CN104609450A - Process and complete industrial installation for producing highly dispersed magnalium hydrotalcite powder bodies - Google Patents
Process and complete industrial installation for producing highly dispersed magnalium hydrotalcite powder bodies Download PDFInfo
- Publication number
- CN104609450A CN104609450A CN201410528456.5A CN201410528456A CN104609450A CN 104609450 A CN104609450 A CN 104609450A CN 201410528456 A CN201410528456 A CN 201410528456A CN 104609450 A CN104609450 A CN 104609450A
- Authority
- CN
- China
- Prior art keywords
- hydrotalcite
- suction filtration
- water
- filter cake
- element type
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a process and a complete industrial installation for producing highly dispersed magnalium hydrotalcite powder bodies, and belongs to the technical field of inorganic functional material industrialization. The installation comprises a slurry storage tank, a filter element type sucking filtrator, a dispersant rectification system, a washing water regeneration system and a continuous tray dryer. The process is as follows: sending the magnalium hydrotalcite slurry from the slurry storage tank into the filter element type sucking filtrator to perform sucking filtrating so as to obtain a filter cake of magnalium hydrotalcite, decontaminating the generated waste water by the water regeneration system to obtain clean water for reuse, adding an organic dispersant and mixing the dispersant with the magnalium hydrotalcite filer cake, modifying the magnalium hydrotalcite under mechanical stirring and/or compressed air bubbling conditions, conducting sucking filtrating by a vacuum pump after modification ends, and transferring the filter cake to the continuous tray dryer to conduct drying. During the entire process, the used organic dispersant is recycled by the rectification system, thereby avoiding the environmental pollution caused by the organic dispersant and reducing the cost. The production process is simplified, a magnalium hydrotalcite product with good dispersion and high specific surface area is obtained, and mass production is realized.
Description
Technical field:
The invention belongs to inorganic functional material industrialization technology field, particularly a kind ofly produce the technique of high dispersive hydrotalcite powder and complete full scale plant.
Background technology:
Layered composite metal hydroxides (Layered Double Hydroxides is called for short LDHs), is hydrotalcite again, and be a kind of typical anionic type laminated material, its chemical constitution formula is [M
2+ 1-xm
3+ x(OH)
2] A
n- x/nmH
2o, wherein M
2+, M
3+be respectively divalence and trivalent metal cation, A
n-be interlayer anion, x is M
3+the molar fraction of ion, m is the quantity of crystal water.The metallic element kind of hydrotalcite main body laminate and proportion of composing, the kind of interlayer object and the number of quantity and water molecules can need modulation in relative broad range according to application, enrich it greatly functional, be widely used in the fields such as ultraviolet-resistant, infrared absorption, PVC heat stabilizer, novel optoelectronic materials, electrochemical energy storage at present.
The industrial traditional method preparing hydrotalcite is on a large scale coprecipitation method and nucleation-crystallization isolation method, after the building-up reactions of hydrotalcite terminates, directly obtains hydrotalcite powdered product after drying with pure water slurry.Due to the surface tension effects in the high surface energy of hydrotalcite self and evaporating pure water process in drying process, cause final product to be reunited comparatively serious, size distribution is uneven, and very low (the about 1-50m of surface-area
2/ g), significantly limit the range of application of hydrotalcite.Only solve the agglomeration traits of hydrotalcite, its special nano effect just can well be embodied in the application, finally makes the performance of the aspects such as its mechanics, optics, calorifics be significantly improved.
Although prepare high dispersive hydrotalcite achieved certain progress in laboratory, if think industrialization scale operation, still there is some problem to need to solve: 1. in amplification process, be amplified to m when the modification kettle adopted is long-pending
3during size, because scale effect can cause system heterogeneity in still, modification is thorough not, affects product quality, causes its performance significantly to decline; 2. laboratory modification needs with a large amount of organic dispersing agent (as obtain 1g hydrotalcite need to use 1L modified by acetone), and reclaims difficulty, and preparation cost is higher; 3. modified filter cake is put into pallet in blast drier drying by laboratory, cannot recycle the dispersion agent of volatilization, result in the wasting of resources and VOCs pollution; 4. first utilize vacuum pump suction filtration in Büchner funnel during the washing of laboratory, be then transferred in flask by filter cake, then use organic dispersing agent modification, finally still in Büchner funnel, suction filtration obtains filter cake, and this process is more loaded down with trivial details, is unfavorable for large scale continuous prod.
Summary of the invention:
For overcoming the scale effect in large reactor modifying process, organic dispersing agent is recycled after a procedure and avoids environmental pollution, simplify Production Flow Chart, obtain the hydrotalcite product of good dispersity, high-specific surface area, realize scale operation, the invention provides and a kind ofly produce the technique of high dispersive hydrotalcite powder and complete full scale plant, as shown in Figure 1.
The complete full scale plant of production high dispersive hydrotalcite powder of the present invention, this device comprises pulp storing tank, filer element type suction filtration machine, dispersion agent distillation system, washing water regeneration system rapidly, continuously pan dryer; Hydrotalcite slurry is entered filer element type suction filtration machine by pulp storing tank and carries out suction filtration, obtain hydrotalcite filter cake, the waste water of generation is purified rear recycling by washing water regeneration system rapidly; Then directly add organic dispersing agent to mix with hydrotalcite filter cake, under mechanical stirring and/or pressurized air bubbling condition, carry out modification to hydrotalcite, modification terminates rear suction filtration, modified filter cake is transferred to continuous pan dryer and carries out drying; In whole technical process, used organic dispersing agent recycles through dispersion agent distillation system.
Described filer element type suction filtration machine, its filter core adopt porous material make, aperture be nano level to micron order, duct is the random state of cross-distribution; During suction filtration, water or organic dispersing agent ooze out through duct, and hydrotalcite is retained down formation filter cake.
Described continuous pan dryer is arranged alternatively up and down by size drying tray, and with rake leaf on each drying tray, rake leaf controls to do turning motion by rake arms to be made rake leaf turn over continuously to copy material; On large drying tray, material moves to center and falls into the little drying tray of lower one deck from center blanking port, after receiving material little drying tray outwards move to immediately below large drying tray outer rim place, material also outwards movement simultaneously on little drying tray, and the large drying tray outer rim immediately below falling from outer rim; Modified filter cake is added on the first layer drying tray of moisture eliminator top, then continues to flow through every layer of drying tray surface along index spiral-line.
Described dispersion agent distillation system by use in modifying process with the organic dispersing agent purification and recover that produces in drying process after enter dispersion agent storage tank, hydrotalcite-modified for next batch; Described dispersion agent distillation system comprises reboiler, dispersion agent rectifying tower, interchanger, condenser, organic dispersing agent is separated, boils again, rectifying, condensation, by the water that contains and impurity removing.
Described washing water regeneration system rapidly, first neutralizes the water reuse acid-base neutralisation principle produced after suction filtration, and maintain pH value between 6.0-8.0, then utilize reverse osmosis membrane to be removed by the metal ion in water, the water be purified enters water tank.
Above-mentioned complete full scale plant is used for the industrialized producing technology of high dispersive hydrotalcite powder, its concrete steps are:
A. be that the hydrotalcite slurry 50-2000L of 1-15wt% adds filer element type suction filtration machine by solid content, filter core aperture is 0.1-300 μm, and arranging suction filtration pressure reduction is 0.01-0.5MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, carries out purification recycling by washing water regeneration system rapidly;
B.20-150 under DEG C condition, 50-2000L organic dispersing agent is added in filer element type suction filtration machine, under mechanical stirring and/or pressurized air bubbling condition, carry out modification to hydrotalcite, arranging mixing speed is 50-3000rpm, and pressurized air bubbling rate is 0.1-1000mL/min; Carry out suction filtration after modification 1-72 hour, arranging suction filtration pressure reduction is 0.01-0.5MPa, and the filter cake obtained is transferred in continuous pan dryer dry, and the temperature arranging pan dryer is 30-200 DEG C, obtains high dispersive hydrotalcite powder after dry 1-48 hour; By use in modifying process with the organic dispersing agent that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch.
The chemical constitution of described hydrotalcite is [M
2+ 1-xm
3+ x(OH)
2] A
n- x/nmH
2o; Wherein M
2+represent divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+in one or both, preferred Mg
2+, Zn
2+, Ca
2+, Ni
2+in one or both; M
3+represent trivalent metal cation Al
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+in one or both, preferred Al
3+, Fe
3+in one or both; Acid radical anion A
n-be selected from one or more in following acid radical anion: (1) inorganic anion: CO
3 2-, NO
3 -, [B
4o
5(OH)
4]
2 –, F
-, Cl
-, Br
-, I
-, ClO
4 -, IO
3 -, H
2pO
4 -, HPO
4 2-, PO
4 3-, SO
4 2-, S
2o
3 2-, WO
4 2-, C
ro
4 2-; (2) organic anion: p-phthalic bridge, P-hydroxybenzoic acid root, succinic, hexanodioic acid root, dodecyl sodium sulfonate root, benzoate anion; (3) with many, heteropolyacid anions: Mo
7o
24 6-, V
10o
28 6-, PW
11cuO
39 6-, SiW
9w
3o
40 7-; A
n-preferred NO
3 -, CO
3 2-, [B
4o
5(OH)
4]
2 –, SO
4 2-, PO
4 3-, succinic, one in benzoate anion; N is the valence number of acid radical anion, n=1-7.
Described hydrotalcite particle diameter is 30nm-5 μm.
Described organic dispersing agent is one or more in acetone, methyl alcohol, ethanol, n-propyl alcohol, Virahol, tetrahydrofuran (THF), acetonitrile, dioxane, methyl-sulphoxide, N-N dimethyl formamide, one or both in preferred acetone, methyl alcohol, ethanol, n-propyl alcohol, Virahol.
The present invention, according to interfacial chemistry principle, for the chemical bond types of hydrotalcite and the physicochemical property on surface, utilizes organic solvent to carry out modification to hydrotalcite surface or interlayer, devises and a kind ofly produce the technique of high dispersive hydrotalcite powder and complete full scale plant.By organic dispersing agent modification, the dispersiveness of hydrotalcite can be improved, suppress the reunion between particle, thus make product specific surface area improve more than 10 times.After hydrotalcite slurry pumps moisture formation filter cake, directly in filer element type suction filtration machine, add organic dispersing agent and carry out modification, namely filer element type suction filtration machine is both as Suction filtration device, again as reforming apparatus, simplifies Production Flow Chart, is conducive to scale operation; In addition, rectifying and condenser system is utilized by organic dispersing agent high efficiente callback recycle, environmental pollution can also to be avoided, and significantly reduce production cost.
Accompanying drawing explanation
The process flow sheet of the production high dispersive hydrotalcite powder of Fig. 1 the present invention design;
Fig. 2 is the XRD spectra of embodiment 1 gained hydrotalcite powder;
Fig. 3 is the infrared spectrum of embodiment 1 gained hydrotalcite powder;
Fig. 4 is the Laser particle-size distribution figure of embodiment 1 gained hydrotalcite powder;
Fig. 5 is the TEM spectrogram of embodiment 1 gained hydrotalcite powder;
Fig. 6 is adsorption isothermal curve and the pore distribution figure of embodiment 1 gained hydrotalcite powder.
Embodiment
Embodiment 1:
The complete full scale plant of production high dispersive hydrotalcite powder: this device comprises pulp storing tank, filer element type suction filtration machine, dispersion agent distillation system, washing water regeneration system rapidly, continuously pan dryer; Hydrotalcite slurry is entered filer element type suction filtration machine by pulp storing tank and carries out suction filtration, obtain hydrotalcite filter cake, the waste water of generation is purified recycling by washing water regeneration system rapidly; Then directly add organic dispersing agent to mix with hydrotalcite filter cake, under mechanical stirring and/or pressurized air bubbling condition, carry out modification to hydrotalcite, modification terminates rear suction filtration, modified filter cake is transferred to continuous pan dryer and carries out drying; In whole technical process, used organic dispersing agent recycles through dispersion agent distillation system.
Described filer element type suction filtration machine, its filter core adopt porous material make, aperture be nano level to micron order, duct is the random state of cross-distribution; During suction filtration, water or organic dispersing agent ooze out through duct, and hydrotalcite is retained down and forms hydrotalcite filter cake.
Described continuous pan dryer is arranged alternatively up and down by size drying tray, and with rake leaf on each drying tray, rake leaf controls to do turning motion by rake arms to be made rake leaf turn over continuously to copy material; On large drying tray, material moves to center and falls into the little drying tray of lower one deck from center blanking port, after receiving material little drying tray outwards move to immediately below large drying tray outer rim place, material also outwards movement simultaneously on little drying tray, and the large drying tray outer rim immediately below falling from outer rim; Modified filter cake is added on the first layer drying tray of moisture eliminator top, then continues to flow through every layer of drying tray surface along index spiral-line.
Described dispersion agent distillation system by use in modifying process with the organic dispersing agent purification and recover that produces in drying process after enter dispersion agent storage tank, hydrotalcite-modified for next batch; Described dispersion agent distillation system comprises reboiler, dispersion agent rectifying tower, interchanger, condenser, organic dispersing agent is separated, boils again, rectifying, condensation, by the water that contains and impurity removing.
Described washing water regeneration system rapidly, first neutralizes the water reuse acid-base neutralisation principle produced after suction filtration, and maintain pH value between 6.0-8.0, then utilize reverse osmosis membrane to be removed by the metal ion in water, the water be purified enters water tank.
Use above-mentioned complete full scale plant for the suitability for industrialized production of high dispersive hydrotalcite powder:
A. be 6wt% by solid content, median size is 145.4nm, chemical formula is Mg
6al
2(OH)
16cO
34H
2the hydrotalcite slurry 100L of O adds filer element type suction filtration machine, and filter core aperture is 0.1 μm, and arranging suction filtration pressure reduction is 0.1MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, carries out purification recycling, arrange and be neutralized to pH=7 by washing water regeneration system rapidly;
B.25 under DEG C condition, 600L acetone is added in filer element type suction filtration machine, under mechanical agitation, modification is carried out to hydrotalcite, mixing speed is 500rpm, modification carried out suction filtration after 48 hours, and arranging suction filtration pressure reduction is 0.1MPa, and the filter cake obtained is transferred in continuous pan dryer dry, the temperature arranging pan dryer is 40 DEG C, obtains high dispersive hydrotalcite powder after dry 12 hours; By use in modifying process with the acetone that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch, the moisture of more than 99% can be removed after treatment, and the purity of acetone can reach more than 98%.
The XRD-6000 type X-ray powder diffractometer of Japanese Shimadzu Corporation is adopted to carry out Crystal Structure to product.Fig. 2 is the XRD spectra of embodiment 1 gained hydrotalcite powder, and as can be seen from the figure, in 2 θ=11.3 °, Mg appearred in 22.7 °, 34.5 °, 60.5 ° and about 61.8 ° places
6al
2-CO
3the characteristic diffraction peak of-LDHs, and peak shape point is alarmmed, baseline is low flat, and product crystal structural integrity is described.
Adopt the infrared absorption spectrum of the Vector22 type infrared spectrometer measure sample of German Brooker company.Fig. 3 is the infrared spectra of embodiment 1 gained hydrotalcite powder, as can be seen from the figure, and 3486cm
-1there is the stretching vibration absorption peak of laminate OH, 1640cm
-1there is the flexural vibration absorption peak of laminate OH, 1570cm
-1for interlayer CO
3 2-stretching vibration absorption peak, 655cm
-1for interlayer CO
3 2-flexural vibration absorption peak, infrared spectra further illustrates product crystal structural integrity.
Adopt the size of the Mastersizer2000 type laser particle analyzer measure sample of Malvern company of Britain.Fig. 4 is the Laser particle-size distribution figure of embodiment 1 gained hydrotalcite powder, and as can be seen from the figure, the median size of product is 145.4nm, and size distribution is more even; Peak without Large stone occurs, shows that product is very well dispersed, without obvious agglomeration.
Adopt NEC instrument company (JEOL) JEM2010 type transmission electron microscope observing grain-size and pattern.Fig. 5 is the TEM spectrogram of embodiment 1 gained hydrotalcite powder, and as can be seen from the figure hydrotalcite particles is single dispersing, soilless sticking phenomenon, and particle diameter is 50-210nm, and median size is about 145nm.
Adopt adsorption isothermal curve and the pore size distribution of U.S. Quantachrome company Autosorb-1C-VP type analysis instrument test sample.Fig. 6 is adsorption isothermal curve and the pore distribution figure of embodiment 1 gained hydrotalcite powder, and as can be seen from the figure product aperture is distributed between 5-20nm.Show that the specific surface area of product is 148m according to adsorption isothermal line
2/ g.
Embodiment 2:
The complete full scale plant using embodiment 1 to design is used for the suitability for industrialized production of high dispersive hydrotalcite powder:
A. be 1wt% by solid content, median size is 5 μm, chemical formula is Mg
6al
2(OH)
16(NO
3)
24H
2o, adopt the obtained hydrotalcite slurry 100L of nucleation-crystallization method to add filer element type suction filtration machine, filter core aperture is 300 μm, and arranging suction filtration pressure reduction is 0.1MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, carries out purification recycling, arrange and be neutralized to pH=7 by washing water regeneration system rapidly;
B.25 under DEG C condition, 600L Virahol is added in filer element type suction filtration machine, under mechanical agitation, modification is carried out to hydrotalcite, mixing speed is 500rpm, modification carried out suction filtration after 24 hours, and arranging suction filtration pressure reduction is 0.1MPa, and the filter cake obtained is transferred in continuous pan dryer dry, the temperature arranging pan dryer is 40 DEG C, obtains high dispersive hydrotalcite powder after dry 12 hours; By use in modifying process with the Virahol that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch, the moisture of more than 99% can be removed after treatment, and the purity of Virahol can reach more than 98%.
Embodiment 3:
The complete full scale plant using embodiment 1 to design is used for the suitability for industrialized production of high dispersive hydrotalcite powder:
A. be 10wt% by solid content, median size is 50nm, chemical formula is Zn
4al
2(OH)
12cO
34H
2o, adopt the obtained hydrotalcite slurry 400L of nucleation-crystallization method to add filer element type suction filtration machine, filter core aperture is 10 μm, and arranging suction filtration pressure reduction is 0.1MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, carries out purification recycling, arrange and be neutralized to pH=7 by washing water regeneration system rapidly;
B.25 under DEG C condition, 600L methyl-sulphoxide is added in filer element type suction filtration machine, under mechanical agitation, modification is carried out to hydrotalcite, mixing speed is 1000rpm, modification carried out suction filtration after 48 hours, and arranging suction filtration pressure reduction is 0.1MPa, and the filter cake obtained is transferred in continuous pan dryer dry, the temperature arranging pan dryer is 80 DEG C, obtains high dispersive hydrotalcite powder after dry 12 hours; By use in modifying process with the methyl-sulphoxide that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch, the moisture of more than 99% can be removed after treatment, and the purity of methyl-sulphoxide can reach more than 98%.
Embodiment 4:
The complete full scale plant using embodiment 1 to design is used for the suitability for industrialized production of high dispersive hydrotalcite powder:
A. be 15wt% by solid content, median size is 520nm, chemical formula is Zn
4al
2(OH)
12(NO
3)
24H
2o, adopt the obtained hydrotalcite slurry 800L of nucleation-crystallization method to add filer element type suction filtration machine, filter core aperture is 100 μm, and arranging suction filtration pressure reduction is 0.1MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, carries out purification recycling, arrange and be neutralized to pH=7 by washing water regeneration system rapidly;
B.25 under DEG C condition, 1200L organic dispersing agent is added in filer element type suction filtration machine, under pressurized air bubbling rate is 800mL/min condition, modification is carried out to hydrotalcite, modification carried out suction filtration after 48 hours, arranging suction filtration pressure reduction is 0.1MPa, the filter cake obtained is transferred in continuous pan dryer dry, and the temperature arranging pan dryer is 40 DEG C, obtains high dispersive hydrotalcite powder after dry 12 hours; By use in modifying process with the organic dispersing agent that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch, the moisture of more than 99% can be removed after treatment, and the purity of organic dispersing agent can reach more than 98%.Organic dispersing agent used is 600L acetone and 600L methyl alcohol.
Embodiment 5:
The complete full scale plant using embodiment 1 to design is used for the suitability for industrialized production of high dispersive hydrotalcite powder:
A. be 15wt% by solid content, median size is 810nm, chemical formula is Mg
4al
2(OH)
12cO
34H
2o, adopt the obtained hydrotalcite slurry 1800L of nucleation-crystallization method to add filer element type suction filtration machine, filter core aperture is 210 μm, and arranging suction filtration pressure reduction is 0.3MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, carries out purification recycling, arrange and be neutralized to pH=7 by washing water regeneration system rapidly;
B.25 under DEG C condition, 2000L organic dispersing agent is added in filer element type suction filtration machine, under mechanical agitation, modification is carried out to hydrotalcite, mixing speed is 1000rpm, modification carried out suction filtration after 24 hours, and arranging suction filtration pressure reduction is 0.3MPa, and the filter cake obtained is transferred in continuous pan dryer dry, the temperature arranging pan dryer is 100 DEG C, obtains high dispersive hydrotalcite powder after dry 12 hours; By use in modifying process with the organic dispersing agent that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch, the moisture of more than 99% can be removed after treatment, and the purity of organic dispersing agent can reach more than 98%.Organic dispersing agent used is 1000L acetone and 1000L tetrahydrofuran (THF).
Embodiment 6:
The complete full scale plant using embodiment 1 to design is used for the suitability for industrialized production of high dispersive hydrotalcite powder:
A. be 12wt% by solid content, median size is 2 μm, chemical formula is Mg
4al
2(OH)
12(NO
3)
24H
2o, adopt the obtained hydrotalcite slurry 400L of nucleation-crystallization method to add filer element type suction filtration machine, filter core aperture is 250 μm, and arranging suction filtration pressure reduction is 0.01MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, carries out purification recycling, arrange and be neutralized to pH=7 by washing water regeneration system rapidly;
B.100 under DEG C condition, 600L organic dispersing agent is added in filer element type suction filtration machine, under pressurized air bubbling condition, modification is carried out to hydrotalcite, pressurized air bubbling rate is 100mL/min, modification carried out suction filtration after 24 hours, and arranging suction filtration pressure reduction is 0.01MPa, and the filter cake obtained is transferred in continuous pan dryer dry, the temperature arranging pan dryer is 200 DEG C, obtains high dispersive hydrotalcite powder after dry 12 hours; By use in modifying process with the organic dispersing agent that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch, the moisture of more than 99% can be removed after treatment, and the purity of organic dispersing agent can reach more than 98%.Organic dispersing agent used is 200L acetone, 200L ethanol, 200LN-N dimethyl formamide.
Claims (9)
1. produce a complete full scale plant for high dispersive hydrotalcite powder, it is characterized in that, this device comprises pulp storing tank, filer element type suction filtration machine, dispersion agent distillation system, washing water regeneration system rapidly, continuously pan dryer; Hydrotalcite slurry is entered filer element type suction filtration machine by pulp storing tank and carries out suction filtration, obtain hydrotalcite filter cake, the waste water of generation is purified rear recycling by washing water regeneration system rapidly; Then directly add organic dispersing agent to mix with hydrotalcite filter cake, under mechanical stirring and/or pressurized air bubbling condition, carry out modification to hydrotalcite, modification terminates rear suction filtration, modified filter cake is transferred to continuous pan dryer and carries out drying; In whole technical process, used organic dispersing agent recycles through dispersion agent distillation system.
2. complete full scale plant according to claim 1, is characterized in that, described filer element type suction filtration machine, its filter core adopt porous material make, aperture be nano level to micron order, duct is the random state of cross-distribution; During suction filtration, water or organic dispersing agent ooze out through duct, and hydrotalcite is retained down formation filter cake.
3. complete full scale plant according to claim 1, is characterized in that, described continuous pan dryer is arranged alternatively up and down by size drying tray, and with rake leaf on each drying tray, rake leaf controls to do turning motion by rake arms to be made rake leaf turn over continuously to copy material; On large drying tray, material moves to center and falls into the little drying tray of lower one deck from center blanking port, after receiving material little drying tray outwards move to immediately below large drying tray outer rim place, material also outwards movement simultaneously on little drying tray, and the large drying tray outer rim immediately below falling from outer rim; Modified filter cake is added on the first layer drying tray of moisture eliminator top, then continues to flow through every layer of drying tray surface along index spiral-line.
4. complete full scale plant according to claim 1, it is characterized in that, described dispersion agent distillation system by use in modifying process reclaim with the organic dispersing agent rectifying that produces in drying process after enter dispersion agent storage tank, hydrotalcite-modified for next batch; Described dispersion agent distillation system comprises reboiler, dispersion agent rectifying tower, interchanger, condenser, organic dispersing agent is separated, boils again, rectifying, condensation, by water wherein and impurity removing.
5. complete full scale plant according to claim 1, it is characterized in that, described washing water regeneration system rapidly, first the water reuse acid-base neutralisation principle produced after suction filtration is neutralized, maintain pH value between 6.0-8.0, then utilize reverse osmosis membrane to be removed by the metal ion in water, the water be purified enters water tank.
6. be used for the industrialized producing technology of high dispersive hydrotalcite powder according to the arbitrary described complete full scale plant of claim 1-5, it is characterized in that, its concrete steps are:
A. be that the hydrotalcite slurry 50-2000L of 1-15wt% adds in filer element type suction filtration machine by solid content, filter core aperture is 0.1-300 μm, and arranging suction filtration pressure reduction is 0.01-0.5MPa, is extracted out by water with vacuum pump, and hydrotalcite filter cake is stayed in filer element type suction filtration machine; The water extracted out enters washing water surge tank, deposits in water tank after utilizing washing water regeneration system rapidly to purify, recycling;
B.20-150 under DEG C condition, 50-2000L organic dispersing agent is added in filer element type suction filtration machine, under mechanical stirring and/or pressurized air bubbling condition, carry out modification to hydrotalcite, arranging mixing speed is 50-3000rpm, and pressurized air bubbling rate is 0.1-1000mL/min; Suction filtration is carried out after modification 1-72 hour, arranging suction filtration pressure reduction is 0.01-0.5MPa, the filter cake obtained is transferred in continuous pan dryer and carries out drying, and the temperature arranging continuous pan dryer is 30-200 DEG C, obtains high dispersive hydrotalcite powder after dry 1-48 hour; By use in modifying process with the organic dispersing agent that produces in drying process by entering dispersion agent storage tank after dispersion agent distillation system purification and recover, hydrotalcite-modified for next batch.
7. industrialized producing technology according to claim 6, is characterized in that, the chemical constitution of described hydrotalcite is [M
2+ 1-xm
3+ x(OH)
2] A
n- x/nmH
2o; Wherein M
2+represent divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+in one or both, preferred Mg
2+, Zn
2+, Ca
2+, Ni
2+in one or both; M
3+represent trivalent metal cation Al
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+in one or both, preferred Al
3+, Fe
3+in one or both; Acid radical anion A
n-be selected from one or more in following acid radical anion: (1) inorganic anion: CO
3 2-, NO
3 -, [B
4o
5(OH)
4]
2 –, F
-, Cl
-, Br
-, I
-, ClO
4 -, IO
3 -, H
2pO
4 -, HPO
4 2-, PO
4 3-, SO
4 2-, S
2o
3 2-, WO
4 2-, CrO
4 2-; (2) organic anion: p-phthalic bridge, P-hydroxybenzoic acid root, succinic, hexanodioic acid root, dodecyl sodium sulfonate root, benzoate anion; (3) with many, heteropolyacid anions: Mo
7o
24 6-, V
10o
28 6-, PW
11cuO
39 6-, SiW
9w
3o
40 7-; A
n-preferred NO
3 -, CO
3 2-, [B
4o
5(OH)
4]
2 –, SO
4 2-, PO
4 3-, succinic, one in benzoate anion; N is the valence number of acid radical anion, n=1-7.
8. industrialized producing technology according to claim 6, is characterized in that, the particle diameter of described hydrotalcite slurry is 30nm-5 μm.
9. industrialized producing technology according to claim 6, it is characterized in that, described organic dispersing agent is one or more in acetone, methyl alcohol, ethanol, n-propyl alcohol, Virahol, tetrahydrofuran (THF), acetonitrile, dioxane, methyl-sulphoxide, N-N dimethyl formamide, one or both in preferred acetone, methyl alcohol, ethanol, n-propyl alcohol, Virahol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410528456.5A CN104609450B (en) | 2014-10-09 | 2014-10-09 | A kind ofly produce the technique of high dispersive hydrotalcite powder and complete full scale plant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410528456.5A CN104609450B (en) | 2014-10-09 | 2014-10-09 | A kind ofly produce the technique of high dispersive hydrotalcite powder and complete full scale plant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104609450A true CN104609450A (en) | 2015-05-13 |
| CN104609450B CN104609450B (en) | 2016-04-20 |
Family
ID=53144150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410528456.5A Expired - Fee Related CN104609450B (en) | 2014-10-09 | 2014-10-09 | A kind ofly produce the technique of high dispersive hydrotalcite powder and complete full scale plant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104609450B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486657A (en) * | 2018-03-30 | 2018-09-04 | 岭南师范学院 | A kind of layered double hydroxide LDH- (NO3)2-SO4The preparation method of whisker |
| CN110065948A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | Method for preparing clay |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008113793A1 (en) * | 2007-03-21 | 2008-09-25 | Akzo Nobel N.V. | Process for preparing a layered double hydroxide |
| CN101381094A (en) * | 2007-09-03 | 2009-03-11 | 襄樊市油建化工有限公司 | Method for preparing nano magnalium hydrotalcite and equipment thereof |
| CN101386424A (en) * | 2008-10-14 | 2009-03-18 | 中国海洋大学 | method for preparing modification forming magnalium hydrotalcite and application |
| JP2012233146A (en) * | 2011-04-18 | 2012-11-29 | Katsuta Kako Kk | New anti-aging agent and rubber composition obtained by blending the same |
| CN103043691A (en) * | 2012-12-14 | 2013-04-17 | 湖南大学 | Preparation method of modified hydrotalcite and application thereof in heavy metal adsorption |
-
2014
- 2014-10-09 CN CN201410528456.5A patent/CN104609450B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008113793A1 (en) * | 2007-03-21 | 2008-09-25 | Akzo Nobel N.V. | Process for preparing a layered double hydroxide |
| CN101381094A (en) * | 2007-09-03 | 2009-03-11 | 襄樊市油建化工有限公司 | Method for preparing nano magnalium hydrotalcite and equipment thereof |
| CN101386424A (en) * | 2008-10-14 | 2009-03-18 | 中国海洋大学 | method for preparing modification forming magnalium hydrotalcite and application |
| JP2012233146A (en) * | 2011-04-18 | 2012-11-29 | Katsuta Kako Kk | New anti-aging agent and rubber composition obtained by blending the same |
| CN103043691A (en) * | 2012-12-14 | 2013-04-17 | 湖南大学 | Preparation method of modified hydrotalcite and application thereof in heavy metal adsorption |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110065948A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | Method for preparing clay |
| CN108486657A (en) * | 2018-03-30 | 2018-09-04 | 岭南师范学院 | A kind of layered double hydroxide LDH- (NO3)2-SO4The preparation method of whisker |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104609450B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | A novel approach to hierarchical sphere-like ZnAl-layered double hydroxides and their enhanced adsorption capability | |
| Li et al. | A facile approach to superhydrophobic and superoleophilic graphene/polymer aerogels | |
| Zhang et al. | Super adsorption capability of rhombic dodecahedral Ca-Al layered double oxides for Congo red removal | |
| Ahsani-Namin et al. | Green mediated combustion synthesis of copper zinc oxide using Eryngium planum leaf extract as a natural green fuel: Excellent adsorption capacity towards Congo red dye | |
| CA2744601C (en) | Method for continuously preparing metal oxides catalyst and apparatus thereof | |
| KR20160139003A (en) | High surface area layered double hydroxides | |
| Dong et al. | Magnetic nano-hybrids adsorbents formulated from acidic leachates of clay minerals | |
| KR102246046B1 (en) | Manufacturing method of mesoporous silica from biomass | |
| Li et al. | Synthesis of uniformly distributed magnesium oxide micro-/nanostructured materials with deep eutectic solvent for dye adsorption | |
| Devarajan et al. | Solvent free transesterification of glycerol into glycerol carbonate over nanostructured CaAl hydrotalcite catalyst | |
| Lv et al. | A general strategy for the synthesis of layered double hydroxide nanoscrolls on arbitrary substrates: its formation and multifunction | |
| Chen et al. | Reduction of 4-nitrophenol and 2-nitroaniline using immobilized CoMn 2 O 4 NPs on lignin supported on FPS | |
| CN104609450B (en) | A kind ofly produce the technique of high dispersive hydrotalcite powder and complete full scale plant | |
| Li et al. | Preparation of MnO 2 and calcium silicate hydrate from electrolytic manganese residue and evaluation of adsorption properties | |
| EP2954010B1 (en) | Method for producing porous or fine-particle solid inorganic materials | |
| US20040192884A1 (en) | Process for purification of crude polyether and adsorbent | |
| CN110496597A (en) | Graphene oxide modified montmorillonoid composite adsorbing material and its preparation method and application | |
| KR101167235B1 (en) | Method for preparation of zeolite 13X and mesoporous silica derived from power plant bottom ash, and carbon dioxide sorbents based on zeolite 13X and mesoporous silica prepared by the method | |
| Jia et al. | Facile preparation of mesoporous nickel oxide microspheres and their adsorption property for methyl orange from aqueous solution | |
| Ohta et al. | Synthesis of allophane from rice husk ash and its use as a phosphate adsorbent: A novel approach | |
| Ariharan et al. | Phosphorous-doped porous carbon derived from paste of newly growing Ficus benghalensis as hydrogen storage material | |
| WO2023148788A1 (en) | Production of ultrafine silicate by wet chemical method from silicate precursor | |
| Liou | Recovery of silica from electronic waste for the synthesis of cubic MCM-48 and its application in preparing ordered mesoporous carbon molecular sieves using a green approach | |
| Zhang et al. | Preparation and characterization of a porous silicate material from silica fume | |
| Zamani et al. | Synthesis of high surface area boehmite and alumina by using walnut shell as template |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160420 Termination date: 20191009 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |