CN103193254B - Novel technology for simultaneously preparing rodlike and sheetlike nano-sized magnesium hydroxide - Google Patents
Novel technology for simultaneously preparing rodlike and sheetlike nano-sized magnesium hydroxide Download PDFInfo
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- CN103193254B CN103193254B CN201310077110.3A CN201310077110A CN103193254B CN 103193254 B CN103193254 B CN 103193254B CN 201310077110 A CN201310077110 A CN 201310077110A CN 103193254 B CN103193254 B CN 103193254B
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- alcohol
- magnesium hydroxide
- ion exchange
- exchange column
- sodium hydroxide
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 71
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 71
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 71
- 238000005516 engineering process Methods 0.000 title abstract description 6
- 239000002105 nanoparticle Substances 0.000 title abstract description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 120
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000005342 ion exchange Methods 0.000 claims abstract description 42
- 239000002073 nanorod Substances 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000001556 precipitation Methods 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000012265 solid product Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 22
- 239000012065 filter cake Substances 0.000 claims description 18
- 238000011426 transformation method Methods 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002135 nanosheet Substances 0.000 abstract 1
- 229960002337 magnesium chloride Drugs 0.000 description 55
- 238000002156 mixing Methods 0.000 description 37
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 22
- 239000000395 magnesium oxide Substances 0.000 description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 14
- 230000032683 aging Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000001131 transforming effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides a novel technology combining a precursor precipitation conversion method and an ion exchange technology for simultaneously preparing rodlike and sheetlike nano-sized magnesium hydroxide. Rodlike basic magnesium chloride [Mg2(OH)3Cl.4H2O] is used as a precursor. A mixed solution of sodium hydroxide, alcohol and water flows an ion exchange column filled with rodlike basic magnesium chloride from top to bottom. A solid product in the ion exchange column is washed and dried to get magnesium hydroxide nanorods with a wideth of 100-500 nm and a length of 15-30 [mu]m. The yield is 40%-45%. The eluant is concentrated and separated by crystallization. Magnesium hydroxide nanosheets with a thickness of 20-50 nm and a diameter of 100-300 nm are then prepared through the processes of filtering, washing and drying. The yield is 42%-46%. The present invention has the advantages that: the preparation operations are performed at ambient temperature, the process is simple, and rodlike and sheetlike magnesium hydroxide are prepared simultaneously.
Description
Technical field
The invention belongs to nano material preparing technical field, particularly a kind ofly prepare bar-shaped and novel process sheeted nanometer magnesium hydroxide simultaneously.
Background technology
Magnesium hydroxide is a kind of flame retardant products of environmental protection, have fire-retardant, eliminate smoke, resistance drips and the multi-functional such as filling.When common magnesium hydroxide uses as fire retardant, reach desirable flame retardant effect, its loading level will could meet actual fire-retardant requirement more than 60% conventionally, thereby has had a strong impact on by the mechanical property of flame retarded polymeric material and and processing characteristics.The magnesium hydroxide nanorods of one dimension Nano structure not only can make loading level decline as fire retardant, can also improve the mechanical mechanics property such as bending strength, unit elongation and axial stress of polymer materials.Magnesium hydroxide nanorods is also the presoma of preparing magnesium oxide nanometer rod, and the latter has optical, electrical, the magnetic, the chemical property that are different from bulk material, is widely used in field of electronic devices.
At present, the magnesium hydroxide products on market mostly is hexagonal plate from pattern, and bar-shaped magnesium hydroxide products is but very rare, and major cause is still immature in the production technology of magnesium hydroxide nanorods.The preparation method of magnesium hydroxide nanorods mainly contain the precipitator method, water (or solvent) Re Fa and, the solid arc discharge method of liquid one.
The precipitator method comprise direct precipitation method, reverse precipitation method and precursor precipitation transformation method.Direct precipitation method is to add people's precipitation agent in the solution that contains Mg, the precipitation generating is separated out from solution, then drying can obtain magnesium hydroxide monodimension nanometer material.Common precipitation agent has sodium hydroxide, potassium hydroxide, ammoniacal liquor etc., simple as the process operation of precipitation agent with ammonia, mild condition, and reaction raw materials is cheap and easy to get; But because the volatility of ammonia is stronger, easily contaminate environment, and also the magnesium hydroxide obtaining is mainly needle-like.And while being precipitation agent with sodium hydroxide or potassium hydroxide solution, in reaction process, there is gel phenomenon, cause very large difficulty to the filtration washing of product.Reverse precipitation method is to grow up on the basis of direct precipitation method, and its building-up process is that the solution that contains magnesium ion is added in precipitation agent and carried out.This method has been avoided the iso-electric point interval that will pass through in direct precipitation method, makes the precipitation particulate generating in preparation process all the time with identical electric charge, has effectively stoped the cohesion between precipitation particulate.Than direct precipitation method, the dispersed and homogeneity of product that reverse precipitation method makes is all significantly improved, but must select suitable dispersion agent to strengthen nucleation, and maintains its good dispersiveness with ultrasonic concussion.Song Xijin etc. [preparation [J] of nano-sized magnesium hydroxide. application foundation and engineering science journal, 2006,14 (4): 523～528] taking magnesium chloride solution as raw material, adopting sodium hydroxide and ammoniacal liquor is mixed precipitant, strengthen into the method for nuclear reaction by reverse precipitation and cold ethanol solution, prepare diameter 8～10nm, the magnesium hydroxide rhabdolith of length 40～60nm, obviously the length of the magnesium hydroxide nanorods obtaining of the method is too short.Precursor precipitation transformation method is the difference according to solubleness between compound, and the concentration, invert point and the tensio-active agent that precipitate transforming agent by change are controlled the growth of particle and prevented intergranular reunion.King precious and etc. [Chinese invention patent CN1769176A] taking light magnesium oxide and magnesium chloride hexahydrate as raw material, first adopt direct precipitation method to prepare basic magnesium chloride, again taking basic magnesium chloride as precursor, employing aqueous ethanolic solution is solvent, sodium hydroxide is precipitation transforming agent (starting point concentration is 0.01～5moL/L), add 1～5% dispersion agent PEG-4000, temperature of reaction is 60～100 DEG C, after adopting constant flow pump dropping mode that sodium hydroxide solution is dripped, again after ageing 6～48h, obtain wide approximately 100～150nm, be about the magnesium hydroxide monocrystal nano rod of 3～5 μ m.[the Nanocrystals to Nanorods:A Precursor Approach for the Synthesis of Magnesium Hydroxide Nanorods from Magnesium Oxychloride Nanorods Starting from Nanocrystalline Magnesium Oxide[J] .Chem.Mater. such as the P.Jeevanandam of the state university of kansas, u.s.a, Vol.19, No.22, 2007:5395～5403] employing precursor precipitation transformation method, taking aqueous ethanolic solution as solvent, sodium hydroxide is precipitation transforming agent, at 25～45 DEG C, react 3～7h, prepare wide approximately 200～400nm, be about the magnesium hydroxide nanorods of 8～15 μ m.Because basic magnesium chloride is soluble in water, and the reaction times that precursor precipitation transformation method is converted into magnesium hydroxide nanorods from precursor basic magnesium chloride is longer, causes the magnesium hydroxide nanorods productive rate low (productive rate is lower than 20%) finally obtaining.
The hot method of water (or solvent) refers in closed reaction vessel, using water (or organic solvent) as medium, by heating, produces the environment of a High Temperature High Pressure in reaction system, then through separating and thermal treatment obtain a kind of method of product.According to [Nanocrystals to Nanorods:A Precursor Approach for the Synthesis of Magnesium Hydroxide Nanorods from Magnesium Oxychloride Nanorods Starting from Nanocrystalline Magnesium Oxide[J] .Chem.Mater. such as Jeevanandam, Vol.19, No.22, 2007:5403] statistics, water (or solvent) Re Fa can obtain wide 8～200nm, the magnesium hydroxide nanorods of long number micron, compared with other preparation methods, the hot method of water (or solvent) has crystal grain and grows complete, granularity is little, be evenly distributed, particle agglomeration is lighter, the advantage such as stoichiometry thing and crystalline form that is easy to get suitable, but the Length Ratio precursor precipitation transformation method of the magnesium hydroxide nanorods obtaining is short, and conversion unit is had to higher requirement, operational condition is harsher, be difficult to realize scale production, consider not have yet at present feasibility from the angle of industrial production cost.
Wide 8～the 10nm of magnesium hydroxide nanorods that the solid arc discharge method of liquid one obtains, is about 250nm, and the length of the magnesium hydroxide nanorods that obviously prepared by the method is short too.
Summary of the invention
For overcoming the existing technological deficiency of preparing magnesium hydroxide nanorods, the invention provides a kind of precursor precipitation transformation method and ion exchange technique and combine and prepare the novel process of magnesium hydroxide nanorods, this technique is with bar-shaped basic magnesium chloride [Mg
2(OH)
3cl4H
2o] be precursor, first bar-shaped basic magnesium chloride is filled in ion exchange column, then make the alcohol-water mixed solution of sodium hydroxide flow through ion exchange column from top to bottom with certain speed, finally the solid oven dry in ion exchange column is obtained to magnesium hydroxide nanorods, simultaneously by concentrated the effluent liquid of the ion exchange column crystallization that makes, again after filtration, washing, the operation such as dry, can obtain magnesium hydroxide nanometer sheet.Different from aforementioned precursor precipitation transformation method is, method provided by the invention is according to ion exchange principle, allow alcohol-water mixed solution Continuous Flow of sodium hydroxide cross basic magnesium chloride powder bed, product NaCl (sodium-chlor) and water that reaction is generated are removed in time, impel balance to move to product direction, be conducive to the generation of magnesium hydroxide nanorods.Because of the alcohol-water mixed solution of sodium hydroxide and the shortening duration of contact of basic magnesium chloride, reduce the loss of basic magnesium chloride because being caused by water dissolution simultaneously, the yield of magnesium hydroxide nanorods is also improved.
The reaction formula of preparing magnesium hydroxide nanorods is:
Mg
2(OH)
3Cl·4H
2O(s)+NaOH→2Mg(OH)
2(s)+NaCl+4H
2O
Concrete technology is as follows:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of certain volume is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, wash 3 times with 9: 1 alcohol-water mixing solutionss, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] nanometer rod;
2, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the alcohol-water mixed solution that drips sodium hydroxide in ion exchange column, until effluent liquid is alkalescence;
3, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanorods.
4, by the concentrated effluent liquid magnesium hydroxide crystallization that makes, filter, filter cake washs by alcohol-water solution, then in 105 DEG C of baking ovens, is dried 3 hours, obtains magnesium hydroxide nanometer sheet.
In the alcohol-water mixed solution of described sodium hydroxide, the volume ratio of alcohol and aqueous sodium hydroxide solution is 1: 1～5: 1, is preferably 4: 1;
In the alcohol-water mixed solution of described sodium hydroxide, the concentration of sodium hydroxide is 0.25～4mol/L, is preferably 0.5mol/L;
In the alcohol-water mixed solution of described sodium hydroxide, alcohol is the one in methyl alcohol or ethanol or propyl alcohol or Virahol, is preferably ethanol.
The advantage of technique of the present invention is: preparation manipulation carries out at normal temperatures, and technique is simple, can obtain bar-shaped and flake magnesium hydroxide simultaneously.Wide 100～the 500nm of magnesium hydroxide nanorods obtaining, long 15～30 μ m, yield is 40%～45%, flake magnesium hydroxide thickness 20～50nm, diameter 100～300nm, yield is 42%～46%.What the precursor precipitation transformation method of the existing bibliographical information of Length Ratio of the magnesium hydroxide nanorods obtaining obtained will grow, and yield is also higher.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of magnesium hydroxide nanorods
Fig. 2 is the scanning electron microscope (SEM) photograph of magnesium hydroxide nanometer sheet
Fig. 3 is the technical process of simultaneously preparing magnesium hydroxide nanorods and magnesium hydroxide nanometer sheet
Specific embodiments:
Embodiment one:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, with alcohol-water mixing solutions washing in 9: 13 times, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, the alcohol-water mixing solutions that dose volume ratio is 1: 1;
3, make solvent with the ethanol-water system of preparing, sodium hydroxide is made solute, the alcohol-water mixing solutions of preparation 0.25mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the alcohol-water mixing solutions that drips the 0.25mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～25 μ m, yield 40%);
6, the effluent liquid that contains crystallization is filtered, alcohol-water mixing solutions washing for filter cake, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 42%).
Embodiment two:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, with alcohol-water mixing solutions washing in 9: 13 times, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, the alcohol-water mixing solutions that dose volume ratio is 2: 1;
3, make solvent with the ethanol-water system of preparing, sodium hydroxide is made solute, the alcohol-water mixing solutions of preparation 2mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the alcohol-water mixing solutions that drips the 2mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～25 μ m, yield 43%);
6, the effluent liquid that contains crystallization is filtered, alcohol-water mixing solutions washing for filter cake, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 43%).
Embodiment three:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, with alcohol-water mixing solutions washing in 9: 13 times, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, the alcohol-water mixing solutions that dose volume ratio is 4: 1;
3, make solvent with the ethanol-water system of preparing, sodium hydroxide is made solute, the alcohol-water mixing solutions of preparation 0.5mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the alcohol-water mixing solutions that drips the 0.5mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～30 μ m, yield 45%);
6, the effluent liquid that contains crystallization is filtered, alcohol-water mixing solutions washing for filter cake, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 46%).
Embodiment four:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, with alcohol-water mixing solutions washing in 9: 13 times, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, the alcohol-water mixing solutions that dose volume ratio is 5: 1;
3, make solvent with the ethanol-water system of preparing, sodium hydroxide is made solute, the alcohol-water mixing solutions of preparation 0.5mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the alcohol-water mixing solutions that drips the 0.5mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～25 μ m, yield 44%);
6, the effluent liquid that contains crystallization is filtered, alcohol-water mixing solutions washing for filter cake, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 42%).
Embodiment five:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, wash 3 times with 9: 1 alcohol-water mixing solutionss, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, the alcohol-water mixing solutions that dose volume ratio is 1: 1;
3, make solvent with ethanol-water system, sodium hydroxide is made solute, the alcohol-water mixing solutions of preparation 4mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the alcohol-water mixing solutions that drips the 4mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～15 μ m, yield 40%);
6, the effluent liquid that contains crystallization is filtered, alcohol-water mixing solutions washing for filter cake, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 42%).
Embodiment six:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, with alcohol-water mixing solutions washing in 9: 13 times, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, the methanol-water mixing solutions that dose volume ratio is 4: 1;
3, make solvent with the methanol-water system of preparing, sodium hydroxide is made solute, the methanol-water mixing solutions of preparation 0.5mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the methanol-water mixing solutions that drips the 0.5mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～30 μ m, yield 45%);
6, the effluent liquid that contains crystallization is filtered, methanol-water mixing solutions washing for filter cake, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 42%).
Embodiment seven:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, with alcohol-water mixing solutions washing in 9: 13 times, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, propyl alcohol-water mixed solution that dose volume ratio is 4: 1;
3, make solvent with the third alcohol-water system of preparing, sodium hydroxide is made solute, propyl alcohol-water mixed solution of preparation 0.5mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the propyl alcohol-water mixed solution that drips the 0.5mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～30 μ m, yield 45%);
6, the effluent liquid containing crystallization is filtered, the washing of propyl alcohol for filter cake-water mixed solution, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 42%).
Embodiment eight:
1, precursor basic magnesium chloride [Mg
2(OH)
3cl4H
2o] preparation.The 4mol/L magnesium chloride solution of 100mL is placed in to there-necked flask, the ratio that is 0.07 in magnesium oxide and the ratio of the amount of substance of magnesium chloride, under stirring, add several times 1.12g magnesium oxide pressed powder, be heated to react 1.5h at 50 DEG C, room temperature ageing 48h, then filter, with alcohol-water mixing solutions washing in 9: 13 times, filter cake is dried and is obtained basic magnesium chloride [Mg at 80 DEG C
2(OH)
3cl4H
2o] and nanometer rod (wide 100～500nm, long 15～25 μ are m);
2, the isopropanol-water mixing solutions that dose volume ratio is 4: 1;
3, make solvent with the isopropanol-water system of preparing, sodium hydroxide is made solute, the isopropanol-water mixing solutions of preparation 0.5mol/LNaOH;
4, the precursor basic magnesium chloride of preparation is placed in to ion exchange column, with constant flow pump from top to down to the isopropanol-water mixing solutions that drips the 0.5mol/LNaOH of preparation in ion exchange column, until effluent liquid is alkalescence;
5, the solid product in ion exchange column is taken out, filter, be washed to after neutrality, at 105 DEG C, be dried 3 hours, obtain magnesium hydroxide nanorods (wide 100～500nm, long 10～30 μ m, yield 45%);
6, the effluent liquid that contains crystallization is filtered, isopropanol-water mixing solutions washing for filter cake, dry, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanometer sheet (thickness 20～50nm, diameter 100～300nm, yield 42%).
Claims (2)
1. precursor precipitation transformation method and ion exchange technique combine and prepare bar-shaped and technique sheeted nanometer magnesium hydroxide simultaneously, are with bar-shaped basic magnesium chloride Mg
2(OH)
3cl4H
2o is precursor, make the alcohol-water mixed solution of sodium hydroxide flow through the ion exchange column of filling with bar-shaped basic magnesium chloride from top to bottom, finally the solid product washing in ion exchange column is drying to obtain to wide 100～500nm, the magnesium hydroxide nanorods of long 15～30 μ m, yield is 40%～45%; Make crystallization by concentrated effluent liquid simultaneously, more after filtration, washing, drying process, obtain thickness 20～50nm, the magnesium hydroxide nanometer sheet of diameter 100～300nm, yield is 42%～46%; Concrete steps: the precursor basic magnesium chloride of preparation is placed in ion exchange column by (1), with constant flow pump from top to bottom to the alcohol-water solution that drips sodium hydroxide in ion exchange column, until effluent liquid is alkalescence; (2) solid product in ion exchange column is taken out, filter, be washed to after neutrality, in 105 DEG C of baking ovens, be dried 3 hours, obtain magnesium hydroxide nanorods; (3) by the concentrated effluent liquid magnesium hydroxide crystallization that makes, filter, filter cake washs by alcohol-water solution, then in 105 DEG C of baking ovens, is dried 3 hours, obtains magnesium hydroxide nanometer sheet; Wherein, in the alcohol-water mixed solution of described sodium hydroxide, the volume ratio of alcohol and aqueous sodium hydroxide solution is 1: 1～5: 1; In the alcohol-water mixed solution of described sodium hydroxide, the concentration of sodium hydroxide is 0.25～4mol/L.
2. as claimed in claim 1ly prepare bar-shaped and technique sheeted nanometer magnesium hydroxide, in the alcohol-water mixed solution of described sodium hydroxide, alcohol is methyl alcohol or ethanol or propyl alcohol or Virahol simultaneously.
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| CN110078101B (en) * | 2019-05-30 | 2022-02-01 | 福建农林大学 | Preparation and application of tea fungus disease resistant nano magnesium hydroxide |
| CN115417436B (en) * | 2022-09-20 | 2023-08-11 | 西部金属材料股份有限公司 | Preparation method of two-dimensional magnesium hydroxide nano-sheet |
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| CN100344539C (en) * | 2005-10-05 | 2007-10-24 | 大连理工大学 | Novel method for preparing magnesium oxide nanometer rod |
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