CN105753022B - A kind of preparation method of magnesium-base layer-shaped complex hydroxide - Google Patents
A kind of preparation method of magnesium-base layer-shaped complex hydroxide Download PDFInfo
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- CN105753022B CN105753022B CN201610182401.2A CN201610182401A CN105753022B CN 105753022 B CN105753022 B CN 105753022B CN 201610182401 A CN201610182401 A CN 201610182401A CN 105753022 B CN105753022 B CN 105753022B
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- magnesium
- slurries
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- hydroxide
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 20
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 13
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 9
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000011229 interlayer Substances 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- -1 p-phthalic bridge Chemical compound 0.000 claims description 6
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 4
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 4
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 4
- 229960001860 salicylate Drugs 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910003202 NH4 Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims 4
- 239000002131 composite material Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000002585 base Substances 0.000 abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000000395 magnesium oxide Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 229910001960 metal nitrate Inorganic materials 0.000 abstract description 3
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000463 material Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- CSQDQMVWMIRHAF-UHFFFAOYSA-N [O-2].[Mg+2].[N+](=O)([O-])[O-].[Mg+2] Chemical compound [O-2].[Mg+2].[N+](=O)([O-])[O-].[Mg+2] CSQDQMVWMIRHAF-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/782—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen containing carbonate ions, e.g. dawsonite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a kind of preparation method of magnesium-base layer-shaped complex hydroxide, the method is with calcium oxide or magnesia calcium as alkali source, magnesium hydrate precipitate is generated by there is precipitation reaction with magnesium salts, again with magnesium hydrate precipitate, divalence and trivalent soluble metal nitrate or chloride as raw material, magnesium-base layer-shaped complex hydroxide is prepared by liquid and solid phase reaction, by-product magnesium chloride or magnesium nitrate can be used as raw material.The method has the advantages that raw material sources are abundant, cheap, preparation process is simple, reaction condition is gentle, be easy to industrialized production, the field such as the LDH of preparation can be widely applied to be catalyzed, adsorb, environmental protection, high molecule plastic.
Description
Art
The present invention relates to inorganic non-metallic functional material preparation field, and in particular to a kind of magnesium-base layer-shaped complex hydroxide
Preparation method.
Background technology
Layered double hydroxide (LayeredDoubleHydroxides, abbreviation LDH) is that an anionoid type stratiform is glued
Soil, its chemical formula is [M2+ 1-xM3+ x(OH)2]x+(An- x/n).mH2O, wherein M2+、M3+Represent respectively divalence and trivalent metal sun from
Son, x represents the change of metal element content, An-Represent interlayer anion.LDH has unique two-dimensional layered structure and interlayer the moon
The interchangeability of ion, gets more and more people's extensive concerning in recent years.LDH unique property makes it be widely used in being catalyzed, adsorbs,
The field such as ion exchange and macromolecular material additive (function additive such as fire retardant, heat stabilizer).
LDH is generally prepared using methods such as coprecipitation, nucleation/crystallization isolation method, sluggish precipitations.Document Cheng
Xiang,Huang Xinrui,Wang Xingzu,and Sun Dezhi,Journal of Hazardous Materials,
2010,177 (1-3), 516-523 are prepared for ZnAl-LDH with NaOH as precipitating reagent using coprecipitation；Document Cui
Guojing,Evans David G,and Li Dianqing,Polymer Degradation and Stability,2010,
95 (10), 2082-2087 are prepared for nanoscale ZnAl-NO with NaOH as alkali source using nucleation/crystallization isolation method3-LDH.But it is heavy
, using NaOH as alkali source, 1 ton of LDH of production is about needed using 0.8 ton of NaOH for shallow lake method and nucleation/crystallization isolation method, but NaOH
Production cost is higher, causes the preparation cost of LDH too high, is unfavorable for applications of the LDH in each field, and these methods can be discharged
The sodium salt of a large amount of low values, causes environmental pollution.Document Abellan Gonzalo, Coronado Eugenio, Marti-
Gastaldo Carlos,Pinilla-Cienfuegos Elena,and Ribera Antonio,Journal of
Materials Chemistry, 2010,20 (35), 7451-7455 is prepared for urea as precipitating reagent using sluggish precipitation
Micron order NiFe-LDH.But the method reaction temperature is high, the heat time is more long, and energy consumption is big and can only prepare micron order LDH.Cause
And carry out LDH low cost preparation researches has important facilitation for promoting and expanding the range of application of LDH.
The content of the invention
It is an object of the invention to provide a kind of low cost preparation method of magnesium-base layer-shaped complex hydroxide, the stratiform is answered
Close hydroxide and can be used for the fields such as adsorbing separation, catalysis, macromolecular material.
This method generates hydrogen with calcium oxide or magnesia calcium as alkali source by there is precipitation reaction with magnesium chloride or magnesium nitrate
Magnesium oxide precipitation, then with the fresh precipitation of magnesium hydroxide, divalence and trivalent soluble metal nitrate or chloride as raw material, utilize
Acid-base reaction principle, magnesium-base layer-shaped complex hydroxide is converted into by liquid and solid phase reaction, and by-product magnesium chloride or magnesium nitrate can
Used as raw material.The chemical general formula of prepared magnesium-base layer-shaped complex hydroxide is：
Mg2+ xM2+ 1-x-yM3+ y(OH)2(An-)y/n·mH2O
Wherein 0.1≤x≤0.8,0.2≤y≤0.4, and x+y≤1, m are interlayer crystalline water molecules number, 0.4≤m≤1；M2+
It is bivalent metal ion Zn2+、Ni2+、Co2+、Fe2+、Mn2+、Cu2+In any one or more, preferably Zn2+、Ni2+、Co2+In
One or two；M3+It is trivalent metal ion Al3+、Co3+、Fe3+、Cr3+、Ga3+、V3+、Mn3+、Rh3+、Ir3+、In3+In appoint
One or more of meaning, preferably Al3+、Co3+、Fe3+In one or two；Interlayer anion An-It is Cl-、NO3 -、ClO4 -、ClO3 -、
CO3 2-、SO4 2-、SO3 2-、S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-Deng inorganic anion or salicylate, p-aminobenzoic acid root, second
Any one in the organic anions such as two acid groups, malonate, p-phthalic bridge, dodecyl sodium sulfonate root, n is cloudy interlayer
Ion An-Valence state.
The invention provides a kind of preparation method of magnesium-base layer-shaped complex hydroxide, specific preparation process is as follows：
A. calcium oxide or magnesia calcium slurries that weight/mass percentage composition is 5~40% are prepared, by slurries in ball mill or
Ground 1~10 minute in colloid mill, obtain A slurries；
B. prepare the magnesium salt solution that molar concentration is 0.1~5mol/L, wherein in magnesium ion and step A calcium oxide mole
Ratio is 1:1, by the magnesium salt solution in being added in A slurries in 10~120 minutes under stirring, addition continues after finishing
Stirring reaction 0.1~6 hour, makes magnesium salts and calcium oxide reaction generation magnesium hydrate precipitate, and reaction sinks magnesium hydroxide after terminating
Form sediment filtering, wash to filtrate not calcium ions；Described magnesium salt solution is the solution of magnesium chloride or magnesium nitrate；
C. M is used2+Salt and M3+Salt prepares mixing salt solution, wherein M2+With M3+The total mol concentration of ion be 0.2~
5mol/L；M2+、M3+Ion is respectively (1-x-y) with the molar ratio of magnesium hydroxide:1 and y:1, wherein x, y is respectively equal to stratiform
Complex hydroxide Mg2+ xM2+ 1-x-yM3+ y(OH)2(An-)y/n·mH2X, y value in O；
Described M2+Salt is Zn2+、Ni2+、Co2+、Fe2+、Mn2+、Cu2+Nitrate or chloride in one or more,
Preferably it is Zn2+、Ni2+、Co2+Nitrate or chloride in one or two.
Described M3+Salt is Al3+、Co3+、Fe3+、Cr3+、Ga3+、V3+、Mn3+、Rh3+、Ir3+、In3+Nitrate or chlorination
Any one or more in thing, preferably Al3+、Co3+、Fe3+Nitrate or chloride in one or more.
D. the magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 1~20%, according to An-With C solution
Middle M3+Mol ratio be 1~4:The ratio of n, uses YnAnPrepare An-Concentration is the solution of 0.1~10mol/L and is added to hydroxide
In magnesium slurries, D slurries are uniformly mixing to obtain；
Described YnAnIn Y be NH4, Na, K or H, An-It is Cl-、NO3 -、ClO4 -、ClO3 -、CO3 2-、SO4 2-、SO3 2-、
S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-、B4O7 2-Deng inorganic anion or salicylate, p-aminobenzoic acid root, ethanedioic acid root, third
Any one in the organic anions such as two acid groups, p-phthalic bridge, dodecyl sodium sulfonate root, that more common is CO3 2-、
SO4 2-、H2PO4 -、HPO4 2-With any one in dodecyl sodium sulfonate root, it acts on the layer for being to provide layered double hydroxide
Between anion；
E. in the mixing salt solution that step C is prepared being dropped into D slurries under stirring, it is added dropwise in 10~240 minutes
Finish, reaction system then is heated into 50~105 DEG C continues stirring reaction 1~12 hour, makes magnesium hydroxide and M2+And M3+Salt
The magnesium-base layer-shaped complex hydroxide precipitation of reaction generation, reaction is magnesium-base layer-shaped by precipitation filtering, washing, drying to obtain after terminating
Complex hydroxide Mg2+ xM2+ 1-x-yM3+ y(OH)2(An-)y/n·mH2O；
Filtrate can use as the magnesium chloride in step B or magnesium nitrate solution, and washing lotion can be recycled, after being used for multiple times also
The magnesium chloride or magnesium nitrate solution that can be used in preparation steps B.Accompanying drawing is the X-ray diffractogram, red of LDH prepared by embodiment 1
Outer spectrogram and scanning electron microscope (SEM) photograph.X-ray diffractogram shows that prepared sample has the typical characteristic diffraction peaks of LDH；INFRARED SPECTRUM
The bright LDH interlayer anions of chart are carbonate；Scanning electron microscope (SEM) photograph shows prepared LDH structures in the form of sheets.
Advantages of the present invention：This method occurs with calcium oxide or magnesia calcium as alkali source by with magnesium chloride or magnesium nitrate
Precipitation reaction generates magnesium hydrate precipitate, then with the fresh precipitation of magnesium hydroxide, divalence and trivalent soluble metal nitrate or chlorine
Compound is raw material, and magnesium-base layer-shaped complex hydroxide is prepared by liquid and solid phase reaction, and by-product magnesium chloride or magnesium nitrate can conducts
Raw material is used.The method has that raw material sources are abundant, cheap, preparation process is simple, reaction condition is gentle, is easy to industrialization
The fields such as the advantages of production, the LDH of preparation can be widely applied to be catalyzed, adsorb, environmental protection, high molecule plastic.
Brief description of the drawings:
Fig. 1 is the X-ray diffractogram of layered double hydroxide prepared by embodiment 1.
Fig. 2 is the infrared spectrum of layered double hydroxide prepared by embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of layered double hydroxide prepared by embodiment 1.
Specific embodiment：
The present invention is further described by way of example below, but does not constitute the limit to the scope of the present invention
System.
Embodiment 1：
Step A：Weigh 3.36g calcium oxide to be added in 50g deionized waters, ground 5 minutes in ball mill, be configured to A
Slurries.
Step B：Weigh 15.384g MgCl2 .6H2O is configured to solution in being added to 100ml deionized waters, in stirring
It is lower by MgCl2Solution then proceedes to stirring reaction 2 hours in A slurries are added in 10 minutes, reacts hydroxide after terminating
Magnesium precipitate filtering, wash to filtrate not calcium ions.
Step C：Weigh 7.5g Al (NO3)3 .9H2O is configured to C solution in being added to 100ml deionized waters.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 5%, 1.92g (NH are weighed4)2CO3Added into magnesium hydroxide slurry after being configured to 50ml solution, be uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 60 minutes completion of dropping, then by reaction system
It is heated to 90 DEG C and continues stirring reaction 6 hours, slurries filtration washing is obtained complex hydroxide filter cake 3 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.666Al0.333(OH)2(CO3)0.167·0.65H2O。
Embodiment 2：
Step A, B：With embodiment 1.
Step C：Weigh 2.975g Zn (NO3)2 .6H2O and 7.5g Al (NO3)3 .9H2O matches somebody with somebody in being added to 50ml deionized waters
It is made C solution.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 8%, 1.44g (NH are weighed4)2CO3Added into magnesium hydroxide slurry after being configured to 50ml solution, be uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 90 minutes completion of dropping, then by reaction system
It is heated to 95 DEG C and continues stirring reaction 5 hours, slurries filtration washing is obtained complex hydroxide filter cake 4 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.5Zn0.167Al0.333(OH)2(CO3)0.167·0.6H2O。
Embodiment 3：
Step A, B：With embodiment 1.
Step C：Weigh 5.95g Zn (NO3)2 .6H2O and 7.5g Al (NO3)3 .9H2O matches somebody with somebody in being added to 150ml deionized waters
It is made C solution.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 10%, 1.85g is weighed
(NH4)2CO3Added into magnesium hydroxide slurry after being configured to 80ml solution, be uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 30 minutes completion of dropping, then by reaction system
It is heated to 80 DEG C and continues stirring reaction 8 hours, slurries filtration washing is obtained complex hydroxide filter cake 4 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.333Zn0.333Al0.333(OH)2(CO3)0.167·0.62H2O。
Embodiment 4：
Step A：Weigh 5.04g calcium oxide to be added in 60g deionized waters, ground 3 minutes in ball mill, be configured to A
Slurries.
Step B：Weigh 23.08g Mg (NO3)2 .6H2O is configured to solution in being added to 100ml deionized waters, in stirring shape
By Mg (NO under state3)2Solution then proceedes to stirring reaction 3 hours in A slurries are added in 30 minutes, reacts hydrogen after terminating
Magnesium oxide precipitation filtering, wash to filtrate not calcium ions.
Step C：Weigh 7.13g NiCl2 .6H2O and 8.11g FeCl3·6H2O is prepared in being added to 120ml deionized waters
Into C solution.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 7%, 9.36g is weighed
NaH2PO4·2H2O is added into magnesium hydroxide slurry after being configured to 100ml solution, is uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 90 minutes completion of dropping, then by reaction system
It is heated to 90 DEG C and continues stirring reaction 4 hours, slurries filtration washing is obtained complex hydroxide filter cake 4 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.333Ni0.333Fe0.333(OH)2(H2PO4)0.333·0.65H2O。
Embodiment 5：
Step A, B：With embodiment 4.
Step C：Weigh 7.14g CoCl2 .6H2O and 7.24g AlCl3·6H2O is prepared in being added to 100ml deionized waters
Into C solution.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 12%, 5.22g is weighed
K2SO4Added into magnesium hydroxide slurry after being configured to 100ml solution, be uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 120 minutes completion of dropping, then by reaction system
It is heated to 100 DEG C and continues stirring reaction 4 hours, slurries filtration washing is obtained complex hydroxide filter cake 4 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.333Co0.333Al0.333(OH)2(SO4)0.167·0.67H2O。
Embodiment 6：
Step A, B：With embodiment 4.
Step C：Weigh 8.75g Co (NO3)2 .6H2O and 9.56g In (NO3)3 .H2O matches somebody with somebody in being added to 120ml deionized waters
It is made C solution.
Step D：By step B obtain magnesium hydroxide filter cake be configured to the slurries that solid content is 10%, weigh 2.92g oneself two
Acid is added into magnesium hydroxide slurry after being configured to 150ml solution, is uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 80 minutes completion of dropping, then by reaction system
It is heated to 100 DEG C and continues stirring reaction 6 hours, slurries filtration washing is obtained complex hydroxide filter cake 4 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.333Co0.333In0.333(OH)2(C6H8O4)0.167·0.74H2O。
Embodiment 7：
Step A：Weigh 5.76g magnesia calcium to be added in 60g deionized waters, ground 6 minutes in ball mill, be configured to
A slurries.
Step B：Weigh 12.2g MgCl2 .6H2O is configured to solution in being added to 150ml deionized waters, under stirring
By MgCl2Solution then proceedes to stirring reaction 4 hours in calcium oxide slurries are added in 60 minutes, reacts hydrogen after terminating
Magnesium oxide precipitation filtering, wash to filtrate not calcium ions.
Step C：Weigh 5.82g Ni (NO3)2 .6H2O、5.95g Zn(NO3)2 .6H2O and 15.01g Al (NO3)3 .9H2O adds
Enter and be configured to C solution in 200ml deionized waters.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 10%, 3.84g is weighed
(NH4)2CO3Added into magnesium hydroxide slurry after being configured to 150ml solution, be uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 90 minutes completion of dropping, then by reaction system
It is heated to 100 DEG C and continues stirring reaction 6 hours, slurries filtration washing is obtained complex hydroxide filter cake 4 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.333Ni0.167Zn0.167Al0.333(OH)2(CO3)0.167·0.65H2O。
Embodiment 8：
Step A, B：With embodiment 7.
Step C weighs 11.9g Zn (NO3)2 .6H2O and 15.01g Al (NO3)3 .9H2O is added in 200ml deionized waters
It is configured to C solution.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 10%, 12.8g bigcatkin willows are weighed
Sour sodium is added into magnesium hydroxide slurry after being configured to 160ml solution, is uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 80 minutes completion of dropping, then by reaction system
It is heated to 102 DEG C and continues stirring reaction 4 hours, slurries filtration washing is obtained complex hydroxide filter cake 5 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.333Zn0.333Al0.333(OH)2(C7H5O3)0.333·0.68H2O。
Embodiment 9：
Step A, B：With embodiment 7.
Step C：Weigh 14.5g Cu (NO3)2 .3H2O and 16.16g Fe (NO3)3 .9H2O is added in 150ml deionized waters
It is configured to C solution.
Step D：The magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 6%, 11.24g is weighed
NaClO4·H2O is added into magnesium hydroxide slurry after being configured to 150ml solution, is uniformly mixing to obtain D slurries.
Step E：During C solution to be dropped to D slurries under stirring, 60 minutes completion of dropping, then by reaction system
It is heated to 90 DEG C and continues stirring reaction 8 hours, slurries filtration washing is obtained complex hydroxide filter cake 5 times by reaction after terminating,
By filter cake, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens.Elementary analysis shows that the chemical constitution formula of product is：
Mg0.167Cu0.5Fe0.333(OH)2(ClO4)0.333·0.72H2O。
Claims (2)
1. a kind of preparation method of magnesium-base layer-shaped complex hydroxide, the chemical general formula of described magnesium-base layer-shaped complex hydroxide
For：
Mg2+ xM2+ 1-x-yM3+ y(OH)2 (An-)y/n·mH2O
Wherein 0.1≤x≤0.8,0.2≤y≤0.4, and x+y≤1, m are interlayer crystalline water molecules number, 0.4≤m≤1；M2+It is two
Valence metal ion Zn2+、Ni2+、Co2+、Fe2+、Mn2+、Cu2+In any one or more；M3+It is trivalent metal ion Al3+、Co3 +、Fe3+、Cr3+、Ga3+、V3+、Mn3+、Rh3+、Ir3+、In3+In any one or more；Interlayer anion An-It is Cl-、NO3 -、
ClO4 -、ClO3 -、CO3 2-、SO4 2-、SO3 2-、S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-Or salicylate, p-aminobenzoic acid root, second two
Any one in acid group, malonate, p-phthalic bridge, dodecyl sodium sulfonate root, n is interlayer anion An-Valence state；
It is characterized in that the magnesium-base layer-shaped complex hydroxide is adopted and prepared in the following method：
A. it is 5 ~ 40% calcium oxide slurries to prepare weight/mass percentage composition, and slurries are ground into 1 ~ 10 in ball mill or colloid mill
Minute, obtain A slurries；
B. it is the magnesium salt solution of 0.1 ~ 5mol/L to prepare molar concentration, the molar ratio of calcium oxide wherein in magnesium ion and step A
It is 1:1, by the magnesium salt solution in being added in A slurries in 10 ~ 120 minutes under stirring, addition continues to stir after finishing
Reaction 0.1 ~ 6 hour, by magnesium hydrate precipitate mistake after terminating magnesium salts and calcium oxide reaction generation magnesium hydrate precipitate, reaction
Filter, wash to filtrate not calcium ions；Described magnesium salt solution is the solution of magnesium chloride or magnesium nitrate；
C. M is used2+Salt and M3+Salt prepares mixing salt solution, wherein M2+With M3+The total mol concentration of ion is 0.2 ~ 5mol/L；M2 +、M3+Ion is respectively (1-x-y) with the molar ratio of magnesium hydroxide:1 and y:1, wherein x, y is respectively equal to lamellar composite
Hydroxide Mg2+ xM2+ 1-x-yM3+ y(OH)2 (An-)y/n·mH2X, y value in O, 0.1≤x≤0.8,0.2≤y≤0.4；
Described M2+Salt is Zn2+、Ni2+、Co2+、Fe2+、Mn2+、Cu2+Nitrate or chloride in one or more；
Described M3+Salt is Al3+、Co3+、Fe3+、Cr3+、Ga3+、V3+、Mn3+、Rh3+、Ir3+、In3+Nitrate or chloride in
Any one or more；
D. the magnesium hydroxide filter cake that step B is obtained is configured to the slurries that solid content is 1 ~ 20%, according to An-With M in C solution3+'s
Mol ratio is 1 ~ 4:The ratio of n, uses YnAnPrepare An-Concentration is the solution of 0.1 ~ 10 mol/L and is added to magnesium hydroxide slurry
In, it is uniformly mixing to obtain D slurries；
Described YnAnIn Y be NH4, Na, K or H, An-It is Cl-、NO3 -、ClO4 -、ClO3 -、CO3 2-、SO4 2-、SO3 2-、S2O3 2-、
H2PO4 -、HPO4 2-、PO4 3-、B4O7 2Or salicylate, p-aminobenzoic acid root, ethanedioic acid root, malonate, terephthalic acid (TPA)
Any one in root, dodecyl sodium sulfonate root, its effect is to provide the interlayer anion of layered double hydroxide；
E. in the mixing salt solution that step C is prepared being dropped into D slurries under stirring, completion of dropping in 10 ~ 240 minutes,
Then reaction system is heated to 50 ~ 105 DEG C and continues stirring reaction 1 ~ 12 hour, make magnesium hydroxide and M2+And M3+Reactant salt is given birth to
Into magnesium-base layer-shaped complex hydroxide precipitation, precipitation is filtered, washed by reaction after terminating, the magnesium-base layer-shaped compound hydrogen of drying to obtain
Oxide M g2+ xM2+ 1-x-yM3+ y(OH)2(An-)y/n·mH2O；
Filtrate can use as the magnesium chloride in step B or magnesium nitrate solution, and washing lotion can be recycled, and also be can use after being used for multiple times
Magnesium chloride or magnesium nitrate solution in preparation steps B.
2. the preparation method of magnesium-base layer-shaped complex hydroxide according to claim 1, it is characterized in that described M2+Salt is
Zn2+、Ni2+、Co2+Nitrate or chloride in one or two；Described M3+Salt is Al3+、Co3+、Fe3+Nitrate or
One or more in chloride；Described YnAnIn An-It is CO3 2-、SO4 2-、H2PO4 -、HPO4 2-With dodecyl sodium sulfonate root
In any one.
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| CN106517099B (en) * | 2016-11-11 | 2019-04-26 | 中国科学院青海盐湖研究所 | The preparation method of complex metal hydroxide |
| CN106517304B (en) * | 2016-11-11 | 2019-04-26 | 中国科学院青海盐湖研究所 | The preparation method of three-dimensional complex metal hydroxide |
| CN106517274B (en) * | 2016-11-11 | 2018-10-09 | 中国科学院青海盐湖研究所 | The method of comprehensive utilization of by-product magnesium hydroxide |
| CN106517270B (en) * | 2016-11-11 | 2019-01-11 | 中国科学院青海盐湖研究所 | The preparation method of nano composite hydroxide |
| CN106745116B (en) * | 2016-11-11 | 2019-07-12 | 中国科学院青海盐湖研究所 | A kind of preparation method of complex metal hydroxide |
| CN106517261B (en) * | 2016-11-11 | 2018-11-02 | 中国科学院青海盐湖研究所 | The preparation method of magnesium-based complex metal hydroxide |
| CN106517269B (en) * | 2016-11-11 | 2019-01-11 | 中国科学院青海盐湖研究所 | A kind of method of comprehensive utilization of by-product magnesium hydroxide |
| CN107651700A (en) * | 2017-09-01 | 2018-02-02 | 中国科学院青海盐湖研究所 | The preparation method of layered composite metal hydroxides with nitrate anion intercalation |
| CN107473187A (en) * | 2017-09-01 | 2017-12-15 | 中国科学院青海盐湖研究所 | The preparation method of layered composite metal hydroxides with sulfate radical intercalation |
| CN107572563A (en) * | 2017-09-01 | 2018-01-12 | 中国科学院青海盐湖研究所 | A kind of preparation method of magnesium-base layer-shaped complex metal hydroxide |
| CN107555454A (en) * | 2017-09-01 | 2018-01-09 | 中国科学院青海盐湖研究所 | The preparation method of layered composite metal hydroxides with chlorion intercalation |
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| CN115155543B (en) * | 2022-05-19 | 2023-10-20 | 浙江科技学院 | Method for preparing magnetic magnesium-iron LDH-biochar composite material in one step and application |
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