CN113174479B - Antimony sulfide concentrate volatilizing roasting process - Google Patents
Antimony sulfide concentrate volatilizing roasting process Download PDFInfo
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- 239000012141 concentrate Substances 0.000 title claims abstract description 55
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 59
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 42
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000003892 spreading Methods 0.000 claims abstract description 3
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 15
- 239000002893 slag Substances 0.000 abstract description 15
- 238000003723 Smelting Methods 0.000 abstract description 9
- 239000000428 dust Substances 0.000 abstract description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 abstract description 3
- 229910000410 antimony oxide Inorganic materials 0.000 abstract description 3
- 229940000489 arsenate Drugs 0.000 abstract description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 19
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 12
- 239000000292 calcium oxide Substances 0.000 description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910052959 stibnite Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052958 orpiment Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940047047 sodium arsenate Drugs 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a volatilization roasting process of antimony sulfide concentrate, which comprises the following steps: (1) mixing materials: carrying out ball milling on the antimony sulfide concentrate and the solid arsenic catalyst to obtain a mixture; (2) low-temperature high-oxygen potential arsenic fixation: spreading the mixture into a thin material layer, and reacting at 200-500 ℃ in a high-oxygen atmosphere, wherein the high-oxygen atmosphere is an oxidizing atmosphere with the oxygen content not lower than 10 vol%; (3) high-temperature low-oxygen potential volatile antimony: after the arsenic fixation is finished, placing the obtained product in a low-oxygen atmosphere, and reacting at the temperature of 600-900 ℃ to volatilize antimony, wherein the low-oxygen atmosphere is an oxidizing atmosphere with the oxygen content of 0.5-5 vol.%. Antimony sulfide concentrate is mixed with solid arsenic, arsenic is solidified at low temperature and high oxygen potential in a first-stage reaction, and arsenic is generated into arsenate which is difficult to volatilize and is left in slag; and then in the second-stage reaction, antimony is volatilized at high temperature and low oxygen potential, antimony is volatilized to generate antimony oxide and enters smoke dust, so that the effective separation of arsenic and antimony is realized, and the generation of arsenic alkali slag is reduced from a smelting source.
Description
Technical Field
The invention relates to a volatilization roasting process of antimony sulfide concentrate, belonging to the field of metallurgy and chemical engineering.
Background
The production of antimony trioxide is an important step of pyrometallurgy of antimony, is a process of oxidation and oxidation enrichment of antimony sulfide concentrate, and is an important link directly influencing the recovery rate of antimony and the grade of crude antimony. At present, the production mode of antimony trioxide in the antimony pyrometallurgy process mainly comprises two modes of volatile roasting and non-volatile roasting. The volatilization roasting is based on that antimony sulfide is heated and oxidized into easily volatilized antimony trioxide under the condition of insufficient air, the antimony trioxide enters a dust collection system, and antimony white is condensed and deposited, so that the separation of antimony and gangue components is realized. It has been widely used in industry.
The chemical properties of arsenic and antimony are very similar, and the antimony is often present in the form of associated ores in nature, is one of the common harmful impurities which are difficult to remove in antimony, and has a very large influence on the application of the antimony. In the current industrial production, the arsenic element is not effectively treated by the two roasting modes. In particular, in the volatilization roasting process, due to the high production temperature, arsenic is oxidized into easily volatilized arsenic trioxide in the roasting process, so that the arsenic trioxide and antimony trioxide enter a dust collecting system together, the quality of antimony white is affected, and the subsequent smelting burden is increased.
The traditional antimony smelting process mainly focuses on the refining link of crude antimony, and the traditional antimony smelting process is mainly operated by adding alkaline substances such as sodium carbonate and the like into the crude antimony to react with arsenic to generate corresponding arsenate, so that the aim of separating arsenic from antimony is fulfilled, and slag generated in the process is called primary arsenic alkali slag. The primary arsenic alkali slag generally contains 20-40% of antimony and 1-5% of arsenic, and because the antimony content is high, smelting enterprises generally need to return the slag to a reverberatory furnace for treatment, so that the flow and energy consumption of smelting are increased undoubtedly, and the slag generated in the process is called secondary arsenic alkali slag, wherein the antimony content is below 10%, and the arsenic content is 4-10%.
The average content of arsenic in the arsenic-alkali residue is 1% -15%, the arsenic exists in the form of soluble sodium arsenate, the arsenic-alkali residue is extremely toxic, and a large amount of residual alkali is also contained in the arsenic-alkali residue, so that the arsenic-alkali residue seriously pollutes the environment and harms the survival safety of human beings. The proper treatment of the arsenic alkali slag is a worldwide problem, large and medium-sized enterprises adopt a special slag storehouse to properly stack the arsenic alkali slag, and the arsenic alkali slag of small-sized smelters is basically stacked in the open air, so that the arsenic alkali slag is extremely harmful. By the end of 2017, the total stacking amount of arsenic-alkali residues in China reaches more than 30 million tons, and the increase amount is about 5000-10000 tons every year. The antimony and arsenic smelting alkaline residue becomes a heavy metal heavy pollution source in China, and a simple and effective treatment way is urgently needed to be found.
Disclosure of Invention
In order to solve the problems that arsenic and antimony can not be separated in the roasting process of the existing antimony sulfide concentrate and arsenic caustic sludge pollutes the environment in the subsequent smelting process, the invention aims to provide a volatilization roasting process of antimony sulfide concentrate, which realizes the preliminary separation of arsenic and antimony in the roasting process of antimony sulfide concentrate and reduces the generation amount of arsenic caustic sludge from the source.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a volatilization roasting process for antimony sulfide concentrate comprises the following steps:
(1) mixing materials: carrying out ball milling and mixing on the antimony sulfide concentrate and the solid arsenic agent to obtain a mixture;
(2) low-temperature high-oxygen potential arsenic fixation: spreading the mixture into a thin material layer, and reacting at 200-500 ℃ in a high-oxygen atmosphere, wherein the high-oxygen atmosphere is an oxidizing atmosphere with the oxygen content not lower than 10 vol%;
(3) high-temperature low-oxygen potential volatile antimony: after the arsenic fixation is finished, placing the obtained product in a low-oxygen atmosphere, and reacting at the temperature of 600-900 ℃ to volatilize antimony, wherein the low-oxygen atmosphere is an oxidizing atmosphere with the oxygen content of 0.5-5 vol.%.
Preferably, in the step (1), the arsenic fixing agent is one or more of lime, soda ash and caustic soda, and the dosage of the arsenic fixing agent is 1-10% of the weight of the antimony sulfide concentrate.
Preferably, in the step (2), the thickness of the thin material layer is 1-5 mm.
Preferably, in the step (2), the oxidizing atmosphere containing oxygen in an amount of not less than 10 vol.% is a pure oxygen atmosphere or a mixed nitrogen-oxygen atmosphere containing oxygen in an amount of not less than 10 vol.%.
Preferably, in the step (2), the reaction temperature is 400-500 ℃, and the reaction time is 30-120 min.
Preferably, in the step (3), the oxidizing atmosphere containing oxygen of not more than 5 vol.% is a nitrogen-oxygen mixed atmosphere containing oxygen of 0.5 to 5 vol.%.
Preferably, in the step (3), the reaction temperature is 800-.
The invention takes lime as an example of a solid arsenic agent, and the reaction principle is as follows:
(1) conversion between arsenic, antimony and their oxysulfides at low temperatures
Sb2S3(s)+4.5O2(g)＝Sb2O3(s)+3SO2(g)
4As(s)+3O2(g)＝2As2O3(s)
As2S3(s)+4.5O2(g)＝As2O3(s)+3SO2(g)
As2S5(s)+6.5O2(g)＝As2O3(s)+5SO2(g)
As2O3(s)+O2(g)＝As2O5(s)
As2O3(s)＝As2O3(g)
(2) Reaction of arsenic with lime at low temperature
As2O3(s)+2CaO(s)+O2(g)＝Ca2As2O7(s)
As2O3(g)+2CaO(s)+O2(g)＝Ca2As2O7(s)
As2O5(s)+2CaO(s)＝Ca2As2O7(s)
(3) Volatilization of arsenic and antimony at high temperature
Sb2S3(s)+4.5O2(g)＝Sb2O3(g)+3SO2(g)
Sb2O3(s)＝Sb2O3(g)
As2O5(s)＝As2O3(g)+O2(g)
As2O3(s)＝As2O3(g)
(4) Fixation of arsenic and antimony by lime at high temperature
As2O3(g)+2CaO(s)+O2(g)＝Ca2As2O7(s)
Sb2O3(s)+2CaO(s)+O2(g)＝Ca2Sb2O7(s)
Sb2O3(g)+2CaO(s)+O2(g)＝Ca2Sb2O7(s)
The invention has the advantages that:
mixing antimony sulfide concentrate with solid arsenic, adopting two-stage heating roasting, strictly controlling two-stage reaction temperature and reaction atmosphere, and in one-stage reaction, fixing arsenic at low temperature and high oxygen potential, wherein arsenic generates arsenate which is difficult to volatilize and is left in slag; and then in the second-stage reaction, antimony is volatilized at high temperature and low oxygen potential, antimony is volatilized to generate antimony oxide, and the antimony oxide enters smoke dust, so that the arsenic and the antimony are effectively separated, and the production of arsenic alkali slag is reduced from a smelting source.
Detailed Description
The substance of the present invention is illustrated by the following examples, but the scope of the present invention is not limited thereto.
Example 1
The main chemical components of the antimony sulfide concentrate are Sb 29.2%, As 0.94%, S30.4%, Fe 18.3%, Ca 0.29% and Zn 0.49%. 10g of antimony sulfide concentrate and 1g of calcium oxide are placed in a ball milling tank, ball milling is carried out for 30min at the rotating speed of 500r/min, and the antimony sulfide concentrate and the calcium oxide concentrate are spread into a thin layer of 2mm and placed in a horizontal tubular furnace. Introducing W into the furnace(O2)60 vol.% nitrogen-oxygen mixed gas (flow rate 500mL/min), heating to 400 ℃, and keeping the temperature for 1 h; after the heat preservation at 400 ℃, W is rapidly introduced(O2)Heating to 800 ℃ at a heating rate of 7 ℃/min and keeping the temperature for 75min, finally cooling to 500 ℃ at a rate of 10 ℃/min, and taking out the material. The calculation shows that the volatilization rate of antimony in the concentrate is 91.21%, the arsenic fixation rate is 64.63%, and the sulfur fixation rate is 17.16%.
Example 2
The main chemical components of the antimony sulfide concentrate are Sb 41.05%, As 0.53%, S26.75%, Fe 10.67%, Ca 0.75% and Zn 0.31%. 10g of antimony sulfide concentrate and 1.5g of calcium oxide are placed in a ball milling tank, ball milling is carried out for 30min at the rotating speed of 500r/min, and the mixture is spread into a thin layer of 2mm and placed in a horizontal tubular furnace. Introducing W into the furnace(O2)20 vol.% nitrogen-oxygen mixed gas (flow rate 500mL/min), heating to 400 ℃, and keeping the temperature for 1 h; after the heat preservation is finished, W is rapidly introduced(O2)Heating the nitrogen-oxygen mixed gas (the flow rate is 2000mL/min) at the temperature rising rate of 7 ℃/min to 800 ℃, keeping the temperature for 75min, finally cooling the nitrogen-oxygen mixed gas at the speed of 10 ℃/min to 500 ℃, and taking out the material. The calculation shows that the volatilization rate of antimony in the concentrate is 93.02%, the arsenic fixation rate is 69.66%, and the sulfur fixation rate is 18.89%.
Comparative example 1
Antimony sulphide concentrate the same as in example 1. 10g of antimony sulfide concentrate and 1g of calcium oxide are placed in a ball milling tank, ball milling is carried out for 30min at the rotating speed of 500r/min, and the antimony sulfide concentrate and the calcium oxide concentrate are spread into a thin layer of 2mm and placed in a horizontal tubular furnace. Introducing W into the furnace(O2)Heating to 800 ℃ at a heating rate of 7 ℃/min and keeping the temperature for 75min, finally cooling to 500 ℃ at a rate of 10 ℃/min, and taking out the material. The calculation shows that the volatilization rate of antimony in the concentrate is 94.03%, the arsenic fixation rate is 19.23% and the sulfur fixation rate is 16.35%.
Comparative example 2
Antimony sulphide concentrate the same as in example 1. 10g of antimony sulfide concentrate and 1g of calcium oxide are placed in a ball milling tank, ball milling is carried out for 30min at the rotating speed of 500r/min, and the antimony sulfide concentrate and the calcium oxide concentrate are spread into a thin layer of 2mm and placed in a horizontal tubular furnace. Introducing W into the furnace(O2)60 vol.% nitrogen-oxygen mixed gas (flow rate 500mL/min), heating to 800 ℃ at a heating rate of 7 ℃/min, keeping the temperature for 75min, finally cooling to 500 ℃ at a speed of 10 ℃/min, and taking out the material. The calculation shows that the volatilization rate of antimony in the concentrate is 28.45%, the arsenic fixing rate is 69.77%, and the sulfur fixing rate is 18.78%.
Comparative example 3
Antimony sulphide concentrate the same as in example 1. 10g of antimony sulfide concentrate and 1g of calcium oxide are placed in a ball milling tank, ball milling is carried out for 30min at the rotating speed of 500r/min, and the mixture is spread into a thin layer of 2mm and placed in a horizontal tubular furnace. Continuously introducing W into the furnace(O2)60 vol.% nitrogen-oxygen mixed gas (flow rate 500mL/min), firstly heating to 400 ℃, and preserving heat for 1 h; then heating to 800 ℃ at the heating rate of 7 ℃/min, preserving the heat for 75min, finally cooling to 500 ℃ at the speed of 10 ℃/min, and taking out the materials. The calculation shows that the volatilization rate of antimony in the concentrate is 25.43%, the arsenic fixing rate is 72.98%, and the sulfur fixing rate is 16.23%.
Comparative example 4
Antimony sulphide concentrate the same as in example 1. Antimony sulphide concentrate the same as in example 1. 10g of antimony sulfide concentrate and 1g of calcium oxide are placed in a ball milling tank, ball milling is carried out for 30min at the rotating speed of 500r/min, and the antimony sulfide concentrate and the calcium oxide concentrate are spread into a thin layer of 2mm and placed in a horizontal tubular furnace. Continuously introducing W into the furnace(O2)1.5 vol.%Heating the nitrogen-oxygen mixed gas (the flow rate is 700mL/min) to 400 ℃ and preserving the heat for 1 h; then heating to 800 ℃ at the heating rate of 7 ℃/min, preserving the heat for 75min, finally cooling to 500 ℃ at the speed of 10 ℃/min, and taking out the materials. The calculation shows that the volatilization rate of antimony in the concentrate is 95.01%, the arsenic fixing rate is 22.45% and the sulfur fixing rate is 17.25%.
Comparative example 5
The main chemical components of the antimony sulfide concentrate are Sb 29.2%, As 0.94%, S30.4%, Fe18.3%, Ca 0.29% and Zn 0.49%. 10g of antimony sulfide concentrate and 1g of calcium oxide are placed in a ball milling tank, ball milling is carried out for 30min at the rotating speed of 500r/min, and the antimony sulfide concentrate and the calcium oxide concentrate are spread into a thin layer of 2mm and placed in a horizontal tubular furnace. Introducing W into the furnace(O2)1.5 vol.% nitrogen-oxygen mixed gas (flow rate 700mL/min), heating to 400 ℃, and keeping the temperature for 1 h; after the heat preservation at 400 ℃, W is rapidly introduced(O2)60 vol.% nitrogen-oxygen mixed gas (flow rate 500mL/min), heating to 800 ℃ at a heating rate of 7 ℃/min, keeping the temperature for 75min, finally cooling to 500 ℃ at a speed of 10 ℃/min, and taking out the material. The calculation shows that the volatilization rate of antimony in the concentrate is 26.45%, the arsenic fixation rate is 70.24% and the sulfur fixation rate is 16.63%.
Claims (7)
1. A volatilization roasting process of antimony sulfide concentrate is characterized by comprising the following steps:
(1) mixing materials: carrying out ball milling and mixing on the antimony sulfide concentrate and the solid arsenic agent to obtain a mixture;
(2) low-temperature high-oxygen potential arsenic fixation: spreading the mixture into a thin material layer, and reacting at 200-500 ℃ in a high-oxygen atmosphere, wherein the high-oxygen atmosphere is an oxidizing atmosphere with the oxygen content not lower than 10 vol%;
(3) high-temperature low-oxygen potential volatile antimony: after the arsenic fixation is finished, placing the obtained product in a low-oxygen atmosphere, and reacting at the temperature of 600-900 ℃ to volatilize antimony, wherein the low-oxygen atmosphere is an oxidizing atmosphere with the oxygen content of 0.5-5 vol.%.
2. The antimony sulfide concentrate volatilizing and roasting process of claim 1, characterized in that: in the step (1), the arsenic fixing agent is one or more of lime, soda ash and caustic soda, and the dosage of the arsenic fixing agent is 1-10% of the weight of the antimony sulfide concentrate.
3. The antimony sulfide concentrate volatilizing and roasting process of claim 1, characterized in that: in the step (1), the thickness of the thin material layer is 1-5 mm.
4. The antimony sulfide concentrate volatilizing and roasting process of claim 1, characterized in that: in the step (2), the oxidizing atmosphere having an oxygen content of not less than 10 vol.% is a pure oxygen atmosphere or a mixed nitrogen-oxygen atmosphere having an oxygen content of not less than 10 vol.%.
5. The antimony sulfide concentrate volatilizing and roasting process of claim 1, characterized in that: in the step (2), the reaction temperature is 400-500 ℃, and the reaction time is 30-120 min.
6. The antimony sulfide concentrate volatilizing and roasting process of claim 1, characterized in that: in the step (3), the oxidizing atmosphere having an oxygen content of not higher than 5 vol.% is a nitrogen-oxygen mixed atmosphere having an oxygen content of 0.5 to 5 vol.%.
7. The volatilizing and roasting process of antimony sulfide concentrate according to claim 1, characterized by comprising the following steps: in the step (3), the reaction temperature is 800-900 ℃, and the reaction time is 30-120 min.
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| CN101423252A (en) * | 2008-11-17 | 2009-05-06 | 河南豫光金铅股份有限公司 | Oxygen-enriched production process of diantimony trioxide |
| CN105648226A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony from arsenic in antimony-arsenic soot |
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| CN101423252A (en) * | 2008-11-17 | 2009-05-06 | 河南豫光金铅股份有限公司 | Oxygen-enriched production process of diantimony trioxide |
| CN105648226A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony from arsenic in antimony-arsenic soot |
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