CN106745118B - 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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- CN106745118B CN106745118B CN201611262309.3A CN201611262309A CN106745118B CN 106745118 B CN106745118 B CN 106745118B CN 201611262309 A CN201611262309 A CN 201611262309A CN 106745118 B CN106745118 B CN 106745118B
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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, with or without oxygen or hydrogen, and containing two or more other elements
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- 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
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- C08K3/26—Carbonates; Bicarbonates
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- C08K9/04—Ingredients treated with organic substances
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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
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Abstract
The present invention relates to hydrotalcite field, discloses a kind of magnalium hydrotalcite and the method for preparing magnalium hydrotalcite, wherein, methods described includes：(1) in the presence of water, magnesium source and/or aluminium hydroxide are subjected to ball milling, obtain sol precursor；(2) sol precursor is diluted with water, the solution obtained after dilution is mixed with magnesium source and aluminium hydroxide, then obtained mixture is contacted with acidic materials, 10 300min are 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.The method of the invention technique is simple, cost is low, and can improve the crystallinity of magnalium hydrotalcite.
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 a kind of anionic clay quickly grown 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,
Multiple functions are filled, are a kind of efficient, Halogen, low cigarette, nontoxic inorganic combustion inhibitor new varieties；As stabilizer, have excellent
Heat endurance, and there is good absorption iris action to ultraviolet light, thus great exploitation potential.
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 to expect for source, 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 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
Calciner, and aquation is stilled need after 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, using 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 complicated method of the prior art for preparing magnalium hydrotalcite, cost height, obtain
The defects 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 subjected to ball milling, obtain sol precursor；
(2) sol precursor is diluted with water, the solution obtained after dilution mixed with magnesium source and aluminium hydroxide, so
Obtained mixture is contacted with acidic materials afterwards, 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 being prepared by method of the present invention.
Compared with prior art, the present invention is with advantages below：
(1) using the mineral of cheap magnesium as magnesium source, using 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, add insoluble magnesium source
With the contact area of silicon source, reduce reaction barrier therebetween, accelerate the progress of reaction；
(3) chemical additives are added so that certain CO is kept in course of reaction3 2-Concentration, promote magnalium hydrotalcite crystal grain
Growth；Simultaneously use hydro-thermal method, so as to get magnalium hydrotalcite crystallinity height；
(4) waste water in preparation process (such as is passed through CO thereto through carbonization2Gas) after can recycle, it is whole raw
Production 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 a part for constitution instruction, with following tool
Body embodiment 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 is that the DSC-TG of embodiment 3 schemes；
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.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value 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
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
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 subjected to ball milling, obtain sol precursor；
(2) sol precursor is diluted with water, the solution obtained after dilution mixed with magnesium source and aluminium hydroxide, so
Obtained mixture is contacted with acidic materials afterwards, 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 dosage and the weight ratio in magnesium source and total dosage of aluminium hydroxide of water are 0.5-20：
1, preferably 3-10：1.
In the present invention, in step (1), there is no particular limitation for the dosage of dosage and aluminium hydroxide to the magnesium source, institute
It can be arbitrary proportion to state the dosage in magnesium source and the dosage of aluminium hydroxide.
In the present invention, the ball milling can be implemented by the conventional means in this area, such as can implement in ball mill,
It is preferred that the condition of the ball milling includes：Rotating speed is 50-1500r/min, time 0.5-4h.
In the present invention, it is preferable that in step (2), the dosage in the magnesium source causes the magnesium in sol precursor to account for institute
State the 0-50 weight % of 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 dosage of aluminium hydroxide causes the hydrogen-oxygen formed in Mg-Al composite colloidal sol
The mol ratio for changing the content and the content of the aluminium hydroxide in 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), the dosage of the acidic materials contains with the magnesium source in the mixture
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, there is no particular limitation for the selection to the acidic materials, preferable case, and the acidic materials are second
In one or more in acid, oxalic acid, hydrochloric acid, carbonic acid, sulfuric acid, nitric acid and phosphoric acid, more preferably 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
Complex sol small, specific surface area is high, surface-active is big, as shown in fig. 6, forming the aluminium hydroxide and magnesium after Mg-Al composite colloidal sol
The surface that source reduces the energy barrier that is reacted in course of reaction, contacts with each other becomes 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 the sol precursor to dilute 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, there is no particular limitation for the selection to the aluminium hydroxide, 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
Charge unbalance on magnesium synusia be present, such magnesium hydroxide synusia understands the anion in adsorption reaction system, such as CO3 2-, most end form
Into the structure of multilayer tablet superposition as shown in Figure 7.In course of reaction, not forming the feed particles of colloidal sol can constantly carry
For magnesium ion and aluminium ion until feed particles consumption is complete, the hydrotalcite synusia to be formed is set constantly to grow up.
In the present invention, it is preferable that in step (3), in the dosage 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
Spend high magnalium hydrotalcite.
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 make it 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 of magnalium hydrotalcite reduces, and can improve magnalium neatly
The compatibility of stone and high polymer material, prevent the reunion between hydrotalcite particle.
In the present invention, the dosage of the surface modifier is preferably the 0.1-6 weights of the dosage of the magnalium hydrotalcite slurry
Measure %, more preferably 2-4 weight %.
In the present invention, there is no particular limitation for the selection to the surface modifier, can be the conventional selection of ability, excellent
Selection of land, the surface modifier are the 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, still, 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 obtained afterwards uses.
Present invention also offers the magnalium hydrotalcite being prepared by method of the present invention.The magnalium hydrotalcite tool
There is higher crystallinity.
The present invention will be described in detail by way of examples below.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 specific surface area of magnalium hydrotalcite automatically quickly compares surface by the ASAP S2460 of 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 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 calculation formula
It is as follows：
η=Sc/S0
Wherein, η is crystallinity；
ScFor the peak area of magnalium hydrotalcite in XRD；
S0For 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, obtains sol precursor；
(2) Mg-Al composite colloidal sol is prepared
100ml sol precursors are taken, are diluted with water to 2L, add 150g magnesite thereto (purchased from the holy fire resisting of Haicheng City China
Materials Co., Ltd's trade mark is 40-70, similarly hereinafter) and 60g aluminium hydroxides (be purchased from the Luoyang Zhong Chao new materials limited company trade mark
For AH-01DG, similarly hereinafter)；5g acetic acid+3g oxalic acid is added after stirring thereto, 30min is incubated at 80 DEG C and obtains magnalium and answers
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) obtains is added in autoclave (pressure 1.3MPa), and thereto
Add 54g NaHCO3With 30g oxalic acid, pH=7.5 magnaliums are obtained after 180 DEG C of hydro-thermal reaction 6h, filtered, washing and slurrying
Hydrotalcite slurry；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) obtains is put into water-bath, 4g laurate is added thereto, at 85 DEG C
2h is incubated, carries out surface-hydrophobicized modification.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 22.4m2/ g, crystallinity 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
2h is ground, obtains sol precursor.
(2) Mg-Al composite colloidal sol is prepared
Take 100ml sol precursors to be diluted with water to 2L, add 100g magnesite, 30g activated magnesias and 60g thereto
Aluminium hydroxide；The nitric acid of 5g oxalic acid and 2ml concentration for 3mol/L is added after stirring thereto, 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) obtains is added in autoclave (pressure 2MPa), and added thereto
Enter 54g Na2CO3With 30g sodium acetates, pH=7.7 magnalium water is obtained after 220 DEG C of hydro-thermal reaction 2h, filtered, washing and slurrying
Talcum slurry；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) obtains is put into water-bath, adds 2g laurate and 2g stearic acid thereto,
2h is incubated at 95 DEG C, carries out surface-hydrophobicized modification.Then magnalium will be obtained after modified slurry filtration, drying, crushing
Hydrotalcite powder.D50=4.836 μm of the magnalium hydrotalcite, specific surface area 15.3m2/ g, crystallinity 97%.By Fig. 2 institutes
The XRD shown 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 to be diluted with water to 2L, add 150g magnesite and 60g aluminium hydroxides thereto；Stirring
The hydrochloric acid and 3g oxalic acid that 2ml concentration is 3mol/L are added after uniformly thereto, it is molten to obtain Mg-Al composite by insulation 60min at 50 DEG C
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) obtains is added in autoclave (pressure 0.5MPa), and thereto
65g oxalic acid and 20g citric acids are added, pH=7.2 magnesium is obtained after 150 DEG C of hydro-thermal reaction 30h, filtered, washing and slurrying
Aluminum hydrotalcite slurry.
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) obtains is put into water-bath, adds 2g laurate and 2g ethene thereto
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 18.6m2/ g, crystallinity 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 largely when being thermally decomposed
Heat, illustrate 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, water 2L is added after mixing, after stirring thereto
5g acetic acid+3g oxalic acid is added, 30min is incubated at 80 DEG C and obtains 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) obtains is added in autoclave (pressure 1.3MPa), and thereto
Add 54g NaHCO3With 30g oxalic acid, pH=7.5 magnaliums are obtained after 180 DEG C of hydro-thermal reaction 6h, filtered, washing and slurrying
Hydrotalcite slurry；
(3) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) obtains is put into water-bath, 4g laurate is added thereto, at 85 DEG C
2h is incubated, carries out surface-hydrophobicized modification.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 24.6m2/ g, crystallinity 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
2h is ground, obtains sol precursor；
(2) Mg-Al composite colloidal sol is prepared
100ml sol precursors are taken, are diluted with water to 2L, add 150g magnesite and 60g aluminium hydroxides thereto；Stirring
After uniformly, 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) obtains is added in autoclave (pressure 1.3MPa), and thereto
Add 54g NaHCO3With 30g oxalic acid, pH=7.5 magnaliums are obtained after 180 DEG C of hydro-thermal reaction 6h, filtered, washing and slurrying
Hydrotalcite slurry；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) obtains is put into water-bath, 4g laurate is added thereto, at 85 DEG C
2h is incubated, carries out surface-hydrophobicized modification.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 32.5m2/ g, crystallinity 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
2h is ground, obtains sol precursor；
(2) Mg-Al composite colloidal sol is prepared
100ml sol precursors are taken, are diluted with water to 2L, add 150g magnesite and 60g aluminium hydroxides thereto；Stirring
5g acetic acid+3g oxalic acid is added thereto after uniformly, and 30min is incubated at 80 DEG C and obtains 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) obtains is added in autoclave (pressure 1.3MPa), in 180 DEG C of water
Thermal response 6h, pH=7.3 magnalium hydrotalcite slurries are obtained after filtered, washing and slurrying；
(4) magnalium hydrotalcite surface is modified
The magnalium hydrotalcite slurry that step (3) obtains is put into water-bath, 4g laurate is added thereto, at 85 DEG C
2h is incubated, carries out surface-hydrophobicized modification.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 72.3m2/ g, crystallinity 23%.XRD as shown in Figure 5
Figure will also realize that the magnalium hydrotalcite crystallinity is simultaneously bad.
Crystallinity can be prepared using the method for the invention it can be seen from the result of above example and comparative example
High magnalium hydrotalcite.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of 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 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 no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, 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 (28)
- A kind of 1. 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 subjected to ball milling, obtain sol precursor；(2) sol precursor is diluted with water, the solution obtained after dilution is mixed with magnesium source and aluminium hydroxide, then will Obtained mixture 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. the method according to claim 11, wherein, in step (1), dosage and the magnesium source and total dosage of aluminium hydroxide of water Weight ratio be 0.5-20：1.
- 3. the method according to claim 11, wherein, in step (1), dosage and the magnesium source and total dosage of aluminium hydroxide of water Weight ratio be 3-10：1.
- 4. according to the method for claim 1, wherein, in step (2), the dosage in the magnesium source to come from sol precursor In the 3-50 weight % of total magnesium amount that accounts in the Mg-Al composite colloidal sol of magnesium.
- 5. according to the method for claim 4, wherein, in step (2), the dosage in the magnesium source to come from sol precursor In the 3-20 weight % of total magnesium amount that accounts in the Mg-Al composite colloidal sol of magnesium.
- 6. according to the method for claim 5, wherein, in step (2), the dosage in the magnesium source to come from sol precursor In the 3-15 weight % of total magnesium amount that accounts in the Mg-Al composite colloidal sol of magnesium.
- 7. the method according to claim 1 or 4, wherein, in step (2), the dosage of aluminium hydroxide make it that Mg-Al composite is molten The mol ratio of the content of the magnesium hydroxide formed in glue and the content of the aluminium hydroxide in the Mg-Al composite colloidal sol is 1-5：1.
- 8. according to the method for claim 7, wherein, in step (2), the dosage of aluminium hydroxide causes in Mg-Al composite colloidal sol The mol ratio of the content of the magnesium hydroxide of formation and the content of the aluminium hydroxide in the Mg-Al composite colloidal sol is 1.5-3：1.
- 9. the method according to claim 1 or 4, wherein, in step (2), the dosage of the acidic materials mixes with described The weight ratio of the content in the magnesium source in thing is 0.1-0.2：1.
- 10. according to the method for claim 9, wherein, the acidic materials are acetic acid, oxalic acid, hydrochloric acid, carbonic acid, sulfuric acid, nitre One or more in acid and phosphoric acid.
- 11. according to the method for claim 9, wherein, the process of the dilution causes the sol precursor dilution 10-20 Times volume.
- 12. according to the method for claim 9, wherein, the pH of the Mg-Al composite colloidal sol is 3-5.
- 13. according to the method described in any one in claim 1-4, wherein, step (1) is identical with the magnesium source in step (2) Or it is different, the magnesium source is the one or more in activated magnesia, magnesite and shepardite.
- 14. the method according to claim 11, wherein, in step (3), the dosage of the chemical additives and the magnalium The weight ratio of the total content of aluminium hydroxide in complex sol is 0.1-10：1.
- 15. the method according to claim 11, wherein, in step (3), the dosage of the chemical additives and the magnalium The weight ratio of the total content of aluminium hydroxide in complex sol is 0.25-3：1.
- 16. according to the method for claim 14, wherein, the chemical additives are NaHCO3、Na2CO3, urea, oxalic acid, Na2C2O4、CO2, glucose, citric acid, the one or more in acetic acid and sodium acetate.
- 17. according to the method for claim 14, wherein, the hydrothermal reaction condition includes：Temperature is 80-300 DEG C, pressure For 0.2-2.5MPa, time 0.5-50h.
- 18. according to the method for claim 17, wherein, the temperature is 120-220 DEG C.
- 19. according to the method for claim 17, wherein, the pressure is 0.5-2MPa.
- 20. according to the method for claim 17, wherein, the time is 2-30h.
- 21. according to the method for claim 1, wherein, in step (4), the dosage of the surface modifier is the magnalium The 0.1-6 weight % of the dosage of hydrotalcite slurry.
- 22. according to the method for claim 21, wherein, in step (4), the dosage of the surface modifier is the magnalium The 2-4 weight % of the dosage of hydrotalcite slurry.
- 23. according to the method for claim 21, wherein, surface modifier is in stearic acid, silane coupler and laurate One or more.
- 24. according to the method for claim 21, wherein, in step (4), the catalytic condition includes：Temperature is 20-95 DEG C, the time is more than 10min.
- 25. according to the method described in any one in claim 1-4,14 and 21, wherein, methods described also includes：By step (3) step (4) is carried out after the magnalium hydrotalcite slurries filtration, washing and the slurrying that obtain again.
- 26. according to the method for claim 25, wherein, methods described also includes：It will be obtained after step (4) surface modification reaction To material filtered, dried and crushed.
- 27. according to the method for claim 26, wherein, methods described also includes：The wastewater carbon that will be obtained after the filtering Change Posterior circle to use.
- 28. the magnalium hydrotalcite being prepared as the method described in any one in claim 1-25.
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