KR20160146249A - Method for recovering tellurium oxide from waste thermoelectric module - Google Patents

Method for recovering tellurium oxide from waste thermoelectric module Download PDF

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Publication number
KR20160146249A
KR20160146249A KR1020150083259A KR20150083259A KR20160146249A KR 20160146249 A KR20160146249 A KR 20160146249A KR 1020150083259 A KR1020150083259 A KR 1020150083259A KR 20150083259 A KR20150083259 A KR 20150083259A KR 20160146249 A KR20160146249 A KR 20160146249A
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tellurium
recovering
waste
thermoelectric module
tellurium precursor
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KR1020150083259A
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Korean (ko)
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공만식
양재교
장대환
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고등기술연구원연구조합
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/004—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a method for recovering tellurium oxide from a waste thermoelectric module, and more particularly, to a method for recovering tellurium oxide from a waste thermoelectric module using a strong acid / strong base organic solvent from a waste heat source including a bismuth-telluride (Bi 2 Te 3 ) And more particularly to a method for recovering and recycling expensive tellurium (Te).
The present invention relates to a method for separating and recovering a thermoelectric material from a waste thermoelectric module, A second step of preparing a tellurium precursor in the thermoelectric material recovered through the first step; A third step of preparing a tellurium precursor solution with the tellurium precursor prepared in the second step; And a fourth step of recovering the tellurium oxide powder from the tellurium precursor solution prepared in the third step, wherein the tellurium oxide powder is recovered from the waste thermoelectric module.

Description

[0001] METHOD FOR RECOVERING TELLURIUM OXIDE FROM WASTE THERMOELECTRIC MODULE [0002]

The present invention relates to a method for recovering tellurium oxide from a waste thermoelectric module, and more particularly, to a method for recovering tellurium oxide from a waste thermoelectric module using a strong acid / strong base organic solvent from a waste heat source including a bismuth-telluride (Bi 2 Te 3 ) And more particularly to a method for recovering and recycling expensive tellurium (Te).

As the use of energy increases rapidly with the rapid industrial development in recent years, it is required to develop energy technology to replace it with exhaustion of fossil energy and environmental regulation. In order to cope with the energy depletion reality, research and development of thermoelectric materials having thermoelectric properties exhibiting endothermic or exothermic characteristics according to the temperature difference are being actively carried out, and the thermoelectric conversion system employing the thermoelectric conversion system is expected to maximize the energy utilization efficiency, In terms of energy development, it is attracting attention as next generation energy technology.

Such a thermoelectric material is attached to a small refrigerator such as a cold / hot water machine or a sheet for cooling a car, thereby providing convenience in life. Recently, the demand for thermoelectric materials is rapidly increasing because it is applied to various fields such as high-tech industry such as aerospace, precision temperature sensor, communication and thermoelectric generator for military space.

Currently, most thermoelectric materials are alloyed with elements such as bismuth (Bi), antimony (Sb), and selenium (Se) based on tellurium (Te), but the most commonly used materials are commercially available Bi- It is known that the material is bismuth-telluride (Bi 2 Te 3 ). Among them, tellurium (Te), which is a core material of thermoelectric materials, is one of the elements with a small amount of reserves, and the price and demand are rapidly increasing every year.

In order to meet the demand for tellurium, which is soaring in the future, it is inevitable to develop a technology for recovery and recycling of tellurium from a large amount of future thermoelectric products. There is no specific method for recovering and recycling the above-mentioned bismuth-telluride (Bi 2 Te 3 ) thermoelectric material, and it is limited to the thermoelectric material recovery technology. Since the thermoelectric material component recovery technology relies on organic solvents in strong acid / strong base form, it can cause not only environmental pollution but also corrosive problems of peripheral devices and devices, and addition reaction such as high temperature heat treatment at 1000 ° C. There is a problem of rising unit price.

Korean Patent Registration No. 10-1451789 (Oct. 10, 2014) has been proposed in connection with the recovery of tellurium. However, as described above, the use of hydrochloric acid as a solution causes problems such as environmental pollution and device corrosion.

Accordingly, the present inventors have focused on the limitations of the prior art and the situation in which the recovery of tellurium is required, and have found that a process capable of recovering tellurium from the waste thermoelectric module without using a strong acid / strong base organic solvent And completed the present invention.

(Document 1) Korean Patent Registration No. 10-1451789 (October 10, 2014)

 Therefore, the present invention does not use a strong acid / strong base type organic solvent in the recovery of tellurium oxide, so it does not cause environmental pollution as well as corrosion problems of peripheral devices and apparatuses, and does not cause a problem of process technology due to addition reaction such as high temperature heat treatment It is an object of the present invention to provide a method of recovering environmentally friendly and economical tellurium oxide by solving the problem of increased risk and process cost.

According to an aspect of the present invention, there is provided a thermoelectric module including: a first step of separating and recovering a thermoelectric material from a waste thermoelectric module; A second step of preparing a tellurium precursor in the thermoelectric material recovered through the first step; A third step of preparing a tellurium precursor solution with the tellurium precursor prepared in the second step; And a fourth step of recovering the tellurium oxide powder from the tellurium precursor solution prepared in the third step, wherein the tellurium oxide powder is recovered from the waste thermoelectric module.

In the first step, it is preferable that the substrate, the solder and the thermoelectric material are separated from the waste thermoelectric module by dry operation at a temperature of 183 to 730 ° C.

In the second step, it is preferable that the thermoelectric material is dissolved in a hydrogen peroxide solution at 10 to 200 ° C, and the tellurium precursor is recovered by washing and filtering, and the concentration of the tellurium precursor is adjusted through concentration.

In the third step, the tellurium precursor is preferably prepared by using 0.1 to 1.0 M tellurium precursor solution using deionized water.

Preferably, the fourth step includes a step of thermally decomposing the tellurium precursor solution through ultrasonic spraying.

The pyrolysis temperature is preferably 600 to 900 ° C.

And an annealing step of converting the amorphous tellurium oxide into the crystalline tellurium oxide after the pyrolysis step.

According to the present invention, since the organic solvent of the strong acid / strong base type is not used in recovering the tellurium oxide, it does not cause the environmental pollution as well as the corrosion problem of the peripheral equipment and the apparatus, and the process due to the addition reaction such as the high temperature heat treatment There is an environmental and economic effect by solving the problem of the technology and the increase of the process cost.

1 is a flow chart schematically showing a method for recovering tellurium according to the present invention.
2 shows the thermoelectric material separated and recovered from the waste thermoelectric module according to the present invention.
FIG. 3 shows the XRD analysis results obtained by the ultrasonic spray pyrolysis and annealing processes by the tellurium precursor according to the present invention.
4 is a SEM photograph of the recovered tellurium powder according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the appended drawings illustrate only the contents and scope of technology of the present invention, and the technical scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

1 is a flow chart schematically showing a method for recovering tellurium according to the present invention. As shown in FIG. 1, a method for recovering tellurium oxide in a waste thermoelectric module according to the present invention includes a first step (S100) of separating and recovering a thermoelectric material from a waste thermoelectric module; A second step (S200) of producing a tellurium precursor in the thermoelectric material recovered through the first step (S100); A third step (S300) of preparing a tellurium precursor solution with the tellurium precursor prepared in the second step (S200); And a fourth step (S400) of recovering the tellurium oxide powder from the tellurium precursor solution prepared in the third step (S300).

First, the first step S100 is a step of separating and recovering the thermoelectric material from the waste thermoelectric module. At this time, the dry method is applied at a temperature of about 183 to 730 ° C, and the Al 2 O 3 substrate, the Pb-Sn solder, and the bismuth-telluride (Bi 2 Te 3 ) thermoelectric material are separated from the waste thermoelectric module .

In the thermoelectric module, the melting point of the Pb-Sn solder is about 183 ° C., and the thermoelectric material to be recovered in the solid state may become liquid when the temperature exceeds 730 ° C. Therefore, the temperature range applied here is preferably between 183 ° C. and 730 ° C. The separation time is suitably between 5 and 30 minutes.

2 shows the thermoelectric material separated and recovered from the waste thermoelectric module according to the present invention. As shown in FIG. 2, the thermoelectric material is separated / recovered from the waste thermoelectric module through a high-temperature drying method.

Next, the second step S200 is a method for producing a tellurium precursor by recovering the bismuth-telluride (Bi 2 Te 3 ) thermoelectric material recovered through the first step S100, The bismuth-telluride (Bi 2 Te 3 ) thermoelectric material can be dissolved, washed and filtered to recover the tellurium precursor, and the concentration of the tellurium precursor can be controlled through concentration. The temperature of the hydrogen peroxide solution is in the range of 10 to 200 ° C, the temperature of 10 ° C is usually the room temperature, and the hydrogen peroxide solution preferably extracts the tellurium precursor and other substances at a temperature of 160 ° C.

Here, the dissolution reaction of the bismuth-telluride thermoelectric material in the hydrogen peroxide solution proceeds according to the following reaction formula 1.

 [Reaction Scheme 1]

2Bi 2 Te 3 + 9H 2 O 2 -> 4Bi + 6HTeO 3 - + 12H +

This tellurium (Te) dissolution may be carried out at 10 to 200 DEG C and may be conducted for 30 minutes to 2 hours. If the dissolution time and temperature of tellurium are less than the above range, Tellurium dissolution may not be sufficiently performed. If the above range is exceeded, the energy cost may be unnecessarily excessive.

These reactions result in the formation of Bi and tellurium lysates where they are washed with ethanol or water to obtain a tellurium precursor, and the tellurium precursor is extracted through centrifugation and filtration. The concentration of the tellurium precursor Can be adjusted.

Next, the third step (S300) is a method for preparing a tellurium precursor solution by the tellurium precursor prepared in the second step (S200). The tellurium precursor is dissolved in 0.1 to 1.0 M tellurium precursor solution .

Next, the fourth step (S400) performs a method of recovering the tellurium oxide powder from the tellurium precursor solution produced through the third step (S300).

First, a 0.1 to 1.0 M tellurium precursor solution can be pyrolyzed through ultrasonic atomization. That is, pyrolysis is performed at a temperature of 600 to 900 ° C. to solidify the liquid phase through drying of the tellurium precursor solution, and Te (OH) 2 is converted into tellurium oxide (TeO 2 ).

When pyrolysis is completed, an annealing process may be performed at a temperature of 200 to 730 ° C for about 1 to 3 hours. Tellurium oxide removing moisture remaining in the (TeO 2) through the annealing process, and tellurium oxide on an amorphous (TeO 2) is changed to tellurium oxide (TeO 2) on the crystalline.

The tellurium oxide (TeO 2 ) produced by the ultrasonic spray pyrolysis process exists in an amorphous state, which is a phenomenon caused by a short residence time during the pyrolysis process. This phenomenon is due to the relatively short duration of the sprayed droplet in the high-temperature reactor, and therefore, it is present in an amorphous state without producing crystals.

When amorphous phase is transformed into tellurium oxide (TeO 2 ) in the crystalline phase by supplying sufficient thermal energy to tellurium oxide (TeO 2 ) through the annealing process, the recrystallized tellurium oxide (TeO 2 ) powder is converted into amorphous and crystalline As shown in FIG.

FIG. 3 shows the XRD (LabX XRD-6100, Shimadzu) analysis result of the tellurium precursor solution according to the present invention after performing an ultrasonic spray pyrolysis and annealing process.

As shown in FIG. 3, the graph Te-precursor shown at the bottom is the XRD pattern of Te (OH) 6 as a tellurium precursor, and the graph shown at the top shows that a solution of 1.0 M is pyrolyzed through ultrasonic spray at 900 ° C. (TeO 2 ) powder prepared by annealing at 400 ° C for 3 hours. As the tellurium precursor undergoes pyrolysis process, it becomes tellurium oxide and undergoes an annealing process, and the tellurium oxide is converted into a crystalline phase, and the strength becomes strong.

4 is a SEM (MIRA3, TESCAN) analysis of the recovered tellurium powder according to the present invention.

As shown in FIG. 4, the powder prepared by the ultrasonic spray pyrolysis process from the tellurium precursor solution was in an amorphous state and the tellurium oxide crystal phase could be confirmed through the annealing process.

The tellurium oxide powder prepared through these steps can be applied to optoelectric or thermoelectric modules, and it is possible to obtain economical advantages by recycling of tellurium (Te).

The present invention relates to a method of recovering and recycling a thermoelectric material in a large amount of waste thermoelectric material which is mostly disposed of in order to meet the rapidly increasing demand for tellurium, thereby recovering a high yield of tellurium (Te) to prepare a precursor, Tellurium oxide powders can be prepared to produce tellurium (Te), which is a high-value-added material that can be used in various fields.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

<Examples>

First, in order to separate and recover the thermoelectric material from the recovered thermoelectric module, the adhesiveness of the Al 2 O 3 substrate, the Pb-Sn solder, and the bismuth-telluride (Bi 2 Te 3 ) thermoelectric material was weakened by the dry method at a temperature of 200 ° C. The substrate, solder and thermoelectric material were separated and recovered.

The recovered thermoelectric material was reacted with hydrogen peroxide at 160 ° C to prepare a tellurium precursor, and the prepared tellurium precursor was prepared with a 0.1 to 1.0 M tellurium precursor solution with deionized water.

The prepared tellurium precursor solution was subjected to an ultrasonic spray pyrolysis process at 600 to 900 ° C and an annealing process at 400 ° C to recover the tellurium oxide.

Therefore, it can be concluded from the results of this embodiment that the method of the present invention can recover the high purity tellurium oxide by recovering the thermoelectric material from the waste thermoelectric module and removing the impurities and the like.

Claims (7)

A first step of separating and recovering the thermoelectric material from the waste thermoelectric module;
A second step of preparing a tellurium precursor in the thermoelectric material recovered through the first step;
A third step of preparing a tellurium precursor solution with the tellurium precursor prepared in the second step; And
And recovering the tellurium oxide powder from the tellurium precursor solution prepared in the third step, wherein the tellurium oxide powder is recovered from the tellurium precursor solution.
The method according to claim 1,
Wherein the first step removes the substrate, the solder, and the thermoelectric material from the waste thermoelectric module dry at a temperature between 183 and 730 캜, recovering the tellurium oxide from the waste thermoelectric module.
The method according to claim 1,
The second step is to dissolve the thermoelectric material in a hydrogen peroxide solution at 10 to 200 ° C to recover the tellurium precursor through washing and filtration and to adjust the concentration of the tellurium precursor through concentration, And recovering the oxide.
The method according to claim 1,
Wherein said third step is to produce a 0.1-1. 0 M tellurium precursor solution using deionized water in said tellurium precursor.
The method according to claim 1,
Wherein said fourth step comprises pyrolysis of the tellurium precursor solution through ultrasonic atomization.
6. The method of claim 5,
Wherein the pyrolysis temperature is 600 to 900 占 폚.
6. The method of claim 5,
Further comprising an annealing step of converting the amorphous tellurium oxide to a crystalline tellurium oxide after the pyrolysis step.
KR1020150083259A 2015-06-12 2015-06-12 Method for recovering tellurium oxide from waste thermoelectric module KR20160146249A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190054644A (en) * 2017-11-14 2019-05-22 (주)엠티아이지 Manufacturing method of bismuth telluride nano powder using waste thermoelectric module
CN110127632A (en) * 2019-05-13 2019-08-16 四川大学 A method of recycling tellurium from bismuth telluride base semiconductor refrigeration sheet waste material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101451789B1 (en) 2012-10-23 2014-10-16 한국과학기술연구원 Separation of tellurium by solvent extraction method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101451789B1 (en) 2012-10-23 2014-10-16 한국과학기술연구원 Separation of tellurium by solvent extraction method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190054644A (en) * 2017-11-14 2019-05-22 (주)엠티아이지 Manufacturing method of bismuth telluride nano powder using waste thermoelectric module
CN110127632A (en) * 2019-05-13 2019-08-16 四川大学 A method of recycling tellurium from bismuth telluride base semiconductor refrigeration sheet waste material
CN110127632B (en) * 2019-05-13 2022-09-02 四川大学 Method for recovering tellurium from bismuth telluride-based semiconductor refrigeration sheet waste

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