CN111185297B - Blast furnace low-grade copper slag enrichment method - Google Patents

Blast furnace low-grade copper slag enrichment method Download PDF

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CN111185297B
CN111185297B CN202010091713.9A CN202010091713A CN111185297B CN 111185297 B CN111185297 B CN 111185297B CN 202010091713 A CN202010091713 A CN 202010091713A CN 111185297 B CN111185297 B CN 111185297B
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copper
flotation
concentrate
blast furnace
scavenging
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CN111185297A (en
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饶金山
陈志强
吕昊子
刘勇
吕建芳
胡红喜
吕先谨
刘超
周吉奎
马致远
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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Institute Of Resources Comprehensive Utilization Guangdong Academy Of Sciences
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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
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B9/00—General arrangement of separating plant, e.g. flow sheets
    • B03B9/04—General arrangement of separating plant, e.g. flow sheets specially adapted for furnace residues, smeltings, or foundry slags
    • 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
    • B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
    • 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
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • 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
    • B03D1/014—Organic compounds containing phosphorus
    • 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
    • B03D1/018—Mixtures of inorganic and 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
    • B03D2201/02—Collectors
    • 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
    • B03D2201/04—Frothers
    • 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

Abstract

The invention belongs to the technical field of solid waste treatment, and particularly discloses a blast furnace low-grade copper slag enrichment method. According to the enrichment method of the low-grade copper slag of the blast furnace, based on the ductility of copper metal and the hard brittleness of melilite matrix, coarse copper particles and thin copper sheets are separated in advance through ore grinding and screening, and high-quality copper concentrate is directly obtained; in view of the characteristic that copper metal is easy to oxidize, a proper amount of collecting agent and foaming agent are added into the classified fine particles for quick flotation, and the obtained foam product, namely quick-floating concentrate, is directly used as copper concentrate with higher quality; the flotation concentrate obtained by the magnetic separation-ball milling-sulfuration flotation process can be used as copper secondary concentrate, so that the problem of high copper content in the tailings is solved, and the comprehensive recovery rate of copper is improved.

Description

Blast furnace low-grade copper slag enrichment method
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a method for enriching and treating low-grade copper slag of a blast furnace.
Background
The copper-containing sludge mainly refers to hazardous solid wastes such as metal surface treatment wastes, copper-containing wastes and non-ferrous metal smelting wastes. The common treatment method for the copper-containing sludge at present comprises the following steps: drying the copper-containing sludge in a rotary kiln, sintering the copper-containing sludge in a vertical kiln to produce a sintered block, mixing the sintered block with ingredients such as limestone, quartz stone, carbon powder and the like, putting the mixture into a blast furnace, and carrying out high-temperature reduction smelting at 1200-1300 ℃ to generate reduced slag and blister copper. The slag is not compatible with the blister copper, and the slag and the blister copper are layered due to the specific gravity difference, the lower layer is blister copper, and the upper layer is melting reduction slag. And discharging the smelting reduction furnace slag to obtain the low-grade copper slag of the blast furnace.
The low-grade copper slag of the blast furnace mainly comprises valuable metal elements of copper with the content of 3-5%, and main non-target elements of silicon dioxide, calcium oxide, iron, aluminum oxide, magnesium oxide and the like. The low-grade copper slag of the blast furnace has low copper content, generally has the copper content of 3-5 percent, and even can be lower, and is not suitable for extracting blister copper by adopting a dilution furnace due to overhigh smelting cost. About 70% of copper contained in the low-grade copper slag of the blast furnace exists in metallic copper, copper alloy, copper sulfide ore and other phases, and about 30% of copper is distributed in oxidation phases of delafossite, glass, magnetite and the like. Wherein the metallic copper or the copper-containing alloy has the characteristics of ductility and difficult crushing and grinding, and the metallic copper, the copper alloy and the blue chalcocite have the characteristics of easy oxidation. At present, no research for separating and enriching the low-grade copper slag of the blast furnace is found.
Disclosure of Invention
The invention mainly solves the technical problem of providing a blast furnace low-grade copper slag enrichment method to realize effective enrichment and recovery of copper in the blast furnace low-grade copper slag.
In order to solve the technical problems, the invention adopts the technical scheme that: a blast furnace low-grade copper slag enrichment method comprises the following steps:
s1: crushing low-grade copper slag in a blast furnace, and grinding the copper slag by using a rod mill to obtain a copper slag crushed grinding material, wherein the grinding fineness of the copper slag crushed grinding material is-0.075 mm, and the mass percentage content of the copper slag crushed grinding material is 55-65%; wherein, the mass percentage of the particles with the particle diameter of less than 0.075mm accounts for 55-65% of the total weight of the crushed grinding material, namely, the particles with the particle diameter of less than 0.075mm accounts for 55-65%;
s2: grading the copper slag crushed grinding materials, wherein the grading granularity is 0.15-0.25 mm, the rough granules obtained by grading are copper concentrate, and the fine granules obtained enter a rapid flotation step;
s3: blending the fine particle materials into slurry with the solid particle mass percentage concentration of 40-60%, then adding a collecting agent and a foaming agent for rapid flotation, wherein the collecting agent is a copper sulfide ore collecting agent, a foam product obtained through rapid flotation is rapid flotation concentrate, and an obtained tank bottom product enters a magnetic separation step;
s4: separating the tank bottom product obtained by the rapid flotation by adopting magnetic separation, wherein the magnetic separation strength is 300-600 mT, and separating to obtain magnetic concentrate and magnetic tailings; collecting the magnetic separation tailings serving as final tailings; grinding the magnetic concentrate until the mass percentage of the magnetic concentrate is 85-100% of-0.038 mm, adjusting the concentration of the ground slurry to 30-40% to obtain ground slurry of the magnetic concentrate, and then performing vulcanization flotation;
s5: adding a vulcanizing agent into the magnetic separation concentrate grinding slurry for vulcanization treatment, then adding a copper sulfide ore collecting agent and a foaming agent for vulcanization flotation, performing primary scavenging on a tank bottom product obtained by the vulcanization flotation, and performing primary concentration on a foam product obtained by the vulcanization flotation;
addition of frother 2 to sulfidized flotation froth product#Oil with the addition of 0-8 g/t, then primary concentration is carried out, the tank bottom product of the primary concentration returns to the vulcanization flotation operation, namely the tank bottom product of the primary concentration returns to the vulcanization flotation again, and the foaming agent 2 is added into the foam product of the primary concentration#Oil with the addition amount of 0-8 g/t is subjected to secondary concentration;
returning the bottom product obtained by the secondary concentration to the primary concentration operation, wherein the foam product obtained by the secondary concentration is flotation concentrate;
adding butyl xanthate and 2 to a tank bottom product obtained by sulfuration flotation#The dosage of the oil and the butyl xanthate is 20-100 g/t, 2#The oil consumption is 0-8 g/t, one scavenging is carried out,
returning the foam product obtained by the primary scavenging to the vulcanization flotation operation, and performing secondary scavenging on the tank bottom product obtained by the primary scavenging;
adding butyl xanthate and 2 into the tank bottom product obtained by one-time scavenging#The dosage of the oil and the butyl xanthate is 20-100 g/t, 2#And (3) carrying out secondary scavenging when the addition amount of the oil is 0-8 g/t, returning a foam product subjected to the secondary scavenging to the primary scavenging operation, and combining a tank bottom product subjected to the secondary scavenging with the magnetic separation tailings to be used as final tailings for collection.
In the step S1, the mass percentage of copper in the treated low-grade copper slag of the blast furnace is 1-5%.
In a preferred embodiment, in step S2, the classifying equipment may be a classifier, a hydrocyclone or an industrial sieve.
In a preferred embodiment, in step S3, the copper sulfide ore collecting agent is butyl xanthate, butylamine black pigment or Z-200, preferably butyl xanthate, and the amount is 50 to 150 g/t; the foaming agent is 2#Oil, MIBC or sodium dodecyl sulfate, preferably 2#The amount of the oil is 8-24 g/t.
In a preferred embodiment, in step S5, the sulfuration reagent is sodium sulfide, ammonium sulfate or ammonium bisulfate, preferably ammonium sulfate, and the amount is 500-1500 g/t.
In a preferred embodiment, in step S5, the copper sulfide ore collecting agent is butyl xanthate, butylamine black pigment or Z-200, preferably butyl xanthate, and the amount is 50 to 150 g/t; the foaming agent is 2#Oil, MIBC or sodium dodecyl sulfate, preferably 2#The amount of the oil is 8-24 g/t.
In the method for enriching the low-grade copper slag of the blast furnace, the dosage of each reagent is calculated relative to the weight of the low-grade copper slag of the blast furnace to be processed. The slurry concentration is calculated as the weight of solid particles as a percentage of the total weight of the slurry.
The blast furnace low-grade copper slag enrichment method provided by the invention comprises the steps of firstly crushing and rod grinding by a rod grinding machine to a certain fineness to dissociate coarse particle copper and flake copper from copper slag, wherein compared with ball grinding, the rod grinding machine can enable ore grinding particles to be more uniform, and then classifying, so that separated coarse particle materials are dissociated coarse particle copper and flake copper, copper separation and enrichment are realized, and high-quality copper concentrate is obtained; then, performing rapid flotation on the screened fine particle materials, wherein a copper sulfide ore collecting agent is selected as the collecting agent, and a foam product obtained by flotation is copper concentrate with higher quality; then carrying out magnetic separation on the tank bottom product subjected to the rapid flotation, and pre-enriching copper in the magnetic separation concentrate; performing sulfuration flotation on the magnetic concentrate after the magnetic concentrate is crushed, ground and mixed by a ball mill, adding sulfuration reagents such as ammonium sulfate and the like for sulfuration, and then adding collecting agents of butyl xanthate and foaming agent 2#And (3) carrying out vulcanization flotation on the oil, and obtaining flotation concentrate which is copper secondary concentrate meeting the requirement of blast furnace smelting through one-time roughing, two-time scavenging and two-time concentrating.
According to the enrichment method of the low-grade copper slag of the blast furnace, provided by the invention, based on the ductility of copper metal and the hard brittleness of melilite matrix, coarse copper particles and thin copper sheets are separated in advance through grinding and screening by a rod mill, so that high-quality copper concentrate is directly obtained, the copper grade is more than 20%, and the copper recovery rate is 15-25%; in view of the characteristic that copper metal is easy to oxidize, a proper amount of collecting agent and foaming agent are added into the classified fine particles for quick flotation, the obtained foam product, namely quick-floating concentrate, is directly used as copper concentrate with higher quality, the copper grade is higher than 20%, and the copper recovery rate is 30-40%; then, according to the magnetism of magnetite or chromite, magnetic separation with the field intensity of 300-600 mT is adopted for the micro-fine particle copper which is oxidized and is wrapped by the magnetite and/or chromite, ball milling and regrinding are adopted for the magnetic separation concentrate, vulcanization flotation is adopted for regrinding ore pulp, flotation concentrate which can be used as copper secondary concentrate is obtained through once roughing, twice scavenging and twice concentration, the copper grade is 3-7%, and the recovery rate is 30-40%.
The enrichment treatment process provided by the invention well solves the technical problem of coarse particle copper/flake copper accumulation in middlings in a grinding-flotation process through screening; then, through rapid flotation, copper with good surface floatability is directly floated to serve as copper concentrate with higher quality, so that the problem that middling is accumulated due to easy oxidation of copper is solved; the tailings with the rapid flotation process can solve the problem that the tailings with the process of grinding, screening, rapid flotation and sulfidation flotation have high copper content by adopting the process of magnetic separation, ball milling and sulfidation flotation, and the comprehensive recovery rate of copper is improved, particularly the recovery rate of copper slag containing about 1-3% of copper can be improved by about 10% through tests. Copper in tailings subjected to rapid flotation is micro-fine particle copper which is oxidized and is wrapped by magnetite and/or chromite, magnetic separation with the field intensity of 300-600 mT can be adopted according to the magnetism of the magnetite or chromite, the micro-fine particle copper which is oxidized and is wrapped by the magnetite and/or chromite is separated out to be used as magnetic separation concentrate, silicate, melilite ore and the like which are separated out through magnetic separation are magnetic separation tailings and can be directly discarded as the tailings without entering a vulcanization flotation process, the operation pressure of a flotation process section is reduced, and the using amount of a flotation reagent can be saved.
The method can realize simple and efficient separation and enrichment of the low-grade copper slag of the blast furnace, can produce copper concentrate with different grades, and can meet the echelon requirement of the blast furnace on the quality of the copper concentrate.
Drawings
FIG. 1 is a process flow chart of the low-grade copper slag enrichment method of the blast furnace provided by the invention.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
The percentages in the following examples and comparative examples are mass percentages.
Example 1
The process flow shown in fig. 1 is adopted to separate and enrich the low-grade copper slag of the blast furnace, the copper slag of the blast furnace processed by the embodiment contains 1.13% of copper, the copper mainly exists in copper simple substance, alloy and chalcocite, and accounts for about 1.21% of the mass of the copper slag, the main matrix is a yellow feldspar mineral, and accounts for about 78.91% of the mass of the copper slag, and the separation and enrichment of the copper comprises the following steps:
(1) blast furnace copper slag crushing mill
Crushing the blast furnace copper slag by using a crusher, and then crushing and grinding the blast furnace copper slag by using a rod mill until the mass percentage of the blast furnace copper slag is-0.075 mm, namely 64.96%, so as to obtain the crushed copper slag grinding material.
(2) Screening of crushed and ground products
And screening the copper slag crushed grinding material by using a vibrating screen, wherein the screen aperture is 0.15mm, the oversize fraction is directly used as high-quality copper concentrate, and the undersize fraction is subjected to rapid flotation.
(3) Rapid flotation
Adding 50g/t of collecting agent butyl xanthate and 2g/t of foaming agent into undersize products obtained by classification#And (4) performing rapid flotation on the oil at the concentration of 8g/t, directly using a foam product as a rapid flotation concentrate, and performing magnetic separation-ball milling-vulcanization flotation on a tank bottom product.
(4) Magnetic separation-ball milling-sulfuration flotation
For a tank bottom product of the rapid flotation, magnetic separation concentrate and magnetic separation tailings are separated by adopting a magnetic separation method, the field intensity is 600mT, the magnetic separation concentrate is concentrated and dehydrated and then enters a ball mill for grinding, the grinding concentration is about 82%, the magnetic separation concentrate is ground to be 90% in mass percentage of-0.038 mm, the slurry concentration is adjusted to be 30.21%, ammonium sulfate is firstly added for vulcanization at 500g/t, and a collecting agent butyl xanthate 50g/t and a foaming agent 2 are added after vulcanization#Oil 8g/t, carrying out vulcanization flotation roughing, carrying out primary scavenging on the obtained tank bottom product, and carrying out fine selection on the foam product; the foam product of the sulfuration roughing is refined for the first time, the product at the bottom of the first refining tank returns to the sulfuration flotation roughing, and the foaming agent 2 is added into the foam of the first refining#4g/t of oil enters secondary concentration; returning the bottom product of the secondary concentration tank to the primary concentration, and taking the foam product as flotation concentrate; adding 20g/t of butyl xanthate into a product at the bottom of a vulcanizing flotation roughing tank, and performing scavenging for one time; returning the foam of one scavenging to the rough concentration of sulfuration flotation, adding 20g/t of butyl xanthate and 2g/t of foaming agent into the product at the bottom of the tank#4g/t of oil, and performing secondary scavenging; returning the secondary scavenging foam product to the primary scavenging, and combining the product at the bottom of the tank and the magnetic separation tailings to be used as the productAnd (5) final tailings.
The product indices obtained were as follows: 0.78% yield of plus 0.15mm on sieve, 22.15% copper, 15.26% recovery rate; the yield of the fast flotation concentrate is 1.64 percent, the copper content is 20.86 percent, and the recovery rate is 30.21 percent; the flotation concentrate yield is 5.56%, the copper content is 5.21%, and the recovery rate is 25.65%; the comprehensive yield of the three products is 7.98%, the copper content is 10.07%, and the copper recovery rate is 71.12%.
Example 2
The process flow shown in fig. 1 is adopted to separate and enrich the low-grade copper slag of the blast furnace, the copper slag of the blast furnace processed by the embodiment contains 2.25% of copper, the copper mainly exists in copper simple substance, alloy and chalcocite, and accounts for about 2.13% of the mass of the copper slag, the main matrix is a yellow feldspar mineral, and accounts for about 76.91% of the mass of the copper slag, and the separation and enrichment of the copper comprises the following steps:
(1) blast furnace copper slag crushing mill
Crushing the blast furnace copper slag by using a crusher, and then crushing and grinding the blast furnace copper slag by using a rod mill until the mass percentage of-0.075 mm accounts for 59.87%, thereby obtaining the crushed copper slag grinding material.
(2) Screening of crushed and ground products
And screening the copper slag crushed grinding material by using a vibrating screen, wherein the screen aperture is 0.20mm, the oversize fraction is directly used as high-quality copper concentrate, and the undersize fraction is subjected to rapid flotation.
(3) Rapid flotation
Adding 70g/t of collecting agent butyl xanthate and 2g/t of foaming agent into undersize product#And (3) performing rapid flotation on the oil at the concentration of 12g/t, directly using a foam product as a rapid flotation concentrate, and performing magnetic separation, ball milling and vulcanization flotation on a tank bottom product.
(4) Magnetic separation-ball milling-sulfuration flotation
For a tank bottom product of the rapid flotation, magnetic separation concentrate and magnetic separation tailings are separated by adopting a magnetic separation method, the field intensity is 500mT, the magnetic separation concentrate is concentrated and dehydrated and then enters a ball mill for grinding, the grinding concentration is about 78%, the magnetic separation concentrate is ground to 85% of minus 0.038mm in mass percentage, the slurry concentration is adjusted to 33.36%, 700g/t of ammonium sulfate is added into the tank bottom product of the rapid flotation for vulcanization, and 70g/t of butyl xanthate serving as a collecting agent is added after vulcanizationFoaming agent 2#Carrying out vulcanization flotation roughing on 12g/t oil, carrying out scavenging operation on a tank bottom product, and carrying out fine selection operation on a foam product; adding foaming agent 2 into vulcanized flotation foam product#4g/t of oil enters primary concentration; returning the bottom product of the primary concentration tank to the sulfuration flotation roughing, adding a foaming agent 2 into the primary concentration foam#4g/t of oil enters secondary concentration, the bottom product of the secondary concentration tank returns to the primary concentration, and the secondary concentration foam product is used as flotation concentrate; adding 50g/t of butyl xanthate and 2g/t of foaming agent into a bottom product of a crude flotation tank in a vulcanization flotation manner#4g/t of oil, carrying out primary scavenging, and returning primary scavenging foam to vulcanization flotation operation; adding 50g/t of butyl xanthate and 2g/t of foaming agent into the product at the bottom of the primary scavenging tank#And 4g/t of oil, carrying out secondary scavenging, returning secondary scavenging foam to the primary scavenging, and taking the product at the bottom of the tank and the magnetic separation tailings as final tailings.
The following indices were obtained: the yield of plus 0.20mm on the sieve is 1.79 percent, the copper content is 23.01 percent, and the recovery rate is 18.26 percent; the yield of the fast flotation concentrate is 4.20 percent, the copper content is 21.05 percent, and the recovery rate is 39.26 percent; the flotation concentrate yield is 7.79 percent, the copper content is 6.83 percent, and the recovery rate is 23.65 percent; the comprehensive yield of the three products is 13.77 percent, the copper content is 13.26 percent, and the copper recovery rate is 81.17 percent.
Example 3
The process flow shown in fig. 1 is adopted to separate and enrich the low-grade copper slag of the blast furnace, the copper slag of the blast furnace processed by the embodiment contains 3.52% of copper, the copper mainly exists in copper simple substance, alloy and chalcocite, and accounts for about 3.30% of the mass of the copper slag, the main matrix is a yellow feldspar mineral, and accounts for about 75.30% of the mass of the copper slag, and the separation and enrichment of the copper comprises the following steps:
(1) blast furnace copper slag crushing mill
And (3) crushing and grinding the blast furnace copper slag by adopting a crusher and a rod mill until the mass percentage of-0.075 mm accounts for 63.15%, so as to obtain the crushed copper slag grinding material.
(2) Screening of crushed and ground products
And screening the copper slag crushed grinding material by using a vibrating screen, wherein the screen aperture is 0.20mm, the oversize fraction is directly used as high-quality copper concentrate, and the undersize fraction is subjected to rapid flotation.
(3) Rapid flotation
Concentrating and dehydrating the obtained undersize product, adjusting slurry concentration, adding collecting agent butyl xanthate 100g/t and foaming agent 2#And (3) performing rapid flotation on the oil at a concentration of 16g/t, directly using a foam product as a rapid flotation concentrate, and performing magnetic separation, ball milling and vulcanization flotation on a tank bottom product.
(4) Magnetic separation-ball milling-sulfuration flotation
For a tank bottom product of the rapid flotation, magnetic separation concentrate and magnetic separation tailings are adopted, the field intensity is 500mT, the magnetic separation concentrate is concentrated and dehydrated and then enters a ball mill for grinding, the grinding concentration is about 73 percent, the magnetic separation concentrate is ground to be 87 percent by mass with the concentration of minus 0.038mm, the slurry concentration is adjusted to 36.56 percent, ammonium sulfate is added for vulcanization at 1000g/t, and a collecting agent butyl xanthate of 100g/t and a foaming agent of 2 are added after vulcanization#Oil of 16g/t is subjected to vulcanization flotation roughing, a tank bottom product enters one scavenging operation, and a foam product enters a fine selection operation; adding foaming agent 2 into the foam product of the rough flotation of the sulfuration flotation#Oil 8g/t enters a first concentration operation, a product at the bottom of the first concentration tank returns to the vulcanization flotation roughing, and a foaming agent 2 is added into the first concentration foam#Oil 8g/t enters secondary concentration, a product at the bottom of the secondary concentration tank returns to primary concentration operation, and a secondary concentration foam product is used as flotation concentrate; adding 70g/t of butyl xanthate and 2g/t of foaming agent into a bottom product of a crude flotation tank in a vulcanization flotation manner#Oil 8g/t, once scavenging, returning once scavenging foam to vulcanization flotation, adding 70g/t of butyl xanthate and 2g of foaming agent into a product at the bottom of the once scavenging tank#And (4) performing secondary scavenging on the oil at 8g/t, returning a secondary scavenging foam product to the primary scavenging, and taking a secondary scavenging tank bottom product and magnetic separation tailings as tailings.
The following indices were obtained: the yield of plus 0.20mm on the sieve is 2.91 percent, the copper content is 22.56 percent, and the recovery rate is 18.63 percent; the yield of the fast-floating concentrate is 6.19 percent, the copper content is 20.95 percent, and the recovery rate is 36.87 percent; the yield of flotation concentrate is 15.98%, the copper content is 6.53%, and the recovery rate is 29.65%; the comprehensive yield of the three products is 25.08 percent, the copper content is 7.64 percent, and the copper recovery rate is 85.15 percent.
Example 4
The process flow shown in fig. 1 is adopted to separate and enrich the low-grade copper slag of the blast furnace, the copper slag of the blast furnace processed by the embodiment contains 4.35% of copper, the copper mainly exists in copper simple substance, alloy and chalcocite, and accounts for about 4.38% of the mass of the copper slag, the main matrix is a yellow feldspar mineral, and accounts for about 73.10% of the mass of the copper slag, and the separation and enrichment of the copper comprises the following steps:
(1) blast furnace copper slag crushing mill
And (3) crushing and grinding the blast furnace copper slag to-0.075 mm by mass percentage of 60.23% by adopting a crusher and a rod mill to obtain the crushed copper slag grinding material.
(2) Screening of crushed and ground products
Screening the copper slag crushed grinding material by using a vibrating screen, wherein the screen aperture is 0.25mm, the oversize fraction is directly used as high-quality copper concentrate, and the undersize fraction is subjected to rapid flotation;
(3) rapid flotation
Adding 120g/t of collecting agent butyl xanthate and 2g/t of foaming agent into undersize product#And (3) performing rapid flotation on the oil at a concentration of 20g/t, directly using a foam product as a rapid flotation concentrate, and performing magnetic separation, ball milling and vulcanization flotation on a tank bottom product.
(4) Magnetic separation-ball milling-sulfuration flotation
For a tank bottom product of the rapid flotation, magnetic separation concentrate and magnetic separation tailings are separated by adopting a magnetic separation method, the field intensity is 550mT, the magnetic separation concentrate is concentrated and dehydrated and then enters a ball mill for grinding, the grinding concentration is about 68%, the magnetic separation concentrate is ground to be 87% in mass percentage of-0.038 mm, the slurry concentration is adjusted to 37.85%, 1300g/t of ammonium sulfate is added into the tank bottom product of the rapid flotation for vulcanization, and 120g/t of butyl xanthate serving as a collecting agent and 2g/t of a foaming agent are added after vulcanization#Oil of 20g/t is subjected to vulcanization flotation roughing, the bottom product of the vulcanization flotation roughing tank enters primary scavenging, and the foam product of the vulcanization flotation roughing enters primary concentration; adding foaming agent 2 into the foam product of the rough flotation of the sulfuration flotation#2g/t of oil enters primary concentration, a product at the bottom of the primary concentration tank returns to the vulcanization flotation roughing, and a foaming agent 2 is added into primary concentration foam#2g/t of oil enters secondary concentration, a product at the bottom of the secondary concentration tank returns to the primary concentration, and a secondary concentration foam product is used as flotation concentrate; adding butyl xanthate 10 into the bottom product of the vulcanizing flotation roughing tank0g/t, blowing agent 2#2g/t of oil, once scavenging, returning once scavenging foam to the operation of vulcanizing flotation roughing, adding 100g/t of butyl xanthate and 2g of foaming agent into the product at the bottom of the once scavenging tank#And (4) performing secondary scavenging on the oil at 2g/t, returning a secondary scavenging foam product to the primary scavenging operation, and combining a secondary scavenging tank bottom product and the magnetic separation tailings to be used as tailings.
The following indices were obtained: the yield of plus 0.25mm on a sieve is 3.86 percent, the copper content is 22.01 percent, and the recovery rate is 19.51 percent; the yield of the fast flotation concentrate is 7.63 percent, the copper content is 21.21 percent, and the recovery rate is 37.20 percent; the flotation concentrate yield is 19.08 percent, the copper content is 6.76 percent, and the recovery rate is 29.65 percent; the comprehensive yield of the three products is 30.56%, the copper content is 6.36%, and the copper recovery rate is 86.36%.
Example 5
The process flow shown in fig. 1 is adopted to separate and enrich the low-grade copper slag of the blast furnace, the copper slag of the blast furnace processed by the embodiment contains 4.96% of copper, the copper mainly exists in copper simple substance, alloy and chalcocite, and accounts for about 4.62% of the mass of the copper slag, the main matrix is a yellow feldspar mineral, and accounts for about 72.50% of the mass of the copper slag, and the separation and enrichment of the copper comprises the following steps:
(1) blast furnace copper slag crushing mill
And (3) crushing and grinding the blast furnace copper slag to-0.075 mm by mass percent and 60.61% by adopting a crusher and a rod mill to obtain the crushed copper slag grinding material.
(2) Screening of crushed and ground products
Screening the copper slag crushed grinding material by using a vibrating screen, wherein the screen aperture is 0.25mm, the oversize fraction is directly used as high-quality copper concentrate, and the undersize fraction is subjected to rapid flotation;
(3) rapid flotation
Adding 150g/t of collecting agent butyl xanthate and 2g/t of foaming agent into undersize product#And (3) performing quick flotation on the oil at the concentration of 24g/t, directly using a foam product as quick-floating concentrate, and performing magnetic separation-ball milling-vulcanization flotation on a tank bottom product.
(4) Magnetic separation-ball milling-sulfuration flotation
For the tank bottom product of the rapid flotation, magnetic separation concentrate and magnetic separation tailings are adopted, the field intensity is 600mT, and the magnetic separation concentrateConcentrating and dehydrating the ore, grinding the ore in a ball mill until the grinding concentration is about 65.6%, grinding the magnetic concentrate to 85% in mass percentage of-0.038 mm, adjusting the slurry concentration to 38.92%, adding 1500g/t of ammonium sulfate for vulcanization, adding 150g/t of butyl xanthate serving as a collecting agent and 2g/t of a foaming agent after vulcanization#Oil 24g/t, carrying out vulcanization flotation roughing, carrying out primary scavenging on a tank bottom product, and carrying out fine selection on a foam product; adding foaming agent 2 into the foam product of the rough flotation of the sulfuration flotation#Oil 6g/t enters first concentration, a product at the bottom of the first concentration tank returns to the vulcanization flotation roughing, and a foaming agent 2 is added into first concentration foam#Oil of 6g/t enters secondary concentration, a product at the bottom of the secondary concentration tank returns to the primary concentration, and a secondary concentration foam product is used as flotation concentrate; adding 100g/t of butyl xanthate and 2g/t of foaming agent into a bottom product of a crude flotation tank in a vulcanization flotation manner#6g/t of oil, once scavenging, returning once scavenging foam to the operation of vulcanizing flotation roughing, adding 100g/t of butyl xanthate and 2g of foaming agent into the product at the bottom of the once scavenging tank#And 6g/t of oil, carrying out secondary scavenging, returning a secondary scavenging foam product to the primary scavenging, and combining a secondary scavenging tank bottom product and the magnetic separation tailings to be used as final tailings.
The following indices were obtained: the yield of the copper on the sieve plus 0.25mm is 4.62 percent, the copper content is 21.01 percent, and the recovery rate is 19.62 percent; the yield of the fast flotation concentrate is 9.69 percent, the copper content is 20.21 percent, and the recovery rate is 39.57 percent; the flotation concentrate yield is 21.80%, the copper content is 6.96%, and the recovery rate is 30.65%; the comprehensive yield of the three products is 36.11%, the copper content is 5.60%, and the copper recovery rate is 89.84%.
Comparative example 1
The blast furnace copper slag processed by the comparative example has the same components as those of the example 3, and the processing method is different from the following steps: the method does not comprise screening, quick flotation, magnetic separation and rod mill operation, only comprises crushing and vulcanizing flotation, and comprises the following steps:
s1: blast furnace copper slag crushing mill
And (3) crushing and grinding the blast furnace copper slag until the mass percentage of-0.075 mm accounts for 87.15%, so as to obtain the crushed copper slag grinding material.
S2: sulfidizing flotation
The copper slag crushed grinding material is prepared by adding waterAdding 1000g/t of ammonium sulfate into slurry for vulcanization, adding 1000g/t of sodium carbonate for dispersion after vulcanization, and then adding 250g/t of butyl xanthate serving as a collecting agent and 2g/t of foaming agent#Oil 32g/t, carrying out vulcanization flotation roughing, carrying out primary scavenging on a tank bottom product, and carrying out fine selection on a foam product; adding foaming agent 2 into the foam product of the rough flotation of the sulfuration flotation#Oil 8g/t enters first concentration, a product at the bottom of the first concentration tank returns to the vulcanization flotation roughing, and a foaming agent 2 is added into first concentration foam#Oil of 16g/t enters secondary concentration, a product at the bottom of the secondary concentration tank returns to the primary concentration, and a secondary concentration foam product is used as flotation concentrate; adding 100g/t of butyl xanthate and 2g/t of foaming agent into a bottom product of a vulcanizing flotation roughing tank#Oil 16g/t, once scavenging, returning foam to the vulcanizing flotation roughing, adding butyl xanthate 40g/t and foaming agent 2 into the product at the bottom of the once scavenging tank#And 8g/t of oil, carrying out secondary scavenging, returning the secondary scavenging foam product to the primary scavenging, and taking the tank bottom product as tailings.
The following indices were obtained: the flotation concentrate yield is 14.60%, the copper content is 14.53%, and the recovery rate is 60.25%.
Compared with the indexes obtained in the embodiment 3, the process of the embodiment 3 of the invention is adopted to treat the same blast furnace copper slag, and the recovery rate is improved by about 25 percent; and middlings are not accumulated, and the flotation operation is easy and stable.
Comparative example 2
The blast furnace copper slag processed by the comparative example has the same components as those of the example 3, and the processing method is different from the following steps: the method does not adopt a rod mill to grind the copper slag, does not adopt magnetic separation to pre-enrich copper after rapid flotation, does not adopt operations such as ball milling and regrinding, and comprises the following steps:
s1: blast furnace copper slag crushing mill
And (3) crushing and grinding the blast furnace copper slag until the mass percentage of the blast furnace copper slag is-0.075 mm and the content of the copper slag accounts for 85.11%, so as to obtain the crushed copper slag grinding material.
S2: screening of crushed and ground products
And screening the copper slag crushed grinding material by using a vibrating screen, wherein the screen aperture is 0.25mm, the oversize fraction is directly used as high-quality copper concentrate, and the undersize fraction is subjected to rapid flotation.
S3: rapid flotation
Adding 100g/t of collecting agent butyl xanthate and 2g/t of foaming agent into the obtained undersize product#16g/t of oil, preparing slurry for quick flotation, directly using a foam product as quick-floating concentrate, and performing vulcanization flotation on a tank bottom product.
S4: sulfidizing flotation
Adding 1000g/t of ammonium sulfate into a bottom product of the rapid flotation tank for vulcanization, and adding 100g/t of butyl xanthate serving as a collecting agent and 2g/t of a foaming agent after vulcanization#Oil of 16g/t is subjected to vulcanization flotation roughing, a tank bottom product enters one scavenging operation, and a foam product enters a fine selection operation; adding foaming agent 2 into the foam product of the rough flotation of the sulfuration flotation#Oil 8g/t enters a first concentration operation, a product at the bottom of the first concentration tank returns to the vulcanization flotation roughing, and a foaming agent 2 is added into the first concentration foam#Oil 8g/t enters secondary concentration, a product at the bottom of the secondary concentration tank returns to primary concentration operation, and a secondary concentration foam product is used as flotation concentrate; adding 70g/t of butyl xanthate and 2g/t of foaming agent into a bottom product of a crude flotation tank in a vulcanization flotation manner#Oil 8g/t, once scavenging, returning once scavenging foam to the vulcanization flotation roughing, adding 70g/t of butyl xanthate and 2g of foaming agent into the product at the bottom of the once scavenging tank#And 8g/t of oil, carrying out secondary scavenging, returning a secondary scavenging foam product to the primary scavenging, and taking a secondary scavenging tank bottom product as tailings.
The following indices were obtained: 0.98% yield of plus 0.25mm on sieve, 59.13% copper, 16.52% recovery rate; the yield of the fast-floating concentrate is 4.40 percent, the copper content is 30.94 percent, and the recovery rate is 38.68 percent; the flotation concentrate yield is 11.58%, the copper content is 5.55%, and the recovery rate is 18.26%; the comprehensive yield of the three products is 16.97%, the copper content is 15.25%, and the copper recovery rate is 73.46%.
Compared with the indexes obtained in the example 3, the recovery rate of the blast furnace copper slag treated by the process in the example 3 is improved by about 12 percent.
The embodiment shows that the method provided by the invention is used for treating the blast furnace copper slag, the problems of middling accumulation, coarse particle/flake copper accumulation, difficulty in stabilizing flotation operation and the like of the blast furnace copper slag in the ore grinding-sulfuration dispersion flotation process are solved, the copper content of tailings in the ore grinding-screening-rapid flotation-sulfuration flotation process is reduced, the comprehensive recovery rate of copper is improved, particularly for slag containing low copper, such as blast furnace copper slag containing 1-3% of copper, the copper recovery rate can be improved by more than 10%, the ore grinding cost can be reduced, and the comprehensive recovery rate of copper is improved.

Claims (6)

1. The method for enriching the low-grade copper slag of the blast furnace is characterized by comprising the following steps of:
s1: crushing low-grade copper slag in a blast furnace, and grinding the copper slag by using a rod mill to obtain a copper slag crushed grinding material, wherein the grinding fineness of the copper slag crushed grinding material is-0.075 mm, and the mass percentage content of the copper slag crushed grinding material is 55-65%;
s2: grading the copper slag crushed grinding materials, wherein the grading granularity is 0.15-0.25 mm, the rough granules obtained by grading are copper concentrate, and the fine granules obtained enter a rapid flotation step;
s3: blending the fine particle materials into slurry with the solid particle mass percentage concentration of 40-60%, then adding a collecting agent and a foaming agent for rapid flotation, wherein the collecting agent is a copper sulfide ore collecting agent, a foam product obtained through rapid flotation is rapid flotation concentrate, and an obtained tank bottom product enters a magnetic separation step;
s4: separating the tank bottom product obtained by the rapid flotation by adopting magnetic separation, wherein the magnetic separation strength is 300-600 mT, and separating to obtain magnetic concentrate and magnetic tailings; collecting the magnetic separation tailings serving as final tailings; grinding the magnetic concentrate until the mass percentage of the magnetic concentrate is 85-100% of-0.038 mm, adjusting the concentration of the ground slurry to 30-40% to obtain ground slurry of the magnetic concentrate, and then performing vulcanization flotation;
s5: adding a vulcanizing agent into the magnetic separation concentrate grinding slurry for vulcanization treatment, then adding a copper sulfide ore collecting agent and a foaming agent for vulcanization flotation, performing primary scavenging on a tank bottom product obtained by the vulcanization flotation, and performing primary concentration on a foam product obtained by the vulcanization flotation;
addition of frother 2 to sulfidized flotation froth product#Oil with the addition amount of 0-8 g/t, and then carrying out primary concentration, i.e. oneReturning the bottom product of the secondary concentration to the vulcanization flotation operation, adding a foaming agent 2 into the foam product of the primary concentration#Oil with the addition amount of 0-8 g/t is subjected to secondary concentration;
returning the bottom product obtained by the secondary concentration to the primary concentration operation, wherein the foam product obtained by the secondary concentration is flotation concentrate;
adding butyl xanthate and 2 to a tank bottom product obtained by sulfuration flotation#The dosage of the oil and the butyl xanthate is 20-100 g/t, 2#The oil consumption is 0-8 g/t, one scavenging is carried out,
returning the foam product obtained by the primary scavenging to the vulcanization flotation operation, and performing secondary scavenging on the tank bottom product obtained by the primary scavenging;
adding butyl xanthate and 2 into the tank bottom product obtained by one-time scavenging#The dosage of the oil and the butyl xanthate is 20-100 g/t, 2#And (3) carrying out secondary scavenging when the addition amount of the oil is 0-8 g/t, returning a foam product subjected to the secondary scavenging to the primary scavenging operation, and combining a tank bottom product subjected to the secondary scavenging with the magnetic separation tailings to be used as final tailings for collection.
2. The method for enriching low-grade copper slag of a blast furnace according to claim 1, wherein in the step S1, the mass percentage of copper in the processed low-grade copper slag of the blast furnace is 1-5%.
3. The method of claim 1, wherein in the step S2, the classifying equipment is a classifier, a hydrocyclone or an industrial sieve.
4. The method for enriching the low-grade copper slag of the blast furnace according to claim 1, wherein in the step S3, the copper sulfide ore collecting agent is butyl xanthate, butylamine black powder or Z-200, and the dosage is 50-150 g/t; the foaming agent is 2#Oil, MIBC or sodium dodecyl sulfate, and the dosage is 8-24 g/t.
5. The method for enriching low-grade copper slag of a blast furnace according to claim 4, wherein in step S5, the vulcanizing agent is sodium sulfide, ammonium sulfate or ammonium bisulfate, and the dosage is 500-1500 g/t.
6. The method for enriching the low-grade copper slag of the blast furnace according to claim 5, wherein in the step S5, the copper sulfide ore collecting agent is butyl xanthate, butylamine black powder or Z-200, and the dosage is 50-150 g/t; the foaming agent is 2#Oil, MIBC or sodium dodecyl sulfate, and the dosage is 8-24 g/t.
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CN105435970A (en) * 2015-12-28 2016-03-30 昆明理工大学 Mineral processing process for recovering copper from copper smelting slag through flotation
CN110882834A (en) * 2019-12-16 2020-03-17 江西理工大学应用科学学院 Beneficiation method for efficiently recovering copper from copper smelting slag

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Publication number Priority date Publication date Assignee Title
US4275847A (en) * 1978-07-12 1981-06-30 Albert Bahr Process for the treatment of aluminum-salt slags
CN102878821A (en) * 2012-10-24 2013-01-16 广西有色再生金属有限公司 Smoke purifying and waste heat recycling device for low-grade composition brass smelting and control method of smoke purifying and waste heat recycling device
CN105435970A (en) * 2015-12-28 2016-03-30 昆明理工大学 Mineral processing process for recovering copper from copper smelting slag through flotation
CN110882834A (en) * 2019-12-16 2020-03-17 江西理工大学应用科学学院 Beneficiation method for efficiently recovering copper from copper smelting slag

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