CN1868587A - Collagenous fibers carried iron catalyst, prepn. method and use thereof - Google Patents
Collagenous fibers carried iron catalyst, prepn. method and use thereof Download PDFInfo
- Publication number
- CN1868587A CN1868587A CN 200610021270 CN200610021270A CN1868587A CN 1868587 A CN1868587 A CN 1868587A CN 200610021270 CN200610021270 CN 200610021270 CN 200610021270 A CN200610021270 A CN 200610021270A CN 1868587 A CN1868587 A CN 1868587A
- Authority
- CN
- China
- Prior art keywords
- parts
- collagen fiber
- concentration
- weight
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
A collagen fiber carried iron catalyst is prepared through pre-treating collagen fibers by formaldehyde, adding them to the solution mixture of sulfuric acid, formic acid, sodium chloride and distilled water, regulating pH=1.5-3.3, stirring, adding Fe salt, stirring while reacting, adding alkali solution, reacting, filtering, washing and drying. Its thermal modifying temp is 75-85 deg.C. Its application is also disclosed.
Description
Technical Field
The invention relates to a collagen fiber loaded iron catalyst, a preparation method and application thereof, belonging to the field of industrial wastewater treatment.
Background
Some of the industrial wastewater belongs to organic wastewater which is difficult to biodegrade, such as printing and dyeing/wool spinning wastewater, chemical wastewater, traditional Chinese medicine wastewater, petroleum/oil wastewater, coking wastewater and the like (yellow amine, cinnabar, Xiaojin, and the like, evaluation of high-concentration organic industrial wastewater treatment technology, industrial water treatment, 2004, 24 (4): 1-5). Chemical Oxygen Demand (COD) of such organic waste waterCr) Meanwhile, different waste water also contains various different biological toxic substances such as nitrobenzene, aniline, phenols and the like, and has serious influence on the environment and human beings. On the other hand, BOD of such organic wastewater5/CODCrVery low (<0.2), much less than the accepted difficult to biochemically 0.3 and difficult to biochemically 0.25 values, and difficult to biodegrade. Therefore, the treatment of refractory organic wastewater is always a key technical problem in the field of environmental protection.
The treatment method of the organic wastewater difficult to degrade mainly comprises a coagulating sedimentation method, a pre-oxidation-biological method, an advanced oxidation method, an adsorption method and the like. The advanced oxidation method is a free radical chain reaction under the actionof a catalyst, has great potential and unique advantages, and has attracted people's attention. The advanced oxidation method uses hydroxyl radical (. OH) as oxidant, the oxidation ability of which is second only to fluorine, and the hydroxyl radical directly reacts with pollutants in the wastewater to degrade the pollutants into carbon dioxide and water (Joe Jun Zhao, ai Ping, Xuxiao Lian, etc. the research of advanced catalytic oxidation method for degrading organic industrial wastewater. environmental science research. 2005, 18 (5): 104-. For example, nanometer titanium dioxide is used as a catalyst to generate hydroxyl radicals under the action of light to degrade organic substances (P.F.Fu, Y.Lu, X.G.Dai.preparation of activated carbon fiber delivered TiO2 photo-catalyst and evaluation of the photo-catalytic activity.J.molecular catalysis A: Chemical, 2004, 221: 81-88). The advanced oxidation technology can also be used as an oxidation means of a preoxidation-biological method to degrade organic matters which are difficult to degrade into organic matters which can be biochemically treated.
Hydroxyl free radicals can also be generated by Fenton reaction to degrade organic matters, namely Fe (II) catalyst and H are utilized2O2Reaction to produce hydroxyl groupsA free radical. The principle is (Mawanhong, Daowei, Lijing, etc.. activate H2O2And molecular oxygen scientific bulletin 2004, 49 (18): 1821-1829):
under the action of ultraviolet light, the reactioncan be accelerated. Also, the above reaction can be carried out using an Fe (III) catalyst, and is generally referred to as a Fenton-like reaction.
The conventional Fenton reaction is carried out using homogeneous catalysts, i.e. salts of Fe (II) or Fe (III) with H2O2The reaction produces hydroxyl radicals. However, the catalyst in this reaction is discharged with the wastewater, which on the one hand increases the cost of wastewater treatment and on the other hand may cause secondary pollution (M.M. Cheng, W.H.Ma, J.Li, et al. visible-light assisted degradation of force polutants over Fe (III) -loaded resin in the presence of H (III))2O2at neutralpH values.Environmental Science&Technology.2004, 38: 1569-1575.). Therefore, the Fenton reaction is more practical and valuable by using the heterogeneous catalyst.
The heterogeneous catalyst used at present is mostly prepared by adopting an impregnation method. However, the catalyst is easily exfoliated due to its poor binding ability to the support, resulting in a decrease in catalytic ability. The supported nano iron catalyst has high catalytic activity, but the subsequent separation is difficult, and the large-scale industrial application is difficult.
Disclosure of Invention
The invention aims to provide a collagen fiber supported iron catalyst and a preparation method and application thereof aiming at the defects of the prior art, and is characterized in that the catalyst is prepared by utilizing the high reaction activity of Fe (III) and collagen fibers and loading Fe (III) on collagen fibers.
The aim of the invention is realized by the following technical measures, wherein the parts of the raw materials are parts by weight except for special specifications.
The formula of the collagen fiber supported iron catalyst comprises the following components:
100 portions of collagen fiber with 80 percent of water content
3-40 parts of formaldehyde with the concentration of 30-40%
5-50 parts of iron salt
1-10 parts of sulfuric acid with the concentration of 1mol/L
1-10 parts of formic acid with the concentration of 1mol/L
2-10 parts of sodium chloride
20 to 100 parts of alkali with the concentration of 100 to 200g/L
Wherein the collagen fiber is non-tanned leftover material of a tannery, and is a granular substance with the average grain diameter of 0.5-2 mm after being crushed, and the thermal denaturation temperature of the collagen fiber loaded iron catalyst is 75-85 ℃.
The iron salt is ferric sulfate or ferric chloride.
The alkali is any one of sodium bicarbonate, sodium acetate or sodium formate.
Preparation method of collagen fiber supported iron catalyst
(1) Pretreatment of collagen fibers
Adding 100 parts of collagen fiber with the water content of 80% into 100-500 parts of water, then adding 3-40 parts of formaldehyde with the concentration of 30% -40%, controlling the pH value to be 6.0-7.0, stirring and reacting for 2-10 hours at normal temperature, raising the temperature to 30-40 ℃, and then stirring and reacting for 3-8 hours; filtering and washing to obtain pretreated collagen fibers, and measuring the thermal denaturation temperature of the pretreated collagen fibers to be 75-81 ℃ by using a differential thermal analyzer (DSC).
(2) Preparation of collagen fiber supported iron catalyst
Adding 100 parts of the pretreated collagen fiber with the water content of 80% into a mixed solution of 1-10 parts of sulfuric acid with the concentration of 1mol/L, 1-10 parts of formic acid with the concentration of 1mol/L, 2-10 parts of sodium chloride and 100-500 parts of distilled water, wherein the pH value of the mixed solution is 1.5-3.3, stirring for 4-12 hours, adding 5-50 parts of ferric salt, reacting at the temperature of 20-45 ℃ for 1-8 hours under stirring, adding 20-100 parts of aqueous alkali with the concentration of 100-200 g/L within 1-8 hours, and reacting for 2-10 hours; filtering and washing to remove unreacted ferric salt, and drying at the temperature of 40-70 ℃ for 12-24 hours to obtain a collagen fiber loaded iron catalyst; the thermal denaturation temperature is 75-85 ℃ measured by a differential thermal analyzer (DSC).
The obtained collagen fiber supported iron catalyst is a heterogeneous catalyst. The catalyst is used for the catalytic degradation of organic wastewater generated in the industries of chemical industry, metallurgy, textile printing and dyeing and the like.
The invention has the following advantages:
1. the prepared collagen fiber supported iron catalyst is prepared by loading Fe (III) on collagen fibers through chemical reaction, solves the problem of the shedding of the Fe (III), and can be repeatedly used for many times.
2. The collagen fiber is solid waste of a tannery, not only has rich raw material sources, but also realizes the resource utilization of the solid waste and changes waste into valuables.
3. The catalyst prepared by pretreating collagen fibers with formaldehyde and then loading iron has better chemical stability.
Drawings
FIG. 1 is a graph showing the change in concentration of orange II during catalytic degradation
C/C0Is the ratio of the concentration of orange II to the initial concentration in the degradation process
The experimental conditions are as follows: (1) h2O2(5mM)+UV(4W)；(2)H2O2(5mM)+UV(8W)；(3)H2O2(5mM) + UV (4W) + catalyst (2.00 g); (4) h2O2(5mM) + UV (8W) + catalyst (2.00 g); (5) h2O2(5mM) + catalyst (2.00 g); (6) UV only (8W); (7) catalyst only (2.00 g).
FIG. 2 shows the variation of TOC during the catalytic degradation of orange II
TOC: total organic carbon content, TOCi: total organic carbon content at the beginning, experimental conditions: h2O2(5mM)，UV(8W)
FIG. 3 shows the reuse of the catalyst
FIG. 4 is the concentration change of malachite green during the catalytic degradation of malachite green
C/C0Is the ratio of the concentration of orange II to the initial concentration in the degradation process
FIG. 5 shows the effect of hydrogen peroxide dosage on the catalytic degradation of malachite green
FIG. 6 is an infrared spectrum of a catalyst before use
FIG. 7 is an infrared spectrum of the catalyst after use
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the teachings of the present invention described above.
Example 1 preparation of iron-supported catalyst for porcine collagen fibers
1. Pretreatment of collagen fibers
Selecting non-tanned pigskin leftover materials of a tannery as raw materials, crushing the raw materials to the granularity of 0.5-2 mm, and then fully washing the raw materials by using distilled water to remove sodium sulfate to obtain the pigskin collagen fibers. 30g (wet weight, moisture content 80%) of pigskin collagen fibers were added to 100ml of a 2% formaldehyde solution at a pH of 6.5. The reaction was stirred at room temperature for 4 hours, then the temperature was raised to 35 ℃ and the reaction was continued for 4 hours. Filtering and washing to obtain the pretreated collagen fiber.
2. Preparation of collagen fiber supported iron catalyst
30g (wet weight) of the pretreated collagen fiber is added into a mixed solution consisting of 1ml of sulfuric acid with the concentration of 1mol/L, 2ml of formic acid with the concentration of 1mol/L, 1.5g of sodium chloride and 200ml of distilled water, and the pH value of the mixed solution is 2.2. Adding 10g of ferric sulfate (dissolved by 150ml of distilled water) after 2 hours, reacting for 4 hours at the temperature of 20-45 ℃ under the condition of stirring, adding 50ml of sodium bicarbonate solution with the concentration of 100g/L within 2 hours to ensure that the pH value of the solution is 4.0, reacting for 4 hours, filtering and washing to remove the unreacted ferric sulfate, drying for 12 hours at the temperature of 50 ℃ to obtain the collagen fiber supported iron catalyst, and measuring the thermal denaturation temperature to be 79 ℃ by using a differential thermal analyzer (DSC).
Example 2 preparation of iron catalyst supported on bovine hide collagen fiber
1. Pretreatment of collagen fibers
Selecting non-tanned cow leather leftover waste of a tannery as a raw material, crushing the raw material to the granularity of 0.5-2 mm, and then fully washing the raw material with distilled water to remove sodium sulfate to obtain cow leather collagen fibers. 100g (wet weight, moisture content 80%) of bovine hide collagen fibers were added to 300ml of a 3% formaldehyde solution at a pH of 6.5. The reaction was stirred at room temperature for 5 hours, then the temperature was raised to 30 ℃ and the reaction was continued for 6 hours. Filtering and washing to obtain the pretreated collagen fiber.
2. Preparation of collagen fiber supported iron catalyst
100g (wet weight, water content 80%) of the pretreated collagen fiber is added into a mixed solution consisting of 5ml of sulfuric acid with the concentration of 1mol/L, 3ml of formic acid with the concentration of 1mol/L, 6.0g of sodium chloride and 300ml of distilled water, and the pH value of the mixed solution is 1.8. After 2 hours, 30g of ferric sulfate (dissolved by 200ml of distilled water) was added, and the mixture was reacted at 35 ℃ for 4 hours with stirring, 80ml of a sodium bicarbonate solution having a concentration of 200g/L was added over 2 hours to adjust the pH of the solution to 4.0, followed by reaction for 4 hours, filtration and washing to remove unreacted ferric sulfate, drying at 50 ℃ for 12 hours to obtain a collagen fiber-supported iron catalyst, and a thermal denaturation temperature of 82 ℃ was measured by a differential thermal analyzer (DSC).
Example 3 preparation of iron-supported catalyst for porcine collagen fibers
1. Pretreatment of collagen fibers
Selecting non-tanned pigskin leftover materials of a tannery as raw materials, crushing the raw materials to the granularity of 0.5-2 mm, and then fully washing the raw materials by using distilled water to remove sodium sulfate to obtain the pigskin collagen fibers. 100g (wet weight, moisture content 80%) of pigskin collagen fibers were added to 300ml of a 2% formaldehyde solution at a pH of 6.5. The reaction was stirred at room temperature for 4 hours, then the temperature was raised to 35 ℃ and the reaction was continued for 4 hours. Filtering and washing to obtain the pretreated collagen fiber.
2. Preparation of collagen fiber supported iron catalyst
100g (wet weight, water content 80%) of the pretreated collagen fiber is added into a mixed solution consisting of 3ml of sulfuric acid with the concentration of 1mol/L, 5ml of formic acid with the concentration of 1mol/L, 4.5g of sodium chloride and 300ml of distilled water, and the pH value of the mixed solution is 2.0. Adding 25g of ferric trichloride (dissolved by 150ml of distilled water firstly) after 2 hours, reacting for 4 hours at the temperature of 20-45 ℃ under the condition of stirring, adding 75ml of sodium bicarbonate solution with the concentration of 200g/L within 2 hours to ensure that the pH value of the solution is 4.0, reacting for 4 hours, filtering and washing to remove unreacted ferric trichloride, drying for 12 hours at the temperature of 50 ℃ to obtain the collagen fiber supported iron catalyst, and measuring the thermal denaturation temperature to be 80 ℃ by using a differential thermal analyzer (DSC).
Application example 1 catalytic degradation of orange II dye wastewater by iron-supported porcine collagen fiber catalyst
Preparing 400ml of orange II dye-containing wastewater, wherein the concentration of orange II is 0.2mmol/L, and the pH value is 3.0; then adding orange II dye wastewater into a photo-assisted catalytic reactor, adding 2.00g of a pigskin collagen fiber supported iron catalyst (example 1), and introducing air to enable the catalyst to be in a fluidized state; the ultraviolet light has a wavelength of 254nm and a power of 4W or 8W. Degradation of orange II under different conditions was examined. Analyzing the concentration change of orange II in the degradation process by using an ultraviolet-visible spectrophotometer, and analyzing the change of the total organic carbon content in the degradation process by using a Total Organic Carbon (TOC) analyzer. The results are shown in FIGS. 1, 2 and 3. As can be seen from figure 1, the collagen fiber loaded iron catalyst can effectively degrade the orange II dye wastewater, and has faster degradation reaction and higher degradation degree under the condition of ultraviolet irradiation. As can be seen from FIG. 2, under otherwise identical conditions, the TOC dropped only 20% when no catalyst was added and 60% when catalyst was added. As can be seen from fig. 3, the degradation ability of the catalyst to orange II was not substantially decreased when the catalyst was repeatedly used three times.
Application example 2 catalytic degradation of malachite green dye wastewater by iron-supported bovine collagen fiber catalyst
Preparing 420ml of malachite green dye wastewater, wherein the concentration of malachite green is 0.2mmol/L, and the pH value is 3.0; then adding the malachite green dye wastewater into a photo-assisted catalytic reactor, adding 1.00g of a bovine hide collagen fiber supported iron catalyst (example 2), and introducing air to enable the catalyst to be in a fluidized state; and long-wave ultraviolet light with the wavelength of 365nm and the power of 8W. The degradation of malachite green under different conditions was examined. The change of the concentration of malachite green during the degradation process is analyzed by an ultraviolet-visible spectrophotometer, and the change of the catalyst before and after use is detected by an infrared spectrum. The results are shown in FIGS. 4 to 7. As can be seen from fig. 4, the concentration of malachite green is almost zero within 120 minutes under the conditions of hydrogen peroxide, catalyst and ultraviolet light. As can be seen from fig. 5, the effect is obvious in the presence or absence of hydrogen peroxide, but the effect of the amount of hydrogen peroxide is not obvious under the experimental conditions. As can be seen from FIGS. 6 and 7, the infrared spectrum of the catalyst is almost unchanged before and after the catalyst is used, indicating that the catalyst has better chemical stability.
Claims (5)
1. The collagen fiber supported iron catalyst is characterized in that the catalyst comprises the following formula components in parts by weight:
100 portions of collagen fiber with 80 percent of water content
3-40 parts of formaldehyde with the concentration of 30-40%
5-50 parts of iron salt
1-10 parts of sulfuric acid with the concentration of 1mol/L
1-10 parts of formic acid with the concentration of 1mol/L
2-10 parts of sodium chloride
20 to 100 parts of alkali with the concentration of 100 to 200g/L
Wherein the collagen fiber is non-tanned leftover material of a tannery, and is a granular substance with the average grain diameter of 0.5-2 mm after being crushed, and the thermal denaturation temperature of the collagen fiber loaded iron catalyst is 75-85 ℃.
2. The collagen fiber-supported iron catalyst according to claim 1, wherein the iron salt is iron sulfate or iron chloride.
3. The collagen fiber-supported iron catalyst according to claim 1, wherein the base is any one of sodium bicarbonate, sodium acetate or sodium formate.
4. A method for preparing a collagen fiber-supported iron catalyst according to any one of claims 1 to 3, which comprises the steps of:
(1) pretreatment of collagen fibers
Adding 100 parts by weight of collagen fiber with the water content of 80% into 100-500 parts by weight of water, adding 3-40 parts by weight of formaldehyde with the concentration of 30% -40%, controlling the pH value to be 6.0-7.0, stirring and reacting for 2-10 hours at normal temperature, raising the temperature to 30-40 ℃, and stirring and reacting for 3-8 hours; filtering and washing to obtain pretreated collagen fibers, and measuring the thermal denaturation temperature of 75-81 ℃ by using a differential thermal analyzer.
(2) Preparation of collagen fiber supported iron catalyst
Adding 100 parts by weight of the pretreated collagen fiber with the water content of 80% into a mixed solution of 1-10 parts by weight of sulfuric acid with the concentration of 1mol/L, 1-10 parts by weight of formic acid with the concentration of 1mol/L, 2-10 parts by weight of sodium chloride and 100-500 parts by weight of distilled water, wherein the pH of the mixed solution is 1.5-3.3, stirring for 4-12 hours, adding 50-200 parts by weight of ferric salt, reacting at the temperature of 20-45 ℃ for 1-8 hours under stirring, adding 20-100 parts by weight of aqueous alkali with the concentration of 100-200 g/L within 1-8 hours, and reacting for 2-10 hours; filtering and washing to remove unreacted ferric salt, and drying at the temperature of 40-70 ℃ for 12-24 hours to obtain a collagen fiber loaded iron catalyst; and measuring the thermal denaturation temperature to be 75-85 ℃ by using a differential calorimeter.
5. The collagen fiber loaded iron catalyst as claimed in claim 1 is used for the catalytic degradation treatment of organic wastewater generated in chemical industry, metallurgy, textile printing and dyeing industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100212706A CN100417441C (en) | 2006-06-27 | 2006-06-27 | Collagenous fibers carried iron catalyst, prepn. method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100212706A CN100417441C (en) | 2006-06-27 | 2006-06-27 | Collagenous fibers carried iron catalyst, prepn. method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1868587A true CN1868587A (en) | 2006-11-29 |
| CN100417441C CN100417441C (en) | 2008-09-10 |
Family
ID=37442448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100212706A Expired - Fee Related CN100417441C (en) | 2006-06-27 | 2006-06-27 | Collagenous fibers carried iron catalyst, prepn. method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100417441C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185889B (en) * | 2007-12-25 | 2011-12-14 | 四川大学 | Collagen fiber supported platinum nano catalyst and use thereof |
| CN101624508B (en) * | 2009-07-28 | 2012-10-03 | 四川大学 | Method for preparing radar absorbing materials with hide glue fibril |
| CN108424081A (en) * | 2018-04-19 | 2018-08-21 | 许水仙 | A kind of preparation method of thermal-insulating type calcium silicate board |
| CN108558285A (en) * | 2018-04-24 | 2018-09-21 | 常州思宇知识产权运营有限公司 | A kind of cracking resistance heat-insulating finishing mortar |
| CN116272990A (en) * | 2023-02-20 | 2023-06-23 | 浙江坤泽环境科技有限公司 | Preparation method and application of transition metal catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3880262B2 (en) * | 1998-11-02 | 2007-02-14 | 株式会社カネカ | Method for producing water-insolubilized regenerated collagen fiber |
| CN1164356C (en) * | 2002-11-27 | 2004-09-01 | 四川大学 | Collagen fiber adsorption material and its preparation method, and its adsorption and separation of tannin |
| CN1270820C (en) * | 2004-07-07 | 2006-08-23 | 四川大学 | Collagen fiber solid borne metallic ion adsorbing material, preparation method and purpose thereof |
-
2006
- 2006-06-27 CN CNB2006100212706A patent/CN100417441C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185889B (en) * | 2007-12-25 | 2011-12-14 | 四川大学 | Collagen fiber supported platinum nano catalyst and use thereof |
| CN101624508B (en) * | 2009-07-28 | 2012-10-03 | 四川大学 | Method for preparing radar absorbing materials with hide glue fibril |
| CN108424081A (en) * | 2018-04-19 | 2018-08-21 | 许水仙 | A kind of preparation method of thermal-insulating type calcium silicate board |
| CN108558285A (en) * | 2018-04-24 | 2018-09-21 | 常州思宇知识产权运营有限公司 | A kind of cracking resistance heat-insulating finishing mortar |
| CN116272990A (en) * | 2023-02-20 | 2023-06-23 | 浙江坤泽环境科技有限公司 | Preparation method and application of transition metal catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100417441C (en) | 2008-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mohajershojaei et al. | Immobilization of laccase enzyme onto titania nanoparticle and decolorization of dyes from single and binary systems | |
| CN110330091B (en) | Magnetic biomass functional carbon fiber based on photo-Fenton catalysis and preparation method and application thereof | |
| CN107744832B (en) | High-molecular-material-modified sludge biochar catalyst, and preparation and application thereof | |
| CN1868587A (en) | Collagenous fibers carried iron catalyst, prepn. method and use thereof | |
| CN111974395B (en) | Red mud-based heterogeneous catalyst, preparation method and pollutant degradation method | |
| CN101549294A (en) | Magnetic nanometer material for processing organic pollutants | |
| CN112121822A (en) | Preparation method of biochar/pyrite composite granular Fenton oxidation catalyst | |
| Shao et al. | Effects of ultrasonic pretreatment on sludge dewaterability and extracellular polymeric substances distribution in mesophilic anaerobic digestion | |
| Tan et al. | Treatment of aerobic treated palm oil mill effluent (AT-POME) by using TiO2 photocatalytic process | |
| CN106215862A (en) | A kind of preparation method and applications of iron oxyhydroxide/graphenoxide oxide composite material | |
| CN111974404A (en) | Photo-assisted BiFe1-xCuxO3Method for treating residual ciprofloxacin in water body by activated peroxymonosulfate | |
| CN110756163A (en) | Nano CoFe2O4Carbon fiber felt composite material and preparation method and application thereof | |
| Ali et al. | Polyacrylamide hybrid nanocomposites hydrogels for efficient water treatment | |
| CN113231059B (en) | Composite catalyst for electron beam sewage treatment and preparation method and application thereof | |
| CN112169798B (en) | Catalyst with collagen-based carbon material loaded with metal cobalt and preparation method and application thereof | |
| CN111411412B (en) | Graphene-polyacrylonitrile-based nano composite material and preparation method and application thereof | |
| CN105964281B (en) | A kind of Preparation method and use of sheet basic copper chloride catalyst | |
| CN112439457B (en) | Visible light response composite catalytic hydrogel and preparation method thereof | |
| CN107473326B (en) | Acidic TiO2Combined method for degrading dye wastewater by hydrosol regeneration aerobic granular sludge | |
| CN110201723A (en) | A kind of dopamine/redox graphene/silver orthophosphate composite photocatalyst material and its preparation | |
| CN114713197A (en) | Preparation method of bamboo processing wastewater treatment material and wastewater treatment method | |
| CN111977776B (en) | Catalytic ozonation-based pretreatment method for acidic wastewater containing difficultly-degradable water-soluble polymers | |
| CN1943851A (en) | Carbon base optic catalytic composite material and its preparing method and using method | |
| CN112499616B (en) | Method for synthesizing fluorescent carbon quantum dots by taking marine product deep processing wastewater as raw material | |
| CN108187647A (en) | A kind of nano graphite flakes and composite titania material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080910 Termination date: 20140627 |
|
| EXPY | Termination of patent right or utility model |