CN110451828A - The method and apparatus that electromagnetism strengthens ardealite removal of impurities - Google Patents

The method and apparatus that electromagnetism strengthens ardealite removal of impurities Download PDF

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Publication number
CN110451828A
CN110451828A CN201910768593.9A CN201910768593A CN110451828A CN 110451828 A CN110451828 A CN 110451828A CN 201910768593 A CN201910768593 A CN 201910768593A CN 110451828 A CN110451828 A CN 110451828A
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China
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ardealite
slurries
electrode
removal
electromagnetism
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瞿广飞
李恒
宁平
李军燕
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Priority to CN201910768593.9A priority Critical patent/CN110451828A/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00Calcium sulfate cements
    • C04B11/02Methods and apparatus for dehydrating gypsum
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00Calcium sulfate cements
    • C04B11/02Methods and apparatus for dehydrating gypsum
    • C04B11/028Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
    • C04B11/032Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the wet process, e.g. dehydrating in solution or under saturated vapour conditions, i.e. to obtain alpha-hemihydrate

Abstract

The invention discloses the method and apparatus that a kind of electromagnetism strengthens ardealite removal of impurities, by ardealite and organic extractant is added in pickling tank by spiral crane and the concentrated sulfuric acid is mixed and made into ardealite slurries, heating, stirring keep slurries uniform, and the impurity in ardealite is allowed sufficiently to leach;Electric field is applied to the slurries after mixing, so that the impurity for wrapping up, being adsorbed on ardealite surface sufficiently releases;It is transported in water scrubber by ardealite slurries of the electrolysis from after, apply electric and magnetic fields in water scrubber, directional migration occurs under the action of electric field force for metal, heavy metal, radioactive metal ion under stirring in ardealite slurries, it is finally deposited in electrode surface, realizes the separation with ardealite slurries;This method and device applicability are wide, to ardealite impurity content non-selectivity;Short processing time, low energy consumption, treatment effeciency is high, without secondary pollution;Metal, heavy metal and the radioactive element in recycling ardealite can be efficiently separated, realizes resource circulation utilization.

Description

The method and apparatus that electromagnetism strengthens ardealite removal of impurities
Technical field
The present invention relates to the method and apparatus that a kind of electromagnetism strengthens ardealite removal of impurities, belong to the resource utilization neck of ardealite Domain.
Background technique
Ardealite is the industrial residue that we are discharged when using Wet-process phosphoric acid (WPPA), the benefit of ardealite in China It is also very low with rate, the especially southwest in China, because not utilizing ardealite effectively, so that the stacking of ardealite, place Setting has become the major issue for influencing environment.The main reason for impurity contained in ardealite is limitation ardealite utilization rate.
Ardealite main component is calcium sulphate dihydrate, and calcium sulfate butt quality score is generally more than 80% in ardealite, very Extremely more than 90%, but its utilization rate is lower, the main reason is that containing a large amount of Phosphorus impurity in ardealite, fluorine class impurity, having Machine class impurity, metal salt and radioactive element etc. are a kind of important reclaimed gypsum resources.
Phosphorus is main objectionable impurities in ardealite, and the phosphorus in ardealite is mainly with titanium pigment, eutectic phosphorus, insoluble phosphorus Three kinds of forms exist, and indissoluble object is covered on ardealite surface, and gypsum is hindered to continue dissolution and aquation, thus extend ardealite and its The condensation firm time of product reduces cement early strength and reduces the intensity of plastering, wherein with titanium pigment to phosphorus stone Cream performance influences maximum.
Fluorine source in ardealite is in rock phosphate in powder, and when rock phosphate in powder is through sulfuric acid decomposition, the fluorine in rock phosphate in powder has 20%~40% It is mixed in ardealite, with soluble fluorine NaF and indissoluble fluorine (CaF, Na2SiF6、Na2AlF6) two kinds of forms exist.Soluble fluoride is The principal mode of ardealite performance is influenced, it has blood coagulation enhancing effect, if soluble fluoride content is lower, to the performance shadow of ardealite Sound is smaller, but when its mass fraction is more than 0.3%, and soluble fluoride can be such that hydrated product crystal is roughened, molecular force between crystal Weaken, short texture, to reduce the intensity of ardealite.Slightly solubility fluorine has inertia, can be used as inert filler to ardealite base This does not have an impact, if there will be very big activity and thermal instabilitys with the presence of syncrystallization complex compound.Fluorine meeting in ardealite It causes damages to environment.
The organic impurities of organic matter in ardealite in rock phosphate in powder, and added in the production of some techniques have Machine additive, impurity composition are mainly ethylene glycol monomethyl ether acetate, different sulphur cyanogen methane, 3- methoxyl group pentane etc..Organic matter Generally present cotton-shaped, they are distributed in dihydrate gypsum crystal surface, and mass fraction increases with the increase of phosphogypsum size.If Ardealite in use, the presence of the impurity can significantly increase water requirement, while can weaken dihydrate gypsum as cementitious material again Engagement between crystal weakens the molecular force between crystal, makes hardenite short texture, strength reduction.
Also containing impurity such as alkali metal salt, silicon, iron, aluminium, magnesium in ardealite, the network in addition also thering is metal and phosphate to be formed Close object and some radioactive elements, such as uranium, radium, cadmium, lead, copper element.Alkali metal is mainly with carbonate, sulfate, phosphoric acid The soluble-salts form such as salt, fluoride exists.Phosphogypsum product can be removed table along hardenite hole by the time of tide, alkali metal ion Face generates dusting and scum in Surface Crystallization after the moisture evaporation such as its meeting.Radioactive element in ardealite derives from phosphorus ore Stone, therefore ardealite can be detrimental to health with certain radioactivity.Currently, finding a kind of processing not yet both at home and abroad The method of radioactive element.
For the removal of impurities of ardealite, mainly there are chemical method, physical method, heat treating process etc. at present, is embodied in alkali and changes The methods of property, washing, flotation, calcining, ageing.There are 1. techniques of problem to have selection to content of organics in ardealite for above method Property;2. one-time investment is big, energy consumption is high, the secondary pollution of sewage discharge and it is other pollution, there are also technique it is more complex the problems such as; 3. energy consumption is high, treating capacity is smaller.
Summary of the invention
For the limitation of existing ardealite removal of impurities, i.e., the low separation efficiency of impurity, resource in existing removal ardealite The problem of circulating benefit is low, can not effectively remove heavy metal and radioactive element, the present invention provides a kind of greens, efficient removal The method of impurity in ardealite, both a kind of electromagnetism strengthened the method and apparatus of ardealite removal of impurities.
The method and apparatus particular content that a kind of electromagnetism of the present invention strengthens ardealite removal of impurities is as follows
(1) be electrolysed from: ardealite and organic extractant are added in pickling tank by spiral crane and the concentrated sulfuric acid mixes system At ardealite slurries, heating, stirring keep slurries uniform, and the impurity in ardealite is allowed sufficiently to leach;Slurries after mixing are applied Electric field, the calcium sulphate dihydrate in ardealite are dissociated into calcium ion and sulfate ion in hot sulfuric acid, so that package, being adsorbed on phosphorus Metal, heavy metal and the radioactive element of gypsum surface and there are its intracell impurity sufficiently to release;In electric field masterpiece With the lower chemical bond for destroying organic and sulfide reference state metallic compound, it is promoted to convert to exchangeable species, to realize Transformation of the impurity from solid phase to liquid phase in ardealite, is segregated into ardealite slurries;Organic extractant is by impurity simultaneously Extraction enters in organic phase;
(2) electromagnetism migration deposits: being transported in water scrubber by ardealite slurries of the electrolysis from after, applies electric field in water scrubber And magnetic field, metal, heavy metal, radioactive metal ion under stirring in ardealite slurries are sent out under the action of electric field force Raw directional migration, the charged ion of migration in magnetic field by the effect of Lorentz force, by control pulsed magnetic generator Current direction make Lorentz force direction suffered by charged ion consistent with electric field force direction, accelerate ion to electrode two sides migrate Speed, the ion concentration near two electrodes is continuously increased, finally deposits in electrode surface, realize and ardealite slurries Separation;Electrode is taken out from electrode card slot, separated and dissolved is carried out to the metal, heavy metal and radioactive element deposited on electrode Metallic solution is obtained, is further recycled;Ardealite slurries after washing are dehydrated, by soluble Phosphorus, fluorine class and Semi-hydrated gypsum is obtained after organic impurity removal.
The present invention selects sulfuric acid as leaching agent, and ardealite and organic extractant are mixed to join by spiral crane In pickling tank, ardealite is allowed to mix well by mechanical stirring.Acidleach trench bottom is equipped with heating device and improves temperature of reaction system, The raising of sulfuric acid temperature increases molecule diffusion, promotes the reactant entropy in reaction system to increase, so that impurity in ardealite It is easier dissolved in acid solution, to improve leaching rate.The raising of temperature reduces the reaction activity of ardealite simultaneously, is conducive to It destroys and contains miscellaneous calcium sulfate lattice, make its chemical bond that dissociation be more easily broken off, allow intracell impurity sufficiently to release and be dissolved in In solution.
The present invention selects electric field action to handle ardealite slurries, and specific effect is divided into two parts: first is that destroying has Machine and sulfide reference state metal, heavy metal chemical bond change by it to exchangeable species, increase exchangeable species in ardealite slurries Heavy metal concentration.Second is that applying electromigration to ardealite, the metal, heavy metal and radiogold of exchangeable species will appear as Category migrates under the action of electric field to cathode zone, negatively charged water-soluble state fluorine ion, fluorate Ion transfer to anode region Domain, two kinds are originally slurry constituents mixed in together to opposite zone migration, realize separation;Third is that the electricity in ardealite slurries Electrode potential is lower than the equilibrium potential of metal ion in the solution, and metal ion is heavy in electrode surface reduction when obtaining certain overpotential Product.Metal ion in ardealite slurries is migrated to electrode surface, moves to the metal ion near electrode surface and chemistry occurs Conversion reaction, ion hydration degree are reduced and are reset, electronics transition between electrode and ion hydration, metal ion and cathode table Charge transfer occurs for face, and metal ion obtains forming adatom in electrode surface after electron reduction, is adsorbed on electrode surface Adatom sloughs remaining hydration shell as metallic atom, and newborn ADSORPTION STATE metallic atom is diffused into appropriate position along electrode surface It sets, into lattice growth, to form crystal.Porous electrode porosity with higher and specific surface area in the present invention, for gold The deposition of category, heavy metal and radioactive metal ion provides sufficient contact area, reduces falling off for deposit.
One controllable magnetic field vertical with DC electric field is provided in the DC electric field space provided inside water scrubber of the present invention, By controlling to adjust electric field strength and applied field strengths, change the motion profile of negative ions in ardealite slurries on demand, Negative ions in ardealite slurries are made to deflect, so that Lorentz force direction suffered by charged ion is consistent with electric field force direction, Accelerate migration velocity of the ion to two electrodes, shortens residence time of the charged ion in washing tower apparatus, allow near two electrodes Ion concentration be continuously increased, the more effective separative efficiency for improving charged ion, to reach metal, heavy metal and radioactivity member Element deposits to recycle on porous electrode surface.Magnetic field is generated by Helmholtz coil, it is by identical circle Conductor coils composition, each conductor coils are loaded with same direction current, and inside generates the higher magnetic field of the uniformity.Helmholtz coil The electromagnetic force that inside generates is to ardealite slurries, especially to the biggish heavy metal of solubility product constant, such as Ni, Ti, Co, Sr, Since its solubility product is larger, these metal ions are more difficult and OH-Insoluble compound is formed, is not susceptible to precipitate, becomes commutative State metal, so that easier migrate under the synergistic effect of electromagnetic force to electrode surface deposits.
The mass concentration of the concentrated sulfuric acid is 25%~35%, and the mass ratio of ardealite and the concentrated sulfuric acid is 1:3~1:5, dense sulphur The Ore Leaching time is 45min~120min.
The organic extractant is tributyl phosphate, carbon tetrachloride, dioctylphosphoric acid ester.
The organic extractant is tributyl phosphate, carbon tetrachloride or dioctylphosphoric acid ester, ardealite and organic extractant Mass volume ratio is 1:5~1:7.
Electric field is generated by stainless steel electrode in the pickling tank, and being passed through current system is direct current, and voltage is 10~30V, Electric field application time is to continuously apply.
Heating temperature is 70~90 DEG C in the pickling tank, and mixing speed is 40~80r/min.
Electric field is generated by porous electrode in the water scrubber, and being passed through current system is direct current, and voltage is 30~60V, electricity Pole material is stainless steel, graphite or carbon;Electric field application time is 1~3h, and the porosity of porous electrode is 20%~50%.
The magnetic field by pulsed magnetic generator helmholtz coil generate, to coil apply voltage be 20~ 50V, helmholtz coil the number of turns are 50~100, and inductance is 5~30 μ H, and magnetic field application time is 60~180min.
Mixing speed is 30~60r/min in the step (2).
The water velocity of the water scrubber water inlet is 5~20m/s, in water scrubber ardealite slurries moisture content be 80%~ 90%。
The electromagnetism that another object of the present invention is to provide a kind of completion above method strengthens the device of impurity in removing ardealite, It include include spiral crane, pickling tank, pump, water scrubber, wherein pickling tank include shell, stainless steel electrode, heating tube, Feeding inlet, discharge port, blender I, stainless steel electrode are arranged in shell, and upper part of the housing is provided with feeding inlet, feeding inlet and spiral Crane connection, housing bottom are provided with discharge port, and heating tube is arranged in shell bottom, is provided with blender I in shell, discharges Mouth is connected by pipeline and pump;Water scrubber includes tower shell, slurry inlet, electromagnetic generator, blender II, water inlet, slurry Liquid outlet, peep hole, are provided with blender II in tower shell, tower shell top is provided with water inlet, and tower shell lower part is provided with slurries Import, slurry inlet are connected by pipeline and pump, and tower shell bottom is provided with serum outlet, and tower casing body side surface is provided with more than one Peep hole, electromagnetic generator are arranged in tower shell, stainless steel electrode, electromagnetic generator, heating tube, blender I, stirring Device II connects to power supply respectively.
The stainless steel electrode includes arc positive plate and arc negative plate, the electric field that arc anode and arc cathode generate Pickling tank inner cavity is covered, arc positive plate and arc negative plate are connect with power positive cathode respectively.
The electromagnetic generator includes bracket, magnetic induction loop, porous electrode, and magnetic induction loop is arranged on bracket, porous Electrode includes arcuated porous positive plate and arcuated porous negative plate, and porous electrode, which runs through, to be arranged in bracket, electromagnetic generator The electric field of generation, magnetic field cover water scrubber inner cavity.
The crane spiral is variable-pitch propeller.
The pump is corrosion resistant sludge pump.
The advantages of the method for the present invention and device and effect are as follows:
1. efficiently separating metal, heavy metal and the radioactive element in recycling ardealite.Realize resource circulation utilization.
2. short processing time, low energy consumption, treatment effeciency is high, without secondary pollution.
3. applicability is wide, to ardealite impurity content non-selectivity.
Detailed description of the invention
Fig. 1 is schematic structural diagram of the device of the invention;
Fig. 2 is electromagnetic generator structural schematic diagram in water scrubber;
In figure: 1- spiral crane;2- shell;3- stainless steel electrode;4- peep hole;5- heating tube;6- feeding inlet;7- discharging Mouthful;8- blender I;9- pump;10- tower shell;11- slurry inlet;12- electromagnetic generator;13- blender II;14- water inlet Mouthful;15- serum outlet;16- bracket;17- magnetic induction loop;18- porous electrode.
Specific embodiment
The present invention is described in detail With reference to embodiment, but the scope of the present invention be not limited to it is described Content.
Embodiment 1: the present embodiment process object is the ardealite of generation during certain phosphoric acid plant Wet-process phosphoric acid (WPPA), wherein Phosphorus impurity content 1.5%, fluorine class impurity content 1.2%, organic impurity content 0.35% and are put metal and heavy metallic oxide Penetrating property metal class impurity content 1.3%.
1, acidleach is handled: ardealite and tributyl phosphate being added in spiral crane, are added to acid after mixing In immersion trough, stainless steel electrode is put into electrode card slot, and the sulfuric acid that concentration is 28%, ardealite and organic extraction are added into pickling tank The mass volume ratio for taking agent is 1:5, and the mass ratio of ardealite and the concentrated sulfuric acid is 1:3, opens pickling tank bottom heating device, allows system Temperature reaches 70 DEG C;It is dissociated into calcium ion and sulfate ion in hot sulfuric acid containing miscellaneous calcium sulphate dihydrate, so that its package, absorption In the metal on ardealite surface, heavy metal and radioactive element and there are the impurity such as its intracell phosphorus, fluorine sufficiently to release. System temperature, which increases, increases ardealite slurries molecule diffusion, promotes the reactant entropy in reaction system to increase, so that phosphorus stone Impurity is easier dissolved in acid solution in cream, to improve leaching rate.The reaction activity of ardealite is reduced simultaneously, is destroyed containing miscellaneous Calcium sulfate lattice makes its chemical bond that dissociation be more easily broken off, and impurity in ardealite is allowed sufficiently to release dissolution in the solution.Electricity Motivation drives agitating shaft, mixing speed 40r/min;Electrode supply is connected, control DC voltage is 15V;Adhere to and is adsorbed on Under electric field force effect directional migration occurs for the charged ion of ardealite surface or intracell, is detached from chemical bond and lattice beam It ties up, is present in ardealite slurries in the form of exchangeable species, achieve the purpose that separation dissolution.Tributyl phosphate is by ardealite slurries In organic impurities extraction enter in organic phase, extraction time 50min;
2, it washing process: will be added by ardealite slurries of the electrolysis from after from water scrubber lower port, clear water is with the flow velocity of 8m/s It is added from water scrubber top, so that ardealite moisture content is 80%.The porous graphite electrode that porosity is 30% is packed into electrode card In slot, control DC voltage is 40V and keeps 1h;Then helmholtz coil is placed in water scrubber, is applied into coil Voltage is 20V, and texture of coil is copper wire, and helmholtz coil the number of turns is 50, and inductance is 8 μ H, and magnetic field application time is 60min, blender mixing speed are 35r/min;Exchangeable species metal, heavy metal, radioactive metal in ardealite slurries from Directional migration occurs under the action of electric field force for son, the charged metal ion of migration in magnetic field by the effect of Lorentz force, Make Lorentz force direction suffered by charged ion and electric field force direction one by the current direction in control pulsed magnetic generator It causes, accelerates migration velocity of the metal ion to cathode, negatively charged water-soluble state fluorine ion, fluorate Ion transfer to anode region Domain, two kinds are originally slurry constituents mixed in together to opposite zone migration, and the ion concentration near two electrodes is continuously increased, Two electrode potentials be lower than the equilibrium potential of metal ion in the solution, when obtaining certain overpotential metal ion electrode surface also Original deposition;The metal that surface deposits is washed away after taking out porous electrode in electrode card slot, realization is completely separated with ardealite.
3. dehydration: by the ardealite slurries after washing by centrifugal dehydrator, realizing solvable in ardealite slurries The removing of property Phosphorus, fluorine class and organic impurity, obtains the semi-hydrated gypsum of lower impurity.It is Phosphorus after electromagnetism intensive treatment Removal of impurity is 95%;Fluorine class removal of impurity is 82%;Organic removal of impurity is 80%;Metal and heavy metallic oxide And radioactive metal class removal of impurity is 65%.
As shown in Figs. 1-2, the device for completing the above method includes spiral crane 1, pickling tank, pumps 9, water scrubber, wherein Pickling tank includes shell 2, stainless steel electrode 3, heating tube 5, feeding inlet 6, discharge port 7, blender I 8, and stainless steel electrode 3 is arranged In shell 2,2 top of shell is provided with feeding inlet 6, and feeding inlet is connected to spiral crane 1, and 2 bottom of shell is provided with discharge port 7, Bottom is arranged in shell 2 in heating tube 5, and blender I 8 is provided in shell, and discharge port 7 is connect by pipeline with pump 9;Stainless steel Electrode 3 includes arc positive plate and arc negative plate, and the electric field that arc anode and arc cathode generate covers pickling tank inner cavity, arc Shape positive plate and arc negative plate are connect with power positive cathode respectively;
Water scrubber includes tower shell 10, slurry inlet 11, electromagnetic generator 12, blender II 13, water inlet 14, serum outlet 15, peep hole 4 are provided with blender II 13 in tower shell 10, and 10 top of tower shell is provided with water inlet 14, and 10 lower part of tower shell is opened There is slurry inlet 11, slurry inlet 11 is connect by pipeline with pump 9, and 10 bottom of tower shell is provided with serum outlet 15, tower shell 10 sides are provided with more than one peep hole 4, and electromagnetic generator 12 is arranged in tower shell 10, and stainless steel electrode 3, electromagnetism occur Device 12, heating tube 5, blender I, blender II connect to power supply respectively;Electromagnetic generator includes bracket 16, magnetic induction loop 17, porous electrode 18, magnetic induction loop 17 are arranged on bracket 16, and porous electrode 18 includes arcuated porous positive plate and arcuated porous Negative plate, arcuated porous positive plate and arcuated porous negative plate, which run through, to be arranged in bracket, the electric field of electromagnetic generator generation, Magnetic field covers water scrubber inner cavity.
Ardealite and organic extractant are added in spiral crane 1 by feed hopper, are driven under the work of motor The certain density concentrated sulfuric acid is added into pickling tank, opens entering in pickling tank after material lifting from feed inlet 6 for helical rotation Stainless steel electrode power supply and heating tube power supply carry out Ore Leaching, and the ardealite slurries after leaching process pass through pipe using pump 9 Road is pumped into water scrubber from feed slurry inlet 11;Clear water is added in water scrubber from water inlet 14, open with porous electrode 18 and The power switch that magnetic induction loop 17 connects, the slurries after Electromagnetic Treatment exclude the dehydration for entering next step from serum outlet 15 Processing.
Embodiment 2: the present embodiment process object is the ardealite inventory that certain ardealite stacks processing center, wherein Phosphorus miscellaneous Matter content 1.1%, fluorine class impurity content 0.9%, organic impurity content 0.22%, metal and heavy metallic oxide and radiogold Belong to class impurity content 0.9%.
Acidleach processing: ardealite and carbon tetrachloride are added in spiral crane, are added to acid after mixing stirring In immersion trough, stainless steel electrode is put into electrode card slot, and the sulfuric acid that concentration is 30%, ardealite and organic extraction are added into pickling tank The mass volume ratio for taking agent is 1:6, and the mass ratio of ardealite and the concentrated sulfuric acid is 1:4, opens pickling tank bottom heating device, allows system Temperature reaches 80 DEG C, is dissociated into calcium ion and sulfate ion in hot sulfuric acid containing miscellaneous calcium sulphate dihydrate, so that its package, absorption In the metal on ardealite surface, heavy metal and radioactive element and there are the impurity such as its intracell phosphorus, fluorine sufficiently to release. System temperature raising allows molecule diffusion in ardealite slurries to reinforce, so that impurities exhibit increases in ardealite, to mention High leaching rate.The reaction activity of ardealite is reduced simultaneously, is destroyed and is contained miscellaneous calcium sulfate lattice, its chemical bond is more easily broken off Dissociation allows intracell impurity sufficiently to release dissolution in the solution.Motor drives agitating shaft, mixing speed 50r/ min.Electrode supply is connected, control DC voltage is 20V.Adhere to and be adsorbed on the charged ion of ardealite surface or intracell Directional migration occurs under electric field force effect, is detached from chemical bond and lattice constraint, ardealite slurry is present in the form of exchangeable species In liquid, achieve the purpose that separation dissolution.Tributyl phosphate enters the organic impurities extraction in ardealite slurries in organic phase, Extraction time is 60min.
Washing process: it will be added by ardealite slurries of the electrolysis from after from water scrubber lower port, clear water is with the stream of 12m/s Speed enters from water scrubber top, so that ardealite moisture content is 85%.The porous graphite electrode that porosity is 35% is packed into electrode In card slot, control DC voltage is 50V and keeps 1.5h.Ardealite applies electromigration, will appear as the gold of exchangeable species Belong to, heavy metal and radioactive metal migrate under the action of electric field to cathode zone, negatively charged water-soluble state fluorine ion, fluoric acid Salt ion is migrated to anode region, and two kinds are originally slurry constituents mixed in together to opposite zone migration;Then by conspicuous nurse Suddenly in hereby coil merging water scrubber, the voltage applied into coil is 30V, and texture of coil is copper wire, helmholtz coil the number of turns It is 80, inductance is 12 μ H, and magnetic field application time is 70min, and blender mixing speed is 45r/min.The charged ion of migration By the effect of Lorentz force in magnetic field, made suffered by charged ion by the current direction in control pulsed magnetic generator Lorentz force direction is consistent with electric field force direction, accelerates migration velocity of the ion to two electrodes, the ion concentration near two electrodes It is continuously increased, is finally deposited on porous electrode surface;Realize the separation with ardealite slurries.
Dehydration: by the ardealite slurries after washing by centrifugal dehydrator, the solubility in ardealite slurries is realized The removing of Phosphorus, fluorine class and organic impurity obtains the semi-hydrated gypsum of lower impurity.It is Phosphorus miscellaneous after electromagnetism intensive treatment Matter removal rate is 96%;Fluorine class removal of impurity is 86%;Organic removal of impurity is 85%;Metal and heavy metallic oxide and Radioactive metal class removal of impurity is 70%.
The present embodiment apparatus structure is the same as embodiment 1.
Embodiment 3: the present embodiment process object is the desulfurized gypsum that certain chemical plant flue gas desulfurization generates, wherein Phosphorus impurity Content 1.5%, fluorine class impurity content 0.3%, organic impurity content 0.18%, metal and heavy metallic oxide and radioactive metal Class impurity content 1.6%.
Acidleach processing: ardealite and dioctylphosphoric acid ester are added in spiral crane, are added to after mixing stirring In pickling tank, stainless steel electrode put into electrode card slot in, into pickling tank be added concentration for 35% sulfuric acid, ardealite with it is organic The mass volume ratio of extractant is 1:7, and the mass ratio of ardealite and the concentrated sulfuric acid is 1:5, opens pickling tank bottom heating device, allows body It is that temperature reaches 85 DEG C.It is dissociated into calcium ion and sulfate ion in hot sulfuric acid containing miscellaneous calcium sulphate dihydrate, so that its package, suction It is attached to metal, heavy metal and the radioactive element on ardealite surface and there are the impurity such as its intracell phosphorus, fluorine sufficiently to release Come.System temperature, which increases, increases molecule diffusion, promotes the reactant entropy in reaction system to increase, so that impurity in ardealite It is easier dissolved in acid solution, to improve leaching rate.The reaction activity of ardealite is reduced simultaneously, is destroyed brilliant containing miscellaneous calcium sulfate Lattice make its chemical bond that dissociation be more easily broken off, and intracell impurity is allowed sufficiently to release dissolution in the solution.Motor drives Agitating shaft, mixing speed 60r/min.Electrode supply is connected, control DC voltage is 25V.Tributyl phosphate starches ardealite Organic impurities extraction in liquid enters in organic phase.Extraction time is 70min.
Washing process: ardealite slurries after acidleach are added from water scrubber lower port, and clear water is with the flow velocity of 15m/s from washing Tower top enters in tower, so that ardealite moisture content is 90%, the porous graphite electrode that porosity is 40% is packed into electrode card slot In, control DC voltage is 60V and keeps 2h.Ardealite applies electromigration, will appear as metal, the huge sum of money of exchangeable species Belong to and radioactive metal migrates under the action of electric field to cathode zone, negatively charged water-soluble state fluorine ion, fluoric acid salt ion It migrates to anode region, two kinds are originally slurry constituents mixed in together to opposite zone migration.Then by Helmholtz line In circle merging water scrubber, the voltage applied into coil is 35V, and texture of coil is copper wire, and helmholtz coil the number of turns is 90, electricity Sensibility reciprocal is 18 μ H, and magnetic field application time is 85min, and blender mixing speed is 50r/min.The charged ion of migration is in magnetic field By the effect of Lorentz force, by controlling to adjust electric field strength and applied field strengths, change in ardealite slurries on demand The motion profile of negative ions makes negative ions in ardealite slurries deflect, so that Lorentz force side suffered by charged ion To, quickening migration velocity from ion to two electrodes consistent with electric field force direction, shortens charged ion and stop in washing tower apparatus The time is stayed, the ion concentration near two electrodes is allowed to be continuously increased.It moves to the metal ion near electrode surface and chemistry turn occurs Change reaction, ion hydration degree is reduced and reset, electronics transition between electrode and ion hydration, metal ion and cathode surface Charge transfer occurs, metal ion obtains forming adatom in electrode surface after electron reduction, is adsorbed on the suction of electrode surface Attached atom sloughs remaining hydration shell as metallic atom.The gold that surface deposits is washed away after taking out porous electrode in electrode card slot Belong to, realization is completely separated with ardealite.
Dehydration: by the ardealite slurries after washing by centrifugal dehydrator, the solubility in ardealite slurries is realized The removing of Phosphorus, fluorine class and organic impurity obtains the semi-hydrated gypsum of lower impurity.It is Phosphorus miscellaneous after electromagnetism intensive treatment Matter removal rate is 97%;Fluorine class removal of impurity is 90%;Organic removal of impurity is 90%;Metal and heavy metallic oxide and Radioactive metal class removal of impurity is 75%.
The present embodiment apparatus structure is the same as embodiment 1.

Claims (13)

1. a kind of method that electromagnetism strengthens ardealite removal of impurities, which is characterized in that specifically includes the following steps:
(1) be electrolysed from: ardealite and organic extractant are added in pickling tank by spiral crane and the concentrated sulfuric acid mixes system At ardealite slurries, heating, stirring keep slurries uniform, and the impurity in ardealite is allowed sufficiently to leach;Slurries after mixing are applied Electric field, the calcium sulphate dihydrate in ardealite are dissociated into calcium ion and sulfate ion in hot sulfuric acid, so that package, being adsorbed on phosphorus Metal, heavy metal and the radioactive element of gypsum surface and there are its intracell impurity sufficiently to release;In electric field masterpiece With the lower chemical bond for destroying organic and sulfide reference state metallic compound, it is promoted to convert to exchangeable species, to realize Transformation of the impurity from solid phase to liquid phase in ardealite, is segregated into ardealite slurries;Organic extractant is by impurity simultaneously Extraction enters in organic phase;
(2) electromagnetism migration deposits: being transported in water scrubber by ardealite slurries of the electrolysis from after, applies electric field in water scrubber And magnetic field, metal, heavy metal, radioactive metal ion under stirring in ardealite slurries are sent out under the action of electric field force Raw directional migration, the charged ion of migration in magnetic field by the effect of Lorentz force, by control pulsed magnetic generator Current direction make Lorentz force direction suffered by charged ion consistent with electric field force direction, accelerate ion to electrode two sides migrate Speed, the ion concentration near two electrodes is continuously increased, finally deposits in electrode surface, realize and ardealite slurries Separation;Electrode is taken out from electrode card slot, separated and dissolved is carried out to the metal, heavy metal and radioactive element deposited on electrode Obtain metallic solution, further recycle, the ardealite slurries after washing are dehydrated, by soluble Phosphorus, fluorine class and Semi-hydrated gypsum is obtained after organic impurity removal.
2. the method that electromagnetism according to claim 1 strengthens ardealite removal of impurities, it is characterised in that: the mass concentration of the concentrated sulfuric acid It is 25%~35%, the mass ratio of ardealite and the concentrated sulfuric acid is 1:3~1:5, and concentrated sulfuric acid extraction time is 45min~120min.
3. the method that electromagnetism according to claim 1 strengthens ardealite removal of impurities, it is characterised in that: organic extractant is phosphoric acid The mass volume ratio of tributyl, carbon tetrachloride or dioctylphosphoric acid ester, ardealite and organic extractant is 1:5~1:7.
4. the method that electromagnetism according to claim 1 strengthens ardealite removal of impurities, it is characterised in that: electric field is not by pickling tank The steel electrode that becomes rusty generates, and being passed through current system is direct current, and voltage is 10~30V, and electric field application time is to continuously apply.
5. the method that volume electromagnetism according to claim 1 strengthens ardealite removal of impurities, it is characterised in that: heat temperature in pickling tank Degree is 70~90 DEG C, and mixing speed is 40~80r/min.
6. the method that electromagnetism according to claim 4 strengthens ardealite removal of impurities, it is characterised in that: electric field is by more in water scrubber Pore electrod generates, and being passed through current system is direct current, and voltage is 30~60V, and electrode material is stainless steel, graphite or carbon;Electric field Application time is 1~3h, and the porosity of porous electrode is 20%~50%.
7. the method that electromagnetism according to claim 6 strengthens ardealite removal of impurities, it is characterised in that: sent out by pulsed magnetic field in magnetic field Helmholtz coil in raw device generates, and the voltage applied to coil is 20~50V, and helmholtz coil the number of turns is 50~100, Inductance is 5~30 μ H, and magnetic field application time is 60~180min.
8. the method that electromagnetism according to claim 1 strengthens ardealite removal of impurities, it is characterised in that: stirring speed in step (2) Degree is 30~60r/min.
9. the method that electromagnetism according to claim 7 strengthens ardealite removal of impurities, it is characterised in that: the water of water scrubber water inlet Flow velocity degree is 5~20m/s, and ardealite slurries moisture content is 80%~90% in water scrubber.
10. realizing that electromagnetism as claimed in claim 9 strengthens the device of the method for ardealite removal of impurities, it is characterised in that: including spiral Crane (1), pickling tank, pump (9), water scrubber, wherein pickling tank include shell (2), stainless steel electrode (3), heating tube (5), Feeding inlet (6), discharge port (7), blender I (8), stainless steel electrode (3) setting in the shell (2), shell (2) top be provided with into Material mouth (6), feeding inlet are connected to spiral crane (1), and shell (2) bottom is provided with discharge port (7), and heating tube (5) is arranged in shell Body (2) interior bottom, blender I (8) is provided in shell, and discharge port (7) is connect by pipeline with (9) are pumped;Water scrubber includes tower Shell (10), slurry inlet (11), electromagnetic generator (12), blender II (13), water inlet (14), serum outlet (15), Peep hole (4), tower shell (10) is interior to be provided with blender II (13), and tower shell (10) top is provided with water inlet (14), tower shell (10) lower part is provided with slurry inlet (11), and slurry inlet (11) is connect by pipeline with pump (9), and tower shell (10) bottom is provided with Serum outlet (15), tower shell (10) side are provided with more than one peep hole (4), and electromagnetic generator (12) is arranged in tower shell (10) in, stainless steel electrode (3), electromagnetic generator (12), heating tube (5), blender I, blender II connect with power supply respectively It connects.
11. the device that electromagnetism according to claim 10 strengthens ardealite removal of impurities, it is characterised in that: electromagnetic generator packet Bracket (16), magnetic induction loop (17), porous electrode (18) are included, magnetic induction loop (17) is arranged on bracket (16), porous electrode It (18) include arcuated porous positive plate and arcuated porous negative plate, porous electrode, which runs through, to be arranged in bracket, electromagnetic generator The electric field of generation, magnetic field cover water scrubber inner cavity.
12. the device that electromagnetism according to claim 10 strengthens ardealite removal of impurities, it is characterised in that: stainless steel electrode (3) Including arc positive plate and arc negative plate, the electric field that arc anode and arc cathode generate covers pickling tank inner cavity, and arc is just Pole plate and arc negative plate are connect with power positive cathode respectively.
13. the device that electromagnetism according to claim 10 strengthens ardealite removal of impurities, it is characterised in that: pump as corrosion resistant dirt Dredge pump.
CN201910768593.9A 2019-08-20 2019-08-20 The method and apparatus that electromagnetism strengthens ardealite removal of impurities Pending CN110451828A (en)

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