CN1868884A - Method of extracting aluminium oxide from fly ash and simultaneously producing white carbon black - Google Patents
Method of extracting aluminium oxide from fly ash and simultaneously producing white carbon black Download PDFInfo
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- CN1868884A CN1868884A CN 200610012780 CN200610012780A CN1868884A CN 1868884 A CN1868884 A CN 1868884A CN 200610012780 CN200610012780 CN 200610012780 CN 200610012780 A CN200610012780 A CN 200610012780A CN 1868884 A CN1868884 A CN 1868884A
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- 238000000034 method Methods 0.000 title claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000006229 carbon black Substances 0.000 title claims abstract description 21
- 239000010881 fly ash Substances 0.000 title claims description 48
- 239000007788 liquid Substances 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 29
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 23
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 22
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 3
- 230000003213 activating effect Effects 0.000 claims abstract 2
- 238000000227 grinding Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 22
- 229960004887 ferric hydroxide Drugs 0.000 claims description 22
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 19
- 235000019353 potassium silicate Nutrition 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 13
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003746 solid phase reaction Methods 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000004131 Bayer process Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000010883 coal ash Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013587 production medium Substances 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A process for extracting alumina from powdered coal ash while generating white carbon black includes such steps as grinding powdered coal ash, activating, adding ammonium sulfate, reacting, adding water, filtering, filling ammonia gas into the filtered liquid to obtain the deposited mixture of aluminum hydroxide and iron hydroxide, adding the solution of sodium hydroxide to dissolve the aluminum hydroxide deposit, adding carbon to obtain pure aluminum hydroxide, and calcining to obtain Al2O3.
Description
Technical Field
The invention relates to a comprehensiveutilization process of fly ash, in particular to a method for extracting alumina from fly ash and co-producing white carbon black.
Background
A large number of thermal power plants in China generate a large amount of fly ash every year. The amount of fly ash discharged to the nature by one million power plants per day reaches more than 2500 tons, which brings great pressure to the environmental protection. The existing method for treating fly ash is mainly used for making bricks or cement, but because the fly ash is rich in various substances such as alumina, silicon dioxide and the like, the fly ash has a very wide comprehensive utilization prospect. At present, two major processes of extracting substances such as alumina and the like from fly ash mainly comprise an acid method and an alkali method, but the fly ash is a mixed material with potential pozzolanic reactivity, has large structural polymerization degree, high bond energy and stable chemical property, and is difficult to directly react with acid and alkali in general. The acid process mostly uses sulfuric acid or hydrochloric acid as a production medium, and has the problems of difficult reaction, low extraction rate and low resource utilization rate. When sulfuric acid is used as a production medium, ammonium sulfate byproduct is produced in an amount approximately 4 times that of alumina; when hydrochloric acid is used as a production medium, a large amount of hydrogen chloride gas is released in the high-temperature reaction process due to the low boiling point of the hydrochloric acid, so that the environment is easily polluted. In the process of producing alumina and cement by using an alkaline process, although the fly ash can be completely utilized, a large amount of limestone is used and is fired with the fly ash at a high temperature. A large amount of energy is consumed in the middle, and low-value cement clinker with the yield of more than 5 times of alumina is also generated. The prior report also records that the coal gangue is treated by using ammonium sulfate, but compared with the coal gangue, the coal ash to be treated by the invention has obvious difference in chemical property and treatment process.
Disclosure of Invention
The invention provides a method for extracting alumina from fly ash and co-producing white carbon black, aiming at solving the problems of complex process, more byproducts, low extraction rate and easy environmental pollution in the prior art.
The invention is realized by the following technical scheme, and the method for extracting alumina from fly ash and co-producing white carbon black simultaneously comprises the following steps:
1. the fly ash is ground to 400-500 meshes, mechanical magnetic force is carried out to remove iron, and then roasting activation is carried out at 600-700 ℃ for 1-2 hours. If the granularity of the fly ash is too coarse, the reaction is incomplete, and the effective extraction rate is lower; if the fly ash particle size is too fine, filtration difficulties can result.
2. Mixing the activated fly ash and ammonium sulfate according to the requirement, uniformly stirring according to the weight ratio of the alumina to the ammonium sulfate in the fly ash of 1: 5-6, and allowing the mixture to enter a reactor for solid-phase reaction at the temperature of 360-460 ℃ for 1-3 hours.
If the reaction temperature is too high, sulfuric acid fume is emitted, and the environment is affected. The content of alumina in the fly ash is different according to coal quality.
In the reaction stage, alumina, ferric oxide and ammonium sulfate in the fly ash react to generate soluble sulfate and release ammonia gas, and the ammonia gas is recovered for later use. The equation involved in this step is:
3. adding water into the reactant, stirring and leaching for 20-40 minutes under a normal pressure boiling state, and filtering. The filtrate (aluminum sulfate and ferric sulfate solution) is used for producing aluminum oxide and ferric hydroxide, and the filter residue is used for producing white carbon black.
4. And (3) adding ammonia gas (ammonia water) into the filtrate obtained in the previous step in proportion, wherein the molar ratio of the reaction amount of the aluminum oxide in the fly ash to the ammonia gas (ammonia water) is 1: 7-8, forming mixed precipitate of aluminum hydroxide and ferric hydroxide and ammonium sulfate solution, carrying out solid-liquid separation, and then evaporating, concentrating and drying the liquid.
The equation involved in this step is:
5. and melting the aluminum hydroxide precipitate by using a sodium hydroxide solution to form a mixture of a sodium aluminate solution and an iron hydroxide precipitate, wherein the alkali dissolution process is carried out at normal pressure and 60-90 ℃. The initial concentration of alkali liquor for alkali dissolution is controlled to be [ Na]2O]The concentration is 140-170 g/L. Stirring for reaction, and boiling for 1-5 minutes after the aluminum hydroxide is completely dissolved so as to be beneficial to the precipitation of the ferric hydroxide. Because the ferric hydroxide does not react with alkali, the ferric hydroxide still exists in a precipitation formFiltering and separating in sodium aluminate liquid to reach the aim of removing iron. And washing filter residues for producing high-purity ferric oxide. Combining the washing liquid and the filtrate, removing the carbon dioxide decomposition process to prepare aluminum hydroxide,
equations involved in this stepComprises the following steps:
6. after filtering and removing iron, adding seed carbon component into sodium aluminate solution, calcining formed aluminium hydroxide to prepare Al2O3。
The equation involved in this step is:
7. in the step 3, adding 3-5 times of water by weight of SiO into the filter residue obtained after filtering2/Na2Adding a sodium hydroxide solution into the mixture with the O being 3.4-4, reacting for 40-60 minutes under the pressure of 0.2-0.3 Mpa, filtering out impurities to obtain a high-modulus sodium silicate liquid (water glass), adding a dispersing agent and a surfactant into the water glass, fully stirring, adding sulfuric acid to adjust the pH value under the stirring state according to requirements to obtain superfine (nano) silica precipitate, and after solid-liquid separation, cleaning, drying and crushing the solid to obtain the nano white carbon black.
The method has the advantages that all elements with extraction and utilization values in the fly ash are basically converted into metallurgical and chemical materials with high added values except a small part of residues, the extraction rate of alumina in the fly ash reaches more than 85 percent, the extraction rate of white carbon black reaches more than 90 percent, the granularity is uniform, and the activity is high.
The invention adopts ammonium sulfate as a circulating medium to extract alumina, thereby not only overcoming the problems of harm and environmental protection caused by corrosion of an acid method (sulfuric acid and hydrochloric acid) process to equipment, but also improving the extraction rate of the alumina. Because the ammonium sulfate does not react with silicon, a complicated desiliconization process is omitted in the process of preparing the aluminum oxide. The silicon dioxide is fully activated in the process of extracting the aluminum, so that the subsequent white carbon black production process is very simple.
Drawings
FIG. 1 is a flow chart of a process for extracting alumina from fly ash
FIG. 2 is a flow chart of white carbon black process
Detailed Description
Example 1: the method for extracting alumina from fly ash and co-producing white carbon black simultaneously comprises the following steps:
1. the fly ash is ground to 400 meshes, and is subjected to mechanical and magnetic deironing, and then is roasted and activated at 600 ℃ for 1 hour.
2. Mixing the activated fly ash and ammonium sulfate according to the requirement, uniformly stirring according to the weight ratio of alumina to ammonium sulfate in the fly ash of 1: 5, and entering a reactor to perform solid phase reaction at 360 ℃ for 1 hour.
3. Adding water into the above reactant, stirring and leaching under boiling state at normal pressure for 20 min, and filtering.
4. Adding ammonia gas (ammonia water) into the filtrate obtained in the previous step in proportion, forming aluminum hydroxide and ferric hydroxide mixed precipitate and ammonium sulfate solution by taking the molar ratio of the reaction amount of aluminum oxide in the fly ash to the ammonia gas (ammonia water) as 1: 7, and after solid-liquid separation, evaporating, concentrating and drying the liquid. If aluminum sulfate is crystallized and precipitated in the leaching solution, the leaching solution is heated to be dissolved and then ammonolysis is carried out. Under the condition of ensuring complete reaction, the adding amount of ammonia water (ammonia gas) is not too large, otherwise, ammonia smell can escape in the subsequent process. Filtering and washing the mixed precipitate of aluminum hydroxide and ferric hydroxide obtained by ammonolysis twice, allowing the filter cake to enter an alkali dissolution process, and allowing the filtrate and the washing liquid to be combined and enter an ammonium sulfate concentration and crystallization process.
5. The solid part is dissolved by sodium hydroxide solution to form a mixture of sodium aluminate solution and ferric hydroxide precipitate, and the alkali dissolution process is carried out at 60 ℃ under normal pressure. The initial concentration of alkali solution for alkali dissolution is [ Na]2O]Stirring and reacting for 30 minutes until the aluminum hydroxide is finished under 140g/LAnd after complete dissolution, boiling for 1-5 minutes to facilitate the precipitation of ferric hydroxide. Because the ferric hydroxide does not react with the alkali, the ferric hydroxide still exists in the sodium aluminate liquid in a precipitation form, and the aim of removing iron is fulfilled by filtering and separating. And washing filter residues for producing high-purity ferric oxide. Combiningthe washing liquid and the filtrate, removing the carbon dioxide decomposition process to prepare aluminum hydroxide,
6. after filtering and removing iron, adding seed carbon component into sodium aluminate solution, calcining formed aluminium hydroxide to prepare Al2O3Preparation of sand-like α -Al by decomposition and sectional firing2O3The working procedure of (2) is carried out according to the Bayer process,
7. in the step 3, adding 3 times of water by weight of the dry matter of the filter residue into the filter residue obtained after filtration,according to SiO2/Na2Adding sodium hydroxide solution into the solution of O3.4, reacting for 40 min under the pressure of 0.2Mpa, filtering to remove impurities to obtain high-modulus sodium silicate liquid (water glass), washing the filter residue twice, and discarding. And combining the filtrate and the washing solution for later use. At this time, SiO in the solution2The content is 5-10%.
Adding 20% NaCl liquid into water glass according to the volume ratio of the water glass liquid to the 20% NaCl liquid of 100: 5; adding n-butanol according to the volume ratio of the water glass liquid to the n-butanol of 10000: 35,
and after fully stirring, adding 20% sulfuric acid to adjust the pH value to 8 under the stirring state, standing for 3 hours at room temperature, then heating to 70 ℃, stirring, adding 20% sulfuric acid to adjust the pH value to 6, curing for 20 minutes, filtering, washing and flashing to obtain the high-activity white carbon black finished product.
Example 2: the method for extracting alumina from fly ash and co-producing white carbon black simultaneously comprises the following steps:
1. the fly ash is ground to 500 meshes, and is subjected tomechanical and magnetic force deferrization, and then is roasted and activated at 700 ℃ for 2 hours.
2. Mixing the activated fly ash and ammonium sulfate according to the requirement, uniformly stirring according to the weight ratio of alumina to ammonium sulfate in the fly ash of 1: 6, feeding the mixture into a reactor, and carrying out solid-phase reaction at 460 ℃ for 3 hours.
3. Adding water into the above reactant, stirring and leaching under boiling state at normal pressure for 40 min, and filtering.
4. Adding ammonia gas (ammonia water) into the filtrate obtained in the previous step in proportion, forming aluminum hydroxide and ferric hydroxide mixed precipitate and ammonium sulfate solution by taking the molar ratio of the reaction amount of aluminum oxide in the fly ash to the ammonia gas (ammonia water) as 1: 8, and after solid-liquid separation, evaporating, concentrating and drying the liquid.
5. The solid part is dissolved by sodium hydroxide solution to form a mixture of sodium aluminate solution and ferric hydroxide precipitate, and the alkali dissolution process is carried out at normal pressure and 90 ℃. The initial concentration of alkali solution for alkali dissolution is [ Na]2O]Stirring and reacting for 30 minutes when the concentration is 170g/L, and boiling for 1-5 minutes after the aluminum hydroxide is completely dissolved so as to be beneficial to the precipitation of the ferric hydroxide. Because the ferric hydroxide does not react with the alkali, the ferric hydroxide still exists in the sodium aluminate liquid in a precipitation form, and the aim of removing iron is fulfilled by filtering and separating. And washing filter residues for producing high-purity ferric oxide. Combining the washing liquid and the filtrate, removing the carbon dioxide decomposition process to prepare aluminum hydroxide,
6. after filtering and removing iron, adding seed carbon component into sodium aluminate solution, calcining formed aluminium hydroxide to prepare Al2O3。
7. In the step 3, adding 3-5 times of water by weight of SiO (in weight ratio) into the filter residue obtained after filtering according to the dry matter of the filter residue2/Na2Adding sodium hydroxide solution into the solution O4, reacting for 60 minutes under the pressure of 0.3Mpa, filtering out impurities to obtain high-modulus sodium silicate liquid (water glass), washing filter residues twice, and discarding. And combining the filtrate and the washing solution for later use. At this time, SiO in the solution2The content is 5-10%.
Adding 20% NaCl liquid into water glass according to the volume ratio of the water glass liquid to the 20% NaCl liquid of 100: 8; adding n-butanol according to the volume ratio of the water glass liquid to the n-butanol of 10000: 40, fully stirring, adding 40% sulfuric acid under the stirring state to adjust the pH value to 9, standing for 5 hours at room temperature, then heating to 80 ℃, stirring, adding 40% sulfuric acid to adjust the pH value to 7, curing for 40 minutes, filtering, washing and flashing to obtain the high-activity white carbon black finished product.
Example 3: the method for extracting alumina from fly ash and co-producing white carbon black simultaneously comprises the following steps:
1. the fly ash is ground to 450 meshes, and is subjected to mechanical magnetic force deferrization, and then is roasted and activated at 650 ℃ for 1.5 hours.
2. Mixing the activated fly ash and ammonium sulfate according to the requirement, uniformly stirring according to the weight ratio of the alumina to the ammonium sulfate in the fly ash of 1: 5.5, and entering a reactor to perform solid phase reaction for 2 hours at the temperature of 410 ℃.
3. Adding water into the above reactant, stirring and leaching for 30 min under boiling condition at normal pressure, and filtering.
4. Adding ammonia gas (ammonia water) into the filtrate obtained in the previous step in proportion, forming aluminum hydroxide and ferric hydroxide mixed precipitate and ammonium sulfate solution by taking the molar ratio of the reaction amount of aluminum oxide in the fly ash to the ammonia gas (ammonia water) as 1: 7.5, and after solid-liquid separation, evaporating, concentrating and drying the liquid.
5. The solid part is dissolved by sodium hydroxide solution to form a mixture of sodium aluminate solution and ferric hydroxide precipitate, and the alkali dissolution process is carried out at 75 ℃ under normal pressure. The initial concentration of alkali solution for alkali dissolution is [ Na]2O]Stirring and reacting for 30 minutes when the concentration is 150g/L, boiling for 1-5 minutes after the aluminum hydroxide is completely dissolved,to facilitate the precipitation of ferric hydroxide. Because the ferric hydroxide does not react with the alkali, the ferric hydroxide still exists in the sodium aluminate liquid in a precipitation form, and the aim of removing iron is fulfilled by filtering and separating. And washing filter residues for producing high-purity ferric oxide. Combining the washing liquid and the filtrate, removing the carbon dioxide decomposition process to prepare aluminum hydroxide,
6. after filtering and removing iron, adding seed carbon component into sodium aluminate solution, calcining formed aluminium hydroxide to prepare Al2O3。
7. In the step 3, adding 4 times of water by weight of SiO (in weight ratio) into the filter residue obtained after filtration according to the dry matter of the filter residue2/Na2Adding sodium hydroxide solution into O3.6, reacting for 50 min under 0.25MPa, filtering to remove impurities to obtain high-modulus silicic acidSodium liquid (water glass), and filter residue is discarded after being washed twice. And combining the filtrate and the washing solution for later use. At this time, SiO in the solution2The content is 5-10%.
Adding 20% NaCl liquid into water glass according to the volume ratio of the water glass liquid to the 20% NaCl liquid of 100: 6; adding n-butyl alcohol according to the volume ratio of the water glass liquid to the n-butyl alcohol of 10000: 37, fully stirring, adding 30% sulfuric acid under the stirring state to adjust the pH value to 8.5, standing for 4 hours at room temperature, then heating to 75 ℃, stirring, adding 30% sulfuric acid to adjust the pH value to 6.5, curing for 30 minutes, filtering, washing and flashing to obtain the high-activity white carbon black finished product.
Claims (3)
1. A method for extracting alumina from fly ash and co-producing white carbon black is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
firstly, grinding the fly ash to 400-500 meshes, removing iron by mechanical magnetic force, and then roasting and activating at 600-700 ℃ for 1-2 hours;
secondly, mixing the activated fly ash and ammonium sulfate according to the requirement, uniformly stirring according to the weight ratio of the alumina to the ammonium sulfate in the fly ash of 1: 5-6, feeding the mixture into a reactor, and carrying out solid-phase reaction at the temperature of 360-460 ℃ for 1-3 hours;
adding water into the reactant, stirring and leaching for 20-40 minutes under a normal pressure boiling state, and filtering;
fourthly, adding ammonia gas into the filtrate obtained in the previous step in proportion, wherein the molar ratio of the reaction amount of alumina in the fly ash to the ammonia gas is 1: 7-8, forming aluminum hydroxide and ferric hydroxide mixed precipitate and an ammonium sulfate solution, and after solid-liquid separation, evaporating, concentrating and drying the liquid;
fifthly, melting the aluminum hydroxide precipitate by using a sodium hydroxide solution to form a mixture of a sodium aluminate solution and an iron hydroxide precipitate, wherein the alkali dissolution process is carried out at normal pressure and 60-90 ℃, and the initial concentration of alkali liquor for alkali dissolution is controlled to be Na2O]Within the range of 140-170 g/L,
sixthly, after filtering and deironingPreparation of Al2O3The process of (2) is carried out according to the Bayer process.
2. The method for extracting aluminum oxide and co-producing white carbon black from fly ash according to claim 1, which is characterized by comprising the following steps:
in the third step, adding 3-5 times of water by weight of SiO into the filter residue obtained after filtering2/Na2Adding a sodium hydroxide solution into the mixture with the O being 3.4-4, reacting for 40-60 minutes under the pressure of 0.2-0.3 Mpa, filtering out impurities to obtain a high-modulus sodium silicate liquid, adding a dispersing agent and a surfactant into water glass, fully stirring, adding sulfuric acid to adjust the pH value under the stirring state according to requirements to obtain superfine silicon dioxide precipitate, and after solid-liquid separation, cleaning, drying and crushing the solid to obtain the white carbon black.
3. The method for extracting aluminum oxide and co-producing white carbon black from fly ash according to claim 1 or 2, which is characterized by comprising the following steps: ammonia may be substituted for ammonia.
Priority Applications (1)
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