CN109850856B - Chlorine doping method for high-purity selenium - Google Patents
Chlorine doping method for high-purity selenium Download PDFInfo
- Publication number
- CN109850856B CN109850856B CN201811552070.2A CN201811552070A CN109850856B CN 109850856 B CN109850856 B CN 109850856B CN 201811552070 A CN201811552070 A CN 201811552070A CN 109850856 B CN109850856 B CN 109850856B
- Authority
- CN
- China
- Prior art keywords
- chlorine
- selenium
- purity
- reactor
- purity selenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a chlorine doping method of high-purity selenium, which comprises the following steps: s1: melting; s2: carrying out reaction; s3: rectifying and dechlorinating; s4: preparing materials; s5: vacuum smelting; s6: and (6) discharging. The invention initiatively prepares the stable chlorine seed selenium with the chlorine content of 1000 +/-300 ppm, then mixes the high-purity selenium and the chlorine seed selenium according to the required proportion, obtains the chlorine-doped high-purity selenium product after smelting, has stable process, can produce the chlorine-doped high-purity selenium with the chlorine content of 50-1200 ppm in batches, and meets different requirements of customers.
Description
Technical Field
The invention relates to the field of preparation of high-purity materials, in particular to a chlorine doping method for high-purity selenium.
Background
Currently, selenium is widely used in the fields of electronic industry, glass industry, chemical pigment industry, metallurgical industry, agriculture, biology, cosmetics, medical and health food, etc., particularly in the field of high-precision technology, such as the manufacturing fields of semiconductor devices, photoelectric devices, selenium solar cells, laser devices, lasers and infrared photoconductive materials.
Selenium is a group VIA element and belongs to semimetals. The abundance of selenium in the crust is 9 x 10-6% is mostly present in the sulphide ore in the form of compounds. The solid selenium is divided into amorphous form and hexagonal form, wherein the hexagonal form is the most stable gray selenium. Amorphous selenium is divided into three forms, namely red powder, glassy state and colloidal state. The red amorphous selenium powder is heated to rapidly transform into gray selenium, and the melting point of the gray selenium is 217 ℃. The gray selenium has semiconductor performance and can be used for radio detection and rectification, and the selenium rectifier has the advantages of load resistance, high temperature resistance, good electrical stability and the like.
In addition, selenium is very sensitive to light, and under sufficient light, the conductivity of selenium increases 1000 times. Therefore, by utilizing this characteristic of selenium, selenium is used to manufacture photoresistors and phototubes, and has been widely used in the fields of automatic control, television manufacturing, and the like.
With the market demand for high-purity selenium increasing significantly, special product demands for high-purity selenium have arisen, for example, 50-1200 mg of chlorine is required to be doped into each kilogram of high-purity selenium with a purity of 5N or more. In actual production, other impurities are introduced by doping in the form of chloride salt, and doping in the form of gas is difficult to form stable melt by the reaction of chlorine and selenium due to low solubility of gas in solid under high temperature environment above the melting point of selenium. At a certain temperature, chlorine gas can react with selenium to generate selenium dichloride or selenium tetrachloride, the boiling point of the selenium dichloride is 130 ℃, and the selenium tetrachloride can be sublimated at 190 ℃. While selenium has a melting point of 217 ℃, both compounds are converted into gaseous state at the melting point of selenium, and it is difficult to uniformly incorporate chlorine into selenium. Therefore, how to uniformly and stably dope chlorine into high-purity selenium without introducing other impurities is a technical problem to be solved urgently.
Therefore, it is necessary to design a method for doping high-purity selenium with chlorine to solve the above technical problems.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a method for doping high-purity selenium with chlorine.
In order to achieve the purpose, the invention adopts the following technical scheme: a chlorine doping method for high-purity selenium comprises the following steps:
s1: melting: adding a high-purity selenium raw material into a reactor resistant to chlorine corrosion, placing the reactor in a heater, introducing protective gas into the reactor to replace air, and controlling the temperature in the reactor to be 230-300 ℃ until the high-purity selenium raw material is completely melted;
s2: reaction: controlling the temperature of the high-purity selenium to be 230-300 ℃, then introducing dried chlorine into the reactor at a certain speed, reacting the chlorine with the selenium to form an initial product, stopping introducing the chlorine after the reaction is finished, and introducing protective gas to completely replace free chlorine and chlorine in the reactor;
s3: rectification dechlorination: transferring the initial product into a corrosion-resistant vessel, cooling to obtain metastable chlorine selenium, then placing the vessel containing the metastable chlorine selenium in a quartz rectifying tower, carrying out heat preservation distillation for 1-4 h under the conditions of pressure of 10-200 Pa and temperature of 220-280 ℃, and sampling to detect the chlorine content after charging and discharging;
s4: preparing materials: the method comprises the following steps of (1) mixing chlorine selenium and high-purity selenium according to a target value and a chlorine content analysis result of the chlorine selenium, then filling the chlorine selenium and the high-purity selenium into a quartz tube, and vacuumizing the quartz tube until the vacuum degree is below 10Pa and sealing the quartz tube;
s5: vacuum smelting: placing the sealed quartz tube in a swinging atmosphere furnace, heating to 230-350 ℃ at a heating rate of 100-500 ℃/h, and carrying out heat preservation reaction for 1-6 h;
s6: discharging: discharging after the heat preservation reaction is finished, and breaking the quartz tube to obtain the chlorine-doped high-purity selenium product.
As a further improvement of the invention, in S2, chlorine gas is diluted by protective gas and then reacted with the high-purity selenium raw material.
As a further improvement of the invention, the purity of the high-purity selenium raw material is 5N or more.
As a further improvement of the invention, the protective gas is 4N or more of nitrogen or inert gas.
As a further improvement of the invention, in S3, the chlorine gas is introduced at a flow rate of 0.5-5L/min.
As a further improvement of the invention, in S3, the amount of chlorine gas consumed per 1kg of selenium is 3-10L.
As a further improvement of the invention, the reactor adopts a temperature-resistant glass or quartz reactor.
As a further improvement of the invention, the atmosphere furnace adopts a swinging atmosphere furnace.
As a further improvement of the invention, the corrosion-resistant vessel is a graphite crucible.
As a further improvement of the invention, the reactor comprises a vent which is located at the bottom of the reactor.
The invention initiatively prepares the stable chlorine seed selenium with the chlorine content of 1000 +/-300 ppm, then mixes the high-purity selenium and the chlorine seed selenium according to the required proportion, obtains the chlorine-doped high-purity selenium product after smelting, has stable process, can produce the chlorine-doped high-purity selenium with the chlorine content of 50-1200 ppm in batches, and meets different requirements of customers.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Aiming at the technical problems in the background art, the invention provides a chlorine doping method for high-purity selenium, which comprises the following steps.
S1: melting: adding a high-purity selenium raw material into a reactor resistant to chlorine corrosion, placing the reactor in a heater, introducing protective gas into the reactor to replace air, and controlling the temperature in the reactor at 230-300 ℃ until the high-purity selenium raw material is completely melted.
S2: reaction: controlling the temperature of the high-purity selenium to be 230-300 ℃, then introducing the dried chlorine into the reactor at a certain speed, reacting the chlorine with the selenium to form an initial product, stopping introducing the chlorine after the reaction is finished, and introducing protective gas to completely replace the free chlorine and the chlorine in the reactor.
S3: rectification dechlorination: transferring the initial product into a corrosion-resistant vessel, cooling to obtain metastable chlorine seed selenium, then placing the vessel containing the metastable chlorine seed selenium in a quartz rectifying tower, carrying out heat preservation distillation for 1-4 h under the conditions of the pressure of 10-200 Pa and the temperature of 220-280 ℃, and sampling to detect the chlorine content after charging and discharging.
S4: preparing materials: and (3) batching the chlorine seed selenium and the high-purity selenium according to the target value and the analysis result of the chlorine content of the chlorine seed selenium, then filling the chlorine seed selenium and the high-purity selenium into a quartz tube, and vacuumizing the quartz tube until the vacuum degree is below 10Pa and sealing the quartz tube.
S5: vacuum smelting: and (3) placing the sealed quartz tube in a swinging atmosphere furnace, heating to 230-350 ℃ at a heating rate of 100-500 ℃/h, and carrying out heat preservation reaction for 1-6 h.
S6: discharging: discharging after the heat preservation reaction is finished, and breaking the quartz tube to obtain the chlorine-doped high-purity selenium product.
In some embodiments of the present invention, in S2, the chlorine gas is diluted with a shielding gas and then reacted with the high purity selenium feedstock. Because the reaction rate of the chlorine and the selenium is low, the chlorine is diluted by the protective gas and then reacts with the high-purity selenium raw material, so that the utilization rate of the chlorine and the uniformity of the product can be improved. The volume concentration of chlorine in the mixed gas diluted by the protective gas is more than 10%, and the volume concentration of chlorine is preferably 20-100%.
In certain embodiments of the invention, the high purity selenium feedstock has a purity of 5N or greater.
In certain embodiments of the present invention, the high purity selenium is in a form that is meltable or solid.
In certain embodiments of the invention, the reactor is a temperature resistant glass or quartz reactor.
In certain embodiments of the invention, the shielding gas is 4N or more nitrogen or an inert gas. In some embodiments of the invention, the shielding gas is 4N or more argon to facilitate air displacement.
In some embodiments of the invention, the reactor comprises a vent at the bottom of the reactor, and further, the vent may be provided with a plurality of bubblers for introducing chlorine gas.
In certain embodiments of the present invention, the corrosion resistant vessel is selected from a graphite crucible.
In certain embodiments of the present invention, the atmosphere furnace is a rocking atmosphere furnace.
In some embodiments of the present invention, the temperature of the high purity selenium is preferably controlled to be 240-260 ℃.
As an alternative, S1 directly uses molten high-purity selenium, which is first replaced with a shielding gas and preheated.
In some embodiments of the present invention, in S3, the flow rate of chlorine gas is 0.5-5L/min.
In some embodiments of the present invention, in S3, the amount of chlorine consumed per 1kg of selenium is 3L or more, and the amount of chlorine consumed per 1kg of selenium is preferably 3 to 10L.
Example 1.
Adding 2kg of 5N selenium blocks into a glass reactor resistant to chlorine corrosion, placing the glass reactor into a heater, introducing argon into the reactor to replace air, and controlling the temperature in the reactor at 230 ℃ to completely melt the 5N selenium blocks; then keeping the temperature at 230 ℃, introducing chlorine at the flow rate of 0.5L/min, stopping introducing the chlorine after 15L of the chlorine is introduced, introducing argon to completely replace the chlorine in the reactor, transferring 5N selenium to a graphite crucible, and cooling to form metastable chlorine seed selenium.
Then placing the metastable chlorine seed selenium in a quartz rectifying tower (a stainless steel shell and a quartz lining layer), carrying out thermal insulation rectification for 4 hours under the conditions of 10Pa of pressure and 280 ℃, charging and discharging after thermal insulation, sampling and detecting the chlorine seed selenium, wherein the detection result shows that the chlorine content is 1200-1250 ppm, and then according to the high-purity selenium: chloro seed selenium = 4: 1, 3kg of ingredients are added, the mixture is put into a quartz tube with the diameter of 60 multiplied by 700mm, then the quartz tube is vacuumized to 10Pa and sealed, the temperature is raised to 230 ℃ at the heating rate of 100 ℃/h, the reaction is carried out for 6h under the condition of heat preservation, the tube is broken and the material is discharged after the product is cooled after the heat preservation is finished, 2.95kg of chlorine-doped high-purity selenium product is obtained, and sampling detection results show that the chlorine content of three samples is respectively: 233ppm, 225ppm and 244 ppm.
Example 2.
Adding 2kg of high-purity 5N selenium blocks into a glass reactor resistant to chlorine corrosion, placing the glass reactor into a heater, introducing argon into the reactor to replace air, and controlling the temperature in the reactor to be 265 ℃ so that the 5N selenium blocks are completely melted; and then keeping the temperature of 265 ℃, introducing mixed gas of chlorine and argon at the introduction flow rate of 3L/min (wherein the volume concentration of the chlorine is 50%), stopping introducing the chlorine after 6L of the chlorine is totally introduced, introducing the argon to completely replace the chlorine in the reactor, and transferring the 5N selenium into a graphite crucible to be cooled to form metastable chlorine seed selenium.
Then placing the metastable chlorine seed selenium in a quartz rectifying tower (a stainless steel shell and a quartz lining layer), carrying out heat preservation and rectification for 4h under the conditions of 100Pa of pressure and 230 ℃, charging and discharging after heat preservation, sampling and detecting the chlorine seed selenium, wherein the detection result shows that the chlorine content is 700-750 ppm, and then carrying out high-purity selenium treatment according to the following steps: chlorin selenium = 9: 1kg of ingredients, namely filling 3kg of ingredients into a quartz tube with the diameter of 60 multiplied by 700mm, vacuumizing to 10Pa, sealing, heating to 350 ℃ at the speed of 500 ℃/h, carrying out heat preservation reaction for 1h, breaking the tube after the product is cooled after the heat preservation is finished, and discharging to obtain 2.94kg of chlorine-doped high-purity selenium product, wherein sampling detection results show that the chlorine contents of three samples are respectively as follows: 58ppm, 49ppm, 61 ppm.
Example 3.
Adding 2kg of high-purity 5N selenium blocks into a glass reactor resistant to chlorine corrosion, placing the glass reactor into a heater, introducing argon into the reactor to replace air, and controlling the temperature in the reactor at 300 ℃ to completely melt the 5N selenium blocks; and then keeping the temperature at 300 ℃, introducing mixed gas of chlorine and argon at the introduction flow rate of 5L/min (wherein the volume concentration of the chlorine is 20%), stopping introducing the chlorine after 20L of the chlorine is totally introduced, introducing the argon to completely replace the chlorine in the reactor, and transferring the 5N selenium into a graphite crucible to be cooled to form metastable chlorine seed selenium.
Then placing the metastable chlorine seed selenium in a quartz rectifying tower (a stainless steel shell and a quartz lining layer), carrying out heat preservation and rectification for 1h under the conditions of the pressure of 200Pa and the temperature of 280 ℃, aerating and discharging after heat preservation is finished, sampling and detecting the chlorine seed selenium, wherein the detection result shows that the chlorine content is 1250-1300 ppm, and then according to the high-purity selenium: chlorin selenium = 1: 9 kg of ingredients are added, the ingredients are put into a quartz tube with the diameter of 60 multiplied by 700mm, the quartz tube is vacuumized to 10Pa and sealed, the temperature is raised to 300 ℃ at the heating rate of 300 ℃/h, the reaction is carried out for 4h, the tube is broken and the materials are discharged after the products are cooled after the heat preservation is finished, 2.95kg of chlorine-doped high-purity selenium products are obtained, and the sampling detection results show that the chlorine contents of three samples are respectively: 1165ppm, 1189ppm, 1182 ppm.
The invention initiatively prepares the stable chlorine seed selenium with the chlorine content of 1000 +/-300 ppm, then mixes the high-purity selenium and the chlorine seed selenium according to the required proportion, obtains the chlorine-doped high-purity selenium product after smelting, has stable process, can produce the chlorine-doped high-purity selenium with the chlorine content of 50-1200 ppm in batches, and meets different requirements of customers.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (9)
1. A chlorine doping method of high-purity selenium is characterized in that: which comprises the following steps:
s1: melting: adding a high-purity selenium raw material into a reactor resistant to chlorine corrosion, placing the reactor in a heater, introducing protective gas into the reactor to replace air, and controlling the temperature in the reactor to be 230-300 ℃ until the high-purity selenium raw material is completely melted;
s2: reaction: controlling the temperature of the high-purity selenium to be 230-300 ℃, then introducing dried chlorine into the reactor at a certain speed, reacting the chlorine with the selenium to form an initial product, stopping introducing the chlorine after the reaction is finished, and introducing protective gas to completely replace free chlorine and chlorine in the reactor;
s3: rectification dechlorination: transferring the initial product into a corrosion-resistant vessel, cooling to obtain metastable chlorine selenium, then placing the vessel containing the metastable chlorine selenium into a quartz rectifying tower, carrying out heat preservation distillation for 1-4 h under the conditions of pressure of 10-200 Pa and temperature of 220-280 ℃, and sampling to detect the chlorine content after charging and discharging;
s4: preparing materials: the method comprises the following steps of (1) mixing chlorine selenium and high-purity selenium according to a target value and a chlorine content analysis result of the chlorine selenium, then filling the chlorine selenium and the high-purity selenium into a quartz tube, and vacuumizing the quartz tube until the vacuum degree is below 10Pa and sealing the quartz tube;
s5: vacuum smelting: placing the sealed quartz tube in a swinging atmosphere furnace, heating to 230-350 ℃ at a heating rate of 100-500 ℃/h, and carrying out heat preservation reaction for 1-6 h;
s6: discharging: discharging after the heat preservation reaction is finished, and breaking the quartz tube to obtain the chlorine-doped high-purity selenium product.
2. The method for doping chlorine in high-purity selenium according to claim 1, wherein: in S2, the chlorine gas is diluted by protective gas and then reacts with the high-purity selenium raw material.
3. The method for doping chlorine in high-purity selenium according to claim 1, wherein: the purity of the high-purity selenium raw material is 5N or more.
4. The method for doping chlorine in high-purity selenium according to claim 1, wherein: the protective gas is nitrogen or inert gas with the purity not lower than 4N.
5. The method for doping chlorine in high-purity selenium according to claim 1, wherein: in S2, the flow rate of chlorine gas is 0.5-5L/min.
6. The method for doping chlorine in high-purity selenium according to claim 1, wherein: in S2, the amount of chlorine consumed per 1kg of selenium is 3-10L.
7. The method for doping chlorine in high-purity selenium according to claim 1, wherein: the reactor adopts a quartz reactor.
8. The method for doping chlorine in high-purity selenium according to claim 1, wherein: the corrosion-resistant vessel is a graphite crucible.
9. The method for doping chlorine in high-purity selenium according to claim 1, wherein: the reactor includes a vent located at the bottom of the reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811552070.2A CN109850856B (en) | 2018-12-18 | 2018-12-18 | Chlorine doping method for high-purity selenium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811552070.2A CN109850856B (en) | 2018-12-18 | 2018-12-18 | Chlorine doping method for high-purity selenium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109850856A CN109850856A (en) | 2019-06-07 |
| CN109850856B true CN109850856B (en) | 2022-05-03 |
Family
ID=66891512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811552070.2A Active CN109850856B (en) | 2018-12-18 | 2018-12-18 | Chlorine doping method for high-purity selenium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109850856B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1300237A (en) * | 1969-04-25 | 1972-12-20 | Siemens Ag | Selenium rectifiers |
| JPS62222259A (en) * | 1986-03-25 | 1987-09-30 | Ricoh Co Ltd | Electrophotographic sensitive body |
-
2018
- 2018-12-18 CN CN201811552070.2A patent/CN109850856B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1300237A (en) * | 1969-04-25 | 1972-12-20 | Siemens Ag | Selenium rectifiers |
| JPS62222259A (en) * | 1986-03-25 | 1987-09-30 | Ricoh Co Ltd | Electrophotographic sensitive body |
Non-Patent Citations (2)
| Title |
|---|
| Determination of chlorine in selenium by a distillation-atomic absorption procedure;Reichel W等;《Analytical Chemistry》;19691231;第41卷(第13期);第1886-1888页 * |
| THE VAPOR PRESSURES OF SELENIUM TETRACHLORIDE.THE EXISTENCE OF SELENIUM DICHLORIDE;DON M. YOST等;《Journal of the American Chemical Society》;19301231;第52卷(第12期);第4680-4685页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109850856A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100552130B1 (en) | Calcium fluoride crystal production method and raw material processing method | |
| US4525334A (en) | Process for the production of silicon | |
| CN108408703A (en) | A kind of production method of black phosphorus | |
| US8658118B2 (en) | High purity crystalline silicon, high purity silicon tetrachloride for processes for producing the same | |
| CN101255598A (en) | Method for preparing solar energy grade polycrystalline silicon | |
| CN102304632B (en) | Method for preparing lead bismuth alloy for nuclear reactor | |
| CN101801847A (en) | Make the method for high purity elemental silicon | |
| CN105039796B (en) | Aluminium tellurium intermediate alloy and preparation method and application | |
| CN101565781A (en) | Method and device for producing high-purity antimony | |
| CN109850856B (en) | Chlorine doping method for high-purity selenium | |
| CN106498445B (en) | A kind of preparation method, its molten salt system and the application of high-purity Chlorides molten salts containing UCl3 | |
| NL8320373A (en) | METHOD AND APPARATUS FOR OBTAINING SILICONE FROM HYDROFLUORIC HYDROXIC ACID. | |
| CN104178809B (en) | A kind of metallurgy method prepares the method for low metal boron foundry alloy | |
| CN101508436B (en) | Process for producing boron added refined silicon | |
| CN102432020A (en) | Manufacturing method of solar grade polysilicon | |
| CN107640749B (en) | High-purity tellurium dioxide and preparation method thereof | |
| CN102001664B (en) | Double-chamber duplex vacuum circulation degassing furnace and preparation of solar grade polycrystalline silicon | |
| CN108101007A (en) | The method for preparing zinc telluridse | |
| US20210292173A1 (en) | Method of making high quality silicon sulfide | |
| CN108588448B (en) | Preparation method of high-purity oxygen-free indium | |
| Forniés et al. | Polysilicon vs. upgraded metallurgical grade silicon (UMG-Si): Technology, quality and costs | |
| CN108249447B (en) | A kind of method of volatility slag gas collaboration purifying polycrystalline silicon | |
| NO154192B (en) | PROCEDURE FOR CLEANING OF SILICONE. | |
| CN106495113A (en) | The preparation method of high-purity zinc phosphide | |
| CN101671027B (en) | Metallurgical silicon purification method and on-line slagging boron removal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220523 Address after: No. 1116-1, building 1, Dianzhong Business Plaza, Dianzhong new area, Kunming, Yunnan 650212 Patentee after: Kunming forerunner New Material Technology Co.,Ltd. Address before: 511517 27-9B, Guangdong Qingyuan hi tech Industrial Park Patentee before: FIRST RARE MATERIALS Co.,Ltd. |