CN108640123B - Preparation method of bismuth-titanium intercalated montmorillonite - Google Patents
Preparation method of bismuth-titanium intercalated montmorillonite Download PDFInfo
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- CN108640123B CN108640123B CN201810408077.0A CN201810408077A CN108640123B CN 108640123 B CN108640123 B CN 108640123B CN 201810408077 A CN201810408077 A CN 201810408077A CN 108640123 B CN108640123 B CN 108640123B
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Abstract
The invention provides a preparation method of bismuth-titanium intercalated montmorillonite, which mainly comprises two parts, namely preparation of titanium crosslinked montmorillonite and reaction of the titanium crosslinked montmorillonite and bismuth ions, and provides a new method for preparing bismuth-titanium-containing intercalated montmorillonite material. The invention belongs to the field of composite material preparation.
Description
Technical Field
The invention relates to a preparation method of a composite material, and belongs to the field of preparation of composite materials.
Background
With the increasing living standard of people, the requirement on the environmental quality is increased, and the problems of environmental pollution and the like need to be solved urgently. Montmorillonite has important application in the aspects of heavy metal ion adsorption, molecular sieve, biological pharmacy, drug carrier, photocatalyst and the like, but the intercalated montmorillonite which is actively researched and has a development prospect at present can be developed into a novel material which is suitable for being used as an adsorbent for sewage treatment, a drug carrier material, a cosmetic additive and the like, and is a material which attracts much attention at home and abroad, wherein the bismuth-titanium intercalated montmorillonite is the material and has much attention.
Disclosure of Invention
The invention aims to: the preparation process of bismuth-titanium intercalated montmorillonite includes two steps of preparation of titanium crosslinked montmorillonite and reaction of titanium crosslinked montmorillonite with bismuth ion, and this provides new method for preparing bismuth-containing titanium intercalated montmorillonite material.
In order to solve the problems, the preparation method of the bismuth-titanium intercalated montmorillonite is specifically as follows:
(1) weighing sodium-based montmorillonite, placing into a beaker, adding distilled water, and stirring; taking the upper suspension;
(2) slowly dripping titanate chelate into isopropanol, stirring and mixing uniformly according to a proportion, adjusting the pH value, and then standing at room temperature; slowly adding the mixture obtained in the step (2) into the mixture obtained in the step (1), stirring at constant temperature, and standing overnight;
(3) centrifuging overnight, washing with purified water until no chloride ion is present, and washing with AgNO3Inspecting the solution, and drying the separated solid in a vacuum drying oven;
(4) crushing the dried solid to obtain a titanium pillared montmorillonite product, and roasting at high temperature to obtain a titanium pillared montmorillonite material;
(5) adding a certain amount of titanium pillared montmorillonite material into a beaker, adding distilled water, and magnetically stirring at normal temperature to uniformly disperse the titanium pillared montmorillonite material;
(6) adding Bi into the suspension liquid of the step (5)3+A solution; stirring the mixed solution in a constant-temperature water bath;
(7) taking out the mixed solution, cooling at normal temperature, and performing centrifugal separation;
(8) washing the obtained powder with nitric acid solution for several times, and detecting the supernatant with color developing agent until no color development;
(9) and washing the powder with deionized water to be neutral, drying and grinding to obtain the bismuth-titanium montmorillonite sample.
In the step (1), the purity of the sodium-based montmorillonite is at least 90%, 6g of the sodium-based montmorillonite is weighed and soaked in 600ml of water, and the stirring time is 90 min;
in the step (1), the concentration of the prepared montmorillonite suspension is 0.50-1.00%;
in the step (2), the titanate chelating agent/isopropyl alcohol is 1:1, regulating the PH value to 9-10, wherein the preparation of the titanium cross-linking agent solution requires room-temperature cross-linking reaction for 30min, and standing for 2 h; 15-20 mmol/g of Ti/montmorillonite in the mixed solution;
in the step (2), the constant temperature is 50 ℃, and the stirring time is 2 hours;
in the step (3), the centrifugal separation rotating speed is 4000 rpm; the standard for detecting no chloride ion is that the supernatant is dripped with AgNO3No white precipitate is generated; the drying temperature in the vacuum drying oven is 55-70 ℃;
in the step (4), the high-temperature roasting temperature is 180 ℃;
in the step (5), the normal temperature is 20 ℃, and the magnetic stirring time is 0.5 h;
in the step (6), the Bi3+The solution is prepared by dissolving bismuth nitrate pentahydrate crystals in 0.1mol/L nitric acid, and the concentration of bismuth ions in the obtained solution is 0.05-0.06 mol/L;
in the step (6), in the prepared mixed solution, the mass of the bismuth ions/the mass of the titanium pillared montmorillonite material is 0.05;
in the step (6), the temperature of the constant-temperature water bath is 80 ℃, and the time is 6 hours;
in the step (7), the centrifugal separation rotating speed is 4000 rpm;
in the step (8), the concentration of the nitric acid solution is 0.01 mol/L;
the color developing agent is a mixed solution of thiourea, potassium iodide and ascorbic acid, and the volume ratio of the thiourea to the potassium iodide to the ascorbic acid is 1: 1: 1.
in the step (9), the drying temperature is 70 ℃.
Compared with the prior art, the invention has the following advantages:
1) when titanium cross-linked montmorillonite is prepared in a laboratory, the interlayer spacing of the montmorillonite is small, if isopropanol is not added, the exchange reaction of the cross-linking agent and exchangeable cations between montmorillonite layers is incomplete, and only a few titanium-based cations enter between the montmorillonite layers. The isopropanol is a non-protic polar solvent, which can enable the montmorillonite to be dispersed more fully, the activity of titanium polymeric hydroxyl cations in a system is improved, the efficiency of the titanium polymeric hydroxyl cations entering the interlayer of the montmorillonite is greatly improved, and the cross-linking reaction is accelerated. Thereby preparing the titanium pillared montmorillonite material with excellent performance.
2) Due to Bi (NO)3)3+H2O→BiONO3↓+2HNO3And bismuth subnitrate precipitates. The bismuth nitrate pentahydrate is dissolved in the dilute nitric acid, so that the hydrolysis of bismuth ions can be inhibited, and the utilization rate of the bismuth ions is improved.
3) The reduction of the crystal spacing of montmorillonite treated with nitric acid or bismuth nitrate is more remarkable, but with Bi in the solution3+Increase of initial concentration of ions, crystals of montmorilloniteThe inter-planar spacing gradually increases. When the concentration of bismuth ions is 0.06mol/L, the utilization rate of bismuth ions can be improved, and the crystal face spacing can not be reduced.
4) This is due to H+The cation between montmorillonite layers is converted into acid soluble salt to be dissolved out, so that the bonding force between layers is weakened, and the crystal lattice between layers is cracked. At the same time, H+Can react with partial aluminum octahedron to change the original six-coordination aluminum into four-coordination aluminum, further destroy the structure of montmorillonite and deteriorate the crystallinity. However, in the presence of Bi3+In an acid solution of (2), H+The probability of contacting montmorillonite is reduced, and Bi is generated because the adsorption of montmorillonite to positive ions is chemical adsorption3+Has a charge intensity stronger than H+So that Bi3+Ratio H+Ions can enter between montmorillonite layers more easily to inhibit H+Enter into the interlayer of montmorillonite and approach the montmorillonite. Therefore, bismuth ions in the acid solution have a certain protective effect on the structure of the montmorillonite.
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FIG. 1 is a process flow diagram of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail with reference to the accompanying drawings, and it should be understood that the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention.
Example (b):
referring to the attached fig. 1, this example provides a method for preparing bismuth titanium intercalated montmorillonite, which specifically includes the following steps:
adding 6g of high-purity sodium-based montmorillonite product into distilled water to prepare montmorillonite suspension with the concentration of 0.8%, and stirring for 90min for later use; slowly dripping a proper amount of titanate chelating agent into a proper amount of isopropanol under the condition of stirring, wherein the volume ratio of the titanate chelating agent to the isopropanol is 1:1, adjusting the pH value to be 9-10, then carrying out crosslinking reaction at room temperature for 30min, and standing for 2h to obtain a titanium crosslinking agent; slowly dripping the prepared titanium cross-linking agent into the montmorillonite suspension under the condition of vigorous stirring, reacting for 2h at 50 ℃, and standing overnight; centrifuging overnight (4000rpm), washing the separated solid with deionized water for 3-5 times, and drying at 65 deg.C in a vacuum drying oven; crushing the dried solid to obtain a primary titanium pillared montmorillonite product, and roasting at high temperature to obtain the titanium pillared montmorillonite; adding the obtained product into 100ml of distilled water, and electromagnetically stirring for 0.5h for later use; dissolving bismuth nitrate pentahydrate by using 0.1mol/L nitric acid solution to prepare 0.06mol/L bismuth ion solution, then slowly adding 20ml of bismuth ion solution into the titanium pillared montmorillonite suspension, and magnetically stirring for 0.5h at normal temperature to uniformly disperse the mixed solution. The mixed solution was stirred in a constant temperature water bath at 80 ℃ for 6 hours. Taking out the mixed solution, cooling at normal temperature, performing centrifugal separation, and washing the obtained powder with 0.01mol/L nitric acid solution for several times until the color development of the supernatant is detected by using a color development agent; and then washing the powder with deionized water to be neutral, drying at 90 ℃, and grinding to obtain the bismuth-titanium intercalated montmorillonite.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The preparation method of the bismuth-titanium intercalated montmorillonite is characterized by comprising the following specific steps of:
(1) weighing sodium-based montmorillonite, placing into a beaker, adding distilled water, and stirring; taking the upper suspension;
(2) slowly dripping titanate chelate into isopropanol, stirring and mixing uniformly according to a proportion, adjusting the pH value, and then standing at room temperature; slowly adding the mixture obtained in the step (2) into the mixture obtained in the step (1), stirring at constant temperature, and standing overnight;
(3) centrifuging overnight, washing with purified water until no chloride ion is present, and washing with AgNO3Inspecting the solution, and drying the separated solid in a vacuum drying oven;
(4) crushing the dried solid to obtain a titanium pillared montmorillonite product, and roasting at high temperature to obtain a titanium pillared montmorillonite material;
(5) adding a certain amount of titanium pillared montmorillonite material into a beaker, adding distilled water, and magnetically stirring at normal temperature to uniformly disperse the titanium pillared montmorillonite material;
(6) adding Bi into the suspension liquid of the step (5)3+A solution; stirring the mixed solution in a constant-temperature water bath;
(7) taking out the mixed solution, cooling at normal temperature, and performing centrifugal separation;
(8) washing the obtained powder with nitric acid solution for several times, and detecting the supernatant with color developing agent until no color development;
(9) and washing the powder with deionized water to be neutral, drying and grinding to obtain the bismuth-titanium intercalated montmorillonite.
2. The method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (1), the purity of the sodium montmorillonite is at least 90%, 6g of the sodium montmorillonite is weighed and soaked in 600ml of water, the stirring time is 90min, and the concentration of the prepared montmorillonite suspension is 0.50-1.00%.
3. The method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (3), the centrifugal separation rotating speed is 4000 rpm; the standard for detecting no chloride ion is that the supernatant is dripped with AgNO3No white precipitate is generated; the drying temperature in the vacuum drying oven is 55-70 ℃.
4. The method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (4), the high-temperature roasting temperature is 180 ℃.
5. The method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (5), the normal temperature is 20 ℃, and the magnetic stirring time is 0.5 h.
6. The method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (6), the Bi3+The solution is dissolved by bismuth nitrate pentahydrate crystalsThe bismuth ions are dissolved in 0.1mol/L nitric acid to prepare the bismuth ion-doped bismuth oxide solution, and the concentration of the bismuth ions in the obtained solution is 0.05-0.06 mol/L; in the prepared mixed solution, the mass of the bismuth ions/the mass of the titanium pillared montmorillonite material is 0.05; in the step (6), the temperature of the constant-temperature water bath is 80 ℃ and the time is 6 hours.
7. The method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (7), the centrifugal separation rotating speed is 4000 rpm.
8. The method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (8), the concentration of the nitric acid solution is 0.01 mol/L; the color developing agent is a mixed solution of thiourea, potassium iodide and ascorbic acid, and the volume ratio of the thiourea to the potassium iodide to the ascorbic acid is 1: 1: 1.
9. the method for preparing bismuth-titanium intercalated montmorillonite according to claim 1, characterized by comprising the following steps: in the step (9), the drying temperature is 70 ℃.
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| CN114713219A (en) * | 2022-04-08 | 2022-07-08 | 贵州大学 | Preparation method of montmorillonite-loaded Bi20O30 & TiO2 composite material with efficient photocatalytic performance |
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| CN102807861A (en) * | 2012-08-20 | 2012-12-05 | 陕西科技大学 | Preparation method for bismuth/montmorillonite photoluminescence material |
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Patent Citations (6)
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| US4176090A (en) * | 1975-11-18 | 1979-11-27 | W. R. Grace & Co. | Pillared interlayered clay materials useful as catalysts and sorbents |
| JP3686939B2 (en) * | 2001-11-27 | 2005-08-24 | 独立行政法人産業技術総合研究所 | Smectite-titanium oxide porous body and synthesis method thereof |
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