CN108083450B - Complexing agent for rare earth wastewater - Google Patents

Complexing agent for rare earth wastewater Download PDF

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CN108083450B
CN108083450B CN201711301631.7A CN201711301631A CN108083450B CN 108083450 B CN108083450 B CN 108083450B CN 201711301631 A CN201711301631 A CN 201711301631A CN 108083450 B CN108083450 B CN 108083450B
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rare earth
weight
agent
mixing
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CN108083450A (en
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龙国华
刘蓉凤
刘沁
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陈云兰
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    • 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
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/348Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
    • 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
    • C02F2101/20Heavy metals or heavy metal compounds
    • 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
    • C02F2103/16Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

Abstract

The invention discloses a complexing agent for rare earth wastewater, belonging to the field of water treatment. The invention extracts a strain capable of adsorbing heavy metals from plant soil, thereby reducing the content of the heavy metals in the rare earth wastewater, and the strain forms a liquid microbial precipitator by centrifugation and is combined with the adsorbent, and the adsorbent is obtained by modifying medical stone by hydrochloric acid and calcination, so that the specific surface area is increased, the adsorption performance is enhanced, the combination rate with the liquid microbial precipitator is improved, and meanwhile, the medical stone can effectively remove the content of ammonia nitrogen in the rare earth wastewater, thereby improving the purification efficiency of the rare earth wastewater. The invention solves the problem that ammonium ions in the precipitating agent are not completely utilized and enter the rare earth wastewater to cause higher ammonia nitrogen content in the rare earth wastewater when the ammonium bicarbonate is mostly adopted as the precipitating agent in the rare earth wastewater precipitation at present.

Description

Complexing agent for rare earth wastewater
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a complexing agent for rare earth wastewater.
Background
China is the most abundant country of rare earth resources in the world and is mainly distributed in inner Mongolia, Jiangxi and the like. The rare earth industry plays an extremely important role in local economic development, but the rare earth preparation process generates a large amount of waste water, and the pollution to the environment is more and more concerned. The rare earth wastewater is industrial wastewater generated in the rare earth smelting separation process, and the rare earth wastewater discharged each year is about 250 ten thousand m taking 'the town of rare earth' as an example of inner Mongolia baotou3Accounting for 4 percent of the total amount of industrial wastewater discharged in Baotou city. The production process comprises the following steps: dissolving rare earth concentrate with the rare earth content of about 90% by hydrochloric acid, removing impurities to obtain mixed rare earth chloride feed liquid, then extracting, grouping or separating the mixed rare earth chloride feed liquid by adopting P507, P204, naphthenic acid, kerosene and the like to obtain single rare earth or compound rare earth compound solution, precipitating and cleaning the solution by oxalic acid, and then firing the solution at low temperature to obtain rare earth oxide. As the industrial production of rare earth enterprises has widely adopted the organic phase extraction technology under the acidic condition, the extractant mainly comprises phosphorus extractants, and the extraction wastewater generated in the production process of smelting and separating the rare earth has the characteristics of high COD concentration, high total phosphorus and ammonia nitrogen and the like. And in the rare earth smelting and precipitating section, oxalic acid is adopted to precipitate rare earth ions obtained by extraction in the extraction section, and precipitated crystals are cleaned to form precipitation wastewater which contains strongly acidic and oxalic acid-containing substances and pollution factors such as high COD concentration and high ammonia nitrogen. A large amount of each kindThe rare earth wastewater of the pollution factors is an important source of pollution in the rare earth smelting separation industry, causes pollution to the surrounding environment and water body of the rare earth smelting separation enterprise, is also a main factor for restricting the healthy and stable development of the rare earth industry, and is important for development of rare earth wastewater treatment technology.
Along with the enhancement of environmental awareness of people, the pollution problem of the rare earth industry has gradually attracted attention, ammonia nitrogen pollutants are main pollution generated in rare earth smelting, the ammonia nitrogen has certain harm to human bodies and water bodies, the ammonia nitrogen in water quality indexes causes an important pollutant of water body eutrophication and environmental pollution, the ammonia nitrogen can enable water to lose a self-purification function, the ammonia nitrogen enters the human bodies to synthesize nitroso compounds to induce canceration, and gastrointestinal disorders and endemic diseases can be generated when the content of the ammonia nitrogen in drinking water is too high. The amount of wastewater generated in the rare earth industry per year reaches more than 1500 million tons, wherein the content of ammonia nitrogen is 8000-12000 mg/L, which exceeds the national discharge standard by dozens of times to hundreds of times. Ammonia nitrogen wastewater is discharged into a water body, particularly flows to a relatively slow lake and a relatively slow gulf, algae and other microorganisms in the water are easily propagated in a large quantity to form eutrophication pollution, besides the running of a water treatment plant is difficult and the peculiar smell of drinking water is caused, dissolved oxygen in the water is reduced in serious cases, fishes die in a large quantity and even the lake is killed, the ammonia nitrogen also increases the chlorine consumption in the processes of water supply disinfection and industrial circulating water sterilization treatment, and the ammonia nitrogen is corrosive to certain metals, particularly copper.
At present, most of rare earth wastewater treatment adopts an anaerobic ammonia oxidation process, a stripping method, a chemical precipitation method and the like to achieve the purpose of separating pollutants from the rare earth wastewater, ammonium bicarbonate is mostly adopted as a precipitator for precipitation, but ammonium ions in the precipitator are not completely utilized and enter the rare earth wastewater, so that the ammonia nitrogen content in the rare earth wastewater is higher. Therefore, the production of a preparation for efficiently treating rare earth wastewater is urgent.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem that ammonium ions in the precipitating agent are not completely utilized and enter the rare earth wastewater to cause high ammonia nitrogen content in the rare earth wastewater by adopting ammonium bicarbonate as the precipitating agent mostly in the rare earth wastewater precipitation at present, the complexing agent for the rare earth wastewater is provided.
In order to solve the technical problems, the invention adopts the following technical scheme:
the complexing agent for the rare earth wastewater comprises an agent A and an agent B, and is characterized in that the preparation method of the agent A comprises the following steps:
(1) putting plant soil and a liquid culture medium into a container for culturing to obtain a culture solution, putting an inoculating loop into the culture solution for dipping to obtain a dipped inoculating loop, streaking the dipped inoculating loop in a solid culture medium to obtain a streaked solid culture medium, culturing the streaked solid culture medium at the temperature of 28-32 ℃ for 20-24 h, picking a bacterial colony with the largest bacterial diameter to obtain a bacterial colony, mixing the bacterial colony with the liquid culture medium, and stirring for 10-15 min to obtain a stirred mixture;
(2) putting the stirred mixture into a fermentation tank, fermenting for 1-2 days at the temperature of 30-35 ℃ to obtain fermentation liquor, centrifuging the fermentation liquor for 20-30 min to obtain a precipitate, and mixing the precipitate and a preservative to obtain a mixture;
(3) crushing medical stone in a crusher to obtain crushed materials, mixing the crushed materials with a hydrochloric acid solution, soaking for 1-2 hours, filtering to obtain soaked filter residues, calcining the soaked filter residues at 400-600 ℃ to obtain calcined materials, mixing the calcined materials and the mixture, soaking for 1-2 hours, and filtering to obtain filter residues;
(4) mixing and dissolving chitosan and acetic acid solution, stirring until the chitosan is completely dissolved to obtain a dissolved solution, mixing filter residue, the dissolved solution and a cross-linking agent, reacting at the temperature of 50-60 ℃ for 1-2 hours to obtain a reactant, washing the reactant with a sodium hydroxide solution to obtain a washed reactant, and freeze-drying the washed reactant to obtain a dried substance, namely an agent A;
the preparation method of the agent B comprises the following steps:
a. mixing 30-40 parts of water, 2-3 parts of sodium carbonate, 1-2 parts of sodium nitrate, 0.8-1 part of dipotassium hydrogen phosphate, 0.2-0.3 part of sodium dihydrogen phosphate, 0.03-0.06 part of magnesium sulfate and 0.01-0.03 part of manganese sulfate in parts by weight, and sterilizing at high temperature to obtain a nutrient solution, wherein the mass ratio of the nutrient solution to the components is 2-3: 7-8, mixing seawater and a nutrient solution, culturing for 4-5 days at the temperature of 24-30 ℃ to obtain a culture solution, dipping an inoculating loop into the culture solution to obtain the dipped inoculating loop, mixing 30-40 parts of water, 2-3 parts of agar, 2-3 parts of sodium carbonate, 1-2 parts of sodium nitrate, 0.8-1 part of dipotassium hydrogen phosphate, 0.2-0.3 part of sodium dihydrogen phosphate, 0.03-0.06 part of magnesium sulfate and 0.01-0.03 part of manganese sulfate according to parts by weight, sterilizing at high temperature to obtain a culture medium, streaking the dipped inoculating loop in the culture medium, and culturing for 20-24 hours at the temperature of 28-32 ℃ to obtain a bacterial colony with the largest bacterial diameter;
b. and inoculating the colony with the largest bacterial diameter into a shake flask for culturing for 4-5 days to obtain a culture, putting the culture into a fermentation tank, and fermenting at the pH of 6-10 and the temperature of 20-28 ℃ to obtain a fermented product, namely the agent B.
The use method of the complexing agent for the rare earth wastewater comprises the following steps: adding an agent A with the mass being 20-30% of that of the rare earth wastewater into the rare earth wastewater, treating for 2-3 h, and taking out to obtain a treated agent A, wherein the treated agent A is prepared from the following raw materials in parts by mass: 1: 0.1-0.2, mixing the water, the treated agent A and the treated agent B, stirring for 1-2 hours at 200-220 r/min, filtering to obtain filter residues, and freeze-drying the filter residues to obtain dried substances for recycling.
The liquid culture medium in the step (1) is prepared by uniformly mixing 50-60 parts by weight of distilled water, 20-30 parts by weight of glucose, 10-15 parts by weight of peptone, 5-8 parts by weight of sodium chloride and 0.5-1 part by weight of beef extract, and sterilizing at high temperature.
The solid culture medium in the step (1) is prepared by uniformly mixing 50-60 parts by weight of distilled water, 20-30 parts by weight of glucose, 20-30 parts by weight of agar, 10-15 parts by weight of peptone, 5-8 parts by weight of sodium chloride and 0.5-1 part by weight of beef extract, and sterilizing at high temperature.
The preservative in the step (2) is any one of potassium sorbate and sodium benzoate.
The cross-linking agent in the step (4) is any one of dicumyl peroxide and dicumyl hydroperoxide.
Compared with other methods, the method has the beneficial technical effects that: in the preparation process of the A agent, a strain capable of adsorbing heavy metals is extracted from plant soil, so that the content of the heavy metals in the rare earth wastewater is reduced, the strain forms a liquid microbial precipitator by centrifugation and is combined with an adsorbent, the adsorbent is formed by modifying medical stone by hydrochloric acid and calcination, the specific surface area of the adsorbent is increased, the adsorption performance is enhanced, so that the combination rate with the liquid microbial precipitator is improved, meanwhile, the medical stone can effectively remove the content of ammonia nitrogen in the rare earth wastewater, so that the purification efficiency of the rare earth wastewater is improved, in addition, chitosan is used for forming a film by a cross-linking agent and can be attached to the surface of the medical stone, so that the problem of secondary pollution caused by exposure of the liquid microbial precipitator is solved, the B agent which is a substance capable of desorbing the A agent is also prepared, and the B agent is a strain separated from seawater and has a metabolism effect, the bacteria consume the ammonia nitrogen absorbed in the agent A through the metabolism, so that the agent A is regenerated, and meanwhile, the bacteria have the absorption effect and are combined with the agent A, so that the absorption performance of the agent A is improved.
Detailed Description
And (3) plant soil: the potato culture soil.
The liquid culture medium is prepared by uniformly mixing 50-60 parts by weight of distilled water, 20-30 parts by weight of glucose, 10-15 parts by weight of peptone, 5-8 parts by weight of sodium chloride and 0.5-1 part by weight of beef extract, and sterilizing at high temperature.
The solid culture medium is prepared by uniformly mixing 50-60 parts by weight of distilled water, 20-30 parts by weight of glucose, 20-30 parts by weight of agar, 10-15 parts by weight of peptone, 5-8 parts by weight of sodium chloride and 0.5-1 part by weight of beef extract, and sterilizing at high temperature.
The antiseptic is one of potassium sorbate and sodium benzoate.
The crosslinking agent is dicumyl peroxide or dicumyl hydroperoxide.
The complexing agent for the rare earth wastewater comprises an agent A and an agent B, and the preparation method of the agent A comprises the following steps:
(1) according to the mass ratio of 1: 3-4, putting plant soil and a liquid culture medium into a container for culture, wherein the culture temperature is 28-32 ℃, the culture time is 10-12 hours, obtaining a culture solution, putting an inoculating loop into the culture solution for dipping, obtaining the dipped inoculating loop, scribing the dipped inoculating loop in a solid culture medium, obtaining the scribed solid culture medium, culturing the scribed solid culture medium at the temperature of 28-32 ℃ for 20-24 hours, picking the bacterial colony with the largest bacterial diameter, obtaining a bacterial colony, and mixing the bacterial colony with the bacterial colony according to the mass ratio of 1: 3-4, mixing the bacterial culture and the liquid culture medium, and stirring for 10-15 min at a speed of 180-200 r/min to obtain a stirring mixture;
(2) putting the stirred mixture into a fermentation tank, fermenting for 1-2 days at the temperature of 30-35 ℃ to obtain fermentation liquor, centrifuging the fermentation liquor for 20-30 min at the temperature of 35-45 ℃ under the pressure of 10MPa to obtain a precipitate, and mixing the precipitate with the fermentation liquor according to the mass ratio of 10-15: 0.5-1, mixing the precipitate and a preservative to obtain a mixture;
(3) putting medical stone into a pulverizer to be pulverized to obtain a pulverized material, wherein the mass ratio of the pulverized material to the pulverized material is 1: 3-4, mixing the crushed material and 1.0mol/L hydrochloric acid solution, soaking for 1-2 hours, filtering to obtain soaked filter residue, and calcining the soaked filter residue at 400-600 ℃ to obtain a calcined material, wherein the mass ratio of the calcined material to the hydrochloric acid solution is 1: 5-6, mixing the calcined substance and the mixture, soaking for 1-2 hours, and filtering to obtain filter residues;
(4) according to the mass ratio of 1: 3-4, mixing and dissolving chitosan and 1.2mol/L acetic acid solution, and stirring at 200-260 r/min until the chitosan is completely dissolved to obtain a dissolved solution, wherein the mass ratio of the chitosan to the acetic acid solution is 1: 3-4, mixing the filter residue, the dissolving solution and the cross-linking agent, reacting for 1-2 hours at the temperature of 50-60 ℃ to obtain a reactant, washing the reactant with 1.0mol/L sodium hydroxide solution to obtain a washed reactant, and freeze-drying the washed reactant to obtain a dried substance, namely the agent A;
the preparation method of the agent B comprises the following steps:
a. mixing 30-40 parts of water, 2-3 parts of sodium carbonate, 1-2 parts of sodium nitrate, 0.8-1 part of dipotassium hydrogen phosphate, 0.2-0.3 part of sodium dihydrogen phosphate, 0.03-0.06 part of magnesium sulfate and 0.01-0.03 part of manganese sulfate in parts by weight, and sterilizing at high temperature to obtain a nutrient solution, wherein the mass ratio of the nutrient solution to the components is 2-3: 7-8, mixing seawater and a nutrient solution, culturing for 4-5 days at the temperature of 24-30 ℃ to obtain a culture solution, dipping an inoculating loop into the culture solution to obtain the dipped inoculating loop, mixing 30-40 parts of water, 2-3 parts of agar, 2-3 parts of sodium carbonate, 1-2 parts of sodium nitrate, 0.8-1 part of dipotassium hydrogen phosphate, 0.2-0.3 part of sodium dihydrogen phosphate, 0.03-0.06 part of magnesium sulfate and 0.01-0.03 part of manganese sulfate according to parts by weight, sterilizing at high temperature to obtain a culture medium, streaking the dipped inoculating loop in the culture medium, and culturing for 20-24 hours at the temperature of 28-32 ℃ to obtain a bacterial colony with the largest bacterial diameter;
b. inoculating the colony with the largest bacterial diameter into a shake flask for culturing at the temperature of 20-28 ℃ and the rotating speed of 200-220 r/min for 4-5 days to obtain a culture, putting the culture into a fermentation tank, and fermenting at the pH of 6-10 and the temperature of 20-28 ℃ to obtain a fermentation product, namely the agent B.
A use method of a complexing agent for rare earth wastewater comprises the following steps: adding an agent A with the mass being 20-30% of that of the rare earth wastewater into the rare earth wastewater, treating for 2-3 h, and taking out to obtain a treated agent A, wherein the treated agent A is prepared from the following raw materials in parts by mass: 1: 0.1-0.2, mixing the water, the treated agent A and the treated agent B, stirring for 1-2 hours at 200-220 r/min, filtering to obtain filter residues, and freeze-drying the filter residues to obtain dried substances for recycling.
Example 1
And (3) plant soil: the potato culture soil.
The liquid culture medium is prepared by uniformly mixing 50 parts by weight of distilled water, 20 parts by weight of glucose, 10 parts by weight of peptone, 5 parts by weight of sodium chloride and 0.5 part by weight of beef extract, and sterilizing at high temperature.
The solid culture medium is prepared by uniformly mixing 50 parts by weight of distilled water, 20 parts by weight of glucose, 20 parts by weight of agar, 10 parts by weight of peptone, 5 parts by weight of sodium chloride and 0.5 part by weight of beef extract, and sterilizing at high temperature.
The preservative is potassium sorbate.
The crosslinking agent is dicumyl peroxide.
The complexing agent for the rare earth wastewater comprises an agent A and an agent B, and the preparation method of the agent A comprises the following steps:
(1) according to the mass ratio of 1: 3, putting plant soil and a liquid culture medium into a container for culture, wherein the culture temperature is 28 ℃, the culture time is 10 hours, obtaining a culture solution, putting an inoculating loop into the culture solution for dipping, obtaining the dipped inoculating loop, scribing the dipped inoculating loop in a solid culture medium, obtaining the scribed solid culture medium, culturing the scribed solid culture medium at the temperature of 28 ℃ for 20 hours, selecting a bacterial colony with the largest bacterial diameter, obtaining a bacterial colony, and mixing the bacterial colony with the bacterial colony according to the mass ratio of 1: 3, mixing the bacterial culture and the liquid culture medium, and stirring for 10min at the speed of 180r/min to obtain a stirring mixture;
(2) putting the stirred mixture into a fermentation tank, fermenting for 1d at the temperature of 30 ℃ to obtain fermentation liquor, centrifuging the fermentation liquor for 20min at the temperature of 35 ℃ under the pressure of 10MPa to obtain precipitate, and mixing the precipitate with the fermentation liquor according to the mass ratio of 10: 0.5, mixing the precipitate and the preservative to obtain a mixture;
(3) putting medical stone into a pulverizer to be pulverized to obtain a pulverized material, wherein the mass ratio of the pulverized material to the pulverized material is 1: 3, mixing the crushed material and 1.0mol/L hydrochloric acid solution, soaking for 1 hour, filtering to obtain soaking filter residue, calcining the soaking filter residue at the temperature of 300 ℃ to obtain a calcined material, wherein the mass ratio of the calcined material to the hydrochloric acid solution is 1: 5, mixing the calcined substance and the mixture, soaking for 1 hour, and filtering to obtain filter residue;
(4) according to the mass ratio of 1: and 3, mixing and dissolving chitosan and 1.2mol/L acetic acid solution, and stirring at 200r/min until the chitosan is completely dissolved to obtain a dissolved solution, wherein the mass ratio of the chitosan to the acetic acid solution is 1: 3, mixing the filter residue, the dissolving solution and the cross-linking agent, reacting for 1h at the temperature of 50 ℃ to obtain a reactant, washing the reactant by using 1.0mol/L sodium hydroxide solution to obtain a washed reactant, and freeze-drying the washed reactant to obtain a dried substance, namely the agent A;
the preparation method of the agent B comprises the following steps:
a. mixing 30 parts of water, 2 parts of sodium carbonate, 1 part of sodium nitrate, 0.8 part of dipotassium hydrogen phosphate, 0.2 part of sodium dihydrogen phosphate, 0.03 part of magnesium sulfate and 0.01 part of manganese sulfate according to parts by weight, and sterilizing at high temperature to obtain a nutrient solution, wherein the mass ratio of the components is 2: 7 mixing seawater and nutrient solution, culturing for 4 days at the temperature of 24 ℃ to obtain a culture solution, putting an inoculating loop into the culture solution to dip to obtain the dipped inoculating loop, mixing 30 parts by weight of water, 2 parts by weight of agar, 2 parts by weight of sodium carbonate, 1 part by weight of sodium nitrate, 0.8 part by weight of dipotassium hydrogen phosphate, 0.2 part by weight of sodium dihydrogen phosphate, 0.03 part by weight of magnesium sulfate and 0.01 part by weight of manganese sulfate, sterilizing at high temperature to obtain a culture medium, streaking the dipped inoculating loop in the culture medium, and culturing for 20 hours at the temperature of 28 ℃ to obtain a bacterial colony with the largest bacterial diameter;
b. inoculating the colony with the largest bacterial diameter into a shake flask for culturing at 20 deg.C and 200r/min for 4d to obtain culture, placing the culture into a fermentation tank, and fermenting at 20 deg.C and pH of 6 to obtain fermented product, i.e. agent B.
A use method of a complexing agent for rare earth wastewater comprises the following steps: adding an agent A accounting for 20% of the rare earth wastewater by mass into the rare earth wastewater, treating for 2h, and taking out to obtain a treated agent A, wherein the weight ratio of the agent A to the rare earth wastewater is 3: 1: 0.1, mixing the water, the treated agent A and the treated agent B, stirring for 1 hour at the speed of 200r/min, filtering to obtain filter residue, and freeze-drying the filter residue to obtain a dried substance for recycling.
Example 2
And (3) plant soil: the potato culture soil.
The liquid culture medium is prepared by uniformly mixing 60 parts by weight of distilled water, 30 parts by weight of glucose, 15 parts by weight of peptone, 8 parts by weight of sodium chloride and 1 part by weight of beef extract, and sterilizing at high temperature.
The solid culture medium is prepared by uniformly mixing 60 parts of distilled water, 30 parts of glucose, 30 parts of agar, 15 parts of peptone, 8 parts of sodium chloride and 1 part of beef extract in parts by weight, and sterilizing at high temperature.
The preservative is sodium benzoate.
The crosslinking agent is dicumyl peroxide.
The complexing agent for the rare earth wastewater comprises an agent A and an agent B, and the preparation method of the agent A comprises the following steps:
(1) according to the mass ratio of 1: 4, putting plant soil and a liquid culture medium into a container for culture, wherein the culture temperature is 32 ℃, the culture time is 12 hours, obtaining a culture solution, putting an inoculating loop into the culture solution for dipping, obtaining the dipped inoculating loop, scribing the dipped inoculating loop in a solid culture medium, obtaining the scribed solid culture medium, culturing the scribed solid culture medium at the temperature of 32 ℃ for 24 hours, selecting a bacterial colony with the largest bacterial diameter, obtaining a bacterial colony, and mixing the bacterial colony with the culture solution according to the mass ratio of 1: 4, mixing the bacterial culture and the liquid culture medium, and stirring for 15min at the speed of 200r/min to obtain a stirring mixture;
(2) putting the stirred mixture into a fermentation tank, fermenting for 2d at the temperature of 35 ℃ to obtain fermentation liquor, centrifuging the fermentation liquor for 30min at the temperature of 45 ℃ under the pressure of 10MPa to obtain precipitate, and mixing the precipitate with the fermentation liquor according to the mass ratio of 15: 1, mixing the precipitate and a preservative to obtain a mixture;
(3) putting medical stone into a pulverizer to be pulverized to obtain a pulverized material, wherein the mass ratio of the pulverized material to the pulverized material is 1: and 4, mixing the crushed material and 1.0mol/L hydrochloric acid solution, soaking for 2 hours, filtering to obtain soaking filter residue, and calcining the soaking filter residue at the temperature of 330 ℃ to obtain a calcined material, wherein the mass ratio of the calcined material to the hydrochloric acid solution is 1: 6, mixing the calcined substance and the mixture, soaking for 2 hours, and filtering to obtain filter residue;
(4) according to the mass ratio of 1: 4, mixing and dissolving chitosan and 1.2mol/L acetic acid solution, and stirring at 260r/min until the chitosan is completely dissolved to obtain a dissolved solution, wherein the mass ratio of the chitosan to the acetic acid solution is 1: 4, mixing the filter residue, the dissolving solution and the cross-linking agent, reacting for 2 hours at the temperature of 60 ℃ to obtain a reactant, washing the reactant by using 1.0mol/L sodium hydroxide solution to obtain a washed reactant, and freeze-drying the washed reactant to obtain a dried substance, namely the agent A;
the preparation method of the agent B comprises the following steps:
a. mixing 40 parts of water, 3 parts of sodium carbonate, 2 parts of sodium nitrate, 1 part of dipotassium hydrogen phosphate, 0.3 part of sodium dihydrogen phosphate, 0.06 part of magnesium sulfate and 0.03 part of manganese sulfate according to parts by weight, and sterilizing at high temperature to obtain a nutrient solution, wherein the mass ratio of the nutrient solution to the components is 3: 8, mixing seawater and nutrient solution, culturing for 5 days at the temperature of 30 ℃ to obtain a culture solution, putting an inoculating loop into the culture solution to dip to obtain the dipped inoculating loop, mixing 40 parts of water, 3 parts of agar, 3 parts of sodium carbonate, 2 parts of sodium nitrate, 1 part of dipotassium hydrogen phosphate, 0.3 part of sodium dihydrogen phosphate, 0.06 part of magnesium sulfate and 0.03 part of manganese sulfate in parts by weight, sterilizing at high temperature to obtain a culture medium, streaking the dipped inoculating loop in the culture medium, and culturing for 24 hours at the temperature of 32 ℃ to obtain a bacterial colony with the largest bacterial diameter;
b. inoculating the colony with the largest bacterial diameter into a shake flask for culturing at 28 deg.C and 220r/min for 5d to obtain culture, placing the culture into a fermentation tank, and fermenting at 28 deg.C and pH of 10 to obtain fermented product, i.e. agent B.
A use method of a complexing agent for rare earth wastewater comprises the following steps: adding an agent A accounting for 30% of the rare earth wastewater by mass into the rare earth wastewater, treating for 3h, and taking out to obtain a treated agent A, wherein the agent A is prepared from the following components in parts by mass of 4: 1: 0.2, mixing the water, the treated agent A and the treated agent B, stirring for 2 hours at 220r/min, filtering to obtain filter residue, and freeze-drying the filter residue to obtain a dried substance for recycling.
Example 3
And (3) plant soil: the potato culture soil.
The liquid culture medium is prepared by uniformly mixing 55 parts by weight of distilled water, 25 parts by weight of glucose, 12.5 parts by weight of peptone, 6.5 parts by weight of sodium chloride and 0.7 part by weight of beef extract, and sterilizing at high temperature.
The solid culture medium is prepared by uniformly mixing 55 parts by weight of distilled water, 25 parts by weight of glucose, 25 parts by weight of agar, 12.5 parts by weight of peptone, 6.5 parts by weight of sodium chloride and 0.7 part by weight of beef extract, and sterilizing at high temperature.
The preservative is potassium sorbate.
The crosslinking agent is dicumyl peroxide.
The complexing agent for the rare earth wastewater comprises an agent A and an agent B, and the preparation method of the agent A comprises the following steps:
(1) according to the mass ratio of 1: 3.5, plant soil and a liquid culture medium are placed into a container for culture, the culture temperature is 30 ℃, the culture time is 11 hours, a culture solution is obtained, an inoculating loop is placed into the culture solution for dipping, the dipped inoculating loop is obtained, the dipped inoculating loop is streaked in a solid culture medium, the streaked solid culture medium is obtained, the streaked solid culture medium is cultured for 22 hours at the temperature of 30 ℃, the bacterial colony with the largest bacterial diameter is selected, a bacterial colony is obtained, and the mass ratio of the bacterial colony to the bacterial colony is 1: 3.5, mixing the bacterial culture and the liquid culture medium, and stirring for 13min at the speed of 190r/min to obtain a stirring mixture;
(2) putting the stirred mixture into a fermentation tank, fermenting for 1.5 days at the temperature of 33 ℃ to obtain fermentation liquor, centrifuging the fermentation liquor for 25min at the temperature of 40 ℃ under the pressure of 10MPa to obtain a precipitate, and mixing the precipitate with the fermentation liquor according to the mass ratio of 13: 0.7, mixing the precipitate and the preservative to obtain a mixture;
(3) putting medical stone into a pulverizer to be pulverized to obtain a pulverized material, wherein the mass ratio of the pulverized material to the pulverized material is 1: 3.5, mixing the crushed material and 1.0mol/L hydrochloric acid solution, soaking for 1.5h, filtering to obtain soaking filter residue, calcining the soaking filter residue at 315 ℃ to obtain a calcined material, wherein the mass ratio of the calcined material to the hydrochloric acid solution is 1: 5.5, mixing the calcined substance and the mixture, soaking for 1.5h, and filtering to obtain filter residue;
(4) according to the mass ratio of 1: 3.5, mixing and dissolving chitosan and 1.2mol/L acetic acid solution, and stirring at 230r/min until the chitosan is completely dissolved to obtain a dissolved solution, wherein the mass ratio of the chitosan to the acetic acid solution is 1: 3.5, mixing the filter residue, the dissolving solution and the cross-linking agent, reacting for 1.5 hours at the temperature of 55 ℃ to obtain a reactant, washing the reactant by using 1.0mol/L sodium hydroxide solution to obtain a washed reactant, and freeze-drying the washed reactant to obtain a dried substance, namely the agent A;
the preparation method of the agent B comprises the following steps:
a. according to the weight parts, 35 parts of water, 2.5 parts of sodium carbonate, 1.5 parts of sodium nitrate, 0.9 part of dipotassium hydrogen phosphate, 0.25 part of sodium dihydrogen phosphate, 0.04 part of magnesium sulfate and 0.02 part of manganese sulfate are mixed and sterilized at high temperature to obtain a nutrient solution, wherein the mass ratio of the nutrient solution to the components is 2.5: 7.5 mixing seawater and nutrient solution, culturing for 4.5 days at the temperature of 27 ℃ to obtain a culture solution, putting an inoculating loop into the culture solution to dip to obtain the dipped inoculating loop, mixing 35 parts of water, 2.5 parts of agar, 2.5 parts of sodium carbonate, 1.5 parts of sodium nitrate, 0.9 part of dipotassium hydrogen phosphate, 0.25 part of sodium dihydrogen phosphate, 0.04 part of magnesium sulfate and 0.02 part of manganese sulfate in parts by weight, sterilizing at high temperature to obtain a culture medium, streaking the dipped inoculating loop in the culture medium, and culturing for 22 hours at the temperature of 30 ℃ to obtain a bacterial colony with the largest bacterial diameter;
b. inoculating the colony with the largest bacterial diameter into a shake flask for culturing at 24 deg.C and 210r/min for 4.5d to obtain culture, placing the culture into a fermentation tank, and fermenting at 24 deg.C and pH of 8 to obtain fermented product, i.e. agent B.
A use method of a complexing agent for rare earth wastewater comprises the following steps: adding an agent A accounting for 25% of the rare earth wastewater by mass into the rare earth wastewater, treating for 2.5h, and taking out to obtain a treated agent A, wherein the weight ratio of the agent A to the rare earth wastewater is 3.5: 1: 0.15, mixing the water, the treated agent A and the treated agent B, stirring for 1.5h at the speed of 210r/min, filtering to obtain filter residue, and freeze-drying the filter residue to obtain a dried substance for recycling.
Comparative example: rare earth wastewater treating agent produced by a certain company in Beijing.
The rare earth wastewater is taken and added with the complexing agent for the rare earth wastewater and the treating agent of the comparative example for treatment. Wherein the initial content is: before treatment, the COD concentration (4569-6124 mg/L), the solid content (678-725 mg/L) and the ammonia nitrogen concentration (9786-12143 mg/L) are obtained. The content after the experiment was recorded separately. The test results are shown in Table 1.
Table 1:
test items Example 1 Example 2 Example 3 Comparative example
COD concentration mg/L 31 36 38 287~306
Solid content mg/L 106 112 108 247~311
Ammonia nitrogen concentration mg/L 9 4.6 6.8 187~204
In conclusion, the complexing agent for the rare earth wastewater has a good treatment effect and is worthy of being widely popularized and used.

Claims (5)

1. The complexing agent for the rare earth wastewater comprises an agent A and an agent B, and is characterized in that the preparation method of the agent A comprises the following steps:
(1) putting plant soil and a liquid culture medium into a container for culturing to obtain a culture solution, putting an inoculating loop into the culture solution for dipping to obtain a dipped inoculating loop, streaking the dipped inoculating loop in a solid culture medium to obtain a streaked solid culture medium, culturing the streaked solid culture medium at the temperature of 28-32 ℃ for 20-24 h, picking a bacterial colony with the largest bacterial diameter to obtain a bacterial colony, mixing the bacterial colony with the liquid culture medium, and stirring for 10-15 min to obtain a stirred mixture; the plant soil is potato culture soil;
(2) putting the stirred mixture into a fermentation tank, fermenting for 1-2 days at the temperature of 30-35 ℃ to obtain fermentation liquor, centrifuging the fermentation liquor for 20-30 min to obtain a precipitate, and mixing the precipitate and a preservative to obtain a mixture;
(3) crushing medical stone in a crusher to obtain crushed materials, mixing the crushed materials with a hydrochloric acid solution, soaking for 1-2 hours, filtering to obtain soaked filter residues, calcining the soaked filter residues at 400-600 ℃ to obtain calcined materials, mixing the calcined materials and the mixture, soaking for 1-2 hours, and filtering to obtain filter residues;
(4) mixing and dissolving chitosan and acetic acid solution, stirring until the chitosan is completely dissolved to obtain a dissolved solution, mixing filter residue, the dissolved solution and a cross-linking agent, reacting at the temperature of 50-60 ℃ for 1-2 hours to obtain a reactant, washing the reactant with a sodium hydroxide solution to obtain a washed reactant, and freeze-drying the washed reactant to obtain a dried substance, namely an agent A;
the preparation method of the agent B comprises the following steps:
a. mixing 30-40 parts of water, 2-3 parts of sodium carbonate, 1-2 parts of sodium nitrate, 0.8-1 part of dipotassium hydrogen phosphate, 0.2-0.3 part of sodium dihydrogen phosphate, 0.03-0.06 part of magnesium sulfate and 0.01-0.03 part of manganese sulfate in parts by weight, and sterilizing at high temperature to obtain a nutrient solution, wherein the mass ratio of the nutrient solution to the components is 2-3: 7-8, mixing seawater and a nutrient solution, culturing for 4-5 days at the temperature of 24-30 ℃ to obtain a culture solution, dipping an inoculating loop into the culture solution to obtain the dipped inoculating loop, mixing 30-40 parts of water, 2-3 parts of agar, 2-3 parts of sodium carbonate, 1-2 parts of sodium nitrate, 0.8-1 part of dipotassium hydrogen phosphate, 0.2-0.3 part of sodium dihydrogen phosphate, 0.03-0.06 part of magnesium sulfate and 0.01-0.03 part of manganese sulfate according to parts by weight, sterilizing at high temperature to obtain a culture medium, streaking the dipped inoculating loop in the culture medium, and culturing for 20-24 hours at the temperature of 28-32 ℃ to obtain a bacterial colony with the largest bacterial diameter;
b. and inoculating the colony with the largest bacterial diameter into a shake flask for culturing for 4-5 days to obtain a culture, putting the culture into a fermentation tank, and fermenting at the pH of 6-10 and the temperature of 20-28 ℃ to obtain a fermented product, namely the agent B.
2. The complexing agent for rare earth wastewater according to claim 1, wherein the liquid culture medium in the step (1) is prepared by uniformly mixing 50-60 parts by weight of distilled water, 20-30 parts by weight of glucose, 10-15 parts by weight of peptone, 5-8 parts by weight of sodium chloride and 0.5-1 part by weight of beef extract, and sterilizing at high temperature.
3. The complexing agent for rare earth wastewater according to claim 1, wherein the solid culture medium in the step (1) is prepared by uniformly mixing 50-60 parts by weight of distilled water, 20-30 parts by weight of glucose, 20-30 parts by weight of agar, 10-15 parts by weight of peptone, 5-8 parts by weight of sodium chloride and 0.5-1 part by weight of beef extract, and sterilizing at high temperature.
4. The complexing agent for rare earth wastewater according to claim 1, wherein the preservative in step (2) is any one of potassium sorbate and sodium benzoate.
5. The complexing agent for rare earth wastewater as set forth in claim 1, wherein the crosslinking agent in the step (4) is any one of dicumyl peroxide and dicumyl hydroperoxide.
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CN105502687A (en) * 2016-01-12 2016-04-20 杨洋 Organic industrial sewage purifying agent and using method thereof
CN105944698A (en) * 2016-07-05 2016-09-21 郭菲 Adsorbent for heavy metal ions in industrial wastewater and preparation method of adsorbent
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EP0536046A3 (en) * 1991-09-30 1993-09-01 Japan Marine Science And Technology Center Microorganism belonging to the genus flavobacterium, hydrocarbon emulsifier and solubilizer and separation method for organic-solvent tolerant microorganism
CN101811779A (en) * 2009-12-14 2010-08-25 国家海洋局天津海水淡化与综合利用研究所 Preparation method of halophilic decontamination bacterial agent and bacterial agent prepared by same
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