CN104709931B - A kind of preparation method of nano hydrotalcite - Google Patents
A kind of preparation method of nano hydrotalcite Download PDFInfo
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- CN104709931B CN104709931B CN201310690715.XA CN201310690715A CN104709931B CN 104709931 B CN104709931 B CN 104709931B CN 201310690715 A CN201310690715 A CN 201310690715A CN 104709931 B CN104709931 B CN 104709931B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The present invention relates to a kind of preparation method of nano hydrotalcite, that is, adopt flow focusing type micro passage reaction, the controllable standby of nano hydrotalcite is realized by introducing the mixing of gas reinforcing microcosmic.By water-soluble divalent metal raw material A2+X and trivalent metal salt raw material B3+X presses finite concentration mixing, takes soluble highly basic or highly basic and is configured to the aqueous solution with carbonate mixture；Metal salt solution, gas, aqueous slkali are simultaneously entered by three entrances of flow focusing type micro passage reaction, mix, react in microchannel；Gained sediment hydrothermal treatment, centrifugation, drying, that is, obtain nano hydrotalcite material.The present invention is with the time of staying is short, flux is big, granularity is controllable and narrowly distributing.Compared with conventional micro passage reaction, the access road of gas is additionally arranged in structure, and due to introducing gas in technique, mixed effect is further strengthened, product granularity is more homogeneous, can solve blockage problem of the micro passage reaction in nano material building-up process in addition.
Description
Technical field
The present invention relates to a kind of preparation method of nano hydrotalcite, should especially with flow focusing type microchannel plate
Device, strengthens the nano hydrotalcite preparation method of course of reaction, belongs to field of nano material preparation by introducing gas.
Background technology
Layered double hydroxide（Layered Double Hydroxides, LDHs）, houghite is also called, is
The important anionic clay materials of one class.LDHs main layer boards are positively charged double-metal hydroxide, and interlayer is negatively charged
The intercalant anion of lotus, main layer board institute is positively charged, and institute is negatively charged with interlayer anion makes whole houghite molecule into electricity
Neutral.Due to LDHs main layer boards metal composition, interlayer anion species and quantity, inner layer space size etc. are respectively provided with can modulation
Property, LDHs has broad application prospects in fields such as catalysis material, sorbing material, biology/medical materials.
For houghite, in prior art, most commonly seen preparation method is liquid-phase precipitation method, generally in intermittent stirring
Carry out in tank reactor.Wang Rongtao etc.（Functional material, 2009,40 (12), 2119-2122）It is prepared for using liquid-phase precipitation method
Nano-calcium carbonate root type magnalium hydrotalcite.Xie Xianmei etc.（Chemistry of fuel journal, 2003,31 (6), 620-623）Using liquid-phase precipitation
Method is prepared for NiMgAl ternary hydrotalcites.However, as in stirred-tank reactor, microcosmic mixing efficiency is poor, Temperature Distribution not
, in kettle, the nucleation rate of diverse location differs larger with growth rate so that conventional production methods have Granularity Distribution
Between uneven, batch the problems such as poor repeatability.For batch stirred tank reactor, for reaching the uniform mixing of microscopic units, past
Toward with high energy consumption as cost, it is unfavorable for industrial production.For make via liquid-phase precipitation method prepare nano hydrotalcite homogeneous grain diameter,
Stable performance, can strengthen microcosmic mixing and conduct heat and technology with low energy consumption in the urgent need to a kind of.
Micro- Chemical Engineering Technology is the Environment Science field of the multi-crossed disciplines that early 1990s rise.The technology main
Feature is to realize various unit operations and course of reaction using characteristic size in the microchannel of tens of to hundreds of micron dimensions.Due to
Channel size is substantially reduced, and Mass and heat transfer process is significantly strengthened, can increase substantially in course of reaction the utilization ratio of the energy and
The production capacity of unit volume, realizes chemical process reinforcing, miniaturization and greenization.In recent years, prepared using micro- Chemical Engineering Technology
Nano material has caused the extensive concern of academia and industrial quarters.However, carry out houghite in micro passage reaction preparing
Report less.Abello etc.（Advanced Materials, 2006,18 (18), 2436-2439）Disclose a kind of small size
The method that reactor prepares hydrotalcite, the reactor outer wall are equipped with rotor equipped with fixed blade, bottom, and rotating speed is reachable
24000rpm.The liquid for rotating at a high speed is sheared by outer wall blade during reaction to strengthen mixing, but gained hydrotalcite product is present
Agglomeration traits.Additionally due to rotor rotates at a high speed, high energy consumption is unfavorable for industrial production.Patent CN103011254A discloses one
Plant the preparation method that acrylic/hydrotalcite-like nano monolithic is prepared using T-shaped micro passage reaction.Known, the passage of micro passage reaction
Size between tens of to hundreds of microns is used it for nano material and synthesizes the problem that most challenges is how to solve to block.Specially
Sharp CN103011254A is not related to discussion and the substantive method for how solving blockage problem with regard to blockage problem, particularly works as
When preparing carbonate form sodium rice hydrotalcite, the material in microchannel is easy to blocking channel, and the patent is not directed to material settling out
Carbonate form sodium rice hydrotalcite synthesis.Shirure etc.（Industrial&engineering chemistry
Research, 2005,44 (15), 5500-5507）Disclose a kind of method that narrow passage reactor prepares houghite, but institute
Obtain product cut size and be all higher than 10 μm.Known, powder body material only can just show entirely different with block in nanoscale
Excellent properties, although and Shirure etc. prepares hydrotalcite-like materials by narrow passage microreactor, due to houghite
Granularity is excessive, and not there is practical value.Therefore it provides a kind of can effectively solving blockage problem and energy using micro passage reaction
The method for preparing nano hydrotalcite material is that the core of the present invention is located.
Content of the invention
It is an object of the invention to overcoming the shortcoming that prior art is present, there is provided a kind of preparation using micro passage reaction is received
The method of rice hydrotalcite-like materials, both can achieve between the controllable standby and batch of nano hydrotalcite material particle size and particle diameter distribution
Duplication of production, also solve the problem that the blockage problem in micro passage reaction.To achieve these goals, using a kind of flow focusing
Type micro passage reaction is continuously prepared, and the flow focusing type micro passage reaction carries two liquid-inlets, gases
Import and one outlet；Its concrete technology step is as follows：
（1）By soluble divalent metal salt raw material A2+X and trivalent metal salt raw material B3+X presses A2+With B3+Total moles than big
In or be equal to 2:1, less than or equal to 4:1 is configured to metal salt solution, A in the metal salt solution2+With B3+Total concentration be
0.1-2.0mol/L；Wherein, A2+Can be Mg2+、Ni2+、Zn2+、Cu2+、Fe2+、Co2+、Ca2+In one or more；B3+Can be
Al3+、Fe3+、Co3+、Mn3+、Cr3+、Ga3+、In3+In one or more；X is Cl-、NO3 -、SO4 2-In one or more；
（2）One or more taken in NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate, potassium carbonate, ammonium carbonate is configured to
Mixed ammonium/alkali solutions, hydroxyl in mixed solution（OH-）Or carbonate（CO3 2-）Or hydroxyl（OH-）And carbonate（CO3 2-）Total
Concentration is 0.2-4.5mol/L；
（3）Gases used one or more in air, nitrogen, argon gas；
（4）The step（1）With（2）The metal salt solution that is prepared and mixed ammonium/alkali solutions are with same traffic respectively from two
Liquid inlet enters；It is micro- that gas then enters flow focusing type with 0.2-5 times of liquid charging stock total flow of flow from gas access
In channel reactor；In inside reactor reaction channel, metal salt solution and mixed ammonium/alkali solutions are divided into independent by gas
Liquid bullet, the two are contacted in liquid bullet, are mixed and react, and are reacted gained houghite slurry and are flowed out from the exit of reactor；
（5）Step（4）Gained houghite slurry hydrothermal treatment；Sediment deionized water after by hydro-thermal process is filled
Divide washing, gained sample is nano hydrotalcite after centrifugation.
Used by above-mentioned technical proposal, flow focusing type micro passage reaction takes monolithic microchannel plate or multi-disc microchannel plate
Superposition makes；When being made using monolithic microchannel plate, reactor includes two blocks of shroudings and a piece of microchannel plate, is specially located at micro-
Four microchannels on channel plate, i.e., two fluid inlet channels, gas inlet channels and are connected with intake channel respectively
A reaction channel, intake channel is connected with three imports respectively, and reaction channel is connected with outlet；Using multi-disc microchannel plate
When superposition makes, reactor includes that two panels shrouding and three microchannel plates, specially gas inlet channel, and two liquid-inlets lead to
One of road is made on another two panels microchannel plate respectively；Another kind of fluid inlet channel is with reaction channel then the 3rd microchannel
Make on plate；Using conventional pore structure connected mode connection intake channel and reaction channel.
Above-mentioned technical proposal gas inlet channel between two fluid inlet channels, with two fluid inlet channel angles
Equal, angle is 20-80 °；
Above-mentioned technical proposal gas inlet channel is equivalently-sized with fluid inlet channel, and hydraulic diameter is 0.2-1mm；Reaction
Passage hydraulic diameter is identical or different with intake channel hydraulic diameter, is 0.2-1mm, and reaction channel length is 10mm-200mm.
The present invention realizes that another feature of nano hydrotalcite method is the control flow focusing type micro passage reaction
The time of staying of middle liquid slurry is in 0.01 second-time, so that described metal salt solution and mixed ammonium/alkali solutions are fast in microchannel
Speed mixing.
The present invention compared with prior art, have the advantages that the time of staying short, flux is big, granularity is controllable and narrowly distributing.By
In introducing gas, it is possible to resolve T-shaped or blockage problem that Y type micro passage reactions are common.The nano hydrotalcite material for preparing,
Uniform particle diameter, good dispersion degree.
Description of the drawings
Flow focusing type micro passage reaction schematic diagram used by Fig. 1, the present invention, is made by monolithic microchannel plate.
In figure, 1,2,3 are respectively liquid one（Slaine/mixed base）Intake channel, liquid two（Mixed base/slaine）Enter
Mouth passage, gas inlet channel；4 is reaction channel；11st, 21,31,41 liquid one is respectively（Slaine/mixed base）Import, liquid
Body two（Mixed base/slaine）Import, gas feed and reaction outlet.
Flow focusing type micro passage reaction schematic diagram used by Fig. 2, the present invention, is made by the superposition of multi-disc microchannel plate.
In figure, A, B, C are respectively：A kind of fluid inlet channel and reaction channel plate, another kind of fluid inlet channel plate, gas
Body intake channel plate；1st, 2,3 is liquid one（Slaine/mixed base）Intake channel, liquid two（Mixed base/slaine）Import is led to
Road, gas inlet channel；4 is reaction channel；11st, 21,31,41 liquid one is respectively（Slaine/mixed base）Import, liquid two
（Mixed base/slaine）Import, gas feed and reaction outlet；5A, 5B are connecting hole.
Fig. 3, the XRD of the embodiment of the present invention 1.
Fig. 4, the TEM figures of the embodiment of the present invention 1.
Fig. 5, the XRD of the embodiment of the present invention 2.
Fig. 6, the XRD of the embodiment of the present invention 3.
Specific embodiment
Describe the present invention by the following examples in detail, but invention is not limited to following examples.
Flow focusing type micro passage reaction in embodiment is briefly described：
As shown in accompanying drawing 1, Fig. 2.Including two panels fluid inlet channel plate A, B, a piece of gas inlet channel plate C, wherein, one
Piece fluid inlet channel plate is with reaction channel on same plate（A）.Three 1,2,3 hydraulic diameter of intake channel is equal, all
For 600 microns, reaction channel is equal with intake channel hydraulic diameter.Press from both sides between gas inlet channel 3 and two fluid inlet channels 1,2
It is 60 ° that angle is equal.Volume about 36 microlitre of the length of reaction channel 4 for 100 millimeters, i.e. reaction channel, then by slush pulp stream
Amount can calculate the time of staying of liquid slurry in micro passage reaction.
Embodiment 1
Weigh the Mg (NO of 48.1g3)2·6H2Al (the NO of O and 23.4g3)3·9H2O, being configured to metal ion total concentration is
The aqueous solution 500ml of 0.5mol/L.Weigh the Na of the NaOH and 13.25g of 16g2CO3It is configured to OH-And CO3 2-Total concentration is
The aqueous solution 500ml of 1.05mol/L.Gas selects air, and flow is 100ml/min.Metal salt solution and aqueous slkali with
The flow of 150ml/min enters micro passage reaction contact, mixing and reacts, and reaction temperature is 80 DEG C. take partly precipitated thing dress
Enter hydrothermal reaction kettle, 6h is processed at 150 DEG C.Precipitate with deionized water after by hydro-thermal process is fully washed, gained after centrifugation
Sediment is nano-calcium carbonate root type MgAl hydrotalcite, and itself XRD and TEM characterization result is respectively as shown in Figure 3, Figure 4.
Embodiment 2
Weigh the Mg (NO of 48.1g3)2·6H2Al (the NO of O, 11.7g3)3·9H2Fe (the NO of O and 12.6g3)3·9H2O,
It is configured to the aqueous solution 500ml that metal ion total concentration is 0.5mol/L.Weigh the Na of the NaOH and 13.25g of 16g2CO3Configuration
Into OH-And CO3 2-Aqueous solution 500ml of the total concentration for 1.05mol/L.Gas selects nitrogen, and flow is 20ml/min.Slaine
Solution and aqueous slkali enter micro passage reaction contact, mixing with the flow of 100ml/min and react, and reaction temperature is 80
DEG C. taking partly precipitated thing and loading hydrothermal reaction kettle, 4h is processed at 100 DEG C.Precipitate with deionized water after by hydro-thermal process is filled
Divide washing, centrifuged pellet thing is nano-calcium carbonate root type MgAlFe hydrotalcite, and the XRD spectrum analysis result of the hydrotalcite is such as
Accompanying drawing 5 shows.
Embodiment 3
Weigh the Mg (NO of 24.0g3)2·6H2Ni (the NO of O, 27.3g3)2·6H2Al (the NO of O, 11.7g3)3·9H2O and
Fe (the NO of 12.6g3)3·9H2O, is configured to the aqueous solution 500ml that metal ion total concentration is 0.5mol/L.Weigh 16g's
The Na of NaOH and 13.25g2CO3It is configured to OH-And CO3 2-Aqueous solution 500ml of the total concentration for 1.05mol/L.Gas selects nitrogen
Gas, flow are 150ml/min.Metal salt solution and aqueous slkali with the flow of 150ml/min enter micro passage reaction contact,
Mixing and reaction, reaction temperature are 80 DEG C. taking partly precipitated thing and loading hydrothermal reaction kettle, 4h is processed at 100 DEG C.At hydro-thermal
Precipitate with deionized water after reason is fully washed, and centrifuged pellet thing is nano-calcium carbonate root type MgNiFeAl hydrotalcite, should
The XRD spectrum analysis result of hydrotalcite such as accompanying drawing 6 shows.
Claims (4)
1. a kind of preparation method of nano hydrotalcite, is carrying two liquid-inlets, a gas feed and one outlets
It is prepared in flow focusing type micro passage reaction, it is characterised in that：
(1) by soluble divalent metal salt raw material A2+X and trivalent metal salt raw material B3+X presses A2+With B3+Total moles ratio more than or
It is equal to 2:1, less than or equal to 4:1 is configured to metal salt solution, A in the metal salt solution2+With B3+Total concentration be 0.1-
2.0mol/L；Wherein, A2+Can be Mg2+、Ni2+、Zn2+、Cu2+、Fe2+、Co2+、Ca2+In one or more；B3+Can be Al3+、
Fe3+、Co3+、Mn3+、Cr3+、Ga3+、In3+In one or more；X is Cl-、NO3 -、SO4 2-In one or more；
(2) take one or more in NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate, potassium carbonate, ammonium carbonate to be configured to mix
Aqueous slkali, hydroxyl (OH in mixed solution-) or carbonate (CO3 2-) or hydroxyl (OH-) and carbonate (CO3 2-) total concentration
For 0.2-4.5mol/L；
(3) gases used one or more in air, nitrogen, argon gas；
(4) step (1) and (2) is prepared metal salt solution and mixed ammonium/alkali solutions are with same traffic respectively from two liquid
Entrance is entered；Gas then enters flow focusing type microchannel with 0.2-5 times of liquid charging stock total flow of flow from gas access
In reactor；In inside reactor reaction channel, metal salt solution and mixed ammonium/alkali solutions are divided into independent liquid bullet by gas,
The two contacts in liquid bullet, mixes and reacts, and reacts gained houghite slurry and flows out from the exit of reactor；
(5) step (4) gained houghite slurry hydrothermal treatment；Sediment deionized water after by hydro-thermal process is fully washed
Wash, after centrifugation, gained sample is nano hydrotalcite.
2. the preparation method of hydrotalcite according to claim 1, it is characterised in that：
The flow focusing type micro passage reaction takes monolithic microchannel plate or the superposition of multi-disc microchannel plate to make；Using monolithic
When microchannel plate makes, reactor includes two blocks of shroudings and a piece of microchannel plate, and four for being specially located on microchannel plate are micro-
The fluid inlet channel of passage, i.e., two, a gas inlet channel, and a reaction channel being connected with intake channel, import
Passage is connected with three imports respectively, and reaction channel is connected with outlet；When being made using the superposition of multi-disc microchannel plate, reactor bag
One of two panels shrouding and three microchannel plates, specially gas inlet channel, and two fluid inlet channels are included respectively in another two panels
Make on microchannel plate；Another kind of fluid inlet channel is then made on the 3rd microchannel plate with reaction channel；Using routine
Pore structure connected mode connection intake channel and reaction channel.
3. the preparation method of hydrotalcite according to claim 2, it is characterised in that：
Between two fluid inlet channels, equal with two fluid inlet channel angles, angle is the gas inlet channel
20-80°；
Gas inlet channel is equivalently-sized with fluid inlet channel, and hydraulic diameter is 0.2-1mm；Reaction channel hydraulic diameter with enter
Mouth passage hydraulic diameter is identical or different, is 0.2-1mm, and reaction channel length is 10mm-200mm.
4. the preparation method of hydrotalcite according to claim 1, it is characterised in that：Control the flow focusing type microchannel
In reactor, the time of staying of liquid slurry is in 0.01 second-time.
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| CN105948085B (en) * | 2016-04-21 | 2017-08-25 | 巢湖学院 | A kind of preparation method of magnetic hydrotalcite |
| CN107837782A (en) * | 2017-12-08 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of method for passing through Nanoparticles Prepared by Precipitation using multichannel blender |
| CN107855091A (en) * | 2017-12-08 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of method for passing through Nanoparticles Prepared by Precipitation using single channel blender |
| CN112023929B (en) * | 2019-11-22 | 2021-12-03 | 天津大学 | Preparation method and application of transition metal double hydroxide nano-film and carbon nano-tube composite material |
| CN112871103A (en) * | 2021-01-14 | 2021-06-01 | 浙江工业大学 | Preparation method of capillary microchannel reactor with internal coated hydrotalcite film |
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| CN101132854A (en) * | 2004-11-16 | 2008-02-27 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
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| WO2013147285A1 (en) * | 2012-03-26 | 2013-10-03 | 協和化学工業株式会社 | Method for manufacturing hydrotalcite particles |
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| CN101132854A (en) * | 2004-11-16 | 2008-02-27 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
| WO2013147285A1 (en) * | 2012-03-26 | 2013-10-03 | 協和化学工業株式会社 | Method for manufacturing hydrotalcite particles |
| CN103011254A (en) * | 2012-12-19 | 2013-04-03 | 青岛科技大学 | Preparation method for nanosheet of uniformly dispersed layered double hydroxides (LDHs) |
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