CN101007635A - Organic-pillared vermiculite mesoporous material and its preparing process and uses - Google Patents
Organic-pillared vermiculite mesoporous material and its preparing process and uses Download PDFInfo
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- CN101007635A CN101007635A CN 200710026416 CN200710026416A CN101007635A CN 101007635 A CN101007635 A CN 101007635A CN 200710026416 CN200710026416 CN 200710026416 CN 200710026416 A CN200710026416 A CN 200710026416A CN 101007635 A CN101007635 A CN 101007635A
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Abstract
The invention discloses an organic column-supported gallery vermiculite dielectric material and making method and usage, which is characterized by the following: guiding organic column structure into vermiculite mineral layer area; displaying vertical inclined single-layer arrangement for columning agent in the vermiculite layer with inclined angle at 54-60 deg; allocating vermiculite mineral suspension; making columning agent; reacting intercalation between columning agent and vermiculite suspension; aging; drying; fitting for adsorbing impurity in the environmental wastewater.
Description
Technical field
The present invention relates to the mesoporous material technology, particularly a kind of preparation method of organic-pillared vermiculite mesoporous material and the application aspect environmental pollution improvement thereof.
Background technology
Vermiculite is the layer aluminosilicate mineral of 2: 1 type structures, has good adsorption, ion-exchange performance etc., in industry, agricultural wide application is arranged all.Layer charge in its structure is 0.16～0.19, higher than smectite (0.12～0.16), lower than mica (1), and the residual negative electric charge that layer charge mainly replaces Si to produce by Al in the tetrahedrallayer causes, part derives from the residue positive charge that the ferric iron of octahedral sheet causes, the net negative charge after both offset is the layer charge number.On the origin cause of formation, vermiculite is the intermediate product of mica family mineral alteration to smectite family mineral.Existing studies show that, the type of clay mineral has tangible influence to the catalytic performance (particularly to proton-catalyzed reaction) of intercalation product.With the intercalation clay that layer charge mainly replaces beidellite that Si causes or saponite to be prepared into from Al in the tetrahedrallayer, its catalysis, absorption property obviously are better than mainly taking off the intercalation clay that stone is prepared into from montmorillonite in the octahedral layer or Hunk with layer charge.The protonation of Si-OH-Al key can produce stronger Blang's phase special acid position in the tetrahedrallayer that has its source in of this difference, and it is less relatively to take off in the stone this Si-OH-Al key at montmorillonite or Hunk.Obviously, for mineral such as vermiculite or micas, layer charge that its tetrahedron displacement produces and the thermostability of self are carried out intercalation modifying far above smectite with them, and its stability, catalytic performance and absorption property will be better.
Vermiculite mineral also is the nonmetal mineral of the advantage of China, its ore deposit reserve is normally large-scale and superhuge, its mineral are also purer relatively, and therefore the ore dressing of vermiculite and purify all easily than wilkinite carries out the environment attribute of vermiculite mineral and the research of Pollution abatement has broad application prospects.Vermiculite has the characteristics of high layer charge, so its uncharged silica face area is few, and this is its shortcoming.But also its layer charge height just, it can adsorb more quaternary ammonium salt cationic by ion-exchange, so organic-pillared vermiculite have meso-hole structure and organic carbon content high and advantage, this help it by distribution process to non-ionic type organic pollutant adsorption in the water.Mesoporous material (Mesoporous material) is the noticeable research object in nanometer material science field in recent years, because the high porosity (aperture size is 2-50nm) and the high-specific surface area of this material, thereby important application prospects is arranged at aspects such as absorption, filtration and catalysis.
Summary of the invention
The object of the present invention is to provide a kind of reaction times short, productive rate is high, be easy to the preparation method of the organic-pillared vermiculite mesoporous material of suitability for industrialized production.
Another object of the present invention is to provide a kind of mesoporous material by method for preparing.
Of the present invention also have a purpose to be to provide a kind of mesoporous material by method for preparing in the application aspect the environmental pollution improvement.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of organic-pillared vermiculite mesoporous material comprises the steps and processing condition:
(1) vermiculite mineral is pulverized, preparation vermiculite mineral suspension, and it is 100～400 purpose powders that vermiculite mineral is ground into fineness with impact type supper micron mill or ball mill, is scattered in to form suspension slurry in the water, the mass ratio of vermiculite mineral and water is 1: 10～1: 20;
(2) prepare organic pillaring agent: pillaring agent is made into the solution that concentration is 0.1～10.0mmol/L; Described organic pillaring agent is selected from a kind of in cats product or the anion surfactant or any two combination;
(3) intercalation between vermiculite mineral suspension and the organic pillaring agent, with proportioning is organic pillaring agent: vermiculite mineral is that stirred 1.0～2.0 hours under 60～80 ℃ of temperature organic pillaring agent and the vermiculite suspension mixing back of 0.5～5.0mmol: 1g, and the ultrasonication that is 20～100KHz with above-mentioned reaction system frequency is 10～30 minutes then;
(4) ageing with reacted product, places 40～60 ℃ of water bath with thermostatic control ageings 1～2 day, and the ageing temperature is controlled at about 40～60 ℃;
(5) drying: the column-supporting product after the ageing is placed the centrifugal clear liquid of removing of whizzer, and water flushing 3～5 times makes the pH value approach 7, at last column-supporting product is dried under 80～100 ℃ of temperature.
Described cats product comprises eight alkyl trimethyl ammonium salts, ten alkyl trimethyl ammonium salts, dodecyl trimethyl ammonium salt, tetradecyl leptodactyline, cetyltrimethyl ammonium salt, octadecyl leptodactyline, cetyl pyridinium salt, double hexadecyl dimethyl ammonium, two octadecyl dimethyl ammonium.
Described anion surfactant comprises sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, tetradecyl sodium sulfonate, 14 dialkyl benzene sulfonic acids sodium, sodium cetanesulfonate, hexadecyl benzene sulfonic acid sodium salt, octadecyl sodium sulfonate or octadecyl benzene sulfonic acid sodium salt.
Described pillaring agent is two kinds, and 0.2～5.0: 1 ratio is made into the solution that concentration is 0.1～10.0mmol/L with two kinds of organic surface active agents in molar ratio.
The present invention adopts ultrasonic technique to induce the organic mesoporous pillared vermiculite mineral of preparation, the mesoporous nano material that can prepare different apertures as required, and adjustable mesoporous pillaring agent is at the arrangement model of vermiculite interlamination region, when pillaring agent concentration is 1.0～2.0mmol/L, pillaring agent is the vertical arrangement of inclination individual layer in the vermiculite interlamination region, the angle of inclination is 54 °～60 °, and the mesoporous material interlamellar spacing is 2.0～3.5nm.When pillaring agent concentration was 2.0～10.0mmol/L, pillaring agent was the vertical arrangement of double-deck inclination in the vermiculite interlamination region, and the angle of inclination is 30 °～58 °, and the mesoporous material interlamellar spacing is 3.4～6.5nm.
Described organic-pillared vermiculite mesoporous material is applied to the absorption of environmental pollutant in the waste water and removes.For phenolic wastewater, the removal condition is neutrality or alkaline environment, pH value scope: 7～12; The dosage of sorbent material is a mesoporous material weight: contain phenol amount 1g: 500～1000ml; Churning time is 1.0～2.0 hours: for containing aniline waste water, the removal condition is neutrality or sour environment, pH value scope: 3～7; The dosage of sorbent material is a mesoporous material weight: contain aniline 1g: 500～1000ml; Churning time is 1.0～2.0 hours.For nitrobenzene-containing waste water, the removal condition is a neutral environment, pH value scope: 6.5～7.5; The dosage of sorbent material is a mesoporous material weight: nitrobenzene-containing 1g: 500～1000ml; Churning time is 1.0～2.0 hours
The principle of the invention: by ion-exchange, with certain organic cation the inorganic hydrated cation of interlayer that vermiculite mineral Central Plains pre-exists is cemented out, make it become hydrophobicity from wetting ability, increase simultaneously organic content and meso-hole structure in the vermiculite mineral again, can increase clay mineral greatly and from water, remove the ability of non-ionic type organic pollutant, thereby the favourable absorption agent that makes organic clay can be used as environmental organic pollutant is used.
The structure of the organic-pillared vermiculite mesoporous material of the present invention preparation and physicochemical property are compared with natural vermiculite mineral has very big difference: vermiculite through mesoporous pillared after its specific surface area by 40m
2/ g brings up to 280～360m
2/ g; Interlamination region is brought up to 2.0～6.5nm by 1.50nm; Absorption property also is improved largely.Simultaneously,, make pillared vermiculite mineral variable charge surface have greatly changed, ability is removed in the absorption of environmental pollutant in the waste water thereby strengthen owing in the vermiculite mineral interlamination region, imported organic rod structure.Vermiculite mineral is after different organic pillaring agents is pillared, and it is different to organic pollutant adsorption amount, adsorption rate and absorption, desorption isotherms such as aniline, phenol, chlorobenzene in the waste water.Adopt different preparation process can prepare the mesoporous absorption of organic-pillared vermiculite of different shape; By the different proportionings of different organic-pillared vermiculite mesoporous adsorption materials, can prepare the different sorts mesoporous adsorption material of organic pollutants not with superpower adsorptive power.
The present invention compared with prior art has following advantage and effect:
(1) the present invention adopts the organic pillaring agent of " copolymerization method " prepared and carries out the organic mesoporous intercalation of vermiculite, the productive rate height, is easy to carry out suitability for industrialized production;
(2) the present invention adopts ultrasonic technique to induce the preparation organic-pillared vermiculite mesoporous material, shortens the mesoporous intercalation time, improves mesoporous pillared efficient, saves running cost;
(3) manufacturing cost of the present invention is lower, and desired raw material is simple, and the main raw material vermiculite mineral is a kind of common at the widely distributed clay of laminar silicate mineral of occurring in nature, cheap, is easy to obtain;
(4) the present invention is the organic mesoporous adsorption material of feedstock production with the natural clay mineral vermiculite, after they are adsorbed with organic pollutants, organic pollutant is had locking action, is easy to recycling, disposes;
(5) the present invention can prepare the mesoporous nano material in different apertures as required, and can regulate and control the arrangement model of mesoporous pillaring agent in the vermiculite interlamination region easily;
(6) less investment of the present invention need not special specific equipment, helps practicing of mesoporous material, and running cost is low, and is good in economic efficiency, and market outlook are wide.
Description of drawings
Fig. 1 is the primary mineral of vermiculite XRD figure;
Fig. 2 is a dodecyl trimethyl ammonium pillared vermiculite mesoporous material XRD figure among the embodiment 1;
Fig. 3 is a tetradecyl trimethyl ammonium pillared vermiculite mesoporous material XRD figure among the embodiment 2;
Fig. 4 is a cetyltrimethyl ammonium pillared vermiculite mesoporous material XRD figure among the embodiment 3;
Fig. 5 is pillaring agent (octadecyl leptodactyline) among the embodiment 4 when concentration is 1.50mmol/L, octadecyl trimethyl ammonium pillared vermiculite mesoporous material XRD figure;
Fig. 6 is pillaring agent (octadecyl leptodactyline) among the embodiment 4 when concentration is 2.5mmol/L, octadecyl trimethyl ammonium pillared vermiculite mesoporous material XRD figure;
Fig. 7 is pillaring agent (octadecyl leptodactyline) among the embodiment 4 when concentration is 7.5mmol/L, octadecyl trimethyl ammonium pillared vermiculite mesoporous material XRD figure;
Fig. 8 is a cetyl pyridinium pillared vermiculite mesoporous material XRD figure among the embodiment 5;
Fig. 9 is ten dimethyl sulfonic acid sodium pillared vermiculite mesoporous material XRD figure among the embodiment 6;
Figure 10 is ten dimethyl sulfonic acid sodium among the embodiment 7, the composite pillared vermiculite mesoporous material XRD figure of cetyltrimethyl ammonium.
Embodiment
The present invention is described further below in conjunction with embodiment, but protection scope of the present invention is not limited to the scope that embodiment represents.
Embodiment 1
The preparation method of dodecyl trimethyl ammonium pillared vermiculite mesoporous material is as follows:
(1) vermiculite deposit stone was pulverized 200 mesh sieves after, add water and make the vermiculite suspension that concentration is 100g/L, promptly the mass ratio of vermiculite and water is 1: 10.
(2) preparation of dodecyl trimethyl ammonium pillaring agent: dodecyl trimethyl ammonium is made into the solution that concentration is 1mmol/L, under 60 ℃ of temperature condition, constantly stirred 20 minutes, make dodecyl trimethyl ammonium pillaring agent solution.
(3) the mesoporous intercalation of vermiculite suspension and dodecyl trimethyl ammonium pillaring agent: post liquid and the vermiculite suspension of getting respective numbers in the ratio of post liquid: vermiculite=1mmol: 1g are put into large beaker simultaneously, use magnetic agitation 2 hours under 65 ℃ of temperature condition; After stirring finished, it was in the ultrasonic washer of 50KHz that above-mentioned reaction system is moved into frequency, used ultrasonication 20 minutes.
(4) ageing: the product that intercalation is obtained places 60 ℃ of water bath with thermostatic control ageings under the temperature condition 2 days.
(5) drying: place whizzer centrifugal product after the ageing, discard clear liquid, water flushing 3～4 times is dried under 80 ℃ of temperature then, obtains the dodecyl trimethyl ammonium pillared vermiculite mesoporous material.
Detect through the powder crystal X ray, as shown in Figure 2, d (the 001)=3.99nm of prepared dodecyl trimethyl ammonium pillared vermiculite mesoporous material, interlamination region is 2.99nm, obviously greater than d (the 001)=1.50nm (as shown in Figure 1) of primary mineral of vermiculite, the dodecyl trimethyl ammonium intercalation interlamination region that enters vermiculite is described.
Embodiment 2
The preparation method of tetradecyl trimethyl ammonium pillared vermiculite mesoporous material is as follows:
(1) vermiculite deposit stone was pulverized 200 mesh sieves after, add water and make the vermiculite suspension that concentration is 100g/L, promptly the mass ratio of vermiculite and water is 1: 10.
(2) preparation of tetradecyl trimethyl ammonium pillaring agent: the tetradecyl trimethyl ammonium is made into the solution that concentration is 1mmol/L, under 60 ℃ of temperature condition, constantly stirred 20 minutes, make tetradecyl trimethyl ammonium pillaring agent solution.
(3) the mesoporous intercalation of vermiculite suspension and tetradecyl trimethyl ammonium pillaring agent: post liquid and the vermiculite suspension of getting respective numbers in the ratio of post liquid: vermiculite=1mmol: 1g are put into large beaker simultaneously, use magnetic agitation 2 hours under 65 ℃ of temperature condition; After stirring finished, it was in the ultrasonic washer of 50KHz that above-mentioned reaction system is moved into frequency, used ultrasonication 20 minutes.
(4) ageing: the product that intercalation is obtained places 60 ℃ of water bath with thermostatic control ageings under the temperature condition 2 days.
(5) drying: place whizzer centrifugal product after the ageing, discard clear liquid, water flushing 3～4 times is dried under 80 ℃ of temperature then, obtains tetradecyl trimethyl ammonium pillared vermiculite mesoporous material.
Detect through the powder crystal X ray, as shown in Figure 3, d (the 001)=4.20nm of prepared tetradecyl trimethyl ammonium pillared vermiculite mesoporous material, interlamination region is 3.20m, obviously greater than d (the 001)=1.50nm (as shown in Figure 1) of primary mineral of vermiculite, the tetradecyl trimethyl ammonium intercalation interlamination region that enters vermiculite is described.
Embodiment 3
The preparation method of cetyltrimethyl ammonium pillared vermiculite mesoporous material is as follows:
(1) vermiculite deposit stone was pulverized 200 mesh sieves after, add water and make the vermiculite suspension that concentration is 100g/L, promptly the mass ratio of vermiculite and water is 1: 10.
(2) preparation of cetyltrimethyl ammonium pillaring agent: cetyltrimethyl ammonium is made into the solution that concentration is 2.5mmol/L, under 60 ℃ of temperature condition, constantly stirred 20 minutes, make cetyltrimethyl ammonium pillaring agent solution.
(3) the mesoporous intercalation of vermiculite suspension and cetyltrimethyl ammonium pillaring agent: post liquid and the vermiculite suspension of getting respective numbers in the ratio of post liquid: vermiculite=1mmol: 1g are put into large beaker simultaneously, use magnetic agitation 2 hours under 65 ℃ of temperature condition; After stirring finished, it was in the ultrasonic washer of 50KHz that above-mentioned reaction system is moved into frequency, used ultrasonication 20 minutes.
(4) ageing: the product that intercalation is obtained places 60 ℃ of water bath with thermostatic control ageings under the temperature condition 2 days.
(5) drying: place whizzer centrifugal product after the ageing, discard clear liquid, water flushing 3～4 times is dried under 80 ℃ of temperature then, obtains the cetyltrimethyl ammonium pillared vermiculite mesoporous material.
Detect through the powder crystal X ray, as shown in Figure 4, d (the 001)=5.16nm of prepared cetyltrimethyl ammonium pillared vermiculite mesoporous material, interlamination region is 4.16nm, obviously greater than d (the 001)=1.50nm (as shown in Figure 1) of primary mineral of vermiculite, the cetyltrimethyl ammonium intercalation interlamination region that enters vermiculite is described.
Embodiment 4
The preparation method of octadecyl trimethyl ammonium pillared vermiculite mesoporous material is as follows:
(1) vermiculite deposit stone was pulverized 200 mesh sieves after, add water and make the vermiculite suspension that concentration is 100g/L, promptly the mass ratio of vermiculite and water is 1: 10.
(2) preparation of octadecyl trimethyl ammonium pillaring agent: the octadecyl trimethyl ammonium is made into the solution that concentration is 1.5mmol/L, 2.5mmol/L, 7.5mmol/L respectively, under 60 ℃ of temperature condition, constantly stirred 20 minutes, make octadecyl trimethyl ammonium pillaring agent solution.
(3) the mesoporous intercalation of vermiculite suspension and octadecyl trimethyl ammonium pillaring agent: post liquid and the vermiculite suspension of getting respective numbers in the ratio of post liquid: vermiculite=1mmol: 1g are put into large beaker simultaneously, use magnetic agitation 2 hours under 65 ℃ of temperature condition; After stirring finished, it was in the ultrasonic washer of 50KHz that above-mentioned reaction system is moved into frequency, used ultrasonication 20 minutes.
(4) ageing: the product that intercalation is obtained places 60 ℃ of water bath with thermostatic control ageings under the temperature condition 2 days.
(5) drying: place whizzer centrifugal product after the ageing, discard clear liquid, water flushing 3～4 times is dried under 80 ℃ of temperature then, obtains octadecyl trimethyl ammonium pillared vermiculite mesoporous material.
Detect through the powder crystal X ray, as shown in Figure 5, when pillaring agent (octadecyl leptodactyline) when concentration is 1.50mmol/L, the d (001) of prepared octadecyl trimethyl ammonium pillared vermiculite mesoporous material is 4.22nm, the octadecyl leptodactyline is the vertical arrangement of inclination individual layer in the vermiculite interlamination region, the angle of inclination is 55 °, and the mesoporous material interlamellar spacing is 3.22nm; Fig. 6 is for when pillaring agent (octadecyl leptodactyline) when concentration is 2.5mmol/L, the d (001) of prepared octadecyl trimethyl ammonium pillared vermiculite mesoporous material is 4.67nm, the octadecyl leptodactyline is to tilt double-deck vertical arrangement in the vermiculite interlamination region, the angle of inclination is 30 °, and the mesoporous material interlamellar spacing is 3.67nm; Fig. 7 is for when pillaring agent (octadecyl leptodactyline) when concentration is 7.5mmol/L, the d (001) of prepared octadecyl trimethyl ammonium pillared vermiculite mesoporous material is 6.41nm, the octadecyl leptodactyline is to tilt double-deck vertical arrangement in the vermiculite interlamination region, the angle of inclination is 54 °, and the mesoporous material interlamellar spacing is 5.41nm.
The preparation method of cetyl pyridinium pillared vermiculite mesoporous material is as follows:
(1) vermiculite deposit stone was pulverized 100 mesh sieves after, add water and make the vermiculite suspension that concentration is 50g/L, promptly the mass ratio of vermiculite and water is 1: 15.
(2) preparation of cetyl pyridinium pillaring agent: cetyl pyridinium is made into the solution that concentration is 2mmol/L, under 60 ℃ of temperature condition, constantly stirred 20 minutes, make cetyl pyridinium pillaring agent solution.
(3) the mesoporous intercalation of vermiculite suspension and cetyl pyridinium pillaring agent pillaring agent: post liquid and the vermiculite suspension of getting respective numbers in the ratio of post liquid: vermiculite=2mmol: 1g are put into large beaker simultaneously, use magnetic agitation 2 hours under 65 ℃ of temperature condition; After stirring finished, it was in the ultrasonic washer of 40KHz that above-mentioned reaction system is moved into frequency, used ultrasonication 15 minutes.
(4) ageing: the product that intercalation is obtained places 60 ℃ of water bath with thermostatic control ageings under the temperature condition 1 day.
(5) drying: place whizzer centrifugal product after the ageing, discard clear liquid, water flushing 3～4 times is dried under 80 ℃ of temperature then, obtains the cetyl pyridinium pillared vermiculite mesoporous material.
Detect through the powder crystal X ray, as shown in Figure 8, the d (001) of prepared cetyl pyridinium pillared vermiculite mesoporous material is 3.91nm, and its interlamination region is 2.91nm.Obviously greater than d (the 001)=1.50nm (as shown in Figure 1) of primary mineral of vermiculite, the cetyl pyridinium intercalation interlamination region that enters vermiculite is described.
Embodiment 6
The preparation method of sodium laurylsulfonate pillared vermiculite mesoporous material is as follows:
(1) vermiculite deposit stone was pulverized 100 mesh sieves after, add water and make the vermiculite suspension that concentration is 50g/L, promptly the mass ratio of vermiculite and water is 1: 20.
(2) preparation of sodium laurylsulfonate pillaring agent: sodium laurylsulfonate is made into the solution that concentration is 2mmol/L respectively, under 60 ℃ of temperature condition, constantly stirred 20 minutes, make sodium laurylsulfonate pillaring agent solution.
(3) the mesoporous intercalation of vermiculite suspension and sodium laurylsulfonate pillaring agent pillaring agent: post liquid and the vermiculite suspension of getting respective numbers in the ratio of post liquid: vermiculite=2mmol: 1g are put into large beaker simultaneously, use magnetic agitation 2 hours under 65 ℃ of temperature condition; After stirring finished, it was in the ultrasonic washer of 20KHz that above-mentioned reaction system is moved into frequency, used ultrasonication 30 minutes.
(4) ageing: the product that intercalation is obtained places 60 ℃ of water bath with thermostatic control ageings under the temperature condition 2 days.
(5) drying: place whizzer centrifugal product after the ageing, discard clear liquid, water flushing 3～4 times is dried under 80 ℃ of temperature then, obtains the sodium laurylsulfonate pillared vermiculite mesoporous material.
Detect through the powder crystal X ray, as shown in Figure 9, the d (001) of prepared sodium laurylsulfonate pillared vermiculite mesoporous material is 3.15nm, and its interlamination region is 2.15nm.Obviously greater than d (the 001)=1.50nm (as shown in Figure 1) of primary mineral of vermiculite, the sodium laurylsulfonate intercalation interlamination region that enters vermiculite is described.
Embodiment 7
The preparation method of sodium laurylsulfonate, the composite pillared vermiculite mesoporous material of cetyltrimethyl ammonium is as follows:
(1) vermiculite deposit stone was pulverized 100 mesh sieves after, add water and make the vermiculite suspension that concentration is 50g/L, promptly the mass ratio of vermiculite and water is 1: 15.
(2) preparation of sodium laurylsulfonate, cetyltrimethyl ammonium pillaring agent: sodium laurylsulfonate is made into the solution that concentration is 3mmol/L respectively, under 60 ℃ of temperature condition, constantly stirred 30 minutes, make sodium laurylsulfonate, cetyltrimethyl ammonium composite columns agent solution.
(3) the mesoporous intercalation of vermiculite suspension and sodium laurylsulfonate, cetyltrimethyl ammonium pillaring agent: post liquid and the vermiculite suspension of getting respective numbers in the ratio of post liquid: vermiculite=2mmol: 1g are put into large beaker simultaneously, use magnetic agitation 2 hours under 65 ℃ of temperature condition; After stirring finished, it was in the ultrasonic washer of 100KHz that above-mentioned reaction system is moved into frequency, used ultrasonication 30 minutes.
(4) ageing: the product that intercalation is obtained places 60 ℃ of water bath with thermostatic control ageings under the temperature condition 2 days.
(5) drying: place whizzer centrifugal product after the ageing, discard clear liquid, water flushing 3～4 times is dried under 80 ℃ of temperature then, obtains sodium laurylsulfonate, the composite pillared vermiculite mesoporous material of cetyltrimethyl ammonium.
Detect through the powder crystal X ray, as shown in figure 10, the d (001) of prepared sodium laurylsulfonate, the composite pillared vermiculite mesoporous material of cetyltrimethyl ammonium is 4.12nm, and its interlamination region is 3.12nm.Obviously greater than d (the 001)=1.50nm (as shown in Figure 1) of primary mineral of vermiculite, sodium laurylsulfonate, the cetyltrimethyl ammonium intercalation interlamination region that enters vermiculite is described.
Embodiment 8
Dodecyl trimethyl ammonium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 1 preparation) is to the absorption of aniline:
Get and contain the waste water 300mL that aniline concentration is 8000mg/L, dodecyl trimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 10 minutes.After reaching balance, aniline concentration is 373mg/L in the mensuration waste water, and its aniline rate of removing is 95%, and taking same method to measure primary mineral of vermiculite only is 24% to the aniline rate of removing.
Embodiment 9
The absorption of tetradecyl trimethyl ammonium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 2 preparations) p-nitrophenyl:
Getting nitrobenzene-containing concentration is the waste water 300mL of 6000mg/L, and tetradecyl trimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 20 minutes.After reaching balance, nitro phenenyl concentration is 246mg/L in the mensuration waste water, and its oil of mirbane rate of removing is 96%, and taking same method to measure the primary mineral of vermiculite p-nitrophenyl rate of removing only is 28%.
Cetyltrimethyl ammonium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 3 preparations) Pyrogentisinic Acid's absorption:
Get and contain the waste water 300mL that phenol concentration is 1000mg/L, cetyltrimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 20 minutes.After reaching balance, measuring phenol in wastewater concentration is 62mg/L, and its phenol rate of removing is 94%, and taking same method to measure the primary mineral of vermiculite Pyrogentisinic Acid rate of removing only is 17%.
Embodiment 11
Cetyltrimethyl ammonium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 3 preparation) is to the absorption of chlorobenzene:
Getting chloride benzene concentration is the waste water 300mL of 100mg/L, and cetyltrimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 20 minutes.After reaching balance, chlorobenzene concentration is 8.1mg/L in the mensuration waste water, and its chlorobenzene rate of removing is 92%, and taking same method to measure primary mineral of vermiculite only is 13% to the chlorobenzene rate of removing.
Embodiment 12
The absorption of octadecyl trimethyl ammonium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 4 preparations) p-nitrophenyl:
Get and contain the waste water 200mL that aniline concentration is 10g/L, octadecyl trimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 10 minutes.After reaching balance, aniline concentration is 594mg/L in the mensuration waste water, and its aniline rate of removing is 94%, and taking same method to measure primary mineral of vermiculite only is 29% to the aniline rate of removing.
Embodiment 13
The absorption of octadecyl trimethyl ammonium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 4 preparations) p-nitrophenyl:
Getting nitrobenzene-containing concentration is the waste water 200mL of 9000mg/L, and octadecyl trimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 15 minutes.After reaching balance, aniline concentration is 437mg/L in the mensuration waste water, and its aniline rate of removing is 95%, and taking same method to measure primary mineral of vermiculite only is 23% to the aniline rate of removing.
Embodiment 14
Cetyl pyridinium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 5 preparations) Pyrogentisinic Acid's absorption:
Get and contain the waste water 300mL that phenol concentration is 1000mg/L, cetyl pyridinium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 30 minutes.After reaching balance, measuring phenol in wastewater concentration is 123mg/L, and its phenol rate of removing is 88%, and taking same method to measure the primary mineral of vermiculite Pyrogentisinic Acid rate of removing only is 14%.
Cetyl pyridinium pillared vermiculite mesoporous material (by the mesoporous material of embodiment 5 preparation) is to the absorption of chlorobenzene:
Getting chloride benzene concentration is the waste water 300mL of 100mg/L, and cetyltrimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 10 minutes.After reaching balance, chlorobenzene concentration is 16.5mg/L in the mensuration waste water, and its chlorobenzene rate of removing is 83.5%, and taking same method to measure primary mineral of vermiculite only is 9% to the chlorobenzene rate of removing.
Embodiment 16
Sodium laurylsulfonate pillared vermiculite mesoporous material (by the mesoporous material of embodiment 6 preparation) is to the absorption of chlorobenzene:
Getting chloride benzene concentration is the waste water 200mL of 100mg/L, and cetyltrimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 60 minutes.After reaching balance, chlorobenzene concentration is 23.9mg/L in the mensuration waste water, and its chlorobenzene rate of removing is 76%, and taking same method to measure primary mineral of vermiculite only is 6% to the chlorobenzene rate of removing.
Embodiment 17
Sodium laurylsulfonate, the composite pillared vermiculite mesoporous material of cetyltrimethyl ammonium (by the mesoporous material of embodiment 7 preparations) Pyrogentisinic Acid's absorption:
Get and contain the waste water 200mL that phenol concentration is 1000mg/L, cetyltrimethyl ammonium pillared vermiculite mesoporous material consumption is 1g, absorption duration of oscillation 40 minutes.After reaching balance, measuring phenol in wastewater concentration is 134mg/L, and its phenol rate of removing is 87%, and taking same method to measure the primary mineral of vermiculite Pyrogentisinic Acid rate of removing only is 14%.
Can better implement the present invention as mentioned above.
Claims (10)
1, a kind of preparation method of organic-pillared vermiculite mesoporous material is characterized in that comprising the steps and processing condition:
(1) vermiculite mineral is pulverized, preparation vermiculite mineral suspension, and it is 100～400 purpose powders that vermiculite mineral is ground into fineness with impact type supper micron mill or ball mill, is scattered in to form suspension slurry in the water, the mass ratio of vermiculite mineral and water is 1: 10～1: 20;
(2) prepare organic pillaring agent: pillaring agent is made into the solution that concentration is 0.1～10.0mmol/L; Described organic pillaring agent is selected from a kind of in cats product or the anion surfactant or any two combination;
(3) intercalation between vermiculite mineral suspension and the organic pillaring agent, with proportioning is organic pillaring agent: the organic pillaring agent of vermiculite mineral=0.5～5.0mmol: 1g and vermiculite suspension mix the back and stirred 1.0～2.0 hours under 60～80 ℃ of temperature, and the ultrasonication that is 20～100KHz with above-mentioned reaction system frequency is 10～30 minutes then;
(4) ageing with reacted product, places 40～60 ℃ of water bath with thermostatic control ageings 1～2 day, and the ageing temperature is controlled at about 40～60 ℃;
(5) drying: the column-supporting product after the ageing is placed the centrifugal clear liquid of removing of whizzer, and water flushing 3～5 times makes the pH value approach 7, at last column-supporting product is dried under 80～100 ℃ of temperature.
2, the preparation method of organic-pillared vermiculite mesoporous material according to claim 1 is characterized in that: described cats product comprises eight alkyl trimethyl ammonium salts, ten alkyl trimethyl ammonium salts, dodecyl trimethyl ammonium salt, tetradecyl leptodactyline, cetyltrimethyl ammonium salt, octadecyl leptodactyline, cetyl pyridinium salt, double hexadecyl dimethyl ammonium or two octadecyl dimethyl ammonium.
3, the preparation method of organic-pillared vermiculite mesoporous material according to claim 1 is characterized in that: described anion surfactant comprises sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, tetradecyl sodium sulfonate, 14 dialkyl benzene sulfonic acids sodium, sodium cetanesulfonate, hexadecyl benzene sulfonic acid sodium salt, octadecyl sodium sulfonate or octadecyl benzene sulfonic acid sodium salt.
4, the preparation method of organic-pillared vermiculite mesoporous material according to claim 1, it is characterized in that: described pillaring agent is two kinds, and 0.2～5.0: 1 ratio is made into the solution that concentration is 0.1～10.0mmol/L with two kinds of organic surface active agents in molar ratio.
5. by the organic-pillared vermiculite mesoporous material of the described method of claim 1 preparation, it is characterized in that: in the vermiculite mineral interlamination region, imported organic rod structure, pillaring agent is the vertical arrangement of inclination individual layer in the vermiculite interlamination region, the angle of inclination is 54 °～60 °, and the mesoporous material interlamellar spacing is 2.0～3.5nm; Perhaps pillaring agent is the vertical arrangement of double-deck inclination in the vermiculite interlamination region, and the angle of inclination is 30 °～58 °, and the mesoporous material interlamellar spacing is 3.4～6.5nm.
6, organic-pillared vermiculite mesoporous material according to claim 4, it is characterized in that described vermiculite through mesoporous pillared after, its specific surface area is 240～360m
2/ g; Interlamination region is 2.0～6.5nm.
7, the application of the described organic-pillared vermiculite mesoporous material of claim 4 is characterized in that: described organic-pillared vermiculite mesoporous material is applied to the absorption of environmental pollutant in the waste water and removes.
8, the application of organic-pillared vermiculite mesoporous material according to claim 6 is characterized in that: for phenolic wastewater, the removal condition is neutrality or alkaline environment, pH value scope: 7～12; The dosage of sorbent material is a mesoporous material weight: contain phenol amount 1g: 100～1000ml; Churning time is 0.15～1.0 hour.
9, the application of organic-pillared vermiculite mesoporous material according to claim 6 is characterized in that: for containing aniline waste water, the removal condition is neutrality or sour environment, pH value scope: 3～7; The dosage of sorbent material is a mesoporous material weight: contain aniline 1g: 100～1000ml; Churning time is 0.15～1.0 hour.
10, the application of organic-pillared vermiculite mesoporous material according to claim 6 is characterized in that: for nitrobenzene-containing waste water, the removal condition is a neutral environment, pH value scope: 6.5～7.5; The dosage of sorbent material is a mesoporous material weight: nitrobenzene-containing 1g: 100～1000ml; Churning time is 0.15～1.0 hour.
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| CN101811021A (en) * | 2010-04-26 | 2010-08-25 | 西北农林科技大学 | Amphiphilic adsorbent capable of adsorbing both organic matter and heavy metal cation and preparation method thereof |
| CN101850983A (en) * | 2010-03-12 | 2010-10-06 | 中国科学院新疆理化技术研究所 | Ball milling method for preparing organic vermiculite with large layer distance |
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| CN101850983A (en) * | 2010-03-12 | 2010-10-06 | 中国科学院新疆理化技术研究所 | Ball milling method for preparing organic vermiculite with large layer distance |
| CN101811021A (en) * | 2010-04-26 | 2010-08-25 | 西北农林科技大学 | Amphiphilic adsorbent capable of adsorbing both organic matter and heavy metal cation and preparation method thereof |
| CN101811021B (en) * | 2010-04-26 | 2011-12-14 | 西北农林科技大学 | Amphiphilic adsorbent capable of adsorbing both organic matter and heavy metal cation and preparation method thereof |
| CN102503202A (en) * | 2011-11-03 | 2012-06-20 | 武汉科技大学 | Al2O3 intercalated expanded vermiculite heat-insulating material and preparation method thereof |
| CN102503202B (en) * | 2011-11-03 | 2013-02-13 | 武汉科技大学 | Al2O3 intercalated expanded vermiculite heat-insulating material and preparation method thereof |
| CN108176353A (en) * | 2018-03-06 | 2018-06-19 | 高姌 | There is the PERFORMANCE OF MODIFIED VERMICULITE adsorbent and its preparation process of adsorption function to hardly degraded organic substance |
| CN108479737A (en) * | 2018-03-21 | 2018-09-04 | 江西德弘环保科技有限公司 | A kind of preparation process of inorganic mineral material meso-hole structure |
| CN108947580A (en) * | 2018-07-26 | 2018-12-07 | 塔里木大学 | A kind of exfoliated vermiculite raw powder's production technology |
| CN108947580B (en) * | 2018-07-26 | 2020-12-08 | 塔里木大学 | Preparation method of layered vermiculite powder |
| CN112094650A (en) * | 2020-09-28 | 2020-12-18 | 杨剑飞 | Soil remediation agent and preparation method and application thereof |
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