CN110698666A - Composite catalyst and application thereof in preparation of polyphenol by oxidative polymerization of phenol-containing wastewater - Google Patents
Composite catalyst and application thereof in preparation of polyphenol by oxidative polymerization of phenol-containing wastewater Download PDFInfo
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- CN110698666A CN110698666A CN201910926730.7A CN201910926730A CN110698666A CN 110698666 A CN110698666 A CN 110698666A CN 201910926730 A CN201910926730 A CN 201910926730A CN 110698666 A CN110698666 A CN 110698666A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
Abstract
The invention discloses a composite catalyst and application thereof in preparing polyphenol by oxidative polymerization of phenol-containing wastewater, wherein the composite catalyst is prepared by taking Cu (NO)3)2、Na2SiO3、FeCl2、MnSO4And Na2CO3Adding absolute ethyl alcohol to obtain a mixed solution I; mixing the NaOH aqueous solution with the mixed solution I to obtain mixed solution II; adding sodium citrate water solution into the mixed solution II, stirring uniformly, raising the reaction temperature to 500 ℃ within 2min, calcining for 12-18 h, naturally cooling to room temperature, pouring out supernatant, washing the residual solid with distilled water, centrifuging, freeze-drying, and grinding into powder. The composite catalyst of the invention can selectively oxidize phenol in the wastewater and can be repeatedly utilized. The raw materials are cheap and easy to obtain, and the environment is protected. The generated polyphenol can be used for preparing coatings, adhesives, heat-insulating materials and the like subsequently, and not only can sewage be treated, but also the resource can be recycled.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and relates to a composite catalyst and application thereof in preparation of polyphenol by oxidative polymerization of phenol-containing wastewater.
Background
Phenol is a toxic organic pollutant, phenol-containing wastewater can cause harm to people, livestock and crops, nerve, kidney, liver and the like of people can be damaged, and chronic poisoning, headache, dizziness, insomnia, tinnitus, leucocyte reduction, anemia, memory deterioration and other symptoms can be caused by long-term drinking of a water source polluted by phenol. The phenol is degraded in water slowly, and the industrial phenol-containing waste water has wide source and high toxicity. The efficient, economic and environment-friendly treatment of the phenol-containing wastewater is an urgent practical problem to be solved at home and abroad, and has great practical significance.
At present, the treatment methods of phenol-containing wastewater mainly comprise an extraction method (such as a patent CN107399779A), an adsorption method (such as a patent CN107774232A), a catalytic oxidation method (such as a patent CN1017987B), an activated sludge method (such as a patent CN105585114A), an electrochemical method (such as a patent CN105858823A) and the like, and only phenol in the wastewater can be mineralized and degraded, but resource recovery cannot be realized. Aiming at phenol recovery, the traditional methods comprise extraction recovery (such as CN105399174B), membrane separation (such as CN105540718B), electrochemical method (such as CN101362677B) and the like, and have the defects of high energy consumption, complex operation, high cost and the like; benglong et al (Chinese patent: CN105540718B, a liquid membrane and its application for enriching and recovering phenolic organic compounds) use a solid-phase liquid membrane to recover phenol in wastewater, although the operation is simple and the cost is low, the method is not suitable for neutral and alkaline wastewater treatment, and the recovery rate of phenol is greatly reduced as the pH value of wastewater is increased.
Based on HO [ E ° (HO./H)2O)＝1.8-2.7V vs.NHE]And SO4 -·[E°(SO4 -·/SO4 2-)＝2.5-3.1V vs.NHE]The advanced oxidation technology can oxidize phenolic pollutants in a non-selective way or even completely mineralize the phenolic pollutants through hydroxylation, ring opening and other reactions of a benzene ring. However, the oxidizing ability of these oxidizing species tends to decrease rapidly with increasing pH. In addition, with the increase of the organic content and the increase of the carbon chain, the amount of the oxidant required for completely mineralizing the organic matter is obviously increased, thereby greatly increasing the operation cost. Therefore, the search for a new oxidation technology for more efficient, economical and safe treatment of phenol wastewater should become an important target for the development of oxidation technology.
The oxidative polymerization of phenolic pollutants into polyphenol is a green oxidation technology with potential application value. Because the polyphenol is not only an important organic semiconductor material, but also a good substitute of an anticorrosive material and phenolic resin, the oxidation technology can pollute phenols in wastewaterChanging waste into valuable. Despite horseradish peroxidase and H2O2The system can polymerize phenolic substances in the wastewater into insoluble polymers, however, the sensitivity of the enzyme to industrial wastewater, the inhibition effect of phenol free radicals on the enzyme activity, the higher price and the limited service life of the enzyme limit the wide application of the technology in the treatment process of the phenol-containing wastewater. Therefore, the idea of converting phenol pollutants in wastewater into polyphenol by seeking a cheaper and durable catalytic system is an important development direction of phenolic wastewater treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a composite catalyst.
The second purpose of the invention is to provide a preparation method of the composite catalyst.
The third purpose of the invention is to provide the application of the composite catalyst in the preparation of polyphenol by using the phenol-containing wastewater through oxidative polymerization.
The technical scheme of the invention is summarized as follows:
a preparation method of the composite catalyst comprises the following steps:
(1) taking 0.1-0.3mol of Cu (NO) according to the proportion3)2、0.1-0.2molNa2SiO3、0.1-0.3molFeCl2、0.2-0.3molMnSO4And 0.1 to 0.25mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I;
(2) mixing a 10M NaOH aqueous solution with the mixed solution I according to the volume ratio of 1.5-2.5:1 to obtain a mixed solution II; adding a 1M sodium citrate aqueous solution into a mixed solution II, wherein the volume ratio of the mixed solution II to the 1M sodium citrate aqueous solution is 150: 0.5 to 1.5, stirring evenly, raising the reaction temperature to 500 ℃ within 2min, calcining for 12 to 18 hours, naturally cooling to room temperature, pouring out supernatant, washing the residual solid with distilled water, centrifuging, freeze drying, grinding or crushing into fine powder.
Preferably, step (1) is to take 0.2mol Cu (NO) in proportion3)2、0.1molNa2SiO3、0.3molFeCl2、0.2molMnSO4And 0.2mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I.
The reaction temperature was 500 ℃.
The composite catalyst prepared by the method.
The application of the composite catalyst in preparing the polyphenol by using the phenol-containing wastewater through oxidative polymerization comprises the following steps:
(1) preparing a composite catalyst water suspension with the concentration of 3-5g/L, and adjusting the pH value to 9-13 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 6-24mM, and adjusting the pH value to 9-13 to obtain a solution b; taking phenol-containing wastewater with the concentration range of 3-15mM, and adjusting the pH value to 9-13 to obtain a solution c;
(2) according to the volume ratio of (0.5-2): (0.5-2): 1, mixing the suspension a, the solution b and the solution c, carrying out oxidative polymerization reaction for 1-1.5 hours at the temperature of 25-35 ℃ and the shaking speed of a shaking table of 100-300r/min, centrifuging, and washing the solid with 0.5-1M hydrochloric acid aqueous solution to obtain the polyphenol.
Preferably, step (1) is: preparing a composite catalyst water suspension with the concentration of 5g/L, and adjusting the pH value to 10-12 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 12mM, and adjusting the pH value to 10-12 to obtain a solution b; the phenol-containing wastewater with the concentration range of 12mM is taken, and the pH value is adjusted to 10-12, so as to obtain a solution c.
The step (2) is as follows: according to the volume ratio of 1: 1: 1, mixing the suspension a, the solution b and the solution c uniformly, carrying out oxidative polymerization reaction for 1 hour at the temperature of 25 ℃ and the shaking speed of a shaking table of 150r/min, centrifuging, and washing the solid with 1M hydrochloric acid aqueous solution to obtain the polyphenol.
The invention has the advantages that:
the composite catalyst of the invention can selectively oxidize phenol in the wastewater, and the composite catalyst can be repeatedly used. The raw materials are cheap and easy to obtain, the reaction does not depend on the pH value of the system, and the heterogeneous catalytic reaction is more efficient and environment-friendly. No other intermediate products are produced in the process, and the polyphenol which is insoluble in acid, alkali and organic solvent is completely generated, so that the polyphenol can be used for preparing coatings, adhesives, heat-insulating materials and the like in the subsequent process, and not only sewage is treated, but also the resource reutilization is realized.
Drawings
FIG. 1 shows the effect of the composite catalyst prepared in examples 1 to 4 on the removal of phenol by oxidative polymerization of phenol-containing wastewater using the method of example 5.
FIG. 2 shows the dephenolizing effect of the phenol-containing wastewater by oxidative polymerization in examples 6 to 8.
FIG. 3 is a diagram showing the effect of the composite catalyst on the catalytic performance after the composite catalyst is recycled.
FIG. 4 is a photograph showing the washing of the product polyphenol obtained in example 5 with 1M aqueous EDTA solution and 1M aqueous hydrochloric acid solution; 1M aqueous hydrochloric acid solution washed polyphenol; 1M EDTA aqueous solution.
FIG. 5 is a solid infrared analysis effect chart of polyphenol. (a:1M aqueous hydrochloric acid solution dissolving the polyphenol obtained in example 5; b:1M aqueous EDTA solution dissolving the polyphenol obtained in example 5)
FIG. 6 is a graph showing the effect of SSNMR measurement of polyphenol obtained in example 5.
FIG. 7 is a flight mass spectrometric detection of soluble polyphenol (dissolved in methanol) obtained in example 5.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of the composite catalyst comprises the following steps:
(1) 0.1mol of Cu (NO)3)2、0.2molNa2SiO3、0.2molFeCl2、0.3molMnSO4And 0.2mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I;
(2) mixing a 10M NaOH aqueous solution with the mixed solution I according to the volume ratio of 2:1 to obtain a mixed solution II; adding a 1M sodium citrate aqueous solution into a mixed solution II, wherein the volume ratio of the mixed solution II to the 1M sodium citrate aqueous solution is 150: 1, stirring uniformly, transferring to a muffle furnace, raising the reaction temperature to 500 ℃ within 2min, calcining for 12 hours, naturally cooling to room temperature, pouring out a supernatant, washing the residual solid with distilled water, centrifuging, freeze-drying, and grinding into fine powder.
Example 2
A preparation method of the composite catalyst comprises the following steps:
(1) 0.2mol of Cu (NO)3)2、0.1molNa2SiO3、0.3molFeCl2、0.2molMnSO4And 0.2mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I;
(2) mixing a 10M NaOH aqueous solution with the mixed solution I according to the volume ratio of 1.5:1 to obtain a mixed solution II; adding a 1M sodium citrate aqueous solution into a mixed solution II, wherein the volume ratio of the mixed solution II to the 1M sodium citrate aqueous solution is 150: 0.5, stirring uniformly, transferring to a muffle furnace, increasing the reaction temperature to 500 ℃ within 2min, calcining for 12 hours, naturally cooling to room temperature, pouring out the supernatant, washing the residual solid with distilled water, centrifuging, freeze-drying, and crushing into fine powder.
Example 3
A preparation method of the composite catalyst comprises the following steps:
(1) 0.25mol of Cu (NO)3)2、0.2molNa2SiO3、0.25molFeCl2、0.2molMnSO4And 0.1mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I;
(2) mixing a 10M NaOH aqueous solution with the mixed solution I according to the volume ratio of 2.5:1 to obtain a mixed solution II; adding a 1M sodium citrate aqueous solution into the mixed solution II, wherein the volume ratio of the mixed solution II to the 1M sodium citrate aqueous solution is 150: 1.5, stirring uniformly, transferring to a muffle furnace, increasing the reaction temperature to 500 ℃ within 2min, calcining for 12 hours, naturally cooling to room temperature, pouring out the supernatant, washing the residual solid with distilled water, centrifuging, freeze-drying, and grinding into fine powder.
Example 4
A preparation method of the composite catalyst comprises the following steps:
(1) 0.3mol of Cu (NO)3)2、0.1molNa2SiO3、0.1molFeCl2、0.25molMnSO4And 0.25mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I;
(2) mixing a 10M NaOH aqueous solution with the mixed solution I according to the volume ratio of 2:1 to obtain a mixed solution II; adding a 1M sodium citrate aqueous solution into the mixed solution II, wherein the volume ratio of the mixed solution II to the 1M sodium citrate aqueous solution is 150: 1, stirring uniformly, transferring to a muffle furnace, raising the reaction temperature to 300 ℃ within 2min, calcining for 18 hours, naturally cooling to room temperature, pouring out a supernatant, washing the residual solid with distilled water, centrifuging, freeze-drying, and grinding into fine powder.
Example 5
The application of the composite catalyst in preparing the polyphenol by the oxidative polymerization of the phenol-containing wastewater comprises the following steps:
(1) preparing a composite catalyst (prepared in examples 1, 2, 3 and 4 respectively) aqueous suspension with a concentration of 5g/L, and adjusting the pH value to 10 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 12mM, and adjusting the pH value to 10 to obtain a solution b; taking phenol-containing wastewater with the concentration of 12mM, and adjusting the pH value to 10 to obtain a solution c;
(2) according to the volume ratio of 1: 1: 1, mixing the suspension a, the solution b and the solution c uniformly, carrying out oxidative polymerization reaction for 1 hour at the temperature of 25 ℃ and the shaking speed of a shaking table of 150r/min, centrifuging, and washing the solid with 1M hydrochloric acid aqueous solution to obtain the polyphenol. The product appearance and characterization are shown in fig. 4, 5, 6 and 7.
The degradation of the effect of the composite catalyst prepared in the examples 1 to 4 on phenol removal by oxidative polymerization of phenol-containing wastewater is shown in FIG. 1, and the reaction is substantially balanced within 1 hour.
Repeatedly using the composite catalyst:
after the centrifugation in step (2) of this example, the composite catalyst with polyphenol was separated and reused, and finally the solid was washed with 1M hydrochloric acid aqueous solution to obtain polyphenol, and the composite catalyst was reused many times, and the catalytic performance effect is shown in fig. 3.
Example 6
The application of the composite catalyst in preparing the polyphenol by the oxidative polymerization of the phenol-containing wastewater comprises the following steps:
(1) preparing a composite catalyst (prepared in example 2) water suspension with the concentration of 5g/L, and adjusting the pH value to 12 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 12mM, and adjusting the pH value to 12 to obtain a solution b; taking phenol-containing wastewater with the concentration of 12mM, and adjusting the pH value to 12 to obtain a solution c;
(2) according to the volume ratio of 1: 1: 1, mixing the suspension a, the solution b and the solution c uniformly, carrying out oxidative polymerization reaction for 1 hour at the temperature of 25 ℃ and the shaking speed of a shaking table of 150r/min, centrifuging, and washing the solid with 1M hydrochloric acid aqueous solution to obtain the polyphenol.
The phenol-containing wastewater is subjected to oxidative polymerization and dephenolization, and the effect is shown in figure 2.
Example 7
The application of the composite catalyst in preparing the polyphenol by the oxidative polymerization of the phenol-containing wastewater comprises the following steps:
(1) preparing a 3g/L aqueous suspension of the composite catalyst (prepared in example 3), and adjusting the pH to 9 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 6mM, and adjusting the pH value to 9 to obtain a solution b; taking phenol-containing wastewater with the concentration of 3mM, and adjusting the pH value to 9 to obtain a solution c;
(2) according to the volume ratio of 0.5: 0.5: 1, mixing the suspension a, the solution b and the solution c, carrying out oxidative polymerization reaction for 1 hour at the temperature of 25 ℃ and the shaking speed of a shaking table of 100r/min, centrifuging, and washing the solid with 0.5M hydrochloric acid aqueous solution to obtain the polyphenol.
The phenol-containing wastewater is subjected to oxidative polymerization and dephenolization, and the effect is shown in figure 2.
Example 8
The application of the composite catalyst in preparing the polyphenol by the oxidative polymerization of the phenol-containing wastewater comprises the following steps:
(1) preparing a composite catalyst (prepared in example 4) water suspension with the concentration of 5g/L, and adjusting the pH to 13 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 24mM, and adjusting the pH value to 13 to obtain a solution b; taking phenol-containing wastewater with the concentration of 15mM, and adjusting the pH value to 13 to obtain a solution c;
(2) according to the volume ratio of 2: 2:1, mixing the suspension a, the solution b and the solution c, carrying out oxidative polymerization reaction for 1.5 hours at the temperature of 35 ℃ and the shaking speed of a shaking table of 300r/min, centrifuging, and washing the solid with 1M hydrochloric acid aqueous solution to obtain the polyphenol.
The phenol-containing wastewater is subjected to oxidative polymerization and dephenolization, and the effect is shown in figure 2.
Detection of phenol: the specific detection method refers to a national standard method 4-aminoantipyrine method for detecting phenol, and the concentration of the phenol can be obtained. After the reaction, samples were taken from the reaction system every hour and detected by uv spectrophotometry, and the amount of phenol consumed was judged by the decrease in concentration, and it was estimated whether the reaction selectively oxidized phenol.
Solid infrared analysis: the solid after the reaction was dissolved with a sufficient amount of 1M aqueous hydrochloric acid solution (a) and 1M aqueous EDTA solution (b) to obtain a remaining undissolved solid, which was dried and then subjected to a test analysis on an infrared spectrometer, as shown in FIG. 5.
SSNMR (solid nuclear magnetic resonance) analysis: dissolving the reacted solid with sufficient hydrochloric acid to obtain the remaining insoluble solid, drying, testing with nuclear magnetic resonance apparatus to obtain the carbon spectrum of the substance to be tested, and performing structural identification with the carbon spectrum, as shown in FIG. 6.
Detecting a flight mass spectrum: the polyphenol was dissolved in methanol, the supernatant was mixed well with CHCA matrix and the flight mass spectral data were recorded on Bruker Autoflex tof/tofIII in the 337nm linear mode, see FIG. 7.
Claims (7)
1. The preparation method of the composite catalyst is characterized by comprising the following steps:
(1) taking 0.1-0.3mol of Cu (NO) according to the proportion3)2、0.1-0.2molNa2SiO3、0.1-0.3molFeCl2、0.2-0.3molMnSO4And 0.1 to 0.25mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I;
(2) mixing a 10M NaOH aqueous solution with the mixed solution I according to the volume ratio of 1.5-2.5:1 to obtain a mixed solution II; adding a 1M sodium citrate aqueous solution into a mixed solution II, wherein the volume ratio of the mixed solution II to the 1M sodium citrate aqueous solution is 150: 0.5 to 1.5, stirring evenly, raising the reaction temperature to 500 ℃ within 2min, calcining for 12 to 18 hours, naturally cooling to room temperature, pouring out supernatant, washing the residual solid with distilled water, centrifuging, freeze drying, grinding or crushing into fine powder.
2. The method as set forth in claim 1, wherein the step (1) is to take 0.2mol of Cu (NO) in proportion3)2、0.1molNa2SiO3、0.3molFeCl2、0.2molMnSO4And 0.2mol Na2CO3Adding absolute ethyl alcohol to 1L to obtain a mixed solution I.
3. The process according to claim 1 or 2, characterized in that the reaction temperature is 500 ℃.
4. A composite catalyst prepared by the process of any of claims 1 to 3.
5. The use of the composite catalyst of claim 4 for the preparation of polyphenol by oxidative polymerization of phenol-containing wastewater, characterized by comprising the steps of:
(1) preparing a composite catalyst water suspension with the concentration of 3-5g/L, and adjusting the pH value to 9-13 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 6-24mM, and adjusting the pH value to 9-13 to obtain a solution b; taking phenol-containing wastewater with the concentration range of 3-15mM, and adjusting the pH value to 9-13 to obtain a solution c;
(2) according to the volume ratio of (0.5-2): (0.5-2): 1, mixing the suspension a, the solution b and the solution c, carrying out oxidative polymerization reaction for 1-1.5 hours at the temperature of 25-35 ℃ and the shaking speed of a shaking table of 100-300r/min, centrifuging, and washing the solid with 0.5-1M hydrochloric acid aqueous solution to obtain the polyphenol.
6. Use according to claim 5, characterized in that said step (1) is: preparing a composite catalyst water suspension with the concentration of 5g/L, and adjusting the pH value to 10-12 to obtain a suspension a; preparing a potassium persulfate aqueous solution with the concentration of 12mM, and adjusting the pH value to 10-12 to obtain a solution b; the phenol-containing wastewater with the concentration range of 12mM is taken, and the pH value is adjusted to 10-12, so as to obtain a solution c.
7. Use according to claim 5, characterized in that said step (2) is: according to the volume ratio of 1: 1: 1, mixing the suspension a, the solution b and the solution c uniformly, carrying out oxidative polymerization reaction for 1 hour at the temperature of 25 ℃ and the shaking speed of a shaking table of 150r/min, centrifuging, and washing the solid with 1M hydrochloric acid aqueous solution to obtain the polyphenol.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072608A (en) * | 1976-01-13 | 1978-02-07 | Phillips Petroleum Company | Polluted water purification |
| CN1228355A (en) * | 1998-03-10 | 1999-09-15 | 北京燕山石油化工公司研究院 | Compound oxide catalyst for phenol hydroxylation and its preparing method |
| CN1361094A (en) * | 2000-12-29 | 2002-07-31 | 北京燕山石油化工公司研究院 | Integrated phenol hydroxylating process of preparing dihydroxylbenzene |
| CN101626830A (en) * | 2007-03-21 | 2010-01-13 | Omya发展股份公司 | Surface treated calcium carbonate and its use in waste water treatment |
| CN106630103A (en) * | 2017-02-22 | 2017-05-10 | 天津工业大学 | Method for degrading phenol by solid catalyst |
| CN109529841A (en) * | 2018-12-20 | 2019-03-29 | 南京工业大学 | A kind of preparation method handling the heterogeneous effective catalyst of phenolic waste water Fenton-like |
-
2019
- 2019-09-27 CN CN201910926730.7A patent/CN110698666A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072608A (en) * | 1976-01-13 | 1978-02-07 | Phillips Petroleum Company | Polluted water purification |
| CN1228355A (en) * | 1998-03-10 | 1999-09-15 | 北京燕山石油化工公司研究院 | Compound oxide catalyst for phenol hydroxylation and its preparing method |
| CN1361094A (en) * | 2000-12-29 | 2002-07-31 | 北京燕山石油化工公司研究院 | Integrated phenol hydroxylating process of preparing dihydroxylbenzene |
| CN101626830A (en) * | 2007-03-21 | 2010-01-13 | Omya发展股份公司 | Surface treated calcium carbonate and its use in waste water treatment |
| CN106630103A (en) * | 2017-02-22 | 2017-05-10 | 天津工业大学 | Method for degrading phenol by solid catalyst |
| CN109529841A (en) * | 2018-12-20 | 2019-03-29 | 南京工业大学 | A kind of preparation method handling the heterogeneous effective catalyst of phenolic waste water Fenton-like |
Non-Patent Citations (1)
| Title |
|---|
| ZHENG ZHAN-WANG 等: ""Heterogeneous UV/Fenton catalytic degradation of wastewater containing phenol with Fe-Cu-Mn-Y catalyst"", 《 JOURNAL OF ZHEJIANG UNIVERSITY SCIENCE 》 * |
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