CN109437291A - Hydrotalcite and preparation method thereof - Google Patents
Hydrotalcite and preparation method thereof Download PDFInfo
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- CN109437291A CN109437291A CN201811584782.2A CN201811584782A CN109437291A CN 109437291 A CN109437291 A CN 109437291A CN 201811584782 A CN201811584782 A CN 201811584782A CN 109437291 A CN109437291 A CN 109437291A
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- C01G23/00—Compounds of titanium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
Abstract
The invention discloses a kind of hydrotalcites and preparation method thereof, the preparation method of the hydrotalcite includes: that the raw material of synthetic hydrotalcite is dry grinded, hydrotalcite basic structure is formed by solid state reaction, wherein raw material includes metal hydroxides, higher valence metal oxide and metal salt.Make to come into full contact between material by way of dry grinding, solid state reaction occurs and forms the hydrotalcite basic structure of high-valence state, and then overcomes liquid phase coprecipitation because pH value and ionic radius difference are difficult to form the obstacle of LDH phase greatly.
Description
Technical field
The present invention relates to mining technique fields, in particular to a kind of hydrotalcite and preparation method thereof.
Background technique
Hydrotalcite (LDH) is a kind of layer structure mineral, and partly or completely trivalent metal can be by four in LDH component
Valence metal (Ti, Sn, Zr etc.) replaces, bivalent metal ion Mg2+、Zn2+、Cu2+And Co2+It can be total with tetravalent metal (Ti, Sn) liquid phase
It precipitates and forms LDH phase, and Ca2+But it is difficult to realize.
Ti element has many-sided functional characteristic, and titanium is a kind of argenteous transition metal, it is characterized in that light-weight, intensity
High, tool metallic luster.The alloy of high-temperature capability, low-temperature flexibility and the fracture toughness that titanium alloy has had, titanium and titanium is largely used to navigate
Empty industry has the title of " spatial metal ", therefore Ti system LDH synthesis and application also obtain extensive concern.Metallic element is variable in LDH
Transsexual imparting LDH extensive use, especially valence variation element, which exist, greatly widens LDH in the application of the fields such as the energy, organic synthesis.Mn
Element valence is changeable, have stronger receiving and losing electrons ability, can enhance into LDH laminate or widen LDH application feature and
Field.Mn system LDH is by compound with other materials, such as graphene, is the research heat of Mn correlation LDH applied to energy field
Point.
Therefore, the prior art lacks a kind of preparation method of hydrotalcite, has both adapted to metal ions M g2+、Zn2+、Cu2+、
Co2Deng, and it is suitble to Ca simultaneously2+With the high price houghite of the formation such as tetravalence such as Ti, Mn.
Summary of the invention
The purpose of the present invention is to provide a kind of hydrotalcites and preparation method thereof, so that obtaining liquid-phase precipitation method can not obtain
The high price houghite obtained.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention provides a kind of preparation methods of hydrotalcite comprising:
The raw material of synthetic hydrotalcite is dry grinded, hydrotalcite basic structure is formed by solid state reaction, wherein former
Material includes metal hydroxides, higher valence metal oxide and metal salt.
The invention further relates to a kind of hydrotalcites, are prepared by the preparation method of above-mentioned hydrotalcite.
Make to come into full contact between material by way of dry grinding, the hydrotalcite that solid state reaction forms high-valence state occurs
Basic structure, and then liquid phase coprecipitation is overcome because pH value and ionic radius difference are difficult to form the obstacle of LDH phase greatly.
Detailed description of the invention
It, below will be to use required in embodiment in order to illustrate more clearly of the technical solution of embodiment of the present invention
Attached drawing be briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not to be seen as
It is the restriction to range, it for those of ordinary skill in the art, without creative efforts, can be with root
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the XRD spectrum of Example 1 and Example 2 of the present invention Product samples；
Fig. 2 is the XRD spectrum of 7 Product samples of the embodiment of the present invention 6 and embodiment；
Fig. 3 is the scanning electron microscope (SEM) photograph of 2 Product samples of the embodiment of the present invention；
Fig. 4 is the scanning electron microscope (SEM) photograph of 7 Product samples of the embodiment of the present invention；
Fig. 5 is different CaCl2·2H2The XRD spectrum of influence of the O dosage to Ca-Ti LDH product；
Fig. 6 is different CaCl2·2H2The XRD spectrum of influence of the O dosage to Ca-Mn LDH product；
Fig. 7 is the XRD spectrum of influence of the different material molar ratio to Ca-Mn LDH product；
Fig. 8 is the XRD spectrum of influence of the different material molar ratio to Ca-Ti LDH product；
Fig. 9 is the XRD spectrum of influence of the wet-milling difference water to Ca-Ti LDH product.
Specific embodiment
It, below will be to embodiment party of the present invention to keep the purposes, technical schemes and advantages of embodiment of the present invention clearer
Technical solution in formula is clearly and completely described.The person that is not specified actual conditions in embodiment or embodiment, according to routine
The condition that condition or manufacturer suggest carries out.Reagents or instruments used without specified manufacturer, being can be by commercially available purchase
Buy the conventional products of acquisition.
A kind of hydrotalcite of embodiment of the present invention being related to and preparation method thereof is specifically described below.
Some embodiments of the present invention improve a kind of preparation method of hydrotalcite comprising:
The raw material of synthetic hydrotalcite is dry grinded, hydrotalcite basic structure is formed by solid state reaction, wherein former
Material includes metal hydroxides, higher valence metal oxide and metal salt.
Inventor's discovery generallys use liquid phase coprecipitation in the prior art to form hydrotalcite phase, wherein metal ion
Mg2+、Zn2+、Cu2+And Co2+LDH phase, and Ca can be formed with tetravalent metal (Ti, Sn etc.) liquid phase coprecipitation2+But it is difficult to realize, sends out
Bright people has found that causing calcium ion that cannot be co-precipitated the reason of forming LDH phase with tetravalent metal may is that one by numerous studies
Aspect, Ca2+It is higher (pH > 12 start to precipitate) to precipitate pH value, and quadrivalent metallic ion precipitating pH value is lower, the two is difficult in liquid phase
Middle co-precipitation forms LDH phase；On the other hand, Ca2+It is larger with other metal ion radius differences, it is difficult to form LDH phase.Therefore,
Inventor proposes the preparation method of above-mentioned hydrotalcite, Ca-M can be prepared again by studying for a long period of time and largely practicing
(IV, M=Ti, Mn) LDH phase, while being also applied for Mg2+、Zn2+、Cu2+And Co2Deng gold more than other metal ions and tetravalence
Belong to element and synthesizes LDH phase.Above-mentioned preparation method, which obtains the reason of said effect, may is that under the mechanism by dry grinding,
Contact with each other effect between material, and solid state reaction occurs, and forms such as Ca-M (IV, M=Ti, Mn) basic structure, in turn
It overcomes raw material liquid phase coprecipitation pH value and ionic radius difference is difficult to form the obstacle of LDH phase greatly, form completely new LDH phase.
In addition, the presence of metal salt be stabilized LDH phase can, and then being capable of synthesis in solid state LDH phase.For example,
In Ca-M (IV, M=Ti, Mn) LDH system, Ca2+Ionic radius is big, since seven coordination combinations can be bigger, Ca2+It is more prone to
In forming seven coordination structures rather than hexa-coordinate structure, Ca2+In addition to the oxygen hexa-coordinate in laminate, it is also necessary to interlayer guest complexation
Form seven coordination rock-steady structures.Using Ca (OH)2When with titanium dioxide or manganese dioxide as raw material, due to lacking anion
Interlayer object, Ca2+It is difficult to be formed and stablizes seven coordination structures.Therefore, in the presence of without the anion in metal salt, Ca2+It can not shape
At seven coordinations rock-steady structure typical in LDH phase, there is the phase interaction of enhancing laminate and interlayer object as third phase in metal salt
With being stabilized LDH phase can.
Further, according to some embodiments, metal salt is to contain CO3 2-Or Cl-Metal salt, preferably comprise Cl-'s
Metal salt.Further, metal salt is one of magnesium salts, calcium salt, mantoquita and zinc salt or a variety of.
According to some embodiments, metal hydroxides is the hydroxide of divalent metal, higher valence metal oxide four
Metal oxide more than valence, i.e. metal in metal oxide are greater than or equal to tetravalence.Further, some embodiments,
Metal hydroxides includes one of magnesium hydroxide, calcium hydroxide, Kocide SD and zinc hydroxide or a variety of, high-valency metal oxygen
Compound is one of titanium dioxide, manganese dioxide, zirconium dioxide, ceria and vanadic anhydride or a variety of, preferably high price
Metal oxide is titanium dioxide or manganese dioxide.
Further, in some embodiments, the metallic element contained in metal hydroxides and metal salt is corresponded to each other,
The metal phase in metal and metal salt i.e. in metal hydroxides is same, for example, metal hydroxides selects calcium hydroxide, metal
Salt can be calcium chloride or calcium carbonate.
In some preferred embodiments of the invention, raw material includes calcium hydroxide, calcium chloride and titanium dioxide, further excellent
The molar ratio for selecting calcium hydroxide, calcium chloride and titanium dioxide is 3:1:1~3.
Or in some preferred embodiments, raw material includes calcium hydroxide, calcium chloride and manganese dioxide, further preferred hydrogen-oxygen
The molar ratio for changing calcium, calcium chloride and manganese dioxide is 3:1:0.25~2.
It should be noted that calcium chloride can be CaCl in some embodiments2·2H2O, titanium dioxide can be TiO2·
H2O。
In some embodiments, the mode of dry grinding is that ball milling is carried out in grinding machine, grinding machine can for planetary ball mill or
Ball-stirring mill.
Further, in order to enable the solid phase synthesis between raw material can be carried out substantially effectively, high quality is obtained
Hydrotalcite, the parameter that grinds when needing to dry grinding controls, and when dry grinding, control ratio of grinding media to material is 7~45, for example, ratio of grinding media to material
It can be 7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,
31,32,33,34,35,36,37,38,39,40,41,42,43 or 44.Grinding rate can be 100~120rpm, for example,
101rpm, 103rpm, 105rpm, 107rpm, 108rpm, 110rpm, 112rpm, 113rpm, 114rpm, 115rpm, 116rpm,
118rpm or 119rpm.The dry grinding time is 20~240min, preferably 60~180min, more preferable 100~130min, for example, can
Think 30min, 40min, 50min, 60min, 70min, 80min, 90min, 110min, 120min, 130min, 140min,
150min, 160min, 170min, 180min etc..
Some embodiments of the present invention provide a kind of preparation method of hydrotalcite comprising: by synthetic hydrotalcite
Raw material is dry grinded, and forms hydrotalcite basic structure by solid state reaction；Water is added in hydrotalcite basic structure again to carry out
Wet-milling.Wherein, the selection of raw material is referring to foregoing teachings, and details are not described herein.
Solid state reaction is completed by way of dry grinding to be formed in hydrotalcite basic structure there is also impurity, and material it
Between relative distribution, by adding water-wet to grind, due to the presence of water, lamella particle mutually agglomerates into larger particles, while further
The generation for promoting LDH phase, promotes the purity of final product.
According to some embodiments, wet-milling is also carried out in grinding machine, and preferably grinding machine is planetary ball mill or Ball-stirring mill.Into
One step, when wet-milling, control ratio of grinding media to material is 7~45, and grinding rate is 100~120rpm, and wet-milling time is 40~80min, excellent
Select 50~70min, more preferable 55~65min.
In order to guarantee that wet-milling achievees the effect that improve product crystallinity, needs to control the amount of water of wet-milling, add water
Very few meeting is so that be not achieved the effect of wet-milling.Therefore, in some embodiments, the amount of water of wet-milling is carried out are as follows: the raw material
The 15%~50% of gross mass.
Some embodiments of the present invention additionally provide a kind of hydrotalcite, are prepared by the preparation method of above-mentioned hydrotalcite
It arrives.In particular, provide the hydrotalcite of new LDH phase i.e. Ca-Ti LDH phase and Ca-Mn LDH phase that synthesis obtains.
Feature and performance of the invention are described in further detail with reference to embodiments.
Equipment used in following embodiment and test example is as follows:
Grinding machine: using planetary ball mill as solid phase reaction device, including Germany goes at express speed Pulverisette-7 type planet
Ball mill；Constant temperature oscillation bain-marie: the permanent instrument Instrument Ltd. of Shanghai one, DKZ-2, China；Utilize X-ray diffractometer
(XRD) the object phase of milled processed products therefrom, Rigaku Rigaku company, MAX-RB/RU-200B type are characterized.Scanning electron
Microscope: JEOL company, Jeol Ltd., JSM-5610LV type.
Embodiment 1
Present embodiments provide a kind of preparation method of Ca-Ti system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and TiO2·H2O is incorporated in ball mill, ratio of grinding media to material 25, ball
Grinding revolving speed control is 600rpm, dry type ball milling material 2h, wherein Ca (OH)2、CaCl2·2H2O and TiO2·H2The molar ratio of O is
3:1:1.5.
Embodiment 2
Present embodiments provide a kind of preparation method of Ca-Ti system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and TiO2·H2O is incorporated in ball mill, ratio of grinding media to material 25, ball
Grinding revolving speed control is 600rpm, dry type ball milling material 2h, wherein Ca (OH)2、CaCl2·2H2O and TiO2·H2The molar ratio of O is
3:1:1.8.
Water 0.3mL is added, ratio of grinding media to material is controlled and revolving speed is constant, carry out wet-milling 1h, the hydrotalcite to be agglomerated.
Embodiment 3
Present embodiments provide a kind of preparation method of Ca-Ti system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and TiO2·H2It is 10 that O, which is incorporated in ball mill ratio of grinding media to material, ball milling
Revolving speed control is 1200rpm, dry type ball milling material 60min, wherein Ca (OH)2、CaCl2·2H2O and TiO2·H2The molar ratio of O
For 3:1:1.5.
Water 0.3mL is added, ratio of grinding media to material is controlled and revolving speed is constant, carry out wet-milling 1h, the hydrotalcite to be agglomerated.
Embodiment 4
Present embodiments provide a kind of preparation method of Ca-Ti system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and TiO2·H2It is 40 that O, which is incorporated in ball mill ratio of grinding media to material, ball milling
Revolving speed control is 150rpm, dry type ball milling material 200min, wherein Ca (OH)2、CaCl2·2H2O and TiO2·H2The molar ratio of O
For 3:1:1.5.
Water 0.4mL is added, ratio of grinding media to material is controlled and revolving speed is constant, carry out wet-milling 50min, the hydrotalcite to be agglomerated.
Embodiment 5
Present embodiments provide a kind of preparation method of Ca-Ti system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and TiO2·H2It is 38 that O, which is incorporated in ball mill ratio of grinding media to material, ball milling
Revolving speed control is 120rpm, dry type ball milling material 220min, wherein Ca (OH)2、CaCl2·2H2O and TiO2·H2The molar ratio of O
For 3:1:1.5.
Water 0.3mL is added, ratio of grinding media to material is controlled and revolving speed is constant, carry out wet-milling 70min, the hydrotalcite to be agglomerated.
Embodiment 6
Present embodiments provide a kind of preparation method of Ca-Mn system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and MnO2Being incorporated in ball mill ratio of grinding media to material is 15, rotational speed of ball-mill
Control is 1100rpm, dry type ball milling material 25min, wherein Ca (OH)2、CaCl2·2H2O and MnO2Molar ratio be 3:1:1.
Embodiment 7
Present embodiments provide a kind of preparation method of Ca-Mn system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and MnO2Being incorporated in ball mill ratio of grinding media to material is 15, rotational speed of ball-mill
Control is 1100rpm, dry type ball milling material 25min, wherein Ca (OH)2、CaCl2·2H2O and MnO2Molar ratio be 3:1:1.
Water 0.3mL is added, ratio of grinding media to material is controlled and revolving speed is constant, carry out wet-milling 65min, the hydrotalcite to be agglomerated.
Embodiment 8
Present embodiments provide a kind of preparation method of Ca-Mn system hydrotalcite comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and MnO2Being incorporated in ball mill ratio of grinding media to material is 30, rotational speed of ball-mill
Control is 600rpm, dry type ball milling material 2h, wherein Ca (OH)2、CaCl2·2H2O and MnO2Molar ratio be 3:1:1.2.
Water 0.3mL is added, ratio of grinding media to material is controlled and revolving speed is constant, carry out wet-milling 60min, the hydrotalcite to be agglomerated.
Test example 1
Embodiment 1 and embodiment 2 are respectively obtained into Ca-Ti hydrotalcite product and carry out XRD analysis, Fig. 1 is obtained, by embodiment
6 and the Ca-Mn hydrotalcite product that respectively obtains of embodiment 7 carry out XRD analysis, obtain Fig. 2.
From figure 2 it can be seen that dry and wet mill two-step method products therefrom three strongest peak d value be respectively 0.83nm, 0.42nm and
0.29nm is in multiple proportion, is typical case's LDH diffractive features, primarily determines that synthesized sample is Ca-Mn LDH phase.Ca-Mn LDH
In synthesis, Ca (OH)2With CaCl2·2H2O ball milling easily generates CaCl2·Ca(OH)2·H2O (JCPDS 02-1099) complex salt
Phase, this object are mutually major impurity phase in Ca-Mn LDH synthesis process, and main diffraction maximum position appears in 15 ° -20 ° of 2-theta.
Also find out that raw material by dry grinding, obvious Ca-Mn LDH phase occurs, illustrates that chemistry occurs for dry type ball milling raw material from Fig. 2 simultaneously
Reaction forms LDH phase, but obvious CaCl occurs at 15 ° -20 ° of 2-theta2·Ca(OH)2·H2O complex salt adds 0.3mL water
After wet-milling, complex salt, which mutually disappears, obtains pure Ca-Mn LDH, this illustrates that water addition promotes MnO2Generation is reacted between calcium compound
Ca-MnLDH.Similarly, it is also seen that identical rule from Fig. 1.
Ca-Ti hydrotalcite product obtained in embodiment 2 and embodiment 7 and Ca-Mn hydrotalcite product are scanned electricity
Sem observation, scanning electron microscope (SEM) photograph are as shown in Figure 3 and Figure 4.Fig. 3 and Fig. 4 is set forth Ca-Ti LDH and Ca-Mn LDH and is amplified to
1000 times and 10000 times of photo, by Fig. 3 and Fig. 4, it is evident that Ca-Ti LDH and Ca-Mn LDH are typical sheet knot
Structure, since water exists during wet-milling, lamella particle, which is mutually reunited, becomes larger particles.
The influence that metal salt synthesizes hydrotalcite
Embodiment 9~11
The preparation method difference from Example 2 of embodiment 9~11 is only that fixed Ca/Ti molar ratio is 2/1, adjusts
Whole Ca (OH)2/CaCl2·2H2O/TiO2·H2O molar ratio is respectively 2/0/1,3/0.5/1.75 and 3/1/2.
XRD analysis is carried out to the product of embodiment 9~11, gained XRD spectrum is shown in Fig. 5, from fig. 5, it can be seen that nothing
CaCl2·2H2In the presence of O, i.e. Ca (OH)2/CaCl2·2H2O/TiO2·H22/0/1 sample of O molar ratio, products therefrom object are mutually
Ca (OH) 2, no Ca-Ti LDH are combined to.Illustrate no CaCl2·2H2O addition, TiO2·H2O and Ca (OH)2Do not occur chemical anti-
It answers, TiO2·H2It is present in product after O ball milling with amorphous state.CaCl2·2H2After O is added, products therefrom object mutually changes,
CaCl2·2H2When O additional amount deficiency, i.e. Ca (OH)2/CaCl2·2H2O/TiO2·H2O molar ratio 3/0.5/1.75 sample produces
Owner is mutually Ca (OH)2, while weak Ca-Ti LDH diffraction maximum is generated, continue growing CaCl22H2O to Ca (OH)2/CaCl2·
2H2O/TiO2·H2O molar ratio is 3/1/2, and products therefrom main phase is Ca-Ti LDH.Statistics indicate that CaCl2·2H2O is ball milling
Method synthesizes the essential raw material of Ca-Ti LDH, provides LDH interlayer anion, and LDH layer structure is promoted to be formed.Experiment knot
In fruit further explanation calcium system LDH synthesis process, third phase compound such as CaCl2·2H2It adds to O to generate LDH phase and play
Decisive role.
Embodiment 12~14
The preparation method difference from Example 2 of embodiment 12~14 is only that, is fixed Ca (OH)2/MnO2Molar ratio is
3/1, it adjusts Ca (OH)2/CaCl2·2H2O/MnO2Molar ratio is respectively 3/0/1,3/0.5/1 and 3/1/1.
XRD analysis is carried out to the product of embodiment 12~14, gained XRD spectrum is shown in Fig. 6, from fig. 6, it can be seen that nothing
CaCl2·2H2In the presence of O, i.e. Ca (OH)2/CaCl2·2H2O/MnO2Molar ratio is 3/0/1, and dry and wet grinds two-step pretreatment MnO2With
Ca(OH)2It is reactionless, sample MnO2With Ca (OH)2Mixed phase.CaCl2·2H2After O addition, Ca (OH)2/CaCl2·2H2O/
MnO2Ca-Mn LDH phase generates in 3/0.5/1 sample of molar ratio, illustrates CaCl2·2H2O promotes LDH phase to generate.3/0.5/1 still
So remain Ca (OH)2, illustrate CaCl2·2H2O dosage is insufficient, continues growing CaCl2·2H2O dosage is to Ca (OH)2/
CaCl2·2H2O/MnO2Molar ratio 3/1/1 obtains pure Ca-Mn LDH product.Above-mentioned data explanation, CaCl2·2H2O is ball milling
The essential component of Ca-Mn LDH is synthesized, third, which is added to, promotes Ca (OH)2With MnO2Reaction generates Ca-Mn LDH, this and Ca-
Ti LDH synthesis third phase role is consistent, further confirms that calcium system LDH synthesis needs to add third phase and promotes product to layer
Shape LDH transformation.
The influence of feed molar comparison product
Embodiment 15~19
15~18 preparation method difference from Example 2 of embodiment is only that the molar ratio of raw material is respectively 3/
1/1,3/1/1.5,3/1/2,3/1/2.5 and 3/1/3, the XRD spectrum for obtaining product is as shown in Figure 7.It can be seen from figure 7 that
Ca(OH)2/CaCl2·2H2O/TiO2·H2When O molar ratio is 3/1/1, product X RD map can determine three kinds of object phases, Ca-Ti
LDH, the Ca (OH) for having neither part nor lot in reaction2And CaCl2·2H2O and Ca (OH)2Reaction generates complex salt (JCPDS 02-
1099CaCl2·Ca(OH)2·H2O), due to Ca (OH)2Remnants illustrate under the molar ratio, TiO2·H2O dosage is insufficient.
Continue growing TiO2·H2O moles of accounting, Ca (OH)2/CaCl2·2H2O/TiO2·H2O molar ratio is 3/1/1.5, has no obvious
Impurity diffraction maximum illustrates the molar ratio for the preparation more excellent molar ratio of material of Ca-TiLDH.Continue growing TiO2·H2O dosage,
CaCl2·Ca(OH)2·H2O complex salt mutually occurs again, as Ca (OH)2/CaCl2·2H2O/TiO2·H2O molar ratio is 3/1/2
When, resulting material is amorphous state, Ca (OH)2/CaCl2·2H2O/TiO2·H2O molar ratio reaches 3/1/3, Ca-Ti LDH cancellation
It loses, products therefrom CaCl2·Ca(OH)2·H2O complex salt.Above-mentioned data explanation, CaCl2·2H2O and Ca (OH)2It generates multiple
It closes reactant salt to be relatively easy to carry out, TiO2·H2When O is excessive and insufficient, leading solid phase reaction process is reacted in complex salt production, only
Appropriate TiO2·H2O addition, which could allow entirely react to LDH phase, generates direction transformation.Therefore, with Ca (OH)2、TiO2·H2O and
CaCl2·2H2O is raw material, and dry and wet grinds the two-step method preparation more excellent Ca of Ca-Ti LDH (OH)2/CaCl2·2H2O/TiO2·H2O rubs
You are than being 3/1/1.5.
Embodiment 20~24
20~24 preparation method difference from Example 8 of embodiment is only that, the molar ratio 3/1/2,3/1/ of raw material
1.5,3/1/1,3/1/0.5 and 3/1/0.25, the XRD spectrum for obtaining product is as shown in Figure 8.
As can be seen from Figure 8, Ca (OH)2With CaCl2·2H2Easily reaction generates CaCl in O mechanical milling process2·Ca
(OH)2·H2O complex salt phase, MnO2A small amount of be added can form Ca-Mn LDH phase.Low MnO2Under the conditions of dosage, i.e. Ca (OH)2/
CaCl2·2H2O/MnO2Molar ratio is 3/1/0.25 and 3/1/0.5, and it is Ca-Mn LDH, Ca (OH) that dry and wet, which grinds products therefrom,2And
CaCl2·Ca(OH)2·H2O complex salt three-phase mixture, calcium compound, which largely remains, illustrates MnO2Dosage is insufficient.It continues growing
MnO2 dosage is to Ca (OH)2/CaCl2·2H2O/MnO2Molar ratio is 3/1/1, Ca (OH)2And CaCl2·Ca(OH)2·H2O is compound
Salt associated diffraction peak disappears, and obtains more pure Ca-Mn LDH phase.Ca(OH)2/CaCl2·2H2O/MnO2Molar ratio is 3/1/
1.5 and 3/1/2, MnO2The influence that dosage continues to increase to product object phase is smaller.3/1/1,3/1/1.5 and 3/,1/2 3 sample
The consistent free from admixture diffraction phase of diffractive features is pure Ca-Mn LDH, but three is poor in the diffracted intensity presence of the main diffraction maximum of d001
Different, diffracted intensity is respectively 5634a.u., 4040a.u. and 2025a.u., with MnO2Dosage increases diffracted intensity and gradually drops
It is low, high MnO2Dosage is unfavorable for forming high-crystallinity Ca-Mn LDH, therefore Ca (OH)2/CaCl2·2H2O/MnO2Optimum molar
It is 3/1/1 than condition.
Influence of the wet-milling water to product
Embodiment 25~28
The preparation method for the Ca-Ti system hydrotalcite that the present embodiment 25~28 provides comprising following steps:
The Ca (OH) for being 2g by gross mass2、CaCl2·2H2O and TiO2·H2O is incorporated in ball mill, ratio of grinding media to material 28, ball
Grinding revolving speed control is 600rpm, dry type ball milling material 2h, wherein Ca (OH)2、CaCl2·2H2O and TiO2·H2The molar ratio of O is
3:1:1.8.
Water is added, ratio of grinding media to material is controlled and revolving speed is constant, carry out wet-milling 1h, the hydrotalcite to be agglomerated.Four examples it
Between the difference is that only, the wet-milling water that water is added is respectively 0.3mL, 0.6mL, 0.8mL and 1.0mL.The XRD diagram of its product
Piece is as shown in Figure 9.
From fig. 9, it can be seen that 0.3mL sample main phase is Ca-Ti LDH phase, 15 ° -20 ° of 2-theta still can be observed
Mutually exist to more obvious calcium correlative, by being continuously increased water consumption, gained sample purity is further promoted, water consumption
When for 1.0mL, impurity phase disappears.During existing research shows synthesis in solid state LDH, water plays catalyst action, the addition of water
Amount has important influence to LDH crystallization process and LDH product crystallinity.Experimental data shows that the appropriate addition of water can promote
LDH phase generates, and promotes final product purity.
In conclusion embodiments of the present invention from conventional Ca-Al LDH synthesis, expand to Ca-M (IV, M=Ti,
Mn) LDH is synthesized, and is overcome raw material precipitating pH value and ionic radius difference to be difficult to form the obstacle of LDH phase greatly by solid phase method, is synthesized
Completely new LDH phase, discloses calcium system LDH synthesis mechanism.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of hydrotalcite, characterized in that it comprises:
The raw material of synthetic hydrotalcite is dry grinded, hydrotalcite basic structure is formed by solid state reaction；
Wherein, the raw material includes metal hydroxides, higher valence metal oxide and metal salt.
2. the preparation method of hydrotalcite according to claim 1, which is characterized in that the metal salt is to contain CO3 2-Or Cl-
Metal salt, preferably comprise Cl-Metal salt.
3. the preparation method of hydrotalcite according to claim 1, which is characterized in that the metal hydroxides is divalent gold
The hydroxide of category, the higher valence metal oxide are the metal oxide of tetravalence or more.
4. the preparation method of hydrotalcite according to claim 1, which is characterized in that the metal hydroxides includes hydrogen-oxygen
Change one of magnesium, calcium hydroxide, Kocide SD and zinc hydroxide or a variety of, the higher valence metal oxide be titanium dioxide,
One of manganese dioxide, zirconium dioxide, ceria and vanadic anhydride are a variety of, and the metal salt is magnesium salts, calcium salt, copper
One of salt and zinc salt are a variety of.
5. the preparation method of hydrotalcite according to claim 2, which is characterized in that the metal hydroxides and the gold
Belong to the metallic element contained in salt to correspond to each other.
6. the preparation method of hydrotalcite according to claim 1, which is characterized in that the raw material includes calcium hydroxide, chlorine
Change calcium and titanium dioxide, the molar ratio of the preferably described calcium hydroxide, the calcium chloride and the titanium dioxide is 3:1:1~3；
Or, the raw material includes calcium hydroxide, calcium chloride and manganese dioxide, the preferably described calcium hydroxide, the calcium chloride and institute
The molar ratio for stating manganese dioxide is 3:1:0.25~2；
Preferably, the calcium chloride is CaCl2·2H2O, the titanium dioxide are TiO2·H2O。
7. the preparation method of hydrotalcite according to claim 1, which is characterized in that when dry grinding, control ratio of grinding media to material be 7~
45, grinding rate be 100~120rpm, the dry grinding time for 20~240min, preferably 60~180min, more preferable 100~
130min。
8. the preparation method of described in any item hydrotalcites according to claim 1~7, which is characterized in that further include: by hydrotalcite
Basic structure is added water and carries out wet-milling；
Preferably, dry grinding and wet-milling carry out in grinding machine, it is preferable that the grinding machine is planetary ball mill or Ball-stirring mill；
Preferably, when wet-milling, control ratio of grinding media to material be 7~45, grinding rate be 100~120rpm, the wet-milling time be 40~
80min, preferably 50~70min, more preferable 55~65min.
9. the preparation method of hydrotalcite according to claim 8, which is characterized in that carry out the amount of water of wet-milling are as follows: described
The 15%~50% of the gross mass of raw material.
10. a kind of hydrotalcite, which is characterized in that it is prepared by the preparation method of hydrotalcite according to any one of claims 1 to 9
It obtains.
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| CN114956143A (en) * | 2022-05-16 | 2022-08-30 | 安徽大学绿色产业创新研究院 | Method for preparing lithium-aluminum hydrotalcite by mechanochemical method |
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