CN107417013A - Reclaim the method for nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor - Google Patents

Reclaim the method for nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor Download PDF

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CN107417013A
CN107417013A CN201710867906.7A CN201710867906A CN107417013A CN 107417013 A CN107417013 A CN 107417013A CN 201710867906 A CN201710867906 A CN 201710867906A CN 107417013 A CN107417013 A CN 107417013A
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rare earth
pickle liquor
earth element
magnetic materials
iron boron
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CN107417013B (en
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王贵超
刘荣丽
易师
余荣旻
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HUNAN RESEARCH INSTITUTE OF RARE EARTH METAL MATERIALS
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HUNAN RESEARCH INSTITUTE OF RARE EARTH METAL MATERIALS
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/38—Nitric acid
    • C01B21/46—Purification; Separation ; Stabilisation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • 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
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The present invention discloses a kind of method of nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor, comprises the following steps：By neodymium iron boron magnetic materials pickle liquor filtering and impurity removing, gained filtrate carries out the separation of acid and salt through diffusion dialysis device, obtains salpeter solution and the residual night containing rare earth element；Toward described containing ammonium hydrogen carbonate is added in rare earth element residual night, 50r/min~100r/min stirring reactions, the turbid solution containing rare-earth precipitation is obtained；By the turbid solution through diaphragm filter press press filtration, rare earth filter residue is obtained；The addition weight of the ammonium hydrogen carbonate：The neodymium iron boron magnetic materials pickle liquor middle rare earth quality is 4:1~7:1.The inventive method is simple to operate, convenient, more than 85% nitric acid and more than 90% rare earth element in recovery pickle liquor that can be rapidly and efficiently, while alleviates the processing pressure of sewage plant, has larger economic benefit and environmental benefit.

Description

Reclaim the method for nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor
Technical field
The invention belongs to chemical industry environmental protection field, and in particular to nitric acid and rare earth in one kind recovery neodymium iron boron magnetic materials pickle liquor The method of element.
Background technology
Pickling is one of essential process in neodymium iron boron magnetic materials pre-electroplating treatment, needs to use a large amount of nitre in the process Acid, it is made into the pickle of mass fraction 10%~15%.With the increase of access times, under the reaction rate of magnetic material and pickle Drop, while substantial amounts of acid mist is produced, influence normal production efficiency and enterprise employee health, it is therefore desirable to change in time.Replace Acid and rare earth element content are all higher in pickle liquor, are needed after being directly discharged to sewage plant after adding a large amount of piece alkali or lime neutralizations It could further handle up to standard, so not only add the processing pressure of sewage plant but also wasted rare earth resources.
Because pickle is almost changed everyday, several tons of waste liquids can be produced daily, and therefore, pickling is given up using appropriate method Acid and rare earth element in liquid carry out separation and recycling, in terms of the resource reclaim or environmental protection for all with actively Meaning.Mainly there are oxalate precipitation method, resin adsorption method, but these techniques in China in the processing method of neodymium iron boron magnetic materials pickle liquor There is the shortcomings of cost height, the rate of recovery are low, and caused waste water easily produces secondary pollution and complex procedures with technology.
The content of the invention
Based on this, it is necessary to a kind of method of nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor is provided, can Nitric acid and rare earth element are separated and reclaimed from pickle liquor with efficient, high-recovery, with reach Resource recovery, reduce into Originally, simplify technique, solve the purpose of environmental pollution.
A kind of method of nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor, comprises the following steps：
The pickle liquor of neodymium iron boron magnetic materials is obtained, acid and 4g/L containing 0.5mol/L~1mol/L in the pickle liquor ~10g/L rare earth element, wherein, rare earth element quality is in terms of rare earth oxide；
By the pickle liquor filtering and impurity removing, pickling filtrate is obtained；
Water and the pickling filtrate are injected separately into the water inlet of diffusion dialysis device and sour inlet, control the water Flow velocity be 1.8L/min~2.2L/min, the flow velocity of the pickling filtrate is 1.8L/min~2.0L/min, is recycled acid With raffinate containing rare earth element；
Ammonium hydrogen carbonate is added into the raffinate containing rare earth element, with 50r/min~100r/min stirrings, reaction, must be contained There is the turbid solution of rare-earth precipitation；The addition quality of the ammonium hydrogen carbonate and the neodymium iron boron magnetic materials pickle liquor Rare Earth Elements quality The ratio between amount is 4:1~7:1；
By the turbid solution containing rare-earth precipitation through diaphragm filter press press filtration, rare earth filter residue is obtained；.
The above method realizes the recovery of nitric acid and rare earth element stage by stage, first by the particle and suspension in pickle liquor After impurity removes, then through diffusion dialysis device the acid in pickling filtrate is separated and recovered, while make the raffinate containing rare earth element be in Faintly acid, reclaimed beneficial to the precipitation of rare earth element, the rare earth element ion reaction added in appropriate ammonium hydrogen carbonate and raffinate Precipitation is formed, and during the course of the reaction, the precipitation prevented by controlling mixing speed, while to improve reaction speed is sunk Product forms the turbid solution beneficial to press filtration in reaction container bottom, finally using diaphragm filter press press filtration, obtains low dilute of water content Native filter residue, reach the purpose of rare earth element recovery.
During experiment, inventor has found, when water and the velocity ratio of pickling filtrate increase, acid recovering rate increase, still, Too high water, pickle liquor velocity ratio can reduce again the concentration of recovery acid, be unfavorable for production reuse or the acid of back segment recovery acid Concentration and recovery；Under conditions of the flow velocity of water is constant, increase with the flow velocity of pickle liquor, acid recovering rate reduces, conversely, pickling Waste liquid flow velocity reduces, acid recovering rate increase；Consider from commercial Application angle, when should improve acid recovery efficiency and control recovery It is long, economize on resources again, suitable water flow velocity and pickle liquor flow velocity is extremely important.Therefore, inventor passes through a large amount of creative Experiment, and consider with reference to commercial Application, the flow velocity for controlling water is 1.8L/min~2.2L/min, and the flow velocity of pickle liquor is It 1.8L/min~2.0L/min, can realize that acid recovering rate is higher, and be reclaimed beneficial to the precipitation of follow-up rare earth element, is unlikely to again Because pickle liquor flow velocity needs very much long recovery time slowly, commercial Application demand can be met.
In addition, ammonium hydrogen carbonate and rare earth ion reaction are as follows：
RE3++NH4HCO3→[REOH]2++NH4 ++CO2↑
RE3++2NH4HCO3→[RE(OH)2]++2NH4 ++2CO2↑
2[RE(OH)2]++3NH4HCO3+(n-2)H2O→RE2(CO3)3·n H2O+NH4++NH3↑。
Therefore, react to form rare earth carbonate precipitation using ammonium hydrogen carbonate and rare earth element ion, all do not have in removal process There is the impurity beyond introducing system, also without the property for changing solution, and the pH of residual waste solution filters close to neutrality after being easy to press filtration The follow-up sewage qualified discharge processing of liquid.
In one of the embodiments, the ratio of the flow velocity of the water and the flow velocity of the pickling filtrate is 1~1.2:1. In one of the embodiments, the addition quality of the ammonium hydrogen carbonate：The neodymium iron boron magnetic materials pickle liquor middle rare earth quality is 6:1~7:1.
In one of the embodiments, the diffusion dialysis device is homogeneous-phase anion exchange film diffusion dialysis device.
Preferably, the homogeneous-phase anion exchange film is one in DF120 types or DF120H type homogeneous-phase anion exchange films Kind.
In one of the embodiments, the filter membrane that the pickle liquor filtering and impurity removing uses for microporous teflon membran or Polyvinylidene fluoride microporous film, the filtering accuracy of the filter membrane≤l μm.
Further, the filter membrane is hydrophilic polyfluortetraethylemicroporous microporous membrane.
In one of the embodiments, the diaphragm filter press is macromolecular elastomer diaphragm filter press, the macromolecule The filter cloth material of elastomeric septum filter press is terylene.
In one of the embodiments, in addition to：The rare earth filter residue is subjected to calcination, obtains rare earth oxide.
Further, the calcination temperature is 800 DEG C~1000 DEG C.
The application method carries out the separation and recovery of acid and rare earth element using diffusion dialysis and precipitation, press filtration stage by stage.Through After being filtered to remove particle and suspended contamination in pickle liquor, then the rationally flow velocity of control water and pickle liquor, oozed through diffusion Acid and rare earth element in analysis apparatus separation pickle liquor, make raffinate containing rare earth element be in faintly acid while recovery acid, then plus Enter the rare earth element ion in appropriate ammonium hydrogen carbonate and raffinate to react to form precipitation, in course of reaction, by controlling stirring speed Degree, the turbid solution beneficial to press filtration is formed, finally using diaphragm filter press press filtration, the low rare earth filter residue of water content is obtained, is burnt Burn, obtain rare earth oxide, complete the recovery of rare earth element；Up to more than 85%, the rate of recovery of rare earth element reaches the rate of recovery of acid To more than 90%.
The impurity that the application method is not introduced beyond system in removal process, easy to operate, used equipment is simple, And diffusion dialysis device hardly consumes the energy, other film methods are not replaced, and recovery acid can be by supplementing eo-acid, adjusting Reuse is directly produced after whole concentration, the rare earth oxide of recovery can carry out reproduction, realize the recycling of resource, reduce production Cost, while the processing pressure of sewage plant is alleviated, there is important economic benefit and environmental benefit.
Brief description of the drawings
Fig. 1 is the structural representation of one embodiment of the invention neodymium iron boron magnetic materials pickle liquor recovery system；
Fig. 2 is the technological process that one embodiment of the invention reclaims nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor Figure.
Embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to relevant drawings.In accompanying drawing Give presently preferred embodiments of the present invention.But the present invention can realize in many different forms, however it is not limited to this paper institutes The embodiment of description.On the contrary, the purpose for providing these embodiments is to make the understanding to the disclosure more thorough Comprehensively.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases The arbitrary and all group of the Listed Items of pass.
As shown in figure 1, be the structural representation of one embodiment of the invention neodymium iron boron magnetic materials pickle liquor recovery system, neodymium iron Boron magnetic material pickle liquor recovery system 100 includes：Acid-restoring plant 60 and pass sequentially through the devil liquor recovery dress that pipeline is connected Put 10, filter 20, sour separator 30, precipitation reaction device 40 and dehydration device 50；Also set on waste liquid recovery apparatus 10 There is waste collection mouth 12, waste collection mouth 12 is connected with descaling bath 70, for collecting the pickle liquor in descaling bath 70；Acid returns Receiving apparatus 60 is connected with descaling bath 70 by pipeline；Acid discharge mouth 32, acid discharge mouth 32 and acid recovery are additionally provided with sour separator 30 Device 60 is connected；Agitator 42 is provided with precipitation reaction device 40.
During the use of neodymium iron boron magnetic materials pickle liquor recovery system 100, it can not will be further continued for making when secondary in descaling bath 70 Pickle liquor is recycled to waste liquid recovery apparatus 10, after natural subsidence, passes through the filtering and impurity removing of filter 20；Cross and filter out Pickle liquor enters sour separator 30 after miscellaneous, and the nitric acid after separation enters acid-restoring plant 60, can be dense by adding in production After acid enter the reuse of descaling bath 70 or for other production among；Raffinate after separation nitric acid enters precipitation reaction device 40, Appropriate rare-earth precipitation agent is added, and is stirred continuously with agitator 42, forms rare-earth precipitation；By the precipitation in precipitation reaction device 40 It is transferred to dehydration device 50 and carries out dewater treatment, obtain rare earth filter residue, the heated decomposition of rare earth filter residue can obtain higher dilute of purity Native oxide, reach the purpose of recovering rare earth element, and the discharging of waste liquid after recovering rare earth element is to sewage plant, it is up to standard through handling After discharge.
In one of the embodiments, flowmeter 34 is additionally provided between filter 20 and sour separator 30, is used for The flow velocity that the pickling filtrate after filtered device 20 filters flows into sour separator 30 is detected, reaches acid recovering rate and recovery speed To production requirement.
In one of the embodiments, sour separator 30 is diffusion dialysis device.
Further, homogeneous-phase anion exchange film is provided with diffusion dialysis device, homogeneous-phase anion exchange film will spread Electrodialysis apparatus inner chamber is separated into dialysing compartment and diffuser casing.The diffuser casing of diffusion dialysis device is provided with water inlet and acid discharge mouth, oozes Analysis room is provided with sour inlet and residual liquid discharge port；One end of dialysing compartment is connected by sour inlet with filter 20, dialysis The other end of room is connected by residual liquid discharge port with precipitation reaction device 40, one end of diffuser casing by water inlet receive come Water from the external world, the other end of diffuser casing are connected by acid discharge mouth with acid-restoring plant.
Preferably, the homogeneous-phase anion exchange film in diffusion dialysis device be selected from DF120 types or DF120H types it is homogeneous it is cloudy from Proton exchange.It is appreciated that the anion-exchange membrane of the acid corrosion-resistant of other models may be selected as acid separation diffusion dialysis dress The exchange membrane put.
Diffusion dialysis device utilizes the selective penetrated property of anion-exchange membrane, makes the H in pickle liquor+By high concentration side The process migrated by film to low concentration side, this process are using concentration difference as power, so electric energy need not be consumed, can be saved Save the energy.
In one of the embodiments, dehydration device 50 is diaphragm filter press.Preferably, diaphragm filter press selects macromolecule Elastomeric septum filter press.
Further, multiple membrane filter plates are provided with diaphragm filter press, the two-sided of membrane filter plate carries diaphragm type chamber, more Individual membrane filter plate is spaced the filter chamber to form a constant volume one by one, after the completion of rare-earth precipitation filtering, to diaphragm type intracavitary The gas (or liquid) of injection certain pressure makes barrier film stick out reversely to filter residue spinning, and can reach reduces filter residue moisture content mesh 's.
In one of the embodiments, the filter membrane of filtering accuracy≤l μm is provided with filter 20.
Further, filter membrane is selected from microporous teflon membran or polyvinylidene fluoride microporous film.Polytetrafluoroethylene (PTFE) micropore Film and polyvinylidene fluoride microporous film are respectively provided with extremely strong chemical stability, the filtering available for severe corrosive chemicals.Preferably, From hydrophilic polyfluortetraethylemicroporous microporous membrane.
In one of the embodiments, be provided with least two series connection in filter 20, and filtering accuracy≤l μm it is poly- Tetrafluoroethene filter core.
In one of the embodiments, first is provided with the pipeline that waste liquid recovery apparatus 10 is connected with filter 20 First booster pump 24 of valve 22 and acid corrosion-resistant.First booster pump 24 is used for flowing into from waste liquid recovery apparatus 10 to pickle liquor Filter 20 provides power.It is appreciated that when the horizontal level of waste liquid recovery apparatus 10 is higher than the horizontal position of filter 20 Put, or the pickle liquor in waste liquid recovery apparatus 10 can flow directly into filter 20, waste liquid recovery apparatus 10 and filtering The first booster pump 34 can be not provided between device 20.
In one of the embodiments, second is provided with the pipeline that precipitation reaction device 40 is connected with dehydration device 50 Second booster pump 54 of valve 52 and acid corrosion-resistant, the second booster pump 54 are used for the solution containing rare-earth precipitation being pumped into dehydration device 50 are dehydrated.
In one of the embodiments, the first booster pump 24 and the second booster pump 54 be can acid-alkali-corrosive-resisting screw rod Pump.
It is specific embodiment below
Embodiment 1
When acidity and rare earth ion total amount in the secondary neodymium iron boron magnetic materials pickle liquor that can not be further continued for using in detection production, Detection finds that the acidity of pickle liquor is 0.98mol/L, and rare earth element total amount is 5.1g/L (in terms of rare earth oxide), and volume is about 300L。
The method of nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor is reclaimed, is returned using neodymium iron boron magnetic materials pickle liquor Receipts system 100 is carried out, and is comprised the following steps (referring to Fig. 2)：
1) the secondary pickle liquor that can not be further continued for using will be worked as in descaling bath 70 and is recycled to waste liquid recovery apparatus 10, it is naturally heavy 30min drops.
2) valve 22 is opened, starts the first booster pump 24, the pickle liquor after sedimentation is pumped into filter 20 and carried out Filter, the impurity such as suspension, particle in removal pickle liquor；Wherein, filter membrane used in filter 20 corrodes for resistance to strong acid Hydrophilic polyfluortetraethylemicroporous filter membrane, its filtering accuracy be l μm.
3) the pickling filtrate after filtering and impurity removing flows into diffusion dialysis device 30 and carries out sour separation and recovery, controls pickling filtrate Flow velocity is 1.8L/min, water flow velocity 1.8L/min, and the nitric acid after recovery enters acid-restoring plant 60, produced back after adding concentrated acid With；Dialyser is that DF120 types homogeneous-phase anion exchange film (is purchased from Shandong marine chemical industry wherein used in diffusion dialysis device 60 Research institute).
4) reclaim the raffinate containing rare earth element after nitric acid and enter precipitation reaction device 40, be charged with 10Kg bicarbonates Ammonium, while be stirred continuously by agitating device 42, reaction generation rare-earth precipitation, mixing speed is controlled in 60r/min~80r/ min.By controlling mixing speed, it on the one hand can accelerate to precipitate generating rate, on the other hand precipitation can be prevented to be deposited on reaction The bottom of container, beneficial to follow-up diaphragm plate frame press filtration.
5) after stirring 20min~25min, the second valve 52 is opened, and starts the second booster pump 54, by precipitation reaction device The turbid solution containing rare-earth precipitation is sent into diaphragm filter press 50 in 40, rare earth filter residue is obtained after press filtration, the discharging of waste liquid after press filtration Discharged to sewage plant after processing is up to standard；The barrier film of the diaphragm filter press 50 is macromolecular elastomer barrier film, the material of filter cloth For the terylene of acid corrosion-resistant.
6) rare earth filter residue obtains the higher rare earth oxide of purity after 850 DEG C of calcinations are decomposed, and reaches recovering rare earth element Purpose.
After testing, the concentration for reclaiming nitric acid in the waste liquid after nitric acid is 0.11mol/L, and the nitric acid rate of recovery is 88.8%；It is dilute Earth elements (count) rate of recovery as 92.7% using oxide.
Embodiment 2
When acidity and rare earth ion total amount in the secondary neodymium iron boron magnetic materials pickle liquor that can not be further continued for using in detection production, Detection finds that the acidity of pickle liquor is 0.76mol/L, and rare earth element total amount is 7.2g/L (in terms of rare earth oxide), and volume is about 300L。
The method of nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor is reclaimed, is returned using neodymium iron boron magnetic materials pickle liquor Receipts system 100 is carried out, and is comprised the following steps (referring to Fig. 2)：
1) the secondary pickle liquor that can not be further continued for using will be worked as in descaling bath 70 and is recycled to waste liquid recovery apparatus 10, it is naturally heavy 60min drops.
2) valve 22 is opened, starts the first booster pump 24, the pickle liquor after sedimentation is pumped into filter 20 and carried out Filter, the impurity such as suspension, particle in removal pickle liquor；Filter membrane is the hydrophilic of resistance to strong acid wherein used in filter 20 Property Kynoar filter membrane, its filtering accuracy be 0.8 μm.
3) the pickling filtrate after filtering and impurity removing flows into diffusion dialysis device 30 and carries out sour separation and recovery, controls pickling filtrate Flow velocity is 2.0L/min, water flow velocity 2.2L/min, and the nitric acid after recovery enters acid-restoring plant 60, produced back after adding concentrated acid With；Dialyser is DF120H type homogeneous-phase anion exchange films wherein used in diffusion dialysis device 60.
4) reclaim the raffinate containing rare earth element after nitric acid and enter precipitation reaction device 40, be charged with 15Kg bicarbonates Ammonium, while be stirred continuously by agitating device 42, reaction generation rare-earth precipitation, mixing speed is controlled in 60r/min~80r/ min.By controlling mixing speed, it on the one hand can accelerate to precipitate generating rate, on the other hand precipitation can be prevented to be deposited on reaction The bottom of container, beneficial to follow-up diaphragm plate frame press filtration.
5) after stirring 20min~25min, the second valve 52 is opened, and starts the second booster pump 54, by precipitation reaction device The turbid solution containing rare-earth precipitation is sent into diaphragm filter press 50 in 40, rare earth filter residue is obtained after press filtration, the discharging of waste liquid after press filtration Discharged to sewage plant after processing is up to standard；The barrier film of the diaphragm filter press 50 is macromolecular elastomer barrier film, the material of filter cloth For the terylene of acid corrosion-resistant.
6) rare earth filter residue obtains the higher rare earth oxide of purity after 850 DEG C of calcinations are decomposed, and reaches recovering rare earth element Purpose.
Waste liquid acid concentration is 0.1mol/L after reclaiming nitric acid after testing, and the nitric acid rate of recovery is 86.8%；Rare earth element is (with oxygen Compound meter) rate of recovery be 94.2%.
Embodiment 3
When acidity and rare earth ion total amount in the secondary neodymium iron boron magnetic materials pickle liquor that can not be further continued for using in detection production, Detection finds that the acidity of pickle liquor is 0.82mol/L, and rare earth element total amount is 6.3g/L (in terms of rare earth oxide), and volume is about 300L。
The method of nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor is reclaimed, is returned using neodymium iron boron magnetic materials pickle liquor Receipts system 100 is carried out, and is comprised the following steps (referring to Fig. 2)：
1) the secondary pickle liquor that can not be further continued for using will be worked as in descaling bath 70 and is recycled to waste liquid recovery apparatus 10, it is naturally heavy 45min drops.
2) valve 22 is opened, starts the first booster pump 24, the pickle liquor after sedimentation is pumped into filter 20 and carried out Filter, the impurity such as suspension, particle in removal pickle liquor；Filter membrane is the hydrophilic of resistance to strong acid wherein used in filter 20 Property teflon membrane filter, its filtering accuracy be 0.6 μm.
3) the pickling filtrate after filtering and impurity removing flows into diffusion dialysis device 30 and carries out sour separation and recovery, controls pickling filtrate Flow velocity is 1.9L/min, water flow velocity 2.2L/min, and the nitric acid after recovery enters acid-restoring plant 60, produced back after adding concentrated acid With；Dialyser is DF120H type homogeneous-phase anion exchange films wherein used in diffusion dialysis device 60.
4) reclaim the raffinate containing rare earth element after nitric acid and enter precipitation reaction device 40, be charged with 8Kg ammonium hydrogen carbonate, It is stirred continuously simultaneously, forms double salt of rare earth precipitation, mixing speed control is for 50r/min~60r/min.
5) after stirring 30min~40min, the second valve 52 is opened, and starts the second booster pump 54, by precipitation reaction device The turbid solution containing rare-earth precipitation is sent into diaphragm filter press 50 in 40, rare earth filter residue is obtained after press filtration, the discharging of waste liquid after press filtration Discharged to sewage plant after processing is up to standard；The barrier film of the diaphragm filter press 50 is macromolecular elastomer barrier film, the material of filter cloth For the terylene of acid corrosion-resistant.
6) rare earth filter residue obtains the higher rare earth oxide of purity after 850 DEG C of calcinations are decomposed, and reaches recovering rare earth element Purpose.
Waste liquid acid concentration is 0.1mol/L after reclaiming nitric acid after testing, and the nitric acid rate of recovery is 87.8%；Rare earth element is (with oxygen Compound meter) rate of recovery be 90.1%.
Embodiment 4
When acidity and rare earth ion total amount in the secondary neodymium iron boron magnetic materials pickle liquor that can not be further continued for using in detection production, Detection finds that the acidity of pickle liquor is 0.76mol/L, and rare earth element total amount is 6.7g/L (in terms of rare earth oxide), and volume is about 300L。
The method of nitric acid and rare earth element in neodymium iron boron magnetic materials pickle liquor is reclaimed, is returned using neodymium iron boron magnetic materials pickle liquor Receipts system 100 is carried out, and is comprised the following steps (referring to Fig. 2)：
1) the secondary pickle liquor that can not be further continued for using will be worked as in descaling bath 70 and is recycled to waste liquid recovery apparatus 10, it is naturally heavy 50min drops.
2) valve 22 is opened, starts the first booster pump 24, the pickle liquor after sedimentation is pumped into filter 20 and carried out Filter, the impurity such as suspension, particle in removal pickle liquor；Filter membrane used in the filter 20 is hydrophilic for resistance to strong acid Property teflon membrane filter, its filtering accuracy be 0.4 μm.
3) the pickling filtrate after filtering and impurity removing flows into diffusion dialysis device 30 and carries out sour separation and recovery, pickling filtrate flow velocity Control as 1.8L/min, water flow velocity 2.0L/min, the nitric acid after recovery enters acid-restoring plant 60, produced back after adding eo-acid With；Dialyser used in the diffusion dialysis device 60 is DF120 type homogeneous-phase anion exchange films.
4) reclaim the raffinate containing rare earth element after nitric acid and enter precipitation reaction device 40, be charged with 10Kg bicarbonates Ammonium, while be stirred continuously by agitating device 42, forms double salt of rare earth precipitation, and mixing speed control is for 80r/min~100r/ min。
5) after stirring 40min~50min, the second valve 52 is opened, and starts the second booster pump 54, by precipitation reaction device The turbid solution containing rare-earth precipitation is sent into diaphragm filter press 50 in 40, rare earth filter residue is obtained after press filtration, the discharging of waste liquid after press filtration Discharged to sewage plant after processing is up to standard；The barrier film of the diaphragm filter press 50 is macromolecular elastomer barrier film, the material of filter cloth For the terylene of acid corrosion-resistant.
6) rare earth filter residue obtains the higher rare earth oxide of purity after 850 DEG C of calcinations are decomposed, and reaches recovering rare earth element Purpose.
Waste liquid acid concentration is 0.11mol/L after reclaiming nitric acid after testing, and the nitric acid rate of recovery is 85.5%；Rare earth element (with Oxide meter) rate of recovery be 90.5%.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, and difference is, pickling filtrate flow velocity is 2.5L/min, and water flow velocity is 2.5L/min, ammonium hydrogen carbonate addition are 4kg, and the nitric acid rate of recovery 75.2%, the rare earth element rate of recovery is 65.3%.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 2, and difference is, mixing speed is 30r/min~45r/min nitric acid The rate of recovery is 86.2%；The rare earth element rate of recovery is 83.2%.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 2, and difference is, step 4) contains rare earth element to reclaim after nitric acid Raffinate enters precipitation reaction device 40, is charged with 15Kg sodium sulphate, while is stirred continuously by agitating device 42, is formed dilute Soil precipitation, mixing speed control is for 60r/min~80r/min.
After testing, the concentration for reclaiming nitric acid in the waste liquid after nitric acid is 0.1mol/L, and the nitric acid rate of recovery is 86.8%；Rare earth Element (counts) rate of recovery as 50.8% using oxide.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of method of nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor, it is characterised in that including following step Suddenly：
The pickle liquor of neodymium iron boron magnetic materials is obtained, the acid containing 0.5mol/L~1mol/L and 4g/L in the pickle liquor~ 10g/L rare earth element, wherein, rare earth element quality is in terms of rare earth oxide；
By the pickle liquor filtering and impurity removing, pickling filtrate is obtained；
Water and the pickling filtrate are injected separately into the water inlet of diffusion dialysis device and sour inlet, control the stream of the water Speed is 1.8L/min~2.2L/min, and the flow velocity of the pickling filtrate is 1.8L/min~2.0L/min, is recycled acid and contains Rare earth element raffinate；
Ammonium hydrogen carbonate is added into the raffinate containing rare earth element, with 50r/min~100r/min stirrings, reaction, is obtained containing dilute The turbid solution of soil precipitation；It is 4 that the ammonium hydrogen carbonate, which adds quality with the neodymium iron boron magnetic materials pickle liquor middle rare earth mass ratio,: 1~7:1；
By the turbid solution containing rare-earth precipitation through diaphragm filter press press filtration, rare earth filter residue is obtained；.
2. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 1, its feature It is, the ratio of the flow velocity of the water and the flow velocity of the pickling filtrate is 1~1.2:1.
3. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 1, its feature It is, the addition quality of the ammonium hydrogen carbonate：The quality of the neodymium iron boron magnetic materials pickle liquor rare earth elements is 6:1~7:1.
4. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 1, its feature It is, the diffusion dialysis device is homogeneous-phase anion exchange film diffusion dialysis device.
5. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 4, its feature It is, the homogeneous-phase anion exchange film is one kind in DF120 types or DF120H type homogeneous-phase anion exchange films.
6. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 1, its feature It is, the filter membrane that the pickle liquor filtering and impurity removing uses is described for microporous teflon membran or polyvinylidene fluoride microporous film The filtering accuracy of filter membrane≤l μm.
7. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 6, its feature It is, the filter membrane is hydrophilic polyfluortetraethylemicroporous microporous membrane.
8. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 1, its feature It is, the diaphragm filter press is macromolecular elastomer diaphragm filter press, the filter cloth of the macromolecular elastomer diaphragm filter press Material is terylene.
9. the side of nitric acid and rare earth element in the recovery neodymium iron boron magnetic materials pickle liquor according to any one of claim 1~8 Method, it is characterised in that also include：The rare earth filter residue is subjected to calcination, obtains rare earth oxide.
10. the method for nitric acid and rare earth element in recovery neodymium iron boron magnetic materials pickle liquor according to claim 9, its feature It is, the calcination temperature is 800 DEG C~1000 DEG C.
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