CN114849677B - Phosphate adsorption material and preparation method thereof - Google Patents
Phosphate adsorption material and preparation method thereof Download PDFInfo
- Publication number
- CN114849677B CN114849677B CN202210656918.6A CN202210656918A CN114849677B CN 114849677 B CN114849677 B CN 114849677B CN 202210656918 A CN202210656918 A CN 202210656918A CN 114849677 B CN114849677 B CN 114849677B
- Authority
- CN
- China
- Prior art keywords
- phosphate
- adsorption material
- hollow silicon
- silicon spheres
- preparing
- 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.)
- Active
Links
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 43
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 39
- 239000010452 phosphate Substances 0.000 title claims abstract description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 45
- 239000010703 silicon Substances 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JZWRCMHMJRWWDL-UHFFFAOYSA-N chloro(trimethyl)silane;toluene Chemical compound C[Si](C)(C)Cl.CC1=CC=CC=C1 JZWRCMHMJRWWDL-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/105—Phosphorus compounds
-
- 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
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (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 discloses a phosphate adsorption material and a preparation method thereof, wherein the preparation method comprises the following steps: putting the hollow silicon spheres into a mixed solution of trimethylchlorosilane and toluene, stirring and soaking for 18-24 hours, and then vacuum drying at 130-150 ℃ to obtain modified hollow silicon spheres; soaking the modified hollow silicon spheres by using a methacryloxyethyl trimethyl ammonium chloride solution, irradiating the modified hollow silicon spheres by using ultraviolet rays in the soaking process, and taking out the hollow silicon spheres after 1 to 1.5 hours to obtain an intermediate for later use; and (3) placing the intermediate in a tube furnace, heating to 600-700 ℃, preserving heat for 2-3 hours, and cooling to room temperature to obtain the phosphate adsorption material. The phosphate adsorption material obtained by the preparation method has hydrophobicity and good selective adsorption capacity for phosphate.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a phosphate adsorption material and a preparation method thereof.
Background
As water pollution becomes more and more of a concern, the search for cost-effective wastewater treatment solutions has become a hot spot. Especially for rural areas with weak economic basis, most of domestic sewage is directly discharged into the environment without treatment, and becomes an important source of environmental pollution around living, and the environment is particularly represented by black and odorous water, and the water is in an extreme pollution state. The domestic sewage contains a large amount of nitrogen, phosphorus, organic matters and other pollution components, and has great harm to human health and ecosystems. The technology which is widely applied at present mainly comprises an MBR membrane bioreactor A 2 A series of biological treatment technologies such as an O anaerobic-aerobic anoxic reaction tank, etc., but the period is too long because the biological treatment system needs to culture and domesticate microorganisms; at the same time go out water PO 4 3- Has direct relation with the removal of climate and microorganism activity, and the stable water output is not easy to achieve. Thus, a stable PO is invented 4 3- The processing technology is particularly important.
The physical adsorption technology is an important technology for treating phosphorus in sewage, the existing physical adsorption materials are mainly carbon materials such as activated carbon and biochar, the carbon materials mainly adsorb molecular-level substances by utilizing Van der Waals force of the carbon materials, ions are not basically adsorbed, and meanwhile, as the carbon materials have hydrophilicity, a small number of points which can be used for adsorbing the ions in sewage treatment can be occupied, so that the adsorption capacity of the carbon materials to phosphorus is very low, and the adsorption and removal of phosphorus in domestic sewage cannot be satisfied.
Based on this, it is an important point of study for those skilled in the art to provide an adsorbent having hydrophobicity and good adsorption ability to phosphate.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a phosphate adsorption material and a preparation method thereof, wherein the phosphate adsorption material obtained by the preparation method has hydrophobicity and good adsorption capacity on phosphate.
The technical scheme of the invention is realized as follows:
the preparation method of the phosphate radical adsorption material comprises the following steps:
s1: putting the hollow silicon spheres into a mixed solution of trimethylchlorosilane and toluene, stirring and soaking for 18-24 hours, and then vacuum drying at 130-150 ℃ to obtain modified hollow silicon spheres;
s2: soaking the modified hollow silicon spheres obtained in the step S1 by using a methacryloxyethyl trimethyl ammonium chloride solution, irradiating by using ultraviolet rays in the soaking process, and taking out after 1-1.5 h to obtain an intermediate for later use;
s3: placing the intermediate in a tube furnace, heating to 600-700 ℃, preserving heat for 2-3 h, and cooling to room temperature to obtain the phosphate adsorption material.
Further, the hollow silicon spheres have a particle size greater than 2mm.
Further, the hollow silicon ball is prepared by the following method:
(1) Adding cetyltrimethylammonium bromide, octadecyl trimethylammonium bromide and cetylpyridinium bromide into ethanol water solution, and stirring and dissolving in water bath at 25 ℃ to obtain a mixed solution I; the volume ratio of deionized water to ethanol in the ethanol water solution is 1:0.7;
(2) Performing ultrasonic treatment on the mixed solution I at 25 ℃ for 25-30 min, adding 25wt% ammonia water to adjust the pH value to 8-9 in the ultrasonic process, adding 0.5-2 mL of tetraethyl silicate, and obtaining a mixed solution II after the ultrasonic treatment is finished;
(3) Stirring the mixed solution II in water bath at 70 ℃ for 4 hours, separating to obtain a white product, drying at 60-70 ℃ for 6 hours, washing with deionized water, and finally freeze-drying at-52 ℃ for 24 hours for later use;
(4) And (3) placing the white product obtained after freeze drying in the step (3) in a muffle furnace, heating to 550 ℃ at a heating rate of 1 ℃/min, calcining for 6 hours, cooling to room temperature, and washing with deionized water to obtain the hollow silicon spheres.
Further, the ratio of the ethanol aqueous solution, cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide and cetylpyridinium bromide is: 100mL:0.25g:0.1g:0.25g.
Further, the mass concentration of the trimethylchlorosilane in the mixed solution in the step S1 is 5-7%.
Further, in the step S1, the mixture is stirred and immersed in a constant-temperature water bath at the temperature of 70-80 ℃ at the stirring speed of 100-120 r/min.
Further, the concentration of the methacryloyloxyethyl trimethyl ammonium chloride solution in the step S2 is 15 to 25mmol/L.
Further, in the step S2, the ultraviolet wavelength is 300-365 nm, and the intensity is 8-10 mw/cm 2 。
Further, the temperature rising speed in the step S3 is 5-15 ℃/min.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the hollow silicon spheres are used as a matrix, the hollow silicon spheres have high specific surface area and good adsorption capacity, and hydrophobic groups such as silicon base, silicon oxygen base, silicon hydroxyl and the like are introduced into the surfaces of the hollow silicon spheres by utilizing the hydrolysis of trimethylchlorosilane, so that the hollow silicon spheres are subjected to hydrophobic modification, the hydrophobic performance of the adsorption material is enhanced, and the adsorption capacity of the adsorption material is not limited by a liquid phase; then, the adsorption effect on phosphate ions is further enhanced by utilizing the electric adsorption effect of the methacryloyloxyethyl trimethyl ammonium chloride carrying positive charges.
2. The hydrophobic modification can cause the problem of blocking the pores of the hollow silicon spheres, and the principle that the high temperature can cause the content of oxygen-containing groups of the material to be reduced and the pores to expand is utilized, so that the pores blocked by the hollow silicon spheres are opened, thereby ensuring that the adsorption material has good adsorption capacity while having hydrophobic requirements.
3. The invention adopts the soft template method to prepare the hollow silicon spheres, has simple preparation process, easily obtained raw materials and low cost, and is beneficial to large-scale production. The mass ratio of silicon base in the prepared phosphate radical adsorption material is about 0.3-1%, and the mass ratio of silicon base is about 1-2%.
Drawings
FIG. 1-SEM image of hollow silicon spheres prepared in example 19.
FIG. 2-SEM image of modified hollow silicon spheres prepared in example 19.
FIG. 3-SEM image of an intermediate prepared in example 19.
FIG. 4-SEM image of the phosphate adsorption material prepared in example 19.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1
To 100mL of deionized water and ethanol solution (volume ratio of water to ethanol is 1:0.7), 0.250g of cetyltrimethylammonium bromide, 0.1g of octadecyl trimethyl ammonium bromide, 0.250g of cetylpyridinium bromide were added, and the mixture was dissolved by stirring in a water bath at 25 ℃; ultrasonic treating the solution at 25deg.C for 25min, adding 25% ammonia water to adjust pH to 8-9 during ultrasonic treating for 3min, adding 0.5mL tetraethyl silicate, and taking out the mixed solution after ultrasonic treating; stirring the obtained solution for 4 hours at 70 ℃ by using an electromagnetic stirring device, taking out a white product in the solution, drying for 6 hours at 60-70 ℃, washing with deionized water, and freeze-drying for 24 hours at-52 ℃; calcining the product in a muffle furnace at 550 ℃ for 6 hours at a heating rate of 1 ℃/min; cooling to room temperature, taking out deionized water, and washing to obtain hollow silicon spheres; and (5) screening out hollow silicon spheres with the particle size of more than 2mm by using an 8-mesh sieve for later use.
Taking the hollow silicon spheres as a matrix, putting the hollow silicon spheres into a toluene solution of TMCS trimethylchlorosilane with the mass concentration of 6%, heating, stirring and soaking in a constant-temperature water bath at the temperature of 75 ℃ for 24 hours, wherein the stirring speed is 120r/min; and (5) drying in vacuum for 2 hours after the impregnation is finished, wherein the drying temperature is 150 ℃ to obtain the modified hollow silicon spheres.
Soaking the modified hollow silicon spheres by using a methacryloxyethyl trimethyl ammonium chloride solution with the concentration of 20mmol/L, and irradiating and reacting for 1h by using an ultraviolet lamp in the soaking process, wherein the wavelength of the ultraviolet lamp is 365nm, and the intensity is 8mw/cm 2 Thereby obtaining an intermediate.
And (3) placing the intermediate in a tube furnace, setting the heating temperature of the tube furnace to be 700 ℃, heating from room temperature at a heating rate of 10 ℃/min, keeping the temperature for 3 hours after heating to 700 ℃, and cooling to room temperature to obtain the phosphate radical adsorption material.
The preparation methods of examples 2 to 27 are the same as those of example 1, except that the mass concentration of tetraethyl silicate, trimethylchlorosilane toluene solution or the concentration of methacryloyloxyethyl trimethyl ammonium chloride are different, and specific process parameters are shown in Table 1.
TABLE 1 Main Process parameters for examples 1-27
Among them, SEM electron microscope images of the hollow silica spheres, the modified hollow silica spheres, and the intermediate obtained in example 19 are shown in fig. 1, fig. 2, fig. 3, and fig. 4, respectively, and it can be seen from the figures: after the hollow silicon spheres are subjected to hydrophobic modification, the pore channels of the hollow silicon spheres are partially blocked by a modifier, and organosilane exists on the surfaces of the hollow silicon spheres, so that the hollow silicon spheres can play a hydrophobic role; after ultraviolet irradiation treatment and introduction of positive charge of the methacryloxyethyl trimethyl ammonium chloride, the electric property of the material is enhanced, the blocked pore is partially opened, and finally, after high-temperature heat treatment, the pore is completely opened, and meanwhile, the oxygen-containing groups on the surface are reduced, so that the material has better hydrophobicity and phosphate adsorption characteristics.
The adsorption performance of the hollow silica spheres, the modified hollow silica spheres, the intermediate and the finally obtained phosphate radical adsorption material prepared in examples 1 to 27 was tested, the volume of the inlet water was 5L, the concentration of phosphate radical in the inlet water was 16mg/L, the inlet water uniformly passed through the adsorption material, the addition amount of the adsorption material was 10g/L, namely 50g of the adsorption material, the adsorption temperature was 25 ℃, and the water flow rate was 3mL/s. The test results are shown in Table 2.
TABLE 2 removal rates of phosphate groups (%)
| Examples | Hollow silicon ball | Modified hollow silicon ball | Intermediate products | Phosphate adsorbing material |
| Example 1 | 48.3 | 68.7 | 78.6 | 90.1 |
| Example 2 | / | / | 84.0 | 87.4 |
| Example 3 | / | / | 83.0 | 93.4 |
| Example 4 | / | 67.2 | 84.2 | 92.4 |
| Example 5 | / | / | 82.4 | 90.4 |
| Example 6 | / | / | 85.5 | 92.8 |
| Example 7 | / | 68.9 | 82.2 | 92.4 |
| Example 8 | / | / | 81.3 | 91.0 |
| Example 9 | / | / | 85.6 | 93.4 |
| Example 10 | 61.6 | 74.5 | 85.2 | 91.8 |
| Example 11 | / | / | 85.5 | 88.8 |
| Example 12 | / | / | 85.2 | 88.7 |
| Example 13 | / | 72.2 | 83.3 | 92.7 |
| Example 14 | / | / | 82.4 | 92.8 |
| Example 15 | / | / | 86.1 | 89.3 |
| Example 16 | / | 71.8 | 81.7 | 87.8 |
| Example 17 | / | / | 81.0 | 87.4 |
| Example 18 | / | / | 85.2 | 93.1 |
| Example 19 | 60.3 | 70.2 | 87.1 | 93.4 |
| Example 20 | / | / | 83.3 | 90.6 |
| Example 21 | / | / | 87.3 | 89.0 |
| Example 22 | / | 70.4 | 84.0 | 90.2 |
| Example 23 | / | / | 82.9 | 88.3 |
| Example 24 | / | / | 83.5 | 87.2 |
| Example 25 | / | 72.8 | 85.9 | 91.0 |
| Example 26 | / | / | 81.9 | 93.4 |
| Example 27 | / | / | 84.0 | 87.2 |
As can be seen from table 2: compared with the hollow silicon spheres, the modified hollow silicon spheres have the advantages that the adsorption efficiency of phosphate is improved by more than 15% due to the improvement of the hydrophobic property, so that the effectiveness of the hydrophobic modification method is proved; comparing the adsorption capacities of the intermediate material and the modified hollow silicon spheres, the introduction of positive charges can be found to effectively enhance the phosphate adsorption capacity of the material; the phosphate adsorption material and the intermediate are compared, and the effectiveness of high-temperature treatment is further verified. Compared with the original hollow silicon sphere adsorption material, the phosphate adsorption capacity of the phosphate adsorption material after the introduction of the positive charges through hydrophobic modification is obviously improved, the phosphate adsorption capacity is generally improved by more than 50%, and the phosphate removal efficiency is more than 87%.
The optimal adding amount of the three substances can be respectively 2mL, 6wt% and 20mmoL by controlling the mass concentration of the tetraethyl silicate, the trimethylchlorosilane toluene solution and the concentration of the methacryloyloxyethyl trimethyl ammonium chloride in the embodiment, and the adsorption capacity of the obtained adsorption material is as high as 93.4 percent, and compared with similar adsorption products, the adsorption capacity of the adsorption material has extremely high phosphate radical adsorption capacity.
Finally, it should be noted that the above-mentioned examples of the present invention are only illustrative of the present invention and are not limiting of the embodiments of the present invention. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. Not all embodiments are exhaustive. Obvious changes and modifications which are extended by the technical proposal of the invention are still within the protection scope of the invention.
Claims (9)
1. The preparation method of the phosphate radical adsorption material is characterized by comprising the following steps:
s1: putting the hollow silicon spheres into a mixed solution of trimethylchlorosilane and toluene, stirring and soaking for 18-24 hours, and then vacuum drying at 130-150 ℃ to obtain modified hollow silicon spheres;
s2: soaking the modified hollow silicon spheres obtained in the step S1 by using a methacryloxyethyl trimethyl ammonium chloride solution, irradiating by using ultraviolet rays in the soaking process, and taking out after 1-1.5 h to obtain an intermediate for later use; wherein the ultraviolet waveThe length is 300-365 nm, and the intensity is 8-10 mw/cm 2 ；
S3: and (3) placing the intermediate in a tube furnace, heating to 600-700 ℃, preserving heat for 2-3 hours, and cooling to room temperature to obtain the phosphate adsorption material, wherein the mass ratio of silicon groups in the phosphate adsorption material is 0.3-1%, and the mass ratio of silicon groups is 1-2%.
2. The method for preparing a phosphate adsorbing material according to claim 1, wherein the particle size of the hollow silica spheres is larger than 2mm.
3. The method for preparing a phosphate adsorption material according to claim 2, wherein the hollow silicon spheres are prepared by the following method:
(1) Adding cetyltrimethylammonium bromide, octadecyl trimethylammonium bromide and cetylpyridinium bromide into ethanol water solution, and stirring and dissolving in water bath at 25 ℃ to obtain a mixed solution I; the volume ratio of deionized water to ethanol in the ethanol water solution is 1:0.7;
(2) Performing ultrasonic treatment on the mixed solution I at 25 ℃ for 25-30 min, adding 25wt% ammonia water to adjust the pH to 8-9 in the ultrasonic process, adding 0.5-2 mL of tetraethyl silicate, and obtaining a mixed solution II after the ultrasonic treatment is finished;
(3) Stirring the mixed solution II in a water bath at 70 ℃ for 4-h, separating to obtain a white product, drying at 60-70 ℃ for 6-h, washing with deionized water, and finally freeze-drying at-52 ℃ for 24-h for later use;
(4) And (3) placing the white product obtained after freeze drying in the step (3) in a muffle furnace, heating to 550 ℃ at a heating rate of 1 ℃/min, calcining for 6 hours, cooling to room temperature, and washing with deionized water to obtain the hollow silicon spheres.
4. The method for preparing a phosphate adsorbing material according to claim 3, wherein the ratio of the aqueous ethanol solution, cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide and cetylpyridinium bromide is: 100mL:0.25g:0.1g:0.25g.
5. The method for preparing a phosphate adsorption material according to claim 1, wherein the mass concentration of trimethylchlorosilane in the mixed solution in the step S1 is 5-7%.
6. The method for preparing a phosphate adsorbing material according to claim 1, wherein in the step S1, the stirring and the soaking are performed in a constant-temperature water bath at 70-80 ℃ at a stirring speed of 100-120 r/min.
7. The method for preparing a phosphate adsorption material according to claim 1, wherein the concentration of the methacryloyloxyethyl trimethyl ammonium chloride solution in the step S2 is 15-25 mmol/L.
8. The method for preparing a phosphate adsorption material according to claim 1, wherein the heating rate in the step S3 is 5-15 ℃/min.
9. The phosphate adsorption material is characterized by being prepared by the preparation method of any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210656918.6A CN114849677B (en) | 2022-06-10 | 2022-06-10 | Phosphate adsorption material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210656918.6A CN114849677B (en) | 2022-06-10 | 2022-06-10 | Phosphate adsorption material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114849677A CN114849677A (en) | 2022-08-05 |
| CN114849677B true CN114849677B (en) | 2024-01-26 |
Family
ID=82625383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210656918.6A Active CN114849677B (en) | 2022-06-10 | 2022-06-10 | Phosphate adsorption material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114849677B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0049936A1 (en) * | 1980-10-13 | 1982-04-21 | European Atomic Energy Community (Euratom) | A method of encapsulating materials in a zeolite in a stable manner |
| JPH10202095A (en) * | 1997-01-28 | 1998-08-04 | Tosoh Corp | Silica-base adsorption separating agent, its production and filter using same |
| JP2004197018A (en) * | 2002-12-20 | 2004-07-15 | National Institute Of Advanced Industrial & Technology | Spherical porous silica particle and method for producing the same |
| KR20050060185A (en) * | 2003-12-16 | 2005-06-22 | 한국생산기술연구원 | Preparation method of the polyelectrolytes-impregnated mesoporous ceramic adsorbents for waste water treatment |
| CN101053827A (en) * | 2007-05-10 | 2007-10-17 | 复旦大学 | Surface fixing metal ions magnetic microspheres and its preparation method and application |
| CN101356003A (en) * | 2005-12-16 | 2009-01-28 | 阿克佐诺贝尔公司 | Silica based material |
| CN102745696A (en) * | 2011-04-19 | 2012-10-24 | 哈尔滨工业大学 | Preparation method of hydrophobic silica fiber film and use of the hydrophobic silica fiber film in removal of organic pollutants |
| CN105709700A (en) * | 2016-05-05 | 2016-06-29 | 济南大学 | Preparation method of dimethyl-diallyl ammonium chloride modified reed stem adsorbent |
| CN105935587A (en) * | 2016-06-28 | 2016-09-14 | 安徽金联地矿科技有限公司 | Method using attapulgite to prepare particles for removing phosphor from water |
| CN106111088A (en) * | 2016-07-11 | 2016-11-16 | 常州大学 | A kind of preparation method of silicon dioxide/cationic-type polyacrylamide hybrid sorbents |
| CN106512921A (en) * | 2016-11-30 | 2017-03-22 | 昆明理工大学 | Modified silicon dioxide nanoparticles, and preparation method and application thereof |
| CN106902781A (en) * | 2017-03-08 | 2017-06-30 | 江苏大学 | The preparation method and applications of modified meso-porous hollow silicon ball adsorbent |
| CN107029669A (en) * | 2017-04-14 | 2017-08-11 | 山西省农业科学院农产品贮藏保鲜研究所 | A kind of fruit and vegetable storage and transportation carbon-dioxide absorbent and preparation method thereof |
| CN108101066A (en) * | 2017-11-23 | 2018-06-01 | 浙江大学 | A kind of preparation method and applications of the spherical ordered multi-stage porous silica adsorbent of hydrophobicity |
| CN109453752A (en) * | 2018-11-30 | 2019-03-12 | 重庆大学 | A kind of cationic magnetic nanoparticle and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009041727A1 (en) * | 2007-09-28 | 2009-04-02 | Nippon Shokubai Co., Ltd. | Water absorbing agent and production method thereof |
| US9943826B2 (en) * | 2013-09-26 | 2018-04-17 | Regents Of The University Of Minnesota | Porous silica having high pore volume and methods of making and using same |
| CN108212080B (en) * | 2017-12-12 | 2019-05-31 | 江苏省农业科学院 | A kind of preparation method and application of composite modified stalk active particle charcoal adsorbent material |
-
2022
- 2022-06-10 CN CN202210656918.6A patent/CN114849677B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0049936A1 (en) * | 1980-10-13 | 1982-04-21 | European Atomic Energy Community (Euratom) | A method of encapsulating materials in a zeolite in a stable manner |
| JPH10202095A (en) * | 1997-01-28 | 1998-08-04 | Tosoh Corp | Silica-base adsorption separating agent, its production and filter using same |
| JP2004197018A (en) * | 2002-12-20 | 2004-07-15 | National Institute Of Advanced Industrial & Technology | Spherical porous silica particle and method for producing the same |
| KR20050060185A (en) * | 2003-12-16 | 2005-06-22 | 한국생산기술연구원 | Preparation method of the polyelectrolytes-impregnated mesoporous ceramic adsorbents for waste water treatment |
| CN101356003A (en) * | 2005-12-16 | 2009-01-28 | 阿克佐诺贝尔公司 | Silica based material |
| CN101053827A (en) * | 2007-05-10 | 2007-10-17 | 复旦大学 | Surface fixing metal ions magnetic microspheres and its preparation method and application |
| CN102745696A (en) * | 2011-04-19 | 2012-10-24 | 哈尔滨工业大学 | Preparation method of hydrophobic silica fiber film and use of the hydrophobic silica fiber film in removal of organic pollutants |
| CN105709700A (en) * | 2016-05-05 | 2016-06-29 | 济南大学 | Preparation method of dimethyl-diallyl ammonium chloride modified reed stem adsorbent |
| CN105935587A (en) * | 2016-06-28 | 2016-09-14 | 安徽金联地矿科技有限公司 | Method using attapulgite to prepare particles for removing phosphor from water |
| CN106111088A (en) * | 2016-07-11 | 2016-11-16 | 常州大学 | A kind of preparation method of silicon dioxide/cationic-type polyacrylamide hybrid sorbents |
| CN106512921A (en) * | 2016-11-30 | 2017-03-22 | 昆明理工大学 | Modified silicon dioxide nanoparticles, and preparation method and application thereof |
| CN106902781A (en) * | 2017-03-08 | 2017-06-30 | 江苏大学 | The preparation method and applications of modified meso-porous hollow silicon ball adsorbent |
| CN107029669A (en) * | 2017-04-14 | 2017-08-11 | 山西省农业科学院农产品贮藏保鲜研究所 | A kind of fruit and vegetable storage and transportation carbon-dioxide absorbent and preparation method thereof |
| CN108101066A (en) * | 2017-11-23 | 2018-06-01 | 浙江大学 | A kind of preparation method and applications of the spherical ordered multi-stage porous silica adsorbent of hydrophobicity |
| CN109453752A (en) * | 2018-11-30 | 2019-03-12 | 重庆大学 | A kind of cationic magnetic nanoparticle and its preparation method and application |
Non-Patent Citations (7)
| Title |
|---|
| "Adsorptive removal of nitrate and phosphate anions from aqueous solutions using functionalised SBA-15: Effects of the organic functional group";Safia Hamoudi et al;《The Canadian Journal of Chemical Engineering》;第90卷;全文 * |
| "Synthesis of hydrophobic zeolite X@SiO2 core-shell composites";Liying Liu et al;《Materials Chemistry and Physics》;第133卷;全文 * |
| "基于离子交换和表面引发接枝聚合制备阴离子表面印迹材料及其识别特性研究";杜俊玫等;《化学学报》;第70卷;全文 * |
| "磷酸修饰中空介孔硅球的制备及其对水中痕量锑（Ⅲ）的去除";晏垚;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第1期);全文 * |
| "纳米二氧化硅复合材料的制备及其对金的吸附性能";付立康;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第1期);第五章 * |
| Characterization of Hydrophobic SiO2 Powders Prepared by Surface Modification on Wet Gel;Ae-Young Jeong et al;Journal of Sol-Gel Science and Technology;第19卷;483-487 * |
| 黄微雅.《功能化有序介孔吸附剂及其在水处理中的应用》.冶金工业出版社,2021,第23-24页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114849677A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105236507B (en) | The method that the adsorbent being combined using beta cyclodextrin chitosan and walnut shell charcoal removes the Cr VI in waste water | |
| CN112844301B (en) | Dimer carboxyl adsorbent and preparation method and application thereof | |
| CN113351237B (en) | Floating type photocatalytic material, preparation method and antibiotic wastewater degradation treatment device thereof | |
| CN111944799B (en) | Preparation method and application of immobilized particles embedded with Thiobacillus denitrificans | |
| CN109876780A (en) | A kind of dephosphorization adsorbent and preparation method thereof | |
| CN111495336A (en) | Chitosan-acrylic acid-based magnetic hydrogel adsorption material and preparation method thereof | |
| CN113713768A (en) | High-temperature-resistant activated carbon composite adsorbent and preparation method and application thereof | |
| CN111495343A (en) | TiO 22Grafted polyacrylic acid hydrogel adsorption-degradation material and preparation method thereof | |
| CN114849677B (en) | Phosphate adsorption material and preparation method thereof | |
| CN112391375B (en) | Preparation method and application of biochar immobilized denitrifying bacteria for rapidly removing nitrate in water body | |
| CN108083452B (en) | Heterotrophic and sulfur autotrophic integrated solid-phase denitrification system for treating high-nitrate water body | |
| CN117003236A (en) | Shell activated carbon and preparation method and application thereof | |
| CN105582902A (en) | Composite gel material for treatment of heavy-metal-containing wastewater | |
| CN110559992B (en) | Preparation process of inorganic strong acid ammonium salt modified coconut shell activated carbon for removing formaldehyde in air at normal temperature, product and application thereof | |
| CN116532084A (en) | Nd-doped Bi 2 WO 6 Preparation and application of nanoflower-biomass porous carbon material | |
| CN110860109A (en) | Disposal method of XDK adsorbent capable of discharging up to standard waste transformer oil | |
| CN114394679B (en) | Microbial adsorbent for industrial wastewater and preparation method thereof | |
| CN109603781A (en) | A kind of adsorbent and its preparation method and application | |
| CN109231463A (en) | A kind of preparation and application of compound diatomite sewage-treating agent | |
| CN106540666B (en) | Adsorb the preparation method of the modified Carbon Materials of heavy metal ion silk cocoon | |
| CN105692583A (en) | Method for preparing beta-cyclodextrin-based boron-doped mesoporous carbon material through soft template method | |
| CN114433084A (en) | Preparation method and application of core-shell structure hollow carbon/silicon composite microsphere catalyst | |
| CN109231488B (en) | Method for synchronously treating nitrogen and phosphorus inorganic nutrients and organic pollutants in water body | |
| CN118204065B (en) | Preparation method of zeolite molecular sieve for VOCs treatment | |
| CN108773873A (en) | A kind of purifying agent for polluted water and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |