CN116553590A - Method for treating solid waste generated in aluminum-titanium-boron production process and anhydrous potassium tetrafluoroaluminate - Google Patents

Method for treating solid waste generated in aluminum-titanium-boron production process and anhydrous potassium tetrafluoroaluminate Download PDF

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Publication number
CN116553590A
CN116553590A CN202310514300.0A CN202310514300A CN116553590A CN 116553590 A CN116553590 A CN 116553590A CN 202310514300 A CN202310514300 A CN 202310514300A CN 116553590 A CN116553590 A CN 116553590A
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aluminum
potassium
tetrafluoroaluminate
temperature
potassium tetrafluoroaluminate
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李水兵
魏丽芳
韦丽珍
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Xinxing Light Alloy Material Luoyang Co ltd
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Xinxing Light Alloy Material Luoyang Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/48Halides, with or without other cations besides aluminium
    • C01F7/50Fluorides
    • C01F7/54Double compounds containing both aluminium and alkali metals or alkaline-earth metals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

An anhydrous potassium tetrafluoroaluminate chemical which is a crystal water-free potassium tetrafluoroaluminate obtained by a hot melt production method (dry method). The production method comprises the following steps: placing derivative fluorine-containing salt slag (salt slag generated in the aluminum alloying process taking potassium fluoroaluminate as a main component) synchronously generated in the aluminum titanium boron alloy production process into a smelting furnace: the reaction temperature is raised to 700-1100 ℃, additives containing aluminum, fluorine and potassium are added, the heating and melting reaction time is controlled between 30-60 minutes, and finally the melt forms highly stable potassium tetrafluoroaluminate. The method can carry out resource treatment on the salt slag which is determined to be solid dangerous waste at present and takes the potassium fluoroaluminate as the main component, thereby not only reducing the burden of enterprises and increasing the income of the enterprises, but also reducing the pollution possibly caused to the environment in the dangerous waste transfer process and creating a new treatment way for the resource utilization of dangerous waste.

Description

Method for treating solid waste generated in aluminum-titanium-boron production process and anhydrous potassium tetrafluoroaluminate
Technical Field
The invention relates to chemical articles, in particular to a method for treating solid waste generated in aluminum titanium boron production and a product generated by the method.
Background
Solid waste-potassium fluoroaluminate generated in the aluminum titanium boron production process is always taken as an accessory product to be sold and treated by production enterprises, and along with the increasing importance of China on environmental protection, the potassium fluoroaluminate is listed as solid dangerous waste by China to be strictly managed, for example: in the national hazardous waste directory (2021 edition) published by the country, aluminum ash residues, salt residues, aluminum ash and the like containing potassium fluoroaluminate are listed as hazardous waste, and after being listed as hazardous waste, the accessory products are strictly controlled by the country, and enterprises cannot process and move by themselves, so that potassium fluoroaluminate sold as a product by the production enterprises in daily life becomes a pollutant strictly controlled by the environmental protection department, and great cost burden is caused to the production enterprises.
Disclosure of Invention
The invention adopts a series of process steps of adding proper additives, selecting proper smelting temperature and the like to further smelt the byproduct potassium fluoroaluminate generated in the aluminum titanium boron production process, and the like to recycle the waste such as potassium fluoroaluminate, thereby changing waste into valuables and solving the technical problems of environmental pollution and large enterprise burden at present.
The invention provides a method for treating solid waste generated in an aluminum titanium boron production process, which aims to solve the technical problems and comprises the following steps:
A. putting the waste slag containing aluminum and/or fluorine components generated in the aluminum-titanium-boron production process into a smelting furnace;
B. heating to 700-1100 ℃, adding additives containing aluminum, fluorine and potassium components, and controlling the heating reaction time between 30 and 60 minutes;
D. the final melt forms and separates out a highly stable pure potassium tetrafluoroaluminate chemical.
The waste residues comprising aluminum and/or fluorine components in the step A are derived from salt residues, aluminum ash residues and corresponding dust collecting matters generated in the aluminum titanium boron production process.
The invention further improves that the smelting temperature in the step B is heated in stages, the first stage firstly heats the temperature to between 800 and 950 ℃, then additives are added, and then the temperature is further raised and controlled to between 950 and 1100 ℃.
More preferably, in the step B, the smelting temperature of the first stage is heated to 850-950 ℃, and the heating temperature of the second stage is controlled to 950-1060 ℃.
The additive in the step B is anhydrous aluminum trifluoride and anhydrous potassium fluoride.
The additive in the step B also comprises slaked lime.
The additive in the step B is anhydrous aluminum trifluoride and anhydrous potassium fluoride, and the addition proportion of the additive is determined according to the waste residue components generated in the aluminum titanium boron production process and the purity of the potassium tetrafluoroaluminate required to be generated in the melting reaction.
The method further comprises the following steps between the step B and the step D:
C. after the heating reaction in the step B, keeping the temperature and standing for 45-90 minutes, and gradually cooling the temperature;
after step D, the method further comprises the following steps:
E. and D, cooling potassium tetrafluoroaluminate formed by the melting reaction in the step to about 700 ℃, condensing and crystallizing to a solid state, crushing, and forming products with different specifications for packaging treatment.
And C, keeping the temperature and standing for 50-90 minutes.
The anhydrous potassium tetrafluoroaluminate produced by the solid waste treatment method produced in the aluminum titanium boron production process is potassium tetrafluoroaluminate which does not contain crystal water and has a different lattice arrangement mode from that of the potassium tetrafluoroaluminate synthesized by the traditional wet method.
By adopting the technical scheme, the invention can carry out recycling treatment on the hazardous waste potassium fluoroaluminate which is originally taken as the burden of enterprises, carry out recycling comprehensive utilization on the solid waste taking potassium fluoroaluminate as the main component, smelt the salt slag taking the potassium fluoroaluminate mixture composed of different molecular structures and molecular weights as the main component into a high-purity single-molecular-structure and molecular-weight potassium tetrafluoroaluminate chemical, and carry out recycling treatment on the salt slag taking potassium fluoroaluminate as the main component which is legal as the solid hazardous waste in some countries at present, thereby not only reducing the environmental protection burden of enterprises, but also reducing the pollution possibly caused to the environment in the hazardous waste transferring process and creating a new treatment way for recycling utilization of hazardous waste.
Drawings
Fig. 1 is a phase diagram of a conventional potassium tetrafluoroaluminate.
FIG. 2 is a phase diagram of anhydrous potassium tetrafluoroaluminate produced by the hot melt process of the present invention.
Fig. 3 is an illustration of the requirements for the raw materials of anhydrous potassium tetrafluoroaluminate with different phase ratios as a product in different application fields.
Detailed Description
The method for treating the solid waste generated in the aluminum titanium boron production process comprises the following steps: A. putting the waste slag containing aluminum and/or fluorine components generated in the aluminum-titanium-boron production process into a smelting furnace;
B. heating to 700-1100 ℃, adding additives containing aluminum, fluorine and potassium components, and controlling the heating reaction time between 30 and 60 minutes;
D. the final melt forms and separates out a highly stable pure potassium tetrafluoroaluminate chemical.
The derivative-fluorine-containing salt slag (white, gray and black slag taking potassium fluoroaluminate as main components) synchronously generated in the production process of the titanium boron alloy is already defined as hazardous waste (hazardous waste), the set of hot melting treatment process can further smelt the potassium fluoroaluminate slag (a plurality of potassium fluoroaluminate mixtures with different molecular structures and molecular weights, aluminum oxide, inclusion of potassium fluoroaluminate and the like) which is defined as hazardous waste by adding a certain proportion of additives containing potassium, aluminum and fluorine, and finally forms the potassium tetrafluoroaluminate chemical (CAS number is 14484-69-6) which accords with the international chemical standard, and the potassium tetrafluoroaluminate produced by the method does not contain crystal water and has crystal lattice which is completely different from the traditional potassium tetrafluoroaluminate, and the quality is far superior to that of the traditional wet chemical synthesized potassium tetrafluoroaluminate. In the past, anhydrous potassium fluoride and anhydrous aluminum fluoride have also been used for melt reaction to synthesize potassium tetrafluoroaluminate (dry process), but no matter what molar ratio is used, anhydrous potassium tetrafluoroaluminate with a phase ratio of more than 90% cannot be obtained, and the obtained product must be a mixture of potassium hexafluoroaluminate and potassium tetrafluoroaluminate. The technology of the patent for producing the high-purity anhydrous potassium tetrafluoroaluminate by adopting a hot melting method (dry method) and matching with proper temperature and smelting time control has uniqueness.
The waste residues comprising aluminum and/or fluorine components in the step A are derived from salt residues, aluminum ash residues and corresponding dust collecting matters generated in the aluminum titanium boron production process. The dangerous waste generated synchronously in the production process of the aluminum-titanium-boron alloy in the step A is divided into three parts: 1, fluoride-containing salt slag (salt slag); 2, aluminum ash residues; 3, dust collection; the fluorine-containing salt slag is molten salt slag suspended on the upper part of the aluminum-titanium-boron alloy, which is synchronously generated in the aluminum-titanium-boron alloying process, the aluminum ash slag is suspended slag generated on the surface of the aluminum-titanium-boron alloy purifying process after the aluminum ingot raw material melting process and the salt slag are separated, the fluorine-containing salt slag mainly contains aluminum oxide and is mixed with potassium fluoroaluminate, and the dust collector is the potassium fluoroaluminate obtained by collecting the salt slag by a bag dust collector after the high-temperature volatilization. The aluminum titanium boron alloy is molten aluminum liquid and potassium fluotitanate and potassium fluoborate, and the alloying process of aluminum, titanium and boron elements is realized by hot melting reaction under high temperature environment, the process synchronously generates molten salt slag composed of a plurality of potassium fluoaluminate mixtures with different molecular structures and molecular weights, and the salt slag mainly comprises KAlF due to different specifications of the produced aluminum titanium boron alloy and different proportions of the added potassium fluotitanate and potassium fluoborate in the production process 4 、K 3 AlF 6 、KAl 4 F 13 、KAlF 5 Al and Al 2 O 3 (Al 2 O 2 F) Such a plurality of fluorides are defined as hazardous waste, since they are mixtures of various substances and contain fluorine element in high concentration.
In the step B, the smelting temperature is heated in stages, the first stage firstly heats the temperature to 800-950 ℃, then additives are added, and then the temperature is further raised and controlled to 950-1100 ℃. Considering the complexity of salt slag components, the method adopts a staged heating mode in the smelting process, and can also adopt a mode of pouring molten salt slag and aluminum ash slag into a smelting container for heating the raw materials in the first stage, then, according to the specific components of the treated objects, selecting and adding proper additives, thereby promoting the conversion of the substances, and then, further heating in the second stage, wherein the additives are preferably aluminum trifluoride and anhydrous potassium fluoride; the proportion of the slag is adjusted according to the produced aluminum-titanium-boron alloy (5% Ti, 1% B/5% Ti, 0.6% B/5% Ti, 0.2% B/3% Ti and 1% B) with different specifications, and the purity of potassium tetrafluoroaluminate generated by the melting reaction can be controlled between 95% and 99% (phase ratio) by adjusting the addition amount and the addition proportion of anhydrous aluminum fluoride, anhydrous potassium fluoride and the slag to be treated, if the slag is accurately regulated, the highest purity can reach 99.8%.
More preferably, in the step B, the smelting temperature of the first stage is heated to 850-950 ℃, and the heating temperature of the second stage is controlled to 950-1060 ℃.
In order to further improve the treatment effect, the additive in the step B also comprises slaked lime.
In order to further improve the treatment effect, the following steps are added between the step B and the step D:
C. after the heating reaction in the step B, keeping the temperature and standing for 45-90 minutes, and gradually cooling the temperature;
after step E, the method further comprises the following steps:
E. and D, cooling potassium tetrafluoroaluminate formed by the melting reaction in the step to about 700 ℃, condensing and crystallizing to a solid state, crushing, and forming products with different specifications for packaging treatment.
The invention further preferably comprises the following steps: and C, controlling the heat preservation standing time in the step between 50 and 90 minutes.
The reaction time is increased in the production process, the reaction time in the heating stage is preferably controlled to be about 30 minutes, different heat preservation standing time is selected according to different material components, the temperature is generally controlled to be 45-90 minutes, the preferred control time is 50-90 minutes, and the more preferred control time is about 90 minutes regardless of the production period.
The anhydrous potassium tetrafluoroaluminate produced by the solid waste treatment method produced in the aluminum titanium boron production process is potassium tetrafluoroaluminate which does not contain crystal water and has different crystal lattice arrangement modes. The traditional potassium tetrafluoroaluminate is synthesized by adopting wet chemistry, and the reaction formula is as follows:
Al(OH) 3 +KOH+HF→KAlF 4 ·mH 2 O;
as can be seen from FIG. 1, which contains water of crystallization, the phase of the water of crystallization can be clearly seen in the interval of coordinates 30-35,
the reaction formula of the potassium tetrafluoroaluminate is as follows:
in fig. 2, it can be seen that the crystal water is not contained, and the crystal lattice structure of the potassium tetrafluoroaluminate is completely different from that of the traditional potassium tetrafluoroaluminate by comparing the phase diffraction of fig. 1 and 2, and in fig. 3, the anhydrous potassium tetrafluoroaluminate with different phase ratios has different requirements on the raw materials when the anhydrous potassium tetrafluoroaluminate is used as a product in different application fields. The anhydrous potassium tetrafluoroaluminate has good flowing effect and more sufficient atomization in the aluminum brazing electrostatic dry spraying process, and can greatly improve the electrostatic dry spraying effect. In the aluminum welding engineering, when the anhydrous potassium tetrafluoroaluminate is used as a brazing flux, the melting of materials can be accelerated, bubbles generated in the welding engineering can be reduced, and the welding quality can be influenced. More importantly, the anhydrous potassium tetrafluoroaluminate is used in aluminum electrolysis, so that the electricity consumption can be greatly saved, and according to the data obtained by the applicant test, the electricity cost of 200-500 yuan can be saved in the production of each ton of electrolytic aluminum, and the energy consumption is reduced. The anhydrous potassium tetrafluoroaluminate of the present invention has been identified by Zhengzhou light industry technology institute of technology, inc. (environmental detection center) and has completely met the national regulation requirements, and the conclusion is that: "according to the general rule for solid waste identification", GB34330-2017: "3.1 solid waste" refers to lost original produced during production, life and other activitiesSolid, semi-solid and gaseous articles, materials placed in containers that are of value or that are discarded or discarded without losing value, as well as articles, materials that are subject to solid waste management by law and administration. The potassium tetrafluoroaluminate product produced by Xinxing light alloy (Luoyang) limited company is produced on a dangerous waste reduction and recycling comprehensive utilization production line, and the components of the product are relatively stable, uniform and single, and do not belong to solid waste, and the reason is that: potassium tetrafluoroaluminate is a chemical substance with CAS number 14484-69-6 and molecular formula KAlF 4 White powder, slightly soluble in water, used as a raw material for pesticides, ceramics, glass industry, aluminum electrolysis and aluminum brazing flux.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.

Claims (10)

1. A method for treating solid waste generated in an aluminum titanium boron production process is characterized by comprising the following steps of: the method comprises the following steps:
A. putting the waste slag containing aluminum and/or fluorine components generated in the aluminum-titanium-boron production process into a smelting furnace;
B. heating to 700-1100 ℃, adding additives containing aluminum, fluorine and potassium components, and controlling the heating reaction time between 30 and 60 minutes;
D. the final melt forms and separates out a highly stable pure potassium tetrafluoroaluminate chemical.
2. A processing method according to claim 1, characterized in that: the waste residues comprising aluminum and/or fluorine components in the step A are derived from salt residues, aluminum ash residues and corresponding dust matters generated in the aluminum titanium boron production process.
3. A processing method according to claim 1, characterized in that: in the step B, the smelting temperature is heated in stages, the first stage firstly heats the temperature to 800-950 ℃, then additives are added, and then the temperature is further raised and controlled to 950-1100 ℃.
4. A process according to claim 3, characterized in that: and in the step B, the smelting temperature of the first stage is heated to 850-950 ℃, and the heating temperature of the second stage is controlled to 950-1060 ℃.
5. A treatment method according to any one of claims 1 to 4, characterized in that: the additive in the step B is anhydrous aluminum trifluoride and anhydrous potassium fluoride.
6. A processing method according to claim 5, characterized in that: the additive in the step B also comprises slaked lime.
7. A processing method according to claim 5, characterized in that: the additive in the step B is anhydrous aluminum trifluoride and anhydrous potassium fluoride, and the addition proportion of the additive is determined according to the waste residue components generated in the aluminum titanium boron production process and the purity of the potassium tetrafluoroaluminate required to be generated in the melting reaction.
8. A treatment method according to any one of claims 1 to 4, characterized in that: the method further comprises the following steps between the step B and the step D:
C. after the heating reaction in the step B, keeping the temperature and standing for 45-90 minutes, and gradually cooling the temperature;
after step D, the method further comprises the following steps:
E. and D, cooling potassium tetrafluoroaluminate formed by the melting reaction in the step to about 700 ℃, condensing and crystallizing to a solid state, crushing, and forming products with different specifications for packaging treatment.
9. A processing method according to claim 8, characterized in that: and D, keeping the temperature and standing for 50-90 minutes.
10. An anhydrous potassium tetrafluoroaluminate, characterized in that: the anhydrous potassium tetrafluoroaluminate is potassium tetrafluoroaluminate which is obtained by the treatment method according to claims 1 to 9, does not contain crystal water and has a different lattice arrangement from that of the conventional wet-synthesized potassium tetrafluoroaluminate.
CN202310514300.0A 2023-05-05 2023-05-05 Method for treating solid waste generated in aluminum-titanium-boron production process and anhydrous potassium tetrafluoroaluminate Pending CN116553590A (en)

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