CN116692941A - Method for preparing high-quality sodium pyroantimonate through gradient purification and oxidation - Google Patents
Method for preparing high-quality sodium pyroantimonate through gradient purification and oxidation Download PDFInfo
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- CN116692941A CN116692941A CN202310826659.1A CN202310826659A CN116692941A CN 116692941 A CN116692941 A CN 116692941A CN 202310826659 A CN202310826659 A CN 202310826659A CN 116692941 A CN116692941 A CN 116692941A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 42
- 230000003647 oxidation Effects 0.000 title claims abstract description 41
- CIWAOCMKRKRDME-UHFFFAOYSA-N tetrasodium dioxido-oxo-stibonatooxy-lambda5-stibane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Sb]([O-])(=O)O[Sb]([O-])([O-])=O CIWAOCMKRKRDME-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052742 iron Inorganic materials 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 34
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 30
- 239000011707 mineral Substances 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 29
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229910052787 antimony Inorganic materials 0.000 claims description 29
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000003828 vacuum filtration Methods 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 230000001698 pyrogenic effect Effects 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 abstract description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229910052569 sulfide mineral Inorganic materials 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- 239000000047 product Substances 0.000 description 28
- 229940079101 sodium sulfide Drugs 0.000 description 18
- 239000002994 raw material Substances 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229960002163 hydrogen peroxide Drugs 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 4
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BJIQCYSMVVESCD-UHFFFAOYSA-N [Sb]([S-])([O-])[O-].[Na+].[Na+].[Na+] Chemical compound [Sb]([S-])([O-])[O-].[Na+].[Na+].[Na+] BJIQCYSMVVESCD-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052973 jamesonite Inorganic materials 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019446 NaSb Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- -1 military industry Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/02—Antimonates; Antimonites
- C01G30/023—Antimonates; Antimonites of ammonium, alkali or alkaline-earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for preparing high-quality sodium pyroantimonate by gradient purification and oxidization includes such steps as leaching the antimonic sulfide minerals in sodium sulfide solution, adding the antimonic sulfide minerals to the leached liquid for preliminary iron removal, adding activated carbon to the liquid after preliminary iron removal, deep iron removal, oxidizing by oxygen at low temp, removing impurities, and oxidizing by oxygen at high temp. The essence of the invention is that the purpose of preparing high-quality sodium pyroantimonate is realized by adopting a combination mode of echelon purification and echelon oxidation. The sodium thiosulfate solution is prepared by adding the preliminary purification of the antimony sulfide-containing mineral and the deep purification of the activated carbon adsorption, and the high-quality sodium pyroantimonate product is prepared by low-temperature pressurized oxidation and high-temperature pressurized oxidation. The invention has the advantages of good product quality, environmental protection and simple operation.
Description
Technical Field
The invention relates to a hydrometallurgical process in the metallurgical field, in particular to a hydrometallurgical method for preparing high-quality sodium pyroantimonate from an antimony sulfide-containing mineral raw material.
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, flame retardant, military industry, glass and the like. Antimony production in the world is mainly concentrated in China, tajistein, russian, australia and Bolivia, and the like, but China is the largest antimony producing country in the world. The mineral raw materials of antimony metallurgy mainly comprise stibium ore, antimonite ore and jamesonite, and antimony in the raw materials exists in the form of stibium ore. Antimony-containing soot produced in heavy metal lead smelting processes is an important secondary material of antimony, in which antimony exists mainly in the form of oxides.
The antimony metallurgy process mainly comprises a fire process and a wet process, wherein the fire process is to firstly oxidize an antimony raw material at a high temperature to produce antimony oxide, then reduce, smelt and refine the antimony oxide to produce metallic antimony ingots, and finally prepare various antimony products by using the antimony ingots. The wet process is to dissolve antimony into solution in sodium sulfide system or chloride system and then to produce antimony product through oxidation or electrodeposition. The industrial products of antimony mainly include three kinds of antimony ingots, antimony white and sodium pyroantimonate.
Sodium pyroantimonate, molecular formula NaSb (OH) 6 Is a white powder which is indissolvable in water, dilute alkali, dilute inorganic acid and acetic acid, and can be dissolved in tartaric acid and hot concentrated sulfuric acid. Jiao Tisuan sodium is widely applied to the fields of high-grade glass clarifying agents, chemical industry and electronic industry, textile flame retardants, milky white agents, paint additives, decoloring agents and the like. Due to the rapid development of the photovoltaic industry, sodium pyroantimonate is mainly used as a clarifying agent in the production process of photovoltaic glass. The sodium pyroantimonate is prepared by oxidizing Sb (III) into Sb (V) under specific conditions by using oxidant such as sodium nitrate, hydrogen peroxide, air or oxygen to obtain sodium pyroantimonate product.
The pyrogenic process is typically represented by the sodium nitrate oxidation process, which is a pyrogenic process for preparing sodium antimonate by oxidizing metallic antimony or antimony trioxide with sodium nitrate under high-temperature alkaline conditions. Although the pyrogenic process has the advantages of simple operation and low production cost, the process has been eliminated at present because sodium nitrate is used as an oxidant in the high-temperature production process, harmful gases are generated in the reaction process, and the defects of poor product quality and serious environmental pollution exist.
The wet process is also divided into an acid system and an alkaline system, wherein the acid system is represented by a chlorination hydrolysis method, the chlorination hydrolysis method is characterized in that antimony-containing materials are leached by chlorine in a hydrochloric acid solution in an oxidizing way, and then sodium hydroxide is added into the leaching solution to hydrolyze antimony pentachloride to produce sodium pyroantimonate products. Although the chlorination hydrolysis method has the advantages of strong raw material adaptability and good product quality, the method has the defects of long process, serious equipment corrosion, poor operation condition and large wastewater yield.
The alkaline system comprises three methods of alkaline oxidation, potassium salt and sodium sulfide. The alkaline oxidation method is also called a sodium salt method or an oxidation reflux method, namely, oxidizing antimony white with hydrogen peroxide in sodium hydroxide solution to generate sodium pyroantimonate products. The method has the advantages of short process flow and simple operation, but has the defects of poor product quality consistency, volume expansion of the solution and high production cost. The potassium salt method is to dissolve antimony white in potassium hydroxide solution by oxydol oxidation, add sodium hydroxide into Jiao Tisuan potassium solution to produce double decomposition reaction to prepare sodium pyroantimonate, and recycle potassium hydroxide after regeneration. The method has the advantage of good product quality, but has the problems of high production cost and volume expansion of the solution.
The sodium sulphide system oxidation process is mainly used for treating antimony sulphide containing mineral raw materials present as antimony trioxide mineral phases. Firstly, leaching stibium ore, antimonite ore or jamesonite in a mixed solution of sodium sulfide and sodium hydroxide to dissolve the antimony sulfide in a matching way to generate a sodium thioantimonite solution; secondly, introducing hydrogen peroxide, air or oxygen into the sodium thiosulfate solution at a high temperature for oxidation, and washing and drying a precipitate product to obtain a sodium pyroantimonate product; finally, neutralizing, concentrating and crystallizing the oxidized liquid to obtain sodium thiosulfate byproducts. The sodium pyroantimonate product is directly prepared from the mineral raw materials by a sodium sulfide system oxidation method, is particularly suitable for treating complex antimony-containing materials, and has a very good selective separation effect.
The quality of sodium pyroantimonate products is difficult to meet the high quality requirement due to the use of mineral raw materials in the oxidation method of the sodium sulfide system. When the air oxidation or the pressure oxidation is adopted to precipitate sodium pyroantimonate, the iron can be precipitated into the sodium pyroantimonate, so that the originally white sodium pyroantimonate product presents brick red, and the product quality is seriously affected. The literature indicates that most of iron can be precipitated in the form of ferrous sulfide after the sodium thioantimonite leaching solution is subjected to standing, however, long-time standing is unfavorable for industrial production continuity on one hand, and iron precipitation is incomplete in the solution standing process, so that the subsequent oxidation process is adversely affected. Based on this, a process for preparing a high quality sodium pyroantimonate product from antimony sulphide containing minerals is proposed.
Disclosure of Invention
In order to overcome the defects of the traditional method for preparing sodium pyroantimonate by using antimony sulfide-containing minerals in a sodium sulfide system, a hydrometallurgical method for preparing sodium pyroantimonate by combining gradient purification and gradient oxidation is provided, and the hydrometallurgical method has the advantages of high impurity removal rate, good product quality and low treatment cost.
The technical scheme adopted by the invention for achieving the purpose is as follows: firstly, leaching antimony sulfide-containing minerals in a sodium sulfide solution, so that most of antimony enters the leaching solution in a sodium thioantimonite form, and obtaining the leaching solution after liquid-solid separation. And adding antimony sulfide-containing minerals into the leaching solution to primarily remove iron, separating out most of iron which is matched with the leaching solution, and separating liquid from solid to obtain primarily de-iron liquid. And adding activated carbon into the primarily deironing liquid again to deeply deironing, so that residual iron in the solution is adsorbed and removed, and obtaining the deeply deironing liquid after liquid-solid separation. Thirdly, introducing oxygen into the deep iron-removed liquid at a low temperature for oxidation impurity removal, and obtaining low-temperature oxidized liquid after liquid-solid separation; and finally, introducing oxygen into the low-temperature oxidized liquid at a high temperature to oxidize to obtain sodium pyroantimonate products. The essence of the invention is that the purpose of preparing high-quality sodium pyroantimonate is realized by adopting a combination mode of echelon purification and echelon oxidation. Pure sodium thiosulfate solution is prepared by adding preliminary purification of antimony sulfide-containing minerals and deep purification by adding activated carbon adsorption, and high-quality sodium pyroantimonate products are prepared by low-temperature pressure oxidation and high-temperature pressure oxidation, the processes are closely related, and the expected effect of preparing high-quality sodium pyroantimonate from the antimony sulfide-containing minerals cannot be achieved in a single process.
The specific technological process and technological parameters are as follows:
1 sodium sulfide leaching
Antimony sulfide-containing minerals leach antimony in sodium sulfide solutions. Preparing 10-20g/L sodium hydroxide solution, adding antimony sulfide-containing mineral according to the ratio of liquid volume L to solid weight kg of 1.0-3.0:1, adding sodium sulfide according to the molar ratio of antimony sulfide to sodium sulfide of 2.7-3.3:1, stirring and reacting at 25 ℃ for 10-25min, carrying out liquid-solid separation in a vacuum filtration mode, and carrying out subsequent preliminary iron removal working procedure on the leaching solution, wherein leaching residues are used for extracting other valuable metals.
2 preliminary iron removal
Adding antimony sulfide-containing minerals into the leaching solution to primarily remove iron. Adding antimony sulfide-containing minerals with the ore quantity of 1-20% into the leaching solution in the leaching process, stirring and reacting for 30-120min at the reaction temperature of 25 ℃, adopting a vacuum filtration mode for liquid-solid separation, and feeding the liquid after preliminary iron removal into a deep iron removal process, wherein the preliminary iron removal slag returns to the leaching process.
3 depth iron removal
And adding activated carbon to the primarily deironing liquid to adsorb the deep deironing liquid. Adding active carbon into the primarily iron-removed liquid, adding 10-30g of active carbon into each liter of primarily iron-removed liquid, controlling the reaction temperature to be 25 ℃, stirring and reacting for 30-120min, performing liquid-solid separation in a vacuum filtration mode, and performing low-temperature pressurized oxidation on the deeply iron-removed liquid and washing deeply iron-removed slag for recycling.
4 low temperature pressure oxidation
And introducing oxygen into the solution after the deep iron removal at a low temperature to pressurize and oxidize precipitated iron. Adding the solution after deep iron removal into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 0.1-0.5MPa, controlling the temperature to be 20-30 ℃ and stirring for reaction for 30-120min, adopting a vacuum filtration mode for liquid-solid separation, sending the solution after low-temperature oxidation to a high-temperature pressurized oxidation process, and sending low-temperature oxidizing slag to a pyrogenic process for smelting antimony to recover antimony.
5 high temperature pressure oxidation
And introducing oxygen into the low-temperature oxidized solution at a high temperature to oxidize and precipitate sodium pyroantimonate. Adding the low-temperature oxidized liquid into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 1.0-2.0MPa, controlling the temperature to be 100-120 ℃ and stirring for reaction for 120-420min, performing liquid-solid separation in a vacuum filtration mode, and washing and drying high-temperature oxidized slag to obtain a qualified sodium pyroantimonate product.
The invention is suitable for treating antimony sulfide-containing minerals, wherein the main component ranges in percentage by weight are as follows: sb1.0-60.0 and S5.0-28.0.
The sodium sulfide and sodium hydroxide are both analytically pure reagents.
Compared with the traditional method for preparing sodium pyroantimonate by using the antimony sulfide-containing mineral in a sodium sulfide system, the invention has the following advantages: 1. after the antimony sulfide-containing mineral is leached in a sodium sulfide system, the method sequentially adopts a combination mode of echelon purification and echelon oxidation to prepare a high-quality sodium pyroantimonate product; 2. purifying the leaching solution in a gradient way to remove iron, primarily removing iron by using antimony sulfide-containing minerals, reducing the iron content in the solution to below 0.10g/L, and reducing the iron content in the solution to below 0.01g/L after deep iron removal after active carbon adsorption is added; 3. treating the solution after deep iron removal in a gradient oxidation mode, wherein the iron content in the solution after low-temperature oxidation is less than 0.001g/L, preparing a high-quality sodium pyroantimonate product by high-temperature pressurized oxidation, wherein the antimony content in the product is more than 48.5%, and the iron, lead and arsenic contents are all less than 0.001%; 4. the invention has the advantages of simple process, stable technical index, low labor intensity, low production cost and the like.
Drawings
Fig. 1: the process flow diagram of the invention is shown.
The specific embodiment is as follows:
example 1:
the main components of the antimony sulfide-containing mineral are respectively as follows in percentage by mass: sb8.20 and S16.35. Sodium hydroxide and sodium sulfide nonahydrate are all analytically pure reagents, and the mass percent of the sodium hydroxide is not less than 96%, and the mass percent of the sodium sulfide nonahydrate is not less than 98%. Preparing 10g/L sodium hydroxide solution, adding antimony sulfide-containing mineral according to the ratio of liquid volume L to solid weight kg of 2.0:1, adding sodium sulfide according to the molar ratio of antimony sulfide to sodium sulfide of 3.0:1, stirring and reacting for 15min at 25 ℃, and performing liquid-solid separation in a vacuum filtration mode, wherein the iron content in the leaching solution is 0.21g/L.
Adding antimony sulfide-containing minerals with the ore quantity of 8% into the leaching solution in the leaching process, stirring and reacting for 60min at the temperature of 25 ℃, and carrying out liquid-solid separation in a vacuum filtration mode, wherein the iron content in the liquid after primary purification is 0.09g/L. Adding active carbon into the primarily iron-removed liquid, adding 20g of active carbon into each liter of primarily iron-removed liquid, controlling the temperature to be 25 ℃, stirring and reacting for 60min, and performing liquid-solid separation in a vacuum filtration mode, wherein the iron content in the deeply purified liquid is 0.008g/L.
Adding the solution after deep iron removal into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 0.3MPa, controlling the temperature to be 25 ℃ and stirring for reaction for 60min, and performing liquid-solid separation in a vacuum filtration mode, wherein the iron content in the solution after low-temperature oxidation is less than 0.001g/L. Adding the low-temperature oxidized solution into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 1.8MPa, controlling the temperature to be 110 ℃, stirring and reacting for 240min, adopting a vacuum filtration mode to carry out liquid-solid separation, washing and drying a precipitate product to obtain a qualified sodium pyroantimonate product, wherein the antimony content is 48.75%, and the iron and arsenic contents are both less than 0.001%.
Example 2:
the main components of the antimony sulfide-containing mineral are respectively as follows in percentage by mass: sb12.30 and S18.64. Sodium hydroxide and sodium sulfide nonahydrate are all analytically pure reagents, and the mass percent of the sodium hydroxide is not less than 96%, and the mass percent of the sodium sulfide nonahydrate is not less than 98%. Preparing 10g/L sodium hydroxide solution, adding antimony sulfide-containing mineral according to the ratio of liquid volume L to solid weight kg of 2.0:1, adding sodium sulfide according to the molar ratio of antimony sulfide to sodium sulfide of 3.0:1, stirring and reacting for 15min at 25 ℃, and performing liquid-solid separation in a vacuum filtration mode, wherein the iron content in the leaching solution is 0.18g/L.
Adding antimony sulfide-containing minerals with the ore quantity of 5.0% into the leaching solution in the leaching process, stirring and reacting for 60min at the temperature of 25 ℃, and carrying out liquid-solid separation in a vacuum filtration mode, wherein the iron content in the liquid after primary purification is 0.08g/L. Adding active carbon into the primarily iron-removed liquid, adding 20g of active carbon into each liter of primarily iron-removed liquid, controlling the temperature to be 25 ℃, stirring and reacting for 60min, and performing liquid-solid separation in a vacuum filtration mode, wherein the iron content in the deeply purified liquid is 0.009g/L.
Adding the solution after deep iron removal into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 0.3MPa, controlling the temperature to be 25 ℃ and stirring for reaction for 60min, and performing liquid-solid separation in a vacuum filtration mode, wherein the iron content in the solution after low-temperature oxidation is less than 0.001g/L. Adding the low-temperature oxidized solution into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 1.8MPa, controlling the temperature to be 110 ℃, stirring and reacting for 240min, adopting a vacuum filtration mode to carry out liquid-solid separation, washing and drying a precipitate product to obtain a qualified sodium pyroantimonate product, wherein the antimony content is 48.69%, and the iron and arsenic contents are both less than 0.001%.
Claims (2)
1. The method for preparing high-quality sodium pyroantimonate by gradient purification and oxidation is characterized by comprising the following steps:
(1) Sodium sulfide leaching
Preparing 10-20g/L sodium hydroxide solution, adding antimony sulfide-containing mineral according to the ratio of liquid volume L to solid weight kg of 1.0-3.0:1, adding sodium sulfide according to the molar ratio of antimony sulfide to sodium sulfide of 2.7-3.3:1, controlling the reaction temperature to be 25 ℃ and stirring for reacting for 10-25min, carrying out liquid-solid separation in a vacuum suction filtration mode, and carrying out a subsequent preliminary iron removal procedure on the leaching solution, wherein leaching residues are used for extracting other valuable metals;
(2) Preliminary iron removal
Adding antimony sulfide-containing minerals with the ore quantity of 1-20% into the leaching solution in the leaching process, controlling the reaction temperature to be 25 ℃ and stirring for reaction for 30-120min, adopting a vacuum filtration mode for liquid-solid separation, and feeding the liquid after preliminary iron removal to a deep iron removal process, and returning the preliminary iron removal slag to leaching;
(3) Deep iron removal
Adding active carbon into the primarily iron-removed liquid, adding 10-30g of active carbon into each liter of primarily iron-removed liquid, controlling the reaction temperature to be 25 ℃, stirring and reacting for 30-120min, performing liquid-solid separation in a vacuum filtration mode, and performing low-temperature pressurized oxidation on the deeply iron-removed liquid and washing deeply iron-removed slag for recycling;
(4) Low temperature pressure oxidation
Adding the solution after deep iron removal into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 0.1-0.5MPa, controlling the temperature to be 20-30 ℃ and stirring for reaction for 30-120min, adopting a vacuum filtration mode for liquid-solid separation, sending the solution after low-temperature oxidation to a high-temperature pressurized oxidation process, and sending low-temperature oxidizing slag to a pyrogenic process for smelting antimony to recover antimony;
(5) High temperature pressure oxidation
Adding the low-temperature oxidized liquid into a high-pressure reaction kettle, introducing oxygen, controlling the pressure to be 1.0-2.0MPa, controlling the temperature to be 100-120 ℃ and stirring for reaction for 120-420min, performing liquid-solid separation in a vacuum filtration mode, and washing and drying high-temperature oxidized slag to obtain a qualified sodium pyroantimonate product.
2. The method for preparing high-quality sodium pyroantimonate by gradient purification and oxidation according to claim 1, wherein the method comprises the following steps: the main components of the antimony sulfide-containing mineral are as follows by weight percent: 1.0 to 60.0 percent of Sb and 5.0 to 28.0 percent of S.
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