CN101905870B - Method for preparing nanoscale anionic laminar material continuously - Google Patents
Method for preparing nanoscale anionic laminar material continuously Download PDFInfo
- Publication number
- CN101905870B CN101905870B CN2010102089011A CN201010208901A CN101905870B CN 101905870 B CN101905870 B CN 101905870B CN 2010102089011 A CN2010102089011 A CN 2010102089011A CN 201010208901 A CN201010208901 A CN 201010208901A CN 101905870 B CN101905870 B CN 101905870B
- Authority
- CN
- China
- Prior art keywords
- laminar material
- rotating bed
- supergravity reactor
- solution
- helix channel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a method for preparing a nanoscale anionic laminar material continuously, which mainly comprises the steps of reacting, filtering, washing and drying. Compared with the conventional method for preparing the anionic laminar material in China, the method has the following advantages: (1) a helix channel rotating bed high gravity reactor is adopted to enable nucleus formation to be formed in a uniform micro hybrid environment quickly with a narrowed particle size distribution, the reaction solution in the reactor is kept under a stable high pH value condition by condensing NH3 so as to avoid generating an impurity phase, the reaction time is short and the operation is simple; (2) crystal seeds are added during reaction to greatly reduce the induction period of nucleus formation and accelerate nucleus formation, the crystallinity is high, the particle size distribution is more uniform, the size and distribution of newly generated particles can be controlled according to the particle size of the added crystal seeds, and thus, the particle size is controllable; (3) a crystallization process is not required for product post processing; and (4), the process is quick and allows for continuous production, and the average particle size of the prepared anionic laminar material is 30 to 90 nanometers.
Description
Technical field
The present invention relates to a kind of continuous method for preparing nanoscale anionic laminar material, the method for the nanoscale anionic laminar material that particularly continuous prepared sizes are evenly distributed under the hypergravity condition.
Background technology
Anion laminated material is as a kind of novel anionic clay materials, has broad application prospects at numerous areas such as catalysis, absorption, fire-retardant, medical, electronics and environmental protection.The preparation method of present domestic comparative maturity is a coprecipitation method, but inhomogeneous because of the mixing of coprecipitation method microcosmic, is prone to cause nucleation and crystallization to carry out simultaneously, produces dephasign, makes that the product grains size is uneven.The while palpus is through subsequent disposal such as crystallization, and crystallization time is long.As utilizing nucleation crystallization isolation method to prepare anion laminated material among the CN1288078, though the reaction times shortens, but still need crystallization, and crystallization time is long, the product particle diameter is (0.2-0.3 μ m) greatly.CN101665233 prepares the layered double hydroxide that particle is 12-80nm, but the autoclave crystallization of reaction needs high energy consumption and adding inflammable substance Peng Qinghuana, complex process, production cost is high, is difficult to large-scale industrial production.The nano hydrotalcite particle diameter that CN101538019 prepares is between 30-70nm, but need extracted in toluene after the reaction, subsequent disposal is complicated, produces the three wastes.The preparation process of ZL01134425.3 magnesia-alumina double-hydroxyl complex metal oxides needs secondary reaction and crystallization, and technological operation is complicated, and reaction conditions is difficult to control.Wang Yong is waiting [Wang Yong is waiting, artificial lens journal .2008,37 (5): 1219-1223] to utilize the microwave hydrothermal single stage method to prepare the Mg-Al hydrotalcite; Its technology weak point consuming time need not crystallization process, but temperature of reaction is high; Be prone to produce dephasign, and production cost is high, can not serialization production.In addition, in reaction, add crystal seed and can shorten crystal nucleation inductive phase greatly, make nucleation rapid, and percent crystallinity high [Deng Xin etc., functional materials .2008,2 (39): 341-345].
Fast a large amount of nucleation, to slow down crystal growth be the be evenly distributed keys of nanoscale anionic laminar material of prepared sizes, transmit and micro mixing between strengthening phase as much as possible, and high-gravity technology has special advantages in this respect.At present domesticly utilize hypergravity to prepare nano material to have become focus; Utilize hypergravity to prepare nanometer and nano composite ceramic coating like ZL200410098906.8; ZL00132275.3 utilizes carburizing reagent to prepare nano silicon, and CN1461731 adopts high-gravity technology to prepare nanometer grade super fine calcium carbonate.But also do not see at present and utilize high-gravity technology, need not crystallization process, continuously the prepared sizes report of nanoscale anionic laminar material that is evenly distributed.
Summary of the invention
The purpose of this invention is to provide a kind ofly be easy to continuous industry production, the reaction times is short, technological operation is simple, the pollution-free method for preparing anion laminated material, prepared little, the even particle size distribution of anion laminated material particle diameter.
The present invention seeks to realize that a kind of continuous method for preparing nanoscale anionic laminar material mainly by reaction, is filtered through following mode, washing, dry several steps is formed:
(1) the preparing metal ionic concn is 0.01～0.10mol/L soluble M
2+And M
3+The metal-salt aqua liquid is pressed M
2+With M
3+Mol ratio be 2～4 to be made into the soluble metallic salt mixed solution; Compound concentration is the precipitant solution of 0.1～10.0mol/L in addition, and the total mol ratio of negatively charged ion in precipitation agent amount of substance and the soluble metal salts solution is 0.5～5.0;
(2) with the soluble metallic salt mixed solution join be preheated to 20～100 ℃ in the fore-warmer tank of rotating bed with helix channel supergravity reactor after; Starting up's rotating bed with helix channel supergravity reactor; After treating that liquid flow rate reaches stationary value of 50～1000L/h in the rotating bed with helix channel supergravity reactor; Is that 10～500L/h evenly adds precipitant solution to the rotating bed with helix channel supergravity reactor with flow, and control rotating bed with helix channel supergravity reactor rotating speed is 500～5000rpm, 20～100 ℃ of reacting liquid temperatures; When effluent pH reach 8.0～10.0 and tend towards stability after; Continue reaction 5～20min, reaction solution is derived, collect reaction solution;
(3) with reacting liquid filtering, washing precipitate is neutral until washings, and drying is ground and promptly got nanoscale anionic laminar material.
Crystal seed is added in the soluble metallic salt mixed solution, and addition is 0.5～5.0% of a soluble metallic salt weight.
Described M
2+Be Mg
2+, Zn
2+, Co
2+, Cu
2+, Ni
2+, Mn
2+Or Ca
2+Metals ion, M
3+Be Al
3+, Fe
3+Or Cr
3+Metals ion; Negatively charged ion in the soluble metallic salt mixed solution is CO
3 2-, SO
4 2-, NO
3 2-Or Cl
-Precipitation agent is volatile salt, urea, sodium hydroxide or yellow soda ash.
Described crystal seed is M
2+The oxide compound of metal, oxyhydroxide or prepared nanoscale anionic laminar material.
The present invention has following advantage: what (1) was adopted is the rotating bed with helix channel supergravity reactor; Rotating bed is provided with the spiral line type passage, and huge cf-makes that liquid height disperses in the passage, and by great shear forces tear into nano level film, silk and droplet; Produce the interface of fast updating; Microcosmic mixes and mass transfer process is further strengthened, and makes nucleation carry out in the microcosmic hybird environment uniformly, thereby realizes that nucleation is quick, narrow particle size distribution.The gas port of condensing works is adopted in rotating bed with helix channel supergravity reactor top, with the CO of reaction generation
2Discharge condensation NH
3Thereby, make rotating bed with helix channel supergravity reactor 4 internal reaction liquid remain on stable higher pH condition, avoided the dephasign generation.(2) reaction adds crystal seed, shortens nucleation inductive phase greatly, quicken nucleation, and percent crystallinity is high, size-grade distribution is more even; According to the grain size that adds crystal seed, the size of the newborn particle of adjustable and distribution thereof, it is controlled to reach particle diameter.(3) the product aftertreatment need not crystallization process.(4) the simple and weak point consuming time of this technology, it is low, pollution-free to consume energy, and can be continuously produced.The anion laminated material median size of preparing is 30～90nm.
Description of drawings
Fig. 1 is a quantity-produced rotating bed with helix channel supergravity reactor apparatus sketch.
The process flow sheet of Fig. 2 rotating bed with helix channel supergravity reactor prepared in reaction nanoscale anionic laminar material.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation.
As shown in Figure 1, the present invention joins soluble metallic salt and crystal seed mixed solution in the circulation groove 12 of quantity-produced rotating bed with helix channel supergravity reactor 4, and solution is heated to 20～100 ℃; Open valve 14, valve-off 3, starting up's rotating bed with helix channel supergravity reactor 4; The rotating bed with helix channel rotor speed that adopts is 500～5000rpm, evenly joins precipitant solution in the rotating bed with helix channel supergravity reactor 4 through opening for feed 7, makes from valve 14 effusive pH of mixed values to reach 8.0～10.0 fast; And tend towards stability gradually, continue reaction 5～20min, valve-off 14; Open valve 3, make reaction solution flow into storage tank 13, obtain the anion laminated material turbid solution; With reacting liquid filtering, washing precipitate is neutral until washings; Drying is ground and is promptly got nanoscale anionic laminar material.
Embodiment 1
Like Fig. 1, shown in Figure 2, the Mg of preparation 3.0L
2+Concentration is 0.0067mol/L, Al
3+Concentration is the MgCl of 0.0033mol/L
26H
2O and AlCl
36H
2O metal-salt aqua liquid is pressed Mg
2+With Al
3+Mol ratio be 2 to be made into soluble metallic salt mixed solution, wherein Mg
2+Be 0.0201mol, Al
3+Be 0.0099mol; Compound concentration is 0.1mol/L volatile salt (NH
4)
2CO
3Solution is as precipitant solution, (NH
4)
2CO
3Negatively charged ion Cl in amount of substance and the soluble metallic salt mixed solution
-Total mol ratio is 0.5.The soluble metallic salt mixed solution is joined be preheated to 20 ℃ in the fore-warmer tank of rotating bed with helix channel supergravity reactor 4 after, valve-off 3 is opened valve 14.Starting up's rotating bed with helix channel supergravity reactor 4; Treat in the rotating bed with helix channel supergravity reactor 4 liquid flow raties reach 50L/h stable after, in rotating bed with helix channel supergravity reactor 4 be that 10L/h passes through opening for feed 7 and evenly adds (NH with the flow
4)
2CO
3Solution, control rotating bed with helix channel supergravity reactor 4 rotating speeds are 500rpm, 20 ℃ of reacting liquid temperatures.When valve 14 effluent pH reach 8.0～10.0 and tend towards stability after, continue reaction 5min.Valve-off 14 is opened valve 3, makes reaction solution flow into storage tank 13, obtains the anion laminated material turbid solution, and with reacting liquid filtering, washing precipitate is neutral until washings, drying, and grinding and promptly getting particle diameter is 30～50nm anion laminated material.
Embodiment 2
Like Fig. 1, shown in Figure 2, the Mg of preparation 3.0L
2+Concentration is 0.04mol/L, Al
3+Concentration is the MgCl of 0.01mol/L
26H
2O and AlCl
36H
2O metal-salt aqua liquid is pressed Mg
2+With Al
3+Mol ratio be 4 to be made into soluble metallic salt mixed solution, wherein Mg
2+Be 0.12mol, Al
3+Be 0.03mol; Compound concentration is 5.0mol/L volatile salt (NH
4)
2CO
3Solution is as precipitant solution, (NH
4)
2CO
3Negatively charged ion Cl in amount of substance and the soluble metallic salt mixed solution
-Total mol ratio is 3.Mg with 0.5% (OH)
2Crystal seed joins in the soluble metallic salt mixed solution, soluble metallic salt and crystal seed mixed solution are joined be preheated to 60 ℃ in the fore-warmer tank of rotating bed with helix channel supergravity reactor 4 after, valve-off 3 is opened valve 14.Starting up's rotating bed with helix channel supergravity reactor 4; Treat in the rotating bed with helix channel supergravity reactor 4 liquid flow raties reach 400L/h stable after, in rotating bed with helix channel supergravity reactor 4 be that 200L/h passes through opening for feed 7 and evenly adds (NH with the flow
4)
2CO
3Solution, control rotating bed with helix channel supergravity reactor 4 rotating speeds are 1000rpm, 60 ℃ of reacting liquid temperatures.When valve 14 effluent pH reach 8.0～10.0 and tend towards stability after, continue reaction 10min.Valve-off 14 is opened valve 3, makes reaction solution flow into storage tank 13, obtains the anion laminated material turbid solution, and with reacting liquid filtering, washing precipitate is neutral until washings, drying, and grinding and promptly getting particle diameter is 50～70nm anion laminated material.
Embodiment 3
Like Fig. 1, shown in Figure 2, the Mg of preparation 3.0L
2+Concentration is 0.075mol/L, Al
3+Concentration is the Mg (NO of 0.025mol/L
3)
26H
2O and Al (NO
3)
39H
2O metal-salt aqua liquid is pressed Mg
2With Al
3+Mol ratio be 3 to be made into soluble metallic salt mixed solution, wherein Mg
2+Be 0.225mol, Al
3+Be 0.075mol; Compound concentration be 10.0mol/L urea as precipitant solution, the anion N O in urea amount of substance and the soluble metallic salt mixed solution
3 -Total mol ratio is 5.MgO crystal seed with 3.0% joins in the soluble metallic salt mixed solution, soluble metallic salt and crystal seed mixed solution are joined be preheated to 95 ℃ in the fore-warmer tank of rotating bed with helix channel supergravity reactor 4 after, valve-off 3 is opened valve 14.Starting up's rotating bed with helix channel supergravity reactor 4; Treat in the rotating bed with helix channel supergravity reactor 4 liquid flow raties reach 700L/h stable after; In rotating bed with helix channel supergravity reactor 4 be that 350L/h passes through opening for feed 7 and evenly adds urea solns with the flow; Control rotating bed with helix channel supergravity reactor 4 rotating speeds are 3000rpm, 95 ℃ of reacting liquid temperatures.When valve 14 effluent pH reach 8.0～10.0 and tend towards stability after, continue reaction 15min.Valve-off 14 is opened valve 3, makes reaction solution flow into storage tank 13, obtains the anion laminated material turbid solution, and with reacting liquid filtering, washing precipitate is neutral until washings, drying, and grinding and obtaining particle diameter is 40～60nm anion laminated material.
Embodiment 4
Like Fig. 1, shown in Figure 2, the Mg of preparation 3.0L
2+Concentration is 0.0200mol/L, Fe
3+Concentration is the Mg (NO of 0.0067mol/L
3)
26H
2O and Fe (NO
3)
39H
2O metal-salt aqua liquid is pressed Mg
2+With Fe
3+Mol ratio be 3 to be made into soluble metallic salt mixed solution, wherein Mg
2+Be 0.06mol, Fe
3+Be 0.02mol; Compound concentration is the NaOH of 0.3125mol/L, the Na of 0.0016mol/L
2CO
3As precipitant solution, the anion N O in NaOH amount of substance and the soluble metallic salt mixed solution
3 -Total mol ratio is 2, NaOH amount of substance and Na
2CO
3The amount of substance ratio is 2.5.0% Mg-Fe hydrotalcite crystal seed is joined in the soluble metallic salt mixed solution, soluble metallic salt and crystal seed mixed solution are joined be preheated to 70 ℃ in the fore-warmer tank of rotating bed with helix channel supergravity reactor 4 after, valve-off 3 is opened valve 14.Starting up's rotating bed with helix channel supergravity reactor 4; Treat in the rotating bed with helix channel supergravity reactor 4 liquid flow raties reach 1000L/h stable after; In rotating bed with helix channel supergravity reactor 4 be that 500L/h passes through opening for feed 7 and evenly adds urea solns with the flow; Control rotating bed with helix channel supergravity reactor 4 rotating speeds are 5000rpm, 70 ℃ of reacting liquid temperatures.When valve 14 effluent pH reach 8.0～10.0 and tend towards stability after, continue reaction 20min.Valve-off 14 is opened valve 3, makes reaction solution flow into storage tank 13, obtains the anion laminated material turbid solution, and with reacting liquid filtering, washing precipitate is neutral until washings, drying, and grinding and obtaining particle diameter is 70～90nm anion laminated material.
Claims (4)
1. a method for preparing nanoscale anionic laminar material continuously mainly by reaction, is filtered, washing, and dry several steps is formed, and it is characterized in that:
(1) the preparing metal ionic concn is 0.01～0.10mol/L soluble M
2+And M
3+The metal-salt aqua liquid is pressed M
2+With M
3+Mol ratio be 2～4 to be made into the soluble metallic salt mixed solution; Compound concentration is the precipitant solution of 0.1～10.0mol/L in addition, and the total mol ratio of negatively charged ion in precipitation agent amount of substance and the soluble metal salts solution is 0.5～5.0;
(2) with the soluble metallic salt mixed solution join be preheated to 20～100 ℃ in the fore-warmer tank of rotating bed with helix channel supergravity reactor after; Starting up's rotating bed with helix channel supergravity reactor; After treating that liquid flow rate reaches stationary value of 50～1000L/h in the rotating bed with helix channel supergravity reactor; Is that 10～500L/h evenly adds precipitant solution to the rotating bed with helix channel supergravity reactor with flow, and control rotating bed with helix channel supergravity reactor rotating speed is 500～5000rpm, 20～100 ℃ of reacting liquid temperatures; When effluent pH reach 8.0～10.0 and tend towards stability after; Continue reaction 5～20min, reaction solution is derived, collect reaction solution;
(3) with reacting liquid filtering, washing precipitate is neutral until washings, and drying is ground and promptly got nanoscale anionic laminar material.
2. a kind of continuous method for preparing nanoscale anionic laminar material according to claim 1 is characterized in that: crystal seed is added in the soluble metallic salt mixed solution, and addition is 0.5～5.0% of a soluble metallic salt weight.
3. a kind of continuous method for preparing nanoscale anionic laminar material according to claim 1 is characterized in that: described M
2+Be Mg
2+, Zn
2+, Co
2+, Cu
2+, Ni
2+, Mn
2+Or Ca
2+Metals ion, M
3+Be Al
3+, Fe
3+Or Cr
3+Metals ion; Negatively charged ion is CO in the soluble metallic salt mixed solution
3 2-, SO
4 2-, NO
3 2-Or Cl
-Precipitation agent is volatile salt, urea, sodium hydroxide or yellow soda ash.
4. a kind of continuous method for preparing nanoscale anionic laminar material according to claim 2, it is characterized in that: crystal seed is M
2+The oxide compound of metal, oxyhydroxide or prepared nanoscale anionic laminar material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102089011A CN101905870B (en) | 2010-06-25 | 2010-06-25 | Method for preparing nanoscale anionic laminar material continuously |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102089011A CN101905870B (en) | 2010-06-25 | 2010-06-25 | Method for preparing nanoscale anionic laminar material continuously |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101905870A CN101905870A (en) | 2010-12-08 |
| CN101905870B true CN101905870B (en) | 2012-02-29 |
Family
ID=43261491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102089011A Expired - Fee Related CN101905870B (en) | 2010-06-25 | 2010-06-25 | Method for preparing nanoscale anionic laminar material continuously |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101905870B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066270B (en) * | 2012-12-28 | 2015-07-22 | 湘潭大学 | Preparation method of nano-spinel type LiMn2O4 |
| CN105776162B (en) * | 2016-02-29 | 2018-02-02 | 中北大学 | A kind of method and device of the ammonium of hypergravity direct heat transfer method crystalline one |
| CN106495192B (en) * | 2016-11-14 | 2018-05-15 | 南华大学 | A kind of method for preparing the uniform hydrotalcite of particle diameter distribution |
| CN109110798B (en) * | 2017-06-26 | 2021-01-12 | 北京化工大学 | Preparation method of nano zinc-aluminum layered double hydroxide |
| CN111525111B (en) * | 2020-04-29 | 2022-04-22 | 蜂巢能源科技有限公司 | Modified cobalt manganese-layered double-metal hydroxide electrode material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142117C (en) * | 2000-12-14 | 2004-03-17 | 北京化工大学 | All return mixing-liquid film reactor and use in prepairng ultrafine anion layer shape material |
-
2010
- 2010-06-25 CN CN2010102089011A patent/CN101905870B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101905870A (en) | 2010-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101234750B (en) | Method of preparing superfine micro-particle and nano granule | |
| Byrappa et al. | Hydrothermal technology for nanotechnology | |
| CN101905870B (en) | Method for preparing nanoscale anionic laminar material continuously | |
| CN105417507B (en) | A kind of preparation method and products obtained therefrom of azotized carbon nano particle | |
| CN102515252B (en) | Film-coating production technology for nano zinc oxide | |
| CN101531362B (en) | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst | |
| Mohajerani et al. | Self-assembled zinc oxide nanostructures via a rapid microwave-assisted route | |
| Liu et al. | Fabrication and photoluminescence properties of hollow Gd 2 O 3: Ln (Ln= Eu3+, Sm3+) spheres via a sacrificial template method | |
| CN101293674A (en) | Method for preparing spindle shaped alpha-Fe2O3 powder | |
| CN105728010A (en) | Preparation method of antibacterial silver molybdate and graphite-phase carbon nitride composite visible-light-induced photocatalyst | |
| CN105618021B (en) | A kind of H2O2Modified anatase/rutile titanium dioxide nano-crystal composite material | |
| CN101920977A (en) | Preparation method of flaky nano-sized magnesium oxide | |
| CN104148047A (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN110078126A (en) | Solid-carrying type tungsten trioxide nano material of different-shape and its preparation method and application | |
| US20240140818A1 (en) | Preparation method and application of amorphous metal oxide hollow multi-shell material | |
| CN102030348B (en) | Device and method for continuously preparing magnesium hydroxide flame retardant | |
| CN105148955A (en) | Preparation process of complex photocatalyst with multiwalled carbon nanotube loading silver/silver phosphate core-shell structure | |
| CN103435097B (en) | Preparation method and application of nano zirconia | |
| CN110538649A (en) | Zinc oxide-based composite photocatalyst with excellent photocatalytic performance under visible light irradiation | |
| CN104709931A (en) | Nanometer hydrotalcite-like compound preparation method | |
| CN101293675B (en) | Method for preparing hexagonal disc shaped alpha-Fe2O3 powder | |
| Zhang et al. | Solvothermal synthesis of manganese sulfides and control of their phase and morphology | |
| CN105469920A (en) | Supergravity preparation method of cysteine modified magnetic nano-material | |
| Landge et al. | Solvent-free synthesis of nanoparticles | |
| CN105126811B (en) | Sodium niobate catalysis material of specific morphology and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120229 Termination date: 20120625 |