CN102351207B - Method for preparing nano attapulgite by solvothermal process - Google Patents
Method for preparing nano attapulgite by solvothermal process Download PDFInfo
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- CN102351207B CN102351207B CN 201110240006 CN201110240006A CN102351207B CN 102351207 B CN102351207 B CN 102351207B CN 201110240006 CN201110240006 CN 201110240006 CN 201110240006 A CN201110240006 A CN 201110240006A CN 102351207 B CN102351207 B CN 102351207B
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 62
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004729 solvothermal method Methods 0.000 title abstract 2
- 239000000047 product Substances 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000004575 stone Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 235000019353 potassium silicate Nutrition 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 159000000013 aluminium salts Chemical class 0.000 claims description 7
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002243 precursor Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- 239000004809 Teflon Substances 0.000 abstract 1
- 229920006362 Teflon® Polymers 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 abstract 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 239000004927 clay Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000009991 scouring Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
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- 239000002071 nanotube Substances 0.000 description 1
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- 150000004965 peroxy acids Chemical class 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 231100000167 toxic agent Toxicity 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing fibrous nano attapulgite by a solvothermal process. The method comprises the following steps: mixing cheap sodium silicate, inorganic magnesium salt and aluminum salt, treating with hydrochloric acid until the pH value is 1-3, alkalifying by slowly and dropwisely adding a sodium hydroxide solution with a certain concentration to form a solid gel precipitate in which the ratio of Si to Al and the ratio of Si to Mg are respectively 2-4, aging the precipitate, separating, washing and drying to obtain a precursor; mixing the precursor and an organic solvent in a solid to liquid ratio of 1:(50-100), reacting in a 200ml teflon/stainless steel reaction kettle at 120-180 DEG C for 48-96 hours, and naturally cooling to obtain different fibrous nano attapulgites. The invention has the advantages of simple technique and facility request, stable product and controllable properties, and can be used in the fields of the preparation of medicine, adsorbents, cosmetics, organic-inorganic nano composite materials and the like.
Description
Technical field
The present invention relates to the method that a kind of solvent-thermal method prepares the fibrous nano attapulgite; Be specially water glass, inorganic magnesium salt and aluminium salt etc. are formed the presoma with different Si/Al and Si/Mg ratio through the collosol and gel effect; Utilize solvent thermal reaction to generate fibrous nano attapulgite crystal again, belong to the nano silicate technical field of material.
Background technology
Attapulgite clay (having another name called polygorskite or Palygorskite) is a kind ofly to have layer 1-dimention nano of chain molecule structure and contain Shuifu County's magnesium, aluminium silicate mineral.Attapulgite clay is made up of the attapulgite crystal; Unique nanometer fibrous microstructure has given that its specific surface area is big, high adsorption capacity, the good and excellent physico-chemical property of reinforcing property of salt tolerant alkalescence, and its good reactive behavior has also been given in the existence of special surface silicon oh group.Therefore, attapulgite clay demonstrates very big application prospect at numerous areas such as oil product decolouring, drilling mud, function supporting material, catalysis or drug carrier material, function compound manure, water treatment and coating.
But natural attapulgite clay rod intergranular exists with brilliant bundle of rod or aggregate form owing to have static or interaction of hydrogen bond usually, only is a kind of presoma of nano material, does not have the nano material characteristic.After the brilliant bundle aggregate of attapulgite clay rod dissociated, the various performances of nano material were able to remarkable lifting, but were difficult to realize with the dissociating fully of the brilliant bundle of attapulgite rod, and excellent crystalline substance also can fracture in dissociation process, and then the loss performance.In addition, attapulgite clay belongs to Nonrenewable resources, and the trichite of different ore deposit point or same ore deposit point different depths attapulgite rod to educate performance differences such as degree, physicochemical property, purity, activity bigger, be unfavorable for realizing batch a stable production and an application.Be so limited, the application of present natural attapulgite clay is main with low value-added product still.Therefore; Obtain the nano-attapulgite stone of stable homogeneous, purity height and good dispersivity through the method for synthetic; Both can avoid complicated the dissociating and purification processes of natural attapulgite clay; Can solve batch problem of unstable that the difference because of different places of production attapulgite clay causes again, the high-end applications that realizes attapulgite clay this " industrial monosodium glutamate " and the sustainable development of attapulgite clay industrial chain are had profound significance and using value.
Synthetic coprecipitation method, hydrothermal method and the solvent-thermal method of mainly containing of present clay mineral; For example: Chinese patent CN101817510A discloses the co-precipitation compound method of the hydrotalcite of crystal phase structure complete sum even grain size; Document (Sun Hongjuan; In. artificial lens journal, 2008,37 (4): 844-848) and patent (CN101289193) reported the hydrothermal method compound method of hectorite and serpentine nanotube respectively.Solvent thermal reaction is the development of hydro-thermal reaction, and the difference of it and hydro-thermal reaction is that employed solvent is not a water, but organic solvent.In solvent thermal reaction, one or more presomas are dissolved in the non-aqueous solvent, under liquid phase or super critical condition, reactant be dispersed in the solution and become more active, react and slowly generate product.This process is simple relatively and be easy to control, and in enclosed system, can effectively prevent the volatilization of toxic substance.In addition, the formation of thing phase, the size of particle diameter, form also can be controlled, and the dispersiveness of product better.Under the solvent thermal condition, the change of properties of solvent is very big, and dissolving, dispersion and the chemical reactivity of reactant (normally solid) improve greatly, and this just makes reaction under lower temperature, to take place.Therefore, solvent process for thermosynthesizing has that the control easily of product pattern, good crystallinity, compound method are simple, repeatability is good, be easy to that industry is amplified, advantages of environment protection, is one of effective way that realizes appearance of nano material control.For this reason; Preparing the high quality nano attapulgite with solvent thermal is target; To solve a series of problems such as batch instability that runs in the current natural attapulgite clay application process, the purification difficult of dissociating is background; To realize that the higher value application of attapulgite clay in the high-end field is guiding, on the basis of lot of experiments work, design utilizes sol-gel technique to combine solvent process for thermosynthesizing to prepare to have the trichite of homogeneous rod educates degree, physicochemical property, purity and active nano-attapulgite stone.Compare other method, this method technology and equipment requirements is simple, reaction conditions is gentle, with low cost, product stable and proterties is controlled can be used for numerous areas such as medicine, sorbent material, makeup and organic-inorganic nanocomposite preparation.
Summary of the invention
A series of problems of utilizing in view of the natural attapulgite clay of the restriction of introducing in the technical background as: (1) exists with brilliant bundle of rod or aggregate usually; Be difficult to bring into play the characteristic of nano material; Dissociate and to significantly improve its nanometer performance; Be difficult to realize but fully dissociate, and will be cost with the excellent crystalline substance that fractures in the dissociation process; (2) to educate performance differences such as degree, physicochemical property, purity, activity bigger in the excellent trichite of different place of production attapulgite, has tangible areal variation, is difficult to realize batch a stable production and an application; (3) attapulgite clay belongs to Nonrenewable resources; Developing artificial synthetic technology is the basic premise of realizing that sustainability is utilized; The solvent thermal technology of preparing that the purpose of this invention is to provide the strong nano-attapulgite stone of a kind of high yield, easy to operate, low-cost, high efficiency and usability; Utilize inexpensive inorganic salt for feedstock production goes out excellent brilliant length homogeneous, good dispersivity, batch stabilized nano attapulgite, for the application of nano-attapulgite clay in high-tech sector lays the foundation.
Principle of the present invention is to utilize water glass, inorganic magnesium salt and aluminium salt after distinguishing acidified and alkalization process, to form solid gel shape product; Regulate Si/Al and Si/Mg ratio in the solid product through the control material rate, with obtaining the attapulgite presoma after jel product ageing, washing, the drying.The gained presoma is with after organic solvent in certain ratio is mixed, crystallization again under high temperature and high pressure solvent thermal condition, and form fibrous nano attapulgite with layer chain-like structure along growth on the certain orientation.Through control Si/Al and Si/Mg ratio, reaction times length, the nano-attapulgite stone that can obtain having the brilliant length of different rod.
Technical solution of the present invention is:
A kind of solvent thermal prepares the method for nano-attapulgite stone, at first water glass, inorganic magnesium salt and aluminium salt is formed the presoma with different Si/Al and Si/Mg ratio through acidifying with the alkalization process, and acidifying pH value is between 1～3, and Si/Al and Si/Mg are than between 2～4.Then this presoma is mixed with organic solvent, solid-to-liquid ratio is controlled at 1: 40～90, and at 120～180 ℃ of scope internal reaction 48～96h, the room temperature cooling can obtain the nano-attapulgite stone product in the stainless steel cauldron of tool tetrafluoroethylene liner.
Below the present invention is done further description, process step is following:
1, the preparation of attapulgite presoma: with water glass, inorganic magnesium salt (sal epsom, magnesium chloride or magnesium nitrate), inorganic aluminate (Tai-Ace S 150, aluminum chloride or aluminum nitrate) by Si/Al and Si/Mg than the mixed that is 2～4; Be acidified to pH 1～3 with the 2mol/L hydrochloric acid soln, alkalize to forming the gel solid with 1mol/L NaOH solution then.The ageing of gel solid product, washing, the drying of gained are obtained the attapulgite presoma.Water glass and inorganic magnesium salt, aluminium salt mixture can realized sol-gel transition after peracid, alkali effect, form the solid gel product, use the attapulgite presoma so can be used for preparing solvent thermal reaction.
2, the solvent thermal reaction of attapulgite presoma: prepared attapulgite presoma is mixed by solid-to-liquid ratio 1: 50～100 with organic solvent; The stainless steel cauldron that places the tool tetrafluoroethylene is accomplished the growth of fibrous crystals at 120～180 ℃ of reaction 48～96h.Described organic solvent is any one or more of methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, terepthaloyl moietie, USP Kosher and acetone etc.
3, nano-attapulgite stone product separation and drying: solvent thermal reaction at room temperature cools off reaction kettle after finishing, and then the product spinning is gone out, and is dry with zero(ppm) water thorough washing final vacuum.Simultaneously organic solvent is recycled.
The present invention is a raw material with water glass, inorganic magnesium salt and the aluminium salt of cheapness, and in conjunction with sol-gel system presoma and solvent thermal synthetic technology efficiently, the nano-attapulgite stone that preparation has filamentary structure has the following advantages:
(1), prepares high yield, excellent brilliant length homogeneous, good dispersivity, nano-attapulgite stone such as Fig. 1 that purity is high through solvent-thermal method.Batch stability of prepared product is better, can carry out persistence production, and can directly be used for industrial applications such as colloidal powder, strengthening agent, need not further to handle.
(2), through the sol-gel technology preparing presoma; And then with solvent heat treatment generation fibrous nano attapulgite such as Fig. 2, whole process need not introduced the structure directing agent of extra rod crystals growth, makes working method simpler; Products obtained therefrom purity is higher, and technology is environmental protection more.
(3), this preparing method's technology and equipment requirements be simple, process is easy to control, productive rate is high.
(4), organic solvent can be recycled in this technology, has reduced discharging when making full use of resource.
Description of drawings
Fig. 1 is the synthetic nano-attapulgite stone XRD figure that obtains of solvent thermal; The nano-attapulgite stone SEM figure that Fig. 2 obtains for solvent thermal is synthetic.
Embodiment
Embodiment one
Under magnetic agitation; The 15g water glass is dissolved in the 900ml zero(ppm) water; Add 10g MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 and 14g anhydrous slufuric acid aluminium again; Adding 2mol/l hydrochloric acid accent pH value of solution is 2, drips the sodium hydroxide solution (about 48ml) of 1mol/l again with 0.4ml/min speed, until forming a large amount of solid gel throw outs.This throw out is placed ageing 24h after scouring, drying, obtain presoma.Claim that the 1.5g precursor powder mixes with the 120ml absolute ethyl alcohol, change in the 200ml stainless steel cauldron of tool tetrafluoroethylene liner that place baking oven to react 48h down at 160 ℃, room temperature condition is cooling down.Behind the separation of gained powdery product, thorough washing, 60 ℃ of following vacuum-dryings, promptly get the nano-attapulgite stone product, product color is a white.
Fig. 1 is the XRD figure of gained nano-attapulgite stone, and the reference standard card can find out that the synthetic material is the nano-attapulgite stone crystalline material of pure phase.Fig. 2 is the SEM figure of gained nano-attapulgite stone, has the filamentary structure of attapulgite.
Embodiment two
Under magnetic agitation; The 15g water glass is dissolved in the 900ml zero(ppm) water; Add 10g MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 and 10g anhydrous slufuric acid aluminium again; Adding 2mol/l hydrochloric acid accent pH value of solution is 2, drips the sodium hydroxide solution (about 48ml) of 1mol/l again with 0.4ml/min speed, until forming a large amount of solid gel throw outs.This throw out is placed ageing 24h after scouring, drying, obtain presoma.Claim that the 1.5g precursor powder mixes with the 120ml absolute ethyl alcohol, change in the 200ml stainless steel cauldron of tool tetrafluoroethylene liner that place baking oven to react 48h down at 160 ℃, room temperature condition is cooling down.Behind the separation of gained powdery product, thorough washing, 60 ℃ of following vacuum-dryings, promptly get the nano-attapulgite stone product, product color is a white.
Embodiment three
Under magnetic agitation; The 15g water glass is dissolved in the 900ml zero(ppm) water; Add 15g MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 and 14g anhydrous slufuric acid aluminium again; Adding 2mol/l hydrochloric acid accent pH value of solution is 2, drips the sodium hydroxide solution (about 48ml) of 1mol/l again with 0.4ml/min speed, until forming a large amount of solid gel throw outs.This throw out is placed ageing 24h after scouring, drying, obtain presoma.Claim that the 1.5g precursor powder mixes with the 120ml absolute ethyl alcohol, change in the 200ml stainless steel cauldron of tool tetrafluoroethylene liner that place baking oven to react 48h down at 160 ℃, room temperature condition is cooling down.Behind the separation of gained powdery product, thorough washing, 60 ℃ of following vacuum-dryings, promptly get the nano-attapulgite stone product, product color is a white.
Embodiment four
Under magnetic agitation; The 15g water glass is dissolved in the 900ml zero(ppm) water; Add 10g MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 and 14g anhydrous slufuric acid aluminium again; Adding 2mol/l hydrochloric acid accent pH value of solution is 2, drips the sodium hydroxide solution (about 48ml) of 1mol/l again with 0.4ml/min speed, until forming a large amount of solid gel throw outs.This throw out is placed ageing 24h after scouring, drying, obtain presoma.Claim that the 1.5g precursor powder mixes with the 120ml absolute ethyl alcohol, change in the 200ml stainless steel cauldron of tool tetrafluoroethylene liner that place baking oven to react 72h down at 180 ℃, room temperature condition is cooling down.With the separation of gained powdery product, thorough washing and 60 ℃ of following vacuum-dryings, promptly get the nano-attapulgite stone product, product color white.
Embodiment five
Under magnetic agitation; The 15g water glass is dissolved in the 900ml zero(ppm) water; Add 10g MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 and 10g anhydrous slufuric acid aluminium again; Adding 2mol/l hydrochloric acid accent pH value of solution is 2, drips the sodium hydroxide solution (about 48ml) of 1mol/l again with 0.4ml/min speed, until forming a large amount of solid gel throw outs.This throw out is placed ageing 24h after scouring, drying, obtain presoma.Claim that the 1.5g precursor powder mixes with the 120ml absolute ethyl alcohol, change in the 200ml stainless steel cauldron of tool tetrafluoroethylene liner that place baking oven to react 72h down at 180 ℃, room temperature condition is cooling down.Behind the separation of gained powdery product, thorough washing, 60 ℃ of following vacuum-dryings, promptly get the nano-attapulgite stone product, product color is a white.
Embodiment six
Under magnetic agitation; The 15g water glass is dissolved in the 900ml zero(ppm) water; Add 15g MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 and 14g anhydrous slufuric acid aluminium again; Adding 2mol/l hydrochloric acid accent pH value of solution is 2, drips the sodium hydroxide solution (about 48ml) of 1mol/l again with 0.4ml/min speed, until forming a large amount of solid gel throw outs.This throw out is placed ageing 24h after scouring, drying, obtain presoma.Claim that the 1.5g precursor powder mixes with the 120ml absolute ethyl alcohol, change in the 200ml stainless steel cauldron of tool tetrafluoroethylene liner that place baking oven to react 72h down at 180 ℃, room temperature condition is cooling down.Behind the separation of gained powdery product, thorough washing, 60 ℃ of following vacuum-dryings, promptly get the nano-attapulgite stone product, product color is a white.
Claims (4)
1. the method for a solvent thermal synthon shape nano-attapulgite stone; It is characterized in that; Earlier water glass, inorganic magnesium salt and aluminium salt are mixed acidifying by a certain percentage; Form solid gel shape product with the alkalization of NaOH solution again, the abundant ageing of gained solid product, washing and drying are obtained Powdered presoma with different Si/Al and Si/Mg ratio; Again this presoma is mixed with organic solvent in certain ratio, change in the stainless steel reactor of 200mL tool tetrafluoroethylene liner and react certain hour at a certain temperature, can obtain the fibrous nano attapulgite after the cooling naturally; Wherein, acidifying pH value is 1～3; Wherein, Si/Al and Si/Mg ratio is 2～4 in the presoma; Wherein, presoma and organic solvent solid-to-liquid ratio are 1: 50-100; The solvent thermal reaction temperature is 120～180 ℃, and the reaction times is 48～96h; Described organic solvent is any one or more of methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, terepthaloyl moietie, USP Kosher and acetone.
2. the method for solvent thermal synthon shape nano-attapulgite stone according to claim 1 is characterized in that described inorganic magnesium salt is any in sal epsom, magnesium chloride or the magnesium nitrate, and aluminium salt is any in Tai-Ace S 150, aluminum chloride or the aluminum nitrate.
3. the method for solvent thermal synthon shape nano-attapulgite stone according to claim 1 is characterized in that the presoma digestion time is 12～36h, and washing times is more than 5 times.
4. the method for solvent thermal synthon shape nano-attapulgite stone according to claim 1; It is characterized in that; This processing unit requires simple, easy handling, the recyclable utilization of organic solvent; Products obtained therefrom homogeneous, excellent brilliant length-to-diameter ratio are big, stable performance, purity height and good dispersivity, can be used for colloidal materials and engineering materials strengthening agent.
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