CN105268417A - Preparation method of composite membrane with functions of adsorbing and separating heavy metal ions - Google Patents
Preparation method of composite membrane with functions of adsorbing and separating heavy metal ions Download PDFInfo
- Publication number
- CN105268417A CN105268417A CN201510707679.2A CN201510707679A CN105268417A CN 105268417 A CN105268417 A CN 105268417A CN 201510707679 A CN201510707679 A CN 201510707679A CN 105268417 A CN105268417 A CN 105268417A
- Authority
- CN
- China
- Prior art keywords
- preparation
- nylon
- bisacrylamide
- over
- methylene
- 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.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses a preparation method of a composite membrane with functions of adsorbing and separating heavy metal ions. Firstly, a nylon-6 nano-fiber membrane is prepared by utilizing an electrostatic spinning method; secondly, hyperbranched poly amidoamine is adsorbed to the surface of the nylon-6 nano-fiber membrane by a physical effect; finally, the hyperbranched poly amidoamine is cross-linked by a chemical reaction so as to form a tubular membrane which is firmly attached to the surface of nylon-6 fibers. The preparation method sufficiently utilizes the characteristics of a large specific surface area and a high porosity of a nylon-6 electrostatic spun membrane and the characteristic of strong adsorption capacity of the hyperbranched poly amidoamine for the heavy metal ions. The material prepared by the preparation method is simple in preparation process, has a novel structure and is strong in adsorption capacity.
Description
One, technical field
The present invention relates to a kind of preparation method with the composite membrane of absorption and separation of heavy metal ions function, belong to the dirty water decontamination handles field.
Two, background technology
Along with the development of industrial civilization, a large amount of heavy metal ion such as copper, cobalt, chromium, cadmium, lead, isoionic industrial wastewater of mercury of containing is discharged in natural environment.Heavy metal ion not only can not to degrade by organism but also can enrichment in organism, thus cause various diseases and physical function is disorderly.The health of what these heavy metal ion were serious compromise natural environment and the mankind.
In the past few decades, the minimizing technology for heavy metal ion mainly contains sedimentation, hyperfiltration, coprecipitation, ion-exchange, absorption method.Wherein, absorption method is one of most effective method.The sorbing material of present extensive use has: activated carbon granule, zeolite granular, Chitosan powder, clay mineral powder etc.But these materials all have some limitations in actual application as: be difficult to recycle and reuse.
A large amount of amino is there is and amide groups can carry out chelating with heavy metal ion in over-branched polyamidoamine (HPAMAM) structure.Therefore over-branched polyamidoamine can be utilized to remove the heavy metal ion in the aqueous solution as adsorbent.But, in application process, over-branched polyamidoamine must be attached to specific carrier surface in some way, recycling of sorbing material could be realized.
At present in visible following research, over-branched polyamidoamine and other polymer is utilized jointly to prepare composite membrane or compound resin adsorbs the heavy metal ion in water.
" membrane science " (JournalofMembraneScience, 396 volume 83 pages in 2012) report and utilize polysulphone film and over-branched polyamidoamine to prepare composite membrane, first author utilizes one kettle way to prepare over-branched polyamidoamine, carry out modified utilizing palmitoyl chloride to it, jointly be dissolved in 1-METHYLPYRROLIDONE with polysulfones, finally utilize mixed solution through the composite membrane of phase inversion preparation containing different quality mark dissaving polymer.And utilize this composite membrane to adsorb the cadmium ion in the aqueous solution.This technology make use of hydrophobic interaction (physical method) and is combined with resin matrix by over-branched polyamidoamine.
" hazardous material " (JournalofHazardousMaterials, 263 volume 311 pages in 2013) reports and utilizes macroreticular weakly base aminostyryl series anion exchange resin chemical graft over-branched polyamidoamine.Finally adding excessive diphenylphosphoryl dichloro to react and obtain end product in 12 hours, take polystyrene microsphere as carrier, through chemical mode in conjunction with over-branched polyamidoamine, and with the sorbing material of phosphate group modification.And utilize this product to adsorb the uranium ion in water.This technology make use of chemical method (covalent bond grafting) and is combined with resin matrix by over-branched polyamidoamine.
" membrane science " (JournalofMembraneScience, 448 volume 125 pages in 2013) reports the polytetrafluoroethylene film of over-branched polyamidoamine modification.Author first utilize ethylenediamine under ultraviolet light to polytetrafluoroethylene film carry out amino modified then utilize Cyanuric Chloride the over-branched polyamidoamine that one pot process is good is grafted to amino modified after polytetrafluoroethylene film prepare laminated film, and utilize and change film adsorption treatment is carried out to copper ion in water.This technology make use of chemical method (covalent bond grafting) and is combined with resin matrix by over-branched polyamidoamine.
Three, summary of the invention
The present invention is directed to the present situation that Most current over-branched polyamidoamine adsorbent for heavy metal preparation process is loaded down with trivial details and tediously long, propose a kind of preparation method of composite membrane with absorption and separation of heavy metal ions function, technique simply, sorbing material with carrier in conjunction with firm.
The present invention has the preparation method of the composite membrane of absorption and separation of heavy metal ions function, comprises the steps:
(1) dissolve nylon 6 with formic acid and acetic acid mixed solvent, preparation quality mark is nylon 6 spinning solution of 17.5wt%, and then regulate receiving range to be 15cm, voltage 20kV, at room temperature electrospinning, obtained thickness is the electrospinning film of 0.08-0.12mm;
(2) gained electrospinning film is cut to 5cm × 4cm size, is immersed into in DMF and the water over-branched polyamidoamine solution that is mixed solvent, dry with in the baking oven being placed on 80 DEG C;
(3) product that step (2) obtains is placed in N, in the mixed solution of N-methylene-bisacrylamide and acetone, crosslinked under the condition of 50 DEG C of condensing refluxes, obtained over-branched polyamidoamine modification of nylon 6 nano-fiber composite film.
In described formic acid and acetic acid mixed solvent, the mass ratio of formic acid and acetic acid is 1:1-3:1.
Described in step (2), the mass concentration of over-branched polyamidoamine solution is 2.5-10wt%.
In the mixed solvent that step (2) uses, the mass ratio of DMF and water is 2:1-4:1.
The N that step (3) uses, in the mixed solution of N-methylene-bisacrylamide and acetone, the mass concentration of N, N-methylene-bisacrylamide is 2-8wt%.
In step (3), crosslinking time is 6-12h.
Described HPAMAM is over-branched polyamidoamine, is to obtain through Michael addition reaction according to the ingredient proportion that mol ratio is 2:1-1:2 by containing amino monomer N-aminoethyl piperazine and the monomer containing two double bonds.Described polymeric reaction temperature is 30-70 DEG C.The described reaction time is 2-7 days.The described monomer containing two double bonds is selected from N, the mixture of one or more in N '-methylene-bisacrylamide, N, N '-cystamine bisacrylamide, BDO double methacrylate.
Method of electrostatic spinning can prepare nano fibrous membrane fast and effectively.Compared with traditional tree adipose membrane, electrospun fibers film has higher specific surface area and porosity.In conjunction with over-branched polyamidoamine and electrospun fibers film advantage made by heavy metal ion adsorbing material can improve adsorption efficiency.
Over-branched polyamidoamine combines with the advantage of static spinning membrane by the present invention, proposes a kind of new process and prepares heavy metal ion adsorbing material.First, the nano fibrous membrane of nylon 6 is obtained with method of electrostatic spinning; Secondly, take out after DMF/ aqueous solution nylon static spinning membrane being placed in over-branched polyamidoamine soaks a period of time, and dry; 3rd, dried over-branched polyamidoamine/nylon membrane is refluxed in the acetone soln of N, N-methylene-bisacrylamide, makes over-branched polyamidoamine generation cross-linking reaction, be attached to securely on nylon nano fiber.First this process utilizes physisorption that over-branched polyamidoamine sorbing material is combined in the surface of nylon electrospun fibers, utilizes chemical crosslinking effect to be combined in securely on nylon electrospun fibers by over-branched polyamidoamine subsequently.Technical process is simple, and sorbing material and carrier are in conjunction with firm.
This novel absorption material has bigger serface, high porosity characteristic; Macroscopically, sorbing material has tridimensional network; On microcosmic, every root network chain all has nucleocapsid structure.Its preparation flow relative ease, film sorbing material is easy to use, has recuperability.
The present invention has following features:
1, method of electrostatic spinning film forming, prepares HPAMAM/ nylon nano composite membrane by the mode of first physics immersion, rear chemical crosslinking, simple to operate, fast, with short production cycle.
2, combine firmly between the HPAMAM/ nylon nano composite membrane sorbing material that use is soaked, prepared by crosslinked method and carrier, can realize repeatedly, recycle.
3, prepared nano composite membrane is as sorbing material, and adsorption operations is simple, the rate of adsorption is fast.
Four, accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of nano-composite fiber film in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of nylon-6 static spinning membrane (left side) and HPAMAM/ nylon-6 electrostatic spinning composite membrane (right side).Contrast known, simple nylon electrostatic spinning diameter is less than 100nm, and after HPAMAM solution soaks, nylon electrostatic spinning all increases to about 200nm, can effectively be attached to nylon electrostatic spinning surface by inference HPAMAM.
Fig. 3 is the microstructure schematic diagram of nano-composite fiber film in embodiment 1.All be attached with HPAMAM on every root nylon-6 fiber surface, form microcosmic tubular structure with it.
Fig. 4 be in embodiment 1 nano-composite fiber film on cobalt ions adsorption time in natural water body on the impact of adsorption effect.Adsorption conditions pH=6, m/v=0.5g/L, c (Co
2+)=30mg/L, (m is adsorbent mass, and v is cobalt ions overall solution volume).By finding out in Fig. 4 that the adsorption efficiency of 100min to Co (II) all increases rapidly and reach stationary value and no longer change before absorption.The adsorption site absorption reaching 60min caudacoria surface when the time is saturated, reaches adsorption equilibrium.Equilibrium adsorption capacity is 32.23mg/g.
Five, detailed description of the invention
Embodiment 1:
(1) nylon 6 is dissolved with formic acid and acetic acid mixed solvent (formic acid, quality of acetic acid are than being 1:1), preparation quality mark is nylon 6 spinning solution of 17.5wt%, then receiving range is regulated to be 15cm, voltage 20kV, at room temperature electrospinning, obtained thickness is the electrospinning film of 0.08-0.12mm;
(2) by MBA (N, N-methylene-bisacrylamide) (10.175g) and AEPZ (N-aminoethyl piperazine) (8.527g) join in 120mL methanol/water mixed solvent (volume ratio of methyl alcohol and water is 7:3), polymerisation 5 days under 50 DEG C of constant temperature and condensing reflux condition, products therefrom is precipitated twice in ice acetone, the polymer precipitated is moved into vacuum drying chamber, dry 12h under room temperature condition ,-0.1MPa vacuum, obtain over-branched polyamidoamine, move in desiccator for subsequent use.
(3) gained electrospinning film is cut to 5cm × 4cm size, is immersed into in DMF and the water over-branched polyamidoamine solution that is mixed solvent, dry with in the baking oven being placed on 80 DEG C; In mixed solvent, the mass ratio of DMF and water is 4:1; The mass concentration of over-branched polyamidoamine solution is 2.5wt%;
(4) product that step (3) obtains is placed in N, in the mixed solution of N-methylene-bisacrylamide and acetone, crosslinked 6h under the condition of 50 DEG C of condensing refluxes, obtained over-branched polyamidoamine modification of nylon 6 nano-fiber composite film.In the mixed solution of wherein N, N-methylene-bisacrylamide and acetone, the mass concentration of N, N-methylene-bisacrylamide is 2wt%.
Embodiment 2:
(1) nylon 6 is dissolved with formic acid and acetic acid mixed solvent (formic acid, quality of acetic acid are than being 1:1), preparation quality mark is nylon 6 spinning solution of 17.5wt%, then receiving range is regulated to be 15cm, voltage 20kV, at room temperature electrospinning, obtained thickness is the electrospinning film of 0.08-0.12mm;
(2) by MBA (N, N-methylene-bisacrylamide) (10.175g) and AEPZ (N-aminoethyl piperazine) (8.527g) join in 120mL methanol/water mixed solvent (volume ratio of methyl alcohol and water is 7:3), polymerisation 5 days under 50 DEG C of constant temperature and condensing reflux condition, products therefrom is precipitated twice in ice acetone, the polymer precipitated is moved into vacuum drying chamber, dry 12h under room temperature condition ,-0.1MPa vacuum, obtain over-branched polyamidoamine, move in desiccator for subsequent use.
(3) gained electrospinning film is cut to 5cm × 4cm size, is immersed into in DMF and the water over-branched polyamidoamine solution that is mixed solvent, dry with in the baking oven being placed on 80 DEG C; In mixed solvent, the mass ratio of DMF and water is 4:1; The mass concentration of over-branched polyamidoamine solution is 5wt%;
(4) product that step (3) obtains is placed in N, in the mixed solution of N-methylene-bisacrylamide and acetone, crosslinked 6h under the condition of 50 DEG C of condensing refluxes, obtained over-branched polyamidoamine modification of nylon 6 nano-fiber composite film.In the mixed solution of wherein N, N-methylene-bisacrylamide and acetone, the mass concentration of N, N-methylene-bisacrylamide is 2wt%.
Embodiment 3:
(1) nylon 6 is dissolved with formic acid and acetic acid mixed solvent (formic acid, quality of acetic acid are than being 1:1), preparation quality mark is nylon 6 spinning solution of 17.5wt%, then receiving range is regulated to be 15cm, voltage 20kV, at room temperature electrospinning, obtained thickness is the electrospinning film of 0.08-0.12mm;
(2) by MBA (N, N-methylene-bisacrylamide) (10.175g) and AEPZ (N-aminoethyl piperazine) (8.527g) join in 120mL methanol/water mixed solvent (volume ratio of methyl alcohol and water is 7:3), polymerisation 5 days under 50 DEG C of constant temperature and condensing reflux condition, products therefrom is precipitated twice in ice acetone, the polymer precipitated is moved into vacuum drying chamber, dry 12h under room temperature condition ,-0.1MPa vacuum, obtain over-branched polyamidoamine, move in desiccator for subsequent use.
(3) gained electrospinning film is cut to 5cm × 4cm size, is immersed into in DMF and the water over-branched polyamidoamine solution that is mixed solvent, dry with in the baking oven being placed on 80 DEG C; In mixed solvent, the mass ratio of DMF and water is 4:1; The mass concentration of over-branched polyamidoamine solution is 7.5wt%;
(4) product that step (3) obtains is placed in N, in the mixed solution of N-methylene-bisacrylamide and acetone, crosslinked 6h under the condition of 50 DEG C of condensing refluxes, obtained over-branched polyamidoamine modification of nylon 6 nano-fiber composite film.In the mixed solution of wherein N, N-methylene-bisacrylamide and acetone, the mass concentration of N, N-methylene-bisacrylamide is 2wt%.
Embodiment 4:
(1) nylon 6 is dissolved with formic acid and acetic acid mixed solvent (formic acid, quality of acetic acid are than being 3:1), preparation quality mark is nylon 6 spinning solution of 17.5wt%, then receiving range is regulated to be 15cm, voltage 20kV, at room temperature electrospinning, obtained thickness is the electrospinning film of 0.08-0.12mm;
(2) by MBA (N, N-methylene-bisacrylamide) (10.175g) and AEPZ (N-aminoethyl piperazine) (8.527g) join in 120mL methanol/water mixed solvent (volume ratio of methyl alcohol and water is 7:3), polymerisation 5 days under 50 DEG C of constant temperature and condensing reflux condition, products therefrom is precipitated twice in ice acetone, the polymer precipitated is moved into vacuum drying chamber, dry 12h under room temperature condition ,-0.1MPa vacuum, obtain over-branched polyamidoamine, move in desiccator for subsequent use.
(3) gained electrospinning film is cut to 5cm × 4cm size, is immersed into in DMF and the water over-branched polyamidoamine solution that is mixed solvent, dry with in the baking oven being placed on 80 DEG C; In mixed solvent, the mass ratio of DMF and water is 4:1; The mass concentration of over-branched polyamidoamine solution is 2.5wt%;
(4) product that step (3) obtains is placed in N, in the mixed solution of N-methylene-bisacrylamide and acetone, crosslinked 6h under the condition of 50 DEG C of condensing refluxes, obtained over-branched polyamidoamine modification of nylon 6 nano-fiber composite film.In the mixed solution of wherein N, N-methylene-bisacrylamide and acetone, the mass concentration of N, N-methylene-bisacrylamide is 4wt%.
Embodiment 5:
(1) nylon 6 is dissolved with formic acid and acetic acid mixed solvent (formic acid, quality of acetic acid are than being 2:1), preparation quality mark is nylon 6 spinning solution of 17.5wt%, then receiving range is regulated to be 15cm, voltage 20kV, at room temperature electrospinning, obtained thickness is the electrospinning film of 0.08-0.12mm;
(2) by MBA (N, N-methylene-bisacrylamide) (10.175g) and AEPZ (N-aminoethyl piperazine) (8.527g) join in 120mL methanol/water mixed solvent (volume ratio of methyl alcohol and water is 7:3), polymerisation 5 days under 50 DEG C of constant temperature and condensing reflux condition, products therefrom is precipitated twice in ice acetone, the polymer precipitated is moved into vacuum drying chamber, dry 12h under room temperature condition ,-0.1MPa vacuum, obtain over-branched polyamidoamine, move in desiccator for subsequent use.
(3) gained electrospinning film is cut to 5cm × 4cm size, is immersed into in DMF and the water over-branched polyamidoamine solution that is mixed solvent, dry with in the baking oven being placed on 80 DEG C; In mixed solvent, the mass ratio of DMF and water is 4:1; The mass concentration of over-branched polyamidoamine solution is 2.5wt%;
(4) product that step (3) obtains is placed in N, in the mixed solution of N-methylene-bisacrylamide and acetone, crosslinked 10h under the condition of 50 DEG C of condensing refluxes, obtained over-branched polyamidoamine modification of nylon 6 nano-fiber composite film.In the mixed solution of wherein N, N-methylene-bisacrylamide and acetone, the mass concentration of N, N-methylene-bisacrylamide is 4wt%.
Claims (9)
1. there is a preparation method for the composite membrane of absorption and separation of heavy metal ions function, it is characterized in that comprising the steps:
(1) dissolve nylon 6 with formic acid and acetic acid mixed solvent, preparation quality mark is nylon 6 spinning solution of 17.5wt%, and then regulate receiving range to be 15cm, voltage 20kV, at room temperature electrospinning, obtained thickness is the electrospinning film of 0.08-0.12mm;
(2) gained electrospinning film is cut to 5cm × 4cm size, is immersed into in DMF and the water over-branched polyamidoamine solution that is mixed solvent, dry with in the baking oven being placed on 80 DEG C;
(3) product that step (2) obtains is placed in N, in the mixed solution of N-methylene-bisacrylamide and acetone, crosslinked under the condition of 50 DEG C of condensing refluxes, obtained over-branched polyamidoamine modification of nylon 6 nano-fiber composite film.
2. preparation method according to claim 1, is characterized in that:
In described formic acid and acetic acid mixed solvent, the mass ratio of formic acid and acetic acid is 1:1-3:1.
3. preparation method according to claim 1, is characterized in that:
Described in step (2), the mass concentration of over-branched polyamidoamine solution is 2.5-10wt%.
4. preparation method according to claim 1, is characterized in that:
In the mixed solvent that step (2) uses, the mass ratio of DMF and water is 2:1-4:1.
5. preparation method according to claim 1, is characterized in that:
The N that step (3) uses, in the mixed solution of N-methylene-bisacrylamide and acetone, the mass concentration of N, N-methylene-bisacrylamide is 2-8wt%.
6. preparation method according to claim 1, is characterized in that:
In step (3), crosslinking time is 6-12h.
7. preparation method according to claim 1, is characterized in that:
Described over-branched polyamidoamine obtains through Michael addition reaction according to the ingredient proportion that mol ratio is 2:1-1:2 by containing amino monomer N-aminoethyl piperazine and the monomer containing two double bonds.
8. preparation method according to claim 7, is characterized in that:
The reaction temperature of described Michael addition reaction is 30-70 DEG C, reaction time 2-7 days.
9. preparation method according to claim 7, is characterized in that:
The described monomer containing two double bonds is selected from N, the mixture of one or more in N '-methylene-bisacrylamide, N, N '-cystamine bisacrylamide, BDO double methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510707679.2A CN105268417B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of the composite membrane with adsorbing separation heavy metal ion function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510707679.2A CN105268417B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of the composite membrane with adsorbing separation heavy metal ion function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105268417A true CN105268417A (en) | 2016-01-27 |
| CN105268417B CN105268417B (en) | 2017-06-30 |
Family
ID=55138771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510707679.2A Expired - Fee Related CN105268417B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of the composite membrane with adsorbing separation heavy metal ion function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105268417B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669986A (en) * | 2016-03-14 | 2016-06-15 | 岭南师范学院 | Hyperbranched polyamide modified chitosan quaternary ammonium salt microsphere for wastewater treatment and preparation method and application thereof |
| CN107433191A (en) * | 2017-07-31 | 2017-12-05 | 河南工程学院 | Insoluble impurities can be filtered and adsorb the preparation method of the multifunctional composite film of heavy metal ion |
| CN108160054A (en) * | 2017-12-28 | 2018-06-15 | 大连海洋大学 | A kind of nylon membrane preparation method for adsorbing heavy metal |
| CN109231344A (en) * | 2018-10-30 | 2019-01-18 | 中国工程物理研究院核物理与化学研究所 | A kind of polyamines class uranium absorption material and preparation method thereof |
| CN113967469A (en) * | 2020-07-22 | 2022-01-25 | 中国科学院上海高等研究院 | Preparation method of heavy metal adsorption material with antibacterial property |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0994157A1 (en) * | 1998-10-12 | 2000-04-19 | Dsm N.V. | Molecular reinforced polymeric composition |
| CN1974634A (en) * | 2006-12-20 | 2007-06-06 | 东华大学 | Method of improving the machinability of polyamide |
-
2015
- 2015-10-27 CN CN201510707679.2A patent/CN105268417B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0994157A1 (en) * | 1998-10-12 | 2000-04-19 | Dsm N.V. | Molecular reinforced polymeric composition |
| CN1974634A (en) * | 2006-12-20 | 2007-06-06 | 东华大学 | Method of improving the machinability of polyamide |
Non-Patent Citations (5)
| Title |
|---|
| KUK NAM HAN等: "Hyperbranched poly(amidoamine)/polysulfone composite membranes for Cd(II) removal from water", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| MAMADOU S . D I A L L O等: "Poly(amidoamine) Dendrimers: A New Class of High Capacity Chelating Agents for Cu(II) Ions", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
| T. HUBER等: "Blends of hyperbranched poly(ether amide)s and polyamide-6", 《MACROMOL. MATER. ENG.》 * |
| WEI WEI等: "Removal of Cd(Ⅱ) from aqueous solution by Electrospun Nylon 6 Nanofibrous Nonwoven containing Attapulgite", 《ADVANCED MATERIALS RESEARCH》 * |
| 占珊等: "超支化聚合物改性P A 6 的研究", 《合成纤维工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669986A (en) * | 2016-03-14 | 2016-06-15 | 岭南师范学院 | Hyperbranched polyamide modified chitosan quaternary ammonium salt microsphere for wastewater treatment and preparation method and application thereof |
| CN105669986B (en) * | 2016-03-14 | 2018-09-28 | 岭南师范学院 | A kind of use in waste water treatment ultrabranching polyamide modified quaternary ammonium salt of chitosan microballoon and its preparation method and application |
| CN107433191A (en) * | 2017-07-31 | 2017-12-05 | 河南工程学院 | Insoluble impurities can be filtered and adsorb the preparation method of the multifunctional composite film of heavy metal ion |
| CN107433191B (en) * | 2017-07-31 | 2019-11-29 | 河南工程学院 | Insoluble impurities can be filtered and adsorb the preparation method of the multifunctional composite film of heavy metal ion |
| CN108160054A (en) * | 2017-12-28 | 2018-06-15 | 大连海洋大学 | A kind of nylon membrane preparation method for adsorbing heavy metal |
| CN109231344A (en) * | 2018-10-30 | 2019-01-18 | 中国工程物理研究院核物理与化学研究所 | A kind of polyamines class uranium absorption material and preparation method thereof |
| CN113967469A (en) * | 2020-07-22 | 2022-01-25 | 中国科学院上海高等研究院 | Preparation method of heavy metal adsorption material with antibacterial property |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105268417B (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Van Tran et al. | Hydrogel applications for adsorption of contaminants in water and wastewater treatment | |
| CN105268417A (en) | Preparation method of composite membrane with functions of adsorbing and separating heavy metal ions | |
| Xu et al. | Functionalized polyethersulfone nanofibrous membranes with ultra-high adsorption capacity for organic dyes by one-step electrospinning | |
| US11560438B2 (en) | Porous polymeric cellulose prepared via cellulose crosslinking | |
| Kwak et al. | Polyethylenimine-functionalized silk sericin beads for high-performance remediation of hexavalent chromium from aqueous solution | |
| Min et al. | Micro-nano structure poly (ether sulfones)/poly (ethyleneimine) nanofibrous affinity membranes for adsorption of anionic dyes and heavy metal ions in aqueous solution | |
| Gao et al. | Electrospun molecularly imprinted sodium alginate/polyethylene oxide nanofibrous membranes for selective adsorption of methylene blue | |
| CN108465377B (en) | Preparation method of regenerated cellulose/chitosan composite antibacterial nanofiltration membrane | |
| Kani et al. | Pollutant decontamination by polyethyleneimine-engineered agricultural waste materials: a review | |
| CN100537021C (en) | Method for preparing ammonifiers adosorbant | |
| CN104587981A (en) | Nanofiber membrane with heavy metal adsorbing function and preparation method of nanofiber membrane | |
| CN102784625A (en) | Radiation synthetic method for high-speed selective adsorption material | |
| Yalçın et al. | Silk fibroin/nylon-6 blend nanofilter matrix for copper removal from aqueous solution | |
| Xu et al. | Hardwood vessel-inspired chitosan-based sponge with superior compressibility, superfast adsorption and remarkable recyclability for microplastics removal in water | |
| Haider et al. | Fabrication of the diethylenetriamine grafted polyacrylonitrile electrospun nanofibers membrane for the aqueous removal of cationic dyes | |
| CN109589943A (en) | A method of preparing cadmium (II) ion blotting composite membrane | |
| CN106824120B (en) | Recyclable carbon fiber adsorbent and preparation and application thereof | |
| CN101875003B (en) | Preparation method of adsorbent resin with Cr ion cavities | |
| CN106592214A (en) | Preparation method of amphoteric ion exchange fiber | |
| KR101521991B1 (en) | Waterborne polyurethane/hydroxyapatite/textile sorbent for heavy metal ions and a method for manufacturing the same | |
| JP4875025B2 (en) | Polyvinyl alcohol molding | |
| CN113000034B (en) | Preparation method of uranium ion affinity membrane based on natural plant polyphenol composite coating | |
| KR101673928B1 (en) | Polyketone cotion exchange membrane and manufacturing method thereof | |
| CN111282556B (en) | Defluorination composite fiber membrane, preparation method and application thereof | |
| CN113880182A (en) | Preparation method of modified activated carbon filter element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20170630 Termination date: 20201027 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |