CN103311426A - Method for preparing N-type Bi2Te3 based thermoelectric materials by refrigeration crystal bar processing waste - Google Patents
Method for preparing N-type Bi2Te3 based thermoelectric materials by refrigeration crystal bar processing waste Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000005057 refrigeration Methods 0.000 title claims abstract description 62
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910002899 Bi2Te3 Inorganic materials 0.000 title abstract 4
- 239000007789 gas Substances 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000010453 quartz Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011261 inert gas Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000005619 thermoelectricity Effects 0.000 claims description 50
- 239000003708 ampul Substances 0.000 claims description 21
- 239000003595 mist Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005538 encapsulation Methods 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000011084 recovery Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- 229910052711 selenium Inorganic materials 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 43
- 239000011669 selenium Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- -1 tellurium Chemical class 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing N-type Bi2Te3 based thermoelectric materials by refrigeration crystal bar processing waste. The technical scheme includes that firstly, the refrigeration crystal bar processing waste is grinded, washed and dried, secondly, dried powder is placed into a gas reduction furnace, mixed gas of reducing gas and inert gas is led in, the gas reduction furnace is heated up to reach 200-550 DEG C, the temperature is kept for 1.0-5.0h and is reduced to room temperature, and the refrigeration crystal bar processing waste with impurities removed is obtained. The refrigeration crystal bar processing waste with the impurities removed is placed into a quartz tube, and according to the chemical formula (BixSb2-xTe3-ySey, wherein 1.5<=x<=2.0 and 0.1<=y<=0.7) of the N-type Bi2Te3 based thermoelectric materials, Bi, Te, Sb and Se raw materials with purity higher than 99.9wt% are added. Finally, the quartz tube is packaged in an evacuated manner and is smelted in a heating furnace at the temperature of 580-850 DEG C, the temperature is kept for 0.5-5.0h, the quartz tube is cooled along with the furnace, and an alloy ingot in the quartz tube is taken out, so that the N-type Bi2Te3 based thermoelectric materials are obtained. The method has the advantages of simple process, short recovery cycle, less environmental pollution and low cost.
Description
Technical field
The invention belongs to N-type Bi
2Te
3The base thermoelectricity material technical field.Be specifically related to a kind ofly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material.
Background technology
Thermoelectric material is a kind ofly can with the direct mutual functional material of conversion of heat energy and electric energy, more and more cause people's attention at society.Bi
2Te
3Based compound has irreplaceable status as the thermoelectric material of near room temperature thermoelectricity capability optimum in the commercial applications process, be widely used in the semiconductor refrigerating industry.Present commercial large-scale production Bi
2Te
3Base thermoelectricity material normally adopts single shaft to the mode of growth, such as Bridgman method and zone melting method, in the hope of obtaining to have the Bi of good thermoelectricity capability
2Te
3Based compound monocrystalline or column crystal.The Bi that adopts above production method to obtain
2Te
3Base refrigeration crystal bar machining property is poor, easily fracture and damaged in the following process process, and percent defective is high, stock utilization less than 50%.
As everyone knows, selenium and tellurium belong to rare and scatter element, and association content in the sulphide ores such as pyrite and chalcopyrite is few, expensive usually, produces Bi in addition
2Te
3Cut loss during base thermoelectricity material large, stock utilization is very low, causes cost of material very high.So the technology of exploitation high efficiente callback refrigeration crystal bar processing waste material is most important.
At present, the cutting powder that produces when cutting refrigeration crystal bar or follow-up cut crystal or damaged material often adopt hydrometallurgy to carry out the single element separating-purifying and are reclaimed.Such as " a kind of bismuth telluride base semiconductor refrigeration material reclaims the method for tellurium " (ZL200610132393.7) patented technology, this technology will add oxidant after will cutting the powder alkali fusion, adopt the acid neutralization to leach and obtain tellurium dioxide, adopting at last alkali dissolving liquid making and electrodeposition to extract has the valency tellurium element.Also can adopt the pyrogenic process oxidation with the villaumite oxidation and open state in conjunction with extract technology extraction Te with Bi(, the technique of semiconductor chilling plate waste recovery tellurium, the non-ferrous metal progress, 2007,1996-2005(5): 550; Chen Peihuan, the research of from the cooling module waste material, reclaiming the valuable metals such as tellurium, strain smelting science and technology, 1991,19(2): 125).The theoretical foundation that adopts above method to extract Te and Bi is with Te or the oxidation of Bi element, then separate separately and purification, and recovery scheme all is that the valuable element in the refrigeration crystal bar processing waste material is carried out independent separating-purifying, minute multi-step and multiple operation progressively carry out separating-purifying with single simple substance element, and its complex process, the cycle is long, environmental pollution is serious and production cost is high.
Summary of the invention
The present invention is intended to overcome the prior art defective, and what provide that a kind of technique is simple, the cycle is short, environmental pollution is little and cost is low prepares N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material.
For achieving the above object, the step of the technical solution used in the present invention is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
The processing waste material of crystal bar of will freezing first grinds to form particle diameter less than 200 purpose fine powders, successively with the deionized water washing with use absolute ethanol washing, puts into the vacuum drying chamber drying and processing; Powder after will drying is again inserted in the gas reduction stove, passes into the mist of reducing gas and inert gas, then the gas reduction stove is warming up to 200～550 ℃, insulation 1.0～5.0h is cooled to room temperature at last, takes out powder, namely get the refrigeration crystal bar processing waste material of imurity-removal, vacuum is preserved.
Second step, N-type Bi
2Te
3The preparation of base thermoelectricity material
The refrigeration crystal bar processing waste material of the imurity-removal that first first step is obtained is put into quartz ampoule, by N-type Bi
2Te
3The chemical formula of base thermoelectricity material adds purity greater than Bi, Te, Sb and the Se raw material of 99.9wt%, N-type Bi
2Te
3The chemical formula of base thermoelectricity material is Bi
xSb
2-xTe
3-ySe
y, wherein: 1.5≤x≤2.0,0.1≤y≤0.7.Again quartz ampoule is vacuumized encapsulation, put into the heating furnace melting, smelting temperature is 580～850 ℃, and temperature retention time is 0.5～5.0h, then cools to room temperature with the furnace, takes out the alloy pig in the quartz ampoule, namely gets N-type Bi
2Te
3Base thermoelectricity material.
The cutting powder that described refrigeration crystal bar processing waste material produces when being cutting refrigeration crystal bar and follow-up cut crystal or damaged material.
The mist of described reducing gas and inert gas is: the volumn concentration of reducing gas is 10～80%, and the volumn concentration of inert gas is 20～90%; Reducing gas is hydrogen or for CO (carbon monoxide converter) gas, inert gas is nitrogen or is argon gas.
Because adopt technique scheme, the present invention compared with prior art has the following advantages:
1) the present invention directly prepares N-type Bi with refrigeration crystal bar processing waste material
2Te
3Base thermoelectricity material, front and back only namely get N-type Bi by removing impurity and two steps of composition adjustment
2Te
3Base thermoelectricity material is different from the method that traditional hydrometallurgy is carried out the individual element separating-purifying fully, reclaims technique simple.
2) the present invention is from refrigeration crystal bar processing waste material to making at last N-type Bi
2Te
3Base thermoelectricity material, the cycle of finishing a recycling only needs 1.5h～10h, compares with the production technology of traditional recovery method, and the cycle shortens greatly.
3) the present invention is in process of production without the discharging of solid waste and poisonous and harmful liquid, environmental protection, and a large amount of solid waste and the discharging of toxic liquid are difficult to avoid in the metallurgical recovery method of conventional wet, therefore environmental pollution is little.
4) Te, Sb, Se and the Bi element in the recycled in its entirety refrigeration crystal bar processing waste material of the present invention, the rate of recovery of valuable element is more than 99%, comparing conventional wet metallurgy, to carry out the method rate of recovery of individual element separating-purifying higher, and economic benefit is better, and production cost is lower.
Therefore, the present invention has the advantages that technique is simple, return period is short, environmental pollution is little and cost is low.
Embodiment
The present invention will be further described below in conjunction with embodiment, is not the restriction to its protection range:
Embodiment 1
A kind ofly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material.The preparation process of the method is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
The processing waste material of crystal bar of will freezing first grinds to form particle diameter less than 200 purpose fine powders, successively with the deionized water washing with use absolute ethanol washing, puts into the vacuum drying chamber drying and processing; Powder after will drying is again inserted in the gas reduction stove, passes into the mist of reducing gas and inert gas, then the gas reduction stove is warming up to 200～280 ℃, insulation 1.0～2.0h is cooled to room temperature at last, takes out powder, namely get the refrigeration crystal bar processing waste material of imurity-removal, vacuum is preserved.
Second step, N-type Bi
2Te
3The preparation of base thermoelectricity material
The refrigeration crystal bar processing waste material of the imurity-removal that first first step is obtained is put into quartz ampoule, by N-type Bi
2Te
3The chemical formula of base thermoelectricity material adds purity greater than Bi, Te, Sb and the Se raw material of 99.9wt%, N-type Bi
2Te
3The chemical formula of base thermoelectricity material is Bi
xSb
2-xTe
3-ySe
y, wherein: 1.9≤x≤2.0,0.55≤y≤0.7.Again quartz ampoule is vacuumized encapsulation, put into the heating furnace melting, smelting temperature is 580～630 ℃, and temperature retention time is 0.5～1.0h, then cools to room temperature with the furnace, takes out the alloy pig in the quartz ampoule, namely gets N-type Bi
2Te
3Base thermoelectricity material.
The cutting powder that the described refrigeration crystal bar of the present embodiment processing waste material produces when being cutting refrigeration crystal bar and follow-up cut crystal.
The mist of the described reducing gas of the present embodiment and inert gas is the mist of hydrogen and nitrogen, and wherein: the volumn concentration of hydrogen is 10～30%, and the volumn concentration of nitrogen is 70～90%.
Embodiment 2
A kind ofly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material.The preparation process of the method is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
The processing waste material of crystal bar of will freezing first grinds to form particle diameter less than 200 purpose fine powders, successively with the deionized water washing with use absolute ethanol washing, puts into the vacuum drying chamber drying and processing; Powder after will drying is again inserted in the gas reduction stove, passes into the mist of reducing gas and inert gas, then the gas reduction stove is warming up to 280～350 ℃, insulation 2.0～3.0h is cooled to room temperature at last, takes out powder, namely get the refrigeration crystal bar processing waste material of imurity-removal, vacuum is preserved.
Second step, N-type Bi
2Te
3The preparation of base thermoelectricity material
The refrigeration crystal bar processing waste material of the imurity-removal that first first step is obtained is put into quartz ampoule, by N-type Bi
2Te
3The chemical formula of base thermoelectricity material adds purity greater than Bi, Te, Sb and the Se raw material of 99.9wt%, N-type Bi
2Te
3The chemical formula of base thermoelectricity material is Bi
xSb
2-xTe
3-ySe
y, wherein: 1.8≤x≤1.9,0.44≤y≤0.55.Again quartz ampoule is vacuumized encapsulation, put into the heating furnace melting, smelting temperature is 630～680 ℃, and temperature retention time is 1.0～2.0h, then cools to room temperature with the furnace, takes out the alloy pig in the quartz ampoule, namely gets N-type Bi
2Te
3Base thermoelectricity material.
The cutting powder that the described refrigeration crystal bar of the present embodiment processing waste material produces when being cutting refrigeration crystal bar and follow-up cut crystal.
The mist of the described reducing gas of the present embodiment and inert gas is the mist of CO (carbon monoxide converter) gas and nitrogen, and wherein: the volumn concentration of CO (carbon monoxide converter) gas is 30～50%, and the volumn concentration of nitrogen is 50～70%.
Embodiment 3
A kind ofly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material.The preparation process of the method is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
The processing waste material of crystal bar of will freezing first grinds to form particle diameter less than 200 purpose fine powders, successively with the deionized water washing with use absolute ethanol washing, puts into the vacuum drying chamber drying and processing; Powder after will drying is again inserted in the gas reduction stove, passes into the mist of reducing gas and inert gas, then the gas reduction stove is warming up to 350～420 ℃, insulation 3.0～4.0h is cooled to room temperature at last, takes out powder, namely get the refrigeration crystal bar processing waste material of imurity-removal, vacuum is preserved.
Second step, N-type Bi
2Te
3The preparation of base thermoelectricity material
The refrigeration crystal bar processing waste material of the imurity-removal that first first step is obtained is put into quartz ampoule, by N-type Bi
2Te
3The chemical formula of base thermoelectricity material adds purity greater than Bi, Te, Sb and the Se raw material of 99.9wt%, N-type Bi
2Te
3The chemical formula of base thermoelectricity material is Bi
xSb
2-xTe
3-ySe
y, wherein: 1.7≤x≤1.8,0.25≤y≤0.4.Again quartz ampoule is vacuumized encapsulation, put into the heating furnace melting, smelting temperature is 680～730 ℃, and temperature retention time is 2.0～3.0h, then cools to room temperature with the furnace, takes out the alloy pig in the quartz ampoule, namely gets N-type Bi
2Te
3Base thermoelectricity material.
The cutting powder that the described refrigeration crystal bar of the present embodiment processing waste material produces when being cutting refrigeration crystal bar and follow-up cut crystal.
The mist of the described reducing gas of the present embodiment and inert gas is the mist of hydrogen and argon gas, and wherein: the volumn concentration of hydrogen is 50～70%, and the volumn concentration of argon gas is 30～50%.
Embodiment 4
A kind ofly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material.The preparation process of the method is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
The processing waste material of crystal bar of will freezing first grinds to form particle diameter less than 200 purpose fine powders, successively with the deionized water washing with use absolute ethanol washing, puts into the vacuum drying chamber drying and processing; Powder after will drying is again inserted in the gas reduction stove, passes into the mist of reducing gas and inert gas, then the gas reduction stove is warming up to 420～500 ℃, insulation 4.0～5.0h is cooled to room temperature at last, takes out powder, namely get the refrigeration crystal bar processing waste material of imurity-removal, vacuum is preserved.
Second step, N-type Bi
2Te
3The preparation of base thermoelectricity material
The refrigeration crystal bar processing waste material of the imurity-removal that first first step is obtained is put into quartz ampoule, by N-type Bi
2Te
3The chemical formula of base thermoelectricity material adds purity greater than Bi, Te, Sb and the Se raw material of 99.9wt%, N-type Bi
2Te
3The chemical formula of base thermoelectricity material is Bi
xSb
2-xTe
3-ySe
y, wherein: 1.6≤x≤1.7,0.10≤y≤0.25.Again quartz ampoule is vacuumized encapsulation, put into the heating furnace melting, smelting temperature is 730～800 ℃, and temperature retention time is 3.0～4.0h, then cools to room temperature with the furnace, takes out the alloy pig in the quartz ampoule, namely gets N-type Bi
2Te
3Base thermoelectricity material.
The breakage material that the described refrigeration crystal bar of the present embodiment processing waste material produces when being cutting refrigeration crystal bar and follow-up cut crystal.
The mist of the described reducing gas of the present embodiment and inert gas is the mist of CO (carbon monoxide converter) gas and argon gas: the volumn concentration of CO (carbon monoxide converter) gas is 70～80%, and the volumn concentration of argon gas is 20～30%.
Embodiment 5
A kind ofly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material.The preparation process of the method is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
The processing waste material of crystal bar of will freezing first grinds to form particle diameter less than 200 purpose fine powders, successively with the deionized water washing with use absolute ethanol washing, puts into the vacuum drying chamber drying and processing; Powder after will drying is again inserted in the gas reduction stove, passes into the mist of reducing gas and inert gas, then the gas reduction stove is warming up to 500～550 ℃, insulation 3.0～3.5h is cooled to room temperature at last, takes out powder, namely get the refrigeration crystal bar processing waste material of imurity-removal, vacuum is preserved.
Second step, N-type Bi
2Te
3The preparation of base thermoelectricity material
The refrigeration crystal bar processing waste material of the imurity-removal that first first step is obtained is put into quartz ampoule, by N-type Bi
2Te
3The chemical formula of base thermoelectricity material adds purity greater than Bi, Te, Sb and the Se raw material of 99.9wt%, N-type Bi
2Te
3The chemical formula of base thermoelectricity material is Bi
xSb
2-xTe
3-ySe
y, wherein: 1.5≤x≤1.6,0.4≤y≤0.55.Again quartz ampoule is vacuumized encapsulation, put into the heating furnace melting, smelting temperature is 800～850 ℃, and temperature retention time is 4.0～5.0h, then cools to room temperature with the furnace, takes out the alloy pig in the quartz ampoule, namely gets N-type Bi
2Te
3Base thermoelectricity material.
The breakage material that the described refrigeration crystal bar of the present embodiment processing waste material produces when being cutting refrigeration crystal bar and follow-up cut crystal.
The mist of the described reducing gas of the present embodiment and inert gas is the mist of hydrogen and argon gas: the volumn concentration of hydrogen is 50～70%, and the volumn concentration of argon gas is 30～50%.
Because adopt technique scheme, the present invention compared with prior art has the following advantages:
1) this embodiment directly prepares N-type Bi with refrigeration crystal bar processing waste material
2Te
3Base thermoelectricity material, front and back only namely get N-type Bi by removing impurity and two steps of composition adjustment
2Te
3Base thermoelectricity material is different from the method that traditional hydrometallurgy is carried out the individual element separating-purifying fully, reclaims technique simple.
2) this embodiment is from refrigeration crystal bar processing waste material to making at last N-type Bi
2Te
3Base thermoelectricity material, the cycle of finishing a recycling only needs 1.5h～10h, compares with the production technology of traditional recovery method, and the cycle shortens greatly.
3) this embodiment is in process of production without the discharging of solid waste and poisonous and harmful liquid, environmental protection, and a large amount of solid waste and the discharging of toxic liquid are difficult to avoid in the metallurgical recovery method of conventional wet, therefore environmental pollution is little.
4) Te, Sb, Se and the Bi element in this embodiment recycled in its entirety refrigeration crystal bar processing waste material, the rate of recovery of valuable element is more than 99%, comparing conventional wet metallurgy, to carry out the method rate of recovery of individual element separating-purifying higher, and economic benefit is better, and production cost is lower.
Therefore, this embodiment has the advantages that technique is simple, return period is short, environmental pollution is little and cost is low.
Claims (3)
1. one kind prepares N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material is characterized in that this preparation method's step is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
The processing waste material of crystal bar of will freezing first grinds to form particle diameter less than 200 purpose fine powders, successively with the deionized water washing with use absolute ethanol washing, puts into the vacuum drying chamber drying and processing; Powder after will drying is again inserted in the gas reduction stove, passes into the mist of reducing gas and inert gas, then the gas reduction stove is warming up to 200～550 ℃, insulation 1.0～5.0h is cooled to room temperature at last, takes out powder, namely get the refrigeration crystal bar processing waste material of imurity-removal, vacuum is preserved;
Second step, N-type Bi
2Te
3The preparation of base thermoelectricity material
The refrigeration crystal bar processing waste material of the imurity-removal that first first step is obtained is put into quartz ampoule, by N-type Bi
2Te
3The chemical formula of base thermoelectricity material adds purity greater than Bi, Te, Sb and the Se raw material of 99.9wt%, N-type Bi
2Te
3The chemical formula of base thermoelectricity material is Bi
xSb
2-xTe
3-ySe
y, wherein: 1.5≤x≤2.0,0.1≤y≤0.7; Again quartz ampoule is vacuumized encapsulation, put into the heating furnace melting, smelting temperature is 580～850 ℃, and temperature retention time is 0.5～5.0h, then cools to room temperature with the furnace, takes out the alloy pig in the quartz ampoule, namely gets N-type Bi
2Te
3Base thermoelectricity material.
2. according to claim 1ly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material is characterized in that cutting powder or damaged material that described refrigeration crystal bar processing waste material produces when being cutting refrigeration crystal bar and follow-up cut crystal.
3. according to claim 1ly prepare N-type Bi with refrigeration crystal bar processing waste material
2Te
3The method of base thermoelectricity material is characterized in that the mist of described reducing gas and inert gas is: the volumn concentration of reducing gas is 10～80%, and the volumn concentration of inert gas is 20～90%; Reducing gas is hydrogen or for CO (carbon monoxide converter) gas, inert gas is nitrogen or is argon gas.
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