CN106587124A - Preparation method of calcium carbonate particles - Google Patents

Preparation method of calcium carbonate particles Download PDF

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Publication number
CN106587124A
CN106587124A CN201610996999.9A CN201610996999A CN106587124A CN 106587124 A CN106587124 A CN 106587124A CN 201610996999 A CN201610996999 A CN 201610996999A CN 106587124 A CN106587124 A CN 106587124A
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calcium carbonate
donor
preparation
speed stage
granule
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CN106587124B (en
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伍芳
胡琮瑾
吴露
向勇
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention relates to the field of preparation of inorganic nonmetallic materials, in particular to a preparation method of calcium carbonate particles. The preparation method of the calcium carbonate particles comprises steps as follows: a solution containing Ca<2+> donors and a solution containing CO3<2-> donors in need are provided, and the Ca<2+> donors and the CO3<2-> donors are soluble salts; the solution containing the Ca<2+> donors and the solution containing the CO3<2-> donors are firstly mixed at a high speed and stirred and then are continuously stirred at a low speed, a calcium carbonate suspension is obtained, and the calcium carbonate particles are obtained accordingly, wherein the stirring speed at the high-speed stage is 300-1200 r/min, and the stirring time is 10-80 s; the stirring speed at the low-speed stage is 50-200 r/min, and the stirring time is 0.5-30 min. The preparation method of the calcium carbonate particles is simple, and the calcium carbonate particles with uniform morphology can be obtained.

Description

A kind of preparation method of calcium carbonate granule
【Technical field】
The present invention relates to Inorganic Non-metallic Materials preparation field, more particularly to a kind of preparation method of calcium carbonate granule.
【Background technology】
Because the pattern of material has a great impact to its physics and chemical property, thus prepare special appearance, size can The granule of control becomes the focus and difficult point of inorganic new material research in recent years.Calcium Carbonate is a kind of important inorganic filler and allusion quotation The biogenic mineral of type, has the advantages that with low cost, nontoxic, nonirritant, and as additive and reinforcing agent rubber is widely used in The industry such as glue, plastics, papermaking, ink, building materials and medicine, by the Calcium Carbonate for preparing special appearance, can give it higher Application performance and added value.
At present, with carbonizatin method, solution deposit, sol-gal process, biomimetic synthesis, electrochemical synthesis etc., can be with Prepare the Calcium Carbonate of regular hexahedron, lamellar, tabular, bar-shaped, aciculiform, spindle and the special appearance such as amorphous.Wherein, positive six Face body microparticle, due to excellent stability and optical property, not only beneficial to the thermostability and astigmatism for improving plastics Can, the glossiness and transparency of ink, and can also be controllable for preparing size and performance as the template of LBL self-assembly Multi-functional microcapsule.However, the homogeneity of the size of Calcium Carbonate and pattern is relatively difficult to achieve, someone is by doping macromolecule or metal The additives such as ion, such as polystyrene, polyacrylic acid, phenol and sodium carboxymethyl cellulose, can enter to the crystal form of Calcium Carbonate Row control to a certain extent, so as to prepare the functional material with particular size, structure and pattern.But doping macromolecule Or the additive such as metal ion, the complicated process of preparation of Calcium Carbonate can be caused.
【The content of the invention】
To overcome the inhomogenous technical barrier of the pattern of existing calcium carbonate granule, the invention provides pattern it is more uniform one Plant the preparation method of calcium carbonate granule.
The present invention is to provide a kind of preparation method of calcium carbonate granule to solve the scheme that above-mentioned technical problem is provided, Comprise the following steps：There is provided need containing Ca2+The solution of donor and containing CO3 2-The solution of donor, the Ca2+Donor and CO3 2-For Body is soluble-salt；By described containing Ca2+The solution of donor and containing CO3 2-The solution of donor first passes through a high speed stage and mixes and stir Low-speed stage stirring is continued through after mixing obtain calcium carbonate suspension, to obtain calcium carbonate granule, the high speed stage is stirred It is 300-1200r/min to mix speed, and mixing time is 10-80s；The mixing speed of the low-speed stage is 50-200r/min, is stirred The time is mixed for 0.5-30min.
Preferably, the mixing speed of the high speed stage is 400-900r/min, and mixing time is 15-40s；The low speed The mixing speed in stage is 80-120r/min, and mixing time is 1-5min.
Preferably, there is provided the Ca2+Donor solution and CO3 2-The molar concentration rate of donor solution is (0.8-1.2)： (0.9-1.5)。
Preferably, there is provided the Ca2+Donor solution and CO3 2-The molar concentration rate of donor solution is 1：1.
Preferably, the Ca2+Donor is one or several the combination in calcium chloride, calcium fluoride, calcium nitrate；It is described CO3 2-Donor is one or several the combination in sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate.
Preferably, the preparation method of calcium carbonate granule further includes step：By the calcium carbonate suspension purified treatment, Calcium carbonate granule is obtained after drying.
Preferably, the purified treatment includes centrifuge washing, and the cleaning mixture of the centrifuge washing is deionized water, anhydrous second A kind of or both mixing in alcohol.
Preferably, the purified treatment is further included：Add in the precipitate obtained after the centrifuge washing Deionized water carries out ripening 12-36h.
Preferably, the calcium carbonate granule of acquisition is in the regular hexahedron that the length of side is 2-10um.
Preferably, the temperature in the high speed stage and low-speed stage stirring is 25-60 DEG C.
Compared with prior art, in a kind of preparation method of calcium carbonate granule that the present invention is provided, by containing Ca2+Donor Solution and containing CO3 2-The solution of donor first passes through and low-speed stage stirring is continued through after high speed stage is mixed and stirred for so as to obtain Calcium carbonate suspension is obtained, to obtain calcium carbonate granule.By making Ca in high speed stage2+The solution of donor and containing CO3 2-Donor it is molten Liquid quickly mixes the homodisperse supersaturated solution of acquisition, so that solution homogeneous nucleation, obtains the nucleus of size uniformity, and And low-speed stage can effectively prevent nucleus in whipping process be subject to high speed stage stirring impact and secondary nucleation, enter One step prevents the destruction of calcium carbonate granule crystal structure during formation, thus the method can to obtain pattern more uniform Calcium carbonate granule, and the preparation method is simple.In order to the size for realizing the calcium carbonate granule of preparation is controllable, can pass through to control at a high speed Mixing time is realizing in stage and low-speed stage.
In order that all of Ca2+With all of CO3 2-Can fully combine as far as possible, completely reaction production calcium carbonate granule, can Ca is provided+Donor solution and CO3 2-The molar concentration rate of donor solution is (0.8-1.2)：(0.9-1.5).
By centrifuge washing, the process calcium carbonate granule that further prepared by purification of ageing, and made by ripening The pattern of calcium carbonate granule more reaches unanimity.
【Description of the drawings】
Fig. 1 is a kind of schematic flow sheet of the preparation method of calcium carbonate granule of the present invention.
Fig. 2 is the XRD diffracting spectrum schematic diagrams of first specific embodiment of the present invention.
Fig. 3 is the scanning electron microscope schematic diagram that first specific embodiment of the present invention amplifies 1000 times.
Fig. 4 is the scanning electron microscope schematic diagram that first specific embodiment of the present invention amplifies 30000 times.
Fig. 5 is the scanning electron microscope schematic diagram that second specific embodiment of the present invention amplifies 20000 times.
【Specific embodiment】
In order that the purpose of the present invention, technical scheme and advantage become more apparent, below in conjunction with accompanying drawing and embodiment, The present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain the present invention, It is not intended to limit the present invention.
Fig. 1 is referred to, the invention provides a kind of preparation method of calcium carbonate granule, including step：
Step S1：There is provided need containing Ca2+The solution of donor and containing CO3 2-The solution of donor, the Ca2+Donor and CO3 2- Donor is soluble-salt；
Step S2：By described containing Ca2+The solution of donor and containing CO3 2-The solution of donor first passes through a high speed stage and mixes simultaneously Low-speed stage stirring is continued through after stirring and obtains calcium carbonate suspension, to obtain calcium carbonate granule, the high speed stage Mixing speed is 300-1200r/min, and mixing time is 10s-80s；The mixing speed of the low-speed stage is 50-200r/ Min, mixing time is 0.5-30min.
In the embodiment of the present invention, in step sl provide need containing Ca2+The solution of donor and containing CO3 2-The solution of donor Method in, there is provided the Ca2+Donor and CO3 2-The molar concentration rate of donor is (0.8-1.2)：(0.9-1.5), rub at this Under your concentration ratio, Ca2+With CO3 2-Acquisition Calcium Carbonate can more sufficiently be reacted.
In order to be further able to make Ca2+Donor solution and CO3 2-Donor solution is sufficiently mixed and obtains calcium carbonate suspension, in order to CO can further be made3 2-And Ca2+Fully reaction obtains Calcium Carbonate, preferred Ca2+Donor solution and CO3 2-Donor solution it is mole dense Degree is than being 1：1.
The Ca2+Donor and the CO3 2-Donor is soluble-salt, the Ca2+Donor is calcium chloride, calcium fluoride, nitric acid One or several combination in calcium；The CO3 2-Donor be sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate in one kind or Several combination of person.
In the embodiment of the present invention, in step s 2 by described containing Ca2+The solution of donor and containing CO3 2-The solution elder generation Jing of donor Cross and low-speed stage stirring acquisition calcium carbonate suspension is continued through after a high speed stage is mixed and stirred for.
Specifically, Ca2+The solution of donor and containing CO3 2-The mixing of the solution of donor is completed when high speed stage is carried out, By carrying out high speed stage stirring when two donor solutions are mixed, reduction speed proceeds low after high speed stage stirring Fast stage stirring, end reaction obtains calcium carbonate suspension.
By Ca2+Donor solution and CO3 2-Donor solution, when high speed stage is mixed, can be by Ca2+Donor is molten Liquid is towards equipped with CO3 2-Add in the container of donor solution；Can also be by CO3 2-Donor solution is towards equipped with Ca2+Donor solution Container in add, can also be Ca2+Donor solution and CO3 2-Donor solution is added in container and mixes simultaneously.Using simultaneously The hybrid mode of addition can grow up during calcium carbonate granule is formed beneficial to crystal homogeneous nucleation, obtain the carbon of size uniformity Sour calcium granule；Asynchronously add and be possible to cause solution also to begin to forming core with regard to crystal without mix homogeneously to grow up, can cause The calcium carbonate granule pattern of acquisition or size are uneven, it is preferable that by Ca2+Donor solution and CO3 2-Donor solution is added simultaneously Mix in container.
Because mixing speed can affect in calcium carbonate granule forming process crystal nucleation and grow up, so as to affect Calcium Carbonate Particle shape crystalline size into during.Ca is made by the stirring of high speed stage2+Donor solution and CO3 2-Donor solution quickly mixes simultaneously Reaction obtains homodisperse supersaturated solution, causes colliding between crystal in the stirring of high speed stage to prevent from continuing Secondary nucleation or crystal structure are destroyed, therefore obtain the calcium carbonate granule of tactical rule by the stirring of low-speed stage.
In some embodiments of the invention in order to further obtain, pattern is homogeneous, the preferable calcium carbonate granule of dispersibility, The mixing speed of the high speed stage is 300-1200r/min, and the mixing speed of the low-speed stage is 50-200r/min.
Further, the mixing speed of the high speed stage is 400-900r/min, it is preferable that the high speed stage is stirred It can be specifically 400r/min, 440r/min, 600r/min, 650r/min, 675r/min, 690r/min, 720r/ to mix speed min、810r/min、900r/min；The mixing speed of the low-speed stage is 80-120r/min, it is preferable that the low-speed stage Mixing speed can be specifically 80r/min, 85r/min, 98r/min, 100r/min, 120r/min.
Due to the mixing time of the high speed stage and low-speed stage can affect the pattern of calcium carbonate granule, size and point Scattered property, if high speed stage mixing time is long, after calcium carbonate granule nucleation, continues to grow up, and is easily caused Calcium Carbonate Collision probability between grain increases, and collision rift causes secondary nucleation, so that the pattern heterogeneity of calcium carbonate granule, it is impossible to uniform Dispersion in the solution；If high speed stage mixing time is too short, Ca can be caused2+Donor solution and CO3 2-Donor solution mixes nothing Method reaches homodisperse saturated solution, therefore the mixing time of the selection high speed stage is 10-80s, is reached in high speed stage To after homodisperse saturated solution, calcium carbonate granule needs to continue to grow up to obtain the pattern of compound with regular structure, therefore proceeds The stirring of low-speed stage, oversized, the selection low-speed stage of the long calcium carbonate granule that can cause to obtain of mixing time Mixing time be 0.5-30min.
In order to further obtain, pattern is homogeneous, the preferable calcium carbonate granule of dispersibility, it is therefore preferable that the stirring of high speed stage Time is 15-40s；The mixing time of low-speed stage is 1-5min.
A kind of preparation method of calcium carbonate granule that the present invention is provided also includes step S3：The calcium carbonate suspension is net Calcium carbonate granule is obtained after change process, drying.
In the embodiment of the present invention, Calcium Carbonate will be obtained after the calcium carbonate suspension purified treatment, drying in step s3 Granule, by the calcium carbonate suspension of acquisition by centrifugation to remove supernatant liquid, the precipitate for staying centrifuge washing again is finally done Calcium carbonate granule is obtained after dry.
Further, in order that the calcium carbonate granule pattern for obtaining is more homogeneous, step S3 is further included：Wash in centrifugation Add in precipitate after washing and Calcium Carbonate ageing liquid is obtained after deionized water ageing 12-36h, by Calcium Carbonate ageing liquid centrifugation Calcium carbonate granule is dried to obtain after washing.Due to ripening need to be carried out using deionized water, therefore by Calcium Carbonate before ageing Cleaning mixture when suspension carries out centrifuge washing is preferably deionized water, and liquid is aged to obtain to further purify Calcium Carbonate The homogeneous calcium carbonate granule of pattern, by Calcium Carbonate ageing liquid recentrifuge washing is carried out, and the cleaning mixture of the centrifuge washing is to go A kind of or both mixing in ionized water, dehydrated alcohol, due to obtaining calcium carbonate granule for last drying faster, Calcium Carbonate is aged cleaning mixture when liquid carries out centrifuge washing and is preferably dehydrated alcohol.
In some specific embodiments of the present invention, selective chlorination calcium is used as Ca2+Donor, and select sodium carbonate conduct CO3 2-Donor, first, by the calcium chloride for weighing 1.11-11.11g calcium chloride, i.e. 0.1-1M, the calcium chloride is added In 100mL deionized waters, stirring 3-5min in the case where temperature is for 25-60 DEG C makes calcium chloride be completely dissolved in deionized water, obtains Calcium chloride solution；1.06-10.6g, i.e. 0.1-1M sodium carbonate are weighed, the sodium carbonate is added in 100mL deionized waters, in temperature Spend to stir 3-5min at 25-60 DEG C, sodium carbonate is completely dissolved in deionized water, obtain sodium carbonate liquor.
Then, one is continued through after the calcium chloride solution for obtaining and sodium carbonate liquor being mixed and stirred for by high speed stage Low-speed stage stirring obtains calcium carbonate suspension, is that under conditions of 25-60 DEG C, the high speed stage is stirred in temperature specifically It is 400-900r/min to mix speed, and the time is 15-40s；Speed is reduced after high speed stage and proceeds low-speed stage stirring, The mixing speed of the low-speed stage is 50-200r/min, and the time is 1-5min, completes to obtain Calcium Carbonate suspension after low-speed stage Liquid.
Calcium carbonate granule will be obtained after the calcium carbonate suspension purified treatment, drying, specifically, will using deionized water Lime deposit is left after the calcium carbonate suspension centrifuge washing, is added in lime deposit under constant temperature and is gone Ionized water is stood to be aged 12-36h, in ageing process, the impurity removed without above-mentioned centrifuge washing in lime deposit Further it is removed, meanwhile, the crystal continued growth in the ageing process of the calcium carbonate granule in lime deposit makes carbonic acid The particle diameter of calcium granule further tends to consistent, and the lime deposit is washed after ageing by recentrifuge.Centrifugation is washed The cleaning mixture washed is a kind of or both the mixing in deionized water, dehydrated alcohol, due to the calcium carbonate suspension that obtains from Need to be aged using deionized water after heart washing, therefore the preferred deionized water of cleaning mixture of the centrifuge washing；Finally need Acquisition calcium carbonate granule is dried, in order to be easier to obtain dry calcium carbonate granule, cleaning mixture when recentrifuge is washed is excellent Select dehydrated alcohol.
In the present embodiment, in order to obtain preferably calcium carbonate granule, specific embodiment can be further provided for, specifically such as Under：
First specific embodiment：
The calcium chloride of 3.66g calcium chloride, i.e. 0.33M is weighed, the calcium chloride is added in deionized water, be 28 in temperature 3min is stirred at DEG C and obtains calcium chloride solution；The sodium carbonate of 3.50g sodium carbonate, i.e. 0.33M is weighed, the sodium carbonate is added In 100mL deionized waters, in the lower stirring 3min that temperature is 28 DEG C sodium carbonate liquor is obtained.
The calcium chloride solution and calcium carbonate soln of above-mentioned acquisition are mixed and stirred in the case where temperature is for 28 DEG C through high speed stage Mix, the mixing speed of the high speed stage is 650r/min, and the time is 30s；After high speed stage is mixed and stirred for, speed is reduced Degree is continued through and carries out low-speed stage stirring, and the low-speed stage mixing speed is 100r/min, and the time is 2min, completes low speed After stage stirring, calcium carbonate suspension is obtained；
By the calcium carbonate suspension using after deionized water centrifuge washing 3 times, lime deposit is left, to Calcium Carbonate Add in precipitate deionized water and temperature be at 25 DEG C after constant temperature ageing 24h using dehydrated alcohol centrifuge washing 1 time, will be logical Cross after dehydrated alcohol centrifuge washing, drying and obtain calcium carbonate granule.
The calcium carbonate granule that detection method 1 prepares the present invention carries out the sign of XRD.
Refer to Fig. 2, it is illustrated that in XRD diffracting spectrums, 2 θ be 23.053 °, 29.399 °, 35.968 °, 39.408 °, Occur diffraction maximum, the diffraction at 43.157 °, 47.504 °, 48.503 °, 56.561 °, 57.397 °, 60.666 ° and 64.658 ° Peak respectively correspond to calcium carbonate granule (012), (104), (110), (113), (202), (018), (116), (211), (122), (214), (300) crystal face, is mutually fitted with the characteristic peak of the calcium carbonate crystal of the calcite type of PDF standard cards, as a result illustrates, this Calcium carbonate granule is obtained prepared by the first bright specific embodiment, and the crystallinity of the calcium carbonate granule is preferable.
The calcium carbonate granule that detection method 2 prepares the present invention carries out the sign of SEM.
Fig. 3 is referred to, when the calcium carbonate granule that the first specific embodiment is obtained amplifies 1000 times, Calcium Carbonate can be observed Granule is well dispersed, distribution is more uniform, and substantially consistent appearance, and 98% calcium carbonate granule is in hexahedron structure；Such as Fig. 4 It is shown, when the calcium carbonate granule that the first specific embodiment is obtained amplifies 30000 times, can clearly observe single Calcium Carbonate The pattern of granule, the calcium carbonate granule is the hexahedron structure of rule, and the size dimension of regular hexahedron is 2.0- 5.5um。
Second specific embodiment：
Second specific embodiment is with the difference of the first specific embodiment：The mixing speed of the high speed stage is 600r/min, the time is 30s；Continuing through after high speed stage is mixed and stirred for carries out low-speed stage stirring, the low speed Stage mixing speed is 50r/min, and the time is 2min.
By with above-mentioned first specific embodiment identical method of testing, the carbonic acid that second specific embodiment is obtained Calcium granule-morphology is more uniform, and 98% calcium carbonate granule is in hexahedron structure.Fig. 5 is referred to, the second specific embodiment is obtained When the calcium carbonate granule for obtaining amplifies 20000 times, the regular hexahedron knot that single calcium carbonate granule is rule can be clearly observed Structure, and it is well dispersed, and the size dimension of its regular hexahedron is 2.5-7.2um.
3rd specific embodiment：
3rd specific embodiment is with the difference of the first specific embodiment：The mixing speed of the high speed stage is 500r/min, the time is 30s；Continuing through after high speed stage is mixed and stirred for carries out low-speed stage stirring, the low speed Stage mixing speed is 85r/min, and the time is 2min.
By with above-mentioned first specific embodiment identical method of testing, the carbonic acid that the 3rd specific embodiment is obtained Calcium granule-morphology is more uniform, and 98% calcium carbonate granule is in hexahedron structure, can be prepared in hexahedron structure Calcium carbonate granule, and its dispersibility is preferably, and the regular hexahedron size dimension is 2.8-8.5um.
4th specific embodiment：
4th specific embodiment is with the difference of the first specific embodiment：The mixing speed of the high speed stage is 700r/min, the time is 30s；Continuing through after high speed stage is mixed and stirred for carries out low-speed stage stirring, the low speed Stage mixing speed is 120r/min, and the time is 2min.
By with above-mentioned first specific embodiment identical method of testing, the carbonic acid that the 4th specific embodiment is obtained Calcium granule-morphology is more uniform, and 98% calcium carbonate granule is in hexahedron structure, and its dispersibility is preferably, described just hexahedro The size dimension of body is 3.2-8.8um.
5th specific embodiment：
6th specific embodiment is with the difference of the first specific embodiment：The mixing speed of the high speed stage is 1000r/min, the time is 30s；Continuing through after high speed stage is mixed and stirred for carries out low-speed stage stirring, the low speed Stage mixing speed is 250r/min, and the time is 2min.
By with above-mentioned first specific embodiment identical method of testing, the carbonic acid that the 5th specific embodiment is obtained Calcium granule-morphology is more uniform, and 97% calcium carbonate granule is in hexahedron structure, and its size dimension is 4.4-9.6um.
In sum, shape can be prepared under the experiment condition of above-mentioned first specific embodiment to the 5th specific embodiment Preferably, in hexahedron structure, and the size dimension of the hexahedron structure is the calcium carbonate granule of 2-10um to looks.Upper Under stating experiment condition, relative to other embodiment, from above-mentioned first embodiment, it is in the mixing time of high speed stage 650r/min, the mixing speed of low-speed stage is 100r/min, can obtain the preferable calcium carbonate granule of scale topography, and speed is higher Or it is lower, the size or pattern heterogeneity of calcium carbonate granule can be caused, because mixing speed is faster, Calcium Carbonate can be made Collide and secondary nucleation between nucleus during granule formation, cause calcium carbonate granule pattern to change；Mixing speed is lower If, calcium carbonate granule can be made to be uniformly dispersed in solution, so as to cause calcium carbonate granule to become large-sized.
Above-mentioned specific embodiment is only example in the present invention, is not intended as the restriction of the present invention.
Compared with prior art, in a kind of preparation method of calcium carbonate granule that the present invention is provided, by containing Ca2+Donor Solution and containing CO3 2-The solution of donor first passes through and low-speed stage stirring is continued through after high speed stage is mixed and stirred for so as to obtain Calcium carbonate suspension is obtained, to obtain calcium carbonate granule.By making Ca in high speed stage2+The solution of donor and containing CO3 2-Donor it is molten Liquid quickly mixes the homodisperse supersaturated solution of acquisition, so that solution homogeneous nucleation, obtains the nucleus of size uniformity, and And low-speed stage can effectively prevent nucleus in whipping process be subject to high speed stage stirring impact and secondary nucleation, enter One step prevents the destruction of calcium carbonate granule crystal structure during formation, thus the method can to obtain pattern more uniform Calcium carbonate granule, and the preparation method is simple.In order to the size for realizing the calcium carbonate granule of preparation is controllable, can pass through to control at a high speed Mixing time is realizing in stage and low-speed stage.
In order that all of Ca2+With all of CO3 2-Can fully combine as far as possible, completely reaction production calcium carbonate granule, can Ca is provided+Donor solution and CO3 2-The molar concentration rate of donor solution is (0.8-1.2)：(0.9-1.5).
By centrifuge washing, the process calcium carbonate granule that further prepared by purification of ageing, and made by ripening The pattern of calcium carbonate granule more reaches unanimity.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all originals in the present invention Any modification made within then, equivalent and improvement etc. all should be comprising within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of calcium carbonate granule, it is characterised in that：Including step：
There is provided need containing Ca2+The solution of donor and containing CO3 2-The solution of donor, the Ca2+Donor and CO3 2-Donor is solubility Salt；By described containing Ca2+The solution of donor and containing CO3 2-The solution of donor is first passed through after a high speed stage is mixed and stirred for and continued on through Cross low-speed stage stirring and obtain calcium carbonate suspension, to obtain calcium carbonate granule, the mixing speed of the high speed stage is 300-1200r/min, mixing time is 10-80s；The mixing speed of the low-speed stage is 50-200r/min, and mixing time is 0.5-30min。
2. the preparation method of calcium carbonate granule as claimed in claim 1, it is characterised in that：The mixing speed of the high speed stage For 400-900r/min, mixing time is 15-40s；The mixing speed of the low-speed stage be 80-120r/min, mixing time For 1-5min.
3. the preparation method of calcium carbonate granule as claimed in claim 1, it is characterised in that：The Ca for providing2+Donor solution With CO3 2-The molar concentration rate of donor solution is (0.8-1.2)：(0.9-1.5).
4. the preparation method of calcium carbonate granule as claimed in claim 3, it is characterised in that：The Ca for providing2+Donor solution With CO3 2-The molar concentration rate of donor solution is 1：1.
5. the preparation method of calcium carbonate granule as claimed in claim 1, it is characterised in that：The Ca2+Donor is calcium chloride, fluorine Change one or several the combination in calcium, calcium nitrate；The CO3 2-Donor is in sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate One or several combination.
6. the preparation method of calcium carbonate granule as claimed in claim 1, it is characterised in that：The preparation method of calcium carbonate granule is entered One step includes step：Calcium carbonate granule will be obtained after the calcium carbonate suspension purified treatment, drying.
7. the preparation method of calcium carbonate granule as claimed in claim 6, it is characterised in that：The purified treatment is washed including centrifugation Wash, the cleaning mixture of the centrifuge washing is a kind of or both the mixing in deionized water, dehydrated alcohol.
8. the preparation method of calcium carbonate granule as claimed in claim 7, it is characterised in that：The purified treatment is further wrapped Include：Deionized water is added to carry out ripening 12-36h in the precipitate obtained after the centrifuge washing.
9. the preparation method of the calcium carbonate granule as described in any one of claim 1-8, it is characterised in that：The carbonic acid for obtaining Calcium granule is in the regular hexahedron that the length of side is 2-10um.
10. the preparation method of the calcium carbonate granule as described in any one of claim 1-8, it is characterised in that：In the high speed rank Mixing temperature in section and low-speed stage stirring is 25-60 DEG C.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112456531A (en) * 2020-12-08 2021-03-09 上海簇睿低碳能源技术有限公司 Preparation method of nano calcium carbonate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1750808A (en) * 2003-02-13 2006-03-22 J·M·休伯有限公司 Precipitated calcium carbonate
CN104445333A (en) * 2014-11-06 2015-03-25 安徽瑞研新材料技术研究院有限公司 Process for producing calcium carbonate employing nano-precipitation method
CN104692437A (en) * 2013-12-09 2015-06-10 中国科学院过程工程研究所 Preparation method of morphology controllable calcium carbonate based on temperature control

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1750808A (en) * 2003-02-13 2006-03-22 J·M·休伯有限公司 Precipitated calcium carbonate
CN104692437A (en) * 2013-12-09 2015-06-10 中国科学院过程工程研究所 Preparation method of morphology controllable calcium carbonate based on temperature control
CN104445333A (en) * 2014-11-06 2015-03-25 安徽瑞研新材料技术研究院有限公司 Process for producing calcium carbonate employing nano-precipitation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112456531A (en) * 2020-12-08 2021-03-09 上海簇睿低碳能源技术有限公司 Preparation method of nano calcium carbonate

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