CN100372610C - Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use - Google Patents
Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use Download PDFInfo
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- CN100372610C CN100372610C CNB2004100480630A CN200410048063A CN100372610C CN 100372610 C CN100372610 C CN 100372610C CN B2004100480630 A CNB2004100480630 A CN B2004100480630A CN 200410048063 A CN200410048063 A CN 200410048063A CN 100372610 C CN100372610 C CN 100372610C
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Abstract
The present invention provides a magnetic microspherical high dispersion supported metal catalyst and a preparation method and application thereof. The preparation technology of the catalyst comprises: spinel soft magnetic ferrite materials whose surfaces are coated are dispersed in aluminum sol, microspherical alumina supporters containing magnetic nuclei are obtained by an oil column forming method, and active metal constituents are supported on the supporters to obtain the magnetic catalyst. The granularity of the supporters is from 2 to 200 mum, the specific surface area is from 10 to 300m, and the pore volume is from 0.7 to 1.5 ml/g. The active metal supported on the catalyst is one or a plurality of kinds in Cu, Ni, Pt, Mn, Pd or Co, the content of the active metal is from 0.01 to 10%, and the dispersion degree of the active metal is from 30 to 60%. The bulk density of the catalyst is from 0.3 to 0.7 g/ml, and the specific saturation magnetization of the supporters and the catalyst is more than 3.0 emu/g. The catalyst is mainly used for the catalytic hydrogenation reaction processes of fluidized bed and magnetically stabilized bed technology.
Description
Technical field
The present invention relates to the purposes of a kind of magnetic microsphere high-dispersion load metallic catalyst and preparation method thereof and this catalyst.
Background technology
Catalytic reaction can be divided into fixed-bed process and fluidized-bed process by the technology type of implementing.Used catalyst generally is to be that carrier is made after by infusion process supported active metal with powdered active carbon, oxide in the fluidized-bed process.Catalyst is to be dispersed in the fluidized-bed reactor after gas reactant is with the bubble form disturbance in fluidized-bed process, and wearing and tearing that catalyst causes because of collision and relative motion and the loss that does not have outer field containment to cause with Flow of Goods and Materials are inevitable.In order to address the above problem, people have expected giving catalyst magnetic, in order, arrange along the magnetic line of force equably, catalyst granules is relative fixed when reaction, thereby reduces or avoided collision, wearing and tearing and the loss of catalyst in fluid bed for catalyst under the constraint of magnetic field force.
Chemical industry progress .2002,21 (8), P536-539; Chemical Reaction Engineering and technology .2002,18 (1), P26-30; Petroleum refining and chemical industry .2003,34 (11), P44-48 has reported the result of study of nickel base amorphous alloy Magnaglo catalyst a plurality of reaction systems of catalytic hydrogenation in magnetic stablizing bed technology, but the magnetic of used catalyst is lower, specific saturation magnetization is generally less than 1.0emu/g, disperses to have caused difficulty effectively for catalyst in magnetic field.If make catalyst be dispersed in magnetic stablizing bed in, the essential intensity that increases the external magnetic field, thus improved running cost.
Process engineering journal .2002,4 (2), P319-324 has reported with Fe
3O
4Magnetic nanoparticle is a magnetic nuclear, adopts the forming oil column legal system to be equipped with the result of study of the spherical alumina support of magnetic.Its weak point is Fe
3O
4Be hard magnetic material, have bigger coercivity after core prepares magnetic alumina carrier and then makes catalyst, catalyst has the magnetic by self to produce the autohemagglutination phenomenon, evenly disperses to have caused difficulty for it.
The carrying method of at present the most frequently used catalyst activity component is an infusion process, is about to carrier and is soaked in the soluble-salt solution that contains reactive metal, makes active component be adsorbed in carrier surface.Owing to be subjected to the surface tension of immersion solvent and the influence of solvation, often active component assembled at carrier surface and easily form large particle crystal at dipping process; In addition, because of active component does not form the extensive chemical effect with the surface in dipping process, for active component is combined more firmly with carrier, often need after the catalyst drying, carry out roasting to it, the metallic crystal cohesion medium and small in this process also progressively is grown to oarse-grained crystallization.Therefore the method for infusion process metal supported catalyst exists the metal specific area less, the defective that metal dispersity is relatively low.
This laboratory application number for 02131248.6 and two patents of invention of 02131246.x in a kind of method that makes the active metal component high degree of dispersion in carrier surface is provided, the i.e. synthetic layered bi-metal complex hydroxide (LDHs) that contains reactive metal of original position in hole, carrier top layer at first, roasting makes lamellar precursor be transformed into corresponding composite metal oxide under higher temperature then, handles the catalyst that obtains the metal high degree of dispersion through hydrogen reducing again.But such catalyst does not have magnetic.
Summary of the invention
The purpose of this invention is to provide a kind of magnetic microsphere high-dispersion load metallic catalyst; Another object of the present invention provides a kind of method for preparing magnetic microsphere high dispersion metal catalyst; A further object of the invention provides the purposes of such catalyst.
Catalyst provided by the invention: carrier is the ball-aluminium oxide that contains spinel-type soft magnetic ferrite magnetic nuclear, and the crystal formation of aluminium oxide is any one in γ, η, δ, θ, the α type, and the granularity of carrier is 2-200 μ m, specific surface 10-300m
2/ g, pore volume 0.7-1.5ml/g; The active metal component of load is one or more among Cu, Ni, Pt, Mn, Pd or the Co on the catalyst, and the content of active metal component is at 0.01-10%; The decentralization of reactive metal is 30-60%, and more excellent decentralization is 45-60%; The bulk density of catalyst is 0.3-0.7g/ml; The specific saturation magnetization of carrier and catalyst is all greater than 3.0emu/g; As the spinel-type soft magnetic ferrite of carrier magnetic nuclear, its chemical general formula can be expressed as MeFe
2O
4, Me
2+Represent radius and Fe
2+Similar bivalent metal ion.Me
2+Can be Mn
2+, Zn
2+, Cu
2+, Ni
2+, Mg
2+Or Co
2+In any one or multiple.
This Preparation of catalysts process route is:
Will be in aluminium colloidal sol through surface coated spinel-type soft magnetic ferrite dispersion of materials, the employing oil-drop method prepares microspheroidal, contains the alumina support of magnetic nuclear, again the reactive metal component is carried to hold on this carrier to obtain magnetic catalyst.
In order to obtain the magnetic catalyst of metal high degree of dispersion, can utilize the aluminium source of aluminium oxide bore area, the synthetic hydrotalcite (LDHs) that contains the reactive metal element of original position in shell aluminium oxide endoporus is then through roasting, the magnetic microsphere load type metal catalyst that obtains the reactive metal high degree of dispersion that reduces.
Concrete preparation method is as follows for catalyst:
The preparation of A ferrite magnetic nuclear
According to Fe
2+Fe
3+=2Me
2+Mol ratio preparation contain bivalent metal ion Me
2+And Fe
2+, Fe
3+The mixing salt solution of ion, wherein the molar concentration of each metal ion species is 0.1-0.6M; With NaOH and solubility inorganic sodium preparation mixed-alkali solution, wherein, NaOH concentration is 1.0-2.5M, and sodium salt concentration is 0-1.7M; At N
2Under the condition of protection, mixed-alkali solution slowly is added drop-wise in the mixing salt solution, when the pH value in the system reaches 7-12, stops to drip, at N
2Protection in 20-65 ℃ of water-bath crystallization 5-25 hour down, after filtration, washing, drying obtain Me
2+-Fe
2+-Fe
3+-LDHs; Be placed in the high temperature furnace, be warming up to 850-1150 ℃, roasting 2-7 hour, obtain ferrite MeFe with the speed of 2-15 ℃/min
2O
4
Anion in the mixing salt solution can be Cl
-, NO
3 -Or SO
4 2-In any one or a few; Me
2+Be ionic radius and Fe
2+Close bivalent metal ion, Me
2+Can be Mn
2+, Zn
2+, Cu
2+, Ni
2+, Mg
2+Or Co
2+In any one or a few; The preferred sodium carbonate of solubility inorganic sodium, sodium sulphate or sodium chloride.
Ferrite magnetic nuclear also can be by traditional method preparation, and the oxide, hydroxide or other precipitation mixture that are about to contain Me, Fe metal obtain MeFe 850～1150 ℃ of roastings 2～7 hours
2O
4Me
2+Be Mn
2+, Zn
2+, Cu
2+, N0
2+, Mg
2+Or Co
2+In any one or multiple.
But the magnetic ferrites with the preparation of lamellar precursor method have the specific saturation magnetization height, the characteristics of be uniformly dispersed (all identical in any microcell stoichiometric proportion), are more suitably used as the magnetic nuclear of carrier of the present invention.
The coating of B ferrite magnetic nuclear
Steps A is obtained ferrite MeFe
2O
4Being crushed to add behind the particle of 0.1-10 μ m and filling in advance in the band stirred reactor of deionized water, keep in the reactor temperature of charge at 15-100 ℃, is the Na of 0.1-2M with the concentration of scheduled volume while stirring simultaneously
2SiO
3With concentration be that the inorganic acid of 0.1-3M adds in the reactor, continue to stir reaction down 2-10 hour.Spend solids in the deionised water reactor to neutral, and under 100-200 ℃ of temperature dry 2-12 hour, obtain the surface and coated SiO
2Ferrite magnetic nuclear.
Na
2SiO
3With the addition of inorganic acid according to surface coated SiO
2Amount and determine the SiO of coating
2With MeFe
2O
4Weight ratio in the 0.3-5 scope, change.Used inorganic acid can be sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
The preparation of C magnetic microsphere aluminum oxide carrier
The aluminium powder of 10-150 μ m is dissolved in preparation aluminium colloidal sol in the soluble aluminum salting liquid of 0.1-2M, adding the magnetic that coated by the 1-20% of the spherical alumina support weight of the magnetic that finally obtains examines in aluminium colloidal sol, be that the ratio of 2-10 adds the organic amine solution that concentration is 0.1-0.5M in said mixture in the mol ratio of Al and organic amine again, mixing the back, to spray into temperature by disperser be moulding in 50-105 ℃ the moulding oil; Isolate the bead of moulding from oil, in 100-180 ℃ of aging 5-20 hour, obtaining granularity after washing, drying and the roasting was the magnetic microsphere aluminum oxide carrier of 2-200 μ m.
Employed aluminum soluble salt can be Al (NO in the process
3)
39H
2O, AlCl
36H
2O, Al
2(SO
4)
318H
2A kind of among the O.Organic amine can be a kind of in hexamethylenetetramine, the urea or the mixture of the two.
The preparation of D magnetic microsphere metallic catalyst:
With solubility inorganic base and Na
2CO
3The mixed ammonium/alkali solutions that total mol concentration is 0.1-2M, wherein inorganic base and the Na of being made into soluble in water
2CO
3Mol ratio be 2-10; The carrier of step C preparation is immersed in the above-mentioned mixed ammonium/alkali solutions, fully adsorb and activate hypsokinesis and remove raffinate, then oven dry; Be dissolved in water with solubility divalence active metal salt and solubility magnesium salts again and be made into the mixing salt solution that total mol concentration is 0.1-3M, wherein the mol ratio of divalence active metal salt and solubility magnesium salts is 0.1-2: 10; Place the hypsokinesis in 2-12 hour of this mixing salt solution dipping to remove raffinate the impregnated magnetic carrier of mixed ammonium/alkali solutions, under 40-100 ℃ of temperature conditions crystallization 4-24 hour, wash to neutral with pure water after reducing to room temperature, and under 80-120 ℃, dry to constant weight, obtain the synthetic LDHs precursor that contains reactive metal of endoporus original position, with this LDHs precursor at 200-700 ℃ of roasting temperature 2-24 hour, preferable roasting condition is at 300-600 ℃ of following roasting 4-12 hour, make the LDHs that contains reactive metal be transformed into composite metal oxide, then the sample after the roasting being positioned in the reduction apparatus, is 0.01-1 with mol ratio: 10 H
2And N
2The mist reduction is handled, and reduction temperature is controlled at 200-400 ℃ of scope, recovery time 2-24 hour, obtains magnetic ball form height spread loads type metallic catalyst.
Used solubility inorganic base is NaOH, NH
4Any among OH, the KOH; Divalence solubility active metal salt is Cu
2+, Ni
2+, Pt
4+, Mn
2+, Pd
2+, Co
2+Deng nitrate, chloride, sulfate etc. in any or multiple.The solubility magnesium salts is Mg (NO
3)
26H
2O, MgSO
47H
2O, MgCl
26H
2O, anhydrous MgSO
4Or MgF
2In any or multiple.
Adopt temperature programming hydroxide titration (H
2-O
2-TPD) method or temperature programming CO adsorption desorption (CO-TPD) method are measured the decentralization of its reactive metal between 45-60%.
The preparation of magnetic microsphere metallic catalyst also can be adopted infusion process, and step is as follows:
The magnetic microsphere aluminum oxide carrier of step C preparation immersed in the soluble-salt solution that contains reactive metal flood, the content of control active metal component in catalyst is at 0.01-10%, 0.5-12 raffinate is removed in a hour hypsokinesis, flood hypsokinesis in 0.5-12 hour and remove raffinate, ageing 12-24 hour, dry to constant weight at 100-200 ℃,, obtain the magnetic microsphere aluminum oxide catalyst through the reduction processing at 250-600 ℃ of roasting 3-12 hour.
The soluble-salt of reactive metal is Cu
2+, Ni
2+, Pt
4+, Mn
2+, Pd
2+, Co
2+Deng nitrate, chloride, sulfate etc. in any or multiple.
Adopt temperature programming hydroxide titration (H
2-O
2-TPD) method or temperature programming CO adsorption desorption (CO-TPD) method are measured the decentralization of its reactive metal at 30%-40%.
Measure microspheres prepared shape magnetic catalyst of the present invention with vibrating specimen magnetometer, its specific saturation magnetization is all greater than 3.0emu/g.
This magnetic microsphere metallic catalyst is mainly used in fluid bed, magnetic stablizing bed technology catalytic hydrogenation reaction, in the hydrogenation and chemical processes such as hydrofinishing in the petrochemical industry and selective hydrogenation as hydrogenation, anthraquinone or the anthraquinone derivative of hexanolactam hydrofining, chlorobenzene hydrogenation-dechlorination, nitrobenzene.
Remarkable result of the present invention is: make it have magnetic owing in the preparing carriers process soft magnetic materials is introduced core, help catalyst all disperses and reduce catalyst under magnetic field environment loss and wearing and tearing; By surface diposition at ferrospinel soft magnetic granules surface coated Si O
2, increased the chemical inertness of magnetic nuclear and the affinity that magnetic is checked outside species; The carrier that specific surface is big, intensity is high, pore structure is good is provided.
The bore area original position is synthetic contain the LDHs of reactive metal after, the carrier bore area contain that divalence, trivalent metal cation are subjected to the influence of lattice energy to be the high degree of dispersion state on the reactive metal LDHs laminate, metal ion is transformed into its corresponding oxide after roasting, make active metallic ion be transformed into the reactive metal of high degree of dispersion state through reduction again, and other divalence, trivalent metal keep its oxide form constant, play interleaving agent and co-catalyst at the catalyst bore area; Highly disperse active metallic catalyst by this method preparation has stronger interaction, thereby makes active component can stably be present in the carrier bore area between its active component and the carrier.
The magnetic microsphere metal supported catalyst, under the constraint of magnetic field force in order, distribute and arrange along the magnetic line of force equably, thereby it is magnetic stablizing bed that fluid bed has been transformed into.Because the distribution of catalyst granules in reaction medium is relatively stable, thereby reduce or avoided collision, wearing and tearing and the loss of catalyst, finally improved the conversion ratio of reactant.
The specific embodiment
Embodiment 1:
A. with passing through N
2Deionized water configuration Mg (NO
3)
26H
2O, Fe
2(SO
4)
3And FeCl
2Mixing salt solution, make respectively Mg of concentration that GOLD FROM PLATING SOLUTION belongs to ion
2+Be 0.2M, Fe
2+Be 0.2M, Fe
3+Be 0.2M.Mixing salt solution is poured in the container, at N
2Under the condition of protection, slowly splashing into NaOH concentration in container is 1.5M, Na
2CO
3Concentration is the mixed ammonium/alkali solutions of 0.5M, when the pH value in the system reaches 11, stops dripping alkali liquid.Then at N
2Under the condition of protection, in 20 ℃ of water-baths, crystallization 8 hours is filtered then, with the frozen water washing by nitrogen, washs 2 times with 0 ℃ ethanol again, and drying obtains Mg
2+-Fe
2+-Fe
3+-CO
3 2-LDHs.LDHs is put in the Muffle furnace, is warming up to 900 ℃, be incubated 5 hours, naturally cool to room temperature and obtain MgFe with the speed of 5 ℃/min
2O
4Ferrite records its specific saturation magnetization 41emu/g, and granularity is 25 μ m.
B. with MgFe
2O
4Adding fills in the reactor of deionized water behind ferrite porphyrize to the 2 μ m, and dripping concentration simultaneously in reactor is the Na of 1M
2SiO
3Solution and concentration are the nitric acid of 0.5M.Keeping the pH value of reactant mixture in the process is 5, and reaction temperature is 60 ℃.Work as Na
2SiO
3The addition of solution reaches SiO
2/ MgFe
2O
4Weight ratio be 4 o'clock, stop to drip, and continued stirring reaction 5 hours.Spend deionised water at last to neutral, and under 120 ℃ of temperature dry 5 hours.
C. with particle diameter the AlCl that the aluminium powder of 100 μ m is dissolved in 1M
36H
2Preparation aluminium colloidal sol in the O solution.With water-soluble 30% the solution of being made in deionized water of hexamethylenetetramine.Adding the magnetic that coated by 10% of the spherical alumina support weight of the magnetic that finally obtains and examine in aluminium colloidal sol, is that 9 ratio adds hexamethylenetetramine solution in said mixture in the mol ratio of Al and hexamethylenetetramine then.It is in 100 ℃ the moulding oil that mixture sprays into temperature by disperser, separate behind the moulding bead in 170 ℃ aging 10 hours, be 60-120 μ m magnetic microsphere gamma-alumina carrier by obtaining granularity after washing, the dry and 550 ℃ of roastings at last.Recording specific saturation magnetization with vibrating specimen magnetometer is 4.1emu/g.
D. with 0.89 mole NaOH and 0.27 mole Na
2CO
3Be dissolved in the 2000ml water and be made into mixed ammonium/alkali solutions.With the 1000g particle diameter be 60-120 μ m magnetic microsphere gamma-alumina carrier impregnation in above-mentioned solution, make mixed base enter in the carrier duct the fully aluminium on activated carrier surface, dry to constant weight then.With 0.02 mole of PdCl
2With 0.25 mole of MgCl
26H
2O is dissolved in the 2000ml water and is made into mixing salt solution, in the carrier immersion mixing salt solution of alkali activation, make salt wherein all enter the carrier duct with above-mentioned, after the maceration extract under 100 ℃ of temperature conditions crystallization 10 hours, incline and spend deionised water behind the raffinate to neutral, under 120 ℃, be dried to constant weight, being put in the Muffle furnace 550 ℃ of following roastings 10 hours, is 0.2: 10 H with ratio in 250 ℃ then again
2/ N
2Gaseous mixture reduction 5 hours palladium content is 0.2% catalyst sample.Recording its palladium decentralization is 54%, and specific saturation magnetization is 3.5emu/g.
Embodiment 2:
Keep the preparation condition of carrier among the embodiment 1 identical, change the Preparation of catalysts method into infusion process by the lamellar precursor method.
Adopt the preparation method 1 of magnetic microsphere metallic catalyst, in the load capacity of palladium is that 0.2% ratio impregnated in above-mentioned magnetic carrier in the chlorine palladium acid solution, hypsokinesis in 2 hours is removed raffinate and be dried to constant weight under 120 ℃, being put in the Muffle furnace 550 ℃ of following roastings 10 hours, is 0.2: 10 H with ratio in 250 ℃ then again
2/ N
2Gaseous mixture reduction 5 hours palladium content is 0.2% catalyst sample.Recording its palladium decentralization is 42%, and specific saturation magnetization is 3.6emu/g.
Embodiment 3:
Keep other preparation condition among the embodiment 1 constant, the Mg (NO during with the preparation ferrite
3)
26H
2O is by Co (NO
3)
2Substitute; When magnetic nuclear is coated by SiO
2/ NiFe
2O
4Weight ratio be that 2 ratio adds Na
2SiO
3Solution and concentration are the nitric acid of 1M; AlCl during preparation aluminium colloidal sol
36H
2O changes Al (NO into
3)
39H
2O, molal quantity is constant; Record the specific saturation magnetization 65emu/g of magnetic nuclear, granularity is 30 μ m; The specific saturation magnetization of carrier is 8.3emu/g, and crystal formation is the γ type; Preparation palladium content is 0.2% catalyst, and the palladium decentralization is 49%, and specific saturation magnetization is 6.9emu/g.
Embodiment 4:
Keep other preparation condition among the embodiment 1 constant, the hexamethylenetetramine during with the preparation magnetic alumina carrier is substituted by urea, and aging temperature and ageing time become 130 ℃ and 18 hours respectively; The specific saturation magnetization of carrier is 4.5emu/g, and crystal formation is the γ type; The synthetic solubility inorganic base that contains palladium LDHs of original position replaces with NH by original NaOH
4OH, the solubility magnesium salts is by MgCl
26H
2O becomes Mg (NO
3)
26H
2O; The palladium decentralization of catalyst is 51%, and specific saturation magnetization is 3.8emu/g.
Embodiment 5:
Other condition is constant among the maintenance embodiment 1, and original position is synthesized PdCl used when containing reactive metal LDHs on the spherical alumina support of magnetic
2By Ni (NO
3)
2Replace, and molal quantity is constant.The nickel decentralization of gained catalyst is 47%, and specific saturation magnetization is 3.6emu/g.
Embodiment 6:
The internal diameter of respectively 2.0g embodiment 1 and embodiment 2 made catalyst samples being packed into is 2.5cm, constitute magnetic stablizing bed in the stainless steel tube of the strap clamp cover of high 400cm, the flow that in anthraquinone concentration is the working solution of 120g/L is 16L/h, 50 ℃, 0.3Mpa under the reaction pressure, the catalyst of embodiment 1 can make the anthraquinone hydrogenation efficient of discharging working solution reach 10.4g/L, and the catalyst of embodiment 2 is 8.5g/L.
Embodiment 7:
Made magnetic nickel-containing catalyst is through NaB among the embodiment 5
HAfter 4 reduction, with 50% ethanol washing 5 times, then with ethanol as solvent, be 0.5mol by active component Ni, in 50 ℃, stirring reaction is 12 hours under the normal pressure in nature of glass reactor for the ratio adding catalyst of chlorobenzene 2.6mol and chlorobenzene.Also should add the HCl that excess NaOH produces with absorption reaction in the reactant mixture.With each components contents in high performance liquid chromatography (HPLC-Shimadzu10AT) analytical reactions thing and the product.By the conversion ratio that calculates reaction with the content before and after the chlorobenzene reaction is 96.4%.
Claims (6)
1. magnetic microsphere high-dispersion load metallic catalyst, the carrier that it is characterized in that this catalyst is the ball-aluminium oxide that contains magnetic ferrites magnetic nuclear, the crystal formation of aluminium oxide is a kind of among γ, η, δ, θ, the α, and the granularity of carrier is 2-200 μ m, and specific surface is 10-300m
2/ g, pore volume are 0.7-1.5ml/g;
The reactive metal of load is one or more among Cu, Ni, Pt, Mn, Pd or the Co on the catalyst, and the content of reactive metal is at 0.01-10%; The decentralization of reactive metal is 30-60%;
The bulk density of catalyst is 0.3-0.7g/ml, and the specific saturation magnetization of catalyst is greater than 3.0emu/g;
The chemical general formula of magnetic ferrites magnetic nuclear is MeFe
2O
4, Me
2+Be Mn
2+, Zn
2+, Cu
2+, Ni
2+, Mg
2+Or Co
2+In any one or multiple.
2. the described magnetic microsphere high-dispersion load of claim 1 metallic catalyst, the decentralization that it is characterized in that catalyst is 45-60%.
3. the preparation method of magnetic microsphere high-dispersion load metallic catalyst, under the concrete preparation process:
A. the preparation of ferrite magnetic nuclear
According to Fe
2++ Fe
3+=2Me
2+Mol ratio preparation contain bivalent metal ion Me
2+And Fe
2+, Fe
3+The mixing salt solution of ion, wherein the molar concentration of each metal ion species is 0.1-0.6M; With NaOH and solubility inorganic sodium preparation mixed-alkali solution, wherein, NaOH concentration is 1.0-2.5M, and sodium salt concentration is 0-1.7M; At N
2Under the condition of protection, mixed-alkali solution slowly is added drop-wise in the mixing salt solution, when the pH value in the system reaches 7-12, stops to drip, at N
2Protection in 20-65 ℃ of water-bath crystallization 5-25 hour down, after filtration, washing, drying obtain Me
2+-Fe
2+-Fe
3+-LDHs is placed in the high temperature furnace, is warming up to 850-1150 ℃ with the speed of 2-15 ℃/min, roasting 2-7 hour, obtains magnetic ferrites MeFe
2O
4
Anion in the above-mentioned mixing salt solution is Cl
-, NO
3 -Or SO
4 2-In any one or a few; Me
2+Be meant Mn
2+, Zn
2+, Cu
2+, Ni
2+, Mg
2+Or Co
2+In any one or a few; The solubility inorganic sodium is sodium carbonate, sodium sulphate or sodium chloride;
Or prepare ferrite magnetic nuclear according to following method:
Oxide, hydroxide or other precipitation mixture that will contain Me, Fe metal obtain MeFe 850～1150 ℃ of roastings 2～7 hours
2O
4, Me wherein
2+Be Mn
2+, Zn
2+, Cu
2+, Ni
2+, Mg
2+Or Co
2+In any one or multiple;
B. the coating of magnetic ferrites magnetic nuclear
With ferrite MeFe
2O
4Be crushed to add behind the particle of 0.1-10 μ m and fill in advance in the band stirred reactor of deionized water, keep in the reactor temperature of charge at 15-100 ℃, while stirring with scheduled volume, concentration is the Na of 0.1-2M
2SiO
3With concentration be that the inorganic acid of 0.1-3M adds in the reactor, continue to stir reaction down 2-10 hour, spend solids in the deionised water reactor to neutral, and under 100-200 ℃ of temperature dry 2-12 hour, obtain the surface and coated SiO
2Ferrite magnetic nuclear;
Na
2SiO
3With the addition of inorganic acid according to surface coated SiO
2Amount and determine, make the SiO of coating
2With MeFe
2O
4Mass ratio be 0.3-5: 1; Used inorganic acid is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid;
C. the preparation of magnetic microsphere aluminum oxide carrier
The aluminium powder of 10-150 μ m is dissolved in preparation aluminium colloidal sol in the soluble aluminum salting liquid of 0.1-2M, adding the magnetic that coated by the 1-20% of the spherical alumina support weight of the magnetic that finally obtains examines in aluminium colloidal sol, mol ratio in Al and organic amine is 2-10 again: 1 ratio adds the organic amine solution that concentration is 0.1-0.5M in above-mentioned colloidal sol, mixing the back, to spray into temperature by disperser be moulding in 50-105 ℃ the moulding oil, from oil, isolate the bead of moulding, in 100-180 ℃ of aging 5-20 hour, washing, obtaining granularity after drying and the roasting is the magnetic microsphere aluminum oxide carrier of 2-200 μ m;
Employed aluminum soluble salt is Al (NO
3)
39H
2O, AlCl
36H
2O, Al
2(SO
4)
318H
2A kind of among the O; Organic amine is a kind of in hexamethylenetetramine, the urea or the mixture of the two;
D. carry and hold active metal component
With solubility inorganic base and Na
2CO
3The mixed ammonium/alkali solutions that total mol concentration is 0.1-2M, wherein inorganic base and the Na of being made into soluble in water
2CO
3Mol ratio be 2-10; The carrier of step C preparation is immersed in the above-mentioned mixed ammonium/alkali solutions, fully adsorb and activate hypsokinesis and remove raffinate, then oven dry; Be dissolved in water with solubility divalence active metal salt and solubility magnesium salts again and be made into the mixing salt solution that total mol concentration is 0.1-3M, wherein the mol ratio of divalence active metal salt and solubility magnesium salts is 0.1-2: 10; Place the hypsokinesis in 2-12 hour of this mixing salt solution dipping to remove raffinate the impregnated magnetic carrier of mixed ammonium/alkali solutions, under 40-100 ℃ of temperature conditions crystallization 4-24 hour, wash to neutral with pure water after reducing to room temperature, and under 80-120 ℃, dry to constant weight, obtain the synthetic LDHs precursor that contains reactive metal of endoporus original position, with this LDHs precursor at 200-700 ℃ of roasting temperature 2-24 hour, make the LDHs that contains reactive metal be transformed into composite metal oxide, then the sample after the roasting being positioned in the reduction apparatus, is 0.01-1 with mol ratio: 10 H
2And N
2The mist reduction is handled, and reduction temperature is controlled at 200-400 ℃ of scope, recovery time 2-24 hour, obtains magnetic ball form height spread loads type metallic catalyst;
Used solubility inorganic base is NaOH, NH
4Any among OH, the KOH; Divalence solubility active metal salt is Cu
2+, Ni
2+, Pt
4+, Mn
2+, Pd
2+, Co
2+Nitrate, chloride, sulfate in any or multiple; The solubility magnesium salts is Mg (NO
3)
26H
2O, MgSO
47H
2O, MgCl
26H
2O, anhydrous MgSO
4Or MgF
2In any or multiple;
Or carry with following method and to hold active metal component:
The magnetic microsphere aluminum oxide carrier of step C preparation immersed in the soluble-salt solution that contains reactive metal flood, the content of control active metal component in catalyst is at 0.01-10%, flood hypsokinesis in 0.5-12 hour and remove raffinate, ageing 12-24 hour, dry to constant weight at 100-200 ℃, at 250-600 ℃ of roasting 3-12 hour, obtain the magnetic microsphere aluminum oxide catalyst through the reduction processing;
The soluble-salt of reactive metal is Cu
2+, Ni
2+, Pt
4+, Mn
2+, Pd
2+Or Co
2+Nitrate, chloride or sulfate in any or multiple.
4. the preparation method of the described magnetic microsphere high-dispersion load of claim 3 metallic catalyst, the sintering temperature that it is characterized in that the LDHs precursor is 300-600 ℃, roasting time is 4-12 hour.
5. the purposes of a magnetic microsphere high-dispersion load metallic catalyst as claimed in claim 1 is characterized in that this catalyst is used for fluid bed, magnetic stablizing bed technology catalytic hydrogenation reaction.
6. the purposes of a magnetic microsphere high-dispersion load metallic catalyst as claimed in claim 1 is characterized in that this catalyst is used in the hydrofinishing and selective hydrogenation chemical process of the hydrogenation of hydrogenation, anthraquinone or anthraquinone derivative of hexanolactam hydrofining, chlorobenzene hydrogenation-dechlorination, nitrobenzene and petrochemical industry.
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| EP2003718B8 (en) * | 2006-03-29 | 2012-06-20 | Cataler Corporation | Electrode catalyst for fuel cell, and solid polymer electrolyte fuel cell |
| CN101172256B (en) * | 2006-10-31 | 2011-02-09 | 中国石油化工股份有限公司石油化工科学研究院 | Method for preparing fire resistant magnetic alumina carrier |
| 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 |
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| EP2294234A1 (en) * | 2008-06-20 | 2011-03-16 | BHP Billiton SSM Development Pty Ltd | Process for the recovery of nickel and/or cobalt from a leach solution |
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| CN102000574B (en) * | 2010-10-12 | 2012-07-25 | 中国石油大学(华东) | Roller flyball method for preparing spherical magnetic alumina carrier |
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| CN108283918B (en) * | 2018-02-13 | 2020-07-31 | 上海市刑事科学技术研究院 | Magnetic microsphere and hair detection application thereof |
| CN111229230B (en) * | 2020-03-11 | 2022-10-21 | 广东工业大学 | Ellipsoidal alumina supported metal catalyst and preparation method and application thereof |
| CN112221504A (en) * | 2020-11-12 | 2021-01-15 | 北京旭阳科技有限公司 | Preparation method of caprolactam hydrofining catalyst, catalyst and method for refining caprolactam by using catalyst |
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