CN116786092A - Organic polymer supported La@Fe-SiO 2 Aerogel microsphere and preparation method and application thereof - Google Patents
Organic polymer supported La@Fe-SiO 2 Aerogel microsphere and preparation method and application thereof Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 104
- 239000004005 microsphere Substances 0.000 title claims abstract description 101
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 84
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000011574 phosphorus Substances 0.000 claims abstract description 74
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000001179 sorption measurement Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 35
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 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 description 13
- 239000000017 hydrogel Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 235000010413 sodium alginate Nutrition 0.000 claims description 13
- 239000000661 sodium alginate Substances 0.000 claims description 13
- 229940005550 sodium alginate Drugs 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000002283 diesel fuel Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 13
- 239000010452 phosphate Substances 0.000 abstract description 13
- 239000003463 adsorbent Substances 0.000 abstract description 10
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 239000010865 sewage Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052746 lanthanum Inorganic materials 0.000 description 11
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 9
- -1 ion exchange Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000002798 spectrophotometry method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
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Abstract
The invention discloses an organic polymer loaded La@Fe-SiO which belongs to the technical field of sewage treatment and adsorbent materials 2 Aerogel microspheres and methods of making and using the same. The metal Fe is filled in SiO 2 In the mesoporous pores of the aerogel microspheres, fe-SiO is obtained 2 Aerogel microspheres; fe-SiO 2 The aerogel microspheres are embedded in a gel network structure of the organic polymer; lanthanum salt is loaded on the surface of the organic polymer to obtain La@Fe-SiO loaded on the organic polymer 2 The dephosphorization adsorbent of the aerogel microsphere. The method combinesLanthanum efficiently adsorbs phosphate and Fe-SiO 2 The aerogel microsphere slowly releases the advantages of iron and phosphorus removal, realizes the deep removal of phosphate and solves the problems of SiO 2 The aerogel is not easy to separate. The method is simple to operate and environment-friendly, and provides a way for developing a novel dephosphorization adsorbent.
Description
Technical Field
The present invention belongs to the field of sewage treating and adsorbing material technologyThe field of organic polymer supported La@Fe-SiO 2 Aerogel microsphere dephosphorization adsorption material, and a preparation method and application thereof.
Background
Phosphorus is a salt essential for growth and survival of all animals and plants. The discharge of domestic sewage and industrial wastewater, the excessive fertilization of agriculture and the like can input phosphorus into the water environment, and when the content of the phosphorus exceeds a certain threshold value, the eutrophication of the water body can be induced. Phosphorus is a non-renewable resource, and has low utilization efficiency due to unidirectional flow to the ocean, so that worldwide phosphorus resource shortage is caused. Therefore, the phosphate is deeply removed, the recovery and the reutilization of the phosphorus are realized, and the strategic development of the phosphorus resource is very important.
Common methods of phosphorus removal include biological, chemical, ion exchange, membrane separation, adsorption, and the like. The adsorption method has the characteristics of good effect, low cost, easy operation, recycling and the like, and is widely applied to the dephosphorization of water bodies. The development of phosphorus adsorption materials in different forms based on different phosphorus removal principles has also become a research hotspot. Some dephosphorization materials incorporate dephosphorization active ingredients such as Fe through the surface 3+ 、La 3+ 、Al 3+ Etc. are coordinately bound to the phosphate. Some dephosphorization materials are prepared by slowly releasing a dephosphorization effect component such as Fe into solution 3+ Hydrolysis and complex precipitation to remove phosphorus occur.
Lanthanum is the most common rare earth element, has excellent affinity and strong anti-interference capability on phosphorus in complex water, and lanthanum salt and hydroxide thereof are often used as active components for phosphorus removal for preparing phosphorus removal materials. The ferric salt and the aluminum salt are common water treatment coagulants, have good dephosphorization performance, and can achieve continuous dephosphorization effect through the slow release control of the iron ions and the aluminum ions. The phosphorus pollution load of the polluted water body is greatly changed, and the development of the phosphorus removal material which is applicable to the water body with low phosphorus pollution and high phosphorus pollution simultaneously has important significance.
SiO 2 The aerogel microsphere has a nanoscale unique three-dimensional network structure, and has the advantages of large specific surface area, high porosity, good adsorption performance and high biocompatibility, so that the aerogel microsphere is commonly used as a carrier for slow release drugs. But SiO 2 Aerogel microspheres are often in powder formThe existing method has low strength and is not easy to separate and regenerate.
For this reason, the invention combines the excellent affinity of lanthanum element to phosphorus, and SiO 2 The slow release iron ion performance of aerogel as carrier uses organic polymer to load lanthanum and Fe-SiO 2 Aerogel microballoons develop a biological friendly adsorption dephosphorization material with high phosphorus adsorption quantity, slow release function and easy separation and recovery.
Disclosure of Invention
In order to solve the problems, the invention provides an organic polymer supported La@Fe-SiO 2 Aerogel microspheres, wherein the metal Fe is filled in SiO 2 In the mesoporous pores of the aerogel microspheres, fe-SiO is obtained 2 Aerogel microspheres; the Fe-SiO 2 The aerogel microspheres are embedded in a gel network structure of the organic polymer; the surface of the organic polymer is loaded with lanthanum salt;
the organic polymer is loaded with La@Fe-SiO 2 The aerogel microspheres are used for removing phosphorus adsorption materials and removing phosphorus elements in the water body.
In some preferred embodiments, the organic polymer is loaded with La@Fe-SiO 2 In the aerogel microspheres, the mass fraction of Fe is 10% -20%; siO (SiO) 2 The mass fraction of (2) is 10% -20%;
the mass fraction of La is 10% -20%;
the mass fraction of the organic polymer is 40% -70%;
in some more preferred embodiments, fe-SiO 2 The total mass fraction of (2) is 20-40%.
The invention utilizes SiO 2 Aerogel supporting Fe to form Fe-SiO 2 Wherein the Fe-SiO 2 In (1) loading to SiO 2 The mass fraction of Fe element in the aerogel is 12.5% -50%, and metal Fe is loaded on SiO 2 Aerogel mesoporous pores. Then embedding Fe-SiO with organic polymer sodium alginate and polyvinyl alcohol 2 Fixing La (III) on the surface of a network structure formed by an organic polymer to prepare and form a supported La@Fe-SiO 2 Organic polymeric dephosphorizing adsorbent material of aerogel microspheres. This isThe seed material can remove phosphate through high-efficiency adsorption of lanthanum on the surface, and can also remove phosphate through Fe-SiO 2 The slow release iron ions remove phosphate, thereby realizing the deep removal of phosphate. By Fe-SiO 2 The aerogel microspheres are embedded into an organic gel network formed by sodium alginate and polyvinyl alcohol, so that the SiO is effectively solved 2 The problem of difficult separation of the aerogel.
The organic polymer provided by the invention is loaded with La@Fe-SiO 2 The preparation method of the dephosphorization material is simple to operate, is environment-friendly, and can be widely used for removing inorganic phosphorus in water.
The invention provides an organic polymer loaded La@Fe-SiO 2 Aerogel microspheres, comprising in particular
The invention also provides an organic polymer supported La@Fe-SiO 2 The preparation method of the aerogel microsphere comprises the following steps of firstly preparing super-hydrophobic SiO 2 Aerogel microspheres, using mechanical milling method to load zero-valent iron to SiO 2 Obtaining Fe-SiO in the mesoporous pores of the aerogel microspheres 2 After aerogel microspheres, the Fe-SiO is embedded by organic polymer 2 Aerogel microspheres, and La (III) is combined on the surface of the organic polymer to react to generate organic polymer loaded La@Fe-SiO 2 Is a dephosphorization adsorption material;
the method comprises the following specific steps:
1) Preparation of SiO 2 Aerogel microspheres: mixing and stirring tetraethoxysilane, acetic acid and absolute ethyl alcohol, and adjusting the pH value to 8-9; adding diesel oil, and continuously stirring; after the reaction is finished, the SiO is obtained through suction filtration, washing, aging and drying 2 Aerogel microspheres;
2) Preparation of Fe-SiO 2 Aerogel microspheres: the simple substance powder of nano metal Fe and SiO 2 Mixing aerogel microspheres to obtain a mixture, and ball milling under argon atmosphere to obtain Fe-SiO 2 Aerogel microspheres;
3) Preparation of organic Polymer Supported La (III) and Fe-SiO 2 Aerogel microspheres:
(1) dissolving sodium alginate and polyvinyl alcohol in deionized water to obtain sodium alginate-polyvinyl alcohol solution;
(2) dissolving lanthanum chloride in deionized water to obtain a lanthanum chloride solution;
(3) mixing sodium alginate-polyvinyl alcohol solution and lanthanum chloride solution, adding into Fe-SiO prepared in step 2) 2 Obtaining sol from aerogel microspheres;
(4) dissolving anhydrous calcium chloride in deionized water to obtain a calcium chloride solution, adding boric acid and anhydrous sodium carbonate, stirring, performing ultrasonic treatment to saturate the solution, and adjusting the pH value to 6.8-7.2 to obtain a cross-linking agent;
(5) dropping the sol into the cross-linking agent at uniform speed dropwise while stirring to obtain La@Fe-SiO containing organic polymer 2 A hydrogel microsphere mixed solution;
(6) standing, washing and drying the mixed solution to obtain the organic polymer loaded La@Fe-SiO 2 Aerogel microspheres.
In some preferred embodiments, in the step 1), the volume ratio of the tetraethoxysilane to the absolute ethanol is 1 (1-3); the volume ratio of the tetraethoxysilane to the acetic acid is (1-3) 1; the volume ratio of the diesel oil to the sum of the volumes of the tetraethoxysilane, the acetic acid and the absolute ethyl alcohol is 1 (1-1.2).
In some preferred embodiments, in the step 1), the stirring temperature of the mixing and stirring of the tetraethoxysilane, the acetic acid and the absolute ethyl alcohol is 40-60 ℃ and the stirring time is 1.5-2.5 h; preferably in a water bath.
In some preferred embodiments, in the step 1), the stirring speed of mixing and stirring the tetraethoxysilane, the acetic acid and the absolute ethyl alcohol is 1000-1500 r/min.
In some preferred embodiments, in the step 1), the diesel oil is mixed with the tetraethoxysilane, the acetic acid and the absolute ethanol for a stirring time of 20 to 40 minutes.
In some preferred embodiments, in the step 1), diesel oil is mixed with ethyl orthosilicate, acetic acid and absolute ethanol, and the stirring speed of continuous stirring is 1200-1500 r/min.
In some preferred embodiments, in the step 1), the specific processes of suction filtration, washing, aging and drying are as follows: siO to be prepared 2 Filtering the hydrogel microspheres, washing the hydrogel microspheres with absolute ethyl alcohol for 2 to 5 times, and removing diesel oil; preparing a mixed solution of tetraethoxysilane and absolute ethyl alcohol with the volume ratio of 1 (1.5-2.5), and mixing SiO 2 Soaking the hydrogel microspheres in the mixed solution for 24-36 h, and filtering to remove the solution; drying in an electrothermal blowing drying oven at 40-45 ℃ for 24h.
In some preferred embodiments, in the step 2), the volume percentage of the elemental powder of metallic Fe in the mixture is 20% to 90%; the mass ratio of the grinding ball to the mixture is (20-50): 1; the rotating speed of the ball mill is 240-300 rpm; the ball milling time is 5-20 h.
In some preferred embodiments, in the sodium alginate-polyvinyl alcohol solution, the mass fraction of sodium alginate is 4% -10%, and the mass fraction of polyvinyl alcohol is 10% -12%; the mass ratio of the sodium alginate to the polyvinyl alcohol is 1 (1-3); in the process of preparing the sodium alginate-polyvinyl alcohol solution, water bath stirring and dissolving are adopted, the water bath temperature is 85-95 ℃, the stirring speed is 1000-1500 r/min, and the stirring time is 20-40 min.
In some preferred embodiments, the lanthanum chloride solution has a mass fraction of lanthanum chloride of 50-80%; in the process of preparing lanthanum chloride solution, ultrasonic dispersion and dissolution are adopted, and the process is as follows: ultrasonic is carried out for 5-15 min under the ultrasonic power of 100-500W.
In some preferred embodiments, the mass fraction of the calcium chloride solution is 2-5%; in the process of preparing the cross-linking agent, the ultrasonic treatment conditions are as follows: ultrasonic treatment is carried out for 3-15 min under the ultrasonic power of 100-500W.
In some preferred embodiments, the step 3) (3) is Fe-SiO in the sol 2 The mass fraction of the mixture is 20-40%, and the stirring speed is 1000-1500 r/min.
In some preferred embodiments, the volume ratio of sol to crosslinker in steps 3) (5) is 1 (7-12); the operation steps of dropping the sol into the cross-linking agent are as follows: 2-3 mL of sol is sucked by a syringe, is dropped at a constant speed and dropwise from a position 15-25 cm away from the liquid surface of the cross-linking agent, and is stirred while dropping, so that the adhesion of hydrogel microspheres is prevented.
In some preferred embodiments, the standing time of step 3) (6) is 5 to 12 hours to ensure adequate crosslinking of the hydrogel microspheres; washing with deionized water for 2-5 times, and absorbing surface moisture with absorbent paper; freeze drying in a refrigerator at-50 to-20 deg.c for 12-48 hr.
The invention also provides an organic polymer supported La@Fe-SiO 2 Use of aerogel microspheres in dephosphorization adsorption.
The invention has the beneficial effects that:
1. the organic polymer prepared by the invention is loaded with La@Fe-SiO 2 Aerogel microsphere composite material combined with SiO 2 Aerogel and multimetal (La and metallic Fe). SiO (SiO) 2 The aerogel microsphere has high loading capacity and excellent adsorption performance, and can play a slow-release role on active molecules loaded by the aerogel microsphere.
On the one hand, siO 2 The aerogel can effectively load Fe, control the slow release of iron ions, and achieve the effect of effectively removing phosphorus in water environment. On the other hand, the rare earth lanthanum has strong affinity and selectivity to phosphorus, and is beneficial to the efficient removal of low-concentration phosphorus in water environment. The prepared organic polymer dephosphorization material has Fe-SiO 2 The synergistic effect of the slow-release iron phosphorus removal and lanthanum adsorption phosphorus removal of the aerogel can meet the requirement of high-efficiency phosphorus removal under different environmental conditions.
2. The three-dimensional reticular porous structure of the sodium alginate and the polyvinyl alcohol can provide an organic polymer frame; the crosslinked sodium alginate has the advantages of no toxicity, high elasticity, high mechanical strength, high biocompatibility, low price and the like; metal ion La 3+ Can be obtained by substituting original Na + And H + Combining with polyvinyl alcohol to form hydrogel with good biodegradability; loading zero-valent iron to SiO 2 Fe-SiO is formed in the mesoporous pores of the aerogel 2 ，Fe-SiO 2 Is continuously oxidized under the oxidation condition to release the dephosphorization active component Fe 2+ /Fe 3+ Can achieve the aim of slow release and dephosphorization, and lead Fe-SiO to be 2 Embedding in organic polymer network structure can solve SiO effectively 2 And the separation is difficult.
3. The preparation method of the dephosphorization adsorbent provided by the invention is simple to operate and environment-friendly, can effectively strengthen the deep removal capability of phosphorus in water, and has the phosphorus removal rate of more than 90-95% when the inorganic phosphorus content in water is 0.3-2 mg/L.
Drawings
FIG. 1 is an organic polymer supported La@Fe-SiO of example 1 2 SEM image of aerogel microspheres;
FIG. 2 is an organic polymer supported La@Fe-SiO of example 1 2 EDS diagram of aerogel microspheres;
FIG. 3 is a graph showing the adsorption amounts of phosphorus in 500mg/L phosphorus solution of the four phosphorus removal materials obtained in example 1 and comparative examples 1 to 3;
wherein La@Fe-SiO 2 The @ P represents La @ Fe-SiO supported on the organic polymer prepared in example 1 2 The phosphorus adsorption performance of the phosphorus removal material under the experimental conditions;
La@P represents the phosphorus adsorption property of the polymer of comparative example 1 supporting only La;
Fe-SiO 2 the phosphorus adsorption performance of the iron-carrying aerogel in comparative example 2 is shown;
p represents that the polymer of comparative example 3 is not supported with La and Fe-SiO 2 Phosphorus adsorption properties of (2);
FIG. 4 is an organic polymer supported La@Fe-SiO of example 1 2 Structure of aerogel microsphere dephosphorization material.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
organic polymer supported La@Fe-SiO 2 A method of preparing aerogel microspheres, the method comprising the steps of:
1) Preparation of SiO 2 Aerogel microspheres: mixing proper amount of ethyl orthosilicate, acetic acid and absolute ethyl alcohol, heating in water bath at 40-60 ℃ and stirring for 1.5-2.5 h to fully hydrolyze a silicon source; adding a proper amount of ammonia water, regulating the pH to 8-9, and enabling the sol to be semi-solid; adding diesel oil with the volume ratio of 1 (1-1.2) to sol (the sum of the volumes of tetraethoxysilane, acetic acid and absolute ethyl alcohol), properly increasing the rotating speed of a rotor, stirring for 20-40 min, and gradually changing the sol from milky to translucent to obtain SiO 2 Hydrogel microspheres; will makeSiO obtained 2 Filtering the hydrogel microspheres, washing the hydrogel microspheres with absolute ethyl alcohol for 2 to 5 times, and removing diesel oil; preparing a mixed solution of tetraethoxysilane and absolute ethyl alcohol with the volume ratio of 1 (1.5-2.5), and mixing SiO 2 Soaking the hydrogel microspheres in the mixed solution for 24-36 h, and filtering to remove the solution; drying in an electrothermal blowing drying oven at 40-45 ℃ for 24h, and collecting for later use.
2) Preparation of Fe-SiO 2 Aerogel microspheres: zero-valent iron powder and SiO prepared in step 1) 2 Mixing aerogel microspheres to obtain a mixture, adding grinding balls, the mixture and absolute ethyl alcohol into a ball mill, wherein the mass ratio of the grinding balls to the mixture is (20-50): 1, charging argon, and ball milling for 5-20 hours at a rotating speed of 240-300 rpm to obtain Fe-SiO 2 Aerogel microspheres.
3) Preparation of organic Polymer Supported La@Fe-SiO 2 Aerogel microspheres:
(1) dissolving sodium alginate and polyvinyl alcohol in deionized water, stirring in a constant-temperature water bath at 85-95 ℃ for 20-40 min to completely dissolve the sodium alginate and the polyvinyl alcohol, and obtaining sodium alginate-polyvinyl alcohol solution;
(2) dissolving lanthanum chloride in deionized water, and stirring and carrying out ultrasonic treatment to completely dissolve the lanthanum chloride to obtain a lanthanum chloride solution;
(3) mixing sodium alginate-polyvinyl alcohol solution and lanthanum chloride solution, and adding Fe-SiO prepared in step (2) 2 Aerogel microspheres such that Fe-SiO 2 The mass fraction of the catalyst is 2-10%, and the catalyst is stirred until no particles exist, so as to obtain sol;
(4) dissolving anhydrous calcium chloride in deionized water to obtain a calcium chloride solution with the mass fraction of 2-5%, adding a proper amount of boric acid until solid is separated out, and accelerating dissolution by using ultrasound to saturate the solution. Adding anhydrous sodium carbonate, stirring, performing ultrasonic treatment, and adjusting the pH value to 6.8-7.2 to obtain a crosslinking agent;
(5) the sol is sucked by a syringe to be about 2mL, and is dropped at a constant speed from the position about 20cm away from the liquid surface of the cross-linking agent, and the mixture is stirred while dropping, so that the adhesion is prevented. The volume ratio of the sol to the cross-linking agent is 1 (7-12).
(6) After crosslinking for 5-12 h, loading La@Fe-SiO to the organic polymer prepared in step (5) 2 Aerogel microspheres (knot thereof)The schematic diagram is shown in FIG. 4, and the metal Fe is filled in SiO 2 In the mesoporous pores of the aerogel microspheres, the obtained Fe-SiO 2 The aerogel microspheres are embedded in a gel network structure of the organic polymer; meanwhile, lanthanum salt is loaded on the surface of the organic polymer) is washed for 2 to 5 times by deionized water, the cross-linking agent remained on the surface is removed, the surface moisture is absorbed by absorbent paper, and the absorbent paper is frozen and dried for 12 to 48 hours in a refrigerator at the temperature of minus 50 ℃ to minus 20 ℃ and is collected for standby.
In the following examples, the phosphorus concentration was measured by ammonium molybdate spectrophotometry (GB 11893-89), the minimum limit of detection being 0.01mg/L and the upper limit being 0.6mg/L.
Example 1
La@Fe-SiO loaded by organic polymer 2 The preparation method of the aerogel microsphere dephosphorization adsorbent comprises the following specific steps:
(1) Preparation of SiO 2 Aerogel microspheres
(1) 110mL of ethyl orthosilicate, 54mL of acetic acid and 225mL of absolute ethanol are sequentially added into a 500mL beaker, and water bath heating and stirring are carried out at 50 ℃ for 2h, so that the silicon source is fully hydrolyzed.
(2) To the above-prepared alcohol sol, an appropriate amount of aqueous ammonia was slowly added and stirring was continued, and the pH was adjusted to 8, whereby the sol was semi-solid.
(3) Adding diesel oil with the same volume as sol, properly increasing rotor rotation speed, stirring for 30min, and gradually changing sol from milky to translucent to obtain SiO 2 Aerogel microspheres.
(4) SiO to be prepared 2 And (3) carrying out suction filtration on the aerogel microspheres, washing with absolute ethyl alcohol for 3 times, and removing diesel oil.
(5) Aging, preparing a mixed solution of tetraethoxysilane and absolute ethyl alcohol in a volume ratio of 1:2, and carrying out the aging treatment on the SiO obtained in the step (4) 2 The hydrogel microspheres were soaked in this mixed solution for 24h, filtered off with suction, and the solution was removed.
(6) Drying in electrothermal blowing drying oven set at 40deg.C for 24 hr to obtain SiO 2 Aerogel microspheres.
(2) Preparation of Fe-SiO 2 Aerogel microspheres
Weighing 2g of nano zero-valent iron powder and SiO 2 2g of aerogel microsphere and grinding20g of ball is added into a ball mill, argon is filled into the ball mill, and ball milling is carried out for 5 to 20 hours at the rotating speed of 240 to 300rpm, thus obtaining Fe-SiO 2 Aerogel microspheres.
(3) Preparation of organic Polymer Supported La (III) @ Fe-SiO 2 Aerogel microspheres
(1) 0.15g sodium alginate and 3g polyvinyl alcohol were weighed into a beaker, 25mL deionized water was added, and stirred in a constant temperature water bath at 90℃for 30min to completely dissolve.
(2) 7.8507g of lanthanum chloride is weighed and dissolved in 10mL of deionized water to obtain a lanthanum chloride solution, and 6g of Fe-SiO is added into the lanthanum chloride solution 2 And (3) uniformly stirring the aerogel microspheres, and then adding the aerogel microspheres into the dissolved sodium alginate-polyvinyl alcohol solution to uniformly mix the aerogel microspheres to obtain sol.
(3) Preparing a cross-linking agent: 8g of anhydrous calcium chloride is weighed and placed in a 500mL beaker, 400mL of deionized water is added to prepare a solution, and the mass fraction is 2%. Adding a proper amount of boric acid until solid is separated out, and enabling the solution to reach saturation. Adding anhydrous sodium carbonate, stirring, performing ultrasonic treatment, and adjusting pH to 7.
(4) Sucking the sol by a 2mL syringe, dripping at a constant speed from the position about 20cm away from the liquid surface of the crosslinking agent, and stirring while dripping to prevent adhesion.
(5) After 5h of crosslinking, the prepared organic polymer is loaded with La@Fe-SiO 2 The aerogel microspheres were washed 3 times with deionized water to remove residual cross-linking agent on the surface, blotted with water absorbing paper to dry the surface moisture, freeze-dried in a-20 ℃ refrigerator for 24h and stored in sealed bags for further use.
FIG. 1 shows the organic polymer supported La@Fe-SiO of example 1 2 As can be seen from fig. 1, a large amount of nano-scale crystals exist on the surface of the material, and EDS point scanning results (as shown in fig. 2) of the surface of the material show that: lanthanum and iron are successfully loaded on an organic polymer SiO 2 On aerogel microspheres, the method used in the invention proves that the development of the adsorbent can be realized.
La@Fe-SiO to the organic polymer of example 1 2 The phosphorus removal material was subjected to an Fe ion release experiment in clear water, and the results are shown in Table 1.
As is clear from the above table, la@Fe-SiO is supported by the organic polymer of the present invention 2 Aerogel microsphere structure utilizing SiO 2 The zero-valent Fe of the effective load in the aerogel controls the slow release of iron ions, so as to achieve the effective and continuous removal of phosphorus in the water environment.
The organic polymeric phosphorus removal adsorbent material obtained in example 1 was tested as follows: 0.2g of the organic polymer adsorption material obtained in example 1 was weighed, 50mL of the simulated phosphorus-containing wastewater with an initial concentration of 500mg/L and a pH=7 was added, shaking was performed for 6 hours at a constant temperature of 150rpm in a shaking table at 25+ -1 ℃, the supernatant was taken and passed through a 0.45 μm filter membrane, and the phosphate concentration in the solution was measured on the obtained filtrate by an ammonium molybdate spectrophotometry, thereby obtaining a phosphorus adsorption amount of 54.4mg P/g.
Example 2
This embodiment differs from embodiment 1 in that: in the step (3), 5.6507g of lanthanum chloride is weighed and dissolved in 10mL of deionized water to obtain a lanthanum chloride solution, and 5g of Fe-SiO is added into the lanthanum chloride solution 2 And (3) uniformly stirring the aerogel microspheres, and then adding the aerogel microspheres into the dissolved sodium alginate-polyvinyl alcohol solution to uniformly mix the aerogel microspheres to obtain sol.
The organic polymeric phosphorus removal adsorbent material obtained in example 2 was tested as follows: 0.2g of the organic polymer adsorption material obtained in example 2 was weighed, 50mL of the simulated phosphorus-containing wastewater with an initial concentration of 500mg/L and a pH=7 was added, shaking was performed for 6 hours at a constant temperature of 150rpm in a shaking table at 25+ -1 ℃, the supernatant was taken and passed through a 0.45 μm filter membrane, and the phosphate concentration in the solution was measured on the obtained filtrate by an ammonium molybdate spectrophotometry, thereby obtaining a phosphorus adsorption amount of 42.3mg P/g.
Comparative example 1
This comparative example differs from example 1 in that: in the step (3), 7.8507g of lanthanum chloride is weighed and dissolved in 10mL of deionized water to obtain a lanthanum chloride solution, and Fe-SiO is not added 2 And (3) uniformly stirring the aerogel microspheres, and then adding the aerogel microspheres into the dissolved sodium alginate-polyvinyl alcohol solution to uniformly mix the aerogel microspheres to obtain sol. Pairing pairsThe organic polymer dephosphorizing adsorption material obtained in the proportion 1 is tested as follows: 0.2g of the organic polymer adsorption material obtained in comparative example 1 was weighed, 50mL of the simulated phosphorus-containing wastewater with an initial concentration of 500mg/L and a pH=7 was added, shaking was performed for 6 hours at a constant temperature of 150rpm in a shaking table at 25+ -1 ℃, the supernatant was taken and passed through a 0.45 μm filter membrane, and the phosphate concentration in the solution was measured on the obtained filtrate by an ammonium molybdate spectrophotometry, thereby obtaining a phosphorus adsorption amount of 32.3mg P/g.
Comparative example 2
For Fe-SiO prepared in example 1 2 The phosphorus adsorption experiment is carried out independently, and is specifically as follows:
0.2g of Fe-SiO prepared in example 1 was weighed out 2 50mL of simulated phosphorus-containing wastewater with initial concentration of 500mg/L and pH=7 is added, shaking is carried out for 6 hours at the temperature of 25+/-1 ℃ at 150rpm of a constant-temperature shaking table, the upper-layer liquid is taken to pass through a 0.45 mu m filter membrane, and the obtained filtrate is used for measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry. The results show that the Fe-SiO obtained in example 1 2 The phosphorus adsorption amount of the aerogel microsphere dephosphorization adsorbent is 25.2mg P/g.
Comparative example 3
This comparative example differs from example 1 in that neither lanthanum chloride nor Fe-SiO was supported 2 The adsorption performance of the organic polymer dephosphorization material to phosphorus is examined, and the specific steps are as follows:
weighing 0.2g of the mixture which is neither loaded with lanthanum chloride nor Fe-SiO 2 The adsorption performance of the organic polymer gel pellets is examined, 50mL of simulated phosphorus-containing wastewater with initial concentration of 500mg/L and pH=7 is added, shaking is carried out for 6 hours at the condition of 25+/-1 ℃ at the constant temperature of 150rpm of a shaking table, the upper liquid is taken to pass through a 0.45 mu m filter membrane, and the concentration of phosphate in the solution is measured by adopting an ammonium molybdate spectrophotometry. The results show that comparative example 3 resulted in neither lanthanum chloride nor Fe-SiO 2 The phosphorus adsorption amount of the organic polymer dephosphorization material of (2) is 5.2mg P/g.
Analysis of results
As can be seen from the results of the phosphorus adsorption amounts of the four phosphorus removal materials obtained in example 1 and comparative examples 1 to 3 in FIG. 3 in 500mg/L of phosphorus solution, in which, in the wastewater having an initial phosphorus concentration of 500mg/L, there was a solidExample 1 (La@Fe-SiO) 2 Organic polymer loaded La@Fe-SiO prepared by @ P) 2 The phosphorus adsorption amount of the phosphorus removal material is 54.4mg P/g;
the phosphorus adsorption amount of the polymer of comparative example 1 (La@P) loaded with La alone was 32.3mg P/g;
comparative example 2 (Fe-SiO) 2 ) The phosphorus adsorption capacity of the iron-carrying aerogel is 25.2mg P/g
Comparative example 3 (P) Polymer was not supported with La and Fe-SiO 2 The phosphorus adsorption amount of (2) is 5.2mg P/g;
as can be seen from the comparison of the phosphorus adsorption amounts, the organic polymer prepared by the invention is loaded with La@Fe-SiO 2 The adsorption dephosphorization effect of the organic polymer dephosphorization material is obviously superior to that of other materials with loading modes, and the prepared organic polymer dephosphorization material has Fe-SiO 2 The synergistic effect of the slow-release iron phosphorus removal and lanthanum adsorption phosphorus removal of the aerogel can meet the requirement of high-efficiency phosphorus removal under different environmental conditions.
Example 3
La@Fe-SiO carried by organic polymer prepared in example 1 2 The dephosphorization material is used for adsorbing and removing simulated phosphorus-containing wastewater with different initial concentrations, and the initial PO of the material is prepared by the following steps of 4 3- -P concentrations are respectively: 0.6,1.0,2.0,20,50mg/L of dephosphorization material, 0.2g of dephosphorization material, and PO in the solution after 8 hours of reaction 4 3- P removal rates of 96%,93%,92%,51% and 21%, respectively, corresponding to PO 4 3- The P adsorption capacities were 2.9,4.7,9.2,51.0 and 52.5mgP/g, respectively.
The rare earth lanthanum has strong affinity and selectivity to phosphorus, and is beneficial to the efficient removal of low-concentration phosphorus in water environment.
Claims (10)
1. Organic polymer supported La@Fe-SiO 2 Aerogel microspheres, wherein the metal Fe is filled in SiO 2 In the mesoporous pores of the aerogel microspheres, fe-SiO is obtained 2 Aerogel microspheres; the Fe-SiO 2 The aerogel microspheres are embedded in a gel network structure of the organic polymer; the surface of the organic polymer is loaded with lanthanum salt;
the organic polymer is loaded with La@Fe-SiO 2 Aerogel microsphere for dephosphorization adsorption materialThe material is used for removing phosphorus elements in the water body.
2. An organic polymer supported La@Fe-SiO according to claim 1 2 Aerogel microspheres, wherein the mass fraction of Fe is 10% -20%; siO (SiO) 2 The mass fraction of (2) is 10% -20%;
the mass fraction of La is 10% -20%;
the mass fraction of the organic polymer is 40% -70%;
preferably Fe-SiO 2 The total mass fraction of (2) is 20-40%.
3. An organic polymer supported La@Fe-SiO as claimed in claim 1 or 2 2 The preparation method of the aerogel microspheres is characterized by comprising the following steps:
1) Preparation of SiO 2 Aerogel microspheres;
2) Preparation of Fe-SiO 2 Aerogel microspheres: mixing simple substance powder of metal Fe with SiO 2 Mixing aerogel microspheres to obtain a mixture, and ball milling under argon atmosphere to obtain Fe-SiO 2 Aerogel microspheres;
3) Preparation of organic Polymer Supported La@Fe-SiO 2 Aerogel microspheres:
(1) dissolving sodium alginate and polyvinyl alcohol in deionized water to obtain sodium alginate-polyvinyl alcohol solution;
(2) dissolving lanthanum chloride in deionized water to obtain a lanthanum chloride solution;
(3) mixing sodium alginate-polyvinyl alcohol solution and lanthanum chloride solution, and adding Fe-SiO prepared in step 2) 2 Aerogel microspheres, stirring and mixing uniformly;
(4) dissolving anhydrous calcium chloride in deionized water to obtain a calcium chloride solution, adding boric acid and anhydrous sodium carbonate, stirring, performing ultrasonic treatment to saturate the solution, and adjusting the pH value to 6.8-7.2 to obtain a cross-linking agent;
(5) dropwise adding the sol obtained in the step (3) into a cross-linking agent solution, and stirring the solution while dripping to obtain the supported La@Fe-SiO 2 Organic polymer hydrogel microspheres;
(6) after the mixed solution is subjected to standing crosslinking reaction, washing and drying are carried out to obtain the organic polymer loaded La@Fe-SiO 2 Aerogel microspheres.
4. The method according to claim 3, wherein in the step 1), the ethyl orthosilicate, acetic acid and absolute ethanol are mixed and stirred, and the pH is adjusted to 8-9; adding diesel oil, and continuously stirring; after the reaction is finished, the SiO is obtained through suction filtration, washing, aging and drying 2 Aerogel microspheres;
the volume ratio of the tetraethoxysilane to the absolute ethyl alcohol is 1 (1-3); the volume ratio of the tetraethoxysilane to the acetic acid is (1-3) 1; the volume ratio of the diesel oil to the sum of the volumes of the tetraethoxysilane, the acetic acid and the absolute ethyl alcohol is 1 (1-1.2).
5. The method according to claim 3, wherein in the step 1), the mixture of ethyl orthosilicate, acetic acid and absolute ethanol is stirred at a temperature of 40-60 ℃ for 1.5-2.5 h;
the stirring time of mixing and continuously stirring the diesel oil, the tetraethoxysilane, the acetic acid and the absolute ethyl alcohol is 20-40 min.
6. The method according to claim 3, wherein in the step 2), the volume percentage of the elemental powder of the metal Fe in the mixture is 20% to 90%; the mass ratio of the grinding ball to the mixture is (20-50): 1; the rotating speed of the ball mill is 240-300 rpm; the ball milling time is 5-20 h.
7. The preparation method according to claim 3, wherein in the sodium alginate-polyvinyl alcohol solution, the mass fraction of sodium alginate is 4% -10%, the mass fraction of polyvinyl alcohol is 10% -12%, and the mass ratio of sodium alginate to polyvinyl alcohol is 1 (1-3);
the mass fraction of lanthanum chloride in the lanthanum chloride solution is 50-80%;
the mass fraction of the calcium chloride solution is 2-5%.
8. The method according to claim 3, wherein the Fe-SiO in the sol obtained in step 3) (3) 2 The mass fraction of (2) is 15-25%.
9. The method according to claim 3, wherein the volume ratio of the sol in the step 3) (5) to the crosslinking agent is 1 (7-12).
10. An organic polymer supported La@Fe-SiO as claimed in claim 1 or 2 2 Use of aerogel microspheres in the removal of phosphorus.
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