CN1281321C - Precious metal carrying hydrogenation catalyst - Google Patents
Precious metal carrying hydrogenation catalyst Download PDFInfo
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- CN1281321C CN1281321C CN 03122855 CN03122855A CN1281321C CN 1281321 C CN1281321 C CN 1281321C CN 03122855 CN03122855 CN 03122855 CN 03122855 A CN03122855 A CN 03122855A CN 1281321 C CN1281321 C CN 1281321C
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Abstract
The present invention discloses a hydrogenation catalyst carrying noble metal, which is mainly prepared from a spherical carrier material and a noble metal active component. The hydrogenation catalyst is characterized in that the spherical carrier material contains 50 to 99 wt% of alumina and 1 to 50 wt% of magnetic particle, wherein the magnetic particles comprise SiO2 coating layers and kernels selected from one or several kinds of Fe3O4, Fe and gamma-Fe2O3, the weight ratio of the SiO2 coating layer to the kernels is (0.05 to 6): 1, and the noble metal active component is selected from one or several kinds of platinum, palladium, ruthenium and rhodium.
Description
Technical field
The invention relates to a kind of catalyst, more specifically say so about a kind of hydrogenation catalyst of carried noble metal.
Background technology
In the hydrogenation process in fields such as petrochemical industry, fine chemistry industry, pharmacy, load type palladium catalyst is the hydrogenation catalyst of using always, and used carrier is generally aluminium oxide, silica, active carbon etc.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.Pat.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.
Along with fine grained magnetic catalyst and magnetic stopping reaction technology (are seen " development of industrial catalyst and exploitation ", Sinopec publishing house, 1997,195 pages) development, when the preparation load type palladium catalyst, iron or other magnetisable material are added in the carrier, can make catalyst have magnetic.
USP 5,208, and 392 disclosed a kind of aluminium oxide loaded Pd-Fe Preparation of catalysts methods are immersed in palladium salt and molysite on the alumina support, then drying, roasting obtains said catalyst in nitrogen atmosphere.This catalyst can be used for the mixture of cyclohexane oxidation preparing cyclohexanone and cyclohexanol.Because iron directly exposes at catalyst surface, may adverse influence be arranged to some reaction, also may pollution be arranged to some material, also may cause the loss of iron.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, providing a kind of is the noble metal catalyst of carrier with the new material.
The hydrogenation catalyst of carried noble metal provided by the invention mainly is made up of ball type carrier material and noble metal active component.
In the said catalyst, the ball type carrier material accounts for 95～99.8 heavy %, noble metal active ingredients constitute 0.2～5 heavy %, preferred 0.3～1.5 heavy %.
Contain the aluminium oxide of 50～99 heavy % and the magnetic-particle of 1～50 heavy %, preferred 2～15 heavy % in the said ball type carrier material, wherein said magnetic-particle is (0.05～6) by weight ratio: 1, preferred (0.3～4.0): 1 SiO
2Clad and be selected from Fe
3O
4, Fe and γ-Fe
2O
3In one or more kernels form.
Said noble metal active component is for being selected from platinum group metal such as platinum, palladium, ruthenium, the rhodium one or more, wherein preferred platinum and/or palladium.
In the catalyst provided by the invention, said ball type carrier material, its particle diameter is between 10 μ m to 6mm.
In the said ball type carrier material, 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, be that the predecessor by aluminium oxide is transformed; 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 the said ball type carrier material, magnetic-particle is dispersed in the structure of alumina support (Fig. 3).Said magnetic-particle is 0.5～3: 1 SiO by weight ratio
2Clad and kernel are formed, and its kernel is 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.
By magnetometer said ball type carrier material is measured, its hysteresis curve 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.
Said ball type carrier material, the SiO on its inner magnetic kernel, surface
2Form certain component echelon and structure gradient between clad and the 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.
Said ball type carrier material is through forming SiO
2Moulding (inner gel) in cladded type magnetic component particle, the oil, further reduce or oxidation processes, the steps such as form of magnetic-particle core obtain in the control carrier.
More particularly, said ball type carrier preparation methods 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.
Wherein, the said alkali of step 1 is selected from KOH, NaOH, NH
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 concentration of wherein said organic amine solution is 12%～40%, and said organic amine is meant that the pH value is approaching neutral at normal temperatures, but through adding the material that thermal decomposition can discharge alkaline matter, as urea or hexamethylenetetramine, can be used singly or in combination.
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 that, aluminium powder thin with metallic aluminium is dissolved in liquor alumini chloridi as preferred version, 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 0～2.0 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, the polyoxyethylene dioleate, 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 and produce γ-Fe
2O
3, make in the carrier kernel of two kinds of forms of coexistence.
Loaded noble metal catalyst provided by the present invention is that the maceration extract that will contain noble metal floods drying behind the ball type carrier material recited above, roasting, and obtains through reduction process.Said maceration extract is made into by precious metal salt (as palladium bichloride, chloroplatinic acid etc.), inorganic acid and deionized water, the preferred hydrochloric acid of said inorganic acid, and the pH value of maceration extract is 2～6; Said baking temperature is 70～120 ℃; The roast temperature is 150～600 ℃;
Said reduction is 80～500 ℃ of reductase 12～6 hour in hydrogen atmosphere, or reduces with formaldehyde, hydrazine etc.
Loaded noble metal catalyst provided by the invention owing to adopted a kind of novel ball type carrier material, has the following advantages:
1, have superparamagnetism, when outside magnetic field exists, good magnetic energy is arranged, when external magnetic field did not exist, the remanent magnetism of product and coercivity were zero, and particle is difficult for assembling during no externally-applied magnetic field, good dispersion so can control easily, separate and reclaim.
2, have good chemical stability, heat endurance and corrosion resistance, the SiO on magnetic-particle surface
2Clad does not expose the ferromagnetism component at catalyst surface, can avoid the loss of ferromagnetism component and to the pollution and toxic hazard of some material.
3, granularity is little, and reaction interface increases, and mass transfer rate is accelerated, and its catalytic performance is fully utilized.
Description of drawings
Fig. 1 is the cross-sectional view of magnetic-particle in the used spherical carrier material of catalyst of the present invention.
Fig. 2 is the XRD spectra of magnetic-particle in the used spherical carrier material of catalyst of the present invention.
Fig. 3 is the cross-sectional view of the used spherical carrier material of catalyst of the present invention.
Fig. 4 is the TEM photo of magnetic-particle in the used spherical carrier material of catalyst of the present invention
Fig. 5 is the hysteresis curve of magnetic-particle in the ball type carrier material of embodiment 1 preparation.
Fig. 6 is the hysteresis curve of the ball type carrier material of embodiment 4,5 and 6 preparations.
Fig. 7,8 is respectively the XRD spectra of the ball type carrier material of embodiment 4 and 9 preparations.
Fig. 9 is the SEM photo of the ball type carrier material of embodiment 1 preparation.
Figure 10 is the SEM photo of the ball type carrier material of embodiment 4 preparations.
The specific embodiment
The present invention is further illustrated below by embodiment, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In an embodiment, the pattern of ball type carrier material sample adopts JSM-5800 type ESEM and H-8100 type transmission electron microscope to observe respectively; B-H loop 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.
The preparation process of the ball type carrier material that is adopted in embodiment 1～9 explanation catalyst provided by the invention.
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
2.4H
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=0kOe), 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 (A.m 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.
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 6Mol/L 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.
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 the 100mlA3 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.
Get ball type carrier material 10 grams of embodiment 4 preparations, with PdCl
2Adding hydrochloric acid, to be made into Pd content 0.12wt%, pH be 30 milliliters of 4.5 dipping solutions, carries Pd with infusion process, and impregnated carrier is 2 hours under the normal temperature, will flood PdCl
2Carrier material 70 ℃ of dryings 2 hours in baking oven, 120 ℃ of dryings 2 hours, 300 ℃ of roastings 4 hours in Muffle furnace then, in 100 ℃ of following hydrogen reducings 4, the catalyst of preparing is called catalyst-1 again, this catalyst consist of Pd content 0.3wt%.
Embodiment 11
Prepare catalyst according to embodiment 10 described methods, just Pd content difference in the maceration extract.During Pd content 0.25wt%, the catalyst of preparing is called catalyst-2 in the maceration extract, this catalyst consist of Pd content 0.7wt%.
Embodiment 12
Prepare catalyst according to embodiment 10 described methods, just Pd content difference in the maceration extract.During Pd content 0.35wt%, the catalyst of preparing is called catalyst-3 in the maceration extract, this catalyst consist of Pd content 1.0wt%.
Embodiment 13
Prepare catalyst according to embodiment 10 described methods, just Pd content difference in the maceration extract.During Pd content 0.52wt%, the catalyst of preparing is called catalyst-4 in the maceration extract, this catalyst consist of Pd content 1.5wt%.
Embodiment 14
Get ball type carrier material 10 grams of embodiment 4 preparations, with H
2PtCl
6Adding hydrochloric acid, to be made into Pt content 0.12wt%, pH be 50 milliliters of 4.5 solution, carries Pt with infusion process, and impregnated carrier is 2 hours under the normal temperature, will flood H
2PtCl
6Carrier material 70 ℃ of dryings 2 hours in baking oven, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 4 hours in Muffle furnace then, in 400 ℃ of following hydrogen reducings 4, the catalyst of preparing is called catalyst-5 again, this catalyst consist of Pt content 0.3wt%.
Embodiment 15
Prepare catalyst according to embodiment 14 described methods, just Pt content difference in the maceration extract.During Pt content 0.25wt%, the catalyst of preparing is called catalyst-6 in the maceration extract, this catalyst consist of Pt content 0.7wt%.
Embodiment 16
Prepare catalyst according to embodiment 14 described methods, just Pt content difference in the maceration extract.During Pt content 0.35wt%, the catalyst of preparing is called catalyst-7 in the maceration extract, this catalyst consist of Pt content 1.0wt%.
Embodiment 17
Prepare catalyst according to embodiment 14 described methods, just Pt content difference in the maceration extract.During Pt content 0.52wt%, the catalyst of preparing is called catalyst-8 in the maceration extract, this catalyst consist of Pt content 1.5wt%.
Comparative Examples 1
Employing pH value is 4.5 PdCl
2Solution, at normal temperature to a kind of commodity γ-Al
2O
3Carrier (about 150 microns of particle diameter, specific area 290m
2/ g, pore volume 0.63mL/g) dipping 2h, 70 ℃ of dry 2h, 120 ℃ of dry 2h then, 300 ℃ of roast 2h, 100 ℃ of following hydrogen reducing 4h prepare the Pd/Al of palladium content 1wt%
2O
3Catalyst is called contrast medium-1.
Comparative Examples 2
Employing pH value is 4.5 H
2PtCl
4Solution, at normal temperature to a kind of commodity γ-Al
2O
3Carrier (about 150 microns of particle diameter, specific area 290m
2/ g, pore volume 0.63mL/g) dipping 2h, 70 ℃ of dry 2h, 120 ℃ of dry 2h then, 500 ℃ of roast 4h, 400 ℃ of following hydrogen reducing 4h prepare the Pt/Al of palladium content 1wt%
2O
3Catalyst is called contrast medium-2.
Embodiment 18
Present embodiment illustrates the hydrogenation effect of catalyst provided by the invention.
The response data of the nitrobenzene hydrogenation of catalyst among the embodiment 12-4 and Comparative Examples agent-1 sees Table 1.In the reactor of 300ml, add the 1g catalyst, 10ml nitrobenzene, 60ml ethanol is made solvent, and reaction condition is 30 ℃ of temperature, pressure 1.0MPa, speed of agitator 630rpm, reaction time 40min.Gas chromatography, hydrogen flame detector are adopted in the analysis of product.
Table 1
| Catalyst | Nitrobenzene conversion ratio % | Aniline selectivity % |
| Catalyst-3 contrast medium-1 | 99.5 99.7 | 99.3 99.1 |
By table 1 as seen, the hydrogenation of chloronitrobenzene of catalyst provided by the invention activity of such catalysts and selectivity active and aniline selectivity and prior art for preparing is suitable.
Embodiment 19
Present embodiment illustrates the hydrogenation effect of catalyst provided by the invention.
The data of the octene-1 hydrogenation reaction of the catalyst of embodiment 16-7 Comparative Examples agent-2 see Table 2.Add the 0.5g catalyst in the reactor of 300ml, 20ml octene-1,80ml cyclohexane give solvent, reaction condition are 80 ℃ of temperature, pressure 1.0MPa, speed of agitator 630rpm, reaction time 20min.Gas chromatography, hydrogen flame detector are adopted in the analysis of product.
Table 2
| Catalyst | Octene-1 conversion ratio % | Octane selectivity % |
| Catalyst-7 contrast medium-2 | 99.8 99.6 | 99.2 99.5 |
By table 2 as seen, the activity of such catalysts and the selectivity of the octene-1 hydrogenation activity of catalyst provided by the invention and octane selectivity and prior art for preparing are suitable.
Claims (10)
1, a kind of hydrogenation catalyst of carried noble metal, mainly form by ball type carrier material and noble metal active component, it is characterized in that containing in the said ball type carrier material aluminium oxide of 50～99 heavy % and the magnetic-particle of 1～50 heavy %, wherein said magnetic-particle is 0.05～6: 1 SiO by weight ratio
2Clad and be selected from Fe
3O
4, Fe and γ-Fe
2O
3In one or more kernels form, said noble metal active component is selected from one or more in platinum, palladium, ruthenium, the rhodium.
2,, it is characterized in that this catalyst is made up of the noble metal active component of the ball type carrier material of 95～99.8 heavy % and 0.2～5 heavy % according to the catalyst of claim 1.
3,, it is characterized in that said noble metal active component is selected from platinum and/or palladium according to the catalyst of claim 1 or 2.
4,, it is characterized in that said noble metal active components contents is 0.3～1.5 heavy % according to the catalyst of claim 2.
5, according to the catalyst of claim 1, it is characterized in that in the said ball type carrier material that 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.
6,, 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 catalyst of claim 1.
7,, it is characterized in that said kernel is that one or more particle diameters are the single domain superparamagnetism particulate of 3～30 nanometers according to claim 1 or 6 said catalyst.
8,, it is characterized in that said ball type carrier material particle size is at 10 μ m to 6mm according to the said catalyst of claim 1.
9,, it is characterized in that containing in the said ball type carrier material magnetic-particle of 2～15 heavy % according to the said catalyst of claim 1.
10,, it is characterized in that said magnetic-particle is 0.5～3: 1 SiO by weight ratio according to claim 1 or 9 said catalyst
2Clad and kernel are formed.
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|---|---|---|---|
| CN 03122855 CN1281321C (en) | 2003-04-29 | 2003-04-29 | Precious metal carrying hydrogenation catalyst |
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| CN100372610C (en) * | 2004-06-14 | 2008-03-05 | 北京化工大学 | Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use |
| 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 |
| CN101402039B (en) * | 2008-11-13 | 2010-12-08 | 北京化工大学 | Method for producing supported metal palladium catalyst |
| CN104140480B (en) * | 2013-05-08 | 2016-10-19 | 中国石油大学(北京) | Method for preparing polycyclohexylethylene by polystyrene hydrogenation |
| CN104415767B (en) * | 2013-09-04 | 2017-01-18 | 中国石油化工股份有限公司 | Palladium and/or platinum-containing catalyst and method for removing H2 in CO raw material |
| CN104549059B (en) * | 2013-10-28 | 2017-03-01 | 中国石油化工股份有限公司 | Anthraquinone legal system hydrogen peroxide slurry bed system hydrogenation reactor and its application |
| CN104667945A (en) * | 2015-01-10 | 2015-06-03 | 安徽大学 | Supported palladium catalyst Fe3O4/SiO2Preparation of Pd and application in Suzuki reaction |
| CN107698757B (en) * | 2017-10-31 | 2020-06-02 | 山西大同大学 | Ferroferric oxide/silicon dioxide/polypyrrole nano composite particles and preparation method thereof |
| CN113634221A (en) * | 2021-08-25 | 2021-11-12 | 天津大学 | Anionic dye-oriented Al2O3Modified Fe3O4Preparation and application of nanoparticles |
| CN114933532B (en) * | 2022-05-13 | 2024-01-30 | 安徽英瑞骐生物科技有限公司 | Method for continuously synthesizing 2-n-butyl acetoacetic acid ethyl ester by fixed bed |
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