CN112427022A - Preparation method of gel balls of nitrogen-doped organic and inorganic ion-crosslinked polymer - Google Patents
Preparation method of gel balls of nitrogen-doped organic and inorganic ion-crosslinked polymer Download PDFInfo
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- CN112427022A CN112427022A CN202011390643.3A CN202011390643A CN112427022A CN 112427022 A CN112427022 A CN 112427022A CN 202011390643 A CN202011390643 A CN 202011390643A CN 112427022 A CN112427022 A CN 112427022A
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- 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
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
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- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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Abstract
The invention discloses a preparation method of a gel ball of a polymer doped with a nitrogen-doped organic material and a nitrogen-doped inorganic ion-crosslinked polymer, which specifically comprises the following steps: firstly, taking Zr as4+Reacting with polyethylene polyamine (ethylenediamine, diethylenetriamine and triethylenetetramine) to prepare zirconia polyethylene polyamine polymer matrix, mixing with tannic acid, and embedding in sodium alginate matrix to form ionomer gel ball. The invention uses Zr4+Salt with polyethylene polyaminePreparing an inorganic base polymer Zr- (EDA/DETA/TETA) by using EDA/DETA/TETA, synthesizing organic-inorganic ion crosslinked polymer gel spheres by using TA and SA-Ca as organic polymer bases, and taking the organic-inorganic ion crosslinked polymer gel spheres as a novel adsorbent to remove Pb (II) Hg (II) and Cr (VI) ions in an aqueous solution, wherein the adsorption amount of ZI-DETA/TA/SA-Ca is the highest. Zr-DETA/TA/SA-Ca is in a macroporous sphere shape and is rich in functional groups such as amino, hydroxyl, phenolic hydroxyl, carboxylic acid group and the like. Has high adsorptivity and selectivity, simple and mild synthesis conditions, and can be effectively applied to heavy metal wastewater treatment.
Description
Technical Field
The invention relates to the technical field of polymer preparation, in particular to a preparation method of a polymer gel ball doped with nitrogen and organic and inorganic ions.
Background
In recent years, various composite adsorbent materials have received much attention. The composite adsorption material is a new material with adsorption function compounded by two or more different materials by a proper method, has selective affinity effect on certain specific ions or molecules, and has superior performance compared with the performance of a single material. The composite adsorption material is a material which utilizes the physical or chemical actions of the adsorption material and the adsorbed substance, wherein the actions comprise physical attraction, coordination, static electricity and the like, so that the adsorption material and the adsorbed substance are temporarily or permanently combined, and the adsorption material further plays a role in adsorption removal, and is an important component of modern adsorption and separation technology. The inorganic component is introduced into the macromolecular matrix through simple compounding or grafting modification, which is a research direction for developing rapidly in recent years, because the addition of the -free component can effectively improve the adsorption capacity, hydrophilicity, thermal stability, chemical stability, structural performance and the like of the composite material, and because most inorganic materials generally have the advantages of wide sources, low price and the like, the introduction of the inorganic substance can also greatly reduce the operation cost. Zr (IV) is generally used as the inorganic component because of its very high stability and its strong resistance to acids, bases, organic solvents and reducing agents. Research shows that the inorganic metal zirconium and the metal oxide thereof have strong binding capacity to organic and inorganic toxic pollutants in wastewater.
The footprint of tannic acid is widespread throughout nature and is widely found in the bark and fruit of various trees. Has the advantages of low price, wide sources, green, cleanness, biodegradability and renewability. The molecular structure of the chelate is rich in phenolic hydroxyl, and the chelate has strong chelating capacity on various heavy metal ions. However, the tannic acid adsorbent prepared on the market at present has a limited ability to adsorb heavy metals. In addition, most prepared adsorbents are powdery, and the problems of difficult separation and difficult reuse occur in the using process. Heavy metals in the wastewater can not be efficiently removed, and the service performance of the adsorption material is enhanced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the gel balls doped with the nitrogen and the organic and inorganic ions, and solves the problem of Zr4+The tannin is matched to prepare the material which can efficiently remove heavy metals in wastewater and enhance the service performance of the adsorption material.
In order to achieve the purpose, the invention is realized by the following technical scheme: a method for preparing a gel ball of a polymer doped with a nitrogen-doped organic and inorganic ion-crosslinked, the method comprising: the method specifically comprises the following steps:
s1, dissolving certain inorganic salt in a three-neck round-bottom flask containing distilled water, and stirring at room temperature for 30 min. Polyethylene polyamine is then added. Continuing to oscillate for 2 hours at room temperature;
s2, adding Sodium Alginate (SA) into a flask containing distilled water, stirring at room temperature, dissolving, adding Tannic Acid (TA) into the solution, and continuously stirring to obtain a homogeneous mixture;
s3, adding the inorganic salt-polyethylene polyamine gel prepared in the S1 step into the SA/TA mixture in the S2 step, and oscillating for 6 hours at room temperature;
s4, then putting the gel into Ca2+In solution, the liquid containing sodium alginate will be in Ca2+Crosslinking reaction in the solution and precipitation to form spherical gel spheres;
s5, hardening the composite balls in the gel liquid for 24h, and washing with distilled water.
Preferably, the inorganic salt in step S1 is Zr4+And (3) salt.
Preferably, in the step S1, the polyethylenepolyamine is a co-product of Ethylenediamine (EDA), Diethylenetriamine (DETA), and triethylenetetramine (TETA), and the molar mass ratio of Ethylenediamine (EDA), Diethylenetriamine (DETA), and triethylenetetramine (TETA) is 1:1: 1.
Preferably, Zr in the step S14+And the polyethylene polyamine in a molar mass ratio of 1: 1.
Advantageous effects
The invention provides a preparation method of a gel ball of a polymer doped with a nitrogen-doped organic material and a nitrogen-doped inorganic ion-crosslinked polymer. Compared with the prior art, the method has the following beneficial effects: the invention uses Zr4+Reaction of the salt with a polyethylenepolyamine (EDA/DETA/TETA) to produce an inorganic-based polymer Zr- (EDA/DETA/TETA), again TA and SA-Ca, synthesizing organic and inorganic ion crosslinked polymer gel balls as organic polymer base, and when the organic and inorganic ion crosslinked polymer gel balls are used as a novel adsorbent to remove Pb (II) Hg (II) and Cr (VI) ions in an aqueous solution, the adsorption amount of ZI-DETA/TA/SA-Ca is the highest. Zr-DETA/TA/SA-Ca is in a macroporous sphere shape and is rich in functional groups such as amino, hydroxyl, phenolic hydroxyl, carboxylic acid group and the like. Has high adsorptivity and selectivity, simple and mild synthesis conditions, and can be effectively applied to heavy metal wastewater treatment. Zr-DETA/TA/SA-Ca can effectively remove Pb (II) and Hg (II) ions at the pH value of 4-7, and the optimum adsorption pH value of Cr (VI) ions is about 2-3. The maximum adsorption capacity for Pb (II), Hg (II) and Cr (VI) ions is obvious for most other adsorbents on the market at present.
Drawings
FIG. 1 is a schematic diagram of the structure of Zr-DETA/TA/SA-Ca ionomer gel spheres of the present invention;
FIG. 2 is an FTIR spectrum of each product of the present invention;
FIG. 3 is an SEM image of Zr-DETA/TA/SA-Ca according to the present invention;
FIG. 4 is a graph comparing the adsorption amounts of Pb (II), Hg (II) and Cr (VI) by Zr (EDA/DETA/TETA)/TA/SA-Ca ionomer gel beads according to the present invention;
FIG. 5 is a graph showing the effect of pH on the adsorption of heavy metal ions by Zr-DETA/TASA-Ca ionomer gel beads according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-5, the embodiment of the present invention provides three technical solutions: the preparation method of the gel balls doped with the nitrogen-doped organic and inorganic ions includes the following specific steps:
example 1
S1, ZrOCl2·8H2O (0.02moL) was dissolved in a three-necked round-bottomed flask containing 50mL of distilled water and stirred at room temperature for 30 min. EDA (0.04moL), DETA (0.04moL) and TETA (0.04moL) were dissolved in 20mL of distilled water and added to the above solution. Continuing to oscillate for 2 hours at room temperature;
s2, adding 5g of Sodium Alginate (SA) into a flask containing 100ml of distilled water, stirring at room temperature, dissolving, adding 2g of Tannic Acid (TA) into the solution, and continuously stirring to obtain a homogeneous mixture;
s3, adding the inorganic salt-polyethylene polyamine gel prepared in the S1 step into the SA/TA mixture in the S2 step, and oscillating for 6 hours at room temperature;
s4, then putting the gel into Ca2+In solution, the liquid containing sodium alginate will be in Ca2+Crosslinking reaction in the solution and precipitation to form spherical gel spheres;
s5, hardening the composite balls in the gel liquid for 24h, and washing with distilled water.
Example 2
S1, ZrOCl2·8H2O (0.03moL) was dissolved in a three-necked round-bottomed flask containing 70mL of distilled water and stirred at room temperature for 30 min. EDA (0.06moL), DETA (0.06moL) and TETA (0.06moL) were dissolved in 30mL of distilled water and added to the above solution. Continuing to oscillate for 2 hours at room temperature;
s2, adding 6g of Sodium Alginate (SA) into a flask containing 120ml of distilled water, stirring at room temperature, dissolving, adding 3g of Tannic Acid (TA) into the solution, and continuously stirring to obtain a homogeneous mixture;
s3, adding the inorganic salt-polyethylene polyamine gel prepared in the S1 step into the SA/TA mixture in the S2 step, and oscillating for 6 hours at room temperature;
s4, then putting the gel into Ca2+In solution, the liquid containing sodium alginate will be in Ca2+Crosslinking reaction in the solution and precipitation to form spherical gel spheres;
s5, hardening the composite balls in the gel liquid for 24h, and washing with distilled water.
Example 3
S1, ZrOCl2·8H2O (0.05moL) was dissolved in a three-necked round-bottomed flask containing 100mL of distilled water and stirred at room temperature for 30 min. EDA (0.1moL), DETA (0.1moL) and TETA (0.1moL) were dissolved in 100mL of distilled water and added to the above solution. Continuing to oscillate for 2 hours at room temperature;
s2, adding 7g of Sodium Alginate (SA) into a flask containing 150ml of distilled water, stirring at room temperature, dissolving, adding 4g of Tannic Acid (TA) into the solution, and continuing stirring to obtain a homogeneous mixture;
s3, adding the inorganic salt-polyethylene polyamine gel prepared in the S1 step into the SA/TA mixture in the S2 step, and oscillating for 6 hours at room temperature;
s4, then putting the gel into Ca2+In solution, the liquid containing sodium alginate will be in Ca2+Crosslinking reaction in the solution and precipitation to form spherical gel spheres;
s5, hardening the composite balls in the gel liquid for 24h, and washing with distilled water.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. A method for preparing a gel ball of a polymer doped with a nitrogen-doped organic and inorganic ion-crosslinked, the method comprising: the method specifically comprises the following steps:
s1, dissolving certain inorganic salt in a three-neck round-bottom flask containing distilled water, and stirring at room temperature for 30 min. Polyethylene polyamine is then added. Continuing to oscillate for 2 hours at room temperature;
s2, adding Sodium Alginate (SA) into a flask containing distilled water, stirring at room temperature, dissolving, adding Tannic Acid (TA) into the solution, and continuously stirring to obtain a homogeneous mixture;
s3, adding the inorganic salt-polyethylene polyamine gel prepared in the S1 step into the SA/TA mixture in the S2 step, and oscillating for 6 hours at room temperature;
s4, then putting the gel into Ca2+In solution, the liquid containing sodium alginate will be in Ca2+Crosslinking reaction in the solution and precipitation to form spherical gel spheres;
s5, hardening the composite balls in the gel liquid for 24h, and washing with distilled water.
2. The method according to claim 1, wherein the method for preparing the gel beads doped with the nitrogen-doped organic and inorganic ions comprises: the inorganic salt in the step S1 is Zr4+And (3) salt.
3. The method according to claim 1, wherein the method for preparing the gel beads doped with the nitrogen-doped organic and inorganic ions comprises: in the step S1, the polyethylene polyamine is a coproduct of Ethylenediamine (EDA), Diethylenetriamine (DETA) and triethylenetetramine (TETA), and the molar mass ratio of Ethylenediamine (EDA), Diethylenetriamine (DETA) and triethylenetetramine (TETA) is 1:1: 1.
4. The method according to claim 1, wherein the method for preparing the gel beads doped with the nitrogen-doped organic and inorganic ions comprises: zr in said step S14+And the polyethylene polyamine in a molar mass ratio of 1: 1.
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