CN102689916B - Preparation method of porous barium sulfate microsphere - Google Patents
Preparation method of porous barium sulfate microsphere Download PDFInfo
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- CN102689916B CN102689916B CN201210194227.5A CN201210194227A CN102689916B CN 102689916 B CN102689916 B CN 102689916B CN 201210194227 A CN201210194227 A CN 201210194227A CN 102689916 B CN102689916 B CN 102689916B
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- barium sulfate
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- sulfate
- barium
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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 130
- 239000004005 microsphere Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 24
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 20
- 229940045511 barium chloride Drugs 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of a porous barium sulfate microsphere in a liquid phase. The preparation method comprises the following steps of: dissolving titanium sulfate and polyvinylpylrrolidone in water, adding a certain quantity of hydrogen dioxide solution in the dissolved titanium sulfate and polyvinylpylrrolidone, and uniformly mixing the hydrogen dioxide solution and the dissolved titanium sulfate and polyvinylpylrrolidone, so as to obtain a titanium sulfate solution; dissolving barium chloride and polyvinylpylrrolidone in water, so as to obtain a barium chloride solution; and uniformly mixing the titanium sulfate solution with the barium chloride solution, transferring the mixed solution into a reaction kettle, reacting the mixed solution at a certain temperature, and carrying out centrifugal washing and drying on a product obtained from the reaction, so as to obtain the porous barium sulfate microsphere. The preparation method of the monoclinic phase barium sulfate microsphere is simple; the product barium sulfate microsphere is of a porous structure or a hollow structure; the feature of the product is easy to control, the specific surface area of the product is large; and by using the preparation method, solves the problems that in the prior art, the structure and feature of barium sulfate are difficult to control and the specific surface area of barium sulfate is small.
Description
Technical field
The invention belongs to new chemical materials field, relate to a kind of preparation method of barium sulfate microballoon, specifically, relate to a kind of liquid phase preparation process of barium sulfate porous microsphere.
Background technology
It is strong that barium sulfate has unreactiveness, good stability, acid and alkali-resistance, hardness is moderate, high whiteness, can absorb the advantages such as harm ray, be a kind of inorganic materials with environment-friendly function, is therefore widely used in the fields such as various coating, medium-to-high grade ink, the synthetic chemical industry of medicine, rubber, papermaking, pottery, makeup.But because its proportion is high, and its application performance is restricted.
At present, the main development trend of barium sulfate powder is the granular of its particle and the variation of structural form, to meet the special requirement of different industries.For example, the particle type barium sulfate of mean particle size below 0.3 μ m, can be used for the weighting agent of high-grade resin and rubber, and the development of X ray double contrast radiograph technology also needs the barium sulfate of fine and even.The method of preparing barium sulfate fine particle mainly contains microemulsion method, complexometry, microreactor method, gravity Method etc.Chinese patent CN1398789A has announced a kind of preparation method of nano barium sulfate, and take bariumchloride and EDTA solution is raw material, and the two mixing is made to Ba
2+ion and EDTA complexing add Na under certain pH value
2sO
4solution reacts, and obtains nano barium sulfate product.Chinese patent CN102167386 A discloses a kind of micropore dispersion legal system of liquid phase cross-flow shearing of utilizing for the method for barium sulfate nanoparticles.Chinese patent CN101423239 A has announced a kind of method that rotating liquid-film reactor that utilizes high speed rotating is prepared nano barium sulfate.
The barium sulphate nano powder that aforesaid method is prepared or easily reunion, cause specific surface area to diminish, complex process, gained pattern is difficult to control, and is difficult to meet the requirement of Vehicles Collected from Market to the increasing property of barium sulfate powder (as lightweight, inhale make an uproar etc.).
For these reasons, how finding that a kind of technique is relatively simple, reaction conditions is gentleer, and can prepare size and pattern, the controlled barium sulfate porous microsphere of micropore size, is subject matter to be solved by this invention.
Summary of the invention
The present invention is directed to the complex technical process of gained barium sulfate sample in prior art, reaction conditions is harsher, the problems such as microstructure is single, specific surface area is low, proposed that a kind of technique is relatively simple, reaction conditions is gentleer, can prepare the method for porous barium sulfate microballoon, and be expected to be widely used in pigment, biotechnology field.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A liquid phase preparation process for barium sulfate porous microsphere, described method comprises the steps:
(1) titanium sulfate is dissolved in the water, then after adding a certain amount of polyvinylpyrrolidone to dissolve, adds a certain amount of superoxol, obtain certain density titanium sulfate solution;
(2) a certain amount of bariumchloride and polyvinylpyrrolidone are dissolved in the water, obtain certain density barium chloride solution;
(3) above-mentioned two kinds of solution are mixed according to a certain volume, transfer in reactor, react for some time at a certain temperature, obtain the mixed solution that contains barium sulfate;
(4), after the above-mentioned mixed solution that contains barium sulfate is cooling, centrifugation under certain rotating speed, and water and ethanol repeated washing, obtain white barium sulfate precipitate thing;
(5) the barium sulfate precipitate thing obtaining in step (4) is put into loft drier dry, obtain barium sulfate microballoon.
Wherein, in step (1), the mass ratio of polyvinylpyrrolidone and titanium sulfate is 1:1-1:10, and the mol ratio of titanium sulfate and superoxol is 1:0-1:10;
Further, in step (2), the mass ratio of polyvinylpyrrolidone and bariumchloride is 1:1-1:10;
Further, in step (3), the mol ratio of titanium sulfate and bariumchloride is 1:1, and temperature of reaction is 150-200 ℃, and the reaction times is 6-24 h;
Further again, in step (4), described centrifugal rotational speed is 3000-4000 r/min, and centrifugation time is 5-10min.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum that utilizes barium sulfate porous microsphere prepared by the method for the invention.
Fig. 2 to Fig. 4 is transmission electron microscope (TEM) photo that utilizes barium sulfate porous microsphere prepared by the method for the invention.
Fig. 5 is the N that utilizes barium sulfate porous microsphere prepared by the method for the invention
2adsorption-desorption thermoisopleth, illustration is the pore size distribution curve of barium sulfate porous microsphere.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further detailed explanation.
embodiment mono-:
(1) titanium sulfate is dissolved in the water, then after adding 0.1 g polyvinylpyrrolidone to dissolve, adds the superoxol of 0.14 ml, obtain the titanium sulfate solution of 2.5 mmol/L;
(2) bariumchloride is dissolved in the water, then adds 0.1 g polyvinylpyrrolidone to dissolve, obtain the barium chloride solution of 2.5 mmol/L;
(3) after above-mentioned two kinds of solution equal-volumes are mixed, transfer in reactor, at 180 ℃, react 24 h, obtain the mixed solution that contains barium sulfate;
(4), after the above-mentioned mixed solution that contains barium sulfate is cooling, centrifugation under 3000 r/min, and water and ethanol repeated washing three times, obtain white barium sulfate precipitate thing;
(5) the barium sulfate precipitate thing obtaining in step (4) is put into 60 ℃ of loft drier dry, obtain barium sulfate microballoon.
Fig. 1 is the x-ray diffractogram of powder spectrum of utilizing the barium sulfate porous microsphere that prepared by method described in the embodiment of the present invention one, and the diffraction peak in spectrogram is carried out to indexing, and peak position is all consistent with the standard spectrogram in card 24-1035, there is no TiO
2deng dephasign, occur, show that prepared product is the barium sulfate of oblique crystal phase structure.
Fig. 2 is the prepared barium sulfate microballoon of embodiment mono-, can find out that barium sulfate microspherulite diameter is evenly distributed, and is obviously hollow, vesicular structure, and size is 600 nanometer left and right.
Fig. 5 is the N that utilizes the barium sulfate porous microsphere that prepared by method described in the embodiment of the present invention one
2adsorption-desorption thermoisopleth.By BET method, trying to achieve specific surface area is 35.0m
2/ g.Illustration is the pore size distribution curve of barium sulfate microballoon, is calculated the size distribution in its hole by BJH method, and hole size mainly concentrates on 4-10 nm.
embodiment bis-:
(1) titanium sulfate is dissolved in the water, then after adding 0.1 g polyvinylpyrrolidone to dissolve, obtains the titanium sulfate solution of 2.5 mmol/L;
(2) bariumchloride is dissolved in the water, then adds 0.1 g polyvinylpyrrolidone to dissolve, obtain the barium chloride solution of 2.5 mmol/L;
(3) after above-mentioned two kinds of solution equal-volumes are mixed, transfer in reactor, at 160 ℃, react 24 h, obtain the mixed solution that contains barium sulfate;
(4), after the above-mentioned mixed solution that contains barium sulfate is cooling, centrifugation under 4000 r/min, and water and ethanol repeated washing three times, obtain white barium sulfate precipitate thing;
(5) the barium sulfate precipitate thing obtaining in step (4) is put into 80 ℃ of loft drier dry, obtain barium sulfate microballoon.
Fig. 3 is the prepared barium sulfate microballoon of embodiment bis-, can find out that gained barium sulfate microballoon is the open structure being assembled by small-particle, and microballoon size evenly, particle diameter 500 nanometer left and right.
embodiment tri-:
(1) titanium sulfate is dissolved in the water, then after adding 0.1 g polyvinylpyrrolidone to dissolve, adds the superoxol of 0.07 ml, obtain the titanium sulfate solution of 2.5 mmol/L;
(2) bariumchloride is dissolved in the water, then adds 0.1 g polyvinylpyrrolidone to dissolve, obtain the barium chloride solution of 2.5 mmol/L;
(3) after above-mentioned two kinds of solution equal-volumes are mixed, transfer in reactor, at 180 ℃, react 18 h, obtain the mixed solution that contains barium sulfate;
(4), after the above-mentioned mixed solution that contains barium sulfate is cooling, centrifugation under 3000 r/min, and water and ethanol repeated washing three times, obtain white barium sulfate precipitate thing;
(5) the barium sulfate precipitate thing obtaining in step (4) is put into 60 ℃ of loft drier dry, obtain barium sulfate microballoon.
Fig. 4 is the prepared barium sulfate microballoon of embodiment tri-, can find out that gained barium sulfate microballoon is also the microballoon of the open structure that assembled by small-particle, microspherulite diameter 300 nanometers left and right.
Transmission electron microscope photo from Fig. 2, Fig. 3, Fig. 4 can be found out, by controlling reaction conditions, can realize the regulation and control to barium sulfate product pattern and structure.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any change of doing in the situation that not deviating from principle of the present invention and technological process, substitute, simplification etc.; be equivalent displacement, within all protection scope of the present invention should being included in.
Claims (1)
1. a liquid phase preparation process for barium sulfate porous microsphere, is characterized in that, described method comprises the steps:
(1) titanium sulfate is dissolved in the water, then after adding 0.1 g polyvinylpyrrolidone to dissolve, obtains the titanium sulfate solution of 2.5 mmol/L;
(2) bariumchloride is dissolved in the water, then adds 0.1 g polyvinylpyrrolidone to dissolve, obtain the barium chloride solution of 2.5 mmol/L;
(3) after above-mentioned two kinds of solution equal-volumes are mixed, transfer in reactor, at 160 ℃, react 24 h, obtain the mixed solution that contains barium sulfate;
(4), after the above-mentioned mixed solution that contains barium sulfate is cooling, centrifugation under 4000 r/min, and water and ethanol repeated washing three times, obtain white barium sulfate precipitate thing;
(5) the barium sulfate precipitate thing obtaining in step (4) is put into 80 ℃ of loft drier dry, obtain barium sulfate microballoon.
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| CN102689916B true CN102689916B (en) | 2014-05-07 |
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| CN113683840B (en) * | 2021-08-19 | 2022-09-09 | 云浮鸿志新材料有限公司 | Modified plastic and preparation method thereof |
| CN113998726B (en) * | 2021-12-08 | 2023-07-28 | 安徽壹石通材料科技股份有限公司 | Hollow barium sulfate and preparation method thereof |
| CN115924954A (en) * | 2022-12-28 | 2023-04-07 | 佛山安亿纳米材料有限公司 | Preparation method and application of mesoporous barium sulfate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398789A (en) * | 2002-08-13 | 2003-02-26 | 华北工学院 | Prepn of nano barium sulfate |
| CN1969017A (en) * | 2004-05-04 | 2007-05-23 | 纳米技术应用中心（Can）股份有限公司 | Process for preparing dispersible sulfate, preferably barium sulfate nanoparticles |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398789A (en) * | 2002-08-13 | 2003-02-26 | 华北工学院 | Prepn of nano barium sulfate |
| CN1969017A (en) * | 2004-05-04 | 2007-05-23 | 纳米技术应用中心（Can）股份有限公司 | Process for preparing dispersible sulfate, preferably barium sulfate nanoparticles |
Non-Patent Citations (2)
| Title |
|---|
| "纳米氧化物的制备与性能研究";杨茂丽;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110415;B020-165 ，正文第53-57页 * |
| 杨茂丽."纳米氧化物的制备与性能研究".《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2011,B020-165 ，正文第53-57页. |
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Effective date of registration: 20191122 Address after: No. 56, South Tianyang Road, Tianning Town, Jiashan County, Jiaxing City, Zhejiang Province Patentee after: JIASHAN HUAYANG WOOD INDUSTRY FLOCKING CO., LTD. Address before: 266061 Shandong Province, Qingdao city Laoshan District Songling Road No. 99, Qingdao University of Science & Technology Patentee before: Qingdao University of Science & Technology |
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