CN108285165A - A kind of preparation method of nanometer calcium sulfate - Google Patents

A kind of preparation method of nanometer calcium sulfate Download PDF

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Publication number
CN108285165A
CN108285165A CN201810059424.3A CN201810059424A CN108285165A CN 108285165 A CN108285165 A CN 108285165A CN 201810059424 A CN201810059424 A CN 201810059424A CN 108285165 A CN108285165 A CN 108285165A
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solution
ethyl alcohol
absolute ethyl
calcium sulfate
supercentrifuge
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CN108285165B (en
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苏英
邱慧琼
贺行洋
陈顺
王迎斌
杨进
徐焰
黄健翔
张海峰
彭凯
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Hubei University of Technology
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Hubei University of Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/46Sulfates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00Calcium sulfate cements
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/60Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65Chroma (C*)

Abstract

The present invention discloses a kind of preparation method of nanometer calcium sulfate, and concentrated sulfuric acid solution, which is added in deionized water, to be diluted, and solution A is obtained;Ca(OH)2And gelatin hydrolysate and/or soybean protein are added in diglycol ethylene, and B solution is obtained after stirring evenly;It is added dropwise in B solution in solution A, magnetic agitation, stands to obtain mixture solution one;Mixture solution one is centrifuged with supercentrifuge, then is washed with absolute ethyl alcohol, disperseed to centrifuge product, and absolute ethyl alcohol is recycled;Centrifugation product is added in n-butanol and/or hexadecanol, and magnetic agitation stands to obtain mixture solution two;Mixture solution two is centrifuged with supercentrifuge, then is washed with absolute ethyl alcohol, disperseed to centrifuge product, and absolute ethyl alcohol is recycled;It is freeze-dried in product vacuum environment, obtains nanometer calcium sulfate particle.Grain diameter produced by the present invention is small, large specific surface area, nano-scale particle content are high, water-tolerant, is suitable for the fields such as building materials, green material, biomaterial.

Description

A kind of preparation method of nanometer calcium sulfate
Technical field
The invention belongs to building material technical fields, and in particular to a kind of preparation method of nanometer calcium sulfate.
Background technology
Nano material is at least one-dimensional material for being in 1~100nm ranges, because its excellent chemical and physical features exists The industries such as traditional material, medical equipment, electronic equipment, coating are widely used.Currently, the nanometer prepared by calcium sulfate Material has sulfuric acid calcium nano, nanotube, nanometer rods etc., it not only remains common the nontoxic of powder calcium sulfate, lightweight, glue The excellent performances such as solidifying property is good, acoustical and thermal, good flame resistance, but with good toughness, intensity it is high be easily surface-treated, high specific heat and The characteristic for the nano-sized materials such as high magnetic susceptibility, affinity is strong, therefore it is many to can be widely applied to medicine, biology, environmental protection etc. Field.
Ultra-fine nanometer calcium sulfate particle in aqueous environments is easy to grow up, and ultimately forms acicular thick sulfuric acid calcium particle, It is general that ultra-fine nanometer calcium sulfate particle cannot be prepared in aqueous environments using classical chemical method.
CN 102234127A disclose a kind of preparation process of nanometer calcium sulfate, with lime, iron oxide pigment production process The ammonium sulfate of discharge is raw material, prevents the superfine nano calcium sulfate particle in preparation process from growing up using resistive agent, obtains Ultra-fine nanometer calcium sulfate powder;Include the following steps:Lime is emulsified, is refined;Resistive agent is added in refined calcium hydroxide emulsion; Calcium hydroxide slurry is reacted with ammonium sulfate;The washing of nanometer calcium sulphate dihydrate slurry by filtration and the fractionation of weak aqua ammonia recycling. But nanometer calcium sulfate is of high cost made from the method, makes complexity, and calcium sulfate crystal form and size are not easy to control and water washed filtering Calcium sulphate crystal is easy to happen agglomeration in journey.
CN 103011230B disclose a kind of method of inexpensive preparing nano calcium sulfate, by containing sulfate brine and contain Calcium salt brine mixes, stirring;After standing, bottom precipitation is added in centrifuge or filter press, removes mother liquor, and water stirring is added to wash It washs, then is dehydrated with centrifuge or filter press, obtain wet calcium sulphate dihydrate;It is ground after drying, obtains nanoscale calcium sulfate.Though it with By-product containing sulfate brine in salt manufacturing and other marine chemical industry production processes or calcic bittern water, can turn waste into wealth, but It is that the sulfuric acid calcium impurities prepared are more, is unable to get high-purity, high-grade nanometer calcium sulfate, and pass through nanoscale grinder The calcium sulfate of generation is ground into nanoscale, it is not only of high cost, and the bad control of crystal form.
Paper《The extensive preparation of nanometer calcium sulfate whisker under room temperature》Using room temperature acidization, with calcium chloride and dense Sulfuric acid is raw material, and alcohol-water is mixed solvent, and cetyl trimethylammonium bromide (CTAB) is chemical additives, room temperature condition It is prepared for nanometer calcium sulfate whisker on a large scale down, prepared calcium sulfate crystal whiskers size uniform, diameter be about under the optimal conditions It is about 30 for 200nm, draw ratio.This paper mainly prepares the calcium sulfate crystal whiskers of nanometer, and shape is joined in research process Although several variations are not obvious for calibration parameters, situation of change is still remained, preparation process is not easily-controllable System.
Invention content
The purpose of the present invention is be directed to above-mentioned present situation, it is desirable to provide a kind of grain diameter is small, large specific surface area, nanoscale Grain content height, water-tolerant;Raw material is easy to get, the preparation method of the simple nanometer calcium sulfate of preparation process economy.
The realization method of the object of the invention is that a kind of preparation method of nanometer calcium sulfate is as follows:
1) 42~60g concentrated sulfuric acid solutions are added in the deionized water of 50~96g, be diluted to mass concentration be 40~ 50%, obtain solution A;
2) by the Ca of 20~25g (OH)2And the chemical additives gelatin hydrolysate and/or soybean protein of 1g be added to 20~ In the diglycol ethylene of 28g, B solution is obtained after stirring evenly;
3) it is added dropwise into the solution A obtained by step 1) in the B solution obtained by 20g steps 2), 25 DEG C, 100r/min Magnetic stirrer 5min obtains mixture solution one after standing 5min;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 5~9min of separation, then with anhydrous Ethyl alcohol washing, dispersion centrifugation product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 600~800W, 1500~3000r/min of centrifugal rotational speed;
5) it will be added in 0.2~1.0g n-butanols and/or hexadecanol through the product obtained by step 4), 25 DEG C, 100r/min Magnetic stirrer 5min obtains mixture solution two after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 5~9min, then uses absolute ethyl alcohol Washing, dispersion centrifugation product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 600~800W, 1500~2700r/min of centrifugal rotational speed;
7) product obtained by step 6) is carried out in -5~-10 DEG C, the vacuum environment of 15~25pa freeze-drying 5~ 10min is to get nanometer calcium sulfate particle.
The present invention has the following advantages:
1, it for the calcium sulfate particle crystal form that solution medium is prepared is spherical particles, size that the present invention, which uses diglycol ethylene, For 10~25nm, specific surface area 300-400m2/g;
2, chemical additives regulation and control Ca (OH) is utilized2The crystal form and ruler of the calcium sulfate generated with dense sulfuric acid solution reaction It is very little, prepare high-purity with characteristics such as nano-scale particle content > 96.2%, whiteness > 95.8, high-grade modified Nano Calcium sulfate;
3, calcium sulfate surface one layer of waterproof membrane of formation can be adsorbed on well using macromolecule biological activity embedding medium to make The nanoscale calcium sulfate of preparation has significant water resistance, solubility < 0.85g/L in water;
4, be added chemical additives and macromolecule biological activity embedding medium be all macromolecular, on the one hand control reaction at Core enhances water resistance, and on the other hand these macromoleculars can be adsorbed on particle surface, generate space steric effect between particles, Improve the dispersion performance of particle;
5, using the processing mode of freeze-drying, reduce the agglomeration that may occur in preparation process;
6, used is all environmentally protective material, and impurity will not be introduced in reacting preparation system.
Raw material of the present invention is easy to get, and preparation process economy is simple, efficient, low cost so that prepare ultra-fine receive using chemical method Rice calcium sulfate product industrialized production is possibly realized;The product particle grain size prepared is small, large specific surface area, nano-scale particle contain Amount height, water-tolerant;Suitable for commercial introduction, and the product prepared is in building materials, green material, biomaterial etc. Aspect has considerable application prospect.
Specific implementation mode
The present invention is that concentrated sulfuric acid solution is added in deionized water to dilute, and obtains solution A;Ca(OH)2With chemical additives water Solution gelatin is added in diglycol ethylene, and B solution is obtained after stirring evenly;It is added dropwise in solution A in B solution, magnetic force stirs It mixes, stands to obtain mixture solution one;Mixture solution one is centrifuged with supercentrifuge, then is washed, disperseed with absolute ethyl alcohol Product is centrifuged, absolute ethyl alcohol is recycled;Centrifugation product be added in n-butanol and/or hexadecanol, magnetic agitation, stand mixture is molten Liquid two;Mixture solution two is centrifuged with supercentrifuge, then is washed with absolute ethyl alcohol, disperseed to centrifuge product, and absolute ethyl alcohol is recycled; It is freeze-dried in product vacuum environment, obtains nanometer calcium sulfate particle.
The chemical additives selection gelatin hydrolysate and/or soybean protein of the present invention is because gelatin hydrolysate is collagen Product through enzyme (acid or alkali) hydrolysis, the derivative of gelatin hydrolysis.The water that can be dissolved under room temperature.A concentration of 20% aqueous solution, Viscosity at 25 DEG C is 50Pas, and soybean protein is a kind of vegetable protein, this one or two kinds of substance is added in reactant Impurity will not be introduced in system, crystal form that is environmentally protective and can controlling the calcium sulfate that reaction generates well is ball-type and control life At the size of calcium sulfate in the process.
The macromolecule biological activity embedding medium selection n-butanol and/or hexadecanol of the present invention, be because n-butanol and/or Hexadecanol is not soluble in water but is dissolved in absolute ethyl alcohol, can be adsorbed on calcium sulfate surface well and form one layer of waterproof membrane, be added simultaneously This one or two kinds of substance can be washed away quickly and not introduce new impurity in preparation process, environmentally protective.
The present invention solution medium select diglycol ethylene, be because diglycol ethylene be water white transparency have it is hygroscopic Thick liquid is dissolved in water and absolute ethyl alcohol, and guarantee, which prepares environment, will not introduce impurity, the CaSO that reaction can be made to generate4Quickly analysis Go out crystallization.
Below by embodiment, invention is further described in detail, and raw materials used in embodiment is analytically pure Ca (OH)2And the concentrated sulfuric acid, gelatin hydrolysate and/or soybean protein, n-butanol and/or hexadecanol, diglycol ethylene are commercial product.
Embodiment 1:
1) 30g concentrated sulfuric acid solutions are added in the deionized water of 30g, dilution obtains solution A;
2) by the Ca of 20g (OH)2It is added in the diglycol ethylene of 20g, stirs with the chemical additives gelatin hydrolysate of 1g B solution is obtained after uniformly;
3) it is added dropwise into the solution A obtained by step 1) in the B solution obtained by 20g steps 2), 25 DEG C, 100r/min Magnetic stirrer 5min obtains mixture solution one after standing 5min;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 5min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 600W, centrifugal rotational speed 1500r/min;
5) it will be added in 0.2g n-butanols through the product obtained by step 4), 25 DEG C, 100r/min magnetic stirrers 5min obtains mixture solution two after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 5min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 600W, centrifugal rotational speed 1500r/min;
7) product obtained by step 6) is carried out to freeze-drying 5min in -5 DEG C, the vacuum environment of 15pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 25nm, specific surface area 300m2/ g, nanoscale Granule content is 96.2%, whiteness 95.8%, and water solubility is 0.85g/L.
Embodiment 2, with embodiment 1, unlike,
1) 44g concentrated sulfuric acid solutions are added in the deionized water of 54g, dilution obtains solution A;
2) by the Ca of 22g (OH)2It is added in the diglycol ethylene of 25g with the gelatin hydrolysate of 1.5g, after stirring evenly To B solution;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 5min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 650W, centrifugal rotational speed 1700r/min;
5) it will be added in 0.5g n-butanols through the product obtained by step 4), 25 DEG C, 100r/min magnetic stirrers 5min obtains mixture solution two after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 5min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 650W, centrifugal rotational speed 1700r/min;
7) product obtained by step 6) is carried out to freeze-drying 7min in -5 DEG C, the vacuum environment of 15pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 20nm, specific surface area 340m2/ g, nanoscale Granule content is 97.9%, whiteness 96.7%, and water solubility is 0.76g/L.
Embodiment 3, with embodiment 1, unlike,
1) 48g concentrated sulfuric acid solutions are added in the deionized water of 96g, dilution obtains solution A;
2) by the Ca of 24g (OH)2It is added in the diglycol ethylene of 24g with the soybean protein of 1.5g, after stirring evenly To B solution;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 6min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 660W, centrifugal rotational speed 2000r/min;
5) it will be added in 0.4g hexadecanols through the product obtained by step 4), 25 DEG C, 100r/min magnetic stirrers 5min obtains mixture solution two after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 5min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 650W, centrifugal rotational speed 1700r/min;
7) product obtained by step 6) is carried out to freeze-drying 10min in -7 DEG C, the vacuum environment of 18pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 23nm, specific surface area 320m2/ g, nanoscale Granule content is 96.9%, whiteness 96.3%, and water solubility is 0.85g/L.
Embodiment 4, with embodiment 1, unlike,
1) 50g concentrated sulfuric acid solutions are added in the deionized water of 56g, dilution obtains solution A;
2) by the Ca of 20g (OH)2It is added in the diglycol ethylene of 20g with the soybean protein of 1g, B is obtained after stirring evenly Solution;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 8min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 750W, centrifugal rotational speed 2300r/min;
5) it will be added in 0.5g hexadecanols through the product obtained by step 4), 25 DEG C, 100r/min magnetic stirrers 5min obtains mixture solution two after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 5min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 750W, centrifugal rotational speed 2300r/min;
7) product obtained by step 6) is carried out to freeze-drying 8min in -8 DEG C, the vacuum environment of 20pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 13nm, specific surface area 380m2/ g, nanoscale Granule content is 97.9%, whiteness 98.3%, and water solubility is 0.65g/L.
Embodiment 5, with embodiment 1, unlike,
1) 62g concentrated sulfuric acid solutions are added in the deionized water of 62g, dilution obtains solution A;
2) by the Ca of 25g (OH)2It is added in the diglycol ethylene of 25g with the soybean protein of 1g, B is obtained after stirring evenly Solution;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 8min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 800W, centrifugal rotational speed 2700r/min;
5) it will be added in the hexadecanol of 0.5g n-butanols and 0.5g through the product obtained by step 4), 25 DEG C, 100r/min magnetic Power blender stirs 5min, and mixture solution two is obtained after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 8min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 800W, centrifugal rotational speed 2700r/min;
7) product obtained by step 6) is carried out to freeze-drying 9min in -10 DEG C, the vacuum environment of 25pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 10nm, specific surface area 400m2/ g, nanoscale Granule content is 98.9%, whiteness 99.2%, and water solubility is 0.45g/L.
Embodiment 6, with embodiment 1, unlike,
1) 42g concentrated sulfuric acid solutions are added in the deionized water of 51g, dilution obtains solution A;
2) by the Ca of 28g (OH)2, the soybean protein of 0.8g and the gelatin hydrolysate of 0.8g be added to the diglycol ethylene of 28g In, obtain B solution after stirring evenly;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 8min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 650W, centrifugal rotational speed 2000r/min;
5) it will be added in the hexadecanol of 0.5g n-butanols and 0.5g through the product obtained by step 4), 25 DEG C, 100r/min magnetic Power blender stirs 5min, and mixture solution two is obtained after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 8min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 650W, centrifugal rotational speed 2000r/min;
7) product obtained by step 6) is subjected to freeze-drying 5-10min to get receiving in -8 DEG C, the vacuum environment of 20pa Rice calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 18nm, specific surface area 360m2/ g, nanoscale Granule content is 96.6%, whiteness 96.2%, and water solubility is 0.67g/L.
Embodiment 7, with embodiment 1, unlike,
1) 50g concentrated sulfuric acid solutions are added in the deionized water of 58g, dilution obtains solution A;
2) by the Ca of 26g (OH)2It is added in the diglycol ethylene of 26g with the gelatin hydrolysate of 2.3g, after stirring evenly To B solution;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 7min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 720W, centrifugal rotational speed 2500r/min;
5) it will be added in the hexadecanol of 0.5g n-butanols and 0.5g through the product obtained by step 4), 25 DEG C, 100r/min magnetic Power blender stirs 5min, and mixture solution two is obtained after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 7min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 720W, centrifugal rotational speed 2500r/min;
7) product obtained by step 6) is carried out to freeze-drying 10min in -9 DEG C, the vacuum environment of 19pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 13nm, specific surface area 380m2/ g, nanoscale Granule content is 98.2%, whiteness 98.5%, and water solubility is 0.55g/L.
Embodiment 8, with embodiment 1, unlike,
1) 50g concentrated sulfuric acid solutions are added in the deionized water of 50g, dilution obtains solution A;
2) by the Ca of 20g (OH)2It is added in the diglycol ethylene of 20g with the soybean protein of 1.5g, after stirring evenly To B solution;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 9min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 780W, centrifugal rotational speed 2600r/min;
5) it will be added in the hexadecanol of 0.5g n-butanols and 0.5g through the product obtained by step 4), 25 DEG C, 100r/min magnetic Power blender stirs 5min, and mixture solution two is obtained after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 9min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 780W, centrifugal rotational speed 2600r/min;
7) product obtained by step 6) is carried out to freeze-drying 8min in -7 DEG C, the vacuum environment of 25pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 13m, specific surface area 380m2/ g, nanoscale Granule content is 98.5, whiteness 98.7%, and water solubility is 0.55/L.
Embodiment 9, with embodiment 1, unlike,
1) 36g concentrated sulfuric acid solutions are added in the deionized water of 54g, dilution obtains solution A;
2) by the Ca of 20g (OH)2, 0.8g soybean protein and 0.8g gelatin hydrolysates be added in the diglycol ethylene of 20g, B solution is obtained after stirring evenly;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 9min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 800W, centrifugal rotational speed 3000r/min;
5) it will be added in the hexadecanol of 0.5g n-butanols and 0.5g through the product obtained by step 4), 25 DEG C, 100r/min magnetic Power blender stirs 5min, and mixture solution two is obtained after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 9min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 800W, centrifugal rotational speed 3000r/min;
7) product obtained by step 6) is carried out to freeze-drying 8min in -8 DEG C, the vacuum environment of 23pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 15nm, specific surface area 370m2/ g, nanoscale Granule content is 98.3%, whiteness 98.7%, and water solubility is 0.59g/L.
Embodiment 10, with embodiment 1, unlike,
1) 60g concentrated sulfuric acid solutions are added in the deionized water of 60g, dilution obtains solution A;
2) by the Ca of 25g (OH)2It is added in the diglycol ethylene of 20g with 2.2g gelatin hydrolysates, B is obtained after stirring evenly Solution;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 7min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 750W, centrifugal rotational speed 2500r/min;
5) it will be added in the hexadecanol of 1.0g through the product obtained by step 4), 25 DEG C, 100r/min magnetic stirrers 5min obtains mixture solution two after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 7min, then is washed with absolute ethyl alcohol It washs, disperse to centrifuge product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 750W, centrifugal rotational speed 2500r/min;
7) product obtained by step 6) is carried out to freeze-drying 7min in -10 DEG C, the vacuum environment of 25pa to get nanometer Calcium sulfate particle.
The average median particle diameter of nanometer calcium sulfate made from the present embodiment is 16nm, specific surface area 378m2/ g, nanoscale Granule content is 97.4%, whiteness 97.6%, and water solubility is 0.53g/L.

Claims (2)

1. a kind of preparation method of nanometer calcium sulfate, it is characterised in that:It is as follows:
1) 42~60g concentrated sulfuric acid solutions are added in the deionized water of 50~96g, it is 40~50% to be diluted to mass concentration (unnecessary), obtains solution A;
2) by the Ca of 20~25g (OH)2And the chemical additives gelatin hydrolysate and/or soybean protein of 1g is added to the contracting of 20~28g In diethylene glycol, B solution is obtained after stirring evenly;
3) it is added dropwise into the solution A obtained by step 1) in the B solution obtained by 20g steps 2), 25 DEG C, 100r/min magnetic force stirs Device stirring 5min is mixed, mixture solution one is obtained after standing 5min;
4) supercentrifuge of the mixture solution one obtained by step 3) is centrifuged into 5~9min of separation, then uses absolute ethyl alcohol Washing, dispersion centrifugation product, repeat 2~3 times, recycle absolute ethyl alcohol;
The supercentrifuge output power is 600~800W, 1500~3000r/min of centrifugal rotational speed;
5) it will be added in 0.2~1.0g n-butanols and/or hexadecanol through the product obtained by step 4), 25 DEG C, 100r/min magnetic force Blender stirs 5min, and mixture solution two is obtained after standing 5min;
6) supercentrifuge of the mixture solution two obtained by step 5) is centrifuged into 5~9min, then washed with absolute ethyl alcohol, Dispersion centrifugation product, repeats 2~3 times, recycles absolute ethyl alcohol;
The supercentrifuge output power is 600~800W, 1500~2700r/min of centrifugal rotational speed;
7) product obtained by step 6) is subjected to 5~10min of freeze-drying in -5~-10 DEG C, the vacuum environment of 15~25pa, Up to nanometer calcium sulfate particle.
2. a kind of preparation method of nanometer calcium sulfate according to claim 1, it is characterised in that:Step) obtained by nanometer Calcium sulfate particle is the spherical particles of water resistance improvement, and size is 10~23nm, and specific surface area is 300~400m2/ g, nanoscale Granule content 96.2~98.9%, whiteness 95.8~99.2, water-soluble 0.85g/L.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603127A (en) * 2021-08-18 2021-11-05 江苏一夫科技股份有限公司 Method for concentrated sulfuric acid treatment of calcium chloride wastewater and co-production of chemical gypsum

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53141194A (en) * 1977-05-16 1978-12-08 Kanegafuchi Chem Ind Co Ltd Process for producing aculeate crystal of alpha type hemihydrate gypsum
CN101838007A (en) * 2010-04-10 2010-09-22 湖南新恒光科技有限公司 Process for preparing nanometer calcium sulfate
CN106379926A (en) * 2016-09-29 2017-02-08 西安建筑科技大学 Method for preparing nano calcium sulfate
CN106745161A (en) * 2017-01-17 2017-05-31 厦门大学 A kind of method that nanometer calcium sulfate and calcium sulfate crystal whiskers are prepared in alcohol water mixed system

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53141194A (en) * 1977-05-16 1978-12-08 Kanegafuchi Chem Ind Co Ltd Process for producing aculeate crystal of alpha type hemihydrate gypsum
CN101838007A (en) * 2010-04-10 2010-09-22 湖南新恒光科技有限公司 Process for preparing nanometer calcium sulfate
CN106379926A (en) * 2016-09-29 2017-02-08 西安建筑科技大学 Method for preparing nano calcium sulfate
CN106745161A (en) * 2017-01-17 2017-05-31 厦门大学 A kind of method that nanometer calcium sulfate and calcium sulfate crystal whiskers are prepared in alcohol water mixed system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603127A (en) * 2021-08-18 2021-11-05 江苏一夫科技股份有限公司 Method for concentrated sulfuric acid treatment of calcium chloride wastewater and co-production of chemical gypsum

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