CN1093414A - A kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material - Google Patents
A kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material Download PDFInfo
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Abstract
The invention belongs to a kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material.
Material handling is most of metal and nonmetal mineral materials.Using solvent is weak volatile acid alkali salt class, processing method is that solid powder is dropped into interior mixing of protection against corrosion lining mixing machine with high density solvent or the metering of its Synergist S-421 95 aqueous solution, make it in the reaction of self-heating under normal pressure and the certain temperature or half self-heating concentrated phase after 0.5-2.0 hours, send leaching prosess or pile to make it continue autothermal reaction 1-30 days on the protection against corrosion ground, send down operation again.This method is than prior art, and the object leaching yield improves 20-50%, and molten time, protection against corrosion expense and the construction investment of soaking reduces more than 30-50%.
Description
The invention belongs to a kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material.
At present wet metallurgical method processing object comprised contain the periodic table of elements the 1st to the VIII subgroup all with the 1st to VI main group part metals, the oxygen of non-metallic element, sulphur, arsenic compound, carbonate, vitriol, silicate and metal form material, use solvent to comprise acids such as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, bases such as caustic soda, ammoniacal liquor, salt such as hydrogen, hydrogen sodium, the sulfide of sodium, potassium, sodium, ammonium, iron, calcium, the villaumite of copper, clorox, iron, ferrous, the vitriol of ammonium, sodium cyanide, and organic amine, water, carbonic acid gas, hydrogen peroxide, chlorine, oxygen etc.
So far, hydrometallurgy exists a kind of pattern from the method that solid materials extracts metal or non-metallic element or its compound, promptly certain solid materials that contains object is crushed to certain granularity, adopting the aqueous solution of being furnished with certain solvent or its Synergist S-421 95 to leach then extracts, comprise dump leaching, drill traverse, heat or do not heat, methods such as pressurization or non-pressurized stirring drill traverse, the metal of aforesaid method, the leaching velocity of nonmetal object, leaching yield, leach liquor concentration and chemical ingredients are subjected to by the specific surface area of extract, leaching agent concentration, extraction temperature, extraction time, reaction product is from solid surface or the speed that removes of inside and the economy of different extract technology methods, the control of many factors such as task difficulty.
As mentioned above, at present Wet-process metallurgy method shows following several aspect in the face of complicated and diversified processing materials like this and employed solvent and fail to adapt with it in many links or main aspect on the processing method:
One, operating efficiency is low.Show to raw materials quality require high, leaching cycle is long, leaching yield is low, for example electric zinc raw materials for production are limited to higher-grade zinc sulfide concentrates calcining, the reducing roasting oxidation flue dust of residues containing zinc, lapis calaminaris and smithsonite ore etc.The zinc leaching rate 73-82% of factory that soaks in adopting one section, quantity of slag 30-36%, slag contain zinc 18-28%.The factory that soak in adopting one section, one section peracid high temperature leaches, process complexity, operational difficulty, equipment corrosion are heavy, and the quantity of slag is growing on and on, and zinc leaching rate is not seen increase, silver-colored recovery rate in ore-dressing 20-30% only in the slag, mine tailing contains 450-500g/tAg.Other adds in May, 1981 Canada's metallurgy meeting will, and ((CIM Bulletin May 1981) carries, produce the Canadian Cominco company zinc of 270,000 t electricity zinc per year and press " oxygen the is pressed the acidleach zinc ore concentrate " patent of invention of soaking pilot plant E, C, Parker, in 145-150 ℃, oxygen partial pressure 600-700kPa, under the total pressure 1140kPa, carry out three sections oxygen and press leaching, equipment and technology requires height, corrosion is heavy, electric energy and heat energy consumption is big, be limited to the concentrate of processing, fail in industrial enforcement so far greater than 40%Zn.
In recent years, the factory of several direct acidleach high silicon zinc oxide crude ore stones appears in area, Yunnan-Guizhou, river, and ore contains zinc greater than 30%, and zinc leaching rate 40-70%, slag contain zinc 12-18%.
Again for example, for being crushed to 6-16mm, 0.27-2.20%Cu cupric oxide raw ore.Sulfuric acid is made leaching agent, and when carrying out drill traverse, dump leaching, leaching cycle respectively is 8-15 days and 40-180 days, and the leach liquor cupric respectively is 12-18g/L and 0.75-3.42g/L, need or send extraction with the iron sheet displacement.
Two, equipment corrosion is heavy.Containing III often need adopt severe corrosive, volatile concentrated hydrochloric acid, nitric acid, hydrofluoric acid and various chloride salt solvent could effectively to leach under High Temperature High Pressure to the material of VI subgroup rare metal, rare earth metal, cause equipment corrosion heavy, must adopt the leaching plant of expensive corrosion resistant material lining cutting, when for example hydrochloric acid decomposes preroasting sheelite, wolframite concentrate, adopt the reactor of vulcanite, graphite brick, enamel one class material lining.Again for example, when hydrofluoric acid decomposes tantalite, niobite and sipylite concentrate and so on material, adopt the container of lining Mo-Ni alloy, tantalum etc., and operating environment is abominable.
Three, the solvent consumption rate is big.Adopt hydrochloric acid, hydrofluoric acid, nitric acid equal solvent, its 2-4 that is generally theoretical value with the proportioning coefficient of excess that is leached object in the material doubly in the operation.
The objective of the invention is to adopt a kind of hydrometallurgy material treatment process to improve the leaching yield and the leach liquor concentration of metal, nonmetal object, shortening is gone into drill traverse and is gone out the time, most of corrosion of getting rid of valuable equipment, or avoid adopting this kind equipment.And make and fail some mineral products material, stacking or the depleted waste residue waste material of processing and utilization and obtain processing and utilization.
For above-mentioned purpose, the present invention realizes like this.
Leach metal in the operation according to hydrometallurgy, the leaching velocity of contained object in the non-metallic minerals material, leaching yield generally is with solvent strength in the leaching agent, the increase of extraction temperature, the prolongation of extraction time and the regularity that increases or increase considerably, employing is under normal pressure, mix and stir mixing or granulation leaching in material and high density solvent or the solvent Synergist S-421 95 aqueous solution metering input mixing equipment, make it carry out self-heating or half self-heating concentrated phase reaction pre-treatment at a certain temperature, level of response or directly send dissolving and leach operation on the estimation then, perhaps be discharged to feed bin, or on the protection against corrosion ground in stock ground, make it proceed self-heating concentrated phase reaction process for some time, fully finish the combination reaction of object, next step can be shortened dissolve extraction time and reach high leaching yield.Thereby (1) has got rid of the control of equipment used device corrosion to reaction process owing to adopted the simple inexpensive corrosion protection equipment of broad big volumetrical to replace valuable corrosion protection equipment.(2), be not subjected to the restriction of factor such as leaching plant corrosion because most of reaction process is carried out, and the reaction times is obeyed the reaction requirement, and is changeable in mixing equipment and in feed bin, stock ground.(3) be beneficial to adopt that reaction is slow, light, the few volatilization of corrosion, solvent cheap and easy to get, as when hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid all can be used as solvent, selection sulfuric acid.(4) pre-treatment job is the chemical reaction that carries out under the agent of high solid loading high density solvent extraction under normal pressure, so the reaction heat that is fully utilized with the accelerated reaction process, reduces or get rid of heat supply, voltage supply facility to reaction process.Therefore, compared with the prior art, the net effect of present method is that the object leaching yield increases 20-50%, goes into groove time shortening 1/2-5/6, and the protection against corrosion expense reduces 50-90%, and the leaching section construction investment reduces 30-50%.
Below the present invention is done further detailed description.
Content of the present invention comprises processing method, equipment and to three aspects of the scope of application of material.
One, processing method.Processing method of the present invention is to containing metal, the material of nonmetal object adopts normal pressure, self-heating or half self-heating concentrated phase reaction pre-treatment, promptly being crushed to the certain particle size scope or being that fine-grained solid materials and high density solvent or its Synergist S-421 95 and other additives (comprise oxygenant originally, reductive agent, promotor, inhibitor, adjust that range request was complied with in agent and different) metering of aqueous solution leaching agent drops into slowly to mix in the mixing machine or granulate and makes its self-heating or half self-heating concentrated phase reaction pre-treatment under normal pressure and certain temperature note regulating compound and be loose shape wet feed to predetermined object level of response.Send dissolving then or directly and leach operation, or be discharged on the protection against corrosion ground in feed bin or stock ground, pile high 2-6m stockpile, make it proceed self-heating concentrated phase reaction pre-treatment, fully finish the combination reaction of object, send subsequent processing again.
Under the felicity condition, most of solid materials can the self-heating concentrated phase react, and handles the caustic soda or the soda agglomerate material of zircon ore concentrate as adopting concentrated sulfuric acid aqueous solution, perhaps zinc sulfide concentrates calcining, perhaps during the copper glance concentrate, strong reaction, process self-heating, temperature reach 115-200 ℃.The reaction heat of process self be enough to support chemical reaction continue carry out and the high as far as possible level of response of the thing that achieves the goal.Some metalliferous mineral material wherein, as contain III some metalliferous material to the VI subgroup, when adopting soda acid salt or its Synergist S-421 95 aqueous solution to handle, perhaps its mineral itself are difficult to leach, the mineral content of perhaps participating in reaction is few, the shortage of heat of reaction output is to keep the desired temperature levels of reaction process, for example 95-2000 ℃ the time, then adopt outer heating means postreaction institute heat requirement, the method of supplementary heating can be respectively to the leaching agent aqueous solution and solid materials preheating before the material pre-treatment, when the warm phegma, also can make it be concentrated to certain concentration, get rid of " tripe rises " problem of the closed circuit middle liquid stream of circulation.
The leaching that the pre-treatment material is finished after the reaction process is different with the conventional content that leaches, mainly be to the dissolving of reaction product in the pre-treatment material, leaching is in second, the operational method that dissolving is leached is to control that leach liquor concentration reaches or a little less than the optimum concn of next step operation, further shorten the activity duration and reduce heat supply.
Two, equipment.Adopt the garden tube mixing machine of ordinary steel, stainless steel or wooden garden tube that required volume in mix, mixing or the granulation of pre-treatment material and the reaction process is provided.Its design conditions is: the overall dimensions of (1) mixing machine garden tube: diameter and length ratio should equal 1: 3-4, its minimum diameter should be not less than and make the people can go into interior size of overhauling, i.e. 2m.(2) garden tube protection against corrosion liner can adopt goods or other non-metallic material or alloy materials such as rubber, graphite, silicon carbide, or not lined, decides on employed solvent and reaction property.(3) establish fixing or adjustable scraper plate in the tube of garden, reserve the 30-70mm gap between scraper plate and the protection against corrosion inner lining surface, promptly reserve one " the buffering bed of material " in order to the wearing and tearing and the mitigate corrosion of protection to liner.(4) garden tube mixing machine material feeding end is established exhaust facility, and discharge end is established able to turn on or off sealing cover.(5) the moving part of garden tube mixing machine body adopts the moving system of tire sets body than large equipment, adopts the moving system of conventional rim gear wheel-carrying roller body than skinny device.
Feed bin, stock ground earth material are based on the pitch mix; then lay the corrosion-resistant coating of materials such as rubber, graphite, silicon carbide during deep-etching solvents such as use hydrochloric acid; protection against corrosion ground and new reaction storeroom are established the metalloid material framework of pitch stain wooden frame or stainless steel; filling quartz sand material or process leached mud therebetween; reserve one " the buffering bed of material " and do not destroyed by discharging machinery in order to protection protection against corrosion ground and its water seepage drainage facility that is provided with down, and mitigate corrosion.
Three, present method disposables material package is drawn together and is contained part metals, the non-metallic minerals solid materials to the most of and III of VIII subgroup to the VI main group of I in the periodic table of elements.For example, cupric, silver, oxidation of sulfureted copper mine beyond the chalcopyrite of gold, copper sponge, composition brass, copper cobalt sulfuric acid salt mine, the aphthonite that contains arsenic antimony, copper glance, native silver, the native state ore, contain zinc, the zinc sulphide calcining of cadmium, the zinc oxide raw ore, zinc soaks slag, Spongy Cadmium, iron Cu, Ni and Co zinc vulcanizing mine stone, contain rare earth, lanthanum, the monazite concentrate of actinium family, hamartite monazite collective concentrate, soda roasting rare earth material, carbonic acid gangue uranium ore and contain rare earth, the loparite concentrate of niobium tantalum, niobium tantalum cerium ore deposit, titaniferous ilmenite, titanium slag and zirconic alkali or soda roasting zircon water logging slag, the sheelite of tungstenic, wolframite, the mixing ore deposit of wolframite sheelite, tungsten medium tin ore and the brightness concentrated molybdenum ore that contains molybdenum, the molybdenum calcining, ammonia soaks high tungsten slag, the prereduction cobalt oxide nickel minerals that contains cobalt nickel, ammonia caustic dip formula nickelous carbonate material, cupric sulfide cobalt concentrate oxidation calcining, matte nickel material, aluminiferous hydrargillite stone ore, plumbiferous plumbous oxide, lead sulfide, the chlorination lead ore, lead vitriol, the carbonic acid lead ore, stanniferous stannic oxide concentrate, the tin scum silica frost is (leaded, bismuth, iron, tungsten, arsenic, antimony, copper, impurity such as silver), medium tin ore (contains, plumbous, iron, bismuth), stibiated stibnite concentrate, tetrahedrite, jamesonite and bismuthiferous tin arsenic hang down bismuth mineral, cupric sulfide bismuth collective concentrate, Cu, Ni and Co bismuth polymetallic ore, the bismuth-containing copper fumes, the bismuth chats, tin arsenic bismuth chats, and the material that contains selen-tellurjum.
The solvent that uses comprises that sulfuric acid in the acids, hydrochloric acid, nitric acid are based on the former, bases has caustic soda, ammonia, salt has vitriol, iron, copper, sodium, the calcium of iron, ferrous, sodium, ammonium, the villaumite of ammonium, soda, sodium bicarbonate, sodium sulphite, sodium bisulfide, clorox and sodium cyanide, potassium or the like.Solubility promoter comprises oxygenant, reductive agent, promotor, inhibitor and adjustment agent.
Introduce embodiments of the invention below.
The sulfuric acid pre-treatment of 1 one kinds of zinc sulfide concentrates calcinings of embodiment is molten soak and soak the back slag sulfuric acid, the villaumite pre-treatment is molten soaks
One, raw material: the zinc sulfide concentrates calcining, granularity 70%-0.074mm, 50%-0.043mm, chemical ingredients is
Chemical ingredients Zn Pb Cd Cu Fe Sb As S
% 65.47 1.37 0.72 0.08 2.80 0.027 0.028 2.70
Chemical ingredients Ce Ge F SiO
2Al
2O
3CaO MgO Agg/t
% 0.05 0.007 0.018 4.65 1.36 1.80 0.92 211.13
Two, solvent: industrial sulphuric acid, ferric sulfate, iron(ic) chloride, salt
Three, processing method:
With above-mentioned zinc baking sand and zinc baking sand: water: sulfuric acid: the ferric sulfate weight ratio is 1: 1.4-1.5: 1.25: 0.03 the Synergist S-421 95 aqueous solution (water and vitriolic metering can be the calculated amount of waste electrolyte and industrial sulphuric acid) metering in batches drops in the tube mixing machine of rubber lining garden mixing slowly and is loose shape wet feed and makes it in normal pressure and 105-115 ℃ of following self-heating concentrated phase reaction 0.5-1.0 hour, is discharged to then to pile high 2-6m stockpile on the pitch mix ground of feed bin and make it proceed self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reached and estimates level of response, promptly metering dropped into slowly in the leaching vat that pump into a washery slag phegma in advance in normal pressure and 65-95 ℃ and stirs molten soaking down in batches, and control filtrate contains 170-180g/LZn, 20-40g/LH
2SO
4Give in next step and deironing, zinc powder send electrolysis after purifying copper removal, cobalt and cadmium.Leached mud send slag to handle through three sections countercurrent washings, and filtrate purifies slag and send cadmium, copper to extract.The molten result that soaks of zinc baking sand sulfuric acid pre-treatment: zinc leaching rate 95-96%, slag contains 8.14%Zn, 11.84%Pb, 1866.18g/tAg.
Last leached mud adopts 1N H
2SO
4, 300g/L NaCl, 5%FeCl
3Synergist S-421 95 carries out that pre-treatment is molten soaks, and leach liquor is in pH=0.5-1.0, and with sheet lead displacement silver, back liquid crystal goes out lead chloride or purifying electrolysis lead under normal pressure and 70-90 ℃.Metal leaching rate 99%Pb, 98%Ag, slag send pyrogenic process to reclaim zinc germanium, and finishing slag discards.
Molten the soaking of sulfuric acid pre-treatment of 2 one kinds of copper sulfide concentrates of embodiment
One, raw material: copper sulfide concentrate, granularity 75%-0.074mm, copper accounts for 73.3% in the copper glance, and chemical ingredients is
Chemical ingredients Cu Fe Pb Zn S Agg/t Seg/t
% 25.11 1.51 0.01 0.02 14.50 1850 1280
Chemical ingredients SiO
2Al
2O
3CaO MgO
% 21.34 3.21 2.60 0.35
Two, solvent: industrial sulphuric acid, ferric sulfate
Three, processing method:
With above-mentioned copper ore concentrates and ore: water: sulfuric acid: ferric sulfate was by weight 1: 1: 1: 1.78 the aqueous solution measures in batches and drops into slowly that mixing is loose shape wet feed in the tube mixing machine of rubber lining garden, make it react 0.5-1.0 hour in normal pressure and 105-115 ℃ of following self-heating concentrated phase, be discharged to then on the feed bin pitch mix ground, pile high 2-6m stockpile and make it proceed self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reached and estimates level of response, promptly metering dropped into slowly and pumps in advance in the leaching vat of a washery slag phegma in batches, stirred molten soaking down in normal pressure and 65-95 ℃, and the control leach liquor contains 80-110g/LCu, 20-40g/LH
2SO
4, or send electrolysis behind the iron purification, aluminium, or crystalline substance goes out blue stone and reclaims silver.
The molten result that soaks of pre-treatment: metal leaching rate 90.72%Cu, 75.84%Ag, slag rate 77.32%, slag contains 4.55%Cu, 499.43g/tAg, 12.19%S.Send pyrogenic attack behind this slag flotation enriching Cu silver and the selenium.The molten infuse of embodiment 3 siderite sulfuric acid pre-treatment is made ferrous sulfate
One, raw material: the spathic iron ore raw ore, chemical ingredients is
Chemical ingredients Fe Cu Au g/t
% 48.10 0.5-0.8 1-4.63
Two, solvent: industrial sulphuric acid
Three, processing method:
" thermal explosion " became powder when last siderite was rich in before gold, copper and the smelting agglomeration, should not be used for ironmaking, can be used for replacing iron filings manufacturing ferrous sulfate.
Above-mentioned siderite is crushed to-1mm be preheating to 95-105 ℃ washery slag phegma and aqueous sulfuric acid by ore: acid: water is that 1: 1: 1.2 weight ratio is measured in batches and dropped in the tube mixing machine of rubber lining garden mixing slowly and make it in normal pressure and 95-105 ℃ of following self-heating-half self-heating concentrated phase reaction 0.5-1.0 hour, directly input pumps in the leaching vat of process phegma in advance then, under 65-95 ℃, carry out and stir molten soaking, note keeping leach liquor to contain Fe
2+100-140g/t, inferior adding iron filings remove Fe
3+, solid-liquid separation then, leach liquor slowly is cooled to 15 ℃, and crystalline substance goes out seven water iron vitriol coarse-grain products, and slag send copper, gold to reclaim.
The water that last Xiang Qishui alum adds its half weight is heated to 65 ℃ of dissolvings, and the crystalline substance of lowering the temperature again goes out seven water alum products.Or be heated to＞95 ℃, make the dehydration of seven water alum form white powder, filtration washing removes residual impurity, dissolves crystalline substance again and goes out pure seven water alum products, leaching yield 99%.
The molten infuse of sulfuric acid pre-treatment of embodiment 4 titanomagnetite smelted furnace cinders is made rutile
One, raw material: the titaniferous smelted furnace cinder, granularity-0.1mm contains anosovite 76%, and chemical ingredients is
Chemical ingredients Fe FeO TiO
2V
2O
5P
2O
5S
% 3.07 4.00 66.00 0.19 0.37 0.006
Chemical ingredients SiO
2Al
2O
3CaO MgO MnO
% 8.80 13.72 1.73 8.61 1.12
Two, solvent: industrial sulphuric acid
Three, processing method:
With above-mentioned being crushed to-0.1mm titanium slag be preheated to 105-115 ℃ sulfuric acid phegma Synergist S-421 95 by pulp water acid weight ratio be 1: 1: 1.6 in batches metering drop into slowly that mixing is loose shape wet feed in the tube mixing machine of rubber lining garden, make it react 1-2 hour in normal pressure and 160-200 ℃ of second self-heating concentrated phase of supplementary heating, be discharged to then on the pitch mix ground of feed bin and push into high 2-6m stockpile, make it proceed self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reached predetermined level of response, metering dropped in the leaching vat that pump into a washery slag phegma in advance slowly and stirred the molten 1-2 of soaking hour down in 65-95 ℃ in batches, solid-liquid separation then, and leach liquor adds iron reduction Fe
3+Be Fe
2+, being cooled to about 15 ℃, crystalline substance goes out the ferrous salt deironing.Add the crystal seed crystalline substance again and go out metatitanic acid, through hydrofluoric acid wash, drying, calcine under＞950 ℃ 97.41%TiO
2The rutile particles product, brilliant back liquid adds in the lime and the back discharging.
Molten the soaking of sulfuric acid pre-treatment of embodiment 5 zircon ore concentrate alkali roasting piece washery slag
One, raw material: zircon ore concentrate caustic soda (or soda) agglomerate washery slag, surmise-0.1mm, contain 32.2%ZrO
2
Two, solvent: industrial sulphuric acid
Three, processing method:
Above-mentioned washery slag system is broken to zircon alkali roasting piece-0.1mm after, contain the washery slag of gained behind the impurity such as 5-10%HCl cold fluid flush away water glass and calcium salt through employing.
Above-mentioned washery slag and the Synergist S-421 95 that is 1: 1: 1 slag, sulfuric acid and water by weight measured in batches drop in the tube mixing machine of rubber lining garden mixing slowly and be loose shape wet feed and make it in normal pressure and 150-200 ℃ of following self-heating concentrated phase reaction 1-2 hour, then or be discharged on the feed bin pitch mix ground, pile high 2-6m stockpile and make it proceed self-heating concentrated phase reaction process 1-30 days, or directly send operation down.
After last pre-treatment material finished and estimated level of response, adopt a washery slag phegma to carry out down in 65-96 ℃ and stir molten soaking, keep leach liquor to contain 120-130g/L Zr, zirconium is with ZrOSO
4And H
2ZrO(SO
4)
2Form enters solution, and silicic acid dehydration is stayed in the slag, zirconium, hafnium leaching yield 98%, uranium, thorium transformation efficiency each 90% and 60%.
Last leach liquor adds equal-volume sulfuric acid and promptly separates out white zirconium crystal, and zirconium deposition rate 95% adds to form the aqueous solution and add the sulfuric acid crystalline substance again with the water of weight with crystal again and goes out zirconium sulfate crystal, Zr(SO
4)
24H
2O, foreign matter content: Fe, Cu, Ag＜0.10ppm, K, Na, Mg, Si＜10ppm.Calcine under 850-900 ℃ pure zirconium dioxide product.
Molten the soaking of hydrochloric acid pre-treatment of embodiment 6 matte nickel
One, raw material: matte nickel, granularity 80%-0.074mm, chemical ingredients is
Chemical ingredients Cu Ni Fe S
% 26.91 47.82 1.04 21.29
Two, solvent: technical hydrochloric acid
Three, processing method:
Above-mentioned matte nickel powder material and the hydrochloric acid of preheating is measured in batches to drop into slowly and is mixed into loose shape wet feed in the tube mixing machine of graphite lining garden and makes it in normal pressure and 95-105 ℃ of second self-heating concentrated phase reaction 1-2 hour, be discharged to then and pile high 2-6m stockpile on the feed bin graphite ground, make it proceed self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reaches and estimates level of response, in batches metering drops into the graphite that pumps into washery slag phegma and concentrated hydrochloric acid Synergist S-421 95 in advance slowly and serves as a contrast leaching vat in normal pressure and 65-95 ℃ following agitation leach 2-3 hour, filter then, keep leach liquor to contain 120-140g/L Ni, 150-160g/L HCl, Fe, Cu, Cr＜2g/L.
Washery slag send copper to smelt and the recovery platinum family element.Leach liquor is in 65-95 ℃ of following air blast Oxidation of Fe
2+Be Fe
3+, H
2S is that elementary sulfur is removed, and rear filtrate is gone into organic phase with tributyl phosphate (TBP) extraction iron, and two octodrines (TIOA) or the N-235 that handle with 2NHCl make Co
2+, Cu
2+, Zn
2+Deng being complex anion MeCl
2-4 forms are gone into organic phase, Ni
2+Stay aqueous phase.Purifying back liquid composition is, g/L:Ni110-120, and HCl150-170, Co＜0.001 Cu＜0.006, Fe＜0.004 send concentrated crystalline substance to go out NiCl
24H
2The O crystal gets the metallic nickel particulate product through 600 ℃ of following roastings, hydrogen reductions.Nickel extraction yield 98%.
Molten the soaking of hydrochloric acid pre-treatment of embodiment 7 oxidation of sulfureted bismuth raw ores
One, raw material: the bismuth raw ore, granularity-0.1mm mainly is bismuth oxide compound and sulfide in the ore mineral, and little metal bismuth, gangue mineral are quartz, potash feldspar, calcite, and chemical ingredients is
Chemical ingredients Bi Cu Ni Co Fe As SiO
2CaO
% 7.01 1.51 0.15 0.10 15.10 4.55 17.82 3.87
Two, solvent: technical hydrochloric acid
Three, processing method:
Above-mentioned being broken to-0.1mm bismuth raw ore is measured in batches to drop into slowly and is mixed into loose shape wet feed in the tube mixing machine of graphite lining garden and makes it in normal pressure and 95-115 ℃ of second self-heating concentrated phase reaction 0.5-1.0 hour with being preheating to 95 ℃ the one section washery slag phegma and the hydrochloric acid Synergist S-421 95 aqueous solution, be discharged to then and pile high 2-6m stockpile on feed bin pitch mix or the graphite linings ground and make it proceed self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reaches and estimates level of response, in batches metering drops into slowly in the leaching vat that pump into displaced liquid in advance in normal pressure and 65-95 ℃ and stirred the molten 0.5-1.0 of soaking hour down, keep leach liquor pH＞0.8, make copper, nickel, cobalt leach liquid and bismuth is hydrolyzed to BiOCl stays in the slag.Adopt new aqueous hydrochloric acid to leach bismuth down in pH=0.5-0.7 then, the bismuth leach liquor send iron displacement, the bismuth rate of recovery 94.9%.
8 one kinds of tin bismuths of embodiment chats hydrochloric acid-the iron(ic) chloride pre-treatment is molten soaks
One, raw material: tin bismuth chats, granularity 78%-0.074mm, chemical ingredients is
Chemical ingredients Sn Bi Pb Fe As S g/tAg g/tAu
% 4.22 11.49 2.11 17.50 21.30 9.14 211.1 18.3
Wherein the mineralogical composition of bismuth is: 9.11% bismuth metal, 2.20% bismuth oxide, 0.18% bismuth sulfide.
Two, solvent: technical hydrochloric acid, iron trichloride
Three, processing method:
With breeze in above-mentioned be preheating to 95-105 ℃ waste electrolyte, hydrochloric acid and the iron trichloride Synergist S-421 95 aqueous solution by the ore deposit: hydrochloric acid: iron(ic) chloride: the weight ratio of water is 1: 0.48: 0.35: 1, in batches metering drops into slowly and is mixed into loose shape wet feed in the tube machine of graphite lining garden and makes it in normal pressure and 95-115 ℃ of second self-heating concentrated phase reaction 1-2 hour, is discharged to then to pile high 2-6m stockpile on feed bin pitch mix or the graphite linings ground and make it proceed self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reached and estimates level of response, metering dropped into slowly in the leaching vat that pump into a washery slag phegma in advance in normal pressure and 95-115 ℃ and stirred the molten 1-2 of soaking hour down in batches, keeps filtrate to contain 70-80g/L Bi
3+, 50g/L HCl send the purification electrodeposition, and in tin, lead, arsenic, silver, the Jinliu's slag, slag send plumbous arsenic and Xi Yinjin separation and Extraction.Bismuth leaching yield 95-97%, back slag contains 0.36-0.58%Bi, stores up and treats aftertreatment.Molten arsenic removal and the antimony of soaking of the caustic soda of 9 one kinds of copper sulfide concentrates of embodiment-sodium bisulfide pre-treatment
One, raw material: copper sulfide concentrate, granularity 81%-0.074mm, chemical ingredients is
Chemical ingredients Cu Sb As Fe Ag g/t Au g/t
% 17.26 7.11 4.12 23.53 6813 19.76
Two, solvent: caustic soda, sodium bisulfide (NaHS)
Three, processing method:
Molten the soaking of the pre-treatment of this kind copper sulfide concentrate is that batch of material is divided into three equal parts, divides two sections processing.
First section is two parts of concentrate and second section leached mud that contains 4%Sb, 2.5%As and the caustic soda phegma of second section leach liquor after extracting antimony, arsenic and saltcake that is preheating to 105-115 ℃ to be replenished the caustic soda of allocating 1/5 amount into and the metering of the sodium bisulfide Synergist S-421 95 aqueous solution drop into slowly and be mixed into loose shape wet feed in the tube mixing machine of rubber lining garden and make it in normal pressure and 105-115 ℃ of second self-heating concentrated phase reaction 1-2 hour, is discharged to then to pile high 2-6m stockpile on the feed bin pitch mix ground and make it proceed self-heating concentrated phase reaction process 5-30 days.
After last pre-treatment material reaches and estimates level of response, in batches metering drops into slowly in the leaching vat of a washery slag phegma that pumps into first section filter residue in advance in normal pressure and 105-115 ℃ and stirred the molten 1-2 of soaking hour down, leached mud filters, the slurry of resetting adds sulfuric acid and is neutralized to pH=7, refilters dryly must contain 20.3%Cu, 0.1-0.2%Sb, 0.3-0.4%As, 7999g/tAg, the 23.2g/tAu prefinished products is invested market.
Second section is that another part concentrate is dropped into slowly and is mixed into loose shape wet feed in the tube mixing machine of rubber lining garden and makes it in normal pressure and 105-115 ℃ of second self-heating concentrated phase reaction 1-2 hour with being preheating to first section leach liquor of 105-115 ℃ and first section slag washing liquid Synergist S-421 95 metering, is discharged to then to pile high 2-6m stockpile on the feed bin pitch mix ground and make it proceed self-heating concentrated phase reaction process 5-30 days.
After last pre-treatment material reaches and estimates level of response, in batches metering drops into slowly in the leaching vat that pump into second section leached mud primary wash liquor in advance in normal pressure and 105-115 ℃ and stirred the molten 1-2 of soaking hour down, filter residue returns first section pre-treatment, and filtrate send down operation to extract sodium antimonate, NaSb(OH)
6The saltcake product, Tricalcium arsenate, Ca
3(AsO
4)
2Send and forever store up the field.
Molten the soaking of caustic soda pre-treatment of 10 1 kinds of wolframites of embodiment, sheelite collective concentrate
One, raw material: wolframite, sheelite collective concentrate, granularity 90%-0.074mm, chemical ingredients is
Chemical ingredients WO
3Mo P
2O
5As SiO
2CaO
% 56.3 4.5 0.06 0.01 5.0 3.5
Two, solvent: caustic soda, soda
Three, processing method:
With above-mentioned black and white tungsten collective concentrate be preheating to two times of mol ratios of 105-115 ℃, the soda Synergist S-421 95 aqueous solution that concentration 600g/L NaOH and CaO equivalent are 1.1 times measures in batches to drop into slowly and is mixed into loose shape wet feed in the tube mixing machine of rubber lining garden and makes it in normal pressure and 105-115 ℃ of second self-heating concentrated phase reaction 0.5-1.0 hour.Be discharged to then and pile high 2-6m stockpile on the feed bin pitch mix ground and make it under normal pressure, proceed self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reached and estimates level of response, metering dropped in the leaching vat that pump into a washery slag phegma in advance in normal pressure and 105-115 ℃ and stirred WO the molten 1-2 of soaking hour down in batches
3Leaching yield 99%, molybdenum are soaked rate 87%, arsenic and phosphorus leaching yield 60%, and leach liquor concentrates crystalline substance and goes out sodium wolframate, and caustic soda returns pre-treatment in the liquid of recovery back simultaneously.Washery slag send molybdenum to reclaim.
Molten the soaking of caustic soda pre-treatment of 11 1 kinds of monazite concentrates of embodiment
One, raw material: monazite concentrate, granularity 79%-0.074mm, chemical ingredients is
Chemical ingredients RE
2O
3U
3O
8P
2O
5ZrO
2TiO
2Fe SiO
2
% 63.6 0.45 26.1 1.51 1.22 0.52 2.55
Two, solvent: caustic soda, hydrochloric acid
Three, processing method:
The above-mentioned monazite concentrate of preheating and remove sodium phosphate phegma and the caustic soda that are preheating to 105-115 ℃ are fitted in the concentration 75%NaOH aqueous solution and measures in batches to drop into slowly by 1: 1.5 weight ratio and be mixed into loose shape wet feed in the tube mixing machine of rubber lining garden and make it in normal pressure and 120-150 ℃ of second self-heating concentrated phase reaction 1-2 hour.
After last pre-treatment material reached and estimates level of response, metering dropped into slowly in the leaching vat that pump into a washery slag phegma in advance in normal pressure and 105-115 ℃ and stirred the molten 1-2 of soaking hour down in batches, filters, and sodium salt throw outs such as rare earth, thorium, uranium, titanium and zirconium stay in the slag.The alkali liquor concentration crystalline substance that leaches goes out sodium phosphate, and mother liquor returns pre-treatment, adopts the 10%HCl aqueous solution to go into liquid in normal pressure and 95 ℃ of following stirring and dissolving rare-earth hydroxides in rubber lining leaching vat after the residue washing dephosphorization, keeps initial pH＜2, adds RE again
2(OH)
3The backflow slag transfers terminal point pH in 4.0-4.5, makes uranium, thorium and Ce(OH)
4The cerium of form stays in the slag.Refilter, filtrate then concentrates crystalline substance and goes out rare earth chloride coarse-grain product in 70-80 ℃ of quantitative down excess sulfuric acid ammonium and the heavy radium of barium chloride solution hydrolysis of adding, and send extracting and separating cerium, thorium, uranium after filter residue acid is molten.
Rare earth chloride coarse-grain product reheat is in 95-115 ℃ of following water dissolution, add zinc powder, ferrous sulfate and lime make the trace uranium reductive hydrolysis remove qualified rare earth chloride product.
Molten the soaking of clorox pre-treatment of 12 1 kinds of molybdenum glance stones of embodiment
One, raw material: molybdenum glance stone, granularity 50%-0.074mm, chemical ingredients is
Chemical ingredients Mo Cu Fe Bi Pb Re S SiO
2
% 35.3 5.5 12.1 0.10 0.15 0.01 29.6 21.0
Chemical ingredients Al
2O
3CaO MgO
% 2.5 1.2 2.1
Two, solvent: clorox, caustic soda, yellow soda ash
Three, processing method:
To go up a molybdenum glance material and weight ratio Mo: NaClO: Na
2CO
3: NaOH=1: 12: 4: 4 cooperation solvent measures in batches to drop into slowly and is mixed into loose shape wet feed in the tube mixing machine of rubber lining garden and makes its self-heating concentrated phase reaction 0.5 hour under normal pressure with returning the aqueous solution that mother liquor forms, is discharged to then to pile high 2-6m stockpile on the feed bin pitch mix ground and make it continue self-heating concentrated phase reaction process 1-30 days.
After last pre-treatment material reaches and estimates level of response, in batches metering drops into the leaching vat that pump into a washery slag phegma in advance in normal pressure and 65 ℃ molten 0.5-1.0 of soaking hour down, filtrate separation and Extraction molybdenum, rhenium and saltcake, mother liquor returns pre-treatment, filter residue send copper to reclaim, metal recovery rate is 99.5%Mo, 98%Re.
Embodiment 13: a kind of sulfuric acid pre-treatment dump leaching of cupric oxide ore
One, raw material: cupric oxide ore, granularity-6.5mm, cupric 0.4%, The copper thing are that chrysocolla is chessylite and malachite, and gangue mineral is sericite, feldspar, quartzose sandstone, mud stone.
Two, solvent: industrial sulphuric acid
Three, processing method:
With above-mentioned cupric oxide raw ore with leach the metering of the displaced liquid sulfuric acid Synergist S-421 95 aqueous solution drop into slowly be mixed into loose shape wet feed in the tube mixing machine of rubber lining garden after, being discharged to continuously to stack on the pitch mixture ground, stock ground makes it in normal pressure self-heating concentrated phase reaction 24 hours, send then and leach spray leaching 3-5 days, copper leaching rate 78-82%
Improve 18-22% than ordinary method, raw ore acid consumption 34-36kg/t.
Leach liquor contains 3-5g/L Cu, and iron powder replacement output copper sponge contains 82-90%Cu, rate of displacement 97%.
Embodiment 14: a kind of sodium cyanide pre-treatment dump leaching of clay Gold Ore.
One, raw material: the clay Gold Ore, granularity-6.5mm, 1.25-0mm15% contains 3.41g/tAu, 13.64g/tAg.
Two, solvent: nacn
Three, processing method:
Above-mentioned Gold Ore, lime, the concentration 1.0g/L NaCN aqueous solution are dropped into mixing granulation in the tube mixing machine of rubber lining garden slowly by weight metering in 1000: 4: 40.Be continuously discharged into and pile high 2-4m stockpile maintenance 24 hours on the pitch mix ground, stockyard, then leached 5-10 days with extracting gold and silver phegma spray, send activated carbon column three sections absorption, gold and silver raising recovery rate respectively 83.6% and 41.0%, respectively improve 13.3% and 14.3% than conventional dump leaching method, raw ore nacn consumption is reduced to 32g/t by 50g/t.
Claims (6)
1, a kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material is characterized in that: the processing method that material is handled comprises the pre-treatment of material concentrated phase and two aspects of dilute phase dissolving leaching.
A, certain solid materials that is crushed to certain particle size and high density solvent or the metering of its Synergist S-421 95 aqueous solution are dropped into mixing or granulation in the mixing machine that is provided with the protection against corrosion liner, self-heating, half self-heating concentrated phase reaction pre-treatment are 0.5-2.0 hour under normal pressure and certain temperature.
B, according to level of response, last pre-treatment material or directly send dissolving leaching operation; Or be discharged on feed bin or the protection against corrosion ground, stock ground, pile high 2-6m stockpile, make it continue self-heating concentrated phase reaction 1-30 days.
C, go up a pre-treatment material reached estimate level of response after, i.e. metering drops into the leaching plant dissolving and leaches.
2, a kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material is characterized in that: the material of handling comprise contain in the periodic table of elements the 1st to the major part of VIII subgroup and III to the part metals of VI main group, the solid materials of non-metallic element mineral.
3, a kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material is characterized in that: material is handled employed solvent and is comprised weak volatile acid alkali salt class and Synergist S-421 95 thereof; Employed additive comprises oxygenant, reductive agent, promotor, inhibitor and adjustment agent.
4, a kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material is characterized in that: it is a kind of garden tube mixing machine of protection against corrosion liner and protection against corrosion ground in a kind of feed bin or stock ground of being provided with that material is handled employed equipment.
5, handling employed equipment according to the described material of claim 4 is a kind of garden tube mixing machine that is provided with the protection against corrosion liner, it is characterized in that:
The garden tube diameter and the length ratio of a, this garden tube mixing machine equal 1: 3-4, garden tube internal diameter should be not less than 2m.
B, garden tube partly are steel, or stainless steel, or wooden.
The protection against corrosion liner of c, garden tube and scraper plate material, processing is decided with solvent, additive and process chemistry reaction property according to material, can be rubber, graphite, silicon carbide or other non-metallic material, or stainless steel or other alloy materials, or not lined.
Reserve the gap of width 30-70mm between the protection against corrosion liner of d, garden tube and the scraper plate, make its formation " the buffering bed of material ".
The body of e, garden tube moves part, and small device adopts the moving system of rim gear wheel-carrying roller body, adopts the moving system of tire sets body than large equipment.
6, handle the protection against corrosion ground in employed a kind of feed bin or stock ground according to the described material of claim 4, it is characterized in that:
The anticorrosive on a, protection against corrosion ground mainly is the pitch mix, secondly is materials such as rubber, graphite, silicon carbide.
Lay pitch stain yoke on b, the protection against corrosion ground, or stainless steel frame, fillers such as inner filling quartz sand, leached mud prevent discharging physical damage protection against corrosion ground and mitigate corrosion.
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|---|---|---|---|
| CN94111643A CN1093414A (en) | 1994-02-17 | 1994-02-17 | A kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material |
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|---|---|---|---|
| CN94111643A CN1093414A (en) | 1994-02-17 | 1994-02-17 | A kind of concentrated phase pre-treatment solution leaching method of hydrometallurgy material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483372A (en) * | 2016-01-19 | 2016-04-13 | 北京科技大学 | Reaction, separation, washing, evaporation and drying integrated device and method |
| CN109161685A (en) * | 2018-09-11 | 2019-01-08 | 辽宁大学 | A method of based on dynamic adsorption method absorption extraction germanium |
| CN117965884A (en) * | 2024-04-01 | 2024-05-03 | 烟台昌久智能科技有限公司 | Metal ore pretreatment processing device and processing method |
-
1994
- 1994-02-17 CN CN94111643A patent/CN1093414A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483372A (en) * | 2016-01-19 | 2016-04-13 | 北京科技大学 | Reaction, separation, washing, evaporation and drying integrated device and method |
| CN105483372B (en) * | 2016-01-19 | 2018-04-03 | 北京科技大学 | A kind of reaction, separation, washing, evaporation and drying integrated device and method |
| CN109161685A (en) * | 2018-09-11 | 2019-01-08 | 辽宁大学 | A method of based on dynamic adsorption method absorption extraction germanium |
| CN117965884A (en) * | 2024-04-01 | 2024-05-03 | 烟台昌久智能科技有限公司 | Metal ore pretreatment processing device and processing method |
| CN117965884B (en) * | 2024-04-01 | 2024-06-11 | 烟台昌久智能科技有限公司 | Metal ore pretreatment processing device and processing method |
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