CN114455620B - A method for preparing square and clustered symbiotic micron-sized calcium carbonate - Google Patents

A method for preparing square and clustered symbiotic micron-sized calcium carbonate Download PDF

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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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aqueous solution
hexane
ctab
calcium carbonate
sodium carbonate
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宋河远
马一童
王农
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Jiangshan Chenghui Calcium Industry Co ltd
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Lanzhou Jiaotong University
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    • C01F11/00Compounds of calcium, strontium, or barium
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Abstract

本发明公开了一种方形与簇状共生一体的微米级碳酸钙的制备方法,该方法包括以下步骤:1)将CTAB、正丁醇、正己烷和氯化钙水溶液混合,配制成CaCl2反相微乳液;2)将CTAB、正己醇、正己烷、蔗糖和碳酸钠水溶液混合,配制成Na2CO3反相微乳液;3)按Na2CO3与CaCl2的摩尔比为2~4:1,将Na2CO3反相微乳液加入到CaCl2反相微乳液中,加入完毕后,陈化,得到所述的方形与簇状共生一体的微米级碳酸钙。与现有方形碳酸钙相比,本发明的碳酸钙作为填料在纸张、涂料、油漆和塑料中具更好的抗掉粉性能和抗沉降性能。

The invention discloses a method for preparing square and clustered micron-sized calcium carbonate. The method includes the following steps: 1) Mix CTAB, n-butanol, n-hexane and calcium chloride aqueous solution to prepare CaCl 2 reaction solution. phase microemulsion; 2) Mix CTAB, n-hexanol, n-hexane, sucrose and sodium carbonate aqueous solution to prepare a Na 2 CO 3 inverse microemulsion; 3) The molar ratio of Na 2 CO 3 to CaCl 2 is 2 to 4 :1. Add Na 2 CO 3 inverse microemulsion to CaCl 2 inverse microemulsion. After the addition is completed, age it to obtain the micron-sized calcium carbonate in which square and cluster shapes are symbiotic. Compared with the existing square calcium carbonate, the calcium carbonate of the present invention has better anti-powder resistance and anti-settling properties as a filler in paper, coatings, paints and plastics.

Description

一种方形与簇状共生一体的微米级碳酸钙的制备方法A method for preparing square and clustered symbiotic micron-sized calcium carbonate

技术领域Technical field

本发明属于碳酸钙领域,具体涉及一种方形与簇状共生一体的微米级碳酸钙的制备方法。The invention belongs to the field of calcium carbonate, and specifically relates to a method for preparing square and cluster-shaped micron-sized calcium carbonate.

背景技术Background technique

碳酸钙 (CaCO3) 是一种无机化合物,通常被称为石灰石、大理石等,其摩尔质量为 100.09 g/mol,密度为 2.93 g/cm3,熔点为 825 ℃。常温下,微溶于水 (Ksp = 2.9×10-9),有文石、方解石和球霰石三种晶型。此外碳酸钙还是地球上储存量最多的物质之一。因为碳酸钙成本低、性能好、广泛应用于橡胶、塑料、造纸、涂料、医药、油墨、食品、牙膏、化妆品等的生产、加工和应用中。Calcium carbonate (CaCO 3 ) is an inorganic compound, commonly known as limestone, marble, etc., with a molar mass of 100.09 g/mol, a density of 2.93 g/cm 3 and a melting point of 825°C. At room temperature, it is slightly soluble in water (Ksp = 2.9×10 -9 ) and has three crystal forms: aragonite, calcite and vaterite. In addition, calcium carbonate is one of the most abundant substances on earth. Because of its low cost and good performance, calcium carbonate is widely used in the production, processing and application of rubber, plastics, papermaking, coatings, medicine, ink, food, toothpaste, cosmetics, etc.

不同形状的碳酸钙有不同的用处,例如立方形碳酸钙在纸张中表现出高白度和不透明度。它作为填料剂加入塑料中,可以改善塑料制品的导热导电性能、阻燃耐热性能、耐冲击腐蚀性能等;它还可以代替白炭黑,使塑料制品表面光亮、抗张力强、耐弯曲性好、抗龟裂性好,是优良的白色补强剂。球形碳酸钙有很好的不透明性、平滑性和流动性,可以应用到各种润滑油中,使润滑油的润滑性能大大提高。亦可用于牙膏、化妆品和电子陶瓷的生产中。纺锤形碳酸钙类似于微生物纤维,因此可以赋予纸张松厚性、不透明性、平滑度、以及可印刷性等优良使用性能。还可以广泛用做橡胶和塑料中的密封剂、压敏胶黏剂等产品的生产制造中。链状碳酸钙被广泛用于合成橡胶中,由于在橡胶合成中,这些链状碳酸钙会受到机械振动和研磨,这将导致某些连接点断裂,从而形成具有较高活性的断点。这些断点可以使之与合成橡胶基体之间发生键连,使连接更加紧密,从而提高了合成橡胶的理化性能。片状碳酸钙由于其分散性能好、光学性能和印刷性能优良、表面涂覆功能强,被广泛应用于涂料和造纸中。片状碳酸钙加入涂料中,可以使涂料具有良好的流动性和分散性;加入纸张中表现出比纺锤状碳酸钙更好的光洁度和松厚度,因此可以代替渐少的片状高岭土。Different shapes of calcium carbonate have different uses. For example, cubic calcium carbonate exhibits high whiteness and opacity in paper. It is added to plastics as a filler to improve the thermal and electrical conductivity, flame retardancy and heat resistance, impact and corrosion resistance of plastic products. It can also replace white carbon black to make plastic products have a bright surface, strong tensile strength and bending resistance. It has good anti-cracking properties and is an excellent white reinforcing agent. Spherical calcium carbonate has good opacity, smoothness and fluidity, and can be applied to various lubricating oils to greatly improve the lubricating performance of the lubricating oil. It can also be used in the production of toothpaste, cosmetics and electronic ceramics. Spindle-shaped calcium carbonate is similar to microbial fibers, so it can give paper excellent properties such as bulk, opacity, smoothness, and printability. It can also be widely used in the production and manufacturing of sealants, pressure-sensitive adhesives and other products in rubber and plastics. Chain-like calcium carbonate is widely used in synthetic rubber. Since these chain-like calcium carbonates are subject to mechanical vibration and grinding during rubber synthesis, this will cause certain connection points to break, thereby forming breakpoints with higher activity. These breakpoints can bond it with the synthetic rubber matrix, making the connection tighter, thus improving the physical and chemical properties of the synthetic rubber. Flake calcium carbonate is widely used in coatings and papermaking due to its good dispersion properties, excellent optical properties and printing properties, and strong surface coating capabilities. Adding flaky calcium carbonate to paint can make the paint have good fluidity and dispersion; adding it to paper shows better smoothness and bulk than spindle-shaped calcium carbonate, so it can replace the decreasing amount of flaky kaolin.

微乳液最早由 Schulman等提出,它是一种由水相、油相、两亲性化合物等组成的分散体系,根据分散介质不同可将微乳液分为水包油型 (O/W) 和油包水型 (W/O)。反相微乳液即油包水型微乳液 (W/O),它以非极性溶剂 (油相) 为分散相,将水溶液均匀地分散在油相中,被两亲性化合物包裹,形成直径为 5 ~ 100 nm 的 “微水池” (也称作液滴)。可通过调节表面活性剂与水的摩尔比,将 “液滴” 大小控制在一定范围之间,这种特殊的微水池是多种化学反应和物理排列共同作用下形成的。目前,微乳液法因其操作简单且无需高温高压设备,已经广泛应用于微纳米材料的制备中,如制备复合催化剂、半导体,超导体材料以及磁性纳米粒子等。Microemulsion was first proposed by Schulman et al. It is a dispersion system composed of water phase, oil phase, amphiphilic compounds, etc. Microemulsions can be divided into oil-in-water (O/W) and oil-in-water types according to different dispersion media. Water-encapsulated type (W/O). Inverse microemulsion is water-in-oil microemulsion (W/O), which uses a non-polar solvent (oil phase) as the dispersed phase. The aqueous solution is evenly dispersed in the oil phase and is wrapped by amphiphilic compounds to form a diameter It is a "micropool" (also called a droplet) of 5 ~ 100 nm. The size of the "droplets" can be controlled within a certain range by adjusting the molar ratio of surfactant to water. This special micro-pool is formed by a variety of chemical reactions and physical arrangements. At present, the microemulsion method has been widely used in the preparation of micro-nano materials, such as the preparation of composite catalysts, semiconductors, superconductor materials and magnetic nanoparticles, because it is simple to operate and does not require high-temperature and high-pressure equipment.

在此之前发明人采用反相微乳法对微纳级碳酸钙的制备做了系列研究(CN11592026A、CN111484061A、CN102583481A、CN111592025A、CN111675235A、CN111675234A,以上专利文献以全文引用的方式并入本文),结果表明采用不同的油相、表面活性剂、助表面活性剂等构建反相微乳体系对碳酸钙的形貌具有显著的影响。Prior to this, the inventor used the inverse microemulsion method to conduct a series of studies on the preparation of micro-nano-scale calcium carbonate (CN11592026A, CN111484061A, CN102583481A, CN111592025A, CN111675235A, CN111675234A, the above patent documents are incorporated herein by reference in full). The results It shows that the use of different oil phases, surfactants, co-surfactants, etc. to construct an inverse microemulsion system has a significant impact on the morphology of calcium carbonate.

发明内容Contents of the invention

基于上述现有技术,本发明的目的在于提供一种方形与簇状共生一体的微米级碳酸钙的制备方法。Based on the above-mentioned prior art, the object of the present invention is to provide a method for preparing square and cluster-shaped micron-sized calcium carbonate.

为实现上述目的,本发明所采用的技术方案如下:In order to achieve the above objects, the technical solutions adopted by the present invention are as follows:

一种方形与簇状共生一体的微米级碳酸钙的制备方法,包括以下步骤:A method for preparing square and cluster-shaped micron-sized calcium carbonate, which includes the following steps:

1) CaCl2反相微乳液的配制:1) Preparation of CaCl 2 reverse microemulsion:

将CTAB、正丁醇、正己烷和氯化钙水溶液混合,配制成CaCl2反相微乳液;Mix CTAB, n-butanol, n-hexane and calcium chloride aqueous solution to prepare a CaCl 2 reverse microemulsion;

2)Na2CO3反相微乳液的配制:2) Preparation of Na 2 CO 3 reverse microemulsion:

将CTAB、正己醇、正己烷、蔗糖和碳酸钠水溶液混合,配制成Na2CO3反相微乳液;Mix CTAB, n-hexanol, n-hexane, sucrose and sodium carbonate aqueous solution to prepare a Na 2 CO 3 reverse microemulsion;

3)按Na2CO3与CaCl2的摩尔比为2~4:1,将Na2CO3反相微乳液加入到CaCl2反相微乳液中,加入完毕后,陈化,得到所述的方形与簇状共生一体的微米级碳酸钙。3) According to the molar ratio of Na 2 CO 3 to CaCl 2 being 2~4:1, add the Na 2 CO 3 reverse microemulsion to the CaCl 2 reverse microemulsion. After the addition is completed, age to obtain the described Square and clustered micron-sized calcium carbonate.

优选地,配制CaCl2反相微乳液时,CTAB、正丁醇和正己烷的质量比为0.2~0.3:0.2~0.3:1,正己烷和氯化钙水溶液的体积比为1:0.35~0.45,氯化钙水溶液的浓度为0.3~0.7mol/L。Preferably, when preparing CaCl2 inverse microemulsion, the mass ratio of CTAB, n-butanol and n-hexane is 0.2~0.3:0.2~0.3:1, and the volume ratio of n-hexane and calcium chloride aqueous solution is 1:0.35~0.45, The concentration of calcium chloride aqueous solution is 0.3~0.7mol/L.

更优选地,CTAB、正丁醇和正己烷的质量比为0.25~0.3:0.2~0.26:1,正己烷和氯化钙水溶液的体积比为1:0.37~0.44,氯化钙水溶液的浓度为0.4~0.6mol/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 and calcium chloride aqueous solution is 1:0.37~0.44, and the concentration of calcium chloride aqueous solution is 0.4 ~0.6mol/L.

最优选地,CTAB、正丁醇和正己烷的质量比为0.28~0.3:0.23~0.26:1,正己烷和氯化钙水溶液的体积比为1:0.41~0.43,氯化钙水溶液的浓度为0.5mol/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 and calcium chloride aqueous solution is 1:0.41~0.43, and the concentration of calcium chloride aqueous solution is 0.5 mol/L.

优选地,配制Na2CO3反相微乳液时,CTAB、正己醇、正己烷和蔗糖的质量比为0.2~0.3:0.2~0.3:1:0.001~ 0.0015,正己烷和碳酸钠水溶液的体积比为1:1.1~1.5,碳酸钠水溶液的浓度为0.3~0.7mol/L。Preferably, when preparing Na 2 CO 3 inverse 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, and the volume ratio of n-hexane and sodium carbonate aqueous solution is The ratio is 1:1.1~1.5, and the concentration of sodium carbonate aqueous solution is 0.3~0.7mol/L.

更优选地,CTAB、正己醇、正己烷和蔗糖的质量比为0.25~0.3:0.2~0.26:1:0.001~0.0013,正己烷和碳酸钠水溶液的体积比为1:1.1~1.4,碳酸钠水溶液的浓度为0.4~0.6mol/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 and sodium carbonate aqueous solution is 1:1.1~1.4, and the sodium carbonate aqueous solution The concentration is 0.4~0.6mol/L.

最优选地,CTAB、正己醇、正己烷和蔗糖的质量比为0.28~0.3:0.23~0.26:1:0.001~ 0.0012,正己烷和碳酸钠水溶液的体积比为1:1.1~1.3,碳酸钠水溶液的浓度为0.5mol/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 and sodium carbonate aqueous solution is 1:1.1~1.3, and the sodium carbonate aqueous solution The concentration is 0.5mol/L.

蔗糖溶于水不溶于正己烷,优选地,配制Na2CO3反相微乳液时,先将蔗糖溶于碳酸钠水溶液,再将碳酸钠水溶液与CTAB、正己醇和正己烷混合。Sucrose is soluble in water and insoluble in n-hexane. Preferably, when preparing the Na 2 CO 3 reverse microemulsion, first dissolve sucrose in a sodium carbonate aqueous solution, and then mix the sodium carbonate aqueous solution with CTAB, n-hexanol and n-hexane.

优选地,Na2CO3与CaCl2的摩尔比为2.5~3.5:1。Preferably, the molar ratio of Na 2 CO 3 to CaCl 2 is 2.5~3.5:1.

最优选地,Na2CO3与CaCl2的摩尔比为2.7~3.1:1。Most preferably, the molar ratio of Na 2 CO 3 to CaCl 2 is 2.7~3.1:1.

优选地,陈化时间为24~48小时。Preferably, the aging time is 24 to 48 hours.

有益效果beneficial effects

采用本发明方法制备了一种新颖的方形与簇状共生一体的微米级碳酸钙。与现有方形碳酸钙相比,本发明的碳酸钙在固体介质中,其方形本体上向外伸展的簇状结构可以起到锚定作用,增大方形本体与介质的接触面积和附着能力,提高碳酸钙在纸张、涂层、漆层和塑料中的抗掉粉性能,在液体介质中方形本体上向外伸展的簇状结构则可以起到类似鱼鳍的作用,提高其在液体介质中的抗沉降性能,可作为一种优良的填料应用于纸张、涂料、油漆和塑料等领域。A novel square-shaped and cluster-shaped micron-sized calcium carbonate is prepared by using the method of the present invention. Compared with the existing square calcium carbonate, the outwardly extending cluster structure on the square body of the calcium carbonate of the present invention can play an anchoring role in a solid medium, increasing the contact area and adhesion capacity between the square body and the medium. Improve the anti-powder resistance of calcium carbonate in paper, coatings, paint layers and plastics. The cluster-like structure extending outward on the square body in the liquid medium can play a role similar to that of a fish fin, improving its performance in the liquid medium. It has excellent anti-settling properties and can be used as an excellent filler in paper, coatings, paints, plastics and other fields.

附图说明Description of the drawings

图l 为本发明制备的微米级碳酸钙的扫描电镜图;其中, a、b为5000倍扫描电镜放大图,c为10000倍扫描电镜放大图。Figure 1 is a scanning electron microscope image of the micron-sized calcium carbonate prepared by the present invention; wherein, a and b are 5000 times magnified images of the scanning electron microscope, and c is a 10000 times magnified image of the scanning electron microscope.

图2为碳酸钙的X射线衍射图;其中,a 为球霰石碳酸钙和方解石碳酸钙的标准X射线衍射图,b 为本发明制备的微米级碳酸钙的X射线衍射图。Figure 2 is the X-ray diffraction pattern of calcium carbonate; where 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 by the present invention.

具体实施方式Detailed ways

以下结合附图及实施例对本发明的技术方案做进一步详细说明。The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and examples.

采用扫描电镜(JSM-6100,JEOL Ltd日本)分析了复合材料粉末样品的尺寸和形貌。采用X射线粉末衍射(XRD; RINT-1000, Rigaku, 日本)分析了其晶体结构。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).

CaCl2反相微乳液体系原料的选择:表面活性剂CTAB(十六烷基三甲基溴化铵),助表面活性剂正丁醇,油相正己烷,水相氯化钙水溶液。Selection of raw materials for CaCl 2 reverse microemulsion system: surfactant CTAB (cetyltrimethylammonium bromide), co-surfactant n-butanol, oil phase n-hexane, and water phase calcium chloride aqueous solution.

Na2CO3反相微乳液体系原料的选择:表面活性剂CTAB,助表面活性剂正己醇,油相正己烷,水相氯化钙水溶液,助剂蔗糖。Selection of raw materials for Na 2 CO 3 reverse microemulsion system: surfactant CTAB, co-surfactant n-hexanol, oil phase n-hexane, water phase calcium chloride aqueous solution, and auxiliary sucrose.

从图1a-b可以看出,本发明实施例制备的微米级碳酸钙具有方形与簇状共生一体的结构,在该结构中,簇状位于方形本体其中的一角或相对的两角上,并向外侧伸展。It can be seen from Figure 1a-b that the micron-sized calcium carbonate prepared in the embodiment of the present invention has a symbiotic structure of square and cluster. In this structure, the cluster is located on one corner or two opposite corners of the square body, and Stretch outward.

进一步从图1c可以看出,簇状碳酸钙是从方形本体上缺失的一个或相对的两个顶角上一节一节首尾相连的向外伸展,多个并排的节之间又呈相互抱拢之状,本文称之为链簇状。It can be further seen from Figure 1c that the clustered calcium carbonate extends outward from one missing or two opposite corners of the square body, with sections connected end to end, and multiple side-by-side sections embracing each other. The clustered shape is called chain cluster shape in this article.

在其它条件不变的情况下,用正丁醇替代正己醇未能得到Na2CO3反相微乳液。When other conditions remained unchanged, replacing n-hexanol with n-butanol failed to obtain a Na 2 CO 3 reverse microemulsion.

从图2a-b可以看出,本发明实施例制备的微米级碳酸钙出现在2θ的29.16°、35.81°、39.25°和42.36°的衍射峰与方解石的标准X射线衍射图相同,而出现在20.81°、24.72°、26.93°、32.60°、43.68°、49.82°和55.64°的衍射峰与球霰石的标准X射线衍射图相同,表明本发明所制备的方形与簇状共生一体的微米级碳酸钙同时存在球霰石(Vaterite)和方解石(Calcite)两种晶型。It can be seen from Figure 2a-b that the diffraction peaks at 29.16 °, 35.81°, 39.25° and 42.36° of the micron-sized calcium carbonate prepared in the embodiment of the present invention are the same as the standard X-ray diffraction pattern of calcite. The diffraction peaks at 20.81°, 24.72°, 26.93°, 32.60°, 43.68°, 49.82° and 55.64° are the same as the standard X-ray diffraction pattern of vaterite, indicating that the square and cluster symbiotic micron-scale particles prepared by the present invention Calcium carbonate exists in two crystal forms: vaterite and calcite.

实施例1Example 1

方形与簇状共生一体的微米级碳酸钙的制备过程如下:The preparation process of square and clustered micron-sized calcium carbonate is as follows:

1) CaCl2反相微乳液的配制:1) Preparation of CaCl 2 reverse microemulsion:

氯化钙水溶液的制备:称取5.549g氯化钙,加少量的水溶解于烧杯中,完全溶解后转移至100ml的容量瓶中定容,得到浓度为0.5mol/L的氯化钙水溶液,备用。Preparation of calcium chloride aqueous solution: Weigh 5.549g of calcium chloride, add a small amount of water and dissolve it in a beaker. After completely dissolved, transfer it to a 100ml volumetric flask and dilute to volume to obtain a calcium chloride aqueous solution with a concentration of 0.5mol/L. spare.

分别取14.5g CTAB、14.8ml (0.81g/cm3,12g)正丁醇、75.3ml (0.66g/cm3,49.7g)正己烷和31ml氯化钙水溶液,混合后进行搅拌,待溶液澄清时在室温下静置,得到CaCl2反相微乳液。Take 14.5g CTAB, 14.8ml (0.81g/cm 3 , 12g) n-butanol, 75.3ml (0.66g/cm 3 , 49.7g) n-hexane and 31ml calcium chloride aqueous solution respectively, mix and stir until the solution is clear When left to stand at room temperature, a CaCl 2 reverse microemulsion was obtained.

2)Na2CO3反相微乳液的配制:2) Preparation of Na 2 CO 3 reverse microemulsion:

碳酸钠水溶液的制备:称取5.300g碳酸钠,加少量的水溶解于烧杯中,完全溶解后转移至100ml的容量瓶中定容,得到浓度为0.5mol/L的碳酸钠水溶液,备用。Preparation of sodium carbonate aqueous solution: Weigh 5.300g of sodium carbonate, add a small amount of water and dissolve it in a beaker. After complete dissolution, transfer it to a 100ml volumetric flask and dilute to volume to obtain a sodium carbonate aqueous solution with a concentration of 0.5mol/L for later use.

分别取14.5g CTAB、14.8ml(0.814g/cm3,12g)正己醇、75.3ml (0.66g/cm3,49.7g)正己烷、0.053g蔗糖和90ml碳酸钠水溶液,先将蔗糖溶于碳酸钠水溶液,再将CTAB、正己醇和正己烷与碳酸钠水溶液混合,混合后进行搅拌,待溶液澄清时在室温下静置,得到Na2CO3反相微乳液。Take 14.5g CTAB, 14.8ml (0.814g/cm 3 , 12g) n-hexanol, 75.3ml (0.66g/cm 3 , 49.7g) n-hexane, 0.053g sucrose and 90ml sodium carbonate aqueous solution respectively. Dissolve the sucrose in carbonic acid Sodium aqueous solution, then mix CTAB, n-hexanol and n-hexane with sodium carbonate aqueous solution, stir after mixing, and let it stand at room temperature until the solution is clear, to obtain a Na 2 CO 3 reverse microemulsion.

3)在搅拌下,将上述Na2CO3反相微乳液缓慢加入到CaCl2反相微乳液中,结束后,在室温下静置、陈化24h后进行离心分离。将所得的碳酸钙在80℃的烘箱中烘12h。3) Under stirring, slowly add the above Na 2 CO 3 reverse microemulsion to the CaCl 2 reverse microemulsion. After completion, let it stand at room temperature and age for 24 hours before centrifuging. The obtained calcium carbonate was baked in an oven at 80°C for 12 hours.

实施例2Example 2

方形与簇状共生一体的微米级碳酸钙的制备过程如下:The preparation process of square and clustered micron-sized calcium carbonate is as follows:

1) CaCl2反相微乳液的配制:1) Preparation of CaCl 2 reverse microemulsion:

氯化钙水溶液的制备:称取5.549g氯化钙,加少量的水溶解于烧杯中,完全溶解后转移至100ml的容量瓶中定容,得到浓度为0.5mol/L的氯化钙水溶液,备用。Preparation of calcium chloride aqueous solution: Weigh 5.549g of calcium chloride, add a small amount of water and dissolve it in a beaker. After completely dissolved, transfer it to a 100ml volumetric flask and dilute to volume to obtain a calcium chloride aqueous solution with a concentration of 0.5mol/L. spare.

分别取14.2g CTAB、14.5ml (0.81g/cm3,11.7g)正丁醇、75.5ml (0.66g/cm3,49.8g)正己烷和30ml氯化钙水溶液,混合后进行搅拌,待溶液澄清时在室温下静置,得到CaCl2反相微乳液。Take 14.2g CTAB, 14.5ml (0.81g/cm 3 , 11.7g) n-butanol, 75.5ml (0.66g/cm 3 , 49.8g) n-hexane and 30ml calcium chloride aqueous solution respectively, mix and stir until the solution When clarified, let it stand at room temperature to obtain a CaCl 2 reverse microemulsion.

2)Na2CO3反相微乳液的配制:2) Preparation of Na 2 CO 3 reverse microemulsion:

碳酸钠水溶液的制备:称取5.300g碳酸钠,加少量的水溶解于烧杯中,完全溶解后转移至100ml的容量瓶中定容,得到浓度为0.5mol/L的碳酸钠水溶液,备用。Preparation of sodium carbonate aqueous solution: Weigh 5.300g of sodium carbonate, add a small amount of water and dissolve it in a beaker. After complete dissolution, transfer it to a 100ml volumetric flask and dilute to volume to obtain a sodium carbonate aqueous solution with a concentration of 0.5mol/L for later use.

分别取14.7g CTAB、15.1ml(0.814g/cm3,12.3g)正己醇、75.1ml (0.66g/cm3,49.5g) 正己烷、0.055g蔗糖和92ml碳酸钠水溶液,先将蔗糖溶于碳酸钠水溶液,再将CTAB、正己醇和正己烷与碳酸钠水溶液混合,混合后进行搅拌,待溶液澄清时在室温下静置,得到Na2CO3反相微乳液。Take 14.7g CTAB, 15.1ml (0.814g/cm 3 , 12.3g) n-hexanol, 75.1ml (0.66g/cm 3 , 49.5g) n-hexane, 0.055g sucrose and 92ml sodium carbonate aqueous solution respectively. Dissolve the sucrose in Sodium carbonate aqueous solution, then mix CTAB, n-hexanol and n-hexane with the sodium carbonate aqueous solution, stir after mixing, and let it stand at room temperature until the solution is clear, to obtain a Na 2 CO 3 reverse microemulsion.

3)在搅拌下,将上述Na2CO3反相微乳液缓慢加入到CaCl2反相微乳液中,结束后,在室温下静置、陈化24h后进行离心分离。将所得的碳酸钙在80℃的烘箱中烘12h。3) Under stirring, slowly add the above Na 2 CO 3 reverse microemulsion to the CaCl 2 reverse microemulsion. After completion, let it stand at room temperature and age for 24 hours before centrifuging. The obtained calcium carbonate was baked in an oven at 80°C for 12 hours.

实施例3Example 3

方形与簇状共生一体的微米级碳酸钙的制备过程如下:The preparation process of square and clustered micron-sized calcium carbonate is as follows:

1) CaCl2反相微乳液的配制:1) Preparation of CaCl 2 reverse microemulsion:

氯化钙水溶液的制备:称取5.549g氯化钙,加少量的水溶解于烧杯中,完全溶解后转移至100ml的容量瓶中定容,得到浓度为0.5mol/L的氯化钙水溶液,备用。Preparation of calcium chloride aqueous solution: Weigh 5.549g of calcium chloride, add a small amount of water and dissolve it in a beaker. After completely dissolved, transfer it to a 100ml volumetric flask and dilute to volume to obtain a calcium chloride aqueous solution with a concentration of 0.5mol/L. spare.

分别取14.7g CTAB、15.1ml (0.81g/cm3,12.2g)正丁醇、75.1ml (0.66g/cm3,49.5g)正己烷和32ml氯化钙水溶液,混合后进行搅拌,待溶液澄清时在室温下静置,得到CaCl2反相微乳液。Take 14.7g CTAB, 15.1ml (0.81g/cm 3 , 12.2g) n-butanol, 75.1ml (0.66g/cm 3 , 49.5g) n-hexane and 32ml calcium chloride aqueous solution respectively, mix and stir until the solution When clarified, let it stand at room temperature to obtain a CaCl 2 reverse microemulsion.

2)Na2CO3反相微乳液的配制:2) Preparation of Na 2 CO 3 reverse microemulsion:

碳酸钠水溶液的制备:称取5.300g碳酸钠,加少量的水溶解于烧杯中,完全溶解后转移至100ml的容量瓶中定容,得到浓度为0.5mol/L的碳酸钠水溶液,备用。Preparation of sodium carbonate aqueous solution: Weigh 5.300g of sodium carbonate, add a small amount of water and dissolve it in a beaker. After complete dissolution, transfer it to a 100ml volumetric flask and dilute to volume to obtain a sodium carbonate aqueous solution with a concentration of 0.5mol/L for later use.

分别取14.2g CTAB、14.5ml(0.814g/cm3,11.8g)正己醇、75.5ml (0.66g/cm3,49.8g) 正己烷、0.051g蔗糖和88ml碳酸钠水溶液,先将蔗糖溶于碳酸钠水溶液,再将CTAB、正己醇和正己烷与碳酸钠水溶液混合,混合后进行搅拌,待溶液澄清时在室温下静置,得到Na2CO3反相微乳液。Take 14.2g CTAB, 14.5ml (0.814g/cm 3 , 11.8g) n-hexanol, 75.5ml (0.66g/cm 3 , 49.8g) n-hexane, 0.051g sucrose and 88ml sodium carbonate aqueous solution respectively. Dissolve the sucrose in Sodium carbonate aqueous solution, then mix CTAB, n-hexanol and n-hexane with the sodium carbonate aqueous solution, stir after mixing, and let it stand at room temperature until the solution is clear, to obtain a Na 2 CO 3 reverse microemulsion.

3)在搅拌下,将上述Na2CO3反相微乳液缓慢加入到CaCl2反相微乳液中,结束后,在室温下静置、陈化48h后进行离心分离。将所得的碳酸钙在80℃的烘箱中烘12h。3) Under stirring, slowly add the above Na 2 CO 3 reverse microemulsion to the CaCl 2 reverse microemulsion. After completion, let it stand at room temperature and age for 48 hours before centrifuging. The obtained calcium carbonate was baked in an oven at 80°C for 12 hours.

最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still The technical solutions described in the foregoing embodiments may be modified, or some of the technical features may be equivalently replaced. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (9)

1.一种方形与簇状共生一体的微米级碳酸钙的制备方法,包括以下步骤:1. A method for preparing square and clustered micron-sized calcium carbonate, which includes the following steps: 1) CaCl2反相微乳液的配制:1) Preparation of CaCl 2 reverse microemulsion: 将CTAB、正丁醇、正己烷和氯化钙水溶液混合,配制成CaCl2反相微乳液;Mix CTAB, n-butanol, n-hexane and calcium chloride aqueous solution to prepare a CaCl 2 reverse microemulsion; 2)Na2CO3反相微乳液的配制:2) Preparation of Na 2 CO 3 reverse microemulsion: 将CTAB、正己醇、正己烷、蔗糖和碳酸钠水溶液混合,配制成Na2CO3反相微乳液;Mix CTAB, n-hexanol, n-hexane, sucrose and sodium carbonate aqueous solution to prepare a Na 2 CO 3 reverse microemulsion; 3)按Na2CO3与CaCl2的摩尔比为2~4:1,将Na2CO3反相微乳液加入到CaCl2反相微乳液中,加入完毕后,陈化,得到所述的方形与簇状共生一体的微米级碳酸钙;3) According to the molar ratio of Na 2 CO 3 to CaCl 2 being 2~4:1, add the Na 2 CO 3 reverse microemulsion to the CaCl 2 reverse microemulsion. After the addition is completed, age to obtain the described Square and clustered micron-sized calcium carbonate; 配制CaCl2反相微乳液时,CTAB、正丁醇和正己烷的质量比为0.2~0.3:0.2~0.3:1,正己烷和氯化钙水溶液的体积比为1:0.35~0.45,氯化钙水溶液的浓度为0.3~0.7mol/L;When preparing CaCl2 inverse 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 and calcium chloride aqueous solution is 1:0.35~0.45, and the volume ratio of calcium chloride is 0.2~0.3:0.2~0.3:1. The concentration of aqueous solution is 0.3~0.7mol/L; 配制Na2CO3反相微乳液时,CTAB、正己醇、正己烷和蔗糖的质量比为0.2~0.3:0.2~0.3:1:0.001~ 0.0015,正己烷和碳酸钠水溶液的体积比为1:1.1~1.5,碳酸钠水溶液的浓度为0.3~0.7mol/L。When preparing Na 2 CO 3 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, and the volume ratio of n-hexane and sodium carbonate aqueous solution is 1: 1.1~1.5, the concentration of sodium carbonate aqueous solution is 0.3~0.7mol/L. 2.根据权利要求1所述的制备方法,其特征在于:配制CaCl2反相微乳液时,CTAB、正丁醇和正己烷的质量比为0.25~0.3:0.2~0.26:1,正己烷和氯化钙水溶液的体积比为1:0.37~0.44,氯化钙水溶液的浓度为0.4~0.6mol/L。2. The preparation method according to claim 1, characterized in that: when preparing CaCl2 reverse microemulsion, the mass ratio of CTAB, n-butanol and n-hexane is 0.25~0.3:0.2~0.26:1, and the mass ratio of n-hexane and chlorine is 0.25~0.3:0.2~0.26:1. The volume ratio of calcium chloride aqueous solution is 1:0.37~0.44, and the concentration of calcium chloride aqueous solution is 0.4~0.6mol/L. 3.根据权利要求2所述的制备方法,其特征在于:CTAB、正丁醇和正己烷的质量比为0.28~0.3:0.23~0.26:1,正己烷和氯化钙水溶液的体积比为1:0.41~0.43,氯化钙水溶液的浓度为0.5mol/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, and the volume ratio of n-hexane and calcium chloride aqueous solution is 1: 0.41~0.43, the concentration of calcium chloride aqueous solution is 0.5mol/L. 4.根据权利要求1所述的制备方法,其特征在于:配制Na2CO3反相微乳液时,CTAB、正己醇、正己烷和蔗糖的质量比为0.25~0.3:0.2~0.26:1:0.001~ 0.0013,正己烷和碳酸钠水溶液的体积比为1:1.1~1.4,碳酸钠水溶液的浓度为0.4~0.6mol/L。4. The preparation method according to claim 1, characterized in that: when preparing Na 2 CO 3 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 and sodium carbonate aqueous solution is 1:1.1~1.4, and the concentration of sodium carbonate aqueous solution is 0.4~0.6mol/L. 5.根据权利要求4所述的制备方法,其特征在于:CTAB、正己醇、正己烷和蔗糖的质量比为0.28~0.3:0.23~0.26:1:0.001~ 0.0012,正己烷和碳酸钠水溶液的体积比为1:1.1~1.3,碳酸钠水溶液的浓度为0.5mol/L。5. The preparation method according to claim 4, characterized in that: 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, and the mass ratio of n-hexane and sodium carbonate aqueous solution is The volume ratio is 1:1.1~1.3, and the concentration of sodium carbonate aqueous solution is 0.5mol/L. 6.根据权利要求1所述的制备方法,其特征在于:配制Na2CO3反相微乳液时,先将蔗糖溶于碳酸钠水溶液,再将碳酸钠水溶液与CTAB、正己醇和正己烷混合。6. The preparation method according to claim 1, characterized in that: when preparing the Na 2 CO 3 reverse microemulsion, first dissolve sucrose in the sodium carbonate aqueous solution, and then mix the sodium carbonate aqueous solution with CTAB, n-hexanol and n-hexane. 7.根据权利要求1所述的制备方法,其特征在于:Na2CO3与CaCl2的摩尔比为2.5~3.5:1。7. The preparation method according to claim 1, characterized in that: the molar ratio of Na 2 CO 3 and CaCl 2 is 2.5~3.5:1. 8.根据权利要求7所述的制备方法,其特征在于:Na2CO3与CaCl2的摩尔比为2.7~3.1:1。8. The preparation method according to claim 7, characterized in that: the molar ratio of Na 2 CO 3 and CaCl 2 is 2.7~3.1:1. 9.根据权利要求1所述的制备方法,其特征在于:陈化时间为24~48小时。9. The preparation method according to claim 1, characterized in that: the aging time is 24 to 48 hours.
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CN101580260A (en) * 2009-05-31 2009-11-18 河南大学 Method for preparing amorphous calcium carbonate by microemulsion method
CN102424415A (en) * 2011-09-14 2012-04-25 陕西科技大学 A kind of preparation method of needle bundle micron grade calcium carbonate
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