CN1238535C - Process for separating antimoney from gold-antimoney ore using wet metallurgical technology - Google Patents
Process for separating antimoney from gold-antimoney ore using wet metallurgical technology Download PDFInfo
- Publication number
- CN1238535C CN1238535C CNB2003101229467A CN200310122946A CN1238535C CN 1238535 C CN1238535 C CN 1238535C CN B2003101229467 A CNB2003101229467 A CN B2003101229467A CN 200310122946 A CN200310122946 A CN 200310122946A CN 1238535 C CN1238535 C CN 1238535C
- Authority
- CN
- China
- Prior art keywords
- antimony
- gold
- hours
- oxide
- ore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005516 engineering process Methods 0.000 title claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 45
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 45
- KAPYVWKEUSXLKC-UHFFFAOYSA-N [Sb].[Au] Chemical compound [Sb].[Au] KAPYVWKEUSXLKC-UHFFFAOYSA-N 0.000 claims abstract description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052737 gold Inorganic materials 0.000 claims abstract description 32
- 239000010931 gold Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003546 flue gas Substances 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000001354 calcination Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000007790 solid phase Substances 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 18
- 229960001545 hydrotalcite Drugs 0.000 claims description 17
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052959 stibnite Inorganic materials 0.000 claims description 17
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical compound S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- ALMSMXCKPCWQMZ-UHFFFAOYSA-N [Mg].[Sb]=O Chemical compound [Mg].[Sb]=O ALMSMXCKPCWQMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000003500 flue dust Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000005188 flotation Methods 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 229910001216 Li2S Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 claims 4
- 150000004677 hydrates Chemical class 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- -1 antimony thioantimonate ions Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001238 wet grinding Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-O azanium;hydron;hydroxide Chemical compound [NH4+].O VHUUQVKOLVNVRT-UHFFFAOYSA-O 0.000 description 2
- 229910052599 brucite Inorganic materials 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- MYLBTCQBKAKUTJ-UHFFFAOYSA-N 7-methyl-6,8-bis(methylsulfanyl)pyrrolo[1,2-a]pyrazine Chemical compound C1=CN=CC2=C(SC)C(C)=C(SC)N21 MYLBTCQBKAKUTJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCCSVJRERUIAGJ-UHFFFAOYSA-N [Mg].[Sb] Chemical compound [Mg].[Sb] HCCSVJRERUIAGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a process for separating antimony from gold antimony ore by wet metallurgical technology. In the process, gold antimony ore powder or fine gold antimony ore is processed in a soluble sulfide solution so that antimonite in the gold antimony ore powder or the fine gold antimony ore is dissolved to separate gold and antimony; formed thioantimonite radical is adsorbed by adsorbent. An adsorbed product is calcined, and the antimony is converted into oxide and is melted in an adsorbent molecule. After SO3 in flue gas is washed by water, the SO3 is used as sulfuric acid to be recovered. The adsorbent can be used as raw material refining the antimony after being repeatedly used for a period of time, or the adsorption activity of the adsorbent is restored after the adsorbent is regenerated and activated.
Description
Technical Field
The invention relates to a method for separating antimony from gold-antimony ore by using a hydrometallurgical technology.
Background
The symbiosis of gold and antimony is common in nature, i.e., both elements are often present in the same ore. The ore usually contains 1-10 g/t of gold and 1-18% of antimony. Gold exists mainly as native gold, and antimony exists mainly as stibnite.
In the process of extracting gold, stibnite in the ore is easily dissolved in an alkaline cyanide gold extraction solution, and the reaction formula is as follows:
the stibnite in the ore is firstly dissolved to form antimonite and thioantimonate, and the thioantimonate reacts with cyanide and dissolved oxygen in the solution to form an antimony sulfide film which is coated on the surface of the natural gold particles, thereby preventing the natural gold from being dissolved and leached. Therefore, the gold-antimony ore is recognized as an ore raw material which is difficult to directly extract gold by a cyanidation method.
The traditional treatment method of the gold-antimony ore is that a flotation method is firstly used to obtain gold-antimony concentrate, then the concentrate is carefully calcined, so that stibnite in the concentrate is sublimated and recovered in flue dust, and gold is left in the residue after calcination. The biggest defect of the method is that gold and stibnite are sublimated into flue dust together with more gold and stibnite during calcination, and part of gold and stibnite are discharged into the atmosphere, so that gold loss is caused. Therefore, the separation of antimony from gold in the gold-antimony ore is a difficult problem in metallurgy and is one of the unsolved problems.
Disclosure of Invention
The invention aims to provide a method for separating antimony from gold-antimony ore by using a hydrometallurgical technology.
The method for separating antimony from gold-antimony ore by using hydrometallurgical technology provided by the invention comprises the following steps:
1) crushing the gold-antimony ore to be smaller than 100 meshes, pouring the gold-antimony ore into a slurry pool, adding soluble sulfide with the weight being 0.8-2.0 times of the amount of antimony metal in the gold-antimony ore, adding water with the weight being 2-8 times of the amount of the gold-antimony ore, uniformly stirring, and continuously stirring for 0.5-3 hours to dissolve stibnite therein to form a thioantimonite radical;
2) separating the solution from the residual solid phase by adopting a precipitation, centrifugation or filtration method, spraying the solid phase for 1-2 times, and allowing the eluent and the solution to enter the next procedure, wherein the solid phase is used as a rawmaterial for extracting gold;
3) adding a bimetallic oxide into the solution, wherein the weight of the bimetallic oxide is 10-20 times of the amount of antimony in the gold antimony ore, uniformly stirring, and continuously stirring for 4-12 hours;
4) separating the reactant from the solution by precipitation, centrifugation or filtration, air-drying or drying at a temperature lower than 90 ℃, allowing the solid phase to enter the next procedure, and allowing the liquid phase to return to the step 2 for reuse;
5) calcining the solid phase obtained in the step 4 at 500-750 ℃ for 2-5 hours to decompose the thioantimonite radical adsorbed by the bimetallic oxide, and fusing the thioantimonite radical into the bimetallic oxide molecules in the form of antimony oxide, SO in the flue gas3And (4) recovering in a water washing mode to obtain sulfuric acid, wherein the calcined residue is still a bimetal oxide and can be returned to the step 3 for reuse.
The gold antimony ore is naturally produced ore or gold antimony concentrate subjected to flotation.
The soluble sulfide being Li2S、Na2S、K2S and (NH)4)2One or more of S.
The bimetal oxide is a product obtained by calcining hydrotalcite at the temperature of 450-750 ℃ for 2-5 hours, and the chemical structural general formula of the bimetal oxide is Mgm·Sbn·OxWhere x is m +3n/2, depending on the hydrotalcite composition.
The preparation steps of the hydrotalcite are as follows:
1) MgO or Mg (OH)2And Sb2O3Mixing the materials according to the molar ratio of 2: 1-5: 1, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-24 hours;
2) adding Sb to the grinding mixture2O3And (3) crystallizing the bicarbonate with the weight of 0.3-0.8 times at the temperature of room temperature-90 ℃ for 10-48 hours under the condition of continuous stirring, dehydrating, washing for 2-3 times, airing or drying at the temperature lower than 90 ℃, calcining for 2-5 hours at the temperature of 500-750 ℃, and grinding to be smaller than 200 meshes for later use. The obtained product is hydrotalcite, and the chemical structure general formula is as follows: [ Mg1-xSbx(OH)2]X+[(HCO3)x·nH2O]，X＝0.5～0.17；n＝2～8，Mg/Sb＝2～5。
The bicarbonate is one or more of sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, ammonium bicarbonate or hydrate thereof.
After the bimetal oxide used as the adsorbent is repeatedly used for 3-10 times, the bimetal oxide is mixed with Sb in a molecular structure2O3The content is increased, the adsorption efficiency of the antimony thioantimonate ions is gradually reduced, and the antimony thioantimonate ions can be used as raw materials for extracting antimony at the moment, namely: calcining at 1000-1500 ℃ for 2-6 hours, wherein Sb is2O3Sublimed and condensed in the flue and recovered as flue dust, and the calcination residue was magnesium oxide.
The adsorption activity of the bimetal oxide can be recovered by repeatedly using the bimetal oxide for 3-10 times through the following steps:
1) mixing the used bimetallic oxide and magnesium oxide or magnesium hydroxide according to the weight ratio of 1: 0.05 to 1: 0.5, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-12 hours;
2) adding bicarbonate which is 0.2-0.8 times of the weight of the bimetallic oxide into the ground mixture, crystallizing for 10-48 hours at the temperature of room temperature-90 ℃ under the condition of continuous stirring, dehydrating, washing for 2-3 times, airing or drying at the temperature lower than 90 ℃, calcining for 2-5 hours at the temperature of 500-750 ℃, and grinding to less than 200 meshes for later use.
The bicarbonate is one or more of sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, ammonium bicarbonate or hydrate thereof.
The invention has the advantages that the wet method is adopted to separate and recover the antimony from the gold-antimony ore, thereby avoiding the interference of the antimony to the gold extraction process and simultaneously avoiding the gold escape caused by the common sublimation of the gold and the antimony during the separation by a pyrogenic process; the main raw material of the bimetal oxide can be reused, so that the production cost is greatly reduced, the process flow is simple, and the equipment investment is low; zero emission can be realized in the production process, and the environment protection is facilitated.
Detailed Description
The invention can be used for treating the naturally produced gold-antimony ore and can also be used for treating the gold-antimony concentrate after flotation. The gold in the ore and concentrate is mainly native gold and antimony is mainly present as stibnite. The natural ore is crushed and ground to be less than 100 meshes before treatment, and the gold-antimony concentrate is not ground.
The stibnite dissolution is carried out in a cylindrical slurry tank with the depth of the tank being the diameter of the tank1-2 times, and a mechanical stirring device is arranged in the middle of the pool so as to keep the ore or ore pulp powder and the sulfide solution uniformly mixed. The sulfide used may be Li2S、Na2S、K2S and (NH)4)2One or more of S, but from the comprehensive consideration of cost, benefit and environmental factors, Na is recommended to be used2And S. Stibnite and S in solution2-Ion reaction to form a thioantimonite:
when the reaction is complete, the dissolved stibnite is equal to the number of moles of sulfide in the solution, but the solubility of stibnite in sulfide solution is only about 60% of theoretical value. Therefore, the sulfide is used in excess in practical operation. If Na is used2S, the dosage of the antimony is about equal to the amount of antimony in the gold antimony ore, the antimony ore is incompletely dissolved when the dosage is too low, the cost is increased when the dosage is too high, and the adsorption rate of antimony in the next procedure is influenced.
After the stibnite is dissolved, the natural gold remains in the solid phase from which gold can be extracted by conventional cyanidation.
The invention adopts bimetallic oxide to adsorb antimony in solution, and the representative reaction is as follows:
the adsorption of the bimetallic oxide to the antimonous sulfate radical in the solution belongs to chemical adsorption, and the adsorption capacity is controlled by the reaction progress degree. Taking into account residual S in the solution2-、OH-And CO2The amount of the bimetallic oxide needs to be excessive, and the amount of the bimetallic oxide is 10-20 timesof the amount of antimony metal in the processed antimony-gold ore. After the adsorption reaction, a small amount of SbS still remains in the liquid phase3 3-And S2-And (4) leading the solution back to the slurry pond for recycling.
The bimetal oxide is an artificial composition composed of two kinds of metal oxides with different valence states, which is called LDO (layered Double oxides) for short. It has a structure similar to brucite (Mg (OH)2) The layered structure of (1), the precursor of which is a hydrotalcite-like compound, is also called anionic clay. The chemical structural general formula of hydrotalcite is:
[M1-x IIMx III(OH)2]X+[Ax/n n-·mH2O]wherein M isIIIs Mg2+，Zn2+，Fe2+，Mn2+，Co2+，Ni2+，Cu2+，Ca2+Divalent metal cations; mIIIIs Al3+，Sb3+，Fe3+，Cr3+，Co3+，Mn3+An iso-trivalent metal cation; a. then-Is CO3 2-，Cl-，NO3 -，SO4 2-Plasma anions; x is 0.5-0.17; mII/MIII＝1～5。
The above structural formula can be regarded as a product of partial replacement of divalent metal cations by trivalent metal cations in brucite, which is used for balancing positive charges of structural layers, and anions and water molecules are filled between the structural layers. The hydrotalcite is calcined at 450-750 ℃ to lose interlayer anions and water molecules, and the corresponding bimetallic oxide (LDO) is obtained. The bimetallic oxide has the general formula: mIImMIIInOx, wherein x is m +3 n/2. Representative reaction formulas are:
the bimetallic oxide can restore and reconstruct a hydrotalcite structure by adsorbing anions and water molecules in the environment, and is easy to accept an object due to larger specific surface area and pore volume. Thus, bimetallic oxides can be used to sulfate antimonite in solution.
The bimetal oxide used in the invention is magnesium antimony oxide, namely, the divalent oxide is MgO and the trivalent oxide is Sb2O3The molecular ratio is 2: 1-5: 1.
The magnesium-antimony bimetallic oxide is a derivative of the same hydrotalcite. The invention adopts wet grinding and crystallization to obtain hydrotalcite, and the specific steps are as follows:
1) MgO or Mg (OH)2And Sb2O3Mixing the materials according to the molar ratio of 2: 1-5: 1, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-24 hours;
2) adding Sb to the grinding mixture2O30.2 to 0.8 times of bicarbonate, crystallizing at room temperature to 90 ℃ for 10 to 48 hours under the condition of continuous stirring, dehydrating, washing for 2 to 3 times, and airing orAnd after drying at the temperature lower than 90 ℃, calcining for 2-5 hours at the temperature of 500-750 ℃, and grinding to less than 200 meshes for later use. The obtained product is hydrotalcite, and the chemical structure general formula is as follows: [ Mg1-xSbx(OH)2]X+[(HCO3)·nH2O]，X＝0.5～0.17；n＝2～8，Mg/Sb＝2～5。
Compared with the traditional coprecipitation method, the method for synthesizing the hydrotalcite has the advantages of simple process flow, low raw material price and no waste water discharge.
The bimetallic oxide adsorbed with the thioantimonite radical is grey, and is dried or baked and then sent into a furnace for calcination. The calcination temperature should not exceed 750 ℃, and is preferably controlled between 550 and 650. The hearth is relatively closed and is provided with a longer flue so as to cool and recover volatile matters. Representative reactions that occur upon calcination are:
the calcined residue is still a bimetallic oxide and can be reused.
After the bimetal oxide used as the adsorbent is repeatedly used for 3-10 times, the bimetal oxide is mixed with Sb in a molecular structure2O3The content is increased, the adsorption efficiency of the antimony thioantimonate ions is gradually reduced, and the antimony thioantimonate ions can be used as raw materials for extracting antimony and sold to antimony smelting plants; antimony can also be recovered by itself, namely: calcining at 1000-1500 ℃ for 2-6 hours, wherein Sb is2O3Sublimed and condensed in the flue and recovered as flue dust, and the calcination residue was magnesium oxide.
The adsorption activity of the bimetal oxide after repeated use for 3-10 times can be recovered through wet ball milling and crystallization:
1) mixing the used bimetallic oxide and magnesium oxide or magnesium hydroxide according to the weight ratio of 1: 0.05 to 1: 0.5, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-12 hours;
2) adding bicarbonate which is 0.2-0.8 times of the weight of the bimetallic oxide into the ground mixture, crystallizing for 10-48 hours at the temperature of room temperature-90 ℃ under the condition of continuous stirring, dehydrating, washing for 2-3 times, airing or drying at the temperature lower than 90 ℃, calcining for 2-5 hours at the temperature of 500-750 ℃, and grinding to less than 200 meshes for later use.
Because magnesium oxide, magnesium hydroxide and antimony oxide are slightly soluble, the wet grinding can ensure that the two raw materials are uniformly mixed on a molecular scale. The ground mixture is hydrolyzed in bicarbonate solution to obtain hydrotalcite. Representative chemical reactions in solution are:
The present invention is further illustrated by the following examples.
Example 1: separation of antimony from gold-antimony ores
1) Crushing and grinding 3g/T gold and 5% antimony in antimony-containing ore to less than 100 meshes, weighing 100Kg ore powder, pouring into a slurry pool, adding 5Kg Na2S, adding 300Kg of water, uniformly stirring, and continuously stirring for 1 hour to dissolve stibnite therein;
2) filtering to separate the solution from the residual solid phase, spraying the solid phase for 2 times, and allowing the eluate and the solution to enter the next process, wherein the solid phase is used as raw material for extracting gold;
3) adding 80Kg of bimetal oxide into the solution, stirring uniformly, and continuously stirring for 10 hours;
4) filtering the solid phase to separate from the solution, drying at the temperature lower than 80 ℃, enabling the solid phase to enter the next procedure, and returning the liquid phase to the step 2 for reuse;
5) calcining the solid phase obtained in the step 4 at 650 ℃ for 3 hours to oxidize the thioantimonite radical adsorbed by the bimetallic oxide, and fusing the thioantimonite radical into an adsorbent to obtain SO in the flue gas3And (4) recovering in a water washing mode to obtain sulfuric acid, wherein the calcined residue is still a bimetal oxide and can be returned to the step 3 for reuse.
Example 2: separation of antimony from gold-antimony concentrates
1) 100Kg of gold-antimony concentrate (containing 20g/T gold and 30% antimony) is poured into a pulp pool, and 40Kg of K is added2S, adding 800Kg of water, uniformly stirring, and continuously stirring for 2 hours to dissolve stibnite therein;
2) filtering to separate the solution from the residual solid phase, spraying the solid phase for 2 times, and allowing the eluate and the solution to enter the next process, wherein the solid phase is used as raw material for extracting gold;
3) adding 400Kg of bimetal oxide into the solution, uniformly stirring, and continuously stirring for 10 hours;
4) filtering the solid phase to separate from the solution,drying at the temperature lower than 80 ℃, enabling the solid phase to enter the next procedure, and returning the liquid phase to the step 2 for reuse;
5) calcining the solid phase obtained in the step 4 at 650 ℃ for 3 hours to oxidize the thioantimonite radical adsorbed by the bimetallic oxide, and fusing the thioantimonite radical into an adsorbent to obtain SO in the flue gas3And (4) recovering in a water washing mode to obtain sulfuric acid, wherein the calcined residue is still a bimetal oxide and can be returned to the step 3 for reuse.
Example 3: preparation of hydrotalcite by wet grinding crystallization method
1) 80kg of MgO and 292 kg of Sb2O3Mixing, adding into a ball mill, adding 372 kg of water, and grinding for 6 hours;
2) adding 88 kg bicarbonate into the ground mixture, crystallizing at 60 deg.C under stirring for 10 hr, dewatering, washing for 2 times, or oven drying at 80 deg.C, calcining at 550 deg.C for 5 hr, and grinding to less than 200 mesh.
Example 4: preparation of hydrotalcite by wet grinding crystallization method
1) 290 kg of Mg (OH)2And 292 kg of Sb2O3Mixing, adding into a ball mill, adding 3000 kg of water, and grinding for 24 hours;
2) adding 234 kg bicarbonate into the ground mixture, crystallizing at 80 deg.C under stirring for 48 hr, dewatering, washing for 3 times, or oven drying at 60 deg.C, calcining at 650 deg.C for 3 hr, and grinding to less than 200 mesh.
Example 5: preparation of bimetallic oxides
5.1 the hydrotalcites prepared or purchased according to example 3 or example 4 were calcined in a muffle furnace at 550 ℃ for 3 hours.
Example 6: separation of antimony from used bimetallic oxides
The bimetal oxide repeatedly used 10 times in example 3 was calcined at 1200 ℃ for 3 hours, wherein Sb was contained2O3Sublimating, condensing in flue, recovering in flue dust form, and recovering magnesium oxide as calcination residue.
Example 7: reactivation of used bimetallic oxides
1) The bimetal oxide and light magnesium oxide used repeatedly 8 times in example 4 were mixed according to a ratio of 1: 0.2: mixing the raw materials according to the weight ratio, adding the mixture into a ball mill, adding 3 times of water, and grinding for 8 hours;
2) adding sodium bicarbonate with a weight 0.3 times of that of the bimetallic oxide into the ground mixture, crystallizing at 60 ℃ for 24 hours under the condition of continuous stirring, dehydrating, washing for 2 times, drying at 70 ℃, calcining at 550 ℃ for 3 hours, and grinding to less than 200 meshes for later use.
Claims (8)
1. A method for separating antimony from gold-antimony ore by using a hydrometallurgical technology is characterized by comprising the following steps:
1) crushing the gold-antimony ore to be smaller than 100 meshes, pouring the gold-antimony ore into a slurry pool, adding soluble sulfide with the weight being 0.8-2.0 times of the amount of antimony metal in the gold-antimony ore, adding water with the weight being 2-8 times of the amount of the gold-antimony ore, uniformly stirring, and continuously stirring for 0.5-3 hours to dissolve stibnite therein to form a thioantimonite radical;
2) separating the solution from the residual solid phase by adopting a precipitation, centrifugation or filtration method, sprayingthe solid phase for 1-2 times, and allowing the eluent and the solution to enter the next procedure, wherein the solid phase is used as a raw material for extracting gold;
3) adding magnesium antimony oxide into the solution, wherein the weight of the magnesium antimony oxide is 10-20 times of the amount of antimony metal in the gold antimony ore, uniformly stirring, and continuously stirring for 4-12 hours;
4) separating the reactant from the solution by precipitation, centrifugation or filtration, air-drying or drying at a temperature lower than 90 ℃, allowing the solid phase to enter the next procedure, and allowing the liquid phase to return to the step 2 for reuse;
5) calcining the solid phase obtained in the step 4 at 500-750 ℃ for 2-5 hours to decompose the thioantimonite radical adsorbed by the magnesium antimony oxide, and fusing the thioantimonite radical into magnesium antimony oxide molecules in the form of antimony oxide, recovering SO3 in flue gas in a water washing mode to obtain sulfuric acid, wherein the calcined residue is still a bimetal oxide and can be returned to the step 3) for reuse.
2. A process for the hydrometallurgical separation of antimony from gold and antimony ores according to claim 1, characterised in that said gold and antimony ores are naturally occurring ores or gold and antimony concentrates after flotation.
3. A process for the hydrometallurgical separation of antimony from gold and antimony ores according to claim 1, characterised in that said soluble sulphide is Li2S、Na2S、K2S and (NH)4)2One or more of S.
4. The method of claim 1, wherein the magnesium antimony oxide is a product obtained by calcining hydrotalcite at 450-750 ℃ for 2-5 hours, and has a chemical structure formula of Mgm·SbnOx, where x is m +3n/2, depending on the hydrotalcite composition.
5. A process for the separation of antimony from gold-antimony ores by hydrometallurgical means according to claim 4, characterised in that said hydrotalcite is prepared by the steps of:
1) MgO or Mg (OH)2And Sb2O3Mixing the materials according to the molar ratio of 2: 1-5: 1, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-24 hours;
2) adding Sb to the grinding mixture2O30.3-0.8 times of bicarbonate by weight, crystallizing for 10-48 hours at room temperature-90 ℃ under the condition of continuous stirring, dehydrating, washing for 2-3 times, airing or drying at the temperature lower than 90 ℃, calcining for 2-5 hours at the temperature of 500-750 ℃, and grinding to less than 200 meshes for later use, wherein the obtained product is hydrotalcite, and the general chemical structure formula of the product is as follows: [ Mg1-xSbx(OH)2]X+[(HCO3)x·nH2O]，X＝0.5～0.17；n＝2～8，Mg/Sb＝2～5。
6. The method according to claim 1, wherein the magnesium antimony oxide used as the adsorbent is calcined at 1000-1500 ℃ for 2-6 hours after being reused 3-10 times, wherein Sb is Sb2O3Sublimed and condensed in the flue and recovered as flue dust, and the calcination residue was magnesium oxide.
7. The method for separating antimony from gold-antimony ore by using hydrometallurgicaltechnique according to claim 1, wherein the magnesium-antimony oxide used as adsorbent is treated by the following steps after repeated use for 3-10 times to restore the adsorption activity:
1) mixing the used magnesium antimony oxide and magnesium oxide or magnesium hydroxide according to the weight ratio of 1: 0.05 to 1: 0.5, adding the mixture into a ball mill or a rod mill, adding 2-8 times of water, and grinding for 6-12 hours;
2) adding bicarbonate which is 0.2-0.8 time of the weight of the magnesium antimony oxide into the ground mixture, crystallizing for 10-48 hours at the temperature of room temperature-90 ℃ under the condition of continuous stirring, dehydrating, washing for 2-3 times, airing or drying at the temperature lower than 90 ℃, calcining for 2-5 hours at the temperature of 500-750 ℃, and grinding to be smaller than 200 meshes for later use.
8. A process according to claim 5 or 7, wherein the bicarbonate is one or more of sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, ammonium bicarbonate or hydrates thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101229467A CN1238535C (en) | 2003-12-25 | 2003-12-25 | Process for separating antimoney from gold-antimoney ore using wet metallurgical technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101229467A CN1238535C (en) | 2003-12-25 | 2003-12-25 | Process for separating antimoney from gold-antimoney ore using wet metallurgical technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554784A CN1554784A (en) | 2004-12-15 |
| CN1238535C true CN1238535C (en) | 2006-01-25 |
Family
ID=34338845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101229467A Expired - Fee Related CN1238535C (en) | 2003-12-25 | 2003-12-25 | Process for separating antimoney from gold-antimoney ore using wet metallurgical technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1238535C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103203281B (en) * | 2013-04-07 | 2015-05-20 | 株洲市兴民科技有限公司 | Method for gold separation by means of removing antimony |
| CN103241771B (en) * | 2013-05-20 | 2014-12-03 | 浙江省地质矿产研究所 | Hydrotalcite-like compound-metallic antimony composite material and preparation method thereof |
| CN103924102B (en) * | 2014-05-07 | 2015-02-04 | 中南大学 | Method for removing antimony from refractory gold ore and preparing cubic crystal sodium pyroantimonate |
| CN105127008A (en) * | 2015-09-30 | 2015-12-09 | 广西大学 | Method for preparing stibnite inhibitor |
| CN106492996A (en) * | 2016-11-02 | 2017-03-15 | 广西大学 | A kind of stibnite and the flotation separation method of realgar |
| CN111057850B (en) * | 2020-01-03 | 2020-12-25 | 四川万邦胜辉新能源科技有限公司 | Method for preparing high-purity lithium metal by vacuum thermal reduction method |
-
2003
- 2003-12-25 CN CNB2003101229467A patent/CN1238535C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1554784A (en) | 2004-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1904094A (en) | Method of extracting gold and silver from arsenic containing aurin ore | |
| CN1865460A (en) | Method for extracting vanadium,molybdenum,nickel,cobalt,aluminium from waste aluminium base catalyst | |
| JP2016504251A (en) | Aluminum ion purification method | |
| CN107090551B (en) | A kind of method of the direct vanadium extraction of vanadium titano-magnetite | |
| CN102863007B (en) | Method for producing high-purity nano-zinc oxide by ammonia method using electrolytic zinc acid-leaching residues | |
| CN1384214A (en) | Carbon reducting roast process of producing RE chloride with mixed RE concentrate | |
| CN102838158B (en) | Method for producing high-purity nano-zinc oxide by ammonia decarburization of electrolytic zinc acid-leaching residues | |
| CN1207409C (en) | Wet process of extracting vanadium and/or molybdenum from waste catalyst | |
| CN1238535C (en) | Process for separating antimoney from gold-antimoney ore using wet metallurgical technology | |
| CN1271224C (en) | Process for electrolytic production of highly pure zinc or zinc compounds from primary and secondary zinc raw materials | |
| CN109097568B (en) | Method for separating selenium and arsenic from alkaline leaching solution containing selenium and arsenic | |
| EP1878806B1 (en) | Alkaline electro- hydrometallurgical process for Zn extraction from electric arc furnace dust | |
| CN1255559C (en) | Method for extracting vanadium by roasting material containing vanadium and its equipment | |
| CN1042349C (en) | Upgrading titaniferous materials | |
| CN1023693C (en) | Process for extracting of vanadium pentoxide by water immersion from cured mixture of stone coal ash with surfuric acid by heating | |
| WO2009136299A2 (en) | Chemical process for recovery of metals contained in industrial steelworks waste | |
| KR101735493B1 (en) | System and method for aluminium black dross recycling | |
| CN108063295A (en) | The method that lithium is extracted in the clinker generated from pyrogenic process recycling lithium battery | |
| CN114655970B (en) | Method for preparing lithium carbonate from scale steaming mother liquor | |
| CN1361295A (en) | Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation | |
| CN1019317B (en) | Method of iron removing in the process of cadmium extraction | |
| CN1033695C (en) | Preparation of high-active zinc oxide by improved all-wet method of ammonium bicarbonate | |
| CN1048287C (en) | Process for direct extraction of sulfide mineral by combound catalytic oxidation | |
| CN113387377A (en) | Method for preparing sulfuric acid system brine from low-grade lithium ore and extracting lithium | |
| CN113265545A (en) | Treatment device and treatment method for blast furnace gas ash |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060125 Termination date: 20100125 |