CN106966416A - A kind of method that high purity aluminium oxide is extracted from coal-powder boiler flyash - Google Patents
A kind of method that high purity aluminium oxide is extracted from coal-powder boiler flyash Download PDFInfo
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- CN106966416A CN106966416A CN201710230784.0A CN201710230784A CN106966416A CN 106966416 A CN106966416 A CN 106966416A CN 201710230784 A CN201710230784 A CN 201710230784A CN 106966416 A CN106966416 A CN 106966416A
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- flyash
- hydrochloric acid
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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
- C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
- C01F7/22—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with halides or halogen acids
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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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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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
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0427—Dry materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
- C04B28/12—Hydraulic lime
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a kind of method that high purity aluminium oxide and white clay are extracted from flyash, this method includes：Coal-powder boiler flyash it is in small, broken bits；The acid extraction of alundum (Al2O3)；The separation of solid and liquid of alundum (Al2O3) and white clay (silica)；The precipitation of aluminium chloride crystal and purifying (removal of the impurity such as calcium, iron, magnesium)；The calcining of crystal aluminum chloride；The process procedure such as the precipitation of calcination stage and aluminium chloride crystal and the recycling of purification phase hydrochloric acid and hydrogen chloride gas.Aluminum oxide and white clay prepared by the present invention, it is high value added product, the recovery rate of aluminum oxide is more than 85% in flyash, white clay can be used to prepare molecular sieve, filler for plastic, by flyash " eating dry bleed ", and technological process is short, and Matter Transfer is utilized, energy consumption is low, non-secondary pollution, is recycling economy.
Description
Technical field
The invention belongs to solid waste recycling-recycling economy technical field, and in particular to a kind of from coal-powder boiler powder
The method that high purity aluminium oxide is extracted in coal ash.
Background technology
In recent years, metallic aluminium and aluminium alloy turn into the second important meals for being only second to steel in the world, its main ore deposit
Thing source is bauxite, and bauxite resource distribution in the world's is concentrated and and uneven (wherein Guinea, Australia, Jamaica, bar
West summation just occupy world's gross reserves 70%).China is the first big primary aluminum country of consumption in the world, and China's high-quality alum clay
Ore resources are deficient, and import dependency degree is up to 50%, and this causes China very passive in price in aluminium industry, and it will influence whole
The safety of national economy.It is therefore desirable to improve China's bauxite production technique or find bauxite alternate resources.
Flyash is the solid waste residue of coal-burning power plant's discharge.At present, the total volume of cargo in storage of flyash is up to 3,000,000,000 tons, this
Substantial amounts of land resource is not only occupied, but also severe contamination environment.Silicon, aluminium are its main components in flyash, especially
It is that alumina content is up to 50% or so in Zhungeer coal field fly ash in electric power plant, silica is 40% or so, and therefore, flyash is one
Plant potential bauxite alternate resources.
As country is mandatory to the requirement more and more higher and national relevant laws and regulations of environmental protection and incentive policy
Influence, over nearly 20 years, starts the upsurge that one flyash extracts aluminum oxide again.(the quasi- energy resource synthetic development of Shenhua has for my company
Limit company) the industrialization pilot plant for having run and having produced 4000 tons of aluminum oxide per year, " one used were successfully built up and gone into operation in 2011
Step acid extracting " extracts alumina technology technology in recirculating fluidized bed and belongs to international pioneering, and the technology was awarded specially in 2012
Economic rights (the patent No.：ZL2011101038619), it has that flow is short, technology condition is wide in range, reusable edible, cost are low,
Environmentally friendly the advantages of, solve the utilization problem that circulating fluid bed coal ash extracts aluminum oxide.
Ignition temperature is about 1300 DEG C when coal-powder boiler works, and gained flyash mainly mutually exists with mullite corundum, should
Plant flyash aluminium oxide active poor, extract difficulty big.Though there are many processing technology routines to propose, eventually because its cost is high, production slag
The reason such as big is measured, coal-powder boiler flyash extracts aluminum oxide and is constantly in the laboratory research stage.At present, the row of coal-powder boiler flyash
It is high-volume 9 times of circulating fluid bed coal ash or so, therefore, only realizes the comprehensive utilization of coal-powder boiler flyash, be only fine coal
The comprehensive utilization of ash truly.As can be seen here, a kind of technique of research is simple, technology is wide in range, cost is low from coal-powder boiler powder
The method that coal ash extracts aluminum oxide, could remold world aluminum resource general layout, increase the chip of aluminum resources.
The content of the invention
The invention aims to overcome low aluminum oxide in the prior art and white clay recovery rate, high energy consumption, complex process,
The big technical problem of level of residue, and provide that a kind of technique is simple, energy consumption is low extracts high purity aluminium oxide from coal-powder boiler flyash
And the method for white clay.
To achieve these goals, the present invention uses following technical scheme, it is characterised in that this method comprises the following steps：
(1) grinding flyash and optional dispersant, is less than 8 μm to particle diameter, preferably less than 4 μm, more preferably 2 μm with
Under；It is preferred that the dispersant is polypropylene dispersant or POLYPROPYLENE GLYCOL dispersant, more preferably POLYPROPYLENE GLYCOL dispersant；It is described scattered
The mass ratio of agent and flyash is 1:800~1:1200；
(2) flyash after grinding is scattered in hydrochloric acid, is filtered after being leached under closed stirring condition, obtain aluminium chloride
Thick liquid；
(3) hydrogen chloride gas is passed through to supersaturation into thick liquid obtained by step (2), separates out coarse crystallization aluminium chloride, filter institute
Coarse crystallization is stated, and is washed with concentrated hydrochloric acid, refining crystallization aluminium chloride is obtained；It is preferred that by filtrate obtained by step (3) and cleaning solution removal of impurities,
It is preferred that by membrane filtration or resin removal of impurities, being recycled hydrochloric acid A；
(4) refining crystallization aluminium chloride obtained by step (3) is calcined, obtains high purity aluminium oxide dry powder；It is preferred that by roasting process
The hydrogen chloride gas of middle generation is reclaimed, and is recycled hydrochloric acid B.
Preferably, recovery hydrochloric acid A obtained by step (3) and/or step (4) gained recovery hydrochloric acid B is circulated for step (2)
Acid leaching process, or low-temperature evaporation produce hydrogen chloride gas be used for step (3).
Further, in step (2), the hydrochloric acid mass concentration is 20-36%, preferably 25-35%；The fine coal grey matter
The solid-to-liquid ratio of amount and hydrochloric acid volume is 1g:3ml~1g:25ml, preferably 1g:7ml~1g:12ml；The leaching temperature is 110-
180 DEG C, preferably 130-170 DEG C, leaching time is 1-3h, preferably 1-2h.
Preferably, in step (3), during hydrogen chloride gas is passed through, the temperature of the thick liquid is no more than 50 DEG C, uses
The number of times of salt acid elution is 1-3 times.
Preferably, the sintering temperature in step (4) is 700-1200 DEG C, and roasting time is 1-3h.
Preferably, it can also include before step (3)：Thick liquid obtained by step (2) is evaporated to nearly saturation or oversaturated step
Suddenly.
Preferably, hydrogen chloride gas to the oversaturated step of solution will be passed through to thick liquid obtained by step (2) in step (3) to replace
It is changed to：Hydrogen chloride gas is passed through into thick liquid obtained by step (2), when the acidity of solution reaches 7-12mol/L, stops ventilation simultaneously
Filtering, obtains a part of refining crystallization aluminium chloride, then continues to be passed through hydrogen chloride gas into filtrate, to supersaturation, filters institute
Coarse crystallization aluminium chloride, above-mentioned coarse crystallization aluminium chloride is washed with concentrated hydrochloric acid 1-3 times, obtains another part refining crystallization aluminium chloride.
Preferably, leaching can be replaced by the concentrated sulfuric acid with hydrochloric acid in step (2), filters and with water washing, obtain after leaching
To the thick liquid of aluminum sulfate；It is preferred that the solid-to-liquid ratio of the flyash and the concentrated sulfuric acid is 1:3~1:12；The leaching temperature is 110-300
DEG C, leaching time is 1-3h.
Preferably, filter residue obtained by step (2) is washed, obtains can be used for making molecular sieve, non-burning brick or plastics
The white clay of filler, the main component of the white clay is silica.
Preferably, one or more replacements in gangue, low-grade bauxite, red mud, nepheline ore deposit and clay ore deposit can be used
Flyash described in step (1).
High purity aluminium oxide of the present invention refer to purity be higher than 99.86% aluminum oxide, its chemical aluminum oxide classification and
The trade mark is named as YS T 619-2007.
In step (1), because the main thing of coal-powder boiler flyash is mutually mullite corundum phase, activity is low.It is of the present invention to grind
The effect of mill powdered coal ash is the compact texture for destroying mullite and vitreous surface, improves the work of aluminum oxide in flyash
Property.
Alleged by the present invention " optional " refer to the situation for including or not including, such as " optional dispersant " refers to comprising scattered
Agent, or not comprising dispersant.
The purpose that the present invention adds " dispersant " is to prevent powdered coal ash from reuniting.
Saturation of the invention alleged nearly refers to that solution begins with the state of epitaxial appearance, or refers to and be determined by aluminium chloride
The state of solution when concentration is 350-400g/L.
The chemical reaction for occurring mainly during step (2) acidleach is as follows：
Al2O3+6HCl→2AlCl3+3H2O
Fe2O3+6HCl→2FeCl3+3H2O
Al6Si2O13+18HCl→6AlCl3+(2-n)H2SiO3+(7+n)H2O+n·SiO2
Al2O3+3H2SO4(dense) → Al2(SO4)3+3H2O
Fe2O3+3H2SO4(dense) → Fe2(SO4)3+3H2O
Al6Si2O13+9H2SO4→3Al2(SO4)3+2SiO2+9H2O
In the stage, dissolution rate (R) calculation formula of aluminum oxide is：
Or
In step (3), percent crystallization in massecuite (J) calculation formula of gained aluminium chloride is：
In step (4), the chemical equation that aluminum oxide calcining mainly occurs is：
2AlCl3·6H2O→Al2O3+6HCl↑+9H2O↑
The calculation formula of alumina extraction ratio (T) is：
Al content is determined and can carried out according to following methods in the present invention：
Method 1：Potassium fluoride replaces EDTA volumetric methods；
Method 2：Inductively coupled plasma launches (icp-OES) method；
Method 3：X-ray fluorescence spectra analyzes (XRF) method；
Specifically it refer to national standard GB/T14506.4-2010 and GB/T6609.
The principle that the present invention removes heteroion is that metal salt becomes under hydrochloric acid system with the rise solubility of concentration of hydrochloric acid
Law is different.Wherein aluminium chloride drastically declines with the rise solubility of concentration of hydrochloric acid, and iron chloride, calcium chloride, magnesium chloride etc.
Impurity salt is not obvious with the increase solubility reduction of concentration, so that only high-purity aluminium chloride crystallization is separated out from system.
In addition, gangue, low-grade bauxite, red mud, nepheline ore deposit and clay ore deposit and flyash are very much like, their master
It is all aluminum oxide and silica to want composition, is silicate mineral, and the activity of its aluminium is all stronger than coal-powder boiler flyash.Therefore
Technical scheme can also be applied to above-mentioned raw mineral materials.
The present invention has advantages below compared with prior art：Present invention activation is simple, (is saltoutd) by hydrogen chloride air elutriation
Reach that removal of impurities crystallization processes are settled at one go, it is not necessary to extra removal of impurities process, reduction equipment investment, flow are shorter, operate more square
Just；The aluminum oxide purity of extraction is high, and recovery rate can be more than 85%；The material of the present invention can be recycled, and energy consumption is relatively low；System
Standby white clay can be used for making molecular sieve, non-burning brick and filler for plastic, realize the secondary utilization of waste；Alumina and white
Residue outside mud is less than the 5% of fine coal ash quantity used；Whole technique can realize closed cycle, non-secondary pollution.Therefore, it is of the invention
Meet《Aluminium industry access condition》The entry criteria of defined flyash extraction aluminum oxide is a kind of with potential industrial value
Technology path, this, which proposes the raising of aluminum technology to China's bauxite and finds bauxite alternate resources, certain help.
Brief description of the drawings
Fig. 1 is that high purity aluminium oxide and the process chart of white clay method are extracted from flyash.
Embodiment
Below by way of instantiation, as example, the present invention is described in detail.It will be appreciated by those skilled in the art that
The effect of embodiment is the scope being not intended to be limiting of the invention in order that reader more fully understands the present invention.
The high alumina coal-powder boiler flyash that the flyash used in embodiment is discharged for certain power plant, the specific following institute of composition
Show：
The flyash component list of table 1
POLYPROPYLENE GLYCOL dispersant, 500g/ bottles, the chemical Science and Technology Ltd. of the excellent rope in Qingdao；
Hydrochloric acid (technical hydrochloric acid), Shandong Zibo；
Hydrogen chloride gas (purity 99%), Shandong Zibo；
Inductively coupled plasma emission analysis instrument, U.S. PE, icp-OES8000；
X-ray fluorescence spectrometer, Dutch PANalytical, axiosmax。
Example 1
(1) by 1200:1 flyash after POLYPROPYLENE GLYCOL dispersant with being ground to less than 2 μm
(2) by flyash and 30% hydrochloric acid levigate in step (1) by flyash quality (g) and hydrochloric acid volume (ml) ratio
For 1:12 solid-to-liquid ratio is well mixed, under conditions of closed stirring, and 160 DEG C of leaching 2h, filtering carries out analysis survey to filtrate
Examination, the dissolution rate of aluminum oxide is 95%.
(3) the thick solution of aluminium chloride obtained by step (2) is passed through hydrogen chloride gas to supersaturation, and control temperature is no more than 50
DEG C, coarse crystallization aluminium chloride is filtered to obtain, percent crystallization in massecuite is more than 99%；Coarse crystallization aluminium chloride is washed 3 times with concentrated hydrochloric acid, obtains high-purity
Crystal aluminum chloride；The filtrate of this process and cleaning solution low-temperature evaporation, prepare hydrogen chloride gas, are back to step (3).
(4) high purity crystalline aluminium chloride obtained by step (3) is obtained into the high pure zirconia of product through being calcined 2h at a temperature of 1000 DEG C
Aluminium.The recovery rate of aluminum oxide is more than 88.58%, and purity is 99.95%, the metallurgical stair oxidation aluminium standard better than 98.6%
(GB-T24487-2009)；Three-level absorption is carried out to the acid gas of calcination process, the hydrochloric acid of recovery is recycling in step (2).
(5) filter residue obtained by step (2) is washed with water to neutrality, mixed with quick lime, gangue, sand, it is dry-pressing formed,
It is made non-burning brick.
Example 2
(1) flyash is ground less than 4 μm；
(2) by flyash quality (g) it is with hydrochloric acid volume (ml) ratio by the levigate flyash of step (1) and 25% hydrochloric acid
1:10 solid-to-liquid ratio is well mixed, under conditions of closed stirring, and 140 DEG C of leaching 1h, filtering carries out analysis test to filtrate,
The dissolution rate of aluminum oxide is 88%；
(3) the thick solution of aluminium chloride obtained by step (2) is evaporated to after supersaturation, is passed through hydrogen chloride gas to supersaturation,
Control temperature to be no more than 50 DEG C, filter to obtain coarse crystallization aluminium chloride, the percent crystallization in massecuite of aluminium chloride is more than 99.10%；With concentrated hydrochloric acid pair
Crystal aluminum chloride carries out washing 2 times, obtains high purity crystalline aluminium chloride.
(4) high purity crystalline aluminium chloride obtained by step (3) is obtained into the high pure zirconia of product through being calcined 2h at a temperature of 1000 DEG C
Aluminium；The recovery rate of aluminum oxide is 85.56%, and purity is 99.94%, better than metallurgical stair oxidation aluminium standard (GB-T24487-
2009)。
(5) filter residue obtained by step (2) is washed with water to neutrality, is mixed with sodium hydroxide and sodium aluminate, molecular sieve is made.
(6) hydrogen chloride gas in step (4) calcination process is subjected to acid recovery, obtains filtering obtained by hydrochloric acid and step (3)
Liquid, hydrogen chloride gas is produced for step (3) for the Acid leaching process of step (2), or low-temperature evaporation.
Example 3
(1) flyash is ground less than 2 μm.
(2) by flyash quality (g) it is with hydrochloric acid volume (ml) ratio by the levigate flyash of step (1) and 30% hydrochloric acid
1:10 solid-to-liquid ratio is well mixed, under conditions of closed stirring, and 170 DEG C of leaching 2h, filtering carries out analysis test to filtrate,
The dissolution rate of aluminum oxide is 99%.
(3) to liquor alumini chloridi obtained by step (2), hydrogen chloride gas is passed through, control temperature is no more than 50 DEG C, controls solution
Acidity obtains a part of high purity crystalline aluminium chloride, percent crystallization in massecuite is 65% in 8mol/l, filtering；Continue to be passed through hydrogen chloride gas to filtrate
Body, to supersaturation, filtering gained coarse crystallization aluminium chloride washs above-mentioned coarse crystallization aluminium chloride with concentrated hydrochloric acid 3 times, obtains another part
High purity crystalline aluminium chloride.Total percent crystallization in massecuite of gained high-purity aluminium chloride is 99.05%.
(4) high purity crystalline aluminium chloride obtained by step (3) is obtained into the high pure zirconia of product through being calcined 2h at a temperature of 1000 DEG C
Aluminium.The recovery rate of aluminum oxide is more than 88%, and purity is 99.93% better than metallurgical stair oxidation aluminium standard (GB-T24487-
2009)；Three-level absorption is carried out to the acid gas of calcination process, the hydrochloric acid of recovery is recycling in step (2).
(5) filter residue obtained by step (2) is washed with water to neutrality, and quick lime, gangue, sand are dry-pressing formed, are made
It is non-burning brick.
Example 4
(1) flyash is ground less than 6 μm.
(2) by step (1) levigate flyash and 98% sulfuric acid, in mass ratio 1:6 ratio is well mixed, closed
Under conditions of stirring, 260 DEG C of leaching 2h, filtering carries out analysis test to filtrate, the dissolution rate of aluminum oxide is 90%.
(3) the thick solution of aluminum sulfate obtained by step (2) is passed through hydrogen chloride gas to supersaturation, and control temperature is no more than 50
DEG C, coarse crystallization aluminium chloride is filtered to obtain, percent crystallization in massecuite is 99.05%；Coarse crystallization aluminium chloride is washed 3 times with concentrated hydrochloric acid, obtains high-purity
Crystal aluminum chloride；The filtrate of this process and cleaning solution low-temperature evaporation, prepare hydrogen chloride gas, are back to step (3).
(4) high purity crystalline aluminium chloride obtained by step (3) is obtained into the high pure zirconia of product through being calcined 2h at a temperature of 1000 DEG C
Aluminium.The recovery rate of aluminum oxide is more than 86.5%, and purity is 99.95%, the metallurgical stair oxidation aluminium standard better than 98.6%
(GB-T24487-2009)；Three-level absorption is carried out to the acid gas of calcination process, the hydrochloric acid of recovery is recycling in step (2).
(5) filter residue obtained by step (2) is washed with water to neutrality, is mixed with sodium hydroxide and sodium aluminate, molecular sieve is made.
Example 5
(1) clay ore deposit is ground to less than 4 μm
(2) by flyash and 30% hydrochloric acid levigate in step (1) by flyash quality (g) and hydrochloric acid volume (ml) ratio
For 1:5 solid-to-liquid ratio is well mixed, under conditions of closed stirring, and 120 DEG C of leaching 2h, filtering carries out analysis test to filtrate,
The dissolution rate of aluminum oxide is 95%.
(3) the thick solution of aluminium chloride obtained by step (2) is passed through hydrogen chloride gas to supersaturation, and control temperature is no more than 50
DEG C, coarse crystallization aluminium chloride is filtered to obtain, percent crystallization in massecuite is more than 99.25%；Coarse crystallization aluminium chloride is washed 3 times with concentrated hydrochloric acid, obtained
High purity crystalline aluminium chloride；The filtrate of this process and cleaning solution low-temperature evaporation, prepare hydrogen chloride gas, are back to step (3).
(4) high purity crystalline aluminium chloride obtained by step (3) is obtained into the high pure zirconia of product through being calcined 2h at a temperature of 1000 DEG C
Aluminium.The recovery rate of aluminum oxide is more than 88.56%, and purity is 99.96%, the metallurgical stair oxidation aluminium standard better than 98.6%
(GB-T24487-2009)；Three-level absorption is carried out to the acid gas of calcination process, the hydrochloric acid of recovery is recycling in step (2).
(5) filter residue obtained by step (2) is washed with water to neutrality, and quick lime, gangue, sand are dry-pressing formed, are made
It is non-burning brick.
Claims (10)
1. a kind of method that high purity aluminium oxide and white clay are extracted from coal-powder boiler flyash, it is characterised in that this method includes following
Step：
(1) grinding flyash and optional dispersant, are less than 8 μm, more preferably preferably less than 4 μm, less than 2 μm to particle diameter；It is excellent
It is polypropylene dispersant or POLYPROPYLENE GLYCOL dispersant, more preferably POLYPROPYLENE GLYCOL dispersant to select the dispersant；The dispersant with
The mass ratio of flyash is 1:800~1:1200；
(2) flyash after grinding is scattered in hydrochloric acid, is filtered after being leached under closed stirring condition, obtain aluminium chloride thick
Liquid；
(3) hydrogen chloride gas is passed through to supersaturation into thick liquid obtained by step (2), separates out coarse crystallization aluminium chloride, filter described thick
Crystallization, and washed with concentrated hydrochloric acid, obtain refining crystallization aluminium chloride；It is preferred that by filtrate obtained by step (3) and cleaning solution removal of impurities, preferably
By membrane filtration or resin removal of impurities, hydrochloric acid A is recycled；
(4) refining crystallization aluminium chloride obtained by step (3) is calcined, obtains high purity aluminium oxide dry powder；It is preferred that will be produced in roasting process
Raw hydrogen chloride gas is reclaimed, and is recycled hydrochloric acid B.
2. according to the method described in claim 1, it is characterised in that hydrochloric acid A and/or step (4) institute will be reclaimed obtained by step (3)
Hydrochloric acid B must be reclaimed and circulate Acid leaching process for step (2), or low-temperature evaporation produces hydrogen chloride gas is used for step (3).
3. method according to claim 1 or 2, it is characterised in that in step (2), the hydrochloric acid mass concentration is 20-
36%, preferably 25-35%；The solid-to-liquid ratio of the flyash quality and hydrochloric acid volume is 1g:3ml~1g:25ml, preferably 1g:7ml
~1g:12ml；The leaching temperature is 110-180 DEG C, and preferably 130-170 DEG C, leaching time is 1-3h, preferably 1-2h.
4. the method according to any one of foregoing claim, it is characterised in that in step (3), be passed through hydrogen chloride gas
During, the temperature of the thick liquid is no more than 50 DEG C, and the number of times washed with concentrated hydrochloric acid is 1-3 times.
5. the method according to any one of foregoing claim, it is characterised in that the sintering temperature in step (4) is 700-
1200 DEG C, roasting time is 1-3h.
6. the method according to any one of foregoing claim, it is characterised in that step can also include before (3)：By step
(2) the thick liquid of gained is evaporated to nearly saturation or oversaturated step.
7. the method according to any one of preceding claims, it is characterised in that by step (3) to thick liquid obtained by step (2)
Hydrogen chloride gas to the oversaturated step of solution is passed through to replace with：Hydrogen chloride gas is passed through into thick liquid obtained by step (2), when molten
When the acidity of liquid reaches 7-12mol/L, stop ventilating and filtering, a part of refining crystallization aluminium chloride is obtained, then into filtrate
Continue to be passed through hydrogen chloride gas, to supersaturation, filtering gained coarse crystallization aluminium chloride washs above-mentioned coarse crystallization aluminium chloride with concentrated hydrochloric acid
1-3 times, obtain another part refining crystallization aluminium chloride.
8. according to the method described in claim 1, it is characterised in that leaching can be replaced by dense sulphur with hydrochloric acid in step (2)
Acid, filters and with water washing after leaching, obtains the thick liquid of aluminum sulfate；It is preferred that the solid-liquid mass ratio of the flyash and the concentrated sulfuric acid is 1:
3~1:12；The leaching temperature is 110-300 DEG C, and leaching time is 1-3h.
9. the method according to any one of foregoing claim, it is characterised in that filter residue obtained by step (2) is washed, obtained
To available for making molecular sieve, non-burning brick or filler for plastic white clay.
10. the method according to any one of preceding claims, it is characterised in that gangue, low-grade bauxite, red can be used
The flyash described in one or more alternative steps (1) in mud, nepheline ore deposit and clay ore deposit.
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