CN114377859B - Complex carbon-containing lead-zinc ore collaborative beneficiation method - Google Patents
Complex carbon-containing lead-zinc ore collaborative beneficiation method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 101
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011701 zinc Substances 0.000 claims abstract description 84
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 83
- 239000012141 concentrate Substances 0.000 claims abstract description 72
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 claims abstract description 55
- 239000010949 copper Substances 0.000 claims abstract description 55
- 238000005188 flotation Methods 0.000 claims abstract description 41
- 239000012267 brine Substances 0.000 claims abstract description 21
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000005261 decarburization Methods 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims description 32
- 230000002000 scavenging effect Effects 0.000 claims description 26
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 23
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 23
- 239000004571 lime Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KOVPITHBHSZRLT-UHFFFAOYSA-N 2-methylpropoxymethanedithioic acid Chemical compound CC(C)COC(S)=S KOVPITHBHSZRLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910001656 zinc mineral Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000002195 synergetic effect Effects 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 40
- 230000008901 benefit Effects 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 28
- 239000011707 mineral Substances 0.000 description 28
- 238000010494 dissociation reaction Methods 0.000 description 14
- 230000005593 dissociations Effects 0.000 description 14
- 239000003112 inhibitor Substances 0.000 description 14
- 238000005262 decarbonization Methods 0.000 description 13
- 229910052950 sphalerite Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 229910052949 galena Inorganic materials 0.000 description 7
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 7
- 238000007670 refining Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
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- 239000003153 chemical reaction reagent Substances 0.000 description 4
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- 239000006260 foam Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- -1 contains Ca 2+ Chemical compound 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- XFXWQRYJIJXOEZ-UHFFFAOYSA-N S(=O)(O)O.[Na+].[S-2].[Na+] Chemical compound S(=O)(O)O.[Na+].[S-2].[Na+] XFXWQRYJIJXOEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
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- 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
-
- 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
- B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
-
- 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
-
- 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a complex carbon-containing lead-zinc ore collaborative beneficiation method, which adopts a low-alkali brine collaborative beneficiation process flow of partial decarburization, preferential lead separation, lead middling regrinding, efficient copper extraction of lead concentrate, rapid lead tailing and asynchronous zinc flotation. The invention has the advantages of high recovery rate, low cost, simple technical circuit and easy industrial application, and is beneficial to improving the technological content and comprehensive competitiveness of nonferrous metal industry.
Description
Technical Field
The invention relates to the technical field of mining and metallurgy, and relates to a complex carbon-containing lead-zinc ore collaborative beneficiation method.
Background
The complex carbon-containing lead-zinc ore distribution areas in China mainly comprise Sichuan, inner Mongolia, guangxi areas and the like, most of carbon in the carbon-containing lead-zinc polymetallic ore is generated from mineral slate, and the carbon in the complex carbon-containing lead-zinc ore distribution areas is generated from mud carbonaceous dolomite and primary lautstone of lautstone. The ore properties of the ore are characterized in that (1) the carbon-containing ore has a plurality of mineral types to be recovered, most of the ore has high pyrite content, and most of the zinc ore is marmatite. (2) The ores have high carbon content and different carbonization degrees, the floatability of the carbon is different, and the carbon is closely connected with the useful minerals and gangue. (3) The carbon-containing lead-zinc multi-metal ore has fine embedding granularity, close symbiotic relation of useful minerals, complex structure and mutually staggered various minerals to form dense intergrowth relation. Inclusion and ex-vivo melting of one mineral can be seen in the other, with inclusion particle sizes being small. Therefore, the multi-metal ore containing carbon, lead and zinc belongs to typical complex refractory ore, and how to select a mineral separation process and a flotation reagent is a key for improving mineral separation indexes.
The complex carbon-containing lead-zinc sulfide ore is treated by adopting a lead-zinc preferential flotation after decarburization or lead-zinc mixed flotation separation process after decarburization, and because the carbon content in the ore is higher, rough scavenging is generally carried out under rough grinding conditions, the obtained rough concentrate is regrind or middling regrind is selected to strengthen the selection effect, the regrind process is determined according to the embedded granularity and the flotation characteristic of the ore, and the reasonable regrind process can not only improve the monomer dissociation degree of target minerals, but also effectively avoid overgrinding of dissociated monomer minerals and improve the selection index. The method has the advantages that the lead zinc ore contains more accompanying elements, when the sphalerite contains impurities such as Fu, cu and the like, the floatability of the sphalerite is good, the inhibition is difficult in the sorting process, when the sphalerite contains impurities such as Fe and the like, the floatability of the sphalerite is poor along with the increase of the Fe content, the floating speed is low, the sphalerite is sensitive to chemicals such as lime and the like, and a collector with high collecting capacity is selected in the beneficiation process so as to improve the recovery index of the sphalerite. When low-grade copper ore resources are associated in lead-zinc ores, because the copper content is low and most of copper is in complex symbiosis with galena, separate copper concentrate products are difficult to obtain, and the copper concentrate products are often recovered in a reinforced manner in the lead concentrate. When the lead concentrate contains only a small amount of copper minerals, the lead-suppression copper flotation process is mostly adopted. The traditional method for suppressing lead and floating copper adopts dichromate as an inhibitor of galena, but the dichromate has strong cancerogenic risk to human bodies, and the tailing wastewater after copper-lead separation has the problem of environmental pollution. The chromium-free process in the lead-inhibition copper-floating scheme mainly utilizes a combined medicament to inhibit galena, such as a water glass mixture method (carboxymethyl cellulose-water glass), a sulfurous acid-starch method, a sulfurous acid-sodium sulfide method and the like and the mutual combination thereof, and the chromium-free process has high inhibitor consumption and limited sorting effect.
The annual evaporation capacity of the inner Mongolia Wulat back flag area is larger than the rainfall capacity, the salt content of the underground water is higher, and fresh water resources are absent. Part of the mine had to be beneficiated with brine. The underground brine mainly contains Ca 2+ , Mg 2+ , Cl - Plasma, it was found that both mineral contact angle and hydrophobic force decrease with increasing ion concentration and increasing pH value due to Ca under alkaline conditions 2+ , Mg 2+ Ion hydrolysis to form hydrophilic trans-baseThe precipitation of the cover on the surface of the compound or hydroxide results in a decrease in the hydrophobicity of the mineral particles, which results in a decrease in the floatability of the sulphide mineral in brine.
Therefore, developing an innovative technology for beneficiating the high-efficiency and environment-friendly complex carbon-containing lead-zinc ore resources has important significance for realizing clean recovery and comprehensive utilization of the ore resources, and a high-efficiency and environment-friendly complex carbon-containing lead-zinc ore resource beneficiation method is needed.
Disclosure of Invention
Aiming at the problem that the loss of lead and zinc in decarburization operation is large frequently existing in the complex carbon-containing lead-zinc ore brine beneficiation process; the quality of the lead and zinc concentrate is poor under the saline condition, and the recovery rate of lead and zinc is low; the regrinding operation efficiency is low, and the lead-zinc minerals are poor in dissociation; the lead concentrate copper extraction inhibitor has the technical difficulties of high toxicity, serious environmental pollution, poor sorting index and the like; the raw copper resources have low grade and cannot be effectively and comprehensively recovered, and the production water salinity is high; through comprehensive research and application of new technology, new technology and new medicament, the integrated innovation technology for green resource development of complex carbon-containing lead-zinc ore is developed, namely, a 'partial decarburization-lead-preferential lead-lead middling regrinding-efficient copper extraction of lead concentrate-rapid lead tail-asynchronous zinc flotation' low-alkali brine synergistic ore dressing technology.
The invention discloses a complex carbon-containing lead-zinc ore collaborative beneficiation method, which adopts a low-alkali brine collaborative beneficiation process flow of partial decarburization, preferential lead selection, lead middling regrinding, efficient copper extraction of lead concentrate, rapid lead tail and asynchronous zinc flotation, and specifically comprises the following steps:
s1, performing preliminary semi-decarburization operation:
adding 500g/t of lime for ore grinding, adding 40g/t of kerosene for one-time decarburization roughing, decarburizing and concentrating the obtained carbon rough concentrate, decarburizing and scavenging the obtained decarburized roughing tailings, leading the obtained decarburized scavenging tailings to a lead-preferential operation, merging the decarburized and concentrated middlings and the decarburized and scavenged middlings, returning to the decarburized roughing operation, and further obtaining the carbon concentrate for lead-preferential operation; in alternative embodiments, the carbon roughing may also be performed in several passes, such as three passes, each of which is suitably used in an amount of 40g/t, 30g/t and 30g/t, respectively.
The invention adopts a partial decarbonization process, mainly aims at the advantages of low grade of lead and zinc of raw ore, high carbon content, fine embedding granularity, carbon mainly existing in graphite, and the distribution rate of the carbon is 67.16 percent, and compared with a non-decarbonization process and a full decarbonization process, the invention adopts a partial decarbonization-lead-zinc preferential flotation process, and has the advantages of high grade of lead and zinc concentrate, high recovery rate, simple process flow, low production cost and the like.
The prior main method for removing carbon has the following defects: the three-coarse and one-fine full decarburization process has the defects of large loss of lead and zinc in carbon concentrate and long process flow; the decarbonization does not cause accumulation of carbon in the operation, and the quality of concentrate is poor; the semi-decarbonization method has the advantages of simple process flow, simple medicament system and small loss of lead and zinc in the carbon concentrate.
As a further improvement of the embodiment of the present invention, in view of the fact that the main metal minerals such as sphalerite and galena in the ore have finer embedding particle sizes, pyrite, pyrrhotite and the like have coarser embedding particle sizes, S1 may further include: grinding raw ore, namely adding crushed raw ore and water into a ball mill according to the proportion of 1:1 to grind, and adding 200-250g/t of sodium sulfide and 500g/t of lime into a grinding machine until the grinding fineness of a grinding product is 75% -85% when the grinding fineness is-74 mu m.
S2, lead preferential flotation: according to the novel process for synergistic mineral separation of brine under the low-alkali condition, only 40-60g/t of ethion and 10-20g/t of kerosene are added, so that the use level of lime and zinc inhibitor is reduced, and the salinity of water for production is determined to be about 4.5 g/L;
the invention adopts a novel brine synergistic mineral separation process under the low-alkali condition, utilizes electrolyte ions in the brine to reduce the bubble size, enhance the foam stability and weaken the advantage of a mineral mud cover cap, and combines Mg in the brine 2+ 、Ca 2+ The ions are hydrolyzed in the high-alkalinity ore pulp to generate hydrophilic hydroxyl complex or hydroxide precipitate which is adhered to the surface of the mineral to reduce the floatability of the mineral, so that the lead-zinc flotation reagent system is optimized, the dosage of lime and zinc inhibitor is properly reduced, and the complex carbon-containing lead-zinc ore brine synergistic beneficiation process under the low-alkali environment is realized.Under the condition that the quality of lead concentrate and zinc concentrate is not reduced, the lead recovery rate is improved by more than 4 percent, and the zinc recovery rate is improved by more than 3 percent.
S3, selectively grinding, and improving lead recovery indexes; the invention adopts a lead middling regrinding process to replace the original lead rough concentrate regrinding process, and strengthens regrinding and dissociation of lead-zinc integrated bodies by merging zinc concentrate-row and scavenging-soaking into lead regrinding; meanwhile, the size of the grinding medium is reduced, the grinding effect is enhanced, and the dissociation degree of galena is improved, so that the mutual content of lead and zinc is reduced, and the recovery rate of lead is improved by more than about 1 percent under the condition that the quality of lead concentrate is not reduced; the regrinding and dissociation of the conjoined is enhanced by regrinding the middling, so that overgrinding of lead is avoided; the size of the grinding medium is reduced in the production process, phi 40 is used, the grinding effect is enhanced, and the lead regrinding effect is improved.
S4, a rapid-asynchronous zinc flotation process improves zinc recovery indexes. The invention adopts a rapid-asynchronous zinc flotation process to replace the original zinc rough concentrate regrinding process. The quick flotation of the easily-floated zinc minerals is realized through the asynchronous roughing, the selective regrinding of the difficultly-floated (intergrowth) zinc minerals is followed by strengthening the carefully-selected process to improve the dissociation degree of the intergrowth, and meanwhile, the overgrinding of the dissociated sphalerite is avoided, so that the zinc-sulfur separation efficiency is improved, and the comprehensive recovery index of zinc is improved.
The specific rapid-asynchronous zinc flotation process specifically comprises:
for lead tailings, 150g/t of copper sulfate and 40g/t of isobutyl xanthate are added for quick flotation, and then a two-stage zinc roughing and regrinding process is adopted, wherein 80g/t of copper sulfate, 8g/t of isobutyl xanthate, 20g/t of copper sulfate and 5g/t of isobutyl xanthate are used respectively to obtain the tailings; the solid particles obtained by rough concentration are subjected to a process of regrinding by adding lime; the zinc concentrate is obtained by using lime of 500g/t, 160g/t and 100g/t respectively.
The invention adopts quick floatation to quickly float the zinc minerals easy to float, avoids circulation in the process and avoids overgrinding at the same time; two sections of zinc roughing and regrinding, and strengthening intergrowth regrinding and dissociation; the isobutyl xanthate is adopted to strengthen the collection of zinc, so that the zinc loss of tailings is reduced; thereby improving the zinc recovery index; the rapid flotation-asynchronous zinc flotation process is adopted to realize closed circuit, and the isobutyl xanthate is used for replacing the on-site xanthate, so that the zinc recovery rate is improved by 8 more percent under the condition of equivalent concentrate grade compared with the on-site process.
S5, copper extraction process of lead concentrate:
copper extraction is carried out on the obtained intermediate product copper-lead mixed concentrate, the addition agent is 10000g/t of sulfuric acid, 10000g/t of ZJ201 6000g/t and 200 g/t of Z, copper coarse ore and lead coarse ore are obtained after the first roughing, ZJ201 1000 g/t is added into copper coarse ore for first refining, ZJ201 1000 g/t and Z200 4g/t are added into copper coarse ore for second refining, and ZJ201 500g/t and Z200 g/t are added into copper coarse ore for third refining; adding ZJ201 3000 g/t and Z200 g/t into the lead coarse ore, performing first-step scavenging, adding ZJ201 1000 g/t and Z200 g/t, and performing second-step scavenging to obtain lead concentrate.
The method adopts the organic inhibitor ZJ201 to strengthen and recycle the ultra-low grade associated copper resource (the copper content of the raw ore is less than 0.05 percent), and the inhibitor has the characteristics of environmental protection, no toxicity, low cost, safe addition, convenient use, easy natural degradation in water and the like. Copper extraction test of lead (copper) concentrate is carried out to obtain the operation indexes that copper grade of copper concentrate is more than 20%, lead content is less than 5%, copper recovery rate is more than 92% and lead loss rate is less than 1%.
The invention provides a recovery scheme with high recovery rate, low cost, simple technical circuit and easy industrial application for the development of complex carbon-containing lead-zinc ores, and provides a new way for realizing clean ore dressing and efficient comprehensive recovery of complex carbon-containing lead-zinc ores, improving economic and social benefits of enterprises and protecting the environment.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a complex carbon-containing lead-zinc ore collaborative beneficiation method.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Aiming at the problem that the loss of lead and zinc in decarburization operation is large frequently existing in the complex carbon-containing lead-zinc ore brine beneficiation process; the quality of the lead and zinc concentrate is poor under the saline condition, and the recovery rate of lead and zinc is low; the regrinding operation efficiency is low, and the lead-zinc minerals are poor in dissociation; the lead concentrate copper extraction inhibitor has the technical difficulties of high toxicity, serious environmental pollution, poor sorting index and the like; the raw copper resources have low grade and cannot be effectively and comprehensively recovered, and the production water salinity is high; through comprehensive research and application of new technology, new technology and new medicament, the integrated innovation technology for green resource development of complex carbon-containing lead-zinc ore is developed, namely, a 'partial decarburization-lead-preferential lead-lead middling regrinding-efficient copper extraction of lead concentrate-rapid lead tail-asynchronous zinc flotation' low-alkali brine synergistic ore dressing technology.
The invention discloses a complex carbon-containing lead-zinc ore collaborative beneficiation method, which adopts a low-alkali brine collaborative beneficiation process flow of partial decarburization, preferential lead selection, lead middling regrinding, efficient copper extraction of lead concentrate, rapid lead tail and asynchronous zinc flotation, and specifically comprises the following steps:
s1, performing preliminary semi-decarburization operation:
adding 500g/t of lime for ore grinding, adding 40g/t of kerosene for one-time decarburization roughing, decarburizing and concentrating the obtained carbon rough concentrate, decarburizing and scavenging the obtained decarburized roughing tailings, leading the obtained decarburized scavenging tailings to a lead-preferential operation, merging the decarburized and concentrated middlings and the decarburized and scavenged middlings, returning to the decarburized roughing operation, and further obtaining the carbon concentrate for lead-preferential operation;
the invention adopts a partial decarbonization process, mainly aims at the advantages of low grade of lead and zinc of raw ore, high carbon content, fine embedding granularity, carbon mainly existing in graphite, and the distribution rate of the carbon is 67.16 percent, and adopts a partial decarbonization-lead and zinc preferential flotation process, compared with a non-decarbonization process and a full decarbonization process, the invention has the advantages of high grade of lead and zinc concentrate, high recovery rate, simple process flow, low production cost and the like.
The prior main method for removing carbon has the following defects: the three-coarse and one-fine full decarburization process has the defects of large loss of lead and zinc in carbon concentrate and long process flow; the decarbonization does not cause accumulation of carbon in the operation, and the quality of concentrate is poor; the semi-decarbonization method has the advantages of simple process flow, simple medicament system and small loss of lead and zinc in the carbon concentrate.
As a further improvement of the embodiment of the present invention, in view of the fact that the main metal minerals such as sphalerite and galena in the ore have finer embedding particle sizes, pyrite, pyrrhotite and the like have coarser embedding particle sizes, S1 may further include: grinding raw ore, namely adding crushed raw ore and water into a ball mill according to the proportion of 1:1 to grind, and adding 200-250g/t of sodium sulfide and 500g/t of lime into a grinding machine until the grinding fineness of a grinding product is 75% -85% when the grinding fineness is-74 mu m.
TABLE 1 decarbonized lime dosage test results
As can be seen from table 1: with the increase of the lime consumption, the carbon grade and the recovery rate of the carbon rough concentrate are basically unchanged, and the lead-zinc loss rate in the carbon rough concentrate is slightly reduced. According to the flotation phenomenon, the addition of lime is favorable for stabilizing the foam in decarburization operation, and the phenomenon is good when the dosage is 500g/t, so that the dosage of the carbon roughing lime is 500g/t.
The types and amounts of the collectors used in the decarburization operation are shown in Table 2.
TABLE 2 carbon roughing collector types and dosage test results
As can be seen from table 2: (1) When the single No. 2 oil is used as a carbon collector in the decarburization operation, the yields of the rough carbon concentrate and the middling are increased, the carbon grade is reduced, and the lead-zinc loss rate is increased along with the increase of the consumption of the No. 2 oil; when the emulsified kerosene is used as a carbon collector in decarburization operation, the emulsified kerosene has no obvious effect on the grade of carbon and the loss rate of lead and zinc, so that a single No. 2 oil is selected as the carbon collector, and the proper dosage of carbon roughings 1, 2 and 3 is 40g/t, 30g/t and 30g/t respectively.
S2, lead preferential flotation: according to the novel process for synergistic mineral separation of brine under the low-alkali condition, only 40-60g/t of ethion and 10-20g/t of kerosene are added, so that the use level of lime and zinc inhibitor is reduced, and the salinity of water for production is determined to be about 4.5 g/L;
the invention adopts a novel brine synergistic mineral separation process under the low-alkali condition, utilizes electrolyte ions in the brine to reduce the bubble size, enhance the foam stability and weaken the advantage of a mineral mud cover cap, and combines Mg in the brine 2+ 、Ca 2+ The ions are hydrolyzed in the high-alkalinity ore pulp to generate hydrophilic hydroxyl complex or hydroxide precipitate which is adhered to the surface of the mineral to reduce the floatability of the mineral, so that the lead-zinc flotation reagent system is optimized, the dosage of lime and zinc inhibitor is properly reduced, and the complex carbon-containing lead-zinc ore brine synergistic beneficiation process under the low-alkali environment is realized. Under the condition that the quality of lead concentrate and zinc concentrate is not reduced, the lead recovery rate is improved by more than 4 percent, and the zinc recovery rate is improved by more than 3 percent.
TABLE 3 lead roughing collector dosage test results
As can be seen from table 3: along with the increase of the consumption of the ethion nitrogen, the lead grade of the lead rough concentrate tends to be reduced; the recovery rate of lead tends to increase, and the consumption of the lead roughing ethylene-sulfur-nitrogen is selected to be 40g/t.
S3, selectively grinding, and improving lead recovery indexes; the invention adopts a lead middling regrinding process to replace the original lead rough concentrate regrinding process, and strengthens regrinding and dissociation of lead-zinc integrated bodies by merging zinc concentrate-row and scavenging-soaking into lead regrinding; meanwhile, the size of the grinding medium is reduced, the grinding effect is enhanced, and the dissociation degree of galena is improved, so that the mutual content of lead and zinc is reduced, and the recovery rate of lead is improved by more than about 1 percent under the condition that the quality of lead concentrate is not reduced; the regrinding and dissociation of the conjoined is enhanced by regrinding the middling, so that overgrinding of lead is avoided; the size of the grinding medium is reduced in the production process, phi 40 is used, the grinding effect is enhanced, and the lead regrinding effect is improved.
S4, a rapid-asynchronous zinc flotation process improves zinc recovery indexes. The invention adopts a rapid-asynchronous zinc flotation process to replace the original zinc rough concentrate regrinding process. The quick flotation of the easily-floated zinc minerals is realized through the asynchronous roughing, the selective regrinding of the difficultly-floated (intergrowth) zinc minerals is followed by strengthening the carefully-selected process to improve the dissociation degree of the intergrowth, and meanwhile, the overgrinding of the dissociated sphalerite is avoided, so that the zinc-sulfur separation efficiency is improved, and the comprehensive recovery index of zinc is improved.
The specific rapid-asynchronous zinc flotation process specifically comprises:
for lead tailings, 150g/t of copper sulfate and 40g/t of isobutyl xanthate are added for quick flotation, and then a two-stage zinc roughing and regrinding process is adopted, wherein 80g/t of copper sulfate, 8g/t of isobutyl xanthate, 20g/t of copper sulfate and 5g/t of isobutyl xanthate are used respectively to obtain the tailings; the solid particles obtained by rough concentration are subjected to a process of regrinding by adding lime; the zinc concentrate is obtained by using lime of 500g/t, 160g/t and 100g/t respectively.
TABLE 4 Zinc scavenging and beneficiation Condition test results
From table 4, it can be seen that: (1) The dosage of the zinc concentration lime is increased, the grade of zinc concentrate is greatly increased, the recovery rate is reduced in a small scale, and the proper dosage is 100g/t; (2) The grade and loss rate of the zinc scavenging tailings are basically unchanged, so that only the collector T is added X Zn 50g/t, no. 2 oil 5g/t.
The invention adopts quick floatation to quickly float the zinc minerals easy to float, avoids circulation in the process and avoids overgrinding at the same time; two sections of zinc roughing and regrinding, and strengthening intergrowth regrinding and dissociation; the isobutyl xanthate is adopted to strengthen the collection of zinc, so that the zinc loss of tailings is reduced; thereby improving the zinc recovery index; the rapid flotation-asynchronous zinc flotation process is adopted to realize closed circuit, and the isobutyl xanthate is used for replacing the on-site xanthate, so that the zinc recovery rate is improved by 8 more percent under the condition of equivalent concentrate grade compared with the on-site process.
S5, copper extraction process of lead concentrate:
copper extraction is carried out on the obtained intermediate product copper-lead mixed concentrate, the addition agent is 10000g/t of sulfuric acid, 10000g/t of ZJ201 6000g/t and 200 g/t of Z, copper coarse ore and lead coarse ore are obtained after the first roughing, ZJ201 1000 g/t is added into copper coarse ore for first refining, ZJ201 1000 g/t and Z200 4g/t are added into copper coarse ore for second refining, and ZJ201 500g/t and Z200 g/t are added into copper coarse ore for third refining; adding ZJ201 3000 g/t and Z200 g/t into the lead coarse ore, performing first-step scavenging, adding ZJ201 1000 g/t and Z200 g/t, and performing second-step scavenging to obtain lead concentrate.
The method adopts the organic inhibitor ZJ201 to strengthen and recycle the ultra-low grade associated copper resource (the copper content of the raw ore is less than 0.05 percent), and the inhibitor has the characteristics of environmental protection, no toxicity, low cost, safe addition, convenient use, easy natural degradation in water and the like. Copper extraction test of lead (copper) concentrate is carried out to obtain the operation indexes that copper grade of copper concentrate is more than 20%, lead content is less than 5%, copper recovery rate is more than 92% and lead loss rate is less than 1%.
The invention provides a recovery scheme with high recovery rate, low cost, simple technical circuit and easy industrial application for the development of complex carbon-containing lead-zinc ores, and provides a new way for realizing clean ore dressing and efficient comprehensive recovery of complex carbon-containing lead-zinc ores, improving economic and social benefits of enterprises and protecting the environment.
In summary, the invention has the following beneficial effects:
1. the half decarbonization process adopted by the invention combines with the lead-zinc preferential flotation process, and has the advantages of high grade of lead and zinc concentrate, high recovery rate, simple process flow, low production cost and the like compared with the non-decarbonization process and the full decarbonization process;
2. the invention adopts a novel process of salt water synergistic beneficiation under low alkali environment, utilizes electrolyte ions in salt water to reduce the bubble size, enhance the foam stability and weaken the advantage of a mineral mud cover cap, and combines Mg in salt water 2+ 、Ca 2+ The method has the advantages that the defect that the floatability of minerals is reduced due to the fact that hydrophilic hydroxyl complex or hydroxide precipitate is generated by hydrolyzing ions in high-alkalinity ore pulp and adheres to the surfaces of the minerals is overcome, the lead-zinc flotation reagent system is optimized, and under the condition that the quality of lead concentrate and zinc concentrate is not reduced, the lead recovery rate is improved by more than 4 percent, and the zinc recovery rate is improved by more than 3 percent;
3. the invention adopts a lead middling regrinding process to replace the original lead rough concentrate regrinding process, and improves the lead recovery rate by more than about 1 percent under the condition of ensuring that the quality of lead concentrate is not reduced;
4. the invention adopts a rapid-asynchronous zinc flotation process to replace the original zinc rough concentrate regrinding process, and the rapid flotation of the easily-floated zinc minerals is realized through the asynchronous roughing, and the selective regrinding of the difficultly-floated (intergrowth) zinc minerals is followed by strengthening the concentration process so as to improve the dissociation degree of the intergrowth, and meanwhile, the regrinding of the dissociated sphalerite is avoided, thereby improving the zinc-sulfur separation efficiency and the comprehensive recovery index of zinc.
5. The method adopts the organic inhibitor ZJ201 to strengthen and recycle the ultra-low grade associated copper resource (the copper content of the raw ore is less than 0.05 percent), and the inhibitor has the characteristics of environmental protection, no toxicity, low cost, safe addition, convenient use, easy natural degradation in water and the like. Copper extraction test of lead (copper) concentrate is carried out to obtain the operation indexes that copper grade of copper concentrate is more than 20%, lead content is less than 5%, copper recovery rate is more than 92% and lead loss rate is less than 1%.
6. The invention also has obvious economic benefit, after the process is applied, the annual average treatment ore quantity of enterprises is 362.77 ten thousand yuan per year in 2017-2019, the crude ore contains 0.61 percent of lead, 2.34 percent of zinc, 0.05 weight percent of newly added lead metal, 0.54 weight percent of zinc, about 0.07 wt percent of newly added copper metal in 2019, the annual average newly added production value is 8600 ten thousand yuan, and the newly added profit is 4000 ten thousand yuan.
Claims (5)
1. A complex carbon-containing lead-zinc ore collaborative beneficiation method is characterized by adopting a low-alkali brine collaborative beneficiation process flow of partial decarburization, preferential lead selection, lead middling regrinding, efficient copper extraction of lead concentrate, rapid lead tail and asynchronous zinc flotation, and comprising the following steps of:
s1, performing preliminary semi-decarburization operation:
adding lime for ore grinding, adding 40g/t of kerosene for one-time decarburization roughing, decarburizing and concentrating the obtained carbon rough concentrate, decarburizing and scavenging the obtained decarburized roughing tailings, leading the obtained decarburized scavenging tailings to a lead-preferential operation, merging the decarburized and concentrated middlings and the decarburized and scavenged middlings, and returning to the decarburized roughing operation-;
s2, lead preferential flotation operation:
adopting a new process of salt water synergistic beneficiation under the low-alkali condition, adding ethion and kerosene to perform preferential lead separation; wherein, the salinity of the production water in the novel process of salt water synergistic beneficiation under the low alkali condition is 4.5g/L, the dosage of lime is reduced, the pH value is controlled to be 8-9, and 40-60g/t of ethionine and 10-20g/t of kerosene are added for preferential lead-selecting roughing operation;
s3, adopting lead middling regrinding to carry out selective grinding operation:
the lead roughing operation concentrate is subjected to three lead concentration operations, the primary lead concentration operation concentrate enters the secondary lead concentration operation, and the secondary lead concentration operation concentrate enters the three lead concentration operations; the secondary lead concentrating operation middling returns to the primary lead concentrating operation, and the tertiary lead concentrating operation middling returns to the secondary lead concentrating operation;
tailings in the lead roughing operation are subjected to lead scavenging operation twice; the ore enters secondary lead scavenging operation in the primary lead scavenging operation; the ore enters a primary lead scavenging operation in the secondary lead scavenging operation;
merging ores in primary lead scavenging operation and ores in primary lead fine selection operation, and then grinding the ores in lead; lead regrinding and returning to the lead roughing operation with preferential lead selection;
the outer diameter of the millstone of the lead regrinding is phi 40;
s4, performing quick-asynchronous zinc flotation operation to obtain zinc concentrate:
for tailings of secondary lead scavenging operation, quick flotation is carried out on the easily-floated zinc minerals through asynchronous roughing, and continuous zinc minerals are selectively regrind;
s5, carrying out copper extraction operation on lead concentrate:
copper extraction operation is carried out on the concentrate of the tertiary lead concentration operation; three beneficiations and two-step scavenging were performed by adding ZJ201 and Z200 to obtain lead concentrate.
2. The complex carbon-containing lead-zinc ore collaborative beneficiation method according to claim 1, wherein the ore grinding operation in the step S1 specifically comprises: adding crushed raw ore and water into a ball mill according to the proportion of 1:1 for grinding, and adding lime with the dosage of 500g/t into the grinding machine until the grinding fineness of a grinding product is 75% -85% when the grinding fineness is-74 mu m.
3. The complex carbon-containing lead-zinc ore collaborative beneficiation method according to claim 1, wherein the rapid-asynchronous zinc flotation process in step S4 specifically comprises: for tailings of secondary lead scavenging operation, copper sulfate and isobutyl xanthate are added for quick flotation, and then two stages of zinc roughing and lead regrinding processes are adopted.
4. A complex carbon-containing lead-zinc ore collaborative beneficiation method according to claim 3, wherein the rapid-asynchronous zinc flotation process in step S4 specifically comprises: for the tailings of the secondary lead scavenging operation, 150g/t of copper sulfate and 40g/t of isobutyl xanthate are added for quick flotation;
the two stages of zinc roughing operation respectively use 80g/t of copper sulfate, 8g/t of isobutyl xanthate, 20g/t of copper sulfate and 5g/t of isobutyl xanthate to obtain tailings;
the solid particles of the tailings obtained by roughing are subjected to a process of regrinding by adding lime; the zinc concentrate is obtained by using lime of 500g/t, 160g/t and 100g/t respectively.
5. The complex carbon-containing lead-zinc ore collaborative beneficiation method according to claim 1, wherein the three-time beneficiation and two-step scavenging by adding ZJ201 and Z200 in the step S5 specifically comprises: the adding agent is 10000g/t of sulfuric acid, 6000g/t of ZJ201 and 16g/t of Z200, copper coarse ore and lead coarse ore are obtained after the first step of roughing, the copper coarse ore is added with 1000 g/t of ZJ201 for first step of fine selection, then 1000 g/t of ZJ201 and 4g/t of Z200 are added for second fine selection, and then 500g/t of ZJ201 and 4g/t of Z200 are added for third fine selection; adding 3000 g/t g g/t ZJ201 and 8g/t Z200 into the lead coarse ore, performing first-step scavenging, adding 1000 g/t g g/t ZJ201 and 4g/t Z200, and performing second-step scavenging to obtain lead concentrate.
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