CN110282640A - A method of by arsenic alkaline slag extraction and separation resource utilization - Google Patents
A method of by arsenic alkaline slag extraction and separation resource utilization Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/24—Crystallisation
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G28/02—Arsenates; Arsenites
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/02—Antimonates; Antimonites
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Abstract
A method of by arsenic alkaline slag extraction and separation resource utilization, the following steps are included: by carrying out soaking molten extraction in leaching can by the arsenic alkaline slag glycerol adding of crushing and grinding or by the slurry after arsenic alkaline slag and glycerol together grinding, it is separated by solid-liquid separation, obtains Sb-rich residue and sweet oil-phase solution；The sweet oil-phase solution of gained is the mixed solution containing arsenate and soda ash, and the mixture through crystallisation by cooling or freezing and crystallizing isolated arsenic acid salt crystal and soda ash crystal, the glycerol that crystallisation by cooling or freezing and crystallizing are isolated is recycling in the molten extraction of leaching of arsenic alkaline slag；Gained Sb-rich residue is the solid mixture containing stibate, aluminosilicate mineral, for returning to antimony refining or processing antimony or antimony oxide and stibate.Process of the present invention is short, and investment is less, generates in separation process without Wastewater Pollutant, and with safety solvent extraction and separation arsenic alkaline slag, and solvent is can be recycled.
Description
Technical field
The present invention relates to a kind of methods of arsenic alkaline slag resource utilization, and in particular to a kind of by arsenic alkaline slag extraction and separation resource
Change the method utilized.
Background technique
Arsenic alkaline slag is generated a kind of containing natrium arsenicum, sodium antimonate, sodium carbonate in the antimony refining arsenic removal process of antimony pyrometallurgical smelting
Based on melting waste slag, because natrium arsenicum severe toxicity and it is soluble easily in water, easily lead to Environment Pollution Event, be difficult to properly locate all the time
The solid hazardous waste of reason constrains the sound development of antimony smelting industry to a certain extent.
For being difficult to the arsenic alkaline slag dealt carefully with, domestic and international scientific worker has been continued for a large amount of research and reality
It tramples, the various technical methods of existing arsenic alkaline slag processing substantially can be summarized as solidification landfill, wet-treating and pyrogenic attack three categories
Method.
The solidification burying method of arsenic alkaline slag include using cement solidification, lime/calcium salt solidification, molysite solidification, plastics solidification,
Then bitumen solidification, melting/vitrification solidifying etc. fill, although solidification landfill can to a certain extent, it is real in certain time
The fixation of existing arsenic, but these solidification burying methods all need a large amount of landfills than the big, later period in the presence of solidification front and back increase-volume and deposit
The long-term pollution hidden danger the problems such as.
The wet treatment method of arsenic alkaline slag mainly can be dissolved in water using alkali, natrium arsenicum and the sodium arsenite in arsenic alkaline slag,
And antimonious acid sodium and sodium antimonate indissoluble or property not soluble in water realize the separation of arsenic antimony, dissolve out arsenic, then use chemical precipitation
Method such as arsenic acid calcium precipitate, precipitated ferric arsenate, arsenones precipitating etc. or the method for direct crystallization natrium arsenicum and soda ash salt-mixture are into one
Step processing leachate.
Existing wet treatment method can be summarized as follows:
1) water logging-natrium arsenicum mixed salt method: being crushed arsenic alkaline slag material with hot water leaching, be separated into leached mud containing antimony and solution, leaching
Slagging tap send blast furnace to handle after drying, solution after evaporating completely is dry for natrium arsenicum salt-mixture (containing natrium arsenicum, sodium carbonate,
Sodium sulphate and a small amount of antimony), mainly as glass fining agent.
2) water logging-calcium slag method: arsenic alkaline slag wet type being crushed, then, is leached with hot water stirs, exhausted most arsenic therein
Sour sodium and sodium carbonate enter solution, are separated into leached mud containing antimony and leachate, send blast furnace to handle after leached mud drying, leachate
Add calcium hydroxide causticization, then is separated into calcium slag (calcium arsenate calcium carbonate) and soda bath.Though the rate of deposition of arsenic reachable 98%, calcium
Arsenic still reaches to 13~126mg/L in aqueous solution in slag, and solubility is bigger under acidic environment, and being still to be processed must have
Malicious danger solid waste.And liquid alkaline or piece alkali is made in soda bath after being concentrated by evaporation, and containing arsenic up to 3% or so, returns and is used as needle antimony essence
It is very unsatisfactory to refine Hydrodearsenic Catalyst effect, causes circulation of the arsenic in smelting system.
3) water logging-CO is aoxidized2Separation arsenic alkaline process: being crushed using hot water Oxidation Leaching or the arsenic alkaline slag of wet-milling, is separated into
Leachate (solution of containing sodium carbonate, natrium arsenicum, sodium sulphate, schlippe's salt etc.) and leached mud (contain sodium antimonate, antimonious acid sodium
With the solids of the gangue minerals such as metallic antimony and other silica).Then, the sodium carbonate in leachate is turned with carbon dioxide
The lower sodium bicarbonate of solubility is turned to, after the sodium bicarbonate (containing arsenic) for isolating crystallization, then Hydrodearsenic Catalyst is added in the solution and sinks
Form sediment natrium arsenicum out (containing alkali).Sodium bicarbonate heat treatment is converted into sodium carbonate (containing arsenic) and is back to antimony refining arsenic removal.
4) the heavy arsenic method of oxidation water logging-neutralization-vulcanization: with molten broken or wet-milling the arsenic alkaline slag of hot water oxidation leaching, it is separated into leaching
It slags tap (containing stibate etc.), leachate, leached mud is dry to return to blast furnace processing；Then, (containing natrium arsenicum, sodium arsenite, carbon
Sour sodium, sodium sulphate etc.) it a large amount of acid (generally with sulfuric acid or hydrochloric acid) is added in leachate neutralizes alkali therein, solution is adjusted to acid
Property, then plus H2S, Na2S sulfides by the arsenic in solution be converted into arsenones precipitating (As2S3).This method not only needs to consume
A large amount of acid goes to neutralize the alkali in leachate, and waste water still contains a certain amount of arsenic and a large amount of inorganic salts.
5) aoxidize water logging-ammonium arsenate metal salts as precipitator: after the oxidation water logging of broken or wet-milling arsenic alkaline slag, be separated by solid-liquid separation for containing
Leachate based on sodium carbonate and natrium arsenicum and containing the leached mud based on stibate；Then, metal ammonium complexing is added in leachate
Solion and crystal growth promoters are reacted, are aged, are crystallized, are precipitated, then solid-liquid separation ammonium arsenate metal salt；Again will
Solution heats de- ammonium, then, then is passed through carbon dioxide reaction and sodium bicarbonate crystal is precipitated, the sodium bicarbonate isolated is through thermally decomposing
For sodium carbonate (containing arsenic) reuse.Such removed with the wet-precipitated dearsenification method of metal-ammonia complex ion solution increase new metal from
Sub outer, dearsenification still has certain limitation, best (effect is optimal in molybdenum acid ammonia purification) the arsenic acid ammonia of even current effect
Magnesium processes, 0.038 gram of solubility in 20 DEG C of water of six water outlet arsenic acid ammonia magnesium of indissoluble, the solubility in 80 DEG C of water is 0.024 gram.
And the zinc ammonia precipitation effect in technology is inferior to ammonia magnesium precipitate effect at present.
Existing wet processing process requires to be dissolved in arsenic alkaline slag in a large amount of water, and precipitation method separation can generate body
The huge arsenious waste solution of product, direct emission can bring huge pollution to environment, advanced treating needed to can be only achieved discharge standard, locate
Manage at high cost, energy consumption height.Wherein the method for direct crystallization natrium arsenicum and soda ash is also to need to evaporate the liquid containing arsenic of large volume, and steam
Micro- foam containing arsenic that hair process is difficult to avoid that splashes, severe operational environment；In addition the natrium arsenicum product impurity content of output is higher, and
The limited backlog of the products market demand such as common natrium arsenicum, arsenones is big, and wet processing operation is unsatisfactory on the whole.
The basic technology of the pyrogenic attack of arsenic alkaline slag is " arsenic alkaline slag blast furnace volatile smelting+reduction smelting in reverberatory furnace refining "
Arsenic alkaline slag investment stibium blast furnace is carried out volatile smelting, while being incorporated enough flux and coke by method, arsenic in arsenic alkaline slag,
Antimony is oxidized together enters flue gas cooling device, thick three oxidation two of the high arsenic of cooling recycling with high-temperature flue gas in the form of the oxide
Antimony reenters addition reducing agent in reverberatory furnace and is reduced to needle antimony, and soda ash then is added in reverberatory furnace again or piece alkali air blast is repeatedly smart
Refining obtains qualified antimony slab.The advantage of pyrogenic attack arsenic alkaline slag is that processing capacity is big, high production efficiency, can use antimony smelting
The equipment of system.But because raw material/return product are high containing arsenic, first operating environment is poor, and personal safety risk is big, and second high arsenic needle antimony is anti-
The return product that multiple refining generates are higher containing arsenic, form the vicious circle of arsenic, moreover require to have perfect, closed cooling to gather dust and be
System.
CN102965517A discloses a kind of processing method of arsenic alkaline slag glass solidification, in the molten state by arsenic alkaline slag first
Sodium antimonate is selectively reduced to metallic antimony for reduction with carbon agent and arsenic is present in slag with arsenic acid na form；Then in slag containing arsenic
Middle addition glass melting dosage form is at low temperature glass phase, and water quenching is at cullet block or the founding directly in ingot mould after glass phase is released
At glass ingot, convenient for storing up and returning pit landfill.
CN104073644B discloses refining lead slag-removed by antimony fire refining process reduction smelting method synchronous with arsenic alkaline slag proportion, including
Following steps: (1) it is lead slag-removed with arsenic alkaline slag by weight, according to sodium in the content and arsenic alkaline slag of lead slag-removed middle phosphate anion from
The content of son determines lead slag-removed and arsenic alkaline slag proportion, wherein the matter of sodium ion and lead slag-removed middle phosphate anion in arsenic alkaline slag
Amount is than being 60~80: 90~120；(2) the lead slag-removed and arsenic alkaline slag matched by step (1) is uniformly mixed, anthracite, institute is added
Adding anthracite is lead slag-removed 3~15% with arsenic alkaline slag total weight, cooling in 800~1000 DEG C of constant temperature processing 30~after sixty minutes
To room temperature, antimony arsenical lead and tertiary sodium phosphate dross are separated,.
CN108220626A discloses a kind of arsenic alkaline slag reduction melting processing method, this method by arsenic alkaline slag and carbonaceous also
Reduction melting obtains arsenic steam, needle antimony and reducing slag after former agent mixing, obtains metallic arsenic product after the condensation of arsenic steam；Reducing slag
Main component is Na2CO3, antimony can be returned to directly as Hydrodearsenic Catalyst and refine dearsenification process, can also pass through water logging-concentration-knot
Brilliant technique obtains Na2CO3Crystal.
CN106636678A discloses a kind of method that arsenic-containing material direct-reduction roasting prepares arsenic, and this method is with arsenate
For raw material, arsenate material and carbonaceous reducing agent after mixing, are placed in inertia or reducing atmosphere, under condition of negative pressure, into
Row reduction roasting collects baking flue gas to get arsenic product.
Above-mentioned pyrogenic processing method, the condition for heat-treating processing is harsh, vacuum arc furnace ignition between needing to seal, using vacuum pumping
Vacuum vacuumizes 1~8 hour in hot conditions are mandatory, the control of this intermittence fire reduction processing require it is very stringent, it is right
Equipment requirement and operation control require height, may only be adapted to laboratory or small batch Metallurgical processing, and large batch of industry is raw
The adaptability of production leaves a question open；Also it is less adapted to handle the arsenic alkaline slag containing a large amount of antimony, vacuum pump is used to continue at >=800 DEG C strong take out
Under the situation of vacuum, the volatilization of antimony steam will occur simultaneously with the distillation (615 DEG C of arsenic distillations) of arsenic, and what is frequently resulted in only can be arsenic
Antimony alloy；And be difficult to largely handle the arsenate containing stibate, using carbon as reducing agent smelting arsenic alkali slag, reduction temperature is lower than 800
DEG C when whole reducing power it is still extremely weak, 900 DEG C or more just have preferable reproducibility, and are directed to hazardous waste disposal temperature
Degree is higher, more than energy consumption height, the higher problem of equipment Requirement, and potential accident risk is bigger, and due to using closing
Reduction furnace, which is stood in its gained needle antimony lead of carbon reducing agent evacuation process, still contains arsenic, still contains not a small amount of arsenic in reducing slag
(including Soluble Arsenic hydrochlorate and insoluble arsenate) has still only achieved the purpose that partial reduction separates, either needle antimony
Return refining, or reducing slag return the circulation of arsenic is all caused as Hydrodearsenic Catalyst.Both just under strict control reaction condition
Still contain a certain amount of arsenic in the water logging slag that its reducing slag separates after water logging, be still that dangerous solid waste needs to locate
Reason；Arsenic steam or arsenic flue gas or elemental arsenic in treatment process are easily oxidized, and force to take out with vacuum pump especially out of high temperature furnace
Out to during cooling, even with the mixed atmosphere of inert gas and/or nitrogen and hydrogen and/or carbon monoxide etc.,
Extremely difficult recycling, easily leads to that economy is bad or pollution atmosphere, and is sucked by vacuum the vacuum pump pair that is relied on of arsenic flue gas
The adaptability of metal particle or exhaust gas dust is very poor, it is difficult to guarantee normal production run；Or need through strict control sodium and
The equivalent proportion of phosphate radical generates the reaction condition of tertiary sodium phosphate, by arsenic alkaline slag stibate and arsenate etc. be reduced into list simultaneously
Matter antimony and elemental arsenic, and the production of actual antimony smelting enterprise control habit is difficult to ensure that it seems simple reaction condition, and
It handles energy consumption height, and potential pollution hidden danger is big, and especially the tertiary sodium phosphate dross containing arsenic easily quietly flows into agricultural fertilizer market and leads
It causes to pollute uncontrollable diffusion.
In conclusion arsenic, antimony, the separation of alkali resource are more difficult in the treatment process of existing all kinds of arsenic alkaline slags, especially
Be arsenic disposition difficulty it is big, it is prominent the problems such as environmental protection and economy.
Summary of the invention
The technical problem to be solved by the present invention is to, overcome drawbacks described above of the existing technology, it is short to provide a kind of process,
It invests less, is generated in separation process without Wastewater Pollutant, with safety solvent extraction and separation arsenic alkaline slag, and the recyclable benefit of solvent
By arsenic alkaline slag extraction and separation resource utilization method.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of by arsenic alkaline slag extraction and separation recycling benefit
Method, comprising the following steps: will be after the arsenic alkaline slag glycerol adding of crushing and grinding or by arsenic alkaline slag and glycerol together grinding
Slurry carry out soaking molten extraction in leaching can, be separated by solid-liquid separation, obtain Sb-rich residue and sweet oil-phase solution；The sweet oil-phase solution of gained be containing
The mixed solution of arsenate and soda ash, the mixing through crystallisation by cooling or freezing and crystallizing isolated arsenic acid salt crystal and soda ash crystal
The glycerol that object, crystallisation by cooling or freezing and crystallizing are isolated is recycling in the molten extraction of leaching of arsenic alkaline slag；Gained Sb-rich residue is containing antimony
The solid mixture of hydrochlorate, aluminosilicate mineral, for returning to antimony refining or processing antimony or antimony oxide and stibate.
Further, the molten extraction of the leaching soaks molten 0.5h~8h for 60 DEG C~150 DEG C stirrings.
Further, partial size < 100 μm of the slurry.
Further, the mesh number of the sieving of the arsenic alkaline slag by crushing and grinding be 160 mesh~800 mesh (preferably 200~
400 mesh).
Further, the dosage of the glycerol is 1~15 times (preferably 2~6 times) of arsenic alkaline slag quality.
Further, the molten extraction of the leaching includes that the molten extraction of single-stage leaching, the molten extraction of multistage leaching or leaching trough counter-current soak molten extraction.
Sufficiently to extract the arsenate and soda ash in arsenic alkaline slag, make arsenate in sweet oil-phase solution, soda ash in the molten extraction of the leaching of setting
At a temperature of reach saturation solubility；
Further, when the pH value of water solution of the arsenic alkaline slag > 11.7, sodium bicarbonate combined grinding is added or adds when soaking molten extraction
Enter sodium bicarbonate, adjusts the pH value of water solution of arsenic alkaline slag or pH value of water solution < 11.7 of sweet oil-phase solution.
Further, the glycerol mix liquid crystallisation by cooling and/or freezing and crystallizing separation crystallized product can directly take out, or
As produce arsenic product, purification soda ash or caustic soda raw material, soda ash/caustic soda also can direct reuse in antimony refine.
Further, the glycerol can use mannitol or xylose alcohol part substitution or replacing whole.
The invention has the advantages that: (1) can dissolve under certain condition using natrium arsenicum, sodium arsenite, soda ash, sodium bicarbonate
Increase changes in solubility in glycerol, and with temperature, and in pH value < 11.7 sodium antimonate, antimonious acid sodium is extremely difficult is dissolved in glycerol
In, and use the glycerol of more cheap physiological-toxicity-free for extractant, the molten extraction arsenic alkaline slag of selective leaching in pH value < 11.7
In arsenate and soda ash, heat preservation separation obtains and removes the Sb-rich residue of arsenic removal, alkali；(2) solubility of the arsenate in glycerol is utilized
It varies with temperature and more sensitive, implements that cooling down isolates arsenic acid salt crystal, freezing and crystallizing isolates soda ash crystal, or is primary
Property freezing and crystallizing isolates salt-mixture.And the glycerol crystal after freezing and crystallizing separation is sharp using recycling after the heating of heat exchange waste heat
With；(3) process flow is simple, and investment is less, and good separating effect, treating capacity is big, and can easily realize no dust work, entire work
It is discharged during skill without dust, without technology waste gas, without technique waste water；(4) one kind is provided for the processing that efficiently separates of arsenic alkaline slag
Completely new technical thought is also soda ash, the production of arsenic product, antimony product provides the raw material convenient for utilizing.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
Embodiment 1
The secondary arsenic alkaline slag in Hunan antimony smeltery is selected, 9 .68% of As content, Sb content 5.68%, carbonate content are detected
41.53%；Selecting commercially available industry glycerol (content 99.5%) is solvent, and selecting commercially available sodium bicarbonate is pH adjusting agent.
The present embodiment the following steps are included: arsenic alkaline slag crushing and grinding crosses 200 meshes, be sent into leaching can, add by arsenic alkaline slag powder
The glycerol of 6 times of arsenic alkaline slag silty amount soaks molten 4h in normal pressure, 100 DEG C of stirrings, and heat preservation separation obtains Sb-rich residue and sweet oil-phase solution.It is sweet
Arsenate crystal seed is precipitated through cooling down in oil-phase solution, filters out arsenic acid salt crystal, then, isolates then at -20 DEG C of freezing and crystallizings
Soda ash.The glycerol that freezing and crystallizing is isolated is recycling in the molten extraction of leaching of arsenic alkaline slag.
Through detecting, the resulting Sb-rich residue main component of the present embodiment is stibate, alumino-silicate etc., arsenic content in Sb-rich residue
For 0.74%, carbonate content 0.23%, TCLP experiment detection arsenic content 0.08mg/L.Illustrate with Glycerol solvents extraction and separation
Arsenic, alkali effect are fine.Sb-rich residue can return to antimony smelting system, or as producing antimony product raw material.Wherein, antimony content in arsenate
0.069%, carbonate content 1.87%.Antimony content 0.034% in soda ash, arsenic content 0.98%.
It takes arsenate to produce al arsenate as raw material: arsenate is dissolved in water, add hydrochloric acid neutralization to be wherein mingled with a small amount of
Soda ash adds equivalent liquor alumini chloridi reaction precipitating, filtering washing obtains high-quality al arsenate to pH7.5；It is molten that phytic acid is added dropwise in filtrate
Liquid purification is settled out wherein micro heavy metal ion.
It takes soda ash as feed purification soda ash product: soda ash is dissolved in water, it is complete that liquor alumini chloridi reaction precipitating is added dropwise
A small amount of arsenate therein, filters to isolate al arsenate solid, and plant acid solution is added dropwise in filtrate to being settled out micro residue completely
Arsenic ion and the above metal ion of other divalent, TCLP experiment detect arsenic content 0.002mg/L in solution, are concentrated by mature technology
Crystallizing and drying grinding obtains soda ash product.
Embodiment 2
The secondary arsenic alkaline slag in Hunan antimony smeltery is selected, 11 .31% of As content, Sb content 4.37%, carbonate content are detected
27.21%；Selecting commercially available industry glycerol (content 99.5%) is solvent, and selecting commercially available sodium bicarbonate is pH adjusting agent.
The present embodiment was the following steps are included: be 74 μm of sieves by the broken glycerol for adding 2 times of quality of arsenic alkaline slag together grinding
Slurry is sent into leaching can, adds 4.5 times that amounts of glycerol reaches arsenic alkaline slag quality, and sodium bicarbonate control pH value is added to be less than
11.7, molten 2h is soaked in normal pressure, 140 DEG C of stirrings, heat preservation separation obtains Sb-rich residue and sweet oil-phase solution.Sweet oil-phase solution is through disposable
Cooling is refrigerated to -5 DEG C of Crystallization Separations and goes out arsenate soda ash mixture.The glycerol that freezing and crystallizing is isolated is recycling in arsenic alkaline slag
The molten extraction of leaching.
Through detecting, the resulting Sb-rich residue main component of the present embodiment is stibate, alumino-silicate etc., arsenic content in Sb-rich residue
For 0.59%, carbonate content 0.52%, TCLP experiment detection arsenic content 0.05mg/L.Illustrate with Glycerol solvents extraction and separation
Arsenic, alkali effect are fine.Sb-rich residue can return to antimony smelting system, or as producing antimony product raw material.Wherein, arsenate soda ash mixes
Antimony content 0.057% in object.
Taking arsenate soda ash mixture is waste copper arsenate and soda ash: arsenate soda ash mixture is dissolved in water,
The copper chloride solution that 1.03 times of equivalents of arsenate are added sufficiently reacts, and is separated by filtration to obtain copper arsenate, plant acid solution is added dropwise in filtrate
To complete precipitate residual copper ion and the above metal ion of other divalent, TCLP experiment detects arsenic content 0.004mg/L in solution,
Sodium chloride and soda ash product are obtained by mature technology Crystallization Separation.
Embodiment 3
Certain antimony smeltery arsenic alkaline slag is selected, ingredient detects in manufacturer are as follows: As: 17.98%, Sb: 21.87%, Na: 28.13%；
Selecting commercially available industry glycerol (content 99.5%) is solvent, and selecting commercially available sodium bicarbonate is pH adjusting agent.
For the present embodiment the following steps are included: by arsenic alkaline slag crushing and grinding to 250 mesh, arsenic alkaline slag powder equivalent is sent into three leachings
In tank, soak molten extractions using three-levels in normal pressure, 120 DEG C, the first order soaks molten plus 3 times of arsenic alkaline slag silty amount glycerol, in normal pressure,
Molten 1h is soaked in 120 DEG C of stirrings, filters separation, and sweet oil-phase solution is transferred to the molten 1h of leaching in the leaching can of the second level, filters separation, and glycerol mixes
Liquid is transferred to the molten 1h of leaching in third level leaching can, filters separation, micro-filtration filters to obtain the sweet oil-phase solution of saturation；It is taken out in first order pot for solvent extraction
After filtering out sweet oil-phase solution, the molten 1h smoke filtrate of the new glycerol leaching of equal amount is added again and is transferred to second level leaching can, is taken out after soaking molten 1h
Filtrate is transferred to third level leaching can, in this way, arsenic alkaline slag sufficiently soaks molten extraction through Glycerol solvents, separates to obtain Sb-rich residue.
It is saturated sweet oil-phase solution and arsenate crystal seed is precipitated through cooling down, arsenic acid salt crystal is filtered out, then, then at -13 DEG C
Freezing and crystallizing isolates soda ash.The glycerol that freezing and crystallizing is isolated is recycling in the molten extraction of leaching of arsenic alkaline slag.
Through detecting, Sb-rich residue main component obtained by the present embodiment is stibate, alumino-silicate etc., and arsenic content is in Sb-rich residue
0.52%, carbonate content 0.16%, TCLP experiment detection arsenic content 0.05mg/L.Illustrate with Glycerol solvents extraction and separation arsenic,
Alkali effect is fine.
Sb-rich residue can return to antimony smelting system, or as producing antimony product raw material.
Antimony content 0.079% in arsenate, carbonate content 1.97%.
Antimony content 0.073% in soda ash, arsenic content 1.75%.
Embodiment 4
Certain antimony smeltery arsenic alkaline slag is selected, ingredient detects in manufacturer are as follows: As: 21.42%, Sb: 34.37%, Na: 28.11%；
Selecting commercially available industry glycerol (content 99.5%) is solvent, and selecting commercially available sodium bicarbonate is pH adjusting agent.
The present embodiment was made 200 the following steps are included: add the sodium bicarbonate of mass ratio 7% when by arsenic alkaline slag crushing and grinding
Purpose arsenic alkaline slag powder, arsenic alkaline slag powder equivalent are sent into three leaching cans, soak molten extraction, the first order using three-level in normal pressure, 135 DEG C
Molten plus 2.5 times of arsenic alkaline slag silty amount glycerol is soaked, molten 0.8h is soaked in normal pressure, 135 DEG C of stirrings, filters separation, sweet oil-phase solution turns
Enter the molten 0.8h of leaching in the leaching can of the second level, suction filtration separation, sweet oil-phase solution is transferred to the molten 0.8h of leaching in third level leaching can, filters and divide
Sweet oil-phase solution must be saturated from, ultra-filtration filters；After filtering out sweet oil-phase solution in first order pot for solvent extraction, it is new that equal amount is added again
Glycerol soaks molten 0.8h smoke filtrate and is transferred to second level leaching can, and smoke filtrate is transferred to third level leaching can after soaking molten 0.8h, in this way, arsenic alkali
Slag sufficiently soaks molten extraction through Glycerol solvents, separates to obtain Sb-rich residue.
Sweet oil-phase solution is refrigerated to -15 DEG C of Crystallization Separations through disposable cooling and goes out arsenate soda ash mixture.Freezing and crystallizing
The glycerol isolated is recycling in the molten extraction of leaching of arsenic alkaline slag.
Through detecting, Sb-rich residue main component obtained by the present embodiment is stibate, alumino-silicate etc., and arsenic content is in Sb-rich residue
0.24%, carbonate content 0.19%, TCLP experiment detection arsenic content 0.02mg/L.Illustrate with Glycerol solvents extraction and separation arsenic,
Alkali effect is fine.
Sb-rich residue can return to antimony smelting system, or as producing antimony product raw material.Wherein, antimony in arsenate soda ash mixture
Content 0.091%.
Sb-rich residue is taken to produce oxidation antimony powder as raw material: by Sb-rich residue and water, glycerol, sodium hydroxide in mass ratio 1: 3: 3:
1.5 ratio is stirred to react the molten 4h of leaching in 90 DEG C, filters to isolate sial slag；Vulcanized sodium reaction is added dropwise in alkali glycerine water solution
It is settled out lead bismuth, vulcanized lead bismuth sulfide is isolated and precipitates to obtain lead skim；Hydrochloric acid is added to be neutralized to pH value in alkali glycerine water solution again
6.5, separate to obtain oxidation antimony powder；Again in glycerine water solution be added dropwise plant acid solution react to the whole divalent being settled out in solution from
Son and heavy metal ion, isolate phytic acid sediment；Micro-filtration filters to obtain glycerol saline solution；Glycerol saline solution is used in 37 DEG C
Nanofiltration membrane analysis separation, UF membrane obtain nanofiltration concentrate and dialyzate glycerine water solution.Glycerine water solution, which returns, soaks molten Sb-rich residue, dense
Sodium chloride product is made in the spray drying of contracting liquid.
Gained aoxidizes antimony powder routinely technique purified treatment, must aoxidize antimony powder product.
Sial slag is detected as aluminosilicate mineral, antimony content 0.87%, arsenic content 0.009%, and TCLP experiment detection arsenic contains
Measure 0.007mg/L.
Embodiment 5
Certain antimony smeltery arsenic alkaline slag is selected, is detected: As content 14.57%, Sb content 8.94%, carbonate content 28.76%；Choosing
It is solvent with commercially available industry glycerol (content 99.5%), selecting commercially available sodium bicarbonate is pH adjusting agent.
The present embodiment is the following steps are included: by arsenic alkaline slag is broken plus the glycerol of 2 times of quality and adds sodium bicarbonate to controlling pH
Value 11.5~11.7, grinding was the slurry of 80 μm of sieves together, was sent into continous way counter-current extraction slot, and counter-current extraction slot uses
Ultrasonic wave stirring, counter-current extraction Glycerol solvents total amount are added to 6 times of arsenic alkaline slag gross mass, in normal pressure, 145 DEG C of ultrasonic wave stirrings
Molten 2h is soaked, heat preservation separation obtains Sb-rich residue and sweet oil-phase solution.Sweet oil-phase solution is refrigerated to -10 DEG C of crystallizations point through disposable cooling
Separate out arsenate soda ash mixture；The glycerol that freezing and crystallizing is isolated is recycling in the molten extraction of leaching of arsenic alkaline slag.
Through detecting, Sb-rich residue main component obtained by the present embodiment is stibate, alumino-silicate etc., and arsenic content is in Sb-rich residue
0.03%, carbonate content 0.86%, TCLP experiment detection arsenic content 0.09mg/L.Illustrate with Glycerol solvents extraction and separation arsenic,
Alkali effect is fine.
Sb-rich residue can return to antimony smelting system, or as producing antimony product raw material.
Antimony content 0.087% in arsenate soda ash mixture.
Claims (10)
1. a kind of method by arsenic alkaline slag extraction and separation resource utilization, it is characterised in that: the following steps are included: will be by broken
The arsenic alkaline slag glycerol adding of grinding carries out the slurry after arsenic alkaline slag and glycerol together grinding to soak molten extraction, solid-liquid in leaching can
Separation, obtains Sb-rich residue and sweet oil-phase solution；The sweet oil-phase solution of gained is the mixed solution containing arsenate and soda ash, through crystallisation by cooling
Or the mixture of freezing and crystallizing isolated arsenic acid salt crystal and soda ash crystal, the glycerol that crystallisation by cooling or freezing and crystallizing are isolated
It is recycling in the molten extraction of leaching of arsenic alkaline slag；Gained Sb-rich residue is the solid mixture containing stibate, aluminosilicate mineral, is used for
Return to antimony refining or processing antimony or antimony oxide and stibate.
2. the method according to claim 1 by arsenic alkaline slag extraction and separation resource utilization, it is characterised in that: the leaching is molten
Extraction soaks molten 0.5h~8h for 60 DEG C~150 DEG C stirrings.
3. the method according to claim 1 or 2 by arsenic alkaline slag extraction and separation resource utilization, it is characterised in that: described
Partial size < 100 μm of slurry.
4. the method according to claim 1 or 2 by arsenic alkaline slag extraction and separation resource utilization, it is characterised in that: described
Mesh number by the sieving of the arsenic alkaline slag of crushing and grinding is 160 mesh~800 mesh.
5. by the method for arsenic alkaline slag extraction and separation resource utilization described according to claim 1~one of 4, it is characterised in that:
The dosage of the glycerol is 1.0~15 times of arsenic alkaline slag quality.
6. the method according to claim 5 by arsenic alkaline slag extraction and separation resource utilization, it is characterised in that: the glycerol
Dosage be 2~6 times of arsenic alkaline slag quality.
7. by the method for arsenic alkaline slag extraction and separation resource utilization described according to claim 1~one of 6, it is characterised in that:
The molten extraction of leaching includes that the molten extraction of single-stage leaching, the molten extraction of multistage leaching or leaching trough counter-current soak molten extraction.
8. by the method for arsenic alkaline slag extraction and separation resource utilization described according to claim 1~one of 7, it is characterised in that:
When the pH value of water solution of the arsenic alkaline slag > 11.7, sodium bicarbonate combined grinding is added or sodium bicarbonate is added when soaking molten extraction,
Adjust the pH value of water solution of arsenic alkaline slag or pH value of water solution < 11.7 of sweet oil-phase solution.
9. by the method for arsenic alkaline slag extraction and separation resource utilization described according to claim 1~one of 8, it is characterised in that:
The glycerol mix liquid crystallisation by cooling and/or freezing and crystallizing separation arsenic acid salt crystal and soda ash crystal and its mixture it is directly outer
It sells or as the raw material for producing arsenic product and/or purification alkali；Gained soda ash/caustic soda is refined for antimony.
10. by the method for arsenic alkaline slag extraction and separation resource utilization described according to claim 1~one of 9, it is characterised in that:
The glycerol can use mannitol or xylose alcohol part substitution or replacing whole.
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| CN112919801A (en) * | 2021-02-23 | 2021-06-08 | 浙江本尊新材料科技有限公司 | Method for preparing arsenic-containing borosilicate glass by arsenic solid waste treatment |
| CN114261979A (en) * | 2021-12-30 | 2022-04-01 | 耒阳市焱鑫有色金属有限公司 | Method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali |
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| CN114261979A (en) * | 2021-12-30 | 2022-04-01 | 耒阳市焱鑫有色金属有限公司 | Method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali |
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