CN113213520A - Method and system for continuously preparing nano barium sulfate - Google Patents
Method and system for continuously preparing nano barium sulfate Download PDFInfo
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Abstract
The invention discloses a method and a system for continuously preparing nano barium sulfate, which are characterized in that a water-soluble barium solution and a sulfate solution are proportionally input into a static pipeline mixing reactor, so that the two solutions rapidly flow in the static pipeline mixing reactor and form turbulent flow for fully mixing, and a nano barium sulfate suspension is rapidly generated through rapid reaction. The static pipeline mixing reactor is one or several of static porous plate type pipeline mixing reactor, static special-shaped plate type pipeline mixing reactor and static spiral plate type pipeline mixing reactor. And filtering and washing the barium sulfate suspension for multiple times, adjusting the pH value, drying and crushing to prepare the nano barium sulfate powder material. The content of the obtained barium sulfate is higher than 99%, the average particle size can be controlled within 20-100nm, the particle size distribution is narrow, the whiteness is better than 98.8%, and the content of volatiles at 105 ℃ is lower than 0.08%. The invention has the advantages of wide application range, controllable barium sulfate particle size, continuous and controllable production process, easy realization of industrialization and the like.
Description
Technical Field
The invention relates to a method and a system for continuously preparing nano barium sulfate, in particular to a process for continuously preparing a barium sulfate nano material through a pipeline mixing reactor, and belongs to the technical field of nano materials.
Background
Barium sulfate is an important chemical material. Barium sulfate is non-toxic, acid and alkali resistant, stable in chemical property, high in brightness and good in dispersibility, and has been widely used in the fields of rubber, plastics, printing ink, coating and the like. The nano barium sulfate has important physicochemical characteristics of nano size effect, surface effect and the like, is an important functional filling material for high-end electronic equipment, plastic mold organic coatings and high-end automobile paints, and has wide application prospect in the fields of ceramics, medicines, magnetic materials, optical materials and composite materials. At present, the preparation method of barium sulfate powder material mainly comprises a black ash-mirabilite method, a chemical precipitation method, a microemulsion method, an additive method, a micro-reactor method, an anion exchange method and the like. The black ash-mirabilite method and the chemical precipitation method are the main methods for producing barium sulfate in factories. The two methods usually adopt a pot-type reaction, have the defects of long mixing time, intermittent reaction, uncontrollable reaction process and the like, and the prepared barium sulfate has large particle size (usually more than 500nm), wide particle size distribution range and poor dispersibility, and is difficult to meet the application requirements of high-end fields such as electronic ink, fine chemicals and the like. The microchannel reactor method is a method which is currently studied in laboratories more extensively. The method controls the reaction speed by controlling the concentration of a continuous phase and a dispersed phase, thereby obtaining the nano barium sulfate with smaller grain diameter. However, the concentration of the solution used in the reaction of the microchannel reactor is low, and the pore channel of the reactor is easy to block, so that the production efficiency is not high, the stability is poor, and the industrial production is difficult. The additive method controls the reaction process by adding additives such as a surfactant, a complexing agent, a chelating agent and the like, and inhibits the agglomeration of barium sulfate so as to regulate and control the grain size of the barium sulfate. Although the method can prepare the barium sulfate with the size of nanometer magnitude, the addition of the additive increases the cost, reduces the purity of the barium sulfate, influences the performance of the barium sulfate and also causes pollution to the environment. In addition, the additive is usually prepared by a tank reaction, and the inherent defect of the tank reaction is also existed. Although the particle size of barium sulfate can be controlled below 300nm by other methods, the yield is low, the cost is high, the industrial production is not realized, and the purity of barium sulfate is reduced due to the introduction of other chemical substances, so that the application of the barium sulfate is influenced.
At present, there are some documents on the preparation of nano barium sulfate materials. The Yasheng et al is prepared by adding ethanol into BaS solution, adding Na2SO4Adding dispersant into the solution, and carrying out liquid phase precipitation reaction by using a rotary packed bed as a forced mixer to prepare barium sulfate (2001, 05, 1002-1124) with the particle size of 50-130 nm. Patent document CN103626219A discloses a method for screening a barium (Ba) (OH)2Adding EDTA to generate Ba-EDTA complex; then adding SO to the Ba-EDTA complex4 2-Can control Ba2+And SO4 2-And (3) combining the rate, thus obtaining the nano barium sulfate material. Research shows that the barium sulfate nanometer material with small particle size can be obtained by adding a dispersing agent or a surfactant and generating a complex, but the dispersing agent, the surfactant and the complexing agent are difficult to recover and high in production cost, and functional groups are introduced, so that the purity and the surface chemical properties of barium sulfate are changed. Patent document CN101423239A discloses a method for preparing BaCl2And Na2SO4The nano barium sulfate with the grain diameter of 30-120nm and narrow grain diameter distribution is obtained by carrying out nucleation reaction on the raw materials through a rotary liquid film reactor rotating at high speed. Patent CN108862355A discloses that the temperature of barium solution and sulfate solution is controlled, and T-type and Y-type microchannel reactors (a micro-reactor) are used as mixers for precipitation reaction, so as to generate nano barium sulfate with controllable particle size distribution. Patent documents CN110294487A and CN109279640A disclose that highly dispersed, hydrophobically modified barium sulfate nanomaterials were prepared by a membrane dispersion microreactor method. The particle size and distribution range of the barium sulfate material can be reduced by the microreactor, but the flow is smoothThe method has the advantages of low speed, low concentration, low production efficiency, easy blockage of equipment and difficult large-scale production. The above documents show that several methods for preparing nano barium sulfate have been developed. However, these methods still remain in the laboratory stage, and it is difficult to realize industrial production.
Disclosure of Invention
The invention aims to provide a method and a system for continuously preparing a nano barium sulfate material, which utilize a static pipeline mixing reactor to carry out continuous, rapid, turbulent and full mixing under the condition of not adding additives such as a dispersing agent, a surfactant, a complexing agent and the like, so that two liquids are mixed to form a plurality of tiny reaction units, and a chemical reaction is rapidly carried out to generate nano barium sulfate grains; and can effectively prevent the agglomeration and growth of the nano barium sulfate, and obtain the nano barium sulfate material with good dispersibility.
The invention is realized by the following technical scheme.
A method for continuously preparing nano barium sulfate comprises the following steps:
respectively preparing water-soluble barium solution and sulfate solution with concentration of 0.5mol/L to saturation concentration at 30-90 deg.C according to [ SO ]4 2-]:[Ba2+]The molar ratio of the water-soluble barium solution to the sulfate solution is (1-2): 1, and the water-soluble barium solution and the sulfate solution are respectively input into a static pipeline mixing reactor and are rapidly mixed and reacted in the reactor to generate the nano barium sulfate suspension.
The static pipeline mixing reactor comprises any one or a plurality of combinations of a static porous plate type pipeline mixing reactor, a static special-shaped plate type pipeline mixing reactor and a static spiral plate type pipeline mixing reactor.
And carrying out solid-liquid separation on the barium sulfate suspension, adding water for washing and filtering for 2-4 times to obtain a barium sulfate filter cake. And adding water into the barium sulfate filter cake for dispersing, and adjusting the pH to 6.5-7.2 to obtain a nearly neutral barium sulfate suspension.
And carrying out solid-liquid separation on the barium sulfate suspension, and then drying and crushing to obtain the nano barium sulfate product with the average particle size of 20-100 nm. The content of barium sulfate in the nano barium sulfate product is higher than 99%, the whiteness is better than 98.8%, and the content of volatile matters at 105 ℃ is lower than 0.08%.
In the technical scheme, the water-soluble barium liquid is prepared by any one of water-soluble barium compounds including barium sulfide, barium chloride, barium nitrate and barium hydroxide; the sulfate comprises any one or a mixture of more of sodium sulfate, ammonium sulfate, potassium sulfate and magnesium sulfate; and the flow velocity of the mixed solution of the water-soluble barium solution and the sulfate solution in the static pipeline mixing reactor is 0.1-5 m/s.
The continuous preparation system of the nano barium sulfate comprises a static pipeline mixing reactor, a barium liquid storage tank, a barium liquid feeding device, a sulfate storage tank, a sulfate feeding device, a first filtering device, a pH adjusting device, a second filtering device and a drying and crushing device, wherein the first filtering device, the pH adjusting device, the second filtering device and the drying and crushing device are sequentially connected with the static pipeline mixing reactor. And the barium liquid storage tank and the sulfate storage tank are respectively fed into the static pipeline mixing reactor through the barium liquid feeding device and the sulfate feeding device. The static pipeline mixing reactor comprises any one or a plurality of combinations of a static porous plate type pipeline mixing reactor, a static special-shaped plate type pipeline mixing reactor and a static spiral plate type pipeline mixing reactor.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the static pipe mixing reactor has an inner diameter of 5mm to 60mm, and a plurality of mixing units are disposed therein; the pressure resistance value of the static pipeline mixer is not lower than 0.2 MPa.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the static pipe-line mixing reactor is a static perforated plate-line mixing reactor, a mixing unit in the static pipe-line mixing reactor is an SMV-type mixing unit and/or a BKM-type mixing unit, and the number of the mixing units is not less than 5. And when the SMV type mixing unit and the BKM type mixing unit are selected, the SMV type mixing unit and the BKM type mixing unit are alternately arranged in series.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the static pipe mixing reactor is a static special-shaped plate-type pipe mixing reactor, a mixing unit in the static pipe mixing reactor is a ross ISG mixer mixing unit, and the number of the mixing units is not less than 6.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the static pipe-line mixing reactor is a static spiral-plate pipe-line mixing reactor, the mixing units in the static pipe-line mixing reactor are Kenics pipe-line mixer mixing units and/or island gas pipe-line mixer mixing units, and the number of the mixing units is not less than 8. And the Kenics pipeline mixer mixing unit and the island pipeline mixer mixing unit are arranged in series at intervals when being selected.
The beneficial effects and advantages of the invention include:
the mixing units such as the perforated plate, the special-shaped plate, the spiral blade and the like in the static tubular mixer pipeline can divide, move and mix two solutions without a stirrer driven by mechanical rotation, and during turbulent flow, strong shearing force is provided to act on the two fluids by using vortex generated by the two fluids in the flowing section direction, so that the fine parts of the fluids are further divided and mixed. Finally, the two solutions can be fully and microscopically mixed within millisecond time, thereby promoting the nucleation of barium sulfate crystals and inhibiting the growth of crystal grains. In addition, in a flowing state, the generated barium sulfate nano crystal grains are quickly discharged out of a pipeline, the retention time in the reactor is short, the subsequent further agglomeration and growth are avoided, and finally the generated barium sulfate particles are small in average particle size and concentrated in particle size distribution.
Compared with the intermittent tank reaction method, the method can produce the nano barium sulfate material with fine particles and concentrated particle size distribution on the premise of not adding additives such as complexing agent, surfactant and the like, and can continuously react. In addition, the invention also has the characteristics of high controllability of particle size, miniaturization of the device, easy amplification production and the like.
Compared with a microchannel reaction method, the preparation method disclosed by the invention has the characteristics of high concentration of the used solution, high yield, stable equipment operation, no hidden danger of pipeline blockage, high efficiency, energy conservation, reduction in equipment maintenance and the like.
The preparation method has flexible capacity, can connect a plurality of static pipeline mixing reactors in parallel for production, and increases or decreases the number of the reactors according to production requirements, thereby not only meeting the requirement of basic debugging of the reaction under a small-scale test, but also meeting the requirement of large-scale industrial production.
Drawings
FIG. 1 is a schematic view of a continuous preparation system of nano barium sulfate according to the present invention.
FIG. 2 is a scanning electron micrograph of a nano barium sulfate product of example 1 according to the present invention.
FIG. 3 is a scanning electron micrograph of a nano barium sulfate product of example 2 according to the present invention.
FIG. 4 is a scanning electron micrograph of a nano barium sulfate product of example 3 according to the present invention.
FIG. 5 is a scanning electron micrograph of a nano barium sulfate product of example 4 according to the present invention.
In the figure: 1-static pipeline mixing reactor; 2-barium liquid storage tank; 3-barium liquid feeding device; 4-a feed inlet; 5-a sulfate feeding device; 6-a sulfate storage tank; 7-discharging port; 8-a first filtration device; 9-a pH adjusting device; 10-a second filtration device; 11-drying and crushing device.
Detailed Description
The following describes the specific embodiments and working procedures of the present invention with reference to the accompanying drawings and examples.
As shown in fig. 1, the system for continuously preparing nano barium sulfate according to the present invention comprises a static pipeline mixing reactor 1, a barium liquid storage tank 3 and a sulfate storage tank 6 respectively connected to a feed inlet 4 end of the static pipeline mixing reactor 1, and a first filtering device 8, a pH adjusting device 9, a second filtering device 10 and a drying and crushing device 11 which are sequentially connected to a discharge outlet 7 of the static pipeline mixing reactor 1. The water-soluble barium solution in the barium solution storage tank 3 and the sulfate solution in the sulfate storage tank 6 are respectively fed into the reactor through the barium solution feeding device 3 and the sulfate feeding device 5 which can control the flow rate.
The static pipeline mixing reactor is a mixing reactor which continuously divides and joins the liquid by using twisted blades, staggered porous plates or special-shaped plates in a pipeline under the condition of no power stirring, so that the two liquids are mixed and reacted in a wide Reynolds number range. The invention utilizes a static pipeline mixing reactor to prepare nano barium sulfate, and sulfate solution and water-soluble barium compound solution can be quickly and fully mixed to form a tiny reaction unit, so nano barium sulfate grains can be prepared; the static pipeline mixing reactor can also directly discharge the generated barium sulfate from the reactor, thereby avoiding the barium sulfate from generating an agglomeration reaction later, and separating the subsequent treatment step from the mixing reaction process, so that the whole production process is continuous and uninterrupted, and the production efficiency of the whole system is improved. According to the characteristics of the precipitation reaction, the shorter the mixing time of the two reactants subjected to the precipitation reaction is, the more sufficient the mixing is, and the more uniform the particle size of the obtained precipitate is. The two fast flowing liquids are mixed through a static pipeline mixing reactor, and the micro mixing time is far shorter than that of a tank reaction. The pipeline mixing reactor has the characteristics of miniaturization and continuous production because the reaction can be continuously carried out through the pipeline. Meanwhile, because the flowing space of the liquid in the pipeline is relatively large, the precipitation reaction can be carried out in the high-concentration solution, and the device has the characteristics of high efficiency and no frequent maintenance and cleaning.
Weighing a proper amount of water-soluble barium compound including any one of barium sulfide, barium chloride, barium nitrate and barium hydroxide, and preparing a water-soluble barium solution with the concentration of 0.5mol/L to saturated concentration in a barium solution storage tank 2 at the temperature of 30-90 ℃. Weighing a proper amount of sulfate, and preparing the sulfate solution with the concentration of 0.5mol/L to saturation concentration in a sulfate storage tank 6 at the temperature of 30-90 ℃. The barium liquid storage tank 2 and the sulfate storage tank 6 adopt heating and heat preservation measures.
The barium solution and the sulfate solution are respectively input into a feed port 4 through a quantitative feeding device (a barium solution feeding device 3 and a sulfate feeding device 5) and enter a static pipeline mixing reactor 1, so that the two solutions are subjected to continuous rapid mixing reaction in the pipeline mixing reactor.
The static pipeline mixing reactor 1 is any one or a combination of a static porous plate type pipeline mixing reactor, a static special-shaped plate type pipeline mixing reactor and a static spiral plate type pipeline mixing reactor. When the combination is selected, a plurality of or more than one of the static porous plate type pipeline mixing reactor, the static special-shaped plate type pipeline mixing reactor and the static spiral plate type pipeline mixing reactor are connected in series and/or in parallel to form the combination. In order to prevent the barium solution and the sulfate from being mixed at the feed inlet of the static pipeline mixing reactor, two liquids at the feed inlet are separated to a mixing unit. The static pipe mixing reactor has an inner diameter of 5mm to 60mm so that the flow rate of the mixed solution of the water-soluble barium solution and the sulfate solution in the static pipe mixing reactor is 0.1 to 5 m/s. In order to enable the water-soluble barium solution and the sulfate solution to rapidly flow in the mixing reactor and form turbulent-type full mixing, so that chemical reaction can be rapidly carried out to generate nano barium sulfate suspension, not less than 5 mixing units are arranged in the mixing reactor. The pressure resistance value of the static pipeline mixer is not lower than 0.2 MPa.
When a static porous plate type pipeline mixing reactor is selected, at least 5 mixing units are arranged in the static porous plate type pipeline mixing reactor, the mixing units are SMV type mixing units, the mixing units are slope format unit bodies which are overlapped alternately, and two adjacent unit bodies are arranged in a staggered mode at 90 degrees; or a BKM type mixing unit is selected, and the mixing unit is formed by arranging a plurality of groups of flat plates in a staggered way at 90 degrees; or simultaneously selecting the SMV type mixing units and the BKM type mixing units, wherein the two mixing units are alternately arranged, namely alternately arranged in series.
When selecting for use static dysmorphism plate-type pipeline mixing reactor, be provided with in it and be no less than 6 mixing unit, mixing unit selects for use luos ISG blender mixing unit.
When a static spiral sheet type pipeline mixing reactor is selected, at least 8 mixing units are arranged in the static spiral sheet type pipeline mixing reactor, the Kenics pipeline mixer mixing units are selected as the mixing units, and blades twisted into 180 degrees are staggered by 90 degrees; or selecting a mixing unit of the Qiqi pipeline mixer, wherein the mixing unit is three helical blades which are alternately combined through a pore plate and are mutually divided into 120 degrees, and the three helical blades are twisted by 90 degrees leftwards or rightwards; or simultaneously selecting a Kenics pipeline mixer mixing unit and an island qi pipeline mixer mixing unit, wherein the two mixing units are alternately arranged, namely alternately arranged in series at intervals.
And inputting the obtained barium sulfate suspension into a first filtering device 8 through a discharge port 7, performing solid-liquid separation, adding water for washing and filtering, repeating for 2-4 times, sending the washed filter cake into a pH adjusting device 9, adding water for dispersing, and adjusting the pH to 6.5-7.2 to obtain the nearly neutral barium sulfate suspension. And (3) introducing the barium sulfate suspension after pH adjustment into a second filtering device 10 for solid-liquid separation, and drying and crushing by a drying and crushing device 11 to obtain a nano barium sulfate product.
Example 1
Selecting industrial BaS as a water-soluble barium compound raw material, and preparing a BaS solution with the concentration of 1mol/L in a barium solution storage tank at 60 ℃. Selecting industrial grade Na2SO4As a sulfate raw material, Na was prepared in a sulfate tank at 40 ℃ at a concentration of 2.0mol/L2SO4And (3) solution. The static pipeline mixing reactor has an inner diameter of 5mm and is internally provided with 5 SMV type mixing units. Inputting the two solutions into a pipeline mixing reactor through a feed inlet, and respectively controlling the flow rate of the BaS solution to be 0.2m/s and Na by using a barium solution feeding device 3 and a sulfate feeding device 52SO4The flow rate of the solution was 0.1m/s at which [ Ba ] was present2+]:[SO4 2-]The mass ratio (molar ratio) of (2) is 1:1.
And inputting the barium sulfate suspension obtained by the reaction into a first filtering device, removing soluble substances in the slurry through solid-liquid separation, adding water according to the ratio of 1:4 of the slurry to wash and filter for 2 times to obtain a barium sulfate filter cake.
And (3) feeding the barium sulfate filter cake obtained after washing for 2 times into a pH adjusting device, adding water according to the proportion of 1:5 of the slurry to the water, stirring and dispersing, and adjusting the pH to 6.7. After the barium sulfate suspension liquid after pH adjustment is subjected to solid-liquid separation by a second filtering device, and is dried and crushed by a drying and crushing device, a nano barium sulfate product is obtained, the morphology of particles is shown in figure 2, and the barium sulfate content, the whiteness, the volatile matter content at 105 ℃, the average particle size of the product and the dispersibility are measured, and the results are shown in table 1.
Example 2
The specification of a static pipeline mixer is changed, the inner diameter of the mixer is 15mm, and the inner part of the mixer is alternately arranged by 5 SMV type mixing units and 5 BKM type mixing units. The other conditions were the same as in example 1. The obtained nano barium sulfate product was subjected to determination of barium sulfate content, whiteness, volatile content at 105 ℃, average particle size of the product and dispersibility, and the results are shown in table 1.
Example 3
Selecting industrial grade BaCl2As a water-soluble barium compound raw material, BaCl with the concentration of 2.4mol/L is prepared in a barium liquid storage tank at the temperature of 70 DEG C2Solution (saturated concentration). Selecting industrial grade Na2SO4As a sulfate raw material, Na was prepared in a sulfate tank at 60 ℃ at a concentration of 3.2mol/L2SO4Solution (saturated concentration). The static pipeline mixing reactor is formed by connecting two mixers in series, 8 SMV-shaped mixing units are arranged in the front-end mixer, and the inner diameter of the mixing units is 10 mm. The rear end mixer has 10 Kenics pipeline mixer mixing units inside, and the internal diameter is 10 mm. The two mixers are connected by a flange. The two solutions are input into a pipeline mixing reactor through a feed inlet, the flow rate of the two solutions is controlled to be 1.5m/s by a barium liquid feeding device 3 and a sulfate feeding device 5, and at the flow rate, [ Ba ] is fed into the pipeline mixing reactor2+]:[SO4 2-]The mass ratio of (a) to (b) is 1: 1.3.
And inputting the barium sulfate suspension obtained by the reaction into a first filtering device, removing soluble substances in the slurry through solid-liquid separation, adding water according to the ratio of 1:4 of the slurry to wash and filter for 4 times to obtain a barium sulfate filter cake.
And (3) feeding the barium sulfate filter cake obtained after washing for 4 times into a pH adjusting device, adding water according to the proportion of 1:5 of the slurry to the water, stirring and dispersing, and adjusting the pH to 6.9. After the barium sulfate suspension liquid after pH adjustment is subjected to solid-liquid separation by a second filtering device, and is dried and crushed by a drying and crushing device, a nano barium sulfate product is obtained, the morphology of particles is shown in figure 3, and the barium sulfate content, the whiteness, the volatile matter content at 105 ℃, the average particle size of the product and the dispersibility of the product are measured, which is shown in Table 1.
Example 4
The specification of the static line mixer of example 3 was changed, the inner diameters of the front and rear mixers were 15mm, the inner parts thereof were provided with 12 mixing units, and other conditions were the same as in example 3, to obtain a nano barium sulfate product, which was measured for barium sulfate content, whiteness, volatile content at 105 ℃, average particle diameter of the product, and dispersibility, as shown in table 1.
Example 5
Selecting technical grade Ba (OH)2Is prepared from water-soluble barium compound at 60 deg.C in a barium liquid tank to obtain Ba (OH) solution with concentration of 0.5mol/L2And (3) solution. Selection of technical grade (NH)4)2SO4As a sulfate raw material, (NH) was prepared in a sulfate tank at 40 ℃ at a concentration of 0.5mol/L4)2SO4And (3) solution. The static pipeline mixing reactor is formed by connecting two mixers in series, 8 BKM type mixing units with the inner diameter of 10mm are arranged in the front-end mixer. The rear end mixer is internally provided with 6 Ross ISG pipeline mixer mixing units with the inner diameter of 10 mm. The two solutions are input into a static pipeline mixing reactor through a feed inlet, and Ba (OH) is controlled by a barium liquid feeding device 3 and a sulfate feeding device 5 respectively2The flow rate of the solution was 1m/s, (NH)4)2SO4The flow rate of the solution was 2m/s at which [ Ba ] was present2+]:[SO4 2-]The mass ratio of (a) to (b) is 1: 2.
And inputting the barium sulfate suspension obtained by the reaction into a first filtering device, removing soluble substances in the slurry through solid-liquid separation, adding water according to the ratio of 1:3 of the slurry to wash and filter for 3 times to obtain a barium sulfate filter cake.
And (3) feeding the barium sulfate filter cake obtained after washing for 3 times into a pH adjusting device, adding water according to the ratio of the slurry to the water of 1:4, stirring and dispersing, and adjusting the pH to 7.2. After the barium sulfate suspension liquid after pH adjustment is subjected to solid-liquid separation by a second filtering device, and is dried and crushed by a drying and crushing device, a nano barium sulfate product is obtained, the morphology of particles is shown in figure 4, and the barium sulfate content, the whiteness, the volatile matter content at 105 ℃, the average particle size of the product and the dispersibility of the product are measured, and the determination is shown in table 1.
Example 6
The specification of the line mixer of example 5 was changed to obtain a nano barium sulfate product having an inner diameter of 15mm and 10 mixing units inside the mixer at the front and rear ends, and the whiteness of the barium sulfate content, the volatile content at 105 ℃ and the average particle diameter and dispersibility of the product were measured as shown in Table 1.
Example 7
Selecting industrial grade BaCl2As a barium source, BaCl with the concentration of 2mol/L is prepared at 80 DEG C2Adding the solution into a barium solution storage tank, and selecting industrial grade (NH)4)2SO4As a sulfate source, (NH) was prepared at 60 ℃ at a concentration of 2.2mol/L4)2SO4The solution was added to the sulfate storage tank. The static pipeline mixing reactor is formed by connecting two mixers in series, 5 SMV-type mixing units and 5 BKM-type mixing units are alternately arranged in the front-end mixer, and the inner diameter is 10 mm. The rear end mixer is internally provided with 10 Qiqi pipeline mixer mixing units with the inner diameter of 10 mm. Inputting two solutions into a static pipeline mixing reactor from a feed inlet, controlling the flow rate of the two solutions to be 2m/s by using a barium liquid feeding device 3 and a sulfate feeding device 5, and controlling the flow rate of [ Ba ] at the flow rate2+]:[SO4 2-]The mass ratio of (a) to (b) is 1: 1.1.
And inputting the barium sulfate suspension obtained by the reaction into a first filtering device, removing soluble substances in the slurry through solid-liquid separation, adding water according to the ratio of 1:3 of the slurry to wash and filter for 2 times to obtain a barium sulfate filter cake.
And (3) feeding the barium sulfate filter cake obtained after washing for 2 times into a pH adjusting device, adding water according to the ratio of the slurry to the water of 1:4, stirring and dispersing, and adjusting the pH to 6.5. After the barium sulfate suspension liquid after pH adjustment is subjected to solid-liquid separation by a second filtering device, and is dried and crushed by a drying and crushing device, a nano barium sulfate product is obtained, the morphology of particles is shown in figure 5, and the barium sulfate content, the whiteness, the volatile matter content at 105 ℃, the average particle size of the product and the dispersibility of the product are measured, and the determination is shown in table 1.
Example 8
The specification of the static line mixer of example 7 was changed so that the inner diameters of the front and rear mixers were 15mm and the inner part thereof had 12 mixing units, to obtain a nano barium sulfate product, which was measured for barium sulfate content, whiteness, volatile content at 105 ℃, average particle diameter of the product, and dispersibility, as shown in Table 1.
Example 9
The specification of the static pipe mixer of example 7 was changed, the static pipe mixer was composed of three mixers, the front end was two static perforated plate pipe mixing reactors, the inside was composed of 5 SMV type mixing units and 5 BKM type mixing units arranged alternately, and the inside diameter was 10 mm. The rear end is a static spiral plate type pipeline mixing reactor, 10 Ishogche pipeline mixer mixing units are arranged in the rear end mixer, and the inner diameter is 10 mm. The discharge ports of the two static porous plate type pipeline mixing reactors at the front end are connected with the two separated inlets of the feed port of the static spiral plate type pipeline mixing reactor at the rear end through flanges. The barium liquid feeding device 3 and the sulfate feeding device 5 are utilized to control the flow velocity of barium liquid and sulfate entering the two static porous plate type pipeline mixing reactors, wherein the flow velocity is BaCl2Flow rate 1.5m/s, (NH)4)2SO4Flow rate 0.5m/s and BaCl2Flow rate 0.5m/s, (NH)4)2SO4The flow rate was 1.5 m/s. The solution flowing through the two static porous plate type pipeline mixing reactors are converged in the back end static spiral plate type pipeline mixing reactor and continuously mixed and reacted. At this time, [ Ba ]2+]:[SO4 2-]The mass ratio of (a) to (b) is 1: 1.1.
The barium sulfate suspension obtained by the reaction was introduced into the first filtration apparatus, and the subsequent treatment was the same as in example 7. After treatment, a nano barium sulfate product is obtained, and the content of barium sulfate, whiteness, volatile matter content at 105 ℃, average particle size and dispersibility of the product are measured, and are shown in table 1.
TABLE 1 determination of the Properties of barium sulfate products prepared in the examples of the present invention
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 |
| BaSO4Content (dry basis%) | 98.97 | 98.93 | 99.32 | 99.35 | 99.21 | 99.21 | 99.53 | 99.55 | 99.58 |
| Whiteness (%) | >98.9 | >98.9 | >98.9 | >98.9 | >98.9 | >98.9 | >98.9 | >98.9 | >98.9 |
| 105 ℃ volatiles (%) | <0.08 | <0.08 | <0.08 | <0.08 | <0.08 | <0.08 | <0.08 | <0.08 | <0.08 |
| Average particle size (nm) of the product | 63 | 68 | 25 | 29 | 46 | 55 | 78 | 80 | 48 |
| Dispersibility | Superior food | Superior food | Superior food | Superior food | Superior food | Superior food | Superior food | Superior food | Superior food |
The results in the table show that the barium sulfate content of the barium sulfate products prepared in all the examples is higher than 98.9%, the whiteness is better than 98.9%, the volatile matter content at 105 ℃ is lower than 0.08%, the average particle size is 20-100nm, and the barium sulfate products have the characteristics of high purity, high whiteness, good dispersibility and small particle size and can meet the corresponding application requirements.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for continuously preparing nano barium sulfate, which is characterized by comprising the following steps:
respectively preparing a water-soluble barium solution and a sulfate solution with the concentration of 0.5mol/L to saturation concentration at the temperature of 30-90 ℃;
according to [ SO ]4 2-]:[Ba2+]The molar ratio of (1-2) to (1), respectively inputting the water-soluble barium solution and the sulfate solution into a static pipeline mixing reactor, and quickly mixing and reacting in the reactor to generate a nano barium sulfate suspension; the static pipeline mixing reactor comprises any one or a plurality of combinations of a static porous plate type pipeline mixing reactor, a static special-shaped plate type pipeline mixing reactor and a static spiral plate type pipeline mixing reactor;
carrying out solid-liquid separation on the barium sulfate suspension, washing and filtering by adding water, and repeating for 2-4 times to obtain a barium sulfate filter cake;
adding water to the barium sulfate filter cake for dispersing, and adjusting the pH to 6.5-7.2 to obtain a neutral barium sulfate suspension;
and carrying out solid-liquid separation on the neutral barium sulfate suspension, and then drying and crushing to obtain the nano barium sulfate product with the average particle size of 20-100 nm.
2. The continuous preparation method of nano barium sulfate according to claim 1, wherein the water-soluble barium solution is prepared by any one of water-soluble barium compounds including barium sulfide, barium chloride, barium nitrate, barium hydroxide; the sulfate comprises any one or a mixture of more of sodium sulfate, ammonium sulfate, potassium sulfate and magnesium sulfate; and the flow velocity of the mixed solution of the water-soluble barium solution and the sulfate solution in the static pipeline mixing reactor is 0.1-5 m/s.
3. The continuous preparation method of nano barium sulfate according to claim 1, wherein the nano barium sulfate product has a nano barium sulfate content higher than 99%, a whiteness degree better than 98.8%, and a volatile matter content at 105 ℃ lower than 0.08%.
4. A continuous preparation system of nano barium sulfate, which can be used for implementing the method according to any one of claims 1 to 3, characterized by comprising a static pipeline mixing reactor (1), a barium liquid storage tank (2), a sulfate storage tank (6), a barium liquid feeding device (3), a sulfate feeding device (5), and a first filtering device (8), a pH adjusting device (9), a second filtering device (10) and a drying and crushing device (11) which are sequentially connected with the static pipeline mixing reactor (1); the static pipeline mixing reactor (1) comprises any one or a plurality of combinations of a static porous plate type pipeline mixing reactor, a static special-shaped plate type pipeline mixing reactor and a static spiral plate type pipeline mixing reactor.
5. The continuous preparation system of nano barium sulfate according to claim 4, wherein the static pipe mixing reactor has an inner diameter of 5mm-60mm, and is provided with a plurality of mixing units therein; the pressure resistance value of the static pipeline mixer is not lower than 0.2 MPa.
6. The continuous preparation system of nano barium sulfate according to claim 5, wherein the static pipe mixing reactor is a static perforated plate type pipe mixing reactor, the mixing units in the static pipe mixing reactor are SMV type mixing units and/or BKM type mixing units, and the number of the mixing units is not less than 5.
7. The continuous preparation system of claim 5, wherein the static pipe mixing reactor is a static profiled plate type pipe mixing reactor, the mixing unit in the static pipe mixing reactor is a Ross ISG mixer mixing unit, and the number of the mixing units is not less than 6.
8. The continuous preparation system of claim 5, wherein the static pipeline mixing reactor is a static spiral-plate pipeline mixing reactor, the mixing units in the static pipeline mixing reactor are Kenics pipeline mixer mixing units and/or Isega pipeline mixer mixing units, and the number of the mixing units is not less than 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022237758A1 (en) * | 2021-05-10 | 2022-11-17 | 清华大学 | Continuous preparation method and system for nano-barium sulfate |
| CN116873964A (en) * | 2023-07-07 | 2023-10-13 | 武汉工程大学 | Flaky barium sulfate, preparation method thereof and lithium ion battery diaphragm |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3703377A1 (en) * | 1987-02-05 | 1988-08-18 | Metallgesellschaft Ag | Process for preparing ultra-fine barium sulphate by precipitation |
| CN101935116A (en) * | 2010-07-22 | 2011-01-05 | 北京交通大学 | Non-degradable organic wastewater treatment method, photocatalysis reactor and micropore static pipeline mixer |
| CN102600743A (en) * | 2012-03-27 | 2012-07-25 | 甘肃金桥给水排水设计与工程(集团)有限公司 | Static pipeline mixer |
| CN202606053U (en) * | 2012-05-20 | 2012-12-19 | 包头市锦园化工科技有限公司 | Totally-closed static pipeline continuous precipitation system for rear earth precipitation and transformation |
| CN105329930A (en) * | 2014-08-11 | 2016-02-17 | 北京化工大学 | Method for preparing nanometer barium sulfate by using molecule mixing strengthening reactor |
| CN205527787U (en) * | 2016-04-19 | 2016-08-31 | 山阳奥科粉体有限公司 | A device for producing high dispersion nano barium sulfate |
| CN108726554A (en) * | 2018-07-10 | 2018-11-02 | 昆明理工大学 | One kind efficiently preparing evengranular nano barium sulfate method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003011760A1 (en) * | 2001-07-31 | 2003-02-13 | Sachtleben Chemie Gmbh | Method for the precipitation of poorly-soluble materials such as barium sulphate for example and precipitation capsule |
| CN1206072C (en) * | 2003-04-29 | 2005-06-15 | 南京工业大学 | Process for continuously preparing superfine nano powder by precipitation method and special equipment thereof |
| DE102004059210A1 (en) * | 2004-12-09 | 2006-06-14 | Merck Patent Gmbh | Production of oxidic nanoparticles |
| CN113213520A (en) * | 2021-05-10 | 2021-08-06 | 清华大学 | Method and system for continuously preparing nano barium sulfate |
-
2021
- 2021-05-10 CN CN202110506205.7A patent/CN113213520A/en active Pending
-
2022
- 2022-05-10 WO PCT/CN2022/091902 patent/WO2022237758A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3703377A1 (en) * | 1987-02-05 | 1988-08-18 | Metallgesellschaft Ag | Process for preparing ultra-fine barium sulphate by precipitation |
| CN101935116A (en) * | 2010-07-22 | 2011-01-05 | 北京交通大学 | Non-degradable organic wastewater treatment method, photocatalysis reactor and micropore static pipeline mixer |
| CN102600743A (en) * | 2012-03-27 | 2012-07-25 | 甘肃金桥给水排水设计与工程(集团)有限公司 | Static pipeline mixer |
| CN202606053U (en) * | 2012-05-20 | 2012-12-19 | 包头市锦园化工科技有限公司 | Totally-closed static pipeline continuous precipitation system for rear earth precipitation and transformation |
| CN105329930A (en) * | 2014-08-11 | 2016-02-17 | 北京化工大学 | Method for preparing nanometer barium sulfate by using molecule mixing strengthening reactor |
| CN205527787U (en) * | 2016-04-19 | 2016-08-31 | 山阳奥科粉体有限公司 | A device for producing high dispersion nano barium sulfate |
| CN108726554A (en) * | 2018-07-10 | 2018-11-02 | 昆明理工大学 | One kind efficiently preparing evengranular nano barium sulfate method |
Non-Patent Citations (1)
| Title |
|---|
| N.KOCKMANN,J.KASTNER,P.WOIAS: "Reactive particle precipitation in liquid microchannel flow", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022237758A1 (en) * | 2021-05-10 | 2022-11-17 | 清华大学 | Continuous preparation method and system for nano-barium sulfate |
| CN116873964A (en) * | 2023-07-07 | 2023-10-13 | 武汉工程大学 | Flaky barium sulfate, preparation method thereof and lithium ion battery diaphragm |
| CN116873964B (en) * | 2023-07-07 | 2024-03-29 | 武汉工程大学 | Flaky barium sulfate, preparation method thereof and lithium ion battery diaphragm |
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