CN112642408A - Preparation method of MgO-loaded bentonite-sodium alginate composite ball - Google Patents
Preparation method of MgO-loaded bentonite-sodium alginate composite ball Download PDFInfo
- Publication number
- CN112642408A CN112642408A CN202011589455.3A CN202011589455A CN112642408A CN 112642408 A CN112642408 A CN 112642408A CN 202011589455 A CN202011589455 A CN 202011589455A CN 112642408 A CN112642408 A CN 112642408A
- Authority
- CN
- China
- Prior art keywords
- bentonite
- mgo
- sodium alginate
- hydrogel
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 67
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000440 bentonite Substances 0.000 claims abstract description 40
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 40
- 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 39
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 39
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 238000004108 freeze drying Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 239000000017 hydrogel Substances 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000000227 grinding Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000002572 peristaltic effect Effects 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 abstract description 10
- 239000010452 phosphate Substances 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 241000446313 Lamella Species 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 239000003337 fertilizer Substances 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 68
- 239000000395 magnesium oxide Substances 0.000 description 23
- 235000021317 phosphate Nutrition 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000002045 lasting effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 Lanthanum modified bentonite Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group 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 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- B01J20/28014—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 form
- B01J20/28047—Gels
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a MgO-loaded bentonite-sodium alginate composite sphere and a preparation method thereof, wherein the composite sphere is a sphere with the diameter of about 2mm and a structure with rich holes inside, and MgCl is added2Mixing the solution with bentonite, stirring, and adding Mg2+Entering bentonite lamella through interlayer replacement, preparing MgO loaded bentonite through co-pyrolysis, and then utilizing sodium alginate and Ca2+Solidifying the mixture through cross-linking reaction, and finally preparing the porous composite ball through tert-butyl alcohol displacement and freeze drying. Compared with the bentonite-sodium alginate composite ball without MgO load, the MgO @ Bt composite ball has the specific surface areaThe porosity and the adsorption performance of phosphate are improved, the composite material after saturated adsorption is convenient to recover, and the composite material can be used as a slow release fertilizer for crop growth to realize the cyclic utilization of phosphorus.
Description
Technical Field
The invention belongs to the field of preparation of green environment-friendly recyclable adsorption materials, and particularly relates to a preparation method of an MgO-loaded bentonite-sodium alginate composite ball.
Background
Population growth and industrialization have been promoted to discharge a large amount of wastewater containing nutrients, and eutrophication of water and rapid consumption of nutrients are seriously threatening sustainable development of human society, wherein phosphorus is a limiting nutrient in water, and common methods for treating wastewater containing phosphorus include biological methods, chemical precipitation methods, membrane separation methods, electrolysis methods, adsorption methods, and the like, wherein the adsorption methods are widely concerned due to simple operation, low cost, and high removal efficiency. The metal (hydroxide) has strong affinity to phosphate, but the application of the metal (hydroxide) is limited by the characteristics that metal (hydroxide) nanoparticles are easy to agglomerate, expensive and difficult to separate solid from liquid to cause secondary pollution to a water environment and the like.
The bentonite is a clay mineral with abundant reserves, the main component is montmorillonite, the bentonite has a unique lamellar structure of two silicon-oxygen tetrahedrons with one aluminum-oxygen octahedron, exchangeable cations are arranged between the two layers, and the bentonite has the advantages of abundant Si-O and Al-O active groups, large specific surface area, stable physicochemical property, large cation exchange capacity, easy modification and the like, so that the bentonite has the potential of becoming an excellent adsorbent. Lanthanum modified bentonite Phosclock was invented by the Australian Federal scientific and Industrial research organization as early as 1990®And has been extensively developed and tested in laboratories, on mesoscopic and on the whole lake scale. However, the potential risk caused by La ion leaching is unknown, and powdered bentonite is difficult to separate solid from liquid, and valuable phosphorus resources cannot be recovered (Diego Copetti, Karin Filter, Laura Marziali. Eurotion management in surface waters using bentonite modified bentonite: A review [ J ]]Water Research, 97(2016) 162-. Metal (hydr) oxides are known to have a strong affinity for phosphates, such as magnesium oxide, zirconium oxide, lanthanum oxide, and are known in the literature (Yan Xia, Kangyu Dong, Xiangmei Xiang. phosphorous hyperaccumulation in nano-MgO using a circular recovery process based on multiple phase transitions from peroxide to broken [ J Xia, K]Science of the Total Environment, 727(2020) 138510) recovering phosphate from aqueous solution by using nano-magnesia, the adsorption capacity is as high as 115.9 mg-P.g-1. However, the industrial application of the metal nanoparticles is limited by the disadvantages of easy agglomeration and difficult recovery of the metal nanoparticles in aqueous solution. Sodium alginate is natural polysaccharide generated by seaweed, and has the characteristics of no toxicity, degradability, environmental friendliness and the like, so that the sodium alginate becomes a research hotspot in the field of water treatment in recent years, and can generate a crosslinking reaction with polyvalent metal ions to form hydrogel spheres, thereby facilitating nutrient recovery. 2019, literature (Xuanqi Huang), Wufeng Wu, Yan Xia. Alkali resistant nanocomposite gel beads as renewable adsorbents for water phosphate recovery [J]Science of the Total Environment, 685(2019) 10-18) preparation of strontium crosslinked sodium alginate hydrogel for removing phosphate from aqueous solution with adsorption capacity up to 52.5 mg-P.g-1. However, the mechanical strength of the sodium alginate hydrogel is poor, so that the industrial application of the sodium alginate hydrogel is limited.
From the above conclusion, the metal nanoparticles are loaded on the bentonite, which can avoid the agglomeration of the nanoparticles, but have the defects of difficult recovery of precious phosphorus resources, potential risk of causing secondary pollution of water and the like, so that the metal nanoparticles are limited in the aspect of practical application. In order to reduce the potential risk of the adsorbent to the environment and recover phosphorus resources, the invention provides that MgO nano particles are used for loading bentonite, sodium alginate is used for solidifying the bentonite, and finally tert-butyl alcohol solvent replacement and freeze drying are used for adjusting the microstructure of the composite ball, so that the porous MgO nano particle loaded bentonite-sodium alginate composite ball is prepared and used for removing excessive phosphate in water.
Disclosure of Invention
Aiming at the characteristics that metal (hydroxide) nanoparticles are easy to agglomerate, high in price and difficult to separate solid from liquid, and secondary pollution to a water environment is caused. The invention provides a preparation method of an MgO-loaded bentonite-sodium alginate composite ball, which utilizes natural bentonite as a matrix material and solidifies the natural bentonite through sodium alginate. With MgCl2Bentonite and sodium alginate as raw materials, and MgCl is controlled2The MgO-loaded bentonite-sodium alginate composite material with rich pore structure, excellent specific surface area and phosphate adsorption performance is obtained under the conditions of the concentration of the solution, the pyrolysis temperature, the pyrolysis time, the doping ratio of the bentonite and the sodium alginate and the like. The MgO-loaded bentonite-sodium alginate composite ball prepared by the method has the characteristics of rich pores, excellent adsorption performance, simple and controllable preparation process, low production cost, green and environment-friendly raw materials and the like.
In order to solve the problems, the invention adopts the following scheme: the method for preparing the MgO-loaded bentonite-sodium alginate composite ball comprises the following steps:
(1) a pretreatment step: MgCl was prepared in 200mL2Adding 10g of bentonite into the solution, magnetically stirring for 12h, and performing ion exchange between bentonite layers to obtain Mg in the solution2+The intercalation layer enters between the bentonite layers, and then the mixed solution is poured into a culture dish, 90 DEGoC, drying in an oven, grinding and sieving with a 100-mesh sieve;
(2) a co-pyrolysis step: taking the pretreated bentonite in the step, spreading the bentonite in a ceramic crucible, calcining the bentonite in a muffle furnace, and washing the calcined bentonite with deionized water until no Cl exists-And Mg2+，60oC, drying and grinding the mixture in an oven, and sieving the mixture through a 100-mesh sieve, and marking as MgO @ Bt;
(3) a crosslinking step: adding Sodium Alginate (SA) into 120mL deionized water, and adding into the deionized water to obtain a mixtureoC, stirring for 1h until sodium alginate is completely dissolved, adding MgO @ Bt in the steps, continuously stirring for 1h to obtain uniform suspension, cooling to room temperature, and then dripping 500mLCaCl into the suspension by using a peristaltic pump2Obtaining MgO @ Bt-SA composite hydrogel spheres in the solution;
(4) tert-butanol replacement-freeze drying step: and (2) placing the MgO @ Bt-SA composite hydrogel in the step into deionized water for washing for a plurality of times, then soaking the hydrogel in 500mL of deionized water for solvent replacement, then placing the hydrogel into a 25% tert-butyl alcohol solution for replacement, placing the hydrogel into a 50% tert-butyl alcohol solution for replacement after 6 hours, then placing the hydrogel into a 100% tert-butyl alcohol solution for replacement after 6 hours, and freeze-drying the hydrogel after 6 hours to obtain the final MgO-loaded bentonite-sodium alginate composite ball.
Preferably, in the step (1), MgCl2The concentration of the solution is 0.05-1.0 mol/L.
Preferably, in the step (2), the calcining temperature is 400-700 DEGoC, the temperature rise speed is 5-10oC/min, and the duration is 2-8 h.
Preferably, in the step (3), the adding amount of sodium alginate is 1.0-2.0 g.
Preferably, in the step (3), the mass ratio of the added MgO @ Bt to the sodium alginate is 5-10: 1.
preferably, in the step (3), CaCl2The concentration of the solution is 1-3 wt%.
The invention is provided withThe beneficial effects are that: the invention provides a preparation method of an MgO-loaded bentonite-sodium alginate composite ball, which is simple and controllable in operation, low in cost, green and environment-friendly, and the composite adsorption material has a rich pore structure and a specific surface area as high as 59.4626m2The removal rate of phosphate can reach 98.8 percent.
Drawings
FIG. 1 is a SEM image of the section of the MgO-loaded bentonite-sodium alginate composite sphere prepared by the method in example 1, and it can be seen that the composite sphere has a diameter of about 2mm, and the inside of the composite sphere is filled with pores, so that phosphate radicals in the solution can enter the inside of the adsorbent and can be fully contacted with the active sites of the MgO nanoparticles.
Fig. 2 shows a nitrogen adsorption/desorption curve and a pore size distribution curve (embedded) of the MgO-loaded bentonite-sodium alginate composite sphere prepared by the method in example 1, and it can be seen from the figure that the composite sphere has a typical type IV isotherm, has the properties of a mesoporous material, and the pore size distribution curve also confirms the conclusion.
Table 1 shows the comparison of the adsorption capacity of the MgO loaded bentonite-sodium alginate composite ball prepared by the method of example 1 with that of other common adsorbents, and it can be seen from the table that the composite ball has a large adsorption capacity, and also has the advantages of easy recovery, environmental protection, and the like.
Detailed Description
The invention is described in detail below with reference to specific examples, which are intended to be illustrative only and not to be limiting of the invention, and all changes that can be made by the description are intended to be within the scope of the invention as defined by the appended claims.
Example 1
(1) 200mL of 0.2mol/L MgCl was prepared2Adding 10g of bentonite into the solution, magnetically stirring for 12h, pouring the mixed solution into a culture dish, and stirring for 90 goC, drying in an oven, grinding and sieving with a 100-mesh sieve;
(2) taking 10g of Mg2+The pretreated bentonite is laid in a ceramic crucible and then placed in a muffle furnace for 5 DEGoThe temperature rises to 550 ℃ at the temperature rising speed of C/minoC, lasting for 5h, and then washing to be Cl-free by deionized water-And Mg2+，60oC oven drying, grinding, sieving with 100 mesh sieve, and recordingIs MgO @ Bt;
(3) adding 1.5g Sodium Alginate (SA) into 120mL deionized water, and adding 60 g sodium alginateoC, stirring for 1h until sodium alginate is completely dissolved, adding 10g of MgO @ Bt, continuously stirring for 1h to obtain a uniform suspension, cooling to room temperature, and dripping 500mLCaCl into the suspension by using a peristaltic pump2Obtaining MgO @ Bt-SA composite hydrogel spheres in the solution;
(4) tert-butanol replacement-freeze drying step: and (2) placing the MgO @ Bt-SA composite hydrogel in the step into deionized water for washing for a plurality of times, then soaking the hydrogel in 500mL of deionized water for solvent replacement, then placing the hydrogel into a 25% tert-butyl alcohol solution for replacement, placing the hydrogel into a 50% tert-butyl alcohol solution for replacement after 6 hours, then placing the hydrogel into a 100% tert-butyl alcohol solution for replacement after 6 hours, and freeze-drying the hydrogel after 6 hours to obtain the final MgO-loaded bentonite-sodium alginate composite ball.
Example 2
(1) 200mL of 0.5mol/L MgCl was prepared2Adding 10g of bentonite into the solution, magnetically stirring for 12h, pouring the mixed solution into a culture dish, and stirring for 90 goC, drying in an oven, grinding and sieving with a 100-mesh sieve;
(2) taking 10g of Mg2+The pretreated bentonite is laid in a ceramic crucible and then placed in a muffle furnace for 5 DEGoThe temperature rises to 550 ℃ at the temperature rising speed of C/minoC, lasting for 5h, and then washing to be Cl-free by deionized water-And Mg2+，60oC, drying and grinding the mixture in an oven, and sieving the mixture through a 100-mesh sieve, and marking as MgO @ Bt;
(3) adding 1.5g Sodium Alginate (SA) into 120mL deionized water, and adding 60 g sodium alginateoC, stirring for 1h until sodium alginate is completely dissolved, adding 10g of MgO @ Bt, continuously stirring for 1h to obtain a uniform suspension, cooling to room temperature, and dripping 500mLCaCl into the suspension by using a peristaltic pump2Obtaining MgO @ Bt-SA composite hydrogel spheres in the solution;
(4) tert-butanol replacement-freeze drying step: and (2) placing the MgO @ Bt-SA composite hydrogel in the step into deionized water for washing for a plurality of times, then soaking the hydrogel in 500mL of deionized water for solvent replacement, then placing the hydrogel into a 25% tert-butyl alcohol solution for replacement, placing the hydrogel into a 50% tert-butyl alcohol solution for replacement after 6 hours, then placing the hydrogel into a 100% tert-butyl alcohol solution for replacement after 6 hours, and freeze-drying the hydrogel after 6 hours to obtain the final MgO-loaded bentonite-sodium alginate composite ball.
Example 3
(1) 200mL of 0.2mol/L MgCl was prepared2Adding 10g of bentonite into the solution, magnetically stirring for 12h, pouring the mixed solution into a culture dish, and stirring for 90 goC, drying in an oven, grinding and sieving with a 100-mesh sieve;
(2) taking 10g of Mg2+The pretreated bentonite is laid in a ceramic crucible and then placed in a muffle furnace for 5 DEGoThe temperature rises to 550 ℃ at the temperature rising speed of C/minoC, lasting for 5h, and then washing to be Cl-free by deionized water-And Mg2+，60oC, drying and grinding the mixture in an oven, and sieving the mixture through a 100-mesh sieve, and marking as MgO @ Bt;
(3) adding 1.0g Sodium Alginate (SA) into 120mL deionized water, and adding 60 g sodium alginateoC, stirring for 1h until sodium alginate is completely dissolved, adding 10g of MgO @ Bt, continuously stirring for 1h to obtain a uniform suspension, cooling to room temperature, and dripping 500mLCaCl into the suspension by using a peristaltic pump2Obtaining MgO @ Bt-SA composite hydrogel spheres in the solution;
(4) tert-butanol replacement-freeze drying step: and (2) placing the MgO @ Bt-SA composite hydrogel in the step into deionized water for washing for a plurality of times, then soaking the hydrogel in 500mL of deionized water for solvent replacement, then placing the hydrogel into a 25% tert-butyl alcohol solution for replacement, placing the hydrogel into a 50% tert-butyl alcohol solution for replacement after 6 hours, then placing the hydrogel into a 100% tert-butyl alcohol solution for replacement after 6 hours, and freeze-drying the hydrogel after 6 hours to obtain the final MgO-loaded bentonite-sodium alginate composite ball.
Example 4
(1) 200mL of 0.2mol/L MgCl was prepared2Adding 10g of bentonite into the solution, magnetically stirring for 12h, pouring the mixed solution into a culture dish, and stirring for 90 goC, drying in an oven, grinding and sieving with a 100-mesh sieve;
(2) taking 10g of Mg2+The pretreated bentonite is laid in a ceramic crucible and then placed in a muffle furnace for 5 DEGoThe temperature rises to 550 ℃ at the temperature rising speed of C/minoC, lasting for 5h, and then washing to be Cl-free by deionized water-And Mg2+，60oC, drying and grinding the mixture in an oven, and sieving the mixture through a 100-mesh sieve, and marking as MgO @ Bt;
(3) 2.0g of Sodium Alginate (SA) was added to 120mL of deionized water, 60oC, stirring for 1h until sodium alginate is completely dissolved, adding 10g of MgO @ Bt, continuously stirring for 1h to obtain a uniform suspension, cooling to room temperature, and dripping 500mLCaCl into the suspension by using a peristaltic pump2Obtaining MgO @ Bt-SA composite hydrogel spheres in the solution;
(4) tert-butanol replacement-freeze drying step: and (2) placing the MgO @ Bt-SA composite hydrogel in the step into deionized water for washing for a plurality of times, then soaking the hydrogel in 500mL of deionized water for solvent replacement, then placing the hydrogel into a 25% tert-butyl alcohol solution for replacement, placing the hydrogel into a 50% tert-butyl alcohol solution for replacement after 6 hours, then placing the hydrogel into a 100% tert-butyl alcohol solution for replacement after 6 hours, and freeze-drying the hydrogel after 6 hours to obtain the final MgO-loaded bentonite-sodium alginate composite ball.
Example 5
(1) 200mL of 0.2mol/L MgCl was prepared2Adding 10g of bentonite into the solution, magnetically stirring for 12h, pouring the mixed solution into a culture dish, and stirring for 90 goC, drying in an oven, grinding and sieving with a 100-mesh sieve;
(2) taking 10g of Mg2+The pretreated bentonite is laid in a ceramic crucible and then placed in a muffle furnace for 5 DEGoThe temperature rises to 450 ℃ at the temperature rising speed of C/minoC, lasting for 3 hours, and then washing to be Cl-free by deionized water-And Mg2+，60oC, drying and grinding the mixture in an oven, and sieving the mixture through a 100-mesh sieve, and marking as MgO @ Bt;
(3) adding 1.5g Sodium Alginate (SA) into 120mL deionized water, and adding 60 g sodium alginateoC, stirring for 1h until sodium alginate is completely dissolved, adding 10g of MgO @ Bt, continuously stirring for 1h to obtain a uniform suspension, cooling to room temperature, and dripping 500mLCaCl into the suspension by using a peristaltic pump2Obtaining MgO @ Bt-SA composite hydrogel spheres in the solution;
(4) tert-butanol replacement-freeze drying step: and (2) placing the MgO @ Bt-SA composite hydrogel in the step into deionized water for washing for a plurality of times, then soaking the hydrogel in 500mL of deionized water for solvent replacement, then placing the hydrogel into a 25% tert-butyl alcohol solution for replacement, placing the hydrogel into a 50% tert-butyl alcohol solution for replacement after 6 hours, then placing the hydrogel into a 100% tert-butyl alcohol solution for replacement after 6 hours, and freeze-drying the hydrogel after 6 hours to obtain the final MgO-loaded bentonite-sodium alginate composite ball.
TABLE 1 comparison of adsorption capacities of MgO-loaded bentonite-sodium alginate composite spheres and other common adsorbents
Claims (6)
1. A preparation method of an MgO-loaded bentonite-sodium alginate composite ball is characterized by comprising the following steps:
(1) a pretreatment step: MgCl was prepared in 200mL2Adding 10g of bentonite into the solution, magnetically stirring for 12h, and performing ion exchange between bentonite layers to obtain Mg in the solution2+The intercalation layer enters between the bentonite layers, and then the mixed solution is poured into a culture dish, 90 DEGoC, drying in an oven, grinding and sieving with a 100-mesh sieve;
(2) a co-pyrolysis step: taking the pretreated bentonite in the step, spreading the bentonite in a ceramic crucible, calcining the bentonite in a muffle furnace, and washing the calcined bentonite with deionized water until no Cl exists-And Mg2+，60oC, drying and grinding the mixture in an oven, and sieving the mixture through a 100-mesh sieve, and marking as MgO @ Bt;
(3) a crosslinking step: adding Sodium Alginate (SA) into 120mL deionized water, and adding into the deionized water to obtain a mixtureoC, stirring for 1h until sodium alginate is completely dissolved, adding MgO @ Bt in the steps, continuously stirring for 1h to obtain uniform suspension, cooling to room temperature, and then dripping 500mLCaCl into the suspension by using a peristaltic pump2Obtaining MgO @ Bt-SA composite hydrogel spheres in the solution;
(4) tert-butanol replacement-freeze drying step: and (2) placing the MgO @ Bt-SA composite hydrogel in the step into deionized water for washing for a plurality of times, then soaking the hydrogel in 500mL of deionized water for solvent replacement, then placing the hydrogel into a 25% tert-butyl alcohol solution for replacement, placing the hydrogel into a 50% tert-butyl alcohol solution for replacement after 6 hours, then placing the hydrogel into a 100% tert-butyl alcohol solution for replacement after 6 hours, and freeze-drying the hydrogel after 6 hours to obtain the final MgO-loaded bentonite-sodium alginate composite ball.
2. The method for preparing MgO-loaded bentonite-sodium alginate composite spheres according to claim 1, wherein in the step (1), MgCl is adopted2The solution has a concentration of0.05~1.0mol/L。
3. The preparation method of the MgO-loaded bentonite-sodium alginate composite sphere according to claim 1, wherein in the step (2), the calcination temperature is 400-700 ℃oC, the temperature rise speed is 5-10oC/min, and the duration is 2-8 h.
4. The preparation method of the MgO-loaded bentonite-sodium alginate composite bead as claimed in claim 1, wherein in the step (3), the amount of sodium alginate added is 1.0-2.0 g.
5. The preparation method of the MgO-loaded bentonite-sodium alginate composite bead as claimed in claim 1, wherein in the step (3), the mass ratio of the added MgO @ Bt to the sodium alginate is 5-10: 1.
6. the method for preparing MgO-loaded bentonite-sodium alginate composite spheres according to claim 1, wherein in the step (3), CaCl is added2The concentration of the solution is 1-3 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011589455.3A CN112642408A (en) | 2020-12-29 | 2020-12-29 | Preparation method of MgO-loaded bentonite-sodium alginate composite ball |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011589455.3A CN112642408A (en) | 2020-12-29 | 2020-12-29 | Preparation method of MgO-loaded bentonite-sodium alginate composite ball |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112642408A true CN112642408A (en) | 2021-04-13 |
Family
ID=75363637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011589455.3A Pending CN112642408A (en) | 2020-12-29 | 2020-12-29 | Preparation method of MgO-loaded bentonite-sodium alginate composite ball |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112642408A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031055A (en) * | 2021-11-05 | 2022-02-11 | 安徽东至广信农化有限公司 | Chlorination kettle cleaning process for phosphorus trichloride production |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1143922A (en) * | 1965-03-05 | 1969-02-26 | Georgia Kaolin Co | Modified montmorillonites, compositions including said modified montmorillonites and methods for obtaining the modified montmorillonites |
| CN106076249A (en) * | 2016-06-13 | 2016-11-09 | 环境保护部南京环境科学研究所 | A kind of modified alta-mud prepares the method for heavy metal particles adsorbent |
| CN109423488A (en) * | 2017-08-29 | 2019-03-05 | 湖南大学 | Immobilization laccase and preparation method thereof |
| CN111729644A (en) * | 2020-07-31 | 2020-10-02 | 河海大学 | Biochar-bentonite porous composite ball and preparation method thereof |
| CN111905698A (en) * | 2020-08-04 | 2020-11-10 | 武汉大学 | Modified bentonite-sodium alginate composite gel ball, preparation method thereof and application of modified bentonite-sodium alginate composite gel ball as adsorption material |
-
2020
- 2020-12-29 CN CN202011589455.3A patent/CN112642408A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1143922A (en) * | 1965-03-05 | 1969-02-26 | Georgia Kaolin Co | Modified montmorillonites, compositions including said modified montmorillonites and methods for obtaining the modified montmorillonites |
| CN106076249A (en) * | 2016-06-13 | 2016-11-09 | 环境保护部南京环境科学研究所 | A kind of modified alta-mud prepares the method for heavy metal particles adsorbent |
| CN109423488A (en) * | 2017-08-29 | 2019-03-05 | 湖南大学 | Immobilization laccase and preparation method thereof |
| CN111729644A (en) * | 2020-07-31 | 2020-10-02 | 河海大学 | Biochar-bentonite porous composite ball and preparation method thereof |
| CN111905698A (en) * | 2020-08-04 | 2020-11-10 | 武汉大学 | Modified bentonite-sodium alginate composite gel ball, preparation method thereof and application of modified bentonite-sodium alginate composite gel ball as adsorption material |
Non-Patent Citations (1)
| Title |
|---|
| 胡巧开: "氨氮废水的吸附处理", 《无机盐工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031055A (en) * | 2021-11-05 | 2022-02-11 | 安徽东至广信农化有限公司 | Chlorination kettle cleaning process for phosphorus trichloride production |
| CN114031055B (en) * | 2021-11-05 | 2023-12-12 | 安徽东至广信农化有限公司 | Chlorination kettle cleaning process for phosphorus trichloride production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102824898B (en) | Three-dimensional porous pressure-resistant and expansion-limiting type bentonite adsorbing material and preparation method thereof | |
| Wu et al. | Facile fabrication of MOF (Fe)@ alginate aerogel and its application for a high-performance slow-release N-fertilizer | |
| CN112808251A (en) | Adsorbent for extracting lithium from salt lake and preparation method thereof | |
| CN107573457B (en) | Porous interpenetrating network poly N-isopropylacrylamide/zirconium alginate gel ball and preparation method and application thereof | |
| CN108435143B (en) | High-hydrophilicity adsorbent, preparation and application of adsorbent in adsorbing rubidium ions or lithium ions | |
| CN111558350A (en) | Preparation method of HTO/cellulose aerogel microspheres for extracting lithium from seawater | |
| CN111701567A (en) | Magnetic magnesium ferrite biochar composite microsphere phosphorus removal adsorbent and preparation method and application thereof | |
| CN112063387B (en) | Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof | |
| CN1304281C (en) | Preparing method for porous carbon with high specific surface area | |
| CN107739031B (en) | Method for preparing lithium ion carbon negative electrode material from mushroom residue waste | |
| CN106824069A (en) | Preparation method for processing the rear-earth-doped iron Carbon Materials of arsenic-containing waste water | |
| CN112642408A (en) | Preparation method of MgO-loaded bentonite-sodium alginate composite ball | |
| Papa et al. | Geopolymer-hydrotalcite hybrid beads by ionotropic gelation | |
| CN114288983A (en) | Titanium-based lithium ion exchanger and preparation method thereof | |
| CN116920807B (en) | Adsorbent for extracting lithium from salt lake and preparation method thereof | |
| CN107732209B (en) | Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste | |
| Qi et al. | Cross-linked HMO/PVA nanofiber mats for efficient lithium extraction from Salt-lake | |
| CN110577223B (en) | Preparation process of porous carbon nanosphere | |
| KR101292524B1 (en) | Preparation Method of complex comprising a porous alginic acid gel | |
| CN116159531A (en) | Preparation method of hollow fiber membrane lithium ion adsorbent | |
| CN113184921B (en) | LDH-based composite material based on nickel-containing sludge and preparation method thereof | |
| Zhang | Current diatom research in China | |
| CN203508037U (en) | Composite hydrogel filter cake used for adsorbing heavy metal ions | |
| CN114073939A (en) | Three-dimensional biochar carrier based on enzymatic hydrolysis method and preparation method thereof | |
| CN110090632B (en) | Composite lithium ion adsorption column material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210413 |