CN103311426B - N-type Bi is prepared with refrigeration crystal bar processing waste material 2te 3the method of base thermoelectricity material - Google Patents
N-type Bi is prepared with refrigeration crystal bar processing waste material 2te 3the method of base thermoelectricity material Download PDFInfo
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- CN103311426B CN103311426B CN201310253561.8A CN201310253561A CN103311426B CN 103311426 B CN103311426 B CN 103311426B CN 201310253561 A CN201310253561 A CN 201310253561A CN 103311426 B CN103311426 B CN 103311426B
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- 239000013078 crystal Substances 0.000 title claims abstract description 76
- 238000005057 refrigeration Methods 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 230000005619 thermoelectricity Effects 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000003708 ampul Substances 0.000 claims abstract description 24
- 239000010453 quartz Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003595 mist Substances 0.000 claims abstract description 20
- 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 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 11
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 238000009413 insulation Methods 0.000 claims abstract description 9
- 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
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005538 encapsulation Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 15
- 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
- 239000012535 impurity Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001291 vacuum drying 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
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 43
- 238000011084 recovery Methods 0.000 description 12
- 239000011669 selenium Substances 0.000 description 9
- 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
- 239000002910 solid waste Substances 0.000 description 4
- 238000009854 hydrometallurgy 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
- 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
- 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
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 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
- 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
- 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 present invention relates to one refrigeration crystal bar processing waste material and prepare N-type Bi
2te
3the method of base thermoelectricity material.Its technical scheme is: first by the processing waste material grinding of refrigeration crystal bar, washing, dries; Inserted in gas reduction stove by powder after drying, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 200 ~ 550 DEG C, insulation 1.0 ~ 5.0h, is cooled to room temperature, obtains the refrigeration crystal bar processing waste material of imurity-removal.Then put it in quartz ampoule, by N-type Bi
2te
3chemical formula (the Bi of base thermoelectricity material
xsb
2-xte
3-yse
y, wherein 1.5≤x≤2.0,0.1≤y≤0.7) add purity and be greater than Bi, Te, Sb and Se raw material of 99.9wt%.Finally vacuumize encapsulation to quartz ampoule, put into heating furnace melting, smelting temperature is 580 ~ 850 DEG C, insulation 0.5 ~ 5.0h, with stove cooling, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.The present invention has the advantages that technique is simple, return period is short, environmental pollution is little and cost is low.
Description
Technical field
The invention belongs to N-type Bi
2te
3base thermoelectricity material technical field.Be specifically related to one refrigeration crystal bar processing waste material and prepare N-type Bi
2te
3the method of base thermoelectricity material.
Background technology
Thermoelectric material is a kind of functional material heat energy and electric energy directly can changed mutually, more and more causes the attention of people at society.Bi
2te
3based compound, as the thermoelectric material of near room temperature thermoelectricity capability optimum, has irreplaceable status in commercial applications process, is widely used in semiconductor refrigerating industry.Current commercial large-scale production Bi
2te
3base thermoelectricity material normally adopts the mode uniaxially grown, as Bridgman method and zone melting method, in the hope of obtaining the Bi with excellent thermoelectricity capability
2te
3based compound monocrystalline or column crystal.Adopt the Bi that above production method obtains
2te
3base refrigeration crystal bar machining property is poor, and easily fracture and breakage in following process process, percent defective is high, and stock utilization is less than 50%.
As everyone knows, selenium and tellurium belong to rare and scatter element, and usual association content in the sulphide ore such as pyrite and chalcopyrite is few, expensive, 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 produced when cutting refrigeration crystal bar or follow-up cut crystal or damaged material, often adopt hydrometallurgy to carry out single element separating-purifying and reclaimed.As " a kind of bismuth telluride base semiconductor refrigeration material reclaims the method for tellurium " (ZL200610132393.7) patented technology, this technology adds oxidant by after cutting powder alkali fusion, adopt sour neutralization to leach and obtain tellurium dioxide, finally adopting alkali dissolving liquid making and electrodeposition to extract has valency tellurium element.Also pyrogenic process can be adopted to be oxidized be oxidized and open state in conjunction with extract technology extraction Te with Bi(with villaumite, the technique of semiconductor chilling plate waste recovery tellurium, non-ferrous metal is in progress, 2007,1996-2005(5): 550; Chen Peihuan, reclaims the research of the valuable metals such as tellurium from cooling module waste material, strain smelting science and technology, 1991,19(2): 125).The theoretical foundation adopting above method to extract Te and Bi is by Te or Bi element oxide, then be separated and purify separately, and recovery scheme is all that the valuable element in refrigeration crystal bar processing waste material is carried out independent separating-purifying, single simple substance element is progressively carried out separating-purifying by point multi-step and multiple operation, 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 prior art defect, provides 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
First the processing waste material of refrigeration crystal bar is ground to form particle diameter and be less than 200 object fine powders, spend deionized water successively and with absolute ethanol washing, put into vacuum drying chamber drying and processing; Again the powder after oven dry is inserted in gas reduction stove, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 200 ~ 550 DEG C, insulation 1.0 ~ 5.0h, is finally cooled to room temperature, takes out powder, obtain 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 first first step obtained puts into quartz ampoule, by N-type Bi
2te
3the chemical formula of base thermoelectricity material, adds Bi, Te, Sb and Se raw material that purity is greater than 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.Vacuumize encapsulation to quartz ampoule again, put into heating furnace melting, smelting temperature is 580 ~ 850 DEG C, and temperature retention time is 0.5 ~ 5.0h, then cools to room temperature with the furnace, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.
Described refrigeration crystal bar processing waste material is the cutting powder that produces when 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 is CO (carbon monoxide converter) gas, and inert gas is nitrogen or is argon gas.
Owing to adopting 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, namely front and back obtain N-type Bi by means of only removal impurity and composition adjustment two step
2te
3base thermoelectricity material, be different from the method that traditional hydrometallurgy carries out individual element separating-purifying completely, recovery process is simple.
2) the present invention is from refrigeration crystal bar processing waste material to last obtained N-type Bi
2te
3base thermoelectricity material, the cycle completing a recycling only needs 1.5h ~ 10h, and compared with the production technology of conventional recovery method, the cycle shortens greatly.
3) the present invention is in process of production without the discharge of solid waste and poisonous and harmful liquid, environmental protection, and in the metallurgical recovery method of conventional wet, the discharge of a large amount of solid waste and toxic liquid is difficult to avoid, therefore environmental pollution is little.
4) Te, Sb, Se and Bi element in 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
Below in conjunction with embodiment, the present invention will be further described, the restriction not to its protection range:
Embodiment 1
One refrigeration crystal bar processing waste material prepares N-type Bi
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
First the processing waste material of refrigeration crystal bar is ground to form particle diameter and be less than 200 object fine powders, spend deionized water successively and with absolute ethanol washing, put into vacuum drying chamber drying and processing; Again the powder after oven dry is inserted in gas reduction stove, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 200 ~ 280 DEG C, insulation 1.0 ~ 2.0h, is finally cooled to room temperature, takes out powder, obtain 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 first first step obtained puts into quartz ampoule, by N-type Bi
2te
3the chemical formula of base thermoelectricity material, adds Bi, Te, Sb and Se raw material that purity is greater than 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.Vacuumize encapsulation to quartz ampoule again, put into heating furnace melting, smelting temperature is 580 ~ 630 DEG C, and temperature retention time is 0.5 ~ 1.0h, then cools to room temperature with the furnace, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.
The cutting powder of refrigeration crystal bar processing waste material described in the present embodiment for producing when cutting refrigeration crystal bar and follow-up cut crystal.
The mist of reducing gas described in the present embodiment and inert gas is the mist of hydrogen and nitrogen, and wherein: the volumn concentration of hydrogen is 10 ~ 30%, the volumn concentration of nitrogen is 70 ~ 90%.
Embodiment 2
One refrigeration crystal bar processing waste material prepares N-type Bi
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
First the processing waste material of refrigeration crystal bar is ground to form particle diameter and be less than 200 object fine powders, spend deionized water successively and with absolute ethanol washing, put into vacuum drying chamber drying and processing; Again the powder after oven dry is inserted in gas reduction stove, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 280 ~ 350 DEG C, insulation 2.0 ~ 3.0h, is finally cooled to room temperature, takes out powder, obtain 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 first first step obtained puts into quartz ampoule, by N-type Bi
2te
3the chemical formula of base thermoelectricity material, adds Bi, Te, Sb and Se raw material that purity is greater than 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.Vacuumize encapsulation to quartz ampoule again, put into heating furnace melting, smelting temperature is 630 ~ 680 DEG C, and temperature retention time is 1.0 ~ 2.0h, then cools to room temperature with the furnace, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.
The cutting powder of refrigeration crystal bar processing waste material described in the present embodiment for producing when cutting refrigeration crystal bar and follow-up cut crystal.
The mist of reducing gas described in 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%, the volumn concentration of nitrogen is 50 ~ 70%.
Embodiment 3
One refrigeration crystal bar processing waste material prepares N-type Bi
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
First the processing waste material of refrigeration crystal bar is ground to form particle diameter and be less than 200 object fine powders, spend deionized water successively and with absolute ethanol washing, put into vacuum drying chamber drying and processing; Again the powder after oven dry is inserted in gas reduction stove, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 350 ~ 420 DEG C, insulation 3.0 ~ 4.0h, is finally cooled to room temperature, takes out powder, obtain 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 first first step obtained puts into quartz ampoule, by N-type Bi
2te
3the chemical formula of base thermoelectricity material, adds Bi, Te, Sb and Se raw material that purity is greater than 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.Vacuumize encapsulation to quartz ampoule again, put into heating furnace melting, smelting temperature is 680 ~ 730 DEG C, and temperature retention time is 2.0 ~ 3.0h, then cools to room temperature with the furnace, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.
The cutting powder of refrigeration crystal bar processing waste material described in the present embodiment for producing when cutting refrigeration crystal bar and follow-up cut crystal.
The mist of reducing gas described in the present embodiment and inert gas is the mist of hydrogen and argon gas, and wherein: the volumn concentration of hydrogen is 50 ~ 70%, the volumn concentration of argon gas is 30 ~ 50%.
Embodiment 4
One refrigeration crystal bar processing waste material prepares N-type Bi
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
First the processing waste material of refrigeration crystal bar is ground to form particle diameter and be less than 200 object fine powders, spend deionized water successively and with absolute ethanol washing, put into vacuum drying chamber drying and processing; Again the powder after oven dry is inserted in gas reduction stove, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 420 ~ 500 DEG C, insulation 4.0 ~ 5.0h, is finally cooled to room temperature, takes out powder, obtain 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 first first step obtained puts into quartz ampoule, by N-type Bi
2te
3the chemical formula of base thermoelectricity material, adds Bi, Te, Sb and Se raw material that purity is greater than 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.Vacuumize encapsulation to quartz ampoule again, put into heating furnace melting, smelting temperature is 730 ~ 800 DEG C, and temperature retention time is 3.0 ~ 4.0h, then cools to room temperature with the furnace, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.
The breakage material of refrigeration crystal bar processing waste material described in the present embodiment for producing when cutting refrigeration crystal bar and follow-up cut crystal.
The mist of reducing gas described in 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
One refrigeration crystal bar processing waste material prepares N-type Bi
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
First the processing waste material of refrigeration crystal bar is ground to form particle diameter and be less than 200 object fine powders, spend deionized water successively and with absolute ethanol washing, put into vacuum drying chamber drying and processing; Again the powder after oven dry is inserted in gas reduction stove, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 500 ~ 550 DEG C, insulation 3.0 ~ 3.5h, is finally cooled to room temperature, takes out powder, obtain 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 first first step obtained puts into quartz ampoule, by N-type Bi
2te
3the chemical formula of base thermoelectricity material, adds Bi, Te, Sb and Se raw material that purity is greater than 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.Vacuumize encapsulation to quartz ampoule again, put into heating furnace melting, smelting temperature is 800 ~ 850 DEG C, and temperature retention time is 4.0 ~ 5.0h, then cools to room temperature with the furnace, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.
The breakage material of refrigeration crystal bar processing waste material described in the present embodiment for producing when cutting refrigeration crystal bar and follow-up cut crystal.
The mist of reducing gas described in 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%.
Owing to adopting 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, namely front and back obtain N-type Bi by means of only removal impurity and composition adjustment two step
2te
3base thermoelectricity material, be different from the method that traditional hydrometallurgy carries out individual element separating-purifying completely, recovery process is simple.
2) this embodiment is from refrigeration crystal bar processing waste material to last obtained N-type Bi
2te
3base thermoelectricity material, the cycle completing a recycling only needs 1.5h ~ 10h, and compared with the production technology of conventional recovery method, the cycle shortens greatly.
3) this embodiment is in process of production without the discharge of solid waste and poisonous and harmful liquid, environmental protection, and in the metallurgical recovery method of conventional wet, the discharge of a large amount of solid waste and toxic liquid is difficult to avoid, therefore environmental pollution is little.
4) Te, Sb, Se and 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. prepare N-type Bi with refrigeration crystal bar processing waste material for one kind
2te
3the method of base thermoelectricity material, is characterized in that the step of this preparation method is:
The removal of impurities of the first step, refrigeration crystal bar processing waste material
First the processing waste material of refrigeration crystal bar is ground to form particle diameter and be less than 200 object fine powders, spend deionized water successively and with absolute ethanol washing, put into vacuum drying chamber drying and processing; Again the powder after oven dry is inserted in gas reduction stove, pass into the mist of reducing gas and inert gas, then gas reduction stove is warming up to 200 ~ 550 DEG C, insulation 1.0 ~ 5.0h, is finally cooled to room temperature, takes out powder, obtain 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 first first step obtained puts into quartz ampoule, by N-type Bi
2te
3the chemical formula of base thermoelectricity material, adds Bi, Te, Sb and Se raw material that purity is greater than 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; Vacuumize encapsulation to quartz ampoule again, put into heating furnace melting, smelting temperature is 580 ~ 850 DEG C, and temperature retention time is 0.5 ~ 5.0h, then cools to room temperature with the furnace, takes out the alloy pig in quartz ampoule, obtains N-type Bi
2te
3base thermoelectricity material.
2. refrigeration crystal bar processing waste material according to claim 1 prepares N-type Bi
2te
3the method of base thermoelectricity material, is characterized in that described refrigeration crystal bar processing waste material is for the cutting powder that produces when cutting refrigeration crystal bar and follow-up cut crystal or damaged material.
3. refrigeration crystal bar processing waste material according to claim 1 prepares N-type Bi
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 is CO (carbon monoxide converter) gas, and inert gas is nitrogen or is argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310253561.8A CN103311426B (en) | 2013-06-24 | 2013-06-24 | N-type Bi is prepared with refrigeration crystal bar processing waste material 2te 3the method of base thermoelectricity material |
Applications Claiming Priority (1)
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| CN109569475A (en) * | 2017-09-28 | 2019-04-05 | 中国电力科学研究院 | A kind of thermoelectric material preparation facilities and method |
| CN108231991A (en) * | 2017-11-24 | 2018-06-29 | 浙江大学 | A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat |
| CN107858545B (en) * | 2017-12-06 | 2019-08-30 | 先导薄膜材料（广东）有限公司 | Dissociate the minimizing technology of tellurium in a kind of high-melting-point telluride alloy |
| CN108649115B (en) * | 2018-05-10 | 2019-07-12 | 广东雷子克热电工程技术有限公司 | Five elements N-shaped thermoelectric material and preparation method based on the sintering phase transformation of crystal topological realization powder metallurgy |
| CN111454060B (en) * | 2020-04-08 | 2021-04-02 | 深圳见炬科技有限公司 | N-type bismuth telluride-based thermoelectric material with modulation structure and preparation method thereof |
| CN114561706A (en) * | 2021-12-16 | 2022-05-31 | 杭州大和热磁电子有限公司 | Method for recycling bismuth telluride crystal bar processing waste and utilization method thereof |
| CN114807655B (en) * | 2022-04-28 | 2024-03-22 | 武汉科技大学 | Preparation method of n-type magnesium-antimony-bismuth-based polycrystalline block thermoelectric material |
| CN114874011B (en) * | 2022-05-31 | 2023-05-30 | 先导薄膜材料（广东）有限公司 | Method for improving electrical property of n-type bismuth telluride-based thermoelectric material |
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