CN115583744A - Method for treating rare earth mine wastewater - Google Patents
Method for treating rare earth mine wastewater Download PDFInfo
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- CN115583744A CN115583744A CN202211198569.4A CN202211198569A CN115583744A CN 115583744 A CN115583744 A CN 115583744A CN 202211198569 A CN202211198569 A CN 202211198569A CN 115583744 A CN115583744 A CN 115583744A
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- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 239000002245 particle Substances 0.000 claims description 19
- 229920001661 Chitosan Polymers 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000004697 Polyetherimide Substances 0.000 claims description 15
- 229920001601 polyetherimide Polymers 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000009287 sand filtration Methods 0.000 claims description 11
- 230000004907 flux Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 7
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- 241000589651 Zoogloea Species 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
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- 229910052748 manganese Inorganic materials 0.000 description 1
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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
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for treating rare earth mine wastewater, which comprises the steps of adding quicklime into the rare earth mine wastewater, carrying out rough filtration treatment, and carrying out pre-impurity removal to obtain first waste liquid; the first waste liquid is introduced into the adsorption unit, and the adsorption unit can adsorb the rare earth elements in the first waste liquid, so that the rare earth elements in the rare earth mine waste water can be effectively recovered, and the rare earth elements are separated from the first waste liquid to obtain a second waste liquid; the second waste liquid flows into the ultrafiltration system, the second waste liquid is filtered, more fine particles and colloid in the second waste liquid flow into the biological filter bed after being filtered, ammonia nitrogen in the waste liquid can be effectively removed due to the enrichment of microorganisms with multiple functions in the biological filter bed, and the target waste liquid is obtained.
Description
Technical Field
The invention belongs to the technical field of rare earth mine wastewater treatment, and particularly relates to a method for treating rare earth mine wastewater.
Background
The south ionic rare earth ore has been developed for over thirty years in China since the last 70 s of mining, the mining process has been developed from the most original 'pool leaching process' to the existing 'in-situ leaching process', and the leaching agent is also changed from sodium chloride to ammonium sulfate. The transformation is friendly to the environment, and on one hand, the 'mountain moving motion' of large-scale ore mining is avoided, and the vegetation on the surface of the mine is protected; and secondly, the use of the ammonium sulfate leaching agent also prevents the efflorescence of sodium chloride to mines, and the ammonia in the ammonium sulfate is necessary nutrition for plant growth and is beneficial to improving the environment to a certain extent. However, the improvement of the above process can not change the ecological environment of the rare earth mine.
For many years, the environment has been severely eroded by wastewater produced by mining and wastewater that flows out of residual rare earth ores left after mining. The waste water contains 0.01-0.1 g/L of rare earth ions, about 2g/L of ammonium sulfate solution and some compounds of heavy metal, fluorine ions and arsenic, the concentration of the waste water containing the substances is higher and higher after long-term accumulation, and the waste water can flow to all corners around a mine along with the washing of rainwater, so that green vegetation is damaged, and the ecological environment of the mine is influenced.
The rare earth resources are precious resources in China and are not renewable, and if the rare earth in the wastewater is directly discharged, the rare earth resources are greatly wasted. On the other hand, the high ammonia nitrogen sulfate wastewater is directly discharged into the water body, which causes water eutrophication and reduces the ornamental value of the water body, and nitrate and nitrite generated by oxidation can cause permanent damage to aquatic organisms and even human health. In 2011, 24 months and 11 days, the environmental protection department releases 14 provincial and level-84 rare earth enterprises in China, and only 15 enterprises meet the environmental protection requirement on the ammonia nitrogen content of wastewater. Therefore, how to conveniently and economically recover valuable rare earth elements in the wastewater discharged in the rare earth production process and reduce the ammonia nitrogen content to the national allowable standard becomes one of the problems to be solved urgently by rare earth production enterprises in China.
Disclosure of Invention
Based on the above, the embodiment of the invention provides a method for treating rare earth mine wastewater, aiming at solving the problems of complex process and high cost in the prior art that valuable rare earth elements in wastewater discharged in the rare earth production process are traditionally recovered, and the ammonia nitrogen content is reduced to the national allowable standard.
The first aspect of the embodiment of the invention provides a method for treating rare earth mine wastewater, which is performed by a device for treating rare earth mine wastewater, wherein the device for treating rare earth mine wastewater comprises a pretreatment tank, an adsorption unit, an ultrafiltration system and a biological filter bed which are sequentially connected, the adsorption unit is further connected with a desorption tank, and the method comprises the following steps:
introducing the rare earth mine wastewater into the pretreatment tank, adding quicklime, and carrying out rough filtration treatment to obtain a first waste liquid;
introducing the first waste liquid into an adsorption unit, wherein the adsorption unit is used for absorbing rare earth elements in the first waste liquid to obtain a second waste liquid, after the adsorption unit is adsorbed and saturated, analyzing the adsorption unit by using a dilute hydrochloric acid solution with a preset mass percentage concentration to obtain a rare earth solution containing the rare earth elements, and introducing the rare earth solution into an analysis pool;
enabling the second waste liquid to flow into the ultrafiltration system, and carrying out filtration treatment to obtain a third waste liquid;
and (3) flowing the third waste liquid into the biological filter bed, and periodically controlling water inflow and aeration to obtain the target waste liquid.
And further, introducing the rare earth mine wastewater into the pretreatment tank, adding quicklime, and performing rough filtration to obtain a first waste liquid, wherein the rough filtration is performed by one of carbon filtration, sand filtration and multi-medium filtration.
Further, the pH value of the first waste liquid is 7-8.
Further, the preset mass percentage concentration of the dilute hydrochloric acid solution is 15-30%.
Further, the material of the adsorption unit is based on polyetherimide modified chitosan derivative.
Further, in the step of flowing the second waste liquid into an ultrafiltration system for filtration to obtain a third waste liquid, the ultrafiltration system is used for removing solid particles and colloids with the granularity of more than 0.1 mu m in the second waste liquid, wherein the operating pressure of the ultrafiltration system is controlled to be 0.2-0.6 Mpa, the inlet water temperature is controlled to be less than 60 ℃, and the membrane flux is controlled to be 300-500L/m 2 h。
Further, the biological filter bed is a soil high-load type microbial filter bed, wherein the biological filter bed is prepared by taking multi-biological-phase zoogloea as a basic filler.
Further, in the step of flowing the third waste liquid into the biological filter bed and periodically controlling water inflow and aeration to obtain the target waste liquid, controlling the water inflow rate of the biological filter bed to be 200-250L/min and periodically performing ammonia nitrogen removal treatment, wherein after controlling the water inflow time to be 20-30 min, the biological filter bed is stopped for 30-40 min, and after re-aeration is performed for 20-30 min, the biological filter bed is stopped for 30-40 min, which is a period.
Further, the amount of the polyetherimide-based chitosan derivative to be added is 0.5 to 1kg/t.
Compared with the prior art, the implementation of the invention has the following beneficial effects:
adding quicklime into the rare earth mine wastewater, and performing rough filtration treatment to obtain a first wastewater which has a neutral pH value and does not contain large particles and colloids; the first waste liquid is introduced into the adsorption unit, and the adsorption unit can adsorb the rare earth elements in the first waste liquid, so that the rare earth elements in the rare earth mine waste water can be effectively recovered, and the rare earth elements are separated from the first waste liquid to obtain a second waste liquid; the second waste liquid flows into an ultrafiltration system for filtration treatment, finer particles and colloids in the second waste liquid flow into a biological filter bed after being filtered, microorganisms with multiple functions are enriched in the biological filter bed, the pH value of the waste water is adjusted to be neutral when pre-impurity removal is carried out, the survival environment of the microorganisms in the biological filter bed is not damaged, ammonia nitrogen in the waste water can be effectively removed through the biological filter bed, target waste liquid is obtained, in addition, pollutants such as ammonia nitrogen and the like are treated by adopting a biological method, the dosage of traditional medicaments is reduced, the process steps are simplified, the operation cost can be effectively reduced, and no secondary pollution exists.
Drawings
FIG. 1 is a schematic view of a process for treating rare earth mine wastewater;
FIG. 2 is a block diagram showing the arrangement of an apparatus for treating rare earth mine wastewater.
The following detailed description will be further described in conjunction with the above-identified drawing figures.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Several embodiments of the invention are presented in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The first aspect of the present invention is directed to the problems of complex process and high cost in the conventional method for recovering valuable rare earth elements from wastewater discharged in the rare earth production process and reducing the ammonia nitrogen content to the national allowable standard, and provides a method for treating rare earth mine wastewater, referring to fig. 1, which is a schematic process flow diagram for treating rare earth mine wastewater, wherein the method comprises the following steps:
introducing the rare earth mine wastewater into a pretreatment tank, adding quicklime, and carrying out rough filtration treatment to obtain a first waste liquid;
introducing the first waste liquid into an adsorption unit, wherein the adsorption unit is used for absorbing rare earth elements in the first waste liquid to obtain a second waste liquid, after the adsorption unit is saturated in adsorption, analyzing the adsorption unit through a dilute hydrochloric acid solution with preset mass percentage concentration to obtain a rare earth solution containing the rare earth elements, and introducing the rare earth solution into an analysis pool;
enabling the second waste liquid to flow into an ultrafiltration system, and carrying out filtration treatment to obtain a third waste liquid;
and (4) flowing the third waste liquid into the biological filter bed, and periodically controlling water inflow and aeration to obtain the target waste liquid.
In some embodiments of the present invention, in the step of introducing the rare earth mine wastewater into the pretreatment tank, adding quicklime, and performing rough filtration to obtain the first waste liquid, adding quicklime into the rare earth mine wastewater, adjusting the pH, and then filtering solid particles and colloids in the rare earth mine wastewater by one of carbon filtration, sand filtration, or multi-media filtration, wherein a medium used in the sand filtration is natural quartz sand or manganese sand, and the particle size of the quartz sand is 0.5 to 1.2mm, so that the large molecular solid particles and colloids in the water can be retained to filter impurities.
In some embodiments of the invention, the pH of the first spent liquor is between 7 and 8.
In some embodiments of the invention, after the adsorption unit is saturated by adsorption, the adsorption unit is analyzed by a dilute hydrochloric acid solution with a preset mass percentage concentration to obtain a rare earth solution containing a rare earth element, and the rare earth solution is introduced into an analysis tank, and after the adsorption unit is saturated by adsorption, the adsorption unit is analyzed by a dilute hydrochloric acid solution with a concentration of 15-30% to obtain a rare earth solution containing a rare earth element, wherein the adsorption unit comprises an adsorption column made of an adsorption material, and the adsorption column is used for adsorbing the rare earth element in the rare earth mine wastewater.
In some embodiments of the present invention, the adsorbing material is a novel material selectively adsorbing rare earth elements, specifically, the material of the adsorbing unit is a polyetherimide-modified chitosan derivative, and the input amount is 0.5 to 1kg/t, that is, 0.5 to 1kg of the polyetherimide-modified chitosan derivative is input into each ton of rare earth mine wastewater, wherein the adsorption rate of the rare earth elements can reach more than 80%.
In some embodiments of the present invention, in the step of flowing the second waste liquid into the ultrafiltration system for filtration to obtain the third waste liquid, the ultrafiltration system is configured to remove solid particles and colloids with a particle size greater than 0.1 μm in the second waste liquid, so as to further filter impurities, wherein the operation pressure of the ultrafiltration system is controlled to be 0.2 to 0.6Mpa, the inlet water temperature is less than 60 ℃, and the membrane flux is 300 to 500L/m 2 And h, the backwashing period is 12h, and the backwashing time is 5min, wherein the ultrafiltration system comprises an ultrafiltration membrane component which is a tubular ultrafiltration membrane and is made of glass fiber synthetic paper with the inner diameter of 4-25mm and the length of 0.3-6 m.
In some embodiments of the present invention, the biofilter bed is a soil high-load type microbial filter bed, wherein the biofilter bed is prepared by using multi-bio-zoogloea as a basic filler, and the ammonia nitrogen concentration of the third waste liquid flowing into the biofilter bed is generally 100-160 mg/L.
The method for treating the rare earth mine wastewater comprises the steps of treating the rare earth mine wastewater through a device for treating the rare earth mine wastewater, as shown in fig. 2, and is a layout block diagram of the device for treating the rare earth mine wastewater, wherein the device comprises a pretreatment tank 1, an adsorption unit 2, an ultrafiltration system 4 and a biological filter bed 5 which are connected in sequence, the adsorption unit 2 is further connected with an analysis tank 3, the adsorption unit 2 is analyzed through a dilute hydrochloric acid solution with preset mass percentage concentration after the adsorption unit 2 is adsorbed and saturated, a rare earth solution containing rare earth elements is obtained, the rare earth solution is introduced into the analysis tank 3, it is required to say that the first waste liquid is introduced into the adsorption unit 2, the concentration of the rare earth elements in the flowing second waste liquid is detected, when the concentration of the rare earth elements reaches the preset concentration, the introduction of the first waste liquid is stopped, the adsorption unit 2 is analyzed, and the introduction of the first waste liquid is resumed after the analysis is completed.
In order to facilitate an understanding of the invention, several embodiments of the invention are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example one
In the embodiment, the rare earth mine wastewater is introduced into the pretreatment tank, quicklime is added into the rare earth mine wastewater in the pretreatment tank, after the pH value is adjusted, sand filtration is carried out to obtain a first waste liquid with the pH value of 7.2, and at normal temperature, the first waste liquid is treated according to the proportion of 50m 3 Introducing the flow of/h into an adsorption unit, wherein the adsorption unit is made of a polyetherimide modified chitosan derivative, the dosage of the polyetherimide modified chitosan derivative is 0.8kg/t, the rare earth element is recovered, a second waste liquid is obtained, the second waste liquid flows into an ultrafiltration system, the operating pressure of the ultrafiltration system is controlled to be 0.3Mpa, the water inlet temperature is controlled to be 20 ℃, and the membrane flux is 400L/m 2 And h, removing solid particles and colloids with the granularity larger than 0.1 mu m in the second waste liquid to obtain a third waste liquid, finally flowing the third waste liquid into a biological filter bed, controlling the water inflow rate of the biological filter bed to be 200L/min, and periodically carrying out ammonia nitrogen removal treatment, wherein after controlling the water inflow time to be 30min, stopping for 30min, after aerating for 30min, stopping for 30min, and carrying out ammonia nitrogen removal treatment to obtain the target waste liquid.
Specifically, in the process of rare earth element recovery, after the adsorption unit is saturated, the adsorption unit is analyzed by a 20% dilute hydrochloric acid solution to obtain a rare earth solution, in addition, the ammonia nitrogen concentration in the rare earth mine wastewater is 150mg/L, and after the process, the ammonia nitrogen concentration in the target waste liquid is 3.4mg/L.
Example two
In the embodiment, the rare earth mine wastewater is introduced into the pretreatment tank, quicklime is added into the rare earth mine wastewater in the pretreatment tank, after the pH value is adjusted, sand filtration is carried out to obtain a first waste liquid with the pH value of 7.5, and at normal temperature, the first waste liquid is treated according to the standard of 60m 3 Introducing flow of/h into an adsorption unit, wherein the material of the adsorption unit is a chitosan derivative modified based on polyetherimide, the adding amount is 0.7kg/t, and the rare earth element recovery treatment is carried out to obtain a secondAnd (3) introducing the second waste liquid into an ultrafiltration system, wherein the operating pressure of the ultrafiltration system is controlled to be 0.3Mpa, the inlet water temperature is controlled to be 20 ℃, and the membrane flux is controlled to be 500L/m 2 And h, removing solid particles and colloid with the granularity of more than 0.1 mu m in the second waste liquid to obtain third waste liquid, finally, flowing the third waste liquid into a biological filter bed, controlling the water inflow rate of the biological filter bed to be 250L/min, and periodically performing ammonia nitrogen removal treatment, wherein after controlling the water inflow time for 30min, stopping for 30min, after aerating for 30min, stopping for 30min, and performing ammonia nitrogen removal treatment to obtain the target waste liquid.
Specifically, in the process of rare earth element recovery, after the adsorption unit is adsorbed and saturated, the adsorption unit is analyzed by a 20% dilute hydrochloric acid solution to obtain a rare earth solution, in addition, the ammonia nitrogen concentration in the rare earth mine wastewater is 143mg/L, and after the process, the ammonia nitrogen concentration in the target waste liquid is 2.6mg/L.
EXAMPLE III
In the embodiment, the rare earth mine wastewater is introduced into the pretreatment tank, quicklime is added into the rare earth mine wastewater in the pretreatment tank, after the pH value is adjusted, sand filtration is carried out to obtain a first waste liquid with the pH value of 7.1, and at normal temperature, the first waste liquid is treated according to the proportion of 50m 3 Introducing the flow of/h into an adsorption unit, wherein the adsorption unit is made of a polyetherimide modified chitosan derivative, the dosage of the polyetherimide modified chitosan derivative is 0.6kg/t, the rare earth element is recovered, a second waste liquid is obtained, the second waste liquid flows into an ultrafiltration system, the operating pressure of the ultrafiltration system is controlled to be 0.3Mpa, the water inlet temperature is controlled to be 20 ℃, and the membrane flux is 400L/m 2 And h, removing solid particles and colloids with the granularity larger than 0.1 mu m in the second waste liquid to obtain a third waste liquid, finally flowing the third waste liquid into a biological filter bed, controlling the water inflow rate of the biological filter bed to be 250L/min, and periodically carrying out ammonia nitrogen removal treatment, wherein the water inflow time is controlled to be 20min, then stopping for 40min, then aerating for 20min, then stopping for 40min, and carrying out ammonia nitrogen removal treatment to obtain the target waste liquid.
Specifically, in the process of rare earth element recovery, after the adsorption unit is saturated, the adsorption unit is analyzed by a dilute hydrochloric acid solution with the concentration of 25% to obtain a rare earth solution, in addition, the ammonia nitrogen concentration in the rare earth mine wastewater is 159mg/L, and after the process, the ammonia nitrogen concentration in the target waste liquid is 2.1mg/L.
Example four
In the embodiment, the rare earth mine wastewater is introduced into the pretreatment tank, quicklime is added into the rare earth mine wastewater in the pretreatment tank, after the pH value is adjusted, sand filtration is carried out to obtain a first waste liquid with the pH value of 7.2, and at normal temperature, the first waste liquid is treated according to the standard of 60m 3 Introducing the flow of/h into an adsorption unit, wherein the adsorption unit is made of a polyetherimide modified chitosan derivative, the dosage of the polyetherimide modified chitosan derivative is 0.8kg/t, the rare earth element is recovered, a second waste liquid is obtained, the second waste liquid flows into an ultrafiltration system, the operating pressure of the ultrafiltration system is controlled to be 0.4Mpa, the water inlet temperature is controlled to be 20 ℃, and the membrane flux is 400L/m 2 And h, removing solid particles and colloid with the granularity of more than 0.1 mu m in the second waste liquid to obtain third waste liquid, finally, flowing the third waste liquid into a biological filter bed, controlling the water inflow rate of the biological filter bed to be 200L/min, and periodically performing ammonia nitrogen removal treatment, wherein the water inflow time is controlled to be 20min, then stopping for 40min, then aerating for 20min, then stopping for 40min, and performing ammonia nitrogen removal treatment to obtain the target waste liquid.
Specifically, in the process of rare earth element recovery, after the adsorption unit is saturated, the adsorption unit is analyzed by a 20% dilute hydrochloric acid solution to obtain a rare earth solution, in addition, the ammonia nitrogen concentration in the rare earth mine wastewater is 138mg/L, and after the process, the ammonia nitrogen concentration in the target waste liquid is 1.9mg/L.
EXAMPLE five
In the embodiment, the rare earth mine wastewater is introduced into the pretreatment tank, quicklime is added into the rare earth mine wastewater in the pretreatment tank, after the pH value is adjusted, sand filtration is carried out to obtain a first waste liquid with the pH value of 7.6, and at normal temperature, the first waste liquid is treated according to the standard of 60m 3 Introducing the flow of the raw materials into an adsorption unit, wherein the material of the adsorption unit is based on polyetherimide modified chitosan derivative, the adding amount is 0.75kg/t, and the rare earth elements are recoveredPerforming element treatment to obtain a second waste liquid, and allowing the second waste liquid to flow into an ultrafiltration system, wherein the operation pressure of the ultrafiltration system is controlled at 0.35Mpa, the inlet water temperature is controlled at 20 deg.C, and the membrane flux is 450L/m 2 And h, removing solid particles and colloids with the granularity larger than 0.1 mu m in the second waste liquid to obtain a third waste liquid, finally flowing the third waste liquid into a biological filter bed, controlling the water inflow rate of the biological filter bed to be 250L/min, and periodically carrying out ammonia nitrogen removal treatment, wherein after controlling the water inflow time to be 30min, stopping for 30min, after aerating for 30min, stopping for 30min, and carrying out ammonia nitrogen removal treatment to obtain the target waste liquid.
Specifically, in the process of rare earth element recovery, after the adsorption unit is saturated, the adsorption unit is analyzed by a 20% dilute hydrochloric acid solution to obtain a rare earth solution, in addition, the ammonia nitrogen concentration in the rare earth mine wastewater is 144mg/L, and after the process, the ammonia nitrogen concentration in the target waste liquid is 1.3mg/L.
EXAMPLE six
In the embodiment, the rare earth mine wastewater is introduced into the pretreatment tank, quicklime is added into the rare earth mine wastewater in the pretreatment tank, after the pH value is adjusted, sand filtration is carried out to obtain a first waste liquid with the pH value of 7.5, and at normal temperature, the first waste liquid is treated according to the proportion of 50m 3 Introducing the flow of/h into an adsorption unit, wherein the adsorption unit is made of a polyetherimide modified chitosan derivative, the dosage of the polyetherimide modified chitosan derivative is 0.8kg/t, the rare earth element is recovered, a second waste liquid is obtained, the second waste liquid flows into an ultrafiltration system, the operating pressure of the ultrafiltration system is controlled to be 0.3Mpa, the water inlet temperature is controlled to be 20 ℃, and the membrane flux is 400L/m 2 And h, removing solid particles and colloid with the granularity of more than 0.1 mu m in the second waste liquid to obtain third waste liquid, finally, flowing the third waste liquid into a biological filter bed, controlling the water inflow rate of the biological filter bed to be 200L/min, and periodically performing ammonia nitrogen removal treatment, wherein after controlling the water inflow time for 30min, stopping for 30min, after aerating for 30min, stopping for 30min, and performing ammonia nitrogen removal treatment to obtain the target waste liquid.
Specifically, in the process of rare earth element recovery, after the adsorption unit is saturated, the adsorption unit is analyzed by a 15% dilute hydrochloric acid solution to obtain a rare earth solution, in addition, the ammonia nitrogen concentration in the rare earth mine wastewater is 155mg/L, and after the process, the ammonia nitrogen concentration in the target waste liquid is 3.0mg/L.
EXAMPLE seven
In the embodiment, the rare earth mine wastewater is introduced into the pretreatment tank, quicklime is added into the rare earth mine wastewater in the pretreatment tank, after the pH value is adjusted, sand filtration is carried out to obtain a first waste liquid with the pH value of 7.8, and at normal temperature, the first waste liquid is treated according to the proportion of 50m 3 Introducing the flow of the solution/h into an adsorption unit, wherein the adsorption unit is made of polyetherimide modified chitosan derivative, the dosage is 0.8kg/t, the rare earth element is recovered, a second waste liquid is obtained, and the second waste liquid flows into an ultrafiltration system, wherein the operating pressure of the ultrafiltration system is controlled to be 0.3Mpa, the inlet water temperature is 20 ℃, and the membrane flux is 400L/m 2 And h, removing solid particles and colloids with the granularity larger than 0.1 mu m in the second waste liquid to obtain a third waste liquid, finally flowing the third waste liquid into a biological filter bed, controlling the water inflow rate of the biological filter bed to be 200L/min, and periodically carrying out ammonia nitrogen removal treatment, wherein after controlling the water inflow time to be 30min, stopping for 30min, after aerating for 30min, stopping for 30min, and carrying out ammonia nitrogen removal treatment to obtain the target waste liquid.
Specifically, in the process of rare earth element recovery, after the adsorption unit is saturated, the adsorption unit is analyzed by a 30% dilute hydrochloric acid solution to obtain a rare earth solution, in addition, the ammonia nitrogen concentration in the rare earth mine wastewater is 148mg/L, and after the process, the ammonia nitrogen concentration in the target waste liquid is 2.9mg/L.
Please refer to table 1 below, which shows the parameters corresponding to the first to seventh embodiments of the present invention;
table 1:
according to the table 1, the method for treating the rare earth mine wastewater provided by the invention has a good purification effect on ammonia nitrogen in the rare earth mine wastewater, the content of the ammonia nitrogen in the purified effluent is greatly reduced, and meanwhile, the rare earth elements in the rare earth mine wastewater are effectively recovered, so that the method for treating the rare earth mine wastewater provided by the embodiment can achieve the purposes of recovering valuable rare earth elements in the wastewater discharged in the rare earth production process and reducing the content of the ammonia nitrogen to the national allowable standard.
In summary, the invention relates to a method for treating rare earth mine wastewater, which comprises the steps of adding quicklime into the rare earth mine wastewater, and carrying out rough filtration treatment to obtain a first waste liquid which has a neutral pH value and does not contain large particles and colloid; the first waste liquid is introduced into the adsorption unit, and the adsorption unit can adsorb the rare earth elements in the first waste liquid, so that the rare earth elements in the rare earth mine waste water can be effectively recovered, and the rare earth elements are separated from the first waste liquid to obtain a second waste liquid; the second waste liquid flows into an ultrafiltration system for filtration treatment, finer particles and colloids in the second waste liquid flow into a biological filter bed after being filtered, microorganisms with multiple functions are enriched in the biological filter bed, the pH value of the waste water is adjusted to be neutral when pre-impurity removal is carried out, the survival environment of the microorganisms in the biological filter bed is not damaged, ammonia nitrogen in the waste water can be effectively removed through the biological filter bed, target waste liquid is obtained, in addition, pollutants such as ammonia nitrogen and the like are treated by adopting a biological method, the dosage of traditional medicaments is reduced, the process steps are simplified, the operation cost can be effectively reduced, and no secondary pollution exists.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A method for treating rare earth mine wastewater, which is characterized in that the treatment is carried out by an apparatus for treating rare earth mine wastewater, wherein the apparatus for treating rare earth mine wastewater comprises a pretreatment tank, an adsorption unit, an ultrafiltration system and a biological filter bed which are connected in sequence, wherein the adsorption unit is also connected with a desorption tank, and the method comprises the following steps:
introducing the rare earth mine wastewater into the pretreatment tank, adding quicklime, and carrying out rough filtration treatment to obtain a first waste liquid;
introducing the first waste liquid into an adsorption unit, wherein the adsorption unit is used for absorbing rare earth elements in the first waste liquid to obtain a second waste liquid, after the adsorption unit is saturated in adsorption, analyzing the adsorption unit by using a dilute hydrochloric acid solution with a preset mass percentage concentration to obtain a rare earth solution containing the rare earth elements, and introducing the rare earth solution into an analysis pool;
enabling the second waste liquid to flow into the ultrafiltration system, and carrying out filtration treatment to obtain a third waste liquid;
and (3) flowing the third waste liquid into the biological filter bed, and periodically controlling water inflow and aeration to obtain the target waste liquid.
2. The method for treating rare earth mine wastewater according to claim 1, wherein in the step of introducing the rare earth mine wastewater into the pretreatment tank, adding quicklime, and performing rough filtration treatment to obtain the first waste liquid, the rough filtration treatment is one of carbon filtration, sand filtration and multi-medium filtration.
3. The method for treating rare earth mine wastewater according to claim 2, wherein the pH of the first spent liquor is 7 to 8.
4. The method for treating rare earth mine wastewater according to claim 1, wherein the preset mass percentage concentration of the dilute hydrochloric acid solution is 15-30%.
5. The method for treating rare earth mine wastewater according to claim 4, wherein the material of the adsorption unit is based on polyetherimide modified chitosan derivatives.
6. The method for treating rare earth mine wastewater according to claim 1, wherein in the step of flowing the second waste liquid into the ultrafiltration system for filtration to obtain the third waste liquid, the ultrafiltration system is used for removing solid particles and colloids with particle sizes larger than 0.1 μm in the second waste liquid, wherein the operating pressure of the ultrafiltration system is controlled to be 0.2-0.6 Mpa, the inlet water temperature is less than 60 ℃, and the membrane flux is controlled to be 300-500L/m 2 h。
7. The method for treating rare earth mine wastewater according to claim 1, wherein the biofilter bed is a soil high-load type microbial filter bed, and the biofilter bed is prepared by using multi-biological zoogloea as a basic filler.
8. The method for treating rare earth mine wastewater according to claim 1, wherein in the step of flowing the third waste liquid into the biological filter bed and periodically controlling water inflow and aeration to obtain the target waste liquid, the water inflow rate of the biological filter bed is controlled to be 200-250L/min, and ammonia nitrogen removal treatment is performed periodically, wherein the period of time for water inflow is controlled to be 20-30 min, then the biological filter bed is stopped for 30-40 min, and then the biological filter bed is stopped for 30-40 min after being aerated for 20-30 min, thus obtaining a period.
9. The method for treating rare earth mine wastewater according to claim 5, wherein the amount of the polyetherimide-based modified chitosan derivative added is 0.5 to 1kg/t.
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