CN115196662B - Preparation method of cubic nano calcium carbonate - Google Patents
Preparation method of cubic nano calcium carbonate Download PDFInfo
- Publication number
- CN115196662B CN115196662B CN202210854126.XA CN202210854126A CN115196662B CN 115196662 B CN115196662 B CN 115196662B CN 202210854126 A CN202210854126 A CN 202210854126A CN 115196662 B CN115196662 B CN 115196662B
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- crown ether
- nano calcium
- cubic
- steps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 129
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000003763 carbonization Methods 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 8
- 239000004571 lime Substances 0.000 claims abstract description 8
- 239000008267 milk Substances 0.000 claims abstract description 8
- 210000004080 milk Anatomy 0.000 claims abstract description 8
- 235000013336 milk Nutrition 0.000 claims abstract description 8
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- -1 crown ether compounds Chemical class 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- FXXRPTKTLVHPAR-UHFFFAOYSA-N 1,3,5-triaza-7-phosphaadamantane Chemical compound C1N(C2)CN3CN1CP2C3 FXXRPTKTLVHPAR-UHFFFAOYSA-N 0.000 claims description 3
- DYQFUHFIBUCCMI-UHFFFAOYSA-N 1,5-diazabicyclo[3.2.2]nonane Chemical compound C1CN2CCN1CCC2 DYQFUHFIBUCCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 claims description 3
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims description 3
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 abstract description 9
- 238000010899 nucleation Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 238000009826 distribution Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KPAMAAOTLJSEAR-UHFFFAOYSA-N [N].O=C=O Chemical compound [N].O=C=O KPAMAAOTLJSEAR-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001502 supplementing effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a preparation method of cubic nano calcium carbonate, which comprises the following steps: the method comprises the steps of screening lime milk suspension through a screen to remove impurities, and preparing refined calcium hydroxide suspension; adding the refined calcium hydroxide suspension into a stirring reaction kettle, starting stirring, and then introducing mixed gas containing carbon dioxide to carry out carbonization reaction; thirdly, adding a cage-shaped crystal form control agent after the carbonization reaction starts for 3-10 minutes; monitoring the carbonization reaction process by using a pH meter, and when the pH value of the suspension is 6.5-7, ending the carbonization reaction to obtain a reaction solution; the reaction liquid is aged, centrifuged, washed and dried to obtain the nano calcium carbonate product. The invention can improve the nucleation and growth rate of calcium carbonate and realize the ultrafining and cube formation of calcium carbonate.
Description
Technical Field
The invention relates to the technical field of nano calcium carbonate manufacturing, in particular to a preparation method of cubic nano calcium carbonate.
Background
The nano calcium carbonate is a calcium carbonate powder material with the particle size of 1-100 nm, and has the characteristics of ultra-fine, ultra-pure, high surface activity and the like. The nano calcium carbonate is a high-end product in the calcium carbonate industry and is widely applied to the industries of plastics, coatings, printing ink, paint, rubber, papermaking, adhesives, cosmetics and the like.
The morphology and particle size of calcium carbonate directly affect its performance and application range. Cubic nano calcium carbonate is the nano calcium carbonate material with the largest application amount at present. The cubic nano calcium carbonate is applied to a polymer and has the double effects of supplementing and reinforcing; the application of the modified polyester ink can improve the glossiness and transparency of ink products and improve rheological property when being applied to the ink.
Luo Ansheng et al (CN 100347086C) realized the preparation of cubic nano calcium carbonate particles by designing and utilizing a microreactor, but the morphology of the obtained product was uneven and less regular. Generally, the addition of crystalline form control agents with different effects during the preparation process is a main means for obtaining nano calcium carbonate with special morphology and size. Qiao Shegang (sea lake salt and chemical industry, 2005, 34 (1): 17) realizes the preparation of cubic nano calcium carbonate by adding 0.5% -5% of crystal form control agent, but the agglomeration of product particles is obvious and the carbonization reaction is neededAfter the end, adding a dispersing agent; liang Jin et al (inorganic salt industry, 2009, 41 (12): 22) in the form of heavy metal salts ZnSO 4 Preparing cubic nano calcium carbonate with the grain diameter of 30-80 nm as a crystal form guiding agent; chengzheng et al (journal of Material science and engineering, 2013, 31 (3): 404) adopts a two-time carbonization method with 4% NaHCO 3 As a crystal form control agent, the cubic nano calcium carbonate with regular morphology is prepared, but the process is complex, and the particle size of the product is larger; tong Zhangfa et al (Guangxi science, 2015, 22 (1): 53) using (NaPO) 3 ) 6 As a crystal form control agent, cubic nano calcium carbonate with a particle size of about 40 nm is prepared, the method requires strict control of process conditions, and the crystal form control agent is special. Besides inorganic salts, the composite crystal form guiding agent and the saccharide compound are also common crystal form control agents for preparing cubic nano calcium carbonate, the crystal form control agents have complex components and high price, and the research on the nucleation mechanism of the nano calcium carbonate is more difficult.
Disclosure of Invention
The invention aims to provide a preparation method of cubic nano calcium carbonate for improving calcium carbonate nucleation and growth rate.
In order to solve the problems, the preparation method of the cubic nano calcium carbonate provided by the invention comprises the following steps:
the method comprises the steps of screening a lime milk suspension through a screen to remove impurities, and preparing refined calcium hydroxide suspension with mass concentration of 5% -15%;
adding the refined calcium hydroxide suspension into a stirring reaction kettle, starting stirring, and then introducing mixed gas containing carbon dioxide to carry out carbonization reaction;
thirdly, adding a cage-shaped crystal form control agent according to 0.5% -3.5% of the theoretical yield of calcium carbonate after the carbonization reaction starts for 3-10 minutes;
monitoring the carbonization reaction process by using a pH meter, and when the pH value of the suspension is 6.5-7, ending the carbonization reaction to obtain a reaction solution; the reaction liquid is aged, centrifuged, washed and dried to obtain the nano calcium carbonate product.
The mesh number of the medium mesh is 80-300 mesh.
The stirring speed in the step is 300-800 r/min.
The flow rate of the mixed gas in the step II is 5-50L/(h L suspension), and the mixed gas consists of 15-60% of carbon dioxide by volume fraction and the balance of other components; the other components are one of nitrogen, argon and air.
And in the step II, the temperature of the carbonization reaction is 10-30 ℃.
The cage-shaped crystal form control agent in the step III is one or more of adamantane compounds, crown ether compounds, aza-polycyclic compounds and cubic silicon ether compounds, and the addition form is a solution form.
The adamantane compound is one or more of adamantane, diamantane and 1,3, 5-triaza-7-phospha adamantane; the crown ether compound is one or more of dibenzo-24-crown ether-8, dicyclohexyl-24-crown ether-8, 18 crown ether-6, aza-18-crown ether-6, benzo-18-crown ether-6, dibenzo-18-crown ether-6, dicyclohexyl-18-crown ether-6, 15 crown ether-5, benzo-15-crown ether-5, aza-15-crown ether-5, 12-crown ether-4, benzo-12-crown ether-4 and aza-12-crown ether-4; the azapolycyclic compound is one or more of hexamethylenetetramine, 1-azabicyclo [2.2.2] octane, 1, 4-diazabicyclo [2.2.2] octane and 1, 5-diazabicyclo [3.2.2] nonane; the cubic silicon ether compound is one or more of octaphenyl octasilsesquioxane (octaphenyl-POSS) and octacyclohexyl pentacyclooctasiloxane (octacyclohexyl-POSS).
And in the step IV, the aging time is 2-10 hours.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a stirring carbonization method commonly used in industrial production at home and abroad, takes lime milk and carbon dioxide as raw materials, improves the nucleation and growth rate of calcium carbonate by adding a cage-shaped crystal form control agent and controlling the technological conditions of carbonization reaction, and realizes the ultrafine and cubic formation of the calcium carbonate.
2. The cage-shaped heterocyclic crystal form control agent added in the invention reduces the activation energy of calcium carbonate crystallization nucleation, accelerates the nucleation rate, shortens the carbonization reaction time and improves the production capacity of the reactor per unit volume.
3. The cage-shaped organic molecule crystal form control agent has single component, simple and clear structure and is easy to study the nucleation mechanism of nano calcium carbonate.
4. The nano calcium carbonate product prepared by the method has the advantages of specific appearance, uniform cubic shape, 30-55 nm of particle size, narrow particle size distribution range, good dispersibility and good reproduction effect.
5. The invention is suitable for bubbling carbonization equipment commonly adopted in the nano calcium carbonate industry, has strong process applicability and large operable space, and does not need to carry out large-scale reconstruction or upgrading on the existing equipment.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 is an X-ray diffraction pattern of cubic nano-calcium carbonate particles prepared in example 3 of the present invention.
FIG. 2 is a scanning electron micrograph (100 nm) of cubic nano-calcium carbonate particles prepared in example 3 of the present invention.
FIG. 3 is a scanning electron micrograph (50 nm) of cubic nano-calcium carbonate particles prepared in example 3 of the present invention.
Detailed Description
The preparation method of the cubic nano calcium carbonate comprises the following steps:
the method comprises the steps of enabling lime milk suspension to pass through a mesh screen with 80-300 meshes, preferably 100-200 meshes. Removing coarse particles and other impurities, and preparing refined calcium hydroxide suspension with the mass concentration of 5% -15%. The concentration of the refined calcium hydroxide suspension is preferably 7% -12%.
And adding the refined calcium hydroxide suspension into a stirring reaction kettle, and starting stirring at a stirring speed of 300-800 r/min, preferably 400-600 r/min. And then introducing a mixed gas containing carbon dioxide, and performing carbonization reaction at 10-30 ℃. The carbonization reaction is preferably carried out at a temperature of 15-20 ℃.
Wherein: the flow rate of the mixed gas is 5-50L/(h L suspension), preferably 10-30L/(h L suspension). The mixed gas consists of 15-60% of carbon dioxide by volume fraction and the balance of other components; the other component is one of nitrogen, argon and air, preferably nitrogen. The concentration of carbon dioxide is preferably 30% -50%.
Thirdly, adding the cage-shaped crystal form control agent according to 0.5% -3.5% of the theoretical yield of the calcium carbonate after the carbonization reaction starts for 3-10 minutes.
Preferably, the time for adding the crystal form control agent is 3-5 minutes after the carbonization reaction starts, and the addition amount is 0.8-2% of the theoretical yield of calcium carbonate.
Wherein: the species of the cage-shaped crystal form control agent is one or more of adamantane compounds, crown ether compounds, aza-polycyclic compounds and cubic silicone ether compounds; the addition form is in the form of a solution, preferably an aqueous solution or an ethanol solution.
The adamantane compound is one or more of adamantane, diamantane and 1,3, 5-triaza-7-phospha adamantane.
Crown ether compounds are one or more of dibenzo-24-crown ether-8, dicyclohexyl-24-crown ether-8, 18 crown ether-6, aza-18-crown ether-6, benzo-18-crown ether-6, dibenzo-18-crown ether-6, dicyclohexyl-18-crown ether-6, 15 crown ether-5, benzo-15-crown ether-5, aza-15-crown ether-5, 12-crown ether-4, benzo-12-crown ether-4, aza-12-crown ether-4.
The aza-polycyclic compound is one or more of hexamethylenetetramine, 1-aza-bicyclo [2.2.2] octane, 1, 4-diazabicyclo [2.2.2] octane and 1, 5-diazabicyclo [3.2.2] nonane.
The cubic silicon ether compound is one or more of octaphenyl octasilsesquioxane (octaphenyl-POSS) and octacyclohexyl pentacyclooctasiloxane (octacyclohexyl-POSS).
Preferably, the crystalline form control agent is at least one of 18 crown ether 6, 12 crown ether-4, 1, 4-diazabicyclo [2.2.2] octane.
Monitoring the carbonization reaction process by using a pH meter, and when the pH value of the suspension is 6.5-7, preferably 6.8, ending the carbonization reaction to obtain a reaction solution; the reaction liquid is aged, centrifuged, washed and dried to obtain the nano calcium carbonate product. The aging time is 2 to 10 hours, preferably 4 to 6 hours.
The crystal form of the obtained nano calcium carbonate product is determined by using X-ray diffraction XRD, and analysis and identification of morphology and particle size are carried out by using a scanning electron microscope SEM.
On the one hand, heterocyclic organic molecules can be used as ligands to produce chelating coordination with calcium ions, so that the activation energy of calcium carbonate crystallization nucleation is reduced, and the nucleation rate is accelerated; on the other hand, the unique dense cage structure of the substance can form steric hindrance in a specific direction, influence the growth orientation of calcium carbonate crystals and further regulate the morphology of nano calcium carbonate.
Example 1 a method for preparing cubic nano calcium carbonate comprising the steps of:
6 liters of lime milk aqueous solution is screened through an 80-target standard sieve, and refined calcium hydroxide suspension with the mass concentration of 12% is prepared;
adding the refined calcium hydroxide suspension into a 10-liter stirring reaction kettle, controlling the initial temperature of the reaction kettle to be 17 ℃, starting stirring at a stirring speed of 400 r/min, and then introducing carbon dioxide-nitrogen mixed gas with a carbon dioxide volume concentration of 50% for carbonization reaction, wherein the gas flow is 60L/h;
thirdly, adding the caged crystal form control agent 18 crown ether 6 according to 1% of the theoretical yield of calcium carbonate after the carbonization reaction starts for 5 minutes, and continuously stirring;
and fourthly, tracking and monitoring the carbonization reaction process by using a digital display pH meter, recording the pH value of the system every 30 seconds, stopping ventilation when the pH value of the reaction liquid is 6.8, and aging the reaction liquid for 4 hours. And centrifuging the obtained product slurry, and vacuum drying at normal temperature to obtain the nano calcium carbonate product.
The nano calcium carbonate product is subjected to X-ray diffraction analysis to form calcite crystal form, the morphology is determined to be cubic by using a scanning electron microscope for observation, the particle size distribution is uniform, the average particle size is about 50nm, and the particle size distribution range is narrow.
Example 2 a method for preparing cubic nano calcium carbonate comprising the steps of:
the method comprises the steps of firstly, screening 6 liters of lime milk aqueous solution through a 100-mesh standard sieve, and preparing refined calcium hydroxide suspension with the mass concentration of 10%;
adding the refined calcium hydroxide suspension into a 10-liter stirring reaction kettle, controlling the initial temperature of the reaction kettle to be 15 ℃, starting stirring at a stirring speed of 500 r/min, and then introducing carbon dioxide-air mixed gas with a carbon dioxide volume concentration of 45% for carbonization reaction, wherein the gas flow is 120L/h;
thirdly, adding the caged crystal form control agent 12 crown ether 4 according to 1.2% of the theoretical yield of calcium carbonate after the carbonization reaction starts for 3 minutes, and continuously stirring;
and fourthly, tracking and monitoring the carbonization reaction process by using a digital display pH meter, recording the pH value of the system every 30 seconds, stopping ventilation when the pH value of the reaction liquid is 6.8, and aging the reaction liquid for 4 hours. And centrifuging the obtained product slurry, and vacuum drying at normal temperature to obtain the nano calcium carbonate product.
The nano calcium carbonate product is subjected to X-ray diffraction analysis to form calcite crystal form, the morphology is determined to be cubic by using a scanning electron microscope for observation, the particle size distribution is uniform, the average particle size is about 45 and nm, and the particle size distribution range is narrow.
Example 3 a method for preparing cubic nano calcium carbonate comprising the steps of:
the method comprises the steps of enabling 6 liters of lime milk aqueous solution to pass through a 160-target standard sieve, and preparing refined calcium hydroxide suspension with mass concentration of 8%;
adding the refined calcium hydroxide suspension into a 10-liter stirring reaction kettle, controlling the initial temperature of the reaction kettle to be 13 ℃, starting stirring, enabling the stirring speed to be 500 r/min, then introducing carbon dioxide-nitrogen mixed gas with the carbon dioxide volume concentration of 40% for carbonization reaction, wherein the gas flow is 180L/h
Thirdly, adding the caged crystal form control agent 1, 4-diazabicyclo [2.2.2] octane according to 1.5% of the theoretical yield of calcium carbonate after the carbonization reaction starts for 5 minutes, and continuously stirring;
and fourthly, tracking and monitoring the carbonization reaction process by using a digital display pH meter, recording the pH value of the system every 30 seconds, stopping ventilation when the pH value of the reaction liquid is 6.8, and aging the reaction liquid for 6 hours. And centrifuging the obtained product slurry, and vacuum drying at normal temperature to obtain the nano calcium carbonate product.
The nano calcium carbonate product is subjected to X-ray diffraction analysis to obtain calcite crystal forms, as shown in figure 1. And the morphology is determined to be cubic by using a scanning electron microscope for observation, the particle size distribution is uniform, the average particle size is 30 nm, and the particle size distribution range is narrow, as shown in fig. 2-3.
Claims (6)
1. The preparation method of the cubic nano calcium carbonate comprises the following steps:
the method comprises the steps of screening a lime milk suspension through a screen to remove impurities, and preparing refined calcium hydroxide suspension with mass concentration of 5% -15%;
adding the refined calcium hydroxide suspension into a stirring reaction kettle, starting stirring, and then introducing mixed gas containing carbon dioxide to carry out carbonization reaction;
thirdly, adding a cage-shaped crystal form control agent according to 0.5% -3.5% of the theoretical yield of calcium carbonate after the carbonization reaction starts for 3-10 minutes; the cage-shaped crystal form control agent is one or more of adamantane compounds, crown ether compounds, aza-polycyclic compounds and cubic silicon ether compounds, and the addition form is a solution form; the adamantane compound is one or more of adamantane, diamantane and 1,3, 5-triaza-7-phospha adamantane; the crown ether compound is one or more of dibenzo-24-crown ether-8, dicyclohexyl-24-crown ether-8, 18 crown ether-6, aza-18-crown ether-6, benzo-18-crown ether-6, dibenzo-18-crown ether-6, dicyclohexyl-18-crown ether-6, 15 crown ether-5, benzo-15-crown ether-5, aza-15-crown ether-5, 12-crown ether-4, benzo-12-crown ether-4 and aza-12-crown ether-4; the azapolycyclic compound is one or more of hexamethylenetetramine, 1-azabicyclo [2.2.2] octane, 1, 4-diazabicyclo [2.2.2] octane and 1, 5-diazabicyclo [3.2.2] nonane; the cubic silicon ether compound is one or more of octaphenyl octasilsesquioxane (octaphenyl-POSS) and octacyclohexyl pentacyclooctasiloxane (octacyclohexyl-POSS);
monitoring the carbonization reaction process by using a pH meter, and when the pH value of the suspension is 6.5-7, ending the carbonization reaction to obtain a reaction solution; the reaction liquid is aged, centrifuged, washed and dried to obtain the nano calcium carbonate product.
2. The method for preparing the cubic nano calcium carbonate according to claim 1, wherein the method comprises the following steps: the mesh number of the medium mesh is 80-300 mesh.
3. The method for preparing the cubic nano calcium carbonate according to claim 1, wherein the method comprises the following steps: the stirring speed in the step is 300-800 r/min.
4. The method for preparing the cubic nano calcium carbonate according to claim 1, wherein the method comprises the following steps: the flow rate of the mixed gas in the step II is 5-50L/(h L suspension), and the mixed gas consists of 15-60% of carbon dioxide by volume fraction and the balance of other components; the other components are one of nitrogen, argon and air.
5. The method for preparing the cubic nano calcium carbonate according to claim 1, wherein the method comprises the following steps: and in the step II, the temperature of the carbonization reaction is 10-30 ℃.
6. The method for preparing the cubic nano calcium carbonate according to claim 1, wherein the method comprises the following steps: and in the step IV, the aging time is 2-10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210854126.XA CN115196662B (en) | 2022-07-20 | 2022-07-20 | Preparation method of cubic nano calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210854126.XA CN115196662B (en) | 2022-07-20 | 2022-07-20 | Preparation method of cubic nano calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115196662A CN115196662A (en) | 2022-10-18 |
| CN115196662B true CN115196662B (en) | 2023-12-19 |
Family
ID=83582080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210854126.XA Active CN115196662B (en) | 2022-07-20 | 2022-07-20 | Preparation method of cubic nano calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115196662B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07267634A (en) * | 1994-03-25 | 1995-10-17 | Yusaku Takita | Method for producing plate-like calcium carbonate |
| CN1361063A (en) * | 2002-01-22 | 2002-07-31 | 广州吉必时科技实业有限公司 | One-step carbonization process of preparing cubic calcium carbonate of 80-100 nm size |
| CN1704338A (en) * | 2004-05-31 | 2005-12-07 | 上海卓越纳米新材料股份有限公司 | Process for preparing active nano calcium carbonate for silicon rubber |
| CN104556185A (en) * | 2015-01-14 | 2015-04-29 | 广西大学 | Method for preparing cubic nano calcium carbonate |
| CN109574057A (en) * | 2019-01-14 | 2019-04-05 | 江油市万山矿业有限公司 | A kind of preparation method of calcium carbonate |
| CN114291836A (en) * | 2021-12-31 | 2022-04-08 | 连州市凯恩斯纳米材料有限公司 | Calcium carbonate crystal form control agent, application thereof and preparation method of cubic calcium carbonate |
-
2022
- 2022-07-20 CN CN202210854126.XA patent/CN115196662B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07267634A (en) * | 1994-03-25 | 1995-10-17 | Yusaku Takita | Method for producing plate-like calcium carbonate |
| CN1361063A (en) * | 2002-01-22 | 2002-07-31 | 广州吉必时科技实业有限公司 | One-step carbonization process of preparing cubic calcium carbonate of 80-100 nm size |
| CN1704338A (en) * | 2004-05-31 | 2005-12-07 | 上海卓越纳米新材料股份有限公司 | Process for preparing active nano calcium carbonate for silicon rubber |
| CN104556185A (en) * | 2015-01-14 | 2015-04-29 | 广西大学 | Method for preparing cubic nano calcium carbonate |
| CN109574057A (en) * | 2019-01-14 | 2019-04-05 | 江油市万山矿业有限公司 | A kind of preparation method of calcium carbonate |
| CN114291836A (en) * | 2021-12-31 | 2022-04-08 | 连州市凯恩斯纳米材料有限公司 | Calcium carbonate crystal form control agent, application thereof and preparation method of cubic calcium carbonate |
Non-Patent Citations (1)
| Title |
|---|
| 聚合物控制碳酸钙晶型、形貌的研究;陈银霞;赵改青;王晓波;;化学进展;21(7/8);1619-1625 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115196662A (en) | 2022-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107215863B (en) | Method for preparing graphene/MOF porous composite hydrogel and aerogel | |
| EP3122687B1 (en) | High surface area layered double hydroxides | |
| US6254845B1 (en) | Synthesis method of spherical hollow aluminosilicate cluster | |
| CN109650430B (en) | Method for preparing nano calcium carbonate from limestone with high magnesium content | |
| Wang et al. | Hydrothermal synthesis of hexagonal magnesium hydroxide nanoflakes | |
| WO2010078821A1 (en) | Method for preparing subsphaeroidal barium sulfate by sulfuric acid process and its use in copper foil substrate | |
| CN111715254A (en) | Preparation method of nitrogen-modified porous carbon-coated cobalt nanoparticle catalyst | |
| CN113004576B (en) | Preparation method of supported nano zinc oxide | |
| Deng et al. | Surface area control of nanocomposites Mg (OH) 2/graphene using a cathodic electrodeposition process: High adsorption capability of methyl orange | |
| CN115196662B (en) | Preparation method of cubic nano calcium carbonate | |
| CN111715289B (en) | In-situ synthesis of FeOOH/Fe 3 O 4 Method for preparing/cellulose composite material and application thereof | |
| CN109694085B (en) | Template-free synthesis method of ammonium type ZSM-5 nanosheet | |
| CN111330520A (en) | Preparation method and application of graphene and UIO-66 composite aerogel | |
| CN109338466B (en) | Preparation of single crystal Fe2O3Method for self-assembling nano-particle into elliptical micro-nano structure | |
| CN115212859A (en) | Method for preparing copper compound nano material by solid phase one-pot at room temperature | |
| CN110371941B (en) | Preparation method of morphology-adjustable copper hydroxyphosphate multi-level micron material | |
| CN113772706A (en) | Preparation method of short column-shaped micron calcium carbonate | |
| Liao et al. | Shape-controllable synthesis of dendritic silver nanostructures at room temperature | |
| CN114425339A (en) | Carbon-based hexagonal close-packed phase cobalt nanocomposite and preparation method and application thereof | |
| CN112316894A (en) | Method for preparing magnetic mesoporous composite adsorbent by using natural mixed clay | |
| CN115872451B (en) | Preparation method of sulfur-free spherical manganese carbonate powder | |
| Yan et al. | Hydrothermal synthesis and photocatalytic degradation ability of nickel phosphide micro/nano materials | |
| CN114314629B (en) | Preparation method of nano calcium carbonate based on surface potential control | |
| CN115057463B (en) | Micron-sized polyhedral calcium carbonate and preparation method thereof | |
| CN114653963B (en) | Preparation method of nanometer copper powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |