CN109694097A - A kind of spherical nanometer calcium carbonate and preparation method thereof - Google Patents
A kind of spherical nanometer calcium carbonate and preparation method thereof Download PDFInfo
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- CN109694097A CN109694097A CN201811350972.8A CN201811350972A CN109694097A CN 109694097 A CN109694097 A CN 109694097A CN 201811350972 A CN201811350972 A CN 201811350972A CN 109694097 A CN109694097 A CN 109694097A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention relates to a kind of spherical nanometer calcium carbonates and preparation method thereof, comprising the following steps: sodium carbonate, potassium carbonate or ammonium hydrogen carbonate are dissolved in water and are configured to CO3 2‑Concentration is the solution A of 0.25-1mol/L；One water calcium acetate or calcium chloride are dissolved in water, form Ca2+Concentration is the solution B of 0.25-1mol/L；It is first separately added into a certain amount of glycerine in different vessels, then adds deionized water to be configured to solution C respectively according still further to the volume ratio of 4:5-8:1；Solution A is separately added into C solution, after stirring 3-5 minutes, under stiring, adds B solution, solution becomes cloudy, and continues to stir 4-5h；Resulting white precipitate is centrifuged, is washed repeatedly with deionized water, be placed on 60 DEG C of baking ovens be dried in vacuum overnight to get；Of the present invention preparation method is simple, at low cost, and spherical nanometer calcium carbonate narrow particle size distribution obtained, dispersion performance is good, reproducible, is easy to large-scale production.
Description
[technical field]
The invention belongs to technical field of inorganic nanometer material, specifically a kind of spherical nanometer calcium carbonate and its preparation
Method.
[background technique]
Calcium carbonate is the widest infant industry raw material of current purposes, additive and reinforcement as a kind of function admirable
Agent is widely used in rubber, plastics, papermaking, coating, weaving, ink, toothpaste, cosmetics, daily necessities, food, medicine etc.
Industry can be improved heat resistance, wearability, dimensional stability, rigidity and the machinability of product, improve the surface colour of product
The overall performance of product is improved in pool.The superiority and inferiority of nanometer calcium carbonate performance depends primarily on the chemical group of nano-calcium carbonate calcium product
At, parameters such as morphological feature, granule size, most important of which is that the pattern and size distribution of calcium carbonate particle.Different-shape
Nanometer calcium carbonate, application field and function are different.It, can since the pattern of calcium carbonate growth is influenced by calcium carbonate crystal form
By artificially controlling calcium carbonate crystal, the spherical nanometer calcium carbonate with unique morphology and performance is made, to assign production
The higher application performance of product and added value are the exploitation hot spots of the sector.
In recent years, people obtain some achievements in the preparation research of spherical nanometer calcium carbonate, but there is also carbonic acid
The problems such as calcium particle granularity is larger, size distribution is less uniform, dispersibility is poor.Therefore, new method need to be developed, control is explored
The process conditions for the spherical nanometer calcium carbonate that granulation degree is tiny and distribution uniform, dispersion performance are good, for industrial production from now on
It lays the foundation.
In addition, nanometer calcium carbonate need to usually be dispersed in organic solvent in fields such as rubber, plastics, ink, coating,
Calcium carbonate belongs to hydrophilic and oleophobic property substance, would generally coat the surfaces such as one layer of CTAB on nanometer calcium carbonate surface in industrial production
Activating agent is modified nanometer calcium carbonate, it is made to become oleophilic substance from hydrophilic substance.Therefore, the quality of covered effect
It is an important performance indexes for determining nanometer calcium carbonate product quality.
[summary of the invention]
A kind of preparation method of spherical nanometer calcium carbonate is provided present invention aim to solve above-mentioned deficiency,
Preparation method is simple for this, and at low cost, spherical nano-calcium carbonate calcium product shape degree obtained is good, narrow particle size distribution, dispersibility
Can be good, it is reproducible, it is easy to large-scale production.
A kind of preparation method of spherical nanometer calcium carbonate is designed to achieve the above object, comprising the following steps: 1) by carbonic acid
One or more of sodium, potassium carbonate, ammonium hydrogen carbonate are dissolved in water and are configured to CO3 2-Concentration is the solution A of 0.25-1mol/L；2)
One water calcium acetate or calcium chloride are dissolved in water, form Ca2+Concentration is the solution B of 0.25-1mol/L；3) divide in different vessels
A certain amount of glycerine is not added, then glycerine is distinguished for regulating and controlling shape and appearance of calcium carbonate according still further to the volume ratio of 4:5-8:1
Deionized water is added to be configured to solution C；4) a certain amount of solution A is separately added into solution C, after stirring 3-5 minutes, is being stirred
Under, a certain amount of solution B is added, solution becomes cloudy, and continues to stir 4-5h；5) stop reaction, supernatant is removed, by step
4) resulting white precipitate centrifugation, is washed repeatedly with deionized water, is placed on 60 DEG C of baking ovens and is dried in vacuum overnight and is to get pattern
Spherical nanometer calcium carbonate.
Further, CO in step 1) acquired solution A3 2-Concentration is 0.25-0.75mol/L.
Further, Ca in step 2) acquired solution B2+Concentration is 0.25-0.75mol/L.
Further, in step 3), the volume ratio of the glycerine and deionized water is 2:1-8:1.
The spherical nanometer calcium carbonate obtained according to above-mentioned preparation method, average grain diameter 450-800nm.
The present invention compared with the existing technology, has the advantages that
(1) present invention makees calcium carbonate crystalline substance by glycerine by changing its volume ratio using glycerol-water solution as solvent
The controlling agent of type has prepared spherical nanometer calcium carbonate, and particle size 450-800nm, size distribution is uniform, prepares
Journey is simple, and cost is relatively low；
(2) spherical nanometer calcium carbonate prepared by the present invention can be with clad surface activating agent, nanometer calcium carbonate easy to accomplish
Modification, be suitble to the industrialized production of spherical nanometer calcium carbonate；
(3) present invention uses that preparation method is simple, and at low cost, product shape degree obtained is good, size distribution
Narrow, pattern is uniform, and dispersion performance is good, reproducible, is easy to large-scale production.
[Detailed description of the invention]
Fig. 1 be the present invention when glycerol-water volume ratio is 4:5 obtained by nanometer spherical calcium carbonate scanning electron microscope (SEM) photograph；
Fig. 2 be the present invention when glycerol-water volume ratio is 2:1 obtained by nanometer spherical calcium carbonate scanning electron microscope (SEM) photograph；
Fig. 3 be the present invention when glycerol-water volume ratio is 8:1 obtained by nanometer spherical calcium carbonate scanning electron microscope (SEM) photograph.
Fig. 4 the present invention when glycerol-water volume ratio is 8:1 obtained by nanometer spherical calcium carbonate, be further amplified after obtain
Scanning electron microscope (SEM) photograph.
[specific embodiment]
The present invention provides a kind of preparation method of spherical nanometer calcium carbonate, experimental studies have found that, lead to by a large amount of
Cross the volume ratio of control glycerol-water, available spherical nanometer calcium carbonate.Realize main technical schemes of the invention are as follows: with
Calcium acetate, sodium carbonate are raw material, change the volume ratio control pattern of glycerine and water and synthesize；Different volumes ratio is prepared first
Glycerine and aqueous solution, sequentially add calcium acetate and sodium carbonate liquor and carry out liquid phase reactor, stirring to there is white precipitate,
It is finally centrifuged, washs, drying to get spherical nanometer calcium carbonate is arrived.
The present invention is specifically includes the following steps: one or more of sodium carbonate, potassium carbonate, ammonium hydrogen carbonate are dissolved in by (1)
Water is configured to CO3 2-Concentration is the solution A of 0.25-1mol/L；(2) a water calcium acetate or calcium chloride are dissolved in water, form Ca2+It is dense
Degree is the solution B of 0.25-1mol/L；(3) it is first separately added into a certain amount of glycerine in six different vessels, then pressed again
Deionized water is added to be configured to solution C respectively according to the volume ratio of 4:5-8:1；(4) a certain amount of calcium acetate solution is separately added into third
In three alcohol-water solutions, after stirring 3-5 minutes, under stiring, a certain amount of sodium carbonate liquor being added, solution becomes cloudy, after
Continuous stirring 4-5h；(5) the resulting white precipitate of step (4) is centrifuged, is washed repeatedly with deionized water, it is true is placed on 60 DEG C of baking ovens
Sky is dried overnight, and obtains final products.
Calcium carbonate soln and calcium acetate solution concentration are lower in above-mentioned steps (1) and (2), conducive to pure spherical calcium carbonate
It is formed.Step (3) glycerine is new addition organic matter, for regulating and controlling shape and appearance of calcium carbonate.Glycerol-water solution in step (3)
Volume ratio is 4:5-8:1, and different volumes ratio forms various sizes of calcium carbonate, and with the increase of glycerine and water ratio, has
Conducive to the formation of spherical nanometer calcium carbonate, and partial size becomes smaller, and dispersibility improves.The pattern of final products is spherical, spherical morphology
Dispersibility, uniformity can be improved, be conducive to the comprehensive mechanical property for improving product.The average grain diameter of final products is 450-
800nm, average grain diameter are that cumulative particle sizes percentile reaches partial size corresponding when 50%, product in the range
Good dispersion, excessive or too small partial size are unfavorable for dispersing, be unfavorable for as product additive.
Following further clarification is made to the present invention combined with specific embodiments below, but the present invention is not limited in following reality
Apply example.
Method described in various embodiments of the present invention is conventional method unless otherwise instructed.
Raw material used in various embodiments of the present invention unless otherwise instructed, can be bought from disclosed commercial sources
It obtains.
The magnitude of chemical substance used in various embodiments of the present invention is determined by pre-set range, with
Gram, milliliter etc. is measurement unit.
Instrument used in various embodiments of the present invention or device model and the information of manufacturer are as follows:
Air dry oven, model DHG-9920A, manufacturer: Shanghai Yiheng Scientific Instruments Co., Ltd；
Vacuum oven, DZF-6030A, Shanghai Yiheng Scientific Instruments Co., Ltd；
Scanning electron microscope (SEM), S-3400N Hitachi, Japan.
Embodiment 1
A kind of preparation method of spherical nanometer calcium carbonate, specifically comprises the following steps:
(1) sodium carbonate is dissolved in water and is configured to CO3 2-Concentration is the solution A of 0.25mol/L；
(2) a water calcium acetate is dissolved in water, forms Ca2+Concentration is the solution B of 0.25mol/L；
(3) it is first separately added into 8mL glycerine in six different vessels, is then separately added into according still further to different volumes ratio
10g, 8g, 6g, 4g, 2g, 1g deionized water are configured to solution C；
(4) 3mLA solution is separately added into C solution, after stirring 3-5 minutes, under stiring, adds 2mLB solution,
Solution becomes cloudy, and continues to stir 4-5h；
(5) stop reaction, remove supernatant, be centrifuged white precipitate obtained, washed, be placed on repeatedly with deionized water
60 DEG C of baking ovens are dried in vacuum overnight, and obtain final products.
By measurement, the pattern of final products is vaterite and aragonite.
Embodiment 2
A kind of preparation method of spherical nanometer calcium carbonate, specifically comprises the following steps:
(1) sodium carbonate is dissolved in water and is configured to CO3 2-Concentration is the solution A of 0.75mol/L；
(2) a water calcium acetate is dissolved in water, forms Ca2+Concentration is the solution B of 0.75mol/L；
(3) it is first separately added into 8mL glycerine in six different vessels, is then separately added into according still further to different volumes ratio
10g, 8g, 6g, 4g, 2g, 1g deionized water are configured to solution C；
(4) 3mLA solution is separately added into C solution, after stirring 3-5 minutes, under stiring, adds 2mLB solution,
Solution becomes cloudy, and continues to stir 4-5h；
(5) stop reaction, remove supernatant, be centrifuged white precipitate obtained, washed, be placed on repeatedly with deionized water
60 DEG C of baking ovens are dried in vacuum overnight, and obtain final products.
(6) above-mentioned resulting calcium carbonate product is observed using scanning electron microscope.As shown in Figure 1, the third three
When alcohol-water product is than being 4:5, the particle size of above-mentioned resulting calcium carbonate is in 1um or so, and even size distribution, pattern are advised
It is whole, it is in calcite shape；As shown in Fig. 2, when glycerol-water volume ratio is 2:1, the particle size of above-mentioned resulting calcium carbonate
In 600-900nm, and even size distribution, regular appearance, in spherical；As shown in figure 3, being 8:1 in glycerol-water volume ratio
When, the particle size of above-mentioned resulting calcium carbonate is in 4500-700nm, and even size distribution, regular appearance, in spherical.With
The increase of glycerine and water volume ratio, the particle size of spherical nanometer calcium carbonate become smaller, illustrate organic matter glycerine to carbonic acid
Calcium crystal form has control action.
Embodiment 3
A kind of preparation method of spherical nanometer calcium carbonate, specifically comprises the following steps:
(1) sodium carbonate is dissolved in water and is configured to CO3 2-Concentration is the solution A of 1mol/L；
(2) a water calcium acetate is dissolved in water, forms Ca2+Concentration is the solution B of 1mol/L；
(3) it is first separately added into 8mL glycerine in six different vessels, is then separately added into according still further to different volumes ratio
10g, 8g, 6g, 4g, 2g, 1g deionized water are configured to solution C；
(4) 3mLA solution is separately added into C solution, after stirring 3-5 minutes, under stiring, adds 2mLB solution,
Solution becomes cloudy, and continues to stir 4-5h；
(5) stop reaction, remove supernatant, be centrifuged white precipitate obtained, washed, be placed on repeatedly with deionized water
60 DEG C of baking ovens are dried in vacuum overnight, and obtain final products.
By measurement, the pattern of final products is amorphous.
Embodiment 4
A kind of preparation method of spherical nanometer calcium carbonate, specifically comprises the following steps:
(1) potassium carbonate is dissolved in water and is configured to CO3 2-Concentration is the solution A of 0.45mol/L；
(2) calcium chloride is dissolved in water, forms Ca2+Concentration is the solution B of 0.45mol/L；
(3) it is first separately added into 8mL glycerine in six different vessels, is then separately added into according still further to different volumes ratio
10g, 8g, 6g, 4g, 2g, 1g deionized water are configured to solution C；
(4) 3mLA solution is separately added into C solution, after stirring 3-5 minutes, under stiring, adds 2mLB solution,
Solution becomes cloudy, and continues to stir 4-5h；
(5) stop reaction, remove supernatant, be centrifuged white precipitate obtained, washed, be placed on repeatedly with deionized water
60 DEG C of baking ovens are dried in vacuum overnight, and obtain final products.
(6) above-mentioned resulting calcium carbonate product is observed using scanning electron microscope.As it can be seen that in glycerol-water
When volume ratio is 4:5, the particle size of resulting calcium carbonate is evenly distributed, regular appearance, is in calcite shape；In glycerol-water
When volume ratio is 2:1, the particle size of resulting calcium carbonate is evenly distributed, regular appearance, in spherical；In glycerol-water volume
When than for 8:1, the particle size of resulting calcium carbonate is evenly distributed, regular appearance, in spherical.With glycerine and deionization
The particle size of the increase of water volume ratio, spherical nanometer calcium carbonate becomes smaller, and illustrates that organic matter glycerine has control to calcium carbonate crystal form
Production is used.
Embodiment 5
A kind of preparation method of spherical nanometer calcium carbonate, specifically comprises the following steps:
(1) ammonium hydrogen carbonate is dissolved in water and is configured to CO3 2-Concentration is the solution A of 0.65mol/L；
(2) calcium chloride is dissolved in water, forms Ca2+Concentration is the solution B of 0.65mol/L；
(3) it is first separately added into 8mL glycerine in six different vessels, is then separately added into according still further to different volumes ratio
10g, 8g, 6g, 4g, 2g, 1g deionized water are configured to solution C；
(4) 3mLA solution is separately added into C solution, after stirring 3-5 minutes, under stiring, adds 2mLB solution,
Solution becomes cloudy, and continues to stir 4-5h；
(5) stop reaction, remove supernatant, be centrifuged white precipitate obtained, washed, be placed on repeatedly with deionized water
60 DEG C of baking ovens are dried in vacuum overnight, and obtain final products.
(6) above-mentioned resulting calcium carbonate product is observed using scanning electron microscope.It is found that in glycerol-water
When volume ratio is 4:5, the particle size of resulting calcium carbonate is evenly distributed, regular appearance, is in calcite shape；In glycerol-water
When volume ratio is 2:1, the particle size of resulting calcium carbonate is evenly distributed, regular appearance, in spherical；In glycerol-water volume
When than for 8:1, the particle size of resulting calcium carbonate is evenly distributed, regular appearance, in spherical.With glycerine and water volume
The particle size of the increase of ratio, spherical nanometer calcium carbonate becomes smaller, and illustrates that organic matter glycerine has control to make calcium carbonate crystal form
With.
The present invention is simultaneously not limited to the embodiments described above, other any without departing from Spirit Essence and original of the invention
Changes, modifications, substitutions, combinations, simplifications made by reason is lower, should be equivalent substitute mode, are included in protection of the invention
Within the scope of.
Claims (6)
1. a kind of preparation method of spherical nanometer calcium carbonate, which comprises the following steps:
1) one or more of sodium carbonate, potassium carbonate, ammonium hydrogen carbonate are dissolved in water and are configured to CO3 2-Concentration is 0.25-1mol/L
Solution A；
2) a water calcium acetate or calcium chloride are dissolved in water, form Ca2+Concentration is the solution B of 0.25-1mol/L；
3) be separately added into a certain amount of glycerine in different vessels, glycerine for regulating and controlling shape and appearance of calcium carbonate, then according still further to
The volume ratio of 4:5-8:1 adds deionized water to be configured to solution C respectively；
4) a certain amount of solution A is separately added into solution C, after stirring 3-5 minutes, under stiring, is added a certain amount of molten
Liquid B, solution become cloudy, and continue to stir 4-5h；
5) stop reaction, remove supernatant, the resulting white precipitate of step 4) is centrifuged, is washed, is placed on repeatedly with deionized water
It is spherical nanometer calcium carbonate that 60 DEG C of baking ovens, which are dried in vacuum overnight to get pattern,.
2. preparation method as described in claim 1, it is characterised in that: CO in step 1) acquired solution A3 2-Concentration is 0.25-
0.75mol/L。
3. preparation method as described in claim 1, it is characterised in that: Ca in step 2) acquired solution B2+Concentration is 0.25-
0.75mol/L。
4. preparation method as described in claim 1, it is characterised in that: in step 3), the body of the glycerine and deionized water
Product is than being 2:1-8:1.
5. a kind of spherical nanometer calcium carbonate that preparation method according to any one of claims 1 to 4 obtains.
6. spherical nanometer calcium carbonate as claimed in claim 5, it is characterised in that: the average grain diameter of the spherical nanometer calcium carbonate
For 450-800nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482585A (en) * | 2019-08-05 | 2019-11-22 | 浙江工业大学 | A kind of synthetic method of amorphous calcium carbonate |
| CN116477652A (en) * | 2023-03-13 | 2023-07-25 | 上海林海生态技术股份有限公司 | Method for preparing black conductive nano calcium carbonate by biogas slurry synchronous double decomposition coating method |
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| CN107673384A (en) * | 2017-08-18 | 2018-02-09 | 湖北工业大学 | A kind of method that metastable state vaterite calcium carbonate is prepared based on glycerine calcium method |
| CN108467053A (en) * | 2018-04-04 | 2018-08-31 | 广西民族大学 | A kind of preparation method of bobbles calcium carbonate nano mixed crystal particle |
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2018
- 2018-11-14 CN CN201811350972.8A patent/CN109694097A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107673384A (en) * | 2017-08-18 | 2018-02-09 | 湖北工业大学 | A kind of method that metastable state vaterite calcium carbonate is prepared based on glycerine calcium method |
| CN108467053A (en) * | 2018-04-04 | 2018-08-31 | 广西民族大学 | A kind of preparation method of bobbles calcium carbonate nano mixed crystal particle |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482585A (en) * | 2019-08-05 | 2019-11-22 | 浙江工业大学 | A kind of synthetic method of amorphous calcium carbonate |
| CN116477652A (en) * | 2023-03-13 | 2023-07-25 | 上海林海生态技术股份有限公司 | Method for preparing black conductive nano calcium carbonate by biogas slurry synchronous double decomposition coating method |
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Application publication date: 20190430 |