CN109663663A - A kind of extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral - Google Patents
A kind of extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral Download PDFInfo
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- CN109663663A CN109663663A CN201910057647.0A CN201910057647A CN109663663A CN 109663663 A CN109663663 A CN 109663663A CN 201910057647 A CN201910057647 A CN 201910057647A CN 109663663 A CN109663663 A CN 109663663A
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- vulcanization
- heavy metal
- minal
- mineral
- metal oxidation
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Links
- 238000004073 vulcanization Methods 0.000 title claims abstract description 54
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 41
- 239000011707 mineral Substances 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011593 sulfur Substances 0.000 claims abstract description 48
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 48
- 238000005188 flotation Methods 0.000 claims abstract description 46
- 238000004090 dissolution Methods 0.000 claims abstract description 39
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000004140 cleaning Methods 0.000 claims abstract description 19
- 230000001376 precipitating effect Effects 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000006228 supernatant Substances 0.000 claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 229910052592 oxide mineral Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 241000907663 Siproeta stelenes Species 0.000 claims description 19
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 12
- 229910000464 lead oxide Inorganic materials 0.000 claims description 11
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 230000002101 lytic effect Effects 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 229910017665 NH4HF2 Inorganic materials 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 26
- 229910052979 sodium sulfide Inorganic materials 0.000 description 24
- 238000000746 purification Methods 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 239000011133 lead Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 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 9
- 229960004643 cupric oxide Drugs 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 229910052955 covellite Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical group CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical group [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910000003 Lead carbonate Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 230000003542 behavioural effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052949 galena Inorganic materials 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000011646 cupric carbonate Substances 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZSFDBVJMDCMTBM-UHFFFAOYSA-N ethane-1,2-diamine;phosphoric acid Chemical compound NCCN.OP(O)(O)=O ZSFDBVJMDCMTBM-UHFFFAOYSA-N 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- UXNBTDLSBQFMEH-UHFFFAOYSA-N [Cu].[Zn].[Pb] Chemical compound [Cu].[Zn].[Pb] UXNBTDLSBQFMEH-UHFFFAOYSA-N 0.000 description 1
- UKTDQTGMXUHPIF-UHFFFAOYSA-N [Na].S(O)(O)=O Chemical compound [Na].S(O)(O)=O UKTDQTGMXUHPIF-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 carbon chain Amine Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
Abstract
The invention discloses a kind of extracting methods of heavy metal oxidation mineral minal vulcanization after cure product, the conditions of vulcanization of the minal of heavy metal oxidation mineral is determined first, vulcanized under identified conditions of vulcanization, ore pulp after being vulcanized, supernatant is removed after ore pulp is stood, then anti-oxidant selective dissolution agent is added into precipitating, the heavy metal oxidation mineral in precipitating are dissolved in selective dissolution agent, and the sulfide generated after oxide mineral vulcanization cannot dissolve still and exist in solid form, obtain solidliquid mixture；Obtained solidliquid mixture is subjected to eccentric cleaning more than once, final bottom slurry is dried, the sulfur product after obtaining the minal vulcanization of heavy metal oxidation mineral；The present invention can quickly, sulfur product that is economic, simply extracting a variety of oxide minerals the sciences problems in oxide ore sulfide flotation field are further solved to the sulfur product test analysis of extraction, develop oxide mineral with optimizing sulfide flotation technique and high-efficiency environment friendly.
Description
Technical field
The present invention relates to a kind of extracting method of substance, in particular to after the minal vulcanization of a kind of heavy metal oxidation mineral
The extracting method of sulfur product belongs to flotation technology field.
Background technique
The ores such as copper oxide, lead, zinc, cobalt are important mineral resources, efficiently using such ore to guaranteeing resources safety,
Meet non-ferrous metal demand to be of great significance.Flotation is the current recycling most economical effective means of heads.With it is corresponding
Sulfide mineral is compared, and oxide mineral surface wettability is big, direct flotation relative difficulty, need to use the fatty acid or fat of Long carbon chain
Amine medicament, but such medicament poor selectivity, dosage are big.Sulfide flotation method is generallyd use in industrial practice to recycle oxide ore
Object, vulcanization are the key links of the technique, and the effect of vulcanization directly affects floatation indicators.
Most common vulcanization process is that sodium sulfide solution is added in ore pulp in industrial practice, which is also referred to as table
Face vulcanization, mechanism is: heterogeneous chemical reaction occurs for sulphion and mineral grain in ore pulp, and generates metal sulfide (MeS)
It is covered on oxide mineral surface layer and forms oxide ore/sulfide multiphase composite construction as shown in Figure 1, due to sulfide surface hydrophobicity
By force, there are stronger adsorption capacity, the flotation of sulfidation energy active oxidation mineral to collecting agent.
In floating agent concentration range, the sulfur product amount generated after vulcanization is few, and since structure shown in FIG. 1 is special
Point, the stroke in sulfur product such as X-ray, infrared light is short, and the signal generated after effect is weak；Use common powder diffraction, red
The analysis means of testing such as external spectrum is difficult to be collected into the useful signal of sulfide, therefore fails in the past to the object phase of sulfur product, object
Physicochemical property etc. is effectively characterized, so that the sulfide flotation progress of oxide mineral is slow for many years.
Vulcanization is the key link of the mineral floatings such as copper oxide, lead, zinc recycling, and the quality of vulcanization directly affects the finger of flotation
Mark, therefore the extraction of the surface sulfide product to the heavy metal oxidations mineral such as copper, lead, zinc, and pass through modern analysis and test means
Its physicochemical properties is characterized, obtains effective information, there is important finger to the sulfide flotation industrial practice of oxide ore
Lead meaning.
Summary of the invention
Described in background technology to solve the problems, such as, the present invention provides a kind of vulcanizations of the minal of heavy metal oxidation mineral
The extracting method of after cure product, and to a variety of physicochemical properties such as object phase, element and its valence states of the sulfur product of extraction
Analysis detection is carried out, obtains effective information, there is important guidance to anticipate the industrial practice of the sulfide flotation of heavy metal oxidation mine
Justice.
To achieve the effect that above-mentioned technical proposal, the technical solution of the present invention is as follows: a kind of pure mine of heavy metal oxidation mineral
The extracting method of object vulcanization after cure product, the specific steps are as follows:
(1) sulfide flotation condition test is carried out to the minal of heavy metal oxidation mineral first, determines heavy metal oxidation mine
The conditions of vulcanization of the minal of object；
Wherein each condition in sulfide flotation condition test includes slurry pH, vulcanizing agent type and dosage, vulcanizing agent
The conditions such as addition manner, vulcanization time, curing temperature, additive types (ammonium salt, ethylenediamine).
(2) minal of heavy metal oxidation mineral is subjected to sulfide flotation under the conditions of optimum cure, after being vulcanized
Ore pulp obtains supernatant and precipitating after ore pulp is stood 1~3min, removes supernatant, and it is molten that selectivity is then added into precipitating
The heavy metal oxidation mineral in precipitating are dissolved in solution agent and antioxidant, selective dissolution agent, and oxide curative generates
Sulfide cannot dissolve and still exist in solid form, obtain solidliquid mixture；
(3) solidliquid mixture for obtaining step (2) carries out eccentric cleaning more than once, after final eccentric cleaning
Bottom slurry carries out low temperature drying, the sulfur product after obtaining the minal vulcanization of heavy metal oxidation mineral.
The heavy metal oxidation mineral are copper oxide ore object, lead oxide mineral or Oxide ores of zinc.
The copper oxide ore object be malachite, chrysocolla or chessy copper, the lead oxide mineral be cerussite or sardinianite,
The Oxide ores of zinc is smithsonite or smithsonite.
The antioxidant of the step (3) is for one of ascorbic acid, hydroxyl sulfate, sodium sulfite or arbitrarily than several
Mixture, antioxidant prevents sulfur product from aoxidizing.
When copper oxide ore object is malachite or chessy copper, corresponding selective dissolution agent is dilute sulfuric acid or ammonium hydroxide and ammonium carbonate
Mixture, copper oxide ore object be chrysocolla when, corresponding selective dissolution agent be dilute sulfuric acid and NH4HF2Mixture, institute
State lead oxide mineral be cerussite when, corresponding selective dissolution agent be acetic acid and sodium acetate mixture, the lead oxide ore
When object is sardinianite, corresponding selective dissolution agent is sodium chloride, when the Oxide ores of zinc is smithsonite, corresponding selectivity
Lytic agent is the mixture or ammonium hydroxide of acetic acid and sodium acetate and the mixture of ammonium carbonate, and the Oxide ores of zinc is smithsonite,
Corresponding selective dissolution agent is ammonium hydroxide, ammonium carbonate and NH4HF2Mixture.
The temperature dried in step (3) is 30~60 DEG C.
It repeats step (1)~(3) more than once, carries out analysis test after the sulfur product extracted more than once is mixed.
The beneficial effects of the present invention are:
The present invention can quickly, it is economical, simply extract the surface sulfide product after a variety of oxide ore minals vulcanizations, and energy
A variety of test analysis are carried out to the sulfur product of extraction, obtain the crystal phase of sulfur product, grain size, crystallinity and other more
Kind physical chemistry information can further solve the existing problem in science in oxide ore sulfide flotation field, optimization oxidation copper-lead zinc
Develop oxide mineral to the sulfide flotation technique of mine and high-efficiency environment friendly.
Detailed description of the invention
Fig. 1 is that oxide ore vulcanizes schematic diagram；
Fig. 2 is process flow diagram of the invention；
Fig. 3 is the XRD spectrum of the sulfur product of 1 cerussite of the embodiment of the present invention；
Fig. 4 is the relation schematic diagram of 2 malachite amount of sodium sulfide and flotation recovery rate of the embodiment of the present invention；
Fig. 5 is the XRD spectrum of the sulfur product of 2 malachite of the embodiment of the present invention.
Specific embodiment
Invention is described further with reference to the accompanying drawings and examples.
Embodiment 1: cerussite is the lead oxide mineral of most commercial recovery value, industrial at present to use vulcanization xanthate
Method recycles lead oxide ore, and vulcanization is the important link of the technique.The reaction equation that vulcanized sodium vulcanizes cerussite can be indicated with formula (1):
PbCO3/PbCO3+Na2S→PbCO3/PbS+Na2CO3 (1)
Domestic and foreign scholars have done a lot of research work in the sulfide flotation field of cerussite, but still there are some unresolved
Problem: as previously mentioned, because of the limitation of XRD instrumental sensitivity, PbS (vulcanization can not be detected in the amount of sodium sulfide range of flotation
Lead) diffracted signal；For the object phase for determining sulfur product, previous researcher will usually add extremely large amount of vulcanizing agent.But oxygen
The dosage of the sulfide flotation behavior and vulcanized sodium of changing mine is closely related, and in certain amount of sodium sulfide range, the rate of recovery is with vulcanization
The increase of sodium dosage and increase；When amount of sodium sulfide is more than optimum amount, as amount of sodium sulfide increases, the rate of recovery drops instead
It is low.It is thus determined that sulfur product object phase when optimum cure sodium dosage, and its physicochemical properties is probed into, to lead oxide
The flotation practice of mine has positive effect.The present embodiment introduces the extracting method of the minal sulfur product of cerussite, and to sulphur
The object phase for changing product, is characterized；
As shown in Fig. 2, the extraction step of the minal surface sulfide product of cerussite is as follows:
(1) sulfide flotation condition test is carried out to the minal of cerussite first, determines the best of the minal of cerussite
Conditions of vulcanization；
The flotation behavior of cerussite minal is studied:
Influence of the amount of sodium sulfide to cerussite flotation behavior is probed into using the single bubble pipe that volume is 50mL, every time using white
Lead ore minal amount is 0.5000g, and slurry temperature is room temperature, and pH keeps 10.20 ± 0.10 ranges, and collecting agent is butyl xanthate,
Dosage is 30mg/L, experiments have shown that having the highest rate of recovery when the dosage of vulcanized sodium is 75mg/L, when the dosage of vulcanized sodium
When more than 75mg/L, the rate of recovery is gradually decreased, therefore determines that the optimum amount of vulcanized sodium is 75mg/L.
(2) acetic acid+sodium acetate mixed solution alternatively property lytic agent is selected according to the property of cerussite, using anti-bad
Hematic acid prevents sulfur product from aoxidizing as antioxidant, configures the mixed solution conduct of 500mL acetic acid, sodium acetate and ascorbic acid
Anti-oxidant selective dissolution agent, quality of acetic acid concentration is 12% in mixed solution, sodium acetate concentration 120g/L, ascorbic acid concentrations
For 40g/L, claim 0.5g cerussite, by the process of above-mentioned flotation, sulphur is carried out to it under conditions of amount of sodium sulfide is 75mg/L
Change, obtains supernatant and precipitating after ore pulp is stood 1min after vulcanization, then remove supernatant, take the anti-oxidant selectivity of 30mL molten
Solution agent is added to beaker, and after reacting 3h, the cerussite in precipitating is dissolved in selective dissolution agent, and raw after cerussite vulcanization
At sulfide cannot dissolve and still exist in solid form, obtain solidliquid mixture；
(3) solidliquid mixture in beaker is transferred in 50mL centrifuge tube, is centrifuged repeatedly cleaning；It will be after 8 cleanings
Bottom slurry is dried at 30 DEG C, obtains sulfur product purification；
Step (1)~(3) is repeated at identical conditions 5 times, 5 purifications are mixed, obtained extract is for more
Kind analysis test, Fig. 3 are the XRD spectrum of purification, the result table consistent with the standard diffraction map of vulcanized lead (galena phase)
The sulfur product purity is high of bright purification, only minimal amount of impurity.
Embodiment 2: malachite is the copper oxide mineral of most industrial significance, industrially also generally using sulfide flotation
Copper oxide mineral resource is recycled, the sulfide flotation of cupric oxide ore was can be traced earliest to early stage in 20th century；1970, Castro etc. was logical
Crossing XRD proves that the sulfur product of black copper ore is CuS (covellite), they propose the vulcanization reaction equation of malachite later
(formula 2), Zhou etc. proposes formula (3) to explain ore pulp generation copper sulfide colloid phenomenon in malachite sulfide flotation later；Later,
People generally recognize that malachite sulfur product is CuS (covellite).Liu Dianwen etc. is by XRD in the extremely excessive item of vulcanized sodium
Sulfur product has been determined under part, has been Cu7S4(Roxbyite).This embodiment describes mentioning for the minal sulfur product of malachite
Method is taken, and the object of sulfur product is mutually identified:
CuCO3Cu(OH)2+HS-+OH-=Cu (OH)2CuS+CO3 2-+H2O (2)
CuCO3Cu(OH)2+ HS-=CuS+Cu2++2OH-+HCO3- (3)
The extraction step of the minal surface sulfide product of malachite is as follows:
(1) malachite sulfide flotation behavioral study:
Influence of the amount of sodium sulfide to malachite flotation behavior is probed into using the single bubble pipe that volume is 50mL, experiment makes every time
It the use of butyl xanthate is collecting agent, dosage 10 with 0.5g malachite minal-4Mol/L, pH keep 9.00 ± 0.10 ranges,
Vulcanization time 3min；As a result see Fig. 4, known by Fig. 4, be 5 × 10 in amount of sodium sulfide-4There is highest recovery when mol/L.
(2) it according to the property of malachite, selects sulfuric acid solution for selective dissolution agent, uses ascorbic acid as anti-oxidant
Agent prevents sulfur product from aoxidizing, and configures the anti-oxidant selective dissolution agent of 500mL, wherein sulfuric acid concentration 0.5%, ascorbic acid concentrations
For 40g/L, claim 0.5g malachite, is 5 × 10 in amount of sodium sulfide by the process of above-mentioned flotation-4Under conditions of mol/L to its into
Row vulcanization, oxide ore ore pulp stands 2min after vulcanization, then removes supernatant；The anti-oxidant selective dissolution agent of 20mL is taken to be added to
Beaker, after reacting 1h, the malachite in precipitating is completely dissolved by selective dissolution agent, and sulfur product then exists in solid form；
(3) slurries in beaker are transferred in 50mL centrifuge tube, are centrifuged repeatedly cleaning；Bottom will be starched after 6 cleanings
Liquid is dried at 40 DEG C, obtains sulfur product purification；
Step (1)~(3) is repeated at identical conditions 8 times, 8 purifications are mixed.To the purification through property XRD points
Analysis, it may be determined that as a result the object phase of sulfur product is shown in Fig. 5, know that malachite sulfur product is mainly Cu by XRD result7S4
(Roxbyite) and a small amount of Cu31S16(Djuleite)。
The present embodiment quick, economical, simple can extract oxide mineral surface sulfide product, and can carry out to sulfur product
A variety of analysis tests, obtain the physical chemistry information of sulfur product.
Embodiment 3: the extraction step of the minal surface sulfide product of lead vanadium is as follows:
(1) lead vanadium sulfide flotation behavioral study:
Influence of the amount of sodium sulfide to sardinianite flotation behavior is probed into using the single bubble pipe that volume is 50mL, experiment uses every time
0.5g sardinianite minal is collecting agent using butyl xanthate, and dosage 50mg/L, pH keep 9.00 ± 0.10 ranges, when vulcanization
Between 3min；Flotation experimental results show that sardinianite has highest recovery when amount of sodium sulfide is 100mg/L.
(2) according to the property of lead vanadium, selective chlorination sodium solution is selective dissolution agent, uses sodium sulfite as anti-oxidant
Agent prevents sulfur product from aoxidizing, and configures the anti-oxidant selective dissolution agent of 500mL, wherein sodium chloride concentration 250g/L, ascorbic acid
Concentration is 40g/L.Claim 0.5g lead vanadium, by the process of above-mentioned flotation, it is carried out under conditions of amount of sodium sulfide is 100mg/L
Vulcanization, oxide ore ore pulp stands 3min after vulcanization, then removes supernatant；The anti-oxidant selective dissolution agent of 30mL is taken to be added to burning
Cup reacts 3h, and the lead vanadium in precipitating is completely dissolved by selective dissolution agent, and sulfur product then exists in solid form；
(3) slurries in beaker are transferred in 50mL centrifuge tube, are centrifuged repeatedly cleaning；By bottom slurry after 6 cleanings
It is dried at 50 DEG C, obtains sulfur product purification.
Embodiment 4: the extraction step of the minal surface sulfide product of chrysocolla is as follows:
(1) chrysocolla sulfide flotation behavioral study:
It is probed under ethylenediamine phosphate effect using the single bubble pipe that volume is 50mL, amount of sodium sulfide is to chrysocolla flotation row
For influence, every time experiment use 0.5g chrysocolla minal, ethylenediamine phosphate dosage be 0.5 × 10-3Mol/L, isoamyl
Base xanthate dosage is 5 × 10-3When mol/L, influence of the amount of sodium sulfide to chrysocolla flotation is had studied.When amount of sodium sulfide is
1.5×10-3When mol/L, the rate of recovery of chrysocolla reaches maximum value.
(2) according to the property of chrysocolla, dilute sulfuric acid+NH is selected4HF2For selective dissolution agent, hydroxyl sulfate and Asia are used
The mixed solution of sodium sulphate prevents sulfur product from aoxidizing as antioxidant, configures the anti-oxidant selective dissolution agent of 500mL, wherein
Dilute sulfuric acid concentration 5%, NH4HF2Concentration is 5%, and hydroxyl sulfate and concentration of sodium sulfite are 30g/L (the two ratio is 1:1), 1.5
×10-3It is vulcanized under conditions of mol/L mol/L, oxide ore ore pulp stands 3min after vulcanization, then removes supernatant；
The anti-oxidant selective dissolution agent of 30mL is taken to be added to beaker, after reacting 5h, selective dissolution agent is complete by the chrysocolla in precipitating
Fully dissolved, sulfur product then exist in solid form；
(3) slurries in beaker are transferred in 50mL centrifuge tube, are centrifuged repeatedly cleaning；Bottom will be starched after 6 cleanings
Liquid is dried at 60 DEG C, obtains sulfur product purification.
Embodiment 5: the extraction step of the minal surface sulfide product of chessy copper is as follows:
Influence of the amount of sodium sulfide to chessy copper flotation behavior is probed into using the single bubble pipe that volume is 50mL, experiment makes every time
It the use of butyl xanthate is collecting agent with 0.5g chessy copper minal, dosage is 2 × 10mol/L, and pH keeps 9.00 ± 0.10 models
It encloses, vulcanization time 5min；Known by flotation experiments, amount of sodium sulfide is 7.5 × 10-4Highest recovery when mol/L.
(2) it according to the property of chessy copper, selects the mixture of ammonium hydroxide and ammonium carbonate for selective dissolution agent, uses sulfurous acid
Sodium antioxidant prevents sulfur product from aoxidizing, and configures the anti-oxidant selective dissolution agent of 500mL, wherein total ammonium concentration is 50%, ammonium
Ammonia ratio is 1:1, sodium sulfate concentration 40g/L, claims 0.5g chessy copper, by the process of above-mentioned flotation, amount of sodium sulfide be 7.5 ×
10-4It is vulcanized under conditions of mol/L, oxide ore ore pulp stands 3min after vulcanization, then removes supernatant；Take 30mL anti-
Oxidation selectivity lytic agent is added to beaker, and after reacting 90min, the chessy copper in precipitating is dissolved in selective dissolution agent, vulcanization
Product then exists in solid form；
(3) slurries in beaker are transferred in 50mL centrifuge tube, are centrifuged repeatedly cleaning；By bottom slurry after 6 cleanings
It is dried at 60 DEG C, obtains sulfur product purification.
Embodiment 6: the extraction step of the minal surface sulfide product of smithsonite is as follows:
The influence of flotation of the amount of sodium sulfide to smithsonite is studied carefully using the hanging groove machine that volume is 40mL, experiment uses 2g every time
Smithsonite, is collecting agent using lauryl amine, and dosage is 1 × 10-3Mol/L, vulcanization time 5min；Known by flotation experiments, vulcanized sodium
Dosage is that 400mg/L has highest recovery.
(2) it according to the property of smithsonite, selects the mixture of ammonium hydroxide and ammonium carbonate for selective dissolution agent, uses Vitamin C
Acid is that antioxidant prevents sulfur product from aoxidizing, and configures the anti-oxidant selective dissolution agent of 500mL, wherein total ammonium concentration is 50%,
Ammonium ammonia ratio is 1:1, ascorbic acid concentrations 40g/L, and title 2g smithsonite is in amount of sodium sulfide by the process of above-mentioned flotation
It is vulcanized under conditions of 400mg/L, oxide ore ore pulp stands 3min after vulcanization, then removes supernatant；Take 30mL anti-
Oxidation selectivity lytic agent is added to beaker, reacts 90min, and lytic agent dissolves the smithsonite in precipitating, sulfur product then with
Solid-state form exists；
(3) slurries in beaker are transferred in 50mL centrifuge tube, are centrifuged repeatedly cleaning；Bottom will be starched after 6 cleanings
Liquid is dried at 60 DEG C, obtains sulfur product purification.
Embodiment 7: the extraction step of the minal surface sulfide product of smithsonite is as follows:
(1) influence of flotation of the amount of sodium sulfide to smithsonite is studied carefully using the hanging groove machine that volume is 40mL, experiment makes every time
It the use of lauryl amine is collecting agent with 2g, dosage 40mg/L, vulcanization time 5min, experiment know that amount of sodium sulfide is 8 × 10- 4Mol/L has highest recovery.
(2) according to the property of smithsonite, ammonium hydroxide, ammonium carbonate+NH are selected4HF2Mixture be selective dissolution agent, use
Hydroxyl sulfate is that antioxidant prevents sulfur product from aoxidizing, and the anti-oxidant selective dissolution agent of 500mL is configured, wherein total ammonium concentration is
50%, ammonium ammonia ratio is 1:1, NH4HF2Concentration is 5%, and hydroxyl sulfate concentration is 30g/L, claims 2g smithsonite, by the stream of above-mentioned flotation
Journey is 8 × 10 in amount of sodium sulfide-4It is vulcanized under conditions of mg/L, oxide ore ore pulp stands 3min after vulcanization, then
Remove supernatant；It takes the anti-oxidant selective dissolution agent of 30mL to be added to beaker, reacts 180min, lytic agent will be heteropolar in precipitating
Mine dissolution, then solid-state form exists sulfur product；
(3) slurries in beaker are transferred in 50mL centrifuge tube, are centrifuged repeatedly cleaning；Bottom will be starched after 6 cleanings
Liquid is dried at 60 DEG C, obtains sulfur product purification.
Above in conjunction with attached drawing, the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned
Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept
Put that various changes can be made.
Claims (7)
1. a kind of extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral, which is characterized in that specific steps
It is as follows:
(1) sulfide flotation condition test is carried out to the minal of heavy metal oxidation mineral first, determines heavy metal oxidation mineral
The conditions of vulcanization of minal；
(2) minal of heavy metal oxidation mineral is vulcanized under identified conditions of vulcanization, the ore pulp after being vulcanized,
Supernatant and precipitating are obtained after ore pulp is stood 1~3min, supernatant is removed, it is molten that anti-oxidant selectivity is then added into precipitating
Agent is solved, anti-oxidant selective dissolution agent is the compounding substances of antioxidant and selective dissolution agent, and selective dissolution agent will precipitate
In heavy metal oxidation mineral dissolved, and the sulfide that oxide mineral vulcanization generates is insoluble still exists in solid form,
Obtain solidliquid mixture；
(3) solidliquid mixture for obtaining step (2) carries out eccentric cleaning more than once, by the bottom after final eccentric cleaning
Slurries are dried, the sulfur product after obtaining the minal vulcanization of heavy metal oxidation mineral.
2. the extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral according to claim 1, special
Sign is: the heavy metal oxidation mineral are copper oxide ore, lead oxide ore or Oxide ores of zinc.
3. the extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral according to claim 2, special
Sign is: the copper oxide ore object be malachite, chrysocolla or chessy copper, the lead oxide mineral be cerussite or sardinianite,
The Zinc oxide mineral are smithsonite or smithsonite.
4. the extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral according to claim 1 or 2,
Be characterized in that: the antioxidant of the step (3) is for one of ascorbic acid, hydroxyl sulfate, sodium sulfite or arbitrarily than several
The mixture of kind.
5. the extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral according to claim 3, special
Sign is: when copper oxide ore object is malachite or chessy copper, corresponding selective dissolution agent is dilute sulfuric acid or ammonium hydroxide and ammonium carbonate
Mixture, copper oxide ore object be chrysocolla when, corresponding selective dissolution agent be dilute sulfuric acid and NH4HF2Mixture, institute
State lead oxide mineral be cerussite when, corresponding selective dissolution agent be acetic acid and sodium acetate mixture, the lead oxide ore
When object is sardinianite, corresponding selective dissolution agent is sodium chloride, when the Oxide ores of zinc is smithsonite, corresponding selectivity
Lytic agent is the mixture or ammonium hydroxide of acetic acid and sodium acetate and the mixture of ammonium carbonate, and the Oxide ores of zinc is smithsonite,
Corresponding selective dissolution agent is ammonium hydroxide, ammonium carbonate and NH4HF2Mixture.
6. the extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral according to claim 3, special
Sign is: the temperature dried in step (3) is 30~60 DEG C.
7. the extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral according to claim 1, special
Sign is: repeating step (1)~(3) more than once, carries out analysis test after the sulfur product extracted more than once is mixed.
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