CN101254933B - Method for extracting high-purity alumina and silica gel from coal ash - Google Patents
Method for extracting high-purity alumina and silica gel from coal ash Download PDFInfo
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- CN101254933B CN101254933B CN2008100178691A CN200810017869A CN101254933B CN 101254933 B CN101254933 B CN 101254933B CN 2008100178691 A CN2008100178691 A CN 2008100178691A CN 200810017869 A CN200810017869 A CN 200810017869A CN 101254933 B CN101254933 B CN 101254933B
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- 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 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000741 silica gel Substances 0.000 title claims abstract description 36
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 36
- 239000010883 coal ash Substances 0.000 title description 3
- 239000010881 fly ash Substances 0.000 claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims description 34
- 229960001866 silicon dioxide Drugs 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 2
- 229960004029 silicic acid Drugs 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 238000004064 recycling Methods 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 26
- 238000005245 sintering Methods 0.000 description 8
- 238000002386 leaching Methods 0.000 description 6
- 239000011449 brick Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 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 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910003641 H2SiO3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- VYOZKLLJJHRFNA-UHFFFAOYSA-N [F].N Chemical compound [F].N VYOZKLLJJHRFNA-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion 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
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011464 hollow brick Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-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
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011031 topaz Substances 0.000 description 1
- 229910052853 topaz Inorganic materials 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a method for extracting high-purity alumina and silica gel from the flyash. The method includes calcining and activating the powdered coal at low temperature; water extracting the alumina; acid extracting the alumina and the silica gel; separating the alumina and the silica gel; separating the alumina and the iron; recycling and reutilizing the CO2 generated during the calcining and recycling the alkali, the sodium chloride, the acid and the water during the extractions. The extracted alumina and silica gel have high purity and are used as high added value products. The separation extraction rates of the alumina and the silica gel in the fly ash reach more than 90%. The residue amount obtained after extracting the alumina and the silica gel from the fly ash is lessthan 10% of the fly ash. The entire technological process is carried out under the normal pressure, therefore the method has low requirement for equipment. Since the CO2 generated during the calcining and the alkali and the acid used in the extraction can be reutilized, the method can realize zero discharge without secondary pollution.
Description
Technical field
The invention belongs to solid waste recovery and utilization technology field, be specifically related to a kind of method of from flyash, extracting high purity aluminium oxide and silica gel.
Background technology
Flyash is the solid waste residue that the coal-burning power plant discharges.At present, the total volume of cargo in storage of China's flyash surpasses 1,000,000,000 tons, but also with about 100,000,000 tons speed increase in every year, not only taken a large amount of land resources, but also severe contamination environment.
Coal-fired enterprise must implement total utilization of PCA in the near future, realizes this target of zero release of waste by recycle.At present flyash being adopted mostly approach such as cement baking, hollow brick both at home and abroad, only is a kind of low-level utilization, often is difficult to obtain good economic benefit.Therefore, how to improve utilization of coal ash and be worth, become the significant problem that needs to be resolved hurrily that electric power and relevant enterprise realize that Sustainable development faced.
Chemical analysis shows, contain more than 80 kind of element in the coal, during burning wherein small part drain with cigarette, major part still is retained in the flyash, its main component is silicon, aluminium, oxygen, iron, secondly also have calcium, magnesium, potassium, sodium, sulphur, vanadium, titanium etc., also compose simultaneously and deposit elements such as some precious rare metal germanium, gallium, uranium, thorium.Therefore, high added value composition wherein if can be extracted and be utilized effectively, can become renewable resource a kind of wide material sources, that can obtain good economic benefit.
The comprehensive utilizating research of flyash, the research of particularly extracting aluminum oxide from aluminous fly-ash began so far from the forties in last century, was a research focus always.Because flyash is to generate through high-temp combustion (temperature is greater than 1300 ℃, combustion flame core temperature even between 1500～1700 ℃), under high temperature like this, coal ash is softening or fluid state mostly.So, in their temperature-fall periods, Al wherein
2O
3Component is vitreous state or high temperature aluminum-containing mineral mullite crystal, topaz crystalline mineral forms and exists.And under the normality condition, very difficult directly dissolved through these vitreums, the mineral crystal of hot environment with acid method molten or that alkali is molten, Al wherein
2O
3Nature can't extract.Many experts both domestic and external, scholar have carried out a large amount of work in this respect, have proposed various extracting method.Wherein, representational mainly containing: limestone sintering method, soda-lime sintering process, alkali burn method, fluorine ammonia hydrotropy method or the like.In these methods, the limestone sintering method is present unique a kind of method that is committed to industrial practice, a variety of causes such as other method is low owing to restriction, the alumina extraction ratio of processing condition, energy consumption is high, production cost is high, bed drain purge is big still rest on the experimental phase at present.
It is pointed out that raw materials for sintering that the limestone sintering method uses Wingdale, manufacturing cost of aluminum oxide is minimized relatively as cheapness.But this method remains in a lot of defectives: at first, when extracting aluminum oxide, can produce a large amount of silico-calcium slags, 1 ton of aluminum oxide of every production will produce the silico-calcium slag about 8～10 tons, if the building materials market can not these silico-calcium slags of complete digestion, will certainly cause waste discharge new, that the stacking amount is bigger; Secondly, the limestone sintering method needs high-temperature calcination (1320 ℃～1400 ℃), belongs to energy processes, and the requirement of its technological process and equipment is also higher; The 3rd, because the quantity of slag is excessive, the rate of recovery of alkali is reduced in the molten process of alkali, cause cost to rise.Therefore, want the aluminum oxide in the flyash is extracted and fully utilizes, above-mentioned three problems all need to be properly settled.
Summary of the invention
The objective of the invention is in order to overcome in the prior art aluminum oxide and the silica gel extraction yield is low, energy consumption is high, complex process, level of residue is big and residue utilizes the low technical problem of added value, and provide a kind of technology simple, energy consumption is low, the method for extracting high purity aluminium oxide and silica gel from flyash that aluminum oxide and silica gel extraction yield and purity are high.
To achieve these goals, the technical solution used in the present invention is: a kind of method of extracting high purity aluminium oxide and silica gel from flyash is characterized in that this method may further comprise the steps:
(1) flyash is ground, and to make its particle diameter is 200～240 orders, flyash and the Na after grinding
2CO
3Flyash by weight percentage: the mixed of yellow soda ash=1: 0.5～5, stirring;
(2) mixture that step (1) is formed was calcined 0.5～2 hour under 600 ℃～1000 ℃ conditions of temperature;
(3) in sintered product, add an amount of water, sinter by weight percentage: water=1: 50～200, the Na in the sintered product
2SiO
3And NaAlO
2Be dissolved in the water 0.5 hour～2 hours after-filtration of leaching under 60 ℃～95 ℃ conditions of temperature;
(4) in step (3) gained concentrated filtrate, feed the CO of step (2) gained
2, charcoal divides 2 hours after-filtration, obtains H
2SiO
3And Al (OH)
3Mixture;
(5) in the filter residue of step (3) and (4) gained, add technical hydrochloric acid, its solid-liquid weight percent is 1: 3～5, extracting temperature is under 50 ℃～90 ℃ conditions, and 20～60 minutes extraction times, separation system is a sour environment, the pH value of separation system is less than 3.0, abstraction reaction after-filtration, gained filter residue are silica gel, and filtrate is AlCl
3With small amount of Fe Cl
3Mixing solutions;
(6) AlCl that obtains of step (5)
3With FeCl
3Mixing solutions through concentrate, crystallization and thermal degradation, obtain Al
2O
3With Fe
2O
3Mixture, hydrogen chloride gas add water by the absorption tower and absorb recovery hydrochloric acid, return step (5) and recycle;
(7) with Al
2O
3With Fe
2O
3Mixture is inserted in 3～10% the NaOH solution, and separation system is an alkaline environment, and its pH value is greater than 8.0, and the temperature of system remains on 60 ℃～90 ℃, the after-filtration that reacts completely, and filtrate is NaAlO
2, filter residue is the iron content residue;
(8) step (7) gained filtrate is fed CO
2, reacting 1 hour after-filtration, the filter residue after the filtration is Al (OH)
3, filtrate is Na
2CO
3Solution, Na
2CO
3Reclaimed by evaporative crystallization, return step (1) and recycle;
(9) with the Al (OH) of gained
3Through 800～1200 ℃ of temperature condition roastings 1～3 hour, obtain the aluminum oxide ultra-fine dry powder;
What (10) step (5) is obtained contains H
2SiO
3Filter residue carry out purifying, separation, obtain pure silica gel and residue;
Described high purity aluminium oxide is meant that purity is 99.86% aluminum oxide, and described high-purity silica gel is meant that silicon-dioxide is greater than 90% hydrated silica gel.
The incinerating time described in the step (2) is 0.5～1 hour.
The weight percent of sinter and water is 1: 70～150 described in the step (3); Extraction temperature is 70 ℃～85 ℃; Extraction time was at 1～1.5 hour.
The solid-liquid weight percent is 1: 3 described in the step (5), and extracting temperature is 60 ℃～80 ℃, and extraction time is 20～40 minutes.
The pH value of separation system is 1.0-3.0 described in the step (5).
The pH value of separation system is 8.5-11.5 described in the step (7).
The present invention is by grinding flyash, and with itself and Na
2CO
3Mix by a certain percentage, stir; Calcine under the certain temperature condition, the main chemical reactions that is taken place in the sintering process is as follows:
Al
6Si
2O
13+4SiO
2+3Na
2CO
3→6NaA1SiO
4+3CO
2↑
Al
2O
3+Na
2CO
3＝2NaAlO
2+CO
2↑
SiO
2+Na
2CO
3＝Na
2SiO
3+CO
2↑
The main thing of the sinter that generates has nepheline and sodium metaaluminate, water glass mutually.The CO that discharges in the sintering process
2Direct recovery.The dissolving of sintered product part used water, Na wherein
2SiO
3And NaAlO
2Be dissolved in the water surplus part A l
2O
3In the solid filter residue.In this stage, aluminum oxide leaching rate (G) calculation formula is:
By in filtrate, feeding CO
2, charcoal divides after-filtration, obtains H
2SiO
3And Al (OH)
3Mixture.Sial miscellany dissolving with hydrochloric acid, reaction after-filtration filter residue is a silica gel, filtrate is AlCl
3With small amount of Fe Cl
3Mixing solutions, AlCl
3With FeCl
3Mixing solutions obtains Al through concentrated, crystallization, thermal degradation
2O
3With Fe
2O
3Mixture, hydrogen chloride gas add water by the absorption tower and absorb recovery hydrochloric acid, Al
2O
3With Fe
2O
3Mixture dissolves with NaOH, and the chemical reaction that is taken place is as follows:
2NaOH+Al
2O
3＝2NaAlO
2+H
2O
Filtrate is NaAlO
2, filter residue is the iron content residue, filtrate feeds CO
2, react 1 hour after-filtration.Filter residue after the filtration is Al (OH)
3The chemical reaction that takes place is:
2NaAlO
2+CO
2+3H
2O＝2Al(OH)
3↓+Na
2CO
3
Filtrate is Na
2CO
3Solution, Na
2CO
3Can be reclaimed repeated use by evaporative crystallization, with the Al (OH) of gained
3Through 800～1200 ℃ of temperature condition roastings 1～3 hour, obtain the aluminum oxide ultra-fine dry powder.The chemical reaction that takes place in the roasting process is:
2Al(OH)
3＝Al
2O
3+3H
2O
The filter residue that contains H2SiO3 that obtains carries out purifying, obtains pure silica gel.Remaining residue, dry-pressing formed after the fusion appropriate amount of auxiliary materials, make non-burning brick.
The present invention compared with prior art has the following advantages: aluminum oxide that the present invention extracts and silica gel purity height, be high value-added product, the separation and Extraction rate of aluminum oxide in the flyash and silicon-dioxide all can reach more than 90%, extraction separation the level of residue after aluminum oxide and the silicon-dioxide less than 10% of used flyash amount, and this residue is made into non-burning brick being used, whole technological process is all carried out under condition of normal pressure, therefore the CO low to the equipment requirements condition, that calcination stage produces in the technological process of the present invention
2And all recyclable utilization of employed alkali, acid in the leaching process, therefore, this technology can realize zero release, can not form secondary pollution.
Below the present invention will be further described by specific embodiment, but the present invention is not limited only to following examples.
Embodiment
Embodiment 1
(1) flyash is ground, and to make its particle diameter is 200 orders, flyash and the Na after grinding
2CO
3Flyash by weight percentage: the mixed of yellow soda ash=1: 2～4, stirring;
(2) mixture that step (1) is formed was calcined 1 hour under 600 ℃ of conditions of temperature;
(3) in sintered product, add an amount of water, sinter by weight percentage: water=1: 50, the Na in the sintered product
2SiO
3And NaAlO
2Be dissolved in the water 0.5 hour after-filtration of leaching under 60 ℃ of conditions of temperature;
(4) in step (3) gained concentrated filtrate, feed the CO of step (2) gained
2, charcoal divides 2 hours after-filtration, obtains H
2SiO
3And Al (OH)
3Mixture;
(5) in the filter residue of step (3) and (4) gained, add technical hydrochloric acid, its solid-liquid weight percent is 1: 3, extracting temperature is under 50 ℃ of conditions, and 20 minutes extraction times, separation system is a sour environment, the pH value of separation system is 1.0, abstraction reaction after-filtration, gained filter residue are silica gel, and filtrate is AlCl
3With small amount of Fe Cl
3Mixing solutions;
(6) AlCl that obtains of step (5)
3With FeCl
3Mixing solutions through concentrate, crystallization and thermal degradation, obtain Al
2O
3With Fe
2O
3Mixture, hydrogen chloride gas add water by the absorption tower and absorb recovery hydrochloric acid, return step (5) and recycle;
(7) with Al
2O
3With Fe
2O
3Mixture is inserted in 3% the NaOH solution, and separation system is an alkaline environment, and its pH value is 8.5, and the temperature of system remains on 60 ℃, the after-filtration that reacts completely, and filtrate is NaAlO
2, filter residue is the iron content residue;
(8) step (7) gained filtrate is fed CO
2, reacting 1 hour after-filtration, the filter residue after the filtration is Al (OH)
3, filtrate is Na
2CO
3Solution, Na
2CO
3Reclaimed by evaporative crystallization, return step (1) and recycle;
(9) with the Al (OH) of gained
3Through 800 ℃ of temperature condition roastings 1 hour, obtain the aluminum oxide ultra-fine dry powder;
What (10) step (5) is obtained contains H
2SiO
3Filter residue carry out purifying, separation, obtain pure silica gel and residue;
(11) residue that step (7) and (10) are obtained is dry-pressing formed after the fusion appropriate amount of auxiliary materials, makes non-burning brick.
Embodiment 2
(1) flyash is ground, and to make its particle diameter is 220 orders, flyash and the Na after grinding
2CO
3Flyash by weight percentage: the mixed of yellow soda ash=1: 0.5～2, stirring;
(2) mixture that step (1) is formed was calcined 2 hours under 800 ℃ of conditions of temperature;
(3) in sintered product, add an amount of water, sinter by weight percentage: water=1: 120, the Na in the sintered product
2SiO
3And NaAlO
2Be dissolved in the water 1 hour after-filtration of leaching under 80 ℃ of conditions of temperature;
(4) in step (3) gained concentrated filtrate, feed the CO of step (2) gained
2, charcoal divides 2 hours after-filtration, obtains H
2SiO
3And Al (OH)
3Mixture;
(5) in the filter residue of step (3) and (4) gained, add technical hydrochloric acid, its solid-liquid weight percent is 1: 4, extracting temperature is under 75 ℃ of conditions, and 40 minutes extraction times, separation system is a sour environment, the pH value of separation system is 2.0, abstraction reaction after-filtration, gained filter residue are silica gel, and filtrate is AlCl
3With small amount of Fe Cl
3Mixing solutions;
(6) AlCl that obtains of step (5)
3With FeCl
3Mixing solutions through concentrate, crystallization and thermal degradation, obtain Al
2O
3With Fe
2O
3Mixture, hydrogen chloride gas add water by the absorption tower and absorb recovery hydrochloric acid, return step (5) and recycle;
(7) with Al
2O
3With Fe
2O
3Mixture is inserted in 5% the NaOH solution, and separation system is an alkaline environment, and its pH value is 10, and the temperature of system remains on 75 ℃, the after-filtration that reacts completely, and filtrate is NaAlO
2, filter residue is the iron content residue;
(8) step (7) gained filtrate is fed CO
2, reacting 1 hour after-filtration, the filter residue after the filtration is Al (OH)
3, filtrate is Na
2CO
3Solution, Na
2CO
3Reclaimed by evaporative crystallization, return step (1) and recycle;
(9) with the Al (OH) of gained
3Through 1000 ℃ of temperature condition roastings 2 hours, obtain the aluminum oxide ultra-fine dry powder;
What (10) step (5) is obtained contains H
2SiO
3Filter residue carry out purifying, separation, obtain pure silica gel and residue;
(11) residue that step (7) and (10) are obtained is dry-pressing formed after the fusion appropriate amount of auxiliary materials, makes non-burning brick.
Embodiment 3
(1) flyash is ground, and to make its particle diameter is 240 orders, flyash and the Na after grinding
2CO
3Flyash by weight percentage: the mixed of yellow soda ash=1: 4～5, stirring;
(2) mixture that step (1) is formed was calcined 2 hours under 1000 ℃ of conditions of temperature;
(3) in sintered product, add an amount of water, sinter by weight percentage: water=1: 200, the Na in the sintered product
2SiO
3And NaAlO
2Be dissolved in the water 0.5 hour～2 hours after-filtration of leaching under 95 ℃ of conditions of temperature;
(4) in step (3) gained concentrated filtrate, feed the CO of step (2) gained
2, charcoal divides 2 hours after-filtration, obtains H
2SiO
3And Al (OH)
3Mixture;
(5) in the filter residue of step (3) and (4) gained, add technical hydrochloric acid, its solid-liquid weight percent is 1: 5, extracting temperature is under 90 ℃ of conditions, and 60 minutes extraction times, separation system is a sour environment, the pH value of separation system is 3.0, abstraction reaction after-filtration, gained filter residue are silica gel, and filtrate is AlCl
3With small amount of Fe Cl
3Mixing solutions;
(6) AlCl that obtains of step (5)
3With FeCl
3Mixing solutions through concentrate, crystallization and thermal degradation, obtain Al
2O
3With Fe
2O
3Mixture, hydrogen chloride gas add water by the absorption tower and absorb recovery hydrochloric acid, return step (5) and recycle;
(7) with Al
2O
3With Fe
2O
3Mixture is inserted in 10% the NaOH solution, and separation system is an alkaline environment, and its pH value is 11.5, and the temperature of system remains on 90 ℃, the after-filtration that reacts completely, and filtrate is NaAlO
2, filter residue is the iron content residue;
(8) step (7) gained filtrate is fed CO
2, reacting 1 hour after-filtration, the filter residue after the filtration is Al (OH)
3, filtrate is Na
2CO
3Solution, Na
2CO
3Reclaimed by evaporative crystallization, return step (1) and recycle;
(9) with the Al (OH) of gained
3Through 1200 ℃ of temperature condition roastings 3 hours, obtain the aluminum oxide ultra-fine dry powder;
What (10) step (5) is obtained contains H
2SiO
3Filter residue carry out purifying, separation, obtain pure silica gel and residue;
(11) residue that step (7) and (10) are obtained is dry-pressing formed after the fusion appropriate amount of auxiliary materials, makes non-burning brick.
Claims (6)
1. method of extracting high purity aluminium oxide and silica gel from flyash is characterized in that this method may further comprise the steps:
(1) flyash is ground, and to make its particle diameter is 200～240 orders, flyash and the Na after grinding
2CO
3By weight flyash: the mixed of yellow soda ash=1: 0.5～5, stirring;
(2) mixture that step (1) is formed was calcined 0.5～2 hour under 600 ℃～1000 ℃ conditions of temperature;
(3) in sintered product, add an amount of water, sinter by weight: water=1: 50～200, the Na in the sintered product
2SiO
3And NaAlO
2Be dissolved in the water 0.5 hour～2 hours after-filtration of lixiviate under 60 ℃～95 ℃ conditions of temperature;
(4) in step (3) gained concentrated filtrate, feed the CO of step (2) gained
2, charcoal divides 2 hours after-filtration, obtains H
2SiO
3And Al (OH)
3Mixture;
(5) in the filter residue of step (3) and (4) gained, add technical hydrochloric acid, its solid-liquid weight ratio is 1: 3～5, extracting temperature is under 50 ℃～90 ℃ conditions, and 20～60 minutes extraction times, separation system is a sour environment, the pH value of separation system is less than 3.0, abstraction reaction after-filtration, gained filter residue are silica gel, and filtrate is AlCl
3With small amount of Fe Cl
3Mixing solutions;
(6) AlCl that obtains of step (5)
3With FeCl
3Mixing solutions through concentrate, crystallization and thermal degradation, obtain Al
2O
3With Fe
2O
3Mixture, hydrogen chloride gas add water by the absorption tower and absorb recovery hydrochloric acid, return step (5) and recycle;
(7) with Al
2O
3With Fe
2O
3Mixture is inserted in 3～10% the NaOH solution, and separation system is an alkaline environment, and its pH value is greater than 8.0, and the temperature of system remains on 60 ℃～90 ℃, the after-filtration that reacts completely, and filtrate is NaAlO
2, filter residue is the iron content residue;
(8) step (7) gained filtrate is fed CO
2, reacting 1 hour after-filtration, the filter residue after the filtration is Al (OH)
3, filtrate is Na
2CO
3Solution, Na
2CO
3Reclaimed by evaporative crystallization, return step (1) and recycle;
(9) with the Al (OH) of gained
3Through 800～1200 ℃ of temperature condition roastings 1～3 hour, obtain the aluminum oxide ultra-fine dry powder;
What (10) step (5) is obtained contains H
2SiO
3Filter residue carry out purifying, separation, obtain pure silica gel and residue;
Described high purity aluminium oxide is meant that purity is 99.86% aluminum oxide, and described high-purity silica gel is meant that silicon-dioxide is greater than 90% hydrated silica gel.
2. the method for extracting high purity aluminium oxide and silica gel from flyash according to claim 1 is characterized in that the incinerating time is 0.5～1 hour described in the step (2).
3. the method for extracting high purity aluminium oxide and silica gel from flyash according to claim 1 is characterized in that the weight ratio of sinter described in the step (3) and water is 1: 70～150; Extraction temperature is 70 ℃～85 ℃; Extraction time was at 1～1.5 hour.
4. the method for extracting high purity aluminium oxide and silica gel from flyash according to claim 1 is characterized in that the solid-liquid weight ratio is 1: 3 described in the step (5), and extracting temperature is 60 ℃～80 ℃, and extraction time is 20～40 minutes.
5. the method for extracting high purity aluminium oxide and silica gel from flyash according to claim 1 is characterized in that the pH value of separation system described in the step (5) is 1.0-3.0.
6. the method for extracting high purity aluminium oxide and silica gel from flyash according to claim 1 is characterized in that the pH value of separation system described in the step (7) is 8.5-11.5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101759210B (en) * | 2010-01-18 | 2012-12-05 | 马昱昭 | Method for extracting high purity alumina and silica gel from coal ash |
| CN101792161B (en) * | 2010-01-18 | 2013-01-16 | 马昱昭 | Method for extracting high purity alumina and silica gel from fly ash in coal-fired power plants |
| CN101759209B (en) * | 2010-01-20 | 2012-07-25 | 潘爱芳 | Method for extracting high purity alumina and silica gel from coal gangue |
| CN101767807B (en) * | 2010-01-20 | 2012-12-05 | 潘爱芳 | Method for extracting high-purity aluminum oxide and silica gel from beauxite |
| CN101811712A (en) | 2010-04-27 | 2010-08-25 | 中国神华能源股份有限公司 | Method for preparing metallurgical-grade aluminum oxide by using fluid-bed fly ash |
| CN101844770A (en) * | 2010-04-27 | 2010-09-29 | 中国神华能源股份有限公司 | Method for preparing white carbon black through extracting aluminum residue by fly ash |
| CN101913615B (en) * | 2010-07-20 | 2012-04-25 | 潘爱芳 | Method for improving alumina silica ratio of low-grade bauxite |
| CN102994745A (en) * | 2012-11-30 | 2013-03-27 | 重庆地质矿产研究院 | Leaching method of coal measure stratum co-associated metal element aluminum |
| CN103833042A (en) * | 2013-12-13 | 2014-06-04 | 中国神华能源股份有限公司 | Method for preparing silicone oxide micro powder by using residues after extracting aluminum from fly ash, and silicone oxide micro powder |
| CN103952557A (en) * | 2014-03-20 | 2014-07-30 | 浙江大学 | Method for secondary acid leaching of alumina in coal ash residues |
| CN103936045B (en) * | 2014-04-01 | 2016-02-10 | 王宝冬 | A kind of method extracting aluminum oxide from flyash |
| CN109231253A (en) * | 2018-11-09 | 2019-01-18 | 长沙万荣粉体设备科技有限公司 | A kind of native sulfate of barium method of purification and equipment |
| CN113061733A (en) * | 2021-03-19 | 2021-07-02 | 大连理工大学 | Method for preparing aluminum-rich leaching solution by using fly ash sintering activation-acid leaching method |
| CN114735732B (en) * | 2022-05-06 | 2023-10-27 | 内蒙古工业大学 | Method for preparing alumina and silicon dioxide from high-alumina fly ash |
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