CN102824962A - Reagent formula used for zinc leaching residue floatation process and application method of reagent formula - Google Patents
Reagent formula used for zinc leaching residue floatation process and application method of reagent formula Download PDFInfo
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Abstract
The invention relates to a reagent formula used for a zinc leaching residue floatation process and an application method of the reagent formula. The reagent is a floatation reagent which is added into floatation processes such as sulfurizing, rough floatation, scavenging and concentration. The reagent formula is characterized in that 1) one or two of sodium sulphide and sodium hydrosulfide are added into a sulfurizing process as a sulfurizing reagent; 2) in the rough floatation process, N,N-sodium diethyldithiocarbamate, butyl ammonium black powder and 25# black powder are added as lead mineral collecting agents, Y89 and (or) pentyl xanthate are added as silver mineral collecting agent(s); 3) in a scavenging process, one or two of sodium sulphide and sodium hydrosulfide are added as the sulfutizing agent(s), N,N-sodium diethyldithiocarbamate, butyl ammonium black powder and 25# black powder are added as the lead mineral collecting agents, and the Y89 and (or) pentyl xanthate are added as the silver mineral collecting agent(s); and 4) carboxymethylcellulose is added as a gangue inhibiting agent in a concentration process. After applying the reagent formula disclosed by the invention, by adopting one-time rougher floatation, one-time scavenging and one-time concentration, lead yield can reach up to more than 95% and lead tail run can reach 0.1-0.2%.
Description
Affiliated technical field
The present invention relates to a kind of floating agent prescription and usage, especially a kind of reagent combination and usage that is used for zinc flotation of leached residue process belongs to wet method selecting and smelting technology field.
Background technology
Zinc soaks the leached mud that slag is a zinc hydrometallurgy leaching process output, and owing to the Zn, Pb and Ag symbiosis is difficult to handle and reasons such as processing method technological means formerly is limited, zinc soaks slag and contains the about 15-22% of zinc, leaded about 5-8%, the about 30-300g/t of argentiferous.It is main with zinc ferrite and zinc sulfate that zinc soaks slag zinc thing, and it is main with sardinianite and lead silicate that zinc soaks the plumbous thing of slag, and it is main with silver sulfide and simple substance silver that zinc soaks slag silver thing.According to " from the leached mud of Fe-laden acid zinc, the reclaiming the method for zinc " of Li Hong osmanthus invention (ZL96118245.8); Zinc soaks slag and contains zinc and be reduced to 7-15%; Make processing zinc soak the slag technology and stepped into major step, but compare with a zinc resource zincblende, zinc soaks slag and belongs to rich zinc resource.Therefore, zinc hydrometallurgy enterprise adopts methods recovery zinc such as leaching of high temperature peracid and Rotary Kiln volatilization to soak zinc and other valuable metal in the slag.Because energy consumption is high and environmental pollution heavily waits problem, most zinc hydrometallurgy enterprise stops to adopt Rotary Kiln technical finesse zinc to soak slag.Because of the zinc after leaching through the high temperature peracid soaks slag, contain zinc and still reach 3-5%, along with the dilution day by day of a zinc resource and the rising day by day of cost of winning, this zinc soaks slag and still belongs to rich zinc resource.Electricity zinc output and zinc soak the about 1:1 of slag output; By 1290.5 ten thousand tons of reckonings of world's electricity zinc output in 2011; World's zinc soaks slag and contains ten thousand tons/year of zinc total amount 38.7-64.5; Ten thousand tons/year of leaded total amount 64.5-103.2, argentiferous total amount 516.2-3871.5 ton/year, zinc soak slag and remain a kind of secondary Zn, Pb and Ag resource that value of exploiting and utilizing is arranged very much.Therefore, necessaryly improve formerly handling the method that zinc soaks slag.
Summary of the invention
The objective of the invention is to propose a kind of new reagent combination and usage to existing zinc flotation of leached residue process, this reagent combination and usage can effectively be extracted zinc and soak metal values in the slag, and medicament does not cause environmental pollution.
The inventor finds through a large amount of tests: zinc soaks slag and contains the high reason of zinc, and the one, the zinc ferrite mineral are wrapped up by sardinianite, have stoped to leach to react to carry out; The 2nd, formerly washing methods desorption zinc sulfate efficient is low, cause zinc sulfate to be soaked slag absorption by zinc and carry secretly, and then causing zinc to soak lead-in-dreg, high more then to contain zinc high more.Zinc soaks the reason of slag lead minerals and the difficult flotation of silver mineral; Be zinc sulfate parcel lead minerals and silver mineral surface formation aquation covering, stoped the effective absorption of medicament, and then causing zinc to soak slag, to contain zinc high more lead minerals and silver mineral; Lead minerals and silver mineral flotation yield are low more, and it is high more that lead concentrate contains zinc.
According to above-mentioned research, the technical scheme that the present invention taked is: a kind of reagent combination that is used for zinc flotation of leached residue process, described medicament, be vulcanize, roughly select, scan with selected floatation process in the floating agent that adds respectively, it is characterized in that:
1) adds one or both vulcanizing agents in vulcanized sodium or the NaHS in sulfidation;
2) add diethyldithiocarbamate, butyl ammonium aerofloat, 25 ﹟ black powder as the lead minerals collecting agent in rougher process, add Y89 with (or) penta xanthate is as the silver mineral collecting agent;
3) add one or both vulcanizing agents in vulcanized sodium or the NaHS in the process of scanning, add diethyldithiocarbamate, butyl ammonium aerofloat, 25 ﹟ black powder as the lead minerals collecting agent, add Y89 with (or) penta xanthate is as the silver mineral collecting agent;
4) add carboxymethyl cellulose as gangue inhibitor at refining process.
A kind of usage that is used for the reagent combination of zinc flotation of leached residue process is:
1) add vulcanizing agent in sulfidation, vulcanizing agent medicament and weight proportion thereof are: vulcanized sodium or NaHS (4-20kg);
2) add lead minerals collecting agent and silver mineral collecting agent in the preposition process of sizing mixing of one roughing, lead minerals collecting agent and silver mineral collecting agent medicament and weight proportion thereof are: diethyldithiocarbamate (200-300g/t), butyl ammonium aerofloat (50-100g/t); 25 ﹟ black powder (25-50g/t), Y89 (40-50g/t), penta xanthate (40-50g/t);
3) add vulcanizing agent, lead minerals collecting agent and silver mineral collecting agent in the preposition process of sizing mixing of once purging selection, vulcanizing agent, lead minerals collecting agent and silver mineral collecting agent medicament and weight proportion thereof are: vulcanized sodium (300-500g/t), diethyldithiocarbamate (50-100g/t), butyl ammonium aerofloat (25-50g/t), 25 ﹟ black powder (10-20g/t), Y89 (20-25g/t), penta Huang (20-25g/t);
4) add gangue inhibitor in the preposition process of sizing mixing of primary cleaning, gangue inhibitor medicament and weight proportion thereof are: carboxymethyl cellulose (50-200g/t).
Further; When Treatment of Copper zinc soaks slag; Increase ethyl ammonia sulfate (50-200g/t) in the preposition process of sizing mixing of one roughing, increase ethyl ammonia sulfate (50-100g/t), increase sodium thioglycolate (20-100g/t) in the preposition process of sizing mixing of primary cleaning in the preposition process of sizing mixing of once purging selection; The primary cleaner tailing slurry of output is copper concentrate, copper concentrate is implemented open circuit handle.
Further, when handling that argentiferous zinc does not soak slag, the preposition process of sizing mixing of one roughing do not add Y89 with (or) penta xanthate, the preposition process of sizing mixing of once purging selection do not add Y89 with (or) penta xanthate.
Advantage of the present invention is:
1) technological process is short, and equipment investment is little, and zinc, lead, silver-colored yield height and cost recovery significantly reduce.
2) can the independent operating mode or combine zinc hydrometallurgy enterprise formerly the production factors mode handle zinc and soak slag.
Description of drawings
Fig. 1 is a kind of ultrasonic dressing and smelting process that zinc soaks slag of handling.
Fig. 2 soaks the ultrasonic dressing and smelting process of slag for a kind of Treatment of Copper zinc.
Among Fig. 1,1, zinc soaks slag; 2, ore mill; 3, ore pulp behind the ore grinding; 4, electrodeposition waste liquid (or industrial sulphuric acid); 5, hydrogen peroxide solution; 6, filter; 7, solution of zinc sulfate; 8, filter; 9, supersound washing filtrating; 10, the preposition back liquid of sizing mixing of ultrasonic leaching; 11, liquid after the ultrasonic leaching; 12, ultrasonic leaching filter residue; 13, hot water; 14, the preposition back liquid of sizing mixing of supersound washing; 15, liquid after the supersound washing; 16, medicament; 17, supersound washing filter residue; 18, paste mixer; 19, ultrasonic leaching machine; 20, medicament; 21, paste mixer; 22, ultrasonic washer; 23, paste mixer; 24, one roughing concentrate slurry; 25, the preposition back ore pulp of sizing mixing of one roughing; 26, medicament; 27, ore pulp after the ultrasonic sulfuration; 28, the preposition back ore pulp of sizing mixing of ultrasonic sulfuration; 29, once purging selection concentrate slurry; 30, one roughing mine tailing slurry; 31, air flotation machine; 32, the preposition ultrasonic dispersion of one roughing back ore pulp; 33, ultrasonic dispersion machine; 34, paste mixer; 35, ultrasonic vulcanizer; 36, once purging selection mine tailing slurry; 37, air flotation machine; 38, the preposition ultrasonic dispersion of once purging selection back ore pulp; 39, ultrasonic dispersion machine; 40, bulk concentrate slurry; 41, medicament; 42, the preposition back ore pulp of sizing mixing of primary cleaning; 43, dewatered tailings; 44, filter; 45, tail water; 46, paste mixer; 47, ultrasonic dispersion machine; 48, the preposition ultrasonic dispersion of primary cleaning back ore pulp; 49, air flotation machine; 50, primary cleaner tailing slurry; 51, lead concentrate.
Among Fig. 2,52, preposition ultrasonic leaching system; 53, rearmounted ultrasonic flotation system.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further description, but protection scope of the present invention is not limited to the described scope of embodiment.
Embodiment one:A kind ofly handle the ultrasonic dressing and smelting process that zinc soaks slag
Can find out that from Fig. 1 and 2 the present invention is a kind of ultrasonic dressing and smelting process that zinc soaks slag of handling.Preposition ultrasonic leaching system 52 is made up of ore mill 2, paste mixer 18, ultrasonic leaching machine 19, filter 6, paste mixer 21, ultrasonic washer 22,8 in filter; Postposition ultrasonic flotation system 53 is made up of paste mixer 23, ultrasonic vulcanizer 35, paste mixer 34, ultrasonic dispersion machine 33, air flotation machine 31, ultrasonic dispersion machine 39, air flotation machine 37, paste mixer 46, ultrasonic dispersion machine 47, air flotation machine 49,44 in filter.Its know-why and the course of work are:
Zinc soaks slag 1 and hot water 13 by solid-to-liquid ratio 2:1 batching, gets into ore mill 2, and output zinc soaks ore pulp 3 behind slag 1 granularity accounts for 90-100% for-0.074mm the ore grinding.
Ore pulp 3 entering stirring paste mixers 18 are sized mixing behind the ore grinding.The solvent of sizing mixing comprises zinc electrodeposition waste liquid (or industrial sulphuric acid) 4 and supersound washing filtrating 9.The solid-to-liquid ratio of sizing mixing is 1:3, initial p H1-2.5, and 70-90 ℃ of adjusting slurry temperature control, hydrogen peroxide solution consumption 10-40ml/L, after sizing mixing 5-30 minute, the preposition back liquid 10 of sizing mixing of the ultrasonic leaching of output.
The preposition back liquid 10 of sizing mixing of ultrasonic leaching pumps into one-way flow in the U type tubular ultrasonic leaching machine 19.Ultrasonic leaching machine 19 forms effective sound intensity greater than 1w/cm in the preposition back liquid 10 of sizing mixing of the ultrasonic leaching of one-way flow
2The ultrasonic wave sound field; The particle flux bump zinc that this ultrasonic wave sound field causes 400 meters flow velocitys of per second soaks slag 1 surface; Reinforcement is degraded zinc and is soaked slag 1 surperficial newborn covering (like iron oxide mineral and zinc sulfate covering) and self covering (like the zinc ferrite covering), and the preposition back liquid 10 of sizing mixing of the ultrasonic leaching of setting granularity, concentration, liquid temperature, PH, pulp potential is implemented ultrasonic leaching.Ultrasonic leaching is after 1-5 minute, and the zinc ferrite that zinc soaks in the slag 1 is decomposed, and output comprises the ultrasonic leaching back liquid 11 of ionic state zinc sulfate and solid oxide iron mineral.
Ultrasonic leaching back liquid 11 pumps into filter 6 under liquid temperature>=70 ℃, PH≤5.2 conditions.Filter process does not have the basic zinc sulfate crystallization to generate, thereby stops ultrasonic leaching filter residue 12 surfaces to form basic zinc sulfate aquation covering.The ultrasonic leaching filtrating of filter 6 outputs is solution of zinc sulfate 7, carries cleaning system to handle with pipeline or chute.
Get into the ultrasonic leaching filter residue 12 that stirs paste mixer 21; Its solvent of sizing mixing is a hot water 13, and solid-to-liquid ratio is that 1:3-4 (obviously, reduces the preposition process solid-to-liquid ratio of sizing mixing of supersound washing to 1:8-10; Then clean result is better); 70-90 ℃ of liquid temperature, after sizing mixing 5-30 minute, the preposition back liquid 14 of sizing mixing of output supersound washing.
The preposition back liquid 14 of sizing mixing of supersound washing pumps into one-way flow in the U type tubular ultrasonic rinsing maching 22.Ultrasonic washer 22 forms effective sound intensity greater than 1w/cm in the preposition back liquid 14 of sizing mixing of the supersound washing of one-way flow
2The ultrasonic wave sound field, the particle flux that this ultrasonic wave sound field causes 400 meters flow velocitys of per second clashes into ultrasonic leaching filter residue 12 surfaces, and the zinc sulfate desorptions that are adsorbed on ultrasonic leaching filter residue 12 surfaces are got in the hot water 13, liquid 15 after the output supersound washing.
Liquid 15 pumps into filter 8 after the supersound washing under the condition of 70-90 ℃ of liquid temperature, PH≤5.2, and filter process does not have the basic zinc sulfate crystallization and generates, and then effectively stops 17 pairs of zinc sulfate generations of supersound washing filter residue absorption to be carried secretly.The supersound washing of filter 8 outputs filtrating 9 is sized mixing from flowing into paste mixer 18, and supersound washing filter residue 17 gets into and stirs paste mixer 23 as the raw material of rearmounted ultrasonic flotation system 53.Accomplish the preposition ultrasonic leaching process that zinc soaks slag 1 thus.
Supersound washing filter residue 17 is prepared burden by solid-to-liquid ratio 1:2-3 with hot water 13 in stirring paste mixer 23; At slurry temperature 60-70 ℃; Under the condition of medicament 16 (like vulcanized sodium) addition 4-20kg/t, stir and sized mixing 3-8 minute, the preposition back ore pulp 28 of sizing mixing of the ultrasonic sulfuration of output.
The preposition back ore pulp 28 of sizing mixing of ultrasonic sulfuration pumps into one-way flow in the U type tubular ultrasonic vulcanizer 35.Ultrasonic vulcanizer 35 forms effective sound intensity greater than 1w/cm in the preposition back ore pulp 28 of sizing mixing of the ultrasonic sulfuration of one-way flow
2The ultrasonic wave sound field; This ultrasonic wave sound field causes particle flux bump supersound washing filter residue 17 surfaces of 400 meters flow velocitys of per second; The ultra-fine gangue sludge that is deposited on supersound washing filter residue 17 surfaces is removed by efficient; Medicament 16 (be vulcanized sodium or NaHS, addition is 4-20kg) preferred deposition is in lead minerals and silver mineral surface, and making lower lead minerals of hydrophobicity and silver mineral surface modification is the higher sulfide cladding surface of hydrophobicity.Ultrasonic sulfuration is 3 minutes under slurry temperature 60-70 ℃ condition, and accomplishing supersound washing filter residue 17 lead minerals and silver mineral surface modification is the sulfidation of sulfide covering, the ultrasonic sulfuration of output back ore pulp 27.
Ultrasonic sulfuration back ore pulp 27 gets into to stir and carries out in the paste mixers 34 that one roughing is preposition sizes mixing.This process of sizing mixing is intended to utilize medicament 26 to implement lead minerals and silver mineral are modified as selective absorption and deposition behind the sulfide covering, further improves the surperficial hydrophobicity of lead minerals and silver mineral.Medicament 26 is: diethyldithiocarbamate (200-300g/t), butyl ammonium aerofloat (50-100g/t); 25 ﹟ black powder (25-50g/t), Y89 (40-50g/t), penta xanthate (40-50g/t).After sizing mixing 3-5 minute, the preposition back ore pulp 25 of sizing mixing of output one roughing.
The preposition back ore pulp 25 of sizing mixing of one roughing pumps into one-way flow in the U type tubular ultrasonic dispersion machine 33.Ultrasonic dispersion machine 33 forms effective sound intensity greater than 1w/cm in the preposition back ore pulp 25 of sizing mixing of the one roughing of one-way flow
2The ultrasonic wave sound field; This ultrasonic wave sound field causes the particle flux bump supersound washing filter residue 17 and medicament 26 of 400 meters flow velocitys of per second; The ultra-fine gangue sludge that is deposited on lead minerals and silver mineral modification sulfide cladding surface is removed by efficient, and medicament 26 efficiently disperses in the preposition back ore pulp 25 of sizing mixing of one roughing.The preposition ultrasonic dispersion of one roughing is after 0.5-1 minute, and medicament 26 is able to firmly be deposited on the modification sulfide cladding surface of supersound washing filter residue 17 lead minerals and silver mineral, for sufficient and necessary condition is created in the efficient completion of rearmounted bubble mineralization process.
The preposition ultrasonic dispersion of one roughing back ore pulp 32 gets in the air flotation machine 31.Air flotation machine 31 adopts the cored screw rotor structure to implement bubble and produces and mineralization process, adopts the mode of N bar helical duct shunting mine tailing slurry to implement the gas solid separation process, is feeding pressure 0.3MPa, flow 3-4m
3Under/h the airflow conditions; Bubbling air stream forms N spiral gas field in the cored screw rotor; The preposition ultrasonic dispersion of one roughing back ore pulp 32 is implemented N gas-liquid mixed, make one roughing be attached to bubble surface fast by the lead minerals and the silver mineral particle of medicament 26 abundant parcels in the ore pulp 32 of back preposition ultrasonic the dispersion.Mineral laden bubble with not by the gangue particle of absorbing bubbles, gas solid separation is accomplished in gas solid separation air flotation machine 31 in zone: mineral laden bubble emersion mineral syrup liquid, outflow air flotation machine 31, output one roughing concentrate slurry 24; Gangue particle flows out output one roughing mine tailing slurry 30 through being located at the N bar helical duct shunting of air flotation machine 31 cell body inwalls from the mine tailing slurry outlet of air flotation machine 31 bottoms.
Utilize the one roughing gas solid separation zone of air flotation machine 31 to add medicament 20, one roughing mine tailing slurry 30 is sized mixing.Medicament 20 is: vulcanized sodium (300-500g/t), diethyldithiocarbamate (50-100g/t), butyl ammonium aerofloat (25-50g/t), 25 ﹟ black powder (10-20g/t), Y89 (20-25g/t), penta Huang (20-25g/t).The process of sizing mixing and the one roughing gas solid separation process of one roughing mine tailing slurry 30 are same process.
One roughing mine tailing slurry 30 gets into ultrasonic dispersion machine 39, go through the ultrasonic dispersion process of the preposition back ore pulp 25 of sizing mixing of one roughing roughly the same after, preposition ultrasonic dispersions of output once purging selection be ore pulp 38 afterwards.
The preposition ultrasonic dispersion of once purging selection back ore pulp 38 gets into air flotation machines 37, goes through after the preposition ultrasonic floatation process that disperses back ore pulp 32 of one roughing roughly the same output once purging selection concentrate slurry 29 and once purging selection mine tailing slurry 36.
One roughing concentrate slurry 24 and once purging selection concentrate slurry 29, can conflux is bulk concentrate slurry 40, gets into to stir to carry out in the paste mixer 46 that primary cleaning is preposition sizes mixing.This process of sizing mixing adds medicament 41, and medicament 41 is carboxymethyl cellulose (50-200g/t).After sizing mixing 3-5 minute, the preposition back ore pulp 42 of sizing mixing of output primary cleaning.
Primary cleaning is preposition, and the back ore pulp 42 of sizing mixing pumps into ultrasonic dispersion machine 47, go through the ultrasonic dispersion process of preposition size mixing back ore pulp 25 and one roughing mine tailing slurry 30 of one roughing roughly the same after, ore pulp 48 after preposition ultrasonic dispersions of output primary cleaning.
The preposition ultrasonic dispersion of primary cleaning back ore pulp 48 gets into air flotation machine 49; Go through one roughing roughly the same preposition ultrasonic dispersion after the preposition ultrasonic floatation process that disperses back ore pulp 38 of back ore pulp 32 and once purging selection, output primary cleaning concentrate slurry is lead concentrate 51 and primary cleaner tailing slurry 50.
Once purging selection mine tailing slurry 36 gets into filter 44, output dewatered tailings 43 and tail water 45.Tail water 45 is middle warm water, returns 23 pairs of supersound washing filter residues of paste mixer 17 after heating and implements to size mixing.Accomplish the rearmounted ultrasonic flotation process of supersound washing filter residue 17 thus.
The air flotation machine that the present invention adopts, open in patents of invention such as PCT/CN2011/078154 and CN102441494A, but do not repel the application of air flotation machine formerly.Formerly the know-why of air flotation machine and the course of work are well-known.
Can find out from Fig. 1 and 2, in the preposition process of sizing mixing of ultrasonic leaching of preposition ultrasonic leaching system 52, leach reaction and begin; Prolong the preposition process time of sizing mixing of ultrasonic leaching; The ultrasonic leaching process time can correspondingly shorten, otherwise the ultrasonic leaching process time can correspondingly prolong.The concrete parameter of the process of sizing mixing depends on factor, especially the ore pulp warm-up time factors such as setting slurry temperature, acidity, solid-to-liquid ratio and medicament interpolation deadline reached.
Can find out from Fig. 1 and 2; The main effect of hydrogen peroxide solution 5; It is the strong oxidizer effect of leaching under the environment setting; Through the disproportionation current potential zinc is soaked slag institute's sulfur compound and ferrous iron and implement oxidation, adjustment is leached pulp potential under the environment and is in the pulp potential that zinc ferrite can not stable existence, and then effectively eliminates zinc sulfate aquation covering.The addition manner of hydrogen peroxide solution 5 is evenly continuous addition manner.The addition manner of assault formula will cause it to consume meaningless increase.
It can also be seen that from Fig. 1 and 2; The degree of association of flotation effect and air flotation machine functional structure is very big; Bubble produces and the mineralization process effect, and gas solid separation process effect, when using the air flotation machine of difference in functionality structure; Cause different roughly selecting number of times thus, scan number of times, selected number of times and air stream parameter, be fully possible.The air flotation machine 31,37,49 that the present invention adopts, its bubble produces and mineralization process, is based on N the bubble under the spiral gas field action and produces and mineralization process; Its gas solid separation process is based on the gas solid separation process that adopts N bar helical duct shunting mine tailing.
Embodiment two:A kind of Treatment of Copper zinc soaks the ultrasonic dressing and smelting process of slag
As can beappreciated from fig. 2; The present invention is the ultrasonic dressing and smelting process that a kind of Treatment of Copper zinc soaks slag; Its engineering design and embodiment one are essentially identical, and difference is: in the medicament 26 that the preposition process of sizing mixing of one roughing adds, increase ethyl ammonia sulfate (50-200g/t); In the medicament 20 that the preposition process of sizing mixing of once purging selection adds, increase ethyl ammonia sulfate (50-100g/t); In the medicament 41 that the preposition process of sizing mixing of primary cleaning adds, increase sodium thioglycolate (20-100g/t); Primary cleaner tailing slurry 50 is a copper concentrate, and copper concentrate is implemented open circuit and handled.
The zinc of using the ultrasonic flotation and metallurgy method Treatment of Copper 0.8% of present embodiment soaks slag 1, obtains the supersound washing filter residue 17 of cuprics 2.4% in preposition ultrasonic leaching system 52, obtains the primary cleaner tailing slurry 50 of cupric 12-15% in rearmounted ultrasonic flotation system 53.Primary cleaner tailing slurry 50 open circuits are implemented subsequent treatment (copper concentrate is selected such as increasing), then can obtain the copper concentrate of commerical grade grade.
Obviously, under the ultrasonic dressing and smelting process condition of present embodiment, cupric zinc soaks the partial oxidation copper mineral in the slag 1, will be got in the solution of zinc sulfate 7 by leaching section inevitably.Adjust ultrasonic leaching process condition, can change the ratio that copper mineral gets into solution of zinc sulfate 7 and primary cleaner tailing slurry 50.Therefore, the present invention is applied to the processing of zinc-lead oxide copper mine, zinc oxide copper mine, can realize zinc lead bronze or zinc-copper high efficiency separation, and output solution of zinc sulfate, copper concentrate adopt zinc dust precipitation to handle then output copper sponge to solution of zinc sulfate.
Embodiment three:The ultrasonic dressing and smelting process of slag is soaked in a kind of processing not argentiferous zinc
As can beappreciated from fig. 2, the present invention be a kind of processing not argentiferous zinc soak the ultrasonic dressing and smelting process of slag, its engineering design and embodiment one are essentially identical, difference is: floatation process need not add Y89 with (or) penta xanthate.The plumbous zinc ore in Zn, Pb and Ag symbiosis or half a lifetime is very general in the lead zinc sulphur ore resource, but in the lead zinc sulphur ore in area, the Chinese western Hunan, hardly silver containing mineral.In plumbous zinc oxide ore, a lot of not argentiferous or the very low plumbous zinc resources of argentiferous are arranged also.Use present embodiment and handle not that the zinc of argentiferous soaks slag, help practicing thrift reagent cost.
Can find out through the foregoing description, the present invention relates to a kind of reagent combination that is used for zinc flotation of leached residue process, described medicament, be vulcanize, roughly select, scan with selected floatation process in the floating agent that adds respectively, it is characterized in that:
1) adds one or both vulcanizing agents in vulcanized sodium or the NaHS in sulfidation;
2) add diethyldithiocarbamate, butyl ammonium aerofloat, 25 ﹟ black powder as the lead minerals collecting agent in rougher process, add Y89 with (or) penta xanthate is as the silver mineral collecting agent;
3) add one or both vulcanizing agents in vulcanized sodium or the NaHS in the process of scanning, add diethyldithiocarbamate, butyl ammonium aerofloat, 25 ﹟ black powder as the lead minerals collecting agent, add Y89 with (or) penta xanthate is as the silver mineral collecting agent;
4) add carboxymethyl cellulose as gangue inhibitor at refining process.
A kind of usage that is used for the reagent combination of zinc flotation of leached residue process is:
1) add vulcanizing agent in sulfidation, vulcanizing agent medicament and weight proportion thereof are: vulcanized sodium or NaHS (4-20kg);
2) add lead minerals collecting agent and silver mineral collecting agent in the preposition process of sizing mixing of one roughing, lead minerals collecting agent and silver mineral collecting agent medicament and weight proportion thereof are: diethyldithiocarbamate (200-300g/t), butyl ammonium aerofloat (50-100g/t); 25 ﹟ black powder (25-50g/t), Y89 (40-50g/t), penta xanthate (40-50g/t);
3) add vulcanizing agent, lead minerals collecting agent and silver mineral collecting agent in the preposition process of sizing mixing of once purging selection, vulcanizing agent, lead minerals collecting agent and silver mineral collecting agent medicament and weight proportion thereof are: vulcanized sodium (300-500g/t), diethyldithiocarbamate (50-100g/t), butyl ammonium aerofloat (25-50g/t), 25 ﹟ black powder (10-20g/t), Y89 (20-25g/t), penta Huang (20-25g/t);
4) add gangue inhibitor in the preposition process of sizing mixing of primary cleaning, gangue inhibitor medicament and weight proportion thereof are: carboxymethyl cellulose (50-200g/t).
Further; When Treatment of Copper zinc soaks slag; Increase ethyl ammonia sulfate (50-200g/t) in the preposition process of sizing mixing of one roughing, increase ethyl ammonia sulfate (50-100g/t), increase sodium thioglycolate (20-100g/t) in the preposition process of sizing mixing of primary cleaning in the preposition process of sizing mixing of once purging selection; The primary cleaner tailing slurry of output is copper concentrate, copper concentrate is implemented open circuit handle.
Further, when handling that argentiferous zinc does not soak slag, the preposition process of sizing mixing of one roughing do not add Y89 with (or) penta xanthate, the preposition process of sizing mixing of once purging selection do not add Y89 with (or) penta xanthate.
For a long time; The ore dressing brainstrust has been neglected the negative effect of solvable zinc sulfate under the flotation environment; And existing ion flotation method research rests on ionic state noble metal recovery field; So, study from the angle of method for floating merely, almost have no chance to find economy high efficiente callback zinc to soak the technical method and the compounding method for medicament of slag lead minerals and silver mineral.The present invention also is based on zinc and soaks the efficient desorption of the contained zinc sulfate of slag a kind of compounding method for medicament afterwards.
The inventor to zinc soak slag, difficulty selects lead-zinc, difficulty to select mineral such as oxidation lead skim; Carrying out the floatation process test finds; Adopt diethyldithiocarbamate and butyl ammonium aerofloat to make the lead minerals collecting agent, plumbous yield can reach more than 90%, but after increasing by 25 ﹟ black powder; Plumbous yield can reach more than 95%, and the plumbous tail that runs is reduced to 0.1%.Refining process adopts gangue inhibitors such as starch, waterglass, calgon, suppresses effect all not as carboxymethyl cellulose.Obviously, adjust the butyl ammonium aerofloat consumption, adopt 2# oil (mixtures of terpenic oil and petrochemical industry intermediate products), also can reach or approaching flotation effect of the present invention as replenishing foaming agent.Use Y89 or penta xanthate separately, the adjustment consumption, zinc flotation of leached residue effect also is rather approaching.
The inventor also confirms from test, soaks slag for leaded 20% above zinc, adopts the mixed lead concentrate of one roughing, once purging selection output, and leaded grade promptly reaches more than 35%, the leaded 0.1-0.2% that is reduced to of once purging selection mine tailing.
Claims (6)
1. reagent combination that is used for zinc flotation of leached residue process, described medicament, be vulcanize, roughly select, scan with selected floatation process in the floating agent that adds respectively, it is characterized in that:
1) adds one or both vulcanizing agents in vulcanized sodium or the NaHS in sulfidation;
2) add diethyldithiocarbamate, butyl ammonium aerofloat, 25 ﹟ black powder as the lead minerals collecting agent in rougher process, add Y89 with (or) penta xanthate is as the silver mineral collecting agent;
3) add one or both vulcanizing agents in vulcanized sodium or the NaHS in the process of scanning, add diethyldithiocarbamate, butyl ammonium aerofloat, 25 ﹟ black powder as the lead minerals collecting agent, add Y89 with (or) penta xanthate is as the silver mineral collecting agent;
4) add carboxymethyl cellulose as gangue inhibitor at refining process.
2. usage that is used for the reagent combination of zinc flotation of leached residue process, it is characterized in that: the usage of said reagent combination is:
1) add vulcanizing agent in sulfidation, vulcanizing agent medicament and weight proportion thereof are: vulcanized sodium or NaHS 4-20kg;
2) add lead minerals collecting agent and silver mineral collecting agent in the preposition process of sizing mixing of one roughing, lead minerals collecting agent and silver mineral collecting agent medicament and weight proportion thereof are: diethyldithiocarbamate 200-300g/t, butyl ammonium aerofloat 50-100g/t; 25 ﹟ black powder 25-50g/t, Y8940-50g/t, penta xanthate 40-50g/t;
3) add vulcanizing agent, lead minerals collecting agent and silver mineral collecting agent in the preposition process of sizing mixing of once purging selection, vulcanizing agent, lead minerals collecting agent and silver mineral collecting agent medicament and weight proportion thereof are: vulcanized sodium 300-500g/t, diethyldithiocarbamate 50-100g/t, butyl ammonium aerofloat 25-50g/t, 25 ﹟ black powder 10-20g/t, Y8920-25g/t, penta yellow 20-25g/t;
4) add gangue inhibitor in the preposition process of sizing mixing of primary cleaning, gangue inhibitor medicament and weight proportion thereof are: carboxymethyl cellulose 50-200g/t.
3. a kind of usage that is used for the reagent combination of zinc flotation of leached residue process as claimed in claim 2; It is characterized in that: when Treatment of Copper zinc soaks slag; Increase ethyl ammonia sulfate 50-200g/t in the preposition process of sizing mixing of one roughing, increase ethyl ammonia sulfate 50-100g/t, increase sodium thioglycolate 20-100g/t in the preposition process of sizing mixing of primary cleaning in the preposition process of sizing mixing of once purging selection; The primary cleaner tailing slurry of output is copper concentrate, copper concentrate is implemented open circuit handle.
4. a kind of usage that is used for the reagent combination of zinc flotation of leached residue process as claimed in claim 2; It is characterized in that: when handling that argentiferous zinc does not soak slag; The preposition process of sizing mixing of one roughing do not add Y89 with (or) penta xanthate, the preposition process of sizing mixing of once purging selection do not add Y89 with (or) penta xanthate.
5. a kind of usage that is used for the reagent combination of zinc flotation of leached residue process as claimed in claim 3, it is characterized in that: described zinc soaks slag, is that the zinc behind the employing flotation and metallurgy method desorption zinc sulfate covering soaks slag.
6. a kind of usage that is used for the reagent combination of zinc flotation of leached residue process as claimed in claim 3; It is characterized in that: soak the lead-in-dreg grade at zinc and be higher than at 20% o'clock; The lead concentrate of the lead concentrate of one roughing process output and once purging selection process output mixes; Can become leaded lead concentrate more than 35%, and the leaded 0.1-0.2% that is reduced to of once purging selection mine tailing, thereby can remove the primary cleaning process from.
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| CN103551256A (en) * | 2013-11-06 | 2014-02-05 | 株洲市湘麒科技开发有限公司 | Activating agent for use in floatation of silver in zinc hydrometallurgy acid leaching pulp |
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| CN103657860B (en) * | 2013-12-11 | 2015-09-30 | 广西大学 | The method of reverse flotation enrichment zinc silicate mineral in acid condition |
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| CN104785356A (en) * | 2015-03-26 | 2015-07-22 | 云南永昌铅锌股份有限公司 | Method and system for processing leaching residues of zinc hydrometallurgy |
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| CN107626441B (en) * | 2017-10-20 | 2019-12-03 | 中国科学院过程工程研究所 | Recycle the beneficiation method and beneficiation reagent of copper in copper slag |
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| CN115445776A (en) * | 2022-08-11 | 2022-12-09 | 昆明理工大学 | Separation method applied to copper-lead bulk concentrates |
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