CN113697838B - Preparation method of spherical hollow nano barium sulfate - Google Patents
Preparation method of spherical hollow nano barium sulfate Download PDFInfo
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 90
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011541 reaction mixture Substances 0.000 claims abstract description 42
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 38
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000000087 stabilizing effect Effects 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 17
- 229910052700 potassium Inorganic materials 0.000 claims description 17
- 239000011591 potassium Substances 0.000 claims description 17
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 17
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 17
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 17
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 17
- 229960003975 potassium Drugs 0.000 claims description 9
- 235000007686 potassium Nutrition 0.000 claims description 9
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 27
- 239000004576 sand Substances 0.000 description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 238000000227 grinding Methods 0.000 description 15
- 239000011324 bead Substances 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of spherical hollow nano barium sulfate, which comprises the following steps: 1) adding hydrochloric acid and a reaction auxiliary agent into the nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; 2) adding hydrochloric acid into a sodium hexametaphosphate solution to prepare a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution, and stabilizing the pH value between 2.0 and 6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) filtering, washing and drying to obtain the hollow spherical nano barium sulfate. The hollow barium sulfate prepared by the method can increase the surface area and volume of the barium sulfate which is removed from the main material when the barium sulfate is used as an additive, thereby greatly improving the application range of the barium sulfate as the additive.
Description
Technical Field
The invention relates to the field of inorganic nano material synthesis, in particular to a preparation method of hollow sphere type nano barium sulfate.
Background
Barium sulfate is one of the most important inorganic chemical products nowadays, is widely applied to industries such as rubber, plastics, coatings, medicines and the like, and is also used as a weighting agent for drilling mud of petroleum and natural gas. The barium sulfate has the characteristics of acid-base resistance and good corrosion resistance, so that the barium sulfate is added into rubber and plastic products as a filler, plays the roles of increasing the volume, increasing the volume and reducing the cost, and can improve the mechanical strength, the thermodynamic property and the corrosion and aging resistance of the products. However, the density of barium sulfate is relatively high, and when the common barium sulfate powder is used as an additive, the density of the product is often greatly improved, the advantage of light weight of plastic and rubber products is weakened and reduced, the production cost is increased, and the product is greatly limited in the use range. Therefore, under the condition of the same mass, the volume and the surface area of the barium sulfate can be increased as much as possible, the density of rubber and plastic products can be effectively reduced, the advantage of light weight is kept, and the production cost is reduced.
At present, the production process of nano precipitated barium sulfate mainly comprises a method of carrying out a displacement reaction or a neutralization reaction on compounds containing barium ions, such as barium carbonate, barium hydroxide, barium chloride, barium sulfide and the like and compounds containing sulfate ions, such as sulfuric acid, sodium sulfate, ammonium sulfate and the like, so as to generate nano precipitated barium sulfate. The modified barium sulfate obviously improves the mechanical properties such as tear strength, impact strength and the like of products such as films and the like; however, the hollow sphere type nano barium sulfate is not reported at present.
Disclosure of Invention
In order to solve the technical problems, the invention aims to invent a preparation method of spherical hollow nano barium sulfate.
In order to achieve the purpose, the technical scheme of the invention is as follows: a method for preparing spherical hollow nano barium sulfate comprises the following steps: 1) adding hydrochloric acid and a reaction auxiliary agent into the nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; 2) adding hydrochloric acid into a sodium hexametaphosphate solution to prepare a pre-reaction mixture B; 3) adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution at the same time, wherein the pH value is stabilized between 2.0 and 6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) filtering, washing and drying to obtain the hollow spherical nano barium sulfate.
Preferably, the reaction assistant in step 1) is at least one of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate.
Preferably, the reaction auxiliary agent in the step 1) is formed by mixing 5-8 parts by mass of sodium hexametaphosphate, 1-3 parts by mass of sodium pyrophosphate and 2-5 parts by mass of potassium tripolyphosphate.
Preferably, the preparation method of the nano barium carbonate slurry in the step 1) is that barium carbonate with an average particle size of 1.0-8.0 μm, deionized water and pentaerythritol or sodium polyacrylate are uniformly stirred, and the mass ratio of barium carbonate to water to pentaerythritol or sodium polyacrylate is 50-100: 50-100: 1-5, sequentially pumping the barium carbonate slurry to a No. 1-4 ceramic horizontal sand mill arranged in a series connection mode by using a metering pump, performing primary grinding on the barium carbonate slurry by using a No. 1 sand mill, performing secondary grinding on the barium carbonate slurry by using a No. 2 sand mill, performing tertiary grinding on the barium carbonate slurry by using a No. 3 sand mill, performing four-stage grinding on the barium carbonate slurry by using a No. 4 sand mill, adding zirconia beads with the bead particle size of 100-2000 mu m into the sand mill, wherein the particle size of the zirconia beads added into the No. 1-2 sand mill is 600-2000 mu m, the particle size of the zirconia beads added into the No. 3-4 sand mill is 100-800 mu m, controlling the flow rate of the metering pump at 2-5L/min, controlling the rotation speed of the sand mill at 500-2000 r/min, and performing four-stage grinding to obtain the nano-grade barium carbonate slurry.
Preferably, in the step 1), 300-600 parts by mass of nano barium carbonate slurry is added with 1-2 parts by mass of 31% hydrochloric acid and 1-10 parts by mass of an auxiliary agent, and the mixture is fully mixed to obtain a pre-reaction mixture A; the auxiliary agent is composed of at least one of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate.
Preferably, in the step 2), 1 to 3 parts by mass of sodium hexametaphosphate is added to 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and then 1 to 5 parts by mass of 31% hydrochloric acid is added to obtain a pre-reaction mixture B.
Preferably, in step 3), the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water.
A method for preparing spherical hollow nano barium sulfate comprises the following steps: 1) adding 1-2 parts by mass of 31% hydrochloric acid and 1-10 parts by mass of an auxiliary agent into the nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; the auxiliary agent consists of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate, wherein the mass ratio of the sodium hexametaphosphate: sodium pyrophosphate: potassium tripolyphosphate = (5-8): (1-3): (2-5); 2) adding 1-3 parts by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 1-5 parts by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution at the same time, wherein the pH value is stabilized between 2.0 and 6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) washing the filter by pressure filtration, and drying to obtain hollow spherical nano barium sulfate; the preparation method of the nano barium carbonate comprises the following steps: uniformly stirring barium carbonate with the average particle size of 1.0-8.0 micrometers, deionized water and pentaerythritol or sodium polyacrylate, wherein the mass ratio of barium carbonate to water to pentaerythritol or sodium polyacrylate is 50-100: 50-100: 1-5, sequentially pumping the barium carbonate slurry to a No. 1-4 ceramic horizontal sand mill arranged in a series connection mode by using a metering pump, performing primary grinding on the barium carbonate slurry by using a No. 1 sand mill, performing secondary grinding on the barium carbonate slurry by using a No. 2 sand mill, performing tertiary grinding on the barium carbonate slurry by using a No. 3 sand mill, performing four-stage grinding on the barium carbonate slurry by using a No. 4 sand mill, adding zirconia beads with the bead particle size of 100-2000 mu m into the sand mill, wherein the particle size of the zirconia beads added into the No. 1-2 sand mill is 600-2000 mu m, the particle size of the zirconia beads added into the No. 3-4 sand mill is 100-800 mu m, controlling the flow rate of the metering pump at 2-5L/min, controlling the rotation speed of the sand mill at 500-2000 r/min, and performing four-stage grinding to obtain the nano-grade barium carbonate slurry.
Drawings
FIG. 1 is a graph showing the results of particle size measurement of nano-sized hollow barium sulfate obtained in example 1
FIG. 2 is an SEM scanning electron micrograph of nano-sized hollow barium sulfate obtained in example 1
FIG. 3 is a graph showing the results of particle size measurement of nano-sized hollow barium sulfate obtained in example 2
FIG. 4 is an SEM scanning electron micrograph of nano-scale hollow barium sulfate obtained in example 2
FIG. 5 shows the results of particle size measurement of nano-sized hollow barium sulfate obtained in example 3
FIG. 6 is an SEM scanning electron micrograph of nano-sized hollow barium sulfate obtained in example 3
FIG. 7 shows the results of particle size measurement of nano-sized hollow barium sulfate obtained in example 4
FIG. 8 is an SEM scanning electron micrograph of nano-sized hollow barium sulfate obtained in example 4
FIG. 9 shows the results of particle size measurement of nano-sized hollow barium sulfate obtained in comparative example 2
FIG. 10 is an SEM scanning electron micrograph of nano-sized hollow barium sulfate obtained in comparative example 2.
Detailed Description
The following further illustrates embodiments of the invention:
the nano barium carbonate is prepared according to the following method: uniformly stirring barium carbonate with the average particle size of 1.0-8.0 micrometers, deionized water and pentaerythritol or sodium polyacrylate, wherein the mass ratio of barium carbonate to water to pentaerythritol or sodium polyacrylate is 50-100: 50-100: 1-5, sequentially pumping the barium carbonate slurry to a No. 1-4 ceramic horizontal sand mill arranged in a series connection mode by using a metering pump, performing primary grinding on the barium carbonate slurry by using a No. 1 sand mill, performing secondary grinding on the barium carbonate slurry by using a No. 2 sand mill, performing tertiary grinding on the barium carbonate slurry by using a No. 3 sand mill, performing four-stage grinding on the barium carbonate slurry by using a No. 4 sand mill, adding zirconia beads with the bead particle size of 100-2000 mu m into the sand mill, wherein the particle size of the zirconia beads added into the No. 1-2 sand mill is 600-2000 mu m, the particle size of the zirconia beads added into the No. 3-4 sand mill is 100-800 mu m, controlling the flow rate of the metering pump at 2-5L/min, controlling the rotation speed of the sand mill at 500-2000 r/min, and performing four-stage grinding to obtain the nano-grade barium carbonate slurry.
Example 1
The hollow nano barium sulfate is prepared according to the following method: 1) adding 1 part by mass of 31% hydrochloric acid and 2 parts by mass of an auxiliary agent into the nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; the auxiliary agent consists of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate, wherein the mass ratio of the sodium hexametaphosphate: sodium pyrophosphate: potassium tripolyphosphate = 5: 1: 2; 2) adding 2 parts by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 1 part by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution, wherein the pH value is stabilized to be 2.0-6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) filtering, washing and drying to obtain the hollow spherical nano barium sulfate, wherein the median particle diameter of the particles is D50: about 98 nm.
Example 2
The hollow nano barium sulfate is prepared according to the following method: 1) adding 1 part by mass of 31% hydrochloric acid and 10 parts by mass of an auxiliary agent into the nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; the auxiliary agent consists of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate, wherein the mass ratio of the sodium hexametaphosphate: sodium pyrophosphate: potassium tripolyphosphate = 8: 1: 5; 2) adding 3 parts by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 1 part by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution, wherein the pH value is stabilized to be 2.0-6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) washing with press filtration water, and drying to obtain nano barium sulfate with a particle median diameter D50: about 110 nm.
Example 3
The hollow nano barium sulfate is prepared according to the following method: 1) adding 2 parts by mass of 31% hydrochloric acid and 8 parts by mass of an auxiliary agent into the nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; the auxiliary agent is sodium hexametaphosphate; 2) adding 3 parts by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 5 parts by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution, wherein the pH value is stabilized to be 2.0-6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) filtering, washing and drying to obtain spherical nano barium sulfate, wherein the median particle size is D50: 89 nm.
Example 4
The hollow nano barium sulfate is prepared according to the following method: 1) adding 2 parts by mass of 31% hydrochloric acid and 6 parts by mass of an auxiliary agent into the nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; the auxiliary agent consists of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate, wherein the mass ratio of the sodium hexametaphosphate: sodium pyrophosphate: potassium tripolyphosphate = 5: 3: 2; 2) adding 1 part by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 5 parts by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution, wherein the pH value is stabilized to be 2.0-6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) washing with press filtration water, and drying to obtain olive-type nano barium sulfate, wherein the particle size is D50: 190 nm.
Comparative example 1
An ordinary precipitated barium sulfate was used as comparative example 1.
Comparative example 2
The hollow barium sulfate was prepared as follows: 1) adding 100 parts by mass of barium carbonate into 200 parts by mass of water, uniformly mixing to obtain barium carbonate slurry, adding 1 part by mass of 31% hydrochloric acid and 2 parts by mass of an auxiliary agent into the barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; the auxiliary agent consists of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate, wherein the mass ratio of the sodium hexametaphosphate: sodium pyrophosphate: potassium tripolyphosphate = 5: 1: 2; 2) adding 2 parts by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 1 part by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B obtained in the step 1) into a sulfuric acid solution, wherein the pH value is stabilized to be 2.0-6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) washing by using press filtration water, and drying to obtain barium sulfate, wherein the median particle size D50: 789 nm.
The hollow spherical nano barium sulfate prepared in the examples 1 to 4 and the comparative examples 1 and 2 are tested to detect the barium sulfate pileDensity, the test results are as follows:
| performance of | Barite powder | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 |
| Bulk density of barium sulfate g/cm 3 | 1.582 | 0.789 | 0.573 | 0.297 | 0.435 | 0.368 | 0.422 |
And (4) conclusion: when the ratio of phosphate to hydrochloric acid is 2: the barium sulfate particles obtained in the step 1 are of a nano hollow spherical shape, which is ideal; in addition, if the raw material is experimentally treated by using non-nano-grade barium carbonate, a satisfactory hollow sphere cannot be obtained, the generated barium sulfate particles are not obviously different from the common barium sulfate particles, the particle size is large, and the generation of hollow barium sulfate is not found.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A method for preparing spherical hollow nano barium sulfate comprises the following steps: 1) adding 1-2 parts by mass of 31% hydrochloric acid and 1-10 parts by mass of an auxiliary agent into 300-600 parts by mass of nano barium carbonate slurry, and fully and uniformly mixing to obtain a pre-reaction mixture A; 2) adding 1-3 parts by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 1-5 parts by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B into a sulfuric acid solution, and stabilizing the pH value between 2.0 and 6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) washing the filter by pressure filtration, and drying to obtain hollow spherical nano barium sulfate; the preparation method of the nano barium carbonate slurry in the step 1) is that 100 parts by mass of nano barium carbonate is added into 200-500 parts by mass of water and mixed uniformly to prepare the nano barium carbonate slurry; in the step 1), the auxiliary agent is at least one of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate.
2. The method for preparing spherical hollow nano barium sulfate according to claim 1, wherein the reaction auxiliary agent in step 1) is prepared by mixing 5-8 parts by mass of sodium hexametaphosphate, 1-3 parts by mass of sodium pyrophosphate and 2-5 parts by mass of potassium tripolyphosphate.
3. The method for preparing spherical hollow nano barium sulfate according to claim 1, wherein in the step 3), the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water.
4. A method for preparing spherical hollow nano barium sulfate comprises the following steps: 1) adding 100 parts by mass of nano barium carbonate into 200-500 parts by mass of water, uniformly mixing to obtain nano barium carbonate slurry, adding 1-2 parts by mass of 31% hydrochloric acid and 1-10 parts by mass of an auxiliary agent into the nano barium carbonate slurry, and fully mixing to obtain a pre-reaction mixture A; the auxiliary agent consists of sodium hexametaphosphate, sodium pyrophosphate and potassium tripolyphosphate, wherein the mass ratio of the sodium hexametaphosphate: sodium pyrophosphate: potassium tripolyphosphate (5-8): (1-3): (2-5); 2) adding 1-3 parts by mass of sodium hexametaphosphate into 100 parts by mass of water to prepare a sodium hexametaphosphate solution, and adding 1-5 parts by mass of 31% hydrochloric acid to obtain a pre-reaction mixture B; 3) simultaneously adding the pre-reaction mixture A and the pre-reaction mixture B into a sulfuric acid solution, and stabilizing the pH value between 2.0 and 6.0 during adding; after all the components are uniformly mixed, the pH value is 1.5-1.8; the sulfuric acid solution is prepared from 50 parts by mass of 98% concentrated sulfuric acid and 300 parts by mass of water; 4) fully stirring the mixture obtained in the step 3) for more than 30min, adjusting the pH value to 7.0-9.0, and stopping the reaction; 5) filtering, washing and drying to obtain the hollow spherical nano barium sulfate.
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Denomination of invention: A preparation method of spherical hollow nano barium sulfate Granted publication date: 20220809 Pledgee: Bank of China Limited by Share Ltd. Yunfu branch Pledgor: YUNFU HONGZHI NEW MATERIAL Co.,Ltd. Registration number: Y2024980006093 |