CN102628105A - Method for comprehensively recycling and using baric waste slag in refined aluminum production process - Google Patents

Method for comprehensively recycling and using baric waste slag in refined aluminum production process Download PDF

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CN102628105A
CN102628105A CN2012101132583A CN201210113258A CN102628105A CN 102628105 A CN102628105 A CN 102628105A CN 2012101132583 A CN2012101132583 A CN 2012101132583A CN 201210113258 A CN201210113258 A CN 201210113258A CN 102628105 A CN102628105 A CN 102628105A
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filtrating
hydrochloric acid
liquor
barium
technology
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CN102628105B (en
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景燕
马军
贾永忠
王小华
姚颖
孙进贺
李磊
林鹏程
田素燕
吕学海
尹刚
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Qinghai Safety Science & Technology Center
Qinghai Institute of Salt Lakes Research of CAS
Qinghai Nationalities University
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Qinghai Safety Science & Technology Center
Qinghai Institute of Salt Lakes Research of CAS
Qinghai Nationalities University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a method for comprehensively recycling and using baric waste slag in a refined aluminum production process, wherein the method is composed of a fluorine ion recycling technology, a leaching liquid separation technology, an iron-aluminum separation technology and a sodium-barium separation technology. The method provided by the invention is easy to control and operate; and according to the method, the baric waste slag generated in the refined aluminum production process can be separated into calcium fluoride, barium chloride, sodium chloride and aluminum hydroxide, so that various major elements in the baric waste slag generated in the refined aluminum production process are separated and recycled, therefore the purposes of comprehensively and cyclically utilizing resources, saving energy, reducing emission, reducing environmental pollution and improving production safety are achieved.

Description

The method of The Barium Residue in a kind of comprehensive reutilization refined aluminium production process
Technical field
The present invention relates to the refined aluminium production field, relate in particular to the method for The Barium Residue in a kind of comprehensive reutilization refined aluminium production process.
Background technology
The sophisticated technology of refined aluminium electrolysis is three layers of liquid refined aluminium electrolysis process both at home and abroad at present, uses chlorine fluorine electrolyte system as the ionogen in the refined aluminium electrolysis usually.
Bariumchloride has played irreplaceable effect as one of main ionogen of three layers of liquid refined aluminium electrolysis process in the refined aluminium generative process.Three layers of liquid refined aluminium electrolysis process are relatively stricter to electrolytical requirement, and ionogen must possess characteristics such as density is moderate, volatility is little, electroconductibility is good, liquidus temperature is low.Bariumchloride and other ionogen acting in conjunction are regulated the various character of the electrolyte system in the refined aluminium electrolysis.The existence of an amount of bariumchloride can effectively reduce whole refined aluminium electrolysis system liquidus temperature in the refined aluminium electrolyte system, when bariumchloride concentration in 50% ~ 70% scope, the bariumchloride of about every increase by 1%, the liquidus temperature of electrolysis system then can descend 1.5 ℃; In existing industrial refined aluminium electrolyte system, the density of electrolyte system is determined by the content of bariumchloride to a great extent.When the concentration of bariumchloride in the electrolyte system greater than 58% the time, the density of electrolyte system increases sharply along with the increase of bariumchloride concentration; The existence of bariumchloride has been led negative interaction to the electricity of electrolyte system, and along with the increase of bariumchloride concentration in the system, the electricity of system is led and presented downward trend.So comprehensive above-mentioned various factors, in existing refined aluminium electrolyte system, the concentration of bariumchloride is about 60%.
In the refined aluminium electrolytic process, possibly produce following impurity substances:
Following side reaction possibly take place in material in electrolysis system:
(1)
(2)
(1) is actual can not take place in reaction, can carry out consumingly and react (2).Newly-generated BaF in the refined aluminium electrolytic process 2Following reaction has taken place with original bariumchloride in the electrolyte system:
(3)
The BaCl that generates in the reaction (3) 2BaF 2Under the refined aluminium electrolysis temperature,, from electrolyte system, separate for being refractory to the material of electrolytic solution.Because the concentration of NaF is low in the electrolyte system, the part bariumchloride has been participated in reaction in the electrolyte system, has formed the waste residue that is refractory to electrolytic solution.
Contain partially fluorinated aluminium in electrolyte system, ALUMNIUM FLUORIDE mainly act as the electricity of regulating whole electrolyte system and leads and liquidus temperature.In the refined aluminium electrolytic process, following reaction has taken place in the little water branch that the ALUMNIUM FLUORIDE of part and airborne moisture and raw material are brought in the electrolyte system:
(4)
The aluminum oxide that generates in the reaction (4) for being refractory to the material of electrolytic solution, is separated from electrolyte system with the form of waste residue under the refined aluminium electrolysis temperature.
In the refined aluminium generative process, the raw material of employing is an xaloy, along with the carrying out of refining process; The impurity iron of the minute quantity in the primary aluminum, silicon are gathered in the anode alloy; Therefore anode alloy is the Al-Cu-Fe-Si quaternary system, in this system, has many infusible compounds, like FeSiAl 5, sosoloid α (Al-Fe-Si), β (Al-Fe-Si) etc.In fusion processes, above-mentioned impurity is transferred in the electrolyte system at anode, separates from system with the form of waste residue.
In the refined aluminium generative process; Part bariumchloride, ALUMNIUM FLUORIDE etc. react and generate infusible compound and from system, separate in the electrolyte system; In actual production process; To analyze the composition of electrolyte system, will in time in electrolyte system, add materials such as bariumchloride, ALUMNIUM FLUORIDE simultaneously.In solubility (water-soluble) The Barium Residue that forms, bariumchloride belongs to the 6.1st type of poisonous substances in the hazardous chemical register, eats more than the 0.2g to cause poisoning, and its lethal quantity is 0.8 ~ 0.9g.Bariumchloride is a highly toxic substance, can cause brain and Leptomeningeal inflammation, and capillary permeability raises during poisoning, simultaneously with hemorrhage and oedema.Secondly bariumchloride can also suppress marrow and cause diseases such as hepatic diseases, splencerqatosis.Symptoms such as that the bariumchloride acute poisoning shows as is nauseating, vomiting, stomachache, diarrhoea, arteries and veins are slow, muscular paralysis, arrhythmia can be because of arrhythmia and paralysis of respiratory muscle death; Symptoms such as shortness of breath, oral mucosa swelling erosion, tachycardia, blood pressure are increased, alopecia appear in long-term contact bariumchloride easily, so in bariumchloride must be stored between cool place, airy storehouse, in order to avoid to surrounding enviroment generation safety, environmental issue.
In the generation of refined aluminium production process the great amount of soluble The Barium Residue is arranged.The solubility The Barium Residue can go underground in water and the surface water through the rain penetration soluble barium salt in the process of storing up, and the environmental safety of periphery is produced bigger influence, and the while has also been caused the waste of resource.
The application is to the solubility The Barium Residue that produces in the refined aluminium production process; Invented a kind of comprehensive utilization method; Realize the comprehensive utilization of waste residue, reduction and elimination waste residue are realized the target of safety, resource circulation utilization and Sustainable development in the refined aluminium production process to the harm of surrounding enviroment.
Summary of the invention
Technical problem to be solved by this invention provides the method for The Barium Residue in a kind of comprehensive reutilization refined aluminium production process that is easy to red-tape operati.
For addressing the above problem, the method for The Barium Residue in a kind of comprehensive reutilization refined aluminium production process of the present invention, it is characterized in that: this method is made up of fluoride recovery technology, leach liquor separating technology, iron aluminum separation technique, sodium barium separating technology; Wherein
Said fluoride recovery technology is meant at first with dropping in the acidleach jar through feeder behind The Barium Residue in the refined aluminium production process and the mass ratio mixing formation compound of calcium chloride by 1:0.2 ~ 1; Add entry and adopt electric blender to stir; Hydrochloric acid is pumped into said acidleach jar from hydrochloric acid tank ; It is that 36% hydrochloric acid is 180 ~ 450 g that every liter of mixing solutions need add mass concentration, obtains pickling liquor behind acidleach 0.5 ~ 2.0 h; The solid-liquid mass volume ratio of liquid is 1:2 ~ 10 in said The Barium Residue and the acidleach jar; Said pickling liquor is pumped into pressure filter ; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 0.5 ~ 1.5 h under the pressure of 0.2MPa ~ 0.5MPa obtains solid phase Calcium Fluoride (Fluorspan) and filtrating A respectively; Last said solid phase Calcium Fluoride (Fluorspan) comes back to electrolysis refined aluminium technology after drying, said filtrating A gets into the removing impurities by oxidation groove in the said leach liquor separating technology;
It is that 27% ydrogen peroxide 50 pumps into said removing impurities by oxidation groove from the ydrogen peroxide 50 storage tank that said leach liquor separating technology is meant at first mass concentration, and to said filtrating A oxide treatment 0.5 ~ 2.5 h, the volume ratio of said liquid phase A and said ydrogen peroxide 50 is 1:0.005 ~ 0.01; Be that 25% ammoniacal liquor pumps into said removing impurities by oxidation groove from tank used for storing ammonia with mass concentration then, and regulate pH value to 6.5 ~ 7.5 of said filtrating A; This moment, said filtrating A pumped into pressure filter , use neutral 300 orders to 500 order filter clothes, press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa obtains liquor B and iron content, aluminium contamination precipitation slag respectively, and this iron content, aluminium contamination precipitation slag get into said iron aluminum separation technique; Secondly said liquor B gets into high temperature deblending slot, simultaneously with saturated NaOH solution from the alkali lye pond In pump into said high temperature deblending slot, regulate pH value to 10.0 ~ 14.0 of said liquor B; This moment, said liquor B pumped into pressure filter , keep the filtrating temperature in 30 ℃ ~ 90 ℃ scopes, use alkaline-resisting type 500 orders to 700 order filter clothes, press filtration 0.5 ~ 1.5 h removes calcium, the magnesium addition in the liquor B under the pressure condition of 0.3MPa ~ 0.8MPa, obtains liquor C, and this liquor C inputs to neutralizing well; Be that 36% hydrochloric acid is from hydrochloric acid tank with mass concentration at last In pump into said neutralizing well, make the pH value of said liquor C be neutral, obtain NaCl, BaCl 2Mixing solutions, this mixing solutions get into the settling bath in the said sodium barium separating technology
Said iron aluminum separation technique is meant that at first the precipitation slag with iron content, aluminium in the said leach liquor separating technology drops in the decomposer through feeder ; Then saturated NaOH solution is pumped into said decomposer from alkali lye pond ; Solid-liquid mass volume ratio by 1:1 ~ 1.5 reacts, and obtains reaction solution B; Said reaction solution B pumps into pressure filter ; Use alkaline-resisting type 300 orders to 500 order filter clothes; Press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa; Obtain solid phase iron content precipitation slag and filtrating E, this filtrating E gets into settling bath ; Secondly be that 36% hydrochloric acid pumps into said settling bath from hydrochloric acid tank with mass concentration, regulate pH value to 3.0 ~ 6.0 of the said E of filtrating; Pump into pressure filter with said filtrating E this moment; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa; Obtain filtrating F and solid phase hydrogen precipitation of alumina, this white lake product comes back to aluminum electrolysis technology; Last said filtrating F gets in the said sodium barium separating technology in the sodium-chlor condensing crystal groove, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains NaCl; Last said NaCl inputs in the drying plant, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology;
Said sodium barium separating technology is meant at first yellow soda ash is passed through feeder Drop into said settling bath In with the reaction of said mixing solutions, obtain reaction solution A; Said reaction solution A pumps into pressure filter , use neutral 300 orders to 500 order filter clothes, press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa obtains solid phase barium carbonate and filtrating D; Said then barium carbonate gets in the acidolysis groove, adds entry by the solid-liquid mass volume ratio of 1:1 ~ 3 and stirs, and the while mass concentration is that 36% hydrochloric acid is from a hydrochloric acid tank In pump in the said acidolysis groove and carry out acidifying, obtain acid hydrolysis solution behind 0.5 ~ 2.0 h, regulate pH to 3.0 ~ 7.0 of acid hydrolysis solution, this acid hydrolysis solution pumps in another condensing crystal groove, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains BaCl 22H 2O; Last said BaCl 22H 2O inputs in another drying plant, under 115 ℃ ~ 150 ℃ conditions, is dried to constant weight and obtains the bariumchloride product, and this bariumchloride product comes back to electrolysis refined aluminium technology; Said filtrating D gets in another condensing crystal groove, and mass concentration is that 36% hydrochloric acid is from another hydrochloric acid tank simultaneously In pump into this condensing crystal groove, regulate filtrating pH to 3.0 ~ 6.0 with hydrochloric acid, under 90 ℃ ~ 100 ℃ conditions, concentrate 0.5 ~ 3 h and obtain NaCl; Last said NaCl inputs in another drying plant, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology; The mass volume ratio of said yellow soda ash and said mixing solutions is 1:20 ~ 40; The mass volume ratio of said barium carbonate and said hydrochloric acid is 1:1 ~ 1.5.
Said acidleach jar; The removing impurities by oxidation groove; The high temperature deblending slot; Neutralizing well; Decomposer; Settling bath ; Settling bath ; Said acidolysis groove; Be equipped with electric blender in two condensing crystal grooves.
The present invention compared with prior art has the following advantages:
1, owing to is provided with fluoride recovery technology among the present invention; This technology is carried out acidleach with hydrochloric acid to The Barium Residue and calcium chloride compound in the acidleach jar; And through pressure filter pickling liquor is separated, obtaining solid phase Calcium Fluoride (Fluorspan), this Calcium Fluoride (Fluorspan) product can return electrolysis refined aluminium technology; Liquid phase then gets into the leach liquor separating technology, thereby the fluorion in the realization The Barium Residue is with the isolated in form of Calcium Fluoride (Fluorspan) and the purpose of recovery.
Wherein: in the acidleach process, adopt the leaching acid of hydrochloric acid, adopt calcium chloride, realize Cl in the leach liquor system as defluorinating agent as the solubility The Barium Residue -, F -Separation.
The staple of solubility The Barium Residue is BaCl 2BaF 2, Al 2O 3And impurity such as formed infusible compound such as aluminium, silicon, iron and sosoloid, adopt hydrochloric acid as leach liquor, can realize the leaching fully of each principal element in the solubility The Barium Residue.
In pickling liquor, add calcium chloride, with the F in the leach liquor -Form CaF 2Deposition can reach and remove F in the leach liquor -Purpose.Because BaF 2Can be dissolved in the hydrochloric acid, and CaF 2Then can not, therefore adopt calcium chloride can realize Cl in the hydrochloric acid leachate -And F -Separation.
2, owing to be provided with the leach liquor separating technology among the present invention; The filtrating that this technology is come fluoride recovery technology is adopted the filtrating after hydrogen peroxide oxidation is handled defluorination; Regulate pH value of filtrate with ammoniacal liquor, remove iron contained in the filtrating, aluminium impurity through pressure filter, precipitation slag gets into the iron aluminum separation technique; Adopt NaOH solution to regulate the pH value of deironing, aluminium rear filtrate again, remove calcium, magnesium in the filtrating through the mode of heat filter; Filtrating after adopting hydrochloric acid soln to removal of impurities is carried out neutralizing treatment, the NaCl that obtains, BaCl 2Mixing solutions gets into sodium barium separating technology, thereby realizes separating of iron aluminium and sodium barium ion in the pickling liquor.
Wherein: contain Al in the leach liquor behind the defluorination 3+With a spot of Fe 2+, the employing ydrogen peroxide 50 can be with Fe 2+Be oxidized to Fe 3+, control liquidus temperature simultaneously, regulate with ammoniacal liquor then and leach liquid pH, can remove iron and aluminium in the leach liquor.
3, owing to be provided with sodium barium separating technology among the present invention, this process using yellow soda ash is as precipitation agent, the NaCl, the BaCl that in settling bath, come with the leach liquor separating technology 2The mixing solutions reaction separates reaction solution through pressure filter, obtains the solid phase barium carbonate, and this barium carbonate obtains the bariumchloride product through hcl acidifying, concentrated, drying process, and the bariumchloride product can return electrolysis refined aluminium technology; Liquid phase then gets into concentrated, drying process, obtains the sodium-chlor product, and the sodium-chlor product can return electrolysis refined aluminium technology, thereby realizes that sodium, barium ion in the The Barium Residue is with the isolated in form of sodium-chlor, bariumchloride and the purpose of recovery.
Wherein: adopt yellow soda ash as precipitation agent, can realize the separation of barium in the mixing solutions, sodium element, form NaCl, BaCl 22H 2The O product.
Liquid phase behind deironing, the aluminium also contains a small amount of Ca 2+, Mg 2+Deng.When pH value of solution >=12, calcium, magnesium exist with the form of oxyhydroxide, barium partly hydrolysed in the liquid phase.Because Mg (OH) 2Solubleness is minimum, Mg 2+Very easily be removed; Ba (OH) 2Solubleness enlarge markedly but Ca (OH) along with solution temperature raises 2Solubleness but raise and obviously descend along with solution temperature.Employing improves method of temperature just can be with Ca (OH) 2Precipitate and separate is come out.Regulate the pH of clear liquid with NaOH solution, and through the overheated deposition that leaches, and with saturated barium chloride solution washing, use in the hydrochloric acid again and liquid phase in Ba (OH) 2, can obtain bariumchloride, sodium-chlor mixing solutions.
Bariumchloride generation chemical reaction in yellow soda ash and the mixing solutions generates precipitated barium carbonate, can make Ba 2+From mixing solutions, separate.The barium carbonate and the hydrochloric acid that generate react, and generate bariumchloride, through operations such as concentrated, dryings, finally can obtain the bariumchloride product.Separate and remove Ba 2+Solution, through concentrating, operation such as drying can obtain the sodium-chlor product.
4, owing to be provided with the iron aluminum separation technique among the present invention, this technology is separated through pressure filter the precipitation slag and the NaOH solution reaction of the iron content that obtains in the leach liquor separating technology, aluminium with reaction solution, obtain solid phase iron content precipitation slag; Liquid phase is then used the salt acid for adjusting pH value; Through pressure filter solution is separated again; Obtain the solid phase hydrogen precipitation of alumina, the white lake product can return aluminum electrolysis technology, and sodium-chlor concentrates in the sodium barium separating technology, drying process and the liquid phase of this moment gets into; Obtain the sodium-chlor product, thereby realize that iron, aluminum ion in the The Barium Residue is with the isolated in form of ironic hydroxide, white lake and the purpose of recovery.
Wherein: isolated Al (OH) 3, Fe (OH) 3Deposition adopts sodium hydroxide solution can realize the separation of the two.Fe (OH) 3With sodium hydroxide chemical reaction not taking place, finally separates from system with sedimentary form, and Al (OH) 3Then form the sodium metaaluminate of solubility with the sodium hydroxide reaction.Adopt the reaction of hydrochloric acid and sodium metaaluminate, can obtain Al (OH) 3Deposition realizes the recycling of aluminium element in the solubility The Barium Residue.
5, the present invention is easy to red-tape operati, has realized separation and the recovery of each principal element in the The Barium Residue that the refined aluminium production process produces.
6, adopt the present invention after, isolated bariumchloride, sodium-chlor, Calcium Fluoride (Fluorspan), white lake all can turn back to the refined aluminium electrolytic system again, reach comprehensive, recycle resource, energy-saving and emission-reduction and reduce environmental pollution and improve the purpose of production safety.
Description of drawings
Do further detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is a fluoride recovery system schematic of the present invention.
Fig. 3 is a leach liquor separation system synoptic diagram of the present invention.
Fig. 4 is an iron aluminium separation system synoptic diagram of the present invention.
Fig. 5 is a sodium barium separation system synoptic diagram of the present invention.
Numerals 1: - fluoride ion recovery system 11 - Feeder 12 - acid leaching tank ? 13 - Filter Press ? 14 - hydrochloric acid tank 2 - leaching liquid separation system 21 - oxidative addition miscellaneous slot 22 - high impurity groove 23 - neutralization tank 24 - Filter Press ? 25 - Hydrogen Peroxide receiver 26 - ammonia storage tank 27 - hydrochloric acid tank 28 - lye pool 29 - Filter Press 3 - almandine separation system? 31 - decomposition tank 32 - settling tank ? 33 - Filter Press 34 - lye pool 35 - hydrochloric acid tank 36 - Feeder ? 37 - Filter Press ? 4 - sodium barium separation system? 41 - settling tank ? 42 - acid hydrolysis tank? 43 - concentration crystallization tank ? 44 - Filter Press 45 - Drying Equipment 46 - hydrochloric acid tank ? 47 - on the feeder .
Embodiment
Embodiment 1Shown in Fig. 1 ~ 5, the method for The Barium Residue in a kind of comprehensive reutilization refined aluminium production process, this method is made up of fluoride recovery technology, leach liquor separating technology, iron aluminum separation technique, sodium barium separating technology.Wherein
Fluoride recovery technology is meant at first with dropping in the acidleach jars 12 through feeder 11 behind The Barium Residue in the refined aluminium production process and the mass ratio mixing formation compound of calcium chloride by 1:0.2; Add entry and adopt electric blender to stir; Hydrochloric acid is pumped into acidleach jar 12 from hydrochloric acid tank 14; It is that 36% hydrochloric acid is 180 g that every liter of mixing solutions need add mass concentration, obtains pickling liquor behind acidleach 2.0 h; The solid-liquid mass volume ratio (kg/L) of liquid is 1:2 in The Barium Residue and the acidleach jar; Pickling liquor is pumped into pressure filter 13; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 1.5 h under the pressure of 0.2MPa obtain solid phase Calcium Fluoride (Fluorspan) and filtrating A respectively; Last solid phase Calcium Fluoride (Fluorspan) comes back to electrolysis refined aluminium technology after drying, filtrating A gets into the removing impurities by oxidation groove 21 in the leach liquor separating technology.
It is that 27% ydrogen peroxide 50 pumps into removing impurities by oxidation groove 21 from ydrogen peroxide 50 storage tank 25 that the leach liquor separating technology is meant at first mass concentration, and to filtrating A oxide treatment 0.5 h, the volume ratio of liquid phase A and ydrogen peroxide 50 (L/L) is 1:0.005; Be that 25% ammoniacal liquor pumps into removing impurities by oxidation groove 21 from tank used for storing ammonia 26 with mass concentration then, and regulate pH value to 6.5 ~ 7.5 of filtrating A; The A that filtrates this moment pumps into pressure filter 24, use neutral 300 orders to 500 order filter clothes, press filtration 1.5 h under the pressure condition of 0.2MPa obtain liquor B and iron content, aluminium contamination precipitation slag respectively, and this iron content, aluminium contamination precipitation slag get into the iron aluminum separation technique; Secondly liquor B gets into high temperature deblending slot 22, simultaneously with saturated NaOH solution from the alkali lye pond Pump into high temperature deblending slot 22 in 28, regulate pH value to 10.0 ~ 14.0 of liquor B; This moment, liquor B pumped into pressure filter 29, keep the filtrating temperature in 30 ℃ ~ 90 ℃ scopes, use alkaline-resisting type 500 orders to 700 order filter clothes, press filtration 1.5 h remove calcium, the magnesium addition in the liquor B under the pressure condition of 0.3MPa, obtain liquor C, and this liquor C inputs to neutralizing well 23; Be that 36% hydrochloric acid is from hydrochloric acid tank with mass concentration at last Pump into neutralizing well 23 in 27, make the pH value of liquor C be neutral, obtain NaCl, BaCl 2Mixing solutions, this mixing solutions get into the settling bath in the sodium barium separating technology 41.
The iron aluminum separation technique is meant that at first the precipitation slag with iron content, aluminium in the said leach liquor separating technology drops in the decomposers 31 through feeder 36; Then saturated NaOH solution is pumped into decomposer 31 from alkali lye pond 34; Solid-liquid mass volume ratio (kg/L) by 1:1 reacts, and obtains reaction solution B; Reaction solution B pumps into pressure filter 33; Use alkaline-resisting type 300 orders to 500 order filter clothes; Press filtration 1.5 h under the pressure condition of 0.2MPa; Obtain solid phase iron content precipitation slag and filtrating E, this filtrating E gets into settling bath 32; Secondly be that 36% hydrochloric acid pumps into settling bath 32 from hydrochloric acid tank 35 with mass concentration, regulate pH value to 3.0 ~ 6.0 of filtrating E; The E that will filtrate this moment pumps into pressure filter 37; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 1.5 h under the pressure condition of 0.2MPa; Obtain filtrating F and solid phase hydrogen precipitation of alumina, this white lake product comes back to aluminum electrolysis technology; The F that filtrates at last gets in the sodium barium separating technology in the sodium-chlor condensing crystal groove 43, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains NaCl; Last NaCl inputs in the drying plant 45, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology.
Sodium barium separating technology is meant at first yellow soda ash is passed through feeder 47 drop into settling bath With the mixing solutions reaction, obtain reaction solution A in 41; Reaction solution A pumps into pressure filter 44, use neutral 300 orders to 500 order filter clothes, press filtration 1.5 h under the pressure condition of 0.2MPa obtain solid phase barium carbonate and filtrating D; Barium carbonate gets in the acidolysis groove 42 then, adds entry by the solid-liquid mass volume ratio (kg/L) of 1:1 and stirs, and the while mass concentration is that 36% hydrochloric acid is from a hydrochloric acid tank Pump in 46 and carry out acidifying in the acidolysis groove 42, obtain acid hydrolysis solution behind 0.5 ~ 2.0 h, regulate pH to 3.0 ~ 7.0 of acid hydrolysis solution, this acid hydrolysis solution pumps in another condensing crystal groove 43, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains BaCl 22H 2O; Last BaCl 22H 2O inputs in another drying plant 45, under 115 ℃ ~ 150 ℃ conditions, is dried to constant weight and obtains the bariumchloride product, and this bariumchloride product comes back to electrolysis refined aluminium technology; Filtrating D gets in another condensing crystal groove 43, and mass concentration is that 36% hydrochloric acid is from another hydrochloric acid tank simultaneously Pump into this condensing crystal groove 43 in 46, regulate filtrating pH to 3.0 ~ 6.0, under 90 ℃ ~ 100 ℃ conditions, concentrate 0.5 ~ 3 h and obtain NaCl with hydrochloric acid; Last NaCl inputs in another drying plant 45, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology; The mass volume ratio of yellow soda ash and mixing solutions (kg/L) is 1:20; The mass volume ratio of barium carbonate and hydrochloric acid (kg/L) is 1:1.
Embodiment 2Shown in Fig. 1 ~ 5, the method for The Barium Residue in a kind of comprehensive reutilization refined aluminium production process, this method is made up of fluoride recovery technology, leach liquor separating technology, iron aluminum separation technique, sodium barium separating technology.Wherein
Fluoride recovery technology is meant at first with dropping in the acidleach jars 12 through feeder 11 behind The Barium Residue in the refined aluminium production process and the mass ratio mixing formation compound of calcium chloride by 1:1; Add entry and adopt electric blender to stir; Hydrochloric acid is pumped into acidleach jar 12 from hydrochloric acid tank 14; It is that 36% hydrochloric acid is 450 g that every liter of mixing solutions need add mass concentration, obtains pickling liquor behind acidleach 0.5 h; The solid-liquid mass volume ratio (kg/L) of liquid is 1:10 in The Barium Residue and the acidleach jar; Pickling liquor is pumped into pressure filter 13; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 0.5 h under the pressure of 0.5MPa obtains solid phase Calcium Fluoride (Fluorspan) and filtrating A respectively; Last solid phase Calcium Fluoride (Fluorspan) comes back to electrolysis refined aluminium technology after drying, filtrating A gets into the removing impurities by oxidation groove 21 in the leach liquor separating technology.
It is that 27% ydrogen peroxide 50 pumps into removing impurities by oxidation groove 21 from ydrogen peroxide 50 storage tank 25 that the leach liquor separating technology is meant at first mass concentration, and to filtrating A oxide treatment 2.5 h, the volume ratio of liquid phase A and ydrogen peroxide 50 (L/L) is 1:0.01; Be that 25% ammoniacal liquor pumps into removing impurities by oxidation groove 21 from tank used for storing ammonia 26 with mass concentration then, and regulate pH value to 6.5 ~ 7.5 of filtrating A; The A that filtrates this moment pumps into pressure filter 24, use neutral 300 orders to 500 order filter clothes, press filtration 0.5 h under the pressure condition of 0.6MPa obtains liquor B and iron content, aluminium contamination precipitation slag respectively, and this iron content, aluminium contamination precipitation slag get into the iron aluminum separation technique; Secondly liquor B gets into high temperature deblending slot 22, simultaneously with saturated NaOH solution from the alkali lye pond Pump into high temperature deblending slot 22 in 28, regulate pH value to 10.0 ~ 14.0 of liquor B; This moment, liquor B pumped into pressure filter 29, keep the filtrating temperature in 30 ℃ ~ 90 ℃ scopes, use alkaline-resisting type 500 orders to 700 order filter clothes, press filtration 0.5 h removes calcium, the magnesium addition in the liquor B under the pressure condition of 0.8MPa, obtains liquor C, and this liquor C inputs to neutralizing well 23; Be that 36% hydrochloric acid is from hydrochloric acid tank with mass concentration at last Pump into neutralizing well 23 in 27, make the pH value of liquor C be neutral, obtain NaCl, BaCl 2Mixing solutions, this mixing solutions get into the settling bath in the sodium barium separating technology 41.
The iron aluminum separation technique is meant that at first the precipitation slag with iron content, aluminium in the said leach liquor separating technology drops in the decomposers 31 through feeder 36; Then saturated NaOH solution is pumped into decomposer 31 from alkali lye pond 34; Solid-liquid mass volume ratio (kg/L) by 1:1.5 reacts, and obtains reaction solution B; Reaction solution B pumps into pressure filter 33; Use alkaline-resisting type 300 orders to 500 order filter clothes; Press filtration 0.5 h under the pressure condition of 0.6MPa; Obtain solid phase iron content precipitation slag and filtrating E, this filtrating E gets into settling bath 32; Secondly be that 36% hydrochloric acid pumps into settling bath 32 from hydrochloric acid tank 35 with mass concentration, regulate pH value to 3.0 ~ 6.0 of filtrating E; The E that will filtrate this moment pumps into pressure filter 37; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 0.5 h under the pressure condition of 0.6MPa; Obtain filtrating F and solid phase hydrogen precipitation of alumina, this white lake product comes back to aluminum electrolysis technology; The F that filtrates at last gets in the sodium barium separating technology in the sodium-chlor condensing crystal groove 43, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains NaCl; Last NaCl inputs in the drying plant 45, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology.
Sodium barium separating technology is meant at first yellow soda ash is passed through feeder 47 drop into settling bath With the mixing solutions reaction, obtain reaction solution A in 41; Reaction solution A pumps into pressure filter 44, use neutral 300 orders to 500 order filter clothes, press filtration 0.5 h under the pressure condition of 0.6MPa obtains solid phase barium carbonate and filtrating D; Barium carbonate gets in the acidolysis groove 42 then, adds entry by the solid-liquid mass volume ratio (kg/L) of 1:3 and stirs, and the while mass concentration is that 36% hydrochloric acid is from a hydrochloric acid tank Pump in 46 and carry out acidifying in the acidolysis groove 42, obtain acid hydrolysis solution behind 0.5 ~ 2.0 h, regulate pH to 3.0 ~ 7.0 of acid hydrolysis solution, this acid hydrolysis solution pumps in another condensing crystal groove 43, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains BaCl 22H 2O; Last BaCl 22H 2O inputs in another drying plant 45, under 115 ℃ ~ 150 ℃ conditions, is dried to constant weight and obtains the bariumchloride product, and this bariumchloride product comes back to electrolysis refined aluminium technology; Filtrating D gets in another condensing crystal groove 43, and mass concentration is that 36% hydrochloric acid is from another hydrochloric acid tank simultaneously Pump into this condensing crystal groove 43 in 46, regulate filtrating pH to 3.0 ~ 6.0, under 90 ℃ ~ 100 ℃ conditions, concentrate 0.5 ~ 3 h and obtain NaCl with hydrochloric acid; Last NaCl inputs in another drying plant 45, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology; The mass volume ratio of yellow soda ash and mixing solutions (kg/L) is 1:40; The mass volume ratio of barium carbonate and hydrochloric acid (kg/L) is 1:1.5.
Embodiment 3Shown in Fig. 1 ~ 5, the method for The Barium Residue in a kind of comprehensive reutilization refined aluminium production process, this method is made up of fluoride recovery technology, leach liquor separating technology, iron aluminum separation technique, sodium barium separating technology.Wherein
Fluoride recovery technology is meant at first with dropping in the acidleach jars 12 through feeder 11 behind The Barium Residue in the refined aluminium production process and the mass ratio mixing formation compound of calcium chloride by 1:0.6; Add entry and adopt electric blender to stir; Hydrochloric acid is pumped into acidleach jar 12 from hydrochloric acid tank 14; It is that 36% hydrochloric acid is 320 g that every liter of mixing solutions need add mass concentration, obtains pickling liquor behind acidleach 1.5 h; The solid-liquid mass volume ratio (kg/L) of liquid is 1:6 in The Barium Residue and the acidleach jar; Pickling liquor is pumped into pressure filter 13; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 1.0 h under the pressure of 0.35MPa obtain solid phase Calcium Fluoride (Fluorspan) and filtrating A respectively; Last solid phase Calcium Fluoride (Fluorspan) comes back to electrolysis refined aluminium technology after drying, filtrating A gets into the removing impurities by oxidation groove 21 in the leach liquor separating technology.
It is that 27% ydrogen peroxide 50 pumps into removing impurities by oxidation groove 21 from ydrogen peroxide 50 storage tank 25 that the leach liquor separating technology is meant at first mass concentration, and to filtrating A oxide treatment 1.0 h, the volume ratio of liquid phase A and ydrogen peroxide 50 (L/L) is 1:0.075; Be that 25% ammoniacal liquor pumps into removing impurities by oxidation groove 21 from tank used for storing ammonia 26 with mass concentration then, and regulate pH value to 6.5 ~ 7.5 of filtrating A; The A that filtrates this moment pumps into pressure filter 24, use neutral 300 orders to 500 order filter clothes, press filtration 1.0 h under the pressure condition of 0.4MPa obtain liquor B and iron content, aluminium contamination precipitation slag respectively, and this iron content, aluminium contamination precipitation slag get into the iron aluminum separation technique; Secondly liquor B gets into high temperature deblending slot 22, simultaneously with saturated NaOH solution from the alkali lye pond Pump into high temperature deblending slot 22 in 28, regulate pH value to 10.0 ~ 14.0 of liquor B; This moment, liquor B pumped into pressure filter 29, keep the filtrating temperature in 30 ℃ ~ 90 ℃ scopes, use alkaline-resisting type 500 orders to 700 order filter clothes, press filtration 1.0 h remove calcium, the magnesium addition in the liquor B under the pressure condition of 0.5MPa, obtain liquor C, and this liquor C inputs to neutralizing well 23; Be that 36% hydrochloric acid is from hydrochloric acid tank with mass concentration at last Pump into neutralizing well 23 in 27, make the pH value of liquor C be neutral, obtain NaCl, BaCl 2Mixing solutions, this mixing solutions get into the settling bath in the sodium barium separating technology 41.
The iron aluminum separation technique is meant that at first the precipitation slag with iron content, aluminium in the said leach liquor separating technology drops in the decomposers 31 through feeder 36; Then saturated NaOH solution is pumped into decomposer 31 from alkali lye pond 34; Solid-liquid mass volume ratio (kg/L) by 1:1.25 reacts, and obtains reaction solution B; Reaction solution B pumps into pressure filter 33; Use alkaline-resisting type 300 orders to 500 order filter clothes; Press filtration 1.0 h under the pressure condition of 0.4MPa; Obtain solid phase iron content precipitation slag and filtrating E, this filtrating E gets into settling bath 32; Secondly be that 36% hydrochloric acid pumps into settling bath 32 from hydrochloric acid tank 35 with mass concentration, regulate pH value to 3.0 ~ 6.0 of filtrating E; The E that will filtrate this moment pumps into pressure filter 37; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 1.0 h under the pressure condition of 0.4MPa; Obtain filtrating F and solid phase hydrogen precipitation of alumina, this white lake product comes back to aluminum electrolysis technology; The F that filtrates at last gets in the sodium barium separating technology in the sodium-chlor condensing crystal groove 43, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains NaCl; Last NaCl inputs in the drying plant 45, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology.
Sodium barium separating technology is meant at first yellow soda ash is passed through feeder 47 drop into settling bath With the mixing solutions reaction, obtain reaction solution A in 41; Reaction solution A pumps into pressure filter 44, use neutral 300 orders to 500 order filter clothes, press filtration 1.0 h under the pressure condition of 0.4MPa obtain solid phase barium carbonate and filtrating D; Barium carbonate gets in the acidolysis groove 42 then, adds entry by the solid-liquid mass volume ratio (kg/L) of 1:2 and stirs, and the while mass concentration is that 36% hydrochloric acid is from a hydrochloric acid tank Pump in 46 and carry out acidifying in the acidolysis groove 42, obtain acid hydrolysis solution behind 0.5 ~ 2.0 h, regulate pH to 3.0 ~ 7.0 of acid hydrolysis solution, this acid hydrolysis solution pumps in another condensing crystal groove 43, under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains BaCl 22H 2O; Last BaCl 22H 2O inputs in another drying plant 45, under 115 ℃ ~ 150 ℃ conditions, is dried to constant weight and obtains the bariumchloride product, and this bariumchloride product comes back to electrolysis refined aluminium technology; Filtrating D gets in another condensing crystal groove 43, and mass concentration is that 36% hydrochloric acid is from another hydrochloric acid tank simultaneously Pump into this condensing crystal groove 43 in 46, regulate filtrating pH to 3.0 ~ 6.0, under 90 ℃ ~ 100 ℃ conditions, concentrate 0.5 ~ 3 h and obtain NaCl with hydrochloric acid; Last NaCl inputs in another drying plant 45, under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology; The mass volume ratio of yellow soda ash and mixing solutions (kg/L) is 1:30; The mass volume ratio of barium carbonate and hydrochloric acid (kg/L) is 1:1.3.
Above-mentioned Embodiment 1 ~ 3In, acidleach jar 12, removing impurities by oxidation groove 21, high temperature deblending slot 22, neutralizing well 23, decomposer 31, settling bath 32, settling bath 41, be equipped with electric blender in acidolysis groove 42, two condensing crystal grooves 43.

Claims (2)

1. the method for The Barium Residue in the comprehensive reutilization refined aluminium production process, it is characterized in that: this method is made up of fluoride recovery technology, leach liquor separating technology, iron aluminum separation technique, sodium barium separating technology; Wherein
Said fluoride recovery technology is meant at first with dropping in the acidleach jar (12) through feeder (11) behind The Barium Residue in the refined aluminium production process and the mass ratio mixing formation compound of calcium chloride by 1:0.2 ~ 1; Add entry and adopt electric blender to stir; Hydrochloric acid is pumped into said acidleach jar (12) from hydrochloric acid tank (14); It is that 36% hydrochloric acid is 180 ~ 450 g that every liter of mixing solutions need add mass concentration, obtains pickling liquor behind acidleach 0.5 ~ 2.0 h; The solid-liquid mass volume ratio of liquid is 1:2 ~ 10 in said The Barium Residue and the acidleach jar; Said pickling liquor is pumped into pressure filter (13); Use anti-acid 300 orders to 500 order filter clothes; Press filtration 0.5 ~ 1.5 h under the pressure of 0.2MPa ~ 0.5MPa obtains solid phase Calcium Fluoride (Fluorspan) and filtrating A respectively; Last said solid phase Calcium Fluoride (Fluorspan) comes back to electrolysis refined aluminium technology after drying, said filtrating A gets into the removing impurities by oxidation groove (21) in the said leach liquor separating technology;
It is that 27% ydrogen peroxide 50 pumps into said removing impurities by oxidation groove (21) from ydrogen peroxide 50 storage tank (25) that said leach liquor separating technology is meant at first mass concentration; To said filtrating A oxide treatment 0.5 ~ 2.5 h, the volume ratio of said liquid phase A and said ydrogen peroxide 50 is 1:0.005 ~ 0.01; Be that 25% ammoniacal liquor pumps into said removing impurities by oxidation groove (21) from tank used for storing ammonia (26) with mass concentration then, and regulate pH value to 6.5 ~ 7.5 of said filtrating A; This moment, said filtrating A pumped into pressure filter (24), use neutral 300 orders to 500 order filter clothes, press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa obtains liquor B and iron content, aluminium contamination precipitation slag respectively, and this iron content, aluminium contamination precipitation slag get into said iron aluminum separation technique; Secondly said liquor B gets into high temperature deblending slot (22), simultaneously with saturated NaOH solution from the alkali lye pond (28) pump into said high temperature deblending slot (22) in, regulate pH value to 10.0 ~ 14.0 of said liquor B; This moment, said liquor B pumped into pressure filter (29); Keep the filtrating temperature in 30 ℃ ~ 90 ℃ scopes, use alkaline-resisting type 500 orders to 700 order filter clothes, press filtration 0.5 ~ 1.5 h removes calcium, the magnesium addition in the liquor B under the pressure condition of 0.3MPa ~ 0.8MPa; Obtain liquor C, this liquor C inputs to neutralizing well (23); Be that 36% hydrochloric acid is from hydrochloric acid tank with mass concentration at last (27) pump into said neutralizing well (23) in, make the pH value of said liquor C be neutral, obtain NaCl, BaCl 2Mixing solutions, this mixing solutions get into the settling bath in the said sodium barium separating technology (41);
Said iron aluminum separation technique is meant that at first the precipitation slag with iron content, aluminium in the said leach liquor separating technology drops in the decomposer (31) through feeder (36); Then saturated NaOH solution is pumped into said decomposer (31) from alkali lye pond (34); Solid-liquid mass volume ratio by 1:1 ~ 1.5 reacts, and obtains reaction solution B; Said reaction solution B pumps into pressure filter (33); Use alkaline-resisting type 300 orders to 500 order filter clothes; Press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa; Obtain solid phase iron content precipitation slag and filtrating E, this filtrating E gets into settling bath (32); Secondly be that 36% hydrochloric acid pumps into said settling bath (32) from hydrochloric acid tank (35) with mass concentration, regulate pH value to 3.0 ~ 6.0 of the said E of filtrating; Pump into pressure filter (37) with said filtrating E this moment; Use anti-acid 300 orders to 500 order filter clothes; Press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa; Obtain filtrating F and solid phase hydrogen precipitation of alumina, this white lake product comes back to aluminum electrolysis technology; Last said filtrating F gets in the said sodium barium separating technology in the sodium-chlor condensing crystal groove (43), under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains NaCl; Last said NaCl inputs in the drying plant (45), under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology;
Said sodium barium separating technology is meant at first yellow soda ash is passed through feeder (47) drop into said settling bath (41) with said mixing solutions reaction, obtain reaction solution A in; Said reaction solution A pumps into pressure filter (44), use neutral 300 orders to 500 order filter clothes, press filtration 0.5 ~ 1.5 h under the pressure condition of 0.2MPa ~ 0.6MPa obtains solid phase barium carbonate and filtrating D; Said then barium carbonate gets in the acidolysis groove (42), adds entry by the solid-liquid mass volume ratio of 1:1 ~ 3 and stirs, and the while mass concentration is that 36% hydrochloric acid is from a hydrochloric acid tank (46) pump in the said acidolysis groove (42) and carry out acidifying, obtain acid hydrolysis solution behind 0.5 ~ 2.0 h, regulate pH to 3.0 ~ 7.0 of acid hydrolysis solution, this acid hydrolysis solution pumps in another condensing crystal groove (43), under 90 ℃ ~ 100 ℃ conditions, concentrates 0.5 ~ 3 h and obtains BaCl 22H 2O; Last said BaCl 22H 2O inputs in another drying plant (45), under 115 ℃ ~ 150 ℃ conditions, is dried to constant weight and obtains the bariumchloride product, and this bariumchloride product comes back to electrolysis refined aluminium technology; Said filtrating D gets in another condensing crystal groove (43), and mass concentration is that 36% hydrochloric acid is from another hydrochloric acid tank simultaneously (46) pump into this condensing crystal groove (43) in, regulate filtrating pH to 3.0 ~ 6.0, under 90 ℃ ~ 100 ℃ conditions, concentrate 0.5 ~ 3 h and obtain NaCl with hydrochloric acid; Last said NaCl inputs in another drying plant (45), under 105 ℃ ~ 115 ℃ conditions, is dried to constant weight and obtains the sodium-chlor product, and this sodium-chlor product comes back to electrolysis refined aluminium technology; The mass volume ratio of said yellow soda ash and said mixing solutions is 1:20 ~ 40; The mass volume ratio of said barium carbonate and said hydrochloric acid is 1:1 ~ 1.5.
2. the method for The Barium Residue in a kind of comprehensive reutilization refined aluminium production process as claimed in claim 1 is characterized in that: be equipped with electric blender in said acidleach jar (12), removing impurities by oxidation groove (21), high temperature deblending slot (22), neutralizing well (23), decomposer (31), settling bath (32), settling bath (41), said acidolysis groove (42), two the condensing crystal grooves (43).
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CN105967216A (en) * 2016-07-01 2016-09-28 丁淑暖 Production method of barium chloride
CN106967884A (en) * 2017-03-20 2017-07-21 北矿力澜科技咨询(北京)有限公司 A kind of method of silver separating residue of copper anode slime step by step arithmetic
CN107177733A (en) * 2017-06-05 2017-09-19 中南大学 A kind of method of barite deposit refining and edulcoration synthetical recovery calcium and magnesium
CN108931589A (en) * 2018-05-15 2018-12-04 中国科学技术大学 The method that a kind of pair of calcium carbonate sample Ba element is recycled

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105967216A (en) * 2016-07-01 2016-09-28 丁淑暖 Production method of barium chloride
CN106967884A (en) * 2017-03-20 2017-07-21 北矿力澜科技咨询(北京)有限公司 A kind of method of silver separating residue of copper anode slime step by step arithmetic
CN106967884B (en) * 2017-03-20 2019-05-21 北矿力澜科技咨询(北京)有限公司 A kind of method of silver separating residue of copper anode slime step by step arithmetic
CN107177733A (en) * 2017-06-05 2017-09-19 中南大学 A kind of method of barite deposit refining and edulcoration synthetical recovery calcium and magnesium
CN107177733B (en) * 2017-06-05 2018-12-21 中南大学 A kind of method of barite deposit refining and edulcoration synthetical recovery calcium and magnesium
CN108931589A (en) * 2018-05-15 2018-12-04 中国科学技术大学 The method that a kind of pair of calcium carbonate sample Ba element is recycled

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