CN116375064B - A mechanical activation combined with oxygen pressure leaching method for extracting alumina from fly ash - Google Patents
A mechanical activation combined with oxygen pressure leaching method for extracting alumina from fly ash Download PDFInfo
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- CN116375064B CN116375064B CN202310387072.5A CN202310387072A CN116375064B CN 116375064 B CN116375064 B CN 116375064B CN 202310387072 A CN202310387072 A CN 202310387072A CN 116375064 B CN116375064 B CN 116375064B
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- alumina
- oxygen pressure
- mechanical activation
- pressure leaching
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- 239000010881 fly ash Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002386 leaching Methods 0.000 title claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 13
- 239000001301 oxygen Substances 0.000 title claims abstract description 13
- 238000004137 mechanical activation Methods 0.000 title claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- -1 aluminum ions Chemical class 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 15
- 238000011084 recovery Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 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 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 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
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910004882 Na2S2O8 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
本发明公开了一种从粉煤灰中提取氧化铝的机械活化结合氧压浸出法，涉及固体废弃物的资源化利用技术。具体发方法包粉煤灰煅烧粉碎、粉煤灰混合焦硫酸钠球磨活化、活化料混合过硫酸钠和去离子水升温反应、固液分离和检测等步骤。本发明具有能耗低，反应条件温和，无污染气体产生等优点，所得Al的最高提取率为98.92％，本发明为从固体废弃物回收有用元素提供了新的技术支撑。
The invention discloses a mechanical activation combined with oxygen pressure leaching method for extracting aluminum oxide from fly ash, and relates to a resource utilization technology for solid waste. The specific method includes the steps of calcining and crushing fly ash, ball milling activation of fly ash mixed with sodium pyrosulfate, heating reaction of activated material mixed with sodium persulfate and deionized water, solid-liquid separation and detection. The invention has the advantages of low energy consumption, mild reaction conditions, no polluting gas generation, etc. The maximum extraction rate of Al obtained is 98.92%. The invention provides new technical support for recovering useful elements from solid waste.
Description
Technical Field
The invention relates to a resource utilization technology of solid waste, in particular to a mechanical activation combined oxygen pressure leaching method for extracting aluminum oxide from fly ash.
Background
Fly ash produced by coal-fired power plants is an industrial solid waste which has small volume and light weight and contains rich heavy metal elements, and long-term accumulation can pollute the atmosphere, soil and water resources, so that the resource utilization of the fly ash has become the focus of attention worldwide. It is worth mentioning that fly ash contains a large amount of valuable elements such as aluminum, silicon, iron, gallium and the like, wherein the content of alumina in the high-alumina fly ash is up to more than 50%, and the fly ash is a precious potential aluminum resource. However, improper recovery methods may cause serious environmental and waste disposal problems. Based on this, it is very interesting to develop a clean and efficient technique for recovering aluminum element from fly ash.
Typical existing metallurgical methods for extracting alumina from fly ash generally include sodium-calcium roasting, acid and molten salt methods (ammonium sulfate/ammonium bisulfate), which have advantages and disadvantages. For example, the sodium-calcium roasting method shows the flexibility of operation and the maturity of technology, but needs higher roasting temperature and generates larger amount of waste residues, and secondly, the sodium-calcium roasting method is easy to dissolve out a large amount of amorphous silicon dioxide in the fly ash, so that silicon-aluminum separation is difficult, and complex technology is needed to further separate and purify the leaching solution, so that the recovery cost is high, the acid method has low energy consumption, generates fewer waste residues and silicon is insoluble in acid, but the reaction system has high equipment requirement and needs strong anti-corrosion treatment equipment, and ammonium sulfate is used as an extracting agent in the molten salt method, and ammonia is generated in the sintering process and pollutes the atmosphere although the recovery efficiency is high. Therefore, developing a new process that can efficiently and cleanly recover alumina under mild conditions is a major and hot spot concern for current researchers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a mechanical activation combined oxygen pressure leaching method for extracting aluminum oxide from fly ash, which utilizes sodium pyrosulfate to mechanically activate the fly ash, and utilizes a sodium persulfate high pressure leaching method to effectively destroy stable crystal phases such as mullite, corundum and the like in the fly ash, so that a higher Al extraction rate is obtained under milder conditions.
In order to achieve the above object, the technical scheme of the present invention is realized by the following technical scheme:
a persulfate high-pressure leaching method for extracting aluminum oxide from fly ash comprises the following steps:
1) Calcining the fly ash at 800 ℃ and grinding to obtain pretreated fly ash;
2) Placing the pretreated fly ash and sodium pyrosulfate into a ball milling tank, and performing ball milling activation to obtain activated clinker;
3) Adding activated clinker into sodium persulfate and deionized water, stirring uniformly, and then transferring all the mixture into a high-pressure reaction kettle for reaction;
4) After the reaction is finished, carrying out solid-liquid separation on clinker to obtain filtrate and filter residue containing aluminum ions;
5) And diluting 2-5 g of filtrate to 50g, measuring the content of Al 3+ in the filtrate by using an inductively coupled plasma-mass spectrometer, and converting the content into the content of alumina.
Further, the calcination of the fly ash in the step 1) is performed in a muffle furnace for 3 hours, and the pulverized fly ash is ground and then screened by a 200-mesh sieve to ensure that the particle size of the fly ash is less than 45 um.
Further, in the step 2), the pretreated fly ash and sodium pyrosulfate are mixed according to the molar ratio of sodium pyrosulfate to alumina in the pretreated fly ash of (0-20): 1, more preferably (0-4): 1, and the ball milling time is 0-10 hours, more preferably 0-4 hours.
Further, in the step 2), the planetary ball mill is adopted to ball-mill and activate the fly ash, the mass ratio of the agate balls to the materials is 3:1, and the replacement time is 15 min/time by adopting a positive and negative replacement ball milling mode.
Wherein, in step 2), the main principle of activating the fly ash by utilizing sodium pyrosulfate is that sodium pyrosulfate is an ionic compound and its sulfur anion has oxidizing property, S 2O7 2- is a dimer of sulfate anions, and SO 4 2- has bridging oxygen atoms, sulfate groups are easy to be connected with Al 3+ to form a complex three-dimensional network, and almost all oxygen atoms in tetrahedral SO 4 2- groups can be combined with Al 3+, and the oxygen atoms are not combined with aluminum terminal but are further connected with sulfur atoms (Al-O-S structure), thereby destroying part of the Al-O-Si structure. While Na + shows an electron acceptor that is interactive with oxygen atoms in the aluminosilicate, contributing to the hopeful formation of anionic sulfate complexes by Al 3+ that disrupt the confinement of the original crystal lattice. The equation for the reaction process is as follows:
Na2S2O7→Na2SO4+SO3 (1)
Al 2O3 (corundum) +3Na 2S2O7→2Na3Al(SO4)3 (2)
Al 6Si2O13 (mullite) +9Na 2S2O7→6Na3Al(SO4)3+2SiO2 (3)
Al 2O3 (glassy phase) +3Na 2S2O7→2Na3Al(SO4)3 (4)
Further, in the step 3), the addition amount of sodium persulfate is (0-20) to 1, more preferably (0-4) to 1 according to the molar ratio of sodium persulfate to aluminum oxide in the fly ash, and the addition amount of deionized water is (1-20) to 1, more preferably (2-8) to 1 according to the liquid-solid ratio of deionized water to (activated clinker plus sodium persulfate);
The main principle of leaching the fly ash by utilizing sodium persulfate under high pressure is that the sodium persulfate can be decomposed into H + generated by HSO 4 - and O 2,HSO4 - when being contacted with water, and can form interfacial hydroxyl with a large amount of unsaturated oxygen in the solution, so that interfacial oxygen is lost, crystal lattice vacancies are generated, the lattice defects of aluminosilicate crystals in the fly ash are caused, and the constraint of oxygen atoms on aluminum atoms is weakened, so that the aluminum atoms are free from lattice constraint and enter the solution. The equation for the reaction process is as follows:
Na2S2O8+H2O→2NaHSO4+1/2O2(pH=3~7) (1)
Al2O3+6NaHSO4→Al2(SO4)3+3Na2SO4+3H2O (2)
In step 3), the stirring rotation speed is set to 300rpm in the reaction process in step 3), the reaction temperature is 140-240 ℃, and the leaching temperature is preferably 140-240 ℃ to mainly create subcritical water environment. When the temperature and pressure of water are lower than its critical temperature Tc (374.3 ℃) and critical pressure Pc (22.1 Mpa), and in the vicinity of the proximity state, it is called subcritical water. Research has shown that subcritical water is an excellent reaction medium capable of promoting the reaction rate and thus the recovery of aluminum.
Further, in the step 3), the initial heating rate of the reaction kettle is set to be 5 ℃ per minute, and the heating rate is set to be 3 ℃ per minute after the initial heating rate is close to 80% of the target temperature, so as to prevent the reaction kettle from suffering from the phenomenon of temperature runaway;
Further, in the step 4), the filter residue is dried at 105 ℃ in a suction filtration mode for solid-liquid separation, and can be further recycled, such as preparing a molecular sieve or a porous material.
Further, in step 5), three parallel filtrates are taken each time, and the content of elements is measured by using an inductively coupled plasma-mass spectrometer, so that the confidence interval of the test result is ensured to be 90-95%.
Further, in step 5), the formula of the concentration of Al 3+ in the solution converted into alumina is: Wherein M Al2O3 and M Al are the relative molecular masses of Al 2O3 and Al respectively, g.mol-1;m is the mass of the fly ash in a single test, g, V is the volume of the aluminum leaching solution, mL, and W Al2O3 is the mass fraction of Al 2O3 in the fly ash.
The invention has the following beneficial effects:
1. Compared with the prior art, the method has the advantages that firstly, the ball milling activation method is adopted to fully mix sodium pyrosulfate with the fly ash, firstly, the Si-O-Al bond and the Al-O bond on the surface of the fly ash are destroyed by utilizing pyrosulfate ions, the Al < 3+ > is hopefully destroyed to form an anionic sulfate complex by the constraint of the original crystal lattice, then, the mullite structure in the fly ash is further destroyed by utilizing the sodium persulfate high-pressure leaching method, the lattice defect of the aluminosilicate crystal is caused, the constraint of oxygen atoms to aluminum atoms is weakened, and therefore, the aluminum atoms are free from the lattice constraint and enter the solution.
2. The method has the advantages that the adopted process is milder, the leaching rate can be higher when the leaching temperature is 200 ℃, and compared with the traditional sodium carbonate or ammonium sulfate/ammonium bisulfate roasting method which can obtain higher Al extraction rate at 800 ℃ or even above, the energy consumption is low and the efficiency is high.
3. The method has the advantages that the used reagent is mild, no corrosiveness is generated, no pollution gas is generated in the reaction process, the problem of treatment of waste acid, alkali and other solutions is not needed to be considered, meanwhile, the recovery rate of aluminum is high, and the maximum recovery rate of aluminum is 98.92 percent, so that the method is a clean and efficient valuable element recovery method.
Drawings
FIG. 1 is a schematic illustration of a process flow of the present invention;
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Extracting alumina from fly ash:
1. Calcining the fly ash, namely selecting low-alumina fly ash, taking the low-alumina fly ash from a power plant of Anhui Huai Nanping, calcining for 3 hours at 800 ℃ in a muffle furnace, taking out, crushing and sieving with a 200-mesh sieve to obtain pretreated fly ash;
2.5 g of pretreated fly ash and 8.6314g of sodium pyrosulfate (CFA/Na 2S2O7 =1:3) are accurately weighed in an agate tank containing 65g of agate balls, the rotating speed of a ball mill is set to be 300rpm, the time interval between forward and reverse alternation is 15 min/time, and ball milling is carried out for 2h.
3. After the ball milling is finished, transferring the materials into a 250ml beaker, weighing 12.3384g of sodium persulfate (CFA/Na 2S2O8 =1:4) in the beaker, adding 104ml of deionized water (the liquid-solid ratio is 4:1), uniformly stirring, transferring the mixed materials into a reaction kettle, setting the rotating speed to 300rpm, heating to 160 ℃ by adopting the heating rate of 5 ℃ per minute, then heating to 200 ℃ by adjusting the heating rate, and keeping the temperature for 120min.
4. And (3) carrying out solid-liquid separation in a suction filtration mode after the reaction is finished to obtain leaching liquid.
Example 2:
Extracting alumina from fly ash:
1. Calcining the fly ash, namely selecting low-alumina fly ash, taking the low-alumina fly ash from a power plant of Anhui Huai Nanping, calcining for 3 hours at 800 ℃ in a muffle furnace, taking out, crushing and sieving with a 200-mesh sieve to obtain pretreated fly ash;
2. Accurately weighing 5g of pretreated fly ash in an agate tank containing 65g of agate balls, setting the rotating speed of a ball mill to be 300rpm, and carrying out ball milling for 2 hours at a forward-reverse transition time interval of 15 min/time.
3. After ball milling, transferring the materials into a 250ml beaker, weighing 24.6773g of sodium persulfate (CFA/Na 2S2O8 =1:8) in the beaker, adding 119ml of deionized water (with a liquid-solid ratio of 4:1), uniformly stirring, transferring the mixed materials into a reaction kettle, setting the rotating speed to 300rpm, heating to 160 ℃ at a heating rate of 5 ℃ per minute, then heating to 200 ℃ at a heating rate of 3 ℃ per minute, and keeping the temperature for 120 minutes.
4. And (3) carrying out solid-liquid separation in a suction filtration mode after the reaction is finished to obtain leaching liquid.
Example 3:
Extracting alumina from fly ash:
1. Calcining the fly ash, namely selecting low-alumina fly ash, taking the low-alumina fly ash from a power plant of Anhui Huai Nanping, calcining for 3 hours at 800 ℃ in a muffle furnace, taking out, crushing and sieving with a 200-mesh sieve to obtain pretreated fly ash;
2.5 g of pretreated fly ash and 8.6314g of sodium pyrosulfate (CFA/Na 2S2O7 =1:3) are accurately weighed in an agate tank containing 65g of agate balls, the rotating speed of a ball mill is set to be 300rpm, the time interval between forward and reverse alternation is 15 min/time, and ball milling is carried out for 2h.
3. After ball milling, the materials are transferred into a 250ml beaker, 24.6773g of sodium persulfate (CFA/Na 2S2O8 =1:8) is weighed into the beaker, 154ml of deionized water (the liquid-solid ratio is 4:1) is added, the mixture is transferred into a reaction kettle after being stirred uniformly, the rotating speed is set to 300rpm, the temperature is firstly increased to 160 ℃ by adopting the temperature increasing rate of 5 ℃ per minute, then the temperature increasing rate is adjusted to 3 ℃ per minute, the temperature is increased to 200 ℃, and the temperature is kept constant for 120 minutes.
4. And (3) carrying out solid-liquid separation in a suction filtration mode after the reaction is finished to obtain leaching liquid.
Example 4:
Extracting alumina from fly ash:
1. Calcining the fly ash, namely selecting low-alumina fly ash, taking the low-alumina fly ash from a power plant of Anhui Huai Nanping, calcining for 3 hours at 800 ℃ in a muffle furnace, taking out, crushing and sieving with a 200-mesh sieve to obtain pretreated fly ash;
2.5 g of pretreated fly ash and 8.6314g of sodium pyrosulfate (CFA/Na 2S2O7 =1:3) are accurately weighed in an agate tank containing 65g of agate balls, the rotating speed of a ball mill is set to be 300rpm, the time interval between forward and reverse alternation is 15 min/time, and ball milling is carried out for 1h.
3. After ball milling, the materials are transferred into a 250ml beaker, 24.6773g of sodium persulfate (CFA/Na 2S2O8 =1:8) is weighed into the beaker, 154ml of deionized water (the liquid-solid ratio is 4:1) is added, the mixture is transferred into a reaction kettle after being stirred uniformly, the rotating speed is set to 300rpm, the temperature is firstly increased to 160 ℃ by adopting the temperature increasing rate of 5 ℃ per minute, then the temperature increasing rate is adjusted to 3 ℃ per minute, the temperature is increased to 200 ℃, and the temperature is kept constant for 120 minutes.
4. And (3) carrying out solid-liquid separation in a suction filtration mode after the reaction is finished to obtain leaching liquid.
Example 5:
Extracting alumina from fly ash:
1. Calcining the fly ash, namely selecting low-alumina fly ash, taking the low-alumina fly ash from a power plant of Anhui Huai Nanping, calcining for 3 hours at 800 ℃ in a muffle furnace, taking out, crushing and sieving with a 200-mesh sieve to obtain pretreated fly ash;
2.5 g of pretreated fly ash and 8.6314g of sodium pyrosulfate (CFA/Na 2S2O7 =1:3) are accurately weighed in an agate tank containing 65g of agate balls, the rotating speed of a ball mill is set to be 300rpm, the time interval between forward and reverse alternation is 15 min/time, and ball milling is carried out for 2h.
3. After the completion, the materials were transferred into a 250ml beaker, 24.6773g of sodium persulfate (CFA/Na 2S2O8 =1:8) was weighed into the beaker, 154ml of deionized water (liquid-solid ratio is 4:1) was added, after stirring uniformly, the mixed materials were transferred into a reaction kettle, the rotational speed was set at 300rpm, the temperature was raised to 160 ℃ by using a temperature raising rate of 5 ℃ per minute, then the temperature raising rate was adjusted to 3 ℃ per minute and raised to 200 ℃, and the temperature was kept constant for 60 minutes.
4. After the reaction is finished, carrying out solid-liquid separation by adopting a suction filtration mode to obtain leaching liquid
Example 6:
Extracting alumina from fly ash:
1. Calcining the fly ash, namely selecting low-alumina fly ash, taking the low-alumina fly ash from a power plant of Anhui Huai Nanping, calcining for 3 hours at 800 ℃ in a muffle furnace, taking out, crushing and sieving with a 200-mesh sieve to obtain pretreated fly ash;
2.5 g of pretreated fly ash and 8.6314g of sodium pyrosulfate (CFA/Na 2S2O7 =1:3) are accurately weighed in an agate tank containing 65g of agate balls, the rotating speed of a ball mill is set to be 300rpm, the time interval between forward and reverse alternation is 15 min/time, and ball milling is carried out for 2h.
3. After the ball milling is finished, transferring the materials into a 250ml beaker, weighing 12.3384g of sodium persulfate (CFA/Na 2S2O8 =1:4) in the beaker, adding 104ml of deionized water (the liquid-solid ratio is 4:1), uniformly stirring, transferring the mixed materials into a reaction kettle, setting the rotating speed to 300rpm, heating to 130 ℃ at a heating rate of 5 ℃ per minute, then heating to 160 ℃ at a heating rate of 3 ℃ per minute, and keeping the temperature for 120 minutes.
4. And (3) carrying out solid-liquid separation in a suction filtration mode after the reaction is finished to obtain leaching liquid.
Example 7:
Extracting alumina from fly ash:
1. Calcining the fly ash, namely selecting low-alumina fly ash, taking the low-alumina fly ash from a power plant of Anhui Huai Nanping, calcining for 3 hours at 800 ℃ in a muffle furnace, taking out, crushing and sieving with a 200-mesh sieve to obtain pretreated fly ash;
2.5 g of pretreated fly ash and 8.6314g of sodium pyrosulfate (CFA/Na 2S2O7 =1:3) are accurately weighed in an agate tank containing 65g of agate balls, the rotating speed of a ball mill is set to be 300rpm, the time interval between forward and reverse alternation is 15 min/time, and ball milling is carried out for 2h.
3. After the ball milling is finished, transferring the materials into a 250ml beaker, weighing 12.3384g of sodium persulfate (CFA/Na 2S2O8 =1:4) in the beaker, adding 77ml of deionized water (liquid-solid ratio is 2:1), uniformly stirring, transferring the mixed materials into a reaction kettle, setting the rotating speed to 300rpm, heating to 160 ℃ by adopting the heating rate of 5 ℃ per minute, then heating to 200 ℃ by adjusting the heating rate, and keeping the temperature for 120min.
4. And (3) carrying out solid-liquid separation in a suction filtration mode after the reaction is finished to obtain leaching liquid.
Sucking 2g of leaching solution, diluting to 50g, and detecting the content of aluminum ions in the leaching solution by using an inductively coupled plasma luminescence spectrometer to obtain the leaching rate of aluminum oxide of 45%;
And (3) detection:
2g each of the leachate obtained in examples 1 to 7 was diluted to 50g, and the content of aluminum ions in the leachate was detected by an inductively coupled plasma-luminescence spectrometer (ICP-MS for short), and the specific results are shown in the following table:
as is clear from the above table, the effect of the extraction of example 3 is optimal.
Finally, it should be noted that the above examples are only for the purpose of clearly illustrating the technical solution of the present invention and are not to be construed as limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and that the modification or replacement does not deviate from the scope of the technical solution of the embodiments of the present invention in nature of the corresponding technical solution.
Claims (8)
1. A mechanical activation combined oxygen pressure leaching method for extracting aluminum oxide from fly ash is characterized by comprising the following steps:
1) Calcining the fly ash at 800 ℃ and grinding to obtain pretreated fly ash;
2) Placing the pretreated fly ash and sodium pyrosulfate into a ball milling tank, and performing ball milling activation to obtain activated clinker, wherein the mixing proportion of the pretreated fly ash and the sodium pyrosulfate is mixed according to the molar proportion of the sodium pyrosulfate to the alumina in the pretreated fly ash (0-20) to 1, and the ball milling time is 0-10 hours;
3) Adding activated clinker into sodium persulfate and deionized water, stirring and uniformly mixing, and then transferring all the mixture into a high-pressure reaction kettle for reaction, wherein the adding amount of the sodium persulfate is added according to the molar ratio of the sodium persulfate to the pretreated fly ash alumina in the activated clinker (0-20) to 1, the adding amount of the deionized water is added according to the liquid-solid ratio of the deionized water to the activated clinker plus the sodium persulfate (1-20) to 1, and the reaction temperature range is 140-240 ℃;
4) And after the reaction is finished, carrying out solid-liquid separation on the clinker to obtain filtrate and filter residues containing aluminum ions.
2. The method for extracting alumina from fly ash by combining mechanical activation and oxygen pressure leaching according to claim 1, wherein the calcination of the fly ash in the step 1) is performed in a muffle furnace for 3h, and the pulverized fly ash is screened by a 200-mesh sieve to ensure that the particle size of the fly ash is below 45 um.
3. The method for extracting aluminum oxide from fly ash by combining mechanical activation and oxygen pressure leaching according to claim 1, wherein in the step 2), a planetary ball mill is adopted to ball-mill and activate the fly ash, the mass ratio of agate balls to materials is 3:1, and a positive and negative transition ball-milling mode is adopted, so that the replacement time is 15 min/time.
4. A mechanical activation combined with oxygen pressure leaching process for extracting alumina from fly ash according to claim 1, wherein: the stirring rotation speed is set to be 300rpm in the reaction process in the step 3).
5. The method of combining mechanical activation and oxygen pressure leaching for extracting aluminum oxide from fly ash according to claim 1, wherein the initial heating rate of the reaction kettle in the step 3) is set to be 5 ℃ per minute, and the heating rate is set to be 3 ℃ per minute after the temperature is raised to 80% of the target temperature.
6. The method for extracting alumina from fly ash by combining mechanical activation and oxygen pressure leaching according to claim 1, wherein the solid-liquid separation in the step 4) adopts a suction filtration mode.
7. The method for extracting aluminum oxide from fly ash by combining mechanical activation and oxygen pressure leaching according to claim 1, wherein in the step 4), three filtrates are parallel each time, and the content of elements is measured by using an inductively coupled plasma-mass spectrometer, so that the confidence interval of the test result is ensured to be 90-95%.
8. The method of claim 1, wherein the step 4) is followed by diluting the filtrate to 50g, and the content of Al 3+ in the filtrate is measured by using an inductively coupled plasma-mass spectrometer, and converted into the content of alumina, and the formula of converting the concentration of Al 3+ in the solution into the content of alumina is as follows:
;
Wherein M Al2O3 and M Al are the relative molecular masses of Al 2O3 and Al, g.mol -1, M is the mass of the fly ash in a single test, g, V is the volume of the aluminum leaching solution, mL, and W Al2O3 is the mass fraction of Al 2O3 in the fly ash.
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