CN107376852B - Preparation method of HKUST-1@ FP composite adsorption material and application of adsorption material in adsorption and purification treatment of lead-containing wastewater - Google Patents
Preparation method of HKUST-1@ FP composite adsorption material and application of adsorption material in adsorption and purification treatment of lead-containing wastewater Download PDFInfo
- Publication number
- CN107376852B CN107376852B CN201710762533.7A CN201710762533A CN107376852B CN 107376852 B CN107376852 B CN 107376852B CN 201710762533 A CN201710762533 A CN 201710762533A CN 107376852 B CN107376852 B CN 107376852B
- Authority
- CN
- China
- Prior art keywords
- hkust
- lead
- solution
- adsorption
- composite
- 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.)
- Expired - Fee Related
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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic 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
Abstract
The invention discloses a preparation method of an HKUST-1@ FP composite adsorbing material and application thereof in adsorption and purification treatment of lead-containing wastewater, wherein 3.114g of Cu (NO) is firstly added3)·3H2Dissolving O in 22.5m L deionized water to obtain a solution A, ultrasonically dissolving 1.5g of 1,3, 5-benzenetricarboxylic acid in a 45m L volume ratio of 1:1 mixed solution of absolute ethyl alcohol and N, N-dimethylformamide to obtain a solution B, mixing the solution A and the solution B, adding 4cm of × cm of filter paper into the mixed system, transferring the mixed system into a polytetrafluoroethylene lining reaction kettle, reacting for 12 hours at 90 ℃, taking out the filter paper after the reaction is finished, repeatedly washing the filter paper with deionized water, and finally drying to obtain the composite adsorbing material.
Description
Technical Field
The invention belongs to the technical field of synthesis of composite adsorbing materials and application of the composite adsorbing materials to adsorption and purification treatment of lead-containing wastewater, and particularly relates to a preparation method of an HKUST-1@ FP composite adsorbing material and application of the HKUST-1@ FP composite adsorbing material to adsorption and purification treatment of lead-containing wastewater.
Background
HKUST-1 has the chemical formula: cu3(C9H3O6)2As one of the metal-organic framework materials, it was first synthesized in 1999 by professor Williams of hong kong science and technology. Has good application prospect in the fields of gas storage, biomedicine, magnetic composite materials, catalysis, fluorescence and the like.
Filter Paper (FP) as a Filter material commonly used in laboratories has some excellent properties: (1) the price is cheap and easy to obtain; (2) the biodegradable film is biodegradable and easy to treat; (3) the mechanical property is good; (4) countless small holes are formed in the filter paper, and the filter paper plays a role of a capillary tube; (5) the cellulose that makes up the filter paper has a large number of hydroxyl functional groups, and these highly reactive hydroxyl groups are capable of undergoing a variety of chemical reactions. Thus, filter paper is a good carrier for the preparation of functional composites.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of an HKUST-1@ FP composite adsorbing material and application thereof in adsorption and purification treatment of lead-containing wastewater, the HKUST-1 is loaded on filter paper to successfully prepare the HKUST-1@ FP composite adsorbing material, and the HKUST-1@ FP composite adsorbing material can be used for selectively adsorbing lead in the wastewater and can be recycled after regeneration.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the HKUST-1@ FP composite adsorbing material is characterized by comprising the following specific steps of: first 3.114g of Cu (NO)3)·3H2Dissolving O in 22.5m L deionized water to obtain solution A, ultrasonically dissolving 1.5g 1,3, 5-benzenetricarboxylic acid in 45m L volume ratio of 1:1 mixed solution of absolute ethyl alcohol and N, N-dimethylformamide to obtain solution B, mixing solution A and solution B, adding 4cm × 4cm of filter paper into the mixed system, and rotatingAnd (3) moving the material into a polytetrafluoroethylene lining reaction kettle to react for 12 hours at 90 ℃, taking out the filter paper after the reaction is finished, repeatedly washing the filter paper by deionized water, and finally drying to obtain the HKUST-1@ FP composite adsorbing material.
The application of the HKUST-1@ FP composite adsorption material in adsorption and purification treatment of lead-containing wastewater is characterized by comprising the steps of adding the HKUST-1@ FP composite adsorption material into the lead-containing wastewater, adsorbing at 30 ℃ for 300min to realize adsorption and purification treatment of the lead-containing wastewater, adding the adsorbed HKUST-1@ FP composite adsorption material into a thiourea solution with the molar concentration of 0.2 mol/L, oscillating and desorbing for 24h, taking out the HKUST-1@ FP composite adsorption material, washing with deionized water, and recycling.
The preparation process is simple in process and controllable in conditions, the prepared HKUST-1@ FP composite adsorbing material can selectively adsorb lead from wastewater, the adsorbed composite adsorbing material is desorbed and re-adsorbed by using thiourea solution with the molar concentration of 0.2 mol/L, and after 5 times of recycling, the HKUST-1@ FP composite adsorbing material still has high lead adsorption performance.
Drawings
FIG. 1 is an infrared spectrum of FP, HKUST-1 and HKUST-1@ FP;
FIG. 2 is an XRD spectrum of FP, HKUST-1 and HKUST-1@ FP;
FIG. 3 is an SEM image of a FP;
FIG. 4 is an SEM image of HKUST-1;
FIG. 5 is an SEM image of HKUST-1@ FP;
FIG. 6 is a kinetic curve of adsorption of lead by HKUST-1@ FP;
FIG. 7 is a graph of the effect of initial concentration on lead removal;
FIG. 8 is a graph showing the influence of pH on the lead adsorption amount.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
1. Preparation of HKUST-1@ FP composite adsorbing material:
first 3.114g of Cu (NO)3)·3H2Dissolving O in 22.5m L deionized water to obtain a solution A, ultrasonically dissolving 1.5g of 1,3, 5-benzenetricarboxylic acid in a 45m L volume ratio of 1:1 mixed solution of absolute ethyl alcohol and N, N-dimethylformamide to obtain a solution B, mixing the solution A and the solution B, adding 4cm of × 4cm of filter paper into the mixed system, transferring the mixed system into a polytetrafluoroethylene lining reaction kettle, reacting at 90 ℃ for 12 hours, taking out the filter paper after the reaction is finished, repeatedly flushing the filter paper with deionized water, and finally drying to obtain the HKUST-1@ FP composite adsorbing material.
2. And (3) characterization:
FIG. 1 is an infrared spectrum of FP, HKUST-1 and HKUST-1@ FP. As can be seen from the figure, the characteristic peak of hydroxyl group on the filter paper is 3404cm-1At 2899cm-1The point (B) represents C-H stretching vibration. The infrared spectrum of HKUST-1 is 1645cm-1The characteristic peak at (a) represents the asymmetric stretching vibration of the carbonyl group of the ligand carboxylic acid. Moreover, the characteristic peak of HKUST-1@ FP contains both the characteristic peak of the filter paper and the characteristic peak of HKUST-1, which indicates that HKUST-1 is successfully immobilized on the filter paper.
FIG. 2 is an XRD spectrum of FP, HKUST-1 and HKUST-1@ FP. The XRD spectrogram of HKUST-1@ FP has characteristic diffraction peaks corresponding to HKUST-1 and also has characteristic diffraction peaks corresponding to filter paper, which shows that HKUST-1 is successfully loaded on the filter paper to prepare HKUST-1@ FP. The crystal structure of HKUST-1 was not destroyed.
FIGS. 3-5 are scanning electron micrographs of FP, HKUST-1 and HKUST-1@ FP, respectively. The three have obvious difference in appearance characteristics. The filter paper fibers are clearly visible, HKUST-1 is blocky, the filter paper fibers cannot be observed on the surface of HKUST-1@ FP, and the blocky HKUST-1 is clearly visible, which indicates that HKUST-1 is successfully loaded on the filter paper.
3. Adsorption performance:
FIG. 6 is a kinetic curve of HKUST-1@ FP adsorption of lead, the adsorption speed of the adsorbent to lead is high, the experimental conditions are that the initial concentration of lead is respectively 200 mg/L and 100 mg/L, the volume is 50m L-1 @ FP composite adsorption material 200mg, the temperature is 30 ℃, and the oscillation rate is 160 rpm.
FIG. 7 is a curve showing the effect of initial concentration on lead removal rate, wherein the lead removal rate reaches over 96% in a wide initial concentration range, and the experimental conditions are that the volume is 50m L-1 @ FP composite adsorbing material 200mg, the temperature is 30 ℃, the oscillation rate is 160rpm, and the time is 300 min.
FIG. 8 is a curve showing the influence of pH on lead adsorption under the experimental conditions that the initial lead concentration is 200 mg/L, the volume is 50m L-1 @ FP composite adsorption material is 200mg, the temperature is 30 ℃, the oscillation rate is 160rpm, and the time is 300 min.
The influence of other coexisting metal ions on the lead adsorption of the HKUST-1@ FP is shown in Table 1, and the HKUST-1@ FP can still effectively adsorb the lead under the condition that common metal ions coexist, and the experimental conditions are that the initial concentration of the lead is 200 mg/L, the concentrations of other coexisting metal ions are 50 mg/L, the volume is 50m L-1 @ FP composite adsorption material is 200mg, the temperature is 30 ℃, the oscillation rate is 160rpm, and the time is 300 min.
TABLE 1 influence of coexisting Metal ions on adsorption of lead by HKUST-1@ FP
Regeneration and recycling of HKUST-1@ FP composite adsorption material
Adding the HKUST-1@ FP after adsorbing the lead ions into a 0.2 mol/L thiourea solution, oscillating for 24h, taking out the HKUST-1@ FP, washing with deionized water, adding the washed HKUST-1@ FP into a solution with the initial lead ion concentration of 200 mg/L, oscillating for 300min, repeating the adsorption-elution-re-adsorption cycle for 5 times, wherein the adsorption amounts of the HKUST-1@ FP on the lead are 46.9mg/g, 46.2mg/g, 45.1mg/g, 43.6mg/g and 42.7mg/g in sequence, which shows that the HKUST-1@ FP composite adsorbing material still has high adsorption capacity on the lead after being repeatedly used for 5 times.
Claims (1)
1. A preparation method of an HKUST-1@ FP composite adsorption material is characterized by comprising the following specific steps: first 3.114gCu (NO)3)·3H2Dissolving O in 22.5m L deionized water to obtain solution A, and ultrasonic dissolving 1.5g 1,3, 5-benzenetricarboxylic acidDissolving the mixed solution of absolute ethyl alcohol and N, N-dimethylformamide in a volume ratio of 45m L of 1:1 to obtain a solution B, mixing the solution A and the solution B, adding filter paper with the length of 4cm × 4cm into the mixed system, transferring the mixed system into a polytetrafluoroethylene-lined reaction kettle, reacting for 12 hours at 90 ℃, taking out the filter paper after the reaction is finished, repeatedly washing the filter paper with deionized water, and finally drying to obtain the HKUST-1@ FP composite adsorbing material;
the application of the prepared HKUST-1@ FP composite adsorption material in adsorption and purification treatment of lead-containing wastewater is characterized by comprising the steps of adding the HKUST-1@ FP composite adsorption material into the lead-containing wastewater, adsorbing at 30 ℃ for 300min to realize adsorption and purification treatment of the lead-containing wastewater, adding the adsorbed HKUST-1@ FP composite adsorption material into a thiourea solution with the molar concentration of 0.2 mol/L, oscillating and desorbing for 24h, taking out the HKUST-1@ FP composite adsorption material, washing with deionized water, and recycling the materials, wherein the common metal ion Cu is used for the adsorption and purification treatment of the lead-containing wastewater2+, Zn2+, Mg2+, Co2+, Mn2+, Hg2+, Ni2+, Cd2+Under the coexistence condition, HKUST-1@ FP can still effectively adsorb lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710762533.7A CN107376852B (en) | 2017-08-30 | 2017-08-30 | Preparation method of HKUST-1@ FP composite adsorption material and application of adsorption material in adsorption and purification treatment of lead-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710762533.7A CN107376852B (en) | 2017-08-30 | 2017-08-30 | Preparation method of HKUST-1@ FP composite adsorption material and application of adsorption material in adsorption and purification treatment of lead-containing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107376852A CN107376852A (en) | 2017-11-24 |
| CN107376852B true CN107376852B (en) | 2020-08-04 |
Family
ID=60348182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710762533.7A Expired - Fee Related CN107376852B (en) | 2017-08-30 | 2017-08-30 | Preparation method of HKUST-1@ FP composite adsorption material and application of adsorption material in adsorption and purification treatment of lead-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107376852B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880278B (en) * | 2017-12-07 | 2021-01-15 | 宁波诺丁汉新材料研究院有限公司 | Preparation method of porous metal organic framework material HKUST-1 |
| CN108854995A (en) * | 2018-06-08 | 2018-11-23 | 河南师范大学 | The preparation method and applications of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II) |
| CN108786758A (en) * | 2018-06-08 | 2018-11-13 | 河南师范大学 | A kind of preparation method and applications of HKUST-1@PS compound adsorbents for selective absorption methylene blue |
| CN110787778A (en) * | 2019-11-01 | 2020-02-14 | 中国工程物理研究院材料研究所 | Modified fiber ball filtering and adsorbing material and preparation method and application thereof |
| CN113368839A (en) * | 2021-06-16 | 2021-09-10 | 南京工业大学 | Polyaniline-modified organic metal framework heavy metal adsorbing material and preparation method thereof |
| CN115501862B (en) * | 2022-09-20 | 2023-11-21 | 河南大学 | Preparation method of wheat bran/HKUST-1 aerogel in aqueous solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143331A (en) * | 2013-03-12 | 2013-06-12 | 复旦大学 | Synthetic method for magnetic metal organic framework composite material coated by [Cu3(btc)2] on surfaces of ferroferric oxide microspheres and application of composite material |
| CN103221126A (en) * | 2011-03-31 | 2013-07-24 | 科学与工业研究委员会 | Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof |
| CN103338858A (en) * | 2010-08-25 | 2013-10-02 | 康奈尔大学 | Metal organic framework modified materials, methods of making and methods of using same |
| CN104959116A (en) * | 2015-06-12 | 2015-10-07 | 华南理工大学 | MOFs (metal-organic frameworks) pulp fiber composite and forming and preparing method thereof |
| CN106622139A (en) * | 2015-11-03 | 2017-05-10 | 中国石油化工股份有限公司 | Metal organic framework material and preparation method and application thereof |
-
2017
- 2017-08-30 CN CN201710762533.7A patent/CN107376852B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103338858A (en) * | 2010-08-25 | 2013-10-02 | 康奈尔大学 | Metal organic framework modified materials, methods of making and methods of using same |
| CN103221126A (en) * | 2011-03-31 | 2013-07-24 | 科学与工业研究委员会 | Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof |
| CN103143331A (en) * | 2013-03-12 | 2013-06-12 | 复旦大学 | Synthetic method for magnetic metal organic framework composite material coated by [Cu3(btc)2] on surfaces of ferroferric oxide microspheres and application of composite material |
| CN104959116A (en) * | 2015-06-12 | 2015-10-07 | 华南理工大学 | MOFs (metal-organic frameworks) pulp fiber composite and forming and preparing method thereof |
| CN106622139A (en) * | 2015-11-03 | 2017-05-10 | 中国石油化工股份有限公司 | Metal organic framework material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| A metal-organic framework nanocomposite made from functionalized magnetite nanoparticles and HKUST-1 (MOF-199) for preconcentration of Cd(II), Pb(II), and Ni(II);Ebrahim Ghorbani-Kalhor等;《Microchim Acta》;20160718;第183卷;第2639-2647页 * |
| In situ synthesis of a Cu-BTC metal–organic framework (MOF 199) onto cellulosic fibrous substrates: cotton;Marcia da Silva Pinto等;《Cellulose》;20120810;第19卷;第1771-1779页 * |
| Marcia da Silva Pinto等.In situ synthesis of a Cu-BTC metal–organic framework (MOF 199) onto cellulosic fibrous substrates: cotton.《Cellulose》.2012,第19卷 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107376852A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107376852B (en) | Preparation method of HKUST-1@ FP composite adsorption material and application of adsorption material in adsorption and purification treatment of lead-containing wastewater | |
| Wen et al. | Magnetic porous carbonaceous material produced from tea waste for efficient removal of As (V), Cr (VI), humic acid, and dyes | |
| Zhang et al. | Covalent organic frameworks constructed by flexible alkyl amines for efficient gold recovery from leaching solution of e-waste | |
| Liao et al. | Equilibriums and kinetics studies for adsorption of Ni (II) ion on chitosan and its triethylenetetramine derivative | |
| He et al. | Synthesis of zeolitic imidazolate framework-7 in a water/ethanol mixture and its ethanol-induced reversible phase transition | |
| Fronczak et al. | Graphitic carbon nitride doped with the s-block metals: adsorbent for the removal of methyl blue and copper (II) ions | |
| CN107159128B (en) | Metal-organic framework material and preparation method and application thereof | |
| CN102553523B (en) | Nano zero-valent iron-supported activated carbon fiber, and preparation method and application thereof | |
| CN105233802B (en) | One kind doping arginic copper base metal organic framework materials of L and preparation method thereof | |
| CN104059167B (en) | A kind of preparation method and applications of polyamine compounds modified magnetic chitosan | |
| Lin et al. | Fabrication of lignin-based biochar containing multi-metal ferrite and efficient removal for oxytetracycline hydrochloride | |
| CN109569725B (en) | Method for preparing magnetic Cu (I) microsphere catalyst by one-step method | |
| CN104258817B (en) | The chitosan magnetic of melamine modification, preparation method and applications | |
| Jiang et al. | In-situ growth of bimetallic FeCo-MOF on magnetic biochar for enhanced clearance of tetracycline and fruit preservation | |
| Wang et al. | Highly effective and selective adsorption of Au (III) from aqueous solution by poly (ethylene sulfide) functionalized chitosan: Kinetics, isothermal adsorption and thermodynamics | |
| Fan et al. | Guanidinium ionic liquid-controlled synthesis of zeolitic imidazolate framework for improving its adsorption property | |
| CN108854975B (en) | Rod-shaped ZIF-8 material and preparation method and application thereof | |
| Cui et al. | Microwave-assisted one-pot rapid synthesis of mesoporous silica-chitosan composites for efficient recovery of rhenium (Ⅶ) | |
| CN110280227B (en) | MnO2Preparation and application of/PEI/TA difunctional composite material | |
| Qu et al. | Adsorption of Ni 2+ and Pb 2+ from water using diethylenetriamine-grafted Spirodela polyrhiza: behavior and mechanism studies | |
| JP6083077B2 (en) | Metal ion adsorbent | |
| Mehdi et al. | Adsorption of cadmium ions on silica coated metal organic framework | |
| CN103303980A (en) | Method for preparing nano iron oxide by lignosulfonate template process | |
| JPWO2014125672A1 (en) | Carbonaceous material and method for producing the same | |
| CN113976049A (en) | COF/CS aerogel 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200804 Termination date: 20210830 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |