CN114212814B - Preparation method of nano calcium carbonate - Google Patents
Preparation method of nano calcium carbonate Download PDFInfo
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- CN114212814B CN114212814B CN202111544971.9A CN202111544971A CN114212814B CN 114212814 B CN114212814 B CN 114212814B CN 202111544971 A CN202111544971 A CN 202111544971A CN 114212814 B CN114212814 B CN 114212814B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
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Abstract
The invention discloses a preparation method of nano calcium carbonate, which takes calcium carbonate ore as raw material, and the method comprises the steps of calcining and decomposing the calcium carbonate ore into calcium oxide, then carrying out digestion and aging, adding a crystal form control agent, introducing carbon dioxide gas for carrying out water bath reaction, monitoring the pH value of the solution, continuously introducing the carbon dioxide gas after the pH value reaches 7 to enable the pH value to be over carbonized until the pH value reaches 6 or below, stopping ventilation, filtering in time, washing and drying, and thus obtaining the nano calcium carbonate. According to the method, carbon dioxide is continuously introduced after the calcium hydroxide is consumed, so that the weak nano calcium carbonate in the chain nano calcium carbonate is redissolved to generate the calcium bicarbonate, and the particles are separated to obtain the monodisperse nano calcium carbonate. The method is simple and controllable, is suitable for industrial production, and can prepare nano calcium carbonate with good monodispersity and uniform particles.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation, and relates to a preparation method of nano calcium carbonate, in particular to a method for preparing nano calcium carbonate with uniform particles and good dispersibility based on super carbonization.
Background
The nano calcium carbonate is a functional filling material, is widely applied to industries such as rubber, plastic, papermaking, adhesives and the like, not only can play a role in filling and reduce cost, but also has a semi-reinforcing or reinforcing function, and endows a substrate with a certain special function.
According to different production methods, the calcium carbonate can be divided into heavy calcium carbonate and light calcium carbonate, wherein the heavy calcium carbonate reduces the particle size of calcium carbonate particles by a physical grinding mode, and the particle size of the calcium carbonate is hardly smaller than 1000nm due to the limitation of grinding equipment. The light calcium carbonate is prepared by a chemical reaction method, and the prepared calcium carbonate is nano-scale. Because of the nano-scale size, the nano calcium carbonate has the property of nano material, and has volume effect, surface effect, quantum size effect and the like. The unique properties of the nano calcium carbonate greatly develop the application field of the calcium carbonate.
Nano calcium carbonate is used as an abrasive in toothpaste, and if the particle size is too large, the nano calcium carbonate is easy to excessively abrade enamel, so that the tooth surface is damaged and defective, and more stains and bacteria are attached and bred. The nano-scale calcium carbonate can not cause excessive abrasion, and can be firmly adsorbed on the tooth surface or filled in the abrasion part to form a protective layer due to the high surface activity. The tooth is protected from erosion when other enamel components which are easy to erode such as subsequent acidity enter the oral cavity, and then the nano calcium carbonate protective layer is supplemented while food residues are removed by brushing.
At present, most of crystal form control agents adopted in the industrial production of nano calcium carbonate are acid (sulfuric acid, acetic acid, phosphoric acid, pyrophosphoric acid and the like), salt (sodium citrate, aluminum sulfate, zinc sulfate, sodium tripolyphosphate and the like) and the like, and the acid crystal form control agents influence the growth of the calcium carbonate through the adsorptivity of acid radical ions (sulfate radicals, carboxylic acid and the like); when ions of the salt crystal form control agent and ions of the calcium carbonate crystal are similar in crystal structure, particles of the crystal form control agent are easy to enter the crystal, the larger the similarity is, the easier the particles enter the crystal, so that the internal structure of the crystal is changed, meanwhile, the addition of the salt crystal form control agent can damage ionization balance of a system, change nucleation rate, change growth capacity of crystal nuclei in certain directions, inhibit growth in other directions, and then the calcium carbonate with specific morphology can be generated. However, the waste liquid containing the crystal form control agents has pollution to the environment, is difficult to ensure complete removal in the cleaning process, can cause harm to human bodies due to residues in the products, cannot be applied to the food and medicine field, and has limited application range. In addition, the existing nano calcium carbonate preparation method is often complicated in steps, so that the invention provides a preparation method of nano calcium carbonate which is nontoxic and harmless and has extremely simple steps.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of nano calcium carbonate, which is extremely simple, is applicable to industrial production, and can prepare nano calcium carbonate with good monodispersity and uniform particles.
The technical scheme adopted by the invention is as follows:
a process for preparing nano calcium carbonate includes calcining calcium carbonate ore, decomposing to become calcium oxide, digestion, ageing, adding crystal form control agent, introducing carbon dioxide gas, water bath reaction, monitoring pH value, continuously introducing carbon dioxide gas until pH value reaches 6 or less, stopping ventilation, filtering, washing and drying.
Specifically, calcium carbonate ore mined in a mining field can be subjected to preliminary crushing and screening, calcined and decomposed into calcium oxide, water is added to enable the mass fraction of the calcium oxide to be 3-5%, water bath heating is carried out at 70-80 ℃ and stirring is carried out at 900-1000 rpm, so that the calcium oxide is fully digested, calcium hydroxide slurry is obtained, and then aging is carried out for at least 24 hours;
the crystal form control agent should contain hydroxyl, aldehyde or carbonyl. Mainly utilizes the electrostatic adsorption effect of oxygen in oxygen-containing functional groups on calcium ions, and takes hydroxyl as an example, the outermost electron orbit of oxygen is 2s 2 p 4 Oxygen attracts 2 electrons to fill the outermost orbit of the oxygen because of stronger electronegativity than hydrogen, so as to form an 8-electron stable structure; the outermost electron orbit of calcium is 4s 2 After losing two electrons, calcium ions are formed, and empty orbitals appear. Oxygen on the hydroxyl group provides two electrons to occupy this empty orbit, forming a coordination bond, allowing oxygen to electrostatically adsorb calcium ions. The growth direction of the calcium ions is controlled by the steric hindrance effect of the adsorbed calcium ions, so that the purpose of controlling the morphology of the calcium carbonate is achieved. The crystal form control agent can adopt sugar substitutes such as xylitol, is friendly to human bodies even if the crystal form control agent in the final product has residues, and can be used in the fields of foods, medicines and the like.
The mass fraction of the crystal form control agent in the total mixed system is not less than 0.2%.
The ratio of the ventilation per minute (milliliter per minute) of the carbon dioxide to the amount of the calcium oxide substance is 1: 40-50.
The temperature of the water bath reaction is kept between 0 and 25 ℃.
According to the invention, the carbon dioxide ventilation process and the treatment process of the product after stopping ventilation are precisely controlled, the overcarbonization is fully utilized, firstly, the calcium carbonate grows into chain calcium carbonate along a certain direction under the limit of a crystal form control agent, then excessive carbon dioxide is introduced for further reaction, the long-chain calcium carbonate is gradually broken and decomposed into granular nano calcium carbonate, the pH value of the solution is precisely controlled, all the chain is completely broken and formed into granules, and the reaction solution is timely filtered, so that the nano calcium carbonate with uniform granules and good dispersibility is obtained, and the particle size of the nano calcium carbonate is 40-60nm.
Compared with the prior art, the invention has the beneficial effects that:
1) The crystal form control agent can adopt substances containing hydroxyl groups, aldehyde groups or carbonyl groups, particularly can adopt sugar substitutes such as xylitol and the like, and does not need to add other substances which are not easy to remove or are toxic and harmful to the environment as the crystal form control agent to control the growth of the calcium carbonate. Therefore, the nano calcium carbonate product prepared by the invention has no negative effect even if the crystalline form control agent remains, and can be used as an additive for food, medicine and the like which needs to ensure the safety of human bodies.
2) The crystal form control agent is added into the calcium hydroxide slurry, and the crystal form control agent attracts calcium ions through coordination bonds (wherein oxygen in oxygen-containing functional groups provides lone pair electrons and calcium ions provide empty orbitals). And after introducing carbon dioxide, the hydroxyl ions react with the carbon dioxide to produce carbonate ions, and the carbonate ions are combined with calcium ions in an ionic bond form to produce calcium carbonate. Neither the calcium ions adsorbed by the form control agent nor the free calcium ions react with carbonate ions to form clusters of calcium carbonate ions. The free calcium carbonate clusters are also connected under the electrostatic attraction of calcium ions adsorbed by the crystal form control agent to form a structure which is connected in a divergent manner with the crystal form control agent as the center. As the reaction proceeds, these calcium ions and carbonate ions between the structures will also gradually grow and link together, and at the same time, calcium carbonate will grow into chains in a certain direction due to the orientation of the lower energy crystalline phase of calcium carbonate, with the sites occupied by the crystalline form control agent at the links. And then dehydrating and crystallizing, wherein the crystal lattice is ordered, calcium carbonate crystals are formed, and the crystal lattice formed by surrounding calcium carbonate is disordered at chain links due to the existence of a crystal form control agent, so that the energy is higher. After the hydroxyl ions are consumed by the carbon dioxide which is introduced later, the carbon dioxide starts to react with the calcium carbonate to generate calcium bicarbonate for dissolution, so that the broken part at the chain link is caused, the nano calcium carbonate of the independent particles is finally obtained, the introduced carbon dioxide also reacts with the calcium carbonate except the chain link, and the particles of the calcium carbonate are more uniform and finer through erosion carving.
3) In the traditional preparation method, the pH value of the mixture is less than or equal to 7 (or 6.8) after the mixture is uniformly stirred to be used as a reaction end point index, namely, the complete reaction of calcium hydroxide, so that the calcium hydroxide is ensured to completely react to generate calcium carbonate. According to a great number of researches, the method is further characterized in that a carbonization means is adopted on the basis of the method, so that sufficient carbon dioxide is introduced, calcium bicarbonate is generated from calcium carbonate, all chain-shaped morphologies are broken to generate granular morphologies, and even if the pH value of a solution system reaches 6 or below, the method can effectively obtain nano calcium carbonate with uniform particles.
4) After the end of the over-carbonization ventilation, if the air is not treated in time, the carbon dioxide gas can gradually escape after long-time aging, the calcium bicarbonate is decomposed again to form calcium carbonate, and the calcium carbonate with a chain shape can be regenerated due to the crosslinking action of the crystal form control agent in the air, so that the meaning of the over-carbonization in the invention is demonstrated from the side.
Drawings
FIG. 1 is a graph showing the morphology of the product obtained in example 1 of the present invention;
FIG. 2 is a graph showing the morphology of the product obtained in example 2 of the present invention, wherein A to F are respectively 15min (B) for 30min (C) for 45min (D) for 60min (E) for 75min (F) for stopping the aeration and aging for 1h after the aeration is stopped, for the calcium hydroxide slurry (A).
Detailed Description
The scheme of the invention is further described below with reference to specific examples and drawings.
Example 1
Step one: the crushed, ground and screened calcium carbonate raw material is put into a muffle furnace for calcination at 1000 ℃.
Step two: 5.6g of calcined calcium oxide was dissolved in 200ml of deionized water, poured into a three-necked flask, digested in a water bath at 70℃and vigorously stirred at 1000rpm for 3 hours with a magnetic stirrer, and aged for 24 hours after completion of the digestion.
Step three: the flask was placed in a 25 ℃ water bath and vigorously stirred at 1000rpm using a magnetic stirrer.
Step four: the catheter with the porous quartz stone connected to the head is inserted below the liquid level, and carbon dioxide is introduced near the bottom as much as possible, wherein the aeration rate is 50ml/min.
Step five: when the aeration is carried out for 45min, the pH value of the solution is=7, the excessive aeration is continued for 30min, the aeration is carried out for 75min, at this time, the pH value of the solution is=6.78, the aeration is stopped, and the product is filtered, washed and dried to obtain the calcium carbonate, as shown in figure 1. The product obtained finally has quite unsatisfactory appearance and serious agglomeration phenomenon which reaches the micrometer scale due to free growth without any crystal form control agent.
Example 2
Step one: the crushed, ground and screened calcium carbonate raw material is put into a muffle furnace for calcination at 1000 ℃.
Step two: 5.6g of calcined calcium oxide was dissolved in 200ml of deionized water, poured into a three-necked flask, digested in a water bath at 70℃and vigorously stirred at 1000rpm for 3 hours with a magnetic stirrer, and aged for 24 hours after completion of the digestion.
Step three: 0.304g of xylitol was taken, a three-necked flask was charged, and the flask was placed in a water bath at 25℃and vigorously stirred at 1000rpm using a magnetic stirrer.
Step four: the catheter with the porous quartz stone connected to the head is inserted below the liquid level on the right side, and carbon dioxide is introduced to the catheter as close as possible to the bottom, wherein the ventilation rate is 50ml/min. Taking samples every 15min for morphology observation.
Step five: after the pH value of the solution is=7, ventilation is continued for 30min, and at the moment, the pH value of the solution is=6, ventilation is stopped, and the product is subjected to suction filtration, washing and drying to obtain nano calcium carbonate, as shown in fig. 2. In the figure, (A) was aerated into the slurry for 15min from the start of the reaction, and there was a large amount of long-chain nano calcium carbonate, and the reaction was insufficient, at which time the pH was 13.08, and calcium hydroxide was not consumed. (B) To aerate the slurry for 30min from the start of the reaction, the pH was 12.67. (C) In order to ventilate 45min from the beginning of the reaction to the slurry, the pH was 6.90, the consumption of calcium hydroxide was completed, the long-chain calcium carbonate had been significantly reduced, and the particulate ratio was increased. (D) To aerate the slurry for 60min from the start of the reaction, the pH was 6.23, at which time it was already aerated for 15min in excess, and calcium carbonate consumption was initiated to form calcium bicarbonate. (E) In order to ventilate 75min from the beginning of the reaction to the slurry at pH 6.02, the excess ventilation was carried out for 30min, calcium carbonate was consumed to form calcium bicarbonate, and long chain breakage was promoted to form granules. (F) In order to stop the aeration, the morphology aged for 1h was found to increase again the proportion of long-chain calcium carbonate, since at this time the carbon dioxide in the solution escapes, decomposing the calcium bicarbonate into calcium carbonate and binding the dispersed particles into long chains.
Claims (3)
1. The preparation method of the nano calcium carbonate is characterized by taking calcium carbonate ore as a raw material, calcining and decomposing the calcium carbonate ore into calcium oxide, then digesting and ageing the calcium oxide, adding a crystal form control agent, introducing carbon dioxide gas to perform water bath reaction, monitoring the pH value of the solution, continuously introducing the carbon dioxide gas to enable the pH value to be over carbonized until the pH value reaches below 6 after the pH value reaches 7, stopping ventilation, filtering in time, washing and drying to obtain the nano calcium carbonate, wherein the timely filtering means that the filtering is performed within 30min after ventilation is stopped to filter and remove the original reaction solution; the crystal form control agent is xylitol; the mass fraction of the crystal form control agent in the total mixed system is not less than 0.2%, and the ratio of ventilation amount of carbon dioxide per minute to the amount of calcium oxide substances is 1: 40-50%, and the temperature of the water bath reaction is kept at 0-25 ℃.
2. The method for preparing nano calcium carbonate according to claim 1, wherein calcium carbonate ore mined in a mining field is subjected to preliminary crushing and screening, calcined and decomposed into calcium oxide, water is added to enable the mass fraction of the calcium oxide to be 3-5%, water bath heating is carried out at 70-80 ℃ and stirring is carried out at 900-1000 rpm, so that the calcium hydroxide slurry is obtained, and then aging is carried out for at least 24-h.
3. The method for preparing nano calcium carbonate according to claim 1, wherein the particle size of the prepared nano calcium carbonate is 40-60nm.
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| CN116239903A (en) * | 2023-03-06 | 2023-06-09 | 湖北工业大学 | Preparation method of carbide slag-based carbonized inorganic refrigeration coating |
| CN116375071A (en) * | 2023-03-30 | 2023-07-04 | 苏州盛耀塑胶新材料有限公司 | Production process of superfine calcium carbonate |
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| BR0305049A (en) * | 2003-08-05 | 2005-05-17 | Carbomil S A Mineracao E Ind | Process for producing precipitated calcium carbonate |
| KR20050026158A (en) * | 2003-09-09 | 2005-03-15 | 김미현 | The process of manufacturing nano technology used high density antibiotic stone |
| KR100720865B1 (en) * | 2005-12-31 | 2007-05-23 | 한국지질자원연구원 | Novel manufacturing method of aragonite calcium carbonate |
| CN102491397A (en) * | 2011-12-09 | 2012-06-13 | 广东嘉维化工实业有限公司 | Preparation method of nano-calcium carbonate SCC-2 special for silicone sealant |
| SE1550647A1 (en) * | 2015-05-21 | 2016-11-22 | Stora Enso Oyj | Production of nanosized precipitated calcium carbonate and use in improving dewatering of fiber webs |
| CN111268712A (en) * | 2018-12-04 | 2020-06-12 | 天津大学 | Method for preparing nano calcium carbonate by using crystal form control agent for regulation and control |
| CN109879303B (en) * | 2019-03-29 | 2022-11-11 | 桂林理工大学 | Preparation method of nano calcium carbonate capable of stably suspending and dispersing in aqueous solution |
| CN110484022A (en) * | 2019-09-09 | 2019-11-22 | 青州宇信钙业股份有限公司 | A kind of production technology of the nanometer calcium carbonate of transparent membrane |
| CN111960455A (en) * | 2020-09-14 | 2020-11-20 | 荆门市东宝区凯龙矿业股份有限公司 | Preparation method and detection method of high-viscosity high-yield-value nano calcium carbonate |
| CN113247936A (en) * | 2021-06-25 | 2021-08-13 | 安徽前江超细粉末科技有限公司 | Method for reducing energy consumption in production of nano calcium carbonate |
| CN113443645A (en) * | 2021-07-19 | 2021-09-28 | 合肥工业大学 | Preparation and modification process of nano calcium carbonate |
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