CN105502445B - A kind of preparation method of nano lamellar complex hydroxide - Google Patents

A kind of preparation method of nano lamellar complex hydroxide Download PDF

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CN105502445B
CN105502445B CN201510887545.3A CN201510887545A CN105502445B CN 105502445 B CN105502445 B CN 105502445B CN 201510887545 A CN201510887545 A CN 201510887545A CN 105502445 B CN105502445 B CN 105502445B
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唐平贵
李殿卿
冯拥军
陈廷伟
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Beijing University of Chemical Technology
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Abstract

The invention provides a kind of low cost preparation method of nano lamellar complex hydroxide, the method adopts bivalence and trivalent soluble metal nitrate or chloride to construct the raw material of LDH laminates, with calcium oxide as alkali source, suppress the formation of calcium deposit impurity using the chelation of calcium ion chelator, highly purified nano lamellar complex hydroxide can be prepared.Preparation method is simple of the present invention, without the need for High Temperature High Pressure, does not require special installation, and abundant raw material source is with low cost.The nano lamellar complex hydroxide can be widely applied to the fields such as adsorbing separation, catalysis, macromolecular material.

Description

A kind of preparation method of nano lamellar complex hydroxide
Art
The present invention relates to inorganic non-metallic functional material preparation field, and in particular to a kind of nano lamellar complex hydroxide Preparation method.
Background technology
Layered double hydroxide (LayeredDoubleHydroxides, abbreviation LDH) is that an anionoid type stratiform is glued Soil, its chemical formula are [M2+ 1-xM3+ x(OH)2]x+(An- x/n).mH2O, wherein M2+、M3+Represent respectively bivalence and trivalent metal sun from Son, x represent the change of metal element content, An-Represent interlayer anion.LDH has unique two-dimensional layered structure and interlayer cloudy The interchangeability of ion, is got more and more people's extensive concerning in recent years.LDH unique property makes which be widely used in being catalyzed, adsorbs, The field such as ion exchange and macromolecular material additive (function additive such as fire retardant, heat stabilizer).
LDH is generally prepared using methods such as coprecipitation, nucleation/crystallization isolation method, sluggish precipitations, document Abello S, Bolshak E, Montane D, Appl.Catal.A, 2013,450,261-274 with NaOH as precipitant, using co-precipitation Method is prepared for the NiFe-LDH of nano-scale；Bai ZM,Wang ZY,Zhang TG,Fu F,Yang N, Appl.Clay.Sci., 2012,59-60,36-41 equally adopt coprecipitation, are prepared for nanometer scale by alkali source of NaOH CoAl-LDH.Document Liu Z, Ma R, Osada M, Iyi N, Ebina Y, Takada K, et al, J.Am.Chem.Soc., 2006,128 (14), 4872-4880 adopt sluggish precipitation to be prepared for size for 5 microns with carbamide as precipitant CoAl-LDH., using NaOH as alkali source, 1 ton of LDH of production is about needed using 0.8 ton for coprecipitation and nucleation/crystallization isolation method NaOH, but the production cost of NaOH is higher, causes the preparation cost of LDH too high, is unfavorable for applications of the LDH in each field. Sluggish precipitation generally adopts carbamide for precipitant, makes carbamide slowly decompose release ammonia by heating and precipitates metal cation LDH is generated, but the method is heat time heating time longer, high energy consumption and micron order LDH can only be prepared, it is difficult to synthesis nano LDH.Cause And carry out nanoscale LDH low cost preparation researches for the application of extension LDH has important facilitation.
The content of the invention
It is an object of the invention to provide a kind of low cost preparation method of nano lamellar complex hydroxide, the stratiform is again Close hydroxide and can be used for the fields such as adsorbing separation, catalysis, macromolecular material.
This method take bivalence and trivalent soluble metal nitrate or chloride as the raw material for constructing LDH laminates, to aoxidize Calcium is alkali source, suppresses the formation of calcium deposit impurity using the chelation of calcium ion chelator, can prepare highly purified nanometer Layered double hydroxide.The chemical general formula of prepared nano lamellar complex hydroxide is：
M2+ 1-xM3+ x(OH)2(An-)x/n·mH2O
Wherein 0.2≤x≤0.4, m is interlayer crystalline water molecules number, 0.4≤m≤1；M2+For bivalent metal ion Mg2+、Zn2 +、Ni2+、Co2+、Fe2+、Mn2+、Cu2+In any one or more, preferred Mg2+、Zn2+、Ni2+、Co2+In one or two； M3+For trivalent metal ion Al3+、Co3+、Fe3+、Cr3+、Ga3+、V3+、Mn3+、Rh3+、Ir3+、In3+In any one or more, It is preferred that Al3+、Co3+、Fe3+In one or two；Interlayer anion An-For Cl-、NO3 -、ClO4 -、ClO3 -、CO3 2-、SO4 2-、 SO3 2-、S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-Deng inorganic anion or salicylate, para-amino benzoic acid root, ethanedioic acid root, third Any one in the organic anions such as two acid groups, p-phthalic bridge, dodecyl sodium sulfonate root, n are interlayer anion An-'s Valence state.
The invention provides a kind of preparation method of nano lamellar complex hydroxide, concrete preparation process is as follows：
A：The calcium oxide serosity that weight/mass percentage composition is 1～15% is prepared, serosity is ground in ball mill or colloid mill Mill 2～20 minutes.Prepare bivalence and trivalent metal saline solution that molar concentration is 0.15～3mol/L, wherein bivalence and trivalent gold The molar ratio of category cation is 2～5:1, and 2 [M2+]+3[M3+]=2 [CaO], wherein [M2+]、[M3+] represent respectively bivalence and The mole of trivalent metal ion, the mole of [CaO] for calcium oxide.
Described divalent metal salt is one or more in the nitrate or chloride of Mg, Zn, Ni, Co, Fe, Cu, Mn, It is preferably one or two in the nitrate or chloride of Mg, Zn, Ni, Co.
Described trivalent metal salt for Al, Co, Fe, Cr, Ga, V, Mn, Rh, Ir, In nitrate or chloride in appoint One or more of meaning, one or more in the nitrate or chloride of preferred Al, Co, Fe.
B：Bivalence and trivalent metal saline solution are dropped in calcium oxide serosity under stirring, dripped in 5～120 minutes Add it is complete, then by reaction system be heated to 30～105 DEG C continue reaction 3～6 hours, reaction terminate after serosity is filtered, wash Wash filter cake 3～6 times.
C：The filter cake obtained by step B is configured to into the serosity that solid content is 1～8%, by filter cake dry weight 0.2～10% Mass ratio is added to calcium ion chelator in the serosity, stirs；A is pressed againn-With the molar ratio of trivalent metal cation For 1.1～2:(n is interlayer anion A to nn-Valence state) ratio weigh containing required anion An-Salt be added in serosity, React 1～4 hour under 30～105 DEG C and stirring condition, reaction is cooled to room temperature after terminating, product is filtered, washing, dry It is dry, obtain nano lamellar complex hydroxide M2+ 1-xM3+ x(OH)2(An-)x/n·mH2O。
Described calcium ion chelator is ethylenediaminetetraacetic acid, aminotriacetic acid, diethylene-triamine pentaacetic acid, Fructus Citri Limoniae Acid, tartaric acid, gluconic acid, hydroxy ethylene diphosphonic acid, ATMP, ethylenediamine tetramethylene phosphonic acid, diethyl Five methylenephosphonic acid of alkene triamine, 2- phosphonobutane -1,2,4- tricarboxylic acids, double five methylenephosphonic acids of hexamethylene triamine, polyacrylic acid Or any one in the sodium salt of polymethylacrylic acid, potassium salt or ammonium salt.Its effect is to form chelate with calcium ion, suppresses calcium The formation of contamination precipitation.
Described An-Salt NnAnRepresent, wherein N is Na, NH4Or K, An-For ClO4 -、ClO3 -、CO3 2-、SO4 2-、SO3 2-、 S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-Deng inorganic anion or salicylate, para-amino benzoic acid root, ethanedioic acid root, malonic acid Any one in the organic anions such as root, p-phthalic bridge, dodecyl sodium sulfonate root.That more common is CO3 2-、SO4 2-、 H2PO4 -、HPO4 2-With any one in dodecyl sodium sulfonate root.The interlayer that its effect is to provide layered double hydroxide is cloudy Ion.
Accompanying drawing is X-ray diffractogram, infrared spectrum and the scanning electron microscope (SEM) photograph of LDH prepared by embodiment 1.X-ray diffractogram Show that prepared sample has the typical characteristic diffraction peaks of LDH；Infrared spectrum shows that LDH interlayer anion is carbonate；Sweep Retouch electron microscope and show prepared LDH structures and in nanometer scale in the form of sheets.
Advantages of the present invention：This method adopts bivalence and trivalent soluble metal nitrate or chloride and calcium oxide for former Material, has the advantages that abundant raw material source, cheap, preparation process are simple, reaction condition is gentle, be easy to industrialized production, The LDH of preparation is in nanometer scale, can be widely applied to be catalyzed, adsorb, environmental protection, the field such as high molecule plastic.
Description of the drawings:
Fig. 1 is the X-ray diffractogram of layered double hydroxide prepared by embodiment 1.
Fig. 2 is the infrared spectrum of layered double hydroxide prepared by embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of layered double hydroxide prepared by embodiment 1.
Specific embodiment：
By way of example the present invention is further described below, but does not constitute the limit to the scope of the present invention System.
Embodiment 1：
Step A：Weigh 5.88g calcium oxide to be added in 110g deionized waters, in grinding in ball grinder 5 minutes, be configured to Calcium oxide serosity.Weigh 12.198g MgCl2 .6H2O and 7.2429g AlCl3 .6H2O is prepared in being added to 100ml deionized waters Into saline solution.
Step B：Under magnetic stirring the saline solution of configuration is added dropwise in calcium oxide serosity, is dripped within 30 minutes Finish, serosity is heated to into 60 DEG C then and continues stirring reaction 6 hours, serosity filtration washing is answered for 3 times after terminating by reaction Close hydroxide filter cake.
C：The filter cake obtained by step B is distributed in 100ml deionized waters and is combined within 2 minutes with ball mill grinding Hydroxide slurry, weighs 0.2g disodiumedetates and is added in the serosity, stir, then weigh 1.9g Na2CO3It is added in serosity, stirring reaction 1 hour at 60 DEG C, reaction is cooled to room temperature, precipitate Jing centrifuge washings after terminating 8 are less than to pH value, drying obtains final product LDH products in 12 hours in 100 DEG C of baking ovens by sample.Elementary analysiss show the chemical group of product An accepted way of doing sth is：Mg0.66Al0.34(OH)2(CO3)0.17·0.6H2O。
Embodiment 2：
Step A：With embodiment 1, it is a difference in that and weighs calcium oxide and MgCl2 .6H2The quality of O be respectively 7.56g and 18.297g。
Step B：Under magnetic stirring the saline solution of configuration is added dropwise in calcium oxide serosity, is dripped within 20 minutes Finish, serosity is heated to into 80 DEG C then and continues stirring reaction 3 hours, serosity filtration washing is answered for 4 times after terminating by reaction Close hydroxide filter cake.
Step C：The filter cake obtained by step B is distributed in 150ml deionized waters and is obtained within 4 minutes with ball mill grinding Complex hydroxide serosity, weighs 0.4g disodiumedetates and is added in the serosity, stir, then weigh 2.0g Na2CO3It is added in serosity, stirring reaction 1 hour at 60 DEG C, reaction is cooled to room temperature, precipitate Jing centrifuge washings after terminating 8 are less than to pH value, drying obtains final product LDH products in 10 hours in 100 DEG C of baking ovens by sample.Elementary analysiss show the chemical group of product An accepted way of doing sth is：Mg0.75Al0.25(OH)2(CO3)0.125·0.65H2O。
Embodiment 3：
Step A：Weigh 5.88g calcium oxide to be added in 100g deionized waters, in grinding in ball grinder 8 minutes, be configured to Calcium oxide serosity.Weigh 15.384gMg (NO3)2 .6H2O and 11.253g Al (NO3)3 .9H2O matches somebody with somebody in being added to 90ml deionized waters Make saline solution.
Step B：Under mechanical stirring the saline solution of configuration is added dropwise in calcium oxide serosity, is dripped within 40 minutes Finish, serosity is heated to into 90 DEG C then and continues stirring reaction 2 hours, serosity filtration washing is answered for 4 times after terminating by reaction Close hydroxide filter cake.
C：The filter cake obtained by step B is distributed in 120ml deionized waters and is combined within 2 minutes with ball mill grinding Hydroxide slurry, weighs 0.5g aminotriacetic acid disodiums and is added in the serosity, 4.68g is weighed after stirring NaH2PO4·2H2O is added in serosity, stirring reaction 2 hours at 70 DEG C, and reaction is cooled to room temperature, precipitate Jing after terminating Centrifuge washing is less than 8 to pH value, and by sample, in 100 DEG C of baking ovens, drying obtains final product LDH products in 12 hours.Elementary analysiss show product Chemical constitution formula be：Mg0.66Al0.34(OH)2(H2PO4)0.34·0.7H2O。
Embodiment 4：
Step A：With embodiment 3, it is a difference in that and weighs 17.448gNi (NO3)2 .6H2O replaces Mg (NO3)2 .6H2O。
Step B：With embodiment 3.
Step C：The filter cake obtained by step B is distributed in 100ml deionized waters and is obtained within 2 minutes with ball mill grinding Complex hydroxide serosity, weighs 0.25g diethylene-triamine pentaacetic acid dipotassiums and is added in the serosity, weigh after stirring 2.97g(NH4)2SO4It is added in serosity, stirring reaction 5 hours at 50 DEG C, reaction is cooled to room temperature, precipitate Jing after terminating Centrifuge washing is less than 8 to pH value, and by sample, in 100 DEG C of baking ovens, drying obtains final product LDH products in 12 hours.Elementary analysiss show product Chemical constitution formula be：Ni0.66Al0.34(OH)2(SO4)0.17·0.74H2O。
Embodiment 5：
Step A, B is with embodiment 3.
Step C：The filter cake obtained by step B is distributed in 80ml deionized waters and is obtained within 3 minutes with ball mill grinding Complex hydroxide serosity, weighs 0.24g tartaric acid and is added in the serosity, and the addition of 6.4g sodium salicylate is weighed after stirring To in serosity, stirring reaction 3 hours at 70 DEG C, reaction are cooled to room temperature after terminating, and precipitate Jing centrifuge washings are little to pH value In 8, by sample, in 100 DEG C of baking ovens, drying obtains final product LDH products in 12 hours.Elementary analysiss show that the chemical constitution formula of product is： Ni0.66Al0.34(OH)2(C7H5O3)0.34·0.63H2O。
Embodiment 6：
Step A, B is with embodiment 3.
Step C：The filter cake obtained by step B is distributed in 120ml deionized waters and is obtained within 3 minutes with ball mill grinding Complex hydroxide serosity, weighs 0.4g hydroxy ethylene diphosphonic acid sodium and is added in the serosity, 7.9g is weighed after stirring Para aminobenzoic acid sodium salt is added in serosity, stirring reaction 2 hours at 90 DEG C, and reaction is cooled to room temperature, precipitate after terminating Jing centrifuge washings are less than 8 to pH value, and by sample, in 100 DEG C of baking ovens, drying obtains final product LDH products in 12 hours.Elementary analysiss show to produce The chemical constitution formula of product is：Ni0.66Al0.34(OH)2(C7H6NO2)0.34·0.72H2O。
Embodiment 7：
Step A：Weigh 5.88g calcium oxide to be added in 100g deionized waters, in grinding in ball grinder 8 minutes, be configured to Calcium oxide serosity.Weigh 7.692gMg (NO3)2 .6H2O、8.925gZn(NO3)2 .6H2O and 12.12g Fe (NO3)3 .9H2O is added Saline solution is configured to in 120ml deionized waters.
Step B：Under mechanical stirring the saline solution of configuration is added dropwise in calcium oxide serosity, is dripped within 20 minutes Finish, serosity is heated to into 40 DEG C then and continues stirring reaction 6 hours, serosity filtration washing is answered for 4 times after terminating by reaction Close hydroxide filter cake.
C：The filter cake obtained by step B is distributed in 150ml deionized waters and is combined within 3 minutes with ball mill grinding Hydroxide slurry, weighs 0.5g ammonium tartrates and is added in the serosity, 8.43gNaClO is weighed after stirring4·H2O is added To in serosity, stirring reaction 4 hours at 50 DEG C, reaction are cooled to room temperature after terminating, and precipitate Jing centrifuge washings are little to pH value In 7, by sample, in 95 DEG C of baking ovens, drying obtains final product LDH products in 12 hours.Elementary analysiss show that the chemical constitution formula of product is： Mg0.33Zn0.33Fe0.34(OH)2(ClO4)0.34·0.65H2O。
Embodiment 8：
Step A：Weigh 5.88g calcium oxide to be added in 200g deionized waters, in grinding in ball grinder 10 minutes, be configured to Calcium oxide serosity.Weigh 10.737gMn (NO3)2With 9.025g In (NO3)3Salt is configured in being added to 150ml deionized waters molten Liquid.
Step B：Under mechanical stirring the saline solution of configuration is added dropwise in calcium oxide serosity, is dripped within 35 minutes Finish, serosity is heated to into 100 DEG C then and continues stirring reaction 2 hours, serosity filtration washing is answered for 5 times after terminating by reaction Close hydroxide filter cake.
C：The filter cake obtained by step B is distributed in 200ml deionized waters and is combined within 6 minutes with ball mill grinding Hydroxide slurry, weighs 0.3g sodium polyacrylate and is added in the serosity, 12.96g dodecyl sulfur is weighed after stirring Sour sodium is added in serosity, stirring reaction 3 hours at 80 DEG C, and reaction is cooled to room temperature, precipitate Jing centrifuge washings after terminating 7 are less than to pH value, drying obtains final product LDH products in 12 hours in 95 DEG C of baking ovens by sample.Elementary analysiss show the chemical group of product An accepted way of doing sth is：Mn0.66In0.34(OH)2(C12H25SO4)0.34·0.55H2O。

Claims (3)

1. a kind of preparation method of nano lamellar complex hydroxide, comprises the following steps that：
A：The calcium oxide serosity that weight/mass percentage composition is 1～15% is prepared, serosity grinds in ball mill or colloid mill 2～ 20 minutes, prepare bivalence and trivalent metal saline solution that molar concentration is 0.15～3mol/L, wherein bivalence and trivalent metal sun The molar ratio of ion is 2～5:1, and 2 [M2+]+3[M3+]=2 [CaO], wherein [M2+]、[M3+] bivalence and trivalent are represented respectively The mole of metal ion, the mole of [CaO] for calcium oxide；
Described divalent metal salt is one or more in the nitrate or chloride of Mg, Zn, Ni, Co, Fe, Cu, Mn；It is described Trivalent metal salt for Al, Co, Fe, Cr, Ga, V, Mn, Rh, Ir, In nitrate or chloride in any one or more；
B：Bivalence and trivalent metal saline solution are dropped in calcium oxide serosity under stirring, dripped in 5～120 minutes Finish, reaction system is heated to into 30～105 DEG C then and continues reaction 3～6 hours, serosity is filtered after terminating by reaction, washing filter Cake 3～6 times；
C：The filter cake obtained by step B is configured to into the serosity that solid content is 1～8%, by the quality of filter cake dry weight 0.2～10% Than calcium ion chelator is added in the serosity, stir；A is pressed againn-Molar ratio with trivalent metal cation is 1.1 ～2:The ratio of n adds A containing anionn-Salt in serosity, n be interlayer anion An-Valence state, 30～105 DEG C and stirring React 1～4 hour under the conditions of mixing, reaction is cooled to room temperature after terminating, product is filtered, wash, be dried, obtain nanometer layer Shape complex hydroxide M2+ 1-xM3+ x(OH)2(An-)x/n·mH2O；
Described calcium ion chelator is ethylenediaminetetraacetic acid, aminotriacetic acid, diethylene-triamine pentaacetic acid, citric acid, wine Stone acid, gluconic acid, hydroxy ethylene diphosphonic acid, ATMP, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine Five methylenephosphonic acids, 2- phosphonobutane -1,2,4- tricarboxylic acids, double five methylenephosphonic acids of hexamethylene triamine, polyacrylic acid or poly- first Any one in the acrylic acid sodium salt of base, potassium salt or ammonium salt；
Described A containing anionn-Salt NnAnRepresent, wherein N is Na, NH4Or K, An-For ClO4 -、ClO3 -、CO3 2-、SO4 2-、 SO3 2-、S2O3 2-、H2PO4 -、HPO4 2-、PO4 3-, salicylate, para-amino benzoic acid root, ethanedioic acid root, malonate, to benzene two Any one in formate, dodecyl sodium sulfonate root.
2. the preparation method of nano lamellar complex hydroxide according to claim 1, is characterized in that two described in step A Valency slaine for Mg, Zn, Ni, Co nitrate or chloride in one or two；Described trivalent metal salt be Al, Co, One or two in the nitrate or chloride of Fe.
3. the preparation method of nano lamellar complex hydroxide according to claim 1, is characterized in that containing described in step C Anion An-Salt, wherein An-For CO3 2-、SO4 2-、H2PO4 -、HPO4 2-With any one in dodecyl sodium sulfonate root.
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