CN114455620B - Preparation method of square and cluster symbiotic micron-sized calcium carbonate - Google Patents
Preparation method of square and cluster symbiotic micron-sized calcium carbonate Download PDFInfo
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- CN114455620B CN114455620B CN202210024322.4A CN202210024322A CN114455620B CN 114455620 B CN114455620 B CN 114455620B CN 202210024322 A CN202210024322 A CN 202210024322A CN 114455620 B CN114455620 B CN 114455620B
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 105
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 49
- 239000007864 aqueous solution Substances 0.000 claims abstract description 48
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 32
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000011734 sodium Substances 0.000 claims abstract description 29
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001110 calcium chloride Substances 0.000 claims abstract description 26
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 26
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 19
- 229930006000 Sucrose Natural products 0.000 claims abstract description 19
- 239000005720 sucrose Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 64
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000004033 plastic Substances 0.000 abstract description 9
- 229920003023 plastic Polymers 0.000 abstract description 9
- 239000000123 paper Substances 0.000 abstract description 8
- 239000003973 paint Substances 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 229910021532 Calcite Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004064 cosurfactant Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000606 toothpaste Substances 0.000 description 2
- 229940034610 toothpaste Drugs 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 210000004690 animal fin Anatomy 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
Abstract
The invention discloses a method for preparing square and cluster symbiotic micron-sized calcium carbonate,the method comprises the following steps: 1) CTAB, n-butanol, n-hexane and calcium chloride aqueous solution are mixed to prepare CaCl 2 An inverse microemulsion; 2) Mixing CTAB, n-hexanol, n-hexane, sucrose and sodium carbonate water solution to prepare Na 2 CO 3 An inverse microemulsion; 3) According to Na 2 CO 3 With CaCl 2 The molar ratio of Na is 2-4:1, na is used as the catalyst 2 CO 3 Adding the reverse microemulsion into CaCl 2 And (3) after the addition of the reverse microemulsion is completed, aging to obtain the square and cluster symbiotic micron-sized calcium carbonate. Compared with the existing square calcium carbonate, the calcium carbonate provided by the invention has better powder falling resistance and sedimentation resistance in paper, paint and plastics as a filler.
Description
Technical Field
The invention belongs to the field of calcium carbonate, and particularly relates to a preparation method of square and cluster symbiotic integrated micron-sized calcium carbonate.
Background
Calcium carbonate (CaCO) 3 ) Is an inorganic compound, commonly called limestone, marble, etc., and has a molar mass of 100.09 g/mol and a density of 2.93 g/cm 3 The melting point was 825 ℃. Is slightly soluble in water at normal temperature (ksp=2.9x10) -9 ) There are three crystal forms of aragonite, calcite and vaterite. Calcium carbonate is also one of the most stored substances on earth. Because the calcium carbonate has low cost and good performance, the calcium carbonate is widely applied to the production, processing and application of rubber, plastics, paper making, coating, medicine, printing ink, food, toothpaste, cosmetics and the like.
Differently shaped calcium carbonates have different uses, for example cubic calcium carbonate exhibits high whiteness and opacity in paper. The modified flame retardant is used as a filler to be added into plastics, so that the heat conduction and electric conduction performance, flame retardant and heat resistance, impact corrosion resistance and the like of plastic products can be improved; it can also replace white carbon black, so that the surface of plastic products is bright, the tension resistance is strong, the bending resistance is good, the cracking resistance is good, and the plastic products are excellent white reinforcing agents. The spherical calcium carbonate has good opacity, smoothness and fluidity, and can be applied to various lubricating oils, so that the lubricating property of the lubricating oil is greatly improved. Can also be used in the production of toothpaste, cosmetics and electronic ceramics. The spindle-shaped calcium carbonate is similar to a microbial fiber, and thus can impart excellent in-use properties such as bulk, opacity, smoothness, and printability to paper. Can also be widely used in the production and manufacture of products such as sealing agents, pressure-sensitive adhesives and the like in rubber and plastics. Chain calcium carbonate is widely used in synthetic rubber, since in rubber synthesis, these chain calcium carbonates are subjected to mechanical vibration and grinding, which will cause some of the connection points to break, thereby forming break points with higher activity. The break points can lead the break points to be bonded with the synthetic rubber matrix, so that the connection is more compact, thereby improving the physical and chemical properties of the synthetic rubber. The flaky calcium carbonate is widely used in paint and paper making due to its good dispersibility, optical properties and printing properties, and strong surface coating function. The flaky calcium carbonate is added into the paint, so that the paint has good fluidity and dispersibility; the addition of paper exhibits a better finish and bulk than spindle-like calcium carbonate and can therefore replace the progressively smaller platy kaolin.
Microemulsions were first proposed by Schulman et al, which is a dispersion system composed of an aqueous phase, an oil phase, an amphiphilic compound, etc., and may be classified into oil-in-water (O/W) and water-in-oil (W/O) depending on the dispersion medium. The reverse microemulsion is water-in-oil microemulsion (W/O), takes a nonpolar solvent (oil phase) as a disperse phase, uniformly disperses an aqueous solution in the oil phase, and is wrapped by an amphiphilic compound to form a micro water pool (also called liquid drops) with the diameter of 5-100 nm. The size of the liquid drop can be controlled between a certain range by adjusting the mol ratio of the surfactant to the water, and the special micro-water pool is formed under the combined action of various chemical reactions and physical arrangement. At present, the microemulsion method has been widely applied to the preparation of micro-nano materials, such as composite catalysts, semiconductors, superconductor materials, magnetic nanoparticles and the like, because of the simple operation and no need of high-temperature and high-pressure equipment.
Prior to this, the inventors carried out a series of studies on the preparation of micro-nano calcium carbonate by reverse microemulsion (CN 11592026A, CN111484061A, CN102583481A, CN111592025A, CN111675235A, CN111675234a, incorporated herein by reference in its entirety), and the results indicate that constructing reverse microemulsion systems using different oil phases, surfactants, cosurfactants, etc. has a significant impact on the morphology of calcium carbonate.
Disclosure of Invention
Based on the prior art, the invention aims to provide a preparation method of square and cluster symbiotic integrated micron-sized calcium carbonate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of square and cluster symbiotic micron-sized calcium carbonate comprises the following steps:
1) CaCl 2 preparing reverse microemulsion:
CTAB, n-butanol, n-hexane and calcium chloride aqueous solution are mixed to prepare CaCl 2 An inverse microemulsion;
2)Na 2 CO 3 preparing reverse microemulsion:
mixing CTAB, n-hexanol, n-hexane, sucrose and sodium carbonate water solution to prepare Na 2 CO 3 An inverse microemulsion;
3) According to Na 2 CO 3 With CaCl 2 The molar ratio of Na is 2-4:1, na is used as the catalyst 2 CO 3 Adding the reverse microemulsion into CaCl 2 And (3) after the addition of the reverse microemulsion is completed, aging to obtain the square and cluster symbiotic micron-sized calcium carbonate.
Preferably, caCl is formulated 2 In the reverse microemulsion, the mass ratio of CTAB, n-butanol and n-hexane is 0.2-0.3:0.2-0.3:1, the volume ratio of n-hexane to calcium chloride aqueous solution is 1:0.35-0.45, and the concentration of the calcium chloride aqueous solution is 0.3-0.7 mol/L.
More preferably, the mass ratio of CTAB, n-butanol and n-hexane is 0.25-0.3:0.2-0.26:1, the volume ratio of n-hexane to calcium chloride aqueous solution is 1:0.37-0.44, and the concentration of the calcium chloride aqueous solution is 0.4-0.6 mol/L.
Most preferably, the mass ratio of CTAB, n-butanol and n-hexane is 0.28-0.3:0.23-0.26:1, the volume ratio of n-hexane to calcium chloride aqueous solution is 1:0.41-0.43, and the concentration of the calcium chloride aqueous solution is 0.5mol/L.
Preferably, formulationNa 2 CO 3 In the reverse microemulsion, the mass ratio of CTAB, n-hexanol, n-hexane and sucrose is 0.2-0.3:0.2-0.3:1:0.001-0.0015, the volume ratio of n-hexane to sodium carbonate aqueous solution is 1:1.1-1.5, and the concentration of sodium carbonate aqueous solution is 0.3-0.7 mol/L.
More preferably, the mass ratio of CTAB, n-hexanol, n-hexane and sucrose is 0.25-0.3:0.2-0.26:1:0.001-0.0013, the volume ratio of n-hexane to sodium carbonate aqueous solution is 1:1.1-1.4, and the concentration of sodium carbonate aqueous solution is 0.4-0.6 mol/L.
Most preferably, the mass ratio of CTAB, n-hexanol, n-hexane and sucrose is 0.28-0.3:0.23-0.26:1:0.001-0.0012, the volume ratio of n-hexane to sodium carbonate aqueous solution is 1:1.1-1.3, and the concentration of sodium carbonate aqueous solution is 0.5mol/L.
Sucrose is soluble in water and insoluble in n-hexane, preferably Na is formulated 2 CO 3 In the case of the inverse microemulsion, sucrose is first dissolved in an aqueous sodium carbonate solution, which is then mixed with CTAB, n-hexanol and n-hexane.
Preferably Na 2 CO 3 With CaCl 2 The molar ratio of (2.5) - (3.5:1).
Most preferably, na 2 CO 3 With CaCl 2 The molar ratio of (2.7-3.1:1).
Preferably, the aging time is 24 to 48 hours.
Advantageous effects
The novel square and cluster symbiotic micron-sized calcium carbonate is prepared by adopting the method. Compared with the existing square calcium carbonate, the outward-extending cluster structure of the square body of the calcium carbonate in the solid medium can play an anchoring role, the contact area and the adhesion capability of the square body and the medium are increased, the powder falling resistance of the calcium carbonate in paper, coating, paint layer and plastics is improved, the outward-extending cluster structure of the square body in the liquid medium can play a role similar to a fish fin, the sedimentation resistance of the calcium carbonate in the liquid medium is improved, and the calcium carbonate can be used as an excellent filler in the fields of paper, paint, plastics and the like.
Drawings
FIG. l is a scanning electron microscope image of the micron-sized calcium carbonate prepared by the invention; wherein a and b are 5000 times of the magnifying diagrams of the scanning electron microscope, and c is 10000 times of the magnifying diagrams of the scanning electron microscope.
FIG. 2 is an X-ray diffraction pattern of calcium carbonate; wherein a is the standard X-ray diffraction pattern of vaterite calcium carbonate and calcite calcium carbonate and b is the X-ray diffraction pattern of the micron-sized calcium carbonate prepared according to the invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings and the examples.
The size and morphology of the composite powder samples were analyzed using a scanning electron microscope (JSM-6100, jeol Ltd japan). The crystal structure was analyzed by X-ray powder diffraction (XRD; RINT-1000, rigaku, japan).
CaCl 2 Selection of raw materials of the reverse microemulsion system: surfactant CTAB (cetyl trimethyl ammonium bromide), cosurfactant n-butanol, oil phase n-hexane, aqueous phase calcium chloride aqueous solution.
Na 2 CO 3 Selection of raw materials of the reverse microemulsion system: surfactant CTAB, cosurfactant n-hexanol, oil phase n-hexane, aqueous phase calcium chloride aqueous solution and auxiliary agent sucrose.
As can be seen from fig. 1a-b, the micro-sized calcium carbonate prepared according to the embodiment of the present invention has a square and cluster-shaped symbiotic structure in which clusters are located at one or both opposite corners of a square body and extend outward.
As further seen in fig. 1c, the clustered calcium carbonate is a cluster of clusters of chains formed by a plurality of side-by-side segments extending outwardly from one or two opposite top corners of the square body, one segment being connected end to end.
Substitution of n-hexanol with n-butanol, under otherwise unchanged conditions, failed to yield Na 2 CO 3 Inverse microemulsion.
As can be seen from FIGS. 2a-b, the micron-sized calcium carbonate prepared in accordance with the examples of the present invention appears at 2θ29.16 °, 35.81 °, 39.25 ° and 42.36 ° derivatives of (c)The peaks are identical to the standard X-ray diffraction pattern of Calcite, while the diffraction peaks appearing at 20.81 °, 24.72 °, 26.93 °, 32.60 °, 43.68 °, 49.82 ° and 55.64 ° are identical to the standard X-ray diffraction pattern of Vaterite, indicating that the square and cluster symbiotic micron-sized calcium carbonate prepared by the present invention has both Vaterite (vanite) and Calcite (Calcite) crystal forms.
Example 1
The preparation process of square and cluster symbiotic micron-sized calcium carbonate is as follows:
1) CaCl 2 preparing reverse microemulsion:
preparation of aqueous calcium chloride solution: 5.549g of calcium chloride is weighed, a small amount of water is added to dissolve in a beaker, and the solution is transferred to a volumetric flask of 100ml to fix the volume after complete dissolution, so as to obtain a calcium chloride aqueous solution with the concentration of 0.5mol/L for later use.
14.5g CTAB and 14.8ml (0.81 g/cm) 3 12 g) n-butanol, 75.3ml (0.66 g/cm) 3 49.7 g) of n-hexane and 31ml of calcium chloride aqueous solution, mixing and stirring, and standing at room temperature when the solution is clear to obtain CaCl 2 Inverse microemulsion.
2)Na 2 CO 3 Preparing reverse microemulsion:
preparation of aqueous sodium carbonate solution: weighing 5.300g of sodium carbonate, adding a small amount of water to dissolve in a beaker, transferring to a volumetric flask of 100ml to fix the volume after complete dissolution, and obtaining sodium carbonate aqueous solution with the concentration of 0.5mol/L for later use.
14.5g CTAB and 14.8ml (0.814 g/cm) were taken respectively 3 12 g) of n-hexanol, 75.3ml (0.66 g/cm) 3 49.7 g) of n-hexane, 0.053g of sucrose and 90ml of sodium carbonate aqueous solution, dissolving sucrose in the sodium carbonate aqueous solution, mixing CTAB, n-hexylene alcohol and n-hexane with the sodium carbonate aqueous solution, stirring after mixing, standing at room temperature when the solution is clear, obtaining Na 2 CO 3 Inverse microemulsion.
3) Stirring the Na 2 CO 3 Slowly adding the reverse microemulsion into CaCl 2 In the reverse microemulsion, after finishing, standing at room temperature, aging for 24h, and centrifugingAnd (5) separating. The calcium carbonate obtained was baked in an oven at 80℃for 12h.
Example 2
The preparation process of square and cluster symbiotic micron-sized calcium carbonate is as follows:
1) CaCl 2 preparing reverse microemulsion:
preparation of aqueous calcium chloride solution: 5.549g of calcium chloride is weighed, a small amount of water is added to dissolve in a beaker, and the solution is transferred to a volumetric flask of 100ml to fix the volume after complete dissolution, so as to obtain a calcium chloride aqueous solution with the concentration of 0.5mol/L for later use.
14.2g CTAB and 14.5ml (0.81 g/cm) 3 11.7 g) of n-butanol, 75.5ml (0.66 g/cm) 3 49.8 g) of n-hexane and 30ml of calcium chloride aqueous solution, mixing and stirring, and standing at room temperature when the solution is clear to obtain CaCl 2 Inverse microemulsion.
2)Na 2 CO 3 Preparing reverse microemulsion:
preparation of aqueous sodium carbonate solution: weighing 5.300g of sodium carbonate, adding a small amount of water to dissolve in a beaker, transferring to a volumetric flask of 100ml to fix the volume after complete dissolution, and obtaining sodium carbonate aqueous solution with the concentration of 0.5mol/L for later use.
14.7g CTAB and 15.1ml (0.814 g/cm) were taken respectively 3 12.3 g) of n-hexanol, 75.1ml (0.66 g/cm) 3 49.5 g) of n-hexane, 0.055g of sucrose and 92ml of sodium carbonate aqueous solution, dissolving sucrose in the sodium carbonate aqueous solution, mixing CTAB, n-hexylene alcohol and n-hexane with the sodium carbonate aqueous solution, stirring after mixing, standing at room temperature when the solution is clear, obtaining Na 2 CO 3 Inverse microemulsion.
3) Stirring the Na 2 CO 3 Slowly adding the reverse microemulsion into CaCl 2 And (3) in the reverse microemulsion, standing at room temperature after finishing, aging for 24 hours, and performing centrifugal separation. The calcium carbonate obtained was baked in an oven at 80℃for 12h.
Example 3
The preparation process of square and cluster symbiotic micron-sized calcium carbonate is as follows:
1) CaCl 2 reverse microemulsionPreparing liquid:
preparation of aqueous calcium chloride solution: 5.549g of calcium chloride is weighed, a small amount of water is added to dissolve in a beaker, and the solution is transferred to a volumetric flask of 100ml to fix the volume after complete dissolution, so as to obtain a calcium chloride aqueous solution with the concentration of 0.5mol/L for later use.
14.7g CTAB and 15.1ml (0.81 g/cm) 3 12.2 g) of n-butanol, 75.1ml (0.66 g/cm) 3 49.5 g) of n-hexane and 32ml of calcium chloride aqueous solution, mixing and stirring, and standing at room temperature when the solution is clear to obtain CaCl 2 Inverse microemulsion.
2)Na 2 CO 3 Preparing reverse microemulsion:
preparation of aqueous sodium carbonate solution: weighing 5.300g of sodium carbonate, adding a small amount of water to dissolve in a beaker, transferring to a volumetric flask of 100ml to fix the volume after complete dissolution, and obtaining sodium carbonate aqueous solution with the concentration of 0.5mol/L for later use.
14.2g CTAB and 14.5ml (0.814 g/cm) were taken respectively 3 11.8 g) of n-hexanol, 75.5ml (0.66 g/cm) 3 49.8 g) of n-hexane, 0.051g of sucrose and 88ml of sodium carbonate aqueous solution, dissolving sucrose in the sodium carbonate aqueous solution, mixing CTAB, n-hexylene alcohol and n-hexane with the sodium carbonate aqueous solution, stirring after mixing, standing at room temperature when the solution is clear, obtaining Na 2 CO 3 Inverse microemulsion.
3) Stirring the Na 2 CO 3 Slowly adding the reverse microemulsion into CaCl 2 And (3) in the reverse microemulsion, standing at room temperature, aging for 48 hours, and performing centrifugal separation. The calcium carbonate obtained was baked in an oven at 80℃for 12h.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of square and cluster symbiotic micron-sized calcium carbonate comprises the following steps:
1) CaCl 2 preparing reverse microemulsion:
CTAB, n-butanol, n-hexane and calcium chloride aqueous solution are mixed to prepare CaCl 2 An inverse microemulsion;
2)Na 2 CO 3 preparing reverse microemulsion:
mixing CTAB, n-hexanol, n-hexane, sucrose and sodium carbonate water solution to prepare Na 2 CO 3 An inverse microemulsion;
3) According to Na 2 CO 3 With CaCl 2 The molar ratio of Na is 2-4:1, na is used as the catalyst 2 CO 3 Adding the reverse microemulsion into CaCl 2 After the reverse microemulsion is added, aging is carried out to obtain the square and cluster symbiotic micron-sized calcium carbonate;
preparing CaCl 2 When the reverse microemulsion is used, the mass ratio of CTAB, n-butanol and n-hexane is 0.2-0.3:0.2-0.3:1, the volume ratio of n-hexane to calcium chloride aqueous solution is 1:0.35-0.45, and the concentration of the calcium chloride aqueous solution is 0.3-0.7 mol/L;
preparing Na 2 CO 3 In the reverse microemulsion, the mass ratio of CTAB, n-hexanol, n-hexane and sucrose is 0.2-0.3:0.2-0.3:1:0.001-0.0015, the volume ratio of n-hexane to sodium carbonate aqueous solution is 1:1.1-1.5, and the concentration of sodium carbonate aqueous solution is 0.3-0.7 mol/L.
2. The method of manufacturing according to claim 1, characterized in that: preparing CaCl 2 In the reverse microemulsion, the mass ratio of CTAB, n-butanol and n-hexane is 0.25-0.3:0.2-0.26:1, the volume ratio of n-hexane to calcium chloride aqueous solution is 1:0.37-0.44, and the concentration of the calcium chloride aqueous solution is 0.4-0.6 mol/L.
3. The preparation method according to claim 2, characterized in that: the mass ratio of CTAB, n-butanol and n-hexane is 0.28-0.3:0.23-0.26:1, the volume ratio of n-hexane to calcium chloride aqueous solution is 1:0.41-0.43, and the concentration of the calcium chloride aqueous solution is 0.5mol/L.
4. The method of manufacturing according to claim 1, characterized in that: preparing Na 2 CO 3 In the reverse microemulsion, the mass ratio of CTAB, n-hexanol, n-hexane and sucrose is 0.25-0.3:0.2-0.26:1:0.001-0.0013, the volume ratio of n-hexane to sodium carbonate aqueous solution is 1:1.1-1.4, and the concentration of sodium carbonate aqueous solution is 0.4-0.6 mol/L.
5. The method of manufacturing according to claim 4, wherein: the mass ratio of CTAB, n-hexanol, n-hexane and sucrose is 0.28-0.3:0.23-0.26:1:0.001-0.0012, the volume ratio of n-hexane to sodium carbonate aqueous solution is 1:1.1-1.3, and the concentration of sodium carbonate aqueous solution is 0.5mol/L.
6. The method of manufacturing according to claim 1, characterized in that: preparing Na 2 CO 3 In the case of the inverse microemulsion, sucrose is first dissolved in an aqueous sodium carbonate solution, which is then mixed with CTAB, n-hexanol and n-hexane.
7. The method of manufacturing according to claim 1, characterized in that: na (Na) 2 CO 3 With CaCl 2 The molar ratio of (2.5) - (3.5:1).
8. The method of manufacturing according to claim 7, wherein: na (Na) 2 CO 3 With CaCl 2 The molar ratio of (2.7-3.1:1).
9. The method of manufacturing according to claim 1, characterized in that: the aging time is 24-48 hours.
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