CN107500328A - The preparation method of calcium base layered composite metal hydroxides - Google Patents
The preparation method of calcium base layered composite metal hydroxides Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C01F11/00—Compounds of calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/006—Compounds containing, besides chromium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
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- C01G49/00—Compounds of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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Abstract
The invention discloses a kind of preparation method of calcium base layered composite metal hydroxides, the calcium base layered composite metal hydroxides include low price main layer board cation, high price main layer board cation and interlayer anion, and its middle or low price main layer board cation comprises at least calcium ion；The preparation method includes step：S1, calcium oxide mixed with the water soluble salt of high-valence cationic, obtain the first mixture；S2, the first mixture is soluble in water, the second mixture of acquisition；S3, the second mixture is reacted to 4h~100h at 80 DEG C~300 DEG C, reaction product the scrubbed drying of gained solid phase, obtains calcium base layered composite metal hydroxides through separation of solid and liquid.According to the preparation method of the calcium based composite metal hydroxide of the present invention during calcium base layered composite metal hydroxides are prepared, avoid using raw materials such as sodium hydroxide, sodium carbonate, and target product, Atom economy 100% are reacted and generated to raw materials used both participate in.
Description
Technical field
The invention belongs to inorganic non-metallic technical field of function materials, specifically, is related to a kind of calcium base lamellar composite gold
Belong to the preparation method of hydroxide.
Background technology
Complex metal hydroxide (abbreviation LDHs) is a kind of stratified material, and LDHs is by positively charged metal hydroxides
Laminate and negatively charged interlayer anion assemble, and the metal sun with different electric charges is carried in layers of metal hydroxides plate
Ion.In existing LDHs, metal cation is mainly divalent metal and trivalent metal cation, thus the LDHs
General structure be represented by：[M+M2+ 1-y-0.5x-2zM3+ yM4+ z(OH)2](An-)y/n·mH2O, wherein M+、M2+、M3+And M4+Respectively
Represent monovalent metal cation, divalent metal, trivalent metal cation and four on layers of metal hydroxides plate
Valency metal cation, An-Expression interlayer anion, 0≤x≤0.4,0≤y≤0.7,0≤z≤0.5,0≤y+0.5x+2z≤1,
Wherein y, z can not be the amount for the material that 0, m is interlayer hydrone simultaneously.
LDHs has the characteristics that Subjective and Objective element species and quantity is adjustable, the elastic adjustable, size of laminate and pattern are adjustable,
LDHs is because the particularity of its structure and performance are greatly strengthened and are ground in catalysis, the energy, biology sensor, absorption, medicine etc.
Study carefully field and cause broad interest and great attention, interrelationship between industries is big, permeability is strong, and it is numerous to can be widely applied to national economy
Field and industry.
Traditional LDHs preparation method mainly has hydro-thermal method, the precipitation method, in-situ synthesis, ion-exchange, roasting also
Former method etc..In traditional LDHs preparation method, on the one hand, need with sodium hydroxide, ammoniacal liquor, sodium carbonate, ammonium carbonate etc. be
Raw material, can introduce new accessory substance, not only need to carry out the lock out operation of LDHs and accessory substance, and the LDHs after separation is also needed
Washed, conventional method often produce 1 ton of LDHs can the accessory substance such as the sodium salt of 2 tons or so of by-product, ammonium salt, it is necessary to tens times very
Water to hundreds of times is washed, and causes a large amount of wastes of water resource；On the other hand, CO is also needed in some methods2Etc. acidity
Gas, operation is increasingly complex, and gas can also bring that Keep Clear-High Voltage using accidentally.
The content of the invention
To solve the above-mentioned problems of the prior art, the invention provides a kind of calcium base layered composite metal hydroxides
Preparation method, the preparation method can avoid using hydroxide during calcium base layered composite metal hydroxides are prepared
The raw materials such as sodium, sodium carbonate, and target product, Atom economy 100% are reacted and generated to raw materials used both participate in.
In order to reach foregoing invention purpose, present invention employs following technical scheme：
A kind of preparation method of calcium base layered composite metal hydroxides, the calcium Ji Cengzhuanfuhejinshuqingyanghuawubao
Low price main layer board cation, high price main layer board cation and interlayer anion are included, wherein, the low price main layer board sun
Ion comprises at least calcium ion；The preparation method includes step：
S1, calcium oxide mixed with the water soluble salt of high-valence cationic, obtain the first mixture；
S2, first mixture is soluble in water, the second mixture of acquisition；
S3, second mixture reacted into 4h~100h at 80 DEG C~300 DEG C, reaction product is through separation of solid and liquid, institute
The scrubbed drying of solid phase is obtained, obtains the calcium base layered composite metal hydroxides.
Further, the high-valence cationic is identical with the high price main layer board cation.
Further, the high-valence cationic is selected from Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、
Sn4+、Ti4+And Zr4+At least one of.
Further, the anion in the water soluble salt of the high-valence cationic is selected from Cl-、NO3 -、CO3 -、SO4 2-、SO3 2-、
S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-, it is p-aminobenzoic acid root, ethanedioic acid root, benzoate anion, salicylate, malonate, right
Any one in phthalic acid root, dodecyl sodium sulfonate root, dodecylbenzoic root and DBSA root.
Further, the amount of the material of calcium ion and the water soluble salt of the high-valence cationic in first mixture
The ratio between amount of material is 1:2~1000:1.
Further, in the step S1, in addition to：The water soluble salt of low price cation and/or hydroxide are added
Enter into first mixture.
Further, calcium ion in first mixture, low price cation total material amount and the high price sun from
The ratio between amount of material of water soluble salt of son is 1:2~1000:1；In first mixture calcium ion and the low price sun from
The ratio between amount of material of son is 1:2~100:1.
Further, the low price cation is identical with the low price main layer board cation.
Further, the low price cation is selected from Li+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+
And Be2+At least one of.
Further, the anion in the water soluble salt of the low price cation is selected from Cl-、NO3 -、CO3 -、SO4 2-、SO3 2-、
S2O3 2-、H2PO4 -、PO4 3-, p-aminobenzoic acid root, ethanedioic acid root, benzoate anion, salicylate, malonate, terephthaldehyde
Any one in acid group, dodecyl sodium sulfonate root, dodecylbenzoic root and DBSA root.
Further, the water soluble salt of the anion in the water soluble salt of the low price cation and the high-valence cationic
In anion it is identical.
The present invention is by reasonable selection reactant while by rationally controlling the ratio between each reactant so that final
It is main to obtain the layered composite metal hydroxides (abbreviation calcium base LDHs) for including calcium ion, without using sodium hydroxide, carbon
The raw materials such as sour sodium, it will not also correspond to and produce the accessory substances such as sodium salt；The calcium base LDHs of acquisition can be used through simple washing, significantly subtract
Lack the use of the freshwater resources such as slurry, while reached the Atom economy close to 100%, meet Green Chemistry
It is required that.At the same time, calcium base LDHs has the performances such as excellent heat endurance, fire resistance, ageing resistance by ultraviolet light, is optimization
The critical function additive of the high polymer material performance such as PVC, PP, PE, EVA.
Embodiment
Hereinafter, embodiments of the invention are described in detail in the future.However, it is possible to implement this hair in many different forms
It is bright, and the specific embodiment of the invention that should not be construed as limited to illustrate here.Conversely, there is provided these embodiments be for
The principle and its practical application of the present invention is explained, so that others skilled in the art are it will be appreciated that the present invention's is various
Embodiment and the various modifications for being suitable for specific intended application.
It will be appreciated that although can be used term " first ", " second " etc. to describe various materials herein, but these
Material should not be limited by these terms.These terms are only used for separating a material with another material.
The invention discloses a kind of preparation method of calcium base layered composite metal hydroxides, the calcium base layered composite metal
Hydroxide includes low price main layer board cation, high price main layer board cation and interlayer anion, wherein, low price main body
Laminate cation comprises at least calcium ion.
Comprised the steps according to the preparation method of the calcium base layered composite metal hydroxides of the present invention：
S1, calcium oxide mixed with the water soluble salt of high-valence cationic, obtain the first mixture.
Preferably, the water soluble salt and/or hydroxide of low price cation are also included in the first mixture；That is,
Calcium oxide, the water soluble salt of low price cation and/or the water soluble salt of hydroxide and high-valence cationic are mixed, obtain institute
State the first mixture.
Specifically, low price cation and the low price main layer board cation phase in calcium base layered composite metal hydroxides
Together, its middle or low price cation is represented with X, when the water soluble salt and/or hydroxide that include low price cation in the first mixture
, can be respectively with X during thing1、X2Deng expression；High-valence cationic is identical with high price main layer board cation, is represented with Y.
Low price cation is selected from Li+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+In at least
It is a kind of；High-valence cationic is selected from Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+In
At least one.
Anion in the water soluble salt of low price cation and the water soluble salt of high-valence cationic may be selected from Cl-、
NO3 -、CO3 -、SO4 2-、SO3 2-、S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-Deng inorganic anion or p-aminobenzoic acid root, ethanedioic acid
Root, benzoate anion, salicylate, malonate, p-phthalic bridge, dodecyl sodium sulfonate root, dodecylbenzoic root, ten
Any one in the organic anions such as dialkyl benzene sulfonic acids root；And preferably, the water soluble salt and high price sun of low price cation
Anion in the water soluble salt of ion is consistent.
Specifically, when the water soluble salt and/or hydroxide of low price cation are not present in the first mixture, first is mixed
The ratio between the amount of the material of calcium ion in compound and the amount of material of water soluble salt of high-valence cationic are 1:2~1000:1；And
When the water soluble salt and/or hydroxide of low price cation in the first mixture be present, then for the calcium in the first mixture from
The material of the amount of the total material of son, the water soluble salt of low price cation and/or hydroxide and the water soluble salt of high-valence cationic
The ratio between amount be 1:2~1000:1.
More specifically, when the water soluble salt and/or hydroxide of low price cation in the first mixture be present, then control
It is preferably 1 to make the ratio between amount of material of calcium ion and low price cation in the first mixture:2~100:1.
S2, the first mixture is soluble in water, the second mixture of acquisition.
Preferably, the quality control of used water is 1~1000 times of quality of the water soluble salt of high-valence cationic.
S3, the second mixture reacted into 4h~100h at 80 DEG C~300 DEG C, reaction product is solid through separation of solid and liquid, gained
Mutually scrubbed drying, obtain calcium base layered composite metal hydroxides.
Before the second mixture reacts, the second mixture is preferably stirred into 0.1h~4h, it is scattered with abundant dissolving,
Form uniform second mixture.
The solid phase of acquisition dries 12h preferably at 80 DEG C.
The pH value of the calcium base layered composite metal hydroxides obtained is determined, is found close to neutrality, that is to say, that according to this
It is prepared by the calcium base layered composite metal hydroxides that the preparation method of the calcium base layered composite metal hydroxides of invention obtains
During without using raw materials such as sodium carbonate, sodium hydroxides, it is corresponding also to produce the accessory substances such as sodium salt, and reactant is also basic
Reaction is complete, needs not move through multiple washing operation and can be used, has not only saved the freshwater resources such as a large amount of slurries.
Hereinafter, by the preparation side with reference to specific embodiment to the calcium base layered composite metal hydroxides according to the present invention
Method is described in detail, and for convenience of being contrasted to each embodiment, analysis in table form contrasts each embodiment.Embodiment
The comparing result under different experiments parameter in 1-7 is as shown in table 1.
Contrasts of the 1-7 under different experiments parameter according to an embodiment of the invention of table 1
Note：In table 1, " the first mol ratio " refer in the first mixture in the absence of low price cation water soluble salt and/or
During hydroxide, the ratio between amount of material of water soluble salt of calcium ion and high-valence cationic in the first mixture, or the first mixing
When the water soluble salt and/or hydroxide of low price cation in thing be present, calcium ion, the water of low price cation in the first mixture
The ratio between the amount of the total material of soluble and/or hydroxide and the amount of material of water soluble salt of high-valence cationic；" second mole
Than " refer to the water soluble salt and/or hydroxide that low price cation in the first mixture be present when, the calcium ion in the first mixture
The ratio between with the amount of material of low price cation.
Certainly, above-described embodiment is not limited to according to the preparation method of the calcium base layered composite metal hydroxides of the present invention
Described in 1-7；In other words, the calcium prepared is enabled to according to a kind of calcium base layered composite metal hydroxides of the present invention
Metal cation on the layers of metal hydroxides plate of base layered composite metal hydroxides is Ca2+With monovalent metal cation,
At least one of trivalent metal cation, tetravalent metal cation, other divalent metals can also be included；Meanwhile
For the metal cation of identical valence state, the cation of various metals can also be included.
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that：
In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (11)
1. a kind of preparation method of calcium base layered composite metal hydroxides, the calcium base layered composite metal hydroxides include
Low price main layer board cation, high price main layer board cation and interlayer anion, wherein, the low price main layer board sun from
Son comprises at least calcium ion；Characterized in that, the preparation method includes step：
S1, calcium oxide mixed with the water soluble salt of high-valence cationic, obtain the first mixture；
S2, first mixture is soluble in water, the second mixture of acquisition；
S3, second mixture reacted into 4h~100h at 80 DEG C~300 DEG C, reaction product is solid through separation of solid and liquid, gained
Mutually scrubbed drying, obtain the calcium base layered composite metal hydroxides.
2. preparation method according to claim 1, it is characterised in that the high-valence cationic and the high price main layer board
Cation is identical.
3. preparation method according to claim 2, it is characterised in that the high-valence cationic is selected from Al3+、Ni3+、Co3+、
Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+At least one of.
4. preparation method according to claim 1, it is characterised in that in the water soluble salt of the high-valence cationic it is cloudy from
Son is selected from Cl-、NO3 -、CO3 -、SO4 2-、SO3 2-、S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-, p-aminobenzoic acid root, ethanedioic acid root, benzene
Formate, salicylate, malonate, p-phthalic bridge, dodecyl sodium sulfonate root, dodecylbenzoic root and dodecane
Any one in base benzene sulfonic acid root.
5. according to any described preparation methods of claim 1-4, it is characterised in that the thing of calcium ion in first mixture
The ratio between the amount of matter and the amount of material of water soluble salt of the high-valence cationic are 1:2~1000:1.
6. according to any described preparation methods of claim 1-4, it is characterised in that in the step S1, in addition to：Will be low
The water soluble salt and/or hydroxide of valency cation are added into first mixture.
7. preparation method according to claim 6, it is characterised in that calcium ion in first mixture, at a low price sun from
The ratio between the amount of the total material of son and the amount of material of water soluble salt of the high-valence cationic are 1:2~1000:1；Described first
The ratio between amount of material of calcium ion and the low price cation is 1 in mixture:2~100:1.
8. preparation method according to claim 6, it is characterised in that the low price cation and the low price main layer board
Cation is identical.
9. preparation method according to claim 8, it is characterised in that the low price cation is selected from Li+、Mg2+、Zn2+、
Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of.
10. preparation method according to claim 6, it is characterised in that the moon in the water soluble salt of the low price cation
Ion is selected from Cl-、NO3 -、CO3 -、SO4 2-、SO3 2-、S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-, p-aminobenzoic acid root, benzoate anion,
Salicylate, ethanedioic acid root, malonate, p-phthalic bridge, dodecyl sodium sulfonate root, dodecylbenzoic root and 12
Any one in benzene sulfonamide acid group.
11. preparation method according to claim 10, it is characterised in that the moon in the water soluble salt of the low price cation
Ion is identical with the anion in the water soluble salt of the high-valence cationic.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759213A (en) * | 2010-01-05 | 2010-06-30 | 北京化工大学 | Method for preparing layered bimetal hydroxide by using metallic powder |
| CN106517304A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method of three-dimensional LDHs (layered double hydroxides) |
| CN106745116A (en) * | 2016-11-11 | 2017-05-31 | 中国科学院青海盐湖研究所 | A kind of preparation method of complex metal hydroxide |
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- 2017-09-01 CN CN201710780268.5A patent/CN107500328A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759213A (en) * | 2010-01-05 | 2010-06-30 | 北京化工大学 | Method for preparing layered bimetal hydroxide by using metallic powder |
| CN106517304A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method of three-dimensional LDHs (layered double hydroxides) |
| CN106745116A (en) * | 2016-11-11 | 2017-05-31 | 中国科学院青海盐湖研究所 | A kind of preparation method of complex metal hydroxide |
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Application publication date: 20171222 |