CN1163298C - Preparing method for ultromicro granule - Google Patents
Preparing method for ultromicro granule Download PDFInfo
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- CN1163298C CN1163298C CNB951053442A CN95105344A CN1163298C CN 1163298 C CN1163298 C CN 1163298C CN B951053442 A CNB951053442 A CN B951053442A CN 95105344 A CN95105344 A CN 95105344A CN 1163298 C CN1163298 C CN 1163298C
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
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Abstract
The present invention relates to a method for preparing ultrafine particles in a supergravity field. A rotary bed supergravity field device is used as a chemical reactor, and multi-phase state object streams are conveyed to a feeding port of a rotary bed and are sprayed to a filling layer. Chemical precipitation reactions under the supergravity field are carried out in the filling layer, and an emulsion after the reactions is discharged from the discharging port of the rotary bed and is conveyed to a post processing process. The present invention greatly intensifies microscopic mixture and mass transfer, the reaction time is shortened by 4 to 100 times, and the production capacity is increased by tens of to hundreds of times. Simultaneously, the quality and the grade of the ultrafine particles are improved, the distribution of particle size is narrow, and the particle size is ultrafine.
Description
The present invention relates to a kind of preparation method of ultramicro powder.Particularly issue the method for biochemical prepared in reaction ultra-fine grain at super gravity field.Also can belong to hypergravity field swinging bed application in ultramicro powder material preparation and Chemical Reaction Engineering.
Ultramicro powder (nano material) is as a kind of new material of superior performance, have wide practical use in numerous areas such as microelectronics, information, aerospace, chemical industry, machinery, automobile, biology, it comprises: metal oxide and composite particles, organic compound, inorganic compound etc.The preparation method of ultramicro powder is divided into physics method and chemical method at present, and is most widely used general with the precipitation method under normal gravitational field again in the chemical method.Generally in tank diameter or stirred tank reactor, finish the chemical precipitation reaction, as: CO
2With Ca (OH)
2The emulsion reaction generates CaCO
3Superfine product.Exist following shortcoming in actual applications: (1) particle size distribution is inhomogeneous, and restive.(2) grade repeatability was bad between product was criticized and criticized.(3) mass transfer is slow, and the reaction time is long, and energy consumption is big, and production efficiency is not high.Trace it to its cause mainly be in the reactor microcosmic mix uneven, due to the undesirable grade of microcosmic mass transfer.
In recent years, rotating bed super gravity field Study on Technology and application solved many under normal gravitational field insoluble problem.Particularly the rotating bed super gravity field device can greatly be strengthened mass transport process, makes tens meters high towers alternative with about 2 meters revolving bed.In separation processes such as absorption, parsing, distillation, use and all obtained unexpected effect.The applicant successively proposes multinomial about the rotating bed super gravity field technical patent through research for many years.Wherein " method of oil-field flooding deoxidation " (patent No.: 921020619) successfully revolving bed is applied to plant-scale separation process.However, because the super gravity field technology is the new technology that the eighties just occurs, internal operation mechanism is also continuing exploration, so its new application also needs continuous developing.Do not see open report as yet as the application in reaction engineering.
Purpose of the present invention: the super gravity field chemical method that utilizes the rotating bed super gravity field device to carry out ultramicro powder synthesizes, the microcosmic of strengthening reaction mass mixes and the microcosmic mass transfer, thereby provides a kind of Granularity Distribution even, and the reaction time is short, energy consumption is low, the ultramicro powder preparation method that efficient is high.
Main points of the present invention: this method comprises chemical reaction process and postprocessing working procedures, and its main points are that course of reaction uses the rotating bed super gravity field device as reactor, make to be reflected under the super gravity field and carry out.The multiple phase material flow of participating in the ultramicro powder synthetic reaction is compared scope by certain metering, feed gas-liquid (liquid) import of revolving bed respectively, the revolving bed rotating speed is generally 100-4000rpm (can be bigger), material enters packing layer, issue biochemical reaction at super gravity field, reacted product emulsion is discharged from the revolving bed discharging opening, directly sends into separation, washing and dry postprocessing working procedures, prepares the ultramicro powder product continuously.Perhaps the emulsion that discharging opening is discharged is sent revolving bed back to again by circulating storage groove, and material (liquid or the gas) circular response with another strand adds all the time continuously after complete reaction, enters subsequent handling, the semi-batch preparing product.
The multiple phase material flow of above-mentioned participation reaction is meant that reaction raw materials thing phase is any combination of gas, liquid, solid three-phase, but at least a be liquid phase stream.As: solution-air, liquid-liquid, gas-liquid-solid, solution-air-liquid, liquid-liquid-solid etc.Wherein gaseous stream is single-component gas or contains the above mist of two components, and reactive component should account for certain proportion in the mist.Liquid phase stream is mono-component liquid or solution, can also be to contain two kinds of components above mixing material or mixed solution.Solid phase is one pack system or multi-component hybrid solid, sneaks in a certain liquid and uses.
Above-mentioned continous way preparation technology and semi-batch preparation technology have the intrinsic reaction half-time selection of time of component meter in mind according to the key of reaction raw materials, as reaction half-time time t
1/2In the time of≤5 seconds, can adopt continuous process, work as t
1/2Preferably adopt batch-type preparation technology in the time of＞5 seconds, so that the raw material thing is reacted completely.
Above-mentioned reaction metering is more relevant with factors such as revolving bed rotating speed, mass flow, concentration than scope, and to different phase logistics, different Process configuration is then controlled different operating parameters and guaranteed that reaction is measured and compare scope.
If reaction equation is:
AA+bB → product
In the formula: A---reactant gas A component or reaction liquid A component;
B---reactant B (in liquid or the liquid-solid phase);
A, b---stoichiometric coefficient.
To solution-air or gas-liquid-solid phase logistics, the revolving bed rotating speed is not less than 100rpm; When adopting semi-batch technology, can control the gas flow scope by following formula.
(1)V
A＝(22.4～448)×10
-3a·n
B/b(m
3/h)
In the formula: V
A---with the volumetric flow of gas (m under the standard conditions of pure A conversion
3/ h).
n
B---the total mole number of B component (mol) in the B material liquid.
If above logistics press following formula and is controlled the solution-air flow-rate ratio when adopting continuous process.
(2)V
A/V
B＝(2.24～224)×10
-3×(aC
B0/b) (m
3/h)
In the formula: V
A, V
B, a, b be with (1) formula;
C
80---B component molarity (mol/m in the B material liquid
3).
To the liquid-liquid phase logistics, rotating speed can be controlled the volume flow ratio of two kinds of liquid materials by following formula greater than 100rpm.
In the formula: V
A, V
B---the volume flow ratio of two kinds of liquid.
C
A0, C
B0---material liquid A, B reactive component molarity.
The above-mentioned chemical reaction that takes place under super gravity field of the present invention is the chemical precipitation reaction, and available sediment is hydroxide, carbonate, oxalates.As: Fe (OH)
2, Zr (OH)
4, Al (OH)
3, Zn (OH)
2CaCO
3, BaCO
3, SrCO
3BaSn (C
2O
4)
21/2H
2O, CaZrO (C
2O
4) 2H
2O, BaTiO (C
2O
4)
24H
2O.Sediment is made oxide ultra micro powder through calcining, as: ZrO
2, Al
2O
3, BaTiO
3Deng.
Above-mentioned precipitation reaction is the precipitation that metal alkoxide and water reaction generate hydroxide, oxide, hydrate.Can prepare ultra micro powder product by convection drying when precipitation is oxide, when precipitation is hydroxide, hydrate, need to make the ultra micro powder through calcining.
Sediment comprises: crystallinity ultra micro powder: BaTiO
3, SrTiO
3, BaZrO
3Crystallization hydroxide powder is through being sintered into the ultra micro powder of oxide: BaSnO
3, SrSnO
3, PbSnO
3Amorphous powder in the calcining, becomes the ultra micro powder of oxide: Pb (Ti mutually without the centre
1-xZrx) O
3, LaAlO
3, NiFe
2O
4Deng.
Above-mentioned precipitation reaction product can also be an organogenous sediment.As Si
3N
4The ultra micro powder.
Effect of the present invention: owing to utilize the rotating bed super gravity field device as reactor, make material under super gravity field, precipitation reaction take place, greatly having strengthened microcosmic mixes and the microcosmic mass transfer, make CONCENTRATION DISTRIBUTION even, thereby produced the effect that reaction is difficult to expect under normal gravitational field, the reaction time can shorten 4-100 doubly (visual response system intrinsic reaction rate and decide).As to Ca (OH)
2CO
2Carbonisation shortens 5-20 doubly, has increased substantially production efficiency.The production capacity of unit interval unit reactor volume equipment can improve tens times to hundreds of times, has reduced energy consumption.Simultaneously, improved the product granularity of ultramicro powder, as CaCO
3Product, under the situation that does not add any inorganic agent, the ultramicro powder average grain diameter of this method preparation is 10-70nm (routine techniques can reach about 50-100nm after generally adding the crystal formation inorganic agent).In addition,, make and form more homogenising in the particle, obviously improved the quality and the grade of product owing to mix.
Be embodiments of the invention below.
Fig. 1 is that the present invention is used for solution-air or gas-liquid-solid phase logistics, the process chart of semi-batch preparing product.
Fig. 2 is used for solution-air or gas, liquid, solid continous way preparation technology flow chart.
Fig. 3 is used for the continuous preparation technology's flow chart of liquid-liquid phase.
Fig. 4 is used for the semi-batch flow chart.
Embodiment 1:
As shown in Figure 1: we are with ultra-fine CaCO
3Semi-batch preparation technology is example explanation implementation process.
Claim a certain amount of CaO (as 2.2Kg), with the digestion of (20 liters) water, form lime emulsion, remove impurity after filtration, place circulation storage tank 13, be heated to about 40 ℃, by pump 12, emulsion sprays to packing layer 8 from revolving bed import 6 through distributor 9.
CO
2Gas is after the decompression of steel cylinder source of the gas, with 3m
3/ h flow enters revolving bed from revolving bed gas feed 4, CO
2With contain Ca (OH)
2The situation of emulsion high turbulence in the porous aggregate 8 of bed issues biochemical precipitation reaction, generates CaCO
3Ultramicro powder.Control revolving bed rotor speed is 720 rev/mins.Reaction back emulsion enters circulation storage tank 13 by executing rotated bed blanking outlet 7, constantly by the pump circulation, with CO
2Continue to react in revolving bed, through behind about 15min, emulsion PH fades to 7-8, shows that carbonization finishes, and takes a sample and makes the X transmission electron microscope analysis, obtains the ultra-fine CaCO of even particle size distribution
3Product, the about 50nm of average grain diameter.
Example 2
Remove CO
2Gas adopts with air Mixture external, and all the other technological processes are with embodiment 1.CO
2-air Mixture is by from CO
2Air behind steel cylinder gas and the compressed machine is mixed and forms, wherein CO
2Content is at 30-40%.
The control mixed gas flow is a certain amount of situation.All the other are with example 1.
Example 3
Technological process is with example 1, Fig. 1, but reaction mass is a gas-liquid system.NaAlO
2Solution and CO
2React between gas, generate Al (OH)
3Ultramicro powder.After carbonization was finished, emulsion after filtration, obtained ultra micro Al (OH) after the washing, drying
3Particle, Al (OH)
3Through calcining, get ultra micro Al
2O
3Powder.The revolving bed rotating speed is 1200rpm.
Example 4
With example 3.But gas is CO
2-air Mixture, CO
2Gas content is controlled at a certain amount of following, gets Al (OH)
3Ultramicro powder and Al
2O
3Superfine powder.The revolving bed rotating speed is with example 3.
Example 5
Technological process as shown in Figure 2, mode of operation is that continous way is applicable to that reactant is the system of solution-air.
As Ba (OH) from the finite concentration 0.5mol/l of raw material flow container 19
2Solution, by pump 12, flow-control is at 1.0m
3Behind/the h, enter revolving bed, CO from the inlet 6 of revolving bed
2Gas is with 15m
3/ h flow velocity enters bed by gas access 4, CO in bed
2With Ba (OH)
2Precipitation reaction takes place, and forms ultra micro BaCO
3, emulsion after reaction is by feed opening 7 continuous dischargings, go that follow-up workshop section filters, washs, after the drying BaCO
3Ultramicro powder.The about 3000rpm of revolving bed rotating speed.
Example 6
With example 5, but solution is SiCl
4Alcoholic solution, reacting gas is NH
3,, obtain Si (NH) by (2) formula scope control gas liquid ratio
2, Si (NH
2)
4Deng mixture precipitation, sediment after filtration, after the washing, dry, calcining silicon nitride (Si
3N
4) the ultra micro powder.
Example 7
Fig. 3 is a liquid-liquid reactions system continous way operating process artwork.Down with the synthetic BaTiO of metal alkoxide hydrolysis
3The ultra micro powder is an example explanation implementation process.Synthetic used initial feed is the alkoxide of Ba and the alkoxide of Ti, and the Ba alkoxide is directly reacted with alcohol by metal Ba and obtains, and the titanium alkoxide is at NH
3Make titanium tetrachloride and alcohol reaction under the existence condition, reaction changes solvent into benzene after finishing, and filters out accessory substance NH
4Cl obtains, after the concentration such as 1.0mol/l of having measured barium alkoxides, titanium alkoxide, in molar ratio: Ti: Ba=1: 1 form is fully mixed two kinds of metal alkoxides, and mixed alcohol saline solution (transparent liquid) places storage tank 14, storage tank 15 mid-deionized water or distilled water.The mixed alcohol saline solution sprays to revolving bed packing layer from interior pipe inlet 16 through liquid distributor 17 through pump, water is from storage tank 15, spray to revolving bed packing layer from outer tube inlet 18 through liquid distributor 9 by pump, two kinds of liquid extremely fast efficiently mix and the generation chemical reaction in packing layer, generate white crystalline BaTiO
3Ultra micro precipitation, and from 7 dischargings of revolving bed feed opening, after filtration, make BaTiO after the washing, drying
3The ultra micro powder.In the operation, pure saline solution/water flow quantity ratio is 4.5, revolving bed rotating speed 250rpm.
Example 8
With example 7, but flow process changes the semi-batch operation into.
Will be from the BaTiO that contains of feed opening 7 outflows
3The emulsion of precipitation enters storage tank 14, mixes with pure saline solution, contacts in revolving bed, reacts with water from storage tank 15 circularly, finishes until hydrolysis of alkoxide.
Example 9
Fig. 4 is the process chart that is used for liquid-solid-liquid system, is the semi-batch operation.Finish SrTiO with the alkoxide of metal Sr, Ti and the precipitation hydrolysis of water
3Be example explanation implementation process.The oversaturated metal Sr of high concentration alkoxide emulsion and the oversaturated metal Ti alkoxide of high concentration emulsion are pressed Ti: Sr=1: 1 molar ratio, mix, and place circulation storage tank 13.Storage tank 15 is put water.The metal alkoxide mixed emulsion through pump with 1m
3/ h flow velocity sprays to the revolving bed packing layer by inlet 18 by liquid distributor 9, and water sprays to packing layer by inlet 16 through liquid distributor 17 through pump, two bursts of material efficient mixing and reaction in revolving bed, generates SrTiO
3Crystallinity ultramicro powder precipitation, reaction back emulsion is gone into storage tank 13 by feed opening 7, and constitutes circulation (circular flow 1m
3/ h), so carry out, finish up to hydrolysis, product is after filtration, washing, drying make SrTiO
3The ultra micro powder.Revolving bed rotating speed 1500rpm.
Example 10
Technological process is basically with example 9, but revolving bed has gas inlet and outlet, is used for solution-air-liquid reaction system.Solution-air-liquid material forms solution-air phase counter current contacting in rotary filler layer, precipitation reacts.
Claims (10)
1, a kind of ultramicro powder preparation of nanomaterials, comprise chemical reaction process and product postprocessing working procedures, it is characterized in that chemical reaction process utilizes the rotating bed super gravity field device to make reactor, the multiple phase material flow of participating in reaction is fed the different feeds mouth of revolving bed respectively than scope by the reaction metering, the revolving bed rotating speed is generally 100-4000rpm, material enters packing layer, under super gravity field, carry out the chemical precipitation reaction, emulsion after reaction is discharged from the revolving bed discharging opening, send into postprocessing working procedures, continous way prepares the nano material product, perhaps send emulsion back to revolving bed again by circulating storage groove,, after complete reaction, send into subsequent handling with material (liquid or the gas) circular response that another strand adds all the time continuously, semi-batch prepares the nano material product, and described ultramicro powder average grain diameter is 10～70nm; The multiple phase material flow of participating in reaction is any combination of gas-liquid-solid phase, and at least a be liquid phase stream, comprising: Gu gas-liquid, liquid-liquid, gas-liquid-, the combination of gas-liquid-liquid, liquid-liquid-solid phase.
2, preparation method according to claim 1 is characterized in that the technical process of continous way preparing product is used for having in mind in the key of reaction raw materials the intrinsic reaction half-time time t of component
1/2≤ 5 seconds precipitation reaction system; The technology of semi-batch preparing product is used for having in mind in the key of reaction raw materials the intrinsic reaction half-time time t of component
1/2＞5 seconds system.
3, preparation method according to claim 1, it is characterized in that wherein said gaseous stream is single-component gas or contains the above multicomponent gas of two components, described liquid phase stream is mono-component liquid or solution, or containing two components above mixing material or mixed solution, described solid phase is one pack system or multi-component hybrid solid.
4, preparation method according to claim 1, when it is characterized in that gas-liquid or gas-liquid-solid phase logistics adopted semi-batch preparation technology, the flow by the control vapor phase stream guarantees that the reaction metering compares scope.Gas flow is pressed following formula (1) according to different material and is calculated:
V
A＝(22.4～448)×10
-3·n
B/b(m
3/h)...(1)
In the formula, V
A-with the gas flow (m under the standard conditions of pure gas component A conversion
3/ h)
n
BThe total mole number of-liquid charging stock B component
The chemical equation stoichiometric coefficient of a, b-A, B reactive component.
5, preparation method according to claim 1, when it is characterized in that gas-liquid or gas-liquid-solid phase logistics adopted continous way preparation technology, press following formula (2) control gas-flow quantity and compare:
V
A/V
B＝(2.24～224)×10
-3×(aC
B0/b)(m
3/h)...(2)
In the formula, V
A-with the gas flow (m under the standard conditions of pure gas component A conversion
3/ h)
V
BVolume flow (the m of-B material solution
3/ h)
C
B0Total mol concentration (the mol/m of B component in the-B material liquid
3)
A, b-stoichiometric coefficient.
6, preparation method according to claim 1 is characterized in that liquid-liquid phase stream, and the volume flow ratio of controlling two kinds of liquid phase reactor things with following formula (3) measures than scope to guarantee reaction:
V
A/V
B＝(0.1～10)×(a/b)×(C
B0/C
A0)...(3)
In the formula, V
A, V
B-contain A, contain the volume flow (m of two kinds of liquid of B
3/ h)
C
A0Reactive component A molarity (mol/m among the-material liquid A
3).
7, preparation method according to claim 1 is characterized in that the reacted sediment of chemical precipitation is oxide, hydroxide, carbonate or oxalates under super gravity field.
8, preparation method according to claim 7 is characterized in that wherein said oxide, hydroxide, carbonate or oxalates are Fe (OH)
2, Zr (OH)
4, Al (OH)
3, Zn (OH)
2, CaCO
3, BaCO
3, SrCO
3, BaSn (C
2O
4)
21/2H
2O, BaTiO (C
2O
4)
24H
2O or CaZrO (C
2O
4)
22H
2O.
9, preparation method according to claim 7 is characterized in that wherein said chemical precipitation reaction is the precipitation that metal alkoxide and water reaction generate hydroxide, oxide or hydrate.
10, preparation method according to claim 7 is characterized in that wherein said precipitation reaction thing is an organic matter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB951053442A CN1163298C (en) | 1995-05-26 | 1995-05-26 | Preparing method for ultromicro granule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB951053442A CN1163298C (en) | 1995-05-26 | 1995-05-26 | Preparing method for ultromicro granule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1116146A CN1116146A (en) | 1996-02-07 |
| CN1163298C true CN1163298C (en) | 2004-08-25 |
Family
ID=5075491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB951053442A Expired - Fee Related CN1163298C (en) | 1995-05-26 | 1995-05-26 | Preparing method for ultromicro granule |
Country Status (1)
| Country | Link |
|---|---|
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-
1995
- 1995-05-26 CN CNB951053442A patent/CN1163298C/en not_active Expired - Fee Related
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|---|---|
| CN1116146A (en) | 1996-02-07 |
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