CN102712492A - Layered double hydroxide variant sepiolite compound, and method for preparing same - Google Patents
Layered double hydroxide variant sepiolite compound, and method for preparing same Download PDFInfo
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Abstract
The present invention relates to a layered double hydroxide variant sepiolite compound and to a method for preparing same. In detail, the present invention relates to a layered double hydroxide variant sepiolite compound and to a method for preparing same wherein a thermal transformation process and a hydration process are performed on layered metal hydroxide which is an anionic compound, so that the layered double hydroxide variant sepiolite compound has a channel structure in which blocks and tunnels intersect each other in a crystallographic axis, and has physicochemical stability, a wide specific surface area, and porosity, and thus improved thermal properties. The sepiolite compound according to the present invention can be applied to a variety of fields including the production of thermal stabilizers, flame retardants, absorbents, filters, spandex, fillers, catalysts, decolorants, etc.
Description
Technical field
Ou Saite (sepiocite) compound and preparation method thereof is warded off in the varient west that the present invention relates to layered double hydroxide; Relate to particularly; Through thermal distortion and hydration reaction; Make module (block) and tunnel (tunnel) of anionic compound layered metal hydroxides demonstrate passage (channel) structure of intersecting with crystallographic axes; And have the specific surface area and the porousness of physical and chemical stability and broad, thereby improve its thermophysical property have varient sepiocite compound with the layered metal hydroxides of similar structure of sepiolite crystalline texture and physics-chem characteristic and preparation method thereof.
Background technology
(Layered Double Hydoroxide is anionic clay, hydrotalcite-similar or brucite-similar compound LDH) to layered double hydroxide, has 2 distinct dimension laminate structures.This layered double hydroxide is usually by chemical formula [M
II+ 1-xM
III+ x(OH)
2] [A
M-]
X/mNH
2O representes, wherein M
N+Be metallic cation, A
M-Be interlayer anion.Metal bi oxyhydroxide has good anion exchange capacity and various chemical constitution; Has swelling property (swelling property); The human body environment-friendly type; Anion, carbonate is had avidity, can be used for a plurality of fields such as human emulation medical material, anion ion exchange body, stablizer, absorption agent, scavenging agent (scavenger), catalyzer (catalyst), catalysis balustrade, precursor.
This layered double hydroxide not only exists with the natural goods form; It also can be artificial synthetic anionic compound; According to compound method or external treatment method; Perhaps,, can cause that phase transition changes through steps such as dehydrationization reaction, dehydroxylation reaction, exhaustion of yin ion reactions according to thermal treatment.This layered double hydroxide is an inorganics; Thermotolerance is high; Harmless; The ability of catching the chlorine between the bilayer structure is stronger, can improve thermostability and the flame retardant resistance (korean granted patent 10-0548645 number, 10-0527978 number, 10-0506123 number, 10-0370961 number, 10-0909220 number) of macromolecule resin etc.But the chlorine through simple IX is caught effect, and at high temperature cl ions can break away from once more, and has the problem that produces hydrogen chloride gas, is badly in need of developing to have stronger chloropexia ability, also has the material of good heat stable property simultaneously.
In addition, the sepiolite (sepiolite) that forms from cationic nature compound-smectite is that chemical formula is Si
12Mg
8O
30(OH)
4(OH
2)
48H
2The natural clay of the grain structure of O.Different ground with common natural clay, sepiolite has the chain channel architecture, and the CEC of the sepiolite of this chain lattice (chain lattice) is very low.Sepiolite is a needle-like, perhaps has the porousness and the non-expansibility of high specific surface area, good adsorption ability and special chlorine character, thus can carry out multiple application.
Contriver of the present invention makes by layered double hydroxide synthetic sepiolite similar compound; This layered double hydroxide is through thermal distortion and hydration reaction; The channel architecture that makes said sepiolite have presents the structure that module that said sepiolite has and tunnel intersect with crystallographic axes; Simultaneously; Because have the specific surface area and the porousness of physical and chemical stability and broad, thereby its thermophysical property also improves, and the present invention is with said compound called after " Ou Saite (sepiocite) is warded off in the west ".
Summary of the invention
The purpose of this invention is to provide a kind of varient compound S epiocite compound of layered metal hydroxides, this compound has and the similar crystalline texture of the crystalline texture of sepiolite, and promptly module and tunnel are with the channel architecture of crystallographic axes intersection.
Another object of the present invention provides the preparation method of said Sepiocite compound.
For realizing above-mentioned purpose; The present invention provides a kind of varient Sepiocite compound of layered double hydroxide; This compound is represented to have and the similar crystalline texture of sepiolite crystalline texture by following Chemical formula 1, reach the channel-style structure that module and tunnel intersect with crystallographic axes.
[M(II)
1-xM(III)
xO
a/b(OH)
2-a(A)
X/n]y·H
2O
Wherein, M (II) is the divalent metallic cation; M (III) is 3 valency metallic cations; A is and the negatively charged ion chemistry species of hydroxide layer covalent linkage that n is a charge number; X is less than 0.5 number more than or equal to 0.1; A is less than 2 number greater than 1; B is greater than 0 number less than a; Y is the real number greater than 0.
The present invention also provides the preparation method of said sepiocite compound, comprising: (a) under 265 ℃ to 275 ℃ conditions, layered double hydroxide is heat-treated the step of the layered double hydroxide of fabrication portion dehydroxylation; (b) layered double hydroxide to said partially dehydroxylatedization carries out hydration reaction, makes the sepiocite compound step with channel architecture.
Other characteristics of the present invention and specific embodiment are described in more details through following detailed description and additional claim.
Description of drawings
Fig. 1 is the transmission electron microscope image that shows the channel-style crystalline texture of sepiolite, and A and B show natural sepiolite compound crystal structure, and C shows the photo of dehydration sepiolite crystalline texture;
Fig. 2 is a layered double hydroxide through overheating deforming and hydrolytic process and the synoptic diagram (a: shape double-hydroxide of the sepiocite compound for preparing; B: the layered double hydroxide of dehydration; C: the layered double hydroxide of partially dehydroxylatedization; D: the sepiocite that makes through hydrolysis reaction, e: the sepiocite of dehydration, and f: the layered double hydroxide of decarboxylation);
Fig. 3 is the X-ray diffraction figure (a: layered double hydroxide of sepiocite; B: the layered double hydroxide of dehydration; C: the layered double hydroxide of partially dehydroxylatedization, d: in air, carry out aquation and the sepiocite that makes, e: in the water of normal temperature, carry out aquation and the sepiocite that makes; F: in 90 ℃ water, carry out aquation and the sepiocite that makes, g: the sepiocite of dehydration);
Fig. 4 is the transmission electron microscope image of sepiocite.(a: the surface tissue of layered double hydroxide, b: the internal structure of layered double hydroxide, the surface tissue of c:sepiocite, and d:sepiocite internal structure);
Fig. 5 is the infrared spectrum analysis result (a: layered double hydroxide, b: the layered double hydroxide of dehydration, c:sepiocite, and d: the sepiocite of dehydration) of sepiocite;
Fig. 6 is sepiocite
27Aluminium magic-angle-spinning nuclear magnetic resonance analytical results (a: layered metal hydroxides, b: dehydrationization layered metal hydroxides, c:sepiocite, and d: the sepiocite of dehydrationization);
Fig. 7 is the thermogravimetric analysis result (a: layered double hydroxide, b: the layered double hydroxide of dehydrationization, c:sepiocite, and d: the sepiocite of dehydrationization) of sepiocite.
Embodiment
The present invention relates to the varient sepiocite compound of layered double hydroxide, said compound is represented to have and the similar crystalline texture of the crystalline texture of sepiolite by following Chemical formula 1.
[M(II)
1-xM(III)
xO
a/b(OH)
2-a(A)
X/n]·yH
2O
Wherein, M (II) is the divalent metallic cation; M (III) is 3 valency metallic cations; A is and the negatively charged ion chemistry species of hydroxide layer covalent linkage that n is a charge number; X is less than 0.5 number more than or equal to 0.1; A is less than 2 number greater than 1; B is greater than 0 number less than a; And y is the real number greater than 0.
Wherein, said divalent metallic cation is Mg
2+, Ca
2+, Co
2+, Cu
2+, Ni
2+Perhaps Zn
2+, said 3 valency metallic cations are Al
3+, Cr
3+, Fe
3+, Ga
3+, In
3+, V
3+Perhaps Ti
3+, said negatively charged ion can be CO
3 2-, NO
3 -, Cl
-, OH
-, O
2-, or SO
4 2-
Among the present invention, said sepiolite can be by 4 expressions of following chemical formula,
Chemical formula 4
Si
12Mg
8O
30(OH)
4(OH
2)
48H
2O (sepiolite)
(Eduardo Ruiz-Hitzky, Journal of Materials Chemistry, 2001 shown in A, B and the C of Fig. 1; 11; 86-91), sepiolite has the crystal type of elongation, and it is the magnesium silicon salt mineral with crystalline texture of the long passage that is communicated with; The octahedra magnesium atom layer that perhaps magnesium silicate aquation thing, central part have discontinuous formation connects the structure of two tetrahedral silicate layers through Sauerstoffatom.
The smectite that this sepiolite is existed by nature receives chemomorphosis hot and that the pressure effect is caused and produces, and smectite is the natural mineral with following chemical formula 5.
Chemical formula 5
(Al
2-xMg
x) (Si
4) O
10[OH]
2M
+ n X/n(smectite)
Wherein, said M is the metals ion of interlayer, is to compare the metals ion of Si in the layer, Al, Mg etc. more easily by the substituted metallic cation of cationic chemical species, and said x is an interlayer metal ionic ratio of components, is 0.2 to 0.7, and said n is a nucleidic mass.In the said chemical formula, when x is 0.2 to 0.7 left and right sides, has the easy substituted character of interlayer cation.
By this smectite distortion synthetic sepiolite; Have very high specific surface area, good adsorption ability and extraordinary decolorizing ability (decolorizng), bonding force, thickening property functions such as (thickening), can be used for packing material (rubber, pigment, coating, plastics), siccative, carrier, catalyzer, substitute the asbestos auxiliary, building materials (mortar, ceramic tile), refractory body, sorbent material, shop sand, packing material, liquid support (carrier), oil absorber, purification agent (discoloring agent), the aqua of holing, brake lining, humextant etc. up and down.
With sepiolite constitutional features and the similar sepiocite compound of the present invention of physical chemistry rerum natura; Specific surface area and porousness, adsorptivity etc. with broad; And consequent good thermophysical property, can be used for the Application Areas that said sepiolite is employed.
Among the present invention, the 2D crystallographic structure of said sepiocite compound is the catenate specific channel type structure that module and tunnel intersect.As shown in Figure 4, the layered double hydroxide of existing layered double hydroxide or partially dehydroxylatedization shown in Fig. 4 (b), has laminate structure, not fracture in the middle of the hydroxide layer.But,, have " the channel-style structure that module and tunnel intersect with crystallographic axes " according to sepiocite compound of the present invention.That is, shown in Fig. 4 (d), hydroxide layer itself produces fracture, forms the tunnel on the hydroxide layer transverse axis, and longitudinal axis upper module (hydroxide layer) intersects with tunnel (space of fracture).And, observe this structure from crystallographic axes a, b, c, then have channel-style or chain-like structure.Compare existing layered double hydroxide, variation has taken place in the structure in the crystallization, and consequent physics-chem characteristic is also similar with the characteristic of sepiolite.
Among the present invention, said sepiocite compound is compared layered metal bi oxyhydroxide and is had big 3 times to 4 times specific surface area.Shown in following embodiment, sepiocite compound of the present invention is compared existing layered double hydroxide and is had big 3.5 times specific surface area.
Among the present invention; Said sepiocite compound is compared layered double hydroxide, and its thermophysical property has improved 30 ℃ to 40 ℃, and is specifically as shown in Figure 7; Compare layered double hydroxide, under high about 30 ℃ to 40 ℃ temperature, produce dehydroxylation reaction.
Among the present invention, the crystalline texture of layered double-metal hydroxide is stratiform, and it is reactive not only to demonstrate special interlayer, and has anion exchange capacity (anion exchange capacity).This is that in order to compensate this electric charge, negatively charged ion is present between the layer because the hydrogenate layer of layered double hydroxide has positive charge, and this interlayer anion can be replaced by other negatively charged ion chemistry species.It can be represented by following Chemical formula 2.
[M(II)
1-xM(III)
x(OH)
2]
X+[A
n-]
X/n·yH
2O
Wherein, M (II) is the divalent metallic cation; M (III) is 3 valency metallic cations; A is negatively charged ion chemistry species, and n is a charge number; X is less than 0.5 number more than or equal to 0.1; And y is the real number greater than 0.
Among the present invention, said sepiolite compound is from layered double hydroxide inductive varient compound, on the trellis face, has different structure, but can keep the granularity and the shape of layered metal hydroxides, also can be out of shape.
Among the present invention, said divalent metallic cation can be selected from by Mg
2+, Ca
2+, Co
2+, Cu
2+, Ni
2+And Zn
2+The crowd who forms, said 3 valency metallic cations can be selected from by Al
3+, Cr
3+, Fe
3+, Ga
3+, In
3+, V
3+And Ti
3+The crowd who forms, said negatively charged ion is selected from by CO
3 2-, NO
3-, Cl-, OH-, O
2-And SO
4 2-The crowd who forms.The ratio of said divalent metallic cation and 3 valency metallic cations is adjusted into 2: 1,3: 1 and 4: 1 etc., thus the layered metal hydroxides that the form layers electric charge is conditioned.Said divalent metallic cation, 3 valency metallic cations and said negatively charged ion are not limited to said kind, can comprise the affiliated known all kinds that belongs to layered double hydroxide of technical field of the present invention.
Layered metal hydroxides is in the preparation process, according to i) temperature of reaction solution; The ii) concentration of reaction solution; The iii) blending ratio between the metallic cation; The iv) temperature of washing water; V) composite factor such as drying temperature and show multiple granularity and shape.
Among the present invention, said sepiocite compound is represented by following chemical formula 3.
Chemical formula 3
[Mg
1-xAl
xO
a/b(OH)
2-a(CO
3)
x/2]·yH
2O
Wherein, x is less than 0.5 number more than or equal to 0.1; A is less than 2 number greater than 0; B is greater than 0 number less than a; And y is the real number greater than 0.
From another angle, the present invention relates to the preparation method of sepiocite compound, comprising: (a) under 265 ℃ to 275 ℃ conditions, layered double hydroxide is heat-treated, prepare the step of the layered double hydroxide of partially dehydroxylatedization; And (b) layered double hydroxide of said partially dehydroxylatedization is carried out hydration reaction, preparation has the step of the sepiocite compound of channel architecture.
Among the present invention, said sepiocite compound has 6 hydroxyls around Mg
2+, Al
3+6 coordinations (octahedral structure) and 4 hydroxyls around Mg
2+, Al
3+The structure that mix to exist of 4 coordinations (tetrahedral structure).
Among the present invention, the layered double hydroxide of said hydration reaction said partially dehydroxylatedization of sedimentation in gas phase that contains moisture or water-soluble solvent and carrying out.
Among the present invention, in said (a) step, produce the channel-style structure in 265 ℃ to 275 ℃ special thermal treatment TR and said (b) step by hydration reaction, and to heat treatment time or not restriction of hydration reaction time.
Among the present invention, as shown in Figure 2, layered double hydroxide (a step) is heated to 180 ℃ and after the dehydration reaction (b step), be heat-treated to 270 ℃, carries out partially dehydroxylatedization reaction (c step).When the inner OH base of hydroxide layer produced partially dehydroxylatedization reaction, carbonate anion and hydroxide layer formed covalent linkage, and the firm 2D layered crystal structure of layered double hydroxide is decomposed.Afterwards, hydration reaction for example is dispersed in the water; Then carry out hydration reaction (d step); Crystalline texture is arranged in channel-style again and generates sepiocite, is heated to 180 ℃ at this, and then dehydrationization reaction (e step) takes place sepiocite; Heat-treat with 580 ℃, decarboxylation reaction (f step) then takes place.
In said reaction process, for example, hydrotalcite is called houghite in the crystallization phases of 260 ℃ of lower section dehydroxylation or aquation in the layered double hydroxide; In water or air, carry out aquation under the normal temperature, then the metal in the covalent linkage of carbonate anion and the hydroxide layer is kept laminate structure with the state that 6 coordinations/4 coordinations mixing exists, but in the water more than 90 ℃, carries out aquation; Then the carbonate anion of covalent bonds and 4 coordinations return to the precursor (Fig.5 of laminate structure of gravitation and the 6 coordination shapes of electrostatic force; TS.Stanimirova et al, Journal of Materials Science, 34; 1999,4153).But, according to sepiocite compound of the present invention,, can not return to original layered double hydroxide even in the water more than 90 ℃, carry out aquation yet, keep the structure of the sepiocite compound of preparation at normal temperatures.
Among the present invention, layered double-metal hydroxide drips the alkali aqueous solution through (a) in the aqueous solution that contains divalent metal-salt and 3 valency metal-salts, prepares the step of sedimentary bedded salt metal hydroxides xln; And the bedded salt metal hydroxides xln that (b) in said (a) step, prepares is through the step of the synthetic preparation of hydro-thermal layered metal hydroxides and prepare.
Among the present invention, said divalent metal-salt is a magnesium salts, and said 3 valency metal-salts are aluminium salt.
Among the present invention, in the said method, if comprise that with divalent metal-salt and 3 valency aqueous metal salts with the titration of alkali solution, when at normal temperatures layered double hydroxide being carried out crystallization and hydro-thermal reaction synthetic step, said divalent metal can be magnesium (Mg
2+), calcium (Ca
2+) or zinc (Zn
2+), said 3 valency metals can be aluminium (Al
3+) or iron (Fe
3+), said salt based sols can be sodium hydroxide (NaOH) or ammonia (NH
3).Form deposition synthetic layered double hydroxide, according to conditions such as the ratio of the concentration of the metals ion in synthetic, metals ion, rate of titration, total reaction times, can obtain having multiple composition, the particle of grain type and granularity.
Among the present invention, said hydrothermal synthesis method improves crystalline synthesis method for the layered double hydroxide with crystallization reacts under high temperature and hyperbaric environment, and temperature is at 50-500 ℃, and pressure can synthesize under the environment more than the normal atmosphere.
The present invention will be described in more detail below in conjunction with embodiment.Following examples are merely explanation example of the present invention, and those skilled in the art should know scope of the present invention and do not limited with embodiment.
Embodiment 1: the preparation of layered double hydroxide and sepiocite compound
The preparation of 1-1, layered double hydroxide
With Mg (NO
3)
26H
2O (0.4M) and Al (NO
3)
39H
2O (0.2M) is dissolved in zero(ppm) water, with dissolving NaHCO
3The NaOH aqueous solution (0.2M) is pH value titration to 9～10, precipitated and the layered double hydroxide xln that forms.Under 100 ℃, layered double hydroxide was stirred 16 hours, remove unreacted salt through washing process after, freeze-dried and obtain layered double hydroxide.
The preparation of 1-2, sepiocite compound
With the layered double hydroxide that said 1-1 obtains, use thermogravimetric analyzer (PerkinElmer Pyris Diamond) under 270 ℃, to carry out thermal treatment in 8 hours, obtain the layered double hydroxide of partially dehydroxylatedization.The layered double hydroxide of partially dehydroxylatedization is dispersed to zero(ppm) water, stirs and carried out aquation on the 7th, the freeze-dried sepiocite compound that obtains.
The preparation of the layered metal hydroxides of comparative example 1, dehydrationization and the sepiocite of dehydrationization
Use thermogravimetric analyzer (PerkinElmer Pyris Diamond) will be from the layered double hydroxide and the sepiocite of said embodiment 1 preparation; Be warming up to 180 ℃ with 10 ℃/minute; To be present in inner moisture and dewater, prepare the layered double hydroxide of dehydration and the sepiocite of dehydration.
The structural analysis of experimental example 1:sepiocite
1-1, X-ray diffraction analysis
In order to confirm to carry out X-ray diffraction (Rigaku, D/Max 2200) analysis in the crystalline texture of the compound of said embodiment 1 and comparative example 1 preparation.Its result is as shown in Figure 3; It is the typical laminate structure that is inserted with carbonate anion that the interlayer of confirming as the layered double hydroxide of layered double hydroxide and dehydrationization is spaced apart 7.58～
, and the layered double hydroxide of partially dehydroxylatedization becomes the undefined structure that the stratiform lattice are decomposed.Sepiocite is because the hydration reaction of the layered double hydroxide of partially dehydroxylatedization is rearranged for the structure that interlayer is spaced apart
.The interlayer of the sepiocite of dehydrationization is spaced apart after
dehydrationization reaction; The interfloor distance that is equivalent to the crystal water size does not reduce, and therefore confirms that sepiocite does not produce expansion.And, when in 90 ℃ water, carrying out aquation, do not return to original LDH yet, demonstrate the XRD figure case identical (Fig. 3 (f)) with the sepiocite compound that in normal temperature, prepares.
1-2, tem study
For shape and the crystalline texture of trickle affirmation, carried out transmission electron microscope (JEOL JEM-2100F) analysis at the compound of said embodiment 1 preparation.Each compound is individually fixed in epoxy resin,, the internal structure of compound is observed with the cutting of 50nm thickness.Its structure is as shown in Figure 4; Layered double-metal hydroxide is the particle (Fig. 4 (a)) of hexagonal configuration, and interlayer is about
at interval be the laminate structure (Fig. 4 (b)) that is inserted with carbonate anion.In contrast; Sepiocite is shown as the surface tissue (4 (c)) that the fishbone grain pattern splits; Confirm as interlayer and be about
at interval it no longer is a stratiform, but module and tunnel are with the channel-style structure (4 (d)) of crystallographic axes decussate texture.The structure decision of sepiocite is with very similar from the natural inductive sepiolite of montmorillonitization compound structure.
1-3, ultraviolet spectral analysis
Be the formation reason of the channel architecture of investigating said sepiocite, carried out ultraviolet spectrogram (JASCOFT/IR-6100) analysis.Through at 1360cm
-1, 1025cm
-1, 3060cm
-1Peak change, can know the sepiocite of partially dehydroxylatedization, because of the gravitation of electrostatic force, make the two coordinations of the carbonate anion that is inserted in interlayer ground covalent bonds on layer (Fig. 5).
1-4,
27The aluminium magic-angle-spinning nuclear magnetic resonance is analyzed
For the formation reason of the channel of investigating said sepiocite, carried out
27The aluminium magic-angle-spinning nuclear magnetic resonance is analyzed (JASCO FT/IR-6100).Utilize 300MHz solid phase NMR spectrometer (Bruker) to measure, the standard test portion has used Al
2O
3, the frequency of projector is 104.21MHz, and reversing speed is 15kHz, and PW is the pulse of 2.3 μ s.
Its result, as shown in Figure 6, use
27Aluminium magic-angle-spinning nuclear magnetic resonance analytical method can be known by centering on Al in the stratiform that Mg-(OH)-Al forms
3+Surrounding enviroment, layered double hydroxide forms 6 hydroxide bases around Al
3+6 coordinations, octahedral structure and 4 hydroxide bases around Al
3+4 coordinations, tetrahedral structure mix and exist, therefore, peak value appears on 5.3ppm and 68ppm simultaneously.((c) and (d))
The specificity analysis of experimental example 2:sepiocite
The mensuration of 2-1, specific surface area
Utilize nitrogen absorption-disengaging method (ASAP 2000) and BET formula to measure the layered double hydroxide of preparation among the said embodiment 1 and porosity characteristic and the specific surface area of sepiocite.
Its result, as shown in table 1, the specific surface area of layered double hydroxide is 34.21m2/g, and the reference area of sepiocite is 128.25m2/g, and because of the channel architecture that thermal distortion and hydration reaction form, its specific surface area has increased about 3.5 times.
[table 1]
| Layered double hydroxide | sepiocite | |
| SBET(m 2/g) | 34.21 | 128.25 |
2-2, thermogravimetric analysis experiment
In order to confirm the thermophysical property of compound prepared in said embodiment 1 and the comparative example 1, carried out thermogravimetric analysis.Utilize thermogravimetric analyzer (PerkinElmer Pyris Diamond), temperature is risen to 800 ℃, observed the quality change that produces according to temperature variation with 10 ℃/minute.
Its result, as shown in Figure 7, layered double hydroxide and sepiocite form heat decomposition curve with 3 steps of typical dehydrated reaction, dehydroxylation reaction, decarboxylation glycosylation reaction.But the temperature range that dehydroxylation reaction takes place sepiocite is compared the layered double hydroxide high temperature about 35 ℃ that rises approximately, can confirm that its thermophysical property increases.This is the stable compartment structure because of channel morphology, and when sepiocite was added into the other media material, affirmation can effectively improve the thermophysical property to this material.
Industrial utilization property
As stated; Varient sepiocite compound according to layered double hydroxide of the present invention; Has the similar crystalline texture of channel-style crystalline texture that module and tunnel with sepiolite intersect with crystallographic axes; Because of the specific surface area and the porousness of broad, its thermophysical property is improved, and can be used for a plurality of Application Areass of sepiolites such as thermo-stabilizer, ignition dope, sorbent material, filtration, spandex, weighting agent, catalyzer, discoloring agent manufacturing and layered double hydroxide.
More than the specific part of content of the present invention is specified, for those of ordinary skill in the art, this concrete technology is merely preferred embodiment, does not limit protection scope of the present invention with this.Real protection scope of the present invention should by appended claim with and equivalent define.
Claims (10)
1. Ou Saite sepiocite compound is warded off in the varient west of a layered double hydroxide, it is characterized in that, is represented by following Chemical formula 1, has the channel-style structure that module and tunnel intersect with crystallographic axes,
Chemical formula 1
[M(II)
1-xM(III)
xO
a/b(OH)
2-a(A)
X/n]·yH
2O
Wherein, M (II) is the divalent metallic cation;
M (III) is 3 valency metallic cations;
A is and the negatively charged ion chemistry species of hydroxide layer covalent bonds that n is a charge number;
X is less than 0.5 number more than or equal to 0.1;
A is less than 2 number greater than 0;
B is greater than 0 number less than a; And
Y is the real number greater than 0.
2. the Ou Saite compound is warded off in west as claimed in claim 1, it is characterized in that, compares the double-deck oxyhydroxide in laminated metal, and said compound has big 3 to 4 times specific surface area.
3. the Ou Saite compound is warded off in west as claimed in claim 1, it is characterized in that, compares layered metal bi oxyhydroxide, and said compound dehydroxylation reaction takes place exceeding under 30 ℃ to 40 ℃ the temperature.
4. ward off the Ou Saite compound like each the described west in the claim 1 to 3, it is characterized in that, said divalent metallic cation is selected from by Mg
2+, Ca
2+, Co
2+, Cu
2+, Ni
2+Perhaps Zn
2+The crowd who forms, said 3 valency metallic cations are selected from by Al
3+, Cr
3+, Fe
3+, Ga
3+, In
3+, V
3+Perhaps Ti
3+The crowd who forms, said negatively charged ion is selected from by CO
3 2-, NO
3-, Cl-, OH-, O
2-, or SO
4 2-The crowd who forms.
5. the Ou Saite compound is warded off in west as claimed in claim 1, it is characterized in that, said compound is by 3 expressions of following chemical formula,
Chemical formula 3
[Mg
1-xAl
xO
a/b(OH)
2-a(CO
3)
x/2]·yH
2O
Wherein, x is less than 0.5 number more than or equal to 0.1;
A is less than 2 number greater than 0;
B is greater than 0 number less than a; And
Y is the real number greater than 0.
6. one kind prepares the method that the Ou Saite compound is warded off in west as claimed in claim 1, comprising:
(a) under 265 ℃ to 275 ℃ conditions, layered double hydroxide is heat-treated, prepare the step of the layered double hydroxide of partially dehydroxylatedization; And
(b) layered double hydroxide with said partially dehydroxylatedization carries out hydration reaction, and preparation has the step of the sepiocite compound of channel architecture.
7. the preparation method of Ou Saite compound is warded off in west as claimed in claim 6, it is characterized in that, layered double-metal hydroxide is for to be represented by following Chemical formula 2,
Chemical formula 2
[M(II)
1-xM(III)
x(OH)
2]
X+[A
n-]
X/n·yH
2O
Wherein, M (II) is the divalent metallic cation;
M (III) is 3 valency metallic cations;
A is negatively charged ion chemistry species, and n is the anionic charge number;
X is less than 0.5 number more than or equal to 0.1; And
Y is the real number greater than 0.
8. the preparation method of Ou Saite compound is warded off in west as claimed in claim 6, it is characterized in that, layered double hydroxide is deposited in the gas phase that contains moisture or water-soluble solvent and carries out said hydration reaction.
9. the preparation method of layered double hydroxide as claimed in claim 6 is characterized in that, comprising:
(a) in the aqueous solution that contains divalent metal-salt and 3 valency metal-salts, drip the alkali aqueous solution, prepare the step of sedimentary bedded salt metal hydroxides xln; And
(b) the bedded salt metal hydroxides xln that in said (a) step, prepares is through the step of the synthetic preparation of hydro-thermal layered metal hydroxides.
10. the preparation method of layered double hydroxide as claimed in claim 9 is characterized in that, said divalent metal is a magnesium salts, and said 3 valency metals are aluminium salt.
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| KR1020090101779A KR101130282B1 (en) | 2009-10-26 | 2009-10-26 | Sepiocite Compound derived from Layered Double Hydroxide and Method for Preparing the Same |
| PCT/KR2010/007057 WO2011052917A2 (en) | 2009-10-26 | 2010-10-14 | Layered double hydroxide variant sepiolite compound, and method for preparing same |
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| CN115466519B (en) * | 2022-10-19 | 2023-06-02 | 浙江理工大学 | Keratin synergistic layered double hydroxide nano flame retardant and preparation method thereof |
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| CN102712492B (en) | 2014-04-02 |
| WO2011052917A2 (en) | 2011-05-05 |
| KR20110045282A (en) | 2011-05-04 |
| KR101130282B1 (en) | 2012-03-26 |
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