CN117509697A - Method for efficiently preparing aluminum fluoride from aluminum ash - Google Patents
Method for efficiently preparing aluminum fluoride from aluminum ash Download PDFInfo
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- CN117509697A CN117509697A CN202311659076.0A CN202311659076A CN117509697A CN 117509697 A CN117509697 A CN 117509697A CN 202311659076 A CN202311659076 A CN 202311659076A CN 117509697 A CN117509697 A CN 117509697A
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- 238000000034 method Methods 0.000 title claims abstract description 66
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 44
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 title claims abstract description 33
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 76
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000008569 process Effects 0.000 claims abstract description 33
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 20
- 238000009833 condensation Methods 0.000 claims abstract description 16
- 230000005494 condensation Effects 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 33
- 238000002485 combustion reaction Methods 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 239000007790 solid phase Substances 0.000 claims description 22
- 238000003682 fluorination reaction Methods 0.000 claims description 19
- 239000003546 flue gas Substances 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005243 fluidization Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004334 fluoridation Methods 0.000 claims description 3
- 238000005338 heat storage Methods 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012320 chlorinating reagent Substances 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000008188 pellet Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 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
- 239000011230 binding agent Substances 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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)
Abstract
The invention discloses a method for efficiently preparing aluminum fluoride from aluminum ash, which comprises the following steps: grinding aluminum ash, preheating, oxidizing and denitrifying, chloridizing aluminum, iron and magnesium in the oxidized aluminum ash into aluminum chloride, ferric chloride and magnesium chloride by adopting silicon chloride, obtaining high-purity aluminum chloride through multistage condensation, separation and purification, gasifying, preheating the aluminum chloride, reacting the aluminum chloride with silicon tetrafluoride to generate aluminum fluoride products and silicon chloride, and recycling the silicon chloride in the chloridizing process. According to the invention, the oxidation denitrification efficiency of the aluminum ash is remarkably improved through grinding and activating, silicon chloride is used as a chlorinating agent in the chlorination process, carbon does not need to be matched, a chlorination product is easy to separate, the operation is simple and convenient, aluminum fluoride is prepared by fluorinating aluminum chloride by adopting silicon tetrafluoride, the byproduct silicon chloride can be recycled in a system, the production cost is effectively reduced, and meanwhile, the system energy utilization rate is high, the harmless treatment of the aluminum ash and the large-scale efficient preparation of the aluminum fluoride can be realized, and the method has good economic benefit and social benefit.
Description
Technical Field
The invention relates to the field of chemical nonferrous metallurgy environmental protection, in particular to a method for efficiently preparing aluminum fluoride from aluminum ash.
Background
The aluminum ash is an industrial byproduct generated in the processes of electrolytic aluminum, cast aluminum production and waste aluminum regeneration, the annual byproduct aluminum ash in the aluminum industry in China is more than 300 ten thousand tons, and because the aluminum ash contains hazardous substances such as aluminum nitride, soluble fluoride salt, chloride salt and the like, the aluminum ash is listed in the national hazardous waste directory, and the harmless treatment and the high-value utilization of the aluminum ash have important significance for the green high-quality development of the aluminum industry.
The harmless treatment of aluminum ash mainly comprises denitrification and desalination, and the most common denitrification method is to bake aluminum ash in air at high temperature to convert aluminum nitride into nitrogen and aluminum oxide, however, a compact aluminum oxide film is easy to form on the surface of aluminum nitride particles in the oxidizing and roasting process, so that the further progress of denitrification reaction is hindered, and the denitrification efficiency is lower. Chinese patent application CN112744850A discloses a comprehensive utilization method of secondary aluminum ash resources, which comprises the steps of firstly preparing the secondary aluminum ash and sodium alkali into pellets with the size of 30-200mm by using a binder, then placing the pellets in a high-temperature kiln for roasting, and converting aluminum oxide generated by oxidizing aluminum nitride into sodium aluminate by using sodium alkali, thereby relieving the blocking effect of the generated aluminum oxide film and strengthening denitrification reaction. The scheme can improve the denitrification efficiency by utilizing the alkali sintering, but the alkali addition amount is larger, the production cost is higher, the pellet diameter is larger, the heating is uneven, the solid phase reaction temperature is higher, the reaction time is long, and the energy consumption is larger. Chinese patent application CN110902706a discloses a method for preparing polyaluminium chloride from aluminum ash, firstly, making the aluminum ash and coke into pellets of 5-20mm under the action of binder, then roasting them in moving bed under 700-1100 deg.c in chlorine gas to convert aluminum nitride into nitrogen gas and aluminum chloride. According to the scheme, although aluminum nitride can be denitrified and aluminum chloride with higher added value can be obtained, the raw materials used in chloridizing roasting are pellets with larger particle size, the heating is uneven, and the diffusion resistance of generated aluminum chloride and nitrogen is larger, so that the reaction rate is slower, the efficiency is lower, and the process energy consumption is higher. Chinese patent application CN112850762A discloses a method for preparing aluminum chloride and utilizing the whole components by chloridizing-oxygen pressure conversion of aluminum ash pellets, firstly, uniformly mixing aluminum ash and coking coal according to a certain proportion to prepare pellets, and then roasting the pellets in chlorine at the temperature of 1000 ℃ of a moving bed to obtain products such as nitrogen and aluminum chloride, silicon chloride, magnesium chloride and the like with higher added values. The scheme can treat aluminum ash harmlessly and realize high-value utilization of elements such as aluminum, silicon, magnesium and the like, but the problems of low reaction rate, low efficiency, high energy consumption and the like caused by high gas phase diffusion resistance due to the adoption of pellet chlorination are also existed.
Therefore, aiming at the current situation that the aluminum ash cannot be efficiently utilized in the current process technology, the denitrification and desalination process is enhanced through the process and the technology innovation, the reaction efficiency is improved, the process energy consumption is reduced, and the preparation of high-added-value products by utilizing the aluminum resources in the aluminum ash is a key point for realizing large-scale efficient cleaning and high-value utilization of the aluminum ash.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for efficiently preparing aluminum fluoride from aluminum ash.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for efficiently preparing aluminum fluoride from aluminum ash comprises the following steps:
s1, grinding: grinding the aluminum ash to obtain fine ash;
s2, preheating: preheating the fine ash obtained in the step S1 to obtain hot fine ash;
s3, combustion preheating I: the combustion of the excessive oxygen and the fuel is utilized to obtain high-temperature oxygen-enriched flue gas, and the high-temperature oxygen-enriched flue gas is sent into the oxidation process of the step S4;
s4, oxidizing: oxidizing and denitrifying the hot fine ash obtained in the step S2 by utilizing high-temperature oxygen-enriched flue gas to obtain high-temperature oxidized flue gas and oxide, wherein the high-temperature oxidized flue gas is sent into a preheating procedure of the step S2 and is used for preheating the fine ash through heat exchange;
s5, chloridizing: carrying out chlorination reaction on high-temperature silicon chloride and the oxide obtained in the step S4 to obtain chlorinated flue gas and chlorinated slag, and sending the chlorinated flue gas into a multistage condensation process in the step S9;
s6, gasifying I: gasifying the silicon chloride to obtain gas-phase silicon chloride, and conveying the gas-phase silicon chloride into a heat exchange cooling step I of the step S6;
s7, heat exchange and cooling I: cooling the chloridized slag obtained in the step S5 by utilizing gas-phase chloridized silicon through heat exchange to obtain hot chloridized silicon and tailings, and sending the hot chloridized silicon into a combustion preheating step II in the step S8;
s8, combustion preheating II: preheating the hot silicon chloride obtained in the step S7 through the combustion of air and fuel to obtain high-temperature silicon chloride and combustion tail gas I, and sending the high-temperature silicon chloride into a chlorination process in the step S5;
s9, multistage condensation: carrying out multistage condensation separation and purification on the chloridized flue gas obtained in the step S5 to respectively obtain solid-phase aluminum chloride, solid-phase ferric chloride and circulating silicon chloride I, wherein the circulating silicon chloride I is sent into a heat exchange cooling I working procedure in the step S7 and is used for cooling chloridized slag through heat exchange;
s10, gasifying II: gasifying the solid-phase aluminum chloride obtained in the step S9 to obtain gas-phase aluminum chloride;
s11, heat exchange: preheating the gas-phase aluminum chloride obtained in the step S10 to obtain hot aluminum chloride;
s12, fluoridation: carrying out a fluorination reaction on high-temperature silicon tetrafluoride and the hot aluminum chloride obtained in the step S11 to obtain hot aluminum fluoride and high-temperature fluorinated flue gas, wherein the high-temperature fluorinated flue gas is sent to a heat exchange procedure of the step S11 and is used for preheating gas-phase aluminum chloride through heat exchange, and the low-temperature fluorinated flue gas after heat exchange is sent to a separation procedure of the step S15;
s13, heat exchange and cooling II: cooling the hot aluminum fluoride obtained in the step S12 by utilizing silicon tetrafluoride through heat exchange to obtain an aluminum fluoride product and hot silicon tetrafluoride;
s14, combustion preheating III: preheating the hot silicon tetrafluoride obtained in the step S13 by utilizing combustion of air and fuel to obtain high-temperature silicon tetrafluoride and combustion tail gas II, and sending the high-temperature silicon tetrafluoride into a fluorination process of the step S12;
s15, separating: and separating the low-temperature fluorinated flue gas to obtain circulating silicon tetrafluoride and circulating silicon chloride II, wherein the circulating silicon tetrafluoride is sent to the heat exchange cooling II process of the step S13 and used for cooling the hot aluminum fluoride through heat exchange, and the circulating silicon chloride II is sent to the heat exchange cooling I process of the step S7 and used for cooling the chloride slag through heat exchange.
Further, in step S1, the fine ash has a particle size <1 μm.
Further, in the step S4, the temperature of the oxidation and denitrification is 400-600 ℃ and the time is 0.1-0.5h, the oxidation and denitrification reactor is a fluidized bed reactor, an inert oxide is arranged in the fluidized bed reactor and is used for assisting fluidization and heat accumulation, the inert oxide is one or a combination of two of spherical alumina particles and spherical zirconia particles, and the particle size of the inert oxide is 0.5-5mm.
Further, in the step S5, the temperature of the chlorination reaction is 700-900 ℃ and the time is 0.5-1h, the chlorination reaction reactor is a fluidized bed reactor, inert oxide is arranged in the fluidized bed reactor and used for assisting fluidization and heat accumulation, the inert oxide is spherical silica particles, and the granularity of the spherical silica particles is 0.5-5mm.
Further, in step S9, solid-phase ferric chloride is obtained by condensing at 200-290 ℃ and then solid-phase aluminum chloride is obtained by condensing at 70-170 ℃.
Further, in the step S12, the temperature of the fluorination reaction is 500-700 ℃ and the time is 0.5-1h, the reactor of the fluorination reaction is a fluidized bed reactor, seed powder is arranged in the fluidized bed reactor, and the seed powder is 0.1-0.5mm of aluminum fluoride particles.
Further, in step S15, the low-temperature fluorinated flue gas is separated at 20-50 ℃ to obtain liquid-phase recycled silicon chloride ii and gas-phase recycled silicon tetrafluoride.
The invention has the beneficial effects that:
1. the invention does not need to pelletize, can obviously improve the reaction activity of aluminum ash oxidation denitrification through grinding and activation, and has high reaction efficiency;
2. according to the invention, the fluidized bed provided with the inert large-particle oxide is adopted for oxidation denitrification and chlorination reaction, the inert large-particle oxide can inhibit fine particle agglomeration, break bubbles, strengthen mass transfer and heat transfer between gas and solid phases, and simultaneously play a role in heat accumulation, so that the reaction efficiency is high and the stability of system operation is effectively improved;
3. according to the invention, silicon chloride is used as a chlorinating agent, carbon is not required, the operation is simple and convenient, no carbon emission is generated in the chlorination process, and the chlorinated product is easy to separate and purify;
4. according to the invention, aluminum fluoride is prepared by the reaction of silicon tetrafluoride and aluminum chloride in a fluidized bed, and seed powder is arranged to provide nucleation sites and matrixes for newly generated aluminum fluoride, so that the fluorination reaction is promoted, the product purity is high, the collection is convenient, and meanwhile, the byproduct silicon chloride can be recycled in the chlorination process, so that the cost is effectively saved;
5. the invention has high waste heat recovery and utilization rate, and effectively improves the heat efficiency of the whole process system;
6. the invention not only can realize innocent treatment of aluminum ash, but also can efficiently convert aluminum resources in the aluminum ash into aluminum fluoride with high added value, and has remarkable economic and social benefits.
Drawings
FIG. 1 is a flow chart of a method according to various embodiments of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that, while the present embodiment provides a detailed implementation and a specific operation process on the premise of the present technical solution, the protection scope of the present invention is not limited to the present embodiment.
Example 1
The embodiment provides a method for efficiently preparing aluminum fluoride from aluminum ash, which comprises the following steps as shown in fig. 1:
s1, grinding: grinding the aluminum ash to obtain fine ash with granularity smaller than 1 mu m.
S2, preheating: and (3) preheating the fine ash obtained in the step (S1) to obtain hot fine ash.
S3, combustion preheating I: and (3) obtaining high-temperature oxygen-enriched flue gas by using the combustion of the excessive oxygen and the fuel, and sending the high-temperature oxygen-enriched flue gas into the oxidation process of the step S4.
S4, oxidizing: oxidizing and denitrifying the hot fine ash obtained in the step S2 by utilizing high-temperature oxygen-enriched flue gas to obtain high-temperature oxidized flue gas and oxide, wherein the high-temperature oxidized flue gas is sent into a preheating procedure of the step S2 and is used for preheating the fine ash through heat exchange; the temperature of the oxidative denitrification is 400 ℃ and the time is 0.5h, the reactor is a fluidized bed reactor, inert oxide is arranged in the fluidized bed reactor and used for assisting fluidization and heat accumulation, and the inert oxide is spherical alumina particles with the granularity of 0.5mm.
S5, chloridizing: carrying out chlorination reaction on high-temperature silicon chloride and the oxide obtained in the step S4 to obtain chlorinated flue gas and chlorinated slag, and sending the chlorinated flue gas into a multistage condensation process in the step S9; the temperature of the chlorination reaction is 700 ℃ and the time is 1h, the reactor is a fluidized bed reactor, inert oxide is arranged in the fluidized bed reactor and used for assisting fluidization and heat accumulation, the inert oxide is spherical silica particles, and the granularity of the spherical silica particles is 5mm.
S6, gasifying I: gasifying the silicon chloride to obtain gas-phase silicon chloride, and conveying the gas-phase silicon chloride into a heat exchange cooling step I of the step S6;
s7, heat exchange and cooling I: cooling the chloridized slag obtained in the step S5 by utilizing gas-phase chloridized silicon through heat exchange to obtain hot chloridized silicon and tailings, and sending the hot chloridized silicon into a combustion preheating step II in the step S8;
s8, combustion preheating II: preheating the hot silicon chloride obtained in the step S7 through the combustion of air and fuel to obtain high-temperature silicon chloride and combustion tail gas I, and sending the high-temperature silicon chloride into a chlorination process in the step S5;
s9, multistage condensation: and (3) carrying out multistage condensation separation and purification on the chlorinated flue gas obtained in the step (S5) to respectively obtain solid-phase aluminum chloride, solid-phase ferric chloride and circulating silicon chloride I, wherein the circulating silicon chloride I is sent into the heat exchange cooling I working procedure in the step (S7) and is used for cooling the chlorinated slag through heat exchange. Wherein, solid-phase ferric chloride is obtained by condensation at 200 ℃ and then solid-phase aluminum chloride is obtained by condensation at 70 ℃.
S10, gasifying II: gasifying the solid-phase aluminum chloride obtained in the step S9 to obtain gas-phase aluminum chloride;
s11, heat exchange: preheating the gas-phase aluminum chloride obtained in the step S10 to obtain hot aluminum chloride;
s12, fluoridation: carrying out a fluorination reaction on high-temperature silicon tetrafluoride and the hot aluminum chloride obtained in the step S11 to obtain hot aluminum fluoride and high-temperature fluorinated flue gas, wherein the high-temperature fluorinated flue gas is sent to a heat exchange procedure of the step S11 and is used for preheating gas-phase aluminum chloride through heat exchange, and the low-temperature fluorinated flue gas after heat exchange is sent to a separation procedure of the step S15; the temperature of the fluorination reaction is 500 ℃ and the time is 1h, the reactor is a fluidized bed reactor, seed powder is arranged in the fluidized bed reactor and is used for providing nucleation sites and matrixes for newly generated aluminum fluoride and promoting the fluorination reaction, and the seed powder is 0.1mm of aluminum fluoride particles.
S13, heat exchange and cooling II: cooling the hot aluminum fluoride obtained in the step S12 by utilizing silicon tetrafluoride through heat exchange to obtain an aluminum fluoride product and hot silicon tetrafluoride;
s14, combustion preheating III: preheating the hot silicon tetrafluoride obtained in the step S13 by utilizing combustion of air and fuel to obtain high-temperature silicon tetrafluoride and combustion tail gas II, and sending the high-temperature silicon tetrafluoride into a fluorination process of the step S12;
s15, separating: and separating the low-temperature fluorinated flue gas at 20 ℃ to obtain liquid-phase circulating silicon chloride II and gas-phase circulating silicon tetrafluoride, wherein the circulating silicon tetrafluoride is sent to a heat exchange cooling II process of the step S13 and used for cooling hot aluminum fluoride through heat exchange, and the circulating silicon chloride II is sent to a heat exchange cooling I process of the step S7 and used for cooling the chloride slag through heat exchange.
Example 2
The process flow of this example is substantially the same as example 1, except that: in the step S4, the temperature of the oxidative denitrification is 600 ℃, the time is 0.1h, and the granularity of spherical alumina particles in the fluidized bed reactor is 5mm; in the step S5, the temperature of the chlorination reaction is 900 ℃, the time is 0.5h, and the granularity of spherical silica particles in the fluidized bed reactor is 0.5mm; in the step S9, firstly condensing at 290 ℃ to obtain solid-phase ferric chloride, and then condensing at 170 ℃ to obtain solid-phase aluminum chloride; in the step S12, the temperature of the fluorination reaction is 700 ℃, the fluorination time is 0.5h, and the seed powder in the fluidized bed reactor is 0.5mm of aluminum fluoride particles; in the step S15, the low-temperature fluorinated flue gas is separated at 50 ℃ to obtain liquid-phase circulating silicon chloride II and gas-phase circulating silicon tetrafluoride.
Example 3
The process flow of this example is substantially the same as example 1, except that: in the step S4, the temperature of the oxidative denitrification is 500 ℃, the time is 0.3h, and the granularity of spherical zirconia particles in the fluidized bed reactor is 0.5mm; in the step S5, the temperature of the chlorination reaction is 800 ℃, the time is 0.6h, and the granularity of spherical silica particles in the fluidized bed reactor is 3mm; in the step S9, firstly, solid-phase ferric chloride is obtained by condensation at 250 ℃, and then solid-phase aluminum chloride is obtained by condensation at 100 ℃; in the step S12, the temperature of the fluorination reaction is 600 ℃, the fluorination time is 0.8h, and the seed powder in the fluidized bed reactor is 0.3mm of aluminum fluoride particles; in the step S15, the low-temperature fluorinated flue gas is separated at the temperature of 30 ℃ to obtain liquid-phase circulating silicon chloride II and gas-phase circulating silicon tetrafluoride.
Example 4
The process flow of this example is substantially the same as example 1, except that: in the step S4, the temperature of the oxidative denitrification is 530 ℃, the time is 0.2h, and the granularity of spherical zirconia particles in the fluidized bed reactor is 5mm; in the step S5, the temperature of the chlorination reaction is 780 ℃, the time is 0.7h, and the granularity of spherical silica particles in the fluidized bed reactor is 1mm; in the step S9, firstly, solid-phase ferric chloride is obtained by condensation at 220 ℃, and then solid-phase aluminum chloride is obtained by condensation at 120 ℃; in the step S12, the temperature of the fluorination reaction is 620 ℃, the fluorination time is 0.7h, and the seed powder in the fluidized bed reactor is 0.2mm of aluminum fluoride particles; in the step S15, the low-temperature fluorinated flue gas is separated at 40 ℃ to obtain liquid-phase circulating silicon chloride II and gas-phase circulating silicon tetrafluoride.
Various modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing teachings and are intended to be included within the scope of the following claims.
Claims (7)
1. A method for efficiently preparing aluminum fluoride from aluminum ash is characterized by comprising the following steps: the method comprises the following steps:
s1, grinding: grinding the aluminum ash to obtain fine ash;
s2, preheating: preheating the fine ash obtained in the step S1 to obtain hot fine ash;
s3, combustion preheating I: the combustion of the excessive oxygen and the fuel is utilized to obtain high-temperature oxygen-enriched flue gas, and the high-temperature oxygen-enriched flue gas is sent into the oxidation process of the step S4;
s4, oxidizing: oxidizing and denitrifying the hot fine ash obtained in the step S2 by utilizing high-temperature oxygen-enriched flue gas to obtain high-temperature oxidized flue gas and oxide, wherein the high-temperature oxidized flue gas is sent into a preheating procedure of the step S2 and is used for preheating the fine ash through heat exchange;
s5, chloridizing: carrying out chlorination reaction on high-temperature silicon chloride and the oxide obtained in the step S4 to obtain chlorinated flue gas and chlorinated slag, and sending the chlorinated flue gas into a multistage condensation process in the step S9;
s6, gasifying I: gasifying the silicon chloride to obtain gas-phase silicon chloride, and conveying the gas-phase silicon chloride into a heat exchange cooling step I of the step S6;
s7, heat exchange and cooling I: cooling the chloridized slag obtained in the step S5 by utilizing gas-phase chloridized silicon through heat exchange to obtain hot chloridized silicon and tailings, and sending the hot chloridized silicon into a combustion preheating step II in the step S8;
s8, combustion preheating II: preheating the hot silicon chloride obtained in the step S7 through the combustion of air and fuel to obtain high-temperature silicon chloride and combustion tail gas I, and sending the high-temperature silicon chloride into a chlorination process in the step S5;
s9, multistage condensation: carrying out multistage condensation separation and purification on the chloridized flue gas obtained in the step S5 to respectively obtain solid-phase aluminum chloride, solid-phase ferric chloride and circulating silicon chloride I, wherein the circulating silicon chloride I is sent into a heat exchange cooling I working procedure in the step S7 and is used for cooling chloridized slag through heat exchange;
s10, gasifying II: gasifying the solid-phase aluminum chloride obtained in the step S9 to obtain gas-phase aluminum chloride;
s11, heat exchange: preheating the gas-phase aluminum chloride obtained in the step S10 to obtain hot aluminum chloride;
s12, fluoridation: carrying out a fluorination reaction on high-temperature silicon tetrafluoride and the hot aluminum chloride obtained in the step S11 to obtain hot aluminum fluoride and high-temperature fluorinated flue gas, wherein the high-temperature fluorinated flue gas is sent to a heat exchange procedure of the step S11 and is used for preheating gas-phase aluminum chloride through heat exchange, and the low-temperature fluorinated flue gas after heat exchange is sent to a separation procedure of the step S15;
s13, heat exchange and cooling II: cooling the hot aluminum fluoride obtained in the step S12 by utilizing silicon tetrafluoride through heat exchange to obtain an aluminum fluoride product and hot silicon tetrafluoride;
s14, combustion preheating III: preheating the hot silicon tetrafluoride obtained in the step S13 by utilizing combustion of air and fuel to obtain high-temperature silicon tetrafluoride and combustion tail gas II, and sending the high-temperature silicon tetrafluoride into a fluorination process of the step S12;
s15, separating: and separating the low-temperature fluorinated flue gas to obtain circulating silicon tetrafluoride and circulating silicon chloride II, wherein the circulating silicon tetrafluoride is sent to the heat exchange cooling II process of the step S13 and used for cooling the hot aluminum fluoride through heat exchange, and the circulating silicon chloride II is sent to the heat exchange cooling I process of the step S7 and used for cooling the chloride slag through heat exchange.
2. The method according to claim 1, characterized in that in step S1, the particle size of the fine ash is <1 μm.
3. The method according to claim 1, wherein in step S4, the temperature of the oxidative denitrification is 400-600 ℃ and the time is 0.1-0.5h, the reactor of the oxidative denitrification is a fluidized bed reactor, inert oxide is arranged in the fluidized bed reactor for assisting fluidization and heat storage, the inert oxide is one or a combination of two of spherical alumina particles and spherical zirconia particles, and the particle size of the inert oxide is 0.5-5mm.
4. The method according to claim 1, wherein in step S5, the temperature of the chlorination reaction is 700-900 ℃ and the time is 0.5-1h, the chlorination reaction is carried out in a fluidized bed reactor, inert oxide is arranged in the fluidized bed reactor for assisting fluidization and heat storage, the inert oxide is spherical silica particles, and the particle size of the spherical silica particles is 0.5-5mm.
5. The method according to claim 1, wherein in step S9, solid phase ferric chloride is obtained by first condensing at 200-290 ℃ and then solid phase aluminum chloride is obtained by condensing at 70-170 ℃.
6. The method according to claim 1, wherein in step S12, the fluorination reaction is performed at a temperature of 500-700 ℃ for a time of 0.5-1h, and the fluorination reaction is performed in a fluidized bed reactor in which seed powder is provided, and the seed powder is 0.1-0.5mm of aluminum fluoride particles.
7. The method according to claim 1, wherein in step S15, the low temperature fluorinated flue gas is separated at 20-50 ℃ to obtain liquid phase recycled silicon ii chloride and gas phase recycled silicon tetrafluoride.
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