CN101797492B - Method for preparing laminated dihydroxy composite metal hydroxide porous microspheres - Google Patents
Method for preparing laminated dihydroxy composite metal hydroxide porous microspheres Download PDFInfo
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- CN101797492B CN101797492B CN2010101512085A CN201010151208A CN101797492B CN 101797492 B CN101797492 B CN 101797492B CN 2010101512085 A CN2010101512085 A CN 2010101512085A CN 201010151208 A CN201010151208 A CN 201010151208A CN 101797492 B CN101797492 B CN 101797492B
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Abstract
The invention discloses a method for preparing laminated dihydroxy composite metal hydroxide porous microspheres, and belongs to the technical field of catalyst forming. The method comprises the following steps of: preparing laminated dihydroxy composite metal hydroxide particles with nano-scale or submicron-scale particle diameter from common hydrotalcite-like materials by using a preparation method, such as a nucleation/separation method; and preparing the porous microsphere material on industrial spray drying equipment by modulating the added polystyrene template amount and using colloidal slurry as raw materials. The material does not need a secondary forming step; PS templates are removed in the activation process; and the product can be directly applied to the field of catalysis or separation after hydration processing.
Description
Technical field
The invention belongs to the field shaping technique of catalyst, being specifically related to a kind of is the molding, granulating method of basic structural unit to have nanoscale or submicron order laminated dihydroxy composite metal hydroxide particulate.
Background technology
Laminated dihydroxy composite metal hydroxide (Layered Double Hydroxide is abbreviated as LDH) is one type of anionic clay the most representative, and its main body generally is made up of the hydroxide of two kinds of metals.Be called hydrotalcite-based compound again, comprise hydrotalcite (Hydrotalcite) and houghite (Hydrotalcite-like compound), the intercalation compound of LDH is called intercalated houghite.1842, the Circa of Swede just found the existence of natural LDHs mineral, and 1969, people such as Allmann measured the structure of LDHs monocrystalline, had confirmed the layer structure of LDHs first.This material is six side's lamellar structures, and lamella itself has extremely strong rigidity, and morphology control becomes the hot issue of current research.Said material is a kind of inorganic material with unique structural characteristics: form adjustable sex change, the adjustable sex change of pore structure and designability of interlayer intercalant anion kind etc. in relative broad range like element and established this type material and might become the industrial catalyst with potential application foreground or the basis of catalyst precursor, the earlier 1900s people have just found the high active of hydrogenation catalysis of LDHs.Through further experiment research; This type material is through high-temperature roasting; The laminate metal cation can change homodisperse composite metal oxide with spinel structure on molecular scale into; Therefore, we can be through obtaining to have the catalyst or the catalyst carrier of specific catalytic performance to designs such as the kind of laminate metal cation and proportionings.
Shaping of catalyst is one of committed step in the catalyst industrial processes.Because the shaping of catalyst method is different with technology, prepared catalyst pores structure, specific surface and surface texture structure also have marked difference, thereby bring different results of use.So the research and development of the forming technique of catalyst are extremely important, on this basis, also develop and various catalyst new varieties.
Concerning a kind of industrial heterogeneous catalyst, must possess the performance of the following aspects:
(1) active good;
(2) selectivity is high;
(3) activity stabilized, long service life;
(4) has suitable physical and chemical performance (specific area, pore volume, aperture etc.);
(5) has necessary strength (crushing strength, tear strength);
(6) suitable shape (particle diameter or size distribution) is arranged.
Above-mentioned each item catalyst serviceability all has relation in various degree with shaping of catalyst.For the reaction of slowly carrying out, pore is favourable; Be decided by diffusion velocity for fast reaction.And the porosity of catalyst and pore structure and forming method and condition of molding are closely related.In the fixed bed catalyst process; Give full play to efficient for making catalyst; The situation such as the grain shape of catalyst in reaction bed, size, filling of just should optimizing are in optimum state; Just can make the efficiency factor of catalyst in practical application in industry, reach maximum, thereby improve the result of use of catalyst greatly.The microspherical catalyst of fluidized-bed reactor diameter 20-150 μ m commonly used or bigger particle diameter.The microballoon of no corner angle has good flowing property and reduces the abrasion that catalyst fluidization produces.So, both at home and abroad moulding as one of important content that improves catalyst performance.Catalyst just can provide the beaded catalyst of suitable shape, size and mechanical strength according to catalyst reaction and reaction unit requirement thereof through processing and forming, and the activity and the selectivity that catalyst are given full play to had, prolongation catalyst service life.When Industrial Catalysis was used, moulding helped increasing the mechanical strength of catalyst on the one hand, helped the Separation and Recovery of catalyst and utilization once more on the other hand.
In the thousands of kinds of catalyst that domestic chemical industry uses, there is quite a few having the forming technique problem in varying degrees.All use houghite materials use powder body material for as catalyst precursor the time more in the document, therefore, this houghite forming materials with extremely strong rigidity will be helped improving the catalytic effect of catalyst and separating and recovery of different-phase catalyst.
At present; There have been many pieces of article report hydrotalcite-based compounds to have excellent performance as materials such as catalyst, catalyst carrier, adsorbent and ion-exchangers; Chem.Eur.J.2005; Among the 11:728-739, people such as Abello have studied and the composite oxides after the roasting of MgAl-LDHs powder are carried out rehydration have handled and recover its layer structure.Investigated the influence of the catalytic activity of MgAl-LDHs in the acetone self-condensation reaction.J.Catal, 2001, among the 203:184-191, people such as Rorlofs find the increase of the initial catalytic activity of MgAl-OH-LDHs along with catalyst particle size, reducing of specific area of BET and reducing.Inter.J.Hydro.Enery; 2007, among the 32:5089-5102, it is being the nickel-base catalyst that precursor obtains activation with NiAl-LDH that people such as Caixia Qi have studied; Be used for methyl alcohol and prepare hydrogen reaction at two kinds of different atmospheres; In this reaction, show, to have good reactivity and selectivity through high activity nickel after the high-temperature atmosphere activation with the synthetic hydrotalcite of coprecipitation method.
In view of existing document; The houghite material has shown good catalytic effect as catalyst and catalyst precursor; Catalyst is by moulding; It is synthetic that catalyst pattern and structure are carried out certain control, more helps improving catalyst separation and recycling after catalytic reaction usefulness and reaction finish.Therefore, the houghite material is carried out controlled moulding preparation, very big Research Significance and scientific value are arranged.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of laminated dihydroxy composite metal hydroxide porous property microballoon; Small particle diameter houghite with nanoscale or submicron order is a raw material; Utilize industrial spray drying device, realize the direct preparation of the laminated dihydroxy composite metal hydroxide material of microballoon form.Promptly at first utilize common houghite preparation methods such as nucleation crystallization/isolation method to prepare laminated dihydroxy composite metal hydroxide (houghite) particle of particle diameter for nanoscale or submicron order; The polystyrene that adds through modulation then (is abbreviated as PS; The laboratory self-control; Average grain diameter is 400nm) template amount difference is initial material is realized the porous micro-sphere material on industrial spray drying device preparation with the colloidal state slurries.This material need be through formative stage once more, and activation process is removed the PS template simultaneously, and after the hydration-treated, product can directly be used for catalysis or separation field again.
Laminated dihydroxy composite metal hydroxide porous microspheres provided by the invention, its chemical general formula is:
[M
2+ 1-xM
3+ x(OH)
2]
x+·(A
n-)
x/n·mH
2O；
Wherein, M
2+Be divalent metal, comprise Mg
2+, Ni
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+, Fe
2+In one or both; M
3+Be trivalent metal cation, comprise Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+, V
3+In one or both; A
N-Be interlayer anion, comprise NO
3 -, Cl
-, CO
3 2-Or SO
4 2-X is M
2+/ (M
2++ M
3+) molar ratio, its span is 0.2≤x≤0.33; M is the number of intermediary water molecule, and its span is 0≤m≤2.
The particle diameter of this microballoon between 5-80 μ m, average grain diameter d
(0.5)=20-30 μ m, bulk density are 0.2-4.5g/cm
3, specific area is at 20-150m
2Between/the g; Pore volume is between the 0.2-2.49cc/g, can near pore-size distribution between 10-1000nm, be to have micropore, and mesoporous, macropore is the microsphere particle of one.
Concrete preparation process of the present invention is following:
A: nanoscale or submicron order houghite are used the deionized water centrifuge washing, and the pH that makes supernatant is 7-8, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for the 10-20% of total solution quality, PS accounts for the 2-10% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: the colloidal state slurries of step B are squeezed into the flow velocity of 10-30ml/min on the atomizing wheel disc of rotary spray dryer with constant flow pump, regulated the atomizing wheel rotating speed ten thousand rev/mins of 1.0-2.0, spray-drying import department temperature is between 120-180 ℃; Obtain spheric granules behind the mist projection granulating;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: 300-800 ℃ keeps naturally cooling to room temperature after 6-15 hour, gets the 0.5-2 gram and puts into the bottom and contain 100-300ml and remove CO
2In the there-necked flask of water, at N
2Protection is hydration-treated down, and product keeps the porous microsphere pattern.
Step C preferred operations condition is: the atomizing wheel rotating speed is ten thousand rev/mins of 1.2-1.5, and charging rate is 5-20mL/min, and inlet temperature is between 140-160 ℃.
Described nanoscale or submicron order houghite adopt nucleation/crystallization isolation method preparation, promptly adopt the mixed liquid film reactor that is all-trans to carry out nucleation, carry out crystallization through temperature programmed control dynamic crystallization method again.
The present invention is prepared into laminated dihydroxy composite metal hydroxide has micropore, and mesoporous, macropore is the porous microsphere particle of one, catalyst separation and recycling after having improved its catalytic reaction usefulness and having helped reacting end.
Description of drawings
Fig. 1 is the XRD spectra of embodiment 1, and wherein 1a is the XRD spectra of step C product; 1b is the XRD spectra of the bimetallic oxide that obtains after the roasting among the step D; 1c is the XRD spectra of step D end product.
Fig. 2 is the SEM picture of embodiment 1, and wherein 2a is the spheric granules of embodiment 1 through obtaining after the spray-drying; 2b be embodiment 1 step D through 500 ℃ of roastings after the SEM spectrogram of microballoon.
Fig. 3 is the SEM spectrogram of the laminated dihydroxy composite metal hydroxide porous microspheres that obtains of embodiment 2 step D, and 3a is the SEM spectrogram of microballoon, and 3b is the microsphere surface partial enlarged drawing.
Fig. 4 is that the pressure of the product that obtains of embodiment 1 step C is moved back the tribute curve.
Fig. 5 is the pressure mercury ejection curve of the laminated dihydroxy composite metal hydroxide porous microspheres that obtains of embodiment 1 step D.
Below in conjunction with embodiment the present invention is further described:
The specific embodiment
Embodiment 1:
A: take by weighing 102.56g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 38.40g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 2 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 20% of total solution quality, PS accounts for 2% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 10mL/min with constant flow pump, and to set spray-drying import department temperature be 150 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 10-80 μ m, average grain diameter is 30 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 200ml and remove CO
2In the water there-necked flask, at N
2The following hydration-treated again of protection, product keeps the porous microsphere pattern.
003 of the 1b hydrotalcite, 006 characteristic diffraction peak disappears among Fig. 1, the substitute is the appearance of the characteristic diffraction peak of the MgO with relatively poor degree of crystallinity; 003,006,110 diffraction maximums of 1c hydrotalcite have occurred again, explain to have obtained the hydrotalcite constructed again, and the process of this structural remodeling is called " memory effect ".This process roasting later hydrotalcite of hydration again is a kind of solid catalyst of excellence, and the process roasting is hydro-combination process again, the CO of interlayer
3 2-By OH
-Replace.
Visible by Fig. 5, roasting is the hydration-treated front and back again, and pore volume has increase by a relatively large margin.
Embodiment 2:
A: take by weighing 102.56g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 38.40g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 2 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 8, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 20% of total solution quality, PS accounts for 5% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 8mL/min with constant flow pump, and to set spray-drying import department temperature be 150 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 10-80 μ m, average grain diameter is 30 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following: be warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cool to room temperature; Getting 1 gram puts into the bottom and contains 200ml and remove CO
2In the water there-necked flask, at N
2The following hydration-treated again of protection, product keeps the porous microsphere pattern.
After Fig. 3 finds out roasting, remove template and stayed more hole, and hydrotalcite returns to single particle strip-like features structure again.
Embodiment 3:
A: take by weighing 102.56g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 38.40g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 2 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7.5, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 20% of total solution quality, PS accounts for 10% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 15mL/min with constant flow pump, and to set spray-drying import department temperature be 150 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 10-80 μ m, average grain diameter is 30 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 200ml and remove CO
2In the water there-necked flask, at N
2Protection down, hydration-treated again, product keeps the porous microsphere pattern.
Embodiment 4:
A: take by weighing 102.56g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 38.40g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 2 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 10% of total solution quality, PS accounts for 10% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 20mL/min with constant flow pump, and to set spray-drying import department temperature be 150 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 10-80 μ m, average grain diameter is 30 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 200ml and remove CO
2In the water there-necked flask, at N
2The following hydration-treated again of protection, product keeps the porous microsphere pattern.
Embodiment 5:
A: take by weighing 102.56g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 38.40g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 2 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 10% of total solution quality, PS accounts for 2% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 10mL/min with constant flow pump, and to set spray-drying import department temperature be 120 ℃, carry out mist projection granulating; The solid spherical particle grain size distribution 10-80 μ m that is obtained, average grain diameter is 25 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 200ml and remove CO
2In the water there-necked flask, at N
2The following hydration-treated again of protection, product keeps the microspheric pattern.
Embodiment 6:
A: take by weighing 102.56g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 38.40g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 2 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 15% of total solution quality, PS accounts for 5% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 15mL/min with constant flow pump, and to set spray-drying import department temperature be 180 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 5-60 μ m, average grain diameter is 28 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 200ml and remove CO
2In the water there-necked flask, at N
2Protection down, hydration-treated again, product keeps the porous microsphere pattern.
Embodiment 7:
A: take by weighing 153.84g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 51.20g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 3 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 20% of total solution quality, PS accounts for 2% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 10mL/min with constant flow pump, and to set spray-drying import department temperature be 150 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 5-80 μ m, average grain diameter is 30 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 250ml and remove CO
2In the water there-necked flask, at N
2Protection down, hydration-treated again, product keeps porous microsphere type pattern.
Embodiment 8:
A: take by weighing 153.84g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 51.20g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 3 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 20% of total solution quality, PS accounts for 10% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 20mL/min with constant flow pump, and to set spray-drying import department temperature be 180 ℃, carry out mist projection granulating; Obtain spheric granules, the 5-60 μ m that directly distributes, average grain diameter is 25 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 250ml and remove CO
2In the water there-necked flask, at N
2Protection down, hydration-treated again, product keeps the porous microsphere pattern.
Embodiment 9:
A: take by weighing 205.12g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 64g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 4 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 8, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 20% of total solution quality, PS accounts for 5% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 12mL/min with constant flow pump, and to set spray-drying import department temperature be 150 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 5-80 μ m, average grain diameter is 30 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature; Getting 1 gram puts into the bottom and contains 300ml and remove CO
2In the water there-necked flask, at N
2Protection down, hydration-treated again, product keeps the porous microsphere pattern.
Embodiment 10:
A: take by weighing 205.12g Mg (NO
3)
26H
2O and 75.02g Al (NO
3)
39H
2O is dissolved in and is made into the 500mL mixing salt solution in the deionized water; And then take by weighing 64g NaOH and 42.40g Na
2CO
3Be dissolved in and be made into the 500mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixed solutions are added full back-mixing liquid film reactor simultaneously, and the slit width between conditioned reaction device rotor and the stator is 0.02mm, and operating voltage is 100V; Rotor speed is 4000rpm, the mixed serum that obtains is added in the there-necked flask stir, and keeping the temperature of mixed serum in the heating jacket is 90 ℃ of backflow crystallization 6 hours; Obtain Mg/Al and be 4 magnesia-alumina hydrotalcite; Use the deionized water centrifuge washing, the pH that makes supernatant is 7.5, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for 10% of total solution quality, PS accounts for 2% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: squeeze into the colloidal state slurries of step B with 1.2 ten thousand rev/mins at a high speed on the atomizing wheel discs of rotation with the flow velocity of 20mL/min with constant flow pump, and to set spray-drying import department temperature be 180 ℃, carry out mist projection granulating; Obtain spheric granules, particle diameter distribution 5-60 μ m, average grain diameter is 25 μ m;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: roasting process is following, is warmed up to 500 ℃ from 20 ℃ of heating rates with 0.5 ℃/min of room temperature, after this temperature keeps 10 hours, naturally cools to room temperature.Getting 1 gram puts into the bottom and contains 300ml and remove CO
2In the water there-necked flask, at N
2Protection down, hydration-treated again, product keeps the porous microsphere pattern.
Claims (3)
1. the preparation method of a laminated dihydroxy composite metal hydroxide porous microspheres is characterized in that, its concrete preparation process is following:
A: nanoscale or submicron order houghite are used the deionized water centrifuge washing, and the pH that makes supernatant is 7-8, gets centrifugal slurry;
B: template PS is added in the centrifugal slurry that steps A obtains, add deionized water, make the houghite quality account for the 10-20% of total solution quality, PS accounts for the 2-10% of total solution quality, fully stirs to make system be even mixed colloidal slurries;
C: the colloidal state slurries of step B are squeezed into the flow velocity of 10-30ml/min on the atomizing wheel disc of rotary spray dryer with constant flow pump, regulated the atomizing wheel rotating speed ten thousand rev/mins of 1.0-2.0, spray-drying import department temperature is between 120-180 ℃; Obtain spheric granules behind the mist projection granulating;
D: the spheric granules that step C is obtained carries out roasting hydration-treated again: 300-800 ℃ keeps naturally cooling to room temperature after 6-15 hour, gets the 0.5-2 gram and puts into the bottom and contain 100-300ml and remove CO
2In the there-necked flask of water, at N
2Protection is hydration-treated down, and product keeps the porous microsphere pattern;
The chemical general formula of the laminated dihydroxy composite metal hydroxide porous microspheres that is made by said method is:
[M
2+ 1-xM
3+ x(OH)
2]
x+·(A
n-)
x/n·mH
2O；
Wherein, M
2+Be divalent metal, be Mg
2+, Ni
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+, Fe
2+In one or both; M
3+Be trivalent metal cation, be Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+, V
3+In one or both; A
nBe interlayer anion, be NO
3 -, Cl
-, CO
3 2-Or SO
4 2-X is M
3+/ (M
2++ M
3+) molar ratio, its span is 0.2≤x≤0.33; M is the number of intermediary water molecule, and its span is 0≤m≤2;
The particle diameter of this microballoon between 5-80 μ m, average grain diameter d
(0.5)=20-30 μ m, bulk density are 0.2-4.5g/cm
3, specific area is at 20-150m
2Between/the g; Pore volume is between the 0.2-2.49cc/g, can near pore-size distribution between 10-1000nm, be to have micropore, and mesoporous, macropore is the microsphere particle of one.
2. the preparation method of a kind of laminated dihydroxy composite metal hydroxide porous microspheres according to claim 1; It is characterized in that; The operating condition of said step C is: the atomizing wheel rotating speed is ten thousand rev/mins of 1.2-1.5, and charging rate is 5-20mL/min, and inlet temperature is between 140-160 ℃.
3. the preparation method of a kind of laminated dihydroxy composite metal hydroxide porous microspheres according to claim 1 and 2; It is characterized in that; Described nanoscale or submicron order houghite adopt nucleation/crystallization isolation method preparation; Promptly adopt the mixed liquid film reactor that is all-trans to carry out nucleation, carry out crystallization through temperature programmed control dynamic crystallization method again.
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| CN102294209B (en) * | 2011-06-13 | 2012-10-17 | 北京化工大学 | Preparation method of hydrotalcite hollow microballoon |
| CN102284264B (en) * | 2011-06-15 | 2012-10-31 | 北京化工大学 | Method for preparing hydrotalcite coated ferroferric oxide microspheres |
| CN102874853B (en) * | 2011-07-12 | 2014-04-09 | 北京化工大学 | Annular Mg-Al double-hydroxy composite metal hydroxide and preparation method thereof |
| CN104971691B (en) * | 2015-06-17 | 2017-08-15 | 北京化工大学 | A kind of nanometer magnesium silicate sorbing material and preparation method thereof |
| CN107022115B (en) * | 2017-05-10 | 2019-08-13 | 北京化工大学 | A kind of intercalated houghite anti-ultraviolet ageing agent for rubber and preparation method thereof and application method |
| CN113000049B (en) * | 2019-12-20 | 2022-12-23 | 中国科学院青岛生物能源与过程研究所 | Method for preparing Ni-Al-based oxide catalyst |
| CN113019364A (en) * | 2021-03-29 | 2021-06-25 | 西北有色金属研究院 | Preparation method of porous ruthenium dioxide-cerium dioxide microsphere composite material |
| CN114573011A (en) * | 2022-03-18 | 2022-06-03 | 北京化工大学 | Controllable preparation method of ultrathin composite metal hydroxides with different thicknesses |
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| US4477492A (en) * | 1983-04-22 | 1984-10-16 | E. I. Du Pont De Nemours And Company | Process for preparing superficially porous supports for chromatography and catalysts |
| CN1211608A (en) * | 1997-09-17 | 1999-03-24 | 中国石油化工总公司 | Laminar column clay microphere cracking catalyst for heavy oil and its preparation |
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477492A (en) * | 1983-04-22 | 1984-10-16 | E. I. Du Pont De Nemours And Company | Process for preparing superficially porous supports for chromatography and catalysts |
| CN1211608A (en) * | 1997-09-17 | 1999-03-24 | 中国石油化工总公司 | Laminar column clay microphere cracking catalyst for heavy oil and its preparation |
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
Non-Patent Citations (1)
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| 陈虹芸等.层状双羟基复合金属氧化物薄膜的研究进展.《中国科学 B 辑:化学》.2008,第38卷(第8期),659-667. * |
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