CN103721851A

CN103721851A - Method for recycling zinc, lead, silver and copper from zinc oxide ore

Info

Publication number: CN103721851A
Application number: CN201310742354.9A
Authority: CN
Inventors: 吴慧; 赵兵伍; 陈长浩; 赵德军
Original assignee: Yunnan Luoping Zinc & Electricity Co Ltd
Current assignee: Yunnan Luoping Zinc & Electricity Co Ltd
Priority date: 2013-12-30
Filing date: 2013-12-30
Publication date: 2014-04-16
Anticipated expiration: 2033-12-30
Also published as: CN103721851B

Abstract

The invention discloses a method for recycling zinc, lead, silver and copper from zinc oxide ore. The flotation technology including one-time rough flotation, two-time fine flotation and two-time scavenging is adopted to conduct flotation on the lead and the silver in the ore, then the flotation technology including one-time rough flotation, two-time fine flotation and two-time scavenging is adopted to conduct flotation on the zinc and the copper in the ore, the copper is obtained from zinc-copper concentrates obtained through flotation through firing, sulfuric acid leaching and zinc plate replacement, zinc sulphate is obtained through a solution through concentration and crystallization, and the aim of separating the zinc from the copper is accordingly achieved; when flotation is carried out, sodium carbonate serves as regulators, sodium sulphide serves as vulcanizing agents, zinc sulfate serves as depressors, butyl amine black powder, butyl xanthate and diethyldithiocarbamate serve as collecting agents, and number two oil serves as foaming agents. According to the method, lead concentrates meeting industrial standards, industrial zinc sulfate meeting the industrial standards and copper powder can be obtained from zinc oxide ore through a flotation and smelting unified method, and the lead in the lead concentrates accounts for 68-70wt%; the zinc sulphate in the industrial zinc sulfate accounts for 95-97wt%; the copper in copper powder accounts for 80-85wt%.

Description

A kind of method that reclaims Zn, Pb and Ag copper from zinc oxide ore

Technical field

The present invention is a kind of method that reclaims zinc, lead, silver, copper from zinc oxide ore.Belong to zinc oxide ore Comprehensive Recovery Technology field.

Background technology

A kind of ore in somewhere, Yunnan, its Main Ingredients and Appearance is that zinc 5.00-10.00wt%, plumbous 5.00-8.00wt%, silver-colored 0.05-0.10wt%, copper 1.80-2.50wt%, sulphur 0.50-1.00wt% belong to zinc oxide ore.

Certain high ferro Ag-pb-zn oxide ore flotation experimental study > > of < < southwest that known Zhang Aiping, Wang Rendong, Tan Bing write, having introduced certain high ferro Ag-pb-zn oxide ore essential mineral of southwest is cerussite, plumbojarosite, smithsonite, smithsonite, limonite, and silver is composed and is stored in lead minerals with isomorph form.Raw ore is containing zinc 8.57%, plumbous 7.67%, silver-colored 210g/t, and test adopts new A F medicament to plumbous and silver flotation simultaneously, obtains that silver lead ore concentrate is leaded 42%, argentiferous 1460g/t, lead recovery 70%, silver raising recovery rate 77%.When Flotation of Zinc Oxide, adopt a new zinc oxide flotation technology, not desliming directly adds novel LW51 collecting agent, obtains zinc concentrate grade 20.15%, zinc recovery 63.92%.

Zhou Kai, the < < Sichuan lead-zinc Experimental study on ore dressing > > that Chen Bo writes, introduced Sichuan lead-zinc stone, raw ore is containing zinc 6.61%, plumbous 4.55%, silver 46.41g/t, adopt first plumbous rear zinc, not desliming direct flotation technique has been carried out the Experimental study on ore dressing of system, experimental study shows, adopt 1 thick 3 essences 2 to sweep floating plumbous, 1 thick 4 essences 2 are swept floating zinc, this ore of closed-circuit test flow processing that chats sequentially returns, can obtain lead concentrate productive rate 5.91%, zinc concentrate productive rate 12.36%, lead concentrate is leaded 61.95%, containing zinc 3.16%, silver-colored 637.5g/t, zinc concentrate is containing zinc 37.53%, leaded 1.18%, argentiferous 24.48g/t, in zinc recovery 80.12%, lead recovery 79.59%, lead concentrate, silver accounts for 81.2% of total amount, and choosing plumbous employing penta xanthate and H are collecting agent, and selecting zinc to adopt LYA and E is collecting agent.

The < < lead-zinc oxide ore flotation technical research > > that Qu Zhiqiang, expense nine light are write, introduced certain lead-zinc Pb in ores oxygenation efficiency 75%, zinc oxygenation efficiency 60%, ore is leaded 0.7%, zinc 1.66%, silver-colored 16.8g/t; Selecting plumbous collecting agent is diethyldithiocarbamate, butyl ammonium aerofloat, selects zinc sulphide collecting agent butyl xanthate, dressing zinc oxide collecting agent A928; Obtaining lead concentrate productive rate is 1.03%, leaded 55.32%, zinc 5.88%, zinc sulfide concentrates productive rate 1.28%, leaded 1.24%, zinc 52.86%, zinc oxide concentrate productive rate 3.18%, leaded 1.22%, zinc 22.85%, lead recovery 81.4%, zinc sulphide zinc recovery 39.8%, zinc oxide zinc recovery 42.74%.

Li Laishun, Liu Sanjun, Zhu Hailing, Zhang Ting, Qin Wenqing write < < Yunnan lead-zinc Experimental study on ore dressing > >, introduced that certain zinc oxide ore raw ore is leaded 1.44%, zinc 7.04%, under the condition of not desliming, adopt the floating plumbous and sulfuration-amine method float zinc technological process of sulfuration-xanthate method, finally obtain that lead concentrate is leaded 30.44%, zinc concentrate is containing zinc 23.51%, lead recovery 64.66%, zinc recovery 71.02%.

ZL201110059283.3 < < soaks from zinc the method > > that reclaims zinc-silver copper slag, introduced the zinc producing and soaked slag employing flotation technology before entering rotary kiln processing in Zinc Hydrometallurgy Process, silver, copper that zinc soaks in slag flotate, zinc partly enters solution, dual-purpose carbonic hydroammonium neutralization precipitation zinc simultaneously.Silver raising recovery rate 75-85%, copper recovery 53-55%, zinc recovery 20-25%.

The method > > of ZL201110438956.6 < < Recovering Copper silver from the high silver ore of low copper, introduced a kind of from the high silver ore of low copper the method for Recovering Copper silver, after adopting the floatation process of " two thick, two essences, two sweep " that silver, copper in the high silver ore of low copper are flotated, concentrate carries out calcination, sulfuric acid leaching and zinc metal sheet displacement copper again, thereby reaches silver, the separated object of copper.Produce the copper powder of cupric 65-72% and the silver preparation concentrate of argentiferous 2.5-3.5%, silver raising recovery rate 88-91%, copper recovery 86-88%.

ZL201210276858.1 < < comprehensive method > > who reclaims plumbous silver from lead skim, introduce the lead skim that Liao electricity zinc factory produces, adopt the floatation process of " one roughing, scan for three times, primary cleaning ", the plumbum floatation in lead skim out, silver enters in lead concentrate, mine tailing enters rotary kiln evaporation, further reclaims the valuable metal in lead skim.Lead recovery can reach 95-97%, silver raising recovery rate can reach 90-95%.

Known from zinc oxide ore the method for flotation of lead, zinc, silver, lead recovery is at 64-82%, zinc recovery 63-82%, silver raising recovery rate 77-82 %; Known ZL201110059283.3 < < soaks from zinc that slag, to reclaim mono-kind of the method > > of zinc-silver copper and the ZL201210276858.1 < < comprehensive method > > that reclaims plumbous silver from lead skim be all the comprehensive zinc that reclaims in the slag producing from electric zinc production process, the method for silver, copper and lead, silver.

The method > > of known ZL201110438956.6 < < Recovering Copper silver from the high silver ore of low copper is a kind of method that reclaims copper, silver from ore.And the method that reclaims zinc, lead, silver, copper from zinc oxide ore has no report.

Summary of the invention

The object of the invention is to overcome prior art deficiency, invent a kind of method that reclaims Zn, Pb and Ag copper from zinc oxide ore.

A kind of method that reclaims Zn, Pb and Ag copper from zinc oxide ore of the present invention realizes by the following technical solutions: adopt zinc sulfate to make inhibitor, with collecting agent butylamine black powder and diethyldithiocarbamate, pass through one roughing, recleaning, the floatation process that secondary is scanned is first the lead in ore, after silver flotates, adopt again collecting agent butyl xanthate and diethyldithiocarbamate, pass through one roughing, recleaning, the floatation process that secondary is scanned is the zinc in ore, copper flotates, the zinc-copper concentrate flotating is through calcination, sulfuric acid leaching and zinc metal sheet displacement copper, solution is through concentrated, crystallization obtains white vitriol, make zinc-copper separated, the sodium carbonate agent that adjusts during flotation, vulcanized sodium is made vulcanizing agent, and butylamine black powder, butyl xanthate and diethyldithiocarbamate are done collecting agent, and No. 2 oil is done foaming agent, and concrete technology step is as follows:

(1), flotation of lead silver:

(1) ore grinding; (2) size mixing; (3) plumbous silver is roughly selected I; (4) plumbous silver is scanned I; (5) plumbous silver is scanned II; (6) plumbous silver-colored selected I; (7) plumbous silver-colored selected II;

(2), flotation zinc-copper:

(1) zinc-copper is roughly selected I; (2) zinc-copper is scanned I; (3) zinc-copper is scanned II; (4) the selected I of zinc-copper; (5) the selected II of zinc-copper;

(3), zinc, copper separation:

(1) calcination; (2) sulfuric acid leaching; (3) displacement; (4) condensing crystallizing.

Described step (one), flotation of lead silver (1) ore grinding are: by dry ball, zinc oxide ore is worn into breeze, breeze granularity 90wt% is less than 120 orders, and described zinc oxide ore is for containing zinc 5.00-10.00wt%, plumbous 5.00-8.00wt%, silver-colored 0.05-0.10wt%, copper 1.80-2.30wt%, sulphur 0.50-1.0wt%;

Described step (one), flotation of lead silver (2) are sized mixing and are: water or No. 2 filtrates are sized mixing to breeze, and being adjusted to pulp density is 50-60wt%.

Described step (one), flotation of lead silver (3) plumbous silver are roughly selected I and are: by breeze per ton, add vulcanized sodium 5.0-10.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; By breeze per ton, add zinc sulfate 1.5-2.5kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt%; By breeze per ton, add sodium carbonate 350.0-450.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; By breeze per ton, add collecting agent butylamine black powder 40.0-50.0g and butylamine black powder are formulated as the aqueous solution of 10-15wt% and add diethyldithiocarbamate 15.0-35.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% by breeze per ton, stir 4-6min; By breeze per ton, add No. 2 oily 40.0-60.0g of foaming agent again, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 concentrate and No. 1 mine tailing, No. 1 mine tailing carries out plumbous silver and scans I;

Described step (one), flotation of lead silver (4) plumbous silver are scanned I and are: by adding vulcanized sodium 1.0-2.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp, stir 20-30min; By adding zinc sulfate 0.5-0.7kg and zinc sulfate to be formulated as in the aqueous solution of 10-15wt% and 1 ton of No. 1 mine tailing ore pulp in 1 ton of No. 1 mine tailing ore pulp, add sodium carbonate 100.0-170.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; By adding collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 15.0-25.0g of foaming agent in 1 ton of No. 1 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 2 mine tailings, No. 2 mine tailings carry out plumbous silver and scan II.

Described step (one), flotation of lead silver (5) plumbous silver are scanned II and are: by adding vulcanized sodium 1.0-2.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stir 20-30min; By adding zinc sulfate 0.5-0.8kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp and by adding sodium carbonate 100.0-175.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stirring 4-6min; By adding collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 15.0-25.0g of foaming agent in 1 ton of No. 2 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 3 mine tailings.Scan I, the resulting concentrate of II all mixes is No. 4 concentrate, No. 3 mine tailing carries out flotation zinc-copper, No. 1 concentrate and No. 4 concentrate mix the selected I of laggard quadrat silver.

Described step (one), the plumbous silver-colored selected I of flotation of lead silver (6) are: water or No. 1 filtrate are sized mixing to No. 1 concentrate and No. 4 concentrate mixed ore pulps, being adjusted to pulp density is 50-60wt%, press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps, to add zinc sulfate 0.3-0.5kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add sodium carbonate 100.0-125.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps, to add collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 concentrate and chats, chats returns to plumbous silver and roughly selects I, and No. 2 concentrate carries out the silver-colored selected II of lead.

Described step (one), the plumbous silver-colored selected II of flotation of lead silver (7) are: it is 50-60wt% that No. 2 concentrate waters are adjusted to pulp density, press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press in 1 ton of No. 2 concentrate pulp that mixes up pulp density, to add zinc sulfate 0.5-1.0kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% and press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add sodium carbonate 100.0-125.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press in 1 ton of No. 2 concentrate pulp that mixes up pulp density, to add collecting agent butylamine black powder 2.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% and press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain chats and No. 3 concentrate, chats returns to plumbous silver and roughly selects I, and No. 3 concentrate filters lead concentrate and No. 1 filtrate that obtains meeting industry standard, and No. 1 filtrate is returned to plumbous silver-colored selected I.

Described step (two) flotation zinc-copper (1) zinc-copper is roughly selected I and is: it is 50-60wt% that No. 3 mine tailing waters are adjusted to pulp density, press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density and add vulcanized sodium 1.5-2.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density, to add collecting agent butyl xanthate 100.0-125.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density and add diethyldithiocarbamate 2.0-7.5g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density again and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 zinc-copper concentrate and No. 4 mine tailings, No. 4 mine tailings carry out zinc-copper and scan I;

Described step (two) flotation zinc-copper (2) zinc-copper is scanned I and is: by adding vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp, stir 20-30min; By adding collecting agent butyl xanthate 25.0-50.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 10.0-15.0g of foaming agent in 1 ton of No. 4 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 5 mine tailings, No. 5 mine tailings carry out zinc-copper and scan II.

Described step (two) flotation zinc-copper (3) zinc-copper is scanned II and is: by adding vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp, stir 20-30min; By adding collecting agent butyl xanthate 25.0-50.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp, stirring 4-6min; Again by adding No. 2 oily 10.0-15.0g of foaming agent in 1 ton of No. 5 mine tailing ore pulp, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 6 mine tailings, No. 6 mine tailing obtains mine tailing and No. 2 filtrates after filtration, mine tailing is stored up, No. 2 filtrate returning sized mixing, and zinc-copper is scanned I and zinc-copper, and to scan that the resulting concentrate of II mixes be No. 4 zinc-copper concentrate, after No. 4 zinc-copper concentrate and No. 1 zinc-copper concentrate mix, carries out the selected I of zinc-copper.

The selected I of described step (two) flotation zinc-copper (4) zinc-copper is: water or No. 3 filtrates are sized mixing to No. 1 zinc-copper concentrate and No. 4 zinc-copper concentrate mixed ore pulps, being adjusted to pulp density is 50-60wt%, press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add vulcanized sodium 0.3-0.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps, to add collecting agent butyl xanthate 20.0-30.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add No. 2 oily 7.5-12.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 zinc-copper concentrate and zinc-copper chats, zinc-copper chats returns to zinc-copper and roughly selects I, and No. 2 zinc-copper concentrate carries out the selected II of zinc-copper.

The selected II of described step (two) flotation zinc-copper (5) zinc-copper: it is 50-60wt% that No. 2 zinc-copper concentrate waters are adjusted to pulp density, press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density and add vulcanized sodium 0.3-0.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Pressing to add collecting agent butyl xanthate 20.0-30.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density adds diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min, press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density and add No. 2 oily 7.5-12.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 3 zinc-copper concentrate and zinc-copper chats, zinc-copper chats returns to zinc-copper and roughly selects I.No. 3 zinc-copper concentrate filter and obtain No. 5 zinc-copper concentrate and No. 3 filtrates that argentiferous 0.002-0.005wt%, copper 10-20wt%, lead are less than 3.0 wt%, zinc 35-45wt%, and No. 3 filtrate is returned to the selected I of zinc-copper, and No. 5 zinc-copper concentrate carries out calcination.

Described step (three) zinc, separated (1) calcination of copper: be that No. 5 zinc-copper concentrate are carried out to calcination 1.0-1.5h at 500 ℃ of-600 ℃ of temperature, No. 5 zinc-copper concentrate after calcination carry out sulfuric acid leaching.

Described step (three) zinc, separated (2) sulfuric acid leaching of copper: be that No. 5 zinc-copper concentrate waters after calcination are adjusted to liquid-solid ratio 4-5:1, add again 98wt% sulfuric acid, acidity is controlled at 200g/L-250g/L, temperature 70 C-75 ℃ and leaches 2.0-3.0h, filter containing zinc 98-110g/L, copper 30-40g/L, whole No. 4 filtrates of sour pH=5.0-5.2 and be less than the leached mud that 6.0wt%, copper are less than 1.5wt% containing zinc, leached mud is sent rotary kiln back to and is further volatilized and reclaim zinc, copper, silver, lead, and No. 4 filtrate is replaced.

Described step (three) zinc, copper separated (3) displacement: displacement is No. 4 filtrates to be warmed up to 20 ℃-30 ℃ add zinc metal sheet to carry out copper displacement, time swap is 80-100min, then filter to obtain copper powder and No. 5 filtrates of cupric 80-85wt%, No. 5 filtrate is carried out condensing crystallizing.

Separated (4) condensing crystallizing of described step (three) zinc, copper is: to No. 5 filtrates evaporation and concentration that heats up, when reaching 300g/ L containing zinc, concentrate carries out liquid-solid separation after crystallisation by cooling, output meets industrial white vitriol and the mother liquor of industry standard, and mother liquor returns to condensing crystallizing again.

Described No. 2 oil of foaming agent are again terpenic oil, it is the most frequently used the widest foaming agent in source of China, it is to take turpentine oil as raw material, then with sulfuric acid, make catalyst, the organic reagent product that terebinthine principal component australene aquation is formed, it is glassy yellow oily liquids, main component is α-terpenol, it is greater than 44%, density 0.9g/cm containing α-terpenol ³, there is rosin fragrance left and right, is conventional foaming agent for ore dressing.

The present invention adopts zinc sulfate to make inhibitor, with butylamine black powder, diethyldithiocarbamate, do collecting agent, after floatation process by " one roughing, secondary are scanned, recleaning " first flotates the lead in ore, silver, adopt butyl xanthate, diethyldithiocarbamate to do collecting agent, the floatation process by " one roughing, secondary are scanned, recleaning " flotates the zinc in ore, copper again.The zinc-copper concentrate flotating is through calcination, sulfuric acid leaching and zinc metal sheet displacement copper, and solution obtains white vitriol, thereby reaches the object of zinc-copper separation through concentrated, crystallization.

In the present invention, " one roughing, recleaning, secondary are scanned " is different with secondary " one roughing, recleaning, secondary are scanned " condition for the first time.First primary " one roughing, recleaning, secondary are scanned " will add inhibitor zinc sulfate is mainly to suppress zinc, and secondary " one roughing, recleaning, secondary are scanned " do not add.

It two is that added collecting agent is different: primary " one roughing, recleaning, secondary are scanned " do not add butyl xanthate, and secondary " one roughing, recleaning, secondary are scanned " will add butyl xanthate.

Be that object is different repeatedly, primary " one roughing, recleaning, secondary are scanned " is flotation of lead and silver, and secondary " one roughing, recleaning, secondary are scanned " is flotation zinc and copper.

It is selected as twice with the material after one roughing that one roughing, recleaning, secondary are scanned finger, recleaning is: the concentrate of one roughing output (concentrate existing with foam-like above) first do selected for the first time after again to the concentrate of selected output (concentrate existing with foam-like above) for the first time do for the second time selected (do altogether twice selected, be the selected I of saying in claims and description, selected II), doing twice selected object is to improve the grade of concentrate.

The present invention's " one roughing " refers to through one roughing;

" recleaning " be exactly by twice selected, use and as selected for the first time raw material, carry out selectedly using roughly selecting for the first time product, selected is for the second time that the selected concentrate existing with foam-like above is for the first time carried out to primary cleaning again;

" secondary is scanned " is: the mine tailing of one roughing output (material of the non-foam shape of lower floor) is done for the second time and scanned that (doing altogether twice scans scanning for the first time the mine tailing (material of the non-foam shape of lower floor) of output again after first doing and scanning for the first time, be scanning I, scanning II of saying in claims and description), doing the object of scanning for twice is the rate of recovery that improves ore dressing.

The sodium carbonate agent that adjusts during flotation, vulcanized sodium is made vulcanizing agent, zinc sulfate is made inhibitor, butylamine black powder, butyl xanthate, diethyldithiocarbamate are done collecting agent, No. 2 oil is done foaming agent, No. 2 oil is again terpenic oil, it is the most frequently used the widest foaming agent in source of China, it is to take turpentine oil as raw material, then with sulfuric acid, makees catalyst, the organic reagent product that terebinthine principal component australene aquation is formed, it is glassy yellow oily liquids, main component is α-terpenol, and it is greater than 44%, density 0.9g/cm containing α-terpenol ³, there is rosin fragrance left and right, is conventional foaming agent for ore dressing.

Product of the present invention is lead concentrate, white vitriol and copper powder; Lead concentrate and white vitriol meet the requirement of industry standard.

Compare advantage and good effect that the present invention has with known technology:

1, the present invention can obtain meeting the lead concentrate of industry standard, the leaded 68-70wt% of lead concentrate from zinc oxide ore by the method for flotation; The industrial sulphuric acid zinc that meets industry standard, containing white vitriol 95-97wt%; Tri-kinds of products of copper powder cupric 80-85wt%.

2, the present invention can reclaim zinc, lead, silver, copper from zinc oxide ore simultaneously.

3, zinc of the present invention, lead, silver, copper recovery are high, lead recovery 95.0-96.0%, silver raising recovery rate 95.0-95.5%, zinc recovery 82.0-84.0%, copper recovery 88.0-91.0%.

4, the present invention compares with known technology, has realized the combination of ore dressing and smelting.

5, the present invention compares with known technology, does not produce waste water, waste gas, meets the requirement of national recycling economy and sustainable development.

Accompanying drawing explanation

Fig. 1 is zinc oxide ore comprehensive recycling process flow chart of the present invention (first paragraph is only processed No. 5 zinc-copper concentrate).

Fig. 2 is zinc oxide ore comprehensive recycling process flow chart of the present invention (second paragraph, No. 5 zinc-copper concentrate of take are raw material, then process).

It should be noted that, because technological process of the present invention is long, so whole flow process forms (on two pages of paper) jointly by the two-stage process of Fig. 1 first paragraph technique and Fig. 2, wherein the 1. stage of Fig. 1 bottom and Fig. 2 top the 1. stage mean that technique interconnects.

The specific embodiment

Below in conjunction with drawings and Examples, the present invention is described in further detail, but they are not limitation of the invention.

One, flotation of lead silver (one roughing, secondary are scanned, recleaning)

1.1 ore grindings: by dry ball, zinc oxide ore is worn into breeze, breeze granularity 90wt% is less than 120 orders.

Described zinc oxide ore is for containing zinc 5.00-10.00wt%, plumbous 5.00-8.00wt%, silver-colored 0.05-0.10wt%, copper 1.80-2.30wt%, sulphur 0.50-1.0wt%.

1.2 size mixing: water or No. 2 filtrates are sized mixing to breeze, and being adjusted to pulp density is 50-60wt%.

1.3 lead, silver are roughly selected I (one roughing): be to add vulcanized sodium 5.0-10.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% by breeze per ton, stir 20-30min; By breeze per ton, add zinc sulfate 1.5-2.5kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt%; By breeze per ton, add sodium carbonate 350.0-450.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; By breeze per ton, add collecting agent butylamine black powder 40.0-50.0g and butylamine black powder are formulated as the aqueous solution of 10-15wt% and add diethyldithiocarbamate 15.0-35.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% by breeze per ton, stir 4-6min; By breeze per ton, add No. 2 oily 40.0-60.0g of foaming agent again, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 concentrate and No. 1 mine tailing, No. 1 mine tailing carries out plumbous silver and scans I.

1.4 lead, silver are scanned I (once purging selection): be by adding vulcanized sodium 1.0-2.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp, stirring 20-30min; By adding zinc sulfate 0.5-0.7kg and zinc sulfate to be formulated as in the aqueous solution of 10-15wt% and 1 ton of No. 1 mine tailing ore pulp in 1 ton of No. 1 mine tailing ore pulp, add sodium carbonate 100.0-170.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; By adding collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 15.0-25.0g of foaming agent in 1 ton of No. 1 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 2 mine tailings, No. 2 mine tailings carry out plumbous silver and scan II.

1.5 lead, silver are scanned II (secondary is scanned): be by adding vulcanized sodium 1.0-2.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stirring 20-30min; By adding zinc sulfate 0.5-0.8kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp and by adding sodium carbonate 100.0-175.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stirring 4-6min; By adding collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 15.0-25.0g of foaming agent in 1 ton of No. 2 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 3 mine tailings.It is No. 4 concentrate that plumbous silver scans that I and the resulting concentrate of plumbous silver-colored II all mix, and No. 3 mine tailing carries out flotation zinc-copper, and No. 4 concentrate and No. 1 concentrate mix the selected I of laggard quadrat silver.

1.6 lead, silver-colored selected I (primary cleaning): be that water or No. 1 filtrate are sized mixing to No. 1 concentrate and No. 4 concentrate mixed ore pulps, being adjusted to pulp density is 50-60wt%, press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps, to add zinc sulfate 0.3-0.5kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add sodium carbonate 100.0-125.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps, to add collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 concentrate and chats, chats returns to plumbous silver and roughly selects I, and No. 2 concentrate carries out the silver-colored selected II of lead.

1.7 lead, silver-colored selected II (recleaning): be that No. 2 concentrate waters are adjusted to pulp density is 50-60wt%, press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press in 1 ton of No. 2 concentrate pulp that mixes up pulp density, to add zinc sulfate 0.5-1.0kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% and press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add sodium carbonate 100.0-125.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press in 1 ton of No. 2 concentrate pulp that mixes up pulp density, to add collecting agent butylamine black powder 2.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% and press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain chats and No. 3 concentrate, chats returns to plumbous silver and roughly selects I, obtains meeting lead concentrate and No. 1 filtrate of industry standard after No. 3 concentrate filters, and No. 1 filtrate is returned to plumbous silver-colored selected I.

Two, flotation zinc-copper (again carry out one roughing, secondary are scanned, recleaning)

2.1 zinc, copper are roughly selected I (one roughing): be that No. 3 mine tailing waters are adjusted to pulp density is 50-60wt%, press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density and add vulcanized sodium 1.5-2.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density, to add collecting agent butyl xanthate 100.0-125.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density and add diethyldithiocarbamate 2.0-7.5g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density again and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 zinc-copper concentrate and No. 4 mine tailings, No. 4 mine tailings carry out zinc-copper and scan I.

2.2 zinc, copper are scanned I (once purging selection): be by adding vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp, stirring 20-30min; By adding collecting agent butyl xanthate 25.0-50.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 10.0-15.0g of foaming agent in 1 ton of No. 4 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 5 mine tailings, No. 5 mine tailings carry out zinc-copper and scan II.

2.3 zinc, copper are scanned II (secondary is scanned): be by adding vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp, stirring 20-30min; By adding collecting agent butyl xanthate 25.0-50.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 10.0-15.0g of foaming agent in 1 ton of No. 5 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 6 mine tailings, No. 6 mine tailing obtains mine tailing and No. 2 filtrates after filtration, mine tailing is stored up, and No. 2 filtrate returning sized mixing; Zinc-copper is scanned I and zinc-copper and is scanned the resulting concentrate of II and mix and be zinc-copper concentrate No. 4, and No. 4 zinc-copper concentrate and No. 1 zinc-copper concentrate mix and carry out the selected I of zinc-copper.

2.5 zinc, the selected I of copper (primary cleaning): be that water or No. 3 filtrates are sized mixing to No. 1 zinc-copper concentrate and No. 4 zinc-copper concentrate mixed ore pulps, being adjusted to pulp density is 50-60wt%, press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add vulcanized sodium 0.3-0.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps, to add collecting agent butyl xanthate 20.0-30.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add No. 2 oily 7.5-12.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 zinc-copper concentrate and zinc-copper chats, zinc-copper chats returns to zinc-copper and roughly selects I, and No. 2 zinc-copper concentrate carries out the selected II of zinc-copper.

2.6 zinc, the selected II of copper (recleaning): be that No. 2 zinc-copper concentrate waters are adjusted to pulp density is 50-60wt%, press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density and add vulcanized sodium 0.3-0.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Pressing to add collecting agent butyl xanthate 20.0-30.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density adds diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min, press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density and add No. 2 oily 7.5-12.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 3 zinc-copper concentrate and zinc-copper chats, zinc-copper chats returns to zinc-copper and roughly selects I.No. 3 zinc-copper concentrate filter and obtain No. 5 zinc-copper concentrate and No. 3 filtrates that argentiferous 0.002-0.005wt%, copper 10-20wt%, lead are less than 3.0 wt%, zinc 35-45wt%, and No. 3 filtrate is returned to the selected I of zinc-copper, and No. 5 zinc-copper concentrate carry out zinc, copper is separated.

Three, zinc, copper separation

3.1 calcinations: calcination is that No. 5 zinc-copper concentrate are carried out to calcination 1.0-1.5h at 500 ℃ of-600 ℃ of temperature.

3.2 sulfuric acid leachings: sulfuric acid leaching is that No. 5 zinc-copper concentrate waters after calcination are sized mixing to liquid-solid ratio 4-5:1, add again 98wt% sulfuric acid, acidity is controlled at 200g/L-250g/L, temperature 70 C-75 ℃ and leaches 2.0-3.0h, filter containing zinc 98-110g/L, copper 30-40g/L, eventually No. 4 filtrates of sour pH=5.0-5.2 and be less than the leached mud that 6.0wt%, copper are less than 1.5wt% containing zinc.Leached mud is sent rotary kiln back to and is further volatilized and reclaim zinc, copper, silver, lead, and No. 4 filtrate is replaced.

3.3 displacements: displacement is No. 4 filtrates to be warmed up to 20 ℃-30 ℃ add zinc metal sheet to carry out copper displacement, and time swap is 80-100min, then filter to obtain copper powder and No. 5 filtrates of cupric 80-85wt%, and No. 5 filtrate is carried out condensing crystallizing.

3.4 condensing crystallizings: condensing crystallizing is to No. 5 filtrates evaporation and concentration that heats up carry out liquid-solid separation after crystallisation by cooling when concentrate reaches 300g/ L containing zinc, and output meets industrial white vitriol and the mother liquor of industry standard, and mother liquor returns to condensing crystallizing again.

The all percentages of the present invention local time, be all mass percent.If 10-15wt% in " and vulcanized sodium be formulated as the aqueous solution of 10-15wt%, " is mass percent.

embodiment 1

Containing somewhere, the Yunnan zinc oxide ore of zinc 6.53wt%, silver-colored 0.0532wt%, copper 2.44wt%, plumbous 5.85wt%, sulphur 0.61wt%, dry type ball milling, breeze granularity 90wt% is less than 120 orders, and getting 15000.00g breeze water, to be adjusted to pulp density be 50wt%.

primary " one roughing, recleaning, secondary are scanned ".ore pulp is carried out to plumbous silver and roughly select I: in ore pulp, add vulcanized sodium 75g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add zinc sulfate 22.5g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 10wt% and sodium carbonate 5.2g and sodium carbonate are formulated as 10wt%, stir 4-6min, add again collecting agent butylamine black powder 0.6g to be formulated as the aqueous solution of 10wt% and the aqueous solution that 0.23g diethyldithiocarbamate is formulated as 10wt%, stir 4-6min, add No. 2 oily 0.6g of foaming agent, stir 2min, open charging valve, scrape bubble 6-8min, obtain No. 1 concentrate and No. 1 mine tailing.

No. 1 mine tailing is carried out to plumbous silver and scan I: in No. 1 mine tailing ore pulp, add vulcanized sodium 30g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add zinc sulfate 15g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 10wt% and sodium carbonate 3g and sodium carbonate are formulated as 10wt%, stir 4-6min, add again collecting agent butylamine black powder 0.15g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.1g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.45g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 2 mine tailings.

No. 2 mine tailings are carried out to plumbous silver and scan II: in No. 2 mine tailing ore pulps, add vulcanized sodium 30g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add zinc sulfate 15g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 10wt% and sodium carbonate 3g and sodium carbonate are formulated as 10wt%, stir 4-6min, add again collecting agent butylamine black powder 0.15g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.1g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.45g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 3 mine tailings.Plumbous silver is scanned I and plumbous silver, and to scan that the resulting concentrate of II all mixes be No. 4 concentrate, and No. 3 mine tailing carries out flotation zinc-copper.

No. 1 concentrate and No. 4 concentrate are carried out to the silver-colored selected I of lead: water is adjusted No. 1 concentrate and No. 4 concentrate mixed ore pulps, being adjusted to pulp density is 50wt%, add vulcanized sodium 15g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add zinc sulfate 9.0g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 10wt% and sodium carbonate 3g and sodium carbonate are formulated as 10wt%, stir 4-6min, add again collecting agent butylamine black powder 0.15g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.1g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.3g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 concentrate and chats.

No. 2 concentrate are carried out to the silver-colored selected II of lead: water is adjusted No. 2 concentrate pulps, being adjusted to pulp density is 50wt%, add vulcanized sodium 15g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add zinc sulfate 15.0g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 10wt% and sodium carbonate 3g and sodium carbonate are formulated as 10wt%, stir 4-6min, add again collecting agent butylamine black powder 0.06g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.75g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.3g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain chats and No. 3 concentrate, after chats filters, composition is moisture content 15wt%, silver 0.152wt%, copper 1.03wt%, plumbous 15.27 wt%, zinc 7.75 wt%, chats weight in wet base 743.6g, productive rate 4.21wt%, No. 3 concentrate filter and obtain lead concentrate, lead concentrate water content 14wt%, silver-colored 0.605wt%, copper 0.88wt%, plumbous 68.12wt%, zinc 2.68wt%, lead concentrate weight in wet base 1273.3g, productive rate 7.30wt%, filtering the filtrate obtaining is No. 1 filtrate, No. 1 filtrate is returned plumbous silver-colored selected I.

again carry out " one roughing, recleaning, secondary are scanned ".No. 3 mine tailings are carried out to zinc-copper and roughly select I: water is adjusted No. 3 mine tailing ore pulps, being adjusted to pulp density is 50wt%, add vulcanized sodium 45g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, then add collecting agent butyl xanthate 3g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.06g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.3g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 zinc-copper concentrate and No. 4 mine tailings.

No. 4 mine tailings are carried out to zinc-copper and scan I: in No. 4 mine tailing ore pulps, add vulcanized sodium 15g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add again collecting agent butyl xanthate 0.75g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.08g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.3g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 5 mine tailings.

No. 5 mine tailings are carried out to zinc-copper and scan II: in No. 5 mine tailing ore pulps, add vulcanized sodium 15g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add again collecting agent butyl xanthate 0.75g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.08g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.3g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 6 mine tailings, No. 6 mine tailing obtains mine tailing after filtering, mine tailing composition is moisture content 16.35wt%, silver 0.0026wt%, copper 0.058wt%, plumbous 0.04wt%, zinc 0.27wt%, mine tailing weight in wet base 12962.2g, productive rate 72.29wt%, filtrate after filtration is No. 2 filtrates, No. 2 filtrate powder of returning mine is sized mixing.

No. 1 zinc-copper concentrate and No. 4 zinc-copper concentrate are carried out to the selected I of zinc-copper: water is adjusted No. 1 zinc-copper concentrate and No. 4 zinc-copper concentrate mixed ore pulps, being adjusted to pulp density is 50wt%, add vulcanized sodium 9.0g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add again collecting agent butyl xanthate 0.6g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.08g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.23g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 zinc-copper concentrate and zinc-copper chats.

No. 2 zinc-copper concentrate are carried out to the selected II of zinc-copper: water is sized mixing to No. 2 zinc-copper concentrate, being adjusted to pulp density is 50wt%, add vulcanized sodium 7.5g and vulcanized sodium to be formulated as the aqueous solution of 10wt%, stir 20-30min, add again collecting agent butyl xanthate 0.75g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 10wt% and diethyldithiocarbamate 0.08g and diethyldithiocarbamate are formulated as 10wt%, stir 4-6min, add No. 2 oily 0.23g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 3 zinc-copper concentrate and zinc-copper chats.After zinc-copper chats filters, its composition is moisture content 14.25wt%, silver-colored 0.0035wt%, copper 8.87wt%, plumbous 2.32 wt%, zinc 18.01wt%, zinc-copper chats weight in wet base 760.9g, productive rate 4.35wt%, and the filtrate after zinc-copper chats filters is returned zinc-copper and roughly selected I; No. 3 zinc-copper concentrate filter and obtain No. 5 its compositions of zinc-copper concentrate is moisture content 12.38wt%, silver-colored 0.0044wt%, copper 16.07wt%, plumbous 0.89wt%, zinc 42.48wt%, No. 5 zinc-copper concentrate weight in wet base 2028.7g, productive rate 11.85wt%, after filtering, solution is No. 3 filtrates, and No. 3 filtrate is returned the selected I of zinc-copper.

No. 5 zinc-copper concentrate 1500g that get after oven dry carry out calcination 1.0h at 500 ℃ of temperature.No. 5 zinc-copper concentrate after calcination are 1426g, and it is containing zinc 44.46wt%, copper 16.84wt%, calcination process zinc volatility 0.51wt%, copper volatility 0.38wt%.Take 1000.00g and burn rear No. 5 zinc-copper concentrate, be added in the dilute sulfuric acid that 5L concentration is 200g/ L, stir 2.0h at 70 ℃ of temperature, filter to such an extent that weight in wet base its composition of leached mud that is 515.3g is moisture content 12.67wt%, copper 1.08wt%, zinc 4.91wt% and containing No. 4 filtrate 4.0L of zinc 105.62g/L, copper 40.84 g/L.Get No. 4 filtrate 3.0L and heat to 20 ℃, add zinc metal sheet 300.0g, time swap is 80min, take out zinc metal sheet and dry the also surplus 160g that weighs, then filter to obtain copper powder 161.00g and No. 5 filtrate 2.93L of water content 9.34wt%, copper 83.68wt%, zinc 6.43wt%, No. 5 filtrate compositions are cupric 0.12g/L, zinc 152.63g/L.Get No. 5 filtrate intensification evaporation and concentration after 2L copper displacement to crystallisation by cooling separated after solution zinc 300g/L, obtain containing the mother liquor 0.3L of zinc 264g/L with containing the white vitriol 1048g of white vitriol 95.23wt%.

By can be calculated each economic target, be:

1 from ore to product lead recovery 95.99%, silver raising recovery rate is 95.06%, zinc recovery 82.47%, copper recovery are 90.44%.

2 zinc leaching rates are 95.02%, copper leaching rate is 97.01%, copper replacement recovery rate 99.72%.

3 lead concentrate compositions are: silver-colored 0.605wt%, copper 0.88wt%, plumbous 68.12wt%, zinc 2.68wt%, arsenic 0.22wt%, magnesia 0.98wt%, alundum (Al2O3) 2.12wt%, meet the requirement of lead concentrate industry standard seconds.

4 white vitriol compositions are: white vitriol 95.23wt%, water-insoluble 0.06 wt%, plumbous 0.005wt%, iron 0.003wt%, manganese 0.04wt%, cadmium 0.05wt%, meet the requirement of industry standard zinc sulfate I class certified products.

5 copper powder cupric 83.68wt%, zinc 6.43wt%.

embodiment 2

carry out for the first time " one roughing, recleaning, secondary are scanned ".Get somewhere, Yunnan zinc oxide ore containing zinc 5.84wt%, silver-colored 0.0506wt%, copper 1.98wt%, plumbous 6.04wt%, sulphur 0.58wt% dry type ball milling, breeze granularity is that 90wt% is less than 120 orders, and getting 18000.00g breeze water, to be adjusted to pulp density be 60wt%.

Ore pulp is carried out to plumbous silver and roughly select I: in ore pulp, add vulcanized sodium 180g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add zinc sulfate 45g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 15wt% and sodium carbonate 8g and sodium carbonate are formulated as 15wt%, stir 4-6min, add again collecting agent butylamine black powder 0.9g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.63g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 1.1g of foaming agent, stir 2min, open charging valve, scrape bubble 6-8min, obtain No. 1 concentrate and No. 1 mine tailing.

No. 1 mine tailing is carried out to plumbous silver and scan for the first time I: in No. 1 mine tailing ore pulp, add 72.0g vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add zinc sulfate 25.0g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 15wt% and sodium carbonate 6.1g and sodium carbonate are formulated as 15wt%, stir 4-6min, add again collecting agent butylamine black powder 0.36g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.18g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.9g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 2 mine tailings.

No. 2 mine tailings are carried out to plumbous silver and scan for the second time II: in No. 2 mine tailing ore pulps, add vulcanized sodium 90g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add zinc sulfate 28.8g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 15wt% and sodium carbonate 6.3g and sodium carbonate are formulated as 15wt%, stir 4-6min, add again collecting agent butylamine black powder 0.36g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.18g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.9g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 3 mine tailings.Scan I, the resulting concentrate of II is all incorporated to concentrate No. 4, No. 3 mine tailing carries out flotation zinc-copper.

No. 1 concentrate and No. 4 concentrate are carried out to plumbous silver selected I for the first time: water is adjusted No. 1 concentrate and No. 4 concentrate mixed ore pulps, being adjusted to pulp density is 60wt%, add vulcanized sodium 36g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add zinc sulfate 18g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 15wt% and sodium carbonate 4.5g and sodium carbonate are formulated as 15wt%, stir 4-6min, add again collecting agent butylamine black powder 0.36g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.18g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.54g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 concentrate and chats.

No. 2 concentrate are carried out to plumbous silver and carry out the second selected II: water is adjusted No. 2 concentrate pulps, being adjusted to pulp density is 60wt%, add vulcanized sodium 36g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add zinc sulfate 36g and zinc sulfate to be formulated as the aqueous solution that the aqueous solution of 15wt% and sodium carbonate 4.5g and sodium carbonate are formulated as 15wt%, stir 4-6min, add again collecting agent butylamine black powder 0.36g and butylamine black powder to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.18g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.54g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain chats and No. 3 concentrate, after chats filters, its composition is moisture content 14.85wt%, silver 0.149wt%, copper 0.94wt%, plumbous 16.51 wt%, zinc 5.64 wt%, chats weight in wet base 885.7g, productive rate 4.19wt%, after No. 3 concentrate filters, obtaining its composition of lead concentrate is moisture content 13.86wt%, silver-colored 0.578wt%, copper 0.82wt%, plumbous 69.48wt%, zinc 2.39wt%, lead concentrate weight in wet base 1521.2g, productive rate 7.28wt%, filtering solution is No. 1 filtrate, and No. 1 filtrate is returned the silver-colored selected I of selected lead.

No. 3 mine tailings are carried out to zinc-copper and again roughly select I: water is adjusted No. 3 mine tailing ore pulps, being adjusted to pulp density is 60wt%, add vulcanized sodium 90g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add again collecting agent butyl xanthate 4.5g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.27g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.54g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 zinc-copper concentrate and No. 4 mine tailings.

No. 4 mine tailings are carried out to zinc-copper and scan I: in No. 4 mine tailing ore pulps, add vulcanized sodium 36g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add again collecting agent butyl xanthate 1.8g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.18g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.54g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 5 mine tailings.

No. 5 mine tailings are carried out to zinc-copper and scan II: at No. 5 mine tailing ore pulps, add vulcanized sodium 36.0g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add again collecting agent butyl xanthate 1.8g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.18g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.54g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 6 mine tailings, No. 6 mine tailings after filtering its composition are moisture content 15.88wt%, silver 0.00256wt%, copper 0.05wt%, plumbous 0.04wt%, zinc 0.24wt%, mine tailing weight in wet base 15445g, productive rate 72.18wt%, filtering solution is No. 2 filtrates, No. 2 filtrate returning sized mixing.

again carry out " one roughing, recleaning, secondary are scanned ".no. 1 zinc-copper concentrate and No. 4 zinc-copper concentrate are carried out to the selected I of zinc-copper: water is adjusted No. 1 zinc-copper concentrate and No. 4 zinc-copper concentrate mixed ore pulp concentration, being adjusted to pulp density is 60wt%, add vulcanized sodium 18g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add again collecting agent butyl xanthate 1.08g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.218g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.43g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 zinc-copper concentrate and zinc-copper chats.

No. 2 zinc-copper concentrate are carried out to the selected II of zinc-copper: water is adjusted No. 2 zinc-copper concentrate pulps, being adjusted to pulp density is 60wt%, add vulcanized sodium 18g and vulcanized sodium to be formulated as the aqueous solution of 15wt%, stir 20-30min, add again collecting agent butyl xanthate 1.08g and butyl xanthate to be formulated as the aqueous solution that the aqueous solution of 15wt% and diethyldithiocarbamate 0.18g and diethyldithiocarbamate are formulated as 15wt%, stir 4-6min, add No. 2 oily 0.43g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 3 zinc-copper concentrate and zinc-copper chats.After zinc-copper chats filters, composition is moisture content 15.18wt%, silver-colored 0.0035wt%, copper 8.26wt%, plumbous 2.72wt%, zinc 20.89wt%, zinc-copper chats weight in wet base 916.8g, productive rate 4.32wt%; No. 3 zinc-copper concentrate filter and obtain No. 5 its compositions of zinc-copper concentrate is moisture content 12.85wt%, silver-colored 0.0024wt%, copper 12.35wt%, plumbous 1.22wt%, zinc 36.17wt%, No. 5 zinc-copper concentrate 2484.7g, productive rate 12.03wt%, filtering solution is No. 3 filtrates, and No. 3 filtrate is returned the selected I of zinc-copper.

No. 5 zinc-copper concentrate 1300g that get after oven dry carry out calcination 1.5h at 600 ℃ of temperature.No. 5 zinc-copper concentrate after calcination are 1236g, and it is containing zinc 37.85wt%, copper 12.92wt%, the zinc volatility 0.51wt% of calcination process, copper volatility 0.54wt%.Take 850g and burn rear No. 5 zinc-copper concentrate, be added in the sulfuric acid that 4L concentration is 250g/ L, 75 ℃ of temperature, stir 3.0h, filter to such an extent that leached mud 429g and the 3.15L of water content 12.84wt%, copper 1.17wt%, zinc 3.44wt% leaches No. 4 filtrates containing zinc 98.05g/L, copper 33.48 g/L.Get No. 4 filtrate 2.5L and heat to 40 ℃, add zinc metal sheet 300g, time swap is 60min, take out zinc metal sheet and dry the also surplus 200g that weighs, then filter to obtain copper powder 111.2g and No. 5 filtrate 2.4L of water content 9.15wt%, copper 82.52wt%, zinc 7.18wt%, No. 5 filtrate components are copper 0.15g/L, zinc 140.78g/L.Get No. 5 filtrate intensification evaporation and concentration after 1.5L copper displacement to crystallisation by cooling separated after solution zinc 300g/L, obtain containing the mother liquor 0.23L of zinc 265.15g/L with containing the white vitriol 688g of white vitriol 96.15wt%.

By can be calculated each economic target, be:

1 from ore to product lead recovery 95.19%, silver raising recovery rate is 95.49%, zinc recovery 83.96%, copper recovery are 88.51%.

2 zinc leaching rates are 96.00%, copper leaching rate is 96.03%; Copper replacement recovery rate 99.58%.

3 lead concentrate compositions are: silver-colored 0.578wt%, copper 0.82wt%, plumbous 69.48 wt%, zinc 2.39 wt%,, arsenic 0.31wt%, magnesia 1.28wt%, alundum (Al2O3) 2.31wt%, meet the requirement of lead concentrate industry standard seconds.

5 white vitriol compositions are: white vitriol 96.15wt%, water-insoluble 0.08 wt%, plumbous 0.007wt%, iron 0.005wt%, meet industry standard industrial sulphuric acid zinc II class certified products standard.

6 copper powder cupric 82.52wt%, zinc 7.18wt%.

Claims

1. a method that reclaims Zn, Pb and Ag copper from zinc oxide ore, it is characterized in that: adopt zinc sulfate to make inhibitor, with collecting agent butylamine black powder and diethyldithiocarbamate, pass through one roughing, recleaning, the floatation process that secondary is scanned is first the lead in ore, after silver flotates, adopt again collecting agent butyl xanthate and diethyldithiocarbamate, pass through one roughing, recleaning, the floatation process that secondary is scanned is the zinc in ore, copper flotates, the zinc-copper concentrate flotating is through calcination, sulfuric acid leaching and zinc metal sheet displacement copper, solution is through concentrated, crystallization obtains white vitriol, make zinc-copper separated, the sodium carbonate agent that adjusts during flotation, vulcanized sodium is made vulcanizing agent, and butylamine black powder, butyl xanthate and diethyldithiocarbamate are done collecting agent, and No. 2 oil is done foaming agent, and concrete technology step is as follows:

(1), flotation of lead silver:

(2), flotation zinc-copper:

(3), zinc, copper separation:

2. the method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (), flotation of lead silver (1) ore grinding are: by dry ball, zinc oxide ore is worn into breeze, breeze granularity 90wt% is less than 120 orders, and described zinc oxide ore is for containing zinc 5.00-10.00wt%, plumbous 5.00-8.00wt%, silver-colored 0.05-0.10wt%, copper 1.80-2.30wt%, sulphur 0.50-1.0wt%;

3. the method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (), flotation of lead silver (3) plumbous silver are roughly selected I and is: by breeze per ton, add vulcanized sodium 5.0-10.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; By breeze per ton, add zinc sulfate 1.5-2.5kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt%; By breeze per ton, add sodium carbonate 350.0-450.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; By breeze per ton, add collecting agent butylamine black powder 40.0-50.0g and butylamine black powder are formulated as the aqueous solution of 10-15wt% and add diethyldithiocarbamate 15.0-35.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% by breeze per ton, stir 4-6min; By breeze per ton, add No. 2 oily 40.0-60.0g of foaming agent again, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 concentrate and No. 1 mine tailing, No. 1 mine tailing carries out plumbous silver and scans I.

4. the method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (), flotation of lead silver (4) plumbous silver are scanned I and is: by adding vulcanized sodium 1.0-2.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp, stir 20-30min; By adding zinc sulfate 0.5-0.7kg and zinc sulfate to be formulated as in the aqueous solution of 10-15wt% and 1 ton of No. 1 mine tailing ore pulp in 1 ton of No. 1 mine tailing ore pulp, add sodium carbonate 100.0-170.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; By adding collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 1 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 15.0-25.0g of foaming agent in 1 ton of No. 1 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 2 mine tailings, No. 2 mine tailings carry out plumbous silver and scan II.

5. the method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (), flotation of lead silver (5) plumbous silver are scanned II and is: by adding vulcanized sodium 1.0-2.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stir 20-30min; By adding zinc sulfate 0.5-0.8kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp and by adding sodium carbonate 100.0-175.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stirring 4-6min; By adding collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 2 mine tailing ore pulp, stirring 4-6min; Again by adding No. 2 oily 15.0-25.0g of foaming agent in 1 ton of No. 2 mine tailing ore pulp, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 concentrate and No. 3 mine tailings, scan I, the resulting concentrate of II all mixes is No. 4 concentrate, No. 3 mine tailing carries out flotation zinc-copper, No. 1 concentrate and No. 4 concentrate mix the selected I of laggard quadrat silver.

6. the method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (), the plumbous silver-colored selected I of flotation of lead silver (6) are: water or No. 1 filtrate are sized mixing to No. 1 concentrate and No. 4 concentrate mixed ore pulps, being adjusted to pulp density is 50-60wt%, press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps, to add zinc sulfate 0.3-0.5kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add sodium carbonate 100.0-125.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps, to add collecting agent butylamine black powder 5.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again to mix up in 1 ton of No. 1 concentrate of pulp density and No. 4 concentrate pulps and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 concentrate and chats, chats returns to plumbous silver and roughly selects I, and No. 2 concentrate carries out the silver-colored selected II of lead.

7. the method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (), the plumbous silver-colored selected II of flotation of lead silver (7) are: it is 50-60wt% that No. 2 concentrate waters are adjusted to pulp density, press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press in 1 ton of No. 2 concentrate pulp that mixes up pulp density, to add zinc sulfate 0.5-1.0kg and zinc sulfate to be formulated as the aqueous solution of 10-15wt% and press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add sodium carbonate 100.0-125.0g and sodium carbonate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press in 1 ton of No. 2 concentrate pulp that mixes up pulp density, to add collecting agent butylamine black powder 2.0-10.0g and butylamine black powder to be formulated as the aqueous solution of 10-15wt% and press in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again in 1 ton of No. 2 concentrate pulp that mixes up pulp density and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain chats and No. 3 concentrate, chats returns to plumbous silver and roughly selects I, and No. 3 concentrate filters lead concentrate and No. 1 filtrate that obtains meeting industry standard, and No. 1 filtrate is returned to plumbous silver-colored selected I.

8. the method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (two) flotation zinc-copper (1) zinc-copper is roughly selected I and is: it is 50-60wt% that No. 3 mine tailing waters are adjusted to pulp density, press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density and add vulcanized sodium 1.5-2.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density, to add collecting agent butyl xanthate 100.0-125.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density and add diethyldithiocarbamate 2.0-7.5g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press in the 1 ton of No. 3 mine tailing ore pulp that mixes up pulp density again and add No. 2 oily 10.0-15.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 1 zinc-copper concentrate and No. 4 mine tailings, No. 4 mine tailings carry out zinc-copper and scan I;

Described step (two) flotation zinc-copper (2) zinc-copper is scanned I and is: by adding vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp, stir 20-30min; By adding collecting agent butyl xanthate 25.0-50.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 4 mine tailing ore pulp, stirring 4-6min; By adding No. 2 oily 10.0-15.0g of foaming agent in 1 ton of No. 4 mine tailing ore pulp, stir 1-3min again, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 5 mine tailings, No. 5 mine tailings carry out zinc-copper and scan II;

Described step (two) flotation zinc-copper (3) zinc-copper is scanned II and is: by adding vulcanized sodium 0.5-1.0kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp, stir 20-30min; By adding collecting agent butyl xanthate 25.0-50.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp and by adding diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt% in 1 ton of No. 5 mine tailing ore pulp, stirring 4-6min; Again by adding No. 2 oily 10.0-15.0g of foaming agent in 1 ton of No. 5 mine tailing ore pulp, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 4 zinc-copper concentrate and No. 6 mine tailings, No. 6 mine tailing obtains mine tailing and No. 2 filtrates after filtration, mine tailing is stored up, No. 2 filtrate returning sized mixing, and zinc-copper is scanned I and zinc-copper, and to scan that the resulting concentrate of II mixes be No. 4 zinc-copper concentrate, after No. 4 zinc-copper concentrate and No. 1 zinc-copper concentrate mix, carries out the selected I of zinc-copper;

The selected I of described step (two) flotation zinc-copper (4) zinc-copper is: water or No. 3 filtrates are sized mixing to No. 1 zinc-copper concentrate and No. 4 zinc-copper concentrate mixed ore pulps, being adjusted to pulp density is 50-60wt%, press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add vulcanized sodium 0.3-0.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min; Press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps, to add collecting agent butyl xanthate 20.0-30.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min; Press again to mix up in 1 ton of No. 1 zinc-copper concentrate of pulp density and No. 4 zinc-copper concentrate pulps and add No. 2 oily 7.5-12.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 2 zinc-copper concentrate and zinc-copper chats, zinc-copper chats returns to zinc-copper and roughly selects I, and No. 2 zinc-copper concentrate carries out the selected II of zinc-copper;

The selected II of described step (two) flotation zinc-copper (5) zinc-copper: it is 50-60wt% that No. 2 zinc-copper concentrate waters are adjusted to pulp density, press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density and add vulcanized sodium 0.3-0.5kg and vulcanized sodium to be formulated as the aqueous solution of 10-15wt%, stir 20-30min, pressing to add collecting agent butyl xanthate 20.0-30.0g and butyl xanthate to be formulated as the aqueous solution of 10-15wt% and press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density adds diethyldithiocarbamate 2.5-5.0g and diethyldithiocarbamate to be formulated as the aqueous solution of 10-15wt%, stir 4-6min, press in the 1 ton of No. 2 zinc-copper concentrate pulp that mixes up pulp density and add No. 2 oily 7.5-12.0g of foaming agent, stir 1-3min, open charging valve, scrape bubble 6-8min, obtain No. 3 zinc-copper concentrate and zinc-copper chats, zinc-copper chats returns to zinc-copper and roughly selects I, No. 3 zinc-copper concentrate filter and obtain argentiferous 0.002-0.005wt%, copper 10-20wt%, lead is less than 3.0 wt%, No. 5 zinc-copper concentrate and No. 3 filtrates of zinc 35-45wt%, No. 3 filtrate is returned to the selected I of zinc-copper, No. 5 zinc-copper concentrate carries out calcination.

9. a kind of method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described step (three) zinc, separated (1) calcination of copper: be that No. 5 zinc-copper concentrate are carried out to calcination 1.0-1.5h at 500 ℃ of-600 ℃ of temperature, No. 5 zinc-copper concentrate after calcination carry out sulfuric acid leaching;

Described step (three) zinc, separated (2) sulfuric acid leaching of copper: be that No. 5 zinc-copper concentrate waters after calcination are adjusted to liquid-solid ratio 4-5:1, add again 98wt% sulfuric acid, acidity is controlled at 200g/L-250g/L, temperature 70 C-75 ℃ and leaches 2.0-3.0h, filter containing zinc 98-110g/L, copper 30-40g/L, whole No. 4 filtrates of sour pH=5.0-5.2 and be less than the leached mud that 6.0wt%, copper are less than 1.5wt% containing zinc, leached mud is sent rotary kiln back to and is further volatilized and reclaim zinc, copper, silver, lead, and No. 4 filtrate is replaced;

Described step (three) zinc, copper separated (3) displacement: displacement is No. 4 filtrates to be warmed up to 20 ℃-30 ℃ add zinc metal sheet to carry out copper displacement, time swap is 80-100min, then filter to obtain copper powder and No. 5 filtrates of cupric 80-85wt%, No. 5 filtrate is carried out condensing crystallizing;

10. a kind of method that reclaims Zn, Pb and Ag copper from zinc oxide ore according to claim 1, it is characterized in that: described No. 2 oil of foaming agent are again terpenic oil, it is the most frequently used the widest foaming agent in source of China, it is to take turpentine oil as raw material, then with sulfuric acid, makees catalyst, the organic reagent product that terebinthine principal component australene aquation is formed, it is glassy yellow oily liquids, main component is α-terpenol, and it is greater than 44%, density 0.9g/cm containing α-terpenol ³, there is rosin fragrance left and right, is conventional foaming agent for ore dressing.