CN102247807B - Preparation method and usage of modified attapulgite adsorption material - Google Patents
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Abstract
The invention discloses a preparation method and usage of a modified attapulgite adsorption material. The method comprises the following steps: modifying attapulgite which has undergone purification and acid activation with an amino-silane coupling agent so as to introduce amino onto the surface of attapulgite; subjecting amino and excess acrylic acid ester to a Michael addition reaction so as tointroduce ester groups, subjecting introduced ester groups and polyethylene polyamine to a Michael addition reaction, carrying out underpressure distillation to remove a solvent and excess reactants,and carrying out vacuum drying, grinding and sieving to obtain a finished product. According to the invention, polyethylene polyamine or alcamine compounds are bonded to the surface of attapulgite through covalent bonds, thereby substantially improving adsorption performance of attapulgite to metal ions.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of Preparation method and use of modified attapulgite sorbing material.
Background technology
Attapulgite claims palygorskite again, be a kind of have a special chain layer structure contain Shuifu County's zeopan class clay mineral, its theoretical chemistry formula is Si
8Mg
5O
20(OH)
2(H
2O)
44H
2O, its natural nano passage and nanocrystal make it to have flourishing interior external surface area, often are used as the absorption that natural low-cost sorbent is used for grease-decolor, pet excrement.
For widening the application of attapulgite, the someone uses it for the absorption of industrial wastewater, but owing to the mineralogical limitation of attapulgite itself, it is directly used in Industrial Wastewater Treatment has the not good enough problem of absorption property.For this reason, many researchers adopt the acid heat activation, organic cation is surfactant-modified, silane coupler modified and mode such as surface grafting is improved the absorption property of attapulgite.Wherein, surface grafting mainly is the reactivity of utilizing the Si-OH that the surface of attapulgite is rich in, the difference in functionality group is grafted to the attapulgite surface, the functional group difference of surface grafting, the absorption property difference of attapulgite after the modification.
Zhao(Yijiang Zhao, Yan Chen, Meisheng Li, etc.Adsorption of Hg
2+From aqueous solution onto polyacrylamide/attapulgite.Journal of Hazardous Materials, 2009,171:640-646.) etc. the people adopt the mode of polymerisation in solution, at attapulgite surface grafting polyacrylamide, improve attapulgite to metal ion Hg
2+Absorption property.Liu(Peng Liu, Tingmei Wang.Adsorption properties of hyperbranched aliphatic polyester grafted attapulgite towards heavy metal ions.Journal of Hazardous Materials, 2007,149:75 – 79.) etc. the people adopts the mode of melt polycondensation, improves attapulgite to configuration metal ions Zn at the hyperbranched aliphatic polyester of attapulgite surface grafting
2+, Cd
2+Absorption property.
CN101658782A discloses the method that a kind of silane coupler modified attapulgite prepares adsorbent, by the amino of amino silicane coupling agent in the introducing of attapulgite surface, thereby, can improve attapulgite to the clearance of reactive dye in the waste water.Because what contain in the amino silicane coupling agent is amino less, therefore, this method is limited to the improvement of attapulgite absorption property.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of surface graft modification attapulgite, and the modified attapulgite that obtains by this preparation method obviously improves the absorption property of transition metal and heavy metal ion.
The technical scheme that the present invention adopts for its technical problem of solution provides a kind of preparation method of modified attapulgite sorbing material, may further comprise the steps:
(1) with through purify, the attapulgite of acid activation is raw material, by with the Silanization reaction of amino silicane coupling agent, introduce aminoly on the attapulgite surface, get silane coupler modified attapulgite;
(2) silane coupler modified attapulgite and acrylate carry out Michael addition reaction, introduce ester group at amino, get the attapulgite that ester group is end group;
(3) ester group is ester group and polyethylene polyamine or the hydramine reaction on the attapulgite of end group, generates modified polyamine attapulgite or alkamine modified attapulgite.
As preferably, a kind of preparation method of modified attapulgite sorbing material may further comprise the steps:
(1) will be scattered in the organic solvent through the attapulgite powder of purification, acid activation, purification, the attapulgite of acid activation and the mass volume ratio of organic solvent are counted 1:10-1:30 with g/ml, ultrasonic dispersion 10-30min, drip amino silicane coupling agent, the mass ratio of amino silicane coupling agent and attapulgite is 1:1-3:1,70-100 ℃ of reaction 6-10h; After reaction finishes, desolventizing, vacuum drying, grinding is sieved, and gets silane coupler modified attapulgite;
(2) silane coupler modified attapulgite is scattered in the methanol solution, the mass volume ratio of silane coupler modified attapulgite and methyl alcohol is counted 1:10-1:25 with g/ml, at 40-60 ℃, dropwise addition of acrylic acid ester under the stirring condition, acrylate and silane coupler modified attapulgite mass ratio are 3:1-5:1, drip afterreaction 12-36h, decompression distillation, desolventizing methyl alcohol and excessive acrylate, vacuum drying then namely is able to the attapulgite that ester group is end group;
(3) be that the attapulgite of ester group is scattered in the methanol solution with end group, end group is that the attapulgite of ester group and the mass volume ratio of methyl alcohol are counted 1:10-1:25 with g/ml, at 40-60 ℃, drip polyethylene polyamine or hydramine under the stirring condition, polyethylene polyamine or hydramine and end group are that the mass ratio of the attapulgite of ester group is 6:1-10:1, after dripping, reaction 12-36h, decompression distillation, desolventizing methyl alcohol and excessive polyethylene polyamine or hydramine, vacuum drying then namely gets polyamines graft modification attapulgite or alkamine modified attapulgite.
As preferably, the preparation method of described modified attapulgite sorbing material is characterized in that purifying, activation step is:
(1) with the pulverizing of raw ore attapulgite, ball milling, sieve, get powdery attapulgite stone, getting the former attapulgite adding of powdery mass fraction is in the sodium hexametaphosphate solution of 3%-5%, the mass ratio of attapulgite and water is 1:20-1:30, behind the stirring 12-36h, leaves standstill naturally, get upper strata suspension filtered, oven dry, grinding, make the purification attapulgite;
(2) the purification attapulgite being added concentration is in the hydrochloric acid solution of 1-6mol//L, the mass volume ratio of attapulgite and hydrochloric acid solution is counted 1:10-1:15 with g/ml, stirring at room 0.5-2h, centrifugation, the precipitate with deionized water washing is dried after detecting no chlorion with the 0.1mol/L liquor argenti nitratis ophthalmicus, namely gets the acid activation attapulgite.
As preferably, organic solvent is toluene or dimethylbenzene.
As preferably, described amino silicane coupling agent is selected from a kind of in gamma-aminopropyl-triethoxy-silane, γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, γ-aminopropyl methyldiethoxysilane, the γ-aminopropyl methyl dimethoxysilane.
As preferably, described acrylate is methyl acrylate or methyl methacrylate.
As preferably, polyethylene polyamine is selected from one or more in ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, the five ethene hexamines.
As preferably, hydramine is selected from diethanol amine or triethanolamine.
The advantage of modified attapulgite sorbing material of the present invention is: exist a plurality of O, N atoms with key lone pair electrons in polyethylene polyamine or the hydramine, these atomic energy and metal ion form coordinate bond, often are used as the functional group of chelating resin.Adopt polyethylene polyamine or hydramine graft modification attapulgite, can introduce a plurality of amino or hydroxyl on the attapulgite surface, significantly improve it to the absorption property of transition metal and heavy metal ion, and processing step is few, simple to operate.The present invention significantly improves attapulgite to Adsorption Properties for Metal Ions, has widened the application of attapulgite in fields such as metal ion sewage, noble metal recovery.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1
With the pulverizing of raw ore attapulgite, ball milling, sieve, get powdery attapulgite stone, getting the former attapulgite of powdery, to add mass fraction be in 3% the sodium hexametaphosphate solution, the mass ratio of attapulgite and water is 1:20, behind the stirring 12h, leaves standstill naturally, get upper strata suspension filtered, oven dry, grinding, make the purification attapulgite;
It is in the hydrochloric acid solution of 1mol//L that the purification attapulgite is added concentration, the mass volume ratio of attapulgite and hydrochloric acid solution is counted 1:10 with g/ml, stirring at room 0.5h, centrifugation, the precipitate with deionized water washing is dried after detecting no chlorion with the 0.1mol/L liquor argenti nitratis ophthalmicus, namely gets the acid activation attapulgite;
10g is scattered in the 100mL toluene through purification, acid activation attapulgite, ultrasonic dispersion 30min under the stirring condition, drips the 10g gamma-aminopropyl-triethoxy-silane, after dripping, be heated to 70 ℃, reaction 10h is after reaction finishes, desolventizing, vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite (I-NH
2);
Above-mentioned silane coupler modified attapulgite is scattered in the 100mL methanol solution, at 50 ℃, under the stirring condition, the dropwise addition of acrylic acid methyl esters, the mass ratio of methyl acrylate and silane coupler modified attapulgite is 3:1, drips afterreaction 24h, decompression distillation, desolventizing methyl alcohol and excessive methyl acrylate, vacuum drying then, namely being able to ester group is the attapulgite (I-CO of end group
2CH
3);
Be that the attapulgite of ester group is scattered in the 100mL methanol solution with above-mentioned end group, at 50 ℃, drip ethylenediamine under the stirring condition, ethylenediamine and end group are that the mass ratio of the attapulgite of ester group is 6:1, after dripping, and reaction 24h, decompression distillation, desolventizing methyl alcohol and excessive ethylenediamine, vacuum drying then namely gets ethylenediamine graft modification attapulgite (I).
Embodiment 2
With the pulverizing of raw ore attapulgite, ball milling, sieve, get powdery attapulgite stone, getting the former attapulgite of powdery, to add mass fraction be in 5% the sodium hexametaphosphate solution, the mass ratio of attapulgite and water is 1:30, behind the stirring 36h, leaves standstill naturally, get upper strata suspension filtered, oven dry, grinding, make the purification attapulgite;
It is in the hydrochloric acid solution of 6mol//L that the purification attapulgite is added concentration, the mass volume ratio of attapulgite and hydrochloric acid solution is counted 1:15 with g/ml, stirring at room 2h, centrifugation, the precipitate with deionized water washing is dried after detecting no chlorion with the 0.1mol/L liquor argenti nitratis ophthalmicus, namely gets the acid activation attapulgite;
The 10g attapulgite is scattered in the 300mL dimethylbenzene, ultrasonic dispersion 10min under the stirring condition, drips 30g γ-aminopropyl methyl dimethoxysilane, after dripping, be heated to 100 ℃, behind the reaction 6h, after reaction finishes, desolventizing, vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite (II-NH
2);
Above-mentioned silane coupler modified attapulgite is scattered in the 250mL methanol solution, at 40 ℃, under the stirring condition, drip methyl methacrylate, the mass ratio of methyl methacrylate and silane coupler modified attapulgite is 5:1, drips afterreaction 12h, decompression distillation, desolventizing methyl alcohol and excessive methyl methacrylate, vacuum drying then, namely being able to ester group is the attapulgite (II-CO of end group
2CH
3);
Be that the attapulgite of ester group is scattered in the 250mL methanol solution with above-mentioned end group, at 60 ℃, drip diethylenetriamine under the stirring condition, diethylenetriamine and end group are that the mass ratio of the attapulgite of ester group is 10:1, after dripping, and reaction 12h, decompression distillation, desolventizing methyl alcohol and excessive diethylenetriamine, vacuum drying then namely gets diethylenetriamine graft modification attapulgite (II).
Embodiment 3
With the pulverizing of raw ore attapulgite, ball milling, sieve, get powdery attapulgite stone, getting the former attapulgite of powdery, to add mass fraction be in 4% the sodium hexametaphosphate solution, the mass ratio of attapulgite and water is 1:23, behind the stirring 24h, leaves standstill naturally, get upper strata suspension filtered, oven dry, grinding, make the purification attapulgite;
It is in the hydrochloric acid solution of 2mol//L that the purification attapulgite is added concentration, the mass volume ratio of attapulgite and hydrochloric acid solution is counted 1:11 with g/ml, stirring at room 1h, centrifugation, the precipitate with deionized water washing is dried after detecting no chlorion with the 0.1mol/L liquor argenti nitratis ophthalmicus, namely gets the acid activation attapulgite;
The 10g attapulgite is scattered in the 200mL toluene, ultrasonic dispersion 20min under the stirring condition, drips the 20g γ-An Bingjisanjiayangjiguiwan, after dripping, be heated to 80 ℃, behind the reaction 8h, after reaction finishes, desolventizing, vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite (III-NH
2);
Above-mentioned silane coupler modified attapulgite is scattered in the 150mL methanol solution, at 60 ℃, under the stirring condition, the dropwise addition of acrylic acid methyl esters, the mass ratio of methyl acrylate and silane coupler modified attapulgite is 4:1, drips afterreaction 36h, decompression distillation, desolventizing methyl alcohol and excessive methyl acrylate, vacuum drying then, namely being able to ester group is the attapulgite (III-CO of end group
2CH
3);
Be that the attapulgite of ester group is scattered in the 150mL methanol solution with above-mentioned end group, at 40 ℃, drip diethanol amine under the stirring condition, diethanol amine and end group are that the mass ratio of the attapulgite of ester group is 8:1, after dripping, and reaction 36h, decompression distillation, desolventizing methyl alcohol and excessive diethanol amine, vacuum drying then namely gets diethanol amine graft modification attapulgite (III).
Embodiment 4
With the pulverizing of raw ore attapulgite, ball milling, sieve, get powdery attapulgite stone, getting the former attapulgite of powdery, to add mass fraction be in 3.5% the sodium hexametaphosphate solution, the mass ratio of attapulgite and water is 1:25, behind the stirring 20h, leaves standstill naturally, get upper strata suspension filtered, oven dry, grinding, make the purification attapulgite;
It is in the hydrochloric acid solution of 2mol//L that the purification attapulgite is added concentration, the mass volume ratio of attapulgite and hydrochloric acid solution is counted 1:12 with g/ml, stirring at room 1.5h, centrifugation, the precipitate with deionized water washing is dried after detecting no chlorion with the 0.1mol/L liquor argenti nitratis ophthalmicus, namely gets the acid activation attapulgite;
The 10g attapulgite is scattered in the 250mL dimethylbenzene, ultrasonic dispersion 20min under the stirring condition, drips 15gN-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, after dripping, be heated to 90 ℃, behind the reaction 7h, after reaction finishes, desolventizing, vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite (IV-NH
2);
Above-mentioned silane coupler modified attapulgite is scattered in the 200mL methanol solution, at 55 ℃, under the stirring condition, drip methyl methacrylate, the mass ratio of methyl methacrylate and silane coupler modified attapulgite is 3:1, drips afterreaction 24h, decompression distillation, desolventizing methyl alcohol and excessive methyl methacrylate, vacuum drying then, namely being able to ester group is the attapulgite (IV-CO of end group
2CH
3);
Be that the attapulgite of ester group is scattered in the 200mL methanol solution with above-mentioned end group, at 55 ℃, drip five ethene hexamines under the stirring condition, five ethene hexamines and end group are that the mass ratio of the attapulgite of ester group is 7:1, after dripping, and reaction 36h, decompression distillation, desolventizing methyl alcohol and five excessive ethene hexamines, vacuum drying then namely gets five ethene hexamine graft modification attapulgites (IV).
Embodiment 5
With the pulverizing of raw ore attapulgite, ball milling, sieve, get powdery attapulgite stone, getting the former attapulgite of powdery, to add mass fraction be in 5% the sodium hexametaphosphate solution, the mass ratio of attapulgite and water is 1:28, behind the stirring 30h, leaves standstill naturally, get upper strata suspension filtered, oven dry, grinding, make the purification attapulgite;
It is in the hydrochloric acid solution of 5mol//L that the purification attapulgite is added concentration, the mass volume ratio of attapulgite and hydrochloric acid solution is counted 1:14 with g/ml, stirring at room 1.5h, centrifugation, the precipitate with deionized water washing is dried after detecting no chlorion with the 0.1mol/L liquor argenti nitratis ophthalmicus, namely gets the acid activation attapulgite;
The 10g attapulgite is scattered in the 150mL dimethylbenzene, ultrasonic dispersion 20min under the stirring condition, drips 15g γ-aminopropyl methyldiethoxysilane, after dripping, be heated to 90 ℃, behind the reaction 7h, after reaction finishes, desolventizing, vacuum drying, grinding is sieved, and namely gets silane coupler modified attapulgite (V-NH
2);
Above-mentioned silane coupler modified attapulgite is scattered in the 150mL methanol solution, at 50 ℃, under the stirring condition, the dropwise addition of acrylic acid methyl esters, the mass ratio of methyl acrylate and silane coupler modified attapulgite is 3:1, drips afterreaction 24h, decompression distillation, desolventizing methyl alcohol and excessive methyl acrylate, vacuum drying then, namely being able to ester group is the attapulgite (V-CO of end group
2CH
3);
Be that the attapulgite of ester group is scattered in the 150mL methanol solution with above-mentioned end group, at 50 ℃, drip the mixture (mass ratio of five ethene hexamines and triethylene tetramine is 2:1) of five ethene hexamines and triethylene tetramine under the stirring condition, polyethylene polyamine mixture and end group are that the mass ratio of the attapulgite of ester group is 9:1, after dripping, reaction 24h, decompression distillation, desolventizing methyl alcohol and excessive reactant, vacuum drying then namely gets the common graft modification attapulgite of five ethene hexamines and triethylene tetramine (V).
Embodiment 6
The adsorption experiment method: take by weighing the 40mg adsorbent, add the metal ion solution of 20mL0.002mol/L respectively, 25 ℃ of constant temperature 20h leave standstill, and filter, and measure the solution metal ion concentration.Variation according to concentration of metal ions before and after the absorption is calculated as follows adsorbance:
In the formula: C
0Concentration (the mgL of metal ion before the-absorption
-1); C
eConcentration (the mgL of-absorption back metal ion
-1); The volume of V-solution (L); The dosage of m-adsorbent (g).
Modified attapulgite among the embodiment 1～5 and former attapulgite are carried out above-mentioned adsorption experiment respectively, and the result is as shown in table 1.
Table 1 attapulgite, modified attapulgite are to various Adsorption Properties for Metal Ions
Can find out that from the experimental result of last table modified attapulgite of the present invention is to metal cations Fe
3+, Zn
2+, Cu
2+, Hg
2+, Cr
3+, Ni
2+, Cd
2+Absorption property obviously improve than former attapulgite, amino modified attapulgite, ester group modified attapulgite.
Be enlightenment with above-mentioned foundation desirable embodiment of the present invention, by above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the specification, must determine its technical scope according to the claim scope.
Claims (6)
1. the preparation method of a modified attapulgite sorbing material may further comprise the steps:
(1) with through purify, the attapulgite of acid activation is raw material, by with the Silanization reaction of amino silicane coupling agent, introduce aminoly on the attapulgite surface, get silane coupler modified attapulgite;
(2) silane coupler modified attapulgite and acrylate carry out Michael addition reaction, introduce ester group at amino, get the attapulgite that ester group is end group;
(3) ester group is ester group and polyethylene polyamine or the hydramine reaction on the attapulgite of end group, generates modified polyamine attapulgite or alkamine modified attapulgite;
Concrete steps are:
(1) will be scattered in the organic solvent through the attapulgite powder of purification, acid activation, purification, the attapulgite of acid activation and the mass volume ratio of organic solvent are counted 1:10-1:30 with g/ml, ultrasonic dispersion 10-30min, drip amino silicane coupling agent, the mass ratio of amino silicane coupling agent and attapulgite is 1:1-3:1,70-100 ℃ of reaction 6-10h; After reaction finishes, desolventizing, vacuum drying, grinding is sieved, and gets silane coupler modified attapulgite;
(2) silane coupler modified attapulgite is scattered in the methanol solution, the mass volume ratio of silane coupler modified attapulgite and methyl alcohol is counted 1:10-1:25 with g/ml, at 40-60 ℃, dropwise addition of acrylic acid ester under the stirring condition, acrylate and silane coupler modified attapulgite mass ratio are 3:1-5:1, drip afterreaction 12-36h, decompression distillation, desolventizing methyl alcohol and excessive acrylate, vacuum drying then namely is able to the attapulgite that ester group is end group;
(3) be that the attapulgite of ester group is scattered in the methanol solution with end group, end group is that the attapulgite of ester group and the mass volume ratio of methyl alcohol are counted 1:10-1:25 with g/ml, at 40-60 ℃, drip polyethylene polyamine or hydramine under the stirring condition, polyethylene polyamine or hydramine and end group are that the mass ratio of the attapulgite of ester group is 6:1-10:1, after dripping, reaction 12-36h, decompression distillation, desolventizing methyl alcohol and excessive polyethylene polyamine or hydramine, vacuum drying then namely gets modified polyamine attapulgite or alkamine modified attapulgite;
Described purification, activation step are:
(1) with the pulverizing of raw ore attapulgite, ball milling, sieve, get powdery attapulgite stone, getting powdery raw ore attapulgite adding mass fraction is in the sodium hexametaphosphate solution of 3%-5%, the mass ratio of attapulgite and water is 1:20-1:30, behind the stirring 12-36h, leaves standstill naturally, get upper strata suspension filtered, oven dry, grinding, make the purification attapulgite;
(2) the purification attapulgite being added concentration is in the hydrochloric acid solution of 1-6mol/L, the mass volume ratio of attapulgite and hydrochloric acid solution is counted 1:10-1:15 with g/ml, stirring at room 0.5-2h, centrifugation, the precipitate with deionized water washing is dried after detecting no chlorion with the 0.1mol/L liquor argenti nitratis ophthalmicus, namely gets the acid activation attapulgite;
Described polyethylene polyamine is selected from one or more in diethylenetriamine, triethylene tetramine, TEPA, the five ethene hexamines.
2. the preparation method of the described modified attapulgite sorbing material of claim 1 is characterized in that organic solvent is toluene or dimethylbenzene.
3. the preparation method of the described modified attapulgite sorbing material of claim 1 is characterized in that described amino silicane coupling agent is selected from a kind of in gamma-aminopropyl-triethoxy-silane, γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, γ-aminopropyl methyldiethoxysilane, the γ-aminopropyl methyl dimethoxysilane.
4. the preparation method of the described modified attapulgite sorbing material of claim 1 is characterized in that described acrylate is methyl acrylate or methyl methacrylate.
5. the preparation method of the described modified attapulgite sorbing material of claim 1 is characterized in that described hydramine is selected from diethanol amine or triethanolamine.
6. the purposes of the attapulgite sorbing material of each described modified attapulgite sorbing material preparation method acquisition of claim 1 to 5 is characterized in that this sorbing material can be used for absorption and the noble metal recovery of metallic wastewater.
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