CN105032342A - Preparation method of stratiform bimetallic oxide sorbent capable of effectively removing low-concentrated phosphate radical - Google Patents
Preparation method of stratiform bimetallic oxide sorbent capable of effectively removing low-concentrated phosphate radical Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 5
- 239000010452 phosphate Substances 0.000 title claims abstract description 5
- 239000002594 sorbent Substances 0.000 title abstract 3
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000003463 adsorbent Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000975 co-precipitation Methods 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 39
- 239000002135 nanosheet Substances 0.000 abstract description 13
- 238000001354 calcination Methods 0.000 abstract description 7
- 239000006184 cosolvent Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 abstract 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract 1
- 229960001545 hydrotalcite Drugs 0.000 abstract 1
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 102100034671 L-lactate dehydrogenase A chain Human genes 0.000 description 12
- 108010088350 Lactate Dehydrogenase 5 Proteins 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 241000446313 Lamella Species 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000012851 eutrophication Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003653 coastal water Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method and application of a stratiform bimetallic oxide sorbent capable of effectively removing low-concentrated phosphate radical. According to the invention, a hydrophobic ionic liquid BmimPF6 is taken as oil phase, and N,N-dimethyl formamide (DMF) is taken as a cosolvent in a Bmim PF6/DMF/H2O ionic liquid-in-water inverse surfactant-free microemulsion system, a small particle diameter ultrathin stratiform bimetallic hydroxide nanosheets precursor is prepared according to a double microemulsion coprecipitation method, calcination of the precursor is carried out at high temperature of 500 DEG C so as to prepare stratiform bimetallic oxides adsorbent. The obtained stratiform bimetallic oxides are 107.36-158.46 cm<2>/g in specific surface area, 8.56-11.17 nm in pore diameter, and 0.358-0.468 cm<3>/g in pore volume. The stratiform bimetallic oxides can restore and form stratiform bimetallic hydroxide nanosheets in an aqueous medium, wherein the particle diameter of nanosheets is 150-200 nm, the thickness is about 5 nm, and the distribution of particle diameters is uniform. The adsorption rate of the stratiform bimetallic oxides is far higher than that of large-grained hydrotalcite prepared from the precursor stratiform bimetallic oxides of the sorbent according to the traditional coprecipitation method.
Description
Technical field:
The present invention relates to a kind of layered bi-metal oxide adsorbent preparation method of effective removal low phosphorus acid group, and the present invention relates to preparation method's gained stratiform bimetallic oxide adsorbent to the adsorption applications of low phosphorus acid group in water body, belong to field of nanometer material technology.
Background technology:
Along with the modern development of industrial or agricultural, the nutriments such as a large amount of nitrogen, phosphorus enter water body with sewage, coastal waters and water body in lake is made to occur eutrophication, algae and other planktonic organism is caused to breed rapidly, cause the consequences such as water quality deterioration, aquatile mortality, not only destroy the ecosystem, and the toxin produced can threaten human health by food chain.Research shows that phosphorus is the crucial governing factor of body eutrophication, and when its concentration is higher than 0.03mg/L, the eutrophication of water body will cause red tide or wawter bloom to occur.Therefore, the content effectively reducing phosphorus in waste discharge occurs significant to suppression body eutrophication, prevention red tide or wawter bloom.The method of domestic and international waste water dephosphorization mainly contains bioanalysis, absorption method, chemical precipitation method, crystallisation and ion-exchange, and ecological method etc., wherein to have equipment simple because of it for absorption method, easy and simple to handle, do not produce the advantages such as secondary pollution, gain great popularity, and clay mineral has unique layer structure because of it, large specific area, good absorption and ion-exchange performance, and rich reserves, cheap, nontoxic to environment, regenerating easily, be widely applied [ZhouJ as new and effective sorbing material in waste water dephosphorization field, YangS, YuJ, ShuZ.Novelhollowmicrospheresofhierarchicalzinc – aluminumlayereddoublehydroxidesandtheirenhancedadsorptio ncapacityforphosphateinwater.J.Hazard.Mater.2011, 192, 1114 – 1121.].
Layered double hydroxide (LayeredDoubleHydroxides, LDH) is an anionoid clay, and its general formula is [M
1-x 2+m
x 3+(OH)
2]
x+(A
n-)
x/nmH
2o, wherein M (OH)
6octahedron shares rib and presents open lamella packed structures, and each octahedra unit is formed with the OH-being positioned at summit by the central metallic ions M of hexa-coordinate.Due to part M
2+by M
3+replacement can make lamella band structure positive charge, and interlayer exists tradable anion makes electric charge reach balance.The engaging force of LDH interlayer is more weak, mezzanine space high resilience, has the features such as larger surface area, higher ion exchange capacity and excellent heat endurance, shows very strong capture ability to organic and inorganic anion.But LDH can produce non-stoichiometric layered bi-metal oxide (LDO) after 400 ~ 800 DEG C of calcinings, due to " memory effect " of LDH, hydration is there is in calcined product LDO in containing the aqueous solution of pollutant, again recover between anionic pollutant insert layer in the process of LDH, thus there is higher adsorption capacity [CaiP, ZhengH, WangC, MaH, HuJ, PuY, LiangP.Competitiveadsorptioncharacteristicsoffluorideand phosphateoncalcinedMg-Al-CO
3layereddoublehydroxides.J.Hazard.Mater.2012,213-214,100-108.].Current LDH and LDO has been used successfully to the removal of silver orthophosphate in waste discharge, seawater.But the conventional method LDH particle diameter of preparing gained is comparatively large and pattern is uncontrollable, and easily assemble when using, the absorption property of calcined product LDO to pollutant obtained is not fully exerted, therefore, improve the surface area of presoma LDH, increase adsorption site and adsorption capacity, the efficient LDO adsorbent of exploitation is had great significance.
Normally countless " the small water droplet " of reverse micro emulsion is dispersed in oil-continuous phase, and the isotropism of formation, transparent and thermodynamically stable dispersion, be made up of with proper proportion components such as water, oil, surfactant and cosurfactants.These stable each " small water droplets " separated from one another are microreactors, have very large interface, the size that it is adjustable can not only control the coring and increment of nano particle, and can also control the size of particle, is considered to the excellent medium of controlled synthesis inorganic nano-particle.All surfactant is contained in conventional inverter microemulsion, the inorganic nano-particle adopting them to prepare all is mixed with surfactant bar none, when particularly adopting reverse micro emulsion to prepare LDH, surfactant can be intercalation into its interlayer with anionic form, or be adsorbed on the surface [HuG of stratified material, O ' HareD.Uniquelayereddoublehydroxidemorphologiesusingrever semicroemulsionsynthesis, J.Am.Chem.Soc.2005, 127, 17808-17813.], secondary pollution can be caused when gained sorbing material is used, and make the regenerative process of sorbing material abnormal loaded down with trivial details, cost is higher.
Research shows, do not having under surfactant, some three component systems also can form microemulsion, and this kind of microemulsion is called as surfactant-free microemulsion (Surfactant-freeMicroemulsion, SFME).SFME system is adopted to prepare LDH, there is not contaminating impurity in the LDH particle not only can control Nanoparticle Size, particle size distribution range is narrow, raising is dispersed, obtaining, and component is simple, easy and simple to handle, fundamentally solve Problems existing when classical microemulsion prepares LDH, simultaneously also for the efficient LDO adsorbent of preparation provides new thinking.But, with hydrophobic ionic liquid BmimPF
6for oil phase, the BmimPF being cosolvent with DMF (DMF)
6/ DMF/H
2first prepare the ultra-thin LDH nanometer sheet of small particle diameter in O ionic liquid bag water anti-phase SFME system, and then LDO is prepared in high-temperature calcination, and the correlative study using it for low concentration Phosphateadsorption in water body have not been reported.
Summary of the invention:
For the demand of the deficiencies in the prior art and this area investigation and application, the object of this invention is to provide a kind of layered bi-metal oxide adsorbent preparation method of effective removal low phosphorus acid group.First with hydrophobic ionic liquid BmimPF
6for oil phase, the BmimPF being cosolvent with DMF (DMF)
6/ DMF/H
2in the anti-phase SFME system of O ionic liquid bag water, prepare the ultra-thin LDH nanometer sheet of small particle diameter with two microemulsion coprecipitation method, and then 500 DEG C of high-temperature calcinations prepare the layered bi-metal oxide adsorbent that specific area is large, absorption property is high.
The preparation method of a kind of layered bi-metal oxide adsorbent provided by the invention, first adopt two microemulsion coprecipitation to prepare its presoma layered double hydroxide, and then high-temperature calcination is carried out to it prepare layered bi-metal oxide, specifically comprise the following steps:
1) MgCl is taken respectively
26H
2o and AlCl
39H
2o, adds deionized water, prepares the MgCl that total concentration of metal ions is 0.05 ~ 3.0mol/L
2and AlCl
3mixed-salt aqueous solution; DMF DMF and hydrophobic ionic liquid BmimPF is added in this mixing salt solution
6, wherein mixed-salt aqueous solution, DMF and BmimPF
6volume ratio be 2 ~ 15:30 ~ 50:40 ~ 70, room temperature lower magnetic force stir 30 ~ 60min, treat that solution is become from muddiness transparent, prepared reverse micro emulsion A;
2) get the ammoniacal liquor that certain volume concentration is 25%, add DMF and BmimPF wherein
6, wherein ammoniacal liquor, DMF and BmimPF of 25%
6volume ratio be 2 ~ 15:30 ~ 50:40 ~ 70, room temperature lower magnetic force stir 30 ~ 60min, treat that solution is become from muddiness transparent, prepared reverse micro emulsion B;
3) under magnetic agitation condition, by reverse micro emulsion A and reverse micro emulsion B titration simultaneously, control pH is between 9.0 ~ 10.0, stirring at room temperature reaction 12h, aging 10 ~ 24h under 25 ~ 75 DEG C of conditions afterwards, gained slurries are centrifugal 10min under 10000rpm rotating speed, washs 2 times respectively successively by DMF, absolute ethyl alcohol and deionized water, under 60 DEG C of vacuum, drying 12 hours, obtains presoma small particle diameter ultra-thin stratiform bimetallic oxide nanometer sheet;
4) by step 3) the presoma small particle diameter ultra-thin layered duplex metal hydroxide nanometer sheet dry powder of gained puts into Muffle furnace, and calcine 3 ~ 8 hours under 500 DEG C of conditions in air atmosphere, obtain layered bi-metal oxide adsorbent.
Step 1) middle MgCl
2and AlCl
3in mixing salt solution, the total concentration of metal ion is 0.45mol/L, MgCl
2and AlCl
3mol ratio be 2:1; Described aqueous phase is the reverse micro emulsion A of mixed-salt aqueous solution and aqueous phase is the aqueous solution, DMF and BmimPF in the reverse micro emulsion B of ammonia spirit
6volume ratio completely equal; Step 3) lateral dimension of the ultra-thin layered duplex metal hydroxide nanometer sheet of presoma small particle diameter of gained is 10 ~ 35nm, average thickness is 0.71nm, is made up of individual layer layered double hydroxide sheet.
The layered bi-metal oxide specific area prepared by above-mentioned preparation method is 107.36 ~ 158.46m
2/ g, aperture is 8.56 ~ 11.17nm, and pore volume is 0.358 ~ 0.468cm
3/ g.
Prepared the layered bi-metal oxide adsorbent of gained by above-mentioned preparation method, can recover to form the layered duplex metal hydroxide nanometer sheet that particle diameter is 150 ~ 200nm, thickness is about 5nm, domain size distribution is homogeneous in aqueous medium.
The layered bi-metal oxide adsorbent of gained is prepared by above-mentioned preparation method, be suitable for the adsorption applications of low phosphorus acid group in water body, described application is that layered bi-metal oxide adsorbent to be joined phosphate concentration be in the aqueous solution of 2mg/L, and shaken at room temperature reacts 5 hours.
Compared with prior art, main beneficial effect and advantage are in the present invention:
1) the layered bi-metal oxide adsorbent preparation method of effective removal low phosphorus acid group of the present invention, solve the gathering existed when traditional co-precipitation method prepares presoma LDH, the defect such as particle diameter is large, particle size distribution range is wide, specific area is little, present the features such as particle diameter is little, particle size distribution range is narrow, specific area is large, lamella is thin, pore volume is little, correspondingly, high-temperature calcination product stratiform bimetallic oxide has the advantage that specific area is large, absorption property is high.
2) preparation method of the present invention, the three component Reverse Microemulsion System components adopted when preparing presoma LDH are simple, not containing surfactant, there is not the complicated processes removing surfactant during product purification; Layered bi-metal oxide adsorbent can be obtained after presoma LDH high-temperature calcination, therefore prepare the more simple environmental protection of efficient layered bi-metal oxide adsorbent.
3) Reverse Microemulsion System of the present invention is ionic liquid bag water reverse micro emulsion, compared to existing microemulsion system, more meets the requirement of Green Chemistry.
4) by the layered bi-metal oxide adsorbent of preparation method's gained of the present invention, greatly LDH is better than to the absorption property of low phosphorus acid group in water body, and preparation method is simple to operate, mild condition, cost are low.
Accompanying drawing illustrates:
Fig. 1 is the XRD diffraction pattern of embodiment 2, comparative example 1 ~ 3 gained sample.
Fig. 2 is the N of embodiment 2, comparative example 1 ~ 2 gained sample
2adsorption/desorption isotherms and graph of pore diameter distribution.
Fig. 3 is the stereoscan photograph of embodiment 2, comparative example 1 ~ 3 gained sample.
Fig. 4 is the crossed section analysis (b) along red straight line in the atomic force microscopy (a) of embodiment 2 gained stratiform bimetallic oxide adsorbent and a figure.
Detailed description of the invention:
For understanding the present invention further, below in conjunction with drawings and Examples, the invention will be further described, but and do not limit the present invention in any way.
Embodiment 1:
1) MgCl is taken respectively
26H
2o and AlCl
39H
2o, adds deionized water, and preparing total concentration of metal ions is 0.45mol/L, MgCl
2and AlCl
3molar concentration rate be 2:1; DMF (DMF) and hydrophobic ionic liquid BmimPF is added in this mixing salt solution
6, wherein mixing salt solution, DMF and BmimPF
6volume ratio be 4:48:48, room temperature lower magnetic force stir 40min, treat that solution is become from muddiness transparent, prepared reverse micro emulsion A;
2) get the ammoniacal liquor that certain volume concentration is 25%, add DMF and BmimPF wherein
6, make the ammoniacal liquor of 25%, DMF and BmimPF
6volume ratio be 4:48:48, room temperature lower magnetic force stir 40min, treat that solution is become from muddiness transparent, prepared reverse micro emulsion B;
3) under magnetic agitation condition, by reverse micro emulsion A and reverse micro emulsion B titration simultaneously, control pH is between 9.0 ~ 10.0, stirring at room temperature reaction 12h, aging 24h under 75 DEG C of conditions afterwards, gained slurries are centrifugal 10min under 10000rpm rotating speed, washs 2 times respectively successively by DMF, absolute ethyl alcohol and deionized water, under 60 DEG C of vacuum, drying 12 hours, obtains presoma small particle diameter ultra-thin stratiform bimetallic oxide nanometer sheet.
4) by step 3) the presoma small particle diameter ultra-thin layered duplex metal hydroxide nanometer sheet dry powder of gained puts into Muffle furnace, and calcine 5 hours under 500 DEG C of conditions in air atmosphere, obtain layered bi-metal oxide adsorbent, be designated as LDO
a.
Embodiment 2:
1) with reference to embodiment 1 step 1) in method and preparation condition, only change mixing salt solution, DMF and BmimPF
6volume ratio be 7:46.5:46.5, prepared reverse micro emulsion A;
2) with reference to embodiment 1 step 2) in method and preparation condition, only change mixing salt solution, DMF and BmimPF
6volume ratio be 7:46.5:46.5, prepared reverse micro emulsion B;
3) adopt embodiment 1 step 3) in method and preparation condition, obtain the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter;
4) adopt embodiment 1 step 4) in method and preparation condition, the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter that in calcining, step obtains, obtains layered bi-metal oxide adsorbent, is designated as LDO
b.
Embodiment 3:
1) with reference to embodiment 1 step 1) in method and preparation condition, only change mixing salt solution, DMF and BmimPF
6volume ratio be 7:31:62, prepared reverse micro emulsion A;
2) with reference to embodiment 1 step 2) in method and preparation condition, only change mixing salt solution, DMF and BmimPF
6volume ratio be 7:31:62, prepared reverse micro emulsion B;
3) adopt embodiment 1 step 3) in method and preparation condition, obtain the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter;
4) adopt embodiment 1 step 4) in method and preparation condition, the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter that in calcining, step obtains, obtains layered bi-metal oxide adsorbent, is designated as LDO
c.
Embodiment 4:
1) adopt embodiment 2 step 1) in method and preparation condition, prepared reverse micro emulsion A;
2) adopt embodiment 2 step 2) in method and preparation condition, prepared reverse micro emulsion B;
3) adopt embodiment 1 step 3) in method and preparation condition, just ageing time is reduced to 12h, obtains the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter;
4) adopt embodiment 1 step 4) in method and preparation condition, the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter that in calcining, step obtains, obtains layered bi-metal oxide adsorbent, is designated as LDO
d.
Embodiment 5:
1) adopt embodiment 2 step 1) in method and preparation condition, prepared reverse micro emulsion A;
2) adopt embodiment 2 step 2) in method and preparation condition, prepared reverse micro emulsion B;
3) adopt embodiment 1 step 3) in method and preparation condition, just reaction temperature is reduced to 25 DEG C, obtains the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter.
4) adopt embodiment 1 step 4) in method and preparation condition, the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter that in calcining, step obtains, obtains layered bi-metal oxide adsorbent, is designated as LDO
e.
Comparative example 1:
1) MgCl is taken respectively
26H
2o and AlCl
39H
2o, adds deionized water, and preparing total concentration of metal ions is 0.45mol/L, MgCl
2and AlCl
3molar concentration rate be 2:1, prepared solution A;
2) concentration is the ammoniacal liquor of 25% (w/w) is solution B;
3) under magnetic agitation condition, by solution A and solution B titration simultaneously, control pH is between 9.0 ~ 10.0, stirring at room temperature reaction 12h, aging 24h under 75 DEG C of conditions afterwards, gained slurries are centrifugal 10min under 10000rpm rotating speed, washs 2 times respectively successively by DMF, absolute ethyl alcohol and deionized water, under 60 DEG C of vacuum, drying 12 hours, obtains LDH.
Comparative example 2:
According to step 1 in enforcement 2) ~ 3) method and condition, prepare the ultra-thin acrylic/hydrotalcite-like nano sheet of presoma small particle diameter, be designated as LDH-M.
Comparative example 3:
By the sample LDH of embodiment 2 gained
bstirring reaction 2 hours in deionized water, the layered double hydroxide be restored, is designated as LDH
r.
Fig. 1 is the XRD result figure of embodiment 2, comparative example 1 ~ 3 gained sample.LDH, LDH-M and LDH in figure
rall there are houghite 003,006 and 009 crystal face three characteristic diffraction peaks, wherein LDH-M and LDH at low 2 θ places in three samples
rcompared with LDH sample characteristic peak, its peak width obviously broadens, and intensity obviously dies down, and illustrates that the presoma LDH nanometer sheet degree of crystallinity adopting of the present invention pair of microemulsion coprecipitation method to prepare is lower, its degree of crystallinity step-down after being recovered by bimetallic oxide hydration.The d of three samples
003value is between 0.78 ~ 0.80nm, suitable with Cl-LDH, their cell parameter a and b (a=b=2d
110) be about
consistent with literature value.The width of diffraction maximum and intensity reflect the degree of crystallinity of sample well.At high 2 θ place also all there are 110 and 113 diffraction maximums in three samples, but clearly LDH-M and LDH
rcompared with LDH sample characteristic peak, 110 and 113 diffraction maximums are not only overlapping, and weakened, peak width have broadened, the presoma LDH nanometer sheet that adopts the of the present invention pair of microemulsion coprecipitation method to prepare is described and recovers the LDH degree of crystallinity of gained by bimetallic oxide hydration all lower, and lamella is very thin.When LDH-M generates layered bi-metal oxide through 500 DEG C of calcinings after 5 hours, XRD shows original lamellar structure and caves in, in conjunction with hydroxyl and the hydrone of interlayer lose, there is the diffraction maximum of new oxide phase simultaneously.
Fig. 2 is the N of embodiment 2, comparative example 1 and 2 gained sample
2adsorption/desorption isotherms and graph of pore diameter distribution.Adsorption isotherm display all samples is with H3-type hysteresis loop (P/P
0>0.4) typical IV thermoisopleth, is indicated as mesoporous material.Wherein the specific area of LDH-M sample is 140.83m
2/ g, higher than LDH sample (53.28m prepared by traditional co-precipitation method
2/ g), illustrate that surfactant-free microemulsion coprecipitation can prepare the large layered double hydroxide ultrathin nanometer sheet of specific area.And its calcined product LDO
bowing to losing the lamellar structure of original houghite, specific area reduces to some extent, is 113.05m
2/ g, but far above LDH sample prepared by traditional co-precipitation method.LDH-M and LDO
baperture be respectively 3.83 and 10.94nm, much smaller than LDH sample (21.87nm) prepared by traditional co-precipitation method, this illustrates that the first two sample lacks orderly lamellar structure, and concrete outcome is in table 1.
The BET specific surface of table 1:LDH nanometer sheet and aperture result.
Fig. 3 is the stereoscan photograph of embodiment 2, comparative example 1 ~ 3 gained sample.Electromicroscopic photograph shows: LDH sample prepared by traditional co-precipitation method has obvious layer structure, and particle is comparatively large and gathering is obvious.And the presoma LDH-M particle diameter adopting surfactant-free microemulsion coprecipitation of the present invention to prepare is less, and present bending dispersed because lamella is thin.And its calcined product LDO
bbecause the lamellar structure of houghite is caved in, present and there is impalpable structure with granule.Work as LDO
bafter recovering in aqueous medium, due to " memory effect " of LDH, LDH
rthere is again the lamellar structure of houghite, and still there is good dispersiveness, but its lamella becomes large, and lamella is also thickening, this is because do not have the confinement effect of " washing basin " in microemulsion system in the process, acrylic/hydrotalcite-like nano sheet can free growth.
Fig. 4 is the crossed section analysis (b) along red straight line in the atomic force microscopy (a) of comparative example 3 gained sample and a figure.Calcined product LDO prepared by atomic force microscopy display
bafter recovering in water, present obvious gathering, although the crossed section analysis result display of red straight line, its particle size is between 20 ~ 60nm, thickness is about 0.96 ~ 3.22nm, but can know and see that other regions present obvious gathering, its particle diameter and thickness should be larger, and this is consistent with ESEM result.
Embodiment 5 effect test example
The product that subjects: embodiment 1-5 is obtained, comparative example 1 products obtained therefrom;
Test objective: the product that investigation embodiment of the present invention 1-5 obtains and comparative example 1 gained LDH are to the absorption property of low phosphorus acid group in water body.
Test grouping:
Test 1 group: the product LDO that embodiment 1 is obtained
a;
Test 2 groups: the product LDO that embodiment 2 is obtained
b;
Test 3 groups: the product LDO that embodiment 3 is obtained
c;
Test 4 groups: the product LDO that embodiment 4 is obtained
d;
Test 5 groups: the product LDO that embodiment 5 is obtained
e;
Contrast test group: product LDH and LDH-M that comparative example 1 and 2 is obtained.
Test method:
Each for subjects of the present invention 50mg is joined 50mL respectively, concentration is in the potassium dihydrogen phosphate aqueous solution of 2mg/L, stirring reaction 5 hours.Often group test repetition six times, measure the rear concentration of its process, and measure its clearance, average, wherein the computing formula of clearance is as follows:
Result of the test:
Table 2: product of the present invention and comparative sample are to the adsorption test result of low phosphorus acid group in water body
| Group | Contrast groups | Contrast groups | Test 1 group | Test 2 groups | Test 3 groups | Test 4 groups | Test 5 groups |
| Test products | LDH | LDH-M | LDO a | LDO b | LDO c | LDO d | LDO e |
| Clearance (%) | 55.33 | 70.12 * | 92.3 *# | 92.6 *# | 90.8 *# | 91.8 *# | 91.4 *# |
Remarks:
*compared with contrast groups LDH, P<0.05;
#compared with contrast groups LDH-M, P<0.05.
Brief summary: can be found out by the result of the test of table 2:
Result shows: adding under equal in quality adsorbent condition, (the test 1 of each experimental group of the present invention, 2, 3, 4 with 5 groups) compare with LDH-M with contrast groups LDH, they all have significant difference to the eliminating rate of absorption of low phosphorus acid group in water body, visible gained stratiform bimetallic oxide adsorbent LDO of the present invention is better than bulky grain houghite prepared by the ultra-thin LDH nanometer sheet of small particle diameter and traditional co-precipitation method to the Adsorption successful of low phosphorus acid group in water body, this is mainly because the layered bi-metal oxide adsorbent LDO of gained of the present invention is except utilizing large specific area absorption, and when structural remodeling forms LDO, phosphate radical take part in the reconstruction of houghite, therefore compared with the bulky grain houghite that prepared by they and the ultra-thin LDH nanometer sheet of small particle diameter and traditional co-precipitation method, achieve unexpected technique effect.
Claims (6)
1. the preparation method of a layered bi-metal oxide adsorbent, it is characterized in that first adopting two microemulsion coprecipitation to prepare its presoma layered double hydroxide, and then high-temperature calcination is carried out to it prepare layered bi-metal oxide, specifically comprise the following steps:
1) MgCl is taken respectively
26H
2o and AlCl
39H
2o, adds deionized water, prepares the MgCl that total concentration of metal ions is 0.05 ~ 3.0mol/L
2and AlCl
3mixed-salt aqueous solution; DMF DMF and hydrophobic ionic liquid BmimPF is added in this mixing salt solution
6, wherein mixed-salt aqueous solution, DMF and BmimPF
6volume ratio be 2 ~ 15:30 ~ 50:40 ~ 70, room temperature lower magnetic force stir 30 ~ 60min, treat that solution is become from muddiness transparent, prepared reverse micro emulsion A;
2) get the ammoniacal liquor that certain volume concentration is 25%, add DMF and BmimPF wherein
6, wherein ammoniacal liquor, DMF and BmimPF of 25%
6volume ratio be 2 ~ 15:30 ~ 50:40 ~ 70, room temperature lower magnetic force stir 30 ~ 60min, treat that solution is become from muddiness transparent, prepared reverse micro emulsion B;
3) under magnetic agitation condition, by reverse micro emulsion A and reverse micro emulsion B titration simultaneously, control pH is between 9.0 ~ 10.0, stirring at room temperature reaction 12h, aging 10 ~ 24h under 25 ~ 75 DEG C of conditions afterwards, gained slurries are centrifugal 10min under 10000rpm rotating speed, washs 2 times respectively successively by DMF, absolute ethyl alcohol and deionized water, under 60 DEG C of vacuum, drying 12 hours, obtains presoma small particle diameter ultra-thin stratiform bimetallic oxide nanometer sheet;
4) by step 3) the presoma small particle diameter ultra-thin layered duplex metal hydroxide nanometer sheet dry powder of gained puts into Muffle furnace, and calcine 3 ~ 8 hours under 500 DEG C of conditions in air atmosphere, obtain layered bi-metal oxide adsorbent.
2. the preparation method of a kind of layered bi-metal oxide adsorbent according to claim 1, is characterized in that step 1) middle MgCl
2and AlCl
3in mixing salt solution, the total concentration of metal ion is 0.45mol/L, MgCl
2and AlCl
3mol ratio be 2:1; Described aqueous phase is the reverse micro emulsion A of mixed-salt aqueous solution and aqueous phase is the aqueous solution, DMF and BmimPF in the reverse micro emulsion B of ammonia spirit
6volume ratio completely equal; Step 3) lateral dimension of the ultra-thin layered duplex metal hydroxide nanometer sheet of presoma small particle diameter of gained is 10 ~ 35nm, average thickness is 0.71nm, is made up of individual layer layered double hydroxide sheet.
3. the preparation method of a kind of layered bi-metal oxide adsorbent according to claim 1, is characterized in that the layered bi-metal oxide specific area utilizing the preparation method described in claim 1 or 2 to prepare is 107.36 ~ 158.46m
2/ g, aperture is 8.56 ~ 11.17nm, and pore volume is 0.358 ~ 0.468cm
3/ g.
4. the preparation method of a kind of layered bi-metal oxide adsorbent according to claim 1 prepares the layered bi-metal oxide adsorbent of gained, it is characterized in that: can recover to form the layered duplex metal hydroxide nanometer sheet that particle diameter is 150 ~ 200nm, thickness is about 5nm, domain size distribution is homogeneous in aqueous medium.
5. layered bi-metal oxide adsorbent according to claim 4, is characterized in that gained adsorbent is suitable for the adsorption applications of low phosphorus acid group in water body.
6. adsorbent according to claim 5 is suitable for the adsorption applications of low phosphorus acid group in water body, it is characterized in that the phosphate concentration in water body is 2mg/L.
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