CN103447027A - Modified nano TiO2/Ag/bamboo charcoal composite material and method for killing microorganisms in medical sewage by virtue of same - Google Patents
Modified nano TiO2/Ag/bamboo charcoal composite material and method for killing microorganisms in medical sewage by virtue of same Download PDFInfo
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- CN103447027A CN103447027A CN2013103825957A CN201310382595A CN103447027A CN 103447027 A CN103447027 A CN 103447027A CN 2013103825957 A CN2013103825957 A CN 2013103825957A CN 201310382595 A CN201310382595 A CN 201310382595A CN 103447027 A CN103447027 A CN 103447027A
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Abstract
The invention discloses a modified nano TiO2/Ag/bamboo charcoal composite material and a method for killing microorganisms in medical sewage by virtue of the same. A preparation method of the composite material comprises the following steps of preparing stable modified TiO2 sol by a sol-gel method, performing ultrasonic treatment to enable titanium dioxide particles to enter internal pores of bamboo charcoal, and roasting to prepare the nano-level titanium dioxide which has photocatalytic activity and is loaded on the bamboo charcoal. According to the invention, very little hydrogen peroxide is added into the medical sewage with certain concentration to adjust the pH to 3-4, the composite material is added into the sewage (wherein the adding amount of the composite material is about 20g/L), and then the microorganisms in the medical sewage can be killed efficiently in the sunlight. After the sewage is treated in the sunlight for 10 minutes, the observation in a microscope shows that a good killing effect for the microorganisms in the medical sewage is obtained.
Description
Technical field
The present invention relates to a kind of modified Nano TiO
2/ Ag/ bamboo charcoal composite material and use it to kill method of microorganism in medical sewage, be specifically related to a kind of TiO
2/ Ag/ bamboo charcoal composite material and adopt this material kill medical sewage under sunshine in method of microorganism.Add the minute quantity hydrogen peroxide, TiO in medical sewage
2/ Ag/ bamboo charcoal composite material can in sewage, produce hydroxyl radical free radical under sunshine and silver ion carrys out the destroy microorganisms eucaryotic cell structure, can kill various microorganisms in sewage, thereby processes medical waste water with extremely low cost.
Background technology
Medical waste water source and composition are very complicated, contain a large amount of pathogenic microbes, poisonous, harmful physical chemistry pollutant, there is the features such as space-pollution, acute infection, latent infection, if can become the important channel of an epidemic disease diffusion without effectively processing direct discharge.
At present, large hospital has certain Waste Water Treatment, but the sewage disposal of hospital aspect of small scale is just weaker, so seek a kind of cheapness, the method that can kill microorganism in sewage and improve water quality simple to operate just seems very necessary.
Chinese invention patent---application number is 201210271494.8 to relate to " a kind of medical field sewage disposal system ".This patent discloses a kind of Medical Wastewater Disposal System, at first sewage remove solid particle in water through MBR membrane filtration pond, then carry out sterilizing through mixing sterilization pool, this system has many good qualities really, we only propose this part of this system sterilizing and adopt ozonization to have following several problem: 1., the medical waste water after processing, and because the ozone residue has penetrating odor; 2., form some ozonation by-products; 3., ozone treatment waste water, can make the biological degradability of dissolubility natural organic matter improve, in pipe network, biological fouling meeting is more serious.As in sterilization, this part adopts our composite and sunshine sterilization, will have low energy consumption, sterilization thoroughly, the efficiency high.
Summary of the invention
The technical problem solved
For fear of the deficiencies in the prior art part, the present invention proposes a kind of TiO
2the preparation method of/Ag/ bamboo charcoal composite material and adopt that this material use sunshine is cheap removes method of microorganism in medical sewage, utilize the method to process medical sewage and there is cheapness, low energy consumption, technique, the operation advantage such as very simple, can make up the problem that China's small-middle hospital waste water is not effectively addressed to a certain extent.Utilize the composite that the method makes to there is the advantages such as the reunion of being difficult for, easily recovery, low energy consumption, environmental protection.
Technical scheme
A kind of modification TiO
2/ Ag/ bamboo charcoal composite material, it is characterized in that the raw material composition is: iron nitrate solution, 0.5 part of glacial acetic acid, 1～3 part of concentration that the butyl titanate of 1 part, 0.3～0.4 part of concentration are 0.21mol/L are 0.01mol/L～0.02mol/L liquor argenti nitratis ophthalmicus and bamboo charcoal, and described umber is parts by volume.
A kind ofly prepare described TiO
2the method of/Ag/ bamboo charcoal composite material is characterized in that step is as follows:
Step 1: the parts by volume proportioning of the butyl titanate of 1 part, 3～4 parts of absolute ethyl alcohols is added in container and stirs, make A solution; The parts by volume proportioning of the iron nitrate solution that is 0.21mol/L by 0.3～0.4 part of concentration again, 1～2 part of absolute ethyl alcohol, 0.5 part of glacial acetic acid adds in container and stirs, and makes B solution;
Step 2: B solution is added in A solution, and the limit edged stirs, and is added dropwise to complete rear continuation and stirs to form colloidal sol, by colloidal sol ageing 5h left and right, obtains vitreosol;
Step 3: bamboo charcoal is put in the vitreosol that step 2 makes, and ultrasonic lower the processings 1h that is 45KHz at 32 ℃ of lower frequencies after stirring makes colloidal sol enter the bamboo charcoal internal void, takes out afterwards bamboo charcoal drying under 80 ℃; The addition of described bamboo charcoal is being as the criterion by the colloidal sol submergence;
Step 4: take out bamboo charcoal and obtain modification TiO at 550 ℃ of lower roasting 3h under nitrogen atmosphere from the drying box of step 3 in tube furnace
2/ bamboo charcoal composite material.
Step 5: the modification TiO that step 4 is obtained
2/ bamboo charcoal composite material immerses the nitric acid of 0.01mol/L～0.02mol/L
In silver solution, utilize concentrator process under sunshine or directly under uviol lamp, process 2h, take out composite, dry under 80 ℃, obtain TiO
2/ Ag/ bamboo charcoal composite material.
Rate of addition when in described step 2, B solution adds A solution is 1/s.
The uviol lamp power of selecting in described step 5 is 12w, and generation ultraviolet wavelength is 360nm.
A kind ofly utilize described modified Nano TiO
2/ Ag/ bamboo charcoal composite material is killed method of microorganism in medical sewage, it is characterized in that: adopt hydrogen peroxide by the pH furnishing 3-4 of medical sewage, add modified Nano TiO
2/ Ag/ bamboo charcoal composite material, under sunshine, process obtain killing medical sewage in microorganism; Described modified Nano TiO
2the addition of/Ag/ bamboo charcoal composite material is 20g/L.
Beneficial effect
The present invention proposes a kind of TiO
2the preparation method of/Ag/ bamboo charcoal composite material and adopt that this material use sunshine is cheap processes method of microorganism in medical sewage, adopt the standby stable modification TiO of Sol-gel legal system
2colloidal sol, process through ultrasonic wave, makes TiO 2 particles can enter the bamboo charcoal internal void, and after roasting, preparation has photocatalytic activity, loads on the Nano titanium dioxide on bamboo charcoal.In the finite concentration medical sewage, add the hydrogen peroxide of minute quantity then by pH furnishing 3-4, by composite add in waste water (the about 20g/L of composite addition) just can efficiently kill medical sewage under sunshine in microorganism, sunshine is processed after 10 minutes and is examined under a microscope microorganism in medical sewage is obtained to extraordinary killing effect.
Kill method of microorganism in medical sewage, relate to a kind of sterilization composite that can recycle.Existing water treatment technical sterilization method is characterized in that ray energy is high, in water, can produce the free radical that density is very high, but its power consumption is also quite large.Sterilization composite of the present invention, every 100ml sewage adds the 2g composite then to splash into the hydrogen peroxide that about 0.1ml mass fraction is 30%, process in 10min and just almost can kill all microorganisms under sunshine, the sterilization composite reclaims very convenient can be recycled, with low cost.Sterilization mechanism is mainly to utilize titanium dioxide and hydrogen peroxide and iron ion can produce hydroxyl radical free radical under the sunshine effect, utilizes hydroxyl radical free radical to carry out killing microorganisms.The oxidability of hydroxyl radical free radical is extremely strong only lower than simple substance fluoride, and the strong oxidability of hydroxyl radical free radical can be inorganic molecules by nearly all mineralization of organic material, so hydroxyl radical free radical almost can be killed all microorganisms.The invention has the beneficial effects as follows: it is a kind of safe, the sewage water treatment method of the energy Killing Microorganisms In Water of low energy consumption, and water quality treatment is improved obviously, and sterilizing rate is high, and easy to operate.
The prepared composite of the present invention has the ability of efficiently killing microorganism in medical sewage, recycles number of times and reaches more than 30 times.
The accompanying drawing explanation
Fig. 1: the flow chart of the inventive method;
Fig. 2: TiO
2the microcosmic scintigram of/Ag/ bamboo charcoal composite material, can see the prosperity of composite pore structure, and area load has TiO
2particle and silver particles;
Fig. 3: at optical microphotograph Microscopic observation medical sewage, a figure amplifies 100 times, and b figure amplifies 400, can find in medical sewage to contain many microorganisms from figure, and wherein many may be pathogenic microorganisms, and directly discharge may become to cause the epidemic disease diffusion.
Fig. 4: the medical sewage after the optical microphotograph Microscopic observation is processed 10 minutes, a figure amplifies 100 times, and b figure amplifies 400, and in the medical sewage after can finding to process from figure, microorganism almost is killed totally, is difficult to find microorganism in the visual field.
The specific embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1: 1., the parts by volume proportioning of the butyl titanate of 1 part, 3 parts of absolute ethyl alcohols is added in a dry clean container and stirs, make A solution, the parts by volume proportioning of the iron nitrate solution that is 0.21mol/L by 0.3 part of concentration again, 1 part of absolute ethyl alcohol, 0.5 part of glacial acetic acid adds in a dry clean container and stirs, and makes B solution; 2., B solution is slowly added in A solution, the limit edged stirs, and is added dropwise to complete rear continuation stir about 30min and forms stable colloidal sol, and the about 5h of colloidal sol ageing is stand-by; 3., bamboo charcoal is put into to the ageing colloidal sol that 2. step make after, process 1h under the ultrasound condition that is 45KHz at 32 ℃ of lower frequencies and make rare gel enter the bamboo charcoal internal void, take out afterwards bamboo charcoal dry under 80 ℃; 4., take out bamboo charcoal drying box 3. from step in tube furnace under nitrogen atmosphere, at 550 ℃ of lower roasting 3h, obtain TiO
2/ bamboo charcoal catalyst, it is immersed to concentration is darkroom disposal a period of time in the 0.01mol/L liquor argenti nitratis ophthalmicus, under sunshine or under uviol lamp, processes afterwards, after taking-up composite drying, obtains TiO
2/ Ag/ bamboo charcoal composite material; 5., get a medical sewage film-making and examine under a microscope microorganism in sewage, record the microorganism shape characteristic; 6., in 100ml finite concentration medical sewage, add the hydrogen peroxide that the 0.1ml mass fraction is 30%, then with dilute sulfuric acid by system pH furnishing acidity; 7., TiO 2g made
2/ Ag/ bamboo charcoal composite material adds medical sewage, and sunshine was processed after 10 minutes, gets a medical sewage film-making and examines under a microscope microorganism in sewage, observes the microorganism removal effect, record data.
Embodiment 2: 1., the parts by volume proportioning of the butyl titanate of 1 part, 3 parts of absolute ethyl alcohols is added in a dry clean container and stirs, make A solution, the parts by volume proportioning of the iron nitrate solution that is 0.21mol/L by 0.4 part of concentration again, 1 part of absolute ethyl alcohol, 0.5 part of glacial acetic acid adds in a dry clean container and stirs, and makes B solution; 2., B solution is slowly added in A solution, the limit edged stirs, and is added dropwise to complete rear continuation stir about 30min and forms stable colloidal sol, and the about 5h of colloidal sol ageing is stand-by; 3., bamboo charcoal is put into to the ageing colloidal sol that 2. step make after, process 1h under the ultrasound condition that is 45KHz at 32 ℃ of lower frequencies and make rare gel enter the bamboo charcoal internal void, take out afterwards bamboo charcoal dry under 80 ℃; 4., take out bamboo charcoal drying box 3. from step in tube furnace under nitrogen atmosphere, at 550 ℃ of lower roasting 3h, obtain TiO
2/ bamboo charcoal catalyst, it is immersed to concentration is darkroom disposal a period of time in the 0.02mol/L liquor argenti nitratis ophthalmicus, under sunshine or under uviol lamp, processes afterwards, after taking-up composite drying, obtains TiO
2/ Ag/ bamboo charcoal composite material; 5., get a medical sewage film-making and examine under a microscope microorganism in sewage, record the microorganism shape characteristic; 6., in 100ml finite concentration medical sewage, add the hydrogen peroxide that the 0.1ml mass fraction is 30%, then with dilute sulfuric acid by system pH furnishing acidity; 7., TiO 2g made
2/ Ag/ bamboo charcoal composite material adds medical sewage, and sunshine was processed after 10 minutes, gets a medical sewage film-making and examines under a microscope microorganism in sewage, observes the microorganism removal effect, record data.
Embodiment 3: 1., the parts by volume proportioning of the butyl titanate of 1 part, 3 parts of absolute ethyl alcohols is added in a dry clean container and stirs, make A solution, the parts by volume proportioning of the iron nitrate solution that is 0.21mol/L by 0.4 part of concentration again, 1 part of absolute ethyl alcohol, 0.5 part of glacial acetic acid adds in a dry clean container and stirs, and makes B solution; 2., B solution is slowly added in A solution, the limit edged stirs, and is added dropwise to complete rear continuation stir about 30min and forms stable colloidal sol, and the about 5h of colloidal sol ageing is stand-by; 3., bamboo charcoal is put into to the ageing colloidal sol that 2. step make after, process 1h under the ultrasound condition that is 45KHz at 32 ℃ of lower frequencies and make rare gel enter the bamboo charcoal internal void, take out afterwards bamboo charcoal dry under 80 ℃; 4., take out bamboo charcoal drying box 3. from step in tube furnace under nitrogen atmosphere, at 550 ℃ of lower roasting 3h, obtain TiO
2/ bamboo charcoal catalyst, it is immersed to concentration is darkroom disposal a period of time in the 0.02mol/L liquor argenti nitratis ophthalmicus, under sunshine or under uviol lamp, processes afterwards, after taking-up composite drying, obtains TiO
2/ Ag/ bamboo charcoal composite material; 5., get a medical sewage film-making and examine under a microscope microorganism in sewage, record the microorganism shape characteristic; 6., in 100ml finite concentration medical sewage, add the hydrogen peroxide that the 0.2ml mass fraction is 30%, then with dilute sulfuric acid by system pH furnishing acidity; 7., TiO 2g made
2/ Ag/ bamboo charcoal composite material adds medical sewage, and sunshine was processed after 10 minutes, gets a medical sewage film-making and examines under a microscope microorganism in sewage, observes the microorganism removal effect, record data.
Embodiment 4: 1., the parts by volume proportioning of the butyl titanate of 1 part, 3 parts of absolute ethyl alcohols is added in a dry clean container and stirs, make A solution, the parts by volume proportioning of the iron nitrate solution that is 0.21mol/L by 0.3 part of concentration again, 1 part of absolute ethyl alcohol, 0.5 part of glacial acetic acid adds in a dry clean container and stirs, and makes B solution; 2., B solution is slowly added in A solution, the limit edged stirs, and is added dropwise to complete rear continuation stir about 30min and forms stable colloidal sol, and the about 5h of colloidal sol ageing is stand-by; 3., bamboo charcoal is put into to the ageing colloidal sol that 2. step make after, process 1h under the ultrasound condition that is 45KHz at 32 ℃ of lower frequencies and make rare gel enter the bamboo charcoal internal void, take out afterwards bamboo charcoal dry under 80 ℃; 4., take out bamboo charcoal drying box 3. from step in tube furnace under nitrogen atmosphere, at 550 ℃ of lower roasting 3h, obtain TiO
2/ bamboo charcoal catalyst, it is immersed to concentration is darkroom disposal a period of time in the 0.02mol/L liquor argenti nitratis ophthalmicus, under sunshine or under uviol lamp, processes afterwards, after taking-up composite drying, obtains TiO
2/ Ag/ bamboo charcoal composite material; 5., get a medical sewage film-making and examine under a microscope microorganism in sewage, record the microorganism shape characteristic; 6., in 100ml finite concentration medical sewage, add the hydrogen peroxide that the 0.1ml mass fraction is 30%, then with dilute sulfuric acid by system pH furnishing acidity; 7., TiO 2g made
2/ Ag/ bamboo charcoal composite material adds medical sewage, and sunshine was processed after 10 minutes, gets a medical sewage film-making and examines under a microscope microorganism in sewage, observes the microorganism removal effect, record data.
Claims (5)
1. a modification TiO
2/ Ag/ bamboo charcoal composite material, it is characterized in that the raw material composition is: iron nitrate solution, 0.5 part of glacial acetic acid, 1～3 part of concentration that the butyl titanate of 1 part, 0.3～0.4 part of concentration are 0.21mol/L are 0.01mol/L～0.02mol/L liquor argenti nitratis ophthalmicus and bamboo charcoal, and described umber is parts by volume.
2. one kind prepares TiO claimed in claim 1
2the method of/Ag/ bamboo charcoal composite material is characterized in that step is as follows:
Step 1: the parts by volume proportioning of the butyl titanate of 1 part, 3～4 parts of absolute ethyl alcohols is added in container and stirs, make A solution; The parts by volume proportioning of the iron nitrate solution that is 0.21mol/L by 0.3～0.4 part of concentration again, 1～2 part of absolute ethyl alcohol, 0.5 part of glacial acetic acid adds in container and stirs, and makes B solution;
Step 2: B solution is added in A solution, and the limit edged stirs, and is added dropwise to complete rear continuation and stirs to form colloidal sol, by colloidal sol ageing 5h left and right, obtains vitreosol;
Step 3: bamboo charcoal is put in the vitreosol that step 2 makes, and ultrasonic lower the processings 1h that is 45KHz at 32 ℃ of lower frequencies after stirring makes colloidal sol enter the bamboo charcoal internal void, takes out afterwards bamboo charcoal drying under 80 ℃; The addition of described bamboo charcoal is being as the criterion by the colloidal sol submergence;
Step 4: take out bamboo charcoal and obtain modification TiO at 550 ℃ of lower roasting 3h under nitrogen atmosphere from the drying box of step 3 in tube furnace
2/ bamboo charcoal composite material.
Step 5: the modification TiO that step 4 is obtained
2/ bamboo charcoal composite material immerses in the liquor argenti nitratis ophthalmicus of 0.01mol/L～0.02mol/L, utilizes concentrator process under sunshine or directly under uviol lamp, process 2h, takes out composite, dry under 80 ℃, obtains TiO
2/ Ag/ bamboo charcoal composite material.
3. method according to claim 2, it is characterized in that: rate of addition when in described step 2, B solution adds A solution is 1/s.
4. method according to claim 2, it is characterized in that: the uviol lamp power of selecting in described step 5 is 12w, generation ultraviolet wavelength is 360nm.
5. one kind is utilized the described modified Nano TiO of claim 1
2/ Ag/ bamboo charcoal composite material is killed method of microorganism in medical sewage, it is characterized in that: adopt hydrogen peroxide by the pH furnishing 3-4 of medical sewage, add modified Nano TiO
2/ Ag/ bamboo charcoal composite material, under sunshine, process obtain killing medical sewage in microorganism; Described modified Nano TiO
2the addition of/Ag/ bamboo charcoal composite material is 20g/L.
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| CN103447051A (en) * | 2013-08-28 | 2013-12-18 | 西北工业大学 | Fe<3+>/Ag/TiO2/bamboo charcoal composite material and method for manufacturing cigarette filter tips by utilizing same |
| CN103566931A (en) * | 2013-10-17 | 2014-02-12 | 华中科技大学 | Photocatalytic material with visible-light response function as well as preparation method and application thereof |
| CN104255797A (en) * | 2014-08-25 | 2015-01-07 | 中国海洋大学 | A silver/titanium oxide nanotube antifouling agent interfacially modified by polydopamine and a preparing method thereof |
| CN106925216A (en) * | 2017-03-31 | 2017-07-07 | 同济大学 | One kind carries silver TiO2Modification bamboo charcoal material and preparation method thereof |
| CN107999062A (en) * | 2017-12-22 | 2018-05-08 | 北京市水科学技术研究院 | Activated carbon fiber loaded Ag/TiO2The preparation method and application of composite catalyzing material |
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| CN110214790A (en) * | 2018-09-04 | 2019-09-10 | 莆田学院 | A kind of magnetic bamboo charcoal/nanometer silver/titanium dioxide compound disinfectant and its preparation method and application |
| CN110583644A (en) * | 2019-09-25 | 2019-12-20 | 中国科学院合肥物质科学研究院 | Preparation method and application of herbicide protectant |
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| CN110583644A (en) * | 2019-09-25 | 2019-12-20 | 中国科学院合肥物质科学研究院 | Preparation method and application of herbicide protectant |
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Application publication date: 20131218 |