阅读说明：本技术 一种氯化钙制备亚微细实心球形碳酸钙的方法 (Method for preparing submicron solid spherical calcium carbonate from calcium chloride ) 是由 黄慨 黄绍权 黄志民 顾传君 杨辉 师德强 于 2020-04-24 设计创作，主要内容包括：本发明提出一种氯化钙制备亚微细实心球形碳酸钙的方法,该方法以氯化钙溶液为原料,采用电化学-络合反应技术制备甘氨酸络合钙,再经与CO<Sub>2</Sub>发生碳化反应获得亚微细实心球形碳酸钙。方法中主要通过控制直流电压、络合反应温度、络合反应pH值、碳化反应温度、CO<Sub>2</Sub>流速、碳化电导率等条件来实现制备亚微细实心球形碳酸钙,本发明解决了矿山尾矿石或大理石边角剩余物的回收利用问题,是实现“重质碳酸钙回收——钙质纯化——制备功能化碳酸钙”重要手段,主要特点是利用废弃剩余物、无高温煅烧、利用清洁能源、CO<Sub>2</Sub>实现生态内循环,是一种清洁生产亚微细实心球形碳酸钙粉体材料的方法。实现碳酸钙产业的高效综合利用,并解决制约碳酸钙产业发展的生态环保问题。(The invention provides a method for preparing submicron solid spherical calcium carbonate by calcium chloride, which takes calcium chloride solution as raw material, adopts electrochemical-complexation reaction technology to prepare glycine complexed calcium, and then reacts with CO 2 Carbonization reaction is carried out to obtain the submicron solid spherical calcium carbonate. The method mainly comprises the steps of controlling direct current voltage, complexation reaction temperature, complexation reaction pH value, carbonization reaction temperature and CO 2 The invention realizes the preparation of submicron solid spherical calcium carbonate under the conditions of flow velocity, carbonization conductivity and the like, solves the problem of recycling mine tailing stones or marble leftover residues, is an important means for realizing 'heavy calcium carbonate recycling-calcium purification-preparation of functional calcium carbonate', and is mainly characterized in that waste residues are utilized, high-temperature calcination is not carried out, clean energy and CO are utilized 2 Realizes ecological internal circulation, and is a method for cleanly producing submicron solid spherical calcium carbonate powder materials. Realizes the high-efficiency comprehensive utilization of the calcium carbonate industry and solves the ecological environmental protection problem which restricts the development of the calcium carbonate industry.)

1. A method for preparing submicron solid spherical calcium carbonate by calcium chloride is characterized by comprising the following steps: taking calcium chloride solution as a raw material, and reacting to obtain glycine by regulating and controlling the direct current voltage, pH value and complexing temperature reaction conditions of electrochemical-complexing reaction under the auxiliary action of glycine and an accelerantComplexing calcium solution; CO by controlling carbonization₂Reaction conditions of flow rate, carbonization conductivity and carbonization temperature are adopted to complex calcium glycinate with CO₂Carbonizing reaction, and separating and drying to obtain submicron solid spherical calcium carbonate powder.

2. The method for preparing submicron solid spherical calcium carbonate with calcium chloride according to claim 1, wherein: the calcium chloride solution is obtained by treating residues of calcium-containing base materials through a hydrometallurgical process, wherein the residues of the calcium-containing base materials are any one or any combination of high-quality marble residual materials, high-quality limestone residual materials and seafood shell residual materials.

3. The method for preparing submicron solid spherical calcium carbonate with calcium chloride according to claim 1, wherein: the accelerator is any one of potassium glycinate and sodium glycinate or any combination thereof.

4. The method for preparing submicron solid spherical calcium carbonate with calcium chloride according to claim 1, wherein: the regulation and control conditions of the electrochemical-complexation reaction are as follows: the direct current voltage is 12-36V, pH, the value is 12-13, and the complexing temperature is 25-40 ℃.

5. The method for preparing submicron solid spherical calcium carbonate by calcium chloride according to claim 1, wherein: the regulation and control conditions of the carbonization reaction are as follows: CO 2₂The flow rate is 500-1500 ml/min, the carbonization conductivity is 200-400 mu s/cm, and the carbonization temperature is 20 +/-5 ℃.

6. The method for preparing submicron solid spherical calcium carbonate with calcium chloride according to claim 1, wherein: the electrochemical-complexing reaction system is composed of an anion-cation exchange membrane and is divided into three parts, wherein the three parts comprise a cathode chamber, an anode chamber and a complexing chamber, the cathode chamber and the complexing chamber are separated by the anion-exchange membrane, the anode chamber and the complexing chamber are separated by the cation-exchange membrane, and the complexing chamber is positioned between the cathode chamber and the anode chamber.

7. The method for preparing submicron solid spherical calcium carbonate with calcium chloride according to claim 6, wherein: the electrolyte in the cathode chamber is 10-15% of potassium hydroxide or sodium hydroxide solution; the electrolyte in the anode chamber is a calcium chloride solution with the mass concentration of 2.2-6.0 mol/L.

8. The method for preparing submicron solid spherical calcium carbonate with calcium chloride according to claim 1, wherein: the dosage of the glycine and the accelerator is as follows according to a molar ratio of 1: 0.1 to 0.5.

Technical Field

The invention is applied to the technical fields of micron-sized powder processing, electrodialysis, electrolytic hydrogen production and the like, and is used for preparing submicron solid spherical calcium carbonate and hydrogen.

Background

Spherical calcium carbonate is one of a plurality of specific calcium carbonates, has the outstanding characteristics of good fluidity, dispersibility, smoothness, large specific surface area, small density and the like, has a simple structure, small stacking volume, low oil absorption value, good smoothness and fluidity, high covering degree and strong ink absorbability, and is mainly used in the fields of papermaking, coatings, printing ink, lubricating oil, electronic ceramics and the like. In the papermaking industry, the spherical calcium carbonate has little difference with light calcium carbonate and heavy calcium carbonate used in paper in the aspects of whiteness, folding resistance, bulk, tensile strength retention rate and the like, but has the minimum reduction in tensile strength, only has low sizing degree and needs to be further researched and improved. Spherical calcium carbonate may perform well in the printing of paper; in the plastic rubber industry, the spherical calcium carbonate has better reinforcing property. The spherical calcium carbonate formed by the nano aggregates is depolymerized under the action of high temperature and high shear force, particles can be better dispersed in a matrix, the interface acting force is increased, and the bearable load is increased; in the coating industry, the spherical calcium carbonate can partially or completely replace the existing heavy and light calcium pigment and filler in the coating, so that the coating has a larger space for reducing the coating cost, and particularly the covering power and the brushing resistance of the fineness of the spherical calcium carbonate are worth paying attention; in the ink industry, the calcium carbonate special for ink is generally spherical or cubic ultrafine calcium carbonate subjected to activation treatment. Has the advantages of good stability, high glossiness, strong adaptability and the like. In the field of electronic ceramics, the functional filler can be applied to electronic ceramic products, such as PTC thermistors, MLCC chip capacitors, semiconductor ceramic capacitors, ceramic substrates and the like; in addition, the spherical calcium carbonate added into the lubricating oil can also play a role of a nano bearing, so that the lubricating property and the compression resistance of the nano bearing are greatly improved. Thus, the submicron solid spherical calcium carbonate prepared herein is expected to have better applications in the fields of paper making and lubrication (e.g., toothpaste).

The spherical calcium carbonate has a simple structure but the shape is difficult to control, and the method for preparing the spherical calcium carbonate with ideal appearance and simple operation is a hotspot of current research. The particle size of the superfine calcium carbonate is between 100 and 1000nm, the particle size of the spherical calcium carbonate obtained by the method is between 1000 and 5000nm, the spherical calcium carbonate is temporarily called submicron solid spherical calcium carbonate, and the application of the submicron solid spherical calcium carbonate is close to that of the superfine spherical calcium carbonate.

The preparation method of the spherical calcium carbonate mainly comprises a carbonization method, a double decomposition method, a micro-emulsion method, a sol-gel method and the like. It is often necessary to control both the process conditions and additives to control the morphology. Several major preparation methods are now aligned as shown in table 1.

TABLE 1 comparison of preparation methods of submicron spherical calcium carbonate

The Chinese patent application with publication number CN103628124A discloses a low-voltage direct-current electrolytic preparation method of calcium carbonate whiskers, which prepares a calcium salt solution by taking an inorganic calcium salt as a solute; preparing alkali liquor by using carbonate as a solute; the calcium carbonate material is prepared by taking inorganic magnesium salt as solute to prepare a crystal form control agent solution, and has obvious whisker characteristics.

In recent years, with the rapid development of the heavy calcium industry, the annual production of marble has been enormous. Because the development and utilization of the coarse whiting have high requirements on the quality of raw ores, a large amount of mine stripping substances, stone processing waste slurry and granite processing waste residues are generated in the marble mining process, and the environmental protection pressure is huge unprecedentedly. According to incomplete statistics, taking Hezhou as an example, the annual wasteland amount is 1200 ten thousand tons, the available amount is only 50 percent, and the residues of low-grade stones (soil), leftover materials and the like newly generated in the year are about 400 ten thousand tons; the storage amount of the plate and the artware processing waste slurry is up to 300 ten thousand tons, and 40 ten thousand tons of waste slurry is newly produced every year; the agglomerated stone production line produces 400 tons of waste residues per month, and the accumulated year of each production line produces approximately 60 million tons of waste residues.

As the industrial scale has increased, the solid waste disposal problem from calcium carbonate processing has risen to government level. In recent years, hundreds of millions of yuan has been put into congratulation state markets to establish a waste discharge area, the current situation of random stacking is stopped to a certain extent, the problem of marble waste utilization is not fundamentally solved, and how to solve resource utilization of marble and calcium-based waste and realize high-value application becomes urgent needs and attention hot spots of the industry. The invention fully considers the problems and the difficulty of producing the submicron calcium carbonate by replacing limestone with heavy calcium processing residues, namely, the heavy calcium carbonate can not obtain the characteristics of calcium oxide through direct calcination, so the method for preparing the submicron calcium carbonate by extracting the calcium-based soluble concentrated solution through a wet method gives consideration to the technical requirements of clean production and secondary emission reduction, and provides the method for preparing the submicron solid spherical calcium carbonate by calcium chloride.

Disclosure of Invention

In order to solve the technical problems, the invention provides a method for preparing submicron solid spherical calcium carbonate by calcium chloride, which aims at the technical route of preparing submicron calcium carbonate by a wet method and solves the problems of preparing submicron calcium carbonate by solid wastes in the heavy calcium industry. Realizes the high-efficiency comprehensive utilization of the calcium carbonate industry and solves the ecological environmental protection problem which restricts the development of the calcium carbonate industry.

In order to realize the purpose, the following technical scheme is provided:

a method for preparing submicron solid spherical calcium carbonate by calcium chloride uses calcium chloride solution as raw material, and reacts to obtain glycine complex calcium solution by regulating and controlling the direct current voltage, pH value and complexing temperature reaction conditions of electrochemical-complexing reaction under the auxiliary action of glycine and an accelerant; CO by controlling carbonization₂Reaction conditions of flow rate, carbonization conductivity and carbonization temperature are adopted to complex calcium glycinate with CO₂Carbonizing reaction, and separating and drying to obtain submicron solid spherical calcium carbonate powder.

The technical principle is as follows:

and (3) anode reaction:

2Cl^--2e→Cl₂

and (3) cathode reaction:

2H₂O+2e→H₂+2OH^-

and (3) carbonization reaction:

Ca²⁺+CO₂+2OH^-→CaCO₃+H₂O

the general reaction formula is as follows:

Ca²⁺+CO₂+2Cl^-+H₂O→CaCO₃+Cl₂+H₂

further, the calcium chloride solution is obtained by processing residues of calcium-containing base materials through a hydrometallurgical process, wherein the residues of the calcium-containing base materials are any one or any combination of high-quality marble residual materials, high-quality limestone residual materials and seafood shell residual materials.

Further, the accelerator is any one of potassium glycinate and sodium glycinate or any combination thereof.

Further, the regulation and control conditions of the electrochemical-complexation reaction are as follows: the direct current voltage is 12-36V, pH, the value is 12-13, and the complexing temperature is 25-40 ℃.

Further, the regulation and control conditions of the carbonization reaction are as follows: CO 2₂The flow rate is 500-1500 ml/min, the carbonization conductivity is 200-400 mu s/cm, and the carbonization temperature is 20 +/-5 ℃. The CO is₂The purity of (A) is more than 99.9%.

Furthermore, the system of the electrochemical-complexation reaction is composed of an anion-cation exchange membrane and is divided into three parts, wherein the three parts comprise a cathode chamber, an anode chamber and a complexation chamber, the cathode chamber and the complexation chamber are separated by the anion-exchange membrane, the anode chamber and the complexation chamber are separated by the cation-exchange membrane, and the complexation chamber is positioned between the cathode chamber and the anode chamber.

Further, the electrolyte in the cathode chamber is 10% -15% of potassium hydroxide or sodium hydroxide solution; the electrolyte in the anode chamber is a calcium chloride solution with the mass concentration of 2.2-6.0 mol/L.

Further, the glycine and the accelerator are used in a molar ratio of 1: 0.1 to 0.5.

The invention has the following advantages and positive effects:

(1) the invention adopts marble and calcium-based waste resource utilization, takes calcium chloride solution obtained by wet extraction and purification as raw material, and adopts an electrochemical auxiliary method to prepare the submicron solid spherical calcium carbonate, thereby realizing high-efficiency comprehensive utilization of the calcium carbonate industry and solving the ecological environmental protection problem restricting the development of the calcium carbonate industry.

(2) The technology of the invention is different from the prior raw materials, and the calcium source is provided in the carbonization process, the traditional technology is provided by dissolving calcium hydroxide slurry, and the technology is provided by the continuous electromigration of calcium chloride in an anode chamber.

(3) The co-product of the invention, namely hydrogen and chlorine, is respectively an important clean energy and an industrial raw material, fully utilizes the electric energy consumed by electrolysis, and indirectly reduces the production cost for preparing the submicron solid spherical calcium carbonate.

(4) The promoter and the glycine only serve as a stability control agent in the reaction system and can be completely recycled.

(5) The invention can also be expanded to other fields of preparing micron-grade or submicron-grade powder materials by using soluble metal salt solution, and is a method for efficiently and cleanly producing submicron-grade powder materials.

Drawings

FIG. 1 is a schematic view of the process for preparing submicron solid spherical calcium carbonate according to the present invention.

Fig. 2 is an XRD detection pattern of the calcium carbonate powder of example 1.

FIG. 3 is a photograph of the calcium carbonate powder of example 1 under a field emission scanning electron microscope of 50 μm.

FIG. 4 is a photograph of the calcium carbonate powder of example 1 under a field emission scanning electron microscope of 4 μm.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present application, the following will clearly and completely describe the technical solutions in the present application with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and all other embodiments obtained by a person of ordinary skill in the art without making creative efforts based on the embodiments in the present application shall fall within the protection scope of the present application.

Preparing raw materials: carrying out back extraction on the solution containing high-concentration chloride ions and the residues of the calcium-containing base materials through wet extraction liquid, and concentrating to obtain a calcium chloride solution with the concentration of 2.2-6.0 mol/L; the calcium-containing base material residue is heavy calcium carbonate tailing ore or marble leftover material or seafood shell residue material, or the mixture of the above materials.

Constructing an electrochemical-complex reaction system: the system is composed of an anion-cation exchange membrane and is divided into three parts, wherein the three parts comprise a cathode chamber, an anode chamber and a complexing chamber, the cathode chamber and the complexing chamber are separated by the anion-exchange membrane, the anode chamber and the complexing chamber are separated by the cation-exchange membrane, and the complexing chamber is positioned between the cathode chamber and the anode chamber.