CN102167386B - Method for preparing barium sulfate nanoparticles - Google Patents
Method for preparing barium sulfate nanoparticles Download PDFInfo
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- CN102167386B CN102167386B CN 201110063603 CN201110063603A CN102167386B CN 102167386 B CN102167386 B CN 102167386B CN 201110063603 CN201110063603 CN 201110063603 CN 201110063603 A CN201110063603 A CN 201110063603A CN 102167386 B CN102167386 B CN 102167386B
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- CN
- China
- Prior art keywords
- barium
- solution
- suspension liquid
- metabisulfite solution
- barium sulfate
- Prior art date
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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 76
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 21
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 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 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for preparing barium sulfate nanoparticles, belonging to the technical field of preparation of chemical materials. The method comprises the following steps: vertically dispersing a sodium sulfate solution into a flowing barium sulphide solution or circularly following barium sulphide suspension liquid through a plurality of micropores, cutting the sodium sulfate solution by means of cross flow, reacting in a mixing way to obtain a barium sulfate precipitate, and carrying out curing, solid-liquid separation, impurity removal in a washing way, drying and smashing on reaction product to obtain the barium sulfate nanoparticles. The method for preparing the barium sulfate nanoparticles is low in raw material cost, high in production capacity, simple and convenient in operation process, and good in repeatability and stability, so that the conventional mirabilite-black ash method can enter into the production sequence of the nanometer level barium sulfate nanoparticles. The method can be used for preparing the barium sulfate nanoparticles with the mean grain sizes of 35-48nm.
Description
Technical field
The invention belongs to technical field of chemical material preparation, particularly a kind of method for preparing the barium sulphate nano particle specifically, relates to the method that a kind of micropore dispersion method of utilizing the liquid phase cross-flow to shear prepares the barium sulphate nano particle.
Background technology
The barium sulphate nano particle has small-size effect and good chemical stability, is widely used in fields such as the packing material of coating, plastics, paint and additive.Barium sulphate nano preparation method of granules at present commonly used mainly contains: (1) saltcake-grey black method-with sodium sulphite, barium bittern and sodium sulfate is raw material, at first obtain barium sulfide solution or slurry, mix with metabisulfite solution afterwards, chemical reaction takes place, regulate the pH value afterwards to reaction end, obtain the barium sulfate slurry, and finally obtain product; (2) complexing-precipitator method-with BaCl
2With EDTA solution be raw material, with the two mixed preparing Ba
2+The complex system of-EDTA is regulated complex system and is reached certain pH value and temperature; The Na that will prepare in advance then
2SO
4React in the solution adding complex system, reaction product namely gets the nano barium sulfate product through centrifugation, washing, drying.These methods or introduce other reactive component strengthen the later separation difficulty; The granularity that perhaps prepares the gained particle is bigger than normal, wider distribution, monodispersity are not good, and as saltcake-grey black method, the existing particle diameter of this handicraft product is difficult to reach nano level.It is poor that the reason that produces this situation is that the material microcosmic mixes, and transmittance process is slow, and the nucleation amount is little when directly precipitating, nucleation is inhomogeneous, and has directly influenced the quality of particle.
On the other hand, utilize the micropore of fluid shearing to disperse for homogeneous phase and heterogeneous mixing good performance is arranged, system heat and mass efficient height, help to solve rapid reaction because transmitting the problem of restriction poor controllability, for direct precipitation method has been created condition making a breakthrough aspect the preparation barium sulphate nano particle.
Summary of the invention
The present invention is intended to propose a kind of new method for preparing the barium sulphate nano particle.Its principle is: what selected system took place among the present invention is the liquid-phase precipitation reaction, and speed of response is fast, and transmittance process is the control step in the preparation process; For this system, utilize the micropore of fluid shearing to disperse to accelerate the carrying out of transmitting, making has higher degree of supersaturation in the system, guaranteed the homogeneity of mixing simultaneously, thereby prepared the barium sulphate nano particle that particle is little and be evenly distributed.
A kind of method for preparing the barium sulphate nano particle, with metabisulfite solution from vertical direction be distributed to mobile barium sulfide solution by micropore or the barium sulphide suspension liquid that circulates, metabisulfite solution is sheared by cross-flow, hybrid reaction, generate barium sulfate precipitate, reaction product makes the barium sulphate nano particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing.
The temperature of described barium sulfide solution or suspension liquid is 10～70 ℃, and the temperature of described metabisulfite solution is 10～70 ℃.
The concentration of described barium sulfide solution or suspension liquid is 0.25～2.5mol/L, and the concentration of described metabisulfite solution is 5～45wt%.
Described micropore equivalent diameter is 0.2～1000 micron.
The flow velocity of barium sulfide solution or suspension liquid is 0.2～3m/s, and the flow velocity of metabisulfite solution is 0.1～5m/s.
Specifically, the method for the invention comprises the steps:
(1) formulating vulcanization barium solution or barium sulphide suspension liquid;
(2) preparation metabisulfite solution;
(3) under pressure, make metabisulfite solution from vertical direction be distributed to mobile barium sulfide solution by micropore or the barium sulphide suspension liquid that circulates, metabisulfite solution is sheared by cross-flow, hybrid reaction;
(4) reaction product obtains final barium sulphate nano particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing (press industrial standards and pulverize, be i.e. 45 μ m screenings content≤0.5%).
In the step (3), the molar flow rate of the molar flow rate of the sodium sulfate of bringing into metabisulfite solution and the barium sulphide brought into barium sulfide solution equates.
In the step (3), the barium sulphide suspension liquid constantly circulates, and barium sulphide molar weight initial in the molar weight of the sodium sulfate of bringing into metabisulfite solution and barium sulphide suspension liquid equates.
Beneficial effect of the present invention is: utilize method of the present invention to prepare the barium sulphate nano particle, raw materials cost is low, and throughput is big, and operating process is easy, repeatability and good stability make traditional saltcake-grey black method can enter the production sequence of nano level barium sulfate particle.Adopt this method can obtain median size at the barium sulphate nano particle of 35～48nm.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
Under 70 ℃, preparation 1000mL volumetric molar concentration is that the barium sulphide suspension liquid of 2.5mol/L and 800g massfraction are 45% metabisulfite solution.Under the effect of pressure reduction, it is that 200 microns micropore mixes with the barium sulphide suspension liquid that circulates do cross-flow, flow velocity is 1m/s that metabisulfite solution passes equivalent diameter with the flow velocity of 0.5m/s, and reaction generates barium sulfate precipitate, and circulating reaction is to stoicheiometry.Product obtains final barium sulfate particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing, and its median size is 48nm.
Embodiment 2:
Under 50 ℃, preparation 1000mL volumetric molar concentration is that the barium sulfide solution of 1.5mol/L and 720g massfraction are 30% metabisulfite solution.Under the effect of pressure reduction, it is that 200 microns micropore is that the barium sulfide solution of 3m/s mixes with making cross-flow passes, flow velocity that metabisulfite solution passes equivalent diameter with the flow velocity of 5m/s, and reaction generates barium sulfate precipitate.Product obtains final barium sulfate particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing, and its median size is 43nm.
Embodiment 3:
Under 20 ℃, preparation 1000mL volumetric molar concentration is that the barium sulphide suspension liquid of 0.5mol/L and 720g massfraction are 10% metabisulfite solution.Under the effect of pressure reduction, it is that 600 microns micropore mixes with the barium sulphide suspension liquid that circulates do cross-flow, flow velocity is 0.3m/s that metabisulfite solution passes equivalent diameter with the flow velocity of 0.1m/s, and reaction generates barium sulfate precipitate, and circulating reaction is to stoicheiometry.Product obtains final barium sulfate particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing, and its median size is 40nm.
Embodiment 4:
Under 10 ℃, preparation 1000mL volumetric molar concentration is that the barium sulfide solution of 0.25mol/L and 720g massfraction are 5% metabisulfite solution.Under the effect of pressure reduction, it is that 0.2 micron micropore is that the barium sulfide solution of 0.2m/s mixes with making cross-flow passes, flow velocity that metabisulfite solution passes equivalent diameter with the flow velocity of 0.2m/s, and reaction generates barium sulfate precipitate.Product obtains final barium sulfate particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing, and its median size is 35nm.
Embodiment 5:
Under 40 ℃, preparation 1000mL volumetric molar concentration is that the barium sulfide solution of 1.0mol/L and 720g massfraction are 20% metabisulfite solution.Under the effect of pressure reduction, it is that 200 microns micropore is that the barium sulfide solution of 1m/s mixes with making cross-flow passes, flow velocity that metabisulfite solution passes equivalent diameter with the flow velocity of 0.5m/s, and reaction generates barium sulfate precipitate.Product obtains final barium sulfate particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing, and its median size is 37nm.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (6)
1. method for preparing the barium sulphate nano particle, it is characterized in that, with metabisulfite solution from vertical direction be distributed to mobile barium sulfide solution by micropore or the barium sulphide suspension liquid that circulates, metabisulfite solution is sheared by cross-flow, hybrid reaction, generate barium sulfate precipitate, reaction product makes the barium sulphate nano particle through aftertreatment; Wherein, the temperature of described barium sulfide solution or barium sulphide suspension liquid is 10 ~ 70 ℃, and the temperature of described metabisulfite solution is 10 ~ 70 ℃; The concentration of described barium sulfide solution or barium sulphide suspension liquid is 0.25 ~ 2.5mol/L, and the concentration of described metabisulfite solution is 5 ~ 45wt%; The flow velocity of described barium sulfide solution or barium sulphide suspension liquid is 0.2 ~ 3m/s, and the flow velocity of metabisulfite solution is 0.1 ~ 5m/s.
2. method according to claim 1, it is characterized in that: described aftertreatment comprises the steps: slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing.
3. method according to claim 1, it is characterized in that: described micropore equivalent diameter is 0.2 ~ 1000 micron.
4. method according to claim 1 is characterized in that, comprises the steps:
(1) formulating vulcanization barium solution or barium sulphide suspension liquid;
(2) preparation metabisulfite solution;
(3) under pressure, make metabisulfite solution from vertical direction be distributed to mobile barium sulfide solution by micropore or the barium sulphide suspension liquid that circulates, metabisulfite solution is sheared by cross-flow, hybrid reaction;
(4) reaction product obtains the barium sulphate nano particle through slaking, solid-liquid separation, washing removal of impurities, drying, pulverizing.
5. method according to claim 4 is characterized in that: in the step (3), the molar flow rate of the molar flow rate of the sodium sulfate of bringing into metabisulfite solution and the barium sulphide brought into barium sulfide solution equates.
6. method according to claim 4, it is characterized in that: in the step (3), the barium sulphide suspension liquid constantly circulates, and barium sulphide molar weight initial in the molar weight of the sodium sulfate of bringing into metabisulfite solution and barium sulphide suspension liquid equates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110063603 CN102167386B (en) | 2011-03-16 | 2011-03-16 | Method for preparing barium sulfate nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110063603 CN102167386B (en) | 2011-03-16 | 2011-03-16 | Method for preparing barium sulfate nanoparticles |
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| CN102167386A CN102167386A (en) | 2011-08-31 |
| CN102167386B true CN102167386B (en) | 2013-07-03 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130260B (en) * | 2013-03-19 | 2014-11-19 | 冉金友 | Production method of barium sulfate |
| CN104512923A (en) * | 2013-09-30 | 2015-04-15 | 上海梅山钢铁股份有限公司 | Preparation method of nano-barium sulfate |
| CN106745152A (en) * | 2015-11-25 | 2017-05-31 | 宜宾丝丽雅股份有限公司 | Method for preparing nano barium sulfate and co-producing sodium chloride |
| CN106241850B (en) * | 2016-07-12 | 2018-01-02 | 重庆工商大学 | The preparation method and applications of insoluble sulfur hydrochlorate photochemical catalyst |
| CN111285389A (en) * | 2018-12-06 | 2020-06-16 | 南风化工集团股份有限公司 | Production method of superfine precipitated barium sulfate |
| CN111362293B (en) * | 2020-04-03 | 2022-09-27 | 河北化工医药职业技术学院 | Preparation method of spindle-shaped barium sulfate and spindle-shaped barium sulfate |
| CN111533153B (en) * | 2020-04-20 | 2023-01-03 | 中国日用化学研究院有限公司 | Preparation method of nano barium sulfate powder |
| CN116588964A (en) * | 2023-04-17 | 2023-08-15 | 贵州红星发展股份有限公司 | Barium sulfate and preparation method thereof |
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| CN101798090A (en) * | 2010-04-07 | 2010-08-11 | 清华大学 | Method for preparing nanometer silicon dioxide |
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2011
- 2011-03-16 CN CN 201110063603 patent/CN102167386B/en active Active
Patent Citations (7)
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|---|---|---|---|---|
| CN1377831A (en) * | 2001-04-03 | 2002-11-06 | 黄榕 | Process for preparing super fine deposited barium sulphate |
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| CN102167386A (en) | 2011-08-31 |
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