CN106745118A - A kind of magnalium hydrotalcite and the method for preparing magnalium hydrotalcite - Google Patents
A kind of magnalium hydrotalcite and the method for preparing magnalium hydrotalcite Download PDFInfo
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- CN106745118A CN106745118A CN201611262309.3A CN201611262309A CN106745118A CN 106745118 A CN106745118 A CN 106745118A CN 201611262309 A CN201611262309 A CN 201611262309A CN 106745118 A CN106745118 A CN 106745118A
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- 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
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08K9/00—Use of pretreated ingredients
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The present invention relates to hydrotalcite field, disclose a kind of magnalium hydrotalcite and prepare the method for magnalium hydrotalcite, wherein, methods described includes：(1) in the presence of water, magnesium source and/or aluminium hydroxide are carried out into ball milling, obtains sol precursor；(2) sol precursor is diluted with water, the solution obtained after dilution is mixed with magnesium source and aluminium hydroxide, the mixture that then will be obtained is contacted with acidic materials, 10 300min are incubated at 30 90 DEG C, obtain Mg-Al composite colloidal sol；(3) under hydrothermal reaction condition, the Mg-Al composite colloidal sol is contacted with chemical additives, obtains magnalium hydrotalcite slurry；(4) by the magnalium hydrotalcite slurry and surface modifier haptoreaction.The method of the invention process is simple, low cost, and the crystallinity of magnalium hydrotalcite can be improved.
Description
Technical field
The present invention relates to hydrotalcite field, in particular it relates to a kind of magnalium hydrotalcite and the method for preparing magnalium hydrotalcite.
Background technology
Hydrotalcite is a kind of layer column double-metal hydroxide, is the anionic clay that a class quickly grows in recent years.
Hydrotalcite has special structure and physicochemical properties, such as alkaline, powered property, anion interchangeability, microcellular structure, heat
Stability, memory effectiveness, absorption property, catalytic performance etc., in plastics, the fire retardant of elastomeric polymeric material, thermal stabilizer, catalysis
Numerous necks such as agent, catalyst carrier, insecticide, sewage-treating agent, electric rheology control agent, medicine, medical carrier and petroleum industry
Domain has a wide range of applications.Magnalium hydrotalcite is a kind of novel multi-effect plastic additive, as fire retardant have concurrently it is fire-retardant, eliminate smoke,
Various functions are filled, is a kind of efficient, Halogen, low cigarette, nontoxic inorganic combustion inhibitor new varieties；As stabilizer, with excellent
Heat endurance, and there is good absorption iris action, thus great exploitation potential to ultraviolet light.
With the continuous extension of hydrotalcite application field, the preparation research of hydrotalcite has also obtained rapid development.Now such as
The preparation method of modern hydrotalcite is still based on coprecipitation, while also hydro-thermal method, sol-gel process, ion-exchange and roasting
Heat reducing process etc..But part is come with some shortcomings in existing hydrotalcite preparation method：Coprecipitation, more using solvable
Property aluminium salt and magnesium salts are as silicon source and magnesium source.In process of production, the sodium salt of low value can be produced, production cost is high, and
It is unfavorable for environmental protection；And sol-gel rule uses the alkoxide compound of metal for source is expected, expensive, hydrolytic process is not allowed
It is easy to control；And substantial amounts of organic solvent is needed to use in process of production, environmental pollution can be caused；Ion-exchange was produced
Journey is more complicated, and raw material requires it is hydrotalcite-like materials in itself, and economic benefit is not high；Roasting thermal reduction needs high temperature
Aquation is stilled need after calciner, and calcining, a certain amount of spinelle impurity is had in final product, product quality is not
It is high.
Hydrothermal synthesis method refers in enclosed system, with water as solvent, at a certain temperature, in the spontaneous pressure of water
Under, a kind of method that reactant mixture is reacted.During Hydrothermal Synthesiss, crystalline phase and crystalline substance can effectively be controlled by HTHP
Particle size, amorphous sediment is converted into the hydrotalcite crystal of high-crystallinity, is commonly used to the slurry prepared to coprecipitation
Carry out hydro-thermal process.The report that magnalium hydrotalcite is directly prepared using hydro-thermal method is also rarely found.
The content of the invention
The purpose of the present invention is to overcome the method complexity for preparing magnalium hydrotalcite of the prior art, high cost, obtain
The defect of magnalium hydrotalcite crystallinity difference, there is provided a kind of magnalium hydrotalcite and the method for preparing magnalium hydrotalcite.
To achieve these goals, the present invention provides a kind of method for preparing magnalium hydrotalcite, wherein, methods described bag
Include：
(1) in the presence of water, magnesium source and/or aluminium hydroxide are carried out into ball milling, obtains sol precursor；
(2) sol precursor is diluted with water, the solution obtained after dilution is mixed with magnesium source and aluminium hydroxide, so
The mixture that will be obtained afterwards is contacted with acidic materials, and 10-300min is incubated at 30-90 DEG C, obtains Mg-Al composite colloidal sol；
(3) under hydrothermal reaction condition, the Mg-Al composite colloidal sol is contacted with chemical additives, obtains magnalium hydrotalcite
Slurry；
(4) by the magnalium hydrotalcite slurry and surface modifier haptoreaction.
Present invention also offers the magnalium hydrotalcite prepared by method of the present invention.
Compared with prior art, the present invention is with advantages below：
(1) it is magnesium source with the mineral of cheap magnesium, with industrial aluminium hydroxide as silicon source, source material wide material sources, valency
Lattice are cheap, so as to substantially reduce production cost；
(2) by adding sol precursor and acidic materials, promote to form Mg-Al composite colloidal sol, increased insoluble magnesium source
With the contact area of silicon source, reduce reaction barrier therebetween, accelerate the carrying out of reaction；
(3) chemical additives are added so that certain CO is kept in course of reaction3 2-Concentration, promotes magnalium hydrotalcite crystal grain
Growth；Simultaneously use hydro-thermal method, so as to get magnalium hydrotalcite crystallinity it is high；
(4) waste water in preparation process (is for example passed through CO thereto through carbonization2Gas) after can recycle, it is whole raw
Product process is environment friendly and pollution-free, and the present invention can be used for industrialized production, high financial profit.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the XRD of embodiment 1；
Fig. 2 is the XRD of embodiment 2；
Fig. 3 is the XRD of embodiment 3；
Fig. 4 schemes for the DSC-TG of embodiment 3；
Fig. 5 is the XRD of comparative example 1；
Fig. 6 is that Mg-Al composite colloidal sol forms schematic diagram；
Fig. 7 is magnalium hydrotalcite growth crystallization process schematic.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
One or more can be obtained with combination with one another between the endpoint value of individual scope and single point value, and individually between point value
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of method for preparing magnalium hydrotalcite, wherein, methods described includes：
(1) in the presence of water, magnesium source and/or aluminium hydroxide are carried out into ball milling, obtains sol precursor；
(2) sol precursor is diluted with water, the solution obtained after dilution is mixed with magnesium source and aluminium hydroxide, so
The mixture that will be obtained afterwards is contacted with acidic materials, and 10-300min is incubated at 30-90 DEG C, obtains Mg-Al composite colloidal sol；
(3) under hydrothermal reaction condition, the Mg-Al composite colloidal sol is contacted with chemical additives, obtains magnalium hydrotalcite
Slurry；
(4) by the magnalium hydrotalcite slurry and surface modifier haptoreaction.
In the present invention, in step (1), the consumption of water is 0.5-20 with the weight ratio of magnesium source and total consumption of aluminium hydroxide：
1, preferably 3-10：1.
In the present invention, in step (1), there is no particular limitation for the consumption of consumption and aluminium hydroxide to the magnesium source, institute
The consumption of the consumption and aluminium hydroxide of stating magnesium source can be arbitrary proportion.
In the present invention, the ball milling can be implemented by the conventional means in this area, for example, can implement in ball mill,
It is preferred that the condition of the ball milling includes：Rotating speed is 50-1500r/min, and the time is 0.5-4h.
In the present invention, it is preferable that in step (2), the consumption in the magnesium source causes to account for institute from the magnesium in sol precursor
State the 0-50 weight % of the total magnesium amount in Mg-Al composite colloidal sol, more preferably preferably 0-20 weight %, 3-15 weight %.
In the present invention, it is preferable that in step (2), the consumption of aluminium hydroxide causes the hydrogen-oxygen formed in Mg-Al composite colloidal sol
The mol ratio for changing the content of the aluminium hydroxide in content and the Mg-Al composite colloidal sol of magnesium is 1-5：1, preferably 1-4, enter one
Step is preferably 1.5-3：1.
In the present invention, it is preferable that in step (2), magnesium source in the consumption of the acidic materials and the mixture contains
The weight ratio of amount is 0-0.2：1, preferably 0.1-0.2：1；Under the preferable case, so as to get the pH of Mg-Al composite colloidal sol be
3-5。
In the present invention, to the selection of the acidic materials, there is no particular limitation, preferable case, and the acidic materials are second
One or more in acid, oxalic acid, hydrochloric acid, carbonic acid, sulfuric acid, nitric acid and phosphoric acid, more preferably in acetic acid, oxalic acid and hydrochloric acid
One or more.
In the presence of above-mentioned sol precursor and acidic materials, the larger aluminium hydroxide of particle and magnesium source form particle
The complex sol that small, specific surface area is high, surface-active is big, as shown in fig. 6, forming aluminium hydroxide and magnesium after Mg-Al composite colloidal sol
Source makes the energy barrier reduction reacted in course of reaction, the surface for contacting with each other become big, so as to accelerate the hydro-thermal reaction of step (3)
Carry out.
In the present invention, in step (2), to the degree of the dilution, there is no particular limitation, under preferable case, the dilution
Process cause that the sol precursor dilutes 10-20 times of volume.
In the present invention, the magnesium source in step (1) and step (2) is identical or different, it is preferable that the magnesium source is active oxidation
One or more in magnesium, magnesite and shepardite.The magnesium source is cheap, wide material sources, can substantially reduce production cost.
In the present invention, to the selection of the aluminium hydroxide, there is no particular limitation, in order to further reduce production cost, institute
It can be industrial aluminium hydroxide of metallurgical grade to state aluminium hydroxide.
In the present invention, it is preferable that the hydrothermal reaction condition includes：Temperature is 80-300 DEG C, preferably 120-220 DEG C；
Pressure is 0.2-2.5MPa, preferably 0.5-2MPa；Time is 0.5-50h, preferably 2-30h.Under the hydrothermal reaction condition,
The Mg-Al composite colloidal sol can firstly generate the magnesium hydroxide multi-layer sheet structure of aluminium atom intercalation, due to the presence of aluminium, hydroxide
There is charge unbalance, the anion in such magnesium hydroxide synusia meeting adsorption reaction system, such as CO on magnesium synusia3 2-, most end form
Into the structure of multilayer tablet superposition as shown in Figure 7.In course of reaction, the feed particles for not forming colloidal sol can be carried constantly
The hydrotalcite synusia to be formed is set constantly to grow up until feed particles consumption is complete with aluminium ion for magnesium ion.
In the present invention, it is preferable that in step (3), in the consumption of the chemical additives and the Mg-Al composite colloidal sol
The weight ratio of the total content of aluminium hydroxide is 0.1-10：1, preferably 0.25-3：1.
In the present invention, the chemical additives are preferably NaHCO3、Na2CO3, urea, oxalic acid, Na2C2O4、CO2, grape
One or more in sugar, citric acid, acetic acid and sodium acetate, more preferably NaHCO3、Na2CO3, in oxalic acid and acetic acid
One or more, more preferably NaHCO3And/or Na2CO3.The chemical additives cause the hydro-thermal reaction system in HCO3 -
With CO3 2-Carried out in buffer solution system, so that CO3 2-Concentration be held essentially constant.The CO being basically unchanged3 2-Concentration be
The growth of magnalium hydrotalcite crystal interlayer provides reliable guarantee, promotes hydrotalcite synusia to be overlapped mutually, so as to form crystallization
Degree magnalium hydrotalcite high.
In the present invention, methods described also includes：Magnalium hydrotalcite slurries filtration, washing and the slurrying that step (3) is obtained
Carry out step (4) again afterwards.The process of the filtering, washing and slurrying causes that the pH value of the magnalium hydrotalcite slurry is 7-8.
In the present invention, in step (4), by the magnalium hydrotalcite slurry and the catalytic purpose of surface modifier be by
The surface of magnalium hydrotalcite carries out hydrophobic modification so that the surface polarity reduction of magnalium hydrotalcite, can improve magnalium neatly
Stone and the compatibility of macromolecular material, prevent the reunion between hydrotalcite particle.
In the present invention, the consumption of the surface modifier is preferably the 0.1-6 weights of the consumption of the magnalium hydrotalcite slurry
Amount %, more preferably 2-4 weight %.
In the present invention, to the selection of the surface modifier, there is no particular limitation, can be the conventional selection of ability, excellent
Selection of land, the surface modifier is one or more in stearic acid, silane coupler and laurate.
In the present invention, to the catalytic condition in step (4), there is no particular limitation, but, in order to promote surface
Modified effect, it is preferable that in step (4), the catalytic condition includes：Temperature be 20-95 DEG C, the time be more than
10min。
In the present invention, in order to obtain magnalium hydrotalcite powder, it is preferable that by what is obtained after step (4) surface modification reaction
Material is filtered, dried and crushed.
In the present invention, in order to further reduce production cost, and environmental pollution is avoided, under preferable case, by the filtering
The waste water carbonization Posterior circle for obtaining afterwards is used.
Present invention also offers the magnalium hydrotalcite prepared by method of the present invention.The magnalium hydrotalcite tool
There is crystallinity higher.
Below will the present invention will be described in detail by embodiment.In following examples and comparative example,
The particle diameter D50 of magnalium hydrotalcite is determined by the laser particle size analyzers of APA 2000 of Malvern companies；
The full-automatic quick specific surfaces of ASAP S2460 that the specific surface area of magnalium hydrotalcite passes through Micromeritics companies
Determined with lacunarity analysis instrument；
The XRD of magnalium hydrotalcite is surveyed by the TD-3500X x ray diffractometer xs of the sensible Science and Technology Co., Ltd. in Dandong
It is fixed；
The heat analysis DSC-TG figures of magnalium hydrotalcite are surveyed by 449 differential thermals of the STA-thermogravimetric analyzer of Metzsch companies
It is fixed；
The crystallinity of magnalium hydrotalcite is calculated by being fitted the method for crystal peak area in XRD, its computing formula
It is as follows：
η=Sc/S0
Wherein, η is crystallinity；
ScIt is the peak area of magnalium hydrotalcite in XRD；
S0It is peak area total in XRD.
Embodiment 1
(1) sol precursor is prepared
50g activated magnesias (being 90 purchased from Haicheng City Hua Sheng Refractory Co., ltds trade mark, similarly hereinafter) are added to ball milling
In tank, 500ml water is added, by ball mill with 800r/min rotating speed ball milling 2h, obtain sol precursor；
(2) Mg-Al composite colloidal sol is prepared
100ml sol precursors are taken, 2L is diluted with water to, 150g magnesite is added thereto to (purchased from the sage's fire resisting of Haicheng City China
Materials Co., Ltd's trade mark is 40-70, similarly hereinafter) and 60g aluminium hydroxides (purchased from the Luoyang Zhong Chao new materials limited company trade mark
It is AH-01DG, similarly hereinafter)；5g acetic acid+3g oxalic acid is added thereto to after stirring, at 80 DEG C be incubated 30min obtain magnalium answer
Close colloidal sol.The pH value of Mg-Al composite colloidal sol is 4.3；
(3) hydro-thermal method prepares magnalium hydrotalcite slurry
The Mg-Al composite colloidal sol that step (2) is obtained is added in autoclave (pressure is 1.3MPa), and thereto
Add 54g NaHCO3With 30g oxalic acid, in 180 DEG C of hydro-thermal reaction 6h, pH=7.5 magnaliums are obtained after filtering, washing and slurrying
Hydrotalcite slurry；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) is obtained is put into water-bath, 4g laurate is added thereto to, at 85 DEG C
Insulation 2h, is carried out surface-hydrophobicized modified.Then magnalium hydrotalcite powder will be obtained after modified slurry filtration, drying, crushing
Body.D50=6.997 μm of the magnalium hydrotalcite, specific surface area is 22.4m2/ g, crystallinity is 98%.XRD as shown in Figure 1
Figure will also realize that the hydrotalcite crystallinity is good.
Embodiment 2
(1) sol precursor is prepared
50g activated magnesias are added in ball grinder, 150ml water are added, by ball mill with 800r/min rotating speed balls
Mill 2h, obtains sol precursor.
(2) Mg-Al composite colloidal sol is prepared
Take 100ml sol precursors and be diluted with water to 2L, be added thereto to 100g magnesite, 30g activated magnesias and 60g
Aluminium hydroxide；It is the nitric acid of 3mol/L that 5g oxalic acid and 2ml concentration are added thereto to after stirring, and 300min is incubated at 30 DEG C
Obtain Mg-Al composite colloidal sol.The pH value of Mg-Al composite colloidal sol is 3.8；
(3) hydro-thermal method prepares magnalium hydrotalcite slurry
The Mg-Al composite colloidal sol that step (2) is obtained is added in autoclave (pressure is 2MPa), and is added thereto
Enter 54g Na2CO3With 30g sodium acetates, in 220 DEG C of hydro-thermal reaction 2h, pH=7.7 magnalium water is obtained after filtering, washing and slurrying
Talcum slurry；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) is obtained is put into water-bath, 2g laurate and 2g stearic acid is added thereto to,
2h is incubated at 95 DEG C, is carried out surface-hydrophobicized modified.Then magnalium will be obtained after modified slurry filtration, drying, crushing
Hydrotalcite powder.D50=4.836 μm of the magnalium hydrotalcite, specific surface area is 15.3m2/ g, crystallinity is 97%.By Fig. 2 institutes
The XRD for showing will also realize that the magnalium hydrotalcite crystallinity is good.
Embodiment 3
(1) sol precursor is prepared
30g activated magnesias and 20g aluminium hydroxides are added in ball grinder, add 250ml water, by ball mill with
800r/min rotating speed ball milling 2h, obtain sol precursor.
(2) Mg-Al composite colloidal sol is prepared
Take 100ml sol precursors and be diluted with water to 2L, be added thereto to 150g magnesite and 60g aluminium hydroxides；Stirring
Hydrochloric acid and 3g oxalic acid that 2ml concentration is 3mol/L are added thereto to after uniform, 60min is incubated at 50 DEG C, and to obtain Mg-Al composite molten
Glue.The pH value of Mg-Al composite colloidal sol is 4.3.
(3) hydro-thermal method prepares magnalium hydrotalcite slurry
The Mg-Al composite colloidal sol that step (2) is obtained is added in autoclave (pressure is 0.5MPa), and thereto
65g oxalic acid and 20g citric acids are added, in 150 DEG C of hydro-thermal reaction 30h, the magnesium of pH=7.2 is obtained after filtering, washing and slurrying
Aluminum hydrotalcite slurry.
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) is obtained is put into water-bath, 2g laurate and 2g ethene is added thereto to
Base trimethoxy silane (being YDH-171 purchased from the Hubei Ming Tai Chemical Co., Ltd.s trade mark), 3h is incubated at 20 DEG C, carries out surface
Hydrophobic modification.Then magnalium hydrotalcite powder will be obtained after modified slurry filtration, drying, crushing.The magnalium hydrotalcite
D50=2.827 μm, specific surface area is 18.6m2/ g, crystallinity is 95%.XRD as shown in Figure 3 will also realize that, the magnalium
Hydrotalcite crystallinity is good；DSC-TG figures as shown in Figure 4 understand that the magnalium hydrotalcite can absorb substantial amounts of when being thermally decomposed
Heat, illustrates that the magnalium hydrotalcite also has preferable anti-flammability and heat endurance.
Embodiment 4
Method according to embodiment 1 prepares magnalium hydrotalcite, unlike, it is not added with sol precursor.Specially：
(1) Mg-Al composite colloidal sol is prepared
10g activated magnesias, 150g magnesite and 60g aluminium hydroxides are taken, add water 2L after mixing, after stirring thereto
5g acetic acid+3g oxalic acid is added, 30min is incubated at 80 DEG C and is obtained Mg-Al composite colloidal sol.The pH value of Mg-Al composite colloidal sol is 4.3；
(2) hydro-thermal method prepares magnalium hydrotalcite slurry
The Mg-Al composite colloidal sol that step (1) is obtained is added in autoclave (pressure is 1.3MPa), and thereto
Add 54g NaHCO3With 30g oxalic acid, in 180 DEG C of hydro-thermal reaction 6h, pH=7.5 magnaliums are obtained after filtering, washing and slurrying
Hydrotalcite slurry；
(3) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) is obtained is put into water-bath, 4g laurate is added thereto to, at 85 DEG C
Insulation 2h, is carried out surface-hydrophobicized modified.Then magnalium hydrotalcite powder will be obtained after modified slurry filtration, drying, crushing
Body.D50=5.324 μm of the magnalium hydrotalcite, specific surface area is 24.6m2/ g, crystallinity is 80%.
Embodiment 5
Method according to embodiment 1 prepares magnalium hydrotalcite, unlike, step is not added with acidic materials in (2).Specifically
For：
(1) sol precursor is prepared
50g activated magnesias are added in ball grinder, 500ml water are added, by ball mill with 800r/min rotating speed balls
Mill 2h, obtains sol precursor；
(2) Mg-Al composite colloidal sol is prepared
100ml sol precursors are taken, 2L is diluted with water to, 150g magnesite and 60g aluminium hydroxides is added thereto to；Stirring
After uniform, insulation 30min obtains Mg-Al composite colloidal sol at 80 DEG C.The pH value of Mg-Al composite colloidal sol is 8.2；
(3) hydro-thermal method prepares magnalium hydrotalcite slurry
The Mg-Al composite colloidal sol that step (2) is obtained is added in autoclave (pressure is 1.3MPa), and thereto
Add 54g NaHCO3With 30g oxalic acid, in 180 DEG C of hydro-thermal reaction 6h, pH=7.5 magnaliums are obtained after filtering, washing and slurrying
Hydrotalcite slurry；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) is obtained is put into water-bath, 4g laurate is added thereto to, at 85 DEG C
Insulation 2h, is carried out surface-hydrophobicized modified.Then magnalium hydrotalcite powder will be obtained after modified slurry filtration, drying, crushing
Body.D50=7.328 μm of the magnalium hydrotalcite, specific surface area is 32.5m2/ g, crystallinity is 75%.
Comparative example 1
Method according to embodiment 1 prepares magnalium hydrotalcite, unlike, it is not added with crystal formation in the hydro-thermal reaction of step (3)
Controlling agent.Specially：
(1) sol precursor is prepared
50g activated magnesias are added in ball grinder, 500ml water are added, by ball mill with 800r/min rotating speed balls
Mill 2h, obtains sol precursor；
(2) Mg-Al composite colloidal sol is prepared
100ml sol precursors are taken, 2L is diluted with water to, 150g magnesite and 60g aluminium hydroxides is added thereto to；Stirring
5g acetic acid+3g oxalic acid is added thereto to after uniform, 30min is incubated at 80 DEG C and is obtained Mg-Al composite colloidal sol.Mg-Al composite colloidal sol
PH value be 4.3；
(3) hydro-thermal method prepares magnalium hydrotalcite slurry
The Mg-Al composite colloidal sol that step (2) is obtained is added in autoclave (pressure is 1.3MPa), in 180 DEG C of water
Thermal response 6h, pH=7.3 magnalium hydrotalcite slurries are obtained after filtering, washing and slurrying；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) is obtained is put into water-bath, 4g laurate is added thereto to, at 85 DEG C
Insulation 2h, is carried out surface-hydrophobicized modified.Then magnalium hydrotalcite powder will be obtained after modified slurry filtration, drying, crushing
Body.D50=8.736 μm of the magnalium hydrotalcite, specific surface area is 72.3m2/ g, crystallinity is 23%.XRD as shown in Figure 5
Figure will also realize that the magnalium hydrotalcite crystallinity is simultaneously bad.
Be can be seen that by the result of above example and comparative example can prepare crystallinity using the method for the invention
Magnalium hydrotalcite high.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method for preparing magnalium hydrotalcite, it is characterised in that methods described includes：
(1) in the presence of water, magnesium source and/or aluminium hydroxide are carried out into ball milling, obtains sol precursor；
(2) sol precursor is diluted with water, the solution obtained after dilution is mixed with magnesium source and aluminium hydroxide, then will
The mixture for obtaining is contacted with acidic materials, and 10-300min is incubated at 30-90 DEG C, obtains Mg-Al composite colloidal sol；
(3) under hydrothermal reaction condition, the Mg-Al composite colloidal sol is contacted with chemical additives, obtains magnalium hydrotalcite slurry
Material；
(4) by the magnalium hydrotalcite slurry and surface modifier haptoreaction.
2. method according to claim 1, wherein, in step (1), consumption and magnesium source and total consumption of aluminium hydroxide of water
Weight ratio be 0.5-20：1, preferably 3-10：1.
3. method according to claim 1, wherein, in step (2), the consumption in the magnesium source is caused from sol precursor
In magnesium 0-50 weight %, preferably the 0-20 weight % of total magnesium amount that account in the Mg-Al composite colloidal sol, more preferably
3-15 weight %.
4. the method according to claim 1 or 3, wherein, in step (2), the consumption of aluminium hydroxide causes that Mg-Al composite is molten
The mol ratio of the content of the aluminium hydroxide in content and the Mg-Al composite colloidal sol of the magnesium hydroxide formed in glue is 1-5：1,
Preferably 1.5-3：1.
5. the method according to claim 1 or 3, wherein, in step (2), the consumption of the acidic materials mixes with described
The weight ratio of the content in the magnesium source in thing is 0-0.2：1, preferably 0.1-0.2：1；
Preferably, the acidic materials are one or more in acetic acid, oxalic acid, hydrochloric acid, carbonic acid, sulfuric acid, nitric acid and phosphoric acid；
It is further preferred that the process of the dilution causes that the sol precursor dilutes 10-20 times of volume；
It is highly preferred that the pH of the Mg-Al composite colloidal sol is 3-5.
6. the method according to any one in claim 1-3, wherein, step (1) it is identical with the magnesium source in step (2) or
Difference, the magnesium source is one or more in activated magnesia, magnesite and shepardite.
7. method according to claim 1, wherein, in step (3), the consumption of the chemical additives is multiple with the magnalium
The weight ratio for closing the total content of the aluminium hydroxide in colloidal sol is 0.1-10：1, preferably 0.25-3：1；
Preferably, the chemical additives are NaHCO3、Na2CO3, urea, oxalic acid, Na2C2O4、CO2, glucose, citric acid, second
One or more in acid and sodium acetate；
It is further preferred that the hydrothermal reaction condition includes：Temperature is 80-300 DEG C, preferably 120-220 DEG C；Pressure is
0.2-2.5MPa, preferably 0.5-2MPa；Time is 0.5-50h, preferably 2-30h.
8. method according to claim 1, wherein, in step (4), the consumption of the surface modifier is the magnalium water
The 0.1-6 weight % of the consumption of talcum slurry, preferably 2-4 weight %；
Preferably, surface modifier is one or more in stearic acid, silane coupler and laurate；
It is further preferred that in step (4), the catalytic condition includes：Temperature be 20-95 DEG C, the time be more than
10min。
9. the method according to any one in claim 1-3,7 and 8, wherein, methods described also includes：By step (3)
Step (4) is carried out again after the magnalium hydrotalcite slurries filtration, washing and the slurrying that obtain；
Preferably, the material obtained after step (4) surface modification reaction is filtered, dried and is crushed；
It is further preferred that the waste water carbonization Posterior circle that will be obtained after the filtering is used.
10. the magnalium hydrotalcite that the method as described in any one in claim 1-9 is prepared.
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| CN110104667B (en) * | 2019-05-16 | 2021-11-02 | 福州大学 | Magnesium-aluminum hydrotalcite for organic sulfur catalysis, and preparation method and application thereof |
| CN113371741A (en) * | 2021-06-08 | 2021-09-10 | 盘锦迪宝催化剂技术有限公司 | Magnesium-aluminum hydrotalcite and preparation method thereof |
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