CN107475736B - A kind of preparation method of the 4N tellurium based on alkaline electrodeposition technology - Google Patents
A kind of preparation method of the 4N tellurium based on alkaline electrodeposition technology Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of 4N tellurium based on alkaline electrodeposition technology, comprising the following steps: at room temperature, sodium hydroxide piece is added in ultrapure water, stirring and dissolving obtains heat alkali liquid；Thick tellurium dioxide powder is added in heat alkali liquid and is reacted, liquid before electrolysis is prepared；Cleanser is added, purified treatment is carried out to liquid before being electrolysed, electrolyte is prepared in filtering；Electrolyte is cooled to room temperature, addition additive, after stirring and dissolving, the processing of constant pressure pre-deposition is carried out to electrolyte, then carries out constant current electrodeposition process, obtains electro-deposition product tellurium block and electrolytic liquid；It after tellurium block is removed from electrode plate, for several times with milli-Q water, then dries, 4N tellurium is prepared.Preparation method of the invention has depositing current density big, and deposition efficiency is high, and short preparation period, tellurium product compactness is good, and electrolyte recycles, low in cost, environmental-friendly and the advantages that be easy to industrialization, can be effectively applied to alkaline electro-deposition preparation 4N essence tellurium.
Description
Technical field
The invention belongs to the electrochemistry of dissipated metal tellurium to purify refining techniques field, specifically, being related to a kind of based on alkali
The preparation method of the 4N tellurium of property electrodeposition technology.
Background technique
Dissipated metal tellurium is a kind of strategic resource of preciousness, is known as " the dimension life of modern industry, national defence and sophisticated technology
Element ", is the important support material of contemporary high-tech art, new material, is widely used in metallurgy, petroleum, chemical industry, electronics, electrical, pottery
Porcelain, pigment and medicine and other fields.The main source of tellurium is the byproduct earth of positive pole of copper refining factory, and wherein tellurium content is usually less than
10%；Other sources are in mud, lead anode slurry, bismuth tellurium concentrate and the sulfuric acid plant of sulfuric acid plant and the precipitator of smeltery
Dust etc..The purity of tellurium will have a direct impact on the physicochemical property of the material containing tellurium, in order to obtain the tellurium of higher purity, separating-purifying at present
The method of tellurium have soda ash roasting method, alkaline high pressure lixiviation process, sulfating roasting method, oxidation acid leaching method, extraction, liquid-film method,
Microbial method and electrolytic refining process etc..These respectively have advantage and disadvantage about the method for purification of tellurium, and most of purification techniques are still located
In the experimental study stage, there is the problems such as environmental pollution is serious, processing technology routine complexity and high production cost in some methods.Electricity
Solution purifying method belongs to electrodeposition technology, has purification technique mature, and effect stability is reliable, and operational administrative is simple, and equipment takes up an area face
The small and advantages of environment protection of product, can obtain the tellurium of high-purity 4N or more, be one of the preferred approach of current tellurium industrialization.But mesh
Preceding electro-deposition prepares the technique of 4N essence tellurium, and there is also the small (50A/m of depositing current density2), deposition efficiency is low (80%), production
Period is long (discharging within 3 days), and tellurium product compactness is poor (poor adhesive force on electrode plate is easy to fall to bottom of electrolytic tank), electricity
Solution liquid utilization rate is low, and overall cost is higher, is unfavorable for the industrialization of 4N essence tellurium and the development of relevant industries.Therefore, one kind is developed
High efficiency, the alkaline electrodeposition technology of low cost for preparing 4N tellurium are extremely important.
Summary of the invention
In view of this, the present invention is directed to above-mentioned problem, a kind of system of 4N tellurium based on alkaline electrodeposition technology is provided
Preparation Method, the preparation method are the alkaline electrodeposition technologies of a kind of high efficiency, low cost.
In order to solve the above-mentioned technical problem, the invention discloses a kind of preparation sides of 4N tellurium based on alkaline electrodeposition technology
Method, comprising the following steps:
Step 1 weighs: weighing following components: 1 part of sodium hydroxide piece, 2~6 parts of ultrapure water, thick titanium dioxide according to parts by weight
1~5 part of telloy；
Load weighted sodium hydroxide piece is added in ultrapure water for step 2, at room temperature, and stirring and dissolving is complete, obtains thermokalite
Liquid；Load weighted thick tellurium dioxide powder is added in heat alkali liquid and is reacted, liquid before electrolysis is prepared；
Cleanser is added to liquid progress purified treatment before being electrolysed in step 3, then filters, electrolyte is prepared；
Electrolyte is cooled to room temperature by step 4, and additive is added, and after stirring and dissolving is complete, it is pre- to carry out constant pressure to electrolyte
Then deposition processes carry out constant current electrodeposition process, obtain electro-deposition product tellurium block and electrolytic liquid；
Step 5 after removing tellurium block from electrode plate, for several times with milli-Q water, is then dried, and 4N tellurium is prepared.
Further, after step 5, to electrolytic liquid Central Asia tellurate ion, hydroxide ion and foreign ion
Concentration is monitored online, and is adjusted with tellurium dioxide raw material, sodium hydroxide, electrolyte and ultrapure water, the electrolytic liquid Central Asia
After the concentration of tellurate ion, hydroxide ion and foreign ion is up to standard, electrolytic liquid is changed into electrolyte and is recycled.
Further, in step 2 in thick tellurium dioxide raw material tellurium purity >=60%, water content 15%~20%.
Further, the thick tellurium dioxide powder in step 2 is 70~90 DEG C with temperature when reacting of heat alkali liquid.
Further, cleanser is vulcanized sodium, ammonium sulfide, thioacetamide, ammonium hydroxide, ammonium thiocyanate, six first in step 3
One of urotropine, disodium edta, ethylenediamine tetraacetic methene sodium phosphate or triethanolamine are a variety of.
Further, purified treatment temperature is 70~90 DEG C in step 3；Cleanser accounts for thick tellurium dioxide powder quality total amount
1~10%.
Further, additive is gelatin, polyacrylamide, chitosan, starch, alum, ferrous sulfate, gathers in step 4
One of silicic acid, poly-silicic acid iron sulfate or poly- phosphorus iron chloride are a variety of.
Further, in step 4 constant pressure pre-deposition processing voltage be 0.6~0.8V, constant pressure pre-deposition handle the time be 1~
24h；The current density of constant current electro-deposition is 80~100A/m2；Constant current electrodeposition time is 12~48h；Additive accounts for thick dioxy
Change the 0.1%~5% of telloy quality total amount.
Further, the concentration of electrolytic liquid Central Asia tellurate ion, hydroxide ion and foreign ion is up to standard in step 6
Condition are as follows: the concentration control of tellurious acid ion is controlled in 200~300g/L, the concentration of hydroxide ion in 80~120g/L,
Concentration impurity ion is controlled in Pb < 20ppm, Se < 30ppm.Compared with prior art, the present invention can be obtained including following technology
Effect:
Preparation method of the invention has depositing current density big, and deposition efficiency is high, short preparation period, tellurium product compactness
Good, electrolyte recycles, low in cost, environmental-friendly and the advantages that be easy to industrialization, can be effectively applied to alkaline electro-deposition
4N (99.99%) smart tellurium is prepared, is 5N, the preparation and application of 6N and 7N high purity tellurium provide raw material.
Certainly, it implements any of the products of the present invention it is not absolutely required to while reaching all the above technical effect.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes a part of the invention, this hair
Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the process flow chart of the preparation method of the 4N tellurium the present invention is based on alkaline electrodeposition technology.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below in conjunction with embodiment, whereby to the present invention how application technology hand
Section solves technical problem and reaches the realization process of technical effect to fully understand and implement.
The invention discloses a kind of preparation methods of 4N tellurium based on alkaline electrodeposition technology, comprising the following steps:
Step 1 weighs: weighing following components: 1 part of sodium hydroxide piece, 2~6 parts of ultrapure water, thick titanium dioxide according to parts by weight
1~5 part of telloy；
Load weighted sodium hydroxide piece is added in ultrapure water for step 2, at room temperature, and stirring and dissolving is complete, obtains thermokalite
Liquid；Load weighted thick tellurium dioxide powder is added in heat alkali liquid and be reacted, temperature control is at 70~90 DEG C when reaction, preparation
It obtains being electrolysed preceding liquid；Purity >=60% of tellurium, water content 15~20% in thick tellurium dioxide powder；
Step 3 is added cleanser and carries out purified treatment to liquid before being electrolysed, and temperature control is at 70~90 DEG C when processing, filtering,
Electrolyte is prepared；Wherein, cleanser accounts for the 1~10% of thick tellurium dioxide powder quality total amount；Cleanser is vulcanized sodium, sulphur
Change ammonium, thioacetamide, ammonium hydroxide, ammonium thiocyanate, hexamethylenetetramine, disodium edta, ethylenediamine tetraacetic methene phosphoric acid
One of sodium and triethanolamine are a variety of；
It can remove some foreign ions, such as lead, arsenic etc. by the way that cleanser is added, these foreign ion theoretical deposition current potentials
It is close with tellurium, it can be co-deposited and be precipitated with tellurium in electrodeposition process, reduce the purity of smart tellurium, removing these foreign ions can have
Effect ensures the quality of tellurium product；The additional amount of cleanser need to control in thick 1~10% range of tellurium dioxide weight, additional amount mistake
It is high then be likely to result in tellurium and excessive cleanser complexing even precipitate, be unfavorable for the electro-deposition in later period；Additional amount is too low then not
Related impurities ion can be sufficiently removed, keeps the purity of tellurium not up to standard, influences the quality of tellurium.
Electrolyte is cooled to room temperature by step 4, and additive is added, after stirring and dissolving is complete, to electrolyte 0.6~
Constant pressure pre-deposition processing 1~for 24 hours is carried out in 0.8V voltage range, then in 80~100A/m2High current density under Constant Electric Current
12~48h is deposited, electro-deposition product tellurium block is obtained；Wherein, additive account for thick tellurium dioxide powder quality total amount 0.1%~
5%；The purpose of constant pressure pre-deposition is further to clean, and sedimentation potential is true by the theoretical deposition current potential and overpotential of impurity and tellurium
It is fixed；Additive is gelatin, polyacrylamide, chitosan, starch, alum, ferrous sulfate, polysilicon acid, poly-silicic acid iron sulfate and gathers
One of phosphorus iron chloride is a variety of；
The deposition process of tellurium can be optimized by the way that additive is added, improve the compactness of tellurium, enhance tellurium in electrode plate surface
Adhesive force, hinder deposition process in tellurium fall to bottom of electrolytic tank, the steady production of effective guarantee tellurium.The additional amount of additive
It need to control in thick 0.1~5% range of tellurium dioxide weight, additional amount is excessively high, and tellurium product can be made excessively fine and compact, is easy
It is mingled with foreign ion, is unfavorable for final wash；Additional amount is too low, and tellurium cannot be made to reach the compactness of needs, and tellurium is made to be easy to fall
To bottom of electrolytic tank, influence to produce.
Step 5 after removing tellurium block from electrode plate, for several times with milli-Q water, is then dried, and 4N tellurium is prepared；
The concentration of leading ion in electrolytic liquid is monitored online in step 6, with tellurium dioxide raw material, sodium hydroxide,
Electrolyte and ultrapure water are adjusted, and after leading ion concentration is up to standard in electrolytic liquid, electrolytic liquid are changed into electrolyte and is followed
Ring utilizes；
Leading ion includes tellurious acid ion, hydroxide ion and foreign ion, leading ion concentration in electrolytic liquid
Condition up to standard are as follows: control the concentration of tellurious acid ion in 200~300g/L, the concentration control of hydroxide ion 80~
120g/L, concentration impurity ion are controlled in Pb < 20ppm, Se < 30ppm.
The alkaline electrodeposition technology of the present invention for being used to prepare high purity tellurium mainly includes that the preparation of electrolyte (including is matched
Set, purify and optimize), the concentration measurement and control of electrolyte, the control of electrodeposition condition and tellurium product washing.The preparation of electrolyte
Journey include thick tellurium dioxide raw material is dissolved in lye obtain be electrolysed before liquid, it is pure to will affect electro-deposition tellurium product in liquid before being electrolysed
The impurity of degree removes or is formed complex compound and purified, and flocculant, which is then added, makes the tellurium in electrolyte is uniform and stable to be deposited on
Electrode plate surface.The concentration measurement and control of electrolyte includes the dense of the concentration of liquid before being electrolysed, the online concentration of electrolyte and electrolytic liquid
Degree monitoring control.The control of electrodeposition condition includes controlling pre-deposition current potential in 0.6~0.8V, deposition current in 80~100A/
M2, tank voltage in 1.5~1.7V, overpotential in 10~100mV, sedimentation time in 12~48h and depositing temperature at 25~45 DEG C.
The washing of tellurium product includes the selection of washing methods, the control for washing water, wash temperature and wash time.It is of the present invention
Alkaline electrodeposition technology has depositing current density big, and deposition efficiency is high, and short preparation period, tellurium product compactness is good, electrolyte
It recycles, it is low in cost, it is environmental-friendly and the advantages that be easy to industrialization, it can be effectively applied to alkaline electro-deposition preparation 4N
(99.99%) smart tellurium, is 5N, and the preparation and application of 6N and 7N high purity tellurium provide raw material.
Embodiment 1
The step of the present embodiment and process conditions are as follows:
100g sodium hydroxide piece is added in 200g ultrapure water, stirring and dissolving is complete, obtains heat alkali liquid.By the thick dioxy of 200g
Changing tellurium, (tellurium 60%, aqueous 15%) powder are added in heat alkali liquid, and temperature control is at 80 DEG C when reaction, before being electrolysed after reaction
Liquid.3g vulcanized sodium is added in liquid to before being electrolysed to be purified, temperature control is at 90 DEG C when processing, and filtering is electrolysed after processing
Liquid.Electrolyte is cooled to room temperature, 0.5g gelatin is added, after stirring and dissolving is complete, carries out perseverance under the conditions of 0.8V to electrolyte
Pre-deposition is pressed to handle 1h, then in 85A/m2High current density under constant current electro-deposition 30h, obtain electro-deposition product tellurium block.It will
After tellurium block is removed from electrode plate, for several times with milli-Q water, then dry, sample detection is spare.Simultaneously in electrolytic liquid
The concentration of tellurious acid ion, hydroxide ion and foreign ion is monitored online, with tellurium dioxide raw material, sodium hydroxide,
Electrolyte and ultrapure water are adjusted, and after leading ion concentration is up to standard in electrolytic liquid, leading ion concentration reaches in electrolytic liquid
Target condition are as follows: control the concentration of tellurious acid ion in 200~300g/L, the concentration control of hydroxide ion 80~
120g/L, concentration impurity ion are controlled in Pb < 20ppm, Se < 30ppm；Electrolytic liquid is changed into electrolyte to recycle.Electricity
Deposition does not find that bottom of electrolytic tank has the tellurium product fallen three times, and the tellurium sample average purity of acquisition is 99.9987%.
Tellurium ingredient, current efficiency and the purity obtained under the alkaline Electrodeposition Conditions of 1 embodiment of table 1
| Sample | Se | Sn | As | Zn | Ca | Ni | Fe | Bi | Pb | Cu | Current efficiency | Tellurium purity |
| Concentration (mg/L) | 1.79 | — | 1.35 | — | — | — | 7.82 | 1.26 | 0.21 | 0.88 | 98.28% | 99.9987% |
Remarks: "-" expression does not detect, and detects beyond equipment offline.
Embodiment 2
120g sodium hydroxide piece is added in 300g ultrapure water, stirring and dissolving is complete, obtains heat alkali liquid.By the thick dioxy of 230g
Changing tellurium, (tellurium 60%, aqueous 15%) powder are added in heat alkali liquid, and temperature control is at 90 DEG C when reaction, before being electrolysed after reaction
Liquid.5g ammonium thiocyanate is added in liquid to before being electrolysed to be purified, temperature control is at 85 DEG C when processing, and filtering is electrolysed after processing
Liquid.Electrolyte is cooled to room temperature, be added 3g polyacrylamide, after stirring and dissolving is complete, to electrolyte under the conditions of 0.75V into
Row constant pressure pre-deposition handles 8h, then in 90A/m2High current density under constant current electro-deposition 25h, obtain electro-deposition product tellurium
Block.After tellurium block is removed from electrode plate, for several times with milli-Q water, then dry, sample detection is spare.Simultaneously to electrolysis after
The concentration of liquid Central Asia tellurate ion, hydroxide ion and foreign ion is monitored online, with tellurium dioxide raw material, hydroxide
Sodium, electrolyte and ultrapure water are adjusted, after leading ion concentration is up to standard in electrolytic liquid, leading ion concentration in electrolytic liquid
Condition up to standard are as follows: control the concentration of tellurious acid ion in 200~300g/L, the concentration control of hydroxide ion 80~
120g/L, concentration impurity ion are controlled in Pb < 20ppm, Se < 30ppm；Electrolytic liquid is changed into electrolyte to recycle.Electricity
Deposition does not find that bottom of electrolytic tank has the tellurium product fallen three times, and the tellurium sample average purity of acquisition is 99.9945%.
Tellurium ingredient, current efficiency and the purity obtained under the alkaline Electrodeposition Conditions of 2 embodiment of table 2
| Sample | Se | Sn | As | Zn | Ca | Ni | Fe | Bi | Pb | Cu | Current efficiency | Tellurium purity |
| Concentration (mg/L | 9.98 | 8.85 | 3.65 | 3.94 | 9.03 | 1.16 | 9 | 2.02 | 2.30 | 5.46 | 99.23% | 99.9945% |
Embodiment 3
150g sodium hydroxide piece is added in 400g ultrapure water, stirring and dissolving is complete, obtains heat alkali liquid.By the thick dioxy of 280g
Changing tellurium, (tellurium 60%, aqueous 15%) powder are added in heat alkali liquid, and temperature control is at 85 DEG C when reaction, before being electrolysed after reaction
Liquid.7g water ammonium sulfide is added in liquid to before being electrolysed to be purified, temperature control is at 85 DEG C when processing, and filtering is electrolysed after processing
Liquid.Electrolyte is cooled to room temperature, 14g chitosan is added, after stirring and dissolving is complete, electrolyte is carried out under the conditions of 0.72V
Constant pressure pre-deposition handles 12h, then in 95A/m2High current density under constant current electro-deposition 20h, obtain electro-deposition product tellurium block.
It after tellurium block is removed from electrode plate, for several times with milli-Q water, then dries, sample detection is spare while in electrolytic liquid
The concentration of tellurious acid ion, hydroxide ion and foreign ion is monitored online, with tellurium dioxide raw material, sodium hydroxide,
Electrolyte and ultrapure water are adjusted, and after leading ion concentration is up to standard in electrolytic liquid, leading ion concentration reaches in electrolytic liquid
Target condition are as follows: control the concentration of tellurious acid ion in 200~300g/L, the concentration control of hydroxide ion 80~
120g/L, concentration impurity ion are controlled in Pb < 20ppm, Se < 30ppm；Electrolytic liquid is changed into electrolyte to recycle.Electricity
Deposition does not find that bottom of electrolytic tank has the tellurium product fallen three times, and the tellurium sample average purity of acquisition is 99.9927%.
Tellurium ingredient, current efficiency and the purity obtained under the alkaline Electrodeposition Conditions of 3 embodiment of table 3
| Sample | Se | Sn | As | Zn | Ca | Ni | Fe | Bi | Pb | Cu | Current efficiency | Tellurium purity (% |
| Concentration (mg/L) | 9.26 | 9.44 | 4.89 | 7.56 | 9.87 | 5.42 | 8.26 | 5.15 | 4.37 | 9.15 | 98.53% | 99.9927 |
Embodiment 4
100g sodium hydroxide piece is added in 600g ultrapure water, stirring and dissolving is complete, obtains heat alkali liquid.By the thick dioxy of 500g
Changing tellurium, (tellurium 62%, aqueous 17%) powder are added in heat alkali liquid, and temperature control is at 70 DEG C when reaction, before being electrolysed after reaction
Liquid.5g disodium edta is added in liquid to before being electrolysed to be purified, temperature control is filtered after processing at 70 DEG C when processing
Obtain electrolyte.Electrolyte is cooled to room temperature, 5g ferrous sulfate is added, after stirring and dissolving is complete, to electrolyte in 0.7V item
Constant pressure pre-deposition is carried out under part and handles 18h, then in 80A/m2High current density under constant current electro-deposition 48h, obtain electro-deposition
Product tellurium block.It after tellurium block is removed from electrode plate, for several times with milli-Q water, then dries, sample detection is spare while right
The concentration of electrolytic liquid Central Asia tellurate ion, hydroxide ion and foreign ion is monitored online, with tellurium dioxide raw material,
Sodium hydroxide, electrolyte and ultrapure water are adjusted, after leading ion concentration is up to standard in electrolytic liquid, in electrolytic liquid mainly from
Sub- concentration condition up to standard are as follows: control the concentration of tellurious acid ion in 200~300g/L, the concentration of hydroxide ion controls
In 80~120g/L, concentration impurity ion is controlled in Pb < 20ppm, Se < 30ppm；Electrolytic liquid is changed into electrolyte circulation benefit
With.Electro-deposition does not find that bottom of electrolytic tank has the tellurium product fallen three times, and the tellurium sample average purity of acquisition is
99.99379981%.
Tellurium ingredient, current efficiency and the purity obtained under the alkaline Electrodeposition Conditions of 4 embodiment of table 4
| Sample | Se | Sn | As | Zn | Ca | Ni | Fe | Bi | Pb | Cu | Current efficiency | Tellurium purity (%) |
| Concentration (mg/L) | 2.56 | 3.15 | 2.36 | - | - | - | 7.62 | 2.31 | 1.02 | 0.23 | 98.62% | 99.99379981 |
Embodiment 5
100g sodium hydroxide piece is added in 400g ultrapure water, stirring and dissolving is complete, obtains heat alkali liquid.By the thick dioxy of 100g
Changing tellurium, (tellurium 65%, aqueous 20%) powder are added in heat alkali liquid, and temperature control is at 90 DEG C when reaction, before being electrolysed after reaction
Liquid.Six methine of 10g, four ammonium amine is added in liquid to before being electrolysed to be purified, temperature control is filtered after processing at 90 DEG C when processing
Obtain electrolyte.Electrolyte is cooled to room temperature, 0.1g poly-silicic acid iron sulfate is added, after stirring and dissolving is complete, exists to electrolyte
The processing of constant pressure pre-deposition is carried out for 24 hours under the conditions of 0.6V, then in 120A/m2High current density under constant current electro-deposition 12h, obtain
Electro-deposition product tellurium block.After tellurium block is removed from electrode plate, for several times with milli-Q water, then dry, sample detection is spare
The concentration of electrolytic liquid Central Asia tellurate ion, hydroxide ion and foreign ion is monitored online simultaneously, uses titanium dioxide
Tellurium raw material, sodium hydroxide, electrolyte and ultrapure water are adjusted, after leading ion concentration is up to standard in electrolytic liquid, electrolytic liquid
Middle leading ion concentration condition up to standard are as follows: control the concentration of tellurious acid ion in 200~300g/L, hydroxide ion
Concentration control is controlled in 80~120g/L, concentration impurity ion in Pb < 20ppm, Se < 30ppm；Electrolytic liquid is changed into electrolysis
Liquid recycles.Electro-deposition does not find that bottom of electrolytic tank has the tellurium product fallen three times, and the tellurium sample average purity of acquisition is
99.99289963%.
Tellurium ingredient, current efficiency and the purity obtained under the alkaline Electrodeposition Conditions of 5 embodiment of table 5
| Sample | Se | Sn | As | Zn | Ca | Ni | Fe | Bi | Pb | Cu | Current efficiency | Tellurium purity (%) |
| Concentration (mg/L) | 4.56 | 5.32 | 2.15 | 3.92 | 5.62 | 3.26 | 4.65 | 2.36 | 3.56 | 2.06 | 98.23% | 99.99289963 |
Embodiment 1- embodiment 5 the result shows that, the present invention by the preparation (including configuration, purification and optimization) of electrolyte,
The alkaline electrodeposition technology optimization such as the control of the concentration measurement and control, electrodeposition condition of electrolyte and the washing of tellurium product, can obtain
4N essence tellurium, the technique can be effectively applied to alkaline electro-deposition and prepares high purity tellurium.
Above description has shown and described several preferred embodiments of invention, but as previously described, it should be understood that invention is not
It is confined to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification
And environment, and can be carried out within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
Change.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of invention, then it all should be in the appended power of invention
In the protection scope that benefit requires.
Claims (9)
1. a kind of preparation method of the 4N tellurium based on alkaline electrodeposition technology, which comprises the following steps:
Step 1 weighs: weighing following components: 1 part of sodium hydroxide piece, 2~6 parts of ultrapure water, thick tellurium dioxide powder according to parts by weight
1~5 part of end；
Load weighted sodium hydroxide piece is added in ultrapure water for step 2, at room temperature, and stirring and dissolving is complete, obtains heat alkali liquid；It will
Load weighted thick tellurium dioxide powder, which is added in heat alkali liquid, to be reacted, and liquid before electrolysis is prepared；
Cleanser is added to liquid progress purified treatment before being electrolysed in step 3, then filters, electrolyte is prepared；
Electrolyte is cooled to room temperature by step 4, and additive is added, and after stirring and dissolving is complete, carries out constant pressure pre-deposition to electrolyte
Then processing carries out constant current electrodeposition process, obtain electro-deposition product tellurium block and electrolytic liquid；
Step 5 after removing tellurium block from electrode plate, for several times with milli-Q water, is then dried, and 4N tellurium is prepared.
2. the preparation method of the 4N tellurium according to claim 1 based on alkaline electrodeposition technology, which is characterized in that in step
After 5, the concentration of electrolytic liquid Central Asia tellurate ion, hydroxide ion and foreign ion is monitored online, dioxy is used
Change tellurium raw material, sodium hydroxide and ultrapure water to be adjusted, electrolytic liquid Central Asia tellurate ion, hydroxide ion and foreign ion
Concentration it is up to standard after, electrolytic liquid is changed into electrolyte and is recycled.
3. the preparation method of the 4N tellurium according to claim 1 based on alkaline electrodeposition technology, which is characterized in that step 2
In in thick tellurium dioxide raw material tellurium purity >=60%, water content 15%~20%.
4. the preparation method of the 4N tellurium according to claim 1 based on alkaline electrodeposition technology, which is characterized in that step 2
In thick tellurium dioxide powder and temperature when reacting of heat alkali liquid be 70~90 DEG C.
5. the preparation method of the 4N tellurium according to claim 1 based on alkaline electrodeposition technology, which is characterized in that step 3
Middle cleanser is vulcanized sodium, ammonium sulfide, thioacetamide, ammonium hydroxide, ammonium thiocyanate, hexamethylenetetramine, sodium ethylene diamine tetracetate
One of salt, ethylenediamine tetraacetic methene sodium phosphate or triethanolamine are a variety of.
6. the preparation method of the 4N tellurium according to claim 1 based on alkaline electrodeposition technology, which is characterized in that step 3
Middle purified treatment temperature is 70~90 DEG C；Cleanser accounts for the 1~10% of thick tellurium dioxide powder quality total amount.
7. the preparation method of the 4N tellurium according to claim 1 based on alkaline electrodeposition technology, which is characterized in that step 4
Middle additive is gelatin, polyacrylamide, chitosan, starch, alum, ferrous sulfate, polysilicon acid, poly-silicic acid iron sulfate or poly- phosphorus
One of iron chloride is a variety of.
8. the preparation method of the 4N tellurium according to claim 1 based on alkaline electrodeposition technology, which is characterized in that step 4
Middle constant pressure pre-deposition processing voltage is 0.6~0.8V, constant pressure pre-deposition handle the time be 1~for 24 hours；The electric current of constant current electro-deposition is close
Degree is 80~100A/m2；Constant current electrodeposition time is 12~48h；Additive accounts for the 0.1% of thick tellurium dioxide powder quality total amount
~5%.
9. the preparation method of the 4N tellurium according to claim 2 based on alkaline electrodeposition technology, which is characterized in that step 6
The concentration condition up to standard of middle electrolytic liquid Central Asia tellurate ion, hydroxide ion and foreign ion are as follows: tellurious acid ion
Concentration control in 200~300g/L, the concentration control of hydroxide ion in 80~120g/L, concentration impurity ion control Pb <
20ppm, Se < 30ppm.
Priority Applications (1)
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| CN110127632B (en) * | 2019-05-13 | 2022-09-02 | 四川大学 | Method for recovering tellurium from bismuth telluride-based semiconductor refrigeration sheet waste |
| CN110195233A (en) * | 2019-07-22 | 2019-09-03 | 阳谷祥光铜业有限公司 | A kind of close continuous technique for extracting tellurium of big electricity |
| CN110656338B (en) * | 2019-09-19 | 2020-09-29 | 中南大学 | Method for deeply recycling tellurium through step cyclone electrolysis |
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| CN104233362A (en) * | 2014-09-18 | 2014-12-24 | 株洲科能新材料有限责任公司 | Preparation method for high-purity tellurium |
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| CN104233362A (en) * | 2014-09-18 | 2014-12-24 | 株洲科能新材料有限责任公司 | Preparation method for high-purity tellurium |
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