CN113564384B - Production method of refined antimony with ultralow arsenic content - Google Patents
Production method of refined antimony with ultralow arsenic content Download PDFInfo
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- CN113564384B CN113564384B CN202110837559.XA CN202110837559A CN113564384B CN 113564384 B CN113564384 B CN 113564384B CN 202110837559 A CN202110837559 A CN 202110837559A CN 113564384 B CN113564384 B CN 113564384B
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a production method of refined antimony with ultra-low arsenic content, which comprises the steps of reducing and smelting antimony oxide by a reducing agent, removing floating slag, adding caustic soda flakes to remove arsenic, wherein the content of arsenic reaches 0.03%; according to the weight ratio of caustic soda flakes to arsenic of 30-60: adding caustic soda flakes according to the proportion of 1, and blowing compressed air to finely remove arsenic; the number of fine arsenic removal is 3-5; skimming dross after each fine arsenic removal; continuously blowing compressed air after fine arsenic removal, wherein the weight ratio of the refined lime to the arsenic is 50-120:1 adding refined lime, and removing floating slag after 1-10 minutes, wherein the operation is carried out for 1-3 times; obtaining the ultra-low arsenic content refined antimony with the arsenic content of less than 0.005 percent. The production method of the invention can controllably produce the refined antimony with ultra-low arsenic content, and provides a wider range for deep processing of refined antimony products.
Description
Technical Field
The invention belongs to the field of antimony smelting, relates to production operation of refined antimony products, and particularly relates to a production method of refined antimony with ultralow arsenic content.
Background
Antimony is a silver-white nonferrous metal with brittleness and poor electrical and thermal conductivity, and is mainly used in the industries of alloy, military industry, flame retardant, glass and the like, and most of antimony products are deeply processed by adopting refined antimony products, such as high-purity antimony oxide, ethylene glycol antimony and the like. China is the country with the largest antimony yield in the world, the world antimony yield in 2010 is 16.7 ten thousand tons, the world antimony yield in 2010 in China reaches 15.0 ten thousand tons, which accounts for more than 89% of the world antimony yield, and China has irreplaceable advantages in antimony resources and production.
The mineral raw materials for smelting antimony mainly comprise stibnite, jamesonite and the like, wherein the stibnite and the stibnite are usually volatilized and smelted by a blast furnace, so that most of antimony is volatilized to form antimony oxide, which is commonly called as antimony oxide, and the antimony oxide is subjected to reduction smelting and oxidation refining in a reverberatory furnace to produce refined antimony.
The oxidation refining of antimony mainly adopts caustic soda flakes or soda ash to remove arsenic, and adopts ammonium dihydrogen phosphate or phosphoric acid to remove lead. The current fine antimony sales generally require that the arsenic content of the fine antimony is below 0.05 percent, and the part of the fine antimony is below 0.03 percent, but with the continuous upgrade of downstream antimony industries, the requirements on the fine antimony are higher and higher, particularly the arsenic content in the fine antimony, and a plurality of customers require that the arsenic content in the fine antimony is below 0.01 percent, even below 0.005 percent. The antimony smelting enterprises can not produce the required refined antimony, and the antimony smelting enterprises are always puzzled.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a production method of refined antimony with ultralow arsenic content, which is used for carrying out oxidation refining on antimony to remove arsenic again to achieve the arsenic content in the refined antimony below 0.005%.
The purpose of the invention is realized by the following scheme:
the invention relates to a production method of refined antimony with ultralow arsenic content, which comprises the steps of adding No. 1 refined antimony into a reverberatory furnace, then adding caustic soda flakes, blowing compressed air for the first time to finely remove arsenic, repeatedly adding caustic soda flakes and finely removing arsenic for 3-5 times to obtain refined antimony A, wherein when fine arsenic is removed at any time, the mass ratio of the added caustic soda flakes to arsenic in No. 1 refined antimony is 30-60: blowing compressed air and adding refined lime for the second time, removing floating slag, repeatedly adding refined lime and removing floating slag for 1-3 times to obtain refined antimony B, finally adding ammonium dihydrogen phosphate or phosphoric acid, blowing compressed air for the third time, removing lead, and then casting ingot; thus obtaining the refined antimony with ultra-low arsenic content.
In the invention, the used caustic soda flakes are industrial grade, and the content is more than 99%.
Preferably, the mass fraction of arsenic in the No. 1 refined antimony is 0.02-0.03%.
Preferably, the preparation method of the No. 1 refined antimony comprises the following steps: reducing and smelting antimony oxide by a reducing agent, removing scum to obtain crude antimony, and adding caustic soda flakes into the crude antimony to remove arsenic to obtain the antimony oxide; the mass ratio of the caustic soda flakes to the crude antimony is 3.5-5:1.
further preferably, the mass fraction of arsenic in the crude antimony is less than or equal to 2.00%, preferably less than or equal to 1.50%, and further preferably less than or equal to 1.30%.
Preferably, the area of the reverberatory furnace is 22m 2 And the following.
The inventor unexpectedly finds that the area of the reverberatory furnace influences the arsenic removal effect, and the area of the reverberatory furnace is controlled to be 22m 2 Hereinafter, a more excellent arsenic removal effect can be obtained.
Further preferred areThe area of the reverberatory furnace is 16m 2 And the following.
Further preferably, the reverberatory furnace is carried out in the first 2 batches after the overhaul.
In the actual production process, because the brick joints of the old furnace platforms, the inner walls of the furnace walls and the like are provided with slag, the first 2 batches after maintenance are used for production, and the refined antimony with ultralow arsenic content can be prepared more easily.
Preferably, the temperature in the reverberatory furnace is 800-1000 ℃.
In the invention, the temperature of the reverberatory furnace is continuously controlled to be 800-1000 ℃ in the whole arsenic removing process,
preferably, the mass ratio of the caustic soda flakes to the arsenic in the No. 1 refined antimony is 40-50:1.
in the invention, the addition amount of caustic soda flakes needs to be effectively controlled, if the addition amount is too small, the arsenic removal target is difficult to achieve, and if the addition amount is too large, the arsenic removal target is difficult to achieve, the antimony is uneconomical, the antimony is lost, the slag amount is large, the antimony liquid level is reduced after slag is removed, the slag removal operation is not facilitated, and the slag removal is not clean.
Preferably, the pressure of the first compressed air blowing is 0.15 to 0.5MPa.
Preferably, the time for any one fine arsenic removal is 10-60min.
Preferably, the mass ratio of the arsenic in the refined lime to the arsenic in the refined antimony A is 50-120:1.
further preferably, the mass ratio of the refined lime to the arsenic in the refined antimony A is 80-110:1.
in the invention, the effective CaO content of the used refined lime is more than 75 percent.
Preferably, the pressure of the compressed air blown in for the second time is 0.15 to 0.5MPa.
Preferably, after adding the refined lime, scum is removed after 1-5 min.
Preferably, the pressure of the compressed air blown in for the third time is 0.15 to 0.5MPa.
Preferably, the furnace temperature of the reverberatory furnace is controlled to be 700-750 ℃ during ingot casting, and is preferably 720-750 DEG C
The inventor finds that the temperature of the reverberatory furnace needs to be effectively controlled during ingot casting, the temperature of the reverberatory furnace cannot be increased, and if the temperature is too high, slag on the inner wall of the furnace wall is melted and added into antimony liquid, so that the content of the ingot is influenced.
Advantageous effects
According to the invention, a proper amount of caustic soda flakes is added into the refined antimony to remove arsenic, and the refined lime is used for cleaning the slag, so that the ultra-low arsenic content refined antimony with the arsenic content of less than 0.005% is provided, a wider range is provided for deep processing of refined antimony products, the antimony quality is improved, and the application range of the products is widened.
Detailed Description
The following examples are intended to illustrate the invention but not to further limit the invention. The invention can be implemented in any of the ways described in the summary of the invention.
Example 1:
reducing and smelting antimony oxide produced by an ash blowing furnace by white coal, removing scum to obtain crude antimony with the arsenic content of 1.80%, and adding caustic soda flakes to remove arsenic until the arsenic content reaches 0.025%;
according to the weight ratio of caustic soda flakes to arsenic of 42:1, adding caustic soda flakes, blowing compressed air for fine arsenic removal, wherein the pressure level of the compressed air is 0.15MPa, and the furnace temperature is about 900 ℃; the fine arsenic removal times are 3 times, and the fine arsenic removal time is controlled to be about 50min each time; scruff out after each fine arsenic removal;
continuously blowing compressed air after fine arsenic removal, wherein the weight ratio of the refined lime to the arsenic is 85:1 adding refined lime, and removing floating slag after 3 minutes, wherein the operation is carried out for 2 times; after the scum is taken off, adding phosphoric acid and blowing compressed air to remove lead; finally obtaining the ultra-low arsenic content refined antimony with the arsenic content of less than 0.0043%; the area of the reverberatory furnace is 20m 2 And the furnace temperature is controlled to be about 720 ℃ during ingot casting.
Example 2:
reducing and smelting antimony oxide produced by an ash blowing furnace by white coal, removing scum to obtain crude antimony with the arsenic content of 1.50%, and adding caustic soda flakes to remove arsenic until the arsenic content reaches 0.027%; according to the weight ratio of caustic soda flakes to arsenic of 50: adding caustic soda flakes according to the proportion of 1, blowing compressed air to carry out fine arsenic removal, wherein the pressure level of the compressed air is 0.15MPa, and the furnace temperature is about 900 ℃; the fine arsenic removal times are 3 times, and the fine arsenic removal time is controlled to be about 50min each time; skimming dross after each fine arsenic removal; continuously blowing compressed air after fine arsenic removal, wherein the weight ratio of the refined lime to the arsenic is 110:1 adding refined lime, and removing floating slag after 3 minutes, wherein the operation is carried out for 2 times; after scum is taken off, adding phosphoric acid and blowing compressed air to remove lead; finally obtaining the ultra-low arsenic content refined antimony with the arsenic content of less than 0.0028 percent; the area of the reverberatory furnace is 20m2, and the furnace temperature is controlled at about 750 ℃ during ingot casting.
Example 3:
reducing and smelting antimony oxide produced by an ash blowing furnace by white coal, removing scum to obtain crude antimony with the arsenic content of 1.35%, and adding caustic soda flakes to remove arsenic until the arsenic content reaches 0.023%; the weight ratio of caustic soda flakes to arsenic is 50: adding caustic soda flakes according to the proportion of 1, blowing compressed air to carry out fine arsenic removal, wherein the pressure level of the compressed air is 0.15MPa, and the furnace temperature is about 900 ℃; the fine arsenic removal times are 3 times, and the fine arsenic removal time is controlled to be about 50min each time; skimming dross after each fine arsenic removal; continuously blowing compressed air after fine arsenic removal, wherein the weight ratio of the refined lime to the arsenic is 110:1 adding refined lime, and removing floating slag after 3 minutes, wherein the operation is carried out for 2 times; after the scum is taken off, adding phosphoric acid and blowing compressed air to remove lead; finally obtaining the ultra-low arsenic content refined antimony with the arsenic content of less than 0.0019%; the area of the reverberatory furnace is 16m 2 And the furnace temperature is controlled to be about 720 ℃ during ingot casting.
Comparative example 1:
reducing and smelting antimony oxide produced by an ash blowing furnace by white coal, removing floating slag to obtain crude antimony with the arsenic content of 1.24%, and adding caustic soda flakes to remove arsenic until the arsenic content reaches 0.016%; according to the weight ratio of caustic soda flakes to arsenic of 40:1, adding caustic soda flakes, blowing compressed air for fine arsenic removal, wherein the pressure level of the compressed air is 0.25MPa, and the furnace temperature is about 900 ℃; the fine arsenic removal times are 3 times, and the fine arsenic removal time is controlled to be about 50min each time; skimming dross after each fine arsenic removal; continuously blowing compressed air after fine arsenic removal, wherein the weight ratio of the refined lime to the arsenic is 100:1 adding refined lime, and removing floating slag after 3 minutes, wherein the operation is carried out for 3 times; skimming off the scumThen adding phosphoric acid and blowing compressed air to remove lead; lead removal reaches the standard. Sampling before furnace discharge, testing to obtain arsenic content of 0.0031%, and discharging. Sampling and testing every 1 hour in the process of placing the furnace, wherein the previous result is respectively 0.0048%, the second and subsequent results exceed 0.005%, respectively 0.0053%, 0.0072%, 0.010% and 0.023%, the subsequent results are higher, and the final ultra-low arsenic content refined antimony which reaches below 0.005% is only 5.5 tons and accounts for about 10% of the whole furnace batch refined antimony; the area of the reverberatory furnace is 24m 2 And the furnace temperature is controlled to be about 720 ℃ during ingot casting.
Comparative example 2:
reducing and smelting antimony oxide produced by an ash blowing furnace by white coal, removing scum to obtain crude antimony with the arsenic content of 1.83%, and adding caustic soda flakes to remove arsenic until the arsenic content reaches 0.025%; according to the weight ratio of caustic soda flakes to arsenic of 80: adding caustic soda flakes according to the proportion of 1, blowing compressed air to carry out fine arsenic removal, wherein the pressure level of the compressed air is 0.35MPa, and the furnace temperature is about 900 ℃; the fine arsenic removal times are 3 times, and the fine arsenic removal time is controlled to be about 50min each time; after each fine arsenic removal, scum is removed. Because the amount of caustic soda flakes added each time is large, the slag removing operation difficulty is increased because the liquid level of antimony is greatly reduced during the third fine arsenic removal and slag removal, and partial slag cannot be removed completely. Continuously blowing compressed air after fine arsenic removal, wherein the weight ratio of the fine lime to the arsenic is 100:1 adding refined lime, and removing floating slag after 3 minutes, wherein the operation is carried out for 3 times; after scum is taken off, adding phosphoric acid and blowing compressed air to remove lead; lead removal reaches the standard. The arsenic content of the sample before the furnace is put into the furnace to be tested is 0.028 percent, which can not meet the requirement. The area of the reverberatory furnace is 20m 2 。
Claims (8)
1. A production method of refined antimony with ultra-low arsenic content is characterized in that: adding No. 1 refined antimony into a reverberatory furnace, adding caustic soda flakes, blowing compressed air for the first time to finely remove arsenic, repeatedly adding caustic soda flakes and finely removing arsenic for 3-5 times to obtain refined antimony A, wherein the mass ratio of the added caustic soda flakes to arsenic in No. 1 refined antimony is 30-60: blowing compressed air and adding refined lime for the second time, removing floating slag, repeatedly adding refined lime and removing floating slag for 1-3 times to obtain refined antimony B, finally adding ammonium dihydrogen phosphate or phosphoric acid, blowing compressed air for the third time, removing lead, and then casting ingots; obtaining the refined antimony with ultra-low arsenic content;
the mass ratio of the refined lime to the arsenic in the refined antimony A is 50-120:1;
and controlling the furnace temperature of the reverberatory furnace at 700-750 ℃ during ingot casting.
2. The method for producing the refined antimony with ultra-low arsenic content as claimed in claim 1, wherein: the mass fraction of arsenic in the No. 1 refined antimony is 0.02-0.03%;
the preparation method of the No. 1 refined antimony comprises the steps of reducing and smelting antimony oxide by a reducing agent, removing floating slag to obtain crude antimony, and adding caustic soda flakes into the crude antimony to remove arsenic to obtain the refined antimony; the mass ratio of the caustic soda flakes to the crude antimony is 3.5-5:1.
3. the method for producing the refined antimony with the ultra-low arsenic content as claimed in claim 2, wherein the method comprises the following steps: the mass fraction of arsenic in the crude antimony is less than or equal to 2.00 percent.
4. The method for producing the refined antimony with ultra-low arsenic content as claimed in claim 1, wherein: the area of the reverberatory furnace is 22m 2 And the following.
5. The method for producing the refined antimony with ultra-low arsenic content as claimed in claim 1, wherein: the temperature in the reverberatory furnace is 800-1000 ℃.
6. The method for producing the refined antimony with ultra-low arsenic content as claimed in claim 1, wherein: the mass ratio of the caustic soda flakes to arsenic in the No. 1 refined antimony is (40-50): 1.
7. the method for producing the refined antimony with the ultra-low arsenic content as claimed in claim 1, wherein the method comprises the following steps: the pressure of the compressed air blown in for the first time is 0.15-0.5MPa; the time for any one time of fine arsenic removal is 10-60min.
8. The method for producing the refined antimony with the ultra-low arsenic content as claimed in claim 1, wherein the method comprises the following steps: the pressure of the compressed air blown in for the second time is 0.15-0.5MPa; after adding the refined lime, removing the floating slag after 1-5 min.
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