CN108393076B - Copper-containing adsorbent, preparation method and application thereof in adsorption of tetracycline in water - Google Patents
Copper-containing adsorbent, preparation method and application thereof in adsorption of tetracycline in water Download PDFInfo
- Publication number
- CN108393076B CN108393076B CN201810230211.2A CN201810230211A CN108393076B CN 108393076 B CN108393076 B CN 108393076B CN 201810230211 A CN201810230211 A CN 201810230211A CN 108393076 B CN108393076 B CN 108393076B
- Authority
- CN
- China
- Prior art keywords
- copper
- adsorbent
- tetracycline
- water
- activated carbon
- 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.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a copper-containing adsorbent, a preparation method and application thereof in adsorbing tetracycline in water, comprising the following steps: dissolving a copper salt in water to form a copper-containing aqueous solution, adding SBA-15 mesoporous molecular sieve or activated carbon into the aqueous solution, adjusting the pH of the mixed solution to 5-7 under the stirring condition, carrying out hydrothermal reaction on the mixed solution in a closed crystallization kettle at the temperature of 100-120 ℃ for 1.0-5.0 h, filtering, washing and drying to obtain the copper-loaded SBA-15 or copper-loaded activated carbon adsorbent. The invention takes SBA-15 mesoporous molecular sieve or active carbon with large specific surface area as a carrier, and adopts a method of combining precipitation-hydrothermal reaction to prepare the active component of Cu (OH)2The uniformly dispersed copper-containing adsorbent adsorbs tetracycline in water by utilizing the coordination complexation of a copper component and the tetracycline, and the adsorbent has high selectivity, large adsorption capacity and mild operation conditions.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a copper-containing adsorbent, a preparation method and application thereof in adsorption of tetracycline in water.
Background
Antibiotics are widely applied to industries such as disease prevention and treatment, agricultural production, livestock raising, aquaculture and the like, China is a big country of aquaculture industry, and in order to prevent and treat fish diseases and accelerate fish growth and reproduction, antibiotics are widely and massively used. At present, the antibiotic wastewater treatment methods mainly comprise a biochemical method, an oxidation method, an adsorption method and the like. The antibiotic wastewater has strong inhibiting effect on microorganisms, and the biodegradability is not ideal. The processing costs of oxidation processes are generally high and new oxidation intermediates are produced. The adsorption method has the advantages of mild operation conditions, wide application range, no introduction of new impurities, capability of performing advanced treatment on wastewater and the like, and is widely researched. At present, active carbon-based adsorbents are researched more and have a better adsorption effect, but due to the fact that actual water bodies contain more pollutants and the antibiotic concentration is not high, the active carbon has some defects in adsorption selectivity and adsorption depth.
Tetracycline is one of the antibiotics with the largest use amount in China at present, tetracycline molecules contain amphoteric functional groups, the forms of the tetracycline molecules change along with the pH value of the environment, and the tetracycline molecules respectively present three forms of cations, zwitterions and anions and have electron supply groups. In the study of the adsorption of tetracycline by CuY molecular sieves, the literature (journal of inorganic chemistry, 2012, 28 (3): 453-458) suggests that tetracycline is associated with Cu exchanged onto Y molecular sieves2+Strong coordination exists between the two, which is favorable for the adsorption of the Cu on the surface of the molecular sieve, but the Cu is exchanged by the ions2+Limited, resulting in limited adsorption capacity. Patent (removing antibiotic pollution in water by copper sulfide adsorption)Method of matter, application No.: 201310160020.0) discloses a method for adsorbing antibiotic pollutants in wastewater by loading copper sulfide in an adsorption bed, which would require large amounts of copper sulfide active components in practical wastewater treatment. The adsorption performance is related to the specific surface area of the adsorbent, and the high dispersion of the active component on the carrier with large specific surface area is beneficial to reducing the using amount of the active component, improving the contact between the active component and pollutants and improving the adsorption effect.
Disclosure of Invention
The invention aims to provide a copper-containing adsorbent, a preparation method and application thereof in adsorbing tetracycline in water. The adsorbent has the advantages of large specific surface area, high copper content of active components, uniform dispersion and capability of selectively removing tetracycline in water by complexation.
The technical scheme of the invention is as follows:
a copper-containing adsorbent is prepared by the following steps: dissolving a certain amount of copper salt in water to form a copper-containing aqueous solution, adding SBA-15 mesoporous molecular sieve or activated carbon into the aqueous solution, dropwise adding an alkaline aqueous solution into the mixed solution under the stirring condition until the pH of the mixed solution reaches 5-7, stopping dropwise adding, performing hydrothermal reaction on the mixed solution in a closed crystallization kettle at the temperature of 100-120 ℃ for 1.0-5.0 h, filtering, washing and drying the substance to obtain Cu (OH)2Supported SBA-15 or Cu (OH)2A supported activated carbon adsorbent.
The invention uses SBA-15 mesoporous molecular sieve or active carbon to generate suspended Cu (OH) by dropping a certain amount of alkali liquor in a proper pH range2Then, through hydrothermal reaction, Cu (OH)2Uniformly dispersing the tetracycline in the carrier to prepare the tetracycline adsorption adsorbent with better activity. If the pH of the mixture is too low, Cu (OH) is not formed2(ii) a If the pH is too high, Cu (OH) is formed2Easily aggregated into particles, and not beneficial to uniform dispersion on the carrier.
Further, the copper salt is any one of copper nitrate, copper chloride or copper acetate.
Furthermore, the alkaline aqueous solution is ammonia water or sodium hydroxide solution, and the concentration range of the appropriate alkali liquor is 20-30%, which is beneficial to accurately adjusting the pH value of the mixed liquor.
Further, the drying temperature is not higher than 120 ℃, and Cu (OH) on the carrier is avoided2The active ingredient decomposes at high temperature.
Furthermore, the proper copper loading amount is 5-30%, the adsorption performance of the adsorbent is affected due to too low copper content, and the specific surface area of the adsorbent is affected due to too high copper content which can block pore channels of the carrier.
Further, the activated carbon is commercially available granular activated carbon or powdered activated carbon with large specific surface area, preferably powdered activated carbon, and the specific surface area is about 950 m2Per g, total pore volume of about 0.90 cm3/g。
Furthermore, the aperture of the SBA-15 mesoporous molecular sieve is 6.2nm, the wall thickness is 5.4nm, and the specific surface area is approximately equal to 1000m2/g。
The adsorbent prepared by the method is applied to adsorbing tetracycline in water, and the adsorbent is contacted with water containing tetracycline for 1-12.0 h at room temperature and normal pressure, and then the water phase is separated from the adsorbent.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes SBA-15 mesoporous molecular sieve or active carbon with large specific surface area as a carrier, and adopts a method of combining precipitation-hydrothermal reaction to prepare the active component of Cu (OH)2The uniformly dispersed copper-containing adsorbent adsorbs tetracycline in water by utilizing the coordination complexation of a copper component and the tetracycline, and the adsorbent has high selectivity, large adsorption capacity and mild operation conditions.
Drawings
Fig. 1 is XRD spectra of adsorbents prepared in example 1, example 2 and example 5 under different conditions.
Detailed Description
The following examples further illustrate the invention, but the content of the invention is not limited thereto at all.
The preparation method of the SBA-15 mesoporous molecular sieve comprises the following steps:
(1) 2.0mL of concentrated hydrochloric acid is taken to be put into 120.0mL of water to prepare hydrochloric acid aqueous solution with the pH value of approximately 1.0;
(2) weighing 100.0mL of hydrochloric acid aqueous solution prepared in the step (1), weighing 4.0g of template agent P123 in the hydrochloric acid aqueous solution, and stirring in a water bath at 40.0 ℃ to fully dissolve the template agent P123 to form a mixed aqueous solution containing P123;
(3) weighing 9.0g of Tetraethoxysilane (TEOS) and placing the Tetraethoxysilane (TEOS) in the hydrochloric acid aqueous solution (about 22.0 mL) remained in the step (1), and pre-hydrolyzing the TEOS in a water bath at 40.0 ℃ for 3.0h to form a mixed aqueous solution containing the Tetraethoxysilane (TEOS);
(4) dropping mixed aqueous solution containing TEOS into the mixed aqueous solution of P123, stirring in water bath at 40.0 deg.C for 24.0 h; then the mixed solution is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining and crystallized for 48.0h at 100 ℃;
(5) after crystallization is finished, filtering, washing and drying the obtained crystallized product at 100 ℃ for 12.0h to obtain SBA-15 molecular sieve raw powder;
(6) heating the SBA-15 raw powder to 550 ℃ at the speed of 2 ℃/min in the air atmosphere, and then roasting for 5.0h at the temperature to obtain the SBA-15 mesoporous molecular sieve.
Example 1:
preparation of the adsorbent: 0.22g of Cu (NO) was weighed3)2· 3H2And (3) putting the O into a 100mL beaker, adding 30.0mL of deionized water, adding 0.5g of SBA-15 under a stirring state, slowly dropwise adding 20% ammonia water solution, stopping dropwise adding the ammonia water when the pH value of the mixed solution reaches 6.5, and continuously stirring for 30 min. And transferring the mixture into a crystallization kettle, carrying out hydrothermal reaction in an oven at 100 ℃ for 3.0h, taking out the crystallization kettle, and filtering, washing and drying substances in the kettle to obtain the copper-loaded adsorbent.
The application comprises the following steps: 100mL of tetracycline aqueous solution with the concentration of 70mg/L is put into a 250mL glass container, 0.01g of adsorbent is added, after stirring for 12.0h at room temperature, the residual tetracycline concentration is measured by an ultraviolet spectrophotometer, and the equilibrium adsorption quantity of the adsorbent to tetracycline is 462 mg/g of adsorbent.
Example 2:
preparation of the adsorbent: 0.22g of Cu (NO) was weighed3)2· 3H2And (3) putting the O into a 100mL beaker, adding 30.0mL of deionized water, adding 0.5g of SBA-15 under a stirring state, slowly dropwise adding 20% ammonia water solution, stopping dropwise adding the ammonia water when the pH value of the mixed solution reaches 5.5, and continuously stirring for 30 min. And transferring the mixture into a crystallization kettle, heating the crystallization kettle in a drying oven at 100 ℃ for 3.0h, taking out the crystallization kettle, and filtering, washing and drying solid substances in the kettle to obtain the copper-loaded adsorbent.
The application comprises the following steps: 100mL of tetracycline aqueous solution with the concentration of 70mg/L is put into a 250mL glass container, 0.01g of adsorbent is added, after stirring for 12.0h at room temperature, the residual tetracycline concentration is measured by an ultraviolet spectrophotometer, and the equilibrium adsorption quantity of the adsorbent to tetracycline is 394 mg/g of adsorbent.
Example 3:
preparation of the adsorbent: by changing only Cu (NO)3)2· 3H2O was 0.11g, and the other procedures were the same as in example 1.
The application comprises the following steps: 100mL of tetracycline aqueous solution with the concentration of 70mg/L is put into a 250mL glass container, 0.01g of adsorbent is added, after stirring for 12.0h at room temperature, the residual tetracycline concentration is measured by an ultraviolet spectrophotometer, and the equilibrium adsorption quantity of the adsorbent to tetracycline is 325 mg/g of adsorbent.
Example 4:
preparation of the adsorbent: the same as in example 1.
The application comprises the following steps: 100mL of tetracycline aqueous solution with the concentration of 30mg/L is put into a 250mL glass container, 0.01g of adsorbent is added, after stirring for 12.0h at room temperature, the residual tetracycline concentration is measured by an ultraviolet spectrophotometer, and the equilibrium adsorption quantity of the adsorbent to tetracycline is 281 mg/g of adsorbent.
Example 5:
preparation of the adsorbent: the procedure of example 1 was followed except that the carrier was changed to activated carbon.
The application comprises the following steps: 100mL of tetracycline aqueous solution with the concentration of 70mg/L is put into a 250mL glass container, 0.01g of adsorbent is added, after stirring for 12.0h at room temperature, the residual tetracycline concentration is measured by an ultraviolet spectrophotometer, and the equilibrium adsorption capacity of the adsorbent to tetracycline is 493 mg/g of adsorbent.
FIG. 1 is an XRD spectrum of adsorbents prepared under different conditions, and in FIG. 1, curve A is the copper-loaded SBA-15 adsorbent of example 2; curve B is the copper-loaded SBA-15 adsorbent of example 1; curve C is the copper-loaded activated carbon adsorbent of example 5, where 2 θ, 12.74, 25.75, 33.63, and 35.55 are cu (oh), respectively, from top2Characteristic diffraction peak of (1).
Claims (10)
1. The preparation method of the copper-containing adsorbent is characterized by comprising the following steps: dissolving a copper salt in water to form a copper-containing aqueous solution, adding SBA-15 mesoporous molecular sieve or activated carbon into the aqueous solution, adjusting the pH of the mixed solution to 5-7 under the stirring condition, carrying out hydrothermal reaction on the mixed solution in a closed crystallization kettle at the temperature of 100-120 ℃ for 1.0-5.0 h, filtering, washing and drying to obtain the copper-loaded SBA-15 or copper-loaded activated carbon adsorbent.
2. The method for preparing a copper-containing adsorbent according to claim 1, wherein the copper salt is any one of copper nitrate, copper chloride or copper acetate.
3. The method for preparing the copper-containing adsorbent according to claim 1, wherein an alkaline aqueous solution is added dropwise until the pH of the mixed solution reaches 5 to 7, wherein the alkaline aqueous solution is 20 to 30wt% of ammonia water or sodium hydroxide solution.
4. The method of preparing a copper-containing adsorbent according to claim 1, wherein the drying temperature is not higher than 120 ℃.
5. The method for preparing a copper-containing adsorbent according to claim 1, wherein the loading amount of copper is 5 to 30 wt%.
6. The method for preparing the adsorbent containing copper according to claim 1, wherein the activated carbon is commercially available granular activated carbon or powdered activated carbon having a large specific surface area, wherein the specific surface area is 950 m2Per g, total poreThe volume is 0.90 cm3/g。
7. The method for producing the copper-containing adsorbent according to claim 1, wherein the pore size of the SBA-15 mesoporous molecular sieve is 6.2nm, the wall thickness is 5.4nm, and the specific surface area is 1000m2/g。
8. The copper-containing adsorbent produced by the production method as set forth in any one of claims 1 to 7.
9. Use of the copper-containing adsorbent prepared by the preparation method according to any one of claims 1 to 7 for adsorbing tetracycline in water.
10. The use of claim 9, wherein the adsorbent is contacted with the aqueous phase containing tetracycline, and the aqueous phase is separated from the adsorbent after the contact for 1-12.0 h at room temperature and normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810230211.2A CN108393076B (en) | 2018-03-20 | 2018-03-20 | Copper-containing adsorbent, preparation method and application thereof in adsorption of tetracycline in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810230211.2A CN108393076B (en) | 2018-03-20 | 2018-03-20 | Copper-containing adsorbent, preparation method and application thereof in adsorption of tetracycline in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108393076A CN108393076A (en) | 2018-08-14 |
| CN108393076B true CN108393076B (en) | 2021-06-11 |
Family
ID=63093005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810230211.2A Active CN108393076B (en) | 2018-03-20 | 2018-03-20 | Copper-containing adsorbent, preparation method and application thereof in adsorption of tetracycline in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108393076B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385173B (en) * | 2021-06-26 | 2022-09-06 | 昆明理工大学 | Preparation method and application of coral stacked biomass charcoal-based catalyst |
| CN113896221B (en) * | 2021-10-28 | 2023-12-01 | 中建材玻璃新材料研究院集团有限公司 | Composite material for CIGS thin film battery tail gas treatment and preparation method thereof |
| CN114433009A (en) * | 2022-01-26 | 2022-05-06 | 南昌大学 | Vermiculite material for adsorbing copper ions and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193041A (en) * | 1997-03-12 | 1998-09-16 | 抚顺市高新技术开发服务部 | Method for series absorption of refined oil products by absorbent |
| CN101333011A (en) * | 2008-08-05 | 2008-12-31 | 南京大学 | Method for removing tetracycline in water by adsorption method |
| CN101829571A (en) * | 2010-06-08 | 2010-09-15 | 厦门大学 | Method for preparing Cu/SiO2 catalyst |
| CN102534607A (en) * | 2010-12-28 | 2012-07-04 | 上海杰远环保科技有限公司 | Ferrous material with alkaline layer on surface and implementing method for ferrous material |
| CN102774847A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院生态环境研究中心 | Preparation and application methods for novel magnetic molecular sieve adsorbent material |
| CN103157501A (en) * | 2013-04-07 | 2013-06-19 | 扬州大学 | Method for preparing catalyst for catalyzing organic pollutants in wet oxidation water |
| CN103331139A (en) * | 2013-06-20 | 2013-10-02 | 南京工业大学 | Preparation method of copper-containing load-type adsorbent |
| CN105406088A (en) * | 2015-10-30 | 2016-03-16 | 苏州大学 | Small-molecular alcohol oxidation electro-catalysis material and preparation method and application therefor |
| CN105536688A (en) * | 2015-12-10 | 2016-05-04 | 中南大学 | Magnetic core nanoparticle coated by copper hydroxide, and preparation and application thereof |
| CN106694026A (en) * | 2016-12-25 | 2017-05-24 | 常州梦泰照明科技有限公司 | Preparation method of core-shell type cuprous oxide photocatalyst |
| CN107159094A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic magnesium hydroxide adsorbent removes tetracycline in waste water |
-
2018
- 2018-03-20 CN CN201810230211.2A patent/CN108393076B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193041A (en) * | 1997-03-12 | 1998-09-16 | 抚顺市高新技术开发服务部 | Method for series absorption of refined oil products by absorbent |
| CN101333011A (en) * | 2008-08-05 | 2008-12-31 | 南京大学 | Method for removing tetracycline in water by adsorption method |
| CN101829571A (en) * | 2010-06-08 | 2010-09-15 | 厦门大学 | Method for preparing Cu/SiO2 catalyst |
| CN102534607A (en) * | 2010-12-28 | 2012-07-04 | 上海杰远环保科技有限公司 | Ferrous material with alkaline layer on surface and implementing method for ferrous material |
| CN102774847A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院生态环境研究中心 | Preparation and application methods for novel magnetic molecular sieve adsorbent material |
| CN103157501A (en) * | 2013-04-07 | 2013-06-19 | 扬州大学 | Method for preparing catalyst for catalyzing organic pollutants in wet oxidation water |
| CN103331139A (en) * | 2013-06-20 | 2013-10-02 | 南京工业大学 | Preparation method of copper-containing load-type adsorbent |
| CN105406088A (en) * | 2015-10-30 | 2016-03-16 | 苏州大学 | Small-molecular alcohol oxidation electro-catalysis material and preparation method and application therefor |
| CN105536688A (en) * | 2015-12-10 | 2016-05-04 | 中南大学 | Magnetic core nanoparticle coated by copper hydroxide, and preparation and application thereof |
| CN106694026A (en) * | 2016-12-25 | 2017-05-24 | 常州梦泰照明科技有限公司 | Preparation method of core-shell type cuprous oxide photocatalyst |
| CN107159094A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic magnesium hydroxide adsorbent removes tetracycline in waste water |
Non-Patent Citations (4)
| Title |
|---|
| "氢氧化铜／石墨烯复合材料的制备与表征";彭林峰，等;《武汉工程大学学报》;20150831;第41-44页 * |
| "纳米氧化铜球的水热法合成与表征;刘娟，等;《应用化工》;20130528;第828-820、834页 * |
| Adsorption and Cosorption of Tetracycline and Copper(II) on Montmorillonite as Affected by Solution pH;Y U - J U N W A N G，等;《Environ. Sci. Technol.》;20080228 * |
| Interactions of tetracycline with Cd (II), Cu (II) and Pb (II) and their cosorption behavior in soils;Yanping Zhao，等;《Environmental Pollution》;20130531 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108393076A (en) | 2018-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108393076B (en) | Copper-containing adsorbent, preparation method and application thereof in adsorption of tetracycline in water | |
| Tosheva et al. | Micron-and nanosized FAU-type zeolites from fly ash for antibacterial applications | |
| CN103351294A (en) | Preparation method of potassium sorbate | |
| CN108940188B (en) | Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent | |
| CN103041805A (en) | Preparation method of high-activity palladium-carbon catalyst for synthesis of imipenem antibiotics | |
| CN106578418B (en) | Mineral mold remover for feed and preparation method thereof | |
| CN109692648B (en) | Adsorbent for efficiently adsorbing sulfate ions in water and preparation method thereof | |
| CN109692653B (en) | Adsorbent for efficiently adsorbing phosphate ions in water and preparation method thereof | |
| CN102500167B (en) | Core-shell structure composite filter material for water treatment and preparation method thereof | |
| CN110559990A (en) | Preparation method of pure water carbon composite material with low nano zero-valent iron and nano silver loading | |
| JP5083748B2 (en) | Method for producing calcium carbonate / zeolite compound composite | |
| CN113908802A (en) | Copper-based compound for adsorbing organic anionic dye | |
| JP6426213B2 (en) | Amorphous aluminum silicate and method for producing the same | |
| CN115448993B (en) | Wrapped salt product and preparation method and application thereof | |
| CN103864604A (en) | Purification treatment technology for iron removal from sodium citrate mother liquor | |
| CN1557728A (en) | Antimicrobial compound for anion water purifying and activating, its pelletized product and preparation method | |
| US8911526B2 (en) | Nano-leucite for slow release nitrogen fertilizer and green environment | |
| CN110734905A (en) | Immobilized microorganism particles, preparation method thereof and water quality purification method | |
| CN106349057A (en) | Treatment process for deferrization purification of sodium citrate mother liquor | |
| CN112250414B (en) | Preparation method of phosphorus removal material | |
| CN103818919A (en) | Synthetic method for preparing Beta zeolite | |
| CN114950351A (en) | Method for enhanced adsorption of VOCs (volatile organic compounds) by doping modified ZSM-5 molecular sieve and application | |
| CN108793288B (en) | Reusable sewage treatment material | |
| KR20010043030A (en) | Material for introducing physiologically-essential inorganic elements into drinkable water | |
| CN112998011A (en) | Strong-oxidizing antibacterial disinfection material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |