CN115518610A - Preparation of hollow flower ball-shaped adsorbent based on layered double hydroxides - Google Patents
Preparation of hollow flower ball-shaped adsorbent based on layered double hydroxides Download PDFInfo
- Publication number
- CN115518610A CN115518610A CN202211326739.2A CN202211326739A CN115518610A CN 115518610 A CN115518610 A CN 115518610A CN 202211326739 A CN202211326739 A CN 202211326739A CN 115518610 A CN115518610 A CN 115518610A
- Authority
- CN
- China
- Prior art keywords
- layered double
- preparation
- double hydroxide
- adsorbent
- ball
- 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.)
- Pending
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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The preparation method of the hollow flower-ball-shaped adsorbent based on the layered double hydroxides is characterized by comprising the following steps: tetraethyl silicate (TEOS) is used as a silicon source, silicon dioxide (SiO 2) is prepared under an alkaline condition, then the SiO2 is used as a substrate, layered Double Hydroxides (LDHs) are used as main components, and a hydrothermal method is adopted to prepare the adsorbent.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a preparation method of a hollow flower-ball-shaped adsorbent based on layered double hydroxides.
Back-shadow technique
Water pollution is a worldwide problem. Among them, the contamination of water by toxic metals is the most serious because these metals are highly toxic to humans and the environment even at low concentrations. Heavy metal water pollution mainly comes from industrial pollution, agricultural pollution and domestic pollution. The well-known "public nuisance" osteodynia is caused by the contamination of heavy metal cadmium (Cd). After entering the water body, the heavy metal elements can directly act on human bodies through drinking water and domestic water, can be enriched by aquatic animals and plants, and enter a food chain to further harm the safety of people and livestock. Heavy metals have strong toxic action on aquatic animals, and the fish exposed to high-concentration heavy metal solution for a short time can cause stress reaction, so that the immunity is reduced. Chromium (Cr) is a trace element essential to the human body, plays a special role in sugar metabolism and lipid metabolism of the body, and becomes a toxic pollutant element at high concentrations. The main sources of chromium pollution in the environment are waste water and smoke discharged from industrial departments such as mining fields, ore dressing plants, smelting and electroplating plants, machine manufacturing plants, automobile manufacturing plants, aircraft manufacturing plants, dye plants, printing plants, pharmaceutical factories and the like of chromium ores. The toxicity of chromium is mainly caused by hexavalent chromium ions.
At present, heavy metals in water environment seriously harm the health of an ecosystem and the sustainable development of human society, and the new global problem of taking effective measures to treat and purify polluted water and realizing the reuse of waste water is concerned. The common treatment methods are many and can be divided into chemical methods, physicochemical methods and biotechnology.
Among the above treatment methods, the adsorption method has the advantages of high treatment effect, simple and convenient operation, good selectivity and the like, and particularly has special application value in the field of heavy metal polluted wastewater which has strong pollution and low concentration and is difficult to effectively treat by other treatment methods. Commonly used adsorbents are activated carbon, resins, etc. However, these adsorbents have limited their practical applications due to their weak adsorption capacity or long adsorption time. Therefore, the research and development of the adsorbent with excellent adsorption performance and short adsorption time has important application value.
Disclosure of Invention
In order to solve the above mentioned disadvantages of the prior art, the present invention provides a method for preparing a hollow flower-ball adsorbent based on layered double hydroxides.
The application provides a preparation method of a hollow flower-ball-shaped adsorbent based on layered double hydroxide, which comprises the steps of taking tetraethyl silicate (TEOS) as a silicon source and preparing silicon dioxide (SiO) under an alkaline condition 2 ) Then with SiO 2 The method is characterized in that the substrate is a Layered Double Hydroxide (LDHs) which is used as a main component, and the adsorbent is prepared by a hydrothermal method;
step (1): measuring ammonia water and absolute ethyl alcohol with a certain volume ratio to mix and dissolve;
step (2): measuring a certain amount of TEOS, dissolving the TEOS in the mixed solution of (1), and stirring for 20-60 min at room temperature;
and (3): centrifuging the mixed solution obtained in the step (2), washing the mixed solution by using a certain solvent, and drying the washed mixed solution for a certain time at the temperature of between 25 and 80 ℃;
and (4): weighing a certain amount of the sample in the step (3), adding the sample into a certain amount of water, performing ultrasonic treatment for 5-60 min, adding the sample into a metal salt (LDHs precursor) solution, performing magnetic stirring for a certain time, reacting at 60-150 ℃ for 3-12 h, cooling, centrifuging, washing, and drying at 25-80 ℃ for a certain time;
and (5): and (3) weighing a certain amount of the sample in the step (4), adding the sample into the alkaline solution, magnetically stirring for 1-12 h, centrifuging, washing, and drying at the temperature of 25-80 ℃ for a certain time.
Further, in the step (1), the volume ratio of ammonia water to absolute ethyl alcohol is 1:4. further, in the step (2), the stirring time of the mixed solution is 60min. .
Further, in the step (3), the sample is washed with ethanol and then three times of water, and then dried for 5 hours at the temperature of 80 ℃.
Further, in the step (4), the ultrasonic time is optimized to 60min, the reaction temperature is optimized to 120 ℃, and the reaction time is optimized to 12h.
Further, in the step (5), the alkaline solution is a 2mol/L sodium hydroxide solution, the stirring time is optimized to 12h, the solution is washed by three times of water, and then the solution is dried for 5h at the temperature of 80 ℃. The adsorbent disclosed by the invention has a hollow and flower-shaped structure, a large specific surface area and an excellent adsorption effect.
The LDHs contained in the adsorbent has a crystal structure of hydrotalcite and a chemical composition general formula of [ M Ⅱ (1-x) M Ⅲ x(OH) 2 ] x+ [A n- x/n ] x- ·mH 2 O, wherein, M Ⅱ May be a divalent metal ion, M Ⅲ Is a trivalent metal ion, A is an n-valent anion, and x is M in every mole of LDHs Ⅲ The number of moles of (a).
Preferably, in the LDHs: mg (magnesium) 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ Or Ca 2+ Either one or both of; m Ⅲ Selected from Al 3+ 、Cr 3+ 、Mn 3+ 、Fe 3+ 、Co 3+ 、Ni 3+ Or La 3+ Either or both of; a is selected from OH - 、Cl - 、NO 3 - Or CO 3 2- Either one or both of; n =1 to 2; x =0.15 to 0.35; m =0.5 to 6.
More preferably, in the LDHs: m is a group of Ⅱ Selected from Mn 2+ ；M Ⅲ Selected from Al 3+ (ii) a A is selected from OH - 、Cl - Or NO 3 - 。
According to the adsorbent disclosed by the invention, the removal rate of a Cd (II) -containing solution with the mass concentration of 50mg/L reaches 92.8% within 120 min.
According to the adsorbent disclosed by the invention, within 120min, the removal rate of the Cr (VI) containing solution with the mass concentration of 50mg/L reaches 94.7%.
Compared with the prior art, the invention has the following beneficial effects:
the adsorbent can adsorb most heavy metal cations (such as Cd) and heavy metal anions (such as Cr) in a short time 2 O 7 2- Etc.) are removed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 (a) TEM and (b) SEM of the adsorbent prepared in example 1;
FIG. 2, BET curve for the adsorbent prepared in example 1;
FIG. 3, adsorbent prepared in example 1 separately treated Cd-and Cr-containing adsorbents 2 O 7 2- A solution adsorption kinetics curve;
FIG. 4, adsorbent prepared in example 1 separately treats Cd and Cr 2 O 7 2- The removal rate is the case.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
(1) Weighing 20mL of ammonia water and 80mL of ethanol for mixing;
(2) Measuring 4ml of TEOS, dissolving in the mixed solution in the step (1), and stirring at room temperature for 60min;
(3) Centrifuging the mixed solution in the step (2), washing twice with ethanol, washing two sides with three times of water, and drying for 5 hours at the temperature of 80 ℃;
(4) 0.06g of the sample in (3) was weighed and added to 60ml of a metal salt (molar ratio: n (Mn (NO)) 3 ) 2 ：n(Al(NO 3 ) 3 ) N (urea) = 3), stirring for 30min, and then reacting for 12h at 120 ℃. Centrifuging, washing and drying.
(5) Weighing 1.0g of adsorbent, adding the adsorbent into 2mol/L sodium hydroxide solution, stirring for 12 hours, centrifuging, washing and drying to obtain the adsorbent.
(6) 0.25g of adsorbent was weighed out and added to 250mL of Cd-containing solution (C) 0 =50 mg/L), the result shows that adsorption equilibrium can be achieved within 120min, and the removal rate reaches 92.8%.
Example 2:
(1) Weighing 20mL of ammonia water and 80mL of ethanol for mixing;
(2) Measuring 4ml of TEOS, dissolving in the mixed solution in the step (1), and stirring at room temperature for 60min;
(3) Centrifuging the mixed solution in the step (2), washing twice with ethanol, washing two sides with three times of water, and drying for 5 hours at the temperature of 80 ℃;
(4) 0.06g of the sample in (3) was weighed and added to 60ml of a metal salt (molar ratio: n (Mn (NO)) 3 ) 2 ：n(Al(NO 3 ) 3 ) N (urea) = 3), stirring for 30min, and then reacting for 12h at 120 ℃. Centrifuging, washing and drying.
(5) Weighing 1.0g of adsorbent, adding the adsorbent into 2mol/L sodium hydroxide solution, stirring for 12 hours, centrifuging, washing and drying to obtain the adsorbent.
(6) 0.25g of adsorbent was weighed out and added to 250ml of Cr-containing solution (C) 0 =50 mg/L), the result shows that the adsorption balance can be achieved within 120min, and the removal rate reaches 94.7%.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The preparation method of the hollow flower ball-shaped adsorbent based on the layered double hydroxide is characterized by comprising the following steps of: preparing silicon dioxide (SiO) under alkaline condition by using tetraethyl silicate (TEOS) as silicon source 2 ) Then with SiO 2 The method is characterized in that the substrate is a Layered Double Hydroxide (LDHs) which is used as a main component, and the adsorbent is prepared by a hydrothermal method;
step (1): measuring ammonia water and absolute ethyl alcohol in a certain volume ratio to mix and dissolve;
step (2): measuring a certain amount of TEOS, dissolving the TEOS in the mixed solution of (1), and stirring for 20-60 min at room temperature;
and (3): centrifuging the mixed solution obtained in the step (2), washing the mixed solution by using a certain solvent, and drying the washed mixed solution for a certain time at the temperature of between 25 and 80 ℃;
and (4): weighing a certain amount of the sample in the step (3), adding the sample into a certain amount of water, performing ultrasonic treatment for 5-60 min, adding the sample into a metal salt (LDHs precursor) solution, performing magnetic stirring for a certain time, reacting at 60-150 ℃ for 3-12 h, cooling, centrifuging, washing, and drying at 25-80 ℃ for a certain time;
and (5): and (3) weighing a certain amount of the sample in the step (4), adding the sample into the alkaline solution, magnetically stirring for 1-12 h, centrifuging, washing, and drying at the temperature of 25-80 ℃ for a certain time.
2. The preparation of the layered double hydroxide-based hollow flower-ball adsorbent according to claim 1, wherein: in the step (1), the volume ratio of ammonia water to absolute ethyl alcohol is 1:4.
3. the preparation of hollow flower-ball adsorbent based on layered double hydroxide according to claim 1, wherein: in the step (2), the stirring time of the mixed solution is 60min.
4. The preparation of the layered double hydroxide-based hollow flower-ball adsorbent according to claim 1, wherein: in the step (3), the sample is washed with ethanol and then three times of water, and then dried for 5 hours at the temperature of 80 ℃.
5. The preparation of the layered double hydroxide-based hollow flower-ball adsorbent according to claim 1, wherein: in the step (4), the ultrasonic time is optimized to be 60min, the reaction temperature is optimized to be 120 ℃, and the reaction time is optimized to be 12h.
6. The preparation of hollow flower-ball adsorbent based on layered double hydroxide according to claim 1, wherein: in the step (5), the alkaline solution is 2mol/L sodium hydroxide solution, the stirring time is optimized to 12h, the solution is washed by three times of water, and then the solution is dried for 5h at the temperature of 80 ℃.
7. The preparation of hollow flower-ball adsorbent based on layered double hydroxide according to claim 1, wherein: the Layered Double Hydroxide (LDHs) has a hydrotalcite crystal structure and a chemical composition general formula of [ M Ⅱ (1-x) M Ⅲ x(OH) 2 ] x+ [A n- x/n ] x- ·mH 2 O, wherein M Ⅱ May be a divalent metal ion, M Ⅲ Is a trivalent metal ion, A is an n-valent anion, and x is M in every mole of LDHs Ⅲ The number of moles of (a). n =1 to 2, x =0.15 to 0.35, and m =0.5 to 6.
8. The preparation of the hollow flower-ball-shaped adsorbent based on the layered double hydroxide as claimed in claim 7, wherein: m in the Layered Double Hydroxide (LDHs) Ⅱ Selected from Mg 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ Or Ca 2+ Either one or both of; m is a group of Ⅲ Selected from Al 3+ 、Cr 3+ 、Mn 3+ 、Fe 3+ 、Co 3+ 、Ni 3+ Or La 3+ Either one or both of; a is selected from OH - 、Cl - 、NO 3 - Or CO 3 2- Either one or both.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211326739.2A CN115518610A (en) | 2022-10-25 | 2022-10-25 | Preparation of hollow flower ball-shaped adsorbent based on layered double hydroxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211326739.2A CN115518610A (en) | 2022-10-25 | 2022-10-25 | Preparation of hollow flower ball-shaped adsorbent based on layered double hydroxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115518610A true CN115518610A (en) | 2022-12-27 |
Family
ID=84703015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211326739.2A Pending CN115518610A (en) | 2022-10-25 | 2022-10-25 | Preparation of hollow flower ball-shaped adsorbent based on layered double hydroxides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115518610A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671645A (en) * | 2012-04-20 | 2012-09-19 | 北京化工大学 | Multi-element composite metal oxide hollow nanosphere and preparation method thereof |
| CN104587950A (en) * | 2015-01-23 | 2015-05-06 | 湖南大学 | Heavy metal ion adsorbent and application thereof |
| CN109621916A (en) * | 2019-01-28 | 2019-04-16 | 菏泽学院 | A kind of preparation method and application of biomass and layered double hydroxide compound |
| CN110102247A (en) * | 2019-04-28 | 2019-08-09 | 华东交通大学 | A kind of zinc-iron layered double hydroxide adsorbent and its dephosphorization remove chromium application |
| CN111659339A (en) * | 2020-06-23 | 2020-09-15 | 华东交通大学 | Preparation method and application of LDHs-loaded layered nano hollow microsphere NiSiO @ NiAlFe adsorbent |
-
2022
- 2022-10-25 CN CN202211326739.2A patent/CN115518610A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671645A (en) * | 2012-04-20 | 2012-09-19 | 北京化工大学 | Multi-element composite metal oxide hollow nanosphere and preparation method thereof |
| CN104587950A (en) * | 2015-01-23 | 2015-05-06 | 湖南大学 | Heavy metal ion adsorbent and application thereof |
| CN109621916A (en) * | 2019-01-28 | 2019-04-16 | 菏泽学院 | A kind of preparation method and application of biomass and layered double hydroxide compound |
| CN110102247A (en) * | 2019-04-28 | 2019-08-09 | 华东交通大学 | A kind of zinc-iron layered double hydroxide adsorbent and its dephosphorization remove chromium application |
| CN111659339A (en) * | 2020-06-23 | 2020-09-15 | 华东交通大学 | Preparation method and application of LDHs-loaded layered nano hollow microsphere NiSiO @ NiAlFe adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| XING WANG ET AL.: "Adsorption performance of tetracycline on NiFe layered double hydroxide hollow microspheres synthesized with silica as the template", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 627, pages 1 - 2 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111547804A (en) | Composite defluorinating agent for industrial wastewater, preparation method and method for defluorinating industrial wastewater | |
| CN105903453A (en) | Preparation method of EDTA modified magnetic adsorbent and method for removing trivalent chromium in water | |
| JP5352853B1 (en) | Method of treating radioactive Cs contaminated water | |
| CN103861564B (en) | Preparation based on the graphene oxide adsorbing material that dendrimer is modified | |
| JP2013146660A (en) | Cleaning agent and cleaning method | |
| CN106552615A (en) | The preparation method of Concave-convex clay rod composite catalyzing material | |
| CN116809034B (en) | Preparation method of dephosphorizing agent based on rare earth modified gangue | |
| CN102923754A (en) | Rare earth elements contained laminated dihydroxy composite metal oxide, and preparation method and application thereof | |
| CN115518610A (en) | Preparation of hollow flower ball-shaped adsorbent based on layered double hydroxides | |
| TW576825B (en) | Method for liquid chromate ion and oxy-metal ions removal and stabilization | |
| EP0832849A1 (en) | Method for eliminating heavy metals from a photographic effluent | |
| JP6257969B2 (en) | Adsorbent manufacturing method | |
| JPH0657354B2 (en) | Simultaneous removal method of arsenic and silicon | |
| CN103342722B (en) | Preparation method of alkaline bismuth gallate | |
| CN103359789B (en) | Preparation method of bismuth subcarbonate | |
| CN102698505B (en) | A kind of preparation method of 13x molecular sieve filter element of purifying drinking water | |
| CN113713754B (en) | Preparation method and application of graphite-phase carbon nitride/magnetic goethite composite material | |
| CN106365244B (en) | A kind of suspended liquid Fe-contg complex reagent and preparation method thereof and the method for efficiently removing selenate in water removal | |
| CN112387246B (en) | Ferroferric oxide-manganese dioxide/molybdenum sulfide complex and preparation method and application thereof | |
| Hesnawi et al. | Heavy metal removal from aqueous solution using natural libyan zeolite and activated carbon | |
| TW202108237A (en) | Water purification material containing iron as main component and method for producing the same | |
| CN110404503B (en) | Fluorine-modified hydrotalcite dephosphorization reagent and preparation method and application thereof | |
| CN113617330B (en) | Low-cost and fast Pb adsorption device 2+ Preparation method of Na-SUZ-4 molecular sieve | |
| CN113262753B (en) | Preparation method and application of millimeter-sized monodisperse magnesium oxide pellets | |
| CN110876919A (en) | Preparation method of high-salinity wastewater nitrate radical adsorbent |
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 |