CN101973586A - Method for preparing polymeric aluminum ferric sulfate by using aluminium ore washing gangue - Google Patents
Method for preparing polymeric aluminum ferric sulfate by using aluminium ore washing gangue Download PDFInfo
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Abstract
The invention discloses a method for preparing polymeric aluminum ferric sulfate by using aluminium ore washing gangue, which is characterized in that washing gangue or/and brasses of a karst accumulated aluminium ore or other aluminium ores is or are used for preparing high-iron pyritic residue iron powder which reacts with sulfuric acid to generate aluminum sulfate and ferric sulfate water solutions, and then an alkalizer is added for polymerizing to produce the polymeric aluminum ferric sulfate. Meanwhile, the gangue has thinnest granularity, wherein the content of fine silt with the granularity of -10 micrometers accounts for 80 percent, and the fine silt is the optimal raw material for producing the polymeric aluminum ferric sulfate, and has the advantages of high reaction ratio and good product quality. The invention has the advantages of being capable of reasonably and effectively utilizing aluminium ore resources, effectively controlling the aluminium ore washing gangue from a pollution source, protecting the environment, realizing the harmony of human beings and the environment, lowering the production cost of the polymeric aluminum ferric sulfate and realizing high-efficiency recycling economy.
Description
Technical field
The invention belongs to mine tailing and handle and the Water Treatment Chemicals technical field, relate to a kind of method for preparing PAFS with aluminium ore washing mine tailing.
Background technology
Current, the bauxite resource of China is abundant, is obtaining the fine metallic aluminium simultaneously, has produced a large amount of waste residues, useless mud, particularly mine tailing very difficult natural subsidence under state of nature, stores up extremely difficult.With regard to one of the main aluminium production base of China Pingguo aluminium, annual meeting produces about 2,000,000 tons of mine tailings, and the geographic landforms in Baise at aluminium place, Pingguo are based on karst, the various karst structure in mining area are complete, tomography, lapies fluid bowl are crisscross, sludge after the discharging has formed the sludge storehouse, and environment is on every side had very big influence, has very big potential risk.The mine tailing of comprehensive reutilization wash to(for) choosing is very necessary.
China's main inorganic flocculating agent now mainly contains Tai-Ace S 150, aluminum chloride, ferric sulfate, iron(ic) chloride etc., and the polymer inorganic flocculating agent mainly contains polyaluminium sulfate, bodied ferric sulfate, polymerize aluminum chloride, poly-ferric chloride etc.These inorganic flocculating agents are because demand is big, polymer inorganic flocculating agent polyaluminium sulfate particularly, and it purifies turbidity removal decolorizing effect and is better than polymerize aluminum chloride and aggregated flow acid iron, is a kind of highly effective inorganic high molecular water purifier.We from relevant literature search to correlation technique, take passages as follows:
1. Chinese patent CN1219507A discloses a kind of " ferric polysulfate solid is criticized sb's faults frankly the aqua one-step method production process ", utilizes Steel Plant and vitriol works to contain ferric oxide waste residue and oxidant reaction, produces the ferrous solid water purification agent bodied ferric sulfate.This patent application only is in the laboratory test stage, the sulfuric acid gradation will be added among the embodiment to contain in the beaker of ferric oxide waste residue, and temperature of reaction need be controlled at 40-70 ℃, this is difficult for grasping in actual production, in addition, production process is oxidizer not, and ferrous iron can not change into ferric iron, do not reach polymerization effect, and material is impure in the scum, and solid, liquid does not separate, and water-insoluble is too high, influence purifying water effect, do not possess suitability for industrialized production.
2. Chinese patent CN1337356A discloses a kind of " production technique of aluminium iron sulfate polymer as composite water purifying agent ", utilize vitriol works's waste residue production PAFS, Fe2O content is 40-70% in the waste residue, Al2O content is 15-20%, by stoichiometry, leaching yield 60-80%, complex acid concentration 45-50%, sulfuric acid concentration are 92.5-98%; Production technique is as follows: according to stoichiometry, earlier water is added in the reactor, slag is poured into again, add sulfuric acid then, airtight natural reaction two hours; The water that adds above-mentioned isodose in the reactant dilutes, and the reactant after will diluting then enters subsider, adds a spot of flocculation agent natural subsidence, precipitates 2-4 hour, solid-liquid separation, and the clear liquid pH value is controlled at about 2; Above-mentioned clear liquid is squeezed into aggregation container, according to Fe
2+Content adds H
2O
2, H
2O
2Enter clear liquid by the container bottom sprinkling,, make Fe with the quick oxypolymerization of clear liquid
2+0.2 of content promptly gets the PAFS finished fluid.Material behind the extraction finished fluid is washed, and the secondary wash water can add in the reactor and sulfuric acid reaction, and one time wash water can be used for the diluting reaction thing.The flocculation agent that adopts is a polyacrylamide.Above-mentioned PAFS finished fluid is through dehydration by evaporation, and degree Beaume is controlled at 58-60 °, and spontaneous nucleation after the discharging is broken into granular or powdery then, promptly gets solid polymeric aluminum ferric sulfate.There is following deficiency in this patent: (1) is burnt iron, aluminium content difference in the slag, thereby ferric sulfate, Tai-Ace S 150 content in the finished product PAFS can't be regulated because of the place of production difference of sulfurous iron ore, can not make the product adaptation market demand; (2) waste residue reaches without fragmentation and only utilizes vitriolic dilution heat release to keep reaction, and reaction is carried out not thorough; (3) use fully extractive reaction thing of flocculation agent natural subsidence three times, product yield is low, and finally the flocculating settling thing is unprocessed causes secondary pollution.
3. Chinese patent CN1600457A discloses a kind of " sulfurous iron ore comprehensive utilization method ", be that Tai-Ace S 150 and sulfate cinder and sulfuric acid polyreaction are produced PAFS, its feature may further comprise the steps: (1) will burn slag and select to such an extent that high ferro is burnt slag and pulverized with magnetic separator; (2) add liquid aluminium sulfate in proportion, high ferro is scratched the sealing back metering of ground-slag material and is pumped into sulfuric acid, keeps certain temperature and pressure, carries out polyreaction and react a timing and ask in reactor; (3) reaction finishes, and first-time filtrate adds oxygenant oxidation Fe
+ 2, becoming liquid product after making it drop to certain numerical value, secondary cleaning water returns produces liquid aluminium sulfate; (5) wash filter residue with clear water, waste water in neutralizing tower and the back discharge; (6) filter residue with after low iron burns slag mixing seasoning as cement filler; (7) liquid product through concentrate, dry after the powdering product.In the above-mentioned technical process, high ferro is burnt slag can be crushed to the 60-100 order, and reaction conditions is: utilize the dilution heat energy of the vitriol oil, keeping temperature of reaction is 100-115 ℃; Pressure is 0.01-0.03MPa; Time is 1.5-3 hour.First-time filtrate makes Fe with oxygenant
+ 2Drop to after 0.2% and make liquid product, liquid product can pass through vacuum concentration, spraying drying, after make the pulverulent solids product.Sulfurous iron ore according to various different components, providing a kind of can both increase economic efficiency according to the dissimilar polyaluminium sulfate iron product of market demand, had expanded sulfuric acid market again, and solved the secondary pollution of filter residue, can improve the economic benefit of existing gas washing in SA production significantly.
4. Chinese patent CN 1136535A discloses a kind of " poly aluminium chloride iron and polyaluminium sulfate iron product and technology ", after its technology is pulverized bauxite, add in the reactor, add hydrochloric acid or sulfuric acid then, in temperature is that 80-100 ℃, pressure are to react under 3-5 the normal atmosphere, carries out its mixture should being poured in the agitated pool of reaction in 2-5 hour, when temperature is 60-75 ℃, add entry and high alumina ash, churning time is that precipitation, separation in 1.5-4 hour get.The proportioning raw materials of described poly aluminium chloride iron is: bauxite 12-18%, high alumina ash 8-10%, 30% hydrochloric acid 35-42%, water 30-45%.The proportioning raw materials of described PAFS is: bauxite 14-18%, high alumina ash 0.26-5%, 90% sulfuric acid 20-35%, water 46.5-65.7%.
5. Chinese patent CN1583593A discloses a kind of " utilizing the technology of industrial residue one-step synthesis inorganic macromolecule flocculant poly aluminium iron sulfate ", be to make host with industrial residue, flyash is auxiliary agent, adopts one-step synthesis synthesizing inorganic macromolecule flocculant one PAFS; In building-up process, with sulfuric acid, the mixed in hydrochloric acid acid of sulfuric acid or 1: 1, the raw material diel is soaked in 50-100 ℃ of stirring down, and as adding auxiliary agent, its concrete steps are as follows behind the suction filtration:
A. raw material is selected for use: industrial residue is a raw material, mainly comprises: steel mill's waste residue, waste Aluminum slag, power plant's electrostatic precipitator flyash, vitriol works's waste residue etc. and contain a certain amount of molysite and aluminium salt material;
B. pre-reaction: 100g places there-necked flask with material (one of steel-making waste residue, waste Aluminum slag, power plant's electrostatic precipitator flyash, kaolin), add water 100g, the vitriol oil that slowly adds 65mL while stirring, be warmed up to 60-80 ℃, pre-reaction 15-25 hour, make the iron in the material be dissolved in the liquid phase to greatest extent;
The C polyreaction: be warming up to 90-120 ℃, polyreaction 2-6 hour, the reactant that takes a morsel was surveyed iron and ferrous content, looked how many decisions of ferrous ion and added catalytic oxidant and add-on.And slowly interpolation increases poly-agent, to increase the basicity of product;
D reacts again: be cooled to 85-110 ℃, add the interpolation auxiliary agent of metering, reacted 10-15 hour;
E keeps reaction: is cooled to 65-85 ℃, kept 1-3 hour, and standing over night, product divides liquid and solid slag two-layer, and the upper strata is product.PAFS solution russet; The OH/Fe+AL mol ratio surpasses 1.5 product and places a few hours and become yellow-green colour colloidal sol.
Described primary industry waste residue mainly comprises: steel mill's waste residue, waste Aluminum slag, power plant's electrostatic precipitator flyash, vitriol works's waste residue, kaolin and contain a certain amount of molysite and aluminium salt material; When using steel-making waste residue, its granularity is 300 orders; When using waste Aluminum slag, its granularity is 200 orders; When using power plant's electrostatic precipitator flyash, its granularity is 300 orders; When using kaolin, its granularity is 200 orders.
Selecting for use of described catalytic oxidant: be to select for use to contain a large amount of bhO
2The low-grade manganese ore that contains of the waste in mine.
6. Chinese patent CN 101279756A discloses a kind of " preparation of polyaluminium sulfate ", and the polyaluminium sulfate preparation is by Tai-Ace S 150: water: phosphoric acid: sodium metaaluminate, 0.8-10.0: 0.00-10.0: 0.01-0.1 by weight: 0.10-2.0 hybrid reaction.Tai-Ace S 150: water: phosphoric acid: sodium metaaluminate weight ratio 1.0-8.0: 0.00-8.0: 0.02-0.06: 0.20-1.20.Said Tai-Ace S 150, solid alumina content are greater than 15.5%, and liquid oxidation aluminium content is greater than 7.6%.Said phosphoric acid is content greater than 85% high-concentration phosphoric acid.Said sodium metaaluminate makes for sodium hydroxide and the industrial aluminium hydroxide reaction by sodium al mole ratio 1.05-1.5.Hybrid reaction is for heating 40-100 ℃, 0.5-8.0 hour digestion time.The digestion temperature is 55-85 ℃, and the digestion time is 0.5-3.0 hour.
7. Chinese patent CN9U04676.3 discloses a kind of " liquid palymeric aluminium sulfate preparation method ", with aluminiferous bauxite mine and sulphuric acid soln reaction, prepare certain density aluminum sulfate aqueous solution, under agitation carry out polyreaction with alkaline earth metal compound or ammonia again, polymer material is through solid-liquid separation, remove the vitriol of impurity and alkaline-earth metal, polyaluminium sulfate filtrate.This method is two step method reaction, and defective is that main raw material white lime produces in sulfuric acid insolubles waste residue and the alkaline-earth metal in the bauxitic clay calcium sulfate is carried polyaluminium sulfate secretly and formed waste residue, and because of not containing Al in alkaline earth metal compound or the ammonia
2O
3Effective constituent, gained polyaluminum sulfate aluminum solutions effective constituents A l
2O
3Percentage composition has only 5-7%.
8. Chinese patent CN94116651.1 discloses a kind of " polyaluminium sulfate production technique ", comprises successively: (1) unslaked lime adds the water reaction, crosses the elimination throw out and gets white lime Ca (OH)
2Slurry, (2) add Tai-Ace S 150 and water in reactor, be warming up to 60 ℃, stir, and all dissolve until Tai-Ace S 150, make the alum liquor of 30% concentration, and (3) add to (1) gained slaked lime slurry in the reactor and mix with Tai-Ace S 150, wherein Ca (OH)
2: Al
2(SO
4)
318H
2O: H
2O (weight)=1: 3: 7 is heated to 60 ℃, and stirring reaction is 1 hour under normal pressure, and (4) add 5% of reaction solution gross weight in above-mentioned reaction solution.NaSO
3, at normal pressure, 50-60 ℃ is stirred after 2-3 hour down and goes out still, elimination precipitate colourless transparent liquid polyaluminium sulfate product.Though this technology is by adding NaSO
3Stablizer, instability problem when having overcome high-polymerization degree, but still can't solve the problem that produces waste residue, and obtain the effective constituents A l of product equally
2O
3Percentage composition hangs down at 5-7%.
9. Chinese patent CN 200510072367.5 disclosed " preparation of polyaluminium sulfate " prepares Tai-Ace S 150 with the directly sour molten industrial spent catalyst of sulfuric acid earlier, makes polyaluminium sulfate with Tai-Ace S 150 and aluminium hydroxide polymerization then.This preparation method is to be starting material with the wax catalysis spent catalyst, the source is subjected to great restriction, and waste material produces product foreign matter content height, simultaneously with aluminium hydroxide as polymerizing agent, because the aluminium hydroxide activity is low, so the products obtained therefrom polymerization degree still is lower than 45%.
10. Chinese patent CN 101423259A disclosed " a kind of preparation method of solid polymeric aluminum ferric sulfate ", comprising: (1) makes ferric subsulfate by ferrous sulfate; (2) in ferric subsulfate, add entry, sulfuric acid and hydrogen peroxide successively, stir, leave standstill; (3) add aluminum contained compound, restir; (4) dry curing voluntarily down separated out; (5) normal temperature ageing, pulverize product.Adopt the air blast oxidizing process, overcome catalyzed oxidation technology is produced in traditional ferric flocculant industry NOx pollution problem environment.PAFS is a solid phase prod, has the advantage of storage, transportation aspect than liquid product, and long service life, need not evaporation or reduction vaporization process, and the coagulation active ingredient in the product obtains maximum the reservation.Quality index such as basicity, active ingredient all is higher than prior art, and in actual water body utilization was implemented, effect also was better than inorganic coagulants such as polymerize aluminum chloride bodied ferric sulfate.
Preparation method's step: (1) takes off crystal water with ferrous sulfate under 60-80 ℃ temperature condition, when treating that the ferrous sulfate crystal transfers white to by green, temperature is risen to 160-250 ℃ and open air blast, and heating and the about 10-14 of blasting time hour promptly get ferric subsulfate; (2) in ferric subsulfate, add entry, sulfuric acid and hydrogen peroxide successively, stir, left standstill 1-2 hour; (3) add aluminum contained compound, restir then; (4) reactant is put solidify voluntarily dry environment 2-3 day and separated out; (5) at last through normal temperature ageing 5-7 day, pulverize product.Add water 500-800ml in the 1kg ferric subsulfate, vitriol oil 90-120ml, perhaps the ratio in the aforementioned water and the vitriol oil adopts dilute sulphuric acid and ferric subsulfate mixing stirring reaction.Described aluminum contained compound is alum liquor or the alkalization aluminium liquid of concentration 1.5-2M.The add-on of described aluminum contained compound is pressed the molar ratio computing of aluminium and iron, and the ferro-aluminum mol ratio is 0.1-1: 3.
11. Chinese patent CN 101784485A disclosed " a kind of method that is used to produce polyaluminium salts ", a kind of alumina-bearing material is mixed with a kind of acidic cpd, and use microwave that this compound is heated to 150-250 ℃ temperature and maintains this temperature, can randomly combine with another thermal source, allow to maintain about 5 seconds to 60 a minutes time period of described mixture reaction of described temperature, and after this this mixture is cooled to 130 ℃ or lower.Wherein, the time period that this mixture reacts is about 15 seconds to 15 minutes, preferably from 30 seconds to 10 minutes, and most preferably from 2 minutes to 10 minutes.This thermal treatment of described use microwave is to carry out under about 170 ℃ to 230 ℃, preferred 180 ℃ to 220 ℃ temperature.Described acidic cpd is sulfuric acid, hydrochloric acid, nitric acid, formic acid, aluminum chloride or polyaluminium salts, useless industrial acidic solution or these mixture, and this polyaluminium salts has the lower basicity of product of producing by the method according to this invention than remaining.Described acidic cpd is a kind of mixture, comprise: sulfuric acid, and at least a in hydrochloric acid, nitric acid, formic acid, aluminum chloride or polymerize aluminum chloride or the useless industrial acidic solution, this polyaluminium salts has an OH/A1 mol ratio lower than this final product.Described alumina-bearing material comprises: the oxyhydroxide class of aluminium, the oxyhydroxide of aluminum oxide, bauxite, kaolin or other clays, the filter cake that comes self etching industry or these mixtures of material, the oxyhydroxide class of preferred aluminium.Described heat treated material at maximum 10 minutes time period internal cooling to maximum 130 ℃ temperature.Described method is used to produce a system of polyaluminium salts and their derivative, comprise: a mixing device, be used for a kind of alumina-bearing material and a kind of acidic cpd are mixed into a mixture, a heating unit, be used to use microwave with this mixture heating up to 150 ℃ to 250 ℃ temperature and maintain this temperature, can randomly combine with one or more other thermals source, a reactor assembly, be used to make about 5 seconds to 60 a minutes time period of this mixture reaction that maintains under the described temperature, and a refrigerating unit, be used for this reaction mixture is cooled to 130 ℃ or lower.A described system further comprises being used to make this mixture to stand ultransonic acoustic device.
When producing inorganic flocculating agent, very high to raw-material requirement, and current China can satisfy the bauxite resource closely exhaustion of these ingredient requirements, could guarantee the sufficient resources supply after must handling by additive method.PAFS is a kind of novel flocculation agent, and it has the advantage of polyaluminium sulfate and bodied ferric sulfate, have for many years about its research, but the production technique difference also is different to raw-material requirement.Contain higher aluminium mineral and iron mineral in the Pingguo aluminium ore washing mine tailing, wherein aluminium sesquioxide content is 36%, and ferric oxide content is 16%, and granularity is superfine, wherein-10 the thin cement content of micron granularity accounts for 80%, and they just in time are the splendid raw materials of production PAFS.We find, use such mine tailing can produce flocculant poly aluminium iron sulfate efficiently fully under certain process conditions.
Summary of the invention
The objective of the invention is: for the rational and efficient use bauxite resource, reduce the production cost of PAFS and, provide a kind of method for preparing PAFS with aluminium ore washing mine tailing effective processing of aluminium ore washing mine tailing.
The present invention is achieved in that
The method for preparing PAFS with aluminium ore washing mine tailing, be to utilize karst accumulation type bauxite washing mine tailing to burn slag iron powder and sulfuric acid reaction generation Tai-Ace S 150 and ferric sulfate aqueous solution or/and sulfurous iron ore is produced the vitriolic high ferro, add basifier polymerization production PAFS again, may further comprise the steps:
1, the underflow acidleach will add in water, mine tailing, sulfuric acid and the hydrogen peroxide of parts by weight of raw materials ratio in the reactor, heat to 148-150 ℃, start to stir and carry out the underflow acid-leaching reaction, underflow leaching time 38-42 minute, or add high ferro after 20 minutes again at acid-leaching reaction and burn the content that slag iron powder continues reaction and control aluminium and iron;
2, the above-mentioned pickling liquor moisturizing of thin liquid acidleach 3.0-3.5 weight part is cooled to 78-80 ℃ of acidleach 4 hours;
3, after the filtration acid-leaching reaction finishes, use ceramic filter to filter and obtain Tai-Ace S 150 and ferric sulfate aqueous solution, filter residue is standby;
4, concentrate and to go up step filtrate and carry out concentration, make strength of fluid reach 40 degree Beaume;
5, polymerization will add the basifier polymerization through spissated Tai-Ace S 150 and ferric sulfate aqueous solution;
6, slaking will be gone up the step polymkeric substance and is incubated slaking and obtain liquid product.
Above-described parts by weight of raw materials ratio is: water: mine tailing: sulfuric acid: the weight part ratio of hydrogen peroxide is 3.7: 1: 1.85: 0.025, perhaps water: mine tailing: high ferro is burnt slag iron powder: sulfuric acid: the weight part ratio of hydrogen peroxide is 3.7: 1: 1.5: 2.78: 0.025, and control Al
2O
3Leaching yield is 65-75%, Fe
2O
3Leaching yield is 92-95%.
The main component of above-described mine tailing and weight content: aluminium sesquioxide content 36%, ferric oxide content 16%.
Above-described high ferro is burnt slag iron powder main component and weight content: aluminium sesquioxide content 1%, iron level 60%
Above-described sulfuric acid is that concentration is 98% the vitriol oil.
The content of above-described control aluminium and iron is the concentration adjustment alumina content that adds liquid aluminium sulfate in step (1) by increase and decrease vitriolic consumption, calculates the increase and decrease high ferro and burns slag and vitriolic quantity regulating iron level.
Above-described polyreaction, condition is: the polymerization stirring velocity is 500r/min, and temperature of reaction is 78-80 ℃, and the time is 1 hour.
Above-described basifier is one or more the mixture in sodium bicarbonate, yellow soda ash and the sodium hydroxide, and its consumption is counted with weight ratio: leach liquor: basifier=1: 0.15.
Above-described slaking, condition is: the slaking stirring velocity is 500r/min, and temperature is 78-80 ℃, and the time is 3h, regulates polymer fluid pH:2.9-3.1.
Above-described filter residue, with after its seasoning as cement filler.
Concrete operational process of craft is: will be 3.7: 1: 1.85 in the parts by weight of raw materials ratio earlier: 0.025 water, sludge, sulfuric acid and hydrogen peroxide add in the reactor, heat to 146-150 ℃, start to stir and carry out the underflow acid-leaching reaction, underflow leaching time 38-42 minute, be 3.7: 1: 1.5 in the parts by weight of raw materials ratio perhaps: 2.78: 0.025 water, sludge, high ferro are burnt slag iron powder, sulfuric acid and hydrogen peroxide, add high ferro burning slag iron powder continuation reaction 18-22 minute, control Al after 20 minutes again at sludge and vitriol lixiviation reaction
2O
3Leaching yield is 65-75%, Fe
2O
3Leaching yield is 92-95%; Water 3.0-3.5 weight part is added in pickling liquor, continued acid-leaching reaction 4 hours after being cooled to 78-80 ℃.After acid-leaching reaction finishes, use ceramic filter to filter and obtain Tai-Ace S 150 and ferric sulfate aqueous solution, filter residue uses as cement filler; Tai-Ace S 150 and ferric sulfate aqueous solution are carried out concentration, when strength of fluid reaches 40 degree Beaume, will add with weight ratio and be: leach liquor: the basifier of sodium bicarbonate=1: 0.15 carries out polymerization, and the controlled polymerization stirring velocity is 500r/min, temperature of reaction is 80 ℃, and the time is 1 hour.Continuing the control stirring velocity then is 500r/min, and temperature is 78-80 ℃, and the time is 3h insulation slaking, regulates polymer fluid pH:2.9-3.1, obtains liquid product.This product be sorrel to reddish black, liquid-transparent, but, easily present pasty state along with iron level increases, polymer fluid is stable, leaves standstill to begin to have banded solids to occur in 25 days, leaves standstill 60 days polymer fluid flocculating effects and does not weaken.
Advantage of the present invention and positively effect:
The present invention adopts aluminium ore washing mine tailing to prepare the method for PAFS, be to utilize karst accumulation type bauxite washing mine tailing as producing the inorganic flocculating agent raw material, and the mine tailing granularity is superfine, wherein-10 the thin cement content of micron granularity accounts for 80%, they just in time are the splendid raw materials of production PAFS, the speed of reaction height, good product quality.Can rationally and effectively utilize bauxite resource; and from the source of polluting to aluminium ore choosing wash mine tailing and effectively administer, protected environment, realize close friend's coexistence of human and environment; also reduce simultaneously the production cost of PAFS, realized recycling economy efficiently.
Description of drawings
Fig. 1: be process flow diagram of the present invention.
Fig. 1 technical process comprises underflow acidleach, thin liquid acidleach, filtration, concentrates, polymerization and curing step.
Embodiment
Below in conjunction with drawings and Examples the present invention is done to describe further, but do not constitute any limitation of the invention.
Embodiment 1:
To be 3.7: 1: 1.85 in the parts by weight of raw materials ratio earlier: 0.025 water, mine tailing, sulfuric acid and hydrogen peroxide add in the reactor, heat to 150 ℃, start to stir and carry out the underflow acid-leaching reaction, underflow leaching time 41 minutes, control Al
2O
3Leaching yield is 72%, Fe
2O
3Leaching yield is 90%; Water 3 weight parts are added in pickling liquor, continued acid-leaching reaction 4 hours after being cooled to 80 ℃.After acid-leaching reaction finishes, use ceramic filter to filter and obtain Tai-Ace S 150 and ferric sulfate aqueous solution, filter residue uses as cement filler; Tai-Ace S 150 and ferric sulfate aqueous solution are carried out concentration, when strength of fluid reaches 40 degree Beaume, will add with weight ratio and be: leach liquor: the basifier of sodium bicarbonate=1: 0.15 carries out polymerization, and the controlled polymerization stirring velocity is 500r/min, temperature of reaction is 80 ℃, and the time is 1 hour.Continuing the control stirring velocity then is 500r/min, and temperature is 80 ℃, and the time is 3h insulation slaking, regulates polymer fluid pH:3.1, obtains liquid product.This product is the sorrel transparent liquid, and polymer fluid is stable, leaves standstill to begin to have banded solids to occur in 25 days, leaves standstill 60 days polymer fluid flocculating effects and does not weaken.
Embodiment 2:
To be 3.7: 1: 1.85 in the parts by weight of raw materials ratio earlier: 0.025 water, sludge (mine tailing), sulfuric acid and hydrogen peroxide add in the reactor, heat to 148 ℃, start to stir and carry out the underflow acid-leaching reaction, underflow leaching time 40 minutes, control Al
2O
3Leaching yield is 75%, Fe
2O
3Leaching yield is 92%; Water 3.2 weight parts are added in pickling liquor, continued acid-leaching reaction 4 hours after being cooled to 79 ℃.After acid-leaching reaction finishes, use ceramic filter to filter and obtain Tai-Ace S 150 and ferric sulfate aqueous solution, filter residue uses as cement filler; Tai-Ace S 150 and ferric sulfate aqueous solution are carried out concentration, when strength of fluid reaches 40 degree Beaume, will add with weight ratio and be: leach liquor: the basifier of yellow soda ash=1: 0.15 carries out polymerization, and the controlled polymerization stirring velocity is 500r/min, temperature of reaction is 79 ℃, and the time is 1 hour.Continuing the control stirring velocity then is 500r/min, and temperature is 79 ℃, and the time is 3h insulation slaking, regulates polymer fluid pH:2.9, obtains liquid product.This product is a sorrel liquid, and polymer fluid is stable, leaves standstill to begin to have banded solids to occur in 25 days, leaves standstill 60 days polymer fluid flocculating effects and does not weaken.
Embodiment 3:
To be 3.7: 1: 2.78 in the parts by weight of raw materials ratio earlier: 0.025 water, sludge (mine tailing), sulfuric acid and hydrogen peroxide add in the reactor, heat to 146 ℃, start to stir and carry out the underflow acid-leaching reaction, acid-leaching reaction adds after 20 minutes again: 1.5 weight part high ferros are burnt slag iron powder and are heated to 150 ℃ of continuation reactions 22 minutes, control Al
2O
3Leaching yield is 75%, Fe
2O
3Leaching yield is 94%; Water 3.5 weight parts are added in pickling liquor, continued acid-leaching reaction 4 hours after being cooled to 80 ℃.After acid-leaching reaction finishes, use ceramic filter to filter and obtain Tai-Ace S 150 and ferric sulfate aqueous solution, filter residue uses as cement filler; Tai-Ace S 150 and ferric sulfate aqueous solution are carried out concentration, when strength of fluid reaches 40 degree Beaume, to add with weight ratio and be: leach liquor: the basifier of the mixture of yellow soda ash and any ratio of sodium hydroxide=1: 0.15 carries out polymerization, the controlled polymerization stirring velocity is 500r/min, temperature of reaction is 80 ℃, and the time is 1 hour.Continuing the control stirring velocity then is 500r/min, and temperature is 80 ℃, and the time is 3h insulation slaking, regulates polymer fluid pH:2.9, obtains liquid product.This product is a reddish black liquid, presents pasty state, and polymer fluid is stable, leaves standstill to begin to have banded solids to occur in 25 days, leaves standstill 60 days polymer fluid flocculating effects and does not weaken.
Claims (9)
1. method for preparing PAFS with aluminium ore washing mine tailing, it is characterized in that: utilize the washing mine tailing of karst accumulation type bauxite or other aluminium ore to burn slag iron powder and sulfuric acid reaction generation Tai-Ace S 150 and ferric sulfate aqueous solution or/and sulfurous iron ore is produced the vitriolic high ferro, add basifier polymerization production PAFS again, may further comprise the steps:
(1) the underflow acidleach will add in water, mine tailing, sulfuric acid and the hydrogen peroxide of parts by weight of raw materials ratio in the reactor, heat to 148-150 ℃, start to stir and carry out the underflow acid-leaching reaction, underflow leaching time 38-42 minute, or add high ferro after 20 minutes again at acid-leaching reaction and burn the content that slag iron powder continues reaction and control aluminium and iron;
Described parts by weight of raw materials ratio is: water: mine tailing: sulfuric acid: the weight part ratio of hydrogen peroxide is 3.7: 1: 1.85: 0.025, perhaps water: mine tailing: high ferro is burnt slag iron powder: sulfuric acid: the weight part ratio of hydrogen peroxide is 3.7: 1: 1.5: 2.78: 0.025, control Al2O3 leaching yield is 65-75%, and the Fe2O3 leaching yield is 92-95%;
(2) the above-mentioned pickling liquor moisturizing of thin liquid acidleach 3.0-3.5 weight part is cooled to 78-80 ℃ of acidleach 4 hours;
(3) after the filtration acid-leaching reaction finishes, use ceramic filter to filter and obtain Tai-Ace S 150 and ferric sulfate aqueous solution, filter residue is standby;
(4) concentrate and to go up step filtrate and carry out concentration, make strength of fluid reach 40 degree Beaume;
(5) polymerization will add the basifier polymerization through spissated Tai-Ace S 150 and ferric sulfate aqueous solution;
(6) slaking will be gone up the step polymkeric substance and is incubated slaking and obtain liquid product.
2. describedly prepare the method for PAFS according to claim 1 and 2, it is characterized in that: described mine tailing main component and weight content: aluminium sesquioxide content 36%, ferric oxide content 16% with aluminium ore washing mine tailing.
3. describedly prepare the method for PAFS with aluminium ore washing mine tailing according to claim 1 and 2, it is characterized in that: described high ferro is burnt slag iron powder main component and weight content: aluminium sesquioxide content 1%, iron level 60%.
4. describedly prepare the method for PAFS with aluminium ore washing mine tailing according to claim 1 and 2, it is characterized in that: described sulfuric acid concentration is 98% the vitriol oil.
5. according to claim 1ly prepare the method for PAFS with aluminium ore washing mine tailing, it is characterized in that: the content of control aluminium and iron is the concentration adjustment alumina content that adds liquid aluminium sulfate in step (1) by increase and decrease vitriolic consumption; Calculate the increase and decrease high ferro and burn slag and vitriolic quantity regulating iron level.
6. according to claim 1ly prepare the method for PAFS, it is characterized in that with aluminium ore washing mine tailing: described polyreaction, condition is: the polymerization stirring velocity is 500r/min, and temperature of reaction is 78-80 ℃, and the time is 1 hour.
7. the method for preparing PAFS with aluminium ore washing mine tailing according to claim 1, it is characterized in that: described basifier, be one or more the mixture in sodium bicarbonate, yellow soda ash and the sodium hydroxide, its consumption is counted with weight ratio: leach liquor: basifier=1: 0.15.
8. according to claim 1ly prepare the method for PAFS with aluminium ore washing mine tailing, it is characterized in that: described slaking condition is: stirring velocity is 500r/min, and temperature is 78-80 ℃, and the time is 3h, regulates polymer fluid pH:2.9-3.1.
9. according to claim 1ly prepare the method for PAFS, it is characterized in that with aluminium ore washing mine tailing: after the described filter residue seasoning as cement filler.
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| CN103553194A (en) * | 2013-07-31 | 2014-02-05 | 乔占印 | Rear-earth poly aluminum ferric sulfate and preparation method thereof |
| CN104591442A (en) * | 2015-01-30 | 2015-05-06 | 河南理工大学 | Gold tailing multistage purification treatment technology |
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