CN118598447B - A method and system for treating fluorine-containing sludge - Google Patents
A method and system for treating fluorine-containing sludge Download PDFInfo
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- CN118598447B CN118598447B CN202411045498.3A CN202411045498A CN118598447B CN 118598447 B CN118598447 B CN 118598447B CN 202411045498 A CN202411045498 A CN 202411045498A CN 118598447 B CN118598447 B CN 118598447B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/192—Preparation from fluorspar
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/196—Separation; Purification by distillation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
The invention provides a method and a system for treating fluorine-containing sludge, and belongs to the technical field of fluorine-containing sludge treatment. According to the method for treating the fluorine-containing sludge, disclosed by the invention, fluorine-containing sludge waste in the photovoltaic and photoelectric industry is taken as a raw material, calcium fluoride and calcium salt in the fluorine-containing sludge are extracted and separated through impurity removal treatment and first acidification treatment, the calcium fluoride is converted into crude HF through second acidification treatment, the impurity of the crude HF is removed through oxidation treatment and rectification treatment, HF liquid is obtained in high yield, and resource utilization of the fluorine-containing sludge is realized.
Description
Technical Field
The invention relates to the technical field of fluorine-containing sludge treatment, in particular to a method and a system for treating fluorine-containing sludge.
Background
In recent years, china supports new energy industry, information technology is developed rapidly, photovoltaic industry is developed rapidly, and market share is over 50% of the world. In the process of cleaning and etching photovoltaic glass and silicon wafers, the photovoltaic photoelectric industry can use a large amount of hydrofluoric acid to corrode silicon materials, so that fluorine-containing wastewater is discharged. At present, the fluorine-containing photovoltaic wastewater is generally treated by adopting methods such as chemical/coagulating sedimentation, floatation, adsorption and the like, a large amount of fluorine-containing sludge is generated after the treatment, and the main components of the fluorine-containing sludge are CaF 2、SiO2、CaSO4、Ca(OH)2, a precipitator, a flocculating agent and the like, so that the problem of difficult subsequent treatment is caused.
The traditional disposal mode of the fluorine-containing sludge is direct landfill treatment, and has the advantages of simplicity and convenience, and the defects of resource waste and occupied land, and along with the extension of landfill time, fluorine ions can leach out to the environment to cause fluorine pollution, and precious fluorine resources are wasted.
The main component of the fluorine-containing sludge is CaF 2, and the fluorine-containing sludge is reasonably treated and efficiently converted, so that potential pollution of the fluorine-containing sludge can be eliminated, and a substitute can be found for nonrenewable fluorite resources.
Disclosure of Invention
The invention provides a treatment method of fluorine-containing sludge, which can realize the resource utilization of fluorine-containing sludge.
The invention also provides a system for executing the treatment method, and the reactors are reasonably connected, so that the treatment of the fluorine-containing sludge can be realized.
The invention provides a method for treating fluorine-containing sludge, which comprises the following steps:
1) Mixing the fluorine-containing sludge, the carbonate solution and the dispersing agent for impurity removal treatment, and obtaining impurity-removed fluorine-containing sludge when the pH value is 7-7.5;
2) Performing first acidification treatment on the impurity-removed fluorine-containing sludge and hydrofluoric acid solution to obtain a crude calcium fluoride product;
3) Performing second acidification treatment on the crude calcium fluoride and sulfuric acid to obtain a crude HF (hydrogen fluoride) product and calcium sulfate; the sulfuric acid comprises 98% sulfuric acid and 20% fuming sulfuric acid;
4) Oxidizing the HF crude product by using fluorine gas to obtain a gas-phase product;
5) And rectifying the gas phase product to obtain refined HF and light impurity gas phase.
The method as described above, wherein before the step 5), further comprises:
Carrying out first condensation treatment on the gas-phase product to obtain a condensate product;
Returning a part of the condensate product to participate in the oxidation treatment, and carrying out the refining treatment on the rest part of the condensate product;
And returning the condensate product participating in the oxidation treatment and the condensate product subjected to the refining treatment to a volume ratio of 3-7.
A method as described above, wherein the second acidification treatment comprises:
pretreating the crude calcium fluoride product, and mixing with sulfuric acid to obtain a solid-liquid mixture;
performing acidification pretreatment on the solid-liquid mixture to obtain an acidification gas phase product and an acidification solid-liquid mixture;
sequentially carrying out acidification intermediate treatment and acidification post-treatment on the acidification solid-liquid mixture to obtain a first HF crude product;
Fractionating the acidified gas phase product to obtain a second HF crude product and an acidic heavy component;
Wherein, the crude HF product in the step 4) comprises a first crude HF product and a second crude HF product;
the pretreatment temperature is 150-200 ℃, the temperature for mixing with sulfuric acid is 50-60 ℃, the temperature for pre-acidification treatment is 80-120 ℃, the temperature for in-acidification treatment is 180-300 ℃, and the temperature for post-acidification treatment is 150-200 ℃.
The method as described above, wherein after the acidic heavy component is subjected to a purification treatment, a purified product is caused to participate in the first acidification treatment as the hydrofluoric acid solution;
and/or; performing second condensation treatment on the light impurity gas phase in the step 5) to obtain a liquid-phase product and gas-phase impurities;
Returning the liquid phase impurities to participate in the rectification treatment; the volume ratio of the liquid phase product to the gas phase impurity is 2-5;
and (3) absorbing the gas-phase impurities by using an absorbent to obtain byproducts calcium fluosilicate and calcium sulfate.
The method comprises the steps of 1) carrying out impurity removal treatment at 40-60 ℃;
And/or, the carbonate solution in the step 1) comprises at least one of Na 2CO3 solution and K 2CO3 solution;
and/or, the dispersing agent in the step 1) comprises at least one of polyethylene glycol and polysorbate;
And/or, the temperature of the first acidification treatment in the step 2) is 20-35 ℃;
and/or, the volume ratio of 98% sulfuric acid to 20% fuming sulfuric acid in the step 3) is 1.5-2;
And/or, the mass ratio of the crude calcium fluoride to the acid solvent in the step 3) is 1-1.4;
and/or, the temperature of the oxidation treatment in the step 4) is 20-35 ℃;
and/or the temperature of the first condensation treatment is 15-25 ℃;
and/or the temperature of the second condensation treatment is 10-15 ℃.
The second aspect of the present invention provides a system for performing the above method, comprising an alkalization reactor, a first acidification reactor, a second acidification reactor, an oxidation column and a rectification column;
The outlet of the alkalization reactor is communicated with the inlet of the first acidification reactor, the outlet of the first acidification reactor is communicated with the inlet of the second acidification reactor, the gas phase outlet of the second acidification reactor is communicated with the gas inlet of the oxidation tower, and the gas phase outlet of the oxidation tower is communicated with the inlet of the rectifying tower.
The system as described above, further comprising a first condenser, wherein the oxidation column and the rectification column are in communication via the first condenser;
The gas phase outlet of the oxidation tower is positioned above the oxidation tower, the gas phase outlet of the first condenser is communicated with the inlet of the rectifying tower, and the liquid phase outlet of the first condenser is communicated with the inlet above the oxidation tower.
The system as described above, wherein the second acidification reactor comprises a pre-reactor and a rotary reaction furnace which are communicated with each other, the pre-reactor and the rotary reaction furnace are detachably connected, the outlet of the first acidification reactor is communicated with the inlet of the pre-reactor, and the gas phase outlet of the rotary reaction furnace is communicated with the inlet of the oxidation tower;
A scraping piece is arranged on a rotating shaft of the pre-reactor, and the rotating directions of the scraping piece and the pre-reactor are opposite;
A slag returning cylinder is arranged on a rotating shaft of the rotary reaction furnace, the rotating directions of the slag returning cylinder and the rotary reaction furnace are opposite, and a material lifting part and a material blocking part which are bent towards the opposite direction of the inlet of the pre-reactor are arranged on the inner wall of the rotary reaction furnace;
the rotary reaction furnace is provided with an electric heating device at the furnace end and the furnace tail respectively;
And/or, further comprising a fractionation column, the gas phase outlet of the pre-reactor being in communication with the inlet of the fractionation column, the gas phase outlet of the fractionation column being in communication with the inlet of the oxidation column.
The system as described above, further comprising a distiller, wherein the liquid phase outlet of the fractionating tower is in communication with the distiller inlet, and the vapor phase outlet of the distiller is in communication with the first acidification reactor inlet.
The system as described above, further comprising a second condenser, wherein the rectification product outlet of the rectification column is communicated with the inlet of the second condenser, the liquid phase product outlet of the second condenser is communicated with the inlet of the rectification column, and the gas phase product outlet of the second condenser is communicated with the gas phase impurity treatment device;
And/or the bottom of the oxidation tower is provided with a reboiling tray, and the reboiling tray is positioned below the gas inlet of the oxidation tower;
And/or the bottom of the oxidation tower is provided with an air inlet and a gas distributor, the top of the oxidation tower is provided with a liquid inlet and a liquid distributor, and a filler layer is arranged between the gas distributor and the liquid distributor;
and/or a liquid storage tank is arranged at the bottom of the rectifying tower, and the temperature of the liquid storage tank is 18-30 ℃.
The invention takes the fluorine-containing sludge waste in the photovoltaic industry as the raw material, and can efficiently convert calcium fluoride into HF products after the fluorine-containing sludge is treated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a schematic diagram of a system provided in an embodiment of the invention;
FIG. 2 is a schematic diagram of a system according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a second acidification reactor provided in an embodiment of the present invention;
FIG. 4 is a schematic diagram of an oxidation column according to one embodiment of the present invention;
fig. 5 is a schematic diagram of a rectifying tower according to an embodiment of the present invention.
Reference numerals illustrate:
1-an alkalization reactor;
2-a first acidification reactor;
3-a second acidification reactor;
301-a pre-reactor;
302-a feed inlet;
303-acid inlet;
304-scraping piece;
305-pre-reactor gas phase outlet;
306-a screw connection port;
307-rotary reaction furnace;
308-a gas phase outlet of the rotary reaction furnace;
309-a slag return cylinder;
310-a material lifting part;
311-material blocking pieces;
312-slag hole;
a 4-oxidation column;
401-an air inlet;
402-reboiling tray;
403-liquid distributor;
404-gas distributor;
405-a circulation tank;
406-fluorine gas inlet;
407-a gas phase outlet;
408-a liquid inlet;
409-a filler layer;
410-reboiler;
5-rectifying tower;
501-a liquid storage tank;
6-a first condenser;
7-fractionating tower;
8-distiller;
9-a second condenser;
10-fluorine gas generator.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for treating fluorine-containing sludge, which comprises the following steps:
1) Mixing the fluorine-containing sludge, the carbonate solution and the dispersing agent for impurity removal treatment, and obtaining impurity-removed fluorine-containing sludge when the pH value is 7-7.5;
2) Performing first acidification treatment on the impurity-removed fluorine-containing sludge and hydrofluoric acid solution to obtain a crude calcium fluoride product;
3) Performing second acidification treatment on the crude calcium fluoride and an acidic solvent to obtain a crude HF (hydrogen fluoride) product and calcium sulfate; the acidic solvent comprises 98% sulfuric acid and 20% fuming sulfuric acid;
4) Oxidizing the HF crude product by using fluorine gas to obtain a gas-phase product;
5) And rectifying the gas phase product to obtain refined HF and light impurity gas phase.
The main components of the fluorine-containing sludge comprise CaF 2、SiO2、CaSO4、Ca(OH)2, a precipitator, a flocculating agent and the like, and the carbonate solution is added in the step 1), so that CaSO 4 in the fluorine-containing sludge can be converted into CaCO 3, and the subsequent extraction of Ca element in the fluorine-containing sludge is facilitated.
The above carbonate solution is not limited too much, and carbonate solutions, such as Na 2CO3 solution, K 2CO3 solution, etc., which are conventional in the art, may be used.
Preferably, the carbonate solution is Na 2CO3 solution with the mass concentration of 10% -30%.
The dispersing agent is added, so that CaF 2 particles can be uniformly dispersed in a mixed system, sedimentation and agglomeration of the CaF 2 particles are prevented, the subsequent treatment is not facilitated, the dispersing agent can effectively dissolve organic impurities in fluorine-containing sludge, and coagulant, flocculant and the like can be dissolved after the mixing and coordination reaction of carbonate solution and the dispersing agent, and are removed after solid-liquid separation.
The dispersing agent comprises at least one of polyethylene glycol and polysorbate.
Further, the polyethylene glycol includes at least one of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800.
Further, the reaction temperature of the step 1) is 40-60 ℃.
In another specific embodiment, the method further comprises the step of refining the fluorine-containing sludge before the step 1), so that the components in the fluorine-containing sludge are fully reacted.
The invention does not limit the refining treatment mode, such as adopting a ball mill to refine the fluorine-containing sludge.
After the treatment of the step 1), the main components of the obtained impurity-removed fluorine-containing sludge are CaF 2、SiO2、CaCO3、Ca(OH)2 and the like.
In the step 2), caCO 3 and Ca (OH) 2 in the fluorine-containing sludge can be converted into CaF 2 by acidification of the hydrofluoric acid solution, and the dispersed fine CaF 2 can form CaF 2 with a larger form in the hydrofluoric acid solution due to the promotion effect of the hydrofluoric acid solution on the dissolution of CaF 2, so that the intensity of HF reaction in the second acidification treatment is reduced; and the hydrofluoric acid reacts with SiO 2 in the impurity-removed fluorine-containing sludge to produce SiF 4 gas, so that solid SiO 2 in the impurity-removed fluorine-containing sludge is removed. The added hydrofluoric acid solution does not introduce other impurity ions in the reaction process.
Further, the mass concentration of the hydrofluoric acid solution is 5% -10%.
Further, the reaction temperature of the first acidification treatment in the step 2) is 20-35 ℃.
After the first acidification treatment, carrying out solid-liquid separation on the mixed system to obtain a solid product, namely a crude calcium fluoride product.
In step 3), the crude calcium fluoride is reacted with sulfuric acid to produce crude HF and a calcium sulfate byproduct, wherein the sulfuric acid is a mixture of 98% sulfuric acid and 20% oleum.
The crude HF contains A S impurity, P impurity and S impurity, wherein the A S element, the P element and the S element exist in low valence state.
In the step 4), fluorine is utilized to oxidize low-valence A S element, P element and S element into AsF 5 high-boiling-point substances, PF 5 and SF 6 low-boiling-point substances respectively. The AsF 5 high boilers can be separated from HF in this step, so that the gas phase products are mainly HF and low boiler impurities of PF 5 and SF 6.
And oxidizing impurities in the HF crude product by using fluorine gas, and introducing no other oxidant impurities.
Further, the mass ratio of fluorine gas to the HF crude product is 0.01-0.03%.
Through the rectification treatment in step 5), low-boiling impurities of PF 5 and SF 6 can be separated from HF to obtain refined HF and a light gas phase, wherein the light gas phase contains SO 2、SiF4 in addition to small amounts of PF 5 and SF 6.
According to the method for treating the fluorine-containing sludge, disclosed by the invention, fluorine-containing sludge waste in the photovoltaic and photoelectric industry is taken as a raw material, calcium fluoride and calcium salt in the fluorine-containing sludge are extracted and separated through impurity removal treatment and first acidification treatment, the calcium fluoride is converted into crude HF through second acidification treatment, the impurity of the crude HF is removed through oxidation treatment and rectification treatment, HF liquid is obtained in high yield, and resource utilization of the fluorine-containing sludge is realized.
In a specific embodiment, before the step 5), the method further includes:
Carrying out first condensation treatment on the gas-phase product to obtain a condensate product;
Returning a part of the condensate product to participate in the oxidation treatment, and carrying out the refining treatment on the rest part of the condensate product;
And returning the condensate product participating in the oxidation treatment and the condensate product subjected to the refining treatment to a volume ratio of 3-7.
By returning part of the condensate product to participate in the oxidation treatment, the low-valence elements A S, P and S which are not completely reacted in the liquid-phase product can be further reacted.
By setting the volume ratio of the condensate product which returns to participate in the oxidation treatment to the condensate product which is subjected to the refining treatment to 3-7, the return of the condensate product can be promoted, and the liquid flow in the reaction device can be increased.
In one embodiment, the second acidification treatment comprises:
pretreating the crude calcium fluoride product, and mixing with sulfuric acid to obtain a solid-liquid mixture;
performing acidification pretreatment on the solid-liquid mixture to obtain an acidification gas phase product and an acidification solid-liquid mixture;
sequentially carrying out acidification intermediate treatment and acidification post-treatment on the acidification solid-liquid mixture to obtain a first HF crude product;
Fractionating the acidified gas phase product to obtain a second HF crude product and an acidic heavy component;
Wherein, the crude HF product in the step 4) comprises a first crude HF product and a second crude HF product;
the pretreatment temperature is 150-200 ℃, the temperature for mixing with sulfuric acid is 50-60 ℃, the temperature for pre-acidification treatment is 80-120 ℃, the temperature for in-acidification treatment is 180-300 ℃, and the temperature for post-acidification treatment is 150-200 ℃.
The method comprises the steps of pre-treating the crude calcium fluoride before mixing the crude calcium fluoride with sulfuric acid, and removing water in the crude calcium fluoride, so that corrosiveness of the crude calcium fluoride to a reaction device in the reaction process of the crude calcium fluoride and the sulfuric acid is reduced, and the pretreated crude calcium fluoride is mixed with the sulfuric acid to obtain a solid-liquid mixture.
Further, the pretreatment temperature is 150-200 ℃, and the heating time is 2-4 hours.
And (3) carrying out acidification pretreatment on the solid-liquid mixture, wherein in the process, a small amount of crude calcium fluoride reacts with sulfuric acid to obtain an acidification gas-phase product and an acidification solid-liquid mixture.
Further, in the acidification pretreatment process, the temperature of the acidification pretreatment is 80-120 ℃, the reaction time is 0.5-1h, the reaction temperature is controlled in a gradient manner, the initial temperature is 50-60 ℃, the heating temperature is 80-120 ℃, the gradient control reaction temperature can slow down the reaction rate of the acidification pretreatment, and the gas generated by the reaction is timely discharged, so that severe reaction in the acidification pretreatment process is further prevented.
And then, sequentially carrying out acidification intermediate treatment and acidification post-treatment on the acidification solid-liquid mixture to obtain a first HF crude product. The time of the acidification middle treatment and the acidification post treatment is 1-2 hours.
The second acidification treatment adopts sectional heating, so that the heat in the reaction process can be fully utilized, and the energy consumption is reduced; the reaction progress is controlled by sectional heating, and the area with the strongest reaction corrosion is controlled in the pre-acidification treatment stage, so that the corrosion to equipment for the in-acidification treatment and the post-acidification treatment is avoided.
And (3) fractionating the acidified gas phase product to obtain a second HF crude product and an acidic heavy component. The first HF crude product and the second HF crude product are mixed and enter the subsequent treatment flow.
Different reaction temperatures are set for the acidification middle treatment and the acidification post treatment, so that the reaction rate can be controlled, the reaction is performed smoothly, and severe reaction is avoided.
Further, the temperature of the acidification treatment is 180-300 ℃, and the temperature of the acidification post-treatment is 150-200 ℃; the reaction time of the acidification middle treatment and the acidification post treatment is 1-2 hours.
In one embodiment, after the acidic heavy component is purified, the purified product is taken as the hydrofluoric acid solution to the first acidification treatment.
The acidic heavy component is mainly HF and sulfuric acid solution, the HF can be separated through purification treatment, and hydrofluoric acid solution can be prepared for the first acidification treatment.
The purification treatment may be, in particular, distillation or other purification treatment methods commonly used in the art.
In a specific embodiment, the light impurity gas phase in the step 5) is subjected to a second condensation treatment to obtain a liquid phase product and gas phase impurities;
returning the liquid phase product to participate in the rectification treatment; the volume ratio of the liquid phase product to the gas phase impurity is 2-5;
and (3) absorbing the gas-phase impurities by using an absorbent to obtain byproducts calcium fluosilicate and calcium sulfate.
And 5) in the step 5), the light impurity gas phase contains HF and PF 5、SF6、SO2、SiF4, the light impurity gas phase is subjected to second condensation treatment to obtain a liquid phase product containing HF and PF 5、SF6 and gas phase impurities containing SO 2、SiF4, the liquid phase product returns to participate in the rectification treatment, the HF contained in the liquid phase product is further separated, and the gas phase impurities are subjected to absorption treatment by an absorbent to obtain byproducts of calcium fluosilicate and calcium sulfate. The gas phase impurity absorbent can be water or lime water.
In a specific embodiment, the temperature of the impurity removal treatment in the step 1) is 40-60 ℃;
the temperature of the first acidification treatment in the step 2) is 20-35 ℃;
The volume ratio of the 98% sulfuric acid to the 20% fuming sulfuric acid in the step 3) is 1.5-2;
The mass ratio of the crude calcium fluoride to the acid solvent in the step 3) is 1-1.4;
the temperature of the oxidation treatment in the step 4) is 20-35 ℃;
The temperature of the first condensation treatment is 15-25 ℃;
the temperature of the second condensation treatment is 10-15 ℃.
The raw material cost and the reaction efficiency can be considered by controlling the reaction temperature and the material proportion of each step.
The second aspect of the present invention provides a system for performing the above method, as depicted in fig. 1, comprising an alkalization reactor 1, a first acidification reactor 2, a second acidification reactor 3, an oxidation column 4 and a rectification column 5;
the outlet of the alkalization reactor 1 is communicated with the inlet of the first acidification reactor 2, the outlet of the first acidification reactor 2 is communicated with the inlet of the second acidification reactor 3, the gas phase outlet of the second acidification reactor 3 is communicated with the gas inlet of the oxidation tower 4, and the gas phase outlet of the oxidation tower 4 is communicated with the inlet of the rectifying tower 5.
According to the system for executing the treatment method of the fluorine-containing sludge, the reactors are reasonably connected, so that the treatment of the fluorine-containing sludge can be realized.
In a specific embodiment, as shown in fig. 2 and 4, the oxidation tower 4 and the rectification tower 5 further comprise a first condenser 6, and the first condenser 6 is communicated with the oxidation tower 4;
Wherein the gas phase outlet 407 of the oxidation tower 4 is located above the oxidation tower 4, the gas phase outlet of the first condenser 6 is communicated with the inlet of the rectifying tower 5, and the liquid phase outlet of the first condenser 6 is communicated with the inlet above the oxidation tower 4.
The liquid flowing out from the liquid phase outlet of the first condenser 6 enters from the liquid inlet 408 at the upper part of the oxidation tower 4 and reversely contacts with the fluorine gas entering from the fluorine gas inlet 406 at the lower part of the oxidation tower 4, and the fluorine gas is generated by the fluorine gas generator 10, so that the sufficient contact of the gas-liquid materials is realized, and the reaction is more sufficient.
Furthermore, the rectifying tower 5 is made of stainless steel and is lined with fluoroplastic, so that the corrosion of HF to the metallic material of the tower body in the rectifying process can be prevented, and the pollution of HF is caused.
In one embodiment, as shown in fig. 4, a reboiling tray 402 is disposed at the bottom of the oxidation tower 4, and the reboiling tray 402 is located below the gas inlet of the oxidation tower 4.
The condensed liquid in the oxidation tower 4 drops onto the reboiling tray 402, rises after being heated and gasified again, and is mixed with HF gas to rise and reversely contact with the mixed fluorine gas again, so that the utilization of the fluorine gas is further promoted. In addition, the reboiling tray 402 forms a complementary heating cycle condensate with the liquid in the circulation tank 405 by heating the liquid dropped thereto, and effectively prevents high boiling substances in the liquid tank from being carried into the mixed gas of the oxidation tower 4 again due to an excessively high temperature while vaporizing the condensate.
Further, the reboiling tray 402 is densely populated with voids.
Further, the temperature of the reboiling tray 402 is 30-40 ℃.
In another embodiment, a liquid distributor 403 is provided above the oxidation column 4, below the upper inlet where the liquid distributor 403 is located.
The liquid distributor 403 sprays the liquid flowing out from the liquid phase outlet of the first condenser 6, and the liquid reversely contacts with fluorine gas in a mist manner, so that the contact area of the gas-liquid material is further enlarged.
Further, the gas inlet and the gas distributor 404 are arranged at a distance of 1/4 from the bottom, the liquid inlet and the liquid distributor 403 are arranged at the top, and the filler layer 409 is arranged between the gas distributor 404 and the liquid distributor 403.
Still further, the filler layer 409 is a layer of polytetrafluoroethylene particles.
In one embodiment, oxidation column 4 is further provided with reboiler 410 for heating the crude HF product entering oxidation column 4.
The gas distributor 404 and the liquid distributor 403 arranged in the oxidation tower can fully disperse gas and liquid materials, so that the reaction materials are fully contacted, the filler layer 409 can slow down the rising speed of fluorine gas in the reaction tower, and the gas distributor has a rectifying tower plate effect, so that the contact surface with HF gas and condensed circulating liquid and the rising resistance of the materials are increased. The oxidized high boiling substances and low boiling substances can be effectively separated from HF in the filler layer 409 and the reflux and condensate circulation.
Further, a circulation tank 405 is provided at the bottom end for enriching and separating heavy component substances generated in the oxidation treatment.
Further, the heating temperature of the circulating tank is 20-30 ℃.
In one embodiment, as shown in fig. 3, the second acidification reactor comprises a pre-reactor 301 and a rotary reaction furnace 307 which are communicated with each other, the pre-reactor 301 and the rotary reaction furnace 307 are detachably connected, the outlet of the first acidification reactor 2 is communicated with the inlet of the pre-reactor 301, and the gas phase outlet of the rotary reaction furnace 307 is communicated with the inlet;
A scraping piece 304 is arranged on the rotating shaft of the pre-reactor 301, and the rotating directions of the scraping piece 304 and the pre-reactor 301 are opposite;
A slag returning cylinder 309 is arranged on the rotating shaft of the rotary reaction furnace 307, the rotating directions of the slag returning cylinder 309 and the rotary reaction furnace 307 are opposite, and a material lifting part 310 and a material blocking part 311 which are bent towards the opposite direction of the inlet of the pre-reactor 301 are arranged on the inner wall of the rotary reaction furnace 307;
The rotary reaction furnace 307 is provided with electric heating devices at the furnace end and the furnace tail respectively, thereby realizing the setting of different reaction temperatures of the acidification middle treatment and the acidification post treatment. The reaction temperature distribution of the rotary reaction furnace 307 reasonably distributes the reaction area of the rotary reaction furnace 307, greatly reduces the corrosion to the rotary reaction furnace 307, and prolongs the service life of the rotary reaction furnace 307.
The material output by the first acidification reactor 2 enters through a feed inlet 302 of a pre-reactor 301; sulfuric acid enters through acid inlet 303; the gas generated by the acidification pretreatment reaction is discharged through a gas phase outlet 305 of the pre-reactor 301; the gas generated by the acidification treatment and the acidification post-treatment reaction is discharged through a gas phase outlet 308 of the rotary reaction furnace 307.
Further, a negative pressure fan is arranged in the pre-reactor 301, so that the gas generated by the reaction can be timely discharged, and the gas generated by the severe reaction and the attached materials are prevented from blocking the pipeline.
Still further, the pre-reactor 301 and the rotary reactor 307 are detachably connected, such as screw-threaded connection, snap-fit connection. In the case of screw connection, as shown in fig. 3, the pre-reactor 301 is connected to the rotary reaction furnace 307 through a screw connection port 306.
In the second acidification treatment, the reaction in the pre-reactor 301 is the most intense, the corrosion to the pre-reactor 301 is the greatest, and the corroded pre-reactor 301 can be conveniently replaced by adopting a detachable connection mode, so that the whole system is prevented from stopping running due to the damage of the pre-reactor 301.
In another embodiment, the material of the pre-reactor 301 is hastelloy or monel, so as to improve the corrosion resistance of the apparatus; the rotary reactor 307 is made of carbon steel or stainless steel.
After the fluorine-containing sludge is subjected to impurity removal treatment and first acidification treatment, the obtained purified CaF 2 particles are fine and easily form sticky substances with sulfuric acid, and are adhered to the inner wall of the pre-reactor 301. The scraping piece 304 is arranged on the rotating shaft of the pre-reactor 301, and the rotation directions of the scraping piece 304 and the pre-reactor 301 are opposite, so that materials adhered on the inner wall can be continuously scraped off by the scraping piece 304, and the materials are prevented from being accumulated in the pre-reactor 301.
The rotating shaft of the rotary reaction furnace 307 is provided with a slag returning cylinder 309, the rotating directions of the slag returning cylinder 309 and the rotary reaction furnace 307 are opposite, and the inner wall of the rotary reaction furnace 307 is provided with a material lifting part 310 and a material blocking part 311 which are bent towards the opposite direction of the inlet of the pre-reactor 301, so as to play a role in stirring materials in the rotary reaction furnace 307. Meanwhile, the byproduct CaSO 4 of the second acidification treatment can be returned to the front part of the rotary reaction furnace 307 under the action of the slag returning cylinder 309 and the material blocking piece 311, so that on one hand, heat can be provided for the mixture of the coarse calcium fluoride and sulfuric acid at the end part of the rotary reaction furnace 307, and on the other hand, dry CaSO 4 slag dilutes the pasty mixture of the coarse calcium fluoride and sulfuric acid to prevent the mixture from forming walls in the furnace.
The material lifting part 310 is arranged in the rotary reaction furnace 307, and under the rotary action of the rotary reaction furnace 307, the contact surface with the materials in the rotary reaction furnace 307 is enlarged, and a secondary paddle stirring effect is formed. The residual materials which are not fully reacted are stirred for the second time under the action of the lifting piece 310 and the blocking piece 311 to complete the reaction, and HF gas contained in the residual materials can be released and separated.
Further, the material raising members 310 are disposed at the middle of the furnace body to the tail position and are uniformly distributed. Further, the surface of the material lifting member 310 is convex toward the burner, so as to further enlarge the contact area with the material.
The internal design of the second acidification reactor 3 can improve the residence time of materials in the second acidification reactor, enhance the internal stirring effect, reasonably utilize the product CaSO 4 to provide heat for the reaction, save the heat consumption, dilute the reaction raw materials and prevent the materials from agglomerating and sticking to the wall. Finally, the calcium sulfate formed in the second acidification reactor 3 is discharged via a slag outlet 312.
In one embodiment, the apparatus further comprises a fractionation column 7, wherein the gas phase outlet of the pre-reactor 301 is in communication with an inlet of the fractionation column 7, and the gas phase outlet of the fractionation column 7 is in communication with said inlet.
The fractionating tower 7 is used for fractionating the gas phase product obtained by the acidification pretreatment. The temperature of the fractionating tower 7 tower body is 35-40 ℃, the temperature of the top of the tower is 25-35 ℃.
In a specific embodiment, the reactor further comprises a distiller 8, wherein the liquid phase outlet of the fractionating tower 7 is communicated with the inlet of the distiller 8, and the gas phase outlet of the distiller 8 is communicated with the inlet of the first acidification reactor 2.
After the gas phase product is subjected to fractional distillation treatment, a second crude HF product and an acidic heavy component are obtained, the acidic heavy component is treated by a distiller 8, HF in the acidic heavy component can be recovered, and the recovered HF can be prepared into a solution for supplementing the hydrofluoric acid solution in the first acidification treatment.
In a specific embodiment, the device further comprises a second condenser 9, wherein the rectification product outlet of the rectification column 5 is communicated with the inlet of the second condenser 9, the liquid-phase product outlet of the second condenser 9 is communicated with the inlet of the rectification column 5, and the gas-phase product outlet of the second condenser 9 is communicated with the gas-phase impurity treatment device.
The second condenser 9 is used for condensing the rectification product, HF and PF 5、SF6 in the rectification product are returned to the rectification tower 5 after condensing, HF in the rectification product is separated, noncondensable gas SO 2、SiF4 is input to the gas phase impurity treatment device, and the byproducts calcium fluosilicate and calcium sulfate are obtained.
The present invention does not limit the gas phase impurity treatment device too much, and can employ conventional devices in the art, such as a gas absorbing device with water, a gas absorbing device with lime water, etc.
In a specific embodiment, as shown in fig. 5, a liquid storage tank 501 is arranged at the bottom of the rectifying tower 5, and the liquid storage tank 501 is provided with a heating device.
Refined HF is formed in a liquid storage tank 501, the liquid storage tank 501 is provided with a heating device, the boiled HF liquid keeps positive pressure in a rectifying tower 5, and simultaneously, the evaporated HF in the tower and materials in the tower can form circulating reflux.
Further, the temperature of the liquid storage tank 501 is 18-30 ℃; the temperature of the top of the rectifying tower is 15-20 ℃.
Furthermore, the rectifying tower 5 is made of stainless steel lined fluoroplastic, so that corrosion of HF to metal materials of the rectifying tower 5 in the rectifying process can be prevented, and HF pollution can be prevented.
The scheme provided by the invention is further described below with reference to specific examples.
Example 1
The treatment method of the fluorine-containing sludge comprises the following specific steps:
1) 500Kg fluorine-containing sludge is conveyed to an alkalization reactor after being refined and dispersed by a ball mill. Preparing polyethylene glycol 600 and 25% sodium carbonate solution into 1% polyethylene glycol 600 concentration, adding into an alkalization reactor, heating to 45 ℃, mixing and stirring, controlling the reaction time to 1.5h, reducing the pH value of the material to about neutral, reducing the pH value to 1/50 of the original stirring rate, and keeping for 3h; and (3) carrying out solid-liquid separation to obtain impurity-removed fluorine-containing sludge, and conveying the impurity-removed fluorine-containing sludge to a first acidification reactor without washing and drying.
2) Mixing the impurity-removed fluorine-containing sludge with 5% hydrofluoric acid solution in a first acidification reactor, wherein the temperature of the acidification reactor is set to be 30 ℃, the stirring speed is set to be 500r/min, so that the reactant is fully stirred in a suspension mode, and the acidification reaction is carried out for 1.5h. And (3) carrying out solid-liquid separation to obtain a coarse calcium fluoride product and an acidic filtrate, wherein the coarse calcium fluoride product can be used for replacing fluorite.
3) The crude calcium fluoride is input into a pre-reactor of a second acidification reactor, is heated to 200 ℃ and then is kept for 3 hours, is cooled to the initial temperature of 55 ℃ of the pre-reaction, and is introduced with mixed acid of 98% sulfuric acid and 20% fuming sulfuric acid with the volume ratio of 1.5:1, wherein the mass ratio of the mixed acid to the crude calcium fluoride is 1.1:1, after rotating reaction for 0.5h, slowly heating to the pre-reaction temperature of 90 ℃ and then maintaining for 0.5h to obtain a gas phase product and a solid-liquid mixed product.
Conveying the solid-liquid mixed product to a rotary reaction furnace, and performing acidification intermediate treatment and acidification post-treatment to obtain a first HF crude product; and fractionating the gas phase product by a fractionating tower to obtain a second HF crude product and an acidic heavy component, mixing the first HF crude product and the second HF crude product, conveying the mixture to an oxidation tower, and distilling the acidic heavy component to prepare an HF solution for the first acidification reaction. And (5) obtaining calcium sulfate solid at the tail of the rotary reaction furnace.
The temperature of the fractionating tower body is set at 35 ℃, and the temperature of the tower top is controlled at 30 ℃. The solid-liquid mixed product is acidolysis reacted in a rotary reaction furnace for 1h, the front end of the rotary reaction furnace body is controlled at 200 ℃ during the acidification treatment, and the rear end of the rotary reaction furnace is set at 160 ℃ after the acidification treatment.
4) Heating the first crude HF product and the second crude HF product by a reboiler at 30 ℃ and then sending the heated crude HF products into an oxidation tower gas distributor, and controlling the aeration rate to be 20Kg/h; fluorine gas is introduced into the oxidation tower at the speed of 5g/h, the temperature of the fluorination reaction tower body is 30 ℃, the condensation temperature of the first condenser is 19 ℃, and the volume ratio of the liquid-phase oxidation product which is returned to participate in the oxidation treatment to the liquid-phase oxidation product which is subjected to the refining treatment is 4.
5) The material flowing out of the first condenser enters a rectifying tower, the rectifying product is condensed by a second condenser, the obtained liquid returns to the rectifying tower again, and the non-condensable gas is absorbed by water and lime water to obtain byproducts calcium fluosilicate and calcium sulfate.
The heating temperature of the liquid storage tank of the rectifying tower is 25 ℃, the temperature of the tower top is 18 ℃, the reflux ratio is controlled to be 3, and 115Kg of HF liquid is obtained after the HF liquid is formed in the liquid storage tank through cyclic rectification.
The preparation method can efficiently convert calcium fluoride in the fluorine-containing sludge and realize the recycling treatment of the fluorine-containing sludge.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The method for treating the fluorine-containing sludge is characterized by comprising the following steps of:
1) Mixing the fluorine-containing sludge, the carbonate solution and the dispersing agent for impurity removal treatment, and obtaining impurity-removed fluorine-containing sludge when the pH value is 7-7.5;
2) Performing first acidification treatment on the impurity-removed fluorine-containing sludge and hydrofluoric acid solution to obtain a crude calcium fluoride product;
3) Performing second acidification treatment on the crude calcium fluoride and sulfuric acid to obtain a crude HF (hydrogen fluoride) product and calcium sulfate; the sulfuric acid comprises 98% sulfuric acid and 20% fuming sulfuric acid;
4) Oxidizing the HF crude product by using fluorine gas to obtain a gas-phase product;
5) Rectifying the gas phase product to obtain refined HF and light impurity gas phase;
the second acidification treatment comprises:
pretreating the crude calcium fluoride product, and mixing with sulfuric acid to obtain a solid-liquid mixture;
performing acidification pretreatment on the solid-liquid mixture to obtain an acidification gas phase product and an acidification solid-liquid mixture;
sequentially carrying out acidification intermediate treatment and acidification post-treatment on the acidification solid-liquid mixture to obtain a first HF crude product;
Fractionating the acidified gas phase product to obtain a second HF crude product and an acidic heavy component;
Wherein, the crude HF product in the step 4) comprises a first crude HF product and a second crude HF product;
the pretreatment temperature is 150-200 ℃, the temperature for mixing with sulfuric acid is 50-60 ℃, the temperature for pre-acidification treatment is 80-120 ℃, the temperature for in-acidification treatment is 180-300 ℃, and the temperature for post-acidification treatment is 150-200 ℃.
2. The method according to claim 1, further comprising, prior to step 5):
Carrying out first condensation treatment on the gas-phase product to obtain a condensate product;
Returning part of the condensate product to participate in the oxidation treatment, and refining the rest part of the condensate product;
And returning the condensate product participating in the oxidation treatment and the condensate product subjected to the refining treatment to a volume ratio of 3-7.
3. The method according to claim 1, wherein after the acidic heavy component is subjected to the purification treatment, a purified product is caused to participate in the first acidification treatment as the hydrofluoric acid solution;
and/or; performing second condensation treatment on the light impurity gas phase in the step 5) to obtain a liquid-phase product and gas-phase impurities;
returning the liquid phase product to participate in the rectification treatment; the volume ratio of the liquid phase product to the gas phase impurity is 2-5;
and (3) absorbing the gas-phase impurities by using an absorbent to obtain byproducts calcium fluosilicate and calcium sulfate.
4. The method according to claim 3, wherein the temperature of the impurity removal treatment in step 1) is 40-60 ℃;
And/or, the carbonate solution in the step 1) comprises at least one of Na 2CO3 solution and K 2CO3 solution;
and/or, the dispersing agent in the step 1) comprises at least one of polyethylene glycol and polysorbate;
And/or, the temperature of the first acidification treatment in the step 2) is 20-35 ℃;
and/or, the volume ratio of 98% sulfuric acid to 20% fuming sulfuric acid in the step 3) is 1.5-2;
And/or, the mass ratio of the crude calcium fluoride to the acid solvent in the step 3) is 1-1.4;
and/or, the temperature of the oxidation treatment in the step 4) is 20-35 ℃;
and/or the temperature of the first condensation treatment is 15-25 ℃;
and/or the temperature of the second condensation treatment is 10-15 ℃.
5. The process of any one of claims 1-4, comprising a system for performing the process, the system comprising an alkalization reactor, a first acidification reactor, a second acidification reactor, an oxidation column, and a rectification column;
The outlet of the alkalization reactor is communicated with the inlet of the first acidification reactor, the outlet of the first acidification reactor is communicated with the inlet of the second acidification reactor, the gas phase outlet of the second acidification reactor is communicated with the gas inlet of the oxidation tower, and the gas phase outlet of the oxidation tower is communicated with the inlet of the rectifying tower.
6. The method of claim 5, wherein the system for performing the method further comprises a first condenser, the oxidation column and rectification column being in communication through the first condenser;
The gas phase outlet of the oxidation tower is positioned above the oxidation tower, the gas phase outlet of the first condenser is communicated with the inlet of the rectifying tower, and the liquid phase outlet of the first condenser is communicated with the inlet above the oxidation tower.
7. The method of claim 6, wherein the second acidification reactor comprises a pre-reactor and a rotary reactor in communication with each other, the pre-reactor and the rotary reactor being detachably connected, the outlet of the first acidification reactor being in communication with the inlet of the pre-reactor, the gas phase outlet of the rotary reactor being in communication with the inlet of the oxidation column;
A scraping piece is arranged on a rotating shaft of the pre-reactor, and the rotating directions of the scraping piece and the pre-reactor are opposite;
A slag returning cylinder is arranged on a rotating shaft of the rotary reaction furnace, the rotating directions of the slag returning cylinder and the rotary reaction furnace are opposite, and a material lifting part and a material blocking part which are bent towards the opposite direction of the inlet of the pre-reactor are arranged on the inner wall of the rotary reaction furnace;
the rotary reaction furnace is provided with an electric heating device at the furnace end and the furnace tail respectively;
And/or, further comprising a fractionation column, the gas phase outlet of the pre-reactor being in communication with the inlet of the fractionation column, the gas phase outlet of the fractionation column being in communication with the inlet of the oxidation column.
8. The method of claim 7, wherein the system for performing the method further comprises a distiller, the liquid phase outlet of the fractionation column being in communication with an inlet of the distiller, the vapor phase outlet of the distiller being in communication with the inlet of the first acidification reactor.
9. The method according to any one of claims 6-8, wherein the system for performing the method further comprises a second condenser, the rectification product outlet of the rectification column being in communication with the inlet of the second condenser, the liquid phase product outlet of the second condenser being in communication with the inlet of the rectification column, the gas phase product outlet of the second condenser being in communication with a gas phase impurity treatment device;
And/or a reboiling tray is arranged at the bottom of the oxidation tower, the reboiling tray is positioned below the gas inlet of the oxidation tower, and the temperature of the reboiling tray is 30-40 ℃;
And/or, the bottom of the oxidation tower is provided with an air inlet and a gas distributor, the top of the oxidation tower is provided with a liquid inlet, a liquid distributor and a circulating groove, a packing layer is arranged between the gas distributor and the liquid distributor, and the heating temperature of the circulating groove is 20-30 ℃;
and/or a liquid storage tank is arranged at the bottom of the rectifying tower, and the temperature of the liquid storage tank is 18-30 ℃.
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| EP3601189A4 (en) * | 2017-03-23 | 2020-12-23 | Al-Ghouleh, Zaid | CARBONIZATION ACTIVATED CLINKER BINDING AGENT FROM COMBUSTION RESIDUES |
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Denomination of invention: A method and system for treating fluorine-containing sludge Granted publication date: 20241112 Pledgee: Kunlun Trust Co.,Ltd. Pledgor: Zhejiang Wole Technology Co.,Ltd. Registration number: Y2025980019919 |