CN112048736A - Method for preparing high-density rod-shaped antimony - Google Patents
Method for preparing high-density rod-shaped antimony Download PDFInfo
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- CN112048736A CN112048736A CN202010915112.5A CN202010915112A CN112048736A CN 112048736 A CN112048736 A CN 112048736A CN 202010915112 A CN202010915112 A CN 202010915112A CN 112048736 A CN112048736 A CN 112048736A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/22—Moulds for peculiarly-shaped castings
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
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Abstract
The invention discloses a method for manufacturing high-density rod-shaped antimony, which relates to the technical field of manufacturing of antimony profiles and comprises the following steps: s1, cleaning and drying the quartz tube; s2, preparing high-purity antimony; s3, loading treatment, step II: preparing antimony particles to a required size, then filling the antimony particles into the cleaned and dried quartz tube, vertically putting the quartz tube into a quartz outer tube, and putting the whole body into a muffle furnace; vacuumizing the inside of the quartz appearance to 10 DEG‑4 ～10‑3Pa; heating the temperature in the muffle furnace to 700 DEG C～750 ℃ and maintain the temperature range at 25 DEG C～35 min; s4, melting antimony particles, cooling and forming; and S5, performing anti-oxidation packaging treatment. The rod-shaped antimony prepared by the method has high purity and density. The preparation method adopts a method of pressurizing, deeply purifying by vacuum distillation and then utilizing diaphragm electrolytic deposition to complete the preparation of high-purity antimony before preparation, so that the prepared rod-shaped antimony has higher compactness.
Description
Technical Field
The invention relates to the technical field of manufacturing of antimony profiles, in particular to a method for manufacturing high-density rod-shaped antimony.
Background
Antimony is one of the elements of main group V of the periodic Table of the elements, and it is a semimetal element interposed between a metal and a semiconductor. Antimony has an atomic weight of 121.75 and an atomic number of 51, and metallic antimony is brittle, and non-ductile, and its mechanical strength decreases as the purity of the metal increases. The melting point of antimony is 903.5K, the antimony is easy to volatilize, the volume change is small when solid-liquid phase transformation occurs, and the volume shrinkage rate of pure antimony is 0.79 +/-0.14% when the pure antimony is solidified. Antimony is a relatively stable metal, can keep its surface gloss and not be oxidized even if placed in humid air for a long time at normal temperature, is insoluble in water, is stable in dilute nitric acid and concentrated hydrofluoric acid, but is dissolved in concentrated hydrochloric acid, hot concentrated nitric acid and concentrated sulfuric acid, and is slightly soluble in phosphoric acid and organic acid.
The high-purity antimony is mainly used in the semiconductor industry, and can form semiconductor compounds such as indium antimonide, gallium antimonide, aluminum antimonide and the like; can be used as a dopant of semiconductor silicon, germanium and the like to form an N-type semiconductor; it can also be used as an alloy. In recent years, with the development of high and new technology industries, the application field of antimony is increasingly wide, and different requirements are made on the shape of antimony materials in the semiconductor industry, so that the preparation of rod-shaped antimony materials with high purity and high density is a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for manufacturing high-density rod-shaped antimony, which solves the problem that the preparation of high-purity and high-density rod-shaped antimony materials is urgently needed to be solved.
In order to achieve the purpose, the invention is realized by the following technical scheme: a method for manufacturing high-density rod-shaped antimony comprises the following steps:
s1, cleaning and drying the quartz tube: washing off white silicon dioxide attached to the inner surface and the outer surface of the quartz tube by hydrofluoric acid through the quartz tube with one open end and one closed end; soaking the quartz tube in the king water for more than 8 hours, and washing impurities on the inner surface and the outer surface of the quartz tube; washing the quartz tube after the acid cleaning by using high-purity water, and drying in an infrared lamp drying box;
s2, preparing high-purity antimony: after completely dissolving antimony sulfate powder, firstly, regulating the pH value of an antimony sulfate solution in advance, then, pressurizing the antimony sulfate solution to perform ion exchange and deep purification on impurities in the antimony sulfate solution through an ion exchange column, then, mixing an antimony product and an arsenic removal agent according to a first mass ratio in the purified antimony sulfate solution by taking 99.99% of high-purity antimony as an anode and taking a pretreated titanium substrate as a cathode for diaphragm electrolytic deposition, after the electrolysis is completed, putting the quartz boat into a furnace, heating the quartz boat to a specified temperature interval, preserving the temperature for a period of time, then, stopping the furnace, cooling and taking out the material, and separating and removing arsenic in a solid slag form to prepare high-purity antimony;
s3, charging treatment: crushing the prepared high-purity antimony raw material to a proper size, loading the crushed high-purity antimony raw material into the quartz tube cleaned and dried in the step S1, vertically placing the quartz tube into the quartz outer tube, then integrally placing the quartz tube into a muffle furnace, and vacuumizing the interior of the quartz outer tube after loading is finished;
s4, processing, cooling and forming: melting antimony particles, cooling and forming: after the vacuum degree in the quartz outer tube reaches a specified interval, heating is started to wait for the temperature in the muffle furnace to reach the specified temperature interval, then the temperature is cooled to the specified interval after the temperature is stable, and antimony particles are completely melted in the cooling process; when the temperature of the heating furnace is kept at the designated temperature for a period of time, starting to raise the quartz outer tube to gradually cool and mold the material; after waiting for the muffle furnace and the quartz tube to be completely cooled, taking out the formed antimony rod:
s5, anti-oxidation packaging treatment: and pouring the prepared lactic acid with the content of a specified numerical value into a specified container, then putting the antimony rod into the container, stirring the lactic acid by using an external stirring device for a specified time, taking out the antimony rod, drying the antimony rod by using high-purity argon gas, and carrying out vacuum packaging treatment.
Preferably, the pressure resistance value of the quartz outer tube in the step S1 is not less than 0.1MPa, and the aqua regia is nitrohydrochloric acid in the step S1.
Preferably, the arsenic removal agent in the step S2 is sodium carbonate, the temperature interval is controlled at 900 ℃ and 600 ℃, and the temperature is kept for 5-30 min.
Preferably, all quartz appliances in the process are made of high-purity quartz, and the temperature control system in the muffle furnace in the steps S3 and S4 comprises a K-type thermocouple for measuring the temperature in the furnace, wherein the thermocouple adopts a compensation lead connected with a precise temperature control instrument, and the precise temperature control instrument controls the heating power of the heater through a thyristor.
Preferably, the vacuum degree interval is 10-4 ～10-3Pa, the temperature in the muffle furnace reaches 700 DEG～Cooling to 600 deg.C again at 750 deg.C～660 ℃, and keeping the constant temperature at 600 DEG C～Within the range of 660 ℃.
Preferably, the quartz tube is dried in a vacuum drying oven for 4 hours in the step S1, the purity of the antimony sulfate particles selected in the step S2 is 5N, and the diameter of the particles is 5～10mm。
Preferably, the designated value in the step S5 is 45% -55%, and the rotation speed of the stirring device in the step S5 is controlled at 500-.
Preferably, the specified time in the step S5 is controlled to be 20-30min, and high-purity argon is used for blow-drying the antimony rod in the drying process.
Advantageous effects
The invention provides a method for manufacturing high-density rod-shaped antimony. Compared with the prior art, the method has the following beneficial effects:
1. the manufacturing method of the high-density rod-shaped antimony lays a foundation for preparing the rod-shaped antimony with high purity and high density by strictly controlling the cleanliness of the prepared quartz tube; all in oneThe quartz outer tube is vertically placed in a muffle furnace so as to be cooled later to form a rod-shaped body; firstly, the quartz outer tube is vacuumized to 10 degrees-4 ～10-3Pa to remove air and avoid antimony being oxidized during heating, and raising the temperature of the furnace to 700 DEG C～Melting antimony at 750 ℃, and improving the utilization rate of antimony particles; finally, the furnace temperature is reduced to 600 DEG～And 660 ℃, slowly lowering the quartz outer tube after the temperature is stable, eliminating the stress in the high-density rod-shaped antimony in the cooling and forming process, ensuring the rod-shaped antimony to be complete and flawless, simultaneously, preparing the high-purity antimony by adopting a method of pressurizing, carrying out solution deep purification through ionic resin and then utilizing diaphragm electrolytic deposition before preparation, mixing an electrolytic antimony product and an arsenic removal agent according to a certain mass ratio after the preparation is finished, loading the electrolytic antimony product and the arsenic removal agent into a quartz boat, then loading the quartz boat into a furnace, heating to the temperature of 600-phase-change 900 ℃, preserving heat for 5-30min, and removing arsenic in the high-purity antimony to obtain the high-density antimony. In addition, the acquisition, adjustment and feedback of temperature information are strictly controlled by adopting a K-type thermocouple, a compensation lead and a controlled silicon, and the purity and density of the rod-shaped antimony are further improved from the control of temperature, so that the prepared rod-shaped antimony has higher compactness.
2. The manufacturing method of the high-density rod-shaped antimony comprises the steps of pouring prepared lactic acid with the content of a specified numerical value into a specified container in step S5, then putting the antimony rod into the container, stirring the antimony rod by using an external stirring device for a specified time, taking the antimony rod out, drying the antimony rod, carrying out vacuum packaging treatment, fully mixing the rod-shaped antimony with the lactic acid in the container, and effectively attaching the lactic acid to the annular outer surface of the rod-shaped antimony.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 of the 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.
Referring to fig. 1, the present invention provides three technical solutions:
example 1
A method for manufacturing high-density rod-shaped antimony comprises the following steps:
s1, cleaning and drying the quartz tube: washing off white silicon dioxide attached to the inner surface and the outer surface of the quartz tube by hydrofluoric acid through the quartz tube with one open end and one closed end; soaking the quartz tube in the king water for more than 8 hours, and washing impurities on the inner surface and the outer surface of the quartz tube; washing the quartz tube after the pickling with high-purity water, and drying in an infrared lamp drying box, wherein the drying time is 4 hours, the withstand voltage value of the quartz outer tube is not less than 0.1MPa, aqua regia is nitrohydrochloric acid, and the melting point of antimony is higher, so that a container for containing antimony particle raw materials needs to be a high-temperature-resistant container, and in view of the need to prepare a rod-shaped antimony material, the quartz tube is selected as the container for containing antimony particles, hydrofluoric acid is selected because the hydrofluoric acid can dissolve quartz glass and white silica attached to the surface, so that the antimony material is prevented from being polluted by the silica, the precondition which is necessary for preparing high-purity antimony is that the ratio of nitric acid to hydrochloric acid in the aqua regia is 1: 3, the corrosion ability of the aqua regia is extremely strong, the cleaning ability is superior to that of all single acid and alkali reagents, and other metals on the quartz tube or other impurities capable of being corroded and decomposed by the aqua regia are removed completely by utilizing the characteristic that the aqua regia can dissolve most metals, so that the impurities on the inner surface and the outer surface of the quartz tube are ensured to be cleaned by acid, and the quartz tube containing the antimony particle raw material is further cleaned;
s2, preparing high-purity antimony: the purity of the adopted particles is 5N, and the diameter of the particles is 5～10mm antimony sulfate, fully dissolving antimony sulfate powder, and pre-adjusting antimony sulfatePressurizing the pH value of the solution, performing ion exchange through an ion exchange column to deeply purify impurities in the antimony sulfate solution, mixing an antimony electrolysis product and an arsenic removal agent according to a first mass ratio after the purified antimony sulfate solution is electrolyzed by using 99.99% high-purity antimony as an anode and a pretreated titanium substrate as a cathode, mixing the antimony electrolysis product and the arsenic removal agent, wherein the arsenic removal agent is sodium carbonate, putting the mixture into a quartz boat, putting the quartz boat into a furnace, heating to the temperature of 600-900 ℃, preserving the temperature for 5-30min, stopping the furnace, cooling, taking out the material, and removing the arsenic in the form of solid slag to prepare high-purity antimony;
s3, charging treatment: crushing the prepared high-purity antimony raw material to a proper size, putting the crushed high-purity antimony raw material into the quartz tube cleaned and dried in the step S1, vertically putting the quartz tube into the quartz outer tube, then integrally putting the quartz outer tube into a muffle furnace, vacuumizing the interior of the quartz outer tube after the charging is finished, arranging a support for uniformly placing the quartz tube in the quartz outer tube, wherein the support can be made into a honeycomb-like structure by using a high-temperature-resistant material so as to uniformly place the quartz tube and ensure that each quartz tube is fully and uniformly heated, so that the internal pressure of the quartz outer tube is forcibly pumped to a vacuum state, and the antimony can be contacted with oxygen to be oxidized under a heating condition;
s4, processing, cooling and forming: melting antimony particles, cooling and forming: when the vacuum degree in the quartz outer tube reaches 10-4～－3After Pa, heating is started to wait for the temperature in the muffle furnace to reach within 700 ℃, then, after the temperature is stable, cooling is carried out to within 600 ℃, and antimony particles are completely melted in the cooling process; after the temperature of the heating furnace is kept at 600 ℃ for a period of time, the quartz outer tube is lifted to gradually cool and form the material, and the gradient cooling method can slow down the thermal stress generated by the antimony rod in the cooling process on one hand and can make the antimony rod more compact in forming on the other hand; after the muffle furnace and the quartz tube are completely cooled, taking out the formed antimony rod, wherein the whole cooling process lasts for more than one hour, and the antimony rod can generate larger thermal stress due to the fact that the antimony has the characteristics of thermal shrinkage and cold expansion, so that the set temperature is only slightly higher than the melting point of the antimony and is better;
s5, anti-oxidation packaging treatment: pouring the prepared lactic acid with the content of 45% into a designated container, then putting an antimony rod into the container, stirring the lactic acid by using an external stirring device with the rotating speed of 500r/min, taking out the antimony rod after stirring for 20min, drying the antimony rod by using high-purity argon in the airing process, and carrying out vacuum packaging treatment.
Further, all quartz appliances in the process are made of high-purity quartz, the temperature control system in the muffle furnace in the steps S3 and S4 comprises a K-type thermocouple for measuring the temperature in the furnace, a compensation lead adopted by the thermocouple is connected with a precise temperature controller, and the precise temperature controller controls the heating power of the heater through a controllable silicon.
Example 2
A method for manufacturing high-density rod-shaped antimony comprises the following steps:
s1, cleaning and drying the quartz tube: washing off white silicon dioxide attached to the inner surface and the outer surface of the quartz tube by hydrofluoric acid through the quartz tube with one open end and one closed end; soaking the quartz tube in the king water for more than 8 hours, and washing impurities on the inner surface and the outer surface of the quartz tube; washing the quartz tube after the pickling with high-purity water, and drying in an infrared lamp drying box, wherein the drying time is 4 hours, the withstand voltage value of the quartz outer tube is not less than 0.1MPa, aqua regia is nitrohydrochloric acid, and the melting point of antimony is higher, so that a container for containing antimony particle raw materials needs to be a high-temperature-resistant container, and in view of the need to prepare a rod-shaped antimony material, the quartz tube is selected as the container for containing antimony particles, hydrofluoric acid is selected because the hydrofluoric acid can dissolve quartz glass and white silica attached to the surface, so that the antimony material is prevented from being polluted by the silica, the precondition which is necessary for preparing high-purity antimony is that the ratio of nitric acid to hydrochloric acid in the aqua regia is 1: 3, the corrosion ability of the aqua regia is extremely strong, the cleaning ability is superior to that of all single acid and alkali reagents, and other metals on the quartz tube or other impurities capable of being corroded and decomposed by the aqua regia are removed completely by utilizing the characteristic that the aqua regia can dissolve most metals, so that the impurities on the inner surface and the outer surface of the quartz tube are ensured to be cleaned by acid, and the quartz tube containing the antimony particle raw material is further cleaned;
s2, preparing high-purity antimony: the purity of the adopted particles is 5N, and the diameter of the particles is 5～Fully dissolving antimony sulfate powder, firstly pre-adjusting the pH value of an antimony sulfate solution, then pressurizing the antimony sulfate solution to perform ion exchange through an ion exchange column to deeply purify impurities in the antimony sulfate solution, then adopting 99.99 percent of high-purity antimony as an anode of the purified antimony sulfate solution, adopting a pretreated stainless steel substrate as a cathode to perform diaphragm electrolytic deposition, after the electrolysis is completed, mixing an antimony raw material and an arsenic removal agent according to a certain mass ratio, mixing the arsenic removal agent which is sodium carbonate, then putting the mixture into a quartz boat, then putting the quartz boat into a furnace to heat up to 750 ℃, preserving the temperature for 17min, then stopping the furnace, cooling and taking out the material, removing arsenic in a solid slag form, and preparing to obtain high-purity antimony;
s3, charging treatment: crushing the prepared high-purity antimony raw material to a proper size, putting the crushed high-purity antimony raw material into the quartz tube cleaned and dried in the step S1, vertically putting the quartz tube into the quartz outer tube, then integrally putting the quartz outer tube into a muffle furnace, vacuumizing the interior of the quartz outer tube after the charging is finished, arranging a support for uniformly placing the quartz tube in the quartz outer tube, wherein the support can be made into a honeycomb-like structure by using a high-temperature-resistant material so as to uniformly place the quartz tube and ensure that each quartz tube is fully and uniformly heated, so that the internal pressure of the quartz outer tube is forcibly pumped to a vacuum state, and the antimony can be contacted with oxygen to be oxidized under a heating condition;
s4, processing, cooling and forming: melting antimony particles, cooling and forming: when the vacuum degree in the quartz outer tube reaches 5 multiplied by 10-3After Pa, heating is started to wait for the temperature in the muffle furnace to reach 730 ℃, then, after the temperature is stable, cooling is carried out to reach 630 ℃, and antimony particles are completely melted in the cooling process; after the temperature of the heating furnace is kept at 630 ℃ for a period of time, the quartz outer tube is lifted to gradually cool and form the material, and the gradient cooling method can slow down the thermal stress generated by the antimony rod in the cooling process on one hand and can make the antimony rod more compact in forming on the other hand; after the muffle furnace and the quartz tube are completely cooled, the formed antimony rod is taken out, the whole cooling process lasts for more than one hour, and the antimony rod is provided with a cooling deviceThe antimony rod has the characteristics of thermal shrinkage and cold expansion, so that the antimony rod generates larger thermal stress when the heating temperature is too high, and the set temperature only needs to be slightly higher than the melting point of antimony to be best;
s5, anti-oxidation packaging treatment: pouring the prepared lactic acid with the content of 50% into a specified container, then putting the antimony rod into the container, stirring the lactic acid by using an external stirring device with the rotating speed of 600r/min, taking out the antimony rod after stirring for 25min, blowing the antimony rod by using an external fan in the airing process, and carrying out vacuum packaging treatment.
Furthermore, all quartz appliances in the process are made of high-purity quartz, the temperature control system in the muffle furnace in the steps S3 and S4 comprises a K-type thermocouple for measuring the temperature in the furnace, a compensation lead adopted by the thermocouple is connected with a precise temperature controller, and the precise temperature controller controls the heating power of the heater through a controllable silicon;
example 3
A method for manufacturing high-density rod-shaped antimony comprises the following steps:
s1, cleaning and drying the quartz tube: washing off white silicon dioxide attached to the inner surface and the outer surface of the quartz tube by hydrofluoric acid through the quartz tube with one open end and one closed end; soaking the quartz tube in the king water for more than 8 hours, and washing impurities on the inner surface and the outer surface of the quartz tube; washing the quartz tube after the pickling with high-purity water, and drying in an infrared lamp drying box, wherein the drying time is 4 hours, the withstand voltage value of the quartz outer tube is not less than 0.1MPa, aqua regia is nitrohydrochloric acid, and the melting point of antimony is higher, so that a container for containing antimony particle raw materials needs to be a high-temperature-resistant container, and in view of the need to prepare a rod-shaped antimony material, the quartz tube is selected as the container for containing antimony particles, hydrofluoric acid is selected because the hydrofluoric acid can dissolve quartz glass and white silica attached to the surface, so that the antimony material is prevented from being polluted by the silica, the precondition which is necessary for preparing high-purity antimony is that the ratio of nitric acid to hydrochloric acid in the aqua regia is 1: 3, the corrosion ability of the aqua regia is extremely strong, the cleaning ability is superior to that of all single acid and alkali reagents, and other metals on the quartz tube or other impurities capable of being corroded and decomposed by the aqua regia are removed completely by utilizing the characteristic that the aqua regia can dissolve most metals, so that the impurities on the inner surface and the outer surface of the quartz tube are ensured to be cleaned by acid, and the quartz tube containing the antimony particle raw material is further cleaned;
s2, preparing high-purity antimony: the purity of the adopted particles is 5N, and the diameter of the particles is 5～Fully dissolving antimony sulfate powder, firstly pre-adjusting the pH value of an antimony sulfate solution, then pressurizing the antimony sulfate solution to perform ion exchange through an ion exchange column to deeply purify impurities in the antimony sulfate solution, then adopting 99.99 percent of high-purity antimony as an anode of the purified antimony sulfate solution, adopting a pretreated stainless steel substrate as a cathode to perform diaphragm electrolytic deposition, after the electrolysis is completed, mixing an antimony raw material and an arsenic removal agent according to a certain mass ratio, mixing the arsenic removal agent which is sodium carbonate, then putting the mixture into a quartz boat, then putting the quartz boat into a furnace, heating to a temperature of 900 ℃, keeping the temperature for 30min, then stopping the furnace, cooling and taking out the material, and removing arsenic in a solid slag form to prepare high-purity antimony;
s3, charging treatment: crushing the prepared high-purity antimony raw material to a proper size, putting the crushed high-purity antimony raw material into the quartz tube cleaned and dried in the step S1, vertically putting the quartz tube into the quartz outer tube, then integrally putting the quartz outer tube into a muffle furnace, vacuumizing the interior of the quartz outer tube after the charging is finished, arranging a support for uniformly placing the quartz tube in the quartz outer tube, wherein the support can be made into a honeycomb-like structure by using a high-temperature-resistant material so as to uniformly place the quartz tube and ensure that each quartz tube is fully and uniformly heated, so that the internal pressure of the quartz outer tube is forcibly pumped to a vacuum state, and the antimony can be contacted with oxygen to be oxidized under a heating condition;
s4, processing, cooling and forming: melting antimony particles, cooling and forming: when the vacuum degree in the quartz outer tube reaches 10-3After Pa, heating is started to wait for the temperature in the muffle furnace to reach 750 ℃, then, after the temperature is stable, cooling is carried out to 660 ℃, and antimony particles are completely melted in the cooling process; after the temperature of the heating furnace is kept at 660 ℃ for a period of time, the quartz outer tube begins to rise to gradually cool and form the material, and the gradient cooling method can slow down the production of antimony rods in the cooling processThe generated thermal stress can make the antimony rod more compact; after the muffle furnace and the quartz tube are completely cooled, taking out the formed antimony rod, wherein the whole cooling process lasts for more than one hour, and the antimony rod can generate larger thermal stress due to the fact that the antimony has the characteristics of thermal shrinkage and cold expansion, so that the set temperature is only slightly higher than the melting point of the antimony and is better;
s5, anti-oxidation packaging treatment: pouring the prepared lactic acid with the content of 55% into a specified container, then putting the antimony rod into the container, stirring the lactic acid by using an external stirring device with the rotating speed of 700r/min, taking out the antimony rod after stirring for 30min, blowing the antimony rod by using an external fan in the airing process, and carrying out vacuum packaging treatment.
Further, all quartz appliances in the process are made of high-purity quartz, the temperature control system in the muffle furnace in the steps S3 and S4 comprises a K-type thermocouple for measuring the temperature in the furnace, a compensation lead adopted by the thermocouple is connected with a precise temperature controller, and the precise temperature controller controls the heating power of the heater through a controllable silicon.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for manufacturing high-density rod-shaped antimony is characterized by comprising the following steps:
s1, cleaning and drying the quartz tube: washing off white silicon dioxide attached to the inner surface and the outer surface of the quartz tube by hydrofluoric acid through the quartz tube with one open end and one closed end; soaking the quartz tube in the king water for more than 8 hours, and washing impurities on the inner surface and the outer surface of the quartz tube; washing the quartz tube after the acid cleaning by using high-purity water, and drying in an infrared lamp drying box;
s2, preparing high-purity antimony: after completely dissolving antimony sulfate powder, firstly, regulating the pH value of an antimony sulfate solution in advance, then, pressurizing the antimony sulfate solution to perform ion exchange and deep purification on impurities in the antimony sulfate solution through an ion exchange column, then, mixing the purified antimony sulfate solution with 99.99% of high-purity antimony as an anode, and performing diaphragm electrolytic deposition by using a pretreated high-purity titanium plate as a cathode, after the electrolysis is completed, mixing the high-purity cathode antimony and an arsenic removal agent according to a first mass ratio, mixing and then loading the antimony into a quartz boat, then loading the quartz boat into a furnace, heating to a specified temperature interval, introducing reducing gas, keeping the temperature for a period of time, then, stopping the furnace, cooling and taking out the material, and separating and removing arsenic in a solid slag form to prepare high-purity antimony;
s3, charging treatment: crushing the prepared high-purity antimony raw material to a proper size, loading the crushed high-purity antimony raw material into the quartz tube cleaned and dried in the step S1, vertically placing the quartz tube into the quartz outer tube, then integrally placing the quartz tube into a muffle furnace, and vacuumizing the interior of the quartz outer tube after loading is finished;
s4, processing, cooling and forming: melting antimony particles, cooling and forming: after the vacuum degree in the quartz outer tube reaches a specified interval, heating is started to wait for the temperature in the muffle furnace to reach the specified temperature interval, then the temperature is cooled to the specified interval after the temperature is stable, and antimony particles are completely melted in the cooling process; when the temperature of the heating furnace is kept at the designated temperature for a period of time, starting to raise the quartz outer tube to gradually cool and mold the material; after waiting for the muffle furnace and the quartz tube to be completely cooled, taking out the formed antimony rod:
s5, anti-oxidation packaging treatment: and pouring the prepared lactic acid with the content of the specified numerical value into a specified container, then putting the antimony rod into the container, stirring the lactic acid by using an external stirring device for a specified time, taking out the antimony rod after stirring for a specified time, drying, and carrying out vacuum packaging treatment.
2. The method for producing highly dense rod-like antimony as claimed in claim 1, wherein: the pressure resistance value of the quartz outer tube in the step S1 is not less than 0.1MPa, and the aqua regia in the step S1 is nitrohydrochloric acid.
3. The method for producing highly dense rod-like antimony as claimed in claim 1, wherein: in the step S2, the arsenic removal agent is sodium carbonate, the temperature range is controlled at 900 ℃ and the temperature is kept for 5-30 min.
4. The method for producing highly dense rod-like antimony as claimed in claim 1, wherein: all quartz appliances in the process are made of high-purity quartz, the temperature control system in the muffle furnace in the steps S3 and S4 comprises a K-type thermocouple for measuring the temperature in the furnace, a compensation lead adopted by the thermocouple is connected with a precise temperature controller, and the precise temperature controller controls the heating power of a heater through a silicon controlled rectifier.
5. The method for producing highly dense rod-like antimony as claimed in claim 1, wherein: the vacuum degree interval is 10-4～10-3Pa, the temperature in the muffle furnace reaches 700-750 ℃, the temperature is reduced to 600-660 ℃ again, and the constant temperature is kept within the range of 600-660 ℃.
6. The method for producing highly dense rod-like antimony as claimed in claim 1, wherein: the drying time of the quartz tube in the vacuum drying oven in the step S1 is 4 hours, the purity of the antimony sulfate particles selected in the step S2 is 5N, and the particle diameter is 5-10 mm.
7. The method for producing highly dense rod-like antimony as claimed in claim 1, wherein: the specified value in the step S5 is 45% -55%, and the rotation speed of the stirring device in the step S5 is controlled at 700 r/min.
8. The method for producing highly dense rod-like antimony as claimed in claim 1, wherein: and in the step S5, the designated time is controlled to be 20-30min, and external high-purity argon is adopted to blow the antimony rod in the airing process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114250371A (en) * | 2021-12-27 | 2022-03-29 | 广东先导微电子科技有限公司 | Preparation method of high-purity antimony rod |
| CN115305361A (en) * | 2022-08-26 | 2022-11-08 | 山东恒邦冶炼股份有限公司 | High-purity antimony rod and high-purity antimony white combined preparation process |
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| CN1295135A (en) * | 2000-07-14 | 2001-05-16 | 柳州市环东金属材料厂 | Dearsenicating method during smelting lead-antimony alloy |
| CN106222452A (en) * | 2016-07-26 | 2016-12-14 | 成都锦沪新材料有限公司 | A kind of preparation method of bar-shaped arsenic |
| CN108179441A (en) * | 2017-12-26 | 2018-06-19 | 广西生富锑业科技股份有限公司 | A kind of production method of high purity antimony |
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| CN106222452A (en) * | 2016-07-26 | 2016-12-14 | 成都锦沪新材料有限公司 | A kind of preparation method of bar-shaped arsenic |
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| CN114250371A (en) * | 2021-12-27 | 2022-03-29 | 广东先导微电子科技有限公司 | Preparation method of high-purity antimony rod |
| CN114250371B (en) * | 2021-12-27 | 2023-08-22 | 广东先导微电子科技有限公司 | Preparation method of high-purity antimony rod |
| CN115305361A (en) * | 2022-08-26 | 2022-11-08 | 山东恒邦冶炼股份有限公司 | High-purity antimony rod and high-purity antimony white combined preparation process |
| CN115305361B (en) * | 2022-08-26 | 2023-05-09 | 山东恒邦冶炼股份有限公司 | High-purity antimony rod and high-purity antimony white combined preparation process |
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