CN111268857A - Method for removing high-concentration ammonia nitrogen in residual ammonium salt leachate of rare earth leaching site by chemical-biological method - Google Patents
Method for removing high-concentration ammonia nitrogen in residual ammonium salt leachate of rare earth leaching site by chemical-biological method Download PDFInfo
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Abstract
The invention relates to a method for removing high-concentration ammonia nitrogen in residual ammonium salt leachate of a rare earth leaching site by utilizing a chemical-biological method. The method comprises the steps of firstly utilizing an ammonium magnesium phosphate precipitation method to pretreat the leachate of the rare earth leaching field with high ammonia nitrogen concentration, and then utilizing the indigenous denitrification microbial flora separated, enriched and screened from the leachate or soil of the rare earth leaching field to perform microbial denitrification treatment on the pretreated leachate, so that the qualified discharge of the leachate is finally realized. The method can treat the leachate with high ammonia nitrogen concentration, and the selected indigenous denitrification microbial community has strong adaptability and high denitrification efficiency, and has the advantages of simple process, environmental friendliness, easy industrialization and the like.
Description
Technical Field
The invention relates to the technical field of rare earth mining and sewage treatment, in particular to a method for removing high-concentration ammonia nitrogen in residual ammonium salt leachate of a rare earth leaching site by utilizing a chemical-biological method.
Background
The ionic rare earth ore is also called weathering crust eluviation type rare earth ore, and the novel exogenous rare earth ore deposit is discovered in the Jiangnan region of China at the end of the 60 th century in 20 th century. The ionic rare earth ore has complete distribution, is rich in rare medium and heavy rare earth elements on the earth, has the characteristics of rich resource reserves, low radioactivity, easy exploitation, high comprehensive utilization value and the like, and is an important strategic resource in China.
The ion type rare earth ore has most of rare earth elements existing in the form of ions, and the low rare earth content can only be exploited by a chemical leaching method, and the ammonium sulfate solution heap leaching process and the ammonium sulfate solution in-situ leaching process are currently more applied exploitation technologies. The two processes can generate a large amount of ammonia nitrogen wastewater in the mining process of a mining area, and in addition, a large amount of residual ammonium salts are also contained in an ion type rare earth mine closed site, and the residual ammonium salts can seriously hinder the environmental recovery and ecological balance of the mining area. The current method is to use clear water or other solutions to leach and collect residual ammonium salts from the closed mine field, and how to effectively treat the leachate is an important part for constructing an environment control system of the ionic rare earth mine closed mine field. Analysis shows that the residual ammonium salt leachate of the ionic rare earth mine closed-mine site has more complex components, large ammonia nitrogen concentration span, indefinite ammonia nitrogen content (as low as about 50Mg/L and as high as 1000Mg/L) in the leachate every time, low C/N ratio, high salinity, and also contains various metal ions such as Ca, Mg, Al and the like and a little rare earth elements.
At present, the treatment method of ammonia nitrogen wastewater mainly comprises a stripping method, a breakpoint chlorination method, a chemical precipitation method, an ion exchange method, a membrane separation method and a biological method. The methods have good treatment effect on the ammonia nitrogen wastewater, but have respective limitations. The stripping method, the breakpoint chlorination method and the chemical precipitation method have good treatment effects on the wastewater with high ammonia nitrogen concentration, but the wastewater with high ammonia nitrogen concentration is difficult to reach the national discharge standard and is easy to cause secondary pollution, so the method is generally used for pretreatment of the wastewater with high ammonia nitrogen concentration. The ion exchange method and the membrane separation method have high cost and are difficult to popularize and apply on a large scale. The biological method can only be used for treating the ammonia nitrogen wastewater with medium and low concentration, but cannot treat the wastewater with high ammonia nitrogen concentration. Aiming at the characteristics of large ammonia nitrogen concentration span and uncertain ammonia nitrogen concentration of the leachates in different batches of the leachates in the ion type rare earth ore closed site, the single treatment method in the solution is difficult to effectively complete the harmless treatment of the leachates, especially the leachates with high ammonia nitrogen concentration. Therefore, the combined process is used for cooperatively treating the leachate of the ionic rare earth mine closed-mine field, which is an important research direction for treating the ammonia nitrogen wastewater in the rare earth industry.
At present, the research reports of treating ammonia nitrogen wastewater by an ammonium magnesium phosphate precipitation method and a microbial method are common, but the research of combining the ammonium magnesium phosphate precipitation method and the microbial method for treating ammonia nitrogen wastewater in rare earth mines has not been reported. The method gives full play to the respective advantages, and aims at the ionic rare earth ore residual ammonium salt leachate with high ammonia nitrogen concentration, the ammonia nitrogen concentration of the ionic rare earth ore residual ammonium salt leachate is firstly reduced to the degree suitable for the survival and propagation of microorganisms through the treatment of an ammonium magnesium phosphate precipitation method, and then the leachate ammonia nitrogen is further treated by utilizing the indigenous denitrification microbial flora, so that the standard emission of the ammonia nitrogen of the leachate is realized.
Disclosure of Invention
The invention aims to provide a method for synergistically removing high-concentration ammonia nitrogen in residual ammonium salt leachate of a rare earth leaching site by using a chemical-biological method, which comprises the following specific steps: (a) pretreating the residual ammonium salt leachate of the rare earth leaching site by using an ammonium magnesium phosphate precipitation method to reduce the ammonia nitrogen concentration of the leachate to be suitable for the growth and the propagation of microorganisms, thereby obtaining the pretreated leachate; (b) separating and enriching leachate or soil of a rare earth leaching field to obtain an indigenous denitrification microbial flora enrichment culture solution, and performing denitrification screening culture on the enrichment culture solution to obtain an indigenous denitrification microbial flora; (c) and (b) carrying out microbial denitrification treatment on the leachate pretreated in the step (a) by utilizing indigenous denitrification microbial flora.
Further, the sources of the residual ammonium salt leachate in the rare earth leaching site in the step (a) are as follows: and adding an eluant into a liquid injection system of the ionic rare earth ore in-situ leaching process, eluting the residual ammonium salt in the rare earth ore leaching site, and collecting the eluent through a liquid collection system to obtain the residual ammonium salt leachate in the rare earth ore leaching site. The detection shows that the ammonia nitrogen concentration in the leachate is 500-1000 mg/L.
Further, the step (a) comprises the following specific steps: and adding magnesium salt, phosphate and a pH regulator into the residual ammonium salt leachate of the rare earth leaching site, fully stirring, and performing precipitation separation to obtain the pretreated leachate.
Furthermore, the magnesium salt, the phosphate and the pH regulator are added in an amount to ensure that the molar ratio of Mg, P and N in the solution is 1.1-1.3:1-1.2:1 and the pH value is 8.5-10. The magnesium salt is selected from at least one of magnesium chloride, magnesium sulfate and magnesium oxide; the phosphate is at least one of disodium hydrogen phosphate or sodium phosphate; the pH regulator is sodium hydroxide aqueous solution or sodium carbonate aqueous solution.
Further, the ammonia nitrogen concentration of the leachate pretreated in the step (a) is 100-300 mg/L.
Further, the separation and enrichment method of the culture solution for enriching the indigenous denitrification microbial flora in the step (b) is as follows: collecting a soil sample from a rare earth leaching site, mixing the soil sample with sterile water according to the proportion of 200-30 g:1L, carrying out constant-temperature shaking culture (the temperature is 28-30 ℃, the shaking time is 20-30min, the rotating speed is 150-170r/min), standing for a period of time (10-15min), and then taking a supernatant to obtain an initial bacterial suspension of the soil sample; then mixing the initial bacterial suspension of the soil sample with a denitrification enrichment medium according to the volume ratio of 1:2-3, and culturing at constant temperature (the culture temperature is 28-30 ℃, the rotating speed is 150-; mixing the first-time enriched soil denitrification microbial flora enrichment culture solution with a denitrification enrichment culture medium under the same culture condition according to the volume ratio of 1:3-4, and carrying out constant-temperature culture again to obtain a second-time enriched soil denitrification microbial flora enrichment culture solution; mixing the soil denitrification microbial community enrichment culture solution enriched for the second time with a denitrification enrichment culture medium under the same culture condition according to the volume ratio of 1:4-5 for carrying out constant temperature culture for the third time; repeating the culture process for 3-5 times to obtain a soil indigenous denitrification microbial community enrichment culture solution; or collecting a leachate sample from a rare earth leaching site, mixing the leachate sample with a denitrification enrichment culture medium according to the volume ratio of 1:2-3, and culturing at constant temperature (the culture temperature is 28-30 ℃, the rotating speed is 150-; mixing the first-time enriched leachate denitrification microbial flora enrichment culture solution with a denitrification enrichment culture medium under the same culture condition according to the volume ratio of 1:3-4, and carrying out constant-temperature culture to obtain a second-time enriched leachate denitrification microbial flora enrichment culture solution; according to the following steps of 1:4-5, mixing the secondary enriched leachate denitrification microbial community enrichment culture solution with a denitrification enrichment culture medium under the same culture condition, and culturing at constant temperature; repeating the culture process for 3-5 times to obtain the leacheate indigenous denitrification microbial community enrichment culture solution.
Furthermore, the denitrification enrichment medium comprises the following components in parts by weight: 8-12 parts of peptone, 8-12 parts of NaCl, 3-7 parts of yeast extract, 1000 parts of distilled water and 7-7.5 of pH value.
Furthermore, the method for collecting the soil sample or the leachate sample comprises the following specific steps: randomly selecting at least 3 points from a rare earth leaching site for sampling, and collecting 100-200g soil samples at each point; randomly selecting at least 3 points from a liquid collecting pool and a liquid collecting ditch of the rare earth leaching site for sampling, and collecting 100-200mL samples of leachate at each point; and (3) storing the collected soil sample and the collected leachate sample in an environment at 0-4 ℃ for later use.
Furthermore, the culture solution for enriching the indigenous denitrification microbial flora in the step (b) is at least one selected from the culture solution for enriching the indigenous denitrification microbial flora in the soil, the culture solution for enriching the indigenous denitrification microbial flora in the leachate, or a mixture formed by mixing the two in any proportion.
Further, the method for screening and culturing the indigenous denitrification microbial flora in the step (b) comprises the following steps: mixing the enrichment culture solution of the indigenous denitrification microbial flora and the denitrification function screening culture medium according to the volume ratio of 1:3-6, and culturing at constant temperature (the culture temperature is 28-30 ℃, the rotating speed is 150-; mixing the first screened indigenous denitrification microbial flora and the denitrification function screening culture medium under the same culture condition and culturing at constant temperature according to the volume ratio of 1:4-8 to obtain a second screened indigenous denitrification microbial flora; mixing the second screened indigenous denitrification microbial community and the denitrification function screening culture medium according to the volume ratio of 1:5-10 under the same culture condition and culturing at constant temperature; repeating the denitrification screening culture process for 3-5 times to obtain indigenous denitrification microbial flora.
Furthermore, the denitrification function screening culture medium comprises the following components in parts by weight: 5-20 parts of glucose or sodium citrate, (NH)4)2SO40.5-2 parts of MgSO (MgSO)4·7H20.3-0.5 part of O, 1.5-3 parts of NaCl and FeSO4·7H20.01 to 0.05 portion of O and MnSO4·4H20.01-0.04 part of O, K2HPO40.5-1.5 parts of distilled water, and the pH value is 7-7.5.
Further, the microbial denitrification treatment process in the step (c) is as follows: inoculating the indigenous denitrification microbial community prepared in the step (b) into a denitrification microbial culture medium for culture (the culture temperature is 28-30 ℃, the rotating speed is 150-; mixing the denitrified microorganism culture solution, the denitrified culture medium and the pretreated leachate according to the volume ratio of 1:2-3:4-5, and culturing at constant temperature (the culture temperature is 28-30 ℃, the rotation speed is 150-.
Further, the denitrification microorganism culture medium comprises the following components in parts by weight: 3-6 parts of sodium citrate, (NH)4)2SO40.3-0.5 part of MgSO (MgSO)4·7H20.3-0.5 part of O, 1.5-3 parts of NaCl and FeSO4·7H20.01 to 0.05 portion of O and MnSO4·4H20.01-0.04 part of O, K2HPO40.5-1.5 parts of distilled water, and the pH value is 7-7.5. The denitrification culture medium comprises the following components in parts by weight: 5-20 parts of sodium citrate and MgSO4·7H20.3-0.5 part of O, 1.5-3 parts of NaCl and FeSO4·7H20.01 to 0.05 portion of O and MnSO4·4H20.01-0.04 part of O, K2HPO40.5-1.5 parts of distilled water, and the pH value is 7-7.5.
Compared with the prior art, the invention has the beneficial effects that: (1) firstly, a chemical method (magnesium ammonium phosphate precipitation method) is utilized to effectively treat leachate with high ammonia nitrogen concentration, so that a foundation is laid for subsequent microbial denitrification, and the obtained precipitate magnesium ammonium phosphate can be used for recovering ammonia nitrogen and preparing magnesium hydrogen phosphate, so that reasonable utilization of resources is fully realized; (2) the indigenous denitrification microbial flora used in the method can be well adapted to the residual ammonium salt leachate environment of the rare earth leaching field, the tolerance to non-ammonia nitrogen impurities in the leachate is strong, and the denitrification rate of microorganisms is over 90 percent; (3) the method has simple process and environmental protection, and is suitable for large-scale treatment of the ammonia nitrogen component in the residual ammonium salt leachate of the ionic rare earth mine closed-mine field.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
In order to make those skilled in the art fully understand the technical solution of the present invention, the following embodiments are further described.
The formula of the culture media used by the invention is as follows:
denitrification enrichment culture medium: 10g of peptone, 10g of NaCl, 5g of yeast extract and 1000mL of distilled water, and the pH value is 7-7.5.
And (3) denitrification function screening culture medium: sodium citrate 15g, (NH)4)2SO41.5g，MgSO4·7H2O 0.5g，NaCl 2g，FeSO4·7H2O 0.04g，MnSO4·4H2O 0.01g，K2HPO41g, 1000mL of distilled water, and a pH value of 7-7.5.
Denitrified microbial culture medium: sodium citrate 5g, (NH)4)2SO40.5g，MgSO4·7H2O 0.5g，NaCl2g，FeSO4·7H2O 0.04g，MnSO4·4H2O 0.01g，K2HPO41g, 1000mL of distilled water, and pH 7-7.5.
Denitrification culture medium: sodium citrate 15g, MgSO4·7H2O 0.5g，NaCl 2g，FeSO4·7H2O 0.04g，MnSO4·4H2O 0.01g，K2HPO41g, 1000mL of distilled water, and pH 7-7.5.
The residual ammonium salt leachate of the rare earth leaching field to be treated comes from an ionic rare earth leaching field in Jiangxi Jiangzhou city Longnan county in Jiangxi province. Before the experiment, an enrichment culture solution of the indigenous denitrification microbial flora in soil, an enrichment culture solution of the indigenous denitrification microbial flora in leachate and an indigenous denitrification microbial flora are prepared in advance according to the following methods.
1. Collection of soil and leachate samples
(1) Collection of soil samples
Randomly selecting points from a rare earth ore closed mine field for sampling, collecting soil samples of 5 points, and collecting 150g of soil samples of each point. 5 soil samples are uniformly mixed and put into a plastic freshness protection package, the plastic freshness protection package is put into an ice box at the temperature of 0-4 ℃, and the ice box is quickly brought back to a laboratory within 24 hours.
(2) Collection of leachate samples
Randomly selecting points from a liquid collecting pool of the closed mine field of the rare earth ore, sampling, collecting eluent samples of 5 points, and collecting 100mL of eluent samples of each point. And (3) uniformly mixing 5 leacheate samples, putting the leacheate samples into a plastic preservation bottle, putting the plastic preservation bottle into an ice box at 0-4 ℃, and quickly bringing the plastic preservation bottle back to the laboratory.
2. Preparation of indigenous denitrification microbial flora enrichment culture solution
(1) Preparation of soil indigenous denitrification microbial community enrichment culture solution
Weighing 300g of soil sample, mixing with 1L of sterile water, and placing into a constant-temperature shaking table for shaking culture at the rotation speed of 160r/min and the temperature of 28 ℃ for 30 min. Standing for 10min after oscillation is finished, and taking supernatant to obtain initial bacterial suspension of the soil sample. Measuring 20mL of initial bacterial suspension of the soil sample, mixing the initial bacterial suspension with 50mL of denitrification enrichment medium, placing the mixture in a constant temperature shaking table, and carrying out shaking culture for 2 days at the temperature of 28 ℃ and at the speed of 160r/min to obtain a first-time enrichment culture solution of the soil denitrification microbial flora. And mixing 10mL of the first-enriched soil denitrification microbial flora enrichment culture solution with 40mL of denitrification enrichment culture medium, placing the mixture in a constant-temperature shaking table, and carrying out shaking culture for 2 days at the temperature of 28 ℃ and at the speed of 160r/min to obtain a second-enriched soil denitrification microbial flora enrichment culture solution. And mixing 10mL of the soil denitrification microbial flora enrichment culture solution subjected to secondary enrichment with 40mL of denitrification enrichment culture medium, placing the mixture in a constant-temperature shaking table, and performing fermentation culture for 2 days at the temperature of 28 ℃ and at the speed of 160r/min to obtain the soil indigenous denitrification microbial flora enrichment culture solution.
(2) Preparation of leacheate indigenous denitrification microbial community enrichment culture solution
Weighing 25mL of leacheate sample, mixing the leacheate sample with 50mL of denitrification enrichment culture medium, and placing the mixture in a constant-temperature shaking table to perform shaking culture for 2 days at the temperature of 28 ℃ and at the speed of 170r/min to obtain a first enrichment culture solution of the denitrification microbial flora of the leacheate. And mixing 10mL of the first-enriched eluent denitrification microbial community enrichment culture solution with 40mL of denitrification enrichment culture medium, placing the mixture in a constant-temperature shaking table, and carrying out shaking culture for 2 days at the temperature of 28 ℃ and at the speed of 170r/min to obtain a second-enriched eluent denitrification microbial community enrichment culture solution. And mixing 10mL of the second-enrichment leacheate denitrification microbial community enrichment culture solution with 50mL of denitrification enrichment culture medium, placing the mixture in a constant-temperature shaking table, and performing fermentation culture for 2 days at the temperature of 28 ℃ and at the speed of 170r/min to obtain the leacheate indigenous denitrification microbial community enrichment culture solution.
(3) Preparation of indigenous denitrification microbial flora
Mixing the soil indigenous denitrification microbial flora enrichment culture solution and the leachate indigenous denitrification microbial flora enrichment culture solution according to the volume ratio of 1:1 to prepare the indigenous denitrification microbial flora enrichment culture solution.
10mL of indigenous denitrification microbial flora enrichment culture solution is measured and mixed with 50mL of denitrification function screening culture medium, and the mixture is placed in a constant temperature shaking table to be subjected to shaking culture for 2 days at the temperature of 28 ℃ and the speed of 165r/min, so that the first screened indigenous denitrification microbial flora is obtained. 10mL of the first screened indigenous denitrification microbial flora is mixed with 40mL of denitrification function screening culture medium and then placed in a constant temperature shaking table for shaking culture for 2 days at 28 ℃ and 165r/min, and the second screened indigenous denitrification microbial flora is obtained. 10mL of the second screened indigenous denitrification microbial flora is mixed with 50mL of the denitrification function screening culture medium and then placed in a constant temperature shaking table for fermentation culture for 2 days at 28 ℃ and 165r/min, and finally the required indigenous denitrification microbial flora is obtained.
Example 1
1. The ammonia nitrogen concentration in the residual ammonium salt leachate of the rare earth leaching site is detected by a nano reagent ultraviolet spectrophotometry, and the result is 583.3 mg/L.
2. As shown in FIG. 1, an appropriate amount of aqueous sodium hydroxide solution was added to the residual ammonium salt leachate at the rare earth leaching site to adjust the pH to 9.12, and the ammonia nitrogen concentration in the solution was again determined to be 521.4 mg/L. The ammonia nitrogen molar concentration n (N) was calculated to be 37.24mmol/L, and magnesium chloride and disodium hydrogen phosphate were added in the proportions of n (Mg), n (N), 1.1:1, n (P), n (N), 1:1 (magnesium chloride was added in an amount of 3.9g/L, and disodium hydrogen phosphate was added in an amount of 5.3 g/L). After the addition is finished, the mixture reacts for 30min at the stirring speed of 1000r/min to fully finish the precipitation reaction, and then the mixture is centrifuged for 10min at the rotating speed of 10000r/min to respectively obtain supernatant and precipitate. Drying the precipitate to obtain crude magnesium ammonium phosphate, and measuring the ammonia nitrogen concentration of the supernatant to be 185.6mg/L by using a nano reagent ultraviolet spectrophotometry.
3. Inoculating the prepared indigenous denitrification microbial flora to a denitrification microbial culture medium, and culturing at 28 ℃ and 170r/min for 12h to reach logarithmic phase to obtain a denitrification microbial culture solution. Uniformly mixing the denitrified microorganism culture solution, the denitrified culture medium and the supernatant (namely the pretreated leacheate) obtained in the step (2) according to the volume ratio of 1:2:5, and then placing the mixture in a constant-temperature shaking table to perform shaking culture for 2 days at the temperature of 28 ℃ and at the speed of 170 r/min. After the culture is finished, the culture solution is centrifugally filtered (the centrifugal speed is 10000r/min, and the time is 10min) to obtain a supernatant. The ammonia nitrogen concentration in the supernatant fluid is measured to be 6.35mg/L by a nano reagent ultraviolet photometry, and the national discharge standard is reached.
Example 2
1. And (3) detecting the ammonia nitrogen concentration in the residual ammonium salt leachate of the rare earth leaching site by using a nano reagent ultraviolet spectrophotometry, wherein the result is 730.6 mg/L.
2. And adding a proper amount of sodium carbonate aqueous solution into the residual ammonium salt leachate of the rare earth leaching site to adjust the pH value to 8.9, and measuring again to obtain the solution with ammonia nitrogen concentration of 642.1 mg/L. The ammonia nitrogen molar concentration n (N) is calculated to be 45.86mmol/L, and magnesium chloride and sodium phosphate are added according to the proportion of n (Mg), n (N) to 1.2:1, n (P) to n (N) to 1.1:1 (the addition amount of the magnesium chloride is 5.24g/L, and the addition amount of the sodium phosphate is 8.27 g/L). After the feeding is finished, the mixture reacts for 50min at the stirring speed of 800r/min to fully finish the precipitation reaction, and then the mixture is centrifuged for 10min at the rotating speed of 10000r/min to respectively obtain supernatant and precipitate. Drying the precipitate to obtain crude magnesium ammonium phosphate, and measuring the ammonia nitrogen concentration of the supernatant to be 126.4mg/L by using a nano reagent ultraviolet spectrophotometry.
3. Inoculating the prepared indigenous denitrification microbial flora to a denitrification microbial culture medium, and culturing at 30 ℃ and 150r/min for 12h to reach logarithmic phase to obtain a denitrification microbial culture solution. Uniformly mixing the denitrified microorganism culture solution, the denitrified culture medium and the supernatant obtained in the step (2) according to the volume ratio of 1:3:5, and then placing the mixture in a constant temperature shaking table for shaking culture for 1 day at the temperature of 30 ℃ and at the speed of 150 r/min. After the culture is finished, the culture solution is centrifugally filtered (the centrifugal speed is 10000r/min, and the time is 10min) to obtain a supernatant. The ammonia nitrogen concentration in the supernatant is 10.53mg/L measured by a nano reagent ultraviolet spectrophotometry and reaches the national discharge standard.
Example 3
1. And (3) detecting the ammonia nitrogen concentration in the residual ammonium salt leachate of the rare earth leaching site by using a nano reagent ultraviolet spectrophotometry, wherein the result is 956.4 mg/L.
2. And adding a proper amount of sodium hydroxide aqueous solution into the residual ammonium salt leachate of the rare earth leaching site to adjust the pH value to 9.3, and measuring again to obtain the solution with ammonia nitrogen concentration of 904.6 mg/L. The ammonia nitrogen molar concentration n (N) is calculated to be 64.61mmol/L, and magnesium sulfate and disodium hydrogen phosphate are added according to the proportion of n (Mg), n (N) to 1.3:1, n (P) to n (N) to 1.2:1 (the addition amount of the magnesium sulfate is 9.98g/L, and the addition amount of the disodium hydrogen phosphate is 11.01 g/L). After the addition, the mixture is reacted for 40min at the stirring speed of 1000r/min to fully complete the precipitation reaction, and then the mixture is centrifuged for 10min at the rotating speed of 10000r/min to respectively obtain supernatant and precipitate. Drying the precipitate to obtain crude magnesium ammonium phosphate, and measuring the ammonia nitrogen concentration of the supernatant to be 220.5mg/L by using a nano reagent ultraviolet spectrophotometry.
3. Inoculating the prepared indigenous denitrification microbial flora to a denitrification microbial culture medium, and culturing at 28 ℃ and 165r/min for 12h to reach logarithmic phase to obtain a denitrification microbial culture solution. Uniformly mixing the denitrified microorganism culture solution, the denitrified culture medium and the supernatant obtained in the step (2) according to the volume ratio of 1:2:5, and then placing the mixture in a constant temperature shaking table for shaking culture for 2 days at the temperature of 28 ℃ and at the speed of 165 r/min. After the culture is finished, the culture solution is centrifugally filtered (the centrifugal speed is 10000r/min, and the time is 10min) to obtain a supernatant. The ammonia nitrogen concentration in the supernatant fluid is measured to be 11.45mg/L by a nano reagent ultraviolet photometry, and the national discharge standard is reached.
Claims (10)
1. The method for removing high-concentration ammonia nitrogen in the residual ammonium salt leachate of the rare earth leaching site by utilizing the chemical-biological method is characterized by comprising the following steps of: (a) pretreating the residual ammonium salt leachate of the rare earth leaching site by adopting an ammonium magnesium phosphate precipitation method to reduce the ammonia nitrogen concentration of the leachate, so as to obtain a pretreated leachate; (b) separating and enriching leachate or soil of a rare earth leaching field to obtain an indigenous denitrification microbial flora enrichment culture solution, and then performing denitrification screening culture on the indigenous denitrification microbial flora enrichment culture solution to obtain an indigenous denitrification microbial flora; (c) and (c) performing microbial denitrification treatment on the pretreated leachate obtained in the step (a) by utilizing indigenous denitrification microbial flora.
2. The method according to claim 1, wherein the source of the residual ammonium salt leachate of the rare earth leaching site in the step (a) is as follows: and adding an eluant into a liquid injection system of the ionic rare earth ore in-situ leaching process, eluting the residual ammonium salt in the rare earth ore leaching site, and collecting the eluent through a liquid collection system to obtain the residual ammonium salt leachate in the rare earth ore leaching site.
3. The method of claim 1, wherein the pretreatment in step (a) is as follows: adding magnesium salt, phosphate and a pH regulator into the residual ammonium salt leachate of the rare earth leaching site, fully stirring, and then carrying out precipitation separation to obtain a pretreated leachate; wherein the addition of magnesium salt, phosphate and pH regulator ensures the molar ratio of Mg, P and N in the solution to be 1.1-1.3:1-1.2:1 and the pH value to be 8.5-10; the magnesium salt is selected from at least one of magnesium chloride, magnesium sulfate and magnesium oxide; the phosphate is at least one of disodium hydrogen phosphate or sodium phosphate; the pH regulator is sodium hydroxide aqueous solution or sodium carbonate aqueous solution.
4. The method of claim 1, wherein: the ammonia nitrogen concentration of the residual ammonium salt leachate in the rare earth leaching site before and after the pretreatment in the step (a) is respectively 500-1000mg/L and 100-300 mg/L.
5. The method of claim 1, wherein: the separation and enrichment method of the indigenous denitrification microbial community enrichment culture solution in the step (b) is as follows: collecting a soil sample from a rare earth leaching site, mixing the soil sample with sterile water according to the proportion of 200-500g:1L, carrying out constant-temperature oscillation culture, standing, and taking a supernatant to obtain an initial bacterial suspension of the soil sample; then mixing the initial bacterial suspension of the soil sample and a denitrification enrichment culture medium according to the volume ratio of 1:2-3, and culturing at constant temperature to obtain a first-time enrichment culture solution of the denitrification microbial flora in the soil; mixing the first-time enriched soil denitrification microbial flora enrichment culture solution with a denitrification enrichment culture medium under the same culture condition according to the volume ratio of 1:3-4, and carrying out constant-temperature culture again to obtain a second-time enriched soil denitrification microbial flora enrichment culture solution; mixing the soil denitrification microbial community enrichment culture solution enriched for the second time with a denitrification enrichment culture medium under the same culture condition according to the volume ratio of 1:4-5 for carrying out constant temperature culture for the third time; repeating the culture process for 3-5 times to obtain a soil indigenous denitrification microbial community enrichment culture solution;
or collecting a leachate sample from a rare earth leaching site, mixing the leachate sample with a denitrification enrichment culture medium according to the volume ratio of 1:2-3, and culturing at constant temperature to obtain a leachate denitrification microbial community enrichment culture solution for first enrichment; mixing the first-time enriched leachate denitrification microbial flora enrichment culture solution with a denitrification enrichment culture medium under the same culture condition according to the volume ratio of 1:3-4, and carrying out constant-temperature culture to obtain a second-time enriched leachate denitrification microbial flora enrichment culture solution; according to the following steps of 1:4-5, mixing the secondary enriched leachate denitrification microbial community enrichment culture solution with a denitrification enrichment culture medium under the same culture condition, and culturing at constant temperature; repeating the culture process for 3-5 times to obtain an enrichment culture solution of indigenous denitrification microbial flora of the leachate;
the denitrification enrichment medium comprises the following components in parts by weight: 8-12 parts of peptone, 8-12 parts of NaCl, 3-7 parts of yeast extract, 1000 parts of distilled water and 7-7.5 of pH value.
6. The method according to claim 5, wherein the soil sample or leachate sample is collected by a method comprising: randomly selecting at least 3 points from a rare earth leaching site for sampling, and collecting 100-200g soil samples at each point; randomly selecting at least 3 points from a liquid collecting pool and a liquid collecting ditch of the rare earth leaching site for sampling, and collecting 100-200mL samples of leachate at each point; and (3) storing the collected soil sample and the collected leachate sample in an environment at 0-4 ℃ for later use.
7. The method of claim 1 or 5, wherein: the culture solution for enriching the indigenous denitrification microbial flora in the step (b) is at least one of culture solution for enriching the indigenous denitrification microbial flora in the soil and culture solution for enriching the indigenous denitrification microbial flora in the leachate, or a mixture formed by mixing the culture solution and the culture solution in any proportion.
8. The method according to claim 1, wherein the step (b) of denitrifying microorganism flora screening culture is as follows: mixing the culture solution for enriching the indigenous denitrification microbial flora and the culture medium for screening the denitrification function according to the volume ratio of 1:3-6, and culturing at constant temperature to obtain the first screened productIndigenous denitrification microbial flora; mixing the first screened indigenous denitrification microbial flora and the denitrification function screening culture medium under the same culture condition and culturing at constant temperature according to the volume ratio of 1:4-8 to obtain a second screened indigenous denitrification microbial flora; mixing the second screened indigenous denitrification microbial community and the denitrification function screening culture medium according to the volume ratio of 1:5-10 under the same culture condition and culturing at constant temperature; repeating the denitrification screening culture process for 3-5 times to obtain indigenous denitrification microbial flora; the denitrification function screening culture medium comprises the following components in parts by weight: 5-20 parts of glucose or sodium citrate, (NH)4)2SO40.5-2 parts of MgSO (MgSO)4·7H20.3-0.5 part of O, 1.5-3 parts of NaCl and FeSO4·7H20.01 to 0.05 portion of O and MnSO4·4H20.01-0.04 part of O, K2HPO40.5-1.5 parts of distilled water, and the pH value is 7-7.5.
9. The method according to claim 1, wherein the denitrification treatment of the microorganisms in the step (c) is as follows: inoculating the indigenous denitrification microbial community prepared in the step (b) into a denitrification microbial culture medium for culture, and obtaining a denitrification microbial culture solution when the microbial community grows to a logarithmic phase; mixing the denitrification microorganism culture solution, the denitrification culture medium and the pretreated leachate according to the volume ratio of 1:2-3:4-5, and then culturing at constant temperature; the denitrification microorganism culture medium comprises the following components in parts by weight: 3-6 parts of sodium citrate, (NH)4)2SO40.3-0.5 part of MgSO (MgSO)4·7H20.3-0.5 part of O, 1.5-3 parts of NaCl and FeSO4·7H20.01 to 0.05 portion of O and MnSO4·4H20.01-0.04 part of O, K2HPO40.5-1.5 parts of distilled water, and the pH value is 7-7.5; the denitrification culture medium comprises the following components in parts by weight: 5-20 parts of sodium citrate and MgSO4·7H20.3-0.5 part of O, 1.5-3 parts of NaCl1, and FeSO4·7H20.01 to 0.05 portion of O and MnSO4·4H20.01-0.04 part of O, K2HPO40.5-1.5 parts of distilled water, and the pH value is 7-7.5.
10. The method according to claim 1, wherein the culture conditions in steps (a) to (c) are as follows: the culture temperature is 28-30 ℃, the rotation speed is 150-.
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