Preparation method of BaSO4 with hollow strip-shaped structure
By using nano-carbon colloidal particles or carbon tar as a carrier and combining it with surfactants to prepare hollow strip-shaped BaSO4, the problem of difficulty in forming hollow porous structures at room temperature has been solved, enabling the material to be widely used in multiple fields.
Patent Information
- Application Number
- CN202511730918.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-24
- Publication Date
- 2026-02-06
AI Technical Summary
Existing technologies make it difficult to form BaSO4 with a hollow porous structure at room temperature using traditional precipitation methods.
Hollow strip-shaped BaSO4 structures were prepared by using nano-carbon colloidal particles or carbon tar as barium ion carriers and polyvinylpyrrolidone (PVP) as a surfactant, and by controlling the pH value and gradually adding sodium sulfate solution.
The prepared BaSO4 material has a significant hollow nanostructure, good compatibility, and is widely used in medical, nuclear construction and industrial papermaking fields.
Smart Images
Figure CN121470529A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of synthesis of multipurpose and multifunctional nanometer metal compound materials, and particularly relates to a preparation method of BaSO4 with an internal hollow strip structure. BACKGROUND
[0002] As a multifunctional metal inorganic compound material, BaSO4 is indispensable in many industries due to its chemical stability and high density characteristics. Therefore, BaSO4 is widely used in medical X-ray contrast, industrial fillers, oil drilling mud weighting agents, radiation shielding materials and special field applications.
[0003] The internal hollow structure changes the X and gamma ray absorption capacity of BaSO4, so that the material can be diversified and applied to medical protective clothing, nuclear power plant protection facilities, etc. As an industrial filler, BaSO4 can improve the whiteness of paper in papermaking, and the design of the internal hole structure controls the weight of the paper while ensuring the whiteness of the paper, improving the applicability of the paper.
[0004] However, the design of the internal hollow porous structure is difficult to form by the traditional precipitation method at room temperature. SUMMARY
[0005] The present application aims to at least solve one of the technical problems existing in the prior art, and provides a preparation method of BaSO4 with an internal hollow strip structure.
[0006] The technical solution of the present application is as follows: In a first aspect, the present application provides a preparation method of BaSO4 with an internal hollow strip structure, comprising the following steps: Mixing a barium ion compound with a nanometer carbon colloidal particle solution or carbon tar, adding an acid to maintain the pH of the system less than 7, adding a surfactant, and gradually adding a sodium sulfate aqueous solution under continuous stirring to form flocculation or precipitate, thereby preparing BaSO4 with an internal hollow strip structure.
[0007] In the method of the present application, the principle is to use nanometer carbon colloidal particles or carbon tar as a barium ion carrier. The nanometer carbon colloidal particle solution or carbon tar is dispersed in water in the form of a micro-particle that is easy to disperse. The carbon surface is rich in oxygen functional groups, which form a bond with metal ions to form an integral whole. The carbon surface functional groups act as tentacles and combine with polyvinylpyrrolidone (PVP) to form a bond, promoting the stable and rapid formation of BaSO4 nanomaterials. Under the action of metal ion bonding, the formation of BaSO4 metal compounds with an internal hollow strip structure is driven. The BaSO4 material prepared under these conditions has a significant internal hollow nanostructure, good compatibility, and other advantages, and can be widely used in medical, nuclear construction, and industrial papermaking, etc. fields, and has great development prospects.
[0008] As a further preferred embodiment, the preparation method of the nanometer carbon colloidal particle solution comprises: Dissolve lithium hydroxide or sodium hydroxide in water to form an electrolyte, add a carbon source to the electrolyte, electrolyze the electrolyte by taking a platinum metal sheet as a counter electrode, centrifugal filtration, collect the red supernatant to obtain a nanometer carbon colloidal particle solution.
[0009] As a further preferred embodiment, in the preparation method of the nanometer carbon colloidal particle solution, the concentration of the electrolyte is 1 M, the carbon source is ethanol, the volume ratio of the electrolyte to the carbon source is 60:15, the voltage of the electrolysis is 15 V, and the electrolysis time is 3 h~5 h.
[0010] As a further preferred embodiment, the preparation method of the carbon tar comprises: After dissolving glucose in water, react and carbonize at 130 ℃~220 ℃ for 10 h~30 h, then centrifugal filtration, separate the supernatant to obtain carbon tar; Wherein, the adding ratio of glucose to water is 3g:30 mL~5g:60 mL.
[0011] A preparation method of an inner hollow bar structure BaSO4, comprising the following specific steps: In an oil bath at 30 ℃~80 ℃, the nanometer carbon colloidal particle solution or the carbon tar is dispersed in deionized water by continuous ultrasonic and stirring, an acid is added to make the solution acidic, a barium ion compound is dissolved in deionized water to form a metal ion solution, an aqueous solution containing a surfactant is added, and a sodium sulfate solution is added dropwise in the process of continuous stirring to form gray flocculation, centrifugal, collect the precipitate to obtain an inner hollow bar structure BaSO4 metal compound.
[0012] As a further preferred embodiment, the concentration of the above-mentioned barium ion compound (metal ion solution) is 0.1 M~2 M. Wherein, the barium ion compound is one of barium chloride and barium hydroxide.
[0013] As a further preferred embodiment, the concentration of the sodium sulfate solution is 0.15 M~2 M, and the molar mass ratio of the above-mentioned metal ion to sodium sulfate is 1:1~1:30.
[0014] As a further preferred embodiment, the acid is one of hydrochloric acid and acetic acid.
[0015] As a further preferred embodiment, the concentration of the aqueous solution containing a surfactant is 0.05 g / L~20 g / L.
[0016] As a further preferred embodiment, the barium ion compound and the polyvinylpyrrolidone are added in a ratio of 10 mmol to 20 mmol: 1.0 g to 2.0 g.
[0017] As a further preferred embodiment, the surfactant is polyvinylpyrrolidone, and the molecular weight of the polyvinylpyrrolidone is 54,000.
[0018] In a second aspect, the present application provides an inner hollow strip-shaped structure BaSO4, which is obtained by the preparation method.
[0019] The inner hollow strip-shaped structure BaSO4 prepared by the present application has the advantages of high specific surface area, large pore volume, good compatibility, etc., and can be widely used in medical treatment, nuclear construction, industrial papermaking and many other fields, and has great development prospects.
[0020] In a third aspect, the present application provides the use of the inner hollow strip-shaped structure BaSO4 in the preparation of medical products or nuclear construction products or industrial papermaking.
[0021] The present application has at least one of the following beneficial effects: The present application provides a simple and stable synthesis method for preparing an inner hollow porous strip-shaped BaSO4, and the prepared material can be used in medical treatment, nuclear construction, papermaking and other fields. The method mainly uses nano carbon colloidal particles or carbon tar as a barium ion carrier, and polyvinylpyrrolidone (PVP) as a surfactant to prepare an inner hollow porous strip-shaped BaSO4 metal compound. BRIEF DESCRIPTION OF DRAWINGS
[0022] Figure 1 The figure shows a digital photo graph of a nano carbon colloidal particle aqueous solution prepared by electrolyzing ethanol with a LiOH alkaline solution in Example 1 (Figure A) and its TEM graph (Figure B).
[0023] Figure 2 The figure shows a digital photo graph of a soluble carbon dot aqueous solution prepared by high-temperature and high-pressure hydrothermal treatment of a glucose aqueous solution in Example 2 (Figure A) and a transmission electron microscope graph (TEM) (Figure B).
[0024] Figure 3 The figure shows a digital photo graph of a soluble carbon dot aqueous solution prepared by high-temperature and high-pressure hydrothermal treatment of a glucose aqueous solution in Example 3 (Figure A) and a transmission electron microscope graph (TEM) (Figure B).
[0025] Figure 4 The figure shows a digital photo graph of carbon tar obtained after drying the soluble carbon dots of Example 2 and Example 3.
[0026] Figure 5A scanning electron microscope (SEM) (Figure A), a transmission electron microscope (TEM) (Figure B-C) and an X-ray energy spectrum element analysis (EDS) (Figure D-E) of the BaSO4 metal compound obtained in Example 1 are shown.
[0027] Figure 6 A SEM (Figure A), EDS (Figure B-C) and X-ray energy spectrum element analysis (EDS) (Figure D-E) of the BaSO4 metal compound obtained in Example 2 are shown.
[0028] Figure 7 A SEM of the BaSO4 metal compound obtained in Example 3 is shown. DETAILED DESCRIPTION
[0029] In order to make the technical problems solved by the present application, technical solutions and beneficial effects more clearly understood, the present application will be further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.
[0030] Example 1 A preparation method of BaSO4 with an inner hollow strip structure, specifically comprising the following steps: (1) Preparation of a water-soluble nano-carbon colloidal particle solution: A 500 mL 1 M LiOH aqueous solution was prepared, 60 mL of the 1 M LiOH aqueous solution was removed as an electrolyte, 15 mL of ethanol was added as a carbon source, and two 1.5 cm*1.5 cm platinum metal foils were used as counter electrodes to electrolyze ethanol at a voltage of 15 V for 3 h. The brown-red transparent water-soluble nano-carbon colloidal particle solution was separated and extracted by high-speed centrifugation and filter paper filtration, and a physical map of the brown-red transparent water-soluble nano-carbon colloidal particle solution is shown in Figure 1 (A). The TEM is shown in Figure 1 (B).
[0031] (2) Preparation of an inner hollow strip structure BaSO4: The prepared brownish red transparent water-soluble nano-carbon colloid particle solution is dissolved and dispersed in 150 mL deionized water, 20 mmol of barium hydroxide is added to the above solution, 3.5 mL of acetic acid is added to promote the dissolution of barium hydroxide, and stirring is continued for 3 days to ensure that barium ions can be adsorbed on the carbon surface; 50 mL of an aqueous solution containing 1.0 g of polyvinylpyrrolidone (PVP, molecular weight 54000) surfactant is added. Then, under the condition of 60°C oil bath, 100 mL of 2M sodium sulfate aqueous solution is gradually added to the above solution under continuous stirring, and the stirring is continued for 30 h to form a stable BaSO4 metal compound precipitate. Finally, a high-purity BaSO4 metal compound is obtained by repeated centrifugal washing.
[0032] The obtained BaSO4 precipitate is centrifugally dried, and microanalysis by scanning electron microscope shows that the material is a hollow strip-shaped porous structure, as shown in Figure 5 (A).
[0033] TEM analysis of the obtained BaSO4 metal compound suspension shows that the internal structure of the material has many hollow points, as shown in Figure 5 (B, C).
[0034] X-ray spectrum analysis of the obtained BaSO4 metal compound suspension shows that the material contains barium, sulfur and oxygen elements, and they are uniformly distributed in the material, as shown in Figure 5 (D, E).
[0035] Example 2 A method for preparing a BaSO4 with a hollow strip structure, which specifically comprises the following steps: (1) Preparation of carbon tar: 60 mL of deionized water containing 5 g of glucose is transferred into the polytetrafluoroethylene inner container of the hydrothermal kettle, and carbonization is carried out at 160°C in the oven for 16 h. The prepared material is washed repeatedly by centrifugation with 200 mL of ethanol and 60 mL of water, and the fine water-soluble carbon material prepared in the reaction is extracted by high-speed centrifugation. Then, the extracted fine water-soluble carbon material is repeatedly centrifuged and filtered to obtain a brownish red transparent supernatant, and the actual photograph of the brownish red transparent supernatant is shown in Figure 2 (A); and the TEM image is shown in Figure 2 (B).
[0036] The prepared brownish red transparent supernatant is dried in an oven to form carbon tar, as shown in Figure 4 The carbon tar is dispersed in 250 mL of deionized water by ultrasonic stirring to form a carbon particle dispersion solution.
[0037] (2) Preparation of hollow strip-shaped BaSO4: 10 mmol of barium hydroxide was added to the above carbon microparticle dispersion solution, followed by 2 mL of acetic acid to promote complete dissolution of barium hydroxide in the solution. 1.0 g of polyvinylpyrrolidone (PVP, molecular weight 54000) was added as a surfactant. Subsequently, the solution was stirred continuously in an oil bath at 30 °C, and 100 mL of 0.15 M sodium sulfate aqueous solution was gradually added dropwise. The mixture was stirred continuously for 15 h to form a stable BaSO4 metal compound precipitate. Finally, excess Na2SO4 was washed away by repeated centrifugation to obtain the BaSO4 metal compound.
[0038] The obtained BaSO4 precipitate was centrifuged and dried, and microscopic analysis by scanning electron microscopy revealed that the BaSO4 metal compound materials prepared in this embodiment all had hollow strip-shaped structures with small internal pore sizes. (See reference...) Figure 6 As shown in (AC).
[0039] X-ray diffraction analysis of the obtained suspension revealed that the material has an orthorhombic crystal structure and is a BaSO4 metallic compound. Figure 6 As shown in (D).
[0040] X-ray energy dispersive spectroscopy (EDS) analysis of the obtained suspended BaSO4 metallic compounds revealed that the material contains elements such as barium, sulfur, and oxygen, which are uniformly distributed throughout the material. Figure 6 As shown in (E).
[0041] Example 3 A method for preparing BaSO4 with a hollow strip structure, specifically comprising the following steps: (1) Preparation of carbon tar: 3 g of glucose was completely dissolved in 30 mL of deionized water. After hydrothermal treatment at 200 °C for 10 h, the mixture was washed repeatedly by centrifugation using 30 mL of water and 120 mL of ethanol. High-speed centrifugation was then used to extract the fine water-soluble carbon material prepared in the reaction. Subsequently, the turbid liquid containing the extracted fine water-soluble carbon material was repeatedly centrifuged and filtered to obtain a brownish-red transparent supernatant. A photograph of the brownish-red transparent supernatant is shown below. Figure 3 As shown in (A); TEM image as follows Figure 3 As shown in (B).
[0042] The brownish-red, transparent supernatant prepared above was dried in an oven to form carbon tar, as follows: Figure 4 As shown, carbon tar was dispersed in 100 mL of deionized water by ultrasonic stirring to form a carbon microparticle dispersion solution.
[0043] (2) Preparation of hollow strip-shaped BaSO4: 15 mmol of barium hydroxide was added to the above carbon microparticle dispersion solution, followed by 4 mL of acetic acid to promote complete dissolution of barium hydroxide in the solution. 2 g of polyvinylpyrrolidone (PVP, molecular weight 54000) was added as a surfactant. Subsequently, the solution was continuously stirred in an oil bath at 30 °C, and 100 mL of 0.2 M sodium sulfate aqueous solution was gradually added dropwise. The mixture was stirred continuously for 21 h to form a stable BaSO4 metal compound precipitate. Finally, excess Na2SO4 was repeatedly washed by centrifugation to obtain the BaSO4 metal compound.
[0044] The obtained BaSO4 precipitate was centrifuged and dried, and microscopic analysis by scanning electron microscopy revealed that the material consisted of hollow, porous, strip-shaped structures. (See [reference needed]). Figure 7 As shown.
[0045] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.
Claims
1. A method for preparing BaSO4 with a hollow strip structure, characterized in that, Includes the following steps: Barium ion compounds are mixed with nano-carbon colloidal particle solutions or carbon tar, acid is added to maintain the pH of the system below 7, surfactants are added, and sodium sulfate aqueous solution is gradually added dropwise under continuous stirring. The reaction forms flocculents or precipitates, thus preparing hollow strip-shaped BaSO4.
2. The preparation method according to claim 1, characterized in that, The preparation method of the nano-carbon colloidal particle solution includes: Lithium hydroxide or sodium hydroxide is dissolved in water to form an electrolyte. A carbon source is added to the electrolyte, and the electrolyte is electrolyzed using a platinum metal sheet as the counter electrode. After centrifugation and filtration, the red supernatant is collected to obtain a solution of nano-carbon colloidal particles.
3. The preparation method according to claim 2, characterized in that, In the preparation method of the nano-carbon colloidal particle solution, the concentration of the electrolyte is 1 M, the carbon source is ethanol, the volume ratio of the electrolyte to the carbon source is 60:15, the electrolysis voltage is 15 V, and the electrolysis time is 3 h to 5 h.
4. The preparation method according to claim 1, characterized in that, The method for preparing the carbon tar includes: Glucose is dissolved in water and then reacted and carbonized at 130 ℃~220 ℃ for 10 h~30 h. After centrifugation and filtration, the supernatant is separated and dried to obtain carbon tar. The ratio of glucose to water added is 3g:30 mL to 5g:60 mL.
5. The preparation method according to claim 1, characterized in that, The preparation method includes the following specific steps: In an oil bath at 30 ℃ to 80 ℃, nano-carbon colloidal particle solution or carbon tar is dispersed in deionized water by continuous ultrasound and stirring. Acid is added to make the solution acidic, and barium ion compound is dissolved in deionized water to form metal ion solution. An aqueous solution containing surfactant is added, and sodium sulfate solution is added dropwise during continuous stirring to form gray flocculent matter. After centrifugation, the precipitate is collected to obtain hollow bar-shaped BaSO4 metal compound.
6. The preparation method according to claim 5, characterized in that, The concentration of the metal ion solution is 0.1 M to 2 M, and the barium ion compound is one of barium chloride and barium hydroxide; The concentration of the sodium sulfate solution is 0.15 M to 2 M, and the molar mass ratio of barium ions to sodium sulfate is 1:1 to 1:
30. The concentration of the aqueous solution containing the surfactant is 0.05 g / L to 20 g / L, and the ratio of barium ion compound to polyvinylpyrrolidone is 10 mmol to 20 mmol: 1.0 g to 2.0 g; The surfactant is polyvinylpyrrolidone, and the molecular weight of polyvinylpyrrolidone is 54,000; The acid is either hydrochloric acid or acetic acid.