Preparation method of superfine BaSO4 / TiO2 composite material

Abstract

This invention belongs to the field of barium sulfate compounds, specifically relating to a method for preparing ultrafine BaSO4 / TiO2 composite materials. The method includes: Step 1: adding a composite modifier to barium carbonate slurry, then adding Na2SO4 solution, and performing an ultrasonic reaction; Step 2: adding titanium oxysulfate, continuing the ultrasonic reaction, filtering, washing, and drying to obtain the ultrafine BaSO4 / TiO2 composite material. This invention utilizes titanium dioxide generated from the hydrolysis of titanium oxysulfate to directly coat ultrafine barium sulfate particles modified with a composite surfactant. The process is simple, resource-recycling is possible, it is economical and environmentally friendly with no waste generation, and it can effectively control the size and properties of the ultrafine barium sulfate, making it suitable for industrial production applications.

Description

Technical Field

[0001] This invention belongs to the field of barium sulfate compounds, specifically relating to a method for preparing an ultrafine BaSO4 / TiO2 composite material. Background Technology

[0002] Barium sulfate is widely used in coatings, inks, rubber, pharmaceuticals, plastics, textiles, drilling, and other fields due to its advantages such as high whiteness, high chemical stability, abundant resources, and low price. In recent years, with the continuous upgrading of products in various application fields, ordinary barium sulfate, due to its large particle size, uneven distribution, limited surface properties, high impurity content, and large batch-to-batch variability, can no longer meet product requirements. Efforts are being made to develop ultrafine functional barium sulfate preparation technologies that meet market demands and establish high-value-added barium sulfate micron powder production lines, thereby enhancing my country's market competitiveness in barium sulfate.

[0003] Patent document CN106976900B discloses a method for preparing barium sulfate by reacting barite (calcined and reduced to barium sulfide) with a solution of sodium sulfate (after removing impurities such as calcium and magnesium). The method further modifies the surface of the newly formed barium sulfate crystal nuclei using surface modification and the dispersant sodium stearate. A surface modifier polymer is then used to further modify the surface of the barium sulfate particles, enabling them to effectively combine with organic polymers in powder coatings and disperse well in the coating. The barium sulfate prepared by this method produces powder coatings with advantages such as high whiteness, good leveling properties, and uniform dispersion. Patent document CN103881418B discloses a method for preparing barium sulfate particles with a particle size of 10-1000 nm using barium sulfate slurry as raw material, with the addition of lubricants, modifiers, dispersants, coupling agents, heat stabilizers, and antioxidants. Patent document CN101418140B discloses a synthesis reaction of barium carbonate, sulfuric acid solution, and a separating agent. The resulting barium sulfate powder suspension is then ripened, separated, washed, slurried, and subjected to surface modification treatment before drying to obtain the finished product. However, the above technology involves complex processes, high equipment investment, and is not easily industrialized. Therefore, there is an urgent need to develop a simple and easily industrially applicable ultrafine functional barium sulfate preparation technology. Summary of the Invention

[0004] To address the technical problems existing in the prior art, the present invention provides a method for preparing surfactant-modified ultrafine BaSO4 / TiO2 composite materials that is simple to process, recyclable in resources, environmentally friendly, and easy to industrialize.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] A method for preparing an ultrafine BaSO4 / TiO2 composite material includes the following steps:

[0007] Step 1: Add a composite modifier to the barium carbonate slurry, then add Na2SO4 solution and sonicate.

[0008] Step 2: Add titanium oxysulfate, continue the ultrasonic reaction, filter, wash, and dry to obtain the ultrafine BaSO4 / TiO2 composite material.

[0009] The preparation reaction formula of the method is as follows:

[0010] BaCO3 + Na2SO4 = BaSO4 + Na2CO3 (1)

[0011] TiOSO4 + H2O = TiO2 + H2SO4 (2)

[0012] BaCO3 + H2SO4= BaSO4 +H2O+CO2 (3)

[0013] Na2CO3 + H2SO4= Na2SO4 +H2O+CO2 (4)

[0014] Preferably, in step 1, the mass concentration of barium carbonate slurry is 30%.

[0015] Preferably, in step 1, the composite modifier is a composite surface modifier obtained by compounding glycoside citrate APG-EC and narrow-distribution fatty alcohol polyoxyethylene ether AEO9, monoalkyl dimethyl hydroxyethyl ammonium chloride or narrow-distribution AEO9 sulfosuccinate disodium salt in a mass ratio of 1:1 to 1:3.

[0016] Preferably, in step 1, the amount of composite modifier added is 1‰ to 5‰ of the barium carbonate content.

[0017] Preferably, in step 1, the molar ratio of barium carbonate to sodium sulfate is 1:1 to 1:1.5.

[0018] Preferably, in step 1, the mass concentration of the Na2SO4 solution is 20% to 40%.

[0019] Preferably, in step 1, the power of the ultrasonic reaction is 1000W to 2000W, the reaction temperature is 30℃ to 50℃, and the reaction time is 2h to 8h.

[0020] Preferably, in step 2, the amount of titanium oxysulfate is 0.05-0.5 times the amount of barium carbonate.

[0021] Preferably, in step 2, the ultrasonic reaction power is 500-1000W, the reaction temperature is 30℃~50℃, and the reaction time is 0.5h~1h.

[0022] Preferably, in step 2, the particle size of the ultrafine BaSO4 / TiO2 composite material is 100 nm to 300 nm, the whiteness is 95% to 98%, and the specific surface area is 20 to 50 g / cm³. 2 .

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] This invention uses inorganic titanium dioxide to coat ultrafine barium sulfate particles, and adds a composite surfactant to modify the ultrafine BaSO4 / TiO2 composite material. On the one hand, the high whiteness of titanium dioxide can solve the problem of low whiteness of barium sulfate as a pigment. On the other hand, the large specific surface area of ​​titanium dioxide can improve the shortcomings of the small specific surface area of ​​ultrafine barium sulfate, thus improving the problem of small addition amount in the application process.

[0025] This invention utilizes the hydrolysis of titanium oxysulfate to produce titanium dioxide, which is then directly coated onto ultrafine barium sulfate particles modified with a composite surfactant. The resulting sulfuric acid, a byproduct, converts unreacted barium carbonate into barium sulfate, increasing the conversion rate. Simultaneously, it reacts with sodium carbonate, another byproduct, to produce sodium sulfate, which can then be used as a raw material for barium sulfate production, thus achieving resource recycling. Furthermore, the added composite surfactant effectively controls the uneven particle size distribution and agglomeration of the ultrafine BaSO4 / TiO2 composite material, thereby effectively regulating the concentrated distribution of small particles in a monodisperse state. Simultaneously, the cavitation effect of ultrasound during the preparation process effectively increases the conversion rate from barium carbonate to barium sulfate. This method is simple, resource-recycling, economical, environmentally friendly, and generates no waste. It also achieves effective control over the size and properties of ultrafine BaSO4 / TiO2, making it suitable for industrial production applications. Detailed Implementation

[0026] To facilitate understanding of the present invention, a more comprehensive description will be given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0027] Example 1

[0028] 60g of barium carbonate was weighed and added to 140ml of distilled water to prepare a 30% slurry. 0.3g (5‰) of a composite surfactant (obtained by compounding glycoside citrate (APG-EC) and narrow-distribution fatty alcohol polyoxyethylene ether AEO9 in a 1:1 mass ratio) was added, followed by a 20% Na₂SO₄ solution. The molar ratio of barium carbonate to sodium sulfate was 1:1. The reaction was carried out at 30℃ for 2 hours under ultrasonic treatment at 1000W power. Then, titanium oxysulfate (0.05 times the amount of barium carbonate) was directly added, and the reaction was continued under ultrasonic treatment at 500W power for 0.5 hours. The filtrate was concentrated, and the Na₂SO₄ recovery rate reached 85%, which could be used for the recycling of the reaction raw material sodium sulfate. The product was filtered, washed, and dried at 110℃ to obtain an ultrafine BaSO₄ / TiO₂ composite material with a particle size of 100nm±10nm, a whiteness Wr of 95.5%, and a specific surface area S. BET 50g / cm 2 .

[0029] Example 2

[0030] 60g of barium carbonate was weighed and added to 140ml of distilled water to prepare a 30% slurry. 0.6g of a composite surfactant (obtained by compounding glycoside citrate (APG-EC) and monoalkyl dimethyl hydroxyethyl ammonium chloride in a mass ratio of 1:2) was added, followed by a 40% Na₂SO₄ solution. The molar ratio of barium carbonate to sodium sulfate was 1:1.5. The reaction was carried out at 50℃ for 8 hours under ultrasonic treatment at a power of 2000W. Then, titanium oxysulfate (0.5 times the amount of barium carbonate) was directly added, and the reaction was continued under ultrasonic treatment at a power of 1000W for 1 hour. The filtrate was concentrated, and the Na₂SO₄ recovery rate reached 90%, which could be used for the recycling of the reaction raw material sodium sulfate. The product was filtered, washed, and dried at 110℃ to obtain an ultrafine BaSO₄ / TiO₂ composite material with a particle size of 300nm ± 20nm, a whiteness Wr of 96%, and a specific surface area S. BET 30g / cm 2 .

[0031] Example 3

[0032] 60g of barium carbonate was weighed and added to 140ml of distilled water to prepare a 30% slurry. 0.4g of a composite surfactant (obtained by compounding glycoside citrate (APG-EC) and narrow-distribution fatty alcohol polyoxyethylene ether AEO9 at a mass ratio of 1:3) was added, followed by a 30% Na₂SO₄ solution. The molar ratio of barium carbonate to sodium sulfate was 1:1.4. The reaction was carried out at 40℃ for 6 hours under ultrasonic treatment at a power of 1500W. Then, titanium oxysulfate (0.1 times the amount of barium carbonate) was directly added, and the reaction was continued under ultrasonic treatment at 800W for 1 hour. The filtrate was concentrated, and the Na₂SO₄ recovery rate reached 90%, allowing for the recycling of the reactant sodium sulfate. The product was filtered, washed, and dried at 110℃ to obtain an ultrafine BaSO₄ / TiO₂ composite material with a particle size of 150nm ± 10nm, a whiteness (Wr) of 97%, and a specific surface area (S). BET 48g / cm 2 .

[0033] Example 4

[0034] 60g of barium carbonate was weighed and added to 140ml of distilled water to prepare a 30% slurry. 0.5g of a composite surfactant (obtained by compounding glycoside citrate (APG-EC) and disodium sulfosuccinate of narrow-distribution AEO9 at a mass ratio of 1:2) was added, followed by a 35% Na₂SO₄ solution. The molar ratio of barium carbonate to sodium sulfate was 1:1.2. The reaction was carried out at 50℃ for 7 hours under ultrasonic treatment at 2000W. Then, titanium oxysulfate (0.3 times the amount of barium carbonate) was directly added, and the reaction was continued under ultrasonic treatment at 1000W for 0.8 hours. The filtrate was concentrated, and the Na₂SO₄ recovery rate reached 92%, allowing for the recycling of the reactant sodium sulfate. The product was filtered, washed, and dried at 110℃ to obtain an ultrafine BaSO₄ / TiO₂ composite material with a particle size of 200nm ± 10nm, a whiteness (Wr) of 98%, and a specific surface area (S). BET 40g / cm 2 .

[0035] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing an ultrafine BaSO4 / TiO2 composite material, characterized in that, Includes the following steps: Step 1: Add a composite modifier to the barium carbonate slurry, then add Na2SO4 solution and sonicate. Step 2: Add titanium oxysulfate, continue the ultrasonic reaction, filter, wash, and dry to obtain the ultrafine BaSO4 / TiO2 composite material; In step 1, the composite modifier is a composite surface modifier obtained by compounding glycoside citrate APG-EC and narrow-distribution fatty alcohol polyoxyethylene ether AEO9, monoalkyl dimethyl hydroxyethyl ammonium chloride or narrow-distribution AEO9 sulfosuccinate disodium salt in a mass ratio of 1:1 to 1:

3.

2. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 1, the mass concentration of barium carbonate slurry is 30%.

3. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 1, the amount of composite modifier added is 5‰ to 1% of the barium carbonate content.

4. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 1, the molar ratio of barium carbonate to sodium sulfate is 1:1 to 1:1.

5.

5. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 1, the mass concentration of the Na2SO4 solution is 20%~40%.

6. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 1, the power of the ultrasonic reaction is 1000W~2000W, the reaction temperature is 30℃~50℃, and the reaction time is 2h-8h.

7. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 2, the amount of titanium oxysulfate is 0.05-0.5 times the amount of barium carbonate.

8. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 2, the ultrasonic reaction power is 500-1000W, the reaction temperature is 30℃~50℃, and the reaction time is 0.5h~1h.

9. The method for preparing an ultrafine BaSO4 / TiO2 composite material according to claim 1, characterized in that, In step 2, the particle size of the ultrafine BaSO4 / TiO2 composite material is 100nm~300nm, the whiteness is 95%~98%, and the specific surface area is 20~50g / cm². 2 .