CN116328674A - Production device and production method for preparing 5N high-purity tellurium from 2N crude tellurium - Google Patents
Production device and production method for preparing 5N high-purity tellurium from 2N crude tellurium Download PDFInfo
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- CN116328674A CN116328674A CN202310082963.XA CN202310082963A CN116328674A CN 116328674 A CN116328674 A CN 116328674A CN 202310082963 A CN202310082963 A CN 202310082963A CN 116328674 A CN116328674 A CN 116328674A
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 238000009833 condensation Methods 0.000 claims abstract description 175
- 230000005494 condensation Effects 0.000 claims abstract description 122
- 238000004821 distillation Methods 0.000 claims abstract description 104
- 238000005070 sampling Methods 0.000 claims abstract description 34
- 238000005292 vacuum distillation Methods 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 42
- 238000004321 preservation Methods 0.000 claims description 22
- 239000011261 inert gas Substances 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005273 aeration Methods 0.000 claims 2
- 239000012535 impurity Substances 0.000 abstract description 57
- 238000000034 method Methods 0.000 abstract description 17
- 238000005204 segregation Methods 0.000 abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 40
- 229910002804 graphite Inorganic materials 0.000 description 38
- 239000010439 graphite Substances 0.000 description 38
- 239000000047 product Substances 0.000 description 31
- 230000001276 controlling effect Effects 0.000 description 17
- 238000001514 detection method Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000011068 loading method Methods 0.000 description 13
- 238000005086 pumping Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 8
- 239000007859 condensation product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910004613 CdTe Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010005 wet pre-treatment Methods 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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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
- C01B19/02—Elemental selenium or tellurium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
-
- 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
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- 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
- B01J19/0006—Controlling or regulating processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a production device for preparing 5N high-purity tellurium by using 2N crude tellurium, which comprises a distillation-condensation system and a vacuum degree control system for controlling the vacuum degree in the distillation-condensation system, wherein the distillation-condensation system sequentially comprises a distillation section, a primary condensation section, a secondary condensation section and a tertiary condensation section from bottom to top, the primary condensation section, the secondary condensation section and the tertiary condensation section are provided with condensation temperature control devices for controlling the temperature of each condensation section to sequentially become lower from the lower condensation section to the upper condensation section, and the distillation section is provided with the distillation temperature control device. The invention also provides a production method for preparing 5N high-purity tellurium by using the production device. The invention has the advantages of short production period, short flow, basically no reagent consumption, simple operation, good impurity segregation effect, convenient sampling, and the like, and the high-purity product is mainly concentrated in the secondary condensation section without causing secondary pollution in the sampling process, thereby having wide market application prospect.
Description
Technical Field
The invention belongs to the field of tellurium purification, and particularly relates to a device and a method for purifying crude tellurium.
Background
Tellurium belongs to semi-metal, has obvious metal property, and is widely applied in the fields of national defense, military industry, aerospace, semiconductors, electronic communication and the like, for example: cdTe is one of important solar cell materials, hgCdTe, znCdTe, pbSnTe is an important material for researching infrared detection, and BiTe and PbTe are good refrigeration function materials. Trace impurities in tellurium can directly influence the material performance, for example, the impurities can cause point defects of CdTe materials, so that the heat treatment process of the CdTe materials is influenced, the forbidden band width of the CdTe is reduced, and the photoelectric conversion efficiency of an absorption layer is reduced. Thus, tellurium purification is of great significance.
Crude tellurium purification techniques include chemical and physical methods. The chemical purification includes precipitation, aqueous solution reduction, electrolysis, extraction, etc. For example, chinese patent CN106276820a discloses a method for preparing high-purity tellurium from crude tellurium powder, which comprises the steps of heating and rinsing crude tellurium powder, pressurizing and oxidizing alkaline leaching of washing slag, neutralizing and precipitating the alkaline leaching liquid with dilute sulfuric acid to obtain precipitate slag; leaching the oxidized alkaline leaching slag by dilute sulfuric acid, and carrying out neutralization and oxalic acid reduction treatment on the pickling liquid to obtain precipitation slag; and (3) performing alkaline leaching liquid making on the precipitation slag obtained in the last two steps, and performing electrolytic refining to obtain high-purity tellurium. The chemical purification method needs to perform wet pretreatment on raw materials, and has the advantages of long flow, complex operation, large reagent consumption, large pollution risk in the operation process and lower current efficiency in electrolysis.
Compared with a chemical method, the physical method purification of crude tellurium can avoid a large amount of reagent consumption, reduce pollution risk and shorten the operation flow to a certain extent. Physical purification of crude tellurium comprises vacuum distillation, zone melting, direct-pulling purification, solid-state electromigration and the like. Tellurium belongs to low-melting-point high-saturation vapor pressure metal, and most impurities in tellurium can be effectively separated by vacuum distillation to obtain distilled tellurium with higher purity, so that the vacuum distillation technology is widely applied. In the prior art for preparing high-purity metal by vacuum distillation, 4N metal is mostly used as a raw material, and 5N-6N high-purity metal is prepared by multiple times of distillation. For example, chinese patent No. CN107313063A discloses a 5N high-purity tellurium smelting method, which comprises the steps of preparing 4N tellurium by a low-current density electro-deposition method, and carrying out low-temperature vacuum distillation on a 4N tellurium ingot to obtain distilled tellurium; and finally, crushing the distilled tellurium into small particles, and heating and casting the ingot under the action of hydrogen flow to obtain the 5N high-purity tellurium. The Chinese patent No. 107585745A discloses a 5N tellurium production process, which is characterized in that the content of partial impurities in the raw materials is obviously reduced through screening or pretreatment, the content of impurities which are difficult to separate in the raw materials is obviously reduced, and then vacuum distillation, hydrogenation selenium reduction and intermediate frequency ingot casting are carried out to obtain 5N high-purity tellurium. By adopting the technical scheme of vacuum distillation, the raw materials need to be pretreated, namely 4N tellurium meeting various indexes needs to be obtained, the production period is still longer, the process flow is complicated, and certain reagent consumption exists.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the background technology, and provides a production device and a production method for preparing 5N high-purity tellurium from 2N crude tellurium, which have the advantages of short production period, simple process, high impurity removal efficiency and no reagent consumption. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the utility model provides a production device with 2N crude tellurium preparation 5N high purity tellurium, includes distillation-condensing system and is used for controlling vacuum degree control system in the distillation-condensing system, distillation-condensing system is from bottom to top including distillation section, one-level condensation section, second grade condensation section and tertiary condensation section in proper order, be equipped with the condensation temperature regulating device that is used for controlling each condensation section temperature to become low in proper order from below condensation section to top condensation section (i.e. first grade condensation section, second grade condensation section and tertiary condensation section become low in proper order) on one-level condensation section, be equipped with distillation temperature regulating device on the distillation section.
In the above production device, preferably, a first perforated baffle is arranged between the distillation section and the primary condensation section, a second perforated baffle is arranged between the primary condensation section and the secondary condensation section, and a third perforated baffle is arranged between the secondary condensation section and the tertiary condensation section.
In the above production device, preferably, the first perforated baffle plate is uniformly provided with a plurality of first through holes, the middle position of the second perforated baffle plate is provided with a second through hole, and the middle position of the third perforated baffle plate is provided with a third through hole; the diameter of the first through hole is 3-4mm, the total area of the openings accounts for 25-30% of the total area of the first opening baffle, the area of the second through hole accounts for 20-25% of the total area of the second opening baffle, and the area of the third through hole accounts for 15-20% of the total area of the third opening baffle. More preferably, the diameter of the first through holes is 3mm, 328 through holes are uniformly distributed, the total area of the holes accounts for 29.5% of the total area of the first hole baffle, the area of the holes of the second through holes accounts for 25% of the total area of the second hole baffle, and the area of the holes of the third through holes accounts for 16% of the total area of the third hole baffle.
In the above production device, preferably, the condensation temperature control device comprises a first heating device, a second heat preservation device and a third cooling device from bottom to top in sequence, wherein the first heating device is arranged on the first-stage condensation section and the middle lower part (about 1/3 of the lower part of the second-stage condensation section is covered by the second-stage condensation device) and is adjacent to the distillation temperature control device, the second heat preservation device is arranged on the middle upper part of the second-stage condensation section and is adjacent to the first heating device, and the third cooling device is arranged on the third-stage condensation section and is used for rapidly reducing the temperature in the third-stage condensation section. The first heating device can provide a heat source for heating, the second heat preservation device can not provide a heat source (such as a detachable heat insulation plate) for heat preservation, and the third cooling device can adopt a cooling water cooling system for rapid cooling. The first heating device and the distillation temperature control device can be also provided with an insulation layer selectively.
In the above production apparatus, preferably, the vacuum degree control system includes a sealed housing, and an air-extracting and inflating assembly provided on the sealed housing, and the distillation-condensing system is provided in the sealed housing.
As a general technical concept, the present invention also provides a method for preparing 5N high purity tellurium from 2N crude tellurium using the above production device, comprising the steps of:
(1) Placing 2N crude tellurium powder into the distillation section, sealing the distillation-condensation system, evacuating, setting the set temperature of the distillation temperature control device to be 530-560 ℃, setting the set temperature of the condensation temperature control device at the first condensation section to be 430-460 ℃ for one-step vacuum distillation, and sampling from the second condensation section after the one-step vacuum distillation is finished to obtain a one-step vacuum distillation product;
(2) Placing the one-step vacuum distillation product obtained in the step into the distillation section, sealing the distillation-condensation system, evacuating, setting the set temperature of the distillation temperature control device to be 510-540 ℃, setting the set temperature of the condensation temperature control device at the first-stage condensation section to be 430-460 ℃ for two-step vacuum distillation, and sampling from the second-stage condensation section after the two-step vacuum distillation is finished to obtain a two-step vacuum distillation product;
(3) And (3) placing the two-step vacuum distillation product obtained in the step into the distillation section, sealing the distillation-condensation system, evacuating, setting the set temperature of the distillation temperature control device to be 570-600 ℃, setting the set temperature of the condensation temperature control device at the first-stage condensation section to be 420-450 ℃ for three-step vacuum distillation, and sampling from the second-stage condensation section after the three-step vacuum distillation is finished to obtain the 5N high-purity tellurium.
In the above production method, preferably, the set temperature of the distillation temperature control device is 10-30 ℃ lower than the set temperature of the distillation temperature control device in the one-step vacuum distillation.
In the above production method, preferably, the distillation time of the one-step vacuum distillation and the two-step vacuum distillation is controlled to be 4 to 6 hours; the distillation time of the three-step vacuum distillation is controlled to be 1-3h. In the invention, the distillation temperature of the one-step vacuum distillation and the two-step vacuum distillation is lower, the sample volatilization rate is slower, and the separation of low-volatility impurities and main metals and the segregation efficiency of high-volatility impurities and main metals are facilitated, so that the distillation time is relatively longer. The three-step vacuum distillation has higher distillation temperature and high volatilization rate, so the distillation time is relatively short.
In the above production method, preferably, the one-step vacuum distillation, the two-step vacuum distillation and the three-step vacuum distillation are performed with a vacuum degree of 0.01Pa or less.
In the above production method, preferably, at the end of the one-step vacuum distillation, the two-step vacuum distillation and the three-step vacuum distillation, inert gas is filled into the distillation-condensation system to normal pressure through the vacuum degree control system, wherein the inert gas is N2 or Ar, and the purity is 5N.
According to the invention, 2N tellurium powder is used as a raw material, impurities in the raw material are separated into high-volatility impurities and medium-volatility and low-volatility impurities through calculation and analysis, the raw material is subjected to fractional temperature control distillation and fractional condensation, the impurities are removed in a sectional manner, the purity of a distilled product reaches 5N, and the impurities reach below a standard value. The specific principle of the invention is as follows:
impurities were classified by calculating the saturated vapor pressure of the impurities at each temperature as shown in table 1 below:
table 1: saturated vapor pressure of each element at each temperature
Impurities are classified into high-volatility impurities such as S, K, as, se, na, etc., medium-and low-volatility impurities such as Ca, mn, al, fe, cu, etc. Wherein, the saturated vapor pressure of Se, na, mg and other impurities is relatively close to that of tellurium, and the Se, na, mg and other impurities are difficult to remove by a conventional vacuum distillation method. The invention adopts the technology of step-by-step impurity removal, multi-stage temperature control and multi-stage condensation to realize the accurate impurity removal.
The vapor pressure of the impurities is related to the content of the impurities in tellurium, and the crude tellurium powder contains Ca, mn, al, fe, cu and other low-volatility impurities with higher content, and the vapor pressure of the low-volatility impurities at lower temperature is greatly different from that of tellurium, so that the first step adopts vacuum distillation at lower temperature, thereby ensuring that the tellurium and the high-volatility impurities volatilize in a large quantity, and the low-volatility impurities basically do not volatilize and remain in distilled slag, so that primary separation of main metal tellurium and the impurities is realized. And in the second step, vacuum distillation at a lower temperature is adopted, so that the distillation rate is further reduced, and the separation efficiency of low-volatility impurities and tellurium and the segregation efficiency of high-volatility impurities and tellurium are improved. And the third step adopts high-temperature vacuum distillation to improve the distillation rate and further reduce the impurity content. The impurities are removed step by vacuum distillation step by step, and the impurity removal is efficient.
On the basis of step vacuum distillation, multi-stage temperature control is performed to finely control the volatilization rate of metal and the segregation efficiency of impurities and main metal. Two sections of temperature control are adopted, one section of temperature control is used for controlling the condensing section, and the two sections of temperature control maintain the raw materials in a molten state, so that tellurium is continuously volatilized at a stable volatilization rate; the first-stage temperature control and the second-stage temperature control are coupled to maintain the balance of the system. And when the temperature is controlled in the first stage, the temperatures of the first-stage condensation section, the second-stage condensation section and the third-stage condensation section are controlled, the condensation rate of impurities and main metal tellurium is reduced, and the impurities and the main metal tellurium are fully separated, so that the segregation effect of the impurities is improved. Specifically, the first heating device covers the whole first-stage condensation section and 1/3 of the lower part of the second-stage condensation section. The second heat preservation device covers the middle upper part of the second-stage condensation section, prevents excessive temperature loss and saves energy. And a third cooling device is adopted on the three-stage condensation section, the temperature is controlled by utilizing circulating cooling water in a coordinated manner, so that the temperature is reduced rapidly, the residual volatile matters are fully condensed, and when the temperature is controlled, the cooling water temperature is controlled to be 20-25 ℃ and the flow is controlled to be 1.0-1.6L/s.
Based on two-stage temperature control, volatile matters are controlled to be subjected to fractional condensation. The condensation is divided into three stages, and the first stage condensation mainly condenses a small amount of volatile low-volatility impurities. The first perforated baffle plate can adopt a porous graphite baffle plate, so that volatilized tellurium and impurities are uniformly dispersed, and the segregation efficiency of tellurium and impurities is improved. The second perforated baffle can adopt a macroporous graphite ring baffle, so that most volatile substances can smoothly pass through the round holes, and volatile low-volatility impurities are retained at the same time, so that the separation of high-purity tellurium products and low-volatility impurities is realized. The second-stage condensation is a main condensation section, and because of the residual temperature of one section of heating, the high-volatility impurities in the section are basically not condensed, and the metal tellurium is largely condensed, so that the separation of the high-purity tellurium product and the high-volatility impurities is realized. The third perforated baffle plate can adopt a small-hole graphite ring baffle plate, so that volatilized tellurium is fully condensed at the second stage, the loss rate of tellurium is reduced, and meanwhile, high-volatility impurities are enriched at the third stage condensation position. The segregation principle is shown in figure 4.
The first-stage condensation product and the third-stage condensation product can be respectively collected, and the first-stage condensation product can be further subjected to low-temperature vacuum distillation treatment due to the high content of low-volatility impurities; the three-stage condensation product has high content of volatile impurities and can be further processed by high-temperature vacuum distillation. The second-stage condensation product is purified high-purity tellurium. The first-stage condensation product can be singly collected for low-temperature distillation, the third-stage condensation product can be singly collected for high-temperature distillation, the utilization rate of raw materials is high, the recovery rate is high, and the product purity is high.
In the invention, the same distillation-condensation system can be adopted in the one-step vacuum distillation, the two-step vacuum distillation and the three-step vacuum distillation, and only a cleaning procedure is needed before each step of vacuum distillation. Of course, multiple distillation-condensation systems may be employed. Taking the same distillation-condensation system as an example, the specific operation and parameters of the present invention can be as follows:
(1) First step, low temperature vacuum distillation: 1) Sample loading: 1.0-3.0kg of 2N crude tellurium powder is put into a graphite crucible, the crucible is put into a distillation section, and a distillation-condensation system is sealed; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 8-12h; 3) Heating: setting the set temperature of the distillation temperature control device to be 530-560 ℃, setting the set temperature of the first heating device to be 430-460 ℃, controlling the distillation heat preservation time to be 4-6h, and maintaining the vacuum degree of the system to be below 0.01Pa in the distillation process; 4) Sampling: and (3) after the distillation-condensation system is cooled to room temperature, filling inert gas to normal pressure, sampling, and cleaning the graphite crucible and the distillation-condensation system.
(2) And a second step of low-temperature vacuum distillation: 1) Sample loading: placing all products of the second-stage condensation section and distilled products above 1/5 of the upper part of the first-stage condensation section in a graphite crucible, placing the graphite crucible in the distillation section, and sealing a distillation-condensation system; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1-2h; 3) Heating: setting the set temperature of the distillation temperature control device to be 510-540 ℃, setting the set temperature of the first heating device to be 430-460 ℃, controlling the distillation heat preservation time to be 4-6h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: and (3) after the distillation-condensation system is cooled to room temperature, filling inert gas to normal pressure, sampling, and cleaning the graphite crucible and the distillation-condensation system.
(3) And step three, high-temperature vacuum distillation: 1) Sample loading: placing all products of the second-stage condensation section and distilled products above 1/5 of the upper part of the first-stage condensation section in a graphite crucible, loading the crucible into the distillation section, and sealing a distillation-condensation system; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1-2h; 3) Heating: setting the set temperature of the distillation temperature control device to 570-600 ℃, setting the set temperature of the first heating device to 420-450 ℃, controlling the distillation heat preservation time to 1-3h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: and (3) after the distillation-condensation system is cooled to room temperature, filling inert gas to normal pressure, sampling from the secondary condensation section to obtain 5N high-purity tellurium, and cleaning a graphite crucible and the distillation-condensation system.
Compared with the prior art, the invention has the advantages that:
the production device and the production method for preparing the 5N high-purity tellurium by using the 2N crude tellurium adopt the methods of step vacuum distillation, multi-stage temperature control and multi-stage condensation, the 2N high-purity tellurium can be directly prepared from the 2N tellurium powder through vacuum distillation, impurities reach below standard values, and compared with the existing technology for preparing the 5N high-purity tellurium from the crude tellurium powder, the production device and the production method have the advantages of short production period, short flow, basically no reagent consumption, simplicity in operation, good impurity segregation effect, convenience in sampling, main concentration of the high-purity product in a secondary condensation section, no secondary pollution in the sampling process and the like, and have wide market application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural diagram of a production apparatus for preparing 5N high-purity tellurium from 2N crude tellurium.
Fig. 2 is a schematic structural view of the first perforated baffle plate in fig. 1.
Fig. 3 is a schematic structural view of the second perforated baffle plate in fig. 1.
Fig. 4 is a schematic drawing showing the segregation principle of the production method of preparing 5N high purity tellurium from 2N crude tellurium.
Legend description:
1. a distillation-condensation system; 11. a distillation section; 12. a first-stage condensation section; 13. a second-stage condensing section; 14. a third-stage condensation section; 15. a first perforated baffle; 151. a first through hole; 16. a second perforated baffle; 161. a second through hole; 17. a third perforated baffle; 171. a third through hole; 18. a condensing temperature control device; 181. a first heating device; 182. a second heat preservation device; 183. a third cooling device; 19. a distillation temperature control device; 2. a vacuum control system; 21. a seal housing; 22. an air extraction-inflation assembly.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
as shown in fig. 1, the production device for preparing 5N high-purity tellurium from 2N crude tellurium in this embodiment includes a distillation-condensation system 1 and a vacuum control system 2 for controlling the vacuum degree in the distillation-condensation system 1, wherein the distillation-condensation system 1 includes, from bottom to top, a distillation section 11, a primary condensation section 12, a secondary condensation section 13 and a tertiary condensation section 14, the primary condensation section 12, the secondary condensation section 13 and the tertiary condensation section 14 are provided with a condensation temperature control device 18 for controlling the temperature of each condensation section to sequentially decrease from the lower condensation section to the upper condensation section, and the distillation section 11 is provided with a distillation temperature control device 19.
As shown in fig. 2 and 3, in this embodiment, a first perforated baffle 15 is disposed between the distillation section 11 and the first condensation section 12, a second perforated baffle 16 is disposed between the first condensation section 12 and the second condensation section 13, and a third perforated baffle 17 is disposed between the second condensation section 13 and the third condensation section 14.
In this embodiment, the first perforated baffle 15 is uniformly provided with a plurality of first through holes 151, the middle position of the second perforated baffle 16 is provided with a second through hole 161, and the middle position of the third perforated baffle 17 is provided with a third through hole 171; the diameter of the first through hole 151 is 3-4mm, the total area of the openings is 25-30% of the total area of the first opening baffle 15, the area of the second through hole 161 is 20-25% of the total area of the second opening baffle 16, and the area of the third through hole 171 is 15-20% of the total area of the third opening baffle 17. In this embodiment, alternatively, the diameter of the first through hole 151 is 3mm, 328 through holes are uniformly distributed, the total area of the openings accounts for 29.5% of the total area of the first opening baffle 15, the area of the openings of the second through holes 161 accounts for 25% of the total area of the second opening baffle 16, and the area of the openings of the third through holes 171 accounts for 16% of the total area of the third opening baffle 17.
In this embodiment, the condensation temperature control device 18 sequentially includes, from bottom to top, a first heating device 181, a second heat preservation device 182 and a third cooling device 183, where the first heating device 181 is disposed on the first condensation section 12 and 1/3 of the lower portion of the second condensation section 13 and is adjacent to the distillation temperature control device 19, the second heat preservation device 182 is disposed on the middle upper portion of the second condensation section 13 and is adjacent to the first heating device 181, and the third cooling device 183 adopts a cooling water system and is disposed on the third condensation section 14 for rapidly reducing the temperature in the third condensation section 14.
In this embodiment, the vacuum control system 2 includes a sealed housing 21 and an air-extracting and inflating assembly 22, the air-extracting and inflating assembly 22 is disposed on the sealed housing 21, and the distillation-condensation system 1 is disposed in the sealed housing 21. The pump-up assembly 22 may be constructed from conventional components such as bellows, molecular pumps, mechanical pumps, etc.
The production method for preparing 5N high-purity tellurium by using 2N crude tellurium in the embodiment comprises the following steps:
(1) First step, low temperature vacuum distillation: 1) Sample loading: 1.8kg of 2N crude tellurium powder (for detection data see Table 2) was placed in a graphite crucible, the crucible was charged into a distillation section 11, and the distillation-condensation system 1 was sealed; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 9h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 530 ℃, setting the set temperature of the first heating device 181 to 430 ℃, controlling the distillation heat preservation time to 6 hours, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, sampling is carried out, and the graphite crucible and the distillation-condensation system 1 are cleaned.
(2) And a second step of low-temperature vacuum distillation: 1) Sample loading: placing the distillation products at the upper parts of the second-stage condensing section 13 and the first-stage condensing section 12 in a graphite crucible, placing the graphite crucible in the graphite crucible, placing the crucible in the distillation section 11, and sealing the distillation-condensing system 1; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 520 ℃, setting the set temperature of the first heating device 181 to 440 ℃, controlling the distillation heat preservation time to 6 hours, and maintaining the vacuum degree of the system to be less than 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, sampling is carried out, and the graphite crucible and the distillation-condensation system 1 are cleaned.
(3) And step three, high-temperature vacuum distillation: 1) Sample loading: placing the distillation products at the upper parts of the second-stage condensing section 13 and the first-stage condensing section 12 in a graphite crucible, placing the graphite crucible in the graphite crucible, placing the crucible in the distillation section 11, and sealing the distillation-condensing system 1; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 570 ℃, setting the set temperature of the first heating device 181 to 430 ℃, and controlling the distillation heat preservation time to 1h, wherein the vacuum degree of the system is maintained below 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, and 5N high-purity tellurium is obtained by sampling from the secondary condensation section 13 (the product detection data are shown in Table 3), and the graphite crucible and the distillation-condensation system 1 are cleaned.
The product obtained in this example was 1.11kg, with a purity of 5N, and impurity levels below the 5N standard.
The raw material detection data of this example are shown in table 2, and the product detection data only list the required element types in the 5N tellurium national standard, and the sum of the contents of other impurity elements is less than 3ppm, as shown in table 3.
Table 2: raw material detection data
Table 3: product detection data
Example 2:
the production apparatus for producing 5N high-purity tellurium from 2N crude tellurium of this example is the same as that of example 1.
The production method for preparing 5N high-purity tellurium by using 2N crude tellurium in the embodiment comprises the following steps:
(1) First step, low temperature vacuum distillation: 1) Sample loading: 2.5kg of 2N crude tellurium powder (for detection data see Table 4) was placed in a graphite crucible, the crucible was charged into a distillation section 11, and the distillation-condensation system 1 was sealed; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 12h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 540 ℃, setting the set temperature of the first heating device 181 to 440 ℃, controlling the distillation heat preservation time to 5.5h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: and (3) after the distillation-condensation system is cooled to the room temperature, filling inert gas to normal pressure, sampling, and cleaning the graphite crucible and the distillation-condensation system 1.
(2) And a second step of low-temperature vacuum distillation: 1) Sample loading: placing the distillation products at the upper parts of the second-stage condensing section 13 and the first-stage condensing section 12 in a graphite crucible, placing the graphite crucible in the graphite crucible, placing the crucible in the distillation section 11, and sealing the distillation-condensing system 1; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1.5h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 530 ℃, setting the set temperature of the first heating device 181 to 430 ℃, controlling the distillation heat preservation time to 5h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, sampling is carried out, and the graphite crucible and the distillation-condensation system 1 are cleaned.
(3) And step three, high-temperature vacuum distillation: 1) Sample loading: placing the distillation products at the upper parts of the second-stage condensing section 13 and the first-stage condensing section 12 in a graphite crucible, placing the graphite crucible in the graphite crucible, placing the crucible in the distillation section 11, and sealing the distillation-condensing system 1; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1.5h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 590 ℃, setting the set temperature of the first heating device 181 to 430 ℃, controlling the distillation heat preservation time to 1.5h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, and 5N high-purity tellurium is obtained by sampling from the secondary condensation section 13 (the product detection data are shown in Table 5), and the graphite crucible and the distillation-condensation system 1 are cleaned.
The product obtained in this example was 1.53kg, with a purity of 5N, and impurity levels below the 5N standard.
The raw material detection data of this example are shown in table 4, and the product detection data only list the required element types in the 5N tellurium national standard, and the sum of the contents of other impurity elements is less than 3ppm, as shown in table 5.
Table 4: raw material detection data
Table 5: product inspection data
Comparative example 1:
comparative example 1 a step-wise impurity removal technique was not employed as a comparative example to example 1.
The production method for preparing 5N high-purity tellurium by using 2N crude tellurium in the comparative example comprises the following steps:
(1) First step, low temperature vacuum distillation: 1) Sample loading: 1.9kg of 2N crude tellurium powder (for detection data see Table 6) was placed in a graphite crucible, the crucible was charged into a distillation section 11, and the distillation-condensation system 1 was sealed; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 8 hours; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 550 ℃, setting the set temperature of the first heating device 181 to 450 ℃, controlling the distillation heat preservation time to 5h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, sampling is carried out, and the graphite crucible and the distillation-condensation system 1 are cleaned.
(2) And a second step of low-temperature vacuum distillation: 1) Sample loading: placing the distillation products at the upper parts of the second-stage condensing section 13 and the first-stage condensing section 12 in a graphite crucible, placing the graphite crucible in the graphite crucible, placing the crucible in the distillation section 11, and sealing the distillation-condensing system 1; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 550 ℃, setting the set temperature of the first heating device 181 to 450 ℃, controlling the distillation heat preservation time to 5h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, sampling is carried out, and the graphite crucible and the distillation-condensation system 1 are cleaned.
(3) And step three, high-temperature vacuum distillation: 1) Sample loading: placing the distillation products at the upper parts of the second-stage condensing section 13 and the first-stage condensing section 12 in a graphite crucible, placing the graphite crucible in the graphite crucible, placing the crucible in the distillation section 11, and sealing the distillation-condensing system 1; 2) Vacuumizing: pumping the vacuum degree of the system to below 0.01Pa, and maintaining for 1h; 3) Heating: setting the set temperature of the distillation temperature control device 19 to 550 ℃, setting the set temperature of the first heating device 181 to 450 ℃, controlling the distillation heat preservation time to 1h, and maintaining the vacuum degree of the system below 0.01Pa in the distillation process; 4) Sampling: after the distillation-condensation system 1 is cooled to room temperature, inert gas is filled to normal pressure, and 4N7 high-purity tellurium is obtained by sampling from the secondary condensation section 13 (the product detection data are shown in Table 7), and the graphite crucible and the distillation-condensation system 1 are cleaned.
The comparative example shows that the product has 1.39kg, the purity of 4N7, and the impurity Na, mg, al, fe, ca content exceeds the 5N standard.
The raw material detection data of this comparative example are shown in table 6, and the product detection data only show the types of elements required in the 5N tellurium national standard, as shown in table 7.
Table 6: raw material detection data
Table 7: product inspection data
Claims (10)
1. The production device for preparing 5N high-purity tellurium by using 2N crude tellurium is characterized by comprising a distillation-condensation system (1) and a vacuum degree control system (2) for controlling the vacuum degree in the distillation-condensation system (1), wherein the distillation-condensation system (1) sequentially comprises a distillation section (11), a primary condensation section (12), a secondary condensation section (13) and a tertiary condensation section (14) from bottom to top, the primary condensation section (12), the secondary condensation section (13) and the tertiary condensation section (14) are provided with condensation temperature control devices (18) for controlling the temperature of each condensation section to sequentially become lower from the lower condensation section to the upper condensation section, and the distillation section (11) is provided with distillation temperature control devices (19).
2. The production device according to claim 1, wherein a first perforated baffle (15) is arranged between the distillation section (11) and the primary condensation section (12), a second perforated baffle (16) is arranged between the primary condensation section (12) and the secondary condensation section (13), and a third perforated baffle (17) is arranged between the secondary condensation section (13) and the tertiary condensation section (14).
3. The production device according to claim 2, wherein a plurality of first through holes (151) are uniformly formed in the first perforated baffle (15), a second through hole (161) is formed in the middle position of the second perforated baffle (16), and a third through hole (171) is formed in the middle position of the third perforated baffle (17); the diameter of the first through hole (151) is 3-4mm, the total area of the openings accounts for 25-30% of the total area of the first opening baffle plate (15), the opening area of the second through hole (161) accounts for 20-25% of the total area of the second opening baffle plate (16), and the opening area of the third through hole (171) accounts for 15-20% of the total area of the third opening baffle plate (17).
4. A production device according to any one of claims 1-3, wherein the condensation temperature control device (18) comprises a first heating device (181), a second heat preservation device (182) and a third cooling device (183) from bottom to top in sequence, the first heating device (181) is arranged on the primary condensation section (12) and the middle lower part of the secondary condensation section (13) and is adjacent to the distillation temperature control device (19), the second heat preservation device (182) is arranged on the middle upper part of the secondary condensation section (13) and is adjacent to the first heating device (181), and the third cooling device (183) is arranged on the tertiary condensation section (14) and is used for rapidly reducing the temperature in the tertiary condensation section (14).
5. A production plant according to any one of claims 1-3, wherein the vacuum control system (2) comprises a sealed housing (21) and a suction-aeration assembly (22), the suction-aeration assembly (22) being provided on the sealed housing (21), the distillation-condensation system (1) being provided in the sealed housing (21).
6. A production method for producing 5N high purity tellurium from 2N crude tellurium using the production device as set forth in any one of claims 1-5, comprising the steps of:
(1) Placing 2N crude tellurium powder into the distillation section (11), sealing the distillation-condensation system (1) and evacuating, setting the set temperature of the distillation temperature control device (19) to be 530-560 ℃, setting the set temperature of the condensation temperature control device (18) at the first-stage condensation section (12) to be 430-460 ℃ for one-step vacuum distillation, and sampling from the second-stage condensation section (13) after the one-step vacuum distillation is finished to obtain a one-step vacuum distillation product;
(2) Placing the one-step vacuum distillation product obtained in the step (1) into the distillation section (11), sealing the distillation-condensation system (1) and evacuating, setting the set temperature of the distillation temperature-control device (19) to be 510-540 ℃, setting the set temperature of the condensation temperature-control device (18) at the first-stage condensation section (12) to be 430-460 ℃ for two-step vacuum distillation, and sampling from the second-stage condensation section (13) after the two-step vacuum distillation is finished to obtain a two-step vacuum distillation product;
(3) And (3) placing the two-step vacuum distillation product obtained in the step (2) into the distillation section (11), sealing the distillation-condensation system (1), evacuating, setting the set temperature of the distillation temperature control device (19) to be 570-600 ℃, setting the set temperature of the condensation temperature control device (18) at the first-stage condensation section (12) to be 420-450 ℃, carrying out three-step vacuum distillation, and sampling from the second-stage condensation section (13) after the three-step vacuum distillation is finished to obtain the 5N high-purity tellurium.
7. The production method according to claim 6, wherein the set temperature of the distillation temperature control device (19) at the time of the two-step vacuum distillation is 10-30 ℃ lower than the set temperature of the distillation temperature control device (19) at the time of the one-step vacuum distillation.
8. The production method according to claim 6, wherein the distillation time of the one-step vacuum distillation and the two-step vacuum distillation is controlled to be 4 to 6 hours; the distillation time of the three-step vacuum distillation is controlled to be 1-3h.
9. The production method according to any one of claims 6 to 8, wherein the vacuum degree is controlled to be 0.01Pa or less at the time of the one-step vacuum distillation, the two-step vacuum distillation, and the three-step vacuum distillation.
10. The production method according to any one of claims 6 to 8, wherein at the end of the one-step vacuum distillation, the two-step vacuum distillation and the three-step vacuum distillation, inert gas, which is N, is charged into the distillation-condensation system (1) to normal pressure through the vacuum degree control system (2) 2 Or Ar, with a purity of 5N.
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