CN109108049A - Containing sodium, the method for transformation of fluorochemical and system in a kind of aluminium electroloysis dangerous waste slag - Google Patents
Containing sodium, the method for transformation of fluorochemical and system in a kind of aluminium electroloysis dangerous waste slag Download PDFInfo
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- CN109108049A CN109108049A CN201810867455.1A CN201810867455A CN109108049A CN 109108049 A CN109108049 A CN 109108049A CN 201810867455 A CN201810867455 A CN 201810867455A CN 109108049 A CN109108049 A CN 109108049A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/02—Gases or liquids enclosed in discarded articles, e.g. aerosol cans or cooling systems of refrigerators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B9/00—General methods of preparing halides
- C01B9/08—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/28—Fluorides
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Abstract
本发明涉及一种铝电解危废渣中含钠、含氟化合物的转化方法与系统。转化方法包括利用转化剂、通过在转化磨中的机械化学转化反应将铝电解危废渣中的含钠化合物转变成不含氟的可溶性钠化合物、含氟化合物转变成不溶性和无害的矿物质氟化合物、氰化合物被氧化转变成无害气体，从而彻底解除铝电解危废渣中氟化物和氰化物的危害。转化系统包括依次连接的危废渣破碎设备、磨粉设备、转化磨、搅拌反应器和固液分离设备，固液分离设备再与浓缩或结晶设备、干燥或热处理设备均直接连接，干燥或热处理设备连接粉碎设备。本发明工艺简单、易于大规模生产、生产成本低、无三废污染、对环境友好，能够实现铝电解危废渣的无害化和资源化的处理目标。
The invention relates to a method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis hazardous waste residues. The conversion method includes using a conversion agent to convert sodium-containing compounds in aluminum electrolysis hazardous waste residues into fluorine-free soluble sodium compounds and fluorine-containing compounds into insoluble and harmless mineral fluorine through a mechanochemical conversion reaction in a conversion mill. Compounds and cyanide compounds are oxidized and transformed into harmless gases, thereby completely eliminating the harm of fluoride and cyanide in the hazardous waste residue of aluminum electrolysis. The conversion system includes hazardous waste slag crushing equipment, grinding equipment, conversion mill, stirring reactor and solid-liquid separation equipment connected in sequence. The solid-liquid separation equipment is directly connected with concentration or crystallization equipment, drying or heat treatment equipment, and drying or heat treatment equipment Connect shredding equipment. The invention has the advantages of simple process, easy mass production, low production cost, no three-waste pollution, and environmental friendliness, and can achieve the treatment goals of harmless and resourceful aluminum electrolysis hazardous waste residues.
Description
Technical field
The present invention relates to, containing sodium, the method for transformation of fluorochemical and system, belong to electrolysis in a kind of aluminium electroloysis dangerous waste slag
Aluminum i ndustry solid waste is innoxious with application technology as the second resource field.
Background technique
It is more than 36,000,000 tons, accounts for global electricity to built about 45,000,000 tons of the aluminium electroloysis production capacity of China in 2017, actual production
Solve 50% or more of aluminium production capacity.During aluminum electrolysis, charcoal cathode due to fluorine-containing salts infiltration and expand, further cause
The breakage of electrolytic cell is scrapped.Aluminium cell generally just needs to stop groove overhaul using 4-6 or so, takes out all waste and old liner materials
Expect (referred to as slag from delining), slag from delining is inevitable solid waste during Aluminum Electrolysis Production.The every life of Aluminum Electrolysis Production
The slag from delining that 1 ton of primary aluminum about discharges 10~30kg is produced, electrolytic aluminium slag from delining is defined as danger in " National Hazard waste register "
Solid waste (classification are as follows: HW48).Slag from delining mainly accounts for about 55%, waste refractory materials by waste cathode carbon block (including thickener)
(calcium silicate board, ceramic beaverboard, insulating brick, Impervious Materials, castable, lateral mass) accounts for about 45% composition.Aluminum electrolysis waste cathode carbon
In block, carbon materials account for 30%~70%, remaining for electrolyte, mainly Na3[AlF6]、NaF、CaF2、MgF2、LiF、AlF3、
NaCN、Na4[Fe(CN)6] etc., there are also a small amount of Al, Al4C3, AlN, Na etc., these substances have soluble and react with water
Activity can generate HF, HCN, H2、CH4、NH3Deng harmful or imflammable gas, it is fluorine-containing, enter environment containing cyanogen compound can be to the mankind
And the health of animals and plants constitutes greatly harm with growth.
Aluminium electroloysis dangerous waste slag is a kind of valuable resource rich in high-graphitized carbon and fluorine-containing electrolyte.Therefore, how thorough
Bottom releases the harm of fluoride and cyanide in aluminium electroloysis dangerous waste slag, realizes the innoxious and resource utilization of aluminium electroloysis dangerous waste slag
Using being the industry difficulty for needing to capture, expert scholar and production line personnel have carried out unremitting for many years for this problem
Exploratory development.
Chinese invention CN106745137A, CN106077038A, CN106077040A, CN106745137A,
CN106587122A, CN101817521A, CN105821445A are proposed using alkali leaching or ultrasonic wave secondary flotation alkaline pressure of oxygen leaching
Method process aluminum electrolytic waste and old cathode carbon or aluminium electroloysis waste material, extract ice crystal and carbon materials respectively.Chinese invention
CN106077037A, CN106077036A, CN106180118A, CN101984984A propose auxiliary using acid processing or ultrasonic wave
Help the method process aluminum electrolytic waste and old cathode carbon or slag from delining of flotation pressurization acid processing.Chinese invention CN107162061A proposition is adopted
With alkali leaching, Ore Leaching and the united method of flyash, harmless treatment and resource are carried out to aluminum cell waste cathode carbon
Change and utilizes.
105964659 A of Chinese invention CN106064813A, CN proposition protects waste and old cathode powdered carbon at 200~400 DEG C
Temperature removes cyanogen, and except cyanogen material obtains breeze and electrolyte slag through FLOTATION SEPARATION, electrolyte slag heats at 550~800 DEG C removes charcoal
Impurity obtains electrolyte powder, and breeze goes soluble matter to obtain the powdered carbon of purity is high by alkali leaching, and alkali lixivium leads to CO2Ice crystal is precipitated
Stone and alumag.
102989744 A of Chinese invention CN, CN102989743A, CN102978659A, CN102992299A,
CN102992300A, CN102976776A are separately recovered using the method process aluminum electrolytic waste residue of water logging, flotation and high-temperature calcination
Carbon dust, refractory material.
Aluminum cell waste cathode carbon powder is soaked in water in 105772486 A of Chinese invention CN proposition, by soluble cyanogen
Compound leaches, then hydrogen peroxide, stabilizer is added (selected from citric acid, tartaric acid, ethylenediamine tetra-acetic acid, amino three in leachate
Methylene phosphonic acid, polyacrylic acid, maleic acid, borax, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, in ammonium citrate), catalyst (choosing
From ZnO, CuO, Fe3O4、WO3In) after so that cyanide oxidation product is resolved into CO in 30~70 DEG C of reactions2、NH3Gas.Document
(China Environmental Science association Annual Conference collection of thesis in 2013: p5401~5407.) is reported using at water logging, flotation, chemistry
The research of reason, evaporative crystallization, waste gas absorption process electrolytic aluminium danger solid waste.
103239828 A of Chinese invention CN proposes a kind of program-controlled, manual electrolytic aluminium slag from delining hamlessizing technology technique,
Any one of sodium chlorate, calcium hypochlorite or hydrogen peroxide are used for except cyanogen agent, using calcium chloride, calcium oxide, calcium hydroxide or carbon
Any one of sour calcium is defluorinating agent, regulates and controls the residual quantity of pH value and fluoride in fluorine conversion process by hydrochloric acid.The patent is same
When provide the reaction warehouse and acid-regulating tank of a kind of strong acid-base resistance and strong oxidizer.
Chinese invention CN100542702C is by waste cathode of aluminum electrolytic cell carbon block and is rich in SiO2And Al2O3Flyash mixing
Carry out calcination process, treated material H2SO4With lime resolution process, obtain waste cathode of aluminum electrolytic cell carbon block innoxious
And resource utilization.Chinese invention CN107285354A by Aluminum carbonaceous dangerous waste, forge, make fluoride salt by the electricity at 1050~1200 DEG C
It is melt into liquid and is saturated separation, again low fluorine carbon granules progress high-temperature electric forged to obtain high-purity carbon product.Chinese invention
CN101054693A, CN101063215A are respectively by waste cathode of aluminum electrolytic cell powdered carbon and aluminium electrolysis anode breeze and organic binder
Mixing compacting is agglomerating, carbonaceous complete oxidation was obtained 97.5% or more electricity in calcination process 4~6 hours at 650~900 DEG C again
Solve matter product.Chinese invention CN103831285A provides a kind of including heating furnace, heat cycles devices, exhaust gas cleaner
The aluminium electroloysis breeze that gives up is carried out 7~8h of harmless treatment by processing system in 1250~1350 DEG C of heating furnace.Chinese invention
CN107628614A use 1200~1700 DEG C of temperature lower calcination electrolytic aluminium waste cathodes, by useless cathode carbon and fluorination
Object, oxide and cyanide are separated, and realize its innoxious and resource utilization.
Chinese invention CN105642649A, CN106185818A, CN106269787A use 2000 DEG C or more of superhigh temperature
With handle electrolytic aluminium waste cathode carbon block under vacuum condition, the fluoride therein of volatilizing decomposes cyanide therein, by carbon in cathode
Element, fluoride and cyanide efficiently separate decomposition, realize its innoxious and resource utilization.
From the point of view of existing technological achievement, the innoxious of aluminium electroloysis dangerous waste slag, recycling treatment are utilized and are segmented into water
The wet-treating of solution and two major class of pyrogenic attack under high temperature.Wet-treating further relate to washing (leaching), alkaline process, acid system,
Acid-alkali combination method simultaneously cooperates floatation process, and mainly for the purpose of recycling electrolyte and carbon materials, oxygen is used in wet-treating
Cyanide is resolved into harmless gaseous matter by agent.Pyrogenic attack technology is mainly negative for the purpose of innoxious, or based on giving up
Extremely middle carbonaceous content 50% or more, its calorific value resource can be effectively utilized；Or electrolyte melting permeability and separation is returned
It receives；Or HF is converted by fluoride and carries out sorption enhanced utilization again；Or it is converted into electrolyte by adding converting additive
Harmless and insoluble fluorine minerals；Or take high-temperature vacuum technology that utilization is separately recovered in carbon materials and electrolyte.?
In pyrogenic attack, it is oxidized at high temperature containing cyanogen compound and resolves into harmless gaseous matter.
From the point of view of existing technological achievement, the wet-treating and pyrogenic attack of aluminium electroloysis dangerous waste slag still have many urgent
Problem to be solved.
At least there is following main problem in current wet processing technique: the first, generated a large amount of saliferous, fluoride waste
It is not effectively addressed, causes secondary pollution；Generated H2、CH4、NH3Gas is not under control and utilizes, produced
HF cause serious pollution.The second, the electrolyte and carbon materials impurity content recycled is excessively high, cannot directly utilize.The
Three, process route is cumbersome, technology is complicated, equipment seriously corroded, and processing cost is excessively high.4th, due to aluminium electroloysis dangerous waste slag chute age
And the influence of the factors such as fluctuation of the difference of capacity, material composition, cause process parameter control difficulty big.
At least there is following main problem in current pyrogenic attack technology: the first, producing a large amount of entrainment HF and dust
Tail gas need to administer.The second, electrolytic salt recycling is not thorough, remains in carbon materials or clinker and need further to locate
Reason.Third, low melting point electrolytic salt occur vitreous clinker in furnace, cause the incomplete residual quantity of Carbon Materials oxidizing fire big,
Vitreous clinker causes production status deterioration, production stability poor in furnace.4th, reaction mass is difficult to realize the uniform of molecular level
It mixes, conversion reaction is caused to be not thorough.5th, equipment seriously corroded, processing energy consumption are high.
Summary of the invention
In order to solve the above technical problem, the present invention provides turns in a kind of aluminium electroloysis dangerous waste slag containing sodium, fluorochemical
Change method and system.The present invention has technical process convenient for control, is easy to industrialize that steady production, process costs are low, no three wastes
The features such as pollution and equipment are corroded.
The invention is realized by the following technical scheme:
Method for transformation containing sodium, fluorochemical in a kind of aluminium electroloysis dangerous waste slag, including the use of transforming agent, by converting
Compounds containing sodium in aluminium electroloysis dangerous waste slag is transformed into not fluorine-containing soluble sodium chemical combination by the mechanochemistry conversion reaction in mill
Object, fluorochemical be transformed into insoluble and harmless minerals fluorine compounds, be oxidized containing cyanogen compound be transformed into it is harmless
N2Or NH3And CO2, to thoroughly release the harm of fluoride and cyanide in aluminium electroloysis dangerous waste slag；Conversion system includes successively connecting
The dangerous waste slag crushing plant that connects, milling equipment, conversion mill, stirred reactor and solid-liquid separating equipment, solid-liquid separating equipment again with
Concentration or crystallizer, drying or Equipment for Heating Processing are directly connected to, and dry or Equipment for Heating Processing connects disintegrating apparatus.
Method for transformation containing sodium, fluorochemical in a kind of aluminium electroloysis dangerous waste slag, including following some or all of step
(sequence of steps below is to express for convenience, does not indicate which part precedence relationship, contained step specifically include directly
It is subject to literal logical specification or logical relation):
(1) aluminium electroloysis dangerous waste slag is broken, milling, screening and homogenizing, obtain the dangerous waste ground-slag of particle≤200 μm；Point
Analyse the molal quantity or quality for determining sodium and fluorine in unit mass dangerous waste ground-slag；It analyzes and determines CN in unit mass dangerous waste ground-slag-
The molal quantity or quality of ion；
Abrasive body is added in conversion mill, then conversion is ground and carries out air emptying or N2Displacement, by the dangerous waste of metering
Ground-slag is added in conversion mill, and the mass ratio for controlling dangerous waste ground-slag and abrasive body is 1:(0.2~10), the water of metering is added to
In conversion mill, the solid-liquid mass ratio for controlling dangerous waste ground-slag and water is 1:(1~10)；
By in dangerous waste ground-slag containing sodium, fluorochemical be converted to corresponding product chemistry stoichiometry 1~3 times of amount,
Or transforming agent is added in conversion mill by the amount of dangerous waste ground-slag quality 5~80%；
Grinding aid is added in conversion mill by the amount of dangerous waste ground-slag quality 0~1%；
(2) it completes to open conversion mill after step (1), the revolving speed of control conversion mill is 10~1000rpm, conversion temperature is
10~110 DEG C；In the conversion process, timing in batches is to slurry sampling analysis inspection, until Na in slurry solid formation+Ion contains
Amount meets company standard, solubility F-Ion concentration stops conversion mill when meeting national emission standard；
(3) slurry is transferred to stirred reactor (reaction kettle or reactive tank or reactor tank) after completion step (2) and carries out brokenly glue
With ripening, 60~150 DEG C of temperature is controlled, the processing time is 0.5~5h；
(4) by slurry that step (3) obtains using filtering or centrifuge separation mode is separated by solid-liquid separation and by aqueous solid phase
Object in conversion mill or stirred reactor (reaction kettle or reactive tank or reactor tank), using water be detergent by 1:(1~10) consolidate
Liquid quality than repeated several times dispensing laundry and be separated by solid-liquid separation, wash into solid formation soluble ion content meet enterprise mark
Until standard, merges separating liquid, respectively obtain the i.e. aqueous solid formation of mixture and solubility of wet fluorine-containing minerals and carbon
The weak solution of mixture；
(5) the aqueous solid formation that step (4) obtains is dried or is heat-treated 1 at a temperature of 80~300 DEG C~
10h, crushed to obtain the mixed powder material of fluorine-containing minerals and carbon again, the average particle size of mixed powder material≤
20 μm, which can be used as merchandise sales or further progress separating-purifying obtains high-quality carbon materials and fluorine
Compound mineral raw material；
The high temperature mixed powder material of fluorine-containing minerals and carbon being placed at a temperature of air atmosphere and 700~1200 DEG C
0.5~5h, the mixture that carbon component complete oxidation therein burns, its residue is fluorine-containing minerals are calcined in furnace；
(6) by the Dilute mixed solutions that step (4) obtains carry out concentration or crystallization treatment obtain mixture concentrated solution or
Person's solid-phase mixture, or Na, K, Li, Al, Mg, Ca compound separating-purifying in mixture are further obtained into more Gao Pin
The series compound raw material of matter and value；
(7) by CN in dangerous waste ground-slag-Ion conversion is at N2Or NH3And CO2Chemical reaction metering ratio 1~5 times of amount,
Perhaps by the amount of dangerous waste ground-slag quality 0.1~10% by cyanide transforming agent be added to or step (2) or step (3),
Or the oxidation containing cyanogen compound is converted to harmless N in step (6)2Or NH3And CO2.Timing carries out transformation system in batches
Analysis checks, until the CN in system-Ion concentration stops conversion reaction when meeting national emission standard；
(8) by generated NH in step (2) or step (3) or step (6)3、CO2、H2O gas carry out sorption enhanced and
Dry, generated reducibility gas is collected or direct oxidation burning.
Above-mentioned aluminium electroloysis dangerous waste slag contains F caused by referring in Aluminum Electrolysis Production-Ionic compound contains CN-Ion combination
Object is more than all solids waste of national emission standard.
There are Al, Al in above-mentioned aluminium electroloysis dangerous waste slag4C3, the substances such as AlN, Na, reaction institute is participated in conversion reaction
Imflammable gas (including the H of generation2、CH4、NH3Deng) it is reducibility gas described in step (8).
In above-mentioned conversion mill, the synchronous effect of high energy mechanical power is anti-in the mechanochemistry conversion containing sodium and fluorochemical
Answer so that solid particle is constantly ground, is levigate with conversion, make reactant and product constantly update from charcoal particle and
Removing, realizes the quick of conversion reaction and is properly completed.
Further, in all steps, pH control does not use protonic acid material for not less than 6, used to contain sodium
The transforming agent of compound and fluorochemical, cyanide transforming agent are free of chlorine element in grinding aid substance.
Further, the essential element that the dangerous waste cinder ladle includes is C (including graphitization C and non-graphitized C), Na, F,
It is two or more in Al, Ca, O, N, Li, Mg, Si, K, Fe；The compounds containing sodium includes NaF, Na3AlF6、NaCN、Na4
[Fe(CN)6] in it is two or more；The fluorochemical includes NaF, Na3AlF6、AlF3、LiF、CaF2、MgF2, in KF
It is two or more.
It further, include that Ca, Al, Mg, Sr, Ba, La, Ce each element are corresponding with the transforming agent of fluorochemical containing sodium
One or more of oxide, hydroxide, sulfate, nitrate, carbonate, acetate, citrate.
After being converted using transforming agent, the not fluorine-containing solubility of the correspondence that the compounds containing sodium in dangerous waste slag is transformed into contains sodium
Closing object includes NaOH, Na2SO4、NaNO3、NaOAc、Na2CO3、Na3C6H5O7、Na2AlO4、Na[Al(OH)6]2(OH)3、
NaAlSi2O6、Na2(H2SiO4)·7H2O、Na6Si8O19、Na2Al2SiO6、Na2Si2O5、Na2SiO3One or both of with
On.
After being converted using transforming agent, the insoluble and harmless minerals of the correspondence that the fluorochemical in dangerous waste slag is transformed into
Fluoride includes CaF2、MgF2、AlF3、SrF2、BaF2、CaF2、LaF3、CeF3、CeF4One or more of.
Further, the cyanide transforming agent includes Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、
CaO2、SrO2、BaO2、H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more of.
Further, the grinding aid includes polymerized polyalcohol, polyalcohol amine, triisopropanolamine, ethylene glycol, the third two
One of alcohol, glycerine, diethylene glycol, triethanolamine, amide, stearic acid, oleic acid, calgon, odium stearate or two
Kind or more.
Further, the transforming agent, grinding aid be with the addition of solid, aqueous solution or gaseous state, using it is primary be added,
Or the mode for being added or being continuously added in batches.
Conversion system containing sodium, fluorochemical in a kind of aluminium electroloysis dangerous waste slag, including sequentially connected dangerous waste slag are broken
Equipment, milling equipment, conversion mill, stirred reactor and solid-liquid separating equipment, solid-liquid separating equipment again with concentration or crystallizer,
Dry or Equipment for Heating Processing is directly connected to, and dry or Equipment for Heating Processing connects disintegrating apparatus.
It further, further include condensing plant, condensing plant is connect with concentration or crystallizer.
It further, further include exhaust collection absorption equipment, exhaust collection absorption equipment grinds with milling equipment, conversion, stirs
Mix reactor, condensing plant is all connected with.
It further, further include storage facilities, storage facilities includes the dusty material storage arrangement connecting with disintegrating apparatus
And the storage arrangement of concentrate or crystalline product.
It further, further include analysis Instrument equipment, analysis Instrument equipment is anti-to milling equipment, conversion mill, stirring is derived from
The sample of the equipment such as device, concentration or crystallizer, drying or Equipment for Heating Processing, storage is answered to carry out analysis detection.
Further, the dangerous waste slag crushing plant include jaw crusher, cone crusher, pillar crusher,
Double-shaft crusher or impact disintegrating machine.
Further, the milling equipment include column mill, Raymond mill, vertical mill, air swept mill or roll squeezer and with
The matched equipment for selecting dressing sieve point and homogenization, to obtain uniform, particle≤200 μm the dangerous waste ground-slag of composition.
Further, concentration or crystallizer are multiple-effect evaporation concentration or crystallization apparatus, for being concentrated or crystallizing solid-liquid point
Separating liquid from obtained soluble mixture is related to thermal energy and provides, evaporates the heat exchange and condensation, the recycling of condensed water of phase
Utilize, concentrate or transmission of crystal etc..
Above-mentioned exhaust collection absorption equipment is used for being crushed, being milled, sieving and being homogenized, and conversion reaction is broken glue and washed
Wash, be concentrated with crystallization etc. during generate tail gas be collected and absorption handle.Material composition in tail gas includes H2O、NH3、
CO2、H2、CH4、N2And micro dust；Gas phase H therein2O passes through condensation reuse, NH3、CO2, dust pass through absorbent absorb
It utilizes, fuel gas H2、CH4It is collected storage or enters combustion furnace as fuel utilization.
Material component detection, substance changing effect and content of the above-mentioned analysis Instrument equipment for each link of production process
Control detection, product quality detection, environmental emission standard monitoring.
Further, the described conversion mill is the air-tightness ball mill by transformation, body be equipped with abrasive body inlet and outlet,
Powder import, liquid material import, gas vent, slurry outlet, clean-drain mouth, gas sample mouth, slurry sample tap；Abrasive body
For one or more of corundum ball, zirconia ball, porcelain ball, steel ball, stainless steel ball, alloying pellet.
The beneficial effects of the present invention are:
(1) present invention has technical process convenient for control, is easy to industrialize that steady production, production cost are low, not will cause
The features such as three-waste pollution and equipment are corroded.
(2) present invention solves the problems of existing wet-treating and pyrogenic attack production technology and deficiency.For
Aluminium electroloysis dangerous waste slag harmlessness and resource utilization, which utilize, provides a kind of advanced, system solution.
Detailed description of the invention
Fig. 1 is the process flow diagram of method for transformation of the present invention.
Fig. 2 is the structural schematic diagram of system of the present invention.
Fig. 3 is the x-ray diffraction pattern of aluminium electroloysis dangerous waste slag used by embodiment.
Fig. 4 is the x-ray diffraction pattern of the obtained fluorine minerals C of embodiment 1.
The SEM that Fig. 5 is the obtained mixed powder material B of embodiment 1 schemes.
Specific embodiment
Below with specific embodiment further illustrate technical solution of the present invention, but the invention is not limited to embodiment,
It is not intended to limit the scope of the invention.
As shown in Fig. 2, system of the invention includes sequentially connected dangerous waste slag crushing plant 1, milling equipment 2, conversion mill
3, stirred reactor 4 and solid-liquid separating equipment 5, solid-liquid separating equipment 5 are set with concentration or crystallizer 7, dry or heat treatment again
Standby 6 are directly connected to, and dry or Equipment for Heating Processing 6 connects disintegrating apparatus 8；It further include condensing plant 9, exhaust collection absorption equipment
10 and storage facilities, condensing plant 9 connect with concentration or crystallizer 7, exhaust collection absorption equipment 10 and milling equipment 2, turn
Change mill 3, stirred reactor 4, condensing plant 9 to be all connected with, storage facilities includes the dusty material storage dress connecting with disintegrating apparatus
Set the storage arrangement 12 of 11 and concentrate or crystalline product.
It further include analysis Instrument equipment, analysis Instrument equipment is to being derived from milling equipment, conversion mill, stirred reactor, concentration
Or the sample of the equipment such as crystallizer, drying or Equipment for Heating Processing, storage carries out analysis detection.
The dangerous waste slag crushing plant includes jaw crusher, cone crusher, pillar crusher, double-shaft crusher
Or impact disintegrating machine.
The milling equipment includes column mill, Raymond mill, vertical mill, air swept mill or roll squeezer and matched choosing
Dressing sieve divides the homogenization equipment of powder, to obtain uniform, particle≤200 μm the waste cathode carbon powder of composition.
Concentration or crystallizer be multiple-effect evaporation be concentrated or crystallization apparatus, for be concentrated or crystallize be separated by solid-liquid separation obtain can
The separating liquid of soluble mixture is related to thermal energy and provides, evaporates the heat exchange and condensation, the recycling of condensed water, concentration of phase
Liquid or the transmission of crystal etc..
Above-mentioned exhaust collection absorption equipment, for broken, milling and homogenizing, glue and washing, concentration to be broken in conversion reaction
With crystallization etc. during generate tail gas be collected and absorption handle.Material composition in tail gas includes H2O、NH3、CO2、H2、
CH4、N2And micro dust；Gas phase H therein2O passes through condensation reuse, NH3、CO2, dust be absorbed and utilized by absorbent, can
Combustion gas body H2、CH4It is collected storage or enters combustion furnace as fuel utilization.
The described conversion mill is the air-tightness ball mill by transformation, body be equipped with abrasive body inlet and outlet, powder import,
Liquid material import, gas vent, slurry outlet, clean-drain mouth, gas sample mouth, slurry sample tap；Abrasive body be corundum ball,
One or more of zirconia ball, porcelain ball, steel ball, stainless steel ball, alloying pellet.
Embodiment 1
(1) aluminium electroloysis dangerous waste slag is crushed in high speed disintegrator, is sieved with the sieve of 200 mesh, using screenings into
Mechanochemistry conversion of the row containing sodium, fluorochemical.Sodium in unit mass aluminium electroloysis dangerous waste ground-slag is determined using chemical analysis
With the mass content of fluorine element, CN in unit mass aluminium electroloysis dangerous waste ground-slag is determined using chemical analysis-The quality of ion contains
Amount.
(2) 200g alloy steel ball is added in conversion mill, weighs 100g dangerous waste ground-slag, 45g CaSO4·2H2O、
2gCaO、1.5g Na2S2O8It is added in conversion mill and is uniformly mixed, use N2The air in conversion mill is replaced, then is added into conversion mill
Enter 300gH2O.Unlatching conversion mill, revolving speed 100rpm, temperature are 25 DEG C, and the conversion reaction time is 3h.
Slurry is transferred to stirred reactor after conversion reaction, mixing speed 1000rpm, temperature are 95 DEG C, and constant temperature stirs
Reaction 90min is mixed to stop.
By tail gas caused by step (1), step (2) respectively by being with the absorber that water is absorbent and with CaO
The absorber of absorbent, dust therein, NH3、CO2It is absorbed, H2、CH4Carry out combustion oxidation.
(3) negative pressure leaching is carried out to the slurry after being stirred to react, filter cake is transferred in conversion mill after suction filtration, is added
200gH2O dispensing laundry in conversion mill filters again, wash repeatedly and filters, BaCl of the washing to last filtrate with 2mol/L2
Until solution is examined without precipitating, filtrate is merged.
Filtrate is evaporated under reduced pressure, be concentrated and is crystallized, dry 8h obtains solubility in 120 DEG C of vacuum ovens by it
Mixture A.
(4) by aqueous filter cake under 100 DEG C of normal pressures dry 20h, dried object is crushed to obtain fluorine-containing minerals and carbon
Mixed powder material B is calcined 3h in the Muffle furnace of air atmosphere and obtains containing without charcoal by mixed powder material B at 900 DEG C
Fluorine minerals C.
As seen from Figure 3, the main object of aluminium electroloysis dangerous waste slag used by embodiment 1 coordinate be divided into C, NaF,
Na3AlF6、AlF3、LiF、MgF2、SiC、Si3N4、Ca5MgSi3O12、Ca2SiO4、MgSiO3、CaSiO3。
As seen from Figure 4, it is by the main component that embodiment 1 handles the obtained Fluoride-bearing Ore substance C without charcoal
CaF2、MgF2、SiC、Si3N4、Al2O3、Al2SiO5、SiO2, illustrate NaF, Na in dangerous waste slag3AlF6、AlF3, the components such as LiF
It is totally converted metallogenic material CaF2And MgF2, carbon content is fully oxidized burning.
As seen from Figure 5, the mixed powder material B of obtained fluorine-containing minerals and carbon is handled by embodiment 1
Grain diameter be no more than 8 μm, particle be random pattern.
From these testing and analysis datas: embodiment 1 realize in aluminium electroloysis dangerous waste slag containing sodium, fluorochemical it is complete
Full conversion, thoroughly relieves the harm of fluoride and cyanide in aluminium electroloysis dangerous waste slag.
Embodiment 2
(1) aluminium electroloysis dangerous waste slag is crushed in high speed disintegrator, is sieved with the sieve of 200 mesh, using screenings into
Mechanochemistry conversion of the row containing sodium, fluorochemical.Sodium in unit mass aluminium electroloysis dangerous waste ground-slag is determined using chemical analysis
With the mass content of fluorine element, CN in unit mass aluminium electroloysis dangerous waste ground-slag is determined using chemical analysis-The quality of ion contains
Amount.
(2) 300g alloy steel ball is added in conversion mill, weighs 100g dangerous waste ground-slag, 30g MgSO4, 1g polyethylene
Alcohol, 4g K2S2O8It is added in conversion mill and is uniformly mixed, use N2Air in displacement conversion mill, then 400g is added into conversion mill
H2O.Unlatching conversion mill, revolving speed 500rpm, temperature are 40 DEG C, and the conversion reaction time is 2.5h.
Slurry is transferred to stirred reactor after conversion reaction, mixing speed 700rpm, temperature are 105 DEG C, and constant temperature stirs
Reaction 100min is mixed to stop.
By tail gas caused by step (1), step (2) respectively by being with the absorber that water is absorbent and with CaO
The absorber of absorbent, dust therein, NH3、CO2It is absorbed, H2、CH4Carry out combustion oxidation.
(3) negative pressure leaching is carried out to the slurry after being stirred to react, filter cake is transferred in conversion mill after suction filtration, is added
400gH2O dispensing laundry in conversion mill filters again, wash repeatedly and filters, BaCl of the washing to last filtrate with 2mol/L2
Until solution is examined without precipitating, filtrate is merged.
Filtrate is evaporated under reduced pressure, be concentrated and is crystallized, dry 8h obtains solubility in 120 DEG C of vacuum ovens by it
Mixture A.
(4) by aqueous filter cake under 100 DEG C of normal pressures dry 20h, dried object is crushed to obtain fluorine-containing minerals and carbon
Mixed powder material B is calcined 3h in the Muffle furnace of air atmosphere and obtains containing without charcoal by mixed powder material B at 1000 DEG C
Fluorine minerals C.
The experimental results showed that embodiment 2 realizes the complete conversion in aluminium electroloysis dangerous waste slag containing sodium, fluorochemical, it is thorough
Bottom relieves the harm of fluoride and cyanide in aluminium electroloysis dangerous waste slag.
Embodiment 3
(1) aluminium electroloysis dangerous waste slag is crushed in high speed disintegrator, is sieved with the sieve of 200 mesh, using screenings into
Mechanochemistry conversion of the row containing sodium, fluorochemical.Sodium in unit mass aluminium electroloysis dangerous waste ground-slag is determined using chemical analysis
With the mass content of fluorine element, CN in unit mass aluminium electroloysis dangerous waste ground-slag is determined using chemical analysis-The quality of ion contains
Amount.
(2) 350g alloy steel ball is added in conversion mill, weighs 100g dangerous waste ground-slag, 25g SrSO4、2g SrO2It is added
It is uniformly mixed into conversion mill, uses N2Air in displacement conversion mill, then 350g H is added into conversion mill2O.Unlatching conversion mill,
Revolving speed is 700rpm, temperature is 50 DEG C, and the conversion reaction time is 3.5h.
Slurry is transferred to stirred reactor after conversion reaction, mixing speed 500rpm, temperature are 100 DEG C, and constant temperature stirs
Reaction 110min is mixed to stop.
By tail gas caused by step (1), step (2) respectively by being with the absorber that water is absorbent and with CaO
The absorber of absorbent, dust therein, NH3、CO2It is absorbed, H2、CH4Carry out combustion oxidation.
(3) negative pressure leaching is carried out to the slurry after being stirred to react, filter cake is transferred in conversion mill after suction filtration, is added
350gH2O dispensing laundry in conversion mill filters again, wash repeatedly and filters, BaCl of the washing to last filtrate with 2mol/L2
Until solution is examined without precipitating, filtrate is merged.
Filtrate is evaporated under reduced pressure, be concentrated and is crystallized, dry 8h obtains solubility in 120 DEG C of vacuum ovens by it
Mixture A.
(4) by aqueous filter cake under 100 DEG C of normal pressures dry 20h, dried object is crushed to obtain fluorine-containing minerals and carbon
Mixed powder material B is calcined 3h in the Muffle furnace of air atmosphere and obtains containing without charcoal by mixed powder material B at 950 DEG C
Fluorine minerals C.
The experimental results showed that embodiment 3 realizes the complete conversion in aluminium electroloysis dangerous waste slag containing sodium, fluorochemical, it is thorough
Bottom relieves the harm of fluoride and cyanide in aluminium electroloysis dangerous waste slag.
Claims (10)
1. the method for transformation in a kind of aluminium electroloysis dangerous waste slag containing sodium, fluorochemical, which is characterized in that including following part or
Overall Steps:
(1) aluminium electroloysis dangerous waste slag is broken, milling, screening and homogenizing, obtain the dangerous waste ground-slag of particle≤200 μm；Analysis is true
Determine the molal quantity or quality of sodium and fluorine in unit mass dangerous waste ground-slag；It analyzes and determines CN in unit mass dangerous waste ground-slag-Ion
Molal quantity or quality；
Abrasive body is added in conversion mill, then conversion is ground and carries out air emptying or N2Displacement, the dangerous waste ground-slag of metering is added
Enter into conversion mill, the mass ratio for controlling dangerous waste ground-slag and abrasive body is 1:(0.2~10), the water of metering is added to conversion mill
In, the solid-liquid mass ratio for controlling dangerous waste ground-slag and water is 1:(1~10)；
By in dangerous waste ground-slag containing sodium, fluorochemical be converted to corresponding product chemistry stoichiometry 1~3 times of amount or
Transforming agent is added in conversion mill by the amount of dangerous waste ground-slag quality 5~80%；
Grinding aid is added in conversion mill by the amount of dangerous waste ground-slag quality 0~1%；
(2) complete to open conversion mill after step (1), the revolving speed of control conversion mill is 10~1000rpm, conversion temperature be 10~
110℃；In the conversion process, timing in batches is to slurry sampling analysis inspection, until Na in slurry solid formation+Ion concentration symbol
Close company standard, solubility F-Ion concentration stops conversion mill when meeting national emission standard；
(3) complete slurry is transferred to stirred reactor after step (2) and carry out broken glue and ripening, control 60~150 DEG C of temperature,
The processing time is 0.5~5h；
(4) slurry that step (3) obtains is separated by solid-liquid separation using filtering or centrifuge separation mode and aqueous solid formation is existed
Be detergent in conversion mill or stirred reactor, using water by 1:(1~10) solid-liquid mass ratio repeated several times dispensing laundry simultaneously
Be separated by solid-liquid separation, washing is until into solid formation, the content of soluble ion meets company standard, merge separating liquid, respectively obtain wet
Fluorine-containing minerals and carbon mixture, that is, aqueous solid formation and soluble mixture weak solution；
(5) the aqueous solid formation that step (4) obtains is dried or is heat-treated 1~10h, again at a temperature of 80~300 DEG C
It is crushed to obtain the mixed powder material of fluorine-containing minerals and carbon；
The mixed powder material of fluorine-containing minerals and carbon is placed in the high temperature furnace at a temperature of air atmosphere and 700~1200 DEG C
Calcine 0.5~5h, the mixture that carbon component complete oxidation therein burns, its residue is fluorine-containing minerals；
(6) Dilute mixed solutions that step (4) obtains are subjected to concentration or crystallization treatment obtains mixture concentrated solution or solid
Phase mixture；
(7) by CN in dangerous waste ground-slag-Ion conversion is at N2Or NH3And CO2Chemical reaction metering ratio 1~5 times of amount or press
Cyanide transforming agent is added to or step (2) or step (3) or step by the amount of dangerous waste ground-slag quality 0.1~10%
Suddenly the oxidation containing cyanogen compound is converted to harmless N in (6)2Or NH3And CO2.Timing carries out analysis inspection to transformation system in batches
It looks into, until the CN in system-Ion concentration stops conversion reaction when meeting national emission standard；
(8) by generated NH in step (2) or step (3) or step (6)3、CO2、H2O gas carries out sorption enhanced and drying,
Generated reducibility gas is collected or direct oxidation burning.
2. the method for transformation in aluminium electroloysis dangerous waste slag according to claim 1 containing sodium, fluorochemical, which is characterized in that
In all steps, pH control does not use protonic acid material, used compounds containing sodium and fluorine-containing chemical combination for not less than 6
The transforming agent of object, cyanide transforming agent are free of chlorine element in grinding aid substance.
3. the method for transformation in aluminium electroloysis dangerous waste slag according to claim 1 containing sodium, fluorochemical, which is characterized in that
The essential element that the dangerous waste cinder ladle includes is two or more in C, Na, F, Al, Ca, O, N, Li, Mg, Si, K, Fe；Described
Compounds containing sodium includes NaF, Na3AlF6、NaCN、Na4[Fe(CN)6] in it is two or more；The fluorochemical includes
NaF、Na3AlF6、AlF3、LiF、CaF2、MgF2, it is two or more in KF.
4. the method for transformation in aluminium electroloysis dangerous waste slag according to claim 1 containing sodium, fluorochemical, which is characterized in that
Compounds containing sodium and the transforming agent of fluorochemical include the corresponding oxide of Ca, Al, Mg, Sr, Ba, La, Ce each element, hydrogen-oxygen
One or more of compound, sulfate, nitrate, carbonate, acetate, citrate.
5. the method for transformation in aluminium electroloysis dangerous waste slag according to claim 1 containing sodium, fluorochemical, which is characterized in that
The cyanide transforming agent includes Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、CaO2、SrO2、BaO2、
H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more of.
6. the method for transformation in aluminium electroloysis dangerous waste slag according to claim 1 containing sodium, fluorochemical, which is characterized in that
The grinding aid include polymerized polyalcohol, polyalcohol amine, triisopropanolamine, ethylene glycol, propylene glycol, glycerine, diethylene glycol,
One or more of triethanolamine, amide, stearic acid, oleic acid, calgon, odium stearate.
7. the method for transformation in aluminium electroloysis dangerous waste slag according to claim 1 containing sodium, fluorochemical, which is characterized in that
The transforming agent, grinding aid with the addition of solid, aqueous solution or gaseous state, using it is primary be added or be added in batches or
The mode that person is continuously added to.
8. the conversion system in a kind of aluminium electroloysis dangerous waste slag containing sodium, fluorochemical, which is characterized in that including sequentially connected danger
Waste residue crushing plant, milling equipment, conversion mill, stirred reactor and solid-liquid separating equipment, solid-liquid separating equipment again with concentration or
Crystallizer, drying or Equipment for Heating Processing are directly connected to, and dry or Equipment for Heating Processing connects disintegrating apparatus.
9. the conversion system in aluminium electroloysis dangerous waste slag according to claim 8 containing sodium, fluorochemical, which is characterized in that
It further include condensing plant, exhaust collection absorption equipment, storage facilities and analysis Instrument equipment, condensing plant is set with concentration or crystallization
Standby connection, exhaust collection absorption equipment are all connected with milling equipment, conversion mill, stirred reactor, condensing plant, storage facilities packet
Include the storage arrangement of the dusty material storage arrangement and concentrate or crystalline product that connect with disintegrating apparatus, analysis Instrument equipment pair
It is derived from the sample of milling equipment, conversion mill, stirred reactor, concentration or crystallizer, drying or Equipment for Heating Processing, storage facilities
Carry out analysis detection.
10. the conversion system in aluminium electroloysis dangerous waste slag according to claim 9 containing sodium, fluorochemical, which is characterized in that
The dangerous waste slag crushing plant is jaw crusher, cone crusher, pillar crusher, double-shaft crusher or impact type fining
Broken machine；The milling equipment is column mill, Raymond mill, vertical mill, air swept mill or roll squeezer and matched selects dressing sieve
Divide the homogenization equipment of powder；The concentration or crystallizer is multiple-effect evaporation concentration or crystallization apparatus；The conversion mill
For by transformation air-tightness ball mill, body be equipped with abrasive body inlet and outlet, powder import, liquid material import, gas vent,
Slurry outlet, clean-drain mouth, gas sample mouth, slurry sample tap；Abrasive body be corundum ball, zirconia ball, porcelain ball, steel ball,
One or more of stainless steel ball, alloying pellet.
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| CN113426808A (en) * | 2021-06-29 | 2021-09-24 | 云南云铝润鑫铝业有限公司 | Method for recovering fluoride salt from aluminum electrolysis overhaul residues through pressurized alkaline leaching |
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