CN102107877B - Method for preparing 0.85nm hydrated kaolinite by direct replacement intercalation - Google Patents
Method for preparing 0.85nm hydrated kaolinite by direct replacement intercalation Download PDFInfo
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- CN102107877B CN102107877B CN2010105996909A CN201010599690A CN102107877B CN 102107877 B CN102107877 B CN 102107877B CN 2010105996909 A CN2010105996909 A CN 2010105996909A CN 201010599690 A CN201010599690 A CN 201010599690A CN 102107877 B CN102107877 B CN 102107877B
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Abstract
The invention discloses a method for preparing a interlayer spacing 0.85nm hydrated kaolinite by direct replacement intercalation, which comprises the following steps: preparing a mixture of a urea/kaolinite intercalation compound and excessive urea by a grinding-subsequent heat treatment process; washing with deionized water to remove the excessive urea, thereby obtaining a urea/kaolinite intercalation compound; and finally, adding the urea/kaolinite intercalation compound into hot water, stirring for a few minutes, and carrying out centrifugal drying to obtain the interlayer spacing 0.85nm hydrated kaolinite. The interlayer spacing 0.85nm hydrated kaolinite prepared by the method disclosed by the invention can stably exist in air for a long time, and can be used for preparing precursors of other kaolinite intercalation compounds. The adopted raw material does not pollute the environment; and the preparation technique is simple and quick, has the advantage of low cost, and can easily implement industrial production.
Description
Technical field
The present invention relates to the kaolinic preparation method of a kind of hydration, the kaolinic method of hydration that especially to relate to a kind of direct replacement intercalation prepared layer spacing be 0.85nm.This hydration kaolinite has stronger displacement intercalation ability; Can be used as a kind of environment-friendly type precursor for preparing other kaolinite intercalated compounds; Belong to field of compound material, have broad application prospects in fields such as nano-catalytic, drug delivery, ionophore, electrode, nano composite materials.
Background technology
Kaolinite is a kind of important nonmetal mineral resource, mainly is made up of kandites such as small sheet, tubulose, laminated, is widely used in papermaking, pottery, paint, rubber, plastics, field of petrochemical industry in the industry.Kaolinite (Al
2Si
2O
5(OH)
4) be a kind of typical 1: 1 type layered silicate, its crystalline structure is made up of as periodic arrangement on the c direction of principal axis alumina octahedral and the multiple layer of silicon-oxy tetrahedron, and layer links to each other through the hydrogen bond that forms between aluminium hydroxyl and the siloxy with interlayer.Under the certain condition, the reactive force that some material (atom, lewis' acid) can overcome interlayer inserts bedding void reversiblely, and does not destroy its original laminate structure, and this effect is called the intercalation effect.
The kaolinite intercalated compound is the focus of industry research always, has bigger scientific research and using value in fields such as electrochemistry, drug delivery, polymer nanocomposites, catalyzer.Owing to have a large amount of hydroxyl activity groups in the kaolinite laminate structure, thereby be different from polynite, when kaolinite and other material formation compound system, in forming process, show special high-performance.But; Lack isomorphous replacement because the kaolinite crystal layer is inner, the structural unit interlayer does not have positively charged ion, therefore kaolinic CEC very a little less than; And there is stronger hydrogen bond in the kaolinite interlayer; General material is difficult to get into the kaolinite interlayer, has only directly intercalation kaolin stone such as stronger organic molecule of minority polarity such as Potassium ethanoate, Hydrazine Hydrate 80, methane amide, methyl-sulphoxide, urea, and other molecules can only get into the kaolinite interlayer through modes such as displacements.
Seek out intercalated compound, need utilize substitution method to carry out usually, also promptly prepare the kaolinite intercalated compound and need select suitable precursor usually with various performances.But existing as above-mentioned direct intercalation kaolin stone mixture is not suitable as the presoma of all molecular replacement intercalations, and preparing suitable presoma sometimes need just can obtain through replacing intercalation several times, thereby preparation time is long, the technology relative complex.
Discover that further the hydration kaolinite can be used as a kind of precursor for preparing the kaolinite intercalated compound; Some are the organic molecule of intercalation in the kaolinite layer directly; Reported like terepthaloyl moietie, acetone, pyrimidine, glycerine, amino acid etc.; Then can through the hydration kaolinite directly and these organic molecule effects form stable intercalated compound.And this is a kind of environmentally friendly intercalation precursor, and some polarity organic molecule such as methyl-sulphoxide etc. strong and that can be used to direct intercalation all have stronger toxicity, can cause certain environmental pollution; And this hydration kaolinite; It itself is a kind of hydrated product; Thereby as the presoma that further prepares various other intercalation compounds; Can not cause any environmental pollution to the downstream link, so it is a kind of product of being used to prepare various relevant intercalation compounds very friendly to environment, will be with a wide range of applications and the market potential.
Yet; The hydration kaolinite of at present having reported still utilizes multistep to replace the graft process preparation mostly; As utilize methyl-sulphoxide/kaolinite to prepare terepthaloyl moietie/kaolinite mixture earlier, can obtain the hydration kaolinite of 0.84nm again after 3 days as intermediate phase and water reaction with terepthaloyl moietie/kaolinite.Through first preparation N-NMF/kaolinite, prepare methyl alcohol/kaolinite mixture with this again, last and water react the hydration kaolinite that obtains 1.00nm after 3 days, when dry air or solution temperature are higher than 30 ℃, can change the hydration kaolinite of 0.85nm again into.Totally see; The hydration kaolinite basically all is to obtain through preparing the higher kaolinite intercalated compound of stability early stage, reacting under coldcondition with water more at present, and reaction time is longer; Usually need several days time, obviously existing technology also difficulty be used for actual production.
Thereby will seek out the production technique with Practical significance at present and really be used for this hydrous kaolin presoma of batch preparations product, its major objective is: change technology, simplify the preparation process, shorten preparation time.This is to the Application and Development of this hydration kaolinite presoma and form specialized produce market and will play important effect.
Summary of the invention
The invention reside in a kind of direct replacement intercalation prepared layer spacing is provided is the kaolinic method of hydration of 0.85nm.Utilize urea to insert the kaolinite interlayer as the middle transition phase, successfully to have prepared interlamellar spacing be the hydration kaolinite of 0.85nm through once replacing intercalation.
The step of the technical scheme that the present invention adopts is following:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture;
B, every 1g kaolinite/urea intercalated compound and urea admixture are added in 10～20ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound;
In c, the deionized water with every 1g kaolinite/urea intercalated compound adding 40～80ml, after 90～100 ℃ of lower magnetic forces stir 3～10min, be centrifugal, use absolute ethanol washing again, after 40 ℃ of oven dry, obtaining Powdered interlamellar spacing is the hydration kaolinite of 0.85nm.
The hydration kaolinite for preparing by above-mentioned steps shows through X-ray diffraction, ir spectra and scanning electron microscope analysis; The interlayer urea of water molecules displacement urea/kaolinite intercalated compound; Obtain a kind of hydration kaolinite, its interlamellar spacing expands 0.85nm to from former kaolinic 0.72nm, and the hydration kaolinite content that obtains is 51%～64%; Wherein water molecules is embedded in the space, kaolinite silicon-oxy tetrahedron compound three hole, can be in air long-time stable existence.
The present invention compares the beneficial effect that has to be had with background technology:
1, employing as precursor, only needs simple step displacement graft process can prepare the hydration kaolinite that interlamellar spacing is 0.85nm with urea/kaolinite intercalated compound, and technology is simple, and is low for equipment requirements, is easy to realize suitability for industrialized production.
2, the interlayer urea reaction speed of water displacement urea/kaolinite intercalated compound is very fast, and the cycle is short, and can be implemented in the interior preparation fast of 3～10min form layers spacing is the hydration kaolinite of 0.85nm.
3, this interlamellar spacing of preparation is that the raw material that the hydration kaolinite of 0.85nm is adopted has only kaolinite, urea and water, preparation process environmentally safe.
The interlamellar spacing of the present invention preparation is only to contain water molecules in the hydration kaolinite of 0.85nm; Can not cause secondary environmental pollution; It is a kind of environment-friendly type precursor for preparing other kaolinite intercalated compounds; Some can not be directly at the organic molecule of kaolinite interlayer intercalation, like terepthaloyl moietie, acetone, pyrimidine, propyl alcohol, THF, glycerine equimolecular, then can be directly through with the effect of hydration kaolinite; Form stable intercalated compound, have broad application prospects in fields such as nano-catalytic, drug delivery, ionophore, electrode, nano composite materials.
Description of drawings
Accompanying drawing is the kaolinite original soil and contains the kaolinic X-ray diffractogram of different hydrations.
In the accompanying drawing:
(a) be kaolinite original soil XRD;
(b) be the XRD of 1g urea/kaolinite mixture and 40ml deionized water sample behind reaction 3min under 90 ℃ of conditions;
(c) be the XRD of 1g urea/kaolinite mixture and 60ml deionized water sample behind reaction 5min under 90 ℃ of conditions;
(d) be the XRD of 1g urea/kaolinite mixture and 80ml deionized water sample behind reaction 10min under 90 ℃ of conditions;
(e) be the XRD of 1g urea/kaolinite mixture and 40ml deionized water sample behind reaction 3min under 100 ℃ of conditions;
(f) be the XRD of 1g urea/kaolinite mixture and 60ml deionized water sample behind reaction 5min under 100 ℃ of conditions;
(g) be the XRD of 1g urea/kaolinite mixture and 80ml deionized water sample behind reaction 10min under 100 ℃ of conditions.
Embodiment
Embodiment 1:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture (1);
B, 1g mixture (1) is added in the 20ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound (2);
In c, the deionized water, after 90 ℃ of lower magnetic forces stir 3min, be centrifugal, use absolute ethanol washing again, after 40 ℃ of oven dry, obtain Powdered 0.85nm hydration kaolinite 1g kaolinite/urea intercalated compound (2) adding 40ml.
By hydration kaolinite X-ray diffraction Fig. 1 (b) that above-mentioned steps prepares, its interlamellar spacing expands 0.85nm to from the 0.72nm of former stone, and the hydration kaolinite content that obtains is 51%.Shown in Fig. 1 (b).
Embodiment 2:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture (1);
B, 1g mixture (1) is added in the 10ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound (2);
In c, the deionized water, after 90 ℃ of lower magnetic forces stir 5min, be centrifugal, use absolute ethanol washing again, after 40 ℃ of oven dry, obtain Powdered 0.85nm hydration kaolinite 1g kaolinite/urea intercalated compound (2) adding 60ml.
By hydration kaolinite X-ray diffraction Fig. 1 (c) that above-mentioned steps prepares, its interlamellar spacing expands 0.85nm to from the 0.72nm of former stone, and the hydration kaolinite content that obtains is 54%.Shown in Fig. 1 (c).
Embodiment 3:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture (1);
B, 1g mixture (1) is added in the 20ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound (2);
In c, the deionized water, after 90 ℃ of lower magnetic forces stir 10min, be centrifugal, use absolute ethanol washing again, after 40 ℃ of oven dry, obtain Powdered 0.85nm hydration kaolinite 1g kaolinite/urea intercalated compound (2) adding 80ml.
By hydration kaolinite X-ray diffraction Fig. 1 (d) that above-mentioned steps prepares, its interlamellar spacing expands 0.85nm to from the 0.72nm of former stone, and the hydration kaolinite content that obtains is 52%.Shown in Fig. 1 (d).
Embodiment 4:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture (1);
B, 1g mixture (1) is added in the 10ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound (2);
In c, the deionized water, after 100 ℃ of lower magnetic forces stir 3min, be centrifugal, use absolute ethanol washing again, after 40 ℃ of oven dry, obtain Powdered 0.85nm hydration kaolinite 1g kaolinite/urea intercalated compound (2) adding 40ml.
By hydration kaolinite X-ray diffraction Fig. 1 (e) that above-mentioned steps prepares, its interlamellar spacing expands 0.85nm to from the 0.72nm of former stone, and the hydration kaolinite content that obtains is 57%.Shown in Fig. 1 (e).
Embodiment 5:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture (1);
B, 1g mixture (1) is added in the 20ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound (2);
In c, the deionized water, after 100 ℃ of lower magnetic forces stir 5min, be centrifugal, use absolute ethanol washing again, after 40 ℃ of oven dry, obtain Powdered 0.85nm hydration kaolinite 1g kaolinite/urea intercalated compound (2) adding 60ml.
By hydration kaolinite X-ray diffraction Fig. 1 (f) that above-mentioned steps prepares, its interlamellar spacing expands 0.85nm to from the 0.72nm of former stone, and the hydration kaolinite content that obtains is 59%.Shown in Fig. 1 (f).
Embodiment 6:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture (1);
B, 1g mixture (1) is added in the 10ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound (2);
In c, the deionized water, after 100 ℃ of lower magnetic forces stir 10min, be centrifugal, use absolute ethanol washing again, after 40 ℃ of oven dry, obtain Powdered 0.85nm hydration kaolinite 1g kaolinite/urea intercalated compound (2) adding 80ml.
By hydration kaolinite X-ray diffraction Fig. 1 (g) that above-mentioned steps prepares, its interlamellar spacing expands 0.85nm to from the 0.72nm of former stone, and the hydration kaolinite content that obtains is 64%.Shown in Fig. 1 (g).
Claims (1)
1. kaolinic method of hydration that direct replacement intercalation prepared layer spacing is 0.85nm is characterized in that the process step of this method is following:
A, to take by weighing weight ratio be that 1: 1 kaolinite and urea mixes and behind grinding 1h, puts into airtight Glass Containers, at 95 ℃ of following thermal treatment 48h, obtains kaolinite/urea intercalated compound and urea admixture (1);
B, every 1g kaolinite/urea intercalated compound and urea admixture (1) are added in 10～20ml deionized water, the unnecessary urea of magnetic agitation 1min flush away is at room temperature used absolute ethanol washing after centrifugal again, obtains kaolinite/urea intercalated compound (2);
In c, the deionized water with every 1g kaolinite/urea intercalated compound (2) adding 40～80ml; Stir 3～10min at 90～100 ℃ of lower magnetic forces; Use absolute ethanol washing after centrifugal again, after 40 ℃ of oven dry, obtaining Powdered interlamellar spacing is the hydration kaolinite of 0.85nm.
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| CN102583432B (en) * | 2011-12-28 | 2014-10-08 | 内蒙古包钢和发稀土有限公司 | Method for synthesizing nanometer Y-shaped molecular sieve by stripping coal series kaolin intercalation |
| CN103289447B (en) * | 2012-02-24 | 2014-12-24 | 中国矿业大学(北京) | Dissociation method of coal-series hard kaolinite rock lamella |
| CN102701229A (en) * | 2012-06-14 | 2012-10-03 | 浙江大学 | Method for preparing 0.84 nm kaolinite hydrate by hydrazine hydrate-kaolinite intercalation complex |
| CN103274424B (en) * | 2013-05-27 | 2014-12-17 | 浙江大学 | Serine/kaolinite intercalation compound prepared from 0.84nm hydrated kaolinite through two-step liquid-phase displacement method and preparation method thereof |
| CN103265047B (en) * | 2013-05-27 | 2014-12-17 | 浙江大学 | Method for preparing glycine-kaolinite intercalation compound by using hydration kaolinite |
| CN103926119B (en) * | 2014-02-19 | 2016-04-06 | 中国矿业大学(北京) | The measuring method of the kaolinic preparation of a kind of high radius-thickness ratio and radius-thickness ratio thereof |
| CN104402011A (en) * | 2014-11-05 | 2015-03-11 | 吴俊荣 | Preparation method of kaolin nanotubes |
| CN115055508B (en) * | 2022-08-09 | 2023-12-22 | 中国科学院兰州化学物理研究所 | Preparation of soil remediation material and application of soil remediation material in soil remediation of composite polluted farmland |
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| CN1544326A (en) * | 2003-11-17 | 2004-11-10 | 陕西科技大学 | Kaolinite intercalation method |
| CN101104517A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Method for preparing kaolinite organic intercalation composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1544326A (en) * | 2003-11-17 | 2004-11-10 | 陕西科技大学 | Kaolinite intercalation method |
| CN101104517A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Method for preparing kaolinite organic intercalation composition |
Non-Patent Citations (2)
| Title |
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| Yoshihiko Komori,et.al.Intercalation of alkylamines and water into kaolinite with methanol kaolinite as an intermediate.《Applied Clay Science》.1999,第15卷241-252. * |
| 徐剑锋等.直接置换插层法0.85 nm 水合高岭石的制备.《无机化学学报》.2011,第27卷(第6期),1121-1127. * |
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