CN111875492A - Preparation method of organic acid anion intercalated hydrotalcite - Google Patents

Preparation method of organic acid anion intercalated hydrotalcite Download PDF

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CN111875492A
CN111875492A CN202010426741.1A CN202010426741A CN111875492A CN 111875492 A CN111875492 A CN 111875492A CN 202010426741 A CN202010426741 A CN 202010426741A CN 111875492 A CN111875492 A CN 111875492A
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hydrotalcite
organic acid
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宋宇飞
张分地
林长亘
陈伟
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Beijing University of Chemical Technology
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Abstract

The invention discloses a preparation method of organic acid anion intercalated hydrotalcite. The method directly adopts carbonate hydrotalcite and organic acid as reactants, and the carbonate hydrotalcite and the organic acid react to remove the carbonate in an alcohol solvent according to the principle of 'strong acid and weak acid', thereby successfully preparing the single organic acid anion intercalation hydrotalcite in one step. The preparation method has the advantages of easily obtained raw materials, simple process flow, no need of heating at room temperature, rapid reaction, short reaction time and wide applicability, and provides a feasible method for various organic acid anion intercalation hydrotalcite.

Description

Preparation method of organic acid anion intercalated hydrotalcite
Technical Field
The invention particularly relates to a preparation method of organic acid anion intercalated hydrotalcite, belonging to the technical field of composite functional materials.
Background
The hydrotalcite is a compound formed by orderly assembling interlayer anions and laminates with positive charges. The general formula is as follows: [ M ] A2 + 1-xM3+ x(OH)2](An-)x/n·mH2And O. Wherein M is2+，M3+Is a metal cation, An-Is an interlayer anion, 0.2<x/(1-x)<0.5，0<m<100. This particular two-dimensional layered structure gives hydrotalcite many unique properties. Such as plate ion tunability, interlayer ion exchangeability, memory effect, etc. The properties of hydrotalcite determine that the hydrotalcite can be widely applied to the fields of catalysts, medical carriers, functional additives and the like.
Hydrotalcite-organic composite materials have been a research hotspot material, and the material combines organic matters and hydrotalcite, combines the respective characteristics of the organic matters and the inorganic matters, and has wide application.
The traditional preparation method of organic acid anion intercalated hydrotalcite mainly comprises the following three steps: coprecipitation, calcination, and ion exchange. The coprecipitation method is similar to the method for preparing carbonate hydrotalcite, except that the alkali solution of sodium carbonate is changed into the alkali solution of the pre-intercalation anions, and then the alkali solution is mixed with the salt solution containing the laminate metal cations. It should be noted that the whole process requires strict isolation of CO2And pollution is prevented. The roasting recovery method is to utilize the 'memory effect' of hydrotalcite and to add the roasted LDO product into organic anion salt solution. In this process, part of the hydrotalcite laminate structure is restored, thereby allowing anions to enter between the layers to give the product. The method is complicated to operate, the heating rate and the roasting temperature need to be strictly controlled, the hydrotalcite layer structure can be damaged by carelessness, and the product often contains some metal oxide residues. Ion exchange is currently the most widely used method. The method comprises the steps of firstly exchanging carbonate hydrotalcite into nitrate hydrotalcite and then reacting the nitrate hydrotalcite with an organic acid salt solution to obtain a product. It can be seen that the conventional ion exchange method is relatively complicated, firstly carbonate hydrotalcite needs to be converted into nitrate, and organic acid needs to be exchanged into sodium salt, and the whole process needs to strictly control CO2. In summary, the conventional methods for preparing organic acid anion intercalated hydrotalcite have different disadvantages.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide a simple and efficient method for preparing organic acid anion intercalated hydrotalcite. The invention directly adopts carbonate hydrotalcite and organic acid as reactants, and the carbonate hydrotalcite and the organic acid react to remove the carbonate in the alcohol solvent according to the principle of 'strong acid and weak acid', thereby successfully preparing the single organic acid anion intercalation hydrotalcite in one step. The preparation method has the advantages of easily obtained raw materials, simple process flow, no need of heating at room temperature, rapid reaction, short reaction time and wide applicability, and provides a feasible method for various organic acid anion intercalation hydrotalcite.
The preparation method of the organic acid anion intercalated hydrotalcite comprises the following steps: dispersing carbonate hydrotalcite in an alcohol solvent; diluting organic acid in alcohol solvent; dropwise adding the obtained organic acid alcohol solution into the vigorously stirred carbonate hydrotalcite dispersion liquid, stirring and reacting for 10-30 minutes at room temperature, and after the reaction is finished, filtering, washing an alcohol solvent and drying in vacuum to obtain the organic acid anion intercalated hydrotalcite.
In the first method, the organic acid is acetic acid, chloroacetic acid, dichloroacetic acid, propionic acid, acrylic acid, p-fluorobenzoic acid, p-methylbenzoic acid, p-nitrobenzoic acid, terephthalic acid, p-hydroxybenzoic acid, glycolic acid, lactic acid, trichloroacetic acid, oxalic acid, malonic acid, succinic acid, benzoic acid and methanesulfonic acid.
The preparation method of the organic acid anion intercalated hydrotalcite comprises the following steps: dispersing carbonate hydrotalcite in an alcohol solvent; diluting glacial acetic acid in an alcohol solvent; diluting organic acid in alcohol solvent; firstly, dropwise adding the obtained alcoholic solution of glacial acetic acid into a vigorously stirred carbonate hydrotalcite dispersion liquid, stirring and reacting for 10-30 minutes at room temperature, then dropwise adding the obtained alcoholic solution of organic acid into the vigorously stirred carbonate hydrotalcite dispersion liquid, stirring and reacting for 10-30 minutes at room temperature, filtering, washing an alcohol solvent and drying in vacuum after the reaction is finished, thus obtaining the organic acid anion intercalated hydrotalcite.
In the second method, the organic acid is aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, aromatic carboxylic acid, organic sulfonic acid or organic phosphonic acid.
The alcohol solvent is one or more of methanol, ethanol, isopropanol and n-propanol.
The calculation formula of the amount of the added substances of the organic acid is as follows: f ═ COOH]/(2×[CO3 2-]And f represents the amount of the substance to which the organic acid is added.
The size of the carbonate hydrotalcite is 10 nanometers to 9 micrometers. And the exchange reaction is easier as the size of the carbonate hydrotalcite is reduced.
The invention is characterized in that carbonate hydrotalcite and organic acid are directly used as reactants, and the organic acid directly reacts with the hydrotalcite in the intercalation reaction process as follows: mg (magnesium)2Al-CO3+R-COOH→Mg2Al-(R- COO)+CO2↑+H2O, which is a "strong acid to weak acid" process, is a metathesis reaction in which two compounds exchange components to form two other compounds. The pKa of carbonic acid is 6.38, and the organic acid pKa is selected<6.38, since carbonate anions between hydrotalcite layers are strong acids relative to carbonic acid, the carbonate anions can be replaced by organic acid radical ions in the solution, meanwhile, hydrogen ions separated by the organic acid are combined with the carbonate to generate carbon dioxide gas which is difficult to ionize, and the carbon dioxide continuously overflows to promote the reaction to proceed in the forward direction, so that the experimental mechanism of the reaction is strong acid-weak acid. Hydrotalcite is an alkaline hydroxide, is relatively weak against acids, and is easily destroyed by acidic substances. Therefore, the alcohol solvent is selected as a reaction medium. The ability of alcohol to accept proton is weaker than that of water, that is, the alcohol is a proton alkali weaker than that of water, so that the alcohol as a reaction medium can effectively inhibit the dissociation rate of organic acid, thereby reducing the acidity of the whole solution, enabling the hydrotalcite to be in an environment with weaker acidity, preventing the hydrotalcite laminate from being etched by acid, greatly enhancing the acid resistance of the hydrotalcite, and achieving the purpose of protecting the hydrotalcite laminate.
Drawings
FIG. 1a is a graph showing the change in concentration of carbon dioxide in the reaction off-gas during intercalation in example 1; FIG. 1b shows XRD patterns before and after reaction of hydrotalcite in comparative example 1 with water as the reaction medium.
Figure 2 is an XRD spectrum of LDH with acetate anion intercalated of different metal element compositions in example 2.
FIG. 3 is the intercalation of acetate anions into Mg of different sizes in example 32The XRD spectrum of the Al-LDH has a:50-80 nm, b:250-500nm and c:2-3 μm.
FIG. 4 is the intercalation of the aliphatic monocarboxylic anion with Mg of example 42And (3) a characterization diagram of the Al-LDH, wherein a is an XRD spectrum and b is an FT-IR spectrum.
FIG. 5 is the intercalation of aliphatic dicarboxylic acid anions with Mg in example 52And (3) a characterization diagram of the Al-LDH, wherein a is an XRD spectrum and b is an FT-IR spectrum.
FIG. 6 is the intercalation of aromatic carboxylic anion with Mg of example 62And (3) a characterization diagram of the Al-LDH, wherein a is an XRD spectrum and b is an FT-IR spectrum.
FIG. 7 is the intercalation of organic sulfonic acid anion with Mg in example 72And (3) a characterization diagram of the Al-LDH, wherein a is an XRD spectrum and b is an FT-IR spectrum.
FIG. 8 is the phosphonic acid anion intercalated Mg of example 82And (3) a characterization diagram of the Al-LDH, wherein a is an XRD spectrum and b is an FT-IR spectrum.
The specific implementation mode is as follows:
the following examples are provided to illustrate specific embodiments of the present invention, but the present invention is not limited to the following examples.
The calculation formula of the amount of the added substances of the organic acid is as follows: f ═ COOH]/(2×[CO3 2-]And f represents the amount of the substance to which the organic acid is added. Specific data for experiments with different hydrotalcites and different organic acids are given in tables 1 and 2.
TABLE 1
Figure RE-GDA0002627317540000041
Figure RE-GDA0002627317540000051
TABLE 2
Figure RE-GDA0002627317540000052
Description of the drawings: mg (magnesium)2Al-S、Mg2Al-M、Mg2Al-L respectively represents 50-80nm, 250-500nm, 2-3 μm CO3 2--Mg2Al-LDH; the amounts of the acids listed in the table are all the amounts of organic acids required for the reaction of 100mg of hydrotalcite.
Example 1: preparation of acetic acid anion intercalation magnalium hydrotalcite
Dispersing 100mg of carbonate magnesium aluminum hydrotalcite into 200mL of methanol; 5mL of glacial acetic acid was diluted in 50mL of methanol and then added dropwise to the vigorously stirred dispersion of the magnesium aluminum hydrotalcite, the reaction was stirred at room temperature for 30 minutes, and the resulting suspension was washed with methanol, centrifuged, filtered, and dried in vacuo.
Comparative example 1: the methanol in example 1 was replaced with water and the remaining reaction conditions were the same.
As can be seen from FIG. 1, under the condition of water as the reaction medium, the organic acid can not enter the interlayer, and from the data in Table 3, the hydrotalcite is seriously damaged under the condition of water as the reaction medium, and the yield is only about 60%.
TABLE 3 LDH yields for the different reaction media
Figure RE-GDA0002627317540000061
Example 2: preparation of acetic acid anion intercalation zinc-aluminum hydrotalcite, cobalt-aluminum hydrotalcite and nickel-iron hydrotalcite
Dispersing 100mg of carbonate zinc-aluminum hydrotalcite, carbonate cobalt-aluminum hydrotalcite and carbonate nickel-iron hydrotalcite into 200mL of methanol respectively; diluting 5mL of glacial acetic acid in 50mL of methanol, then respectively dropwise adding the glacial acetic acid into vigorously stirred dispersion liquid of carbonate zinc-aluminum hydrotalcite, carbonate cobalt-aluminum hydrotalcite and carbonate nickel-iron hydrotalcite, stirring and reacting for 30 minutes at room temperature, respectively washing obtained suspension liquid with methanol, centrifugally filtering, and drying in vacuum.
Example 3: preparation of hydrotalcite with acetate anion intercalation different sizes
100mg of carbonate magnesium aluminum hydrotalcite with the sizes of 50-80nm, 250-500nm and 2-3 mu m are respectively dispersed into 200mL of methanol; 5mL of glacial acetic acid was diluted in 50mL of methanol and then added dropwise to vigorously stirred dispersions of different sizes of carbonate magnesium aluminum hydrotalcite, the reaction was stirred at room temperature for 30 minutes, and the resulting suspension was washed with methanol, centrifuged, filtered, and dried in vacuo.
Example 4: preparation of aliphatic monocarboxylic acid anion intercalation hydrotalcite
Dispersing 100mg of carbonate magnesium aluminum hydrotalcite into 200mL of methanol; 5mg of aliphatic monocarboxylic acid (structural formula shown in FIG. 4) was diluted in 50mL of methanol, and then added dropwise to the vigorously stirred dispersion of carbonate magnesium aluminum hydrotalcite, and the reaction was stirred at room temperature for 30 minutes, and the resulting suspension was washed with methanol, centrifuged, and dried in vacuo.
Example 5: preparation of aliphatic dicarboxylic acid anion intercalation hydrotalcite
Dispersing 100mg of carbonate magnesium aluminum hydrotalcite into 200mL of methanol; 5mg of aliphatic dicarboxylic acid (structural formula shown in fig. 5) was diluted in 50mL of methanol, and then added dropwise to the vigorously stirred dispersion of carbonate magnesium aluminum hydrotalcite, and the reaction was stirred at room temperature for 30 minutes, and the resulting suspension was washed with methanol, centrifuged, and dried in vacuum.
Example 6: preparation of aromatic carboxylic acid anion intercalation hydrotalcite
Dispersing 100mg of carbonate magnesium aluminum hydrotalcite into 200mL of methanol; 5mg of an aromatic carboxylic acid (structural formula shown in FIG. 6) was diluted in 50mL of methanol, and then added dropwise to a vigorously stirred dispersion of a carbonate magnesium aluminum hydrotalcite, and the reaction was stirred at room temperature for 30 minutes, and the resulting suspension was washed with methanol, centrifuged, and dried in vacuo.
Example 7: preparation of organic sulfonic acid anion intercalation hydrotalcite
Firstly, 100mg of magnesium-aluminum carbonate hydrotalcite precursor is dispersed into 300mL of methanol, 5mL of glacial acetic acid is diluted into 50mL of methanol, then the diluted glacial acetic acid is dropwise added into the vigorously stirred hydrotalcite suspension, after the mixed suspension is stirred for 30 minutes at room temperature, 5mg of organic sulfonic acid (the structural formula is shown in figure 7) is diluted into 50mL of methanol and then is dropwise added into the vigorously stirred hydrotalcite suspension, and the reaction is continued for 30 minutes. The resulting suspension was washed with methanol, centrifuged, filtered and dried in vacuo.
Example 8: preparation of organic phosphonic acid anion intercalation hydrotalcite
Firstly, 100mg of magnesium-aluminum carbonate hydrotalcite precursor is dispersed into 300mL of methanol, 5mL of glacial acetic acid is diluted into 50mL of methanol, then the diluted glacial acetic acid is dropwise added into the vigorously stirred hydrotalcite suspension, after the mixed suspension is stirred for 30 minutes at room temperature, 5mg of organic phosphonic acid (the structural formula is shown in figure 8) is diluted into 50mL of methanol and then is dropwise added into the vigorously stirred hydrotalcite suspension, and the reaction is continued for 30 minutes. The resulting suspension was washed with methanol, centrifuged, filtered and dried in vacuo.

Claims (10)

1. A preparation method of organic acid anion intercalated hydrotalcite is characterized by comprising the following specific steps: dispersing carbonate hydrotalcite in an alcohol solvent; diluting organic acid in alcohol solvent; dropwise adding the obtained organic acid alcohol solution into the vigorously stirred carbonate hydrotalcite dispersion liquid, stirring and reacting for 10-30 minutes at room temperature, and after the reaction is finished, filtering, washing an alcohol solvent and drying in vacuum to obtain the organic acid anion intercalated hydrotalcite.
2. The method according to claim 1, wherein the organic acid is acetic acid, chloroacetic acid, dichloroacetic acid, propionic acid, acrylic acid, p-fluorobenzoic acid, p-methylbenzoic acid, p-nitrobenzoic acid, terephthalic acid, p-hydroxybenzoic acid, glycolic acid, lactic acid, trichloroacetic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, or methanesulfonic acid.
3. The preparation method according to claim 1, wherein the alcohol solvent is one or more of methanol, ethanol, isopropanol and n-propanol.
4. The method according to claim 1, wherein the amount of the organic acid added is calculated by the formula: f ═ COOH]/(2×[CO3 2-]And f represents the amount of the substance to which the organic acid is added.
5. The preparation method according to claim 1, wherein the size of the carbonate hydrotalcite is 10 nm to 9 μm, and the exchange reaction is easier as the size of the carbonate hydrotalcite decreases.
6. A preparation method of organic acid anion intercalated hydrotalcite is characterized by comprising the following specific steps: dispersing carbonate hydrotalcite in an alcohol solvent; diluting glacial acetic acid in an alcohol solvent; diluting organic acid in alcohol solvent; firstly, dropwise adding the obtained alcoholic solution of glacial acetic acid into a vigorously stirred carbonate hydrotalcite dispersion liquid, stirring and reacting for 10-30 minutes at room temperature, then dropwise adding the obtained alcoholic solution of organic acid into the vigorously stirred carbonate hydrotalcite dispersion liquid, stirring and reacting for 10-30 minutes at room temperature, filtering, washing an alcohol solvent and drying in vacuum after the reaction is finished, thus obtaining the organic acid anion intercalated hydrotalcite.
7. The method according to claim 6, wherein the organic acid is selected from the group consisting of aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aromatic carboxylic acids, organic sulfonic acids, and organic phosphonic acids.
8. The preparation method according to claim 6, wherein the alcohol solvent is one or more of methanol, ethanol, isopropanol and n-propanol.
9. The method according to claim 6, wherein the amount of the organic acid added is calculated by the formula: f ═ COOH]/(2×[CO3 2-]And f represents the amount of the substance to which the organic acid is added.
10. The preparation method according to claim 6, wherein the size of the carbonate hydrotalcite is 10 nm-9 μm, and the exchange reaction is easier as the size of the carbonate hydrotalcite decreases.
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