CN104085898A - Method of preparing tubular clay by polar polymer intercalation - Google Patents
Method of preparing tubular clay by polar polymer intercalation Download PDFInfo
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- CN104085898A CN104085898A CN201410330738.4A CN201410330738A CN104085898A CN 104085898 A CN104085898 A CN 104085898A CN 201410330738 A CN201410330738 A CN 201410330738A CN 104085898 A CN104085898 A CN 104085898A
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- clay
- tubulose
- intercalation
- mud
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
Abstract
The invention relates to a method of preparing tubular clay by polar polymer intercalation and belongs to the field of functional ceramic materials. The clay used by the functional ceramic material is Suzhou soil which mainly comprises mineral compositions of millite and kaolinite; the intercalator is polar low molecular polyacrylic acid, of which the viscosity average molecular weigh is 1800-2400g/mol and the additive amount is 0.5-1wt%. The preparation method comprises the following steps: weighing a certain amount of Suzhou soil and mixing with a proper amount of distilled water to obtain slurry, wherein the distilled water is weighed in a mass ratio of distilled water to clay of 1 to 1; adding 0.5-1wt% of stronger ammonia water based on mass of slurry, wherein the mass fraction of NH3 in stronger ammonia water is 25.0-28.0%; pouring into a ball mill tank to grind for 12 hours; then, adding 0.5-1wt% of polyacrylic acid based on mass of slurry, and grinding for 24 hours to obtain intercalated slurry; grinding the intercalated slurry by a millstone mill for 1 hour; then, drying and dispersing to obtain the dry powder tubular clay. The clay provided by the invention can be used as a harmful substance adsorbent, a clarifying agent for turbid water and a sealant for radioactive wastes and toxic materials and has important meaning in the field of environmental protection, water safety and the like.
Description
Technical field
The invention belongs to ceramic material field, be specifically related to a kind of method that polar polymer intercalation is prepared tubulose clay.
Technical background
The industry such as textile printing and dyeing, papermaking, plastics and leather all produce a large amount of waste water from dyestuff every year, because many dyestuffs are the complicated organism containing azo bond, poly aromatic nucleus, can teratogenesis, carcinogenic, mutagenesis, therefore, the removal of this class Wastewater Dyes is extremely important.Many dyestuffs are anti-oxidant, difficult degradation, and the dyestuff that adopts sorbent material to remove in waste water has greater advantage.Gac is a kind of effectively sorbent material, but expensive, has limited its widespread use.
Clay mineral has the characteristics such as adsorptivity, ion exchangeable, dispersiveness with it, aspect environmental improvement, clay mineral can be used as objectionable impurities sorbent material, the finings of muddy water, the sealing agent of atomic waste and poisonous material etc.But it is very large that the adsorptivity of clay particle, ion exchangeable, dispersiveness etc. are affected by clay particle microscopic appearance.And the microscopic appearance of its particle of natural clay mineral how in the form of sheets, bar-shaped, particle size is generally tens microns, has limited the application of clay in environmental improvement.
The present invention is by the processing treatment to natural clay mineral; increasing specific surface area, the particle size that reduces, change granule-morphology etc.; the tubulose clay that obtains high absorbability, macroion exchangeability, polymolecularity, this tubulose clay has a good application prospect in the field such as environment protection and purifying water process.
Summary of the invention
The deficiency that the object of the invention is to apply in environmental improvement for natural clay, provides the preparation method of the tubulose clay of a kind of high-specific surface area, low particle diameter, high absorption property.
Technical scheme of the present invention and technical characterictic are:
Taking clay as intercalation object, intercalator is the acid of polarity low-molecular polypropylene, polyacrylic acid viscosity-average molecular weight is that 1800～2400g/mol, addition are 5wt ‰～10wt ‰, take a certain amount of Suzhou soil and be mixed into mud with appropriate distilled water, the amount of distilled water is by being to measure at 1: 1 with clay mass ratio, adds the strong aqua of the 5wt ‰～10wt ‰ of quality of mud fluid to pour into mill in ball grinder 12h.Add again the polyacrylic acid of the 5wt ‰～10wt ‰ of quality of mud fluid to obtain intercalation mud through the 24h that mills, adopt mill by the intercalation mud 1h that mills, then drying and disperse after obtain dry powder tubulose clay.
Clay used is the raw clay of the composition taking kaolinite and illite as essential mineral.
Strong aqua used is the 5wt ‰～10wt ‰ of quality of mud fluid, NH3 massfraction content 25.0%～28.0% in strong aqua.
Low-molecular polypropylene acid viscosity-average molecular weight used is 1800～2400g/mol.
Length 5～20 μ m of the tubulose clay that obtains, diameter 100～200nm.
Embodiment
Embodiment 1
Select the Suzhou soil of the composition taking illite and kaolinite as essential mineral as intercalation object, take 150g Suzhou soil, measure 150ml distilled water, the amount of distilled water, by being to measure at 1: 1 with clay mass ratio, adds in ball grinder.Taking ammoniacal liquor as guiding agent, measure 1.5ml strong aqua, in strong aqua, NH
3massfraction is content 25.0%～28.0%, pour the 12h that mills in ball grinder into and obtain mud, the polyacrylic acid that takes 2g viscosity-average molecular weight and be 1800g/mol is poured in ball grinder, the 24h that mills again obtains intercalation mud, adopt mill by the 1h that mills in intercalation mud, then obtain dry powder tubulose clay after drying and dispersion.
This tubulose clay is through laser particle size analysis, and clay particle differential volume medium is at 5.60 μ m, and differential volume peak value particle diameter is 4.05 μ m; Through scanning electron microscope analysis and projection electronic microscope photos, how in a tubular form, length is 5～10 μ m to clay particle, diameter 100～150nm.And without the blank sample of intercalation processing, clay particle differential volume medium is at 13.08 μ m, differential volume peak value particle diameter is 34.58 μ m; Through scanning electron microscope analysis and projection electronic microscope photos, clay particle multilayer shape, particle size is 30～50 μ m.Therefore the method can effectively reduce clay particle diameter, forms the effect of tubular structure.
Embodiment 2
Select the Suzhou soil of the composition taking illite and kaolinite as essential mineral as intercalation object, take 150g Suzhou soil, measure 150ml distilled water, the amount of distilled water, by being to measure at 1: 1 with clay mass ratio, adds in ball grinder.Taking ammoniacal liquor as guiding agent, measure 1.5ml strong aqua, in strong aqua, NH
3massfraction is content 25.0%～28.0%, pour the 12h that mills in ball grinder into and obtain mud, the polyacrylic acid that takes 2g viscosity-average molecular weight and be 2400g/mol is poured in ball grinder, the 24h that mills again obtains intercalation mud, adopt mill by the 1h that mills in intercalation mud, then obtain dry powder tubulose clay after drying and dispersion.
This tubulose clay is through laser particle size analysis, and clay particle differential volume medium is at 9.03 μ m, and differential volume peak value particle diameter is 5.37 μ m; Through scanning electron microscope analysis and projection electronic microscope photos, how in a tubular form, length is 8～15 μ m to clay particle, diameter 130～200nm.With the blank sample comparison without intercalation processing, the method can effectively reduce clay particle diameter, forms the effect of tubular structure.And with intercalator molecular weight be 1800g/mol sample contrast, intercalator molecular weight has a significant effect to clay particle particle diameter and tubular structure, intercalator viscosity-average molecular weight is that 1800g/mol is advisable.
Embodiment 3
Select the Suzhou soil of the composition taking illite and kaolinite as essential mineral as intercalation object, take 150g Suzhou soil, measure 150ml distilled water, the amount of distilled water, by being to measure at 1: 1 with clay mass ratio, adds in ball grinder.Taking ammoniacal liquor as guiding agent, measure 1.5ml strong aqua, in strong aqua, NH
3massfraction is content 25.0%～28.0%, pour the 12h that mills in ball grinder into and obtain mud, the polyacrylic acid that takes 3g viscosity-average molecular weight and be 1800g/mol is poured in ball grinder, the 24h that mills again obtains intercalation mud, adopt mill by the 1h that mills in intercalation mud, then obtain dry powder tubulose clay after drying and dispersion.
This tubulose clay is through laser particle size analysis, and clay particle differential volume medium is at 5.89 μ m, and differential volume peak value particle diameter is 4.43 μ m; Through scanning electron microscope analysis and projection electronic microscope photos, how in a tubular form, length is 10～20 μ m to clay particle, diameter 150～200nm.With the blank sample comparison without inserting processing, the method can effectively reduce clay particle diameter, forms the effect of tubular structure.And with intercalator addition be 2g, intercalator addition is the sample contrast of 5wt ‰, intercalator addition is to clay particle particle diameter and tubular structure are had a significant effect, intercalator addition is that 5wt ‰ is advisable.
Embodiment 4
Select the Suzhou soil of the composition taking illite and kaolinite as essential mineral as intercalation object, take 150g Suzhou soil, measure 150ml distilled water, the amount of distilled water, by being to measure at 1: 1 with clay mass ratio, adds in ball grinder.Taking ammoniacal liquor as guiding agent, measure 1.5ml strong aqua, in strong aqua, NH
3massfraction is content 25.0%～28.0%, pour the 12h that mills in ball grinder into and obtain mud, the polyacrylic acid that takes 2g viscosity-average molecular weight and be 1800g/mol is poured in ball grinder, the 24h that mills again obtains intercalation mud, adopt mill by the 1h that mills in intercalation mud, then obtain dry powder tubulose clay after drying and dispersion.
This tubulose clay, through the test of cationic exchange specific surface area and volume test, test result is: the total specific surface area of tubulose clay is 220m
2/ g, cation exchange capacity is 86.3 milligramequivalents/100g.And without inserting the blank sample of processing, total specific surface area is 135m
2/ g, cation exchange capacity is 59.6 milligramequivalents/100g.With the blank sample contrast without inserting processing, obtain its total specific surface area of tubulose clay through intercalation processing and improved 63%, cation exchange capacity has improved 45%, and the total specific surface area and the cation exchange capacity that as seen obtain tubulose clay through intercalation processing obviously improve.
Claims (7)
1. a polar polymer intercalation is prepared the method for tubulose clay, it is characterized in that taking principal constituent as illite and kaolinic clay is intercalation object, taking the acid of polarity low-molecular polypropylene as intercalator, the preparation method of this tubulose clay comprises the following steps: slurrying; Clay intercalated processing; Machine-shaping; Dry dispersion.
2. a kind of polar polymer intercalation as claimed in claim 1 is prepared the method for tubulose clay, it is characterized in that principal constituent used is that kaolinite and illitic clay are intercalation object, in clay, to consist of kaolinite content be 70wt%～80wt% to essential mineral, illite content is 5wt%～10wt%, other compositions are 10wt%～25wt%, and particle diameter is 30～50 μ m.
3. a kind of polar polymer intercalation as claimed in claim 1 is prepared the method for tubulose clay, and the viscosity-average molecular weight that it is characterized in that polarity low-molecular polypropylene used acid is 1800～2400g/mol, 5wt ‰～10wt ‰ that addition is quality of mud fluid.
4. a kind of polar polymer intercalation as claimed in claim 1 is prepared the method for tubulose clay, the method that it is characterized in that slurrying is 49.5wt%～49.75wt%, 49.5wt%～49.75wt% that distilled water accounts for quality of mud fluid, the 5wt ‰～10wt ‰ that ammoniacal liquor accounts for quality of mud fluid that clay accounts for quality of mud fluid, NH in ammoniacal liquor
3massfraction content 25.0wt%～28.0wt%, by above-mentioned three kinds of raw materials 12h that mills in ball mill.
5. a kind of polar polymer intercalation as claimed in claim 1 is prepared the method for tubulose clay, the polyacrylic acid that the method that it is characterized in that clay intercalated processing is is 1800～2400g/mol by viscosity-average molecular weight joins in mud by the 5wt ‰～10wt ‰ of quality of mud fluid, by mud ball milling 24h in ball mill, obtain intercalation clay mud again.
6. a kind of polar polymer intercalation as claimed in claim 1 is prepared the method for tubulose clay, the method that it is characterized in that machine-shaping be by intercalation mud through the mill 1h that mills, obtain tubulose clay mud.
7. a kind of polar polymer intercalation as claimed in claim 1 is prepared the method for tubulose clay, it is characterized in that dry method of disperseing is that tubulose clay mud is toasted to 12h at 80 DEG C, through ball milling 1h, obtaining length of tube is 5～20 μ m, the tubulose clay that diameter is 100～200nm again.
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| CN201410330738.4A CN104085898B (en) | 2014-07-08 | 2014-07-08 | Method of preparing tubular clay by polar polymer intercalation |
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| CN201410330738.4A CN104085898B (en) | 2014-07-08 | 2014-07-08 | Method of preparing tubular clay by polar polymer intercalation |
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| CN104085898B CN104085898B (en) | 2017-05-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401566A (en) * | 2002-09-24 | 2003-03-12 | 华南理工大学 | Intercalation type or amorphous kaoline and preparing process thereof |
| US20040059037A1 (en) * | 2002-09-25 | 2004-03-25 | Eastman Kodak Company | Materials and method for making splayed layered materials |
| US20100040653A1 (en) * | 2004-12-02 | 2010-02-18 | Grah Michael D | Intercalated layered silicate |
| CN103880032A (en) * | 2014-04-13 | 2014-06-25 | 北京化工大学 | Thiourea intercalation modified kaolin and preparation method thereof |
-
2014
- 2014-07-08 CN CN201410330738.4A patent/CN104085898B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401566A (en) * | 2002-09-24 | 2003-03-12 | 华南理工大学 | Intercalation type or amorphous kaoline and preparing process thereof |
| US20040059037A1 (en) * | 2002-09-25 | 2004-03-25 | Eastman Kodak Company | Materials and method for making splayed layered materials |
| US20100040653A1 (en) * | 2004-12-02 | 2010-02-18 | Grah Michael D | Intercalated layered silicate |
| CN103880032A (en) * | 2014-04-13 | 2014-06-25 | 北京化工大学 | Thiourea intercalation modified kaolin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 曾雄丰等: "插层改性粘土的可加工性能研究", 《中国陶瓷》 * |
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