CN108854995A - The preparation method and applications of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II) - Google Patents
The preparation method and applications of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II) Download PDFInfo
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- CN108854995A CN108854995A CN201810589968.0A CN201810589968A CN108854995A CN 108854995 A CN108854995 A CN 108854995A CN 201810589968 A CN201810589968 A CN 201810589968A CN 108854995 A CN108854995 A CN 108854995A
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- 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]
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- 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
- B01J20/26—Synthetic macromolecular compounds
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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of preparation method and applications of HKUST-1@PMMA composite material, preparation process is in the N-Methyl pyrrolidone solution that the HKUST-1 material that will be dried is distributed to polymethyl methacrylate under conditions of drying anhydrous closing, then above-mentioned solution is added drop-wise in deionized water and is stayed overnight, separation, is dried to obtain HKUST-1@PMMA composite material.The composite material preparation process is simple; easily promote; realize the granulating of HKUST-1; easily recycling is 200mg/L containing pb (II) waste water to concentration, and HKUST-1@PMMA composite material dosage is 400mg; the adsorption rate of pb (II) reaches 99.49%; the thiourea solution of 0.2mol/L can make the HKUST-1@PMMA composite material regeneration after absorption, and repeated 5 elutions adsorption experiment, absorption property still remains initial 74%.
Description
Technical field
The invention belongs to the adsorption technology fields of heavy metal in waste water, and in particular to one kind is for adsorbing Pb's (II)
The preparation method and applications of HKUST-1@PMMA composite material.
Background technique
The chemical formula of HKUST-1 is：Cu3(C9H3O6)2Or Cu3(TMA)2, TMA-H3For trimesic acid.What HKUST-1 had
The characteristics such as porous structure, high-specific surface area and chemical stability, therefore HKUST-1 has boundless application in many fields
Prospect.
HKUST-1 has a wide range of applications as a kind of new material in adsorbing domain, to methylene blue and Congo red
Selectivity and adjustability with height.HKUST-1 also has the potentiality as gas separation, is primarily due to two reasons,
First is it with good absorption property, and cellular structure abundant and a large amount of metal active site are in terms of adsorbed gas
There is natural advantage；Second be its multi-grade cellular structure it is selective to gas, nonpolar molecule is easy to be attracted to
In tetrahedron cage structure, and polar molecule is then readily adsorbed near metal active site.
HKUST-1 is used as adsorbent, due to large specific surface area, itself be again it is powdered, there are adsorbents after absorption
The problem of difficult separation and recycling.The technical problem to be solved by the present invention is to granulate HKUST-1, its separating property is improved, is
Lead waste water provides a kind of new adsorbent.
Summary of the invention
It is simple, low in cost and can be recycled that the technical problem to be solved by the present invention is to provide a kind of preparation processes
For adsorbing the preparation method and applications of the HKUST-1@PMMA composite material of Pb (II).
The present invention adopts the following technical scheme that one kind is for adsorbing the HKUST-1@of Pb (II) to solve above-mentioned technical problem
The preparation method of PMMA composite material, it is characterised in that the specific steps are：
（1）The preparation of HKUST-1 material, it is 1 that 1,3,5- benzenetricarboxylic acid of 1.5g, which is dissolved in 45mL volume ratio,:1 ethyl alcohol and N, N-
Solution A is obtained in the mixed solution of dimethylformamide, then 3.114g nitrate trihydrate copper is dissolved in 22.5mL deionized water and is obtained
To solution B, solution A and solution B are then mixed and are stirred at room temperature 10min, mixed solution is then transferred to polytetrafluoroethyl-ne
In the autoclave of the 100mL capacity of alkene liner and in 100 DEG C of hydro-thermal reaction 10h, the blue colored crystal of generation is passed through into filtering
Method collect, washed for several times with methanol, the blue colored crystal of preparation finally obtained into HKUST-1 material in 60 DEG C of vacuum drying 12h
Expect spare；
（2）1g polymethyl methacrylate is added to 10g N- crassitude by the preparation of HKUST-1@PMMA composite material
In ketone solution, it is stirred at room temperature under the conditions of close drying is anhydrous and is dissolved to obtain solution C for 24 hours, then will be made from 4g
HKUST-1 material is dispersed evenly by stirring in solution C under the closed water-less environment of drying and obtains solution D, and solution D is dripped
It is added in deionized water and stays overnight, separation is washed with water, obtains HKUST-1@PMMA composite wood then at 60 DEG C of vacuum drying 12h
Material.
The application of HKUST-1@PMMA composite material of the present invention Pb (II) in absorption waste water, wherein adsorption temp
For room temperature, adsorption time 50-100min, the HKUST-1@PMMA composite material after absorption Pb (II) is added to molar concentration and is
In the thiourea solution of 0.2mol/L, it is stored at room temperature the elution for realizing HKUST-1@PMMA composite material for 24 hours, after zeolite regeneration
HKUST-1@PMMA composite material repetitive cycling uses.
Preparation process of the present invention is simple and low in cost, and HKUST-1@PMMA composite material obtained is easy to separate and recover simultaneously
Recycling can be repeated several times.
Detailed description of the invention
Fig. 1 is the infared spectrum of HKUST-1 material and HKUST-1@PMMA composite material；
Fig. 2 is the XRD spectrum of HKUST-1 material and HKUST-1@PMMA composite material；
Fig. 3 is influence curve of the time to HKUST-1@PMMA composite material adsorbance；
Fig. 4 is influence curve of the initial concentration to HKUST-1@PMMA composite material adsorbance；
Fig. 5 is influence curve of the adsorbent material dosage to HKUST-1@PMMA composite material adsorbance；
Fig. 6 is the circulation absorption performance map of HKUST-1@PMMA composite material.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment
The preparation of HKUST-1 material, it is 1 that 1,3,5- benzenetricarboxylic acid of 1.5g, which is dissolved in 45mL volume ratio,:1 ethyl alcohol and N,
Solution A is obtained in the mixed solution of dinethylformamide, then 3.114g nitrate trihydrate copper is dissolved in 22.5mL deionized water
Solution B is obtained, solution A and solution B are then mixed and are stirred at room temperature 10min, mixed solution is then transferred to polytetrafluoro
In the autoclave of the 100mL capacity of ethylene liner and in 100 DEG C of hydro-thermal reaction 10h, the blue colored crystal of generation was passed through
The method of filter is collected, and is washed for several times with methanol, the blue colored crystal of preparation is finally obtained HKUST-1 in 60 DEG C of vacuum drying 12h
Materials for later use；
It is molten to be added to 10g N-Methyl pyrrolidone by the preparation of HKUST-1@PMMA composite material for 1g polymethyl methacrylate
It in liquid, is stirred at room temperature under the conditions of close drying is anhydrous and is dissolved to obtain solution C for 24 hours, then by HKUST-1 made from 4g
Material is dispersed evenly by stirring in solution C under the closed water-less environment of drying and obtains solution D, and solution D is added drop-wise to
In ionized water and overnight, separation is washed with water, obtains HKUST-1@PMMA composite material then at 60 DEG C of vacuum drying 12h.
Fig. 1 is the infrared spectrum of HKUST-1 material and HKUST-1@PMMA composite material.The infrared figure of HKUST-1 material
Spectrum and reported in the literature completely the same, 1645cm-1The characteristic peak at place is the asymmetric stretching vibration of carbonyl group, 730cm-1With
770cm-1What place's characteristic absorption peak indicated is the chelating of metal ion Cu and the carboxylic acid functional on 1,3,5- benzenetricarboxylic acid
Key.
Fig. 2 is the XRD spectrum of HKUST-1 material and HKUST-1@PMMA composite material, by XRD spectrum it is found that
The characteristic absorption peak of HKUST-1 material is observed in HKUST-1@PMMA composite material map.
Absorption property
Fig. 3 is influence curve of the adsorption time to HKUST-1@PMMA composite material adsorbance.A series of volumes are pipetted respectively
50mL, concentration are Pb (II) solution of 200mg/L and 100mg/L in conical flask, are separately added into 200mg HKUST-1@PMMA
Composite material is vibrated in 30 DEG C with 160rpm.In the preceding 30min of absorption, the increase of adsorbance at any time quickly, after 60min
Adsorbance tends to balance state.When initial concentration is 200mg/L and 100mg/L, HKUST-1@PMMA composite material is to Pb
(II) adsorbance is 47.54mg/g and 23.89mg/g respectively.
Fig. 4 is influence curve of the initial concentration to HKUST-1@PMMA composite material adsorbance.It pipettes respectively a series of
50mL, various concentration Pb (II) solution in conical flask, 200mg HKUST-1@PMMA composite material is separately added into, in 30 DEG C
300min is vibrated with 160rpm.When Pb (II) ion initial concentration be 50mg/L, 100mg/L, 150mg/L, 200mg/L,
When 250mg/L, 300mg/L, when the dosage of HKUST-1@PMMA composite material is 200mg, adsorbance is respectively 24.87mg/
g,32.75mg/g,47.53mg/g,91.38mg/g,169.45mg/g.The initial concentration of metal ion is bigger, and adsorbance also increases
Greatly.
Fig. 5 is influence curve of the adsorbent material quality to HKUST-1@PMMA composite material adsorbance.A system is pipetted respectively
Column volume 50mL, concentration are Pb (II) solution of 200mg/L in conical flask, are separately added into the HKUST-1@PMMA of different quality
Composite material vibrates 300min in 30 DEG C with 160rpm.When HKUST-1@PMMA composite material quality is 400mg, Pb (II)
Adsorption rate reach 99.49%.
Fig. 6 is elution and the regenerability figure of adsorbent.HKUST-1/PMMA composite material after absorption Pb (II) is added
Enter into the thiourea solution of 0.2mol/L, is placed at room temperature for for 24 hours, takes out HKUST-1@PMMA composite material, be then then added to
In Pb (II) solution of 200mg/L, with this circulation absorption elution 5 times.After eluting the 5th, HKUST-1@PMMA composite material
Adsorbance still has 35.64mg/g, and absorption property still remains initial 74%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. the preparation method of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II), it is characterised in that specific steps
For：
（1）The preparation of HKUST-1 material, it is 1 that 1,3,5- benzenetricarboxylic acid of 1.5g, which is dissolved in 45mL volume ratio,:1 ethyl alcohol and N, N-
Solution A is obtained in the mixed solution of dimethylformamide, then 3.114g nitrate trihydrate copper is dissolved in 22.5mL deionized water and is obtained
To solution B, solution A and solution B are then mixed and are stirred at room temperature 10min, mixed solution is then transferred to polytetrafluoroethyl-ne
In the autoclave of the 100mL capacity of alkene liner and in 100 DEG C of hydro-thermal reaction 10h, the blue colored crystal of generation is passed through into filtering
Method collect, washed for several times with methanol, the blue colored crystal of preparation finally obtained into HKUST-1 material in 60 DEG C of vacuum drying 12h
Expect spare；
（2）1g polymethyl methacrylate is added to 10g N- crassitude by the preparation of HKUST-1@PMMA composite material
In ketone solution, it is stirred at room temperature under the conditions of close drying is anhydrous and is dissolved to obtain solution C for 24 hours, then will be made from 4g
HKUST-1 material is dispersed evenly by stirring in solution C under the closed water-less environment of drying and obtains solution D, and solution D is dripped
It is added in deionized water and stays overnight, separation is washed with water, obtains HKUST-1@PMMA composite wood then at 60 DEG C of vacuum drying 12h
Material.
2. HKUST-1@PMMA composite material made from a kind of method described in claim 1 in absorption waste water Pb (II) is answered
With wherein adsorption temp is room temperature, adsorption time 50-100min, the HKUST-1@PMMA composite material after absorption Pb (II)
It is added in the thiourea solution that molar concentration is 0.2mol/L, is stored at room temperature and realizes washing for HKUST-1@PMMA composite material for 24 hours
De-, the HKUST-1@PMMA composite material repetitive cycling after zeolite regeneration uses.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810589968.0A CN108854995A (en) | 2018-06-08 | 2018-06-08 | The preparation method and applications of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II) |
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| CN201810589968.0A CN108854995A (en) | 2018-06-08 | 2018-06-08 | The preparation method and applications of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2022062100A1 (en) * | 2020-09-25 | 2022-03-31 | 常州大学 | Electrochemical luminescent aptamer sensor for detecting kanamycin and preparation method therefor |
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| CN103785363A (en) * | 2014-02-13 | 2014-05-14 | 天津大学 | Preparation method for preparing polymer skeleton with surface coated with HKUST-1 through 3D printing, and application of polymer skeleton |
| CN106237990A (en) * | 2016-08-15 | 2016-12-21 | 河南师范大学 | A kind of for CPB@ZIF 8 composite adsorbing methyl orange and preparation method thereof |
| CN107376852A (en) * | 2017-08-30 | 2017-11-24 | 河南师范大学 | A kind of preparation method of@FP composite adsorbing materials of HKUST 1 and its application in adsorption cleaning handles lead waste water |
| CN107486165A (en) * | 2017-08-30 | 2017-12-19 | 河南师范大学 | A kind of preparation method of@FP composite adsorbing materials of ZIF 67 and its application in separation and concentration high-salt wastewater containing cadmium |
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2018
- 2018-06-08 CN CN201810589968.0A patent/CN108854995A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785363A (en) * | 2014-02-13 | 2014-05-14 | 天津大学 | Preparation method for preparing polymer skeleton with surface coated with HKUST-1 through 3D printing, and application of polymer skeleton |
| CN106237990A (en) * | 2016-08-15 | 2016-12-21 | 河南师范大学 | A kind of for CPB@ZIF 8 composite adsorbing methyl orange and preparation method thereof |
| CN107376852A (en) * | 2017-08-30 | 2017-11-24 | 河南师范大学 | A kind of preparation method of@FP composite adsorbing materials of HKUST 1 and its application in adsorption cleaning handles lead waste water |
| CN107486165A (en) * | 2017-08-30 | 2017-12-19 | 河南师范大学 | A kind of preparation method of@FP composite adsorbing materials of ZIF 67 and its application in separation and concentration high-salt wastewater containing cadmium |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022062100A1 (en) * | 2020-09-25 | 2022-03-31 | 常州大学 | Electrochemical luminescent aptamer sensor for detecting kanamycin and preparation method therefor |
| 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 |
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Application publication date: 20181123 |