CN100536982C - Nano granule water purifying material for removing bacteria and virus, and preparation thereof - Google Patents
Nano granule water purifying material for removing bacteria and virus, and preparation thereof Download PDFInfo
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- CN100536982C CN100536982C CNB2007103003092A CN200710300309A CN100536982C CN 100536982 C CN100536982 C CN 100536982C CN B2007103003092 A CNB2007103003092 A CN B2007103003092A CN 200710300309 A CN200710300309 A CN 200710300309A CN 100536982 C CN100536982 C CN 100536982C
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Abstract
The invention relates to a series of nano-particle water purification materials, which take quartz sand or zeolite particle as a substrate, nanometer aluminum (iron) oxide or nanometer aluminum (iron) oxidized hydrogen oxide as a modified filtration coating, and can effectively and completely remove bacilli and virus from wastewater and sewage. The invention also relates to a preparation method of the nano-particle water purification materials. In the preparation method, acidic solution with 40 to100 meshes of quartz sand or 60 to120 meshes of clinoptilolite is poured into secondary deionized water, uniformly mixed and heated, nano-aluminum powder, aluminum nitride powder or iron powder is poured into the acidic solution and ultrasonically mixed and ethanol solution of ester is then poured into the mixed acidic solution, ultrasonically mixed again, filtrated and dried so as to gain nano-fibriform AlO(OH) or FeOOH which is the particle water purification materials of filtration coating which are further roasted so as to gain Gamma-Al2O3 or Fe2O3 which is the particle water purification materials of filtration coating. The nano-particle water purification materials of the invention have the advantages of strong removal ability, high cleanliness, great saturated adsorption capacity, etc.
Description
Technical field
The invention belongs to waste water, sewage purification field, being specifically related to a series of is matrix with quartz sand or zeolite granular, nano aluminum (iron) oxide or nano aluminum (iron) hydrogen oxide oxide are that coating is filtered in modification, can be to the nano granule water purifying material of the bacterium in waste water, the sewage, viral removal in full force and effect, and the preparation method of this nano granule water purifying material.
Technical background
Enter 21 century, since the fast development of economic society, the continuous quickening of industrialization, urbanization process, and the environment development of the situation of China is to very severe stage.Environmental pollution continues enrichment on higher level, ecological disruption continues to increase the weight of, and some area surroundings pollute and ecological disruption has hindered economic continuing, develop in a healthy way, even people's health has been constituted direct threat.Wherein the water pollution situation is particularly outstanding, and especially the pollution of water head site causes that poisonous and harmful substance obviously increases in the drinking water, and increasing pathogenic microorganisms, bacterium, virus in the water has had a strong impact on daily life and work.Show according to World Health Organization's survey data, the disease in the whole world 80% is all relevant with poor water quality with 50% child mortality, find in addition, the people and the cancer mortality of drinking chlorination water are closely related, even some abundance of water area, the mutagenesis activity increases after also finding the running water chlorination, and Ames (test of salmonella mutagenicity) is positive.The shortcoming of chemical agent sterilization (chlorination is representative) and harm be subjected to widely in the last few years to be paid close attention to, and the accessory substance (organic chloride etc.) that sterilization produces is detrimental to health, even causes the tissue canceration.Though the disinfection by ultraviolet light germicidal efficiency is strong, does not continue disinfective action, and a little less than the penetration power, be mainly used in the air sterillization sterilization at present.
At present, water technology mainly contains: distillation technique, " coagulation-precipitation-filtration " technology, sterilizing technology, carbon filter technology, biologic treating technique, ion exchange technique, membrane separation technique and photochemical treatment technology or the like.These water technologies can make purification of water quality reach higher index, but there are a lot of shortcomings in they: efficient is low, cost is high, regeneration is difficult, have secondary pollution problems.The bacterium diameter is generally between 0.1 micron to tens microns, virus is more tiny, generally arrive between the hundreds of nanometer in tens nanometers, for tiny particle like this, people play the effect that purifies water by discovering various filtration, purification materials by mechanical sieving and absorption crown_interception.Filtration is to utilize medium that the solid matter in suspension liquid or the gas is held back, and liquid or gas then pass medium and clarified or purify.People are producing, are utilizing the history in existing several thousand of filtering technique in the life, are to be accompanied by the development of new material in recent decades and the new direction of rising with filtering material filtering virus, bacterium, also are hot research in recent years.Along with people's environmental consciousness strengthens day by day, the requirement of quality of the life is improved day by day, filtration sterilization has also obtained fast development and extensive use with scavenging material.Utilize filter method to remove virus and bacteria and in drinking water, food sterilization, medical treatment, pharmaceutical industry, have the not available superiority of other technologies.Aspect drinking water disinfection, utilize filtering technique, can effectively microorganism be held back as membrane filtration technique, reach the purpose of sterilization.The pure water of producing can reach the standard of drinking water fully.Aspect blood processing, filtering technique can effectively be removed virus and bacteria, and other technologies just might be destroyed the haemocyte in the blood.Also be so in pharmaceutical industry, heating or ultraviolet ray can destroy drug ingedient, and filtration sterilization this moment technology is a best choice.It is abundant with the source of scavenging material to filter bacterium, and along with modern people's growth in the living standard, the enhancing of environmental consciousness, can be more widely used in daily life, production as a kind of efficient, free of contamination sterilization technique, be accompanied by continually developing of new technology, new technology, increasing novel degerming scavenging material also can be produced out the needs that satisfy people.
Summary of the invention
The purpose of this invention is to provide a series of with quartz sand or zeolite granular etc. be matrix, nanometer fibrous AlO (OH) (FeOOH) oxide of particle or nano aluminum (iron) be the nano granule water purifying material that modification is filtered coating and can effectively be removed the virus in the water and bacterium, and provide the preparation method of above-mentioned nano granule water purifying material.
Nano granule water purifying material of the present invention, it is to be the matrix filtrate with 40～100 order quartz sands or 60～120 purpose zeolites, it is nanometer fibrous AlO (OH) particle or the nanometer Y-Al of 0.3～3.3 μ m (ESEM Thickness Measurement by Microwave) that thickness is arranged thereon
2O
3Coating is filtered in modification, and the quality that coating is filtered in modification accounts for 0.5～5% of filtrate and coating gross mass, nanometer fibrous AlO (OH) particle or nanometer Y-Al
2O
3Particle diameter be 15～120 nanometers, specific area 200～550m
2/ g;
Nano granule water purifying material of the present invention, it is to be the matrix filtrate with 40～100 order quartz sands or 60～120 purpose zeolites, it is nanometer fibrous FeOOH particle or the nanometer Fe of 0.1～3.7 μ m that thickness is arranged thereon
2O
3Coating is filtered in modification, and the quality that coating is filtered in modification accounts for 1～10% of filtrate and coating gross mass, nanometer fibrous FeOOH particle or nanometer Fe
2O
3Particle diameter be 15～120 nanometers, specific area 200～550m
2/ g.
The modification filtration coating for preparing big particle diameter, bigger serface, big mass content, big thickness need add more aluminium powder and positive tetraethyl orthosilicate, and constant temperature is preserved the longer time, grows in order to product.
Nanometer aluminium powder (or iron powder) itself is hydrolyzed into fibrous AlO (OH) or FeOOH, just has some gatherings after supporting on quartz sand or the zeolite, forms filamentary structure.Nano particle diameter is relevant with the preparation method, as hydrolysis temperature, hydrolysis time, support carrier, hydrating solution (neutral water, acid water, the water of alkalescence), plus solvent experiment conditions such as (as regular sour tetra-ethyl esters) and parameter relation all arranged, in addition with adding aluminium powder or the particle diameter of iron powder relation is also arranged, particle diameter is more little, reacts thorough more, fully, and the purity of Nano metal powder is high more good more, and surface area is relevant with particle diameter, and particle diameter is more little, and surface area is big more.
SEM is surveyed particle diameter, JSM-6480-L type, place of production Japan; Nitrogen adsorption method specific surface area analysis instrument (Micromet ricsASAP2010, place of production Japan), measurement the specific area.
The preparation method of nano granule water purifying material of the present invention is as follows:
1. the preceding preliminary treatment of modification to the matrix filtrate
Quartz sand is water factory of Running-water Company filter tank sand, and zeolite is the high silicon clinoptilolite that commercially available Gongyi City sea space filler factory produces.Because quartz sand, zeolite surface in natural environment have been subjected to polluting or having suffered destruction, thereby changed original surface nature, need carry out preliminary treatment, removed the impurity on surface it, recover quartz sand, the original surface property of zeolite, make the modifier adhesiving effect better.
Process for surface preparation:
The quartz sand that to fetch from the waterworks washes repeatedly with running water, and sieving out particle diameter is 40～100 purpose particles, puts in the baking oven, 80～120 ℃ of oven dry down; Take out after 20～24 hours with the immersion of 0.8～1.5mol/L salpeter solution, wash repeatedly with running water again, then with the distilled water flushing multipass removing the organic matter that the surface may adhere to, up to the nearly neutrality of the pH value of flushing water outlet, with quartz sand 110～120 ℃ of oven dry in baking oven, store for future use again.
It was 60～120 purpose particles that clinoptilolite goes out particle diameter through crushing and screening, and the running water flushing is fully stirred, and to remove smalls, clay and other impurity, soaks in the distilled water 48～60 hours, changed a water every 3～6 hours, to reduce the alkalescence of zeolite.Then, in baking oven, dried 5～10 hours for 120 ℃, obtain washing zeolite, store for future use.
The composition of the quartz sand after the processing: SiO
2, accounting for 97.5～98.3%, all the other compositions are Al
2O
3, account for 0.8～1.0%, Fe
2O
3, accounting for 0.7～1.2%, other is MgO, CaO and the K of trace
2O;
The composition of using natural clinoptilolite: SiO
2, account for 69.3～70.2%, Al
2O
3, account for 9.7～10.1%, H
2O accounts for 9.1～12.4%.All the other are the MgO of trace, CaO, K
2O, Na
2O.
2. the preparation of modified coating
1) is that the acid solution (boric acid or sodium salicylate) of 0.1～6g/L, 10～100mL is rendered in 150～350 milliliters of secondary deionized water with the quartz sand after 20～100g surface treatment (or clinoptilolite) and concentration, is heated to 80～100 degree after mixing;
2) be nanometer aluminium powder, aluminum nitride powder or the iron powder that the discharge-induced explosion silk method of 15～150nm makes to wherein dropping into 2～12g particle diameter then, place ultrasonic generator, strong agitation, under 80～100 ℃ of temperature ultrasonic 0.2～1.5 hour;
3) add the ethanolic solution 40～100mL of the positive tetraethyl orthosilicate of 1.5～8g/L afterwards, the volume ratio of ethanol and positive tetraethyl orthosilicate is 6.5～1.5:1, continues ultrasonic agitation and handles 10～30 minutes, close ultrasonic, with groove insulation 2～6 hours;
4) solidliquid mixture that makes is filtered with Buchner funnel, filtrate is cleaned repeatedly to the washing lotion behind the no filter residue with secondary deionized water, and promptly obtaining with nanometer fibrous AlO (OH) particle or nanometer fibrous FeOOH particle in dry 5～12 hours in drying box under 60～80 ℃ of temperature is the particle water-purifying material of filtration coating;
5) material that step 4) is made is further transferred in the Muffle furnace and is spent roastings 2～5 hours 400～600, promptly obtains nano aluminum oxide (Y-Al
2O
3) for filtering the particle water-purifying material of coating; Or, promptly obtain nano-iron oxide (Fe 300～500 degree roastings 2～6 hours
2O
3) for filtering the particle water-purifying material of coating.
The effect experiment
Table 1 contains in the sewage process of bacterium the time dependent data of total number of bacteria for handling with nano granule water purifying material of the present invention.Owing in the bacteriology of water is measured, directly check various pathogenic microorganisms in the water, method is complicated, and difficulty is big, and negative can not the assurance of check result is perfectly safe.So, the frequent hygiene quality of judging water with the total number of bacteria of checking water indirectly in real work.The water quality standard that goes out of prescribed bacteria sum is 100/ml in China's drinking water sanitary standard (GB 5749-85).The removal efficient of 40min all material is 100% before in the table, and material reduces gradually to the removal efficient of bacterium in the water subsequently, and at 550min, material 2,4,5,6 totals number of bacteria begin to exceed standard, and material 1 is at 610min, and material 3 exceeds standard in the 670min total number of bacteria.Each material reaches maximum to the disposal ability of bacterium in the water about 920min, this shows, nano water purifying material of the present invention is removed the efficient height, and disposal ability is strong, has sizable saturated extent of adsorption.
Table 1: removal total number of bacteria experimental data (concentration: individual/ml)
Annotate: adopt the post adsorption experiment: column diameter: 2.0cm; Post height: 30cm; Filling filtrate quality: 30g;
Loading height: 5.4cm; 450/L of initial soln bacterial concentration (microscopic visual measurement counting)
Flow velocity: 4.6-5.3ml/min.
From the water sample that South Lake Park, Changchun water body is adopted, after the water sample bottle is airtight, be placed on shady and cool place and preserve.Measured result includes only the mesophilic aerobic total number of bacterial colonies that a group energy is grown on nutrient agar.Comprise colon bacillus, typhoid bacillus, helicobacter pylori, proteus, Cray Bai Shi bacillus etc.Water sample with the abundant mixing of sterile working method absorption 1mL injects the test tube that fills the 9mL sterile saline, is mixed into the 1:10 dilution.The dilution 1mL that draws 1:10 injects the test tube that fills the 9mL sterile saline, is mixed into the 1:100 dilution.Be diluted to 1:1000 by the same method successively, 1:10000 dilution etc. are standby.So increase progressively dilution once, must change a 1mL sterilization suction pipe.Get 2～3 suitable dilution water sample 1mL with the sterilization suction pipe, inject respectively in the sterilization plate.Pour into about 15mL and melted and be cooled to nutrient agar about 45 ℃, and shaking by swirling plate immediately, make the abundant mixing of water sample and culture medium.Should do a parallel inoculation during each the check, only pour into nutrient agar as blank with a plate in addition simultaneously.After to be cooled the solidifying, the upset plate makes the bottom surface upwards, places and cultivates 24h in 36 ± 1 ℃ of incubators, carries out colony counting, is the total number of bacteria among the water sample 1mL.Enlarging 1000 times of clump counts that promptly obtain in the 1L water sample.Can directly carry out colony counting with microscope.
Table 2 contains in the sewage process of bacterium the time dependent data of total number of bacteria for handling with the nano granule water purifying material of regenerating.With used nano granule water purifying material with 0.4～1.0mol/LHNO
3Regeneration, the filtrate after (adsorption column of flowing through is through 3h regeneration back) will regenerate then is applied to handle in the sewage that contains bacterium once more.The removal efficient of 40min material is 100% before in the table, and material reduces gradually to the removal efficient of bacterium in the water subsequently, and total number of bacteria begins to exceed standard in the 530min left and right sides, 920min left and right sides material to water in the disposal ability of bacterium all reach maximum saturation.This shows that nano granule water purifying material regeneration of the present invention is simple, the materials purification effect after the regeneration is almost constant, reusable.
Table 2: the material after the regeneration is removed the total number of bacteria experimental data
Annotate: adopt the post adsorption experiment: column diameter: 2.0cm; Post height: 30cm; Filling filtrate quality: 30g;
Loading height: 5.4cm; 450/L of initial soln bacterial concentration;
Flow velocity: 4.6-5.3ml/min.
In sum, nano granule water purifying material of the present invention is used to handle the black water that contains bacterium and virus, compares with existing water technology and to have following advantage:
1. the preparation method is simple, and is easy to use, long service life;
2. removal ability is strong, removes the cleanliness height, to the bacterium in the water, just can reach 100% removal effect in the virus short time, and has sizable saturated extent of adsorption;
3. can reuse, regeneration is simple, and does not have secondary pollution.
Nano granule water purifying material of the present invention is because it removes the cleanliness height, so can be widely used in the various sewage of advanced treating.
Description of drawings
Fig. 1: the experiment SEM pattern of quartz sand particle;
Fig. 2: the SEM pattern that filters coating AlO (OH) is sticked in experiment with quartz sand surface;
Fig. 3: AlO (OH) particle standard x RD diffraction spectrogram;
Fig. 4: (a) quartz sand (60～80 order) XRD diffraction spectrogram;
(b) the XRD diffraction spectrogram of modified particles water-purifying material;
Fig. 5: Y-Al
2O
3Particle standard x RD diffraction spectrogram;
Fig. 6: (a) quartz sand surface sticks the product X RD diffraction spectrogram of AlO (OH) after 400 degree roastings;
(b) quartz sand surface sticks the product X RD diffraction spectrogram of AlO (OH) after 450 degree roastings;
(c) quartz sand surface sticks the product X RD diffraction spectrogram of AlO (OH) after 500 degree roastings;
(d) quartz sand surface sticks the product X RD diffraction spectrogram of AlO (OH) after 600 degree roastings
The thermogravimetric curve of Fig. 7: AlO (OH).
Fig. 2-Fig. 7 is the sample for preparing under embodiment 1 condition.
As shown in Figure 3, show that the characteristic peak of AlO (OH) particle standard x RD diffraction is 14.492 ° according to JCPDS-83-2384,28.213 °, 38.361 °, 48.940 °, have the orthorhombic system structure, brilliant bag parameter is a=3.693, b=12.21, c=2.867;
Shown in Fig. 4 (b), standard x RD diffracting spectrum with the AlO (OH) of Fig. 3, the XRD diffraction peak of modified particles water-purifying material coating is 14.38 °, 28.19 °, 38.27 °, 48.89 °, very nearly the same with standard diagram, as seen the coating that applies of quartz sand surface is AlO (OH), this characteristic peak not then on the XRD spectra on the quartz sand;
As shown in Figure 5, show Y-Al according to JCPDS-77-0396
2O
3The characteristic peak of particle standard x RD diffraction is 37.707 °, 45.875 °, and 66.893 °, have cubic crystal structure, brilliant bag parameter is a=7.906;
As shown in Figure 6, under the different sintering temperatures, the position that quartz sand surface sticks three strongest ones' peak appearance of product of roasting is respectively 37.57 °, and 45.84 °, 66.87 °, with standard Y-Al
2O
3The position at XRD diffraction spectrogram three strongest ones peak is very nearly the same, and (a) as seen between 400～600 degree, the quartz sand surface product of roasting is Y-Al to Fig. 4 with reference to the XRD diffraction spectrogram of quartz sand itself
2O
3
As shown in Figure 7, thermogravimetric TG curve has twice dehydration, on the corresponding DTA curve two place's endothermic peaks (respectively at 78.86 ℃ and 390.38 ℃) are arranged, dehydration for the first time (78.86 ℃) is the physical absorption water of this sample and losing of the crystallization water, dehydration for the second time (390.38 ℃) be Al-OH group adjacent in the sample concentrate the i.e. variation of phase structure.
The specific embodiment
This patent is to set forth the present invention with embodiment; rather than limitation of the present invention; every a kind of can be on quartz sand or zeolite; adopt the method for nano metal powder hydrolysis; the method of sedimentation and filtration coating on above-mentioned matrix; every to relate to metal oxide/hydroxide or metal oxide be main filter component, and the filtration coating of preparation in this way, is our rights protection scope.
Embodiment 1:
Get the pretreated quartz sand of 30g (60～80 order) put into mix in the 200mL secondary deionized water after, the boric acid 10mL that adds 1.5g/L, after mixing 20min, under 80 ℃, adding nanometer aluminium powder (is made by discharge-induced explosion silk method, average grain diameter 45nm) 2.6g places ultrasonic tank sonic oscillation (K-100 type ultrasonic cleaner, supersonic frequency 235KHz) 30min; In mixture, add the positive silicic acid four of the 2g/L ethanol of ester (alcohol, ester volume ratio 2.5:1) solution 50mL then, continue ultrasonic agitation and handle 20min, stop ultrasonic, with groove insulation 3 hours; The solidliquid mixture that makes is filtered with Buchner funnel, and filtrate cleans repeatedly to the washing lotion with secondary deionized water and behind the no filter residue, filtrate is moved in the drying box, and dry 10h under 60 ℃ of temperature promptly obtains 30.8g AlO (OH) nano granule water purifying material.
Filtering coating composition is AlO (OH), and coating accounts for 2.59% of matrix and coating gross weight, and the coating average grain diameter is 71nm, and specific area is 382m
2/ g, coating layer thickness are 1.81 μ m.
Embodiment 2:
The sample of embodiment 1 preparation is moved in the Muffle furnace, be raised to 450 ℃ with the heating rate of 10 ℃/min, roasting 2.5 hours afterwards with the stove cool to room temperature, promptly obtains 30.6g Y-Al
2O
3Nano water purifying material.Filtering coating composition is Y-Al
2O
3, coating accounts for 1.96% of matrix and coating gross weight, and the coating average grain diameter is 92nm, and specific area is 205m
2/ g, coating layer thickness are 1.42 μ m.
Embodiment 3:
Get the pretreated quartz sand of 30g (40～60 order) put into mix in the 200ml secondary deionized water after, the sodium salicylate 20ml that adds 4g/L, after mixing 30min, under 85 ℃ of temperature, adding the 4.56g nanometer iron powder (is made by discharge-induced explosion silk method, average grain diameter 85nm), place ultrasonic tank sonic oscillation (supersonic frequency 235KHz) 45min, in mixture, add the positive silicic acid four of the 4.5g/L ethanolic solution of ester (alcohol, ester volume ratio 3:1) 55mL then, continue sonic oscillation 30min, close ultrasonic, with groove insulation 5h; The above-mentioned solidliquid mixture that makes is filtered with Buchner funnel, filtrate is cleaned repeatedly to the washing lotion behind the no filter residue with secondary deionized water, with filtrate in drying box in 80 ℃ times dry 10h of temperature, promptly obtain 30.88g FeOOH nano granule water purifying material.
Filtering coating composition is FeOOH, and coating accounts for 2.86% of matrix and coating gross weight, and the coating average grain diameter is 95nm, and specific area is 348m
2/ g, coating layer thickness are 2.11 μ m.
Embodiment 4:
The sample of embodiment 3 preparation is moved in the Muffle furnace, be raised to 400 ℃ with the heating rate of 8 ℃/min, roasting 4 hours afterwards with the stove cool to room temperature, promptly obtains 30.79g Fe
2O
3Nano water purifying material.
Filtering coating composition is Fe
2O
3, coating accounts for 2.57% of matrix and coating gross weight, and the coating average grain diameter is 113nm, and specific area is 269m
2/ g, coating layer thickness are 2.01 μ m.
Embodiment 5:
Get the pretreated clinoptilolite of 30g (80～100 order), put in the secondary deionized water of 230mL and mix, the sodium salicylate 20mL that adds 6.0g/L, under 85 ℃ of temperature, adding the 4.5g nanometer aluminium powder (is made by discharge-induced explosion silk method, average grain diameter 60nm), place ultrasonic tank sonic oscillation (supersonic frequency 235KHz) 0.7h then, in mixture, add the positive silicic acid four of the 5.5g/L ethanolic solution of ester (alcohol, ester volume ratio 4:1) 40mL then, continue sonic oscillation 20min, close subsequently ultrasonic, with groove insulation 6h; Above-mentioned two kinds of solidliquid mixtures that make are filtered, filtrate is cleaned repeatedly to the washing lotion with secondary deionized water behind the no filter residue, in drying box,, promptly obtain 30.76g AlO (OH) nano granule water purifying material in 70 ℃ times dry 8h of temperature.
Filtering coating composition is AlO (OH), and coating accounts for 2.47% of matrix and coating gross weight, and the coating average grain diameter is 69nm, and specific area is 401m
2/ g, coating layer thickness are 1.96 μ m.
Embodiment 6:
Get the pretreated clinoptilolite of 30g (60～80 order), put in the secondary deionized water of 180mL and mix, the sodium salicylate 30mL that adds 1.5g/L, under 85 ℃ of temperature, adding the 3.7g nanometer iron powder (is made by discharge-induced explosion silk method, average grain diameter 65nm), place ultrasonic tank sonic oscillation (supersonic frequency 235KHz) 0.6h, in mixture, add the positive silicic acid four of the 5.5g/L ethanolic solution of ester (alcohol, ester volume ratio 4.5:1) 50mL then, continue sonic oscillation 30min, close subsequently ultrasonic, with groove insulation 6h; Above-mentioned two kinds of solidliquid mixtures that make are filtered, filtrate is cleaned repeatedly to the washing lotion with secondary deionized water behind the no filter residue, in drying box,, promptly obtain 30.93g FeOOH nano granule water purifying material in 60 ℃ times dry 12h of temperature.
Filtering coating composition is FeOOH, and coating accounts for 3.01% of matrix and coating gross weight, and the coating average grain diameter is 91nm, and specific area is 392m
2/ g, coating layer thickness are 2.19 μ m.
Embodiment 7:
Get the pretreated quartz sand of 20g (80～100 order), put in the secondary deionized water of 180mL and mix, the sodium salicylate 70mL that adds 5.5g/L, under 85 ℃ of temperature, adding the 10g nanometer aluminium powder (is made by discharge-induced explosion silk method, average grain diameter 35nm), place ultrasonic tank sonic oscillation (supersonic frequency 235KHz) 1.0h, in mixture, add the positive silicic acid four of the 7g/L ethanolic solution of ester (alcohol, ester volume ratio 1.5:1) 80mL then, continue sonic oscillation 30min, close subsequently ultrasonic, with groove insulation 6h; Above-mentioned two kinds of solidliquid mixtures that make are filtered, filtrate is cleaned repeatedly to the washing lotion with secondary deionized water behind the no filter residue, in drying box,, promptly obtain 20.60g AlO (OH) nano granule water purifying material in 60 ℃ times dry 12h of temperature.
Filtering coating composition is AlO (OH), and coating accounts for 2.92% of matrix and coating gross weight, and the coating average grain diameter is 51nm, and specific area is 522m
2/ g, coating layer thickness are 3.06 μ m
Embodiment 8:
Get the pretreated clinoptilolite of 20g (100～120 order), put in the secondary deionized water of 200mL and mix, the sodium salicylate 80mL that adds 5.5g/L, under 85 ℃ of temperature, adding the 10g nanometer iron powder (is made by discharge-induced explosion silk method, average grain diameter 25nm), place ultrasonic tank sonic oscillation (supersonic frequency 235KHz) 1.0h, in mixture, add the positive silicic acid four of the 7.5g/L ethanolic solution of ester (alcohol, ester volume ratio 1.5:1) 80mL then, continue sonic oscillation 30min, close subsequently ultrasonic, with groove insulation 6h; Above-mentioned two kinds of solidliquid mixtures that make are filtered, filtrate is cleaned repeatedly to the washing lotion with secondary deionized water behind the no filter residue, in drying box,, promptly obtain 20.76g FeOOH nano granule water purifying material in 60 ℃ times dry 12h of temperature.
Filtering coating composition is FeOOH, and coating accounts for 3.65% of matrix and coating gross weight, and the coating average grain diameter is 43nm, and specific area is 539m
2/ g, coating layer thickness are 3.19 μ m.
Claims (5)
1, remove the nano granule water purifying material of virus and bacterium, it is characterized in that: with 40～100 order quartz sands or 60～120 purpose zeolites is the matrix filtrate, and it is nanometer fibrous AIO (OH) particle or the nanometer Y-Al of 0.3～3.3 μ m that thickness is arranged thereon
2O
3Coating is filtered in modification, and the quality that coating is filtered in modification accounts for 0.5～5% of filtrate and coating gross mass, nanometer fibrous AIO (OH) particle or nanometer Y-Al
2O
3Particle diameter be 15～120 nanometers, specific area 200～550m
2/ g.
2, remove the nano granule water purifying material of virus and bacterium, it is characterized in that: with 40～100 order quartz sands or 60～120 purpose zeolites is the matrix filtrate, and it is nanometer fibrous FeOOH particle or the nanometer Fe of 0.1～3.7 μ m that thickness is arranged thereon
2O
3Coating is filtered in modification, and the quality that coating is filtered in modification accounts for 1～10% of filtrate and coating gross mass, nanometer fibrous FeOOH particle or nanometer Fe
2O
3Particle diameter be 15～120 nanometers, specific area 200～550m
2/ g.
3, the preparation method of the nano granule water purifying material of claim 1 or 2 described removal viruses and bacterium, its step is as follows:
1) is that boric acid or the sodium salicylate acid solution of 0.1～6g/L, 10～100mL rendered in 150～350 milliliters of secondary deionized water with the quartz sand after 20～100g surface treatment or clinoptilolite and concentration, is heated to 80～100 degree after mixing;
2) then to wherein dropping into nanometer aluminium powder, aluminum nitride powder or the iron powder that 2～12g particle diameter is 15～150nm, place ultrasonic generator, strong agitation, under 80～100 ℃ of temperature ultrasonic 0.2～1.5 hour;
3) add the ethanolic solution 40～100mL of the positive tetraethyl orthosilicate of 1.5～8g/L afterwards, the volume ratio of ethanol and positive tetraethyl orthosilicate is 6.5～1.5:1, continues ultrasonic agitation and handles 10～30 minutes, close ultrasonic, with groove insulation 2～6 hours;
4) solidliquid mixture that makes is filtered with Buchner funnel, filtrate is cleaned repeatedly to the washing lotion behind the no filter residue with secondary deionized water, and promptly obtaining with nanometer fibrous AIO (OH) particle or nanometer fibrous FeOOH particle in dry 5～12 hours in drying box under 60～80 ℃ of temperature is the particle water-purifying material of filtration coating;
5) material that step 4) is made is further transferred in the Muffle furnace and is spent roastings 2～5 hours 400～600, promptly obtains nano aluminum oxide Y-Al
2O
3For filtering the particle water-purifying material of coating; Or, promptly obtain nano-iron oxide Fe 300～500 degree roastings 2～6 hours
2O
3For filtering the particle water-purifying material of coating.
4, the preparation method of the nano granule water purifying material of removal virus as claimed in claim 3 and bacterium, it is characterized in that: the surface treatment of quartz sand is that quartz sand is washed repeatedly with running water, sieving out particle diameter is 40～100 purpose particles, puts in the baking oven, 80～120 ℃ of oven dry down; Take out after 20～24 hours with the immersion of 0.8～1.5mol/L salpeter solution, wash repeatedly with running water again, use the distilled water flushing multipass then, near neutral up to the pH value of flushing water outlet, with quartz sand 110～120 ℃ of oven dry in baking oven, store for future use again.
5, the preparation method of the nano granule water purifying material of removal virus as claimed in claim 3 and bacterium, it is characterized in that: the surface treatment of zeolite is that clinoptilolite is gone out particle diameter through crushing and screening is 60～120 purpose particles, the running water flushing, fully stir,, soaked in the distilled water 48～60 hours to remove smalls, clay and other impurity, changed a water every 3～6 hours, then in baking oven 120 ℃ the oven dry 5～10 hours, obtain washing zeolite, store for future use.
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| CN101716489B (en) * | 2009-11-27 | 2012-01-25 | 北京科技大学 | Denitrification dephosphorization antibacterial composite water treatment material used for water reclamation |
| CN102357323B (en) * | 2011-07-12 | 2014-06-18 | 广东工业大学 | Nanometer iron oxide-modified quartz sand filter material and preparation method thereof |
| KR20150021564A (en) | 2012-06-27 | 2015-03-02 | 아고나이드 코포레이션 | Aluminized silicious sorbent and water purification device incorporating the same |
| CN107583597B (en) * | 2017-09-26 | 2020-04-03 | 上海大学 | Preparation method and application of mesoporous iron oxyhydroxide Cr (VI) adsorbent |
| CN111530167B (en) * | 2020-05-22 | 2021-03-02 | 江苏睿泽环保科技有限公司 | Filter element based on charge adsorption filtration principle for nuclear water filtration and preparation method thereof |
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