CN1226088C - High Dispersing palladium catalyst prepared by lamellar precursor and preparation method thererof - Google Patents

High Dispersing palladium catalyst prepared by lamellar precursor and preparation method thererof Download PDF

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CN1226088C
CN1226088C CN 02131246 CN02131246A CN1226088C CN 1226088 C CN1226088 C CN 1226088C CN 02131246 CN02131246 CN 02131246 CN 02131246 A CN02131246 A CN 02131246A CN 1226088 C CN1226088 C CN 1226088C
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palladium
carrier
catalyst
salt
anthraquinone
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CN1483512A (en
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段雪
李殿卿
张法智
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium

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Abstract

The present invention relates to a novel palladium catalyst and a preparing method thereof. The method has the steps: firstly, hydrotalcite layered precursors containing palladium are formed in an in-situ synthesis mode at the inner parts of the holes in the surface layers of carriers; after that the layered precursors are converted into corresponding complex metal oxides under the roasting at a high temperature; the complex metal oxides are processed by hydrogen gas reducing treatment to obtain a supported highly dispersed catalyst of which the palladium is highly dispersed on the surfaces of the inner holes of the carriers. Because the prepared supported catalyst has highly dispersed metal active constituents in the geometric space positions, and have energy limitation, the metal active constituents can stably exist on the surfaces of the inner holes of the carriers. In addition, the other metals, such as magnesium and aluminum which are synthesized together with metal palladium into the hydrotalcite and are converted into corresponding oxides perform the functions of a cocatalyst and an isolating agent in the catalyst. The catalyst is mainly used for the anthraquinone hydrogenization process for producing hydrogen peroxide by an anthraquinone method, and the catalyst has the advantages of high activity, good selectivity and long service life.

Description

A kind of high dispersive palladium catalyst through lamellar precursor preparation and preparation method thereof
Technical field
The present invention relates to a kind of support type high dispersive palladium catalyst by lamellar precursor preparation and preparation method thereof, this catalyst is mainly used in the anthraquinone in the anthraquinone preparation hydrogen peroxide or the hydrogenation process of anthraquinone derivative, also can be applied to other hydrogenation catalyst process.
Background technology
The catalyst that uses in anthraquinone preparing hydrogen peroxide process is mainly load type palladium catalyst, and at present, the preparation method of the loaded catalyst of industrial use generally adopts dipping.In USP.6126914 and USP.5853693, described with SiO 2Be carrier, carry the method that Metal Palladium prepares the anthraquinone hydrogenation catalyst of holding, because SiO 2Can not be firm between the less and active component in the aperture of carrier and the carrier combine, thereby can not give full play to catalytic performance and may cause the loss of active component phenomenon; Reported that at USP.3635841 the ball-aluminium oxide by δ, θ or δ and θ mixing crystal formation is a carrier, load prepares the method for anthraquinone hydrogenation catalyst greater than 0.05% Metal Palladium, still, carries the reason of the method for holding owing to preparing carriers method and active component, activity is lower, and stability in use is relatively poor.
There are two factors directly to influence the decentralization of reactive metal on carrier in the process of employing immersion process for preparing catalyst.The one,, be subjected to the surface tension of immersion solvent and the influence of solvation, often active component is assembled and the formation large particle crystal at carrier surface at dipping process; They are two years old, 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 carry out roasting to it after the catalyst drying He before the roasting, the metallic crystal coalescence medium and small in this process progressively is grown to oarse-grained crystallization.The metal specific area of the load type metal catalyst that so obtains is little, and metal dispersity only can reach about 35%.The further raising that this has not only limited the loaded catalyst catalytic capability has also caused the significant wastage of precious metal.
Hydrotalcite (Layered Double Hydroxides is called for short LDH) has similar structure to the magnesium hydroxide of lamellar structure, is the product that two valency magnesium ions in the little octahedron of laminate are partly replaced by the metal ion of trivalent.Two-dimentional laminate is vertically arranged in order and is formed three-dimensional crystalline structure among the LDH, and the atom on the laminate is weak chemical bond between interlayer anion and the laminate, as ionic bond, hydrogen bond etc. with covalent bonds.Introduce Tricationic on the LDH laminate and make the laminate skeleton positively charged, the anion of interlayer opposite charges balances each other with it, makes whole crystal show electroneutral.Can form the principle of hydrotalcite according to suitable bivalent metal ion and trivalent metal ion, someone cooperates the atom of metal active component with introducing hydrotalcite laminate with other divalent metal atom, be subjected to the influencing jointly of orientation effect of atom in the minimum and crystal of lattice energy, this metal active master part high degree of dispersion in hydrotalcite precursor can be prepared the palladium catalyst of function admirable.
All introduced among document Applied Catalysis B:Environmental 25 (2000) 191-203, Applied ClayScience 18 (2001) 51-57 and Applied Catalysis B:Environmental 32 (2001) 167-179 by the synthetic palladium hydrotalcite that contains, again through roasting or further reduce the catalyst of the different purposes of Processing of Preparation.But its preparation be unsupported catalyst, the intensity of such catalyst is not high, and the inner active component of catalyst can not be fully utilized, and does not preponderate economically.
Summary of the invention
The purpose of this invention is to provide a kind of high-dispersion loading type palladium catalyst and preparation method thereof.This method has overcome the defective of conventional infusion process, can make the palladium high degree of dispersion in the carrier bore area with the method, prepares a kind of high-dispersion loading type palladium catalyst, thereby activity of such catalysts is increased substantially.
The present invention adopts the synthetic hydrotalcite lamellar precursor that contains palladium of original position in hole, carrier top layer, roasting makes lamellar precursor be transformed into corresponding composite metal oxide under higher temperature then, handle the catalyst that obtains the palladium high degree of dispersion through hydrogen reducing again, this catalyst is mainly used in the anthraquinone hydrogenation process of anthraquinone preparing hydrogen peroxide.
The concrete preparation method of this catalyst is as follows.
A. with solubility inorganic base and Na 2CO 3The mixed ammonium/alkali solutions that every liter of total mole number is 0.1-2M, wherein inorganic base and the Na of being made into soluble in water 2CO 3Mol ratio be 2-10; Carrier is immersed in the above-mentioned mixed ammonium/alkali solutions, fully adsorb and activate hypsokinesis and remove raffinate, then oven dry.
Used solubility inorganic base can be NaOH, NH 4OH, KOH, Ca (OH) 2In any; Used carrier can be Al 2O 3, SiO 2, any in the active carbon, the shape of carrier can be sphere, bar shaped, cloverleaf pattern, cylindrical particle or unformed powder, granularity is between the 5-200 order.Al wherein 2O 3The crystal formation of carrier can be two or more a mixing crystal formation of any among γ, η, δ, θ, the α or they; SiO 2With the pore structure of absorbent charcoal carrier can be mesopore or gross porosity.
B. prepare mixing salt solution: should prepare different mixing salt solutions with the carrier that does not contain aluminium for the carrier that contains aluminium:
For the carrier that does not contain aluminium, as SiO 2And absorbent charcoal carrier, mixing salt solution is dissolved in water by divalence palladium salt, solubility magnesium salts and aluminum soluble salt and is made into, and wherein the mol ratio of divalence palladium salt, magnesium salts and aluminium salt is 0.1-0.5: 2-4: 1, its total mol concentration is 0.1-3M;
For the carrier that contains aluminium, as Al 2O 3Carrier, owing to utilize carrier surface aluminium source, mixing salt solution needn't add aluminium salt.Mixed solution is dissolved in water and is made into by divalence palladium salt, solubility magnesium salts, and wherein the mol ratio of divalence palladium salt and solubility magnesium salts is 0.1-2: 10, and its total mol concentration is 0.1-3M;
To place the mixing salt solution dipping hypsokinesis in 2-12 hour of above-mentioned correspondence to remove raffinate through the impregnated carrier of steps A aqueous slkali, under 40-100 ℃ of temperature conditions crystallization 4-24 hour, reduce to after the room temperature with the pure water washing to neutral, and under 80-120 ℃, dry to constant weight get the endoporus original position synthetic contain palladium hydrotalcite precursor.Wherein contain the 1.7-17% that palladium hydrotalcite content accounts for gross weight, preferably account for 3.4-8.5%;
Used divalence palladium salt can be Pd (NO 3) 2, PdCl 2, Pd (AC) 2Or PdBr 2In any; The solubility magnesium salts can be Mg (NO 3) 26H 2O, MgSO 47H 2O, MgCl 26H 2O, anhydrous MgSO 4Or MgF 2In any; Aluminum soluble salt can be AlCl 36H 2O, Al 2(SO 4) 318H 2O, Al (NO 3) 39H 2O, AlBr 36H 2Any among the O.
C. with the above-mentioned palladium hydrotalcite precursor that contains at 200-700 ℃ of roasting temperature 2-24 hour, preferably under 300-500 ℃ of condition roasting 5-12 hour, make and contain palladium hydrotalcite precursor and 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 the high-dispersion loading type palladium catalyst.
In the above-mentioned carrier, that first-selected is Al 2O 3Carrier is not only because Al 2O 3Carrier has suitable pore structure and good heat endurance, Another reason is to utilize the synthetic palladium hydrotalcite lamellar precursor that contains in aluminium source of carrier bore area, can make between Metal Palladium and the carrier in the catalyst to combine securely, make the catalyst of preparation have longer stability in use and service life.
Adopt temperature programming hydroxide titration (H 2-O 2-TPD) method is measured the palladium decentralization of the catalyst of the present invention's preparation, and the result is all between 45-60%.And adopt traditional catalyst prepared, by measuring with quadrat method, the decentralization of its Metal Palladium is less than 35%.
The high dispersive palladium catalyst of the present invention's preparation is used for anthraquinone hydrogenation preparing hydrogen peroxide mould examination examination, prepare in the hydrogen peroxide bath scaled model experimental device in whole process and to keep hydrogenation pressure 0.15-0.35MPa, hydrogenation temperature 40-70 ℃, anthraquinone hydrogenation efficient reaches more than the 10g/L, amounts to into the hydrogen peroxide manufacture ability greater than 1700kg100%H 2O 2/ (kgPdd) (the kilogram number of 100% hydrogen peroxide of per kilogram palladium production every day); In the selectivity experiment, keep hydrogenation pressure 0.3MPa, 70 ℃ of hydrogenation temperatures, the working solution that will contain anthraquinone passes through beds, forced circulation hydrogenation 7 hours, anthraquinone almost 100% changes into hydrogen anthraquinone and tetrahydro-anthraquinone, does not find degradation product.The explanation of above experimental result, the high dispersive palladium catalyst of this patent invention has better activity and selectivity than other palladium catalyst of present use.
Remarkable result of the present invention is, owing to be at the synthetic palladium LDH that contains of carrier bore area original position, grow in that divalence, trivalent metal cation are subjected to the influence of lattice energy to be the high degree of dispersion state on the laminate that contains palladium LDH lamellar precursor of carrier bore area, metal ion all is transformed into its corresponding oxide after roasting, make PdO be transformed into the Metal Palladium of high degree of dispersion state through reduction again, its oxide form is constant to play interleaving agent and co-catalyst at the catalyst bore area and other divalence, trivalent metal keep; High dispersive palladium 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.This catalyst is mainly used in the anthraquinone in the anthraquinone preparation hydrogen peroxide or the hydrogenation process of anthraquinone derivative, has high activity, good selectivity and long life-span.
The specific embodiment
Embodiment 1:
With 35.610g (0.8903mol) NaOH and 28.279g (0.2668mol) Na 2CO 3Being dissolved in the 2000ml water and being made into mixed ammonium/alkali solutions, is spherical δ-Al of φ 2-3mm with the 1000g diameter 2O 3Carrier impregnation is in above-mentioned solution, and evaporating water progressively under constantly stirring makes mixed base enter the aluminium on the abundant activated carrier surface carrier duct in, dries to constant weight at 120 ℃ then.With 3.330g (0.01878mol) PdCl 2And 50.358g (0.2480mol) MgCl 26H 2O is dissolved in the 2000ml water and is made into mixing salt solution, with above-mentioned Al through the alkali activation 2O 3Made salt wherein all enter the carrier duct in 2 hours in the carrier immersion mixing salt solution, 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 500 ℃ of following roastings 12 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%.
With the 1000g catalyst sample internal diameter of packing into is 2.5cm, constitute fixed 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, 0.25MPa under the reaction pressure, the anthraquinone hydrogenation efficient of catalyst is 10.4g/L, and the hydrogen peroxide manufacture ability is 1997kg100%H 2O 2/ (kgPdd).Running is 332 hours continuously, and the anthraquinone degradation products in the working solution is 3.3g/L only.
Embodiment 2:
With 44.842g (0.8008mol) KOH and 33.952g (0.3203mol) Na 2CO 3Being dissolved in the 2000ml water and being made into mixed ammonium/alkali solutions, is that φ 2.8mm average length is the bar shaped θ of 5mm, the Al of α mixing crystal formation with the 1000g diameter 2O 3Carrier impregnation is in above-mentioned solution, and wherein alpha-crystal form accounts for 8%.Evaporating water progressively under constantly stirring makes mixed base enter the aluminium on the abundant activated carrier surface carrier duct in, dries to constant weight then.With 4.327g (0.01878mol) Pd (NO 3) 2And 61.122g (0.2480mol) MgSO 47H 2O is dissolved in the 2000ml water and is made into mixing salt solution, with above-mentioned bar shaped Al through the alkali activation 2O 3Made salt wherein all enter the carrier duct in 6 hours in the carrier immersion mixing salt solution, after the maceration extract under 80 ℃ of temperature conditions crystallization 18 hours, incline and spend deionised water behind the raffinate to neutral, under 80 ℃, be dried to constant weight, 450 ℃ of following roastings 6 hours, with ratio 1: 10 H in 300 ℃ then 2/ N 2Gaseous mixture reduction 3 hours palladium content is 0.2% catalyst sample.Recording its palladium decentralization is 52%.
With the condition of embodiment 1, the anthraquinone hydrogenation efficient that records this catalyst is 10.9g/L, and the hydrogen peroxide manufacture ability is 2093kg100%H 2O 2/ (kgPdd).Running is 374 hours continuously, and the anthraquinone degradation products in the working solution is 3.6g/L only.
Embodiment 3:
With 64.025g (1.6008mol) NaOH and 70.6975g (0.6670mol) Na 2CO 3Being dissolved in the 2000ml water and being made into mixed ammonium/alkali solutions, is spherical δ-Al of φ 2-3mm with the 1000g diameter 2O 3Carrier impregnation is in above-mentioned solution, and evaporating water progressively under constantly stirring is dried to constant weight again.With 10.818g (0.04695mol) Pd (NO 3) 2And 125.895g (0.6200mol) MgCl 26H 2O is dissolved in the 2000ml water and is made into mixing salt solution, with above-mentioned Al through the alkali activation 2O 3Carrier immerses in the mixing salt solution and to make salt wherein all enter the carrier duct in 8 hours, in maceration extract under 100 ℃ of temperature conditions crystallization 6 hours, under 100 ℃, be dried to constant weight behind the raffinate that inclines.Making in the hole growth have the catalyst precarsor that contains the palladium hydrotalcite to be put in the Muffle furnace 450 ℃ of following roastings 6 hours, is 0.2: 10 H with ratio in 230 ℃ then 2/ N 2Gaseous mixture reduction 3 hours palladium content is 0.5% catalyst sample.Recording its palladium decentralization is 47%.
With the method for embodiment 1, the anthraquinone hydrogenation efficient that records this catalyst is 12.1g/L, and the hydrogen peroxide manufacture ability is 1742kg100%H 2O 2/ (kgPdd).Running is 278 hours continuously, and the anthraquinone degradation products in the working solution is 2.8g/L only.
Embodiment 4:
With diameter in the example 3 is spherical δ-Al of φ 2-3mm 2O 3Carrier changes microspheroidal δ-Al that diameter is a φ 0.10-0.25mm scope into 2O 3Carrier, keeping the constant preparation palladium of other condition content is 0.5% fluid catalyst.Recording its palladium decentralization is 55%.
With the 100g catalyst sample internal diameter of packing into is 5cm, in the stainless steel fluid bed of the strap clamp cover of high 200cm, the flow that in anthraquinone concentration is the working solution of 120g/L is 4L/h, maintenance 0.25MPa reaction pressure also has under the situation of appropriate amount of hydrogen emptying, the anthraquinone hydrogenation efficient of catalyst is 12.4g/L, and the hydrogen peroxide manufacture ability is 2381kg100%H 2O 2/ (kgPdd).Running is 72 hours continuously, and the anthraquinone degradation products in the working solution is less than 1g/L.
Embodiment 5:
With 44.842g (0.8008mol) KOH and 28.279g (0.2668mol) Na 2CO 3Add in the 2000ml water and be made into mixed ammonium/alkali solutions, with the 1000g diameter be the gross porosity spherical silica gel carrier impregnation of φ 2-4mm in above-mentioned solution, evaporating water progressively under constantly stirring is dried to constant weight at 120 ℃ then.With 3.330g (0.01878mol) PdCl 2, 50.358g (0.2480mol) MgCl 26H 2O and 29.937g (0.1240mol) AlCl 36H 2O is dissolved in the 2000ml water and is made into mixing salt solution, the silica-gel carrier of above-mentioned caustic dip immersed in the mixing salt solution made salt wherein all enter the carrier duct in 4 hours, under 100 ℃ of temperature conditions, changing 10 hours after the maceration extract, incline and spend deionised water behind the raffinate to neutral, under 120 ℃, be dried to constant weight, being put in the Muffle furnace 500 ℃ of following roastings 5 hours, under 280 ℃ of temperature is 0.5: 10 H then with ratio again 2/ N 2Gaseous mixture reduction 5 hours palladium content is 0.2% catalyst sample.Recording its palladium decentralization is 49%.
With the method for embodiment 1, the anthraquinone hydrogenation efficient that records this catalyst is 8.9g/L, and the hydrogen peroxide manufacture ability is 1708kg100%H 2O 2/ (kgPdd).Running is 112 hours continuously, and the anthraquinone degradation products in the working solution is 1.3g/L only.
Embodiment 6:
With H among the embodiment 1 2/ N 2The reduction temperature of gaseous mixture increases to 400 ℃, and keeping the constant preparation palladium of other condition content is 0.2% fixed bde catalyst.Recording its palladium decentralization is 46%.
With the method for embodiment 1, the anthraquinone hydrogenation efficient that records this catalyst is 8.8g/L, and the hydrogen peroxide manufacture ability is 1690kg100%H 2O 2/ (kgPdd).Running is 161 hours continuously, the anthraquinone degradation products 0.9g/L in the working solution.

Claims (7)

1. one kind prepares the method for high dispersive palladium catalyst through lamellar precursor, and this method comprises the following steps:
A. with solubility inorganic base and Na 2CO 3The mixed ammonium/alkali solutions that every liter of total mole number is 0.1-2M, wherein inorganic base and the Na of being made into soluble in water 2CO 3Mol ratio be 2-10; Carrier is immersed in the above-mentioned mixed ammonium/alkali solutions, fully adsorb and activate hypsokinesis and remove raffinate, then oven dry;
B. prepare mixing salt solution: for Al 2O 3Carrier and non-Al 2O 3Carrier should be prepared different mixing salt solutions:
For non-Al 2O 3Carrier, mixing salt solution is dissolved in water by divalence palladium salt, solubility magnesium salts and aluminum soluble salt and is made into, and wherein the mol ratio of divalence palladium salt, magnesium salts and aluminium salt is 0.1-0.5: 2-4: 1, its total mol concentration is 0.1-3M;
For Al 2O 3Carrier, owing to utilize carrier surface aluminium source, mixing salt solution needn't add aluminium salt, and mixed solution is dissolved in water and is made into by divalence palladium salt, solubility magnesium salts, and wherein the mol ratio of divalence palladium salt and magnesium salts is 0.1-2: 10, its total mol concentration is 0.1-3M;
To place the mixing salt solution dipping hypsokinesis in 2-12 hour of above-mentioned correspondence to remove raffinate through the impregnated carrier of steps A aqueous slkali, 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, the endoporus original position synthetic contain palladium hydrotalcite precursor, wherein contain the 1.7-17% that palladium hydrotalcite content accounts for gross weight;
C. with the above-mentioned palladium hydrotalcite precursor that contains at 200-700 ℃ of roasting temperature 2-24 hour, make to contain palladium hydrotalcite precursor and be transformed into composite metal oxide, then the sample after the roasting is positioned in the reduction apparatus, be 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 the high-dispersion loading type palladium catalyst.
2. Preparation of catalysts method according to claim 1 is characterized in that:
In the steps A, used solubility inorganic base is NaOH, NH 4OH, KOH, Ca (OH) 2In any; Used carrier is Al 2O 3, SiO 2, any in the active carbon, the shape of carrier is sphere, bar shaped, cloverleaf pattern, cylindrical particle or unformed powder, granularity is between the 5-200 order; Al wherein 2O 3The crystal formation of carrier is two or more a mixing crystal formation of any among γ, η, δ, θ, the α or they; SiO 2With the pore structure of absorbent charcoal carrier be mesopore or gross porosity;
Among the step B, used divalence palladium salt is Pd (NO 3) 2, PdCl 2, Pd (AC) 2Or PdBr 2In any; The solubility magnesium salts is Mg (NO 3) 26H 2O, MgSO 47H 2O, MgCl 26H 2O, anhydrous MgSO 4Or MgF 2In any; Aluminum soluble salt is AlCl 36H 2O, Al 2(SO 4) 318H 2O, Al (NO 3) 39H 2O, AlBr 36H 2Any among the O.
3. Preparation of catalysts method according to claim 1, wherein carrier is Al 2O 3Carrier.
4. Preparation of catalysts method according to claim 1 is characterized in that:
Among the step B, carrier endoporus original position synthetic contain the 3.4-8.5% that palladium hydrotalcite content accounts for gross weight;
Among the step C, containing palladium hydrotalcite precursor sintering temperature is 300-500 ℃, roasting time 5-12 hour.
5. high dispersive palladium catalyst by the preparation of the described method of claim 1, the feature of this catalyst be, activity component metal palladium high degree of dispersion is in the carrier bore area, and the palladium decentralization reaches 45-60%.
6. high dispersive palladium catalyst as claimed in claim 5, wherein the activity component metal palladium stably is present in the carrier bore area.
A high dispersive palladium catalyst as claimed in claim 5 in anthraquinone preparing hydrogen peroxide anthraquinone or the application in the hydrogenation process of anthraquinone derivative.
CN 02131246 2002-09-19 2002-09-19 High Dispersing palladium catalyst prepared by lamellar precursor and preparation method thererof Expired - Fee Related CN1226088C (en)

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AU2003248229A AU2003248229A1 (en) 2002-09-19 2003-08-01 The highly dispersing catalyst from layed precursor and the process for preparing it
PCT/CN2003/000616 WO2004026474A1 (en) 2002-09-19 2003-08-01 The highly dispersing catalyst from layed precursor and the process for preparing it

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