CN102627305B - Method using alkaline process to extract alumina in coal ash - Google Patents
Method using alkaline process to extract alumina in coal ash Download PDFInfo
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- CN102627305B CN102627305B CN201210084915.6A CN201210084915A CN102627305B CN 102627305 B CN102627305 B CN 102627305B CN 201210084915 A CN201210084915 A CN 201210084915A CN 102627305 B CN102627305 B CN 102627305B
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- liquid
- leaching
- coal ash
- aluminum oxide
- grog
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- 238000000034 method Methods 0.000 title claims abstract description 79
- 239000010883 coal ash Substances 0.000 title claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002386 leaching Methods 0.000 claims abstract description 69
- 239000007790 solid phase Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 21
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 21
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 21
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 21
- 239000004571 lime Substances 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000010304 firing Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 41
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 40
- 239000011734 sodium Substances 0.000 claims description 30
- 238000000354 decomposition reaction Methods 0.000 claims description 29
- 239000000284 extract Substances 0.000 claims description 27
- 239000010881 fly ash Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 238000001704 evaporation Methods 0.000 claims description 20
- 230000008020 evaporation Effects 0.000 claims description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 239000004568 cement Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000006210 lotion Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 abstract description 11
- 239000006028 limestone Substances 0.000 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000003518 caustics Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 7
- 229910001948 sodium oxide Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C01F7/0613—Pretreatment of the minerals, e.g. grinding
-
- 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
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Structural Engineering (AREA)
- Combustion & Propulsion (AREA)
- Civil Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method using an alkaline process to extract alumina in coal ash relates to a method using coal ash to produce alumina and is characterized by comprising the steps of (1) manufacturing coal ash, limestone or lime into raw slurry with alkali liquid; (2) firing the raw slurry into clinker; (3) performing alkaline leaching on the clinker; (4) desiliconizing leaching liquid to perform liquid-solid separation; (5) carbonating and resolving desiliconized liquid after liquid-solid separation to obtain aluminium hydroxide; (6) roasting the aluminium hydroxide to achieve alumina; (7) performing alkaline leaching on solid phase residues obtained from the step (3); (8) using leaching liquid obtained from the step (7) to adjust molecular ratio of a system in desiliconization treatment; or adding lime in the leaching liquid obtained from the step (7), filtering after reaction, and obtaining filter residues which are used for desiliconization of the step (4). The method can be used for treating coal ash raw materials from different sources to produce alumina.
Description
Technical field
The present invention relates to the method for aluminum oxide in a kind of alkaline process extract powder coal ash.
Background technology
Flyash is the tiny powdered material of collecting in the flue gas from coal combustion.The mineralogical composition of flyash is relevant with the source of chemical composition and coal, and its thing phase composite, take vitreum as main, contains the pulverulent material of mullite, quartz, rhombohedral iron ore, magnetite, anhydrite, tricalcium phosphate and melilith etc. simultaneously; Chemical composition is mainly Al
2o
3, SiO
2, Fe
2o
3, CaO, MgO etc., also contain a small amount of rare elements simultaneously.Flyash is stored up and will be taken a large amount of soils, and also can cause pollution to a certain degree to surrounding enviroment.Therefore, the comprehensive utilization of flyash is studied, turned waste into wealth, to environment protection and raising resource utilization, build environmental protection economical society and be all significant.
From the technique of flyash extraction aluminum oxide (aluminium hydroxide) or aluminium salt, be summed up and can be divided into acid system, alkaline process and soda acid hybrid system.These processing methodes respectively have its feature on operational path.
Acid system advantage is flyash main component SiO
2do not enter solution, but shortcoming be to process with aluminium altogether the impurity metallic elements of stripping need purifying treatment, removal of impurities operation is tediously long, acid consumption is large and need acid-resistant system.The representative method of alkaline process is limestone sintering method and soda-lime sintering process.Flyash alkaline process extracts aluminum oxide advantage and is that metallic impurity interference is little, technology maturation.Alkaline process, because its clinker quantity is large, causes energy consumption too high, and after alumina extraction, becomes the quantity of slag large.
Flyash alkaline process extracts the solid slag producing in alumina process can contain a certain amount of alkali and aluminum oxide.Effectively reducing alkali and the alumina content in solid slag, is to realize the prerequisite that flyash alkaline process extracts aluminum oxide maximization of economic benefit, realizes the extensive recycling of solid slag.
Summary of the invention
Object of the present invention is exactly the deficiency existing for above-mentioned prior art, provide a kind of explained hereafter flow process short, alkaline consumption is low, and quality product is easy to control, and can effectively realize the method for aluminum oxide in the alkaline process extract powder coal ash that extracts solid phase residue comprehensive utilization after aluminum oxide.
The object of the invention is to be achieved through the following technical solutions.
A method for aluminum oxide in alkaline process extract powder coal ash, is characterized in that the step of its leaching process comprises:
(1) in flyash, add lime and alkali lye, make charge pulp;
(2) charge pulp is fired into grog;
(3) grog is carried out to alkali leaching, leaching slurry is carried out to liquid-solid separation, obtain solid phase residue 1 and leach liquor 1;
(4) leach liquor 1 is carried out, after desiliconization processing, carrying out liquid-solid separation;
(5) by liquid after the desiliconization filtering to isolate, carry out carbonating decomposition, obtain aluminium hydroxide;
(6) aluminium hydroxide obtains alumina product after roasting;
(7) the solid phase residue 1 obtaining in step (3) is carried out to alkali leaching again, leaching slurry is carried out to liquid-solid separation, obtain solid phase residue 2 and leach liquor 2, further reclaim aluminum oxide and alkali;
(8) molecular ratio of adjustment System when the leach liquor 2 obtaining in step (7) is processed for step (4) desiliconization; In the leach liquor that also can obtain in step (7), add lime, reaction is filtered afterwards, and the filter residue excessively obtaining is for the desiliconization process of step (4);
(9) the solid phase residue 2 obtaining in step (7) is as the raw material of producing the material of construction such as cement.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, is characterized in that the fineness of flyash in its step (1) is-0.18mm; The fineness of limestone powder or lime powder is-0.18mm.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, is characterized in that alkali lye that its step (1) adds is the mixed solution of the carbonating decomposition nut liquid after the evaporation of sodium carbonate and aluminum oxide production process.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, is characterized in that the mixing process of the charge pulp of its step (1), and the addition of Wingdale or lime is by SiO in system
2amount determine, the addition of Wingdale or lime is according to CaO and SiO
2mol ratio be 0.8～2.2 control, sodium carbonate addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be 0.9～1.7 control.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, the charge pulp firing temperature that it is characterized in that its step (2) is 900～1380 ℃, the firing time is 10-120 minute.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, is characterized in that its step (3) is under the condition of 40～105 ℃ of temperature, to leach grog with adjusting liquid, and leaching slurry is carried out to liquid-solid separation, obtains solid phase residue 1 and leach liquor 1.
The method that a kind of flyash of the present invention is produced aluminum oxide-alkali and soaked the alkali that reclaims in solid slag and aluminum oxide-solid slag and can be used as the raw material of material of construction, the leach liquor 1 that it is characterized in that its step (3) carries out carrying out after desiliconization processing the some or all of raw material that returns to step (1) and do charge pulp preparation of solid residue that liquid-solid separation obtains.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, it is characterized in that its step (5) carbonating decompose after mother liquor through evaporation after return to step (1), for charge pulp, prepare.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, is characterized in that it leaches the washing lotion allotment of solid phase residue after the liquid-solid separation of slurries that the adjustment liquid used of grog be who knows by leaching and forms.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, it is characterized in that carrying out in its step (7) strength of solution that alkali leaches use is NaO
2K30 ~ 250g/L, extraction temperature is 60 ~ 250 ℃, and extraction time is 5 ~ 360 minutes, and leaching liquid-solid ratio is 1 ~ 5, and leaching slurry is carried out to liquid-solid separation, obtains solid phase residue 2 and leach liquor 2.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, is characterized in that the molecular ratio of adjustment System when the leach liquor 2 that obtains in its step (7) is for step (4) desiliconization.
In a kind of alkaline process extract powder coal ash of the present invention, the method for aluminum oxide, adds lime in the leach liquor 2 that it is characterized in that obtaining in step (7), and reaction is filtered afterwards, and the filter residue excessively obtaining is for the desiliconization process of step (4);
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention, is characterized in that the solid phase residue 2 obtaining in its step (7) is as the raw material of producing the material of construction such as cement.
The method of aluminum oxide in a kind of alkaline process extract powder coal ash of the present invention; can be used for processing the powdered coal ash production aluminum oxide of different sources, different chemical composition and mineral composition; in solid slag, alkali content is low; can be used as the raw material of material of construction, the technology of the present invention mature and reliable, compares with existing alkaline process production technique; mass flow is little; solid phase level of residue is few, and can realize the zero release of whole process, is conducive to environment protection.Really realized flyash and produced the full-range high yield of aluminum oxide and low energy expenditure, and the solid phase residue extracting after aluminum oxide can be realized large-scale recycling completely.
Embodiment
A kind of method of aluminum oxide in alkaline process extract powder coal ash, the step of its production process comprises: 1) that flyash is (levigate if desired, fineness is preferably-80 orders), limestone powder or lime powder (fineness is preferably-80 orders) after levigate, and the carbonating decomposition nut liquid after sodium carbonate and evaporation is mixed and made into charge pulp according to a certain percentage; 2) charge pulp is fired into grog under certain temperature condition; 3) with the solution that contains sodium carbonate and sodium hydroxide etc., grog is leached under certain condition, leaching slurry is carried out to liquid-solid separation; 4) leach liquor is carried out carrying out carbonating decomposition after desiliconization again, obtain aluminium hydroxide; 5) aluminium hydroxide obtains alumina product after roasting; 6) solid product forming in desiliconization process can return to the raw material of charge pulp preparation stage as preparation charge pulp; 7) mother liquor after carbonating decomposition returns after evaporation, for preparing charge pulp; 8) after the liquid-solid separation of slurries that the adjustment liquid that leaching grog is used be who knows by leaching, the washing lotion allotment of solid phase residue forms; 9) by 3) in the solid phase residue that obtains carry out again alkali leaching, leaching slurry is carried out to liquid-solid separation, further reclaim aluminum oxide and alkali; The leach liquor obtaining is for 4) desiliconization process time adjustment System molecular ratio; Also can in the leach liquor obtaining, add lime, reaction after filter, obtain cross filter residue for 4) desiliconization process; 10) the solid phase residue finally obtaining is as the raw material of producing the material of construction such as cement.
Embodiment 1
Raw material is the flyash of certain heat power plant, and main chemical compositions is Al
2o
339%, SiO
244.1%, by grinding rear fineness, be that carbonating decomposition nut liquid after-80 order limestone powders or lime powder and sodium carbonate and evaporation is according to CaO and SiO
2mol ratio be 1.0 controls, sodium carbonate (comprises the Na in the carbonating decomposition nut liquid after evaporation
2o) addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be that 1.1 controls are prepared burden and prepared charge pulp; By charge pulp, in temperature, be to fire under 1110 ℃ of conditions, obtain qualified grog; With adjusting liquid, under the condition of 80-90 ℃, leach grog, in grog, leaching rate of alumina can reach 69.97%, and in grog, sodium oxide leaching yield can reach 70.46%.Clinker leaching liquor carries out carbonating decomposition after desiliconization, obtains aluminium hydroxide, and aluminium hydroxide obtains metallurgical-grade aluminum oxide product after roasting.
Solid phase residue caustic sodium concentration after grog stripping is NaO
2Kthe alkali lye of 50g/L is under 90 ℃ of conditions in temperature, leaches 360 minutes, and leaching liquid-solid ratio is 2, Al in solid phase residue
2o
3leaching yield be 15%, Na in solid phase residue
2the leaching yield of O is 91%.The solid phase residue finally obtaining is as the raw material of producing cement.
Embodiment 2
Raw material is the flyash of certain heat power plant, and main chemical compositions is Al
2o
341%, SiO
247%, by grinding rear fineness, be that carbonating decomposition nut liquid after-80 order limestone powders or lime powder and sodium carbonate and evaporation is according to CaO and SiO
2mol ratio be 1.3 controls, sodium carbonate (comprises the Na in the carbonating decomposition nut liquid after evaporation
2o) addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be that 1.0 controls are prepared burden and prepared charge pulp; By charge pulp, in temperature, be to fire under 1200 ℃ of conditions, obtain qualified grog; With adjusting liquid, under the condition of 80-90 ℃, leach grog, in grog, leaching rate of alumina can reach 77.76%, and in grog, sodium oxide leaching yield can reach 82.78%.Clinker leaching liquor carries out carbonating decomposition after desiliconization, obtains aluminium hydroxide, and aluminium hydroxide obtains metallurgical-grade aluminum oxide product after roasting.
Solid phase residue caustic sodium concentration after grog stripping is NaO
2Kthe alkali lye of 100g/L is under 120 ℃ of conditions in temperature, leaches 20 minutes, and leaching liquid-solid ratio is 2, Al in solid phase residue
2o
3leaching yield be 16%, Na in solid phase residue
2the leaching yield of O is 89%.The solid phase residue finally obtaining is as the raw material of producing cement.
Embodiment 3
Raw material is the flyash of certain heat power plant, and main chemical compositions is Al
2o
347%, SiO
243%, by grinding rear fineness, be that carbonating decomposition nut liquid after-80 order limestone powders or lime powder and sodium carbonate and evaporation is according to CaO and SiO
2mol ratio be 1.5 controls, sodium carbonate (comprises the Na in the carbonating decomposition nut liquid after evaporation
2o) addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be that 1.2 controls are prepared burden and prepared charge pulp; By charge pulp, in temperature, be to fire under 1120 ℃ of conditions, obtain qualified grog; With adjusting liquid, under the condition of 80-90 ℃, leach grog, in grog, leaching rate of alumina can reach 84.97%, and in grog, sodium oxide leaching yield can reach 92.82%.Clinker leaching liquor carries out carbonating decomposition after desiliconization, obtains aluminium hydroxide, and aluminium hydroxide obtains metallurgical-grade aluminum oxide product after roasting.
Solid phase residue caustic sodium concentration after grog stripping is NaO
2Kthe alkali lye of 140g/L is under 160 ℃ of conditions in temperature, leaches 15 minutes, and leaching liquid-solid ratio is 3, Al in solid phase residue
2o
3leaching yield be 17%, Na in solid phase residue
2the leaching yield of O is 88%.The solid phase residue finally obtaining is as the raw material of producing cement.
Embodiment 4
Raw material is the flyash of certain heat power plant, and main chemical compositions is Al
2o
351%, SiO
238%, by grinding rear fineness, be that carbonating decomposition nut liquid after-80 order limestone powders or lime powder and sodium carbonate and evaporation is according to CaO and SiO
2mol ratio be 1.4 controls, sodium carbonate (comprises the Na in the carbonating decomposition nut liquid after evaporation
2o) addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be that 1.05 controls are prepared burden and prepared charge pulp; By charge pulp, in temperature, be to fire under 1250 ℃ of conditions, obtain qualified grog; With adjusting liquid, under the condition of 80-90 ℃, leach grog, in grog, leaching rate of alumina can reach 84.17%, and in grog, sodium oxide leaching yield can reach 88.21%.Clinker leaching liquor carries out carbonating decomposition after desiliconization, obtains aluminium hydroxide, and aluminium hydroxide obtains metallurgical-grade aluminum oxide product after roasting.
Solid phase residue caustic sodium concentration after grog stripping is NaO
2Kthe alkali lye of 200g/L is under 200 ℃ of conditions in temperature, leaches 10 minutes, and leaching liquid-solid ratio is 3, Al in solid phase residue
2o
3leaching yield be 18%, Na in solid phase residue
2the leaching yield of O is 89%.The solid phase residue finally obtaining is as the raw material of producing cement.
Embodiment 5
Raw material is the flyash of certain heat power plant, and main chemical compositions is Al
2o
355%, SiO
237%, by grinding rear fineness, be that carbonating decomposition nut liquid after-80 order limestone powders or lime powder and sodium carbonate and evaporation is according to CaO and SiO
2mol ratio be 1.6 controls, sodium carbonate (comprises the Na in the carbonating decomposition nut liquid after evaporation
2o) addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be that 1.0 controls are prepared burden and prepared charge pulp; By charge pulp, in temperature, be to fire under 1150 ℃ of conditions, obtain qualified grog; With adjusting liquid, under the condition of 80-90 ℃, leach grog, in grog, leaching rate of alumina can reach 86.21%, and in grog, sodium oxide leaching yield can reach 94.12%.Clinker leaching liquor carries out carbonating decomposition after desiliconization, obtains aluminium hydroxide, and aluminium hydroxide obtains metallurgical-grade aluminum oxide product after roasting.
Solid phase residue caustic sodium concentration after grog stripping is NaO
2Kthe alkali lye of 200g/L is under 220 ℃ of conditions in temperature, leaches 8 minutes, and leaching liquid-solid ratio is 3, Al in solid phase residue
2o
3leaching yield be 18%, Na in solid phase residue
2the leaching yield of O is 87%.The solid phase residue finally obtaining is as the raw material of producing cement.
Embodiment 6
Raw material is the flyash of certain heat power plant, and main chemical compositions is Al
2o
353%, SiO
238%, by grinding rear fineness, be that carbonating decomposition nut liquid after-80 order limestone powders and sodium carbonate and evaporation is according to CaO and SiO
2mol ratio be 1.5 controls, sodium carbonate (comprises the Na in the carbonating decomposition nut liquid after evaporation
2o) addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be that 0.98 control is prepared burden and prepared charge pulp; By charge pulp, in temperature, be to fire under 1230 ℃ of conditions, obtain qualified grog; With adjusting liquid, under the condition of 80-90 ℃, leach grog, in grog, leaching rate of alumina can reach 84.46%, and in grog, sodium oxide leaching yield can reach 92.78%.Clinker leaching liquor carries out carbonating decomposition after desiliconization, controls carbonating decomposition condition, obtains pseudo-boehmite product.
Solid phase residue caustic sodium concentration after grog stripping is NaO
2Kthe alkali lye of 70g/L is under 100 ℃ of conditions in temperature, leaches 240 minutes, and leaching liquid-solid ratio is 3, Al in solid phase residue
2o
3leaching yield be 13%, Na in solid phase residue
2the leaching yield of O is 81%.The solid phase residue finally obtaining is as the raw material of producing cement.
Embodiment 7
Raw material is the flyash of certain heat power plant, and main chemical compositions is Al
2o
355%, SiO
237%, by grinding rear fineness, be that carbonating decomposition nut liquid after-80 order limestone powders or lime powder and sodium carbonate and evaporation is according to CaO and SiO
2mol ratio be 2.05 controls, sodium carbonate (comprises the Na in the carbonating decomposition nut liquid after evaporation
2o) addition is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be that 0.97 control is prepared burden and prepared charge pulp; By charge pulp, in temperature, be to fire under 1250 ℃ of conditions, obtain qualified grog; With adjusting liquid, under the condition of 80-90 ℃, leach grog, in grog, leaching rate of alumina can reach 88.21%, and in grog, sodium oxide leaching yield can reach 96.16%.Clinker leaching liquor carries out carbonating decomposition after desiliconization, obtains aluminium hydroxide, and aluminium hydroxide obtains metallurgical-grade aluminum oxide product after roasting.
Solid phase residue caustic sodium concentration after grog stripping is NaO
2Kthe alkali lye of 200g/L is under 220 ℃ of conditions in temperature, leaches 8 minutes, and leaching liquid-solid ratio is 3, Al in solid phase residue
2o
3leaching yield be 11%, Na in solid phase residue
2the leaching yield of O is 81%.The solid phase residue finally obtaining is as the raw material of producing cement.
Claims (6)
1. a method for aluminum oxide in alkaline process extract powder coal ash, the step of its production process comprises:
(1) in flyash, add lime and alkali lye, make charge pulp; The alkali lye adding is the mixed solution of the carbonating decomposition nut liquid after sodium carbonate and evaporation; The mixing process of its charge pulp, the addition of lime is by SiO in system
2amount determine, the addition of lime is according to CaO and SiO
2mol ratio be 0.8～2.2 control, the addition of sodium carbonate is according to Na
2o and Al
2o
3+ Fe
2o
3mol ratio be 0.9～1.7 control;
(2) charge pulp is fired into grog; The temperature that its charge pulp is fired is 900～1380 ℃, and the firing time is 10-120 minute;
(3) grog is carried out to alkali leaching, leaching slurry is carried out to liquid-solid separation, obtain solid phase residue 1 and leach liquor 1; Under the condition of 40～105 ℃ of temperature, to leach grog with adjusting liquid;
(4) leach liquor 1 is carried out, after desiliconization processing, carrying out liquid-solid separation;
(5) by liquid after the desiliconization filtering to isolate, carry out carbonating decomposition, obtain aluminium hydroxide;
(6) aluminium hydroxide obtains alumina product after roasting;
The step that it is characterized in that its process also comprises:
(7) the solid phase residue 1 obtaining in step (3) is carried out to alkali leaching again, leaching slurry is carried out to liquid-solid separation, obtain solid phase residue 2 and leach liquor 2, further reclaim aluminum oxide and alkali; Its strength of solution of carrying out alkali leaching use is NaO
2k30 ~ 250g/L;
Its extraction temperature that carries out alkali leaching is 60 ~ 250 ℃; Its extraction time that carries out alkali leaching is 5 ~ 360 minutes; Liquid-solid ratio when it carries out alkali leaching is 1 ~ 5;
(8) molecular ratio of adjustment System when the leach liquor 2 obtaining in step (7) is processed for step (4) desiliconization; In the leach liquor that also can obtain in step (7), add lime, reaction is filtered afterwards, and the filter residue excessively obtaining is for the desiliconization process of step (4);
(9) the solid phase residue 2 obtaining in step (7) is as the raw material of producing cement constructional material.
2. the method for aluminum oxide in a kind of alkaline process extract powder coal ash according to claim 1, is characterized in that the fineness of flyash in its step (1) is-0.18mm; The fineness of lime is-0.18mm.
3. the method for aluminum oxide in a kind of alkaline process extract powder coal ash according to claim 1, it is characterized in that its step (4) obtains the some or all of raw material that returns to step (1) and do charge pulp preparation of solid residue.
4. the method for aluminum oxide in a kind of alkaline process extract powder coal ash according to claim 1, it is characterized in that its step (5) carbonating decompose after mother liquor through evaporation after return to step (1), for charge pulp, prepare.
5. the method for aluminum oxide in a kind of alkaline process extract powder coal ash according to claim 1, it is characterized in that its leach the adjustment liquid used of grog by the liquid-solid separation of the slurries that leach grog after the washing lotion allotment of solid phase residue form.
6. the method for aluminum oxide in a kind of alkaline process extract powder coal ash according to claim 1, is characterized in that the molecular ratio of adjustment System when the leach liquor 2 that obtains in its step (7) is for step (4) desiliconization, and the molecular ratio of desiliconization dope is adjusted into 1.4 ~ 2.0.
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| CN201210084915.6A CN102627305B (en) | 2012-03-28 | 2012-03-28 | Method using alkaline process to extract alumina in coal ash |
| PCT/CN2012/087467 WO2013143335A1 (en) | 2012-03-28 | 2012-12-26 | Method for extracting aluminium oxide in fly ash by alkaline process |
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| CN102627305B (en) * | 2012-03-28 | 2014-05-07 | 中国铝业股份有限公司 | Method using alkaline process to extract alumina in coal ash |
| CN103663516B (en) * | 2012-09-26 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of method utilizing aluminous fly-ash to prepare aluminium hydroxide |
| CN103130254A (en) * | 2013-03-18 | 2013-06-05 | 中国铝业股份有限公司 | Method for producing aluminum oxide by using alkaline method |
| CN103130257A (en) * | 2013-03-18 | 2013-06-05 | 中国铝业股份有限公司 | Improved aluminum oxide production method |
| CN103349994B (en) * | 2013-06-28 | 2015-12-09 | 新奥科技发展有限公司 | A kind of catalyst that reclaims from coal ash is also separated the method obtaining aluminum contained compound |
| CN103771471B (en) * | 2014-01-26 | 2015-02-25 | 乌鲁木齐金石徽龙矿业有限公司 | Method for preparing aluminum oxide through coal ash |
| CN105776263B (en) * | 2016-02-06 | 2017-08-25 | 杭州锦江集团有限公司 | A kind of method that dry method burns till Bayer process alkali red mud |
| CN105565350B (en) * | 2016-02-06 | 2017-10-31 | 杭州锦江集团有限公司 | A kind of method that utilization aluminous fly-ash produces aluminum oxide |
| CN105776268B (en) * | 2016-02-06 | 2017-08-08 | 杭州锦江集团有限公司 | A kind of dry method process for calcining using flyash as raw material |
| CN105776265B (en) * | 2016-02-06 | 2017-07-04 | 杭州锦江集团有限公司 | A kind of method for producing aluminum oxide using low-grade bauxite based on pelletizing method |
| CN105565352B (en) * | 2016-02-06 | 2017-11-03 | 杭州锦江集团有限公司 | A kind of method that aluminum oxide is produced with aluminous fly-ash |
| CN106348323A (en) * | 2016-08-30 | 2017-01-25 | 内蒙古大唐国际再生资源开发有限公司 | Method for producing aluminum oxide from raw meal nodule |
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| CN101100305A (en) * | 2007-07-06 | 2008-01-09 | 内蒙古联合工业有限公司 | Fine comprehensive utilization technique of fly ash |
| CN101607725B (en) * | 2008-06-19 | 2011-04-20 | 中国科学院过程工程研究所 | Method for reclaiming alumina and sodium oxide in red mud of Bayer process |
| CN101654267A (en) * | 2008-08-19 | 2010-02-24 | 沈阳铝镁设计研究院 | Method for preparing aluminum and coproducing cement from flyash |
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| CN102351226B (en) * | 2011-09-26 | 2014-05-07 | 中国铝业股份有限公司 | Method for producing aluminum oxide from fly ash |
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Effective date of registration: 20180529 Address after: 450041 No. 82, Jiyuan Road, Zhengzhou District, Henan Co-patentee after: Aluminum Corporation of China Limited Patentee after: Henan Hua Hui Nonferrous Engineering Design Co., Ltd. Address before: 100082 Xizhimen North Street, Haidian District, Haidian District, Beijing Patentee before: Aluminum Corporation of China Limited |