CN105329930B - A kind of method that utilization molecular mixing enhanced reactor prepares nano barium sulfate - Google Patents
A kind of method that utilization molecular mixing enhanced reactor prepares nano barium sulfate Download PDFInfo
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- CN105329930B CN105329930B CN201410392622.3A CN201410392622A CN105329930B CN 105329930 B CN105329930 B CN 105329930B CN 201410392622 A CN201410392622 A CN 201410392622A CN 105329930 B CN105329930 B CN 105329930B
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Abstract
The invention discloses a kind of method that utilization molecular mixing enhanced reactor prepares nano barium sulfate；React including barium salt solution and dilute sulfuric acid or sulfate liquor are added in molecular mixing enhanced reactor, after reaction, obtain barium sulfate suspension；The molecular mixing enhanced reactor is rotating packed bed reactor or bushing type micro passage reaction；Will be the barium sulfate suspension for obtaining post-treated, obtain nano barium sulfate powder.This method adopts high gravity rotating packed bed reactor or bushing type micro passage reaction, by controlling reaction temperature, the concentration of reaction solution, charge velocity, charge velocity simultaneously than the product nano barium sulfate for finally giving can be caused to reach particle diameter minimum (respectively less than 30nm), be distributed most narrow requirement.
Description
Technical field
The invention belongs to chemical technology field, is related to the preparation method of nano material, prepares nanometer more particularly, to one kind
The method of barium sulfate.
Background technology
Barium sulfate is a kind of important Inorganic Chemicals, is widely used in filler, coating, high-grade paint, high-grade ink, modeling
The industries such as material, ceramics.With the exploitation of New function device and flourishing for materials industry, barium sulfate is used as numerous industries
Important source material, its application expanding day significantly improved to its prescription.In recent years, many countries actively develop right
The improvement of traditional synthesis, particularly seeks new at the raising aspect such as product structure and quality, reducing energy consumption, Simplified flowsheet
Break through, while strengthen the development and application research of micropowder Yu the nano powder, electronics and special barium salt kind high to surcharge, more
Focus on releasing high-purity nm, there are the micropowders new varieties of special value in terms of granularity and related specification.So that barium salt is produced
Product occupy considerable position in modern industry.Most of barium sulfate product of domestic production is in some performance sides of powder
Still there is obvious gap in face with external product, such as：Powder granule granularity is big, pattern irregular, and main content is low, stability between batch
Difference etc..
In the prior art, prepare barium sulfate and be mainly liquid phase direct precipitation method, majority is processed using sulphuric acid, 1984
Year Japanese chemical industrial company of boundary have developed one kind makes barite and alkali carbonate mixing, reacts at high temperature, uses
20% sulfuric acid treatment produces blanc fixe, and alkali carbonate plays catalyst in the reaction, in an amount of from barite
The 0.5%-1% of barium content (theoretical value), reaction temperature are controlled at 850-1100 DEG C, make the lattice structure of barite occur to become
Change.The bulky grain barium sulfate that particle size range is at 2-20 μm can be prepared with the method.
There are microemulsion method and complexometry in addition.Microemulsion method is by BaCl2And Na2SO4Solution is configured to respectively accordingly
W/o type microemulsion system, due to mutually colliding between microemulsion micelle granule, there occurs mass exchange or transmission in water core, causes
Chemical reaction in core.As radius of water droplet is fixed so that reaction nucleation and growth are limited solely to fixed water core
Interior, the particle size for then generating wherein is also just under control.As can be seen here, the size of water core controls nanoparticle
Particle diameter, thus affect the factor of microemulsion micelle water core size to affect the size of the nanoparticle of reaction generation.Complexometry be by
BaCl2Ba is hybridly prepared into EDTA solution2+The complex system of-EDTA, then by the Na for preparing in advance2SO4Solution pours network into
React in fit system, product is centrifuged, washs, being dried, and obtains nano barium sulfate product.The barium sulfate of gained is average
Particle diameter is 47nm.
There is the shortcomings of product cut size is big, purification difficulty is high, post processing is complicated in above several method.Therefore, develop a kind of
It is more and more important that production efficiency is high, product purity is high, particle diameter is little, narrow diameter distribution production technology becomes.
During reaction precipitation method prepares nano-particle, the particle size distribution of granule depends primarily on nucleation process.Into
In nuclear process, there are two characteristic times：Nucleation induction period τ and molecular mixing characteristic time tm.Work as tm>During τ, crystallization process is received
The control of molecular mixing state, the crystal grain distribution of formation are wide；And work as tm<During τ, crystallization process is controlled by crystallization kineticses,
The homogeneous grain diameter of formation.
Molecular mixing enhanced reactor is that a class should realize molecular mixing process intensification by the special field of force or space minor effect
Reactor, they can meet tm<τ, so as to prepare the nano-particle that particle diameter is little and is evenly distributed.Hypergravity rotation filling
Bed reactor and micro passage reaction are exactly two kinds of molecular mixing enhanced reactors.
High-gravity technology (high gravity rotating packed bed) is using the Elevated Gravity more much bigger than terrestrial gravitation acceleration
The new technique strengthened to mass transfer and micro mixing, is obtained by rotating the Elevated Gravity for producing simulation on earth
.It can increase substantially the conversion ratio and selectivity of reaction, significantly the volume of diminution reactor, Simplified flowsheet, flow process,
Realize the energy-efficient of process.High gravity rotating packed bed reactor is that the extremely mixing of reinforcing micro molecule and a mass transfer sets
Standby, liquid-liquid is biphase in Elevated Gravity, the flowing contact in porous micro medium, and huge shearing force is by fluid breakup Cheng Na
The film of meter level, silk and drop, produce the interface of huge and quick renewal, promote biphase coalescence and separation, make alternate transmission fast
Degree is increased substantially, and the more conventional equipment of mass tranfer coefficient improves 10-1000 times.Research shows, in rotating packed-bed reactor, micro-
See molecular mixing characteristic time tm0.1ms or less is can reach, the t of theory calls is metm<τ, this just makes nucleation process in microcosmic
Carry out in uniform environment, the nano-particle of narrow particle size distribution so as to nucleation process is controllable, can be obtained.Li Jun equalitys have been delivered and have been received
Nano-barium sulfate ion gravity Method prepare and its characterize, text in test temperature be 40-80 DEG C, reactant concentration be 0.6-
1.4M, rotating speed are that, using the high-gravity rotating bed method for preparing nano barium sulfate under 800-1600rpm, experimental result is：Temperature
When being increased to 80 DEG C from 40 DEG C, particle size increases to 120nm from 25nm；Reactant concentration is increased to 1.4M, product from 0.6M
Particle diameter is decreased to 20nm from 60nm；Rotating speed increases to 1600rpm from 800rpm, and particle size is first decreased to 35nm from 70nm, it
Increase to 60nm again afterwards；Thus, this article draws to draw a conclusion：Temperature should be controlled within 60 DEG C；Improve the concentration of reactant
Be conducive to the reduction of product cut size；When rotating speed is less than 1200rpm, rotating speed increases, and particle diameter reduces；When rotating speed is higher than 1200rpm, turn
Speed increases, particle diameter increase.
Micro passage reaction is the chemical reaction system of the miniaturization that a kind of unit process interface yardstick is micron dimension, is
Micro- Chemical Engineering Technology that the nineties in last century rises.The features such as there is small size, bigger serface and regular microchannel due to it,
Which shows extraordinary ability at aspects such as mixing, mass transfer, heat transfers, hence it is evident that better than traditional reactor, while meeting tm<τ。
A kind of 20071017729.1 membrane dispersion type micro-channel reactors, disclose using barium chloride and sodium sulfate liquid-phase reaction system system
Standby ultra-fine barium sulfate granule.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind and prepares nano barium sulfate using molecular mixing enhanced reactor
Method.This method adopts high gravity rotating packed bed reactor or bushing type micro passage reaction, by controlling reaction simultaneously
Temperature, the concentration of reaction solution, charge velocity, charge velocity are reached than causing the product nano barium sulfate for finally giving
The most narrow requirement of particle diameter minimum (respectively less than 30nm), distribution.
To solve above-mentioned technical problem, the present invention adopts following technical proposals：
A kind of method that utilization molecular mixing enhanced reactor prepares nano barium sulfate, comprises the following steps：
1) barium salt solution and dilute sulfuric acid or sulfate liquor are added in molecular mixing enhanced reactor and are reacted, after reaction
Obtain barium sulfate suspension；
The molecular mixing enhanced reactor is rotating packed bed reactor or bushing type micro passage reaction；
The reaction temperature is 20-40 DEG C；
When reacting in rotating packed bed reactor, the concentration of the barium salt solution is 1.0mol/L-1.8mol/L；
The concentration of the sulfate liquor is 1.0mol/L-1.6mol/L；The charge velocity of the barium salt solution is 0.8-2.2L/min；
The charge velocity of the dilute sulfuric acid or sulfate liquor is 0.8-2.2L/min；The barium salt solution and dilute sulfuric acid or sulfate are molten
The charge velocity ratio of liquid is 1-1.2：1；
When reacting in bushing type micro passage reaction, the concentration of the barium salt solution is 1.2mol/L-1.7mol/L；
The concentration of the sulfate liquor is 1mol/L-1.7mol/L；The charge velocity of the barium salt solution is 6-7L/min, described dilute
The charge velocity of sulphuric acid or sulfate liquor is 1-1.4L/min；The injection of the barium salt solution and dilute sulfuric acid or sulfate liquor
Speed ratio is 5-7：1；
When the concentration of two kinds of reactants is less than above range, the collision probability of unit cell is reduced, and can cause product
The speed of growth of grain is more than nucleation rate, and then increases the particle diameter of product grain, while being also easy to cause the reunion of product；When
Concentration be higher than above range when, not by external condition in the case of, it is easy to beyond the saturated concentration of solution, can so give
The enforcement of experimentation and experiment condition causes certain difficulty；When the charge velocity of two kinds of reactants is less than above range
When, the linear speed of reactant liquor at nozzle can be caused to reduce, weaken the collision between reactant liquor, to strengthening mass transfer, reinforcing mixing
Have the opposite effect, and then affect the particle diameter of product grain；When charge velocity is higher than the scope, can improve and reaction kit is wanted
Ask, increase experimental cost, while the danger of experiment can be increased；When the charge velocity ratio of two kinds of reactants is below or above the model
When enclosing, the impurity increase in product can be caused, be that the subsequent treatment of experiment increases difficulty.
2) will be the barium sulfate suspension for obtaining post-treated, obtain nano barium sulfate powder.
The present invention is had found after the defect for studying prior art, while the concentration of controlling reaction temperature, reaction solution, note
Enter speed, charge velocity than can so that the product nano barium sulfate for finally giving reach particle diameter minimum (respectively less than 30nm),
The most narrow requirement of distribution, is tested using scanning electron microscope to product, and the mean diameter of product is 20nm or so.Its reason is this
The control of several parameters can increase the density of unit volume reaction mass, improve nucleation rate of the reactant in unit volume,
And then the purpose for suppressing product particle particle size growth is reached, the control of feed rate can cause reactant entering molecular mixing
It is more fierce after enhanced reactor to strike on filler, and then reactant is preferably cut, reactant after cutting
Grain diameter is less, equally reaches the purpose for suppressing product particle particle size growth.
Preferably, step 1) in, the barium salt solution is the aqueous solution of one or more or organic molten in following material
Agent solution：Barium nitrate, barium hydroxide, barium chloride.
It is highly preferred that the organic solvent is one or more in following material：Methanol, ethanol, ethylene glycol, isopropyl
Alcohol, glycerol, butanol, acetone, butanone, ethyl acetate, butyl acetate, tetrahydrofuran, benzene,toluene,xylene, dimethyl are sub-
Sulfone, normal hexane, hexamethylene.
Preferably, step 1) in, the sulfate liquor is the aqueous solution of one or more or organic in following material
Solvent solution：Ammonium sulfate, sodium sulfate, aluminium potassium sulfate.
It is highly preferred that the organic solvent is one or more in following material：Methanol, ethanol, ethylene glycol, isopropyl
Alcohol, glycerol, butanol, acetone, butanone, ethyl acetate, butyl acetate, tetrahydrofuran, benzene,toluene,xylene, dimethyl are sub-
Sulfone, normal hexane, hexamethylene.
Preferably, step 1) in, the dilute sulfuric acid concentration is 40%-60%.
Preferably, the rotating packed bed reactor is deflection type overgravity rotary bed reactor, rotor hypergravity
Rotary drill reactor, RPB rotating packed bed reactor, helical duct rotating packed bed reactor or rotation dish
Piece rotating packed bed reactor.
Preferably, the rotor speed scope of application of the rotating packed bed reactor is 100-6000rpm；More preferably
Ground, is 300-4000rpm；Most preferably, it is 1000-2000rpm.Rotor speed is adjusted using frequency modulation speed change instrument.Work as revolving bed
It is when rotor speed is too low, not big enough for the shearing force of reaction solution, the drop that reaction solution is cut will be caused not little enough,
Reinforcing mass transfer, the requirement of reinforcing microcosmic mixing are not reached, and then affects the grain diameter of product；The increasing of microcosmic mixing rate
Plus, be conducive to nucleation, and the increase of micromixing speed is favourable to crystal growth.When revolving bed rotor speed is too high, macroscopic view
Mixing is occupied an leading position, and then affects the grain diameter of product, while excessive speeds can improve the requirement to reactor, increases
Addition sheet, and make the dangerous of experiment become big.
Preferably, the decline structure of channel reactor of described sleeve pipe is：By an outer tube and an inner tube forming sleeves,
Annular space is left between inner tube, outer tube and constitutes annular microchannel, annular microchannel radial spacing is 100-500 μm；On the outer tube
It is provided with continuous phase inlet and outlet；Said inner tube one end is provided with dispersion phase import, other end closure, and closed end profile is circular cone
Body or bullet-shaped；Micropore is furnished with circumferentially along wall on the column inner pipe wall adjacent with closed end, micropore size scope is
0.05-100 μm, column inner pipe wall percent opening is 3%-60%, and the micropore in inner tube is that dispersion phase is exported.
The subsidiary effusion meter of centrifugal pump, peristaltic pump or dosing pump can be adopted to adjust the charge velocity of each reaction solution.
Further, the step 2) it is that the barium sulfate suspension that will be obtained is centrifuged, filters, washs, is dried, grinds, obtain
To nano barium sulfate powder.
Preferably, step 2) in, the rotor speed of the centrifugation is 3000-15000rpm；Preferably, rotor speed is
5000-13000rpm；The washing is washed selected from following one or more solution：Water, methanol, ethanol etc.；The grinding choosing
From roll grinding machine, oscillating mill, centrifugal grinder, erratic current grinding mill or mixer grinder.
Nano barium sulfate obtained in of the invention can be used for various coating (aqueouss, oiliness and powdery paints, automobile coating, wood
Device paint, exterior wall paint, corrosion resistant coating, high lac varnish, e-inks, printing-ink etc.), modified plastics (PA, PBT, PET, PC, POM,
PMMA, PP, ABS, PE, PS, automobile plastic, appliance shell, thin film, building materials plastics etc.), rubber, elastomer, papermaking, cosmetics
Deng filler, swallow agent (becoming barium meal) when being also used as having an X-rayed the intestines and stomach, the cathode expansion rod of accumulator, manufacture ceramics,
The surface smearss of the glazing type material of enamel, impression paper and art paper, the sizing agent of textile industry, glass are used as clarification
Agent, can play froth breaking and increase gloss.
Beneficial effects of the present invention are as follows：
1st, this method adopts high gravity rotating packed bed reactor or bushing type micro passage reaction, is proposed by same first
When controlling reaction temperature, the concentration of reaction solution, charge velocity, charge velocity is than the product nanometer to cause to finally give
Barium sulfate reaches particle diameter minimum (respectively less than 30nm), is distributed most narrow requirement.Its reason is that the control of these three parameters can increase
The density of unit volume reaction mass, improves nucleation rate of the reactant in unit volume, and then reaches suppression product particle
The purpose of particle size growth, the control of feed rate can cause reactant more fierce after into molecular mixing enhanced reactor
Strike on filler, and then cause reactant preferably cut, after cutting, the grain diameter of reactant is less, equally reaches
Suppress the purpose of product particle particle size growth.
2nd, this method is obtained nano barium sulfate particle diameter is little and is evenly distributed, and mean diameter is 20nm or so.This method is very
It is good to solve that nano barium sulfate particle diameter in original production is big and problem pockety, it is higher so as to give product
Application performance and added value.
3rd, present invention process flow process is simple, it is easy to operate, and repeatability is high, good product quality, it is easy to which industry is amplified.
Description of the drawings
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in further detail.
Fig. 1 is the process chart of high gravity rotating packed bed used in the present invention；
Fig. 2 is the enlarged diagram of high gravity rotating packed bed reactor used in the present invention；
Fig. 3 is the process chart of bushing type micro passage reaction used in the present invention；
The enlarged diagram of the bushing type micro passage reaction during Fig. 4 is of the invention；
Stereoscan photograph of the Fig. 5 for 1 products obtained therefrom of the embodiment of the present invention；
Stereoscan photograph of the Fig. 6 for 4 products obtained therefrom of the embodiment of the present invention；
Stereoscan photograph of the Fig. 7 for 5 products obtained therefrom of the embodiment of the present invention；
Transmission electron microscope photos of the Fig. 8 for 9 products obtained therefrom of the embodiment of the present invention.
Specific embodiment
In order to be illustrated more clearly that the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.In accompanying drawing, similar part is indicated with identical reference.It will be appreciated by those skilled in the art that institute is concrete below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
1st, high gravity rotating packed bed reactor used in the present invention is prior art, such as disclosed patent
(ZL952154307)；A kind of reacting flow chart of embodiment of the high gravity rotating packed bed reactor that the present invention is adopted is such as
Shown in Fig. 1, high gravity rotating packed bed reactor schematic diagram is as shown in Figure 2.Embodiment is as follows：
Hypergravity rotary apparatuss 1 are opened, adjusting rotating speed makes the rotating speed in super-gravity device rotor reach predetermined value.Barium salt is molten
The barium salt solution charging aperture 12 that barium salt solution Jing pumps in liquid storage tank 2 are squeezed in hypergravity rotary apparatuss；Sulfate liquor storage tank 3
In the sulfate liquor charging aperture 13 squeezed in hypergravity rotary apparatuss of sulfate liquor Jing pumps；Rotor in super-gravity device
11 drive rotation at a high speed by motor 10, produce Elevated Gravity；Barium salt solution and sulfate liquor are via the liquid on feed pipe
Distributor spray to after the inner edge of hypergravity rotary apparatuss rotor is collided and is entered in filler with filler；Into the barium in packing layer
Saline solution and sulfate liquor produce a large amount of quick surface areas for updating, strengthen significantly through segmentation, the broken, tear of silk screen
The mass transport process of molecule, shortens the nucleus growth time of both reaction postprecipitations crystallizations once controlling into the granulated of nuclear particle
Looks；Suspension Jing after hypergravity rotary apparatuss reaction precipitation is from the reacting product outlet 14 positioned at hypergravity rotary apparatuss bottom
Flow out, flow in product receiving slit 4；Suspension is put in centrifugal device 5 and is centrifuged；Centrifugation is filled in sucking filtration after finishing
Carry out washing in putting 6, filter；Afterwards product is put in drying device 7 and is dried 10-30h；Finally by dried object in lapping device
It is ground in 8 and prepares nano barium sulfate, is placed in product storage device 9.
2nd, the present invention used in bushing type micro passage reaction be prior art, such as published patent
(2007101772911).Reacting flow chart such as Fig. 3 institute of the present invention using a kind of embodiment of bushing type micro passage reaction
Show, bushing type micro passage reaction schematic diagram is as shown in Figure 4：Described sleeve pipe declines channel reactor 17 by an inner tube 25 and
27 forming sleeves of root outer tube, have annular space to constitute annular microchannel 30 between inner and outer pipe, and outer tube 27 is provided with continuous phase import 28
With outlet 31, in inner tube, one end is provided with a dispersed phase fluid import 24, and the other end is circumferentially evenly equipped with microporous micro- for tube wall
Pore membrane 29, inner and outer pipe are fixedly connected or are directly welded and fixed by flange 26 is concentric.Bushing type annular used in the present invention
The inside and outside sleeve pipe of micro passage reaction can be macromolecular material pipe or metal tube, and the inner peripheral surface of the outer peripheral face and outer tube of inner tube be
The shiny surface of polishing.The setting of the fluid import and export of inner and outer pipes be preferably make the fluid that flows out from inner tube Jing micropore with
The fluid way of contact entered from outer tube is cross-flow.Embodiment is as follows：
Bushing type annular micro passage reaction 29 is opened, the barium salt solution in barium salt solution storage tank 15 squeezes into sleeve pipe using pump
Barium salt solution charging aperture 24 in formula annular micro passage reaction；Sulfate liquor in sulfate liquor storage tank 16 is beaten using pump
Enter the sulfate liquor charging aperture 28 in bushing type annular micro passage reaction；Narrow and small ring of the reaction raw materials liquid between inner and outer pipes
Gap type is fully reacted in microchannel；The charging rate of two strands of reaction raw materials liquid can pass through to adjust the rotating speed of pump and be controlled
System, and the charging rate for adjusting reaction raw materials liquid can also reach the purpose of regulation and control particle size；Jing bushing types annular microchannel
Suspension after reactor reaction precipitation is flowed out from outlet 31, is flowed in product receiving slit 18；Suspension is put into into centrifugation
It is centrifuged in device 19；Centrifugation is carried out washing after finishing in Suction filtration device 20, is filtered；Product is put into into drying device afterwards
10-30h is dried in 21；Finally dried object is ground in lapping device 22 and prepares nano barium sulfate, be placed in product storage
In cryopreservation device 23.
The following examples are that the present invention is further illustrated, and are not limited the invention.
Embodiment 1
Aqueous solution 4000ml of the barium chloride molar concentration for 1.5mol/L is added in barium salt solution storage tank；By sodium sulfate
Molar concentration is added in sulfate liquor storage tank for the aqueous solution 4000ml of 1.5mol/L；
Hypergravity rotary apparatuss are opened, and rotating speed are adjusted to 1000rpm；Feed pump is opened, will be barium salt solution and sulfate molten
Liquid carries out precipitated crystal reaction in being transported to revolving bed simultaneously, and controls the charging charge velocity of barium salt solution and sulfate liquor
1000ml/min is, the temperature for controlling reaction system is 25 DEG C；Treat that barium salt solution and sulfate liquor charging are finished, react institute
After obtaining suspension whole outflow hypergravity rotary apparatuss, hypergravity rotary apparatuss are closed；
Gained suspension is centrifuged, and rotating speed is adjusted to 5000rpm, centrifugation time 10min；After centrifugation, solid matter is used
Pure water is washed；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 10-25nm.
Stereoscan photograph of the Fig. 5 for 1 products obtained therefrom of the embodiment of the present invention.From the figure, it can be seen that Barium sulfate crystals grain
Footpath is little and is evenly distributed.
Embodiment 2
Aqueous solution 5000ml of the barium chloride molar concentration for 1.2mol/L is added in barium salt solution storage tank；By ammonium sulfate
Molar concentration is added in sulfate liquor storage tank for the aqueous solution 5000ml of 1.2mol/L；
Hypergravity rotary apparatuss are opened, and rotating speed are adjusted to 1200rpm；Feed pump is opened, will be barium salt solution and sulfate molten
Liquid carries out precipitated crystal reaction in being transported to revolving bed simultaneously, and controls the charging charge velocity of barium salt solution and sulfate liquor
800ml/min is, the temperature for controlling reaction system is 30 DEG C；Treat that barium salt solution and sulfate liquor charging are finished, react institute
After obtaining suspension whole outflow hypergravity rotary apparatuss, hypergravity rotary apparatuss are closed；
Gained suspension is centrifuged, and rotating speed is adjusted to 5000rpm, centrifugation time 10min；After centrifugation, solid matter is used
Pure water is washed；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 5-30nm.
Embodiment 3
Aqueous solution 4500ml of the barium nitrate molar concentration for 1.3mol/L is added in barium salt solution storage tank；By dilute sulfuric acid
(concentration is 40-45%) 4500ml is added in sulfate liquor storage tank；
Hypergravity rotary apparatuss are opened, and rotating speed are adjusted to 1300rpm；Feed pump is opened, will be barium salt solution and dilute sulfuric acid same
When be transported to revolving bed in carry out precipitated crystal reaction, and control the charging charge velocity of barium salt solution and dilute sulfuric acid and be
1100ml/min, the temperature for controlling reaction system are 35 DEG C；Treat that barium salt solution and dilute sulfuric acid charging are finished, reaction gained suspension
After all flowing out hypergravity rotary apparatuss, hypergravity rotary apparatuss are closed；
Gained suspension is centrifuged, and rotating speed is adjusted to 8000rpm, centrifugation time 10min；After centrifugation, solid matter is used
Pure water is washed；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 10-25nm.
Embodiment 4
Methanol solution 6000ml of the barium hydroxide molar concentration for 1.5mol/L is added in barium salt solution storage tank；By sulfur
Sour sodium molar concentration is added in sulfate liquor storage tank for the aqueous solution 6000ml of 1.5mol/L；
Hypergravity rotary apparatuss are opened, and rotating speed are adjusted to 1800rpm；Feed pump is opened, will be barium salt solution and sulfate molten
Liquid carries out precipitated crystal reaction in being transported to revolving bed simultaneously, and controls the charging charge velocity of barium salt solution and sulfate liquor
900ml/min is, the temperature for controlling reaction system is 30 DEG C；Treat that barium salt solution and sulfate liquor charging are finished, react institute
After obtaining suspension whole outflow hypergravity rotary apparatuss, hypergravity rotary apparatuss are closed；
Gained suspension is centrifuged, and rotating speed is adjusted to 10000rpm, centrifugation time 20min；Solid matter after centrifugation
Washed with pure water；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 5-20nm.
Stereoscan photograph of the Fig. 6 for 4 products obtained therefrom of the embodiment of the present invention.
Embodiment 5
Methanol solution 5000ml of the barium chloride molar concentration for 1mol/L is added in barium salt solution storage tank；By sodium sulfate
Molar concentration is added in sulfate liquor storage tank for the methanol solution 5000ml of 1mol/L；
Hypergravity rotary apparatuss are opened, and rotating speed are adjusted to 1500rpm；Feed pump is opened, will be barium salt solution and sulfate molten
Liquid carries out precipitated crystal reaction in being transported to revolving bed simultaneously, and controls the charging charge velocity of barium salt solution and sulfate liquor
1500ml/min is, the temperature for controlling reaction system is 40 DEG C；Treat that barium salt solution and sulfate liquor charging are finished, react institute
After obtaining suspension whole outflow hypergravity rotary apparatuss, hypergravity rotary apparatuss are closed；
Gained suspension is centrifuged, and rotating speed is adjusted to 12000rpm, centrifugation time 10min；Solid matter after centrifugation
Washed with pure water；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 5-20nm.
Stereoscan photograph of the Fig. 7 for 5 products obtained therefrom of the embodiment of the present invention.
Embodiment 6
Aqueous solution 6000ml of the barium chloride molar concentration for 1.3mol/L is added in barium salt solution storage tank；By sodium sulfate
Molar concentration is added in sulfate liquor storage tank for the aqueous solution 6000ml of 1.3mol/L；
Hypergravity rotary apparatuss are opened, and rotating speed are adjusted to 1200rpm；Feed pump is opened, will be barium salt solution and sulfate molten
Liquid carries out precipitated crystal reaction in being transported to revolving bed simultaneously, and controls the charging charge velocity of barium salt solution and sulfate liquor
1800ml/min is, the temperature for controlling reaction system is 40 DEG C；Treat that barium salt solution and sulfate liquor charging are finished, react institute
After obtaining suspension whole outflow hypergravity rotary apparatuss, hypergravity rotary apparatuss are closed；
Gained suspension is centrifuged, and rotating speed is adjusted to 10000rpm, centrifugation time 20min；Solid matter after centrifugation
Washed with pure water；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 5-20nm.
Embodiment 7
Aqueous solution 10000ml of the barium chloride molar concentration for 1.3mol/L is added in barium salt solution storage tank；By sulphuric acid
Sodium molar concentration is added in sulfate liquor storage tank for the aqueous solution 5000ml of 1.3mol/L；
Bushing type micro passage reaction is first opened, feed pump is then turned on, barium salt solution and sulfate liquor are conveyed simultaneously
Precipitated crystal reaction is carried out into bushing type annular micro passage reaction, and barium salt solution feed rate is controlled for 6100ml/
Min, sulfate liquor feed rate are 1000ml/min, and the temperature for controlling reaction system is 30 DEG C；Treat barium salt solution and sulphuric acid
Saline solution charging is finished, and after reaction gained suspension all flows out micro passage reaction, closes micro passage reaction；
Gained suspension is centrifuged, and rotating speed is adjusted to 10000rpm, centrifugation time 10min；Solid matter after centrifugation
Washed with pure water；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 10-30nm.
Embodiment 8
Aqueous solution 10000ml of the barium hydroxide molar concentration for 1.5mol/L is added in barium salt solution storage tank；By sulfur
Sour sodium molar concentration is added in sulfate liquor storage tank for the aqueous solution 6000ml of 1.5mol/L；
Bushing type annular micro passage reaction is first opened, feed pump is then turned on, by barium salt solution and sulfate liquor simultaneously
Precipitated crystal reaction is carried out in being delivered to bushing type annular micro passage reaction, and is controlled barium salt solution feed rate and is
6300ml/min, sulfate liquor feed rate are 1400ml/min, and the temperature for controlling reaction system is 25 DEG C；Treat barium salt solution
Finish with sulfate liquor charging, after reaction gained suspension all flows out micro passage reaction, close micro passage reaction；
Gained suspension is centrifuged, and rotating speed is adjusted to 12000rpm, centrifugation time 20min；Solid matter after centrifugation
Washed with pure water；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 5-25nm.
Embodiment 9
Aqueous solution 10000ml of the barium chloride molar concentration for 1.2mol/L is added in barium salt solution storage tank；By sulphuric acid
Sodium molar concentration is added in sulfate liquor storage tank for the aqueous solution 5000ml of 1mol/L；
Bushing type annular micro passage reaction is first opened, feed pump is then turned on, by barium salt solution and sulfate liquor simultaneously
Precipitated crystal reaction is carried out in being delivered to bushing type annular micro passage reaction, and is controlled barium salt solution feed rate and is
6600ml/min, sulfate liquor feed rate are 1100ml/min, and the temperature for controlling reaction system is 30 DEG C；Treat barium salt solution
Finish with sulfate liquor charging, after reaction gained suspension all flows out micro passage reaction, close micro passage reaction；
Gained suspension is centrifuged, and rotating speed is adjusted to 12000rpm, centrifugation time 20min；Solid matter after centrifugation
Washed with pure water；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 10-20nm.
Transmission electron microscope photos of the Fig. 8 for 9 products obtained therefrom of the embodiment of the present invention.
Embodiment 10
Tetrahydrofuran solution 10000ml of the barium chloride molar concentration for 1.2mol/L is added in barium salt solution storage tank；
Tetrahydrofuran solution 4000ml of the sodium sulfate molar concentration for 1.2mol/L is added in sulfate liquor storage tank；
Bushing type annular micro passage reaction is first opened, feed pump is then turned on, by barium salt solution and sulfate liquor simultaneously
Precipitated crystal reaction is carried out in being delivered to bushing type annular micro passage reaction, and is controlled barium salt solution feed rate and is
6000ml/min, sulfate liquor feed rate are 1000ml/min, and the temperature for controlling reaction system is 25 DEG C；Treat barium salt solution
Finish with sulfate liquor charging, after reaction gained suspension all flows out micro passage reaction, close micro passage reaction；
Gained suspension is centrifuged, and rotating speed is adjusted to 12000rpm, centrifugation time 20min；Solid matter after centrifugation
Washed with pure water；It is placed in vacuum drying oven again and is dried 20h；Gained solid is ground and obtains product nano barium sulfate.
After testing, the one-dimensional size of nanometer barium sulfate grains is 5-20nm.
Embodiment 11-21
Repeat embodiment 10, which the difference is that only：The organic solvent of dissolving barium chloride in following material one
Plant or various：Isopropanol, glycerol, butanol, propanol, butanone, ethyl acetate, butyl acetate, benzene,toluene,xylene, dimethyl
Sulfoxide；As a result it is close with embodiment 10.
Embodiment 22-35
Repeat embodiment 1, which the difference is that only：The one kind of the organic solvent of dissolving sodium sulfate in following material
Or it is various：Isopropanol, glycerol, butanol, acetone, butanone, ethyl acetate, butyl acetate, benzene,toluene,xylene, dimethyl are sub-
Sulfone, normal hexane, hexamethylene, acetone and butanone (volume ratio 1：1)；As a result it is close with embodiment 1.
Embodiment 36
Repeat embodiment 1, which the difference is that only：The sulfate is aluminium potassium sulfate.As a result it is close with embodiment 1
Seemingly.
Embodiment 37
Repeat embodiment 1, which the difference is that only：The reaction temperature is 20 DEG C.As a result it is close with embodiment 1.
Embodiment 38
Repeat embodiment 1, which the difference is that only：The concentration of the barium salt solution is 1.8mol/L；The sulfate
The concentration of solution is 1.6mol/L；The charge velocity of the barium salt solution is 2.2L/min；The dilute sulfuric acid or sulfate liquor
Charge velocity be 2.2L/min.As a result it is close with embodiment 1.
Embodiment 39
Repeat embodiment 1, which the difference is that only：The concentration of the barium salt solution is 1.5mol/L；The sulfate
The concentration of solution is 1.4mol/L；The charge velocity of the barium salt solution is 1.5L/min；The dilute sulfuric acid or sulfate liquor
Charge velocity be 1.8L/min.As a result it is close with embodiment 1.
Embodiment 40
Repeat embodiment 7, which the difference is that only：The concentration of the barium salt solution is 1.7mol/L；The sulfate
The concentration of solution is 1.7mol/L；The charge velocity of the barium salt solution is 7L/min；The dilute sulfuric acid or sulfate liquor
Charge velocity is 1.4L/min.As a result it is close with embodiment 7.
Some embodiments and comparative example
When the first, using rotating packed bed reactor, impact of the temperature of the measurement to product：
Barium salt solution is barium chloride solution, and sulfate liquor is metabisulfite solution, and sulfate liquor concentration is 1.3mol/L,
The charge velocity of barium salt solution is 1.9L/min, and barium salt is 1.1 with the charge velocity ratio of sulfate：1.
Impact of the temperature to product (rotor speed is 1500rpm)：
| Temperature (DEG C) | 10 | 15 | 20 | 25 | 35 | 40 | 50 | 60 | 70 | 80 | 90 |
| Product mean diameter (nm) | 40 | 35 | 29 | 24 | 27 | 30 | 35 | 38 | 42 | 44 | 43 |
When the 2nd, using rotating packed bed reactor：
Barium salt solution is barium chloride solution, and sulfate liquor is metabisulfite solution, and reaction temperature is 25 DEG C, hypergravity rotation
The rotor speed of bed reactor is 1500rpm.Condition determination changes the impact to product.
Barium salt solution concentrations on product impact (sulfate liquor concentration be 1.3mol/L, the charge velocity of barium salt solution
For 1.9L/min, barium salt is 1.1 with the charge velocity ratio of sulfate：1)：
| Barium salt solution concentration (mol/L) | 0.05 | 0.1 | 0.5 | 1 | 1.2 | 1.5 | 1.7 | 1.9 | 2.1 |
| Product mean diameter (nm) | 65 | 58 | 55 | 30 | 29 | 25 | 27 | 35 | 37 |
Sulfate liquor concentrations on product impact (barium salt solution concentration be 1.25mol/L, the charge velocity of barium salt solution
For 1.9L/min, barium salt is 1.1 with the charge velocity ratio of sulfate：1)：
| Sulfate liquor concentration (mol/L) | 0.05 | 0.1 | 0.5 | 1 | 1.3 | 1.6 | 1.7 | 1.9 | 2.1 |
| Product mean diameter (nm) | 70 | 65 | 52 | 30 | 24 | 23 | 32 | 40 | 39 |
(barium salt solution concentration is 1.25mol/L, sulfate liquor concentration for impact of the charge velocity of barium salt solution to product
For 1.3mol/L, barium salt is 1.1 with the charge velocity ratio of sulfate：1)：
| The charge velocity (L/min) of barium salt solution | 0.6 | 0.8 | 1.5 | 2.2 | 3 | 3.5 |
| Product mean diameter (nm) | 50 | 29 | 25 | 24 | 36 | 37 |
(barium salt solution concentration is 1.25mol/L, and sulfate liquor is dense for impact of the charge velocity of sulfate liquor to product
Spend for 1.3mol/L, barium salt is 1.1 with the charge velocity ratio of sulfate：1)：
| The charge velocity (L/min) of sulfate liquor | 0.6 | 0.8 | 1.5 | 2.2 | 3.5 |
| Product mean diameter (nm) | 48 | 30 | 24 | 22 | 33 |
The charge velocity of barium salt solution and sulfate liquor compare product impact (barium salt solution concentration is 1.25mol/L,
Sulfate liquor concentration is 1.3mol/L, and the charge velocity of barium salt solution is 1.9L/min)：
| The charge velocity ratio of barium salt solution and sulfate liquor | 0.1 | 0.3 | 1.0 | 1.2 | 1.8 | 2.8 |
| Product mean diameter (nm) | 74 | 57 | 25 | 24 | 56 | 67 |
When the 3rd, using bushing type micro passage reaction：
Barium salt solution is barium chloride solution, and sulfate liquor is metabisulfite solution, and reaction temperature is 25 DEG C.Condition determination changes
Become the impact to product.
Barium salt solution concentrations on product impact (sulfate liquor concentration be 1.3mol/L, the charge velocity of barium salt solution
For 6.1L/min, barium salt is 5 with the charge velocity ratio of sulfate：1)：
| Barium salt solution concentration (mol/L) | 0.1 | 0.5 | 1 | 1.2 | 1.5 | 1.7 | 1.9 | 2.1 |
| Product mean diameter (nm) | 59 | 42 | 31 | 24 | 23 | 27 | 31 | 34 |
Sulfate liquor concentrations on product impact (barium salt solution concentration be 1.25mol/L, the charge velocity of barium salt solution
For 6.1L/min, barium salt is 5 with the charge velocity ratio of sulfate：1)：
| Sulfate liquor concentration (mol/L) | 0.1 | 0.5 | 1 | 1.3 | 1.6 | 1.7 | 1.9 | 2.1 |
| Product mean diameter (nm) | 54 | 43 | 27 | 25 | 25 | 29 | 31 | 29 |
(barium salt solution concentration is 1.25mol/L, sulfate liquor concentration for impact of the charge velocity of barium salt solution to product
For 1.3mol/L, barium salt is 5 with the charge velocity ratio of sulfate：1)：
| The charge velocity (L/min) of barium salt solution | 2.0 | 4.5 | 6 | 7 | 8 |
| Product mean diameter (nm) | 64 | 33 | 24 | 22 | 33 |
(barium salt solution concentration is 1.25mol/L, and sulfate liquor is dense for impact of the charge velocity of sulfate liquor to product
Spend for 1.3mol/L, barium salt is 5 with the charge velocity ratio of sulfate：1)：
| The charge velocity (L/min) of sulfate liquor | 0.15 | 0.3 | 1.0 | 1.4 | 3 |
| Product mean diameter (nm) | 67 | 56 | 29 | 24 | 34 |
The charge velocity of barium salt solution and sulfate liquor compare product impact (barium salt solution concentration is 1.25mol/L,
Sulfate liquor concentration is 1.3mol/L, and the charge velocity of barium salt solution is 6.0L/min)：
| The charge velocity ratio of barium salt solution and sulfate liquor | 1 | 3 | 5 | 7 | 10 | 12 |
| Product mean diameter (nm) | 55 | 46 | 27 | 26 | 33 | 52 |
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all of embodiment cannot be exhaustive here, it is every to belong to this
Bright technical scheme it is extended obvious change or change still in protection scope of the present invention row.
Claims (13)
1. a kind of method that utilization molecular mixing enhanced reactor prepares nano barium sulfate, it is characterised in that comprise the following steps：
1）Barium salt solution and dilute sulfuric acid or sulfate liquor are added in molecular mixing enhanced reactor and are reacted, obtained after reaction
Barium sulfate suspension；
The molecular mixing enhanced reactor is rotating packed bed reactor or bushing type micro passage reaction；
2）Will be the barium sulfate suspension for obtaining post-treated, obtain nano barium sulfate powder；
The reaction temperature is 20-40 DEG C；
When reacting in rotating packed bed reactor, the concentration of the barium salt solution is 1.0mol/L-1.8mol/L；It is described
The concentration of sulfate liquor is 1.0mol/L-1.6mol/L；The charge velocity of the barium salt solution is 0.8-2.2L/min；It is described
The charge velocity of dilute sulfuric acid or sulfate liquor is 0.8-2.2L/min；The barium salt solution and dilute sulfuric acid or sulfate liquor
Charge velocity ratio is 1-1.2：1；
When reacting in bushing type micro passage reaction, the concentration of the barium salt solution is 1.2mol/L-1.7mol/L；It is described
The concentration of sulfate liquor is 1mol/L-1.7mol/L；The charge velocity of the barium salt solution be 6-7L/min, the dilute sulfuric acid
Or the charge velocity of sulfate liquor is 1-1.4L/min；The charge velocity of the barium salt solution and dilute sulfuric acid or sulfate liquor
Than for 5-7：1.
2. the method that a kind of utilization molecular mixing enhanced reactor according to claim 1 prepares nano barium sulfate, which is special
Levy and be, the barium salt solution is the aqueous solution of one or more or organic solvent solution in following material：Barium nitrate, hydrogen-oxygen
Change barium, barium chloride.
3. the method that a kind of utilization molecular mixing enhanced reactor according to claim 2 prepares nano barium sulfate, which is special
Levy and be, the organic solvent is one or more in following material：Methanol, ethanol, ethylene glycol, isopropanol, glycerol, fourth
Alcohol, acetone, butanone, ethyl acetate, butyl acetate, tetrahydrofuran, benzene,toluene,xylene, dimethyl sulfoxide, normal hexane, ring
Hexane.
4. the method that a kind of utilization molecular mixing enhanced reactor according to claim 1 prepares nano barium sulfate, which is special
Levy and be, the sulfate liquor is the aqueous solution of one or more or organic solvent solution in following material：Ammonium sulfate, sulfur
Sour sodium, aluminium potassium sulfate.
5. the method that a kind of utilization molecular mixing enhanced reactor according to claim 4 prepares nano barium sulfate, which is special
Levy and be, the organic solvent is one or more in following material：Methanol, ethanol, ethylene glycol, isopropanol, glycerol, fourth
Alcohol, acetone, butanone, ethyl acetate, butyl acetate, tetrahydrofuran, benzene,toluene,xylene, dimethyl sulfoxide, normal hexane, ring
Hexane.
6. the method that a kind of utilization molecular mixing enhanced reactor according to claim 1 prepares nano barium sulfate, which is special
Levy and be, the dilute sulfuric acid concentration is 40%-60%.
7. the method that a kind of utilization molecular mixing enhanced reactor according to claim 1 prepares nano barium sulfate, which is special
Levy and be, the rotor speed scope of application of the rotating packed bed reactor is 100-6000rpm.
8. the method that a kind of utilization molecular mixing enhanced reactor according to claim 1 prepares nano barium sulfate, which is special
Levy and be, the rotor speed scope of application of the rotating packed bed reactor is 300-4000rpm.
9. the method that a kind of utilization molecular mixing enhanced reactor according to claim 1 prepares nano barium sulfate, which is special
Levy and be, the rotor speed scope of application of the rotating packed bed reactor is 1000-2000rpm.
10. the method that a kind of utilization molecular mixing enhanced reactor according to claim 1 prepares nano barium sulfate, which is special
Levy and be,
The rotating packed bed reactor is deflection type overgravity rotary bed reactor, the high-gravity rotating bed reaction of rotor
The rotation of device, RPB rotating packed bed reactor, helical duct rotating packed bed reactor or rotating compact disc hypergravity
Rotated bed reactor；
The decline structure of channel reactor of described sleeve pipe is：By an outer tube and an inner tube forming sleeves, inner tube, outer tube it
Between leave annular space and constitute annular microchannel, annular microchannel radial spacing is 100-500 μm；The outer tube is provided with continuous phase and enters
Mouth and outlet；Said inner tube one end is provided with dispersion phase import, other end closure, and closed end profile is cone or sub-warhead
Shape；Micropore is furnished with circumferentially along wall on the column inner pipe wall adjacent with closed end, micropore size scope is 0.05-100 μm, post
Shape inner pipe wall percent opening is 3%-60%, and the micropore in inner tube is that dispersion phase is exported.
The method that a kind of 11. utilization molecular mixing enhanced reactors according to claim 1 prepare nano barium sulfate, which is special
Levy and be, the step 2）It is that the barium sulfate suspension that will be obtained is centrifuged, filters, washs, is dried, grinds, obtains a nanometer sulphuric acid
Barium dust.
The method that a kind of 12. utilization molecular mixing enhanced reactors according to claim 11 prepare nano barium sulfate, its
It is characterised by, the rotor speed of the centrifugation is 3000-15000rpm；The washing is washed selected from following one or more solution
Wash：Water, methanol, ethanol；The grinding is selected from roll grinding machine, oscillating mill, centrifugal grinder, erratic current grinding mill or stirring
Grinder.
The method that a kind of 13. utilization molecular mixing enhanced reactors according to claim 11 prepare nano barium sulfate, its
It is characterised by, the rotor speed of the centrifugation is 5000-13000rpm.
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| CN107285364B (en) * | 2016-04-05 | 2019-02-15 | 宜宾丝丽雅集团有限公司 | A method of using viscose rayon produce in sodium sulfate waste liquid produce nano barium sulfate |
| CN107285365A (en) * | 2016-04-05 | 2017-10-24 | 宜宾丝丽雅集团有限公司 | The technique that sodium sulfate waste liquid produces nanometer calcium sulfate in a kind of utilization viscose rayon production |
| CN107285363B (en) * | 2016-04-05 | 2019-02-12 | 宜宾丝丽雅集团有限公司 | A method of using viscose rayon produce in sodium sulfate waste liquid produce nanometer calcium sulfate |
| CN107285366A (en) * | 2016-04-05 | 2017-10-24 | 宜宾丝丽雅集团有限公司 | The technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production |
| CN107281983A (en) * | 2016-04-05 | 2017-10-24 | 宜宾丝丽雅集团有限公司 | A kind of micro passage reaction for producing nanometer sulfate |
| CN108793226B (en) * | 2017-05-03 | 2021-07-13 | 北京化工大学 | Method for preparing transparent zinc oxide liquid-phase dispersion by supergravity technology |
| CN109133139A (en) * | 2017-06-16 | 2019-01-04 | 南风化工集团股份有限公司 | A method of sub-micro nano-barium sulfate is prepared using pump type reaction |
| CN108862355B (en) * | 2018-07-13 | 2020-08-18 | 北京石油化工学院 | Method for preparing barium sulfate particles by micro-channel method |
| CN110294487A (en) * | 2019-05-29 | 2019-10-01 | 清华大学 | A kind of microreactor prepares the new process of polymolecularity barium sulfate material |
| CN112299467B (en) * | 2019-07-31 | 2022-10-28 | 北京化工大学 | Preparation method of monodisperse oil-phase nano barium sulfate dispersoid |
| CN110976901A (en) * | 2019-12-31 | 2020-04-10 | 湘潭大学 | Preparation method of nano copper powder |
| 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 |
| CN111569780B (en) * | 2020-05-24 | 2021-12-28 | 西安交通大学 | Internal mixing type supercritical hydrothermal synthesis nano powder reactor |
| CN113213520A (en) * | 2021-05-10 | 2021-08-06 | 清华大学 | Method and system for continuously preparing nano barium sulfate |
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