, wherein the wire mesh is fixedly connected with the positioning pipe and the inner wall of the tank body through welding.
Further, when the filling material layer is yttrium balls, the diameter of the filling material layer is smaller than 3mm; when yttrium wires are adopted as the filling material layer, the wire diameter is smaller than 0.5mm.
Further, when the getter is zirconium, the support mechanism for supporting the zirconium getter in the getter assembly comprises a zirconium sheet disc made of a zirconium sheet roll and a zirconium sheet disc positioning tube arranged at the center of the zirconium sheet disc, wherein the zirconium sheet disc is arranged in the tank body through a disc-shaped structure formed by the lower part of the zirconium sheet disc.
Further, the interval between the zirconium lamella discs of each layer is 1mm, and the inter-layer rolling pleat width of the zirconium lamella discs is 5mm.
Further, the heat sink device further comprises a temperature control system, the temperature control system comprises an electric heating device, a heat preservation layer and an air cooling system, wherein the electric heating device is uniformly wound on the outer sides of the tank body and the pipeline and used for preserving heat of working medium lithium in the tank body, the air cooling system is arranged on the outer side of the tank body and used for cooling a part, which needs to be cooled, of the tank body, and the heat preservation layer is arranged on the outer side of the electric heating device.
Compared with the prior art, the beneficial technical effects that this scheme had are:
1. The method is suitable for online purification of lithium, and works stably and reliably;
2. the whole heat trap system has small volume, does not contain special structural parts, and is convenient to process and manufacture;
3. The purifying effect of the system is far better than that of other purifying means in the current stage.
Drawings
FIG. 1 is a schematic diagram of a heat sink system for purifying a high temperature lithium circuit according to the present invention.
FIG. 2 is a schematic diagram of a heat sink device according to the present invention.
FIG. 3 is a schematic diagram of a titanium sponge getter assembly according to the present invention.
Fig. 4 is a schematic diagram of an yttrium getter assembly according to the present invention.
Fig. 5 is a schematic diagram of a zirconium getter assembly used in the present invention.
FIG. 6 is a graph of equilibrium concentration of nitrogen impurities at various temperatures after purification treatment with titanium, yttrium and zirconium getters in accordance with the present invention.
FIG. 7 is a graph of equilibrium concentration of hydrogen impurities at various temperatures after purification treatment with titanium, yttrium and zirconium getters in accordance with the present invention.
FIG. 8 is a graph of the equilibrium concentration of oxygen impurities at various temperatures after purification treatment with titanium, yttrium and zirconium getters in accordance with the present invention.
FIG. 9 is a schematic diagram of a thermal trap device layout according to the present invention.
In the figure:
1-lithium storage tank, 2-electromagnetic pump, 3-hot trap device, 4-lithium recovery tank, 5-pipeline, 31-tank body, 32-inlet pipe, 33-outlet pipe, 34-getter assembly, 341-positioning pipe, 342-getter layer, 343-silk screen, 35-supporting disk, 36-thermocouple trap.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
The scheme aims at the defect that the cold trap method which is relatively mature in the prior art can only realize preliminary filtration and purification of lithium, but cannot reach the cleanliness standard used as a coolant, and further provides a hot trap system for purifying a high-temperature lithium loop, which can effectively purify nonmetallic impurities of the lithium loop, and the whole system is stable and reliable in operation and obvious in purification effect.
Referring to fig. 1 and 2, there are respectively shown schematic structural diagrams of a heat sink system and a heat sink device for purifying a high-temperature lithium circuit in this embodiment. The heat trap system in the embodiment comprises a lithium storage tank 1 for containing liquid lithium, a lithium recovery tank 4 for recovering purified lithium, a pipeline 5 connected between the lithium storage tank 1 and the lithium recovery tank 4, an electromagnetic pump 2 arranged on the pipeline 5 and a group of heat trap devices 3 arranged on at least the pipeline 5 and used for purifying the lithium. It should be noted that, in practice, since the different getter materials used have different purifying capacities for impurities and different respective operating temperatures, one or more heat sink devices 3 may be arranged in the heat sink system according to the need in the present embodiment, and may be freely connected in series or parallel according to the operating characteristics and purifying requirements. Each group of heat trap devices 3 comprises a tank body 31, an outlet pipe 33, an inlet pipe 32 and at least one group of getter assemblies 34, wherein the outlet pipe 33 and the inlet pipe 32 are arranged in the tank body 31, the at least one group of getter assemblies 34 are used for purifying liquid lithium, the outlet pipe 33 is arranged at the upper part of the tank body 31, the inlet pipe 32 is arranged at the lower part of the tank body 31, so that the liquid lithium flows in from the inlet pipe 32 below and flows through the getter assemblies 34, and the getter assemblies 34 can effectively absorb impurities in the lithium to achieve the aim of purification. Purified lithium flows out of the upper outlet pipe 33 back into the lithium circuit. Each group of getter assemblies 34 comprises a getter 342 for adsorbing and removing nonmetallic impurities in the liquid lithium and a supporting mechanism for fixedly mounting the getter 342 inside the tank, wherein the outlet pipe 33 and the inlet pipe 32 are respectively communicated with the pipeline 5 for flowing the liquid lithium into the tank 31 and flowing the liquid lithium out of the tank 31. The heat sink device 3 further comprises a temperature control system, the temperature control system comprises an electric heating device, a heat preservation layer and an air cooling system, wherein the electric heating device is uniformly wound on the outer side of the tank body 31 and the outer side of the pipeline and used for preserving heat of working medium lithium in the electric heating device, the air cooling system is arranged on the outer side of the tank body 31 and used for cooling a part of the tank body 31 needing cooling, and the heat preservation layer is arranged on the outer side of the electric heating device. In addition, a thermocouple trap 36 is also arranged in the heat trap device 3, and a thermocouple is arranged in the thermocouple trap to measure the temperature of the lithium working medium, so that the operation temperature control of the heat trap is realized.
The getter assembly 34 in the heat sink device 3 is a critical component in the overall system, i.e. the choice of getter and the structural arrangement of the getter are critical. The getter is selected mainly by considering its thermodynamic properties and compatibility with the working medium. Referring to table 2 below, which shows gibbs energy data for stable compounds formed by alkali metal and getter materials, respectively, with impurity elements under standard conditions (25 ℃), getter metals having higher negative free energies in the table are theoretically all possible as alternative materials for the absorption of impurity gases. Therefore, the getter can be selected from a series of materials with high adsorption capacity, such as zirconium, titanium, yttrium, tantalum, lanthanum and the like, which are sensitive to nonmetallic elements such as oxygen, hydrogen, nitrogen and the like. At the same time, the influence of temperature on the Gibbs energy must be considered when selecting the getter, and the Gibbs energy of each substance varies with the temperature, so that the effect of each getter at different operating temperatures is also greatly different. The getters selected in this embodiment are preferably three of titanium, yttrium and zirconium. For convenience of description, the heat sink devices using the getters of titanium, yttrium and zirconium will be selected correspondingly and simply referred to as a titanium heat sink device, an yttrium heat sink device and a zirconium heat sink device, respectively.
TABLE 2 Standard Gibbs free energy of formation data for partially stabilized compounds
Referring now to FIG. 3, a schematic diagram of a titanium getter assembly utilizing a titanium getter is shown. The supporting mechanism for supporting the titanium getter in the getter assembly comprises a filling material layer formed by using titanium sponge as the getter, a wire mesh 343 arranged on the outer surface of the filling material layer, a positioning tube 341 vertically arranged in the middle of the filling material layer, and a supporting disc 35 arranged at the bottom end of the wire mesh 343, wherein the wire mesh 343 is fixedly connected with the positioning tube 341 and the inner wall of the tank body 31 through welding. In the structure, the titanium sponge adopts national standard grade 0 titanium sponge specified in GB-T-2524-2010 as a filling material of the getter, and the specific surface area of the titanium sponge is about 4000m 2/m3. Because the titanium sponge is fragile and difficult to process into a regular shape, titanium sponge with granularity not less than 30mm is selected for filling, and is coated by a 300-mesh stainless steel wire mesh 343, so that the titanium sponge is prevented from being broken to generate slag under the flushing of a lithium working medium, and a hot well and the lithium working medium are prevented from being polluted.
Referring now to fig. 4, a schematic diagram of a titanium getter assembly utilizing an yttrium getter is shown. The supporting mechanism for supporting the yttrium getter in the getter assembly comprises a filling material layer formed by yttrium balls or yttrium wires serving as the getter, a wire mesh 343 arranged on the outer surface of the filling material layer, a positioning tube 341 vertically arranged in the middle of the filling material layer, and a supporting disc 35 arranged at the bottom end of the wire mesh 343, wherein the wire mesh 343 is fixedly connected with the positioning tube 341 and the inner wall of the tank body 31 through welding. In actual manufacturing, the yttrium balls with the diameter smaller than 3mm or the yttrium wires with the wire diameter smaller than 0.5mm are selected as filling materials, and the contact area between the getter and the working medium lithium can be enlarged. Because yttrium has larger hardness and difficult processing, the specific specification and roundness of yttrium balls can not be excessively required, and the yttrium balls can also well meet the purification requirement.
Referring now to FIG. 5, a schematic diagram of a titanium getter assembly constructed using a zirconium getter is shown. The support mechanism for supporting the zirconium getter in the getter assembly comprises a zirconium plate made of a zirconium plate roll and a zirconium plate positioning tube 341 arranged at the center of the zirconium plate, wherein the zirconium plate is mounted in the can 31 by a disk-shaped structure formed at the lower part thereof. In actual manufacturing, a zirconium platelet disc rolled by zirconium platelets with the thickness of 0.1mm is used as a getter component, wherein the specific surface area of the getter is more than 300m 2/m3. The interval between each layer of zirconium sheets is 1mm, and the width of the interlayer rolling folds is 5mm.
Referring to fig. 2, it should be finally noted that the getter assembly in the present embodiment is installed in the heat sink by the positioning tube 341, specifically, in the case of the titanium heat sink device, the titanium getter assembly is installed by wrapping the positioning tube 341 on the getter assembly outside the inlet tube 32, that is, by welding the positioning tube 341 inside the getter assembly outside the inlet tube 32, so as to install the titanium getter assembly in the can body; also, when the yttrium thermal trap device or the zirconium thermal trap device is adopted, the positioning tube 341 in the yttrium thermal trap device is correspondingly welded on the outer side of the inlet tube 32, so that the getter assembly is fixedly installed.
The working temperatures and the operating characteristics of the titanium, yttrium and zirconium in this embodiment, respectively, and the corresponding purifying effects are summarized as follows:
Titanium hot-trap device:
The titanium heat trap device can be used for purifying nitrogen in working medium lithium, but is not suitable for purifying hydrogen and oxygen, the operating temperature is not particularly required, and can be the same as the operating temperature of a lithium loop, so that a cooling or heating device is not required, and the nitrogen content can be reduced to below 1ppm on the premise of sufficient purification.
Yttrium thermal trap device:
Yttrium thermal trap devices can be used for purifying nitrogen, hydrogen and oxygen, but the respective operating temperature ranges are different.
1. When absorbing hydrogen, the use temperature range is 520K-600K in view of the requirements of cleanliness and purification rate, and the hydrogen content can be reduced to below 10ppm on the premise of full purification;
2. when absorbing oxygen, the use temperature is not more than 1000K in view of the requirements of cleanliness and purification rate, and the oxygen content can be reduced to below 10ppm on the premise of full purification;
3. When absorbing nitrogen, the operating temperature has no specific requirement, and can be the same as the operating temperature of a loop, so that a cooling or heating device is not needed, the nitrogen content can be reduced to below 1ppm on the premise of full purification, but the purification rate is lower than that of a titanium hot trap device and a zirconium hot trap device.
Zirconium hot-trap device:
the zirconium heat trap device can be used for purifying nitrogen in working medium lithium, but is not suitable for purifying hydrogen and oxygen, the operating temperature has no specific requirement, and can be the same as the operating temperature of a loop, so that a cooling or heating device is not needed, and the nitrogen content can be reduced to below 1ppm on the premise of full purification.
The purification rate of the heat trap device is obviously affected by temperature, and when the temperature is increased from 200 ℃ to 600 ℃, the purification rate can be increased by 10 5 times, so that under the premise that the strength of the structural materials is enough, if the purification time is required, the working medium can be properly heated or can be at a higher operating temperature in the allowable temperature range.
The present embodiment is described in further detail below in conjunction with theoretical calculations:
According to the relations between the equilibrium constant, the equilibrium constant and the Gibbs energy of the reaction of the impurity element and the metal element (including lithium and getter material) shown in the formulas 2 and 3, the equilibrium concentration of the impurity after the purification by the hot trap can be calculated as shown in the formula 4.
Wherein: gibbs energy G unit is kJ/mol; the molar gas constant R is 8.314J/(mol.K), and the unit of the reaction temperature T is K; m is the relative atomic weight of the corresponding impurity element; ρ is the density of lithium at the operating temperature in kg/m 3.
aA+bB＝cC+dD，ΔHf (1)
G＝-RTlnKeq (3)
The equilibrium concentrations of impurities after purification of three getters, titanium, yttrium and zirconium, are shown below with reference to figures 6 to 8, at different temperatures. According to the impurity content after purification corresponding to different getter materials, the applicability of the getter materials can be effectively judged, and the working temperature of the getter materials can be determined.
Referring to fig. 9, a schematic layout of a heat sink system in this embodiment is shown. As can be seen from fig. 9, the yttrium heat sink device is connected in parallel with the composite heat sink device composed of the titanium getter assembly and the zirconium getter assembly, wherein the yttrium heat sink device is provided with a plurality of yttrium getter assemblies, the quantity of the yttrium getter assemblies can be flexibly adjusted according to the working requirement, and the quantity of the getter assemblies on the composite heat sink device composed of the titanium getter assembly and the zirconium getter assembly is flexibly increased and decreased according to the working requirement.
The heat sink is connected in a liquid lithium circuit driven by the electromagnetic pump 2 and mainly comprises an inlet pipe 32, an outlet pipe 33, a tank 31, a temperature control system and a getter assembly. The temperature control system comprises an electric heating device, an insulating layer and an air cooling system. The heating device is uniformly wound on the outer side of the tank body and is used for preserving heat of working medium lithium and preventing the lithium from solidifying (melting point 180 ℃). Part of the heat traps with the working temperature lower than the loop operating temperature need to be additionally provided with a controllable air cooling system so as to control the operating temperature of the heat traps and achieve better purifying effect. The heat preservation layer is uniformly and reasonably wrapped outside the heat trap, so that heat dissipation is reduced. The thermocouple well 36 is arranged in the heat well, and a thermocouple is arranged in the heat well to measure the temperature of the lithium working medium, so that the operation temperature control of the heat well is realized. When the device works, the heat trap is connected in the high-temperature lithium loop system, so that the heat trap and the loop are vacuumized together before being filled with working medium, gas replacement is carried out, and leakage inspection is carried out on the whole loop, so that pollution caused by residual gas in the loop is avoided. In operation of the heat sink, working fluid lithium flows in from the lower inlet tube 32 and through the getter assembly. The getter component can effectively absorb impurities in lithium, so as to achieve the aim of purification. The purified lithium flows out of the upper outlet pipe 33 and returns to the lithium loop, wherein each heat sink inlet pipe 33 and each heat sink outlet pipe 33 are respectively provided with a corresponding valve, and the opening and closing of the heat sink can be controlled. When the hot trap operates, the hot trap can be filled with lithium working medium, and the hot trap is kept stand for a period of time, and then purified lithium liquid is discharged back into a lithium loop; the lithium loop can continuously flow through the heat trap under the drive of the electromagnetic pump 2 to continuously purify the working medium.
Finally, it should be noted that the purification method of lithium can also be generalized to the preparation process of high purity lithium. At present, the cleanliness of the lithium simple substance can only be controlled from the aspect of raw material purity, and the purification means of a hot trap can directly add a getter into prepared lithium and control the storage temperature of the lithium so as to realize the adsorption of nonmetallic impurities and achieve the aim of purification.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. The utility model provides a high temperature lithium loop purifies uses hot trap system which characterized in that: the heat trap system comprises a lithium storage tank for containing liquid lithium, a lithium recovery tank for recovering and purifying the lithium, a pipeline connected between the lithium storage tank and the lithium recovery tank, an electromagnetic pump arranged on the pipeline and at least one group of heat trap devices arranged on the pipeline and used for purifying the lithium, wherein each group of heat trap devices comprises a tank body, an outlet pipe, an inlet pipe and at least one group of getter components, the outlet pipe and the inlet pipe are arranged in the tank body, the getter components are used for purifying the liquid lithium, each group of getter components comprises a getter used for removing nonmetallic impurities in the liquid lithium by adsorption, and a supporting mechanism used for fixedly installing the getter in the tank body, and the outlet pipe and the inlet pipe are respectively communicated with the pipeline and are used for flowing the liquid lithium into the tank body and flowing out of the liquid lithium in the tank body; when the getter is zirconium, the supporting mechanism in the getter component for supporting the zirconium getter comprises a zirconium sheet disc made of a zirconium sheet roll and a zirconium sheet disc positioning tube arranged at the center of the zirconium sheet disc, wherein the zirconium sheet disc is arranged in the tank body through a disc-shaped structure formed by the lower part of the zirconium sheet disc; the interval between each two layers of the zirconium lamella discs is 1mm, and the inter-layer rolling pleat width of the zirconium lamella discs is 5mm.
2. The high temperature lithium loop purification heat sink system according to claim 1, wherein: when the heat sink devices are in a plurality of groups, the heat sink devices are arranged among the pipelines in a series or parallel mode.
3. The high temperature lithium loop purification heat sink system according to claim 2, wherein: the getters of the rest heat sink devices are any one or more of titanium, yttrium and zirconium except zirconium.
4. A high temperature lithium loop purification heat sink system as claimed in claim 3, wherein: when the getter is titanium, the supporting mechanism for supporting the titanium getter in the getter assembly comprises a filling material layer formed by using titanium sponge as the getter, a wire mesh arranged on the outer surface of the filling material layer, a positioning pipe vertically arranged in the middle of the filling material layer and a supporting disc arranged at the bottom end of the wire mesh, wherein the wire mesh is fixedly connected with the positioning pipe and the inner wall of the tank body through welding.
5. The high temperature lithium loop purification heat sink system according to claim 4, wherein: the titanium sponge is made of a national standard zero-order titanium sponge material with granularity not less than 30 mm.
6. A high temperature lithium loop purification heat sink system as claimed in claim 3, wherein: when the getter is yttrium, the supporting mechanism for supporting the yttrium getter in the getter assembly comprises a filling material layer formed by yttrium balls or yttrium wires serving as the getter, a wire mesh arranged on the outer surface of the filling material layer, a positioning pipe vertically arranged in the middle of the filling material layer and a supporting disc arranged at the bottom end of the wire mesh, wherein the wire mesh is fixedly connected with the positioning pipe and the inner wall of the tank body through welding.
7. The high temperature lithium loop purification heat sink system according to claim 6, wherein: when the filling material layer adopts yttrium balls, the diameter of the filling material layer is smaller than 3mm; when yttrium wires are adopted as the filling material layer, the wire diameter is smaller than 0.5mm.
8. The high temperature lithium loop purification heat sink system according to claim 1, wherein: the heat sink device further comprises a temperature control system, the temperature control system comprises an electric heating device, an insulating layer and an air cooling system, wherein the electric heating device is uniformly wound on the outer sides of the tank body and the pipeline and used for insulating working medium lithium in the tank body, the air cooling system is arranged on the outer side of the tank body and used for cooling a part, which needs to be cooled, of the tank body, and the insulating layer is arranged on the outer side of the electric heating device.
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| CN201910024947.9A CN109859868B (en) | 2019-01-10 | 2019-01-10 | Hot trap system for purifying high-temperature lithium loop |
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| CN201910024947.9A CN109859868B (en) | 2019-01-10 | 2019-01-10 | Hot trap system for purifying high-temperature lithium loop |
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