CN102674384B - Hydrotalcite like compound-kaolin composite material and preparation method thereof - Google Patents
Hydrotalcite like compound-kaolin composite material and preparation method thereof Download PDFInfo
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- CN102674384B CN102674384B CN201110064457.5A CN201110064457A CN102674384B CN 102674384 B CN102674384 B CN 102674384B CN 201110064457 A CN201110064457 A CN 201110064457A CN 102674384 B CN102674384 B CN 102674384B
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- kaolin
- houghite
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- hydrotalcite
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Abstract
The invention discloses a hydrotalcite like compound-kaolin composite material which comprises a hydrotalcite like compound sheet and a kaolin substrate. The hydrotalcite like compound sheet grows on the kaolin substrate, an angle between the hydrotalcite like compound sheet and the the kaolin substrate is larger than 0 and smaller than 180 degrees. The invention further discloses a preparation method of the hydrotalcite like compound-kaolin composite material. The preparation method comprises the following steps of (1) conducting pretreatment on the kaolin substrate, and enabling kaolin raw materials or microballoons molded by atomizing to rise at temperature until a high temperature condition to roast; (2) enabling urea and soluble bivalence inorganic salt to be soluble in deionized water, adding the kaolin obtained in the step (1), stirring for warming crystallization at room temperature, using the deionized water to wash, then filtering, and drying to obtain the hydrotalcite like compound-kaolin composite material. The preparation method of the hydrotalcite like compound-kaolin composite material is simple in operation and soft in condition and has wide application prospect. The hydrotalcite like compound sheet in the hydrotalcite like compound-kaolin composite material prepared by using the preparation method has the advantages of being good in orientation, not easy to drop and the like.
Description
Technical field
The present invention relates to negatively charged ion stratiform structure function material technology field, be specifically related to a kind of houghite-kaolin composite material and preparation method thereof.
Background technology
Houghite (Hydrotalcite-like Compound) is a kind of anionic inorganic stratified material, and its crystal belongs to hexagonal system, and it is by positively charged layers of metal hydroxides plate and the negatively charged ion and the neutral water molecular composition that are filled in interlayer.Its chemical general formula:
, wherein
with
be to lay respectively at divalence on laminate and the metallic cation of trivalent, x is
amount of substance mark, A
n-for interlayer anion, m represents interlayer crystallization water number.Metallic cation in houghite laminate can be by other close metallic cation isomorphous substitution of radius with it, and interlayer anion also can be by other anionresin, therefore houghite material has adjustable sex change largely.Houghite material makes it in fields such as catalysis, fractionation by adsorption, photoelectromagnetism materials, be widely used because of its unique structure and character.
The houghite thin slice of synthetic vertical matrix growth has been reported, at document (1) Adv.Mater., 2006, in 18:3089-3093, Duan Xue etc. are used in-situ crystallization method, and utilizing the aluminium flake through anodic oxidation treatment is matrix, and provide aluminium source by matrix, use ammoniacal liquor as pH adjusting agent, synthesize the nitrate radical intercalation nickel aluminum hydrotalcite perpendicular to matrix growth, find that this material has ultra-hydrophobicity.
At document (2) Chemical Engineering Science, 2007, in 62:6069-6075, the polystyrene that Duan Xue etc. are used surface to process through sulfonation is matrix, use urea to regulate pH to synthesize the magnesium aluminum-hydrotalcite of vertical matrix growth, and dynamic process and the synthesis condition of growth are studied in detail.
At document (3) Chemical Engineering Science; 2008; in 63:4055-4062; it is matrix that Duan Xue etc. utilize the aluminium flake through anodic oxidation treatment; and by matrix, provide aluminium source, use ammoniacal liquor as pH adjusting agent, synthesize the carbonate Intercalated perpendicular to matrix growth; the method rehydrated by roasting under nitrogen protection activates, and investigated its catalytic performance in aldol reaction.
At document (4) Ind.Eng.Chem.Res., 2009, in 48:10864-10869, it is matrix that Duan Xue etc. utilize the aluminium flake through anodic oxidation treatment, and by matrix, provide aluminium source, use urea as pH adjusting agent, synthesize the carbonate Intercalated perpendicular to matrix growth, the Al-Mg composite metal oxide thin slice generating after high-temperature roasting still can keep the pattern perpendicular to matrix, and finds that this material has lower specific inductivity.
The present invention proposes to use kaolin for matrix, and by original position synthetic technology, in the synthetic houghite-kaolin composite material obtaining, houghite thin slice grows in kaolin matrix surface, and angle is between the two for being greater than 0 degree and being less than 180 degree.Preparation method of the present invention is simple to operate, and mild condition, for providing a kind of new thinking at kaolin surface in situ synthesis hydrotalcite-like material material, has wider application prospect.
The invention provides a kind of houghite-kaolin composite material, innovation ground is using kaolin as matrix, overcome in the past in in-situ crystallization houghite material that hydrotalcite crystal orientation is poor, the easy technological deficiency such as come off, both kept kaolinic high strength, and made again hydrotalcite be combined firmly difficult drop-off with kaolin.Meanwhile, be different from same type of material in prior art, the angled growth in kaolin matrix of the houghite thin slice in houghite-kaolin composite material of the present invention, rather than simply wrap up or physical mixed, pattern is rule comparatively.In the preparation method of houghite-kaolin composite material of the present invention, take kaolin as matrix, houghite thin slice is angled to be grown in kaolin matrix, not parallel mutually, uses activated kaolin as matrix and unique aluminium source original position synthesis hydrotalcite-like material-kaolin composite material.The advantages such as that preparation method of the present invention has is simple to operate, mild condition.
Summary of the invention
The present invention proposes a kind of houghite-kaolin composite material, it is characterized in that, comprise houghite thin slice and kaolin matrix; Wherein, described houghite thin slice grows in described kaolin matrix, and angle is between the two for being greater than 0 degree and being less than 180 degree.
In the present invention, described houghite thin slice can be vertical and grow in kaolin matrix, and angle [alpha] is between the two 90 degree or approaches 90 degree.
The present invention also provides a kind of preparation method of described houghite-kaolin composite material, it is characterized in that, described method comprises the following steps successively:
1) kaolin matrix pre-treatment: the former powder of kaolin is warming up to and carries out roasting under hot conditions;
2) urea and solubility divalence inorganic salt are dissolved in deionized water, the described kaolin that adds again step 1) gained, and under room temperature, stir and heat up after crystallization, after deionized water wash, filtration, being dried, obtain described houghite-kaolin composite material.
In preparation method of the present invention, the former powder of kaolin described in described step 1) can be made microballoon by spray shaping before intensification, roasting, described microsphere diameter size 20-150 μ m.
In preparation method of the present invention, temperature rise rate 1-10 described in described step 1) ℃/min; Described hot conditions is 500-900 ℃, and the time of described roasting is 1-5h.
The chemical formula of the described solubility divalence inorganic salt in preparation method of the present invention, described step 2)
in,
mg
2+, Zn
2+, Fe
2+, Ni
2+, Ca
2+or Mn
2+, Y is
.Wherein,
mg preferably
2+, Zn
2+or Ni
2+.
In preparation method of the present invention, the mol ratio of the described urea described step 2) and described solubility divalence inorganic salt is 1:1-10, described solubility divalence inorganic salt concentration is 0.0125-1.25M, and described kaolinic dosage is that described deionized water and described kaolinic mass ratio are 1:10-100.
The time of the described stirring in preparation method of the present invention, described step 2) is 15 min-2 h, and described crystallization is carried out 6 h-14 d at 70 ~ 100 ℃, described dry be to carry out at 60-200 ℃.
In houghite-kaolin composite material that the present invention proposes, the angled upright orientation of houghite thin slice is grown on the kaolin matrix surface of activated processing, and the angle between houghite thin slice and kaolin matrix is for being greater than 0 degree and being less than 180 degree.The chemical general formula of houghite thin slice is:
, 0.2≤x≤0.4, m=3-6 is interlayer crystal water molecule number, wherein
represent divalent metal Mg
2+, Zn
2+, Fe
2+, Ni
2+, Ca
2+, Mn
2+in any, preferred Mg
2+, Zn
2+, Ni
2+.In houghite-kaolin composite material of the present invention, the size of houghite thin slice and kaolin matrix, thickness, length can be arbitrarily, unrestricted.
The present invention also provides a kind of preparation method of houghite-kaolin composite material, has an angled upright orientation houghite thin slice the kaolin surface in situ of activated processing is synthetic.Houghite-kaolin composite material that the present invention prepares has overcome in the past in in-situ crystallization houghite material that hydrotalcite crystal orientation is poor, the easy problem such as come off.
The preparation method of houghite-kaolin composite material of the present invention adopts original position synthetic technology, the kaolin that uses activated processing is matrix, the aluminium source that utilizes alukalin to provide hydrotalcite to grow required, by urea, activate the pH value of aluminium source regulation system, thereby synthesize houghite thin slice, have angled upright orientation, hydrotalcite (00
l) angle is greater than 0 degree and is less than 180 degree between crystal face and kaolin matrix, not parallel mutually.
The preparation method of houghite-kaolin composite material of the present invention, concrete steps are as follows:
(1) kaolin matrix pre-treatment: by the former powder of kaolin directly or add microballoon that binding agent spray shaping obtains 20-150 μ m in muffle furnace with 1-10 ℃/min temperature rise rate, appreciate to 500-900 ℃, roasting 1-5h.Described binding agent can be silicon sol, aluminium colloidal sol, colloidal state boehmite or its mixture.
(2) by urea and solubility divalence inorganic salt
by the mol ratio of 1:1-10, be dissolved in deionized water divalent-metal ion M
2+concentration is 0.0125-1.25M, kaolin after the activation of step 1 gained is added in solution with water and kaolinic mass ratio 1:10-100, and stir 15min-2h under room temperature after in 70 ~ 100 ℃ of crystallization 6h-14d, use again deionized water wash 3-5 time, at baking oven 60-200 ℃ temperature, dry 6-24h, to remove excessive moisture, obtains houghite-kaolin composite material.
Wherein, in step (2)
for Mg
2+, Zn
2+, Fe
2+, Ni
2+, Ca
2+, Mn
2+in any, preferred Mg
2+, Zn
2+, Ni
2+, Y is
in any.
The preparation method of houghite-kaolin composite material of the present invention, it is characterized in that, use activated kaolin as matrix and unique aluminium source original position synthesis hydrotalcite-like material-kaolin composite material, product has kept kaolinic high strength, and hydrotalcite is combined firmly difficult drop-off with kaolin, solve the problem that common in-situ crystallization product easily runs off, and houghite thin slice is angled upright orientation growth in kaolin matrix, rather than simply wrap up, pattern is rule comparatively.
Accompanying drawing explanation
Fig. 1 is the structural representation of houghite-kaolin composite material of the present invention.
Fig. 2 is the XRD figure of the former powder of kaolin and pretreated kaolin powder, and a represents the former powder of kaolin; B represents pretreated kaolin powder.
Fig. 3 (a), (b) are XRD figure and the SEM figure of the houghite-kaolin composite material of the present invention of embodiment 1 preparation.
Fig. 4 (a), (b) are XRD figure and the SEM figure of the houghite-kaolin composite material of the present invention of embodiment 2 preparations.
Fig. 5 (a), (b) are XRD figure and the SEM figure of the houghite-kaolin composite material of the present invention of embodiment 3 preparations.
Fig. 6 (a), (b) are XRD figure and the SEM figure of the houghite-kaolin composite material of the present invention of embodiment 4 preparations.
Fig. 7 is the XRD figure of the houghite-kaolin composite material of the present invention of embodiment 5 preparations.
Fig. 8 (a), (b) are XRD figure and the SEM figure of the houghite-kaolin composite material of the present invention of embodiment 6 preparations.
Fig. 9 (a), (b) are XRD figure and the SEM figure of the houghite-kaolin composite material of the present invention of embodiment 7 preparations.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail.
Fig. 1 is the angled single chip architecture schematic diagram growing on kaolin matrix of houghite thin slice.Houghite-kaolin composite material of the present invention as shown in Figure 1, comprises houghite thin slice 1 and kaolin matrix 2; Wherein, houghite thin slice 1 is angled to be grown in kaolin matrix 2, and the angle [alpha] forming is between the two for being greater than 0 degree and being less than 180 degree.Houghite thin slice 1 can be vertical and grow between kaolin matrix 2, and angle [alpha] is between the two 90 degree or approaches 90 degree.Matrix material of the present invention is as Fig. 3 (b), 4(b), 5(b), 6(b), 8(b), 9(b) as shown in, the angle [alpha] between houghite thin slice and kaolin matrix can be any number within the scope of 0-180 degree.Angle [alpha] between houghite thin slice and kaolin matrix is not equal to 0 degree or 180 degree, is not parallel to each other mutually between the two.
Embodiment 1:
(1) kaolin matrix pre-treatment: by the former powder of kaolin in muffle furnace with 1 ℃/min temperature rise rate, be warming up to 830 ℃ of roasting 2 h, before and after processing, sample is shown in Fig. 2 through XRD characterization result, in Fig. 2, (a) represents the XRD figure of the former powder of kaolin; (b) represent the XRD figure of pretreated kaolin powder.
(2) claim 1.017 g MgCl
26H
2o and 3.003g urea are dissolved in 20 g deionized waters, add the pretreated kaolin of 1 g, stir 30 min, be incorporated with the spontaneous pressure crystallizing kettle of stainless steel of polytetrafluoro liner, in 80 ℃ of crystallization 1 day, reaction finish rear with deionized water wash 3-5 all over and filter, put into 80 ℃ of oven dryings.
In houghite-kaolin composite material that the present embodiment prepares, the XRD of houghite thin slice and SEM characterization result are as shown in Fig. 3 (a), Fig. 3 (b).
Embodiment 2:
(1) according to the method for using in example 1, kaolin matrix is carried out to pre-treatment.
(2) claim 1.017 g MgCl
26H
2o and 1.802 g urea are dissolved in 20 g deionized waters, add the pretreated kaolin of 1 g, stir 15 min, and in 70 ℃ of crystallization 7 days, reaction finished rear with deionized water wash and filter, dry in 80 ℃.
In houghite-kaolin composite material that the present embodiment prepares, the XRD of houghite thin slice and SEM characterization result are as shown in Fig. 4 (a), Fig. 4 (b).
Embodiment 3:
(1) according to the method for using in example 1, kaolin matrix is carried out to pre-treatment.
(2) claim 0.509 g MgCl
26H
2o and 0.903 g urea are dissolved in 20 g deionized waters, add the pretreated kaolin of 1 g, stir 30 min, and in 100 ℃ of crystallization 16 h, reaction finishes rear with deionized water wash filtration, dry in 100 ℃.
In houghite-kaolin composite material that the present embodiment prepares, the XRD of houghite thin slice and SEM characterization result are as shown in Fig. 5 (a), Fig. 5 (b).
Embodiment 4:
(1) kaolin matrix pre-treatment: the former powder of kaolin is heated up with 10 ℃/min temperature rise rate, to 900 ℃ of roasting 2h.
(2) claim 1.016 g MgCl
26H
2o and 0.300 g urea are dissolved in 100 g deionized waters, add the pretreated kaolin of 1 g, stir 30 min, be incorporated with the spontaneous pressure crystallizing kettle of stainless steel of polytetrafluoro liner, 90 ℃ of crystallization 1 d, reaction finishes rear with deionized water wash filtration, dry in 60 ℃.
In houghite-kaolin composite material that the present embodiment prepares, the XRD of houghite thin slice and SEM characterization result are as shown in Fig. 6 (a), Fig. 6 (b).
Embodiment 5:
(1) according to the method for using in example 4, kaolin matrix is carried out to pre-treatment.
(2) claim 1.524 g MgCl
26H
2o and 2.702 g urea are dissolved in 20 g deionized waters, add the pretreated kaolin of 1 g, stir 30 min, and in 80 ℃ of crystallization 2 d, reaction finishes rear with deionized water wash filtration, dry in 120 ℃.
In houghite-kaolin composite material that the present embodiment prepares, the XRD characterization result of houghite thin slice as shown in Figure 7.
Embodiment 6:
(1) kaolin matrix pre-treatment: by former powder 2000 g of kaolin, water glass 4%, to add chemical water to be prepared into kaolin solid content be 42% mixed serum, spraying is dry obtains 1840 g particle diameters at the kaolin spray shaping microballoon of 20-110 μ m.Kaolin spray shaping microballoon, with 5 ℃/min temperature rise rate, is warming up to 550 ℃ of roasting 2 h.
(2) claim 5.128 g Mg (NO
3)
26H
2o and 12.012 g urea are dissolved in 80 g deionized waters, add the pretreated kaolin microsphere of 4 g, stir 60min, and in 80 ℃ of crystallization 1 d, reaction finishes rear with deionized water wash filtration, dry in 100 ℃.
In houghite-kaolin composite material that the present embodiment prepares, the XRD of houghite thin slice and SEM characterization result are as shown in Fig. 8 (a), Fig. 8 (b).
Embodiment 7:
(1) according to the method for using in example 6, kaolin matrix is carried out to pre-treatment.
(2) claim 2.038 g MgCl
26H
2o and 3.604 g urea are dissolved in 20 g deionized waters, add the pretreated kaolin microsphere of 2 g, stir 30 min, and in 70 ℃ of crystallization 7 d, reaction finishes rear with deionized water wash filtration, dry in 100 ℃.
In houghite-kaolin composite material that the present embodiment prepares, the XRD of houghite thin slice and SEM characterization result are as shown in Fig. 9 (a), Fig. 9 (b).
Embodiment 8:
(1) according to the method for using in example 6, kaolin matrix is carried out to pre-treatment.
(2) claim 1.5 g Zn (NO
3)
26H
2o and 7.2 g urea are dissolved in 20 g deionized waters, add the pretreated kaolin microsphere of 2 g, stir 2 h, and in 70 ℃ of crystallization 14 d, reaction finishes rear with deionized water wash filtration, dry in 100 ℃.
In houghite-kaolin composite material that the present embodiment prepares, the XRD of houghite thin slice and SEM characterization result and Fig. 7 are similar.
Houghite-kaolin composite material of the present invention is compared with prior art same type of material, have houghite thin slice angularly vertical growth in kaolin matrix, expose more active sites, be also conducive to construct the open advantages such as pore structure.In preparation method of the present invention, use urea but not NaOH and/or sodium carbonate etc. as precipitation agent, thereby realize the vertical-growth of houghite thin slice in kaolin matrix.Preparation method of the present invention adopts the chemical formula M of solubility divalence inorganic salt
2+y, wherein,
mg
2+, Zn
2+, Fe
2+, Ni
2+, Ca
2+or Mn
2+, Y is NO
3 -, Cl
-, Br
-, F
-.Houghite thin slice in houghite-kaolin composite material that the present invention prepares XRD and the result of SEM characterization result and above-described embodiment similar.Protection content of the present invention is not limited to above-described embodiment.Do not deviating under the spirit and scope of inventive concept, variation and advantage that those skilled in the art can expect are all included in the present invention, and take appending claims as protection domain.
Claims (7)
1. a preparation method for houghite-kaolin composite material, is characterized in that, described method comprises the following steps successively:
1) kaolin matrix pre-treatment: the former powder of kaolin is warming up to and carries out roasting under hot conditions;
2) urea and solubility divalence inorganic salt are dissolved in deionized water, the described kaolin that adds again step 1) gained, and under room temperature, stir and heat up after crystallization, after deionized water wash, filtration, being dried, obtain described houghite-kaolin composite material;
In described houghite-kaolin composite material, houghite thin slice grows in described kaolin matrix, and angle is between the two for being greater than 0 degree and being less than 180 degree; Described houghite thin slice can be vertical and grow in described kaolin matrix, and angle [alpha] is between the two 90 degree or approaches 90 degree.
2. preparation method as claimed in claim 1, is characterized in that, the former powder of kaolin described in described step 1) was made microballoon by spray shaping before intensification, roasting, described microsphere diameter size 20-150 μ m.
3. preparation method as claimed in claim 1, is characterized in that, the temperature rise rate 1-10 in described step 1) ℃/min; Described hot conditions is 500-900 ℃, and the time of described roasting is 1-5h.
4. preparation method as claimed in claim 1, is characterized in that, described step 2) in the chemical formula M of described solubility divalence inorganic salt
2+y
2in, M
2+mg
2+, Zn
2+, Fe
2+, Ni
2+, Ca
2+or Mn
2+, Y
2for NO
3 -, Cl
-, Br
-, F
-.
5. preparation method as claimed in claim 4, is characterized in that, the chemical formula M of described solubility divalence inorganic salt
2+in Y, M
2+mg
2+, Zn
2+or Ni
2+.
6. preparation method as claimed in claim 1, it is characterized in that, the mol ratio of the described urea described step 2) and described solubility divalence inorganic salt is 1:1-10, described solubility divalence inorganic salt concentration is 0.0125-1.25M, and described kaolinic dosage is that described deionized water and described kaolinic mass ratio are 1:10-100.
7. preparation method as claimed in claim 1, is characterized in that, described step 2) in time of described stirring be 15min-2h, described crystallization is carried out 6h-14d at 70～100 ℃, described dry be to carry out at 60-200 ℃.
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| Title |
|---|
| Mg-Fe-HTlc/高岭土悬浮体流变性研究;戴肖南等;《化学学报》;20051231;第63卷(第8期);1 实验部分 * |
| 戴肖南等.Mg-Fe-HTlc/高岭土悬浮体流变性研究.《化学学报》.2005,第63卷(第8期),1 实验部分. |
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