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CN113461260A - Method for recycling and denitrifying ion type rare earth mine tail water rare earth - Google Patents

Method for recycling and denitrifying ion type rare earth mine tail water rare earth Download PDF

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Publication number
CN113461260A
CN113461260A CN202110753201.9A CN202110753201A CN113461260A CN 113461260 A CN113461260 A CN 113461260A CN 202110753201 A CN202110753201 A CN 202110753201A CN 113461260 A CN113461260 A CN 113461260A
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rare earth
short
wastewater
denitrification
reaction
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张大超
黄磊欢
邓玉坤
苏昊
赵杰俊
陈国梁
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Ganzhou Ecological Environment Engineering Investment Co ltd
Ganzhou Rare Earth Mineral Industry Co ltd
Jiangxi University of Science and Technology
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Ganzhou Ecological Environment Engineering Investment Co ltd
Ganzhou Rare Earth Mineral Industry Co ltd
Jiangxi University of Science and Technology
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Priority to CN202110753201.9A priority Critical patent/CN113461260A/en
Publication of CN113461260A publication Critical patent/CN113461260A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00Obtaining rare earth metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • C02F2101/163Nitrates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • C02F2101/166Nitrites
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes
    • C02F3/302Nitrification and denitrification treatment
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Environmental & Geological Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

The invention discloses a method for recovering and denitrifying ion type rare earth mine tail water and aims to solve the technical problems that in the prior art, the treatment cost of the traditional process is high, the environment friendliness is poor, the environmental pollution is easy to form, and the newly developed treatment process is difficult to control and realize in the treatment of the ion type rare earth mine tail water. According to the treatment method, precious rare earth resources in the ammonia nitrogen tail water of the ionic rare earth mine are recycled firstly, so that the recovery rate of mineral resources is improved, then the nitration process is controlled in a nitrosation stage, and then denitrification is performed by directly utilizing nitrite nitrogen, so that the reaction flow is shortened, the reaction speed can be accelerated, the aeration energy consumption and the consumption of an organic carbon source can be greatly reduced, the process cost of wastewater denitrification is remarkably saved, and economic benefits can be created by recycling the rare earth resources.

Description

Method for recycling and denitrifying ion type rare earth mine tail water rare earth
Technical Field
The invention belongs to the field of sewage treatment, and particularly belongs to a method for recovering and denitrifying rare earth in tail water of an ionic rare earth mine.
Background
At present, the mining of the ionic rare earth ore is mainly carried out by in-situ ore leaching, namely, ammonium sulfate is injected into an ore deposit to be used as an ore leaching agent for leaching and recovering rare earth; in the process of extracting rare earth by in-situ leaching, the injected ammonium sulfate leaching agent is still remained in the ore deposit soil in a large amount except that part of the ammonium sulfate leaching agent is recovered by rare earth mother liquor. Under the action of atmospheric rainfall leaching, the rare earth mine after in-situ leaching mining can continuously leach NH for a long period of time4 +、NO3 -And rare earth metal ions form the rare earth mine ammonia nitrogen tail water, so the problem of water environment pollution of the rare earth mine watershed is more prominent; therefore, aiming at the problem, the ion type rare earth mine ammonia nitrogen tail water must be treated, on one hand, precious rare earth resources in the tail water are recovered, on the other hand, nitrogen in the tail water is removed, and the pollution to the environment is eliminated.
Aiming at the water quality of ionic rare earth mine tail water, the method is mainly characterized in that: firstly, the pH value of the waste water is low and is acidic, and the pH value is generally between 2 and 5; secondly, the carbon-nitrogen ratio is extremely low, and the organic carbon source is extremely deficient; and thirdly, ammonium nitrogen and nitrate nitrogen coexist, wherein the concentration of the ammonium nitrogen is generally 30-350mg/L, the concentration of the nitrate nitrogen is generally 20-150mg/L, and the nitrate nitrogen is generally 30% -50% of the total nitrogen in the wastewater.
At present, the ionic rare earth mine tail water denitrification treatment method mainly comprises two methods, namely biological denitrification and chemical denitrification, wherein the biological denitrification basically adopts the traditional nitrification/denitrification process, and the chemical denitrification mainly adopts the chemical treatment process of a breakpoint chlorination method. However, because the organic carbon source in the wastewater is extremely deficient, a large amount of organic carbon source needs to be added in the traditional biological denitrification process by nitrification/denitrification, which causes the treatment cost of the denitrification process to be higher; the chemical denitrification requires a large amount of chemical reagents, has high treatment cost, poor environmental friendliness and easy environmental pollution, so the biological denitrification is most applied in practical engineering nowadays. In addition, biological denitrification also has a newly developed anaerobic ammonia oxidation denitrification treatment process, and although the process does not need an organic carbon source, the start-up time is long, the operation control requirement is extremely high, and the process is not easy to realize. Therefore, the development of a novel biological denitrification process with high denitrification efficiency and simple operation control and the recycling of the rare earth resources in the ionic rare earth mine tailing water are more and more urgent.
Disclosure of Invention
(1) Technical problem to be solved
Aiming at the defects of the prior art, the invention aims to provide a method for recovering and denitrifying ion type rare earth mine tail water, which aims to solve the technical problems that the treatment of the ion type rare earth mine tail water in the prior art has higher treatment cost of the traditional process, poor environmental friendliness and easy environmental pollution, and the newly developed treatment process is difficult to control and realize.
(2) Technical scheme
In order to solve the technical problems, the invention provides a method for recovering and denitrifying ion type rare earth mine tail water rare earth, which can be used for treating by an ion type rare earth mine tail water rare earth recovery and denitrifying treatment device, wherein the device comprises a raw water tank, a rare earth recovery component, a short-cut nitration reaction component and a denitrification reaction component; the rare earth recovery assembly is communicated with an outlet of the raw water tank, the shortcut nitrification reaction assembly is communicated with the rare earth recovery assembly, and the denitrification reaction assembly is communicated with the shortcut nitrification reaction assembly.
The method is used for recovering and denitrifying the rare earth in the tail water of the ionic rare earth mine, and comprises the following steps: firstly, carrying out neutralization and precipitation on ionic rare earth mine ammonia nitrogen tail water raw wastewater, recovering rare earth resources in the raw wastewater, then inoculating shortcut nitrification activated sludge to the wastewater, carrying out shortcut nitrification reaction on the wastewater to completely oxidize ammonia nitrogen in the wastewater into nitrite nitrogen, finally inoculating denitrification activated sludge to the wastewater, carrying out denitrification on the wastewater through denitrification reaction, and reducing the nitrite nitrogen and the original nitrate nitrogen in the tail water into nitrogen to be removed.
According to the method for recovering and denitrifying the rare earth in the ionic rare earth mine tail water, precious rare earth resources in the ionic rare earth mine ammonia nitrogen tail water are recovered at first, the recovery rate of mineral resources is improved, then the nitrification process is controlled in the nitrosation stage, and denitrification is directly carried out by using nitrite nitrogen, so that the reaction process is shortened, the reaction speed is increased, the aeration energy consumption and the consumption of organic carbon sources can be greatly reduced, the process cost of wastewater denitrification is remarkably saved, and economic benefits can be created by recovering the rare earth resources.
Preferably, the agent used for neutralizing the precipitate is Ca (OH)2
(3) Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
1. the treatment method recovers the rare earth resources through the neutralization precipitation, not only can recover the precious rare earth resources for further recovery and utilization, improve the comprehensive recovery rate of the rare earth resources, create benefits, but also can avoid the situation that the rare earth metals inhibit microorganisms in the subsequent biological wastewater treatment link, so that the biological wastewater treatment link cannot be smoothly carried out; in addition, the acid rare earth mine tail water can be neutralized, and the pH value of the acid rare earth mine tail water is increased, so that the acid rare earth mine tail water can meet the requirement of biological wastewater treatment on the pH value.
2. The treatment method comprises the steps of connecting a short-cut nitrification component and a denitrification component in series for use, firstly oxidizing all ammonium nitrogen contained in the wastewater into nitrite nitrogen by using a short-cut nitrification process, keeping the original nitrate nitrogen, and then reducing the nitrite nitrogen and the nitrate nitrogen into nitrogen by using denitrification to achieve the aim of denitrification; the process controls the nitration process in the nitrosation stage, directly utilizes nitrite nitrogen to carry out denitrification, shortens the reaction process, can accelerate the reaction speed, greatly saves the aeration energy consumption and the consumption of organic carbon sources, and obviously saves the process cost of wastewater denitrification.
3. The treatment method utilizes the short-cut nitrification reaction, partial ammonium nitrogen in the wastewater is oxidized into nitrite nitrogen through the activated sludge in the short-cut nitrification reaction, so that a necessary nitrite nitrogen substrate is provided for the subsequent anaerobic ammonia oxidation reaction, and compared with the whole-process nitrification, the oxygen supply amount is saved, so that the aeration energy consumption is saved, and the wastewater treatment cost is saved.
4. The treatment method reduces untreated nitrate nitrogen and generated nitrate nitrogen in the wastewater into nitrogen gas for removal through denitrification reaction, can control the nitrate nitrogen of the wastewater to be at a lower concentration, improves the removal rate of total nitrogen, solves the problem that COD dosage is not determined well due to water inflow quality fluctuation, and prevents the waste of organic carbon sources and the problem of high COD concentration of treated effluent.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easily understood and obvious, the technical solutions in the embodiments of the present invention are clearly and completely described below to further illustrate the invention, and obviously, the described embodiments are only a part of the embodiments of the present invention, but not all the embodiments.
Ion type rare earth mine tail water treatment facilities includes: the device comprises a raw water tank, a rare earth recovery component, a short-cut nitrification reaction component and a denitrification reaction component; the rare earth recovery component is communicated with an outlet of the raw water pool through a centrifugal pump, and the rare earth recovery component is used for recovering rare earth from raw wastewater; the short-cut nitrification reaction component is communicated with the rare earth recovery component through a centrifugal pump, and the short-cut nitrification reaction is carried out on the pretreated wastewater to generate ammonium nitrogen into nitrite nitrogen; the denitrification reaction component is communicated with the short-cut nitrification reaction component, and carries out denitrification reaction on the wastewater from the short-cut nitrification reaction component so as to reduce the original nitrate nitrogen in the wastewater and the nitrite nitrogen generated by the short-cut nitrification reaction component into nitrogen.
The rare earth recovery assembly comprises a rare earth recovery reaction tank, a sedimentation tank, a first medicine storage tank, a second medicine storage tank, a pH monitor and a computer controller, wherein the rare earth recovery reaction tank is used for carrying out neutralization reaction on rare earth metals in the wastewater; the first medicine storage box stores medicine liquid Ca (OH) which can be neutralized with rare earth metal2The first medicine storage box is used for conveying liquid medicine to the rare earth recovery reaction tank; a flocculating agent PAC is stored in the second medicine storage box, and the first medicine storage box is used for conveying liquid medicine to the rare earth recovery reaction tank; the computer controller is respectively connected with the pH monitor, the first medicine storage box and the second medicine storage box, and the computer controller receives data of the pH monitor so as to feedback control the adding amount of the first medicine storage box; the sedimentation tank is communicated with the rare earth recovery reaction tank and is used for collecting sediments generated by the neutralization reaction for rare earth recovery.
The short-cut nitrification reaction component comprises a nitrification reactor, a blast aeration device, a second medicine storage box, a pH monitor, a dissolved oxygen monitor and a computer controller; the short-cut nitrification reactor is communicated with the rare earth recovery assembly through a centrifugal pump, short-cut nitrification activated sludge is inoculated in the short-cut nitrification reactor, and the short-cut nitrification reactor carries out short-cut nitrification reaction on the wastewater to generate nitrite nitrogen from ammonium nitrogen; the blast aeration device is communicated with the short-cut nitrification reactor, and supplies oxygen to the wastewater and adjusts the concentration of dissolved oxygen; the second medicine storage box is communicated with the short-cut nitrification reactor, and the second medicine storage box conveys liquid medicine to the short-cut nitrification reactor to keep the pH value of the wastewater so as to ensure that the short-cut nitrification reactor normally operates; the computer controller is respectively connected with the pH monitor, the dissolved oxygen monitor, the third medicine storage box and the blast aeration device, the computer controller receives data of the pH monitor to feedback control the alkali liquor adding amount of the third medicine storage box, and the computer controller receives data of the dissolved oxygen monitor to feedback control the start and stop of the blast aeration device; the short path nitration reactor may be a sequencing batch reactor or a continuous flow reactor.
The denitrification reaction component comprises a denitrification reactor, a nitrate nitrogen online monitor, a COD monitor, a computer controller and a third medicine storage box; the denitrification reactor is communicated with the shortcut nitrification reaction component and is used for inoculating denitrification sludge to carry out denitrification reaction on the wastewater, so that untreated nitrate nitrogen in the wastewater and nitrite nitrogen generated by the shortcut nitrification reaction component are removed; the third medicine storage box is communicated with the denitrification reactor, and the second medicine storage box is used for providing an organic carbon source for the denitrification reactor; the computer controller receives the data of the nitrate nitrogen on-line monitor and the COD monitor to obtain the nitrate nitrogen concentration and the COD concentration of the inlet and outlet water, automatically calculates the adding amount of the organic carbon source through a computer program, and finally feeds the adding amount back to the third medicine storage box to realize the accurate control of the adding amount of the organic carbon source.
The short-cut nitrification reactor and the denitrification reactor are not limited by whether the short-cut nitrification reactor and the denitrification reactor are sequencing batch reactors or continuous flow reactors, as long as corresponding biological reaction treatment functions can be realized, but when the two reactors are a sequencing batch reactor and a continuous flow reactor, an intermediate water tank needs to be additionally arranged between the two reactors, so that the sequencing batch reactor and the continuous flow reactor can be effectively connected.
In order to achieve the effect that the wastewater can be uniformly mixed in the reactor, stirring devices can be respectively arranged in the rare earth recovery reaction tank and the short-cut nitrification reactor.
In order to realize the automatic adjustment of the pH in the rare earth recovery reaction tank assembly and the short-cut nitrification reaction assembly, pH monitors are arranged in the rare earth recovery reaction tank and the short-cut nitrification reactor and are linked with corresponding dosing devices, so that the automatic adjustment of the pH is realized.
The working principle of the ionic rare earth mine ammonia nitrogen tail water treatment device is as follows: firstly, inoculating corresponding activated sludge in a short-cut nitrification reactor and a denitrification reactor, then conveying wastewater from a raw water tank to a rare earth recovery reaction tank, adding liquid medicine into the rare earth recovery reaction tank by utilizing a first medicine storage tank and a second medicine storage tank to enable rare earth metal to generate neutralization reaction, introducing the reacted wastewater into a sedimentation tank for sedimentation, wherein sediments collected in the sedimentation tank contain the rare earth metal, and the rare earth metal can be recovered by conveying the sediments to a rare earth smelting enterprise. And then, conveying the supernatant in the sedimentation tank to a short-cut nitrification reactor through a centrifugal pump so as to perform short-cut nitrification reaction in the short-cut nitrification reactor, simultaneously adding alkali liquor into the short-cut nitrification reactor through a third medicine storage box so as to perform short-cut nitrification reaction on short-cut nitrifying bacteria under a proper pH condition, and naturally overflowing the wastewater treated by the short-cut nitrification reaction into the denitrification reactor. And finally, carrying out denitrification reaction in the denitrification reactor, and simultaneously accurately controlling the amount of the organic carbon source added into the denitrification reactor by the third medicine storage box through the computer controller, so that the denitrifying bacteria carry out denitrification reaction under the proper C/N condition, and the problem that the adding amount of the organic carbon source is not well determined due to fluctuation of the quality of inlet water in the denitrification process is solved.
The ionic rare earth mine tail water rare earth recovery and denitrification treatment device firstly utilizes a short-cut nitrification process technology to oxidize ammonium nitrogen contained in the wastewater into nitrite nitrogen and keep nitrate nitrogen originally contained in the wastewater by coupling the short-cut nitrification reaction component and the denitrification reaction component, and then utilizes a denitrification technology to reduce the nitrite nitrogen and the nitrate nitrogen into nitrogen, so as to achieve the aim of denitrification; the process firstly controls the nitration process in the nitrosation stage, directly utilizes nitrite nitrogen to carry out denitrification, shortens the denitrification reaction process, not only can accelerate the reaction speed, but also can greatly save aeration energy consumption and organic carbon source consumption; and secondly, in the denitrification process, the waste of an organic carbon source is prevented by a real-time control system under the condition of realizing the stable operation of denitrification, and the cost of the wastewater denitrification process is obviously saved.
The ion type rare earth mine tail water rare earth recovery and denitrification treatment device comprises an ion type rare earth mine ammonia nitrogen tail water biological treatment device, and is characterized in that activated sludge is inoculated in the ion type rare earth mine ammonia nitrogen tail water biological treatment device, and then wastewater is introduced to carry out rare earth recovery reaction, short-cut nitrification reaction and denitrification reaction in sequence.
Specifically, the rare earth recovery reaction comprises the following steps: introducing the wastewater in the raw water tank into a rare earth recovery reaction tank through a centrifugal pump, adding alkali liquor into a pretreatment regulating tank to control the pH of the wastewater in the rare earth recovery reaction tank to be 8.0-9.0, performing neutralization reaction on rare earth metal and the alkali liquor for precipitation, and then sending the precipitation into a precipitation tank.
The short-cut nitration reaction comprises the following steps: the supernatant in the sedimentation tank is sent into the short-cut nitrification reactor through a centrifugal pump, DO of the wastewater in the short-cut nitrification reactor is controlled to be 0.2-0.7mg/L through a blast aeration device, the pH of the wastewater in the short-cut nitrification reactor is adjusted to be 7.0-9.0 through a second medicine storage box, so that under the environment, the short-cut nitrification bacteria can oxidize ammonium nitrogen of the wastewater to generate nitrite nitrogen, and then the wastewater after the short-cut nitrification reaction enters the denitrification reactor.
The denitrification reaction comprises the following steps: after the wastewater reacted by the short-cut nitrification reactor enters the denitrification reactor, the amount of the added organic carbon source is accurately controlled by the computer controller, and the C/N is controlled to be 3-6, so that the denitrifying bacteria can further remove the original nitrate nitrogen in the wastewater and the nitrite nitrogen generated by the short-cut nitrification reaction component under the environment through denitrification, and the purpose of improving the total nitrogen removal effect of the wastewater is achieved.
By sequentially carrying out rare earth recovery reaction, short-range nitration reaction and denitrification reaction on the wastewater, firstly, the nitration process is controlled in a nitrosation stage, and denitrification is directly carried out by using nitrite nitrogen, so that the reaction process is shortened, the reaction speed can be accelerated, and the aeration energy consumption and the organic carbon source consumption can be greatly saved; and secondly, in the denitrification process, the waste of an organic carbon source is prevented by a real-time control system under the condition of realizing the stable operation of denitrification, and the cost of the wastewater denitrification process is obviously saved.
Wherein NH of the wastewater to be treated4 +N concentration of 100mg/L, NO3 -The concentration of N was 60mg/L and the pH was 4.0. The short-cut nitrification reactor and the short-cut denitrification reactor are respectively inoculated with nitrification formed by culturing mixed sludge taken from a municipal sewage plant in a laboratory for a period of timeThe concentration of the inoculated activated sludge is 2000-3000 mg/L.
In the treatment process, firstly, the wastewater in the raw water tank is conveyed into a rare earth recovery reaction tank by using a peristaltic pump, the pH is adjusted to 8.5, and then the wastewater is discharged into a sedimentation tank.
And then conveying the supernatant wastewater in the sedimentation tank to a short-cut nitrification reactor by a peristaltic pump, wherein the short-cut nitrification reactor is an SBR reactor, the hydraulic retention time is 2-6h, and DO is controlled within the range of 0.2-0.7 mg/L. And (4) allowing the water after the short-cut nitration to enter a denitrification reactor.
When the wastewater is subjected to denitrification reaction in the denitrification reactor, the C/N in the wastewater is controlled to be 3-6 by using the computer controller. The hydraulic retention time of the denitrification reactor is 2-6 h.
And (3) processing results: after 60 days of start-up, a stable treatment effect can be obtained, and NO is discharged from the short-cut nitrification reactor3 --N concentration 60-67mg/L, NO2 --N concentration 88-95mg/L, NH4 +-N concentration is 0-8 mg/L; NO of effluent of denitrification reactor3 --N concentration 2-8mg/L, NO2 --N concentration of 0.1mg/L to 2mg/L, NH4 +The concentration of-N is 0.5mg/L to 12 mg/L.
Having thus described the principal technical features and basic principles of the invention, and the advantages associated therewith, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description is described in terms of various embodiments, not every embodiment includes only a single embodiment, and such descriptions are provided for clarity only, and those skilled in the art will recognize that the embodiments described herein can be combined as a whole to form other embodiments as would be understood by those skilled in the art.

Claims (6)

1.一种离子型稀土矿山尾水稀土回收及脱氮处理的方法,其特征在于,该方法的步骤包括:首先,对离子型稀土矿山氨氮尾水原废水进行中和沉淀,回收原废水中的稀土资源,之后,对废水接种短程硝化活性污泥,并将废水通过短程硝化反应,将废水中的氨氮全部氧化为亚硝酸盐氮,最后,对废水接种反硝化活性污泥,并将废水通过反硝化反应,对废水进行脱氮,将亚硝酸盐氮和尾水中原有的硝酸盐氮还原为氮气去除。1. a method for ion type rare earth mine tail water rare earth recovery and denitrification treatment, it is characterized in that, the step of this method comprises: First, neutralize and precipitate the ion type rare earth mine ammonia nitrogen tail water raw waste water, reclaim the original waste water. Rare earth resources, after that, the wastewater is inoculated with short-range nitrification activated sludge, and the wastewater is subjected to short-range nitrification to oxidize all ammonia nitrogen in the wastewater to nitrite nitrogen. Finally, the wastewater is inoculated with denitrification activated sludge, and the wastewater is passed through The denitrification reaction is used to denitrify the wastewater, and the nitrite nitrogen and the original nitrate nitrogen in the tail water are reduced to nitrogen for removal. 2.根据权利要求1所述的一种离子型稀土矿山尾水稀土回收及脱氮处理的方法,其特征在于,所述中和沉淀使用的药剂为Ca(OH)22 . The method for recovering and denitrifying ionic rare earth mine tail water according to claim 1 , wherein the agent used for the neutralization and precipitation is Ca(OH) 2 . 3 . 3.根据权利要求2所述的一种离子型稀土矿山尾水稀土回收及脱氮处理的方法,其特征在于,该方法使用离子型稀土矿山尾水处理装置,该装置包括原水池、稀土回收组件、短程硝化反应组件、反硝化反应组件;其中,稀土回收组件与原水池出口通过离心泵接通接通,稀土回收组件对原废水进行稀土回收;短程硝化反应组件与稀土回收组件通过离心泵接通,对预处理后的废水进行短程硝化反应以将其中的铵态氮生成为亚硝酸盐氮;反硝化反应组件与短程硝化反应组件接通,反硝化反应组件对来自短程硝化反应组件的废水进行反硝化反应,以将废水中原有的硝酸盐氮和短程硝化反应组件生成的亚硝酸盐氮还原为氮气;3. The method for recovering rare earth and denitrifying treatment of ionic rare earth mine tail water according to claim 2, wherein the method uses an ionic rare earth mine tail water treatment device, and the device comprises a raw water tank, a rare earth recovery Components, short-range nitrification reaction components, and denitrification reaction components; wherein, the rare earth recovery component is connected to the outlet of the raw water tank through a centrifugal pump, and the rare earth recovery component performs rare earth recovery on the raw wastewater; the short-range nitrification reaction component and the rare earth recovery component are connected by a centrifugal pump Connected, short-range nitrification reaction is performed on the pretreated wastewater to generate ammonium nitrogen into nitrite nitrogen; the denitrification reaction component is connected with the short-range nitrification reaction component, and the denitrification reaction component is used for The wastewater is subjected to a denitrification reaction to reduce the original nitrate nitrogen in the wastewater and the nitrite nitrogen generated by the short-range nitrification reaction component to nitrogen; 稀土回收组件包括稀土回收反应池、沉淀池、第一储药箱、第二储药箱、pH监测仪和计算机控制器,稀土回收反应池用于对废水中的稀土金属进行中和反应;第一储药箱内存储可与稀土金属进行中和反应的药液Ca(OH)2,第一储药箱用于向稀土回收反应池输送药液;第二储药箱内存储絮凝剂PAC,第一储药箱用于向稀土回收反应池输送药液;计算机控制器分别与pH监测仪、第一储药箱和第二储药箱连接,计算机控制器通过接收pH监测仪的数据,从而反馈控制第一储药箱的投加量;沉淀池与稀土回收反应池接通,沉淀池用于收集中和反应生成的沉淀物进行稀土回收;The rare earth recovery component includes a rare earth recovery reaction tank, a sedimentation tank, a first medicine storage tank, a second medicine storage tank, a pH monitor and a computer controller, and the rare earth recovery reaction tank is used for neutralizing the rare earth metals in the wastewater; A medicine storage box stores the chemical liquid Ca(OH) 2 that can neutralize the rare earth metals, the first medicine storage box is used to transport the medicine liquid to the rare earth recovery reaction tank; the second medicine storage box stores the flocculant PAC, The first medicine storage box is used to transport the medicine liquid to the rare earth recovery reaction tank; the computer controller is respectively connected with the pH monitor, the first medicine storage box and the second medicine storage box, and the computer controller receives the data of the pH monitor, thereby Feedback controls the dosage of the first medicine storage tank; the sedimentation tank is connected with the rare earth recovery reaction tank, and the sedimentation tank is used to collect the precipitate generated by the neutralization reaction for rare earth recovery; 短程硝化反应组件包括硝化反应器、鼓风曝气装置、第二储药箱、pH监测仪、溶解氧监测仪和计算机控制器;短程硝化反应器与稀土回收组件通过离心泵接通,短程硝化反应器内接种短程硝化活性污泥,短程硝化反应器对废水进行短程硝化反应,将铵态氮生成亚硝酸盐氮;鼓风曝气装置与短程硝化反应器接通,鼓风曝气装置对废水供氧及对溶解氧浓度进行调节;第二储药箱与短程硝化反应器接通,第二储药箱向短程硝化反应器输送药液以保持废水的pH值从而使短程硝化反应正常运行;计算机控制器分别与pH监测仪、溶解氧监测仪、第三储药箱和鼓风曝气装置连接,计算机控制器通过接收pH监测仪的数据,从而反馈控制第三储药箱的碱液投加量,计算机控制器通过接收溶解氧监测仪的数据,从而反馈控制鼓风曝气装置的启停;短程硝化反应器可以是序批式反应器或连续流反应器;The short-range nitrification reaction component includes a nitrification reactor, a blast aeration device, a second medicine storage tank, a pH monitor, a dissolved oxygen monitor and a computer controller; the short-range nitrification reactor and the rare earth recovery component are connected through a centrifugal pump, and the short-range nitrification The short-range nitrification activated sludge is inoculated in the reactor, and the short-range nitrification reactor performs short-range nitrification reaction on the wastewater to generate nitrite nitrogen from ammonium nitrogen; the blast aeration device is connected to the short-range nitrification reactor, and the blast aeration device The waste water supplies oxygen and adjusts the dissolved oxygen concentration; the second medicine storage tank is connected to the short-range nitrification reactor, and the second medicine storage tank sends the liquid medicine to the short-range nitrification reactor to maintain the pH value of the waste water so that the short-range nitrification reaction can operate normally ;The computer controller is respectively connected with the pH monitor, dissolved oxygen monitor, the third medicine storage tank and the blast aeration device, and the computer controller receives the data of the pH monitor to feedback control the lye of the third medicine storage tank Dosing amount, the computer controller receives the data of the dissolved oxygen monitor, so as to feedback control the start and stop of the blast aeration device; the short-range nitrification reactor can be a sequence batch reactor or a continuous flow reactor; 反硝化反应组件包括反硝化反应器、硝酸盐氮在线监测仪、COD监测仪、计算机控制器和第三储药箱;反硝化反应器与短程硝化反应组件接通,反硝化反应器内用于接种反硝化污泥对废水进行反硝化反应,使得废水中未处理的硝态氮以及短程硝化反应组件生成的亚硝态氮被去除;第三储药箱与反硝化反应器接通,第二储药箱用于为反硝化反应器提供有机碳源;计算机控制器通过接收硝酸盐氮在线监测仪和COD监测仪的数据,获得的进出水的硝酸盐氮浓度和COD浓度,再经电脑程序自动计算出有机碳源的投加量,最后反馈给第三储药箱,实现精确控制有机碳源的投加量。The denitrification reaction component includes a denitrification reactor, a nitrate nitrogen online monitor, a COD monitor, a computer controller and a third medicine storage tank; the denitrification reactor is connected to the short-range nitrification reaction component, and the denitrification reactor is used for Inoculating denitrification sludge to denitrify the wastewater, so that the untreated nitrate nitrogen in the wastewater and the nitrite nitrogen generated by the short-range nitrification reaction components are removed; the third medicine storage tank is connected to the denitrification reactor, and the second The medicine storage box is used to provide the organic carbon source for the denitrification reactor; the computer controller receives the data of the nitrate nitrogen online monitor and COD monitor, and obtains the nitrate nitrogen concentration and COD concentration of the incoming and outgoing water, and then passes the computer program. The dosage of the organic carbon source is automatically calculated and fed back to the third medicine storage box to achieve precise control of the dosage of the organic carbon source. 4.根据权利要求3所述的一种离子型稀土矿山尾水稀土回收及脱氮处理的方法,其特征在于,所述稀土回收反应包括以下步骤:通过离心泵将原水池内的废水通入至稀土回收反应池,往预处理调节池内加碱液以控制稀土回收反应池的废水pH为8.0-9.0,使得稀土金属与碱液进行中和反应沉淀,然后送入沉淀池。4. The method for recovering and denitrifying the tail water of an ionic rare earth mine according to claim 3, wherein the rare earth recovery reaction comprises the following steps: passing the waste water in the raw water tank into the Rare earth recovery reaction tank, add lye into the pretreatment adjustment tank to control the pH of the wastewater in the rare earth recovery reaction tank to be 8.0-9.0, so that the rare earth metal and the alkali solution are neutralized and precipitated, and then sent to the sedimentation tank. 5.根据权利要求3所述的一种离子型稀土矿山尾水稀土回收及脱氮处理的方法,其特征在于,所述短程硝化反应包括以下步骤:通过离心泵将沉淀池内的上清液送入至短程硝化反应器中,通过鼓风曝气装置控制短程硝化反应器内废水的DO为0.2-0.7mg/L,通过第二储药箱调节短程硝化反应器内废水的pH为7.0-9.0,从而使得在此环境下,短程硝化细菌可以将废水的铵态氮氧化生成亚硝酸盐氮,然后将短程硝化反应后的废水进反硝化反应器。5. The method for recovering and denitrifying the tail water of an ionic rare earth mine according to claim 3, wherein the short-range nitrification reaction comprises the steps of: sending the supernatant in the sedimentation tank by a centrifugal pump Put it into the short-path nitrification reactor, control the DO of the wastewater in the short-path nitrification reactor to be 0.2-0.7mg/L through the blast aeration device, and adjust the pH of the wastewater in the short-path nitrification reactor to 7.0-9.0 through the second medicine storage tank , so that in this environment, short-range nitrifying bacteria can oxidize ammonium nitrogen in wastewater to form nitrite nitrogen, and then feed the wastewater after short-range nitrification into the denitrification reactor. 6.根据权利要求3所述的一种离子型稀土矿山尾水稀土回收及脱氮处理的方法,其特征在于,所述反硝化反应包括以下步骤:短程硝化反应器反应后的废水进入反硝化反应器后,通过计算机控制器精确控制投加的有机碳源量,将C/N控制为3-6,使得在此环境下反硝化细菌可以将废水中原有硝酸盐氮、短程硝化反应组件生成的亚硝酸盐氮进一步通过反硝化作用去除。6 . The method for recovering rare earth and denitrifying treatment of ionic rare earth mine tail water according to claim 3 , wherein the denitrification reaction comprises the following steps: the wastewater after the short-path nitrification reactor reaction enters the denitrification process. 7 . After the reactor, the amount of organic carbon source added is precisely controlled by the computer controller, and the C/N ratio is controlled to 3-6, so that the denitrifying bacteria can generate the original nitrate nitrogen and short-range nitrification reaction components in the wastewater under this environment. The nitrite nitrogen is further removed by denitrification.
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