CN104671437A - Method for remedying U (VI) polluted water body by decomposing ground phosphate rock with Aspergillus niger - Google Patents
Method for remedying U (VI) polluted water body by decomposing ground phosphate rock with Aspergillus niger Download PDFInfo
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- CN104671437A CN104671437A CN201510093104.6A CN201510093104A CN104671437A CN 104671437 A CN104671437 A CN 104671437A CN 201510093104 A CN201510093104 A CN 201510093104A CN 104671437 A CN104671437 A CN 104671437A
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Abstract
The invention relates to a method for remedying a U (VI) polluted water body by decomposing ground phosphate rock with Aspergillus niger. The method comprises steps as follows: firstly, a Morgina culture medium taking the ground phosphate rock as an inorganic phosphorous source is added to the U (VI) polluted water body, then the pH value of the polluted water body is adjusted to range from 6.0 to 8.0, then the polluted water body is inoculated with an Aspergillus niger spore suspension for culture, citric acid and oxalic acid are produced, phosphorus in the ground phosphate rock is decomposed into phosphate radicals to be released to the U (VI) polluted water body, and the released phosphate radicals and uranyl ions in the water body have a precipitation reaction to produce (UO2)3(PO4)2*4H2O precipitate, so that the U (VI) polluted water body is remedied. The method has multiple advantages that the remediation cost is low, the remediation effect is good, secondary pollution is avoided and the like.
Description
Technical field
The present invention relates to U (VI) polluted-water, particularly the reparation of U (VI) polluted-water.Specifically one utilizes aspergillus niger to produce organic acid, in order to ground phosphate rock is resolved into phosphate radical, and then in order to form (UO with the U (VI) in water body
2)
3(PO
4)
24H
2o precipitates, thus realizes the method to the reparation of U (VI) polluted-water.
Background technology
Uranium is the important nuclear fuel of national defence and nuclear power, along with the fast development of national defense construction and Construction of Nuclear Electricity, increasing to the demand of natural uranium, make uranium mining, uranium ore processes and the scale of uranium hydrometallurgy increases day by day, thus cause the radiocontamination of water body in surrounding enviroment.Although the concentration of U (VI) is lower in this kind of radiocontamination water body, but it has very strong transport property, finally human body can be entered by food chain, accumulate in the liver of people, kidney and bone, and according to dosage size, acute or chronic poisoning can be caused, bring out various diseases, even cause hepar damnification, bring out cancer.In this kind of water body, U (VI) is main with uranyl (UO
2 2+), the form such as uranyl hydroxide and uranyl carbonate salt exists.China standard GB/T 23727-2009 specifies, in waste discharge, the concentration of uranium can not higher than 0.05 mg/L.
The traditional method of current China process radioactive wastewater mainly contains chemical precipitation method, ion exchange method, evaporation concentration method, extraction process etc.Adopt conventional process this kind of U (VI) polluted-water, there is technical process complexity, secondary treatment difficulty, cost is high, processing power is little, sludge quantity causes the shortcomings such as secondary environmental pollution greatly, easily after process.In recent years, some new treatment processs are there is, as biosorption process, swelling local method, emulsification embrane method, Zero-valence Iron Process.Although the sludge quantity problem such as greatly, easily cause secondary pollution, processing power little, also has its limitation after at present these new technologies can solve the process that conventional purge treatment process exists.Although biosorption process, Zero-valence Iron Process and emulsification embrane method treatment process are simple, responsive to environmental change, be therefore also in laboratory stage.It is large that swelling local method has treatment capacity, low cost and other advantages, but when processing this kind of uranium waste water, the interference by other chemical composition is large, and processing efficiency is low.
In sum, adopt method process U (VI) polluted-water researched and developed at present, there is secondary treatment difficulty, easily cause the shortcomings such as secondary environmental pollution, processing efficiency are low, processing cost is high.Thus, research and development are efficient, cheap, U (VI) polluted water body repairing method of non-secondary pollution, are still a difficult problem urgently to be resolved hurrily in the process of sustainable development of Uranium field.
Summary of the invention
For above situation, the invention provides one and utilize aspergillus niger to produce organic acid, in order to ground phosphate rock is resolved into phosphate radical, and then in order to form (UO with the U (VI) in water body
2)
3(PO
4)
24H
2o precipitates, thus realizes the method to the reparation of uranium U (VI) polluted-water.
For realizing above-mentioned target, invention is a kind of first to add with ground phosphate rock is that the Meng Jinna substratum of inorganic phosphorous sources is in uranium U (VI) polluted-water, again the pH value of polluted-water is adjusted to 6.0-8.0, then in inoculated aspergillus niger spore suspension to polluted-water to produce citric acid and oxalic acid, and then the phosphorus in ground phosphate rock is resolved into phosphate radical be discharged in U (VI) polluted-water, there is precipitin reaction in the U (VI) in phosphate radical and the water body of release, production (UO
2)
3(PO
4)
24H
2o precipitates, thus realizes the reparation to U (VI) polluted-water.The method has the multiple advantages such as rehabilitation cost is low, repairing effect good, non-secondary pollution.
Concrete measure is:
1, the Meng Jinna inorganic phosphorus bacteria substratum of preparation improvement, by 5-10 g glucose (C
6h
12o
6), 0.3-0.5 g ammonium sulfate [(NH
4)
2sO
4], 0.2-0.3 g sodium-chlor (NaCl), 0.2-0.3 g magnesium sulfate (MgSO
47H
2o), 0.02-0.03 g ferrous sulfate (FeSO
4), 0.02-0.03 g manganous sulfate (MnSO
4h
2o), 0.1-0.3 g Repone K (KCl), 1-10 g ground phosphate rock (phosphorus content is more than 3%) mixing, make Meng Jinna inorganic phosphorus bacteria substratum;
Add 10-15 g Meng Jinna inorganic phosphorus bacteria substratum in often liter of U (VI) polluted-water, and adopt the HCl solution of NaOH and 1:1 of 2 mol/L that polluted-water pH value is adjusted to 6.0-8.0.
2, will with the addition of U (VI) polluted-water sterilizing 30 min at 121 DEG C of Meng Jinna inorganic phosphorus bacteria substratum, the OD value of inoculation 10-50 ml/L is that the aspergillus niger spore suspension inoculation of 0.05-0.2 is in U (VI) polluted-water.After inoculated aspergillus niger spore suspension, in the temperature range of 25-30 DEG C, concussion is cultivated or logical oxygen is cultivated.In culturing process, when the pH of U (VI) polluted-water drops to below 4.0, be adjusted to more than 4.0 immediately, to prevent established (UO
2)
3(PO
4)
24H
2o is deposited in pH value affects repairing effect lower than dissolving under the condition of 4.0.
3, solid-liquid separation, when the density loss of U in water body (VI) is after 0.05 below mg/L, by method that is centrifugal or that filter by aspergillus strain, (UO
2)
3(PO
4)
24H
2o precipitation, phosphoric residue breeze are separated with water body.The aspergillus niger mycelia of separating and remaining ground phosphate rock can continue on for repairing U (VI) polluted-water.
4, saturated lime milk solution is adopted the pH value of filtrate to be adjusted to neutral rear discharge.
The invention provides one utilizes aspergillus niger to produce organic acid, in order to ground phosphate rock is resolved into phosphate radical, and then in order to form (UO with the U (VI) in water body
2)
3(PO
4)
24H
2o precipitates, thus realizes the method to the reparation of U (VI) polluted-water.
Compared with the existing methods, the present invention has following advantage:
Raw materials used ground phosphate rock price is low, and phosphorus mine tailing can be adopted to substitute, and can recycle, reduces the cost adopting soluble sources or organic phosphorus sources to repair U (VI) polluted-water.
In the process of repairing U (VI) polluted-water, do not add toxic chemical substance in waste water, decrease secondary pollution.
U (VI) polluted-water of the present invention to uranium mine pit water, uranium tailings pond steep water, hydrometallurgical process of uranium waste water, uranium polluted underground water and other type all has good repairing effect.
Ground phosphate rock of the present invention contains the materials such as calcium carbonate, when processing acid U (VI) polluted-water, can reduce the alkali charge of neutralized wastewater.
Compared with current existing Spent Radioactive water treatment method, the uranium in recoverable wastewater of the present invention, with low cost, flow process are simple, equipment easy care, do not produce secondary pollution, can wide U (VI) polluted-water of concentration for the treatment of scope.The present invention, to the progress promoting China's Uranium radioactive wastewater pollutant abatement technology, has great importance.
Embodiment
I material composition
Glucose, ammonium sulfate, sodium-chlor, magnesium sulfate, ferrous sulfate, manganous sulfate, Repone K, ground phosphate rock (phosphorus content is more than 3%), aspergillus niger spore, U (VI) polluted-water.
II embodiment
The Meng Jinna inorganic phosphorus bacteria substratum that preparation improves, main component is 5-10 g glucose (C
6h
12o
6), 0.3-0.5 g ammonium sulfate [(NH
4)
2sO
4], 0.2-0.3 g sodium-chlor (NaCl), 0.2-0.3 g magnesium sulfate (MgSO
47H
2o), 0.02-0.03 g ferrous sulfate (FeSO
4), 0.02-0.03 g manganous sulfate (MnSO
4h
2o), 0.1-0.3 g Repone K (KCl), 1-10 g ground phosphate rock (phosphorus content is more than 3%).Add 10-15 g Meng Jinna inorganic phosphorus bacteria substratum in often liter of U (VI) polluted-water, and adopt the HCl solution of NaOH and 1:1 of 2 mol/L that pH value is adjusted to 6.0-8.0.To with the addition of U (VI) polluted-water sterilizing 30 min at 121 DEG C of Meng Jinna inorganic phosphorus bacteria substratum, the OD value of inoculation 10-50 ml/L is that the aspergillus niger spore suspension inoculation of 0.05-0.2 is in U (VI) polluted-water.After inoculation, at 25-30 DEG C, concussion is cultivated or logical oxygen is cultivated.In culturing process, when the pH of U (VI) polluted-water drops to below 4.0, be adjusted to more than 4.0 immediately, to prevent established (UO
2)
3(PO
4)
24H
2o (s) be deposited in pH lower than 4.0 time discharge because solubleness significantly rises.When U (VI) density loss in water body is after 0.05 below mg/L, by method that is centrifugal or that filter by aspergillus strain wherein, (UO
2)
3(PO
4)
24H
2o precipitation, phosphoric residue breeze are separated with water body.Discharge after utilizing saturated lime milk solution that the pH value of filtrate is adjusted to neutrality.
III principle
Phosphorus in ground phosphate rock generally in indissoluble form, how by the release at low cost of the phosphate radical in ground phosphate rock, forms the very low (UO of solubleness to make itself and U (VI)
2)
3(PO
4)
24H
2o precipitates, and is the gordian technique adopting ground phosphate rock process U (VI) polluted-water.Normal temperature aspergillus niger spore in Meng Jinna inorganic phosphorus bacteria substratum, aspergillus niger is while growth and breeding, a large amount of organic acids can be produced, as oxalic acid, citric acid etc., these organic acid energy dissolved phosphorus breezes also discharge phosphate radical, when pH is in the scope of 4.0-6.0, U (VI) ion in the phosphate radical be released and waste water forms (UO
2)
3(PO
4)
24H
2o precipitates, thus removes the U (VI) in polluted-water.Should the pH value of control U (VI) polluted-water in culturing process, when pH close to 4.0 time should add alkaline matter by pH regulator in the scope of 4.0-6.0, to prevent established (UO
2)
3(PO
4)
24H
2o again dissolves under being deposited in too low pH and affects repairing effect.
IV embodiment
Embodiment 1, is in U (VI) polluted-water of 50 mg/L 1 liter of concentration, adds Meng Jinna substratum 15 g that ground phosphate rock content is 2 g/L, pH value is adjusted to 6.0.At 121 DEG C after sterilizing 30 min, cool to room temperature, inoculates the aspergillus niger spore suspension that 10 ml OD values are 0.1, cultivates 96 h at 25 DEG C.Now, in polluted-water, the density loss of U (VI) is to 0.042 mg/L, and pH value drops to 4.1.After adopting qualitative filter paper to filter, discharge after adopting saturated lime milk solution the pH value of filtrate to be adjusted to 7.0.
Embodiment 2, is in U (VI) polluted-water of 1 mg/L 1 liter of concentration, adds Meng Jinna substratum 13 g that ground phosphate rock content is 2 g/L, pH value is adjusted to 6.0.At 121 DEG C after sterilizing 30 min, cool to room temperature, inoculates the aspergillus niger spore suspension that 10 ml OD values are 0.1, cultivates 84 h at 25 DEG C.Now, in polluted-water, the density loss of U (VI) is to 0.036 mg/L, and pH value drops to 4.5.After adopting qualitative filter paper to filter, discharge after adopting saturated lime milk solution the pH value of filtrate to be adjusted to 7.0.
Embodiment 3, is in U (VI) polluted-water of 0.5 mg/L 1 liter of concentration, adds Meng Jinna substratum 12 g that ground phosphate rock content is 1 g/L, pH value is adjusted to 7.0.At 121 DEG C after sterilizing 30 min, cool to room temperature, inoculates the aspergillus niger spore suspension that 10 ml OD values are 0.1, cultivates 82 h at 30 DEG C.Now, in polluted-water, the density loss of U (VI) is to 0.032 mg/L, and pH value drops to 4.9.After adopting qualitative filter paper to filter, discharge after adopting saturated lime milk solution the pH value of filtrate to be adjusted to 7.0.
Embodiment 4, is in U (VI) polluted-water of 0.3 mg/L 1 liter of concentration, adds Meng Jinna substratum 11 g that ground phosphate rock content is 1 g/L, pH value is adjusted to 7.0.At 121 DEG C after sterilizing 30 min, cool to room temperature, inoculates the aspergillus niger spore suspension that 10 ml OD values are 0.1, cultivates 80 h at 30 DEG C.Now, in polluted-water, the density loss of U (VI) is to 0.031 mg/L, and pH value drops to 5.3.After adopting qualitative filter paper to filter, discharge after adopting saturated lime milk solution the pH value of filtrate to be adjusted to 7.0.
Embodiment 5, is in U (VI) polluted-water of 0.1 mg/L 1 liter of concentration, adds Meng Jinna substratum 10 g that ground phosphate rock content is 1 g/L, pH value is adjusted to 8.0.At 121 DEG C after sterilizing 30 min, cool to room temperature, inoculates the aspergillus niger spore suspension that 10 ml OD values are 0.1, cultivates 72 h at 28 DEG C.Now, in polluted-water, the density loss of U (VI) is to 0.030 mg/L, and pH value drops to 6.5.After adopting qualitative filter paper to filter, discharge after adopting saturated lime milk solution the pH value of filtrate to be adjusted to 7.0.
Be more than better implementation method of the present invention, according to above design of the present invention, those skilled in the art also can carry out various amendment and conversion to this.Such as, adopt the ground phosphate rock of different grade, adopt other carbon source such as starch, Sodium.alpha.-hydroxypropionate, inoculate the aspergillus niger spore suspension of different OD value, cultivate or adopt this method to repair U (VI) polluted-water of dissimilar, different concns and other heavy metal wastewater thereby or adjustment U (VI) polluted-water to repair to different pH at different temperatures.But similar this change and amendment still all belong to essence of the present invention.
Claims (2)
1. one kind utilizes aspergillus niger decomposing rock phosphate with hydrogen to repair U(VI) method of polluted-water, it is characterized in that, first add with ground phosphate rock is that the Meng Jinna substratum of inorganic phosphorous sources is in U (VI) polluted-water, again the pH value of polluted-water is adjusted to 6.0-8.0, then inoculated aspergillus niger spore suspension is in polluted-water, aspergillus niger produces citric acid and oxalic acid in growth metabolism process, and then the phosphorus in ground phosphate rock is resolved into phosphate radical be discharged in U (VI) polluted-water, uranyl ion generation precipitin reaction in phosphate radical and the water body of release, production (UO
2)
3(PO
4)
24H
2o precipitates, thus realizes the reparation to U (VI) polluted-water, and concrete steps are as follows:
The Meng Jinna inorganic phosphorus bacteria substratum that step 1, preparation are improved, by 5-10 g glucose, 0.3-0.5 g ammonium sulfate, 0.2-0.3 g sodium-chlor, 0.2-0.3 g magnesium sulfate, 0.02-0.03 g ferrous sulfate, 0.02-0.03 g manganous sulfate, 0.1-0.3 g Repone K, the mixing of 1-10 g ground phosphate rock, make Meng Jinna inorganic phosphorus bacteria substratum;
Add 10-15 g Meng Jinna inorganic phosphorus bacteria substratum in often liter of U (VI) polluted-water, and adopt the HCl solution of NaOH and 1:1 of 2 mol/L that uranium polluted-water pH value is adjusted to 6.0-8.0;
Step 2, U (VI) polluted-water sterilizing 30 min at 121 DEG C of Meng Jinna inorganic phosphorus bacteria substratum will be with the addition of, the OD value of inoculation 10-50 ml/L is that the aspergillus niger spore suspension inoculation of 0.05-0.2 is in U (VI) polluted-water, after inoculated aspergillus niger spore suspension, in the temperature range of 25-30 DEG C, concussion is cultivated or logical oxygen is cultivated;
Step 3, U(VI) solid-liquid separation of polluted-water, as U(VI) in polluted-water the density loss of uranium after 0.05 below mg/L, by centrifugal or filter type by aspergillus strain, (UO
2)
3(PO
4)
24H
2o precipitation, phosphoric residue breeze are separated with water body;
Step 4, adopt saturated lime milk solution the pH value of filtrate is adjusted to neutral after discharge.
2. one according to claim 1 utilizes aspergillus niger decomposing rock phosphate with hydrogen to repair the method for U (VI) polluted-water, it is characterized in that, in repair process, when the pH of U (VI) polluted-water drops to below 4.0, be adjusted to more than 4.0 immediately, to prevent established (UO
2)
3(PO
4)
24H
2o be deposited in pH value lower than 4.0 time dissolve and affect repairing effect.
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Cited By (4)
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| CN109182136A (en) * | 2018-08-31 | 2019-01-11 | 南京农业大学 | The separation and application of one plant of aspergillus niger JXZ01 with a variety of Insoluble phosphates capacities of decomposition |
| CN109626598A (en) * | 2019-01-23 | 2019-04-16 | 南华大学 | A method of utilizing Tabin aspergillus and phytate in-situ immobilization hexavalent uranium polluted surface water |
| CN111471859A (en) * | 2020-03-25 | 2020-07-31 | 南华大学 | Method for leaching uranium from low-grade uranium ore by macro-particle reinforced aspergillus niger |
| CN114561302A (en) * | 2022-02-10 | 2022-05-31 | 天津科技大学 | Aspergillus niger strain with high citric acid yield, method and application |
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| CN114561302B (en) * | 2022-02-10 | 2024-03-26 | 天津科技大学 | Aspergillus niger strain capable of producing citric acid in high yield, method and application |
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