CN106587124B - A kind of preparation method of calcium carbonate granule - Google Patents

A kind of preparation method of calcium carbonate granule Download PDF

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Publication number
CN106587124B
CN106587124B CN201610996999.9A CN201610996999A CN106587124B CN 106587124 B CN106587124 B CN 106587124B CN 201610996999 A CN201610996999 A CN 201610996999A CN 106587124 B CN106587124 B CN 106587124B
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calcium carbonate
donor
solution
speed stage
carbonate granule
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CN106587124A (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

Abstract

The present invention relates to inorganic non-metallic material preparation field, more particularly to a kind of preparation method of calcium carbonate granule, a kind of preparation method of calcium carbonate granule provided by the invention, including step：There is provided needs contains Ca2+The solution of donor and containing CO3 2‑The solution of donor, the Ca2+Donor and CO3 2‑Donor is soluble-salt；Contain Ca by described in2+The solution of donor and containing CO3 2‑The solution of donor, which first passes through, continues through a low-speed stage stirring to obtain calcium carbonate suspension after a high speed stage is mixed and stirred for, to obtain calcium carbonate granule, the mixing speed of the high speed stage is 300 1200r/min, and mixing time is 10 80s；The mixing speed of the low-speed stage is 50 200r/min, and mixing time is 0.5 30min.The preparation method of the calcium carbonate granule of the present invention is simple, and can obtain the homogeneous calcium carbonate granule of pattern.

Description

A kind of preparation method of calcium carbonate granule
【Technical field】
The present invention relates to inorganic non-metallic material 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 particle of control turns into 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, have the advantages that cost is cheap, nontoxic, nonirritant, be widely used in rubber as additive and reinforcing agent The industry such as glue, plastics, papermaking, ink, building materials and medicine, by preparing the calcium carbonate of special appearance, it is higher that it can be assigned Application performance and added value.
At present, can be with carbonizatin method, solution deposit, sol-gal process, biomimetic synthesis, electrochemical synthesis etc. Prepare the calcium carbonate of regular hexahedron, sheet, 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, being not only beneficial to the heat resistance 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 microcapsules.However, the size of calcium carbonate and the homogeneity of pattern are relatively difficult to achieve, someone is by adulterating macromolecule or metal The additives such as ion, such as polystyrene, polyacrylic acid, phenol and sodium carboxymethylcellulose, the crystalline form of calcium carbonate can be entered The control of row 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 preparation technology that can cause calcium carbonate are complicated.
【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 The preparation method of kind 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 provides, Comprise the following steps：There is provided needs contains Ca2+The solution of donor and containing CO3 2-The solution of donor, the Ca2+Donor and CO3 2-For Body is soluble-salt；Contain Ca by described in2+The solution of donor and containing CO3 2-The solution of donor first passes through a high speed stage and mixes and stir A low-speed stage stirring to obtain calcium carbonate suspension is continued through after mixing, to obtain calcium carbonate granule, the high speed stage stirs It is 300-1200r/min, mixing time 10-80s to mix speed；The mixing speed of the low-speed stage is 50-200r/min, is stirred It is 0.5-30min to mix the time；The calcium carbonate granule of hexahedron structure is prepared, and the size dimension of regular hexahedron is 2.0-5.5μm。
Preferably, the mixing speed of the high speed stage is 400-900r/min, mixing time 15-40s；The low speed The mixing speed in stage is 80-120r/min, mixing time 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 kinds of combinations in calcium chloride, calcirm-fluoride, calcium nitrate；It is described CO3 2-Donor is one or several kinds of combinations in sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate.
Preferably, the preparation method of calcium carbonate granule further comprises 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 solution of the centrifuge washing is deionized water, anhydrous second A kind of or both mixing in alcohol.
Preferably, the purified treatment further comprises：Added in the sediment obtained after the centrifuge washing Deionized water carries out ripening 12-36h.
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 provided by the invention, by containing Ca2+Donor Solution and containing CO3 2-The solution of donor, which first passes through, continues through low-speed stage stirring so as to obtain after high speed stage is mixed and stirred for 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, which quickly mixes, obtains dispersed supersaturated solution, so that solution homogeneous nucleation, obtains the nucleus of size uniformity, and And nucleus secondary nucleation by the influence that high speed stage stirs in whipping process can be effectively prevented in low-speed stage, enter One step prevents the destruction of calcium carbonate granule crystal structure during formation, therefore can to obtain pattern more uniform for this method Calcium carbonate granule, and the preparation method is simple., can be by controlling at a high speed in order to realize that the size of the calcium carbonate granule of preparation is controllable Mixing time is realized in stage and low-speed stage.
In order that all Ca2+With all CO3 2-Can fully it 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 processing calcium carbonate granule that further prepared by purification of ageing, and made by ripening The pattern of calcium carbonate granule more reaches unanimity.
【Brief 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 diagrames of the first specific embodiment of the present invention.
Fig. 3 is that the first specific embodiment of the present invention amplifies 1000 times of ESEM schematic diagram.
Fig. 4 is that the first specific embodiment of the present invention amplifies 30000 times of ESEM schematic diagram.
Fig. 5 is that the second specific embodiment of the present invention amplifies 20000 times of ESEM schematic diagram.
【Embodiment】
In order that the purpose of the present invention, technical scheme and advantage are more clearly understood, below in conjunction with accompanying drawing and embodiment, The present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, It is not intended to limit the present invention.
Referring to Fig. 1, the invention provides a kind of preparation method of calcium carbonate granule, including step：
Step S1：There is provided needs contains 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：Contain Ca by described in2+The solution of donor and containing CO3 2-The solution of donor first passes through high speed stage mixing simultaneously A low-speed stage stirring to obtain calcium carbonate suspension, to obtain calcium carbonate granule, the high speed stage are continued through after stirring Mixing speed is 300-1200r/min, mixing time 10s-80s；The mixing speed of the low-speed stage is 50-200r/ Min, mixing time 0.5-30min.
In the embodiment of the present invention, provide needs in step sl contains 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), rubs 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 to obtain calcium carbonate suspension, in order to CO can further be made3 2-And Ca2+Fully reaction obtains calcium carbonate, preferably 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, calcirm-fluoride, nitric acid One or several kinds of combinations in calcium；The CO3 2-Donor be sodium carbonate, potassium carbonate, ammonium carbonate, one kind in lithium carbonate or Several combination of person.
In the embodiment of the present invention, contain Ca by described in step s 22+The solution of donor and containing CO3 2-The solution of donor first passes through Cross after a high speed stage is mixed and stirred for and continue through a low-speed stage stirring to obtain calcium carbonate suspension.
Specifically, Ca2+The solution of donor and containing CO3 2-The mixing of the solution of donor is the completion when high speed stage is carried out, By carrying out high speed stage stirring when two donor solutions are mixed, reduction speed continues low after high speed stage stirs Fast stage stirring, end reaction obtain calcium carbonate suspension.
By Ca2+Donor solution and CO3 2-Donor solution can be by Ca when high speed stage is mixed2+Donor is molten Liquid is towards equipped with CO3 2-Added 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 mixed 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 particle；Asynchronously add and be possible to cause solution also to begin to forming core without well mixed with regard to crystal and grow up, can cause The calcium carbonate granule pattern or size of acquisition are uneven, it is preferable that by Ca2+Donor solution and CO3 2-Donor solution adds simultaneously Mixed into container.
Because mixing speed can influence crystal nucleation in calcium carbonate granule forming process and grow up, so as to influence calcium carbonate Particle shape crystalline size during.Ca is made by the stirring of high speed stage2+Donor solution and CO3 2-Donor solution quickly mixes simultaneously Reaction obtains dispersed supersaturated solution, to prevent from continuing to collide between crystal in the stirring of high speed stage to cause Secondary nucleation or crystal structure destroy, therefore the calcium carbonate granule for the stirring to obtain tactical rule for passing through low-speed stage.
Pattern is homogeneous, dispersed preferable calcium carbonate granule in order to further obtain in some embodiments of the invention, 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 stirs 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 influence the pattern of calcium carbonate granule, size and point Property is dissipated, if high speed stage mixing time is long, after calcium carbonate granule nucleation, continues to grow up, and easily cause calcium carbonate Collision probability increase between grain, collision rift causes secondary nucleation, so that the pattern heterogeneity of calcium carbonate granule, can not be uniform It is scattered 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 dispersed saturated solution, therefore the mixing time of the selection high speed stage is 10-80s, is reached in high speed stage To after dispersed saturated solution, calcium carbonate granule needs to continue to grow up to obtain the pattern of compound with regular structure, therefore continues The stirring of low-speed stage, the calcium carbonate granule that mixing time is long to be caused to obtain it is oversized, select the low-speed stage Mixing time be 0.5-30min.
Pattern is homogeneous, dispersed preferable calcium carbonate granule in order to further obtain, 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 provided by the invention also includes step S3：The calcium carbonate suspension is net Change processing, obtain calcium carbonate granule after drying.
In the embodiment of the present invention, calcium carbonate will be obtained after the calcium carbonate suspension purified treatment, drying in step s3 Particle, the calcium carbonate suspension of acquisition is removed into supernatant liquid by centrifuging, the sediment left centrifuge washing again, finally done Calcium carbonate granule is obtained after dry.
Further, in order that the calcium carbonate granule pattern obtained is more homogeneous, step S3 further comprises：Washed in centrifugation Calcium carbonate ageing liquid is obtained after deionized water ageing 12-36h is added in sediment after washing, 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 solution during suspension progress centrifuge washing is preferably deionized water, in order to further purify calcium carbonate ageing liquid to obtain The homogeneous calcium carbonate granule of pattern, calcium carbonate ageing liquid is subjected to centrifuge washing again, the cleaning solution of the centrifuge washing is to go A kind of or both mixing in ionized water, absolute ethyl alcohol, due to obtaining calcium carbonate granule for last dry faster, Cleaning solution when calcium carbonate ageing liquid to be carried out to centrifuge washing is preferably absolute ethyl alcohol.
In some specific embodiments of the present invention, selective chlorination calcium is as Ca2+Donor, and selection sodium carbonate conduct CO3 2-Donor, first, by weighing 1.11-11.11g calcium chloride, i.e. 0.1-1M calcium chloride, the calcium chloride is added In 100mL deionized waters, stirring 3-5min makes calcium chloride be completely dissolved in deionized water at being 25-60 DEG C in temperature, 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 obtained calcium chloride solution and sodium carbonate liquor being mixed and stirred for by high speed stage Low-speed stage stirring to obtain calcium carbonate suspension, specifically, under conditions of temperature is 25-60 DEG C, the high speed stage stirs It is 400-900r/min, time 15-40s to mix speed；Speed is reduced after high speed stage and continues low-speed stage stirring, The mixing speed of the low-speed stage is 50-200r/min, time 1-5min, and calcium carbonate suspension is obtained after completing 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, adds and goes into lime deposit under constant temperature Ionized water is stood to be aged 12-36h, in ageing process, the impurity without the removal of above-mentioned centrifuge washing in lime deposit Further it is removed, meanwhile, calcium carbonate granule crystal continued growth in the ageing process in lime deposit, make carbonic acid The particle diameter of calcium particle further tends to consistent, and the lime deposit passes through centrifuge washing again after ageing.Centrifugation is washed The cleaning solution washed is deionized water, a kind of or both mixing in absolute ethyl alcohol, due to acquisition calcium carbonate suspension from Need to be aged using deionized water after heart washing, therefore the preferred deionized water of cleaning solution of the centrifuge washing；Finally need Acquisition calcium carbonate granule is dried, in order to be easier to obtain dry calcium carbonate granule, cleaning solution during centrifuge washing is excellent again Select absolute ethyl 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：
3.66g calcium chloride, i.e. 0.33M calcium chloride are weighed, the calcium chloride is added in deionized water, is 28 in temperature 3min is stirred at DEG C and obtains calcium chloride solution；3.50g sodium carbonate, i.e. 0.33M sodium carbonate are weighed, the sodium carbonate is added In 100mL deionized waters, sodium carbonate liquor is obtained in the lower stirring 3min that temperature is 28 DEG C.
Mix and stir by high speed stage at being 28 DEG C in temperature by the calcium chloride solution of above-mentioned acquisition and calcium carbonate soln Mix, the mixing speed of the high speed stage is 650r/min, time 30s；After high speed stage is mixed and stirred for, speed is reduced Degree, which continues through, carries out low-speed stage stirring, and the low-speed stage mixing speed is 100r/min, time 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 Deionized water is added in sediment and utilizes absolute ethyl alcohol centrifuge washing 1 time after constant temperature at temperature is 25 DEG C is aged 24h, will be logical Calcium carbonate granule is obtained after crossing absolute ethyl alcohol centrifuge washing, drying.
The calcium carbonate granule that the present invention is prepared detection method 1 carries out XRD sign.
Referring to Fig. 2, diagram XRD diffracting spectrums in, 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 correspond to respectively (012) of calcium carbonate granule, (104), (110), (113), (202), (018), (116), (211), (122), (214), (300) crystal face, mutually it is fitted, as a result illustrates, this hair with the characteristic peak of the calcium carbonate crystal of the calcite type of PDF standard cards 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 the present invention is prepared detection method 2 carries out SEM sign.
Referring to Fig. 3, when the calcium carbonate granule that the first specific embodiment is obtained amplifies 1000 times, calcium carbonate can be observed Particle 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, it can clearly observe single calcium carbonate The pattern of particle, the calcium carbonate granule is regular hexahedron structure, and the size dimension of regular hexahedron is 2.0- 5.5um。
Second specific embodiment：
The difference of second specific embodiment and the first specific embodiment is：The mixing speed of the high speed stage is 600r/min, time 30s；Continued through after high speed stage is mixed and stirred for and carry out low-speed stage stirring, the low speed Stage mixing speed is 50r/min, time 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.Referring to Fig. 5, the second specific embodiment is obtained When the calcium carbonate granule obtained amplifies 20000 times, regular hexahedron knot of the single calcium carbonate granule for 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：
The difference of 3rd specific embodiment and the first specific embodiment is：The mixing speed of the high speed stage is 500r/min, time 30s；Continued through after high speed stage is mixed and stirred for and carry out low-speed stage stirring, the low speed Stage mixing speed is 85r/min, time 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 dispersiveness preferably, the regular hexahedron size dimension is 2.8-8.5um.
4th specific embodiment：
The difference of 4th specific embodiment and the first specific embodiment is：The mixing speed of the high speed stage is 700r/min, time 30s；Continued through after high speed stage is mixed and stirred for and carry out low-speed stage stirring, the low speed Stage mixing speed is 120r/min, time 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 dispersiveness is preferably, positive six face The size dimension of body is 3.2-8.8um.
5th specific embodiment：
The difference of 6th specific embodiment and the first specific embodiment is：The mixing speed of the high speed stage is 1000r/min, time 30s；Continued through after high speed stage is mixed and stirred for and carry out low-speed stage stirring, the low speed Stage mixing speed is 250r/min, time 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 summary, shape can be prepared under the experiment condition of above-mentioned first specific embodiment to the 5th specific embodiment Looks are preferable, and in hexahedron structure, and the size dimension of the hexahedron structure is 2-10um calcium carbonate granule.Upper State under experiment condition, relative to other embodiment, from above-mentioned first embodiment, be 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 Collided and secondary nucleation between nucleus during particle is formed, cause calcium carbonate granule pattern to change；Mixing speed is lower If, calcium carbonate granule can be made not 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 provided by the invention, by containing Ca2+Donor Solution and containing CO3 2-The solution of donor, which first passes through, continues through low-speed stage stirring so as to obtain after high speed stage is mixed and stirred for 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, which quickly mixes, obtains dispersed supersaturated solution, so that solution homogeneous nucleation, obtains the nucleus of size uniformity, and And nucleus secondary nucleation by the influence that high speed stage stirs in whipping process can be effectively prevented in low-speed stage, enter One step prevents the destruction of calcium carbonate granule crystal structure during formation, therefore can to obtain pattern more uniform for this method Calcium carbonate granule, and the preparation method is simple., can be by controlling at a high speed in order to realize that the size of the calcium carbonate granule of preparation is controllable Mixing time is realized in stage and low-speed stage.
In order that all Ca2+With all CO3 2-Can fully it 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 processing calcium carbonate granule that further prepared by purification of ageing, and made by ripening The pattern of calcium carbonate granule more reaches unanimity.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all originals in the present invention Any modification made within then, equivalent substitution and improvement etc. all should be included within protection scope of the present invention.

Claims (9)

  1. A kind of 1. preparation method of calcium carbonate granule, it is characterised in that：Including step：
    There is provided needs contains Ca2+The solution of donor and containing CO3 2-The solution of donor, the Ca2+Donor and CO3 2-Donor is solubility Salt；Contain Ca by described in2+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 A low-speed stage stirring to obtain calcium carbonate suspension is crossed, to obtain calcium carbonate granule, the mixing speed of the high speed stage is 300-1200r/min, mixing time 10-80s；The mixing speed of the low-speed stage is 50-200r/min, and mixing time is 0.5-30min；The calcium carbonate granule of hexahedron structure is prepared, and the size dimension of regular hexahedron is 2.0-5.5 μm.
  2. 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 15-40s；The mixing speed of the low-speed stage is 80-120r/min, mixing time For 1-5min.
  3. 3. the preparation method of calcium carbonate granule as claimed in claim 1, it is characterised in that：The Ca provided2+Donor solution With CO3 2-The molar concentration rate of donor solution is (0.8-1.2)：(0.9-1.5).
  4. 4. the preparation method of calcium carbonate granule as claimed in claim 3, it is characterised in that：The Ca provided2+Donor solution With CO3 2-The molar concentration rate of donor solution is 1：1.
  5. 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 kinds of combinations in calcium, calcium nitrate；The CO3 2-Donor is in sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate One or several kinds of combinations.
  6. 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. 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 solution of the centrifuge washing is deionized water, a kind of or both mixing in absolute ethyl alcohol.
  8. 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 in the sediment obtained after the centrifuge washing and carries out ripening 12-36h.
  9. 9. the preparation method of the calcium carbonate granule as described in claim any one of 1-8, it is characterised in that：In the high speed stage Mixing temperature in being stirred with the low-speed stage is 25-60 DEG C.
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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

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