CN101700925B - Method for preparing biological composite nano-water-purifying materials for removing radioactive substances in water - Google Patents
Method for preparing biological composite nano-water-purifying materials for removing radioactive substances in water Download PDFInfo
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- CN101700925B CN101700925B CN2009102178633A CN200910217863A CN101700925B CN 101700925 B CN101700925 B CN 101700925B CN 2009102178633 A CN2009102178633 A CN 2009102178633A CN 200910217863 A CN200910217863 A CN 200910217863A CN 101700925 B CN101700925 B CN 101700925B
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Abstract
The invention belongs to the environment protection field, not only belonging to the treatment methods for controlling sewage disposal in the nuke industry and the radiochemistry industry but also belonging to the methods for eliminating radioactive isotopes in the nature water. The invention in particular relates to a method for preparing a series of biological composite nano-water-purifying materials which take mildews with different features as the matrices and various metallic nano materials (such as oxides and hydroxides of titanium, aluminum and iron, etc.) in different nano shapes (nano particles, nano fibers and nano tubes) as the modified materials and can effectively remove the radioactive substances in the water. The method fully utilizes the adsorption effect of the microbes on the surrounding substances to attach the nano materials on the surfaces of the microbial cells, thus obviously improving the capabilities of the nano materials in adsorption and dirt removal; therefore, the nano materials can effectively remove the radioactive substances in the water.
Description
Technical field
The invention belongs to field of environment protection, both belonged to the processing method of administering nuclear industry and radio chemistry industrial discharge sewage, also belong to the radioisotopic method in the natural water of removing.Being specifically related to a series of bacterium of mildewing with different-shape is matrix, various metal nano materials (oxide and the hydroxide of metals such as titanium, aluminium, iron) with different nanometer shapes (nano particle, nanofiber, nanotube) are material modified, can effectively remove the preparation method of the biological composite nano water-purifying material of waterborne radioactivity material.
Technical background
The nuclear energy volume is little, and energy is big, pollutes and lacks, and reserves are abundant, and the characteristics that cost is low more and more come into one's own its today in energy crisis.Along with the increasingly extensive application of nuclear energy, its radioactive pollution that brings is also serious day by day.Radioactive pollution causes after entering environment by radioactive substance.Radioactive pollutant is mainly derived from the cooling water that nuclear power factory is discharged, and to the radwaste of ocean dumping, nuclear explosion drops to the fall-out of water body, the nuclear fuel of atomic-powered ship accident leakage; Exploitation, refine and when using radioactive substance,, also can cause radioactive pollution if deal with improperly.Wherein the radioactive pollutant in the water body can also can enter organism and accumulate attached to organism surface, also can cause canceration by food chain enrichment and human body produced internal radiation hazard in human body.
New " drinking water sanitary standard " put into effect of China 2006 (GB5749-2006) newly revised the water quality detection limit value of radioactive substance concentration, relevant radioactive substance water quality conventional index and limit value such as following table:
| Radioactive indicator | Standard |
| Total (Bq/L) | 0.5 |
The main technology of water purification technology of removing radioactive substance at present has: Coagulation Method, absorption method, ion-exchange and biological treatment.In the processing method of routine, metal nano material has bigger specific area and higher charge density because of it, radioactive substance in the water there is higher suction-operated, but, cause at the water treatment characterization of adsorption that can not give full play to these materials in service because these metallic compounds are separated difficulty from water.Biological treatment carries out suitable physical and chemical modified to it on this basis and can significantly improve its absorption dirty removal capacities because of its extensive, various in style, alternative big, lower-cost characteristic of drawing materials is subjected to using widely.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method that can remove the biological composite nano water-purifying material of waterborne radioactivity material.The present invention utilizes the suction-operated of microorganism to the surrounding environment material, with nanometer material for making clothes material attached to the microbial cell surface, thereby significantly improve its absorption scrubbing ability, can remove the waterborne radioactivity material effectively.
The preparation method of the biological composite nano material of removal radioactive substance of the present invention, its step is as follows:
1,16～20 gram peptones, 20～25 gram glucose, 12.5～15.0 gram agar are joined in 1000 ml distilled waters, evenly stir, be heated to boiling, boiled 20～30 minutes, make the organic matter that is added be dissolved in the water fully and sterilization simultaneously; In 85～95 ℃ of solid nutrient media that cool off a little, add 5～8 gram glycerine again, in desinfection chamber, 18～36 gram solid nutrient media are injected in the plastic culture dish then;
2, with the bacterium liquid of bacterial classification (as aspergillus niger and mucor mucedo) preparation 50～100CFU/ml, inoculate bacterial classification in above-mentioned solid medium under aseptic condition, each plastic culture dish adds 2～4ml bacterium liquid, and cultivation cycle is 72～80 hours, and cultivation temperature is 37～38 ℃.
3, be that the sodium citrate aqueous solution of 0.05～0.1% citric acid and mass fraction 1～2% joins in the 1L distilled water and stirred 10～20 minutes with 9～20 nano particles and 25 milliliters of mass fractions, mixed solution;
4, the mould thalline that will cultivate gained in the solid nutrient medium and the mixed solution for preparing are with 10～20 grams: 1 liter ratio is mixed, and stirs; Under 37～38 ℃ of conditions, placed 6～8 days then;
5, by filtration or centrifugal action thalline is separated from mixed liquor, handle the biological composite nano water-purifying material that obtains removal radioactive substance of the present invention postmenstruation.
In the above-mentioned steps, described post-processed is to add acetone in thalline gradually, makes the cut of acetone in acetone soln reach 20～30% at first, makes cut reach 40～50% after 15～20 minutes excessively, makes cut reach 75～80% after 15～20 minutes; The open-top receptacle that thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of drier, temperature keeps 56～60 ℃, continues 3～5 hours.The dehydration thalline of gained put into have CaCl
2Preserve in the container of drier.
The nano particle that relates in the above-mentioned steps is metal oxide/hydroxide nano particle or metal oxide nanoparticles, and concrete can be TiO
2Nanotube, AlOOH (boehmite) nanofiber, a-FeOOH nanofiber etc.
Description of drawings
Fig. 1: embodiment 1 described mucor mucedo electromicroscopic photograph through the AlOOH modification;
Length through the mucor mucedo of AlOOH modification is 2.6～6 μ m, and particle diameter is 327nm-394nm, is bar-shaped.
The specific embodiment
This patent is to set forth the present invention with embodiment, rather than limitation of the present invention, and every to relate to metal oxide/hydroxide or metal oxide be main altered contents, and the composite nano materials of preparation in this way, is our rights protection scope.
Embodiment 1:
Radiation absorber system by AlOOH (boehmite) nanofiber and mucor mucedo (Mucor mucedo) preparation hybridization.
16 gram peptones, 20 gram glucose, 12.5 gram agar are joined in 1000 ml distilled waters, evenly stir, be heated to boiling, boil made in 30 minutes add organic matter consoluet simultaneously the sterilization, add glycerine 5 grams in the medium that a little a bit cools off (93 ℃), with consumptions of each 36 gram the solid medium that makes being injected into diameter in desinfection chamber is in 9 millimeters the plastic culture dish.
In the solid medium that is making under 37 ℃ of aseptic conditions, inoculate the commercially available mucor mucedo bacterium liquid of 2ml, 80CFU/ml, cultivated 72 hours.With scraper the mucor mucedo thalline that grows out is scraped off from the solid culture primary surface.
(with the aluminium powder is raw material to get 9 gram laboratory self-control AlOOH nanofibers, its hydrolysis in 70～90 ℃ distilled water is obtained, its particle diameter is 50～100nm) to join in 1 liter of distilled water, adding 25 milliliters again, to contain mass fraction be that 0.05% citric acid and mass fraction are the aqueous solution of 1% natrium citricum, add the mucor mucedo thalline that 10 gram above-mentioned steps cultivate again in the above-mentioned mixed liquor and stir, under 37 ℃ of conditions, placed 6 days.For the differentiation of living cells and dead cell, the hybridization mycelium of growing is dyeed every vitality of observing the hybridization microorganism round the clock with propidium iodide (PI) and adenylase (7-AAD).Lasting 6 observe the vitality of mucor mucedo cell round the clock.With mucor mucedo thalline from the mixed liquor isolated by filtration of funnel with modification, obtain 17 gram thalline solution, in thalline, add acetone gradually, make the cut of acetone in solution reach 25% at first, make cut reach 40% after spending 15 minutes, after 15 minutes, make cut reach 75%; The open-top receptacle that thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of drier, temperature keeps 60 ℃, continues 4 hours, the dehydration thalline of gained is put into to have CaCl again
2Preserve in the container of drier.
The uranyl nitrtate that takes by weighing 0.0109g joins in the distilled water of 1L, fully stirs, and is made into the aqueous solution of uranyl nitrtate.Get 5 small beakers, pour the aqueous solution of this uranyl nitrtate that 30ml configures in each beaker into, the mucor mucedos through the AlOOH modification that dewatered (0.1087g, 0.2020g, 0.2983g, 0.3951g, do not add) that add different amounts in the beaker fully stir, after ultrasonic 20 minutes, leave standstill and leached supernatant liquor in 2 days, survey supernatant liquor with ICP-MS7500a/ce (icp ms)? the concentration of middle uranium element.
Table 1: after placing two days (48h), the adsorpting data of the uranium element in the supernatant
| Numbering | Adsorbent mass (g) | Uranium element concentration (ppb) | Adsorption rate (%) |
| 0 | 0.0000 | 6956 | 0 |
| 1 | 0.1087 | 192.2 | 97.2369 |
| 2 | 0.2020 | 201.4 | 97.1047 |
| 3 | 0.2983 | 125.8 | 98.1915 |
| 4 | 0.3951 | 129.0 | 98.1455 |
Embodiment 2:
By TiO
2The radiation of (titanium dioxide) nanotube and aspergillus niger (Aspergillus niger) preparation hybridization absorbs thalline system.
16 gram peptones, 20 gram glucose, 12.5 gram agar are joined in 1000 ml distilled waters, evenly stir, be heated to boiling, boil made in 30 minutes add organic matter consoluet simultaneously the sterilization, add glycerine 5 grams in the medium that a little a bit cools off (93 ℃), with consumptions of each 36 gram the solid medium that makes being injected into diameter in desinfection chamber is in 9 millimeters the plastic culture dish.
The commercially available black-koji mould liquid of inoculation 2ml100CFU/ml was cultivated 72 hours in the solid medium that is making under 37 ℃ of aseptic conditions.Scrape off from the solid culture primary surface with the scraper aspergillus niger thalline that will grow out.
Get 20 gram laboratory self-control TiO
2(with nanometer powder TiO
2Powder and NaOH are raw material, use Hydrothermal Preparation at 110～150 ℃, particle diameter 30～180nm) nanotubes join in 1 liter of distilled water, adding 25 milliliters again, to contain mass fraction be that 0.05% citric acid and mass fraction are the aqueous solution that 1% citric acid is received, add the aspergillus niger thalline that 10 grams cultivate in the mixed liquor and stir, place 8 down round the clock at 37 ℃.The aspergillus niger that to grow for the differentiation of living cells and dead cell dyes with propidium iodide (PI) and adenylase (7-AAD), every vitality of observing the hybridization microorganism round the clock.With aspergillus niger thalline from the mixed liquor isolated by filtration of funnel with modification, obtain 26 gram thalline solution, in thalline, add acetone gradually, make the cut of acetone in solution reach 30% at first, make cut reach 50% after spending 20 minutes, after 20 minutes, make cut reach 80%; The open-top receptacle that the aspergillus niger thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of drier, temperature keeps 60 ℃, continues 5 hours.The dehydration thalline of gained put into have CaCl
2Preserve in the container of drier.
The uranyl nitrtate that takes by weighing 0.0109g joins in the distilled water of 1L, fully stirs, and is made into the aqueous solution of uranyl nitrtate.Get 5 small beakers, pour the aqueous solution of this uranyl nitrtate that 30ml configures in each beaker into, in beaker, add the dehydrations of different amounts through TiO
2The aspergillus niger of nanotube modification (0.1053g, 0.2109g, 0.3011g, 0.4139g, do not add) fully stirs, after ultrasonic 20 minutes, leave standstill and leached supernatant liquor in 2 days, survey the concentration of uranium element in the molten supernatant liquor with ICP-MS7500a/ce (icp ms).
Table 2: after placing two days (48h), the adsorpting data of the uranium element in the supernatant
| Numbering | Adsorbent mass (g) | Uranium element concentration (ppb) | Adsorption rate (%) |
| 0 | 0.0000 | 7034 | 0 |
| 1 | 0.1053 | 282.3 | 95.9866 |
| 2 | 0.2109 | 264.8 | 96.2354 |
| 3 | 0.3011 | 183.2 | 97.3955 |
| 4 | 0.4139 | 210.1 | 97.0131 |
Claims (2)
1. preparation method of removing the biological composite nano material of waterborne radioactivity material, its step is as follows:
A) 16～20 gram peptones, 20～25 gram glucose, 12.5～15.0 gram agar are joined in 1000 ml distilled waters, evenly stir, be heated to boiling, boiled 20～30 minutes, make the organic matter that is added be dissolved in the water fully and sterilization simultaneously; In 85～95 ℃ of solid nutrient media that cool off a little, add 5～8 gram glycerine again, in desinfection chamber, 18～36 gram solid nutrient media are injected in the plastic culture dish then;
B) with the bacterium liquid of bacterial classification preparation 50～100CFU/ml, inoculate bacterial classification under aseptic condition in solid medium, each plastic culture dish adds 2～4ml bacterium liquid, and cultivation cycle is 72～80 hours, and cultivation temperature is 37～38 ℃;
C) aqueous solution that is 0.05～0.1% citric acid and mass fraction 1～2% natrium citricum with 9～20 gram nano particles and 25 milliliters of mass fractions joins in the 1L distilled water and stirred 10～20 minutes, must mixed solution;
D) the mould thalline that will cultivate gained in the solid nutrient medium and the mixed solution for preparing are with 10～20 grams: 1 liter ratio is mixed, and stirs; Under 37～38 ℃ of conditions, placed 6～8 days then;
E) by filtration or centrifugal action thalline is separated from mixed liquor, handle the biological composite nano material that obtains removing the waterborne radioactivity material postmenstruation;
Wherein, nano particle is TiO
2Nanotube or AIOOH nanofiber; Post-processed is to add acetone in thalline gradually, makes the cut of acetone in solution reach 20～30% at first, makes cut reach 40～50% after 15～20 minutes excessively, makes cut reach 75～80% after 15～20 minutes; The open-top receptacle that thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of drier, temperature keeps 56～60 ℃, continues 3～5 hours, the dehydration thalline of gained is put into have CaCl
2Preserve in the container of drier.
2. a kind of preparation method of removing the biological composite nano material of waterborne radioactivity material as claimed in claim 1, it is characterized in that: bacterial classification is aspergillus niger or mucor mucedo.
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| DE102013207197A1 (en) | 2013-04-22 | 2014-10-23 | Helmholtz-Zentrum Dresden - Rossendorf E.V. | Process and system for the separation of heavy metals |
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| CN102603083B (en) * | 2012-04-09 | 2013-07-10 | 吉林大学 | Biological nanocomposite materials for removing organic matter out of water |
| CN102603082B (en) * | 2012-04-09 | 2013-10-16 | 吉林大学 | Biological nanocomposite for removing heavy metals in water |
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| CN115093012B (en) * | 2022-06-27 | 2023-11-17 | 陕西科技大学 | TiO (titanium dioxide) 2 Aspergillus niger carbonized carbon compound and preparation method and application thereof |
| CN115050586B (en) * | 2022-06-27 | 2024-04-12 | 陕西科技大学 | MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof |
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| DE102013207197A1 (en) | 2013-04-22 | 2014-10-23 | Helmholtz-Zentrum Dresden - Rossendorf E.V. | Process and system for the separation of heavy metals |
| DE102013207197B4 (en) | 2013-04-22 | 2019-05-02 | Helmholtz-Zentrum Dresden - Rossendorf E.V. | Process for the separation of heavy metals, use of the process and use of a system for the purification of heavy metals contaminated waters or for the detection of heavy metals in waters |
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