CN117654447A - Defluorination composite material and preparation method thereof - Google Patents
Defluorination composite material and preparation method thereof Download PDFInfo
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- CN117654447A CN117654447A CN202410127645.5A CN202410127645A CN117654447A CN 117654447 A CN117654447 A CN 117654447A CN 202410127645 A CN202410127645 A CN 202410127645A CN 117654447 A CN117654447 A CN 117654447A
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- iminodiacetic acid
- alginate
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- aluminum
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- 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 claims abstract description 23
- 239000000661 sodium alginate Substances 0.000 claims abstract description 23
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 23
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 23
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 21
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 20
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 15
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 239000000648 calcium alginate Substances 0.000 claims abstract description 12
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 12
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 12
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 12
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical group CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004781 alginic acids Chemical group 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 229960001126 alginic acid Drugs 0.000 claims description 4
- 239000000783 alginic acid Substances 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 abstract description 18
- 239000011737 fluorine Substances 0.000 abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 16
- 238000011069 regeneration method Methods 0.000 abstract description 12
- 230000008929 regeneration Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003463 adsorbent Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 15
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
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- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
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- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
A defluorination composite material comprises a calcium alginate shell and aluminum alginate-aluminum iminodiacetic acid gel inside the calcium alginate shell. A method of making the defluorinated composite comprising the steps of: carrying out dehydration condensation reaction on the sodium alginate and graphene oxide mixed solution and iminodiacetic acid to obtain sodium alginate-iminodiacetic acid composite gel; reacting the sodium alginate-iminodiacetic acid composite gel with a calcium chloride solution to prepare a hemispherical calcium alginate-iminodiacetic acid composite material; and reacting the calcium alginate-iminodiacetic acid composite material with an aluminum sulfate solution to form the aluminum alginate-iminodiacetic acid composite material coated by the calcium alginate shell. Compared with the existing fluorine adsorbent, the fluorine-removing composite material provided by the invention has good adsorption capacity, excellent cyclic regeneration capacity and ion selectivity.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a defluorination composite material and a preparation method thereof.
Background
Fluoride is classified by the World Health Organization (WHO) as one of the water resource pollutants that has a significant impact on health, and fluoride groundwater pollution has been recognized as one of the serious problems worldwide. Industries that drain wastewater containing high fluoride concentrations include glass and plastic production, nonferrous metallurgy, semiconductor manufacturing, electroplating, coal-fired power stations, beryllium extraction plants, brick and phosphate production, and aluminum smelting plants. Prolonged excessive exposure to fluoride (total intake of 14mg per day) results in increased risk of fluorosis and fracture. Excessive intake of fluoride can lead to various diseases such as osteoporosis, arthritis, cancer, infertility, brain injury, alzheimer's syndrome, and parathyroid compensatory hyperplasia. In view of the toxic effects of fluoride on human health, there is an urgent need to find an effective technique for removing excess fluoride from drinking water and industrial wastewater.
Among various methods for removing fluorine, an adsorption method using an industrial resin as an adsorbent is widely used, however, at present, the conventional industrial resin synthesis process and raw materials have great environmental hazard, the resin activation and regeneration process is complex, the amount of consumed medicine is large, and the adsorption selectivity is low.
It should be noted that the information disclosed in the above background section is only for understanding the background of the present application and thus may include information that does not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
Aiming at the defect that the existing fluorine adsorbent has difficult consideration of adsorption capacity, cycle regeneration capacity and adsorption selectivity, the invention provides a fluorine removal composite material and a preparation method thereof, which have good adsorption capacity, excellent cycle regeneration capacity and ion selectivity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a defluorination composite material comprises a calcium alginate shell and aluminum alginate-aluminum iminodiacetic acid gel inside the calcium alginate shell.
Further, in the aluminum alginate-iminodiacetic acid aluminum gel, the skeleton is an alginic acid main chain, the functional group is carboxyl chelated with aluminum, and the carboxyl is provided by alginic acid molecules and iminodiacetic acid molecules together.
A method of making the defluorinated composite comprising the steps of:
carrying out dehydration condensation reaction on the sodium alginate and graphene oxide mixed solution and iminodiacetic acid to obtain sodium alginate-iminodiacetic acid composite gel;
reacting the sodium alginate-iminodiacetic acid composite gel with a calcium chloride solution to prepare a hemispherical calcium alginate-iminodiacetic acid composite material;
and reacting the calcium alginate-iminodiacetic acid composite material with an aluminum sulfate solution to form the aluminum alginate-iminodiacetic acid composite material coated by the calcium alginate shell.
Further, the method specifically comprises the following steps:
(1) Preparing a mixed solution of sodium alginate with the concentration of 8-18 g/L and graphene oxide with the concentration of 1.6-3.5 g/L, and stirring 5-10 h to completely dissolve and uniformly mix the mixed solution;
(2) Adding an effective amount of a dehydration condensing agent, preferably an amount of the dehydration condensing agent with substances such as sodium alginate, into the mixed solution obtained in the step (1), and stirring for 20-60 min;
(3) Adding iminodiacetic acid into the mixed solution obtained in the step (2) to make the concentration of the iminodiacetic acid be 8-9 g/L, stirring for 2-5 h, and then standing for more than 5 h to form sodium alginate-iminodiacetic acid composite gel;
(4) Dropwise adding the composite gel obtained in the step (3) into 4.5-6.5 g/L of calcium chloride solution, standing for 10-30 min to obtain a hemispherical calcium alginate-iminodiacetic acid composite material, filtering and washing;
(5) Adding the composite material obtained in the step (3) into an aluminum sulfate solution with the concentration of 100-250 g/L, stirring and oscillating to react for 0.5-5 h, and filtering to obtain the aluminum alginate-aluminum iminodiacetic acid composite material.
The invention has the following beneficial effects:
the invention provides a defluorination composite material and a preparation method thereof, wherein the defluorination composite material has good fluorine adsorption capacity, excellent recycling capability and ion selectivity. The defluorination composite material can realize high-efficiency defluorination in a high-calcium environment and can be stably recycled.
Compared with the prior art, the invention has the following advantages:
(1) The adsorption capacity is large, compared with the resin which is put into use, the adsorption capacity of the festuca arundinacea is 1.3 times and 1.8 times of that of the Dusheng CH87 sulfonic acid resin and the Dupont Amberlite IRC76CRF carboxyl resin respectively, and the residual fluoride ion concentration after the adsorption saturation is 0.1 times and 0.05 times of that of the Dusheng CH87 sulfonic acid resin and the Dupont Amberlite IRC76CRF carboxyl resin respectively under the same condition.
(2) The calcium ions slightly promote the defluorination adsorption performance of the composite material, and can be used in a high-calcium environment.
(3) The adsorption defluorination rate is faster, and the adsorption capacity is close to the saturated adsorption capacity after 2h is more than twice the adsorption rate of the resin which is put into use.
(4) The fluorine removal composite material with low adsorption lower limit and high fluorine removal efficiency of 0.4 and g can reduce the solution with initial fluorine ion concentration of 10 mg/L of 100 mL to 0.012 mg/L within 5min, and the fluorine removal efficiency within 5min is 99.88%.
(5) The regeneration method is simple and has good effect, and the regeneration efficiency is higher than 92% only by putting the regeneration method in aluminum sulfate solution again for stirring or shaking.
(6) The sodium alginate serving as a raw material is a natural macromolecular organic matter, and is environment-friendly and harmless to the health of operators.
(7) The reaction is mild, and compared with the organic synthesis reaction at high temperature, high pressure and the like in the traditional PS resin manufacturing process, the fluorine removal material manufacturing process is carried out under the conditions of normal temperature and aqueous solution.
Other advantages of embodiments of the present invention are further described below.
Drawings
FIG. 1 is F of a defluorinated composite according to an embodiment of the invention - The adsorption rate varies with time.
FIG. 2 is a graph showing the adsorption capacity of the defluorinated composite according to the embodiment of the present invention as a function of the number of regenerations.
Detailed Description
The following describes embodiments of the present invention in detail. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its applications.
The embodiment of the invention provides a defluorination composite material, which comprises a calcium alginate shell and aluminum alginate-aluminum iminodiacetic acid gel inside the calcium alginate shell.
In some embodiments, in the aluminum alginate-iminodiacetic acid aluminum gel, the backbone is an alginic acid backbone, the functional groups are carboxyl groups chelated with aluminum, the carboxyl groups being provided by alginic acid molecules in combination with iminodiacetic acid molecules.
In some embodiments, the surface diameter of the defluorinated composite is 2000-4000 microns.
The embodiment of the invention also provides a method for preparing the defluorination composite material, which comprises the following steps:
carrying out dehydration condensation reaction on the sodium alginate and graphene oxide mixed solution and iminodiacetic acid to obtain sodium alginate-iminodiacetic acid composite gel;
reacting the sodium alginate-iminodiacetic acid composite gel with a calcium chloride solution to prepare a hemispherical calcium alginate-iminodiacetic acid composite material;
and (3) reacting the calcium alginate-iminodiacetic acid composite material with aluminum sulfate solution, and complexing with aluminum sulfate to form the aluminum alginate-iminodiacetic acid composite material coated by the calcium alginate shell.
In some embodiments, the method specifically comprises the steps of:
(1) Preparing a mixed solution of sodium alginate with the concentration of 8-18 g/L and graphene oxide with the concentration of 1.6-3.5 g/L, and stirring 5-10 h to completely dissolve and uniformly mix the mixed solution;
(2) Adding an effective amount of a dehydration condensing agent, preferably an amount of the dehydration condensing agent with substances such as sodium alginate, into the mixed solution obtained in the step (1), and stirring for 20-60 min;
(3) Adding iminodiacetic acid into the mixed solution obtained in the step (2) to make the concentration of the iminodiacetic acid be 8-9 g/L, stirring for 2-5 h, and then standing for more than 5 h to form sodium alginate-iminodiacetic acid composite gel;
(4) Dropwise adding the composite gel obtained in the step (3) into 4.5-6.5 g/L of calcium chloride solution, standing for 10-30 min to obtain a hemispherical calcium alginate-iminodiacetic acid composite material, filtering and washing;
(5) Adding the composite material obtained in the step (3) into an aluminum sulfate solution with the concentration of 100-250 g/L, stirring and oscillating to react for 0.5-5 h, and filtering to obtain the aluminum alginate-aluminum iminodiacetic acid composite material.
In a preferred embodiment, in step (1) sodium alginate powder having a viscosity of 200.+ -.20 mpa.s is used.
In a preferred embodiment, in the step (1), a mixed solution of sodium alginate with the concentration of 12-15 g/L and graphene oxide with the concentration of 2.0-3.0 g/L is prepared.
In a preferred embodiment, in step (2), the dehydration condensing agent is Diisopropylcarbodiimide (DIC), dicyclohexylcarbodiimide (DCC), or 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDC).
In a preferred embodiment, in step (2), the stirring period is 20-30 min.
In a preferred embodiment, in step (3), the iminodiacetic acid concentration is 8-9 g/L.
In a preferred embodiment, in step (4), the calcium chloride solution concentration is 5-6 g/L.
In a preferred embodiment, in step (5), the aluminum sulfate concentration is 180-220 g/L.
Specific embodiments of the present invention are described further below.
Example 1
Preparation of a defluorination material:
(1) Adding 0.4 g sodium alginate and 0.06 g graphene oxide into 30 mL water to form a mixed solution, stirring 10 h to completely dissolve and uniformly mix.
(2) Adding diisopropylcarbodiimide, which is a dehydration condensing agent with sodium alginate 0.26-g, into the mixed solution in the step (1), and stirring for 60 min.
(3) To the mixture in (2), 0.256% g% iminodiacetic acid was added, and 4. 4 h% was stirred. And then standing for 5 h to form the sodium alginate-iminodiacetic acid composite gel.
(4) The calcium chloride solution was prepared by dissolving 0.555 g calcium chloride in 100 mL water.
(5) And (3) dropwise adding the composite gel in the step (3) into the calcium chloride solution in the step (4), and standing for 20 min to obtain the hemispherical calcium alginate-iminodiacetic acid composite material. Filtered using gauze and washed with pure water.
(6) The 60 g aluminum sulfate powder was added to 300 mL pure water to prepare an aluminum sulfate solution, which was added to the composite material of 30 mL (5). And (3) oscillating for 2 hours, and filtering to obtain the aluminum alginate-aluminum iminodiacetic acid composite material.
Fluorine removal evaluation test:
0.4 of g of each fluorine removal material was added to 100 mL sodium fluoride solutions having initial concentrations of 11.875, 23.75, 47.5, 95, 190 mg/L, respectively. After magnetic stirring 4 h, the concentration of fluoride ions in the solution was measured using a fluoride ion electrode. The fluoride ion concentration was measured to be reduced to 0.01, 0.03, 5.36, 7.01, 72.70 mg/L, respectively.
Example 2
Preparation of a defluorination material:
(1) Adding 0.4 g sodium alginate and 0.09 g graphene oxide into 30 mL water to form a mixed solution, stirring 10 h to completely dissolve and uniformly mix.
(2) Adding diisopropylcarbodiimide, which is a dehydration condensing agent with sodium alginate 0.26-g, into the mixed solution in the step (1), and stirring for 30 min.
(3) To the mixture in (2), 0.269/g iminodiacetic acid was added, and the mixture was stirred for 4: 4 h. And then standing for 10 h to form the sodium alginate-iminodiacetic acid composite gel.
(4) The calcium chloride solution was prepared by dissolving 0.555 g calcium chloride in 100 mL water.
(5) And (3) dropwise adding the composite gel in the step (3) into the calcium chloride solution in the step (4), and standing for 20 min to obtain the hemispherical calcium alginate-iminodiacetic acid composite material. Filtered using gauze and washed with pure water.
(6) The 60 g aluminum sulfate powder was added to 300 mL pure water to prepare an aluminum sulfate solution, which was added to the composite material of 30 mL (5). And (3) oscillating for 2 hours, and filtering to obtain the aluminum alginate-aluminum iminodiacetic acid composite material.
Fluorine removal evaluation test:
0.4 of each of the g fluorine-removing materials was added to the 100 mL sodium fluoride solution having an initial concentration of 95 mg/L. The fluorine ion concentration in the solution is respectively reduced to 48.74, 42.26, 22.19, 16.68, 9.20 and 7.01 mg/L by adopting a fluorine ion electrode after magnetic stirring for 5min, 10 min, 20 min, 0.5 h, 1 h and 4 h.
Example 3
Preparation of a defluorination material:
(1) Adding 1 g sodium alginate and 0.2 g graphene oxide into 100 mL water to form a mixed solution, stirring 8 h to completely dissolve and uniformly mix.
(2) Adding diisopropylcarbodiimide, which is a dehydration condensing agent with sodium alginate 0.65-g, into the mixed solution in the step (1), and stirring for 40 min.
(3) To the mixture in (2), 0.673. 0.673 g iminodiacetic acid was added, and 4. 4 h was stirred. And then standing for 10 h to form the sodium alginate-iminodiacetic acid composite gel.
(4) A calcium chloride solution was prepared by dissolving 1.665 g calcium chloride in 300 mL water.
(5) And (3) dropwise adding the composite gel in the step (3) into the calcium chloride solution in the step (4), and standing for 20 min to obtain the hemispherical calcium alginate-iminodiacetic acid composite material. Filtered using gauze and washed with pure water.
(6) The 60 g aluminum sulfate powder was added to 300 mL pure water to prepare an aluminum sulfate solution, which was added to the composite material of 30 mL (5). And (3) oscillating for 2 hours, and filtering to obtain the aluminum alginate-aluminum iminodiacetic acid composite material.
Fluorine removal evaluation test:
0.4 of each of the g fluorine-removing materials was added to the 100 mL sodium fluoride solution having an initial concentration of 95 mg/L. After magnetic stirring 4 h, the concentration of fluoride ions in the solution was measured using a fluoride ion electrode, and then regenerated using 200 g/L aluminum sulfate solution, and this was repeated 5 times. The adsorption capacities were measured to be 23.6, 23.1, 22.2, 20.9, 19.2 and mg/g with the increase in the number of regenerations, respectively. The regeneration efficiency is more than 92 percent each time.
Example 4
Preparation of a defluorination material:
(1) Adding 0.5 g sodium alginate and 0.1 g graphene oxide into 40 mL water to form a mixed solution, stirring 10 h to completely dissolve and uniformly mix.
(2) Adding diisopropylcarbodiimide, which is a dehydration condensing agent with sodium alginate 0.33 g, into the mixed solution in the step (1), and stirring for 30 min.
(3) To the mixture in (2), 0.337, 0.337 g iminodiacetic acid was added, and 4, 4 h was stirred. And then standing for 10 h to form the sodium alginate-iminodiacetic acid composite gel.
(4) A calcium chloride solution was prepared by dissolving 1.665 g calcium chloride in 300 mL water.
(5) And (3) dropwise adding the composite gel in the step (3) into the calcium chloride solution in the step (4), and standing for 20 min to obtain the hemispherical calcium alginate-iminodiacetic acid composite material. Filtered using gauze and washed with pure water.
(6) The 60 g aluminum sulfate powder was added to 300 mL pure water to prepare an aluminum sulfate solution, which was added to the composite material of 30 mL (5). And (3) oscillating for 2 hours, and filtering to obtain the aluminum alginate-aluminum iminodiacetic acid composite material.
Fluorine removal evaluation test:
0.4 of g fluorine removal material is added into 100 mL sodium fluoride solution with initial concentration of calcium ions of 0, 100, 200 and 300 mg/L respectively, wherein the initial concentration of fluorine ions is 95 mg/L. After magnetic stirring 4 h, the concentration of fluorine ions in the solution was reduced to 7.12, 6.24, 4.96 and 2.12 mg/L respectively by using a fluorine ion electrode. This shows that the defluorination performance of the defluorination material is slightly improved by calcium ions.
By way of example, FIG. 1 shows F of the defluorinated composite of example 2 of the invention - Adsorption rate varies with time, reaction conditions: f (F) - The initial concentration was 95 mg/L, pH=7, the addition amount of the adsorbent material was 4 g/L, and the solution volume was 100 mL. Fig. 2 shows the adsorption capacity of the defluorinated composite material of example 3 according to the invention as a function of the number of regenerations, the reaction conditions: f (F) - The initial concentration was 95 mg/L, pH=7, the addition amount of the adsorbent material was 4 g/L, the solution volume was 100 mL, and the reaction time was 4 h.
Compared with the existing fluorine adsorbent, the fluorine-removing composite material provided by the invention has good adsorption capacity, excellent cyclic regeneration capacity and ion selectivity.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention. In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "preferred embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Those skilled in the art may combine and combine the features of the different embodiments or examples described in this specification and of the different embodiments or examples without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The defluorination composite material is characterized by comprising a calcium alginate shell and aluminum alginate-aluminum iminodiacetate gel inside the calcium alginate shell.
2. The defluorinated composite of claim 1, wherein in the aluminum alginate-iminodiacetic acid gel, the backbone is an alginic acid backbone, the functional group is a carboxyl group chelated with aluminum, the carboxyl group being provided by alginic acid molecules in combination with iminodiacetic acid molecules.
3. The defluorinated composite of claim 1 or 2, wherein the surface diameter of the material is 2000-4000 microns.
4. A method of preparing a defluorinated composite material according to any one of claims 1 to 3, comprising the steps of:
carrying out dehydration condensation reaction on the sodium alginate and graphene oxide mixed solution and iminodiacetic acid to obtain sodium alginate-iminodiacetic acid composite gel;
reacting the sodium alginate-iminodiacetic acid composite gel with a calcium chloride solution to prepare a hemispherical calcium alginate-iminodiacetic acid composite material;
and reacting the calcium alginate-iminodiacetic acid composite material with an aluminum sulfate solution to form the aluminum alginate-iminodiacetic acid composite material coated by the calcium alginate shell.
5. The method according to claim 4, characterized in that it comprises the following steps:
(1) Preparing a mixed solution of sodium alginate with the concentration of 8-18 g/L and graphene oxide with the concentration of 1.6-3.5 g/L, and stirring 5-10 h to completely dissolve and uniformly mix the mixed solution;
(2) Adding a dehydration condensing agent in an amount equal to that of sodium alginate and the like into the mixed solution obtained in the step (1), and stirring for 20-60 min;
(3) Adding iminodiacetic acid into the mixed solution obtained in the step (2) to make the concentration of the iminodiacetic acid be 8-9 g/L, stirring for 2-5 h, and then standing for more than 5 h to form sodium alginate-iminodiacetic acid composite gel;
(4) Dropwise adding the composite gel obtained in the step (3) into 4.5-6.5 g/L of calcium chloride solution, standing for 10-30 min to obtain a hemispherical calcium alginate-iminodiacetic acid composite material, filtering and washing;
(5) Adding the composite material obtained in the step (3) into an aluminum sulfate solution with the concentration of 100-250 g/L, stirring and oscillating to react for 0.5-5 h, and filtering to obtain the aluminum alginate-aluminum iminodiacetic acid composite material.
6. The method according to claim 5, wherein in the step (1), sodium alginate powder having a viscosity of 200.+ -.20 mpa.s is used to prepare a mixed solution of sodium alginate having a concentration of 12 to 15 g/L and graphene oxide having a concentration of 2.0 to 3.0 g/L.
7. The method of claim 5 or 6, wherein in step (2), the dehydration condensing agent is Diisopropylcarbodiimide (DIC), dicyclohexylcarbodiimide (DCC), or 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDC); the stirring time is 20-30 min.
8. The method of claim 5 or 6, wherein in step (3), the iminodiacetic acid concentration is 8 to 9 g/L.
9. The method of claim 5 or 6, wherein in step (4), the concentration of the calcium chloride solution is 5-6 g/L.
10. The method according to claim 5 or 6, wherein in step (5), the aluminum sulfate concentration is 180 to 220 g/L.
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