CN101700925A - 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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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 treatment process 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 compound and the oxyhydroxide of metals such as titanium, aluminium, iron) with different nanometer shapes (nanoparticle, 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 dilemma.Along with the increasingly extensive application of nuclear energy, its radiocontamination that brings is also serious day by day.Radiocontamination causes after entering environment by radioactive substance.Radioactive pollutant is mainly derived from the water coolant that nuclear power factory is discharged, and to the radwaste of ocean dumping, nuclear explosion drops to the fallout of water body, the nuclear fuel of atomic-powered ship accident leakage; Exploitation, refine and when using radioactive substance,, also can cause radiocontamination 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 method and biological treatment.In the treatment process of routine, metal nano material has bigger specific surface area and higher electric density because of it, radioactive substance in the water there is higher adsorption, 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 adsorption of microorganism to the surrounding environment material, with nanometer material for making clothes material attached to the microorganism cells surface, thereby significantly improve its absorption scrubbing ability, can remove the waterborne radioactivity material effectively.
The making 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 organism that is added be dissolved in the water fully and sterilization simultaneously; Add 5～8 gram glycerine in the refrigerative solid nutrient medium a little to 85～95 ℃ again, in sterilisable 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 culture cycle is 72～80 hours, and culture temperature is 37～38 ℃.
3, be that the sodium citrate aqueous solution of 0.05～0.1% citric acid and massfraction 1～2% joins in the 1L distilled water and stirred 10～20 minutes with 9～20 nanoparticles and 25 milliliters of massfractions, mixing solutions;
4, the mould thalline that will cultivate gained in the solid nutrient medium and the mixing solutions for preparing are with 10～20 grams: 1 liter mixed, and stir; Under 37～38 ℃ of conditions, placed 6～8 days then;
5, by filtration or centrifugation thalline is separated from mixed solution, 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 container that thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of siccative, temperature keeps 56～60 ℃, continues 3～5 hours.The dehydration thalline of gained put into have CaCl
2Preserve in the freight container of siccative.
The nanoparticle that relates in the above-mentioned steps is metal oxide/hydroxide nanoparticle 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.
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 organism 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 sterilisable 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 massfraction be that 0.05% citric acid and massfraction are the aqueous solution of 1% Trisodium Citrate, add the mucor mucedo thalline that 10 gram above-mentioned steps cultivate again in the above-mentioned mixed solution and stir, under 37 ℃ of conditions, placed 6 days.For the differentiation of viable cell 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 solution filtering separation 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 container that thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of siccative, temperature keeps 60 ℃, continues 4 hours, the dehydration thalline of gained is put into to have CaCl again
2Preserve in the freight container of siccative.
The uranyl nitrate that takes by weighing 0.0109g joins in the distilled water of 1L, fully stirs, and is made into the aqueous solution of uranyl nitrate.Get 5 small beakers, pour the aqueous solution of this uranyl nitrate 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 liquid in 2 days, survey supernatant liquid 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 liquor
| 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 organism 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 sterilisable 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 massfraction be that 0.05% citric acid and massfraction are the aqueous solution that 1% citric acid is received, add the aspergillus niger thalline that 10 grams cultivate in the mixed solution and stir, place 8 down round the clock at 37 ℃.The aspergillus niger that to grow for the differentiation of viable cell 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 solution filtering separation 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 container that the aspergillus niger thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of siccative, temperature keeps 60 ℃, continues 5 hours.The dehydration thalline of gained put into have CaCl
2Preserve in the freight container of siccative.
The uranyl nitrate that takes by weighing 0.0109g joins in the distilled water of 1L, fully stirs, and is made into the aqueous solution of uranyl nitrate.Get 5 small beakers, pour the aqueous solution of this uranyl nitrate 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 liquid in 2 days, survey the concentration of uranium element in the molten supernatant liquid with ICP-MS7500a/ce (icp ms).
Table 2: after placing two days (48h), the adsorpting data of the uranium element in the supernatant liquor
| 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 (5)
1. making 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 organism that is added be dissolved in the water fully and sterilization simultaneously; Add 5～8 gram glycerine in the refrigerative solid nutrient medium a little to 85～95 ℃ again, in sterilisable 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 in above-mentioned solid medium under aseptic condition, each plastic culture dish adds 2～4ml bacterium liquid, and culture cycle is 72～80 hours, and culture temperature is 37～38 ℃.
C) aqueous solution that is 0.05～0.1% citric acid and massfraction 1～2% Trisodium Citrate with 9～20 nanoparticles and 25 milliliters of massfractions joins in the 1L distilled water and stirred 10～20 minutes, mixing solutions;
D) the mould thalline that will cultivate gained in the solid nutrient medium and the mixing solutions for preparing are with 10～20 grams: 1 liter mixed, and stir; Under 37～38 ℃ of conditions, placed 6～8 days then;
E) by filtration or centrifugation thalline is separated from mixed solution, handle the biological composite nano water-purifying material that obtains removing the waterborne radioactivity material postmenstruation.
2. a kind of making 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.
3. a kind of making method of removing the biological composite nano material of waterborne radioactivity material as claimed in claim 1, it is characterized in that: post-processed is to add acetone in thalline gradually, make the cut of acetone in acetone soln reach 20～30% at first, make cut reach 40～50% after spending 15～20 minutes, after 15～20 minutes, make cut reach 75～80%; The open container that thalline will be housed is then put into and is had anhydrous CaCl
2In the drying cupboard of siccative, temperature keeps 56～60 ℃, continues 3～5 hours, the dehydration thalline of gained is put into have CaCl
2Preserve in the freight container of siccative.
4. a kind of making method of removing the biological composite nano material of waterborne radioactivity material as claimed in claim 1, it is characterized in that: nanoparticle is metal oxide/hydroxide nanoparticle or metal oxide nanoparticles.
5. a kind of making method of removing the biological composite nano material of waterborne radioactivity material as claimed in claim 4, it is characterized in that: nanoparticle is TiO
2Nanotube, AlOOH nanofiber or a-FeOOH nanofiber.
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