CN116726887A - Calcium peroxide slow-release gel composite material, preparation method and application thereof - Google Patents
Calcium peroxide slow-release gel composite material, preparation method and application thereof Download PDFInfo
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- CN116726887A CN116726887A CN202310951184.9A CN202310951184A CN116726887A CN 116726887 A CN116726887 A CN 116726887A CN 202310951184 A CN202310951184 A CN 202310951184A CN 116726887 A CN116726887 A CN 116726887A
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- release gel
- composite material
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- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 239000004343 Calcium peroxide Substances 0.000 title claims abstract description 48
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 235000019402 calcium peroxide Nutrition 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 85
- 239000011159 matrix material Substances 0.000 claims abstract description 80
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 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 33
- 239000000661 sodium alginate Substances 0.000 claims abstract description 33
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 33
- 150000001768 cations Chemical class 0.000 claims abstract description 18
- 239000011247 coating layer Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 73
- 239000002734 clay mineral Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 33
- 239000011575 calcium Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000012266 salt solution Substances 0.000 claims description 25
- 238000013268 sustained release Methods 0.000 claims description 19
- 239000012730 sustained-release form Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 159000000007 calcium salts Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000004113 Sepiolite Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910052624 sepiolite Inorganic materials 0.000 claims description 11
- 235000019355 sepiolite Nutrition 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 6
- 150000004677 hydrates Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 45
- 239000011574 phosphorus Substances 0.000 abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 40
- 230000000694 effects Effects 0.000 abstract description 25
- 239000000843 powder Substances 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 101100219043 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) BRE2 gene Proteins 0.000 description 68
- 239000000499 gel Substances 0.000 description 68
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000013049 sediment Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- -1 peroxide compound Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic 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
- B01J20/02—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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
-
- 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
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 relates to the technical field of eutrophic water body treatment, in particular to a calcium peroxide slow-release gel composite material, a preparation method and application thereof. The calcium peroxide slow release gel composite material comprises: loaded with CaO 2 A matrix material of nanoparticles; coated on the CaO-loaded components 2 A coating layer on the outer surface of the matrix material of the nanoparticles; the coating layer comprises metal cation crosslinked sodium alginate. CaO (CaO) 2 Nanoparticle support onThe surface and pores of the matrix material are conducive to improving the dispersibility of the nanoparticles; the sodium alginate is adopted to coat the formed composite material, so that CaO can be reduced 2 The contact opportunity of nano particles and water solves the problem of CaO 2 The powder reacts with water at too high a rate. In addition, the sodium alginate has higher porosity, and abundant hydroxyl and carboxyl in the molecular structure can be combined with high-valence metal cations, and the metal cations are introduced as phosphorus removal functional components, so that the phosphorus removal effect on the eutrophic water body is enhanced.
Description
Technical Field
The invention relates to the technical field of eutrophic water body treatment, in particular to a calcium peroxide slow-release gel composite material, a preparation method and application thereof.
Background
Phosphorus is a key limiting factor for lake eutrophication, and effectively controlling the content of phosphorus in water body has important significance for controlling water body eutrophication. In addition to limiting the input of exogenous phosphorus, it is also critical to reduce or fix the release of endogenous phosphorus contaminants in the overburden and sediment. Currently, the control means commonly used for endogenous nutrients (especially phosphorus) in surface waters include aquatic plant control techniques, oxygen supply techniques, in situ treatment techniques, and cover treatment techniques. The in-situ covering technology attracts wide attention because of simple operation and stable treatment effect, and is characterized by searching or developing a covering or passivation material with good selectivity, high adsorption capacity, strong anti-interference capability and stable use effect on low-concentration phosphorus.
Calcium peroxide (CaO) 2 ) Is a common and safe solid inorganic peroxide compound, shows stronger adsorption affinity to phosphate, and can realize the rapid removal of phosphorus with different concentrations. And, during the application process, caO 2 Can also react with water to release a large amount of oxygen to improve the water bodyThe content of dissolved oxygen in the sludge-water interface can avoid the release of endogenous phosphorus or other pollutants caused by anaerobic conditions, and has been widely applied to the purification of soil and groundwater.
However, caO 2 The nano particles are easy to agglomerate, and the powdered CaO 2 The reaction of the sample and water is too rapid, the dissolved oxygen level of the water body cannot be maintained for a long time, the slow release effect is not achieved, and a large amount of O is formed in a short time 2 The release of (2) also causes a decrease in the utilization properties of the material itself; in addition, due to CaO 2 The organic phosphorus-free composite material has a strong oxidation effect, and can convert part of unstable organic phosphorus or phosphorus in other forms in overlying water and bottom sludge into inorganic phosphorus and release the inorganic phosphorus in the overlying water when in use, but the adsorption capacity of the inorganic phosphorus-free composite material on phosphorus is insufficient, so that the fixing effect on endogenous phosphorus is unstable when in use, and the long-term phosphorus removal performance is insufficient.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a calcium peroxide slow-release gel composite material, a preparation method and application thereof.
The invention provides a calcium peroxide slow-release gel composite material, which comprises the following components:
loaded with CaO 2 A matrix material of nanoparticles;
coated on the CaO-loaded components 2 A coating layer on the outer surface of the matrix material of the nanoparticles;
the coating layer comprises metal cation crosslinked sodium alginate.
Preferably, the matrix material comprises a natural clay mineral matrix and/or a modified natural clay mineral matrix;
the natural clay mineral matrix comprises at least one of sepiolite, bentonite, halloysite, diatomite, attapulgite, kaolin, montmorillonite, illite, vermiculite and dolomite;
the metal cation comprises Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of them.
Preferably, the preparation method of the modified natural clay mineral substrate comprises the following steps:
mixing the natural clay mineral matrix with a strong acid solution, and boiling for reaction to obtain a modified natural clay mineral matrix;
the strong acid solution comprises concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid; the mass concentration of the strong acid solution is 1-10%;
the dosage ratio of the natural clay mineral matrix to the strong acid solution is 1g:1 mL-1 g:20mL;
the boiling reaction time is 0.5-2 h;
after the boiling reaction, the method further comprises the following steps: and cleaning, drying, grinding and sieving the reacted product.
Preferably, the CaO 2 The particle size of the nano particles is 20-100 nm;
the average grain diameter of the calcium peroxide slow-release gel composite material is 2-5 mm.
The invention also provides a preparation method of the calcium peroxide slow-release gel composite material, which comprises the following steps:
a) Mixing matrix material, soluble calcium salt solution, dispersant and precipitant, stirring to react to obtain CaO 2 A precursor solution;
the matrix material comprises a natural clay mineral matrix and/or a modified natural clay mineral matrix;
b) At the CaO 2 Dropwise adding H into the precursor solution 2 O 2 Stirring the solution in ice bath or at normal temperature to obtain CaO-loaded solution 2 A matrix material of nanoparticles;
c) Loading the CaO on the steel plate 2 Uniformly mixing the matrix material of the nano particles with the sodium alginate solution, and dripping the obtained mixed solution into the metal salt solution for curing reaction to obtain the calcium peroxide slow-release gel composite material.
Preferably, in step A), the soluble calcium salt comprises CaCl 2 、Ca(NO 3 ) 2 And at least one of its hydrates;
in the soluble calcium salt solution, ca 2+ The concentration of (2) is 0.05-3.0 mol/L;
ca in the soluble calcium salt solution 2+ The mass ratio of the polymer to the matrix material is 0.2-1: 1, a step of;
the dispersing agent comprises at least one of Cetyl Trimethyl Ammonium Bromide (CTAB), sodium citrate, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) 200 and PEG 400;
the precipitant comprises NH 3 ·H 2 O, naOH solution and KOH solution.
Preferably, in step B), the H 2 O 2 With CaO 2 Ca in precursor solution 2+ The molar ratio of (2) is 1:1 to 25:1, a step of;
the H is 2 O 2 The mass concentration of the solution is 5-30%;
the H is 2 O 2 The dropping rate of the solution is 0.1-10 mL/min;
the stirring reaction time is 30 min-2 h;
after the stirring reaction, the method further comprises the following steps:
and centrifugally collecting, cleaning, drying and grinding the product after the stirring reaction.
Preferably, in the step C), the mass concentration of the sodium alginate solution is 10-20 g/L;
the sodium alginate and the CaO-loaded 2 The mass ratio of the matrix material of the nano particles is 10:1 to 1:1, a step of;
the metal ions in the metal salt comprise Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of (a) and (b);
the metal salt solution comprises Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of soluble chloride, sulfate, nitrate and hydrates thereof;
the mass concentration of the metal salt solution is 0.1-2 mol/L;
the speed of dripping the mixed solution into the metal salt solution is 2-15 drops/min;
the curing reaction is carried out at normal temperature, and the reaction time is 0.5-6 h;
after the curing reaction, the method further comprises the following steps: filtering and cleaning.
The invention also provides an application of the calcium peroxide slow-release gel composite material or the calcium peroxide slow-release gel composite material prepared by the preparation method as described above as an eutrophic water body purification material.
The invention also provides a purification method of the eutrophic water body, which comprises the following steps:
mixing the calcium peroxide slow-release gel composite material with the eutrophic water body to obtain a purified water body;
the calcium peroxide slow-release gel composite material is the calcium peroxide slow-release gel composite material or the calcium peroxide slow-release gel composite material prepared by the preparation method.
The invention provides a calcium peroxide slow-release gel composite material, which comprises the following components: loaded with CaO 2 A matrix material of nanoparticles; coated on the CaO-loaded components 2 A coating layer on the outer surface of the matrix material of the nanoparticles; the coating layer comprises metal cations and sodium alginate. In the invention, caO 2 The nano particles are loaded on the surface and pores of the matrix material, so that the dispersibility of the nano particles is improved; sodium Alginate (SA) is adopted to coat the formed composite material to form slow release gel microspheres, which can reduce CaO 2 The contact opportunity of nano particles and water solves the problem of CaO 2 The powder reacts too fast with water, resulting in a problem of lack of slow release effect. In addition, the sodium alginate has higher porosity, and the hydroxyl and carboxyl groups abundant in the molecular structure can be obtained by the method of the sodium alginate and high-valence metal cations (such as Zr 4+ 、La 3+ 、Ce 3+ Or Fe (Fe) 3+ ) Combining, introducing metal cations as a dephosphorization functional component, and enhancing the removal effect of phosphorus in the eutrophic water body; meanwhile, the metal cations can be introduced to increase the active sites of the metal cations, so that the selectivity and the adsorption capacity of the composite adsorbent to phosphorus are expected to be improved. The invention is further limited toThe specific components of the metal cations are determined, which helps to improve the above effects.
Drawings
FIG. 1 is an XRD pattern of a modified natural clay mineral matrix and CPS60@SA/La sustained release gel composite material according to example 1 of the present invention;
FIG. 2 is an SEM image of a CPS60@SA/La sustained release gel composite material of example 1 of the present invention;
FIG. 3 is an elemental analysis chart of a CPS60@SA/La sustained release gel composite material of example 1 of the present invention;
FIG. 4 is a FTIR chart of the CPS60@SA/La sustained release gel composite material of example 1 of the present invention before and after dephosphorization;
FIG. 5 is a graph showing the effect of CPS60@SA/La and CPS60@SA/Ca sustained-release gel composite material in application example 1 on pH value;
FIG. 6 is a graph showing the effect of CPS60@SA/La and CPS60@SA/Ca sustained-release gel composite materials in application example 1 on Dissolved Oxygen (DO);
FIG. 7 is a graph showing the effect of CPS60@SA/La and CPS60@SA/Ca sustained-release gel composite materials in application example 1 on removal of the concentration of water-soluble inorganic phosphorus (DIP) on an overlying surface;
FIG. 8 is a graph showing the effect of CPS60@SA/La in application example 1 and CPS60@SA/Ca in comparative example 1 on the removal of interstitial water-soluble inorganic phosphorus (DIP) concentration.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a calcium peroxide slow-release gel composite material, which comprises the following components:
loaded with CaO 2 A matrix material of nanoparticles;
coated on the CaO-loaded components 2 Package of outer surface of matrix material of nanoparticlesA coating layer;
the coating layer comprises metal cations and sodium alginate.
In certain embodiments of the invention, the CaO 2 The nanoparticles are supported on the surface and pores of the matrix material.
In certain embodiments of the invention, the matrix material acts as a carrier, including a natural clay mineral matrix and/or a modified natural clay mineral matrix. The natural clay mineral matrix comprises at least one of sepiolite, bentonite, halloysite, diatomite, attapulgite, kaolin, montmorillonite, illite, vermiculite and dolomite. The specific surface area of the natural clay mineral matrix is not less than 0.1m 2 And/g. The natural clay mineral matrix and/or the modified natural clay mineral matrix helps to improve the dispersibility of the nanoparticles.
In certain embodiments of the invention, the method of preparing the modified natural clay mineral substrate comprises the steps of:
mixing the natural clay mineral matrix with a strong acid solution, and boiling for reaction to obtain the modified natural clay mineral matrix.
The strong acid solution comprises concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid. The mass concentration of the strong acid solution is 1-10%.
The dosage ratio of the natural clay mineral matrix to the strong acid solution is 1g:1 mL-1 g:20mL; specifically 1g:10mL.
The boiling reaction time is 0.5-2 h; specifically 0.5h.
After the boiling reaction, the method further comprises the following steps: and cleaning, drying, grinding and sieving the reacted product. The cleaning is carried out by deionized water until the cleaning is neutral. The drying temperature is 70-80 ℃, and the drying is carried out in a vacuum drying oven. After the drying, the method further comprises the following steps: cooled to room temperature. The sieve pore diameter of the sieve is 50-100 meshes; specifically 80 mesh.
In certain embodiments of the invention, the CaO 2 The particle size of the nano particles is 20-100 nm.
In certain embodiments of the present invention, the metal cation is a high valence metal cationA seed, the high valence metal cation including Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of them.
In the invention, the metal cation crosslinked sodium alginate is coated on the CaO-loaded substrate 2 The outer surface of the matrix material of the nano particles forms a gel microsphere structure.
In certain embodiments of the present invention, the calcium peroxide sustained release gel composite has an average particle size of 2 to 5mm. The surface of the calcium peroxide slow-release gel composite material is provided with a plurality of honeycomb pore structures, and the surface is loose and porous.
The invention also provides a preparation method of the calcium peroxide slow-release gel composite material, which comprises the following steps:
a) Mixing matrix material, soluble calcium salt solution, dispersant and precipitant, stirring to react to obtain CaO 2 A precursor solution;
the matrix material comprises a natural clay mineral matrix and/or a modified natural clay mineral matrix;
b) At the CaO 2 Dropwise adding H into the precursor solution 2 O 2 Stirring the solution in ice bath or at normal temperature to obtain CaO-loaded solution 2 A matrix material of nanoparticles;
c) Loading the CaO on the steel plate 2 Uniformly mixing the matrix material of the nano particles with the sodium alginate solution, and dripping the obtained mixed solution into the metal salt solution for curing reaction to obtain the calcium peroxide slow-release gel composite material.
In step A):
mixing matrix material, soluble calcium salt solution, dispersant and precipitant, stirring to react to obtain CaO 2 Precursor solution.
Specifically, the method comprises the following steps:
a1 Stirring and mixing the matrix material and the soluble calcium salt solution to form a suspension;
a2 Dropwise adding a dispersing agent and a precipitating agent into the suspension while stirring, and stirring to react after the dropwise addition is completed to obtain CaO 2 Precursor solution.
In certain embodiments of the invention, in steps A1) and A2), the stirring is carried out at a speed of 400 to 600rpm, such as 500rpm.
The matrix material comprises a natural clay mineral matrix and/or a modified natural clay mineral matrix.
In certain embodiments of the invention, the soluble calcium salt comprises CaCl 2 、Ca(NO 3 ) 2 And at least one of its hydrates; in the soluble calcium salt solution, ca 2+ The concentration of (2) is 0.05-3.0 mol/L; specifically, the concentration is 0.1mol/L.
The dispersing agent comprises at least one of Cetyl Trimethyl Ammonium Bromide (CTAB), sodium citrate, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) 200 and PEG 400; specifically, PEG 200 may be used. The CaO is 2 In the precursor solution, the mass content of the dispersing agent is 0.05-10%; specifically, the content may be 1% or 2%.
The precipitant comprises NH 3 ·H 2 O, naOH solution and KOH solution; specifically, it may be 0.5mol/LNaOH solution. OH-in the precipitant and Ca in the soluble calcium salt solution 2+ The molar ratio of (2) is 10:1 to 1:1, a step of; specifically, it may be 1.6:1.
ca in the soluble calcium salt solution 2+ The mass ratio of the polymer to the matrix material is 0.2-1: 1, such as 0.5:1.
the stirring reaction time is 10 min-4 h, such as 10min.
In step B):
at the CaO 2 Dropwise adding H into the precursor solution 2 O 2 Stirring the solution in ice bath or at normal temperature to obtain CaO-loaded solution 2 A matrix material of the nanoparticle.
In certain embodiments of the invention, the H 2 O 2 With CaO 2 Ca in precursor solution 2+ The molar ratio of (2) is 1:1 to 25:1, such as 10:1, a step of;
the H is 2 O 2 The mass concentration of the solution is 5% -30%, such as 30%;
the H is 2 O 2 The dropping rate of the solution is 0.1 to 10mL/min, such as 0.2mL/min.
In certain embodiments of the invention, the dropwise addition is performed under stirring. The rotational speed of the stirring is 400 to 600rpm, such as 500rpm.
In certain embodiments of the invention, the stirring reaction is for a period of time ranging from 30 minutes to 2 hours, such as 2 hours; the rotation speed is 400 to 600rpm, such as 500rpm.
In some embodiments of the present invention, after the stirring reaction, the method further comprises:
and centrifugally collecting, cleaning, drying and grinding the product after the stirring reaction. The cleaning adopts pure water cleaning. The drying temperature is 50-70 ℃, and the drying is carried out in a vacuum drying oven.
In step C):
loading the CaO on the steel plate 2 Uniformly mixing the matrix material of the nano particles with the sodium alginate solution, and dripping the obtained mixed solution into the metal salt solution for curing reaction to obtain the calcium peroxide slow-release gel composite material.
In certain embodiments of the invention, the sodium alginate solution has a mass concentration of 10-20 g/L, such as 12g/L. And the sodium alginate solution is prepared by dissolving sodium alginate in deionized water and stirring. The stirring speed is 700-900 rpm.
In certain embodiments of the invention, the sodium alginate is mixed with the CaO-loaded compounds 2 The mass ratio of the matrix material of the nano particles is 10:1 to 1:1, a step of; such as 2:1.
the mixing is stirring and mixing. The stirring speed is 700-900 rpm.
In certain embodiments of the present invention, the metal ion in the metal salt comprises Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of them. The metal salt solution comprises Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of soluble chloride, sulfate, nitrate and hydrates thereof; specifically, la (NO 3 ) 3 ·6H 2 O. The mass concentration of the metal salt solution is 0.1-2 mol/L, such as 0.1mol/L.
The dosage ratio of the metal salt to the sodium alginate is 2-60 mmol/g, and specifically, can be 10mmol/g.
In some embodiments of the invention, the mixed solution is dropped into the metal salt solution at a rate of 2 to 15 drops/min; specifically, the content may be 5 drops/min.
In certain embodiments of the present invention, the curing reaction is performed at ambient temperature for a reaction time of 0.5 to 6 hours; specifically, the time may be 2 hours.
In some embodiments of the present invention, after the curing reaction, the method further comprises: filtering and cleaning. The cleaning is carried out by adopting deionized water. After the cleaning, the product can be stored in a refrigerator at the temperature of 4 ℃.
The invention also provides an application of the calcium peroxide slow-release gel composite material or the calcium peroxide slow-release gel composite material prepared by the preparation method as described above as an eutrophic water body purification material. Specifically, the method is applied to a purification material for long-term in-situ repair of eutrophic water bodies and/or phosphorus passivation of bottom sludge; or as a dephosphorization material for eutrophic water bodies.
The invention also provides a purification method of the eutrophic water body, which comprises the following steps:
mixing the calcium peroxide slow-release gel composite material with the eutrophic water body to obtain the purified water body.
Specifically, the method comprises the following steps:
and (3) adding the calcium peroxide slow-release gel composite material to the surface layer of the eutrophic water body sediment, and obtaining the purified water body after passivation treatment.
In certain embodiments of the invention, the eutrophic water body comprises an urban river, a natural river, a lake, a pond, or a landscape water body; the pH value of the eutrophic water body is 6.5-11.0, the dissolved oxygen content is 0-10 mg/L, and the content of soluble inorganic phosphorus (DIP) in the eutrophic water body is 0.01-1.5 mg/L.
In some embodiments of the invention, the calcium peroxide slow-release gel composite material is added in an amount of 0.01-1.0 g/L, specifically, 0.05g/L.
In certain embodiments of the invention, the passivation treatment is performed at room temperature for a period of time not less than 0.5 hours, such as from 0.5 hours to 30 days.
The calcium peroxide slow-release gel composite material is used as a phosphorus removal material for eutrophic water, and has a better removal effect.
Compared with the prior art, the invention has the following beneficial technical effects:
1) The calcium peroxide slow-release gel composite material provided by the invention has active sites of Ca and high-valence metal, has strong selectivity to phosphate, and the saturated adsorption capacity can reach 198.25mg/g; the solubility product constant of the precipitate of calcium phosphate and phosphate (such as lanthanum phosphate) formed after adsorption is smaller, and the phosphorus fixation effect is obvious and stable.
2) The calcium peroxide slow-release gel composite material provided by the invention solves the problem of CaO better 2 The nano particles react fast in the aqueous solution, so that the problem of high pH value of the solution and insufficient utilization of Ca active sites is caused. The slow release gel formed by the cladding of the sodium alginate prolongs the action time of the composite material and endows CaO 2 Sustained release effect, can provide O permanently 2 The DO content of the overlying water is maintained at a higher level, the micro-interface of the overlying water and the sediment is ensured to be in an aerobic state, and further, the secondary release of the sediment phosphorus is inhibited, so that the method has important significance for solving the serious endogenous phosphorus pollution of the sediment.
3) Adopts natural clay mineral matrix and/or modified natural clay mineral matrix to CaO 2 The nano particles are dispersed and coated by SA, and the high-valence metal cations are crosslinked to form the slow-release composite microspheres, so that the CaO is hopeful to be solved 2 Easy agglomeration and poor long-term application effect. And the natural clay mineral matrix used for dispersion can also improve the mechanical strength of the formed slow-release gel composite material and increase the applicability of the slow-release gel composite material.
Therefore, the calcium peroxide slow-release gel composite material provided by the invention can provide a new choice for the treatment of eutrophic water bodies.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe in detail a calcium peroxide sustained-release gel composite material, its preparation method and application, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Preparation of modified natural clay mineral matrix:
weighing 20g of sepiolite, mixing with 200mL of sulfuric acid solution with mass concentration of 5%, boiling for reaction for 0.5h, washing with deionized water to neutrality, drying in a vacuum drying oven at 75 ℃, cooling to room temperature, grinding, and sieving with a 80-mesh sieve to obtain the modified natural clay mineral matrix.
2) 3g of anhydrous CaCl was weighed 2 Adding deionized water into a three-neck flask to prepare 0.1mol/L CaCl 2 A solution. Afterwards, caCl is added 2 Adding 5g of modified natural clay mineral matrix into the solution, stirring at 500rpm to form suspension, dropwise adding PEG 200 dispersant solution and 0.5mol/LNaOH solution (ensuring OH-and Ca) 2+ The molar ratio is 1.6: 1) Continuously stirring and reacting for 10min after the dripping is finished to obtain CaO 2 A precursor solution; the CaO is 2 In the precursor solution, the mass content of the PEG 200 dispersing agent is 1%.
3) To CaO under stirring (500 rpm) 2 Dropwise adding 30% H in mass concentration into the precursor solution at a rate of 0.2mL/min 2 O 2 Solution (H) 2 O 2 With Ca 2+ The molar ratio of (2) is 10: 1) The reaction (500 rpm) was stirred for 2h. After the reaction is finished, centrifugally collecting the obtained product, cleaning the product by deionized water, drying the product in a vacuum drying oven at 60 ℃, and grinding the product to obtain the CaO-loaded product 2 A matrix material of the nanoparticle. For convenience of description, the obtained CaO-loaded products are 2 The matrix material of the nanoparticles is denoted CPS 60.
4) Weighing 0.6g sodium alginate, dissolving in 50mL deionized water, stirring at 800rpm to obtain sodium alginate solution0.3g CPS60 powder was added and stirring was continued for 30min to uniformly disperse it in sodium alginate solution, the resulting slurry was withdrawn with a 5mL syringe and dropped into 100mL of 0.1mol/L La (NO) 3 ) 3 And (3) in the solution (the dropping speed is 5 drops/min), carrying out crosslinking and curing reaction for 2 hours, filtering, collecting spherical particles with the diameter of 2-5 mm by using a filter screen, cleaning by using deionized water, and placing in a refrigerator with the temperature of 4 ℃ for standby, thereby obtaining the calcium peroxide slow-release gel composite material (marked as CPS60@SA/La slow-release gel composite material).
FIG. 1 is an XRD pattern of a modified natural clay mineral matrix (pretreated sepiolite) and CPS60@SA/La sustained release gel composite material according to example 1 of the present invention. As can be seen from FIG. 1, the characteristic diffraction peaks of the pretreated sepiolite can be respectively compared with those of Mg 7 Si 8 O 22 (OH) 2 、Mg 2 Si 5 Al 2 O 18 And SiO 2 Corresponds to the XRD standard pattern of (c). Nano CaO-loaded 2 Particles, and pass through lanthanum ion (La 3+ ) After crosslinking and SA compounding, the obtained CPS60@SA/La slow-release gel composite material has new characteristic diffraction peaks at 2 theta=30.27 DEG, 47.31 DEG and 53.21 DEG, and the diffraction peaks are matched with CaO 2 The XRD standard spectrum (PDF No. 03-0865) showed consistent positions of the characteristic diffraction peaks, indicating CaO 2 Has been successfully synthesized and loaded into CPS60@SA/La slow-release gel composite material.
FIG. 2 is an SEM image of a CPS60@SA/La sustained release gel composite material of example 1 of the present invention. As can be seen from FIG. 2, caO-loaded 2 After the nanoparticles, a large number of uniformly dispersed nanospheres appear on the surface of the rod-shaped sepiolite, the diameter of the nanospheres is 20-100 nm, so that the smooth surface of the sepiolite becomes rough, and a spherical and rod-shaped staggered micro-nano composite structure is formed. Will carry nano CaO 2 After the sepiolite is coated into the sodium alginate microspheres, uniform spherical hydrogel particles are formed, and after the sepiolite is dried, a large number of honeycomb pore structures are found on the surfaces of the gel spheres, and the surfaces of the gel spheres become more loose and porous.
FIG. 3 is an elemental analysis chart of CPS60@SA/La sustained release gel composite material of example 1 of the present invention. As can be seen from FIG. 3, the high-efficiency CaO is 2 The main element of the surface distribution of the slow release gel composite material is Ca, la, O, si,indicating CaO 2 The nanoparticle and lanthanum sites have been integrated into the cps60@sa/La sustained release gel composite.
FIG. 4 is a FTIR chart of the CPS60@SA/La sustained release gel composite material of example 1 of the present invention before and after dephosphorization (static adsorption experiment, initial phosphorus concentration of 10mg/L, CPS60@SA/La usage of 0.2g/L, pH=7, 25 ℃ C., reaction time of 12 h). As can be seen from FIG. 4, before dephosphorization, the CPS60@SA/La slow-release gel composite material is 470cm in length -1 The characteristic peak at the position is the stretching vibration peak of La-O bond, at 875cm -1 The characteristic peak at the wave number is CaO 2 O-O bond in (B) further confirms CaO 2 Has been successfully coated onto composite gel, and La 3+ Plays a role in crosslinking and curing; at 1494cm -1 The absorption peak at the site is CO 3 2- An asymmetric stretching vibration peak of (2) indicates CO in air during preparation 2 Also participate in the reaction due to La 3+ And Ca 2+ All are against CO 2 Exhibits a strong affinity. After adsorbing phosphate, CPS60@SA/La slow-release gel composite material is in 875cm and 1494cm -1 The absorption peak at the position is basically disappeared, which indicates that CaO is removed in the dephosphorization process 2 In which the O-O bond is completely broken and CO 3 2- Ion exchange with phosphate occurs. It is presumed that surface precipitation and inner layer complexation may exist in the phosphate removal process of the CPS60@SA/La slow release gel composite material.
Example 2
The difference from example 1 is that:
la (NO) in step 4) 3 ) 3 Solution replacement with Zr (NO) 3 ) 4 A solution.
Example 3
The difference from example 1 is that:
la (NO) in step 4) 3 ) 3 Replacement of solution with Fe (NO) 3 ) 3 A solution.
Comparative example 1
The difference from example 1 is that:
la (NO) in step 4) 3 ) 3 Replacement of solution with CaCl 2 Solution, the material obtained is designated CPS60@SA/Ca composite material.
Application example 1
The CPS60@SA/La prepared in example 1 and the CPS60@SA/Ca composite material prepared in comparative example 1 are used for removing phosphate in eutrophic water bodies and bottom sludge, and the specific operations comprise:
prior to the experiment, a grab bucket type sediment sampler was used to collect approximately 8cm sediment and water on the surface of the Taihu lake. After the collected mud sample and the water sample are brought back to the experiment, the sediment sample is filtered through a 100-mesh sieve and is uniformly mixed for standby, and the water sample is filtered by suction and is preserved in a dark place for standby. In the experiment, an organic glass tube with an inner diameter of 120mm and a height of 300mm is used as an experimental device, pretreated bottom mud is added into the device, and five experimental groups (E0, E1, E2, E3 and E4) are arranged for the experiment. Wherein E0 is a blank group, and no material is added; in E1, the surface of the bottom mud is covered with 0.1kg/m 2 CPS60@SA/La slow release gel containing 5.2g of CPS60 composite material; in E2, the surface of the bottom mud is uniformly covered with 0.1kg/m 2 CPS60@SA/Ca slow release gel containing 5.2g of CPS60 composite material; in E3, uniformly covering 5.2g CPS60 composite material on the surface of the bottom mud; in E4, the surface of the bottom mud is uniformly covered with 5.2g of pure CaO 2 And (3) powder. To avoid causing sediment disturbance, overburden water containing 0.45mg/L phosphorus content collected from the river was added to the experimental set-up by siphoning. The experiment was carried out at room temperature for 30 days, the overlying water was periodically taken, the pH, dissolved Oxygen (DO) and the concentration of soluble inorganic phosphorus (DIP) were measured, and the DIP content in the interstitial water was measured every three days. After the daily sampling is finished, raw water is added in a siphoning mode, and the water loss is supplemented.
FIG. 5 is a graph showing the effect of CPS60@SA/La and CPS60@SA/Ca sustained-release gel composite material in application example 1 on pH. As can be seen from FIG. 5, the pH of the control group was relatively stable throughout the experimental period without the additional material, with an average value of about 7.44. CaO is adopted 2 After the powder is covered, due to CaO 2 React with water to release a large amount of OH - ，CaO 2 The pH of the group of water covers increased rapidly within 1-5 d and reached a maximum of 11.36, after which it was maintained at an average level of about 10.5. In CPS60 composite coverage, the pH of the overlying water also showed a rapid rise in the first 7dAnd then gradually stabilized and maintained at a pH of about 9.39. In contrast, the pH value of the water covered by the CPS60@SA/La and CPS60@SA/Ca slow-release gel experimental groups only slowly rises in the first 5 days, becomes a descending trend after that, is maintained at 7.87-8.59 in the whole experimental period, and has far less influence on the pH value of the water covered by CPS60 composite material and CaO 2 And (3) powder.
FIG. 6 is a graph showing the effect of CPS60@SA/La and CPS60@SA/Ca sustained-release gel composite materials in application example 1 of the present invention on Dissolved Oxygen (DO). As can be seen from FIG. 6, the DO concentration of the overlying water was relatively stable without the additional material, with an average value of about 2.93mg/L, which was much lower than that of the experimental group. CaO is adopted 2 After being covered with the material, due to CaO 2 Oxygen is released by reaction with water, and DO concentration in overlying water of each experimental group is greatly increased. Wherein, caO 2 The DO concentration of the water covered by the group is most obviously increased, and the DO concentration can be sharply increased to 10.75mg/L when the experiment is carried out for 7 days, and then gradually reduced to about 6.5 mg/L. DO concentration variation trend and CaO of CPS60 composite material group overlying water 2 The groups are more similar but due to their lower CaO presence 2 The DO concentration in the overlying water can reach 9.42mg/L. Unlike two kinds of powder materials, the DO concentration of the overlying water in the CPS60@SA/Ca and CPS60@SA/La slow-release gel groups is slowly increased firstly and then is stably maintained at a higher level. After 21d from the beginning of the experiment, the DO concentration of the water covering the two gel groups was all anti-super CaO 2 Maintaining such a stable aerobic environment with the CPS60 composite set may be advantageous for the retention and adsorption of phosphorus by the substrate sludge and various microorganisms, etc. The application of CPS60@SA/Ca and CPS60@SA/La can reduce the influence or impact of material addition on the micro-environment of the overlying water environment or the bottom mud.
FIG. 7 is a graph showing the effect of CPS60@SA/La and CPS60@SA/Ca sustained-release gel composite materials in application example 1 on removal of the concentration of water-soluble inorganic phosphorus (DIP) on the coating. As can be seen from FIG. 7, in CPS60 composite, CPS60@SA/Ca, CPS60@SA/La and CaO 2 With powder coating, the DIP concentration of the overlying water was lower than that of the control group and maintained at a steady level. Wherein, caO 2 The DIP concentration in the water covered by the experimental group drops most rapidly, the residual phosphorus concentration is lowest, the phosphorus removal effect is most remarkable, but the DIP concentration has an ascending trend from 21 d; second CPS60 complexComposite material, CPS60@SA/La and CPS60@SA/Ca slow release gel. Due to CaO contained in the composite material 2 The proportion is reduced, and the SA embedding reduces CaO 2 The contact area with water is observed to decrease the DIP concentration more slowly in the overlying water in the composite set. From 18d, the DIP concentration of the CPS60@SA/Ca group prepared in comparative example 1 was maintained at about 0.21mg/L, while the DIP concentration of the CPS60@SA/La group prepared in example 1 was still steadily decreased below the detection limit until the end of the experimental period, probably due to La 3+ The phosphate in the overlying water can be combined with the active site in CPS60@SA/La through electrostatic attraction, surface precipitation, complexation and the like, and is fixed on the surface of the phosphate, so that the removal potential of the phosphate is increased.
FIG. 8 is a graph showing the effect of CPS60@SA/La in application example 1 and CPS60@SA/Ca in comparative example 1 on the removal of interstitial water-soluble inorganic phosphorus (DIP) concentration. As can be seen from FIG. 8, in the experimental period, the DIP concentration in the interstitial water of the CPS60@SA/Ca experimental group was about 0.34mg/L, and the tendency of the gradual rise was shown at 18d, and the DIP concentration in the interstitial water of the CPS60@SA/La experimental group was about 0.20mg/L, and was maintained substantially steady. Whereas CaO 2 DIP in interstitial water in experimental group and CPS60 composite material experimental group continuously rises, caO 2 The rise rate of the experimental group is obviously higher than that of the CPS60 composite material experimental group and the control group. CaO (CaO) 2 The rapid increase in gap water DIP in the experimental group was due to CaO 2 The oxidation is strong, a part of organic phosphorus or polyphosphate fixed in the sediment is converted into orthophosphate, but the adsorption site is insufficient, so that part of phosphorus is released into the overlying water, and CPS60 composite material experimental group is characterized by CaO 2 CPS60 composite material adsorption sites are increased after being loaded on the sepiolite surface, which is beneficial to CaO 2 And (3) removing phosphate. CPS60@SA/Ca and CPS60@SA/La enable the overlying water to be in an aerobic environment so as to be beneficial to the adsorption of phosphorus by the adsorbent, the surface of the bottom mud is oxidized, lanthanum sites in CPS60@SA/La have higher affinity to phosphorus, and can generate a fixing effect on phosphate, so that the adsorption effect of the slow-release gel on phosphorus is more stable.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A calcium peroxide sustained release gel composite comprising:
loaded with CaO 2 A matrix material of nanoparticles;
coated on the CaO-loaded components 2 A coating layer on the outer surface of the matrix material of the nanoparticles;
the coating layer comprises metal cation crosslinked sodium alginate.
2. The calcium peroxide slow release gel composite of claim 1, wherein the matrix material comprises a natural clay mineral matrix and/or a modified natural clay mineral matrix;
the natural clay mineral matrix comprises at least one of sepiolite, bentonite, halloysite, diatomite, attapulgite, kaolin, montmorillonite, illite, vermiculite and dolomite;
the metal cation comprises Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of them.
3. The calcium peroxide slow release gel composite of claim 2, wherein the method of preparing the modified natural clay mineral matrix comprises the steps of:
mixing the natural clay mineral matrix with a strong acid solution, and boiling for reaction to obtain a modified natural clay mineral matrix;
the strong acid solution comprises concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid; the mass concentration of the strong acid solution is 1-10%;
the dosage ratio of the natural clay mineral matrix to the strong acid solution is 1g:1 mL-1 g:20mL;
the boiling reaction time is 0.5-2 h;
after the boiling reaction, the method further comprises the following steps: and cleaning, drying, grinding and sieving the reacted product.
4. The calcium peroxide slow release gel composite of claim 1, wherein the CaO 2 The particle size of the nano particles is 20-100 nm;
the average grain diameter of the calcium peroxide slow-release gel composite material is 2-5 mm.
5. The preparation method of the calcium peroxide slow-release gel composite material comprises the following steps:
a) Mixing matrix material, soluble calcium salt solution, dispersant and precipitant, stirring to react to obtain CaO 2 A precursor solution;
the matrix material comprises a natural clay mineral matrix and/or a modified natural clay mineral matrix;
b) At the CaO 2 Dropwise adding H into the precursor solution 2 O 2 Stirring the solution in ice bath or at normal temperature to obtain CaO-loaded solution 2 A matrix material of nanoparticles;
c) Loading the CaO on the steel plate 2 Uniformly mixing the matrix material of the nano particles with the sodium alginate solution, and dripping the obtained mixed solution into the metal salt solution for curing reaction to obtain the calcium peroxide slow-release gel composite material.
6. The method of claim 5, wherein in step A) the soluble calcium salt comprises CaCl 2 、Ca(NO 3 ) 2 And at least one of its hydrates;
in the soluble calcium salt solution, ca 2+ The concentration of (2) is 0.05-3.0 mol/L;
ca in the soluble calcium salt solution 2+ The mass ratio of the polymer to the matrix material is 0.2-1: 1, a step of;
the dispersing agent comprises at least one of Cetyl Trimethyl Ammonium Bromide (CTAB), sodium citrate, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) 200 and PEG 400;
the precipitant comprises NH 3 ·H 2 O, naOH solution and KOH solution.
7. The process according to claim 5, wherein in step B), the H is 2 O 2 With CaO 2 Ca in precursor solution 2+ The molar ratio of (2) is 1:1 to 25:1, a step of;
the H is 2 O 2 The mass concentration of the solution is 5-30%;
the H is 2 O 2 The dropping rate of the solution is 0.1-10 mL/min;
the stirring reaction time is 30 min-2 h;
after the stirring reaction, the method further comprises the following steps:
and centrifugally collecting, cleaning, drying and grinding the product after the stirring reaction.
8. The preparation method according to claim 5, wherein in the step C), the mass concentration of the sodium alginate solution is 10-20 g/L;
the sodium alginate and the CaO-loaded 2 The mass ratio of the matrix material of the nano particles is 10:1 to 1:1, a step of;
the metal ions in the metal salt comprise Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of (a) and (b);
the metal salt solution comprises Zr 4+ 、La 3+ 、Ce 3+ And Fe (Fe) 3+ At least one of soluble chloride, sulfate, nitrate and hydrates thereof;
the mass concentration of the metal salt solution is 0.1-2 mol/L;
the speed of dripping the mixed solution into the metal salt solution is 2-15 drops/min;
the curing reaction is carried out at normal temperature, and the reaction time is 0.5-6 h;
after the curing reaction, the method further comprises the following steps: filtering and cleaning.
9. Use of the calcium peroxide slow release gel composite material according to any one of claims 1 to 4 or the calcium peroxide slow release gel composite material prepared by the preparation method according to any one of claims 5 to 8 as an eutrophic water purification material.
10. A method for purifying eutrophic water body comprises the following steps:
mixing the calcium peroxide slow-release gel composite material with the eutrophic water body to obtain a purified water body;
the calcium peroxide slow release gel composite material is the calcium peroxide slow release gel composite material according to any one of claims 1 to 4 or the calcium peroxide slow release gel composite material prepared by the preparation method according to any one of claims 5 to 8.
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