CN113751206A - Ore dressing method for arsenic-lead-zinc ore - Google Patents

Ore dressing method for arsenic-lead-zinc ore Download PDF

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CN113751206A
CN113751206A CN202111080077.0A CN202111080077A CN113751206A CN 113751206 A CN113751206 A CN 113751206A CN 202111080077 A CN202111080077 A CN 202111080077A CN 113751206 A CN113751206 A CN 113751206A
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lead
arsenic
flotation
zinc
ore
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CN113751206B (en
Inventor
刘进
刘志成
张红英
高连启
刘牡丹
惠世和
王成行
郎召有
刘建国
何艳平
彭芬兰
林恬盛
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Chihong Technology & Engineering Co ltd
Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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Chihong Technology & Engineering Co ltd
Institute of Resource Utilization and Rare Earth Development of 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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention belongs to the technical field of mineral processing, and particularly discloses a beneficiation method for arsenic-lead-zinc ore. The ore dressing method for treating the arsenic-lead-zinc-containing ores containing the ash, the sulfur and the lead ore comprises the following steps: grinding the arsenic-lead-zinc ore to prepare ore pulp, then performing arsenic flotation to obtain arsenic concentrate, and then performing lead flotation to obtain lead concentrate. The ore dressing method for the arsenic-lead-zinc ore provided by the invention is characterized in that arsenic flotation is firstly carried out innovatively, arsenic concentrate is obtained by flotation through ore grinding and adopting a proper arsenic flotation process and a proper flotation reagent, and the ash, sulfur, arsenic and lead ore contained in the arsenic-lead-zinc ore is basically recycled and enters the arsenic concentrate, so that the arsenic concentrate does not enter lead flotation operation; and then, performing lead flotation on the tailings obtained by arsenic flotation, and obviously reducing the arsenic content in lead concentrate obtained by flotation under the condition of a proper lead flotation process and a proper flotation reagent, wherein the arsenic grade is controlled to be below 0.4%. The method also has the advantages of small dosage of the medicament and good separation effect.

Description

Ore dressing method for arsenic-lead-zinc ore
Technical Field
The invention relates to the technical field of mineral processing, in particular to a beneficiation method of arsenic-lead-zinc ore.
Background
As-removing and As-reducing of lead concentrate products in the beneficiation of As-containing lead-zinc ores is an important research topic. At present, the arsenic reduction by the ore dressing method mainly aims at arsenic-containing minerals such as arsenic pyrite, realgar and arsenopyrite. For example, chinese patent No. CN105251620B discloses a complex beneficiation method for arsenic-containing lead-zinc sulfide ore, which can obtain qualified lead and zinc concentrate products containing arsenic. Chinese patent application publication No. CN106513182A discloses a beneficiation method of arsenic-containing lead sulfide ore, which can obtain lead concentrate and arsenic concentrate, wherein the lead grade of the lead concentrate is 66.30%, the lead recovery rate is 85.04%, the arsenic grade of the arsenic concentrate is 8.48%, and the arsenic recovery rate is 79.84%. The above patents are directed to arsenic reduction of arsenious ore of arsenious sands, because the arsenious ore of arsenious sands can realize the dissociation or separation of arsenic and lead-zinc sulfide ore by physical means such as ore grinding, the arsenic in the arsenious ore is easy to remove, and a corresponding qualified concentrate product is obtained.
However, for the ash arsenic lead ore mineral with the crystal lattice containing arsenic and similar to the galena, research on arsenic reduction of lead concentrate has not been carried out. Arsenopyrite (Pb)5(Sb,As)2S8) The crystal is plate-shaped, has a pseudo-hexagonal shape, is gray with lead, is opaque, has metallic luster, is shell-shaped with fracture, is brittle, has the hardness of 3 and has the density of 6.44g/cm3. The ash arsenic lead ore and the galena are closely related in intergrowth, the embedded granularity is fine, and a small part of the ash arsenic lead ore is contained in the galena in an inclusion body smaller than 10 microns, so that the arsenic content in lead concentrate exceeds the standard. As the properties of the ash, sulfur, arsenic and lead ore are very similar to those of galena, the flow direction of the ash, sulfur, arsenic and lead ore in ore dressing is basically consistent with that of the galena, once the raw ore contains the arsenic-containing minerals, the arsenic-containing minerals can enter lead concentrate in the flotation process, and the arsenic in the lead concentrate is easy to exceed the standard. If the arsenic content in the lead concentrate exceeds the standard, the quality of smelting products can be seriously influenced, and in the smelting process, the arsenic can also generate harmful substances, corrode equipment and pollute the atmosphere.
Therefore, it is necessary to conduct an in-depth research on the arsenious lead-zinc-containing ores such as arsenious lead ore to effectively solve the problem of separation from galena and obtain lead concentrate with satisfactory arsenic content.
Disclosure of Invention
The invention mainly solves the technical problem of providing an arsenic-containing lead-zinc ore beneficiation method, which can obtain lead concentrate products with the arsenic content lower than 0.4%.
In order to solve the technical problems, the invention adopts the technical scheme that: the beneficiation method for the arsenic-lead-zinc-containing ores comprises the following steps: grinding the arsenic-lead-zinc ore to prepare ore pulp, then performing arsenic flotation to obtain arsenic concentrate, and then performing lead flotation to obtain lead concentrate.
And performing zinc flotation on the obtained lead tailings to obtain zinc concentrate.
As a preferred embodiment of the present invention, the arsenic flotation comprises one arsenic rougher flotation, at least one cleaner flotation and at least one scavenger flotation; the reagent adopted by the arsenic roughing comprises an arsenic collecting agent and a combined inhibitor; and/or the reagent used for beneficiation comprises a combined inhibitor, and/or the reagent used for scavenging comprises an arsenic collector;
wherein the arsenic collecting agent comprises aniline black powder and modified ethioamine; the combined inhibitor comprises at least one of sodium carbonate, humate, bleaching powder, sodium sulfite and zinc sulfate.
As a preferred embodiment of the invention, the combined inhibitor is a mixture of sodium carbonate, humate, bleaching powder, sodium sulfite and zinc sulfate, and the mass ratio of the sodium carbonate, the humate, the bleaching powder, the sodium sulfite and the zinc sulfate in the combined inhibitor is (15-25): 5-10): 10-20): 20-30): 30-50;
the modified ethioamine is a mixture of ethioamine and diesel oil, and preferably the ethioamine and the diesel oil are mixed according to a mass ratio of 1 (2-4).
As a preferred embodiment of the invention, the arsenic flotation comprises one arsenic rougher, 1-2 cleaner and 1-2 scavenger, preferably the arsenic flotation comprises one arsenic rougher, 2 cleaner and 2 scavenger.
According to a preferred embodiment of the invention, the reagents adopted by the arsenic roughing are a combined inhibitor, aniline black and modified ethionamide, wherein the dosage of the combined inhibitor is 1000-2500 g/t, the dosage of the aniline black is 5-50 g/t and the dosage of the modified ethionamide is 10-50 g/t based on the mass of the raw ore of the arsenic-lead-zinc ore;
the agent adopted in the first concentration is a combined inhibitor, and the dosage of the combined inhibitor is 100-500 g/t based on the mass of the arsenic-lead-zinc ore raw ore; and/or taking a medicament adopted in the second concentration as a combined inhibitor, wherein the dosage of the combined inhibitor is 50-100 g/t based on the mass of the raw ore of the arsenic-lead-zinc ore;
the first scavenging adopts aniline black and modified ethionamide, the dosage of the aniline black is 2-20 g/t, and the dosage of the modified ethionamide is 4-20 g/t based on the mass of the arsenic-lead-zinc ore; and/or the reagents adopted by the second scavenging are aniline black and modified ethionamide, the dosage of the aniline black is 1-10 g/t, and the dosage of the modified ethionamide is 1-10 g/t based on the mass of the arsenious plumbum and zincite raw ore.
As a preferred embodiment of the invention, the lead flotation comprises one lead roughing, at least one concentration and at least one scavenging; the lead roughing adopts medicaments comprising lime, zinc sulfate, ethidium and azote, ammonium nitrate and No. 2 oil; and/or the concentration adopted agents comprise lime and zinc sulfate; and/or the scavenging agent comprises ethidium nitrate and ammonium nitrate.
As a preferred embodiment of the invention, the lead flotation comprises one lead rougher flotation, 1-2 cleaner flotation and 1-3 scavenger flotation, preferably the lead flotation comprises one lead rougher flotation, 2 cleaner flotation and 3 scavenger flotation.
In a preferred embodiment of the invention, the lead roughing adopts the agents of lime, zinc sulfate, ethidium and azote, ammonium nitrate and No. 2 oil; based on the mass of the raw ore of the arsenic-lead-zinc ore, the lime, the zinc sulfate, the ethidium-sulfur nitrogen, the ammonium nitrate heicide and the No. 2 oil (namely 2)#Oil) is 1000-5000 g/t, 1000-2000 g/t, 40-100 g/t, 20-50 g/t, 5-30 g/t;
the first selection adopts lime and zinc sulfate as reagents, and the dosage of the lime and the zinc sulfate is respectively 200-500 g/t and 100-200 g/t based on the mass of the raw ore of the zinc ore containing arsenic and lead; and/or the reagents adopted in the second concentration are lime and zinc sulfate, and the dosage of the lime and the dosage of the zinc sulfate are respectively 100-200 g/t and 50-100 g/t based on the mass of the raw ore of the arsenic-lead-zinc ore;
the first scavenging adopts the reagents of ethidium and ammonium nitrate, and the dosages of the ethidium and the ammonium nitrate are respectively 20-50 g/t and 10-25 g/t based on the mass of the raw ore of the arsenious plumbum and zincite; and/or the reagents adopted by the second scavenging are ethidium and ammonium nitrate black chemicals, and the dosage of the ethidium and the ammonium nitrate black chemicals is 10-25 g/t and 5-15 g/t respectively based on the mass of the arsenious plumbum and zincite raw ore; and/or the reagents adopted by the third scavenging are ethidium and ammonium nitrate black chemicals, and the dosage of the ethidium and the ammonium nitrate black chemicals is 1-10 g/t and 1-10 g/t respectively based on the mass of the arsenious plumbum and zincite raw ore.
In the invention, the fineness of the ore grinding of the zinc ore containing arsenic and lead is-0.075 mm and accounts for 65-85%, namely the mass percentage of minerals with the particle size of less than 0.075mm in the ore grinding product accounts for 65-85%.
The invention provides a beneficiation method for arsenic-lead-zinc ore, wherein arsenic in the arsenic-lead-zinc ore is mainly in the form of arsenopyrite and arsenopyrite. Wherein the crystal lattices of the lead arsenic oxysulfide mineral contain arsenic, and the arsenic in the lead arsenic oxysulfide mineral cannot be removed by a physical method. And as various physical and chemical properties of the lead-arsenic-lime ore are similar to those of the galena, the flow direction of the lead-arsenic-lime ore in ore dressing is basically consistent with that of the galena, arsenic easily enters lead concentrate in a flotation process, arsenic in the lead concentrate obtained by flotation exceeds the standard, the arsenic content in the lead concentrate obtained by flotation is more than 0.5 percent, and the next use of the lead concentrate is seriously influenced. Therefore, how to obtain lead concentrate products with qualified arsenic content is a problem to be solved.
At present, when arsenic-lead-zinc ore containing ash, sulfur, arsenic and lead ore is treated, a method of firstly performing lead flotation to obtain lead concentrate and then performing ore dressing to the lead concentrate to reduce arsenic is adopted. The existing beneficiation process has the problems of large medicament dosage and poor arsenic reduction and separation effect. Because lead concentrate obtained by flotation contains more chemicals, in order to achieve the arsenic reduction separation effect, firstly, chemicals need to be removed, and then, arsenic reduction flotation is carried out, so that the using amount of inhibitors is more.
The ore dressing method for the zinc ore containing arsenic, lead and zinc provided by the invention adopts a process of preferentially floating arsenic and then floating lead for the first time innovatively, namely arsenic flotation is carried out firstly, and the method specifically comprises the following steps: grinding ore, then adopting a proper arsenic flotation process and a proper flotation reagent to float to obtain arsenic concentrate, and basically recycling the ash, arsenic, sulfur and lead ore contained in the arsenic-lead-zinc ore into the arsenic concentrate so as not to enter lead flotation operation; then, lead flotation is carried out on tailings obtained by arsenic flotation, under the condition of a proper lead flotation process and a proper flotation reagent, the arsenic content in lead concentrate obtained by flotation is obviously reduced, wherein the arsenic grade can be controlled to be below 0.4 percent and about 0.35 percent, and the problem that the arsenic content of the lead concentrate exceeds the standard is effectively solved; and then, performing zinc flotation on the tailings obtained by the lead flotation, wherein the problem that the content of arsenic generally exceeds the standard is avoided in zinc concentrate, and qualified zinc concentrate can be obtained by recovering zinc in the obtained lead tailings by adopting the conventional zinc flotation method. The method can be used for treating arsenic-containing lead-zinc ore, is particularly suitable for treating arsenic-containing lead-zinc ore containing ash, sulfur, arsenic and lead ore, can respectively obtain arsenic concentrate, qualified lead concentrate containing arsenic and zinc concentrate products, and effectively separates minerals in the arsenic-containing lead-zinc ore.
Drawings
FIG. 1 is a process flow chart of the beneficiation method of the arsenic-lead-zinc ore provided by the invention;
FIG. 2 is a process flow chart of the beneficiation method for the arsenic-lead-zinc-containing ores adopted in comparative examples 1 to 3 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
In the following examples, the drugs used are all commercially available products unless otherwise specified. The concentrations or contents in the respective examples are mass percentages.
It is to be noted that the combination inhibitors (the combination inhibitor is denoted by Tf in the following examples) used in examples 1 to 3 are a mixture of sodium carbonate, humate, bleaching powder, sodium sulfite and zinc sulfate, and the mass ratio of sodium carbonate, humate, bleaching powder, sodium sulfite and zinc sulfate in the combination inhibitor is: 20:8:15:25:40. Wherein, the humate comprises sodium humate, potassium humate, magnesium humate, zinc humate and the like.
The used collector modified ethioamine is a mixture of ethioamine and diesel oil, and the ethioamine and the diesel oil are mixed according to the mass ratio of 1: 3.
The dosage g/t of the medicament is relative to the weight of the raw ore to be treated.
During the flotation operation, the times of scavenging and concentration can be adjusted according to the actual situation.
Because the problem that the arsenic content of the zinc concentrate exceeds the standard generally does not occur when the tailings obtained by the lead flotation are subjected to the zinc flotation, the qualified zinc concentrate product can be obtained by adopting the conventional zinc flotation method for the tailings obtained by the lead flotation. For example, in the following examples and comparative examples, zinc flotation can be carried out using the following process to obtain zinc concentrate, which is not required by the present invention.
The zinc flotation process comprises the following steps: adding sulfur inhibitor (0-4000 g/t lime), zinc activator (50-300 g/t copper sulfate), zinc collector (5-100 g/t butyl xanthate), and foaming agent (5-30 g/t 2)#Oil), and performing zinc roughing for 1-2 times to obtain zinc roughing concentrate and zinc roughing tailings; adding a sulfur inhibitor (lime with the use amount of 0-1000 g/t) into the zinc roughing concentrate, and carrying out zinc concentration for 0-4 times to obtain zinc concentrate; adding 0-50g/t of butyl xanthate into the zinc roughing tailings, and performing zinc scavenging for 1-5 times to obtain zinc scavenging tailings. Wherein, the middlings of any one of the zinc scavenging and the zinc concentration respectively return to the previous layer of operation in sequence.
Example 1
The process flow shown in FIG. 1 is adopted to treat raw ore of arsenic-lead-zinc ore, wherein the raw ore contains 6.25 percent of lead, 0.25 percent of arsenic and 82.35 percent of lead sulfide; arsenic exists mainly in the form of arsenopyrite and arsenopyrite. The flotation process comprises the following steps:
(1) grinding the raw ore to a grinding fineness of-0.075 mm accounting for 70%;
(2) adding the ground ore pulp into a flotation machine, adding 1500g/t of Tf, stirring, adding 5g/t of aniline black and 10g/t of modified ethioamine, and performing arsenic roughing to obtain arsenic roughing concentrate and arsenic roughing tailings;
(3) adding 2g/t of aniline black and 5g/t of modified ethioamine into the arsenic roughing tailings, stirring and then performing arsenic primary scavenging to obtain arsenic primary scavenging concentrate and arsenic primary scavenging tailings, and returning the arsenic primary scavenging concentrate to the previous stage;
(4) adding 1g/t of aniline black and 2g/t of modified ethioamine into the arsenic primary scavenging tailings, stirring and then carrying out arsenic secondary scavenging to obtain arsenic secondary scavenging concentrate and arsenic secondary scavenging tailings, and returning the arsenic secondary scavenging concentrate to the previous-stage operation;
(5) adding 100g/t Tf into the arsenic rough concentration concentrate, stirring, and then carrying out arsenic first concentration to obtain arsenic first concentration concentrate and arsenic first concentration tailings, wherein the arsenic first concentration tailings return to the previous-stage operation;
(6) adding 50g/t Tf into the arsenic primary concentration concentrate, stirring, and then carrying out arsenic secondary concentration to obtain arsenic secondary concentration concentrate and arsenic secondary concentration tailings, returning the arsenic secondary concentration tailings to the previous-stage operation, and obtaining arsenic secondary concentration concentrate, namely arsenic concentrate;
(7) adding 2000g/t lime, 1500g/t zinc sulfate, 50g/t ethidium nitrate, 30g/t ammonium nitrate black powder and 10g/t 2#Performing lead roughing to obtain lead roughing concentrate and lead roughing tailings;
(8) adding 25g/t of ethidium and sulfur nitrogen and 15g/t of ammonium nitrate black powder into the lead roughing tailings, stirring and then carrying out primary lead scavenging to obtain primary lead scavenging concentrate and primary lead scavenging tailings; returning the lead primary scavenging concentrate to the previous stage;
(9) adding 10g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead primary scavenging tailings, stirring and then carrying out lead secondary scavenging to obtain lead secondary scavenging concentrate and lead secondary scavenging tailings; returning the lead secondary scavenging concentrate to the previous stage;
(10) adding 2g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead secondary scavenging tailings, stirring and then scavenging lead for three times to obtain lead tertiary scavenging concentrate and lead tertiary scavenging tailings; returning the lead concentrate subjected to tertiary scavenging to the previous stage;
(11) adding 300g/t lime and 150g/t zinc sulfate into the lead roughing concentrate, stirring and then carrying out lead first-time concentration to obtain lead first-time concentration concentrate and lead first-time concentration tailings; returning the lead primary concentration tailings to the previous-stage operation;
(12) adding 100g/t lime and 50g/t zinc sulfate into the lead primary concentration concentrate, stirring and then carrying out lead secondary concentration to obtain lead secondary concentration concentrate and lead secondary concentration tailings, and returning the lead secondary concentration tailings to the previous-stage operation; the obtained lead secondary concentration concentrate is lead concentrate;
(13) the obtained lead tailings after the three-time scavenging is the lead tailings, and the zinc concentrate product can be obtained by performing conventional zinc flotation on the lead tailings.
In the embodiment, by adopting the beneficiation process of lead flotation after preferential arsenic flotation, the lead grade of the obtained lead concentrate product is 66.25%, wherein the content of arsenic is 0.35% and is lower than 0.4%, and the content of arsenic does not exceed the standard.
This example also obtained an arsenic concentrate product containing 5.10% arsenic.
Example 2
The process flow shown in FIG. 1 is adopted to treat raw ore of arsenic-lead-zinc ore, the raw ore contains 5.39% of lead, 0.28% of arsenic and 86.77% of lead sulfide, and the arsenic mainly exists in the form of arsenopyrite. The flotation process comprises the following steps:
(1) grinding the raw ore to-0.075 mm ore grinding fineness of 68.95%;
(2) adding the ground ore pulp into a flotation machine, adding 1800g/t of Tf, stirring, adding 8g/t of aniline black and 13g/t of modified ethioamine, and performing arsenic roughing to obtain arsenic roughing concentrate and arsenic roughing tailings;
(3) adding 3g/t of aniline black and 6g/t of modified ethioamine into the arsenic roughing tailings, stirring and then performing primary arsenic scavenging to obtain primary arsenic scavenging concentrate and primary arsenic scavenging tailings; returning the arsenic concentrate subjected to primary scavenging to the previous stage;
(4) adding 1g/t of aniline black and 2g/t of modified ethioamine into the arsenic primary scavenging tailings, stirring and then carrying out arsenic secondary scavenging to obtain arsenic secondary scavenging concentrate and arsenic secondary scavenging tailings; returning the arsenic second scavenging concentrate to the previous stage;
(5) adding 130g/t Tf into the arsenic rough concentration concentrate, stirring and then carrying out arsenic first concentration to obtain arsenic first concentration concentrate and arsenic first concentration tailings; returning the arsenic first-time concentration tailings to the previous-stage operation;
(6) adding 60g/t of Tf into the arsenic primary concentration concentrate, stirring, and then carrying out arsenic secondary concentration to obtain arsenic secondary concentration concentrate and arsenic secondary concentration tailings; returning the arsenic second concentration tailings to the previous stage operation; arsenic secondary concentration concentrate, namely arsenic concentrate;
(7) 2100g/t of lime, 1600g/t of zinc sulfate, 55g/t of ethion nitrogen, 35g/t of ammonium nitrate-black drug and 10g/t 2 of ammonium nitrate-black drug are added into arsenic secondary scavenging tailings#Performing lead roughing to obtain lead roughing concentrate and lead roughing tailings;
(8) adding 30g/t of ethidium and nitrogen and 15g/t of ammonium nitrate black powder into the lead roughing tailings, stirring and then carrying out primary lead scavenging to obtain primary lead scavenging concentrate and primary lead scavenging tailings; returning the lead concentrate subjected to primary scavenging to the previous stage;
(9) adding 15g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead primary scavenging tailings, stirring and then carrying out lead secondary scavenging to obtain lead secondary scavenging concentrate and lead secondary scavenging tailings; returning the lead secondary scavenging concentrate to the previous stage;
(10) adding 3g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead secondary scavenging tailings, stirring and then scavenging lead for three times to obtain lead tertiary scavenging concentrate and lead tertiary scavenging tailings; returning the lead concentrate subjected to three times of scavenging to the previous stage;
(11) adding 320g/t lime and 180g/t zinc sulfate into the lead roughing concentrate, stirring and then carrying out lead first-time concentration to obtain lead first-time concentration concentrate and lead first-time concentration tailings; returning the lead primary concentration tailings to the previous stage operation;
(12) adding 110g/t lime and 60g/t zinc sulfate into the lead primary concentration concentrate, stirring and then carrying out lead secondary concentration to obtain lead secondary concentration concentrate and lead secondary concentration tailings; returning the lead secondary concentration tailings to the previous stage operation, wherein the lead secondary concentration concentrate is lead concentrate;
(13) the obtained lead tailings after the three-time scavenging is the lead tailings, and the zinc concentrate product can be obtained by performing conventional zinc flotation on the lead tailings.
In the embodiment, by adopting the beneficiation process of lead flotation after preferential arsenic flotation, the lead grade of the obtained lead concentrate product is 68.39%, wherein the arsenic content is 0.37% and is lower than 0.4%, and the arsenic does not exceed the standard.
This example also obtained an arsenic concentrate product containing 4.88% arsenic.
Example 3
The process flow shown in FIG. 1 is adopted to treat raw ore of arsenic-lead-zinc ore, the raw ore contains 6.45% of lead, 0.33% of arsenic and 84.30% of lead sulfide, and the arsenic mainly exists in the form of arsenopyrite and arsenopyrite. The flotation process comprises the following steps:
(1) grinding the raw ore to-0.075 mm ore grinding fineness of 71.05%;
(2) adding the ground ore pulp into a flotation machine, adding 1600g/t of Tf, stirring, adding 8g/t of aniline black and 12g/t of modified ethioamine, and performing arsenic roughing to obtain arsenic roughing concentrate and arsenic roughing tailings;
(3) adding 3g/t of aniline black and 4g/t of modified ethioamine into the arsenic roughing tailings, stirring and then performing primary arsenic scavenging to obtain primary arsenic scavenging concentrate and primary arsenic scavenging tailings; returning the arsenic concentrate subjected to primary scavenging to the previous stage;
(4) adding 2g/t of aniline black and 2g/t of modified ethioamine into the arsenic primary scavenging tailings, stirring and then carrying out arsenic secondary scavenging to obtain arsenic secondary scavenging concentrate and arsenic secondary scavenging tailings; returning the arsenic second scavenging concentrate to the previous stage;
(5) adding 150g/t Tf into the arsenic rough concentration concentrate, stirring and then carrying out arsenic first concentration to obtain arsenic first concentration concentrate and arsenic first concentration tailings; returning the arsenic first-time concentration tailings to the previous-stage operation;
(6) adding 80g/t Tf into the arsenic primary concentration concentrate, stirring, and then carrying out arsenic secondary concentration to obtain arsenic secondary concentration concentrate and arsenic secondary concentration tailings; returning the arsenic second concentration tailings to the previous stage operation; arsenic secondary concentration concentrate is arsenic concentrate;
(7) 1800g/t lime, 1600g/t zinc sulfate, 70g/t ethion nitrogen, 25g/t ammonium nitrate black powder and 15g/t 2 are added into arsenic secondary scavenging tailings#Oil, lead roughing is carried out to obtain lead roughing concentrate and lead roughing tailings;
(8) adding 20g/t of ethidium and 20g/t of ammonium nitrate black powder into the lead roughing tailings, stirring and then carrying out primary lead scavenging to obtain primary lead scavenging concentrate and primary lead scavenging tailings; returning the lead concentrate subjected to primary scavenging to the previous stage;
(9) adding 15g/t of ethidium and nitrogen and 10g/t of ammonium nitrate black powder into the lead primary scavenging tailings, stirring and then carrying out lead secondary scavenging to obtain lead secondary scavenging concentrate and lead secondary scavenging tailings; returning the lead secondary scavenging concentrate to the previous stage;
(10) adding 1g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead secondary scavenging tailings, stirring and then scavenging lead for three times to obtain lead tertiary scavenging concentrate and lead tertiary scavenging tailings; returning the lead concentrate subjected to three times of scavenging to the previous stage;
(11) adding 250g/t of lime and 180g/t of zinc sulfate into the lead roughing concentrate, stirring and then carrying out lead first-time concentration to obtain lead first-time concentration concentrate and lead first-time concentration tailings; returning the lead primary concentration tailings to the previous stage operation;
(12) adding 120g/t lime and 60g/t zinc sulfate into the lead primary concentration concentrate, stirring and then carrying out lead secondary concentration to obtain lead secondary concentration concentrate and lead secondary concentration tailings; returning the lead secondary concentration tailings to the previous stage operation; lead concentrate is lead concentrate after secondary concentration;
(13) the obtained lead tailings after the three-time scavenging is the lead tailings, and the zinc concentrate product can be obtained by performing conventional zinc flotation on the lead tailings.
In the embodiment, by adopting the beneficiation process of lead flotation after preferential arsenic flotation, the lead grade of the obtained lead concentrate product is 63.64%, wherein the arsenic content is 0.34% and is lower than 0.4%, and the arsenic does not exceed the standard.
This example also obtained an arsenic concentrate product containing 5.25% arsenic.
Comparative example 1
The process flow shown in fig. 2 is adopted to treat raw ore of arsenic-lead-zinc ore, and lead flotation is directly carried out on the raw ore, and the raw ore is the same as the raw ore in example 1, and is mainly different from the raw ore in example 1 in that no preferential arsenic flotation process exists. The flotation process is as follows:
(1) grinding the raw ore to a grinding fineness of-0.075 mm accounting for 70%;
(2) adding the ground ore pulp into a flotation machine, adding 2500g/t lime and 16 g/t lime00g/t zinc sulfate, 60g/t ethidium nitrate, 35g/t butylammonium nigricans and 10g/t 2#Oil, lead roughing is carried out to obtain lead roughing concentrate and lead roughing tailings;
(3) adding 25g/t of ethidium and sulfur nitrogen and 15g/t of ammonium nitrate black powder into the lead roughing tailings, stirring and then carrying out primary lead scavenging to obtain primary lead scavenging concentrate and primary lead scavenging tailings; returning the lead concentrate subjected to primary scavenging to the previous stage;
(4) adding 10g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead primary scavenging tailings, stirring and then carrying out lead secondary scavenging to obtain lead secondary scavenging concentrate and lead secondary scavenging tailings; returning the lead secondary scavenging concentrate to the previous stage;
(5) adding 2g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead secondary scavenging tailings, stirring and then scavenging lead for three times to obtain lead tertiary scavenging concentrate and lead tertiary scavenging tailings; returning the lead concentrate subjected to three times of scavenging to the previous stage;
(6) adding 300g/t lime and 150g/t zinc sulfate into the lead roughing concentrate, stirring and then carrying out lead first-time concentration to obtain lead first-time concentration concentrate and lead first-time concentration tailings; returning the lead primary concentration tailings to the previous stage operation;
(7) adding 100g/t lime and 50g/t zinc sulfate into the lead primary concentration concentrate, stirring and then carrying out lead secondary concentration to obtain lead secondary concentration concentrate and lead secondary concentration tailings; and returning the lead secondary concentration tailings to the previous stage of operation.
And the lead secondary concentration concentrate is lead concentrate. The lead grade of the obtained lead concentrate is 61.21%, wherein the arsenic content is 0.48%, and the arsenic content exceeds the standard.
Comparative example 2
The process flow shown in fig. 2 is adopted to treat raw ore of arsenic-lead-zinc ore, and lead flotation is directly carried out on the raw ore, and the raw ore is the same as the raw ore in example 2, and is mainly different from the raw ore in example 2 in that no preferential arsenic flotation process exists. The flotation process is as follows:
(1) grinding the raw ore to-0.075 mm ore grinding fineness of 68.95%;
(2) adding the ground ore pulp into a flotation machine, adding 2300g/t lime, 1800g/t zinc sulfate, 65g/t ethidium-nitrogen, 30g/t ammonium-butyl-ammonium-blackened and 10g/t 2#Oil, lead roughing is carried out to obtain lead roughing concentrate and lead roughing tailings;
(3) adding 30g/t of ethidium and nitrogen and 15g/t of ammonium nitrate black powder into the lead roughing tailings, stirring and then carrying out primary lead scavenging to obtain primary lead scavenging concentrate and primary lead scavenging tailings; returning the lead concentrate subjected to primary scavenging to the previous stage;
(4) adding 15g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead primary scavenging tailings, stirring and then carrying out lead secondary scavenging to obtain lead secondary scavenging concentrate and lead secondary scavenging tailings; returning the lead secondary scavenging concentrate to the previous stage;
(5) adding 3g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead secondary scavenging tailings, stirring and then scavenging lead for three times to obtain lead tertiary scavenging concentrate and lead tertiary scavenging tailings; returning the lead concentrate subjected to three times of scavenging to the previous stage;
(6) adding 320g/t lime and 180g/t zinc sulfate into the lead roughing concentrate, stirring and then carrying out lead first-time concentration to obtain lead first-time concentration concentrate and lead first-time concentration tailings; returning the lead primary concentration tailings to the previous stage operation;
(7) adding 110g/t lime and 60g/t zinc sulfate into the lead primary concentration concentrate, stirring and then carrying out lead secondary concentration to obtain lead secondary concentration concentrate and lead secondary concentration tailings; and returning the lead secondary concentration tailings to the previous stage of operation.
The lead concentrate obtained by the secondary lead concentration is lead concentrate, the lead grade of the obtained lead concentrate is 64.21%, the arsenic content is 0.50%, and the arsenic exceeds the standard.
Comparative example 3
The process flow shown in fig. 2 is adopted to treat raw ore of arsenic-lead-zinc ore, and lead flotation is directly carried out on the raw ore, and the raw ore is the same as the raw ore in example 3, and is mainly different from the raw ore in example 3 in that no preferential arsenic flotation process exists. The flotation process is as follows:
(1) grinding the raw ore to-0.075 mm ore grinding fineness of 71.05%;
(2) adding the ground ore pulp into a flotation machine, adding 1700g/t lime, 1500g/t zinc sulfate, 65g/t ethidium-nitrogen, 30g/t ammonium-butyl-ammonium-blackened and 15g/t 2#Oil, lead roughing is carried out to obtain lead roughing concentrate and lead roughing tailings;
(3) adding 20g/t of ethidium and 20g/t of ammonium nitrate black powder into the lead roughing tailings, stirring and then carrying out primary lead scavenging to obtain primary lead scavenging concentrate and primary lead scavenging tailings; returning the lead concentrate subjected to primary scavenging to the previous stage;
(4) adding 15g/t of ethidium and nitrogen and 10g/t of ammonium nitrate black powder into the lead primary scavenging tailings, stirring and then carrying out lead secondary scavenging to obtain lead secondary scavenging concentrate and lead secondary scavenging tailings; returning the lead secondary scavenging concentrate to the previous stage;
(5) adding 1g/t of ethidium and sulfur nitrogen and 5g/t of ammonium nitrate black powder into the lead secondary scavenging tailings, stirring and then scavenging lead for three times to obtain lead tertiary scavenging concentrate and lead tertiary scavenging tailings; returning the lead concentrate subjected to three times of scavenging to the previous stage;
(6) adding 250g/t of lime and 180g/t of zinc sulfate into the lead roughing concentrate, stirring and then carrying out lead first-time concentration to obtain lead first-time concentration concentrate and lead first-time concentration tailings; returning the lead primary concentration tailings to the previous stage operation;
(7) adding 120g/t lime and 60g/t zinc sulfate into the lead primary concentration concentrate, stirring and then carrying out lead secondary concentration to obtain lead secondary concentration concentrate and lead secondary concentration tailings; and returning the lead secondary concentration tailings to the previous stage of operation.
The lead concentrate obtained by secondary lead concentration is lead concentrate, the lead grade in the obtained lead concentrate is 61.04%, the arsenic content is 0.52%, and the arsenic exceeds the standard.
The lead concentrates obtained by the comparative examples 1-3 have the problem of excessive arsenic, and the lead concentrates meeting the requirements can be obtained only by performing arsenic reduction treatment. During the subsequent arsenic reduction treatment, because the lead concentrate contains more flotation reagents, the reagent removal is needed firstly, and then the arsenic reduction treatment is needed. Has the problems of large dosage of medicament and poor arsenic reduction and separation effect.
Examples 1 to 3 the beneficiation method according to the present invention for lead flotation after preferential arsenic flotation can stably reduce the content of arsenic, which is a harmful impurity in lead concentrate, in complex minerals containing arsenic, lead, and zinc, which contain arsenopyrite minerals, and lead concentrate products with arsenic content of less than 0.4% can be obtained.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The beneficiation method for the arsenic-lead-zinc-containing ores is characterized in that the arsenic-lead-zinc-containing ores contain arsenopyrite and arsenopyrite, and the beneficiation method comprises the following steps: grinding the arsenic-lead-zinc ore to prepare ore pulp, then performing arsenic flotation to obtain arsenic concentrate, and then performing lead flotation to obtain lead concentrate.
2. The beneficiation method for lead-arsenic zinc ores according to claim 1, wherein the arsenic flotation includes one arsenic roughing, at least one concentration and at least one scavenging; the reagent adopted by the arsenic roughing comprises an arsenic collecting agent and a combined inhibitor; and/or the reagent used for beneficiation comprises a combined inhibitor, and/or the reagent used for scavenging comprises an arsenic collector;
wherein the arsenic collecting agent comprises aniline black powder and modified ethioamine; the combined inhibitor comprises at least one of sodium carbonate, humate, bleaching powder, sodium sulfite and zinc sulfate.
3. The beneficiation method for the arsenic-lead-zinc ore according to claim 2, wherein the combined inhibitor is a mixture of sodium carbonate, humate, bleaching powder, sodium sulfite and zinc sulfate, preferably the combined inhibitor comprises sodium carbonate, humate, bleaching powder, sodium sulfite and zinc sulfate in a mass ratio of (15-25): 5-10): 10-20): 20-30): 30-50;
the modified ethioamine is a mixture of ethioamine and diesel oil, and preferably the ethioamine and the diesel oil are mixed according to a mass ratio of 1 (2-4).
4. The beneficiation method for arsenic, lead and zinc bearing ores according to claim 2 or 3, wherein the arsenic flotation comprises one arsenic rougher flotation, 1-2 cleaner flotation and 1-2 scavenger flotation, preferably wherein the arsenic flotation comprises one arsenic rougher flotation, 2 cleaner flotation and 2 scavenger flotation.
5. The beneficiation method for the arsenic-lead-zinc ore according to claim 4, wherein the reagents adopted for the arsenic roughing are a combined inhibitor, aniline black and modified ethionamide, the combined inhibitor is used in an amount of 1000-2500 g/t, the aniline black is used in an amount of 5-50 g/t, and the modified ethionamide is used in an amount of 10-50 g/t based on the mass of the arsenic-lead-zinc ore;
the agent adopted in the first concentration is a combined inhibitor, and the dosage of the combined inhibitor is 100-500 g/t based on the mass of the arsenic-lead-zinc ore raw ore; and/or taking a medicament adopted in the second concentration as a combined inhibitor, wherein the dosage of the combined inhibitor is 50-100 g/t based on the mass of the raw ore of the arsenic-lead-zinc ore;
the first scavenging adopts aniline black and modified ethionamide, the dosage of the aniline black is 2-20 g/t, and the dosage of the modified ethionamide is 4-20 g/t based on the mass of the arsenic-lead-zinc ore; and/or the reagents adopted by the second scavenging are aniline black and modified ethionamide, the dosage of the aniline black is 1-10 g/t, and the dosage of the modified ethionamide is 1-10 g/t based on the mass of the arsenious plumbum and zincite raw ore.
6. The beneficiation method for lead-arsenic-containing zinc ores according to any one of claims 1 to 5, wherein the lead flotation comprises one lead roughing, at least one concentration and at least one scavenging; the lead roughing adopts medicaments comprising lime, zinc sulfate, ethidium and azote, ammonium nitrate and No. 2 oil; and/or the concentration adopted agents comprise lime and zinc sulfate; and/or the scavenging agent comprises ethidium nitrate and ammonium nitrate.
7. The beneficiation method for lead-arsenic zinc ores according to claim 6, wherein the lead flotation comprises one lead rougher flotation, 1-2 cleaner flotation and 1-3 scavenger flotation, preferably the lead flotation comprises one lead rougher flotation, 2 cleaner flotation and 3 scavenger flotation.
8. The beneficiation method for the zinc and arsenic ores according to claim 7, wherein the lead roughing adopts the reagents of lime, zinc sulfate, ethion nitrogen, ammonium nitrate black powder and No. 2 oil; the using amounts of the lime, the zinc sulfate, the ethidium and the ammonium nitrate are respectively 1000-5000 g/t, 1000-2000 g/t, 40-100 g/t, 20-50 g/t and 5-30g/t based on the mass of the raw ore of the arsenic-lead-zinc ore;
the first selection adopts lime and zinc sulfate as reagents, and the dosage of the lime and the zinc sulfate is respectively 200-500 g/t and 100-200 g/t based on the mass of the raw ore of the zinc ore containing arsenic and lead; and/or the reagents adopted in the second concentration are lime and zinc sulfate, and the dosage of the lime and the dosage of the zinc sulfate are respectively 100-200 g/t and 50-100 g/t based on the mass of the raw ore of the arsenic-lead-zinc ore;
the first scavenging adopts the reagents of ethidium and ammonium nitrate, and the dosages of the ethidium and the ammonium nitrate are respectively 20-50 g/t and 10-25 g/t based on the mass of the raw ore of the arsenious plumbum and zincite; and/or the reagents adopted by the second scavenging are ethidium and ammonium nitrate black chemicals, and the dosage of the ethidium and the ammonium nitrate black chemicals is 10-25 g/t and 5-15 g/t respectively based on the mass of the arsenious plumbum and zincite raw ore; and/or the reagents adopted by the third scavenging are ethidium and ammonium nitrate black chemicals, and the dosage of the ethidium and the ammonium nitrate black chemicals is 1-10 g/t and 1-10 g/t respectively based on the mass of the arsenious plumbum and zincite raw ore.
9. The beneficiation method for the arsenic-lead-zinc ore according to any one of claims 1 to 8, wherein the fineness of the ore grinding of the arsenic-lead-zinc ore is-0.075 mm and accounts for 65-85%.
10. The beneficiation method for lead-zinc-arsenic ores according to claim 9, wherein the arsenic content in the lead concentrate is less than 0.4%.
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