CN109231225A - A method of comprehensive utilization flyash - Google Patents
A method of comprehensive utilization flyash Download PDFInfo
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- CN109231225A CN109231225A CN201811173144.1A CN201811173144A CN109231225A CN 109231225 A CN109231225 A CN 109231225A CN 201811173144 A CN201811173144 A CN 201811173144A CN 109231225 A CN109231225 A CN 109231225A
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- alkali
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
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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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
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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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
- C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
Abstract
The present invention relates to a kind of methods for comprehensively utilizing flyash, S1 mix: by flyash, lime and alkali and mother liquor mix and dry, obtain mixed raw material；S2 sintering: mixed raw material is placed in 800~1250 DEG C of temperature sintering reactions, obtains sintered clinker；S3 Leach reaction: Leach reaction is carried out to the sintered clinker, solid-liquor separation obtains leached mud and leachate；S4 proposes aluminium processing: being handled using any combination of evaporating, concentrating and crystallizing, decomposition of crystal seed, carbonation decomposition or first three mode the leachate, obtains mentioning aluminium mother liquor and Al (OH)3Or NaAlO2Crystal returns to step S1 after mentioning aluminium mother liquor concentrations；S5 leached mud dealkalize: by leached mud and sodium hydroxide solution mixing de-alkali reaction, separation of solid and liquid obtains calcium silicate powder and lye；The lye of S6 recycling step S5.The present invention has recycled aluminium oxide and silica in flyash, and alumina extraction ratio is up to 90% or more, and almost non-pollutant discharge, recycling and utilization to flyash almost full constituent, realize the effect to Ash Utilization processing and high added value comprehensive utilization.
Description
Technical field
The invention belongs to the technical fields of total utilization of PCA, and in particular to a method of comprehensive utilization flyash.
Background technique
Flyash is the flour that a kind of particle is tiny and can flow in air.Usually said flyash refers to
The substance being discharged after levigate coal dust burns in the boiler in coal-burning power plant from flue and furnace bottom.Flyash is the main of coal-burning power plant
Byproduct is the maximum industrial waste of discharge amount.According to calculating, every burning 1t coal just generates the flyash of 250-300kg.It is coal-fired
Thermal power plant is every to generate 1kWh electricity, need to consume coal about 300g, generate flyash about 100g.By 2008, the year of Coal Ash in China was arranged
200Mt is high-volume alreadyd exceed, but also is increased with faster speed.
Environment is not only polluted in a large amount of discharges of flyash, but also occupies a large amount of arable lands, while power plant will also pay expensive grey field
Construction and administration fee.With the fast development of power industry, this contradiction will be protruded more.However, if flyash
Regard kind of a resource as, carry out comprehensive utilization, be allowed to recycling, so that it may turn waste into wealth, be conducive to environment, economy, society association
The exhibition of readjusting the distribution.
Currently, the utilization of China's flyash is concentrated mainly on building materials, agricultural aspect, feature is that usage amount is big, but flyash
Value be underutilized, 70% or more flyash quality score is by Al2O3、SiO2Composition, further include Fe, Ca,
The oxide and various trace elements of Mg, S, K, Na, Ti, P, there are also uncombusted charcoals.Carry out high added value for flyash
Fining comprehensive utilization can not only bring huge economic benefit, and objectively solve china natural resources anxiety and flyash
Bring environmental problem.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of method for comprehensively utilizing flyash.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
A method of comprehensive utilization flyash includes the following steps:
S1: it mix: by flyash, lime and alkali and mother liquor mix and dries, obtains mixed raw material, wherein institute
It states and contains sodium carbonate and sodium aluminate in mother liquor；
S2: sintering: sintering reaction at a temperature of mixed raw material is placed in 800~1250 DEG C obtains sintered clinker；
S3: Leach reaction: Leach reaction is carried out to the sintered clinker, solid-liquor separation obtains leached mud and leaching after reaction
Liquid leaches the mixed liquor of main component sodium aluminate and sodium carbonate in medium, molar concentration/aluminium oxide molar concentration of sodium oxide molybdena
Molecular proportion αKFor 1.2~1.5, AO (alumina concentration)=45~65g/L, Na2OC(carbon alkali concentration)=5~20g/L, it is described
Leachate contains sodium aluminate；
S4: aluminium processing is proposed: using any combination pair of evaporative crystallization, decomposition of crystal seed, carbonation decomposition or first three mode
The leachate is handled, and obtains mentioning aluminium mother liquor and Al (OH)3Or NaAlO2Crystal, by it is described mention aluminium mother liquor concentrations after return to
The mixing step of step S1；
S5: leached mud dealkalize: leached mud being mixed with sodium hydroxide solution and carries out de-alkali reaction, is separated by solid-liquid separation after reaction,
Obtain calcium silicates and lye；
S6: the lye of recycling step S5.
As a preferred embodiment of the present invention, in step S1, the flyash, lime and alkali and mother liquor are according to liquid-solid ratio
The ratio of 1:3 is dried outside kiln in the ball mill after mixing.
Through the resulting mixed raw material of step S1, sodium, iron, aluminium, calcium, silicon, titanium total amount existing for each form are respectively with oxide
Mole percent, each component is as follows:
Alkali ingredient is [Na2O]Always=[Na2O]1+[Na2O]2+[Na2O]3,
Wherein: [Na2O]1=[Fe2O3]；[Na2O]2=[Al2O3]；[Na2O]3=XN×[SiO2],
XN=0.3~1.0；
Calcium ingredient is [CaO]Always=[CaO]1+[CaO]2,
Wherein, [CaO]1=[TiO2]；[CaO]2=XC×[SiO2], XC=0.5~1.5.
Since mother liquor is obtained from evaporating, concentrating and crystallizing, decomposition of crystal seed or carbonation decomposition course, contain in mother liquor
There are sodium hydroxide (being concentrated by evaporation mother liquor containing sodium hydroxide) and sodium carbonate (carbonation decomposition generation sodium carbonate) or sodium aluminate (crystal seed
Decomposition nut liquid contains sodium aluminate), therefore mother liquor and flyash, lime and alkali mix are used, on the one hand mixing helps in the liquid phase
In obtain mixing the higher mixed raw material of dispersed homogeneous degree；On the other hand, sodium aluminate, carbonic acid contained in recoverable mother liquor
Sodium, sodium hydroxide etc..
As a preferred embodiment of the present invention, in step S1, the alkali is the mixed of carbon alkali, caustic alkali or carbon alkali and caustic alkali
Close alkali.
As a preferred embodiment of the present invention, in step S2, the sintering temperature is preferably 1100 DEG C~1150 DEG C, is burnt
Tie 0.5~2h of time, preferably 1~1.5h.
It is main therebetween that following chemical reaction occurs if being sintered in air:
Al2O3+Na2CO3=Na2O·Al2O3+CO2；
Fe2O3+Na2CO3=Na2O·Fe2O3+CO2；
CaCO3+TiO2=CaOTiO2+CO2；
mNa2CO3+nCaCO3+qSiO2=mNa2O·nCaO·qSiO2+CO2；
Wherein m, n, q are respectively independent and are greater than 0.
As a preferred embodiment of the present invention, in step S3, the Leach reaction are as follows: dense using sodium oxide molybdena mole
The sodium aluminate solution of degree/aluminium oxide molar concentration=1.2~1.5, leach liquid-solid ratio be 3~6 (sodium aluminate solution with sintering it is ripe
The volume mass ratio of material), alumina concentration=45~65g/L, Leach reaction temperature is 70~90 DEG C, extraction time 15~
60min。
After step S3 processing, acquired leachate mainly contains sodium aluminate solution, the leached mud mainly siliceous calcification
Close object and calcium titanate etc..
It is specific to operate are as follows: to be concentrated by evaporation leachate a part in step S4 as a preferred embodiment of the present invention
Crystallization, a part of decomposition of crystal seed；Or by a part of evaporating, concentrating and crystallizing of leachate, a part of carbonation decomposition；Or it will leaching
A part of decomposition of crystal seed of liquid out, a part of carbonation decomposition.
Wherein decomposition of crystal seed is (excellent by putting into high activity aluminium hydroxide crystal seed into leachate of a part containing sodium aluminate
Selecting additional amount is 50g/L), it is crystallized at 50~60 DEG C, obtains aluminium hydroxide and seed precipitation solution, aluminium is contained in the seed precipitation solution
Sour sodium, preferably decomposition temperature are 50~60 DEG C, the resolving time >=10h；Another part leachate evaporating, concentrating and crystallizing obtains aluminic acid
Sodium crystal and evaporation mother liquor.After two kinds of mother liquors merge collection, it is concentrated and return step S1 is used for mix.
Wherein carbonation decomposition is by putting into aluminium hydroxide crystal seed into the leachate containing sodium aluminate and being passed through CO2Gas
Body decomposes it and crystalline aluminum hydroxide is precipitated, while obtaining the evaporation mother liquor of containing sodium carbonate.This partial mother liquid can also return
Mix and recycling are carried out into step S1.
As a preferred embodiment of the present invention, in step S5, during leached mud dealkalize: reaction temperature is 120~
200 DEG C, dealkalize time 30min~for 24 hours, liquid-solid ratio=3~6 (volume mass of sodium hydroxide solution and leached mud ratio), lye
Middle oxidation na concn=20~120g/L.
Preferably, liquid-solid ratio=5, it is preferable that reaction temperature is 160~180 DEG C.
In this process, on the one hand calcium silicates can be converted by other calcium salts, to obtain calcium silicate powder material, separately
On the one hand the sodium in slag can be recycled, be transferred in lye, sold directly as sodium hydroxide product.Calcium silicates can be used as Building wood
Material, thermal insulation material, refractory material, filter aid etc..
As a preferred embodiment of the present invention, in step S6, lye a part that step S5 is generated is used to produce
NaOH product, remaining returns to step S5 for de-alkali reaction after diluting.
As a preferred embodiment of the present invention, in step S1, the flyash by mass percentage, chemical component
Are as follows: aluminium oxide (Al2O3) 50.7%, silica (SiO2) 38.3%, sodium oxide molybdena (Na2O) 0.37%, calcium oxide (CaO)
3.61%, iron oxide (Fe2O3) 2.17%, titanium dioxide (TiO2) 1.81%, alumina silica ratio 1.19；
Alternatively, the flyash is by mass percentage, chemical component are as follows: aluminium oxide (Al2O3) 38.18%, silica
(SiO2) 32.86%, sodium oxide molybdena (Na2O) 0.07%, calcium oxide (CaO) 11.60%, iron oxide (Fe2O3) 3.01%, titanium dioxide
Titanium (TiO2) 1.81%, alumina silica ratio 1.16；
Alternatively, the flyash is by mass percentage, chemical component are as follows: aluminium oxide (Al2O3) 42.11%, silica
(SiO2) 45.90%, sodium oxide molybdena (Na2O) 0.37%, calcium oxide (CaO) 2.21%, iron oxide (Fe2O3) 2.02%, titanium dioxide
Titanium (TiO2) 1.39%, alumina silica ratio 1.19.
(3) beneficial effect
The beneficial effects of the present invention are:
The present invention is sintered the mixed raw material of drying, then Leach reaction, recycled aluminium oxide in flyash and
Silica, alumina extraction ratio can reach 90% or more, produce the aluminum-containing products and calcium silicate powder material of high added value,
It is used for mix after the crystalline mother solution of leachate is concentrated simultaneously, facilitates aluminic acid in the uniformity and mother liquor of mix
The recycling of sodium/sodium carbonate etc., and the lye of de-alkali reaction is recovered and recycles, therefore the present invention almost arrange by contamination-free
It puts, there is environment friendly；The recycling and utilization that almost full constituent has been carried out to flyash, realize at Ash Utilization
Reason and the effect of high added value comprehensive utilization.
The method of the present invention is suitable for can be according to market when to leachate crystallization treatment to the large consumption of flyash progress
Demand adjusts product category and ratio (such as obtaining aluminum hydroxide crystals or aluminic acid sodium crystal), flexible and changeable, also can be used as raw material
Metallurgical-grade aluminum oxide is prepared by simple Bayer process, and calcium silicate material is then a kind of high added value thermal insulation material, market is answered
With wide, potentiality are big.
Compared with traditional soda lime sintering process technique, method of the invention is low with calcium amount, and sintering temperature is low, and to leaching
It slags tap be recycled and obtains calcium silicates.Compared with acidity extraction alumina technology, present device is mature and can produce
Metallurgical-grade aluminum oxide product.The comprehensive utilization to flyash is realized by means of the present invention, while obtaining containing for high added value
Aluminium product and calcium silicate powder have carried out the efficient utilization of green to flyash.
Detailed description of the invention
Fig. 1 is a kind of flow chart for the method for comprehensively utilizing flyash of the present invention.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.
As shown in connection with fig. 1, the present invention provides a kind of method for comprehensively utilizing flyash comprising step:
S1: it mix: by flyash, lime and alkali and mother liquor mix and dries, obtains mixed raw material, wherein institute
It states and contains sodium carbonate and sodium aluminate in mother liquor.
Through the resulting mixed raw material of step S1, sodium, iron, aluminium, calcium, silicon, titanium total amount existing for each form are respectively with oxide
Mole percent, each component is as follows:
Alkali ingredient is [Na2O]Always=[Na2O]1+[Na2O]2+[Na2O]3,
Wherein: [Na2O]1=[Fe2O3]；[Na2O]2=[Al2O3]；[Na2O]3=XN×[SiO2],
XN=0.3~1.0；
Calcium ingredient is [CaO]Always=[CaO]1+[CaO]2,
Wherein, [CaO]1=[TiO2]；[CaO]2=XC×[SiO2], XC=0.5~1.5.
S2: sintering: at a temperature of mixed raw material is placed in 800~1250 DEG C, low-temperature sintering reacts 0.5~2h, is sintered
Clinker；
S3: Leach reaction: Leach reaction is carried out to the sintered clinker, solid-liquor separation obtains leached mud and leaching after reaction
Liquid leaches the mixed liquor of medium main component sodium aluminate and sodium carbonate, molar concentration/aluminium oxide molar concentration of sodium oxide molybdena
Molecular proportion αKFor 1.2~1.5, AO (alumina concentration)=45~65g/L, Na2OC(carbon alkali concentration)=5~20g/L, the leaching
Liquid contains sodium aluminate out；
S4: aluminium processing is proposed: using any combination pair of evaporative crystallization, decomposition of crystal seed, carbonation decomposition or first three mode
The leachate is handled, and obtains mentioning aluminium mother liquor and Al (OH)3Or NaAlO2Crystal, by it is described mention aluminium mother liquor concentrations after return to
The mixing step of step S1；
S5: being modulated molten aluminum is proposed in step S4, after circulating mother liquor used in step S1 is made, in return step S1
Participate in mixing；
S6: dealkalize liquid is added in leached mud in step S3 and carries out recycling alkali process, during dealkalize: reaction temperature is
120~200 DEG C, dealkalize time 30min~for 24 hours, NaOH solution is mainly used in liquid-solid ratio=3~6, dealkalize, wherein oxygen in dealkalize liquid
Change na concn=20~120g/L.Separation of solid and liquid obtains calcium silicate powder and lye, and lye a part is sold directly as product,
Remaining is for recycling alkali process next time.To help to understand, below in conjunction with specific embodiment, to technical solution of the present invention feature
It is illustrated with effect.
Embodiment 1
The present embodiment uses flyash, main chemical compositions (mass percent, wt%) are as follows: aluminium oxide (Al2O3)
50.7%, silica (SiO2) 38.3%, sodium oxide molybdena (Na2O) 0.37%, calcium oxide (CaO) 3.61%, iron oxide (Fe2O3)
2.17%, titanium dioxide (TiO2) 1.81%, alumina silica ratio 1.19.
According to the flow processing of Fig. 1:
S1 mix: it will be mixed after flyash desiliconization with a small amount of lime, carbon alkali and circulating mother liquor, according to the ratio of L/S=3
Example be uniformly mixed in the ball mill with circulating mother liquor, after dried outside kiln.
The lime and supplement carbon alkali of the mix of step S1 are general industry grade product；XN=0.5；XC=1.0.
S2 sintering: by drying material in 1100 DEG C of sintering reaction 1h, sintered clinker is obtained after reaction.
S3 Leach reaction: sintered clinker is subjected to Leach reaction, obtains leached mud and leachate after solid-liquor separation.The process
In, extraction temperature is 75 DEG C, extraction time 15min, leaches liquid-solid ratio L/S=3 and (leaches the volume of solution and sintered clinker used
Mass ratio), leach solution composition used: AO (aluminium oxide) concentration=55g/L；Aoxidize na concn=10g/L.
Dissolution reaction by this step, alumina extraction ratio can reach 95% or more；
S4 mentions aluminium: by a part of evaporating, concentrating and crystallizing of leachate, a part of decomposition of crystal seed.By 50g/L aluminium hydroxide crystal seed
It is added in leachate, carries out crystallization 20h at 55 DEG C, obtain aluminium hydroxide and seed precipitation solution；Another part leachate evaporation knot
Crystalline substance obtains aluminic acid sodium crystal and evaporation mother liquor.Aluminium hydroxide and sodium aluminate are as output of products, and after two kinds of mother liquor mixing, concentration is returned
Return step S1.
S5 leached mud dealkalize: leached mud carries out dealkalize under the action of sodium hydroxide solution (oxidation na concn=50g/L)
Reaction.Wherein, de-alkali reaction temperature is 180 DEG C, dealkalize time 40min, liquid-solid ratio L/S=5 (sodium hydroxide lye and leached mud
Volume mass ratio).
S6: recycle of alkali liquor: calcium silicate powder and dealkalize liquid are obtained after separation of solid and liquid, dealkalize liquid a part is directly as product
Output, return step S5 is recycled after a part dilution.Calcium silicate powder page is as output of products, part dealkalize liquid return step
S5。
The product of the present embodiment includes: aluminic acid sodium crystal, aluminium hydroxide, lye and calcium silicate powder material.
Embodiment 2
The present embodiment uses flyash, main chemical compositions (mass percent, wt%) are as follows: aluminium oxide (Al2O3)
38.18%, silica (SiO2) 32.86%, sodium oxide molybdena (Na2O) 0.07%, calcium oxide (CaO) 11.60%, iron oxide
(Fe2O3) 3.01%, titanium dioxide (TiO2) 1.81%, alumina silica ratio 1.16.
According to the flow processing of Fig. 1:
S1 mix: it will be mixed after flyash desiliconization with a small amount of lime, carbon alkali and circulating mother liquor, according to the ratio of L/S=3
Example be uniformly mixed in the ball mill with circulating mother liquor, after dried outside kiln；
The lime and supplement caustic alkali of the mix of step S1 are general industry grade product；XN=1.0；XC=1.0.
S2 sintering: by drying material in 1150 DEG C of sintering reaction 1h, sintered clinker is obtained after reaction；
S3 Leach reaction: sintered clinker is subjected to Leach reaction, obtains leached mud and leachate after solid-liquor separation.This step
In, extraction temperature is 70 DEG C, extraction time 30min, leaches liquid-solid ratio L/S=4, and it is dense to leach solution composition AO (aluminium oxide) used
Degree=55g/L aoxidizes na concn=15g/L.
Dissolution reaction by this step, alumina extraction ratio can reach 90% or more.
S4 mentions aluminium: by a part of evaporative crystallization of leachate, a part of decomposition of crystal seed.
50g/L crystal seed is added in leachate, crystallization 10h is carried out at 50 DEG C, obtains aluminium hydroxide and crystalline mother solution.Separately
A part of evaporative crystallization obtains aluminic acid sodium crystal and evaporation mother liquor.Aluminium hydroxide and sodium aluminate are directly as product, two kinds of mother liquors
After mixing, adjustment concentration returns to mixing.
S5 leached mud dealkalize: leached mud carries out de-alkali reaction under the action of dealkalize liquid hydrogen sodium hydroxide solution.De-alkali reaction
Temperature is 160 DEG C, dealkalize time 90min, liquid-solid ratio L/S=5, takes off concentration of lye Na2OK(sodium oxide molybdena)=50g/L.
S6 recycle of alkali liquor: calcium silicate powder and lye are obtained after solid-liquor separation.Calcium silicate powder material and part lye are made
For output of products；Remaining dealkalize liquid return step S5.
The product of the present embodiment includes: aluminic acid sodium crystal, aluminium hydroxide and calcium silicate powder material.
Embodiment 3
The present embodiment uses flyash, main chemical compositions (mass percent, wt%) are as follows: aluminium oxide (Al2O3)
42.11%, silica (SiO2) 45.90%, sodium oxide molybdena (Na2O) 0.37%, calcium oxide (CaO) 2.21%, iron oxide
(Fe2O3) 2.02%, titanium dioxide (TiO2) 1.39%, alumina silica ratio 1.19.
According to the flow processing of Fig. 1:
S1: it will be mixed after flyash desiliconization with a small amount of lime, carbon alkali and circulating mother liquor, according to the ratio and circulation of L/S=3
Mother liquor is uniformly mixed in the ball mill, after dried outside kiln；
The lime and supplement carbon alkali of the mix of step S1 are general industry grade product；XN=1.0；XC=1.5.
S2: by drying material in 1150 DEG C of sintering reaction 1h, sintered clinker is obtained after reaction.
S3: sintered clinker is subjected to Leach reaction, obtains leached mud and leachate after solid-liquor separation.Wherein, extraction temperature
It is 65 DEG C, extraction time 30min, leaches liquid-solid ratio L/S=4, leaches solution composition AO (aluminium oxide)=55g/L used；Na2OC
(sodium oxide molybdena)=10g/L.
Dissolution reaction by this step, alumina extraction ratio can reach 90% or more；
S4: by a part of evaporative crystallization of leachate, a part of decomposition of crystal seed.
50g/L aluminium hydroxide crystal seed is added in leachate, crystallization 10h is carried out at 60 DEG C, obtains aluminium hydroxide and knot
Brilliant mother liquor；The aluminium hydroxide crystal seed of 80g/L is added in another part leachate, evaporative crystallization obtains aluminic acid sodium crystal and evaporation is female
Liquid.Return step S1 is concentrated directly as output of products, and after two kinds of crystalline mother solution mixing in aluminium hydroxide and sodium aluminate.
S5: leached mud carries out de-alkali reaction under the action of sodium hydroxide solution.De-alkali reaction temperature is 170 DEG C, dealkalize
Time 60min, liquid-solid ratio L/S=5, concentration of lye Na2OK=50g/L.
S6: separation of solid and liquid obtains calcium silicate powder material as output of products, and dealkalize liquid returns to S5 or production caustic alkali.
The product of the present embodiment includes: aluminic acid sodium crystal, aluminium hydroxide and calcium silicate powder material.
Finally, it should be noted that above-described embodiments are merely to illustrate the technical scheme, rather than to it
Limitation；Although the present invention is described in detail referring to the foregoing embodiments, those skilled in the art should understand that:
It can still modify to technical solution documented by previous embodiment, or to part of or all technical features into
Row equivalent replacement；And these modifications or substitutions, it does not separate the essence of the corresponding technical solution various embodiments of the present invention technical side
The range of case.
Claims (9)
1. a kind of method for comprehensively utilizing flyash, which comprises the steps of:
S1: it mix: by flyash, lime, alkali and mother liquor mix and dries, obtains mixed raw material, wherein the mother
Contain sodium carbonate and sodium aluminate in liquid；
S2: sintering: sintering reaction at a temperature of mixed raw material is placed in 800~1250 DEG C obtains sintered clinker；
S3: Leach reaction: Leach reaction is carried out to the sintered clinker, solid-liquor separation obtains leached mud and leachate, the leaching
Liquid contains sodium aluminate out；
S4: aluminium processing is proposed: using any combination of evaporative crystallization, decomposition of crystal seed, carbonation decomposition or first three mode to described
Leachate is handled, and obtains mentioning aluminium mother liquor and Al (OH)3Or NaAlO2Crystal, by it is described mention aluminium mother liquor concentrations after return to step
The mixing step of S1；
S5: leached mud dealkalize: leached mud is mixed with sodium hydroxide solution and carries out de-alkali reaction, is separated by solid-liquid separation, obtains after reaction
Calcium silicates and lye；
The lye of S6 recycling step S5.
2. the method according to claim 1, wherein the flyash, lime and alkali and mother liquor are pressed in step S1
According to the ratio of liquid-solid ratio 1:3, in the ball mill after mixing, dried outside kiln.
3. the method according to claim 1, wherein in step S1, the alkali be carbon alkali, caustic alkali or carbon alkali with
The mixed base of caustic alkali.
4. method according to claim 1 or 2 or 3, which is characterized in that former through the resulting mixing of step S1 in step S1
Expect, for sodium, iron, aluminium, calcium, silicon, titanium total amount existing for each form respectively with the mole percent of oxide, each component is as follows:
Alkali ingredient is [Na2O]Always=[Na2O]1+[Na2O]2+[Na2O]3,
Wherein: [Na2O]1=[Fe2O3]；[Na2O]2=[Al2O3]；[Na2O]3=XN×[SiO2], XN=0.3~1.0；
Calcium ingredient is [CaO]Always=[CaO]1+[CaO]2,
Wherein, [CaO]1=[TiO2]；[CaO]2=XC×[SiO2], XC=0.5~1.5.
5. the method according to claim 1, wherein in step S2, the sintering temperature is preferably 1100 DEG C~
1150 DEG C, 0.5~2h of sintering time, preferably 1~1.5h.
6. the method according to claim 1, wherein in step S3, the Leach reaction are as follows: use sodium oxide molybdena
The sodium aluminate solution of molar concentration/aluminium oxide molar concentration=1.2~1.5, leaching liquid-solid ratio is 3~6, alumina concentration=
45~65g/L, Leach reaction temperature are 70~90 DEG C, 15~60min of extraction time.
7. the method according to claim 1, wherein being divided using evaporative crystallization, crystal seed in step S4 leachate
Three kinds of solution, carbonation decomposition modes are freely combined to obtain Al (OH)3Or NaAlO2Crystal.
8. the method according to claim 1, wherein in step S5, during leached mud dealkalize: reaction temperature
It is 120~200 DEG C, dealkalize time 30min~for 24 hours, liquid-solid ratio=3~6 aoxidize na concn=20~120g/L in lye.
9. the method according to claim 1, wherein the lye for generating step S5, a part is directly in step S6
It connects and does NaOH product, another part returns to step S5 after diluting, is re-used for de-alkali reaction.
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| CN112813284A (en) * | 2020-12-29 | 2021-05-18 | 中国科学院过程工程研究所 | Method for extracting aluminum from aluminum-containing mineral |
| CN112934912A (en) * | 2021-01-26 | 2021-06-11 | 湖南青涟环保科技有限公司 | Pretreatment method of waste incineration fly ash |
| CN113149718A (en) * | 2021-04-28 | 2021-07-23 | 东北大学 | Method for preparing silicon-potassium compound fertilizer by using fly ash |
| CN115321568A (en) * | 2022-01-21 | 2022-11-11 | 重庆龙健金属制造有限公司 | Method for preparing sodium aluminate by resource utilization of aluminum ash |
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