CN103288108A - Method for preparing hydrotalcite compound using brucite - Google Patents
Method for preparing hydrotalcite compound using brucite Download PDFInfo
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- CN103288108A CN103288108A CN2013102422450A CN201310242245A CN103288108A CN 103288108 A CN103288108 A CN 103288108A CN 2013102422450 A CN2013102422450 A CN 2013102422450A CN 201310242245 A CN201310242245 A CN 201310242245A CN 103288108 A CN103288108 A CN 103288108A
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- brucite
- hydrotalcite
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- magnesium
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Abstract
The invention relates to the technical field of hydrotalcite compounds, and in particular relates to a method for preparing a hydrotalcite compound by taking brucite as a magnesium source. The treatment process comprises the following steps of: combining brucite, an aluminum source, a carbon source and water according to a certain proportion for feeding, or selectively adding certain amount of other hydroxides, oxides or salts of divalent metals or trivalent metals, carrying out reaction in a hydrothermal reactor for 1-20 hours within a temperature range of 100-250 DEG C, and finally washing, filtrating and drying the reaction product to obtain the hydrotalcite compound. The method provided by the invention takes the cheap brucite as a raw material, all the raw materials do not need to be pretreated, and are directly added into the reactor simultaneously without precedence order, and the target product is synthesized by one step. The method provided by the invention is simplified in production process, greatly reduces the production cost of the hydrotalcite compound and causes the industrial large-scale production of the cheap hydrotalcite compound possible.
Description
Technical field
The present invention relates to the hydrotalcite-based compound preparing technical field, be specifically related to a kind of method for preparing hydrotalcite-based compound with the brucite for the magnesium source.
Background technology
Hydrotalcite-based compound (LDHs) is the anion type laminated compound that a class has broad prospect of application, mainly comprises hydrotalcite (HT), houghite (being called for short HTLC) and their intercalation chemistry product pillared hydrotalcite (Pillared LDH).Its chemical constitution can be expressed as [M II
1-xThe M III
x(OH)
2]
x+ (A
N-)
X/nMH
2O, wherein the M II is Mg
2+, Ni
2+, Co
2+, Zn
2+, Cu
2+Deng divalent metal; The M III is Al
3+, Cr
3+, Fe
3+, Sc
3+Deng trivalent metal cation; A
N-Be negatively charged ion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6H
4(COO)
2 2-Etc. inorganic and organic ion and complexing ion.Typical hydrotalcite molecular formula is Mg
6A
L2(OH)
16CO
34H
2O has the brucite of being similar to [Mg (OH)
2] the regular octahedron structure, adjacent octahedron becomes unit layer by sharing prismatic, is positioned at the Mg on the layer
2+Can be within the specific limits by the Al of similar radius
3+Isomorphous substitution causes the positive charge accumulation on the hydroxyl layer, and these skeleton positive charges are positioned at the negatively charged ion CO of interlayer
3 2-Balance makes entire structure be electric neutrality.At interlayer, some water moleculess exist with crystalline state, can remove under the condition of breakable layer rod structure not.Special chemical structure and crystalline structure, given the performance of a series of excellences of hydrotalcite, as Modulatory character of the Modulatory character of laminate chemical constitution, interlayer anion interchangeability, grain size distribution etc., it is widely used in the fields such as rubber, plastics and catalysis, according to user demand, can on the magnesium aluminum-hydrotalcite basis, suitably introduce other metal ion to improve its respective performances.
At present, the most coprecipitation methods that adopt of synthetic hydrotalcite compounds, selected magnesium, aluminium source are the salt of solubility, this method by product is many, production efficiency is low, cost is high; It is raw material that human magnesium oxide, aluminium hydroxide are arranged, the synthetic magnesium aluminum-hydrotalcite of a step hydro-thermal, and the used magnesium oxide of this method is activated magnesia, and is on the high side; It is the magnesium source with brucite that the person is also arranged, adopt the synthetic magnesium aluminum-hydrotalcite of mechanics of machinery method, this method requires and must carry out pre-treatment to raw material, namely at first magnesium, aluminium source material to be carried out mixed grinding, mixture after will grinding subsequently carries out hydrothermal crystallizing again, this method exists shortcomings such as technical process parameter long, that will control is many, brings difficulty to large-scale commercial production.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of is the method for magnesium source hydro-thermal synthetic hydrotalcite compounds with the brucite, and all raw materials need not pre-treatment, directly adds the branch of no precedence, one-step synthesis target product simultaneously.This method has been simplified the hydrotalcite production technique, has shortened the production cycle, has significantly reduced production cost.
The method for preparing hydrotalcite-based compound with the brucite for the magnesium source of the present invention may further comprise the steps: brucite, aluminium source, alkali source and water are fed intake by a certain percentage, wherein Mg
2+/ Al
3+Mol ratio is 1-6:1, also can be as required, and optionally adding mol ratio is Al
3+0.01-0.5 doubly other two, trivalent metal hydroxides, oxide compound or salt, in 100-250 ℃ of temperature range, reaction is 1-20 hour in hydrothermal reaction kettle, finally by washing, filtration, drying, namely obtains hydrotalcite-based compound.
According to preparation method's of the present invention further feature, described magnesium source is brucite.
According to preparation method's of the present invention further feature, described aluminium source is to be selected from: at least a in gibbsite, aluminium hydroxide, aluminum oxide, sodium aluminate, sodium metaaluminate, aluminum nitrate, Tai-Ace S 150, the aluminum chloride.
According to preparation method's of the present invention further feature, described other two, trivalent metal ion is Ca
2+, Zn
2+, Fe
2+, Fe
3+, Co
2+, Co
3+, Ni
2+, Ni
3+, Cu
2+, Mn
3+, Cr
3+, Cd
2+, Ti
3+, La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+In at least a.
According to preparation method's of the present invention further feature, described alkali source is that sodium hydroxide, potassium hydroxide, ammoniacal liquor, urea and negatively charged ion are A
N-Corresponding ammonium salt, sodium salt, sylvite at least a, perhaps in building-up process, can react the compound that generates sodium hydroxide, potassium hydroxide, ammoniacal liquor.
According to preparation method's of the present invention further feature, described negatively charged ion A
N-Be CO
3 2-, HCO
3 -, SO
4 2-, HSO
4 -, SO
3 2-, NO
3 -, PO
4 3-, HPO
4 2-, H
2PO
4 -, HPO
3 2-, H
2PO
2 -, BO
3 3-, HB
4O
7 -, B
4O
7 2-, B
5O
8 -, BO
3 3-, P
2W
18O
60 6-, Mo
7O
24 6-, P
2Mo
18O
60 6-In at least a.
According to preparation method's of the present invention further feature, described method is hydrothermal synthesis method, and temperature of reaction is 100 ~ 250 ℃, reaction times is 1 ~ 20 hour, and all materials need not pre-treatment, directly adds simultaneously, the branch of no precedence, the one-step synthesis target product.
Of the present invention is the method for magnesium source one-step synthesis hydrotalcite-based compound with the brucite, and its advantage is: adopting brucite is the magnesium source, greatly reduces production cost; Adopt hydrothermal synthesis method, all raw materials need not pre-treatment, directly add the branch of no precedence, one-step synthesis target product simultaneously.Method provided by the present invention has significantly reduced the hydrotalcite production cost, has simplified production technique, has shortened the production cycle, for the hydrotalcite-based compound of industrial mass production of cheap provides possibility.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of embodiment 1 synthetic hydrotalcite.
Fig. 2 is infrared spectra (FTIR) figure of embodiment 1 synthetic hydrotalcite.
Fig. 3 is scanning electron microscope (SEM) figure of embodiment 1 synthetic back hydrotalcite.
Embodiment
Below in conjunction with concrete exemplifying embodiment the present invention is described in more detail and illustrates.
The brucite that adopts in the embodiment of the invention is produced by Yingkou, Liaoning, and its chemical ingredients is as shown in table 1:
Table 1: brucite chemical component table
| Composition | MgO | CaO | SiO 2 | Fe 2O 3 |
| Content (﹪) | 65 | 1.2 | 1.0 | 0.2 |
Known to those skilled in the art, the brucite in the different places of production, the magnesian content of its major ingredient between 60-69%, all can reach the requirement of the technology of the present invention usually, therefore, also can adopt the brucite of any products to implement technical scheme of the present invention.
Weighing 2.48g brucite, the 3.28g sodium metaaluminate, 4.42g yellow soda ash and a certain amount of water stir in hydrothermal reaction kettle, in 120 ℃ of constant temperature 16h, cooling back suction filtration, washing, 90 ℃ of dry 12h namely get magnesium aluminum-hydrotalcite.
The mensuration of embodiment 1 preparation products obtained therefrom.Shown in the XRD figure of Fig. 1, the diffraction peak of product all matches with card JCPDS22-700, and does not have other dephasign diffraction peak to occur, and shows that synthetic product is magnesium aluminum-hydrotalcite, and the structure homogeneous, the degree of crystallinity height.Shown in the FTIR figure of Fig. 2, there are hydroxyl and CO in the product
3 2-, wave number is 3454cm
-1The place is the hydroxyl vibration absorption peak, and wave number is 1369cm
-1Be CO
3 2-Vibration absorption peak, wave number are 451cm
-1Be hydrotalcite skeletal vibration charateristic avsorption band.Shown in the SEM figure of Fig. 3, the hydrotalcite that is synthesized is sheet.The result shows according to said determination, successfully synthetic magnesium aluminum-hydrotalcite.
Embodiment 2
Weighing 5.54g brucite, the 5.63g aluminum nitrate, the 0.84g sodium bicarbonate, 4ml ammoniacal liquor, a certain amount of water stirs in hydrothermal reaction kettle, in 200 ℃ of constant temperature 1h, cooling back suction filtration, washing, 90 ℃ of dry 12h namely get magnesium aluminum-hydrotalcite.
Embodiment 3
Weighing 3.69g brucite, 1.02g aluminum oxide, 0.99g zinc hydroxide, 0.90g urea, 1.12g a certain amount of water of potassium hydroxide stirs in hydrothermal reaction kettle, in 180 ℃ of constant temperature 4h, cooling back suction filtration, washing, 90 ℃ of dry 12h namely get magnalium zinc hydrotalcite.
Embodiment 4
Weighing 7.38g brucite, 2.37g aluminium hydroxide, 0.05g lanthanum trioxide, 3.18g yellow soda ash, 0.4g sodium hydroxide and a certain amount of water stir in hydrothermal reaction kettle, in 110 ℃ of constant temperature 24h, cooling back suction filtration, washing, 90 ℃ of dry 12h namely get magnalium zinc hydrotalcite.
Embodiment 5
Weighing 2.46g brucite, 2.67g aluminum chloride, 1.15g primary ammonium phosphate, 0.8g sodium hydroxide and a certain amount of water stir in hydrothermal reaction kettle, in 250 ℃ of constant temperature 12h, cooling back suction filtration, washing, 90 ℃ of dry 12h namely get the magnesium aluminum-hydrotalcite that interlayer anion is phosphate radical.
Embodiment 6
Weighing 3.69g brucite, 3.42g Tai-Ace S 150,5.96g K
6Mo
7O
24, the potassium hydroxide of 1.5ml 28% and a certain amount of water add it in reactor, stirs, and in 160 ℃ of constant temperature 6h, cooling back suction filtration, washing, 90 ℃ of dry 12h namely get Mo
7O
24 6-Pillared hydrotalcite.
Above-mentioned these embodiment only are used for illustrating content of the present invention, do not comprise the four corner of technical solution of the present invention.It will be appreciated by those skilled in the art that chemical structure and crystalline structure that hydrotalcite is special, given the performance of its a series of excellences, as Modulatory character, the interlayer anion interchangeability of laminate chemical constitution.As long as metallic cation has suitable ionic radius and charge number, namely with Mg
2+Ionic radius the M II, the M III that are more or less the same just can hold into by OH
-Close-packed forms the octahedral coordination center, constitutes stable class brucite laminate, and different metallic cation combinations can be synthesized the LDHs of a series of binary, ternary even quaternary.Of the present invention other two, trivalent metal ion can be selected from Ca
2+, Zn
2+, Fe
2+, Fe
3+, Co
2+, Co
3+, Ni
2+, Ni
3+, Cu
2+, Mn
3+, Cr
3+, Cd
2+, Ti
3+, La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+In at least a; Utilize hydrotalcite layers negatively charged ion interchangeability, in different solion atmosphere, can form interlayer anion A
N-LDHs, described negatively charged ion A
N-Can be selected from: CO
3 2-, HCO
3 -, SO
4 2-, HSO
4 -, SO
3 2-, HSO
3 -, NO
3 -, PO
4 3-, HPO
4 2-, H
2PO
4 -, HPO
3 2-, H
2PO
2 -, BO
3 3-, HB
4O
7 -, B
4O
7 2-, B
5O
8 -, P
2W
18O
60 6-, Mo
7O
24 6-Or P
2Mo
18O
60 6-In at least a.
Claims (6)
1. method that adopts brucite to prepare hydrotalcite-based compound is characterized in that may further comprise the steps:
, brucite, aluminium source, alkali source and water made up by a certain percentage feed intake as the magnesium source with brucite, wherein Mg
2+/ Al
3+Mol ratio is 1-6:1, and in 100-250 ℃ of temperature range, reaction is 1-20 hour in hydrothermal reaction kettle, finally by washing, filtration, drying, namely obtains hydrotalcite-based compound.
2. preparation method according to claim 1 is characterized in that: when combination feeds intake, can add Al
3+Mole number 0.01-0.5 doubly except aluminium, magnesium other two, oxyhydroxide, oxide compound or the salt of trivalent metal.
3. preparation method according to claim 1 is characterized in that, described aluminium source is to be selected from: gibbsite, aluminium hydroxide, aluminum oxide, sodium aluminate, sodium metaaluminate, aluminum nitrate, Tai-Ace S 150 or aluminum chloride.
4. preparation method according to claim 1 is characterized in that, described except aluminium, magnesium other two, trivalent metal ion is to be selected from: Ca
2+, Zn
2+, Fe
2+, Fe
3+, Co
2+, Co
3+, Ni
2+, Ni
3+, Cu
2+, Mn
3+, Cr
3+, Cd
2+, Ti
3+, La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+Or Gd
3+
5. preparation method according to claim 1 is characterized in that, described alkali source is to be selected from: sodium hydroxide, potassium hydroxide, ammoniacal liquor, urea, or negatively charged ion is A
N-Corresponding sodium salt, sylvite, ammonium salt perhaps can react the compound that generates sodium hydroxide, potassium hydroxide, ammoniacal liquor in building-up process.
6. preparation method according to claim 5 is characterized in that, described negatively charged ion is to be selected from: CO
3 2-, HCO
3 -, SO
4 2-, HSO
4 -, SO
3 2-, HSO
3 -, NO
3 -, PO
4 3-, HPO
4 2-, H
2PO
4 -, HPO
3 2-, H
2PO
2 -, BO
3 3-, HB
4O
7 -, B
4O
7 2-, B
5O
8 -, P
2W
18O
60 6-, Mo
7O
24 6-Or P
2Mo
18O
60 6-
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108946773A (en) * | 2018-09-21 | 2018-12-07 | 中国科学院山西煤炭化学研究所 | A kind of carbonate form hydrotalcite-based compound raw powder's production technology |
| CN110182833A (en) * | 2019-06-03 | 2019-08-30 | 肇庆学院 | It is a kind of to be crosslinked the preparation method of houghite, water paint and preparation method thereof |
| CN110496589A (en) * | 2019-08-27 | 2019-11-26 | 西安交通大学 | A kind of hydrotalcite and preparation method thereof and application of the hydrotalcite in adsorbed water body in PFOS pollutant |
| CN113526532A (en) * | 2021-06-30 | 2021-10-22 | 云南创能斐源金属燃料电池有限公司 | Method for treating waste electrolyte of aluminum-air battery |
| CN113697833A (en) * | 2021-08-09 | 2021-11-26 | 云南创能斐源金属燃料电池有限公司 | Method for preparing hydrotalcite and application thereof |
| CN114753160A (en) * | 2022-03-21 | 2022-07-15 | 南方科技大学 | Anti-ultraviolet flame retardant, preparation method thereof, anti-ultraviolet flame-retardant composition and product |
| WO2023056675A1 (en) * | 2021-10-09 | 2023-04-13 | 安徽大学绿色产业创新研究院 | Method for preparing magnesium-aluminum hydrotalcite by means of mother liquor circulation |
| CN117736500A (en) * | 2024-02-21 | 2024-03-22 | 山东艾科高分子材料有限公司 | Method for synthesizing phosphate radical intercalation magnalium hydrotalcite flame retardant in one step |
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| US20020110520A1 (en) * | 2001-02-09 | 2002-08-15 | Dennis Stamires | Process for the preparation of anionic clay |
| CN101229927A (en) * | 2007-01-26 | 2008-07-30 | 山东理工大学 | Water-heat one-step synthesis of nanocrystalline Mg-Al hydrotalcite |
| CN101905861A (en) * | 2009-06-05 | 2010-12-08 | 北京化工大学 | Preparation method of nanometer laminated composite metal hydroxide |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108946773A (en) * | 2018-09-21 | 2018-12-07 | 中国科学院山西煤炭化学研究所 | A kind of carbonate form hydrotalcite-based compound raw powder's production technology |
| CN110182833A (en) * | 2019-06-03 | 2019-08-30 | 肇庆学院 | It is a kind of to be crosslinked the preparation method of houghite, water paint and preparation method thereof |
| CN110182833B (en) * | 2019-06-03 | 2021-06-15 | 肇庆学院 | Preparation method of cross-linked hydrotalcite-like compound, water-based paint and preparation method thereof |
| CN110496589A (en) * | 2019-08-27 | 2019-11-26 | 西安交通大学 | A kind of hydrotalcite and preparation method thereof and application of the hydrotalcite in adsorbed water body in PFOS pollutant |
| CN110496589B (en) * | 2019-08-27 | 2020-11-10 | 西安交通大学 | Hydrotalcite, preparation method thereof and application of hydrotalcite in PFOS (Perfluorooctane sulfonate) pollutant adsorption in water body |
| CN113526532A (en) * | 2021-06-30 | 2021-10-22 | 云南创能斐源金属燃料电池有限公司 | Method for treating waste electrolyte of aluminum-air battery |
| CN113697833A (en) * | 2021-08-09 | 2021-11-26 | 云南创能斐源金属燃料电池有限公司 | Method for preparing hydrotalcite and application thereof |
| WO2023056675A1 (en) * | 2021-10-09 | 2023-04-13 | 安徽大学绿色产业创新研究院 | Method for preparing magnesium-aluminum hydrotalcite by means of mother liquor circulation |
| CN114753160A (en) * | 2022-03-21 | 2022-07-15 | 南方科技大学 | Anti-ultraviolet flame retardant, preparation method thereof, anti-ultraviolet flame-retardant composition and product |
| CN114753160B (en) * | 2022-03-21 | 2023-10-27 | 南方科技大学 | Anti-ultraviolet flame retardant, preparation method thereof, anti-ultraviolet flame retardant composition and product |
| CN117736500A (en) * | 2024-02-21 | 2024-03-22 | 山东艾科高分子材料有限公司 | Method for synthesizing phosphate radical intercalation magnalium hydrotalcite flame retardant in one step |
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Application publication date: 20130911 |