CN106517261B - The preparation method of magnesium-based complex metal hydroxide - Google Patents
The preparation method of magnesium-based complex metal hydroxide Download PDFInfo
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- CN106517261B CN106517261B CN201610994643.1A CN201610994643A CN106517261B CN 106517261 B CN106517261 B CN 106517261B CN 201610994643 A CN201610994643 A CN 201610994643A CN 106517261 B CN106517261 B CN 106517261B
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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
- C01F5/00—Compounds of magnesium
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
Abstract
The invention discloses a kind of preparation methods of magnesium-based complex metal hydroxide, the magnesium-based complex metal hydroxide includes that low price main layer board cation, high price main layer board cation and interlayer anion, middle or low price main layer board cation include at least magnesium ion；The preparation method includes step：S1, the by-product magnesium hydroxide by purity not less than 60% are mixed with the water soluble salt of the first low price cation, obtain the first mixture；S2, the first mixture is mixed and soluble in water with the water soluble salt of high-valence cationic, obtains the second mixture；S3, the second mixture is reacted to 4h~100h at 80 DEG C~300 DEG C, reaction product is through being separated by solid-liquid separation, the washed drying of gained solid phase, obtains magnesium-based complex metal hydroxide.The preparation method of magnesium-based composition metal magnesium hydroxide according to the present invention realizes the recycling of waste using by-product magnesium hydroxide as raw material, reduces pollution and waste.
Description
Technical field
The invention belongs to inorganic non-metallic technical field of function materials, in particular, being related to a kind of magnesium-based composition metal hydrogen
The preparation method of oxide.
Background technology
China is richly stored with extra large lake bittern water and ore magnesium resource.Byproduct in process quantity is developed and used in magnesium resource
Considerable magnesium hydroxide, since by-product magnesium hydroxide (magnesium hydroxide content is not less than 60%) purity is relatively low, foreign ion type
It is more, it can not directly utilize and be discarded by most enterprises.A large amount of by-product magnesium hydroxide not only restricts the further progress of production,
The waste of resource and unreasonable exploitation are also created simultaneously, therefore by-product magnesium hydroxide is recycled with critically important
Meaning.
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, with the metal sun with different charges 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
Indicate the monovalent metal cation being located on layers of metal hydroxides plate, divalent metal, trivalent metal cation and four
Valence 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 cannot be the amount for the substance that 0, m is interlayer hydrone simultaneously.
LDHs have the characteristics that Subjective and Objective element species and quantity is adjustable, laminate it is elastic it is adjustable, size and shape is adjustable,
LDHs is ground due to the particularity of its structure and performance are greatly strengthened in catalysis, the energy, biosensor, absorption, drug 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.
The preparation method of traditional LDHs mainly has hydro-thermal method, the precipitation method, in-situ synthesis, ion-exchange, roasting also
Former method etc..In the preparation method of traditional LDHs, on the one hand, need with sodium hydroxide, ammonium hydroxide, sodium carbonate, ammonium carbonate etc. be
Raw material, can introduce new by-product, not only need to carry out the lock out operation of LDHs and by-product, but also the LDHs after separation is also needed
Washed, conventional method often produce 1 ton of LDHs can 2 tons or so of by-product the by-products such as sodium salt, ammonium salt, need tens times very
Water to hundreds of times is washed, and a large amount of wastes of water resource are caused；On the other hand, CO is also needed in certain methods2Etc. acidity
Gas, operation is increasingly complex, and gas can also bring that Keep Clear-High Voltage using accidentally.
Invention content
To solve the above-mentioned problems of the prior art, the present invention provides a kind of systems of magnesium-based complex metal hydroxide
By-product magnesium hydroxide can be used to prepare magnesium-based complex metal hydroxide by Preparation Method, the preparation method, realize returning for waste
It receives and recycles, reduce pollution and waste.
In order to reach foregoing invention purpose, present invention employs the following technical solutions：
A kind of preparation method of magnesium-based complex metal hydroxide, the magnesium-based complex metal hydroxide include main at a low price
Body laminate cation, high price main layer board cation and interlayer anion, wherein the low price main layer board cation is at least
Including magnesium ion；The preparation method includes step：S1, by-product magnesium hydroxide and the water soluble salt of the first low price cation are mixed
It closes, obtains the first mixture；Wherein, the mass percent of the magnesium hydroxide in the by-product magnesium hydroxide is not less than 60%；S2,
First mixture is mixed and soluble in water with the water soluble salt of high-valence cationic, obtains the second mixture；S3, will be described
Second mixture reacts 4h~100h at 80 DEG C~300 DEG C, and reaction product is through being separated by solid-liquid separation, the washed drying of gained solid phase,
Obtain the magnesium-based complex metal hydroxide.
Further, described first is cationic identical as the low price main layer board cation at a low price；The high price sun from
It is sub identical as the high price main layer board cation.
Further, described first is cationic selected from Li at a low price+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、
Cd2+And Be2+At least one of；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 moon in the water soluble salt of the first low price cation and the water soluble salt of the high-valence cationic
Ion is selected from Cl-、SO4 2-、CO3 2-、NO3 -In any one.
Further, it is described first at a low price cation water soluble salt in anion and the high-valence cationic it is water-soluble
Anion in property salt is identical.
Further, the amount of the total material of magnesium ion, the first low price cation and the high price in first mixture
The ratio between amount of substance of water soluble salt of cation is 1:2~6:1；Magnesium ion and first low price in first mixture
The ratio between amount of substance of cation is 1:1~1000:1.
Further, in the step S1, further include：The hydroxide of second cation at a low price is added to described the
In one mixture.
Further, magnesium ion, the first cationic at a low price, the second low price cation total material in first mixture
The ratio between the amount of substance of water soluble salt of amount and the high-valence cationic be 1:2~6:1；In first mixture magnesium from
The amount of the total material of cation and the ratio between amount of substance of the first low price cation are 1 at a low price for son, second:1~1000:1.
Further, described second is cationic identical as the low price main layer board cation at a low price.
Further, described second is cationic selected from Li at a low price+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、
Cd2+And Be2+At least one of.
The present invention is by reasonably selecting reactant while by rationally controlling the ratio between each reactant so that final
Main acquisition includes the complex metal hydroxide (abbreviation magnesium-based LDHs) of magnesium ion, without association sodium hydroxide, sodium carbonate
Equal by-products；The magnesium-based LDHs of acquisition can be used through simple washing, and the use of the freshwater resources such as slurry is greatly reduced,
Reach the Atom economy close to 100% simultaneously, meets the requirement of Green Chemistry.At the same time, magnesium-based LDHs has excellent
The performances such as different thermal stability, flame retardant property, ageing resistance by ultraviolet light are the high polymer materials performances such as optimization PVC, PP, PE, EVA
Critical function additive.Magnesium-based LDHs is prepared by raw material of industrial by-product magnesium hydroxide, can not only realize the recycling profit of waste
With reducing cost, moreover it is possible to which the higher value application of magnesium resource is realized in the development for promoting related industry chain.
Specific implementation mode
Hereinafter, detailed description of the present invention embodiment in future.However, it is possible to implement this hair in many different forms
It is bright, and the present invention should not be construed as limited to the specific embodiment illustrated here.On the contrary, provide these embodiments be for
Explanation the principle of the present invention and its practical application, to make others skilled in the art it will be appreciated that the present invention's is various
Embodiment and the various modifications for being suitable for specific intended application.
Term " first ", " second " etc. herein can be used to describe various substances although will be appreciated that, these
Substance should not be limited by these terms.These terms are only used to separate a substance with another substance.
The invention discloses a kind of preparation method of magnesium-based complex metal hydroxide, the magnesium-based complex metal hydroxides
Including low price main layer board cation, high price main layer board cation and interlayer anion, wherein low price main layer board sun from
Son includes at least magnesium ion.
The preparation method of magnesium-based complex metal hydroxide according to the present invention includes the following steps：
S1, by-product magnesium hydroxide is mixed with the water soluble salt of the first low price cation, obtains the first mixture.
Specifically, by-product magnesium hydroxide refers to that the mass percent of wherein magnesium hydroxide is not less than 60% magnesium hydroxide
It is rough, the by-product that other mineral generate in process can be derived from；The purity of by-product magnesium hydroxide is preferably greater than
70%.
Preferably, further include the hydroxide of the second low price cation in the first mixture；That is, by by-product hydrogen-oxygen
Change the hydroxide mixing of magnesium, the water soluble salt of the first low price cation and the second low price cation, acquisition described first is mixed
Close object.
Specifically, first cationic at a low price, the second low price cation and the low price master in magnesium-based complex metal hydroxide
Body laminate cation is identical, wherein the first low price cation and the second low price cation use X respectively1、X2It indicates.
It is two respectively that two classes in pre-prepared magnesium-based complex metal hydroxide, which have the metal cation of different valence state,
Valence metal cation and trivalent metal cation；The first low price cation and the second low price cation are selected from Li as a result,+、Mg2 +、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of.
Anion in the water soluble salt of first low price cation is selected from Cl-、SO4 2-、CO3 2-、NO3 -In any one.
When the second hydroxide of cation at a low price is not present in the first mixture, magnesium ion in the first mixture with
The ratio between amount of substance of water soluble salt of first low price cation preferably 1:1~1000:1；When there are in the first mixture
Two at a low price the hydroxide of cation when, then be the hydroxide of magnesium ion, the second cation at a low price in the first mixture
The ratio between the amount of total material and amount of substance of water soluble salt of the first low price cation preferably 1:1~1000:1.
S2, the first mixture is mixed and soluble in water with the water soluble salt of high-valence cationic, obtains the second mixture.
Specifically, high-valence cationic is identical as high price main layer board cation, is indicated with Y；High-valence cationic is selected from Al3+、
Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+At least one of.
More specifically, when the second hydroxide of cation at a low price is not present in the first mixture, the first mixture
In magnesium ion, the first water soluble salt of the amount and high-valence cationic of the total material of the water soluble salt of cation at a low price substance
The ratio between amount is 1:2~6:1；When in the first mixture there are second at a low price cation hydroxide when, then be the first mixture
In magnesium ion, first at a low price the water soluble salt of cation, second at a low price the amount of the total material of the hydroxide of cation with it is high
The ratio between amount of substance of water soluble salt of valence cation is 1:2~6:1.
Preferably, the quality control of used water is 1~100 times of quality of the water soluble salt of high-valence cationic.
S3, the second mixture is reacted to 4h~100h at 80 DEG C~300 DEG C, for reaction product through being separated by solid-liquid separation, gained is solid
Mutually washed drying obtains magnesium-based complex metal hydroxide.
Before the second mixture reacts, the second mixture is preferably stirred into 0.1h~4h, is disperseed with abundant dissolving,
Form uniform second mixture.
Second mixture carries out hydro-thermal reaction preferably in hydrothermal reaction kettle at 80 DEG C~250 DEG C.
The solid phase of acquisition dry 12h preferably at 80 DEG C.
The pH value of the magnesium-based complex metal hydroxide obtained is measured, is found close to neutrality, that is to say, that according to the present invention
Magnesium-based complex metal hydroxide preparation method obtain magnesium-based complex metal hydroxide will not be big in preparation process
Amount generates the basic by-products such as sodium carbonate, sodium hydroxide, and also fundamental reaction is complete for reactant, needs not move through multiple washing operation
It can be used, not only saved the freshwater resources such as a large amount of slurries, while also using a large amount of by-product magnesium hydroxides as former
Material reduces wastes and pollution, reduces cost, and simplifies technique.
Hereinafter, by with reference to specific embodiment to the preparation method of magnesium-based complex metal hydroxide according to the present invention into
The detailed description of row, for convenience of being compared to each embodiment, analysis in table form compares each embodiment.Embodiment 1-7
In the comparing result under different experiments parameter it is as shown in table 1.
Comparisons of the 1-7 under different experiments parameter according to an embodiment of the invention of table 1
Note：In table 1, when " molar ratio " refers to the hydroxide that the second low price cation is not present in the first mixture, the
The water soluble salt of the amount and high-valence cationic of the total material of magnesium ion, the first cationic water soluble salt of low price in one mixture
In the ratio between amount of substance or the first mixture there are second at a low price the hydroxide of cation when, magnesium ion in the first mixture,
The water of the amount and high-valence cationic of the total material of the water soluble salt of first low price cation, the second cationic hydroxide of low price
The ratio between amount of substance of soluble.
Certainly, the preparation method of magnesium-based complex metal hydroxide according to the present invention is not limited to above-described embodiment 1-7
It is described；In other words, a kind of by-product magnesium hydroxide according to the present invention using method enables to the magnesium-based prepared multiple
It is Mg to close the metal cation on the layers of metal hydroxides plate of metal hydroxides2+With monovalent metal cation, trivalent metal
At least one of cation, tetravalent metal cation, can also include other divalent metals；Meanwhile for identical
The metal cation of valence state can also include the cation of various metals.
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 (6)
1. a kind of preparation method of magnesium-based complex metal hydroxide, the magnesium-based complex metal hydroxide include low price main body
Laminate cation, high price main layer board cation and interlayer anion, wherein the low price main layer board cation at least wraps
Include magnesium ion；It is characterized in that, the preparation method includes step：
S1, by-product magnesium hydroxide is mixed with the water soluble salt of the first low price cation, obtains the first mixture；Wherein, described
The mass percent of magnesium hydroxide in by-product magnesium hydroxide is not less than 60%；Described first is cationic selected from Li at a low price+、Mg2+、
Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of, and the water of the first low price cation
Anion in soluble is identical with the anion in the water soluble salt of the high-valence cationic；
S2, first mixture is mixed and soluble in water with the water soluble salt of high-valence cationic, obtains the second mixture；Institute
It states high-valence cationic and is selected from Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+In extremely
Few one kind；Anion in the water soluble salt of the first low price cation and the water soluble salt of the high-valence cationic is selected from
Cl-、SO4 2-、CO3 2-、NO3 -In any one；
S3, second mixture is reacted to 4h~100h at 80 DEG C~300 DEG C, for reaction product through being separated by solid-liquid separation, gained is solid
Mutually washed drying obtains the magnesium-based complex metal hydroxide.
2. preparation method according to claim 1, which is characterized in that magnesium ion, the first low price in first mixture
The ratio between the amount of the total material of cation and the amount of substance of water soluble salt of the high-valence cationic are 1:2~6:1；Described first
The ratio between amount of substance of magnesium ion and the first low price cation is 1 in mixture:1~1000:1.
3. preparation method according to claim 1, which is characterized in that in the step S1, further include：At a low price by second
The hydroxide of cation is added into first mixture.
4. preparation method according to claim 3, which is characterized in that magnesium ion, the first low price in first mixture
The ratio between the amount of the total material of cation and the amount of substance of water soluble salt of the high-valence cationic are 1 at a low price for cation, second:
2~6:1；The amount of the total material of cation and first low price are cationic at a low price for magnesium ion, second in first mixture
The ratio between the amount of substance be 1:1~1000:1.
5. preparation method according to claim 3, which is characterized in that the second low price cation and the low price main body
Laminate cation is identical.
6. preparation method according to claim 5, which is characterized in that described second is cationic selected from Li at a low price+、Mg2+、Zn2 +、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of.
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| CN109052437B (en) * | 2018-09-19 | 2020-07-07 | 常州大学 | Preparation method of flower-shaped mesoporous magnesium oxide composed of nanoparticles |
| CN113371739A (en) * | 2020-02-25 | 2021-09-10 | 中国科学院青海盐湖研究所 | Preparation method of hexagonal flaky magnesium hydroxide nanosheet |
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| CN101759213B (en) * | 2010-01-05 | 2011-12-28 | 北京化工大学 | Method for preparing layered bimetal hydroxide by using metallic powder |
| KR101028350B1 (en) * | 2010-04-08 | 2011-04-11 | 신원산업 주식회사 | Layered mg-ti-al composite metal hydroxide and method of preparing the same |
| CN103964391B (en) * | 2013-01-28 | 2015-10-14 | 北京化工大学 | A kind of sheet structure layered double hydroxide and preparation method thereof |
| CN104860337B (en) * | 2015-05-06 | 2017-02-01 | 北京化工大学 | High pressure intercalation assembly method and application in preparation field of intercalation structure composite material |
| CN105753022B (en) * | 2016-03-28 | 2017-06-20 | 北京化工大学 | A kind of preparation method of magnesium-base layer-shaped complex hydroxide |
| CN105836769B (en) * | 2016-03-28 | 2017-06-23 | 北京化工大学 | A kind of clean method for preparing of magnesium-aluminum-based layered double hydroxide |
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