CN1195582C - Spherical aluminium oxide carrier material and preparation process thereof - Google Patents
Spherical aluminium oxide carrier material and preparation process thereof Download PDFInfo
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- CN1195582C CN1195582C CNB021215847A CN02121584A CN1195582C CN 1195582 C CN1195582 C CN 1195582C CN B021215847 A CNB021215847 A CN B021215847A CN 02121584 A CN02121584 A CN 02121584A CN 1195582 C CN1195582 C CN 1195582C
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Abstract
The present invention discloses a spherical alumina supporter material and a preparation method thereof. The supporter material contains 50 to 99 wt% of alumina and 1 to 50 wt% of magnetic particle, wherein the magnetic particles are composed of SiO2 coating layers and kernels selected from one or several kinds of Fe3O4, Fe and gamma-Fe2O3, and the weight ratio of the coating layers to the kernels is (0.01 to 6): 1. After nanometer Fe3O4 particles are slowly acidified in a sodium silicate solution to form the SiO2 coating layers, the magnetic particles are obtained and are mixed with aluminum hydroxide sol and organic amine to form uniformly dispersed water phases; after the uniformly dispersed water phases and oil phases form water-in-oil liquid droplets, the sol liquid droplets in the water phases are gelled and solidified by heating systems; the supporter material is obtained by the conventional processes of hydrothermal treatment, aging, drying and sintering. The spherical alumina supporter material provided by the present invention has super paramagnetic properties, is capable of being particularly used as catalyst supporters in external magnetic field reaction processes, is convenient for positioning control, separation and recovery by external magnetic fields, and the purpose of repeated and circulatory use is achieved.
Description
Technical field
The invention relates to a kind of ball-aluminium oxide carrier material and preparation method thereof.
Technical background
It is big that fine grain catalysis material has specific area, mass transfer rate is fast, advantages such as catalytic efficiency height, the development of finely grained catalyst is the important development direction of heterogeneous catalysis research in recent years, but because catalyst granules is tiny, not only in course of reaction, be difficult to control, and exist the difficult problem of post catalyst reaction separation recovery.The new approach of having opened up is used in the research that develops into the functionalization finely grained catalyst of fine grained magnetic catalyst and magnetic stopping reaction technology (seeing " development of industrial catalyst and exploitation ", Sinopec publishing house, 1997,195 pages).
In petrochemical industry, aluminium oxide is widely used in can directly being used as catalyst activity component and adsorbent in addition in the multiple reactions such as oxidation, hydrogenation, dehydrogenation, reformation, isomerization, disproportionation, polymerization as the catalyst carrier that has the call.
About aluminium oxide and preparation method thereof, there are a lot of documents to report.For example, US.Pat.2,620,314 disclosed ball-aluminium oxide carriers splash into curing molding in the oil column of heat by the solution that plate hole will contain aluminum hydroxide sol and organic amine, form through ageing and sintering.US.Pat.4,273,735 disclosed γ-Al
2O
3Carrier is that the aluminium hydroxide of the curing that will obtain in oil column carries out hydrothermal treatment consists in oily medium, and the aluminium hydroxide that obtains having the boehmite structure is made behind ageing and sintering.US.Pa t.4, the alumina support of 315,839 disclosed high strength with better crystallization, light weight, high pore volume is in aluminium hydroxide granulating and forming process, mixes ultra-fine boehmite or false boehmite, obtains behind sintering.US.Pat.2,915,365, US.Pat.3,480,389 and US.Pat.3,628, the 914 disclosed alumina supports that higher mechanical strength, specific surface and greater activity arranged are that the product that will contain after the gibbsite granulation of gibbsite carries out high-temperature water heat treatment in acid medium, and sintering obtains then.
Above-mentioned document has mainly disclosed the preparation aluminium oxide and to the control of performances such as aluminium oxide crystal formation, structure or intensity, but does not all relate to the magnetic property of aluminium oxide, up to now, also find no close have superparamagnetism can the report of alumina supporting material.
The object of the present invention is to provide a kind of have superparamagnetism can the ball-aluminium oxide carrier material and its preparation method is provided.
Summary of the invention
Ball-aluminium oxide carrier material provided by the invention contains the aluminium oxide of 50～99 heavy % and the magnetic-particle of 1～50 heavy %, and wherein said magnetic-particle is by SiO
2Clad and be selected from Fe
3O
4, Fe and γ-Fe
2O
3In one or more kernels form said SiO
2The weight ratio of clad and kernel is (0.01～6): 1, preferred (0.3～4.0): 1.
Ball-aluminium oxide carrier material provided by the present invention, its particle diameter is between 10 μ m to 6mm.
Said aluminium oxide be selected from amorphous alumina, various low temperature transition aluminas (ρ-, χ-, η-, γ-), various high temperature transition aluminas (κ-, δ-, θ-) or Alpha-alumina in one or more mixture.Said aluminium oxide is that the predecessor by aluminium oxide is transformed, and the predecessor of said aluminium oxide mainly is alkaline aluminium salt, unformed aluminium hydroxide, gibbsite, gibbsite, visit aluminium stone, promise diaspore, a water aluminium oxide, diaspore and boehmite, false boehmite etc.
In ball-aluminium oxide carrier material provided by the invention, magnetic-particle is dispersed in the structure of alumina support (Fig. 3).Said magnetic-particle, kernel are the single domain superparamagnetism particulates of one or more particle diameters in 3～30 nanometers, and clad is the amorphous Si O that closely coats kernel
2Layer (Fig. 1) has good hydrophily, shows that by X-ray diffraction (XRD) spectrogram bigger ripple bag is arranged, and this is amorphous Si O in ° scope of 2 θ=20～30
2Characteristic peak (Fig. 2), unbodied SiO
2Clad and kernel strong bonded form magnetic-particle.For the magnetic-particle that kernel has a plurality of particulates, between a plurality of particulates because SiO
2Obstruct and evenly distribute.
Ball-aluminium oxide hysteresis curve that carrier material is surveyed provided by the invention does not have hysteresis, when outside magnetic field exists, good magnetic property is arranged, and is adding magnetic field H=0 o'clock, and remanent magnetization Mr and coercivity H are zero, have superparamagnetism.
Ball-aluminium oxide carrier material provided by the present invention, the SiO on its inner magnetic kernel, surface
2Form certain component echelon and structure gradient between clad and the carrier component aluminium oxide, have good heat endurance and corrosion resistance, because SiO
2The buffer action of clad, the bad reaction that can avoid kernel iron component and alumina catalyst support component to take place in addition, in the application process of this carrier material, also can be avoided iron component poisoning some catalyst activity component in the kernel.
The present invention also provides the preparation method of above-mentioned ball-aluminium oxide carrier material, and this preparation method contains preparation SiO
2The process of moulding (inner gel) prepares the magnetic ball-aluminium oxide in cladded type magnetic component particle, the employing oil, further reduces or oxidation processes the steps such as form of magnetic-particle core in the control carrier.
More particularly, the preparation method of ball-aluminium oxide carrier material provided by the present invention contains the following step:
1, at 50～100 ℃, to containing Fe
2+With Fe
3+Add alkali in the aqueous solution of salt, with the nanometer Fe of deposition
3O
4Particle changes in the sodium silicate solution, under the protection of inert gas, adds acid solution is transferred to neutrality or below the neutrality, obtains SiO
2Coat Fe
3O
4The magnetic particle of particle, wherein, Fe in the said molysite
2+With Fe
3+Mol ratio be 1: (0.5～2.5), preferred 1: (1.5～2), the OH of said alkali
-With ∑ (Fe
2++ Fe
3+) mol ratio be 1: (0.1～1.0), said sodium metasilicate and Fe
3O
4Mol ratio be 1: (0.043～5.2), preferred 1: (0.065～0.864);
2, under-10～35 ℃, the magnetic particle three of aluminum hydroxide sol, organic amine solution and step 1 is mixed, after forming finely dispersed water, volume ratio with water and oil phase is 1: (3～20), preferred 1: the ratio of (4～10) is scattered in the oil phase, after forming the water-in-oil type drop, heating systems solidifies the aluminum hydroxide sol drop gelling of aqueous phase, hydrothermal treatment consists, ageing, drying and sintering process through routine obtains the ball type carrier material again, wherein, the volume ratio of organic amine solution and aluminum hydroxide sol is 1: (0.3～2.5);
3, in reducing atmosphere or oxidizing atmosphere, heat-treat or adopt oxidant or reducing agent that carrier is handled, the kernel type in the carrier material magnetic-particle is changed carrier.
In the preparation method of ball-aluminium oxide carrier material provided by the present invention, said alkali is selected from KOH, NaOH, NH in the step 1
4OH, Na
2CO
3Or NaHCO
3A kind of or its mixture wherein.Said acid is selected from a kind of in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid or the acetate or their mixture.
In step 2, make organic amine solution, aluminum hydroxide sol and magnetic-particle three mix the formation water by means such as stirring, vibration, ultrasonic dispersions; The mass concentration of wherein said organic amine solution is 12%～40%, said organic amine is meant that the pH value is near neutral at normal temperatures, but,, can be used singly or in combination as urea or hexamethylenetetramine through adding the material that thermal decomposition can discharge alkaline matter.
The volume ratio of said organic amine solution and aluminum hydroxide sol is 1 in the step 2: (0.3～2.5), preferred 1: (0.8～1.3).Said aluminum hydroxide sol, its preparation method can be referring to US.Pat.2,620,314, US.Pat.4,273, the method of narrating in the patents such as 735, generally be to obtain in the aluminum salt solutions such as the aluminium salt that under higher temperature, is dissolved in halogen such as the oxide that adopts metallic aluminium, aluminium, aluminium hydroxide, aluminum sulfate, aluminum nitrate, in preparation method provided by the present invention, be to be dissolved in liquor alumini chloridi as preferred version with metal aluminum foil, aluminium powder, wherein the aluminium in the colloidal sol/chlorine weight ratio is controlled at 0.3～2.0, and preferable range is 1.3～1.6.
Said oil phase Ying Yushui does not dissolve each other, its density near or less than the density of aqueous phase solution, can be selected from one or more the mixture that comprises gasoline, kerosene, diesel oil, transformer oil, benzene, biphenyl, halogenated hydrocarbons etc., can use separately or multiple being used in combination.
In step 2, in oil phase, can also add emulsifying agent, the addition of emulsifying agent is 0.02～2.0 volume % of oil phase.Said emulsifying agent is meant the low-molecular-weight surfactant of hydrophilic lipophilic balance (HLB value)＜9, as Span80 (sorbitan monooleate), Span85 (sorbitan trioleate), Span65 (anhydrous sorbitol three hard fatty acid esters), Span60 (sorbitan monostearate), Span40 (anhydrous sorbitol monopalmitate), Span20 (sorbitan mono-laurate), the Macrogol 200 dioleic acid ester, ethylene glycol monostearate, glyceryl monostearate, polyoxyethylene fatty acid ester, the two stearates of PEG400, lanolin etc. can be that a kind of or wherein several surfactant in them makes up the emulsifying agent of HLB value＜9 that obtain each other.
In the step 2, contents such as the hydrothermal treatment consists of said routine, ageing, drying and sintering can be with reference to US.Pat.2, and 620,314, US.Pat.4, the content of narrating in 273,735 patent documentations such as grade.Said hydrothermal treatment consists condition be the product that in autoclave, the gelling of aluminum hydroxide sol drop solidified at oil or aqueous medium, handled 1～10 hour, preferred 2～5 hours for 105～260 ℃, preferred 120～200 ℃ in the preferred oil medium.
Said sintering processes process be with through hydrothermal treatment consists, ageing and dry formed aluminum oxide precursor thing according to requirement, in the process of corresponding roasting temperature to end product aluminium oxide crystal formation.Said aluminum oxide precursor thing can be alkaline aluminium salt, amorphous hydroted alumina, gibbsite, gibbsite, visit a kind of in aluminium stone, promise diaspore, a water aluminium oxide, diaspore, boehmite, the false boehmite or their mixture.
Step 3 is that carrier material is reduced and oxidation processes, makes that the magnetic kernel in the magnetic component changes in the carrier, to change the magnetic property of carrier material.Magnetic kernel Fe
3O
4, γ-Fe
2O
3And the transformation rule between the Fe generally is: magnetic Fe
3O
4Kernel easily is oxidized to the more weak but γ-Fe of stable performance of magnetic under high temperature oxidation stability atmosphere
2O
3Kernel; And γ-Fe
2O
3Reducible in the reducing atmosphere of kernel about 300 ℃ is Fe
3O
4Kernel; Fe
3O
4Or γ-Fe
2O
3Kernel reduces in reducing atmosphere more than 460 ℃ and obtains the Fe kernel; Under the sufficient inadequately situation of reduction, the kernel in the carrier may occur with the form of two or three kernel coexistence; Has Fe
3O
4The carrier of kernel in higher temperature oxidizing atmosphere use, part Fe
3O
4Can be oxidized to γ-Fe
2O
3, make in the carrier kernel of two kinds of forms of coexistence.
Ball-aluminium oxide carrier material provided by the invention has following characteristics:
1, has good magnetic performance, SiO
2Cladded type magnetic component uniform particles is dispersed in the aluminium oxide, wherein, the granularity of cladding internal magnetization kernel is less than its critical spontaneous manetization size, thereby the characteristics of carrier superparamagnetism have been given, under the externally-applied magnetic field effect, can in reactor, position control easily, separate and reclaim, during no externally-applied magnetic field, magnetic does not take place particle assembles good dispersion.Such characteristics make it by the magnetic field effect, reach the purpose that recycles repeatedly in catalytic reaction, have prevented the loss of catalyst or carrier material, have reduced cost.
2, have special microstructure, inner by the oxide magnetic kernel of iron or iron and the SiO of magnetic kernel surface strong bonded
2Clad forms magnetic-particle, and the loose relatively alumina component of structure forms the gradient of structure and the echelon of component in the carrier on microcosmic.Because steric hindrance, at the surface coated SiO of the oxide of iron or iron
2Layer has improved the dispersed and stable of core granule, strengthens its anticorrosive, antioxygenic property; As carrier material, magnetic kernel wherein not with the subsequent applications process in the catalytic active component of institute's load directly contact, can avoid of the toxic action of iron component to some catalyst, special in the reaction of some acid medium because SiO
2The protective effect of compacted zone, magnetic kernel component can strippings, and carrier has good tolerance.
Description of drawings
Fig. 1 is the cross-sectional view of magnetic-particle in the ball-aluminium oxide carrier material.
Fig. 2 is the XRD spectra of magnetic-particle in the ball-aluminium oxide carrier material.
Fig. 3 is the cross-sectional view of ball-aluminium oxide carrier material.
Fig. 4 is the TEM photo of magnetic-particle in the ball-aluminium oxide carrier material
Fig. 5 is the hysteresis curve of magnetic-particle in the ball-aluminium oxide carrier of embodiment 1 preparation.
Fig. 6 is the hysteresis curve of the ball-aluminium oxide carrier of embodiment 4,5 and 6 preparations.
Fig. 7,8 is respectively the XRD spectra of the ball-aluminium oxide carrier of embodiment 4 and 9 preparations.
Fig. 9 is the SEM photo of the ball-aluminium oxide carrier of embodiment 1 preparation.
Figure 10 is the ball-aluminium oxide carrier S EM photo of embodiment 4 preparations.
The specific embodiment
Following example will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these examples.
In example, the pattern of sample adopts JSM-5800 type ESEM and H-8100 type transmission electron microscope to observe respectively; The B-H loop of sample adopts Model-155 type vibrating specimen magnetometer to measure measurement category 0-8 (kOe) in normal temperature.X-ray diffraction (XRD) carries out Cu target K alpha ray, wavelength X=1.54, sweep limits 10-90 ℃ on D/Max-2400Rigaku (Japan is of science) diffractometer.
Embodiment 1
With 189g Na
2SiO
39H
2O (Wenzhou, Zhejiang east rises chemical reagent factory) is dissolved in the 800mL distilled water, slowly drips 3mol/L HCl solution under stirring condition, and the pH value of solution is transferred to 13, and is standby after the filtration.
In 2 liters of stirring reactors that 1000mL distilled water is housed, add 23.4g FeCl
36H
2O (Tong Hui chemical plant, Chaoyang, Beijing) and 8.6g FeCl
24H
2O (Beijing dicyclo chemical reagent factory) under nitrogen protection, is warming up to 85～90 ℃, adds the NH of 30mL25% in the high-speed stirred process
3H
2O solution behind the high-speed stirred 3min, adopts magnetic separator to isolate Fe
3O
4Nano-particle product.To clean the back sedimentation products ultrasonic be dispersed in above-mentioned through pretreated Na
2SiO
3In the solution, move into then in 2 liters of stirring reactors, be warming up to 85 ℃, under nitrogen protection and stirring condition, in solution, slowly drip the HCl solution of the about 2mol/L of concentration, the pH value of solution is transferred to 6 by 13.Reaction is isolated product after finishing, and fully washing obtains SiO
2Coat Fe
3O
4The magnetic particle of particle is labeled as SF1.
Above-mentioned coating Fe
3O
4About 50 grams of the magnetic particle product gross weight of particle wherein contain Fe
3O
4About 10 grams, Fe
3O
4The SiO on surface
2About 40 grams are amorphous Si O
2(SiO
2Covering amount is about 400%).Through scanning electron microscopic observation, product is thyrsiform (lumps) aggregate, the about 2 μ m of particle mean size, and through transmission electron microscope observing, nanometer Fe
3O
4Magnetic-particle is dispersed in the product, the Fe of core
3O
4Magnetic-particle is bordering on ball-type, and particle mean size is 7 nanometers, and is peripheral by fine and close SiO
2(see Fig. 4, black point-like thing is a nanometer Fe in layer coating
3O
4Magnetic-particle, light color matter are SiO
2Cladding), find that by XRD spectra (Fig. 2) bigger ripple bag is arranged in ° scope of 2 θ=20～30, this is amorphous Si O
2Characteristic peak.Show by its hysteresis curve (Fig. 5), the magnetization curve of product and demagnetizing curve overlap, when no external magnetic field (H=OkOe), intensity of magnetization M=0, along with the increase of external magnetic field H, total magnetization intensity M increases rapidly, until reaching capacity, illustrate that magnetic particle has superparamagnetism, the about 11emu/g (Am of saturation magnetization
2/ Kg).
Take by weighing AlCl
36H
2O (the two ship chemical reagent factories in Tianjin) 92.5 grams, be dissolved in the 600ml deionized water, be heated to 80-100 ℃, slowly add 42.6 gram high-purity aluminum foils (Xing Jin chemical plant, Beijing), under this temperature, kept 60-72 hour, make aluminium foil fully be dissolved in the solution after, the liquor capacity heating is concentrated into 300ml, obtain clarifying translucent colloidal sol, standby.This colloidal sol composition is formed (or claiming aluminium chloride) by aluminium hydroxide and aluminium chloride, and wherein aluminium/chlorine weight ratio is about 1.3: 1.0, and the aluminium in the colloidal sol is converted to aluminium oxide and is about 100 grams.This colloidal sol is labeled as A1.
At room temperature, measuring 100ml A1 aluminum hydroxide sol, is that the hexamethylenetetramine (Beijing benefit sharp fine chemicals company) of 10 ℃ of 120g/L mixes with 95ml concentration, stirs, and adds 1.75 gram SF1 again, stirs the uniform aqueous phase solution of formation.The 1400ml that packs in 3 liters of column type stirring reactors contains the sulfonated kerosene of 0.05 volume %Span80 (Beijing chemical reagents corporation), above-mentioned aqueous phase solution is added in the sulfonated kerosene,, under the rotating speed of 800rpm, be uniformly dispersed in room temperature, form water-in-oil emulsion, system is warming up to 85～90 ℃ subsequently, keep 15min, this moment, organic amine decomposed, and discharged ammonia, aqueous phase solution pH value raises gradually, makes the aluminum hydroxide sol gelling be solidified into the spherical Al (OH) of magnetic
3
With the spherical Al (OH) of magnetic
3After the product cleaning oil removing, ageing 6 hours under room temperature after 60 ℃ of oven dry, can obtain visiing diaspore structure (β-Al in the ammoniacal liquor of 7 heavy %
2O
33H
2O) magnetic Al (OH)
3Particle, this product sintering 2 hours in 400 ℃ of air can obtain about 40g and contain γ-Fe
2O
3Spherical η-the Al of the magnetic of magnetic kernel
2O
3Carrier.
Pattern photo Fig. 9 of prepared ball-aluminium oxide carrier material, as can be seen from Figure 9, the average grain diameter of this material is about 140 μ m.
Each constituent content ratio (weight ratio) is in the carrier: γ-Fe
2O
3: SiO
2: Al
2O
3=1: 4: 95 (in addition, also containing part water in the carrier).This carrier has the superparamagnetism feature.
Embodiment 2
With 28.4g Na
2SiO
39H
2O (Wenzhou, Zhejiang east rises chemical reagent factory) is dissolved in the 600mL distilled water, slowly drips 3mol/L HCl solution under stirring condition, and the pH value of solution is transferred to 13, and is standby after the filtration.
In 2 liters of stirring reactors that 1000mL distilled water is housed, add 46.7g FeCl
36H
2O (Tong Hui chemical plant, Chaoyang, Beijing) and 17.2g FeCl
24H
2O (Beijing dicyclo chemical reagent factory) under nitrogen protection, is warming up to 85～90 ℃, adds the NaOH solution of 160mL 6MolL in the high-speed stirred process, behind the high-speed stirred 3min, adopts magnetic separator to isolate Fe
3O
4Nano-particle product.To clean the back sedimentation products ultrasonic be dispersed in above-mentioned through pretreated Na
2SiO
3In the solution, move into then in 2 liters of stirring reactors, be warming up to 85 ℃, under nitrogen protection and stirring condition, in solution, slowly drip the HCl solution of the about 1.5mol/L of concentration, in about 3 hours, the pH value of solution is transferred to 6 by 13.Obtain SiO
2Coat Fe
3O
4The magnetic particle of particle is labeled as SF2.
Above-mentioned SiO
2Coat Fe
3O
4About 26 grams of the magnetic particle gross weight of particle wherein contain Fe
3O
4About 20 grams, Fe
3O
4The SiO on surface
2About 6 grams are amorphous Si O
2(SiO
2Covering amount is about 30%).The hysteresis curve that detects through vibrating specimen magnetometer (VSM) shows that magnetic particle has superparamagnetism.
Take by weighing AlCl
36H
2O (the two ship chemical reagent factories in Tianjin) 75.1 grams, be dissolved in the 600ml deionized water, be heated to 80～100 ℃, slowly add 44.6 gram 300 order atomized aluminiums (mechanics institute of Chinese Academy of Sciences product) in batches, under this temperature conditions, kept 48 hours, after making aluminium powder fully be dissolved in the solution, the liquor capacity heating is concentrated into 300ml, obtain clarifying translucent colloidal sol, wherein aluminium/chlorine weight ratio is about 1.6: 1.0, and the aluminium in the colloidal sol is converted to aluminium oxide and is about 100 grams.This colloidal sol is labeled as A2.
Under the room temperature, measuring 100ml A2 aluminum hydroxide sol, is that 400g/L, 10 ℃ hexamethylenetetramine (Beijing benefit sharp fine chemicals company) mix with 80mL concentration, stirs, and adds 21.3 gram SF2 again, stirs the uniform aqueous phase solution of formation.The 1300ml that packs in 3 liters of column type stirring reactors contains 0.02 volume %Span60 (lucidification factory, China Drug Co.'s Beijing purchasing and supply station is sold) sulfonated kerosene, above-mentioned aqueous phase solution is added in the sulfonated kerosene, under the rotating speed of 400rpm, be uniformly dispersed in room temperature, form water-in-oil emulsion, system is warming up to 85～90 ℃ subsequently, behind the maintenance 15min, cooling, isolate product, obtain the spherical Al (OH) of magnetic
3Be labeled as AL1.
With the spherical Al (OH) of above-mentioned AL1 magnetic
3Product is removed surperficial oil slick with the solution washing that contains a small amount of Tween80, (measures under the room temperature) in the weak aqua ammonia of pH=10 in 80 ℃ of ageings 4 hours (removing wherein partial impurities), after 60 ℃ of oven dry, can obtain the magnetic Al (OH) of impalpable structure
3Microballoon, this product sintering 2 hours under 350 ℃ of hydrogen atmospheres can obtain about 65g and contain Fe
3O
4The Al of the spherical impalpable structure of the magnetic of magnetic kernel
2O
3Carrier.The average grain diameter of this carrier material is about 1mm, and wherein each constituent content ratio (weight ratio) is: Fe
3O
4: SiO
2: Al
2O
3=30: 9: 61 (in addition, also containing part water in the carrier).This carrier has the superparamagnetism feature.
Embodiment 3
With the spherical Al (OH) of above-mentioned AL1 magnetic
3Product; pack into and contain in the 1L autoclave of 0.7L sulfonated kerosene medium; the following 140 ℃ of hydrothermal treatment consists of nitrogen protection 3 hours; after the product cleaning oil removing; in the weak aqua ammonia of pH=11, (measure under the room temperature) subsequently in 80 ℃ of ageings 6 hours (removing wherein partial impurities); after 60 ℃ of oven dry, can obtain boehmite structure (the spherical Al (OH) of the magnetic of α-AlOOH)
3Product, this product sintering 2 hours under 580 ℃ of air atmospheres can obtain about 60g and contain γ-Fe
2O
3Spherical gamma-the Al of magnetic kernel
2O
3Carrier.Each constituent content ratio (weight ratio) is in this carrier material: γ-Fe
2O
3: SiO
2: Al
2O
3=30: 9: 61 (in addition, also containing part water in the carrier).This carrier has the superparamagnetism feature.
Embodiment 4
With 189g Na
2SiO
39H
2O (Wenzhou, Zhejiang east rises chemical reagent factory) is dissolved in the 1000mL distilled water, slowly drips 3mol/L HCl solution under stirring condition, and the pH value of solution is transferred to 13, and is standby after the filtration.
In 3 liters of stirring reactors that 1200mL distilled water is housed, add 42.2g FeCl
36H
2O (Tong Hui chemical plant, Chaoyang, Beijing) and 20.6g FeCl
24H
2O (Beijing dicyclo chemical reagent factory) is warming up to 85～90 ℃, adds the NH of 60mL25% in the high-speed stirred process
3H
2O solution behind the high-speed stirred 3min, adopts magnetic separator to isolate Fe
3O
4Nano-particle product.To clean the back sedimentation products ultrasonic be dispersed in above-mentioned through pretreated Na
2SiO
3In the solution, move into then in 3 liters of stirring reactors, be warming up to 85 ℃, under nitrogen protection and stirring condition, in solution, slowly drip the HCl solution of the about 2mol/L of concentration, in about 3 hours, the pH value of solution is transferred to 6 by 13.Obtain SiO
2Coat Fe
3O
4The magnetic particle of particle.
About 60 grams of above-mentioned product magnetic particle gross weight wherein contain Fe
3O
4About 20 grams, Fe
3O
4The SiO on surface
2About 40 grams are amorphous Si O
2(SiO
2Covering amount is about 200%).The hysteresis curve that detects through vibrating specimen magnetometer (VSM) shows that magnetic particle has superparamagnetism.This component is labeled as SF3.
Take by weighing AlCl
36H
2O (the two ship chemical reagent factories in Tianjin) 80 grams, be dissolved in the 600ml deionized water, add 44 gram high-purity aluminum foils (Xing Jin chemical plant, Beijing), under 80～100 ℃ of conditions, kept 60-72 hour, after making aluminium foil fully be dissolved in the solution, the liquor capacity heating is concentrated into 300ml, obtains clarifying translucent colloidal sol, wherein aluminium/chlorine weight ratio is about 1.5: 1.0, and the aluminium in the colloidal sol is converted to aluminium oxide and is about 100 grams.This colloidal sol is labeled as A3.
Under 10 ℃ of temperature, measure 100ml A3 aluminum hydroxide sol, mix with the organic amine solution (containing hexamethylenetetramine (Beijing sharp fine chemicals of benefit company) 300g/L and urea (Beijing Chemical Plant) 150g/L) of 90ml, stir, add 7.3 gram SF3 cladded type magnetic component particles again, stir and form uniform aqueous phase solution.The 1600ml that packs in 3 liters of column type stirring reactors contains the sulfonated kerosene of 0.05 volume %Span80 (Beijing chemical reagents corporation), above-mentioned aqueous phase solution is added in the sulfonated kerosene, in room temperature under the rotating speed of 700rpm, be uniformly dispersed, form water-in-oil emulsion, system is warming up to 85-90 ℃ subsequently, after keeping 15min, product is isolated in cooling, obtains the spherical Al (OH) of magnetic
3Be labeled as AL2.
With the spherical Al (OH) of the magnetic of above-mentioned AL2
3Product; pack into and contain in the 1L autoclave of 0.7L sulfonated kerosene medium; the following 180 ℃ of hydrothermal treatment consists of nitrogen protection 2 hours; after the product cleaning oil removing; in the weak aqua ammonia of pH=10, (measure under the room temperature) subsequently in 80 ℃ of ageings 5 hours (removing wherein partial impurities); after 60 ℃ of oven dry, can obtain boehmite structure (the spherical Al (OH) of the magnetic of α-AlOOH)
3Product.Be labeled as AL3.The XRD spectra of this product is seen Fig. 7, and product is by α-AlOOH, Fe
3O
4And γ-Fe
2O
3Deng composition, in hydrothermal treatment consists, ageing and dry run, the Fe in the product
3O
4Partial oxidation is γ-Fe
2O
3
Above-mentioned boehmite product A L3 can obtain about 45g and contain γ-Fe through 580 ℃ of air atmosphere sintering 2 hours
2O
3Spherical gamma-the Al of magnetic kernel
2O
3Carrier;
The average grain diameter of carrier material is about 200 μ m (Figure 10), and wherein each constituent content ratio (weight ratio) is: γ-Fe
2O
3: SiO
2: Al
2O
3=6: 12: 82, to measure through VSM, carrier has the superparamagnetism feature, and specific saturation magnetization is 2.97Am
2/ Kg.Among Fig. 6-●-curve is the hysteresis curve of this carrier.Through the BET determination of adsorption method, the about 200+10m of the specific surface of carrier
2/ g, pore volume is about 0.75 ± 0.1mL/g.
Embodiment 5
Other conditions are with embodiment 4, and difference is that the amount of the SF3 cladded type magnetic component particle that will add in the system is adjusted into 3.3 grams, can obtain about 40g and contain γ-Fe
2O
3Spherical gamma-the Al of magnetic kernel
2O
3Carrier, wherein each constituent content ratio (weight ratio) is: γ-Fe
2O
3: SiO
2: Al
2O
3=3: 6: 91, to measure through VSM, carrier has the superparamagnetism feature, and specific saturation magnetization is 1.78Am
2/ Kg, among Fig. 6-■-curve is the hysteresis curve of this carrier.
Embodiment 6
Other conditions are with embodiment 4, and difference is that the amount of the SF3 cladded type magnetic component particle that will add in the system is adjusted into 12.3 grams, can obtain about 50g and contain γ-Fe
2O
3Spherical gamma-the Al of magnetic kernel
2O
3Carrier, wherein each constituent content ratio (weight ratio) is: γ-Fe
2O
3: SiO
2: Al
2O
3=9: 18: 73, to measure through VSM, carrier has the superparamagnetism feature, and specific saturation magnetization is 5.03Am
2/ Kg.Among Fig. 6-▲-curve is the hysteresis curve of this carrier.
Embodiment 7
Other conditions are with embodiment 4, and difference is that the boehmite product A L3 that will obtain through 920 ℃ of air atmosphere sintering 2 hours, can obtain about 42g and contain γ-Fe
2O
3Spherical δ-the Al of the magnetic of magnetic kernel
2O
3Carrier (wherein contains a spot of θ-Al
2O
3), wherein each constituent content ratio (weight ratio) is: γ-Fe
2O
3: SiO
2: Al
2O
3=6: 12: 82, to measure through VSM, carrier has the superparamagnetism feature.
At room temperature, measure 100ml A3 aluminum hydroxide sol, mix, stir with 120mL10 ℃ organic amine solution (containing hexamethylenetetramine (Beijing sharp fine chemicals of benefit company) 400g/L), add 33 gram SF3 cladded type magnetic component particles again, stir and form uniform aqueous phase solution.The 1500ml that packs in 3 liters of column type stirring reactors contains the sulfonated kerosene of 0.07vol.%Span80 (Beijing chemical reagents corporation), above-mentioned aqueous phase solution is added in the sulfonated kerosene, in room temperature under the rotating speed of 800rpm, be uniformly dispersed, form water-in-oil emulsion, system is warming up to 85-90 ℃ subsequently, keeps 15min, obtain the spherical Al (OH) of magnetic
3
With the spherical Al (OH) of magnetic
3After the product cleaning oil removing, ageing 6 hours under room temperature after 60 ℃ of oven dry, can obtain visiing diaspore structure (β-Al in the ammoniacal liquor of 7wt.%
2O
33H
2O) magnetic Al (OH)
3Particle, this product sintering 2 hours in 920 ℃ of air can obtain about 68g and contain γ-Fe
2O
3Spherical θ-the Al of magnetic kernel
2O
3Carrier.Each constituent content ratio (weight ratio) is in the carrier: γ-Fe
2O
3: SiO
2: Al
2O
3=16.7: 33.3: 50 (in addition, also containing part water in the carrier).This carrier has the superparamagnetism feature.
Embodiment 9
Will be by the spherical Al (OH) that obtains among the embodiment 4
3Product A L2, clean to remove surperficial oil slick after, ageing after 5 hours in the ammoniacal liquor of room temperature 7%, after fully cleaning with deionized water, oven dry.The main component of product is for visiing diaspore, SiO at this moment
2And Fe
3O
4This product in 1180 ℃ of temperature sintering 2 hours, obtains the spherical α-Al of about 41g containing metal Fe magnetic kernel under nitrogen protection
2O
3Carrier.α-Al in the carrier
2O
3Shared weight ratio is about 82%.XRD spectra is seen Fig. 8, and as can be seen from Figure 8, carrier is mainly by α-Al
2O
3, SiO
2, alumina silicate, metallic iron form.At high temperature, organic amine residual in the particle is decomposed to form reducing atmosphere, with magnetic Nano Fe wherein
3O
4Kernel is reduced into metal Fe kernel, and Fe
3O
4The part Si O on top layer
2With Al
2O
3Have an effect and form a spot of alumina silicate.The VSM test result shows that carrier has tangible superparamagnetism feature, the about 7.0Am of specific saturation magnetization
2/ Kg.
Claims (24)
1, a kind of ball-aluminium oxide carrier material is characterized in that this carrier material contains the aluminium oxide of 50～99 heavy % and the magnetic-particle of 1～50 heavy %, and wherein said magnetic-particle is 0.01～6: 1 SiO by weight ratio
2Clad and be selected from Fe
3O
4, Fe and γ-Fe
2O
3In one or more kernels form.
2,, it is characterized in that said aluminium oxide is selected from one or more the mixture in following: amorphous alumina, ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, Alpha-alumina according to the said carrier material of claim 1.
3,, it is characterized in that said magnetic-particle is that 0.3～4.0: 1 clad and kernel are formed by weight ratio according to the said carrier material of claim 1.
4,, it is characterized in that said kernel is that one or more particle diameters are the single domain superparamagnetism particulate of 3～30 nanometers in the magnetic-particle according to claim 1 or 3 said carrier materials.
5, according to the said alumina supporting material of claim 1, the particle diameter that it is characterized in that this carrier material is at 10 μ m to 6mm.
6, the preparation method of the described ball-aluminium oxide carrier material of claim 1 is characterized in that this method contains following step:
(1) at 50～100 ℃, to containing Fe
2+With Fe
3+Add alkali in the aqueous solution of salt, with the nanometer Fe of deposition
3O
4Particle changes in the sodium silicate solution, under the protection of inert gas, adds acid solution is transferred to neutrality or below the neutrality, obtains SiO
2Coat Fe
3O
4The magnetic particle of particle, wherein, Fe in the said molysite
2+With Fe
3+Mol ratio be 1: (0.5～2.5), the OH of said alkali
-With ∑ (Fe
2++ Fe
3+) mol ratio be 1: (0.1～1.0), said sodium metasilicate and Fe
3O
4Mol ratio be 1: (0.043～5.2);
(2) under-10～35 ℃, the magnetic particle three of aluminum hydroxide sol, organic amine solution and step (1) is mixed, after forming finely dispersed water, be scattered in the oil phase, behind the formation water-in-oil type drop, heating systems solidifies the aluminum hydroxide sol drop gelling of aqueous phase again, again through hydrothermal treatment consists, ageing, drying and the sintering of routine, wherein, the volume ratio of organic amine solution and aluminum hydroxide sol is 1: (0.3～2.5), the volume ratio of water and oil phase are 1: (3～20);
(3) in reducing atmosphere or oxidizing atmosphere, heat-treat or adopt oxidant or reducing agent that carrier is handled, the kernel type in the carrier material magnetic-particle is changed carrier.
7, in accordance with the method for claim 6, it is characterized in that the said alkali of step (1) is selected from KOH, NaOH, NH
4OH, Na
2CO
3Or NaHCO
3A kind of or its mixture wherein.
8, in accordance with the method for claim 6, it is characterized in that in the said molysite of step (1) Fe
2+With Fe
3+Mol ratio be 1: (1.5～2).
9, in accordance with the method for claim 6, it is characterized in that said sodium metasilicate of step (1) and Fe
3O
4Mol ratio be 1: (0.065～0.864).
10, in accordance with the method for claim 6, it is characterized in that the said acid of step (1) is selected from wherein a kind of of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid or acetate or their mixture.
11, in accordance with the method for claim 6, it is characterized in that in the step (2) that aluminium/chlorine weight ratio is 0.3～2.0 in the said aluminum hydroxide sol.
12, in accordance with the method for claim 11, it is characterized in that in the step (2) that aluminium/chlorine weight ratio is 1.3～1.6 in the said aluminum hydroxide sol.
13, in accordance with the method for claim 6, the mass concentration that it is characterized in that said organic amine solution in the step (2) is 12%～40%.
14, in accordance with the method for claim 6, it is characterized in that said organic amine is that the pH value is approaching neutral under the normal temperature in the step (2), but, can be used alone or in combination through adding the material that thermal decomposition can discharge alkaline matter.
15, in accordance with the method for claim 14, it is characterized in that said organic amine is urea and/or hexamethylenetetramine.
16, in accordance with the method for claim 6, it is characterized in that the volume ratio of said organic amine solution and aluminum hydroxide sol is 1 in the step (2): (0.8～1.3).
17, in accordance with the method for claim 6, it is characterized in that said oil phase in the step (2) is selected from one or more the mixture in gasoline, kerosene, diesel oil, transformer oil, benzene, biphenyl, the halogenated hydrocarbons.
18, in accordance with the method for claim 6, it is characterized in that the volume ratio of said water and oil phase is 1 in the step (2): (4～10).
19, in accordance with the method for claim 6, it is characterized in that also containing in the said oil phase in the step (2) emulsifying agent of 0.02～2.0 volume %.
20, in accordance with the method for claim 19, it is characterized in that said emulsifying agent is one or more low-molecular-weight surfactants.
21, in accordance with the method for claim 20, it is characterized in that said HLB VALUE OF SURFACTANTS＜9.
22,, it is characterized in that said surfactant is selected from Span80, Span85, Span65, Span60, Span40, Span20, Macrogol 200 dioleic acid ester, ethylene glycol monostearate, glyceryl monostearate, polyoxyethylene fatty acid ester, the two stearates of PEG400, lanolin according to claim 20 or 21 described methods.
23, in accordance with the method for claim 6, it is characterized in that the said hydrothermal treatment consists process of step (2) is in autoclave, the product that the gelling of aluminum hydroxide sol drop is solidified in oil or aqueous medium 105～260 ℃ handled 1～10 hour.
24, in accordance with the method for claim 23, it is characterized in that the said hydrothermal treatment consists process of step (2) is in autoclave, the product that the gelling of aluminum hydroxide sol drop is solidified in oily medium 120～200 ℃ handled 2～5 hours.
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| KR100647309B1 (en) * | 2005-01-21 | 2006-11-23 | 삼성에스디아이 주식회사 | Support for fuel gas reforming catalyst with excellent heat and mass transfer characteristics and manufacturing method thereof |
| CN1321895C (en) * | 2005-04-26 | 2007-06-20 | 北京化工大学 | Magnetic continuous separating refiner and its use during process of aluminium gum preparation |
| CN101172255B (en) * | 2006-10-31 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing magnetic microspheric alumina support |
| CN101279295B (en) * | 2007-04-03 | 2010-12-08 | 中国科学院过程工程研究所 | Preparation method of spherical magnetic nano alumina supporting material |
| CN101318148B (en) * | 2007-06-06 | 2010-05-26 | 中国石油化工股份有限公司 | Method for preparation of spherical magnetic alumina support |
| CN101543786B (en) * | 2008-03-27 | 2012-05-30 | 中国石油化工股份有限公司 | Magnetic solid acid catalyst and preparation method and application thereof |
| CN101388267B (en) * | 2008-07-09 | 2011-04-13 | 长春市博坤生物科技有限公司 | Silicon dioxide magnetic composite particle and preparation |
| CN103059987B (en) * | 2011-10-21 | 2015-06-17 | 中国石油化工股份有限公司 | Hydrotreatment method for coal tar |
| CN105478100A (en) * | 2015-11-13 | 2016-04-13 | 无锡清杨机械制造有限公司 | Method for preparing silicon-containing gamma-Al2O3 microsphere |
| CN115608410B (en) * | 2021-07-13 | 2023-10-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing n-butyl acetate and preparation method and application thereof |
| CN114100506A (en) * | 2021-11-04 | 2022-03-01 | 北京新风航天装备有限公司 | Continuous flow synthesis method of coated nano magnetic particles |
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