CN117509569A - Method for efficiently preparing aluminum nitride from aluminum ash - Google Patents
Method for efficiently preparing aluminum nitride from aluminum ash Download PDFInfo
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- CN117509569A CN117509569A CN202311658972.5A CN202311658972A CN117509569A CN 117509569 A CN117509569 A CN 117509569A CN 202311658972 A CN202311658972 A CN 202311658972A CN 117509569 A CN117509569 A CN 117509569A
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- 238000000034 method Methods 0.000 title claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 47
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 25
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 62
- 238000005121 nitriding Methods 0.000 claims abstract description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 55
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000460 chlorine Substances 0.000 claims abstract description 49
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 49
- 239000011777 magnesium Substances 0.000 claims abstract description 39
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 32
- -1 magnesium nitride Chemical class 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 11
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000005243 fluidization Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 25
- 238000002485 combustion reaction Methods 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002893 slag Substances 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 6
- 238000009825 accumulation Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005338 heat storage Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000008188 pellet Substances 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for efficiently preparing aluminum nitride from aluminum ash, which comprises the following steps: grinding aluminum ash, preheating, performing fluidization chlorination denitrification under the assistance of large particles, converting aluminum and aluminum nitride in the aluminum ash into aluminum chloride and nitrogen, condensing, recycling, gasifying and preheating the aluminum chloride, reacting with magnesium nitride to generate a mixture of aluminum nitride and magnesium chloride, crystallizing and purifying the mixture to obtain high-purity aluminum nitride, electrolyzing by-product magnesium chloride to generate magnesium and chlorine, recycling the chlorine for aluminum ash denitrification, and reacting the magnesium and nitrogen to generate magnesium nitride for recycling the aluminum chloride. The invention does not need to pelletize and match carbon, has low temperature and high efficiency of chloridizing and denitriding, adopts magnesium nitride to carry out nitriding on aluminum chloride to prepare aluminum nitride, is easy to separate and purify, and can provide magnesium and chlorine for a system through electrolysis by a byproduct magnesium chloride, has high cyclic utilization rate and high system energy utilization rate, can realize innocuous treatment of aluminum ash and large-scale and efficient preparation of aluminum nitride, and 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 nitride 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 nitride from aluminum ash.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for efficiently preparing aluminum nitride from aluminum ash comprises the following steps:
s1, grinding: grinding aluminum ash into fine powder to obtain fine ash;
s2, preheating I: preheating the fine ash obtained in the step S1 to obtain hot fine ash;
s3, chloridizing: performing chloridizing denitrification on the hot fine ash obtained in the step S2 by utilizing high-temperature chlorine to obtain high-temperature chloridized flue gas and hot chloridized slag; the high-temperature chlorinated flue gas is sent to a preheating step I of the step S2 and is used for carrying out heat exchange preheating on fine ash, and the low-temperature chlorinated flue gas after heat exchange is sent to a condensation recovery step of the step S7;
s4, heat exchange and cooling: cooling the hot chloridized slag obtained in the step S3 by utilizing normal-temperature chlorine through heat exchange to obtain cold chloridized slag and hot chlorine, and sending the hot chlorine into a combustion preheating step I in the step S5;
s5, combustion preheating I: heating the hot chlorine obtained in the step S4 through the combustion of air and fuel to obtain high-temperature chlorine and combustion tail gas I, and sending the high-temperature chlorine into the chlorination process of the step S3;
s6, washing and drying: washing and drying the cold chlorination slag obtained in the step S4 by using deionized water to obtain washing liquid and tailings;
s7, condensing and recycling: condensing low-temperature chloridized flue gas obtained after heat exchange and preheating of fine ash to obtain chlorine, nitrogen and solid-phase aluminum chloride, and sending the chlorine and the nitrogen into a separation procedure of the step S8;
s8, separating: separating the chlorine and the nitrogen obtained in the step S7 to obtain circulating chlorine I and circulating nitrogen, wherein the circulating chlorine I is sent to the heat exchange cooling process of the step S4 and used for carrying out heat exchange cooling on hot chloridized slag, and the circulating nitrogen is sent to the nitriding process of the step S15;
s9, gasifying: gasifying the solid-phase aluminum chloride obtained in the step S7 to obtain gas-phase aluminum chloride;
s10, combustion preheating II: heating the gas-phase aluminum chloride obtained in the step S9 through the combustion of air and fuel to obtain high-temperature aluminum chloride and combustion tail gas II;
s11, preheating II: preheating magnesium nitride to obtain hot magnesium nitride, and feeding the hot magnesium nitride into the procedure I of the step S12;
s12, nitriding I: carrying out nitridation reaction on the high-temperature aluminum chloride obtained in the step S10 and the hot magnesium nitride obtained in the step S11 to obtain nitride and high-temperature nitriding smoke, and sending the high-temperature nitriding smoke into a heat exchange preheating step II of the step S11 for carrying out heat exchange preheating on the magnesium nitride;
s13, crystallizing: crystallizing and purifying the nitride obtained in the step S12 to obtain aluminum nitride and magnesium chloride;
s14, electrolysis: electrolyzing the magnesium chloride obtained in the step S13 to obtain magnesium and circulating chlorine II, and sending the circulating chlorine II into a heat exchange cooling process of the step S4 for carrying out heat exchange cooling on hot chloride slag;
s15, nitriding II: and (3) nitriding the magnesium obtained in the step (S14) by utilizing nitrogen and the circulating nitrogen obtained in the step (S8) to obtain circulating magnesium nitride, and sending the circulating magnesium nitride into a heat exchange preheating step (II) of the step (S12) to perform nitridation reaction with high-temperature aluminum chloride.
Further, in step S1, the fine ash has a particle size <1 μm.
Further, in the step S3, the temperature of the chloridizing denitrification is 400-600 ℃ and the time is 0.1-1h; the chloridizing denitrification reactor is a fluidized bed reactor, wherein an inert oxide is arranged in the fluidized bed reactor and 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 0.5-3mm.
Further, in step S7, the condensation temperature is 20-170 ℃.
Further, in step S12, the particle size of the thermal magnesium nitride is less than 1 μm, the nitriding reaction temperature is 450-650 ℃, the nitriding reaction time is 0.1-1h, the nitriding reaction 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 0.5-3mm.
Further, in step S2 and step S11, the preheating is performed by indirect heat exchange.
Further, in step S15, the nitriding temperature is 400-600 ℃ and the nitriding time is 0.1-1h.
Further, in step S13, the crystallization temperature is 1500-1700 ℃, and the crystallization time is 0.5-2h.
The invention has the beneficial effects that:
1. according to the invention, the chloridizing reaction activity of the aluminum ash can be obviously improved without pelletizing and grinding activation, the reaction temperature is reduced, the energy consumption is saved, the aluminum and aluminum nitride in the aluminum ash are directly chloridized by adopting chlorine, no carbon is required, the operation is simple and convenient, the tail gas does not contain carbon dioxide, the environment is protected, and meanwhile, excessive chlorine is easy to separate and recycle;
2. according to the invention, the fluidized bed provided with the inert large-particle oxide is adopted to carry out chloridizing denitrification of fine aluminum ash and nitriding reaction of fine magnesium nitride and aluminum chloride, the inert large-particle oxide can inhibit fine particle agglomeration, break bubbles, strengthen mass and heat transfer between gas and solid phases, and simultaneously play a role in heat storage, so that the reaction efficiency and the stability of system operation are effectively improved;
3. compared with an alumina carbothermic reduction nitriding method, the reaction temperature is obviously reduced, the reaction product is easy to separate and purify, and the product purity is high;
4. according to the invention, magnesium nitride is used as a nitrogen source for preparing aluminum nitride, and the byproduct magnesium chloride is easy to separate, and can be recycled in a system by generating magnesium and chlorine through electrolysis, 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 nitride 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 nitride from aluminum ash, which comprises the following steps as shown in fig. 1:
s1, grinding: grinding aluminum ash into fine powder to obtain fine ash with granularity smaller than 1 μm.
S2, preheating I: and (3) preheating the fine ash obtained in the step (S1) to obtain hot fine ash.
S3, chloridizing: performing chloridizing denitrification on the hot fine ash obtained in the step S2 by utilizing high-temperature chlorine to obtain high-temperature chloridized flue gas and hot chloridized slag; the high-temperature chlorinated flue gas is sent to a preheating step I of the step S2 and is used for carrying out heat exchange preheating on fine ash, and the low-temperature chlorinated flue gas after heat exchange is sent to a condensation recovery step of the step S7; in the chloridizing denitrification, the temperature is 400 ℃ and the time is 1h, the reactor is a fluidized bed reactor, and spherical zirconia particles with the granularity of 3mm are arranged in the fluidized bed reactor and are used for assisting fluidization and heat accumulation.
S4, heat exchange and cooling: cooling the hot chloridized slag obtained in the step S3 by utilizing normal-temperature chlorine through heat exchange to obtain cold chloridized slag and hot chlorine, and sending the hot chlorine into a combustion preheating step I in the step S5;
s5, combustion preheating I: heating the hot chlorine obtained in the step S4 through the combustion of air and fuel to obtain high-temperature chlorine and combustion tail gas I, and sending the high-temperature chlorine into the chlorination process of the step S3;
s6, washing and drying: washing and drying the cold chlorination slag obtained in the step S4 by using deionized water to obtain washing liquid and tailings;
s7, condensing and recycling: condensing low-temperature chloridized flue gas obtained after heat exchange and preheating of fine ash, wherein the condensing temperature is 20 ℃, chlorine, nitrogen and solid-phase aluminum chloride are obtained, and the chlorine and the nitrogen are sent to a separation procedure of the step S8;
s8, separating: separating the chlorine and the nitrogen obtained in the step S7 to obtain circulating chlorine I and circulating nitrogen, wherein the circulating chlorine I is sent to the heat exchange cooling process of the step S4 and used for carrying out heat exchange cooling on hot chloridized slag, and the circulating nitrogen is sent to the nitriding process of the step S15;
s9, gasifying: gasifying the solid-phase aluminum chloride obtained in the step S7 to obtain gas-phase aluminum chloride;
s10, combustion preheating II: heating the gas-phase aluminum chloride obtained in the step S9 through the combustion of air and fuel to obtain high-temperature aluminum chloride and combustion tail gas II;
s11, preheating II: preheating magnesium nitride to obtain hot magnesium nitride, and feeding the hot magnesium nitride into the procedure I of the step S12; the particle size of the magnesium nitride is <1 μm.
S12, nitriding I: carrying out nitridation reaction on the high-temperature aluminum chloride obtained in the step S10 and the hot magnesium nitride obtained in the step S11 to obtain nitride and high-temperature nitriding smoke, and sending the high-temperature nitriding smoke into a heat exchange preheating step II of the step S11 for carrying out heat exchange preheating on the magnesium nitride; wherein the nitriding reaction temperature is 450 ℃, the nitriding reaction time is 1h, the nitriding reaction reactor is a fluidized bed reactor, and spherical alumina particles with the granularity of 0.5mm are arranged in the fluidized bed reactor and are used for assisting fluidization and heat accumulation.
S13, crystallizing: performing crystallization and purification on the nitride obtained in the step S12, wherein the crystallization temperature is 1500 ℃, and the crystallization time is 2 hours, so that aluminum nitride and magnesium chloride are obtained;
s14, electrolysis: electrolyzing the magnesium chloride obtained in the step S13 to obtain magnesium and circulating chlorine II, and sending the circulating chlorine II into a heat exchange cooling process of the step S4 for carrying out heat exchange cooling on hot chloride slag;
s15, nitriding II: nitriding the magnesium obtained in the step S14 by utilizing nitrogen and the circulating nitrogen obtained in the step S8, wherein the nitriding temperature is 400 ℃, the nitriding time is 1h, and the circulating magnesium nitride is obtained and is sent into a heat exchange preheating II process of the step S12 to perform nitriding reaction with high-temperature aluminum chloride.
Example 2
The process flow of this example is substantially the same as example 1, except that: in the step S3, the temperature of the chloridizing and denitrifying is 600 ℃, the chloridizing and denitrifying time is 0.1h, and spherical zirconia particles with the granularity of 0.5mm are arranged in a fluidized bed reactor of the chloridizing reaction; in step S7, the condensing temperature is 170 ℃; in the step S12, the nitriding reaction temperature is 650 ℃, the nitriding reaction time is 0.1h, and spherical alumina particles with the granularity of 3mm are arranged in a fluidized bed reactor for the nitriding reaction; in the step S13, the crystallization temperature is 1700 ℃, and the crystallization time is 0.5h; in step S15, the nitriding temperature is 600 ℃ and the nitriding time is 0.1h.
Example 3
The process flow of this example is substantially the same as example 1, except that: in the step S3, the chloridizing and denitriding temperature is 500 ℃, the chloridizing and denitriding time is 0.5h, and spherical alumina particles with the granularity of 0.5mm are arranged in a fluidized bed reactor for chloridizing reaction; in the step S7, the condensing temperature is 100 ℃; in the step S12, the nitriding reaction temperature is 550 ℃, the nitriding reaction time is 0.4h, and spherical zirconia particles with the granularity of 3mm are arranged in a fluidized bed reactor for the nitriding reaction; in the step S13, the crystallization temperature is 1600 ℃, and the crystallization time is 0.9h; in step S15, the nitriding temperature is 500 ℃ and the nitriding time is 0.6h.
Example 4
The process flow of this example is substantially the same as example 1, except that: in the step S3, the chloridizing and denitriding temperature is 530 ℃, the chloridizing and denitriding time is 0.4h, and spherical alumina particles with the granularity of 3mm are arranged in a fluidized bed reactor for chloridizing reaction; in the step S7, the condensing temperature is 80 ℃; in the step S12, the nitriding reaction temperature is 480 ℃, the nitriding reaction time is 0.7h, and spherical zirconia particles with the granularity of 0.5mm are arranged in a fluidized bed reactor for the nitriding reaction; in the step S13, the crystallization temperature is 1580 ℃ and the crystallization time is 1.1h; in step S15, the nitriding temperature is 530 ℃, and the nitriding time is 0.5h.
Example 5
The process flow of this example is substantially the same as example 1, except that: in the step S3, the chloridizing and denitriding temperature is 450 ℃, the chloridizing and denitriding time is 0.8h, and spherical alumina particles with the granularity of 1.5mm are arranged in a fluidized bed reactor for chloridizing reaction; in the step S7, the condensing temperature is 70 ℃; in the step S12, the nitriding reaction temperature is 580 ℃, the nitriding reaction time is 0.3h, and spherical zirconia particles with the granularity of 1.5mm are arranged in a fluidized bed reactor for the nitriding reaction; in the step S13, the crystallization temperature is 1550 ℃ and the crystallization time is 1.6h; in step S15, the nitriding temperature was 570℃and the nitriding time was 0.3h.
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 (8)
1. A method for efficiently preparing aluminum nitride from aluminum ash is characterized by comprising the following steps: the method comprises the following steps:
s1, grinding: grinding aluminum ash into fine powder to obtain fine ash;
s2, preheating I: preheating the fine ash obtained in the step S1 to obtain hot fine ash;
s3, chloridizing: performing chloridizing denitrification on the hot fine ash obtained in the step S2 by utilizing high-temperature chlorine to obtain high-temperature chloridized flue gas and hot chloridized slag; the high-temperature chlorinated flue gas is sent to a preheating step I of the step S2 and is used for carrying out heat exchange preheating on fine ash, and the low-temperature chlorinated flue gas after heat exchange is sent to a condensation recovery step of the step S7;
s4, heat exchange and cooling: cooling the hot chloridized slag obtained in the step S3 by utilizing normal-temperature chlorine through heat exchange to obtain cold chloridized slag and hot chlorine, and sending the hot chlorine into a combustion preheating step I in the step S5;
s5, combustion preheating I: heating the hot chlorine obtained in the step S4 through the combustion of air and fuel to obtain high-temperature chlorine and combustion tail gas I, and sending the high-temperature chlorine into the chlorination process of the step S3;
s6, washing and drying: washing and drying the cold chlorination slag obtained in the step S4 by using deionized water to obtain washing liquid and tailings;
s7, condensing and recycling: condensing low-temperature chloridized flue gas obtained after heat exchange and preheating of fine ash to obtain chlorine, nitrogen and solid-phase aluminum chloride, and sending the chlorine and the nitrogen into a separation procedure of the step S8;
s8, separating: separating the chlorine and the nitrogen obtained in the step S7 to obtain circulating chlorine I and circulating nitrogen, wherein the circulating chlorine I is sent to the heat exchange cooling process of the step S4 and used for carrying out heat exchange cooling on hot chloridized slag, and the circulating nitrogen is sent to the nitriding process of the step S15;
s9, gasifying: gasifying the solid-phase aluminum chloride obtained in the step S7 to obtain gas-phase aluminum chloride;
s10, combustion preheating II: heating the gas-phase aluminum chloride obtained in the step S9 through the combustion of air and fuel to obtain high-temperature aluminum chloride and combustion tail gas II;
s11, preheating II: preheating magnesium nitride to obtain hot magnesium nitride, and feeding the hot magnesium nitride into the procedure I of the step S12;
s12, nitriding I: carrying out nitridation reaction on the high-temperature aluminum chloride obtained in the step S10 and the hot magnesium nitride obtained in the step S11 to obtain nitride and high-temperature nitriding smoke, and sending the high-temperature nitriding smoke into a heat exchange preheating step II of the step S11 for carrying out heat exchange preheating on the magnesium nitride;
s13, crystallizing: crystallizing and purifying the nitride obtained in the step S12 to obtain aluminum nitride and magnesium chloride;
s14, electrolysis: electrolyzing the magnesium chloride obtained in the step S13 to obtain magnesium and circulating chlorine II, and sending the circulating chlorine II into a heat exchange cooling process of the step S4 for carrying out heat exchange cooling on hot chloride slag;
s15, nitriding II: and (3) nitriding the magnesium obtained in the step (S14) by utilizing nitrogen and the circulating nitrogen obtained in the step (S8) to obtain circulating magnesium nitride, and sending the circulating magnesium nitride into a heat exchange preheating step (II) of the step (S12) to perform nitridation reaction with high-temperature aluminum chloride.
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 S3, the temperature of the chloridizing denitrification is 400-600 ℃ for 0.1-1h; the chloridizing denitrification reactor is a fluidized bed reactor, wherein an inert oxide is arranged in the fluidized bed reactor and 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 0.5-3mm.
4. The method according to claim 1, wherein in step S7, the condensing temperature is 20-170 ℃.
5. The method according to claim 1, wherein in step S12, the particle size of the magnesium nitride is less than 1 μm, the nitriding reaction temperature is 450-650 ℃, the nitriding reaction time is 0.1-1h, the nitriding reaction reactor 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 0.5-3mm.
6. The method according to claim 1, wherein in step S2 and step S11, the preheating is performed by indirect heat exchange.
7. The method according to claim 1, wherein in step S15, the nitriding temperature is 400-600 ℃ and the nitriding time is 0.1-1h.
8. The method according to claim 1, wherein in step S13, the crystallization temperature is 1500-1700 ℃ and the crystallization time is 0.5-2h.
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