CN101157472B - Method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology - Google Patents
Method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology Download PDFInfo
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- CN101157472B CN101157472B CN2007101443168A CN200710144316A CN101157472B CN 101157472 B CN101157472 B CN 101157472B CN 2007101443168 A CN2007101443168 A CN 2007101443168A CN 200710144316 A CN200710144316 A CN 200710144316A CN 101157472 B CN101157472 B CN 101157472B
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- earth metal
- alkaline
- different crystal
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Abstract
A method for preparing nanometer alkaline earth metal sulfate powder of different crystal shapes belongs to the technical field of nanometer material preparation. The invention solves the problem that the powder prepared with the prior method has high impurity content and large particle diameters and is disadvantageous to application due to morphological irregularity. The invention comprises the following steps: preparing mixed solution with alkaline earth metal salt and anhydrous ethanol; adding the solution prepared with soluble sulfate to obtain precipitate; with centrifugal precipitation, washing repeatedly the precipitate to clear away impurity ions; continuing centrifugal washing with anhydrous ethanol; placing the precipitate obtained after the centrifugal washing in an autoclave and injecting ethanol; raising the temperature to 245-270 DEG C with a constant speed and adjusting the pressure in the autoclave to 4-8MPa; stabilizing the temperature for one to two hours and then discharging the ethanol slowly; purging the residual ethanol for 0.5 hour with nitrogen with a flow rate of 5-20ml/min; and taking dried powder out after the autoclave is cooled to room temperature. The method of the invention has simple process; the purity of the product is higher than 99.9 percent; the final morphology of the powder can be controlled.
Description
Technical field
The invention belongs to the nano material preparation technical field, particularly a kind of employing directly precipitation-supercritical fluid drying prepares nano alkaline-earth metal sulfate powder with different crystal morphology.
Background technology
Alkaline earth metal sulphate is a kind of important chemical product.Growing along with continuous progress in science and technology and information and biological industry, market requires also more and more higher to material quality, particularly, also more and more high to purity, particle diameter and the uniformity requirement of product in fields such as the wider pottery of alkaline earth metal sulphate Application Areas, coating, papermaking and medical science.The existing big purity of sulfate powder foreign matter content is below 97%, its pattern majority is irregular particulate state, grain diameter generally more greatly the millimeter or micron order, size-grade distribution is big, and powder reuniting is serious, these all influence its moulding, sintering and application performance that some are special, as the high-temperature solid lubrication performance, therefore can't satisfy high-end industrial requirement.
Summary of the invention
Big for the powder foreign matter content that solves existing method preparation, the powder granule particle diameter is big, the irregular problem used of being unfavorable for of pattern, the invention provides a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology.The present invention adopts direct precipitation-supercritical fluid drying to prepare nano alkaline-earth metal sulfate powder with different crystal morphology, be to finish: one, at ambient temperature by the following step, utilize the alkaline earth salt and the vitriol of solubility, be mixed with alkaline-earth metal salt solution and sulfate liquor that concentration is 0.5～1.5mol/L respectively; Two, with alkaline-earth metal salt solution under 100～300rpm speed agitation condition, dehydrated alcohol is joined mixing in the alkaline-earth metal salt solution, the volume of the dehydrated alcohol of adding is 30～60% of an alkaline-earth metal salt solution volume; Three, under agitation condition with 500～1000rpm speed, join sulfate liquor in the mixing solutions fast, the volume of the sulfate liquor that adds is to get 1～1.5 times of alkaline-earth metal salt solution volume in the step 2, add the back and continue to stir 20～30min, resulting throw out washs with the method for centrifuge washing, centrifuge speed is 3000～5000rpm in the centrifuge washing process, with throw out with deionized water repetitive scrubbing 3～4 times, then with dehydrated alcohol centrifuge washing 1～3 time again; Four, the throw out behind the dehydrated alcohol centrifuge washing is placed autoclave and injects ethanol, be warming up to 245～270 ℃ with constant rate of speed, and adjusting still internal pressure is 4～8MPa, constant temperature 1～2 hour, slowly emit ethanol then, and, after autoclave is cooled to room temperature, obtain nano alkaline-earth metal sulfate powder with residual ethanol in the nitrogen purging still of 5～20ml/min flow 0.5 hour.
Method technology of the present invention is simple, product purity is up to 99.9% or more and the final morphology microstructure of may command, can prepare to be different from the powder that has pattern now, has special application performance.
Description of drawings
Fig. 1 is that pattern is the SrSO of diamond platy
4The scanning electron microscope picture of powder, Fig. 2 are that crystal morphology is the XRD spectra of diamond platy nanometer Strontium Sulphate powder, and Fig. 3 is that crystal morphology is the TG-DSC figure of diamond platy nanometer Strontium Sulphate powder, and Fig. 4 is that pattern is needle bar shape nanometer SrSO
4The scanning electron microscope picture of powder, Fig. 5 are that crystal morphology is the XRD spectra of needle bar shape nanometer Strontium Sulphate powder, and Fig. 6 is that crystal morphology is the TG-DSC figure of needle bar shape nanometer Strontium Sulphate powder, and Fig. 7 is that pattern is the Ba of ball shape
0.5Sr
0.5SO
4The scanning electron microscope picture of powder, Fig. 8 are that crystal morphology is ball shaped nano barium strontium sulfate sosoloid (Ba
0.5Sr
0.5SO
4) XRD spectra of powder, Fig. 9 is that crystal morphology is ball shaped nano barium strontium sulfate sosoloid (Ba
0.5Sr
0.5SO
4) the TG-DSC figure of powder.
Embodiment
Embodiment one: present embodiment prepares the method for nano alkaline-earth metal sulfate powder with different crystal morphology and is finished by the following step: one, at ambient temperature, utilize the alkaline earth salt and the vitriol of solubility, be mixed with alkaline-earth metal salt solution and sulfate liquor that concentration is 0.5～1.5mol/L respectively; Two, with alkaline-earth metal salt solution under 100～300rpm speed agitation condition, dehydrated alcohol is joined mixing in the alkaline-earth metal salt solution, the volume of the dehydrated alcohol of adding is the 30-60% of alkaline-earth metal salt solution volume; Three, under agitation condition with 500～1000rpm speed, join sulfate liquor in the mixing solutions fast, the volume of the sulfate liquor that adds is to get 1～1.5 times of alkaline-earth metal salt solution volume in the step 2, add the back and continue to stir 20～30min, resulting throw out washs with the method for centrifuge washing, centrifuge speed is 3000～5000rpm in the centrifuge washing process, with throw out with deionized water repetitive scrubbing 3～4 times, then with dehydrated alcohol centrifuge washing 1～3 time again; Four, the throw out behind the dehydrated alcohol centrifuge washing is placed autoclave and injects ethanol, be warming up to 245-270 ℃ with constant rate of speed, and adjusting still internal pressure is 4～8MPa, constant temperature 1～2 hour, slowly emit ethanol then, and, treat to take out after autoclave is cooled to room temperature with residual ethanol in the nitrogen purging still of 5～20ml/min flow 0.5 hour,, promptly obtain nano alkaline-earth metal sulfate powder.
Embodiment two: present embodiment is with the different of embodiment one: the alkaline earth salt in step 1 is a kind of of alkaline earth metal chloride or alkine earth metal nitrate, described alkine earth metal nitrate is one or both the combination in nitrocalcite, nitrate of baryta, the strontium nitrate, and described alkaline earth metal chloride is one or both the combination in calcium chloride, bariumchloride, the strontium chloride.
When alkaline earth salt is the composition of nitrocalcite and nitrate of baryta, perhaps during the composition of calcium chloride and bariumchloride, the mol ratio of Ca and Ba is 2: 3; When alkaline earth salt is the composition of nitrocalcite and strontium nitrate, perhaps the mol ratio of Ca and Sr is 7: 3 during the composition of calcium chloride and strontium chloride; When alkaline earth salt is the composition of strontium nitrate and nitrate of baryta, perhaps the mol ratio of Sr and Ba is 3: 1,1: 1 or 1: 3 during the composition of strontium chloride and bariumchloride.
Embodiment three: present embodiment is that with the different of embodiment one vitriol in step 1 is Na
2SO
4Or K
2SO
4A kind of.Other is identical with embodiment one.
Embodiment four: present embodiment and embodiment one different are that the concentration of alkaline-earth metal salt solution and sulfate liquor is 0.25～1.2mol/L in step 1.Other is identical with embodiment one.
Embodiment five: present embodiment and embodiment one different are that the concentration of alkaline-earth metal salt solution and sulfate liquor is 0.5mol/L in step 1.Other is identical with embodiment one.
Embodiment six: present embodiment and embodiment one different are that the volume of the dehydrated alcohol that adds is 35～55% of an alkaline-earth metal salt solution volume in step 2.Other is identical with embodiment one.
Embodiment seven: present embodiment and embodiment one different are that the volume of the dehydrated alcohol that adds is 40～50% of an alkaline-earth metal salt solution volume in step 2.Other is identical with embodiment one.
Embodiment eight: present embodiment and embodiment one different are that the volume of the dehydrated alcohol that adds is 45% of an alkaline-earth metal salt solution volume in step 2.Other is identical with embodiment one.
Embodiment nine: present embodiment and embodiment one different are that in step 3 centrifuge speed is 3500～4500rpm in the centrifuge washing process.Other is identical with embodiment one.
Embodiment ten: present embodiment and embodiment one different are that in step 3 centrifuge speed is 4000rpm in the centrifuge washing process.Other is identical with embodiment one.
Embodiment 11: what present embodiment and embodiment one were different is in step 4 temperature to be increased to 250-265 ℃.Other is identical with embodiment one.
Embodiment 12: present embodiment is that with the different of embodiment one temperature is increased to 260 ℃ in the step 4.Other is identical with embodiment one.
Embodiment 13: present embodiment is that with the different of embodiment one in step 4 mesohigh still internal pressure be 5～7MPa.Other is identical with embodiment one.
Embodiment 14: present embodiment is that with the different of embodiment 16 step 4 mesohigh still internal pressure is 6MPa.Other is identical with embodiment one.
Embodiment 15: present embodiment nanometer SrSO
4Powder is finished by the following step: one, at ambient temperature, get pure SrCl
26H
2O and Na
2SO
4, be mixed with the SrCl that concentration is 0.5mol/L respectively
2Solution and Na
2SO
4Solution; Two, get the SrCl of 120ml
2Solution adds the 72ml dehydrated alcohol under with 100～300rpm speed agitation condition, and continues to stir 30～60min; Three, under with 500～1000rpm speed agitation condition, with the Na of 100ml
2SO
4Solution join fast in the mixing solutions, add the back and continue to stir 20～30 minutes, resultant throw out does not extremely contain Cl with throw out with the deionized water repetitive scrubbing with the method washing of centrifuge washing
-Ion, centrifuge speed are 3000～5000rpm, continue centrifuge washing 1～3 time with dehydrated alcohol then; Four, the throw out behind the dehydrated alcohol centrifuge washing is placed autoclave and injects ethanol, be warming up to 270 ℃ with 100 ℃/h, and make the still internal pressure reach 7.2MPa, constant temperature is slowly emitted ethanol after 1.5 hours, then with in the nitrogen purging still of 5-20ml/min flow 0.5 hour, after autoclave is cooled to room temperature, obtain nanometer SrSO
4Powder.
Analyze the nanometer SrSO that present embodiment prepares in conjunction with Fig. 1～3
4Powder all is single oblique side's phase structure, product purity height (up to more than 99.9%); Morphology microstructure is a diamond platy, and sheet is thick about 50～70nm.The pattern that studies show that diamond platy can help high-temperature solid lubrication.
Embodiment 16: present embodiment adopts pure BaCl with the different alkaline-earth metal salt solutions that are of embodiment 15
26H
2The O configuration, other step is identical with embodiment 15.
The nanometer BaSO that present embodiment prepares
4Powder all is single oblique side's phase structure, product purity height (up to more than 99.9%); Morphology microstructure is spherical, and particle diameter is about 50～70nm.
Embodiment 17: present embodiment nanometer SrSO
4Powder is finished by the following step: one, at ambient temperature, get pure Sr (NO
3)
2And K
2SO
4, being mixed with concentration respectively is the Sr (NO of 1.0mol/L
3)
2Solution and K
2SO
4Solution; Two, get the Sr (NO of 100ml
3)
2Solution adds the 60ml dehydrated alcohol under with 100～300rpm speed agitation condition, and continues to stir 30～60min; Three, under with 500～1000rpm speed agitation condition, with the K of 100ml
2SO
4Solution join fast in the mixing solutions, add the back and continue to stir 20～30 minutes, resultant throw out is with the method washing of centrifuge washing, with throw out with the deionized water repetitive scrubbing to alkali-free earth metals and SO
4 2-Ion, centrifuge speed are 3000～5000rpm, continue centrifuge washing 1～3 time with dehydrated alcohol then; Four, the throw out behind the dehydrated alcohol centrifuge washing is placed autoclave and injects ethanol, be warming up to 270 ℃ with 100 ℃/h, and make the still internal pressure reach 7.2MPa, constant temperature is slowly emitted ethanol after 1.5 hours, then with in the nitrogen purging still of 5～20ml/min flow 0.5 hour, treat to take out after autoclave is cooled to room temperature, promptly obtain nanometer SrSO
4Powder.
Analyze the nanometer SrSO that present embodiment prepares in conjunction with Fig. 4～6
4Powder all is single oblique side's phase structure, product purity height (up to more than 99.9%); Morphology microstructure is a needle bar shape, and diameter is about 60～80nm.
Embodiment 18: this side of enforcement nanometer Ba
0.5Sr
0.5SO
4Powder is finished by the following step: one, at ambient temperature, get pure BaCl
2, SrCl
2And Na
2SO
4, be mixed with Sr
2+, Ba
2+Mixing solutions and concentration that ionic concn is all 0.5mol/L are the Na of 1.0mol/L
2SO
4Solution; Two, get the BaCl of 200ml
2And SrCl
2Mixing solutions adds the 120ml dehydrated alcohol under with 100～300rpm speed agitation condition, and continues to stir 30～60min; Three, under with 500～1000rpm speed agitation condition, with the Na of 210ml
2SO
4Solution join fast in the mixing solutions, add the back and continue to stir 20～30 minutes, resultant throw out does not extremely contain Cl with throw out with the deionized water repetitive scrubbing with the method washing of centrifuge washing
-Ion and SO
4 2-Ion, centrifuge speed are 3000～5000rpm, continue centrifuge washing l～3 times with dehydrated alcohol then; Four, the throw out behind the dehydrated alcohol centrifuge washing is placed autoclave and injects ethanol, be warming up to 270 ℃ with 100 ℃/h, and make the still internal pressure reach 7.2MPa, constant temperature is slowly emitted ethanol after 1.5 hours, then with in the nitrogen purging still of 5-20ml/min flow 0.5 hour, treat to take out after autoclave is cooled to room temperature, promptly obtain nanometer Ba
0.5Sr
0.5SO
4Powder.
Analyze the nanometer Ba that present embodiment prepares in conjunction with Fig. 7～9
0.5Sr
0.5SO
4Powder all is single oblique side's phase structure, product purity height (up to more than 99.9%); Morphology microstructure is spherical, and particle diameter is at 80～100nm.
Embodiment 19: present embodiment and embodiment 18 different being: in step 1, at ambient temperature, get pure BaCl
2, SrCl
2And Na
2SO
4, be mixed with Sr
2+Ionic concn is 0.25mol/L, Ba
2+Ionic concn is that mixing solutions and the concentration of 0.75mol/L is the Na of 1.0mol/L
2SO
4Solution.Other step is identical with embodiment 19.
The nanometer Ba for preparing
0.75Sr
0.25SO
4Powder all is single oblique side's phase structure, product purity height (up to more than 99.9%); Morphology microstructure is spherical, and particle diameter is at 80～100nm.
Embodiment 20: present embodiment and embodiment 18 different being: in step 1, at ambient temperature, get pure BaCl
2, SrCl
2And Na
2SO
4, be mixed with Sr
2+Ionic concn is 0.75M, Ba
2+Ionic concn is that mixing solutions and the concentration of 0.25mol/L is the Na of 1.0M
2SO
4Solution.Other step is identical with embodiment 19.
The nanometer Ba that present embodiment prepares
0.25Sr
0.75SO
4Powder all is single oblique side's phase structure, product purity height (up to more than 99.9%); Morphology microstructure is spherical, and particle diameter is at 80～100nm.
Claims (10)
1. method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology, it is characterized in that it is finished by the following step: one, at ambient temperature, utilize the alkaline earth salt and the vitriol of solubility, be mixed with alkaline-earth metal salt solution and sulfate liquor that concentration is 0.5～1.5mol/L respectively; Two, with alkaline-earth metal salt solution under 100～300rpm speed agitation condition, dehydrated alcohol is joined mixing in the alkaline-earth metal salt solution, the volume of the dehydrated alcohol of adding is 30～60% of an alkaline-earth metal salt solution volume; Three, under agitation condition with 500～1000rpm speed, join sulfate liquor in the mixing solutions fast, the volume of the sulfate liquor that adds is to get 1～1.5 times of alkaline-earth metal salt solution volume in the step 2, add the back and continue to stir 20～30min, resulting throw out washs with the method for centrifuge washing, centrifuge speed is 3000～5000rpm in the centrifuge washing process, with throw out with deionized water repetitive scrubbing 3～4 times, then with dehydrated alcohol centrifuge washing 1～3 time again; Four, the throw out behind the dehydrated alcohol centrifuge washing is placed autoclave and injects ethanol, be warming up to 245～270 ℃ with constant rate of speed, and adjusting still internal pressure is 4～8MPa, constant temperature 1～2 hour, slowly emit ethanol then, and, after autoclave is cooled to room temperature, obtain nano alkaline-earth metal sulfate powder with residual ethanol in the nitrogen purging still of 5～20ml/min flow 0.5 hour.
2. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 1 is characterized in that the alkaline earth salt in step 1 is alkaline earth metal chloride or alkine earth metal nitrate.
3. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 2 is characterized in that alkine earth metal nitrate is one or both the combination in nitrocalcite, nitrate of baryta, the strontium nitrate.
4. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 2 is characterized in that described alkaline earth metal chloride is one or both the combination in calcium chloride, bariumchloride, the strontium chloride.
5. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 1 is characterized in that the vitriol in step 1 is Na
2SO
4Or K
2SO
4
6. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 1 is characterized in that the concentration of alkaline-earth metal salt solution and sulfate liquor is 1.2mol/L in step 1.
7. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 1 is characterized in that the concentration of alkaline-earth metal salt solution and sulfate liquor is 0.5mol/L in step 1.
8. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 1 is characterized in that the volume of the dehydrated alcohol that adds is 35～55% of an alkaline-earth metal salt solution volume in step 2.
9. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 1 is characterized in that step 4 mesohigh still internal pressure is 5～7MPa.
10. a kind of method for preparing nano alkaline-earth metal sulfate powder with different crystal morphology according to claim 1 is characterized in that in step 4 mesohigh still internal pressure be 6MPa.
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| CN102351233B (en) * | 2011-07-22 | 2013-06-19 | 中南大学 | Production process for nanometer barium sulfate |
| CN112624173A (en) * | 2020-12-30 | 2021-04-09 | 天津科技大学 | Preparation method of barium sulfate crystal with controllable shape |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609242A (en) * | 2004-02-03 | 2005-04-27 | 祁顺东 | Process for recovering strontium and aluminium from metal strontium residue |
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| CN1609242A (en) * | 2004-02-03 | 2005-04-27 | 祁顺东 | Process for recovering strontium and aluminium from metal strontium residue |
Non-Patent Citations (3)
| Title |
|---|
| 李彩虹 等.单分散纳米硫酸锶粉体的制备.化工学报55 1.2004,55(1),116-120. * |
| 李彩虹 等.硫酸锶晶体生长动力学研究.无机盐工业37 3.2005,37(3),14-16. |
| 李彩虹 等.硫酸锶晶体生长动力学研究.无机盐工业37 3.2005,37(3),14-16. * |
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