CN115869915B - Phosphoric acid functionalized sodium alginate composite material and preparation and application thereof - Google Patents
Phosphoric acid functionalized sodium alginate composite material and preparation and application thereof Download PDFInfo
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 128
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 128
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 128
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011325 microbead Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 9
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 54
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 description 50
- 239000000706 filtrate Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- LMFWXTZEFKLNSB-UHFFFAOYSA-N OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.P.P Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.P.P LMFWXTZEFKLNSB-UHFFFAOYSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 244000184734 Pyrus japonica Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000196252 Ulva Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a phosphoric acid functionalized sodium alginate composite material and preparation and application thereof. The method comprises the following steps: dissolving sodium alginate in deionized water to form sodium alginate sol, slowly dripping the sodium alginate sol into a calcium chloride solution, and standing for a period of time to form sodium alginate microbeads; adding the sodium alginate microbeads into a tetrakis (hydroxymethyl) phosphonium sulfate solution, soaking for a period of time, separating, washing, and freeze-drying to obtain the phosphoric acid functionalized sodium alginate composite material. The preparation method of the phosphoric acid functionalized sodium alginate composite material disclosed by the invention has the advantages of simplicity and convenience in operation, mild conditions, rapidness, effectiveness and the like, and the prepared product can effectively reduce the concentration of Cr (VI) ions in water, so that the final residual concentration of the product reaches the national emission standard. The highest adsorption capacity of the phosphoric acid functionalized sodium alginate composite material prepared by the invention to Cr (VI) can reach 357.5mg/g.
Description
Technical Field
The invention belongs to the technical field of preparation of green adsorption materials and application of the green adsorption materials in water pollution treatment of heavy metal ions, and mainly relates to a phosphoric acid functionalized sodium alginate composite material and preparation and application thereof.
Background
In the background of the increasing progress of industrial development, the problem of industrial wastewater pollution becomes a hidden danger, and the treatment of wastewater metal ion water pollution by factories becomes an important gateway. The harm of Cr (VI) metal ions, which is a toxic pollutant of heavy metals, is particularly serious, and the Cr (VI) metal ions can invade the digestive system, the respiratory system and the endocrine system of a human body and can be accumulated for a long time to form chronic poisoning, so that the Cr (VI) metal ions gradually cause harm to the human body. Aiming at the problem of Cr (VI) sewage treatment, the adsorption method has the advantages of simple operation, easy recovery and the like, and is widely concerned.
Sodium alginate is used as a rich renewable resource, has the advantages of good hydrophilicity, degradability, rich natural resources and the like, and also contains rich carboxyl (-COOH) which can carry out chelation with various metal ions, so that the sodium alginate is more and more concerned in the field of heavy metal wastewater treatment. Paudyal et al Paudyal H, pangani B, inoue K, et al preparation of novel alginate based anion exchanger from Ulva japonica and its application for the removal of trace concentrations of fluoride from water [ J].Bioresource technology,2013,148:221-227.]In the process of mixing sodium alginate with Ca 2+ On the basis of forming sodium alginate calcium microbeads by ion combination, the adsorption performance of the material is improved by loading other metals, and the result shows that the adsorption capacity of the unmodified sodium alginate microsphere material is very small, and the maximum adsorption capacity of the unmodified sodium alginate microsphere material to Cr (VI) is only 29.7mg/g. Therefore, further exploration of modified sodium alginate materials with high adsorption capacity and rapid adsorption kinetics has practical significance.
Tetrahydroxymethylphosphorous sulfate (THPS) is a completely water-soluble quaternary phosphonium salt that was originally used as a green, inexpensive biocide in industrial cooling water systems. THPS is readily biodegradable and cannot accumulate in the environment because it is readily oxidized rapidly to trimethylol oxidationPhosphorus (THPO) can be further decomposed into CO 2 Water and phosphate, and thus can be a potential new modifier.
Chinese patent application CN112551631A discloses a method for rapidly reducing the concentration of heavy metal chromium ions in water, which achieves the aim of reducing the concentration of the chromium ions in water by using the prepared sodium alginate/tannic acid microsphere, has the maximum adsorption removal rate of 91.4 percent for 20-100mg/L chromium ion-containing wastewater, and has the problem that the residual concentration of the chromium ions after adsorption can not reach the national discharge standard.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a phosphoric acid functionalized sodium alginate composite material. Compared with the traditional sodium alginate adsorbent material, the invention provides the preparation method of the phosphoric acid functionalized sodium alginate composite material which is easy to prepare, easy to separate and recycle, easy to obtain raw materials, rapid in Cr (VI) adsorption, high in adsorption capacity and capable of enabling the residual concentration of Cr (VI) after adsorption to reach the national emission standard.
The invention also aims to provide the phosphoric acid functionalized sodium alginate composite material prepared by the method.
It is still another object of the present invention to provide the use of the above-described phosphate functionalized sodium alginate composite material.
The invention solves the technical problems by adopting the following preparation scheme:
a preparation method of a phosphoric acid functionalized sodium alginate composite material comprises the following steps:
(1) Preparing sodium alginate sol: weighing sodium alginate, adding the sodium alginate into deionized water, and stirring for a period of time at room temperature to obtain sodium alginate sol;
(2) Preparation of sodium alginate microbeads: slowly dripping the sodium alginate sol prepared in the step (1) into a pre-prepared calcium chloride solution, standing for a period of time at room temperature, separating and washing at normal temperature and normal pressure to obtain water-containing sodium alginate microbeads;
(3) Preparing a phosphoric acid functionalized sodium alginate composite material: and (3) adding the sodium alginate microbeads prepared in the step (2) into a tetrakis (hydroxymethyl) phosphonium sulfate solution, soaking for a period of time, separating and washing to obtain wet phosphoric acid functionalized sodium alginate microbeads, and freeze-drying the wet phosphoric acid functionalized sodium alginate microbeads to obtain the phosphoric acid functionalized sodium alginate composite material.
The mass fraction of the sodium alginate sol in the step (1) is 1.5-2%, and the stirring time is 1h.
In the step (2), the volume ratio of the sodium alginate sol to the calcium chloride solution is 1:20.
And (3) the mass fraction of the calcium chloride solution in the step (2) is 5%, and the standing time is 8 hours.
The diameter of the aqueous sodium alginate microbead in the step (2) is 2-5mm.
The mass fraction of the tetrakis (hydroxymethyl) phosphonium sulfate solution in the step (3) is 5-10%, preferably 7-10%; the soaking time is 12-24h.
The temperature of the freeze drying in the step (3) is-20 ℃ and the time is 12 hours.
The washing in the step (2) and the washing in the step (3) are carried out by washing with deionized water for 2-3 times until the pH value is neutral.
The phosphoric acid functionalized sodium alginate composite material in the step (3) is a microbead material with the diameter of 1-2 mm.
The phosphoric acid functionalized sodium alginate composite material prepared by the invention can be used for adsorbing Cr (VI) in sewage.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts sodium alginate as raw material, has low price, abundant sources, mild preparation condition and simple operation, and the product phosphoric acid functionalized sodium alginate composite material belongs to macromolecular material and is easy to recycle.
(2) The adsorption performance of the phosphoric acid functionalized sodium alginate composite material prepared by the invention to Cr (VI) is obviously improved, the adsorption rate to Cr (VI) is extremely fast, the highest adsorption removal rate to Cr (VI) solution with initial concentration of 100mg/L in 30min reaches 99.8%, the rapid and effective adsorption can be realized, and the concentration of residual Cr (VI) reaches the national emission standard; the highest adsorption capacity of Cr (VI) can reach 357.5mg/g.
Drawings
FIG. 1 is a schematic diagram of the preparation method of the invention.
FIG. 2 is an SEM image of SAB prepared in example 1.
FIG. 3 is an SEM image of SAB-THPS-2 prepared in example 2.
FIG. 4 is a graph showing adsorption kinetics of Cr (VI) to samples prepared in examples 1 to 5.
FIG. 5 is an enlarged view of a portion of the adsorption kinetics curve of Cr (VI) in FIG. 4 and a comparison of adsorption removal rates for samples prepared in examples 1-5.
FIG. 6 is an adsorption isotherm plot of SAB-THPS-2 prepared in example 2.
FIG. 7 is a FTIR plot of SAB, SAB-THPS-2 and their respective samples after 12h adsorption to 50mL, pH=3, 100mg/L Cr (VI) solution.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market, and the process parameters which are not specially noted can be carried out by referring to the conventional technology. The concentration of Cr (VI) in the examples was determined by diphenylcarbodihydrazide spectrophotometry using an ultraviolet-visible spectrophotometer model number TU-1901.
The room temperature in the examples is 25 ℃. The Cr (VI) solution for adsorption performance test was prepared in advance to have an initial concentration of 100mg/L, and was adjusted to ph=3 with 5% by mass hydrochloric acid.
Example 1
1. Preparation of phosphoric acid functionalized sodium alginate composite material
(1) Preparing sodium alginate sol: 1g of sodium alginate is weighed and added into 50mL of deionized water, and the mixture is stirred for 1h at the room temperature at the rotating speed of 300r/min, so as to obtain sodium alginate sol.
(2) Preparation of sodium alginate microbeads: slowly dripping the sodium alginate sol prepared in the step (1) into 100mL of 5% calcium chloride solution by mass fraction through a 5mL sterile syringe, standing at room temperature for 8h, separating at room temperature and normal pressure, and washing with deionized water for 2-3 times until the pH value is neutral to obtain water-containing sodium alginate microbeads with the diameter of 2-5 mm; the aqueous sodium alginate microbeads were freeze-dried at-20℃for 12h to obtain sodium alginate SAB as a control.
(3) Preparing a phosphoric acid functionalized sodium alginate composite material: adding the sodium alginate microbeads prepared in the step (2) into 100mL of a 7% mass fraction of tetrakis (hydroxymethyl) phosphonium sulfate solution, immersing for 18h, separating and washing with deionized water for 2-3 times until the pH value is neutral to obtain wet phosphoric acid functionalized sodium alginate microbeads, and freeze-drying the wet phosphoric acid functionalized sodium alginate microbeads at-20 ℃ for 12h to obtain the phosphoric acid functionalized sodium alginate composite material SAB-THPS-1.
2. Adsorption performance test of phosphoric acid functionalized sodium alginate composite material on Cr (VI)
At room temperature, 50mg of SAB and 50mg of SAB-THPS-1 were added to 50mL of a pre-formulated Cr (VI) solution, respectively, for Cr (VI) adsorption test. The residual concentration of Cr (VI) in the filtrate was 70.27mg/L, as measured by the adsorption of SAB to equilibrium, and the adsorption rate of Cr (VI) was 29.7%. The residual concentration of Cr (VI) in the filtrate was found to be 4.93mg/L when the SAB-THPS-1 adsorption was equilibrated, and the adsorption rate of Cr (VI) was found to be 95.1%.
Example 2
1. Preparation of phosphoric acid functionalized sodium alginate composite material
(1) Preparing sodium alginate sol: 0.75g of sodium alginate is weighed and added into 50mL of deionized water, and the mixture is stirred for 1h at the room temperature at the rotating speed of 300r/min, so as to obtain sodium alginate sol.
(2) Preparation of sodium alginate microbeads: slowly dripping the sodium alginate sol prepared in the step (1) into 100mL of 5% calcium chloride solution by mass fraction through a 5mL sterile syringe, standing for 8h at room temperature, separating at normal temperature and normal pressure, and washing with deionized water for 2-3 times until the pH value is neutral, thus obtaining the aqueous sodium alginate microbeads with the diameter of 2-5mm.
(3) Preparing a phosphoric acid functionalized sodium alginate composite material: adding the sodium alginate microbeads prepared in the step (2) into 100mL of a tetra-methylol phosphorus sulfate solution with the mass fraction of 10% for soaking for 24 hours, separating and washing with deionized water for 2-3 times until the pH value is neutral to obtain wet phosphoric acid functionalized sodium alginate microbeads, and freeze-drying the wet phosphoric acid functionalized sodium alginate microbeads at the temperature of-20 ℃ for 12 hours to obtain the phosphoric acid functionalized sodium alginate composite material SAB-THPS-2.
2. Adsorption performance test of phosphoric acid functionalized sodium alginate composite material on Cr (VI)
At room temperature, 50mg of SAB-THPS-2 was added to 50mL of a pre-formulated Cr (VI) solution for Cr (VI) adsorption test. The residual concentration of Cr (VI) in the filtrate was 0.15mg/L as measured when SAB-THPS-2 adsorption reached equilibrium, and the adsorption rate of Cr (VI) was 99.8%.
Example 3
1. Preparation of phosphoric acid functionalized sodium alginate composite material
(1) Preparing sodium alginate sol: 0.80g of sodium alginate is weighed and added into 50mL of deionized water, and the mixture is stirred for 1h at the room temperature at the rotating speed of 300r/min to obtain sodium alginate sol.
(2) Preparation of sodium alginate microbeads: slowly dripping the sodium alginate sol prepared in the step (1) into 100mL of 5% calcium chloride solution by mass fraction through a 5mL sterile syringe, standing for 8h at room temperature, separating at normal temperature and normal pressure, and washing with deionized water for 2-3 times until the pH value is neutral, thus obtaining the aqueous sodium alginate microbeads with the diameter of 2-5mm.
(3) Preparing a phosphoric acid functionalized sodium alginate composite material: adding the sodium alginate microbeads prepared in the step (2) into 100mL of a tetra-methylol phosphorus sulfate solution with the mass fraction of 8% for soaking for 14 hours, separating and washing with deionized water for 2-3 times until the pH value is neutral to obtain wet phosphoric acid functionalized sodium alginate microbeads, and freeze-drying the wet phosphoric acid functionalized sodium alginate microbeads at the temperature of-20 ℃ for 12 hours to obtain the phosphoric acid functionalized sodium alginate composite material SAB-THPS-3.
2. Adsorption performance test of phosphoric acid functionalized sodium alginate composite material on Cr (VI)
At room temperature, 50mg of SAB-THPS-3 was added to 50mL of a pre-formulated Cr (VI) solution for Cr (VI) adsorption test. The residual concentration of Cr (VI) in the filtrate was found to be 0.26mg/L when the SAB-THPS-3 adsorption was equilibrated, and the adsorption rate of Cr (VI) was found to be 99.7%.
Example 4
1. Preparation of phosphoric acid functionalized sodium alginate composite material
(1) Preparing sodium alginate sol: 0.90g of sodium alginate is weighed and added into 50mL of deionized water, and the mixture is stirred for 1h at the room temperature at the rotating speed of 300r/min to obtain sodium alginate sol.
(2) Preparation of sodium alginate microbeads: slowly dripping the sodium alginate sol prepared in the step (1) into 100mL of 5% calcium chloride solution by mass fraction through a 5mL sterile syringe, standing for 8h at room temperature, separating at normal temperature and normal pressure, and washing with deionized water for 2-3 times until the pH value is neutral, thus obtaining the aqueous sodium alginate microbeads with the diameter of 2-5mm.
(3) Preparing a phosphoric acid functionalized sodium alginate composite material: adding the sodium alginate microbeads prepared in the step (2) into 100mL of a tetra-methylol phosphorus sulfate solution with the mass fraction of 10% for soaking for 12 hours, separating and washing with deionized water for 2-3 times until the pH value is neutral to obtain wet phosphoric acid functionalized sodium alginate microbeads, and freeze-drying the wet phosphoric acid functionalized sodium alginate microbeads at the temperature of-20 ℃ for 12 hours to obtain the phosphoric acid functionalized sodium alginate composite material SAB-THPS-4.
2. Adsorption performance test of phosphoric acid functionalized sodium alginate composite material on Cr (VI)
At room temperature, 50mg of SAB-THPS-4 was added to 50mL of a pre-formulated Cr (VI) solution for Cr (VI) adsorption test. The residual concentration of Cr (VI) in the filtrate was found to be 0.41mg/L when the adsorption of SAB-THPS-4 reached equilibrium, and the adsorption rate of Cr (VI) was found to be 99.6%.
Example 5
1. Preparation of phosphoric acid functionalized sodium alginate composite material
(1) Preparing sodium alginate sol: 1.0g of sodium alginate is weighed and added into 50mL of deionized water, and the mixture is stirred for 1h at the room temperature at the rotating speed of 300r/min to obtain sodium alginate sol.
(2) Preparation of sodium alginate microbeads: slowly dripping the sodium alginate sol prepared in the step (1) into 100mL of 5% calcium chloride solution by mass fraction through a 5mL sterile syringe, standing for 8h at room temperature, separating at normal temperature and normal pressure, and washing with deionized water for 2-3 times until the pH value is neutral, thus obtaining the aqueous sodium alginate microbeads with the diameter of 2-5mm.
(3) Preparing a phosphoric acid functionalized sodium alginate composite material: adding the sodium alginate microbeads prepared in the step (2) into 100mL of a tetrakis (hydroxymethyl) phosphonium sulfate solution with the mass fraction of 9% for soaking for 16 hours, separating and washing with deionized water for 2-3 times until the pH value is neutral to obtain wet phosphoric acid functionalized sodium alginate microbeads, and freeze-drying the wet phosphoric acid functionalized sodium alginate microbeads at the temperature of-20 ℃ for 12 hours to obtain the phosphoric acid functionalized sodium alginate composite material SAB-THPS-5.
2. Adsorption performance test of phosphoric acid functionalized sodium alginate composite material on Cr (VI)
At room temperature, 50mg of SAB-THPS-5 was added to 50mL of a pre-formulated Cr (VI) solution for Cr (VI) adsorption test. The residual concentration of Cr (VI) in the filtrate was found to be 0.41mg/L when the adsorption of SAB-THPS-5 reached equilibrium, and the adsorption rate of Cr (VI) was found to be 99.6%.
Example 6
In order to examine the adsorption performance of the phosphoric acid functionalized sodium alginate composite material on Cr (VI) solutions with different concentrations, the adsorption performance of the phosphoric acid functionalized sodium alginate composite material on the Cr (VI) solutions with different initial concentrations was tested by taking SAB-THPS-2 prepared in example 2 as an example. The adsorption process is as follows: 50mL of Cr (VI) solutions with pH=3 and concentrations of 10mg/L, 20mg/L, 50mg/L, 100mg/L, 200mg/L, 300mg/L, 400mg/L and 500mg/L were prepared, and then 0.05g of SAB-THPS-2 was added, respectively, and the parameters of the constant temperature shaking oven were set at 25℃and 150r/min. The adsorption isotherm of SAB-THPS-2 is shown in FIG. 6, and the maximum adsorption amount is 357.5mg/g.
TABLE 1 examples 1-5 preparation of samples adsorption Rate of Cr (VI) and residual equilibrium concentration of Cr (VI) after adsorption
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the phosphoric acid functionalized sodium alginate composite material is characterized by comprising the following steps of:
(1) Weighing sodium alginate, adding the sodium alginate into water, and stirring at room temperature to obtain sodium alginate sol;
(2) Dropwise adding the sodium alginate sol prepared in the step (1) into a calcium chloride solution, standing for a period of time at room temperature, separating and washing at normal temperature and normal pressure to obtain sodium alginate microbeads;
(3) Adding the sodium alginate microbeads prepared in the step (2) into a tetrakis (hydroxymethyl) phosphonium sulfate solution for soaking, separating and washing to obtain wet phosphoric acid functionalized sodium alginate microbeads, and freeze-drying the wet phosphoric acid functionalized sodium alginate microbeads to obtain a phosphoric acid functionalized sodium alginate composite material; the mass fraction of the tetrakis (hydroxymethyl) phosphonium sulfate solution is 5-10%, and the soaking time is 12-24h.
2. The preparation method according to claim 1, wherein the mass fraction of the sodium alginate sol in the step (1) is 1.5-2%, and the stirring time is 1h.
3. The method according to claim 1, wherein the volume ratio of the sodium alginate sol to the calcium chloride solution in the step (2) is 1:20.
4. The method according to claim 1, wherein the calcium chloride solution in the step (2) has a mass fraction of 5%, and the standing time is 8 hours.
5. The method according to claim 1, wherein the freeze-drying in step (3) is carried out at a temperature of-20 ℃ for a period of 12 hours.
6. The method according to claim 1, wherein the washing in step (2) and step (3) means washing with deionized water 2 to 3 times to neutral pH.
7. A phosphoric acid functionalized sodium alginate composite material made by the method of any one of claims 1-6.
8. The phosphate functionalized sodium alginate composite of claim 7, wherein the phosphate functionalized sodium alginate composite is a microbead material having a diameter of 1-2 mm.
9. The use of the phosphate functionalized sodium alginate composite material of claim 7 in the treatment of Cr (VI) containing wastewater.
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