CN101591044B - Metal oxide nanometer material for treating wastewater containing dyes or heavy metal ions, preparation method thereof - Google Patents
Metal oxide nanometer material for treating wastewater containing dyes or heavy metal ions, preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a metal oxide nanometer material for treating wastewater containing dyes or heavy metal ions, a preparation method and application thereof. Compositions of the metal oxide nanometer material is one or a mixture of more than two of CaO, ZrO2, SiO, ZnO, TiO2, MgO, Fe2O3 and NiO. The preparation method comprises the following steps: dissolving one or a mixture of more than two of calcium nitrate containing crystallization water, zirconium nitrate, ethyl orthosilicate, zinc nitrate, butyl titanate, magnesium nitrate, ferric nitrate and nickel nitrate into methanol, ethanol or propanol, adding a phenylcarbinol or benzylcarbinol structure-directing agent into the obtained solution, moving the mixture into a high-pressure kettle after the mixture is mixed evenly, heating the mixture to between 120 and 200 DEG C for 2 to 6h to ensure that nitrate is completely alcoholized under the protection of chlorine gas with the pressure of between 10<6> and 1.5*10<6> Pa, then heating the mixture to between 261 and 269 DEG C for 15h, drying the obtained product, and then performing high-temperature roasting at a temperature of between 300 and 500 DEG C to obtain the metal oxide nanometer material. The metal oxide nanometer material is added into the wastewater containing the dyes or the heavy metal ions to ensure that the metal oxide nanometer material and the wastewater are fully contacted to decolorize, absorb or degrade the wastewater containing the dyes.
Description
Technical field
The present invention relates to a kind of metal oxide nano-material and preparation method who contains dyestuff or effluent containing heavy metal ions that be used to handle.
Background technology
Over past ten years, the dye industry of China has been obtained huge development.China can produce 11 big classes more than totally ten ten thousand tons of dyestuffs every year now.Dyestuff is widely used in industrial circles such as weaving, leather, papermaking, rubber, plastics, cosmetics, pharmacy and food, and dyestuff widely-used certainly leads to a large amount of waste water from dyestuff and be discharged in the environment water, causes the pollution of natural water.
Waste water from dyestuff generally has following characteristics:
(1) the organic matter great majority in the waste water be with aromatic groups such as benzene, naphthalene, anthracene, quinones as parent, and have color base group, color is very dark, colourity reaches 500-500000, and very strong pollution sense is arranged.
(2) because the needs of production process and molecular structure, dye substance and intermediate molecule often contain polar group, have increased water-solublely, and the material number of dropouts is strengthened, and cause COD to strengthen, and generally can reach 1000-73000mg/L.
(3) waste water is acid more, and being of also having is alkaline, and general salt content is all very big.
(4) because the kind of dyestuff is more and more, and towards anti-photodissociation, anti-oxidant, the development of antibiosis degraded makes that these waste water more and more are difficult to handle with general method.
According to investigations, the waste water total amount of China's dye industry year in 2002 discharging just reaches 1,400,000,000 tons.At present, treated sewage quantity accounts for 34% of total release, and up to standardly in disposing of sewage only accounts for 58.3%.These waste water enter water body, cause the destruction of water ecosystem, and human beings'health also is harmful to.
The harm of waste water from dyestuff integrates the consideration following points:
(1) colourity of waste water from dyestuff makes water body outward appearance severe exacerbation, thereby to cause the principal element of colourity be dyestuff.Dyestuff in the waste water can absorb light, reduces water transparency, influences aquatile and growth of microorganism, is unfavorable for the self-purification of water, easily causes visual pollution.
(2) there are harmful heavy metals such as chromium, lead, mercury in the dyestuff, these heavy metallic salts are difficult to degraded with general biochemical method, so their energy long-term existence in natural environment, and can with regard to once taking place, heavy metal Hg and cadmium pollution cause public hazard incidents such as " Mad Hatter's disease ", " bone aching " in Japan by harm humans health such as food chains.Cr particularly
6+Being confirmed to be can be carcinogenic, therefore should be specifically noted that discharging and comprehensive utilization.
(3) dyestuff is that aromatic compounds benzene ring hydrogen is replaced many phenyl ring substituted compounds such as the later aromatic halide that generates, aromatic nitro compound, aromatic amines compound, biphenyl by halogen, nitro, amido, and bio-toxicity is all bigger.Germany find the azo dyes of part based on aromatic amine be used for printed fabrics can to human body have a negative impact the back oneself ban use of and these azo dyes of import, India also forbids the production and the use of similar azo dyes in preparation.
China is one of more serious country of shortage of water resources and water damage ratio.Aggravation along with water resources crisis; how to carry out cleaner production in each operation of printing and dyeing; reduce water consumption and wastewater discharge; and the production technology of in waste water treatment, using cleaning; prevent the transfer of secondary pollution and pollutant; and the reuse after the realization wastewater treatment, this is of great immediate significance and economic implications to the sustainable development of alleviating water resources crisis, keeping dyeing.Therefore the comprehensive regulation of dyeing waste water has become a problem that presses for solution.The domestic research of carrying out many dye wastewater treatment technologies.Once adopted several different methods such as electrolysis, absorption, photocatalysis, molysite, coagulation, biology enzyme, effect is all undesirable.Processing material to waste water from dyestuff has at present: 1. the Liao Wen of Southwest Petrol University chrysanthemum, Zou Changjun have synthesized the imvite (patent publication No.: CN101177310A) that contains cyclodextrin; 2. people such as the Xu Hui of Shenyang Inst. of Applied Ecology, Chinese Academy of Sciences, woods person of outstanding talent has prepared alloy material (mass percent C 0.06%Si 0.70%Mn 0.80%Ni 0.10%Mo 0.50%Cr 1.6%Nb 0.4%Cu 4.8%Fe surplus) (patent publication No.: 101200322A); 3. people such as the Ma Jianfeng of Jiangsu Polytechnic University, Li Dinglong have synthesized bentonite cation adsorbent (patent publication No.: CN101229505A); Zhongshan University once people such as Chinese, Lu Yun synthesized activated carbon fiber (patent publication No.: CN1204622A); 5. people such as the Deng Nansheng of Wuhan University, Deng Lin have reported for work and have contained iron complex (patent publication No.: 1415565A); 6. Wuhan University of Technology's thunder continues, and to have prepared a kind of regeneration activating inorganic composite materials-Main Ingredients and Appearance be silicate, porlandite, calcium carbonate and silica (patent publication No.: CN1903737A) to people such as the people, Yuan Lingqun.Though above-mentioned material be to can both reaching on the dye decolored efficient more than 90%, some material to the adsorbance of dyestuff very little as: alloy material is 0.115mg/g to the adsorbance of dyestuff, and the imvite that contains cyclodextrin is 197.2mg/g to the adsorbance of dyestuff.Though the treatment effect of bentonite and activated carbon fiber is satisfactory, but its cost is higher and the regeneration difficulty, wants more than 800 ℃ as the activation temperature of activated carbon fiber, and uses steam activation 6h, strengthen cost so greatly, made practical application be restricted.Iron is that complex compound is better to the decoloring dye waste water effect, but condition some harsh it need transfer pH≤2.5 with acid, and under the condition of ultraviolet light illumination, dye molecule be reduced, this also makes practical application be subjected to very big restriction.The regenerable inorganic composite make that its relative cost is very low, but its consumption is very big because it can use repeatedly, and the waste water from dyestuff of 100ml needs its percent of decolourization of processing material of 10g just can reach more than 90%.Because the drawback of above material this make the research and development new material have realistic meaning and economic implications, this also meets the requirements of the times that realize sustainable development view.
Summary of the invention
The present invention is in order to overcome problem and the shortcoming that above-mentioned prior art exists, a kind of metal oxide nano-material and preparation method and purposes that contains dyestuff or effluent containing heavy metal ions that be used to handle is provided, adopts metal oxide nano-material to make dye molecule, heavy metal ion in the waste water obtain decolouring, adsorb or degrade and be removed.Metal oxide nano-material provided by the present invention to high adsorption capacity, the treatment effect height of dyestuff, effluent containing heavy metal ions, technology is simple, cost is low, renewable is strong.Minimum adsorbance to waste water from dyestuff is 250mg/g.Calcination and regeneration under 500 ℃ condition, its adsorbance to waste water from dyestuff is still constant.
Technical solution of the present invention is:
A kind ofly be used to handle the metal oxide nano-material that contains dyestuff or effluent containing heavy metal ions, it is characterized in that: the metal oxide nano-material composition is: CaO, ZrO
2, SiO, ZnO, TiO
2, MgO, Fe
2O
3, one or two or more kinds mixture among the NiO.Described metal oxide nano-material is the metal oxide flaky nanocrystalline that strong polar surfaces oriented growth is arranged.Described metal oxide nano-material is flakelike powder or particle, and powder size is 0.5nm-100nm, and grain graininess is 0.5nm-200nm, and specific area is 50-600m
2/ g.
The preparation method of metal oxide nano-material, it is characterized in that: carry out according to the following steps: the calcium nitrate that will contain the crystallization water, zirconium nitrate, ethyl orthosilicate, zinc nitrate, butyl titanate, magnesium nitrate, ferric nitrate, one or two or more kinds mixture material is dissolved in methyl alcohol in the nickel nitrate, in ethanol or the propyl alcohol, methyl alcohol, one or two or more kinds mixture material mol ratio of ethanol or propyl alcohol and adding is 60-280: 1, add phenmethylol or benzyl carbinol structure directing agent, one or two or more kinds mixture material that adds and the mol ratio of structure directing agent are 1: 0.5-2, mixing the back moves in the autoclave, 1.0 * 10
6-1.5 * 10
6The protection of Pa chlorine down; be heated to 120 ℃ to 200 ℃ and keep 2-6h; make one or two or more kinds mixture material complete alcoholysis of adding; to be heated to temperature range then be 261 ℃～269 ℃ and keep 15h; drying obtains the metal oxide nano-material precursor, makes metal oxide nano-material through 300 ℃ to 500 ℃ high temperature roasts.
Described metal oxide nano-material is used to handle the purposes that contains dyestuff or effluent containing heavy metal ions, with metal oxide nano-material and input contains dyestuff or the effluent containing heavy metal ions mass ratio is 1: 10-4000, both are fully contacted, waste water is decoloured, degrades and adsorbs, clearance to dyestuff is more than 90%, and the clearance of heavy metal ion is more than 91%.
Contain dyestuff or effluent containing heavy metal ions treatment temperature and be controlled at 10～100 ℃, the pH value of waste water can be between 3～14.
Among the present invention, metal oxide nano-material and waste water from dyestuff effect also make the principle of its decolouring, degraded and absorption be: metal oxide nano-material itself has band structure and photoelectric characteristic.When energy shone the metal oxide nano-material surface more than or equal to luminous point of energy gap, material granule absorbed it, and with electron excitation in the valence band to conduction band, stay the hole in valence band, become electron-hole pair.Photohole has the very strong electronic capability that gets, and has strong oxidizing property, can win the electronics of surperficial adsorbent, makes not light absorbing originally goods and materials oxidized.Light induced electron then has strong reducing property, can go back the original surface adsorbent.Metal oxide nano-material is strong polar surfaces nanometer materials in addition.Because its surface area is big, form strong potential energy in its surface so active site is many, bigger adsorbance is arranged at normal temperatures.Intermolecular motion quickening under high relatively temperature, surface-active point increase makes adsorbance strengthen.Cause structure, form and the performance of dye molecule to change like this, finally produce phenomenons such as decolouring, degraded and absorption.Not only dyestuff there is good clearance, good suction-operated is also arranged for heavy metal ion.Because the strong polar surfaces of metal oxide nano-material, make to have very strong electric charge on the nano-material surface that these electric charges can adsorb heavy metal ion in the waste water by electrostatic interaction, thereby reach the purpose of removing heavy metal ion.
The present invention utilizes the photocatalytic and the adsorptivity of metal oxide nano-material, make dye molecule, removal of heavy metal ions in dyestuff, the heavy metal wastewater thereby, improve the degraded and the rate of adsorption thereby improve the active site that temperature can increase metal oxide nano-material.Common reduced iron powder method, activated carbon method etc., iron powder more just can reach equal effect with the consumption of acid, though the fine power of regeneration of active carbon effect is poor, the cost height.Therefore, under the condition of equal clearance, effect height of the present invention particularly is fit to different PH waste water, consumes less power, thereby can reduce running cost, cuts down the consumption of energy.The present invention has tangible society, economic benefit.
2, the present invention is applicable to azo dye wastewater and azo free dyes waste water, and azo free dyes waste water wherein is as anthraquinone, triaryl methane type, xanthene type, arylmethane dye, nitro and nitroso-dyes waste water etc.
3, the present invention is applicable to waste water such as lead ion, arsenic ion, nickel ion, copper ion, chromium ion, cadmium ion.
The present invention prepares successfully that its specific area of new oxide nano material is big, high adsorption capacity, efficient height to dye molecule and heavy metal ion, handles that waster water process is simple, cost is low, renewable is strong by solvent heat treatment and supercritical drying.
The specific embodiment
By the following examples treatment effect of the present invention is described further.
Embodiment 1:
In the ethanol with the magnesium nitrate 100ml of 18g, add the phenmethylol structure directing agent of 13.5g, mix the back and move in the autoclave, 10
6Being heated to 200 ℃ under the protection of Pa chlorine kept 6 hours, make the magnesium nitrate complete alcoholysis, be heated to 264 ℃ and keep 15h then, drying obtains the bitter earth nano material precursor of sheet 111, accompany burning through 500 ℃ of high temperature, get the brilliant material of bitter earth nano of sheet 111 crystal faces; The 0.9g metal oxide nano-material that makes is put into the Congo red waste water from dyestuff of 3.5L, Congo red initial concentration is 75mg/L in the waste water from dyestuff, and temperature is 10 ℃, and rotating speed is 150r/min, after reacting half an hour, Congo red dyestuff clearance is more than 90%.
Operating condition
Wastewater volume: 120ml
Waste water initial concentration: 100mg/L
Alr mode: rotating speed is 150r/min
Reaction temperature: 10 ℃
2. result of the test
The decolouring result such as the table 1 of Congo red waste water from dyestuff
Table 1
| Time (min) | Percent of decolourization % |
| 0 | 76.91 |
| 5 | 57.68 |
| 10 | 80.44 |
| 20 | 91.25 |
| 30 | 98.99 |
Embodiment 2:
The magnesium nitrate of 18g, the ferric nitrate of 28.4g are dissolved in the ethanol of 200ml, add the phenmethylol structure directing agent of 26.8g, mix the back and move in the autoclave, 10
6Be heated to 200 ℃ under the protection of Pa chlorine and kept 6 hours, make the nitrate complete alcoholysis, be heated to 265 ℃ and keep 15h then, drying obtains the metal oxide nano-material precursor, accompanies burning through 500 ℃ of high temperature, metal oxide nano-material.The 0.09g metal oxide nano-material that makes is put into the Congo red waste water from dyestuff of 120ml, Congo red initial concentration is 100mg/L in the waste water from dyestuff, the pH value scope is 3.29-11.03, temperature is 10 ℃, rotating speed is 150r/min, after reacting half an hour, Congo red dyestuff clearance is more than 90%.
Operating condition
Wastewater volume: 120ml
Waste water initial concentration: 100mg/L
Alr mode: rotating speed is 150r/min
PH value scope: 3.29～11.03
Reaction temperature: normal temperature
2. result of the test
The decolouring result such as the table 1 of Congo red waste water from dyestuff
Table 1
| Time (min) | PH | Percent of decolourization |
| ? | ? | ％ |
| 0 | 7.15 | 0 |
| 5 | 7.15 | 97.08 |
| 10 | 7.15 | 97.71 |
| 20 | 7.15 | 97.95 |
| 30 | 7.15 | 98.5 |
The decolouring result such as the table 2 of the Congo red waste water from dyestuff of different PH
Table 2
| Time (min) | PH | Percent of decolourization % |
| 30 | 2.07 | 97.35 |
| 30 | 4.32 | 97.16 |
| 30 | 5.1 | 96.42 |
| 30 | 8.24 | 95.47 |
| 30 | 12.15 | 95.21 |
Embodiment 3:
The calcium nitrate of magnesium nitrate, 20.88g zinc nitrate and the 20.77g of 18g is dissolved in the ethanol of 600ml, adds the phenmethylol structure directing agent of 40.2g, mix the back and move in the autoclave, 1.5 * 10
6Be heated to 200 ℃ under the protection of Pa chlorine and kept 6 hours, make the nitrate complete alcoholysis, be heated to 267 ℃ and keep 15h then, drying obtains the metal oxide nano-material precursor, accompanies burning through 500 ℃ of high temperature, promptly gets metal oxide nano-material.The 0.09g metal oxide nano-material is put into the X3B waste water from dyestuff of 120ml, and the waste water from dyestuff initial concentration is 100mg/L, and the pH value scope is 3.29-11.03, and temperature is 10 ℃, and rotating speed is 150r/min, and clearance is more than 90% after reaction half an hour.
Operating condition
Wastewater volume: 120ml
Waste water initial concentration: 100mg/L
Alr mode: rotating speed is 150r/min
PH value scope: 3.29～11.03
Reaction temperature: normal temperature
2. result of the test
The decolouring result such as the table 3 of reactive brilliant red (X3B) waste water from dyestuff
Table 3
| Time (min) | PH | Percent of decolourization % |
| 0 | 5.1 | 0 |
| 5 | 5.1 | 85.67 |
| 10 | 5.1 | 90.45 |
| 20 | 5.1 | 93.73 |
| 30 | 5.1 | 96.42 |
The decolouring result such as the table 4 of different PH reactive brilliant red (X3B) waste water from dyestuff
Table 4
| Time (min) | PH | Percent of decolourization % |
| 30 | 3.29 | 99.85 |
| 30 | 4.94 | 99.19 |
| 30 | 7.15 | 99.4 |
| 30 | 9.37 | 99.82 |
| 30 | 11.03 | 98.5 |
Embodiment 4:
Magnesium nitrate, the ferric nitrate of 28.36g, the 20.88g zinc nitrate of 18g are dissolved in the ethanol of 800ml, add the phenmethylol structure directing agent of 53.6g, mix the back and move in the autoclave, 1.2 * 10
6Be heated to 200 ℃ under the protection of Pa chlorine and kept 6 hours, make the nitrate complete alcoholysis, be heated to 261 ℃ and keep 15h then, drying obtains the metal oxide nano-material precursor, accompanies burning through 500 ℃ of high temperature, promptly gets metal oxide nano-material.The 0.09g metal oxide nano-material is put into the acid fuchsin waste water from dyestuff of 120ml, the waste water from dyestuff initial concentration is 100mg/L, and the pH value scope is 3.29-11.03, and temperature is 10 ℃, rotating speed is 150r/min, and clearance is more than 90% after reacting half an hour.Three kinds of waste water from dyestuff can both reach satisfied percent of decolourization, and the present invention all has decolorizing effect preferably to the azo and the azo free dyes waste water of variable concentrations as can be seen.
Operating condition
Wastewater volume: 120ml
Waste water initial concentration: 100mg/L
Alr mode: rotating speed is 150r/min
PH value scope: 3.29-11.03
Reaction temperature: normal temperature
2. result of the test
The decolouring result such as the table 5 of acid fuchsin waste water from dyestuff
Table 5
| Time (min) | PH | Percent of decolourization % |
| 0 | 5.5 | 0 |
| 5 | 5.5 | 98.95 |
| 10 | 5.5 | 99.12 |
| 20 | 5.5 | 99.34 |
| 30 | 5.5 | 99.65 |
Embodiment 5:
Metal oxide nano-material after embodiment 1 reclaimed is put into and is calcined 3h in the Muffle furnace, 500 ℃ of calcining heats.The metal oxide nano-material of getting 0.09g is then put into the Congo red waste water from dyestuff of 120ml, and the waste water from dyestuff initial concentration is 100mg/L, and the pH value scope is 3.29-11.03, temperature is 10 ℃, rotating speed is 150r/min, and after reacting half an hour, clearance is more than 90%.
Operating condition
Wastewater volume: 120ml
Waste water initial concentration: 100mg/L
Alr mode: rotating speed is 150r/min
PH value scope: 3.29～11.03
Reaction temperature: normal temperature
2. result of the test
The decolouring result such as the following table of Congo red waste water from dyestuff are the same with table 1 data.
| Time (min) | PH | Percent of decolourization % |
| 0 | 7.15 | 0 |
| 5 | 7.15 | 97.0 |
| 10 | 7.15 | 97.67 |
| 20 | 7.15 | 97.88 |
| 30 | 7.15 | 98.47 |
Embodiment 6:
The Titanium Nitrate of ferric nitrate, 20.88g nickel nitrate and the 20.77g of the magnesium nitrate of 18g, 28.36g is dissolved in the ethanol of 800ml, adds the phenmethylol structure directing agent of 53.6g, mix the back and move in the autoclave, 1.5 * 10
6Be heated to 200 ℃ under the protection of Pa chlorine and kept 6 hours, make the nitrate complete alcoholysis, be heated to 269 ℃ and keep 15h then, drying obtains the metal oxide nano-material precursor, accompanies burning through 600 ℃ of high temperature, promptly gets metal oxide nano-material.The 0.764g metal oxide nano-material of equal in quality is put into the Cr that contains of 120ml respectively
3+, Pb
2+, As
2+Effluent containing heavy metal ions in, fully contact.Effluent containing heavy metal ions initial concentration: Cr
3+=100mg/L, Pb
2+=100mg/L, As
2+=100mg/L, pH value are 2, and temperature is 10 ℃, and rotating speed is 200r/min, in reaction centrifugal filtration after two hours.
Operating condition
Wastewater volume: 120ml
Effluent containing heavy metal ions initial concentration: Cr
3+=100mg/L, Pb
2+=100mg/L, As
2+=100mg/L
Alr mode: rotating speed is 200r/min
PH value: 2
Reaction temperature: normal temperature
2. result of the test
Handle the result such as the table 6 of effluent containing heavy metal ions
Embodiment result shows, the present invention utilizes metal oxide nano-material to make dye molecule in the waste water containing dye obtain decolouring, degraded, and removed processing method, metal oxide nano-material is dropped in the waste water, metal oxide nano-material is fully contacted with waste water from dyestuff.In addition, to some waste water from dyestuff, need to regulate wastewater temperature to 20-100 ℃.Simultaneously, compound material also makes the heavy metal ion in the heavy metal ion-containing waste water well be removed method, and metal oxide nano-material is fully contacted with heavy metal wastewater thereby, and the waste water after the processing reaches national grade one discharge standard.The present invention can remove multiple dye molecule and contents of many kinds of heavy metal ion apace.Compare with other prior aries, efficient height of the present invention, technology is simple, cost is low, renewable is strong.Therefore, adopt the present invention to reduce processing cost greatly, the danger of having avoided organic dyestuff and heavy metal ion to accumulate in natural water body has tangible economic and social benefit.
Claims (3)
1. one kind is used to handle the metal oxide nano-material that contains dyestuff or effluent containing heavy metal ions, it is characterized in that: the metal oxide nano-material composition is: CaO, ZrO
2, SiO, ZnO, TiO
2, MgO, Fe
2O
3, one or two or more kinds mixture among the NiO; Described metal oxide nano-material is the metal oxide flaky nanocrystalline that strong polar surfaces oriented growth is arranged; Described metal oxide nano-material is flakelike powder or particle, and powder size is 0.5nm-100nm, and grain graininess is 0.5nm-200nm, and specific area is 50-600m
2/ g.
2. the preparation method of metal oxide nano-material according to claim 1, it is characterized in that: carry out according to the following steps: the calcium nitrate that will contain the crystallization water, zirconium nitrate, ethyl orthosilicate, zinc nitrate, butyl titanate, magnesium nitrate, ferric nitrate, one or two or more kinds mixture material is dissolved in methyl alcohol in the nickel nitrate, in ethanol or the propyl alcohol, methyl alcohol, one or two or more kinds mixture material mol ratio of ethanol or propyl alcohol and adding is 60-280: 1, add phenmethylol or benzyl carbinol structure directing agent, one or two or more kinds mixture material that adds and the mol ratio of structure directing agent are 1: 0.5-2, mixing the back moves in the autoclave, 1.0 * 10
6-1.5 * 10
6The protection of Pa chlorine down; be heated to 120 ℃ to 200 ℃ and keep 2-6h; make one or two or more kinds mixture material complete alcoholysis of adding; to be heated to temperature range then be 261 ℃～269 ℃ and keep 15h; drying obtains the metal oxide nano-material precursor, makes metal oxide nano-material through 300 ℃ to 500 ℃ high temperature roasts.
3. metal oxide nano-material according to claim 1 is used to handle the purposes that contains dyestuff or effluent containing heavy metal ions, metal oxide nano-material put into contain in dyestuff or the effluent containing heavy metal ions, wherein metal oxide nano-material is 1 with the mass ratio that contains dyestuff or effluent containing heavy metal ions: 10-4000, both are fully contacted, waste water is decoloured, degrades and adsorbs, clearance to dyestuff is more than 90%, and the clearance of heavy metal ion is more than 91%.
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| CN107603425A (en) * | 2017-09-25 | 2018-01-19 | 常州市协旺纺织品有限公司 | A kind of preparation method of Superhydrophilic coating |
| CN110170323A (en) * | 2019-07-09 | 2019-08-27 | 湘潭大学 | A kind of preparation method of photochemical catalyst and its application in Photocatalytic Degradation of Phenol |
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