CN113042010A - Heavy metal chelating adsorption material and preparation method and application thereof - Google Patents
Heavy metal chelating adsorption material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113042010A CN113042010A CN202110273327.6A CN202110273327A CN113042010A CN 113042010 A CN113042010 A CN 113042010A CN 202110273327 A CN202110273327 A CN 202110273327A CN 113042010 A CN113042010 A CN 113042010A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- metal chelating
- adsorption
- ions
- adsorption material
- 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
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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a heavy metal chelating adsorption material, and a preparation method and application thereof, and belongs to the field of porous material preparation and functionalization. According to the invention, firstly, a high internal phase emulsion template method is used for preparing polyHIPE, then, amino is introduced by utilizing an epoxy functional group of a hydrophobic monomer in the polyHIPE, and then a heavy metal chelating agent is fixed on a polyHIPE carrier through the amino to prepare the heavy metal chelating adsorption material which is easy to separate, can circulate and has a good adsorption effect. The data of the examples show that the adsorption equilibrium values of the heavy metal chelate adsorbent prepared by the invention on Cu (II) ions and Cr (III) ions are 0.6mg/L and 0.3mg/L respectively.
Description
Technical Field
The invention relates to the technical field of porous material preparation and functionalization, and particularly relates to a heavy metal chelating adsorption material and a preparation method and application thereof.
Background
The increasing water pollution, especially heavy metal pollution, has posed a serious threat to human society and ecological environment. With the development of industrialization, various heavy metal ion wastewater is inevitably generated in many industries. When heavy metal ions such as arsenic, lead, cadmium, nickel, chromium, zinc, copper, mercury, cobalt and the like generated in the production of metal plating, mining, tanning, paint, batteries, chemical fertilizers and the like enter a water body in a direct or indirect mode, the heavy metal pollution of the water body is caused. The heavy metal ions are extremely toxic and non-degradable, can be enriched in organisms, seriously damage the ecological environment and threaten the human health. Therefore, it is necessary to treat the water body contaminated with heavy metal ions. Commonly used methods for removing heavy metal ions from water are membrane filtration, flocculation, adsorption, chemical precipitation, electrolysis and ion exchange. In contrast, adsorption is the most efficient, low cost and easy to operate, cyclic process.
Aminocarboxylic acids (APCAs) have good chelating properties and are useful as metal chelators for removing metal ions from sewage. The more carboxyl groups are contained in APCAs, the more stable the chelate formed by metal ions, the diethylenetriaminepentaacetic acid is one of the most carboxyl groups in common APCAs, and compared with other APCAs functionalized adsorbents, the diethylenetriaminepentaacetic acid-chitosan adsorbent has excellent absorption capacity in a strong acid solution (pH is 1.5-3.0), and Co (II) ions can be extracted from an aqueous solution of the chelate formed by EDTA and metal ions. However, the adsorption efficiency of the diethylenetriaminepentaacetic acid-chitosan to Cu (II) ions and Cr (III) ions is less than or equal to 90 percent, and the problem of low adsorption efficiency exists.
Disclosure of Invention
In view of the above, the present invention aims to provide a heavy metal chelating adsorption material, and a preparation method and an application thereof. The heavy metal chelate adsorption material prepared by the invention has high adsorption efficiency on Cu (II) ions and Cr (III) ions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a heavy metal chelating adsorption material, which comprises the following steps:
mixing an emulsifier, a photoinitiator, a cross-linking agent and a hydrophobic monomer to obtain an oil phase; the hydrophobic monomer contains an epoxy functional group;
mixing an electrolyte with water to obtain a water phase;
adding the aqueous phase to the stirred oil phase to obtain a high internal phase emulsion;
dispersing the high internal phase emulsion, and then carrying out photoinitiated polymerization to obtain a porous polymer;
mixing the porous polymer with an amination modifier to perform amination modification to obtain a modified product;
and mixing the modified product with a heavy metal chelating agent for grafting modification to obtain the heavy metal chelating adsorption material.
Preferably, the hydrophobic monomer is lauryl acrylate, tetradecyl methacrylate, or glycidyl methacrylate.
Preferably, the emulsifier comprises one or more of Span80, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, polyglycerol alkenyl succinate, and hypermer t 96.
Preferably, the cross-linking agent comprises ethylene glycol dimethacrylate and/or divinylbenzene.
Preferably, the amination modifier is hexamethylene diamine or ethylene diamine.
Preferably, the heavy metal chelating agent comprises one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid.
Preferably, the photoinitiator comprises one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and a, a-dimethoxy-a-phenylacetophenone.
Preferably, the mass ratio of the modified product to the heavy metal chelating agent is 2 +/-0.1: 10.
the invention also provides the heavy metal chelating adsorption material prepared by the preparation method of the technical scheme.
The invention also provides application of the heavy metal chelating adsorption material in the technical scheme in the field of heavy metal adsorption.
The invention provides a preparation method of a heavy metal chelating adsorption material, which comprises the following steps:
mixing an emulsifier, a photoinitiator, a cross-linking agent and a hydrophobic monomer to obtain an oil phase; the hydrophobic monomer contains an epoxy functional group; mixing an electrolyte with water to obtain a water phase; adding the aqueous phase to the stirred oil phase to obtain a high internal phase emulsion; dispersing the high internal phase emulsion, and then carrying out photoinitiated polymerization to obtain a porous polymer; mixing the porous polymer with an amination modifier to perform amination modification to obtain a modified product; and mixing the modified product with a heavy metal chelating agent for grafting modification to obtain the heavy metal chelating adsorption material.
Compared with the prior art, the invention has the following beneficial effects:
the principle of the invention is as follows: high Internal Phase Emulsions (HIPE) are defined as emulsions having a volume fraction of internal phase or droplet phase of greater than or equal to 74%, at least 74% by volume of the high internal phase emulsion being composed of droplets. 74% is the maximum internal phase volume fraction that can be achieved when spherical droplets of uniform size are closely packed (without deformation). The volume of the internal phase can be made higher when the droplets are not uniform in size or are extruded as polyhedrons. HIPEs are mainly classified into W/O (water-in-oil) type, O/W (oil-in-water) type and O/O (oil-in-oil) type according to the hydrophilic and hydrophobic properties of the inner and outer phases. Porous materials prepared by solidifying the continuous (or non-droplet) phase of a high internal phase emulsion are known as polyHIPEs. Dissolving the monomer in oil phase, dispersing the oil phase in water phase by stirring to form HIPE, polymerizing to obtain solid material, and removing internal phase to obtain porous polymer (polyHIPEs). The spherical cavities formed by the emulsion droplets are called "macropores" (voids), and the interconnected pores between macropores are called "interconnected pores" (windows).
The performance of the adsorbent is closely related to the specific surface area, internal pore structure and surface functional group properties. The porous material has high specific surface area, large pore volume, regular pore diameter and distribution and highly communicated through hole structure besides good physical and chemical stability. The PolyHIPEs have a super-macroporous structure, and the macropores are mutually communicated to form a highly open-pore structure, so that the specific surface area of the polymer material is increased, the mass transfer process can be faster and more efficient, the amination modification and metal chelating agent access effects are further improved in subsequent grafting modification, and the method is particularly suitable for mass transfer of macromolecular substances.
According to the invention, firstly, a high internal phase emulsion template method is used for preparing polyHIPE, then, amino is introduced by utilizing an epoxy functional group of a hydrophobic monomer in the polyHIPE, and then a heavy metal chelating agent is fixed on a polyHIPE carrier through the amino to prepare the heavy metal chelating adsorption material which is easy to separate, can circulate and has a good adsorption effect. The data of the examples show that the adsorption equilibrium values of the heavy metal chelate adsorbent prepared by the invention on Cu (II) ions and Cr (III) ions are 0.6mg/L and 0.3mg/L respectively.
Detailed Description
The invention provides a preparation method of a heavy metal chelating adsorption material, which comprises the following steps:
mixing an emulsifier, a photoinitiator, a cross-linking agent and a hydrophobic monomer to obtain an oil phase; the hydrophobic monomer contains an epoxy functional group;
mixing an electrolyte with water to obtain a water phase;
adding the aqueous phase to the stirred oil phase to obtain a high internal phase emulsion;
dispersing the high internal phase emulsion, and then carrying out photoinitiated polymerization to obtain a porous polymer;
mixing the porous polymer with an amination modifier to perform amination modification to obtain a modified product;
and mixing the modified product with a heavy metal chelating agent for grafting modification to obtain the heavy metal chelating adsorption material.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
Mixing an emulsifier, a photoinitiator, a cross-linking agent and a hydrophobic monomer to obtain an oil phase; the hydrophobic monomer contains an epoxy functional group.
In the present invention, the hydrophobic monomer is preferably lauryl acrylate, tetradecyl methacrylate, or glycidyl methacrylate; the mass fraction of the hydrophobic monomer in the oil phase is preferably 50% to 70%.
In the present invention, the emulsifier preferably comprises one or more of Span80, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer (L-81), polyglycerol alkenyl succinate and hypermer t 96; the mass fraction of the emulsifier in the oil phase is preferably 10-25%.
In the present invention, the crosslinking agent preferably includes ethylene glycol dimethacrylate and/or divinylbenzene; the mass fraction of the cross-linking agent in the oil phase is preferably 20% to 24%.
In the present invention, the photoinitiator preferably comprises one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and a, a-dimethoxy-a-phenylacetophenone; the mass fraction of the photoinitiator in the oil phase is preferably 0.01-0.03%; the photoinitiator can enable the water-in-oil type high internal phase emulsion to contain the photoinitiator, the photoinitiator can be used for initiating a hydrophobic monomer in the emulsion under the ultraviolet light initiation condition, so that a porous polymer with an adjustable pore structure can be obtained, and then amination modification and introduction of a metal chelating agent are carried out on the obtained porous polymer.
In the present invention, the photoinitiator is preferably used in an amount of 1% to 3% by mass based on the hydrophobic monomer.
The invention mixes the electrolyte and water to obtain water phase.
In the present invention, the electrolyte is preferably calcium chloride or sodium chloride; the mass fraction of the electrolyte in the water phase is preferably 0.5-3%.
The electrolyte is added into water to obtain the water phase.
After the water phase and the oil phase are obtained, the invention adds the water phase to the oil phase while stirring to obtain the high internal phase emulsion.
In the invention, the volume ratio of the oil phase to the water phase is preferably 1: 8-1: 20.
In the present invention, the rotation speed of the oil phase during the stirring is preferably 300 to 500 rpm.
After obtaining the high internal phase emulsion, the invention disperses the high internal phase emulsion and then carries out photoinitiated polymerization to obtain the porous polymer (GMA).
In the present invention, the dispersion is preferably a bead, a block or a plate-like droplet, and more preferably a bead because the bead has a larger specific surface area and higher adsorption efficiency.
The present invention preferably employs a syringe pump to bead the high internal phase emulsion into an aqueous solution of polyvinyl alcohol. The concentration and amount of the aqueous polyvinyl alcohol solution are not particularly limited, and the rate of dropping the high internal phase emulsion into the aqueous polyvinyl alcohol solution is not particularly limited.
In the invention, the photo-initiated polymerization is preferably carried out by using an ultraviolet lamp with the wavelength of 254nm or 365nm, and the time for photo-initiated polymerization is preferably 6-12 h, and more preferably 8-10 h.
After the photo-initiated polymerization is completed, the photo-initiated polymerization product is preferably washed by a rinsing solvent and then dried to obtain the porous polymer, and the porous polymer is a white bead polymer.
In the present invention, the rinsing solvent is preferably water and/or ethanol, and the specific parameters for rinsing are not particularly limited in the present invention.
The temperature and time for drying are not particularly limited in the present invention.
After the porous polymer is obtained, the porous polymer and an amination modifier are mixed for amination modification to obtain a modified product.
In the present invention, the amination modifier is preferably hexamethylenediamine or ethylenediamine.
In the present invention, the mass ratio of the porous polymer to the amination modifier is preferably 2 ± 0.1: 5, the amination modifier is preferably used in the form of an aqueous amination modifier solution, the concentration of which is preferably 4 wt.%.
In the invention, the temperature of the amination modification is preferably 55 +/-15 ℃ and the time is preferably 24 +/-3 h, and the amination modification is preferably carried out at N2The reaction is carried out under the atmosphere; in the amination modification process, the amino group in the amination modifier and an epoxy group on GMA undergo a ring opening reaction.
After the amination modification is finished, the amination modification is preferably sequentially stirred in an acetic acid solution at a low speed, washed by a leaching solvent and then dried to obtain the modified product.
In the present invention, the rotation speed of the low-speed stirring is preferably 150 rpm.
In the present invention, the rinsing solvent is preferably water and/or ethanol, and the specific parameters for rinsing are not particularly limited in the present invention.
The temperature and time for drying are not particularly limited in the present invention.
After the modified product is obtained, the modified product is mixed with a heavy metal chelating agent for grafting modification, so that the heavy metal chelating adsorption material is obtained.
In the present invention, the heavy metal chelating agent preferably comprises one or more of iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA).
In the present invention, the mass ratio of the modified product to the heavy metal chelator is preferably 2 ± 0.1: 10.
in the present invention, during the graft modification, the heavy metal chelating agent is immobilized on the porous polymer through an amino group.
In the invention, the temperature of the grafting modification is preferably 40-70 ℃, and the time is preferably 21-27 h.
In the invention, the pH value of the grafting modification is preferably 8-9, more preferably 8.5, and the pH value of 8-9 is favorable for the reaction of the heavy metal chelating agent and amino. The present invention is not particularly limited with respect to the type, concentration and amount of the pH adjustor.
In the present invention, it is preferable to mix the modified product with a solution of DMTMM (4- (4, 6-dimethoxytriazin-2-yl) -4-methylmorpholine hydrochloride) and then with the heavy metal chelating agent. The concentration of the DMTMM solution is not particularly limited in the present invention.
The invention also provides the heavy metal chelating adsorption material prepared by the preparation method of the technical scheme.
The invention also provides application of the heavy metal chelating adsorption material in the technical scheme in the field of heavy metal adsorption.
In the present invention, the heavy metal is preferably Cu (II) ion and/or Cr (III).
The present invention is not particularly limited to the specific operation of the adsorption.
In order to further illustrate the present invention, the following examples are provided to describe the heavy metal chelating adsorption material and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention.
In the embodiment of the invention, the microscopic morphology of the heavy metal chelate adsorption material is observed by a scanning electron microscope (SEM, Hitachi S-3400, Hitachi), the mass and the volume of the heavy metal chelate adsorption material are respectively measured by a balance and a vernier caliper, the porosity is calculated, and the concentrations of Cu (II) ions and Cr (III) before and after adsorption are tested by ICP-OES (Agilent725 ES).
Example 1
Taking monomer glycidyl methacrylate (2.32g), crosslinking agent ethylene glycol dimethacrylate (1.44g), photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (129mg) and emulsifier (L-81)0.65g as oil phase, weighing 0.18g of calcium chloride dihydrate, adding the calcium chloride dihydrate into 10.12g of water solution as water phase, and adding the water phase into the oil phase which is stirred (500rpm) to obtain the high internal phase emulsion. Then dripping the high internal phase emulsion into a polyvinyl alcohol aqueous solution by a syringe pump drop by drop, and initiating a reaction (254nm ultraviolet lamp, 12h) by ultraviolet light after the reaction is finishedThus obtaining the bead-shaped porous polymer. 2g of the beaded porous polymer was then weighed into a round bottom flask, and a solution of hexamethylenediamine (4% by weight, 120mL) was poured in an oil bath N at 50 deg.C2The reaction was stirred under atmosphere for 24 h. After the reaction, the reaction mixture was thoroughly immersed in ultrapure water to remove excess hexamethylenediamine. The aminated porous bead polymer thus prepared was placed in a round-bottomed flask, poured into an acetic acid solution and stirred at a low speed (150rpm) for 5 hours, followed by being placed in ultrapure water and then transferred to the round-bottomed flask after being sufficiently soaked. Preparing 30mL of diethylenetriamine pentaacetic acid aqueous solution (containing 2g of diethylenetriamine pentaacetic acid) and 4mL of DMTMM solution (mixing 4mL of DMTMM solution and 10g of aminated bead-shaped porous polymer), mixing, adjusting the pH value of the mixed solution to 8-9, and pouring into a round-bottom flask. Stirring at the rotating speed of 250rpm for 5h at room temperature to carry out grafting reaction, and fully soaking the product in ultrapure water after the reaction is finished. And finally, drying the product in a vacuum oven to obtain the bead-shaped heavy metal chelating adsorption material which is easy to separate and recycle.
Taking 0.3g of bead-shaped heavy metal chelate adsorption material and 10mL of prepared solution containing 25mg/L of Cu (II) ions and Cr (III) ions at the same time, carrying out ICP-OES (Agilent725ES) test on the filtrate after adsorbing for a certain time, and determining the concentrations of the Cu (II) ions and the Cr (III).
And (3) observing the morphology of the porous material by adopting a scanning electron microscope (SEM, Hitachi S-3400, Hitachi), wherein the pore diameter of the obtained porous material is 5-15 mu m.
The adsorption effect of the heavy metal chelate adsorption material prepared in example 1 is tested, different grouping experiments of the same batch of samples are carried out, the error is reduced, the maximum saturated adsorption amount can be reached in 15min, the time is far shorter than the time of saturated adsorption of Cu (II) ions and Cr (III) ions by the existing heavy metal ion adsorption material and is more than or equal to 70 minutes, the results are shown in Table 1, the heavy metal chelate adsorption material prepared by the invention has good adsorption efficiency on the Cu (II) ions and the Cr (III) ions, the adsorption efficiency on the Cu (II) ions and the Cr (III) ions is respectively 97.6 percent and 98.8 percent, the adsorption efficiency is far better than that of the existing adsorption material on the Cu (II) ions and the Cr (III) ions and is generally less than or equal to 90 percent, the adsorption equilibrium values of the prepared heavy metal adsorption material on the Cu (II) ions and the Cr (III) ions are respectively 0.6mg/L and 0.3mg/, respectively lower than 1.0mg/L specified by the national drinking water standard and 0.5mg/L specified by the ground water standard.
Table 1 adsorption effect data of the heavy metal chelate adsorption material prepared in example 1
| Ion type | Cu (II) ion | Cr (III) ion |
| Before adsorption | 25mg/L | 25mg/L |
| After adsorption | 0.6mg/L | 0.3mg/L |
And (3) putting the adsorption material reaching the maximum saturated adsorption quantity into hydrochloric acid and nitric acid 1: 1, oscillating and desorbing the mixed solution, and performing an adsorption experiment again by using an ICP-OES (Agilent725ES) test element analysis to prove that the adsorption amount in the table 1 can be still maintained after the adsorption material is repeatedly and circularly adsorbed for 10 times.
Example 2
Taking monomer glycidyl methacrylate (2.30g), crosslinking agent ethylene glycol dimethacrylate (1.42g), photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (132mg) and emulsifier (L-81)0.60g as oil phase, weighing 0.12g of calcium chloride dihydrate, adding the calcium chloride dihydrate into 9.26g of water solution as water phase, and adding the water phase into the oil phase which is stirred (300rpm) to obtain the high internal phase emulsion. Then using a syringe pumpDropwise adding the high internal phase emulsion into a polyvinyl alcohol aqueous solution, and initiating a reaction by using ultraviolet light (365nm ultraviolet lamp for 6 hours) to obtain the bead-shaped porous polymer. 2g of the beaded porous polymer was then weighed into a round bottom flask, and a solution of hexamethylenediamine (4% by weight, 120mL) was poured in an oil bath N at 60 ℃ C2The reaction was stirred under atmosphere for 24 h. After the reaction, the reaction mixture was thoroughly immersed in ultrapure water to remove excess hexamethylenediamine. The aminated porous bead polymer thus prepared was placed in a round-bottomed flask, poured into an acetic acid solution and stirred at a low speed (150rpm) for 6 hours, followed by being placed in ultrapure water and then transferred to the round-bottomed flask after being sufficiently soaked. 30mL of diethylenetriamine pentaacetic acid aqueous solution (containing 2g of diethylenetriamine pentaacetic acid) and 4mL of DMTMM solution (containing 10g of aminated beaded porous polymer) are mixed, and the pH of the mixed solution is adjusted to 8.5 and poured into a round-bottom flask. Stirring at the rotating speed of 250rpm for 6h at room temperature to carry out grafting reaction, and fully soaking the product in ultrapure water after the reaction is finished. And finally, drying the product in a vacuum oven to obtain the bead-shaped heavy metal chelating adsorption material which is easy to separate and recycle.
Taking 0.2g of bead-shaped heavy metal chelate adsorption material and 10mL of prepared solution containing 25mg/L of Cu (II) ions and Cr (III) ions at the same time, carrying out ICP-OES (Agilent725ES) test on the filtrate after adsorbing for a certain time, and determining the concentrations of the Cu (II) ions and the Cr (III).
And (3) observing the morphology of the porous material by adopting a scanning electron microscope (SEM, Hitachi S-3400, Hitachi), wherein the pore diameter of the obtained porous material is 5-20 mu m.
The adsorption effect of the heavy metal chelate adsorption material prepared in example 2 is tested, different grouping experiments of the same batch of samples are carried out, the error is reduced, the maximum saturated adsorption amount can be reached in 15min, the time is far shorter than the time of saturated adsorption of Cu (II) ions and Cr (III) ions by the existing heavy metal ion adsorption material and is more than or equal to 70 minutes, the results are shown in Table 2, the heavy metal chelate adsorption material prepared by the invention has good adsorption efficiency on the Cu (II) ions and the Cr (III) ions, the adsorption efficiency on the Cu (II) ions and the Cr (III) ions is respectively 96.8 percent and 98.4 percent, the adsorption efficiency is far better than that of the existing adsorption material on the Cu (II) ions and the Cr (III) ions and is generally less than or equal to 90 percent, the adsorption equilibrium values of the prepared heavy metal adsorption material on the Cu (II) ions and the Cr (III) ions are respectively 0.8mg/L and 0.4mg/, respectively lower than 1.0mg/L specified by the national drinking water standard and 0.5mg/L specified by the ground water standard.
Table 2 adsorption effect data of the heavy metal chelate adsorption material prepared in example 2
| Ion type | Cu (II) ion | Cr (III) ion |
| Before adsorption | 25mg/L | 25mg/L |
| After adsorption | 0.8mg/L | 0.4mg/L |
And (3) putting the adsorption material reaching the maximum saturated adsorption quantity into hydrochloric acid and nitric acid 1: 1, oscillating and desorbing the mixed solution, testing element analysis by ICP-OES (Agilent725ES) to prove that metal ions are desorbed into the solution again, performing adsorption experiment again, and after the adsorption material is repeatedly and circularly adsorbed for 10 times, keeping the adsorption equilibrium values of Cu (II) ions and Cr (III) ions at 0.5-0.8 mg/L and 0.3-0.5 mg/L after being circularly adsorbed for ten times.
Example 3
Monomer glycidyl methacrylate (2.42g), crosslinker ethylene glycol dimethacrylate (1.46g), photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (132mg) and emulsifier (L-81)0.70gAs the oil phase, 0.24g of calcium chloride dihydrate was weighed into 12.26g of the aqueous solution as the water phase and added to the oil phase while stirring (300rpm) to obtain a high internal phase emulsion. Then, the high internal phase emulsion is dripped into a polyvinyl alcohol aqueous solution by a syringe pump, and the bead-shaped porous polymer is obtained after the initiation reaction (365nm ultraviolet lamp, 8 hours) by ultraviolet light is finished. 2g of the beaded porous polymer was then weighed into a round bottom flask, and a solution of hexamethylenediamine (4% by weight, 120mL) was poured in an oil bath N at 70 deg.C2The reaction was stirred under atmosphere for 24 h. After the reaction, the reaction mixture was thoroughly immersed in ultrapure water to remove excess hexamethylenediamine. The aminated porous bead polymer thus prepared was placed in a round-bottomed flask, poured into an acetic acid solution and stirred at a low speed (150rpm) for 6 hours, followed by being placed in ultrapure water and then transferred to the round-bottomed flask after being sufficiently soaked. 30mL of diethylenetriamine pentaacetic acid aqueous solution (containing 2g of diethylenetriamine pentaacetic acid) and 4mL of MTMM solution (containing 10g of aminated beaded porous polymer) are mixed, the pH of the mixed solution is adjusted to 8.5, and the mixed solution is poured into a round bottom flask. Stirring at the rotating speed of 250rpm for 6h at room temperature to carry out grafting reaction, and fully soaking the product in ultrapure water after the reaction is finished. And finally, drying the product in a vacuum oven to obtain the bead-shaped heavy metal chelating adsorption material which is easy to separate and recycle.
Taking 0.2g of bead-shaped heavy metal chelate adsorption material and 10mL of prepared solution containing 25mg/L of Cu (II) ions and Cr (III) ions at the same time, carrying out ICP-OES (Agilent725ES) test on the filtrate after adsorbing for a certain time, and determining the concentrations of the Cu (II) ions and the Cr (III).
And (3) observing the morphology of the porous material by adopting a scanning electron microscope (SEM, Hitachi S-3400, Hitachi), wherein the pore diameter of the obtained porous material is 5-25 mu m.
The adsorption effect of the heavy metal chelate adsorption material prepared in example 3 is tested, different grouping experiments of the same batch of samples are carried out, the error is reduced, the maximum saturated adsorption amount can be reached in 15min, the time is far shorter than the time of saturated adsorption of Cu (II) ions and Cr (III) ions by the existing heavy metal ion adsorption material and is more than or equal to 70 minutes, the results are shown in Table 3, the heavy metal chelate adsorption material prepared by the invention has good adsorption efficiency on the Cu (II) ions and the Cr (III) ions, the adsorption efficiency on the Cu (II) ions and the Cr (III) ions is respectively 96.8 percent and 98.0 percent, the adsorption efficiency is far better than that of the existing adsorption material on the Cu (II) ions and the Cr (III) ions and is generally less than or equal to 90 percent, the adsorption equilibrium values of the prepared heavy metal adsorption material on the Cu (II) ions and the Cr (III) ions are respectively 0.8mg/L and 0.5mg/, respectively not higher than 1.0mg/L specified by the national drinking water standard and 0.5mg/L specified by the ground water standard.
Table 3 adsorption effect data of the heavy metal chelate adsorption material prepared in example 3
| Ion type | Cu (II) ion | Cr (III) ion |
| Before adsorption | 25mg/L | 25mg/L |
| After adsorption | 0.8mg/L | 0.5mg/L |
And (3) putting the adsorption material reaching the maximum saturated adsorption quantity into hydrochloric acid and nitric acid 1: 1, oscillating and desorbing the mixed solution, and performing an adsorption experiment again by using ICP-OES (Agilent725ES) test element analysis to prove that the metal ions are desorbed into the solution again, wherein the adsorption amount in the table 3 can still be maintained after the adsorption material is repeatedly and circularly adsorbed for 10 times and is circularly adsorbed for ten times.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The preparation method of the heavy metal chelating adsorption material is characterized by comprising the following steps:
mixing an emulsifier, a photoinitiator, a cross-linking agent and a hydrophobic monomer to obtain an oil phase; the hydrophobic monomer contains an epoxy functional group;
mixing an electrolyte with water to obtain a water phase;
adding the aqueous phase to the stirred oil phase to obtain a high internal phase emulsion;
dispersing the high internal phase emulsion, and then carrying out photoinitiated polymerization to obtain a porous polymer;
mixing the porous polymer with an amination modifier to perform amination modification to obtain a modified product;
and mixing the modified product with a heavy metal chelating agent for grafting modification to obtain the heavy metal chelating adsorption material.
2. The method according to claim 1, wherein the hydrophobic monomer is lauryl acrylate, tetradecyl methacrylate, or glycidyl methacrylate.
3. The method of claim 1, wherein the emulsifier comprises one or more of Span80, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, polyglycerol alkenyl succinate, and hypermer t 96.
4. The method of claim 1, wherein the crosslinking agent comprises ethylene glycol dimethacrylate and/or divinylbenzene.
5. The method of claim 1, wherein the amination modifier is hexamethylenediamine or ethylenediamine.
6. The method of claim 1, wherein the heavy metal chelating agent comprises one or more of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid.
7. The method of claim 1, wherein the photoinitiator comprises one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, and a, a-dimethoxy-a-phenylacetophenone.
8. The preparation method according to claim 1, wherein the mass ratio of the modified product to the heavy metal chelating agent is 2 ± 0.1: 10.
9. the heavy metal chelating adsorption material prepared by the preparation method of any one of claims 1 to 8.
10. The use of the heavy metal chelating adsorbent material of claim 9 in the field of adsorption of heavy metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110273327.6A CN113042010A (en) | 2021-03-15 | 2021-03-15 | Heavy metal chelating adsorption material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110273327.6A CN113042010A (en) | 2021-03-15 | 2021-03-15 | Heavy metal chelating adsorption material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113042010A true CN113042010A (en) | 2021-06-29 |
Family
ID=76513154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110273327.6A Pending CN113042010A (en) | 2021-03-15 | 2021-03-15 | Heavy metal chelating adsorption material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113042010A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113511926A (en) * | 2021-04-28 | 2021-10-19 | 新至农业生态科技有限公司 | Method for comprehensively utilizing livestock and poultry manure resources and returning to field |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667891A (en) * | 2015-02-09 | 2015-06-03 | 南京工业大学 | Method for preparing chelating fiber material capable of adsorbing heavy metals in water |
| CN104931691A (en) * | 2015-05-26 | 2015-09-23 | 中生北控生物科技股份有限公司 | Method for coupling carboxyl microspheres with amino |
| CN106902775A (en) * | 2017-04-07 | 2017-06-30 | 重庆沐联环境工程有限公司 | A kind of porous polymer method for preparing microsphere with heavy metal chelating function |
| CN107337759A (en) * | 2016-03-17 | 2017-11-10 | 青岛大学 | A kind of single hole polymeric hollow microsphere and preparation method thereof |
| CN108404870A (en) * | 2018-04-20 | 2018-08-17 | 中国科学院合肥物质科学研究院 | A kind of micropore carboxylated silica gel, preparation method and applications |
| CN110115983A (en) * | 2019-05-20 | 2019-08-13 | 湖南科技大学 | A kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid and preparation method thereof |
-
2021
- 2021-03-15 CN CN202110273327.6A patent/CN113042010A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667891A (en) * | 2015-02-09 | 2015-06-03 | 南京工业大学 | Method for preparing chelating fiber material capable of adsorbing heavy metals in water |
| CN104931691A (en) * | 2015-05-26 | 2015-09-23 | 中生北控生物科技股份有限公司 | Method for coupling carboxyl microspheres with amino |
| CN107337759A (en) * | 2016-03-17 | 2017-11-10 | 青岛大学 | A kind of single hole polymeric hollow microsphere and preparation method thereof |
| CN106902775A (en) * | 2017-04-07 | 2017-06-30 | 重庆沐联环境工程有限公司 | A kind of porous polymer method for preparing microsphere with heavy metal chelating function |
| CN108404870A (en) * | 2018-04-20 | 2018-08-17 | 中国科学院合肥物质科学研究院 | A kind of micropore carboxylated silica gel, preparation method and applications |
| CN110115983A (en) * | 2019-05-20 | 2019-08-13 | 湖南科技大学 | A kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| E. HILAL MERT，ET AL.: "Preparation and Characterization of Polyester–Glycidyl Methacrylate PolyHIPE Monoliths to Use in Heavy Metal Removal", 《DESIGNED MONOMERS AND POLYMERS》 * |
| ROBERT MOGLIA，ET AL.: "Solvent-Free Fabrication of polyHIPE Microspheres for Controlled Release of Growth Factors", 《MACROMOL. RAPID COMMUN.》 * |
| 黄伯云主编: "《中国战略性新兴产业-新材料 环境工程材料》", 30 November 2018, 中国铁道出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113511926A (en) * | 2021-04-28 | 2021-10-19 | 新至农业生态科技有限公司 | Method for comprehensively utilizing livestock and poultry manure resources and returning to field |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Cross-linked succinyl chitosan as an adsorbent for the removal of Methylene Blue from aqueous solution | |
| CN108579709B (en) | Porous structure elastic composite material for extracting uranium from seawater and preparation method thereof | |
| Denizli et al. | Metal-complexing ligand methacryloylamidocysteine containing polymer beads for Cd (II) removal | |
| Jiang et al. | Effect of solvent/monomer feed ratio on the structure and adsorption properties of Cu2+-imprinted microporous polymer particles | |
| Denizli et al. | Synthesis and characterization of poly (hydroxyethyl methacrylate-N-methacryloyl-(l)-glutamic acid) copolymer beads for removal of lead ions | |
| Denizli et al. | Methacryloylamidoglutamic acid functionalized poly (2-hydroxyethyl methacrylate) beads for UO22+ removal | |
| CN107892733B (en) | Heavy metal wastewater ion adsorption resin and preparation method thereof | |
| Arslan | Preparation and use of amine-functionalized glycidyl methacrylate-g-poly (ethylene terephthalate) fibers for removal of chromium (VI) from aqueous solution | |
| CN109078616B (en) | Tannin modified graphene/gelatin porous composite material and preparation method and application thereof | |
| CN113908815B (en) | High-molecular modified adsorbent and preparation method and application thereof | |
| CN108503880A (en) | A kind of method of the calcium alginate compounded microballoon of Synthesis of Polyacrylamide Using Anti-phase Microemulsion Polymerization- | |
| CN109574166A (en) | A kind of sewage-treating agent and its preparation process | |
| CN113042010A (en) | Heavy metal chelating adsorption material and preparation method and application thereof | |
| CN110026167A (en) | A kind of particulate adsorbent material and preparation method thereof for removing formaldehyde | |
| CN113929819B (en) | Chitosan polyacrylamide composite porous hydrogel, metal ion detection reagent, and preparation method and application thereof | |
| Meng et al. | Synthesis of novel ion-imprinted polymers by two different RAFT polymerization strategies for the removal of Cs (I) from aqueous solutions | |
| CN112390347A (en) | Filler with salt-tolerant functional microorganism enrichment function and preparation method thereof | |
| CN106630082B (en) | Preparation method of polyvinyl chloride-based flocculant | |
| CN113388154A (en) | Biodegradable hydrophilic oleophobic foam with adsorption function | |
| US11932717B2 (en) | Green synthesis method of antibacterial super-porous hydrogel, product of antibacterial super-porous hydrogel and application of antibacterial super-porous hydrogel to degradation of various pollutants in wastewater treatment | |
| CN115141303B (en) | Preparation method of porous material capable of efficiently removing aromatic sulfonic acid compounds in water body | |
| Hashem et al. | Application of some starch hydrogels for the removal of mercury (II) ions from aqueous solutions | |
| CN109160553A (en) | A kind of dedicated sewage-treating agent of chemical fibre industry and preparation method thereof | |
| CN105217766B (en) | Solid is except deodorizing coagulant and its preparation method and application | |
| CN109942737A (en) | The amphiphilic polymer micro-sphere material of uniform particle sizes, preparation method and application |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210629 |
|
| RJ01 | Rejection of invention patent application after publication |