CN111115684B - Preparation method of high-purity antimony sulfide - Google Patents
Preparation method of high-purity antimony sulfide Download PDFInfo
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- CN111115684B CN111115684B CN201911403754.0A CN201911403754A CN111115684B CN 111115684 B CN111115684 B CN 111115684B CN 201911403754 A CN201911403754 A CN 201911403754A CN 111115684 B CN111115684 B CN 111115684B
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Abstract
The invention discloses a preparation method of high-purity antimony sulfide, which comprises the following steps: placing low-purity antimony sulfide or antimony sulfide concentrate into a vacuum furnace, carrying out primary distillation under the condition of a first preset temperature to simultaneously volatilize impurities with boiling points lower than that of antimony sulfide and antimony sulfide, and collecting antimony sulfide only containing low-boiling-point impurities by controlling the conditions of vacuum distillation and condensation; and (3) placing the antimony sulfide containing the low-boiling-point impurities into another vacuum furnace, homogenizing and resynthesizing the collected antimony sulfide under the condition of a second preset temperature at normal pressure, and then carrying out secondary distillation under the vacuum condition to remove impurities, so that the impurities with the boiling point lower than that of the antimony sulfide volatilize and the antimony sulfide does not volatilize, thereby obtaining high-purity antimony sulfide, wherein the second preset temperature is lower than the first preset temperature. The method provided by the invention does not use chemical agents such as acid and alkali, has no three-waste emission, simple and easy-to-operate process flow and high production efficiency; the purity of the antimony sulfide prepared by the method is as high as more than 99.9%.
Description
Technical Field
The invention relates to the field of nonferrous metallurgy, in particular to a preparation method of high-purity antimony sulfide.
Background
Antimony sulfide is black solid powder with a melting point of 548 ℃, antimony oxide generated after pyrolysis and metal antimony generated in the presence of a reducing agent can prevent oxidation combustion of the material at high temperature, maintain the friction stability of the material, improve the anti-combustion performance of the material, reduce the decomposition speed of an organic adhesive at high temperature, improve the service life of the material, and play roles of a high-temperature inorganic adhesive and a lubricating friction regulator. In addition, antimony sulfide has low hardness in high-temperature reaction, and can reduce noise and vibration generated when the friction material brakes. The outstanding performance of adjusting the friction coefficient of antimony sulfide has enabled the antimony sulfide to be widely applied in the friction material industry, and become one of the important materials of the disc brake pad with heavier load. The antimony sulfide can also be used for manufacturing matches and fireworks, various antimony salts and colored glass, and vulcanizing agents for rubber industry, and has good application prospects in the fields of photoelectron materials, solar cells, photoelectrochemistry and the like.
The preparation method of antimony sulfide mainly comprises a natural ore processing method, an antimony white conversion method and a direct synthesis method. Natural mineral processing method: the antimony sulfide concentrate is directly processed to obtain blocky antimony sulfide concentrate with antimony content higher than 45%, and pure antimony trisulfide (commonly called as raw antimony) can be prepared by a liquation method. Antimony white conversion method: the reaction equation is Sb 2 O 3 +4Na 2 S+3H 2 O→Sb 2 S 3 +8NaOH + CaS, and proper steps and conditions are controlled to obtain antimony sulfide. Direct chemical combination method: reaction equation is 2Sb +3S → Sb 2 S 3 Antimony sulfide can be prepared by mixing antimony metal with sulfur for vulcanization, or by introducing sulfur vapor into liquid antimony metal.
Chinese patent CN201634454U discloses a device for producing high-purity antimony sulfide by using antimony sulfide concentrate, the device uses antimony sulfide concentrate as raw material, the grade requirement is high, the liquation purification mode is easy to oxidize, and the clean production is difficult to realize; chinese patent CN107892328A discloses a wet method for preparing nanometer-level high-purity antimony sulfide from antimony chloride and sulfur, wherein the raw materials used in the method are secondary industrial products, the preparation process is complex, and large-scale production is difficult to form; chinese patent CN1994237A discloses a process for preparing industrial grade pure antimony sulfide by removing impurities in antimony sulfide ore by a wet method, wherein the process needs to crush antimony ore and uses strong acid and strong alkali, so that the environmental pollution is large.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of high-purity antimony sulfide, and aims to solve the problems that the existing antimony sulfide production process is complex, has high environmental pollution, is difficult to realize large-scale production and the prepared antimony sulfide has low purity.
The technical scheme of the invention is as follows:
a preparation method of high-purity antimony sulfide comprises the following steps:
placing antimony sulfide concentrate or low-purity antimony sulfide in a vacuum furnace, carrying out primary distillation under the condition of a first preset temperature, volatilizing impurities with boiling points lower than that of the antimony sulfide and the antimony sulfide at the same time at the temperature, and collecting antimony sulfide containing only low-boiling-point impurities by controlling the conditions of vacuum distillation and condensation;
and (2) placing the antimony sulfide containing the low-boiling-point impurities into another vacuum furnace, adding proper sulfur according to the proportion of metal antimony and sulfur contained in the collected antimony sulfide to ensure that the molar ratio of Sb to S is 2.
The preparation method of the high-purity antimony sulfide comprises the following steps of (1) preparing a high-purity antimony sulfide, wherein the first preset distillation temperature is 900-1200 ℃, and the vacuum degree is 5-200 Pa; the conditions of volatile matter condensation are that the condensation distance is 30-100 cm and the condensation temperature is 100-250 ℃. .
The preparation method of the high-purity antimony sulfide comprises the following steps of setting the second preset temperature to be 560-610 ℃ and setting the vacuum degree to be 5-200 Pa.
The preparation method of the high-purity antimony sulfide comprises the following steps of:
granulating antimony alloy, mixing with sulfur, heating to 300-500 ℃ and vulcanizing to obtain low-purity antimony sulfide;
or heating and melting the antimony alloy, and then introducing sulfur steam for vulcanization to prepare the low-purity antimony sulfide.
The preparation method of the high-purity antimony sulfide comprises the step of preparing the low-purity antimony sulfide by using a chemical reaction method 2 S 3 、S、Sb、In、Cu、As、Pb、Bi、、As 2 S 3 、Sb 2 S 3 、PbS、ZnS、Cu 2 S and FeS.
The preparation method of the high-purity antimony comprises the step of preparing antimony sulfide concentrate, wherein the antimony sulfide concentrate comprises Sb 2 S 3 、As 2 S 3 、S、Sb 2 O 3 PbS, feS, znS and gangue.
The preparation method of the high-purity antimony sulfide is characterized in that the purity of the high-purity antimony sulfide is more than 99.9%.
Has the advantages that: the invention provides a preparation method of high-purity antimony sulfide, which directly takes antimony sulfide concentrate or low-purity antimony sulfide as a raw material to prepare the high-purity antimony sulfide, and removes impurities by carrying out vacuum fractional distillation treatment on the antimony sulfide concentrate or low-purity antimony sulfide to obtain the high-purity antimony sulfide, thereby expanding the application range of the raw material; the invention does not use chemical agents such as acid, alkali and the like, does not discharge three wastes, and has simple and easy operation process and high production efficiency; the invention has high impurity removal rate in the antimony sulfide through the working procedures of vacuum distillation, homogenization, chemical combination and vacuum impurity removal, the purity of the prepared antimony sulfide reaches more than 99.9 percent, and the direct yield of Sb is more than 99 percent.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of the process for preparing high purity antimony sulfide of the present invention.
Detailed Description
The invention provides a preparation method of high-purity antimony sulfide, which is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A preparation method of high-purity antimony sulfide comprises the following steps:
s10, placing low-purity antimony sulfide or antimony sulfide concentrate in a vacuum furnace, carrying out primary distillation at a first temperature, wherein at the first temperature, impurities with a boiling point lower than that of antimony sulfide volatilize at the same time, impurities with a high boiling point do not volatilize, and collecting antimony sulfide only containing low-boiling-point impurities by controlling the conditions of vacuum distillation and condensation;
s20, placing the antimony sulfide containing the low-boiling-point impurities into another vacuum furnace, adding a proper amount of sulfur, homogenizing and resynthesizing the collected antimony sulfide under the condition of a second temperature at normal pressure, and then carrying out secondary distillation under the vacuum condition to remove impurities, wherein at the temperature, the impurities with the boiling point lower than that of the antimony sulfide volatilize, but the antimony sulfide does not volatilize, so that high-purity antimony sulfide is obtained, and the second preset temperature is lower than the first preset temperature.
The preparation of the low-purity antimony sulfide is that antimony alloy is prepared by sulfur vulcanization, and the preparation method comprises the following steps:
mixing antimony alloy particles with sulfur, heating to 300-700 ℃ for vulcanization to prepare low-purity antimony sulfide; or heating and melting the antimony alloy, and then introducing sulfur steam for vulcanization to prepare low-purity antimony sulfide; or mixing antimony particles and sulfur, putting the mixture into an oxygen-free closed container, heating to 320-400 ℃, and stirring to enable the antimony particles and the sulfur to react at a first stage; continuously heating to 550-650 ℃ under the conditions of no oxygen and stirring to obtain the low-purity antimony sulfide.
Specifically, low purity antimony sulfide generally includes Sb 2 S 3 、S、Sb、In、Cu、As、Pb、Bi、As 2 S 3 、PbS、ZnS、Cu 2 S and FeS, the saturated vapor pressure of each component is S > As in the order of high to low 2 S 3 ＞Sb 2 S 3 ＞Pb＞Bi＞Sb＞In＞PbS＞ZnS＞Cu 2 S is larger than FeS, and based on the characteristic that the saturated vapor pressure of antimony sulfide and other impurity components has larger difference, proper conditions are controlled for vacuum distillation to separate antimony sulfide and impurities.
Placing the low-purity antimony sulfide in a vacuum furnace at 900-1200 DEG CThe first distillation is carried out under conditions to obtain As in the low-purity antimony sulfide 2 S 3 S and antimony sulfide are volatilized simultaneously to make Sb 2 S 3 And enriching in volatile matters to obtain antimony sulfide only containing low-boiling-point impurities. Under the condition of isolating oxygen, sb 2 S 3 In order to avoid or reduce the decomposition of antimony sulfide in the first distillation process, the form of volatilized antimony sulfide is changed into a gas state-a solid state under the conditions of the condensation temperature and the distance of a condensation area, and the residence time of antimony sulfide in a decomposition temperature interval is reduced by adjusting the condensation distance and the temperature, so that the decomposition of antimony sulfide is reduced. A small amount of decomposed antimony sulfide is directly condensed into a solid state through a condensation area and collected, and the collected product is Sb 2 S 3 Sb, S and part of low boiling point impurities.
Further, sb is added 2 S 3 Placing the mixture of Sb, S and low-boiling point impurities into another vacuum furnace, homogenizing and synthesizing at 560-700 ℃ to react to generate antimony sulfide, then carrying out secondary distillation under vacuum condition to remove impurities, and volatilizing the impurities with the boiling point lower than that of the antimony sulfide and not volatilizing the antimony sulfide at the temperature to obtain the high-purity antimony sulfide with the purity of more than 99.9%.
Antimony sulphide concentrates usually contain Sb 2 S 3 、As 2 S 3 、S、Sb 2 O 3 PbS, feS, znS and the like, the saturated vapor pressure of each component being S > As in the order of high to low 2 S 3 ＞Sb 2 O 3 ＞Sb 2 S 3 PbS is greater than ZnS is greater than FeS, and based on the characteristic that the saturated vapor pressure difference of antimony sulfide and other impurity components is large, proper conditions are controlled for vacuum distillation, so that the antimony sulfide and the impurities are separated.
Putting the antimony sulfide concentrate into a vacuum furnace, and carrying out primary distillation at 900-1200 ℃ to obtain As in low-purity antimony sulfide 2 S 3 S and antimony sulfide are volatilized simultaneously to make Sb 2 S 3 Is enriched in volatiles to obtain onlyAntimony sulfide containing low boiling point impurities. Under the condition of isolating oxygen, sb 2 S 3 Decomposition can occur in the temperature range above the boiling point (1150 ℃), in order to avoid or reduce the decomposition of antimony sulfide in the first distillation process, the form of volatilized antimony sulfide is changed into gas state-solid state under the conditions of the condensation temperature and the distance of a condensation area, a small part of decomposed antimony sulfide is directly condensed into solid state through the condensation area for collection, and the collected product is Sb 2 S 3 Sb, S and low boiling impurities.
Further, sb is added 2 S 3 And placing the mixture of Sb, S and low-boiling point impurities into another vacuum furnace, homogenizing and synthesizing at 560-600 ℃ to react to generate antimony sulfide, and then carrying out secondary distillation under vacuum condition to remove impurities, wherein at the temperature, the impurities with the boiling point lower than that of the antimony sulfide volatilize, but the antimony sulfide does not volatilize, so that the high-purity antimony sulfide with the purity of more than 99.9% is obtained.
The preparation of antimony sulphide according to the invention is further illustrated by the following specific examples:
example 1
1. Fully mixing 210Kg of granular antimony alloy (containing Sb-99.9%, pb-0.05%, bi-0.053% and As-0.02%) with the diameter of less than or equal to 2mm and 85Kg of sulfur powder by using a stirrer, adding the mixture into a closed container, heating to 400 ℃, preserving the heat, and reacting for 2 hours to obtain 291.40Kg of low-purity antimony sulfide;
2. placing the low-purity antimony sulfide in a vacuum furnace, vacuumizing to 5-50Pa in a condensation area which is 35cm away from a heating area, slowly heating to 950 ℃, keeping the temperature for 8 hours under the condition, controlling the temperature of the condensation area to be 150 ℃, and collecting 285.4Kg of a mixture of low-boiling-point impurities and antimony sulfide in volatile matters after distillation is finished;
3. placing the mixture of the low-boiling point impurities and the antimony sulfide in a vacuum furnace without adhering impurities, adding 1% of sulfur, and homogenizing and synthesizing the collected antimony sulfide at the normal pressure and the temperature of 560 ℃; then vacuumizing to 5-50Pa, slowly heating to 630 ℃, preserving heat for 3h under the condition, collecting 258.70Kg of residue after distillation is finished, and detecting the obtained residueThe residue is Sb 2 S 3 The purity was 99.93%.
Example 2
1. Fully mixing 210Kg of granular crude antimony alloy (containing Sb-97.42%, pb-0.83%, bi-0.53%, cu-0.37%, fe-0.29% and As-0.02%) with 85Kg of sulfur powder by using a stirrer, adding the mixture into a closed container, heating to 400 ℃, preserving heat, and reacting for 1.5h to obtain 293.35Kg of low-purity antimony sulfide;
2. placing the low-purity antimony sulfide in a vacuum furnace, vacuumizing to 5-50Pa in a condensation area which is 80cm away from a heating area, slowly heating to 1200 ℃, keeping the temperature for 5 hours under the condition, controlling the temperature of the condensation area to be 200 ℃, and collecting 285.43Kg of a mixture of low-boiling-point impurities and antimony sulfide in volatile matters after distillation is finished;
3. placing the mixture of the low-boiling-point impurities and antimony sulfide in a vacuum furnace without adhering impurities, adding 2% of sulfur, and homogenizing and synthesizing the collected antimony sulfide at 580 ℃ under normal pressure; then vacuumizing to 5-50Pa, slowly heating to 650 ℃, preserving heat for 3h under the condition, collecting 257.50Kg of residue after distillation is finished, and detecting that the obtained residue is Sb 2 S 3 The purity was 99.95%.
Example 3
1. Placing 300Kg of antimony sulfide concentrate containing Sb-40% in a vacuum furnace, vacuumizing to 5-50Pa in a condensation area which is 50cm away from a heating area, slowly heating to 1100 ℃, preserving heat for 7 hours under the condition, controlling the temperature of the condensation area to be 200 ℃, and collecting 228.4Kg of a mixture of low-boiling-point impurities and antimony sulfide in volatile matters after distillation is finished;
2. placing the mixture of the low-boiling-point impurities and antimony sulfide in a vacuum furnace without adhering impurities, adding 2% of sulfur, and homogenizing and synthesizing the collected antimony sulfide at 600 ℃ under normal pressure; then vacuumizing to 5-50Pa, slowly heating to 680 ℃, preserving heat for 3h under the condition, collecting 158.6Kg of residue after distillation is finished, and detecting that the obtained residue is Sb 2 S 3 The purity thereof was 99.92%.
Example 4
1. Placing 300Kg of antimony sulfide concentrate containing Sb-45% in a vacuum furnace, vacuumizing to 5-50Pa in a condensation area 100cm away from a heating area, slowly heating to 1200 ℃, preserving heat for 6h under the condition, controlling the temperature of the condensation area to be 230 ℃, and collecting 248.4Kg of a mixture of low-boiling-point impurities and antimony sulfide in volatile matters after distillation is finished;
2. placing the mixture of the low-boiling point impurities and the antimony sulfide in a vacuum furnace without adhering impurities, adding 2% of sulfur, and homogenizing and synthesizing the collected antimony sulfide at the temperature of 610 ℃ under normal pressure; then vacuumizing to 5-50Pa, slowly heating to 700 ℃, preserving heat for 3h under the condition, collecting 179.3Kg of residue after distillation is finished, and detecting that the obtained residue is Sb 2 S 3 In conclusion, the purity of the antimony sulfide is 99.91 percent, the preparation method of antimony sulfide provided by the invention can use antimony sulfide concentrate as a raw material and also can use antimony alloy and sulfur as raw materials, and the requirements on the grade of the antimony sulfide concentrate and the purity of metal antimony alloy and sulfur are low. The preparation method of the high-purity antimony sulfide provided by the invention does not use chemical agents such as acid, alkali and the like, does not discharge three wastes, and has simple process flow, easy operation and high production efficiency; the purity of the antimony sulfide prepared by the method is as high as more than 99.9 percent, and the antimony sulfide can be applied to manufacturing brake pads and the like.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (1)
1. A preparation method of high-purity antimony sulfide is characterized by comprising the following steps:
putting antimony sulfide concentrate or low-purity antimony sulfide into a vacuum furnace, carrying out primary distillation at the temperature of 900-1200 ℃ and the vacuum degree of 5-50Pa, volatilizing impurities with boiling points lower than that of the antimony sulfide and the antimony sulfide at the temperature, and collecting and obtaining the antimony sulfide only containing low-boiling-point impurities by controlling the conditions of vacuum distillation and condensation, wherein the antimony sulfide containing the low-boiling-point impurities is Sb 2 S 3 Sb, S and low boiling point impurities; the condition of volatile matter condensation is that the condensation distance is 30-100 cm, and the condensation temperature is 100-250 ℃;
placing the antimony sulfide containing the low-boiling-point impurities into a vacuum furnace, adding sulfur, homogenizing and resynthesizing the collected antimony sulfide at the second temperature under the normal pressure, and then carrying out secondary distillation under the vacuum condition to remove impurities, wherein at the temperature, the impurities with the boiling point lower than that of the antimony sulfide volatilize, but the antimony sulfide does not volatilize, so as to obtain high-purity antimony sulfide;
the second temperature is 560-600 ℃, after the homogenization of the materials is finished under normal pressure, the materials are vacuumized until the vacuum degree is 5-50Pa, and secondary impurity removal is carried out at the temperature of 630-700 ℃;
wherein, the preparation of the low-purity antimony sulfide is prepared by vulcanizing antimony alloy with sulfur, and the preparation method comprises the following steps:
mixing antimony alloy particles with sulfur, heating to 300-700 ℃ for vulcanization to prepare low-purity antimony sulfide; or heating and melting the antimony alloy, and then introducing sulfur steam for vulcanization to prepare low-purity antimony sulfide; or mixing antimony particles and sulfur, putting the mixture into an oxygen-free closed container, heating to 320-400 ℃, and stirring to enable the antimony particles and the sulfur to react at a first stage; continuously heating to 550-650 ℃ under the conditions of no oxygen and stirring to prepare low-purity antimony sulfide;
the low-purity antimony sulfide comprises Sb 2 S 3 、S、Sb、In、Cu、As、Pb、Bi、As 2 S 3 、Sb 2 S 3 、PbS、ZnS、Cu 2 S and FeS;
the antimony sulfide concentrate comprises Sb 2 S 3 、As 2 S 3 、S、Sb 2 O 3 PbS, feS, znS and gangue components;
the purity of the high-purity antimony sulfide is more than 99.9%.
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