CN101733172A - Supported metal catalyst, preparation method thereof and use thereof - Google Patents
Supported metal catalyst, preparation method thereof and use thereof Download PDFInfo
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- CN101733172A CN101733172A CN200810227414A CN200810227414A CN101733172A CN 101733172 A CN101733172 A CN 101733172A CN 200810227414 A CN200810227414 A CN 200810227414A CN 200810227414 A CN200810227414 A CN 200810227414A CN 101733172 A CN101733172 A CN 101733172A
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Abstract
The invention discloses a supported metal catalyst, a preparation method thereof and use thereof. The supported metal catalyst of the invention is prepared by reducing a precursor of a metal active ingredient supported by a carrier by ionizing radiation, wherein the metal active ingredient is an elementary substance; and the average diameter of the metal particles is less than 8 nanometers. The catalyst of the invention can be widely used in hydrogenation or selective hydrogenation in petrochemical production and has the advantages of high activity, high selectively, no pre-hydrogen reduction, direct use and the like.
Description
Technical field
The present invention relates to load type metal catalyst and its production and application.
Background technology
Load type metal catalyst is the most common catalyst, is widely used in the petro chemical industry, and wherein load hydrogenation catalyst is widely used in the hydrotreatment or the selectively removing of component such as alkene, alkynes in the logistics.For example, contain a spot of alkynes or alkadienes in the products such as the ethene that produces in steam cracking, catalytic cracking or the thermal cracking process, propylene, butylene, these impurity are harmful to for follow-up reactions such as polymerization.Their existence not only can make the polymer performance variation, also may cause explosion danger.Usually use the selective catalytic hydrogenation method, the concentration of alkynes and alkadienes wherein is removed to very low level (molar fraction＜1 * 10
-6), to obtain the product of polymer grade; Also can increase the output of monoolefine simultaneously, improve resource utilization.At C
4In the cut,, to carry out selective hydrogenation and removing alkynes to obtain product butadiene to rich butadiene cut sometimes according to the difference of raw material with to the demand of product.In catalytically cracked gasoline, comprise more alkadienes usually, generally also use the method for catalytic hydrogenation to remove.Because crude oil price skyrockets and causes the rise of petrochemicals price, and subsequent technique is to improving constantly that material purity requires, and petroleum chemical industry is to the selectivity of load hydrogenation catalyst and actively also proposed more and more higher requirement.
Load hydrogenation catalyst is generally by carrier, main active component with help active component to form.Carrier is the skeleton that supports active component, the heat endurance that also can play and improve the active component utilization rate, improves catalyst, provides effect such as activated centre.Common carrier material has aluminium oxide, silica, molecular sieve, active carbon, magnesia, titanium oxide, diatomite or the like.Main active component is generally the metallic element with high active of hydrogenation catalysis, is generally VIII family element, as Pd, Pt, Ni etc.Help active component to can be used for regulating activity of such catalysts or selectivity, auxiliary agent commonly used such as Cu, Ag, Au etc.
Load hydrogenation catalyst adopts dipping-roasting method production more.The solution (mostly being salting liquid) that will contain active component fully contacts with the carrier for preparing, and makes active constituent loading to carrier, and dry back roasting under high temperature makes slaine be decomposed into corresponding oxide.Catalyst after the roasting need lead to hydrogen reducing before use just can be used for hydrogenation reaction.Make to prepare catalyst in this way, maximum problem is that the high temperature in the roasting process may cause the active component sintering, makes the degradation of catalyst.
At present, remove calcination steps in many new method for preparing catalyst, used methods such as electronation instead active component is directly reduced under temperate condition, obtained to have more high activity and optionally catalyst.U.S. Pat 5968860 discloses a kind of hydrogenization catalyst preparation method that the gaseous ethene legal system is equipped with vinylacetate that is used for.With Pd, Au active constituent loading behind carrier, use sodium borohydride, hydrazine or formic acid at room temperature to finish reduction process, and in preparation process, introduce the ultrasonic wave radiation, the selectivity of the hydrogenation catalyst of acquisition is higher than the sample that uses the conventional method preparation.Introduced a kind of preparation method of supported metal catalyst among the Chinese patent CN 1579618.This method is a thermal source with the microwave radiation, is reducing agent and protective agent with the polyalcohol, can prepare the polynary supported catalyst of load capacity at 1wt%～99wt% fast, and the metallic particle diameter can be controlled in 0.5～10nm.
Chinese patent CN 1511634 has announced a kind of preparation of ethylene through selective hydrogenation of acetylene Preparation of catalysts method.Use the high energy active specy in the radio frequency plasma and load on Modification on Al
2O
3On the effect of palladium series catalyst precursor, can under temperate condition, catalyst be activated rapidly.The catalyst of preparation has advantages such as low temperature active height, ethylene selectivity height, green oil yield poorly, good stability.Use the ultraviolet light reducing process to prepare hydrogenation catalyst in the U.S. Pat 6268522, its active component is eggshell state and distributes, and shell thickness can be controlled by conditions such as ultraviolet wavelength, radiant power, radiated times.The catalyst of preparation shows good activity and selectivity in the gaseous ethene legal system is equipped with the reaction of vinylacetate.
Above-mentioned improving one's methods omitted calcination steps, makes the performance of catalyst be improved, but also exists many deficiencies, is in particular in: (1) needs to use a large amount of compounds as reducing agent or protective agent, makes the production cost raising and causes the wasting of resources; (2) ultra-violet radiation and plasma penetration ability require height to equipment, only can be used for Preparation of catalysts in a small amount, are difficult to realize industrial production.
In sum, provide a kind of novel method for preparing catalyst, prepare have excellent activity and optionally load type metal catalyst be very necessary.
Summary of the invention
The object of the present invention is to provide a kind of load type metal catalyst.
Concrete, load type metal catalyst of the present invention comprises carrier and the metal active constituent that is carried on the carrier, wherein said catalyst makes by the reducing loaded metal active constituent precursor on carrier of ionising radiation, described metal active constituent is the simple substance attitude, and the average diameter of described metal active constituent particle is less than 8nm.
Preferably, the metal active constituent described in the catalyst of the present invention comprises:
A) be selected from a kind of metal in group VIII element and the IB family element, its content is the 0.01wt%～20wt% of carrier gross weight;
B) optional, at least a metal that is selected among group VIII, IB family, Bi, Sb, In, Cs and the Rb, its content is the 0wt%～20wt% of carrier gross weight;
And it is components b) a) inequality with component.
In catalyst of the present invention, active component is present in the catalyst with the metal simple-substance form; Component is main active component a), is selected from a kind of in group VIII element or the IB family element, preferred Pd, Pt, Ni, more preferably Pd; Also preferably add second kind or more kinds of metal active constituent, as Ag, Au, Cu, Bi, Sb, In, Cs, Rb or be different from component group VIII element a).In addition, also can add the active component that helps of other adjusting catalyst performances commonly used in the hydrogenation catalyst, as alkali metal or alkaline-earth metal, halogen etc.
Preferably, in catalyst of the present invention, described metal active constituent content a) is the 0.01wt%～10wt% of carrier gross weight, more preferably 0.01wt%～1wt%; Active component b) content is the 0wt%～10wt% of carrier gross weight.
The carrier of preferred catalyst of the present invention is selected from Al
2O
3, SiO
2, TiO
2, one or both and two or more mixtures in MgO, diatomite, active carbon and the molecular sieve; More preferably described carrier be shaped as that granular, spherical, sheet, tooth are spherical, special-shaped strip such as strip or clover; More preferably using specific area is 1～200m
3The carrier of/g.
Load hydrogenation catalyst of the present invention uses ionising radiation to reduce described metal active constituent precursor and obtains the active component of metal simple-substance attitude, preferred described ionising radiation comprises one of the following method that is selected from, use high-energy ray source irradiation, described active component precursor be reduced to the metal simple-substance of described active component:
A) load is had the carrier of described active component precursor use to contain the solution-wet of free radical scavenger after, irradiation under wetting state is preferably under vacuum or inert atmosphere;
B) load there is the carrier adding of described active component precursor contain in the solution of free radical scavenger irradiation under the solution submerged state;
C) described carrier adding is contained in the maceration extract of free radical scavenger and described active component precursor irradiation under the solution submerged state.
Method a) and b) in, at first use active component precursor maceration extract impregnated carrier, add the solution contain free radical scavenger again, it is under moisture state or the solution submerged state carries out irradiation; At method c) in, be that carrier directly is immersed in the maceration extract that contains free radical scavenger and active component precursor.
Ionising radiation of the present invention is gamma-rays, X ray or electron beam, and radiographic source is optional
60Co (γ source),
137Cs (γ source), x-ray source or electron accelerator (electron beam), preferred
60Co, x-ray source or electron accelerator, more preferably
60Co.
The absorbed dose rate in the high-energy ray source that ionising radiation irradiation of the present invention is used is 10-10000Gy/min.
Active component precursor of the present invention is the metallic compound of described active component correspondence, can be selected from chloride, nitrate, acetate, sulfate and metallo-organic compound.
Described active component precursor can load on the carrier by a step dipping or step impregnation; Described active component precursor is formulated as solution in advance, and solvent is selected from one or more the mixing in water, hydrochloric acid, nitric acid, acetate, the alcohols; Preferred water.
The pH value of maceration extract can impact particle size and the distribution situation that makes the catalyst activity component.Thereby, can come to carry out appropriate regulation by the pH that regulates maceration extract making activity of such catalysts and selectivity.In catalyst of the present invention, the pH scope of control maceration extract is 2-10, preferred 2-7.The pH value of maceration extract can use solution such as NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate or sodium acid carbonate to regulate.
Preferably before catalyst of the present invention carries out the irradiation reduction step, use fixative to handle the carrier of described carrier or described load active component precursor; Wherein said fixative is an alkali compounds, the aqueous solution such as preferred NaOH, potassium hydroxide, sodium acid carbonate, sodium carbonate and ammoniacal liquor etc.Generally can adopt the mode of spraying that fixative is mixed with carrier, its objective is that making soluble metal salt change insoluble metallic compound into is fixed on carrier surface.
Described free radical scavenger is selected from one or more in alcohols and the formic acid, preferably a kind of in methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol and formic acid.
Another object of the present invention provides a kind of preparation method of load type metal catalyst of the present invention.
Particularly, may further comprise the steps:
(1) one or more described active component precursors is loaded to carrier surface;
(2) add free radical scavenger, use ionising radiation to reduce described active component precursor under wetting state or under the solution submerged state.
In preparation method of the present invention, described active component precursor can use dipping method commonly used in the Preparation of Catalyst to load on the carrier, as spraying, incipient impregnation, supersaturation impregnating.When using the supersaturation infusion process, the active component precursor in the maceration extract then should be determined the volume and the active component concentration of maceration extract according to the absorption ratio if can not adsorb fully by suppressed by vector, satisfies pre-provisioning request with proof load to the active component content on the carrier.
When comprising two or more active component in the catalyst, can adopt a step infusion process or a step impregnation method.Use a step infusion process, several active component precursors can be dissolved in the same solution carrier is flooded.For the active component precursor that can not be formulated in the same solution, then can adopt the method for step impregnation, several active component precursors are mixed with solution respectively carrier is flooded, may need behind each dipping carrier drying.
Before using preparation method's irradiation reduction of the present invention, also can make the metal active constituent precursor change oxide into soaked carrier roasting at high temperature, carry out the irradiation reduction again.
Because effects of ionizing radiation is when aqueous solvent, water is generated hydrated electron (e by radiolysis
Aq -), hydrogen atom (H), hydroxy radical products such as (OH).E wherein
Aq -Be strong reductant, most of metal ion can be reduced to simple substance.The metallic that is reduced is stable in carrier surface growth and final suppressed by vector, forms the metallic with catalytic activity.But H, OH that the water radiolysis generates are oxidative free radical, can make the metallic atom that has just generated in the radiation reduction process heavily be oxidized to ion.Take place for fear of this reaction, need to add a certain amount of free radical scavenger in system at predose, free radical scavenger is generally alcohols, can react with H or OH, generate the pure free radical of reproducibility, thereby improve the radiation reduction yield of metal ion, improve the reducing power of system.
In preparation method of the present invention, free radical scavenger can be selected from alcohols and the derivative thereof of C1-C5, as ethanol, ethylene glycol, isopropyl alcohol, tert-butyl alcohol or derivatives thereof etc., also can use formic acid; Preferred isopropyl alcohol and ethylene glycol.When specifically adding free radical scavenger, use its aqueous solution usually, the concentration of control radicals scavenging agent solution can realize the present invention in certain scope.In containing the solution of free radical scavenger, the volume ratio of free radical scavenger and water optional 1%～50%, preferred 5%～20%.
At using method c) when flooding, can determine the adding dosage of free radical scavenger by the volume ratio of free radical scavenger-maceration extract, the concentration of solution is got final product in above-mentioned scope.
When using preparation method's radiation of the present invention to reduce, described carrier can be wetting state or solution submerged state.In the present invention, described wetting state or solution submerged state are not had special requirement, those skilled in the art can judge by prior art and operating experience.Usually can adopt following method: when wetting state irradiation, in advance that soaked carrier is fully wetting in the mixed solution of free radical scavenger and water, filtering redundant solution afterwards is with carrier irradiation in vacuum or inert gas (as nitrogen) of surface wettability.When solution submerged state irradiation, soaked carrier is packed in the container, add the mixed solution submergence carrier of free radical scavenger and water after, seal irradiation.For the carrier that uses supersaturation infusion process dipping, can directly in maceration extract, add a certain amount of free radical scavenger, seal irradiation after mixing and make solution submergence carrier.
According to the difference of composition, pH and the radiation parameter of maceration extract, make active component be reduced the required optional 5～100kGy of absorbed dose of radiation fully.Those skilled in the art can determine to make active component to be reduced required suitable dose fully easily.
Optional 10～the 10000Gy/min of absorbed dose rate of preferred irradiation reduction, preferred 20～100Gy/min.
Described ionising radiation reduction process can be carried out under room temperature or low temperature, preferably at room temperature carries out.
In preparation method of the present invention, preferably the carrier after the ionising radiation reduction is used appropriate amount of deionized water to wash 1～6 time to remove foreign ion, fully dry afterwards.Drying can be carried out under air atmosphere or vacuum, preferably carries out under air atmosphere.Optional 50～200 ℃ of baking temperature, preferred 50～100 ℃.Optional 5～48 hours of drying time, preferred 5～24 hours.Promptly obtain catalyst of the present invention after the drying.
Load type metal catalyst of the present invention can use x-ray photoelectron power spectrum (XPS) to analyze, and confirms that the activity of such catalysts component is the simple substance form; Can use transmission electron microscope (TEM) to observe the particle diameter and the particle diameter distribution situation of particles of active components; Can use SEM (SEM) to observe the distribution situation of active component on carrier surface and cross section.
A further object of the present invention is described catalyst to be applied in the hydrogenation or selective hydrogenation of petrochemical industry in producing the selectively removing of alkynes and alkadienes in the product that is selected from one of ethene, propylene, butylene and gasoline that is preferably applied to produce in steam cracking, catalytic cracking or the thermal cracking process.
Active component uniform particle diameter in the catalyst of the present invention is at hydrotreatment or the selectively removing to components such as alkene, alkynes, particularly at C
2, C
3, C
4The selective hydrogenation of cracking cut removes in the alkynes and shows good activity and selectivity.
Load type metal catalyst of the present invention and preparation method thereof has the following advantages:
(1) catalyst activity component of the present invention is the metal simple-substance attitude, and the particles of active components uniform particle diameter is compared with the catalyst of conventional method preparation and to be had higher activity and selectivity;
(2) because activity of such catalysts component of the present invention exists with the simple substance form, can directly come into operation, not need to use hydrogen to reduce in advance;
(3) the present invention uses ionising radiation irradiation to be impregnated with the carrier of active component precursor, promptly use normal temperature radiation reducing process to replace the high-temperature roasting-hydrogen reducing in the conventional method, avoided the active component sintering that causes in the roasting process, thereby make catalyst activity component particle uniform particle diameter of the present invention, and simplified preparation technology, lowered the discharging of energy consumption and gas pollutant;
(4) because in the catalyst preparation process, condition such as the kind of carrier state, free radical scavenger and content, radiation reducing agent dose rate all can exert an influence to particle size and the distribution that makes the catalyst activity component when kind of carrier, maceration extract pH, dip time, dipping method, irradiation.Therefore, use method of the present invention to prepare catalyst, to be adapted to the needs of multiple choices hydrogenation reaction easily by the above-mentioned preparation condition of regulation and control with different qualities.
(5) used gamma-rays, X ray or the electron beam of ionising radiation irradiation reducing process of the present invention has stronger penetration capacity, can be used for the production of a large amount of catalyst.
Description of drawings
Fig. 1 is the Pd/Al of embodiment 1
2O
3The XPS spectrum figure of catalyst.From figure, can clearly be seen that, on the 335.19eV position, have the absworption peak of simple substance Pd (3d).
Fig. 2 is to use the Pd/Al of prior art for preparing
2O
3The XPS spectrum figure of catalyst.Pd on the catalyst exists with the PdO form, and its Pd (3d) absworption peak position is 336.76eV.
The specific embodiment
Following examples are to more detailed the describing for example of the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
Get 83.3mg PdCl
2, be dissolved in the 25ml 1.0mol/L hydrochloric acid, use deionized water to be diluted to 100ml, using 1mol/L NaOH solution to regulate its pH is 3.0.Take by weighing Al
2O
3Carrier 100g adds PdCl
2Solution leaves standstill dipping 20min.In maceration extract, add isopropyl alcohol 10ml afterwards, evenly disperse hypsokinesis to go out excess solution, carrier is used under vacuum
60The Co gamma emitter is irradiation 15h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained described catalyst A, and its Pd content is 0.032wt%, and the Pd average diameter is 3.3nm.
Embodiment 2
Get 83.3mg PdCl
2, be dissolved in the 25ml 1.0mol/L hydrochloric acid, use deionized water to be diluted to 100ml, using 1mol/L NaOH solution to regulate its pH is 3.0.Take by weighing Al
2O
3Carrier 100g adds PdCl
2Solution leaves standstill dipping 20min.In maceration extract, add isopropyl alcohol 10ml afterwards, after evenly disperseing carrier and solution are moved in the test tube, seal the back and use
60The Co gamma emitter is irradiation 15h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained described catalyst B, and its Pd content is 0.033wt%, and average diameter is 5.4nm.
Embodiment 3
Change free radical scavenger into ethanol, all the other are operated all with embodiment 1, obtain described catalyst C, and its Pd content is 0.032wt%, and average diameter is 3.5nm.
Embodiment 4
Close rate changes 80Gy/min into during with irradiation, and all the other are operated all with embodiment 1, obtain described catalyst D, and its Pd content is 0.031wt%, and average diameter is 3.8nm.
Comparative Examples
Get 83.3mg PdCl
2, be dissolved in the 25ml 1.0mol/L hydrochloric acid, use deionized water to be diluted to 100ml, using 1mol/L NaOH solution to regulate its pH is 3.0.In dry beaker, take by weighing Al
2O
3Carrier 100g adds PdCl
2Solution leaves standstill dipping 20min.Make PdCl at 550 ℃ of following roasting 8h after the carrier drying
2Decompose, use hydrogen purge to make it reduction in 2 hours down at 150 ℃ afterwards, obtain catalyst E, wherein Pd content is 0.032wt%.
Above-mentioned catalyst A-the E of preparation is carried out cracking of ethylene unstripped gas front-end hydrogenation reaction experiment, and reaction condition is as follows:
The 1ml catalyst is loaded in the stainless steel tube reactor that internal diameter is 7.8mm, use nitrogen replacement after, feed reactor after unstripped gas joined hydrogen.The composition of unstripped gas (molar fraction) is a methane 36.5%, ethane 8%, and ethene 38%, propylene 10%, acetylene 0.8%, propine 0.4%, allene 0.2%, and a small amount of butylene, butadiene, pentane etc., hydrogen content (with respect to unstripped gas) is about 16%.The experiment air speed is 10000h
-1
Above-mentioned catalyst is estimated the selection hydrogenation performance of ethene and propine allene (MAPD), and each catalyst is ethene to acetylene hydrogenation under different temperatures and MAPD is hydrogenated to propylene conversion and corresponding selectivity is listed in table 1.The computational methods of the conversion ratio of ethene and MAPD (Conversion) and selectivity (Selectivity) are:
Experimental result shows, uses the catalyst of radiation method of reducing preparation of the present invention, and for acetylene hydrogenation reaction and MAPD hydrogenation reaction, under the close situation of selectivity, its activity is far above Comparative Examples.
Table 1 embodiments of the invention and Comparative Examples catalytic perfomance
Claims (13)
1. load type metal catalyst, comprise carrier and the metal active constituent that is carried on the carrier, it is characterized in that: described catalyst makes by the reducing loaded metal active constituent precursor on carrier of ionising radiation, described metal active constituent is the simple substance attitude, and the average diameter of described metal active constituent particle is less than 8nm.
2. catalyst according to claim 1 is characterized in that: described metal active constituent comprises:
A) be selected from a kind of metal in group VIII element and the IB family element, its content is the 0.01wt%～20wt% of carrier gross weight;
B) optional, at least a metal that is selected among group VIII, IB family, Bi, Sb, In, Cs and the Rb, its content is the 0wt%～20wt% of carrier gross weight;
And it is components b) a) inequality with component.
3. catalyst according to claim 2 is characterized in that: described metal active constituent content a) is the 0.01wt%～10wt% of carrier gross weight; Active component b) content is the 0wt%～10wt% of carrier gross weight.
4. catalyst according to claim 1 is characterized in that described carrier is selected from Al
2O
3, SiO
2, TiO
2, one or both and two or more mixtures in MgO, diatomite, active carbon and the molecular sieve.
5. according to the described catalyst of one of claim 1-4, it is characterized in that using the high-energy ray source to carry out ionising radiation irradiation, described active component precursor is reduced to the metal simple-substance of described active component, irradiance method is selected one of following method:
A) load is had the carrier of described active component precursor use to contain the solution-wet of free radical scavenger after, irradiation under wetting state is preferably under vacuum or inert atmosphere;
B) load there is the carrier adding of described active component precursor contain in the solution of free radical scavenger irradiation under the solution submerged state;
C) described carrier adding is contained in the maceration extract of free radical scavenger and described active component precursor irradiation under the solution submerged state.
6. catalyst according to claim 5 is characterized in that used high-energy ray source is gamma-rays, X ray or electron beam.
7. catalyst according to claim 6, the absorbed dose rate that it is characterized in that used high-energy ray source is 10-10000Gy/min.
8. catalyst according to claim 5, it is characterized in that described active component precursor be described active component correspondence be selected from chloride, nitrate, acetate, sulfate and metal-organic metallic compound.
9. catalyst according to claim 8 is characterized in that described active component precursor can load on the carrier by a step dipping or step impregnation; Described active component precursor is formulated as solution in advance, and solvent is selected from one or more the mixing in water, hydrochloric acid, nitric acid, acetate, the alcohols.
10. catalyst according to claim 5 is characterized in that: use fixative to handle the carrier of described carrier or described load active component precursor; Wherein said fixative is an alkali compounds, preferred NaOH, potassium hydroxide, sodium acid carbonate or ammoniacal liquor.
11. catalyst according to claim 5 is characterized in that: described free radical scavenger is selected from one or more in alcohols and the formic acid, preferably a kind of in methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol and formic acid.
12. the described Preparation of catalysts method of one of claim 1-11, it may further comprise the steps:
(1) one or more described active component precursors is loaded to carrier surface;
(2) add free radical scavenger, use ionising radiation to reduce described active component precursor under wetting state or under the solution submerged state.
13. the described catalyst of one of claim 1-11 is applied in the hydrogenation or selective hydrogenation of petrochemical industry in producing, the selectively removing of alkynes and alkadienes in the product that is selected from one of ethene, propylene, butylene and gasoline that is preferably applied to produce in steam cracking, catalytic cracking or the thermal cracking process.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810227414A CN101733172A (en) | 2008-11-26 | 2008-11-26 | Supported metal catalyst, preparation method thereof and use thereof |
| KR1020117014269A KR101605055B1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| EP09828542.2A EP2368629B1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| US13/131,226 US20110288353A1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| RU2011126193/04A RU2514438C2 (en) | 2008-11-26 | 2009-11-26 | Metal-loaded catalyst and method for preparation thereof |
| BRPI0920995-6A BRPI0920995B1 (en) | 2008-11-26 | 2009-11-26 | LOADED METAL CATALYST AND PREPARATION METHOD OF THE SAME. |
| PCT/CN2009/001332 WO2010060281A1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| US14/885,838 US9643172B2 (en) | 2008-11-26 | 2015-10-16 | Metal loaded catalyst and preparation method thereof |
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